Liquid, method for producing the same and use thereof

文档序号：689537 发布日期：2021-04-30 浏览：9次中文

阅读说明：本技术液体 (Liquid, method for producing the same and use thereof ) 是由 J·W·德波尔 K·玛金 Y·P·A·罗洛夫森 R·哈格于 2019-07-04 设计创作，主要内容包括：本发明涉及包含不饱和树脂、过氧化物以及能够通过三个、四个或五个氮原子螯合至少一个过渡金属离子的螯合剂的液体的固化和硬化,所述螯合剂可以各自任选地与一个或两个过渡金属离子络合,通常是铁或锰离子。本发明还提供了制备相关组合物、由这种液体的固化产生的组合物、以及包含两种或多种物理上彼此分离的组合物的相关试剂盒的方法和制剂,当混合时,试剂盒可用于提供可固化的液体。(The present invention relates to the curing and hardening of liquids comprising an unsaturated resin, a peroxide and a chelating agent capable of chelating at least one transition metal ion through three, four or five nitrogen atoms, which chelating agent may each optionally be complexed with one or two transition metal ions, typically iron or manganese ions. The invention also provides methods and formulations for making related compositions, compositions resulting from the curing of such liquids, and related kits comprising two or more compositions physically separated from one another, which kits, when mixed, can be used to provide curable liquids.)

1. A composition, comprising:

(i)5 to 95% w/w of an unsaturated resin;

(ii)0.001 to 10% w/w peroxide;

(iii)0.00001 to 0.2% w/w of a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV):

X((CY₂)_nR1)₃ (I)

(R1(CY₂)_n)₂X(CY₂)_nR2-Q-R2(CY₂)_nX((CY₂)_nR1)₂ (I-B)

wherein:

the or each X is N or CZ, wherein Z is selected from hydrogen, optionally substituted by C_1-6Alkyl substituted C_1-24Alkyl, optionally substituted by C_1-6Alkyl substituted C_1-24alkyl-O-C_1-24Alkyl, optionally substituted by C_1-6Alkyl substituted C_1-24alkyl-O-C_6-10Aryl, optionally substituted by C_1-6Alkyl substituted C_1-24alkyl-O-C_6-10Aryl radical C_1-24Alkyl, optionally substituted by C_1-6Alkyl-substituted hydroxy C_1-24Alkyl, optionally substituted by C_1-6Alkyl substituted C_6-10Aryl and optionally substituted by C_1-6Alkyl substituted C_6-10Aryl radical C_1-24An alkyl group;

if X is CZ, n is 0; if X is N, then N is 1;

each Y is independently selected from H, CH₃、C₂H₅And C₃H₇；

each-R1 is independently selected from-CY₂N(C_1-24Alkyl radical)₂；-CY₂NR3 in which R3 and the nitrogen atom N to which it is attached represent optionally substituted by one or more C_1-6Alkyl-substituted heterocycloalkyl radicals bound to the adjacent CY via the nitrogen atom N₂Partially connecting; or represents optionally substituted by C_1-6An alkyl-substituted heteroaryl group selected from pyridin-2-yl, pyrazin-2-yl, quinolin-2-yl, pyrazol-1-yl, pyrazol-3-yl, pyrrol-2-yl, imidazol-4-yl, benzimidazol-2-yl, pyrimidin-2-yl, 1, 2, 3-triazol-1-yl, 1, 2, 3-triazol-2-yl, 1, 2, 3-triazol-4-yl, 1, 2, 4-triazol-1-yl, 1, 2, 4-triazol-3-yl, thiazol-2-yl, and thiazol-4-yl;

if present, the two-R2-moieties are independently selected from optionally C_1-6An alkyl-substituted heteroarylene group selected from the group consisting of pyridine-2, 6-diyl, pyrazine-2, 6-diyl, quinoline-2, 8-diyl, pyrazole-1, 3-diyl, pyrrole-2, 5-diyl, imidazole-1, 4-diyl, imidazole-2, 5-diyl, pyrimidine-2, 6-diyl, 1, 2, 3-triazole-2, 5-diyl, 1, 2, 4-triazole-1, 3-diyl, 1, 2, 4-triazole-3, 5-diyl and thiazole-2, 4-diyl;

q represents a bridge selected from the group consisting of: c_1-6Alkylene moiety, C_6-10Arylene moieties or containing one or two C_1-3Alkylene unit and one C_6-10Part of an arylene unit, the bridge optionally being independently selected C_1-24Alkyl and OH groups are substituted one or more times;

wherein:

each-R5 is independently selected from-CH₂N(C_1-24Alkyl radical)₂、-CH₂NR9 or optionally substituted by C_1-6An alkyl-substituted heteroaryl group selected from pyridin-2-yl, pyrazin-2-yl, quinolin-2-yl, pyrazol-1-yl, pyrazol-3-yl, pyrrol-2-yl, imidazol-2-yl, imidOxazol-4-yl, benzimidazol-2-yl, pyrimidin-2-yl, 1, 2, 3-triazol-1-yl, 1, 2, 3-triazol-2-yl, 1, 2, 3-triazol-4-yl, 1, 2, 4-triazol-1-yl, 1, 2, 4-triazol-3-yl, thiazol-2-yl, and thiazol-4-yl;

the or each-R6 independently represents-R10-R11;

the or each-R7 and the or each-R8 each independently represent hydrogen, or are selected from C_1-18Alkyl radical, C_6-10Aryl radical, C_5-10Heteroaryl group, C_6-10Aryl radical C_1-6Alkyl and C_5-10Heteroaryl C_1-6Alkyl radicals, each of which may optionally be substituted by C_1-6Alkyl substitution, provided that-R7 or-R8 may not be one of the allowed possibilities for-R5;

the or each-RI 0 independently represents optionally substituted C_1-6Alkyl substituted C_1-6An alkylene group;

the or each-R11 independently represents hydrogen, C_1-6Alkyl, optionally substituted by C_1-6Alkyl substituted C_6-10Aryl, optionally substituted by C_1-6Alkyl substituted C_5-10Heteroaryl, optionally substituted by C_1-6Alkyl substituted C_5-10Heteroaryl C_1-6Alkyl, CY₂N(C_1-24Alkyl radical)₂Radical or CY₂NR9；

each-NR 9 independently represents a moiety in which R9 and the nitrogen atom to which it is attached N represent optionally substituted by one or more C_1-20An alkyl-substituted heterocycloalkyl group attached to the remainder of the chelating agent through the nitrogen atom N; and

q2 represents a bridge selected from the group consisting of: c_1-6Alkylene moiety, C_6-10Arylene moieties or containing one or two C_1-3Alkylene unit and one C_6-10Part of an arylene unit, the bridge optionally being independently selected C_1-24Alkyl and OH groups are substituted one or more times;

wherein:

each D is independently selected from the group consisting of: thiazol-2-yl, thiazol-4-yl, pyrazin-2-yl, quinolin-2-yl, pyrazol-3-yl, pyrazol-1-yl, pyrrol-2-yl, imidazol-4-yl, benzimidazol-2-yl, pyrimidin-2-yl, 1, 2, 4-triazol-3-yl, 1, 2, 4-triazol-1-yl, 1, 2, 3-triazol-2-yl, and 1, 2, 3-triazol-4-yl, each of which may be optionally substituted with one or more groups independently selected from the group consisting of: -F, -Cl, -Br, -OH, -OC₁-C₄Alkyl, -NH-CO-H, -NH-CO-C₁-C₄Alkyl, -NH₂、-NH-C₁-C₄Alkyl and-C₁-C₄An alkyl group;

each E is independently selected from the group consisting of: pyridin-2-yl, thiazol-4-yl, pyrazin-2-yl, quinolin-2-yl, pyrazol-3-yl, pyrazol-1-yl, pyrrol-2-yl, imidazol-2-yl, imidazol-4-yl, benzimidazol-2-yl, pyrimidin-2-yl, 1, 2, 4-triazol-3-yl, 1, 2, 4-triazol-1-yl, 1, 2, 3-triazol-2-yl, and 1, 2, 3-triazol-4-yl, each of which may be optionally substituted with one or more groups independently selected from the group consisting of: -F, -Cl, -Br, -OH, -OC₁-C₄Alkyl, -NH-CO-H, -NH-CO-C₁-C₄Alkyl, -NH₂、-NH-C₁-C₄Alkyl and-C₁-C₄An alkyl group;

r1 and the or each R2 is independently selected from the group consisting of: c₁-C₂₄Alkyl radical, C_6-10Aryl radical C₁-C₆Alkyl radical, C_6-10Aryl radical, C₅-C₁₀Heteroaryl C₁-C₆Alkyl, each of which may be optionally substituted with one or more groups independently selected from the group consisting of: -F, -Cl, -Br, -OH, -OC₁-C₄Alkyl, -NH-CO-H, -NH-CO-C₁-C₄Alkyl, -NH₂、-NH-C₁-C₄Alkyl and-SC₁-C₄An alkyl group; and CH₂CH₂N(R8)(R9)，

Wherein N (R8) (R9) is selected from the group consisting of: two (C)_1-44Alkyl) amino; two (C)_6-10Aryl) amino, wherein each aryl group is independently optionally substituted with one or more C_1-20Alkyl substitution; two (C)_6-10Aryl radical C_1-6Alkyl) amino, wherein each aryl group is independently optionally substituted with one or more C_1-20Alkyl substitution; NR7 in which R7 and the nitrogen atom N attached thereto represent optionally substituted by one or more C_1-20An alkyl-substituted heterocycloalkyl group attached through the nitrogen atom N to the remainder of R1 or R2; bis (heterocycloalkyl C)_1-6Alkyl) amino, wherein each heterocycloalkyl is independently optionally substituted with one or more C_1-20Alkyl substitution; and bis (heteroaryl C)_1-6Alkyl) amino, wherein each heteroaryl is independently optionally substituted by one or more C_1-20Alkyl substitution;

r3 and R4 are independently selected from hydrogen, C₁-C₈Alkyl radical, C₁-C₈alkyl-O-C₁-C₈Alkyl radical, C₆-C₁₀Aryloxy radical C₁-C₈Alkyl radical, C₆-C₁₀Aryl radical, C₁-C₈Hydroxyalkyl radical, C₆-C₁₀Aryl radical C₁-C₆Alkyl and C₅-C₁₀Heteroaryl C₁-C₆Alkyl and- (CH)₂)_0-4C (O) OR5, wherein R5 is independently selected from: hydrogen, C₁-C₈Alkyl and C_6-10An aryl group;

x is selected from C ═ O, - [ C (R6)₂]_0-3-, wherein each R6 is independently selected from hydrogen, hydroxy, C₁-C₄Alkoxy and C₁-C₄An alkyl group;

wherein:

-R¹、-R²、-R³and-R⁴Each independently represents-H, -C_1-24Alkyl radical, C_6-10An aryl group or a group containing a heteroatom capable of coordinating to a metal ion;

f represents a methylene or ethylene group, wherein one or more hydrogen atoms may optionally be independently replaced by C_1-24Alkyl or C_6-10Aryl substitution; and

f' represents ethylene or n-propylene, wherein one or more hydrogen atoms may optionally be independently replaced by C_1-24Alkyl or C_6-10Aryl substitution.

2. The composition of claim 1, wherein:

the chelating agent is of formula (I), (I-B), (II-B) or (II-C), wherein:

the or each X is N or CZ, wherein Z is selected from H, methyl, hydroxymethyl, methoxymethyl and benzyl;

each Y, if present, is H;

each-R1 is pyridin-2-yl, imidazol-4-yl, benzimidazol-2-yl, each optionally substituted with one or more C_1-6Alkyl substitution;

both-R2-moieties, if present, are pyridine-2, 6-diyl, imidazole-1, 4-diyl, or imidazole-2, 5-diyl;

each R5 is optionally substituted pyridin-2-yl;

the or each-R7 is selected from-H, methyl and benzyl;

the or each-R8 is selected from-H, C_1-18Alkyl and benzyl;

the or each-R10 is-CH₂-；

The or each R11 is optionally substituted pyridin-2-yl, imidazol-4-yl or benzimidazol-2-yl, for example unsubstituted pyridin-2-yl; and

each Q and Q2, if present, is selected from-CH₂CH₂-、-CH₂CH₂CH₂-and-CH₂CHOHCH₂-, 1, 2-phenylene and 1, 4-phenylene, each of which is optionally substituted by C_1-6Alkyl substitution, e.g. each of Q and Q2, if present, is-CH₂CH₂-；

Or wherein the chelating agent is of formula (III) or (III-B), wherein:

each D, if present, is the same and is thiazol-2-yl or thiazol-4-yl;

each E, if present, is pyridin-2 yl;

in the formula (III), one of R1 and R2 is C₁-C₈Alkyl and the other is C₅-C₁₀Heteroaryl group CH₂Or CH₂CH₂N (R8) (R9), wherein-N (R8) (R9) is selected from-NMe 2, -NEt2, -N (i-Pr)2,And

in formula (III-B), each R2 is the same and is pyridin-2-ylmethyl or CH₂CH₂N (R8) (R9), wherein-N (R8) (R9) is selected from-NMe₂、-NEt₂、-N(i-Pr)₂、And

-Q-, if present, is selected from-CH₂CH₂-、-CH₂CH₂CH₂-and-CH₂CHOHCH₂-；

X is C ═ O or C (OH)₂(ii) a And

r3 and R4 are selected from-C (═ O) OR5, wherein R5 is selected from C1-C4 alkyl); or

Wherein the chelating agent is of formula (V):

wherein:

each of-R¹Independently is-H, -C_1-24Alkyl, -C_6-10Aryl or pyridin-2-ylmethyl wherein aryl or pyridyl is optionally substituted by C_1-4Alkyl substitution;

-R²represents-H or-CH₃(ii) a And

-R³and-R⁴Each independently is-H, -C_1-24Alkyl radical, -C_6-10Aryl or pyridin-2-ylmethyl wherein aryl or pyridyl is optionally substituted by C_1-4The substitution of the alkyl group is carried out,

for example, wherein:

-R¹each independently is-H, -C_1-24Alkyl or pyridin-2-ylmethyl wherein pyridyl is optionally substituted by C_1-4Alkyl substitution;

-R²represents-H or-CH₃(ii) a And

-R³and-R⁴Each independently is-H, -C_1-24Alkyl or pyridin-2-ylmethyl wherein pyridyl is optionally substituted by C_1-4Alkyl substitution.

3. The composition of claim 1 wherein the chelating agent is selected from the group consisting of 6-dimethylamino-1, 4-bis (pyridin-2-ylmethyl) -6-methyl-1, 4-diazepane, 6-amino-1, 4-bis (pyridin-2-ylmethyl) -6-methyl-1, 4-diazepane, 1, 4, 6-trimethyl-6- { N- (pyridin-2-ylmethyl) -N-methylamino } -1, 4-diazepane, 6-amino-1, 4, 6-trimethyl-1, 4-diazepane, 6-dimethylamino-1, 4, 6-trimethyl-1, 4-diazepane, 1, 4, 6-trimethyl-6- (pyridin-2-ylmethyl) amino-1, 4-diazepane, 6- { N, N-bis (pyridin-2-ylmethyl) amino } -1, 4, 6-trimethyl-1, 4-diazepane, 6- { N- (pyridin-2-ylmethyl) -N-methylamino } -1, 4-bis (pyridin-2-ylmethyl) -6-methyl-1, 4-diazepane, N-methyl-N- (pyridin-2-ylmethyl) -bis (pyridin-2-yl) methylamine, N-benzyl-N- (pyridin-2-yl-methyl) -bis (pyridin-2-yl) 2-yl) methylamine, N-dimethyl-bis (pyridin-2-yl) methylamine, N-methyl-N- (pyridin-2-yl) ylmethyl-1, 1-bis (pyridin-2-yl) -1-aminoethane, N-benzyl-N- (pyridin-2-yl-methyl-1, 1-bis (pyridin-2-yl) -1-aminoethane, N-methyl-N- (pyridin-2-ylmethyl-1, 1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane), N-benzyl-N- (pyridin-2-ylmethyl-1, 1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane, N, N, N-tris (pyridin-2-ylmethyl) amine, tris (pyridin-2-yl) methane, N-methyl-N- (pyridin-2-ylmethyl) -bis (pyridin-2-yl) methylamine, N-benzyl-N- (pyridin-2-yl-methyl) -bis (pyridin-2-yl) methylamine, dimethyl 2, 4-bis (thiazol-2-yl) -3-methyl-7- (pyridin-2-ylmethyl) -3, 7-diazabicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-4-yl) -3-methyl-7- (pyridin-2-yl) -3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, dimethyl 9, 9-dihydroxy-3-methyl-2, 4-bis (thiazol-2-yl) -7- (1- (N, N-dimethylamine) -eth-2-yl) -3, 7-diaza-bicyclo [3.3.1] nonane-1, 5-dicarboxylate, dimethyl 9, 9-dihydroxy-3-methyl-2, 4-bis (thiazol-4-yl) -7- (1- (N, n-dimethylamine) -eth-2-yl) -3, 7-diaza-bicyclo [3.3.1] nonane-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-2-yl) -3- (pyridin-2-ylmethyl) -7-methyl-3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-4-yl) -3- (pyridin-2-ylmethyl) -7-methyl-3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, dimethyl 9, 9-dihydroxy-2, 4-bis (thiazol-2-yl) -3- (1- (N, N-dimethylamine) -eth-2-yl) -7-methyl-3, 7-diaza-bicyclo [3.3.1] nonane-1, 5-dicarboxylate, dimethyl 9, 9-dihydroxy-2, 4-bis (thiazol-4-yl) -3- (1- (N, N-dimethylamine) -eth-2-yl) -7-methyl-3, 7-diaza-bicyclo [3.3.1] nonane-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-2-yl) -3, 7-dimethyl-3, 7-diaza-bicyclo [3.3.1] nonan-9-one-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-4-yl) -3, 7-dimethyl-3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, 1, 2-bis {1, 5-bis (methoxycarbonyl) -3- (pyridin-2-ylmethyl) -9-oxo-2, 4-bis (pyridin-2-yl) -3, 7-diazabicyclo [3.3.1] non-7-yl } ethane, 1, 3-bis {1, 5-bis (methoxycarbonyl) -3- (pyridin-2-ylmethyl) -9-oxo-2, 4-bis (pyridin-2-yl) -3, 7-diazabicyclo [3.3.1] non-7-yl } propane, 1, 2-bis {1, 5-di (methoxycarbonyl) -3-methyl-9-oxo-2, 4-bis (pyridin-2-yl) -3, 7-diazabicyclo [3.3.1] non-7-yl } ethane and 1, 3-bis {1, 5-bis (methoxycarbonyl) -3-methyl-9-oxo-2, 4-bis (pyridin-2-yl) -3-diazabicyclo [3.3.1] non-7-yl } propane.

4. The composition of claim 3 wherein the chelating agent is selected from the group consisting of N, N, N-tris (pyridin-2-yl-methyl) amine, N-methyl-N- (pyridin-2-ylmethyl) -bis (pyridin-2-yl) methylamine, 1, 4, 6-trimethyl-6- { N- (pyridin-2-ylmethyl) -N-methylamino } -1, 4-diazepane, 6-amino-1, 4-bis (pyridin-2-ylmethyl) -6-methyl-1, 4-diazepane, dimethyl 2, 4-bis (thiazol-2-yl) -3-methyl-7- (pyridin-2-ylmethyl) -3, 7-diazabicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, 2, 4-bis (thiazol-4-yl) -3-methyl-7- (pyridin-2-ylmethyl) -3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-2-yl) -3- (pyridin-2-ylmethyl) -7-methyl-3, 7-diazabicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, 2, 4-bis (thiazol-4-yl) -3- (pyridin-2-ylmethyl) -7-methyl-3, 7-diazabicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, 1, 2-bis {1, 5-bis (methoxycarbonyl) -3- (pyridin-2-ylmethyl) -9-oxo-2, 4-bis (pyridin-2-yl) -3, 7-diazabicyclo [3.3.1] non-7-yl } ethane, and 1, 3-bis {1, 5-bis (methoxycarbonyl) -3- (pyridin-2-ylmethyl) -9-oxo-2, 4-bis (pyridin-2-yl) -3, 7-diazabicyclo [3.3.1] non-7-yl } propane.

5. The composition according to any one of claims 1-4, wherein the resin is an unsaturated polyester resin or a vinyl ester resin, such as an acrylic resin.

6. The composition of any one of claims 1-5, comprising a complex comprising the chelating agent and a transition metal ion selected from the group consisting of transition metal ions of iron, manganese, vanadium, and copper, such as ions of iron and manganese.

7. A method of preparing a composition according to any one of claims 1 to 6, the method comprising contacting a first formulation comprising a peroxide, a second formulation comprising a chelating agent according to any one of claims 1 to 4; and a third formulation comprising an unsaturated resin.

8. The method of claim 7, wherein the method is for preparing the complex-containing formulation of claim 6, and wherein the contacting comprises contacting with the transition metal ion source, optionally wherein the second formulation comprises a complex of a chelating agent.

9. The method of claim 8, wherein:

said peroxide and unsaturated resin being contained in the same formulation, which is in contact with said second formulation and said source of said transition metal ion; or

The chelating agent and peroxide are contained in the same formulation, the formulation comprising less than 0.001% by weight of ions of each of iron, manganese, vanadium, cobalt and copper, the formulation being in contact with the third formulation and the source of transition metal ions; or

Said chelating agent and said unsaturated resin are contained in the same formulation, said formulation further comprising said source of transition metal ions, said formulation being contacted with said first formulation.

10. The method of claim 8 or 9, wherein the second formulation comprises a mixture of the chelating agent and a salt of iron or manganese, such as an optional hydrated salt selected from the group consisting of: MnCl₂、FeCl₂、FeCl₃、MnBr₂、Mn(NO₃)₂、Fe(NO₃)₃、MnSO₄、FeSO₄、(Fe)₂(SO₄)₃Mn (acetylacetone)₂Fe (acetylacetone)₂Mn (acetylacetone)₃Fe (acetylacetone)₂、Mn(R₄COO)₃、Fe(R₄COO)₃、Mn(R₄COO)₂、Fe(R₄COO)₂Wherein each R is₄Independently is C₁-C₂₄An alkyl group.

11. A composition produced by curing a composition as defined in claim 6, or capable of being produced by a method according to any one of claims 8 to 10.

12. A formulation comprising a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) and (IV) according to any one of claims 1 to 4 and an unsaturated resin or peroxide.

13. A kit comprising a first formulation which is a composition as defined in any one of claims 1 to 6 and which comprises less than 0.001% by weight of ions of each of at least iron, manganese, vanadium, cobalt and copper, and separately a second formulation which comprises transition metal ions selected from the group consisting of iron, manganese, vanadium and copper ions.

14. A kit comprising a first formulation comprising an unsaturated resin, a chelating agent as defined in any of claims 1 to 4 and a transition metal ion selected from the group consisting of iron, manganese, vanadium and copper ions, and separately a second formulation comprising a peroxide.

15. A kit, comprising:

(i) a first formulation comprising an unsaturated resin;

(ii) a second formulation comprising a complex comprising one or two transition metal ions selected from the group consisting of iron, manganese, vanadium and copper ions and a chelating agent as defined in any one of claims 1 to 4; and

(iii) a third formulation comprising a peroxide.

Technical Field

The present invention relates to the curing and hardening of liquids comprising an unsaturated resin, a peroxide and a chelating agent capable of chelating at least one transition metal ion through three, four or five nitrogen atoms, which chelating agent may each optionally be complexed with one or two transition metal ions, typically iron or manganese ions. The invention also provides methods and formulations for making related compositions, compositions resulting from the curing of such liquids, and related kits comprising two or more compositions physically separated from one another, which kits, when mixed, can be used to provide curable liquids.

Prior Art

Thermosetting resins, including unsaturated polyester and vinyl ester types, are commonly used in a variety of manufacturing applications, such as casting materials, fiber reinforcements, and coatings. These resins are typically dissolved in an unsaturated vinyl monomer (often referred to as a reactive diluent), such as styrene, to promote crosslinking (curing) and reduce viscosity. The resins are typically cured by a free radical copolymerization mechanism with peroxide or azo type initiators to form solid articles. The accelerator is used to accelerate the decomposition of the peroxide.

Peroxide type initiators are commonly used to cure unsaturated resins. The initiator is typically dissociated with the accelerator using heat, UV light, or at ambient temperature (typically about 18 ℃ to about 25 ℃) to form the free radicals needed to initiate polymerization. Accelerators are commonly used with peroxides for, but not limited to, ambient cure applications: peroxides are commonly used to cure unsaturated resins at higher temperatures.

The current state of the art for ambient curing of unsaturated polyester and vinyl ester resins is the use of peroxides which are accelerated by the presence of metal compounds, in particular cobalt salts (known as accelerators). Cobalt naphthenate and cobalt octoate are the most widely used accelerators. The peroxides most commonly used in combination with cobalt accelerators are ketone peroxides, hydroperoxides and peresters. The use of Methyl Ethyl Ketone Peroxide (MEKP) is particularly prevalent. Modified acrylic resins containing a large amount of styrene mixed with acrylate monomers can also be cured by the MEKP/cobalt system.

Their ability to activate a variety of different initiators and compatibility with a variety of resin systems has led to the widespread use of cobalt accelerators. However, cobalt-containing promoters have become undesirable due to their health and environmental impact: cobalt soaps (including cobalt octoate) may need to be registered as carcinogens. Cobalt promoters also have other technical disadvantages. These disadvantages include poor reactivity at low temperatures (< 15 ℃), staining of the resin with color (cobalt octoate and naphthenic acid are very dark), and poor reactivity with acrylic and methacrylic monomers, especially in acrylic resins. Although molding applications are conducted at ambient temperatures above 15 ℃, ambient temperatures can be well below 15-40 ℃, particularly in the winter season, which is a typical working temperature range for ambient curing using cobalt accelerators.

When used as a primary accelerator at typical concentrations of about 0.02% w/w (metal basis), the color from the cobalt accelerator can affect the color of the cured gel coat or molded composite. Lower cobalt promoter levels can be used but the gel and peak exotherm times are longer and the peak exotherm temperatures are lower.

Finally, as a means of meeting recent government regulations to limit styrene emissions in open molding equipment, low volatility acrylic and methacrylic monomers have been incorporated into unsaturated polyesters and vinyl ester resins. However, the amount of styrene substitution is generally limited by the poor copolymerization of most acrylate and methacrylate moieties with maleate and fumarate moieties in the unsaturated polyester backbone and the ability of the cobalt promoted MEKP system to efficiently form acrylic monomer radicals. The latter is particularly evident in acrylic systems where the cobalt accelerated MEKP system is almost unreactive in the absence of styrene.

There is therefore a continuing need in connection with the curing of unsaturated resins, in particular unsaturated polyesters and vinyl esters, in particular in the production of cured gel coats and molded composites, to develop a process which on the one hand avoids the use of cobalt as accelerator and on the other hand maintains good curing properties.

WO 2008/003492 a1(DSM IP assemblies b.v.) discloses a resin composition comprising an unsaturated polyester resin or vinyl ester resin, a peroxide, a metal salt, such as iron or manganese, as an accelerator and a base.

WO 2008/003496 a1(DSM IP assests BV) discloses a resin composition comprising an unsaturated polyester resin or vinyl ester resin, a manganese compound and a thiol-containing compound and a peroxide compound having the formula ROOH, wherein R is hydrogen or an optionally substituted alkyl group.

WO 2008/003495 a1(DSM IP assests b.v.) discloses an unsaturated polyester resin composition comprising an unsaturated polyester resin, a manganese compound, a1, 3-dioxo compound and a base. The resin composition may be cured with a peroxide.

WO2011/083309 a1(Unilever plc) describes a liquid curable medium comprising an unsaturated resin composition, a peroxide and an iron or manganese complex containing a specific tridentate, tetradentate, pentadentate or hexadentate chelating agent. The chelating agents mentioned are bispidon ligands: based on 9-oxo-3, 7-diazabicyclo [3.3.1]Of nonanes [3.3.1]Bicyclic nitrogen donor ligands and related structures, wherein the 9-oxo moiety may be substituted by- [ C (Rx)₂]_0-3-, wherein each Rx is independently hydrogen, hydroxy, C_1-4Alkoxy or C_1-4An alkyl group. The bispidon feature described in this publication-the bispidon-type catalyst is described as the most active promoter of all the promoter classes tested-there are two 2-pyridyl groups attached to a carbon atom, one of the two pendant groups being a symmetric nitrogen atom (at position 3 or 7). An example of such a bispidon cited in this publication is WO 00/60045A 1 (Procter)&Gamble Company) and WO02/48301A 1 and WO 03/104379A 1(Unilever plc et al).

WO 2013/083630 a1(DSM assests b.v.) describes the use of iron-bispidon complexes to accelerate peroxide initiated free radical copolymerization of resin compositions comprising unsaturated polyester resins and vinyl esters. Although direct bis (2-pyridyl) substitution of the bicyclic scaffold is not mandatory, bis (2-pyridyl) substitution is preferred, with exemplary bispidons having this substitution pattern.

WO 2013/083632 a1(DSM ipassests BV) describes a multicomponent system comprising a first component comprising a resin composition comprising a specific hydroxy-functional unsaturated polyester and/or vinyl resin, a reactive diluent, a bispidon chelating agent and an iron salt and/or complex; a specific isocyanate compound; and a peroxide compound. Although direct bis (2-pyridyl) substitution of the bicyclic scaffold is not mandatory, it is preferred that one or two direct 2-pyridyl substituents be present, more preferably two direct 2-pyridyl substituents be present, and no other substituents be present, these positions being described as preferred substituents. In addition, exemplary bispidons do not contain the substituent bis (2-pyridyl) substituent on two of the four carbon atoms adjacent to the common N-3 or N-7 nitrogen atom.

While these aforementioned publications do bring promoters not based on cobalt into the art, in part in view of the need in the art for technology that seeks to replace cobalt-based systems, it would be at least advantageous to develop alternative additional systems for curing unsaturated resins, particularly with (liquid) peroxides. The present invention solves this problem.

Summary of The Invention

We have found that transition metal ion-containing compounds, particularly compounds containing iron, manganese, copper or vanadium (typically iron or manganese, more typically iron), which contain specific chelating agents capable of chelating at least one such transition metal ion through three, four or five nitrogen atoms, are effective at lower concentrations as accelerators for curing unsaturated resins in the presence of peroxides. This allows toxic cobalt accelerators to be reduced or avoided so that the resulting composition exhibits less color disturbance and less dependence on temperature to promote curing.

Furthermore, the efficacy of the chelating agents described herein as a component of the cure accelerator is surprising. In particular, we have found that transition metal complexes comprising bispidon ligands with heteroaryl groups other than 2-pyridyl directly attached to the bicyclic moiety within the bispidon catalyze curing of unsaturated resins faster than expected in the presence of peroxide, in view of close structural similarity to analogous complexes comprising bis (2-pyridyl) bispidon. In addition, the present invention is based on the recognition of the ability to bridge bispidons in these reactions. Still further, we have found that transition metal complexes comprising other specific chelating agents capable of chelating from three to five nitrogen donor atoms have promoter activity (towards peroxide-initiated curing of unsaturated resins), comparable to or even better than those containing bispidon chelating agents. This activity is also surprising in view of the efficacy of the promoter containing bispidon as previously described in the art.

The invention is particularly applicable to curing media that require a reduced amount of cobalt accelerator while still functioning effectively. Indeed, the present invention allows cobalt promoters to be avoided.

Thus, viewed from a first aspect, the invention provides a composition comprising:

(i)5 to 95% w/w of an unsaturated resin;

(ii)0.001 to 10% w/w peroxide;

(iii)0.00001 to 0.2% w/w of a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV):

X((CY₂)_nR1)₃ (I)

(R1(CY₂)_n)₂X(CY₂)_nR2-Q-R2(CY₂)_nX((CY₂)_nR1)₂ (I-B)

wherein:

the or each X is N or CZ, wherein Z is selected from hydrogen, orQuilt selection area C₁-₆Alkyl substituted C_1-24Alkyl, optionally substituted by C_1-6Alkyl substituted C_1-24alkyl-O-C_1-24Alkyl, optionally substituted by C_1-6Alkyl substituted C_1-24alkyl-O-C_6-10Aryl, optionally substituted by C_1-6Alkyl substituted C_1-24alkyl-O-C_6-10Aryl radical C_1-24Alkyl, optionally substituted by C_1-6Alkyl-substituted hydroxy C_1-24Alkyl, optionally substituted by C_1-6Alkyl substituted C_6-10Aryl and optionally substituted by C_1-6Alkyl substituted C_6-10Aryl radical C_1-24An alkyl group;

if X is CZ, n is 0; if X is N, then N is 1;

each Y is independently selected from H, CH₃、C₂H₅And C₃ H₇；

if present, the two-R2-moieties are independently selected from optionally C₁-₆An alkyl-substituted heteroarylene group selected from the group consisting of pyridine-2, 6-diyl, pyrazine-2, 6-diyl, quinoline-2, 8-diyl, pyrazole-1, 3-diyl, pyrrole-2, 5-diyl, imidazole-1, 4-diyl, imidazole-2, 5-diyl, pyrimidine-2, 6-diyl, 1, 2, 3-triazole-2, 5-diyl, 1, 2, 4-triazole-1, 3-diyl, 1, 2, 4-triazole-3, 5-diyl and thiazole-2, 4-diyl;

q represents a group selected fromA bridge of the group consisting of: c_1-6Alkylene moiety, C_6-10Arylene moieties or containing one or two C_1-3Alkylene unit and one C_6-10Part of an arylene unit, the bridge optionally being independently selected C_1-24Alkyl and OH groups are substituted one or more times;

wherein:

each-R5 is independently selected from-CH₂N(C_1-24Alkyl radical)₂、-CH₂NR9 or optionally a bridge of the group consisting of: c_1-6An alkyl-substituted heteroaryl group selected from pyridin-2-yl, pyrazin-2-yl, quinolin-2-yl, pyrazol-1-yl, pyrazol-3-yl, pyrrol-2-yl, imidazol-4-yl, benzimidazol-2-yl, pyrimidin-2-yl, 1, 2, 3-triazol-1-yl, 1, 2, 3-triazol-2-yl, 1, 2, 3-triazol-4-yl, 1, 2, 4-triazol-1-yl, 1, 2, 4-triazol-3-yl, thiazol-2-yl, and thiazol-4-yl;

the or each-R6 independently represents-R10-R11;

the or each-R10 independently represents optionally substituted by C_1-6Alkyl substituted C_1-6An alkylene group;

wherein:

each E is independently selected from the group consisting of: pyridin-2-yl, thiazol-4-yl, pyrazin-2-yl, quinolin-2-yl, pyrazol-3-yl, pyrazol-1-yl, pyrrol-2-yl, imidazol-4-yl, benzimidazol-2-yl, pyrimidin-2-yl, 1, 2, 4-triazol-3-yl, 1, 2, 4-triazol-1-yl, 1, 2, 3-triazol-2-yl, and 1, 2, 3-triazol-4-yl, each of which may be optionally independently selected from the group consisting ofSubstituted with one or more groups of (a): -F, -Cl, -Br, -OH, -OC₁-C₄Alkyl, -NH-CO-H, -NH-CO-C₁-C₄Alkyl, -NH₂、-NH-C₁-C₄Alkyl and-C₁-C₄An alkyl group;

x is selected from C ═ O, - [ C (R6)₂]_0-3-, wherein each R6 is selected from hydrogen, hydroxy, C₁-C₄Alkoxy and C₁-C₄An alkyl group;

wherein:

-R¹、-R²、-R³and-R⁴Each independently represents-H, -C_1-24Alkyl radical, C_6-10An aryl group or a group containing a heteroatom capable of coordinating to a metal ion;

f represents a methylene or ethylene group, wherein one or more hydrogen atoms may optionally be independently replaced by C_1-24Alkyl or C_6-10Aryl substitution; and

f' represents ethylene or n-propylene, wherein one or more hydrogen atoms may optionally be independently replaced by C_1-24Alkyl or C_6-10Aryl substitution.

The chelating agent in the composition of the first aspect may or may not be part of a complex comprising one or two transition metal ions, typically ions of iron, manganese, copper or vanadium, more typically ions of iron or manganese and typically iron.

Viewed from a second aspect, the invention provides a process for the preparation of a composition according to the first aspect of the invention, the process comprising contacting a first formulation comprising a peroxide, a second formulation comprising a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV); and a third formulation comprising an unsaturated resin. The chelating agent in the second formulation may or may not be part of a complex comprising one or two transition metal ions, typically selected from iron, manganese, copper or vanadium, more typically iron or manganese, especially typically iron.

Viewed from a third aspect, the present invention provides a composition obtainable by curing a composition according to the first aspect of the invention, or obtainable by curing a composition according to the second aspect of the invention.

Related formulations and kits are also provided.

Thus viewed from a fourth aspect the invention provides a formulation comprising a chelating agent of formulae (I), (IB), (II-B), (II-C), (III-B) and (IV) as defined in relation to the first aspect of the invention, and an unsaturated resin or peroxide.

Viewed from a fifth aspect, the invention provides a kit comprising a first formulation which is a composition according to the first aspect of the invention or obtainable according to the second aspect of the invention and comprises less than 0.001% by mass of ions of at least iron, manganese, vanadium, cobalt and copper and separately a second formulation selected from transition metal ions of the group consisting of iron, manganese, vanadium and copper ions.

Viewed from a sixth aspect the present invention provides a kit comprising a first formulation comprising an unsaturated resin, a chelating agent of formulae (I), (I-B), (II-B), (II-C), (III-B) and (IV) as defined in relation to the first aspect of the invention and a transition metal ion selected from the group consisting of iron, manganese, vanadium and copper ions, and separately a second formulation comprising a second formulation of a peroxide.

Viewed from a seventh aspect, the present invention provides a kit comprising:

(i) a first formulation comprising an unsaturated resin;

(iii) a third formulation comprising a peroxide.

Other aspects of embodiments of the invention will become apparent from the following discussion.

Detailed Description

As outlined above, the present invention is based in part on the following recognition: complexation of the transition metal ion (particularly, although not necessarily, iron or manganese ion, often, but not necessarily, iron ion) with a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) is effective to accelerate curing of the unsaturated resin by the peroxide.

The present invention therefore relates to accelerators for curing unsaturated polyester resins, vinyl ester resins, including acrylic and methacrylic (═ meth) acrylic resins, together with peroxide-type initiators. The promoters are typically based on iron/manganese complexes of the nitrogen donor chelating agents described herein. Also disclosed are curable resin compositions comprising the above accelerators and curing methods using these accelerators. These resin compositions exhibit good curing properties and do not require the use of cobalt accelerators. The invention further relates to gel coats and molded composites prepared from such unsaturated polyesters, vinyl esters and acrylic resins.

The unsaturated resin present in the composition of the first aspect of the invention and other related aspects and embodiments of the invention is typically an unsaturated polyester resin or vinyl ester resin as is well known in the art. It is to be understood that more than one type of resin (e.g., a mixture of resins) may be used in accordance with the present invention. The resin may contain a reactive diluent for crosslinking. Unsaturated polyester resins and vinyl ester resins useful according to the present invention are often subdivided in the art into different categories as described below.

Ortho-position resin: these are based on phthalic anhydride, maleic anhydride or fumaric acid and glycols, for example ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, dipropylene glycol, tributylene glycol, neopentyl glycol or hydrogenated bisphenol A. Those derived from 1, 2-propanediol are typically used in combination with a reactive diluent such as styrene.

Different resins: typically made from isophthalic, maleic or fumaric acid and a glycol. These resins typically contain higher levels of reactive diluent than conventional resins.

Bisphenol a-fumarate: these are based on ethoxylated bisphenol a and fumaric acid.

Chloride resin: are resins prepared from chlorine/bromine-containing anhydrides or phenols in the preparation of UP resins.

Vinyl ester resin: are frequently used because of their hydrolysis resistance and excellent mechanical properties, having unsaturated sites only in the terminal positions, which are introduced by the reaction of the epoxy resin with (meth) acrylic acid. Typical types of epoxy resins include bisphenol a, pivalic acid, tetraphenylethane, cycloaliphatic, tetrabromobisphenol a, and the like. A common vinyl ester resin is an acrylic resin, which will be described in more detail below.

Similar to the iso-and ortho-resins are unsaturated polyester resins containing terephthalic acid. In addition to these kinds of resins, so-called dicyclopentadiene (DCPD) resins can also be considered as unsaturated polyester resins. As used herein, a vinyl ester resin may be a (meth) acrylate functional resin. Likewise, vinyl ester urethane resins (also referred to as urethane methacrylate resins) are considered to be vinyl ester resins. Preferably, the vinyl ester resin used in the present invention is a resin obtained by esterifying an epoxy resin with (meth) acrylic acid or (meth) acrylamide.

All of these resins, which may be used in the context of the present invention, may be modified according to methods known in the art, e.g. by the method of the present invention. For obtaining a lower acid, hydroxyl or anhydride value, or to become more flexible by incorporating flexible units in the backbone, etc.

Also, other reactive groups that can be cured by reaction with peroxides may be present in the resin, such as reactive groups derived from itaconic acid, citraconic acid, and allyl groups, among others. Thus, according to the present invention, compositions and formulations comprising the unsaturated resins referred to herein (typically the polyester resins or vinyl ester resins described above) may comprise a solvent. The solvents may be inert to the resin system, or they may be reactive with the resin during the curing step. The latter are called reactive diluents, their use being noteworthy in the context of the present invention. Thus, the unsaturated resins used according to various aspects of the present invention are typically present in a composition or formulation that also comprises a reactive diluent. Examples of suitable reactive diluents are styrene, vinyltoluene, divinylbenzene, methyl methacrylate, diallyl phthalate, alpha-methylstyrene, triallyl cyanurate, (meth) acrylate, N-vinylpyrrolidone and N-vinylcaprolactam. Mixtures of reactive diluents, particularly mixtures comprising styrene, may be used. The amount of styrene and/or other reactive diluent may be up to 60% w/w, but is typically between 25% w/w and 35% w/w.

The unsaturated polyester resins and vinyl ester resins useful according to the present invention may be any type of such resins, but are generally selected from the group consisting of DCPD resins, isophthalic resins, phthalic resins and vinyl ester resins, or mixtures of the foregoing.

The composition according to the first aspect of the present invention typically has an acid number of from 0.001 to 300mg KOH/g resin composition. As used herein, the acid number of the resin composition is determined according to ISO 2114-2000 titration. Generally, the molecular weight of the unsaturated polyester resin is from 500 to 200.000 g/mol. As used herein, the molecular weight of the resin is determined using gel permeation chromatography according to ISO 13885-1. The composition according to the first aspect of the invention typically comprises less than 5% w/w water.

The acrylic resins useful according to the present invention may be selected from, for example, thermosetting acrylic resins or acrylic modified resins known in the art. Examples of the acrylic resin or acrylic-modified resin are listed below.

Acrylic resin: based on acrylic monomers, which generally comprise an acrylate or methacrylate function of general structure:

wherein R may be hydrogen, a linear, branched or cyclic aliphatic group and/or an aromatic group.

Acrylic monomers, also known as acrylate and methacrylate monomers, are typically synthesized from acrylic or methacrylic acid and an alcohol. In addition to standard side chains, special functional groups can also be added to the (meth) acrylate monomers by using appropriate functional alcohols. Examples include glycidyl methacrylate, t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, and the like, as well as hydroxy (meth) acrylates made from glycidyl esters of carboxylic acids.

Functional monomers related to methacrylic acid, acrylic acid and itaconic acid are also included in the vinyl monomers, such as the polyfunctional monomers 1, 4-butene dimethacrylate, ethylene glycol dimethacrylate, 1, 6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, bisphenol A dimethacrylate, ethoxylated bisphenol A dimethacrylate, trimethylolpropane triarylate, trimethylolpropane methacrylate and ethoxylated trimethylolpropane trimethacrylate.

Acrylic resins may also incorporate oligomeric acrylates, which are acrylated urethanes, epoxies, polyesters, polyethers, and acrylics. Oligomeric acrylates are formed by reacting acrylate functional monomers with primary or secondary functional groups on the oligomer. The acrylate functional monomer may be added directly to the oligomer or attached to the oligomer using a secondary difunctional monomer. For example, urethane acrylate oligomers are formed by reacting polyester or polyether polyol oligomers with diisocyanates (aliphatic or aromatic) and hydroxy (meth) acrylates. The epoxy acrylate oligomer is formed by reacting an epoxy resin with a carboxy functional (meth) acrylate. For example, the polyether oligomer may also be reacted with a carboxy-functional (meth) acrylate to form a polyethylene glycol dimethacrylate.

In addition, the acrylic resin may be prepared using pre-reacted monomer polymerization syrup obtained by polymerizing an acrylic monomer or copolymerizing a mixture of different acrylic monomers to a specific degree of polymerization (generally 10 to 60%). The polymerization is generally carried out at from 50 to 110 ℃ using a small amount of a polymerization initiator and optionally a chain transfer agent. The reaction was carried out to a predetermined viscosity, close to the degree of polymerization, and then cooled to room temperature. Optionally, the reaction is quenched by the addition of cold monomer containing polymerization inhibitor.

Acrylic modified resins are a wide variety of resins similar to oligomeric acrylates, except that the acrylic modified resins use a base resin with sufficient molecular weight and are therefore not considered oligomers. Examples of base resins include polyols, unsaturated polyols, polyesters, unsaturated dicyclopentadienyl polyesters, polyisocyanates (chain extended and/or polyfunctional), epoxy resins (bisphenol a, pivalate, and chain extended), and polyacids, which are typically the product of a polyol and a polycarboxylic acid or anhydride. The acrylic modified resin is formed by reacting the primary and/or secondary functional groups of the base resin directly with the functionalized acrylic monomer to produce primary and/or secondary (meth) acrylic double bonds on the base resin. Modification of the base resin with (meth) acrylic double bonds may also be achieved indirectly by initially reacting the primary and/or secondary functional groups of the resin with other di-or polyfunctional compounds, such as isocyanates, acids or anhydrides. In addition, the acrylic resin may be further modified by reacting the secondary functional group formed during the initial modification. Methods for preparing acrylic modified resins are well known to those skilled in the art.

Thus, the acrylic modified resin useful in the present invention may contain a solvent. The solvents may be inert to the resin system, or they may react with it during the curing step (i.e., reactive diluents). Reactive diluents are particularly preferred. The acrylic monomeric and/or oligomeric acrylates discussed above are examples of reactive diluents commonly used with acrylic modified resins. Alternatively, acrylic monomers may be copolymerized with styrene, vinyl toluene, divinyl benzene, acrylonitrile, vinyl acetate, vinyl esters of carboxylic acids, and the like in acrylic acid and acrylic acid modified resins.

Curing or crosslinking using acrylic monomers and/or oligomeric acrylates as reactive diluents further expands the definition of acrylic modified resins to include resins modified with allyl functionality introduced into the base resin by allyl glycidyl ether, trimethylolpropane diallyl ether, allyl pentaerythritol and related derivatives.

Compositions and formulations according to the present invention or otherwise described herein comprising an unsaturated resin typically further comprise one or more reactive diluents, typically in an amount of at least 5% w/w. As previously mentioned, amounts up to 60% w/w may be used, although amounts between 25% w/w and 35% w/w are typical. Such reactive diluents can be used to reduce the viscosity of unsaturated resins to improve handling properties, particularly in vacuum infusion, spray coating, and the like. However, it is to be understood that the amount of reactive diluent in the compositions and formulations according to the present invention or otherwise described herein is not critical and that useful amounts can be obtained by one skilled in the art without undue burden. Typically, the reactive diluent is a methacrylate and/or styrene.

Aspects of the invention feature the use of chelating agents of formula (I), (IB), (II-B), (II-C), (III-B) and (IV). Complexes comprising one of these chelating agents with one or more suitable transition metal ions (especially ions of iron, manganese, vanadium and copper, more typically iron and manganese) will accelerate the curing of unsaturated resins by peroxides, whereas this acceleration is not the case in the absence of suitable transition metal ions.

The nature of the chelating agents of formulae (I), (I-B), (II-B), (II-C), (III-B) and (IV) as defined above will now be described. It is to be understood that more than one such chelating agent may be used in accordance with various aspects of the present invention. Furthermore, one or more of these chelating agents may be used in combination with chelating agents described elsewhere, such as those described in WO2011/083309 a 1. However, only one type of chelating agent is generally used.

A chelant capable of chelating at least one transition metal ion through, for example, three nitrogen atoms refers to a multidentate chelant capable of chelating one or more transition metal ions by forming coordinate bonds with common transition metal ions through the three nitrogen atoms of the chelant, chelation as used herein and as a term generally in the art requires that three nitrogen atoms in the chelant coordinate to the same transition metal ion, typically (but not necessarily) an iron or manganese ion. Thus, the chelating agents useful in the present invention are at least tridentate. However, some of these chelants may have a tooth density greater than 3. For example, the chelating agents described herein capable of chelating at least one transition metal ion through three nitrogen atoms are hexadentate or heptadentate, capable of coordination through six or seven nitrogen atoms. However, for these chelating agents, chelation can still be achieved by forming coordinate bonds between the three nitrogen atoms and the common transition metal ion: for example, three of the six or seven nitrogen atoms in these hexadentate or heptadentate chelators may be chelated to the first transition metal ion, and the other three or four donor nitrogen atoms may be chelated to the second transition metal ion. This is typically achieved by a multidentate chelant whose two parts of the structure create two separate chelating regions, typically separated by a bridge, as explained and illustrated in more detail herein with reference to specific multidentate chelants useful in accordance with the present invention.

The chelating agents of the formulae (I), (I-B), (II-B), (II-C), (III-B) and (IV) are capable of chelating at least one transition metal ion through three, four or five nitrogen atoms, i.e. some chelating agents are capable of chelating at least one transition metal ion through three nitrogen atoms, other chelating agents are capable of chelating at least one transition metal ion through four nitrogen atoms, while others are capable of chelating at least one transition metal ion through five nitrogen atoms. Some of the chelating agents described herein, particularly those of formulae (I-B), (II-C), and (III-B), may be capable of chelating one transition metal ion through three nitrogen atoms and another transition metal ion through four nitrogen atoms. However, typically, in the case of such chelating agents capable of chelating two transition metal ions, each transition metal ion is chelated by the same number of nitrogen atoms, typically because the chelating agents involved are symmetric about the bridge (Q or Q2).

For the avoidance of doubt, while the overall tooth density of the chelants described herein may be greater than three to five, the phrase "chelants capable of chelating at least one transition ion through three nitrogen atoms" does not allow chelation through four (or more) or two (or less) nitrogen atoms. Likewise, the phrase "a chelating agent capable of chelating at least one transition ion through four nitrogen atoms" does not allow for chelation through five (or more) or three (or less) nitrogen atoms.

It will be appreciated that the chelating agent of formula (I-B) is in fact a dimer of the chelating agent of formula (I) wherein the moiety-R2-Q-R2-has replaced two R1 groups. Of the chelating agents of formulae (I) and (I-B), the chelating agent of formula (I) is more typical.

The following features, alone or in combination, are typical (but not essential) of chelating agents of formulae (I) and (I-B) within the context of the context in question (i.e. without conflict):

there are multiple parts with the same descriptor, e.g., X, Y, R1 and R2 with the same descriptor are the same part.

Each Y (if present) is H;

the or each X is selected from N and CZ, wherein Z is selected from hydrogen, optionally substituted by C_1-6Alkyl substituted C_1-24Alkyl, optionally substituted by C_1-6Alkyl substituted C_1-24alkyl-O-C_1-24Alkyl, optionally substituted by C_1-6Alkyl-substituted hydroxy C_1-24Alkyl, and optionally C_1-6Alkyl substituted C_6-10Aryl radical C_1-24Alkyl, especially wherein Z is hydrogen, C_1-24Alkyl or C_6-10Aryl radical C_1-24Alkyl, even more particularly wherein X is N, or X is CZ, wherein Z is hydrogen, C_1-18Alkyl or C_6-10An arylmethyl group;

x or each X is N or X is CZ, wherein Z is selected from H or CH₃Hydroxymethyl (CH)₂-OH), methoxymethyl (CH)₂OCH₃) And benzyl (CH)₂-C₆H₅)；

X or each X is N;

q is selected from-CH₂、-CH₂CH₂-、-CH₂CH₂CH₂-and-CH₂CHOHCH₂-, 1, 2-phenylene and 1, 4-phenylene, each of which is optionally substituted by C_1-6Alkyl substituted, Q is typically unsubstituted;

the two-R2-moieties are the same, e.g. pyridine-2, 6-diyl, imidazole-1, 4-diyl or imidazole-2, 5-diyl, typically pyridine-2, 6-diyl;

if any of the moieties-R1 is-CY₂N(C_1-24Alkyl radical)₂or-CY₂NR₃Is usually-CH₂N(C_1-24Alkyl radical)₂or-CH₂NR₃And said CY₂Or CH₂The nitrogen-containing group to which the groups are attached is selected from the group consisting of-NMe 2, -NEt2, -N (i-Pr)2,Anda group of (a);

each-R1 is optionally substituted pyridin-2-yl, imidazol-4-yl, benzimidazol-2-yl, thiazol-4-yl, more often optionally substituted pyridin-2-yl, especially each-R1 is unsubstituted pyridin-2-yl;

r1 or each R1 is the same;

according to a specific embodiment, the chelating agent of formula (I) may be N, N-tris (pyridin-2-yl-methyl) amine (TPA), which has been described, for example, in U.S. Pat. nos. 5,850,086(Que, jr. et al) and 6,153,576(Blum et al).

It will be appreciated that the chelating agents of formulae (II-B) and (II-C) are in fact dimers of the chelating agent of formula (II) wherein the bridge Q2 replaces the R8 or R7 group respectively. Of the chelating agents of the formulae (II), (II-B) and (II-C), the chelating agent of the formula (II) is most typical. Of the bridging chelators, the chelator of formula (II-B) is more typical than the chelator of formula (II-C). The following features, alone or in combination, are typical (but not essential) features of the chelating agents of formulae (II), (II-B) and (II-C) within the context of the context in question (i.e. without conflict):

when there are multiple parts with the same descriptor, for example R5, R6 (and within the definition of R6, R10 and R11), R7 and R8, the parts with the same descriptor are identical;

r5 is optionally substituted pyridin-2-yl, in particular unsubstituted pyridin-2-yl;

at-R5 is-CY₂N(C_1-24Alkyl radical)₂or-CY₂NR₃Is usually-CH₂N(C_1-24Alkyl radical)₂or-CH₂NR₃In embodiments of (1) and (CY)₂Or methylene (-CH)₂-) the attached nitrogen-containing group is selected from the group consisting of-NMe 2, -NEt2, -N (i-Pr)2,Anda group of (a);

r10-or each R10-is-CH₂-；

R11 or each R11 independently represents C_5-10Heteroaryl group, C_5-10Heteroaryl C_1-6Alkyl, -CY₂N(C_1-24Alkyl radical)₂or-CY₂NR9；

R11 or each R11 is selected from-H, C_1-5Alkyl, phenyl, -CY₂N(C_1-24Alkyl radical)₂、-CY₂NR9 or optionally substituted by C_1-6Alkyl-substituted heteroaryl selected from pyridin-2-yl, pyrazin-2-yl, quinolin-2-yl, pyrazol-1-yl, pyrazol-3-yl, pyrrol-2-yl, imidazol-4-yl, benzimidazol-2-yl, pyrimidin-2-yl, 1, 2, 3-triazol-1-yl, 1, 2, 3-triazol-2-yl, 1, 2, 3-triazol-4-yl, 1, 2, 4-triazol-1-yl, 1, 2, 4-triazol-3-yl, thiazol-2-yl, and thiazol-4-yl;

r11 or each R11 is selected from-H, phenyl, -CY₂N(C_1-8Alkyl radical)₂or-CY₂NR9, wherein R9 and the nitrogen atom N to which it is attached represent an unsubstituted heterocycloalkyl group, which is attached to the remainder of the chelating agent through nitrogen atom N;

r11 or each R11 is an optionally alkyl-substituted heteroaryl group, typically an optionally substituted pyridin-2-yl group, most typically an unsubstituted pyridin-2-yl group;

r11 or each R11 is selected from-CY₂N(C_1-24Alkyl radical)₂or-CY₂NR₃Part of (2), usually-CH₂N(C_1-24Alkyl radical)₂or-CH₂NR₃And said CY₂Or methylene (-CH)₂-) the attached nitrogen-containing group is selected from the group consisting of-NMe 2, -NEt2, -N (i-Pr)2,Anda group of (a);

r7 or each R7 and R8 or each R8 independently represents-H, or is selected from C_1-6Alkyl radical, C_6-10Aryl and C_6-10Aryl radical C_1-6The radical of an alkyl radical, each radical optionally being substituted by C_1-6Alkyl substitution;

-R7 or each-R7 is selected from-H, methyl and benzyl;

r8 or each R8 is typically selected from-H, methyl and benzyl, typically methyl and benzyl;

bridge Q2 is selected from-CH₂CH₂-、-CH₂CH₂CH₂-and-CH₂CHOHCH₂-, 1, 2-phenylene and 1, 4-phenylene, each of which is optionally substituted by C₁-₆Alkyl is substituted, and the bridge is usually unsubstituted, and is often-CH₂CH₂-or-CH₂CH₂CH₂-。

According to a particular embodiment, the chelating agent of formula (II) is N-methyl-N- (pyridin-2-yl-methyl) -bis (pyridin-2-yl) methylamine (MeN3py) or N-benzyl-N- (pyridin-2-yl-methyl) -bis (pyridin-2-yl) methylamine (BzN3py), both disclosed by Klopsra et al (Eur. J. Inorg. Chem., 4, Acone 856 (2004)). Other examples of chelating agents of formula (II) include: n, N-dimethyl-bis (pyridin-2-yl) methylamine, N-methyl-N- (pyridin-2-yl-methyl-1, 1-bis (pyridin-2-yl) -1-aminoethane, N-benzyl-N- (pyridin-2-yl-methyl-1, 1-bis (pyridin-2-yl) -1-aminoethane, N-methyl-N- (pyridin-2-ylmethyl) -1, 1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane and N-benzyl-N- (pyridin-2-yl-methyl) -1, 1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane.

It will be appreciated that each of the bridge-containing chelators of formulae (I-B), (II-B) and (II-C) is capable of chelating two transition metal ions. Such multidentate chelants, as well as other multidentate chelants described herein, are readily available to those skilled in the art.

Particularly suitable chelating agents according to class (I) or (II) are N, N-tris (pyridin-2-ylmethyl) amine, N-methyl-N- (pyridin-2-ylmethyl) -bis (pyridin-2-yl) methylamine or N-benzyl-N- (pyridin-2-ylmethyl) -bis (pyridin-2-yl) methylamine.

With regard to the chelating agent of formula (I-B), various examples have been disclosed in the literature, such as 1, 2-bis [ 2-bis (6-methylpyridin-2-yl) methyl) -pyridinyl-6-yl ] ethane (M Kodera et al, j.am. chem. soc., 121, 11006(1999)), 1, 2-bis [ 2-bis (6-methyl-pyridin-2-yl) (pyridin-6-yl) -1, 1, 1-ethyl ] ethane (M Kodera et al, angelw.chem., int.ed.engl., 43334(2004)), 1, 2-bis [ 2-bis (pyridin-2-ylmethyl) aminomethyl ] -pyridin-6-yl ] ethane (M Kodera et al, angelw.chem., int.ed.engl., vol., 44, page 7104 (2005). KD Karlin et al (inorg. chem.33, 4625(1994) and j.am. chem.soc., 117, 12498(1995)) have described ethylene bridged TPA chelators (the ethylene bridge is linked at the 5-position on the pyridin-2-yl group).

With respect to the chelating agent of formula (II-B), the skilled person will recognize that, for example, N- (pyridin-2-yl-methyl) -bis (pyridin-2-yl) methylamine (N3py) (synthesis described by G Roelfes et al (j.am. chem. soc., 122, 11517-11518(2000)) may be reacted with 1, 2-dibromoethane, e.g. to give 1, 2-bis (N- (pyridin-2-yl-methyl) -bis (pyridin-2-yl) methylamine) -ethane, a synthesis of a bridged TACN chelating agent similar to that described by KO Schaefer et al (supra) or a method described by M klopsra et al (supra) involves reacting N3py with benzyl chloride to give BzN3 py.

With respect to the chelating agent of formula (II-C), the skilled person will recognize that, for example, N-methyl-N- (pyridin-2-yl-methyl) -bis (pyridin-2-yl) methylamine (MeN3py), the synthesis of which is described by M Klopstra et al (supra), can be reacted with BuLi at low temperatures and then with dibromoethane to produce a bridged chelating agent, similar to the synthesis of MeN4py and BzN4py described elsewhere (see, e.g., examples 1 and 2 of EP 0909809 a 2).

It will be appreciated that the chelating agent of formula (III-B) is in fact a dimer of the chelating agent of formula (III) in which two R1 groups are partially-Q-substituted. Of the chelating agents of formulae (III) and (III-B), the chelating agent of formula (III) is more typical. Such chelating agents (i.e., chelating agents of formulae (III) and (III-B)) are examples of bispidons.

The following features, taken alone or in combination, are typical (but not required) features of bispidon where the context permits (i.e., without conflict):

each D group being unsubstituted or substituted by one or more, usually one C₁-C₄Alkyl substitution;

each D group is identical;

each D group is optionally substituted thiazol-2-yl or thiazol-4-yl;

each D group is unsubstituted thiazol-2-yl or thiazol-4-yl;

each E group is the same;

each E group is optionally substituted pyridin-2-yl, optionally substituted thiazol-2-yl or optionally substituted thiazol-4-yl;

each E group is unsubstituted pyridin-2-yl, unsubstituted thiazol-2-yl or unsubstituted thiazol-4-yl;

each E group is unsubstituted pyridin-2-yl;

q is selected from-CH₂CH₂-、-CH₂CH₂CH₂-and-CH₂CHOHCH₂-, each of which is optionally substituted by C_1-6Alkyl substitution;

q is unsubstituted-CH₂CH₂-、-CH₂CH₂CH₂-or-CH₂CHOHCH₂-；

Q is unsubstituted-CH₂CH₂CH₂-or-CH₂CHOHCH₂-；

For formula (III), each R1 and R2 group is independently selected from C₁-C₂₄Alkyl radical, C₆-C₁₀Aryl radical, C₆-C₁₀Aryl radical C₁-C₆Alkyl radical, C₅-C₁₀Heteroaryl group CH₂And CH₂CH₂N (R8) (R9), wherein-N (R8) (R9) is selected from-NMe₂、-NEt₂、-N(i-Pr)₂、And

for formula (III), at any R1 or R2 group is independently C₁-C₂₄Alkyl radical, C₆-C₁₀Aryl or C₆-C₁₀Aryl radical C₁-C₆In the case of alkyl, it is generally independently selected from C₁-C₁₈Alkyl and C₆-C₁₀Aryl radical C₁-C₆Alkyl, even more typically independently selected from: c₁-C₈Alkyl and C₆-C₁₀Aryl radical CH₂；

For formula (III), at any R1 or R2 independently is C₅-C₁₀Heteroaryl group CH₂In the case of radicals, which (and usually also R1) are preferably selected from pyridin-2-ylmethyl, pyrazin-2-ylmethyl, quinolin-2-ylmethyl, pyrazol-1-methyl, pyrazol-3-ylmethyl, pyrrol-2-ylmethyl, imidazol-4-ylmethyl, benzimidazol-2-ylmethyl, pyrimidin-2-ylmethyl, 1, 2, 3-triazol-1-ylmethyl, 1, 2, 3-triazol-2-ylmethyl, 1, 2, 3-triazol-4-ylmethyl, 1, 2, 4-triazol-3-ylmethyl, 1, 2, 4-triazol-1-ylmethyl and thiazol-2-ylmethyl, typically pyridin-2-ylmethyl, quinolin-2-ylmethyl, imidazol-2-ylmethyl, thiazol-2-ylmethyl, and thiazol-4-ylmethyl;

for formula (III), one of the R1 and R2 groups (very often R2 in particular) is usually C₁-C₂₄Alkyl or C_6-10Aryl radical C₁-C₆Alkyl, and the other of the R1 and R2 groups (especially often R1) is C₅-C₁₀Heteroaryl group CH₂Group or CH₂CH₂N (R8) (R9), wherein-N (R8) (R9) is selected from-NMe₂、-NEt₂、-N(i-Pr)₂、And

for formula (III), one of the R1 and R2 groups (especially often R2) is most typically C₁-C₁₈Alkyl, more preferably C₁-C₁₂Alkyl, even more preferably C₁-C₈Alkyl, most preferably CH₃(ii) a The other of the R1 or R2 groups (especially often R1) is typically an optionally substituted pyridin-2-ylmethyl group, most typically unsubstituted pyridin-2-ylmethyl group, or is selected from CH₂CH₂N (R8) (R9), wherein-N (R8) (R9) is selected from-NMe 2, -NEt₂、-N(i-Pr)₂、And

for formula (III), R1 is different from R2, thus R1 is typically pyridin-2-ylmethyl, R2 is typically methyl; or R1 is methyl, R2 is pyridin-2-ylmethyl;

for formula (III-B), each R2 group is independently selected from C₁-C₂₄Alkyl radical, C₆-C₁₀Aryl radical, C_6-10Aryl radical C₁-C₆Alkyl radical, C₅-C₁₀Heteroaryl group CH₂And CH₂CH₂N (R8) (R9), wherein-N (R8) (R9) is selected from-NMe₂、-NEt₂、-N(i-Pr)₂、And

for formula (III-B), more typically both R2 groups are the same;

for formula (III-B), any R2 group is independently C₁-C₂₄Alkyl radical, C₆-C₁₀Aryl or C₆-₁₀Aryl radical C₁-C₆In the case of alkyl groups, they are more typically independently selected from C₁-C₁₈Alkyl and C₆-C₁₀Aryl radical C₁-C₆Alkyl, even more typically independently selected from: c₁-C₈Alkyl and C₆-C₁₀Aryl radical CH₂；

For formula (III-B), at any R2 independently is C₅-C₁₀Heteroaryl group CH₂In the case of radicals, they are preferably selected from pyridin-2-ylmethyl, pyrazin-2-ylmethyl, quinolin-2-ylmethyl, pyrazol-1-ylmethyl, pyrazol-3-ylmethyl, pyrrol-2-ylmethyl, imidazol-4-ylmethyl, benzimidazol-2-ylmethyl, pyrimidin-2-ylmethyl, 1, 2, 3-triazol-1-ylmethyl, 1, 2, 3-triazol-2-ylmethyl, 1, 2, 3-triazol-4-ylmethyl, 1, 2, 4-triazol-3-ylmethyl, 1, 2, 4-triazol-1-ylmethyl, thiazol-2-ylmethyl.Yl and thiazol-4-ylmethyl, typically pyridin-2-ylmethyl, quinolin-2-ylmethyl, imidazol-2-ylmethyl, thiazol-2-ylmethyl and thiazol-4-ylmethyl;

for formula (III-B), any R2 is CH₂CH₂In the case of N (R8) (R9), it is preferably chosen from-NMe₂、-NEt₂、-N(i-Pr)₂、And

for formula (III-B), each R2 is the same, typically pyridin-2-ylmethyl;

the radicals R3 and R4 are of the formula C (O) OR5, wherein each R5 is independently selected from hydrogen, C₁-C₈Alkyl and C_6-10Aryl (although each R5 is typically the same);

the radicals R3 and R4 are of the formula C (O) OR5, wherein each R5 is independently selected from C₁-C₈Alkyl and C_6-10Aryl (although each R5 is typically the same);

the radicals R3 and R4 are of the formula C (O) OR5, wherein each R5 is independently C₁-C₄Alkyl (although each R5 is typically the same);

the radicals R3 and R4 are identical and are usually C (O) OCH₃；

X is selected from C ═ O, - [ C (R6)₂]_0-3-, wherein each R6 is independently selected from hydrogen, hydroxy, C₁-C₄An alkoxy group;

x is selected from C ═ O and- [ C (R6)₂]-, wherein each R6 is independently selected from hydrogen, hydroxy and C₁-C₄Alkoxy (although each R6 is typically the same);

x is selected from C ═ O and- [ C (R6)₂]-, wherein each R6 is independently selected from hydroxy and C₁-C₄Alkoxy (although each R6 is typically the same); and

x is selected from C ═ O, C (OH)₂And C (OCH)₃)₂Wherein C ═ O or C (OH)₂Most typically.

The skilled artisan is aware of strategies for synthesizing bispidons and is therefore able to synthesize the bispidons described herein without undue burden. For example, in addition to the examples herein, reference may be made to:

WO 2008/003652A 1(Unilever PLC et al), which describes tetradentate, pentadentate or hexadentate nitrogen ligands bound to manganese and iron as drying agents for drying alkyd resins, and WO 00/60045A 1(The Procter & Gamble company) and WO 02/48301A 1 and WO 03/104379A 1 (both Unilever PLC et al), which describe examples of such bispidons cited in WO 2008/003652A 1.

WO 2005/042532A 1(Unilever plc et al);

WO 2017/085154 a1(Akzo Nobel Coatings International BV) which describes a coating composition comprising a desiccant composition comprising an iron complex comprising a bis (2-pyridyl) bispidon and a vanadium compound;

WO 2012/079624 A1(PPG Europe BV)；

WO 2013/045475 A1(PPG Europe BV)；

US 2014/0262917 A1(Valspar Sourcing，Inc.)；

WO 2014/070661 A1(Ashland Licnesing and Intellectual Property LLC)；

WO 2015/082553 A1(PPG Europe B.V.)；

WO 2013/083630 a1 and WO 2013/083632 a1 (both DSM asseses b.v., supra);

et al (Inorganica Chemica Acta, 337, 407-419 (2002));

et al (Inorg. chem., 41, 5440-) -5452 (2002)); and

p Comba et al (Angew. chem. int. Ed. Engl., 42, 4536-.

As mentioned above, the formulae (III) andx in (III-B) is most usually C ═ O or C (OH)₂. As the skilled worker knows, in this case gem-diol C (OH)₂Represents a hydrated ketone group. Generally, there is a fast dynamic equilibrium between the gem-diol and its parent ketone groups, making it difficult to isolate the gem-diol. However, as is known to those skilled in the art, ketones or gem-diols may be found in complexed bispidon. For example, complexes prepared in anhydrous solution may comprise ketone-containing bispidons, while those prepared under less dry conditions may comprise gem-diols (see, e.g., for exampleEt al (Inorganica Chemica Acta, supra) and P Comba et al (Angew. chem. int. Ed. Engl., supra). Thus, where reference is made herein to complexed bispidon (i.e., with a suitable transition metal ion as described herein), it is to be understood that such reference extends to complexes comprising bispidon and X ═ C ═ O and hydrates thereof (i.e., where X is C (oh))₂)。

When it is desired to synthesize bridged bispidons, i.e. the desired chelating agent of formula (III-B), the person skilled in the art is aware of how to prepare these as synthetic strategies for obtaining the chelating agent of formula (III). In particular, reference may be made toEt al (Inorg. chem., 41, 5440-. For example, the skilled person will recognize that if Q ═ 1, 3-propene (-CH) in formula (III-B)₂CH₂CH₂-) the desired bridged bispidon chelator of formula (III-B) can be obtained by reacting the appropriate piperidone precursor, formaldehyde and 1, 3-diaminopropane.

According to a particular embodiment, the bispidon according to formula (III) is one of the following chelating agents:

dimethyl 2, 4-bis (thiazol-2-yl) -3-methyl-7- (pyridin-2-ylmethyl) -3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-4-yl) -3-methyl-7- (pyridin-2-ylmethyl) -3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, and analogous 3, 7 isomer variants thereof: dimethyl 2, 4-bis (thiazol-2-yl) -3- (pyridin-2-ylmethyl) -7-methyl-3, 7-diaza-bicyclomethyl [3.3.1] non-9-one-1, 5-dicarboxylate and dimethyl 2, 4-bis (thiazol-4-yl) -3- (pyridin-2-ylmethyl) -7-methyl-3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate. Also preferred are tetradentate bispidons, in particular dimethyl 2, 4-bis (thiazol-2-yl) -3, 7-dimethyl-3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dimethyldicarboxylate and dimethyl 2, 4-bis (thiazol-4-yl) -3, 7-dimethyl-3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate.

According to other particular embodiments, the bispidon is according to formula (III-B), wherein:

e-pyridin-2-yl, R2-pyridin-2-ylmethyl; x ═ O (C ═ O); r3 ═ R4 ═ C (O) OCH₃And Q ═ CH₂CH₂(1, 2-bis {1, 5-bis (methoxycarbonyl) -3- (pyridin-2-ylmethyl) -9-oxo-2, 4-bis (pyridin) -2-yl) -3, 7-diazabicyclo [3.3.1]Non-7-yl } ethane);

e-pyridin-2-yl, R2-pyridin-2-ylmethyl; x ═ O (C ═ O); r3 ═ R4 ═ C (O) OCH₃And Q ═ CH₂CH₂CH₂(1, 3-bis {1, 5-bis (methoxycarbonyl) -3- (pyridin-2-ylmethyl) -9-oxo-2, 4-bis (pyridin) -2-yl) -3, 7-diazabicyclo [3.3.1]Non-7-yl } propane);

e-pyridin-2-yl, R2-methyl; x ═ O (C ═ O); r3 ═ R4 ═ C (O) OCH₃And Q ═ CH₂CH₂: (1, 2-bis {1, 5-bis (methoxycarbonyl) -3-methyl-9-oxo-2, 4-bis (pyridin-2-yl) -3, 7-diazabicyclo [3.3.1]Non-7-yl } ethane); or

E-pyridin-2-yl, R2-methyl; x ═ O (C ═ O); r3 ═ R4 ═ C (O) OCH₃And Q ═ CH₂CH₂CH₂(1, 3-bis {1, 5-bis (methoxycarbonyl) -3-methyl-9-oxo-2, 4-bis (pyridin-2-yl) -3, 7-diazabicyclo [3.3.1]Non-7-yl } propane).

Among the chelating agents of formula (III) or formula (III-B), most preferred are dimethyl 2, 4-bis (thiazol-2-yl) -3-methyl-7- (pyridin-2-ylmethyl) -3, 7-diaza-bicyclo [3.3.1] non-9-mono-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-2-yl) -3- (pyridin-2-ylmethyl) -7-methyl-dimethyl 3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-4-yl) -3-methyl-7- (pyridin-2-ylmethyl) dimethyl) -3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-4-yl) -3- (pyridin-2-ylmethyl) -7-methyl-3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, 1, 2-bis {3- (pyridin-2-ylmethyl) -9-oxo-2, 4-bis (pyridin-2-yl) - (3, 7-diaza-bicyclo [3.3.1] non-7-yl) -1, 5-dicarboxylate) methyl ester } ethane and 1, 3-bis {3- (pyridin-2-ylmethyl) -9-oxo-2, 4-bis (pyridin-2-yl) - (3, 7-diaza-bicyclo [3.3.1] non-7-yl) -1, 5-bis (carboxylic acid methyl ester } propane.

For such chelating agents, iron complexes are preferred, especially fe (ii).

The following features, alone or in combination, are typical (but not essential) features of the chelating agent of formula (IV) within the context of the context (i.e. without conflict):

according to a particular embodiment, wherein R¹、R²、R³Or R⁴Is C_1-24When alkyl, it may be C_1-10Alkyl, which according to a more specific embodiment may be C_1-6Alkyl groups, such as methyl.

If R is¹、R²、R³Or R⁴Are groups containing a heteroatom capable of coordinating to a metal ion, these groups may be the same or different. Heteroatoms often present in heteroaryl or non-aromatic heterocycles, usually optionally substituted by one or more (usually none or one) C_1-4Alkyl substituted heteroaryl containing groups. In particular embodiments, the heteroatom-containing group comprises one or more nitrogen atoms, for example one or two nitrogen atoms, typically one nitrogen atom; and/or a ring containing hetero atoms, e.g. one or more nitrogen atoms, e.g. one or two nitrogen atoms, often one nitrogen atom, with a ring of formula (IV) via an alkylene linkerThe remainder being linked, the alkylene linker being generally a straight chain containing from 1 to 6 carbon atoms (i.e., typically methylene, ethylene, n-propylene, n-butylene, n-pentylene, and n-hexylene), typically methylene or ethylene, and especially typically methylene.

When R is¹、R²、R³And R⁴When one or more of them comprises a heteroaryl group as described herein, the heteroaryl group may be, for example, pyridin-2-yl, pyrazin-2-yl, quinolin-2-yl, pyrazol-1-yl, pyrazol-3-yl, pyrrol-2-yl, imidazol-4-yl, benzimidazol-2-yl, pyrimidin-2-yl, 1, 2, 3-triazol-1-yl, 1, 2, 3-triazol-2-yl, 1, 2, 3-triazol-4-yl, 1, 2, 4-triazol-1-yl, 1, 2, 4-triazol-3-yl, thiazol-2-yl, and thiazol-4-yl. According to a particular embodiment, the heteroaryl group is pyridine. When R is¹、R²、R³Or R⁴When any of (a) contains a heteroaryl group, the heteroaryl group may optionally be substituted with C_1-4Alkyl groups are substituted one or more times. In general, R¹、R²、R³Or R⁴Any heteroaryl in (a) is unsubstituted or substituted by C_1-4Alkyl is substituted once. In certain embodiments, such heteroaryl groups are unsubstituted.

Usually, although not necessarily, when R¹、R²、R³And R⁴When one or more of (a) contains a pyridine ring, it is optionally substituted by a 2-position (i.e. heteroaryl is optionally C)_1-4Alkyl substituted 2-pyridyl, such as 2-pyridyl) is attached to the remainder of formula (IV). More typically, although also not necessarily, the pyridyl (especially 2-pyridyl) group is linked to the remainder of formula (IV), e.g. methylene, by an alkylene linker (as described herein). According to a particular embodiment, R¹、R²、R³And R⁴One or more of which is 2-pyridylmethyl. According to other particular embodiments, R¹、R²、R³And R⁴Is 2-pyridylmethyl, and optionally R²Is hydrogen or methyl.

F and F' are as defined aboveOptionally substituted alkylene of (a). Substituted by these alkylene groups may be C_1-24Alkyl, more usually C_1-18An alkyl group. C_6-10Aryl may be phenyl or naphthyl. According to other particular embodiments, F is optionally substituted methylene and F' is optionally substituted ethylene. According to a more specific embodiment, F and F 'are unsubstituted, e.g. F is unsubstituted methylene and F' is unsubstituted ethylene.

Reflecting in part certain embodiments of the chelating agent of formula (IV) above, embodiments of the chelating agent of formula (IV) can be defined by a chelating agent of formula (V):

wherein:

each of-R¹Independently is-H, -C_1-24Alkyl, -C_6-10Aryl or pyridin-2-ylmethyl wherein aryl or pyridyl is optionally substituted by C_1-4Alkyl substitution;

-R²represents-H or-CH₃(ii) a And

-R³and-R⁴Each independently is-H, -C_1-24Alkyl, -C_6-10Aryl or pyridin-2-ylmethyl wherein aryl or pyridyl is optionally substituted by C_1-4The substitution of the alkyl group is carried out,

for example, wherein:

each of-R¹Independently is-H, -C_1-24Alkyl or pyridin-2-ylmethyl wherein pyridyl is optionally substituted by C_1-4Alkyl substitution;

-R²represents-H or-CH₃(ii) a And

-R³and-R⁴Each independently is-H, -C_1-24Alkyl, or pyridin-2-ylmethyl wherein the pyridyl is optionally substituted with C_1-4Alkyl substitution.

In many embodiments of the chelating agents of formula (V) (and (IV)), both R1 groups are the same.

Further features of the chelating agent according to formula (V) (and (IV))According to another embodiment, each R¹Independently represents methyl or pyridin-2-ylmethyl, -R²Represents a methyl group, and-R³and-R⁴Each independently represents-C_1-24Alkyl or-C_6-10Aryl or pyridin-2-ylmethyl.

Specific chelating agents of formulae (IV) and (V) are:

6-dimethylamino-1, 4-bis (pyridin-2-ylmethyl) -6-methyl-1, 4-diazepane;

6-amino-1, 4-bis (pyridin-2-ylmethyl) -6-methyl-1, 4-diazepane;

1, 4, 6-trimethyl-6- { N- (pyridin-2-ylmethyl) -N-methylamino } -1, 4-diazepane;

6-amino-1, 4, 6-trimethyl-1, 4-diazepane;

6-dimethylamino-1, 4, 6-trimethyl-1, 4-diazepane;

1, 4, 6-trimethyl-6- (pyridin-2-ylmethyl) amino) -1, 4-diazepane;

6- { N, N-bis (pyridin-2-ylmethyl) amino } -1, 4, 6-trimethyl-1, 4-diazepane; and

6- { N- (pyridin-2-ylmethyl) -N-methylamino } -1, 4-bis (pyridin-2-ylmethyl) -6-methyl-1, 4-diazepane, typically 6-amino-1, 4-bis (pyridin-2-ylmethyl) -6-methyl-1, 4-diazepane and 1, 4, 6-trimethyl-6- { N- (pyridin-2-ylmethyl) -N-methylamino } -1, 4-diazepane.

According to a particular embodiment of all aspects of the invention, the chelating agent is of formula (I), (II), (III-B) or (V).

The chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) is typically present in those compositions and formulations described herein which also comprise from 0.00005 to 0.5 wt%, typically from 0.0001 to 0.1 wt% of an unsaturated resin (e.g. the composition of the first aspect of the invention, the resin-containing formulation of the fourth aspect of the invention and the first formulation of the kit of the fifth and sixth aspects of the invention).

Where weight percentages are mentioned herein (e.g.% w/w, wt% or wt%), these refer to weight percentages relative to the total weight of the curable components in the formulation or composition, which are typically the unsaturated resin and optional reactive diluent (if present), unless the context clearly indicates otherwise. For example, the composition according to the first aspect of the invention comprises 0.00005% w/w of a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV), relative to the weight of the curable components of the composition (i.e. the weight of the unsaturated resin(s), including the weight of any reactive diluent present).

Typically, the composition of the first aspect of the invention will comprise a complex of a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) with a suitable transition metal ion, typically one or two transition metal ions. These are typically ions of iron, manganese, copper or vanadium, more typically ions of iron or manganese, and even more typically ions of iron. When the complex comprises more than one transition metal ion, these ions are generally the same.

According to some embodiments, the composition of the first aspect of the invention does not comprise a complex of a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV). This is because we have recognised that it would be technically advantageous to provide a composition comprising an unsaturated resin, a peroxide and a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV), which composition is substantially free of at least iron, manganese, cobalt, vanadium and copper ions. These ions, if present in the composition, may form, together with the chelating agent, a metal complex capable of accelerating oxidative cure with peroxide.

Thus, manufacturers of unsaturated resins and accelerators suitable for oxidative curing with peroxides may include chelating agents of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) in the unsaturated resin-containing composition in amounts suitable for a given composition. In this way, the unsaturated resin-containing formulation according to the fourth aspect of the invention can be provided.

Each type of oxidatively curable unsaturated resin can, and typically does, have a different sensitivity to free radical curing by peroxides, and therefore a particular concentration of a chelator-containing complex (metal drier) may be required to achieve optimal curing. The producer of the unsaturated resin can determine the optimum amount of metal drier for a given liquid curable medium (i.e. a formulation comprising an unsaturated resin and a peroxide) and add to its batch (or a formulation comprising an unsaturated resin but no peroxide) an appropriate amount of a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV), but excluding transition metal ions which allow the formation of a catalytically active drier, which are typically, but not necessarily, iron, manganese, vanadium or copper ions. An appropriate amount of transition metal ion (typically selected from iron, manganese, vanadium and copper, more typically selected from iron and manganese) may then be added to the composition comprising the unsaturated resin, the peroxide and the chelating agent, by for example the manufacturer of the casting material, the fibre reinforcement and the coating.

Alternatively, the resin manufacturer may contact the complex of the chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) with the unsaturated resin, or the uncomplexed chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) with a transition metal ion (typically selected from iron, manganese, vanadium and copper, more typically selected from iron and manganese) suitable for forming a complex of the chelating agent) and the unsaturated resin, neither of which contacts need include contact with a peroxide (which may be added later).

Similarly, for example, the peroxide producer may include a suitable amount of a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) in the peroxide-containing formulation. In this way, a peroxide-containing formulation according to the fourth aspect of the invention may be provided. In such embodiments, the chelating agent will not typically be part of the complex comprising it, as such formulations may pose a safety hazard depending on the nature of the peroxide and/or its concentration: such formulations can be hazardous (e.g., explosive). The skilled person is able to take such a problem into account. The formulation may then be contacted with the unsaturated resin, and such formulation is typically substantially free of at least iron, manganese, cobalt, vanadium and copper ions. Also, the manufacturer of the material produced by curing the activated resin composition (composition according to the first aspect of the invention) may add an appropriate amount of a transition metal ion, typically selected from iron, manganese, vanadium and copper, more typically from iron and manganese, to the formulation comprising the unsaturated resin, the peroxide and the chelating agent.

Furthermore, we have found that mixing a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) in a formulation comprising an unsaturated resin and/or a peroxide in the substantial absence of at least iron, manganese, cobalt, vanadium and copper ions has a second advantage: we have found that when the compositions or formulations of the invention are prepared by contacting a chelant of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) with an unsaturated resin and/or peroxide formulation in the substantial absence of at least iron, manganese, vanadium and copper ions, the resulting formulation, after contact with a suitable source of transition metal ions (such as a source of iron or manganese ions), typically cures faster than a similar liquid curable medium prepared by contacting an unsaturated resin and peroxide with a formulation comprising a well-defined complex containing the same chelant. Such compositions and formulations therefore constitute notable embodiments of the first and fourth aspects of the present invention, respectively.

It is particularly surprising that the complex-containing composition according to the first aspect of the invention, which is not prepared from a well-defined complex, can cure more rapidly than a well-defined complex. Such compositions are described in more detail herein, particularly in connection with the methods of the second aspect of the invention, certain formulations of the fourth aspect of the invention and kits of the fifth aspect of the invention.

In these ways, the manufacturer of the unsaturated resin may add a chelating agent to the unsaturated resin it produces (thereby providing the particular unsaturated resin-containing formulation of the fourth aspect of the invention) for subsequent addition of peroxide and transition metal ions (typically as separate acts, but may subsequently add a formulation containing both peroxide and transition metal ions); or the manufacturer of the peroxide may add a chelating agent to the peroxide-containing formulation it produces (thereby providing the particular peroxide-containing formulation of the fourth aspect of the invention) for subsequent addition of the unsaturated resin and transition metal ion (typically as separate acts, although subsequent addition of a formulation comprising both unsaturated resin and transition metal ion is possible).

In view of such considerations, the formulation of the fourth aspect of the invention is substantially free of at least iron, manganese, cobalt, vanadium and copper ions, and the kit of the fifth aspect of the invention has utility: the formulation (of the fourth aspect) of the invention and the first formulation of these kits correspond to the composition according to the first aspect of the invention, but at least iron, manganese, cobalt, vanadium and copper ions are substantially absent. Ions may be added to such a formulation (conveniently provided by the second formulation within the kit of the fifth aspect of the invention).

The first formulation of the kit of the fifth aspect of the invention may be obtained by mixing a chelating agent according to formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) to a formulation comprising an unsaturated resin and a peroxide, or it can be obtained by mixing a chelating agent according to formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) into a formulation comprising an unsaturated resin prior to the addition of a peroxide, or it may be obtained by mixing a chelating agent according to formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) to the peroxide containing formulation before adding the unsaturated resin.

Alternatively, it may be advantageous, for example, to provide a formulation from the producer of an unsaturated resin comprising an unsaturated resin and a chelating agent in combination with a suitable transition metal ion, typically selected from iron, manganese, vanadium or copper, more typically iron or manganese, i.e. wherein such formulation lacks the peroxide present in the composition of the first aspect of the invention. Such formulations constitute embodiments of the fourth aspect of the invention. The complex of the chelating agent bound to such transition metal ions may or may not be a well-defined complex.

The advantage of omitting peroxide is that the cure of the unsaturated resin can be postponed until the peroxide is added to the formulation (to provide the composition of the invention) to initiate cure, for the manufacturer of the finished product, e.g. anyone who wishes to produce a cured product on demand. The producer of the unsaturated resin can determine the optimum content of chelating agent and transition metal ion to be included in such formulations in the form of a well-defined complex or a well-defined complex. Entities wishing to produce a cured product need only add an optimum amount of peroxide to the formulation to obtain the desired cure, and the formulation manufacturer can be guided in this regard.

In view of such consideration, the kit of the sixth aspect of the present invention has utility: the first formulation of these kits corresponds to the composition according to the first aspect of the invention, but typically no or substantially no peroxide is present, and the unsaturated resin-containing formulation of the fourth aspect of the invention, which also typically no or substantially no peroxide is present. Peroxides are provided in the second formulation of these kits.

By substantially no peroxide is meant herein less than about 0.001% w/w peroxide (i.e., relative to the curable component of the formulation concerned), typically less than about 0.01% w/w, typically less than about 0.1% w/w peroxide.

In view of the considerations outlined above, kits according to the fifth and sixth aspects of the invention are therefore of utility, and it will therefore be appreciated how kits according to the seventh aspect of the invention are useful. The kit of the seventh aspect of the invention is a three-component system in which the three formulations (as with the two formulations of the kit of the fifth and sixth aspects) are physically separated from each other, for example in separate cassettes or the like.

In each kit of the invention, one or more of the two (or three) formulations may comprise additional components (e.g., the formulation comprising the unsaturated resin may also comprise a reactive diluent). The components of such a kit are typically combined with each other to provide a composition according to the first aspect of the invention which may be cured to provide a composition according to the third aspect of the invention. Similarly, it will be appreciated that the formulation of the fourth aspect of the invention may comprise further components (for example, a formulation comprising an unsaturated resin may also comprise a reactive diluent).

A well-defined complex is defined herein (as that term is commonly used in the art) to mean a complex that has been isolated so that it can be readily characterized (i.e., defined) and analyzed (e.g., to determine its structure and purity). In contrast, a complex that is not well defined is prepared without isolation from the medium in which it is prepared (e.g., the reaction medium). Well-defined complexes usually consist of a single active ingredient, whereas non-well-defined complexes usually (but not necessarily) comprise a plurality of active ingredients. For example, there may be a mixture of mononuclear and dinuclear species, or there may be a mixture of different ancillary ligands.

The composition of the first aspect of the invention, including such formulations present in the kit of the fifth aspect of the invention, in which at least iron, manganese, cobalt, vanadium and copper ions are substantially absent, comprises less than 0.001 wt% of ions of each of at least iron, manganese, cobalt, vanadium and copper. This means that the composition of the invention is free of 0.001 wt% manganese ions, free of 0.001 wt% iron ions, free of 0.001 wt% cobalt ions, free of 0.001 wt% vanadium ions and free of 0.001 wt% copper ions. After preparation of such compositions, for example when introducing optional additional components to form an oxidatively curable medium, an appropriate amount of a suitable transition metal cation (e.g., an ion of one or more of iron, manganese, vanadium and copper) can be added. If desired, particular compositions of the first aspect of the invention may comprise less than 0.0001 wt% of each of at least iron, manganese, cobalt, vanadium and copper ions. Ideally, embodiments of the compositions of the present invention in which the concentration of the particular transition metal ion is less than 0.001% w/w or 0.0001% w/w are absent any specified transition metal ion. (it will be appreciated that similar considerations apply to certain formulations of the fourth aspect of the invention and to the first formulation of the kit of the fifth aspect of the invention). However, it is clear that this is practically impossible to achieve. Therefore, it is preferred that these transition metal ions are not present within the maximum feasible range. In particular, in view of the possible safety issues as described above, the formulation of the fourth aspect of the invention comprising a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) as defined in relation to the first aspect of the invention and a peroxide will generally be absent the above specified transition metal ions to the greatest extent possible.

In order to prepare a composition according to the first aspect of the invention, a formulation comprising an unsaturated resin, a formulation comprising a peroxide and a formulation comprising a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) according to the process of the second aspect of the invention. As discussed in more detail herein, it is understood that such contacting can be achieved by contacting less than three formulations. For example, if one formulation comprises both a peroxide and a chelating agent (such a formulation is an embodiment of the fourth aspect of the invention) which is contacted with a second formulation comprising an unsaturated resin, the method according to the second aspect of the invention may contact both formulations. In some embodiments, the formulation comprising a chelating agent may comprise a transition metal ion-containing complex comprising a chelating agent. This may or may not be a well-defined complex. Furthermore, mixtures of well-defined complexes and uncomplexed chelating agents can be used.

There is no particular order of contacting in which the method of the second aspect of the invention may be practiced. For example, the unsaturated resin may be mixed with the chelating agent (to provide another formulation of the fourth aspect of the invention, wherein the chelating agent is optionally part of the transition metal ion complex) and then the peroxide added. Alternatively, the peroxide may be mixed with the chelating agent (again providing a formulation of the fourth aspect of the invention, but for the reasons described herein the chelating agent is typically not part of the transition metal ion complex) prior to addition to the unsaturated resin; alternatively, the unsaturated resin may be mixed with the peroxide and then the chelating agent may be added.

In some embodiments of the process of the second aspect of the invention, the chelating agent is not part of the transition metal ion-containing complex, in which case, if desired, a source of transition metal ions may be subsequently added (or indeed the transition metal ions may have been formulated with the unsaturated resin prior to contacting the resulting mixture with the chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV)) to form a complex comprising the chelating agent in situ (i.e. in a formulation comprising the unsaturated resin and optionally including a peroxide if not already added). It will be understood that such complexes are considered to be undefined.

Thus, in some embodiments of the method of the second aspect of the invention, the composition of the first aspect of the invention may be provided by contacting the unsaturated resin, the peroxide and the uncomplexed chelating agent with each other in the substantial absence of at least ions of iron, manganese, cobalt, vanadium and copper. If desired, a suitable source of transition metal ions may be subsequently added to form the complex comprising the chelating agent in situ.

Typical molar ratios between any transition metal ion and the chelating agent are from about 0.1: 1 to about 10: 1, usually from about 0.3: 1 to about 3: 1. The molar ratio between the chelating agent and the transition metal ion is generally about 1: 2 to 1: 1. However, this need not necessarily be the case. Without being bound by theory, an excess of transition metal ions may be advantageous to allow curing behavior to proceed following a mechanism different from that involving a clearly or unambiguously defined transition metal complex. Conversely, a stoichiometric excess of chelating agent may be beneficial to improve regeneration of the catalytically active species during curing, which may improve curing performance despite the use of lower amounts of transition metal ions. It may also be advantageous to use a stoichiometric excess of chelating agent by reducing the strength of the non-ferrous metal ions and/or complexes. The skilled person will be able to take these considerations into account when implementing the invention.

If the chelating agent of the formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) is introduced as a complex containing transition metal ions,the complex may be, for example, a well-defined complex, or prepared, for example, by contacting a suitable chelating agent with a suitable transition metal salt in a suitable solvent, meaning that either or both of the chelating agent and transition metal salt may be in a suitable solvent prior to contacting each other. The salts may be soaps, which are metal soaps, a term commonly used in the art (and herein), and refer to alkyl carboxylates of metals, typically the C of the metal (e.g., cobalt, manganese, lead, zirconium, zinc, vanadium, strontium, calcium, and iron)₆-C₁₈A carboxylate salt. The resulting complex-containing mixture is then contacted with a formulation comprising an unsaturated resin and a peroxide, which are typically dissolved in an organic solvent.

As will be appreciated from the above discussion of the composition of the first aspect of the invention, such embodiments are notable with respect to both the first and second aspects of the invention in that according to the method of the second aspect of the invention, a complex, which is not well defined, is contacted with a formulation comprising an unsaturated resin and a peroxide. According to such an embodiment, there is provided an unsaturated resin composition according to the first aspect of the invention, obtainable by carrying out the method of the second aspect of the invention, wherein the chelating agent is not part of a well-defined complex comprising a suitable transition metal ion (e.g. an ion selected from iron, manganese, vanadium and copper, such as manganese or iron ions).

Alternatively, it is envisaged that such a composition may be obtained by the method of the second aspect of the present invention, which further comprises providing the chelant of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) as a complex obtained or obtainable by contacting the chelant of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) with a suitable transition metal salt, which may be a soap, in a suitable solvent. Typically, the resulting mixture is contacted as such (i.e., without further manipulation, including purification) with a formulation comprising an unsaturated resin and a peroxide. In other words, a particular embodiment of the second aspect of the invention comprises contacting a formulation comprising an unsaturated resin and a peroxide with a mixture of a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) and a suitable salt comprising a transition metal ion, typically an iron, manganese, vanadium or copper ion.

Typically, the metal salt used is an iron or manganese salt, typically in a divalent or trivalent redox state. Upon contact of the iron or manganese (or other transition metal ion) salt with the chelator, an iron or manganese chelator complex (or other transition metal chelator complex) is formed.

The transition metal salts used may be solid, in suspension or in solution in a variety of solvents. Typically, the salt comprises an iron (II), iron (III), manganese (II) or manganese (III) ion, although other salts such as manganese (IV) (or other transition metal ion) salts may also be used. Although a single salt is typically used, the present invention also contemplates the use of mixtures of metal salts.

The addition of the chelating agent in the form of a solution may be advantageous in allowing for improved and/or easier mixing with (a solution of) the unsaturated resin and/or the peroxide. If it is desired to introduce a very small amount of chelating agent, it may be beneficial to dilute the chelating agent in a suitable solvent before addition to the binder, since a higher dosing accuracy may be obtained. Suitable solvents are polar depending on the nature of the chelating agent and the unsaturated resin-chelating agent formulation desired. Preferred examples of polar solvents are ethylene glycol, propylene glycol, ethanol, isopropanol and acetonitrile. The skilled person will be able to readily formulate such solutions, typically using one or more solvents as described above.

Where chelating agents are used, they may be provided in the form of salts in which one or more of the nitrogen atoms is protonated. Sometimes, it may be desirable to neutralize these protonated salts to enable the chelating agent to chelate to iron or manganese ions. This can be achieved in a straightforward manner by contacting the salt of the chelate with a suitable base, for example sodium hydroxide or potassium hydroxide. For example, for the chelating agent N, N-tris (pyridin-2-ylmethyl) amine, the ordinarily skilled artisan readily obtains its hydrochloride (tpa.3hcl) form. When such a salt is used, three molar equivalents of potassium hydroxide or sodium hydroxide may be used to neutralize the hydrochloride salt. This neutralization step may be carried out prior to the process of the second aspect of the invention (i.e. prior to contacting the formulation comprising the unsaturated resin with the chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) or as part of the process itself). The same chelating agents are also commercially available as neutral chelating agents, i.e. not present as protonated salts, thus no neutralization step is required.

Alternatively, even if the chelating agent is provided in salt form, neutralization may not be required because of the presence of large excesses of other materials, such as in unsaturated resin formulations, which may effect deprotonation upon introduction of the chelating agent. Although the introduction of the chelating agent in the form of a salt may render the composition of the first aspect of the invention more acidic and possibly less reactive (e.g. towards complexation), the small amount of chelating agent involved (due to its role as a catalyst) is less likely to affect the binding of the metal ion and chelating agent to a higher degree. However, the person skilled in the art will take these factors into account by routine modification of the system affected, for example by observing changes in reaction conditions, stoichiometry and (in the present case) pre-neutralization of the chelator salt.

It will be understood that there is no particular limitation on the source of the transition metal ions. However, typically where the transition metal ion is a manganese or iron salt, the salt is selected from the group consisting of optionally hydrated MnCl₂、FeCl₂、FeCl₃、MnBr₂、Mn(NO₃)₂、Fe(NO₃)₃、MnSO₄、FeSO₄、(Fe)₂(SO₄)₃Mn (acetylacetone salt)₂Fe (acetylacetonate)₂Mn (acetylacetone salt)₃Fe (acetylacetonate)₃、Mn(R₄COO)₃(including Mn (acetate)₃)、Fe(R₄COO)₃、Mn(R₄COO)₂(including Mn (acetate)₂) And Fe (R)₄COO)₂(including Fe (acetate)₂) Wherein R is₄Is selected from C_1-24Alkyl groups. When the salt contains two R₄When the groups are present, they may be the same or different. Alkyl radicalThe moiety (meaning saturated hydrocarbon group) may be linear or contain branched and/or cyclic moieties. Indeed, throughout the specification, unless otherwise specified, it means C_1-24Alkyl, which may be linear or branched, and may be cycloalkyl or contain a cyclic moiety (e.g. alkyl may be cyclohexylmethyl), for example C_1-10Alkyl or C_1-6Alkyl groups, such as methyl.

The manganese or iron salt is generally selected from Mn (R)₅COO)₂Or Fe (R)₅COO)₂In particular R₅COO(^-) Selected from the group consisting of acetate, octanoate, 2-ethylhexanoate, neodecanoate (3, 3,5, 5-tetramethylhexanoate) and naphthenate. Furthermore, iron (chloride) is often optionally hydrated₂Manganese (chloride)₂Iron (nitrate)₃Manganese (nitrate)₂Iron sulfate or manganese sulfate. Most often, iron salts are used. Particularly frequently, iron salts are used, for example selected from iron (chloride)₂Iron (acetate)₂Iron (octoate)₂Iron (naphthenate)₂Iron (2-ethylhexanoate)₂And iron (neodecanoate)₂. The invention also contemplates the use of mixtures of different redox states of the metal ion with the same counterion, such as iron (neodecanoate)₂And iron (neodecanoate)₃A mixture of (a).

The term optionally hydrated is well known in the art. The metal salt usually contains water molecules in the crystal lattice, which will always be present unless the hydrated metal salt is subjected to a specific drying step by heating or drying under reduced pressure. However, partially or completely dehydrated metal salts may also be used. For example, iron (II) chloride, manganese (II) acetate, and manganese (II) chloride may be purchased as tetrahydrate salts or as dehydrated salts. Commercially available manganese (II) sulfate has the tetrahydrate and monohydrate forms, and iron (II) sulfate has the heptahydrate and monohydrate forms.

These transition metal salts are usually marketed in solution, in particular if they are of the above formula Fe (R)₄COO)₂Or Mn (R)₄COO)₂For example in a hydrocarbon solution to facilitate dissolution in the curable composition.However, other solvents may be used including alcohols, ketones and water (or aqueous solutions), particularly for the chlorides, sulphates and acetates of manganese and iron.

Compositions or formulations of the present invention comprising less than 0.001% (or 0.0001%) by weight of each ion of at least iron, manganese, vanadium and copper may be prepared by contacting (e.g., adding to) a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) with an unsaturated resin formulation.

As mentioned above, the chelating agent may be dissolved in the above organic solvent (or emulsified in an aqueous liquid). The chelating agent may be added to the formulation containing the unsaturated resin just after it is made, before it is cured with the peroxide, or at any time in between. The chelating agent may be added to the unsaturated resin as a pure material or as a solution. The addition of the chelating agent in the form of a solution may be advantageous in allowing for improved and/or easier mixing with (a solution of) the resin. If it is desired to introduce a very small amount of chelating agent, it may be beneficial to dilute the chelating agent in a suitable solvent before addition to the binder, since a higher dosing accuracy may be obtained. Depending on the nature of the chelant and the desired resin-chelant formulation, suitable solvents include aliphatic hydrocarbons such as heptane, water, alcohols such as ethanol, isopropanol, ethylene glycol or propylene glycol, or mixtures thereof. The skilled person will be able to readily formulate such solutions, typically using solvents such as those described above.

Alternatively, compositions or formulations of the invention comprising less than 0.001% (or 0.0001%) by weight of at least each ion of iron, manganese, vanadium and copper may also be prepared by contacting (e.g., adding) a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) with (e.g., to) a peroxide-containing formulation, provided that the resulting complex comprising the chelating agent and the peroxide comprises less than 0.001% (or 0.0001%) by weight of at least each ion of iron, manganese, vanadium and copper. The chelating agent may be added to the peroxide-containing formulation after it is made, before it is contacted with the peroxide to cure the unsaturated resin, or at any time in between. This includes the time from preparation of the peroxide until shipment to the manufacturer of the cured resin product. The chelating agent may be added to the peroxide as a pure substance or may be added as a solution. The addition of a chelating agent as a solution may be advantageous in allowing for improved and/or easier mixing with (a solution of) the resin. If it is desired to introduce a very small amount of chelating agent, it may be beneficial to dilute the chelating agent in a suitable solvent before addition to the peroxide, since a higher dosing accuracy may be obtained. Depending on the nature of the chelating agent and the desired peroxide-chelating agent formulation, suitable solvents include aliphatic hydrocarbons, such as heptane, water, alcohols, such as ethanol, isopropanol, ethylene glycol or propylene glycol, or mixtures thereof. The skilled person will be able to readily formulate such solutions, typically using solvents such as those described above.

As can be appreciated from the above discussion of the composition of the first aspect of the invention, such embodiments are notable with respect to both the first and second aspects of the invention when the composition is prepared in this manner.

Thus, as described herein, the compositions of the present invention comprising a complex of a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) and a transition metal ion may be prepared by contacting a formulation comprising an unsaturated resin directly with such a complex, or may be prepared by contacting a formulation comprising an unsaturated resin with a chelating agent that is not part of such a complex, and then adding a source of transition metal ions to the resulting formulation. Also, the composition of the present invention comprising a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) may be prepared by contacting a peroxide-containing formulation with a chelating agent, the composition comprising less than 0.001% (or 0.0001%) by weight of ions of each of at least iron, manganese, cobalt, vanadium and copper, and then adding to the resulting composition an unsaturated resin and a source of transition metal ions.

As a further embodiment of the process of the second aspect of the invention, a formulation comprising an unsaturated resin, a peroxide and a suitable transition metal ion may be contacted with a chelating agent of formulae (I), (I-B), (II-B), (II-C), (III-B) and (IV). Typically, the formulation comprising the unsaturated resin, peroxide and transition metal ion comprises a suitable transition metal ion at a concentration of from about 0.00001% w/w to about 0.02% w/w, for example from about 0.00002% w/w to about 0.01% w/w, for example from about 0.00005% w/w to about 0.005% w/w, as described below.

According to a particular embodiment, the transition metal ion (the metal promoter to which the chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) can coordinate to provide (the transition metal ion-containing complex of the unsaturated resin which can be cured with the peroxide in the formulation of the invention)) may be an iron and manganese ion or a mixture of any of these metal ions. The valency of the metal ion may be from +1 to +6, typically from +2 to + 5. Examples include metal ions selected from the group consisting of fe (ii), (iii), (iv), (v), (iii), (iv), (v), (iv), (v.

In the complex comprising a chelating agent of formula (I-B), (II-C) or (III-B), the number of metal ions per chelating agent molecule may be 1 or 2. Since the chelators of formulae (I-B), (II-C), and (III-B) comprise two tridentate, tetradentate, or pentadentate nitrogen donor moieties, each tridentate, tetradentate, or pentadentate nitrogen donor moiety may be bound to a transition metal (e.g., iron or manganese) ion. Thus, it can be seen that the molar ratio of the chelating agent of the formula (I-B), (II-C) or (III-B) to the metal ion is 1: 2. Complexes or species may also be obtained in which a chelator of formula (I-B), (II-C) or (III-B) containing two tridentate, tetradentate or pentadentate nitrogen donor moieties binds only one metal ion, for example if a molar excess of chelator is used. In this way, a 1: 1 molar ratio of chelating agent to metal ion complex having formula (I-B), (II-C) or (III-B) is provided, wherein one of the tridentate, tetradentate or pentadentate nitrogen donor moieties will not coordinate to manganese or iron ions.

The complex comprising the chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) may for example be of the general formula (VI):

[M_aL_kX_n]Y_m (VI)

wherein:

m represents an ion selected from iron, manganese, vanadium and copper;

each X independently represents a coordinating species selected from any mono-, di-or tri-charged anion capable of coordinating metal ion M in a mono-, di-or tridentate fashion and any neutral molecule;

each Y is independently a non-coordinating counterion;

a represents an integer of 1 to 10;

k represents an integer of 1 to 10;

n represents an integer of 1 to 10;

m represents an integer of 0 to 20; and

l represents a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) and (IV),

or a hydrate thereof.

Typically, M in formula (VI) represents a transition metal ion selected from Fe (II), Fe (III), Fe (IV), Fe (V), Mn (II), Mn (III), Mn (IV) and Mn (V).

Particular embodiments according to formula (VI), including wherein M represents a compound selected from fe (ii), (iii), (iv), (v), (iv), (v), (VI), (v), (:

m represents a metal ion selected from Fe (II), Fe (III), Mn (II), Mn (III), and Mn (IV);

x represents a group selected from O^2-、[R⁶BO₂]^2-、R⁶COO^-、[R⁶CONR⁶]^-、OH^-、NO₃ ^-、NO、S^2-、R⁶S^-、PO₄ ^3-、HPO₄ ^2-、H₂PO₄ ^-、[PO₃OR⁶]^3-、H₂O、CO₃ ^2-、HCO₃ ^-、R⁶OH、NR⁶R⁷R⁸、R⁶OO^-、O₂ ^2-、O₂ ^-、R⁶CN、Cl^-、Br^-、I^-、OCN^-、SCN^-、CN^-、N3^-、F^-、R⁶O^-、ClO₄ ^-、CF₃SO₃ ^-A coordinating substance of (1);

y represents a group selected from ClO₄ ^-、CF₃SO₃ ^-、[B(R⁶)₄]^-、[FeCl₄]^-、PF₆ ^-、R⁶COO^-、NO₃ ^-、R⁶O^-、N⁺R⁶R⁷R⁸R⁹、Cl^-、Br^-、I^-、F^-、S₂O₆ ^2-、OCN^-、SCN^-、H₂O，BF₄ ^-、SO₄ ^2-A counter ion of (a);

R⁶、R⁷、R⁸and R⁹Each independently represents hydrogen, optionally substituted alkyl or optionally substituted aryl;

a represents an integer of 1 to 4;

k represents an integer of 1 to 10;

n represents an integer of 1 to 4. And

m represents an integer of 1 to 8.

As used herein, in the definitions provided above for formula (VI) and elsewhere, the following definitions apply unless the context clearly indicates otherwise:

alkyl means herein a saturated hydrocarbon group, which may be linear, cyclic and/or branched. Alkylene refers to an alkyl group that formally abstracts one hydrogen atom. Typically, alkyl and alkylene groups contain 1 to 25 carbon atoms, more typically 1 to 10 carbon atoms, and more typically 1 to 6 carbon atoms. The simplest alkylene group is methylene (-CH)₂-)。

The aromatic moiety may be polycyclic, i.e. contain two or more fused (carbocyclic) aromatic rings. Typically, the aryl group will contain 1 to 14 carbon atoms. The simplest aryl group is phenyl. Naphthalene and anthracene are examples of polycyclic aromatic moieties.

Heteroaromatic moieties are aromatic heterocyclic moieties which contain one or more heteroatoms, typically oxygen, nitrogen or sulfur, more typically nitrogen, in place of one or more ring carbon atoms and any hydrogen atoms attached thereto in the corresponding aromatic moiety. Heteroaromatic moieties include, for example, pyridine, furan, pyrrole, and pyrimidine. Benzimidazoles are examples of polycyclic heteroaromatic moieties.

Aryl and arylene divalent groups are formed by abstraction of one and two hydrogen atoms, respectively, from an aromatic moiety. Thus, phenyl and phenylene are aryl and arylene diradicals corresponding to benzene. Similarly, pyridyl and pyridylidene (synonymous with pyridyldiyl) are heteroaryl and heteroarylidenediyl radicals corresponding to pyridine. Unless the context indicates otherwise, pyridyl and pyridylidene are typically 2-pyridyl and pyridin-2, 6-diyl, respectively.

Heterocycloalkanes are cycloalkanes, usually C_5-6Cycloalkanes in which one or more CH₂The moiety is substituted with a heteroatom, typically selected from nitrogen, oxygen and sulfur. When the heteroatom is nitrogen, it is understood that CH₂Some are formally substituted with NH instead of N. Heterocycloalkyl refers herein to a group formally formed by abstraction of a hydrogen atom from a heterocyclic alkane. Typical examples of heterocycloalkyl groups are those alkyl groups formally formed by abstraction of a hydrogen atom from a nitrogen atom. Typical heterocycloalkyl groups include pyrrolidinyl 1-yl, piperidin-1-yl, and morpholin-4-yl, i.e., wherein the heterocycloalkyl group is formally formed by abstraction of a hydrogen atom from a nitrogen atom of a parent heterocycloalkyl.

Arylalkyl means an aryl-substituted alkyl group. Similarly, aminoalkyl refers to alkyl substituted with amino, hydroxyalkyl refers to alkyl substituted with hydroxy, and so on.

Various alkylene bridges are described herein. Such alkylene bridges are usually, but not necessarily, linear alkylene bridges. However, they may be cyclic alkylene (e.g., C)₆The alkylene bridge may be cyclohexylene and, if so, may beIf any, is typically cyclohexyl-1, 4-ylidene). At bridges such as C_6-10In the case of an arylene bridge, this may be, for example, a phenylene group or the corresponding arylene group formed by abstraction of two hydrogen atoms from a naphthalene. When the bridge contains one or two C_1-3Alkylene unit and one C_6-10In the case of arylene units, such a bridge may be, for example, -CH₂C₆H₄CH₂-or-CH₂C₆H₄-. When present, phenylene is typically phenyl-1, 4-ylidene. It will be understood that each of these bridges may optionally be independently selected C_1-24Alkyl (e.g. C)_1-18Alkyl) groups are substituted one or more times, for example once.

Alkyl ethers are radicals of the formula-alkylene-O-alkyl, where alkylene and alkyl are defined as described herein.

Where an alkyl OR aryl group is optionally substituted, it may have one OR more substituents independently selected from-halo, -OH, -OR, unless the context clearly indicates otherwise¹⁰、-NH₂、-NHR¹⁰、-N(R¹⁰)₂、-N(R¹⁰)₃ ⁺、-C(O)R¹⁰、-OC(O)R¹⁰、-CO₂H、-CO₂ ^-、-CO₂R¹⁰、-C(O)NH₂、-C(O)NHR¹⁰、-C(O)N(R¹⁰)₂-heteroaryl, -R¹⁰、-SR¹⁰、-SH、-P(R¹⁰)₂、-P(O)(R¹⁰)₂、-P(O)(OH)₂、-P(O)(OR¹⁰)₂、NO₂、SO₃H、-SO₃ ^-、-S(O)₂R¹⁰、-NHC(O)R¹⁰and-N (R)¹⁰)C(O)R¹⁰A substituent of the group consisting of wherein each R¹⁰Independently selected from optionally-halogenated, -NH₃ ⁺、-SO₃H、-SO₃ ^-、-CO₂H、-CO₂ ^-、-P(O)(OH)₂、-P(O)(O^-)₂Alkyl, aryl, arylalkyl substituted once or twice or more.

When a particular part described herein is stated as optionally being, for example, C_1-6When alkyl is substituted, one or more such substituents may be present on any part of the moiety so substituted. For example, when referring to optionally substituted with C_1-6Alkyl substituted C_6-10Aryl radical C_1-24When alkyl is present, C_6-10Aryl moiety or C_1-24The alkylene moiety or both may be substituted by one or more C_1-6Alkyl substitution. However, in general, in this case, the specific portion is substituted only once.

According to a particular embodiment, a is 1 or 2 and k is 1 or 2.

It is well known that the ability of metal driers to catalyze the curing of unsaturated resins together with peroxides stems from their ability to participate in redox chemistry: the nature of the counterion Y is not critical. The choice of these compounds may be influenced by the solubility of the metal ion and the chelator complex of formula (I), (I-B), (II-B), (II-C), (HI) or (IV) in a given formulation or composition. For example, a counterion Y such as chloride, sulfate or acetate may be used to provide a complex that is readily soluble in water. When solvent-based (i.e., non-aqueous) compositions are used, it may be desirable to use a larger, less polar counterion, such as 2-ethylhexanoate. The person skilled in the art can select suitable counterions Y (and coordinating species X) without difficulty.

According to particular embodiments, X and Y may be independently selected from the group consisting of bromide, iodide, nitrate, sulfate, methoxide, ethoxide, formate, acetate, propionate, 2-ethylhexanoate, octanoate, neodecanoate, (3, 3,5, 5-tetramethylhexanoate), naphthenate, oxide, and hydroxide.

An example of a neutral molecule capable of coordinating a metal is acetonitrile, for example to provide the formula [ ML (CH)₃CN)₂]Cl₂A complex of (a).

It will be appreciated that the counterion Y serves to balance the charge generated by the complex formed by the metal ion M, the coordinating species X and the chelating agent L. Thus, if the charge on the complex is positive, one or more anions Y will be present. Conversely, if the charge on the complex is negative, one or more cations, Y, will be present.

When mononuclear complexes of the formula (VI) are used, they are preferably present in the following form: [ FeLCl₂]、[FeLBr₂]、[FeLCl]Cl、[MnLCl₂]、[MnLBr₂]、[MnLCl]Cl、[FeL(CH₃CN)]Cl₂、[MnL(CH₃CN)₂Cl₂、[FeL(CH₃CN)₂]Cl₂And [ MnL (CH)₃CN)₂]Cl₂。

It will be understood from the foregoing discussion that complexes of formula (VI) include dinuclear complexes (i.e., comprising two transition metal ions M), such as those containing hydroxide, oxo, carboxylate, or halide as bridging chelators (the bridging ligand being represented by mu (μ)). If a chelating agent according to formula (I-B), (II-C) or (III-B) is bound in a conventional manner to two transition metal ions, each metal ion passing 3, 4 or5 nitrogen donors, respectively, one, two or three bridging molecules may be present. A combination of bridging and non-bridging chelators X may be present. Non-limiting examples of binuclear manganese and iron complexes include [ LFe (. mu. -O) [ mu. -RCOO ] FeL](Y)₂、[LFe(μ-O)(μ-RCOO)FeL](Y)3、[LFe(X)(μ-O)Fe(X)L](Y)₃、[LFe(μ-O)FeL](Y)₃、[LFe(μ-OH)₂FeL](Y)₃、[LMn(μ-RCOO)₃MnL](Y) and [ LMn (. mu. -O) (. mu. -RCOO)₂MnL](Y)₂Wherein RCOO ═ acetate or 2-ethylhexanoate, L is a chelator according to formula (I), (II-B), (II-C), (III-B) or (IV), if present, wherein only one of the two tetradentate or pentadentate nitrogen donor moieties of the chelator of formula (I-B), (II-C) or (III-B) is bound to the Mn or Fe ion, and X ═ H₂O、OH^-、Cl^-Mn is in its oxidation state II or III and Fe is in its oxidation state II or III.

If both of the quadridentate or pentadentate nitrogen donor moieties of the chelating agent of formula (I-B), (II-C) or (III-B) combine with Fe or Mn ions to form a binuclear complex, the two metal ions may be bound via hydroxide, oxo, carboxylate or halide groups ((I-B), (II-C) or (III-B))Except for bridging with a chelating agent of formula (I-B), (II-C) or (III-B). Thus, the following non-limiting examples of complexes of formula (VI) can be obtained: [ LFe (. mu. -O) (. mu. -RCOO) Fe](Y)₂、[LFe(μ-O)(μ-RCOO)Fe](Y)₃、[LFe(X)(μ-O)Fe(X)](Y)₃、[LFe(μO)Fe](Y)₃、[LFe(μ-OH)₂Fe](Y)₃Or [ LMn (mu-O)₂Mn]Y₃Wherein RCOO is acetate or 2-ethylhexanoate and L is a chelating agent according to formula (IB), (II-B), (II-C) or (III-B), X is H₂O、OH^-、Cl^-Mn is in its oxidation state II or III and Fe is in its oxidation state II or III.

Alternatively, a chelating agent according to formula (I-B), (II-C) or (III-B) may bind two Fe or Mn ions, wherein the complex formed does not comprise any additional bridging ligands between the two metal ions coordinated to the same chelating agent. For example, for a chelator of formula (III-B) comprising two bispidon units bridged by a bridge Q, if the bispidon is pentadentate (i.e., each E is, for example, a pyridin-2-yl, and each R2 is a pyridin-2-ylmethyl group), the sixth position of the readily coordinatable iron or manganese ion may be outward, and may be bound to, for example, a hydroxide, oxo, carboxylate, or halide group (these groups are not otherwise bound to the Fe or Mn ion of another identical chelator of formula (III-B)). It is possible that a hydroxide, oxo, carboxylate or halide group R bound to a Fe or Mn ion binds to another Fe or Mn ion coordinated to another chelator of formula (III-B). In this way, oligomeric complexes can be obtained. If there are no bridging groups, the preferred structure is similar to a mononuclear ligand, e.g. [ L (FeCl)₂)₂]、[L(FeBr₂)₂]、[L(FeCl)₂]、[L(MnCl₂)₂]、[L(MnBr₂)₂]、[L(MnCl)₂]、[L(Fe(CH₃CN)₂)]Cl₂、[L(Mn(CH₃CN))₂]Cl₂、[L(Fe(CH₃CN)₂])₂]Cl₂、[L(Mn(CH₃CN)₂)₂]Cl₂。

The metal chelator complex comprising a suitable counterion Y may be contacted with (e.g. added to) the unsaturated resin with peroxide to form the composition of the first aspect of the invention. However, it will be appreciated from the above discussion that many embodiments of the method of the second aspect of the present invention comprise mixing the chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) with a transition metal ion salt (typically an iron or manganese salt), rather than introducing the chelating agent as a pre-formed, well-defined complex (such as those described above). In a particular embodiment, the iron salt is mixed with a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV).

The kit of the fifth aspect of the invention may optionally include instructions or other guidance regarding methods by which the first formulation and transition metal ions may be contacted. In this way, after optimizing the properties of the transition metal ion source (e.g., by preparing a particular solution of a particular transition metal ion salt), the manufacture of cured thermoset resin materials (e.g., casting materials, fiber reinforcements, and coatings) can optimize the manner in which formulations containing transition metal complexes can be prepared. The preparation of the activated resin composition may be accomplished by the manufacturer of the cured thermoset, who may contact the transition metal ion source with an otherwise fully formulated activated resin composition. Similarly, the kit of the sixth aspect of the invention may optionally comprise instructions or other guidance regarding the methods by which the first formulation and peroxide may be contacted; and the kit of the seventh aspect of the invention may optionally contain instructions or other guidance regarding the methods by which the three formulations may be contacted. In this way, the manufacture of unsaturated resins can provide guidance to the producer of cured thermosetting resin materials, i.e. which peroxide and optimal dosage can be used. Likewise, the manufacture of peroxides may provide guidance to the producer of cured thermosetting resin materials, which unsaturated resins and which optimal dosages may be used.

Co-accelerator (Secondary accelerator)

Composition of the first aspect of the invention, fourth aspectThe formulation and kit of (a) may further compriseIn totalAccelerators (secondary accelerators).In totalExamples of accelerators are:

(1) a metal system: typically including metal carboxylates containing cobalt (lower if Co is used), manganese, copper, iron, zinc, vanadium, nickel, tin, magnesium, titanium, potassium, lithium, etc., acetylacetonates, dicyclopentadiene, complexes and derivatives thereof. In general, any suchIn totalNone of the promoters are cobalt-based.

(2) Amine: typically aniline, various amides, derivatives of aromatic and aliphatic amines; such as dimethylaniline, diethylaniline, 2-aminopyridine, phenyldiethanolamine, dimethyl-p-toluidine, dimethylacetamide, acetoacetanilide, bipyridine, N- (2-hydroxyethyl) -N-methyl-p-toluidine, and the like.

(3) Oxygen-containing compound: typically comprising an oxygenated organic compound with an aldehyde, ketone, ether, ester or alcohol group capable of forming a complex with a metal salt. In particular keto and aldehyde esters, ethers or alcohols, 1, 3-diketones and aldehydes, 1, 2-diketones and certain polyols and other alcohols; for example, ethyl acetylacetonate, mono-and diesters of ketoglutaric acid, esters of pyruvic acid, glucose, fructose, acetylacetone, benzoylacetone, dibenzoylmethane, diethylmalonate, diacetyl, glyoxal, diethylene glycol, benzylglycol, ascorbyl palmitate and the like.

(4) Thiol compounds: thiol compounds include thiols, and more preferably materials comprising at least two thiol groups, and their adducts with anhydrides or epoxides, all of which are capable of forming complexes with metal salts. For example, n-dodecylmercaptan, t-dodecylmercaptan, 2-mercaptoethanol, dipentene dithiol, ethylcyclohexyl dithiol, ethylene-1, 2-bis-3-mercaptoester, 1, 2, 6-hexanetriol, tetramercaptoacetate, thioester of polyhydric alcohol, etc.

(5) Quaternary salts: can form a complex with a metal salt; for example, trimethylbenzylammonium chloride, tris- (p-chlorophenyl) -benzylphosphonium chloride, tetramethylphosphonium chloride, ammonium acetate, ammonium caprylate, and the like.

(6) Phosphorus-containing compounds: capable of forming complexes with metal compounds including alkyl phosphites, alkyl phosphates, phosphoric acid, hypophosphorous acid, phosphorous acid, trialkyl phosphates, triaryl phosphates; for example, tris (2-ethylhexyl) phosphite, dibutyl phosphate, phenylphosphinic acid, dihexyl phosphite, and the like.

(7) Lewis acid: such as boron fluoride dihydrate, ferric chloride, perchloric acid, and the like.

(8) Alkali: such as tetraethanolammonium hydroxide, tetramethylammonium hydroxide, and the like.

(9) And others: not in the above categories, but have been found to have a promoting effect on certain peroxy catalysts; for example, sodium sulfoxylate formaldehyde, chlorotrityl methane, ascorbic acid, isoascorbic acid, and the like.

The skilled person will appreciate that the formulation comprising a chelating agent and a peroxide according to the fourth aspect of the invention will typically not compriseIn totalAccelerators, as such formulations will generally be absent of a primary accelerator.

Peroxides and their use in the preparation of pharmaceutical preparations

The composition according to the first aspect and the kit of the invention comprise a peroxide compound and the formulation of the fourth aspect of the invention may comprise a peroxide compound. Any peroxide known to the skilled artisan can be used to cure the unsaturated resins described herein. Such peroxides include organic and inorganic peroxides, which may be solid or liquid. Hydrogen peroxide may also be used. Examples of suitable peroxides include those containing the functional groups-OO- (peroxycarbonate), -c (o) OO- (peroxyester), -c (o) ooc (o) - (dialkyl peroxide), -OO- (dialkyl peroxide) and the like. These peroxides may also be natural oligomers or polymers. An extensive list of suitable peroxide compounds can be found in particular in paragraph [0018] of US 2002/0091214 a 1.

Typically, the peroxide is an organic peroxide. Examples of suitable peroxides are tertiary alkyl hydroperoxides (e.g., t-butyl hydroperoxide), other hydroperoxides (e.g., cumyl hydroperoxide), ketone peroxides (e.g., peroxides formed by mixing a ketone with hydrogen peroxide, such as acetylacetone peroxide or methyl ethyl ketone peroxide), peroxy esters or peracids (e.g., t-butyl perester, benzoyl peroxide, peracetate, perbenzoate, lauryl peroxide, peroxydiethyl ether) Methyl isobutyl ketone peroxide, cyclohexanone peroxide and acetylacetone peroxide. Organic peroxides commonly used as curing agents are tertiary peresters or tertiary hydroperoxides, i.e., peroxy moieties having a tertiary carbon directly bonded to an OO-acyl or OOH group. Also, mixtures of various peroxide compounds may be used.

Preferably, liquid peroxyesters, liquid hydroperoxides or liquid mixtures of hydroperoxides are used. Handling of liquid peroxides is generally easier: mixing is easier and the dissolution rate in the resin to be cured is higher. Most preferred is the use of liquid peroxides, especially Methyl Ethyl Ketone Peroxide (MEKP) or liquid alkyl hydroperoxides, especially cumyl hydroperoxide.

The optimum peroxide content to be used depends on the type of peroxide, the unsaturated resin used and the intended application. The skilled person will be able to optimise the peroxide content and type in conjunction with the unsaturated resin and metal chelating agent mixture or complex used. The peroxide is present in an amount of 0.001 to 10% w/w, more preferably 0.01 to 8% w/w, still more preferably 0.1 to 6% w/w, even more preferably 0.3 to 4% w/w, and most preferably 0.5 to 2% w/w.

The activated resin composition of the first aspect of the present invention and other formulations described herein may further comprise one or more free radical inhibitors, typically selected from phenolic compounds, stable free radicals, such as gavagen-based free radicals, N-oxyl compounds, urushiol and/or phenothiazine. Suitable examples of free radical inhibitors which may be used are 2-methoxyphenol, 4-methoxyphenol, 2, 6-dibutyl-4-methylphenol, 2, 6-dibutylphenol, 2, 4, 6-trimethylphenol, 2, 4, 6-tris-dimethylaminomethylphenol, 4 '-thiobis (3-methyl-6-tert-butylphenol), 4' -isopropylbisphenol, 2, 4-di-tert-butylphenol, 6 '-di-tert-butyl-2, 2' -methylene-di-p-cresol, hydroquinone, 2-methylhydroquinone, 2, 5-di-tert-butylhydroquinone, 2, 6-dimethylt-butylphenol, and mixtures thereof, 2, 6-dimethylhydroquinone, 2, 3, 5-trimethylhydroquinone, catechol, 4-tert-butylcatechol, 4, 6-di-tert-butylcatechol, benzoquinone, 2, 3,5, 6-tetrachloro-1, 4-benzoquinone, methylbenzoquinone, 2, 6-dimethylbenzoquinone, naphthoquinone, 1-oxy-2, 2, 6, 6-Tetramethylpiperidine (TEMPO), 1-oxy-2, 2, 6, 6-tetramethylpiperidin-4-ol (TEMPOL), 1-oxy-1, 2, 2, 6, 6-tetramethylpiperidin-4-one (TEMPON), 1-oxy-1, 2, 2, 6, 6-tetramethyl-4-carboxy-piperidine (4-carboxy-TEMPO), 1-oxo-2, 2, 5, 5-tetramethylpyrrolidine, 1-oxo-2, 2, 5, 5-tetramethyl-3-carboxypyrrolidine, aluminum-N-nitrosophenylhydroxylamine, diethylhydroxylamine, phenothiazine, and/or a derivative or combination of any of these free radical inhibitors.

The amount of free radical inhibitor, if present, may vary depending on the desired cure time. Free radical inhibitors, such as phenolic inhibitors, are generally used in amounts of 0.0001 to 10% by weight. More preferably, the amount of the radical inhibitor in the resin composition is in the range of 0.001 to 1 wt%.

The composition of the first aspect of the invention, which comprises a complex of a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV) may be used for all typical applications of such resins. In particular, they may be suitable for use in closed mould applications, but may also be used in open mould applications. For closed mould applications it is particularly important that the manufacturer of the closed mould product can reliably use the advantageous properties of the resin according to the invention. The ends to which the composition according to the first aspect of the invention may be applied include marine applications, chemical anchoring, construction, lining, roofing, flooring, windmill blades, containers, tanks, pipes, automotive parts, corrosion, electrical, transportation, and the like.

The invention further relates to a method of radically curing an unsaturated resin, for example by providing a composition according to the first aspect of the invention, or by carrying out the method of the second aspect of the invention, wherein the chelating agent is part of a transition metal ion complex and allowing the composition to cure, for example by mixing the compositions of the kit of the fifth to seventh aspects of the invention with each other and allowing the resulting composition to cure. It has been found that the transition metal ion complexes (particularly complexes of iron or manganese ions) of the chelating agents described herein promote free radical curing of unsaturated polyester resins, vinyl ester resins and acrylic resins. In general, curing is carried out at a temperature between-20 and +200 ℃, preferably in the range-20 to +100 ℃, most preferably at a temperature of-10 to +60 ℃ (so-called cold cure).

The present invention, in particular the third aspect thereof, also relates to all cured gel coats and molded composites obtained when curing unsaturated resins according to the invention, typically unsaturated polyester resins, vinyl ester resins (e.g. acrylic resins), wherein the gel coats comprise coloured or colourless gel coats, as well as in-mold coatings, preferably for marine, sanitary or automotive applications, typically having a film thickness not exceeding 0.75mm and suitable weatherability, hydrolytic stability and mechanical properties. The molded composite is believed to have a thickness of at least 0.5mm and suitable mechanical properties, preferably as a reinforced composite product, and is used in the fields of chemical anchoring, construction, roofing, flooring, marine applications, windmill blades, containers, tanks, piping, ships, corrosion, electrical, transportation, aerospace, and the like.

Each of the patent and non-patent references cited herein is incorporated by reference in its entirety as if each reference were set forth in its entirety herein.

The invention may be further understood with reference to the following non-limiting clauses:

1. a composition, comprising:

(i)5 to 95% w/w of an unsaturated resin;

(ii)0.001 to 10% w/w peroxide;

(iii)0.00001 to 0.2% w/w of a chelating agent of formula (I), (I-B), (II-B), (II-C), (III-B) or (IV):

X((CY₂)_nR1)₃ (I)

(R1(CY₂)_n)₂X(CY₂)_nR2-Q-R2(CY₂)_nX((CY₂)_nR1)₂ (I-B)

wherein:

if X is CZ, n is 0; if X is N, then N is 1;

each Y is independently selected from H, CH₃、C₂H₅And C₃H₇；

each-R1 is independently selected from-CY₂N(C_1-24Alkyl radical)₂；-CY₂NR3 in which R3 and the nitrogen atom N to which it is attached represent optionally substituted by one or more C_1-6Alkyl-substituted heterocycloalkyl radicals bound to the adjacent CY via the nitrogen atom N₂Partially connecting; or represents optionally substituted by C₁-₆An alkyl-substituted heteroaryl group selected from pyridin-2-yl, pyrazin-2-yl, quinolin-2-yl, pyrazol-1-yl, pyrazol-3-yl, pyrrol-2-yl, imidazol-4-yl, benzimidazol-2-yl, pyrimidin-2-yl, 1, 2, 3-triazol-1-yl, 1, 2, 3-triazol-2-yl, 1, 2, 3-triazol-4-yl, 1, 2, 4-triazol-1-yl, 12, 4-triazol-3-yl, thiazol-2-yl and thiazol-4-yl;

wherein:

each-R5 is independently selected from-CH₂N(C_1-24Alkyl radical)₂、-CH₂NR9 or optionally substituted by C_1-6An alkyl-substituted heteroaryl group selected from pyridin-2-yl, pyrazin-2-yl, quinolin-2-yl, pyrazol-1-yl, pyrazol-3-yl, pyrrol-2-yl, imidazol-4-yl, benzimidazol-2-yl, pyrimidin-2-yl, 1, 2, 3-triazol-1-yl, 1, 2, 3-triazol-2-yl, 1, 2, 3-triazol-4-yl, 1, 2, 4-triazol-1-yl, 1, 2, 4-triazol-3-yl, thiazol-2-yl, and thiazol-4-yl;

the or each-R6 independently represents-R10-R11;

the or each-R7 and the or each-R8 each independently represent hydrogen, or are selected from C_1-18Alkyl radical, C_6-10Aryl radical, C_5-10Heteroaryl group, C_6-10Aryl radical C_1-6Alkyl and C_5-10Heteroaryl C_1-6Alkyl radicals, each of which may optionally be substituted by C_1-6Alkyl is substituted with the proviso that-R7 or-R8 may not be one of the allowed possibilities for-R5;

the or each-R10-independently represents optionally substituted by C_1-6Alkyl substituted C_1-6An alkylene group;

each-NR 9 independently represents a moiety in which R9 and the nitrogen atom to which it is attached N represent optionally substituted by one or more C_1-20An alkyl-substituted heterocycloalkyl group, which moiety is linked to the remainder of the chelating agent through the nitrogen atom N; and

wherein:

Wherein N (R8) (R9) is selected from the group consisting of: two (C)_1-44Alkyl) amino; two (C)_6-10Aryl) amino, wherein each aryl group is independently optionally substituted with one or more C_1-20Alkyl substitution; two (C)_6-10Aryl radical C_1-6Alkyl) amino, wherein each aryl group is independently optionally substituted with one or more C_1-20Alkyl substitution; NR7 in which R7 and the nitrogen atom N attached thereto represent optionally substituted by one or more C_1-20An alkyl-substituted heterocycloalkyl group attached through the nitrogen atom N to the remainder of R1 or R2; bis (heterocycloalkyl C)_1-6Alkyl) amino group, whichWherein each heterocycloalkyl group is independently optionally substituted by one or more C_1-20Alkyl substitution; and bis (heteroaryl C)_1-6Alkyl) amino, wherein each heteroaryl is independently optionally substituted by one or more C_1-20Alkyl substitution;

x is selected from C ═ O, - [ C (R6)₂]_0-3-, wherein each R6 is independently selected from hydrogen, hydroxy, C₁-C₄Alkoxy and C₁-C₄An alkyl group;

wherein:

-R¹、-R²、-R³and-R⁴Each independently represents-H, -C_1-24Alkyl radical, C_6-10An aryl group or a group containing a heteroatom capable of coordinating to a metal ion;

f represents a methylene or ethylene group, wherein one or more hydrogen atoms may optionally be independently replaced by C_1-24Alkyl or C_6-10Aryl substitution; and

f' represents ethylene or n-propylene, wherein one or more hydrogen atoms may optionally be independently replaced by C_1-24Alkyl or C_6-10Aryl substitution.

2. The composition of clause 1, wherein the chelating agent is of formula (I), (I-B), (II-B), or (II-C), e.g., of formula (I), (I-B), (II), or (II-B).

3. The composition of clause 2, wherein each Y (if present) is H.

4. A composition according to clause 2 or according to clause 3, wherein the or each X is N or CZ, wherein Z is selected from hydrogen, optionally substituted with C_1-6Alkyl substituted C_1-24Alkyl, optionally substituted by C_1-6Alkyl substituted C_1-24alkyl-O-C_1-24Alkyl, optionally substituted by C_1-6Alkyl-substituted hydroxy C_1-24Alkyl and optionally substituted by C_1-6Alkyl substituted C_6-10Aryl radical C_1-24An alkyl group.

5. The composition of clause 4, wherein Z is hydrogen, C_1-24Alkyl or C_6-10Aryl radical C_1-24An alkyl group.

6. The composition of clause 5, wherein the or each X is N or CZ, wherein Z is hydrogen, C_1-18Alkyl or C_6-10An arylmethyl group.

7. The composition of clause 4, wherein the or each X is N or CZ, wherein Z is selected from H, methyl, hydroxymethyl, methoxymethyl, and benzyl.

8. A composition according to clause 2 or according to clause 3, wherein the or each X is N.

9. The composition of any of clauses 2-8, wherein each-R1 moiety is-CY₂N(C_1-24Alkyl radical)₂or-CY₂NR3 with said CY₂The nitrogen-containing group to which the groups are attached is selected from the group consisting of-NMe 2, -NEt2, -N (i-Pr)2,Andgroup (d) of (a).

10. The composition of clause 9, wherein each-R1 moiety is-CH₂N(C_1-24Alkyl radical)₂or-CH₂NR3。

11. The composition of any of clauses 2-8, wherein each-R1 is pyridin-2-yl, imidazol-4-yl, benzimidazol-2-yl, each optionally substituted with one or more C_1-6Alkyl substitution.

12. The composition of clause 11, wherein each-R1 is optionally substituted pyridin-2-yl.

13. The composition of clause 12, wherein each-R1 is unsubstituted pyridin-2-yl.

14. The composition of any of clauses 2-13, wherein each-R5 is optionally substituted pyridin-2-yl.

15. The composition of clause 14, wherein each-R5 is unsubstituted pyridin-2-yl.

16. A composition according to any of clauses 2 to 13, wherein each of the moieties-R5 is-CY₂N(C_1-24Alkyl radical)₂or-CY₂NR3 with said CY₂The nitrogen-containing group to which the groups are attached is selected from the group consisting of-NMe 2, -NEt2, -N (i-Pr)2,Andgroup (d) of (a).

17. The composition of clause 16, wherein each moiety-R5 is-CH₂N(C_1-24Alkyl radical)₂or-CH₂NR3。

18. The composition of any one of clauses 2 to 17, wherein-R10-or each-R10-is-CH₂-。

19. A composition according to any one of clauses 2 to 18, wherein the or each-R11 independently represents C_5-10Heteroaryl group, C_5-10Heteroaryl C_1-6Alkyl, -CY₂N(C_1-24Alkyl radical)₂or-CY₂NR9。

20. As in clause 2A composition according to any one of claims 18, wherein the or each-R11 is selected from-H, C_1-5Alkyl, phenyl, -CY₂N(C_1-24Alkyl radical)₂、-CY₂NR9 or optionally substituted by C_1-6Alkyl-substituted heteroaryl selected from pyridin-2-yl, pyrazin-2-yl, quinolin-2-yl, pyrazol-1-yl, pyrazol-3-yl, pyrrol-2-yl, imidazol-4-yl, benzimidazol-2-yl, pyrimidin-2-yl, 1, 2, 3-triazol-1-yl, 1, 2, 3-triazol-2-yl, 1, 2, 3-triazol-4-yl, 1, 2, 4-triazol-1-yl, 1, 2, 4-triazol-3-yl, thiazol-2-yl, and thiazol-4-yl.

21. A composition according to any of clauses 2 to 18, wherein the or each-R11 is selected from-H, phenyl, -CY₂N(C_1-8Alkyl radical)₂or-CY₂NR9, wherein R9 and the nitrogen atom N to which it is attached represent an unsubstituted heterocycloalkyl group, which is attached to the remainder of the chelating agent through nitrogen atom N.

22. The composition of clause 21, wherein the or each-R11 moiety is-CY₂N(C_1-24Alkyl radical)₂or-CY₂NR9 with said CY₂The nitrogen-containing group to which the groups are attached is selected from the group consisting of-NMe 2, -NEt2, -N (i-Pr)2,Andgroup (d) of (a).

23. The composition of clause 22, wherein the or each-R11 moiety is-CH₂N(C_1-24Alkyl radical)₂or-CH₂NR9。

24. A composition according to any one of clauses 2 to 18, wherein the or each R11 is selected from the group consisting of pyridin-2-yl, pyrazin-2-yl, quinolin-2-yl, pyrazol-1-yl, pyrazol-3-yl, pyrrol-2-yl, imidazol-4-yl, a heteroaryl group optionally substituted with alkyl of the group consisting of benzimidazol-2-yl, pyrimidin-2-yl, 1, 2, 3-triazol-1-yl, 1, 2, 3-triazol-2-yl, 1, 2, 3-triazol-4-yl, 1, 2, 4-triazol-1-yl, 1, 2, 4-triazol-3-yl, thiazol-2-yl and thiazol-4-yl.

25. The composition of clause 24, wherein the or each R11 is optionally substituted pyridin-2-yl, imidazol-4-yl, or benzimidazol-2-yl.

26. The composition of clause 25, wherein the or each R11 is optionally substituted pyridin-2-yl.

27. The composition of clause 26, wherein the or each R11 is unsubstituted pyridin-2-yl.

28. A composition according to any one of clauses 2 to 27, wherein-the or each-R7 and the or each-R8 independently represent-H, or are selected from C_1-6Alkyl radical, C_6-10Aryl and C_6-10Aryl radical C_1-6The radical of an alkyl radical, each of which may optionally be substituted by C_1-6Alkyl substitution.

29. The composition of clause 28, wherein the or each-R7 is selected from the group consisting of-H, methyl, and benzyl.

30. The composition of clause 28 or of clause 29, wherein the or each-R8 is selected from the group consisting of-H, methyl, and benzyl.

31. The composition of clause 30, wherein the or each-R8 is methyl.

32. The composition of any of clauses 2 to 31, wherein the chelating agent is of formula (I) or (II).

33. The composition of any of clauses 2-31, wherein the chelating agent is of formula (I-B), (II-B), or (II-C).

34. The composition of clause 33, wherein Q is selected from-CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-and-CH₂CHOHCH₂-, 1, 2-phenylene and 1, 4-phenylene, each of which is optionally substituted by C_1-6Alkyl substitution.

35. The composition of clause 33 or clause 34, wherein Q is unsubstituted.

36. The composition of any of clauses 33-35, wherein both-R2-moieties are the same.

37. The composition of clause 36, wherein both-R2-moieties are pyridine-2, 6-diyl, imidazole-1, 4-diyl, or imidazole-2, 5-diyl.

38. The composition of clause 36 or as clause 37, wherein the-R2-moieties are all pyridine 2, 6-diyl.

39. The composition of any of clauses 33-38, wherein the bridge Q2 is selected from-CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-and-CH₂CHOHCH₂-, 1, 2-phenylene and 1, 4-phenylene, each of which is optionally substituted by C_1-6Alkyl substitution.

40. The composition of any of clauses 33 to 39, wherein the bridge Q2 is unsubstituted.

41. The composition of clause 40, wherein the bridge Q2 is-CH₂CH₂-。

42. The composition of any of clauses 2 to 41, wherein:

the or each X is N or CZ, wherein Z is selected from H, methyl, hydroxymethyl, methoxymethyl and benzyl;

each Y (if present) is H;

each-R1 is pyridin-2-yl, imidazol-4-yl, benzimidazol-2-yl, each optionally substituted with one or more C₁-₆Alkyl substitution;

both-R2-moieties, if present, are pyridine-2, 6-diyl, imidazole-1, 4-diyl, or imidazole-2, 5-diyl;

each R5 is optionally substituted pyridin-2-yl;

the or each-R7 is selected from-H, methyl and benzyl;

the or each-R8 is selected from-H, C_1-18Alkyl and benzyl;

the or each-R10-is-CH₂-；

The or each R11 is optionally substituted pyridin-2-yl, imidazol-4-yl or benzimidazol-2-yl, for example unsubstituted pyridin-2-yl; and

each Q and Q2 (if present) is selected from-CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-and-CH₂CHOHCH₂-、1，2-phenylene and 1, 4-phenylene, each optionally substituted with C₁-₆Alkyl substitution, e.g. each of Q and Q2 (if present) is-CH₂CH₂-。

43. The composition of any of clauses 2-42, wherein the chelating agent is capable of chelating at least one transition metal ion through four donor nitrogen atoms.

44. The composition of clause 1, wherein the chelating agent is N, N-tris (pyridin-2-yl-methyl) amine.

45. The composition of any of clauses 1, wherein the chelating agent is N-methyl-N- (pyridin-2-ylmethyl) -bis (pyridin-2-yl) methylamine, N-benzyl-N- (pyridin-2-butylmethyl) -bis (pyridin-2-yl) methylamine, N-dimethyl-bis (pyridin-2-yl) methylamine, N-methyl-N- (pyridin-2-yl-methyl-1, 1-bis (pyridin-2-yl) -1-aminoethane, N-benzyl-N- (pyridin-2-ylmethyl-1, 1-bis (pyridin-2-yl) -1-aminoethane, N-benzyl-N- (pyridin-2-yl) methyl-1, 1-bis (pyridin-2, N-methyl-N- (pyridin-2-ylmethyl-1, 1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane or N-benzyl-N- (pyridin-2-ylmethyl-1, 1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane.

46. The composition of clause 1, wherein the chelating agent is N, N-tris (pyridin-2-yl-methyl) amine, N-methyl-N- (pyridin-2-yl-methyl) -bis (pyridin-2-yl) methylamine, or N-benzyl-N- (pyridin-2-yl-methyl) -bis (pyridin-2-yl) methylamine.

47. The composition of clause 1, wherein the chelating agent has formula (III) or (III-B).

48. The composition of clause 47, wherein R3 and R4 have the formula C (o) OR5, wherein each R5 is independently selected from hydrogen, C₁-C₈Alkyl and C_6-10And (4) an aryl group.

49. The composition of clause 48, wherein R3 and R4 have the formula C (o) OR5, wherein each R5 is independently C₁-C₄An alkyl group.

50. A composition according to any one of clauses 43 to 49, wherein R3 ═ R4.

51. The composition of clause 50, wherein the R3 and R4 groups are C (O) OCH₃。

52. The composition of any one of clauses 47 to 51Wherein X is selected from the group consisting of C ═ O and [ C (R6)₂]-, wherein each R6 is independently selected from hydrogen, hydroxy and C₁-C₄An alkoxy group.

53. The composition of clause 52, wherein X is selected from C ═ O, C (OH)₂And C (OCH)₃)₂。

54. The composition of clause 53, wherein X is C ═ O or C (oh)₂。

55. The composition of any of clauses 47-54, wherein the chelating agent is of formula (III).

56. The composition of clause 55, wherein each D is unsubstituted.

57. The composition of clause 55 or clause 56, wherein each D is the same.

58. The composition of clause 57, wherein each D is thiazol-2-yl or thiazol-4-yl.

59. The composition of any of clauses 55-58, wherein R1 and R2 are each independently selected from C₁-C₂₄Alkyl radical, C₆-C₁₀Aryl radical, C_6-10Aryl radical C₁-C₆Alkyl radical, C₅-C₁₀Heteroaryl group CH₂And CH₂CH₂N (R8) (R9), wherein-N (R8) (R9) is selected from-NMe 2, -NEt2, -N (i-Pr)2,And

60. the composition of clause 59, wherein one of R1 and R2 is C₁-C₂₄Alkyl or C_6-10Aryl radical C₁-C₆Alkyl, and the other of R1 and R2 is C₅-C₁₀Heteroaryl group CH₂Group or CH₂CH₂N(R8)(R9)。

61. The composition of clause 59 or as clause 60, wherein at least one of R1 and R2 is independently selected from C₁-C₁₈Alkyl and C₆-C₁₀Aryl radical C₁-C₆An alkyl group.

62. The composition of clause 61, wherein at least one of R1 and R2 is C₁-C₁₈An alkyl group.

63. The composition of clause 62, wherein at least one of R1 and R2 is C₁-C₁₂An alkyl group.

64. The composition of clause 61, wherein at least one of R1 and R2 is independently selected from C₁-C₈Alkyl and C₆-C₁₀Aryl radical CH₂。

65. The composition of any one of clauses 59 to 64, wherein at least one of R1 and R2 is methyl.

66. The composition of any of clauses 59-65, wherein at least one of R1 and R2 is independently selected from pyridin-2-ylmethyl, pyrazin-2-ylmethyl, quinolin-2-ylmethyl, pyrazol-1-ylmethyl, pyrazol-3-ylmethyl, pyrrol-2-ylmethyl, imidazol-4-ylmethyl, benzimidazol-2-ylmethyl, pyrimidin-2-ylmethyl, 1, 2, 3-triazol-1-ylmethyl, 1, 2, 3-triazol-2-ylmethyl, 1, 2, 3-triazol-4-ylmethyl, 1, 2, 4-triazol-3-ylmethyl, 1, 2, 4-triazol-1-ylmethyl, Thiazol-2-ylmethyl and thiazol-4-ylmethyl.

67. The composition of any of clauses 59-65, wherein at least one of R1 and R2 is independently selected from pyridin-2-ylmethyl, quinolin-2-ylmethyl, imidazol-2-ylmethyl, thiazol-2-ylmethyl, and thiazol-4-ylmethyl.

68. The composition of any of clauses 59-65, wherein one or each of R1 and R2 is optionally substituted pyridin-2-ylmethyl or CH₂CH₂N(R8)(R9)。

69. The composition of clause 68, wherein one or each of R1 and R2 is pyridin-2-ylmethyl.

70. The composition of any one of clauses 47 to 54, wherein the chelating agent has formula (III-B).

71. The composition of clause 70, wherein each E is unsubstituted.

72. The composition of clause 70 or the composition of clause 71, wherein each E is the same.

73. The composition of clause 72, wherein each E is pyridin-2-yl, thiazol-2-yl, or thiazol-4-yl.

74. The composition of clause 73, wherein each E is pyridin-2-yl.

75. The composition of any of clauses 70 to 74, wherein-Q-is selected from-CH₂CH₂-、-CH₂CH₂CH₂-and-CH₂CHOHCH₂-, each of which is optionally substituted by C₁-C₆Alkyl substitution.

76. The composition of clause 75, wherein-Q-is selected from-CH₂CH₂-、-CH₂CH₂CH₂-and-CH₂CHOHCH₂-。

77. The composition of any of clauses 70-76, wherein R2 is selected from C₅-C₁₀Heteroaryl group CH₂And CH₂CH₂N (R8) (R9), wherein-N (R8) (R9) is selected from-NMe 2, -NEt2, -N (i-Pr)2,And

78. the composition of clause 77, wherein R2 is selected from pyridin-2-ylmethyl, pyrazin-2-ylmethyl, quinolin-2-ylmethyl, pyrazol-1-ylmethyl, pyrazol-3-ylmethyl, pyrrol-2-ylmethyl, imidazol-4-ylmethyl, benzimidazol-2-ylmethyl, pyrimidin-2-ylmethyl, 1, 2, 3-triazol-1-ylmethyl, 1, 2, 3-triazol-2-ylmethyl, 1, 2, 3-triazol-4-ylmethyl, 1, 2, 4-triazol-3-ylmethyl, 1, 2, 4-triazol-1-ylmethyl, thiazol-2-ylmethyl, and thiazol-4-ylmethyl.

79. The composition of clause 77, wherein R2 is selected from pyridin-2-ylmethyl, quinolin-2-ylmethyl, imidazol-2-ylmethyl, thiazol-4-ylmethyl, and CH₂CH₂N(R8)(R9)。

80. The composition of clause 77, wherein R2 is selected from optionally substituted pyridin-2-ylmethyl and CH₂CH₂N(R8)(R9)。

81. The composition of clause 80, wherein R2 is pyridin-2-ylmethyl.

82. The composition of clause 1, wherein the chelating agent is selected from the group consisting of: dimethyl 2, 4-bis (thiazol-2-yl) -3-methyl-7- (pyridin-2-ylmethyl) -3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-2-yl) -3- (pyridin-2-ylmethyl) -7-methyl-3, 7-diazabicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-4-yl) -3-methyl-7- (pyridin-2-ylmethyl) -3, 7-diazabicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-4-yl) -3- (pyridin-2-ylmethyl) -7-methyl-3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-2-yl) -3, 7-dimethyl-3, 7-dimethyldiaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-4-yl) -3, 7-dimethyl-3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, hydrochloride, di-carboxylic acid, di-methyl-2, 4-bis (thiazol-4-yl) -3, 7-dimethyl-3, 7-diaza-bicyclo [3.3.1] non-9-one-1, 5-, 1, 2-bis {1, 5-bis (methoxycarbonyl) -3- (pyridin-2-ylmethyl) -9-oxo-2, 4-bis (pyridin-2-yl) -3, 7-diazabicyclo [3.3.1] non-7-yl } ethane, 1, 3-bis {1, 5-bis (methoxycarbonyl) -3- (pyridin-2-ylmethyl) -9-oxo-2, 4-bis (pyridin-2-yl) -3, 7-diazabicyclo [3.3.1] non-7-yl } propane, 1, 2-bis {1, 5-bis (methoxycarbonyl) -3-methyl-9-oxo-2, 4-bis (pyridin-2-yl) -3, 7-diazabicyclo [3.3.1] non-7-yl } ethane and 1, 3-bis {1, 5-bis (methoxycarbonyl) -3-methyl-9-oxo-2, 4-bis (pyridin-2-yl) -3, 7-diazabicyclo [3.3.1] non-7-yl } propane.

83. The composition of clause 82, wherein the chelating agent is selected from the group consisting of: dimethyl 2, 4-bis (thiazol-2-yl) -3-methyl-7- (pyridin-2-ylmethyl) -3, 7-diazabicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-2-yl) -3- (pyridin-2-ylmethyl) -7-methyl-3, 7-diazabicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-4-yl) -3-methyl-7- (pyridin-2-ylmethyl) -3, 7-diazabicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, dimethyl 2, 4-bis (thiazol-4-yl) -3- (pyridin-2-ylmethyl) -7-methyl-3, 7-diazabicyclo [3.3.1] non-9-one-1, 5-dicarboxylate, 1, 2-bis {1, 5-bis (methoxycarbonyl) -3- (pyridin-2-ylmethyl) -9-oxo-2, 4-bis (pyridin-2-yl) -3, 7-diazabicyclo [3.3.1] non-7-yl } ethane and 1, 3-bis {1, 5-bis (methoxycarbonyl) -3- (pyridin-2-ylmethyl) -9-oxo-2, 4-bis (pyridin-2-yl) -3, 7-diazabicyclo [3.3.1] non-7-yl } propane.

84. The composition of clause 1, wherein the chelating agent has formula (IV).

85. The composition of clause 84, wherein F represents methylene or ethylene and F' represents ethylene or n-propylene.

86. The composition of clause 84 or as clause 85, wherein-R¹、-R²、-R³and-R⁴Each independently represents-H, -C_1-6Alkyl radical, C_6-10An aryl group or a group containing a heteroatom capable of coordinating to a metal ion.

87. The composition of clause 86, wherein-R¹、-R²、-R³and-R⁴Each independently represents-H, -C_1-6Alkyl radical, C_6-10An aryl group or a group containing a heteroatom capable of coordinating to a metal ion.

88. The composition of any of clauses 84 to 87, wherein-R¹、-R²、-R³and-R⁴Each independently represents-H, -methyl, C_6-10An aryl group or a group containing a heteroatom capable of coordinating to a metal ion.

89. The composition of any of clauses 84 to 88, wherein the heteroatom capable of coordinating to a metal ion is contained in a heteroaryl or non-aromatic heterocycle, which is optionally substituted with C_1-4Alkyl substitution.

90. The composition of any of clauses 84 to 89, wherein the heteroatom capable of coordinating to a metal ion is contained in a heteroaryl ring.

91. The composition of clauses 89 or 90, wherein the heteroaryl ring is unsubstituted.

92. The composition of any one of clauses 89 to 91, wherein the heteroaryl ring is selected from the group consisting of: pyridin-2-yl, pyrazin-2-yl, quinolin-2-yl, pyrazol-1-yl, pyrazol-3-yl, pyrrol-2-yl, imidazol-4-yl, benzimidazol-2-yl, pyrimidin-2-yl, 1, 2, 3-triazol-1-yl, 1, 2, 3-triazol-2-yl, 1, 2, 3-triazol-4-yl, 1, 2, 4-triazol-1-yl, 1, 2, 4-triazol-3-yl, and thiazol-2-yl and thiazol-4-yl.

93. The composition of clause 92, wherein the heteroaryl ring is pyridin-2-yl.

94. The composition of any of clauses 90 to 93, wherein the ring is attached to the remainder of formula (IV) through an alkylene linker.

95. The composition of clause 94, wherein the alkylene linker is methylene.

96. The composition of any of clauses 84 to 95, wherein-R¹、-R²、-R³and-R⁴One or more of which is pyridin-2-ylmethyl.

97. The composition of clause 84, wherein the chelating agent has formula (V):

wherein:

each of-R¹Independently is-H, -C_1-24Alkyl, -C_6-10Aryl or pyridin-2-ylmethyl wherein aryl or pyridyl is optionally substituted by C_1-4Alkyl substitution;

-R²represents-H or-CH₃(ii) a And

each of-R³and-R⁴Independently is-H, -C_1-24Alkyl radical, -C_6-10Aryl or pyridin-2-ylmethyl wherein aryl or pyridyl is optionally substituted by C_1-4Alkyl substitution.

98. The composition of clause 97, wherein the chelating agent is selected from the group consisting of:

6-dimethylamino-1, 4-bis (pyridin-2-ylmethyl) -6-methyl-1, 4-diazepane;

6-amino-1, 4-bis (pyridin-2-ylmethyl) -6-methyl-1, 4-diazepane;

1, 4, 6-trimethyl-6- { N- (pyridin-2-ylmethyl) -N-methylamino } -1, 4-diazepane;

6-amino-1, 4, 6-trimethyl-1, 4-diazepane;

6-dimethylamino-1, 4, 6-trimethyl-1, 4-diazepane;

1, 4, 6-trimethyl-6- (pyridin-2-ylmethyl) amino) -1, 4-diazepane;

6- { N, N-bis (pyridin-2-ylmethyl) amino } -1, 4, 6-trimethyl-1, 4-diazepane; and

6- { N- (pyridin-2-ylmethyl) -N-methylamino } -1, 4-bis (pyridin-2-ylmethyl) -6-methyl-1, 4-diazepane.

99. The composition of clause 98, wherein the chelating agent is selected from the group consisting of 6-amino-1, 4-bis (pyridin-2-ylmethyl) -6-methyl-1, 4-diazepane and 1, 4, 6-trimethyl-6- { N- (pyridin-2-ylmethyl) -N-methylamino } -1, 4-diazepane.

100. The composition of any of clauses 1 to 99, wherein the concentration of the chelating agent relative to the unsaturated resin and any reactive diluent (if present) is between about 0.00005 to about 0.5% w/w.

101. The composition of clause 100, wherein the concentration of the chelating agent relative to the unsaturated resin and any reactive diluent (if present) is between about 0.0001 to about 0.1% w/w.

102. The composition of any of clauses 1 to 101, comprising a complex comprising a chelating agent and a transition metal ion selected from the group consisting of ions of iron, manganese, vanadium, and copper.

103. The composition of clause 102, comprising a complex comprising a chelating agent and a transition metal ion selected from the group consisting of iron and manganese ions.

104. The composition of clause 102 or clause 103, comprising a complex comprising a chelating agent and iron ions.

105. The composition of any of clauses 102 to 104, wherein the complex is not explicitly defined.

106. The composition of any one of clauses 1 to 101, comprising less than 0.001 weight percent of ions of each of iron, manganese, cobalt, vanadium, and copper.

107. The composition of any of clauses 1 to 106, wherein the concentration of the peroxide relative to the unsaturated resin is between about 0.01% to about 8% w/w.

108. The composition of clause 107, wherein the concentration of the peroxide relative to the unsaturated resin is between about 0.1% and about 6% w/w.

109. The composition of clause 108, wherein the concentration of the peroxide relative to the unsaturated resin is between about 0.3 to about 4% w/w.

110. The composition of clause 109, wherein the concentration of the peroxide relative to the unsaturated resin is between about 0.5 to about 2% w/w.

111. The composition of any of clauses 1-110, wherein the peroxide is an organic peroxide, such as a hydroperoxide or a ketone peroxide.

112. The composition of clause 111, wherein the peroxide is selected from the group consisting of: cumyl hydroperoxide, 1, 3, 3-tetramethylbutyl hydroperoxide, tert-butyl hydroperoxide, isopropylcumyl hydroperoxide, tert-amyl hydroperoxide, 2, 5-dimethyl-2, 5-dihydroperoxide, pinane hydroperoxide and pinene hydroperoxide.

113. The composition of clause 111, wherein the peroxide is selected from the group consisting of methyl ethyl ketone peroxide, methyl isopropyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide.

114. The composition of any of clauses 1-113, wherein the unsaturated resin is an unsaturated polyester resin or a vinyl ester resin

115. The composition of clause 114, wherein the vinyl ester resin is a (meth) acrylic resin.

116. The composition of any of clauses 1-115, wherein the composition comprises a reactive diluent.

117. The composition of clause 116, wherein the reactive diluent is selected from the group consisting of styrene, vinyl toluene, divinylbenzene, methyl methacrylate, diallyl phthalate, alpha-methylstyrene, triallyl cyanurate, (meth) acrylate, N-vinyl pyrrolidone, and N-vinyl caprolactam.

118. A method of preparing a composition as defined in any of clauses 1 to 117, the method comprising contacting a first formulation comprising a peroxide, a second formulation comprising a chelating agent as defined in any of clauses 1 to 99; and a third formulation comprising an unsaturated resin.

119. The method of clause 118, wherein the composition is as recited in clause 106.

120. The method of clause 119, further comprising contacting the composition with a source of transition metal ions.

121. The method of any of clauses 118 to 120, wherein the peroxide and the unsaturated resin are contained in the same formulation, which formulation is contacted with a second formulation and a source of transition metal ions.

122. The method of any of clauses 118-120, wherein the chelating agent and the peroxide are contained in the same formulation, the formulation comprising less than 0.001 weight percent of ions of each of iron, manganese, vanadium, cobalt, and copper, the formulation being contacted with a third formulation and a source of transition metal ions.

123. The method of any of clauses 118-120, wherein the chelating agent and unsaturated resin are contained in the same formulation, the formulation further comprising a source of transition metal ions, the formulation being contacted with the first formulation.

124. The method of any of clauses 120 to 123, wherein the transition metal ion is an iron, manganese, vanadium, or copper ion.

125. The method of any of clauses 120 to 124, wherein the transition metal ion is in solution.

126. The method of any of clauses 120 to 125, wherein the transition metal ion is an iron or manganese ion.

127. The method of clause 126, whichWherein said source of transition metal ions is an optionally hydrated salt selected from the group consisting of: MnCl₂、FeCl₂、FeCl₃、MnBr₂、Mn(NO₃)₂、Fe(NO₃)₃、MnSO₄、FeSO₄、(Fe)₂(SO₄)₃Mn (acetylacetone)₂Fe (acetylacetone)₂Mn (acetylacetone)₃Fe (acetylacetone)₂、Mn(R₄COO)₃、Fe(R₄COO)₃、Mn(R₄COO)₂And Fe (R)₄COO)₂。

128. The method of any of clauses 120 to 127, wherein the transition metal ion is an iron ion.

129. The method of clause 128, wherein the transition metal ion source is an optionally hydrated salt selected from the group consisting of: FeCl₂、FeCl₃、Fe(NO₃)₃、FeSO₄、(Fe)₂(SO₄)₃Fe (acetylacetone)₂Fe (acetylacetone)₃Fe (acetate)₂Fe (acetate)₃Fe (caprylate)₂Fe (2-ethylhexanoate)₂Fe (naphthenate)₂And Fe (neodecanoate)₂。

130. The method of clause 118, wherein the second formulation comprises a mixture of a chelating agent and a salt of a transition metal ion selected from the group consisting of ions of iron, manganese, vanadium, and copper.

131. The method of clause 130, wherein the second formulation comprises a salt of iron or manganese.

132. The method of clause 131, wherein the salt is as defined in any one of clauses 127 to 129.

133. The method of clause 121, wherein the second formulation comprises a complex as defined in clause 105.

134. The method of any of clauses 118 to 133, wherein the peroxide is as defined in any of clauses 111 to 113.

135. The composition of clause 105, obtained or obtainable by the method as defined in any one of clauses 118 to 134.

136. A composition obtained by curing a composition as defined in any of clauses 102 to 105 or 135.

137. A formulation comprising a chelating agent of formulae (I), (I-B), (II-B), (II-C), (III-B) and (IV) as defined in any one of clauses 1 to 99 and an unsaturated resin or peroxide.

138. The formulation of clause 137, comprising a complex comprising a chelating agent and a transition metal ion selected from the group consisting of ions of iron, manganese, vanadium, and copper.

139. The formulation of clause 138, comprising a complex comprising a chelating agent and a transition metal ion selected from iron and manganese ions.

140. The formulation of clause 138 or clause 139, comprising a complex comprising a chelating agent and an iron ion.

141. The formulation of any one of clauses 138 to 140, wherein the complex is not explicitly defined.

142. The formulation as in any one of clauses 137-141 comprising an unsaturated resin, such as an unsaturated polyester resin or a vinyl ester resin, and optionally a reactive diluent, such as the reactive diluent as defined in clause 117.

143. The formulation of clause 142, wherein the vinyl ester resin is a (meth) acrylic resin.

144. The formulation of clause 137, wherein the formulation comprises an unsaturated resin as defined in clause 142 or as defined in clause 143 and optionally a reactive diluent, for example a reactive diluent as defined in clause 117, and the formulation comprises less than 0.001% by weight of ions of each of iron, manganese, cobalt, vanadium, and copper.

145. The formulation of any one of clauses 137 to 141, comprising a peroxide.

146. The formulation of clause 145, wherein the peroxide is as defined in any one of clauses 111 to 113.

147. A kit comprising a first formulation which is a composition as defined in clause 106 and a separate second formulation comprising a transition metal ion selected from the group consisting of iron, manganese, vanadium and copper ions.

148. A kit comprising a first formulation comprising an unsaturated resin, a chelating agent of formula (I), (II-B), (III-B), (III-C) or (IV) as defined in any of clauses 1 to 99 and a transition metal ion selected from iron, manganese, vanadium and copper ions, and independently, a second formulation comprising a peroxide.

149. A kit, comprising:

(i) a first formulation comprising an unsaturated resin;

(iii) a third formulation comprising a peroxide.

150. The kit of clause 148 or clause 149, wherein the unsaturated resin is an unsaturated polyester resin or a vinyl ester resin

151. The kit of clause 150, wherein the vinyl ester resin is a (meth) acrylic resin.

152. The kit of any one of clauses 148 to 151, wherein the first formulation further comprises a reactive diluent.

153. The kit of clause 152, wherein the reactive diluent is selected from the group consisting of styrene, vinyl toluene, divinylbenzene, methyl methacrylate, diallyl phthalate, alpha-methylstyrene, triallyl cyanurate, (meth) acrylate, N-vinyl pyrrolidone, and N-vinyl caprolactam.

154. The kit of any one of clauses 148 to 153, wherein the transition metal ion is an iron or manganese ion.

155. The kit of clause 154, wherein the ion is provided in the form of a salt as defined in clause 127.

156. The kit of clause 154 or as clause 155, wherein the transition metal ion is an iron ion.

157. The kit of clause 156, wherein the transition metal ion is provided in the form of a salt as described in clause 129.

Experiment of

[(2-TBP)Fe^IICl](Cl) meoh.1.5h2o (2-TBP ═ dimethyl 3-methyl-9-oxo-2, 4-bis (thiazol-2-yl) -7- (pyridin-2-ylmethyl) -3, 7-diazabicyclo [3.3.1]Nonane-1, 5-dicarboxylate) and [ (4-TBP) Fe^IICl](Cl) meoh.1.5h2o (4-TBP ═ dimethyl 3-methyl-9-oxo-2, 4-bis (thiazol-4-yl) -7- (pyridin-2-ylmethyl) -3, 7-diazabicyclo [3.3.1]Nonane-1, 5-dicarboxylate) was achieved as follows. The synthesis of the ligand is described first, followed by the synthesis of the iron complex. Ligand synthesis has been accomplished in two steps, as outlined below. The iron complex is then prepared in a one-step process.

2, 6-bis (thiazol-2-yl) -3, 5-dimethyl-N-methyl-4-piperidine-3, 5-dicarboxylate

2-Thiazolecarboxaldehyde (12.0g, 106mmol) was dissolved in MeOH (32ml) and the solution was cooled with a water bath at room temperature. Dropwise addition of methylamine (H)₂O40% w/w) (4.59ml, 53.0mmol) and then dimethyl-1, 3-acetonedicarboxylate (7.65ml, 53.0mmol) was added dropwise. The reaction mixture was stirred at 65 ℃ for 90 minutes and then stored in a refrigerator for 7 days. The resulting suspension was suction filtered with a glass filter P4 and the solid was rinsed with cold EtOH (absolute) (3X 10 ml). The last traces of volatiles were evaporated in vacuo to give a white solid (9.00g, 22.8mmol, 43%).¹H NMR (400MHz, CDCl3) delta ketone: 2.05(s, 3H), 3.74(s, 6H), 4.31(d, J ═ 11.0Hz, 2H), 5.11(d, J ═ 10.9Hz, 2H), 7.41-7.42(m, 2H), 7.68-7.70(m, 2H); enol alcohol: 2.37(s, 3H), 3.74(s, 3H), 3.77(s, 3H), 4.08(d, J ═ 9.0Hz, 1H), 4.84(d, J ═ 9.0Hz, 1H), 4.99(s, 1H), 7.33 to 7.35(m, 2H), 7.68 to 7.70(m, 1H), 7.71 to 7.72(m, 1H), 12.48(s, 1H), 13C NMR (100.6MHz, CDCl3) δ ketone: 32.28, 52.45, 55.80, 64.55, 121.20, 141.82, 167.80, 167.86, 197.94; enol alcohol: 36.89, 45.23, 51.98, 52.78, 58.83, 60.75, 98.29, 120.05, 120.41, 141.86, 142.38, 166.03, 168.15, 169.59, 171.46, 172.51. ESI-MS M/z 396.3[ M + H ]]⁺。HRMS(APCI)(C₁₆H₁₈N₃O₅S₂The calculated value of (a): 396.068) found: 396.068[ M + H]⁺。

Dimethyl 3-methyl-9-oxo-2, 4-bis (thiazol-2-yl) -7- (pyridin-2-ylmethyl) -3, 7-diazabicyclo [3.3.1] nonane-1, 5-dicarboxylate (2-TBP).

2-Piperidinamine (2.44ml, 23.7mmol) was dissolved in isobutanol (125ml) and the solution was cooled with a water bath at room temperature. Formaldehyde (37%) (3.52ml, 47.3mmol) was added dropwise followed by slow addition of 2, 6-bis (thiazol-2-yl) -3, 5-dimethyl-N-methyl-4-piperidine-3, 5-dicarboxylate (8.50g, 21.5 mmol). The reaction mixture was stirred at reflux for 90 minutes and then allowed to cool to room temperature. The suspension was filtered with suction on a glass filter P4 and the solid was washed with isobutanol (3X 10 ml). The last traces of volatiles were evaporated in vacuo to yield a white solid (6.80g, 12.9mmol, 60%).¹H NMR(400MHz，CDCl₃)δ2.41(s，3H)，2.84(d，J＝12.5Hz，2H)，3.03(d，J＝12.9Hz，2H)，3.71(s，2H)，3.84(s，6H)，5.19(s，2H)，7.16-7.19(m，1H)，7.31-7.33(m，3H)，7.62-7.66(m，1H)，7.71-7.74(m，2H)，8.47-8.48(m，1H).¹³C NMR(100.6MHz，CDCl3)δ45.40，52.83，57.54，62.64，62.80，70.05，120.40，122.31，124.66，136.09，142.77，149.05，155.67，167.63，170.83，201.90。ESI-MS m/z 528.3[M+H]⁺There is a minor peak at m/z 451.2. HRMS (APCI) (C)₂₄H₂₆N₅O₅S₂The calculation of (2): 528.137) found: 528.138[ M + H]⁺。

2, 6-bis (thiazol-4-yl) -3, 5-dimethyl-N-methyl-4-piperidine-3, 5-dicarboxylate

Dimethylacetone dicarboxylate (1.67ml, 0.0111mol) and methylamine (40 wt% in water) (0.96ml, 0.0111mol) were added dropwise to an ice-cold solution of thiazole-4-carbaldehyde in MeOH (25 ml) (2.52g, 0.0222 mol)l) in (1). After stirring at this temperature for 2.5 hours and then at room temperature for a further 1.5 hours, the cloudy orange solution was stored in a refrigerator (-20 ℃ C.) overnight. The product was collected, washed with cold EtOH (5ml) and the last traces of volatiles were evaporated in vacuo. Two further batches were obtained by evaporation of the filtrate and recrystallization. The total yield of the product in the keto form (off-white powder) and the enol form (white crystals) was 1.87g (4.72mmol, 43%). Ketone form:¹H NMR(400MHz，CDCl₃)δ8.84(d，J＝1.8Hz，2H)，7.21(s，2H)，4.78(d，J＝6.0Hz，2H)，4.13(d，J＝6.0Hz，2H)，3.76(s，6H)，2.06(s，3H).¹³c NMR (101MHz, CDCl3) δ 207.07, 168.59, 153.49, 117.69, 61.60, 60.26, 52.86, 40.35, 31.08. enol form: 1H NMR (400MHz, CDCl)₃)δ8.82(d，J＝1.9Hz，1H)，8.77(d，J＝2.0Hz，1H)，7.38(s，1H)，7.16(s，1H)，5.11(s，1H)，4.52(d，J＝9.7Hz，1H)，4.18(d，J＝9.7Hz，1H)，3.69(s，3H)，3.66(s，3H)，2.19(s，3H)，1.57(s，1H)。¹³C NMR(101MHz，CDCl₃)δ171.59，171.07，166.62，157.04，154.91，153.13，152.50，117.25，102.50，100.02，59.12，57.03，52.78，52.10，48.49，38.28。

Dimethyl 3-methyl-9-oxo-2, 4-bis (thiazol-4-yl) -7- (pyridin-2-ylmethyl) -3, 7-diazabicyclo [3.3.1] nonane-1, 5-dicarboxylate (4-TBP)

Formaldehyde (37 wt%, aqueous solution) (1.97ml, 0.0264mol) and 2-pyridylamine (1.36ml, 0.0132mol) were added to a suspension of pLG (in the keto and enol form) (5.21g, 0.0132mol) in ethanol (100 ml). The reaction mixture was heated at reflux temperature and the solid slowly dissolved to give a clear colorless solution after heating. After a few minutes, the reaction mixture became cloudy again and a white precipitate was observed. After 5 hours, the reaction mixture was cooled to room temperature. The suspension was filtered with suction on a glass filter P4 and subsequently washed with cold EtOH (15 ml). The last traces of volatiles were evaporated in vacuo to give an off-white powder (3.45g, 6.54mmol, 50%).¹H NMR(400MHz，CDCl₃)δ8.66(d，J＝2.1Hz，2H)，8.62(d，J＝4.1Hz，1H)，7.63(td，J＝7.7，1.7Hz，1H)，7.57(d，J＝2.0Hz，2H)，7.35(d，J＝7.7Hz，1H)，7.24-7.19(m，1H)，4.79(s，2H)，3.75(s，6H)，3.63(s，2H)，3.40(d，J＝12.0 Hz，2H)，3.00(d，J＝11.8Hz，2H)，2.01(s，3H)。¹³C NMR(101MHz，CDCl3)δ202.87，168.68，157.74，154.77，152.47，149.46，136.50，124.17，122.57，118.52，69.75，63.31，62.81，58.22，52.65，42.78。

[ (2-TBP) FeIICl ] (Cl) meoh.1.5h2o (2-TBP ═ dimethyl 3-methyl-9-oxo-2, 4-bis (thiazol-2-yl) -7- (pyridine-2- (methyl) -3, 7-diazabicyclo [3.3.1] nonane-1, 5-dicarboxylate)

MeOH (20ml) was purged with argon for 20 minutes. Iron (II) chloride tetrahydrate (279mg, 1.40mmol) was added. Subsequently, dimethyl 3-methyl-9-oxo-2, 4-bis (thiazol-2-yl) -7- (pyridin-2-ylmethyl) -3, 7-diazabicyclo [3.3.1]Nonane-1, 5-dicarboxylate (750mg, 1.42mmol) was added and the resulting mixture was stirred at 50 ℃ for 10 min. The reaction mixture was cooled to room temperature and the volatiles were evaporated in vacuo to give a yellow oil. EtOAc (20ml) was added and the mixture was sonicated at room temperature for 60 min. The resulting yellow suspension was filtered with suction through a glass filter P4 and the solid was washed with EtOAc (5X 20ml) and Et 2O (5X 20 ml). The last traces of volatiles were evaporated in vacuo to give a yellow powder (817mg, 1.15mmol, 82%). ESI-MS m/z 300.8[ LFe^II(H2O)]²⁺，307.7[LFe^II(MeOH)]²⁺，328.4[LFe^III(ⁱBuO)]²⁺Or [ LFe ]^II(MeOH)(CH₃CN)]²⁺，636.2[LFe^II(Cl)(H₂O)]⁺，650.3[LFe^II(Cl)(MeOH)]⁺，660.3[LFe^II(HCO₂)(MeOH)]⁺. Elemental analysis (C)₂₄H₂₅N₅O₅S₂FeCl₂.CH₃OH.1.5H₂Calculated value of O: c42.09%, H4.52%, N9.82%, S8.99%), found: c42.03%, H4.42%, N9.53%, S8.73%.

[(4-TBP)Fe^IICl](Cl).0.5MeOH.2H₂O (4-TBP ═ dimethyl 3-methyl-9-oxo-2, 4-bis (thiazol-2-yl) -7- (pyridin-2- (methyl) -3, 7-diaza-bisRing [3.3.1]Nonane-1, 5-dicarboxylic acid salts)

In N₂Dimethyl 3-methyl-9-oxo-7- (pyridin-2-ylmethyl) -2, 4-bis (thiazol-4-yl) -3, 7-diazabicyclo [3.3.1] under an atmosphere]Nonane-1, 5-dicarboxylate ligand (4-TBP) (420mg, 0.79mmol, 1.0 equiv.) was dissolved in degassed MeOH (10 ml). The reaction mixture was heated at 60 ℃ and a white powder was observed to be suspended in a colorless solution. Then in N₂Adding FeCl at the bottom₂.4H₂O (158mg, 0.79mmol, 1.0 equiv.) gives a clear yellow solution. The resulting mixture was heated at 60 ℃ for an additional 1.5 hours. Subsequently, the mixture was allowed to cool to room temperature. The mixture was filtered using pleated filter paper and the residue was rinsed with MeOH (10 ml). The filtrates were combined and the volatiles evaporated in vacuo to give a yellow oil. The solid was obtained by dissolving the oil in a minimum amount of MeOH, and the solution was slowly added dropwise to Et₂O (150ml) with stirring and vortexing (1500 rpm). The suspension is filtered off with suction on a glass filter P4 and subsequently Et₂O (15ml) wash. The last traces of volatiles were evaporated in vacuo to give a yellow powder (495mg, 0.70mmol, 88%). ESI-MS m/z 172.8[ (L) Fe^II(CH₃CN)]²⁺，193.3[LFe^II(2CH₃CN)]²⁺，339.3[LFe^IICl]⁺. Elemental analysis (C)_24.5H₃₁C₁₂FeN₅O_7.5S₂The calculated value of (a): c41.66%, H4.42%, N9.91%, S9.08%); measured value: c41.82%, H4.23%, N9.86%, S9.47%).

All curing experiments described below used Palatal P6-01 (Aliamys), Palatal P6-01 being an unsaturated polyester based on phthalic acid and a diol dissolved in styrene. The solids content was 65% and, when tested on the 5g scale, the amount of unsaturated polyester was 3.25g in each case.

Cumene Hydroperoxide (CHP) was used as peroxide at a content of 0.1M.

The amount of catalyst is from 10 to 100ppm (based on metal relative to solid content).

The standard procedure is as follows:

5g of Palatal P6-01 were weighed into a 20mL glass vial.

60.6. mu.L of CHP 80% (100 mM based on resin solids) was added with a glass pipette and stirred manually through the Palatal resin. This corresponds to about 1% CHP (based on total Palatal solution).

100. mu.L of the catalyst mother liquor was added to obtain a metal content of 100ppm, 10ppm or 1ppm (based on the solid content). The choice of solvent depends on the catalyst or chelating agent/metal salt used.

The catalyst solution (or chelator/metal salt solution) was stirred manually through Palatal and a timer was started.

Solidification of Palatal was checked at room temperature by manual stirring/feeling with a glass pipette.

The iron and manganese complexes or chelating agents/metal salts used in the experiments were obtained as follows. In the reference experiment, cobalt (2-ethylhexanoate) was used₂And [ Fe (N2py3) Cl]Cl was used as a catalyst.

It should be noted that the given amounts of metal salt and chelating agent were, given 100. mu.L of solvent (mixture) in each experiment, added to the unsaturated resin solution so that 5g was produced in each experiment. Obviously, due to the accuracy of weighing the samples, larger stock solutions can be prepared and 100 μ L of each stock solution used in each experiment. When lower levels of metal/chelating agent (relative to the resin) are used, the mother liquor is further diluted in the same solvent mixture to ensure that the same volume of solvent is always present in the solution of unsaturated resin, catalyst and peroxide. For example, as shown below, when 100ppm Fe is required, 1.72mg of tris (pyridin-2-ylmethyl) amine (abbreviated TPA) and 1.16mg of FeCl₂.4H₂O was dissolved in 50. mu.L of Dowanol DPM, respectively, and then mixed. The mixture was then added to the resin to give a 5g sample of activated resin (Dowanol DPM ═ dipropylene glycol monomethyl ether). In practice, when at least 5mg of TPA is first weighed (to achieve the correct weighing accuracy), this amount needs to be dissolved in Dowanol DPM, which amount corresponds to 1.16mg in 50 μ L of Dowanol DPM. From this mother liquor 50. mu.L of 1.12mg FeCl added to 50. mu.L of DoL Dowanol DPM₂.4H₂In O (obviously, the solution is also prepared first on a larger scale in order to accurately weigh out the FeCl₂.4H₂O(＞5mg))。

For the same experiment with only 10ppm Fe, 1.72mg of TPA was dissolved in 50. mu.L of Dowanol DPM and 1.16mg of FeCl₂.4H₂O was dissolved in 50. mu.L of Dowanol DPM (as described above). 450 μ L of Dowanol DPM was then added to each solution, and the diluted solution was multiplied by 10. Then 50 μ L of each solution was taken out, mixed together (Fe-TPA mixture in 100 μ L of Dowanol DPM) and then added to the resin solution.

Reference 1: cobalt 2 (65% w/w, from Sigma Aldrich), abbreviated Co (EH)₂: 2.93mg were dissolved in 100. mu.L heptane.

Reference 2: manganese (2-ethylhexanoate) (37% w/w from Alfa Aesar), abbreviated Mn (EH) 2: 5.46mg dissolved in 100. mu.L of Dowanol DPM.

Reference 3: iron (chloride) 2.4H2O (from Merck), abbreviated FeCl 2: 1.16mg dissolved in 100. mu.L methanol.

Reference 4: [ Fe (N2py3) Cl ] Cl (N2py3 ═ dimethyl 2, 4-bis (pyridin-2-yl) -3-methyl-7- (pyridin-2-ylmethyl) -3, 7-diazabicyclo [3.3.1] non-9-one-1, 5-dicarboxylate) was prepared as described in WO 02/48301A 1.4 mg of [ Fe (N2py3) Cl ] Cl was dissolved in 100. mu.L of ethylene glycol.

1: [ Fe (2-TBP) Cl ] Cl was prepared as described above. 4.1mg of [ Fe (2-TBP) Cl ] Cl was dissolved in 100. mu.L of methanol and then further diluted as necessary for correct metering.

Cndot (2): [ Fe (4-TBP) Cl ] Cl was prepared as described above. 4.1mg of [ Fe (4-TBP) Cl ] Cl were dissolved in 100. mu.L of methanol and then further diluted as necessary for correct metering.

·(3)：[Fe₂(μ-O)(μ-CH₃COO)(TPA)₂](ClO₄)₃Preparation of (d) has been described by L quee Jr and colleagues: J.am.chem.Soc., 112, 1554-. 4.86mg were dissolved in 100. mu.L Dowanol DPM (from Merck) and further diluted to the appropriate dose.

Cndot (4): tris (pyridine)-2-ylmethyl) amine (abbreviated TPA) was obtained from PI chemicals. FeCl₂.4H₂O was obtained from Merck. 1.16mg of FeCl₂.4H₂O was dissolved in 50. mu.L of methanol and 1.72mg of TPA was dissolved in 50. mu.L of Dowanol DPM. The two solutions were mixed and then added to the resin solution.

Cndot (5): tris (pyridin-2-ylmethyl) amine (1.72mg) was dissolved in 50. mu.L of Dowanol DPM and reacted with 5.4mg of (2-ethylhexanoic acid) dissolved in 50. mu.L of Dowanol DPM₂Manganese (6% w/wMn from Alfa Aesar mix)) to give a 100. mu.L solution of Mn-TPA in Dowanol DPM. This mixture is added to the unsaturated resin as described in the general method.

10 (6): N-methyl-N- (pyridin-2-yl-methyl) -bis (pyridin-2-yl) methylamine (abbreviated MeN3Py) was obtained as described in M Klopsla et al (Eur. J. Inorg. chem., 4, 846-856(2004))₂.4H₂And O. 1.16mg FeCl₂.4H₂O and 1.72mg of MeN3py were dissolved separately in 50. mu.L of Dowanol DPM and then mixed (to produce a MeN3py/Fe mixture in 100. mu.L of Dowanol DPM) and the mixture was added to the unsaturated resin as described in the general procedure.

Section (7): MeN3py (1.72mg) was dissolved in 50. mu.L of Dowanol DPM and mixed with 5.4mg of (2-ethylhexanoic acid) dissolved in 50. mu.L of Dowanol DPM₂Manganese (6% w/w Mn from Alfa Aesar) mixed to produce a Mn-MeN3py solution in 100. mu.L of lowanol DPM. This mixture is added to the unsaturated resin as described in the general method.

Cndot (8): 1, 4, 6-trimethyl-6- { N- (pyridin-2-ylmethyl) -N-methylamino } -1, 4-diazepane (abbreviated TMPD) was prepared as described in WO 01/85717A 1. MPD (1.55mg) was mixed with 5.4mg of (2-ethylhexanoic acid)₂Manganese was mixed in 100. mu.L methanol/heptane (1/1 v/v).

9: manganese complex of 1, 4, 6-trimethyl-6- { N- (pyridin-2-ylmethyl) -N-methylamino } -1, 4-diazepan (TMPD) [ Mn (TMPD) Cl₂By mixing equimolar amounts of TMPD and FeCl in methanol under argon₂.4H₂O. Removing the solvent and washing with diethyl etherAfter washing, the white powder obtained was dried and used without further purification.

10: 6-amino-1, 4-bis (pyridin-2-ylmethyl) -6-methyl-1, 4-diazepane (abbreviated ABPD) was prepared as disclosed in WO 01/85717A 1. ABPD (1.81mg) was mixed with 1.16mg FeCl₂.4H₂O was mixed in 100. mu.L of methanol.

Cndot (11): iron complex of 6-amino-1, 4-bis (pyridin-2-ylmethyl) -6-methyl-1, 4-diazepane (ABPD) [ Fe (ABPD) Cl ]]Cl₂By mixing equimolar amounts of TMPD and FeCl at 55 ℃ in methanol under argon₃.6H₂O. After cooling, the precipitate is filtered off and washed with some cold methanol and then with diethyl ether.

(12) other experiments were performed to test mixing of chelating agent with unsaturated resin (without transition metal salt), placing the mixture of unsaturated resin and chelating agent for 2 weeks at room temperature, and then FeCl₂And CHP is added to the mixture:

5g of Palatal P6-01 were weighed into a 20mL glass vial, and 0.173mg of TPA in 50. mu.L of CH was added₃CN, then manually stirred (Note; first 1.73mg of TPA in 50. mu.L of CH was prepared₃CN, then 450 μ L CH3CN was added, and 50 μ L was taken from the solution and added to the resin).

The solution was left at room temperature for two weeks, then 60.6. mu.L of CHP 80% (100 mM based on resin solids content) was added, and 0.116mg FeCl in 50. mu.L of methanol was added₂.4H₂O, then stirred manually and the time required for curing was monitored (note; 1.16mg FeCl was first prepared)₂.4H₂A solution of O in 50 μ L of methanol, then 450 μ L of methanol was added, then 50 μ L was taken from the solution and added to the resin).

(13) similarly, by combining a chelating agent with FeCl₂.4H₂O was mixed with the unsaturated resin, the resulting mixture of unsaturated resin and Fe-chelator complex was left at room temperature for 2 weeks, and then CHP was added to the mixture to conduct an experiment:

weighing in 20mL glass vials5g of Palatal P6-01, to which 100. mu.L of CH was added₃0.173mg TPA in CN and 0.116mg FeCl in 50. mu.L methanol₂.4H₂O, then stirred manually.

The solution was allowed to stand at room temperature for two weeks, then 60.6. mu.L of CHP 80% (100 mM based on resin solids) was added, followed by manual stirring and timer start.

(14) similarly, the mixture of chelating agent and CHP was left for 2 weeks, then unsaturated resin and FeCl were added₂：

Preparation of 8.66mg TPA in 2.5mL CH₃Mother liquor in CN. 50 μ L of this solution was taken and mixed with 60.6 μ L of CHP. The mixture was kept at room temperature for 2 weeks. After two weeks, 0.116mg FeCl dissolved in 50. mu.L methanol was added₂.4H₂O and 5g of Palatal P6-01, determining the curing time (iron content 10 ppm).

TABLE 1 curing time for different complexes or chelant/metal salt mixtures (1/1 mole ratio).

molar ratio).

n.d.: uncertainty

Note that: all values are in ppm metal relative to the unsaturated resin solids content (65 w/w%).

The results shown above show the following:

cobalt, manganese or iron salts without ligands did not show any significant curing activity (ref 1, ref 2 and ref 3).

Examples of 3 different classes of chelating agents with Mn or Fe (or both) according to the invention show a better than industry standard Co cobalt (cobalt 2-ethylhexanoate)₂The curing time of (3) is shorter.

[ (2-TBP) Fe, tested only at 1ppm^IICl](Cl) and [ (4-TBP) Fe^IICl](Cl) Cure times were all greater than using [ Fe (N2py3) Cl measured at 10ppm]Short Cl, the latter being a very active curing catalyst according to WO2011/083309 (1, 2 and reference 4).

Likewise, both the TPA/iron salt mixture (4) or the TPA-Fe complex (3) showed very good curing activity, again significantly better than using [ Fe (N2py3) Cl ] Cl (ref 4), despite the fact that TPA chelants have fewer coordinating nitrogen atoms (four) than iron and N2py3 chelants (with 5N donor groups). A similar mixture of Mn-soap and TPA (5) showed lower curing activity than the Fe-TPA complex, but still had higher activity than Mn-soap without ligand.

100ppm FeCl, tested at the same iron content₂.4H₂O with TPA (4) and well-defined complexes [ Fe ]₂(μ-O)(μ-CH₃COO)(TPA)₂](ClO₄)₃(3) Mixing and curing time were similar. When 10ppm of the Fe salt was used in combination with the TPA sequestrant (4), the cure speed was somewhat faster than for the well-defined complex (3) at the same Fe content.

Manganese soaps containing MeN3py (7) have similar or slightly better activity than the analogous Mn-TPA mixtures (5), whereas Fe-MeN3py (6) is significantly less active than Fe-TPA mixtures (4) (although in both cases its activity is more active than the metal salts without MeN3py ligands).

Complexes (not well defined) of Fe and Mn with two diazepan based chelating agents (8 and 10) also show a clear curing activity, again, Fe chelating agents are more active than Mn chelating agents.

The activity of manganese complexes with well-defined TMPD ligands is much lower than the in-situ formed Mn-soap/TMPD mixtures (9 vs 8) and the activity of iron complexes with well-defined ABPD ligands is also much lower than the in-situ formed FeCl₂ABPD mixtures (11 vs 10).

Pre-mixing the TPA chelating agent with the unsaturated resin, leaving the mixture for 2 weeks, then adding the peroxide and the iron salt, resulting in a curing time similar to that obtained when the chelating agent and the iron salt were added to the resin together with the peroxide (12 vs 4).

Similarly, premixing the TPA sequestrant and iron salt into the unsaturated resin, leaving this mixture for 2 weeks, then adding peroxide, also gives good cure times (and possibly even faster) (13 vs 4).

Also, premixing the TPA chelating agent with the peroxide, followed by addition of the unsaturated resin and iron salt, gives good curing activity (13 vs 4).

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