Novel flame retardant compositions for polyolefins

文档序号：1145558 发布日期：2020-09-11 浏览：30次中文

阅读说明：本技术 用于聚烯烃的新的阻燃剂组合物 (Novel flame retardant compositions for polyolefins ) 是由 S·赫罗德 T·王 J-P·兰斯 Y·郑于 2018-11-09 设计创作，主要内容包括：本发明涉及组合物,其包含作为组分(A)的式(I)的膦酸酯低聚物或聚合物,其中,Ar为芳族基团；R为C1-C20-烷基、C2-C20-烯烃、C2-C20-炔烃、C5-C20-环烷基或C6-C20-芳基；n为2至200的整数；—O—Ar—O—衍生自选自由间苯二酚类、氢醌类和双酚类及其组合组成的组的化合物；作为组分(B)的式(II)的氨基醚,其中,m可以小于或等于E中的碳原子数,和E为C1-至C1000000-烷基或C5-C6-环烷基,其中烷基链可以包含烷基取代基、芳族取代基和极性基团作为取代基,和可以被烯烃单元和/或杂原子中断；其中,G1和G2可以相同或不同并且彼此独立地为氢、卤素、NO2、氰基、CONR5R6、(R9)COOR4、C(O)-R7、OR8、SR8、NHR8、N(R18)2、氨基甲酰基、二(C1-C18-烷基)氨基甲酰基、C(＝NR5)(NHR6)、C1-C18-烷基；C3-C18-烯基；C3-C18-炔基、C7-C9-苯基烷基、C3-C12-环烷基或C2-C12-杂环烷基；被至少一个O原子和/或被-NR5-中断的C2-C18-烷基；C6-C10-芳基；苯基或萘基,其在每种情况下被下述取代：C1-C4-烷基、C1-C4-烷氧基、C1-C4-烷硫基、卤素、氰基、羟基、羧基、COOR21、C(O)-R22、C1-C4-烷基氨基或二(C1-C4-烷基)氨基；或者G1和G2与它们所键合的碳原子一起形成C3-C12-环；T’为氢、伯C1-C18-烷基、仲C3-C18-烷基、叔C4-C18-烷基或苯基基团,其每一个为未取代的或被下述取代：卤素、OH、COOR21或C(O)-R22；或C5-C12-环烷基或被至少一个O或-N(R18)-中断的C5-C12-环烷基；或具有7至18个碳原子的多环烷基基团,或被至少一个-O-或-N(R18)-中断的相同基团；或T’为C-(G1)(G2)-T”；T”为氢、卤素、NO2、氰基或具有1至50个碳原子的一价有机基团；或T"和T’一起形成二价有机连接基团,其与空间受阻胺氮原子和被G1和G2取代的季碳原子一起形成任选被取代的五元或六元环结构,和R4为氢、C1-C18-烷基、苯基、碱金属离子或四烷基铵阳离子；R5和R6彼此独立地为氢、C1-C18-烷基、被羟基取代的C2-C18-烷基,或者一起形成C2-C12-亚烷基桥或被-O-或/和-N(R18)-中断的C2-C12-亚烷基桥；R7为氢、C1-C18-烷基或C6-C10-芳基；R8为氢、C1-C18-烷基或C2-C18-羟基烷基；R9为C1-C12-亚烷基或键；R18为C1-C12-烷基或苯基,其为未取代的或被卤素、OH、COOR21或C(O)-R22取代；R21为氢、碱金属原子或C1-C18-烷基；R22为C1-C18-烷基；和作为组分(C)的热塑性聚合物。<Image he="634" wi="700" file="DDA0002489705560000021.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention relates to a composition comprising as component (a) a phosphonate oligomer or polymer of formula (I) wherein Ar is an aromatic group; r is C 1 ‑C 20 Alkyl radical, C 2 ‑C 20 -olefins, C 2 ‑C 20 -alkyne, C 5 ‑C 20 -cycloalkyl or C 6 ‑C 20 -an aryl group; n is an integer from 2 to 200; -O-Ar-O-is derived from a compound selected from the group consisting of resorcinols, hydroquinones and bisphenols and combinations thereof; as component (B) aminoethers of the formula (II) in which m may be smallEqual to or greater than the number of carbon atoms in E, and E is C 1 -to C 1000000 -alkyl or C 5 ‑C 6 -cycloalkyl, wherein the alkyl chain may comprise alkyl substituents, aromatic substituents and polar groups as substituents, and may be interrupted by alkene units and/or heteroatoms; wherein G1 and G2 may be the same or different and are independently of each other hydrogen, halogen, NO 2 Cyano, CONR 5 R 6 、(R 9 )COOR 4 、C(O)‑R 7 、OR 8 、SR 8 、NHR 8 、N(R 18 ) 2 Carbamoyl, di (C) 1 ‑C 18 -alkyl) carbamoyl, C (═ NR) 5 )(NHR 6 )、C 1 ‑C 18 -an alkyl group; c 3 ‑C 18 -an alkenyl group; c 3 ‑C 18 -alkynyl, C 7 ‑C 9 Phenylalkyl, C 3 ‑C 12 -cycloalkyl or C 2 ‑C 12 -a heterocycloalkyl group; by at least one O atom and/or by-NR 5 -C of the interrupt 2 ‑C 18 -an alkyl group; c 6 ‑C 10 -an aryl group; phenyl or naphthyl, which is substituted in each case by: c 1 ‑C 4 Alkyl radical, C 1 ‑C 4 -alkoxy, C 1 ‑C 4 Alkylthio, halogen, cyano, hydroxy, carboxy, COOR 21 、C(O)‑R 22 、C 1 ‑C 4 Alkylamino or di (C) 1 ‑C 4 -alkyl) amino; or G1 and G2 form C together with the carbon atom to which they are bonded 3 ‑C 12 -a ring; t' is hydrogen, primary C 1 ‑C 18 Alkyl, sec-C 3 ‑C 18 Alkyl, tertiary C 4 ‑C 18 -an alkyl or phenyl group, each of which is unsubstituted or substituted by: halogen, OH, COOR 21 Or C (O) -R 22 (ii) a Or C 5 ‑C 12 Cycloalkyl or substituted by at least one O or-N (R) 18 ) -C of the interrupt 5 ‑C 12 -a cycloalkyl group; or a polycycloalkyl group having 7 to 18 carbon atoms, or substituted with at least one-O-or-N (R) 18 ) -interrupted identical groups; or T' is C- (G) 1 )(G 2 ) -T "; t' is hydrogen, halogen, NO 2 Cyano or a monovalent organic group having 1 to 50 carbon atoms; or T 'and T' together form a divalent organic linking group with the sterically hindered amine nitrogen atom and the group G 1 And G 2 The substituted quaternary carbon atoms together form an optionally substituted five-or six-membered ring structure, and R 4 Is hydrogen, C 1 ‑C 18 -an alkyl group, a phenyl group, an alkali metal ion or a tetraalkylammonium cation; r 5 And R 6 Independently of one another are hydrogen, C 1 ‑C 18 Alkyl, C substituted by hydroxy 2 ‑C 18 -alkyl, or together form C 2 ‑C 12 An alkylene bridge or a substituted or unsubstituted alkylene bridge with one or more of-O-and-N (R) 18 ) -C of the interrupt 2 ‑C 12 -an alkylene bridge; r 7 Is hydrogen, C 1 ‑C 18 -alkyl or C 6 ‑C 10 -an aryl group; r 8 Is hydrogen, C 1 ‑C 18 -alkyl or C 2 ‑C 18 -a hydroxyalkyl group; r9 is C 1 ‑C 12 -an alkylene group or a bond; r18 is C 1 ‑C 12 Alkyl or phenyl, unsubstituted or substituted by halogen, OH, COOR 21 Or C (O) -R 22 Substitution; r 21 Is hydrogen, an alkali metal atom or C 1 ‑C 18 -an alkyl group; r 22 Is C 1 ‑C 18 -an alkyl group; and a thermoplastic polymer as component (C).)

1. Compositions comprising as component (A) phosphonate oligomers or polymers of formula (I)

Wherein the content of the first and second substances,

ar is an aromatic group;

r is C₁-C₂₀Alkyl radical, C₂-C₂₀-olefins, C₂-C₂₀-alkyne, C₅-C₂₀-cycloalkyl or C₆-C₂₀-an aryl group;

n is an integer from 2 to 200;

-O-Ar-O-is derived from a compound selected from the group consisting of resorcinols, hydroquinones and bisphenols and combinations thereof;

an aminoether of the formula (II) as component (B),

wherein the content of the first and second substances,

m may be less than or equal to the number of carbon atoms in E, and

e is C₁-to C_1000000-alkyl or C₅-C₆-cycloalkyl, wherein the alkyl chain may comprise alkyl substituents, aromatic substituents and polar groups as substituents, and may be interrupted by alkene units and/or heteroatoms;

wherein the content of the first and second substances,

g1 and G2 may be the same or different and are each independently of the other

Hydrogen, halogen, NO₂Cyano, CONR₅R₆、(R₉)COOR₄、C(O)-R₇、OR₈、SR₈、NHR₈、N(R₁₈)₂Carbamoyl, di (C)₁-C₁₈-alkyl) carbamoyl, C (═ NR)₅)(NHR₆)、C₁-C₁₈-an alkyl group; c₃-C₁₈-an alkenyl group; c₃-C₁₈-alkynyl, C₇-C₉Phenylalkyl, C₃-C₁₂-cycloalkyl or C₂-C₁₂-a heterocycloalkyl group;

by at least one O atom and/or by-NR₅-C of the interrupt₂-C₁₈-an alkyl group;

C₆-C₁₀-an aryl group;

phenyl or naphthyl, which is substituted in each case by: c₁-C₄Alkyl radical, C₁-C₄-alkoxy, C₁-C₄Alkylthio, halogen, cyano, hydroxy, carboxy, COOR₂₁、C(O)-R₂₂、C₁-C₄Alkylamino or di (C)₁-C₄-alkyl) amino;

G1 and G2 form C together with the carbon atom to which they are bonded₃-C₁₂-a ring;

t' is hydrogen, primary C₁-C₁₈Alkyl, sec-C₃-C₁₈Alkyl, tertiary C₄-C₁₈-an alkyl or phenyl group, each of which is unsubstituted or substituted by: halogen, OH, COOR₂₁Or C (O) -R₂₂(ii) a Or C₅-C₁₂Cycloalkyl or substituted by at least one O or-N (R)₁₈) -C of the interrupt₅-C₁₂-a cycloalkyl group; or a polycycloalkyl group having 7 to 18 carbon atoms, or substituted with at least one-O-or-N (R)₁₈) -interrupted identical groups; or T' is C- (G)₁)(G₂)-T”；

T' is hydrogen, halogen, NO₂Cyano or a monovalent organic group having 1 to 50 carbon atoms; or T 'and T' together form a divalent organic linking group with the sterically hindered amine nitrogen atom and the group G₁And G₂The substituted quaternary carbon atoms together form an optionally substituted five-or six-membered ring structure, and

R₄is hydrogen, C₁-C₁₈-an alkyl group, a phenyl group, an alkali metal ion or a tetraalkylammonium cation;

R₅and R₆Independently of one another are hydrogen, C₁-C₁₈Alkyl, C substituted by hydroxy₂-C₁₈-alkyl, or together form C₂-C₁₂An alkylene bridge or a substituted or unsubstituted alkylene bridge with one or more of-O-and-N (R)₁₈) -C of the interrupt₂-C₁₂-an alkylene bridge;

R₇is hydrogen, C₁-C₁₈-alkyl or C₆-C₁₀-an aryl group;

R₈is hydrogen, C₁-C₁₈-alkyl or C₂-C₁₈-a hydroxyalkyl group;

R₉is C₁-C₁₂-an alkylene group or a bond;

R₁₈is C₁-C₁₂Alkyl or phenyl, unsubstituted or substituted by halogen, OH, COOR₂₁Or C (O) -R₂₂Substitution;

R₂₁is hydrogen, an alkali metal atom or C₁-C₁₈-an alkyl group;

R₂₂is C₁-C₁₈-an alkyl group;

and a thermoplastic polymer as component (C).

2. The composition according to claim 1, which additionally contains component D as a compatibiliser.

3. The composition of claim 1, wherein the group consisting of resorcinols, hydroquinones, bisphenols, and combinations thereof, comprises bisphenol a, bisphenol F, and 4,4 ' -biphenol, phenolphthalein and derivatives thereof, 4 ' -thiodiphenol, 4 ' -sulfonyldiphenol, 1-bis- (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, and combinations thereof.

4. The composition of claim 1, wherein E is C₆₀-to C_1000000-an alkyl group.

5. The composition of claim 1 wherein component B is the reaction product of fatty acids 2,2,6, 6-tetramethylpiperidin-4-yl-hexadecanoate and 2,2,6, 6-tetramethylpiperidin-4-yl-octadecanoate with an oxidized polyethylene of the formula

Wherein the content of the first and second substances,

C_15/17the alkyl group which is the major constituent and at the N-O-has an average molecular weight of about 2000.

6. The composition of claim 1, wherein n in formula (I) is an integer from 2 to 100.

7. The composition of claim 1, wherein n in formula (I) is an integer from 2 to 50.

8. The composition of claim 1, wherein n in formula (I) is an integer from 2 to 20.

9. The composition of claim 1, wherein n in formula (I) is an integer from 2 to 5.

10. The composition of claim 2, wherein component D is a maleic anhydride grafted polyolefin, a glycidyl methacrylate grafted polyolefin, a maleic anhydride-olefin copolymer, a glycidyl methacrylate-olefin copolymer, a maleic anhydride-acrylate-olefin terpolymer, a glycidyl methacrylate-acrylate-olefin terpolymer and/or a maleic anhydride-acrylate copolymer, a glycidyl methacrylate-acrylate copolymer.

11. The composition of claim 2, wherein the composition comprises 0.2 to 10 weight percent of component (a), 0.1 to 5 weight percent of component (B), 80 to 99.7 weight percent of component (C), and 0 to 5 weight percent of component (D).

12. The composition of claim 2, wherein the composition comprises 0.5 to 5 weight percent of component (a), 0.2 to 2 weight percent of component (B), 90 to 99.3 weight percent of component (C), and 0 to 3 weight percent of component (D).

13. The composition of claim 2, wherein the composition comprises 0.2 to 2 weight percent of component (a), 0.5 to 2 weight percent of component (B), 94 to 99.2 weight percent of component (C), and 0.1 to 2.0 weight percent of component (D).

14. The composition of claim 1, wherein the thermoplastic polymer is a polyolefin.

15. The composition according to claim 1 or 2, wherein the composition is processed into a transparent sheet or film having a thickness of 50-500 μ ι η.

16. A shaped article, film or fiber produced with the composition of claim 1 or 2.

Technical Field

The present invention relates to compositions comprising a synergistic mixture of a thermoplastic polymer and a specific amino ether and phosphonate oligomer, polymer or copolymer.

The composition is particularly useful as a flame retardant for thin gauge materials such as for polyolefin sheets and films and polyolefin fibers.

Background

Polyolefins are increasingly used in applications requiring flame retardancy. Flame retardancy is typically achieved by the addition of bromine or phosphorus compounds. Bromine compounds, however, significantly reduce the light stability of olefins and can therefore only be used to a very limited extent for external applications.

Phosphorus-containing flame retardants need to be used in large amounts and also often do not work in thin gauge applications such as fibers and sheets and films.

US-A-6,599,963 describes A polymeric substrate comprising A flame retardant system comprising A sterically hindered amine and A brominated flame retardant.

WO-A-1999/000450 describes the use of sterically hindered amine compounds as flame retardants for polymers.

WO-A-2010/026230 describes mixtures of cyclic phosphonates, one or more 1,3, 5-triazine compounds and sterically hindered amino ethers. The document describes polyethylene sheets and films that meet fire classification DIN4102B 2. There is a disadvantage in that transparent sheets and films cannot be produced.

WO-A-2015/010775 claims combinations of amino ethers from sterically hindered amines together with finely divided phosphinates. By this combination, flame retardancy can be greatly improved, but a transparent flame-retardant film cannot be realized.

WO-A-2011/117266 describes polymeric substances comprising A salt of phosphinic acid and A tetraalkylpiperidine or tetraalkylpiperazine derivative. The polypropylene achieves fire classification V-2 with the addition of 8% of a flame retardant. This mixture is unsuitable for sheets and films and fibers because of the particle size and high filler content of the phosphinate used.

Flame retardants can impair the processing stability of plastic materials due to their chemical reactivity which is required for flame retardancy at high temperatures. For example, increased polymer degradation, crosslinking reactions, gas evolution or discoloration may occur. For the processing of plastic materials in the absence of the flame retardant, these effects occur in a reduced form, if at all.

A difficulty with the incorporation of sterically hindered amines into sheets and films or fibers as described in WO-A-1999/000450 is that odour and/or discoloration problems are encountered during incorporation. Furthermore, low molecular weight compounds may migrate out of the plastic material.

Polyphosphonates or phosphonate oligomers have also shown flame retardant activity in many plastics. However, these polyphosphonates require high loadings in the thermoplastic resin even with the addition of typical melamine based synergists (US-A-2009/0043013).

Disclosure of Invention

It is therefore an object of the present invention to provide an innovative combination of polyolefin and flame retardant for the aforementioned applications, which does not have the existing drawbacks of the current aminoether-based flame retardants and is superior in performance to the hitherto known patented combinations.

Some embodiments provide a composition comprising

Phosphonate oligomers or polymers of the formula (I) as component (A)

Wherein:

ar is an aromatic group;

r is C₁-C₂₀Alkyl radical, C₂-C₂₀-olefins, C₂-C₂₀-alkyne, C₅-C₂₀-cycloalkyl or C₆-C₂₀-an aryl group;

n is an integer from 2 to 200;

-O-Ar-O-is derived from a compound selected from the group consisting of resorcinols, hydroquinones and bisphenols and combinations thereof;

an aminoether of the formula (II) as component (B),

wherein the content of the first and second substances,

m may be less than or equal to the number of carbon atoms in E, and

wherein the content of the first and second substances,

g1 and G2 may be the same or different and are each independently of the other

by at least one O atom and/or by-NR₅-C of the interrupt₂-C₁₈-an alkyl group;

C₆-C₁₀-an aryl group;

G1 and G2 form C together with the carbon atom to which they are bonded₃-C₁₂-a ring;

R₄is hydrogen, C₁-C₁₈-an alkyl group, a phenyl group, an alkali metal ion or a tetraalkylammonium cation;

R₇is hydrogen, C₁-C₁₈-alkyl or C₆-C₁₀-an aryl group;

R₈is hydrogen, C₁-C₁₈-alkyl or C₂-C₁₈-a hydroxyalkyl group;

R₉is C₁-C₁₂-an alkylene group or a bond;

R₁₈is C₁-C₁₂Alkyl or phenyl, unsubstituted or substituted by halogen, OH, COOR₂₁Or C (O) -R₂₂Substitution;

R₂₁is hydrogen, an alkali metal atom or C₁-C₁₈-an alkyl group;

R₂₂is C₁-C₁₈-an alkyl group;

a thermoplastic polymer as component (C);

and optionally as component D a compatibilising agent for the phosphonate oligomer or polymer and the thermoplastic polymer C.

In some embodiments, the group consisting of resorcinols, hydroquinones, and bisphenols and combinations thereof include bisphenol a, bisphenol F, and 4,4 ' -biphenol, phenolphthalein and derivatives thereof, 4 ' -thiodiphenol, 4 ' -sulfonyldiphenol, 1-bis- (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, and combinations thereof.

In some embodiments, n in formula (I) is an integer equal to 2 or greater than 2; in some embodiments, n in formula (I) is an integer from 2 to 100; in some embodiments, n in formula (I) is an integer from 2 to 50; in some embodiments, n in formula (I) is an integer from 2 to 20; and in some embodiments, n in formula (I) is an integer from 2 to 5.

In some embodiments, E is C₆₀-to C_1000000-an alkyl group.

In some embodiments, component B may be the reaction product of fatty acids 2,2,6, 6-tetramethylpiperidin-4-yl-hexadecanoate and 2,2,6, 6-tetramethylpiperidin-4-yl-octadecanoate with an oxidized polyethylene of the formula

Wherein the content of the first and second substances,

C₁₅H_31/C₁₇H₃₅the alkyl group which is the major constituent and at the N-O-has an average molecular weight of about 2000.

In some embodiments, component D is a typical compatibilizer for polar and non-polar polymers composed of bipolar molecules, such as maleic anhydride grafted polyolefins, glycidyl methacrylate grafted polyolefins, maleic anhydride-olefin copolymers, glycidyl methacrylate-olefin copolymers, maleic anhydride-acrylate-olefin terpolymers, glycidyl methacrylate-acrylate-olefin terpolymers and/or maleic anhydride-acrylate copolymers, glycidyl methacrylate-acrylate copolymers.

In some embodiments, the composition comprises 0.2 to 10 weight percent of component (a), 0.1 to 5 weight percent of component (B), and 80 to 99.7 weight percent of component (C) and 0 to 5 weight percent of component D.

In some embodiments, the composition comprises 0.5 to 5 weight percent of component (a), 0.2 to 2 weight percent of component (B), and 90 to 99.3 weight percent of component (C) and 0 to 3 weight percent of component D.

In some embodiments, the composition comprises 0.2 to 2 weight percent of component (a), 0.5 to 2 weight percent of component (B), and 94 to 99.2 weight percent of component (C), and 0.1 to 2.0 weight percent of component D.

In some embodiments, the thermoplastic polymer is a polyolefin.

In some embodiments, the composition is processed into a transparent sheet having a thickness of 50 to 500 μm.

Some embodiments provide shaped articles, films, sheets, or fibers produced with the composition or the composition as described herein.

Detailed Description

It has now surprisingly been found that mixtures of amino ethers from sterically hindered amines with polyphosphonates or phosphonate oligomers exhibit improved flame retardant action in polyolefins. Various flame retardant classifications can be achieved at low loadings and the negative impact on physical properties is mitigated.

The flame-retardant polyolefin materials of the invention also exhibit very good transparency, UV resistance, flowability, extrudability and moldability.

The present invention therefore relates to compositions comprising as component (A) phosphonate oligomers or polymers of formula (I)

Wherein the content of the first and second substances,

ar is an aromatic group;

r is C₁-C₂₀Alkyl radical, C₂-C₂₀-olefins, C₂-C₂₀-alkyne, C₅-C₂₀-cycloalkyl or C₆-C₂₀-an aryl group;

n is an integer from 2 to 200;

-O-Ar-O-is derived from a compound selected from the group consisting of resorcinols, hydroquinones and bisphenols and combinations thereof;

an aminoether of the formula (II) as component (B),

wherein the content of the first and second substances,

m may be less than or equal to the number of carbon atoms in E, and

wherein the content of the first and second substances,

g1 and G2 may be the same or different and are each independently of the other

by at least one O atom and/or by-NR₅-C of the interrupt₂-C₁₈-an alkyl group;

C₆-C₁₀-an aryl group;

phenyl or naphthyl, which is substituted in each case by:C₁-C₄alkyl radical, C₁-C₄-alkoxy, C₁-C₄Alkylthio, halogen, cyano, hydroxy, carboxy, COOR₂₁、C(O)-R₂₂、C₁-C₄Alkylamino or di (C)₁-C₄-alkyl) amino;

G1 and G2 form C together with the carbon atom to which they are bonded₃-C₁₂-a ring;

R₄is hydrogen, C₁-C₁₈-an alkyl group, a phenyl group, an alkali metal ion or a tetraalkylammonium cation;

R₇is hydrogen, C₁-C₁₈-alkyl or C₆-C₁₀-an aryl group;

R₈is hydrogen, C₁-C₁₈-alkyl or C₂-C₁₈-a hydroxyalkyl group;

R₉is C₁-C₁₂-an alkylene group or a bond;

R₁₈is C₁-C₁₂Alkyl or phenyl, unsubstituted or substituted by halogen, OH, COOR₂₁Or C (O) -R₂₂Substitution;

R₂₁is hydrogen, an alkali metal atom or C₁-C₁₈-an alkyl group;

R₂₂is C₁-C₁₈-an alkyl group;

a thermoplastic polymer as component (C);

and optionally as component D a compatibilising agent for the phosphonate oligomer or polymer and the thermoplastic polymer C.

In some embodiments, E is C₆₀-to C_1000000-an alkyl group.

Wherein the content of the first and second substances,

C₁₅H_31/C₁₇H₃₅the alkyl group which is the major constituent and at the N-O-has an average molecular weight of about 2000.

In some embodiments, the thermoplastic polymer is a polyolefin.

In some embodiments, the composition is processed into a transparent sheet having a thickness of 50 to 500 μm.

The present invention includes various shaped articles, films, sheets or fibers made from the compositions described above.

Phosphonate oligomers and polymers, which are linear or branched, are well known in the literature. See, for example, US-A-7449526, US-A-7816486, US-A-8530044, US-A-8563638 and US-A-8779041.

In certain embodiments, the phosphonate component may be a long chain polyphosphonate containing structural units of formula I having n > 20.

In some embodiments, the polyphosphonate can have a weight average molecular weight (Mw) of about 10,000 g/mole to about 150,000 g/mole as determined by Gel Permeation Chromatography (GPC) based on polystyrene standards. In other embodiments, the polyphosphonate can have a Mw of about 12,000 to about 80,000 g/mole as determined by GPC based on polystyrene standards.

The number average molecular weight (Mn), as determined by GPC based on polystyrene standards, may be in such embodiments from about 5,000 g/mole to about 75,000 g/mole, or from about 8,000 g/mole to about 15,000 g/mole, and in certain embodiments, the Mn may be greater than about 9,000 g/mole.

The molecular weight distribution (i.e., Mw/Mn) of such polyphosphonates may be in some embodiments from about 2 to about 10, and in other embodiments from about 2 to about 5.

In certain embodiments, the phosphonate component can be a phosphonate oligomer containing structural units of formula I and n is from 2 to about 20, 2 to about 10, or 2 to about 5, or any integer between these ranges.

In some embodiments, the Mw of the phosphonate oligomer as determined by GPC based on polystyrene calibration may be from about 1,000 g/mole to about 10,000 g/mole or any value within this range.

In other embodiments, the Mw may be from about 1,500 g/mole to about 8,000 g/mole, from about 2,000 g/mole to about 4,000 g/mole, or any value within these ranges.

The phosphorus content of the polyphosphonates and oligomeric phosphonates may vary between embodiments and the embodiments are not limited by the phosphorus content or the range of phosphorus content. For example, in some embodiments, the phosphonate ester of the oligomer may have a phosphorus content of about 1% to about 20% by weight of the total oligomer, and in other embodiments, the phosphorus content may be about 2% to about 15% by weight of the total oligomer, about 2% to about 12% by weight of the total oligomer, or about 2% to about 10% by weight of the total oligomer.

In some embodiments, the phosphonate oligomers or polymers may be branched or linear and may be prepared with up to about 50 mole% branching agent.

In certain embodiments, component B is the reaction product of fatty acids 2,2,6, 6-tetramethylpiperidin-4-yl-hexadecanoate and 2,2,6, 6-tetramethylpiperidin-4-yl-octadecanoate with an oxidized polyethylene of the formula

Wherein the content of the first and second substances,

C_15/17the alkyl group, which is the major constituent and at the N-O-has an average molecular weight of about 2000 (CAS number 86403-32-9).

In some embodiments, E is C₅-to C₆-a cycloalkyl group.

In some embodiments, E is C₆₀-to C_1000000-an alkyl group.

In some embodiments, E is a wax.

Waxes are natural or synthetic materials which are solid at 20 ℃ and kneadable and melt above 40 ℃ without decomposition and have a low viscosity. Waxes usually transition to the molten, low-viscosity state at temperatures between 50 ℃ and 90 ℃ and in particular cases up to about 200 ℃. There is a distinction between natural waxes (e.g., carnauba wax), chemically modified waxes (e.g., montan ester waxes) and synthetic waxes (e.g., polyethylene waxes).

The wax may be a hydrocarbon wax, an ester wax, an oxidized polyolefin wax, an oxidized hydrocarbon wax, an amide wax, a wax acid, a wax soap, a natural wax, and/or combinations of these components.

Examples of suitable natural waxes include, but are not limited to, vegetable waxes such as carnauba wax or candelilla wax, or waxes of animal origin, such as shellac wax.

Polar or non-polar fully synthetic waxes, such as polyolefin waxes, may also be used. The non-polar polyolefin waxes may be produced by thermal degradation of branched or unbranched polyolefin plastic materials or by direct polymerization of olefins.

Polar polyolefin waxes are formed by suitable modification of nonpolar waxes, for example by oxidation with air or by grafting onto polar olefin monomers, for example α, β -unsaturated carboxylic acids and/or derivatives thereof, for example acrylic acid or maleic anhydride.

Polar polyolefin waxes can additionally be prepared by copolymerization of ethylene with polar comonomers, such as vinyl acetate or acrylic acid, and furthermore by oxidative degradation of relatively high molecular weight, non-waxy ethylene homo-and copolymers. Corresponding examples can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5 th edition, volume A28, Weinheim 1996, chapter 6.1.5, page 155-.

Suitable polyolefin waxes include degraded waxes prepared by thermal degradation of ethylene or 1-olefin homopolymers and copolymers, such as polyethylene or polypropylene.

Also suitable are polar waxes prepared by modification of the polyolefin waxes described above. The modification is effected by methods known per se, for example by oxidation with an oxygen-containing gas, for example air, and/or by grafting with an α, β -unsaturated acid or derivatives thereof, for example acrylic acid, acrylic esters, maleic anhydride, maleic acid.

It has now been surprisingly found that mixtures of phosphonate oligomers or polymers with aminoether compounds having the structure R-O-N, wherein R is an alkyl group and N is a sterically hindered amine, are very effective flame retardants in polyolefin sheets and films, and that the sheets and films are transparent and light stable. The compounds are thermally stable, transparent and do not exhibit discoloration or odor problems when incorporated into polymers.

The terms "transparency", "optical transparency", "transmittance" and "light transmittance" as used herein are intended to describe the amount of visible light (wavelength range of about 300nm to 700nm) that can pass through the thickness of a given sample, typically expressed as a percentage of less than 100%. Transparency is typically measured using a visible spectrophotometer by placing the sample in a beam of light and recording the amount of light that passes through. The transparent sheets and films of the present invention exhibit a transparency equal to or greater than 50%.

The R-O-N compounds preferably have a high molecular weight and therefore do not exhibit a tendency to migrate out of the plastic material.

In particular, the invention relates to the use of synergistic mixtures of phosphonate oligomers or polymers and amino ethers of the formulae D and D' as flame retardants and multifunctional additives,

wherein m may be 1 to 50.

E is C₁-to C_1000000-alkyl or C₅-to C₆Cycloalkyl, wherein the alkyl chain may comprise alkyl substituents, aromatic substituents and polar groups as substituents.

The alkyl chain may also be interrupted by alkene units and heteroatoms.

Specific examples of amino ethers according to the invention are

The aminoethers composed of wax (E) and of sterically hindered amines are thermally stable and neither decompose the polymer during processing nor affect the production process of the plastic material molding compounds. The reaction product consisting of the wax and the sterically hindered amine is not volatile and does not have a tendency to migrate out of the plastic material under typical production and processing conditions of thermoplastic polymers.

The polymers which can be used according to the invention are thermoplastic polymers.

According to Hans Dominghaus in "Die Kunststoffe and ihre Eigenschaften", 5 th edition (1998), pages 14 to 25, thermoplastic polymers (component C) are understood to mean polymers whose molecular chains do not have lateral branching or a varying number of lateral branches of greater or lesser length and soften on heating and can be shaped virtually indefinitely.

The polymer may be a polymer of monoolefins and diolefins, for example polypropylene, polyisobutylene, poly-1-butene, poly-4-methyl-1-pentene, polyisoprene or polybutadiene, and polymers of cycloolefins, for example polymers of cyclopentene or norbornene; and also polyethylene (which may optionally be crosslinked), such as High Density Polyethylene (HDPE), high density high molecular weight polyethylene (HDPE-HMW), high density ultra high molecular weight polyethylene (HDPE-UHMW), Medium Density Polyethylene (MDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), Branched Low Density Polyethylene (BLDPE) and mixtures thereof.

The polymers may be copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene-propylene copolymers, Linear Low Density Polyethylene (LLDPE) and mixtures thereof with Low Density Polyethylene (LDPE), propylene-1-butene copolymers, propylene-isobutylene copolymers, ethylene-1-butene copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and copolymers thereof with carbon monoxide, or ethylene-acrylic acid copolymers and salts thereof (ionomers), and also terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene norbornene; and also mixtures of such copolymers with one another, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers, LDPE/ethylene-acrylic acid copolymers, LLDPE/ethylene-vinyl acetate copolymers, LLDPE/ethylene-acrylic acid copolymers and alternating or random polyolefin/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

The polymer may be a hydrocarbon resin (e.g., C)₅-to C₉) Including hydrogenated versions thereof (e.g., tackifying resins) and mixtures of polyolefins and starch.

The polymer may be polystyrene (A)

143e (basf), poly (p-methylstyrene), poly (α -methylstyrene).

The polymer may be a copolymer of styrene or alpha-methylstyrene with a diene or acrylic derivative, such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; high impact blends of styrene copolymers with another polymer, such as a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and block copolymers of styrene, such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrene.

The polymer may be a graft copolymer of styrene or alpha-methylstyrene, for example styrene grafted on polybutadiene, styrene grafted on polybutadiene-styrene or polybutadiene-acrylonitrile copolymer, styrene and acrylonitrile (or methacrylonitrile) grafted on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene, styrene and alkyl acrylate/methacrylate on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, and mixtures thereof, such as those known as ABS, MBS, ASA or AES polymers.

The polymer may be a halogenated polymer, such as polychloroprene, chlorine rubber, chlorinated or brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogenated vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and copolymers thereof, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

The polymers may be polymers derived from α, β -unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, butyl acrylate-impact-modified polymethyl methacrylates, polyacrylamides and polyacrylonitriles, and copolymers of the monomers mentioned with one another or with other unsaturated monomers, for example acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkyl alkoxy acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.

The polymer may be a polymer derived from unsaturated alcohols and amines/a polymer derived from acyl derivatives or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate or polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine; and copolymers thereof with olefins.

The polymers may be homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

The polymer may be polyacetal, such as polyoxymethylene, and those polyoxymethylenes which contain comonomers, such as ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

The polymers are preferably polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides.

The polymer may be a polyurethane derived from polyethers, polyesters and polybutadienes having two terminal hydroxyl groups as well as aliphatic or aromatic polyisocyanates and precursors thereof.

The polymer may be a polyamide or copolyamide derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 6 (polycaprolactam, poly-6-aminocaproic acid,DuPont；

K122，DSM；7301，DuPont；

b29, Bayer) and polyamide 6/6 (poly (N, N' -hexamethylene adipamide);6/6，DuPont；101，DuPont；

A30、AKV、AM，Bayer；a3, BASF), with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers, or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Furthermore, EPDM-modified or ABS-modified polyamides or copolyamides; and polyamides condensed during processing ("RIM polyamide systems").

The polymers may be polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

The polymers are preferably polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate: (

2500、2002，Celanese；

BASF), poly-1, 4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates, and block polyetheresters derived from polyethers having hydroxyl end groups; furthermore, polyesters modified with polycarbonates or MBS.

The polymers may be polycarbonates and polyester carbonates.

The polymer may be a polysulfone, a polyethersulfone, and a polyetherketone.

The polymer may be a mixture (polymer blend) of the aforementioned polymers, for example PP/EPDM (polypropylene/ethylene-propylene-diene rubber), polyamide/EPDM or ABS (polyamide/ethylene-propylene-diene rubber or acrylonitrile-butadiene-styrene), PVC/EVA (polyvinyl chloride/ethylene-vinyl acetate), PVC/ABS (polyvinyl chloride/acrylonitrile-butadiene-styrene), PVC/MBS (polyvinyl chloride/methacrylate-butadiene-styrene), PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene), PBTP/ABS (polybutylene terephthalate/acrylonitrile-butadiene-styrene), PC/ASA (polycarbonate/acrylate-styrene-acrylonitrile), PC/PBT (polycarbonate/polybutylene terephthalate), PVC/CPE (polyvinyl chloride/chlorinated polyethylene), PVC acrylates (polyvinyl chloride acrylate, POM/thermoplastic PUR (polyoxymethylene/thermoplastic polyurethane), PC/thermoplastic PUR (polycarbonate/thermoplastic polyurethane), POM acrylates (polyoxymethylene acrylate), POM/MBS (polyoxymethylene/methacrylate-butadiene-styrene), PPO/HIPS (polyphenylene oxide/high impact polystyrene), PPO/PA 6,6 (polyphenylene oxide/nylon 6,6) and copolymers, PA/HDPE (polyamide/high density polyethylene), PA/PP (polyamide/polyethylene), PA/PPO (polyamide/polyphenylene oxide), PVC/CPE (polyvinyl chloride/chlorinated polyethylene), PVC/acrylate (polyvinyl chloride acrylate, POM/thermoplastic PUR (polyoxymethylene/thermoplastic polyurethane), POM/MBS (polyoxymethylene/butadiene-styrene), PPO/HIPS (polyphenylene oxide/high impact polystyrene), PPO/PA 6,6 (polyphenylene oxide/nylon 6, PBT/PC/ABS (polybutylene terephthalate/polycarbonate/acrylonitrile-butadiene-styrene) and/or PBT/PET/PC (polybutylene terephthalate/polyethylene terephthalate/polycarbonate).

The polymer-shaped articles, films, threads and fibers are characterized by the fact that they are polyolefins such as polyethylene, polypropylene, ethylene-vinyl acetate.

The polymer films are characterized in that they are transparent.

The processing comprises premixing the components A and B in the form of powders and/or pellets and optionally component D in a mixer and subsequently homogenizing said components in a polymer melt (corresponding to component C) in a compounding device (e.g.a twin-screw extruder). The melt is typically extruded, cooled and pelletized. Component A, B and optionally D may also be introduced directly into the compounding device separately via a metering unit.

It is likewise possible to mix components A and B and optionally component D with the polymer pellets/powder prepared (component C) and to process the mixture directly, for example on a blown film line or a fiber spinning line.

Additional additives may be added to the blend. The additive may be an antioxidant, an antistatic agent, a blowing agent, an additional flame retardant, a heat stabilizer, an impact modifier, a processing aid, a flow aid, a light stabilizer, an anti-dripping agent, an additional compatibilizer, a reinforcing agent, a filler, a nucleating agent, an additive for laser marking, a hydrolysis stabilizer, a chain extender, a pigment, a softener, and/or a plasticizer.

The flame retardant plastic material molding compounds are suitable for the production of shaped articles, films and sheets, threads and fibers, for example by injection molding, extrusion, blow molding or press molding.

The compositions according to the invention are particularly suitable for blown films. Blown films are characterized by extremely high film cohesion and particularly high resistance to perforation and tear propagation. There are sheets and films consisting of only one layer (so-called monolayer blown films) and sheets and films made of multiple layers (so-called coextrusion blown films). Coextruded blown films provide for combining the frontal properties of different materials in one sheet.

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