阅读说明：本技术 用于制备官能化的聚酯的方法 (Process for preparing functionalized polyesters ) 是由 S·弗洛雷斯佩纳尔瓦 M·帕拉达斯-帕洛莫 J·加西亚米拉莱斯 H-G·金策尔曼 R·M·塞 于 2018-05-22 设计创作，主要内容包括：本申请涉及一种制备氨基官能的聚酯的方法,所述方法包括：提供包含至少一种内酯单体、催化剂以及具有至少一个伯胺基团和至少一个仲胺基团的多胺的混合物；以及使所述混合物经受开环聚合条件。(The present application relates to a process for preparing an amino-functional polyester, the process comprising: providing a mixture comprising at least one lactone monomer, a catalyst, and a polyamine having at least one primary amine group and at least one secondary amine group; and subjecting the mixture to ring-opening polymerization conditions.)

1. A process for preparing an amino-functional polyester, the process comprising:

providing a mixture comprising at least one lactone monomer, a catalyst, and a polyamine having at least one primary amine group and at least one secondary amine group; and

subjecting the mixture to ring-opening polymerization conditions.

2. The method of claim 1, wherein the mixture comprises at least one lactone monomer according to formula (1):

wherein: n is more than or equal to 1;

each R is independently selected from hydrogen, C1-C6 alkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, and C6 aryl, with the proviso that at least n of the Rs are hydrogen.

3. The method of claim 2, wherein the mixture comprises at least one lactone monomer according to formula (1 a):

wherein: n is an integer of 1 to 4; and is

Each R is independently selected from hydrogen and C1-C6 alkyl, provided that at least n + 2R are hydrogen.

4. The method of claim 1, wherein the mixture comprises at least one lactone monomer selected from the group consisting of β -propiolactone, β -butyrolactone, β -valerolactone, γ -butyrolactone, γ -valerolactone, δ -valerolactone, monomethyl- δ -valerolactone, monoethyl- δ -valerolactone, monohexyl- δ -valerolactone, ε -caprolactone, monomethyl- ε -caprolactone, monoethyl- ε -caprolactone, monohexyl- ε -caprolactone, dimethyl- ε -caprolactone, di-n-propyl- ε -caprolactone, di-n-hexyl- ε -caprolactone, trimethyl- ε -caprolactone, triethyl- ε -caprolactone, pivalolactone, and 5-methyloxepin-2-one.

5. The process of any one of claims 1 to 4, wherein the reaction mixture comprises, based on the total weight of monomers:

80-100 wt.% of the at least one lactone monomer; and

0 to 20 wt.% of at least one comonomer selected from: epoxy compounds, cyclic carbonates, glycolides, and lactides.

6. The method of any one of claims 1 to 5, wherein the polyamine is aliphatic or cycloaliphatic.

7. The method of any one of claims 1 to 6, wherein the polyamine has at least two primary amine groups and at least one secondary amine group.

8. The method of any one of claims 1 to 7, wherein the molar ratio of lactone monomer to polyamine is from 1:1 to 500:1, preferably from 2:1 to 50:1, and more preferably from 2:1 to 20: 1.

9. The process of any one of claims 1 to 8, wherein the catalyst is metal-free.

10. The process of any one of claims 1 to 9, wherein the catalyst comprises 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD) and/or 1, 8-diazabicyclo- (5,4,0) -undecene-7 (DBU).

11. The process according to any one of claims 1 to 10, wherein the catalyst is provided in an amount of 0.1-5 wt.%, preferably 0.1-2.0 wt.%, based on the total weight of monomers.

12. The method of any one of claims 1 to 11, wherein the mixture subjected to ring-opening polymerization conditions is substantially free of solvent.

13. The process of any one of claims 1 to 12, wherein the ring-opening polymerization conditions comprise a temperature of 50-200 ℃, preferably 60-150 ℃.

14. An amino-functional polyester obtained by the process as defined in any one of claims 1 to 13, said polyester preferably being characterized by at least one of the following:

i) a weight average molecular weight (Mw) of from 300 to 5000g/mol, preferably from 500 to 4000 g/mol;

ii) a polydispersity index of less than 2.5, preferably less than 2.3;

iii) an amine number (NHv) of 20 to 350mg KOH/g, preferably 25 to 250mg KOH/g; and

iv) a total hydroxyl number and amine number (OHV + NHv) of 40 to 500mg KOH/g, preferably 50 to 400mg KOH/g.

15. A curable coating, adhesive or sealant composition comprising:

an amino-functional polyester as defined in claim 14; and

at least one polyfunctional compound (H) having at least two functional groups (F) selected from: epoxy groups, isocyanate groups, and cyclic carbonate groups.

Technical Field

The present application relates to a process for preparing functionalized polyesters. More specifically, the present application relates to a process for preparing amino-and hydroxy-functionalized polyesters, and to the use of said polyesters in coating, adhesive or sealant compositions.

Background

Diamines, triamines and higher functionality polyamines are versatile and are commonly used curing agents that can react with a variety of polymers or resin systems: for illustrative purposes, compositions based solely on epoxy resins, polyisocyanates, and cyclic carbonates may be cured with polyamines. However, it is problematic that most low molecular aliphatic polyamines are volatile, have limited complementary functionalities, and provide only a limited contribution to the mechanical properties of the cured system. In addition, such low molecular weight polyamines have many Health hazards, such as acute toxicity, irritation, and skin and lung allergies, as mentioned by Sullivan et al in Clinical Environmental Health and Toxic Exposures (2 nd edition, 2001) and by Tarvainen et al in Journal of Environmental Medicine (1999) 1.1.3.

The present invention relates to the development of polymeric amino curing agents having a polyester backbone, wherein the amino curing agent is stable and non-volatile, and may contribute to the mechanical properties of the final curable composition. In the course of developing higher molecular weight amino curing agents, the present invention seeks to alleviate those environmental health issues associated with migration and diffusion of amines in fluid systems.

U.S. patent No.4,379,914(Lundberg) describes a method of forming a polylactone polymer in which one end of the polylactone polymer is terminated with a tertiary amine group and the other end is terminated with a hydroxyl group. In its synthesis, epsilon-caprolactone reacts with diamines in the presence of stannous octoate catalysts: the diamine is characterized in that one of the amine groups is a tertiary amine group and the other amine group is a primary or secondary amine group. The polylactone polymers of this citation do not have reactive amino groups. And similar polylactone polymers are also disclosed in U.S. patent nos. 4,463,168 and 4,512,776 (also issued to Lundberg).

The formation of polyesters by ring-opening polymerization of, inter alia, epsilon-caprolactone, is also discussed in Macromolecules (1992, 25, 2614-2618), using diethylaluminum alkoxide and triethylaluminum-amine systems as initiators. The polymerization reaction was terminated by acid hydrolysis. And by this mechanism the derivatized polyester does not have any amino groups as the amine introduced by the initiator reacts to form an amide.

US 20100179282a1(Evonik Degussa) describes polyesters which have been modified with one or more polyamines having at least one primary and at least one secondary amino group. This citation reports the synthesis of storage-stable polyesters having reactive secondary amino groups. Specifically, the synthesis is carried out by ammonolysis of polyester polyols with polyamines: the amine group attacks the carbonyl group of the ester, thereby forming an amide bond and releasing the diol or oligoester. In this way, amino-free by-products are also released during the reaction, resulting in the formation of a complex mixture of diols, oligoesters and aminopolyester chains with a broad molecular weight distribution.

Disclosure of Invention

According to a first aspect of the present invention there is provided a process for the preparation of an amino-functional polyester, the process comprising:

providing a mixture comprising at least one lactone monomer, a catalyst, and a polyamine having at least one primary amine group and at least one secondary amine group; and

subjecting the mixture to ring-opening polymerization conditions.

The polyamine herein acts as an initiator in the ring-opening polymerization reaction. The initiator is incorporated into the polyester structure by a polyamine having two amine groups of different reactivity, the residue of which retains the secondary amine groups. The polyesters obtained according to the invention are also characterized by having at least one terminal hydroxyl group due to the mechanism of ring-opening polymerization.

In an embodiment of the invention, the reaction mixture comprises, based on the total weight of the monomers: 80-100 wt.% of the at least one lactone monomer; and 0 to 20 wt.% of at least one comonomer selected from: epoxy compounds, cyclic carbonates, glycolides, and lactides.

Regardless of the presence or absence of such comonomers, it is preferred that the reaction mixture comprises at least one lactone monomer according to formula (1):

wherein: n is more than or equal to 1;

each R is independently selected from hydrogen, C1-C6 alkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, and C6 aryl, provided that at least n of the Rs are hydrogen.

More specifically, the reaction mixture should comprise at least one lactone monomer according to formula (1 a):

wherein: n is an integer of 1 to 4; and is

Each R is independently selected from hydrogen and C1-C6 alkyl, provided that at least n + 2R are hydrogen.

The polyamine initiators listed may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic. However, aliphatic and/or cycloaliphatic polyamines may preferably be mentioned. And also preferably polyamines comprising at least two primary amine groups and at least one secondary amine group. For example, highly suitable polyamine initiators can be characterized as having at least two primary amine groups and at least one secondary amine group.

The ring-opening polymerization catalyst is typically provided in an amount of 0.1 to 5 wt.%, preferably 0.1 to 2.0 wt.%, based on the total weight of the monomers. In a preferred embodiment, the catalyst provided is tin (Sn) -free or even metal-free: for example, the use of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD) and/or 1, 8-diazabicyclo- (5,4,0) -undecene-7 (DBU) has proven effective.

According to a second aspect of the present invention, there is provided an amino-functional polyester obtained by the process defined above and in the appended claims, said polyester preferably being characterized by at least one of the following:

i) a weight average molecular weight (Mw) of from 300 to 5000g/mol, preferably from 500 to 4000 g/mol;

ii) a polydispersity index of less than 2.5, preferably less than 2.3;

iii) an amine number (NHv) of 20 to 350mg KOH/g, preferably 25 to 250mg KOH/g; and

iv) a total hydroxyl number and amine number (OHV + NHv) of 40 to 500mg KOH/g, preferably 50 to 400mg KOH/g.

According to a third aspect of the present invention there is provided a curable coating, adhesive or sealant composition comprising: an amino-functional polyester as defined above and in the appended claims; and at least one polyfunctional compound (H) having at least two functional groups (F) selected from: epoxy groups, isocyanate groups, and cyclic carbonate groups.

Definition of

As used herein, the singular forms "a," "an," "the," and "the" include plural referents unless the context clearly dictates otherwise.

The terms "comprising" and "consisting of … …," as used herein, are synonymous with "including," "containing," and are inclusive or open-ended and do not exclude additional unrecited members, elements, or method steps.

When equivalents, concentrations, dimensions, and other parameters are expressed in terms of ranges, preferred ranges, upper values, lower values, or preferred upper and lower values, it is understood that any range that can be obtained by combining any upper limit or preferred value with any lower limit or preferred value is also specifically disclosed, regardless of whether the obtained range is explicitly mentioned in the context.

The terms "preferred," "preferably," "intended," "particularly," and "particularly" are often used herein to refer to embodiments of the disclosure that may provide particular benefits under certain circumstances. However, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude those other embodiments from the scope of the disclosure.

Unless otherwise specified, molecular weights given herein refer to weight average molecular weight (Mw). Unless otherwise specified, all molecular weight data refer to values obtained by Gel Permeation Chromatography (GPC).

As used herein, "polydispersity index" refers to a measure of the molecular weight distribution in a given polymer sample. The polydispersity index is calculated by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn).

Unless otherwise stated, the OH numbers given herein are obtained according to Deutsche (DGF) Einheitsmethodenuzu r Untershung von Fetten, Fettprodukten, Tensiden und verwandten Stoffen (Gesamtingsvertzeichnis 2016) C-V17 b (53).

Unless otherwise stated, the amine value-according to ASTM D2572-91-was obtained by titration with 0.1N hydrochloric acid, after which it was calculated back to mg KOH/g.

In view of the amino-functional polyester, the total hydroxyl number and amine number (OHv + NHv) were measured in an established manner, specifically where hydroxyl and amine groups were reacted with excess acetic anhydride, and the resulting free acetate groups were back-titrated with KOH to assess the total millimolar amount of hydroxyl and amine groups in a1 gram sample. The amine number itself was evaluated by titration with 0.1N hydrochloric acid according to ASTM D2572-91, after which it was calculated back to mg KOH/g. A hydroxyl value is calculated based on the determined amine value and the determined total amine value and hydroxyl value.

As used herein, room temperature is 23 ℃ ± 2 ℃.

As used herein, the term "equivalent (eq.) refers to the relative number of reactive groups present in a reaction as is common in chemical notation; the term "milliequivalents (meq)" is one thousandth (10) of a stoichiometric equivalent^-3)。

As used herein, the term "equivalent weight" refers to the molecular weight divided by the number of functional groups (functions) of interest. Thus, "epoxy equivalent weight" (EEW) refers to the weight (in grams) of the resin containing one equivalent of epoxy groups.

As used herein, the term "aromatic group" refers to a mononuclear or polynuclear aromatic hydrocarbon group.

As used herein, "alkyl group" refers to a monovalent group that is a radical of an alkane and includes straight-chain and branched organic groups, which groups may be substituted or unsubstituted. The term "alkylene" refers to a divalent group that is a radical of an alkane and includes linear and branched organic groups, which groups may be substituted or unsubstituted.

Specifically, as used herein, "C" is₁-C₆An alkyl "group refers to an alkyl group containing 1 to 6 carbon atoms. Examples of alkyl groups include, but are not limited to: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl. In the present invention, such alkyl groups may be unsubstituted or may be substituted with one or more substituents such as halogen, nitro, cyano, amido, amino, sulfonyl, sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfonamide, and hydroxyl. The halogenated derivatives of the exemplary hydrocarbon groups listed above may be mentioned in particular as examples of suitable substituted alkyl groups. However, in general, it should be noted that preference is givenUnsubstituted alkyl (C) containing 1 to 6 carbon atoms₁-C₆Alkyl), for example unsubstituted alkyl (C) containing 1 to 4 carbon atoms₁-C₄Alkyl) or unsubstituted alkyl (C) containing 1 or 2 carbon atoms₁-C₂Alkyl groups).

As used herein, "C1-C6 alkoxy" refers to a C1-C6 alkyl group, as defined above, attached to an oxygen atom. Examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy or hexyloxy.

As used herein, "C3-C8 cycloalkyl" refers to saturated cyclic hydrocarbons having 3-8 carbon atoms. Examples thereof include cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

As used herein, the term "aryl" refers to a monocyclic or polycyclic aromatic group comprising carbon and hydrogen atoms. Here, the aryl group may be unsubstituted or may be substituted by one or two C1-C6 alkyl groups. Specifically, herein, the term "C6 aryl" refers to a monocyclic ring wherein the ring contains 6 carbon atoms.

As used herein, "lactone" or "lactone ring" refers to a cyclic ester that can nominally be considered a condensation product of an alcohol group and a carboxylic acid group in the same molecule, the prefix may indicate the size of the ring: β -lactone (4-membered), γ -lactone (5-membered), δ -lactone (6-membered ring.) as is known in the art, lactones may be prepared by the reaction of peracetic acid with cyclic ketones, particularly the disclosure of Starcher et al in the Journal of the American Chemistry Society (80, 4079, 1958) may be instructive in this regard.

As used herein, "lactide" (CAS 4511-42-6 and 95-96-5) refers to a cyclic diester obtained by dehydration-condensation of two lactic acid molecules. Note that this diester exists in three optical isomers: l-lactide formed from two L-lactic acid molecules; d-lactide formed from two D-lactic acid molecules; and meso-lactide formed from L-lactic acid and D-lactic acid. If applicable, the lactyl units of the polyester copolymer may be derived from one, two or three of the isomers.

As used herein, polymerization conditions are those conditions that result in the formation of a polymer from at least one monomer, such as temperature, pressure, atmosphere, proportions of starting components used in the polymerization mixture, reaction time, or external stimulus to the polymerization mixture. The polymerization process may be carried out in bulk, solution or other conventional polymerization manner. The process is carried out under any reaction conditions suitable for the polymerization mechanism.

As used herein, the terms "ring opening" and "ring opening reaction" refer to the conversion of a cyclic monomer to its acyclic form. Further, as used herein, the term "ring-opening polymerization" refers to the formation of a chain of a plurality of ring-opened cyclic monomers. Specifically herein, the term ring-opening polymerization is intended to include both: i) an "open-ring homopolymerization" of a lactone compound; and ii) a "ring-opening copolymerization" of two or more different lactone compounds.

As used herein, "polyol" refers to any compound comprising two or more hydroxyl groups. The term thus encompasses diols, triols and compounds containing four or more-OH groups.

The term "epoxy compound" denotes monoepoxy compounds and polyepoxy compounds (polyepoxide compounds): it is intended to encompass epoxy functional prepolymers. The term "polyepoxide" is therefore intended to mean an epoxy compound having at least two epoxide groups. Furthermore, the term "diepoxy compound" is therefore intended to mean an epoxy compound having two epoxy groups.

As used herein, "polyisocyanate" refers to a compound comprising at least two-N ═ C ═ O functional groups, for example, 2 to 5 or 2 to 4-N ═ C ═ O functional groups. Suitable polyisocyanates include aliphatic, cycloaliphatic, aromatic and heterocyclic isocyanates, dimers and trimers thereof, and mixtures thereof.

Aliphatic and cycloaliphatic polyisocyanates may contain from 6 to 100 carbon atoms which are linked or cyclized in a straight chain and have at least two isocyanate-reactive groups. Examples of suitable aliphatic isocyanates include, but are not limited to: straight-chain isocyanates such as ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, 1, 6-Hexamethylene Diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 1,6, 11-undecane triisocyanate, 1,3, 6-hexamethylene triisocyanate, bis (isocyanatoethyl) carbonate and bis (isocyanatoethyl) ether. Exemplary cycloaliphatic polyisocyanates include, but are not limited to: dicyclohexylmethane 4,4' -diisocyanate (H)₁₂MDI), 1-isocyanatomethyl-3-isocyanato-1, 5, 5-trimethyl-cyclohexane (isophorone diisocyanate, IPDI), cyclohexane 1, 4-diisocyanate, hydrogenated xylylene diisocyanate (H)₆XDI), 1-methyl-2, 4-diisocyanato-cyclohexane, m-or p-tetramethylxylene diisocyanate (m-TMXDI, p-TMXDI) and dimer fatty acid diisocyanate.

The term "aromatic polyisocyanate" is used herein to describe organic isocyanates in which the isocyanate groups are directly attached to the rings of a mononuclear or polynuclear aromatic hydrocarbon group. Further, the mononuclear or polynuclear aromatic hydrocarbon group refers to a substantially planar cyclic hydrocarbon moiety of a conjugated double bond, which may be a single ring or may comprise a plurality of fused (fused) or covalently linked rings. The term aromatic also includes alkylaryl. Typically, the hydrocarbon (main) chain comprises 5, 6, 7 or 8 main chain atoms in one ring. Examples of such planar cyclic hydrocarbon moieties include, but are not limited to: cyclopentadienyl, phenyl, naphthyl- (napthalenyl-), [10]Rotanyl- (1,3,5,7, 9-cyclopentadecenyl-) ([ 10)]annulenyl-(1,3,5,7,9-cyclodecapentaenyl-))、[12]Rotanyl-, [8 ]]Cycloalkene-, phenalene (perinaphthalene), 1, 9-dihydropyrene,

(1, 2-triphenylene). Examples of alkylaryl moieties are benzyl, phenethyl, 1-phenylpropyl, 2-phenylpropylPhenyl, 3-phenylpropyl, 1-naphthylpropyl, 2-naphthylpropyl, 3-naphthylpropyl and 3-naphthylbutyl.

Exemplary aromatic polyisocyanates include, but are not limited to: all isomers of Toluene Diisocyanate (TDI), in isomerically pure form or as a mixture of several isomers; naphthalene 1, 5-diisocyanate; diphenylmethane 4,4' -diisocyanate (MDI); diphenylmethane-2, 4' -diisocyanate and mixtures of diphenylmethane 4,4' -diisocyanate with the 2,4' -isomer or with higher-functional oligomers (so-called crude MDI); xylylene Diisocyanate (XDI); diphenyl-dimethylmethane 4,4' -diisocyanate; dialkyl-and tetraalkyl-diphenylmethane diisocyanates; dibenzyl 4,4' -diisocyanate; phenylene 1, 3-diisocyanate; and phenylene 1, 4-diisocyanate.

Note that the term "polyisocyanate" is intended to encompass prepolymers formed by the partial reaction of the aforementioned aliphatic, cycloaliphatic, aromatic and heterocyclic isocyanates with polyols to give isocyanate-functional oligomers, which may be used alone or in combination with one or more free isocyanates.

For the sake of completeness: a) the primary amino group being-NH₂"(R-H) type radical; b) the secondary amine group is an atomic group of the type "-NHR"; and c) the tertiary amine group is-NR₂"type of radical. By amino-functional polymer is meant a polymer having at least one amine group.

As used herein, the term "catalytic amount" refers to a sub-stoichiometric amount of catalyst relative to the reactants.

The term "substantially free" is intended herein to mean that the applicable group, compound, mixture, or component constitutes less than 0.1 wt.%, based on the weight of the defined composition.

Drawings

Figure 1, appended hereto, is a chromatogram obtained from Gel Permeation Chromatography (GPC) analysis of a polyester prepared according to an embodiment of the present invention.

Figure 2, appended hereto, is a comparative chromatogram obtained from Gel Permeation Chromatography (GPC) analysis of a polyester prepared according to the disclosure of US 20100179282a1(Evonik Degussa).

Detailed Description

As previously described, the present invention provides a process for preparing an amino-functional polyester, the process comprising: providing a mixture comprising at least one lactone monomer, a catalyst, and a polyamine having at least one primary amine group and at least one secondary amine group; and subjecting the mixture to ring-opening polymerization conditions.

The lactone compound which can be used as a monomer in the present invention is not particularly intended to be limited as long as the compound can be subjected to ring-opening polymerization in the presence of a catalyst. In general, however, suitable lactone monomers conform to the following general formula (1):

wherein: n is more than or equal to 1;

each R is independently selected from hydrogen, C1-C6 alkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, and C6 aryl, with the proviso that at least n of the Rs are hydrogen.

Preferred lactone monomers corresponding to formula (1) are characterized by the following limitations: n is an integer of 1 to 4; and each R is independently selected from hydrogen and C1-C6 alkyl, provided that at least n + 2R are hydrogen.

As exemplary lactone monomers which may be used alone or in combination, β -propiolactone, β -butyrolactone, β -valerolactone, γ -butyrolactone, γ -valerolactone, δ -valerolactone, monomethyl- δ -valerolactone, monoethyl- δ -valerolactone, monohexyl- δ -valerolactone, ε -caprolactone, monomethyl- ε -caprolactone, monoethyl- ε -caprolactone, monohexyl- ε -caprolactone, dimethyl- ε -caprolactone, di-n-propyl- ε -caprolactone, di-n-hexyl- ε -caprolactone, trimethyl- ε -caprolactone, triethyl- ε -caprolactone, pivalolactone, and 5-methyloxepan-2-one may be mentioned.

In addition to the lactones described above, no more than 20 wt.% of other comonomers may be included in the polymerization mixture, based on the total weight of the monomers. When present, the comonomer is desirably selected from: epoxy compounds such as glycidyl ethers, monoepoxides of dienes and polyenes, glycidyl esters and alkylene oxides; a cyclic carbonate; glycolide; lactide; and combinations thereof.

Non-limiting examples of suitable epoxy compounds that can be used as comonomers include: ethylene oxide, propylene oxide, butylene oxide, 3, 4-epoxy-1-pentene, styrene oxide, vinyl glycidyl ether, isopropenyl glycidyl ether, butylene oxide (butadiene monooxide), and phenyl glycidyl ether. Preference may be given to ethylene oxide and/or propylene oxide.

Non-limiting examples of suitable cyclic carbonates include those represented by the formula:

wherein: f and g are integers from 1 to 3;

for each carbon unit (i.e. for each (C)_fAnd (C)_gUnit), R¹、R²、R³And R⁴Independently selected from hydrogen, C1-C6 alkyl, C6-aryl or-OC₆H₅。

h is 0 or 1; and is

E is-O-.

As specific examples of suitable cyclic carbonate comonomers, mention may be made of: trimethylene carbonate (TMC), tetramethylene carbonate (TEMC), pentamethylene carbonate (PMC), and 1, 2-propanediol carbonate.

The ring-opening polymerization of the present invention involves using, as an initiator, a polyamine having the following groups: at least one and preferably at least two primary amine groups, and at least one secondary amine group. In principle, all polyamines which satisfy this condition with such amine groups of different reactivity are suitable. The polyamine initiator may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic. However, preference may be given to aliphatic and/or cycloaliphatic polyamines. Without intending to limit the present invention, exemplary polyamines comprising at least one secondary amino group and at least one secondary amino group include: n-methylethylenediamine, N-ethylethylenediamine, N-propylethylenediamine, N-butylethylenediamine, N-benzylethylenediamine, N-phenylethylenediamine, N-methylpropanediamine, N-ethylpropylenediamine, N-propylpropylenediamine, N-butylpropylenediamine, N-benzylpropylenediamine, N-phenylpropylenediamine, N-hydroxyethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dihexamethylenetriamine, N-cyclohexylpropylenediamine, and N- [3- (tridecyloxy) propyl ] -1, 3-propylenediamine (Adogen 583).

It is mentioned here that in general and in view of the exemplary polyamines listed above, aliphatic and/or cycloaliphatic polyamines are preferably present.

The ratio of lactone monomer to initiator in the process can vary widely depending on the particular properties desired in the polyester or product derived therefrom. Obviously, where the polyester is to have substantially the nature of a product containing a series of lactone residues, the ratio of initiator to lactone may be very small, since theoretically one molecule of initiator is sufficient to initiate polymerization of a myriad of lactone molecules. Rather, the relative proportions may be approximately equal, particularly where the initiator used is at least trifunctional and/or where the polyester product is intended to be a conjugated structure with more or less alternating distribution of lactone residues.

The above-identified molar ratio of lactone monomer to the polyamine initiator is generally in the range of 1:1 to 500:1, preferably in the range of 2:1 to 50:1, and more preferably in the range of 2:1 to 20: 1.

As previously mentioned, the ring polymerization process of the present invention is carried out in the presence of a suitable catalyst. A guide to suitable ionic or non-ionic catalysts for Ring-Opening Polymerization is described in Ring Opening Polymerization (Vol.1, p.461-521, K.J.Ivin and T.Saegusa (1984)). Known catalysts that may be used alone or in combination include, but are not limited to: amine compounds or salts thereof with carboxylic acids, e.g. butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminoPropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,5, 7-triazabicyclo [4.4.0]]Dec-5-ene (TBD) and 1, 8-diazabicyclo- (5,4,0) -undecene-7 (DBU); tin 2-ethylhexanoate (tin octanoate); tin dichloride (SnCl)₂) (ii) a A porphyrin aluminum complex; (n-C)₄H₉O)₄Al₂O₂Zn; a composite metal cyanide compound; diethyl zinc or diethyl cadmium containing water; aluminum triisopropoxide; titanium tetrabutoxide; zirconium tetrabutoxide; tributyltin methoxide; tetraphenyltin; lead oxide; zinc stearate; bismuth 2-ethylhexanoate; potassium alcoholate; antimony fluoride; and catalysts based on yttrium or lanthanide rare earth metals (coordination catalysts), for example as described in us patent No. 5,028,667.

Preferably, the catalyst is metal-free. In particular, but not intending to limit the invention, good results have been obtained with the use of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD) and/or 1, 8-diazabicyclo- (5,4,0) -undecene-7 (DBU) as polymerization catalyst.

Although the determination of a suitable catalytic amount of the compound is easy for a person skilled in the art, it is preferred that the polymerization catalyst is used in an amount of 0.1 to 5 wt.%, for example 0.1 to 2.0 wt.%, based on the total weight of the monomers.

The ring-opening polymerization reaction may be initiated at room temperature. The exothermic nature of the reaction naturally raises the temperature of the reactants. That is, the reaction temperature should be maintained in the range of 50 to 200 ℃ or 60 to 150 ℃. If the temperature is maintained below 50 ℃, the reaction rate may be disadvantageously low. On the other hand, if the temperature is maintained above 200 ℃, the polymer degradation rate increases and low molecular weight components may form and even vaporize.

As is known in the art, the polymerization vessel may be dried and purged with an inert gas (e.g., nitrogen or argon) prior to initiating the ring-opening polymerization reaction. Furthermore, to avoid the formation of discolored polyester products, a partial vacuum or inert atmosphere may be maintained in the reaction vessel during polymerization: by creating such a partial vacuum or by passing nitrogen or argon through the reaction mixture, the presence of oxygen in the reaction vessel can be excluded or minimized.

The polymerization can be carried out in solution or in a solvent-free melt, but in either case the vessel should be equipped with an effective stirrer, for example a mechanical stirrer: it has been observed that good agitation can drive the polymerization reaction to completion.

It is preferred here that the polymerization mixture is substantially free of solvent: for completeness, this preferred statement includes that the polymerization mixture is substantially free of water. However, if the polymerization is chosen to be carried out in solution, a suitable solvent should be a non-reactive, substantially anhydrous organic liquid capable of dissolving at least 1 wt%, preferably more than 10 wt%, of the amino-functional polyester product at 25 ℃. As suitable organic solvents, mention may be made of: aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as heptane and decane; alicyclic hydrocarbons such as cyclohexane and decalin; chlorinated hydrocarbons such as chloroform and trichloroethylene; esters such as ethyl acetate and methyl butyrate; and ethers such as Tetrahydrofuran (THF) and dioxane.

The progress of the polymerization reaction can be monitored by Nuclear Magnetic Resonance (NMR) spectroscopy, wherein the reaction is considered complete when the signal associated with the initial lactone is completely absent. Depending on the lactone monomer, it is believed that the progress of the reaction can also be monitored by: refractive index measurements, where the reaction can be considered complete as long as the refractive index becomes constant; and thermal analysis, since the reaction of the lactone promotes an exotherm such that complete consumption of the lactone corresponds to cooling of the mixture. In any case, the polymerization time is usually from 0.1 to 10 hours, for example from 0.5 to 5 hours. If applicable and desired, a vacuum may be applied at elevated temperature (e.g., 120 ℃ to 160 ℃) to remove any unreacted monomer.

Although this is not critical for its later administration, the reaction product (hereinafter denoted AF-PES) can be isolated and purified by using methods known in the art: mention may be made in this connection of extraction, evaporation, distillation and chromatography. If the (optionally purified) reaction product (AF-PES) is intended to be stored immediately after preparation, the polyester should be arranged in a container having a gas-tight seal and a moisture-tight seal.

The polyester obtained according to this process is characterized by having at least one terminal hydroxyl group. An initiator is incorporated into the polyester structure, which is thus also characterized by having secondary amine groups.

According to a preferred embodiment of the invention, the derivatized amino-functional polyester (AF-PES) is characterized by at least one of the following:

i) a weight average molecular weight of 300 to 5000g/mol, preferably 500 to 4000 g/mol;

ii) a polydispersity index of less than 2.5, preferably less than 2.3;

iii) an amine number (NHv) of 20 to 350mg KOH/g, preferably 25 to 250mg KOH/g; and

iv) a total hydroxyl number and amine number (or alkalinity (OHv + NHv) of 40 to 500mg KOH/g, preferably 50 to 400mg KOH/g.

For the sake of completeness, it is noted that these limitations are not mutually exclusive, and thus one, two, three or four of these features may apply.

Coating, sealant and adhesive compositions

The amino-functional polyester (AF-PES) obtained using the process of the present invention may be used as a reactive component in curable coating, adhesive or sealant compositions. The further reactants of such compositions are typically one or more polyfunctional compounds (H) having at least two functional groups (F) selected from: (i) activated unsaturated groups, such as (meth) acryloyl groups; (ii) activated methylene groups such as acetoacetate and malonate groups; (iii) an epoxy group; (iv) an isocyanate group; (v) an aromatic activated aldehyde group; (vi) a cyclic carbonate group; and (vii) acid, anhydride, and ester groups, including oxalates. Also contemplated are latent compounds in which the functional group (F) is blocked but can be activated under specific physicochemical conditions as suitable additional reactants for coating, adhesive or sealant compositions.

The number of functional groups (F) possessed by the (activated) compound (H) is not particularly limited: for example, compounds having 2, 3,4, 5, 6, 7, 8, 9, or 10 functional groups may be used. Furthermore, the reactant compound (H) may be a low molecular weight species (i.e., having a molecular weight of less than 500g/mol), or an oligomeric or polymeric species having a number average molecular weight (Mn) of greater than 500 g/mol. Moreover, it is of course possible to use mixtures of compounds (H).

In one embodiment of the coating, adhesive or sealant composition, the reactant compound (H) having at least two functional groups is selected from: a polyepoxide; a cyclic carbonate; and a polyisocyanate. More particularly, the reactant compound (H) having at least two functional groups is selected from: a polyepoxide; and a cyclic carbonate.

Suitable polyepoxides can be liquid, solid, or in solution in a solvent. Furthermore, the epoxy equivalent weight of such polyepoxides should be from 100 to 700g/eq, for example from 120 to 320 g/eq. Also, in general, diepoxy compounds having an epoxy equivalent weight of less than 500 or even less than 400 are preferred.

Suitable diglycidyl ether compounds can be aromatic, aliphatic, or cycloaliphatic in nature and can likewise be derived from dihydric phenols and dihydric alcohols. Useful classes of such diglycidyl ethers are: diglycidyl ethers of aliphatic and cycloaliphatic diols, such as 1, 2-ethanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 12-dodecanediol, cyclopentanediol and cyclohexanediol; diglycidyl ethers based on bisphenol a; bisphenol F diglycidyl ether; diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate; polyglycidyl ethers based on polyalkylene glycols, in particular polypropylene glycol diglycidyl ether; and glycidyl ethers based on polycarbonate diols. Other suitable diepoxy compounds that may also be mentioned include: diepoxy compounds of di-unsaturated fatty acid C1-C18 alkyl esters; dibutylene diepoxide (butadiene diepoxide); polybutadiene diglycidyl ether; vinylcyclohexene diepoxide; and limonene diepoxide.

Exemplary polyepoxides include, but are not limited to: glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, and sorbitol polyglycidyl ether.

Examples of highly preferred polyepoxides for use as compound (H), without intending to limit the present invention, include: bisphenol-A epoxy resins, e.g. DER^TM331 and DER^TM383 (b); bisphenol-F epoxy resins, e.g. DER^TM354; bisphenol-A/F epoxy resin blends, e.g. DER^TM353; aliphatic glycidyl ethers, e.g. DER^TM736; polypropylene glycol diglycidyl ethers, e.g. DER^TM732; solid bisphenol-A epoxy resins, e.g. DER^TM661 and DER^TM664 UE; solutions of bisphenol-A solid epoxy resins, e.g. DER^TM671-X75; epoxy novolac resins, e.g. DEN^TM438; brominated epoxy resins, e.g. DER^TM542; castor oil triglycidyl ethers, e.g. ERISYS^TMGE-35H; polyglycerol-3-polyglycidyl ethers, e.g. ERISYS^TMGE-38; and sorbitol glycidyl ethers, e.g. ERISYS^TMGE-60。

As examples of suitable cyclic carbonate group-containing monomeric and oligomeric compounds, mention may be made of: a compound prepared by reacting a hydroxy-functional cyclic carbonate with a polyisocyanate; and by introducing CO₂A compound prepared by addition to an epoxy group-containing monomer or oligomer. The following citation disclosures may be instructive in disclosing suitable cyclic carbonate functional compounds: U.S. Pat. No.3,535,342, U.S. Pat. No.4,835,289, U.S. Pat. No.4,892,954, British patent No. GB-A-1,485,925, and EP-A-0119840.

The total amount of compound (H) present in the curable composition is preferably selected such that the molar ratio of amine groups of the functional polyester (AF-PES) to functional groups (F) is from 1:10 to 10:1, for example from 5:1 to 1:5, and preferably in the range from 1:2 to 2: 1. For example, the molar ratio of amine groups of the functional polyester (AF-PES) to epoxy or cyclic carbonate groups in the hardening compound (H) may be from 1:2 to 3:2 or from 2:3 to 4: 3.

In an alternative expression of the composition, the total amount of compound (H) is suitably 0.1-50 wt.%, preferably 0.5-40 wt.% and more preferably 1-30 wt.%, based on the added total amount of amino-functional polyester (AF-PES) and compound (H).

The curable composition may contain additives and auxiliary ingredients as is standard in the art. Suitable additives and adjunct ingredients include: catalysts, antioxidants, ultraviolet absorbers/light stabilizers, metal deactivators, antistatic agents, reinforcing agents, fillers, antifogging agents, propellants, biocides, plasticizers, lubricants, emulsifiers, dyes, pigments, rheology agents, impact modifiers, adhesion modifiers, optical brighteners, flame retardants, anti-drip agents (anti-drip agents), nucleating agents, wetting agents, thickeners, protective colloids, defoamers, tackifiers, solvents, reactive diluents, and mixtures thereof. The choice of suitable conventional additives for the composition depends on its particular intended use and can be determined by the skilled person in individual cases.

In certain embodiments of the present invention, no catalyst is required to catalyze the reaction of the cyclic amine group with the functional group (F) of compound (H): this is generally the case when a cyclic carbonate group or an epoxy group is present as functional group (F). However, in other cases, and preferably where compound (H) has a reactive group F different from the cyclic carbonate or epoxy group, a catalyst may be required: suitable catalysts for hardening are then determined in a known manner depending on the type of reactive functional group (F). When desired, the catalyst is used in an amount of 0.01 to 10 wt.%, preferably 0.01 to 5 wt.%, based on the total weight of the curable composition.

The curable coating, adhesive or sealant composition should contain less than 5 wt.% water, based on the weight of the composition, and is most preferably an anhydrous composition that is substantially free of water. These embodiments do not preclude the composition from comprising or being substantially free of organic solvents.

Broadly, all organic solvents known to the person skilled in the art can be used as solvents, but preferably the organic solvent is selected from: esters, ketones, halogenated hydrocarbons, alkanes, alkenes, and aromatic hydrocarbons. Exemplary solvents are dichloromethane, trichloroethylene, toluene, xylene, butyl acetate, amyl acetate, isobutyl acetate, methyl isobutyl ketone, methoxybutyl acetate, cyclohexane, cyclohexanone, dichlorobenzene, diethyl ketone, diisobutyl ketone, dioxane, ethyl acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl acetate, 2-ethylhexyl acetate, ethylene glycol diacetate, heptane, hexane, isobutyl acetate, isooctane, isopropyl acetate, methyl ethyl ketone, tetrahydrofuran or tetrachloroethylene, or a mixture of two or more of the foregoing solvents.

Method and use

To form a coating, sealant or adhesive composition, the reactive compounds are brought together and mixed in a manner that causes the adhesive to harden. More particularly, the amino-functional polyester (AF-PES) and the compound (H) can be mixed in predetermined amounts by hand, by machine, by (co) extrusion or by any other means capable of ensuring a fine and highly homogeneous mixing thereof.

The hardening of the adhesive composition of the invention generally takes place at a temperature in the range from-10 ℃ to 150 ℃, preferably from 0 ℃ to 100 ℃ and in particular from 10 ℃ to 70 ℃. The appropriate temperature depends on the particular compound (H) and the desired rate of hardening and can be determined in individual cases by the skilled person as desired using simple preliminary tests. Of course, hardening at a temperature of 5 ℃ to 35 ℃ or 20 ℃ to 30 ℃ is particularly advantageous as it avoids the need to heat or cool the mixture considerably from the ambient temperature which normally prevails. However, where applicable, the temperature of the mixture of amino-functional polyester (AF-PES) and compound (H) may be increased above the mixing temperature by using conventional means, including microwave induction.

The composition according to the invention can be used in particular in: varnish; printing ink; an elastomer; foaming; a binder for the fibers and/or particles; coating of glass; coatings for mineral building materials, such as lime-and/or cement-bonded plasters, gypsum-containing surfaces, fiber cement building materials and concrete; coating and sealing of wood and wood materials (e.g., particle board, fiber board, and paper); coating of metal surfaces; asphalt-containing and asphalt-containing road surface coatings; coating and sealing of various plastic surfaces; and coatings for leather and textiles.

The compositions of the present invention are also believed to be suitable as pourable-sealing compounds for electrical building components, such as cables, optical fibres, cover strips (plugs) or plugs. Sealants may be used to protect those components from the ingress of water and other contaminants, from thermal exposure, temperature fluctuations and thermal shock, and from mechanical damage.

Since the compositions of the invention are often capable of producing high adhesive strengths in a short time at room temperature, in particular in the case of epoxy or cyclic carbonate hardeners (H), the compositions are optimally used for forming composite structures by surface-to-surface bonding of identical or different materials to one another. As exemplary adhesive applications of the composition of the present invention, mention may be made of the bonding together of wood and wooden materials and the bonding together of metallic materials (e.g. mild steel).

In a particularly preferred embodiment of the invention, the curable composition is used as a solvent-free or solvent-containing laminating adhesive for bonding plastics and polymer films, such as polyolefin films, poly (methyl methacrylate) films, polycarbonate films and Acrylonitrile Butadiene Styrene (ABS) films.

In each of the applications described above, the composition may be applied by conventional application methods such as: brushing; roll coating, for example, using a 4-coat roll apparatus in which the composition is solvent-free or a 2-coat roll apparatus for a solvent-containing composition; coating by a scraper; a printing method; and spray coating methods including, but not limited to, air atomized spray coating, air assisted spray coating, airless spray coating, and high volume low pressure spray coating. For the application of coatings and adhesives, it is advisable to apply the compositions in a wet film thickness of from 10 to 500 μm. Thinner layers in this range are more economical to apply and reduce the likelihood of thick cured areas (for paint applications) that may require sanding. However, tight control must be exercised in applying thinner coatings or layers to avoid the formation of a discontinuous cured film.

Various features and embodiments of the present disclosure are described in the following examples, which are intended to be representative and not limiting.