阅读说明：本技术 官能化聚酯的制备方法 (Process for preparing functionalized polyesters ) 是由 M·帕拉达斯-帕洛莫 S·弗洛雷斯-佩纳尔瓦 J·加西亚-米拉莱斯 H-G·金策尔曼 R·M 于 2018-05-02 设计创作，主要内容包括：本申请涉及一种用于制备环状碳酸酯官能聚酯的方法,所述方法包括：使碳酸甘油酯与酸酐反应以形成加合物(A)；以及使所述加合物(A)与至少一种聚环氧化合物反应以形成所述环状碳酸酯官能聚酯(CC-PES)。更具体地,本申请涉及一种用于制备环状碳酸酯官能聚酯的方法,所述方法包括以下阶段：A)使碳酸甘油酯与酸酐反应以形成加合物(A)；B)提供聚羧酸；C)使所述聚羧酸与至少一种二缩水甘油醚反应以形成环氧官能聚酯；以及D)使所述环氧官能聚酯与所述加合物(A)反应以形成所述环状碳酸酯官能聚酯。(The present application relates to a process for preparing a cyclic carbonate functional polyester, the process comprising: reacting glycerol carbonate with an anhydride to form an adduct (a); and reacting the adduct (a) with at least one polyepoxide to form the cyclic carbonate functional polyester (CC-PES). More specifically, the present application relates to a process for the preparation of a cyclic carbonate functional polyester comprising the following stages: A) reacting glycerol carbonate with an anhydride to form an adduct (a); B) providing a polycarboxylic acid; C) reacting the polycarboxylic acid with at least one diglycidyl ether to form an epoxy-functional polyester; and D) reacting the epoxy functional polyester with the adduct (A) to form the cyclic carbonate functional polyester.)

1. A method for preparing a cyclic carbonate functional polyester, the method comprising:

reacting glycerol carbonate with an anhydride to form an adduct (a); and

reacting the adduct (A) with at least one polyepoxide to form the cyclic carbonate functional polyester (CC-PES).

2. The process for the preparation of a cyclic carbonate functional polyester according to claim 1, comprising the following stages:

A) reacting glycerol carbonate with an anhydride to form an adduct (a);

B) providing a polycarboxylic acid;

C) reacting the polycarboxylic acid with at least one diglycidyl ether to form an epoxy-functional polyester; and

D) reacting the epoxy functional polyester with the adduct (A) to form the cyclic carbonate functional polyester.

3. The process of claim 1 or claim 2, wherein the reactant anhydride is selected from the group consisting of: maleic anhydride; adipic anhydride; succinic anhydride; alkyl succinic anhydrides; alkenyl succinic anhydrides; glutaric anhydride; alkyl glutaric anhydride; alkenyl glutaric anhydride; and mixtures thereof.

4. A process according to any one of claims 1 to 3, wherein the reaction of the glycerol carbonate with the anhydride is carried out under at least one of the following limiting conditions:

i) acid anhydride: the molar ratio of glycerol carbonate is from 2:1 to 0.8:1, preferably from 1.2:1 to 0.8:1, and more preferably from 1.1:1 to 0.9: 1;

ii) a temperature of from 60 ℃ to 180 ℃, preferably from 80 ℃ to 150 ℃; and

iii) under anhydrous conditions.

5. Process according to any one of claims 2 to 4, wherein the polycarboxylic acid of stage B is a carboxyl-functional polyester (Carboxy-PES), preferably characterized by an acid value (Av) of from 50 to 500mgKOH/g, preferably from 80 to 430 mgKOH/g.

6. The process according to claim 5, wherein the Carboxy functional polyester (Carboxy-PES) is provided by:

i) providing a polyester having two or more hydroxyl groups; and

ii) reacting the hydroxy functional polyester with a carboxylic acid or anhydride thereof.

7. The process according to claim 6, wherein the hydroxy-functional polyester has a hydroxyl number of from 50 to 300mgKOH/g, preferably from 80 to 150 mgKOH/g.

8. The process of claim 5, wherein the Carboxy-functional polyester (Carboxy-PES) is provided by the reaction of a stoichiometric excess of a dicarboxylic acid with at least one diol in the presence of a catalytic amount of an esterification catalyst.

9. A process according to any one of claims 2 to 8 wherein in stage C the or each diglycidyl ether has an epoxy equivalent weight of from 100 to 700g/eq, preferably from 120 to 320 g/eq.

10. The process according to any one of claims 2 to 9, wherein in stage C the molar ratio of the diglycidyl ether compound to the carboxy-functional polyester is from 1.5:1 to 3:1, preferably from 1.8:1 to 2.2: 1.

11. The process according to any one of claims 2 to 10, wherein phases C and D are carried out under the following conditions:

i) at a temperature of from 40 ℃ to 180 ℃, preferably from 60 ℃ to 170 ℃; and/or

ii) in the presence of a catalytic amount of a basic catalyst.

12. The process according to any one of claims 2 to 11, wherein stages B to D are carried out successively in one vessel and without isolation of intermediates.

13. The process according to any one of claims 1 to 12, wherein in the reaction of the adduct (a) the equivalent ratio of carboxyl groups to epoxide groups is at least 1:1, and preferably is (1.0-1.2): 1 or is (1.0-1.1): 1.

14. a cyclic carbonate functional polyester obtained by the process as defined in any one of claims 1 to 13, said cyclic carbonate functional polyester preferably being characterized by at least one of the following features:

a cyclic carbonate equivalent weight of 400 to 2500g/eq, preferably 500 to 1500 g/eq;

a number average molecular weight (Mn) of from 500 to 5000g/mol, preferably from 800 to 3000 g/mol; and

an OH number of from 50 to 300mgKOH/g, preferably from 100 to 200 mgKOH/g.

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

a cyclic carbonate functional polyester as defined in claim 14; and

at least one polyfunctional compound (H), wherein the at least one polyfunctional compound (H) has at least two functional groups (F) selected from: a primary amino group; a secondary amino group; a hydroxyl group; a phosphine group; a phosphonate group; and a thiol group.

Technical Field

The present application relates to a process for preparing functionalized polyesters. More particularly, the present application relates to a process for preparing cyclic carbonate functional polyesters and to the use of said polyesters in coating, adhesive or sealant compositions.

Background

The use of polyurethanes in coating, adhesive and sealant formulations is well known and has long been established. This polyurethane contains precursor materials that cure in situ to form the adhesive layer: conventionally, the curing agent compound comprises one or more polyisocyanate compounds and one or more isocyanate-reactive compounds (e.g., polyols). Depending on the selection of those curing agent compounds, a given polyurethane coating, adhesive, or sealant can be formulated to cure at room temperature or upon exposure to certain physicochemical conditions.

The presence of isocyanates in such conventional polyurethane formulations poses toxicological risks. On the one hand, this relates to the processing of these materials during their use, since isocyanates generally have a high toxicity and a high sensitization potential. On the other hand, there is a risk that: in flexible substrates, incompletely reacted aromatic isocyanates migrate through the substrate and are hydrolyzed by moisture or aqueous components to carcinogenic aromatic amines.

Accordingly, there is a desire for isocyanate-free mono (1K) and bis (2K) component systems for hardenable coating compositions that have good hardening properties, ideally even at room temperature. And it has been recognized in the art that cyclic carbonates that can be reacted with amines at room temperature to form carbamates can represent an important alternative to polyurethane formation by the aforementioned isocyanate/polyol reaction. However, there are known obstacles to the more general use of cyclic carbonates to form NCO-free polyurethanes (NIPU): i) cyclic carbonates generally have limited reactivity even in the presence of catalysts such as amidines, guanidines, and thioureas; ii) the ring-opening reaction of the cyclic carbonate is less selective, so that a mixture of stable secondary alcohols and less stable primary alcohols is formed; and iii) as a result of extrapolation, the polyurethanes formed tend to have low molecular weights, which limits their utility.

The limited Reactivity of 5- (2-propenyl) -1, 3-dioxan-2-one (1) and 4- (3-butenyl) -1, 3-dioxan-2-one (2) with hexylamine and benzylamine was noted in the article "Reactivity compliance of five-and six-member cyclic carbonates with amines", published by Tomita et al in Journal of Polymer Science, 1.2001, 1, 39, page 162 and 168, Basic evaluation for synthesis of poly (hydroxuurethane). However, the authors also found that the reactivity of those cyclic carbonates depends on the substituent group (R) located at its 4-position. For example, the reactivity increases in the order in which R is the following group or atom: me < H < phenyl < CH₂OPh＜CF₃. Although beneficial, such fluorinated compounds are not readily available, are expensive, and are potentially toxic. Furthermore, monomeric cyclic compounds are not suitable for use as binders in coating, adhesive or sealant formulations.

An article "Activated lipid cyclic carbonates for non-isocyanate polyurethanes" published by Lamarzelle et al in Polymer Chemistry 2016 (7 th stage 1439) 1451 describes a way to activate cyclic carbonate rings by introducing an electron withdrawing group comprising an ester or ether moiety at the beta position to increase its reactivity towards amines. The cited literature content (position) itself is limited in its commercial application: the synthesis procedures and catalysts used to prepare the bifunctional ester-cyclic carbonate materials are not industrially feasible due to the high cost; and the synthesis yields a crystalline material at room temperature. Furthermore, the inventors of the present invention have recognized the potential to develop high molecular weight cyclic carbonate functional polyesters in which the ester group is in the beta-position to a 5-membered cyclic carbonate group.

WO 2016/124518A 1(Evonik Degussa GMBH) describes a process for preparing polymers with cyclic carbonates, and in particular polyesters with cyclic carbonates. In the latter embodiment, the polyester is obtained in a two-step process. First, a carboxyl-terminated polyester is synthesized. In a second step, the carboxyl-terminated polyester is esterified with glycerol carbonate. This second step is typically carried out in the presence of a lewis acid or strong acid (e.g., methanesulfonic acid), which would need to be removed from the final product and may also blacken the final product. Furthermore, in an exemplary embodiment of this second step, a reaction temperature of 180 ℃ or higher is employed at which the glycerol carbonate is unstable.

WO2012/007254(Total Petrochemical res. feloy et al) describes a process for the preparation of poly (carbonate-urethane) or poly (ester-urethane) comprising the steps of: a) ring-opening polymerization of a first 5-, 6-or 7-membered cyclic carbonate or cyclic ester or diester (which optionally carries a functional group) in the presence of a first catalyst system and in the presence of one or more diols or polyols which act both as co-initiator and chain transfer agent; b) chemically modifying a hydroxyl chain terminal group to a carboxyl group in the presence of a second catalyst system; c) performing a coupling reaction with at least 2 equivalents of a second 5-, 6-or 7-membered cyclic carbonate bearing at least one functional group enabling coupling with a carboxyl moiety in the presence of a third catalyst system; d) addition polymerization of a diamine or polyamine via ring opening of the second terminal 5-, 6-or 7-membered cyclic carbonate of step c); and e) recovering the poly (carbonate-urethane) or poly (ester-urethane).

EP 2582687B 1(Construction Research & Technology GMBH) describes a two-step process for the preparation of cyclic carbonate-functional polyesters. The first step provides for the formation of a 5-membered cyclic carbonate according to the following illustrative reaction scheme:

in the second step, the derivatized cyclic carbonate is transesterified with a polyol, but in the necessary presence of an exogenous catalyst, more specifically an enzymatic catalyst or an acidic cation exchanger. An exemplary second step according to this citation is illustrated below:

2

in view of the above cited documents, there is still a need in the art to provide a simple, cost-effective and industrially feasible method for the synthesis of 5-membered cyclic carbonate functional oligomers or polymers, wherein the polyester group is in the beta position.

Disclosure of Invention

According to a first aspect of the present invention there is provided a process for the preparation of a cyclic carbonate functional polyester, the process comprising: reacting glycerol carbonate with an anhydride to form an adduct (a); and reacting the adduct (a) with at least one polyepoxide compound to form the cyclic carbonate functional polyester (CC-PES).

The reactant anhydride is typically an anhydride of an acid selected from: maleic acid; fumaric acid; citraconic acid; itaconic acid; glutaconic acid; phthalic acid; isophthalic Acid (IA); terephthalic acid; cyclohexane dicarboxylic acid; adipic acid; sebacic acid (SeA); azelaic acid (azealic acid); malonic acid; succinic acid; alkyl succinic acids; alkenyl succinic acid; glutaric acid; alkyl glutaric acid; alkenyl glutaric acid; and mixtures thereof. Preferably, the reactant anhydride is selected from: maleic anhydride; adipic anhydride; succinic anhydride; alkyl succinic anhydrides; alkenyl succinic anhydrides; glutaric anhydride; alkyl glutaric anhydride; alkenyl glutaric anhydride; and mixtures thereof.

The reaction of glycerol carbonate with the anhydride, referred to as stage a in certain embodiments below, is generally carried out under at least one of the following constraints: i) acid anhydride: the molar ratio of glycerol carbonate is from 2:1 to 0.8:1, preferably from 1.2:1 to 0.8:1, and more preferably from 1.1:1 to 0.9: 1; ii) a temperature of from 60 ℃ to 180 ℃, preferably from 80 ℃ to 150 ℃; and iii) anhydrous conditions. For the sake of completeness, it is noted that these process limitations are not mutually exclusive and that one, two or three of these limitations may be implemented.

When the reaction of the adduct (A) with at least one polyepoxide is carried out, it is ensured that all the epoxide groups initially present have reacted. Thus, the compounds may be reacted in an equivalent ratio of carboxyl groups to epoxide groups of at least 1:1 (e.g., in an equivalent ratio of (1.0-1.2): 1 or (1.0-1.1): 1).

In an important embodiment of the present invention, there is provided a process for the preparation of a cyclic carbonate functional polyester comprising the stages of: A) reacting glycerol carbonate with an anhydride to form an adduct (a); B) providing a polycarboxylic acid; C) reacting the polycarboxylic acid with at least one diglycidyl ether to form an Epoxy-functional polyester (Epoxy-PES); and D) reacting the epoxy functional polyester with the adduct (A) to form the cyclic carbonate functional polyester (CC-PES).

Preferably, the polycarboxylic acid provided in stage B is a dicarboxylic acid or a tricarboxylic acid, of which dicarboxylic acids are particularly desirable. In an alternative, but not mutually exclusive, preferred expression, the polycarboxylic acid provided should generally be characterized by an acid value (Av) of from 50 to 1200mgKOH/g, and preferably from 80 to 1100 mgKOH/g.

In an important embodiment, the polycarboxylic acid is a carboxyl-functional polyester (Carboxy-PES). The manner in which such carboxyl functional polyesters are prepared or provided in stage B is not particularly limited. However, it is desirable to provide a carboxyl functional polyester (Carboxy-PES) characterized by an acid value (Av) of 50 to 500mgKOH/g, preferably 80 to 430 mgKOH/g.

In an exemplary process, the Carboxyl-functional polyester of stage B (Carboxyl-PES) is provided by: i) providing a polyester having two or more hydroxyl groups; and ii) reacting the hydroxy functional polyester with a carboxylic acid or anhydride thereof. The hydroxy-functional polyester so provided may preferably be characterized as having a hydroxyl number of from 50 to 300mgKOH/g, preferably from 80 to 150 mgKOH/g.

In an alternative process, the carboxyl-functional polyester of stage B (Carboxy-PES) is provided by the reaction of a stoichiometric excess of a dicarboxylic acid with at least one diol in the presence of a catalytic amount of an esterification catalyst.

In stage C of the process defined above, it is preferred that the or each diglycidyl ether has an epoxy equivalent weight (epoxy equivalent weight) of from 100 to 700g/eq, preferably from 120 to 320 g/eq. Independently of this, however, it is preferred in stage C that the molar ratio of diglycidyl ether compound to polycarboxylic acid, if applicable carboxyl-functional polyester, is from 1.5:1 to 3:1, preferably from 1.8:1 to 2.2: 1.

The aforementioned equivalent ratios of carboxyl groups to epoxide groups still apply to the reaction of the adduct (a) with the epoxy-functional polyester (identified polyepoxide) in stage D. Illustratively, in the stage D reaction, the molar ratio of adduct (a) to Epoxy-functional polyester (Epoxy-PES) may be from 2:1 to 3:1, preferably from 2:1 to 2.5: 1.

It is worth noting that the effective process according to the invention comprises the implementation of both stages C and D under the following conditions: i) at a temperature of from 40 ℃ to 180 ℃, preferably from 60 ℃ to 170 ℃; and/or ii) in the presence of a catalytic amount of a basic catalyst. This temperature range corresponds to mild conditions; in the stage D reaction, the mild conditions may prevent the 5-membered cyclic carbonate ring of the adduct from opening.

It is further noted that the process of the present invention has been carried out efficiently, wherein stages B to D have been carried out successively in one vessel and without isolation of the intermediate products. This "one-pot" solution makes the implementation of the invention extremely simple.

The process of the present invention provides oligomeric and polymeric compounds functionalized with 5-membered cyclic carbonate groups; the polyester group is in the beta position relative to the cyclic carbonate and thus acts as an electron withdrawing group that serves to increase the reactivity of the 5-membered cyclic carbonate ring. Furthermore, the present method provides for the synthesis of functionalized compounds having a broad molecular weight range: in certain embodiments, the molecular weight and structure of the provided carboxyl-functional polyester (Carboxy-PES) will substantially determine the molecular weight and structure of the cyclic carbonate-functional polyester.

According to a second aspect of the present invention there is provided a cyclic carbonate functional polyester obtainable by the process defined above and in the appended claims. Preferably, the cyclic carbonate functional polyester is characterized by at least one of the following features: a cyclic carbonate equivalent weight of 400 to 2500g/eq, preferably 500 to 1500 g/eq; a number average molecular weight (Mn) of from 500 to 5000g/mol, preferably from 800 to 3000 g/mol; and an OH number of from 50 to 300mgKOH/g, preferably from 100 to 200 mgKOH/g.

According to a third aspect of the present invention there is provided a curable coating, adhesive or sealant composition comprising: a cyclic carbonate functional polyester as defined above; and at least one polyfunctional compound (H) having at least two functional groups (F) selected from: a primary amino group; a secondary amino group; a hydroxyl group; a phosphine group; a phosphonate group; and a thiol group.

Definition of

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

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

When amounts, concentrations, dimensions, and other parameters are expressed as ranges, preferred ranges, upper values, lower values, or preferred upper and lower values, it is to be understood that any range that can be obtained by combining any upper value or preferred value with any lower value or preferred value, whether or not such obtained range is explicitly recited in the context, is also specifically disclosed.

The terms "preferred," "preferably," "desirably," "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 or 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 number average molecular weight (Mn). Unless otherwise specified, all molecular weight data refer to values obtained by Gel Permeation Chromatography (GPC).

"acid number" or "acid value" is a measure of the amount of free acid present in a compound: the acid number is the number of milligrams of potassium hydroxide (mgKOH/g) required to neutralize the free acid present in one gram of material. Any measured acid number given herein has been determined according to german standard DIN 53402.

The OH numbers given herein are obtained according to "Deutsche (DGF) Einheitethoden zur Untershuchung von Fetten, Fettprodukten, Tensiden und verwandten Stoffen (Gesamtingsvertzeichnis 2016) C-V17 b (53)".

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

As used herein, the term "equivalent (eq.)" as in chemical notation generally refers to the relative number of reactive groups present in a reaction; 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 of interest. Thus, "epoxy equivalent weight" (EEW) represents the weight (in grams) of a resin containing one equivalent of epoxy groups.

As used herein, "aliphatic group" refers to a saturated or unsaturated linear (i.e., straight chain), branched, or cyclic (including bicyclic) organic group: the term "aliphatic group" thus encompasses "cycloaliphatic group," which is a cyclic hydrocarbon group having properties similar to those of an aliphatic group. 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 group" 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: a methyl group; an ethyl group; propyl; isopropyl group; n-butyl; an isobutyl group; sec-butyl; a tertiary butyl group; n-pentyl; and n-hexyl. In the present invention, such an alkyl group may be unsubstituted or may be substituted with one or more substituents (e.g., halo, nitro, cyano, amido, amino, sulfonyl, sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfonamide, and hydroxyl). Halogenated derivatives of the exemplary hydrocarbon radicals listed above may be mentioned inter alia as examples of suitable substituted alkyl groups. In general, however, it should be noted that unsubstituted alkyl groups (C) containing 1 to 6 carbon atoms are preferred₁-C₆Alkyl), for example an unsubstituted alkyl radical (C) containing from 1 to 4 carbon atoms₁-C₄Alkyl) or unsubstituted alkyl groups containing 1 or 2 carbon atoms (C)₁-C₂Alkyl groups).

As used herein, "C" is₄-C₂₀An alkenyl "group means a group containing from 4 to 20 carbon atoms and at least oneAn aliphatic hydrocarbon group having a double bond. Like the aforementioned alkyl groups, the alkenyl groups may be linear or branched, and may be optionally substituted. As understood by those of ordinary skill in the art, the term "alkenyl" also encompasses radicals having "cis" and "trans" configurations, or alternatively having "E" and "Z" configurations. However, in general, it should be noted that it is preferable to contain 4 to 18 (C)_4-18) Or 4 to 12 (C)_2-12) Unsubstituted alkenyl groups of carbon atoms. And C₄-C₂₀Examples of alkenyl groups include, but are not limited to: 2-butenyl; 4-methylbutenyl; 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, 1-heptenyl, 1-octenyl and n-dodecenyl.

As used herein, "polycarboxylic acid" includes any organic structure having more than one carboxylic acid functional group. In particular, the term encompasses polymers bearing at least two carboxyl functional groups, and thus specifically encompasses: a carboxyl-functional polyester resin; a carboxyl functional polyacrylate resin; a carboxyl functional polymethacrylate resin; a carboxyl-functional polyamide resin; a carboxyl functional polyimide resin; and a carboxyl functional polyolefin resin.

As used herein, "polyol" refers to any compound that includes two or more hydroxyl groups. Thus, the term encompasses diols, triols, and compounds containing four or more-OH groups.

The term "epoxy compound" means monoepoxy compounds, polyepoxy compounds, and epoxy functional prepolymers. Thus, the term "polyepoxide" is intended to mean an epoxy compound having at least two epoxy groups. Further, the term "diepoxy compound" is therefore intended to mean an epoxy compound having two epoxy groups.

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.

Detailed Description

At its broadest, the present invention provides a process for preparing a cyclic carbonate functional polyester, the process comprising: reacting glycerol carbonate with an anhydride to form an adduct (a); and reacting the adduct (a) with at least one polyepoxide to form the cyclic carbonate functional polyester (CC-PES).

Preparation of adduct (A)

In the first stage of the process defined above, which may be referred to hereinafter as stage a, the glycerol carbonate is reacted with a polyfunctional acid anhydride. The esterification reaction produces an adduct (a) having a carboxylic acid group; in this adduct, the ester group is located in the β (β -) position, as exemplified below.

The reactant glycerol carbonate may alternatively be identified as 4-hydroxymethyl-1, 3-dioxolan-2-one. The compound can be used as Jeffsol manufactured by Huntsman Corporation^TMAre commercially available. Alternatively, the compounds may be synthesized by methods known in the art, including: by reaction of glycerol with a carbonate source such as phosgene, with a dialkyl carbonate or with an alkylene carbonate; by reaction of glycerol with urea, carbon dioxide and oxygen; or by reaction of carbon dioxide with glycidol. The following documents are of guiding interest for this synthesis: U.S. patent No. 2,915,529; U.S. patent No. 6,025,504; european patent No. 1,156,042; and U.S. Pat. No. 5,359,094.

Although there is no particular intention to limit the reactant polyfunctional acid anhydride, most suitable is an anhydride of an acid selected from: maleic acid; fumaric acid; citraconic acid; itaconic acid; glutaconic acid; phthalic acid; isophthalic Acid (IA); terephthalic acid; cyclohexane dicarboxylic acid; adipic acid; sebacic acid (SeA); azelaic acid; malonic acid; succinic acid; alkyl succinic acids; alkenyl succinic acid; glutaric acid; alkyl glutaric acid; alkenyl glutaric acid; and mixtures thereof.

The polyfunctional acid anhydride is preferably an anhydride selected from the group consisting of: maleic anhydride; adipic anhydride; succinic anhydride; alkyl succinic anhydrides; alkyl succinic anhydrides; glutaric anhydride; alkyl glutaric anhydride; alkenyl glutaric anhydride; and mixtures thereof. More preferably, the polyfunctional acid anhydride is an anhydride selected from the group consisting of: maleic anhydride; adipic anhydride; succinic anhydride; glutaric anhydride; and mixtures thereof.

For completeness, the most suitable alkyl succinic anhydrides are those defined by the following formula a:

wherein: r¹、R²、R³And R⁴Independently selected from hydrogen and C₁-C₆An alkyl group.

The most suitable alkenyl succinic anhydrides are those defined by the formula B:

wherein: r⁵、R⁶And R⁷Independently selected from hydrogen and C₁-C₆An alkyl group; and is

R⁸Is C₄-C₂₀An alkenyl group.

By inference, the most suitable alkyl glutaric anhydrides are those anhydrides defined by the following formula C:

wherein: r¹、R²、R³、R⁴、R⁵And R⁶Independently selected from hydrogen and C₁-C₆An alkyl group.

The most suitable alkenyl glutaric anhydrides are those 3-glutaric acid (glutaric) derivatives defined by formula D:

wherein: r⁷、R⁸、R⁹、R¹¹And R¹²Independently selected from hydrogen and C₁-C₆An alkyl group; and is

R¹⁰Is C₄-C₂₀An alkenyl group.

The relative amounts of glycerol carbonate and polyfunctional acid anhydride can vary over a fairly wide range, but a significant excess of anhydride is undesirable because the reactants can be expensive and can be difficult to recover and reuse. Preferably, the acid anhydride: the molar ratio of the glycerol carbonate is 2:1 to 0.8: 1; more preferably, the molar ratio is from 1.2:1 to 0.8: 1; and most preferably, the ratio is from 1.1:1 to 0.9: 1.

The first stage of the present invention can be carried out in any known suitable vessel designed to hold the reactants, products and any solvent employed, including those described in U.S. patent No. 4,310,708 (Strege et al). Of course, the material of the container should be inert under the conditions employed during the process stage.

The process stage may be carried out at any suitable temperature, taking into account those conditions. Although the optimum operating temperature for the reaction can be determined by the skilled person by experimentation, suitable temperatures in the range of 60 ℃ to 180 ℃ and preferred temperatures in the range of 80 ℃ to 150 ℃ may be mentioned.

The process pressure is not critical. Thus, the reaction may be carried out at subatmospheric, atmospheric or superatmospheric pressures, but atmospheric or superatmospheric pressures are preferred.

Good results have been obtained in the case of carrying out the first stage reaction under anhydrous conditions. Exposure to atmospheric humidity may be avoided, if desired, by providing the reaction vessel with a blanket of inert dry gas. Although dry nitrogen, helium and argon can be used as blanket gases, precautions should be taken when using ordinary nitrogen as the blanket, since such nitrogen may not be sufficiently dry due to its susceptibility to moisture entrainment; in this context, this nitrogen may require an additional drying step before use.

The first reaction stage can also be carried out in the absence of solvent and this is desirable in practice. Suitable solvents, if employed, should be inert: it should not contain functional groups that react with the starting compounds. Thus, mention may be made of: aromatic hydrocarbons, illustratively toluene or benzene; an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, such as heptane, hexane or octane; ethers such as diethyl ether, methyl ethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; and esters such as ethyl acetate, amyl acetate, and methyl formate. Among these solvents, aromatic solvents are the least preferred due to their potentially toxic association.

No catalyst need be employed in this reaction step and catalyst-free conditions are desirable in practice. However, the use of catalysts is not excluded and suitable catalysts (including titanium, zirconium and tin catalysts, such as titanium, zirconium and tin alkoxides, carboxylates and chelates) are identified, inter alia, in the following documents: U.S. Pat. No. 3,056,818 (Werber); and U.S. patent No. 5,969,056 (Nava). Further suitable catalysts include alkali or alkaline earth metal acetates, bicarbonates, carbonates, succinates, glutarates, adipates, oxides, hydroxides or mixtures thereof: sodium carbonate, potassium carbonate, sodium acetate and potassium acetate are said to be preferred because they are inexpensive, readily available and effective. When used, the amount of catalyst is preferably from 0.05 to 5 wt% or from 0.05 to 3 wt%, based on the total amount of reaction compounds.

The reaction time to achieve sufficient conversion of the reactant anhydride will depend on various factors such as temperature, type of catalyst and type of polyfunctional acid anhydride. The reaction can be monitored by analyzing the acid value (Av) of the reactant mixture over time; and the reaction is stopped when the determined acid value is constant at a value close to the theoretical acid value. Typically, the time sufficient to effect the reaction is2 to 20 hours, for example 4 to 8 hours or 4 to 7 hours.

In view of the preferred embodiment of the anhydride reaction, an exemplary illustrative reaction scheme for the first step of the claimed process is as follows (where n is 1,2 or 3):

exemplary reaction scheme, step A

The adduct (a) prepared according to the first step of the present invention may be used as such or may be isolated and purified using methods known in the art: mention may be made in this connection of extraction, evaporation, distillation and chromatography.

Reacting the adduct (A) with at least one polyepoxide compound

Reacting the derivatized adduct (A) with at least one polyepoxide to form the cyclic carbonate functional polyester (CC-PES). Whatever polyepoxide is chosen, the reaction should be characterized by: the equivalent ratio of carboxyl groups to epoxide groups is at least 1:1, and preferably (1.0-1.2): 1 or is (1.0-1.1): 1.

while it is recognized that it is preferred to select as a reactant an Epoxy-functional polyester (Epoxy-PES), which as described below can be derived from stages B) and C), other polyepoxides can be used alone or in combination with the Epoxy-functional polyester at this stage of the reaction.

Such suitable other polyepoxides may be liquid, solid or in solution in a solvent. Further, such polyepoxides should have an epoxy equivalent weight of from 100 to 700g/eq (e.g., from 120 to 320 g/eq). And in general, diepoxy compounds having an epoxy equivalent of less than 500 or even less than 400 are preferred: this is primarily from a cost perspective, as lower molecular weight epoxy resins require more limited processing in their preparation in purification.

Suitable diglycidyl ether compounds can be aromatic, aliphatic, or cycloaliphatic in nature, and thus can be derived from dihydric phenols and diols. And 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; a butadiene diepoxy compound; polybutadiene diglycidyl ether; vinylcyclohexene diepoxy compound; and limonene diepoxy compounds.

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

without intending to limit the invention, examples of highly preferred polyepoxides 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; and brominated epoxy resins, e.g. DER^TM542。

Although the reaction of epoxide groups with carboxyl groups can be carried out in the absence of a catalyst, basic catalysis is required here to achieve both acceptable reaction rates and the desired reaction product. Examples of suitable basic catalysts include, but are not limited to: alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium alkoxides such as sodium methoxide, sodium ethoxide, and sodium butoxide; quaternary ammonium hydroxides, such as benzyltrimethylammonium hydroxide and tetrabutylammonium hydroxide; ammonium salts as phase transfer catalysts, such as benzyltrimethylammonium chloride, benzyltriethylammonium chloride, methyltridecanylammonium chloride, methyltributylammonium chloride, methyltrioctylammonium chloride and tetra-n-octylammonium bromide; phosphonium salts as phase transfer catalysts, such as hexadecyltributylphosphonium bromide, tetramethylphosphonium bromide, tetraphenylphosphonium chloride and trihexyltetradecylphosphonium bromide; and strongly basic ion exchange resins. Although the skilled artisan can determine suitable and optimal catalytic amounts of such compounds, it is suggested that typical amounts of catalyst are from 0.05 to 5% by weight or from 0.05 to 3% by weight, based on the total amount of reaction compounds.

Although the optimum operating temperature for this stage of the process can be determined by the skilled person by experimentation, suitable temperatures in the range of 40 ℃ to 180 ℃, preferably in the range of 60 ℃ to 170 ℃ or even 160 ℃ may be mentioned. The process pressure is not critical: thus, the reaction may be carried out at subatmospheric, atmospheric or superatmospheric pressures, but atmospheric or superatmospheric pressures are preferred.

Good results have been obtained in case this stage is carried out under anhydrous conditions; wherein the reaction vessel has been provided with a blanket of an inert dry gas, such as dry nitrogen, helium or argon. It is also noteworthy that this reaction stage should also desirably be carried out in the absence of solvent. Suitable solvents, if employed, should be inert: it should be free of reactive groups that react with the starting compound.

The progress of the reaction can be monitored by analyzing the acid value (Av) of the reaction mixture over time: when the acid value determined is a value of less than 1mgKOH/g, the reaction may be stopped. Typically, the time sufficient for the reaction to reach this point is 0.5 to 20 hours, for example 1 to 8 hours or 2 to 6 hours.

The reaction product (CC-PES) can be isolated and purified using methods known in the art: extraction, evaporation, distillation and chromatography may again be mentioned in this connection. If the cyclic carbonate functional polyester (CC-PES) is intended to be stored after preparation, the polyester should be placed in a container having a hermetic and moisture-tight seal.

Detailed description of the invention

In an important embodiment, the process for preparing a cyclic carbonate functional polyester comprises the following stages: A) reacting glycerol carbonate with an anhydride to form an adduct (a), as described above; B) providing a polycarboxylic acid; C) reacting the polycarboxylic acid with at least one diglycidyl ether to form an epoxy-functional polyester; and D) reacting the epoxy functional polyester with the adduct (A) to form the cyclic carbonate functional polyester.

It is to be noted that the reaction stages B to D can be carried out independently in one or more suitable vessels. In this case, the intermediate reaction products formed after stages B and C, respectively, can be isolated and/or purified using methods known in the art (e.g., extraction, evaporation, distillation, and chromatography). However, this method is not preferred. Desirably, stages B to D are carried out sequentially in one vessel; this "one-pot" solution eliminates the need for intermediate separation and purification steps. Furthermore, it is preferred that each of stages B to D is carried out substantially free of solvent.

Stage B

Stage B of this mode of the invention consists of providing a polycarboxylic acid. In general, any polycarboxylic acid can be used in which the carboxylic acid groups are separated by a divalent hydrocarbon group which may be saturated or unsaturated, aliphatic, aromatic or alicyclic, or may have two or more aliphatic, aromatic or alicyclic moieties. Preference may be given to dicarboxylic acids and tricarboxylic acids, the former being particularly preferred. In addition, preferred polycarboxylic acids should generally be characterized by an acid value (Av) of from 50 to 1200mgKOH/g (e.g., from 80 to 1100 mgKOH/g).

Exemplary suitable dicarboxylic acids include: phthalic acid; isophthalic Acid (IA); terephthalic acid; phthalic acid; naphthalenedicarboxylic acid; 1, 3-and 1, 4-cyclohexanedicarboxylic acid; p-phenylene diacetic acid; sebacic acid (SeA); brassylic acid; maleic acid; fumaric acid; oxalic acid; succinic acid; itaconic acid; adipic acid; beta-methyladipic acid; trimethyladipic acid, glutaric acid; azelaic acid; malonic acid; suberic acid; pimelic acid; dodecanedioic acid; dimerized fatty acid; and mixtures thereof.

Exemplary suitable tricarboxylic acids include: citric acid; aconitic acid; 1,3, 5-pentanetricarboxylic acid; 1,2, 3-propanetricarboxylic acid; 1,2,3, 4-butanetetracarboxylic acid; 1,2, 4-benzenetricarboxylic acid; and 1,3, 5-benzenetricarboxylic acid.

In a particularly preferred embodiment of the invention, the polycarboxylic acid of stage B is a carboxyl-functional polyester (Carboxy-PES), which polymer may preferably be characterized by an acid value (Av) of from 50 to 500mgKOH/g, preferably from 80 to 430 mgKOH/g.

The Carboxy-functional polyester (Carboxy-PES) of this embodiment may be obtained by the reaction of: (i) at least one aromatic, aliphatic or cycloaliphatic dicarboxylic acid or anhydride thereof; ii) at least one diol compound, more particularly a compound having two aliphatic hydroxyl groups, which may each independently be a primary or secondary hydroxyl group.

Suitable dicarboxylic acids include saturated, unsaturated, aliphatic, cycloaliphatic or aromatic dicarboxylic acids and/or anhydrides. Exemplary dicarboxylic acids are: phthalic acid; isophthalic acid; terephthalic acid; phthalic acid; naphthalenedicarboxylic acid; 1, 3-and 1, 4-cyclohexanedicarboxylic acid; p-phenylene diacetic acid; sebacic acid; brassylic acid; maleic acid; fumaric acid; succinic acid; itaconic acid; adipic acid; beta-methyladipic acid; trimethyladipic acid, glutaric acid; azelaic acid; malonic acid; suberic acid; dodecanedioic acid; and mixtures thereof. Preferably, the dicarboxylic acid or anhydride of a dicarboxylic acid has 4 to 12 carbon atoms.

Suitable diols having two aliphatic hydroxyl groups may have a molecular weight of 62 to 5000 and may optionally contain ether groups, ester groups and/or carbonate groups. Exemplary aliphatic diols are: ethylene glycol; 1, 2-propanediol; 2-methyl-1, 3-propanediol; 1, 3-and 1, 4-butanediol; 1, 6-hexanediol; diethylene glycol; dipropylene glycol; neopentyl glycol; triethylene glycol; tetraethylene glycol; tripropylene glycol; tetrapropylene glycol; a polycarbonate diol; a polyester diol; dimerized fatty alcohols; and mixtures thereof.

The use of other reactants in the derivatization of carboxyl-functional polyesters (Carboxy-PES) is not excluded, and in this connection mention may be made of: iii) a dihydroxy monocarboxylic acid, wherein each hydroxyl group can independently be a primary or secondary hydroxyl group; iv) trifunctional and/or tetrafunctional hydroxyl compounds which comprise three and/or four aliphatic hydroxyl groups, respectively (which may each independently be a primary or secondary hydroxyl group), such as trimethylolethane, trimethylolpropane, hexanetriol or pentaerythritol.

It will be apparent to those of ordinary skill in the art that there are many alternative ways to synthesize Carboxy-functional polyesters (Carboxy-PES) from the reactants, and therefore it is not intended to limit the invention to only one of those ways. However, certain preferred synthetic methods will be discussed below.

In a first method, a hydroxy-functional polyester may be reacted with a carboxylic acid or anhydride thereof to form a carboxy-functional polyester. The first method may consist of a two-stage process: reacting, in a first stage, a dicarboxylic acid and a diol under water removal conditions to form a hydroxyl functional prepolymer; in the second stage, the prepolymer is reacted with a carboxylic acid or anhydride thereof. The water removal conditions typically consist of one or more of the following conditions: a temperature of 120 ℃ to 250 ℃; applying a vacuum; and the use of a solvent to facilitate azeotropic distillation.

The amount of acid or anhydride agent used is determined in the case of a two-stage process by the hydroxyl number of the polyester or intermediate prepolymer, which is desirably from 50 to 300mgKOH/g, and preferably from 80 to 150 mgKOH/g. Generally, 80% to 100% of the stoichiometric amount required to end-cap all of the hydroxyl functional groups of the polyester is typically added. The reagent is added to the hydroxy-functional polyester or prepolymer and esterification is continued until the desired acid number (Av) is obtained. Typically, the total reaction time is from 5 to 15 hours.

Conventional catalysts for promoting the esterification reaction may be used in the (capping) reaction and, if applicable, in one or both of the first and second stages. The catalyst (which may be used in an amount of 0.01 to 1 wt%, for example 0.01 to 0.5 wt%, based on the combined weight of the reactants) is typically a compound of tin, antimony, titanium or zirconium. Mention may be made in this respect of: titanium alkoxides and derivatives thereof, such as tetraethyl titanate, tetraisopropyl titanate (TIPT), tetra-n-propyl titanate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, isopropyl butyl titanate, tetrastearyl titanate, diisopropoxybis (acetylacetonate) titanium, di-n-butoxybis (triethanolamino) titanium (di-n-butoxy-bis (triethanolamminoato) titanium), tributylmonoacetyltitanate, triisopropylmonoacetyltitanate, and tetrabenzoate titanate; titanium complex salts, for example alkali metal titanium oxalates and malonates, potassium hexafluorotitanate and titanium complexes with hydroxycarboxylic acids such as tartaric acid, citric acid or lactic acid; a titanium dioxide/silicon dioxide coprecipitate; hydrated alkali-containing titanium dioxide (hydrated alkali-containing titanium dioxide); and the corresponding zirconium compounds.

According to a second desired method of synthesizing carboxyl-functional polyesters (Carboxy-PES), a stoichiometric excess of a dicarboxylic acid is reacted with at least one diol in the presence of a catalytic amount of an esterification catalyst, such as those mentioned above. The stoichiometric excess of dicarboxylic acid should be sufficient to achieve the desired ester linkage and to have additional carboxyl groups to produce terminal carboxyl groups. Further, the polycondensation reaction should be conducted under water removal conditions.

Stage C

In this stage of the process of the present invention, a polycarboxylic acid, which is a Carboxy-functional polyester (Carboxy-PES) where applicable, is reacted with one or more diglycidyl ether compounds to produce an Epoxy-functional polyester (Epoxy-PES). Broadly, suitable diglycidyl ether compounds can be liquid, solid, or in solution in a solvent. The diglycidyl ether compounds may be aromatic, aliphatic, or cycloaliphatic in nature, and thus may be derived from dihydric phenols and dihydric alcohols. And useful classes of such diglycidyl ethers (epoxy resins) are: diglycidyl ethers of aliphatic and cycloaliphatic diols, such as 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; polyglycidyl ethers based on polyalkylene glycols, in particular polypropylene glycol diglycidyl ether; and glycidyl ethers based on polycarbonate diols.

Preferably, the diglycidyl ether compound has an epoxy equivalent weight of 100 to 700g/eq (e.g., 120 to 320 g/eq). In general, diglycidyl ether compounds having an epoxy equivalent of less than 500 or even less than 400 are preferred: this is primarily from a cost perspective, as lower molecular weight epoxy resins require more limited processing in their preparation in purification.

Without intending to limit the invention, examples of suitable epoxy resins 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; and brominated epoxy resins, e.g. DER^TM542。

The molar ratio of diglycidyl ether compound to carboxyl-functional polyester (Carboxy-PES) should preferably be from 1.5:1 to 3:1, and more preferably from 1.8:1 to 2.2: 1.

Although the reaction of epoxide groups with carboxyl groups can be carried out in the absence of a catalyst, basic catalysis is required here to achieve both acceptable reaction rates and acceptable yields of the desired reaction product. Examples of suitable basic catalysts for stage C include, but are not limited to: alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium alkoxides such as sodium methoxide, sodium ethoxide, and sodium butoxide; quaternary ammonium hydroxides, such as benzyltrimethylammonium hydroxide and tetrabutylammonium hydroxide; ammonium salts as phase transfer catalysts, such as benzyltrimethylammonium chloride, benzyltriethylammonium chloride, methyltridecanylammonium chloride, methyltributylammonium chloride, methyltrioctylammonium chloride and tetra-n-octylammonium bromide; phosphonium salts as phase transfer catalysts, such as hexadecyltributylphosphonium bromide, tetramethylphosphonium bromide, tetraphenylphosphonium chloride and trihexyltetradecylphosphonium bromide; and strongly basic ion exchange resins. Although the skilled artisan can determine suitable and optimal catalytic amounts of such compounds, it is suggested that typical amounts of catalyst are from 0.05 to 5% by weight or from 0.05 to 3% by weight, based on the total amount of reaction compounds.

Although the optimum operating temperature for stage C of the process can be determined by the skilled person by experimentation, suitable temperatures in the range of 40 ℃ to 180 ℃, preferably in the range of 60 ℃ to 170 ℃ or even 160 ℃ may be mentioned. The process pressure is not critical: thus, the reaction may be carried out at subatmospheric, atmospheric or superatmospheric pressures, but atmospheric or superatmospheric pressures are preferred.

Good results have been obtained in case this stage is carried out under anhydrous conditions; wherein the reaction vessel has been provided with a blanket of an inert dry gas, such as dry nitrogen, helium or argon. It is also noteworthy that this reaction stage should also desirably be carried out in the absence of solvent. Suitable solvents, if employed, should be inert: it should be free of reactive groups that react with the starting compound.

The progress of the epoxidation reaction can be monitored by analyzing the acid value (Av) of the reactant mixture over time: when the acid value determined is a value of less than 1mgKOH/g, the reaction may be stopped. Typically, the time sufficient to carry out the epoxidation reaction is from 0.5 to 20 hours, for example from 1 to 8 hours or from 2 to 6 hours.

In view of the preferred embodiment of the epoxidation reaction, an exemplary illustrative reaction scheme for the first step of the claimed process is as follows:

exemplary reaction scheme, stage C

Wherein: r is the residue of a dihydric phenol or a dihydric alcohol; and Y is the residue of a Polyester (PES) or a polycarboxylic acid.

Stage D

In this stage of the process, the adduct (a) of stage a is reacted with the Epoxy-functional polyester (Epoxy-PES) obtained from stage C. By this reaction, a polyester having a terminal cyclic carbonate group (CC-PES) is obtained.

The adduct should be added to the reaction medium in an amount sufficient to ensure an equivalent ratio of carboxylic acid groups to epoxide groups of at least 1: 1. This may correspond to a molar ratio of adduct (a) to Epoxy-functional polyester (Epoxy-PES) of from 2:1 to 3:1 and more preferably from 2:1 to 2.5: 1.

Although the reaction of epoxide groups with carboxyl groups can be carried out in the absence of a catalyst, basic catalysis is required here to achieve both acceptable reaction rates and the desired reaction product. Examples of suitable basic catalysts for stage D include, but are not limited to: alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium alkoxides such as sodium methoxide, sodium ethoxide, and sodium butoxide; quaternary ammonium hydroxides, such as benzyltrimethylammonium hydroxide and tetrabutylammonium hydroxide; ammonium salts as phase transfer catalysts, such as benzyltrimethylammonium chloride, benzyltriethylammonium chloride, methyltridecanylammonium chloride, methyltributylammonium chloride, methyltrioctylammonium chloride and tetra-n-octylammonium bromide; phosphonium salts as phase transfer catalysts, such as hexadecyltributylphosphonium bromide, tetramethylphosphonium bromide, tetraphenylphosphonium chloride and trihexyltetradecylphosphonium bromide; and strongly basic ion exchange resins. Although the skilled artisan can determine suitable and optimal catalytic amounts of such compounds, it is suggested that typical amounts of catalyst are from 0.05 to 5% by weight or from 0.05 to 3% by weight, based on the total amount of reaction compounds.

Although the optimum operating temperature for stage D of the process can be determined by the skilled person by experimentation, suitable temperatures in the range of 40 ℃ to 180 ℃, preferably in the range of 60 ℃ to 170 ℃ or even 160 ℃ may be mentioned. The process pressure is not critical: thus, the reaction may be carried out at subatmospheric, atmospheric or superatmospheric pressures, but atmospheric or superatmospheric pressures are preferred.

Good results have been obtained in case this stage is carried out under anhydrous conditions; wherein the reaction vessel has been provided with a blanket of an inert dry gas, such as dry nitrogen, helium or argon. It is also noteworthy that this reaction stage should also desirably be carried out in the absence of solvent. Suitable solvents, if employed, should be inert: it should be free of reactive groups that react with the starting compound.

The progress of the reaction can be monitored by analyzing the acid value (Av) of the reaction mixture over time: when the acid value determined is a value of less than 1mgKOH/g, the reaction may be stopped. Typically, the time sufficient for the reaction to reach this point is 0.5 to 20 hours, for example 1 to 8 hours or 2 to 6 hours.

With a preferred embodiment in mind, an exemplary illustrative reaction scheme for this step of the claimed process is as follows:

exemplary reaction scheme, stage D

Wherein: r is the residue of a dihydric phenol or a dihydric alcohol; y is the residue of a Polyester (PES) or a polycarboxylic acid; and n is 1,2 or 3.

The product of stage D (CC-PES) can be isolated and purified using methods known in the art: extraction, evaporation, distillation and chromatography may again be mentioned in this connection.

If the cyclic carbonate functional polyester (CC-PES) is intended to be stored after preparation, the polyester should be placed in a container having a hermetic and moisture-tight seal.

Coating, sealant and adhesive compositions

As previously mentioned, the cyclic carbonate functional polyester (CC-PES) obtained using the process of the present invention may be used as a reactive component in curable coating, adhesive or sealant compositions. The other reactant(s) of such compositions are typically one or more polyfunctional compounds (H) having at least two functional groups (F) selected from: a primary amino group; a secondary amino group; a hydroxyl group; a phosphine group; a phosphonate group; and a thiol group. Latent compounds in which the functional group (F) is blocked, but which are activatable under specific physicochemical conditions, are also envisaged as further reactants suitable 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. Further, the reactant compound (H) may be a low molecular weight substance (i.e., a substance having a molecular weight of less than 500g/mol) or an oligomeric or polymeric substance having a number average molecular weight (Mn) of 500g/mol or more. Also, it is of course possible to use mixtures of compounds (H), for example mixtures of alcohols and amine hardeners.

In an important embodiment, the functional group (F) of compound (H) is selected from: an aliphatic hydroxyl group; an aliphatic primary amino group; secondary aliphatic amino groups; an aliphatic phosphine group; an aliphatic phosphonate group; an aliphatic thiol group; and mixtures thereof.

In a preferred embodiment, compound (H) comprises or consists of an amine (or amine) or alcohol compound; and more particularly, the functional group (F) of compound (H) is selected from: an aliphatic hydroxyl group; an aliphatic primary amino group; secondary aliphatic amino groups; and combinations thereof.

Without intending to limit the invention, exemplary amine compounds (H) suitable for inclusion in the curable composition comprising the cyclic carbonate functional polyester (CC-PES) are:

a) aliphatic polyamines such as ethylenediamine, 1, 2-and 1, 3-propanediamine, neopentyldiamine, hexamethylenediamine, octamethylenediamine, 1, 10-diaminodecane, 1, 12-diaminododecane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 2-dimethylpropylenediamine, trimethylhexamethylenediamine, 1- (3-aminopropyl) -3-aminopropane, 1, 3-bis (3-aminopropyl) propane and 4-ethyl-4-methylamino-1-octylamine;

b) alicyclic diamines, for example 1, 2-diaminocyclohexane, 1,2-, 1, 3-and 1, 4-bis (aminomethyl) cyclohexane, 1-methyl-2, 4-diaminocyclohexane, N-cyclohexylpropylene-1, 3-diamine, 4- (2-aminopropyl-2-yl) -1-methylcyclohexan-1-amine, isophoronediamine, 4 '-diaminodicyclohexylmethane (Dicykan), 3' -dimethyl-4, 4 '-diaminodicyclohexylmethane, 3',5,5 '-tetramethyl-4, 4' -diaminodicyclohexylmethane, 4, 8-diaminotricyclo [5.2.1.0] decane, norbornanediamine, menthanediamine and menthenediamine;

c) aromatic diamines, for example: toluene diamine, xylylenediamine (especially m-xylylenediamine (MXDA)), bis (4-aminophenyl) methane (MDA or methylenedianiline) and bis (4-aminophenyl) sulfone (also known as DADS, DDS or dapsone);

d) cyclic polyamines such as piperazine and N-aminoethyl piperazine;

e) polyetheramines, especially difunctional and trifunctional primary polyetheramines based on polypropylene glycol, polyethylene glycol, polybutylene oxide (polybutylene oxide), poly (1, 4-butanediol), polytetrahydrofuran (PolyTHF) or polypentene oxide (polypentylene oxide);

f) polyamidoamines (amidopolyamines) which can be obtained by reacting dimeric fatty acids (e.g. dimeric linoleic acid) with low molecular weight polyamines (e.g. diethylenetriamine, 1- (3-aminopropyl) -3-aminopropane or triethylenetetramine) or with other diamines (e.g. the aforementioned aliphatic or cycloaliphatic diamines);

g) adducts, which can be obtained by reacting an amine (especially a diamine) with insufficient epoxy resin or reactive diluent, wherein such adducts are preferably used in case about 5-20% of the epoxy groups have reacted with the amine (especially a diamine);

h) phenolic amines (phenalkamine), as known from epoxide chemistry; and

i) mannich bases, which can generally be prepared by condensation of polyamines (preferably diethylenetriamine, triethylenetetramine, isophoronediamine, 2, 4-or 2,4, 4-trimethylhexamethylenediamine, 1, 3-and 1, 4-bis (aminomethyl) cyclohexane) with aldehydes (preferably formaldehyde) and monohydric or polyhydric phenols having at least one aldehyde-reactive core site (e.g. the various cresols and xylenols, p-tert-butylphenol, resorcinol, 4,4 '-dihydroxydiphenylmethane, 4,4' -dihydroxydiphenyl-2, 2-propane, but preferably phenol).

The alcoholic hardener crosslinks through reaction of the primary or secondary alcohol functional groups with the 1, 3-dioxolan-2-one groups to form carbonate polymers, where carbonate diesters are formed. Thus, preferred alcoholic hardeners for use in the present invention have an average of at least two primary or secondary hydroxyl groups per molecule; in this connection, mention may be made of alcoholic hardeners having two, three or four primary or secondary hydroxyl groups per molecule.

Broadly, the alcohol compound (H) may be selected from the group consisting essentially of low molecular weight and higher molecular weight aliphatic and cycloaliphatic alcohols. Without intending to limit the invention, exemplary low molecular weight alcohols (H) suitable for inclusion in the curable composition containing the cyclic carbonate functional polyester (CC-PES) are: 1, 4-butanediol; ethylene glycol; diethylene glycol; triethylene glycol; neopentyl glycol; 1, 3-propanediol; 1, 5-pentanediol; 1, 6-hexanediol; glycerol; diglycerin; pentaerythritol; dipentaerythritol; and sugar alcohols such as sorbitol and mannitol. Exemplary higher molecular weight polymer polyols include, but are not limited to: a polyester polyol; a polycarbonate polyol; a polyether polyol; a polyacrylate polyol; and polyvinyl alcohol. These polymer polyol compounds (H) should generally be characterized by one or more of the following properties: i) an average OH functionality of at least 1.5mol and preferably at least 1.8, for example an OH functionality of 1.5 to 10 or 1.8 to 4, wherein the average OH functionality is understood to be the average number of OH groups per polymer chain; ii) a number average molecular weight (Mn) of 250 to 50000g/mol, preferably 500 to 10000 g/mol; and iii) making at least 50 mole% of the hydroxyl groups contained in the polymer polyol component primary hydroxyl groups.

The total amount of compound (H) present in the curable composition is preferably selected such that the molar ratio of 1, 3-dioxolan-2-one groups of the functional polyester (CC-PES) to functional groups (F) is from 1:10 to 10:1, for example from 5:1 to 1:5, and preferably from 1:2 to 2: 1.

In an alternative expression of the composition, the total amount of compound (H) is suitably from 0.1 to 50 wt%, preferably from 0.5 to 40 wt%, and more preferably from 1 to 30 wt%, based on the combined total amount of cyclic carbonate functional polyester (CC-PES) and compound (H).

It is standard in the art that curable compositions may include additives and auxiliary ingredients. Suitable additives and adjunct ingredients include: a catalyst; an antioxidant; ultraviolet absorbers/light stabilizers; a metal deactivating agent; an antistatic agent; an enhancer; a filler; an antifogging agent; a propellant; a biocide; a plasticizer; a lubricant; an emulsifier; a dye; a pigment; a rheological agent; an impact modifier; an adhesion modifier; an optical brightener; a flame retardant; an anti-drip agent; a nucleating agent; a wetting agent; a thickener; a protective colloid; defoaming agents; a tackifier; a solvent; a reactive diluent; and mixtures thereof. The choice of suitable conventional additives for use in the composition depends on its particular intended use and can be determined in individual cases by the skilled person.

In certain embodiments of the present invention, no catalyst is required to catalyze the reaction of the cyclic carbonate group with the functional group (F) of compound (H): this is generally the case in the case of primary and secondary amino groups present as functional groups (F). However, in other cases, and preferably where compound (H) has a reactive group F different from the amino group, a catalyst may be required: suitable catalysts for hardening will then be 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.

Basic catalysts (and especially organic amines and organic phosphines) are an important class of catalysts in the present invention. Preferred among the organic amines are: amidine bases, e.g. 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU) and 1, 5-diazabicyclo [4.3.0]Non-5-ene (DBN); mono-C₁-C₆-an alkylamine; di-C₁-C₆-an alkylamine; and tri-C₁-C₆Alkylamines, especially triethylamine and tert-butylamine. Preferred among the organophosphines are: trialkylphosphines, such as tri-n-butylphosphine; and triarylphosphines, such as triphenylphosphine. Of course, such basic catalysts can also be used as mixtures, optionally with tri-C₁-C₆-alkylammonium halides and copper salts in combination; as examples, mention may be made of triphenylphosphine and tri-C₁-C₆A combination of an alkylammonium halide and a copper salt, such as copper (I) chloride, copper (I) bromide, copper (II) chloride or copper (II) sulfate.

The curable coating, adhesive or sealant composition should contain less than 5% by weight water based on the weight of the composition, and is most preferably an anhydrous composition substantially free of water. These embodiments do not exclude that the composition either comprises an organic solvent or is substantially free of an organic solvent.

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; a halogenated hydrocarbon; an alkane; an olefin; 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 listed 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 binder to harden. More specifically, the cyclic carbonate functional polyester (CC-PES) and the compound (H) may be mixed in predetermined amounts by hand, by machine, by (co) extrusion or by any other means capable of ensuring a fine and highly uniform mixing thereof.

The hardening of the binder composition of the invention generally takes place at temperatures of-10 ℃ to 150 ℃, preferably 0 ℃ to 100 ℃ and especially 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 worker, using simple preliminary tests if necessary. Of course, hardening at temperatures of 5 ℃ to 35 ℃ or 20 ℃ to 30 ℃ is particularly advantageous, since this eliminates the need to heat or cool the mixture to a large extent from the ambient temperature which normally prevails. However, where applicable, the temperature of the mixture of cyclic carbonate functional polyester (CC-PES) and compound (H) may be raised above the mixing temperature by using conventional methods, including microwave induction.

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

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

Since the compositions according to the invention are capable of giving high bond strengths in a short time, the compositions are optimum for forming composite structures by bonding identical or different materials to one another face to face, usually at room temperature, in particular with the use of amine hardeners (H). As exemplary adhesive applications of the composition of the invention, mention may be made of the bonding together of wood and wood materials and the bonding together of metal materials.

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

In each of the above applications, the composition may be applied by conventional application methods such as: brushing; roll coating, for example, using a 4-application roll apparatus in the case of solvent-free compositions, or using a 2-application roll apparatus for solvent-containing compositions; applying with 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 coating and adhesive applications, it is recommended to apply the composition to a wet film thickness of 10 to 500 μm. Thinner layers in this range are more economical to apply and reduce the likelihood of thick cured areas (for coating 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.