Method for preparing functionalized polyesters

Abstract

The present application is directed to a method for preparing a cyclic carbonate-functional polyester, The method comprises: (A) reacting glycerol carbonate with an anhydride to form adduct (A); (B) reacting the adduct (A) with at least one polyepoxide compound to form the adduct (B); and (C) reacting said adduct (B) with at least one polycarboxylic acid to form said cyclic carbonate functional polyester; Includes.

Description

[Technical field]

[0001] This application is directed to a method for making functionalized polyesters. More particularly, the application is directed to a method for making cyclic carbonate functionalized polyesters and the use of said polyesters in coating, adhesive or sealant compositions. [Background technology]

[0002] The use of polyurethanes in coating, adhesive and sealant formulations is well known and long established. Such polyurethanes include precursors that cure in situ to form the adhesive layer: traditionally, the curable compounds contain one or more polyisocyanate compounds and one or more compounds that react with isocyanates, such as polyols. Depending on the selection of these curable compounds, a given polyurethane coating, adhesive or sealant can be formulated to cure at room temperature or upon exposure to specific physicochemical conditions.

[0003] The isocyanates present in such conventional polyurethane formulations represent a toxicological risk, which on the one hand is also relevant for the handling of the materials when they are used, since isocyanates are usually highly toxic and highly allergenic, and on the other hand, in flexible substrates there is a risk that incompletely reacted aromatic isocyanates can migrate within the substrate and be hydrolyzed by moisture or water-containing components to carcinogenic aromatic amines.

[0004] Therefore, ideally, isocyanate-free one-component (1K) and two-component (2K) systems for curable coating compositions with good curing performance even at room temperature are desirable. And, cyclic carbonates that can react with amines to form urethanes at room temperature have been recognized in the art as potentially important alternatives to the polyurethane formation by the isocyanate / polyol reaction described above. However, there are obstacles to the more widespread use of cyclic carbonates to produce non-isocyanate polyurethanes (NIPUs): i) cyclic carbonates typically have limited reactivity, even in the presence of catalysts such as amidines, guanidines and thioureas; ii) the ring-opening reaction of cyclic carbonates is less selective, resulting in the formation of a mixture of stable secondary alcohols and less stable primary alcohols; and iii) As a corollary, the polyurethanes that form tend to be of low molecular weight, limiting their usefulness; It is known that.

[0005] Tomita et al., "Reactivity comparison of five- and six-membered cyclic carbonates with amines: Basic evaluation for synthesis of poly(hydroxyurethane)," Journal of Polymer Science, January 1, 2001, Vol. 39, No. 1, pp. 162-168, describes limited reactivity of 5-(2-propenyl)-1,3-dioxan-2-one (1) and 4-(3-butenyl)-1,3-dioxolan-2-one (2) with hexylamine and benzylamine. However, the authors found that the reactivity of these cyclic carbonates depends on the substituent (R) located at their 4-position. For example, when R is Me <H<フェニル<CH 2 OPh <CF 3While this has been helpful, 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.

[0006] Lamarzelle et al., "Activated lipidic cyclic carbonates for non-isocyanate polyurethane synthesis", Polymer Chemistry, 2016, No. 7, pp. 1439-1451, describes a method to activate the cyclic carbonate ring by introducing an electron-withdrawing group containing an ester or ether moiety at the β-position to increase the reactivity towards amines. The citation itself is limited to its commercial application: the synthetic procedures and catalysts employed to prepare the bifunctional ester-cyclic carbonate materials are not industrially feasible due to their high cost, and the synthesis leads to crystalline materials at room temperature. Regardless, the inventors recognize the promise of developing high molecular weight cyclic carbonate functional polyesters in which an ester group is located at the β-position of a five-membered cyclic carbonate group.

[0007] WO 2016 / 124518 (Evonik Degussa GMBH) describes a method for preparing cyclic carbonate-containing polymers, in particular cyclic carbonate-containing polyesters. 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 strong acid, such as Lewis acid or methanesulfonic acid, which requires removal from the final product and may darken it. Moreover, the exemplified embodiment of the second step employs reaction temperatures of 180° C. or higher, at which glycerol carbonate is not stable.

[0008] WO 2012 / 007254 (Total Petrochemical Res. Feluy et al.) describes the following: a) ring-opening polymerization of a first 5-, 6- or 7-membered ring cyclic carbonate or cyclic ester or diester, optionally with functional groups, in the presence of a first catalyst system and in the presence of one or more diols or polyols acting as both coinitiators and chain transfer agents; b) chemical modification of the hydroxyl chain end groups to carboxyl groups in the presence of a second catalytic system; c) coupling reaction with at least two equivalents of a second 5-, 6- or 7-membered cyclic carbonate having at least one functional group that allows for coupling with a carboxyl moiety in the presence of a third catalytic system; d) the polyaddition of a diamine or polyamine by ring-opening of the second terminal 5-, 6-, or 7-membered cyclic carbonate of step c); and e) recovery of poly(carbonate-urethane) or poly(ester-urethane); US Pat. No. 5,999,363 describes a method for preparing a poly(carbonate-urethane) or poly(ester-urethane) comprising:

[0009] EP 2582687 (Construction Research & Technology GMBH) describes a two-step process for preparing cyclic carbonate functional polyesters. The first step provides for the formation of a five-membered cyclic carbonate according to the following exemplary reaction scheme:

[0010] [ka]

[0011] In the second step, the derivatized cyclic carbonate is transesterified with a polyol, but requires the presence of an exotic catalyst, more specifically either an enzyme catalyst or an acidic cation exchanger. A representative second step from this reference is shown below:

[0012] [ka]

[0013] WO 2017 / 156132 (3D Systems) discloses a reaction pathway for forming cyclic carbonate monomers suitable for use in 3D printing inks. Specifically, a short CC end capper undergoes reaction with an isocyanate moiety bearing an acrylate functionality at the other end of the chain: the synthesis is carried out under solvent-free conditions and with a tin-based catalyst. The ester functionality is provided from the acrylate moiety or from the reaction of said end capper with an acyl chloride. However, isocyanates, toxic acyl chlorides and tin catalysts are used in the reaction pathway, which is therefore an obstacle from a health and safety perspective.

[0014] Recently, EP 3401350 (Henkel) has disclosed a method for the synthesis of cyclic carbonate-functionalized polyesters bearing an ester group at the β-position. The first step is the preparation of a cyclic carbonate-carboxylic acid adduct resulting from the reaction of glycerol carbonate with a cyclic anhydride, followed by the reaction of this adduct with an epoxy-functional polyester. However, this synthesis procedure requires the use of a basic catalyst (Na 2 O 3 ) for the complete reaction of the epoxide with the carboxylic acid. 2 CO 3 ) and the need to use high temperatures (150-155 °C). This fact often leads to problems of homopolymerization of the reaction mixture when synthesizing certain products with complex structures. [Prior art documents] [Patent documents]

[0015] [Patent Document 1] International Publication No. 2016 / 124518 [Patent Document 2] International Publication No. 2012 / 007254 [Patent Document 3] European Patent No. 2582687 [Patent Document 4] International Publication No. 2017 / 156132 [Patent Document 5] European Patent Application Publication No. 3401350 [Non-patent literature]

[0016] [Non-Patent Document 1] , Journal of Polymer Science, 2001, Volume 39, Issue 1, p.162-168 [Non-Patent Document 2] Polymer Chemistry, 2016, Issue 7, p.1439-1451 Summary of the Invention [Problem to be solved by the invention]

[0017] In view of the above citations, there remains a need in the art to provide a simple, cost-effective and industrially feasible method for the synthesis under mild reaction conditions of five-membered cyclic carbonate functionalized oligomers or polymers bearing β-position-located ester groups with high functionality and high cyclic carbonate content. [Means for solving the problem]

[0018] In a first aspect of the present invention, there is provided a method for preparing a cyclic carbonate functional polyester, the method comprising: (1) reacting glycerol carbonate with an anhydride to form an adduct (A) having the general structure of formula (I);

[0019] [ka]

[0020] wherein n is 1, 2 or 3;

[0021] (2) reacting the adduct (A) with at least one polyepoxide compound to form an adduct (B) having the general structure of formula (II);

[0022] [ka]

[0023] In the formula, R 1 represents the residue of a dihydric phenol or a dihydric alcohol, and n represents 1, 2 or 3; and

[0024] (3) reacting said adduct (B) with at least one polycarboxylic acid to form said cyclic carbonate functional polyester; Includes.

[0025] The reactive anhydride is usually an anhydride of an acid selected from the group consisting of maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, azealic acid, malonic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, glutaric acid, alkyl glutaric acid, alkenyl glutaric acid and mixtures thereof. Preferably, the reactive anhydride is selected from the group consisting of maleic anhydride, adipic anhydride, succinic anhydride, alkyl succinic anhydride, alkenyl succinic anhydride, glutaric anhydride, alkyl glutaric anhydride, alkenyl glutaric anhydride and mixtures thereof.

[0026] The reaction of glycerol carbonate with the anhydride (referred to as step A in certain embodiments herein below) is typically subject to the following limitations: i) a molar ratio of glycerol anhydride:glycerol carbonate in the range of 2:1 to 0.8:1, preferably in the range of 1.2:1 to 0.8:1, more preferably in the range of 1.1:1 to 0.9:1; ii) a temperature in the range of 60° C. to 120° C., preferably 80° C. to 110° C.; and iii) nitrogen atmosphere; The above-mentioned measures will be implemented under at least one of the following: For completeness, it is noted that these method limitations are not mutually exclusive and one, two or three limitations may be affected.

[0027] When reacting adduct (A) with at least one polyepoxide compound to form adduct (B), the reaction may be carried out at an equivalent ratio of carboxyl groups to epoxy groups of at least 1:1.5, for example, 1:(1.5-3) or 1:(1.8-2.2).

[0028] When the reaction of adduct (B) with at least one polycarboxylic acid is carried out to form said cyclic carbonate-functional polyester, said polycarboxylic acid is a carboxyl-functional polyester (carboxy-PES) 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.

[0029] In a significant embodiment of the present invention, a method for preparing a cyclic carbonate functional polyester is provided, the method comprising the steps of: (A) reacting glycerol carbonate with an anhydride to form an adduct (A) having the general structure of formula (I);

[0030] [ka]

[0031] wherein n is 1, 2 or 3;

[0032] (B) reacting the adduct (A) with at least one polyepoxide compound to form an adduct (B) having the general structure of formula (II):

[0033] [ka]

[0034] In the formula, R 1 represents the residue of a dihydric phenol or dihydric alcohol, and n is 1, 2 or 3;

[0035] (C) providing a polycarboxylic acid; and (D) reacting said adduct (B) with a polycarboxylic acid to form said cyclic carbonate functional polyester; Includes.

[0036] In step B of the above defined process, it is preferred that the polyepoxide compound, preferably the diglycidyl ether, has an epoxy equivalent weight of 100 to 700 g / eq, preferably 120 to 320 g / eq. However, independently of this, it is preferred that in step B the molar ratio of the polyepoxide compound, preferably the diglycidyl ether compound, to the polycarboxylic acid (if applicable, the carboxyl functional polyester) is from 1.5:1 to 3:1, preferably from 1.8:1 to 2.2:1.

[0037] Preferably, the polycarboxylic acid provided in step C is a dicarboxylic or tricarboxylic acid. In alternative, non-mutually exclusive preferred terms, the polycarboxylic acid provided should generally be characterized by an acid value (Av) of 50 to 1000 mg KOH / g, preferably by an acid value (Av) of 80 to 950 mg KOH / g.

[0038] In an important embodiment, the polycarboxylic acid is a carboxyl-functional polyester (carboxy-PES). Suitable examples are compounds represented by formulae (III) and (IV):

[0039] [ka]

[0040] In the formula, R 2represents the residue of a trihydroxy alcohol.

[0041] [ka]

[0042] In the formula, R 3 represents the residue of a dihydroxy alcohol.

[0043] The means of producing or providing such a carboxyl functional polyester in step C is not particularly limited. However, it is preferred that the provided carboxyl functional polyester (carboxy-PES) is characterized by an acid value (Av) of 50-500 mg KOH / g, preferably 80-430 mg KOH / g.

[0044] In an exemplary method, the carboxyl functional polyester (carboxyl-PES) of Step C is i) providing a polyester having two or more hydroxyl groups; and ii) reacting the hydroxyl functional polyester with a carboxylic acid or anhydride thereof; The hydroxyl functional polyesters thus provided are preferably characterized by having a hydroxyl number of from 50 to 300 mg KOH / g, preferably from 80 to 150 mg KOH / g.

[0045] In another method, the carboxyl functional polyester (carboxy-PES) of Step C is provided by 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.

[0046] The above equivalent ratios of carboxyl groups to epoxy groups are still applicable to the reaction of adduct (B) with a carboxy-functional polyester in step D. Illustratively, in the reaction of step D, adduct (B) is reacted with a carboxy-functional polyester in an equivalent ratio of carboxylic acid to epoxide of 0.5:1 to 2:1, preferably 0.8:1 to 1.2:1.

[0047] An effective method according to the present invention is to improve the performance of both stages B and D: i) at a temperature range of 40° C. to 100° C., preferably 60° C. to 85° C.; and / or ii) in the presence of a catalytic amount of a phase transfer catalyst; Note that it contains Such a temperature range corresponds to a mild condition that can prevent the opening of the 5-membered cyclic carbonate ring of the adduct in the reaction of Step D and avoid the problem of homopolymerization of the reaction mixture when synthesizing certain products having complex structures, which may occur especially when targeting products having three or more functionalities or in the case of cyclic carbonate functional polyesters having low molecular weight and high cyclic carbonate equivalent weight (CCEW) or carbonate content.

[0048] It should further be noted that the process of the present invention can be effectively carried out when steps A to D are carried out continuously in one vessel, without separation of intermediate products. This "one-pot" solution makes the present invention extremely simple to carry out.

[0049] The method of the present invention provides oligomeric and polymeric compounds functionalized with five-membered cyclic carbonate groups; the polyester group is located at the β-position relative to the cyclic carbonate, and therefore acts as an electron-withdrawing group that helps to increase the reactivity of the five-membered cyclic carbonate ring. Furthermore, the method provides for the synthesis of functionalized compounds with a wide range of molecular weights: in certain embodiments, the molecular weight and structure of the provided carboxy-functional polyester (carboxy-PES) substantially determines the molecular weight and structure of the cyclic carbonate-functional polyester. Furthermore, the method provides for the synthesis of functionalized compounds with high functionality of the five-membered cyclic carbonate ring: in certain embodiments, the functionality of the five-membered cyclic carbonate ring of the provided carboxy-functional polyester (carboxy-PES) is at least two or at least three.

[0050] According to a second aspect of the present invention there is provided a cyclic carbonate functional polyester obtainable by the process described hereinabove and in the appended claims, preferably characterized by at least one of a cyclic carbonate equivalent weight of 300-2500 g / eq, preferably 400-1500 g / eq, a number average molecular weight (Mn) of 500-5000 g / mol, preferably 800-3000 g / mol, and an OH number of 50-300 mg KOH / g, preferably 100-200 mg KOH / g.

[0051] According to a third aspect of the present invention there is provided a curable coating, adhesive or sealant composition comprising the above cyclic carbonate functional polyester and at least one multifunctional compound (H) having at least two functional groups (F) selected from the group consisting of primary amino groups, secondary amino groups, hydroxy groups, phosphine groups, phosphonate groups and mercaptan groups.

[0052] <Definition> As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0053] As used herein, the terms "comprising," "comprises," and "comprised of" are synonymous with "including," "includes," "containing," or "contains," and are inclusive or open-ended and do not exclude additional, unrecited elements, components, or method steps.

[0054] When amounts, concentrations, dimensions, and other parameters are expressed in the form of ranges, preferred ranges, upper limits, lower limits, or preferred upper limits, it is to be understood that any range obtained by combining any upper limit or preferred value with any lower limit or preferred value is also specifically disclosed, regardless of whether the resulting range is clearly stated in the context.

[0055] The terms "preferred," "preferably," "desirably," "in particular," and "particularly" are frequently used herein to refer to embodiments of the disclosure that may be particularly advantageous, under particular circumstances. However, the recitation of one or more preferred or preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude such other embodiments from the scope of the disclosure.

[0056] Molecular weights given in the text refer to number average molecular weights (Mn) unless otherwise specified. All molecular weight data refer to values ​​obtained by gel permeation chromatography (GPC) unless otherwise specified.

[0057] "Acid value" or "acid number" is a measure of the amount of free acid present in a compound: the acid number is the number of milligrams of potassium hydroxide (mg KOH / g) required to neutralize the free acid present in 1 gram of material. Any measured acid numbers given in the specification are determined according to German standard DIN 53402.

[0058] The OH numbers given herein were obtained according to the "German (DGF) Standard Methods for the Investigation of Fats, Oils and Fat Products, Surfactants and Related Substances (Deutsche (DGF) Einheitsmethoden zur Untersuchung von Fetten, Fettprodukten, Tensiden und verwandten Stoffen)" (Table of Contents (Gesamtinhaltsverzeichnis) 2016) CV 17b (53).

[0059] In this specification, room temperature is 23°C ± 2°C.

[0060] As used herein, the term "equivalent (eq.)," as in normal chemical notation, refers to the relative number of reactive groups present in a reaction; the term "milliequivalent (meq)" refers to one thousandth (10 -3 ).

[0061] The term "equivalent weight" as used herein refers to the molecular weight divided by the number of functional groups involved. Thus, "epoxy equivalent weight" (EEW) means the weight in grams of a resin that contains one equivalent of epoxy.

[0062] As used herein, "aliphatic group" means a saturated or unsaturated linear (i.e. straight-chain), branched, cyclic (including bicyclic) organic group; the term "aliphatic group" therefore includes "alicyclic groups", which are cyclic hydrocarbon groups having properties similar to those of aliphatic groups. The term "aromatic group" means a monocyclic or polycyclic aromatic hydrocarbon group.

[0063] As used herein, the term "alkyl group" refers to a monovalent group that is a radical of an alkane and contains linear and branched organic groups, which may be substituted or unsubstituted. The term "alkylene group" refers to a divalent group that is a radical of an alkane and contains linear and branched organic groups, which may be substituted or unsubstituted.

[0064] Specifically, in this specification, "C 1 ~C 6 An "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 substituted with one or more substituents such as halo, nitro, cyano, amido, amino, sulfonyl, sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamido, and hydroxy. Halogenated derivatives of the above exemplary hydrocarbon groups may be specifically mentioned as examples of suitable substituted alkyl groups. Generally, however, alkyl groups containing 1 to 6 carbon atoms (C 1 ~C 6 Unsubstituted alkyl groups containing 1 to 4 carbon atoms (C alkyl) 1 ~C 4 alkyl) or 1 or 2 carbon atoms (C 1 ~C 2 It should be noted that unsubstituted alkyl groups, including alkyl, are preferred.

[0065] In this specification, "C 4 -C 20 An "alkenyl" group refers to an aliphatic carbon group containing 4 to 20 carbon atoms and at least one double bond. Like the alkyl groups described above, alkenyl groups can be straight or branched and optionally substituted. The term "alkenyl" also encompasses groups having "cis" and "trans" configurations, or alternatively, "E" and "Z" configurations, as will be recognized by those of skill in the art. Generally, however, groups having 4 to 18 (C 4~18) or 4~12(C 2~12 It should be noted that unsubstituted alkenyl groups containing carbon atoms of C 4 ~C 20 Examples of alkenyl groups include, but are not limited to, 2-butenyl, 4-methylbutenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, 1-heptenyl, 1-octenyl, and n-dodecenyl.

[0066] As used herein, "polycarboxylic acid" includes any organic structure having two or more carboxylic acid functional groups. Specifically, the term includes polymers having at least two carboxyl functional groups, and thus specifically includes carboxyl-functional polyester resins, carboxyl-functional polyacrylate resins, carboxyl-functional polymethacrylate resins, carboxyl-functional polyamide resins, carboxyl-functional polyimide resins, and carboxyl-functional polyolefin resins.

[0067] As used herein, "polyol" refers to any compound that contains two or more hydroxyl groups. Thus, the term encompasses diols, triols, and compounds containing four or more -OH groups.

[0068] The term "epoxide compound" refers to monoepoxide compounds, polyepoxide compounds, and epoxide-functional prepolymers. The term "polyepoxide compound" is therefore intended to refer to an epoxide compound having at least two epoxy groups. Moreover, the term "diepoxide compound" is therefore intended to refer to an epoxide compound having two epoxy groups.

[0069] As used herein, the term "catalytic amount" means a substoichiometric amount of catalyst relative to a reactant.

[0070] The term "essentially free" is intended herein to mean that the applicable group, compound, mixture or component constitutes less than 0.1% by weight, based on the weight of the defined composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0071] In its broadest terms, the present invention provides a process for preparing a cyclic carbonate functional polyester, the process comprising: (1) reacting glycerol carbonate with an anhydride to form an adduct (A) having the general structure of formula (I);

[0072] [ka]

[0073] wherein n is 1, 2 or 3;

[0074] (2) reacting the adduct (A) with at least one polyepoxide compound to form an adduct (B) having the general structure of formula (II);

[0075] [ka]

[0076] In the formula, R 1 represents the residue of a dihydric phenol or a dihydric alcohol, n is 1, 2 or 3; and

[0077] (3) reacting said adduct (B) with at least one polycarboxylic acid to form said cyclic carbonate functional polyester; Includes.

[0078] <Preparation of Adduct (A)> In the first step of the above defined process (hereinafter sometimes referred to as step A), the glycerol carbonate is reacted with a polyfunctional anhydride. This esterification reaction results in an adduct (A) of formula (1) above, which has a carboxylic acid group and an ester group arranged in the beta (β-) position, as exemplified below in the specification.

[0079] The glycerol carbonate reactant may alternatively be identified as 4-hydroxymethyl-1,3-dioxolan-2-one. This compound is manufactured by Huntsman Corporation and sold by Jeffsol. TM Alternatively, the compound can be synthesized by methods known in the art, including the reaction of glycerin with a carbonate source such as phosgene, a dialkyl carbonate or an alkylene carbonate; the reaction of glycerin with urea, carbon dioxide and oxygen; or the reaction of carbon dioxide with glycidol. The following documents are referenced for such synthesis methods: U.S. Pat. No. 2,915,529; U.S. Pat. No. 6,025,504; European Patent No. 1,156,042; and U.S. Pat. No. 5,359,094.

[0080] While there is no particular intent to limit the reactive polyfunctional anhydride, most suitable are anhydrides of acids selected from the group consisting of maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, azealic acid, malonic acid, succinic acid, alkylsuccinic acid, alkenylsuccinic acid, glutaric acid, alkylglutaric acid, alkenylglutaric acid, and mixtures thereof.

[0081] Preferably, the polyfunctional anhydride is an anhydride selected from the group consisting of maleic anhydride, adipic anhydride, succinic anhydride, alkyl succinic anhydride, alkenyl succinic anhydride, glutaric anhydride, alkyl glutaric anhydride, alkenyl glutaric anhydride, and mixtures thereof. More preferably, the polyfunctional anhydride is an anhydride selected from the group consisting of maleic anhydride, adipic anhydride, succinic anhydride, glutaric anhydride, and mixtures thereof.

[0082] For the sake of completeness, the most suitable alkyl succinic anhydrides are those defined by the following general formula A:

[0083] [ka]

[0084] In the formula: R 1 , R 2 , R 3 and R 4 is hydrogen and C 1 ~C 6 The alkyl groups are independently selected from the group consisting of aryl, aryl groups, and alkyl groups.

[0085] The most suitable alkenyl succinic anhydrides are those defined by general formula B:

[0086] [ka]

[0087] In the formula: R 5 , R 6 and R 7 is hydrogen and C 1 ~C 6 alkyl groups; and R 8 is C 4 ~C 20 It is an alkenyl group.

[0088] Of course, the most suitable alkyl glutaric anhydrides are those defined by the following general formula C:

[0089] [ka]

[0090] In the formula: R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is hydrogen and C 1 ~C 6 The alkyl groups are independently selected from the group consisting of aryl, aryl groups, and alkyl groups.

[0091] The most suitable alkenyl glutaric anhydrides are those derived from 3-glutaric acid defined by the general formula D:

[0092] [ka]

[0093] In the formula: R 7 , R 8 , R 9 , R 11 and R 12 is hydrogen and C 1 ~C 6 alkyl groups; and R 10 is C 4 ~C 20 It is an alkenyl group.

[0094] The relative amounts of glycerol carbonate to polyfunctional anhydride can vary over a fairly wide range, although a significant excess of anhydride is not desirable because the reactants can be expensive and difficult to recover and reuse. Preferably, the molar ratio of anhydride:glycerol carbonate is from 2:1 to 0.8:1, more preferably, said ratio is within the range of 1.2:1 to 0.8:1, and most preferably, said ratio is within the range of 1.1:1 to 0.9:1.

[0095] The first step of the present invention may be carried out in any known suitable vessel, including those described in U.S. Patent No. 4,310,708 (Strege et al.), designed to contain the reactants, products and any solvent employed. The vessel materials should, of course, be inert under the conditions employed during the process steps.

[0096] Considering these conditions, the process steps may be carried out at any suitable temperature. The optimum operating temperature for the reaction may be determined by the skilled artisan through experimentation, but a suitable temperature range of 60° C. to 120° C., with a preferred temperature range of 80° C. to 110° C. may be mentioned.

[0097] The pressure of the process is not critical: thus, the reaction can be operated at subatmospheric, atmospheric or superatmospheric pressures, although atmospheric or greater pressures are preferred.

[0098] The first stage reaction has been carried out under anhydrous conditions with good results. If desired, exposure to atmospheric moisture may be avoided by providing an inert, dry blanket gas to the reaction vessel. Dry nitrogen, helium and argon may be used as a blanket gas, but care should be taken when using common nitrogen gas as a blanket, as such nitrogen may not be sufficiently dry due to its susceptibility to moisture absorption; nitrogen may require an additional drying step before use herein.

[0099] The first reaction step can also be carried out under solvent-free conditions, which is indeed desirable. If employed, suitable solvents should be inert and they should not contain functional groups that react with the starting compounds. Thus, aromatic hydrocarbons, illustratively toluene or benzene; aliphatic hydrocarbon solvents 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; esters, such as ethyl acetate, amyl acetate and methyl formate, may be mentioned. Of these solvents, aromatic solvents are the least preferred due to their potential toxic associations.

[0100] It is not necessary to employ a catalyst in this reaction step, and conditions that do not include a catalyst are preferred. However, the use of a catalyst is not precluded when the reaction is carried out at a temperature not higher than 100° C. If used, the amount of catalyst is preferably 0.05-5% by weight or 0.05-3% by weight, based on the total amount of reacting compounds.

[0101] The reaction time to obtain a suitable conversion of the reactive anhydride depends on various factors such as temperature and the type of polyfunctional anhydride. The reaction can be monitored by analyzing the acid value (Av) of the reaction mixture over time, and the reaction is stopped when the determined acid value is constant at a value close to the theoretical acid value. Generally, the time sufficient for the reaction to occur is 2 to 20 hours, for example, 4 to 8 hours or 4 to 7 hours.

[0102] Considering the preferred embodiment of the reaction of anhydrides, an exemplary reaction scheme for the first step of the claimed method is as follows, where n is 1, 2 or 3:

[0103] [ka]

[0104] The adduct (A) produced according to the first step of the present invention may be used as it is or may be isolated and purified using methods known in the art: extraction, evaporation, distillation and chromatography may be mentioned in this regard.

[0105] <Preparation of Adduct (B)> The derived adduct (A) is reacted with at least one polyepoxide compound to form the adduct (B) having the general structure of formula (II).

[0106] [ka]

[0107] In the formula, R 1 represents the residue of a dihydric phenol or a dihydric alcohol, and n is 1, 2 or 3. Preferably, R 1 represents an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, an ether group having 2 to 20 carbon atoms, or a divalent aromatic group having 6 to 12 carbon atoms.

[0108] Regardless of the choice of polyepoxide compound, the reaction should be characterized in that the molar ratio of said adduct (A) to the at least one polyepoxide compound is from 1:1.5 to 1:3, preferably from 1:1.8 to 1:2.2.

[0109] Suitable polyepoxide compounds may be liquid, solid, or solution in a solvent. Moreover, such polyepoxide compounds should have an epoxy equivalent of 100-700 g / eq, for example 145-155 g / eq. And generally, diepoxide compounds with epoxy equivalents less than 500 or less than 400 are preferred: this is mainly from the viewpoint of cost, and in production, low molecular weight epoxy resins require more special purification treatment.

[0110] Suitable diglycidyl ether compounds may be aromatic, aliphatic or cycloaliphatic in nature and thus derivable from dihydric phenols and dihydric alcohols. Useful classes of such diglycidyl ethers are the 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 o-phthalate, diglycidyl isophthalate and diglycidyl terephthalate, diglycidyl ethers based on polyalkylene glycols, in particular polypropylene glycol diglycidyl ether, and glycidyl ethers based on polycarbonate diols. Other suitable diepoxides that may be mentioned are the diunsaturated fatty acid C 1 ~C 18 Includes diepoxides of alkyl esters, butadiene diepoxide, polybutadiene diglycidyl ether, vinylcyclohexene diepoxide, and limonene diepoxide.

[0111] Exemplary polyepoxide compounds 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.

[0112] Although not intended to limit the invention, highly preferred examples of polyepoxide compounds include alkyl epoxy resins such as Araldite DY-H (also known as Grilonit RV 1812) and Araldite DY-D (also known as Grilonit RV 1806); TM 331, D.E.R. TM 332 and DER TM Bisphenol A epoxy resins such as DER 383; TMBisphenol-F epoxy resins such as DER 354; TM Bisphenol A / F epoxy resin blends such as 353; DER TM Aliphatic glycidyl ethers such as DER 736; TM Polypropylene glycol diglycidyl ether such as DER 732; TM 661 and DER TM Solid bisphenol A epoxy resins such as 664UE;DER TM A solution of bisphenol A solid epoxy resin such as 671-X75; DEN TM Epoxy novolac resins such as DER 438 TM Contains brominated epoxy resins such as 542.

[0113] Although the reaction between epoxy and carboxyl groups can proceed without a catalyst, a phase transfer catalyst is required here to achieve both a satisfactory reaction rate and the desired adduct. Examples of suitable phase transfer catalysts include, but are not limited to, ammonium salts such as benzyltrimethylammonium chloride, benzyltriethylammonium chloride (TEBAC), methyltricaprylammonium chloride, methyltributylammonium chloride, methyltrioctylammonium chloride, and tetra-n-octylammonium bromide; and phosphonium salts as phase transfer catalysts such as hexadecyltributylphosphonium bromide, tetramethylphosphonium bromide, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, and trihexyltetradecylphosphonium bromide. Although a person skilled in the art can determine the appropriate and optimal catalytic amount of such compounds, a typical amount of catalyst is proposed to be 0.05-5 wt.%, or 0.05-3 wt.%, based on the total amount of reacting compounds.

[0114] The optimum operating temperature for this stage of the process may be determined by the skilled artisan through experimentation, but a suitable temperature range of 40° C. to 100° C., with a preferred temperature range of 60° C. to 85° C. or even 75° C. may be mentioned. If the reaction temperature is higher than 100° C., the desired adduct (B) may not be obtained in sufficient yield or in good condition for polymerization. The pressure of the process is not critical: thus, the reaction can be operated at subatmospheric, atmospheric or superatmospheric pressures, although atmospheric or higher pressures are preferred.

[0115] Good results are obtained if this step is carried out under anhydrous conditions, where the reaction vessel is provided with an inert, dry blanket gas, for example dry nitrogen, helium or argon. It should also be noted that this reaction step should desirably be carried out under solvent-free conditions. Suitable solvents, if employed, should be inert: they should not contain reactive groups that will react with the starting compounds.

[0116] The progress of the reaction can be monitored by analyzing the acid value (Av) of the reaction mixture over time: when the acid value reaches the desired level (less than 5 mg KOH / g PES) and there is no remaining epoxide detected by NMR, the reaction may be stopped. Generally, a period of 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.

[0117] The adduct (B) produced according to the second step of the present invention may be used as is or may be isolated and purified using methods known in the art: extraction, evaporation, distillation and chromatography may again be mentioned in this regard.

[0118] Preparation of Cyclic Carbonate-Functional Polyesters In a further step, the adduct (B) is reacted with at least one polycarboxylic acid to form a cyclic carbonate functional polyester.

[0119] 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 cycloaliphatic, or may have two or more aliphatic, aromatic or cycloaliphatic moieties. Dicarboxylic and tricarboxylic acids are mentioned as being preferred, the former being particularly preferred. Moreover, the preferred polycarboxylic acids should generally be characterized by an acid value (Av) of 50 to 1000 mg KOH / g, for example 80 to 950 mg KOH / g.

[0120] Representative suitable dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, p-phenylenediacetic acid, sebacic acid (SeA), brassylic acid, maleic acid, fumaric acid, oxalic acid, succinic acid, itaconic acid, adipic acid, β-methyladipic acid, trimethyladipic acid, glutaric acid, azelaic acid, malonic acid, suberic acid, pimelic acid, dodecanedioic acid, fatty acid dimers, and mixtures thereof.

[0121] Representative 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.

[0122] In a particularly preferred embodiment of the invention, the polycarboxylic acid of step C is a carboxyl functional polyester (carboxy-PES), which polymer is preferably characterized by an acid value (Av) of 50 to 500 mg KOH / g, preferably 80 to 430 mg KOH / g.

[0123] The carboxyl functional polyester (carboxy-PES) of this embodiment is (i) at least one aromatic, aliphatic or cycloaliphatic dicarboxylic acid or anhydride; (ii) at least one diol compound, more particularly a compound having two aliphatic hydroxyl groups, each of which may independently be a primary or secondary hydroxyl group; It can be obtained by the reaction:

[0124] Suitable dicarboxylic acids include saturated, unsaturated, aliphatic, cycloaliphatic or aromatic dicarboxylic acids and / or anhydrides. Representative dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, p-phenylenediacetic acid, sebacic acid, brassylic acid, maleic acid, fumaric acid, succinic acid, itaconic acid, adipic acid, β-methyladipic acid, trimethyladipic acid, glutaric acid, azelaic acid, malonic acid, suberic acid, dodecanedioic acid and mixtures thereof. Preferably, the dicarboxylic acid or anhydride of the dicarboxylic acid has 4 to 12 carbon atoms.

[0125] Suitable diols having two aliphatic hydroxyl groups may have a molecular weight of 62 to 5000 and may optionally contain ether, ester and / or carbonate groups. Representative 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, polycarbonate diols, polyester diols, dimeric aliphatic alcohols and mixtures thereof.

[0126] The use of further reactants in the derivation of the carboxyl functional polyesters (carboxy-PES) is not excluded and in this regard the following is mentioned: iii) dihydroxymonocarboxylic acids in which each hydroxyl group may independently be a primary or secondary hydroxyl; iv) trifunctional and / or tetrafunctional hydroxyl compounds containing three, four aliphatic hydroxyl groups, respectively, each of which may independently be primary or secondary hydroxyl groups, such as trimethylolethane, trimethylolpropane, hexanetriol or pentaerythritol; may be stated.

[0127] It will be apparent to one skilled in the art that there are multiple alternative methods for synthesizing carboxyl functional polyesters (carboxy-PES) from the above reactants, and thus it is not intended that the present invention be limited to any one of these methods, however, certain preferred synthetic methods are discussed below.

[0128] In the first method, a hydroxyl functional polyester may be reacted with a carboxylic acid or anhydride thereof to form a carboxyl functional polyester. This first method may consist of a two-step process in which, in the first step, a dicarboxylic acid and a diol are reacted to form a hydroxyl functional prepolymer under conditions for removing water; in the second step, the prepolymer is reacted with a carboxylic acid or anhydride thereof. The conditions for removing water typically consist of one or more of a temperature of 120° C. to 250° C.; application of a vacuum; and the use of a solvent to promote azeotropic distillation.

[0129] The amount of acid or anhydride reagent used is determined by the hydroxyl value of the polyester or intermediate prepolymer in the two-stage process, which is desirably 50-300 mg KOH / g, preferably 80-150 mg KOH / g. Generally, 80-100% of the stoichiometric amount required to cap all of the hydroxyl functional groups of the polyester is added. The reagent is added to the hydroxyl functional polyester or prepolymer and the esterification is continued until the desired acid value (Av) is obtained. The total reaction time is usually 5-15 hours.

[0130] Conventional catalysts for promoting esterification reactions can be employed in the (endcapping) reaction and, where applicable, in one or both of the first and second stages. The catalysts, which may be used in an amount of 0.01 to 1% by weight, for example 0.01 to 0.5% by weight, based on the total weight of the reactants, are typically compounds of tin, antimony, titanium or zirconium. In this respect, mention may be made 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, diisopropoxy-bis(acetylacetonato)titanium, di-n-butoxybis(triethanolaminoato)titanium, tributyl monoacetyl titanate, triisopropyl monoacetyl titanate and tetrabenzoate titanate; titanium complex salts, such as alkali titanium oxalates and malonates, potassium hexafluorotitanate; and titanium complexes with hydroxycarboxylic acids, such as tartaric acid, citric acid or lactic acid; titanium dioxide / silicon dioxide coprecipitates; hydrated alkali titanium dioxide; and the corresponding zirconium compounds.

[0131] According to a second desired method of synthesizing carboxyl functional polyesters (carboxy-PES), a stoichiometric excess of dicarboxylic acid is reacted with at least one diol in the presence of a catalytic amount of an esterification catalyst, such as those described above. The stoichiometric excess of dicarboxylic acid should be sufficient to achieve the desired ester linkage and have additional carboxyl groups to obtain terminal carboxyl groups. Moreover, such condensation polymerization reaction should be carried out under conditions that exclude moisture.

[0132] Considering its preferred embodiment, an exemplary reaction scheme for this step of the claimed process is as follows:

[0133] [ka]

[0134] In the formula: R 1 is the residue of a dihydric phenol or a dihydric alcohol; Y is the residue of an oligopolyester or polyester (PES) moiety or a polycarboxylic acid; and n is 1, 2, or 3.

[0135] Although the reaction between epoxy and carboxyl groups can proceed without a catalyst, a phase transfer catalyst is required here to achieve both a satisfactory reaction rate and the desired adduct. Examples of suitable phase transfer catalysts include, but are not limited to, ammonium salts such as benzyltrimethylammonium chloride, benzyltriethylammonium chloride (TEBAC), methyltricaprylammonium chloride, methyltributylammonium chloride, methyltrioctylammonium chloride, and tetra-n-octylammonium bromide; and phosphonium salts as phase transfer catalysts such as hexadecyltributylphosphonium bromide, tetramethylphosphonium bromide, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, and trihexyltetradecylphosphonium bromide. Although a person skilled in the art can determine the appropriate and optimal catalytic amount of such compounds, a typical amount of catalyst is proposed to be 0.05-5% by weight, or 0.05-3% by weight, based on the total amount of reacting compounds.

[0136] The optimum operating temperature for this stage of the process can be determined by the skilled person through experimentation, but a suitable temperature range of 40° C. to 100° C., with a preferred temperature range of 60° C. to 85° C. or even 75° C. may be mentioned. If the reaction temperature is higher than 100° C., the reaction product may not be obtained in sufficient yield. The pressure of the process is not critical: thus, the reaction can be operated at subatmospheric, atmospheric or superatmospheric pressure, although atmospheric or higher pressures are preferred.

[0137] Good results are obtained if this step is carried out under anhydrous conditions, where the reaction vessel is provided with an inert, dry blanket gas, for example dry nitrogen, helium or argon. It should also be noted that this reaction step should desirably be carried out under solvent-free conditions. Suitable solvents, if employed, should be inert: they should not contain reactive groups that will react with the starting compounds.

[0138] The progress of the reaction can be monitored by analyzing the acid value (Av) of the reaction mixture over time: when the acid value reaches the desired level (less than 5 mg KOH / g PES) and there is no remaining epoxide detected by NMR, the reaction may be stopped. Generally, a period of 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.

[0139] The product of step D (CC-PES) may be used as is or may be separated and purified using methods known in the art: extraction, evaporation, distillation and chromatography may again be mentioned in this regard. In a preferred embodiment, after step D there is no further separation or purification step of the CC-PES.

[0140] If it is intended at the time of manufacture that the cyclic carbonate functional polyester (CC-PES) be stored, the polyester should be placed in a container having an air-tight and moisture-proof seal.

[0141] According to the method of the present invention, cyclic carbonate functional polyesters (CC-PES) with functionality of 2 or more or 3 or more (i.e. CC-PES with 3 or more cyclic carbonate rings) are achieved under mild reaction conditions with reaction temperatures below 110°C or even below 100°C in all steps and below 100°C or even below 85°C in the final step of synthesizing the cyclic carbonate functional polyester. The reaction temperature range can prevent the opening of the cyclic carbonate ring during the reaction by observing the consumption of hydroxyl groups (KOH / g value). The milder reaction temperature also minimizes the problem of homopolymerization of epoxide during the synthesis. Meanwhile, the final cyclic carbonate content is approximately 98% of the expected value, close to the theoretical content. The method according to the present invention also allows structural diversity in terms of molecular weight, viscosity, and polymer chain design, without changing the simplicity of the process or increasing the overall cost. The cyclic carbonate functional polyesters are synthesized under solvent-free conditions and do not require any additional purification or separation steps. Furthermore, the additional hydroxyl functionality in the backbone introduced during the synthesis by ring opening of the epoxide provides the potential for additional hydrogen bonding and further crosslinking.

[0142] <Coating, sealant and adhesive compositions> As described above, the cyclic carbonate functional polyesters (CC-PES) obtained by the method of the present invention can be employed as reactive components of curable coating, adhesive or sealant compositions. The further reactants of such compositions are generally one or more multifunctional compounds (H) having at least two functional groups (F) selected from the group consisting of primary amino groups, secondary amino groups, hydroxyl groups, phosphine groups, phosphonate groups and mercaptan groups. Latent compounds in which the functional groups (F) are protected but can be activated under certain physicochemical conditions are also envisaged as suitable further reactants for coating, adhesive or sealant compositions.

[0143] There is no particular limit to the number of functional groups (F) that the (activated) compound (H) has: for example compounds with 2, 3, 4, 5, 6, 7, 8, 9 or 10 functional groups may be used. Moreover, the reactive compound (H) may be a low molecular weight substance, the molecular weight of which is less than 500 g / mol, or an oligomeric or polymeric substance with a number average molecular weight (Mn) of more than 500 g / mol. Of course, mixtures of compounds (H) may also be used, for example mixtures of alcohols and amine hardeners.

[0144] In important embodiments, the functional group (F) of compound (H) is selected from the group consisting of an aliphatic hydroxyl group, an aliphatic primary amino group, an aliphatic secondary amino group, an aliphatic phosphine group, an aliphatic phosphonate group, an aliphatic mercaptan group, and mixtures thereof.

[0145] In a preferred embodiment, compound (H) comprises or consists of an amine (or amino) or alcohol compound, more particularly, the functional group (F) of compound (H) is selected from the group consisting of an aliphatic hydroxyl group, an aliphatic primary amino group, an aliphatic secondary amino group, and combinations thereof.

[0146] Although not intended to limit the invention, exemplary amino compounds (H) suitable for inclusion in the curable compositions containing cyclic carbonate-functional polyesters (CC-PES) are: a) aliphatic polyamines such as ethylenediamine, 1,2- and 1,3-propanediamine, neopentanediamine, hexamethylenediamine, octamethylenediamine, 1,10-diaminodecane, 1,12-diaminododecane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 2,2-dimethylpropylenediamine, trimethylhexamethylenediamine, 1-(3-aminopropyl)-3-aminopropane, 1,3-bis(3-aminopropyl)propane, and 4-ethyl-4-methylamino-1-octylamine; b) alicyclic diamines such as 1,2-diaminocyclohexane, 1,2-, 1,3- and 1,4-bis(amino-methyl)cyclohexane, 1-methyl-2,4-diaminocyclohexane, N-cyclohexylpropylene-1,3-diamine, 4-(2-aminopropan-2-yl)-1-methylcyclohexane-1-amine, isophorone diamine, 4,4'-diaminodicyclohexylmethane (Dicykan), 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 4,8-diaminotricyclo[5.2.1.0]decane, norbornane diamines, menthane diamines and menthene diamines; c) aromatic diamines such as toluylenediamines, xylylenediamines, especially meta-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-aminoethylpiperazine; e) polyetheramines, in particular di- and trifunctional primary polyetheramines based on polypropylene glycol, polyethylene glycol, polybutylene oxide, poly(1,4-butanediol), polytetrahydrofuran (PolyTHF) or polypentylene oxide; f) polyamidoamines (amidopolyamines) obtainable by reacting dimeric fatty acids (for example dimeric linoleic acid) with low molecular weight polyamines such as diethylenetriamine, 1-(3-aminopropyl)-3-aminopropane or triethylenetetramine, or with other diamines such as the aliphatic or cycloaliphatic diamines mentioned above; g) adducts obtained by reacting amines, especially diamines, with a deficit of epoxy resins or reactive diluents, preferably such adducts are used when about 5-20% of the epoxy groups have reacted with amines, especially diamines; h) phenalkamines, known in epoxide chemistry; and i) Mannich bases which may typically be prepared by condensation of a polyamine, preferably diethylenetriamine, triethylenetetramine, isophoronediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- and 1,4-bis(aminomethyl)cyclohexane, with an aldehyde, preferably formaldehyde, and a mono- or polyhydric phenol having at least one aldehyde-reactive core site, such as the various cresols and xylenols, p-tert-butylphenol, resorcinol, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl-2,2-propane, but preferably phenol; It is.

[0147] Alcohol hardeners crosslink and form carbonate polymers by reaction of the primary or secondary alcohol functional groups with the 1,3-dioxolan-2-one groups with formation of a carbonic acid diester. Thus, preferred alcohol hardeners for use in the present invention have an average of at least two primary or secondary hydroxy groups per molecule; in this regard, alcohol hardeners having two, three or four primary or secondary hydroxy groups per molecule may be described.

[0148] Generally, the alcohol compound (H) may be selected primarily from low and high molecular weight aliphatic and cycloaliphatic alcohols. Without intending to limit the invention, representative low molecular weight alcohol compounds (H) suitable for inclusion in the curable composition containing cyclic carbonate functional polyesters (CC-PES) are 1,4-butanediol, ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, glycerol, diglycerol, pentaerythritol, dipentaerythritol, and sugar alcohols such as sorbitol and mannitol. Representative high molecular weight polymeric polyols include, but are not limited to, polyester polyols, polycarbonate polyols, polyether polyols, polyacrylate polyols, and polyvinyl alcohols. These polymeric polyol compounds (H) typically have the following properties: i) an average OH functionality of at least 1.5 mol and preferably at least 1.8 mol, for example an OH functionality ranging from 1.5 to 10 or from 1.8 to 4, whereby said 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 50,000 g / mol, preferably 500 to 10,000 g / mol; and iii) at least 50 mole percent of the hydroxyl groups in the polymeric polyol component are primary hydroxyl groups; should be characterized by one or more of the following:

[0149] The total amount of compounds (H) present in the curable composition is preferably selected such that the molar ratio of 1,3-dioxolan-2-one groups of said functional polyester (CC-PES) to functional groups (F) is in the range of 1:10 to 10:1, for example 5:1 to 1:5, preferably in the range of 1:2 to 2:1.

[0150] In another expression of the composition, the total amount of compound (H) based on the total amount of the cyclic carbonate functional polyester (CC-PES) and compound (H) is suitably 0.1 to 50% by weight, preferably 0.5 to 40% by weight, and more preferably 1 to 30% by weight.

[0151] As is standard in the art, the curable composition may include additives and auxiliary components.Suitable additives and auxiliary components include catalysts, antioxidants, UV absorbers / light stabilizers, metal deactivators, antistatic agents, reinforcing agents, fillers, antifogging agents, propellants, biocides, plasticizers, lubricants, emulsifiers, dyes, pigments, rheological agents, impact modifiers, adhesion modifiers, optical brighteners, flame retardants, drip-proofing agents, nucleating agents, wetting agents, thickeners, protective colloids, defoamers, tackifiers, solvents, reactive diluents, and mixtures thereof.The selection of suitable conventional additives for the composition depends on its specific intended use and can be determined in each case by those skilled in the art.

[0152] 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 the compound (H): this may typically be the case when primary and secondary amino groups are present as functional groups (F). However, in other cases, preferably when the compound (H) has a reactive group F different from the amino group, a catalyst may be required: the appropriate catalyst for curing is then determined in a known manner depending on the type of reactive functional group (F). The catalyst is optionally used in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight, based on the total weight of the curable composition.

[0153] Basic catalysts, especially organic amines and organic phosphines, represent important classes of catalysts in the present invention. Among the organic amines, preferred are 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), mono-C 1 ~C 6 -Alkylamines, di-C 1 ~C 6 -Alkylamines and tri-C1 ~C 6 Among the organic phosphines, preferred are the trialkylphosphines, such as tri-n-butylphosphine, and the triarylphosphines, such as triphenylphosphine. Of course, such basic catalysts can also be used in mixtures, if desired tri-C 1 ~C 6 -alkylammonium halides and copper salts. As an example, triphenylphosphine and tri-C 1 ~C 6 -Combinations of alkylammonium halides and copper salts such as copper(I) chloride, copper(I) bromide, copper(II) chloride or copper(II) sulfate may also be mentioned.

[0154] The curable coating, adhesive or sealant compositions should contain less than 5% by weight of water, based on the weight of the composition, and are most preferably anhydrous compositions that are substantially free of water. These embodiments do not preclude the composition from either containing organic solvents or being substantially free of organic solvents.

[0155] Generally, all organic solvents known to those skilled in the art can be used as solvent, but it is preferred that said organic solvent is selected from the group consisting of esters, ketones, halogenated hydrocarbons, alkanes, alkenes and aromatic hydrocarbons. Representative solvents are methylene chloride, trichloroethylene, toluene, xylene, butyl acetate, amyl acetate, isobutyl acetate, methyl isobutyl ketone, methoxybutyl acetate, cyclohexane, cyclohexanone, dichlorobenzene, diethyl ketone, di-isobutyl ketone, dioxane, ethyl acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl acetate, 2-ethylhexyl acetate, glycol diacetate, heptane, hexane, isobutyl acetate, isooctane, isopropyl acetate, methyl ethyl ketone, tetrahydrofuran or tetrachloroethylene or a mixture of two or more of these solvents.

[0156] <Methods and Applications> To form the coating, sealant or adhesive composition, the reactive compounds are mixed together in such a way as to cause the curing of the binder. More specifically, the cyclic carbonate functional polyester (CC-PES) and compound (H) may be mixed in a given amount by hand, machine, (co)extrusion or any other means capable of ensuring their fine and highly uniform mixing.

[0157] Curing of the binder compositions of the invention typically takes place at temperatures ranging from -10°C to 150°C, preferably from 0°C to 100°C, in particular from 10°C to 70°C. The appropriate temperature depends on the particular compound (H) and the desired curing rate and can be determined in each individual case by the person skilled in the art, if necessary using simple preliminary tests. Of course, curing at temperatures of 5°C to 35°C or 20°C to 30°C is particularly advantageous, since this usually avoids the need to substantially heat or cool the mixture from the prevailing ambient temperature. 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 using conventional means, including microwave induction.

[0158] The compositions according to the invention may find utility in particular in varnishes, inks, elastomers, binders for fibers and / or particles, coatings of glass, lime- and / or cement-bonded plaster, gypsum-containing surfaces, coatings of mineral building materials such as fiber cement building materials and concrete, coatings and sealings of wood and wood-based materials such as chipboard, fiberboard and paper, coatings of metal surfaces, coatings of asphalt- and bitumen-containing pavements, coatings and sealings of various plastic surfaces, and coatings of leather and textiles.

[0159] The compositions of the present invention are also believed to be suitable as pourable sealing compounds for electrical building components such as cables, optical fibers, cover strips or plugs. The sealants can help protect these components against the ingress of water and other contaminants, against heat exposure, temperature fluctuations and thermal shock, and against mechanical damage.

[0160] Due to the fact that the compositions of the present invention can produce high bond strengths, often in a short time at room temperature, especially when an amine hardener (H) is employed, the compositions are best used to form composite structures by bonding the same or different materials to each other surface-to-surface.As exemplary adhesive applications of the compositions of the present invention, bonding wood and wooden materials together and bonding metal materials together may be mentioned.

[0161] In a particularly preferred embodiment of the present invention, the curable compositions are used as solventless or solvent-borne laminating adhesives for adhesively bonding plastic and polymeric films such as polyolefin films, poly(methyl methacrylate) films, polycarbonate films, and acrylonitrile butadiene styrene (ABS) films.

[0162] In each of the above applications, the composition may be applied by conventional application methods such as brushing, roll coating, e.g., using 4-application roll equipment where the composition is solvent-free or 2-application roll equipment for compositions containing solvent, doctor blade application, printing methods, and spraying methods including, but not limited to, air atomized spray, air assisted spray, airless spray, and high volume low pressure spray. For coating and adhesive applications, it is recommended that the composition be applied to a wet film thickness of 10 to 500 μm. Applying thinner layers within this range can be more economical and reduce the possibility of thick cured areas that require sanding for application of the coating. However, a high degree of control must be exercised when applying thinner coatings or layers to avoid the formation of discontinuous cured films.

[0163] Various features and embodiments of the present disclosure are described in the following examples, which are intended to be representative and not limiting. EXAMPLES

[0164] In the examples, the following materials are used: Glycerin Carbonate: Glycerin Carbonate, Jeffsol, available from Huntsman TM . SuccAnh: Succinic anhydride, available from Sigma-Aldrich. Grillonit RV 1812: 1,6-hexane diglycidyl ether available from EMS-CHEMIE AG. TEBAC: benzyltriethylammonium chloride, available from Sigma-Aldrich. Adiansol: Adiansol GO 2280 T, a polyether triol containing primary hydroxyl groups and having a hydroxyl number of 130 mg KOH / g, available from Arkema; TMP: Trimethylolpropane, available from Sigma-Aldrich. TPG: Tripropylene glycol, available from Sigma-Aldrich. Glycerol: Glycerol available from Alfa Aesar. SeA: Sebacic acid, available from Sigma-Aldrich. PEI: Polyethylenimine with a weight average molecular weight (Mw) of 800 g / mol, available from Sigma-Aldrich.

[0165] <Reaction of glycerol carbonate with succinic anhydride (GC-Succ)>

[0166] [ka]

[0167] Glycerol carbonate (135 g) and succinic anhydride (120 g) were dissolved in N 2 The mixture was stirred under atmosphere in a round bottom flask. The initial temperature was set at 85°C and gradually increased to 100°C following the consumption of succinic anhydride. The reaction was monitored by 1H-NMR and followed by disappearance of the glycerol carbonate peak: after 20 hours, the reaction was stopped when the percentage of starting carbonate approached 1%. The carbonate equivalent weight (CEW) (208.06 g / eq) was calculated by titration using toluene as an internal standard. 1H-NMR (250MHz, DMSO-d6): δ=5.08-4.99(m, 1H), 4.57(t, J=8.6Hz, 1H), 4.30- 4.24(m, 3H), 2.65-2.41(m, 4H);13CNMR(62.5MHz, DMSO-d6):δ=173.5, 172.0, 1 54.8, 74.4, 66.1, 63.6, 28.7; FT-IR(cm-1):3019(br), 2660(w), 1781(s), 173 0(s), 1696(s), 1397(m), 1160(s), 1087(m), 1053(m), 995(m), 952(m), 769(s).

[0168] <Synthesis of CC-epoxy terminal capper (adduct B)>

[0169]

Chem.

[0170] A mixture of GC-Succ (258 g), Grilonit RV 1812 (363 g), and TEBAC (9.30 g, 1.5 wt%) was stirred in a three-necked round-bottom flask under an N 2 atmosphere. The temperature was set at 75 °C, and the reaction was monitored by 1H-NMR. After the procedure was completed, the carbonate equivalent (540 g / equivalent) was determined by titration with toluene.

[0171] <Synthesis of carboxy-PESs>

[0172]

Chem.

[0173] Procedure A: A mixture of trifunctional alcohol (1 mol) and succinic anhydride (3 mol) was stirred in a three-necked round-bottom flask under an N 2 atmosphere. The temperature was set at 100 °C, and the reaction was monitored by 1H-NMR. The reaction mixture was maintained under these conditions until the OH signal in the NMR spectrum completely disappeared and Av became constant and approached the desired value.

[0174] Procedure B: A mixture of bifunctional alcohol (1 mol) and succinic anhydride (2 mol) was stirred in a three-necked round-bottom flask under an N 2 atmosphere. The temperature was set at 100 °C, and the reaction was monitored by 1H-NMR. The reaction mixture was maintained under these conditions until the OH signal in the NMR spectrum completely disappeared and Av became constant and approached the desired value.

[0175] Carboxy-PESs (C-1 to C-4) were prepared according to the composition shown in Table 1 and the above method.

[0176] [Table 1]

[0177] <Synthesis of cyclic carbonate-PESs> The following procedure was used to prepare the cyclic carbonate-PESs.

[0178] [ka]

[0179] Procedure A: In a three-neck round-bottom flask and N 2 Under atmosphere, a mixture of trifunctional carboxy-PESs (1 mole), adduct B (3 moles) and TEBAC (1.5 wt%) was slowly heated to 65° C. (95° C. for C-2) and stirred. The reaction mixture was maintained under these conditions until no epoxy signal was detected in the NMR spectrum.

[0180] Procedure B: In a three-neck round-bottom flask and N 2 Under atmosphere, a mixture of bifunctional carboxy-PESs (1 mole), adduct B (2 moles) and TEBAC (1.5 wt%) was slowly heated and stirred to 85° C. The reaction mixture was maintained under these conditions until the Av was less than 5 mg KOH / g.

[0181] Procedure C: In a three-neck round-bottom flask and N 2 A mixture of dicarboxylic acid (1 mole), adduct B (2 moles) and TEBAC (1.5 wt%) was slowly heated to 85° C. under atmosphere and stirred. The reaction mixture was maintained under these conditions until the Av was less than 5 mg KOH / g.

[0182] [Table 2]

[0183] As in Example 1, the trifunctional compounds of Examples 2, 3 and 5 were synthesized using the synthesis route under mild conditions according to the invention. Attempts to prepare the same products as in Example 1 using the conditions reported in EP 3 401 350 A1 gave homopolymerization of the reaction mixture. The reaction conditions according to the invention allowed the preparation of all products without such problems.

[0184] <Adhesive Compound> Three adhesive formulations (AF1-AF3) were prepared by mixing three of the cyclic carbonate functionalized polyesters defined above (Table 3: Examples 2, 4 and 5) with a nucleophile. The formulations are defined in Table 4 below.

[0185] [Table 3]

[0186] These adhesive formulations were used to carry out lap shear tests using PET-PE substrates according to DINEN 1465. The results of the tests carried out at room temperature and at 40° C. are shown in Table 5 below.

[0187] [Table 4]

[0188] It is clear that all adhesive formulations exhibited good adhesive strength.

Claims

1. 1. A method for preparing a cyclic carbonate functional polyester comprising the steps of: (1) reacting glycerol carbonate with an anhydride to form an adduct (A) having the general structure of formula (I); 【Chemistry 1】 wherein n is 1, 2 or 3; (2) reacting the adduct (A) with at least one polyepoxide compound to form an adduct (B) having the general structure of formula (II); 【Chemistry 2】 In the formula, R １ represents the residue of a dihydric phenol or a dihydric alcohol, n is 1, 2 or 3; and (3) reacting said adduct (B) with at least one polycarboxylic acid to form said cyclic carbonate functional polyester; A method comprising:

2. 10. The method of claim 1 for preparing a cyclic carbonate functional polyester, comprising the steps of: (A) reacting glycerol carbonate with an anhydride to form an adduct (A) having the general structure of formula (I); 【Chemistry 3】 wherein n is 1, 2 or 3; (B) reacting the adduct (A) with at least one polyepoxide compound to form an adduct (B) having the general structure of formula (II): 【Chemistry 4】 In the formula, R １ represents a residue of a dihydric phenol or a dihydric alcohol, n is 1, 2 or 3, (C) providing at least one polycarboxylic acid; and (D) reacting said adduct (B) with at least one polycarboxylic acid to form said cyclic carbonate functional polyester; A method comprising:

3. The method of claim 1, wherein the anhydride is selected from the group consisting of maleic anhydride, adipic anhydride, succinic anhydride, alkyl succinic anhydride, alkenyl succinic anhydride, glutaric anhydride, alkyl glutaric anhydride, alkenyl glutaric anhydride, and mixtures thereof.

4. 4. The reaction of the glycerol carbonate with the anhydride, wherein the anhydride is reacted with the glycerol carbonate within the following limitations: i) a molar ratio of anhydride:glycerol carbonate ranging from 2:1 to 0.8:1; ii) a temperature in the range of 60°C to 120°C; and iii) under anhydrous conditions; The method according to any one of claims 1 to 3, wherein the method is carried out under at least one of the following conditions:

5. The process according to any one of claims 2 to 4, wherein the polycarboxylic acid of step C is a carboxyl-functional polyester (carboxy-PES).

6. The carboxyl functional polyester (carboxy-PES) is i) providing a hydroxyl functional polyester having two or more hydroxyl groups; and ii) reacting said hydroxyl functional polyester with a carboxylic acid or anhydride thereof; The method of claim 5 provided by

7. The method of claim 6, wherein the hydroxyl functional polyester has a hydroxyl number of from 50 to 300 mg KOH / g.

8. 6. The method of claim 5, wherein the carboxyl 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. 9. The method according to claim 2, wherein in step B, the polyepoxide compound has an epoxy equivalent weight of 100 to 700 g / eq.

10. 10. The process according to any one of claims 2 to 9, wherein in step B, the molar ratio of the adduct (A) to the at least one polyepoxide compound is from 1:1.5 to 1:

3.

11. Steps B and D are as follows: i) at a temperature in the range of 40°C to 100°C; and / or ii) in the presence of a catalytic amount of a phase transfer catalyst; The method according to any one of claims 2 to 10,

12. The process according to any one of claims 2 to 11, wherein steps A to D are carried out continuously in one vessel without separation of intermediate products.

13. 13. The method of any one of claims 1 to 12, wherein in step D, the equivalent ratio of carboxyl groups to epoxy groups is in the range of (1.0-1.2):1.

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