Coatings, adhesives and elastomers utilizing acetoacetate endblocked polyols derived from thermoplastic polyesters - Patents.com

Abstract

The present invention relates to acetoacetate end-capped polyols comprising at least one residue of a polyol derived from a thermoplastic polyester, polymers comprising the end-capped polyols, and uses of such end-capped polyol-containing materials. The present invention also relates to a method of making a polymer composition comprising an acetoacetate end-capped polyol comprising at least one residue of a polyol derived from a thermoplastic polyester.

Description

[Technical field]

[0001] The present invention relates to an acetoacetate end-capped polyol comprising at least one residue of a polyol derived from a thermoplastic polyester, a polymer comprising the end-capped polyol, and the use of such end-capped polyol-containing materials. The present invention also relates to a method of making a polymer composition comprising the acetoacetate end-capped polyol. In particular, the method of making the polymer composition may advantageously utilize the C-Michael addition reaction, the use of which is facilitated by the composition of the end-capped polyol.

[0002] The acetoacetate endblocked polyol of the present invention can be used to make a replacement for polyurethanes prepared from free isocyanates.Polyurethanes are extremely versatile materials and are used in a wide variety of applications, such as foam insulation, car seats, paint coatings, adhesives, sealants, tubing and wiring, elastomers, and wear-resistant coatings.Polyurethanes can be used in protective coatings (e.g., applied to wood, metal, or plastic), adhesives for rigid substrates (e.g., composites, metals), adhesives for flexible substrates (fabrics, plastic films), applications that require moisture resistance (e.g., products for outdoor use, or product encapsulation, for example, in electronic devices), and tough and wear-resistant elastomers.

[0003] Polyurethanes are also used in a wide variety of forms, including non-porous materials such as elastomers, and porous materials such as low density flexible foams, high density flexible foams, and microcellular foams.

[0004] Polyurethanes, both in dispersed and undispersed form, are also known to find use in adhesives, such as hot melt adhesives, moisture curing adhesives and two-component reactive adhesives, for example in the furniture industry.

[0005] Polyurethanes, in both cast thermoset and thermoplastic forms, are known to find use in composites, For example, polyurethanes can be used as pre-matrix, fiber impregnating resins, and as binder resins in composites reinforced with fibers such as carbon, glass, or polyester.

[0006] Polyurethane elastomers can be used in wiring, tubing, belting, sportswear (e.g., sports shoes, goggles, ski boots), films / sheets, automotive interiors (e.g., grips, armrests, consoles), and many other applications.

[0007] Typically, polyurethane resins (and the subsequent corresponding cured polyurethane polymer matrix products) can be made by reacting isocyanates with polyols. Although such polyurethanes prepared from isocyanates have their advantages, they pose limitations when considering the safety, environmental and health factors associated with the use and handling of isocyanates. The toxicity profile of the monomeric isocyanates in the polyisocyanate curing agents present in such polyurethanes has been the subject of investigation in recent years, and changes driven by legislation have led the polyurethane manufacturing industry to search for new polymer resins and matrices, particularly new polymer resins and matrices that do not require the presence of isocyanates, but where the performance of the polymer for its intended end use is not compromised. For this reason, new technologies are required to produce polymers that provide the beneficial polyurethane mechanical and chemical properties, but do not use isocyanates. Such new technologies are believed to be more sustainable.

[0008] Michael addition (or Michael reaction) chemistry is believed to provide an alternative sustainable process by which useful polymers can be prepared in the absence of isocyanates. Michael addition chemistry has been studied and used in several applications (Noomen, A., Prog. Org. Coat, 32, 137-142 (1997)).

[0009] The key chemical components of the Michael addition system are an electron-deficient C=C double bond, an acidic C-H bond, and a base catalyst strong enough to abstract a proton from this C-H bond to provide a nucleophilic carbanion that can add to the C=C double bond. Thus, a carbon-carbon bond is formed between two molecules through the reaction of the donor molecule's nucleophilic carbanion. The second proton of the donor molecule is available for a similar subsequent reaction.

[0010] [ka]

[0011] The present invention seeks to provide improved polyols that may find utility in polymer compositions so as to overcome the problems associated with isocyanate-derived polyurethanes.

[0012] Thus, the present invention provides an acetoacetate end-capped polyol, at least one residue of a polyol derived from virgin thermoplastic polyester, recycled thermoplastic polyester, and mixtures thereof; and optionally a) at least one dimer fatty residue selected from dimer fatty acid residues, dimer fatty diol residues, and dimer fatty diamine residues; and b) at least one residue of a linear or branched C2 to C36 diacid or diol.

[0013] In an alternative embodiment, the present invention provides a polymer composition comprising the acetoacetate endcapped polyol.

[0014] The present invention also provides a method for preparing a polyol having an acetoacetate endblocked polyol, comprising reacting the acetoacetate endblocked polyol with an acrylate to form a polyol having an acetoacetate endblocked polyol. (i) a polymeric resin, or (ii) providing a method of making a polymer composition comprising forming a polymer matrix.

[0015] The invention further provides the use of a polyol of the first aspect to form a polymer composition.

[0016] Additionally, the present invention provides a coating comprising the acetoacetate endblocked polyol or the polymer composition comprising the acetoacetate endblocked polyol.

[0017] It will be understood that any upper or lower quantity or range limits set forth herein may be independently combined.

[0018] It will be understood by one of ordinary skill in the art that when describing the number of carbon atoms in a substituent (e.g., "C1-C6"), the number refers to the total number of carbon atoms present in the substituent, including any present in any branching groups. Additionally, when describing the number of carbon atoms in, for example, a fatty acid, this refers to the total number of carbon atoms, including the carbon atoms in the carboxylic acid and any carbon atoms present in any branching groups.

[0019] Many of the chemicals that can be used to produce the polyol or polymer compositions of the present invention are obtained from natural sources. Such chemicals typically contain mixtures of chemical species due to their natural origin. Due to the existence of such mixtures, the various parameters defined herein may be average values ​​and may be non-integer values.

[0020] The term "polyol" is well known in the art and refers to a molecule that contains two or more hydroxyl groups.

[0021] As used herein, the term "polyester" refers to a molecule or group that has two or more ester bonds.

[0022] As used herein, unless otherwise defined, the term "dimer fatty residue" refers to a residue of a dimer fatty acid (also called a dimer fatty diacid) or a residue of a dimer fatty acid derivative, such as a dimer fatty diol or a dimer fatty diamine.

[0023] The term "functionality" as used herein with respect to a molecule or a portion of a molecule refers to the number of functional groups in that molecule or portion of a molecule. A "functional group" refers to a group in a molecule that can participate in a chemical reaction. For example, carboxylic acid groups, hydroxyl groups, and amine groups are all examples of functional groups. For example, a diacid (having two carboxylic acid groups) and a diol (having two hydroxyl groups) both have a functionality of two, and a triacid and a triol both have a functionality of three.

[0024] The term "dimeric fatty acid" (also called dimeric fatty diacid) is well known in the art and refers to the dimerization products of mono- or polyunsaturated fatty acids and / or esters thereof. The related term trimer fatty acid similarly refers to the trimerization products of mono- or polyunsaturated fatty acids and / or esters thereof.

[0025] The terms polyols derived from virgin thermoplastic polyesters, recycled thermoplastic polyesters, and mixtures are well known in the art and refer to the product obtained from heating a thermoplastic polyester with glycol to give a digested polyol.

[0026] The present invention provides an acetoacetate end-capped polyol, The polyol comprises at least one residue of a polyol derived from virgin thermoplastic polyester, recycled thermoplastic polyester, and mixtures thereof.

[0027] The acetoacetate endcapped polyols of the present invention optionally and preferably comprise a) at least one dimer fatty residue selected from dimer fatty acid residues, dimer fatty diol residues, and dimer fatty diamine residues; and / or b) contains at least one residue of a linear or branched C2-C36 diacid or diol.

[0028] Thus, the acetoacetate end-blocked polyol can be considered to include at least two components, one of which is an acetoacetate end-blocking component, and the other of which is at least one residue of a polyol derived from a virgin thermoplastic polyester, a recycled thermoplastic polyester, and a mixture thereof, as defined above. Alternatively, in some embodiments, the acetoacetate end-blocked polyester polyol includes three components, one of which is an acetoacetate end-blocking component, and the other two of which are at least one residue of a polyol derived from a virgin thermoplastic polyester, a recycled thermoplastic polyester, and a mixture thereof, and the presence of a) or b) as defined above (b) is particularly preferred). Additionally, in a further alternative embodiment, the acetoacetate end-blocked polyester polyol includes four components, one of which is an acetoacetate end-blocking component, and the other three of which are at least one residue of a polyol derived from a virgin thermoplastic polyester, a recycled thermoplastic polyester, and a mixture thereof, and a) and b) as defined above.

[0029] Suitably, the polyol, prior to endcapping, may be a diol, triol, tetrol, pentol, or hexol. Preferably, the polyol, prior to endcapping, is a diol, triol, or tetrol, more preferably a diol or triol. Most preferably, the polyol, prior to endcapping, is a diol.

[0030] The polyol may contain at least two ester bonds, preferably at least three ester bonds, more preferably at least four ester bonds, and even more preferably at least five ester bonds.

[0031] The polyol may contain up to 10 ester bonds, preferably up to 8 ester bonds, and more preferably up to 7 ester bonds.

[0032] The polyol may be a polyester.

[0033] The polyol may include at least one ether linkage. The polyol may be a polyester ether.

[0034] In a less preferred embodiment, the polyol may contain at least one amide bond.

[0035] In a less preferred embodiment, the polyol may be a polyesteramide.

[0036] In a less preferred embodiment, the polyol may be a polycarbonate.

[0037] The acetoacetate endcapped polyol may have a molecular weight (number average) of at least 500, preferably at least 800, more preferably at least 1000, even more preferably at least 1500, and particularly preferably at least 1800.

[0038] The acetoacetate end-capped polyol may have a molecular weight (number average) of up to 5000, preferably up to 4000, more preferably up to 3000, even more preferably up to 2500, and particularly preferably up to 2200.

[0039] The acetoacetate endblocking component of the acetoacetate endblocked polyol may be selected from one or more of the following: methyl acetoacetate, ethyl acetoacetate, tert-butyl acetoacetate, isopropyl acetoacetate, isobutyl acetoacetate, and ketene derivatives. Preferably, the acetoacetate endblocking is methyl acetoacetate.

[0040] The acetoacetate end-capped polyol may contain at least 10% by weight acetoacetate end-blocking, preferably at least 40% by weight, more preferably at least 50% by weight acetoacetate end-blocking.The acetoacetate end-capped polyol may contain up to 95% by weight acetoacetate end-blocking, preferably up to 85% by weight, more preferably up to 75% by weight acetoacetate end-blocking.

[0041] The polyols include at least one residue of polyols derived from virgin thermoplastic polyesters, recycled thermoplastic polyesters, and mixtures, which are described in more detail herein.

[0042] Polyols derived from virgin thermoplastic polyesters, recycled thermoplastic polyesters and mixtures are well known in the art and refer to the products obtained from heating thermoplastic polyesters with glycols to give digested polyols.

[0043] Thermoplastic polyesters suitable for use in making polyester polyols are well known in the art. Virgin thermoplastic polyesters are condensation polymers produced from the reaction of glycols with aromatic dicarboxylic acids or acid derivatives. Recycled thermoplastic polyesters are generally derived from recycled virgin thermoplastic polyester waste, and previously recycled thermoplastic polyester waste can also be utilized in the present invention. Examples of suitable thermoplastic polyesters include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), glycol-modified polyethylene terephthalate (PETG), copolymers of terephthalic acid and 1,4-cyclohexanedimethanol (PCT), PCTA (isophthalic acid modified PCT), polyhydroxyalkanoates (e.g., polyhydroxybutyrate), copolymers of diols and 2,5-furandicarboxylic acid or dialkyl 2,5-furandicarboxylate (e.g., polyethylene furanoate), copolymers of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and isophthalic acid, terephthalic acid, or orthophthalic acid derivatives, dihydroferulic acid polymers, and the like. Further examples of polyester thermoplastics are described in Modern Polyesters: Chemistry and Technology of Polyesters and Copolyesters, J. Scheirs and T. Long, eds., Wiley Series in Polymer Science, 2003, John Wiley & Sons, Ltd. Hoboken, NJ. Other examples of thermoplastic polyesters can be found in Chapters 18-20 of Handbook of Thermoplastics, O. Olabisi, ed., 1997, Marcel Dekker, Inc. New York.For further examples of suitable thermoplastic polyesters, see US Patent Application Publication No. 2009 / 0131625, the teachings of which are incorporated herein by reference.

[0044] Additionally, polyols derived from polyethylene terephthalate, particularly recycled polyethylene terephthalate (rPET), virgin PET, and mixtures thereof are particularly preferred in the present invention. rPET suitable for use in making the polyester polyols of the present invention can come from a variety of sources. The most common source is post-consumer waste streams of PET from plastic bottles or other containers. rPET can be colorless or contain dyes (e.g., green, blue, or other colors), or mixtures thereof. Small amounts of organic or inorganic foreign matter (e.g., paper, other plastics, glass, metal, etc.) may be present. A desirable source of rPET is "flake" rPET, from which many of the common impurities present in scrap PET bottles have previously been removed. Another desirable source of rPET is pelletized rPET, which is made by melting rPET and extruding it through a metal filter mesh to further remove particulate impurities. Because PET plastic bottles are currently produced in much greater quantities than any recycling effort can match, scrap PET will continue to be available in abundance. The present invention allows these scrap PETs to enjoy wider utility in products made from the original PET material, since the polyols can undergo new reactions to form polymers with properties different from those of the original PET; direct recycling of PET to rPET does not allow for such divergence in product properties to be realized.

[0045] Glycols suitable for use in making polyester polyols are also well known in the art. In this context, "glycol" means a linear or branched aliphatic or cycloaliphatic compound or mixture of compounds having two or more hydroxyl groups. However, other functional groups, especially ether or ester groups, may be present in the glycol. In the preferred glycols, two of the hydroxyl groups are separated by 2 to 10 carbons, preferably 2 to 5 carbons. Suitable glycols include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, pentaerythritol, sorbitol, neopentyl glycol, glycerol, trimethylolpropane, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, bisphenol A ethoxylate, diethylene glycol, dipropylene glycol, triethylene glycol, 1,6-hexanediol, tripropylene glycol, tetraethylene glycol, polyethylene glycols with a number average molecular weight of up to about 400 g / mol, block or random copolymers of ethylene oxide and propylene oxide, etc. Propylene glycol is particularly preferred. Most preferably, the glycol is recycled glycol, in particular recycled propylene glycol. Propylene glycol recovered from used de-icing fluids is one example of a usable source of used glycol that can be recovered and made into recycled propylene glycol; as such a particularly preferred embodiment, polyol can be produced from rPET digested in the presence of recycled propylene glycol to produce polyol from 100% recycled material.

[0046] As described above, methods for preparing polyols from thermoplastic polyesters are known via heating the thermoplastic polyester with a glycol to obtain a digested polyol. However, a brief overview of the preparation method is provided here. The thermoplastic polyester and glycol are heated, optionally in the presence of a catalyst, to give a digested intermediate. The digested intermediate is typically a mixture of glycol reactants, glycol generated from the thermoplastic polyester, terephthalate oligomers, and other glycolysis products. For example, when PET or rPET is the thermoplastic polyester, the digested intermediate includes a mixture of glycol reactants, ethylene glycol (generated from PET or rPET), bis(2-hydroxyalkyl)terephthalate ("bis(2-hydroxyalkyl)terephthalate, BHAT"), higher PET oligomers, and other glycolysis products. Various forms of similar digestion mixtures have been prepared and characterized previously (see, for example, D. Paszun et al., Ind. Eng. Chem. Res. 36 (1997) 1373 and N. Ikladious, J. Elast. Plast. 32 (2000) 140). Heating is advantageously carried out at a temperature in the range of 80° C. to 260° C. In one embodiment, when the thermoplastic polyester is polyethylene terephthalate, the digestion intermediate comprises glycol and terephthalate components. The terephthalate component preferably comprises 45 to 70% by weight of bis(hydroxyalkyl) terephthalate (as measured by gel permeation chromatography using ultraviolet detection). In a preferred embodiment, the terephthalate component further comprises 20 to 40% by weight of terephthalate dimer. In another preferred embodiment, the terephthalate component of the digestion intermediate comprises 45-65% by weight of bis(hydroxyalkyl)-terephthalate, 20-35% by weight of terephthalate dimer, and 5-15% by weight of terephthalate trimer. In another preferred embodiment, the terephthalate component comprises 50-60% by weight of bis(hydroxyalkyl)-terephthalate, 25-30% by weight of terephthalate dimer, and 8-12% by weight of terephthalate trimer.

[0047] component a) at least one dimer fatty residue selected from dimer fatty acid residues, dimer fatty diol residues, and dimer fatty diamine residues of the acetoacetate endcapped polyester polyol; This is explained in more detail here.

[0048] Generally, the at least one dimer fatty residue may include any of the characteristics or preferences described herein with respect to a dimer fatty acid, a dimer fatty diol, or a dimer fatty diamine, as detailed below.

[0049] Suitably, at least one dimeric fatty residue may be saturated or unsaturated, however, preferably, at least one dimeric fatty residue is saturated.

[0050] The dimer fatty residue is essentially fatty, which may increase the hydrophobicity of the polyol. The presence of the dimer fatty residue may make the polyol more amorphous, non-crystalline or substantially non-crystalline. The amorphous nature of the polyol may increase the flexibility and / or decrease the tensile strength of a polymer matrix containing the polyol, as further described below.

[0051] The acetoacetate end-capped polyol may contain at least 5% by weight, preferably at least 10% by weight, of dimeric fatty residues. The polyol may contain up to 90% by weight, preferably up to 85% by weight, more preferably up to 80% by weight, of dimeric fatty residues.

[0052] The at least one dimeric fatty residue selected can be a dimeric fatty acid residue.

[0053] Suitably, the acetoacetate endcapped polyol may contain at least 5% by weight, preferably at least 10% by weight, of dimeric fatty acid residues. The polyol may contain up to 30% by weight, preferably up to 20% by weight, of dimeric fatty acid residues.

[0054] Dimer fatty acids are described in TE Breuer, "Dimer Acids," in JI Kroschwitz (ed.), Kirk-Othmer Encyclopaedia of Chemical Technology, 4th Ed., Wily, New York, 1993, Vol. 8, pp. 223-237. They are prepared by polymerizing fatty acids under pressure and then removing most of the unreacted fatty acid starting material by distillation. The final product usually contains some small amounts of mono- and trimer fatty acids, but is mostly made from dimer fatty acids. The resulting product can be prepared with various ratios of different fatty acids as desired.

[0055] The ratio of dimer to trimer fatty acids can be varied by modifying the process conditions and / or the unsaturated fatty acid feedstock, as known to those skilled in the art. The dimer fatty acids can be isolated in substantially pure form from the product mixture using purification techniques known in the art, or alternatively, a mixture of dimer and trimer fatty acids can be used.

[0056] The dimeric fatty acid or dimeric fatty residue used in the present invention is preferably derived from the dimerization product of C10-C30 fatty acids, more preferably C12-C24 fatty acids, in particular C14-C22 fatty acids, even more preferably C16-C20 fatty acids, and specifically C18 fatty acids. Thus, the dimeric fatty acid obtained preferably contains 20-60, more preferably 24-48, in particular 28-44, even more preferably 32-40, and specifically 36 carbon atoms.

[0057] Suitably, the fatty acid from which the dimeric fatty acid is derived may be selected from linear or branched unsaturated fatty acids, with linear fatty acids being preferred. The unsaturated fatty acids may be selected from fatty acids having either cis / trans configuration and may have one or more unsaturated double bonds. However, monounsaturated fatty acids are particularly preferred. Most preferably, the fatty acid is a linear monounsaturated fatty acid.

[0058] Suitably, the dimer fatty acid may be non-hydrogenated, hydrogenated or partially hydrogenated. Hydrogenated dimer fatty acid residues (whether derived from diacids, diols or diamines) may have better oxidative or thermal stability and may be desirable in polymers containing polyols, and therefore preferably the dimer fatty acid is hydrogenated or partially hydrogenated.

[0059] Suitable dimer fatty acids are preferably derived from the dimerization products of oleic acid, linoleic acid, linolenic acid, palmitoleic acid, or elaidic acid (i.e., are dimer equivalents thereof). In particular, suitable dimer fatty acids are preferably derived from oleic acid.

[0060] The dimeric fatty acid may be the dimerization product of a mixture of unsaturated fatty acids obtained from the hydrolysis of natural fats and oils, such as sunflower oil, soybean oil, olive oil, rapeseed oil, cottonseed oil, or tall oil.

[0061] The molecular weight (weight average) of the dimeric fatty acid is preferably in the range of 450-690, more preferably 500-640, particularly 530-610, and specifically 550-590.

[0062] In addition to dimeric fatty acids, dimerization usually results in the presence of various amounts of trimeric fatty acids (so-called "trimers"), oligomeric fatty acids, and monomeric fatty acids (so-called "monomers"), or their esters. The amount of monomers can be reduced, for example, by distillation. The presence of these optional dimerization reaction products is tolerated, since distillation of dimeric fatty acid products increases production costs, however, purification by distillation of dimeric fatty acids may be preferred for some niche applications.

[0063] Suitably, the trimer fatty acid is preferably derived from the trimerization product of the materials mentioned for the dimer fatty acid, and is preferably a trimer of C10-C30, more preferably C12-C24, particularly C14-C22, even more preferably C16-C20, and especially C18 fatty acids.To this end, the trimer fatty acid preferably contains in the range of 30-90, more preferably 36-72, especially 42-66, even more preferably 48-60, and in particular 54 carbon atoms.

[0064] The molecular weight (weight average) of the trimer fatty acid is preferably in the range of 750-950, more preferably 790-910, particularly 810-890, and specifically 830-870.

[0065] Additionally or alternatively, tetrameric fatty acids and higher oligomers (hereinafter both referred to as oligomeric acids) may be formed during the production of dimeric fatty acids. Thus, such oligomeric acids may be present in the dimeric fatty acids used in the present invention in combination with trimer fatty acids and / or dimer fatty acids and / or mono-fatty acid mono-acids, as mentioned above.

[0066] The oligomeric acid is preferably an oligomer containing 4 or more units derived from a C10-C30, more preferably a C12-C24, particularly a C14-C22, and specifically a C18 fatty acid. The molecular weight (weight average) of the oligomeric acid is suitably greater than 1000, preferably 1200-1800, more preferably 1300-1700, particularly 1400-1600, and specifically 1400-1550.

[0067] The dimeric fatty acid used in the present invention may preferably have a dimeric fatty acid (or dimer) content of more than 60% by weight, more preferably more than 70% by weight, in particular more than 80% by weight, and in particular more than 85% by weight. Most preferably, the dimer content of the dimeric fatty acid is in the range of 90% to 99% by weight.

[0068] In an alternative embodiment, the dimeric fatty acid preferably has a dimeric fatty acid (or dimer) content in the range of 70% to 96% by weight, which may be particularly applicable to two-component or cross-linked systems.

[0069] Additionally or alternatively, particularly preferred dimeric fatty acids may have a trimer fatty acid (or trimer) content of less than 40% by weight, more preferably less than 30% by weight, in particular less than 20% by weight, and particularly less than 15% by weight. The trimer fatty acid content may be less than 4% by weight.

[0070] Furthermore, the dimer fatty acids preferably contain less than 10% by weight, more preferably less than 5% by weight, in particular less than 4% by weight, and particularly less than 2.5% by weight of mono fatty mono acids (or monomers).

[0071] All of the above weight percentage values ​​are based on the total weight of polymerized fatty acid and mono fatty acid present in the dimer fatty acid.

[0072] The at least one dimer fatty residue selected can be a dimer fatty diol residue.

[0073] Suitable dimer fatty diols can be formed by hydrogenation of the corresponding dimer fatty acids.

[0074] Dimer fatty acid (or dimer fatty diacid) can be converted to dimer fatty diol as known in the art. Dimer fatty diol can have properties as described herein for dimer fatty acid (or dimer fatty diacid), except that the acid group in the dimer fatty acid is replaced with a hydroxyl group in the dimer fatty diol. In a similar manner, trimer fatty triacid can be converted to trimer fatty triol, which can have properties as described herein for trimer fatty triacid. Thus, the same preferred embodiments detailed herein for dimer fatty acid can be applied to the corresponding preferred embodiments of the dimer fatty diol residue component of the polyol.

[0075] Suitably, prior to endcapping, the polyol may comprise at least 50% by weight, preferably at least 60% by weight, of dimeric fatty diol residues. The polyol may comprise up to 90% by weight, preferably up to 80% by weight, of dimeric fatty diol residues. These amounts of dimeric fatty residues may provide the polyol with a suitable amount of hydrophobicity and / or amorphous character without excessively decreasing the tensile strength or hardness of a polymer matrix comprising the polyol.

[0076] Suitably, the acetoacetate endcapped polyol may contain at least 5% by weight, preferably at least 10% by weight, of dimeric fatty acid residues. The polyol may contain up to 30% by weight, preferably up to 20% by weight, of dimeric fatty diol residues.

[0077] The dimer fatty diol may be hydrogenated. The dimer fatty diol may be non-hydrogenated.

[0078] Additionally or alternatively, the polyol may comprise at least one dimer fatty diamine residue, so that the at least one selected dimer fatty diamine residue may be a dimer fatty diamine residue, however, this embodiment is less preferred and the polyol may not comprise a dimer fatty diamine residue and therefore may not comprise an associated amine group in component a) of the polyol.

[0079] component b) at least one residue of a linear or branched C2-C36 diacid or diol of the acetoacetate end-capped polyester polyol is This is explained in more detail here.

[0080] Preferably, at least one residue of a C2-C36 diacid or diol has at least two functional groups selected from a carboxylic acid group, a hydroxyl group, and mixtures thereof. In some embodiments, the diacid or diol preferably has only two functional groups selected from a carboxylic acid group, a hydroxyl group, and mixtures thereof.

[0081] The polyol before end-capping may contain at least 10% by weight, preferably at least 15% by weight, more preferably at least 20% by weight of component b). The polyol before end-capping may contain up to 50% by weight, preferably up to 40% by weight of b). It will be understood that the level of component b) in the end-capping polyol is at least 0.10% by weight, preferably at least 0.15% by weight, more preferably at least 0.20% by weight. It will be further understood that the level of component b) in the end-capping polyol may contain up to 15% by weight, preferably up to 8% by weight of dimeric fatty diol residues. These amounts of b) may provide a suitable amount of crystallinity to the polyol without excessively reducing the flexibility of the polymer matrix containing the polyol.

[0082] It should be understood that component b) is a non-dimeric diacid or diol and is different from the dimeric fatty acids and diols described above for component a).

[0083] Suitable non-dimer diacids can be aliphatic or aromatic (such as phthalic acid, isophthalic acid, and terephthalic acid) and include dicarboxylic acids and their esters, preferably alkyl esters thereof.

[0084] Preferably, the polyol comprises at least two residues of a linear or branched C2-C36 diacid or diol, and in some embodiments may comprise at least three residues of a linear or branched C2-C36 diacid or diol, each independently selected from the preferred embodiments detailed below. The inclusion of more than one type of residue of a linear or branched C2-C36 diacid or diol allows the physical properties of the polymer comprising the polyol to be tailored to its particular end use.

[0085] In a preferred embodiment, b) comprises at least one residue of a linear or branched C6-C36 dicarboxylic acid or diol. The presence of b) in the polyol may make the polyol more crystalline due to the long aliphatic carbon chain present in the at least one residue of a C6-C36 linear or branched dicarboxylic acid or diol. The increased crystallinity may increase the tensile strength and / or hardness of a polymer matrix containing the polyol. It may also increase the green strength of an adhesive formed from such a polyol-containing polymer. The at least one residue of a C6-C36 linear or branched diacid may comprise an ester thereof, preferably an alkyl ester, more preferably a dimethyl ester.

[0086] At least one residue of a C6-C36 linear or branched dicarboxylic acid or diol may be linear, which may include terminal carboxyl or hydroxyl groups that are bridged by alkyl or alkenyl groups.

[0087] At least one residue of a C6-C36 linear or branched diacid or diol may be branched. At least one residue of a C6-C36 linear or branched diacid or diol may include at least one methyl branch. At least one residue of a C6-C36 linear or branched diacid or diol may include at least one ethyl branch.

[0088] At least one residue of the C6-C36 straight or branched dicarboxylic acid or diol can be saturated or unsaturated, preferably saturated.

[0089] Preferably, the C6 to C36 dicarboxylic acid or diol is a straight-chain dicarboxylic acid.

[0090] The C6-C36 dicarboxylic acid or diol may be preferably a C18-C26 dicarboxylic acid or diol, more preferably a C18-C26 dicarboxylic acid or diol. The C6-C36 dicarboxylic acid or diol may be preferably a C18 dicarboxylic acid. The C6-C36 dicarboxylic acid or diol may be preferably a C26 dicarboxylic acid.

[0091] The C6-C36 diacid or diol may be derived from a C6-C36 diacid or dialkyl ester obtained by a metathesis reaction, preferably a self-metathesis reaction. The metathesis reaction may occur in the presence of a catalyst. Suitable metathesis catalysts are disclosed in WO 2008 / 065187 and WO 2008 / 034552, which are incorporated herein by reference.

[0092] Additionally or alternatively, it is particularly preferred that component b) comprises at least one residue of a linear dicarboxylic acid having a carbon chain in the range of 4 to 12 carbon atoms, more preferably b) comprises at least one residue of a linear dicarboxylic acid having 6 to 10 carbon atoms. Particularly preferred examples include adipic acid, glutaric acid, succinic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, heptanedicarboxylic acid, octanedicarboxylic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and dodecanedicarboxylic acid. Adipic acid is particularly preferred. More specifically, this embodiment is particularly preferred when component b) comprises at least two or more residues of said C2-C36 diacids or diols.

[0093] Alternatively, and preferably, b) may comprise at least one residue of a diol having from 2 to 10 carbon atoms, more preferably from 5 to 8 carbon atoms. This embodiment is particularly preferred when component b) comprises at least two or more residues of a C2 to C36 diacid or diol.

[0094] Suitable non-dimer diols may be independently selected from linear aliphatic diols or branched aliphatic diols, or combinations thereof.

[0095] Suitable non-dimer diols include linear aliphatic diols such as ethylene glycol, diethylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol (also known as hexanediol) and mixtures thereof, branched diols such as neopentyl glycol, 3-methylpentane glycol, 1,2-propylene glycol and mixtures thereof, and cyclic diols such as 1,4-bis(hydroxymethyl)cyclohexane and 1,4-cyclohexanedimethanol and mixtures thereof. Hexanediol is particularly preferred.

[0096] The linear aliphatic diols may be independently selected from ethylene glycol, diethylene glycol, 1,3-propylene glycol (better known as 1,3-propanediol), 1,4-butanediol, and 1,6-hexanediol. Such materials are particularly preferred.

[0097] The branched aliphatic diols may be independently selected from 1,2-propylene glycol, 1,2-butanediol, 2,3-butanediol, and 1,3-butanediol.

[0098] Component b) may comprise at least one residue of a polyether diol, such as polyethylene glycol, polypropylene glycol or polytetrahydrofuran (also known as polytetramethylene ether glycol or PTMEG). The PTMEG may have a molecular weight (number average) of 200 to 2000, preferably 200 to 1000, more preferably 200 to 500. This embodiment is particularly preferred when component b) comprises at least two or more residues of a C2 to C36 diacid or diol.

[0099] Component b) may include at least one residue of a polyol having a hydroxyl functionality greater than 2. Such polyols may include glycerol, pentaerythritol, or trimethylolpropane.

[0100] Component b) is preferably derived from renewable and / or bio-based sources, and most preferably from plant-derived sources. The level of renewable carbon content of b) is: 14 It may be determinable by ASTM D6866 as a standardized analytical method for determining the biobased content of a sample using C radiocarbon dating. ASTM D6866 distinguishes carbon originating from biobased sources from carbon derived from fossil-based sources. Using this standard, the percentage of carbon from renewable sources can be calculated from the total carbon in the test sample. Suitably, component b) may have a renewable carbon content of at least 50% by weight, preferably at least 65% by weight, more preferably at least 80% by weight, as determined using ASTM D6866.

[0101] Suitably, the weight ratio of a) to b) in the polyol may be in the range of 100:0 to 0:100, preferably in the range of 45:55 to 15:85. 5% by weight of a) in the acetoacetate end-capped polyol may be at least 95% by weight of b). These relative amounts of a) and b) in the acetoacetate end-capped polyester polyol may provide an advantageous balance of flexibility, tensile strength, hardness, and hydrolysis resistance in the polymer matrix formed from the polyester polyol.

[0102] The polyol before endcapping preferably has a hydroxyl number (measured as described herein) in the range of 10 to 150, more preferably 30 to 140, particularly preferably 60 to 120, and particularly preferably 75 to 110 mg KOH / g.

[0103] In addition, the polyol prior to endcapping preferably has an acid number (measured as described herein) of less than 2, more preferably less than 1.7, particularly preferably less than 1.3, and particularly preferably less than 1.0 mg KOH / g.

[0104] Additionally or alternatively, the present invention provides polymer compositions comprising acetoacetate end-capped polyols as described above. Such polymer compositions may have one or more desirable physical properties and may be particularly suited for their intended end use.

[0105] Suitably, the polymer composition may be a resin (i.e., a polymeric material in its intermediate form before hardening) or a polymeric matrix (i.e., a polymeric material in its final form after hardening). Thus, the polymeric composition may be considered to encompass two separate embodiments, the first being a resin and the second being a polymeric matrix. There is a large amount of overlap between the two polymeric composition embodiments, since additives required for the intended use or processing of the polymeric matrix final product may be introduced during the manufacture of the polymeric resin to facilitate post-processing or handling. Thus, the following embodiments referring to a "polymeric composition" apply equally to the polymeric resin and polymeric matrix embodiments.

[0106] The polymer composition may be provided as a resin, which may then be converted to a polymer matrix via curing. The difference between a polymer resin and a polymer matrix, as will be understood by those skilled in the art, is that crosslinking of polymer chains occurs in the polymer matrix. Curing to crosslink the polymer chains may be accomplished by any suitable means, although preferred means are further described below.

[0107] The dimeric fatty residue content of the polymer composition is preferably in the range of from 5 to 50 wt%, more preferably from 8 to 40 wt%, especially from 12 to 30 wt%, and particularly from 15 to 20 wt%.

[0108] The polymer composition is preferably derived from renewable and / or bio-based sources. This level can be determined by ASTM D6866, as briefly described herein. Preferably, the polymer composition has a renewable carbon content of at least 50% as determined using ASTM D6866. More preferably, it is at least 65%. Most preferably, it is at least 80%.

[0109] A particular advantage of the polymer composition of the present invention is that it is free of isocyanates. Thus, the polymer composition does not contain isocyanates. The polymer composition is substantially free of isocyanates.

[0110] Preferably, the polymer composition is the reaction product of the acetoacetate endblocked polyol and an acrylate described above. Thus, the polymer composition comprises an acetoacetate endblocked polyol and an acrylate.

[0111] Suitably, the acrylate may be selected from one or more acrylates, multifunctional acrylates, oligomeric acrylates or derivatives thereof.

[0112] Preferably, the acrylate is provided by an oligomeric acrylate or a derivative thereof. Particularly preferred oligomeric acrylates are urethane acrylates and epoxy acrylates. Such oligomeric acrylates may preferably be oligomeric acrylate resins as further detailed below. Commercially available oligomeric acrylate resins include Photomer® from IGM Resins, Laromer® from BASF, and Ebecryl® from Allnex, among others.

[0113] A preferred multifunctional acrylate or derivative thereof has a functionality of 2 or more. Suitably, the multifunctional acrylate derivative may be selected from the group consisting of any monomeric or oligomeric molecule having an acrylate, a methacrylate, an ethacrylate, and a combination thereof.

[0114] Preferably, the acrylate derivative may be selected from the group consisting of hexafunctional urethane acrylate, dipentaerythritol pentaacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, butanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane trimethacrylate, difunctional urethane acrylate, tetraacrylate monomer, polyester acrylate oligomer, and combinations thereof.

[0115] In one particularly preferred embodiment, the multifunctional acrylate derivative is a urethane acrylate oligomer.

[0116] In an alternative particularly preferred embodiment, the acrylate is a multifunctional acrylate oligomer selected from oligomeric epoxy acrylate resins, or oligomeric polyether acrylate resins, or oligomeric polyester acrylates, or combinations thereof.

[0117] The polymeric composition may optionally contain other additives such as blowing agents, catalysts, pigments, fillers, surfactants, and stabilizers.

[0118] The polymeric composition may optionally include a blowing agent, which may include water, fluorocarbons such as trichlorofluoromethane, dichlorodifluoromethane, and trichlorodifluoroethane, or mixtures thereof.

[0119] The polymer composition may optionally include a catalyst. The catalyst may be present in the polymer resin to aid in post-processing, or may be present in the polymer matrix due to immobilization in the polymer matrix during processing. Such catalysts tend to be homogeneous catalysts. Preferred homogeneous catalysts are salts of basic anionic groups. Examples of useful cations include inorganic cations, preferably alkali or alkaline earth metal cations, more preferably K+, Na+ and Li+, or organic cations such as tetraalkylammonium and tetraalkylphosphonium salts, but also cations that have a proton but are highly non-acidic, such as protonated species of strongly basic organic bases, for example 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-Diazabicyclo[4.3.0]non-5-ene (DBN) or tetramethylguanidine.

[0120] The polymer composition may optionally include a surfactant. Preferred surfactants may include one or more of silicone surfactants such as dimethylpolysiloxane, polyoxyalkylene polyol-modified dimethylpolysiloxane, and alkylene glycol-modified dimethylpolysiloxane, and / or anionic surfactants such as fatty acid salts, sulfate ester salts, phosphate ester salts, and sulfonates.

[0121] The polymer composition may optionally include a stabilizer. Suitably, the stabilizer may be selected from radical scavengers, antioxidants, or ultraviolet absorbers. Suitable stabilizers may be selected by those skilled in the art depending on the intended end use of the polymer composition. Examples of stabilizers include hindered phenol radical scavengers such as dibutylhydroxytoluene, pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], and isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, antioxidants such as phosphorous compounds such as triphenylphosphite, triethylphosphite, and triphenylphosphine, ultraviolet absorbers such as 2-(5-methyl-2-hydroxyphenyl)benzotriazole, and condensates of methyl-3-[3-t-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate with polyethylene glycol.

[0122] The polymer composition may optionally include a pigment or dye. Suitable pigments include inorganic pigments, such as transition metal salts, organic pigments, such as azo compounds, and carbon powders.

[0123] The polymer composition may optionally include a filler. Suitable fillers include inorganic fillers such as clay, chalk, and silica.

[0124] The polymer composition may optionally include a chain extender component. The chain extender component may be in the form of a chain extender composition. The chain extender composition is preferably prepared, for example, by simple premixing of the chain extender, the acrylate (as described above), and other additives (such as pigments and / or fillers as described above). At least one acrylate oligomer may be added together with the chain extender component and reacted with the prepolymer to form the polymer composition. Advantageously, the formation is carried out via C-Michael addition, as further described below, to provide a C-Michael polymer.

[0125] The chain extender component used to form the polymer preferably comprises a low molecular weight compound having two or more active acrylic functional groups. Examples of such acrylic functional group-containing compounds include hexafunctional urethane acrylate, dipentaerythritol pentaacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, butanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane trimethacrylate, difunctional urethane acrylate, and the acrylate group consisting of tetraacrylate monomers.

[0126] The molar ratio of the chain extender of the first aspect used in the present invention to the acetoacetate endblocked polyol is preferably in the range of 1 to 10:1, more preferably 1.5 to 8:1, particularly 2 to 5:1, and specifically 2.5 to 4:1.

[0127] The present invention also provides a method for preparing a polyol having an acetoacetate endblocked polyol, comprising reacting the acetoacetate endblocked polyol with an acrylate to form a polyol having an acetoacetate endblocked polyol. (i) a polymeric resin, or (ii) providing a method of making a polymer composition comprising forming a polymer matrix.

[0128] The preferred features of the acetoacetate endblocked polyol and the preferred features of the acrylate are as described above with respect to the composition embodiments.

[0129] Suitably, the method comprises the steps of i) forming a polymer resin, and then subsequently ii) forming a polymer matrix from the pre-formed resin. It is envisaged that the step of i) forming the polymer resin may be carried out in one geographic location and then the subsequent step of ii) forming a polymer matrix from the polymer resin may be carried out in a second, different geographic location.

[0130] A method of making the polymer composition may include mixing an acetoacetate endblocked polyol together with an acrylate to ensure that the two reactants are in close proximity resulting in a homogenous polymer composition.

[0131] Suitably, the molar ratio of acetoacetate endblocked polyol to acrylate reactant is in the range 1:0.2-4, preferably 1:0.25-3, more preferably 1:0.25-2.5, and most preferably 1:0.25-1.8.

[0132] As alluded to above, the main difference between the polymer composition resin and the polymer composition matrix is ​​the fact that the matrix is ​​further processed to achieve crosslinking between the polymer chains. Therefore, in the process of making the polymer composition into (ii) a polymer matrix, the process must include a step of crosslinking the polymer chains. Methods of crosslinking the polymer resin to provide a polymer matrix are known in the art of polymer manufacturing and are generally referred to as curing methods. In the process of the present invention, crosslinking of the polymer chains can be achieved by any suitable means. However, crosslinking via free radical polymerization or via Michael addition reaction is particularly preferred.

[0133] Crosslinking via free radical polymerization or via Michael addition reaction can be achieved at ambient temperature, more desirably at room temperature. In particular, crosslinking via free radical polymerization or via Michael addition reaction can be advantageously achieved at temperatures between 0°C and 120°C, preferably between 15°C and 60°C, more preferably between 20°C and 25°C.

[0134] More specifically, crosslinking via the Michael addition reaction is preferred, and such materials may be referred to as carbon-Michael reaction polymers, or C-Michael polymers for short. Thus, the endcapped polyol-containing polymer composition matrix products formed via this particularly preferred method may be conveniently referred to herein as C-Michael polymers.

[0135] An important advantage of the present invention is that crosslinking (or curing) can be achieved by carbon crosslinking through Michael addition reaction. The ability to utilize the Michael addition reaction method to achieve carbon-carbon bonds is facilitated by the presence of acetoacetate endblocked polyol as described herein. The fact that a relatively mild method to achieve carbon-carbon bonds can be utilized means that polymer manufacturing methods utilizing isocyanates as reactants can be substituted without unexpected loss of product performance when the polymer matrix is ​​utilized in its intended end use, compared to polymers prepared utilizing isocyanates. Such isocyanate-free polymer manufacturing methods have clear health and environmental advantages over conventional isocyanate polymer manufacturing methods. Additionally, the fact that the Michael addition reaction can be achieved at ambient and / or room temperature provides the benefit of ease of manufacturing.

[0136] The present invention further provides the use of acetoacetate endblocked polyol as described herein to form a polymer composition. The polymer composition described herein, more specifically, the C-Michael polymer, can be used in many applications. The polymer of the present invention can be preferably used in a coating composition, an adhesive composition, a sealant composition, or an elastomer composition. In particular, the polymer can find application in a coating, an adhesive, an elastomer, or a sealant, more preferably in an elastomer or a sealant.

[0137] Additionally, the present invention provides a coating composition, an adhesive composition, a sealant composition, or an elastomer comprising the acetoacetate endblocked polyol described above. Preferably, an adhesive composition, a sealant composition, or an elastomer composition comprising the acetoacetate endblocked polyol described above is provided.

[0138] More specifically, the preferred adhesive, sealant or elastomer composition comprises a polymeric composition matrix as described herein. Advantageously, the adhesive, sealant or elastomer composition comprises a C-Michael polymer as described herein.

[0139] All of the features described in this specification may be combined with any of the above aspects in any combination. EXAMPLES

[0140] The invention will now be further described, by way of example only, with reference to the following examples in which all parts and percentages are by weight unless otherwise stated.

[0141] It will be understood that all tests and physical properties listed are determined at atmospheric pressure and room temperature (i.e., about 20° C.) unless otherwise noted herein or in the referenced test methods and procedures.

[0142] The materials used in the following examples are identified as follows: Adipic acid (C9 dicarboxylic acid) as Crodacid DC1195 from Croda - bio-based version ■ Croda Pripol™ 1006 Dimer Fatty Diacid - Hydrogenated C 36 Dicarboxylic acids ■ NEOGROUP's NEOPOLYOL240-r PET polyol ■ Sigma-Aldrich PPG1000 ■Methylacetoacetate (MAA) manufactured by Lonza ■IGM Resins Photomer(TM) 3016-Acrylate ■IGM Resins Photomer(TM) 4028-Acrylate ■ Imerys Nyad® 400 - Wollastonite ■Add-2272-Degassing agent made by ADD-additives ■Aerosil 200-fumed silica manufactured by Evonik Industries.

[0143] Test Method: (iii) The number average molecular weight was determined by end group analysis with reference to the hydroxyl value. (iii) The number average molecular weight was determined by end group analysis with reference to the hydroxyl value. The hydroxyl number is defined as the number of milligrams of potassium hydroxide equivalent to the hydroxyl content of 1 g of sample and was determined by acetylation followed by hydrolysis with an excess of acetic anhydride. The acetic acid formed was then titrated with an ethanolic potassium hydroxide solution. ■Acid value is defined as the number of milligrams of potassium hydroxide required to neutralize the free fatty acids in 1 g of sample, and was measured by direct titration with a standard potassium hydroxide solution. ■ Shore A hardness was measured in accordance with DIN 53505. ■ Elongation was measured using an Instron tensile testing machine according to ISO 37 using type 2 dumbbell specimens unless otherwise specified. ■ Tensile strength was measured using an Instron tensile testing machine according to ISO 37 using type 2 dumbbell specimens unless otherwise specified. ■ Tear strength was measured using an Instron tensile tester according to ISO 34-1 using Method B unless otherwise specified. ■ Adhesive strength was tested according to ISO4587.

[0144] Example 1: Preparation and Examples of Acetoacetate End-Capped Polyols P1-dimeric fatty acids and polyols containing them In a reactor equipped with a stirrer, thermometer, gas inlet, and condenser, 100 parts by weight of Pripol 1006 and 200 parts of NEOPOL 240 were charged. The temperature of the reactor was then increased from ambient temperature to 220-230°C under nitrogen atmosphere and normal pressure. Under these conditions, an esterification reaction was carried out to obtain a polyester polyol. The esterification reaction was carried out until the desired acid / hydroxyl value was observed, in this example, the resulting polyester polyol had an acid value of less than 1 mg KOH / g and a hydroxyl value of 103 mg KOH / g. The resulting polyester polyol had a calculated number average molecular weight of about 1000 g / mol.

[0145] Polyols containing P2-azelaic acid and rPET polyol In a reactor equipped with a stirrer, thermometer, gas inlet, and condenser, 70 parts by weight of Crodacid DC1195 and 100 parts of NEOPOLYOL 240 were charged. The temperature of the reactor was then increased from ambient temperature to 220-230°C under normal pressure in a nitrogen atmosphere. Under these conditions, the esterification reaction was carried out until the desired acid / hydroxyl value was observed. In this example, the resulting polyester polyol had an acid value of less than 1 mg KOH / g and a hydroxyl value of 112 mg KOH / g. The resulting polyester polyol had a calculated number average molecular weight of about 1000 g / mol.

[0146] A general method for the conversion of acetoacetate end-capped polyols. Each of the polyester polyols and comparative PPG polyols prepared above were then modified to endcap them with acetoacetate in accordance with the present invention.

[0147] Into a reactor equipped with agitator, thermometer, gas inlet, and condenser was charged 100 parts by weight of each of the polyols prepared above and 25 parts by weight of methyl acetoacetate (Lonza MAA).

[0148] The temperature of the reactor is increased to 150-160° C. under normal pressure in a nitrogen atmosphere. Under these conditions, the reaction is continued until the theoretical amount of methanol distillate is reached.

[0149] If necessary, a vacuum can be applied to ensure completion of the reaction.

[0150] Gel chromatography can be used to determine reaction completion.

[0151] Example 2: Preparation and Analysis of Elastomers / Sealants Containing Example Polyols and Comparative Polyols Various elastomer / sealant compositions were prepared as detailed in Table 1 below. C-Michael addition reactions carried out at room temperature were used when utilizing available acrylate-based oligomers of the exemplary acetoacetate end-capped polyester polyols as described above. The elastomer / sealant was prepared using a two-component process. The C-Michael crosslinking achieved within the polymer matrix can be accelerated, if desired, by the use of an organic base catalyst such as DBU (1,8-diazabicyclo[5.4.0]undec-7-ene).

[0152] The acetoacetate endblocked polyol and the acrylate oligomer were reacted in a 1:1 molar ratio, as shown in Table 1 below. The two commercially available acrylate oligomers tested were Photomer™ 3016 (an epoxy acrylate from IGM Resins) and / or Photomer 4028 (an acrylate from IGM Resins). Thus, the resulting elastomer / sealant is a two component based product, but advantageously formulated in the absence of isocyanate. The elastomer / sealant compositions were cast for mechanical property evaluation, including Shore A hardness, tensile strength, elongation, and tear strength.

[0153] The elastomer / sealant properties were evaluated and the results are shown in Tables 1 and 2.

[0154] [Table 1]

[0155] [Table 2]

[0156] When considering the mechanical properties detailed in Table 2 above, the C-Michael polymer matrix material formed at room temperature from the acetoacetate end-capped polyols of the present invention in combination with acrylate oligomers provides an elastomer or sealant that offers higher tensile strength, elongation, and improved tear strength without adversely affecting Shore A hardness (when compared to an elastomer or sealant on a benchmark basis).

[0157] The more crystalline structure of Example 2 enhances tear strength over the more amorphous Example 1. When the acetoacetate end-capped polyols of the present invention are combined with a single acrylate oligomer, an elastomer / sealant is provided that provides higher tensile strength, elongation, and improved tear strength with no or only a slight effect on Shore A hardness (when comparing elastomers / sealants on a benchmark basis). The more crystalline structure of Example 2a enhances tear strength over the more amorphous Example 1a.

[0158] [Table 3]

[0159] [Table 4]

[0160] As can be seen from Table 4 above, compositions including acrylate oligomer blends containing more than 20% to less than 40%, e.g., 26-34%, of filler, such as Example 4, have higher tear strength, tensile strength and elongation when compared to single-use acrylate oligomers such as Example 5 at comparable Shore A hardness.

[0161] [Table 5] *) Glass-filled epoxy resin

[0162] When considering the adhesive strengths detailed in Table 5, the C-Michael polymer matrix material formed from the acetoacetate end-capped polyols of the present invention in combination with acrylate oligomers at room temperature provides adhesive formulations with higher adhesive strengths than Example 7. The adhesive strength is provided by the aromatic and semi-crystalline structure of the acetoacetate end-capped polyols.

Claims

1. at least one residue of a polyol derived from virgin thermoplastic polyester, recycled thermoplastic polyester, and mixtures thereof; and a) at least one dimer fatty residue selected from dimer fatty acid residues, dimer fatty diol residues, and dimer fatty diamine residues, and / or b) at least one residue of a linear or branched C2-C36 diacid or diol 4. An acetoacetate end-capped polyol comprising:

2. 2. The acetoacetate endcapped polyol of claim 1, comprising b) at least one residue of a linear or branched C2-C36 diacid or diol.

3. 3. The acetoacetate endblocked polyol of claim 1, wherein the weight ratio of a) to b) in said polyol is in the range of 45:55 to 15:

85.

4. 4. The acetoacetate end-capped polyol of claim 1, wherein the acetoacetate end-capped component of the acetoacetate end-capped polyol is selected from one or more of the following: methyl acetoacetate, ethyl acetoacetate, tert-butyl acetoacetate, isopropyl acetoacetate, isobutyl acetoacetate, and ketene derivatives.

5. 5. The acetoacetate endcapped polyol of any one of claims 1 to 4, wherein the at least one residue of a polyol derived from virgin thermoplastic polyester, recycled thermoplastic polyester, and mixtures thereof is derived from polyethylene terephthalate.

6. 6. The acetoacetate endcapped polyol according to any one of claims 1 to 5, comprising at least 5% by weight of dimer fatty residues, preferably at least 10% by weight of dimer fatty residues, and / or up to 90% by weight of dimer fatty residues.

7. 7. The acetoacetate end-capped polyol of any one of claims 1 to 6, comprising at least one dimeric fatty residue selected from dimeric fatty acid residues derived from the dimerization products of oleic acid, linoleic acid, linolenic acid, palmitoleic acid, or elaidic acid.

8. 8. The acetoacetate endcapped polyol of any one of claims 1 to 7, wherein the amount of component b) in the endcapped polyol is at least 0.10 wt%, preferably at least 0.15 wt%, more preferably at least 0.20 wt%.

9. The acetoacetate endblocked polyol of any one of claims 1 to 8, wherein component b) comprises at least one residue of a linear dicarboxylic acid having a carbon chain in the range of from 4 to 12 carbon atoms.

10. 10. The acetoacetate endcapped polyol of claim 9, wherein component b) comprises at least one residue of a linear dicarboxylic acid derived from adipic acid, glutaric acid, succinic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, heptanedicarboxylic acid, octanedicarboxylic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and dodecanedicarboxylic acid, and optionally component b) comprises at least one residue of a linear dicarboxylic acid derived from azelaic acid.

11. A polymer composition comprising the acetoacetate endblocked polyol of any one of claims 1 to 10.

12. 12. The polymer composition of claim 11, wherein the polymer composition is isocyanate-free.

13. A method of making a polymer composition comprising reacting an acetoacetate endblocked polyol according to any one of claims 1 to 10 with an acrylate, (i) a polymer resin, or (ii) forming a polymer matrix.

14. Use of the acetoacetate endblocked polyol of any one of claims 1 to 10 to form a polymer composition.

15. Use of the acetoacetate endblocked polyol according to any one of claims 1 to 10 in a coating composition, an adhesive composition, a sealant composition, or an elastomeric composition.