Cardanol derivative-modified polymer and coating composition containing same

Abstract

The present invention provides cardanol derivative-modified polymers obtained by reacting epoxy groups in a cardanol derivative compound with carboxyl groups in a carboxyl-functional polymer, where the cardanol derivative compound is the reaction product of a cardanol derivative modified with a haloalkylene oxide having 3 to 10 carbon atoms, preferably 3 to 6, and more preferably 3 to 4 carbon atoms. The present invention also provides methods for preparing the cardanol derivative-modified polymers, methods for using the cardanol derivative-modified polymers in automotive coatings, and the resulting coating compositions.

Description

[Technical Field]

[0001] The present invention relates to cardanol derivative-modified polymers and coating compositions containing the cardanol derivative-modified polymers, in particular automotive coating compositions containing the cardanol derivative-modified polymers. [Background technology]

[0002] In solvent-based coatings, coatings with low VOC or high solids content are gaining increasing market attention due to increasingly stringent VOC (volatile organic compound) regulations. In the field of automotive coatings, "high solids content" refers to a high non-volatile content (e.g., >40% by weight) in a solvent-based coating composition or paint. Typically, the non-volatile content is determined according to ASTM D2369, in which test samples are heated at 110°C for 60 minutes.

[0003] However, coating compositions with "high solids" also tend to be highly viscous, which leads to a number of problems, such as long filtration times in the manufacturing process and poor flowability when spraying or dusting the coating composition onto the article to be coated.

[0004] For example, in the case of epoxy acrylate resins, traditional types, such as bisphenol A epoxy acrylates, suffer from high viscosity, and resin modification is one solution to overcome this problem. Cardanol, a natural phenolic compound extracted from cashew nut shells, a by-product of the cashew nut industry, offers advantages such as low cost and natural decomposition, making cardanol-modified acrylate resins a good option. Chinese Patent Application CN107022061A discloses a method for synthesizing UV-cured biomass epoxy acrylate prepolymers, the resulting prepolymers, and their applications in coatings, inks, and adhesives. The synthesis method includes using cardanol as the main raw material, reacting the phenolic hydroxyl groups in the cardanol molecule with epichlorohydrin, reacting the double bonds in the cardanol molecule with hydrogen peroxide to produce multiple epoxy groups, and reacting the epoxy groups with (meth)acrylic acid to obtain UV-cured biomass epoxy acrylate prepolymers. According to Table 1 of CN107022061A, the minimum viscosity reached is 5.2 Pa·s. However, under certain circumstances, even lower viscosities are required that cannot be met by the method of CN107022061A. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] CN107022061A Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, new types of cardanol-modified acrylate resins are still needed to achieve even lower viscosities, and therefore coating compositions require even less solvent to meet the stringent requirements of low VOCs. [Means for solving the problem]

[0007] In one aspect, the present invention provides a cardanol derivative-modified polymer obtained from the reaction of an epoxy group in a cardanol derivative compound with a carboxyl group in a carboxyl-functional polymer, wherein the cardanol derivative compound is the reaction product of cardanol and a haloalkylene oxide having 3 to 10 carbon atoms, preferably 3 to 6 carbon atoms, and more preferably 3 to 4 carbon atoms.

[0008] In another aspect, the present invention provides a method for preparing the cardanol derivative-modified polymer of the present invention.

[0009] In another aspect, the present invention provides a coating composition comprising the cardanol derivative-modified polymer of the present invention.

[0010] In another aspect, the present invention provides a method for preparing a coating composition comprising the cardanol derivative-modified polymer of the present invention.

[0011] In a further aspect, the present invention provides the use of the coating composition of the present invention in automotive OEM manufacturing or automotive refinishing, particularly automotive clearcoats.

[0012] Surprisingly, it has been found that the cardanol derivative-modified polymers of the present invention result in coating compositions with higher non-volatile content and lower viscosity than coating compositions containing the same amount of the unmodified corresponding polymer. As a result, coating compositions containing the cardanol derivative-modified polymer require less solvent, thus resulting in low VOC coatings.

[0013] As used in this specification and the appended claims, the following terms are defined as follows:

[0014] The terms "a," "an," and "the," when used to define a term, include both the plural and the singular form of that term.

[0015] Unless otherwise specified, all percentages and ratios are by weight.

[0016] The term "and / or" includes the meanings of "and", "or" and also all other possible combinations of the elements connected to this term.

[0017] As used herein, the term "polymer" includes both homopolymers (i.e., polymers prepared from a single reactive compound) and copolymers (i.e., polymers prepared by the reaction of at least two polymer-forming reactive monomeric compounds).

[0018] The term "(meth)acrylic" is hereinafter intended to denote acrylic and / or methacrylic. The term "(meth)acrylate" is hereinafter intended to denote acrylate and / or methacrylate.

[0019] The measurement methods employed for the purposes of the present invention to determine particular parameters can be found in the Examples section, and unless otherwise specified, these measurement methods are the ones used to determine the parameters in question.

[0020] In the present invention, "binder" refers to the film-forming component of the coating composition. Thus, the binder includes resins, curing agents, and other film-forming agents, but does not include solvents, pigments, or additives such as antioxidants, HALS, UV absorbers, or leveling agents. In the present invention, when referred to, "binder resin" refers to the polymer resin component used in the coating composition.

[0021] In the context of the present invention, the concept of "curing" a coating composition on a substrate refers to the transformation of a film of the coating composition applied to a substrate into a service-ready state, in other words, into a state in which the substrate provided with the coating film can be transported, stored, and used as intended. Thus, the cured coating film is in particular no longer soft or tacky, but instead is prepared as a solid coating film that no longer shows substantial changes in properties such as hardness or adhesion to the substrate, even when further exposed to the curing conditions described below.

[0022] Carboxyl-functional polymers The carboxyl functional polymer of the present invention is used in coatings as a binder resin and is any kind of carboxyl group-containing polymer having an acid value of 100-200 mg KOH / g.

[0023] Preferably, the carboxyl-functional polymer is at least one selected from the group consisting of carboxyl-functional polyacrylics, carboxyl-functional polyesters, carboxyl-functional polyurethanes, and carboxyl-functional polyamides, having an acid value of 100 to 200 mg KOH / g.

[0024] Preferably, the weight average molecular weight of the carboxyl functional polymer is from 1000 g / mol to 12000 g / mol, more preferably from 1000 g / mol to 10000 g / mol, even more preferably from 1000 g / mol to 5000 g / mol, and most preferably from 1500 g / mol to 3500 g / mol.

[0025] Preferably, the carboxyl-functional polymer comprises at least one carboxyl-functional poly(meth)acrylate. Alternatively, the carboxyl-functional polyacrylic suitable for the present invention can be obtained by polymerizing a monomer mixture containing a hydroxyalkyl(meth)acrylate monomer with a linear or cyclic alkyl dicarboxylic acid or its anhydride, such as a linear or cyclic C2-C6 alkyl dicarboxylic acid or its anhydride. Furthermore, in an embodiment of the present invention, the monomer mixture may further contain a lactone monomer.

[0026] Non-limiting examples of hydroxyalkyl (meth)acrylate monomers that can be used in the present invention include hydroxy C2-C4 alkyl (meth)acrylates, such as hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate.

[0027] Non-limiting examples of lactone monomers that can be used in the present invention include gamma-butyrolactone, delta-valerolactone, and epsilon-caprolactone.

[0028] Non-limiting examples of linear or cyclic alkyl dicarboxylic acids or anhydrides thereof that can be used in the present invention include succinic acid, glutaric acid, adipic acid, cyclobutane-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and anhydrides thereof.

[0029] In a preferred embodiment of the present invention, the carboxyl functional polymer of the present invention is obtained from the polymerization of hydroxyethyl (meth)acrylate, ε-caprolactone, and 1,2-cyclohexanedicarboxylic anhydride. In an embodiment of the present invention, the monomer mixture for obtaining the carboxyl functional polymer of the present invention may also contain (meth)acrylic acid monomers in addition to hydroxyethyl (meth)acrylate, ε-caprolactone, and 1,2-cyclohexanedicarboxylic anhydride.

[0030] Other monomers may also be used as comonomers in preparing the carboxyl-functional polyacrylics suitable for the present invention. Such comonomers may be, for example, styrene, (meth)acrylates, etc. For example, the (meth)acrylate may be selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 3,3,5-trimethylhexyl acrylate, and 3,3,5-trimethylhexyl methacrylate.

[0031] Carboxyl-functional polyacrylics suitable for the present invention can be prepared using conventional free-radical polymerization techniques, for example, by heating monomers in the presence of a polymerization initiator. Those skilled in the art will be able to select an appropriate temperature for polymerization. For example, the temperature may range from 20 to 200°C. A polymerization initiator for free-radical polymerization can be used. Typical initiators include organic peroxides, such as alkyl peroxides, e.g., di-t-butyl peroxide; peroxyesters, e.g., t-butyl peroxy 2-ethylhexanoate and t-butyl peracetate; peroxydicarbonates; diacyl peroxides; hydroperoxides, e.g., t-butyl hydroperoxide, and peroxyketals; azo compounds, e.g., 2,2'-azobis(2-methylbutanenitrile) and 1,1'-azobis(cyclohexanecarbonitrile); and combinations thereof.

[0032] The carboxyl functional polymer of the present invention may be a carboxyl functional polyester, a carboxyl functional polyurethane, or a carboxyl functional polyamide suitable for use as a binder resin in a coating composition. These carboxyl functional polymers can be obtained by those skilled in the art according to conventional processes.

[0033] Preferably, the acid number of the carboxyl functional polymer is in the range of 100 to 200 mg KOH / g, for example, the acid number of the carboxyl functional polymer of the present invention is in the range of 120 to 180 mg KOH / g, such as in the range of 130 to 150 mg KOH / g.

[0034] Cardanol derivative compounds Cardanol is a phenolic lipid obtained from anacardic acid, a major component of cashew nut shell liquid, a by-product of cashew nut processing.

[0035] Starting from cardanol, a cardanol derivative compound is prepared by reacting it with at least one haloalkylene oxide. Preferably, the haloalkylene oxide has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and even more preferably 3 to 4 carbon atoms. The halogen element in the haloalkylene oxide is at least one selected from the group consisting of F, Cl, Br, and I.

[0036] Preferably, the haloalkylene oxide is at least one selected from epichlorohydrin, epibromohydrin, epiiodohydrin, 1-chloro-3,4-epoxybutane, 1-bromo-3,4-epoxybutane, 1-iodo-3,4-epoxybutane, 1-chloro-4,5-epoxypentane, 1-bromo-4,5-epoxypentane, 1-iodo-4,5-epoxypentane, 1-chloro-5,6-epoxyhexane, 1-bromo-5,6-epoxyhexane, and 1-iodo-5,6-epoxyhexane.

[0037] Preferably, the molar ratio of cardanol to haloalkylene oxide in the reaction is 1:1 to 1:1.1. The synthesis method of said cardanol derivatives is known in the art, for example, CN108299165A.

[0038] Cardanol derivative modified polymer The cardanol derivative modified polymers of the present invention can be obtained from the reaction of epoxy groups in the cardanol derivative compounds with carboxyl groups in the carboxyl functional polymers based on a typical epoxy-acid reaction.

[0039] In the epoxy-acid reaction of the present invention, the molar ratio of the total epoxy groups from the cardanol derivative compound to the total carboxy groups from the carboxyl-functional polymer may be 1:1 or less. Furthermore, for purposes of the present invention, it is preferable that the total carboxy groups from the carboxyl-functional polymer be slightly in excess of the total epoxy groups from the cardanol derivative compound of the present invention. For example, the molar ratio of the total epoxy groups from the cardanol derivative compound to the total carboxy groups from the carboxyl-functional polymer may be in the range of 2:3 to 1:1, for example, 3:4 to 1:1.

[0040] Preferably, in the epoxy-acid reaction of the present invention, at least 60% of the carboxy groups in the carboxyl-functional polymer are reacted with the epoxy groups in the cardanol derivative compound, such as, particularly, at least 65%, e.g., at least 75%, of the carboxy groups in the carboxyl-functional polymer are reacted with the epoxy groups in the cardanol derivative compound.

[0041] The epoxy-acid reaction of the present invention is carried out in the presence of a solvent at a temperature below 200° C. Preferably, the epoxy-acid reaction of the present invention is carried out at a temperature between 120° C. and 180° C., more preferably between 140° C. and 160° C.

[0042] Solvents suitable for the epoxy-acid reaction of the present invention are those that are inert to the epoxy-acid reaction. Non-limiting examples of suitable solvents include aromatic hydrocarbons, alcohol solvents, ester solvents, ketones, glycol ethers, and esters of glycol ethers. Specific examples include, but are not limited to, toluene, xylene, ethyl acetate, butyl acetate, hexyl acetate, acetone, butanone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, m-amyl acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, tert-butanol, N-methylpyrrolidone, N-ethylpyrrolidone, Aromatic 100, Aromatic 150, naphtha, mineral spirits, and butyl glycol.

[0043] Optionally, a catalyst is used in the epoxy-acid reaction of the present invention. In the present invention, all catalysts commonly used in epoxy-acid reactions are applicable, such as phosphorus-containing catalysts. In one embodiment of the present invention, the catalyst is at least one selected from the group consisting of triphenylphosphine, triphenylantimony, and chromium(III) acetylacetonate.

[0044] Suitably, the weight average molecular weight of the cardanol derivative-modified polymer of the present invention may be from 1200 g / mol to 20000 g / mol, preferably from 1500 g / mol to 15000 g / mol, more preferably from 2000 g / mol to 10000 g / mol, and even more preferably from 3000 g / mol to 5000 g / mol.

[0045] The cardanol derivative-modified polymer of the present invention may have a glass transition temperature (Tg) of -30°C to 50°C, preferably -10°C to 50°C, and more preferably 5°C to 35°C.

[0046] The viscosity of the cardanol derivative modified polymer of the present invention at 25° C. can be 300-1000 mPa·s according to the method CAP 2000, Brookfield, 3# spin.

[0047] The cardanol derivative-modified polymers of the present invention can be used in the preparation of coatings, paints, etc.

[0048] Coatings obtained using the cardanol derivative-modified polymers of the present invention have higher non-volatile content and reduced viscosity compared to corresponding conventional coatings.

[0049] Coating Composition The present invention further relates to a coating composition containing the cardanol derivative-modified polymer of the present invention, wherein the cardanol derivative-modified polymer of the present invention is used as a binder resin. In an embodiment of the present invention, the cardanol derivative-modified polymer of the present invention may be the only binder resin of the coating composition.

[0050] In the coating composition of the present invention, the amount of the cardanol derivative-modified polymer of the present invention may be 30% by mass to 60% by mass, preferably 40% by mass to 60% by mass, based on the total mass of the coating composition of the present invention.

[0051] Another advantage of the present invention is that the cardanol derivative-modified polymers of the present invention, when used as binder resins in coating compositions, can be cured by two approaches: The cardanol derivative-modified polymers of the present invention can be cured through the C=C double bonds and hydroxyl groups in the polymer, which allows the cardanol derivative-modified polymers to be cured more efficiently.

[0052] Curing agents suitable for the coating compositions of the present invention include, but are not limited to, isocyanate curing agents, such as polyisocyanate curing agents or blocked polyisocyanate curing agents. Useful polyisocyanate curing agents include, but are not limited to, isocyanurates, biurets, allophanates, uredione compounds, and isocyanate-functional prepolymers, such as the reaction product of one mole of a triol with three moles of a diisocyanate. The polyisocyanate may be blocked with a lower alcohol, oxime, or other such material that volatilizes at cure temperatures to regenerate the isocyanate groups.

[0053] The polyisocyanate curing agent or blocked polyisocyanate curing agent may be used in an equivalent ratio of 0.1 to 1.1, or in an equivalent ratio of 0.5 to 1.0, for each equivalent of functional groups reactive therewith available from the curable binder resin.

[0054] Aminoplasts can also be used as curing agents in the coating compositions of the present invention. For purposes of the present invention, aminoplasts are materials obtained by reacting an activated nitrogen with a low molecular weight aldehyde, optionally with an alcohol (preferably a monoalcohol having 1 to 4 carbon atoms) to form an ether group. Preferred examples of activated nitrogen include activated amines such as melamine, benzoguanamine, cyclohexylcarboguanamine, and acetoguanamine; ureas, including urea itself, thiourea, ethyleneurea, dihydroxyethyleneurea, and guanylurea; glycoluril; amides such as dicyandiamide; and carbamate-functional compounds having at least one primary carbamate group or at least two secondary carbamate groups.

[0055] The activated nitrogen is reacted with a low molecular weight aldehyde. The aldehyde can be selected from formaldehyde, acetaldehyde, crotonaldehyde, benzaldehyde, or other aldehydes used in the production of aminoplast resins, with formaldehyde and acetaldehyde, especially formaldehyde, being preferred. The activated nitrogen group is at least partially alkylolated with the aldehyde, and may be fully alkylolated, preferably fully alkylolated. This reaction may be acid-catalyzed, as taught, for example, in U.S. Pat. No. 3,082,180, the contents of which are incorporated herein by reference.

[0056] The alkylol groups formed by the reaction of the activated nitrogen with the aldehyde may be partially or fully etherified with one or more monofunctional alcohols. Suitable examples of monofunctional alcohols include, but are not limited to, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butyl alcohol, benzyl alcohol, and the like. Monofunctional alcohols having 1 to 4 carbon atoms and mixtures thereof are preferred. Etherification may be carried out, for example, by the processes disclosed in U.S. Pat. Nos. 4,105,708 and 4,293,692, the inventions of which are incorporated herein by reference.

[0057] The aminoplast may be at least partially etherified, and in a different embodiment, the aminoplast is fully etherified.

[0058] Amine curing agents may also be used in the coating compositions of the present invention. Examples of amine curing agents include ethylenediamine, diethylenetriamine, tetraethylenepentamine, isophoronediamine, N-aminoethylpiperazine, m-xylylenediamine, etc. In particular, melamine and blocked isocyanates are used as curing agents in 1k coating systems, while isocyanates are used in 2k coating systems.

[0059] In the coating composition of the present invention, the amount of the curing agent may be 15% to 30% by mass, preferably 20% to 30% by mass, based on the total mass of the binder in the coating composition of the present invention.

[0060] The coating composition of the present invention may contain a catalyst to accelerate the curing reaction. For example, a strong acid catalyst can be utilized to accelerate the curing reaction, particularly when monomeric melamine is used as the curing agent. Such catalysts are well known in the art and include, but are not limited to, p-toluenesulfonic acid, dinonylnaphthalenedisulfonic acid, dodecylbenzenesulfonic acid, phenyl acid phosphate, monobutyl maleate, butyl phosphate, and hydroxyphosphate esters. Strong acid catalysts are often blocked, for example, with amines. For the reaction of polyisocyanates with suitable curable binder resin functional groups, suitable catalysts include tin compounds, such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin oxide, tertiary amines, zinc salts, and manganese salts. The reaction of epoxide groups with carboxyl groups during the curing reaction may be catalyzed by tertiary amines or quaternary ammonium salts (e.g., benzyldimethylamine, dimethylaminocyclohexane, triethylamine, N-methylimidazole, tetramethylammonium bromide, and tetrabutylammonium hydroxide), tin and / or phosphorus complex salts (e.g., (CH3)3SNI, (CH3)4PI, triphenylphosphine, ethyltriphenylphosphonium iodide, tetrabutylphosphonium iodide), and the like.

[0061] The coating composition of the present invention contains a solvent. The solvent contained in the coating composition may be partly from the preparation of the cardanol derivative-modified polymer of the present invention. The solvent used to formulate the coating composition of the present invention may be the same as the solvent used to prepare the cardanol derivative-modified polymer of the present invention, or may be selected from the same group of solvents suitable for preparing the cardanol derivative-modified polymer of the present invention. The amount of solvent in the coating composition of the present invention may be selected by those skilled in the art according to the actual application.

[0062] The coating compositions of the present invention may optionally further comprise a rheology control agent, including a high molecular weight mixed cellulose ester, such as CAB-381-0.1, CAB-381-20.1, CAB-381-20, CAB-531-1, CAB-551-0.01, and CAB-171-15S (available from Eastman Chemical Company, Kingsport, Tennessee), in an amount of up to 5 wt. %, or from 0.1 to 5 wt. %, or from 1.5 to 4.5 wt. %, based on the total weight of the binder in the coating composition of the present invention. Further examples include microgel rheology control agents, such as crosslinked acrylic polymer microparticles, which may be present in an amount of 5% by weight or less, based on the total weight of the binder in the coating composition of the present invention; wax rheology control agents, such as acrylic acid-modified polyethylene waxes (e.g., Honeywell AC® Performance Additives), poly(ethylene-vinyl acetate) copolymers, and polyethylene waxes, including oxidized polyethylene, which may be present in an amount of 2% by weight or less, based on the total weight of the binder in the coating composition of the present invention; and fumed silica, which may be present in an amount of 10% by weight or less, based on the total weight of the binder in the coating composition of the present invention, or from 3 to 12% by weight, based on the total weight of the binder in the coating composition of the present invention.

[0063] The coating composition of the present invention may further contain a pigment. Non-limiting examples of suitable pigments include inorganic and organic pigments, such as titanium dioxide, barium sulfate, carbon black, yellow ochre, sienna, amber, hematite, limonite, red iron oxide, transparent red iron oxide, black iron oxide, brown iron oxide, chromium oxide green, strontium chromate, zinc phosphate, silica, such as fumed silica, calcium carbonate, talc, barite, ferric ammonium ferrocyanide (Prussian blue), ultramarine, metallized and non-metallized azo red, quinacridone red and violet, perylene red, copper phthalocyanine blue and green, carbazole violet, monoarylide and diarylide yellow, benzimidazolone yellow, tolyl orange, naphthol orange, etc. The pigment is preferably dispersed in a resin or polymer or using a pigment dispersant according to known methods, for example, in the cardanol derivative-modified polymer of the present invention. Generally, the pigment and dispersing resin, polymer, or dispersant are contacted under high shear forces sufficient to break down the pigment agglomerates into primary pigment particles and wet the surfaces of the pigment particles with the dispersing resin, polymer, or dispersant. Breaking down the agglomerates and wetting the pigment to the primary pigment particles are important for pigment stability and color development. The pigment may be utilized in an amount typically up to 40% by weight, based on the total weight of the coating composition.

[0064] The coating composition of the present invention may further contain additional additives, such as hindered amine light stabilizers, ultraviolet absorbers, antioxidants, surfactants, stabilizers, wetting agents, adhesion promoters, etc. Those skilled in the art will select the appropriate amounts of these additives when formulating the coating composition of the present invention according to the actual application.

[0065] The coating composition of the present invention can be used in various applications. In particular, the coating composition of the present invention can be used as an automotive coating, for example, an automotive coating for automobile OEM manufacturing (original equipment manufacturing) or automobile refinishing. In a preferred embodiment of the present invention, the coating composition of the present invention can be used as an automotive clear coat coating. DETAILED DESCRIPTION OF THE INVENTION

[0066] The present invention will be described more specifically using the following embodiments.

[0067] A first embodiment is a cardanol derivative modified polymer obtained from the reaction of epoxy groups in a cardanol derivative compound with carboxyl groups in a carboxyl functional polymer, wherein the cardanol derivative compound is a reaction product of cardanol and a haloalkylene oxide having 3 to 10 carbon atoms, preferably 3 to 6 carbon atoms, the acid value of the carboxyl functional polymer is 100 to 200 mg KOH / g, preferably 120 to 180 mg KOH / g, and at least 60%, preferably at least 65%, of the carboxyl groups in the carboxyl functional polymer are reacted with epoxy groups in the cardanol derivative compound.

[0068] The second embodiment is the cardanol derivative-modified polymer described in the first embodiment, wherein the Mw (weight average molecular weight) of the carboxyl functional polymer is from 1000 g / mol to 12000 g / mol, more preferably from 1000 g / mol to 10000 g / mol, even more preferably from 1000 g / mol to 5000 g / mol, and most preferably from 1500 g / mol to 3500 g / mol.

[0069] A third embodiment is a cardanol derivative-modified polymer according to embodiment 1 or 2, wherein the carboxyl-functional polymer is at least one selected from the group consisting of carboxyl-functional polyacrylics, carboxyl-functional polyesters, carboxyl-functional polyurethanes, and carboxyl-functional polyamides.

[0070] A fourth embodiment is a cardanol derivative-modified polymer according to any one of the first to third embodiments, wherein the carboxyl functional polymer is obtained from the polymerization of monomers comprising (meth)acrylic acid and preferably further comprising a styrene monomer.

[0071] A fifth embodiment is the cardanol derivative-modified polymer of any one of embodiments 1 to 3, wherein the carboxyl functional polymer is obtained from the copolymerization of a monomer selected from the group consisting of hydroxyalkyl (meth)acrylates with a monomer selected from the group consisting of linear or cyclic alkyl dicarboxylic acids or anhydrides and lactones, preferably the linear or cyclic alkyl dicarboxylic acids or anhydrides are linear or cyclic C2-C6 alkyl dicarboxylic acids or anhydrides, preferably the hydroxyalkyl (meth)acrylate monomer is a hydroxy C2-C4 alkyl (meth)acrylate, preferably the lactone monomer is selected from the group consisting of γ-butyrolactone, δ-valerolactone, and ε-caprolactone, and preferably the monomers for copolymerization further comprise a monomer selected from the group consisting of (meth)acrylic acid and styrene.

[0072] A sixth embodiment is the cardanol derivative-modified polymer of any one of the first to third embodiments, wherein the carboxyl functional polymer is obtained from the copolymerization of a monomer selected from the group consisting of (meth)acrylic acid and a monomer selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 3,3,5-trimethylhexyl acrylate, 3,3,5-trimethylhexyl methacrylate, and preferably the monomers for copolymerization further comprise styrene.

[0073] A seventh embodiment includes the following steps: i) providing a mixture containing a cardanol derivative compound and a carboxyl functional polymer, preferably further containing at least one catalyst selected from triphenylphosphine, triphenylantimony, and chromium (III) acetylacetonate; ii) heating the mixture obtained in step i) in the presence of a solvent at a temperature of less than 200°C, preferably between 120°C and 180°C; 7. A method for preparing the cardanol derivative-modified polymer of any one of embodiments 1 to 6, comprising:

[0074] An eighth embodiment is the method according to the seventh embodiment, wherein in the mixture obtained in step i), the molar ratio of the total epoxy groups of the cardanol derivative compound to the total carboxyl groups of the carboxyl-functional polymer is 1:1 or less, preferably 3:5 to 1:1.

[0075] A ninth embodiment is a coating composition containing the cardanol derivative-modified polymer of any one of embodiments 1 to 6, or obtainable by the method of embodiment 7 or 8.

[0076] The tenth embodiment is (A) 30% by weight to 60% by weight, preferably 40% by weight to 60% by weight, of the cardanol derivative-modified polymer according to any one of embodiments 1 to 6 or the cardanol derivative-modified polymer obtainable by the method according to embodiment 7 or 8, based on the total weight of the coating composition; and (B) 15% by mass to 30% by mass, preferably 20% by mass to 30% by mass, of a curing agent based on the total mass of the binder in the coating composition, and the remaining solvent. Including, Preferably, in the coating composition of embodiment 9, the curing agent is at least one selected from the group consisting of an isocyanate curing agent, an aminoplast curing agent, and an amine curing agent.

[0077] An eleventh embodiment is a method for preparing an automotive coating, comprising incorporating into the automotive coating a cardanol derivative-modified polymer described in any one of embodiments 1 to 6, or obtainable by the method described in embodiment 7 or 8.

[0078] A twelfth embodiment is a method of using a cardanol derivative-modified polymer according to any one of embodiments 1 to 6, or obtainable by the method according to embodiment 7 or 8, in the preparation of a coating for automotive OEM manufacturing or automotive refinishing. [Example]

[0079] The invention is further illustrated by the following examples, which do not limit the scope of the invention as described and claimed. Unless otherwise defined, all parts are parts by weight.

[0080] How to determine the acid number The acid number was determined using "Method A" in accordance with DIN EN ISO 2114 (date: June 2002). The acid number corresponds to the mass (mg) of potassium hydroxide required to neutralize 1 g of sample under the conditions specified in DIN EN ISO 2114. The stated acid number corresponds to the total acid number specified in the DIN standard.

[0081] How to determine viscosity Brookfield CAP 2000+ rotational viscometer, spindle 3, shear rate: 10,000 s at 25°C -1 The viscosity was measured using

[0082] How to determine Mw (mass average molecular weight) Mn was determined by gel permeation chromatography (GPC) according to DIN 55672-1 (date: August 2007). Tetrahydrofuran was used as the eluent and polystyrene was used as the calibration polymer. The column material was a styrene-divinylbenzene copolymer.

[0083] Method for determining non-volatile content In the present invention, the non-volatile content of the samples was determined according to DIN EN ISO 3251 (June 1, 2008) at 125°C for 60 minutes with an initial mass of 1.0 g (Table A.2 of DIN EN ISO 3251, Method C). The non-volatile content of the samples was determined according to Table A.1 of DIN EN ISO 3251 (date: June 1, 2008). For this determination, 1 g of sample was weighed onto a pre-dried aluminum dish, dried in a drying oven at 130°C for 60 minutes, cooled in a desiccator, and then weighed again. The remaining amount relative to the total amount of sample introduced corresponds to the non-volatile content.

[0084] How to determine the Tg (glass transition temperature) of a polymer For the purposes of this invention, Tg was experimentally determined according to DIN 51005 "Thermal Analysis (TA) - Terminology" and DIN 53765 (March 1994) "Thermal Analysis - Differential Scanning Calorimetry (DSC)." A 15 mg sample was weighed into a sample boat and inserted into the DSC instrument. After cooling to the starting temperature, measurements were performed in runs 1 and 2 at a heating rate of 10 K / min under an inert gas blanket (N2) of 50 ml / min, with cooling to the starting temperature between runs. Measurements were typically performed in the temperature range from approximately 50°C below the expected glass transition temperature to approximately 50°C above the glass transition temperature. For the purposes of this invention, the glass transition temperature according to DIN 53765, section 8.1, is the temperature in the second measurement run at which half the change in specific heat capacity (0.5 delta cp) was reached. This was determined from the DSC diagram (heat flow versus temperature plot). This represents the temperature corresponding to the intersection of the measured plot and the center line between the extrapolated baselines before and after the glass transition.

[0085] Example 1: Preparation of a Carboxyl-Functional Acrylic Polymer A 2L glass flask was charged with 24.4 parts of solvent naphtha. When the temperature stabilized at 150°C, 5.6 parts of tert-butyl peroxy-2-ethylhexanoate and 1.2 parts of solvent naphtha were slowly added dropwise to the flask. 15 minutes after the initiator addition, 8.3 parts of styrene, 18.4 parts of n-butyl methacrylate, 5.1 parts of 2-hydroxyethyl methacrylate, 2.7 parts of ethylhexyl acrylate, and 18.0 parts of acrylic acid were slowly added dropwise to the flask. After the monomer addition was completed, the initiator addition continued for another 30 minutes. After a single post-polymerization period of 60 minutes, the mixture in the glass flask was cooled to 80°C, and 16.3 parts of solvent naphtha was added. The acid value of the resulting carboxyl-functional acrylic polymer was 134 mgKOH / g.

[0086] Example 2: Preparation of cardanol derivative modified polymer based on the product obtained from Example 1 1 kg of the polymer suspension obtained from Example 1 (content of the carboxyl-functional acrylic polymer obtained from Example 1: 61.5 wt %; solvent: naphtha) and 0.896 kg of Cardolite NC513 (Cardolite Corporation, Zhuhai, China) were charged into a reactor (in the reaction system in the reactor, the molar ratio of epoxy groups (from Cardolite NC513) to acid groups (from the carboxyl-functional acrylic polymer prepared in Example 1) was 1:1) and heated to 120°C. 0.86 g of triphenylphosphine was added as a reaction catalyst. The temperature was raised to 140°C in the first hour and then maintained at a temperature in the range of 140°C to 150°C.

[0087] The progress of the reaction was monitored by acid value and EEW (epoxy equivalent weight). The reaction was complete when the EEW was undetectable (i.e., the epoxy groups were completely consumed) and the acid value dropped to only 1.5 mg KOH / g. The resulting polymer was a Cardolite NC513-modified carboxyl-functional acrylic polymer, corresponding to the cardanol derivative-modified polymer of the present invention.

[0088] The non-volatile content and viscosity of the resulting product in the reactor were measured according to the methods described herein. Table 1 shows a comparison of the non-volatile content and viscosity of the products obtained from Example 1 and Example 2.

[0089] [Table 1]

[0090] Example 3: Preparation of Carboxyl-Functional Polyester Polymer 37.4 parts of hexahydrophthalic anhydride, 10.6 parts of adipic acid, 0.8 parts of xylene, 17.4 parts of trimethylolpropane, and 5 parts of hexanediol were charged into a reactor, and the temperature was slowly raised to 230°C, and the head temperature of the column separation was maintained below 95°C; after reaching the target acid value (in the range of 117 to 123 mg KOH / g), the mixture in the reactor was cooled to 100°C, and 30.8 parts of naphtha was added as a solvent.

[0091] Example 4: Preparation of cardanol derivative modified polymer based on the product obtained from Example 3 1 kg of the polymer suspension obtained from Example 3 (content of the carboxyl functional acrylic polymer obtained from Example 3: 63.5 wt %; solvent: naphtha) and 0.8 kg of Cardolite NC513 were charged into a reactor (in the reaction system in the reactor, the molar ratio of epoxy groups from Cardolite NC513 to acid groups from the carboxyl functional polyester polymer was 1:1) and heated to 120°C. 0.77 g of triphenylphosphine was added as a reaction catalyst. The temperature was raised to 140°C in the first hour and then maintained at a temperature in the range of 140°C to 150°C.

[0092] The progress of the reaction was monitored by the acid value and EEW (epoxy equivalent weight). The reaction was complete when the EEW was undetectable (i.e., the epoxy groups were completely consumed) and the acid value dropped to only 3.9 mg KOH / g. The resulting polymer was a Cardolite NC513-modified carboxyl-functional polyester polymer, corresponding to the cardanol derivative-modified polymer of the present invention.

[0093] The non-volatile content and viscosity of the resulting product in the reactor were measured according to the methods described herein. Table 2 shows a comparison of the non-volatile content and viscosity of the products obtained from Example 3 and Example 4.

[0094] [Table 2]

Claims

1. A cardanol derivative modified polymer obtained by reacting an epoxy group in a cardanol derivative compound with a carboxyl group in a carboxyl functional polymer, wherein the cardanol derivative compound is a reaction product of cardanol and a haloalkylene oxide having 3 to 10 carbon atoms, the acid value of the carboxyl functional polymer is 100 to 200 mg KOH / g, and at least 60% of the carboxyl groups in the carboxyl functional polymer have reacted with the epoxy group in the cardanol derivative compound; the carboxyl functional polymer is at least one selected from the group consisting of carboxyl functional polyacrylics, carboxyl functional polyesters, carboxyl functional polyurethanes, and carboxyl functional polyamides; Cardanol derivative modified polymer.

2. 2. The cardanol derivative-modified polymer of claim 1, wherein the weight average molecular weight of the carboxyl functional polymer is from 1,000 g / mol to 12,000 g / mol.

3. 3. The cardanol derivative modified polymer of claim 1 or 2, wherein the carboxyl functional polymer is obtained from the polymerization of (meth)acrylic acid.

4. The carboxyl functional polymer is obtained by the polymerization of a monomer selected from the group consisting of hydroxyalkyl(meth)acrylates and a monomer selected from the group consisting of linear or cyclic alkyl dicarboxylic acids or anhydrides, or by the polymerization of a monomer selected from the group consisting of hydroxyalkyl(meth)acrylates and a monomer selected from the group consisting of linear or cyclic alkyl dicarboxylic acids or anhydrides and lactones, wherein the linear or cyclic alkyl dicarboxylic acids or anhydrides are linear or cyclic C ２ ~C ６ alkyl dicarboxylic acid or anhydride, and the hydroxyalkyl (meth)acrylate monomer is hydroxy C ２ ~C ４ 3. The cardanol derivative-modified polymer according to claim 1 or 2, wherein the lactone monomer is an alkyl (meth)acrylate and is selected from the group consisting of γ-butyrolactone, δ-valerolactone, and ε-caprolactone.

5. 3. The cardanol derivative-modified polymer of claim 1 or 2, wherein the carboxyl functional polymer is obtained from the copolymerization of a monomer selected from the group consisting of (meth)acrylic acid and a monomer selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 3,3,5-trimethylhexyl acrylate, and 3,3,5-trimethylhexyl methacrylate.

6. The following steps: i) providing a mixture containing a cardanol derivative compound and a carboxyl functional polymer; ii) heating the mixture obtained in step i) at a temperature below 200° C. in the presence of a solvent; 6. A method for preparing the cardanol derivative-modified polymer of claim 1, comprising:

7. 7. The method of claim 6, wherein in the mixture obtained in step i), the molar ratio of total epoxy groups of the cardanol derivative compound to total carboxyl groups of the carboxyl functional polymer is from 3:5 to 1:

1.

8. A coating composition comprising the cardanol derivative-modified polymer according to any one of claims 1 to 5.

9. (A) 30% to 60% by weight, based on the total weight of the coating composition, of the cardanol derivative-modified polymer according to any one of claims 1 to 5; and (B) 15% to 30% by weight of a curing agent, based on the total weight of the binder in the coating composition, and the remainder a solvent. Including, 9. The coating composition of claim 8, wherein the curing agent is at least one selected from the group consisting of an isocyanate curing agent, an aminoplast curing agent, and an amine curing agent.

10. 8. A method for preparing an automotive coating, comprising incorporating into the automotive coating a cardanol derivative-modified polymer according to any one of claims 1 to 5, or a cardanol derivative-modified polymer obtained by the method according to claim 6 or 7.

11. 8. Use of a cardanol derivative modified polymer according to any one of claims 1 to 5 or obtainable by the method according to claim 6 or 7 for the preparation of coatings for automotive OEM manufacturing or automotive refinishing.

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