Glycidyl esters of alpha, alpha branched acids derived from renewable sources and blends thereof

Abstract

The present invention relates to compositions of α,α-branched alkanecarboxylic acid glycidyl esters derived from rosin and / or hydrogenated rosin reacted with epihalohydrins. The glycidyl ester compositions can be used, for example, as monomers in binder compositions for coatings and adhesives, as reactive diluents, or as acid scavengers. The present invention also relates to the use of rosin and / or hydrogenated rosin glycidyl esters in combination with polyester polyols, acrylic polyols, or polyether polyols.

Description

[Technical field]

[0001] The present invention relates to a composition of α,α-branched alkanecarboxylic acid glycidyl esters derived from rosin (from various sources: e.g. gum, tall oil) or hydrogenated rosin, reacted with epihalohydrins. The rosins used in the present invention have the general formula C 19 H 29 It is composed of diterpene monocarboxylic acids with COOH. The carboxylic acid is a trialkylacetic acid derivative and further has a three-ring carbon skeleton. The crude rosin is a mixture of several isomers with two or three unsaturations, which may be conjugated or not. The crude rosin is a solid brittle product with a dark brown color, and lighter products are obtained after partial or complete hydrogenation of the unsaturations. The tertiary carboxylic acid reacts with epihalohydrins to produce glycidyl esters equivalent to neoalkanoic acid glycidyl esters, such as neononanoic or neodecanoic acid glycidyl esters. The present invention, in combination with some polymers, such as polyester polyols, provides various unexpected performances, such as improved hardness, higher glass transition temperature (Tg), and faster drying of coatings derived therefrom. Summary of the Invention

[0002] The glycidyl esters of rosin derivatives can be obtained according to JPS5560575, JPS6469680, JPH03115480, JPH09143430 or other glycidylation methods known in the art.

[0003] The glycidyl ester composition can be used, for example, as a monomer in a binder composition for a coating or adhesive, as a reactive diluent, or as an acid scavenger.

[0004] Another use of glycidyl esters is in combination with polyester polyols, or acrylic polyols, or polyether polyols, or polyether-ester polyols, or alkyd resins. The combination of acrylic polyols with polyester polyols, such as those used in coatings in the automotive industry, results in fast-drying coating systems with attractive coating properties. The coating compositions may be in organic solvents, may be water-based, or may be solids used in powder coating applications. The coatings can be applied to metals, plastics, or wood using appropriate techniques.

[0005] The glycidyl ester compositions can be used, for example, as reactive diluents in formulations containing epoxy resins such as EPIKOTE 828. The curing agent can be an amine, an anhydride, or an acid, such as diethylenetriamine, methylnadic anhydride, or cyclohexanedicarboxylic acid, respectively.

[0006] The present invention relates to a method for preparing an epoxy resin hardener composition, which is obtained by incorporating a mixture of glycidyl esters, as described above, into a mixture comprising an epoxy resin and a hardener.

[0007] Said resins may be, for example, aromatic or aliphatic halogenated or non-halogenated glycidyl ether resins. Commercially available halogenated resins are, for example, EPON 1163, EPIKOTE 5123, EPIKOTE 5119 and EPIKOTE 5112 (EPON / EPIKOTE from Hexion) or any other glycidyl ether of tetra-bromo-bis-phenol derivatives containing more than 10% by weight of bromine in the resinous material. Examples of non-halogenated epoxy resins are the diglycidyl ethers of bisphenol A and / or bisphenol F and / or the polyglycidyl ethers of phenol / cresol-formaldehyde novolac. Commercially available examples of such resins are EPIKOTE 828, EPIKOTE 834, EPIKOTE 1001, EPIKOTE 1002, EPIKOTE 154, EPIKOTE 164.

[0008] Amines, anhydrides and acids can be used as hardener hardening materials.

[0009] The amines may be aliphatic amines such as, for example, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), isophoronediamine (IPD), para-aminocyclohexanemethylene (PACM), diaminocyclohexane (DCH), meta-xylenediamine (mXDA), 4,4'-diamino-3,3'-dimethyldicyclohexylmethane (DDCM) and adducts of aliphatic amines such as those based on DETA, TETA, TEPA, IPD, PACM, DCH, mXDA, DDCM, etc., or aromatic amines such as MDA.

[0010] The above-mentioned anhydrides usable as curing agents may be, for example, cycloaliphatic anhydrides. The curable compositions disclosed herein may include one or more cycloaliphatic anhydride curing agents. The cycloaliphatic anhydride curing agents may include, for example, methylnadic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, dodecenyl succinic anhydride, phthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride, among others. The anhydride curing agent may also include copolymers of styrene and maleic anhydride and other anhydrides, as described in US 6,613,839. The curing agents usable in the curable compositions disclosed herein may also include, for example, acids derived from any of the above-mentioned anhydrides.

[0011] The present invention also relates to an epoxy resin curable composition useful for impregnating fibers applicable in the manufacture of composite structures, laminates, coatings, flooring and putty applications comprising at least the mixture of glycidyl esters described above.

[0012] According to another embodiment of the present invention, the composition as specified above can be used in flooring applications where high chemical resistance is required.

[0013] In accordance with yet another aspect of the present invention, the compositions described above can be used to make composite materials with glass, carbon or natural fibers by techniques known in the art.

[0014] In accordance with yet another aspect of the invention, the glycidyl esters described above can be used in combination with polyester fibers (as acid scavengers) to improve hydrolytic stability during extrusion and subsequent use.

[0015] As used herein, "rosin" (from various sources: e.g., gum, tall oil) or "rosin portion" is intended to include rosin, include rosin acids, and further include rosin derivatives that are rosin that have been processed, e.g., disproportionated or hydrogenated. As is known in the art, rosin is a mixture of at least eight monocarboxylic acids (abietic acid, palustric acid, dehydroabietic acid, neoabietic acid, levopimaric acid, pimaric acid, sandaracopimaric acid, and isopimaric acid). Abietic acid may be the predominant species, with the other seven acids being isomers thereof. Due to the composition of rosin, the synonym "rosin acid" is often used to describe various rosin-derived products. The rosin portion includes chemically modified rosin such as partially or fully hydrogenated rosin acids, partially or fully dimerized rosin acids, functionalized rosin acids, disproportionated rosin acids, isomerized rosin acids, or combinations thereof, as known in the art. Rosin is commercially available in several forms, such as rosin acids, rosin esters, and dimerized rosin, and hydrogenated rosin is available, for example, from Eastman Chemicals in the product lines Poly-Pale™, Dymerex™, Staybelite-E™, Foral™ Ax-E, Lewisol™, and Pentalyn™, from Arizona Chemicals in the product lines Sylvalite™ and Sylvatac™, and from Arakawa-USA in the product lines Pensel and Hypal.

[0016] Another aspect of the invention is further illustrated by the synthesis of glycidyl esters of rosin (rosin GE) or glycidyl esters of hydrogenated rosin (H-rosin GE). The glycidylation of the acid functional groups of rosin or hydrogenated rosin is carried out according to the method of claim 1 and is further illustrated in the examples.

[0017] Such glycidyl esters can be made by reacting an alkali salt of a carboxylic acid with a halo-substituted monoepoxide, such as an epihalohydrin, e.g., epichlorohydrin (1-20 molar excess). The mixture is heated (50-150°C) in the presence of a catalyst to form the glycidyl ester and the alkali salt and water. The water and excess epihalohydrin are removed by azeotropic distillation, and salt by-products, e.g., NaCl, are removed by filtration and / or washing. Glycidyl esters can also be made by reacting a carboxylic acid directly with epichlorohydrin under similar process conditions. The chlorohydrin ester intermediate formed during this reaction is subsequently treated with an alkaline material, e.g., sodium hydroxide or potassium hydroxide, to yield the desired glycidyl ester. The by-product salts are removed by washing and / or filtration, and the water is removed by drying.

[0018] 1. A process for the preparation of "rosin" or hydrogenated rosin glycidyl esters, comprising the steps of: (a) reaction of rosin acid with a 2-20 molar excess of a halo-substituted monoepoxide, such as epihalohydrin (e.g., epichlorohydrin), in the presence of water and water-miscible solvents, in the presence of a catalyst, in an amount up to 45 mol % molar amount of "rosin" acid, at a temperature ranging from 30° C. to 110° C. for a period ranging from 0.5 to 2.5 hours; (b) adding additional alkali metal hydroxide or alkali metal alkanolate in a maximum molar ratio in the range of 0.9:1 to 1.2:1, preferably 0.95:1 to 1.10:1, relative to the monocarboxylic acid groups, and reacting at a temperature of 0 to 80° C.; (c) distillation of the resulting reaction mixture to remove excess halo-substituted monoepoxide and solvent and generated water; and (d) optional treatment of the residual product with concentrated aqueous alkali metal hydroxide or alkali metal alcoholate solution to complete the dehydrohalogenation (preferably dehydrochlorination), followed by removal of the alkali metal halide salt, for example by washing the resulting glycidyl ester with water. A method comprising:

[0019] Another preparation of "rosin" glycidyl esters is by reacting "rosin" with an epoxyalkyl halide containing 3 to 13 carbon atoms in the presence of a catalyst; a total amount of epoxy alkyl halide in excess of the stoichiometric amount reacts in a coupling reaction with an acid (e.g., preferably in a molar ratio of epoxy alkyl halide to acid in the range of 1.02:1 to 1.50:1) to form an intermediate reaction product that includes a halohydrin; When the epoxy alkyl halide is added to the acid with adequate cooling of the reactants and / or reaction mixture to keep the temperature of the reaction mixture below 80°C, the epoxy alkyl halide and the acid react at a temperature below 80°C (preferably in the range of 55-75°C) for a time sufficient to completely convert the total amount of acid; - optionally removing excess epoxy alkyl halide from the reaction product prior to the ring closure reaction; subjecting the reaction product to a ring closure reaction (DHC) and, optionally, one or more post-treatment steps (ADHC) for removal of residual halo functionality; Optionally adding a solvent before or after DHC to reduce viscosity and promote phase separation after a water wash to remove salts; For temperature control, optionally, a vacuum on the reactor is used to reflux excess epoxy alkyl halide to the reactor.

[0020] The catalyst used in the process of the invention is preferably a homogeneous catalyst that does not require a solvent. The catalyst may be selected from catalysts known in the prior art. The catalyst may thus be an alkali metal hydroxide, an alkali metal carbonate, an alkaline earth hydroxide, an alkali metal or alkaline earth metal alcoholate, or an ammonium salt, in particular of the formula R'R''R'''R''N + Y - wherein R', R'' and R'" may each independently represent an alkyl group having 1 to 16 carbon atoms, which may be optionally substituted with one or more hydroxyl groups, where R''" represents an alkyl group having 1 to 16 carbon atoms, represents phenyl or represents benzyl, and Y represents hydroxyl or a halogen, such as chlorine, bromine or iodine. Also their corresponding phosphonium salts and aromatic forms, such as ethyltriphenylphosphonium iodide, can be used.

[0021] Preferred catalysts in the coupling reaction are ammonium salts, particularly those of the formula R'R''R'''R''''N + Y - wherein R1, R2 and R3 may each independently represent an alkyl group having 1 to 10 carbon atoms, and Y represents chlorine or bromine.

[0022] As noted above, the method involves two steps; a coupling reaction and a ring-closing reaction to convert the intermediate halohydrin to the desired glycidyl ester.

[0023] In the ring-closing reactions known in the art, preferably relatively strong, water-soluble metal hydroxides or metal alcoholates are used. This so-called DHC reaction can be carried out by addition of an alkali metal hydroxide or an alkali metal alkanolate. The reaction is preferably carried out at a temperature between 50 and 90° C., more preferably between 60 and 80° C. The brine formed during the ring-closing reaction may be completely or partially removed, so that the product may be subjected to an optional work-up.

[0024] The alkali metal hydroxides or alkali metal alkanolates usable in the above steps for DHC and ADHC are preferably selected from sodium hydroxide or potassium hydroxide, from sodium alkanoates having 1 to 6 carbon atoms, such as sodium isopropanoate, or from potassium alcoholates. Most preferably, sodium hydroxide is used, or from sodium alkanoates having 1 to 6 carbon atoms.

[0025] In these steps, sodium hydroxide is used as an aqueous solution preferably having a concentration of 15 to 60% by weight, more preferably 20 to 50% by weight.

[0026] Removal of solvent and water from the reaction product may be accomplished by stripping or distillation, it being understood that a drying step may be performed after the final wash step, if desired. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] Methods used Test methods for characterizing resins The molecular weight of the resins is measured using gel permeation chromatography (Perkin Elmer / Water) in THF solution using polystyrene standards. The viscosity of the resins is measured using a Brookfield viscometer (LVDV-I) at the indicated temperatures. The solids content is calculated using the function (Ww-Wd) / Ww x 100%, where Ww is the weight of the wet sample and Wd is the weight of the sample after drying in an oven at a temperature of 110°C for 1 hour.

[0028] Tg (glass transition temperature) was determined using a Perkin Elmer DSC7 or a TA Instruments Thermal Analysis instrument. Scan rates were 20 and 10°C / min, respectively. Only data obtained under the same experimental conditions were compared. Otherwise, temperature differences resulting from different scan rates were demonstrated to be insignificant for the compared results.

[0029] Yellowness Value Measurements taken on platinum-cobalt scale using a Hach Lange Lico500 Methods for Characterization of Coatings Pot Life Pot life is determined by observing the time elapsed for the starting viscosity to double at room temperature, usually 24.0±0.5° C.

[0030] Clearcoat Application A Q-panel is used as a substrate. The panel is then cleaned with the fast evaporating solvents methyl ethyl ketone or acetone.

[0031] Dry time to touch The dry-to-touch time (DFT) of clearcoats is evaluated by dropping a purified cotton ball vertically from a specified distance onto a flat substrate. When the cotton ball makes contact with the substrate, the substrate is immediately turned over. The dry-to-touch time is defined as the time interval at which the purified cotton ball no longer adheres to the substrate.

[0032] Hardness evolution The hardness evolution is followed using a pendulum hardness tester according to the Koenig method.

[0033] Chemicals used Rosin: available from Sigma-Aldrich Hydrogenated Rosin: Available from Foreverest Glycidyl ester of rosin: Synthesized according to the method of Example 1 Glycidyl ester of hydrogenated rosin: Synthesized according to the method of Example 1 Cardura™ E10P: available from Hexion Cardura™ 9: Available from Hexion Ethylene glycol: from Aldrich · Monopentaerythritol: available from Sigma-Aldrich Methylhexahydrophthalic anhydride: available from Sigma-Aldrich Acrylic acid: available from Sigma-Aldrich Methacrylic acid: available from Sigma-Aldrich Hydroxyethyl methacrylate: available from Sigma-Aldrich Styrene: available from Sigma-Aldrich 2-Ethylhexyl acrylate: available from Sigma-Aldrich Methyl methacrylate: available from Sigma-Aldrich Butyl acrylate: available from Sigma-Aldrich Isobornyl methacrylate: available from Sigma-Aldrich Xylene Di-t-amyl peroxide is Luperox DTA from Arkema tert-Butylperoxy-3,5,5-trimethylhexanoate: available from Akzo Nobel ·Aldrich n-Butyl Acetate Biosolve Dichloromethane Thinner A is a mixture of 50 wt% xylene, 30 wt% toluene, 10 wt% Shellsol A, and 10 wt% 2-ethoxyethyl acetate. ·Thinner B is butyl acetate. Hardener, HDI: 1,6-Hexamethylene diisocyanate trimer, Desmodur N3390BA from Bayer Material Science, i.e. Covestro, or Tolonate HDT LV2 from Perstorp Leveling agent: "BYK10wt%" which is BYK-331 diluted to 10% with butyl acetate Catalyst: Dibutyltin dilaurate diluted to 1 wt% with butyl acetate (DBTDL 1 wt%) Pigment dispersant: BYK Disperbyk110 Surface levelling for paints: BYK358N from BYK Defoamer: BYK 077 Sedimentation control: Lubrizol Solthix 250 Titanium dioxide pigment: Ti-Pure TS6200 from The Chemours Company Thinners for paint formulations: Ethyl ethoxypropionate from Sigma-Aldrich, Methyl amyl ketone from Sigma-Aldrich HALS additive: Tinuvin 123 from BASF UVA additive: BASF Tinuvin 1130 Hardener for paints: Desmodur N3300 from Covestro Synthesis of glycidyl esters of rosin and hydrogenated rosin EXAMPLES

[0034] [Example 1] 750 grams of hydrogenated gum rosin, 321 grams of toluene, and 21.8 grams of tetramethylammonium chloride (as a 50% aqueous solution) (0.04 mol / mol hydrogenated gum rosin) were charged to a reactor and heated to 70°C.

[0035] Epichlorohydrin was added to the reactor while the reaction medium was cooled to about 70° C., the rate of addition being kept slow to allow adequate cooling. A total of 253 grams of epichlorohydrin was added over a period of about 90 minutes (1.1 mol / mol hydrogenated gum rosin). The addition time is therefore a function of the efficiency of cooling. The reaction was monitored and took approximately 7 hours under these conditions.

[0036] The ring closure reaction was carried out at 70° C. in the presence of caustic. A total of 246 g NaOH 50% (1.24 mol / mol hydrogenated gum rosin) was used. A linear profile was used to add the NaOH over 90 minutes. After a post reaction time of 210 minutes, the ring closure reaction was complete. An additional 1375 grams of toluene and 653 grams of water were added to wash out the salt. The brine phase was removed after phase separation, followed by a final water wash. Toluene was removed from the product by stripping under reduced pressure.

[0037] The product was analyzed for EGC and found to be 2567 mmol / kg. Gardner color (50% in toluene) was 1.

[0038] Binder Preparation and Formulation Examples

[0039] [Example 1] Comparison The following components were charged to a reaction vessel equipped with a stirrer, condenser, and thermometer: 92.4 grams of Cardura™ E10P, 24.0 grams of butyl acetate. This initial reactor charge was heated up to 135° C. Then the following mixture was added over a period of 1 hour and 20 minutes while keeping the temperature constant: 27.5 grams of acrylic acid, 1.2 grams of Di-t-amyl peroxide, 12.0 grams of n-butyl acetate. After an additional addition of 1.2 grams of Di-t-amyl peroxide and 20.4 grams of n-butyl acetate, the post-cooking process was continued at 135° C. for 1 hour.

[0040] [Example 2a] The following components were charged to a reaction vessel equipped with a stirrer, condenser, and thermometer: 92.4 grams of Rosin GE, 24.0 grams of Butyl Acetate. This initial reactor charge was heated up to 135° C. Then the following mixture was added over a period of 1 hour and 18 minutes while keeping the temperature constant: 16.7 grams of Acrylic Acid, 1.2 grams of Di-t-Amyl Peroxide, 12.0 grams of n-Butyl Acetate. After an additional addition of 1.2 grams of Di-t-Amyl Peroxide and 20.4 grams of n-Butyl Acetate, the post-cooking process was continued at 135° C. for 1 hour.

[0041] Example 2b The following components were charged to a reaction vessel equipped with a stirrer, condenser, and thermometer: H-rosin GE, 92.4 grams; Butyl acetate, 24.0 grams. This initial reactor charge was heated up to 135° C. Then the following mixture was added over a period of 1 hour and 18 minutes while keeping the temperature constant: Acrylic acid, 16.8 grams; Di-t-amyl peroxide, 1.2 grams; n-Butyl acetate, 12.0 grams. After an additional addition of 1.2 grams of Di-t-amyl peroxide and 20.4 grams of n-Butyl acetate, the post-cooking process was continued at 135° C. for 1 hour.

[0042] Observation: The Tg of the acrylic polyol is influenced by the choice of glycidyl ester.

[0043] [Example 3] Rosin GE or H-Rosin GE adducts with acrylic acid (ACE-adducts) and methacrylic acid (MACE-adducts) (see Table 3) are acrylic monomers that can be used to formulate hydroxyl-functional (meth)acrylic polymers.

[0044] [Table 1]

[0045] · DABCO T9 and 4-methoxyphenol (185 ppm calculated on the weight of the glycidyl ester) are charged to the reactor. The reaction is carried out under air flow (to recycle the radical inhibitor). The reactor charge is heated slowly, under constant stirring, to about 80°C, where an exothermic reaction begins, increasing the temperature to about 100°C. The temperature is maintained at 100°C until an epoxy group content of less than 30 meq / kg is achieved. The reaction mixture is cooled to room temperature.

[0046] [Example 4] Acrylic Resin A glass reactor equipped with a stirrer was flushed with nitrogen and the initial reactor charge (see Table 4) was heated to 140° C. The monomer mixture with initiator was then gradually added to the reactor via pump over a period of 5 hours at this temperature. Additional initiator was then fed to the reactor for an additional hour at 140° C. Finally, the polymer was cooled to 135° C. and diluted with butyl acetate to a solids content of about 75%.

[0047] [Table 2]

[0048] A clearcoat was then formulated using the following ingredients (Table 5) and applied with a film formation of 80 μm wet.

[0049] [Table 3]

[0050] Comparative properties are shown in Table 6.

[0051] [Table 4]

[0052] Acrylic Resin A glass reactor equipped with a stirrer was flushed with nitrogen and the initial reactor charge (see Table 7) was heated to 150° C. The monomer mixture with initiator was then gradually added to the reactor via pump over a period of 5 hours at this temperature. Additional initiator was then fed to the reactor for an additional hour at 150° C. Finally, the polymer was cooled to 135° C. and diluted with butyl acetate to a solids content of about 70%.

[0053] [Table 5]

[0054] A clearcoat was then formulated using the following ingredients (Table 8) and applied with a film build of 80 μm wet.

[0055] [Table 6]

[0056] Comparative properties are shown in Table 9.

[0057] [Table 7]

[0058] Acrylic Resin A glass reactor equipped with a stirrer was flushed with nitrogen and the initial reactor charge (see Table 10) was heated to 140° C. The monomer mixture with initiator was then gradually added to the reactor via pump over a period of 5 hours at this temperature. Additional initiator was then fed to the reactor for an additional hour at 140° C. Finally, the polymer was cooled to 135° C. and diluted with butyl acetate to a solids content of about 75%.

[0059] [Table 8]

[0060] A clearcoat was then formulated using the following ingredients (Table 11) and applied with a film build of 80 μm wet.

[0061] [Table 9]

[0062] Comparative properties are shown in Table 12.

[0063] [Table 10]

[0064] [Example 5] Clearcoat for Automotive Refinishing The solvents were mixed to give a thinner mixture of the following composition (Table 13):

[0065] [Table 11]

[0066] A clearcoat was then formulated using the following ingredients (Table 14) (parts by weight):

[0067] [Table 12]

[0068] These clearcoats can be applied by spraying.

[0069] Pigmented 2K polyurethane The same resins can also be used in pigmented systems for industrial applications. An example of a white paint formulation is shown below.

[0070] [Table 13]

[0071] [Example 6] Acrylic polymer based on Rosin GE or H-Rosin GE for medium solids first finish clearcoat

[0072] The reactor for acrylic polyol is flushed with nitrogen and the initial reactor charge (see Table 16) is heated to 140°C. At this temperature, the monomer mixture with initiator is added to the reactor via pump over 5 hours. Additional initiator is fed to the reactor over 1 hour, and then the mixture is held at 140°C to complete the post-reaction conversion. Finally, the polymer is cooled and diluted with butyl acetate to a solids content of about 60%.

[0073] [Table 14]

[0074] Clear lacquer formulation A clear lacquer is formulated from an acrylic polymer with the addition of Cymel 1158 (a hardener from CYTEC) and a solvent to dilute to spray viscosity (see Table 17). The acidity of the polymer is sufficient to catalyze the curing process, so no additional acid catalyst is added. The lacquer is thoroughly stirred to obtain a homogeneous composition.

[0075] [Table 15]

[0076] Application and Curing Coatings are applied to Q-panels using a bar coater to achieve a dry film thickness of approximately 40 μm. The system is allowed to flash off at room temperature for 15 minutes and then baked at 140° C. for 30 minutes. Tests on the cured system are carried out after 1 day at 23° C.

[0077] [Example 7] A glass reactor equipped with a stirrer was flushed with nitrogen and the initial reactor charge (see Table 18) was heated to 140° C. The monomer mixture with initiator was then gradually added to the reactor via pump over a period of 5 hours at this temperature. Additional initiator was then fed to the reactor for an additional hour at 140° C. Finally, the polymer was cooled to 135° C. and diluted with butyl acetate to a solids content of about 75%.

[0078] [Table 16]

[0079] [Example 8] Polyesters by polyaddition Trimethylolpropane, methylhexahydrophthalic anhydride or succinic anhydride and n-butyl acetate were charged to a reaction vessel and heated at the boiling point of butyl acetate until complete conversion. Cardura E10P or Rosin GE or H-Rosin GE was then added dropwise and the reaction continued at 150°C until an acceptable acid number was achieved. The polyester has a solids content of about 80.0 wt%. The formulation and properties are specified in Table 19.

[0080] [Table 17]

[0081] The resin of Example 8 can be formulated into coating compositions such as 2K (polyurethane) that have low VOC (volatile organic compound) levels and can provide excellent appearance combined with fast drying speed.

[0082] Polyester by polycondensation The same types of polyesters described in Table 20 can also be prepared by using polyfunctional acids instead of anhydrides. The reaction of the acid functionality with the hydroxyls is carried out at temperatures of about 200-240°C until full conversion in the presence of an azeotropic solvent such as xylene to remove water evolved during the process.

[0083] [Example 9] The resin of Example 8 can be mixed with acrylic polyols to obtain a resin suitable for, for example, automotive coatings. Examples of acrylic resins are shown in Table 19.

[0084] A glass reactor equipped with a stirrer was flushed with nitrogen and the initial reactor charge (see Table 20) was heated to 140° C. The monomer mixture with initiator was then gradually added to the reactor via pump over a period of 5 hours at this temperature. Additional initiator was then fed to the reactor for an additional hour at 140° C. Finally, the polymer was cooled to 135° C. and diluted with butyl acetate to a solids content of about 75%.

[0085] [Table 18]

[0086] The acrylic polyol is then blended with the polyester polyol of Example 8 at a level of 25 wt% polyester polyol to 75 wt% acrylic polyol. The blend is used to formulate a clearcoat (Table 21) and applied with a film formation of 80 μm wet.

[0087] [Table 19]

[0088] Comparative properties are shown in Table 22.

[0089] [Table 20]

[0090] [Example 10] The acrylic polyol and polyester polyol of Examples 8 and 9 can be prepared in the same reactor in a hybrid process. The polyester polyol is synthesized first and used as the initial reactor charge to prepare the acrylic polyol simultaneously in the same reaction. An example of such a process is given in Table 23, where Cardura E10P was used for the polyester polyol, but Rosin GE or H-Rosin GE can also be used for the preparation.

[0091] Trimethylolpropane, methylhexahydrophthalic anhydride and n-butyl acetate were charged into the reactor and heated at the boiling point of butyl acetate until complete conversion. Then Cardura E10P or Rosin GE or H-Rosin GE was added dropwise and the reaction was continued for another hour at 150°C to complete the acid conversion. The temperature inside the reactor was then lowered to 140°C, and then the monomer mixture with initiator was gradually added to the reactor via a pump at this temperature over a period of 5 hours. Additional initiator was then fed into the reactor at 140°C for another hour. Finally, the polymer was cooled to 135°C and diluted with butyl acetate to a solids content of about 75%.

[0092] [Table 21]

[0093] When applied to coatings, it has been observed that combining Rosin GE or H-Rosin GE with such a hybrid method significantly improves both VOC (volatile organic compounds) and premature drying development.

[0094] [Example 11] The polyether was obtained by charging the following components into a reaction vessel: 2.5500 grams of rosin GE, 1.1571 grams of dichloromethane, 0.0137 grams of boron trifluoride diethyl etherate. The reaction was carried out at room temperature for 3 days, and then the solvent was completely removed by evaporation.

[0095] [Example 12] The polyether was obtained by charging the following components into a reaction vessel: 2.5500 grams of H-rosin GE, 1.1571 grams of dichloromethane, 0.0137 grams of boron trifluoride diethyl etherate. The reaction was carried out at room temperature for 3 days, and then the solvent was completely removed by evaporation.

[0096] [Example 13] Comparison The polyether was obtained by charging the following components into a reaction vessel: 2.5500 grams of Cardura E10P, 1.1571 grams of dichloromethane, 0.0137 grams of boron trifluoride diethyl etherate. The reaction was carried out at room temperature for 3 days and then the solvent was completely removed by evaporation.

[0097] Observations: The Tg of modified polyether resins is influenced by the composition of the glycidyl ester type, with rosin-based glycidyl esters resulting in higher Tg.

[0098] [Example 14] Polyether Resin The following components were charged to a reaction vessel equipped with a stirrer, thermometer and condenser: 138 grams of di-trimethylolpropane (DTMP), 862 grams of rosin GE, 135.5 grams of n-butyl acetate (BAC) and 2.5 grams of stannous dioctoate. The mixture was heated to its reflux temperature of about 180° C. for about 4 hours until the rosin GE was converted to an epoxy group content of less than 0.12 mg / g. After cooling, the polyether had a solids content of about 88%.

[0099] [Example 15] Polyether Resin The following components were charged to a reaction vessel equipped with a stirrer, thermometer and condenser: 139 grams of di-trimethylolpropane (DTMP), 861 grams of H-rosin GE, 135.5 grams of n-butyl acetate (BAC) and 2.5 grams of stannous dioctanoate. The mixture was heated to its reflux temperature of about 180° C. for about 4 hours until the H-rosin GE was converted to an epoxy group content of less than 0.12 mg / g. After cooling, the polyether had a solids content of about 88%.

[0100] [Example 16] Comparison Polyether Resin The following components were charged to a reaction vessel equipped with a stirrer, thermometer and condenser: 123 grams of monopentaerythritol, 877 grams of Cardura E10P, 194 grams of n-butyl acetate and 3.552 grams of tin(II) 2-ethylhexanoate. The mixture was heated to a temperature of about 180° C. for about 6 hours until the Cardura E10P was converted to an epoxy group content of about 25 mmol / kg. After cooling, the polyether had a solids content of about 95%.

[0101] [Example 17] Polyether Resin The following components were charged to a reaction vessel equipped with a stirrer, thermometer and condenser: 79 grams of monopentaerythritol, 921 grams of rosin GE, 183 grams of n-butyl acetate and 0.3550 grams of tin(II) 2-ethylhexanoate. The mixture was heated to a temperature of about 180° C. for about 6 hours until the rosin GE was converted to an epoxy group content of about 25 mmol / kg. After cooling, the polyether had a solids content of about 95%.

[0102] [Example 18] Polyether Resin The following components were charged to a reaction vessel equipped with a stirrer, thermometer and condenser: 79 grams of monopentaerythritol, 921 grams of H-rosin GE, 185 grams of n-butyl acetate and 3.572 grams of tin(II) 2-ethylhexanoate. The mixture was heated to a temperature of about 180° C. for about 6 hours until the H-rosin GE was converted to an epoxy group content of about 25 mmol / kg. After cooling, the polyether had a solids content of about 95%.

[0103] Observation: When Cardura E10P is replaced with Rosin Ge or H-Rosin GE in the polyether heat treatment, a significant improvement (faster hardness development) is observed.

[0104] [Example 19] Preparation of composite structures for vacuum infusion A resin for vacuum infusion of large structures such as yachts and wind turbines was prepared by mixing 27.7 parts by weight of the hardener blend and 100 parts of the epoxy resin blend described herein.

[0105] Epoxy resin blend: 850 parts by weight Epikote 828 and 150 parts Rosin GE or H-Rosin GE.

[0106] Hardener blend: 650 parts by weight Jeffamine D230 and 350 parts by weight isophorone diamine (IPDA).

[0107] Jeffamine D230 is a polyoxyalkyleneamine available from Huntsman Corporation. Epikote 828 is an epoxy resin available from Hexion Chemicals.

[0108] [Example 20] Examples of Floor and Patching Compounds that can be Applied with a Trowel The ingredients set forth in Table 24 below were mixed to prepare a trowelable flooring compound.

[0109] [Table 22]

[0110] [Example 21] Water-based self-leveling flooring formulations The ingredients set out in Table 25 below were mixed to prepare a water-based self-leveling flooring system.

[0111] [Table 23]

[0112] [Example 22] Preparation of water-based acrylic polyols obtained via secondary dispersion.

[0113] A glass reactor equipped with a stirrer was flushed with nitrogen and the initial reactor charge (see Table 26) was heated to 140°C. The monomer mixture with initiator was then gradually added to the reactor via pump over 5 hours at this temperature. Additional initiator was then fed to the reactor for an additional hour at 140°C. The polymer was then cooled to 80°C and n,n-dimethylethanolamine was added and allowed to react for 15 minutes under vigorous stirring. Water preheated at 80°C was gradually added to the reactor over 2 hours with the temperature maintained at 80°C. The aqueous resin was then cooled to room temperature and discharged.

[0114] [Table 24]

[0115] The resin of Example 22 can be formulated into coating compositions such as 2K water-based (polyurethane) with near-zero VOC (volatile organic compound) levels, and can provide excellent appearance while maintaining high drying speed. It has been observed that acrylic polyols containing Rosin GE or H-Rosin GE induce faster dry-to-touch times and early hardness development.

Claims

1. A process for the preparation of hydrogenated rosin glycidyl esters, comprising the steps of: (a) reacting hydrogenated rosin acid with epichlorohydrin in the presence of water and a water miscible solvent in the presence of a catalyst at a temperature ranging from 55 to 75° C. for a period ranging from 0.5 to 2.5 hours, with a molar amount of hydrogenated rosin acid of up to 45 mol % and a molar ratio of epichlorohydrin to hydrogenated rosin acid ranging from 1.02:1 to 1.50:1; (b) adding additional alkali metal hydroxide or alkali metal alkanolate in a maximum molar ratio in the range of 0.9:1 to 1.2:1 relative to the monocarboxylic acid groups and reacting at a temperature of 0 to 80° C.; (c) distillation of the resulting reaction mixture to remove excess epichlorohydrin and solvent and formed water; and (d) removal of alkali metal halide salts, optionally followed by treatment of the residual product with concentrated aqueous alkali metal hydroxide or alkali metal alcoholate solutions to complete the dehydrohalogenation. A method comprising:

2. A blend of polyester polyol resin, acrylic polyol resin, polyether polyol resin, or polyether-ester polyol resin containing a glycidyl ester of hydrogenated rosin obtained by the method of claim 1, The polyester polyol resin is obtained by reacting a polycarboxylic acid compound with a hydrogenated rosin glycidyl ester, and the polycarboxylic acid compound is obtained by reacting one or more polyfunctional polyols with one or more acid anhydrides; the acrylic polyol resin is obtained by reacting, in one or more steps, one or more unsaturated monomers with a hydroxyl ethylene carboxylic acid ester monomer by a radical polymerization reaction, the hydroxyl ethylene carboxylic acid ester monomer being obtained by reacting an epoxy group of a glycidyl ester of a hydrogenated rosin with a carboxylic acid group of an ethylene carboxylic acid compound; The polyether polyol resin is obtained by reacting at least one polyol having at least three hydroxyl groups with a hydrogenated rosin glycidyl ester; compound.

3. 3. The formulation of claim 2, wherein the polyester polyol resin has an acid value of less than 20 mg KOH / g of solid resin.

4. 4. The formulation according to claim 2 or 3, characterized in that the number average molecular weight (Mn) of the polyester polyol resin is comprised between 300 and 7000 Daltons according to polystyrene standard and / or the hydroxyl number of the polyester polyol resin is comprised between 40 and 320 mg KOH / g solids.

5. A binder composition useful as a coating composition, comprising at least the polyester polyol resin according to any one of claims 2 to 4.

6. 3. The formulation of claim 2, characterized in that the calculated hydroxyl number of the acrylic polyol resin is 50-180 mg KOH / g of solids and / or the number average molecular weight (Mn) of the acrylic polyol resin is 1500-50000 Daltons according to polystyrene standard.

7. A binder composition useful as a coating composition, comprising at least the acrylic polyol resin according to claim 2 or 6.

8. 1. A transparent coating composition comprising 10-40 wt. % of an aliphatic isocyanate, 0-25 wt. % of the polyester polyol resin of claim 2 or 4, and 40-70 wt. % of the acrylic polyol resin of claim 2 or 6, all weight percentages based on solids after evaporation of the solvent.

9. The acrylic polyol resin of claim 2 or 6, prepared in the same reactor in the presence of the polyester polyol resin of claim 2.

10. The formulation of claim 2, characterized in that the polyether polyol resin has a number average molecular weight (Mn) of less than 4500 Daltons according to polystyrene standards and / or a hydroxyl number of the polyether polyol resin of greater than 120 mg KOH / g solids.

11. 13. A binder composition useful in coating compositions, comprising at least the polyether polyol resin of claim 2 or 10.

12. 12. A metal, wood or plastic substrate coated with the binder composition of any of claims 5, 7 or 11.

13. 3. The formulation of claim 2, wherein the hydrogenated rosin glycidyl ester is used as a reactive diluent for preparing the polyester polyol resin.

14. 3. Use of the formulation according to claim 2 in binder compositions for coatings, adhesives, as reactive diluents or as acid scavengers.

15. 4. The formulation of claim 3, wherein the polyester polyol resin has an acid value of less than 10 mg KOH / g of solid resin.

16. 4. The formulation of claim 3, wherein the polyester polyol resin has an acid value of less than 6 mg KOH / g of solid resin.

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