Vinyl-containing compounds and processes for making the same

Abstract

The present invention provides a process for forming vinyl-containing compounds including the steps of: a) reacting in a nitrogen atmosphere a dicarboxylic acid and/or anhydride and a functional mono or polyfunctional alcohol to provide a hydroxyl-containing polyester; b) reacting the hydroxyl-containing polyester with a vinyl-containing organic acid in the presence of an esterification catalyst, a polymerization inhibitor and an azeotropic agent; and c) reacting the vinyl functional esterified intermediate, residual esterification catalyst and residual vinyl-containing organic acid with an epoxy to provide the vinyl-containing compound.

Claims

1. A process for forming vinyl-containing compounds, the process comprising the steps of: a) reacting in a nitrogen atmosphere at least one dicarboxylic acid and/or anhydride and a monofunctional or polyfunctional alcohol to an endpoint of an acid number of 10 or less to provide a hydroxyl-containing polyester; b) reacting the hydroxyl-containing polyester with a vinyl-containing organic acid in the presence of an esterification catalyst, and a polymerization inhibitor while in the nitrogen atmosphere to provide a vinyl functional esterified intermediate group; and c) reacting the vinyl functional esterified intermediate, residual esterification catalyst and residual vinyl-containing organic acid with an epoxy while in the nitrogen atmosphere to provide the vinyl-containing compound wherein the nitrogen atmosphere in steps a)-c) is devoid of oxygen and the reactions are under inert conditions.

2. The process according to claim 1, wherein the at least one dicarboxylic acid is selected from the group consisting of isophthalic acid, terephthalic acid, adipic acid, cyclohexane dicarboxylic acid, succinic acid, succinic anhydride, sebacic acid, azealic acid, malonic acid, malonic anhydride, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, and alkenyl succinic acids, and anhydrides thereof.

3. The process according to claim 2, wherein the anhydride of the dicarboxylic acid is selected from the group consisting of phthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride, itaconic anhydride and hexahydrophthalic anhydride.

4. The process according to claim 1, wherein the alcohol is selected from the group consisting of n-butanol, n-hexanol, octanol, undecanol, dodecanol, cyclohexylmethanol, benzyl alcohol, phenoxy ethanol, ethylene glycol, diethylene glycol, neopentyl glycol, dibromoneopentyldiol, polytetramethylene glycol, 1,5-pentanediol, 1,4-butanediol, 2-methyl propanediol, 2,2,4-trimethyl-1,3pentadiol, 2-butyl-2ethyl-1,3-propanediol, ethoxylated hydrogenated bisphenol A, 1,4-cyclohexane dimenthanol, sorbitol, 1,2,3,6-hexatetrol, 1,4-sorbitol, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methyl propanetriol, 2-methyl-1,2,4-butanetriol, trimethylol ethane, trimethylol propane, 1,3,5-trihydroxyethyl benzene, polyTHF, polyethyleneoxide, and polypropyleneoxide, catechol, resorcinol, and bisphenol intermediates, and mixtures thereof.

5. The process according to claim 1, wherein the vinyl-containing organic acid is selected from the group consisting of methacrylic acid, acrylic acid, cinnamic acid and crotonic acid, and mixtures of any thereof.

6. The process according to claim 1, wherein the epoxy is selected from the group consisting of Bisphenol A epoxy, Bisphenol F epoxy, butyl glycidyl ether, C12-C14 glycidyl ether, cresyl glycidyl ether, glycidyl neodecanoate, diglycidyl ether of neopentyl glycol, diglycidyl ether of 1,4 butanediol, and diglycidyl ether of resorcinol.

7. The process according to claim 1, wherein a second esterification catalyst is added with the epoxy in step (c).

8. The process according to claim 1, wherein the second esterification catalyst is selected from the group consisting of organophosphonium salts and quaternary ammonium salts.

9. A vinyl-containing compound prepared by the process of claim 1 comprising no more than 10% of an ethylenically unsaturated vinyl monomer.

10. A thermosetting resin comprising a vinyl-containing compound prepared by the process of claim 1.

11. The thermosetting resin of claim 10 further includes and initiator comprising one or more organic peroxides and curing accelerators comprising a tertiary amine, an acetoacetamide, and one or more metal salts.

12. The thermosetting resin of claim 10, further comprising an additional additive selected from any one of the group consisting of flame retardant compounds, fillers, reinforcements, thixotropic agents, paraffin waxes, fatty acids, fatty acid derivatives, lubricants, shrink-reducing additives, thermoplastic polymeric materials, low profile agents (LPA), antioxidants, pigments, dyes, paraffins, lubricants, flow agents, air release agents, wetting agents, UV stabilizers, internal release agents, and mixtures of any thereof.

13. A composite component, laminate, structural adhesive, polymer concrete component, or molding component comprising the thermosetting composition according to claim 10.

14. A prepreg comprising the thermosetting composition of claim 10.

15. A coating resin applying the thermosetting composition of claim 10.

16. A method of using a thermosetting composition comprising applying the thermosetting composition of claim 10 by a pultrusion route, casting, hand lay-up, spray-up, filament winding, sheet molding compounding (SMC), UV cured resins, or resin transfer molding.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a graphic comparison of viscosity versus time at room temperature and at 65 C. for 60 days.

(2) FIG. 2 is a graphic comparison of molecular weight versus time at room temperature and at 65 C. for 60 days.

(3) FIG. 3 is a graphic comparison of AHPA color versus time at room temperature and at 65 C. for 60 days.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

(4) The foregoing and other aspects of the present invention will now be described in more detail with respect to the description and methodologies provided herein. It should be appreciated that the invention can be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

(5) The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the description of the embodiments of the invention and the appended claims, the singular forms a, an and the are intended to include the plural forms as well, unless the context clearly indicates otherwise. Also, as used herein, and/or refers to and encompasses any and all possible combinations of one or more of the associated listed items. Furthermore, the term about, as used herein when referring to a measurable value such as an amount of a compound, dose, time, temperature, and the like, is meant to encompass variations of 20%, 10%, 5%, 1%, 0.5%, or even 0.1% of the specified amount.

(6) It will be further understood that the terms comprises and/or comprising, when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. Unless otherwise defined, all terms, including technical and scientific terms used in the description, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

(7) The term consists essentially of (and grammatical variants), as applied to the methods in this invention, means the methods or compositions can contain additional steps as long as the additional steps or components do not materially alter the basic and novel characteristic(s) of the present invention.

(8) The term consisting of excludes any additional step that is not specified in the claim.

(9) Unless the context indicates otherwise, it is specifically intended that the various features of the invention described herein can be used in any combination.

(10) Moreover, the present invention also contemplates that in some embodiments of the invention, any feature or combination of features set forth herein can be excluded or omitted.

(11) All patents, patent applications and publications referred to herein are incorporated by reference in their entirety. In case of a conflict in terminology, the present specification is controlling.

(12) As one of ordinary skill in the art may appreciate, the parameters described herein may vary greatly depending on the process, formulation and/or apparatus as well as the desired properties of the final product.

(13) In one aspect, the invention relates to a process for preparing vinyl-containing components. The process as described above includes reacting in or under a nitrogen atmosphere, a dicarboxylic acid and/or anhydride, and a polyhydric alcohol to provide a hydroxyl-containing polyester. The hydroxyl-containing polyester is reacted with a vinyl-containing organic acid in the presence of an esterification catalyst, a polymerization inhibitor and an azeotropic agent. The reaction then continued using a residual esterification catalyst and residual vinyl-containing organic acid and reacting with an epoxy to provide the vinyl-containing compound.

(14) In accordance with embodiments of the present invention, hydrogen-containing polyesters, typically having a low molecular weight, are prepared by the condensation of dicarboxylic acid or anhydrides with polyhydric alcohols under a nitrogen atmosphere. Anhydrides that can be employed in the making of a polyester are preferably cyclic or acyclic, saturated or unsaturated. In a cyclic anhydride, the anhydride functionality is contained within a ring, such as in phthalic anhydride and maleic anhydride. Saturated anhydrides contain no ethylenic unsaturation, although they may contain aromatic rings. Phthalic anhydride and succinic anhydride are examples of saturated anhydrides. Unsaturated anhydrides contain ethylenic unsaturation. This unsaturation typically becomes incorporated into the polyetherester, and can be used for crosslinking. Examples include maleic anhydride, itaconic anhydride, and the like.

(15) Specific examples of suitable anhydrides include, but are not limited to, propionic anhydride, maleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, citraconic anhydride, itaconic anhydride, and aryl-, alkyl-, and halogen-substituted derivatives of the above. Mixtures of these anhydrides may be used. The selection of the amounts of polyether and anhydride that may be used can be determined by one skilled in the art depending on end use, and may depend, for example, upon the types of physical properties or degree of crosslinking that is desired for such use.

(16) Specific examples of dicarboxylic acids include but are not limited to, isophthalic acid, terephthalic acid, adipic acid, cyclohexane dicarboxylic acid, succinic anhydride, adipic acid, sebacic acid, azealic acid, malonic acid, alkenyl succinic acids such as n-dodecenylsuccinic acid, docecylsuccinic acid, octadecenylsuccinic acid, and anhydrides thereof. Lower alkyl esters of any of the above may also be employed. Mixtures of any of the above are suitable.

(17) Additionally, polybasic acids or anhydrides thereof having not less than three carboxylic acid groups may be employed. Such compounds include 1,2,4-benzenetricarboxylic acid, 1,3,5-benzene tricarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid, 2,5,7-naphthalene tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, 1,3,4-butane tricarboxylic acid, 1,2,5-hexane tricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-carboxymethylpropane, tetra(carboxymethyl)methane, 1,2,7,8-octane tetracarboxylic acid, and mixtures thereof.

(18) A wide range of alcohols may be used in the method of the invention, the selection of which can be determined by one skilled in the art. Examples include monofunctional alcohols and polyfunctional alcohols. It is preferred that these alcohols have sufficiently high boiling points such that themselves and their corresponding esters formed therefrom are not volatilized and lost under the reaction condition. As an example, monoalcohols or polyols containing two or more carbons and alcohols containing at least one or more hydroxy groups having sufficiently high boiling points may be used in the invention. The alcohols may include, but are not limited to, n-butanol, n-hexanol, octanol, undecanol, dodecanol, cyclohexylmethanol, benzyl alcohol, phenoxy ethanol, ethylene glycol, diethylene glycol, neopentyl glycol, dibromoneopentyldiol, polytetramethylene glycol, 1,5-pentanediol, 1,4-butanediol, 2-methyl propanediol, 2,2,4-trimethyl-1,3pentadiol, 2-butyl-2ethyl-1,3-propanediol, ethoxylated hydrogenated bisphenol A, 1,4-cyclohexane dimenthanol, sorbitol, 1,2,3,6-hexatetrol, 1,4-sorbitol, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methyl propanetriol, 2-methyl-1,2,4-butanetriol, trimethylol ethane, trimethylol propane, 1,3,5-trihydroxyethyl benzene, polyTHF, polyethyleneoxide, and polypropyleneoxide. Hydroxyalkyl phenols may also be used and they may be contained as hydroxyethyl, hydroxypropyl, or hydroxybutyl, where the degree of ethoxylation or propoxylation may be from 1 to 20 repeating units. Examples of some useful polyhydric phenols, which are hydroxyalkoxylated, include, catechol, resorcinol, bisphenol intermediates, and the like. Other alkyl or aryl alcohols may be included along with mixtures of any of the above.

(19) The resulting hydroxyl-containing polyester is reacted with a vinyl-containing organic acid in the presence of an esterification catalyst, a polymerization inhibitor and an azeotropic agent to provide an esterified intermediate. An azeotropic agent is present to facilitate removal of water generated during this reaction. The organic acid is present in a molar excess relative to the alcohol and carrying the reaction under nitrogen inert conditions until neutralized. During this reaction, the esterified intermediate and/or the azeotropic agent may serve as a reaction diluent. The reaction between the epoxy, the unreacted organic acid, and the excess esterification catalyst forms a vinyl-containing compound. Preferably, the unreacted organic acid and excess esterification acid catalyst are completely consumed by the process of the invention.

(20) The organic acid that may be used in accordance with the invention may be selected from any number of acids that are used in esterification reactions. Typically, acids having at least two or more carbon and oxygen atoms may be used. Examples of these acids include, but are not limited to, halogenated acrylic or methacrylic acids, cinnamic acid, and crotonic acid, as well as mixtures of the above. Hydroxyalkyl acrylate or methacrylate half esters of dicarboxylic acids as described can also be utilized, and particularly those having from two to six carbon atoms. Examples of these compounds are described in U.S. Pat. No. 3,367,992, the disclosure of which is incorporated herein by reference in its entirety. The organic acid and alcohol may be selected in various amounts relative to one another. Preferably, these materials are used such that the weight equivalent ratio of organic acid to alcohol ranges from about 1:1 to about 10:1.

(21) Any number of esterification acid catalysts can be used for the purposes of the invention. Acid catalysts include, but are not limited to, strong protic acids and Lewis acids. Examples of Lewis acids are sulfuric acid, hydrochloric acid, alkyl sulfonic acids, 2-methyl-1-phenol-4-sulfonic acid, alkylbenzene sulfonic acids, and mixtures thereof. Toluenesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, and methanesulfonic acid are preferably employed. In general, sulfur-containing acid catalysts are preferably employed. Mixtures of any of the above may also be used.

(22) Various amounts of catalyst may be employed. Preferably, the catalyst ranges from about 0.1 to about 5 percent based on the weight of the reactants, and more preferably from about 0.5 to about 2 percent by weight.

(23) Polymerization inhibitors may also be included in the polymerization mixture such as triphenyl antimony, phenothiazine, phenol, 2,6-di-tert-butyl-4-methyl phenol, hydroquinone (HQ), tolu-hydroquinone (THQ), bisphenol A (BPA), naphthoquinone (NQ), p-benzoquinone (p-BQ), butylated hydroxy toluene (BHT), Hydroquinone monomethyl ether (HQMME), 4-ethoxyphenol, 4-propoxyphenol, and propyl isomers thereof, monotertiary butyl hydroquinone (MTBHQ), ditertiary butyl hydroquinone (DTBHQ), tertiary butyl catechol (TBC), 1,2-dihydroxybenzene, 2,5-dichlorohydroquinone, 2-acetylhydroquinone, 1,4-dimercaptobenzene, 2,3,5-trimethylhydroquinone, 2-aminophenol, 2-N,N,-dimethylaminophenol, catechol, 2,3-dihrydroxyacetrophenone, pyrogallol, 2-methylthiophenol. Other substituted and un-substituted phenols and mixtures of the above.

(24) As recited, an azeotropic agent is employ to facilitate removal of water generated during the reaction between the organic acid and the alcohol. Preferably, an inert organic azeotropic agent is used. Examples of the azeotropic agent include, but are not limited to, hydrocarbons such as benzene, toluene, xylene, hexane, and cyclohexane. Mixtures of these solvents may also be used. In general, it is preferable to employ solvents having a boiling point ranging from about 70 C. to about 150 C.

(25) The azeotropic agent may be used in varying amounts. In one embodiment, the azeotropic agent is used in an amount ranging from about 5 to about 50 percent based on the weight of the total reaction mixture. Alternatively, the azeotropic agent is used in an amount ranging from about 10 to about 30 percent by weight.

(26) The esterification is carried out under nitrogen and at atmospheric, subatmospheric or reduced pressure, the selection of which is within the skill of one in the art.

(27) Any number of epoxies can be used for the purposes of the invention. Typically, polyepoxides are used. Preferably the polyepoxides are glycicyl methacrylate, glycidyl polyethers of both polyhydric alcohols and polyhydric phenols, flame retardant epoxy resins based on tetrabromo bisphenol A, epoxy novolacs, epoxidized fatty acids or drying oil acids, epoxidized diolefins, epoxidized unsaturated acid esters as well as epoxidized unsaturated polyesters. Mixtures of the above may be employed. The polyepoxides may be monomeric or polymeric. In one embodiment, the polyepoxides are glycidyl ethers of polyhydric alcohols or polyhydric phenols having equivalent weights per epoxide groups ranging from about 150 to about 1500, alternatively from about 150 to about 1000.

(28) The epoxy component can be used in varying amounts. As an example, an epoxy may be reacted with an acid in a proportion of about 1 equivalent of epoxy per each equivalent of acid. The term acid in the preceding sentence encompasses excess esterification catalyst and unreacted organic acid. In one embodiment, the proportions of equivalents may range from about 0.8:1 to about 1.2:1. Upon completion of the reaction between the organic acid and the alcohol, the resulting reaction mixture typically contains ester-containing products, unreacted organic acid, an esterification acid catalyst, and azeotropic agent. The reactor is then charged with the epoxy, to react with the excess organic acid and catalyst. In the event that an epoxide is employed, a second esterification catalyst may be used to catalyze the reactions between the epoxide and: (1) unreacted organic acid and (2) esterification acid catalyst. A number of catalysts may be employed for this purpose. Exemplary second esterification catalysts include, but are not limited to, organophosphonium salts, and tertiary amines such as 2,4,6-tri(dimethylaminomethyl)phenol and the like. Tertiary amines and quaternary ammonium salts may be used. Examples include, but are not limited to, tetramethylammonium chloride, tetramethylammonium hydroxide, tetramethylammonium bromide, tetramethylammonium hydrogensulfate, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydrogen sulfate, benzyltributylammonium chloride, benzyltributylammonium bromide, benzyltributylammonium hydrogen sulfate, 1,4-diazabicyclo[2.2.2]octane, diazabicyclo[4.3.0]-nonene-(5), 2-methyl imidazol, piperidine, morpholine, triethyl amine, tributyl amine, and the like. Mixtures of the above may also be employed.

(29) Phosphorous containing compounds may also be used as a catalyst involving the epoxide. Examples include, but are not limited to, and may have the formula:
(R.sub.4).sub.3P or (R.sub.4).sub.4PY
where R.sub.4 is an aliphatic, cycloaliphatic or aromatic group containing from C.sub.4 to C.sub.20, and may be linear or branched, wherein Y is a group selected from chlorine, bromine, fluorine, iodine, acetate or bicarbonate.

(30) The mixtures formed as a result of the invention can also be combined with materials that are well known to one skilled in the art. Examples of these materials include, for example, waxes, fillers, low shrinking agents, and pigments. Reinforcements can also be used such as, for example, glass fiber and carbon fiber. Accelerators that are known in the art can be used in the processing of the resins and include, for example, peroxides and promoters to form a molded or shaped article.

(31) In the event that the composition is used as a gelcoat and employs an ethylenically unsaturated monomer such as, for example, a vinyl monomer, the laminating resin often comprises less than about 15 percent by weight of such monomer. Employing less than 15 percent by weight of such a monomer may be potentially advantageous from an environmental standpoint relative to conventional resins. As known, the potential risk of any monomer often depends on various processing conditions relating to, for example, temperature, pressure, and monomer concentration. As an example, OSHA has suggested an allowable eight hours time weight average styrene exposure level of 50 ppm. Ethylenically unsaturated monomers that may be included as a diluent, reactant, co-reactant or may be post added once the polymerization of the desired polymer and/or oligomer was completed, and may include those such as, for example, styrene and styrene derivatives such as -methyl styrene, p-methyl styrene, divinyl benzene, divinyl toluene, ethyl styrene, vinyl toluene, tert-butyl styrene, monochloro styrenes, dichloro styrenes, vinyl benzyl chloride, fluorostyrenes, tribromostyrenes, tetrabromostyrenes, and alkoxystyrenes (e.g., paramethoxy styrene). Other monomers which may be used include, 2-vinyl pyridine, 6-vinyl pyridine, 2-vinyl pyrrole, 2-vinyl pyrrole, 5-vinyl pyrrole, 2-vinyl oxazole, 5-vinyl oxazole, 2-vinyl thiazole, 5-vinyl thiazole, 2-vinyl imidazole, 5-vinyl imidazole, 3-vinyl pyrazole, 5-vinyl pyrazole, 3-vinyl pyridazine, 6-vinyl pyridazine, 3-vinyl isoxozole, 3-vinyl isothiazole, 2-vinyl pyrimidine, 4-vinyl pyrimidine, 6-vinyl pyrimidine, any vinyl pyrazine. Classes of other vinyl monomers also include, but are not limited to, (meth)acrylates, vinyl aromatic monomers, vinyl halides and vinyl esters of carboxylic acids. As is used herein and in the claims, by (meth)acrylate and the like terms is meant both (meth)acrylates and acrylates. Examples include but are not limited to oxyranyl (meth)acrylates like 2,3-epoxybutyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 10,11 epoxyundecyl (meth)acrylate, 2,3-epoxycyclohexyl (meth)acrylate, glycidyl (meth)acrylate, hydroxyalkyl (meth) acrylates like 3-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2,5-dimethyl-1,6-hexanediol (meth)acrylate, 1,10-decanediol (meth)acrylate, aminoalkyl (meth)acrylates like N-(3-dimethylaminopentyl (meth)acrylate, 3-dibutylaminohexadecyl (meth)acrylate; (meth)acrylic acid, nitriles of (meth)acrylic acid and other nitrogen containing (meth)acrylates like N-((meth)acryloyloxyethyl)diisobutylketimine, N-((meth)acryloylethoxyethyl)dihexadecylketimine, (meth)acryloylamidoacetonitrile, 2-(meth)acryloxyethylmethylcyanamide, cyanoethyl (meth)acrylate, aryl (meth)acrylates like benzyl (meth)acrylate or phenyl (meth)acrylate, where the acryl residue in each case can be unsubstitute or substituted up to four times; carbonyl-containing (meth)acrylates like 2-carboxyethyl (meth)acrylate, carboxymethyl (meth)acrylate, oxazolidinylethyl (meth)acrylate, N-((meth)acryloyloxy) formamide, acetonyl (meth)acrylate, N-(meth)acryloylmorpholine, N-(meth)acryloyl-2-pyrrolidinone, N-(2-(meth)acryloxyoxyethyl)-2-pyrrolidinone, N-(3-(meth)acryloyloxypropyl)-2-pyrrolidinone, N-(2-(meth)ylacryloyloxypentadecenyl)-2-pyrrolidinone, N-(3-(meth)acryloyloxyheptadecenyl)-2-pyrrolidinone; (meth)acrylates of ether alcohols like tetrahydrofurfuryl (meth)acrylate, vinyloxyethoxyethyl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, 1-butoxypropyl (meth)acrylate, 1-methyl-(2-vinyloxy)ethyl (meth)acrylate, cyclohexyloxymethyl (meth)acrylate, methoxymethoxyethyl (meth)acrylate, bezyloxymethyl (meth)acrylate, furfuryl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-ethoxyethoxymethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, allyloxymethyl (meth)acrylate, 1-ethoxybutyl (meth)acrylate, ethoxymethyl(meth)acrylate; (meth)acrylates of halogenated alcohols, like 2,3-dibromopropyl (meth)acrylate, 4-bromophenyl (meth)acrylate 1,3-dichloro-2-propyl (meth)acrylate, 2-bromoethyl (meth)acrylate, 2-iodoethyl (meth)acrylate, chloromethyl (meth)acrylate; phosphorus-, boron, and/or silicon-containing (meth)acrylates like 2-(dimethylphosphato)propyl (meth)acrylate, 2-(ethylphosphito)propyl (meth)acrylate, dimethylphosphinoethyl (meth)acrylate, dimethylphosphinomethyl (meth)acrylate, dimethylphosphonoethyl (meth)acrylate, dimethy(meth)acryloyl phosphonate, dipropyl(meth)acryloyl phosphate, 2-(dibutylphosphono)ethyl methacrylate, 2,3-butelene(meth)acryloylethyl borate, methyldiethoxy(meth)acryloylethoxysilane, diethylphospahtoethyl (meth)acrylate;sulfur-containing (meth)acrylates like ethylsulfinylethyl (meth)acrylate, 4-thiocyanatobutyl (meth)acrylate, ethylsulfonylethyl (meth)acrylate, thiocyanathomethyl (meth)acrylate, methylsulfonylmethyl (meth)acrylate, bis((meth)acryloyloxyethyl) sulfide.

(32) The gelcoat composition may include an agent such as an organic peroxide compound to facilitate curing of the composition. Exemplary organic peroxides may be used and include, for example, cumene hydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, acetyl acetone peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, tert-butyl peroxybenzoate, di-tert-butyl perphthalate, dicumylperoxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexyne 3, bis (tert-butylperoxyisopropyl) benzene di-tert-butyl peroxide, 1,1-di (tert-amylperoxy)-cyclohexane, 1,1-di-(tert-butylperoxy)-3,3,5-trymethylcyclohexane, 1,1-di-(tert-butylperoxy)-cyclohexane, 2,2-di-(tert-butylperoxy)-butane, n-butyl 4,4-di-(tert-butylperoxy)-valerate, ethyl 3,3-di-(tert-amylperoxy)-butyrate, ethyl 3,3-di-(tert-butylperoxy)-butyrate and the like. Mixtures of any of the above may be used. The agent is preferably employed in an amount from about 1 to 5 percent based on the weight of the laminating resin, more preferably from about 1 to 3 percent by weight, and most preferably from about 1 to 2 percent by weight.

(33) Suitable curing accelerators or promoters may also be used and include, for example, cobalt naphthanate, cobalt octoate, N,N-diethyl aniline, N,N-dimethyl aniline, N,N-dimethyl acetamide, and N,N-dimethyl p-toluidine. Other salts of lithium, potassium, zirconium, calcium and copper. Mixtures of the above may be used. The curing accelerators or promoters in one embodiment are employed in amounts from about 0.005 to about 1.0 percent by weight, sometimes from about 0.1 to 0.5 percent by weight, and often from about 0.1 to 0.3 percent by weight of the resin.

(34) In one embodiment of this invention, the free radical initiator is a photoinitiator, and the gelcoat composition is cured by UV radiation. These include photoinitiators such as benzophenone, acetophenone and its derivatives, benzoin, benzoin ethers, thiozanthones, halogenated compounds, oximes, and acyl phosphine oxides. In one embodiment, the photoinitiators do not discolor when exposed to sunlight, and include, e.g. acyl phosphines oxides and 2-hydroxy-2-methyl-1-phenylpropan-1-one.

(35) Additional additives known by the skilled artisan may be employed in the laminating resin composition of the present invention including, for example, thixotropic agents, pigments, paraffins, fatty acids, fatty acid derivatives, lubricants, antioxideants, air release agents, fillers, and shrink-reducing additives. Various percentages of these additives can be used in the laminating resin composition.

(36) Fillers used in the invention include calcium carbonate of various forms and origins, silica of various forms and origins, silicates, silicon dioxides of various forms and origins, clays of various forms and origins, feldspar, kaolin, zirconia, calcium sulfates, micas, talcs, wood in various forms, glass(milled, platelets, spheres, micro-balloons), plastics (milled, platelets, spheres, micro-balloons), recycled polymer composite particles, metals in various forms, metallic oxides or hydroxides (except those that alter shelf life or viscosity), metal hydrides or metal hydrates, carbon particles or granules, alumina, alumina powder, aramid, bronze, carbon black, carbon fiber, coal (powder), fibrous glass, graphite, molybdenum, nylon, orlon, rayon, silica amorphous, and fluorocarbons.

(37) The resins formed as a result of the processes of the invention can advantageously be employed in a number of other applications such as, for example, sheet molding compounding (SMC) resins, castings resins, UV cured resins and adhesives, pultrusion resins, corrosion resistant resins, flame retardant resins, low or zero styrene content resins, gel coats, filament winding, hand lay-up, resin transfer molding, prepregs, and coating resins.

(38) The invention is highly advantageous relative to prior art processes. For example, the invention allows the preparation of low color (meth)acrylic intermediates, obtain excellent mechanical properties alone or in combination with a reduced level of ethylenically unsaturated vinyl monomer (e.g., styrene) to be employed during the usage of the resin mixture, preferably no more than 10% percent based on the weight of the reactants.

(39) Moreover, since the invention is a relatively simple two step, one pot synthesis, a number of extra processing steps described in the prior art relating to extracting, washing, separating and/or concentrating of various materials can be avoided (i.e., eliminated), particularly washing and separating with aqueous solution to remove excess acid and catalyst. Applicants believe this to be a significant and unexpected advantage of the invention particularly a significant improvement on the preparation of (meth)acrylic intermediates with a low color by using nitrogen.

(40) The present invention will now be described in more detail with reference to the following examples. However, these examples are given for the purpose of illustration and are not to be construed as limiting the scope of the invention.

EXAMPLES

Example 1

(41) 1st Stage: In a 3 liter four-neck flask equipped with a thermometer, stainless steel stirrer, nitrogen inlet, and condenser were placed 458 g of Neopentyl glycol (NPG), 466 g of Diethylene glycol (DEG), 688 g of cyclohexane diacid (CHDA). The materials are reacted under a nitrogen sparge at 210 C. until a 1st stage endpoint of an acid number of 10 or less is achieved.

(42) 2nd Stage: The reactor is cooled to a temperature of about 100 C. and then 0.48 g (200 ppm) of Phenothiazin, 0.24 g (100 ppm) of triphenyl antimony, 420 g of Toluene, 757 g of Methacrylic acid, and 9 g of Methane sulfonic acid are added to the first stage components above. The temperature is gradually increased to 115 C. and held to azeotropically distill the water from the esterification reaction. After water distillation slow down or stopped, toluene is stripped off from the reaction. Vacuum is applied to completely remove the toluene.

(43) 3rd Stage: Temperature is reduced to 90 C. and 95 g of liquid epoxy is added. Temperature is maintained between 90-100 C. and held for one hour. The reactor is cooled to 40 C., the product is filtrated and transfer to storage. The obtained resin was clear liquid and had acid value of 17.8 mg/g, AHPA color of 40 and viscosity of 260 cps. The resin was identified as resin 1 in table 1.

Examples 2-11

(44) The vinyl-containing compounds in Examples 2-11 were prepared using the similar method described in Example 1, except that the reactants molar ratios in the first stage reaction were varied. The molar ratios of the compositions for the vinyl-containing compounds in Examples 1-11 are summarized in Table 1.

(45) TABLE-US-00001 TABLE 1 Composition (molar ratio) Resin# ISO THPA HHPA CHDA AA DDSA NPG DEG TEG MPDiol 1 100 110 110 2 100 109 109 3 100 109 109 4 100 106 106 5 100 106 106 6 70 30 106 106 7 30 40 30 218 8 100 106 106 9 30 70 218 10 100 131 87 11 60 24 16 218 ISO: Isophthalic Acid THPA: Tetrahydrophthalic Anhydride HHPA: Hexahydrophthalic Anhydride CHDA: Cyclohexane Diacid AA: Adipic Acid DDSA: Dodecenyl Succinic Anhydride NPG: Neopentyl Glycol DEG: Diethylene Glycol TEG: Triethylene Glycol MPDiol: 2-Methyl-1,3-Propanediol

Samples Testing

(46) Using the resulting vinyl-containing compounds, the following tests were carried out. The viscosity was measured using a Brookfield LV viscometer, Spindle #2 at 30 RPM and at 25 C. The molecular weights (Mw) were measured by GPC. The room temperature gel time (RTG), total time to Peak (TTP) and peak exotherm (RTP) were measured as follows: To a 100 grams of resin were added: 0.15 g of a 12% Cobalt/0.25 g DMAA/100 g resin, Initiator: 1.25 g MEKP-9 (Syrgis)/100 g resin. The results are summarized in Table 2.

(47) TABLE-US-00002 TABLE 2 Resins Properties Resin Viscosity RTG TTP # AN (cps) Color Mw (min.) (min.) Exo. 1 17.8 260 AHPA: 40 764 25.7 29.7 119 C. 2 23.0 250 AHPA: 50 583 36.7 41.2 122 C. 3 18.9 75 AHPA: 30 717 25.5 30.7 137 C. 4 23.3 265 Gardner: 3 552 12.5 16.7 131 C. 5 26.2 850 AHPA: 55 738 13.3 16.8 132 C. 6 28.2 375 AHPA: 55 686 8..5 11.7 137 C. 7 21.9 310 Gardner: 4 675 14.3 18.1 131 C. 8 32.0 3300 Gardner: 3 758 15.3 19.3 129 C. 9 17.5 250 Gardner: 4 729 15.0 18.8 133 C. 10 23.0 810 Gardner: 4 791 6.5 9.8 131 C. 11 20.0 480 Gardner: 4 767 21.0 24.5 121 C.

Examples 12 and 13

(48) The resin of Example 6 was selected to perform room temperature gel tests with different promoters. In addition, styrene was added to observe curing behavior with the reactive monomer. The resin of Example 6 was blended with 5% styrene and is identified as Example 12 in Table 3. The resin of Example 6 was blended with 10% styrene and is identified as Example 13 in Table 3. Data is summarized in Table 3.

(49) TABLE-US-00003 TABLE 3 Room Temperature Gel: 100 g resin w/ different Promoters Example Promoter RTG TTP Exo. 6 0.15 g 12% cobalt 48.3 min 53.6 min 137 C. 6 0.15 g 12% cobalt 8.5 min 11.7 min 137 C. 0.25 g DMAA 6 0.15 g 12% cobalt 35 min 39.5 min 134 C. 0.3 g Potassium Octoate 6 0.15 g 12% cobalt 2 min 5 min 134 C. 0.1 g DMA 12 0.15 g 12% cobalt 27.5 min 36.7 min 141 C. 13 0.15 g 12% cobalt 28.3 min 41.7 min 147 C. DMAA: N,N-Dimethylacetoacetamide DMA: N,N-Dimethylaniline

Comparative Examples A-C

(50) A sample with composition similar to the resin of Example 6 was made in an air atmosphere (instead of a nitrogen atmosphere as in Example 6), and is identified as Comparative Example A in Table 4.

(51) Photomer 5429 is a polyester based vinyl compound obtained from Cognis Corp. and is identified as Comparative Example B.

(52) Genomer 3485 is a polyester based vinyl compound, identified as Comparative Example C in Table 4 and available from Rahn Corp.

(53) Table 4 shows that the resin of Example 6 of the present invention has very light color and good cure at room temperature, while the Comparative Example resin A made under an air atmosphere had dark color. Comparative Example resins B and C were not able to cure at room temperature even after 3 weeks under the same curing conditions as the resin of Example 6. This suggests that the Comparative Example resins B and C may contain a large amount of inhibitors or other processing components that prevent premature gelation during the esterification reaction with acrylic intermediates and to keep the color at a relatively low level. However, by increasing the inhibitors or other processing components, curing at room temperature with amine and cobalt salts promoters and peroxides is not possible as shown in Table 4.

(54) TABLE-US-00004 TABLE 4 Resins Properties comparison Vis- cosity RTG TTP Example AN (cps) Color Mw (min.) (min.) Exo. 6 28.2 375 AHPA: 55 686 8..5 11.7 137 C. A 16.0 600 Gardner: 9 703 7.5 10.5 134 C. B 18.0 420 Gardner: 1 1128 Not gel or cure after 3 weeks C 5.9 532 Gardner: 2 1523 Not gel or cure after 3 weeks

Comparative Examples D and E

(55) A Bisphenol A conventional epoxy vinyl ester resin, DION VER 9100, identified as Comparative Example D, and an lsophthalic/NPG based unsaturated polyester resin POLYLITE 31211-00, identified as Comparative Example E in Table 5 and available from Reichhold Inc. were compared with the resins of Examples 5 and 6 and resins of Comparative Examples B and C. As shown, the resins of the present invention have excellent physical properties compared to Comparative Examples D and E while employing zero or reduced level of styrene. Castings were prepared by adding 1.0% Benzoyl Peroxide (Lupersol A-98) to the resin, follow by overnight curing at 130 F. and postcuring 2 hrs. at 180 F. and 2 hrs. at 250 F.

(56) TABLE-US-00005 TABLE 5 Physical Properties of Clear-Cast Resins Example 5 6 12 13 D E Styrene Content (wt %) 0 0 5 10 44 35 Barcol Hardness 39-41 42-46 46-49 48-49 35 40 HDT ( C.) 77 80 73 75 104 103 Tensile Strength (psi) 12,196 12,627 12,573 12,702 11,600 11,700 Tensile Modulus (kpsi) 559 577 538 521 460 560 % Elongation at Break 2.7 3.0 3.4 3.7 5.2 2.9 Flexural Strength (psi) 24,073 23,482 22,985 22,934 23,000 18,100 Flexural Modulus (kpsi) 688 665 610 607 500 550 Comp Strength (psi) 22,286 20,687 NA NA NA NA Comp Modulus (kpsi) 458 435 NA NA NA NA

(57) The physical properties of glass fiber reinforced laminates of resins of Examples 6, 12, and 13 were listed in Table 6. In this Table, resins of Examples 6, 12 and 13 of the present invention provide excellent physical properties compared to Comparative Example D resin while employing zero or a small amount of styrene. Laminates were prepared by adding to the resin, 0.2% Cobalt (12% conc.), 0.1% dimethyl aniline (DMA) and 1.25% MEKP-900 peroxide (Syrgis). Curing was performed at room temperature followed by postcuring for 2 hrs. at 250 F.

(58) TABLE-US-00006 TABLE 6 Physical Properties of Laminates Example 6 12 13 D Styrene Content 0 5 10 44 (Wt %) Glass Content (Wt %) 25 25 25 33 Barcol Hardness 55-65 55-63 55-62 NA Tensile Strength (psi) 19,453 18,162 19,060 18,130 Tensile Modulus (kpsi) 1,306 1,311 1,318 1,131 % Elongation at Break 2.6 1.8 1.9 2.1 Flexural Strength (psi) 43,441 25,782 25,507 29,008 Flexural Modulus 1,822 1,387 1.325 1,059 (kpsi) Comp Strength (psi) 23,688 18,880 20,376 NA Comp Modulus (kpsi) 1,194 922 963 NA

Other Physical Test Examples

(59) Physical properties of clear-cast resins of Examples 1-4, 7-9 and 11 are listed in Tables 7 and 8. Tables 7 and 8 show that the properties of the resins of the present invention can covered a wide range physical properties based on the changes in the compositions while employing zero styrene. Castings were prepared by adding 1.0% Benzoyl Peroxide (Lupersol A-98) to the resin, follow by overnight curing at 130 F. and postcuring 2 hrs. at 180 F. and 2 hrs. at 250 F.

(60) TABLE-US-00007 TABLE 7 Physical Properties of Clear-Cast Resins 1-4 Example 1 2 3 4 Styrene Content (wt %) 0 0 0 0 Barcol Hardness 38-40 45-48 10-12 39-41 HDT ( C.) 63 59 43 57 Tensile Strength (psi) 9,717 8,963 3,856 10,956 Tensile Modulus (kpsi) 387 493 138 507 % Elongation at Break 3.6 2.5 10.6 4.1 Flexural Strength (psi) 16,391 16,894 5,404 NA Flexural Modulus (kpsi) 473 534 134 NA

(61) TABLE-US-00008 TABLE 8 Physical Properties of Clear-Cast Resins 7-9 and 11 Example 7 8 9 11 Styrene Content (wt %) 0 0 0 0 Tensile Strength (psi) 8,598 6,702 3,997 3,425 Tensile Modulus (kpsi) 380 289 218 103 % Elongation at Break 6.5 8.8 6.9 24.0

Stability Test Examples

(62) The Example 6 resin was selected for the stability tests at both room temperature (RT) and 60 C. oven for 60 days. The tests included viscosity, molecular weight (MW), and color. As see from FIGS. 1-3, the Example 6 resin has excellent stability even at 65 C. for up to 60 days.

(63) Having thus described certain embodiments of the present invention, it is to be understood that the invention defined by the appended claims is not to be limited by particular details set forth in the above description as many apparent variations thereof are possible without departing from the spirit or scope thereof as hereinafter claimed.