WO2001027183A1

WO2001027183A1 - Preparation of acrylic compounds containing resins with vinyl functionality

Info

Publication number: WO2001027183A1
Application number: PCT/US2000/028329
Authority: WO
Inventors: Hildeberto Nava; Lixin Jin
Original assignee: Reichhold, Inc.
Priority date: 1999-10-13
Filing date: 2000-10-13
Publication date: 2001-04-19
Also published as: AU7879200A

Abstract

A process for preparing a vinyl-containing compound comprises reacting an alcohol and an organic acid in the presence of an esterification acid catalyst to form an esterified intermediate, wherein an azeotropic agent is present to facilitate removal of water generated during the reaction, and wherein the organic acid is present in an excess of its weight equivalent relative to the alcohol; and reacting an epoxide, a carbodiimide, or both with: (1) unreacted organic acid and (2) excess esterification acid catalyst such that the acid catalyst becomes neutralized. The reaction between the epoxide, the unreacted organic acid, and the excess esterification catalyst forms a vinyl ester resin; and the reaction between the carbodiimide, the unreacted organic acid, and the excess esterification catalyst forms a vinyl-functional carbodiimide.

Description

PREPARATION OF ACRYLIC COMPOUNDS CONTAINING RESINS WITH VINYL FUNCTIONALITY

Field of the Invention

The present invention generally relates to processes for preparing compounds having vinyl functionality.

Background of the Invention

Several methods have been proposed as possible ways to reduce styrene to minimize monomer emissions during the curing process of unsaturated polyesters and vinyl ester resins. One of them involves forming a low molecular weight polymer backbone allowing a substantial decrease of styrene monomer addition. Nonetheless, low molecular weight materials are not desirable in that they often exhibit poor performance in various applications. For example, low molecular weight vinyl esters show insufficient glass wetting in the preparation of glass fiber laminates. Therefore, the surface of the sprayed glass fiber resin typically must be contacted with a roller to minimize glass fibers protruding from the surface of the laminate. Moreover, the physical properties of these low molecular weight vinyl ester resins are potentially inferior to the conventional higher molecular weight vinyl ester resins, particularly with respect to toughness and chemical resistance. In response to the above-mentioned problems, it has been proposed to employ acrylic monomers such as methyl methacrylate. Nonetheless, the use of methyl methacrylate is potentially undesirable since this monomer is volatile, possesses a strong odor, and often causes skin and eye irritation. Other proposals have focused on replacing styrene with acrylic monomers with high boiling points such as poiyfunctional acrylic or methacrylic esters. Although a potential reduction in volatile emissions can be realized by using these materials, employing poiyfunctional acrylic or methacrylic esters has been shown to be impractical from a commercial standpoint. In particular, multiple processing steps are typically necessary to produce acrylic ester compounds having acceptable purity and stability levels. Furthermore, the kinetics of this reaction may potentially limit the yield of final product.

In view of the above, it has been proposed to employ a strong acid catalyst to attempt to increase the degree of conversion. In a system that employs the strong acid catalyst, it is also desirable to utilize an excess of methacrylic acid and an alcohol as proposed in German Patent Application No. 87-3723196. In the event that water is produced by the reaction, it is typically desirable to employ an azeotropic distillation that uses an inert diluent such as a hydrocarbon solvent.

Methods have been proposed to remove excess acid and alcohol during the reaction. For example, Japanese Patent Application Nos.

JP61243046, JP10045669, JP6287162, JP6016594, JP5310636, propose methods in which the reaction liquid is treated with an aqueous alkaline solution for neutralization. Notwithstanding any advantages, typically a large quantity of alkali is needed for effective neutralization. Moreover, the treated alkaline solution needs to be separated from the acrylic monomer after the reaction and disposed as a waste to obtain a pure product. This separation, however, is often difficult.

European Patent No. 0618187 ("the '187 patent") proposes an improved method of removing the strong catalyst by washing the reaction mixture with water, followed by separation of the organic monomer and an aqueous solution containing the acid catalyst. The aqueous catalyst is then recycled after it is concentrated by evaporation. This method can minimize the production of large quantities of waste water. Nonetheless, this process is potentially undesirable in that it typically involves additional steps such as washing, separating, concentrating, and recycling the reaction liquid.

Moreover, specially designed equipment such as an extraction column are typically needed to facilitate efficient removal of residual acids that may be present. In summary, the process proposed in the '187 patent is time and energy intensive and therefore results in poiyfunctional (meth)acrylic esters produced therefrom being expensive.

In view of the above, there is a need in the art to address the problems noted above in producing the poiyfunctional acrylic compounds. Specifically, it would be advantageous to minimize the use of ethylenically unsaturated monomer and also obtain a process that does not require the extra steps often required in forming vinyl-containing compounds such as, for example, extraction, separation, and/or washing. This would be particularly desirable.

Summary of the Invention

It is one object of the invention to provide a method for forming vinyl- containing compounds that eliminate the need for the multiple steps referred to herein that are taught in prior art processes.

This and other objects and advantages are provided by the invention. in addressing the above concerns, the present invention provides a process for preparing vinyl-containing compounds. The process comprises first reacting an alcohol and an organic acid in the presence of an esterification acid catalyst to form an esterified intermediate. An azeotropic agent is present during this reaction step to facilitate removal of water generated during the reaction, and the organic acid is present in an excess of its weight equivalent ratio relative to the alcohol. Next, a compound selected from the group consisting of an epoxide, a carbodiimide, or both are reacted with: (1 ) unreacted organic acid, and (2) excess esterification acid catalyst such that the acid catalyst becomes neutralized. If the epoxide is employed, the product of the epoxide, the unreacted organic acid, and excess esterification acid catalyst is a vinyl ester resin. If the carbodiimide is employed, the product of the carbodiimide, the unreacted organic acid, and excess esterification acid catalyst is a vinyl-functional carbodiimide.

This and other advantages of the invention are described by the detailed description section of the invention which follows. Detailed Description of Preferred Embodiments

The invention will now be described in greater detail with respect to the preferred embodiments set forth herein below. It should be appreciated however that these embodiments are for illustrative purposes only, and that the scope of the invention is defined by the claims.

In one aspect, the invention relates to a process for preparing vinyl- containing components. Various vinyl-containing components may be formed such as, for example, an esterified intermediate (e.g., an acrylic-containing compound such as a poiyfunctional acrylate), a vinyl ester resin, and a vinyl- functional carbodiimide (e.g., an acrylic-functional carbodiimide , namely a poiyfunctional acrylic resin derived from a polycarbodiimide). All of these reaction products are described in detail herein. The process is preferably focused on providing the esterified intermediates.

The process comprises first reacting an alcohol and an organic acid in the presence of an acid catalyst to form an esterified intermediate, namely a component containing an ester group such as, for example, a poiyfunctional acrylate. 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. Subsequently, a material selected from the group consisting of an epoxide, a carbodiimide, and mixtures thereof is reacted with: (1 ) unreacted organic acid, and (2) excess esterification acid catalyst such that the acid catalyst becomes neutralized. During this reaction, the esterified intermediate and/or the azeotropic agent may serve as a reaction diluent. The reaction between the epoxide, the unreacted organic acid, and the excess esterification catalyst forms a vinyl ester resin. The reaction between the carbodiimide, the unreacted organic acid, and the excess esterification catalyst forms an acrylic-functional carbodiimide. Preferably, the unreacted organic acid and excess esterification acid catalyst are completely consumed by the process of the invention. 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. Patent No. 3,367,992, the disclosure of which is incorporated herein by reference in its entirety.

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 poiyfunctional alcohols. Exemplary alcohols that may be employed can be expressed by the formulas selected from the group consisting of:

{X} [R] m

X— [R]— X n

X-R-~[Rι]-R~-X n

X-CH₂-[Rι]-CH₂-X n

X-CH₂— R--[Rι] — R-CH₂-X n

wherein :

X is OH or SH;

R is an aliphatic or cycloaliphatic group containing Ci to C o linear or branched, α,β-unsaturated straight or branched alkenyl or alkynyl; and wherein R may contain a group selected from Cι-C₂₀₎ OH, halogen, OR₂, and SR₃, wherein R₂ is an alkyl containing from 1 to 20 carbon atoms in which each of the hydrogen atoms may be independently replaced by a halide. R₃ is aryl, or a straight-chained or branched Ci to C₂₀ alkyl group, and wherein the two R₃ groups (when present) may be joined to form a 5- to 6-membered heterocyclic ring; R is an aliphatic, cycloaliphatic, or aromatic group containing Ci to C ₀ linear or branched, α,β-unsaturated straight or branched alkenyl or alkynyl; and wherein Ri may contain a group selected from Cι-C₂₀, OH, halogen, OR₂, and SR₃, wherein R₂ is an alkyl from 1 to 20 carbon atoms in which each of the hydrogen atoms may be independently replaced by a halide, R₃ is aryl or a straight-chained or branched Ci to C₂o alkyl group, or wherein the two R₃ groups (when present) may be joined to form a 5- to 6-membered heterocyclic ring, and wherein Ri may be linked to R by O, S, C(=O), or S(=0)₂; n may represent 0 to 20 repeating units; and. m may range from 1 to 10.

The alcohols may be used alone or in combination with alcohols which are appropriate in forming, for example, poiyfunctional (meth)acrylic esters. 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, mono alcohols or polyols containing 2 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-hexanoi, octanol, undecanol, dodecanol, cyclohexylmethanol, benzyl alcohol, phenoxy ethanol, ethylene glycol, diethylene glycol, neopentyl glycol, polytetramethylene glycol, 1 ,5-pentanediol, 1 ,4-butanediol, 2-methyl 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 poiyhydric 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.

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.

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. 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.

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^CC to about 150°C. The azeotropic agent may be used in varying amounts. Preferably, 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. More preferably, the azeotropic agent is used in an amount ranging from about 10 to about 30 percent by weight. Any number of epoxides can be used for the purposes of the invention. Typically, polyepoxides are used. Preferably the polyepoxides are 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. Particularly preferred polyepoxides are glycidyl ethers of polyhydric alcohols or polyhydric phenols having equivalent weights per epoxide groups ranging from about 150 to about 1500, more preferably from about 150 to about 1000.

The epoxide component can be used in varying amounts. As an example, a epoxide may be reacted with an acid in a proportion of about 1 equivalent of epoxide per each equivalent of acid. The term "acid" in the preceding sentence encompasses excess esterification catalyst and unreacted organic acid. More preferably, the proportions of equivalents may range from about 0.8:1 to about 1.2:1.

The process of the invention may employ a carbodiimide, preferably a carbodiimide intermediate containing from about 1 to about 1000 repeating units. Polycarbodiimides are preferably utilized. Exemplary carbodiimides are described in U.S. Patent No. 5,115,072 to Nava et al., the disclosure of which is incorporated herein by reference in its entirety.

In general, the carbodiimides preferably are polycarbodiimides that include aliphatic, cycloaliphatic, or aromatic polycarbodiimides. The polycarbodiimides can be prepared by a number of reaction schemes known to those skilled in the art. For example, the polycarbodiimides may be synthesized by reacting an isocyanate-containing intermediate and a diisocyante under suitable reaction conditions. The isocyanate containing intermediate may be formed by the reaction between a component, typically a monomer containing active hydrogens, and a diisocyanate. Included are also polycarbodiimides prepared by the polymerization of isocyanates to form a polycarbodiimide, which subsequently react with a component containing active hydrogens. Preferably, the carbodiimide intermediate is represented by the formula selected from the group consisting of: R₅-N=C=N ^R₄-N=C=N^— R₅ and

wherein:

R4 and R₅ are independently selected from the group consisting of alkyl, aryl, and a compound containing at least one radical;

Re may be a monomeric unit or a polymeric unit having from 1 to 1000 repeating units; and n ranges from 0 to 100;

The carbodiimide is preferably used in an percentage ranging from about 0.10 to about 50 based on the weight of reactants, and more preferably from about 1 to about 20 percent.

Other components may be employed in accordance with the present invention. Examples of components include, but are not limited to, polymerization inhibitors, free radical scavengers, and antioxidants. These materials can be used to minimize the loss of organic acid or esters formed during the method due to the occurrence of unfavorable side reactions. The method of the invention may be carried out using known and existing equipment. The method may take place in various vessels or reactors, the selection known to those skilled in the art. Preferably, the vessel or reactor is fabricated from equipment that are inert under the conditions of the reaction such as, but not limited to, glass, carbon steel, and the like. A conventional reactor equipped with a reflux set up and vacuum is typically employed. The reactor or vessel may employ an agitator for stirring the contents of the reactor, and may also employ a heater which may encompass, but is not limited to, a heat lamp, a heating mantle, an oil bath, and the like. The method of the invention typically begins by reacting alcohol, organic acid, esterification acid catalyst, and an azeotropic agent in the reactor. This reaction step is preferably carried out at a temperature ranging from about 70°C to about 150°C, more preferably from about 90°C to about 120°C. During the course of this reaction, water is produced as a by-product and is preferably removed by distillation such as, for example, by an azeotropic distillation.

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 an epoxide, a carbodiimide, or both to react with the excess organic acid and catalyst. In the event that an epoxide is employed, a second 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 catalysts include, but are not limited to, organophosphonium salts, and tertiary amines such as 2,4,6- tri(dimethylaminomethyl)phenol[DMP-30] 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, benzyitributylammonium chloride, benzyitributylammonium bromide, benzyitributylammonium 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.

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:

(F )₃P or (R₄)₄PY where R₄ is an aliphatic, cycloaliphatic or aromatic group containing from C₄ to C₂₀, and may be linear or branched.

Y is a group selected from chlorine, bromine, fluorine, iodine, acetate or bicarbonate.

Preferred examples include, but are not limited to, triphenyl phosphine, tributyl phosphine, tributylphosphonium acetate, tributylphosphonium bromide, tributylphosphonium chloride, tributylphosphonium fluoride, tributylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium acetate, and phosphine salts as those described in U.S. Patent No. 4,310,708, the disclosure of which is incorporated herein by reference in its entirety.

The reaction involving the epoxide or the carbodiimide is preferably carried out at a temperature ranging from about 15^CC to about 120°C, and more preferably from about 30°C to about 115°C. The completion of the reaction involving the epoxide or carbodiimide is then determined, and typically the azeotropic agent is subsequently removed, preferably by distillation under vacuum. It should be appreciated, however, that the azeotropic agent may be removed during other stages of the invention.

The final composition of the mixture upon completion includes various vinyl-containing reaction products. Preferably, the composition comprises the esterified intermediate (e.g., a poiyfunctional acrylic or methacrylic ester compound), a vinyl ester resin (e.g., an epoxy acrylate), as well as an vinyl- functional carbodiimide resin (e.g., an acrylic derivative of a polycarbodiimide). These reaction products mentioned above have vinyl- functionality which enables them to be able to react with other compounds as desired by one who is skilled in the art. In various embodiments, the vinyl ester resin and/or vinyl-functional carbodiimide each may be a sulfonate- containing material. As an example, when alkyl toluene sulfonic acids are used, a reaction product of an epoxide, unreacted organic acid, and excess esterification acid catalyst may be illustrated by formula (I):

The vinyl ester resin and/or the vinyl-functional carbodiimide typically each contain a plurality of polymer chains. In various embodiments, it should be appreciated that a sulfonate group may be only present in a relatively small portion of the vinyl ester resin and/or vinyl-functional carbodiimide, usually by virtue of the reaction with a sulfur-containing esterification acid catalyst. Although not wishing to be bound by theory, Applicants believe this is due to the small amount of excess esterification catalyst used in proportion to epoxide and/or carbodiimide. In general, the number of sulfonate groups in the vinyl ester resin and/or vinyl-functional carbodiimide is typically proportionate to the amount of esterification acid catalyst employed in the process of the invention.

Advantageously, the esterified intermediates are capable of becoming incorporated into the network of a final cured vinyl-containing resin. Depending on the ratios of acrylic or methacrylic acid to the alcohol and the epoxide equivalent weight of the polyepoxides that may be formed, the ratio of acrylic or methacrylic esters to vinyl esters can widely vary. If a large excess of acrylic or methacrylic acid is used (a 3:1 to 10:1 weight equivalent ratio relative to alcohol), the final composition of the resin may comprise high percentages of vinyl-containing resins (e.g., resins formed from the epoxide and/or carbodiimide) and low percentages of acrylic or methacrylic ester compounds (e.g., formed from the reaction product or organic acid and alcohol). The viscosity of such a resin may be high, and these resins may be diluted to prepare, for example, laminates, glass reinforced plastic pipe, and reinforced molded parts. If only a slight excess of acrylic or methacrylic acid is used, the final composition of the resin may comprise primarily acrylic or methacrylic ester compounds and a low percentage of vinyl-containing resins. The viscosity of such a resin may be excessively low, and thus the resin can be used as a blending agent with other resins such as unsaturated polyesters or other vinyl esters to reduce their volatile monomer content and potentially improve their properties. The vinyl-containing compounds (i.e., the reaction products of the organic acid and alcohol) of the invention may be used in combination with other resins such as polyesters and suitable monomeric components to form a liquid resin. The liquid resin may be employed, for example, as a laminating resin or a gel coat resin as a coating on a suitable substrate. A number of substrates may be employed such as, for example, a marine vessel, a vehicle, or an aircraft.

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 to form a molded or shaped article.

The resins formed as a result of the processes of the invention can advantageously be employed in a number of 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. The invention is highly advantageous relative to prior art processes.

For example, the invention allows for 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 35 percent based on the weight of the reactants. The invention instead is capable of utilizing the esterified intermediate formed during the reaction as a diluent during the reaction involving the epoxide or the carbodiimide.

By virtue of the process of the invention, vinyl-containing resins, (e.g., vinyl esters, having relatively high molecular weights) can be formed from epoxy with improved physical properties using low amounts of ethylenically unsaturated compounds as diluents. Preferably, the number average molecular weight of the vinyl-containing resins range from about 500 to about 5000. The invention also allows for a high conversion of the vinyl- containing compounds, preferably from about 95 to about 100.

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.

The following examples are provided to illustrate the present invention, and should not be construed as limiting thereof.

Example 1

A three liter reaction flask equipped with a stirrer, thermometer, air/nitrogen inlet tube, and Dean Stark distillation heads was charged with 93 grams (1.5 moles) of ethylene glycol, 430 grams (5 moles) of methacrylic acid, 2.6 grams of toluenesulfonic acid (PTSA), 100 grams of cyclohexane, 15 grams of toluene and 0.44 grams of THQ (Toluhydroquinone). The mixture was heated to a temperature between 95°C to 110°C and held at that temperature, the progress of the reaction was monitored by the water distilled off azeotropically and by acid number titration. After about 6 to 7 hours, there was no more water distilled off and acid number dropped to 185. 1000 grams (1 moles) of a polyepoxide Epon 1001® (available from Shell Chemicals) having an epoxy equivalent weight of 490-510 and 5.5 grams of 2,4,6- tri(dimethyl aminomethyl)phenol [DMP-30] was then added. The reaction was continued between 100°C and 115°C until an acid number of below 13 and an epoxy equivalent weight of above 10,000 were obtained. The azeotropic solvents were then removed under slight vacuum. 750 grams of styrene and 0.1 grams of phenothiazine inhibitor was then added and the product was cooled to room temperature and poured from the reaction flask. The resin obtained was identified as resin "1" in Table 1. Example 2 The procedure described in Example 1 was essentially repeated with the following initial reactor charges: 277 grams (1.85 moles) of phenoxy ethanol, 417 grams (4.85 moles) of methacrylic acid, 7 grams of PTSA, 70 grams of cyclohexane, 70 grams of toluene as azeotropic solvents and 0.6 grams of methoxyphenol. The reaction was carried out from 105°C to 115°C until a acid number of 210 was reached. 1373 grams (1.37 moles) of Epon 1001® and 6 grams of DMP-30 were then charged and the reaction was continued between 105°C and 115°C, during which the azeotropic solvents were removed simultaneously. After an acid number of below 13 and an epoxy equivalent weight of above 5500 were reached, 1045 grams of styrene and 0.15 grams of phenothiazine were then charged. The resin was then cooled. The resin is identified as resin "2" in Table 1.

Comparative Example 3

A Bisphenol A conventional epoxy vinyl ester resin, DION VER^®9100, identified as resin "3" in Table 1 and available from Reichhold Inc. of Durham,

North Carolina was compared with Resins 1 and 2. As shown, the resins of the invention possess good physical properties with respect to Resin 3 while employing a reduced level of styrene.

Table 1

Resin: 1 2 3

Styrene Content (wt%) 34 34 44

Molecular Weight (Mn) 1720 1760 1700

Polydispersity 2.1 2.1 2.1

Water absorption % (2 hour 0.45 0.53 0.46 boil)

Viscosity(cps) (Neat resin) 400 430 450

HDT @ 264psi, °C 106 91 104

Flexural Strength(psi) 19,021 20,480 23,000

Flexural Modulus(10⁵ psi) 5.29 5.58 5.00

Tensile Strength(psi) 12,403 12,120 11 ,600

Tensile Modulus(10⁵ psi) 4.97 5.02 4.60

% Elongation at break 3.75 7.1 5.2

Example 4

A five liter reaction flask equipped with a stirrer, thermometer, air/nitrogen inlet tube, and Dean Stark distillation heads was charged with 1175 grams (8.5 moles) of phenoxy ethanol, 1590 grams (18.5 moles) of methacrylic acid, 22 grams of PTSA, 360 grams of toluene and 2.1 grams of methoxyphenol. The resulting mixture was heated to a temperature between about 105°C and 115°C and held at that temperature until no water was distilled off (at about 188 acid number). 1807 grams (9.6 moles) of diglycidyl ether of Bisphenol A (epoxy equivalent weight from 186 to 192) and 10 grams of tetramethylamonium chloride (TMAC) was then charged. The mixture was heated back to between 105°C and 115°C and reaction continued while toluene was distilled off simultaneously. The mixture was stopped and cooled to room temperature when acid number of 13 and epoxy equivalent weight of 5000 was reached. The viscosity of the mixture was about 1400 cps. The resin was identified as "4".

Example 5 A procedure similar to Example 4 was employed except that the following charge weights were used: 1567 grams (11.35 moles) of phenoxy ethanol, 1700 grams (19.75 moles) of methacrylic acid, 22 grams of PTSA, 400 grams of toluene, 2 grams of (MEHQ) and 1600 grams (4.2 moles) of diglycidyl ether of Bisphenol A. The viscosity of the reaction mixture was about 225 cps. The resin was identified as "5".

Example 6

A procedure similar to Example 4 was employed except that the following charge weights were used: 1949 grams (14.1 moles) of phenoxy ethanol, 1642 grams (19.1 moles) of methacrylic acid, 30 grams of PTSA, 450 grams of toluene, 2.4 grams of MEHQ, 1084 grams (2.85 moles) of diglycidyl ether of Bisphenol A (EEW 187-192) and 8 grams of triphenyl phosphine. The viscosity of the reaction mixture was about 95 cps. The resin was identified as "6".

Example 7 Resins "5" and "6" at 1 to 1 ratio to produce a resin with a viscosity of

500 cps, identified as resin "7" in Table 2.

Example 8

A procedure similar to Example 4 was employed except that the following charge weights were used: 792 grams (7.6 moles) of neopentyl glycol, 2000 grams ( 23.2 moles) of methacrylic acid, 25 grams of PTSA, 400 grams of toluene, 2 grams of MEHQ, and 1520 grams (4 moles) of diglycidyl ether of Bisphenol A. The viscosity of the reaction mixture was about 450 cps.

The resin was identified as resin "8" in Table 2.

Example 9

A procedure similar to Example 4 was employed except that the following charge weights were used: 559 grams (6.2 moles) of 1 , 4 butandiol,

1895 grams ( 22 moles) of methacrylic acid, 25 grams of PTSA, 400 grams of toluene, 2 grams of MEHQ, 1800 grams ( 4.6 moles ) of diglycidyl ether of

Bisphenol A.(EEW 187-192) and 9 grams of TMAC. The viscosity of the reaction mixture was about 450 cps and the acid number was 15. The resin was identified as resin "9" Example 10 50 grams of DION CIPP™ 1070, a polycarbodiimide available from Reichhold, was well mixed into resin "9" and allowed to sit over night. The acid number of the mixture fell to 1. This resin was identified as resin "10" in Table 2.

Example 11 A procedure similar to Example 4 was employed except that the following charge weights were used: 834 grams (2.3 moles) of polyoxyethylene bisphenol A containing an average of 3 moles of ethylene oxide per mole of bisphenol A, 570 grams (6.6 moles) of methacrylic acid, 0.7 grams of THQ, 10 grams of PTSA, 200 grams of toluene, 380 grams ( 1 mole) of diglycidyl ether of bisphenol A (EEW 187-192) and 1.8 grams of TMAC. The viscosity of the reaction mixture was about 7150 cps. 500 grams of 1 ,6 hexanediol dimethacrylate and 100 grams of DION CIPP™ 1070, a polycarbodiimide available from Reichhold, was well mixed into the resin and allowed to sit over night. The acid number of the mixture fell to 3 and the viscosity of the final resin is 492 cps. This resin was identified as resin "11" in

Table 2.

Example 12

A procedure similar to Example 4 was employed except that the following charge weights were used: 1151 grams (3.55 moles) of polyoxyethylene bisphenol A containing an average of 2 moles of ethylene oxide per mole of bisphenol A, 870 grams (10.1 moles) of methacrylic acid, 1.1 grams of MEHQ, 17 grams of PTSA and 3 grams of triphenyl phosphate as catalyst, 345 grams of toluene, 560 grams ( 1.5 mole) diglycidyl ether of bisphenol A (EEW 187-192) and 5.7 grams of TMAC. The viscosity of the final mixture was about 8350 cps. 690 grams of 1 ,6 hexandiol dimethacrylate was added to the mixture, and the viscosity of the final resin became 465 cps. The resin was identified as resin "12" in Table 2.

As described below, the resins illustrated in Table 2 display good physical properties. Table 2

Resin 7 8 10 11 12

Functional acrylates PEMA NPG BD DMA 3EBPA 2EBPA

DMA DMA DMA

Stability at 55 °C (days) 220 > 210

Barcol: 47-48 55-57 54-56 48-50 43-45

HDT @ 264psi, °C 77 169 142 99 105

Flexural Strength(psi) 10,685 9,232 5642 10,263 6,750 Flexural Modulus(10 psi) 6.3 6.8 5.4 5.7 5.0

Tensile Strength(psi) 6,332 3,423 3349 6,813 4,783 Tensile Modulus(10 psi) 6 6.2 5.55 5.0 5.0

% Elongation at Max. Load 1.13 0.6 0.64 1.49 1.0

PEMA - 2-phenoxyethyl methacrylate.

NPGDMA - Neopentyl glycol dimethacrylate.

BDDMA - Butanediol dimethacrylate.

3EBPA DMA - Ethoxylated Bisphenol A (3EO) dimethacrylate.

2EBPA DMA - Ethoxylated Bisphenol A (2EO) dimethacrylate.

Example 13 200 grams of resin "7" was mixed with 800 grams of resin "3" resulting in a homogeneous resin solution. The resin is identified as resin "13" in Table 3.

Example 14 200 grams of resin "11" was mixed into 800 grams of resin "3" resulting a homogeneous resin solution. The resin is identified as resin "14" in Table 3.

Example 15 200 grams of resin "12" was mixed into 800 grams of resin "3", resulting a homogeneous resin solution. The resin is identified as resin "15" in Table 3.

Table 3

Resin 13 14 15 3

Styrene Content (%) 35 35 35 44 Water absorption % 0.55 0.43 0.39 0.46 (2 hour boil) Barcol: 33-36 33-36 35-38 45 HDT 264psi, ^UC 98 106 109 104 Flexural Strength(psi 21252 20079 20080 23000 Flexural Modulus(10 psi) 5.4 5.01 5.05 5.0 Tensile Strength(psi) 1281 1 12730 12136 11 ,600 Tensile Modulus(10 psi) 5.13 4.72 4.79 4.6 % Elongation at max. load 6.84 5.87 4.36 5.2

As see from Table 3, the resins 13-15 of the invention provide good physical properties relative to comparative resin 3 while employing less styrene.

Comparative Example 16 A bisphenol A fumaric polyester resin, ATLAC^® 382-05A available from Reichhold, Inc, is identified as resin "16" in Table 4.

Example 17 300 grams of resin "8" was mixed into 700 grams of resin "16", resulting a homogeneous resin solution, identified as resin "17" in Table 4.

Comparative Example 18 A modified bisphenol A fumaric polyester resin, DION^® 6694 available from Reichhold, Inc. is identified as resin "18" in Table 4.

Example 19 300 grams of resin "8" was mixed with 700 grams of resin "18", resulting a homogeneous resin solution. The resin is identified as resin "19" in Table 4.

Table 4

Resin 16 17 18 19

Styrene Content (%) 49 35 49 35

Water absorption % 0.66 0.43 0.3 0.46

(2 hour boil)

Barcol: 38 38-41 35-40 36-42

HDT @ 264psi, °C 131 131 131 132

Flexural Strength(psi) 17000 19329 14600 18830 Flexural Modulus(10 psi) 4.3 5.8 4.9 5.7

Tensile Strength(psi) 10000 10124 8200 9116 Tensile Modulus(10⁵ psi) 4.3 4.84 3.4 4.79 % Elongation at break 2.5 2.5 2.4 2.22

As seen from Table 4, resins 17 and 19 of the invention offer excellent physical properties relative to comparative resins 16 and 18 while employing less styrene.

Example 20

A five liter reaction flask equipped with a stirrer, thermometer, nitrogen inlet tube, and Dean Stark distillation head was charged with 196 grams (2 moles) of maleic acid, 1368 grams (4 moles ) of polyoxyethylene bisphenol A containing an average of 2 moles of ethylene oxide per mole of bisphenol A. 580 grams (6.75 moles) of methacrylic acid, 16.5 grams of PTSA, 250 grams of toluene and 0.65 grams of MEHQ. The resulting mixture was heated to a temperature between about 105°C-115°C and held at that temperature until water ceased to be distilled off (at about 55 acid number). 380 grams (1 moles) of diglycidyl ether of bisphenol A (epoxy equivalent weight from 186 to 192) and 5 grams of tetramethylammonium chloride (TMAC) was then added. The mixture was heated back to between 105°C and 115°C and reaction continued while toluene was distilled off simultaneously. When an acid number of 13 and epoxy equivalent weight of 4000 was reached, the reaction was stopped by charging 750 grams of styrene and cooled to room temperature. The viscosity of the mixture was about 305 cps. The resin is identified as "20" in Table 5.

Example 21 500 grams of resin "20" was mixed with 500 grams of resin "3", resulting a homogeneous resin solution. The resin is identified as resin "21" in Table 5.

Example 22 500 grams of resin "20" was mixed with 500 grams of resin "16", resulting a homogeneous resin solution. The resin is identified as resin "22" in Table 5. Example 23 500 grams of resin "20" was mixed with 500 grams of resin "18", resulting a homogeneous resin solution. The resin is identified as resin "23" in Table 5.

Table 5

Resin 20 21 22 23

Styrene Content (%) 23 33 36 36

Water absorption % 0.42 0.43 0.45 0.38

(2 hour boil)

Barcol: 36-37 39-41 41-43 44-47

HDT @ 264psi, °C 61 86 110 114

Flexural Strength(psi) 16540 20259 21352 18787 Flexural Modulus(10 psi) 5.07 5.62 5.65 5.68

Tensile Strength(psi) 8265 11692 11127 11263 Tensile Modulus(10 psi) 4.91 5.15 5.14 5.25

% Elongation at max. load 2.39 3.76 3.04 3 As seen from Table 5, the listed resins of the invention display good physical properties.

The invention has been described in detail with reference to its preferred embodiments and its example. However, it will be apparent that numerous variations and modifications can be made without departure from the spirit and scope of the invention as described in the foregoing detailed specification and claims.

Claims

THAT WHICH IS CLAIMED:

1. A process for preparing a vinyl-containing compound, said process comprising: reacting an alcohol and an organic acid in the presence of an esterification acid catalyst to form an esterified intermediate, wherein an azeotropic agent is present to facilitate removal of water generated during the reaction, and wherein the organic acid is present in a excess of its weight equivalent relative to the alcohol; and reacting an epoxide, a carbodiimide, or both with: (1 ) unreacted organic acid and (2) excess esterification acid catalyst such that the acid catalyst becomes neutralized; wherein the reaction between the epoxide, the unreacted organic acid, and the excess esterification catalyst forms a vinyl ester resin; and wherein the reaction between the carbodiimide, the unreacted organic acid, and the excess esterification catalyst forms an vinyl-functional carbodiimide.

2. The process according to Claim 1 , wherein the esterification acid catalyst is a sulfur-containing catalyst.

3. The process according to Claim 1 , wherein the alcohol is a monofunctional alcohol or a poiyfunctional alcohol.

4. The process according to Claim 1 , wherein the alcohol is represented by formulas selected from the group consisting of {X} [R] m

X— [R]— X n

X-R--[Rι]-R-X n

X-CH2-[Rι]-CH2-X n

-CH2— R--[Rι] — R-CH2-X n

wherein :

X is OH or SH;

R is an aliphatic or cycloaliphatic group containing Ci to C₄o linear or branched, α,β-unsaturated straight or branched alkenyl or alkynyl; and wherein R may contain a group selected from C₁-C₂₀, OH, halogen, OR₂, and SR_3l wherein R₂ is an alkyl containing from 1 to 20 carbon atoms in which each of the hydrogen atoms may be independently replaced by a halide. R3 is aryl, or a straight-chained or branched Ci to C₂o alkyl group, and wherein the two R₃ groups (when present) may be joined to form a 5- to 6-membered heterocyclic ring;

Ri is an aliphatic, cycloaliphatic, or aromatic group containing Ci to C _υ linear or branched, α,β-unsatu rated straight or branched alkenyl or alkynyl; and wherein Ri may contain a group selected from

OH, halogen, OR₂, and SR₃, wherein R₂ is an alkyl from 1 to 20 carbon atoms in which each of the hydrogen atoms may be independently replaced by a halide, R₃ is aryl or a straight-chained or branched d to C₂o alkyl group, or wherein the two R₃ groups (when present) may be joined to form a 5- to 6-membered heterocyclic ring, and wherein Ri may be linked to R by O, S, C(=0), or S(=0)₂; n may be from 0 to 20 repeating units; and. m may be from 1 to 10. O 01/27183 PCΪYUSOO/28329

5. The process according to Claim 1 , wherein the organic acid is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, and mixtures thereof.

6. The process according to Claim 1 , wherein the esterification acid catalyst is a Lewis Acid catalyst.

7. The process according to Claim 1 , wherein the azeotropic agent is an inert solvent.

8. The process according to Claim 7, wherein the inert solvent is selected from the group consisting of benzene, toluene, xylene, hexane, cyclohexane, and mixtures thereof.

9. The process according to Claim 1 , wherein the molar ratio of organic acid to poiyfunctional alcohol ranges from about 1:1 to about 10:1.

10. The process according to Claim 1 , wherein the said step of reacting a compound with the unreacted organic acid and the esterification acid catalyst comprises reacting an epoxide.

11. The process according to Claim 10, wherein the epoxide is a monofunctional epoxide or the poiyfunctional epoxide is a glycidyl ether of a polyhydric alcohol or polyhydric phenol.

12. The process according to Claim 1 , wherein the said step of reacting a compound with the unreacted organic acid and the acid catalyst comprises reacting a carbodiimide.

13. The process according to Claim 12, wherein the carbodiimide is a carbodiimide intermediate represented by the formula selected from the group consisting of:

wherein: n is an integer ranging from 0 to 100;

R₄ and R₅ are independently selected from the group consisting of alkyl, aryl, and a compound containing at least one radical; and

Re may be a monomeric unit or a polymeric unit having from 1 to 1000 repeating units.

14. The process according to Claim 1 , wherein the esterified intermediate is an acrylic intermediate.

15. A process for preparing an vinyl-containing compound, said process comprising: reacting an alcohol and an organic acid selected from the group consisting of acrylic acid, crotonic acid, methacrylic acid, and mixtures thereof in the presence of an acid catalyst to form an acrylic intermediate, and wherein an azeotropic agent is present during the reaction to facilitate removal of water generated during the reaction, wherein the weight equivalent ratio of the organic acid to the alcohol ranges from about 1 :1 to about 10:1 ; and reacting an epoxide, a carbodiimide, or both with: (1 ) unreacted organic acid and (2) excess esterification acid catalyst such that the acid catalyst becomes neutralized; wherein the reaction between the epoxide, the unreacted organic acid, and the excess esterification catalyst forms a vinyl ester resin; and wherein the reaction between the carbodiimide, the unreacted organic acid, and the excess esterification catalyst forms an vinyl-functional carbodiimide.

16. The process according to Claim 15, wherein the esterification acid catalyst is a sulfur-containing catalyst.

17. The process according to Claim 15, wherein the alcohol is a monofunctional alcohol or a poiyfunctional alcohol.

18. The process according to Claim 15, wherein the alcohol is represented by formulas selected from the group consisting of

{X} [R] m

X— [R]— X n

X-R~-[R₁]-R~X n

X-CH₂-[Rι]-CH₂-X n

X-CH₂— R----[Ri] — R-CH₂-X n

wherein :

X is OH or SH;

R is an aliphatic or cycloaliphatic group containing Ci to C o linear or branched, α,β-unsaturated straight or branched alkenyl or alkynyl; and wherein R may contain a group selected from C-ι-C₂₀, OH, halogen, OR₂, and SR₃, wherein R₂ is an alkyl containing from 1 to 20 carbon atoms in which each of the hydrogen atoms may be independently replaced by a halide. R₃ is aryl, or a straight-chained or branched Ci to C₂o alkyl group, and wherein the two R₃ groups (when present) may be joined to form a 5- to 6-membered heterocyclic ring;

Ri is an aliphatic, cycloaliphatic, or aromatic group containing Ci to C o linear or branched, α,β-unsaturated straight or branched alkenyl or alkynyl; and wherein Ri may contain a group selected from CrC₂o, OH, halogen, OR₂, and SR₃, wherein R₂ is an alkyl from 1 to 20 carbon atoms in which each of the hydrogen atoms may be independently replaced by a halide, R₃ is aryl or a straight-chained or branched Ci to C₂₀ alkyl group, or wherein the two R₃ groups (when present) may be joined to form a 5- to 6-membered heterocyclic ring, and wherein Ri may be linked to R by O, S, C(=0), or S(=0)₂; n may be from 0 to 20 repeating units; and. m may be from 1 to 10.

19. The process according to Claim 15, wherein the esterification acid catalyst is a Lewis Acid catalyst.

20. The process according to Claim 15, wherein the azeotropic agent is an inert solvent.

21. The process according to Claim 20, wherein the inert solvent is selected from the group consisting of benzene, toluene, xylene, hexane, cyclohexane, and mixtures thereof.

22. The process according to Claim 15, wherein the said step of reacting a compound with the unreacted organic acid and the esterification acid catalyst comprises reacting an epoxide.

23. The process according to Claim 22, wherein the epoxide is a monofunctional epoxide or the poiyfunctional epoxide is a glycidyl ether of a polyhydric alcohol or polyhydric phenol.

24. The process according to Claim 15, wherein the said step of reacting a compound with the unreacted organic acid and the esterification acid catalyst comprises reacting a carbodiimide.

25. The process according to Claim 25, wherein the carbodiimide is a carbodiimide intermediate is represented by the formula selected from the group consisting of:

R₅-N=C=N ^R₄-N=C=N^— R₅ and

wherein: n is an integer ranging from 0 to 100;