US20110207950A1 - Vinyl-containing compounds and processes for making the same - Google Patents

Vinyl-containing compounds and processes for making the same Download PDF

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US20110207950A1
US20110207950A1 US13/024,547 US201113024547A US2011207950A1 US 20110207950 A1 US20110207950 A1 US 20110207950A1 US 201113024547 A US201113024547 A US 201113024547A US 2011207950 A1 US2011207950 A1 US 2011207950A1
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vinyl
acid
meth
anhydride
acrylate
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Hildeberto Nava
Yongning Liu
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REICHHOLD 2 LLC
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Priority to US13/024,547 priority Critical patent/US20110207950A1/en
Priority to DK11707248.8T priority patent/DK2539387T3/da
Priority to EP11707248.8A priority patent/EP2539387B1/en
Priority to PCT/US2011/024970 priority patent/WO2011106212A1/en
Priority to ES11707248T priority patent/ES2743954T3/es
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Priority to US15/233,318 priority patent/US9957243B2/en
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Priority to US15/941,586 priority patent/US10570107B2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • C08G63/47—Polyesters chemically modified by esterification by unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds

Definitions

  • the present invention generally relates to processes for preparing compounds having vinyl functionality.
  • esters are (meth)acrylic acid esters which are based on polyhydric alcohols and oligoesters formed from polyhydric alcohols reacted with polyfunctional acids or anhydrides. Their area of application is mainly in coating compositions curable by UV or electron beam.
  • One preferred method of preparing (meth)acrylates is the direct esterification of the polyhydric aligo-alcohols with acrylic or methacrylic acid in the presence of esterification catalyst and of a solvent which forms and azeotropic mixture with water entraining agent.
  • Typical reaction temperatures can range from 90° C. to 150° C.
  • High reaction temperatures require a large amount of inhibitors in order to achieve good yields of the esterification products and for effectively suppressing the polymerization of (meth)acrylic acid esters.
  • a stream of air needs to be added to maintain the inhibitors active and prevent polymerization of the (meth)acrylate intermediates.
  • the polymerization inhibitors in combination with air and high temperatures generate a strong color in the reaction mixture, therefore making difficult to prepare materials with low color.
  • Exemplary prior art references include U.S. Pat. Nos. 5,874,503 and 4,546,142 and describe the use of waxes with a variety of unsaturated polyester resins.
  • the wax is pre-dispersed in the resin and during the curing process, the wax forms a thin film on the laminates prepared.
  • the film of wax act as a barrier preventing styrene from evaporating at the moment of curing the laminates.
  • a disadvantage on using waxes is that the wax separates from the resin when the resin mixture is exposed to cold temperatures, becoming inefficient at the time of curing the composite systems.
  • U.S. Pat. Nos. 5,393,830, 5,492,668, and 5,501,830 propose laminating resins which employs a reduce amount of styrene so as to meet a specified volatile emission level according to test standards.
  • the disclosed resin mixtures include a polyester resin, ethylene glycol dimethacrylate, vinyl toluene, cyclohexyl methacrylate, and bisphenol dimethacrylate.
  • the compositions require high cost diluents and have more difficulty in wetting fibers.
  • U.S. Pat. No. 6,468,662 describes using a low molecular weight epoxy acrylate in combination with reduce amount of styrene and methacrylate monomers. Glass fiber wetting is improved but cost may be compromised in certain applications.
  • U.S. Patent Publication Nos. 2004/00776830 and 2007/0179250 propose the preparation of low molecular weight saturated polyester polyols end-capped with at least one (meth)acrylic acid.
  • the esterification process requires a large amount of inhibitors and air during the process which leads to dark products.
  • the (meth)acrylate intermediates are mixed with styrene.
  • U.S. Pat. No. 6,153,788 describes the preparation of monohydric and polyhydric alcohols and polyesters reacted with (metha)acrylate end groups.
  • the esterification is carried in the presence of an esterification catalyst, phenolic inhibitors, a solvent to help azeotropically remove the water generated, air is passed though the reaction medium, and a monofunctional epoxy to neutralize the mixture.
  • High viscosities are reported for the polyester acrylate intermediate is reported.
  • U.S. Pat. No. 6,458,991 proposes the preparation of hydroxyl containing polyfunctional intermediates esterified with acrylic or methacrylic acid in the presence of esterification catalyst, hypophosphorus acid, a Cupper salt, a solvent and an air flow passed through the mixture.
  • Acid neutralization is done using calcium oxide and sodium sulfide. Problems are encountered with the process removing completely the calcium oxide and having residual sodium sulfide which prevents crosslinking of the acrylate intermediate under room temperature curing conditions.
  • U.S. Pat. Nos. 6,063,957, 6,150,458, and 5,821,383 describe hydroxyl containing polyfunctional alcohols and polyesters, esterified acrylic acid, an esterification catalyst, a solvent, peholic inhibitors, antioxidants and in the presence of air. Amines are used to scavenge the catalyst and residual acid. It is common to observe that amines in the presence of air and temperature oxidize thereby increasing the color of the mixtures.
  • U.S. Pat. No. 6,268,467 describes unsaturated polyester resins for gelcoat applications having a number average molecular weight of 700-2500 and a weight average of 2600 to 6000.
  • the resins are dissolved in a styrene content ranging from 28 to 35%.
  • the low styrene content is added to minimize the problem with volatile organic emissions (VOC).
  • U.S. Patent Publication No. 2009/0022998 describes unsaturated polyester for gelcoat applications containing styrene in a concentration as low as 28%. The low styrene content is added to control the VOC emissions.
  • U.S. Patent Publication No. 2009/076218 describes unsaturated polyesters for gelcoat applications end-capped with glycidyl methacrylate having a number average molecular weight from about 500 to 2500.
  • the references propose that if the molecular weight is less than 560, the curing and gelcoat properties will be poor. In addition, if the molecular weight is higher than about 2500, the resulting resin will have a high viscosity and can not be used to make a low VOC gelcoat.
  • the reference proposes styrene content of up to 30% in combination with 30 percent 1,6-hexanediol diacrylate.
  • Such a process could advantageously be employed in the preparation of gelcoats, and applied 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, filament winding, hand lay-up, resin transfer molding, prepregs, coating resins and the like.
  • SMC sheet molding compounding
  • the present invention provides a process for forming vinyl-containing compounds. Such a process eliminates the need for the multiple steps of the prior art processes and provides vinyl-containing compounds with low color.
  • a resin system is substantially free of hazardous air pollutants and/or have a minimum amount of reactive solvent such as styrene or polyfunctional (meth)acrylates.
  • the present invention provides a process for preparing vinyl-containing compounds used, for example, in gelcoats having a low molecular weight, low viscosity and reactive groups within the molecule.
  • the process for forming vinyl-containing compounds comprises 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.
  • FIG. 1 is a graphic comparison of viscosity versus time at room temperature and at 65° C. for 60 days.
  • FIG. 2 is a graphic comparison of molecular weight versus time at room temperature and at 65° C. for 60 days.
  • FIG. 3 is a graphic comparison of AHPA color versus time at room temperature and at 65° C. for 60 days.
  • 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.
  • hydrogen-containing polyesters typically having a low molecular weight
  • Anhydrides that can be employed in the making of a polyester are preferably cyclic or acyclic, saturated or unsaturated.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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-1,3-pentadiol, 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,
  • 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.
  • 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.
  • 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.
  • 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. 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.
  • Acid catalysts include, but are not limited to, strong protic acids and Lewis acids.
  • 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.
  • sulfur-containing acid catalysts are preferably employed. Mixtures of any of the above may also be used.
  • 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.
  • 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-trimethylhydro
  • an azeotropic agent is employ to facilitate removal of water generated during the reaction between the organic acid and the alcohol.
  • an inert organic azeotropic agent is used.
  • 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.
  • 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.
  • 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.
  • any number of epoxies can be used for the purposes of the invention.
  • polyepoxides are used.
  • 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.
  • 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.
  • the epoxy component can be used in varying amounts.
  • 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.
  • 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.
  • 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.
  • 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 4 is an aliphatic, cycloaliphatic or aromatic group containing from C 4 to C 20 , and may be linear or branched, wherein Y is a group selected from chlorine, bromine, fluorine, iodine, acetate or bicarbonate.
  • 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.
  • 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.
  • 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.
  • 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).
  • styrene and styrene derivatives such as
  • 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.
  • (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
  • the gelcoat composition may include an agent such as an organic peroxide compound to facilitate curing of the composition.
  • 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-butyl peroxyisopropyl)benzene di-tert-butyl peroxide, 1,1-di (tert-amylperoxy)-cyclohexane, 1,1-di-(tert
  • 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 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.
  • the free radical initiator is a photoinitiator
  • the gelcoat composition is cured by UV radiation.
  • photoinitiators such as benzophenone, acetophenone and its derivatives, benzoin, benzoin ethers, thiozanthones, halogenated compounds, oximes, and acyl phosphine oxides.
  • 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.
  • 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.
  • 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.
  • 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.
  • SMC sheet molding compounding
  • the invention is highly advantageous relative to prior art processes.
  • 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.
  • ethylenically unsaturated vinyl monomer e.g., styrene
  • 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.
  • 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.
  • NPG Neopentyl glycol
  • DEG Diethylene glycol
  • CHDA cyclohexane diacid
  • 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.
  • 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.
  • 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.
  • Example 6 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.
  • Photomer 5429 is a polyester based vinyl compound obtained from Cognis Corp. and is identified as Comparative Example B.
  • Genomer 3485 is a polyester based vinyl compound, identified as Comparative Example C in Table 4 and available from Rahn Corp.
  • 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.
  • a Bisphenol A conventional epoxy vinyl ester resin, DION VER® 9100, identified as Comparative Example D, and an Isophthalic/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.
  • 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.
  • Tables 7 and 8 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.
  • Benzoyl Peroxide Lipersol A-98
  • 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.
  • RT room temperature
  • MW molecular weight
  • color color
  • the Example 6 resin has excellent stability even at 65° C. for up to 60 days.

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EP11707248.8A EP2539387B1 (en) 2010-02-24 2011-02-16 Vinyl-containing compounds and processes for making the same
PCT/US2011/024970 WO2011106212A1 (en) 2010-02-24 2011-02-16 Vinyl-containing compounds and processes for making the same
ES11707248T ES2743954T3 (es) 2010-02-24 2011-02-16 Compuestos que contienen vinilo y procesos para la fabricación de los mismos
US15/233,318 US9957243B2 (en) 2010-02-24 2016-08-10 Vinyl-containing compounds and processes for making the same
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CN103421170A (zh) * 2013-08-13 2013-12-04 江门市制漆厂有限公司 环氧树脂-丙烯酸树脂改性水分散醇酸树脂及其制备和应用
US10544299B2 (en) 2012-12-18 2020-01-28 Reichhold Llc 2 Vinyl-containing compounds with high heat distortion
US10570107B2 (en) 2010-02-24 2020-02-25 Reichhold Llc 2 Vinyl-containing compounds and processes for making the same
CN114981373A (zh) * 2020-01-16 2022-08-30 巴斯夫涂料有限公司 包含聚(乙烯-丙烯酸酯)共聚物的涂料组合物和涂覆基材的方法

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US10570107B2 (en) 2010-02-24 2020-02-25 Reichhold Llc 2 Vinyl-containing compounds and processes for making the same
US10544299B2 (en) 2012-12-18 2020-01-28 Reichhold Llc 2 Vinyl-containing compounds with high heat distortion
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CN114981373A (zh) * 2020-01-16 2022-08-30 巴斯夫涂料有限公司 包含聚(乙烯-丙烯酸酯)共聚物的涂料组合物和涂覆基材的方法

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