(Meth)acrylate-based reactive diluent composition for unsaturated polyester resins

Abstract

The present invention relates to a (meth)acrylate-based reactive diluent composition that enables styrene-free curing of unsaturated polyester resins. The reactive diluent composition contains a (meth)acrylic acid ester monomer and a compatibilizer that contains at least one (meth)acrylate moiety and at least one additional ethylenically unsaturated moiety.

Description

[Technical field]

[0001] 2. Background of the Invention Unsaturated polyester (UP) resins are unsaturated synthetic resins formed by the reaction of dibasic organic acids with polyhydric alcohols. Unsaturated polyester resins are widely used in various applications, for example, coatings, adhesives, relinings, gel coats, or composite materials. In composite materials, such as sheet molding compounds (SMC) or bulk molding compounds (BMC), UP resins are reinforced with solid materials, such as glass fibers, resulting in fiber-reinforced plastics (FRP). UP resins with high filler content are used in putties, polymer concretes, chemical anchors, colored pastes, or artificial marble.

[0002] UP resins can be cured using reactive diluents such as styrene, i.e. solvents with crosslinking / curing reactivity. Typically, UP resins are cured with high styrene content (usually up to 50% by weight). Thus, most UP resins consist of styrene solutions of unsaturated polyesters. For regulatory, health, and safety reasons, many companies aim to reduce the amount of styrene in the resins, which is presumed to be organ damaging and reproductive toxic, and thus develop styrene-reduced or even styrene-free systems. Although structural analogues of styrene are often used to replace styrene, this is only a stop-gap solution to avoid the direct use of styrene. Examples of such workarounds are 4-methylstyrene, 4-tert-butylstyrene, or 2,4,6-trimethylstyrene.

[0003] Despite its adverse physiological properties, styrene continues to be used in UP resins because it is very cheap, has good diluting power, and copolymerizes readily with the unsaturated portions of polyester resins.

[0004] Since (meth)acrylic acid and its esters (i.e. (meth)acrylates) are less hazardous and can be handled safely compared to styrene, it is considered particularly desirable to use (meth)acrylates as reactive diluents or in reactive diluent compositions, respectively. Methacrylates are said to be reactive diluents for vinyl ester resins. Vinyl ester resins are epoxy resins functionalized with (meth)acrylate end groups by reaction with (meth)acrylic acid or hydroxy (meth)acrylates. The end groups crosslink easily in the final curing step with methacrylate as reactive diluent. However, (meth)acrylates do not easily copolymerize / crosslink with UP resins and therefore cannot be used as reactive diluents for such resins.

[0005] In view of the above, it was an object of the present invention to provide a novel styrene-free (meth)acrylate-based reactive diluent composition for UP resins. Ideally, such a (meth)acrylate-based reactive diluent composition would contain (meth)acrylates with low vapor pressure, resulting in a VOC-free or even reduced VOC (VOC = volatile organic compounds) reactive diluent composition.

[0006] technical level CN111978477 relates to the field of composite materials, especially sheet molding compound raw materials, sheet molding compound products, and their manufacturing methods and applications. The sheet molding compound contains unsaturated polyester resin, low shrinkage agent, initiator, diluent monomer, sulfhydryl-containing compound, glass microspheres, flame retardant, and reinforcing material.

[0007] The same specification does not describe the reactive diluent composition according to the present invention, nor does it describe a curable resin composition containing the reactive diluent composition, or a pre-accelerated formulation containing the curable resin composition, nor does it disclose a method of curing an unsaturated polyester resin by providing a curable resin composition containing the reactive diluent composition of the present application.

[0008] WO 2013 / 124273 relates to a thermosetting radically curable resin composition comprising a methacrylate-containing resin suitable for (re)lining.

[0009] The resin composition comprises: (a) 30 to 70% by weight of a methacrylate-containing resin, (b) 2.5 to 20% by weight of an unsaturated polyester resin comprising a fumaric acid building block as an unsaturated dicarboxylic acid building block and an alkoxylated bisphenol A and / or alkoxylated bisphenol F building block as a diol building block; (c) 1 to 40% by weight of an ethylenically unsaturated compound copolymerizable with (a), (b), and (d), which is not benzyl methacrylate; (d) 5 to 60% by weight of benzyl methacrylate (see Claim 1 and from page 1, line 26 to page 2, line 3) Contains.

[0010] The same publication does not describe the reactive diluent composition according to the present invention, nor does it describe a curable resin composition containing the reactive diluent composition or a pre-accelerated formulation containing the curable resin composition, nor does it disclose a method of curing an unsaturated polyester resin by providing a curable resin composition containing the reactive diluent composition of the present application.

[0011] JP 2003-206306 A relates to a methyl methacrylate-containing molding material. This molding material contains a resin (A) containing a vinyl monomer (a), a vinyl monomer (b) and a polymer (c), a filler (B) and a curing agent (C).

[0012] The publication does not describe the reactive diluent composition according to the present invention, nor does it describe a curable resin composition containing the reactive diluent composition or a pre-accelerated formulation containing the curable resin composition, nor does it disclose a method of curing an unsaturated polyester resin by providing a curable resin composition containing the reactive diluent composition of the present application.

[0013] Summary of the Invention In a first aspect, the present invention provides a reactive diluent composition containing or consisting of a (meth)acrylic acid ester monomer and a compatibilizer, the compatibilizer comprising at least one (meth)acrylate moiety and at least one additional ethylenically unsaturated moiety.

[0014] In a second aspect, the present invention relates to a curable resin composition comprising at least an unsaturated polyester resin (UPR) and the reactive diluent composition described above.

[0015] In a third aspect, the present invention relates to a pre-accelerated formulation comprising the above-described curable resin composition and at least one accelerator.

[0016] In a fourth aspect, the present invention provides a styrene-free method for curing an unsaturated polyester resin, comprising the steps of: (a) providing the curable resin composition or the pre-accelerated formulation; (b) optionally adding at least one organic or inorganic additive as described above; and (c) Initiating the curing process by adding an initiator. The present invention provides a method comprising:

[0017] Detailed Description of the Invention The present inventors have developed a (meth)acrylate-based reactive diluent composition that enables styrene-free curing of UP resins.

[0018] More specifically, the inventors have found that the addition of a compatibilizer, i.e., a multifunctional, preferably difunctional, molecule containing at least one (meth)acrylate moiety and at least one additional ethylenically unsaturated moiety, which may be, for example, vinyl, allyl, or alkenyl, causes the UP resin to copolymerize with the (meth)acrylate.

[0019] The present invention therefore provides a reactive diluent composition comprising or consisting of a (meth)acrylic acid ester monomer and a compatibilizer, the compatibilizer comprising at least one (meth)acrylate moiety and at least one additional ethylenically unsaturated moiety, the (meth)acrylic acid ester monomer and the compatibilizer being different compounds.

[0020] In the context of the present invention, the term "(meth)acrylate" refers to an ester of methacrylic acid or acrylic acid.

[0021] In the compatibilizer, at least one (meth)acrylate moiety and at least one additional ethylenically unsaturated moiety are selected from the group consisting of C 1 ~C 20 and optionally containing one or more heteroatoms such as O, N, or S.

[0022] The compatibilizer can be selected from the group consisting of vinyl ether (meth)acrylate, allyl ether (meth)acrylate, and alkenyl (meth)acrylate. The vinyl ether (meth)acrylate can be, for example, monovinyl ether mono(meth)acrylate, monovinyl ether di(meth)acrylate, monovinyl ether tri(meth)acrylate, monovinyl ether tetra(meth)acrylate; divinyl ether mono(meth)acrylate, divinyl ether di(meth)acrylate, divinyl ether tri(meth)acrylate; and trivinyl ether mono(meth)acrylate, trivinyl ether di(meth)acrylate. Allyl ether (meth)acrylates include, for example, monoallyl ether mono(meth)acrylate, monoallyl ether di(meth)acrylate, monoallyl ether tri(meth)acrylate, monoallyl ether tetra(meth)acrylate; diallyl ether mono(meth)acrylate, diallyl ether di(meth)acrylate, diallyl ether tri(meth)acrylate; and triallyl ether mono(meth)acrylate, triallyl ether di(meth)acrylate. Alkenyl (meth)acrylates include mono-, di-, tri-, and tetra(meth)acrylates that contain one or more ethylenically unsaturated alkenyl (C=C) moieties different from (meth)acrylate.

[0023] Advantageously, the compatibilizer is selected from the group consisting of 4-(vinyloxy)butyl methacrylate, 2-(allyloxy)ethyl methacrylate, isoprenol methacrylate, 2,2-bis((allyloxy)methyl)butyl methacrylate, 2-((allyloxy)methyl)-2-ethylpropane-1,3-diylbis(2-methylacrylate), and eugenol methacrylate; 4-(vinyloxy)butyl methacrylate, 2-(allyloxy)ethyl methacrylate, and isoprenol methacrylate are particularly preferred as they exhibit good resin compatibility and curing properties.

[0024] The (meth)acrylic acid ester monomer may be selected from linear or branched alkyl C1-C20 alkyl (meth)acrylates, (alkyl)aryl (meth)acrylates, hydroxyalkyl (meth)acrylates, (poly)ether methacrylates, dimethacrylates, trimethacrylates, tetramethacrylates, and mixtures thereof.

[0025] Examples of suitable (meth)acrylic acid ester monomers are methyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, tert-butyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, cyclohexyl (meth)acrylate, iso-hexyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-propylheptyl (meth)acrylate, iso-decyl (meth)acrylate, iso-tridecyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, 3,3,5-trimethylcyclohexyl methacrylate, norbornyl (Meth)acrylate, dihydrodicyclopentadienyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyethyl phosphate (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl triglycol (meth)acrylate, butyl diglycol (meth)acrylate, glycidyl (meth)acrylate, glycerol formal (meth)acrylate, isopropylidene glycerin (meth)acrylate, isosorbide mono(meth)acrylate, isosorbide di(meth)acrylate, 3(4),8(9)-dimethacryloyloxymethyl-tricyclo[5.2.1.0 (2.6) ]decane (3,8-dihydroxymethyl-tricyclo[5.2.1.0 2.6]Dimethacrylate of decane), allyl (meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol 200 di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 2,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate and its isomers, glycerol di(meth)acrylate, trimethylolpropane and mixtures thereof.

[0026] Advantageously, the (meth)acrylic acid ester monomer is chosen from methyl methacrylate, glycerol formal methacrylate, benzyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 1,4-butanediol dimethacrylate, polyethylene glycol 200 dimethacrylate, ethylene glycol dimethacrylate, butyl diglycol methacrylate, and ethyl triglycol methacrylate.

[0027] It is noted that methacrylate monomers as reactive diluents with low vapor pressure are advantageous for formulating low-VOC and even no-VOC resin compositions. The use of styrene in composite resins releases styrene vapor into the working atmosphere. This exposes workers and the environment to dangerous vapors. Although methyl methacrylate is a less dangerous compound compared to styrene, it is also classified as a VOC due to its high vapor pressure. Therefore, to reduce the VOC content, it is preferable to use methacrylate monomers such as benzyl methacrylate, glycerol formal methacrylate, or 1,4-butanediol dimethacrylate, which have higher molecular weights and therefore lower vapor pressures.

[0028] In particularly preferred embodiments of the invention, the (meth)acrylic acid ester monomer is benzyl methacrylate and the compatibilizer is 4-(vinyloxy)butyl methacrylate, 2-(allyloxy)ethyl methacrylate, or isoprenol methacrylate.

[0029] The present invention further comprises: (a) 50% to 99% by weight of a (meth)acrylic acid ester monomer or a mixture of different (meth)acrylic acid ester monomers; (b) 1% to 50% by weight of a compatibilizer comprising at least one (meth)acrylate moiety and at least one additional ethylenically unsaturated moiety; (c) 0% by weight to 0.5% by weight of polymerization inhibitor The present invention relates to a reactive diluent composition comprising the reactive diluent.

[0030] The content of each of the components (a), (b), and (c) is based on the total amount of the reactive diluent composition. In certain embodiments, the percentages of (a), (b), and (c) total 100% by weight.

[0031] The (meth)acrylic acid ester monomers and the compatibilizers have the meanings specifically defined above.

[0032] The ratio of the amount of (meth)acrylic ester monomer to the amount of compatibilizer is from 1:1 to 70:1, or from 3:1 to 40:1, or from 10:1 to 25:1, preferably 20:1.

[0033] To prevent undesired polymerization, a polymerization inhibitor (stabilizer) can be used in the reactive diluent composition according to the invention. In the context of the present invention, the terms "(polymerization) inhibitor" and "stabilizer" are used synonymously. Advantageously, the polymerization inhibitor is selected from the group consisting of hydroquinone, hydroquinone ethers, such as hydroquinone monomethyl ether or di-tert-butylcatechol, phenothiazine, N,N'-(diphenyl)-p-phenylenediamine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, p-phenylenediamine, methylene blue, or sterically hindered phenols. Preferably, the polymerization inhibitor is selected from hydroquinone monomethyl ether, phenothiazine, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methyl-phenol, octadecyl-3-(3,5)-di-tert-butyl-4-hydroxyphenyl)-propionate (such as IRGANOX1076), and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and mixtures thereof.

[0034] Furthermore, the present invention relates to a curable resin composition containing at least an unsaturated polyester resin and the above-mentioned reactive diluent composition.

[0035] In a preferred embodiment, the curable resin composition comprises: (a) 30% by weight to 65% by weight of an unsaturated polyester resin, (b) 35% by weight to 70% by weight of a reactive diluent composition; (c) 0% to 20% by weight of one or more further organic or inorganic additives Contains.

[0036] The content of each of the components (a), (b), and (c) is based on the total amount of the curable resin composition. In a specific embodiment, the proportions of (a), (b), and (c) total 100% by weight.

[0037] Suitable UP resins which can be cured by the method of the present invention are the so-called ortho-resins, iso-resins, iso-NPG-resins and dicyclopentadiene (DCPD)-resins. The UP resins defined above are generally known and commercially available.

[0038] For example, ortho resins are based on phthalic anhydride, maleic anhydride, or fumaric acid and glycols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, or hydrogenated bisphenol A. Typically, those derived from 1,2-propylene glycol are used in combination with reactive diluents. Iso resins are usually prepared from isophthalic acid, maleic anhydride, or fumaric acid and glycols. These resins may typically contain higher levels of reactive diluents than ortho resins. Bisphenol A fumarate is based on ethoxylated bisphenol A and fumaric acid. Chlorend is a resin prepared from chlorine / bromine containing anhydrides or phenols in the preparation of UP resins.

[0039] The curable resin composition may further comprise organic or inorganic additives such as fillers, fibers, pigments, dispersants, inhibitors, auxiliaries, and accelerators. Examples of fibers for producing fiber-reinforced plastics are glass fibers, carbon fibers, aramid fibers, polyamide fibers, boron fibers, ceramic fibers, metal fibers, and natural fibers (e.g. jute, kenaf, industrial hemp, flax (linen), ramie, etc.), or any combination thereof. The fiber content varies depending on the type of fiber, the manufacturing process used, and the final application field. For example, in SMC formulations, for example the glass fiber content is preferably up to 35% by weight in combination with a high filler content of up to 40% by weight. The resin content in SMC applications is preferably 10% to 20% by weight. BMC formulations contain a high filler content, preferably 60% by weight, and a low fiber content, preferably 15% by weight. For hand lay-up, a fiber content of up to 60% by weight is preferred. For spray-up applications, a moderate glass fiber content of 30-35% by weight is preferred, primarily using chopped glass fibers. For filament winding and pultrusion, 30-80% by weight glass roving is used.

[0040] The curable resin composition may include at least one filler. Such fillers may be selected from the group consisting of calcium carbonate, barium sulfate, quartz, talc, calcium sulfate, calcium silicate, and / or kaolin. For flame retardancy, ATH (aluminum trihydroxide) or antimony oxide is added as a filler. Alternatively or in addition, the fiber reinforced resin may also include at least one further additive selected from the group consisting of inhibitors, retarders, thixotropic agents (such as fumed silica), and / or UV absorbers, or mixtures thereof.

[0041] The curable resin composition may further comprise as pigments iron oxide, titanium dioxide, zinc sulfide, zinc oxide, and / or organic or inorganic color pigments.

[0042] Suitable accelerators are ammonium, alkali metal or alkaline earth metal carboxylates and 1,3-diketones, such as acetylacetone or diethylacetoacetamide.

[0043] In addition to the above, the present invention provides a pre-accelerated formulation containing the reactive curable resin composition and at least one accelerator. Suitable accelerators are cobalt(II) salts or complexes, such as cobalt halides, nitrates, sulfates, sulfonates, phosphates, phosphonates, oxides, or carboxylates. Suitable carboxylates are, for example, lactates, 2-ethylhexanoates, acetates, propionates, butyrates, oxalates, laurates, oleates, linoleates, palmitates, stearates, acetylacetonates, octanoates, nonanoates, heptanoates, neodecanoates, or naphthenates. The cobalt(II) salts or complexes are preferably cobalt alkyl carboxylates, such as cobalt(II) ethylhexanoate, cobalt(II) octanoate, or cobalt acetylacetonate, or cyclopentadienyl complexes of cobalt. Cobalt(2-ethylhexanoate), cobalt(neodecanoate), or cobalt(naphthenate) are particularly preferred. Additionally, polymer-bound cobalt promoters are suitable.

[0044] Alternatively, promoters based on copper(I) or copper(II) salts or complexes are suitable. Suitable copper salts or complexes are, for example, copper halides (such as chlorides), nitrates, sulfates, or alkylcarboxylates. Suitable carboxylates are, for example, lactates, 2-ethylhexanoates, acetates, propionates, butyrates, oxalates, laurates, oleates, linoleates, palmitates, stearates, acetylacetonates, octanoates, nonanoates, heptanoates, neodecanoates, or naphthenates. The copper(I) or copper(II) salts or complexes are preferably alkylcarboxylates. Copper(II) acetonates and copper(II)-(2-ethylhexanoates) are particularly preferred.

[0045] Alternatively, promoters based on iron salts or iron complexes are also suitable. Preferably, the iron(II) coordination compound is selected from the group consisting of iron(II) species coordinated with monodentate and polydentate N-donor and / or O-donor ligands. Alternatively, the iron salt or iron complex present in promoter system (b) can be selected from the group consisting of iron halides, carboxylates, 1,3-dioxo complexes, and cyclopentadienyl-based iron complexes.

[0046] Curing is usually initiated by adding an accelerator and initiator to a curable resin composition according to the invention, or by adding an initiator to a pre-accelerated formulation.

[0047] Accordingly, the present invention provides a styrene-free method for curing an unsaturated polyester resin, comprising the steps of: (a) providing the curable resin composition or the pre-accelerated formulation; (b) optionally adding at least one organic or inorganic additive as described above; and (c) Initiating the curing process by adding an initiator. Includes.

[0048] Suitable peroxides for curing UP resins include inorganic and organic peroxides such as the traditionally used ketone peroxides, peroxyesters, diaryl peroxides, dialkyl peroxides, and peroxydicarbonates, but also peroxycarbonates, peroxyketals, hydroperoxides, diacyl peroxides, and hydrogen peroxide. Preferred peroxides are organic hydroperoxides, ketone peroxides, peroxyesters, and peroxycarbonates. Even more preferred are hydroperoxides and ketone peroxides. Preferred hydroperoxides include cumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butyl hydroperoxide, isopropyl cumyl hydroperoxide, tert-amyl hydroperoxide, 2,5-dimethylhexyl-2,5-dihydroperoxide, pinane hydroperoxide, paramenthane hydroperoxide, terpene hydroperoxide, and pinene hydroperoxide. Preferred ketone peroxides include methyl ethyl ketone peroxide, methyl isopropyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, and acetylacetone peroxide. Mixtures of two or more peroxides can also be used, such as a combination of a hydroperoxide or a ketone peroxide with a peroxyester.

[0049] A particularly preferred peroxide is methyl ethyl ketone peroxide. Those skilled in the art will understand that these peroxides can be combined with conventional additives, such as fillers, pigments, and desensitizers. Examples of desensitizers are hydrophilic esters and hydrocarbon solvents. The amount of peroxide used to cure the resin is preferably at least 0.1 per 100 resin (phr), more preferably at least 0.5 phr, and most preferably at least 1 phr. The amount of peroxide is preferably 8 phr or less, more preferably 5 phr or less, and most preferably 2 phr or less.

[0050] Advantageously, the initiator is an organic peroxide, preferably selected from the group consisting of methyl ethyl ketone peroxide (MEKP), benzoyl peroxide (BPO), cumene hydroperoxide (CuHP), or any combination thereof.

[0051] The curing process of fiber reinforced plastic products can be carried out at any temperature from -15°C to 250°C, depending on the initiator system, accelerator system, compounds to adjust the cure rate, and the resin composition to be cured. Preferably, this is carried out at ambient temperatures commonly used in applications such as hand lay-up, spray-up, filament winding, resin transfer molding, coating (e.g. gel coat and standard coating), button making, centrifugal casting, corrugated sheets or flat panels, relining systems, kitchen sinks with poured compounds, etc. However, it can also be used in sheet molding compounds (SMC), bulk molding compounds (BMC), pultrusion techniques, etc., where temperatures of up to 180°C, more preferably up to 150°C, and most preferably up to 100°C are used.

[0052] Generally, fiber reinforced plastics (FRP) have the advantages of high relative strength, good surface condition, high corrosion resistance, and high chemical resistance. Taking advantage of such advantages, they are basically used as parts for housing materials, industrial materials, tanks, containers, ships, automobiles, trains, etc.

[0053] Working Example 1 Monomer synthesis procedure 1.1 Basic synthesis procedure for monomers All reactions and product handling were carried out in common laboratory glassware at ambient conditions. Methyl (meth)acrylate, (meth)acrylic anhydride (MAAH), (meth)acryloyl chloride, 2-allyloxyethanol, 4-hydroxybutyl vinyl ether, isoprenol, eugenol, 2-((allyloxy)methyl)-2-ethylpropane-1,3-diol, 2,2-bis((allyloxy)methyl)butan-1-ol were obtained from commercial / industrial suppliers and used as received without further purification.

[0054] Eugenol methacrylate was synthesized according to literature procedures such as those described in Stanzione, JF, III, Sadler, JM, La Scala, JJ and Wool, RP (2012), Lignin Model Compounds as Bio-Based Reactive Diluents for Liquid Molding Resins. ChemSusChem, 5: 1291-1297.

[0055] Isoprenol methacrylate was synthesized according to literature procedures such as those described in Jacob M. Berlin, Katie Campbell, Tobias Ritter, Timothy W. Funk, Anatoly Chlenov, and Robert H. Grubbs, Ruthenium-Catalyzed Ring-Closing Metathesis to Form Tetrasubstituted Olefins Org. Lett. 2007 9 (7), 1339-1342.

[0056] 4-(Vinyloxy)butyl methacrylate was synthesized according to literature procedures, such as those described in Farzad Seidi, a Victor Druet, a Nguyen Huynh, a Treethip Phakkeereea and Daniel Crespy Hemiaminal ether linkages provide a selective release of payloads from polymer conjugates Chem. Commun., 2018,54, 13730-13733.

[0057] 2-(Allyloxy)ethyl methacrylate was synthesized according to literature procedures such as those described in Xiao-Guang Sun, Craig L. Reeder, and John B. Kerr Synthesis and Characterization of Network Type Single Ion Conductors Macromolecules 2004, 37, 6, 2219-2227.

[0058] 2,2-Bis((allyloxy)methyl)butyl methacrylate and 2-((allyloxy)methyl)-2-ethylpropane-1,3-diyldimethylacrylate were synthesized according to literature procedures such as those described in US Pat. No. 4,640,940.

[0059] 2 Basic Analysis Methods for Monomers NMR spectra were recorded on a Bruker Avance 300 or 400 spectrometer at 300 K unless otherwise stated, and residual solvent resonances were used as internal references ( 1 H NMR: THF-d8: 1.72 ppm, C 6 D 6 : 7.16 ppm, Toluene-d8 (tol-d8): 2.08 ppm; CDCl 3 :7.26ppm. 13 C{ 1 H}NMR: THF-d8: 25.31 ppm, C 6 D6 : 128.06 ppm, CDCl 3 Chemical shifts δ are given in ppm relative to the external standard tetramethylsilane ( 1 H, 13 C{ 1 H}). 1 H and 13 The C NMR signals are partially reflected in the 2D NMR spectrum ( 1 H, 1 H-COSY; 1 H, 13 C-HSQC; 1 H, 13 C-HMQC).

[0060] 3 Polymers and Composite Resins 3.1 Ingredients Used [Table 1-1] [Table 1-2]

[0061] 3.2 Method 3.2.1 Bulk polymerization and determination of polymerization time For bulk polymerization, stock solutions of UPR resin and various reactive diluents were prepared. Solid UPR resin was melted at 100°C for 3 hours. The reactive diluents were added to the heated resin and homogenized on a roller bed for 12-24 hours. The prepared stock solutions were mixed with various compatibilizers according to Tables 1-3. The accelerator was added and the mixture was homogenized by stirring for 2 minutes, followed by the addition of the initiator solution. The mixture was stirred again for 1.5 minutes and then transferred to standard test tubes (18 x 180 mm) and cured. The cured resin was post-cured in a drying oven at 80°C for 8 hours.

[0062] 3.2.2 Mechanical testing Tensile tests were performed according to EN ISO 527-1. Approximately 110-115 g of resin formulation was used to cast films (calculated for a wet film thickness of 4 mm). Films were cured at room temperature for 24 hours. All samples were post-cured in an oven at 80°C for 8 hours before tensile testing.

[0063] [Table 2-1] [Table 2-2] [Table 2-3]

[0064] The reference examples show that without the addition of a compatibilizer, an opaque polymer resin is formed. The opacity represents phase separation and therefore incompatibility between the reactive diluent and the UPR resin. Examples 1-6 show that with the addition of a compatibilizer, a transparent polymer is formed without exhibiting phase separation. Examples 7-12 show that mixtures of reactive diluents can also be used. Examples 11-12 also show that the performance of the compatibilizer depends on the proper selection of the reactive diluent. The performance of the compatibilizer does not depend on the cure system used, as shown by using two different peroxides and two different accelerators.

[0065] [Table 3]

[0066] The addition of the compatibilizer compounds tested demonstrated the formation of clear polymers, with the exception of the compatibilizer TMP-monoallyl ether dimethacrylate.

[0067] [Table 4]

[0068] Mechanical testing showed that styrene-free UPR formulations using benzyl methacrylate as a reactive diluent in combination with a compatibilizer provided mechanical properties comparable to standard styrene-based UPR resins.

Claims

1. A reactive diluent composition comprising a (meth)acrylic acid ester monomer and a compatibilizer, the compatibilizer comprises at least one (meth)acrylate moiety and at least one additional ethylenically unsaturated moiety and is selected from the group consisting of vinyl ether (meth)acrylates, allyl ether (meth)acrylates, and alkenyl (meth)acrylates; the (meth)acrylic acid ester monomer and the compatibilizer are different compounds; Reactive diluent compositions.

2. 2. The reactive diluent composition of claim 1, wherein the vinyl ether (meth)acrylate is selected from monovinyl ether mono(meth)acrylate, monovinyl ether di(meth)acrylate, monovinyl ether tri(meth)acrylate, monovinyl ether tetra(meth)acrylate, divinyl ether mono(meth)acrylate, divinyl ether di(meth)acrylate, divinyl ether tri(meth)acrylate, trivinyl ether mono(meth)acrylate, and trivinyl ether di(meth)acrylate.

3. 3. The reactive diluent composition according to claim 1 or 2, wherein the allyl ether (meth)acrylate is selected from monoallyl ether mono(meth)acrylate, monoallyl ether di(meth)acrylate, monoallyl ether tri(meth)acrylate, monoallyl ether tetra(meth)acrylate, diallyl ether mono(meth)acrylate, diallyl ether di(meth)acrylate, diallyl ether tri(meth)acrylate, triallyl ether mono(meth)acrylate, and triallyl ether di(meth)acrylate.

4. 3. The reactive diluent composition of claim 1 or 2, wherein the alkenyl (meth)acrylate is selected from mono(meth)acrylates, di(meth)acrylates, tri(meth)acrylates, and tetra(meth)acrylates that contain one or more ethylenically unsaturated alkenyl (C=C) moieties different from the (meth)acrylate.

5. 3. The reactive diluent composition of claim 1 or 2, wherein the compatibilizer is selected from the group consisting of 4-(vinyloxy)butyl methacrylate, 2-(allyloxy)ethyl methacrylate, isoprenol methacrylate, 2,2-bis((allyloxy)methyl)butyl methacrylate, 2-((allyloxy)methyl)-2-ethylpropane-1,3-diylbis(2-methylacrylate), and eugenol methacrylate.

6. The reactive diluent composition of claim 1 or 2, wherein the compatibilizer is 4-(vinyloxy)butyl methacrylate, 2-(allyloxy)ethyl methacrylate, and isoprenol methacrylate.

7. The (meth)acrylic acid ester monomer is a linear or branched alkyl C １ ~C ２０ 3. The reactive diluent composition according to claim 1, wherein the diluent is selected from alkyl (meth)acrylates, (alkyl)aryl (meth)acrylates, hydroxyalkyl (meth)acrylates, (poly)ether methacrylates, and dimethacrylates, trimethacrylates, and tetramethacrylates.

8. 3. The reactive diluent composition of claim 1 or 2, wherein the (meth)acrylic acid ester monomer is selected from methyl methacrylate, glycerol formal methacrylate, isopropylidene glycerol methacrylate, benzyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, polyethylene glycol 200 dimethacrylate, ethylene glycol dimethacrylate, butyl diglycol methacrylate, and ethyl triglycol methacrylate.

9. 3. The reactive diluent composition of claim 1, wherein the (meth)acrylic acid ester monomer is benzyl methacrylate and the compatibilizer is 4-(vinyloxy)butyl methacrylate, 2-(allyloxy)ethyl methacrylate, or isoprenol methacrylate.

10. The reactive diluent composition of claim 1 or 2, wherein the ratio of the amount of said (meth)acrylic ester monomer to the amount of said compatibilizer is from 1:1 to 70:

1.

11. The reactive diluent composition of claim 1 or 2, wherein the ratio of the amount of said (meth)acrylic ester monomer to the amount of said compatibilizer is from 10:1 to 25:

1.

12. 3. The reactive diluent composition according to claim 1 or 2, further comprising a polymerization inhibitor.

13. 13. The reactive diluent composition of claim 12, wherein the polymerization inhibitor is selected from the group consisting of hydroquinone, hydroquinone ether, phenothiazine, N,N'-(diphenyl)-p-phenylenediamine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, p-phenylenediamine, methylene blue, or a sterically hindered phenol.

14. (a) 50% to 99% by weight of the (meth)acrylic acid ester monomer; (b) 1% to 50% by weight of the reactive diluent composition; (c) 0% to 0.5% by weight of inhibitor The reactive diluent composition according to claim 1 or 2, comprising:

15. A curable resin composition comprising at least an unsaturated polyester resin and the reactive diluent composition according to claim 1 or 2.

16. 16. The curable resin composition of claim 15, further comprising at least one organic or inorganic additive.

17. 16. A pre-accelerated formulation comprising the curable resin composition of claim 15 and at least one accelerator.

18. 1. A method for curing an unsaturated polyester resin, comprising the steps of: (a) providing a curable resin composition according to claim 15; and (b) Initiating the curing process by adding an initiator. A method comprising: