Composite resin containing unsaturated phosphate compounds

Abstract

The present invention relates to a reactive diluent system for composite resins comprising: (a) a reactive diluent composition comprising or consisting of an organophosphorus compound; and (b) an accelerator system comprising: (i) at least one iron salt or complex, (ii) at least one transition metal salt or complex selected from cobalt and copper, and (iii) optionally at least one solvent.

Description

[Technical Field]

[0001] The present invention relates to a reactive diluent system for composite resins, comprising (a) a reactive diluent composition containing an organic (meth)acrylate-based phosphorus compound, and (b) an accelerator system.

[0002] prior art Unsaturated (meth)acrylate-based phosphate esters, such as 2-hydroxyethyl methacrylate phosphate, are well-known adhesion promoters in applications such as adhesives and coating resins, improving adhesion to polar substrates. Furthermore, the incorporation of (meth)acrylate-based phosphate esters can improve corrosion protection of emulsion-based coating formulations due to improved adhesion. In addition, phosphorus compounds are well-known for improving flame retardancy. Incorporation of unsaturated (meth)acrylate-based phosphate esters into polymer resins creates flame-retardant materials. Flame retardancy is particularly important in composite material applications such as transportation and construction. In these application areas, vinyl ester resins and unsaturated polyester resins are the main types of resins used. These resins typically contain styrene as a reactive diluent. Other reactive diluents or solvents, such as vinyltoluene and (meth)acrylate esters, are also used. Unsaturated (meth)acrylate-based phosphate esters offer an option for use as a reactive diluent to impart flame retardancy. This is particularly important in application areas where a combination of flame retardancy and light transmittance is required. Furthermore, unsaturated (meth)acrylate-based phosphate esters improve glass-fiber adhesion in fiber-reinforced plastics.

[0003] For curing composite resins, redox systems containing an oxidizing agent (e.g., a peroxide) and soluble cobalt ions as an accelerator are commonly used. The accelerator increases the activity of the oxidizing agent at low temperatures, such as room temperature (RT), thereby increasing the curing rate. Cobalt ions can exist in the form of cobalt salts and / or cobalt complexes.

[0004] However, composite resins combined with unsaturated phosphate esters do not cure sufficiently with standard cobalt-based RT curing systems. The phosphate esters reduce the stability of the cobalt complex, thus reducing the activity of the accelerator. Furthermore, cobalt-accelerated methyl ethyl ketone peroxide (MEKP) systems are well known to have a poor ability to effectively form radicals with acrylic monomers in the absence of styrene. The most common initiator / accelerator system currently in practical use in acrylic resin systems is benzoyl peroxide (BPO) with a tertiary amine accelerator. However, the use of amines is not ideal due to the possibility of salt formation with unsaturated phosphate esters and the known problem of discoloration of the final composite material when exposed to light or heat.

[0005] Therefore, the object of the present invention was to provide an accelerator system suitable for such phosphate-reactive diluents. In other words, the problem that the present invention aims to solve is to provide a reactive diluent system and an optimized accelerator system comprising an organic (meth)acrylate-based phosphorus compound as a reactive diluent.

[0006] Summary of the Invention This problem has been successfully solved by the present invention. Specifically, the inventors have unexpectedly found that a resin composition containing a reactive diluent system based on an organic (meth)acrylate-based phosphorus compound can be efficiently cured together with a curable resin composition under mild conditions (i.e., by RT curing) using an accelerator system containing at least one iron salt or complex combined with at least one cobalt or copper salt or complex.

[0007] As a general and simple explanation, the main aspects of the present invention can be described as follows.

[0008] In a first aspect, the present invention relates to a reactive diluent system for a composite resin comprising (a) a reactive diluent composition and (b) an accelerator system, Reactive diluent composition (a) is general formula (I)

Chemical

Chemical

[0009] In a second aspect, the present invention relates to a curable resin composition comprising a curable resin and the above-described reactive diluent system; in a third aspect, the invention relates to use of the reactive diluent system or the curable resin composition for preparing a composite resin having flame retardancy, or for preparing a composite resin having improved glass fiber adhesion.

[0010] In a fourth aspect, the present invention provides a method for preparing a cured composite resin composition, comprising: (a) providing the above-described curable resin composition, (b) optionally adding at least one organic or inorganic additive, (c) Initiating the curing process by adding an initiator. This provides a method that includes [something].

[0011] In a fifth aspect, the present invention relates to a fiber-reinforced material, (a) A polymer resin selected from the group consisting of (meth)acrylate resin, unsaturated polyester resin (UPR), or vinyl ester resin (VER), (b) at least one type of reinforcing fiber material and Includes, This can be obtained by curing components (a) and (b) in the presence of an initiator using the reactive diluent system described above. Regarding fiber-reinforced materials.

[0012] Detailed description of the invention Elements of the present invention are described below. While these elements are listed together with specific embodiments, it should be understood that they can be combined in any form and in any number to form additional embodiments. The various examples and preferred embodiments described should not be construed as limiting the invention to only the explicitly described embodiments. This description should be understood to support and encompass embodiments that combine two or more explicitly described embodiments, or embodiments that combine one or more explicitly described embodiments with any number of disclosed and / or preferred elements. Furthermore, any permutations and combinations of all elements described in this application should be considered disclosed by the description of this application unless the context specifically indicates otherwise.

[0013] As used herein, terms such as "[of this] invention," "according to the present invention," and "according to the present invention" are intended to refer to all aspects and embodiments of the invention described and / or claimed herein.

[0014] As used herein, the term “including” should be interpreted as encompassing both “including” and “consisting of,” and both meanings are specifically intended in the individually disclosed embodiments according to the Invention. As used herein, “and / or” should be considered a specific disclosure in which each of two designated features or components is accompanied by or without the other. For example, “A and / or B” should be considered as the respective specific disclosures of (i) A, (ii) B, and (iii) A and B, as each of which is described separately herein.

[0015] It should be understood that applying the teachings of the present invention to specific problems or environments, and including variations of the invention or additional features therein (such as further aspects and embodiments), is within the scope of the ability of a person of ordinary skill in the art, based on the teachings contained herein.

[0016] Unless otherwise indicated by the context, the above descriptions and definitions of features are not limited to any particular aspect or embodiment of the present invention, but apply equally to all aspects and embodiments described herein.

[0017] In the context of this invention, the term "(meth)acrylate" refers to an ester of methacrylic acid or acrylic acid.

[0018] As used herein, the terms “reactive diluent” or “reactive solvent” refer to solvents that react during the curing process. They are typically composed of ethylenically unsaturated monomer compounds. In the context of the present invention, “reactive diluent composition” is a composition comprising at least one reactive diluent or consisting of reactive diluents. “Reactive diluent system” includes a reactive diluent composition and an accelerator system.

[0019] A coordination compound is a substance consisting of one or more metal atoms or ions surrounded by an array of bonding molecules or ions known as ligands or complexing agents. Coordination compounds centered around a metal atom / ion are called metal complexes. Coordination compounds may be ionic and exist as cationic or anionic species in combination with various corresponding counterions.

[0020] All references, patents, and publications cited herein are incorporated herein by reference in their entirety.

[0021] The present invention is based on the remarkable discovery that a resin composition comprising a curable resin and a reactive diluent system based on an organic (meth)acrylate-based phosphorus compound can be efficiently cured under mild conditions (i.e., by RT curing) using an accelerator system comprising at least one iron salt or complex combined with at least one salt or complex selected from cobalt and copper.

[0022] Reactive diluent system Reactive diluent composition (a) Reactive diluent composition (a) is general formula (I) [ka] [In the formula, R 1 =H, Me, R n , R m =O - OH, Z, X 2 -P(=X 3 )R n+1 R m+1 And, n and m = 2 to 15. X 1 , X 2 =O, CH2, S, NH X 3 =O, S, [ka] And, L is a hydrocarbon linking group that optionally contains one or more heteroatoms. It contains or consists of the organophosphorus compound.

[0023] Therefore, the linking group site links a phosphorus unit with an ethylenically unsaturated polymerizable monomer unit. As used in the context of the present invention, the term "hydrocarbon linking group" includes linear and / or branched aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl), and aromatic groups, aromatic substituents substituted with aliphatic or alicyclic groups, as well as cyclic substituents in which the ring is completed via another part of the molecule (e.g., two substituents that together form a single ring).

[0024] The term "hydrocarbon linking group" includes linking groups having substituted hydrocarbon substituents, i.e., substituents that include non-hydrocarbon groups that do not alter the properties of the main hydrocarbon of the linking group (e.g., chloro, fluoro, bromo, iodo, hydroxy, alkoxy, mercapto, alkylmercapto, alkylhydroxy, nitro, amino, nitroso, sulfoxy).

[0025] The term "hydrocarbon linking group" includes heterosubstituted groups, which have the characteristics of a major hydrocarbon but contain substituents other than carbon in a ring or chain composed of carbon atoms. It also includes linking groups that are ethylene oxide (EO) and propylene oxide (PO). Examples of heteroatoms include sulfur, oxygen, and nitrogen, and encompass substituents such as pyridyl, furyl, imidazolyl, and other heterocyclic groups.

[0026] Hydrocarbon linking groups are C0-C groups having oxygen and / or nitrogen and / or sulfur atoms substituted for carbon atoms. 70 It may be a hydrocarbon linking group.

[0027] A linking group is, for example, X 1 (CH2CH2O) x -P(X in this case) 2It is acceptable that (=O, x=1 to 20)

[0028] In one embodiment of the present invention, the organophosphorus compound of formula (I) is optionally used in the presence of H3PO4, H4P2O7, their salts, as well as acyclic / cyclic (poly)phosphates and their salts, and methyl (meth)acrylates. [ka] [In the formula, R 1 =H, Me, R n , R m =O - OH, Z, OP(=O)R n+1 R m+1 And, n and m = 2 to 15. X = 1, 2, 3..., 50, [ka] And, x' = x, 1, 2, 3..., 50. That is the case.

[0029] The polyphosphate site may contain a monophosphate, diphosphate, triphosphate, or more phosphates, or a monophosphonate and / or diphosphonate.

[0030] Reactive diluent compositions may contain solvents such as reactive solvents.

[0031] The organophosphorus compound of formula (I) present in the reactive diluent composition is preferably a 2-hydroxyalkyl (meth)acrylate phosphate, such as 2-hydroxyethyl methacrylate phosphate.

[0032] The reactive diluent composition may further contain an organic solvent, such as an aliphatic hydrocarbon solvent or an aromatic hydrocarbon solvent, preferably a (meth)acrylate solvent.

[0033] Preferably, the reactive diluent composition contains 70% by weight of a phosphate component and 30% by weight of a reactive solvent.

[0034] In certain embodiments of the present invention, the reactive diluent composition is a solution of 2-hydroxyethyl methacrylate phosphate in methyl methacrylate (MMA). Preferably, the reactive diluent composition is a solution comprising 70% by weight of 2-hydroxyethyl methacrylate phosphate in 30% by weight of MMA.

[0035] In many cases, commercially available precursor molecules are mixtures such as Sipomer PAM-4000, PAM-100, or PAM-200 (from Solvay) or VISIOMER® HEMA-P70M / 100 (from Evonik). Such mixtures are assumed herein to be as well as pure precursor monomer units. HEMA (poly)phosphate (e.g., Solvay's PAM-4000) can be prepared directly from HEMA and P2O5 or (poly)phosphate. Alternatively, other monomers such as hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate can be used instead of HEMA. Other examples include polyethylene glycol (meth)acrylate (poly)phosphate ester (Solvay's PAM-100) and polypropylene glycol (meth)acrylate (poly)phosphate ester (Solvay's PAM-200).

[0036] Accelerator system (b) At least one iron salt or complex (i) present in the accelerator system (b) may be an iron(II) salt or complex, an iron(III) salt or complex, or a mixture of iron(II) and iron(III) salts and complexes.

[0037] Advantageously, the iron salt or complex present in the accelerator system (b) is an iron(II) coordination compound. Preferably, the iron(II) coordination compound is selected from the group consisting of iron(II) species coordinated with monodentate and polydentate N and / or O donor ligands. Alternatively, the iron salt or complex present in the accelerator system (b) may be selected from the group consisting of iron halides, carboxylates, 1,3-dioxo complexes, and cyclopentadienyl iron complexes.

[0038] Suitable examples of iron carboxylates are iron lactate, iron naphthenate, iron 2-ethylhexanoate (i.e., iron octanoate), iron formate, iron acetate, iron propionate, iron butyrate, iron valerate, iron hexanoate, iron heptanoate, iron octanoate, iron nonanoate, iron decanoate, iron neodecanoate, and iron dodecanoate. Examples of iron 1,3-dioxo complexes are iron acetylacetonate, as well as acetylacetone, benzoylacetone, dibenzoylmethane, and iron complexes of acetylacetonate, such as diethylacetateacetamide, dimethylacetateamide, dipropylacetateamide, dibutylacetateamide, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, and butyl acetoacetate. An example of an iron cyclopentadienyl complex is a complex comprising iron and two substituted or unsubstituted cyclopentadienyl ligands, wherein the optional substituents on the cyclopentadienyl ring are selected from the group consisting of alkyl, aryl, and alkenyl groups having 1 to 12 carbon atoms, and these may be optionally substituted with heteroatoms selected from O, N, S, Si, and P. An example of an iron cyclopentadienyl complex is ferrocene.

[0039] In one embodiment of the present invention, at least one iron salt or complex (i) present in the accelerator system (b) is the following formula (II) [ka] Iron(1+), chloro[dimethyl-9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl-κN)-7-[(2-pyridinyl-κN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate-κN], which has iron in oxidation state +II. 3 κN 7 ] - It is chloride (1-) (CAS: 478945-46-9).

[0040] Such Fe complexes are commercially available, for example, as Nouryact CF40 (Nouryon) or Borchi Oxy-Coat 1410 (Borchers GmbH). These are typically supplied as solutions in a solvent such as 1,2-propanediol or in a reactive diluent such as hydroxyethyl methacrylate.

[0041] The (ii) salt or complex of at least one transition metal present in the accelerator system (b) may be a salt or complex of cobalt, a salt or complex of copper, or a mixture of at least one salt or complex of cobalt and at least one salt or complex of copper.

[0042] Advantageously, the salt or complex (ii) of at least one transition metal selected from cobalt and copper present in the accelerator system (b) is a salt or complex of cobalt(II). Suitable cobalt salts or complexes are, for example, cobalt halides, nitrates, sulfates, sulfonates, phosphates, phosphonates, oxides, or carboxylates. Suitable carboxylates are, for example, lactates, 2-ethylhexanoates, acetates, propions, butyrates, oxalates, laurates, oleates, linoleates, palmitates, stearates, acetylacetones, octanoates, nonanoates, heptanoates, neodecanoates, or naphthenates. The cobalt(II) salt or complex is preferably an alkyl cobalt carboxylate, such as cobalt(II) ethylhexanoate, cobalt(II) octanoate, acetylacetone cobalt, or a cyclopentadienyl complex of cobalt. Cobalt 2-ethylhexanoate, cobalt neodecanoate, or cobalt naphthenate are particularly preferred.

[0043] Alternatively, the salt or complex (ii) of at least one transition metal selected from cobalt and copper present in the accelerator system (b) is a salt or complex of copper(I) or copper(II). 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, propions, butyrates, oxalates, laurates, oleates, linoleates, palmitates, stearates, acetylacetones, octanoates, nonanoates, heptanoates, neodecanoates, or naphthenates. The salt or complex of copper(I) or copper(II) is preferably an alkylcarboxylate. Copper 2-ethylhexanoate is particularly preferred.

[0044] The ratio of at least one iron salt or complex (i) to the transition metal salt or complex (ii) may be in the range of 2:1 to 500:1, preferably 10:1 to 300:1. A ratio of at least one iron salt or complex (i) to the transition metal salt or complex (ii) of 10:1 to 200:1 is particularly preferred.

[0045] The ratio of the organophosphorus compound in the reactive diluent composition (a) to the metal content in the accelerator system (b) may be in the range of 80:1 to 4000:1.

[0046] The accelerator composition may contain at least one solvent. The solvents for the cobalt (or copper) compound and the iron compound may be the same or different, and may be, for example, a hydroxyl-functionalized solvent.

[0047] The term "hydroxy-functional solvent" is defined by formula (III) HO-(CH2-C(R 1 )2-(CH2) m -O-) n -R 2 (III) [In the formula, each R 1 R is independently selected from the group consisting of hydrogen, alkyl groups having 1 to 10 carbon atoms, and hydroxyalkyl groups having 1 to 10 carbon atoms, where n=1 to 10, m=0 or 1, and R 2 [It is either hydrogen or an alkyl group having 1 to 10 carbon atoms.] The compound is included. Most preferably, each R 1 The compound is independently selected from H, CH3, and CH2OH. Examples of suitable hydroxy-functional solvents include glycols such as diethylene monobutyl ether, ethylene glycol, diethylene glycol, dipropylene glycol, and polyethylene glycol, as well as glycerols and pentaerythritol.

[0048] Furthermore, the accelerator solution according to the present invention may further contain additional organic compounds such as aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and solvents having aldehyde groups, ketone groups, ether groups, ester groups, alcohol groups, phosphate groups, or carboxylic acid groups. Examples of suitable solvents include aliphatic hydrocarbon solvents such as white spirits and odorless mineral spirits (OMS), aromatic hydrocarbon solvents such as naphthenes and mixtures of naphthenes and paraffins, isobutanol; pentanol; 1,2-dioxime, N-methylpyrrolidinone, N-ethylpyrrolidinone; dimethylformamide (DMF); dimethyl sulfoxide (DMSO); 2,2,4-trimethylpentanediol diisobutyrate (TxlB); esters, such as dibutyl maleate, dibutyl succinate, ethyl acetate, butyl acetate, monoesters and diesters of ketoglutaric acid, pyruvate esters, and esters of ascorbic acid such as ascorbyl palmitate; aldehydes; mono- and diesters, more specifically diethyl malonate and diethyl succinate; 1,2-diketones, especially diacetyl and glyoxal; benzyl alcohol, aliphatic alcohols, and reactive diluents, such as styrene, styrene derivatives, or (meth)acrylates.

[0049] The total amount of solvent preferably present in the accelerator solution is 1 to 50% by weight, preferably 5 to 30% by weight.

[0050] When the accelerator composition is an accelerator solution, cobalt or copper may be present in an amount of at least 0.5 mmol, preferably at least 2 mmol, per 1 kg of reactive diluent-containing resin. Cobalt or copper is preferably present in the accelerator solution in an amount of less than 200 mmol / kg of resin, preferably less than 50 mmol / kg of resin, and more preferably less than 25 mmol / kg of resin.

[0051] When the accelerator composition is an accelerator solution, iron may be present in an amount of at least 0.0001 mmol / kg resin, more preferably at least 0.01 mmol / kg resin. Iron is preferably present in the accelerator solution in an amount of less than 20 mmol / kg resin, more preferably less than 10 mmol / kg resin, and most preferably less than 1 mmol / kg resin.

[0052] The total amount of transition metal used in the method and composition according to the present invention is preferably 0.5 to 100 mmol / kg, more preferably 1 to 50 mmol / kg, and most preferably 1 to 10 mmol / kg of reactive diluent-containing resin.

[0053] The accelerator composition may optionally include one or more accelerators, a base, water, an inhibitor, an additive, and / or a filler.

[0054] There are three important classifications of accelerators: ammonium, alkali metal, or alkaline earth metal carboxylates, phosphorus-containing compounds, and 1,3-diketones. Examples of 1,3-diketones include acetylacetone, benzoylacetone, and dibenzoylmethane, as well as acetoacetate esters, such as diethylacetacetamide, dimethylacetacetamide, dipropylacetacetamide, dibutylacetacetamide, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, and butyl acetoacetate.

[0055] Suitable examples of metal carboxylate salts of ammonium, alkali metals, and alkaline earth metals are 2-ethylhexanoates (i.e., octanoates), nonanoates, heptanoates, neodecanoates, and naphthenates. A preferred alkali metal is potassium (K). The salts can be added directly to the accelerator composition or resin, or they can be formed in situ. For example, after adding alkali metal hydroxides and 2-ethylhexanoic acid to a solution, alkali metal 2-ethylhexanoate salts can be prepared in situ in the accelerator composition.

[0056] Suitable phosphorus compounds are those having the formulas P(R)3 and P(R)3=O, where each R is independently selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. Preferably, at least two R groups are selected from either alkyl or alkoxy groups. Specific examples of suitable phosphorus-containing compounds are diethyl phosphate, dibutyl phosphate, tributyl phosphate, triethyl phosphate (TEP), dibutyl phosphate, and triethyl phosphate.

[0057] Acetoacetate esters are particularly preferred accelerators. Diethylacetacetamide is particularly preferred. A combination of diethylacetacetamide and potassium 2-ethylhexanoate is even more preferred.

[0058] If one or more accelerators are present in the accelerator composition, their amounts are preferably at least 0.01% by weight, more preferably at least 0.1% by weight, even more preferably at least 1% by weight, more preferably at least 10% by weight, most preferably at least 20% by weight, preferably 90% by weight or less, more preferably 80% by weight or less, and most preferably 70% by weight or less, based on the total weight of the accelerator composition.

[0059] Suitable nitrogen-containing bases present in the accelerator composition and the pre-accelerated resin include primary, secondary, and tertiary amines, such as triethylamine, dimethylaniline, diethylaniline, or N,N-dimethyl-p-toluidine (DMPT); polyamines, such as 1,2-(dimethylamine)ethane; secondary amines, such as diethylamine; ethoxylated amines, such as triethanolamine, dimethylaminoethanol, diethanolamine, or monoethanolamine; and aromatic amines, such as pyridine or bipyridine. The nitrogen-containing base is preferably present in the accelerator composition in an amount of 5 to 50% by weight.

[0060] To prevent undesirable polymerization, a polymerization inhibitor (stabilizer) can be used in the accelerator composition according to the present 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 ether, e.g., 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 phenol, and the amount of stabilizer is 0 to 1000 ppm. Preferably, the amount of stabilizer is 5 to 500 ppm, and most preferably 20 to 300 ppm. Preferably, the polymerization inhibitor is selected from hydroquinone monomethyl ether, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate (such as IRGANOX1076), and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, as well as mixtures thereof.

[0061] In a particularly preferred embodiment of the present invention, the reactive diluent composition (a) comprises or consists of 2-hydroxyethyl methacrylate phosphate, and the accelerator system (b) comprises iron(1+), chloro[dimethyl-9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl-κN)-7-[(2-pyridinyl-κN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate-κN 3 κN 7 ] - It contains chloride (1-) (CAS: 478945-46-9) and 2-ethylhexanoate Co(II).

[0062] In another embodiment, the reactive diluent composition (a) contains or consists of 2-hydroxyethyl methacrylate phosphate, and the accelerator system (b) is iron(1+), chloro[dimethyl-9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl-κN)-7-[(2-pyridinyl-κN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate-κN 3 κN 7 ] - It contains chloride (1-) (CAS: 478945-46-9) and 2-ethylhexanoate Cu(II).

[0063] The reactive diluent system according to the present invention is particularly suitable for preparing flame-retardant composite resins and / or composite resins with improved glass fiber adhesion.

[0064] Curable resin composition The present invention further relates to a curable resin composition comprising a curable resin and a reactive diluent system in the various embodiments described above.

[0065] In a particularly preferred embodiment of the present invention, the organophosphorus compound of general formula (I) is 2-hydroxyethyl methacrylate phosphate.

[0066] Suitable resins cured using the reactive diluent system according to the present invention include alkyd resins, unsaturated polyester (UP) resins, vinyl ester (VE) resins, (meth)acrylate resins, polyurethanes, epoxy resins, and mixtures thereof.

[0067] Preferred resins are (meth)acrylate resins, UP resins, and vinyl ester resins. In relation to this application, the terms “unsaturated polyester resin” and “UP resin” refer to a combination of an unsaturated polyester resin and an ethylenically unsaturated monomer compound. The term “(meth)acrylate resin” refers to a combination of an acrylate resin or methacrylate resin and an ethylenically unsaturated monomer compound. The UP resins and acrylate resins defined above are generally known and commercially available.

[0068] Curing is typically initiated by adding the accelerator solution and initiator (peroxide) according to the present invention to the resin, or by adding the initiator (peroxide) to a pre-accelerated resin.

[0069] Suitable UP resins cured by the method of the present invention are so-called ortho resins, iso resins, isoNPG resins, and dicyclopentadiene (DCPD) resins. Examples of such resins are phthalate-type, isophthalate-type, maleate-type, fumarate-type, allyl-type, vinyl-type, and epoxy-type resins, bisphenol A resins, terephthalate resins, and hybrid resins.

[0070] Vinyl ester resins have unsaturated moieties only at the terminal positions, introduced by the reaction of epoxy resin with (meth)acrylic acid or hydroxyethyl (meth)acrylic acid. Typical examples of epoxy resins include bisphenol-A, novolac, tetraphenylethane, alicyclic compounds, and tetrabromobisphenol-A. Therefore, vinyl ester resins are (meth)acrylate-functional resins. An additional classification of vinyl ester resins is vinyl ester urethane resin, also called urethane methacrylate resin.

[0071] The acrylic resin contained in the resin composition can be selected from thermosetting acrylic resins or acrylic-modified resins well known in the art. Examples of acrylic resins include acrylates, methacrylates, diacrylates, and dimethacrylates, as well as their oligomers. Oligomer acrylates may be acrylicated urethanes, epoxy, polyesters, polyethers, and acrylics. Furthermore, the acrylic resin can be a pre-reacted polymer-in-monomer syrup produced by polymerizing acrylic monomers or copolymerizing a mixture of different acrylic monomers to a specific degree of polymerization. Acrylic-modified resins are a broad category of resins similar to oligomer acrylates, except that the acrylic-modified resin uses a base resin with a molecular weight sufficient so that it is not considered an oligomer. Methods for preparing acrylic-modified resins are well known to those skilled in the art. As a result, acrylic-modified resins may contain a solvent. The solvent may be inert to the resin system or may react with the resin system during the curing process. Reactive solvents or so-called reactive diluents are particularly preferred. They typically consist of ethylenically unsaturated monomer compounds. Examples of ethylenically unsaturated monomer compounds include styrene and styrene derivatives such as α-methylstyrene, vinyltoluene, indene, divinylbenzene, vinylpyrrolidone, vinylsiloxane, vinylcaprolactam, and stilbene, as well as diallyl phthalate, dibenzylideneacetone, allylbenzene, methyl methacrylate, methyl acrylate, (meth)acrylic acid, diacrylate, dimethacrylate, acrylamide; vinyl acetate, triallyl cyanurate, triallyl isocyanurate, allyl compounds used in optical applications (such as (di)ethylene glycol diallyl carbonate), chlorostyrene, tert-butylstyrene, tert-butyl acrylate, butanediol dimethacrylate, and mixtures thereof.

[0072] Suitable examples of reactive diluents that are (meth)acrylates include PEG200 di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 2,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate and its isomers, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, neopentyl glycol These include di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, PPG250 di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycidyl(meth)acrylate, (bis)maleimide, (bis)citraconimide, (bis)itaconimide, and mixtures thereof.

[0073] The amount of ethylenically unsaturated monomer in the pre-treated resin is preferably at least 0.1% by weight, more preferably at least 1% by weight, and most preferably at least 5% by weight, based on the weight of the resin. The amount of ethylenically unsaturated monomer is preferably 50% by weight or less, more preferably 40% by weight or less, and most preferably 35% by weight or less.

[0074] Furthermore, the present invention provides a two-component composition comprising (a) the above-described curable resin composition as a first component, and (b) an initiator, such as a peroxide, as a second component.

[0075] Peroxides suitable for curing resins and for presence in the second component of a two-component composition include not only conventionally used inorganic and organic peroxides such as 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, isopropylcumyl hydroperoxide, tert-amyl hydroperoxide, 2,5-dimethylhexyl-2,5-dihydroperoxide, pinan hydroperoxide, paramentane 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, such as combinations of hydroperoxides or ketone peroxides with peroxyesters, can also be used.

[0076] Particularly preferred peroxides are methyl ethyl ketone peroxides. 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 phr (per hundred resin), more preferably at least 0.5 phr, and most preferably at least 1 phr per 100 parts of resin. The amount of peroxide is preferably 8 phr or less, more preferably 5 phr or less, and most preferably 2 phr or less.

[0077] The reactive diluent systems and / or curable resin compositions described above in various embodiments can be used to prepare flame-retardant composite resins and / or composite resins with improved glass fiber adhesion.

[0078] Method for preparing a cured composite resin composition In an additional aspect, the present invention relates to a method for preparing a cured composite resin composition, (a) Prepare the curable resin composition described above. (b) optionally adding at least one organic or inorganic additive, (c) Initiating the curing process by adding an initiator. This includes methods.

[0079] The curing process can be carried out at any temperature from -15°C to a maximum of 250°C, depending on the initiator system, accelerator system, curing rate adjusting compound, and the resin composition to be cured. Preferably, it 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 manufacturing, centrifugal casting, corrugated or flat panels, relining systems, and kitchen sinks by injection compounding. However, this can also be used in sheet molding compounds (SMC), bulk molding compounds (BMC), pultrusion techniques, etc., in which case temperatures up to 180°C, more preferably up to 150°C, and most preferably up to 100°C are used.

[0080] Other optional additives such as fillers, fibers, pigments, dispersants, inhibitors, auxiliaries, and accelerators can be used in the curing process. Examples of fibers include glass fibers, carbon fibers, aramid fibers, polyamide fibers, boron fibers, ceramic fibers, metal fibers, carbon 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 area. For example, in SMC formulations, the glass fiber content is preferably up to 35% by weight, combined 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 preferably contain a high filler content of 60% by weight and a low fiber content of preferably 15% by weight. In hand lay-up applications, a fiber content of up to 60% by weight is preferred. In spray-up applications, a moderate glass fiber content of 30-35% by weight is preferred, mainly using chopped glass fibers. For filament winding and drawing, 30–80% by weight of glass roving is used.

[0081] The initiator may be as defined above. 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.

[0082] Cured fiber-reinforced composite resin composition Generally, fiber-reinforced plastics (FRP) have advantages such as high relative strength, good surface finish, high corrosion resistance, and high chemical resistance. Due to these advantages, they are primarily used as components in building materials, industrial materials, tanks, containers, ships, automobiles, and trains. Fiber-reinforced plastics consist of a synthetic resin as a binder and reinforcing fibers added to it, which are then cured. Insufficient adhesion between the reinforcing fibers and the resin often results in insufficient mechanical strength, including rigidity and flexibility.

[0083] Based on the above findings, the present invention relates to a fiber-reinforced material, (a) A polymer resin selected from the group consisting of (meth)acrylate resin, unsaturated polyester resin (UPR), or vinyl ester resin (VER), (b) at least one reinforcing fiber material, preferably glass fiber and Includes, This can be obtained by curing components (a) and (b) in the presence of an initiator using the reactive diluent system according to the present invention. We also provide fiber-reinforced materials.

[0084] The initiator and curing conditions may also be as described above.

[0085] The reinforcing fibers used in the fiber-reinforced material may be as defined above. In the fiber-reinforced material according to the present invention, any ordinary fiber that can be used for reinforcing a resin can be used. Specifically, these include, for example, glass fibers, carbon fibers, aramid fibers, polyamide fibers, boron fibers, ceramic fibers (e.g., silicon carbide fibers, alumina fibers), metal fibers, or natural fibers. These reinforcing fibers can have any form, such as yarn, roving, strand, chopped strand, yarn cloth, roving cloth, etc.

[0086] The fiber-reinforced resin composition may further contain at least one filler. Such fillers may be selected from the group consisting of ATH (aluminum trihydrate) or antimony oxide, calcium carbonate, and / or kaolin for flame retardancy. Alternatively, or in addition thereto, the fiber-reinforced resin may also contain at least one additional additive selected from the group consisting of inhibitors, retarders, thixotropes (such as fumed silica), and / or UV absorbers, or mixtures thereof.

[0087] The present invention will be described below by non-limiting examples and exemplary embodiments.

[0088] Examples [Table 1]

[0089] method Determination of bulk polymerization and polymerization time For bulk polymerization, UPR was mixed with reactive diluents and / or phosphate compounds according to Tables 2 and 3. The accelerator or accelerator mixture was added and the mixture was homogenized by stirring for 1 minute, followed by the addition of the initiator solution. The mixture was stirred again for 1 minute, then transferred to a standard test tube (18 × 180 mm) and the polymerization time was monitored. A temperature sensor was used to record the reaction temperature profile. This temperature sensor was located in a second, smaller tube filled with tetraethylene glycol as the transfer fluid, and was fixed in the center of the test tube so as to be sufficiently immersed in the sample liquid to allow for accurate measurement of the sample temperature. The start of the measurement was considered to be the time it took to mix the redox components. The maximum reaction temperature T max The position corresponds to the polymerization time.

[0090] DSC measurement (determination of glass transition temperature) Before determining the glass temperature, all samples were post-cured at 80°C for 8 hours. Differential scanning calorimetry (DSC), a commonly used analytical method, was used to determine the glass transition temperature (Reference: Ehrenstein, Gottfried W. Riedel, Gabriela, Trawiel, Pia (2004); Thermal Analysis of Plastics - Theory and Practice, Hanser Publishers). Specimens prepared by bulk polymerization were analyzed in an aluminum crucible with a perforated lid under nitrogen at a heating rate of 10 K / min over a temperature range of -50°C to 150°C (after rapid cooling) (Mettler Toledo DSC instrument with liquid nitrogen cooling).

[0091] Mechanical testing Tensile testing was performed in accordance with ISO 527-2. Dog bones were cast using 200g of resin compound. All samples were cured in an oven at 80°C for 24 hours prior to tensile testing.

[0092] water absorption The cast sample materials from Examples A-C and Reference Example 1 were immersed in desalinated water for 3 weeks. The samples were weighed after 7 and 21 days, and the weight increase was recorded.

[0093] [Table 2]

[0094] result: As is clear from the polymerization time measurements shown in Table 2, UPR curing under standard conditions using a cobalt-based curing system is impossible in the presence of phosphorus compounds such as VISIOMER® HEMA-P70M.

[0095] [Table 3]

[0096] result: Examples 3-8 demonstrate that curing is possible with different reactive diluent concentrations and variations in Fe-based accelerators.

[0097] Examples 3-8 demonstrate that VISIOMER® HEMA-P70M containing 20% ​​by weight of resin can be cured using cobalt and iron-based accelerators and the described accelerator system. A comparison of Examples 3 and 7 shows that the Fe metal content can be significantly reduced depending on the form of accelerator supply. Nouryact CF40 is provided in hydroxyethyl methacrylate at a reactive diluent concentration of 0.8-0.9 mg / kg. The reactive diluent increases the reactivity and solubility of the accelerator in the resin mixture.

[0098] Novel catalyst system and mechanical testing of UPR2-VISIOMER(registered trademark)HEMA-P70M [Table 4]

[0099] Examples 9-11 and Reference Example 3 were cured according to the formulations shown in Tables 4 and 5. The accelerator solution was mixed before being added to the resin. The initiator was added to the accelerated resin. All resins cured within 2.5-3.5 hours at room temperature when 50 grams of resin formulation with a layer thickness of 2 cm was cast.

[0100] [Table 5]

[0101] Examples 9-11 cured well, and the mechanical data were in good agreement with the styrene-based reference example. The mechanical properties of Examples 9 and 10 were equivalent to the pure styrene-based reference system. Due to the hydrophilicity of HEMA-P, water absorption increased as the amount of HEMA-P increased. [Brief explanation of the drawing]

[0102] [Figure 1] This figure shows the polymerization time of UPR1 in the presence of VISIOMER® HEMA-P70M compared to a styrene-based reference using a standard cobalt-based curing system.

Claims

1. A reactive diluent system for composite resins comprising (a) a reactive diluent composition and (b) an accelerator system, The reactive diluent composition (a) is a general formula (I) 【Chemistry 1】 [In the formula, R １ = H, Me, R ｎ , R ｍ = O － OH, Z, X ２ -P(=X) ３ ) R ｎ＋１ R ｍ＋１ And, n, m = 2 to 15, X １ , X ２ =O, CH ２ , S, or NH, X ３ = O, S, 【Chemistry 2】 And, L is a hydrocarbon linking group that optionally contains one or more heteroatoms. It contains or consists of the organophosphorus compound, The aforementioned accelerator system (b) (i) at least one iron salt or complex, (ii) at least one cobalt(II) salt or complex, and (iii) At least one solvent, optionally selected containing or consisting of these components Reactive diluent system.

2. The organophosphorus compound of the general formula (I) is optionally H ３ PO ４ H ４ P ２ O ７ , their salts, as well as acyclic / cyclic (poly)phosphates and their salts, and in the presence of methyl (meth)acrylates, 【Transformation 3】 [In the formula, R １ = H, Me, R ｎ , R ｍ =O － , OH, Z, O-P(=O)R ｎ＋１ R ｍ＋１ , wherein n, m = 2 to 15, X = 1, 2, 3..., 50, 【Chemistry 4】 And, x' = x, 1, 2, 3..., 50. The reactive diluent system according to claim 1, wherein the polyphosphate moiety in formula (I) may contain a monophosphate, a diphosphate, a triphosphate, or more phosphates.

3. The organophosphorus compound of formula (I) present in the reactive diluent composition (a) optionally contains H ３ PO ４ H ４ P ２ O ７ The reactive diluent system according to claim 1 or 2, comprising a 2-hydroxyalkyl (meth)acrylate phosphate in the presence of the salts thereof, as well as acyclic / cyclic (poly)phosphates and their salts, and methyl (meth)acrylate, wherein the polyphosphate moiety in formula (I) may comprise a monophosphate, diphosphate, triphosphate, or more phosphates.

4. The organophosphorus compound of formula (I) present in the reactive diluent composition (a) optionally contains H ３ PO ４ H ４ P ２ O ７ The reactive diluent system according to claim 1 or 2, comprising 2-hydroxyethyl methacrylate phosphate in the presence of , salts thereof, acyclic / cyclic (poly)phosphates and salts thereof, and methyl (meth)acrylate, wherein the polyphosphate moiety in formula (I) may comprise a monophosphate, diphosphate, triphosphate, or more phosphates.

5. The at least one iron salt or complex (i) present in the accelerator system (b) is selected from the group consisting of iron(II) species to which monodentate and polydentate N and / or O donor ligands are coordinated, or The at least one iron salt or complex (i) present in the accelerator system (b) is selected from the group consisting of iron halides, carboxylates, 1,3-dioxo complexes, and cyclopentadienyl iron complexes. The reactive diluent system according to claim 1 or 2.

6. The reactive diluent system according to claim 1 or 2, wherein the at least one iron salt or complex (i) present in the accelerator system (b) is an iron complex containing a tridentate, quadentate, quindentate, or hexadentate nitrogen / oxygen donor ligand.

7. The aforementioned cobalt(II) salt or complex is an alkylcarboxylate salt. The reactive diluent system according to any one of claims 1 to 6.

8. The reactive diluent system according to any one of claims 1 to 7, wherein the weight ratio of the at least one iron salt or complex (i) to the transition metal salt or complex (ii) is in the range of 2:1 to 100:

1.

9. The reactive diluent system according to any one of claims 1 to 8, wherein the weight ratio of the at least one iron salt or complex (i) to the transition metal salt or complex (ii) is in the range of 10:1 to 20:

1.

10. The reactive diluent system according to any one of claims 1 to 9, wherein the weight ratio of the organophosphorus compound in the reactive diluent composition (a) to the metal content in the accelerator system (b) is in the range of 90:1 to 3000:

1.

11. A curable resin composition comprising a curable resin and a reactive diluent system according to any one of claims 1 to 10.

12. Use of a reactive diluent system according to any one of claims 1 to 10 or a curable resin composition according to claim 11 for preparing a flame-retardant composite resin and / or a composite resin having improved glass fiber adhesion.

13. A method for preparing a cured composite resin composition, (a) Prepare the curable resin composition according to claim 11, (b) optionally adding at least one organic or inorganic additive, (c) Initiating the curing process by adding an initiator. Methods that include...

14. The at least one organic or inorganic additive is a pigment, a dispersant, and / or a fiber material. The fibrous material is selected from the group consisting of glass fibers, carbon fibers, aramid fibers, polyamide fibers, boron fibers, ceramic fibers, metal fibers, carbon fibers, and natural fibers, or any combination thereof. The method according to claim 13.

15. The method according to claim 13 or 14, wherein the initiator is an organic peroxide selected from the group consisting of methyl ethyl ketone peroxide (MEKP), benzoyl peroxide (BPO), cumene hydroperoxide (CuHP), or any combination thereof.

16. Fiber-reinforced material, (a) A polymer resin selected from the group consisting of (meth)acrylate resin, unsaturated polyester resin (UPR), or vinyl ester resin (VER), (b) at least one type of reinforcing fiber material and Includes, This can be obtained by curing components (a) and (b) in the presence of an initiator using the reactive diluent system described in any one of claims 1 to 10. Fiber-reinforced material.

17. The product further comprises at least one filler selected from the group consisting of aluminum trihydrate (ATH), antimony oxide, calcium carbonate, kaolin, or mixtures thereof, and / or The present invention further comprises at least one additive selected from the group consisting of inhibitors, retarders, thixotropes, or UV absorbers, or mixtures thereof. The fiber-reinforced material according to claim 16.

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