Low-color curing system

Abstract

This disclosure provides an accelerator solution, an unaccelerated resin composition containing the aforementioned accelerator solution, a curable resin composition containing the aforementioned unaccelerated resin composition, and a method for curing the curable resin. [Solution] The following composition is used as an accelerator solution: (i) a copper compound, (ii) a fatty acid ester of ascorbic acid and / or ascorbic acid, (iii) bipyridine, and (iv) a solvent comprising at least one phosphorus compound having the formula P(R)3 and / or P(R)3=O, wherein each R is independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

Description

[Technical Field]

[0001] This disclosure relates to an accelerator composition, an unaccelerated resin composition containing the aforementioned accelerator composition, a curable resin composition containing the aforementioned unaccelerated resin composition, and a method for curing a curable resin. The compositions and methods of this disclosure provide a colorless cured product. [Background technology]

[0002] It is well known that curable resins (e.g., unsaturated polyester resins, vinyl ester resins, (meth)acrylate resins) can be cured using organic peroxides, and that this curing can be accelerated using metal-based accelerators (e.g., International Publication 2012 / 126917, International Publication 2015 / 1211778, International Publication 2020 / 168201). However, a substantial problem with such metal-based accelerators is that they can be unstable (i.e., precipitate and / or lose performance when stored for long periods) and tend to lead to strong discoloration and / or frosting of the cured resin, both of which are undesirable in many applications. Furthermore, many known and commercially available accelerators use cobalt metal and / or alkylamine or alkanolamine stabilizers (e.g., diethanolamine, International Publication 2012 / 126917), but both components have poor environmental and toxicity profiles, which pose a significant risk of legislative prohibition (e.g., REACH in Europe).

[0003] Therefore, the object of this disclosure was to provide a curing system that avoids all of these drawbacks. [Overview of the project]

[0004] These technical problems have been found to be solved by curing curable resins using specific accelerator compositions and ketone peroxides or hydrogen peroxide. Therefore, this disclosure can be summarized in the following embodiments.

[0005] Aspect 1. A composition comprising: (i) a copper compound; (ii) ascorbic acid and / or a fatty acid ester of ascorbic acid; (iii) bipyridine; (iv) a solvent, wherein the solvent contains at least one phosphorus compound having the formula P(R)3 and / or P(R)3=O, where each R is independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, a composition.

[0006] Aspect 2. The composition according to Aspect 1, wherein the copper compound (i) contains a copper (II) compound.

[0007] Aspect 3. The composition according to Aspect 1 or 2, wherein the copper compound (i) is copper (II) acetate.

[0008] Aspect 4. The composition according to any one of the preceding aspects, wherein the fatty acid ester of ascorbic acid is

[0009]

Chemical formula

[0010] Aspect 5. The composition according to any one of the preceding aspects, wherein the fatty acid ester of ascorbic acid is ascorbyl palmitate.

[0011] Aspect 6. The composition according to any one of the preceding aspects, wherein (iii) is 2,2'-bipyridine of formula (I),

[0012]

Chemical formula

[0013] Aspect 7. The composition according to any one of the preceding aspects, wherein (iii) is 2,2'-bipyridine of formula (II),

[0014]

Chemical formula

[0015]

Chemical formula

[0016] A composition in which Ra and Ra' are H, or alternatively, Ra and Ra' together form a ring, preferably a C6 aromatic ring (to form 1,10-phenanthroline).

[0017] Embodiment 8. A composition according to any one of the embodiments described above, wherein (iii) is unsubstituted 2,2'-bipyridine.

[0018] [ka]

[0019] Embodiment 9. The composition according to any one of the embodiments described above, wherein at least two R groups of the at least one phosphorus compound are alkyl groups or alkoxy groups, more preferably all R groups are alkyl groups or alkoxy groups, and most preferably all R groups are alkoxy groups.

[0020] Embodiment 10. The composition according to any one of the embodiments described above, wherein solvent (iv) contains or consists of triethyl phosphate.

[0021] Embodiment 11. A composition of any one of the preceding embodiments, (i) is copper(II) acetate, (ii) is ascorbic acid and / or ascorbyl palmitate, (iii) is 2,2-bipyridine. (iv) is a composition comprising or containing triethyl phosphate.

[0022] Embodiment 12. The composition according to any one of the embodiments described above, wherein the accelerator solution comprises components (i), (ii), (iii), and (iv).

[0023] Embodiment 13. An unaccelerated resin composition, (i) Curable resin and (ii) A composition according to any one of embodiments 1 to 12, and (iii) an unaccelerated resin composition comprising, optionally, a filler.

[0024] Embodiment 14. The unaccelerated resin composition according to Embodiment 13, wherein the curable resin is an unsaturated polyester resin, a vinyl ester resin, or a (meth)acrylate resin.

[0025] Embodiment 15. The unaccelerated resin composition according to Embodiment 13 or 14, wherein the optionally selected filler is an inorganic filler.

[0026] Embodiment 16. A curable resin composition, (i) an unaccelerated resin composition according to any one of embodiments 12 to 15, (ii) A curable resin composition comprising a ketone peroxide, an organic peroxide containing hydrogen peroxide, hydrogen peroxide, and a mixture thereof, preferably at least one peroxide selected from ketone peroxide or hydrogen peroxide, most preferably ketone peroxide.

[0027] Embodiment 17. The curable resin composition according to Embodiment 16, wherein the at least one ketone peroxide is methyl ethyl ketone peroxide (MEKP), methyl isobutyl ketone peroxide (MIBK), methyl isopropyl ketone peroxide (MIKP), cyclohexanone peroxide (CYHP), acetylacetone peroxide, or a combination thereof.

[0028] Appearance 18. A parts kit, (i) A first component comprising a curable resin, (ii) A second component comprising the composition described in any one of embodiments 1 to 12, (iii) A component kit comprising an organic peroxide comprising ketone peroxide, hydrogen peroxide, hydrogen peroxide, and mixtures thereof, preferably a third component comprising at least one peroxide selected from ketone peroxide or hydrogen peroxide, most preferably ketone peroxide.

[0029] Embodiment 19. A method for curing a curable resin, comprising contacting the curable resin with a composition according to any one of Embodiments 1 to 12, and at least one peroxide selected from ketone peroxide, organic peroxide containing hydrogen peroxide, hydrogen peroxide, and mixtures thereof, preferably ketone peroxide or hydrogen peroxide, most preferably ketone peroxide.

[0030] Embodiment 20. The method according to Embodiment 19, wherein the curable resin is an unsaturated polyester resin, a vinyl ester resin, or a (meth)acrylate resin.

[0031] Embodiment 21. Embodiment 19 or the method according to Embodiment 19, wherein the ketone peroxide is methyl ethyl ketone peroxide (MEKP), methyl isobutyl ketone peroxide (MIBK), methyl isopropyl ketone peroxide (MIKP), cyclohexanone peroxide (CYHP), acetylacetone peroxide, or a combination thereof. [Brief explanation of the drawing]

[0032] [Figure 1] Figure 1 is a magnified photograph of the cured resin according to this disclosure. [Figure 2] Figure 2A is a magnified photograph of the cured resin of Example 2J (comparative example), and Figure 2B is a magnified photograph of the cured resin of Example 2G (comparative example). [Modes for carrying out the invention]

[0033] In a first aspect, the present disclosure relates to an accelerator composition (preferably an accelerator solution), (i) Copper compounds and, (ii) Ascorbic acid and / or fatty acid esters of ascorbic acid, (iii) Bipyridine and (iv) The present invention relates to a composition comprising a solvent which comprises at least one phosphorus compound having the formula P(R)3 and / or P(R)3=O, wherein each R is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

[0034] This accelerator composition was found to be remarkably stable, and when combined with ketone peroxide or hydrogen peroxide, it resulted in excellent curing of the curable resin without significant discoloration or opacity.

[0035] Component (i) of the accelerator composition of the first aspect of the present disclosure is a copper compound. Suitable copper compounds include, but are not limited to, halides, nitrates, sulfates, sulfonates, phosphates, phosphonates, oxides, and carboxylates. Examples of suitable carboxylates are lactates, 2-ethylhexanoates, acetates, propionates, butyrates, oxalates, lauates, oleates, linoleates, palmitates, stearics, acetylacetonates, octanates, nonanoates, heptanoates, neodecanoates, acetylacetonates, or naphthenates. Preferred copper compounds are copper chloride, nitrates, sulfates, lactates, 2-ethylhexanoates, octanates, nonanoates, heptanoates, neodecanoates, acetylacetonates, naphthenates, and acetates. Copper(II) compounds are preferred. The most preferred copper compound of the present disclosure is copper(II) acetate, preferably copper(II) acetate monohydrate.

[0036] The copper compound is preferably present in the accelerator in an amount of 0.01 to 2% by weight, preferably 0.05 to 1% by weight, and preferably 0.1 to 0.5% by weight, relative to the total weight of the accelerator composition.

[0037] Component (ii) of the accelerator composition of the first aspect of the present disclosure is ascorbic acid and / or a fatty acid ester of ascorbic acid. As used in the present disclosure, ascorbic acid includes L-ascorbic acid (CAS number 50-81-7) and D-isoascorbic acid (CAS number 89-65-6). Fatty acid esters of ascorbic acid can be obtained by reacting the free OH group of ascorbic acid with a fatty acid to produce the respective ester. Any suitable esterification process may be used to obtain the fatty acid ester of ascorbic acid. The fatty acid is preferably derived from a renewable source such as natural fats and oils. In one preferred embodiment, the fatty acid is palmitic acid (hexadecanoic acid), a linearly saturated C16 fatty acid found in animals, plants and microorganisms. In one embodiment, the fatty acid ester of ascorbic acid is

[0038] [ka] The formula is such that R is a C8-C30 alkyl group, preferably a C12-C18 alkyl group. The alkyl group may be saturated or unsaturated, and may be branched or linear. The fatty acid ester of ascorbic acid is preferably ascorbyl palmitate (CAS number 137-66-6).

[0039] Component (ii) is preferably present in the accelerator in an amount of 5 to 50% by weight, preferably 10 to 40% by weight, relative to the total weight of the accelerator composition.

[0040] Component (iii) of the accelerator composition of the first aspect of this disclosure is bipyridine. The remarkable stability of the accelerator composition is partly attributable to the bipyridine component, and comparative examples using nicotinamide instead of bipyridine were found to be stable for less than 9 hours (thereby rapidly degrading performance). Component (iii) is preferably 2,2'-bipyridine of formula (I),

[0041] [ka] During the ceremony, Each R can independently be H, alkyl, aryl, heteroaryl, or -AR 2 Selected from, A is O or NR 3 And R 2 and R 3 Each of these is independently H, alkyl, aryl, or heteroaryl. Ra is H, alkyl, aryl, heteroaryl, or -AR 2 Selected from Ah, O, or NR 3 And R 2 and R 3 Each of these is independently H, alkyl, aryl, or heteroaryl. Ra' stands for H, alkyl, aryl, heteroaryl, or -AR. 2 Selected from, A is O or NR 3 And R 2 and R 3 Each of these is independently H, alkyl, aryl, or heteroaryl, or Ra and Ra' both form a ring, preferably a C6 aromatic ring (forming 1,10-phenanthroline). More preferably, component (iii) is 2,2'-bipyridine of formula (II),

[0042] [ka] or 2,2'-bipyridine of formula (III),

[0043] [ka] During the ceremony, Each R can independently be H, alkyl, aryl, heteroaryl, or AR 2 Selected from, in the formula, A is O or NR 3 And R 2 and R 3 However, each is independently H, alkyl, aryl, or heteroaryl. Ra and Ra' are either H or together form a ring, preferably a C6 aromatic ring (to form 1,10-phenanthroline). Preferably, each R is independently H, C1-C6 alkyl, or -AR 2 Selected from, where A is O and R 2 It is H or C1-C6 alkyl. Ra and R a’ It is preferable that is H. Non-limiting examples of suitable bipyridines for use as component (iii) include 2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 4,4'-dimethoxy-2-2-bipyridine, 4,4'-di-tert-butyl-2,2'-dipyridyl, and combinations thereof. Most preferably, component (iii) is 2,2'-bipyridine.

[0044] [ka] Component (iii) is preferably present in the accelerator in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, and more preferably 0.5 to 2% by weight, relative to the total weight of the accelerator composition.

[0045] Component (iv) of the accelerator composition of the first aspect of the present disclosure is a solvent, which comprises or consists of at least one phosphorus compound having the formula P(R)3 (phosphine) and / or P(R)3=O (phosphine oxide), where each R is independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Solvents that do not contain at least one of the phosphorus compounds have been found to result in an unstable composition (rapid formation of a solid). Preferably, at least two R groups are selected from either alkyl groups or alkoxy groups, more preferably all R groups are selected from either alkyl groups or alkoxy groups, and more preferably all R groups are selected from alkoxy groups. Preferably, each R is independently an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. More preferably, each R is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (i.e., tri-(C) 1-6 The solvent is an alkyl phosphate, more preferably an alkoxy group having 1 to 4 carbon atoms, most preferably 1 to 3 carbon atoms, such as methoxy (R=MeO-), ethoxy (R=EtO-), propoxy (R=PrO-), or isopropoxy (R=iPrO-). Preferably, the solvent comprises at least one phosphorus compound having the formula P(R)3=O, where each R is independently an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms. Triethyl phosphate (triethoxyphosphine oxide; CAS 78-40-0; R=EtO- [i.e., P(OEt)3=O]) is most preferred.

[0046] The solvent component (iv) may contain or consist of at least one of the above-mentioned phosphorus compounds. Preferably, at least one phosphorus compound constitutes at least 50% by weight of the solvent component (iv), preferably at least 75% by weight of the solvent component (iv), more preferably at least 90% by weight of the solvent component (iv), and most preferably at least 99% by weight of the solvent component (iv), for example, 100% by weight of the solvent component (iv), relative to the total weight of the solvent component (iv). If one or more cosolvents are included in the solvent component (iv), it is preferable that they be included in a weight ratio of one or more phosphorus compounds to one or more cosolvents of about 50:50 to greater than 99:1, preferably about 75:25 to greater than 99:1, and preferably about 90:10 to greater than 99:1. For example, when a solvent mixture of 90:10 triethyl phosphate and butyl diglycol was used instead of 100% triethyl phosphate, stable analogs of Example 1B (hereinafter) were obtained.

[0047] The solvent component (iv) typically complements the mass balance of the accelerator composition and is typically present in the accelerator composition in an amount of about 10 to about 90% by weight, preferably about 50 to about 90% by weight, relative to the total weight of the accelerator composition.

[0048] The accelerator composition may optionally contain water. The water content is preferably 50% by weight or less, more preferably 40% by weight or less, more preferably 20% by weight or less, even more preferably 10% by weight or less, and most preferably 5% by weight or less, all based on the total weight of the accelerator composition.

[0049] In a preferred embodiment of the first aspect, the accelerator composition is (i) 0.01 to 2% by weight of a copper compound, (ii) 5-50% by weight of ascorbic acid and / or fatty acid esters of ascorbic acid, (iii) 0.05 to 5% by weight of bipyridine, (iv) A solvent comprising at least one phosphorus compound having the formula P(R)3 and / or P(R)3=O, wherein each R is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

[0050] In a more preferred embodiment of the first aspect, the accelerator composition is: (i) 0.01 to 2% by weight of a copper(II) compound, (ii) 5 to 50% by weight of ascorbic acid, wherein the fatty acid ester of ascorbic acid is

[0051] [ka] The formula is such that R is a C12-C18 alkyl group, and the ascorbic acid and / or fatty acid esters of ascorbic acid, (iii) 0.05 to 5% by weight of 2,2'-bipyridine of formula (II),

[0052] [ka] or 2,2'-bipyridine of formula (III),

[0053] [ka] During the ceremony, Each R can independently be H, alkyl, aryl, heteroaryl, or -AR 2 Selected from, where A is O or NR 3 And R 2 and R 3 Each of these is independently H, alkyl, aryl, or heteroaryl. Ra and Ra' are either H or together form a ring, preferably a C6 aromatic ring (to form 1,10-phenanthroline), (iv) A solvent comprising at least one phosphorus compound having the formula P(R)3 and / or P(R)3=O, wherein each R is independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

[0054] In a more preferred embodiment of the first aspect, the accelerator composition is: (i) 0.01 to 2% by weight of copper(II) acetate, (ii) 5-50% by weight of ascorbic acid and / or ascorbyl palmitate (iii) 0.05 to 5% by weight of bipyridine selected from 2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 4,4'-dimethoxy-2-2-bipyridine, 4,4'-di-tert-butyl-2,2'-dipyridine, and combinations thereof, preferably 2,2'-bipyridine, (iv) A solvent comprising one or more phosphorus compounds having the formula P(R)3=O, wherein each R is independently an alkoxy group having 1 to 3 carbon atoms, preferably 2 carbon atoms (i.e., triethyl phosphate).

[0055] In one embodiment, the accelerator composition of the first embodiment may consist of the above-described components (i) to (iv).

[0056] The accelerator composition may be prepared by simply mixing the components with an optional intermediate heating step and / or mixing step.

[0057] In a second aspect, the present disclosure relates to an unaccelerated resin composition, (i) Curable resin and (ii) an accelerator composition of the first aspect of the present disclosure, (iii) The present invention relates to an unaccelerated resin composition comprising, optionally, fillers and / or reinforcing fibers.

[0058] Any (radical) curable resin may be used in the unaccelerated resin composition. Suitable resins include alkyl resins, unsaturated polyester (UP) resins, vinyl ester resins, (meth)acrylate resins, polyurethanes, epoxy resins, and mixtures thereof. Preferred resins are (meth)acrylate resins, UP resins, and vinyl ester resins. In the context of 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” includes a combination of an acrylate or methacrylate resin and an ethylenically unsaturated monomer compound. The UP resins and acrylate resins defined above are common practice and commercially available.

[0059] Suitable UP resins cured by the process of the present invention are so-called orthoresin, isoresin, iso-NPG resin, and dicyclopentadiene (DCPD) resin. Examples of such resins include malein resin, fuma resin, aryl resin, vinyl resin, and epoxy resin, bisphenol A resin, terephthalic acid resin, and hybrid resin.

[0060] Vinyl ester resins include, for example, methacrylate, diacrylate, dimethacrylate, and acrylate resins based on their oligomers.

[0061] (Meth)acrylate resins include acrylate, methacrylate, diacrylate and dimethacrylate, as well as their oligomers.

[0062] Examples of ethylenically unsaturated monomer compounds include styrene and styrene derivatives such as alpha-methylstyrene, vinyltoluene, indene, divinylbenzene, vinylpyrrolidone, vinylsiloxane, vinylcaprolactam, and stilbene, as well as diaryl phthalates, dibenzylideneacetone, allylbenzene, methyl methacrylate, methyl acrylate, (meth)acrylic acid, diacrylate, dimethacrylate, acrylamide, vinyl acetate, cyanurate tolyl, isocyanurate tolyl, allyl compounds used in optical applications (such as (di)ethylene glycol diaryl carbonate), chlorostyrene, tert-butylstyrene, tert-butyl acrylate, butanediol dimethacrylate, and mixtures thereof. Suitable examples of (meth)acrylate reactive diluents include PEG200 di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 2,3-butanedial 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 di( Examples include meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, PPG250 di(meth)acrylate, tricyclodecanedimethylol 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.

[0063] The amount of ethylenically unsaturated monomer in the unenhanced resin composition is preferably at least 1% by weight, more preferably at least 10% by weight, more preferably at least 25% by weight, and most preferably at least 50% by weight, based on the weight of the resin.

[0064] The unaccelerated resin composition preferably contains the accelerator composition in an amount of at least 0.01 parts by weight (pbw) per 100 pbw of curable resin (i), preferably at least 0.1 pbw per 100 pbw of curable resin (i), preferably 5 pbw or less per 100 pbw of curable resin (i), and more preferably 3 pbw or less per 100 pbw of curable resin (i). Preferably, the unaccelerated resin composition contains the accelerator composition in an amount of 0.01 to 5 pbw per 100 pbw of curable resin (i), preferably 0.1 to 3 pbw per 100 pbw of curable resin (i).

[0065] The unaccelerated resin composition may also contain fillers and / or reinforcing fibers (iii). Examples of reinforcing fibers include glass fibers, carbon fibers, aramid fibers (e.g., Twaron®), and natural fibers (e.g., jute, kenaf, industrial hemp, flax (linen), ramie, etc.). The fibers may be in the form of fabric. Examples of fillers include quartz, sand, aluminum trihydrate, magnesium hydroxide, chalk, calcium hydroxide, clay, titanium dioxide, and lime. The properties of the filler components are not limited to any particular filler type. Any suitable amount of filler may be included in the unaccelerated resin composition, up to about 500 parts by weight (pbw) per 100 pbw of the curable resin (i), for example, up to 200 parts by weight (pbw) per 100 pbw of the curable resin (i).

[0066] Further optional additives that may be present in the unpromoted resin composition include, but are not limited to, pigments, radical inhibitors, flame retardants, and promoters.

[0067] In a preferred embodiment, the un-accelerated resin composition is (i) Curable resin and (ii) 0.01 to 5 parts by weight of the accelerator composition of the first embodiment of this disclosure per 100 parts by weight of (i), (iii)(i) comprises 0 to 500 parts by weight of filler and / or reinforcing fibers per 100 parts by weight of (i).

[0068] In other preferred embodiments, the unenhanced resin composition is (i) A curable resin which is an unsaturated polyester resin, a vinyl ester resin, a (meth)acrylate resin, or a combination thereof, (ii) 0.01 to 5 parts by weight of the accelerator composition of the first embodiment of this disclosure per 100 parts by weight of (i), (iii) comprising 0 to 200 parts by weight of filler and / or reinforcing fibers per 100 parts by weight of (i).

[0069] Unaccelerated resin compositions of a second aspect of this disclosure can be prepared in various ways, for example, by mixing individual components of an accelerator composition with a resin and an optional filler, or by mixing a resin containing an optional monomer and an optional filler with a pre-prepared accelerator composition according to this disclosure. The latter method is preferred.

[0070] In a third aspect, the present disclosure relates to a curable resin, (i) an unenhanced resin composition of the second embodiment, (ii) The present invention relates to a curable resin comprising ketone peroxide, organic peroxide containing hydrogen peroxide, hydrogen peroxide, and mixtures thereof, preferably ketone peroxide or hydrogen peroxide, most preferably at least one peroxide selected from ketone peroxide.

[0071] At least one peroxide (ii) is preferably one or more ketone peroxides, more preferably one or more ketone peroxides selected from the group consisting of methyl ethyl ketone peroxide (MEKP), methyl isopropyl ketone peroxide (MIKP), methyl isobutyl ketone peroxide (MIBK), cyclohexanone peroxide (CYHP), acetylacetone peroxide, and combinations thereof. MEKP and MIKP are particularly preferred, with MIKP being the most preferred.

[0072] The total amount of (ketone) peroxide in the curable resin composition is preferably 0.03 to 5 parts by weight (pbw), expressed as parts by weight of pure peroxide per 100 pbw of the unaccelerated resin composition, and more preferably 0.5 to 4 parts by weight (pbw), expressed as parts by weight of pure peroxide per 100 pbw of the unaccelerated resin composition.

[0073] In a fourth aspect, the present disclosure is a parts kit, (i) A first component comprising a curable resin, (ii) A second component comprising the accelerator composition of the first embodiment, (iii) relating to a component kit comprising an organic peroxide comprising ketone peroxide, hydrogen peroxide, hydrogen peroxide, and mixtures thereof, preferably a third component comprising at least one peroxide selected from ketone peroxide or hydrogen peroxide, most preferably ketone peroxide.

[0074] The curable resin, accelerator composition, and (ketone) peroxide are as described above. The first component (i) may optionally further include fillers and / or reinforcing fibers. Non-limiting examples of suitable reinforcing fibers include glass fibers, carbon fibers, aramid fibers (e.g., Twaron®), and natural fibers (e.g., jute, kenaf, industrial hemp, flax (solid line), ramie, etc.). The fibers may be in the form of fabric. Examples of fillers include quartz, sand, aluminum trihydrate, magnesium hydroxide, chalk, calcium hydroxide, clay, titanium dioxide, and lime. The properties of the filler component are not limited to any particular type of filler. Any suitable amount of filler may be included in the first component (i), such as up to about 200 parts by weight (pbw) of filler per 100 pbw of curable resin. Further optional additives that may be present in the first component (i) include, but are not limited to, pigments, radical inhibitors, flame retardants, and accelerators. If the first component includes a filler or additive, the third component preferably includes a ketone peroxide.

[0075] During use, the first, second, and third components are mixed together, and the resulting mixture is cured to form a cured resin.

[0076] In a fifth aspect, the disclosure relates to a method for curing a curable resin, comprising contacting the curable resin with an accelerator composition of the first aspect and at least one peroxide selected from ketone peroxides, organic peroxides including hydrogen peroxide, hydrogen peroxide, and mixtures thereof, preferably ketone peroxides or hydrogen peroxide, most preferably ketone peroxides. In a preferred embodiment, the accelerator composition is added to the curable resin to form a mixture, and then at least one ketone peroxide is added to the mixture. In an alternative embodiment, at least one ketone peroxide is added to the curable resin to form a mixture, and then the accelerator composition is added to the mixture.

[0077] Again, the curable resin, accelerator composition, and (ketone) peroxide are as described above.

[0078] When a curable resin, (ketone) peroxide, accelerator composition, and any other components are combined, these compounds are mixed and dispersed. The curing process can be carried out at any temperature from -15°C to 250°C. Preferably, this is carried out at ambient temperatures commonly used in applications such as hand lay-up, spray-up, filament winding, resin transfer molds, coatings (e.g., gel coatings and standard coatings), button manufacturing, centrifugal casting, corrugated sheets or flat panels, relining systems, and kitchen sinks via injected compounds. However, temperatures up to 180°C, more preferably up to 150°C, and most preferably up to 100°C may also be used in SMC, BMC, pultrusion techniques, etc. The cured composition may be subjected to post-curing treatment to further optimize hardness. Such post-curing treatment is generally carried out at temperatures in the range of 40 to 180°C for 30 minutes to 15 hours.

[0079] Curing resins can be used in a wide range of applications, including marine applications, chemical anchors, roofing, construction, lining, pipes and tanks, flooring, wind turbine blades, laminates, polymer concrete, tabletops, washers, and sanitary products.

[0080] It should be noted that the various elements of this disclosure, including but not limited to preferred ranges of various parameters, can be combined in any way, provided they are not mutually exclusive. [Examples]

[0081] This disclosure is illustrated by the following embodiments, but is not limited to them.

[0082] Reactivity was measured by exothermic measurement according to the modified standard NEN-ENISO584. Experiments in the examples were carried out by applying a constant starting temperature of 20°C. Temperature-time curves were recorded on a EurothermChessell recorder type 6100A. Gel time (GT) = time in minutes elapsed between the start of the experiment and the monitored temperature rise to 5.6°C higher than the starting temperature. Time to peak (TTP) = time elapsed between the start of the experiment and the point at which the peak temperature was reached. Peak exothermic reaction (PE) = maximum temperature reached. In the examples below, gel time (GT), time to peak (TTP), and peak exothermic reaction (PE) were determined using a EurothermChessell recorder type 6100A. The opacity and color of the cured resin were determined visually.

[0083] Example 1 The following accelerator compositions were prepared by combining the components listed in the table below in the specified amounts, and then mixing (stirring) the resulting compositions at 50°C for 60 minutes (in 200g batches).

[0084] [Table 1]

[0085] [Table 2]

[0086] [Table 3]

[0087] [Table 4]

[0088] [Table 5]

[0089] [Table 6]

[0090] These accelerator compositions were found to be remarkably stable, showing no significant precipitate formation or loss of performance even after a four-week storage period. The remarkable stability of the accelerator compositions is attributed to the bipyridine component in combination with the solvent type; a comparative example using nicotinamide instead of the bipyridine component was found to be stable for less than nine hours (with rapid and substantial precipitate formation), as was another comparative example using tris(2-ethylhexyl) phosphate instead of triethyl phosphate (where performance rapidly deteriorated thereafter). Thus, these stable accelerator compositions present a viable alternative to those using cobalt metal accelerators and / or amine stabilizers, which are under threat of legislative prohibition due to their poor toxicity profiles.

[0091] Example 2 Example 1B of the accelerator composition was tested with various types of peroxides in an attempt to solve the known problems of "yellowing" and "frosting." A surprising finding was that these problems were solved when ketone peroxides were used. Using other organic peroxides resulted in discoloration (X), frosting (O), or both. A further unexpected finding was that these problems were also solved when hydrogen peroxide (H2O2) was used. Interestingly, these problems were not solved with pure organic hydroperoxides, e.g., cumene hydroperoxide (e.g., 2J) and t-butyl hydroperoxide (the resin did not cure). Based on these findings, and without wishing to be constrained or limited to theory, it is hypothesized that the effectiveness of ketone peroxides in this curing system may be partly related to ketone peroxides that generally contain a certain amount of hydrogen peroxide (due to the dynamic equilibrium in which ketone peroxides tend to exist under standard laboratory conditions). Each of Examples 2A-2M was performed by mixing the reagents in the indicated amounts (parts by weight) in a test tube (first adding the accelerator and resin, then adding the peroxide), and then curing the MMA resin.

[0092] [Table 7] C=colorless X = yellow or brown CX = Nearly colorless (very slight yellowing) T=transparent O = Opaque (Frost) N / A=poor curing * MMA = Methyl methacrylate 1 Methylisopropyl ketone peroxide (MIKP) 2 Methyl ethyl ketone peroxide (MEKP) 3 tert-butylperoxybenzoate 4 Dibenzoyl peroxide 5 Dibenzoyl peroxide 6 Dilauroyl peroxide 7 2,5-Dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane 8 tert-butylperoxy-2-ethylhexanoate 9 tert-butylperoxy-3,5,5-trimethylhexanoate 10 Cumyl hydroperoxide 11 tert-butylperoxy-2-ethylhexyl carbonate 12 1,1-Di(tert-butylperoxy)cyclohexane

[0093] Certain accelerator compositions disclosed herein, combined with ketone peroxides or hydrogen peroxide, have solved both the discoloration and frosting problems associated with curing resins that can be cured using metal-based accelerators. To aid in understanding the substantial improvements provided by the curing systems disclosed herein, close-up photographs of cured resins are provided in Figures 1 and 2. Figure 1 is a magnified photograph of a cured resin (in a test tube) obtained using the accelerator compositions of this disclosure combined with ketone peroxides (colorless and transparent, glassy), where the inserted wire is clearly visible and there is no discoloration or gloss of the resin. Figure 2A is a magnified photograph of Example 2J (in a test tube), where the cured resin has undergone slight discoloration and severe frosting (the cured resin is opaque and the inserted wire is not visible). Figure 2B is a magnified photograph of Example 2G (in a test tube), where the cured resin is brown and frosted (the cured resin is opaque and the inserted wire is not visible).

[0094] Example 3 Examples 1A-D were combined with ketone peroxides to investigate whether the substantial improvement observed in Example 2 could be replicated with other accelerators and other unsaturated resins from Example 1. In all cases, the cured resins were colorless and transparent, and no discoloration or gloss (opacity) issues occurred. All showed excellent gel time (GT), peak time (TTP), and peak exothermic (PE).

[0095] [Table 8] 1 Advalite35065-0 2 Beyone700-T-01 3 Butanox P-50 § The reaction was too fast to carry out the experiment.

[0096] [Table 9] 1 PalatalP4-01 2 Butanox M-50 3 Butanox P-50

[0097] [Table 10]

[0098] Example 4 A further advantage of the curing system of this disclosure is its ability to successfully incorporate fillers into the cured resin. For example, aluminum trihydrate (ATH) and quartz were successfully incorporated into the cured resin, and a deliberately opaque cured resin was obtained in which the opacity and color of the cured resin originated solely from the fillers.

[0099] [Table 11] 1 PalatalP4-01

[0100] Therefore, the curing system disclosed herein enables the production of a filled cured resin, and the resin does not affect the visual properties provided by the filler.

[0101] Example 5 It was also observed that the time peak (TTP) could be manipulated by changing the ratio of ascorbic acid (AA) to ascorbic acid fatty acid ester (e.g., ascorbyl palmitate, AAP) in the accelerator composition. Examples 5A to 5G used 2pbw of the following accelerator compositions, the compositions having various weight ratios of AAP:AA.

[0102] [Table 12]

[0103] [Table 13]

[0104] The ability to controllably manipulate TTP is a further substantial benefit of the accelerator compositions and curing systems of this disclosure.

[0105] Example 6 The curing system worked well with various bipyridines, with or without aluminum trihydrate (ATH) fillers. The plant compositions were formulated as follows:

[0106] [Table 14]

[0107] [Table 15] *The amounts in the table correspond to the amount of the specified bipyridine-containing accelerator composition (PBW), not the amount of the specified bipyridine itself.

[0108] Example 7 Further experiments confirmed that the curing system disclosed herein is highly effective even with very small amounts of accelerator and oxidizer.

[0109] [Table 16] Styrene-free resin based on dimethyl itaconate

[0110] In this disclosure, unless expressly indicated otherwise, the word “or” is used to mean an operator that returns true when either or both of the stated conditions are met, in contrast to the “exclusive or” operator, which requires only one of the stated conditions to be met. The word “comprising” is used to mean “including,” and not “consisting of.” All prior teachings identified above are incorporated herein by reference. No reference herein to previously published documents should be construed as an acknowledgment or representation that such teachings were common knowledge in Europe or elsewhere as of the date of this specification.

Claims

1. A composition, (i) Copper compounds and, (ii) Ascorbic acid and / or fatty acid esters of ascorbic acid, (iii) Bipyridine and, (iv) A solvent, which has the formula P(R) ３ and / or P(R) ３ A composition comprising a solvent containing at least one phosphorus compound having =O, wherein each R is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

2. The composition according to claim 1, wherein the copper compound (i) comprises a copper (II) compound.

3. The composition according to claim 1 or 2, wherein the copper compound (i) is copper(II) acetate.

4. A composition according to any one of claims 1 to 3, wherein the fatty acid ester of ascorbic acid is 【Chemistry 1】 A composition in which R is a C8-C30 alkyl group.

5. The composition according to any one of claims 1 to 4, wherein the fatty acid ester of ascorbic acid is ascorbyl palmitate, preferably ascorbyl palmitate.

6. A composition according to any one of claims 1 to 5, wherein (iii) is 2,2'-bipyridine of formula (II), 【Chemistry 2】 or 2,2'-bipyridine of formula (III), 【Transformation 3】 During the ceremony, Each R can independently be H, alkyl, aryl, heteroaryl, or A-R ２ Selected from, A is either O or NR ３ And R ２ and R ３ Each of these is independently H, alkyl, aryl, or heteroaryl. A composition in which Ra and Ra' are either H or both form a ring, preferably a C6 aromatic ring (to form 1,10-phenanthroline).

7. The solvent (iv) is the one specified by formula P(R) ３ The composition according to any one of claims 1 to 6, comprising or consisting of one or more phosphorus compounds having =O, wherein each R is independently an alkoxy group having 1 to 3 carbon atoms.

8. A composition according to any one of claims 1 to 7, Component (i) is copper(II) acetate, Component (ii) is ascorbic acid and / or ascorbyl palmitate, Component (iii) is 2,2'-bipyridine. The component (iv) is a composition comprising or consisting of triethyl phosphate.

9. The composition according to any one of claims 1 to 8, wherein the composition comprises components (i), (ii), (iii), and (iv).

10. An unaccelerated resin composition, (i) Curable resin and (ii) A composition according to any one of claims 1 to 9, (iii) An unaccelerated resin composition comprising fillers and / or reinforcing fibers as desired.

11. The unaccelerated resin composition according to claim 10, wherein the curable resin is an unsaturated polyester resin, a vinyl ester resin, a (meth)acrylate resin, or a combination thereof.

12. A curable resin composition, (i) The unaccelerated resin composition according to claim 10 or 11, (ii) A curable resin composition comprising a ketone peroxide, an organic peroxide containing hydrogen peroxide, hydrogen peroxide, and a mixture thereof, preferably at least one peroxide selected from ketone peroxides.

13. It is a parts kit, (i) A first component comprising a curable resin, (ii) A second component comprising the composition according to any one of claims 1 to 9, (iii) A component kit comprising a third component comprising an organic peroxide, preferably at least one peroxide selected from ketone peroxides, hydrogen peroxides, hydrogen peroxides, and mixtures thereof.

14. A method for curing a curable resin, comprising contacting the curable resin with a composition according to any one of claims 1 to 9 and at least one peroxide selected from ketone peroxide, organic peroxide containing hydrogen peroxide, hydrogen peroxide, and mixtures thereof, preferably ketone peroxide.

15. A cured resin that can be obtained by the method described in claim 14.

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