Accelerated peroxide-cured resin composition with extended open time

Abstract

Curable resin compositions having extended open times at ambient temperatures and short cure times at high temperatures are prepared using a curable resin curable by one or more liquid organic peroxides or blends thereof and an accelerator / activator accelerator comprising a metal salt and a thiol-functionalized organic compound.

Description

Technical Field

[0001] This disclosure relates to resin compositions that can be cured using liquid organic peroxides, organic peroxide formulations and blends thereof, and that have an extended pot life (open time) at ambient (room temperature) temperatures but can still be cured rapidly at higher temperatures, thus making them particularly suitable for composite material applications such as pultrusion, cure-in-place pipes and resin transfer molding. Background Technology

[0002] Composites based on curable thermosetting resins (such as unsaturated polyester and vinyl ester resins) and optional reinforcing fillers (such as glass or carbon fibers) typically exhibit advantageous mechanical properties, such as high strength and stiffness. Curing of the resin in such systems is often achieved by using organic peroxides to initiate a free radical reaction, leading to crosslinking of the curable resin. In at least some end-use applications of such composite systems, rapid curing of the resin at high temperatures is desirable to reduce production costs and improve the efficiency of composite manufacturing operations. Heating a peroxide-containing curable resin causes the peroxide to decompose and generate free radicals, which then initiate the curing of the resin, resulting in the hardening of the liquid resin and providing the improved physical properties desired in the composite system. The composite is considered cured when the physical form and shape of the composite part are permanently fixed or permanently hardened at the intended service temperature of the composite part, forming a rigid thermosetting composite part. However, simultaneously, the curable resin / peroxide / reinforcing filler mixture or blend should ideally have a relatively slow curing rate at ambient temperature (room temperature) to allow sufficient time for such mixture or blend to mold into the target form of the composite part. In this disclosure, a curable thermosetting resin (e.g., an unsaturated polyester resin) and optional reinforcing fillers are cured by organic peroxides, organic peroxide formulations and blends thereof as described herein.

[0003] Generally, high-temperature curing using organic peroxides relies on the thermal degradation of these organic peroxides to initiate the polymerization of the curable resin (e.g., unsaturated polyester resin). To achieve a sufficiently short curing time to ensure reasonable cycle times, peroxides with relatively short half-lives at room temperature are used as the primary initiator. These peroxides are typically selected from certain peroxide esters or peroxydicarbonates that must be stored below ambient temperature (freezing temperature) due to their instability, such as tert-butylperoxyneodecanate, or solid peroxydicarbonates, such as di(2-ethylhexyl)peroxydicarbonate or di-(4-tert-butylcyclohexyl)peroxydicarbonate.

[0004] Despite their effectiveness, these peroxides are not optimal because they either require frozen storage (in the case of liquid peroxides), which increases storage costs and safety risks, or (in the case of solid peroxides) require additional effort and cost to disperse into curable resins, and their storage is regulated due to their fire code classification.

[0005] Traditional composite material applications typically use one of two types of initiation packages: either a mixture with a solid (or paste) peroxide as the primary initiator, or a mixture based on cryogenic storage. An example of a solid peroxide is di(4-tert-butylcyclohexyl) peroxide (trade name Perkadox). ® 16 or Norox ® 600-CL2). The recommended storage temperature for this solid dicarbonate peroxide is 20°C, but this applies only to its solid form. The liquid solution form of this peroxide requires cryogenic storage. An example of a liquid cryogenically stored peroxide is LUPEROX. ® 233 and LUPEROX ® 10. Both types of systems have drawbacks. Solid organic peroxide systems require thorough mixing with the resin to ensure proper dispersion and dissolution. Therefore, they are typically diluted in styrene or other solvents before being introduced into the resin, which increases costs, reduces efficiency, adds processing steps, and may increase harmful environmental impacts.

[0006] Those skilled in the art will know that organic peroxides, such as peroxide esters, hemiperoxy ketals, peroxy ketals, monoperoxy carbonates, ketone peroxides, diacid peroxides, and hydroperoxides, should not come into direct contact with transition metal salts, as these salts are generally considered destabilizing agents in the presence of these organic peroxides. These transition metal salts or metal soaps are commonly referred to in the art as accelerators, activators, or promoters. Furthermore, it is recommended that these peroxides not come into contact with the transition metals themselves (e.g., iron or copper). For example, many safety data sheets for organic peroxides warn of storage incompatibility between transition metal salts, metal soaps, and / or metal activators.

[0007] U.S. Patent No. 4,380,605 discloses the crosslinking of unsaturated polyester resins at room temperature in the presence of a peroxide ester initiator, which is accelerated by a thiol compound and a metal salt, wherein the metal is selected from the group consisting of copper and iron or a mixture of metal salts thereof.

[0008] U.S. Patent No. 5,310,826 discloses accelerator compositions for the free radical polymerization of unsaturated polyesters and the curing of unsaturated polyesters and polyurethanes.

[0009] U.S. Patent No. 5,235,010 discloses accelerator compositions for the curing of various unsaturated resins, including complexes of certain metal salts with oxygen-containing compounds, wherein thiols may also be present. Peroxide initiators may be used in combination with such complexes.

[0010] U.S. Patent Application Publication No. 2010 / 0120977 A1 discloses an accelerator solution comprising a complexing agent selected from those having nitrogen atoms and hydroxyl groups and bipyridine, a metal salt selected from transition metals, magnesium and lithium, and an optional solvent.

[0011] U.S. Patent Application Publication No. 2011 / 0250373 discloses the use of nitroxide to control free radical curing resin systems in the production of thermosetting materials, wherein free radical initiators (free radical polymerization initiators) selected from diacyl peroxides, peroxide esters, peroxydicarbonates and mixtures thereof can be used.

[0012] International Publication No. WO 2008 / 003496 describes a two-component composition comprising a first component and a second component, wherein the first component is a resin composition comprising an unsaturated polyester or vinyl ester resin, a manganese compound and a thiol compound, and the second component comprises hydrogen peroxide or an alkyl hydroperoxide.

[0013] US Patent No. 11,873,381 discloses a curable resin composition comprising a curable resin, a room-temperature-stable organic peroxide [non-perketal, which is liquid at 25°C], a room-temperature-stable perketal (liquid at 25°C), a metal salt, a thiol-functionalized organic compound, and a free radical trap. The curable resin composition remains substantially liquid at 25°C. Summary of the Invention

[0014] A curable resin composition is provided, which is prepared using a curable unsaturated polyester resin that can be cured with at least one liquid organic peroxide formulation and blended with a first component and a second component. The first component comprises at least one non-room temperature stable liquid organic peroxide and at least one room temperature stable liquid organic peroxide. The second component (also referred to as an accelerator / activator / promoter) comprises at least one metal salt, at least one thiol-functionalized organic compound, and optionally a solvent.

[0015] Non-room temperature liquid organic peroxide formulations are defined as formulations with a 1-hour half-life of less than 100°C; while room temperature stable liquid organic peroxide formulations have a 1-hour half-life of 100°C or higher.

[0016] Preferred curable resins may comprise (meth)acrylate resins, unsaturated polyester resins, and vinyl ester resins. Curable resins may include reinforcing fillers. Curable resin compositions can be refrigerated prior to the curing process to extend shelf life. Curable resin compositions can be used in pultrusion, in-situ cured pipe (CIPP), and resin transfer molding (RTM), etc. Furthermore, the first and second components can be blended together before being incorporated with the curable resin. Thus, transition metal salts (e.g., ZnCl2) and thiol organic compounds dissolved in suitable solvents can be safely blended with various organic peroxides without visible reaction for several hours at ambient temperature. This result is unexpected because transition metal halides are known promoters of the degradation of organic peroxides.

[0017] Furthermore, the inventors were surprised to discover that the peroxide blend component could be mixed with the accelerator / activator / promoter component (metal salt and thiol-functionalized organic compound) without the use of any free radical scavengers, the free radical scavengers including nitroxide free radicals (e.g., TEMPO (2,2,6,6-tetramethylpiperidine-1-oxy), 4-OH TEMPO or SG-1 nitroxide free radical) and quinones (e.g., MTBHQ or monotert-butylhydroquinone, HQMME or hydroquinone monomethyl ether).

[0018] Surprisingly, the preferred organic peroxide formulations containing accelerator components described in this disclosure are relatively stable. Stability means that the formulation (composition or blend) does not immediately decompose at temperatures up to 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, or even up to 30°C for at least 1 hour, at least 2-3 hours, at least 5-8 hours, at least 8-10 hours, or at least 10-15 hours, or even up to 24 hours, as measured by the temperature rise of the composition. Such organic peroxide-activator compositions provide the additional beneficial effect of enabling more thorough blending of the peroxide and activator into unsaturated polyester resins. Once the peroxide blend containing the metal salt and thiol-functionalized organic compound is added to the curable resin and heated, the resin begins to exothermically cure. In other words, when a combination of metal salts and thiol-functionalized organic compounds is directly added to organic peroxide formulations as an accelerator / activator / promoter system, it provides a surprisingly temperature-stable and fully cured system, while also enabling rapid and efficient curing of unsaturated polyesters at high temperatures. It is quite unexpected that blends of transition metal salts and thiol-functionalized compounds can be safely stored at ambient temperatures and directly added to organic peroxides without immediate decomposition of the organic peroxides.

[0019] A curable resin composition is provided. The curable resin composition comprises:

[0020] a) At least one curable resin that can be cured by a liquid organic peroxide;

[0021] b) At least one room-temperature stable organic peroxide that is liquid at 25°C and has a half-life temperature of 100°C or higher at one hour;

[0022] c) Optionally, at least one non-room-temperature stable organic peroxide is liquid at 10°C or lower and has a half-life temperature of less than 100°C in one hour.

[0023] d) At least one salt of at least one metal, said metal comprising at least one of the following: Li, Al, Mg, Co, Fe, Cu, Zn, Ni, Mn, Cr, Sn, Au, Pd, or Pt;

[0024] e) at least one thiol-functionalized organic compound; and

[0025] f) Optionally, at least one solvent, said solvent comprising at least one of alcohol, glycol or glycol ether.

[0026] A method for preparing a cured composition is also provided. This method includes the following steps:

[0027] The following substances are combined to provide a curable resin composition:

[0028] a) At least one curable resin that can be cured by an organic peroxide;

[0029] b) At least one room-temperature stable organic peroxide that is liquid at 25°C and has a half-life temperature of 100°C or higher at one hour;

[0030] c) Optionally, at least one non-room-temperature stable organic peroxide is liquid at 10°C or lower and has a half-life temperature of less than 100°C in one hour.

[0031] d) At least one salt of at least one metal, said metal comprising at least one of the following: Li, Al, Mg, Co, Fe, Cu, Zn, Ni, Mn, Cr, Sn, Au, Pd, or Pt;

[0032] e) at least one thiol-functionalized organic compound; and

[0033] f) Optionally, at least one solvent, said solvent comprising at least one of an alcohol, a glycol, or a glycol ether;

[0034] and

[0035] The curable resin composition is heated to a temperature that effectively initiates the curing of the curable composition.

[0036] A curing system is also provided. This curing system includes i) a first component and ii) a second component. The first component comprises:

[0037] At least one room-temperature stable organic peroxide, which is liquid at 25°C and has a one-hour half-life temperature of 100°C or higher; and

[0038] At least one non-room-temperature stable organic peroxide, which is liquid at 10°C or lower and has a half-life temperature of less than 100°C in one hour.

[0039] The second component of the curing system comprises:

[0040] At least one salt of at least one metal, said metal comprising at least one of the following: Li, Al, Mg, Co, Fe, Cu, Zn, Ni, Mn, Cr, Sn, Au, Pd, or Pt;

[0041] At least one thiol-functionalized organic compound; and

[0042] Optionally, at least one solvent, said solvent comprising at least one of an alcohol, a glycol, or a glycol ether.

[0043] According to one implementation, the first component is substantially free of or contains no styrene.

[0044] A curing system is provided in which the above i) first component and ii) second component are combined to form a single, room temperature stable liquid curing system.

[0045] A curable resin composition is also provided. This curable resin composition comprises the following:

[0046] a) At least one curable resin, said curable resin comprising at least one of alkyd resin, unsaturated polyester resin, vinyl ester resin or (meth)acrylate resin, or mixtures or blends thereof, wherein said curable resin is curable by means of a liquid organic peroxide.

[0047] b) At least one liquid organic peroxide selected from the group consisting of:

[0048] i) Room temperature stable organic peroxides that are liquid at 25°C and have a one-hour half-life temperature of 100°C or higher; or

[0049] ii) Non-room-temperature stable organic peroxides that are liquid at 10°C or lower and have a one-hour half-life temperature of less than 100°C; or

[0050] iii) Blends or mixtures of organic peroxides (i) and organic peroxides (ii);

[0051] c) At least one salt of at least one metal, said metal comprising at least one of the following: Li, Al, Mg, Co, Fe, Cu, Zn, Ni, Mn, Cr, Sn, Au, Pd, or Pt;

[0052] d) At least one thiol-functionalized organic compound; and

[0053] e) Optionally, at least one solvent, said solvent comprising at least one of an alcohol, a glycol, or a glycol ether.

[0054] A liquid organic peroxide composition is also provided. The liquid organic peroxide composition comprises a blend of the following components:

[0055] First organic peroxide;

[0056] Second organic peroxide;

[0057] At least one transition metal salt dissolved in a solvent, said solvent comprising at least one of an alcohol, a glycol, or a glycol ether; and

[0058] At least one thiol-functionalized organic compound is provided. The blend is stable at 18°C ​​or higher, preferably 20°C or higher, more preferably 23°C or higher for at least 1 hour, preferably at least 2-8 hours, more preferably at least 8-15 hours, and most preferably at least 24 hours. Attached Figure Description

[0059] Figure 1 The results of peroxide curing of unsaturated polyester resin (UPR) using our novel accelerator solution are shown according to an exemplary embodiment of this disclosure.

[0060] Figure 2 The results of peroxide curing of UPR using our novel accelerator solution are shown in another exemplary embodiment according to this disclosure.

[0061] Figure 3 An exemplary embodiment according to this disclosure is shown, in which the peroxide exhibits unexpected stability when blended with our novel accelerator solution, followed by an effective exothermic reaction.

[0062] Figure 4 A comparative example is shown where the stability of the peroxide decreases when pure peroxide (without resin) is mixed with ZnCl2 [a transition metal known to destabilize organic peroxides].

[0063] Figure 5 An example is shown whereby the peroxide exhibits unexpected stability when blended with a novel accelerator solution of an exemplary embodiment of this disclosure.

[0064] Figure 6 The following diagram illustrates the results of peroxide curing of UPR using our novel accelerator solution according to an exemplary embodiment of this disclosure; and

[0065] Figure 7 The results of peroxide curing of UPR using our novel accelerator solution are shown in another exemplary embodiment according to this disclosure. Detailed Implementation

[0066] Information on the one-hour half-life of various organic peroxides is available on LUPEROX. ® Organic peroxides can be found in the Arkema Corporation General Catalog ● Americas and the Arkema Corporation's polymer catalog (Colombes Cedex), the full contents of which are included in this article for all purposes.

[0067] Half-life refers to the time it takes for 50% of a peroxide to decompose at a specific temperature. Half-life temperature refers to the temperature at which 50% of a peroxide decomposes within a specific time, as described in "Safety and Handling of Organic Peroxides: A Guide Prepared by the Organic Peroxide Producers Safety Division of Plastics Industry Association," Plastics Industry Association, Inc., OPPSD Announcement AS-109 (August 2018), the entire contents of which are incorporated herein by reference for all purposes.

[0068] As used herein, the terms “liquid” and “liquid state” mean that a material is liquid (flowable or pourable) at the stated temperature and is in solution form, or that it is (pure) liquid (flowable or pourable).

[0069] As used herein, the term "stable" in relation to an organic peroxide formulation, composition, or blend means that the formulation (composition or blend) does not immediately decompose at temperatures up to 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, or even up to 30°C for at least 1 hour, at least 2-3 hours, at least 5-8 hours, at least 8-10 hours, or at least 10-15 hours, or even up to 24 hours, as measured by the temperature rise of the formulation, composition, or blend. Such organic peroxide-activator compositions provide the additional beneficial effect of enabling more thorough blending of the peroxide and activator into the peroxide-curable resin. Once the peroxide blend containing the metal salt and thiol-functionalized organic compound is added to the curable resin and heated, the combination of the resin and the peroxide formulation begins to exothermically and cure. In other words, when a combination of metal salts and thiol-functionalized organic compounds is directly added to organic peroxide formulations as an accelerator / activator / promoter system, it provides a surprisingly temperature-stable and fully cured system, while also enabling rapid and efficient curing of curable resins at high temperatures. It is quite unexpected that blends of transition metal salts and thiol-functionalized compounds can be safely stored at ambient temperatures and added directly to organic peroxides without immediate decomposition of the organic peroxides.

[0070] Curable resin

[0071] As used herein, curable resins are those that are initially liquid but undergo polymerization or other reactions when combined with organic peroxide formulations and heated to form solid (thermosetting) articles.

[0072] Suitable curable resins that can be used in embodiments of this disclosure include, but are not limited to, alkyd resins, unsaturated polyester (UP) resins, vinyl ester resins, (meth)acrylate resins (also known as acrylic resins), and mixtures thereof. Preferred resins comprise (meth)acrylate resins, unsaturated polyester 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 olefinically unsaturated monomer compound (e.g., styrene), which is generally used to reduce the viscosity of (uncured) unsaturated polyester resins and promote crosslinking and the formation of physical properties useful for cured composite articles. The term "(meth)acrylate resin" refers to a combination of acrylate and / or methacrylate resins with an olefinically unsaturated monomer compound. Such UP resins and acrylate resins are well known in the art and are commercially available.

[0073] The unsaturated polyester resins available in embodiments of this disclosure include reactive resins dissolved in polymerizable monomers or mixtures of monomers. These reactive resins are formed by the condensation of saturated dicarboxylic acids or anhydrides with unsaturated dicarboxylic acids or anhydrides and diols. Examples of these polyester resins include products of the reaction of saturated dicarboxylic acids or anhydrides (e.g., phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, bridged methylenetetrahydrophthalic anhydride, tetrachlorophthalic anhydride, hexachlorobridged methylenetetrahydrophthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, or sebacic acid) and unsaturated dicarboxylic acids or anhydrides (e.g., maleic anhydride, fumaric acid, chloromaleic acid, itaconic acid, citric acid, or mesocarboxylic acid) with diols (e.g., ethylene glycol, propylene glycol, butanediol, diethylene glycol, triethylene glycol, or neopentyl glycol). Small amounts of polyols (such as glycerol, pentaerythritol, trimethylpropane, or sorbitol) can be used with diols.

[0074] According to some embodiments, the curable resin may comprise at least one of the following: alkyd resin, unsaturated polyester resin, vinyl ester resin, or (meth)acrylate resin, or a mixture or blend thereof. According to some embodiments, the curable resin may comprise at least one of unsaturated polyester resin or vinyl ester resin, or a combination thereof. According to some embodiments, the curable resin may comprise an unsaturated polyester resin. According to some embodiments, the curable resin may comprise a vinyl ester resin.

[0075] In the case of unsaturated polyester resins, the final three-dimensional (crosslinked) structure can be generated by reacting the unsaturated polyester with an unsaturated acid component that can react with the unsaturated polyester to form a crosslink. Suitable unsaturated monomers include styrene, methylstyrene, dimethylstyrene, vinyltoluene, divinylbenzene, dichlorostyrene, methyl acrylate, methyl methacrylate, ethyl acrylate, diallyl phthalate, vinyl acetate, triallyl cyanurate, acrylonitrile, acrylamide, and mixtures thereof. The relative amounts of unsaturated polyester and unsaturated monomers in the unsaturated polyester resin composition can vary over a wide range. Typically, the unsaturated polyester resin composition contains 20% to 80% by weight of monomers, preferably in the range of 30% to 70% by weight.

[0076] Alkyd resins comprise a resin that is a polymer of a polyol and a polyacid modified with a monofatty acid, typically containing at least some unsaturated fatty acids. The polyacid can be a dicarboxylic acid, most commonly represented by phthalic anhydride, isophthalic acid, maleic anhydride, itaconic acid, etc. Mixtures of two or more acids (or their anhydrides) may also be used. The second acid component is a monocarboxylic acid, represented by oleic acid, such as linoleic acid, linolenic acid, linolenic acid, and other acids containing two or more carbon-carbon conjugated double bonds or non-conjugated double bonds.

[0077] Vinyl ester resins include resins prepared by esterification of epoxy resins with unsaturated carboxylic acids (such as acrylic acid and methacrylic acid), and then dissolving the resulting product in a reactive solvent (such as styrene) (typically at a concentration of 35 to 45% by weight).

[0078] (Meth)acrylate resins include acrylate and / or methacrylate-functionalized substances, such as acrylates; methacrylates; diacrylates; dimethacrylates; acrylates and methacrylates with higher functionality, including monomers and oligomers; and combinations thereof.

[0079] Non-limiting examples of suitable olefinically unsaturated monomeric compounds include styrene and styrene derivatives, such as α-methylstyrene; vinyltoluene; indene; divinylbenzene; vinylpyrrolidone; vinylsiloxane; vinylcaprolactam; stilbene; and diallyl phthalate; dibenzylacetone; allylbenzene; methyl methacrylate; methyl acrylate; acrylic acid; methacrylic acid; diacrylate; dimethacrylate; acrylamide; vinyl acetate; triallyl cyanurate; triallyl isocyanurate; allyl compounds (e.g., (di)ethylene glycol diallyl carbonate); chlorostyrene; tert-butylstyrene; tert-butyl acrylate; butanediol dimethacrylate; and mixtures thereof. Suitable examples of (meth)acrylate reactive diluents are 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 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)citrate imide; (bis)itaconimide; and mixtures thereof.

[0080] Based on the weight of the curable resin component, the amount of olefinically unsaturated monomer in the curable resin used according to the embodiments of this disclosure is preferably at least 0.1% by weight, more preferably at least 1% by weight, and most preferably at least 5% by weight. The amount of olefinically unsaturated monomer is preferably no more than 50% by weight, more preferably no more than 40% by weight, and most preferably no more than 35% by weight.

[0081] Examples of commercially available unsaturated polyester resins suitable for the applications described in this disclosure include Pultru from AOC. ® Resins; VIPEL resin from AOC; COR31 and COR30 resins from Interplastic; Aropol resin from Ashland. ® Resins; and DION and STYPOL resins from Polynt / Reichold.

[0082] Examples of commercially available vinyl ester resins suitable for the applications described in this disclosure include Pultru from AOC. ®Resin; VIPEL from AOC ® Resins; CORVE resin from Interplastic; and Derakane resin from Ashland. ® Resin.

[0083] Examples of commercially available (meth)acrylate resins suitable for the applications described in this disclosure include MODAR from Ashland. ® And Elium from Arkema ® .

[0084] Organic peroxides

[0085] In one embodiment of the invention, the curable resin comprises at least one room-temperature stable organic peroxide (liquid at 25°C). These room-temperature stable liquid peroxides have a one-hour half-life temperature of 100°C or higher and are capable of curing the curable resin composition as described herein.

[0086] In one embodiment of the invention, the curable resin comprises at least one non-room temperature stable organic peroxide, which is liquid at 10 °C and has a one-hour half-life temperature of less than 100 °C.

[0087] In another embodiment, the curable resin composition is characterized by comprising at least two different types of organic peroxides capable of being cured together as described herein. Advantageously, the two types of organic peroxides are liquid, or blends thereof may be liquid. One class of organic peroxides can be stored stably at room temperature or even higher temperatures. These are referred to herein as “room temperature stable” organic peroxides. They can be safely stored for six months at temperatures of 20°C or higher, 25°C or higher, or even up to 30°C, with a peroxide concentration loss not exceeding 2% by weight. The 1-hour half-life temperature of room temperature stable organic peroxides is typically at least 100°C. The 10-hour half-life temperature of such room temperature stable organic peroxides may be at least 80°C or higher. In the context of this disclosure, “room temperature stable” means that the recommended maximum storage temperature for an organic peroxide is 30°C or higher to maintain a peroxide concentration loss of no more than 2% over 6 months to 1 year. However, according to certain aspects of this disclosure, the 10-hour half-life temperature of the room temperature stable organic peroxide present in the curable resin composition is 80°C or higher. According to other sources, the room-temperature stable organic peroxide exhibits a peroxide concentration loss of no more than 2% after storage for 3 months, 6 months, 9 months, or up to 12 months at storage temperature limits of up to 30°C or up to 38°C (100°F). Appropriate storage temperature limits for maintaining organic peroxide content can be found in Material Safety Data Sheets (SDS) or commercial product catalogs.

[0088] Room-temperature stable organic peroxides that can be used in the embodiments of this disclosure may include: peroxide esters, hemiperoxy ketals, peroxy ketals, monoperoxy carbonates, diacyl compounds, ketone peroxides, and hydroperoxides. Preferred room-temperature stable organic peroxides are peroxide esters, hemiperoxy ketals, peroxy ketals, and monoperoxy carbonates. Most preferred are peroxide esters, hemiperoxy ketals, peroxy ketals, and monoperoxy carbonates. Even more preferred are peroxide ester peroxides, peroxy ketals, and monoperoxy carbonate peroxides. More preferably, room-temperature stable organic peroxides are peroxide esters and monoperoxy carbonates. Preferred and more preferred room-temperature stable organic peroxides may have tert-butyl peroxy functional groups, tert-amyl peroxy functional groups, tert-hexyl peroxy functional groups, or tert-octyl peroxy functional groups.

[0089] Non-limiting examples of suitable room-temperature stable organic peroxides include: 1-tert-amylperoxy-1-methoxycyclohexane (LUPEROX) ® V10); 1,1-Di(tert-butylperoxy)-3,3,5-trimethylcyclohexane (LUPEROX) ® 231); 1,1-Di(tert-amylperoxy)cyclohexane (LUPEROX) ® 531M80); 1,1-Di(1-Butylperoxy)cyclohexane (LUPEROX) ® 331M80); 2,2-Di(tert-butylperoxy)butane (LUPEROX) ® 520M50); n-Butyl 4,4-di(tert-butylperoxy)valerate (LUPEROX) ® 230); Ethyl 3,3-di(tert-butylperoxy)butyrate (LUPEROX) ® PST); OO-tert-butyl-O-(2-ethylhexyl)-monoperoxycarbonate (LUPEROX) ® TBEC); OO-tert-amyl-O-(2-ethylhexyl)-monoperoxycarbonate (LUPEROX) ® TAEC); OO-tert-butylperoxy-O-isopropyl-monoperoxycarbonate (LUPEROX) ® TBICM75); Polyether tetra(tert-butyl peroxycarbonate) [LUPEROX] ® JWEB-50]; Di-tert-butyldisperoxide phthalate (LUPEROX) ® KDB); 2,5-Dimethyl-2,5-di(benzoylperoxy)hexane (LUPEROX) ® 118); tert-butyl peroxybenzoate (LUPEROX) ® P); tert-amyl peroxybenzoate (LUPEROX) ® TAP); tert-butyl peracetate (LUPEROX)® 7); tert-amyl peracetic acid (LUPEROX) ® 555); tert-butylperacetic acid (LUPEROX) ® 7M75); tert-butyl peroxyisobutyrate (LUPEROX) ® 80); 2-Butanone peroxide (LUPEROX) ® DDM-9 or a combination thereof.

[0090] Preferred room-temperature stable peroxides are: hemiperoxyketal; peroxide ester, monoperoxycarbonate; peroxyketal; 1-tert-amylperoxy-1-methoxycyclohexane; tert-butylperoxyacetate; tert-amylperoxyacetate; tert-butylperoxybenzoate; 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane; 1,1-di(tert-amylperoxy)-cyclohexane; 1,1-di(1-butylperoxy)-cyclohexane; 2,2-di(tert-butylperoxy)butane; OO-tert-butyl-O-(2-ethylhexyl)-monoperoxycarbonate; OO-tert-amyl-O-(2-ethylhexyl)-monoperoxycarbonate; OO-tert-amylperoxy-O-isopropyl-monoperoxycarbonate; OO-tert-butylperoxy-O-isopropyl monoperoxycarbonate; polyether tetra(tert-butylperoxycarbonate); or tert-amylperoxybenzoate.

[0091] The preferred room-temperature stable organic peroxide is: 1-tert-amylperoxy-1-methoxycyclohexane (LUPEROX) ® V10); 1,1-Di(tert-butylperoxy)-3,3,5-trimethylcyclohexane (LUPEROX) ® 231); 1,1-Di(tert-butylperoxy)cyclohexane (LUPEROX) ® 331M80); tert-amyl peroxybenzoate (LUPEROX) ® TAP); tert-butyl peroxybenzoate (LUPEROX) ® P); OO-tert-butyl-O-(2-ethylhexyl)-monoperoxycarbonate (LUPEROX) ® TBEC); OO-tert-butylperoxy-O-isopropyl-monoperoxycarbonate (LUPEROX) ® TBICM75); OO-tert-amylperoxy-O-isopropyl-monoperoxycarbonate (LUPEROX) ® TAICM75); OO-tert-amyl-O-(2-ethylhexyl)-monoperoxycarbonate (LUPEROX) ® TAEC); polyether tetra(tert-butyl percarbonate) [LUPEROX] ® JWEB-50]; tert-amyl peroxyacetate; 4,4-di(tert-butylperoxy)valerate n-butyl ester (LUPEROX) ®230).

[0092] A more preferred room-temperature stable organic peroxide is tert-amyl peroxybenzoate (LUPEROX). ® TAP); tert-butyl peroxybenzoate (LUPEROX) ® P); OO-tert-butyl-O-(2-ethylhexyl)-monoperoxycarbonate (LUPEROX) ® TBEC); OO-tert-butylperoxy-O-isopropyl-monoperoxycarbonate (LUPEROX) ® TBICM75); OO-tert-amylperoxy-O-isopropyl-monoperoxycarbonate (LUPEROX) ® TAICM75); OO-tert-amyl-O-(2-ethylhexyl)-monoperoxycarbonate (LUPEROX) ® TAEC); polyether tetra(tert-butyl percarbonate) [LUPEROX] ® [JWEB-50]; 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane; 1,1-di-tert-pentylperoxyhexane (LUPEROX) ® 531M80); 1,1-Di(tert-butylperoxy)cyclohexane (LUPEROX) ® 331M80); and 2,2-di(tert-amylperoxy)butane (LUPEROX) ® 520).

[0093] Even more preferred room-temperature stable organic peroxides are: tert-amyl peroxybenzoate (LUPEROX) ® TAP); tert-butyl peroxybenzoate (LUPEROX) ® P); OO-tert-butyl-O-(2-ethylhexyl)-monoperoxycarbonate (LUPEROX) ® TBEC); OO-tert-amyl-O-(2-ethylhexyl)-monoperoxycarbonate (LUPEROX) ® TAEC); 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane LUPEROX ® 231; 1,1-Di(tert-butylperoxy)cyclohexane LUPEROX ® 331M80; and 1,1-di-tert-pentylperoxyhexane (LUPEROX) ® 531M80).

[0094] Another type of organic peroxide is the non-room-temperature stable organic peroxide, which is liquid at 10°C or lower. These peroxides are unstable liquids at room temperature and are stored below room temperature (in a refrigerator or freezer). The 1-hour and 10-hour half-life temperatures of these more thermally unstable organic peroxides are lower than those of the room-temperature stable organic peroxides contained in the composition, thus requiring temperature-controlled refrigeration or freezing storage. For example, the 1-hour half-life temperatures of these non-room-temperature stable organic peroxides are less than 100°C, or less than 98°C, or less than 95°C, or less than 90°C, or less than 88°C, or less than 75°C. The 10-hour half-life temperatures of these non-room-temperature stable peroxides are 78°C or lower, 75°C or lower, 70°C or lower, or 60°C or lower. The most preferred non-room-temperature stable peroxides have a 1-hour half-life of less than 96°C to more than 85°C and a 10-hour half-life temperature of less than 78°C to more than 65°C. According to some implementation methods, the recommended maximum storage temperature for "non-room temperature stable" organic peroxides may not exceed 10°C, or for long-term storage of up to six months, not exceed 5°C.

[0095] For example, tert-butylperoxy-2-ethylhexanoate (LUPEROX) ® 26) The recommended maximum storage temperature in its original container is 50℉ (10°C) to maintain a peroxide concentration loss of no more than 2% over six months. Trigonox ® The maximum storage temperature for 421 (1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate) is 41℉ (5°C) to maintain a peroxide concentration loss of no more than 2% over a six-month period. Therefore, the maximum recommended storage temperature for various non-room-temperature stable organic peroxides may be 16°C or lower, or 10°C, or 5°C, or 0°C, or -5°C, or -10°C, or -15°C or lower, depending on the organic peroxide. According to certain aspects of this disclosure, the ten-hour half-life temperature of non-room-temperature stable organic compounds present in the curable resin composition may be 77°C or lower, or 75°C, or 65°C, or 60°C, or 55°C, or 50°C or lower. According to yet other aspects, the peroxide concentration loss of non-room-temperature stable organic peroxides after storage at 10°C or lower for 3 months, 6 months, 9 months, or longer does not exceed 2%.

[0096] According to some embodiments, the preferred non-room-temperature stable organic peroxides have a ten-hour half-life temperature range of 78°C or below to 69°C or below, and a one-hour half-life temperature range of 95°C or below to 88°C or below. According to some embodiments, the maximum storage temperature range for non-room-temperature stored liquid peroxides can be less than or equal to 16°C to less than or equal to 5°C.

[0097] Non-limiting examples of suitable types of liquid non-room temperature stable organic peroxide formulations that require frozen storage (below 0°C) are peroxide dicarbonates and peroxide esters.

[0098] Non-limiting examples of suitable liquid non-room temperature stable organic peroxide formulations that require refrigerated storage (greater than 0°C to less than 20°C) are diacyl groups and peroxide esters of organic peroxides.

[0099] Non-limiting examples of suitable non-room-temperature stable liquid organic peroxides are di(n-propyl)peroxydicarbonate; di(sec-butyl)peroxydicarbonate; di(2-ethylhexyl)peroxydicarbonate; 3-hydroxy-1,1-dimethylbutylperoxyneodecanate; 1,1-di(tert-butylperoxy)cyclohexane; tert-butylperoxy-2-ethylhexanoate; α-cumylperoxyneodecanate; tert-pentylperoxyneodecanate; tert-butylperoxyneodecanate; tert-pentylperoxynepentate; tert-butylperoxynepentate; 2,5-di(2-ethylhexanoylperoxy)-2,5-dimethylhexane; tert-pentylperoxy-2-ethylhexanoate; tert-butylperoxy-2-ethylhexanoate; tert-pentylperoxy-2-ethylhexanoate (LUPEROX) ® 575); tert-butylperoxy-2-ethylhexanoate (LUPEROX) ® 26); 2,5-Di(2-ethylhexanoylperoxy)-2,5-dimethylhexane (LUPEROX) ® 256); 1,1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate (Trigonox) ® 421); tert-hexylperoxy-2-ethylhexanoate; 2-Butanone peroxide (LUPEROX) ® DDM-9); or liquid dibenzoyl peroxide, or a combination thereof.

[0100] Preferably, the non-room-temperature stable organic peroxide ester is tert-amyl peroxide-2-ethylhexanoate (LUPEROX). ® 575); tert-butylperoxy-2-ethylhexanoate (LUPEROX) ® 26); 2,5-Di(2-ethylhexanoylperoxy)-2,5-dimethylhexane (LUPEROX) ® 256); 1,1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate (Trigonox) ® 421); tert-hexyl peroxy-2-ethylhexanoate; liquid dibenzoyl peroxide, or combinations thereof.

[0101] To avoid ambiguity, when benzoyl peroxide (also known as benzoyl peroxide) is in a liquid state (e.g., dissolved in a suitable solvent), it is classified as a non-room-temperature stable organic peroxide with a 1-hour half-life temperature of 91°C (i.e., less than 100°C). Benzoyl peroxide is only stable when stored in its solid state at 38°C (i.e., room temperature or higher).

[0102] More preferably, the non-room-temperature stable organic peroxide is tert-amyl peroxy-2-ethylhexanoate (LUPEROX). ® 575); 1,1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate (Trigonox ® 421); 2,5-Di(2-ethylhexanoylperoxy)-2,5-dimethylhexane (LUPEROX) ® 256); tert-butylperoxy-2-ethylhexanoate and tert-hexylperoxy-2-ethylhexanoate, used alone or in combination.

[0103] Most preferably, the non-room-temperature stable organic peroxide is tert-butylperoxy-2-ethylhexanoate; tert-amylperoxy-2-ethylhexanoate; and 2,5-di(2-ethylhexanoylperoxy)-2,5-dimethylhexane, used alone or in combination. Preferred combinations of room-temperature stable and non-room-temperature stable peroxides are selected from the following preferred room-temperature stable peroxides: tert-amylperoxybenzoate (LUPEROX) ® TAP); tert-butyl peroxybenzoate (LUPEROX) ® P); OO-tert-butyl-O-(2-ethylhexyl)-monoperoxycarbonate (LUPEROX) ® TBEC); LUPEROX ® JWEB-50; OO-tert-amyl-O-(2-ethylhexyl)-monoperoxycarbonate (LUPEROX) ® TAEC); 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane; 1,1-di-tert-pentylperoxyhexane (LUPEROX) ® 531M80) and 1,1-di-tert-butylperoxycyclohexane (LUPEROX) ® 331M80).

[0104] The following preferred non-room temperature stable peroxides may be selected from: tert-butylperoxy-2-ethylhexanoate; tert-amylperoxy-2-ethylhexanoate; 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate; and 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane.

[0105] In one embodiment, the non-room temperature stable peroxide may be free of perketal.

[0106] In one embodiment, the combination of room-temperature stable and non-room-temperature stable peroxides comprises 1,1-di-tert-butylperoxycyclohexane (LUPEROX). ® 331M80) and tert-amyl peroxy-2-ethylhexanoate (LUPEROX) ® 575) blends.

[0107] In another embodiment, the combination of room temperature stable and non-room temperature stable peroxides comprises a blend of tert-butyl peroxybenzoate and 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane.

[0108] In another embodiment, the combination of room temperature stable and non-room temperature stable peroxides comprises a blend of 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane and tert-butylperoxy-2-ethylhexanoate.

[0109] In another embodiment, the combination of room temperature stable and non-room temperature stable peroxides comprises a blend of 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane and tert-amylperoxy-2-ethylhexanoate.

[0110] In another embodiment, the combination of room temperature stable and non-room temperature stable peroxides comprises a blend of tert-butyl peroxybenzoate and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate.

[0111] In yet another embodiment, the combination of room temperature stable and non-room temperature stable peroxides comprises a blend of tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate.

[0112] In yet another embodiment, the combination of room-temperature stable and non-room-temperature stable peroxides comprises tert-butyl peroxybenzoate (LUPEROX). ® P) and tert-amyl peroxy-2-ethylhexanoate (LUPEROX) ® 575) blends.

[0113] In another embodiment, the combination of room-temperature stable and non-room-temperature stable peroxides comprises a blend of tert-amyl peroxybenzoate and tert-butyl peroxybenzoate, and a blend of tert-butyl peroxy-2-ethylhexanoate and tert-amyl peroxy-2-ethylhexanoate.

[0114] In yet another embodiment, the combination of room temperature stable and non-room temperature stable peroxides comprises a blend of OO-tert-butyl-O-(2-ethylhexyl)-monoperoxycarbonate and tert-butylperoxy-2-ethylhexanoate.

[0115] In yet another embodiment, the combination of room temperature stable and non-room temperature stable peroxides comprises a blend of OO-tert-butyl-O-(2-ethylhexyl)-monoperoxycarbonate and tert-amylperoxy-2-ethylhexanoate.

[0116] In yet another embodiment, the combination of room-temperature stable and non-room-temperature stable peroxides comprises a blend of OO-tert-amyl-O-(2-ethylhexyl)-monoperoxycarbonate and tert-amylperoxy-2-ethylhexanoate. According to one embodiment, the combination of room-temperature stable and non-room-temperature stable peroxides comprises tert-butylperoxybenzoate (LUPEROX). ® P) and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane (LUPEROX) ® 256) blends.

[0117] According to one embodiment, the combination of room-temperature stable and non-room-temperature stable peroxides comprises OO-tert-butyl-O-(2-ethylhexyl)-monoperoxycarbonate (LUPEROX). ® TBEC) and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane (LUPEROX) ® 256) blends.

[0118] According to one embodiment, the combination of room-temperature stable and non-room-temperature stable peroxides comprises tert-butyl peroxybenzoate (LUPEROX). ® P) and tert-amyl peroxy-2-ethylhexanoate (LUPEROX) ® 575) blends.

[0119] According to one embodiment, the combination of room-temperature stable and non-room-temperature stable peroxides comprises OO-tert-amyl-O-(2-ethylhexyl)-monoperoxycarbonate (LUPEROX). ® TAEC) and tert-amyl peroxy-2-ethylhexanoate (LUPEROX) ® 575) blends.

[0120] According to one embodiment, the combination of room-temperature stable and non-room-temperature stable peroxides comprises tert-butylperacetic acid (LUPEROX). ® 7M75) and tert-amyl peroxy-2-ethylhexanoate (LUPEROX) ® 575) blends.

[0121] According to one embodiment, the combination of room-temperature stable and non-room-temperature stable peroxides comprises poly(tert-butyl)peroxycarbonate (LUPEROX). ® JWEB50) and tert-amyl peroxy-2-ethylhexanoate (LUPEROX) ®575) blends.

[0122] According to one embodiment, the combination of room-temperature stable and non-room-temperature stable peroxides comprises OO-tert-amyl-O-(2-ethylhexyl)-monoperoxycarbonate (LUPEROX). ® TAEC) and tert-butylperoxy-2-ethylhexanoate (LUPEROX) ® 26) blends.

[0123] According to one embodiment, the combination of room-temperature stable and non-room-temperature stable peroxides comprises tert-butyl peroxybenzoate (LUPEROX). ® P) and tert-butylperoxy-2-ethylhexanoate (LUPEROX) ® 26) blends.

[0124] According to one embodiment, the combination of room-temperature stable and non-room-temperature stable peroxides includes 2-butanone peroxide (LUPEROX). ® DDM-9) and tert-amyl peroxy-2-ethylhexanoate (LUPEROX) ® 575) blends.

[0125] According to one embodiment, at least one non-room-temperature stable organic peroxide comprises at least one of the following: diacyl peroxide, ketone peroxide; hydroperoxide; peroxydicarbonate; peroxide ester; diacyl peroxide; di(n-propyl)peroxydicarbonate, di(sec-butyl)peroxydicarbonate; di(2-ethylhexyl)peroxydicarbonate; 3-hydroxy-1,1-dimethylbutylperoxyneodecanate; α-cumylperoxyneodecanate; tert-amylperoxyneodecanate; α-cumylperoxyneodecanate; tert-butylperoxyneodecanate; tert-amyl ... Butyl peroxyneopentate; 2,5-di(2-ethylhexanoylperoxy)-2,5-dimethylhexane; tert-amyl peroxy-2-ethylhexanoate; 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate; tert-hexyl peroxy-2-ethylhexanoate; tert-butyl peroxy-2-ethylhexanoate; dilauroyl peroxide solution; or dibenzoyl peroxide solution; preferably tert-amyl peroxy-2-ethylhexanoate; tert-butyl peroxy-2-ethylhexanoate; tert-hexyl peroxy-2-ethylhexanoate; or 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate.

[0126] According to yet another embodiment, at least one non-room-temperature stable organic peroxide comprises at least one of the following: peroxydicarbonate; peroxide ester; diacyl peroxide; tert-amyl peroxy-2-ethylhexanoate (LUPEROX). ® 575); tert-butylperoxy-2-ethylhexanoate (LUPEROX) ®26); 2,5-Di(2-ethylhexanoylperoxy)-2,5-dimethylhexane (LUPEROX) ® 256), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Trigonox) ® 421); tert-hexyl peroxide-2-ethylhexanoate; dilauryl peroxide solution; or dibenzoyl peroxide solution.

[0127] Desiredly, the curable resin composition comprises an amount of organic peroxide that effectively cures (polymerizes) the curable resin present in the curable resin composition substantially completely under selected curing conditions. This amount can vary considerably depending on parameters such as the selected organic peroxide, the components of the activator system (e.g., the specific metal salt and thiol-functionalized organic compounds present and their relative amounts), the reactivity of the curable resin, and the desired curing profile. However, generally, in various embodiments of this disclosure, the curable resin composition may advantageously comprise a total of at least 0.05 wt%, at least 0.1 wt%, at least 0.15 wt%, at least 0.2 wt%, at least 0.25 wt%, at least 0.3 wt%, at least 0.35 wt%, at least 0.4 wt%, or at least 0.6 wt% or more of organic peroxide, based on the weight of the curable resin. An advantage of embodiments of this disclosure is that, in at least some embodiments of this disclosure, relatively low amounts of organic peroxide can be used due to the accelerating effect of the combination of promoter salt and thiol-functionalized organic compounds. Therefore, the curable resin composition may contain an organic peroxide in total of no more than 2% by weight, no more than 1.5% by weight, or no more than 1% by weight, based on the weight of the curable resin.

[0128] According to other embodiments, the curable resin composition may contain a total of no more than 2% by weight of organic peroxides, based on the weight of the curable resin. For example, the curable resin composition may contain a total of up to 5% by weight of organic peroxides, based on the weight of the curable resin. According to some embodiments, the curable resin composition may contain a total of up to 5, 4.75, 4.5, 4.25, 4, 3.75, 3.5, 3.25, 3, 2.75, 2.5, 2.25, or up to 2% by weight of organic peroxides, based on the weight of the curable resin.

[0129] To achieve a target curing profile for the curable resin composition, the weight ratio of the room-temperature stable liquid organic peroxide to the non-room-temperature stable liquid organic peroxide can be varied as needed. For example, the weight ratio can be 4:1 to 1:4; 3:1 to 1:3; 2:1 to 1:2; or 1:1; or preferably 3:1 to 1:1; or 2:1 to 1:1; or 1:2 to 1:3; or 3:1 to 1:4, but higher or lower weight ratios are also possible. For example, the weight ratio can be 10:1 to 1:10; 9:1 to 1:9; 8:1 to 1:8; 7:1 to 1:7; 6:1 to 1:6; 5:1 to 1:5; or 4:1 to 1:4.

[0130] One advantage of the liquid organic peroxide formulations used in this disclosure is that a well-dispersed liquid can be prepared without diluting the organic peroxide / formulation / blend in styrene before mixing with the resin and impregnating the substrate to be cured. Therefore, the liquid organic peroxides, liquid peroxide formulations, and liquid organic peroxide blends used in this disclosure may contain less than 30% by weight, less than 20% by weight, less than 10% by weight, less than 5% by weight, less than 3% by weight, less than 2% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.1% by weight, or even 0% by weight of styrene, based on the total weight of the organic peroxide blend. Eliminating styrene eliminates the need for separate storage and handling of styrene, as well as additional processing steps, which is more environmentally friendly.

[0131] Metal salts (accelerators / activators / promoters)

[0132] One or more metal salts may be present in the curable resin composition of this disclosure. Such salts, accelerators, or promoters promote or activate the decomposition of one or more organic peroxides present in the curable resin composition, thereby accelerating the curing of the curable resin composition by the organic peroxides. Without wishing to be bound by any particular theory, it is believed that such metal salts can react with thiol-functionalized organic compounds also present in the curable resin composition to form complexes, which are the substances responsible for accelerating curing at high temperatures; or, thiols may otherwise assist in the decomposition of peroxides and the curing of the resin.

[0133] Suitable metal salts comprise salts of metals selected from the group consisting of Li, Al, Mg, Co, Fe, Cu, Zn, Ni, Mn, Cr, Sn, Au, Pd, or Pt. The anionic moiety of the salt may be a halide, nitrate, sulfate, or carboxylate. Other suitable anions include, for example, lactate, acetate, hexanoate, or naphthenate. Halide salts of transition metals are preferred. Halide salts of transition metals, especially chloride salts, are particularly preferred.

[0134] According to certain embodiments of this disclosure, at least one metal salt may comprise at least one transition metal halide. In a particularly preferred aspect, the at least one metal salt comprises at least one of the following: zinc, copper, or lithium halides, such as zinc chloride, lithium chloride, or copper(II) chloride. Preferred are zinc chloride, lithium chloride, copper(II) chloride, or combinations thereof. More preferred are zinc chloride and / or lithium chloride. Zinc chloride is a particularly preferred metal salt used in embodiments of this disclosure.

[0135] Typically, the curable resin composition contains a metal salt in an amount that effectively reduces the curing time of the curable resin compared to the curing time of a curable resin composition without the metal salt. This amount can vary depending on various factors, but in various embodiments of this disclosure, the metal salt is present in an amount providing a total of at least 5, 10, 20, 30, 40, or 50 ppm of a metal (selected from Li, Al, Mg, Co, Fe, Cu, Zn, Ni, Mn, Cr, Sn, Au, Pd, and Pt), based on the weight of the curable resin in the curable resin composition. In other embodiments, the curable composition contains a metal salt in an amount providing no more than 500, 400, 300, 200, or 100 ppm of such a metal in the curable resin composition, based on the weight of the curable resin.

[0136] Thiol-functionalized organic compounds

[0137] The curable resin compositions disclosed herein may comprise at least one thiol-functionalized organic compound. Such thiol-functionalized organic compounds are characterized in that each molecule of the organic compound contains at least one thiol (-SH) functional group, which, when used in embodiments of this disclosure, enhances the curing rate of the curable resin composition. According to some embodiments of this disclosure, at least one thiol-functionalized organic compound comprises two or more thiol functional groups per molecule. In one embodiment of this disclosure, the thiol group in the thiol-functionalized organic compound may be a single aliphatic thiol group or multiple aliphatic thiol groups (wherein each thiol group is attached to an aliphatic carbon atom). In still other embodiments, the thiol group is one or more primary aliphatic thiol groups. At least one thiol-functionalized organic compound may comprise an α-mercaptoacetate or β-mercaptopropionate of at least one alcohol. The alcohol may be a polyol containing two or more hydroxyl groups per molecule, such as ethylene glycol; trimethylolpropane; pentaerythritol, etc. Exemplary examples of suitable thiol-functionalized organic compounds include dipentene dithiol; ethylcyclohexyl dithiol; ethylene-1,2-bis-3-mercaptoacetate; ethylene-1,2-bis-3-mercaptopropionate; 1,2,3-propane trithiol; 1,2,6-hexane trithiol; pentaerythritol thiol; pentaerythritol tetra(2-mercaptoacetate); pentaerythritol tetra(3-mercaptopropionate); trimethylolpropane tri(3-mercaptopropionate); 1,1,1-propanetriyltri(mercaptoacetate); and thiolic derivatives having the general formula: R-(R'-CH(OH)-CH2-SH) n Wherein R is a straight-chain alkyl group having 3-30 carbon atoms, R' is a straight-chain alkylene group having 3-30 carbon atoms, and n is an integer from 2 to 6. Suitable thiol-functionalized organic compounds for embodiments of this disclosure also include any thiol compound disclosed in U.S. Patent No. 5,310,826, the entire disclosure of which is incorporated herein by reference for all purposes. Combinations of two or more different thiol-functionalized organic compounds may be used.

[0138] The most preferred thiol-functionalized organic compounds include trimethylolpropane tris(3-mercaptopropionate); pentaerythritol tetra(2-mercaptoacetate); pentaerythritol tetra(3-mercaptopropionate); and 1,1,1-propanetriyltris(mercaptoacetate). Among these, pentaerythritol tetra(3-mercaptopropionate) is even more preferred.

[0139] The amount of thiol-functionalized organic compounds present in a curable resin composition can vary as desired or required, depending on the activity of the thiol-functionalized organic compounds, the type and reactivity of other components in the curable resin composition, the desired curing profile, and other factors. However, generally, a curable resin composition may contain a total of at least 0.005% by weight, at least 0.01% by weight, or at least 0.02% by weight, but not more than 2% by weight, not more than 1% by weight, or not more than 0.5% by weight of thiol-functionalized organic compounds, based on the weight of the curable resin in the curable resin composition.

[0140] The weight ratio of the metal salt to the thiol-functionalized organic compound can be appropriately or desiredly varied depending on a variety of factors, including the specific metal salt and thiol-functionalized organic compound used, and the target curing profile of the curable resin composition. However, according to certain non-limiting aspects of this disclosure, the weight ratio can vary in the range of 1:1 to 1:10.

[0141] solvent

[0142] The curable resin compositions of this disclosure may additionally contain at least one solvent. Non-limiting examples of suitable solvents are alcohols, glycols, or glycol ethers.

[0143] Suitable alcohols are alkyl monools containing 1 to 30 carbon atoms. Non-limiting examples of suitable alcohols are tert-butanol, tert-amyl alcohol, ethanol, or isopropanol.

[0144] Non-limiting examples of suitable diols include ethylene glycol, propylene glycol, butanediol, dipropylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, pentaerythritol, or combinations thereof. Dipropylene glycol is preferred. As mentioned above, these diols can react with certain curable resin systems.

[0145] Non-limiting examples of suitable glycol ethers are methoxyethanol, ethoxyethanol, butoxyethanol, methoxypropanol, diethylene glycol monobutyl ether (DGMBE), or combinations thereof. Glycol ethers are preferred solvents in curable resin compositions, with diethylene glycol monobutyl ether (DGMBE) being the most preferred.

[0146] Other components

[0147] The aforementioned curable resins, peroxides, accelerator salts, and thiol-functionalized organic compounds can be combined with other additives commonly used in the field of cured resins, such as fillers, fibers, pigments, phlegmatizers, inhibitors (e.g., oxidative, thermal, and / or UV degradation inhibitors), lubricants, thixotropic agents, auxiliaries, and accelerators.

[0148] Examples of suitable fibers include glass fibers, carbon fibers, polymer fibers (e.g., polyamide fibers), natural fibers, and combinations thereof. The fiber may be in any suitable form, including in the form of a mat, in the form of a tow, or in other forms known in the art.

[0149] Examples of suitable fillers include talc, calcium carbonate, quartz, sand, silica, aluminum hydroxide, magnesium hydroxide, chalk, calcium hydroxide, clay, carbon black, titanium dioxide, and lime, as well as organic fillers (such as thermoplastics and rubber), and any mixtures of these fillers.

[0150] In one embodiment, this disclosure relates to an organic peroxide composition comprising a blend of:

[0151] • Non-room temperature stable organic peroxides;

[0152] • Room temperature stable organic peroxides;

[0153] • At least one transition metal halide salt dissolved in an alcohol, glycol, or glycol ether;

[0154] • At least one thiol-functionalized organic compound;

[0155] The organic peroxide composition is stable at room temperature for at least 1, 2, 3, 4, 5, 6, 7, 8, 10, 12, 14 or up to 24 hours.

[0156] In another embodiment, this disclosure relates to an organic peroxide composition comprising the following component: a non-room-temperature stable peroxide, namely tert-amyl peroxide-2-ethylhexanoate LUPEROX. ® 575 or 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Trigonox) ® 421); a room-temperature stable peroxide, which is tert-butyl peroxybenzoate (LUPEROX). ® P); a metal halide, preferably a Zn halide (ZnCl2), dissolved in a glycol ether, preferably in diethylene glycol monobutyl ether; and a thiol compound, preferably pentaerythritol tetra(3-mercaptopropionate). The organic peroxide composition described in this embodiment is stable at room temperature for at least 1, 2, 3, 4, 5, 6, 7, 8, 10, 12, 14 or up to 24 hours.

[0157] Formulation of curable resin compositions

[0158] The preparation of the curable resin composition according to embodiments of this disclosure can be carried out by any suitable method. For example, at least one curable resin; at least one room temperature stable organic peroxide (liquid at 25°C); at least one liquid non-room temperature stable peroxide (liquid at 10°C); at least one salt of at least one metal, said metal including at least one of the following: Li, Al, Mg, Co, Fe, Cu, Zn, Ni, Mn, Cr, Sn, Au, Pd, and Pt; at least one thiol-functionalized organic compound; and optionally at least one solvent comprising an alcohol, glycol, or glycol ether, which can be combined at approximately room temperature (e.g., 20°C to 30°C) to form a liquid and / or flowable curable resin composition, which is then heated to a temperature at which the curable composition is effectively cured.

[0159] Alternatively, certain components of the curable resin composition may be premixed to provide separate, storage-stable components, which are then combined when a curable resin composition is needed, and the cured composition is produced from the curable resin composition using the curable resin composition.

[0160] For example, one embodiment of this disclosure provides a system that can be used as a curable resin curing system. The system may include a first component and a second component. The first component may include at least one room-temperature stable organic peroxide that is liquid at 25°C and has a one-hour half-life temperature of 100°C or higher; and at least one non-room-temperature stable peroxide that is liquid at 10°C or lower and has a one-hour half-life temperature of less than 100°C, and optionally, the peroxide is substantially styrene-free, or optionally, is styrene-free. The second component may include at least one salt of at least one metal selected from the group consisting of Li, Al, Mg, Co, Fe, Cu, Zn, Ni, Mn, Cr, Sn, Au, Pd, and Pt; at least one thiol-functionalized organic compound; and optionally, at least one solvent comprising at least one of an alcohol, a glycol, or a glycol ether. The second component may be formulated as a solution or dispersion, wherein a solvent or dispersant, or a combination of solvents or dispersants, is used to dissolve the accelerator salt and the thiol-functionalized organic compound. To prepare a curable resin composition, a first component and a second component are combined with a third component comprising at least one curable resin in a desired proportion.

[0161] In another embodiment of this disclosure, a curable resin, a metal salt, and a thiol-functionalized organic compound are premixed for several days or weeks prior to the addition of a peroxide to form a curable resin composition, thereby initiating the actual curing process. This allows for the commercial production and sale of compositions already comprising a metal salt / thiol system, which, when combined with the peroxide described herein, provide the curable resin compositions of embodiments of this disclosure.

[0162] In another embodiment, the curing system comprises at least one room-temperature stable organic peroxide, which is liquid at 25°C and has a 1-hour half-life temperature of 100°C or higher; and at least one non-room-temperature stable peroxide, which is liquid at 10°C or lower and has a 1-hour half-life temperature below 100°C; at least one salt of at least one metal selected from the group consisting of Li, Al, Mg, Co, Fe, Cu, Zn, Ni, Mn, Cr, Sn, Au, Pd, and Pt; at least one thiol-functionalized organic compound; and optionally, at least one solvent comprising at least one of an alcohol, a glycol, or a glycol ether. Even though the system contains two peroxides, thiols, and metal salts in a single composition, the system retains storage stability.

[0163] Another embodiment of this disclosure is a cured system comprising at least one room-temperature stable organic peroxide, which is liquid at 25°C and has a one-hour half-life temperature of 100°C or higher; and at least one non-room-temperature stable peroxide, which is liquid at 10°C or lower and has a one-hour half-life temperature below 100°C; at least one salt of at least one metal selected from the group consisting of Li, Al, Mg, Co, Fe, Cu, Zn, Ni, Mn, Cr, Sn, Au, Pd, and Pt; at least one thiol-functionalized organic compound; and at least one solvent comprising at least one alcohol, glycol, or glycol ether, preferably a glycol ether solvent. Even if the system contains two peroxides, thiols, metal salts, and at least one alcohol, glycol, or glycol ether in a single composition, the system still exhibits storage stability.

[0164] In another embodiment, the combination of room-temperature stable and non-room-temperature stable peroxides comprises tert-butyl peroxybenzoate (LUPEROX). ® P), tert-amyl peroxy-2-ethylhexanoate (LUPEROX) ® A blend of 575), ZnCl2, PETMP (pentaerythritol tetra(3-mercaptopropionate)) and diethylene glycol monobutyl ether (DGMBE) (as an optional solvent).

[0165] Embodiments of this disclosure also contemplate two-component systems comprising a first component and a second component, wherein the first component comprises at least one pre-accelerated curable resin (a combination of at least one curable resin, at least one metal salt, and at least one thiol-functionalized organic compound), and the second component comprises a mixture of different organic peroxides used in embodiments of this disclosure. In addition to room-temperature stable peroxides and non-room-temperature stable peroxides, the second component may also comprise the metal salts, thiol compounds, and solvents disclosed herein. As used herein, the term "two-component system" refers to a system in which two components (A and B) are physically separated from each other [e.g., in separate cylinders, compartments, totes, barrels, or other containers], wherein components A and B are physically combined (mixed) only when the system is used to form a cured resin.

[0166] In a particularly preferred embodiment of this disclosure, a curing system comprising the following is provided:

[0167] i) The first component, which includes:

[0168] At least one room-temperature stable organic peroxide, which is liquid at 25°C and has a 1-hour half-life temperature of 100°C or higher; and

[0169] At least one non-room-temperature stable organic peroxide, which is liquid at 10°C or lower and has a one-hour half-life temperature of less than 100°C; and

[0170] ii) The second component, which includes:

[0171] At least one salt of at least one metal, said metal comprising at least one of the following: Li, Al, Mg, Co, Fe, Cu, Zn, Ni, Mn, Cr, Sn, Au, Pd, or Pt;

[0172] At least one thiol-functionalized organic compound; and

[0173] Optionally, at least one solvent, said solvent comprising at least one of an alcohol, a glycol, or a glycol ether.

[0174] Optionally, the first component may be styrene-free.

[0175] Uses of Curable Resin Compositions

[0176] The curable resin compositions of this disclosure are particularly suitable for applications requiring a prolonged open time at ambient temperature (e.g., room temperature or 25°C) but a relatively short curing time when the curable resin composition is heated to a high temperature (e.g., at least 50°C, 60°C, 70°C, or 80°C, but typically not exceeding 250°C, 240°C, 230°C, 220°C, 210°C, or 200°C). In various embodiments of this disclosure, the curing time (i.e., the heating time of the curable resin composition) is at least 0.5, 1, 2, 3, 4, or 5 minutes, but not exceeding 10 hours, 9 hours, 8 hours, 7 hours, 6 hours, 5 hours, 4 hours, 3 hours, 2 hours, 1 hour, or 0.5 hours. For example, the curable resin composition may be heated for 1 minute to 20 minutes. The heating of the curable resin composition may be carried out at a temperature and time sufficient to allow the initial monomer reaction rate in the cured resin to reach at least 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or even 100%. The percentage of monomer reaction can be calculated by analyzing the percentage of unreacted monomer remaining in the cured resin relative to the total composition formulation.

[0177] Such applications include, for example, composite material systems in which a matrix (e.g., a sheet-like or filamentous fibrous matrix, such as glass fiber, polymer fiber, or carbon fiber) is impregnated with a curable resin composition to form an impregnated matrix, which is then shaped into the desired configuration and cured to provide a composite material article.

[0178] For example, the curable resin compositions of embodiments of this disclosure can be used in so-called “curing-in-situ” piping systems. Curing-in-situ pipe (CIPP) is one of several trenchless repair methods for repairing existing pipelines, such as water, sewage, gas, and chemical pipelines. CIPP is a seamless, pipe-within-a-pipe approach that can repair pipes of varying diameters and constructions, thus avoiding the need to excavate existing pipelines for repair or replacement. In the context of this disclosure, a flexible liner [including polyester fabric, fiberglass cloth, or other types of fabric (woven or nonwoven)] can be impregnated with a curable resin composition to provide a resin-impregnated liner, which is then flipped or pulled into the damaged pipe (e.g., as described in U.S. Patent Nos. 4,009,063 and 4,064,211, the entire disclosure of each of which is incorporated herein by reference for all purposes). The liner may be in the form of a laminate comprising a layer of nonwoven fabric coated with a thermoplastic sheet material, wherein the nonwoven fabric has been impregnated with the curable resin composition. The resin-impregnated liner can be flipped using water or air pressure. Once located in a damaged pipe, the resin-impregnated liner can be heated to a temperature that effectively initiates curing of the curable composition by any suitable method. For example, hot water or steam can be introduced into the resin-impregnated liner already placed in the damaged pipe to provide heat. In some cases, the ambient temperature within the damaged pipe containing the resin-impregnated liner can be high enough to achieve the desired curing. Once cured, the resin-impregnated liner becomes relatively hard and rigid, and is therefore capable of serving as a conduit for conveying liquids, gases, etc. The long open-time characteristics of the curable resin composition of the present disclosure provide a significant advantage for in-situ curing piping systems, as the resin-impregnated liner maintains flexibility and maneuverability for an extended period and can be prepared in advance prior to its actual deployment, provided it is kept below the temperature at which the curable resin begins to cure at a significant rate. While the open time of the resin-impregnated lining can be further extended by refrigeration, in some embodiments of this disclosure, refrigeration is not required because the curable resin composition has sufficient open time (e.g., 15, 30, 45, 60 minutes or longer) even at ambient temperatures of 20-25°C.

[0179] Therefore, embodiments of this disclosure include resin-impregnated linings comprising a lining impregnated with a curable resin composition according to any embodiment described herein. Another embodiment of this disclosure provides a method for preparing a resin-impregnated lining suitable for in-situ curing pipe methods, wherein the method includes impregnating the lining with a curable resin composition according to any embodiment described herein. Embodiments of this disclosure also provide a method for lining a channel or pipe cavity having an inner surface, comprising a) introducing a resin-impregnated lining into the cavity, wherein the resin-impregnated lining comprises a lining impregnated with a curable resin composition according to any embodiment described herein, and b) introducing steam or hot water into an inner opening of the resin-impregnated lining to bring the resin-impregnated lining into close contact with the inner surface of the channel or pipe, and activating the curing of the curable resin composition present in the resin-impregnated lining. The resin-impregnated lining is initially flexible but subsequently cures into a rigid state within the channel or pipe.

[0180] The curable resin compositions of this disclosure can also be used in pultrusion processes. As is known in the art, pultrusion is a combination of stretching and extrusion processes. A reinforcing structure (which may be fiber, fabric, or other forms) is continuously drawn from a spool or the like and impregnated with a matrix material, which in the context of this disclosure may be a curable resin material as described herein. For example, such impregnation can be performed in a wet bath. The reinforcing structure impregnated with the curable resin composition is drawn through a heated die to form its final shape. Final curing of the composite material typically also occurs in the downstream portion of the die. The long opening time but short curing time of the curable resin compositions of this disclosure make them particularly suitable for such pultrusion processes.

[0181] An exemplary embodiment of this type of pultrusion process can be generally described as follows: A reinforcing material in the form of fibers is held on a frame or spindle or other suitable support. Fiber bundles may be passed through preforming guides to bond the fibers in a preliminary grouping manner, or the fibers may be pre-bonded to form woven or braided bundles. A tank is provided containing a volume of liquid curable resin composition (as a resin bath), which is maintained at a temperature at which curing does not occur at a significant rate. The reinforcing material made of fiber bundles (e.g., filaments) is drawn through the resin bath, allowing the curable resin composition to immerse the reinforcing material. The wetted filaments may be drawn through rollers and a second material guide, further shaping the composite material. The composite filaments are formed in a pultrusion die, where they may also be cured under the action of one or more heaters. Composite products that can be manufactured by pultrusion include, for example, ladder assemblies, door and window profiles, structural members, cable trays, tool handles, pipes; conduits; reinforcing bars; wind turbine blade assemblies, panels; and so on.

[0182] In addition to the methods described above, the curable resin compositions of the embodiments of the present invention can also be used in resin transfer molding processes. As is well known in the art, resin transfer molding comprises a process in which reinforcing material (e.g., a fiber pad, matrix, or preform) is placed in a mating molding tool. The tool is closed and a gap is filled with curable resin, injecting the reinforcing material. The tool is typically heated, and curing is initiated under high temperature and tool compression conditions. Further explanation of conventional resin transfer molding appears in U.S. Patent No. 4,762,740, which is incorporated herein by reference in its entirety for all purposes. In one type of resin transfer molding, one of the half-molding components is a flexible bag or sheet called a vacuum bag.

[0183] An exemplary implementation of this type of resin transfer molding process can be generally described as follows: A reinforcing material in the form of woven fibers is laid in a matching molding tool, or inserted as a preform. The tool is closed, and a curable resin is injected into the gap; this resin can be injected as a fully pre-mixed resin or after mixing multiple components at the injection point. The heated tool compresses the resin / reinforcing system, and curing occurs. The tool is opened, the cured part is removed, and the process is repeated.

[0184] The curable resin composition of this disclosure can also be used in the manufacture of prepreg sheets, strips, or fabrics, wherein a fiber matrix (non-woven or woven glass fiber, polymer fiber, carbon fiber, etc.) is impregnated with the curable resin composition. Then, multiple layers of fiber matrices impregnated with the curable resin composition are arranged or layered, with the fibers in each layer aligned in the same or different directions. The layers are then molded and cured by pressing or other types of compaction while heated, thereby forming a cured composite material article.

[0185] In this specification, embodiments have been described in a manner that allows for clear and concise explanation; however, it is intended and should be understood that embodiments may be combined or separated in various ways without departing from this disclosure. For example, it should be understood that all preferred features described herein apply to all aspects of this disclosure.

[0186] In some embodiments, this disclosure may be interpreted as excluding any elements or method steps that do not materially affect the fundamental and novel characteristics of the composition or method. Furthermore, in some embodiments, this disclosure may be interpreted as excluding any elements or methods not specified herein.

[0187] Although this disclosure has been shown and described herein with reference to specific embodiments, it is not intended to be limited to the details shown. Rather, various modifications in detail may be made within the scope of the claims without departing from this disclosure.

[0188] Example

[0189] The following materials were used in the embodiments:

[0190] Base resin: UPR (unsaturated polyester resin) Aropol ® 2036C (isophthalic acid resin from Ashland).

[0191] PETMP: Pentaerythritol tetra(3-mercaptopropionate).

[0192] LUPEROX ® 575: Tert-butylperoxy-2-ethylhexanoate (Arkema). (Non-room temperature stable)

[0193] LUPEROX ® M520M50: 2,2-Di(tert-amylperoxy)butane (Arkema) (room temperature stable)

[0194] LUPEROX ® 331M80: 1,1-Di(tert-butylperoxy)cyclohexane (Arkema) (room temperature stable)

[0195] LUPEROX ® 531M80: 1,1-Di(tert-amylperoxy)cyclohexane (Arkema) (room temperature stable)

[0196] LUPEROX ® P: tert-butylperoxybenzoate. (Room temperature stable)

[0197] LUPEROX ® TBEC: Tert-butylperoxy-2-ethylhexyl carbonate (Arkema). (Room temperature stable)

[0198] DGMBE: Diethylene glycol monobutyl ether

[0199] ZnCl2: Zinc chloride

[0200] LiCl: Lithium chloride

[0201] UPR: Unsaturated polyester resin

[0202] Example 1: Combination of non-room temperature stable peroxides with room temperature stable peroxides

[0203] Formulations in the uncured base resins shown in Table 1 were prepared, which contained tert-butylperoxy-2-ethylhexanoate (LUPEROX). ® 575), zinc chloride (ZnCl2), and pentaerythritol tetramercaptopropionate (PETMP).

[0204] Table 1:

[0205]

[0206] Table 1 shows the combination of UPR base resin with PETMP (thiol-functionalized organic compound) and ZnCl2, with 0.20% by weight of LUPEROX added. ® 575 (Non-room temperature stable organic peroxide). Using the compositions in Table 1 as reservoirs, a portion of the resin compositions in Table 1 were used to prepare various combinations of non-room temperature stable organic peroxides and room temperature stable peroxides, as shown in Table 2.

[0207] Therefore, the formulations containing non-room-temperature stable organic peroxides shown in Table 1 were combined with various additional room-temperature stable organic peroxides shown in Table 2. Each room-temperature stable peroxide was added to the resin in the following amounts to achieve a final concentration of 0.20% by weight (based on pure peroxide), and any solvents in the peroxide formulations were corrected. For example, LUPEROX... ® 520M50 is a room-temperature stable peroxide, diluted to 50% by weight in mineral oil. Therefore, 0.4% by weight of LUPEROX is required. ® The 520M50 peroxide formulation provides 0.2% by weight (based on pure peroxide). See Table 2.

[0208] Table 2

[0209]

[0210] Organic peroxide blends were added to the resins shown in Table 2, cured, and the exothermic temperature was monitored to observe the curing rate. The UPR resins containing various peroxide blends in Table 2 were subjected to the standard SPI gel test in an 80°C oil bath. The curing results for each organic peroxide are as follows: Figure 1 As shown.

[0211] It is worth noting that all peroxides in Table 2 (including LUPEROX used alone) ® 575) are all blended with the novel accelerator system of this disclosure, as shown in Table 1. Due to the use of the accelerator solution, all Figure 1 The peroxides shown (including LUPEROX used alone) ® Both 575 and 575 achieved faster curing curves (compared to those without accelerator solutions).

[0212] Even without accelerator solutions, the fast-curing non-room temperature (refrigerated) peroxide LUPEROX... ® 575 also cures more slowly. This can be seen from... Figure 2This can be seen from the example: when Luperox is used without any accelerator solution. ® When 575 (a non-room temperature stable peroxide) is tested at 60°C, it takes a very long time to reach peak exothermic activity, up to 60 minutes.

[0213] In contrast, when Luperox ® When 575 is mixed with our accelerator solution and tested at 60°C, it reaches peak exothermic activity much faster, in just 23 minutes, as shown in Example 2. Figure 2 As shown.

[0214] Reference Figure 1 Surprisingly, when UPR resin was cured with zinc chloride metal salt and PETMP thiol-functionalized organic compounds, the better thermal stability (room temperature stable organic peroxide) was achieved when combined with LUPEROX. ® The combined use of 575 (a non-room temperature stable organic peroxide) produced a more desirable, faster, and equivalent exothermic curing profile; compared to using LUPEROX alone, which has lower thermal stability. ® 575. refer to Figure 1 Specifically, [LUPEROX] ® TBEC & LUPEROX ® Blends of

[575] ; and [LUPEROX] ® 520 & LUPEROX ® The blend of 575 was unexpectedly better than using LUPEROX alone. ® 575 achieves a more desirable, faster curing curve. Note: LUPEROX ® TBEC and LUPEROX ® 520 is a slower, more thermally stable room-temperature stable peroxide. This result was quite unexpected, as it is significantly different from LUPEROX. ® When 575 is blended with slower room-temperature stable peroxides, it is expected that using non-room-temperature stable peroxides (LUPEROX) alone will be more effective. ® 575) will cure faster.

[0215] [LUPEROX ® P & LUPEROX ® Blends of

[575] ; and [LUPEROX] ® 331M50 & LUPEROX ® The blend of

[575] provides an equivalent curing onset time, but compared to using LUPEROX alone... ®Compared to 575, it exhibits an unexpectedly higher, more expected, extended curing heat of release 8 minutes after peak exothermic reaction. This higher extended curing heat of release will contribute to achieving more complete curing.

[0216] [LUPEROX ® 575 & LUPEROX ® The blend of 531M80 achieved peak exothermic response in ~9 minutes, compared to using LUPEROX alone. ® 575 is 1 minute slower than the same accelerator system. However, it is worth noting that [LUPEROX] ® 575 & LUPEROX ® The blend of 531M80, when mixed with our accelerator system, still achieved faster curing than the system without our novel accelerator solution.

[0217] Example 2: Using Luperox alone ® 575 (non-room temperature stable organic peroxide), with and without our novel accelerator system.

[0218] This demonstrates how our novel accelerator system accelerates the curing of Luperox (used only) at 60°C compared to solutions without the accelerator. ® 575 unsaturated polyester resin (UPR). Please refer to [reference needed]. Figure 2 Without using any accelerator solution, for LUPEROX ® 575 (a non-room-temperature stable organic peroxide) underwent a gelation test at 60°C, reaching a peak exothermic response at 60 minutes. However, when Luperox... ® When 575 was mixed with the accelerator solution of this embodiment and tested at 60°C, the peak exothermic reaction was reached in just 23 minutes. A comparison chart is shown below. Figure 2 As shown.

[0219] Table 3

[0220]

[0221] Example 3: Organic peroxide blends containing transition metal salts and thiol-functionalized organic compounds

[0222] This embodiment illustrates the novelty of our accelerator solution. In this embodiment, we teach that a safe, one-component solution comprising an organic peroxide and the accelerator solution of this disclosure can be produced unexpectedly. Producing a safe, one-component solution of an organic peroxide containing an accelerator solution is highly unusual, unexpected, and novel. Those skilled in the art will know that adding any accelerator system directly to an organic peroxide is extremely unsafe, as spontaneous and very dangerous decomposition of the organic peroxide is expected. Therefore, the ability to prepare a safe organic peroxide solution containing an accelerator solution is novel and provides a degree of safety assurance to the customer, as no violent decomposition will occur even if the accelerator blend is accidentally mixed with the organic peroxide.

[0223] A room temperature stable mixture was prepared comprising a non-room temperature stable peroxide, a room temperature stable peroxide, and an accelerator system according to embodiments of the present disclosure, wherein the accelerator system comprises a blend of DGMBE, ZnCl2, and PETMP.

[0224] Figure 3 Comparison of tert-butyl peroxybenzoate (Luperox) ® P (room temperature stable organic peroxide) and tert-amyl peroxy-2-ethylhexanoate (LUPEROX) ® The high-temperature stability at 30°C of a blend of 575 (a non-room-temperature stable organic peroxide) in a weight ratio of (2:1) was evaluated with and without our novel accelerator solution. (Note: Unsaturated polyester resin was not used in this embodiment.) According to the practice of embodiments of this disclosure, it is unusual to add the accelerator solution directly to the organic peroxide formulation under ambient conditions, as those skilled in the art would expect the peroxide to decompose rapidly. Furthermore, even when the peroxide composition and accelerator package were kept in a 30°C water bath for four hours, unexpected and sustained high-temperature stability (no decomposition) was observed.

[0225] Specifically, two glass tubes were prepared by adding a peroxide blend totaling 0.9 g to each tube. The blend consisted of tert-butyl peroxybenzoate and tert-amyl peroxy-2-ethylhexanoate in a 2:1 weight ratio. An accelerator solution was also added to one of these tubes. This accelerator blend solution composition consisted of 86.5% DGMBE, 11% PETMP, and 2.5% ZnCl2. This accelerator solution was added directly to the pure peroxide blend. Surprisingly, at a laboratory ambient temperature of 73℉ (22.7℃), neither a reaction nor immediate decomposition occurred. This was highly unexpected. Those skilled in the art would expect immediate decomposition of the peroxides.

[0226] To further investigate the peroxide blends, two test tubes (containing and without the accelerator solution) were placed in a water bath set at 30°C (86°F) and kept at the high temperature for 4 hours. Figure 3 The results showed that neither the peroxide blends containing any accelerator solution nor the peroxide blends containing the accelerator solution exhibited any visible signs of peroxide decomposition. This data indicates that, unexpectedly, the novel accelerator solution, when added to the peroxide blends, possessed the same thermal stability as the peroxide blends without any accelerator solution. Therefore, this data demonstrates that we can prepare unexpectedly safe one-component solutions of organic peroxides plus our novel accelerator solution.

[0227] Furthermore, after maintaining the solution at 30°C for four hours, both solutions were removed from the water bath and placed in a heating block. The heating block was heated at a rate of 4°C / min. (Reference) Figure 3 The study showed that the two solutions were similarly exothermic, indicating that blending organic peroxides with accelerator solutions remains feasible.

[0228] In summary, we have demonstrated that the room-temperature stable and non-room-temperature stable organic peroxide blends containing our novel accelerator solution exhibit good thermal stability and good peroxide decomposition performance at high temperatures. We have also demonstrated that, unexpectedly, further blending of the non-room-temperature stable blends and the room-temperature stable peroxide blends with the accelerator solution of this disclosure results in stability comparable to that of the peroxide blends without any accelerator solution.

[0229] This data shows that the pure peroxide blend containing the accelerator system used in the practice of the embodiments of this disclosure has completely unexpected environmental temperature (22.7°C) stability and high temperature stability at 30°C.

[0230] Comparative Example 4: Decomposition ratio of room temperature organic peroxides and the same room temperature organic peroxides blended only with ZnCl2 Comparison

[0231] By placing approximately 1 gram of pure tert-butyl perbenzoate (LUPEROX) in a test tube ® A rapid thermal decomposition test was performed using tert-butyl perbenzoate (P). Approximately 1 gram of the same organic peroxide was placed in a second test tube, along with 0.02 g of zinc chloride (ZnCl2). Both test tubes were placed in a block heated at a rate of approximately 4 °C / min. The results were then compared. ® The decomposition temperature of P). The results are as follows: Figure 4 As shown. As expected, Figure 4 The results show that ZnCl2 destabilizes organic peroxides, causing them to exotherm earlier than pure organic peroxides.

[0232] Example 5: Room temperature organic peroxides and the same room temperature organic compounds already combined with our novel accelerator solution Comparison of peroxide decomposition

[0233] Our accelerator solution contains: 86.5 wt% DGMBE, 11 wt% PETMP, and 2.5 wt% ZnCl2

[0234] In this embodiment, the selected room-temperature organic peroxide is Luperox. ® P (tert-butyl perbenzoate) is the same peroxide used in Example 4. For this test, approximately 1 gram of pure Luperox... ® P is placed in a test tube. Approximately 1 gram of pure Luperox is added to a second test tube. ® P and 0.20 g of accelerator solution. The amount of this accelerator solution results in 1 g of Luperox. ® 0.005 g of ZnCl2 was added to the P-peroxide solution. (Note: PETMP is also present in our novel accelerator solution.) Both solutions were heated at a rate of 4 °C / min to rapidly decompose the organic peroxide. Figure 5 )

[0235] Figure 5 The solid line in the figure indicates that pure Luperox mixed with our novel accelerator solution... ® P-peroxide is more effective than pure Luperox without our novel accelerator solution. ® P-peroxide (dashed line) surprisingly exhibits better thermal stability. Therefore, quite unexpectedly, we show that stable room-temperature peroxide solutions containing accelerators can be prepared using the teachings of embodiments of this disclosure.

[0236] Example 6: In practice of the embodiments of this disclosure, the effect of LiCl (instead of ZnCl2) on promoting the curing of unsaturated polyester resins by room temperature organic peroxides at 80°C was evaluated.

[0237] Table 4

[0238]

[0239] The lithium chloride accelerator solution contains 88% by weight diethylene glycol monobutyl ether (DGMBE), 10% by weight PETMP, and 2% by weight lithium chloride.

[0240] Standard gel tests were performed on the curing of UPR at 80°C, comparing two formulations: Formulation 1 used 2.50% by weight of Luperox. ® P and 0.50 wt% of our novel accelerator solution (using LiCl), Formulation 2 uses 2.50 wt% Luperox. ® P, but does not contain any accelerator solutions containing LiCl. Figure 6 The results shown clearly demonstrate that our LiCl-containing accelerator solution readily promotes Luperox. ® P, thereby enabling the unsaturated polyester resin to cure rapidly.

[0241] Example 7: Promotion by a single room-temperature organic peroxide

[0242] In this embodiment, a gelation test was performed at 60°C to compare the results with those of products containing Luperox. ® P or Luperox solutions containing our novel ZnCl2-based accelerator ® The curing properties of P's unsaturated polyester resin were tested. The formulations used in this test are shown in Table 5.

[0243] Table 5

[0244]

[0245] The accelerator solution consists of 86.5% DGMBE, 11% PETMP, and 2.5% ZnCl2.

[0246] like Figure 7 As can be seen, the formulation containing our novel accelerator solution exothermics and solidifies within 30 minutes. In contrast, the formulation without any accelerator solution did not exhibit any exothermic reaction after two hours of operation.

Claims

1. A curable resin composition comprising: a) At least one curable resin that can be cured by a liquid organic peroxide; b) At least one room-temperature stable organic peroxide that is liquid at 25°C and has a half-life temperature of 100°C or higher at one hour; c) Optionally, at least one non-room-temperature stable organic peroxide is liquid at 10°C or lower and has a half-life temperature of less than 100°C in one hour. d) At least one salt of at least one metal, said metal comprising at least one of the following: Li, Al, Mg, Co, Fe, Cu, Zn, Ni, Mn, Cr, Sn, Au, Pd, or Pt; e) at least one thiol-functionalized organic compound; and f) Optionally, at least one solvent, said solvent comprising at least one of alcohol, glycol or glycol ether.

2. The curable resin composition of claim 1, wherein c) a non-room temperature stable organic peroxide is contained.

3. The curable resin composition of claim 1 or claim 2, wherein the at least one thiol-functionalized organic compound comprises at least one thiol-functionalized organic compound containing two or more thiol functional groups.

4. The curable resin composition according to any one of claims 1-3, wherein the at least one thiol-functionalized organic compound comprises an α-mercaptoacetate or β-mercaptopropionate of at least one alcohol.

5. The curable resin composition according to any one of claims 1-4, wherein the at least one thiol-functionalized organic compound comprises at least one thiol-functionalized organic compound containing at least one of the following: dipeptene dithiol; ethylcyclohexyl dithiol; ethylene-1,2-bis-3-mercaptoacetate; ethylene-1,2-bis-3-mercaptopropionate; 1,2,3-propane trithiol; 1,2,6-hexane trithiol; pentaerythritol thiol; pentaerythritol tetra(2-mercaptoacetate); pentaerythritol tetra(3-mercaptopropionate); trimethylolpropane tri(3-mercaptopropionate); 1,1,1-propanetriyltri(mercaptoacetate); and thiol derivatives having the general formula: R-(R'-CH(OH)-CH2-SH) n , where R is a straight-chain alkyl group having 3-30 carbon atoms, R' is a straight-chain alkylene group having 3-30 carbon atoms, and n is an integer from 2 to 6.

6. The curable resin composition according to any one of claims 2-5, wherein the at least one non-room temperature stable organic peroxide comprises at least one of the following: diacyl peroxide, peroxydicarbonate; peroxide ester; di(n-propyl)peroxydicarbonate; di(sec-butyl)peroxydicarbonate; di(2-ethylhexyl)peroxydicarbonate; 3-hydroxy-1,1-dimethylbutylperoxyneodecanate; α-cumylperoxyneodecanate; tert-amylperoxyneodecanate Ester acid esters; α-cumyl peroxyneodecanate; tert-butyl peroxyneodecanate; tert-pentyl peroxyneovatate; tert-butyl peroxyneovatate; 2,5-di(2-ethylhexanoylperoxy)-2,5-dimethylhexane; tert-pentyl peroxy-2-ethylhexanoate; 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate; tert-hexyl peroxy-2-ethylhexanoate; tert-butyl peroxy-2-ethylhexanoate; dilauroyl peroxide solution; or dibenzoyl peroxide solution; Preferred esters include tert-amyl peroxy-2-ethylhexanoate; tert-butyl peroxy-2-ethylhexanoate; tert-hexyl peroxy-2-ethylhexanoate; or 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate.

7. The curable resin composition according to any one of claims 2-6, wherein the at least one non-room temperature stable organic peroxide comprises at least one of the following: peroxydicarbonate; peroxide ester; diacyl peroxide; tert-amyl peroxy-2-ethylhexanoate; tert-butyl peroxy-2-ethylhexanoate; 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate; tert-hexyl peroxy-2-ethylhexanoate; dilauryl peroxide solution; or dibenzoyl peroxide solution.

8. The curable resin composition according to any one of claims 1-7, wherein the at least one room-temperature stable organic peroxide comprises at least one of the following: hemiperoxyketal; peroxide ester, monoperoxycarbonate; peroxyketal; 1-tert-amylperoxy-1-methoxycyclohexane; tert-butylperoxyacetate; tert-amylperoxyacetate; tert-butylperoxybenzoate; 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane; 1,1-di(tert-amyl)-3,3,5-trimethylcyclohexane; Peroxy-cyclohexane; 1,1-di(1-butylperoxy)-cyclohexane; 2,2-di(tert-butylperoxy)butane; OO-tert-butyl-O-(2-ethylhexyl)-monoperoxycarbonate; OO-tert-pentyl-O-(2-ethylhexyl)-monoperoxycarbonate; OO-tert-pentylperoxy-O-isopropyl-monoperoxycarbonate; OO-tert-butylperoxy-O-isopropyl-monoperoxycarbonate; polyether tetra(tert-butylperoxycarbonate); or tert-pentylperoxybenzoate.

9. The curable resin composition according to any one of claims 1-8, wherein at least one salt of the at least one metal comprises a halide, nitrate, sulfate, carboxylate, lactate, acetate, hexanoate, or cycloalkanoate of at least one transition metal.

10. The curable resin composition according to any one of claims 1-9, wherein at least one salt of the at least one metal comprises at least one of copper halide, zinc halide, or lithium halide, preferably ZnCl2 and / or LiCl and / or copper(II) chloride, most preferably ZnCl2.

11. The curable resin composition according to any one of claims 1-10, wherein the at least one curable resin composition comprises at least one of the following: alkyd resin, unsaturated polyester resin, vinyl ester resin, (meth)acrylate resin, or a mixture or blend thereof.

12. A cured resin composition obtained by curing the curable resin composition according to any one of claims 1-11.

13. A composite material comprising the cured resin composition as described in claim 13 and at least one reinforcing filler.

14. The composite material of claim 13, wherein the composite material is in the form of a pultruded product or an in-situ cured conduit.

15. An impregnated article comprising at least a reinforcing filler impregnated with a curable resin composition as described in any one of claims 1-11.

16. A method for preparing pultruded fiber-reinforced resin articles, comprising: A continuous fiber bundle is obtained by coating a curable resin composition as described in any one of claims 1-11 with the resin to obtain a resin-coated continuous fiber bundle. The resin-coated continuous fiber bundle is drawn through the molding area to form an elongated structure; and The curable resin composition is heated to a temperature that effectively initiates the curing of the curable composition.

17. A method for preparing an in-situ solidified pipe, comprising: Impregnate the lining with the curable resin composition as described in any one of claims 1-11 to obtain an impregnated lining; The impregnated lining material is placed inside the existing pipe; and The impregnated lining inside the existing pipe is heated to a temperature that effectively initiates the curing of the curable resin composition.

18. A method for preparing a resin transfer molded article, comprising: The fiber reinforcement is impregnated in a matching molding tool with the curable resin composition as described in any one of claims 1-11 to obtain a composite component.

19. A method for preparing a cured composition, the method comprising: The following substances are combined to provide a curable resin composition: a) At least one curable resin that can be cured by an organic peroxide; b) At least one room-temperature stable organic peroxide that is liquid at 25°C and has a half-life temperature of 100°C or higher at 1 hour; c) Optionally, at least one non-room-temperature stable organic peroxide is liquid at 10°C or lower and has a half-life temperature of less than 100°C in one hour. d) At least one salt of at least one metal, said metal comprising at least one of the following: Li, Al, Mg, Co, Fe, Cu, Zn, Ni, Mn, Cr, Sn, Au, Pd, or Pt; e) at least one thiol-functionalized organic compound; and f) Optionally, at least one solvent, said solvent comprising at least one of an alcohol, a glycol, or a glycol ether; and The curable resin composition is heated to a temperature that effectively initiates the curing of the curable composition.

20. A curing system, comprising: i) The first component, which includes: At least one room-temperature stable organic peroxide, which is liquid at 25°C and has a 1-hour half-life temperature of 100°C or higher; and At least one non-room-temperature stable organic peroxide, which is liquid at 10°C or lower and has a half-life temperature of less than 100°C in one hour; The first component optionally contains substantially no styrene, and ii) The second component, which includes: At least one salt of at least one metal, said metal comprising at least one of the following: Li, Al, Mg, Co, Fe, Cu, Zn, Ni, Mn, Cr, Sn, Au, Pd, or Pt; At least one thiol-functionalized organic compound; and Optionally, at least one solvent, said solvent comprising at least one of an alcohol, a glycol, or a glycol ether.

21. The curing system of claim 20, wherein the first component is substantially free of styrene, and the second component comprises at least one solvent, said solvent comprising at least one of an alcohol, a glycol, or a glycol ether.

22. The curing system as described in claim 20 or claim 21, wherein: The at least one non-room-temperature stable organic peroxide comprises at least one of the following: diacyl peroxide; peroxydicarbonate; peroxide ester; di(n-propyl)peroxydicarbonate; di(sec-butyl)peroxydicarbonate; di(2-ethylhexyl)peroxydicarbonate; 3-hydroxy-1,1-dimethylbutylperoxyneodecanate; α-cumylperoxyneodecanate; tert-amylperoxyneodecanate; tert-butylperoxyneodecanate; tert-amylperoxyneodecanate; tert-butylperoxyneodecanate; 2,5-di(2-ethylhexyl) Peroxy-2,5-dimethylhexane; tert-amyl peroxy-2-ethylhexanoate; tert-butyl peroxy-2-ethylhexanoate; (1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate); tert-hexyl peroxy-2-ethylhexanoate; dilauroyl peroxide solution; or dibenzoyl peroxide solution; preferably tert-amyl peroxy-2-ethylhexanoate; tert-butyl peroxy-2-ethylhexanoate; tert-hexyl peroxy-2-ethylhexanoate; or 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate; and The at least one room-temperature stable organic peroxide comprises at least one of the following: hemiperoxyketal; peroxide ester; monoperoxycarbonate; peroxyketal; 1-tert-amylperoxy-1-methoxycyclohexane; tert-amylperoxyacetate; tert-butylperoxyacetate; tert-butylperoxybenzoate; 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane; 1,1-di(tert-amylperoxy)-cyclohexane; 1,1-di(1-butylperoxy)-cyclohexane; 2,2-di(tert-butylperoxy)butane; OO-tert-butyl-O-(2-ethylhexyl)-monoperoxycarbonate; OO-tert-amyl-O-(2-ethylhexyl)-monoperoxycarbonate; OO-tert-amylperoxy-O-isopropyl-monoperoxycarbonate; OO-tert-butylperoxy-O-isopropyl monoperoxycarbonate; polyether tetra(tert-butylperoxycarbonate); or tert-amylperoxybenzoate.

23. The curing system according to any one of claims 20-22, wherein the at least one thiol-functionalized organic compound comprises at least one thiol-functionalized organic compound containing two or more thiol functional groups.

24. The curing system according to any one of claims 20-23, wherein the at least one thiol-functionalized organic compound comprises an α-mercaptoacetate or β-mercaptopropionate of at least one alcohol.

25. The curing system according to any one of claims 20-24, wherein the at least one thiol-functionalized organic compound comprises at least one thiol-functionalized organic compound containing at least one of the following: dipeptene dithiol; ethylcyclohexyl dithiol; ethylene-1,2-bis-3-mercaptoacetate; ethylene-1,2-bis-3-mercaptopropionate; 1,2,3-propane trithiol; 1,2,6-hexane trithiol; pentaerythritol thiol; pentaerythritol tetra(2-mercaptoacetate); pentaerythritol tetra(3-mercaptopropionate); trimethylolpropane tri(3-mercaptopropionate); 1,1,1-propanetriyltri(mercaptoacetate); and thiol derivatives having the general formula: R-(R'-CH(OH)-CH2-SH) n , where R is a straight-chain alkyl group having 3-30 carbon atoms, R' is a straight-chain alkylene group having 3-30 carbon atoms, and n is an integer from 2 to 6.

26. The curing system according to any one of claims 20-25, wherein the at least one thiol-functionalized organic compound comprises pentaerythritol tetra(3-mercaptopropionate), the at least one salt of the at least one metal comprises ZnCl2, and the solvent comprises a glycol ether.

27. A curable resin composition comprising: a) At least one curable resin, said curable resin comprising at least one of alkyd resin, unsaturated polyester resin, vinyl ester resin or (meth)acrylate resin, or mixtures or blends thereof, wherein said curable resin is curable by means of a liquid organic peroxide. b) At least one liquid organic peroxide selected from the group consisting of: i) Room temperature stable organic peroxides that are liquid at 25°C and have a one-hour half-life temperature of 100°C or higher; or ii) Non-room-temperature stable organic peroxides that are liquid at 10°C or lower and have a one-hour half-life temperature of less than 100°C; or iii) Blends or mixtures of organic peroxides (i) and organic peroxides (ii); c) At least one salt of at least one metal, said metal comprising at least one of the following: Li, Al, Mg, Co, Fe, Cu, Zn, Ni, Mn, Cr, Sn, Au, Pd, or Pt; d) At least one thiol-functionalized organic compound; and e) Optionally, at least one solvent, said solvent comprising at least one of an alcohol, a glycol, or a glycol ether.

28. A liquid organic peroxide composition comprising a blend of the following: First organic peroxide; Second organic peroxide; At least one transition metal salt dissolved in a solvent, said solvent comprising at least one of an alcohol, a glycol, or a glycol ether; and At least one thiol-functionalized organic compound; The blend is stable at 18°C ​​or higher, preferably 20°C or higher, more preferably 23°C or higher for at least 1 hour, preferably at least 2-8 hours, more preferably at least 8-15 hours, and most preferably at least 24 hours.

29. The liquid organic peroxide composition of claim 28, wherein the first organic peroxide is a non-room temperature stable organic peroxide with a one-hour half-life temperature of less than 100°C.

30. The liquid organic peroxide composition of claim 28 or claim 29, wherein the second organic peroxide is a room temperature stable organic peroxide having a one-hour half-life temperature of 100°C or higher.

31. The liquid organic peroxide blend of claim 29 or claim 30, wherein the non-room temperature stable peroxide comprises at least one of the following: tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, 2,5-di(2-ethylhexanoylperoxy)-2,5-dimethylhexane, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate, or benzoyl peroxide.

32. The liquid organic peroxide blend according to any one of claims 29-31, wherein the room-temperature stable organic peroxide comprises at least one of the following: hemiperoxyketal; peroxide ester; monoperoxycarbonate; peroxyketal; 1-tert-amylperoxy-1-methoxycyclohexane; tert-butylperoxyacetate; tert-amylperoxyacetate; tert-butylperoxybenzoate; 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane; 1,1-di(tert-amylperoxy)-3,3,5-trimethylcyclohexane; 1,1-Di(1-butylperoxy)-cyclohexane; 2,2-Di(tert-butylperoxy)butane; OO-tert-butyl-O-(2-ethylhexyl)-monoperoxycarbonate; OO-tert-pentyl-O-(2-ethylhexyl)-monoperoxycarbonate; OO-tert-pentylperoxy-O-isopropyl-monoperoxycarbonate; OO-tert-butylperoxy-O-isopropyl-monoperoxycarbonate; polyether tetra(tert-butylperoxycarbonate); or tert-pentylperoxybenzoate.

33. The liquid organic peroxide composition according to any one of claims 28-32, wherein: The first peroxide comprises tert-amyl peroxy-2-ethylhexanoate; tert-butyl peroxy-2-ethylhexanoate; or 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate.

34. The liquid organic peroxide composition according to any one of claims 28-33, wherein: The second peroxide comprises tert-butyl peroxybenzoate; tert-amyl peroxybenzoate; or tert-butyl peroxyacetate.

35. The liquid organic peroxide composition according to any one of claims 28-34, wherein: The metal halide comprises ZnCl2.

36. The liquid organic peroxide composition according to any one of claims 28-35, wherein: The solvent contains diethylene glycol monobutyl ether.

37. The liquid organic peroxide composition according to any one of claims 28-36, wherein: The thiol compound comprises pentaerythritol tetra(3-mercaptopropionate).

38. The liquid organic peroxide composition according to any one of claims 28-32, wherein: The first peroxide comprises tert-amyl peroxy-2-ethylhexanoate or 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate; The second peroxide comprises tert-butyl peroxybenzoate; The metal halide comprises ZnCl2; The solvent comprises diethylene glycol monobutyl ether; and The thiol compound comprises pentaerythritol tetra(3-mercaptopropionate).

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