Radical polymerizable composition

Abstract

A polymerizable composition containing a radically polymerizable resin can be polymerized in the absence of peroxide initiators and other undesirable components. The polymerizable composition and method utilize a manganese- or iron-containing salt or organic complex and a 1,3-dioxo compound together with one or more other components. The polymerizable composition has better storage stability and reduced gel time drift.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the benefit of the filing date and priority of U.S. Provisional Application No. 62 / 787,648, filed on 2 January 2019, which is incorporated herein by reference.

[0002] Field of Invention This disclosure relates to compositions and methods for polymerizing radical polymerizable compositions, wherein the compositions are substantially free of peroxide initiators and / or other undesirable components. The polymerizable compositions and methods utilize manganese or iron-containing salts or organic complexes and 1,3-dioxo compounds together with one or more other components. [Background technology]

[0003] background Thermosetting resins used in casting or open and closed applications are typically cured by free radical polymerization processes. Examples of such thermosetting resins include unsaturated polyester resins, vinyl ester resins, and urethane (meth)acrylates. The backbone of these resins typically contains ethylenically unsaturated groups, such as fumarate or (meth)acrylate, and dissolves in liquid copolymerizable monomers, such as styrene, vinyltoluene, or various methacrylic acid esters. These resins are generally liquid at standard conditions, but when treated with a free radical source, such as an organic peroxide initiator, in the presence of an accelerator, they rapidly form a rigid thermosetting crosslinked network. This process is used, for example, in the manufacture of castings, motors, coatings, adhesives, and fiber-reinforced products. The plastics and composites industry uses organic peroxides most frequently. Organic peroxides and organic peroxide-containing mixtures are used as catalysts, vulcanizing agents, curing agents, or initiators. Organic peroxides and organic peroxide-containing mixtures are often referred to by these terms. The actual designation will depend on the industry and application of the material.

[0004] Organic peroxides are available as solids (usually fine powders), liquids, or pastes. Several materials, such as water, odorless mineral spirits, certain phthalates, or other phlegmatizing agents, do not react with organic peroxides and are often used to dilute them. Diluted mixtures or formulations are less flammable than undiluted organic peroxides when exposed to thermal shock or physical impact. Dilution makes unstable peroxides safer to manufacture, handle, and use. The primary hazards associated with organic peroxides are the potential for fire and explosion. Organic peroxides can also be toxic or corrosive. What makes organic peroxides both useful and dangerous is the double oxygen (-OO-) in the "peroxy" group. The peroxy group is chemically unstable. Organic peroxides can readily decompose thermally, releasing heat at a rate that increases with increasing temperature, leading to what is known as a runaway reaction. Many organic peroxides release flammable vapors when decomposed. These vapors are highly flammable. Most undiluted organic peroxides are highly flammable and can burn very rapidly and violently. This is because organic peroxides contain both fuel (carbon) and oxygen in the same compound. These reactivity hazards have been reported as one of the leading causes of fires and explosions in process industries.

[0005] Organic peroxides have a self-accelerating decomposition temperature (SADT). SADT represents the temperature at which a particular organic peroxide formulation undergoes self-accelerating decomposition (initiating a chemical process that can lead to explosion) in its commercially packaged state. The SADT value will vary depending on the size and shape of each organic peroxide formulation and its packaging. Some organic peroxides are dangerously reactive; they may decompose very rapidly or explosively upon exposure to even slight heat, friction, mechanical shock, or contamination by incompatible substances, such as amines or metal salts or their organic complexes. Organic peroxides can also be powerful oxidizing agents. Most flammable materials contaminated with organic peroxides are highly susceptible to ignition and burning very violently (i.e., deflagration). This means the rate of combustion is extremely fast: it can range from 1 m / s to several hundred m / s. The rate of combustion also increases with increasing pressure, and the combustion (or reaction) zone can travel at ultra-high speeds through the air or gaseous medium.

[0006] Commercially available systems for room-temperature curing thermosetting resins include accelerators and / or promoters used in combination with initiators (peroxides). These include salts of metals selected from, for example, lithium, calcium, copper, vanadium, zirconium, titanium, nickel, iron, sodium, potassium, magnesium, manganese, barium, and cobalt, along with one or more alkyl organic acid compounds. The selection of metal ions and their salts is determined by several parameters, such as activity at ambient temperature, possible coloring effects, toxicity, stability in the thermosetting product, and price. It should be considered that the activity of the metal ion also depends on the type of coordinating group. Due to their good performance at ambient temperature, cobalt-containing accelerators are the most widely used co-promoters. However, a drawback of cobalt is that cobalt carboxylates are suspected to be highly toxic (carcinogenic). Therefore, there is a growing demand in the thermosetting resin industry for accelerators that can provide proper curing without compromising the performance of the resulting product. Recently, thermosetting systems that can gel and harden by free radical polymerization with various accelerators have attracted considerable attention. In particular, since cobalt carboxylates are suspected of being highly toxic (carcinogenic), accelerators that do not contain any cobalt salts are attracting attention.

[0007] Among the important parameters for maintaining the useful life of a resin system during storage, i.e., its "storage life," are the gelation and curing times of the resin system. Variations in the reaction times of gelation and subsequent curing of polyester resin systems during storage can be characterized as "gelation time drift." These variations are typically measured as the difference between the gelation time after storage and the gelation time immediately after formulation of the resin system. Generally, polyester systems stored for long periods result in longer gelation or curing times. However, some polyester systems may exhibit shorter gelation times after long storage periods than the initial curing time of a freshly manufactured batch. Typical commercially available polyester systems often have gelation time drift ranging from minus 50 percent to plus 200-300 percent. Such variations frequently cause problems during molding or coating application processes where predictability of gelation time is required. Gelation time drift in polyester resin systems presents a complex issue, as it can be caused by several interrelated factors, namely the physical parameters of the resin formulation, the chemical composition of the resin system, the promotional packaging, the presence of contaminants, and the transportation, handling, and storage conditions. The problem of gelation time drift is particularly serious for more reactive resin systems that may contain chemical accelerators to accelerate the gelation rate, or when lowering the reaction temperature required in casting operations. It has been found that accelerated polyester systems can not only exhibit large variations in gelation time drift, but also that gelation time drift can vary widely between samples within a single batch of polyester formulations due to different storage and handling conditions.

[0008] Reducing styrene emissions remains a critical issue in open processes using styrene-containing materials, such as unsaturated polyesters, vinyl esters, and other thermosetting resins. One of the largest application areas is open processes, particularly hand lay-up, spray-up, unreinforced casting, gel coat, and filament winding. New environmental concerns demand better control over the emission of organic compounds into the environment. This presents a promising industry for finding means to develop technologies that can reduce the potential hazards to workers in contact with thermosetting resins. At the same time, the market demands that new products have minimal cost increases at commercialization and do not impair the reactivity of the resin. Key factors to consider are that all materials should have good compatibility with all components in the mixture, and that viscosity should remain within an acceptable range so as not to impair pouring or spraying. Furthermore, wetting of glass or fillers is also necessary for maintenance, and physical properties should be similar to or better than currently used standard materials.

[0009] Several methods have been proposed as possible means to reduce styrene and minimize monomer emissions during the curing process of unsaturated polyesters or vinyl esters. One common method is to replace styrene with another reactive diluent that results in less emissions during curing. This technique may result in systems with slower reactivity, incomplete curing, and higher costs. Reducing the amount of styrene or reactive diluent has been used as an attempt to reduce emissions. However, this technique results in higher viscosity, making hand layup, rolling, or spraying of the resin more difficult. Another approach involves the preparation of low molecular weight polymers. Low molecular weight polymers require less styrene or other reactive diluents to produce lower viscosity. A problem associated with lower molecular weight thermosetting systems is that the physical properties of the resulting final product are significantly impaired. Generally, these products perform inferiorly to those produced with higher molecular weight polymers.

[0010] Another common technique used to reduce styrene emissions is the addition of wax to thermosetting resins. While the wax helps limit the emission of diluent vapors during curing and reduces any oxygen inhibition on the surface of the product, the problem this technique encounters is poor interlayer bonding. Oxygen inhibition is a known drawback in the curing process of vinyl-containing thermosetting resins due to oxygen present in the air. Polymerization of monomers on the surface of the product is significantly limited due to contact with air, which leads to the formation of sticky or oily residues. This is problematic for producing materials of good quality, as impurities may adhere to the surface or semi-liquid residues may remain on the underside of the surface, making the product unpleasantly sticky during handling. Wax has perhaps been the most commonly used technique in the composites industry to minimize or eliminate surface stickiness. Wax partially dissolves or disperses in the thermosetting resin, and as it cures, it becomes incompatible with the mixture as it moves to the surface, thus protecting it from contact with oxygen in the air. There are several drawbacks to using wax. For example, using polyester resins containing dicyclopentadiene (DCPD) makes the hydrocarbon properties of the polymer more compatible with paraffin wax. As a result, the wax does not move properly to the surface, and the resulting material remains sticky. The wax must be incorporated into the mixture and remain as a fine dispersion, and therefore its performance is highly dependent on the chemical composition of the thermosetting resin. On the other hand, as mentioned above, wax on the surface of glass-reinforced composites can impair interlayer adhesion. Adhesion problems are frequently encountered when thick composites are prepared in subsequent layers.

[0011] In addition to oxygen inhibition, other problems that can contribute to poor surface quality and the general performance of composite materials include poor curing or insufficient crosslinking of thermosetting resins. Understanding the curing behavior of vinyl-containing thermosetting resins is crucial for establishing appropriate processing procedures to ensure satisfactory quality and on-site performance of composite products. The curing behavior of vinyl-containing thermosetting resins is characterized by a complex mechanism involving copolymerization of the vinyl component in the polymer with molecules induced by the decomposition of the initiator and co-promoter of the vinyl-containing diluent. Heat is generated during copolymerization. Reaction heat, also known as heat of polymerization, is the temperature change of the reaction mixture occurring at constant pressure. It is a thermodynamic unit of measurement useful for calculating the amount of energy released or produced during a reaction. High exothermic reactions, which begin when the heat generated by the reaction exceeds the heat removed, can lead to decomposition products, so the risk must be assessed during the curing of resin and / or monomer mixtures. Excess heat increases the temperature of the reaction products and increases the reaction rate. This, in turn, accelerates the rate of heat generation. An approximate rule of thumb is that the reaction rate, and therefore the rate of heat generation, doubles for every 10°C increase in temperature. As the temperature rises, thermal runaway can occur because the rate at which heat is removed by the surrounding environment increases linearly, rather than exponentially, the rate at which heat is generated. As soon as heat control is lost, the temperature rises rapidly, with little time for correction. The molds used during production may be at risk of deformation due to the sudden increase in temperature and rapid gas generation. The elevated temperature may induce derivative, more harmful by-products or decomposition. The release of flammable materials from the process may reach their flash point, potentially causing a fire or explosion in the workplace. High-temperature gases and toxic substances may contaminate the workplace or form toxic clouds that can spread away from the site. There is a serious risk of injury, even death, to plant operators and could harm the public and the local environment.

[0012] The scale of the curing reaction significantly impacts the potential for excessive heat generation. While the heat generated increases with the volume of the reaction mixture, the heat removed depends on the available surface area of ​​the mold for heat transfer. As the mass-to-surface area ratio increases, cooling can become insufficient. This has crucial implications for scaling up the process from experiment to production. A typical assessment would require one or more of the following: defining the process and manipulating conditions in the plant; identifying potential hazards; assessing the risks arising from these hazards and determining whether existing preventive measures are sufficient or if more should be taken; selecting and identifying appropriate safety measures; and implementing and maintaining the selected safety measures. Once the process design is clear, predictable deviations from the normal process, such as equipment failure or operator error, should be considered.

[0013] A crucial parameter during the preparation of composite materials is that the reactive components of the curing system must generate the appropriate heat of polymerization during crosslinking. Proper heat generation is extremely important because the final mechanical properties of the finished product depend on the proper crosslinking of the mixture. Systems that generate only a small amount of heat of polymerization will be problematic, as resin mixtures may not fully cure or crosslink, leaving uncured material in the product and affecting its final physical properties. In some cases, residual monomers may remain in the composite, diffuse outside the product, and contaminate the environment. Composite materials made of vinyl-containing thermosetting resins are typically cured at low temperatures, moderate temperatures, or room temperature using a peroxide initiator with cobalt salts alone or in combination with tertiary amines. As mentioned above, the drawbacks of these systems are that peroxides are heat-sensitive and cobalt is a toxic and carcinogenic agent. Several methods have been presented, for example, in US10,000,602;US9,068,045;US8,039,559;WO2008 / 003497, to eliminate cobalt as an accelerator from resin mixtures. However, none of these methods solve the problem characterized by the use of peroxides in combination with cobalt salts.

[0014] Few reports have been published regarding polymerizable vinyl thermosetting resins that cure without any peroxides or cobalt salts. U.S. Patent 6,552,140 by Kneafsey and Barnes discloses an air-activatable polymerizable composition useful for preparing adhesives, comprising a methacrylic acid monomer, a cobalt salt, a weak acid, and a 1,3-dioxo compound. This composition requires air to generate free radicals and crosslink the polymerizable composition, and uses potentially toxic metal salts. Nothing is mentioned regarding the gelation time drift, polymerization heat, or degree of curing of the prepared mixture.

[0015] Pfeil's U.S. Patent Application Publication 2016 / 0152754A1 describes a composition having a resin component comprising a radical polymerizable compound, an α-halocarboxylic acid ester, a copper(I) salt, and a nitrogen-containing ligand. Typical reported gelation times range from 45 seconds to 1.5 hours, with polymerization exothermic reactions reported up to 172°C. The composition requires a toxic halogenated intermediate. Any potential gelation time drift of the composition is not mentioned. Pfeil's U.S. Patent Application Publication 2016 / 0168286A1 describes a radically polymerizable composition comprising a copper salt and a nitrogen-containing ligand. According to the claims, crosslinking of the monomer mixture requires concentrations of 3-5% copper salt and ligand. The large amount required darkens the mixture. Nothing is mentioned regarding gelation time drift and polymerization heat. In this patent, Pfeil also refers to his patent application DE102011078785A1, which contains a peroxide-free curing agent 1,3-dicarbonyl compound and a manganese compound used as an accelerator to crosslink the resin composition based on the radically polymerizable compound. He states that this system tends not to fully cure under certain conditions where performance would be reduced by the cured mass, particularly for use in plugging masses, and under conditions requiring reliable ultra-high values. Pfeil's US2016 / 0168286A1, in paragraph

[0011] on page 1, also states that his composition DE102011078785A1 has the drawback that the ratio between the curing agent 1,3-dicarbonyl compound and the manganese compound used as an accelerator must be maintained for each of them so that the binder can fully cure and the required properties of the cured mass can be achieved. Based on Pfeil's own conclusions, his composition '785 does not appear to present a reliable method for obtaining reproducible properties. It would be little expected that the composition would have stable or minimal gelation time drift. Furthermore, nothing is mentioned regarding obtaining non-stick properties with respect to polymerization heat or the resulting cured system.

[0016] P. Garra et al. published a paper in Macromlecules, 2018, 51, 6395-6404, titled "Peroxide-free and amine-free redox-free radical polymerization: Metal acetylacetonates / stable carbonyl compounds for highly efficient synthesis of composites." Table 1 on page 6399 shows experiments using manganese and copper salts in combination with various acetylacetonates. Long curing times and low exothermic reactions are reported. No additional information is provided regarding gelation time drift stability or the reproducibility of the properties obtained for the prepared composite materials. Therefore, this paper does not appear to address the shortcomings of the composition reported by Pfeil. Therefore, it would be desirable to provide a composition that does not require peroxides, is free of cobalt-containing salts, generates appropriate polymerization heat that can lead to a product with stable or minimal gelation time drift and a non-stick surface, achieves good curing to produce the required physical properties, and, if necessary, releases reduced amounts of volatile organic compounds. [Overview of the project]

[0017] Summary of the Invention Considering the above issues, it is necessary to address one or more of the listed challenges. Specifically, it would be advantageous to obtain a highly reactive composition that can crosslink at room temperature or mild high temperatures, reduces or minimizes gelation time drift to provide a non-stick surface and excellent physical properties. This would be particularly advantageous in several application areas, such as sheet molding compound (SMC) resins, casting resins, adhesives, pultrusion resins, corrosion-resistant resins, flame-retardant resins, low or zero-styrene content resins, filament winding, hand lay-up, resin transfer molding, prepregs, gel coats, and coating resins. The present invention provides a polymerizable composition comprising a radical polymerizable component, a manganese or iron-containing salt or organic complex, a 1,3-dioxo compound, and one or more other components, as described later. The polymerizable composition may be curable and / or a thermosetting composition is available for use in the above-mentioned fields of application. The present composition and method are noteworthy for avoiding certain commonly used initiators or catalysts and differ from prior compositions. In some embodiments, the present composition and method are substantially free of peroxides, such as organic peroxides. In some embodiments, the present composition and method are substantially free of cobalt-containing salts or complexes. In some embodiments, the present composition and method are substantially free of copper-containing salts or complexes. In some embodiments, the present composition and method are substantially free of initiators other than 1,3-dioxo compounds. In some embodiments, the composition and method have a heat of polymerization of 100 to 950 kJ / kg, as measured by differential scanning calorimetry. In some embodiments, the heat of polymerization is preferably 150 to 850 kJ / kg, and more preferably 150 to 750 kJ / kg. The amount of heat generated will depend on the composition of the reactive components and various additives that may be part of the polymerizable composition. [Modes for carrying out the invention]

[0018] Definitions of technical terms The technical terms used in this application are for the sole purpose of describing specific embodiments and are not intended to be limiting. In addition to the technical and scientific meanings of the terms defined, they are used as they are generally understood and accepted in the art of this instruction. As used herein and in the appended claims, the terms “a,” “an,” and “the” encompass both singular and plural referents unless the context clearly indicates otherwise. For example, “a component” includes both one and multiple components. Where used herein and in the appended claims, in addition to their ordinary meanings, the terms “substantial” or “substantially” mean to an acceptable extent or degree. For example, “substantially free of a certain component” means that a person skilled in the art would consider that the composition does not contain a significant amount of that component. Where used in this specification and the appended claims, in addition to their ordinary meanings, the term “approximately” means to the extent or quantity acceptable to a person skilled in the art. For example, “approximately identical” means that a person skilled in the art would consider them to be identical by comparison. For example, the term "approximately" as used in this application, when referring to measurable values ​​such as the number of carbon atoms, time, temperature, and days, is intended to encompass variations of ±20%, ±10%, ±5%, ±1%, ±0.5%, or even ±0.1% of the specified quantity.

[0019] As shown in the attached drawings, relative terms, such as "up," "down," "upper part," "lower part," "above," and "below," may be used to describe the relationships between various elements. These relative terms are intended to encompass different geometric arrangements of the coating and / or article, in addition to the geometric arrangement described. For example, if the article is turned over, an element described as "up" another element is now "down" of that element. Similarly, if the article is rotated 90°, an element described as "up" or "down" another element is now "adjacent" to the other element; this "adjacent" means that it is in contact with another element or that there is one or more layers, materials, structures, etc., between the elements.

[0020] The technical terms used herein are for the sole purpose of describing specific embodiments and are not intended to limit the invention. Where used herein, the singular forms "a," "an," and "the" are intended to include the plural form unless the context clearly indicates otherwise. Furthermore, where used herein, there is a common understanding that the terms "comprises" and / or "comprising" specify the presence of certain features, integers, processes, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, integers, processes, operations, elements, components, and / or groups thereof. Where used herein, the term "and / or" includes any combination of one or more of the relevant list items. Where used herein, the term "accelerator" or "promoter" includes any combination and may refer to metal complexes, metal salts, amines, or quaternary ammonium salts. Where used herein, the term "co-accelerator" or "co-promoter" includes any combination and may refer to tertiary amines and / or quaternary ammonium salts.

[0021] Unless otherwise defined, all terms used in this application (including technical and scientific terms) have the same meaning as those generally understood by those skilled in the art to which this invention pertains. Furthermore, terms such as those defined in commonly used dictionaries should be interpreted as having the same meaning as their meanings in the context of the relevant art, and there is a common understanding that they should not be interpreted ideally or overly formally unless explicitly defined in this application. In this application, the term "radical polymerizable" refers to a substance containing a group that participates in radical polymerization reactions. Examples of radical polymerizable groups include ethylenically unsaturated groups, such as vinyl groups and (meth)acrylate groups. The radical polymerizable component may be a monomer, oligomer, polymer, or other component. In some embodiments, the radical polymerizable component is a vinyl monomer, for example, of the formula CHR 1 =CR 2 R 3 (In the formula, R 1 , R 2 , and R 3The group contains a group characterized by a hydrogen atom or an organic group, respectively.

[0022] As used in this application, “alkyl” refers to a linear or branched hydrocarbon group that may contain 1, 2, 3, 4, 5, or 6 carbon atoms, or about 10, 15, 20, or 25 carbon atoms. Representative examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, n-octyl, n-nonyl, and n-decyl. As used in this application, “lower alkyl” refers to a subset of alkyl groups that, in some preferred embodiments, refer to a linear or branched hydrocarbon group containing about 1 to about 4 carbon atoms. Representative examples of lower alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.The terms "alkyl" or "lower alkyl" are intended to include both substituted and unsubstituted alkyl or lower alkyl groups unless otherwise indicated, and these groups include halo, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclo, heterocycloalkyl, hydroxyl, alkoxy (thereby producing polyalkoxy, e.g., polyethylene glycol), alkenyloxy, alkynyloxy, haloalkoxy, cycloalkoxy, cycloalkylalkyloxy, aryloxy, arylalkyloxy, heterocyclooxy, heterocycloalkyloxy, mercapto, alkyl-S(O)m, haloalkyl-S(O)m, and aryl It may be substituted with kenyl-S(O)m, alkynyl-S(O)m, cycloalkyl-S(O)m, cycloalkylalkyl-S(O)m, aryl-S(O)m, arylalkyl-S(O)m, heterocyclo-S(O)m, heterocycloalkyl-S(O)m, amino, carboxy, alkylamino, alkenylamino, alkynylamino, haloalkylamino, cycloalkylamino, cycloalkylalkylamino, arylamino, arylalkylamino, heterocycloamino, heterocycloalkylamino, disubstituted amino, acylamino, acyloxy, ester, amide, sulfonamide, urea, alkoxyacylamino, aminoacyloxy, nitro, or cyano, and m = 0, 1, 2, or 3.

[0023] As used in this application, "alkenyl," either alone or as part of another group, refers to a linear or branched hydrocarbon containing 1, 2, 3, 4, 5, or 6 carbon atoms to about 10, 15, or 20 carbon atoms (or about 1 to about 4 carbon atoms in lower alkenyls), and containing 1 to 4 double bonds in the linear chain. Representative examples of alkenyls, but not limited to, include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, and 2,4-heptadiene. Unless otherwise indicated, the terms "alkenyl" or "lower alkenyl" are intended to include both substituted and unsubstituted alkenyls or lower alkenyls, and these groups may be substituted with the groups described above in relation to alkyl and lower alkyl groups. As used in this application, "alkynyl," either alone or as part of another group, refers to a linear or branched hydrocarbon that may contain 1, 2, 3, 4, 5, or 6 carbon atoms, or about 10, 15, or 20 carbon atoms (or 1 to 4 carbon atoms in the case of lower alkynyls), and contains one triple bond in the linear chain. Representative examples of alkynyls, but not limited to, include 2-propynyl, 3-butynyl, 2-butynyl, 4-pentynyl, and 3-pentynyl. Unless otherwise indicated, the terms "alkynyl" or "lower alkynyl" are intended to include both substituted and unsubstituted alkynyls or lower alkynyls, and these groups may be substituted with the same groups as those shown above in relation to alkyl and lower alkyl.

[0024] As used in this application, "aryl," either alone or as part of another group, refers to monocyclic or bicyclic carbocyclic fused ring systems that may have one or more aromatic rings. Representative examples of aryls include azlenyl, indanyl, indenyl, naphthyl, phenyl, and tetrahydronaphthyl. Unless otherwise indicated, the term "aryl" is intended to include both substituted and unsubstituted aryls, and these groups may be substituted with the same groups shown above in relation to alkyls and lower alkyls. As used herein, "arylalkyl" refers to an aryl group, as defined herein, attached to the parent molecule via an alkyl group as defined herein. Representative examples of arylalkyls, but not limited to, include benzyl, 2-phenylethyl, 3-phenylpropyl, and 2-naphtha-2-ylethyl.

[0025] "Reactive diluent" means a liquid or low-viscosity monomer and base resin that dilutes other base resins or resin components, thereby imparting the viscosity required for their application fields, contains functional groups that can react with the base resin or itself, and, during polymerization (curing), largely becomes a component of the cured composite material system. A layer can adhere to another surface directly or indirectly. "Indirect" adhesion of one layer to another means that there is an intermediate layer between them. For example, when there is a second clear layer between a first clear layer and a color layer, the first clear layer can be said to be indirectly adhered to the color layer. Unless otherwise specified in this application, the term "viscosity" refers to the viscosity of a polymer in a monomer at 25°C (77°C) measured in centipoise (cps) using a Brookfield RV model viscometer. Viscosity under high shear is measured at a shear rate of 10,000 l / s using a cone-plate (CAP) viscometer. The term "NVM" refers to a non-volatile material dispersed in a volatile substance (e.g., a monomer) as measured according to ASTM D1259. All percentages, quantities, and concentrations in this disclosure are given by mass unless otherwise indicated.

[0026] Detailed explanation In the detailed description below, representative embodiments are shown for illustrative purposes only, not as an limitation, but to provide specific details for a complete understanding of this teaching. Descriptions of known systems, apparatus, materials, operating procedures, and manufacturing procedures may be omitted to avoid obscuring the description of the embodiments. Nevertheless, systems, apparatus, materials, and methods within the understanding of those skilled in the art can be used according to the representative embodiments. Polymerizable compositions containing a radical polymerizable component together with one or more other components, as described in this application, have been found to have a stabilized gelation time over their shelf life or useful life. In some embodiments, the radical polymerizable composition comprises a manganese or iron-containing salt or organic complex, a tertiary amine or phosphine, and a nitrogen-containing heterocyclic or thiol compound. In other embodiments, the radical polymerizable composition comprises a 1,3-dioxo compound, a tertiary amine or phosphine, and a nitrogen-containing heterocyclic or thiol compound. In some embodiments, the radical polymerizable composition comprises a 1,3-dioxo compound and a polyhydroxycarboxylic acid or thiol compound. Various components are included in the polymerizable composition in amounts sufficient to reduce, suppress, or minimize gelation time drift for a desirable usable shelf life of the polymerizable composition compared to the untreated corresponding composition. When curing is desired, the composition is mixed with the 1,3-dioxo compound to initiate radical polymerization and crosslinking (curing) of the composition.

[0027] Manganese or iron-containing salts or complexes can be added in several different ways. For example, the metal may be pre-mixed to form a metal salt or metal complex before being added to the polymerizable composition. Another option is to add the individual components of the manganese or iron-containing salt or complex to the polymerizable composition and form the metal salt or complex in situ. The preferred method will depend on the specific curing process being carried out. Another alternative method involves mixing the 1,3-dioxo compound with the radical polymerizable component, along with one or more other components such as polyhydroxycarboxylic acids or thiol compounds to stabilize the gelation time drift of the polymerizable component, and then adding the manganese or iron-containing salt or complex. This mixing can, in practice, be achieved by any of the conventional mixing methods. The advantage of this composition and method is that it provides a radical polymerizable composition characterized by an effectively extended shelf life to suppress gelation time drift. Therefore, a wide variety of resins can be used in molding or coating applications where the gelation time is predictable and requires to differ only slightly from the initial gelation time, which is the property of the resin system immediately after manufacturing. Radical polymerizable resin systems treated according to the method of the present invention exhibit a post-storage gelation time drift that is approximately a percentage lower than the gelation time drift of the untreated corresponding resin system.

[0028] Gelation time drift can be evaluated by measuring the gelation time of the first part of the polymerizable composition at the first time point and the gelation time of the second part of the same composition at one or more subsequent time points. In this case, the polymerization conditions and components are otherwise identical. Gelation time drift can be expressed by finding the difference between the first gelation time and the subsequent gelation times and dividing it by the first gelation time. Gelation time drift can be calculated as average gelation time drift, where the difference is the average difference between the first gelation time and several subsequent gelation times, or as maximum gelation time drift, where the difference is the maximum difference between the first gelation time and any of the subsequent gelation times. The gelation time drift of the composition can be expressed so that it remains within a range during the storage period. For example, some embodiments of this composition have gelation time drifts of less than 20%, or less than 15%, or less than 10%. The first gelation time is generally measured within one or two days of compounding the polymerizable resin with other components. Subsequent gelation times are typically measured 15, 30, 60 days, or other times after the initial gelation time measurement, allowing for evaluation of the storage stability of the polymerizable composition over that period.

[0029] By incorporating a curing system into the polymerizable composition, the thermosetting resin can be given a gelation time of less than 60 minutes at temperatures of about 0°C to about 40°C, or about 5°C to about 25°C. In some embodiments, the polymerizable composition has a gelation time of 10 seconds to 60 minutes, 30 seconds to 60 minutes, or 2 minutes to 60 minutes, or 2 minutes to 25 minutes. In some embodiments, the polymerizable composition has a time to peak exothermic reaction of 5 minutes to 60 minutes, or 5 minutes to 30 minutes. In another embodiment, the present invention gives the thermosetting resin a gelation time drift of less than 20% over a shelf life of about 30 days to about 90 days or more. Various embodiments of this composition offer one or more of the following advantages: The manganese and iron-containing components are common, non-toxic, air-stable metals capable of forming salts and complexes that have the ability to cure this thermosetting system. The 1,3-dioxo compounds are more thermally stable than peroxides and are not susceptible to decomposition in the presence of oxygen in the air. The metal salts and 1,3-dioxo compounds do not pose a hazard in the thermosetting system or during storage. This composition provides a predictable system with a gelation time that differs only slightly from the initial gelation time, which is a characteristic of the resin system immediately after production. The curing system provides excellent performance for obtaining products with non-stick surfaces. The curing system of the present invention provides suitable reaction (polymerization) heat to obtain the expected physical properties. By using a suitable vinyl-containing thermosetting monomer, low-VOC compositions can be produced. Other embodiments and advantages will be evident from the description below and the appended claims. The present invention will be described in more detail below. However, since the present invention can be carried out in many different forms, it should not be understood as being limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure may be complete and comprehensive and fully convey the scope of the invention to those skilled in the art.

[0030] According to several embodiments of the present invention, polymerizable compositions and curing systems comprising manganese or iron-containing salt complexes and 1,3-dioxo compounds are provided, which have been found to surprisingly provide solutions to one or more of the aforementioned problems. In some embodiments, the present composition and method for curing thermosetting resins comprises the following components: (a) Radical polymerizable resin, (b) Manganese or iron-containing salts or organic complexes, (c) Any tertiary amine or phosphine, (d) Any nitrogen-containing aromatic ring or thiol-containing compound, (e) Any polyhydroxycarboxylic acid, (f) 1,3-dioxo compounds, (g) Any transition metal or alkali metal This includes various combinations of Here, the polymerizable composition is substantially free of cobalt, copper, and peroxide initiators, and the polymerizable composition is as follows: (1)(i) a combination of a tertiary amine or phosphine, and (ii) a nitrogen-containing aromatic heterocycle or thiol-containing compound; (2) Polyhydroxycarboxylic acid; or (3) Thiol-containing compounds It includes at least one of the following: Here, the polymerizable composition has a gelation time drift of less than 20% or less than 15% for at least 15 days, or at least 30 days, or at least 60 days.

[0031] In some embodiments, the polymerization composition and method include a radical polymerizable component (a) in combination with a manganese (or iron) salt or complex (b), together with a tertiary amine or phosphine or thiol-containing compound (c) and a nitrogen-containing heterocycle (d). A 1,3-dioxo compound (f) is then added to this mixture to initiate polymerization and form a crosslinked material. In some embodiments, the polymerization composition and method include a radical polymerizable component (a) in combination with a polyhydroxycarboxylic acid or thiol compound, or a mixture thereof (e) and a 1,3-dioxo compound (f). A manganese (or iron) salt or complex (b) is then added to this polymerization composition to initiate polymerization and form a crosslinked network. Separately, component (a) can be mixed with a tertiary amine or phosphine (c), a nitrogen-containing aromatic heterocyclic or thiol-containing compound (d), and a 1,3-dioxo compound (f), after which a manganese or iron-containing salt or organic complex (b) can be added to form a crosslinking network. Depending on the chemical properties of component (a) and its composition, other combinations and methods for using components (a) to (g) may be appropriate. Preferred methods for combining radical polymerizable components with other components will depend on the thermosetting components, inhibitors, any additives that are part of the composition, and the final intended application area.

[0032] Typically, the gelation time of polymerizable compositions can drift from one day to several weeks or even months. It is also desirable that the compositions of the present invention maintain a stable gelation time with minimal variation over a specific service life. In another aspect of the present invention, a polymerized composition is provided that has reduced or minimal drift with respect to gelation time over about 30 days, or about 60 days, or about 90 days or more. In some embodiments, a curing system is provided for curing a polymerizable composition, comprising a manganese or iron-containing salt or an organic complex and one or more other components, including a 1,3-dioxo compound. The curing system may be incorporated into the polymerizable composition all at once or at different times. For example, the first portion may remain part of the composition for 30 days or more. In some embodiments, the manganese or iron-containing complex may be derived from the reaction of copper with an alkyl organic acid, a carboxylate, and a naphthenate, as prepared according to U.S. Patent No. 5,859,267.

[0033] In some embodiments, the manganese or iron-containing complex is as follows: (M)(RCOO-) 2 (In the formula, M is either manganese or iron, and R may be H, a substituted or unsubstituted linear alkyl, a substituted or unsubstituted branched alkyl, a substituted or unsubstituted linear alkenyl, a substituted or unsubstituted branched alkenyl, a substituted or unsubstituted linear alkynyl, a substituted or unsubstituted branched alkynyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted alkylaryl.) That is the case. In another embodiment, the manganese or iron-containing complex may be a naphthenate. The naphthenate may be a mixture of various cyclopentyl and cyclohexyl carboxylic acids or alicyclic carboxylic acids with molecular weights ranging from about 120 daltons to well over 700 daltons. Generally, most naphthenic acids have a carbon skeleton containing about 9 to about 20 carbon atoms. In some embodiments, the naphthenic acid has a carbon skeleton containing about 10 to about 16 carbon atoms. In some embodiments, the naphthenate may be, for example, the following:

[0034] [ka]

[0035] In the formula, M is either manganese or iron, m and n are independently integers greater than or equal to 0, for example, 0, 1, 2, 3, 4, 5, 6, 10, 15, 20 or greater, and R' and R'' are independently H, a substituted or unsubstituted linear alkyl, a substituted or unsubstituted branched alkyl, a substituted or unsubstituted linear alkenyl, a substituted or unsubstituted branched alkenyl, a substituted or unsubstituted linear alkynyl, a substituted or unsubstituted branched alkynyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted alkylaryl. Separately, in some embodiments, the manganese or iron-containing complex is one of those described in U.S. Patent No. 4,138,385, for example, as follows:

[0036] [ka]

[0037] (where M is either manganese or iron, and R 1 , R 2 , R 3 and R 4 can each independently be H, a substituted or unsubstituted linear alkyl, a substituted or unsubstituted branched alkyl, a substituted or unsubstituted linear alkenyl, a substituted or unsubstituted branched alkenyl, a substituted or unsubstituted linear alkynyl, a substituted or unsubstituted branched alkynyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted alkylaryl) and may be given as a complex of acetylacetonate such as . The manganese or iron-containing complex may also include salts contained as chlorides, bromides, iodides, nitrates, sulfates, phosphates, oxalates, salicylates, etc. They may be incorporated alone, in pairs or together with one, two or a mixture of the above metals. In some embodiments, the manganese or iron-containing complex added to the resin may range from 0.0001 to about 3.0 percent based on the mass of the resin. For example, the amount of the manganese or iron-containing complex added to the resin may range from 0.0005 to about 1.5 mass percent based on the mass of the resin. The level of the manganese or iron-containing complex added to the resin and the level of any optionally added transition metal salt essentially free of cobalt can be selected based on the final gelation time and the desired curing of the thermosetting resin. In some embodiments, the manganese or iron-containing complex is an organophosphine metal complex. The organophosphine metal complex has the following formula P-I:

[0038]

Chemical formula

[0040] [ka]

[0041] (In the formula, R 1 In each case, independently, these are H, hydroxyl, C1-C6 containing branched or cyclic aliphatic, C1-C4 alkoxy; aryl, e.g., C6-C20 monocyclic or polycyclic aryl, e.g., phenyl, toluyl, naphthyl, biphenyl, terphenyl, halogen-containing aryl aromatic, amino, silyl; heteroalkyl, e.g., C6-C20 monocyclic or polycyclic heteroaryl, e.g., thienyl, furyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridadinyl, indolyl, quinolyl and isoquinolyl; R 2 In each case, independently, H, C1-C14-containing linear, branched or cyclic aliphatic, alkyl aromatic, halogen-containing aryl aromatic, amino, silyl or alkoxy group, and R 1 Group, R 2 Base or R 1 and R 2 (Linked together by alicyclic or aromatic rings between the groups; n is 0-4; Y is either N or P) It has the structure of [the object]. In another embodiment, the organophosphine of the manganese or iron-containing complex is given by the following formula P-III:

[0042] [ka]

[0043] (In the formula, R 1 In each case, independently, H, hydroxyl, C1-C6 containing branched or cyclic aliphatic, C1-C4 alkoxy; aryl, e.g., C6-C20 monocyclic or polycyclic aryl, e.g., phenyl, toluyl, naphthyl, biphenyl, terphenyl, halogen-containing aryl aromatic, amino, silyl; heteroalkyl, e.g., C6-C20 monocyclic or polycyclic heteroaryl, e.g., thienyl, furyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridadinyl, indolyl, quinolyl, and isoquinolyl; Y is either N or P. It has the structure of [the object]. In another embodiment, the organophosphine of the manganese or iron-containing complex is given by the following formula P-IV:

[0044] [ka]

[0045] (In each case, R is independently H, a C1-C14-containing linear, branched or cyclic aliphatic, alkyl aromatic, halogen-containing aryl aromatic, amino or alkoxy group; R 1 In each case, independently, these are H, hydroxyl, C1-C6 containing branched or cyclic aliphatic, C1-C4 alkoxy; aryl, e.g., C6-C20 monocyclic or polycyclic aryl, e.g., phenyl, toluyl, naphthyl, biphenyl, terphenyl, halogen-containing aryl aromatic, amino, silyl; heteroalkyl, e.g., C6-C20 monocyclic or polycyclic heteroaryl, e.g., thienyl, furyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridadinyl, indolyl, quinolyl and isoquinolyl; R 2In each case, these are independently H, C1-C14-containing linear, branched or cyclic aliphatic, alkyl aromatic, halogen-containing aryl aromatic, silyl, amino or alkoxy groups, linked to each other by an alicyclic or aromatic ring; Y is either N or P. It has the structure of [the object].

[0046] Examples of organophosphine metal complexes, though not limited to those mentioned above, include those containing the following ligands: (2,4)-bis(di-tert-butylphosphino)pentane, 1,4-bis(di-tert-butylphosphino)butane, 1,2-bis(di-tert-butylphosphino)ethane, bis(di-tert-butylphosphino)methane, bis(di-tert-butylphosphino)pentane, 1,3-bis(di-tert-butylphosphino)propane, 1,2-bis(di- (Crohexylphosphino)ethane, 1,3-bis(dicyclohexylphosphino)propane, 1,4-bis(dimethylphosphino)butane, 1,2-bis(dimethylphosphino)ethane, 1,3-bis(dimethylphosphino)propane, bis(dimethylamino)methylphosphine, di-tert-butylmethylphosphine, di-tert-butylneopentylphosphine, di-tert-butylphenylphosphine, dicyclohexylnorbornylphosphine, dri-propylphosphine, triiso Propylphosphine, tri-tert-butylphosphine, triisobutylphosphine, tricyclohexylphosphine, tris(2-furyl)phosphine, tris(3-methoxypropyl)phosphine, tris(1-naphthyl)phosphine, trimethylphosphine, triethylphosphine, diethylphenylphosphine, triphenylphosphine, ortho-phenylenebis(diphenylphosphine), ortho-phenylenebis(dimethylphosphine), ortho-phenylenebis(diethylphosphine), ortho-phenylenebis(ethylphenylphosphine), tris(diphenylphosphinoethyl)phosphine, tris(diethylphosphinoethyl)phosphine, tris(dimethylphosphinoethyl)phosphine, tris(ethylphenylphosphinoethyl)phosphine, (2-methoxyphenyl)methylphenylphosphine, 1-bromo-2-diphenylphosphinobenzene, dimethyl(phenyl)phosphine, cyclohexyldiphenylphosphine, CI-cyclohexylphenylphosphine, bis(3,5-Ditrifluoromethylphenyl)phenylphosphine, di-tert-butyl(4-dimethylaminophenyl)phosphine, (4-dimethylaminophenyl)diphenylphosphine, bis(2-(bis(diethylamide)phosphino)phenyl)ether, bis(2-diphenylphosphinoethyl)phenylphosphine, 2,6-bis(diphenylphosphinomethyl)pyridine, 2,6-bis[bis(3,5-dimethylphenyl)phosphinomethyl]pyridine, 2-(diphenylphosphino)pyridine, bis(2-diphenyl (Phenylphosphinofenophenyl) ether, diphenylphosphinostyrene, ethyldiphenylphosphine, methyldiphenylphosphine, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, (2,3)-bis(diphenylphosphino)butane, (2,5)-bis(diphenylphosphino)hexane, 1,2-bis(diphenylphosphino)propane, (1,2)-bis[(2-methoxyphenyl)phenylphosphino]ethane, 2,2'-bis[bis(3,5-dimethylphenyl)phosphino]-1,1'-bi Naphthyl, 1,4-bis[bis(3,5-dimethylphenyl)phosphino]butane, 1,2-bis[bis(3,5-dimethylphenyl)phosphino]ethane, bis[bis(3,5-dimethylphenyl)phosphino]methane, 1,5-bis[bis(3,5-dimethylphenyl)phosphino]pentane, 1,3-bis[bis(3,5-dimethylphenyl)phosphino]propane, 2,2'-bis[bis(3,5-ditrifluoromethylphenyl)phosphino]-1,1'-binaphthyl, 2,2'-bis(di-p-tolylphosphino) (no)-1,1'-binaphthyl, (1,2)-bis[(2-methoxyphenyl)phenylphosphino]ethane, 1,3-bis[bis(0-methoxyphenyl)phosphino]propane, 1A-bis[bis(3,5-ditrifluoromethylphenyl (phellyl))phosphino]butane, 1,2-bis[bis(3,5-ditrifluoromethylphenyl)phosphino]ethane, bis[bis(3,5-ditrifluoromethylphenyl)phosphino]methane, 1,3-bis[bis(3,5-ditrifluoromethylphenyl (pheny I))phosphino]propane, bis[bis(3,5-25-ditrifluoromethylphenyl)phosphino]methane, 1,2-Bis(di-tert-butylphosphino)benzene, 2,2'-Bis(di-tert-butylphosphino)biphenyl, 1,2-Bis(di-tert-butylphosphinomethyl)benzene, 1,3-Bis(di-tert-butylphosphinomethyl)benzene, 1,2-Bis(dicyclohexylphosphino)benzene, 2,2'-Bis(dicyclohexylphosphino)-1,1'-Binaphthyl, 2,2'-Bis(dicyclohexylphosphino)biphenyl, 1,2-Bis(diphenylphosphino) Finoden)benzene, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 2,2'-bis(diphenylphosphino)-1,1'-biphenyl, 1,4-bis(is)(diphenylphosphino)butane, 1,2-bis(diphenylphosphino(phospltino))ethane, bis(2-diphenylphosphino(phospltino))ethyl ether, bis(2-diphenylphosphinoethyl)phenylphosphine, 1,6-bis(diphenylphosphino(pho (spltino)) Hexane, bis(diphenylphosphino)methane, 1,5-bis(diphenylphosphino)pentane, bis(2-diphenylphosphinophenyl) ether, 1,3-bis(diphenylphosphino)propane, 2,2'-bis[bis(3,5-dimethylphenyl)phosphino]-1,1'-binaphthyl, 2,2'-bis[bis(3,5-ditrifluoromethylphenyl)phosphino]-1,1'-binaphthyl, 2,2'-bis[bis(4-methylphenyl)phosphino] [ino]-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl, (1R,2R)-bis[(2-methoxyphenyl)phenylphosphino]ethane, 1,1'-bis[bis(diethylamino)phosphino]ferrocene, 1,1'-bis(di-tert-butylphosphino)ferrocene, 1,1'-bis(dicyclohexylphosphino)ferrocene, 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro(perhydro-l,)-l,3,Examples include 2-diazaphosphorine, tert-butylimino-tri(pyrrolidino)phosphoran, hexaethylphosphoramide, hexisopropylphosphoramide, tris(4-morpholino)phosphine, and combinations thereof. In some embodiments, the organophosphine metal complex-containing compound added to the resin may range from 0.0001 to about 3.0 percent based on the mass of the resin. In one embodiment, the amount of organophosphine metal complex-containing compound added to the resin may range from 0.001 to about 1.0 mass percent based on the mass of the resin. In another embodiment, the amount of organophosphine metal complex-containing compound added to the resin may range from 0.001 to about 0.5 mass percent based on the mass of the resin. The amount of organophosphine metal complex-containing compound and any optional transition metal salts that are essentially cobalt-free may be determined by the final gelation time of the thermosetting resin and the desired curing. In other embodiments, the thermosetting resin may include a tertiary amine and an optional quaternary ammonium salt used as co-accelerators for curing the resin system.

[0047] In some embodiments, the radical polymerizable composition comprises at least one metal complex selected from manganese (Mn) or iron (Fe)-containing complexes containing monodentate, bidentate, tridentate, quadentate, pentate, or hexadentate nitrogen-donating ligands. In some embodiments, the at least one metal complex is a Mn or Fe complex with a bidentate, tridentate, quadentate, pentate, or hexadentate nitrogen-donating ligand. For example, the iron ion can be selected from Fe(II) and Fe(III), and the manganese ion can be selected from Mn(II), Mn(III), and Mn(IV). In some embodiments, ligand L exists in one or more forms of [MnLCl2], [FeLCl2], [FeLCl]Cl, [FeL(H2O)](PF6)2, [FeL]Cl2, [FeLCl]PF6, and [FeL(H2O)](BF4)2. Preferably, ligand L exists in one or more forms of [MnLCl2], [FeLCl2], [FeLCl]Cl, [FeL]Cl2, and [FeL(H2O)](BF4)2.

[0048] As used in this application, the terms “nitrogen-donating ligand,” “ligand,” or “L” refer to an organic structure or molecule that will support a coordinating nitrogen atom. In this invention, the at least one nitrogen-donating ligand is selected from the group including monodentate, bidentate, tridentate, quaternate, pentate, and hexadentate nitrogen-donating ligands. For suitable non-limiting examples of monodentate, bidentate, tridentate, quaternate, pentate, and hexadentate nitrogen-donating ligands, see U.S. Patents 2,526,718, 2,565,897, 4,311,625, WO2008 / 003652, and DE4032546, which are incorporated herein by reference in their entirety. In some embodiments, the composition comprises at least one accelerator, which is a tridentate, quadentate, quindentate, or hexadentate nitrogen-donating ligand, an N-heterocyclic compound, or an iron or manganese-containing complex of an N-heteroaromatic compound. In some embodiments, the at least one nitrogen-donating ligand is selected from the group comprising ligands of the following formulas: NI, N-II, N-III, N-IV, NV, N-VI, N-VII, and / or ligands comprising N-heterocyclic compounds or N-heteroaromatic compounds.

[0049] [ka]

[0050] [ka]

[0051] In some embodiments, the manganese or iron-containing complex generally belongs to the bisspidone classification and is preferably in the form of a manganese metal complex, as shown in formula NI below.

[0052] [ka]

[0053] It has ligands. In the formula, R 1 and R2 Independently, C 1-24 Alkyl, C 6-10 Aryl, heteroaryl, heteroaryl C 1-6 A heteroaryl is selected from the group consisting of alkyl and -CH2-CH2-N(CH3)2, where the heteroaryl is selected from the group consisting of pyridyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl, and thiazolyl; R 3 and R 4 These are independently -H, C 1-8 Alkyl, C 1-8 Alkyl-OC 1-8 Alkyl, C 1-8 Alkyl-OC 6-10 Ariel, C 6-10 Ariel, C 1-8 -Hydroxyalkyl and -(CH2) m C(O)OR 5 Selected from the group consisting of; R 5 is -H or C 1-4 It is selected from alkyl, and m is an integer selected from 0 to 4; R 6 and R 7 These are, independently, -H, -F, -Cl, -Br, ---OH, and C. 1-4 Alkoxy, -NH-C(O)-H, -NH-C(O)-C 1-4 Alkyl, -NH2, -NH-C I-4 Alkyl and C 1-4 Selected from the group consisting of alkyl groups; X 1 is -C(O)- or -[C(R 8 )2] n Selected from, where n is an integer selected from 0 to 3, and each R 8 These are independently -H, -OH, and C 1-4 Alkoxy and C 1-4 Selected from the group consisting of alkyl groups.

[0054] In some embodiments, R 3 and R 4The heteroatoms are selected from -C(O)O-CH3, -C(O)-O-CH2-CH3, -C(O)-O-CH2-C6H5, and CH2OH. In some embodiments, the heteroatoms capable of coordinating with the transition metal are optionally C 1-4 It is pyridine-2-ylmethyl which may be substituted with alkyl. In some embodiments, X 1 C=O and / or R 1 and R 2 CH3, C2H5, C3H7, benzyl, C4H9, C 12 H 25 , and C 18 H 37 It is CH2-pyridyl or pyridine-2-yl. An example classification of bispidone is R 1 or R 2 At least one of them is pyridine-2-ylmethyl or benzyl, preferably pyridine-2-ylmethyl. In some embodiments, R 1 is pyridine-2-ylmethyl, and R 2 It is methyl. Preferred bispitones are dimethyl 2,4-di-(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonane-9-one-1,5-dicarboxylate (N2py30-Cl) and its manganese complex. FeN2py30-Cl can be prepared as described in WO02 / 48301. Other preferred bispitones have a longer alkyl chain instead of a methyl group at the 3-position, namely isobutyl, (n-hexyl)C6, (n-octyl)C8, (n-dodecyl)C 12 (n-tetradecyl)C 14 (n-octadecyl)C 18 These have the same properties, and these were prepared similarly. Preferred tetraconjugate bispitone is also described in WO00 / 60045, and preferred pentaconjugate bispitone is described in W002 / 48301 and W0031104379, the entire disclosure is incorporated herein by reference to each of them. In some embodiments, the metal complex may also be called an "N4py type ligand," and is preferably in the form of a manganese metal complex, as shown in the following formula N-II

[0055] [ka]

[0056] (In the formula, R 11 and R 12 These are, independently, equation -R 14 -R 15 It is the basis of; R 13 -H, -R 14 -R 15 , and C 1-6 Alkyl, C 6-10 Aryl and C 6-10 Aryl-C 1-6 Selected from the group consisting of alkyl groups, and from the group consisting of optionally substituted groups; Each R 14 These are independently, single covalent bonds or C 1-6 Alkylene, C 2-6 Alkenylene, C 1-6 Alkylene oxy, Amino C 1-6 Alkylene, C 2-6 A group selected from the group consisting of alkylene ethers, carboxylic acid esters and carboxylic acid amides, which may be optionally substituted; and Each R 15 (These are independently selected from an optionally N-substituted aminoalkyl group or an optionally substituted heteroaryl group selected from the group consisting of pyridyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl, and thiazolyl.) It has ligands.

[0057] In some embodiments, R 11 represents pyridine-2-yl or R 12 represents pyridine (pyriclin)-2-yl-methyl. Preferably R 12 or R 11represents 2-amino-ethyl, 2-(N-ethyl)amino-ethyl or 2-(N-methyl)amino-ethyl or 2-(N,N-di(methyl)amino-ethyl. When substituted, R 15 may represent 3-methylpyridin-2-yl. R 13 may represent hydrogen, benzyl or methyl. In some embodiments, preferred ligands are N4Py (i.e., N,N-bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)methylamine) described in W095 / 34628 and MeN4py (i.e., N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-aminoethane) described in EP0909809, the entire contents of each document being incorporated herein by reference. In some embodiments, the metal complex comprises a ligand of the following formula N-III, sometimes referred to as TACN-Nx. The ligand has a basic 1,4,7-triazacyclononane structure and has one or more pendant nitrogen groups that form a complex with a metal to give a tetracoordinate, pentacoordinate or hexacoordinate ligand.

[0058] [Chemical formula]

[0059] In the formula, each R 20 is independently selected from the group consisting of C 1-6 alkyl, C 3_8 cycloalkyl, heterocycloalkyl, heteroaryl, C 6-10 aryl and C 6-10 aryl-C 1-6 alkyl, and may be optionally substituted with a substituent selected from the group consisting of -OH, C 1-6 alkoxy, phenoxy, carboxylate, carboxamide, carboxylic acid ester, sulfonate, amine, C 1-6 alkylamine and N + (R 21 )3; each R 21 is C 1-6 alkyl, C2-6 Alkenil, C 6-10 Aryl-C 1-6 Alkyl, C 6-10 Aryl-C 2-6 Alkenil, C 1-6 Alkyloxy, C 2-6 Alkenyloxy, AminoC 1-6 Alkyl, amino C 2-6 Alkenil, C 1-6 Alkyl ether, C 2-6 Alkenyl ethers and -CX 2 2-R 22 Selected from; each X 2 These are independently -H or C 1-3 Selected from alkyl, where each R 22 R is independently selected from an optionally substituted heteroaryl group selected from the group consisting of pyridyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and R 21 At least one of them is -CX 2 -R 22 That is the case. In some embodiments, R 22 R is selected from pyridine-2-yl, imidazole-4-yl, pyrazole-1-yl, and quinoline-2-yl groups, which may be optionally substituted. For example, R 22 This can be pyridine-2-yl or quinoline-2-yl. In some embodiments, the basic 1,4,7-triazacyclononane structure has two pendant nitrogen groups (TACN-N2) that form complexes with transition metals. In some embodiments, the metal complex may also be called a cyclome and a bridging ligand, and preferably contains a ligand of the following formula N-IV, which is in the form of a manganese metal complex.

[0060] [ka]

[0061] In the formula, each 3 The formula is as follows:

[0062] [ka]

[0063] (In the formula, p is 4; each R 37 These are independently -H, C 1-6 Selected from the group consisting of alkyl, --CH2CH20H, pyridine-2-ylmethyl and -CH2C(O)OH; and R 31 , R 32 , R 33 , R 34 , R 35 and R 36 These are, independently, -C 1-4 Alkyl and C 1-4 (Selected from hydroxyalkyl groups) Selected independently from. In some embodiments, the cyclam ligand is selected from 1,4,8,11-tetraazacyclotetradecane (cyclam), 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (Me4 cyclam), 1,4,7,10-tetraazacyclododecane (cyclam), 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane (Me4 cyclam), and 1,4,7,10-tetrakis(pyridine-2-ylmethyl)-1,4,7,10-tetraazacyclododecane (Py4 cyclam (cyclan)). Iron complexes are preferred for the Py4 cyclam. A preferred bridging ligand is preferably a ligand of the following formula NV.

[0064] [ka]

[0065] In the formula, each R 40 These are independently -H or C 1-20 Alkyl, C 1-6 Alkyl, C 6-10 Ariel, C 2-6 Alkenil or C 2-6- Selected from the group consisting of alkynyl groups, which may be optionally substituted; and all nitrogen atoms of the polycyclic group are coordinated to a transition metal. In some embodiments, R 40 The ligand for the complex [Mn(B-cyclum)CI2] is methyl, and can be synthesized as described in WO98 / 39098, which is incorporated herein by reference in its entirety. Other suitable bridging ligands are also described in W098 / 39098, which is incorporated herein by reference in its entirety. In some embodiments, the metal complex contains a ligand of the following formula N-VI, sometimes referred to as the “trispicene type.” The “trispicene” is preferably in the form of a manganese metal complex.

[0066] [ka]

[0067] In the formula, X 4 It is selected from -CH2CH2-, -CH2CH2CH2-, and -CH2C(OH)HCH2-; Each R 50 These are independently -H, C 1-6 Alkyl, C 3-8 Cycloalkyl, heterocycloalkyl, heteroaryl, C 6-10 Aryl and C 6-10 Aryl-C 1-6 Selected from the group consisting of alkyl groups, -OH, C 1-6 Alkoxy, phenoxy, carboxylate, carboxamide, carboxylic acid ester, sulfonate, aniline, C 1-6 Alkylamines and -N + (R 51 )3 may be optionally substituted with substituents selected from 3; Here, each R 51 is -H, C 1-6 Alkyl, C 2-6 Alkenil, C 6-10 Ariel, C 1-6 Alkyl, C 6-10Ariel, C 2-6 Alkenil, C 1-6 Alkyloxy, C 2-6 Alkenyloxy, AminoC 1-6 Alkyl, amino C 2-6 Alkenil, C 1-6 Alkyl ether, C 2-6 Alkenyl ethers, and -C(X 5 )2-R 52 Selected from; each X 5 These are independently -H or C 1-3 Selected from alkyl groups, each R 52 The group is independently selected from an optionally substituted heteroaryl group chosen from the group consisting of pyridyl, pyrazinyl, pyrazolyl, pyroyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and R 50 At least two of them are -C(X 5 )2-R 52 The heterogenous child-donating group is preferably -C. 0-4 The pyridinyl may be optionally substituted with alkyl groups. Other preferred heterogenodonating groups are imidazole-2-yl, 1-methylimidazole-2-yl, 4-methylimidazole-2-yl, imidazole-4-yl, 2-methylimidazole-4-yl, 1-methylimidazole-4-yl, benzimidazole-2-yl and 1-methyl-benzimidazole-2-yl. Preferably R 50 These three are C(X 5 )2-R 52 That is the case.

[0068] The following are preferred trispicenes: N-methyltris(pyridine-2-ylmethyl)ethylene-1,2-diamine; N-octyl-tris(pyridine-2-ylmethyl)ethylene-1,2-diamine; N-octadecyl-tris(pyridine-2-ylmethyl)ethylene-1,2-diamine; N-methyl-N,N',N'-tris(3-methylpyridine-2-ylmethyl)ethylene-1,2-diamine; N-ethyl-N,N',N'-tris(3-methylpyridine-2-ylmethyl)ethylene-1,2-diamine; N-methyl-N,N ',N'-Tris(5-methylpyridine-2-ylmethyl)ethylene-1,2-diamine; N-Ethyl-N,N',N'-Tris(5-methylpyridine-2-ylmethyl)ethylene-1,2-diamine; N-Benzyl-N,N',N'-Tris(3-methylpyridine-2-ylmethyl)ethylene-1,2-diamine; N-Benzyl-N,N',N'-Tris(5-methylpyridine-2-ylmethyl)ethylene-1,2-diamine; N-Butyl-N,N',N'-Tris(pyridine-2-ylmethyl)ethylene-1,2-diamine; N-O Cutyl-N,N',N'-tris(pyridine-2-ylmethyl)ethylene-1,2-diamine; N-dodecyl-N,N',N'-tris(pyridine-2-ylmethyl)ethylene-1,2-diamine; N-octadecyl-N,N',N'-tris(pyridine-2-ylmethyl)ethylene-1,2-diamine; N-methyl-N,N',N'-tris(imidazole-2-ylmethyl)-ethylenediamine; N-ethyl-N,N',N'-tris(imidazole-2-ylmethyl)ethylenediamine; N,N'-dimethyl-N,N'-bis(imidazole N-2-ylmethyl)ethylenediamine; N-(1-propan-2-ol)-N,N',N'-tris(imidazole-2-ylmethyl)ethylenediamine; N-(1-propan-2-ol)N,N',N'-tris(1-methylimidazole-2-ylmethyl)ethylenediamine; N,N-diethyl-N',N",N"-tris(5-methylimidazole-4-ylmethyl)diethylenetriamine; N-(3-propan-1-ol)-N,N',N'-tris(1-methylimidazole-2-ylmethyl)ethylenediamine;N-hexyl-N,N',N'-tris(imidazole-2-ylmethyl)ethylenediamine; N-methyl-N,N',N'-tris(benzimidazole-2-ylmethyl)ethylenediamine; and N-(3-propan-1-ol)methyl-N,N',N'-tris(benzimidazole-2-ylmethyl)ethylenedianiline. Other suitable trispicenes are described in WO02 / 077145. Other nitrogen-donating ligands suitable for manganese-containing and iron-containing complexes are the ligands of the following formula N-VII.

[0069] [ka]

[0070] In the formula, each R 60 These are independently -H, C 1-6 Alkyl, C 6-10 Ariel, C 1-6 Alkyl-C 6-10 Aryl and C 2-6 Selected from the group consisting of alkenils. In some embodiments, bisspidone and the TACN-Nx ligand are used. Examples of non-limiting preferred nitrogen-donating ligands are shown in the following formulas: N-Ia, N-XIb, N-XIII, N-XIV, N-XV Selected from the group consisting of the following compounds.

[0071] [ka]

[0072] [ka]

[0073] In some embodiments, the metal complex is of the following formula N-XX.

[0074] [ka]

[0075] In some embodiments, the metal complex is of the following formula N-XXI.

[0076] [ka]

[0077] The complex of formula N-XXI is the active ingredient in Drycoat. In some embodiments, the ligand of the manganese or iron-containing complex is selected from porphyrin ligands. Porphyrins are compounds containing four nitrogen heterocycles arranged in a cyclic structure. For example, in some embodiments, the porphyrin ligand of interest has the structure of the following formula YI.

[0078] [ka]

[0079] In the formula, X 1 , X 2 , X 3 , and X 4 These are independently selected from C and N; R 1 ~R 12 These are independently hydrogen, halo, and C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkinyl, C5-C 20 Ariel, C6-C 24 Alkaline, C6-C 24 Aralkyl, hydroxyl, C1-C 24 Alkoxy, C2-C 24 Alkenyloxy, C2-C 24 Alkynyloxy, C5-C 20 Aryloxy, Acyloxy, Acyl, C2-C 24 Alkoxycarbonyl (earbonyl), C6-C 20 Aryloxycarbonyl, C2-C 24Alkylcarbonyl, C6-C 20 Arylcarbonyl, Halocarbonyl, Formyl, Thioformyl, C2-C 24 Alkylcarbonate, C6-C 20 Arylcarbonato, Carboxylate, Carboxyl, Carbamoyl, Thiocarbamoyl, Carbamato, Carbamide, Cyano, Isocyano, Cyanato, Isocyanato, Isothiocyanato, Amino, C2-C 24 Alkylamide, C6-C 20 Arylamide, imino, alkylimino, arylimino, nitro, nitroso, sulfhydryl, C1-C 24 Alkyl sulfanyl, C5-C 20 Selected from arylsulfanyl, sulfo, sulfino, sulfonyl, phosphino, phosphono, and O-phosphono, except X 1 , X 2 , X 3 , or X 4 When is N, the corresponding R group (each, R 1 , R 2 , R 3 , or R 4 ) does not exist. Each of the groups may be unsubstituted or substituted, and may contain one or more heteroatoms as necessary (i.e., if the chemical properties of the group allow for such substitution or heteroatoms). Furthermore, any two adjacent groups selected from R1 to R12 may together form a ring, which may be aliphatic, aromatic, heteroatom-containing, and / or substituted as necessary.

[0080] For example, in some embodiments, X 1 , X 2 , X 3 , and X 4 N is R 1 , R 2 , R 3 , and R 4 It does not exist. In some embodiments, R 1 , X 2 , X 3 , and X 4 C is R 1 , R2 , R 3 , and R 4 In some embodiments, X 1 , X 2 , X 3 , and X 4 One or more of the following are C, and X 1 , X 2 , X 3 , and X 4 One or more of these are N. For example, R 1 ~R 12 These are independently hydrogen; halos, e.g., F, CI, Br, and I; substituted or unsubstituted C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkinyl, C5-C 20 Ariel, C6-C 24 Alkaline, and C6-C 24 Aalkyl; substituted or unsubstituted heteroatom-containing carbon 1 -C 24 Alkyl, C 2 -C 24 Alkenil, C 2 -C 24 Alkinyl, C5-C 20 Ariel, C6-C 24 Alkaline, and C6-C 24 Aralkyl; Hydroxyl; Substituted or unsubstituted C1-C 24 Alkoxy, C2-C 24 Alkenyloxy, C2-C 24 Alkynyloxy, C5-C 20 Aryloxy and acyloxy; acyl, C2-C 24 Alkoxycarbonyl, C6-C 20 Aryloxycarbonyl, C2-C 24 Alkylcarbonyl, C6-C 20 Arylcarbonyl, halocarbonyl, formyl, and thioformyl; C2-C 24 Alkylcarbonates and C6-C 20 Arylcarbonates; Carboxylates and Carboxylates (C2-C 24 Alkylcarboxylates and C6-C 20Contains arylcarboxylates); carbamoyl (mono(C1-C) 24 Alkyl)-substituted carbamoyl, di(C1-C 24 Alkyl)-substituted carbamoyl, monosubstituted aryl carbamoyl, and mixed alkyl / aryl-substituted carbamoyl) and thiocarbamoyl; carbamato(mono(C1-C) 24 Alkyl)-substituted carbamates, di(C1-C 24 (Includes alkyl)-substituted carbamatoses, monosubstituted aryl carbamatoses, and mixed alkyl / aryl-substituted carbamatoses); carbamides, cyano, isocyanos, cyanato, isocyanato, and isothiocyanato; amino(mono and di(C1-C) 24 Alkyl)-substituted amino, mono and di(C5-C 20 (Alyric)-substituted amino acids, and mixed alkyl / aryl-substituted amino acids); alkylamides and C6-C 20 Arylamides; iminos, alkyliminos, and aryliminos; nitros; nitroso; sulfhydryls (C1-C 24 Alkyl sulfanyl and C5-C 20 Contains arylsulfanils; sulfo(C1-C) 24 Alkyl sulfonates, and C5-C 20 Contains aryl sulfonates); sulfino (C1-C 24 Alkyl sulfinyl and sulfinyl-containing); aryl sulfinyl; sulfonyl (C1-C 24 Alkyl sulfonyl and C5-C 20 Contains arylsulfonyl); phosphino(mono, di, and tri(C1-C) 24 Alkyl)-substituted phosphinates, mono, di, and tri(C5-C 20 (Alyric)-substituted phosphinates, mixed alkyl / aryl-substituted phosphinates, and phosphine oxides); and phosphono(mono and di(C1-C) 24 Alkyl)-substituted phosphonates, mono and di(C5-C 20 Selected from (aryl)-substituted phosphonates, mixed alkyl / aryl-substituted phosphonates, and O-phosphonates.

[0081] R 1~R 12 These may also be selected from enols, ketones, esters, aldehydes, acid anhydrides, acyl halides, ethers, epoxides, phosphonics, phosphates, phospinites, phosphate esters, imides, azides, azos, nitrates, nitriles, carbimides, aziridines, hydroxylamines, ketoximes, aldoximes, nitrate esters, enamines, azoles, imidazoles, pyrroles, indoles, purines, pyrimidines, piperidines, pyridazines, pyridyls and derivatives, linear, cyclic and aromatic compounds, oxyhalides, sulfides, thioethers, thioesters, sulfonates, sulfinyls, thiocyanates, disulfides, sulfones, thioamides, sulfoxides, isothiocyanates, sulfonamides, sulfonyl halides, thioureates, and thiophosphate esters. In some embodiments, R 1 , R 2 , R 3 , and R 4 They are identical. For example, in some embodiments, R 1 , R 2 , R 3 , and R 4 These are identical, and contain hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted heteroatoms C1-C 24 Alkyl, substituted, or unsubstituted C5-C 20 Aryl, and substituted or unsubstituted C5-C 20 Selected from heteroaryls. For example, R 1 , R 2 , R 3 , and R 4 These are identical and are selected from hydrogen, phenyl, and methoxyphenyl. In some embodiments, R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 They are identical. For example, in some embodiments, R 5 , R6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 They are identical, and they are hydrogen. In some embodiments, R 1 , R 2 , R 3 , and R 4 They are identical, and are the first base, R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 The first group is identical and is the second group, while the second group is a different group. In some embodiments, X 1 , X 2 , X 3 , and X 4 They are identical. In other embodiments, X 1 , X 2 , X 3 , and X 4 They are not identical. In some embodiments, the ligand of interest has the structure of the following formula Y-II.

[0082] [ka]

[0083] In the formula, X 1 , X 2 , X 3 , X 4 , R 1 , R 2 , R 3 , and R 4 This is as defined in the above equation YI; n1, n2, n3, and n4 are independently selected from the integers 0, 1, 2, 3, and 4; R 13 , R 14 , R 15 , and R 16 Each of these independently corresponds to R in equation (1) above. 1 ~R 12The bases are selected as defined for . For example, in some embodiments, n1, n2, n3, and n4 are each 0. In some embodiments, R 13 , R 14 , R 15 , and R 16 Pairs of substituents selected from may collectively form a further ring, which may be aliphatic, aromatic, heteroatom-containing, and / or substituted. For example, in some embodiments, the ligand of siccative is phthalocyanine, tetrabenzoporphyrin, tetraazaporphyrin, or porphyrin. Accordingly, in some embodiments, the composition comprises one or more accelerators having the structure of the following formula Y-Ia or Y-IIa.

[0084] [ka]

[0085] In the formula, M is selected from Fe and Mn; n1 to n4, X 1 ~X 4 , and R 1 ~R 16 As described above, equations YI and Y-II are as described above. It should be noted that the dashed lines and double bonds shown in the equations herein are drawn in a specific direction, but are not intended to represent a definite or fixed position of the bond. In other words, the resonance structures of the equations described herein are intended to be within the scope of the present invention. Ligands of interest include tetraarylporphyrins, diarylporphyrins, tetraalkylporphyrins, dialkylporphyrins, and mixed aryl / alkylporphyrins, as well as porphyrins containing alkenyl substituents, alkynyl substituents, heteroatom-containing substituents (e.g., heteroaryls), and functionalized substituents (e.g., alkyls substituted with carboxyl groups). Specific ligands of interest, though not limited to them, include: phthalocyanine; tetrabenzoporphyrin; tetraazaporphyrin; tetratolylporphyrin; porphyrin; porphyrazine; 5,10,15,20-tetrakisphenylporphyrin; 5,10,15,20-tetrakis(4'-methoxyphenyl)porphyrin; 5-azaprotoporphyrin dimethyl ester; bis-porphyrin; coproporphyrin III; coproporphyrin III tetramethyl ester; deuteroporphyrin; deuteroporphyrin IX dimethyl ester; diformyl deuteroporphyrin IX dimethyl ester, dodecaphenylporphyrin; hematoporphyrin; hematoporphyrin IX; hematoporphyrin monomer; hematoporphyrin dimer; hematoporphyrin derivative; hematoporphyrin IX dimethyl ester; hematoporphyrin IX dimethyl ester Esters; Mesoporphyrin dimethyl ester; Mesoporphyrin IX dimethyl ester; Monoformyl-monovine-duteroporphyrin IX dimethyl ester; Monohydroxyethyl vinyl duuteroporphyrin; 5,10,15,20-Tetra(o-hydroxyphenyl)porphyrin; 5,10,15,20-Tetra(m-hydroxyphenyl)porphyrin; 5,10,15,20-Tetrakis-(m-hydroxyphenyl)porphyrin; 5,10,15,20-Tetra(p-hydroxyphenyl)porphyrin; 5,10,15,20-Tetrakis-(3-methoxyphenyl)porphyrin; 5,10,15,20-Tetrakis-(3,4-dimethoxyphenyl)porphyrin; 5,10,15,20-Tetrakis(3s-dimethoxyphenyl)porphyrin; 5,10,15,20-Tetrakis-(3,4,5-trimethoxyphenyl)porphyrin;2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-Tetraphenylporphyrin; Photofrin; Porphyrin c; Protoporphyrin; Protoporphyrin IX; Protoporphyrin dimethyl ester; Protoporphyrin IX dimethyl ester; Protoporphyrin propylaminoethylformamide iodide; Protoporphyrin, N-dimethylaminopropylformamide (fonnamide); Protoporphyrin propylaminopropylformamide iodide; Protoporphyrin butylformamide ; Protoporphyrin N,N-dimethylaminoformamide; Protoporphyrinformamide; Sapphyrin 13,12,13,22-tetraethyl-2,7,18,23-tetramethylsapphyrin-8,17-dipropanol; Sapphyrin 2,3,12,13,22-tetraethyl-2,7,15,23-tetramethylsapphyrin-8-monoglycoside; Sapphyrin 3; Meso-tetra-(4-N-carboxyphenyl)-porfin; Tetra-(3-methoxyphenyl)-porfin; Tetra-(3-methoxy-2,4-di Fluorophenyl)-porfin; 5,10,15,20-tetrakis(4-N-methylpyridyl)porfin; mesotetra-(4-N-methylpyridyl)porfintetrachloride; meso-tetra(4-N-methylpyridyl)porfin; meso-tetra-(3-N-methylpyridyl)-porfin; meso-tetra-(2-N-methylpyridyl)porfin; tetra(4-N,N,N-trimethylanifinium)porfin; mesotetra-(4-N,N,N-trimethylaminophenyl)porfintetrachloride; tetra Lanafthaloporphyrin; 5,10,15,20-tetraphenylporphyrin; tetraphenylporphyrin; meso-tetra-(4-N-sulfonatophenyl)-porfin; tetraphenylporfin tetrasulfonate; meso-tetra-(4-sulfonatophenyl)porfin; tetra-(4-sulfonatophenyl)porfin; tetraphenylporphyrin sulfonate; mesotetra-(4-sulfonatophenyl)porfin; tetrakis-(4-sulfonatophenyl)porphyrin; meso-tetra(4-sulfonatophenyl)porfin;Examples include meso-(4-sulfonatophenyl)porphine; meso-tetra-(4-sulfonatophenyl)porphine; tetrakis(4-sulfonatophenyl)porphyrin; meso-tetra-(4-N-trimethylanilinium)-porphine; uroporphyrin; uroporphyrin I; uroporphyrin IX; and uroporphyrin III. In some embodiments, naturally occurring porphyrins, such as porphyrin ligands found in heme or chlorophyll, are suitable. Further specific ligands and methods for their preparation can be found in relevant literature, for example, Kadish et al., Handbook of Porphyrin Science: With Applications to Chemistry, Physics, and Materials (World Scientific, 2010), the contents of which are incorporated herein by reference. This composition and method contain a 1,3-dioxo compound. The 1,3-dioxo compound is thought to function as a polymerization initiator for radical polymerizable components. The 1,3-dioxo compound can be selected from compounds having the following formulas DI to D-VI.

[0086] [ka]

[0087] In the formula, A is O or S, n is an integer from 1 to 6, and m is a repeating unit from 2 to 20. R is H, linear or branched C1-C 20 Alkyl, C6-C 20 They are aryl, alkylaryl, and arylalkyl. R 1 , R 2 H, linear or branched C1-C 20 Alkyl, C6-C 20 Aryl, alkylaryl, arylalkyl, part of a polymer chain, OR 3 , NR 3 R 4 and; R 1 , R 2, R 3 , and R 4 Each of these is C1-C individually. 20 Alkyl, C6-C 20 It may represent an aryl, alkylaryl, or arylalkyl group, each optionally containing one or more heteroatoms and / or substituents; or R 1 and / or R 2 During and / or R 1 and R 3 During and / or R 1 and R 4 A ring may exist between them; or R 3 and / or R 4 It may be part of the polymer chain, attached to the polymer chain, or contain polymerizable groups. Preferably, R 1 and / or R 2 is C1-C 20 Alkyl and / or C1-C 20 It is aryl. More preferably, R 1 and / or R 2 The group is a methyl group. In some embodiments, the 1,3-dioxo compound is an acetylacetonate. The 1,3-dioxo compound may be a polymer or a polymerizable monomer or oligomer. In some embodiments, the amount of the 1,3-dioxo compound is 0.05 to 5% by mass, calculated based on the total mass of the polymerizable composition. The amount of the 1,3-dioxo compound is 0.1 to 2 parts per 100 parts of the radical polymerizable resin.

[0088] In some embodiments, the 1,3-dioxo compound is selected from the compounds of formula D-II. In some embodiments, the 1,3-dioxo compound may optionally be a mono or polyethoxylated and propoxylated diol, triol, and polyol acetacetate, such as ethylene glycol monoacetate, ethylene glycol diacetate, 1,2-propanediol monoacetate, 1,2-propanediol diacetate, 1,3-propanediol monoacetate, 1,3-propanediol diacetate, 1,4-butanediol monoacetate, 1,4-butanediol diacetate, 1,6-hexanediol monoacetate, 1,6-hexanediol diacetate, neopentyl glycol monoacetate, neopentyl glycol diacetate, trimethylol Selected from ropane monoacetate, trimethylolpropane diacetate, or trimethylolpropane triacetate, glycerin monoacetate, glycerin diacetate, glycerin triacetate, pentaerythritol diacetate, pentaerythritol monoacetoerythritol, pentaerythritol biacetate, pentaerythritol triacetate, pentaerythritol tetraacetate, dipentaerythritol monoacetate, dipentaerythritol diacetate, dipentaerythritol triacetate, dipentaerythritol tetraacetate, dipentaerythritol pentaacetate, or dipentaerythritol hexaacetate, etc.

[0089] In some embodiments, the 1,3-dioxo compound may include monofunctional or polyfunctional compounds. Examples, though not limited to them, include methyl acetate, ethyl acetate, t-butyl acetate, 2-ethylhexyl acetate, lauryl acetate, acetate anilide, pentanedione, acetylacetone, 2-(aceto-acetoxy)ethyl methacrylate, benzyl acetate, α-acetyl-γ-butyrolactone, 2-acetylcyclopentanone, 2-acetylcaprolactone, cyclohexanedimethanol diacetate, diethyl malonate, dimethyl malonate, ethoxylated or propoxylated bisphenol A diacetate, 3-methyl-2,4-pentanedione, 2,2-dimethyl-1,3-dioxan-4,6-dione, glycerin triacetate, polycaprolantone triacetate, 2-acetyl-polybutyrolactone, and 2-acetyl-polycaprolactone. 1,3-Dioxo compounds can be used alone or in mixtures of two or more. The 1,3-Dioxo compounds can be selected based on the desired reactivity of the system, the compatibility of the mixture, the color after curing, the physical properties, and the cost of the raw materials.

[0090] In some embodiments, the composition and method include one or more different tertiary amines that can be used as accelerators and gelation time drift stabilizers. For example, the tertiary amines can be selected from N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyltoluidine, N,N-diethyltoluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, ethoxylated p-toluidine, N,N-bis-(2-hydroxyethyl)-p-toluidine, and mixtures thereof. Toluidine derivatives are considered particularly preferred activators, with N,N-dialkyltoluidines and alkoxylated p-toluidines being particularly preferred. The tertiary amines can be used alone or as a mixture of two or more. In some embodiments, the compositions and methods include one or more various heterocyclic amines that can be used as accelerators and gelation time drift stabilizers. For example, the heterocyclic amine can be selected from compounds of the following formula H-I, H-II, or H-III.

[0091]

Chemical formula

[0092] In the formula, R 1 , R 2 , and R 3 are H, halogen, linear or branched C1-C 20 alkyl, C6-C 20 aryl, alkylaryl, arylalkyl, part of a polymer chain, OR 4 , NR 4 R 4 ; R 4 is H, linear or branched C1-C 20 alkyl, C6-C 20 aryl, alkylaryl, arylalkyl. Examples include 2,2'-bipyridine and 1,10-phenanthroline. The heterocyclic amine may be included in the polymerizable composition in an amount of 0.0005 to 1.0 parts, for example, 0.001 to 2.0 parts per 100 parts of the radically polymerizable component calculated based on the mass of the polymerizable component. In some embodiments, polyhydroxycarboxylic acids, such as tartaric acid or ascorbic acid (vitamin C), are included as additives also used to control gelation time drift. The acid intermediate for controlling gelation time drift may be added in an amount of 0.0005 to 2.0 parts, or 0.001 to 0.5 parts per 100 parts of the polymerizable component calculated based on the total mass of the polymerizable composition.

[0093] In some embodiments, the composition and method comprises one or more thiol (mercaptan) compounds. While this disclosure is not theoretically bound, the thiol compounds are considered to function as accelerators and / or gelation time drift stabilizers in the composition and method. The thiol compounds may be monofunctional or difunctional. Non-limiting examples of thiol compounds include: mercaptobenzothiazole (MBT), ethanethiol, propyl mercaptan, butanethiol, pentanethiol, 1-hexanethiol, octanthiol, 1-heptanethiol, 1-nonathiol, allyl mercaptan, furfuryl mercaptan, 2-mercaptoethanol, decanethiol, 1-undecanethiol, n-dodecyl mercaptan, 1-hexadecanethiol, n-octadecyl mercaptan, d-limonene dimercaptan, methyl-3-mercaptopropionate, 2-mercaptoethyl palmitate, dibutyl mercaptosuccinate, ferrous mercaptobenzothiazolate, cyclohexanethiol, thiophenol, tolyl mercaptan, phenethyl mercaptan, bromobenzyl mercaptan, and copperdic mercaptobenzothiazolate. Suitable polythiol compounds include mercaptoacetates and mercaptopropions of low molecular weight polyols having 2 to 8, preferably 2 to 4, hydroxyl groups and up to about 75 equivalents, some or all of which are esterified with mercaptoacetates and / or mercaptopropionates. Examples of such low molecular weight polyols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, trimethylolethane, erythritol, pentaerythritol, sorbitol, sucrose, and the like.Other suitable polythiol compounds include alkylenedithiols, e.g., 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc.; trithiols, e.g., 1,2,3-trimercaptopropane, 1,2,3-tri(mercaptomethyl)propane, 1,2,3-tri(mercaptoethyl)ethane, (2,3-di((2-mercaptoethyl)thio)-1-propanechiol, etc.; yet another useful polythiol compound is a mercapto-substituted fatty acid having at least two mercapto substituents in the fatty acid chain. Other examples of polyfunctional thiols are described, for example, in U.S. Patent 9,290,462; the contents of that disclosure are incorporated herein by reference in their entirety. Mixtures of the above may also be used.

[0094] Thioureas such as 1,3-di-o-tolyl-2-thiourea, 1,3-di-p-tolyl-2-thiourea, 1,3-di-tert-butyl-2-thiourea, 1,3-diallyl-2-thiourea, 1,3-dibenzyl-2-thiourea, 1-(3-pyridyl)-2-thiourea, 1-butyl-2-thiourea, 1-butyl-3-phenyl-2-thiourea, acetylthiourea, tetramethylthiourea, thiourea, N-ethylthiourea, N,N'-dibutylthiourea, N,N'-diethylthiourea, N,N'-dimethylthiourea, N,N'-diphenylthiourea, N,N'-diphenylthiourea, and N-phenylthiourea may be incorporated into this composition and method. Examples of thioureas are described in U.S. Patent Nos. 3,338,876; 3,970,505; 4,569,976; 7,173,074; and 7,498,367; the disclosures of these are incorporated herein by reference in their entirety. Mixtures of the above may also be used.

[0095] In some embodiments, a key parameter during the preparation of the composite material is that an appropriate heat of polymerization should be generated during the crosslinking of the reactive components in the thermosetting system. Accordingly, in some embodiments, the composition and method have a heat of polymerization of less than 950 KJ / Kg, or less than 925 KJ / Kg, or less than 900 KJ / Kg, or less than 875 KJ / Kg, or 850 KJ / Kg, or less than 825 KJ / Kg, or less than 800 KJ / Kg, or less than 775 KJ / Kg, or less than 750 KJ / Kg, or less than 700 KJ / Kg, or less than 650 KJ / Kg, or less than 600 KJ / Kg. In some embodiments, the heat of polymerization is greater than 100 KJ / Kg, or greater than 125 KJ / Kg, or greater than 150 KJ / Kg, or greater than 175 KJ / Kg, or greater than 200 KJ / Kg. The express intention is that a range can be formed by combining either the aforementioned maximum and minimum values. The generation of appropriate heat of polymerization is selectable under this disclosure and is of great importance, as the final mechanical properties of the finished product will be determined by the appropriate crosslinking of the mixture. The heat of polymerization will vary depending on the actual amounts of vinyl-containing compounds and other components in the mixture. In some embodiments, the peak exothermic reaction must be kept below a desired level during the crosslinking of the reactive components in the thermosetting system. Accordingly, in some embodiments, the composition and method have a peak exothermic reaction of less than 300°C, or less than 280°C, or less than 260°C, or less than 250°C. In some embodiments, the time to peak exothermic reaction is 5 to 60 minutes, or 5 to 30 minutes. In some embodiments, the gelation time is 2 to 60 minutes, or 2 to 25 minutes.

[0096] Optionally, the composition and method may include one or more transition metal salts or complexes in addition to manganese or iron-containing salts or complexes, and may include metals such as lithium, calcium, vanadium, zirconium, titanium, nickel, sodium, copper, potassium, magnesium, and barium. The transition metal salts may be given as chlorides, bromides, iodides, nitrates, sulfates, phosphates, oxalates, salicylates, alkyl organic acids, other carboxylates, naphthenates, etc. They may be incorporated alone, in pairs, or with one, two, or mixtures of the above metals. The transition metal complexes may have the above ligands. In some embodiments, polymers, copolymers, or oligomers containing reactive functional groups according to the present invention can form mixtures that undergo crosslinking reactions with other thermosetting resins, or in the presence of thermoplastics or mixtures thereof, to form composite materials. For the purposes of the present invention, it is preferable to use unsaturated polyester resins, saturated polyester resins, vinyl ester resins, and urethanes containing vinyl functional groups. Unsaturated polyester resins can be formed by conventional methods. Typically, the resins are formed from the reaction of polyfunctional organic acids or acid anhydrides with polyhydric alcohols under technically well-known conditions. Available polyfunctional organic acids or acid anhydrides are any of many known compounds. Suitable polyfunctional acids or their anhydrides include, but are not limited to, maleic acid and its anhydride, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid and its anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, cyclohexanedicarboxylic acid, succinic anhydride, adipic acid, sebacic acid, azelaic acid, malonic acid, alkenyl succinic acid, e.g., n-dodecenyl succinic acid, dodecyl succinic acid, octadecenyl succinic acid, and their anhydrides. Any of the above lower alkyl esters may be used. Any mixture of the above is suitable without the limitations intended thereby.

[0097] Furthermore, polybasic acids having three or more carboxylic acid groups or their anhydrides may be used. These compounds include 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalentricarboxylic acid, 1,2,4-naphthalentricarboxylic acid, 1,3,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-carboxymethylpropane, tetra(carboxymethyl)methane, 1,2,7,8-octanetetracarboxylic acid, citric acid, and mixtures thereof. Suitable polyhydric alcohols that can be used to form unsaturated polyester resins include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,3-hexanediol, neopentyl glycol, 2-methyl-1,3-pentanediol, 1,3-butylene glycol, 1,6-hexanediol, hydrogenated bisphenol A, cyclohexanedimethanol, 1,4-cyclohexanol, ethylene oxide adduct of bisphenol, propylene oxide adduct of bisphenol, sorbitol, 1,2,3,6-hexatetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, Examples include 1,2,5-pentanetriol, glycerol, 2-methyl-propanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxyethylbenzene. A mixture of any of the above alcohols may be used.

[0098] The DCPD resins used in the present composition and method are known to those skilled in the art. These resins are typically DCPD polyester resins and derivatives and can be prepared according to a variety of accepted procedures. For example, these resins can be prepared by reacting DCPD, an ethylenically unsaturated dicarboxylic acid, and a compound having two groups, each containing a reactive hydrogen atom that reacts with a carboxylic acid group. For the purposes of the present invention, DCPD resins prepared from DCPD, maleic anhydride, maleic acid, fumaric acid, orthophthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, water, and glycols, such as, but not limited to, ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, dipropylene glycol, and polytetramethylene glycol, are particularly preferred. The DCPD resin may include a nadiic acid ester segment that can be prepared in situ from the reaction of pentadiene and maleic anhydride, or added in its anhydride form during the preparation of the polyester. Examples of the preparation of DCPD unsaturated polyester resins can be found in U.S. Patents No. 3,883,612 and No. 3,986,922.

[0099] DCPD resin can be used in various amounts when laminating the resin composition of the present invention. Preferably, the laminated resin composition contains about 10 to about 80 mass percent, more preferably about 20 to about 40 mass percent, of DCPD resin. Preferably, the DCPD resin has a number average molecular weight in the range of about 450 to about 1500, more preferably about 500 to about 1000. Furthermore, the DCPD resin preferably has an ethylenically unsaturated monomer content of less than 35 percent at an applicable viscosity of 200 to 800 cps. The vinyl ester resins used in this composition and method include reaction products of unsaturated monocarboxylic acids or anhydrides with epoxy resins. Examples of acids and anhydrides include (meth)acrylic acid or anhydride, α-phenylacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid or fumaric acid monomethyl and monoethyl esters, vinyl acetic acid, sorbic acid, cinnamic acid, etc., along with mixtures thereof. Known epoxy resins are available and include substantially any reaction product of polyfunctional halohydrins, such as epichlorohydrin, with phenols or polyhydric phenols. Suitable phenols or polyhydric phenols include, for example, resorcinol, tetraphenolethane, and various bisphenols, such as bisphenol A, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylmethane, and 2,2'-dihydroxydiphenyl oxide. Novolac epoxy resins may also be used. Any mixture of the above may be used. Furthermore, the vinyl ester resin may have pendant carboxyl groups formed by the reaction of esters and acid anhydrides with hydroxyl groups of the vinyl ester skeleton.

[0100] Other components in the resin may include epoxy acrylate oligomers known to those skilled in the art. For example, the term “epoxy acrylate oligomer” may be defined for the purposes of this invention as a reaction product of acrylic acid and / or methacrylic acid with an epoxy resin. An example of a process relating to the preparation of epoxy acrylates can be found in U.S. Patent No. 3,179,623, the entire disclosure of which is incorporated herein by reference. Available epoxy resins are known and include substantially any reaction product of polyfunctional halohydrins, such as epichlorohydrin, for example, but not limited to, epichlorohydrin, with phenol or polyhydric phenol. Examples of phenol or polyhydric phenols include, but not limited to, resorcinol, tetraphenolethane, and various bisphenols, such as bisphenol A, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylmethane, 2,2'-dihydroxydiphenyl oxide, phenol or cresol-formaldehyde condensates, etc. Any mixture of the above may be used. Preferred epoxy resins for forming epoxy acrylates are those derived from bisphenol A and bisphenol F, and in particular, liquid condensates thereof with epichlorohydrin having a molecular weight in the range of about 300 to about 800 are preferred. It is preferable to use epoxy acrylate of the following formula EI.

[0101] [ka]

[0102] In the formula, R1 and R2 are H or CH3, and n is between 1 and 3, more preferably between 1 and 2. Other examples of usable epoxy acrylate oligomers include relatively low-viscosity epoxy acrylates. For example, these materials can be obtained by the reaction of epichlorohydrin with a diglycidyl ether of an aliphatic diol or polyol. Polyacrylate is also useful in this composition for the preparation of molding compositions. Urethane poly(acrylate) of the following formula AI may be used as part of the mixture.

[0103] [ka]

[0104] In the formula, R1 is hydrogen or methyl; R2 is a linear or branched divalent alkylene or oxyalkylene group having 2 to 5 carbon atoms; R3 is a divalent group remaining after the reaction of a substituted or unsubstituted diisocyanate; R4 is a hydroxyl-free residue of an organic polyhydric alcohol containing a hydroxyl group bonded to a different atom; and f has an average value of 2 to 4. These compounds are typically reaction products of polyols, in which the hydroxyl group first reacts with the diisocyanate using 1 equivalent per hydroxyl group, and the free isocyanate group reacts with the hydroxyalkyl ester of acrylic acid or methacrylic acid. Polyhydric alcohols suitable for the preparation of urethane poly(acrylate) typically contain at least two carbon atoms and may contain two to four (including two and four) hydroxyl groups. Examples include polyols based on polycaprolactone esters of polyhydric alcohols, such as those described in U.S. Patent No. 3,169,945. Unsaturated polyols, such as those described in U.S. Patents No. 3,929,929 and 4,182,830, may also be used. Diisocyanates suitable for the preparation of urethane poly(acrylates) are technically well known and include aromatic, aliphatic, and alicyclic diisocyanates. These isocyanates can be diluted with a small amount of glycol to lower their melting point and form liquid isocyanates. Suitable hydroxyalkyl esters for the final reaction of the polyisocyanate formed from the polyol and diisocyanate are exemplified by hydroxyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate. However, any acrylic acid ester or amide, or methacrylate ester or amide containing a socyanate-reactive group, may be used. The urethane poly(acrylate) as described above is described, for example, in U.S. Patent Nos. 3,700,643; 4,131,602; 4,213,837; 3,772,404 and 4,777,209. In some embodiments, the composition comprises a urethane poly(acrylate) of the following formula C-I.

[0105]

Chemical formula

[0106] Wherein, R1 is hydrogen or methyl; R2 is a linear or branched alkylene or oxyalkylene group having 2 to about 6 carbon atoms; R3 is a polyvalent residue remaining after the reaction of a substituted or unsubstituted polyisocyanate; g has an average value of about 2 to 4. These compounds are typically reaction products of a polyisocyanate and a hydroxyalkyl ester per isocyanate group. Polyisocyanates suitable for the preparation of urethane poly(acrylates) are well known in the art and include aromatic, aliphatic and cycloaliphatic polyisocyanates. Some diisocyanates can be extended with a small amount of glycol to lower their melting points and form liquid isocyanates. The urethane poly(acrylate) as described above is described, for example, in U.S. Patent No. 3,297,745 and British Patent No. 1,159,552. In some embodiments, the composition comprises a half ester or half amide characterized by the following formula C-II.

[0107] [[ID=​​​​​​​​​​​​​​​

[0110] It may contain, W and Z are independently -O- or the following base

[0111] [ka]

[0112] And, R3 is hydrogen or a lower alkyl group. The compound is typically a semi-ester or semi-amide product formed by the reaction of a hydroxyl, amino, or alkylamino-containing ester or amide derivative of acrylic acid or methacrylic acid with maleic anhydride, maleic acid, or fumaric acid. These are described, for example, in U.S. Patents 3,150,118 and 3,367,992. In some embodiments, the composition comprises an unsaturated isocyanurate characterized by the following formula C-III.

[0113] [ka]

[0114] In the formula, R1 is hydrogen or methyl, R2 is a linear or branched alkylene or oxyalkylene group having 2 to 6 carbon atoms, and R3 is a divalent group remaining after the reaction of a substituted or unsubstituted diisocyanate. The product is typically produced by the trimerization of the remaining free isocyanate after the reaction of a diisocyanate with 1 equivalent of hydroxyalkyl ester of acrylic acid or methacrylic acid. There is a common understanding that during isocyanurate formation, diisocyanates participate in the formation of two isocyanurate rings, thereby creating a cross-linked structure in which the isocyanurate rings can be linked by the diisocyanates used. It may also be possible to increase this type of cross-linking using polyisocyanates. Diisocyanates suitable for the preparation of urethane poly(acrylate) are technically well known and include aromatic, aliphatic, and alicyclic diisocyanates. These isocyanates can be diluted with a small amount of glycol to lower their melting points and form liquid isocyanates. Suitable hydroxyalkyl esters for the final reaction with the polyisocyanate formed from the polyol and diisocyanate are exemplified by hydroxyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate. However, any acrylic acid ester or methacrylic acid ester or acrylamide or acrylamide containing an isocyanate-reactive group can be used here. Other alcohols containing one hydroxyl group may also be used. The monoalcohol may be a monomer or polymer. The unsaturated isocyanurate is described, for example, in U.S. Patent No. 4,195,146. In some embodiments, the composition comprises a poly(amide-ester) characterized by the following formula C-IV.

[0115] [ka]

[0116] In the formula, R1 is independently hydrogen or methyl, R2 is independently hydrogen or a lower alkyl, and h is 0 or 1. These compounds are typically reaction products of vinyl addition prepolymers having multiple pendant oxazolines or 5,6-dihydro-4H-1,3-oxazine groups with acrylic acid or methacrylic acid. The poly(amide-ester) is described, for example, in British Patent No. 1,490,308. In some embodiments, the composition comprises a poly(acrylamide) or poly(acrylate-acrylamide) characterized by the following formula CV.

[0117] [ka]

[0118] In the formula, R1 is a primary or secondary amino group bonded to different carbon atoms, or, in the case of an amino alcohol, a polyvalent residue of an organic polyhydric amine or polyhydric amino alcohol containing amine and alcohol groups bonded to different carbon atoms; R2 and R3 are independently hydrogen or methyl; K is independently -O- or the following group

[0119] [ka]

[0120] And, In the formula, R4 is hydrogen or a lower alkyl group; i is 1 to 3. Polyhydric amines suitable for the preparation of poly(acrylamide) contain at least two carbon atoms and may contain 2 to 4 (including 2 and 4) amine or alcohol groups, wherein at least one group is a primary or secondary amine. These include alkane-amino alcohols and aromatic-containing amino alcohols. Polyhydric amino alcohols containing ether, amino, amide, and ester groups in the organic residues are also included. Examples of the above compounds are described, for example, in Japanese Public Publication Nos. JP80030502, JP80030503, and JP800330504, as well as in U.S. Patent No. 3,470,079 and British Patent No. 905,186.

[0121] Those skilled in the art will have the common understanding that the thermosetting organic materials described above are merely representative examples of those that can be used in carrying out the present invention. Saturated polyesters, polyethers, and polyurethanes that may be used in this composition include, for example, those described in U.S. Patents 4,871,811, 3,427,346, and 4,760,111. Saturated polyester resins and polyurethanes are particularly useful in applications of hand lay-up, spray-up, sheet molding compounding, hot melt adhesives, and pressure-sensitive adhesives. Suitable saturated polyester resins include, but are not limited to, crystalline and amorphous resins. These resins can be formed by any suitable technique. For example, saturated polyester resins can be formed by polycondensation of aromatic or aliphatic dicarboxylic acids or polycarboxylic acids with aliphatic or alicyclic diols or polyols or their prepolymers. Optionally, an excess of polyol can be added to obtain hydroxyl-terminated groups, or an excess of dicarboxylate monomer can be added to obtain carboxylic acid-terminated groups. Suitable polyurethane resins can be formed by the reaction of diols or polyols with diisocyanates, such as those described in U.S. Patent 4,760,111. By adding an excess of diol, hydroxyl terminal groups are obtained at the chain ends of the polyurethane. The saturated polyester and polyurethane may also contain various other components, such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, etc.

[0122] Thermoplastic polymer materials that reduce shrinkage during molding may also be included in this composition. Using these thermoplastic materials, molded articles with improved surface smoothness can be produced. Thermoplastic resins are added to the unsaturated polyester composition of the present invention to suppress shrinkage during curing. The thermoplastic resin is supplied in liquid form and prepared so that 30 to 45 percent thermoplastic resin is dissolved in 55 to 70 percent by mass of polymerizable resin having several polymerizable double bonds per molecule. Examples of thermoplastic resins include styrene polymers, polyethylene, polyvinyl acetate polymers, polyvinyl chloride polymers, polyethyl methacrylate, polymethyl methacrylate or copolymers, ABS copolymers, hydrogenated ABS, polycaprolactone, polyurethane, butadiene styrene copolymers, and saturated polyester resins. Further examples of thermoplastic resins are listed below: vinyl chloride and vinyl acetate; vinyl acetate and acrylic acid or methacrylic acid; styrene and acrylonitrile; styrene acrylic acid and allyl acrylate or allyl methacrylate; methyl methacrylate and alkyl esters of acrylic acid; methyl methacrylate and styrene; and copolymers of methyl methacrylate and acrylamide. In some embodiments, a mixture of 5 to 50 mass percent of liquid thermoplastic resin is used; preferably 10 to 30 mass percent of liquid thermoplastic resin.

[0123] Low-profile agents (LPAs) are mainly composed of thermoplastic polymer materials. LPAs may be included in the present composition. These thermoplastic intermediates exhibit several remaining compatibility issues with almost all types of thermosetting resin systems. Incompatibility between polymer materials leads to processing difficulties due to insufficient homogeneity between resins. Problems caused by phase separation of resin mixtures include scumming, poor color uniformity, low surface smoothness, and low gloss. Therefore, it is important to incorporate components that will help stabilize the resin mixture to obtain a homogeneous system that does not separate after preparation. For this purpose, a variety of stabilizers can be used in the present invention, including block copolymers obtained from polystyrene-polyethylene oxide, as described in U.S. Patents 3,836,600 and 3,947,422. Block copolymer stabilizers are made from styrene and polyethylene oxide-containing maleic anhydride semi-esters, as described in U.S. Patent 3,947,422. A saturated polyester prepared from hexanediol, adipic acid, and polyethylene oxide, available from BYK Chemie under code number W-972, is also a useful stabilizer. Other types of stabilizers include addition polymers prepared from vinyl acetate block copolymers and saturated polyesters, as described in Japanese Patent Publication No. 03-174424.

[0124] Fatty acids may be used without limitation in the preparation of polyesters and are usable in this composition. Prepolymerized fatty acids or their fatty acid esters prepared according to known processes are commonly used. Polybasic polymerized fatty acids prepared by polymerization of higher fatty acids or higher fatty acid esters are preferred because they provide good adhesion, flexibility, water resistance and heat resistance along with improved properties. The fatty acids may be either saturated or unsaturated fatty acids, and the number of carbon atoms may be 8 to 30, preferably 12 to 24, and more preferably 16 to 20, such as methyl, ethyl, propyl, butyl, amyl and cyclohexyl esters. Preferred polymerized fatty acids include polymerized products of unsaturated higher fatty acids, such as oleic acid, linoleic acid, ricinoleic acid, and eleacostearic acid. Polymerized products of tall oil fatty acids and beef tallow fatty acids can also be used. Hydrogenated polymerized fatty acid esters or oils can also be used. The proportion of dibasic carboxylic acids (hereinafter referred to as "dimer acids" herein) and tribasic or higher carboxylic acids in the polymerized fatty acids is not limited, and the ratio may be appropriately selected according to the expected final properties. Trimer acids or higher carboxylic acids may also be used.

[0125] The polymerization of fatty acid esters is not particularly limited. Typically, alkyl esters of the polymerized fatty acids are used as polymerized fatty acid esters. While alkyl esters such as methyl esters, ethyl esters, propyl esters, isopropyl esters, butyl esters, amyl esters, hexyl esters, etc., and higher alkyl esters such as octyl esters, decyl esters, dodecyl esters, pentadecyl esters, octadecyl esters, etc. can be used, lower alkyl esters are preferred, and methyl esters, ethyl esters, and butyl esters are even more preferred. These polymerized fatty acids and polymerized fatty acid esters can be used individually or in combination of two or more. The total ratio of polymerized fatty acids and polymerized fatty acid esters in the total polybasic carboxylic acid is not particularly limited and may be used in various proportions ranging from 3 to 40% by mass of the resin composition.

[0126] Similarly, a wide variety of epoxy compounds may be included in this composition. Typically, epoxy compounds are epoxy resins, also known as polyepoxides. Useful polyepoxides here may be monomers polymerized into homopolymers or copolymers (i.e., diglycidyl ether of bisphenol A), advanced high molecular weight resins, or unsaturated monoepoxides (i.e., glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, etc.). Most preferably, the epoxy compound contains, on average, at least one pendant or terminal 1,2-epoxy group (i.e., a vicinal epoxy group per molecule). Examples of useful polyepoxides include polyglycidyl ethers, polyglycidylamines, polyglycidylamides, polyglycidylimides, polyglycidyl hydantoins, polyglycidyl thioethers, polyglycidyl fatty acids, or drying oils, epoxidized polyolefins, epoxidized diunsaturated acid esters, epoxidized unsaturated polyesters, and mixtures thereof. Numerous epoxides prepared from polyhydric phenols include, for example, those disclosed in U.S. Patent No. 4,431,782. Polyepoxides can be prepared from monohydric, dihydric, and trihydric phenols and may include novolac resins. Polyepoxides may also include epoxidized cycloolefins; and polymeric polyepoxides, which are polymers and copolymers of glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ethers. Suitable polyepoxides are disclosed in U.S. Patents No. 3,804,735; No. 3,893,829; No. 3,948,698; No. 4,014,771 and No. 4,119,609; and in Lee and Naville, Handbook of Epoxy Resins, Chapter 2, McGraw Hill, New York (1967).

[0127] The present invention is applicable to various polyepoxides, and generally preferred polyepoxides are glycidyl polyethers of polyhydric alcohols or polyhydric phenols having a mass of 150 to 2,000 per epoxide. These polyepoxides are usually prepared by reacting at least 2 moles of epihalohydrin or glycerol dihalohydrin with 1 mole of polyhydric alcohol or polyhydric phenol and a sufficient amount of caustic alkali to bond with the halogen of the halohydrin. The product is characterized by the presence of one or more epoxides, i.e., a 1,2-epoxy equivalent greater than 1. The composition may contain a monoepoxide, such as butyl glycidyl ether, phenyl glycidyl ether, or cresyl glycidyl ether, as a reactive diluent. This reactive diluent is generally added to polyepoxide formulations to reduce their working viscosity and to provide better wetting of the formulation.

[0128] Vinyl monomers may be included as diluents along with vinyl esters, urethanes, and unsaturated and saturated resins. Suitable monomers include, for example, styrene and styrene derivatives such as α-methylstyrene, p-methylstyrene, divinylbenzene, divinyltoluene, ethylstyrene, vinyltoluene, tert-butylstyrene, monochlorostyrene, dichlorostyrene, vinylbenzyl chloride, fluorostyrene, and alkoxystyrene (e.g., paramethoxystyrene). Other usable monomers include vinylpyridines such as 2-vinylpyridine, 6-vinylpyridine, 2-vinylpyrrole, 2-vinylpyrrole, 5-vinylpyrrole, 2-vinyloxazole, 5-vinyloxazole, 2-vinylthiazole, 5-vinylthiazole, 2-vinylimidazole, 5-vinylimidazole, 3-vinylpyrazole, 5-vinylpyrazole, 3-vinylpyridazine, 6-vinylpyridazine, 3-vinylisoxazole, 3-vinylisothiazole, 2-vinylpyrimidine, 4-vinylpyrimidine, and 6-vinylpyrimidine. Other classifications of vinyl monomers, though not limited to them, include (meth)acrylates, vinyl aromatic monomers, vinyl halides, and vinyl carboxylates. Other usable monomers include, for example, diallyl phthalate, hexyl acrylate, octyl acrylate, octyl methacrylate, diallyl taconate, diallyl maleate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate. Mixtures of the above may also be used.

[0129] As used herein and in the claims, “(meth)acrylate” and similar terms refer to both methacrylate and acrylate. Any suitable monofunctional or polyfunctional acrylate may be used in the resin composition, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, cyclohexanol (meth)acrylate, phenoxyethyl (meth)acrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane tri(meth) These include tyrolpropane triacrylate, trimethylolmethane tetramethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, ethoxylated polyvalent phenol diacrylate and dimethacrylate (containing 1 to 30 ethylene oxide units per OH group of phenol), and propoxylated polyvalent phenol diacrylate and dimethacrylate (containing 1 to 30 propylene oxide groups per OH group of phenol). Some examples of useful divalent and polyvalent phenols include catechol; resorcinol; hydroquinone; 4,4'-biphenol; 4,4'-isopropylidenebis(o-cresol); 4,4'-isopropylidenebis(2-phenylphenol); alkylidene diphenols, e.g., bisphenol A; pyrogallol; phloroglucidol; naphthalenediol; phenol / formaldehyde resins; resorcinol / formaldehyde resins;and phenol / resorcinol / formaldehyde resins are also examples. Mixtures of the above diacrylates and polyacrylates may be used. Other examples, but not limited to, include oxyranyl (meth)acrylates, e.g., 2,3-epoxybutyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 10,11-epoxyundecyl (meth)acrylate, 2,3-epoxycyclohexyl (meth)acrylate, glycidyl (meth)acrylate, hydroxyalkyl (meth)acrylates, e.g., 3-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2,5-dimethyl- 1,6-Hexanediol (meth)acrylate, 1,10-Decanediol (meth)acrylate, aminoalkyl (meth)acrylate, e.g., N-(3-dimethylaminopentyl (meth)acrylate, 3-dibutylaminohexadecyl (meth)acrylate; (meth)acrylic acid, nitrile and other nitrogen-containing (meth)acrylates of (meth)acrylic acid, e.g., N-((meth)acryloyloxyethyl)diisobutylketimine, N-((meth)acryloylethoxyethyl)dihexadecylketamine Min, (meth)acryloylamide acetonitrile, 2-(meth)acryloyloxyethyl methyl cyanamide, cyanoethyl (meth)acrylate, aryl (meth)acrylate, e.g., benzyl (meth)acrylate or phenyl (meth)acrylate (in all cases the acrylic residue may be unsubstituted or substituted up to four times); carbonyl-containing (meth)acrylate, e.g., 2-carboxyethyl (meth)acrylate, carboxymethyl (meth)acrylate, oxazolidinylethyl (meth) Acrylate, N-((meth)acryloyloxy)formamide, acetonyl(meth)acrylate, N-(meth)acryloylmorpholine, N-(meth)acryloyl-2-pyrrolidinone, N-(2-(meth)acryloyloxyoxyethyl)-2-pyrrolidinone, N-(3-(meth)acryloyloxypropyl)-2-pyrrolidinone, N-(2-(meth)ylacryloyloxypentadecenyl)-2-pyrrolidinone, N-(3-(meth)acryloyloxyheptadecenyl)-2-pyrrolidinone;Ether alcohol (meth)acrylates, such as tetrahydrofurfuryl (meth)acrylate, vinyloxyethoxyethyl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, 1-butoxypropyl (meth)acrylate, 1-methyl-(2-vinyloxy)ethyl (meth)acrylate, cyclohexyloxymethyl (meth)acrylate, methoxymethoxyethyl (meth)acrylate, benzyloxymethyl (meth)acrylate, furfuryl (meth)acrylate, 2-butoxyethyl (meth) Acrylates, 2-ethoxyethoxymethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, allyloxymethyl (meth)acrylate, 1-ethoxybutyl (meth)acrylate, ethoxymethyl (meth)acrylate; halogenated alcohol (meth)acrylates, e.g., 2,3-dibromopropyl (meth)acrylate, 4-bromophenyl (meth)acrylate, 1,3-dichloro-2-propyl (meth)acrylate, 2-bromoethyl (meth)acrylate, 2-iodoethyl (meth)acrylate, Rolomethyl (meth)acrylate; phosphorus, boron, and / or silicon-containing (meth)acrylates, e.g., 2-(dimethylphosphato)propyl (meth)acrylate, 2-(ethylphosphyto)propyl (meth)acrylate, dimethylphosphinoethyl (meth)acrylate, dimethylphosphinomethyl (meth)acrylate, dimethylphosphonoethyl (meth)acrylate, dimethyl (meth)acryloylphosphonate, dipropyl (meth)acryloyl phosphate, 2-(dibutylphosphono)ethyl methacrylate, 2,3- Examples include buterene (meth)acryloylethyl borate, methyldiethoxy(meth)acryloylethoxysilane, diethyl phospahto(ethyl)(meth)acrylate; sulfur-containing (meth)acrylates, such as ethylsulfinylethyl(meth)acrylate, 4-thiocyanatobutyl(meth)acrylate, ethylsulfonylethyl(meth)acrylate, thiocyanatomethyl(meth)acrylate, methylsulfonylmethyl(meth)acrylate, and bis((meth)acryloyloxyethyl) sulfide.

[0130] Vinyl monomers and polyfunctional acrylates used with vinyl esters, unsaturated polyesters, saturated polyesters, and polyurethanes may be used in various amounts, preferably about 10 to 50, more preferably about 20 to 40 mass percent, based on the mass of the components that can be dissolved in them. Additives include inhibitors added to resin mixtures to stop or delay any crosslinking chain reactions that may be initiated by the expected formation of free radicals. The possibility of free radical formation is very high, as free radicals can form at carbon-carbon double bonds through several different mechanisms, including thermal and photointermolecular interactions. If this occurs, there is a fairly large possibility that the resin will crosslink during storage. Therefore, an appropriate amount of inhibitor in the system is useful in minimizing stability problems. Suitable inhibitors include, but are not limited to, hydroquinone (HQ), tolu-hydroquinone (THQ), bisphenol A (BPA), naphthoquinone (NQ), p-benzoquinone (p-BQ), butylated hydroxytoluene (BHT), hydroquinone monomethyl ether (HQMME), monotertiary butylhydroquinone (MTBHQ), ditertiary butylhydroquinone (DTBHQ), tertiary butylcatechol (TBC), and other substituted and unsubstituted phenols, as well as mixtures of the above. In this invention, a nitroxide initiator can also be used as an inhibitor.

[0131] Other polymerization inhibitors include stable hindered nitroxyl compounds, such as N,N-di-tert-butylnitroxide; N,N-di-tert-amylnitroxide; N-tert-butyl-2-methyl-1-phenylpropylnitroxide; N-tert-butyl-1-diethylphosphono-2,2-dimethylpropylnitroxide; 2,2,6,6-tetramethyl-piperidinyloxy; 4-amino-2,2,6,6-tetramethyl-piperidinyloxy; 4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy; 4-Oxo-2,2,6,6-tetramethyl-piperidinyloxy; 4-dimethylamino-2,2,6,6-tetramethyl-piperidinyloxy; 4-Ethanoloxy-2,2,6,6-tetramethyl-piperidinyloxy; 2,2,5,5-tetramethylpyrrolidinyloxy; 3-amino-2,2,5,5-tetramethylpyrrolidinyloxy; 2,2,4,4-tetramethyl-1-oxa-3-azacyclopentyl(pcntyl)-3-oxy; 2,2,4,4-tetramethyl-1-oxa-3-pyrrolinyl-1-oxy-3 -carboxylic acid; 2,2,3,3,5,5,6,6-octamethyl-1,4-diazacyclohexyl-1,4-dioxy; 4-bromo-2,2,6,6-tetramethyl-piperidinyloxy; 4-chloro-2,2,6,6-tetramethyl-piperidinyloxy; 4-iodo-2,2,6,6-tetramethyl-piperidinyloxy; 4-fluoro-2,2,6,6-tetramethyl-piperidinyloxy; 4-cyano-2,2,6,6-tetramethyl-piperidinyloxy; 4-carboxy-2,2,6,6-tetramethyl-piperidinyl Oxy; 4-Carbomethoxy-2,2,6,6-tetramethyl-1-piperidinyloxy; 4-Carboethoxy-2,2,6,6-tetramethyl-piperidinyloxy; 4-Cyano-4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy; 4-Methyl-2,2,6,6-tetramethyl-1-piperidinyloxy; 4-Carboethoxy-4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy; 4-Hydroxy-4-(1-hydroxypropyl)-2,2,6,6-tetramethyl-piperidinyloxy;Examples include 4-methyl(mcthyl)-2,2,6,6-tetramethyl(nlcthyl)-1,2,5,6-tetrahydropyridinyloxyl. Further useful stable hindered nitroxyl inhibitors are described in the following patent publications WO01 / 40404A1, WO01 / 40149A2, WO01 / 42313A1, U.S. Patents 4,141,883, US6,200,460, and US5,728,872, which are incorporated herein by reference. According to some embodiments of the present invention, various amounts of inhibitor may be used. Preferably, the amount of inhibitor ranges from about 0.001 to about 0.5 mass percent, and more preferably from about 0.04 to about 0.1 mass percent, based on the mass of the reactants.

[0132] Suitable non-fibrous fillers are inert granular additives that are essentially a means of reducing the cost of the final product while often degrading some of the physical properties of the polymerized and cured compound. Fillers used in the present invention include calcium carbonate in various forms and origins, silica in various forms and origins, silicates, silicon dioxide in various forms and origins, clay in various forms and origins, feldspar, kaolin, flax, zirconia, calcium sulfate, mica, talc, wood in various forms, glass (crushed, platelets, spheres, microballoons), plastics (crushed, platelets, spheres, microballoons), recycled polymer composite particles, metals in various forms, metal oxides or hydroxides (except those that alter shelf life or viscosity), metal hydrides or metal hydrates, carbon particles or granules, alumina, alumina powder, aramid, bronze, carbon black, carbon fiber, cellulose, α-cellulose, coal (powder), cotton, fibrous glass, graphite, jute, molybdenum, nylon, auron, rayon, amorphous silica, sisal fiber, fluorocarbons, and wood flour. Fibrous materials may be incorporated into the resin according to techniques known in the art. The addition of fibers provides a means to strengthen or harden the polymerization curing composition forming the substrate. Commonly used types include inorganic crystals or polymers, such as glass fibers, quartz fibers, silica fibers, fibrous ceramics, such as alumina-silica (refractory ceramic fibers); boron fibers, silicon carbide, silicon carbide whiskers or monofilaments, and metal oxide fibers, such as alumina-boron-silica, alumina-chromia-silica, zirconia-silica, etc. Organic polymer fibers, such as carbon fibers, fibrous graphite, acetate, acrylic resins (including acrylonitrile), aliphatic polyamides (e.g., nylon), aromatic polyamides, olefins (e.g., polypropylene, polyester, ultra-high molecular weight polyethylene), polyurethanes (e.g., Spandex), α-cellulose, cellulose, regenerated cellulose (e.g., rayon), jute, sisal, vinyl chloride, vinylidene, flax, and thermoplastic fibers; metallic fibers, such as aluminum, boron, bronze, chromium, nickel, stainless steel, titanium, or alloys thereof; and "whiskers," single, inorganic crystals. Preferably, fillers are added in an amount of 0 to 80% by mass, more preferably 20 to 60% by mass, based on the resin composition.

[0133] The present invention may include flame retardant compounds such as those described in many published documents and patents known to those skilled in the art. Brominated flame retardant compounds are useful for preparing flame retardant compositions, for example. Preferred brominated flame retardant compounds include, for example, 1,3,5-tris(2,4,6-tribromophenoxy)triazine, brominated polystyrene, brominated cyclodecane, brominated bisphenol A diglycidyl ether, alkyl or aryl or mixed aromatic-aliphatic phosphate esters, such as triphenyl, tricresyl phosphate, diphenyl-(2-ethylhexyl) phosphate, tris(2-chloroiso(SiO)propyl) phosphate, trityl phosphate, tri-n-butyl phosphate, tri-isobutyl phosphate, di-n-butyl phosphate, tris(allylphenyl phosphate), tris(2-methoxy-4-allyl phosphate), tris(2-propyl phosphate) Examples include phenyl(phenyl) phosphate, tri(4-vinylphenyl) phosphate, bisphenols such as bisphenol-A, bis(diphenyl phosphate ester) of resorcinol or hydroquinone, resorcinol bis(2,6-dixylenyl phosphate), bis(diphenylphosphoramide), phosphonates such as dimethyl(dimethy)methylphosphonate and dimethylpropylphosphonate, phosphites such as dimethyl phosphite, diethyl phosphite, trimethyl phosphite, triethyl phosphite, melamine polyphosphate, melamine cyanurate, metal phosphite, inorganic metal phosphite, red phosphorus, ammonium polyphosphate, and mixtures thereof.

[0134] When using the composition for bulk molding compounding or sheer molding compounding, a thickener may optionally be added in an amount of 0.05 to 10 percent, preferably 0.2 to 5 percent, by mass of the chemical thickener, based on the mass of the molding compound. The thickener is added to promote an increase in the viscosity of the compounding mixture. Examples include CaO, Ca(OH)2, MgO, or Mg(OH)2. Any suitable chemical thickener as conceivable by those skilled in the art of molding compounding may be used. The thickener coordinates with the carboxyl groups present in the polymer of the present invention or with any other polymer added together with it. Other thickeners that may be included are isocyanates. These substances react with hydroxyl groups that may be present in the polymer of the present invention or in other polymers added together with it. The polyisocyanates used in the present invention are aromatic, aliphatic, and alicyclic polyisocyanates having two or more isocyanate groups per molecule and having an isocyanate equivalent of less than 300. Preferably, the isocyanates are essentially ethylenically unsaturated and do not have other substituents capable of reacting with unsaturated polyesters. Polyfunctional isocyanates used in the above reactions are well known to those skilled in the art. For the purposes of the present invention, diisocyanates include, for example, aliphatic, alicyclic, araliphatic, aromatic, and heterocyclic diisocyanates of the type described by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pp. 75-136, (1949), for example, those corresponding to the following formulas. OCN-R-(NCO) n In the formula, n is equal to 1 to 3, and R represents a bifunctional aliphatic, alicyclic, aromatic, or aromatic aliphatic group having about 4 to 25 carbon atoms, preferably 4 to 15 carbon atoms, and not containing any group that can react with an isocyanate group. Examples of diisocyanates, though not limited to these, include toluene diisocyanate; 1,4-tetramethylene diisocyanate; 1,4-hexamethylene diisocyanate; 1,6-hexamethylene diisocyanate; 1,12-dodecane diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate; and 1-isocyanate-3,3,5-trimethyl-5-isocyanate. Methylcyclohexane; 2,4-Hexahydrotolylene diisocyanate; 2,6-Hexahydrotolylene diisocyanate; 2,6-Hexahydro-1,3-phenylenediisocyanate; 2,6-Hexahydro-1,4-phenylenediisocyanate; Perhydro-2,4'-Diphenylmethane diisocyanate; Perhydro-4,4'-Diphenylmethane diisocyanate; 1,3-Phenylenediisocyanate; 1,4-Phenylenediisocyanate; 2,4- Lylene diisocyanate; 2,6-toluene diisocyanate; biphenylmethane-2,4'-diisocyanate; biphenylmethane-4,4'-diisocyanate; naphthalene-1,5-diisocyanate; 1,3-xylene diisocyanate; 1,4-xylene diisocyanate; 4,4'-methylene-bis(cyclohexyl isocyanate); 4,4'-isopropyl-bis-(cyclohexyl isocyanate); 1,4-cyclohexyl diisocyanate; 3- Examples include isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI); 1-methyoxy-2,4-phenylenediisocyanate; 1-chlorophenyl-2,4-diisocyanate; p-(1-isocyanatoethyl)-phenylisocyanate; m-(3-isocyanatobutyl)-phenylisocyanate; and 4-(2-isocyanate-cyclohexyl-methyl)-phenylisocyanate. A mixture of any of the above may be used.If deemed appropriate, diisocyanates containing other functional groups, such as amino functional groups, may be used.

[0135] A preferred polyfunctional isocyanate additive for this molding composition may consist of a bifunctional additive prepared by a one-step addition reaction between one equivalent of a diol or triol having a molecular weight of 60 to 3000 and an excess of polyfunctional isocyanate. The excess amount of polyfunctional isocyanate is added in an amount sufficient to leave unreacted polyfunctional isocyanate free in the mixture after the reaction with the diol or triol in an amount of 0.01 to 50 mass percent of the total mixture, most preferably 1 to 30 mass percent of the mixture. It is preferable to utilize a catalyst in the reaction involving the diol or triol with the polyfunctional isocyanate. Many catalysts known to those skilled in the art may be used for this purpose. Suitable catalysts are described in U.S. Patents 5,925,409 and 4,857,579, the disclosures of which are incorporated herein by reference. Examples of polyhydric alcohols having at least two hydroxyl groups in the molecule and a hydroxyl value of 35 to 1,100 mg KOH / g include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol and polypropylene glycol having molecular weights of 200 to 3000, and polytetramethylene glycol having molecular weights of 200 to 3000.

[0136] The composition and method may use a carbodiimide, preferably a carbodiimide intermediate containing about 1 to about 1000 repeating units. Polycarbodiimide is preferred. Depending on the amount added, carbodiimide may be used to react with a resin or component containing active hydrogen. For example, to reduce the acid value of an unsaturated polyester resin or to increase the viscosity of the resin to form a gel-like substance. An example of a carbodiimide is described in U.S. Patent No. 5,115,072 by Nava et al., the entire disclosure of which is incorporated herein by reference. In general, carbodiimides are preferably polycarbodiimides, which include aliphatic, alicyclic, or aromatic polycarbodiimides. Polycarbodiimides can be prepared by many reaction schemes known to those skilled in the art. For example, polycarbodiimides can be synthesized by reacting an isocyanate-containing intermediate and a diisocyanate under appropriate reaction conditions. The isocyanate-containing intermediate can be formed by a reaction between a component that is typically an active hydrogen-containing monomer and a diisocyanate. Polycarbodiimides prepared by polymerization of isocyanates to form polycarbodiimides are also included, which subsequently react with an active hydrogen-containing component. In some embodiments, the carbodiimide intermediate is represented by a formula selected from the group consisting of the following formulas.

[0137] [ka]

[0138] In the formula, R4 and R5 are independently selected from the group consisting of alkyl, aryl, and compounds containing at least one radical; R6 may be a monomer unit or polymer unit having 1 to 1000 repeating units; and n is in the range of 0 to 100. Carbodiimide is preferably used in a proportion ranging from about 0.10 to about 50% by mass, and more preferably from about 1 to about 20% by mass, based on the mass of the reactants. The term "additive" is understood to mean any product used to modify the properties of a polymer. For example, in the preparation of a blend, the use of reinforcing agents enhances the mechanical properties of the resulting cured material, and the addition of UV stabilizers prevents degradation due to UV irradiation. Additives include phenolic antioxidants, such as those described on pages 1-104 of “Plastic additives”, Hanser Publishers, 1990, by R. Gachter and Muller. Mannich antioxidants, particularly phenols and naphthols suitable for the purposes of this application, include hindered aromatic alcohols, such as hindered phenols and naphthols, such as those described in U.S. Patent No. 4,324,717, the entire disclosure of which is incorporated herein by reference. Further additives known to those skilled in the art may be used in the resin composition of the present invention, such as paraffins, lubricants, fluids, defoaming agents, wetting agents, UV stabilizers, radiation curing initiators (i.e., UV curing initiators), and shrinkage-reducing additives. These additives can be used in the resin composition in various proportions. It is preferable to add an internal release agent to the molding composition of the present invention. Aliphatic metal salts, such as zinc stearate, magnesium stearate, calcium stearate, or aluminum stearate, can be used as the internal release agent. The amount of internal release agent added is in the range of 0.5 to 5.0 mass percent, preferably in the range of 0.4 to 4.0 mass percent. Therefore, stable release can be achieved without any cracks occurring in the molded product when it is removed from the mold.

[0139] Acrylic resins prepared by radical polymerization can be used in the mixture. The acrylic resin has an acid value preferably in the range of about 1 to 100 mg of KOH / g, more preferably about 5 to 50 mg of KOH / g, and most preferably about 10 to 30 mg of KOH / g. The acrylic resin has a hydroxyl value preferably in the range of 5 to 300, more preferably about 25 to 200, and most preferably 50 to 150. The acrylic resin has a preferred number average molecular weight of about 1,000 to about 100,000, more preferably about 2,000 to about 50,000, as determined by GPC against a polystyrene standard. The acrylic resin has a polydispersity of preferably about 1.5 to about 30, more preferably about 2 to 15. The Tg of the acrylic resin, as measured by differential scanning calorimetry, is preferably about -30°C to about 150°C, more preferably about -10°C to about 80°C. The styrene-acrylic resin used is preferably formed from about 0.5 to 30 mass percent (most preferably about 1 to 15 mass percent) of a functional mercaptan containing carboxyl, hydroxyl, siloxy, or sulfonic acid groups, and about 70 to about 99.5 mass percent (most preferably 85 to 99 mass percent) of an ethylenically unsaturated monomer. Examples of styrene / acrylic resins are described in Boutevin et al., Eur. Polym. J., 30; No. 5, pp. 615-619, and Rimmer et al., Polymer, 37; No. 18, pp. 4135-4139. Block copolymers of alkenyl aromatic hydrocarbons and alkylene oxides described in U.S. Patents 3,050,511 and 3,836,600 are also included.

[0140] Various hydroxyl and carboxyl-terminated rubbers may be used as reinforcing agents. Examples of such materials are presented in U.S. Patent No. 4,100,229, whose entire disclosure is incorporated herein by reference; and in JP Kennedy, J. Macromol. Sci. Chem. A21, pp. 929 (1984). Examples of such rubbers include carbonyl-terminated and hydroxyl polydienes. An example carbonyl-terminated polydiene is commercially available from BF Goodrich of Cleveland, OH under the trade name Hycar™. An ​​example hydroxyl-terminated polydiene is commercially available from Atochem, Inc. in Malvern, PA, and Shell Chemical in Houston, TX. Several polysiloxanes may be used as reinforcing agents. Suitable examples of polysiloxanes include poly(alkylsiloxanes), (e.g., poly(dimethylsiloxane)), and compounds containing silanol, carboxyl, and hydroxyl groups. Examples of polysiloxanes are described in Chiang and Shu, J. Appl. Pol. Sci. 361, pp. 889-1907, (1988). Various hydroxyl and carboxyl-terminated polyesters are prepared from lactones (e.g., γ-butyrolactone, etha-caprolactone), as described in Zhang and Wang, Macromol. Chem. Phys. 195, 2401-2407 (1994); In't Velt et al, J. Polym. Sci. Part A, 35, 219-216 (1997); and Youqing et al, Polym. Bull. 37, 21-28 (1996).

[0141] The present invention also includes various telechelic polymers, such as those described in “Telechelic Polymers: Synthesis and Applications”, Editor: Eric J. Goethals, CRC Press, Inc. 1989. Various polyethoxylated and polypropoxylated hydroxyl-terminated polyethers obtained from alcohols, phenols (including alkylphenols), and carboxylic acids can be used as reinforcing agents. Alcohols that can be used in forming these substances include, but are not limited to, tridecyl alcohol, lauryl alcohol, and mixtures thereof. Commercially suitable polyethoxylated and polypropoxylated oleyl alcohols are sold under the trade name Rhodasurf® by Rhone-Poulenc of Cranbury, NJ, along with Trycol® by Emery Industries of Cincinnati, Ohio. Examples of usable phenols and alkylphenols include, but are not limited to, octylphenol, nonylphenol, tristyrylphenol, and mixtures thereof. Commercially suitable tristyrylphenols include, but are not limited to, Igepal® by Rhone-Poulenc and Triton® by Rohm and Haas of Philadelphia, PA.

[0142] Unsaturated resins are particularly well suited for forming molded articles, including storage tanks, vehicle panels, boat structures, tub showers, artificial marble, solid surfaces, polymer concrete, and inner liners for pipe and pipeline reconstruction. Other application areas include gel coats and coatings. Unsaturated resins may be used alone or in combination with other suitable materials. When resins are used with other materials (e.g., fiber reinforcements and fillers), they are typically used to form reinforced products such as storage tanks, vehicle panels, boat structures, and tub showers by any known process, such as pultrusion, sheet molding compounding (SMC), spray-up, hand lay-up, resin transfer molding, vacuum injection molding, resin transfer molding, and vacuum-assisted resin transfer molding.

[0143] The compositions of the present invention offer several advantages. Because the products have a greater amount of carbon-carbon bonds than any typical thermosetting resin containing ester or urethane bonds, they are less susceptible to thermal and hydrolytic stability. Replacing these ester bonds with simple but highly stable carbon-carbon σ bonds yields unsaturated thermosetting resins that are not only more stable to hydrolysis and heat, but also chemically resistant. A critical problem with thermosetting resins is that their linear shrinkage can reach 5 percent for most common resins. Furthermore, the resins of the present invention have hydroxyl groups that can react with isocyanates or acid anhydrides and acid groups that can react with other epoxy-containing substances. The acid groups can also be used to coordinate with metal salts such as magnesium, zinc, or calcium oxides. These reactions are particularly important in SMC application fields, pultrusion, adhesives, and the preparation of open-type products. The resins of the present invention have low shrinkage rates, either alone or in combination with other thermosetting or thermoplastic resins. Examples illustrating these advantages are given below.

[0144] Polymers, copolymers, or oligomers containing reactive functional groups that can polymerize with other ethylenically unsaturated monomers or polymers are prepared by using styrene monomer as the main monomer in combination with various ethylenically unsaturated monomers. For the purposes of the present invention, it is preferable to prepare low molecular weight polymers, copolymers, and oligomers useful for the present invention by nitroxide-mediated radical polymerization. Polymer intermediates and / or oligomer intermediates are formed from ethylenically unsaturated monomers incorporated as repeating units in the backbone. The ethylenically unsaturated monomers function as solvents to carry out polymerization and as reactive monomers to form polymer and / or oligomer resin products. At least one of the monomers contains a reactive functional group that can react with other parts. Reactive functional groups contained in the monomers include, but are not limited to, hydroxyl, epoxy, phenol, thiol, amino, and other active hydrogen-containing monomers. Preferred functional groups are epoxy, hydroxyl, carboxyl, amino, and phenol.

[0145] Polystyrene intermediates containing functional groups can be further reacted with other monomers containing ethylenically unsaturated moieties. For example, a polystyrene intermediate containing epoxy groups along its skeleton can be further reacted with monomers such as acrylic acid or methacrylic acid. Another example is the preparation of a polystyrene intermediate containing a hydroxyl functional group that can be further reacted with isocyanate acrylates such as 2-isocyanatoethyl methacrylate. Diisocyanate reacted with 1 equivalent of hydroxyethyl methacrylate may be used. Another example is the preparation of a polystyrene intermediate containing acidic group functionality that can be further reacted with acrylates or methacrylates containing epoxy functionality. An objective of the present invention is to prepare a curable composition using polystyrene intermediates containing functional groups, preferably those containing reactive groups. Furthermore, polymer intermediates and / or oligomer intermediates can be used in combination with various polymers to form mixtures having a wide range of properties depending on the structure and properties of the materials in the mixture. In some embodiments of the present invention, a composite can be formed by applying a curable thermosetting composition to a substrate or reinforcing material, for example, by impregnating or coating the substrate or reinforcing material, and then curing the curable composition. The properties achieved from these materials provide composite systems that can be used in a variety of application fields, including molding, lamination, infusion, pultrusion, encapsulation, coating, adhesives, prepregs, electrical components, and electronic components. [Examples]

[0146] Examples Technical terms: Mn-Hydro-Cure(registered trademark) III - 9.0% Manganese AcBL-α-acetyl-γ-butyrolactone EtAcAc-Ethylacetylacetonate MAcAc-Methylacetylacetonate TAcAc-Tert-butylacetylacetonate DDD-2,2-dimethyl-1,3-dioxane-4,6-dione NQ-1,4-Naphthoquinone PBQ-para-benzoquinone THQ-Tolhydroquinone Ethanox 4703-2,6-di-tert-butyl-α-dimethylamino-p-cresol Potassium octoate DMPT-N,N-dimethyl-p-toluidine BiPy-2,2'-bipyridine DDSH - Dodecyl mercaptan TaAcid-Tartaric acid Ascorbic Acid (Vitamin C) Sty-Styrene MMA (Methyl Methacrylate) PEMA-Phenoxyethyl Methacrylate CHMA-Cyclohexyl Methacrylate BuDMA-Butanediol dimethacrylate HDDA-Hexanediol diacrylate NPGDMA - Neopentyl glycol dimethacrylate TMPTA - Trimethylol Triacrylate Polylite is a 31612-25-propylene glycol / maleic anhydride unsaturated polyester. Polylite HS 35060 is a dimethacrylate intermediate for bisphenol A. Polylite HS 35065 is an isophthalic acid-type dimethacrylate intermediate. DION 44070-00 is a low molecular weight epoxy bisphenol A vinyl ester. DION 32774-00 is a novolac epoxy vinyl ester. DION is a 9102-70-bisphenol A chain-extended epoxy vinyl ester. GT-Gelation time (minutes). TTP - Total time (minutes) until maximum heat is achieved. EXO - Peak heat generation (°C) achieved during the curing process. For components incorporated into polymerizable mixtures, the amounts shown in the table below are given as parts per hundred (pph) or parts per million (ppm) based on 100 parts of the reactive mixture. Amounts and concentrations are given in wt / wt units unless otherwise indicated in this text or context. The following examples are provided for illustrative purposes only and should not be construed as limitations of the present invention.

[0147] Sample preparation: A predetermined amount of the components claimed in the present invention, as described later, was added to 100 grams of liquid thermosetting resin. All components were mixed, and the gelation of the resin was checked periodically using a tongue depressor. Once the resin gelled, the time was recorded, and a thermocouple was inserted into the resin to measure the heat generated from the curing reaction. The heat generated was recorded along with the highest temperature observed. Examples of various methods for curing the thermosetting system are shown in the table below. Several methods can be used for the preparation and curing of polymerizable compositions. For example, in one method, a radical polymerizable component (a) is mixed with a manganese or iron-containing salt or complex (b), a tertiary amine or phosphine (c), and a nitrogen-containing heterocyclic or thiol compound (d). This polymerizable composition is stored for a desired period, and when the composition is to be used as a thermosetting resin, the polymerizable composition is mixed with a 1,3-dioxo compound (f) to initiate polymerization and form a crosslinked material. As a second method, a radical polymerizable component (a) is mixed with a polyhydroxycarboxylic acid (e.g., tartaric acid or ascorbic acid) or thiol compound (e), and a 1,3-dioxo compound (f). This polymerizable composition is stored for a desired period, and when the composition is to be used as a thermosetting resin, a manganese or iron-containing salt or complex (b) is mixed with the polymerizable composition to initiate polymerization and form a crosslinked network. Other possible methods, though not limited to them, include mixing (a) with (c), (d), and (f) and then adding (b) to form a crosslinked network. Depending on the chemical properties of (a) and its composition, other combinations of components (a) to (g) may be appropriate. In some embodiments, the method of combining the components of the polymerizable composition will be selected based on the thermosetting component, inhibitor, any additives that are part of the composition, and the final intended application field.

[0148] To evaluate the mechanical properties (e.g., strain temperature (HDT) and physical properties) of cured materials produced from polymerizable compositions, clear castings were prepared using the above method, cured overnight at room temperature, and then post-cured the following day at 180°F (82.2°C) for 2 hours and 250°F (121.1°C) for 2 hours. Mechanical properties were analyzed at room temperature using an Instron apparatus. The tensile strength of the resin was measured according to ASTM standard D-638; the flexural strength was measured according to ASTM standard D-79; the Barcol hardness was determined according to ASTM standard D-2583; the elongation was measured according to ASTM standard D-638; the thermal strain was measured according to ASTM standard D-648; and the Barcol hardness was determined according to the ASTM 2583-01 test method. The results are summarized in the table below. The heat of polymerization was determined using DSC (Differential Scanning Calorimetry) on the TA Instruments Q2000 system. The instrument was started with approximately 10 mg of catalyzed sample at 25°C in isothermal holding mode until complete exothermic polymerization was observed. The heat of curing generated due to the heat of polymerization was integrated using either a linear or sigmoid horizontal baseline. The results for the heat of polymerization are given in kJ / kg. Table 1 shows the curing behavior of 50 / 50 wt.% HDDA / PEMA mixtures with various amounts of BiPy, DMPT, Mn, and AcBL added.

[0149] [Table 1]

[0150] Table 2 shows the gelation time drift stability of 50 / 50 wt.% HDDA / PEMA mixtures with various amounts of BiPy, DMPT, Mn, and AcBL added.

[0151] [Table 2]

[0152] Table 3 shows the gelation time drift performance of 50 / 50 HDDA / MMA mixtures. (Meth)acrylate mixtures were accelerated with 1.0% AcBL and 500 ppm tartaric acid. Samples were catalyzed with 0.75% manganese salt to test gelation times over various number of days. RTG and TTP are given in minutes. Exo (peak exothermic) is given in °C.

[0153] [Table 3]

[0154] Table 4 shows the gelation time drift performance of 50 / 50 HDDA / MMA mixtures. (Meth)acrylate mixtures were accelerated with 1.0% AcBL and 250 ppm ascorbic acid (vitamin C). Samples were catalyzed with 0.75% manganese salt to test gelation times over various days. RTG and TTP are given in minutes. Exo (peak exothermic) is given in °C.

[0155] [Table 4]

[0156] Table 5 shows the curing behavior of HDDA / PEMA with BiPy, DMPT, Mn, and a mixture of AcBL and EtAcAc added. The samples were first accelerated with BiPy / DMPT along with MN. AcBL and EtAcAc were added to measure the gelation time.

[0157] [Table 5]

[0158] Table 6 shows the curing behavior of various (meth)acrylates in the presence and absence of mercaptan (thiol) compounds. In these examples, the (meth)acrylate monomer was first mixed with an acetylacetonate intermediate and a mercaptan compound, and then the polymerization was initiated by adding a manganese-containing salt. As can be observed, the thiol compound is useful for shortening the gelation time or obtaining a non-stick surface on a thin film without impairing the exothermic properties of polymerization.

[0159] [Table 6]

[0160] Table 7 shows the curing behavior of 32774-00 when mixed with BDDMA, HDDA, or MMA, and with the addition of BiPy, DMPT, Mn, and AcBL. The table also shows the heat of polymerization in joules / gram for samples 1 and 6.

[0161] [Table 7]

[0162] Table 8 shows the curing behavior of 31612-25 when mixed with MMA and supplemented with BiPy, DMPT, Mn, and AcBL.

[0163] [Table 8]

[0164] Physical properties: Table 9 shows the physical properties of castings of vinyl esters DION 9300-00 and DION 9102-70. The two resins were cured with cobalt salt (Co) and manganese salt. The cobalt-cured resin was accelerated with cobalt and dimethylaniline, and a room temperature gel time of 20 minutes was obtained using methyl ethyl ketone peroxide as a radical initiator. The manganese-cured resin was accelerated with manganese salt, BiPy, and DMPT, and a room temperature gel time of 20 minutes was obtained using AcBL as a radical initiator.

[0165] [Table 9]

[0166] Table 10 shows the physical properties of castings 31612-25, 32774-00, and HDDA / PEMA. The resins were promoted with Mn salt, BiPy, and DMPT, and AcBL was used as a radical initiator, resulting in a room temperature gelation time of 20 minutes.

[0167] [Table 10]

[0168] Table 10B shows the curing behavior of BuDMA with various amounts of para-benzoquinone (PBQ).

[0169] [Table 11]

[0170] Table 11 shows the curing behavior of BuDMA with various amounts of 1,4-naphthoquinone (NQ).

[0171] [Table 12]

[0172] Table 12 shows the curing behavior of BuDMA using various amounts of Ethanox 4703 (2,6-di-tert-butyl-α-dimethylamino-p-cresol).

[0173] [Table 13]

[0174] Table 13 shows the hardening behavior of HDDA using various amounts of Ethanox 4703.

[0175] [Table 14]

[0176] Table 14 shows the hardening behavior of HDDA / BuDMA using various amounts of THQ.

[0177] [Table 15]

[0178] Table 15 shows the hardening behavior of HDDA / BuDMA using various amounts of PBQ.

[0179] [Table 16]

[0180] Table 16 shows the curing behavior of HDDA / BuDMA using various amounts of tartaric acid.

[0181] [Table 17]

[0182] Table 17 shows the curing behavior of 35060-00 / HDDA using various amounts of PBQ, DMPT, and quaternary ammonium salt (alkyldimethylbenzylammonium chloride).

[0183] [Table 18]

[0184] Table 18 shows the curing behavior of 35060-00 / HDDA using various amounts of tartaric acid, potassium octate, ethyl acetylacetonate, and acetyl butyrolactone.

[0185] [Table 19]

[0186] Table 19 shows the curing behavior of 35065-00 / BuDMA using various amounts of tartaric acid, potassium octate, methylacetylacetonate, and acetylbutyrolactone.

[0187] [Table 20]

[0188] Table 20 shows the curing behavior of 35065-00 / BuDMA using various amounts of tartaric acid, potassium octate, tert-butylacetylacetonate, and acetylbutyrolactone.

[0189] [Table 21]

[0190] Table 21 shows the curing behavior of 35060-00 / HDDA using various amounts of tartaric acid, potassium octate, 2,2-dimethyl-1,3-dioxane-4,6-dione (DDD), and acetylbutyrolactone.

[0191] [Table 22]

[0192] Table 22 shows the mechanical properties and polymerization heat of resin 44070 blends with BuDMA and HDDA.

[0193] [Table 23]

[0194] Table 23 shows the mechanical properties and polymerization heat of resin 44070 blends with HDDA and NPGDMA.

[0195] [Table 24]

[0196] Considering this disclosure, it is evident that the composition and method can be carried out in accordance with this teaching. Furthermore, various components, materials, structures and parameters are included for illustrative purposes only and not in any limiting sense. Considering this disclosure, this teaching can be incorporated into other applications, and while remaining within the scope of the appended claims, the components, materials, structures and equipment for carrying out these applications can be determined.

[0197] Exemplary Embodiments The following exemplary embodiments are provided for illustrative purposes only and should not be construed as limitations of the present invention. Embodiment 1A. A polymerizable composition comprising: a) a radical polymerizable component; b) a manganese-containing or iron-containing salt or complex; c) an optional tertiary amine or phosphine; d) an optional nitrogen-containing aromatic heterocycle or thiol-containing compound; e) an optional polyhydroxycarboxylic acid; f) a 1,3-dioxo compound; and g) an optional transition metal salt other than manganese or iron-containing salts or complexes, wherein the polymerizable composition substantially does not contain one or more (preferably all) of cobalt, copper, and peroxide initiators, and the polymerizable composition comprises: (1) a combination of (i) a tertiary amine or phosphine and (ii) a nitrogen-containing aromatic heterocycle or thiol-containing compound; (2) a polyhydroxycarboxylic acid; or (3) at least one thiol-containing compound; wherein the polymerizable composition has a gelation time drift of less than about 20% or less than about 15% over 30 days or 60 days. Embodiment 1B. A polymerizable composition comprising the following: a) a radical polymerizable component; b) a manganese-containing or iron-containing salt or organic complex; c) a tertiary amine or phosphine; d) a nitrogen-containing aromatic heterocycle or thiol-containing compound; f) a 1,3-dioxo compound; and g) an optional transition metal salt other than a manganese or iron-containing salt or organic complex, wherein the polymerizable composition substantially does not contain one or more of cobalt, copper, and peroxide initiators. Embodiment 1C. A polymerizable composition comprising the following: a) a radical polymerizable component; b) a manganese-containing or iron-containing salt or organic complex; e) a polyhydroxycarboxylic acid; f) a 1,3-dioxo compound; and g) an optional transition metal salt other than a manganese- or iron-containing salt or organic complex, wherein the polymerizable composition substantially does not contain one or more of cobalt, copper, and peroxide initiators. Embodiment 1D. A polymerizable composition comprising the following: a) a radical polymerizable component; b) a manganese-containing or iron-containing salt or organic complex; d) a thiol-containing compound; f) a 1,3-dioxo compound; and g) an optional transition metal salt other than a manganese- or iron-containing salt or organic complex, wherein the polymerizable composition substantially does not contain one or more of cobalt, copper, and peroxide initiators. Embodiment 1E. A polymerizable composition comprising: a) a radical polymerizable component; b) a manganese-containing or iron-containing salt or organic complex; c) an optional tertiary amine or phosphine; d) an optional nitrogen-containing aromatic heterocycle or thiol-containing compound; and e) an optional polyhydroxycarboxylic acid, wherein the polymerizable composition has a characteristic gelation time when combined with a 1,3-dioxo compound, and the polymerizable composition has a gelation time drift of less than about 20% or less than about 15% over 30 days or 60 days. Embodiment 1F. A polymerizable composition comprising: a) a radical polymerizable component; c) an optional tertiary amine or phosphine; d) an optional nitrogen-containing aromatic heterocyclic or thiol-containing compound; e) an optional polyhydroxycarboxylic acid; and f) a 1,3-dioxo compound, wherein the polymerizable composition has a characteristic gelation time when combined with a manganese-containing or iron-containing salt or an organic complex, and the polymerizable composition has a gelation time drift of less than about 20% or less than about 15% over 30 days or 60 days.

[0198] Embodiment 2. A polymerizable composition according to any of Embodiments 1A to 1F, wherein the manganese or iron-containing salt or complex is selected from salts and complexes of the following formula and mixtures thereof; salts selected from the salts of the above formula (M)(RCOO-)2; the above naphthenate complex; or the above acetylacetonate complex. Embodiment 3. A polymerizable composition according to any of Embodiments 1A to 1F, wherein the manganese or iron-containing salt or complex is selected from organophosphine metal complexes containing organophosphine having the structure of formula PI, P-II, P-III, or P-IV, and mixtures thereof. Embodiment 4. A polymerizable composition according to any one of Embodiments 1A to 1F, wherein the manganese or iron-containing salt or complex is selected from complexes containing the nitrogen-donating ligand of the above formulas NI, N-II, N-III, N-IV, NV, N-VI, or N-VII. Embodiment 5. A polymerizable composition according to any of Embodiments 1A to 1F, wherein the 1,3-dioxo compound is selected from the compounds of formulas DI to DV and mixtures thereof. Embodiment 6. A polymerizable composition according to any one of Embodiments 1A to 1F, comprising a tertiary amine selected from the group consisting of N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyltoluidine, N,N-diethyltoluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, ethoxylated p-toluidine, N,N-bis-(2-hydroxyethyl)-p-toluidine, and mixtures thereof. Embodiment 7. A polymerizable composition according to any one of Embodiments 1A to 1F, comprising a nitrogen-containing heterocyclic amine selected from the group consisting of compounds of formula HI, H-II, or H-III and mixtures thereof. Embodiment 8. A polymerizable composition according to any one of Embodiments 1A to 1F, comprising a polyhydroxycarboxylic acid selected from tartaric acid, ascorbic acid, or a mixture thereof. Embodiment 9. A polymerizable composition according to any of Embodiments 1A to 1F, wherein the manganese or iron-containing salt or organic complex is selected from manganese octoate and manganese naphthenate, the heterocycle is 2,2'-bipyridine, the tertiary amine is N,N-dimethyl-p-toluidine, and the 1,3-dioxo compound is α-acetyl-γ-butyrolactone.

[0199] Embodiment 10. A curing system for curing a radical polymerizable component, comprising b) a manganese-containing or iron-containing salt or organic complex; c) an optional tertiary amine or phosphine; d) an optional nitrogen-containing aromatic heterocycle or thiol-containing compound; e) an optional polyhydroxycarboxylic acid; and f) a 1,3-dioxo compound, wherein the curing system substantially does not contain one or more of cobalt, copper, and peroxide initiators, and comprises at least one of the following: (i) a tertiary amine or phosphine, and (ii) a combination of a nitrogen-containing aromatic heterocycle or thiol-containing compound; (2) a polyhydroxycarboxylic acid; or (3) a thiol-containing compound. Embodiment 11. The curing system of Embodiment 10, wherein the curing system essentially consists of a manganese-containing salt or organic complex, a tertiary amine, and a nitrogen heterocycle. In some embodiments, the curing system also includes an inhibitor. Embodiment 12. The curing system of Embodiment 10 or 11, wherein the curing system consists essentially of a manganese-containing salt or organic complex, a polyhydroxycarboxylic acid, and a 1,3-dioxo compound. In some embodiments, the curing system also includes an inhibitor. Embodiment 13. A curing system according to any of Embodiments 10 to 12, wherein the curing system essentially consists of a manganese-containing salt or organic complex, a 1,3-dioxo compound, and a thiol-containing compound. In some embodiments, the curing system also includes an inhibitor.

[0200] Embodiment 14. A method for curing a polymerizable composition, A method comprising: a) a radical polymerizable component; b) a manganese-containing or iron-containing salt or organic complex; c) an optional tertiary amine or phosphine; d) an optional nitrogen-containing aromatic heterocycle or thiol-containing compound; e) an optional polyhydroxycarboxylic acid; and f) forming a mixture of 1,3-dioxo compounds; wherein the polymerizable composition substantially does not contain one or more of cobalt, copper, and peroxide initiators, and the polymerizable composition contains at least one of the following: (1) a combination of (i) a tertiary amine or phosphine and (ii) a nitrogen-containing aromatic heterocycle or thiol-containing compound; (2) a polyhydroxycarboxylic acid; or (3) a thiol-containing compound. Embodiment 15. The method of Embodiment 14, further comprising preparing a polymerizable composition comprising: a) a radical polymerizable component; b) a manganese-containing or iron-containing salt or organic complex; c) an optional tertiary amine or phosphine; d) an optional nitrogen-containing aromatic heterocycle or thiol-containing compound; and e) an optional polyhydroxycarboxylic acid. The method further comprises storing the polymerizable composition for at least 30 days or at least 60 days; and then mixing the polymerizable composition with a 1,3-dioxo compound. Embodiment 16. The method of Embodiment 14, further comprising preparing a polymerizable composition comprising: a) a radical polymerizable component; c) an optional tertiary amine or phosphine; d) an optional nitrogen-containing aromatic heterocyclic or thiol-containing compound; e) an optional polyhydroxycarboxylic acid; and f) a 1,3-dioxo compound. The method further comprises storing the polymerizable composition for at least 30 days or at least 60 days; and then mixing the polymerizable composition with a manganese-containing or iron-containing salt or an organic complex.

[0201] Embodiment 17. Any method according to Embodiments 14 to 16, wherein the radical polymerizable component is selected from the group consisting of polyester resin, vinyl ester resin, urethane acrylate resin, vinyl hydride resin, and combinations thereof. Embodiment 18. Any method of Embodiment 15, wherein a radical polymerizable component, a manganese or iron-containing salt or organic complex, a tertiary amine or phosphine, and a nitrogen-containing aromatic heterocycle or thiol-containing compound are mixed and stored for at least 30 days to form a mixture with a 1,3-dioxo compound. Embodiment 19. The method of Embodiment 14, wherein a radical polymerizable component, a manganese or iron-containing salt or organic complex and a polyhydroxyl carboxylic acid or thiol compound are mixed and stored for at least 30 days to form a mixture with a 1,3-dioxo compound. Embodiment 20. The method of Embodiment 14, wherein a radical polymerizable component and a 1,3-dioxo compound, a tertiary amine or phosphine, and a nitrogen-containing aromatic heterocycle or thiol-containing compound are mixed and stored for at least 30 days to form a mixture with a manganese or iron-containing salt or an organic complex. Embodiment 21. The method of Embodiment 14, wherein a radical polymerizable component and a 1,3-dioxo compound, along with a polyhydroxylcarboxylic acid or thiol compound, are mixed and stored for at least 30 days to form a mixture with a manganese or iron-containing salt or an organic complex. Embodiment 22. Any method of Embodiments 14 to 21, further comprising applying the mixture as a coating, layer, or casting before or during the curing of the polymerizable composition. Embodiment 23. Any method of Embodiments 14 to 21, wherein the polymerizable composition is applied as a sheet molding compound (SMC) resin, casting resin, adhesive, pultrusion resin, corrosion-resistant resin, flame-retardant resin, low or zero-styrene content resin, filament winding resin, hand lay-up resin, resin transfer molding resin, prepreg, gel coat, or coating resin.

[0202] Embodiment 24. A resin comprising a polymerizable composition of any of Embodiments 1A to 1F, wherein the resin is a sheet molding compound (SMC) resin, a resin transfer molding (RTM) resin, a casting resin, an adhesive resin, a pultrusion resin, a corrosion-resistant resin, a flame-retardant resin, a low or zero styrene content resin, a prepreg, a gel coat, or a coating resin. Embodiment 25. A polymerizable composition according to any of the above embodiments, wherein the polymerizable composition has a heat of polymerization of less than 950 kJ / kg. Embodiment 26. A polymerizable composition according to any of the above embodiments, wherein the polymerizable composition has a peak exothermic temperature of less than 300°C. Embodiment 27. A polymerizable composition according to any of the above embodiments, wherein the polymerizable composition has a time to peak exothermic reaction of 5 to 60 minutes. Embodiment 28. A polymerizable composition according to any of the above embodiments, wherein the polymerizable composition has a gelation time of 10 seconds to 60 minutes.

[0203] All patents and published documents referenced herein are expressly invoked by reference. As disclosed herein, a wide range of values ​​are provided. There is a common understanding that, unless the context clearly indicates otherwise, each intermediate value (intervening value) between the upper and lower limits of such ranges, up to one-tenth of the lower limit, is also specifically disclosed.

Claims

1. the below described: a) a radically polymerizable component; b) manganese- or iron-containing salts or organic complexes; c) an optional tertiary amine or phosphine; d) optional nitrogen-containing aromatic heterocycle or thiol-containing compounds; e) optional polyhydroxycarboxylic acids; f) 1,3-dioxo compounds; and g) optionally, a transition metal salt or organic complex other than the manganese- or iron-containing salt or organic complex; A polymerizable composition comprising: the polymerizable composition is substantially free of one or more of cobalt, copper, and peroxide initiators; and The polymerizable composition comprises: (1) A combination of (i) a tertiary amine or a phosphine, and (ii) a nitrogen-containing aromatic heterocycle or a thiol-containing compound; (2) polyhydroxycarboxylic acids; or (3) Thiol-containing compounds and the polymerizable composition has a gel time drift of less than about 20% over 30 days; The polymerizable composition.

2. The manganese or iron containing salts or complexes are salts and complexes of the formula: i) Formula (M)(RCOO-) 2 wherein M is either manganese or iron, and each R is independently selected from H, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted straight chain alkenyl, substituted or unsubstituted branched alkenyl, substituted or unsubstituted straight chain alkynyl, substituted or unsubstituted branched alkynyl, substituted or unsubstituted aryl, or substituted or unsubstituted alkylaryl; ii) The following formula 【Chemistry 1】 wherein M is either manganese or iron, m and n are independently 0 or greater, and R′ and R″ are independently selected from H, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted straight chain alkenyl, substituted or unsubstituted branched alkenyl, substituted or unsubstituted straight chain alkynyl, substituted or unsubstituted branched alkynyl, substituted or unsubstituted aryl, and substituted or unsubstituted alkylaryl. a naphthenate complex selected from the group consisting of iii) a compound of the formula: 【Chemistry 2】 where M is either manganese or iron, and R 1 , R 2 , R 3 and R 4 are each independently selected from H, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted straight chain alkenyl, substituted or unsubstituted branched alkenyl, substituted or unsubstituted straight chain alkynyl, substituted or unsubstituted branched alkynyl, substituted or unsubstituted aryl, and substituted or unsubstituted alkylaryl. An acetylacetonate complex selected from the complexes and mixtures thereof. The polymerizable composition according to claim 1.

3. The manganese or iron-containing salt or complex has the following formula PI, P-II, P-III or P-IV: 【Transformation 3】 wherein R1 in each occurrence is independently H, hydroxyl, C1-C6-containing branched or cyclic aliphatic; C1-C4 alkoxy; aryl, e.g., C6-C20 monocyclic or polycyclic aryl, such as phenyl, toluoyl, naphthyl, biphenyl, terphenyl, halogen-containing aryl aromatic, amino, silyl; heteroalkyl, e.g., C6-C20 monocyclic or polycyclic heteroaryl, such as thienyl, furyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, indolyl, quinolyl, and isoquinolyl; 【Chemistry 4】 (In the formula, R 1 is independently in each occurrence H, hydroxyl, C1-C6-containing branched or cyclic aliphatic, C1-C4 alkoxy; aryl, e.g., C6-C20 monocyclic or polycyclic aryl, such as phenyl, toluoyl, naphthyl, biphenyl, terphenyl, halogen-containing aryl aromatic, amino, silyl; heteroalkyl, e.g., C6-C20 monocyclic or polycyclic heteroaryl, such as thienyl, furyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, indolyl, quinolyl, and isoquinolyl; R 2 is independently in each occurrence H, a C1-C14 containing straight chain, branched or cyclic aliphatic, alkyl aromatic, halogen containing aryl aromatic, amino, silyl or alkoxy group, and R 1 Group, R 2 group or R 1 and R 2 the groups are interconnected by alicyclic or aromatic rings; n is 0 to 4; and Y is either N or P; 【Transformation 5】 (In the formula, R 1 is independently in each occurrence H, hydroxyl, C1-C6-containing branched or cyclic aliphatic, C1-C4 alkoxy; aryl, e.g., C6-C20 monocyclic or polycyclic aryl, such as phenyl, toluoyl, naphthyl, biphenyl, terphenyl, halogen-containing aryl aromatic, amino, silyl; heteroalkyl, e.g., C6-C20 monocyclic or polycyclic heteroaryl, such as thienyl, furyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, indolyl, quinolyl, and isoquinolyl; Y is N or P; 【Transformation 6】 wherein R is, independently in each occurrence, H, a C1-C14-containing linear, branched, or cyclic aliphatic, alkylaromatic, halogen-containing arylaromatic, amino, or alkoxy group; R 1 is independently in each occurrence H, hydroxyl, C1-C6-containing branched or cyclic aliphatic, C1-C4 alkoxy; aryl, e.g., C6-C20 monocyclic or polycyclic aryl, such as phenyl, toluoyl, naphthyl, biphenyl, terphenyl, halogen-containing aryl aromatic, amino, silyl; heteroalkyl, e.g., C6-C20 monocyclic or polycyclic heteroaryl, such as thienyl, furyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, indolyl, quinolyl, and isoquinolyl; R 2 are independently in each occurrence H, C1-C14 containing linear, branched or cyclic aliphatic, alkylaromatic, halogen-containing arylaromatic, silyl, amino or alkoxy groups, interconnected by alicyclic or aromatic rings; Y is either N or P.

2. The polymerizable composition according to claim 1, wherein the organophosphine metal complex is selected from organophosphine metal complexes containing organophosphines having the structure:

4. The manganese or iron containing salt or complex has the following formula NI, N-II, N-III, N-IV, NV, N-VI, or N-VII: 【Transformation 7】 (In the formula, R 1 and R 2 are independently, C 1-24 Alkyl, C 6-10 Aryl, heteroaryl, heteroaryl C 1-6 Alkyl, and -CH 2 -CH 2 -N(CH 3 ) 2 wherein heteroaryl is selected from the group consisting of pyridyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl, and thiazolyl; R 3 and R 4 are independently -H, C 1-8 Alkyl, C 1-8 Alkyl-OC 1-8 Alkyl, C 1 - 8 Alkyl-OC 6-10 Aryl, C 6-10 Aryl, C 1-8 -hydroxyalkyl, and -(CH 2 ) m C(O)OR 5 selected from the group consisting of: R 5 is -H or C 1-4 alkyl, and m is an integer selected from 0 to 4; R 6 and R 7 are each independently -H, -F, -Cl, -Br, ---OH, C 1-4 Alkoxy, -NH-C(O)-H, -NH-C(O)-C 1-4 Alkyl, -NH 2 , -NH-C I-4 Alkyl, and C 1-4 selected from the group consisting of alkyl; X 1 is -C(O)- or -[C(R 8 ) 2 ] n where n is an integer selected from 0 to 3, and each R 8 are independently -H, -OH, C 1-4 Alkoxy and C 1-4 alkyl) 2. The polymerizable composition of claim 1, wherein the nitrogen donor ligand is selected from the group consisting of:

5. The 1,3-dioxo compound is represented by the following formulae DI to D-VI: 【Transformation 8】 wherein A is O or S; n is an integer from 1 to 6 and m is from 2 to 20 repeat units; R is H, substituted or unsubstituted straight chain or branched C 1 -C 20 Alkyl, C 6 -C 20 aryl, alkylaryl, or arylalkyl; R 1 and R 2 are independently H, substituted or unsubstituted straight chain or branched C 1 -C 20 Alkyl, C 6 -C 20 Aryl, alkylaryl, arylalkyl, part of a polymer chain, OR 3 , or NR 3 R 4 and R 1 , R 2 , R 3 , and R 4 are each individually C 1 -C 20 Alkyl, C 6 -C 20 may represent an aryl, alkylaryl, or arylalkyl group, each of which may optionally contain one or more heteroatoms and / or substituents; or R 1 and R 2 Between and / or R 1 and R 3 Between and / or R 1 and R 4 There may be a ring between R 3 and / or R 4 may be part of or attached to a polymer chain or may contain a polymerizable group 2. The polymerizable composition of claim 1, wherein the compound is selected from the group consisting of the compounds of formula (I) and mixtures thereof.

6. 10. The polymerizable composition of claim 1, comprising a tertiary amine selected from the group consisting of N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-toluidine, N,N-diethyltoluidine, N,N-bis(2-hydroxy-ethyl)-p-toluidine, ethoxylated p-toluidine, N,N-bis-(2-hydroxyethyl)-p-toluidine, and mixtures thereof.

7. Formula HI, H-II, or H-III: 【Chemistry 9】 (In the formula, R 1 , R 2 , and R 3 are each independently H, halogen, straight-chain or branched C 1 -C 20 Alkyl, C 6 -C 20 Aryl, alkylaryl, arylalkyl, part of a polymer chain, OR 4 , N.R. 4 R 4 Selected from: R 4 is H, linear or branched C 1 -C 20 Alkyl, C 6 -C 20 aryl, alkylaryl, or arylalkyl) and mixtures thereof, The polymerizable composition according to claim 1.

8. 10. The composition of claim 1, comprising a polyhydroxycarboxylic acid selected from tartaric acid, ascorbic acid, or a mixture thereof.

9. 2. The polymerizable composition of claim 1, wherein the manganese or iron-containing salt or organic complex is selected from manganese octoate and manganese naphthenate, the heterocycle is 2,2'-bipyridine, the tertiary amine is N,N-dimethyl-p-toluidine, and the 1,3-dioxo compound is α-acetyl-γ-butyrolactone.

10. 1. A curing system for curing a radically polymerizable component, comprising: b) manganese- or iron-containing salts or organic complexes; c) an optional tertiary amine or phosphine; d) optional nitrogen-containing aromatic heterocycle or thiol-containing compounds; e) optional polyhydroxycarboxylic acids; f) 1,3-dioxo compounds Including; The cure system is substantially free of one or more of cobalt, copper, and peroxide initiators, and the cure system comprises: (1) A combination of (i) a tertiary amine or a phosphine, and (ii) a nitrogen-containing aromatic heterocycle or a thiol-containing compound; (2) polyhydroxycarboxylic acids; or (3) Thiol-containing compounds The curing system comprises at least one of the following:

11. 11. The cure system of claim 10, wherein the cure system consists essentially of a manganese-containing salt or organic complex, a tertiary amine, and a nitrogen heterocycle.

12. 11. The cure system of claim 10, wherein the cure system consists essentially of a manganese-containing salt or organic complex, a polyhydroxycarboxylic acid, and a 1,3-dioxo compound.

13. 11. The cure system of claim 10, wherein the cure system consists essentially of a manganese-containing salt or organic complex, a 1,3-dioxo compound, and a thiol-containing compound.

14. 1. A method for curing a polymerizable composition, comprising: a) a radically polymerizable component; b) manganese- or iron-containing salts or organic complexes; c) an optional tertiary amine or phosphine; d) optional nitrogen-containing aromatic heterocycle or thiol-containing compounds; e) optional polyhydroxycarboxylic acids; f) 1,3-dioxo compounds forming a mixture comprising: The polymerizable composition is substantially free of one or more of cobalt, copper, and peroxide initiators, and the polymerizable composition comprises: (1) A combination of (i) a tertiary amine or a phosphine, and (ii) a nitrogen-containing aromatic heterocycle or a thiol-containing compound; (2) polyhydroxycarboxylic acids; or (3) Thiol-containing compounds The method, comprising at least one of the following:

15. the below described: a) a radically polymerizable component; b) manganese- or iron-containing salts or organic complexes; c) an optional tertiary amine or phosphine; d) optional nitrogen-containing aromatic heterocycle or thiol-containing compounds; e) optional polyhydroxycarboxylic acids; preparing a polymerizable composition comprising: storing the polymerizable composition for at least 30 days; then combining the polymerizable composition with a 1,3-dioxo compound; 15. The method of claim 14, further comprising:

16. the below described: a) a radically polymerizable component; c) an optional tertiary amine or phosphine; d) optional nitrogen-containing aromatic heterocycle or thiol-containing compounds; e) optional polyhydroxycarboxylic acids; f) 1,3-dioxo compounds preparing a polymerizable composition comprising: storing the polymerizable composition for at least 30 days; thereafter combining the polymerizable composition with a manganese- or iron-containing salt or organic complex; 15. The method of claim 14, further comprising:

17. 15. The method of claim 14, wherein the polymerizable composition is applied as a sheet molding compound (SMC) resin, a casting resin, an adhesive, a pultrusion resin, a corrosion resistant resin, a flame retardant resin, a low or zero styrene content resin, a filament winding resin, a hand lay-up resin, a resin transfer molding resin, a prepreg, a gel coat, or a coating resin.

18. 15. The method of claim 14, wherein the radically polymerizable component is selected from the group consisting of polyester resins, vinyl ester resins, urethane acrylate resins, vinyl hydride resins, and combinations thereof.

19. 15. The method of claim 14, wherein the radically polymerizable component, the manganese- or iron-containing salt or organic complex, the tertiary amine or phosphine, and the nitrogen-containing aromatic heterocycle- or thiol-containing compound are combined and stored for at least 30 days before forming a mixture with the 1,3-dioxo compound.

20. 15. The method of claim 14, wherein the radically polymerizable component, the manganese or iron-containing salt or organic complex, and the polyhydroxyl carboxylic acid or thiol compound are combined and stored for at least 30 days before forming a mixture with the 1,3-dioxo compound.

21. 15. The method of claim 14, wherein the radical polymerizable component and the 1,3-dioxo compound, the tertiary amine or phosphine, and the nitrogen-containing aromatic heterocycle or thiol-containing compound are combined and stored for at least 30 days before forming a mixture with the manganese or iron-containing salt or organic complex.

22. 15. The method of claim 14, wherein the radically polymerizable component and the 1,3-dioxo compound, and the polyhydroxyl carboxylic acid or thiol compound are combined and stored for at least 30 days before forming a mixture with the manganese or iron-containing salt or organic complex.

23. 15. The method of claim 14, further comprising applying the mixture as a coating, layer, or casting before or while the polymerizable composition is curing.

24. 15. The method of claim 14, wherein the polymerizable composition is applied as a sheet molding compound (SMC) resin, a casting resin, an adhesive, a pultrusion resin, a corrosion resistant resin, a flame retardant resin, a low or zero styrene content resin, a filament winding resin, a hand lay-up resin, a resin transfer molding resin, a prepreg, a gel coat, or a coating resin.

25. 10. A resin comprising the polymerizable composition of claim 1, wherein the resin is a sheet molding compound (SMC) resin, a resin transfer molding (RTM) resin, a casting resin, an adhesive resin, a pultrusion resin, a corrosion resistant resin, a flame retardant resin, a low or zero styrene content resin, a prepreg, a gel coat, or a coating resin.

26. 10. The polymerizable composition of claim 1, wherein the polymerizable composition has a heat of polymerization of less than 950 kJ / kg.

27. 10. The polymerizable composition of claim 1, wherein the polymerizable composition has a peak exotherm of less than 300°C.

28. 10. The polymerizable composition of claim 1, wherein the polymerizable composition has a time to peak exotherm of 5 minutes to 60 minutes.

29. 10. The polymerizable composition of claim 1, wherein the polymerizable composition has a gel time of 10 seconds to 60 minutes.