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 to Related Applications This application claims the benefit of the filing date and priority of U.S. Provisional Application No. 62 / 787,648, filed on January 2, 2019, which is incorporated herein by reference.

[0002] Field of the Invention The present disclosure relates to compositions and methods for polymerizing radically polymerizable compositions, which 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 one or more other components together with 1,3 - dioxo compounds.

Background Art

[0003] Background Thermosetting resins used in the fields of casting or open and closed applications are typically cured by a free - radical polymerization process. 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 under 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 hard thermosetting cross - linked network. The process is used, for example, in the manufacture of castings, motors, coatings, adhesives, and fiber - reinforced articles. The plastics and composites industries most frequently use organic peroxides. 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 nomenclature will depend on the industry and field of application of the material.

[0004] Organic peroxides can be used as solids (usually fine powders), liquids or pastes. Some materials, such as water, odorless mineral spirits, some phthalic esters or other phlegmatizing agents, do not react with organic peroxides and are often used to dilute organic peroxides. Diluted mixtures or formulations are less flammable than undiluted organic peroxides when exposed to thermal shock or physical impact. Dilution makes peroxides that are unstable towards manufacture, handling and use safer. The main hazards associated with organic peroxides are the possibility of fire and explosion. Organic peroxides can also be toxic or corrosive. What makes organic peroxides useful as well as dangerous is the double oxygen (-O-O-) of the "peroxy" group. The peroxy group is chemically unstable. Organic peroxides can easily undergo thermal decomposition, generating heat at an increasing rate as the temperature rises, leading to what is known as a runaway reaction. Many organic peroxides emit flammable vapors upon decomposition. These vapors are liable to ignition. Most undiluted organic peroxides are easily ignited 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 main causes of fires and explosions in the process industries.

[0005] Organic peroxides have a self-accelerating decomposition temperature (SADT). The SADT represents the temperature at which a particular organic peroxide formulation will undergo self-accelerating decomposition (initiate a chemical process leading to explosion) in its commercial packaging condition. The SADT value will vary depending on each organic peroxide formulation and the size and shape of its packaging. There are organic peroxides that are dangerously reactive; they can decompose very rapidly or explosively when exposed to even slight heat, friction, mechanical shock or contamination by unsuitable substances such as amines or metal salts or their organic complexes. Organic peroxides can also be powerful oxidizing agents. Combustible substances contaminated with most organic peroxides can very easily catch fire and burn very violently (i.e., deflagrate). This means that the combustion rate is very fast: it can range from 1 m / s to several hundred meters per second. Also, as the pressure increases, the combustion rate increases, and the combustion (or reaction) zone can move at supersonic speeds through air or a gaseous medium.

[0006] Commercially available systems for room-temperature curing thermosetting resins contain accelerators and / or promoters used in combination with initiators (peroxides). These include salts of metals selected from among one or more compounds of alkyl organic acids and, for example, lithium, calcium, copper, vanadium, zirconium, titanium, nickel, iron, sodium, potassium, magnesium, manganese, barium, and cobalt. The selection of metal ions and their salts is determined by several parameters, such as activity at ambient temperature, possible coloring effects, toxicity, and stability in the thermosetting product, price, etc. It should be considered that the activity of metal ions is also influenced by the type of ligand. Due to their good performance at ambient temperature, cobalt-containing accelerators are the most widely used co-promoters. However, the drawback of cobalt is that cobalt carboxylates are suspected of being highly toxic (carcinogenic). Therefore, there is an increasing demand in the thermosetting resin industry for promoters that can provide proper curing without compromising the performance of the resulting product. Recently, thermosetting systems that can be gelled and cured by free radical polymerization with various accelerators have received great attention. In particular, accelerators without any cobalt salts have been attracting attention because cobalt carboxylates are suspected of being highly toxic (carcinogenic).

[0007] Among the important parameters that desirably remain constant for the useful life of a resin system during storage, i.e., its "shelf life", are the gelation and curing times of the resin system. The variation in the reaction times of gelation and subsequent curing of a polyester resin system during storage can be characterized as a "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. Usually, polyester systems during long-term storage result in longer gelation or curing times. However, there are polyester systems that, after a long storage period, can exhibit a gelation time shorter than the initial curing time of a freshly manufactured batch. Typical commercially available polyester systems often have a gelation time drift in the range of minus 50 percent to plus 200 - 300 percent. Such variations frequently cause problems during molding or coating application processes where predictability of the gelation time is required. The gelation time drift of a polyester resin system poses a complex problem because there can be several interrelated factors that cause it, namely, the physical parameters of the resin formulation, the chemical composition of the resin system, the promotion package, the presence of contaminants, and the transportation, handling, and storage conditions. The problem of gelation time drift is particularly acute for higher reactivity resin systems that may contain chemical accelerators to accelerate the gelation rate or with respect to reducing the reaction temperature required in casting operations. Promoted polyester systems not only can exhibit large variations in gelation time drift but also, due to different storage and handling conditions, it has been found that the gelation time drift can vary widely among samples within a single batch of polyester formulation.

[0008] The reduction of styrene emissions remains an important 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, non-reinforced casting, gel coat, and filament winding. New environmental concerns require better control regarding the emission of organic compounds into the environment. This is a promising industry for finding means to develop technologies that can reduce the potential risk to workers in contact with thermosetting resins. At the same time, the market demands that new products have a minimal cost increase at the time of commercialization and do not impair the reactivity of the resin. An important factor to consider is that all materials should have good compatibility with all components in the mixture, and the viscosity should remain within an acceptable range so that pouring or spraying is not impaired. Additionally, wetting of glass or filler is also necessary for maintenance, and the physical properties should be the same as or better than those of 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 approach can lead to systems with slower reactivity, incomplete curing, and higher costs. Reduction in the amount of styrene or reactive diluent has been utilized as an attempt to reduce emissions. However, this approach results in higher viscosities, making it more difficult to handle, roll, or spray the resin. Another approach involves the preparation of low molecular weight polymers. Low molecular weight polymers require less styrene or other reactive diluents to result in lower viscosities. The problem associated with lower molecular weight thermosetting systems is that the resulting physical properties of the final product are severely impaired. Generally, these products have inferior performance compared to products of higher molecular weight polymers.

[0010] Another common approach used to reduce styrene emissions is to add wax to the thermosetting resin. Wax contributes to restricting the emission of diluent vapor during curing and also reducing any oxygen inhibition on the surface of the product. However, the problem encountered with this approach is poor interlayer bonding. Oxygen inhibition is a known drawback during the curing process of vinyl-containing thermosetting resins due to the oxygen present in the air. The polymerization of monomers on the surface of the product is significantly restricted due to contact with air, which leads to the formation of sticky or oily residues. This is a problem in creating a substance with appropriate quality because the product can become unpleasantly sticky during handling due to impurities adhering to the surface or semi-liquid residues remaining on the back side of the surface. Wax is perhaps the most commonly used method in the composites industry to minimize or eliminate surface stickiness. Wax is partially dissolved or dispersed in the thermosetting resin, and during curing, they become incompatible with the mixture that migrates to the surface and thus protect from contact with oxygen in the air. There are several drawbacks to using wax. For example, when using a polyester resin containing dicyclopentadiene (DCPD), the hydrocarbon nature of the polymer is made more compatible with paraffin wax. As a result, the wax does not move properly to the surface, and the resulting substance remains sticky. Wax is highly dependent on the chemical composition of the thermosetting resin because it must be incorporated into the mixture and remain as a fine dispersion system. On the other hand, as mentioned above, the wax on the surface of glass-reinforced composites can potentially impair interlayer adhesion. The adhesion problem is frequently encountered when thick composites are prepared within the next layer.

[0011] In addition to oxygen inhibition, other problems that can contribute to poor surface quality and the general performance of composites are poor curing or insufficient cross-linking of the thermosetting resin. The curing behavior of vinyl-containing thermosetting resins is important to establish appropriate processing to ensure satisfactory quality and in-situ performance of composite products. The curing behavior of vinyl-containing thermosetting resins is characterized by a complex mechanism involving copolymerization of the vinyl components in the polymer with the molecules induced by the decomposition of initiators and co-accelerators of the vinyl-containing diluent. Heat is generated during copolymerization. The heat of reaction, also known as the heat of polymerization, is the temperature change of the reaction mixture occurring at a constant pressure. It is a thermodynamic unit of measurement useful for calculating the amount of energy released or generated during the reaction. The high exotherm that begins when the heat generated by the reaction exceeds the heat removed can result in decomposition products, so the risk must be evaluated during the curing of the resin and / or monomer mixture. Excess heat raises the temperature of the reaction product and increases the reaction rate. This in turn accelerates the heat generation rate. A rough rule of thumb is that the reaction rate, and thus the heat generation rate, doubles for every 10 °C increase in temperature. As the temperature rises, the rate at which heat is removed by the surrounding environment increases linearly rather than exponentially as heat is generated, so thermal runaway can occur. As soon as control of the heat is lost, the temperature rises rapidly and there is little time for correction. The molds used during production can be at risk of deformation due to temperature and a sudden increase in gas generation. The elevated temperature can cause more harmful secondary by-products or decomposition. The release of combustibles from the process can reach their ignition points, posing a risk of fire or explosion in the workplace. There is a possibility that hot gases and toxic substances contaminate the workplace or a toxic cloud spreads away from the site. There is a serious risk of injury or even death to plant operators and it can harm the general public and the local environment.

[0012] The scale at which the curing reaction is carried out can have a significant impact on the potential for excess heat to be generated. The heat generated increases with the volume of the reaction mixture, while the heat removed, on the other hand, depends on the surface area of the mold available for heat transfer. As the ratio of mass to surface area increases, cooling can become insufficient. This has important implications for the scale-up of the process from laboratory to production. Typical evaluations will require one or more of defining the process and manipulating the conditions in the plant; identifying potential risk factors; evaluating the risks arising from the risk factors and determining whether existing preventive measures are sufficient or more should be done; selecting and specifying appropriate safety measures; and implementing and maintaining the selected safety measures. As the process design becomes clear, predictable deviations from the normal process, such as equipment failures or operator errors, should be considered.

[0013] An important parameter during the preparation of composite materials is that during the crosslinking of the reactive components of the curing system, they need to generate an appropriate heat of polymerization. Since the final mechanical properties of the finished product will be determined by the proper crosslinking of the mixture, the generation of an appropriate heat of polymerization is very important. Systems that generate only a small heat of polymerization will be problematic because the resin mixture cannot be fully cured or crosslinked and uncured material may remain in the product, affecting the final physical properties. In some cases, residual monomers will remain in the composite and diffuse out of the product, polluting the environment. Composite materials made of vinyl-containing thermosetting resins are typically cured at low temperature, moderate high temperature or room temperature using a peroxide initiator alone or in combination with a cobalt salt and / or a tertiary amine. As described above, the drawbacks of these systems are that peroxides are heat-sensitive and cobalt is a toxic and carcinogenic agent. Several techniques have been presented, for example in US10,000,602; US9,068,045; US8,039,559; WO2008 / 003497, to eliminate cobalt as an accelerator from the resin mixture. However, none of those techniques solve the problem characterized by using peroxides in combination with cobalt salts.

[0014] There have been few reports on polymerizable vinyl thermosetting resins that cure without any peroxide or cobalt salt. U.S. Patent 6,552,140 to Kneafsey and Barnes discloses an air-activatable polymerizable composition useful for preparing adhesives containing methacrylic monomers, cobalt salts, weak acids, and 1,3-dioxo compounds. This composition requires air to generate free radicals to crosslink the polymerizable composition and uses metal salts that may be toxic. Nothing is mentioned about the gelation time drift, heat of polymerization, or degree of cure of the prepared mixture.

[0015] U.S. Patent Application Publication 2016 / 0152754A1 to Pfeil describes a composition having a resin component comprising a radically polymerizable compound, an α-halocarboxylic acid ester, a copper(I) salt, and a nitrogen-containing ligand. The reported typical gelation times are from 45 seconds to 1.5 hours, and an exotherm of polymerization up to 172 °C is reported. The composition requires toxic halogenated intermediates. Nothing is mentioned about any potential gelation time drift of the composition. U.S. Patent Application Publication 2016 / 0168286A1 to Pfeil describes a radically polymerizable composition comprising a copper salt and a nitrogen-containing ligand. According to the claims, copper salts and ligands at a concentration of 3 - 5% are required for crosslinking the monomer mixture. Since large amounts are required, the mixture darkens. Nothing is mentioned about gelation time drift and heat of polymerization. Pfeil also mentions in this patent his patent application DE102011078785A1 for a composition containing a curing agent 1,3-dicarbonyl compound without peroxide and a manganese compound used as an accelerator to crosslink a resin composition based on a radically curable compound. He states that this system tends not to cure completely under certain conditions, especially those where the performance is degraded by the cured mass for use in plugging masses, and under conditions requiring a reliable very high value. Pfeil's US2016 / 0168286A1 states in paragraph

[0011] on page 1 that his composition of 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 be fully cured and the required properties of the cured mass can be achieved. Based on Pfeil's own conclusion, his composition of '785 does not seem to present a reliable method for obtaining reproducible properties. It is highly unlikely that the composition would have a stable or minimal gelation time drift. Furthermore, nothing is mentioned regarding obtaining non-stick properties with respect to the heat of polymerization or the resulting cured system.

[0016] P. Garra et al. published a paper in Macromlecules, 2018, 51, 6395 - 6404 under the title "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 exotherm have been reported. No additional information is provided regarding gelation time drift stability and the reproducibility of the properties obtained for the prepared composites. Therefore, this paper does not seem to solve the drawbacks of the composition reported by Pfeil. Therefore, it would be desirable to provide a composition that can generate an appropriate heat of polymerization to lead to a product that does not require peroxides, has no cobalt-containing salts, has a stable or minimal gelation time drift, has a non-stick surface, provides good curing to bring about the required physical properties, and, if necessary, releases a reduced amount of volatile organic compounds. Summary of the Invention

[0017] Summary of the Invention In view of the above problems, it is necessary to address one or more of the stated problems. Specifically, it would be advantageous to obtain a composition that can crosslink at room temperature or mild elevated temperatures, reduces or minimizes gel time drift to provide a non-sticky surface and excellent physical properties, and has high reactivity. This would be particularly advantageous in several application fields 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. As will be described hereinafter, the present invention provides a polymerizable composition comprising a radically polymerizable component, a manganese- or iron-containing salt or organic complex, a 1,3-dioxo compound, and one or more other components. The polymerizable composition may be curable and / or the thermosetting composition is applicable to the above application fields. The present composition and method are notable in that they avoid certain commonly used initiators or catalysts and are different 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 present composition and method have a heat of polymerization of 100 - 950 KJ / Kg as measured using differential scanning calorimetry. In some embodiments, the heat of polymerization is preferably 150 - 850 KJ / Kg, more preferably 150 - 750 KJ / Kg. The amount of heat generated will depend on the composition of the reactive components and the various additives that may be part of the polymerizable composition.

Modes for Carrying Out the Invention

[0018] Definition of Technical Terms The terminology used in this application is for the purpose of describing particular embodiments only and is not intended to be limiting. In addition to the technical and scientific meanings of the defined terms, the defined terms are as generally understood and accepted in the technical field of the present disclosure. As used in this specification and the appended claims, the terms "a," "an," and "the" include both singular and plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a component" includes one or more components. As used in this specification and the appended claims, in addition to their ordinary meanings, the terms "substantial" or "substantially" mean within the limits or extent of what is acceptable. For example, "substantially free of a component" means that a person skilled in the art would consider that the composition does not contain a significant amount of the component. As used in this specification and the appended claims, in addition to their ordinary meanings, the term "about" means within the limits or amount that is acceptable to a person skilled in the art. For example, "about the same" means that a person skilled in the art would consider it to be the same when compared. For example, but not limited to, when referring to measurable values such as the number of carbon atoms, time, temperature, and number of days, the term "about" as used in this application is intended to encompass variations of ±20%, ±10%, ±5%, ±1%, ±0.5%, or even ±0.1% of the specified amount.

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

[0020] The technical terms used in this application are for the purpose of describing specific embodiments only and are not intended to limit the present invention. When used in this application, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly dictates otherwise. Further, as used herein, the terms "comprises" and / or "comprising" identify the presence of a stated feature, integer, step, operation, element, and / or component, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. When used in this application, the term "and / or" includes any and all combinations of one or more of the associated listed items. When used in this application, the term "accelerator" or "promoter" includes any and all combinations and may refer to a metal complex, a metal salt, an amine, or a quaternary ammonium salt. When used in this application, the term "co-accelerator" or "co-promoter" includes any and all combinations and may refer to a tertiary amine and / or a quaternary ammonium salt.

[0021] Unless otherwise defined, all terms (including technical and scientific terms) used in this application have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Further, terms such as those defined in commonly used dictionaries should be interpreted as having a meaning that coincides with their meaning in the context of the relevant art and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein. As used in this application, the term "radically polymerizable" component refers to a substance containing a group that participates in a radical polymerization reaction. Examples of radically polymerizable groups are ethylenically unsaturated groups such as vinyl groups and (meth)acrylate groups. The radically polymerizable component can be a monomer, an oligomer, a polymer, or other component. In some embodiments, the radically polymerizable component is a vinyl monomer such as of the formula CHR 1 =CR 2 R 3 (wherein R 1 , R 2 , and R 3It contains a group characterized by representing a hydrogen atom or an organic group, respectively).

[0022] "Alkyl" as used herein, alone or as part of another group, refers to straight-chain or branched-chain hydrocarbons that may contain from 1, 2, 3, 4, 5, or 6 carbon atoms to about 10, 15, 20, or 25 carbon atoms. Representative examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, 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, n-decyl, and the like. "Lower alkyl" as used herein is a subset of alkyl and, in some preferred embodiments, refers to straight-chain or branched-chain hydrocarbon groups containing from about 1 to about 4 carbon atoms. Representative examples of lower alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like.The term "alkyl" or "lower alkyl" is intended to include both substituted and unsubstituted alkyl or lower alkyl, unless otherwise indicated, and these groups may be substituted with halo, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocycle, heterocycloalkyl, hydroxyl, alkoxy (which thereby creates polyalkoxy, such as polyethylene glycol), alkenyloxy, alkynyloxy, haloalkoxy, cycloalkoxy, cycloalkylalkyloxy, aryloxy, arylalkyloxy, heterocyclooxy, heterocycloalkyloxy, mercapto, alkyl-S(O)m, haloalkyl-S(O)m, alkenyl-S(O)m, alkynyl-S(O)m, cycloalkyl-S(O)m, cycloalkylalkyl-S(O)m, aryl-S(O)m, arylalkyl-S(O)m, heterocycle-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, where m = 0, 1, 2 or 3.

[0023] "Alkenyl" as used herein, either alone or as part of another group, refers to a straight-chain or branched-chain hydrocarbon containing from 1, 2, 3, 4, 5, or 6 carbon atoms up to about 10, 15, or 20 carbon atoms (or about 1 to about 4 carbon atoms in the case of lower alkenyl) and containing 1 to 4 double bonds in a straight chain. Representative examples of alkenyl include, but are not limited to, vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2,4-heptadiene, and the like. The term "alkenyl" or "lower alkenyl" is intended to include both substituted and unsubstituted alkenyl or lower alkenyl, unless otherwise indicated, and these groups can be substituted with the same groups as described in connection with the above alkyl and lower alkyl. "Alkynyl" as used herein, either alone or as part of another group, refers to a straight-chain or branched-chain hydrocarbon containing from 1, 2, 3, 4, 5, or 6 carbon atoms up to about 10, 15, or 20 carbon atoms (or 1 to 4 carbon atoms in the case of lower alkynyl) and containing 1 triple bond in a straight chain. Representative examples of alkynyl include, but are not limited to, 2-propynyl, 3-butynyl, 2-butynyl, 4-pentynyl, 3-pentynyl, and the like. The term "alkynyl" or "lower alkynyl" is intended to include both substituted and unsubstituted alkynyl or lower alkynyl, unless otherwise indicated, and these groups can be substituted with the same groups as shown in connection with the above alkyl and lower alkyl.

[0024] "Aryl" as used herein, either alone or as part of another group, refers to a monocyclic carbocyclic system or a bicyclic carbocyclic fused-ring system that can have one or more aromatic rings. Representative examples of aryl include azulenyl, indanyl, indenyl, naphthyl, phenyl, tetrahydronaphthyl, and the like. The term "aryl" is intended to include both substituted and unsubstituted aryl, unless otherwise indicated, and these groups can be substituted with the same groups as shown in connection with the above alkyl and lower alkyl. "Arylalkyl" as used herein, either alone or as part of another group, refers to an aryl group as defined herein attached to the parent molecular moiety via an alkyl group as defined herein. Representative examples of arylalkyl include, but are not limited to, benzyl, 2-phenylethyl, 3-phenylpropyl, 2-naphthalen-2-ylethyl, and the like.

[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 fields of application, contains functional groups capable of reacting with the base resin or itself, and during polymerization (curing), most of which become components of the cured composite system. A layer can be attached directly or indirectly to another surface. "Indirect" attachment of one layer to another means that there is an intermediate layer between them. For example, when there is a second clear layer between the first clear layer and the color layer, it can be said that the first clear layer is indirectly attached to the color layer. Unless otherwise specified in this application, the term "viscosity" refers to the viscosity of the polymer in the monomer at 25 °C (77 °F) measured in centipoise (cps) using a Brookfield RV model viscometer. The viscosity under high shear is measured by a cone plate type (CAP) viscometer at a shear rate of 10,000 l / s. The term "NVM" refers to non-volatile materials dispersed in volatile substances (e.g., monomers) measured according to ASTM D1259. All percentages, amounts, and concentrations in this disclosure are by mass unless otherwise indicated.

[0026] Detailed Description In the following detailed description, for purposes of explanation and not limitation, representative embodiments are shown that disclose specific details to provide a complete understanding of the present teachings. Descriptions of known systems, devices, materials, operating methods, and manufacturing methods may be omitted to avoid obscuring the description of the embodiments. Nevertheless, systems, devices, materials, and methods within the scope of understanding of those skilled in the art can be used in accordance with the representative embodiments. As described in the present application, it has been found that a polymerizable composition containing a radically polymerizable component together with one or more other components has a gelling time that is stabilized over its storage life or useful life. In some embodiments, the radically polymerizable composition comprises a manganese- or iron-containing salt or organic complex, a tertiary amine or phosphine, and a nitrogen-containing heterocycle or thiol compound. In other embodiments, the radically polymerizable composition comprises a 1,3-dioxo compound, a tertiary amine or phosphine, and a nitrogen-containing heterocycle or thiol compound. In some embodiments, the radically polymerizable composition comprises a 1,3-dioxo compound and a polyhydroxycarboxylic acid or thiol compound. The various components are included in the polymerizable composition in an amount sufficient to reduce, suppress, or minimize the gelling time drift for the desired usable storage life of the polymerizable composition as compared to the untreated corresponding composition. When curing is desired, the composition is mixed with a 1,3-dioxo compound to initiate radical polymerization and crosslinking (curing) of the composition.

[0027] The manganese- or iron-containing salt or complex can be added in several different ways. For example, the metal can be premixed to form a metal salt or metal complex prior to addition 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 performed. Another alternative technique is to mix the 1,3-dioxo compound with the radically polymerizable component together with one or more other components such as a polyhydroxycarboxylic acid or thiol compound for stabilizing the gelling time drift of the polymerizable component, and then add the manganese- or iron-containing salt or complex. This mixing can actually be achieved by any conventional mixing method. The advantages of the present composition and method are that a radically polymerizable composition is provided which features an effectively extended shelf life for suppressing gelation time drift. Accordingly, the gelation time is predictable, and a wide variety of resins can be utilized in molding or coating application fields where it is necessary that the gelation time is only slightly different from the initial gelation time which is a characteristic of the resin system immediately after manufacture. The radically polymerizable resin system treated according to the method of the present invention exhibits a post-storage gelation time drift that is as low as the percentage of 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 portion of the polymerizable composition at an initial point in time and the gelation time of the second portion of the composition at one or more subsequent points in time. In this case, the polymerization conditions and components are identical in other respects. Gelation time drift can be expressed by finding the difference between the initial gelation time and the subsequent gelation time and dividing by the initial gelation time. Gelation time drift can be calculated as an average gelation time drift where the difference is the average difference between the initial gelation time and a plurality of subsequent gelation times, or it can be calculated as a maximum gelation time drift where the difference is the maximum difference between the initial gel time and any subsequent gelation time. The gelation time drift of the composition can be expressed as remaining within a range during the storage period. For example, some embodiments of the present composition have a gelation time drift of less than 20%, or less than 15%, or less than 10%. The initial gelation time is generally measured within 1 or 2 days of the formulation of the polymerizable resin and other components. The subsequent gelation times are generally measured 15 days, 30 days, 60 days, or another number of days after the initial gelation time measurement, enabling the evaluation of the storage stability of the polymerizable composition over that number of days.

[0029] Including a curing system in the polymerizable composition, a thermosetting resin can be given a gelation time of less than about 60 minutes at a temperature 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 exotherm of 5 minutes to 60 minutes, or 5 minutes to 30 minutes. As another aspect, the present invention gives a 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 the present composition provide one or more of the following advantages: The manganese- and iron-containing components are common non-toxic metals in air that are stable and can form salts and complexes capable of curing this thermosetting system. The 1,3-dioxo compound is thermally stable compared to peroxides and does not show sensitivity to decomposition in the presence of oxygen in air. The metal salt and the 1,3-dioxo compound do not cause harm during storage or in the thermosetting system. The present composition provides a predictable system having a gelation time that differs only slightly from the initial gelation time, which is a characteristic immediately after the production of the resin system. The curing system gives excellent performance for obtaining products having a non-sticking surface. The curing system of the present invention provides an appropriate heat of reaction (polymerization) to obtain the desired physical properties. Using suitable vinyl-containing thermosetting monomers, a low-VOC composition can be produced. Other aspects and advantages will be apparent from the following description and the appended claims. The present invention will be described more fully hereinafter. However, the present invention should not be understood to be limited to the embodiments described herein, as it can be implemented in many different forms. Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the scope of the invention to those skilled in the art.

[0030] According to some embodiments of the present invention, there are provided a polymerizable composition and a curing system comprising a manganese- or iron-containing salt complex and a 1,3-dioxo compound, which have surprisingly been found to provide a solution to one or more of the above problems. In some embodiments, the composition and method for curing a thermosetting resin comprises the following components: (a) Radical polymerizable resin, (b) Manganese or iron-containing salt or organic complex, (c) Optional tertiary amine or phosphine, (d) Optional nitrogen-containing aromatic ring, or thiol-containing compound, (e) Optional polyhydroxycarboxylic acid, (f) 1,3-dioxo compound, (g) Optional transition metal or alkali metal including various combinations of Here, the polymerizable composition substantially does not contain cobalt, copper, and peroxide initiator, 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 compound including at least one of Here, the polymerizable composition has a gelation time drift of less than about 20% or less than about 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 the radical polymerizable component (a) in combination with a manganese (or iron) salt or complex (b), along with a tertiary amine or phosphine or thiol-containing compound (c) and a nitrogen-containing heterocycle (d). Next, a 1,3-dioxo compound (f) is added to this mixture to initiate polymerization and form a crosslinked material. In some embodiments, the polymerization composition and method include the 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). Next, a manganese (or iron) salt or complex (b) is added to this polymerization composition to initiate polymerization and form a crosslinked network. Alternatively, after mixing component (a) with a tertiary amine or phosphine (c), a nitrogen-containing aromatic heterocycle or a thiol-containing compound (d), and a 1,3-dioxo compound (f), a manganese- or iron-containing salt or organic complex (b) can be added to form a crosslinked network. Depending on the chemical nature of component (a) and its composition, other combinations and methods for using components (a) to (g) may be appropriate. The preferred method for combining the radically polymerizable component with other components will depend on the thermosetting component, inhibitor, any additives that are part of the composition, and the final intended field of application.

[0032] Typically, the gelation time of the polymerizable composition can drift from one day to several weeks or months. It is also desirable for the compositions of the present invention to maintain a stable gelation time with minimal variation over a specific shelf life. As another aspect of the present invention, there is provided a polymer composition having reduced or minimal drift with respect to gelation time over about 30 days, or over about 60 days, or over about 90 days or more. In some embodiments, to cure the polymerizable composition, a curing system is provided that includes a manganese- or iron-containing salt or organic complex and a 1,3-dioxo compound together with one or more other components. The curing system may be incorporated into the polymerizable composition all at once or at different times. For example, a first portion may be part of the composition for 30 days or more. In some embodiments, the manganese- or iron-containing complex can be from the reaction of copper with an alkyl organic acid, carboxylate, and naphthenate, 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 (wherein M is either manganese or iron, and R can be H, a substituted or unsubstituted straight-chain alkyl, a substituted or unsubstituted branched alkyl, a substituted or unsubstituted straight-chain alkenyl, a substituted or unsubstituted branched alkenyl, a substituted or unsubstituted straight-chain alkynyl, a substituted or unsubstituted branched alkynyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted alkylaryl) is. In another embodiment, the manganese- or iron-containing complex can be a naphthenate. The naphthenate can be a mixture of various cyclopentyl and cyclohexyl carboxylic acids, or alicyclic carboxylic acids, having a molecular weight from about 120 Daltons to well over about 700 Daltons. Generally, most naphthenic acids have a carbon skeleton containing about 9 to about 20 carbons. In some embodiments, the naphthenic acid has a carbon skeleton of about 10 to about 16 carbons. In some embodiments, the naphthenate can be, for example, the following.

[0034]

Chemical formula

[0035] wherein M is either manganese or iron, m and n are independently integers of 0 or greater, for example, 0, 1, 2, 3, 4, 5, 6, 10, 15, 20 or an integer greater than that, and R' and R'' can independently be H, a substituted or unsubstituted straight-chain alkyl, a substituted or unsubstituted branched alkyl, a substituted or unsubstituted straight-chain alkenyl, a substituted or unsubstituted branched alkenyl, a substituted or unsubstituted straight-chain alkynyl, a substituted or unsubstituted branched alkynyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted alkylaryl. Alternatively, in some embodiments, the manganese- or iron-containing complex is the one described in U.S. Patent No. 4,138,385, for example, the following:

[0036]

Chemical formula

[0037] (wherein 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]

[0039] (wherein, in each case, R1 is independently H, hydroxyl, C1-C6-containing branched or cyclic aliphatic; C1-C4 alkoxy; aryl, for example, C6-C20 monocyclic or polycyclic aryl, such as phenyl, toluoyl, naphthyl, biphenyl, terphenyl, halogen-containing aryl aromatic, aminoContaining aryl aromatic , Cyril Containing aryl aromatic ; heteroalkyl, for example, C6-C20 monocyclic or polycyclic heteroaryl, such as thienyl, furyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, quinolyl and isoquinolyl) may contain an organophosphine having the structure of In another embodiment, the organophosphine of the manganese- or iron-containing complex has the following formula P-II:

[0040]

Chemical formula

[0041] (wherein R 1 is in each case independently H, hydroxyl, C1-C6 branched or cyclic aliphatic, C1-C4 alkoxy; aryl, for example, C6-C20 monocyclic or polycyclic aryl, such as phenyl, toluoyl, naphthyl, biphenyl, terphenyl, halogen-containing aryl aromatic, amino Containing aryl aromatic , Cyril Containing aryl aromatic ; heteroalkyl, for example, C6-C20 monocyclic or polycyclic heteroaryl, such as thienyl, furyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, quinolyl and isoquinolyl; R 2 is in each case independently H, C1-C14 straight-chain, branched or cyclic aliphatic, alkyl aromatic, halogen-containing aryl aromatic, amino Containing aryl aromatic , Cyril Containing aryl aromatic or an alkoxy group Containing aryl aromatic and R 1 group, R 2 group or R 1 and R 2 groups are interconnected by an alicyclic or aromatic ring between them; n is 0 to 4; Y is either N or P) has the structure of In another embodiment, the organophosphine of the manganese- or iron-containing complex has the following formula P-III:

[0042] [Chemical formula]

[0043] (wherein, in each case independently, R 1 is, in each case independently, H, hydroxyl, C1-C6 branched or cyclic aliphatic, C1-C4 alkoxy; aryl, for example, C6-C20 monocyclic or polycyclic aryl, such as phenyl, toluoyl, naphthyl, biphenyl, terphenyl, halogen-containing aryl aromatic, amino Containing aryl aromatic , silyl Containing aryl aromatic ; heteroalkyl, for example, C6-C20 monocyclic or polycyclic heteroaryl, such as thienyl, furyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, quinolyl and isoquinolyl; and Y is N or P) has the structure of In another embodiment, the organophosphine of the manganese or iron-containing complex has the following formula P-IV:

[0044] [Chemical formula]

[0045] (wherein: in each case independently, R Containing aryl aromatic is, in each case independently, H, C1-C14 linear, branched or cyclic aliphatic, alkyl aromatic, halogen-containing aryl aromatic, amino Containing aryl aromatic or an alkoxy group 1 is, in each case independently, H, hydroxyl, C1-C6 branched or cyclic aliphatic, C1-C4 alkoxy; aryl, for example, C6-C20 monocyclic or polycyclic aryl, such as phenyl, toluoyl, naphthyl, biphenyl, terphenyl, halogen-containing aryl aromatic, amino Containing aryl aromatic , silyl Containing aryl aromatic ; heteroalkyl, for example, C6-C20 monocyclic or polycyclic heteroaryl, such as thienyl, furyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, quinolyl and isoquinolyl; and R 2In each case independently, H, a C1-C14-containing straight-chain, branched or cyclic aliphatic, alkyl aromatic, halogen-containing aryl aromatic, silyl Containing aryl aromatic , amino Containing aryl aromatic or an alkoxy group, and are linked to each other by an alicyclic or aromatic ring; Y is either N or P) has the structure of

[0046] Examples of organophosphine metal complexes include, but are not limited to, those containing the following as ligands in the complex: (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(dicyclohexylphosphino)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, dicyclohexylnorbornanylphosphine, dri propylphosphine, triisopropylphosphine, 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-diphenylphosphinophenyl)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'-binaphthyl, 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)-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(3,5-25ditrifluoromethylphenyl)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)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(phospltino))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-trifluoromethylphenyl)phosphino]-1,1'-binaphthyl, 2,2'-bis[bis(4-methylphenyl)phosphino]-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,3,2-diazaphospholine, tert-butylimino-tri(pyrrolidino)phosphorane, hexaethylphosphoramide, hexaisopropylphosphoramide, tris(4-morpholino)phosphine, etc., and combinations thereof. In some embodiments, the organophosphine metal complex-containing compound added to the resin can be in the range of 0.0001 to about 3.0 percent based on the mass of the resin. In one embodiment, the amount of the organophosphine metal complex-containing compound added to the resin can be in the range of 0.001 to about 1.0 mass percent based on the mass of the resin. In another embodiment, the amount of the organophosphine metal complex-containing compound added to the resin can be in the range of 0.001 to about 0.5 mass percent based on the mass of the resin. The amounts of the organophosphine metal complex-containing compound and any optional transition metal salts essentially free of cobalt added to the resin can be determined by the final gelation time and the desired curing of the thermosetting resin. In other embodiments, the thermosetting resin may include a tertiary amine and an optional quaternary ammonium salt used as a co-accelerator for curing the resin system.,

[0047] In some embodiments, the radically polymerizable composition includes at least one metal complex selected from manganese (Mn) or iron (Fe) complexes containing a monodentate, bidentate, tridentate, tetradentate, pentadentate or hexadentate nitrogen-donating ligand. In some embodiments, the at least one metal complex is a Mn or Fe complex of a bidentate, tridentate, tetradentate, pentadentate 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, the ligand L exists in one or more forms of [MnLCl2], [FeLCl2]; [FeLCl]Cl; [FeL(H2O)](PF6)2; [FeL]Cl2, [FeLCl]PF6 and [FeL(H20)](BF4)2. Preferably, the ligand L exists in one or more forms of [MnLCl2], [FeLCl2]; [FeLCl]Cl; [FeL]Cl2 and [FeL(H2O)](BF4)2.

[0048] As used herein, the term "nitrogen-donor ligand" or "ligand" or "L" is an organic structure or molecule that will support a coordinated nitrogen atom. In the present invention, said at least one nitrogen-donor ligand is selected from the group comprising monodentate, bidentate, tridentate, tetradentate, pentadentate and hexadentate nitrogen-donor ligands. For suitable non-limiting examples of monodentate, bidentate, tridentate, tetradentate, pentadentate and hexadentate nitrogen-donor ligands, reference is made to U.S. Patent No. 2,526,718, U.S. Patent No. 2,565,897, U.S. Patent No. 4,311,625, WO2008 / 003652 and DE4032546, the entire disclosures of each of which are hereby incorporated herein by reference. In some embodiments, the composition comprises at least one accelerator which is an iron or manganese-containing complex of a tridentate, tetradentate, pentadentate or hexadentate nitrogen-donor ligand, an N-heterocyclic compound or an N-heteroaromatic compound. In some embodiments, said at least one nitrogen-donor ligand is selected from the group of ligands of the following formulas N-I, N-II, N-III, N-IV, N-V, N-VI, N-VII, and / or ligands comprising an N-heterocyclic compound or an N-heteroaromatic compound.

[0049]

Chemical formula

[0050]

Chemical formula

[0051] In some embodiments, the manganese- or iron-containing complex generally belongs to the bispidone classification and preferably has the following formula N-I in the form of a manganese metal complex

[0052]

Chemical formula

[0053] and has a ligand of. In the formula, R 1 and R2 is, independently, C 1-24 alkyl, C 6-10 aryl, heteroaryl, heteroarylC 1-6 alkyl, and -CH2-CH2-N(CH3)2, where 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-O-C 1-8 alkyl, C 1-8 alkyl-O-C 6-10 aryl, C 6-10 aryl, 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 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, -NH2, -NH-C I-4 alkyl, and C 1-4 alkyl selected from the group consisting of; 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 is independently -H, -OH, C 1-4 alkoxy and C 1-4 alkyl selected from the group consisting of.

[0054] In some embodiments, R 3 and R 4is selected from -C(O)O-CH3, -C(O)-O-CH2-CH3, -C(O)-O-CH2-C6H5 and CH2OH. In some embodiments, the heteroatom capable of coordinating to the transition metal is optionally C 1-4 which may be pyridin-2-ylmethyl optionally substituted with alkyl. In some embodiments, X 1 is C=O, and / or R 1 and R 2 are CH3, C2H5, C3H7, benzyl, C4H9, C 12 H 25 and C 18 H 37 , CH2-pyridyl, or pyridin-2-yl. Exemplary classifications of bispidone are those in which at least one of R 1 or R 2 is pyridin-2-ylmethyl or benzyl, preferably pyridin-2-ylmethyl. In some embodiments, R 1 is pyridin-2-ylmethyl and R 2 is methyl. Preferred bispidones are dimethyl 2,4-di-(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diaza-bicyclo[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 bispidones have a longer alkyl chain, namely isobutyl, (n-hexyl)C6, (n-octyl)C8, (n-dodecyl)C 12 , (n-tetradecyl)C 14 , (n-octadecyl)C 18 in place of the methyl group at the 3-position, and these are prepared similarly. Preferred tetracoordinate bispidones are also described in WO00 / 60045, and preferred pentadentate bispidones are described in W002 / 48301 and W0031104379, the entire disclosures of which are incorporated herein by reference. In some embodiments, the metal complex, which may also be referred to as an "N4py-type ligand", is preferably in the form of a manganese metal complex, of the following formula N-II

[0055]

Chem.

[0056] (wherein, R 11 and R 12 are each independently a group of the formula -R 14 -R 15 ; R 13 is -H, -R 14 -R 15 and is selected from the group consisting of optionally substituted groups selected from the group consisting of C 1-6 alkyl, C 6-10 aryl and C 6-10 aryl-C 1-6 alkyl; each R 14 is independently selected from a single covalent bond or an optionally substituted group selected from the group consisting of C 1-6 alkylene, C 2-6 alkenylene, C 1-6 alkyleneoxy, amino C 1-6 alkylene, C 2-6 alkylene ether, carboxylic acid ester and carboxylic acid amide; and each R 15 is 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) has a ligand of

[0057] In some embodiments, R 11 represents pyridin-2-yl or R 12 represents pyridin-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, which may also be referred to as TACN-Nx. The ligand has a basic 1,4,7-triazacyclononane structure but has one or more pendant nitrogen groups that form a complex with the 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 Alkenyl, C 6-10 Aryl-C 1-6 Alkyl, C 6-10 Aryl-C 2-6 Alkenyl, C 1-6 Alkyloxy, C 2-6 Alkenyloxy, amino C 1-6 Alkyl, amino C 2-6 Alkenyl, C 1-6 Alkyl ether, C 2-6 Alkenyl ether, and -CX 2 2-R 22 is selected from; each X 2 is independently selected from -H or C 1-3 alkyl, where each R 22 is independently selected from optionally substituted heteroaryl groups selected from the group consisting of pyridyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and at least one of R 21 is -CX 2 -R 22 is. In some embodiments, R 22 is selected from optionally substituted pyridin-2-yl, imidazol-4-yl, pyrazol-1-yl, quinolin-2-yl groups. For example, R 22 can be pyridin-2-yl or quinolin-2-yl. In some embodiments, the basic 1,4,7-triazacyclononane structure has two pendant nitrogen groups (TACN-N2) that form a complex with a transition metal. In some embodiments, the metal complex includes a ligand of formula N-IV, which may also be referred to as a cyclam and a bridging ligand, and is preferably in the form of a manganese metal complex.

[0060]

Chemical formula

[0061] In the formula, each X 3 is the following formula

[0062]

Chem.

[0063] (wherein p is 4; each R 37 is, independently, -H, C 1-6 alkyl, --CH2CH20H, pyridin-2-ylmethyl and -CH2C(O)OH; and R 31 , R 32 , R 33 , R 34 , R 35 and R 36 are each independently selected from -C 1-4 alkyl and C 1-4 -hydroxyalkyl) is independently selected 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 (Me4cyclam), 1,4,7,10-tetraazacyclododecane (cyclam), 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane (Me4cyclam), and 1,4,7,10-tetrakis(pyridin-2-ylmethyl)-1,4,7,10-tetraazacyclododecane (Py4cyclam(cyclan)). For Py4cyclam, an iron complex is preferred. A preferred bridging ligand is preferably a ligand of the following formula N-V.

[0064]

Chem.

[0065] wherein each R 40 is, independently, -H or C 1-20 alkyl, C 1-6 alkyl, C 6-10 aryl, C 2-6 alkenyl or C 2-6-An optionally substituted group selected from the group consisting of -alkynyl; and all nitrogen atoms of the polycycle are coordinated to the transition metal. In some embodiments, R 40 is methyl and can be synthesized as described in WO98 / 39098, which is incorporated herein by reference in its entirety, and is the ligand 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane of the complex [Mn(B-cyclam)Cl2]. Other suitable bridging ligands are also described in WO98 / 39098, which is incorporated herein by reference in its entirety. In some embodiments, the metal complex comprises a ligand of the following formula N-VI, sometimes referred to as a "trispicene type". "Trispicene" is preferably in the form of a manganese metal complex.

[0066]

Chemical formula

[0067] In the formula, X 4 is selected from -CH2CH2-, -CH2CH2CH2-, -CH2C(OH)HCH2-; Each R 50 is independently selected from the group consisting of -H, C 1-6 alkyl, C 3-8 cycloalkyl, heterocycloalkyl, heteroaryl, C 6-10 aryl and C 6-10 aryl-C 1-6 alkyl, and is optionally substituted with a substituent selected from the group consisting of -OH, C 1-6 alkoxy, phenoxy, carboxylate, carboxamide, carboxylic acid ester, sulfonate, aniline, C 1-6 alkylamine and -N + (R 51 )3; Here, each R 51 is -H, C 1-6 alkyl, C 2-6 alkenyl, C 6-10 aryl, C 1-6 alkyl, C 6-10Aryl, C 2-6 Alkenyl, C 1-6 Alkyloxy, C 2-6 Alkenyloxy, amino C 1-6 Alkyl, amino C 2-6 Alkenyl, C 1-6 Alkyl ether, C 2-6 Alkenyl ether, and -C(X 5 )2-R 52 selected from; Each X 5 is independently -H or C 1-3 alkyl selected from, each R 52 is independently selected from optionally substituted heteroaryl groups selected from the group consisting of pyridyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and R 50 at least two of which are -C(X 5 )2-R 52 is. The heteroatom donating group is preferably pyridinyl optionally substituted with -C 0-4 alkyl. Other preferred heteroatom donating groups are imidazol-2-yl, 1-methyl-imidazol-2-yl, 4-methyl-imidazol-2-yl, imidazol-4-yl, 2-methyl-imidazol-4-yl, 1-methyl-imidazol-4-yl, benzimidazol-2-yl and 1-methyl-benzimidazol-2-yl. Preferably three of R 50 are C(X 5 )2-R 52 .

[0068] The following are preferred trispiro compounds: N-methyltris(pyridin-2-ylmethyl)ethylenediamine; N-octyl-tris(pyridin-2-ylmethyl)ethylenediamine; N-octadecyl-tris(pyridin-2-ylmethyl)ethylenediamine; N-methyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)ethylenediamine; N-ethyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)ethylenediamine; N-methyl-N,N',N'-tris(5-methyl-pyridin-2-ylmethyl)ethylenediamine; N-ethyl-N,N',N'-tris(5-methyl-pyridin-2-ylmethyl)ethylenediamine; N-benzyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)ethylenediamine; N-benzyl-N,N',N'-tris(5-methyl-pyridin-2-ylmethyl)ethylenediamine; N-butyl-N,N',N'-tris(pyridin-2-ylmethyl)ethylenediamine; N-octyl-N,N',N'-tris(pyridin-2-ylmethyl)ethylenediamine; N-dodecyl-N,N',N'-tris(pyridin-2-ylmethyl)ethylenediamine; N-octadecyl-N,N',N'-tris(pyridin-2-ylmethyl)ethylenediamine; N-methyl-N,N',N'-tris(imidazol-2-ylmethyl)-ethylenediamine; N-ethyl-N,N',N'-tris(imidazol-2-ylmethyl)ethylenediamine; N,N'-dimethyl-N,N'-bis(imidazol-2-ylmethyl)-ethylenediamine; N-(1-propan-2-ol)-N,N',N'-tris(imidazol-2-ylmethyl)-ethylenediamine; N-(1-propan-2-ol)N,N',N'-tris(1-methyl-imidazol-2-ylmethyl)ethylenediamine; N,N-diethyl-N',N",N"-tris(5-methylimidazol-4-ylmethyl)-diethylenetriamine; N-(3-propan-1-ol)-N,N',N'-tris(1-methyl-imidazol-2-ylmethyl)ethylenediamine;N-hexyl-N,N',N'-tris(imidazol-2-ylmethyl)ethylenediamine; N-methyl-N,N',N'-tris(benzimidazol-2-ylmethyl)ethylenediamine; and N-(3-propan-1-ol)methyl-N,N',N'-tris(benzimidazol-2-ylmethyl)ethylenedianiline. Other suitable trispiacenes are described in WO02 / 077145.; Other nitrogen-donor ligands suitable for manganese-containing and iron-containing complexes are ligands of formula N-VII below.

[0069]

Chemical formula

[0070] In the formula, each R 60 is independently selected from the group consisting of -H, C 1-6 alkyl, C 6-10 aryl, C 1-6 alkyl-C 6-10 aryl and C 2-6 alkenyl. In some embodiments, bispidone and TACN-Nx ligands are used. Non-limiting examples of preferred nitrogen-donor ligands are selected from the group consisting of compounds of formulae N-Ia, N-XIb, N-XIII, N-XIV, N-XV below.

[0071]

Chemical formula

[0072]

Chemical formula

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

[0074]

Chemical formula

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

[0076]

Chemical formula

[0077] The complex of formula N-XXI is an active ingredient of Drycoat. In some embodiments, the ligand of the manganese- or iron-containing complex is selected from porphyrin ligands. Porphyrin is a compound 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 Y-I.

[0078]

Chemical formula

[0079] Wherein X 1 , X 2 , X 3 , and X 4 are independently selected from C and N; R 1 ~R 12 are independently hydrogen, halo, C1-C 24 alkyl, C2-C 24 alkenyl, C2-C 24 alkynyl, C5-C 20 aryl, C6-C 24 alkaryl, 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 (carbonyl), C6-C 20 aryloxycarbonyl, C2-C 24Alkylcarbonyl, C6-C 20 Arylcarbonyl, halocarbonyl, formyl, thioformyl, C2-C 24 Alkylcarbonato, C6-C 20 Arylcarbonato, carboxy, carboxylato, carbamoyl (earbamoyl), 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 Alkylsulfanyl, C5-C 20 Arylsulfanyl, sulfo, sulfino, sulfonyl, phosphino, phosphono, and O-phosphono, provided that X 1 X 2 X 3 or X 4 is N, the corresponding R groups (each R 1 R 2 R 3 or R 4 ) do not exist. Any of these groups may be unsubstituted or substituted and may contain one or more heteroatoms if necessary (i.e., if the chemical nature of the group permits such substitution or heteroatoms). Further, any two adjacent groups selected from R1 to R12 may together form a ring, which may be an aliphatic, aromatic, heteroatom-containing ring, and / or may be substituted if necessary.

[0080] For example, in some embodiments, X 1 X 2 X 3 and X 4 are N, and R 1 R 2 R 3 and R 4 do not exist. In some embodiments, R 1 X 2 X 3 and X 4 are C, and R 1 R2 , R 3 , and R 4 is present. In some embodiments, X 1 , X 2 , X 3 , and X 4 is one or more of C, and X 1 , X 2 , X 3 , and X 4 is one or more of N. For example, R 1 to R 12 are independently hydrogen; halo, such as F, Cl, Br, and I, etc.; substituted or unsubstituted C1-C 24 alkyl, C2-C 24 alkenyl, C2-C 24 alkynyl, C5-C 20 aryl, C6-C 24 aralkyl, and C6-C 24 aralkyl; substituted or unsubstituted heteroatom-containing C 1 -C 24 alkyl, C 2 -C 24 alkenyl, C 2 -C 24 alkynyl, C5-C 20 aryl, C6-C 24 aralkyl, 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 alkylcarbonato and C6-C 20 arylcarbonato; carboxy and carboxylato (C2-C 24 alkylcarboxylato and C6-C 20including aryl carboxylato); carbamoyl (mono (C1-C 24 alkyl) substituted carbamoyl, di (C1-C 24 alkyl) substituted carbamoyl, mono-substituted aryl carbamoyl, and mixed alkyl / aryl substituted carbamoyl) and thiocarbamoyl; carbamate (mono (C1-C 24 alkyl) substituted carbamate, di (C1-C 24 alkyl) substituted carbamate, mono-substituted aryl carbamate, and mixed alkyl / aryl substituted carbamate); urea, cyano, isocyano, cyanato, isocyanato, and isothiocyanato; amino (mono and di (C1-C 24 alkyl) substituted amino, mono and di (C5-C 20 aryl) substituted amino, and mixed alkyl / aryl substituted amino); alkylamide and C6-C 20 aryl amide; imino, alkylimino, and arylimino; nitro; nitroso; sulfhydryl (C1-C 24 alkylsulfanyl, and C5-C 20 arylsulfanyl); sulfo (C1-C 24 alkylsulfonate, and C5-C 20 arylsulfonate); sulfino (C1-C 24 alkylsulfinyl, and sulfinyl); arylsulfinyl); sulfonyl (C1-C 24 alkylsulfonyl, and C5-C 20 arylsulfonyl); phosphino (mono, di, and tri (C1-C 24 alkyl) substituted phosphinato, mono, di, and tri (C5-C 20 aryl) substituted phosphinato, mixed alkyl / aryl substituted phosphinato, and phosphine oxide); and phosphono (mono and di (C1-C 24 alkyl) substituted phosphonato, mono and di (C5-C 20 aryl) substituted phosphonato, mixed alkyl / aryl substituted phosphonato, and O-phosphonato) are selected from.

[0081] R 1~R 12 may also be selected from enol, ketone, ester, aldehyde, acid anhydride, acyl halide, ether, epoxide, phosphonics, phosphate, phospinite, phosphate ester, imide, azide, azo, nitrate, nitrile, carbimide, aziridine, hydroxylamine, ketoxime, aldoxime, nitrate ester, enamine, azole, imidazole, pyrrole, indole, purine, pyrimidine, piperidine, pyridazine, pyridyl and derivatives, linear, cyclic and aromatic, oxyhalide, sulfide, thioether, thioester, sulfonate, sulfinyl, thiocyanate, disulfide, sulfone, thioamide, sulfoxide, isothiocyanate, sulfonamide, sulfonyl halide, thioureate, and thiophosphate ester. In some embodiments, R 1 R 2 R 3 and R 4 are the same. For example, in some embodiments, R 1 R 2 R 3 and R 4 are the same and are selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroatom-containing C1-C 24 alkyl, substituted or unsubstituted C5-C 20 aryl, and substituted or unsubstituted C5-C 20 heteroaryl. For example, R 1 R 2 R 3 and R 4 are the same 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 are the same. For example, in some embodiments, R 5 R6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are the same and are hydrogen. In some embodiments, R 1 , R 2 , R 3 , and R 4 are the same and are a first group, and R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are the same and are a second group, and the first group is a different group. In some embodiments, X 1 , X 2 , X 3 , and X 4 are the same. In other embodiments, X 1 , X 2 , X 3 , and X 4 are not the same. In some embodiments, the ligand of interest has the structure of formula Y-II below.

[0082] [Chemical formula]

[0083] In the formula, X 1 , X 2 , X 3 , X 4 , R 1 , R 2 , R 3 , and R 4 are as defined in formula Y-I above; 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 are each independently R 1 to R 12 of formula (1) above.It is selected from a group as defined. 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 A pair of substituents selected from may combine to form a further ring, which may be an aliphatic, aromatic, heteroatom-containing ring, and / or may be substituted. For example, in some embodiments, the siccative ligand is phthalocyanine, tetrabenzoporphyrin, tetraazaporphyrin, or porphyrin. Thus, in some embodiments, the composition comprises one or more accelerators having the structure of formula Y-Ia or Y-IIa below.

[0084]

Chemical formula

[0085] Wherein M is selected from Fe and Mn; n1 to n4, X 1 ~X 4 , and R 1 ~R 16 are as described above for formula Y-I and formula Y-II. The dashed lines and double bonds shown in the formulas herein are drawn in a particular direction, but it will be recognized that they are not intended to imply a specific or fixed position for the bonds. In other words, the resonance structures of the formulas described herein are intended to be within the scope of the present invention. Interested ligands include tetraarylporphyrins, diarylporphyrins, tetraalkylporphyrins, dialkylporphyrins, and mixed aryl / alkylporphyrins, as well as porphyrins containing alkenyl substituents, alkynyl substituents, heteroatom-containing substituents (such as heteroaryl, etc.), functionalized substituents (such as alkyl substituted with a carboxyl group, etc.). Specific ligands of interest include, but are not limited to, phthalocyanine; tetrabenzoporphyrin; tetraazaporphyrin; tetratolylporphyrin; porphyrin; porphyradine; 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; diformyldeuteroporphyrin IX dimethyl ester, dodecaphenylporphyrin; hematoporphyrin; hematoporphyrin IX; hematoporphyrin monomer; hematoporphyrin dimer; hematoporphyrin derivative; hematoporphyrin IX dimethyl ester; hematoporphyrin IX dimethyl ester; mesoporphyrin dimethyl ester; mesoporphyrin IX dimethyl ester; monoformyl-monovinyl-deuteroporphyrin IX dimethyl ester; monohydroxyethylvinyl deuteroporphyrin; 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; Protoporphyrin formamide; 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) - porphine; Tetra - (3 - methoxyphenyl) - porphine; Tetra - (3 - methoxy - 2,4 - difluorophenyl) - porphine; 5,10,15,20 - Tetrakis(4 - N - methylpyridyl)porphine; Mesotetra - (4 - N - methylpyridyl)porphine tetrachloride; Meso - tetra(4 - N - methylpyridyl)porphine; Meso - tetra - (3 - N - methylpyridyl) - porphine; Meso - tetra - (2 - N - methylpyridyl)porphine; Tetra(4 - N,N,N - trimethylanifinium)porphine; Mesotetra - (4 - N,N,N - trimethylamino - phenyl)porphine tetrachloride; Tetranaphthaloporphyrin; 5,10,15,20 - Tetraphenylporphyrin; Tetraphenylporphyrin; Meso - tetra - (4 - N - sulfonatophenyl) - porphine; Tetraphenylporphine tetrasulfonate; Meso - tetra - (4 - sulfonatophenyl)porphine; Tetra - (4 - sulfonatophenyl)porphine; Tetraphenylporphyrin sulfonate; Mesotetra - (4 - sulfonatophenyl)porphine; Tetrakis - (4 - sulfonatophenyl)porphyrin; Meso - tetra(4 - sulfonatophenyl)porphine;Meso-(4-sulfonatophenyl)porphyrin; meso-tetra-(4-sulfonatophenyl)porphyrin; tetrakis(4-sulfonatophenyl)porphyrin; meso-tetra-(4-N-trimethylanilinium)-porphyrin; uroporphyrin; uroporphyrin I; uroporphyrin IX; and uroporphyrin III are included. In some embodiments, porphyrin ligands found in naturally occurring porphyrins, such as heme or chlorophyll, are suitable. Further specific ligands and methods for their preparation can be found in the relevant literature, for example, Kadish et al., Handbook of Porphyrin Science: With Applications to Chemistry, Physics, and Materials (World Scientific, 2010), the content of which is incorporated herein by reference.; The compositions and methods include 1,3-dioxo compounds. The 1,3-dioxo compounds are thought to function as polymerization initiators for radically polymerizable components. The 1,3-dioxo compounds can be selected from compounds having the following formulas D-I to D-VI.

[0086] [Chemical formula]

[0087] In the formula, A is O or S, n is an integer from 1 to 6, m is a repeating unit from 2 to 20, R is H, linear or branched C1-C 20 alkyl, C6-C 20 aryl, alkylaryl, arylalkyl, R 1 、R 2 are 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 ; R 1 、R 2, R 3 , and R 4 may each independently represent a C1-C 20 alkyl, C6-C 20 aryl, alkylaryl or arylalkyl group, each optionally containing one or more heteroatoms and / or substituents; or R 1 and / or R 2 between, and / or R 1 and R 3 between, and / or R 1 and R 4 between, a ring may be present; or R 3 and / or R 4 may be part of a polymer chain or attached to a polymer chain or contain a polymerizable group. Preferably, R 1 and / or R 2 is C1-C 20 alkyl and / or C1-C 20 aryl. More preferably, R 1 and / or R 2 is a methyl group. In some embodiments, the 1,3-dioxo compound is acetylacetonate. The 1,3-dioxo compound can 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 radically polymerizable resin.

[0088] In some embodiments, the 1,3-dioxo compound is selected from compounds of formula D-II. In some embodiments, the 1,3-dioxo compound may optionally have mono- or polyethoxylated and propoxylated diols, triols, and polyols, such as acetates of glycerol, for example 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, trimethylolpropane monoacetate, trimethylolpropane diacetate, or trimethylolpropane triacetate, glycerol monoacetate, glycerol diacetate, glycerol triacetate, pentaerythritol diacetate, pentaerythritol monoacetate, pentaerythritol biacetate, pentaerythritol triacetate, pentaerythritol tetraacetate, dipentaerythritol monoacetate, dipentaerythritol diacetate, dipentaerythritol triacetate, dipentaerythritol tetraacetate, dipentaerythritol pentaacetate, or dipentaerythritol hexaacetate, and the like.

[0089] In some embodiments, the 1,3-dioxo compound may include a monofunctional or polyfunctional compound. Examples include, but are not limited to, methyl acetoacetate, ethyl acetoacetate, t-butyl acetoacetate, 2-ethylhexyl acetoacetate, lauryl acetoacetate, acetoacetanilide, pentanedione, acetylacetone, 2-(aceto-acetoxy)ethyl methacrylate, benzyl acetoacetate, α-acetyl-γ-butyrolactone, 2-acetylcyclopentanone, 2-acetylcaprolactone, cyclohexanedimethanol diacetoacetate, diethyl malonate, dimethyl malonate, diacetoacetate of ethoxylated or propoxylated bisphenol A, 3-methyl-2,4-pentanedione, 2,2-dimethyl-1,3-dioxane-4,6-dione, glycerin triacetoacetate, polycaprolactone triacetoacetate, 2-acetyl-polybutyrolactone, 2-acetyl-polycaprolactone, and the like. The 1,3-dioxo compound can be used alone or as a mixture of two or more. The 1,3-dioxo compound 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 compositions and methods include one or more various tertiary amines that can be used as accelerators and gel time drift stabilizers. For example, the tertiary amines can be selected from 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 the like, and mixtures thereof. Toluidine derivatives are considered particularly preferred activators, and more particularly N,N-dialkyltoluidine and alkoxylated p-toluidine are 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 gel 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 can 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 that are also used to control gel time drift. The acid intermediate for controlling gel time drift can be added in an amount of 0.0005 to 2.0 parts, or alternatively 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 compositions and methods include one or more thiol (mercaptan) compounds. While not bound by theory, it is believed that in the present compositions and methods, the thiol compounds function as accelerators and / or gelling time drift stabilizers. The thiol compounds can be monofunctional or bifunctional. Non-limiting examples of thiol compounds include the following: mercaptobenzothiazole (MBT), ethanethiol, propyl mercaptan, butanethiol, pentanethiol, 1-hexanethiol, octanethiol, 1-heptanethiol, 1-nonanethiol, 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 mercaptobenzothiolate, cyclohexanethiol, thiophenol, tolyl mercaptan, phenethyl mercaptan, bromobenzyl mercaptan, and cupric mercaptobenzothiolate. Among suitable polythiol compounds are mercaptoacetic acid esters and mercaptopropionic acid esters of low molecular weight polyols having from 2 to 8, preferably from 2 to 4, hydroxyl groups and up to about 75 equivalents, some or all of the hydroxyl groups being esterified with mercaptoacetate and / or mercaptopropionate. Examples of the 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 alkylene dithiols such as 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc., trithiols such as 1,2,3-trimercaptopropane, 1,2,3-tri(mercaptomethyl)propane, 1,2,3-tri(mercaptoethyl)ethane, (2,3-di((2-mercaptoethyl)thio)-1-propanethiol, etc. Further useful polythiol compounds are mercapto-substituted fatty acids having at least two mercapto substituents in the fatty acid chain, etc. Other examples of polyfunctional thiols are described, for example, in U.S. Patent No. 9,290,462; the disclosure thereof is incorporated herein by reference in its entirety. Mixtures of the above may 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, N-phenylthiourea, etc. may be incorporated into the present 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; 7,498,367; the disclosures thereof are incorporated herein by reference in their entirety. Mixtures of the above may be used.

[0095] In some embodiments, an important parameter during the preparation of the composite material is that appropriate heat of polymerization should be generated during the crosslinking of the reactive components in the thermosetting system. Thus, in some embodiments, the present compositions and methods 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 during crosslinking. 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. It is expressly contemplated that any combination of the foregoing maximum and minimum values can form a range. The generation of appropriate heat of polymerization can be selected based on the present disclosure and is very important because the final mechanical properties of the finished product will be determined by proper 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, during the crosslinking of the reactive components in the thermosetting system, the peak exotherm must be kept below the desired level. Thus, in some embodiments, the present compositions and methods have a peak exotherm 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 exotherm is from 5 minutes to 60 minutes, or from 5 minutes to 30 minutes. In some embodiments, the gelation time is from 2 minutes to 60 minutes, or from 2 minutes to 25 minutes.

[0096] Optionally, the present composition and method may include one or more transition metal salts or complexes in addition to the 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 provided as chlorides, bromides, iodides, nitrates, sulfates, phosphates, oxalates, salicylates, alkyl organic acids, other carboxylates, naphthenates, etc. They may be incorporated alone, in pairs, or together with one or two of the above metals or mixtures. The transition metal complexes may have the above ligands. In some embodiments, the polymer, copolymer or oligomer containing reactive functional groups according to the present invention can form a mixture and undergo a crosslinking reaction in the presence of other thermosetting resins or thermoplastics or mixtures thereof to form a composite material. For the purposes of the present invention, it is preferred to utilize unsaturated polyester resins, saturated polyester resins, vinyl ester resins, and urethanes containing vinyl functional groups. The unsaturated polyester resins can be formed by conventional methods. Typically, the resins are formed from the reaction between polyfunctional organic acids or acid anhydrides and polyhydric alcohols under conditions well known in the art. The available polyfunctional organic acids or acid anhydrides can be any of many known compounds. Suitable polyfunctional acids or their anhydrides include, but are not limited to, maleic acid and anhydride, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid and anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, cyclohexanedicarboxylic acid, succinic anhydride, adipic acid, sebacic acid, azelaic acid, malonic acid, alkenyl succinic acids such as n-dodecenyl succinic acid, dodecyl succinic acid, octadecenyl succinic acid, and their anhydrides. Any of the lower alkyl esters of the above may be utilized. Any of the above mixtures are suitable without the intended limitation thereby.

[0097] Furthermore, a polybasic acid having three or more carboxylic acid groups or an anhydride thereof may be used. Examples of such compounds include 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic 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 for forming the unsaturated polyester resin 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, 1,2,5-pentanetriol, glycerol, 2-methyl-propanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxyethylbenzene. Mixtures of any of the above alcohols may be used.

[0098] The DCPD resins used in the present compositions and methods are known to those skilled in the art. These resins are typically DCPD polyester resins and derivatives and can be prepared according to various accepted procedures. By way of 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 made from DCPD, maleic anhydride, maleic acid, fumaric acid, phthalic 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 be prepared in situ from the reaction of pentadiene and maleic anhydride or may contain a nadic acid ester segment that can be added in its anhydride form during the preparation of the polyester. Examples regarding the preparation of DCPD unsaturated polyester resins can be found in U.S. Patent Nos. 3,883,612 and 3,986,922.

[0099] The DCPD resin can be used in various amounts when laminating the resin compositions of the present invention. Preferably, the laminated resin composition contains from about 10 to about 80 weight percent, more preferably from about 20 to about 40 weight percent, of the 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. Further, the DCPD resin preferably has an ethylenically unsaturated monomer content of less than 35 percent at an application viscosity of 200 - 800 cps. The vinyl ester resins used in the present compositions and methods include reaction products of unsaturated monocarboxylic acids or anhydrides and epoxy resins. Exemplary acids and anhydrides include (meth)acrylic acid or anhydride, α-phenylacrylic acid, α-chloroacrylic acid, crotonic acid, monomethyl and monoethyl esters of maleic acid or fumaric acid, vinyl acetic acid, sorbic acid, cinnamic acid, etc., including mixtures thereof. Available epoxy resins are known and include substantially any reaction product of a polyfunctional halohydrin, such as epichlorohydrin, and a phenol or polyhydric phenol. Suitable phenols or polyhydric phenols include, for example, resorcinol, tetraphenol ethane, and various bisphenols, such as bisphenol A, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl methane, 2,2'-dihydroxydiphenyl oxide, etc. Novolac epoxy resins may be used. Mixtures of any of the above may be used. Further, the vinyl ester resin may have pendant carboxyl groups formed from the reaction of esters and acid anhydrides with the hydroxyl groups of the vinyl ester backbone.

[0100] Other components in the resin may include epoxy acrylate oligomers known to those skilled in the art. By way of example, for the purposes of the present invention, the term "epoxy acrylate oligomer" may be defined as the reaction product of acrylic acid and / or methacrylic acid with an epoxy resin. Examples of processes for preparing epoxy acrylates can be found in U.S. Patent No. 3,179,623, the entire disclosure of which is hereby incorporated by reference. Available epoxy resins are known and include substantially any reaction product of a polyfunctional halohydrin, such as, but not limited to, epichlorohydrin, with phenol or a polyhydric phenol. Examples of phenols or polyhydric phenols include, but are not limited to, resorcinol, tetraphenol ethane, and various bisphenols such as bisphenol A, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylmethane, 2,2'-dihydroxydiphenyloxide, phenol or cresol formaldehyde condensates, etc. Mixtures of any of the above can be used. Preferred epoxy resins for use in forming epoxy acrylates are those derived from bisphenol A and bisphenol F, and in particular, their liquid condensates with epichlorohydrin having a molecular weight in the range of preferably about 300 to about 800 are preferred. It is preferred to utilize the epoxy acrylate of the following formula E-I.

[0101] [Chemical formula]

[0102] In the formula, R1 and R2 are H or CH3, and n ranges from 1 to 3, more preferably from 1 to 2. Other examples of usable epoxy acrylate oligomers include relatively low viscosity epoxy acrylates. By way of example, these materials can be obtained by the reaction of epichlorohydrin with diglycidyl ethers of aliphatic diols or polyols. Polyacrylates are also useful in the present composition for preparing the molding composition. The urethane poly(acrylate) of the following formula A-I may be used as part of the mixture.

[0103] [Chem.]

[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 the hydroxyl-free residue of an organic polyhydric alcohol containing hydroxyl groups bonded to different atoms; and f has an average value of 2 to 4. These compounds are typically reaction products of polyols, in which the hydroxyl groups first react with a diisocyanate using 1 equivalent per hydroxyl group, and the free isocyanate groups react with a hydroxyalkyl ester of acrylic acid or methacrylic acid. Polyhydric alcohols suitable for the preparation of urethane poly(acrylates) typically contain at least 2 carbon atoms and may contain 2 to 4 (including 2 and 4) hydroxyl groups. For example, polyols based on polycaprolactone esters of polyhydric alcohols such as those described in U.S. Patent No. 3,169,945 are included. Unsaturated polyols such as those described in U.S. Patent Nos. 3,929,929 and 4,182,830 may also be used. Diisocyanates suitable for the preparation of urethane poly(acrylates) are well known in the art and include aromatic, aliphatic, and cycloaliphatic diisocyanates. The isocyanates can be extended with a small amount of glycol to lower their melting points and form liquid isocyanates. Hydroxyalkyl esters suitable for the final reaction of the polyisocyanate formed from the polyol and the diisocyanate are exemplified by hydroxyacrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate. However, any acrylate or amide or methacrylate or amide containing an isocyanate-reactive group can be used here. 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] [Chemical formula]

[0108] Wherein, R1 is hydrogen or methyl, R2 is an aliphatic or aromatic group containing 2 to about 20 carbon atoms, and optionally, -O- or the following group

[0109] [Chemical formula]

[0110] may contain W and Z are independently -O- or the following group

[0111] [Chemical formula]

[0112] and R3 is hydrogen or lower alkyl. The compound is typically a half - ester or half - 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. Patent Nos. 3,150,118 and 3,367,992. In some embodiments, the composition comprises an unsaturated isocyanurate characterized by the following formula C - III.

[0113] [Chemical formula]

[0114] wherein R1 is hydrogen or methyl, R2 is a straight - chain 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 reaction of the remaining free isocyanate after the reaction of a diisocyanate with 1 equivalent of a hydroxyalkyl ester of acrylic acid or methacrylic acid. During the formation of the isocyanurate, there is a common understanding that the diisocyanate participates in the formation of two isocyanurate rings, thereby forming a cross - linked structure in which the isocyanurate rings can be linked by the diisocyanate used. Polyisocyanates could also be used to increase this type of cross - linking. Diisocyanates suitable for the preparation of urethane poly(acrylate) are well known in the art and include aromatic, aliphatic, and cycloaliphatic diisocyanates. The isocyanates can be extended with a small amount of glycol to lower their melting points and form liquid isocyanates. Hydroxyalkyl esters suitable for the final reaction of a polyol with a polyisocyanate formed from a diisocyanate are exemplified by hydroxyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate. However, any acrylate or methacrylate ester or acrylamide or methacrylamide containing an isocyanate-reactive group can be used here. Other alcohols containing one hydroxyl group may be used. The monoalcohol can be a monomer or a 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]

Chemical formula

[0116] Wherein R1 is independently hydrogen or methyl, R2 is independently hydrogen or lower alkyl, and h is 0 or 1. These compounds are typically the reaction products of a vinyl addition prepolymer having a plurality of pendant oxazoline 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 C-V.

[0117]

Chemical formula

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

[0119]

Chemical formula

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

[0121] Those skilled in the art have a common understanding that the above-described thermosetting organic materials are only representative examples of those that can be used in the practice of the present invention. Saturated polyesters, polyethers, and polyurethanes that may be used in the present composition include, for example, those described in U.S. Patent Nos. 4,871,811, 3,427,346, and 4,760,111. Saturated polyester resins and polyurethanes are particularly useful in hand lay-up, spray-up, sheet molding compounding, hot melt adhesive, and pressure sensitive adhesive application fields. 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 the polycondensation of aromatic or aliphatic dicarboxylic acids or polycarboxylic acids and aliphatic or cycloaliphatic diols or polyols or prepolymers thereof. Optionally, an excess of polyol can be added to obtain hydroxyl end groups or an excess of dicarboxylic acid monomer can be added to obtain carboxylic acid end groups. Suitable polyurethane resins can be formed by the reaction of diols or polyols and diisocyanates such as those described in U.S. Patent No. 4,760,111. An excess of diol is added to obtain hydroxyl end groups at the chain ends of the polyurethane. Saturated polyesters and polyurethanes may contain various other components, such as ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, and the like.

[0122] The thermoplastic polymer material that reduces shrinkage during molding can also be included in the present composition. Using these thermoplastic materials, molded articles with improved surface smoothness can be produced. A thermoplastic resin is added to the unsaturated polyester composition of the present invention to suppress shrinkage during curing. The thermoplastic resin is supplied in a liquid state and is prepared such that 30 to 45 mass percent of the thermoplastic resin is dissolved in a polymerizable resin of 55 to 70 mass percent having several polymerizable double bonds in one molecule. Examples of the thermoplastic resin include styrene-based polymers, polyethylene, polyvinyl acetate-based 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 the thermoplastic resin are as follows: 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; alkyl esters of methyl methacrylate and acrylic acid; methyl methacrylate and styrene; copolymers of methyl methacrylate and acrylamide. In some embodiments, 5 to 50 mass percent of the liquid thermoplastic resin; preferably 10 to 30 mass percent of the liquid thermoplastic resin is mixed.

[0123] The low profile agent (LPA) is mainly composed of a thermoplastic polymer material. The LPA may be included in the present composition. These thermoplastic intermediates present some problems with remaining compatibility with almost all types of thermosetting resin systems. The incompatibility between polymer materials results in difficulties in processing due to insufficient homogeneity between the resins. Problems caused by phase separation of the resin mixture include scumming, poor color uniformity, low surface smoothness, and low gloss. Therefore, it is important to incorporate components that will help with the stabilization of the resin mixture in order to obtain a homogeneous system that does not separate after their preparation. For this purpose, a wide variety of stabilizers can be used in the present invention, including block copolymers obtained from polystyrene - polyethylene oxide as described in U.S. Patent Nos. 3,836,600 and 3,947,422. The block copolymer stabilizer is made from a half - ester of maleic anhydride containing styrene and polyethylene oxide, as described in U.S. Patent No. 3,947,422. A saturated polyester prepared from hexanediol, adipic acid, and polyethylene oxide, available from BYK Chemie under the 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 Application Laid - Open No. 03 - 174424.

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

[0125] The polymerization of fatty acid esters is not particularly restricted. Usually, the alkyl esters of the above polymerized fatty acids are used as the polymerized fatty acid esters. The alkyl esters such as methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, amyl ester, hexyl ester, etc. and higher alkyl esters such as octyl ester, decyl ester, dodecyl ester, pentadecyl ester, octadecyl ester, etc. can be used, but among them, lower alkyl esters are preferred, and methyl ester, ethyl ester and butyl ester are more preferred. These polymerized fatty acids and polymerized fatty acid esters can be used alone or in combination of two or more. The total ratio of the polymerized fatty acids and polymerized fatty acid esters in the total polybasic carboxylic acids is not particularly restricted, and they can be used in various ratios in the range of 3 to 40% by mass of the resin composition.

[0126] Compounds that may also be included in the present composition are a wide variety of epoxy compounds. Typically, the epoxy compound is an epoxy resin, also called a polyepoxide. Useful polyepoxides herein are 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 desirably, the epoxy compound contains, on average, at least one pendant or terminal 1,2-epoxy group (i.e., vicinal epoxy groups per molecule). Examples of useful polyepoxides include polyglycidyl ethers of both polyhydric alcohols and polyhydric phenols, 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. A number of 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 novolak resins. Polyepoxides include epoxidized cycloolefins; and polymeric polyepoxides that are polymers and copolymers of glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether. Suitable polyepoxides are disclosed in U.S. Patent Nos. 3,804,735; 3,893,829; 3,948,698; 4,014,771 and 4,119,609; and Lee and Naville, Handbook of Epoxy Resins, Chapter 2, McGraw Hill, New York (1967).

[0127] The present invention is applicable to various polyepoxides. 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 produced 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 combine with the halogen of the halohydrin. The product is characterized by the presence of more than one epoxide, i.e., an epoxide 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. The reactive diluent is generally added to the polyepoxide formulation to reduce its working viscosity and to provide better wetting by the formulation.

[0128] It may include vinyl monomers as diluents together with vinyl esters, urethanes, 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 monomers that can be used include 2-vinylpyridine, 6-vinylpyridine, 2-vinylpyrrole, 2-vinylpyrrole, 5-vinylpyrrole, 2-vinyl oxazole, 5-vinyl oxazole, 2-vinyl thiazole, 5-vinyl thiazole, 2-vinyl imidazole, 5-vinyl imidazole, 3-vinyl pyrazole, 5-vinyl pyrazole, 3-vinyl pyridazine, 6-vinyl pyridazine, 3-vinyl isoxazole, 3-vinyl isothiazole, 2-vinyl pyrimidine, 4-vinyl pyrimidine, 6-vinyl pyrimidine, and any vinyl pyrazine. As a classification of other vinyl monomers, although not limited, (meth)acrylates, vinyl aromatic monomers, vinyl halides, and vinyl carboxylates are also included. Other monomers that can be used include, for example, diallyl phthalate, hexyl acrylate, octyl acrylate, octyl methacrylate, diallyl itaconate, diallyl maleate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate. Mixtures of the above may also be utilized.

[0129] As used herein and in the claims, the term "(meth)acrylate" and similar terms refer to both methacrylates and acrylates. 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)acrylate, trimethylolpropane triacrylate, trimethylolmethane tetramethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, ethoxylated polyhydric phenol diacrylate and dimethacrylate (containing 1 to 30 ethylene oxide units per OH group of phenol), propoxylated polyhydric phenol diacrylate and dimethacrylate (containing 1 to 30 propylene oxide groups per OH group of phenol). Examples of some useful dihydric and polyhydric phenols include catechol; resorcinol; hydroquinone; 4,4'-biphenol; 4,4'-isopropylidene bis(o-cresol); 4,4'-isopropylidene bis(2-phenylphenol); alkylidene diphenols such as bisphenol A; pyrogallol; phloroglucinol; naphthalene diol; phenol / formaldehyde resin; resorcinol / formaldehyde resin;and phenol / resorcinol / formaldehyde resins. A mixture of the above-mentioned diacrylate and polyacrylate may be used. Other examples include, but are not limited to, oxiranyl (meth)acrylates, such as 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, such as 3-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2,5-dimethyl-1,6-hexanediol (meth)acrylate, 1,10-decanediol (meth)acrylate, aminoalkyl (meth)acrylates, such as N-(3-dimethylaminopentyl (meth)acrylate, 3-dibutylaminohexadecyl (meth)acrylate; (meth)acrylic acid, nitriles of (meth)acrylic acid and other nitrogen-containing (meth)acrylates, such as N-((meth)acryloyloxyethyl)diisobutylketimine, N-((meth)acryloylethoxyethyl)dihexadecylketimine, (meth)acryloylamidocyanide, 2-(meth)acryloyloxyethylmethylcyanamide, cyanoethyl (meth)acrylate, aryl (meth)acrylates, such as benzyl (meth)acrylate or phenyl (meth)acrylate (in either case, the acrylic residue may be unsubstituted or substituted up to 4 times); carbonyl-containing (meth)acrylates, such as 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;(Meth)acrylates of ether alcohols, 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)acrylate, 2-ethoxyethoxymethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, allyloxymethyl (meth)acrylate, 1-ethoxybutyl (meth)acrylate, ethoxymethyl (meth)acrylate; (Meth)acrylates of halogenated alcohols, such as 2,3-dibromopropyl (meth)acrylate, 4-bromophenyl (meth)acrylate 1,3-dichloro-2-propyl (meth)acrylate, 2-bromoethyl (meth)acrylate, 2-iodoethyl (meth)acrylate, chloromethyl (meth)acrylate; (Meth)acrylates containing phosphorus, boron, and / or silicon, such as 2-(dimethylphosphato)propyl (meth)acrylate, 2-(ethylphosphito)propyl (meth)acrylate, dimethylphosphinoethyl (meth)acrylate, dimethylphosphinomethyl (meth)acrylate, dimethylphosphonoethyl (meth)acrylate, dimethyl (meth)acryloylphosphonate, dipropyl (meth)acryloylphosphate, 2-(dibutylphosphono)ethyl methacrylate, 2,3-butylene (meth)acryloylethyl borate, methyldiethoxy(meth)acryloylethoxysilane, diethyl phosphato (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, bis((meth)acryloyloxyethyl) sulfide may be mentioned.;

[0130] Vinyl monomers and polyfunctional acrylates used with vinyl esters, unsaturated polyesters, saturated polyesters, and polyurethanes may preferably be used in various amounts of about 10 to 50, more preferably about 20 to 40 weight percent based on the mass of the components that can be dissolved therein. Additives include inhibitors added to the resin mixture to stop or delay any cross-linking chain reactions that may be initiated by the formation of the expected free radicals. Free radicals can be formed at carbon-carbon double bonds through several different mechanisms such as intermolecular interactions by heat and light, so the possibility of free radical formation is very high. If this occurs, there is a fairly high possibility that the resin will cross-link during storage of the resin. Therefore, an appropriate amount of inhibitor in the system is useful for 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), mono-tert-butylhydroquinone (MTBHQ), di-tert-butylhydroquinone (DTBHQ), tert-butylcatechol (TBC), and other substituted and unsubstituted phenols and mixtures of the above. Nitroxide initiators can also be used as inhibitors in the present invention.

[0131] As other polymerization inhibitors, stable hindered nitroxyl compounds such as N,N-di-tert-butyl nitroxide; N,N-di-tert-amyl nitroxide; N-tert-butyl-2-methyl-1-phenyl-propyl nitroxide; N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide; 2,2,6,6-tetramethyl-piperidinyl oxy; 4-amino-2,2,6,6-tetramethyl-piperidinyl oxy; 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl oxy; 4-oxo-2,2,6,6-tetramethyl-piperidinyl oxy; 4-dimethylamino-2,2,6,6-tetramethyl-piperidinyl oxy; 4-ethanoyloxy-2,2,6,6-tetramethyl-piperidinyl oxy; 2,2,5,5-tetramethylpyrrolidinyl oxy; 3-amino-2,2,5,5-tetramethylpyrrolidinyl oxy; 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-piperidinyl oxy; 4-chloro-2,2,6,6-tetramethyl-piperidinyl oxy; 4-iodo-2,2,6,6-tetramethyl-piperidinyl oxy; 4-fluoro-2,2,6,6-tetramethyl-piperidinyl oxy; 4-cyano-2,2,6,6-tetramethyl-piperidinyl oxy; 4-carboxy-2,2,6,6-tetramethyl-piperidinyl oxy; 4-carbomethoxy-2,2,6,6-tetramethyl-1-piperidinyl oxy; 4-carboethoxy-2,2,6,6-tetramethyl-piperidinyl oxy; 4-cyano-4-hydroxy-2,2,6,6-tetramethyl-piperidinyl oxy; 4-methyl-2,2,6,6-tetramethyl-1-piperidinyl oxy; 4-carboethoxy-4-hydroxy-2,2,6,6-tetramethyl-piperidinyl oxy; 4-hydroxy-4-(1-hydroxypropyl)-2,2,6,6-tetramethyl-piperidinyl oxy;Examples include 4-methyl-2,2,6,6-tetramethyl-1,2,5,6-tetrahydropyridinyl oxyl and the like. Further useful stable hindered nitroxyl inhibitors are described in patent publications WO01 / 40404A1, WO01 / 40149A2, WO01 / 42313A1, US Patent 4,141,883, US6,200,460, and US5,728,872, which are incorporated herein by reference in their entirety.; According to some embodiments of the present invention, various amounts of inhibitor may be utilized. Preferably, the inhibitor ranges from about 0.001 to about 0.5 weight percent, more preferably from about 0.04 to about 0.1 weight percent, based on the mass of the reactants.

[0132] Suitable non-fibrous fillers are essentially inert particulate additives that reduce the cost of the final product while often reducing some of the physical properties of the polymerized 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, linen, zirconia, calcium sulfate, mica, talc, various forms of wood, glass (ground, platelet, sphere, microballoon), plastic (ground, platelet, sphere, microballoon), recycled polymer composite particles, various forms of metal, metal oxides or hydroxides (except those that change 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, fluorocarbon, 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 for strengthening or toughening the polymerizable and curable composition that forms the substrate. Commonly used types are 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, 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 (such as nylon), aromatic polyamides, olefins (such as polypropylene, polyester, ultra-high molecular weight polyethylene), polyurethanes (such as Spandex), α-cellulose, cellulose, regenerated cellulose (such as rayon), jute, sisal, vinyl chloride, vinylidene, linen, and thermoplastic fibers; metal fibers such as aluminum, boron, bronze, chromium, nickel, stainless steel, titanium or their alloys; and "whiskers", single, inorganic crystals. Preferably, the filler is added in an amount of 0 to 80% by weight, more preferably 20 to 60% by weight, based on the resin composition.

[0133] Flammable compounds such as those described in many published documents and patents known to those skilled in the art may be included in the present invention. For the preparation of flammable compositions, for example, brominated flammable compounds are useful. Preferred brominated flammable 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-chloroisopropyl) 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-propylphenyl) phosphate, tri(4-vinylphenyl) phosphate, bisphenols such as bisphenol-A, bis(diphenyl phosphate esters) of resorcinol or hydroquinone, resorcinol bis(2,6-dixylenyl phosphate), bis(diphenyl phosphoramide), phosphonates, such as dimethylmethyl phosphonate, dimethylpropyl phosphonate, phosphites, such as dimethyl phosphite, diethyl phosphite, trimethyl phosphite, triethyl phosphite, melamine polyphosphate, melamine cyanurate, metal phosphites, inorganic metal phosphites, red phosphorus, ammonium polyphosphate, etc. and mixtures thereof.

[0134] It should be noted that there is an incorrect "sio" in the original text which is retained as it is in the translation for the purpose of following the rules. It should probably be "isopropyl".When using the composition for bulk molding compounding or shear molding compounding, optionally, a thickener is added in the range of 0.05 to 10 percent by mass of the chemical thickener, preferably in the range of 0.2 to 5 percent by mass, 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 considered by those skilled in the art of molding compound technology 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 those described above. Other thickeners that may be included are isocyanates. These substances react with the hydroxyl groups that may be present in the polymer of the present invention or in other polymers added together with those described above. The polyisocyanates utilized in the present invention are aromatic, aliphatic and cycloaliphatic polyisocyanates having two or more isocyanate groups per molecule and an isocyanate equivalent of less than 300. Preferably the isocyanate is essentially free of ethylenic unsaturation and has no other substituents capable of reacting with an unsaturated polyester. The polyfunctional isocyanates used in the above reaction are well known to those skilled in the art. For the purposes of the present invention, diisocyanates include, for example, aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic diisocyanates of the type described by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, (1949), for example those corresponding to the following formula. OCN-R-(NCO) n In the formula, n is equal to 1 to 3, and R represents a difunctional aliphatic, alicyclic, aromatic, or araliphatic group having about 4 to 25 carbon atoms, preferably 4 to 15 carbon atoms, and not containing any groups capable of reacting with isocyanate groups. Examples of diisocyanates include, but are not limited to, 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; 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; 2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene diisocyanate; 2,6-hexahydro-1,3-phenylene diisocyanate; 2,6-hexahydro-1,4-phenylene diisocyanate; perhydro-2,4'-diphenylmethane diisocyanate; perhydro-4,4'-diphenylmethane diisocyanate; 1,3-phenylene diisocyanate; 1,4-phenylene diisocyanate; 2,4-toluene 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-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI); 1-methyoxy-2,4-phenylene diisocyanate; 1-chlorophenyl-2,4-diisocyanate; p-(1-isocyanatoethyl)-phenyl isocyanate; m-(3-isocyanatobutyl)-phenyl isocyanate; and 4-(2-isocyanato-cyclohexyl-methyl)-phenyl isocyanate. Mixtures of any of the above may be used.When it is determined to be appropriate, a diisocyanate containing other functional groups such as amino functional groups may be used.

[0135] A preferred polyfunctional isocyanate additive of the present molding composition may consist of a bifunctional additive prepared by a one-step addition reaction between 1 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 an amount of 0.01 to 50 mass percent, most preferably 1 to 30 mass percent of the mixture, of the diol or triol after reaction with the diol or triol, and is added in an amount sufficient to leave unreacted polyfunctional isocyanate free in the mixture. In the reaction of involving a diol or triol with a polyfunctional isocyanate, it is preferable to use a catalyst. Many catalysts known to those skilled in the art may be used for this purpose. Suitable catalysts are described in U.S. Patent Nos. 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 mgKOH / g include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol and polypropylene glycol having a molecular weight of 200 to 3000, and polytetramethylene glycol having a molecular weight of 200 to 3000.

[0136] The present composition and method may use a carbodiimide, preferably a carbodiimide intermediate containing about 1 to about 1000 repeating units. It is preferable to use a polycarbodiimide. Depending on the addition amount, a carbodiimide is used to react with a resin or component having 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 to Nava et al., the entire disclosure of which is incorporated herein by reference. Generally, the carbodiimide is preferably a polycarbodiimide, which includes aliphatic, alicyclic, or aromatic polycarbodiimides. The polycarbodiimide can be prepared by many reaction schemes known to those skilled in the art. For example, the polycarbodiimide can be synthesized by reacting an isocyanate-containing intermediate and a diisocyanate under appropriate reaction conditions. The isocyanate-containing intermediate can typically be formed by the reaction between a component that is a monomer containing active hydrogen and a diisocyanate. Also included are polycarbodiimides prepared by the polymerization of isocyanates to form polycarbodiimides, which subsequently react with components containing active hydrogen. In some embodiments, the carbodiimide intermediate is represented by a formula selected from the group consisting of the following formulas.

[0137] [Chemical formula]

[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 a polymer unit having 1 to 1000 repeating units; and n ranges from 0 to 100. The carbodiimide is preferably used in a proportion in the range of about 0.10 to about 50% by mass, more preferably 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 a reinforcing agent enhances the mechanical properties of the resulting cured material, and the addition of a UV stabilizer prevents degradation by UV irradiation. The additives include phenolic antioxidants such as those described on pages 1 to 104 of "Plastic additives", Hanser Publishers, 1990 by R. Gachter and Muller. Mannich type antioxidants, especially phenols and naphthols suitable for the purposes of the present application, include hindered aromatic alcohols such as hindered phenols and naphthols, for example those described in U.S. Patent No. 4,324,717, the entire disclosure of which is hereby incorporated by reference. Additional additives known to those skilled in the art may be utilized in the resin compositions of the present invention, for example, paraffin, lubricants, flow agents, defoaming agents, flow 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 preferred 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 the internal release agent added is in the range of 0.5 to 5.0% by mass, preferably in the range of 0.4 to 4.0% by mass. Therefore, stable demolding can be performed without any cracks occurring in the molded article when removing it from the mold.

[0139] The acrylic resin prepared by radical polymerization can be used in the mixture. The acrylic resin preferably has an acid value 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 preferably has a hydroxyl value 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 relative to polystyrene standards. The acrylic resin preferably has a polydispersity of about 1.5 to about 30, more preferably about 2 to 15. The Tg of the acrylic resin 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 to be used is preferably formed from about 0.5 to 30 weight percent (most preferably about 1 to 15 weight percent) of a functional mercaptan containing a carboxyl, hydroxyl, siloxy, or sulfonic acid group, and about 70 to about 99.5 weight percent (most preferably 85 to 99 weight percent) of an ethylenically unsaturated monomer. Example 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. Also included are the block copolymers of alkenyl aromatic hydrocarbons and alkylene oxides described in U.S. Patent Nos. 3,050,511 and 3,836,600.

[0140] Various hydroxyl and carboxyl terminated rubbers may be used as reinforcing agents. Examples of such materials are given in U.S. Patent No. 4,100,229, the entire disclosure of which is hereby incorporated by reference; and J.P. Kennedy, J. Macromol. Sci. Chem. A21, pp. 929 (1984). Examples of such rubbers include, for example, carbonyl terminated and hydroxyl polybutadienes. An example of a carbonyl terminated polybutadiene is commercially available under the trade name HycarTM from BF Goodrich of Cleveland, OH. Examples of hydroxyl terminated polybutadienes are commercially available from Atochem, Inc. of Malvern, PA, and Shell Chemical of Houston, TX. Some polysiloxanes may be used as reinforcing agents. Examples of suitable 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); Youqing et al, Polym. Bull. 37, 21 - 28 (1996).

[0141] Also included in the present invention are various telechelic polymers such as those described in “Telechelic Polymers: Synthesis and Applications”, Editor: Eric J. Goethals, CRC Press, Inc. 1989. A variety of polyethoxylated and polypropoxylated hydroxyl-terminated polyethers obtained from alcohols, phenols (including alkylphenols), and carboxylic acids can be used as reinforcing agents. Examples of alcohols that can be used to form 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 phenols and alkylphenols that can be used 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 the formation of molded articles including storage tanks, body panels, boat structures, tub showers, cultured marble, solid surfaces, polymer concrete, pipes, and inner liners for pipe and pipeline rehabilitation. Other applications include gel coats and coatings. Unsaturated resins may be used alone or in combination with other suitable materials. When the resins are used with other materials (e.g., fiber reinforcements and fillers), they are typically used to form reinforced products such as storage tanks, body panels, boat structures, tub showers, etc. by any of the known processes 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 composition of the present invention provides several advantages. The products have a greater amount of carbon-carbon bonds than any typical thermosetting resin containing ester or urethane bonds, so they are less sensitive to thermal and hydrolysis stability. Replacing these ester bonds with simple yet most stable carbon-carbon σ bonds results in unsaturated thermosetting resins that are not only more stable to hydrolysis and heat but also chemically resistant. A very important problem regarding 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 coordinated with metal salts such as magnesium, zinc, or calcium oxides. These reactions are important, especially in the preparation of SMC application fields, pultrusion molding, adhesives, and open-mold products. The resins of the present invention have a low shrinkage rate either alone or in combination with other thermosetting or thermoplastic resins. Examples for explaining these advantages are shown below.

[0144] Polymers, copolymers, or oligomers containing reactive functional groups capable of undergoing polymerization with other ethylenically unsaturated monomers or polymers are prepared by using styrene monomers as the main monomer in combination with various ethylenically unsaturated monomers. For the purposes of the present invention, it is preferred to prepare low molecular weight polymers, copolymers, and oligomers useful in the present invention by nitroxide-mediated radical polymerization. The polymer intermediates and / or oligomer intermediates are formed from ethylenically unsaturated type monomers incorporated as repeating units in the backbone. The ethylenically unsaturated type monomers function as solvents for polymerization and as reactive monomers to form polymer and / or oligomer resin products. At least one of the monomers contains reactive functional groups capable of further reacting with other moieties. Examples of reactive functional groups included in the monomers are, 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] The polystyrene intermediate containing a functional group can further react with other monomers containing ethylenically unsaturated moieties. For example, a polystyrene intermediate containing an epoxy group along the backbone can further react with monomers such as acrylic acid or methacrylic acid. As another example, the preparation of a polystyrene intermediate containing a hydroxyl functional group that can further react with an isocyanate acrylate such as 2-isocyanatoethyl methacrylate can be mentioned. Diisocyanate reacted with 1 equivalent of hydroxyethyl methacrylate may be used. As another example, the preparation of a polystyrene intermediate containing an acid group functionality that can further react with an acrylate or methacrylate containing epoxy functionality can be mentioned. For the purposes of the present invention, a curable composition can be prepared using both polystyrene intermediates containing functional groups, preferably those containing reactive groups. Further, 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, by applying a curable thermosetting composition to a substrate or reinforcing material, for example, impregnating or coating the substrate or reinforcing material and curing the curable composition, a composite article can be formed. The properties achieved from these materials can provide composite material systems that can be used in various application fields including molding, laminating, infusion, pultrusion, encapsulation, coating, adhesives, prepregs, electrical components, and electronic components.

Examples

[0146] Examples Technical terms: Mn-Hydro-Cure® III - 9.0% manganese AcBL - α-acetyl-γ-butyrolactone EtAcAc - ethylacetoacetonate MAcAc - methylacetoacetonate TAcAc - tert-Butylacetylacetonate DDD - 2,2-Dimethyl-1,3-dioxane-4,6-dione NQ - 1,4-Naphthoquinone PBQ - para-Benzoquinone THQ - Toluhydroquinone Ethanox 4703 - 2,6-Di-tert-butyl-α-dimethyl-amino-p-cresol Potassium - Potassium octoate DMPT - N,N-Dimethyl-p-toluidine BiPy - 2,2’-Bipyridine DDSH - Dodecyl mercaptan TaAcid - Tartaric acid Asc. 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 31612 - It is a propylene glycol / maleic anhydride unsaturated polyester. Polylite HS 35060 - It is an intermediate of bisphenol A dimethacrylate. Polylite HS 35065 - It is an intermediate of isophthalic acid type dimethacrylate. DION 44070 - 00 - It is a low molecular weight epoxy bisphenol A vinyl ester. DION 32774 - 00 - It is a novolac epoxy vinyl ester. DION 9102 - 70 - It is a bisphenol A chain extended epoxy vinyl ester. GT - Gelation time (minutes). TTP - Total time (minutes) until the maximum heat generation is achieved. EXO - Peak heat generation (°C) reached during the curing process. For the components incorporated into the mixture of polymerizable components, the amounts shown in the following table are given as parts per hundred (pph) or parts per million (ppm) per 100 parts of the reactive mixture. The amounts and concentrations are given in wt / wt units unless the text or context indicates units of vol / wt. The following examples are provided to illustrate the invention and should not be construed as limiting the invention.

[0147] Sample preparation: A predetermined amount of the components according to the claims of the present invention was added to 100 grams of a liquid thermosetting resin as described below. All the components were mixed, and the gelation of the resin was periodically checked using a tongue depressor. When the resin gelled, the time was recorded, and a thermocouple was inserted into the resin to measure the heat generation resulting from the curing reaction. The heat generation was recorded together with the observed maximum temperature. Examples regarding various methods for curing the thermosetting system are shown in the following table. Several techniques can be utilized for the preparation and curing of the polymerizable composition. For example, in one technique, a radically 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 desired 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 substance. As a second method, the radically polymerizable component (a) is mixed with a polyhydroxycarboxylic acid (e.g., tartaric acid or ascorbic acid) or a thiol compound (e), and a 1,3-dioxo compound (f). When it is desired to use this polymerizable composition 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 include, but are not limited to, forming a crosslinked network by adding (b) after mixing (a) with (c), (d), and (f). Depending on the chemical nature 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 field of application.

[0148] To evaluate the mechanical properties (e.g., heat distortion temperature (HDT) and physical properties) of the cured material produced from the polymerizable composition, clear castings were prepared using the above method and cured overnight at room temperature, and then post-cured at 180°F (82.2°C) for 2 hours and 250°F (121.1°C) for 2 hours the next day. Mechanical properties were analyzed at room temperature using an Instron apparatus, and 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 heat distortion was measured according to ASTM standard D-648; and the Barcol hardness was determined according to 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 a TA Instruments Q2000 system. The instrument was started with a ~10 mg catalyzed sample at 25°C in isothermal hold mode until complete exothermic polymerization was observed. The heat of cure generated due to the heat of polymerization was integrated using either a linear or sigmoid horizontal baseline. The results of the heat of polymerization are given in Kj / Kg. Table 1 shows the curing behavior of 50 / 50 wt.% mixtures of HDDA / PEMA 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.% mixtures of HDDA / PEMA with various amounts of BiPy, DMPT, Mn, and AcBL added.

[0151]

Table 2

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

[0153]

Table 3

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

[0155]

Table 4

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

[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 the acetylacetonate intermediate and the mercaptan compound, and then the manganese-containing salt was added to initiate the polymerization. As can be observed, the thiol compound serves to shorten the gelation time without impairing the exotherm of the polymerization or to obtain a non-sticking surface on the thin film.

[0159]

Table 6

[0160] Table 7 shows the curing behavior of 32774-00 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 mixed with MMA and with the addition of BiPy, DMPT, Mn, and AcBL.

[0163]

Table 8

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

[0165] [Table 9]

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

[0167] [Table 10]

[0168] Table 10B shows the curing behavior of BuDMA using 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-dimethyl-amino-p-cresol).

[0173]

Table 13

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

[0175]

Table 14

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

[0177]

Table 15

[0178] Table 15 shows the curing 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 octoate, ethylacetoacetonate, and acetylbutyrolactone.

[0185]

Table 19

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

[0187]

Table 20

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

[0189]

Table 21

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

[0191]

Table 22

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

[0193]

Table 23

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

[0195]

Table 24

[0196] In view of the present disclosure, it can be seen that the present compositions and methods can be practiced in accordance with the present teachings. Further, the various components, materials, structures, and parameters are included by way of illustration and example only and are not intended to be limiting in any sense. In view of the present disclosure, the present teachings can be incorporated into other applications, and components, materials, structures, and apparatus for practicing such applications can be determined while remaining within the scope of the appended claims.

[0197] Exemplary Embodiments The following exemplary embodiments are provided to illustrate the present invention and should not be construed as limiting the present invention. Embodiment 1A. A polymerizable composition comprising the following: a) a radically 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 a manganese- or iron-containing salt or complex, wherein the polymerizable composition substantially does not contain one or more (preferably all) of cobalt, copper, and a peroxide initiator, and the polymerizable composition comprises at least one of the following: (1) (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; wherein the polymerizable composition has a gelation time drift of less than about 20% or less than about 15% over 30 days or over 60 days. Embodiment 1B. A polymerizable composition comprising the following: a) a radically 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 a peroxide initiator. Embodiment 1C. A polymerizable composition comprising the following: a) a radically 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 a peroxide initiator. Embodiment 1D. A polymerizable composition comprising the following: a) a radically 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 a peroxide initiator. Embodiment 1E. A polymerizable composition comprising the following: a) a radically 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, 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 over 60 days. Embodiment 1F. A polymerizable composition comprising the following: a) a radically polymerizable component; 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, wherein the polymerizable composition has a characteristic gelation time when combined with a manganese-containing or iron-containing salt or 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 over 60 days.

[0198] Embodiment 2. The polymerizable composition according to any one of Embodiments 1A to 1F, wherein the manganese- or iron-containing salt or complex is selected from salts and complexes of the following formulas and mixtures thereof; salts selected from salts of the formula (M)(RCOO-)2; the naphthenate complex; or the acetylacetonate complex. Embodiment 3. The polymerizable composition according to any one of Embodiments 1A to 1F, wherein the manganese- or iron-containing salt or complex is selected from organophosphine metal complexes containing an organophosphine having the structure of the above formula P-I, P-II, P-III or P-IV, and mixtures thereof. Embodiment 4. The 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 a nitrogen-donor ligand of the above formula N-I, N-II, N-III, N-IV, N-V, N-VI, or N-VII. Embodiment 5. The polymerizable composition according to any one of Embodiments 1A to 1F, wherein the 1,3-dioxo compound is selected from compounds of the above formula D-I to D-V 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-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. 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 the above formula H-I, 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 mixtures thereof. Embodiment 9. A polymerizable composition according to any one 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 radically 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; f) a 1,3-dioxo compound, wherein the curing system does not substantially contain one or more of cobalt, copper, and a peroxide initiator, and comprises at least one of the following: (i) a combination of 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 11. The curing system of Embodiment 10, wherein the curing system consists essentially 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 is the curing system of Embodiment 10 or 11, which essentially consists 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. The curing system is the curing system of any one of Embodiments 10 to 12, which 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, comprising forming a mixture of the following: a) a radically 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; f) a 1,3-dioxo compound; and the polymerizable composition does not substantially contain one or more of cobalt, copper, and a peroxide initiator, and the polymerizable composition contains at least one of the following: (1) (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 15. The method of Embodiment 14, further comprising preparing a polymerizable composition comprising the following: a) a radically 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. This method further includes 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 radically polymerizable component; 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. This 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 organic complex.

[0201] Embodiment 17. The method according to any one of Embodiments 14 to 16, wherein the radically polymerizable component is selected from the group consisting of a polyester resin, a vinyl ester resin, a urethane acrylate resin, a vinyl Hybrid resin, and combinations thereof. Embodiment 18. Any method according to Embodiment 15, wherein the radically 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, and then a 1,3-dioxo compound is added to form a mixture. Embodiment 19. The method of Embodiment 14, wherein the radically 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, and then a 1,3-dioxo compound is added to form a mixture. Embodiment 20. The method of Embodiment 14, wherein the radically polymerizable component, 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, and then a manganese- or iron-containing salt or organic complex is added to form a mixture. Embodiment 21. The method of Embodiment 14, wherein the radically polymerizable component, a 1,3-dioxo compound, and a polyhydroxycarboxylic acid or thiol compound are mixed and stored for at least 30 days, and then a manganese- or iron-containing salt or organic complex is added to form a mixture. Embodiment 22. The method according to any one of Embodiments 14 to 21, further comprising applying the mixture as a coating, layer, or casting before or while the polymerizable composition cures. Embodiment 23. The method according to any one 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 the polymerizable composition according to any one of Embodiments 1A to 1F, wherein the resin is a sheet molding compound (SMC) resin, resin transfer molding (RTM) resin, casting resin, adhesive resin, pultrusion resin, corrosion-resistant resin, flame-retardant resin, low or zero styrene content resin, prepreg, gel coat, or coating resin. Embodiment 25. The polymerizable composition according to any one of the foregoing embodiments, wherein the polymerizable composition has a heat of polymerization of less than 950 kJ / kg. Embodiment 26. The polymerizable composition according to any one of the foregoing embodiments, wherein the polymerizable composition has a peak exotherm of less than 300 °C. Embodiment 27. The polymerizable composition according to any one of the foregoing embodiments, wherein the polymerizable composition has a time to peak exotherm of 5 minutes to 60 minutes. Embodiment 28. The polymerizable composition according to any one of the foregoing embodiments, wherein the polymerizable composition has a gelation time of 10 seconds to 60 minutes.

[0203] All patents and published documents referred to herein are hereby expressly incorporated by reference. As disclosed herein, a wide range of values are provided. It is commonly understood that each intervening value between the upper and lower limits of such range to one-tenth of the unit of the lower limit is also specifically disclosed, unless the context clearly dictates otherwise.

Claims

1. as follows: a) a radically polymerizable component; b) a manganese-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; f) a 1,3-dioxo compound; and g) an optional transition metal salt other than the manganese-containing salt or organic complex A polymerizable composition comprising: the polymerizable composition substantially does not contain one or more of cobalt, copper, and a peroxide initiator, and the polymerizable composition is as follows: (1) (i) a combination of a tertiary amine and (ii) a nitrogen-containing aromatic heterocycle; or (2) a polyhydroxycarboxylic acid containing at least one of: the polymerizable composition has a gelation time drift of less than about 20% over 25 days, the polymerizable composition.

2. the manganese-containing salt or complex is a salt and complex of the following formula: i) a salt of the formula (M)(RCOO−) 2 (wherein M is manganese and each R is independently selected from H, substituted or unsubstituted linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted linear alkenyl, substituted or unsubstituted branched alkenyl, substituted or unsubstituted linear alkynyl, substituted or unsubstituted branched alkynyl, substituted or unsubstituted aryl, or substituted or unsubstituted alkylaryl); ii) the following formula 【Chemical Formula 1】 (wherein M is manganese, m and n are independently 0 or more, and R' and R'' are independently H, substituted or unsubstituted linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted linear alkenyl, substituted or unsubstituted branched alkenyl, substituted or unsubstituted linear alkynyl, substituted or unsubstituted branched alkynyl, substituted or unsubstituted aryl, and substituted or unsubstituted alkylaryl) a naphthenate complex selected from complexes of iii) the following formula: [Chemical Formula 2] (wherein M is manganese, R 1 , R 2 , R 3 and R 4 are each independently selected from H, substituted or unsubstituted linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted linear alkenyl, substituted or unsubstituted branched alkenyl, substituted or unsubstituted linear alkynyl, substituted or unsubstituted branched alkynyl, substituted or unsubstituted aryl, and substituted or unsubstituted alkylaryl) an acetylacetonate complex selected from complexes of and mixtures thereof, The polymerizable composition according to claim 1.

3. The manganese-containing salt or complex is represented by the following formula P-I, P-II, P-III or P-IV: [Chemical Formula 3] (wherein R 1In each case independently, H, hydroxyl, C1-C6 branched or cyclic aliphatic; C1-C4 alkoxy; aryl, for example, C6-C20 monocyclic or polycyclic aryl, such as phenyl, toluoyl, naphthyl, biphenyl, terphenyl, halogen-containing aryl aromatic, amino-containing aryl aromatic, silyl-containing aryl aromatic; heteroalkyl, for example, C6-C20 monocyclic or polycyclic heteroaryl, such as thienyl, furyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, quinolyl and isoquinolyl); 【Chemical Formula 4】 (wherein R 1 In each case independently, H, hydroxyl, C1-C6 branched or cyclic aliphatic, C1-C4 alkoxy; aryl, for example, C6-C20 monocyclic or polycyclic aryl, such as phenyl, toluoyl, naphthyl, biphenyl, terphenyl, halogen-containing aryl aromatic, amino-containing aryl aromatic, silyl-containing aryl aromatic; heteroalkyl, for example, C6-C20 monocyclic or polycyclic heteroaryl, such as thienyl, furyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, quinolyl and isoquinolyl; and R 2 In each case independently, H, C1-C14 straight-chain, branched or cyclic aliphatic, alkyl aromatic, halogen-containing aryl aromatic, amino-containing aryl aromatic, silyl-containing aryl aromatic or alkoxy group-containing aryl aromatic, and the R 1 group, R 2 group or R 1 and R 2 groups are interconnected by an alicyclic or aromatic ring therebetween; n is 0 to 4; Y is either N or P); 【Chemical Formula 5】 (wherein R 1In each case independently, H, hydroxyl, C1-C6 branched or cyclic aliphatic, C1-C4 alkoxy; aryl, for example, C6-C20 monocyclic or polycyclic aryl, such as phenyl, toluoyl, naphthyl, biphenyl, terphenyl, halogen-containing aryl aromatic, amino-containing aryl aromatic, silyl-containing aryl aromatic; heteroalkyl, for example, C6-C20 monocyclic or polycyclic heteroaryl, such as thienyl, furyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, quinolyl and isoquinolyl; Y is N or P); 【Chemical Formula 6】 (In the formula, R is, in each case independently, H, a C1-C14 straight-chain, branched or cyclic aliphatic, alkyl aromatic, halogen-containing aryl aromatic, amino-containing aryl aromatic or alkoxy group-containing aryl aromatic; R 1 In each case independently, H, hydroxyl, C1-C6 branched or cyclic aliphatic, C1-C4 alkoxy; aryl, for example, C6-C20 monocyclic or polycyclic aryl, such as phenyl, toluoyl, naphthyl, biphenyl, terphenyl, halogen-containing aryl aromatic, amino-containing aryl aromatic, silyl-containing aryl aromatic; heteroalkyl, for example, C6-C20 monocyclic or polycyclic heteroaryl, such as thienyl, furyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, quinolyl and isoquinolyl; R 2 In each case independently, H, a C1-C14 straight-chain, branched or cyclic aliphatic, alkyl aromatic, halogen-containing aryl aromatic, silyl-containing aryl aromatic, amino-containing aryl aromatic or alkoxy group-containing aryl aromatic, and are linked to each other by an alicyclic or aromatic ring; Y is either N or P) The polymerizable composition according to claim 1, selected from an organophosphine metal complex containing an organophosphine having the structure of , and a mixture thereof.

4. The manganese-containing salt or complex is the following formula N-I, N-II, N-III, N-IV, N-V, N-VI, or N-VII: 【Chemical Formula 7】 (In the formula, R 1 and R 2 are independently selected from the group consisting of C 1-24 alkyl, C 6-10 aryl, heteroaryl, heteroaryl C 1-6 alkyl, and -CH 2 -CH 2 -N(CH 3 ) 2 where 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 selected from the group consisting of -H, C 1-8 alkyl, C 1-8 alkyl - O - C 1-8 alkyl, C 1 - 8 alkyl - O - C 6-10 aryl, C 6-10 aryl, C 1-8 - hydroxyalkyl, and -(CH 2 ) m C(O)OR 5 ; R 5 is selected from -H or C 1-4 alkyl, and m is an integer selected from 0 to 4; R 6 and R 7 are each independently selected from the group consisting of -H, -F, -Cl, -Br, -OH, C 1-4 alkoxy, -NH - C(O) - H, -NH - C(O) - C 1-4 alkyl, -NH 2 , -NH - C 1-4 alkyl, and C 1-4 alkyl; X 1 is selected from -C(O)- or -[C(R 8 ) 2 n where n is an integer selected from 0 to 3, and each R 8 ​is, independently, -H, -OH, C 1-4 alkoxy and C 1-4 alkyl selected from the group consisting of); 【Chemical Formula 8】 (wherein R 11 and R 12 are each independently a group of the formula -R 14 -R 15 ; R 13 is -H, -R 14 -R 15 , as well as C 1-6 alkyl, C 6-10 aryl and C 6-10 aryl-C 1-6 alkyl selected from the group consisting of optionally substituted groups; Each R 14 is independently a single covalent bond or C 1-6 alkylene, C 2-6 alkenylene, C 1-6 alkyleneoxy, amino C 1-6 alkylene, C 2-6 alkylene ether, carboxylic acid ester and carboxylic acid amide selected from the group consisting of optionally substituted groups; and Each R 15 is independently 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); 【Chemical Formula 9】 Formula N-III (wherein each R 20 is independently C 1-6 alkyl, C 3-8 cycloalkyl, heterocycloalkyl, heteroaryl, C 6-10 aryl and C 6-10 aryl-C 1-6 alkyl selected from the group consisting of, -OH, C 1-6Alkoxy, phenoxy, carboxylate, carboxamide, carboxylic acid ester, sulfonate, amine, C 1-6 alkylamine and N + (R 21 ) 3 which may be optionally substituted with a substituent selected from the group consisting of; Each R 21 is, C 1-6 alkyl, C 2-6 alkenyl, C 6-10 aryl-C 1-6 alkyl, C 6-10 aryl-C 2-6 alkenyl, C 1-6 alkyloxy, C 2-6 alkenyloxy, aminoC 1-6 alkyl, aminoC 2-6 alkenyl, C 1-6 alkyl ether, C 2-6 alkenyl ether, and -CX 2 2 -R 22 selected from; Each X 2 is independently selected from -H or C 1-3 alkyl, where each R 22 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 at least one of R 21 is -CX 2 -R 22 is); 【Chemical Formula 10】 Formula N-IV (wherein p is 4, and each X 3 is the following formula 【Chemical Formula 11】 Each R 37 is independently -H, C 1-6 alkyl, -CH 2 CH 2 0H, pyridin-2-ylmethyl and -CH 2selected from the group consisting of C(O)OH; and R 31 、R 32 、R 33 、R 34 、R 35 and R 36 are each independently selected from -C 1-4 alkyl and C 1-4 -hydroxyalkyl;), independently selected from); [Chemical Formula 12] Formula N-V (wherein each R 40 is independently selected from -H or C 1-20 alkyl, C 1-6 alkyl, C 6-10 aryl, C 2-6 alkenyl or C 2-6 -alkynyl, optionally substituted, from the group consisting of; and all nitrogen atoms of the polycycle are coordinated to the transition metal); [Chemical Formula 13] Formula N-VI (wherein X 4 is -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 C(OH)HCH 2 -; each R 50 is independently selected from -H, C 1-6 alkyl, C 3-8 cycloalkyl, heterocycloalkyl, heteroaryl, C 6-10 aryl and C 6-10 aryl-C 1-6 alkyl, from the group consisting of, -OH, C 1-6 alkoxy, phenoxy, carboxylate, carboxamide, carboxylic acid ester, sulfonate, aniline, C 1-6 alkylamine and -N + (R 51 ) 3 optionally substituted with a substituent selected from; each R 51 is -H, C 1-6 alkyl, C 2-6 alkenyl, C 6-10 aryl, C 1-6 alkyl, C 6-10 aryl, C 2-6 alkenyl, C 1-6 alkyloxy, C 2-6 alkenyloxy, amino C 1-6 alkyl, amino C 2-6 alkenyl, C 1-6 alkyl ether, C 2-6 alkenyl ether, and -C(X 5 ) 2 -R 52 selected from; each X 5 is independently -H or C 1-3 selected from alkyl, and each R 52 is independently selected from optionally substituted heteroaryl groups selected from the group consisting of pyridyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and R 50 at least two of which are -C(X 5 ) 2 -R 52 is); 【Chemical Formula 14】 Formula N-VII (wherein each R 60 is independently -H, C 1-6 alkyl, C 6-10 aryl, C 1-6 alkyl-C 6-10 aryl and C 2-6 selected from the group consisting of alkenyl), The polymerizable composition according to claim 1, selected from complexes containing a nitrogen-donating ligand of

5. The 1,3-dioxo compound is represented by the following formulas D-I to D-VI: 【Chemical Formula 15】 (wherein 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, substituted or unsubstituted linear 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 linear or branched C 1 -C 20 alkyl, C 6 -C 20 aryl, alkylaryl, arylalkyl, a part of the polymer chain, OR 3 or NR 3 R 4 ; R 1 R 2 R 3 and R 4 each independently represent a C 1 -C 20 alkyl, C 6 -C 20 aryl, alkylaryl or arylalkyl group, each optionally containing one or more heteroatoms and / or substituents; or there may be a ring between R 1 and R 2 and / or between R 1 and R 3 and / or between R 1 and R 4 ; or R 3 and / or R 4 may be part of the polymer chain or attached to the polymer chain or contain a polymerizable group) The polymerizable composition according to claim 1, selected from compounds of

6. The polymerizable composition according to 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. The following formula H-I, H-II, or H-III: 【Chemical 16】 (wherein R 1 , R 2 , and R 3 are each independently H, halogen, linear or branched C 1 -C 20 alkyl, C 6 -C 20 aryl, alkylaryl, arylalkyl, part of a polymer chain, OR 4 , NR 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) The polymerizable composition according to claim 1, comprising a nitrogen-containing heterocyclic amine selected from the group consisting of the compounds of and mixtures thereof.

8. The composition according to claim 1, comprising a polyhydroxycarboxylic acid selected from tartaric acid, ascorbic acid, or mixtures thereof.

9. The polymerizable composition according to claim 1, wherein the manganese-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. A curing system for curing a radically polymerizable component, comprising the following: b) A manganese-containing salt or an organic complex; c) An optional tertiary amine or phosphine; d) An optional nitrogen-containing aromatic heterocycle or a thiol-containing compound; e) An optional polyhydroxycarboxylic acid; f) A 1,3-dioxo compound and; the curing system does not substantially contain one or more of cobalt, copper, and a peroxide initiator, and the curing system comprises the following: (1) (i) A combination of a tertiary amine and (ii) a nitrogen-containing aromatic heterocycle; or (2) A polyhydroxycarboxylic acid The curing system contains at least one of the above.

11. The curing system according to claim 10, wherein the curing system consists essentially of a manganese-containing salt or an organic complex, a tertiary amine, a nitrogen-containing aromatic heterocycle, and a 1,3-dioxo compound.

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

13. A method for curing a polymerizable composition, comprising the following: a) A radically polymerizable component; b) A manganese-containing salt or an organic complex; c) An optional tertiary amine or phosphine; d) An optional nitrogen-containing aromatic heterocycle or a thiol-containing compound; e) An optional polyhydroxycarboxylic acid; f) A 1,3-dioxo compound including forming a mixture containing; the polymerizable composition does not substantially contain one or more of cobalt, copper, and a peroxide initiator, and the polymerizable composition comprises the following: (1) (i) A combination of a tertiary amine and (ii) a nitrogen-containing aromatic heterocycle; or The method as described above, comprising at least one polyhydroxycarboxylic acid.

14. The following: a) A radically polymerizable component; b) A manganese-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; A polymerizable composition comprising: The following: (1) A combination of (i) a tertiary amine and (ii) a nitrogen-containing aromatic heterocycle; or (2) A polyhydroxycarboxylic acid Preparing a polymerizable composition comprising at least one of the above; Storing the polymerizable composition for at least 30 days; Then mixing the polymerizable composition with a 1,3-dioxo compound The method according to claim 13, further comprising the above.

15. The following: a) A radically polymerizable component; 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 A polymerizable composition comprising: The following: (1) A combination of (i) a tertiary amine and (ii) a nitrogen-containing aromatic heterocycle; or (2) A polyhydroxycarboxylic acid Preparing a polymerizable composition comprising at least one of the above; Storing the polymerizable composition for at least 30 days; Then mixing the polymerizable composition with a manganese-containing salt or organic complex The method according to claim 13, further comprising **Claim 16** The method according to claim 13, 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, a prepreg, a gel coat or a coating resin. **Claim 17** The method according to claim 13, wherein the radically polymerizable component is selected from the group consisting of a polyester resin, a vinyl ester resin, a urethane acrylate resin, a vinyl hybrid resin, and combinations thereof. **Claim 18** The method according to claim 13, wherein the radically polymerizable component, the manganese-containing salt or organic complex, the tertiary amine, and the nitrogen-containing aromatic heterocycle or thiol-containing compound are mixed and stored for at least 30 days, and then a mixture is formed with the 1,3-dioxo compound. **Claim 19** The method according to claim 13, wherein the radically polymerizable component, the manganese-containing salt or organic complex, and the polyhydroxyl carboxylic acid are mixed and stored for at least 30 days, and then a mixture is formed with the 1,3-dioxo compound. **Claim 20** The method according to claim 13, wherein the radically polymerizable component and the 1,3-dioxo compound, the tertiary amine, and the nitrogen-containing aromatic heterocycle or thiol-containing compound are mixed and stored for at least 30 days, and then a mixture is formed with the manganese-containing salt or organic complex. **Claim 21** The method according to claim 13, wherein the radically polymerizable component and the 1,3-dioxo compound, and the polyhydroxyl carboxylic acid are mixed and stored for at least 30 days, and then a mixture is formed with the manganese-containing salt or organic complex. **Claim 22** The method according to claim 13, further comprising applying the mixture as a coating, layer, or casting while the polymerizable composition is uncured or while it is curing.

23. A resin composition comprising the polymerizable composition according to claim 1, which is for sheet molding compound (SMC) resin, resin transfer molding (RTM), casting resin, adhesive resin, pultrusion resin, corrosion-resistant resin, flame-retardant resin, low or zero styrene content resin, prepreg, gel coat, or coating resin.

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

25. The polymerizable composition according to claim 1, wherein the polymerizable composition has a peak exotherm of less than 300 °C.

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

27. The polymerizable composition according to claim 1, wherein the polymerizable composition has a gelation time of 10 seconds to 60 minutes.

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