Multi-step curing polymer composition that starts at ambient temperature

Abstract

A polymer composition comprising part A and part B adapted to react with part A, wherein when part A and part B come into contact, heat is generated by a first exothermic reaction, thereby raising the temperature of the composition to a temperature sufficiently high to trigger a second exothermic reaction.

Description

Technical Field

[0001] This application claims the benefit of the filing date of U.S. Provisional Application No. 63 / 468,314, filed on May 23, 2023, the content of which is hereby incorporated by reference in its entirety for all purposes.

[0002] The present teachings generally relate to polymer compositions suitable for forming room-temperature-curing products that meet performance criteria with little or no external influence. In one embodiment, the present teachings relate to multi-stage reaction-curing high glass transition (Tg) thermosetting polymers that initiate at ambient temperature and cure without the use of an external heating mechanism. The invention is set forth in the appended claims.

Background Art

[0003] Polymer compositions often exhibit good performance under conditions that exceed ambient conditions (temperature, pressure, chemical environment). As the use environment deviates further from ambient conditions, there is a continuing need to improve the performance of polymer systems. This often results in external conditions that exceed ambient conditions to react and cure the polymer composition to achieve the required performance goals. For example, it is well known that thermosetting epoxy resins can have a much higher glass transition temperature (Tg), as well as higher tensile modulus and other physical properties, compared to ambient temperature cured epoxy thermosets.

[0004] There is also a conflicting desire to minimize these external curing conditions that involve economics, productivity, and environmental costs. Unfortunately, single-stage curing acceleration starting from ambient conditions not only results in an extremely short working time under ambient conditions but also causes uncontrollable reactions and may impair product performance.

[0005] High glass transition temperature polymer compositions are an example of an improved performance target. High-Tg polymer compositions are useful in applications such as tool plates, circuit boards, and components in industries such as aerospace, automotive, construction, and marine. High-Tg compositions enable use under high-temperature conditions by maintaining their physical properties even in high-temperature environments. Other performance targets may include tensile modulus, compressive modulus, and flexural modulus.

[0006] As a specific example, high-Tg polymer compositions used to manufacture tool plates are typically prepared by compounding and / or mixing various polymer materials, and then heating the high-Tg composition in an oven to a temperature at which it can be achieved. This operation is usually necessary to achieve the desired glass transition temperature. These oven temperatures are often the same as or higher than the desired glass transition temperature. Additional notable properties of tool plates may include the coefficient of thermal expansion, hardness, tensile strength, flexural strength, compressive strength, fracture strain, density, and fracture toughness.

[0007] High-Tg polymer compositions are generally made from vinyl esters, acrylics, urethanes, phenols, or epoxy resins. Certain resin systems can provide cured products with glass transition temperatures exceeding 100°C, which can be used in applications requiring high-temperature performance.

[0008] Existing processes for producing high-Tg compositions involve mixing various components together, pouring the mixture into a mold, waiting up to a day for the reaction mixture to partially cure, and then heating the mixture in an oven for a certain period of time until complete curing is achieved. Stepped curing schedules are also common to avoid warping and cracking during the curing process. This entire process can take up to a week. This process requires the use of a curing oven, which represents an investment, occupies valuable manufacturing space, and incurs significant operating costs. As a result, the amount of product that can be produced per unit time is limited, creating a manufacturing bottleneck. These factors also contribute significantly to the environmental footprint of high-Tg compositions.

[0009] Essentially, achieving a high Tg polymer composition involves mixing curable materials and then heating them to a Tg above or near a theoretically feasible Tg for those materials.

[0010] The process for producing high-Tg compositions also requires that the reactant mixture has a reasonable amount of working time to mix and extrude into molds or trays. These molds are very large, and the material volume can exceed 100 liters, and larger volumes are desirable if possible, thus further increasing the need for reasonable working time.

[0011] Furthermore, high-Tg polymer compositions should not contain carbides (burnt and / or blackened material), which can be an indicator of property degradation. In the worst case, the cured composition may spontaneously combust. In addition, high-Tg polymer compositions should be fully cured to reduce waste, ensure consistent mechanical properties throughout the volume, and achieve long-term product stability. [Overview of the Initiative] [Problems that the invention aims to solve]

[0012] Therefore, it is desirable to produce high-Tg polymer compositions with little to no external heating. This would significantly reduce the required capital, manufacturing costs, and the environmental footprint of the produced compositions. Unfortunately, accelerating the normal curing reaction and curing in a single-step process under ambient conditions results in unacceptably short working times and can lead to carbonization and consequently, degraded compositions. [Means for solving the problem]

[0013] Since Tg represents one aspect of a polymer composition, this teaching overcomes the current limitations faced in the production of high-Tg compositions by providing compositions that have a reasonable working time, initiate curing under ambient conditions or nearby, and produce high-Tg, carbide-free, and fully cured materials without requiring external heating.

[0014] The teachings herein relate to a polymer composition comprising part A and part B adapted to react with part A, wherein when part A and part B are brought into contact, heat is generated by a first exothermic reaction, thereby raising the temperature of the composition to a temperature sufficiently high to trigger a second exothermic reaction.

[0015] The first exothermic reaction may be initiated at a temperature below 40°C.

[0016] The peak temperature of the composition may be higher than 100°C. The composition may have a glass transition temperature (Tg) of approximately 100°C or higher.

[0017] The composition may also contain reinforcing components.

[0018] The composition may include a thermally conductive material.

[0019] The composition may contain components that include hollow spherical bodies.

[0020] Part A, part B, or both may include one or more thermally induced phase change materials.

[0021] Part A, Part B, or both may contain a physical blowing agent. Part A, Part B, or both may contain a chemical blowing agent.

[0022] The composition may contain one or more toughening agents. The one or more toughening agents may include one or more core-shell particulate toughening agents.

[0023] The composition may contain one or more rheology control agents.

[0024] Part A may contain one or more epoxy resins.

[0025] The composition may contain one or more carboxylic acid cyclic anhydrides.

[0026] Part B may contain one or more acidic phosphorus components.

[0027] Part A, part B, or both may contain one or more catalysts for causing a reaction between epoxy and carboxylic acid cyclic anhydride.

[0028] The composition may contain one or more (meth)acrylate monomers and / or one or more (meth)acrylic functional resins.

[0029] Part A, part B, or both may contain one or more peroxides. Part A, part B, or both may contain one or more peroxide decomposition accelerators.

[0030] Part A, part B, or both may contain one or more free radical inhibitors.

[0031] Part A, part B, or both may contain one or more isocyanate resins.

[0032] Part A, part B, or both may contain one or more resins reactive with isocyanate.

[0033] Part A, part B, or both may contain one or more amine resins.

[0034] Part A, part B, or both may contain one or more latent catalysts.

[0035] Part A, part B, or both may contain one or more ring strain components suitable for an exothermic ring-opening reaction.

[0036] Part A, Part B, or both may comprise one or more components selected from epoxy resins, cyclic anhydrides of carboxylic acids, cyclic carbonates, cyclic lactones, dicyclopentadienes, benzoxazines, or combinations thereof. The composition may comprise one or more materials that react with epoxy resins, cyclic anhydrides of carboxylic acids, cyclic carbonates, cyclic lactones, dicyclopentadienes, benzoxazines, or combinations thereof. Part A, Part B, or both may comprise one or more catalysts that catalyze the reaction with epoxy resins, cyclic anhydrides of carboxylic acids, cyclic carbonates, cyclic lactones, dicyclopentadienes, benzoxazines, or combinations thereof.

[0037] Part A, Part B, or both, are (i) a silica rheological agent, preferably a fumed silica rheological agent or a hydrophilic fumed silica rheological agent or both, and / or (ii) an aliphatic amine, preferably modified for epoxy curing, and / or (iii) methyltetrahydrophthalic anhydride, and / or (iv) triglycidyl para-aminophenol, and / or (v) tetraglycidyl methylenedianiline resin, and / or (vi) a dispersion of 50 wt% benzoyl peroxide free radical initiator, and / or (vii) boron nitride, preferably a thermally conductive particulate filler, and / or (viii) a wettability enhancer and / or dispersant, and / Alternatively, (ix) a tertiary amine catalyst, and / or (x) a phosphonium ion liquid epoxy curing agent, and / or (xi) a dicyandiamide in a pulverized form, and / or (xii) liquid bisphenol A diglycidyl ether may be independently of each other, preferably in amounts of at least 5% by weight, or at least 15% by weight, or at least 35% by weight, or at least 55% by weight, or at least 75% by weight, or at least 95% by weight, and / or up to 95% by weight, or up to 75% by weight, or up to 55% by weight, or up to 35% by weight, or up to 15% by weight, or up to 5% by weight, in any case based on the total weight of the polymer composition or part A or part B.

[0038] Part A, Part B, or both are (i) an epoxy resin derived from o-cresol novolac, and / or (ii) a liquid diglycidyl ether of bisphenol F resin, and / or (iii) an epoxy resin derived from phenol novolac, and / or (iv) a tetraglycidyl methylenedianiline resin, and / or (v) a sorbitol polyglycidyl ether, and / or (vi) a dry powder of thermally expandable microspheres, and / or (vii) ferrocene, and / or (viii) a nanoclay additive, and / or (ix) HEMA phosphate, and / or (x) calcium carbonate particles, and / or (xi) 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, which is a free radical polymerization inhibitor, and / or (xii) isobornyl methacrylate. IBOMA, and / or (xiii) soda-lime glass microspheres, and / or (xiv) a mixture of core-shell particles dispersed in liquid bisphenol F and diglycidyl ether, and / or (xv) liquid diglycidyl ether of bisphenol A, and / or (xvi) tert-butyl peroxide benzoic acid free radical initiator may be independently of each other, preferably in amounts of at least 5% by weight, or at least 15% by weight, or at least 35% by weight, or at least 55% by weight, or at least 75% by weight, or at least 95% by weight, and / or up to 95% by weight, or up to 75% by weight, or up to 55% by weight, or up to 35% by weight, or up to 15% by weight, or up to 5% by weight, in any case based on the total weight of the polymer composition or part A or part B.

[0039] Part A, Part B, or both are (i) a 40% active dispersion of 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane crosslinked peroxide on calcium carbonate, and / or (ii) methacrylic acid, and / or (iii) tris(2-hydroxyethyl) isocyanurate triacrylate, and / or (iv) nasic methyl anhydride (NMA), which is a cyclic anhydride, and / or (v) expandable graphite particles, and / or (vi) PE13, which is an acidic phosphate ester obtained from a stoichiometric (phosphorus / epoxy) reaction of Eriysis GE13 (phenyl glycidyl ether) with 85 wt% aqueous phosphoric acid, and / or (vii) PE20, which is an acidic phosphate ester obtained from a stoichiometric (phosphorus / epoxy) reaction of Eriysis GE20 (neopentyl glycol diglycidyl ether) with 85 wt% aqueous phosphoric acid, and / or (viii) Eriysis PE30 is an acidic phosphate ester obtained from the stoichiometric (phosphorus / epoxy) reaction of GE30 (trimethrillylpropane triglycidyl ether) with 85 wt% water-soluble phosphoric acid, and / or (ix) phosphoric acid (H3PO4), preferably a food-grade 85 wt% aqueous solution, and / or (x) urea accelerator, and / or (xi) dimeric fatty acid, and / or (xii) hollow glass microspheres, and / or (xiii) spherical aluminum powder, and / or (xiv) 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl Suncarboxylate and / or (xv) air-sprayed aluminum powder may be contained independently of each other, preferably in amounts of at least 5% by weight, or at least 15% by weight, or at least 35% by weight, or at least 55% by weight, or at least 75% by weight, or at least 95% by weight, and / or up to 95% by weight, or up to 75% by weight, or up to 55% by weight, or up to 35% by weight, or up to 15% by weight, or up to 5% by weight, in any case based on the total weight of the polymer composition or part A or part B.

[0040] The composition may be suitable for tool plate applications and / or may be configured for tool plate applications.

[0041] The second exothermic reaction may produce physical properties that cannot be achieved by the first exothermic reaction alone.

[0042] The teachings herein further include a method for producing any of the polymer compositions of the foregoing claims, comprising the steps of (i) providing a portion A in accordance with the teachings herein, (ii) providing a portion B in accordance with the teachings herein and adapted to react with portion A, and (iii) bringing portion A and portion B into contact. When portion A and portion B are brought into contact, heat is generated by a first exothermic reaction, thereby raising the temperature of the composition to a temperature sufficiently high to trigger a second exothermic reaction.

[0043] The teachings herein further apply to the use of compositions prepared in accordance with these teachings for tool plate applications.

[0044] The teachings herein also relate to a polymer composition comprising part A, which contains at least 20% by weight of a first epoxy resin, and part B, which contains an acidic component adapted to react with part A. When part A and part B come into contact, a first exothermic reaction generates heat, thereby raising the temperature of the composition to a temperature high enough to trigger a second exothermic reaction.

[0045] The acidic component may be phosphoric acid.

[0046] The acidic component may be present in an amount of at least 7% of part B.

[0047] The acidic component can also be methacrylic acid.

[0048] Part B may contain a phosphate ester.

[0049] Part A may contain at least a first epoxy and a second epoxy, and optionally a third epoxy. [Brief explanation of the drawing]

[0050] [Figure 1] Table 1D shows a graph of temperature as a function of time obtained with the formulations listed in the table. It illustrates the epoxy-acid phosphoric acid / epoxy-anhydride reaction system. [Figure 2] This figure shows the reduction in carbonization in formulation 53-14 containing aluminum powder. [Figure 3] This graph shows the temperature rise over time of an example composition following this instruction. [Figure 4] This graph shows the temperature rise over time of an example composition following this instruction. [Figure 5] This figure shows compositions formed using a phosphonium ionic liquid catalyst and compositions formed without using one. [Figure 6] This graph shows the temperature of an exemplary composition prepared according to this instruction as a function of time. [Modes for carrying out the invention]

[0051] The descriptions and figures provided herein are intended to enable those skilled in the art to understand the teachings, their principles, and their practical applications. The detailed embodiments of the teachings described herein are not intended to be exhaustive or limiting. The scope of the teachings should be determined by reference to the entire scope of the appended claims and equivalents to which such claims are entitled. All disclosures of documents and references, including patent applications and published documents, are incorporated by reference for all purposes. Other combinations are possible, as will become apparent from the following claims, and these claims are also incorporated by reference into the text herein. Percentages herein refer to weight percentages unless otherwise specified.

[0052] The teachings herein relate to compositions adapted for multi-stage curing such that the components of the composition begin curing at or near ambient conditions (e.g., below 40°C) and proceed to complete curing with minimal external influence. The compositions herein may enable the production of high-Tg polymer compositions by multi-stage curing. In the first stage of curing, initial reaction exothermic activity occurs, and the resulting temperature rise activates the second stage of curing. Once a sufficiently high temperature is reached, the second stage of curing further promotes exothermic activity, producing a high-Tg polymer composition.

[0053] The multi-stage curing systems disclosed herein may be used for high Tg, as well as for improving the fracture strain of polymer materials, providing higher fracture toughness, increasing stiffness, improving solvent resistance, changing the decomposition temperature, or any combination of these improvements.

[0054] By incorporating two or more different curing reactions, the initial curing can be reduced to a level less than necessary to fully cure the product. This helps mitigate the initial heat generation. Subsequent curing phases do not significantly affect the preceding curing phases until the required high activation temperature is reached. The multi-step exothermic curing mechanism approach allows the reaction to proceed in multiple steps across multiple temperature ranges, enabling longer working times while still allowing the system to reach complete curing.

[0055] This instruction combines ambient temperature exothermic reaction systems with typical oven-curing exothermic reaction systems in various amounts, aiming to ensure that the ambient temperature system provides sufficient heat to activate the oven-curing system without the need for an oven. This instruction envisions multiple exothermic reactions to achieve multi-step in-situ curing starting at or near ambient temperature. The ambient temperature reaction systems include ring-opening of strained ring groups in epoxy, cyclic lactone, cyclic carbonate, cyclic anhydride, dicyclopentadiene, benzoxazine, etc., addition polymerization of vinyl esters and / or (meth)acrylate resins, and reactions involving isocyanate resins.

[0056] Ring-opening of epoxy resins initiated at ambient temperature can occur via acidic phosphorus or sulfonic acid groups in the absence of any catalyst. Other epoxy resin ring-opening reactions, such as epoxy-thiol, epoxy-phenol, epoxy-hydroxy, epoxy-amine, and epoxy-carboxylic acid, require a catalyst to obtain sufficient reaction at ambient temperature. Epoxy homopolymerization is a type of epoxy-hydroxy reaction and is another exothermic reaction that can be initiated at ambient temperature with sufficient catalyst.

[0057] Ambient temperature-initiated addition polymerization of vinyl ester resins and / or (meth)acrylate resins, using peroxides and appropriate peroxide degradation accelerators, is well known in the art. Non-limiting examples include tertiary aromatic amines (N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-o-toluidine, N,N-diethyl-p-toluidine, N-(2-hydroxyethyl),N-methyl-p-toluidine), transition metals, transition metal carboxylates (cobalt-2-ethylhexanoate, copper acetylacetonate, copper naphthalate), metallocenes (ferrocenes), 1-acetyl,2-phenylhydrazine, and sulfonyl chlorides (tosyl chloride, mesyl chloride, chlorosulfonated polyethylene).

[0058] Cyclic carbonates react with primary amines at room temperature.

[0059] Isocyanates react not only with materials containing active hydrogen (primary amines, secondary amines, polyols, thiols), but also with themselves (trimer formation).

[0060] Oven-curing systems may incorporate ambient temperature reaction systems, as well as reactions involving cyclic anhydrides and benzoxazines. Using reaction systems under oven-curing conditions may require different catalysts / accelerators, or it may be necessary to completely remove certain catalysts / accelerators. Curing agents and / or catalysts that undergo physical (melting, dissolution) or chemical (reversible thermal reaction) changes at high temperatures can be used. For example, latent curing agents such as dicyandiamide curing agents in epoxy-amine reactions are usable in high-temperature curing reactions. Blocked isocyanates are another example of reaction systems usable at high temperatures. Latent accelerators such as urea, known in the field of epoxy-amine reaction systems, are also included. Blocked catalysts, such as acid-blocked tertiary amines, are also considered.

[0061] Polymer compositions may include additional raw materials in the mixture. Reinforcements such as reinforcing components, fillers, wettability enhancers, rheology control agents, reinforcing fibers, thermoplastic polymers, flame retardants, pigments, and core-shell particles, as well as blowing agents, may also be part of the mixture. As a possible non-limiting example, additives can be used to alter the thermal conductivity and heat capacity of the composition. Additives that alter the curing density (hollow particles, thermal / chemical blowing agents) are also possible. Additional additives may be used to improve the machinability of the cured composition.

[0062] Thermal control fillers are useful for altering the heat capacity and thermal conductivity of a composition, thereby changing the effect of reaction exothermic reactions. Suitable thermal control fillers include aluminum powder, boron nitride, graphite, graphene, aluminum hydroxide, iron powder, iron oxide, powdered polymers, and alumina.

[0063] In the case of tool plate materials, glass microspheres (e.g., 3M K15, K20) are suitable components for reducing density and improving machinability. Preferred glass microspheres have low isotactic crush strength and are generally thin, allowing them to be easily fractured during cutting, for example, with a CNC router. This results in shorter cutting times and reduced wear on CNC-machined parts. Hollow particles can also be used to modify the temperature profile by providing components that occupy volume but do not impart reactive functional groups, and can also be used to adjust thermal conductivity and heat capacity.

[0064] Physical blowing agents, such as expandable microspheres (e.g., Noryon's Expanse), may also be included to reduce the density of the molded material, but chemical blowing agents can be considered in a similar manner.

[0065] In the case of formulations that cannot be stirred before mixing, one or more thixotropic agents may be included to help prevent the settling or floating of the packing material, which include, for example, mixed inorganic thixotropes such as fumed silica, Aerosil® R208, or Garamite 1958, or combinations thereof. [Examples]

[0066] The following examples demonstrate suitable exothermic reaction chemistry that can initiate curing at or near ambient temperature and produce cured polymer compositions with a high Tg.

[0067] Aerosil® R-208 is a treated fumed silica rheology agent available from Evonik.

[0068] Aerosil® 200 is a hydrophilic fumed silica rheology agent available from Evonik.

[0069] Ancamine® 1644 is a modified aliphatic amine used to cure epoxy resins available from Evonik.

[0070] Aradur® HY-918 is a methyltetrahydrophthalic anhydride available from Huntsman.

[0071] Araldite(registered trademark) MY0510 is a triglycidylated para-aminophenol available from Huntsman.

[0072] Araldite® MY-721 is a tetraglycidylmethylenedianiline resin available from Huntsman.

[0073] Benox® B-50 is a dispersion of 50% by weight benzoyl peroxide free radical initiator from United Initiators.

[0074] Boron nitride is a thermally conductive particulate filler available from 3M.

[0075] Byk® W996 is a wettability enhancer and dispersant available from Byk.

[0076] Cardolite® NT1300 is a tertiary amine catalyst available from Cardolite.

[0077] Cyphos IL169 is a phosphonium ionic liquid epoxy curing agent available from Solvay.

[0078] Dicyanex(registered trademark) 1200 is a dicyandiamide in a finely powdered form available from Evonik.

[0079] Epokukdo YD-128 is a liquid bisphenol A diglycidyl ether available from Kukdo Chemical Company.

[0080] Epokukdo YDCN-500 80P is an o-cresol novolac-derived epoxy resin available from Kukdo Chemical Company.

[0081] Epokukdo YDF-170 is a liquid diglycidyl ether of bisphenol F resin, available from Kukdo Chemical Company.

[0082] Epokukdo YDPN631 is a phenol novolac-derived epoxy resin available from Kukdo Chemical Company.

[0083] Epotec(registered trademark) YDM441 is a tetraglycidylmethylenedianiline resin available from Aditya Birla.

[0084] Erisys® GE-60 is a sorbitol polyglycidyl ether available from Huntsman.

[0085] Expancel® 951DU120 is a dry powder of thermally expandable microspheres available from Nouryon.

[0086] Ferrocene is an organometallic compound available from Millipore Sigma.

[0087] Garamite1958 is a processed nanoclay additive available from BYK.

[0088] The HEMA phosphate is Naxonac® HP1000 HEMA phosphate, available from Nease.

[0089] Hubercarb® Q2 is calcium carbonate particles available from Huber Engineered Materials.

[0090] 4-HydroxyTEMPO is a 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical polymerization inhibitor available from Millipore Sigma.

[0091] IBOMA is an isobornyl methacrylate available from Solvay as Sipomer® IBOMA-HP.

[0092] K20 is a soda-lime glass microsphere available from 3M.

[0093] K15 is a soda-lime glass microsphere available from 3M.

[0094] Kane Ace™ MX-267 is a mixed core-shell particle dispersed in liquid bisphenol F diglycidyl ether, available from Kaneka.

[0095] KDS 8805 is a liquid diglycidyl ether of bisphenol A, available from Kukdo Chemical Company.

[0096] Luperox P is a tert-butyl benzoic acid peroxide free radical initiator available from Arkema.

[0097] Luperox231XL40 is a 40% active dispersion of 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane bridged peroxide on calcium carbonate, available from Arkema.

[0098] Methacrylic acid is available from Millipore Sigma.

[0099] Miramer M370 is a tris(2-hydroxyethyl) isocyanurate triacrylate available from Miwon.

[0100] Nasic methyl anhydride (NMA) is a cyclic anhydride available from Dixie Chemical.

[0101] Nyagraph35 is an expandable graphite particle available from Nyacol Nano Technologies Inc.

[0102] PE13, i.e., an acidic phosphate ester obtained from the stoichiometric (phosphorus / epoxy) reaction of Eriysis GE13 (phenyl glycidyl ether available from Huntsman) with an 85 wt% aqueous solution of phosphoric acid.

[0103] PE20, i.e., an acidic phosphate ester obtained from the stoichiometric (phosphorus / epoxy) reaction of Eriysis GE20 (neopentyl glycol diglycidyl ether available from Huntsman) with an 85 wt% aqueous solution of phosphoric acid.

[0104] PE30, i.e., an acidic phosphate ester obtained from the stoichiometric (phosphorus / epoxy) reaction of Eriysis GE30 (trimethrillylpropane triglycidyl ether available from Huntsman) with an 85 wt% aqueous solution of phosphoric acid.

[0105] An 85% by weight aqueous solution of phosphoric acid (H3PO4), i.e., food-grade phosphoric acid available from Innophos.

[0106] SP-AD0052, i.e., a urea-based accelerator available from Springfield Industries.

[0107] Pripol® 1013 is a dimerized fatty acid available from Cargill.

[0108] Q-Cel(registered trademark) 7023S is a hollow glass microsphere available from Potters Industries.

[0109] S60HS is a hollow glass microsphere available from 3M®.

[0110] SP75-100 is a spherical aluminum powder available from Toyal America.

[0111] Syna Epoxy21 is a 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate available from Synasia.

[0112] Toyal101 is an air-sprayed aluminum powder available from Toyal America.

[0113] Example 1B-H-epoxy acid phosphorus / epoxy-acid / anhydride system. In Example 1, an ambient temperature reaction system containing epoxy groups and acidic phosphorus groups is combined with a typical oven-curable epoxy-cyclic anhydride reaction system. The acidic phosphorus material is selected from phosphoric acid, polyphosphoric acid, phosphonic acid, acidic phosphoric acid esters, and materials having multiple acidic phosphorus groups.

[0114] Example 1B The formulation in Example 1B demonstrates a method that utilizes a second reaction to control the initial curing stage, thereby extending the opening time.

[0115] The formulation of Example 1B is prepared by mixing A and part B separately in a dual asymmetric centrifugal mixer (SpeedMixer® by FlackTek), and then mixing A and B together in a high-speed mixer at 3500 rpm for 15 seconds.

[0116] The amounts of components in the formulation, including the stoichiometric ratio of acid to epoxy and whether the formulation is liquid or solid when removed from the mixer, are shown in weight percentages in Table 1B. This is assessed by gently shaking the mixture and recording the time until no further movement is observed. If the resulting mixture is solid immediately after being removed from the mixer, the material is not a practical solution because it requires a reasonable open time or working time (the time required to maintain fluidity as the mixed material is discharged). Using an acid anhydride such as nasic methyl anhydride (NMA) in part B may result in a longer open time at the same total acid level (measured in the stoichiometric ratio of acid to epoxy).

[0117] Formulations 5, 7, 8, and 9 (shown in Table 1B) exhibit longer open times when NMA is used in the same stoichiometric ratio. Formulation 5 solidifies almost instantaneously, while formulation 7 remains liquid even after 10 minutes. The presence of NMA dilutes the phosphoric acid, resulting in a less pronounced reaction at ambient temperature. The presence of at least one additional reaction eliminates the need for complete curing at ambient temperature, resulting in longer working times.

[0118] [Table 1]

[0119] Example 1C Example 1C demonstrates the effectiveness of incorporating a buffering agent into an acid-curing composition as a strategy to control peak reaction exothermicity.

[0120] The formulation in this embodiment is mixed, filled into a cartridge, adjusted to 55°C, and then dispensed into a 400 ml HDPE mold.

[0121] When incorporated into part B of the curing agent, basic materials such as calcium carbonate can act as buffers, potentially lowering the exothermic reaction temperature by buffering the curing agent before mixing with the epoxy resin (part A).

[0122] The component amounts of the example compositions, including their corresponding peak temperatures, are shown in parts by weight in Table 1C below. Sample 53-9, which does not contain calcium carbonate (Q2), shows a much higher peak temperature than Sample 53-7, which contains calcium carbonate.

[0123] [Table 2]

[0124] Example 1D The formulation of Example 1D demonstrates a method that allows the double-curing composition to generate a sufficiently high temperature necessary to produce a high-Tg material while having a sufficient open time.

[0125] The formulations shown in Table 1D below are prepared by filling a cartridge with parts A and B and extruding them into a rectangular high-density polyethylene mold using a static mixer. The total capacity of the cartridge is 400 ml. The mixing ratio is 4 parts epoxy part A and 1 part acid / anhydride part B. The cartridge is heated to 50°C before extrusion. The dimensions of the resulting composition are approximately 11 cm × 9 cm × 4 cm. After the material is extruded, a thermocouple is inserted approximately in the center of the mold.

[0126] [Table 3]

[0127] Figure 1 shows the temperature of the formulations in Table 1D as a function of time. As shown in Figure 1, the exothermic reaction from the epoxy-acid phosphorus reaction is sufficient to heat the mixture to the point where the epoxy-anhydride reaction begins, and to further increase the temperature.

[0128] Example 1E The formulation in this example (see Table 1E below) is prepared in the same manner as in Example 1D.

[0129] Incorporating aluminum powder (e.g., Toyal Grade 101) at levels of approximately 5% to a maximum of approximately 20% by weight reduces carbide formation. Aluminum has high thermal conductivity, which facilitates heat transfer throughout the casting from the reaction. Figure 2 visually illustrates the reduction in carbide in formulations 53-14 containing aluminum powder. Both formulations, shown in Table 1E below, heat up to the same temperature at the center. The formulation without aluminum (50-2") has a soft, waxy edge. This is evidence of insufficient hardening because the temperature at the edge did not rise high enough. Although not bound by theory, some foaming is also observed in the aluminum-containing formulation (43-14), which is presumed to be due to the generation of hydrogen gas from the reaction between aluminum, phosphoric acid, and water.

[0130] Figures 3 and 4 are graphs showing the temperature rise over time for Examples 50-2" and 53-14, respectively.

[0131] [Table 4]

[0132] Example 1F Example 1F demonstrates the effect of incorporating a catalyst into the formulation to achieve more complete curing throughout the entire object.

[0133] The formulation of Example 1F was adjusted to 43°C and dispensed from a 200ml cartridge into a 400ml HDPE beaker to a height of approximately 5cm.

[0134] Heat loss to the environment can cause a decrease in temperature at the corners of the molded sample. The temperature at these locations may be insufficient to initiate or complete secondary reactions.

[0135] Incorporating a phosphonium ionic liquid catalyst (Solvay Cyphos IL169) allows for more complete curing at the corners of molded samples. The phosphonium catalyst may lower the activation temperature of the reaction between the epoxy and the anhydride. It may also increase the core peak exothermic temperature, which is the temperature at the center of the object, measured by placing a thermocouple in the center after material extrusion. Table 1F shows the difference in core temperature between systems with and without the catalyst.

[0136] The amounts of ingredients in the formulation are shown in weight percentage in Table 1F.

[0137] Examples of compositions formed with and without the phosphonium ionic liquid catalyst can be seen in Figure 5. Formulation 53-15A1 without the catalyst has very soft edges, and the uncured material can be easily removed with a spatula. Formulation 53-15A4 with the catalyst is completely cured throughout its entire volume.

[0138] [Table 5]

[0139] Example 1G It has also been shown that polyfunctional phosphate ester curing agents, such as the reaction product of phosphoric acid with epoxidized neopentyl glycol (e.g., Erisys GE-20) with a theoretical number of 4 acidic functional groups, and epoxidized trimethylolpropane (e.g., Erisys GE30) with a theoretical number of 6 acidic functional groups, have the ability to increase the Tg compared to systems using epoxidized phenolic phosphate esters with a lower average number of functional groups (e.g., Erisys GE13) with a theoretical number of 2 acidic functional groups. Tg was measured using TA instruments Q800DMA.

[0140] The formulation of Example 1G is prepared in the same manner as in Example 1A. The amounts of components in the formulation are shown in weight percentage in Table 1G.

[0141] [Table 6]

[0142] Example 1H Example 1H demonstrates the advantages of incorporating foaming ability into the formulation. The formulation of Example 1H (see Table 1H below) is prepared in the same manner as in Example 1A.

[0143] Low-density compositions may be desirable in tool sheet applications to improve machining speed and quality, and to facilitate handling of larger volumes. Tool sheets typically incorporate hollow glass spheres to reduce density. Expansion can also be induced by incorporating thermoplastic expandable microspheres (e.g., Nouryon Expancel). Chemical blowing agents, or the reaction of acid compositions (part B) with metal carbonates, are also potential strategies for foaming, both of which can result in lower densities.

[0144] Table 1H includes a formulation (Sample KE) with a theoretical hardening density of 1.09 g / cc, but by incorporating expandable microspheres (Expancel 951DU120) into the formulation (Sample JK), it has a measured density of 0.75 g / cc as measured by hydrostatic metrology.

[0145] [Table 7]

[0146] Example 2 (Epoxy + amine / Epoxy + latent amine) The formulation of Example 2 demonstrates another chemical reaction involving multi-step curing that can be used to promote exothermic reactions to a level higher than that achievable with a single curing agent. In this example, the epoxy resin is cured by a combination of an ambient temperature-reactive amine and a latent amine. The mixture is formulated such that the exothermic reaction from the ambient temperature amine-epoxy reaction is sufficient to raise the temperature of the composition to a point where the latent amine-epoxy reaction significantly occurs. The exothermic reaction from this second reaction raises the temperature of the mixture, enabling compositions with higher Tg.

[0147] The formulation of Example 2 is prepared by mixing the epoxy (A) portion and the amine (B) portion separately in a high-speed mixer, and then mixing A and B together in a high-speed mixer at 3500 rpm for 15 seconds.

[0148] The amounts of components in the formulation are shown in weight percent in Table 2, and include the stoichiometric ratio of acid to epoxy, the maximum exothermic temperature, and the associated Tg as measured using TA Instruments' Q800 DMA. The amine (Ancamine® 1644) provides a sufficiently high exothermic reaction to allow dicyanamide (Dicyanex® 1200) to continue the reaction. Using both the amine and the dicyanamide curing agent yields higher exothermic reactions and Tg than using the amine alone.

[0149] [Table 8]

[0150] Example 3 (Epoxy + Acidic Phosphorus / Acrylic) Example 3A demonstrates the use of an exothermic reaction between an acidic phosphorus material and an epoxide to induce the thermal decomposition of a peroxide and cure a high-Tg (meth)acrylate or (meth)acrylate blend. Furthermore, the use of HEMA phosphate in the formulation indicates the use of two or more components involved in the exothermic reaction.

[0151] YDCN-500-80P is pre-dissolved in the blend of YDPN-631 and Kane Ace MX267 in the ratios listed in Table 3A. 1 part of 4-hydroxyTEMPO is heated above its melting point, and then the heated material is rapidly mixed to dissolve it in 99 parts of YDPN-631. The formulations listed in Table 3A are mixed under vacuum using a high-speed mixer. Part A of Table 3A is used to fill the larger side of a 2:1 volume ratio cartridge, and part B is used to fill the adjacent side. The two components are extruded through a 10-24 helical static mixer at 30°C into a 1 L (10cm × 10cm × 10cm) rock wool insulated mold lined with aluminum foil and allowed to cure.

[0152] [Table 9]

[0153] The exothermic peak of the resulting mixture is 182.2°C at the center of the block. This temperature significantly exceeds the 1-hour half-lives of both Luperox P (125.3°C) and 231XL40 (110°C). Free radicals generated by the thermal decomposition of the peroxide polymerize the available (meth)acrylate unsaturated material. This is evident from the DMA-analyzed Tg of the sample, with an initial Tg of 138°C and a tan delta of 177°C.

[0154] Example 4 (Acrylic + Acrylic + Anhydrous Epoxy) Example 4 demonstrates the use of room-temperature initiated (meth)acrylate polymerization to initiate latent peroxide and epoxy-anhydride polymerization.

[0155] One part of 4-hydroxyTEMPO is heated above its melting point, and then dissolved in 99 parts of YDPN-631 by high-speed mixing of the heated material. One part of ferrocene is dissolved in Miramer M-370 by high-speed mixing. The mixture is mixed and degassed in a high-speed mixer according to Table 4 below. The mixture is then filled into a 400 mL 2:1 cartridge with an appropriate mixing ratio of part B:part A to 2:1. The material is extruded at 31.1°C through a 10-24 helical static mixer into a 20 cm × 20 cm × 10 cm galvanized steel mold installed in rock wool insulation.

[0156] [Table 10]

[0157] In Example 4, ferrocene was used to catalyze the decomposition of benzoyl peroxide at ambient temperature, initiating the polymerization of the (meth)acrylate blend. 4-hydroxytempo was used to mediate this reaction and extend the working time. The peak exothermic temperature of the resulting material was 229°C, significantly exceeding the decomposition temperature of Luperox P described in Example 3, and also exceeding the initiation temperature of epoxy-anhydride polymerization described in the previous examples. The resulting polymer showed no signs of exothermic carbonization. The initial Tg of the composition material was 162°C, and the tandela Tg was 201°C.

[0158] Example 5 Epoxy monomer polymerization / Epoxy-anhydride polymerization In Example 5, a high Tg composition is obtained by gradually increasing the temperature until epoxy homopolymerization is sufficiently catalyzed and the epoxy-anhydride reaction occurs. The amounts of components in the formulation are shown in Table 5 as weights per 100 parts by weight of resin.

[0159] [Table 11]

[0160] Figure 6 shows the temperature tracking of a 78-liter sheet material made from the XX-3 formulation. Inert hollow glass microspheres were partially used to reduce the density of the sheet material. All raw materials were placed in a Farfly planetary mixer and mixed under vacuum for 30 minutes. The mixture was then poured into a non-insulated metal mold at ambient temperature at 30°C to form a sheet material measuring 960 × 480 × 170 mm.

[0161] The rise in material temperature was measured with a probe at the center of the plate. The initial reaction temperature rise was approximately 0.08°C / min, the subsequent reaction start temperature was 65°C, and the temperature rise was 11.4°C / min. The highest temperature recorded was 178°C. The resulting composition material, measured using Metravib DMA, had an initial Tg of 140°C and a tan delta Tg of 160°C.

[0162] It should be understood that the above description is illustrative and not limiting. Those skilled in the art will recognize many embodiments and applications beyond those provided. Therefore, the scope of the invention should not be determined by reference to the above description, but rather by reference to the entire scope of the appended claims and their equivalents. All disclosures in the literature and references, including patent applications and published documents, are incorporated by reference for all purposes. The omission of any aspect of the subject matter disclosed herein in the following claims shall not constitute a waiver of such subject matter, nor should it be construed as the inventors not considering such subject matter to be part of the disclosed subject matter of the invention.

[0163] The descriptions and figures presented herein are intended to help those skilled in the art to understand the invention, its principles, and its practical applications. The above description is illustrative and not limiting. Those skilled in the art can adapt and apply the invention to its various forms in a way that best suits the requirements of a particular application.

[0164] Accordingly, the detailed embodiments of the invention described herein are not intended to be exhaustive or restrictive of the teachings. Therefore, the scope of these teachings should not be determined by reference to this specification, but rather by reference to the appended claims and the entire scope of their equivalents. In the following claims, the omission of any aspect of the subject matter disclosed herein does not constitute a waiver of such subject matter, nor should it be construed as the inventors not considering such subject matter to be part of the disclosed subject matter of the invention.

[0165] Multiple elements or steps may be provided by a single, integrated element or step. Alternatively, a single element or step may be divided into multiple individual elements or steps.

[0166] The disclosure of “a” or “one” describing an element or step is not intended to exclude any additional elements or steps.

[0167] The terms "generally" or "substantially" used to describe angle measurements may mean approximately ±10° or less, approximately ±5° or less, or even approximately ±1° or less. The terms "generally" or "substantially" used to describe angle measurements may mean approximately ±0.01° or more, approximately ±0.1° or more, or even approximately ±0.5° or more. The terms "generally" or "substantially" used to describe linear measurements, percentages, or ratios may mean approximately ±10% or less, approximately ±5% or less, or even approximately ±1% or less. The terms "generally" or "substantially" used to describe linear measurements, percentages, or ratios may mean approximately ±0.01% or more, approximately ±0.1% or more, or even approximately ±0.5% or more.

[0168] Unless otherwise specified, all ranges include both endpoints and all values ​​between the endpoints. The use of "about" or "approximately" in relation to a range applies to both ends of the range. Therefore, "about 20-30" includes "about 20-about 30" and is intended to include at least the specified endpoint.

[0169] Unless otherwise specified, the numerical values ​​described herein include all values ​​from the lower limit to the upper limit in increments of one unit, provided that there is at least a difference of two units between the lower and upper limits. For example, if the values ​​of the quantity, properties, or process variables of a component, such as temperature, pressure, or time, are in the ranges of, for example, 1 to 90, 20 to 80, or 30 to 70, then intermediate range values ​​(e.g., 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc.) are included in the teachings herein. Similarly, individual intermediate values ​​are also included in the teachings herein. For values ​​less than 1, one unit is considered to be 0.0001, 0.001, 0.01, or 0.1 as appropriate. These are merely examples of what is specifically intended, and all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to be expressly described in a similar manner in this application. Unless otherwise specified, all ranges include all numerical values ​​at both endpoints and between the endpoints.

[0170] To be understood, the teachings of quantities indicated herein as “parts by weight” are also intended to be expressed as weight percentages. Thus, the expression of a range in the form “at least x parts by weight of the resulting composition” is also intended to be a teaching of a range expressed as a weight percentage of the resulting composition for the same amount “x”.

[0171] The term "consisting essentially of" used to describe a combination includes any other such elements, materials, materials, or processes that do not substantially affect the basic and novel properties of the identified elements, materials, materials, or processes of the combination. In this specification, the use of the terms "comprising" or "including" when describing a combination of elements, materials, materials, or processes also intends to include embodiments that are essentially composed of those elements, materials, materials, or processes. The terms "including" and "comprising" are interchangeable.

[0172] All disclosures of documents and references, including patent applications and published literature, are incorporated by reference for any purpose. Other combinations are also possible, as is evident from the following claims, and these claims are also incorporated by reference into this text.

Claims

1. Part A, and Part B adapted to react with part A In a polymer composition containing, When parts A and B come into contact, a first exothermic reaction generates heat, which raises the temperature of the composition to a temperature high enough to trigger a second exothermic reaction. Polymer composition.

2. The composition according to claim 1, wherein the first exothermic reaction is initiated at a temperature of less than 40°C.

3. The composition according to claim 1 or 2, wherein the peak temperature of the composition is higher than 100°C.

4. The composition according to claim 1 or 2, wherein the composition has a glass transition temperature (Tg) of about 100°C or higher.

5. The composition according to claim 1 or 2, comprising a reinforcing component.

6. The composition according to claim 1 or 2, comprising a thermally conductive material.

7. The composition according to claim 1 or 2, comprising a component containing a hollow spherical body.

8. The composition according to claim 1 or 2, wherein part A, part B, or both comprises one or more thermally induced phase change materials.

9. The composition according to claim 1 or 2, wherein part A, part B, or both of the above comprises a physical foaming agent.

10. The composition according to claim 1 or 2, wherein part A, part B, or both of the above comprises a chemical blowing agent.

11. The composition according to claim 1 or 2, comprising one or more reinforcing agents.

12. The composition according to claim 11, wherein one or more reinforcing agents comprise one or more core-shell particulate reinforcing agents.

13. The composition according to claim 1 or 2, comprising one or more rheology control agents.

14. The composition according to claim 1 or 2, wherein portion A comprises one or more epoxy resins.

15. The composition according to claim 1 or 2, comprising one or more cyclic anhydrides of carboxylic acids.

16. The composition according to claim 1 or 2, wherein portion B comprises one or more acidic phosphorus components.

17. The composition according to claim 1 or 2, wherein part A, part B, or both comprises one or more catalysts for causing a reaction between an epoxy and a carboxylic acid cyclic anhydride.

18. The composition according to claim 1 or 2, comprising one or more (meth)acrylate monomers and / or one or more (meth)acrylic functional resins.

19. The composition according to claim 1 or 2, wherein part A, part B, or both thereof comprises one or more peroxides.

20. The composition according to claim 19, wherein part A, part B, or both comprises one or more peroxide decomposition accelerators.

21. The composition according to claim 1 or 2, wherein part A, part B, or both thereof comprises one or more free radical inhibitors.

22. The composition according to claim 1 or 2, wherein part A, part B, or both thereof comprises one or more isocyanate resins.

23. The composition according to claim 1 or 2, wherein part A, part B, or both comprises one or more resins that are reactive with isocyanate.

24. The composition according to claim 1 or 2, wherein part A, part B, or both thereof comprises one or more amine resins.

25. The composition according to claim 1 or 2, wherein part A, part B, or both thereof comprises one or more latent catalysts.

26. The composition according to claim 1 or 2, wherein part A, part B, or both of them contain one or more ring straining components suitable for an exothermic ring-opening reaction.

27. The composition according to claim 1 or 2, wherein part A, part B, or both, independently contain, preferably, at least 5% by weight, or at least 15% by weight, or at least 35% by weight, or at least 55% by weight, or at least 75% by weight, or at least 95% by weight, and / or up to 95% by weight, or up to 75% by weight, or up to 55% by weight, or up to 35% by weight, or up to 15% by weight, or up to 5% by weight, in any case based on the total weight of the polymer composition or part A or part B.

28. The composition according to claim 27, further comprising one or more materials that react with an epoxy resin, a carboxylic acid cyclic anhydride, a cyclic carbonate, a cyclic lactone, a dicyclopentadiene, a benzoxazine, or a combination thereof.

29. The composition according to claim 1 or 2, wherein part A, part B, or both comprises one or more catalysts that catalyze a reaction with an epoxy resin, a cyclic anhydride carboxylic acid, a cyclic carbonate, a cyclic lactone, a dicyclopentadiene, a benzoxazine, or a combination thereof.

30. The composition according to claim 1 or 2, wherein portion A, portion B, or both thereof, comprises one or more components for causing a third or fourth exothermic reaction.

31. Part A, Part B, or both, (i) Silica rheological agents, preferably fumed silica rheological agents or hydrophilic fumed silica rheological agents or both, and / or (ii) Aliphatic amines, preferably modified for curing epoxy, and / or (iii) Methyltetrahydrophthalic anhydride, and / or (iv) Triglycidylated para-aminophenol, and / or (v) Tetraglycidylmethylenedianiline resin, and / or (vi) A dispersion of 50% by weight of benzoyl peroxide free radical initiator, and / or (vii) Boron nitride, preferably as a thermally conductive particulate filler, and / or (viiii) Wettability enhancers and / or dispersants, and / or (ix) Tertiary amine catalyst, and / or (x) Phosphonium ion liquid epoxy curing agent, and / or (xi) dicyandiamide in a finely powdered form, and / or (xi) Liquid bisphenol A diglycidyl ether The composition according to claim 1 or 2, comprising, independently of each other, preferably in amounts of at least 5% by weight, or at least 15% by weight, or at least 35% by weight, or at least 55% by weight, or at least 75% by weight, or at least 95% by weight, and / or up to 95% by weight, or up to 75% by weight, or up to 55% by weight, or up to 35% by weight, or up to 15% by weight, or up to 5% by weight, in any case based on the total weight of the polymer composition or part A or part B.

32. Part A, Part B, or both, (i) epoxy resins derived from o-cresol novolac, and / or (ii) liquid diglycidyl ether of bisphenol F resin, and / or (iii) Epoxy resins derived from phenol novolacs, and / or (iv) Tetraglycidylmethylenedianiline resin, and / or (v) Sorbitol polyglycidyl ether, and / or (vi) Dry powder of thermally expandable microspheres, and / or (vii) ferrocene, and / or (viiii) Nanoclay additives, and / or (ix) HEMA phosphate, and / or (x) Calcium carbonate particles, and / or (xi) 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical polymerization inhibitor 4-hydroxyTEMPO, and / or (xi) IBOMA, which is isobornyl methacrylate, and / or (xiiii) Soda-lime glass microspheres, and / or (xiv) A mixture of core-shell particles dispersed in liquid bisphenol F and diglycidyl ether, and / or (xv) liquid diglycidyl ether of bisphenol A, and / or (xvi) tert-butyl peroxide benzoic acid free radical initiator The composition according to claim 1 or 2, comprising, independently of each other, preferably in amounts of at least 5% by weight, or at least 15% by weight, or at least 35% by weight, or at least 55% by weight, or at least 75% by weight, or at least 95% by weight, and / or up to 95% by weight, or up to 75% by weight, or up to 55% by weight, or up to 35% by weight, or up to 15% by weight, or up to 5% by weight, in any case based on the total weight of the polymer composition or part A or part B.

33. Part A, Part B, or both, (i) a 40% active dispersion of 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane crosslinked peroxide on calcium carbonate, and / or (ii) Methacrylic acid, and / or (iii) Tris(2-hydroxyethyl) isocyanurate triacrylate, and / or (iv) Nasic methyl anhydride (NMA), which is a cyclic anhydride, and / or (v) Expandable graphite particles, and / or (vi) PE13, an acidic phosphate ester obtained from the stoichiometric (phosphorus / epoxy) reaction of Eriysis GE13 (phenylglycidyl ether) with an 85 wt% aqueous solution of phosphoric acid, and / or (vii) PE20, an acidic phosphate ester obtained from the stoichiometric (phosphorus / epoxy) reaction of Eriysis GE20 (neopentyl glycol diglycidyl ether) with an 85 wt% aqueous solution of phosphoric acid, and / or (viiii) PE30, an acidic phosphate ester obtained from the stoichiometric (phosphorus / epoxy) reaction of Eriysis GE30 (trimethrillylpropane triglycidyl ether) with an 85 wt% aqueous solution of phosphoric acid, and / or (ix) Phosphate (H3PO4), preferably a food-grade 85% by weight aqueous solution, and / or (x) Urea accelerators, and / or (xi) Dimeric fatty acids, and / or (xi) Hollow glass microspheres, and / or (xiiii) Spherical aluminum powder, and / or (xiv) 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and / or (xv) Air-sprayed aluminum powder The composition according to claim 1 or 2, comprising, independently of each other, preferably in amounts of at least 5% by weight, or at least 15% by weight, or at least 35% by weight, or at least 55% by weight, or at least 75% by weight, or at least 95% by weight, and / or up to 95% by weight, or up to 75% by weight, or up to 55% by weight, or up to 35% by weight, or up to 15% by weight, or up to 5% by weight, in any case based on the total weight of the polymer composition or part A or part B.

34. Suitable for and / or configured for tool plate applications. The composition according to claim 1 or 2.

35. The composition according to claim 1 or 2, wherein the second exothermic reaction produces physical properties that cannot be achieved by the first exothermic reaction alone.

36. A method for producing the polymer composition described in claim 1 or 2, (i) the step of providing part A according to claim 1 or 2, (ii) the step of providing a portion B as described in claim 1 or 2 and adapted to react with portion A, and (iii) Step of bringing part A and part B into contact. The material contains such a component that when part A and part B are brought into contact, a first exothermic reaction generates heat, which raises the temperature of the composition to a temperature high enough to trigger a second exothermic reaction. method.

37. Use of the composition according to claim 1 or 2 for tool plate material applications.

38. Part A comprising at least 20% by weight of a first epoxy resin, and Part B contains an acidic component adapted to react with Part A. In a polymer composition containing, When parts A and B come into contact, a first exothermic reaction generates heat, which raises the temperature of the composition to a temperature high enough to trigger a second exothermic reaction. Polymer composition.

39. The composition according to claim 38, wherein the acidic component is phosphoric acid.

40. The composition according to claim 38 or 39, wherein the acidic component is present in an amount of at least 7% of portion B.

41. The composition according to claim 38 or 39, wherein the acidic component is methacrylic acid.

42. The composition according to claim 38 or 39, wherein part B comprises a phosphate ester.

43. The composition according to claim 38 or 39, wherein portion A comprises at least a first epoxy and a second epoxy, and optionally comprises a third epoxy.

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