Latent accelerator based on acid anhydride-tertiary amine dynamic ion pair and its preparation and use

Abstract

The application provides a latent promoter based on an acid anhydride-tertiary amine dynamic ion pair and a preparation method and application thereof. The latent promoter is a reaction product of a first component and a second component, the first component comprises a substance with an acid anhydride structure, the second component comprises a compound with a tertiary amine structure, and the latent promoter has an acid anhydride-tertiary amine dynamic ion pair. The latent promoter provided by the application can realize long-term storage and medium-low temperature curing of a single-component thermosetting material, especially when the latent promoter is applied to an epoxy-acid anhydride system, an epoxy-phenolic system, an epoxy-dicyandiamide system, an epoxy-thiol system, an epoxy-hydrazine system, an epoxy-4,4'-diaminodiphenyl sulfone system and other epoxy resin systems, the latent promoter can reduce the curing temperature of the epoxy resin systems and enable long-term storage of the epoxy resin systems.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a latent promoter based on anhydride-tertiary amine dynamic ion pairs, its preparation method, and its uses. Background Technology

[0002] Thermosetting plastics, due to their three-dimensional cross-linked network structure, possess excellent thermal properties, mechanical properties, chemical stability, and dimensional stability, making them widely used in numerous fields such as electronic packaging materials, coatings, adhesives, and composite materials. Two-component thermosetting materials require mixing the thermosetting material (e.g., epoxy resin, unsaturated polyester, phenolic resin, polyurethane, rubber, etc.) with a curing agent before use. This necessitates on-site preparation, which is not only cumbersome and time-consuming but also compromises quality. Furthermore, leftover materials can sometimes lead to environmental pollution and waste. Currently, most thermosetting materials are two-component; for example, the production of two-component epoxy resin has reached tens of millions of tons. In contrast, single-component thermosetting materials allow for pre-mixing of the thermosetting resin monomers and cross-linking agents, eliminating the cumbersome on-site preparation. However, current single-component thermosetting materials suffer from high curing temperatures; for example, the mixture of dicyandiamide and epoxy requires temperatures above 200°C to cure. Therefore, developing single-component thermosetting materials with low curing temperatures and a certain shelf life has become a key research focus. Summary of the Invention

[0003] To solve all or part of the above-mentioned technical problems, the present invention provides the following technical solutions:

[0004] One objective of this invention is to provide a latent promoter based on an anhydride-tertiary amine dynamic ion pair, wherein the latent promoter is a reaction product of a first component and a second component, the first component comprising a substance having an anhydride structure, the second component comprising a compound having a tertiary amine structure, and the latent promoter having an anhydride-tertiary amine dynamic ion pair.

[0005] The latent accelerator exhibits no accelerating activity under relatively low temperature (e.g., room temperature) conditions, but exhibits high accelerating activity when heated, as the dynamic structure of the anhydride-tertiary amine is unwound. As a latent accelerator for thermosetting resins, it can effectively inhibit and control the reactivity of releasing highly active accelerators, enabling long-term storage of single-component thermosetting materials at room temperature and rapid crosslinking at medium and low temperature conditions (e.g., 90–130°C), thereby reducing the curing temperature of thermosetting resins such as epoxy resins.

[0006] In some embodiments, the first component is an unsaturated anhydride copolymer, which is a binary or multi-component copolymer of an unsaturated anhydride and a comonomer. The latent accelerator prepared using the unsaturated anhydride copolymer and a compound with a tertiary amine structure is a crosslinked network with a dynamic anhydride-tertiary amine structure.

[0007] In some embodiments, the unsaturated anhydride includes one or a combination of maleic anhydride, itaconic anhydride, and citraconic anhydride.

[0008] In some embodiments, the comonomer includes one or more of the following: methacrylate compounds, acrylate compounds, styrene compounds, or itaconic acid ester compounds.

[0009] In some embodiments, the comonomer includes one or more of the following: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isooctyl methacrylate, lauryl methacrylate, isobutyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isooctyl acrylate, lauryl acrylate, isobutyl acrylate, isobornyl acrylate, styrene, acrylonitrile, dimethyl itaconic acid, diethyl itaconic acid, dipropyl itaconic acid, dibutyl itaconic acid, and diisooctyl itaconic acid, but is not limited thereto.

[0010] In some embodiments, the second component comprises one or more of a first tertiary amine compound and / or a second tertiary amine compound. The first tertiary amine compound has three R groups simultaneously attached to its N atom. These R groups are alkyl groups or heteroatom-containing alkyl groups, and the three R groups may be the same or different. The second tertiary amine compound is an imidazole-based tertiary amine compound. The heteroatom in the heteroatom-containing alkyl group can be N, O, S, or other heteroatoms commonly recognized in the art.

[0011] In some embodiments, the first tertiary amine compound includes 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethylbenzylamine, 3-methoxy-N,N-dimethylbenzylamine, triethylamine, tripentylamine, N,N-dimethylcyclohexylamine, N,N-dimethyl-p-toluidine, N,N-dimethylethylamine, N,N-dimethylethanolamine, N,N-dimethylpropenylamine, N,N,N′,N′-tetramethylethylenediamine, pentamethyldivinyltriamine, N,N,N′,N′-tetramethyl-1,6-hexanediamine, pyridine, N-methylpiperidine, 2-(dimethylaminomethyl)phenol, N,N-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)-1,3,5-hexahydrotriazine, N,N-dimethyldecylamine, N,N-dimethylbutylamine, N,N-dimethylpropyl-1-amine, N, One or more of the following: N-dimethylisopropylamine, N,N-dimethyln-octylamine, tris(N,N-dimethylaminopropyl)amine, N,N-dimethyldodecylamine, N,N-dimethylferroceneamine, N,N-dimethylhexadecylamine, N,N-dimethyltetradecylamine, N,N-dimethyln-octadecylamine, N,N-dimethylhexylamine, N,N-dimethyl-2-naphthylamine, N,N-dimethylaniline, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,6-di[(dimethylamino)methyl]phenol, 2,4-di[(dimethylamino)methyl]phenol, bis(2-dimethylaminoethyl) ether, 1,8-diazabicyclo[5.4.0]undec-7-ene, triethanolamine, 1,5,7-trizabicyclo[4.4.0]dec-5-ene, and 4-dimethylaminopyridine.

[0012] In some embodiments, the second tertiary amine compound includes imidazole, 2-methylimidazolium, 2-ethylimidazolium, 2-phenylimidazolium, benzimidazole, 2-ethyl-4-methylimidazolium, 2,4-dimethylimidazolium, 1,2-dimethylimidazolium, 1-isopropylimidazolium, 1,4,5-trimethyl-1H-imidazolium, 1-ethyl-2-methylimidazolium, 4-phenylimidazolium, 2,2′-biimidazole, N,N'-carbonyldiimidazole, 2-undecylimidazolium, vinylimidazolium, 1-(2-hydroxyethyl)imidazolium, 4-hydroxyimidazolium, 2-aminoimidazolium, 1-(3-aminopropyl)imidazolium, 4-nitroimidazolium, 1-phenylethylimidazolium, 2-formylimidazolium, 4-formylimidazolium, 2-acetyl Benzimazole, imidazo[1,2-a]pyridine-6-carboxylic acid, 1H-imidazo[1,2-F]phenanthridine, N-n-heptylimidazolium, 1,2′-bis(2-chlorophenyl)-tetraphenylbiimidazole, 5-chloro-3H-imidazo[4,5-B]pyridine, imidazo-4,5-dicarboxylic acid, astemizole, N-BOC-imidazolium, 1H-imidazo[4,5-B]pyridine-2(3H)one, 2-(1-naphthyl)-1H-benzimidazole, 4-chloromethylimidazolium, (2R)-2,3-dihydro-2-phenylimidazo[2,1-B]benzothiazole, 2-octylbenzimidazole, 2-chloro-4-(1H-2-imidazolyl)pyridine, 2-(3-pyridyl)benzimidazole, imidazolyl Ethyl pyrazin-3-carboxylate, imidazo[1,2-A]pyridin-7-carboxylic acid, imidazo[1,5-a]pyrido[2,3-E]pyrazin-4(5H)-one, 2-(4-fluorophenyl)imidazo[1,2-a]pyridine, imidazo[1,2-a]pyrimidine, imidazodimethylpyridine, 3H-imidazo[4,5-B]pyridine, 2-methyl-3H-imidazo[4,5-b]pyridine, 2-fluoro-6-(1H-imidazo-2-yl)-pyridine, 4,5-dichloroimidazolium, (9ci)-2-(2-oxazolium)-1H-benzimidazole, 1H-benzimidazole-2-sulfonic acid, 3,6-bis(1H-imidazo-L-1-yl)pyridyl Azine, 3-cyclohexylimidazo[1,5-A]pyrazine, 1H-imidazo[4,5-e]tetrazo[1,5-a]pyridine, 2H-thienozo[2′,3′:4,5]pyrrolo[1,2-c]imidazolium (9CI), imidazo[1,2-a]pyridine-6-methanol, (9CI)-1-acetyl-1H-imidazo[1,2-b]pyrazole, (6-phenylimidazo[2,1-B]thiazo-5-yl)methanol, (9CI)-1H-benzimidazol-5-acetic acid, 3-[(1-imidazolyl)methyl]piperidine, 3-chloro-5,6,7,8-tetrahydroimidazo[1,2-a]pyrazine, 2H-imidazo[4,5-g]quinoxaline (8CI,9ci), 2-methoxyimidazoline, 5-(difluoromethoxy)-2-mercapto-1H-benzimidazole, 2-mercapto-5-methoxy-1H-benzimidazole, and 5-methoxybenzimidazole, or a combination of one or more of these.

[0013] The second objective of this invention is to provide a method for preparing a latent promoter based on an anhydride-tertiary amine dynamic ion pair, comprising: reacting a mixed reaction system containing a first component and a second component, wherein the first component comprises a substance having an anhydride structure and the second component comprises a compound having a tertiary amine structure, to obtain a latent promoter having an anhydride-tertiary amine dynamic ion pair.

[0014] In some embodiments, the reaction temperature is 0–80°C, preferably 0–50°C. Within this temperature range, higher reaction efficiency and a more complete reaction can be achieved. If the reaction temperature is too low or too high, the reaction may be incomplete or fail to occur, resulting in the inability to form dynamic anhydride-tertiary amine ion pairs.

[0015] In some embodiments, the reaction time is 0.3 to 72 hours, preferably 0.3 to 12 hours.

[0016] In some embodiments, the mass ratio of the first component to the second component is 0.6 to 70:1, preferably 1 to 10:1, and more preferably 1 to 5:1. If the content of substances with anhydride structures is low, the storage effect is poor; if the content of compounds with tertiary amine structures is low, the active ingredient content is low, and the content of added accelerators is high, exceeding the general range of added accelerator content, thus increasing economic costs.

[0017] In some embodiments, the mixed reaction system further includes a solvent, wherein the mass ratio of the solvent to the second component is 0.5–15:1, for example 1–15:1, preferably 1–10:1, and more preferably 1–5:1. Using a solvent makes the product easier to obtain. The solvent can be one or more commonly used solvents, and the present invention does not impose any particular limitation on it. For example, one or a combination of two or more of butanone, acetone, N,N-dimethylformamide, dimethyl sulfoxide, chloroform, dichloromethane, tetrahydrofuran, N-methylpyrrolidone, anisole, toluene, and 1,4-dioxane.

[0018] In some embodiments, the reactions occurring in the preparation method of the latent promoter include one or more of the following: nucleophilic addition reaction of tertiary amine with acid anhydride, esterification reaction of phenolic hydroxyl group with acid anhydride, salt formation reaction of tertiary amine with carboxyl group, and amidation reaction of acid anhydride with secondary amine.

[0019] In some embodiments, the preparation method further includes post-processing, such as solvent removal, drying, etc.

[0020] In some embodiments, the first component is an unsaturated anhydride copolymer, which is a binary or multi-component copolymer of an unsaturated anhydride and a comonomer.

[0021] In some embodiments, the second component includes one or more of a first tertiary amine compound and / or a second tertiary amine compound, wherein the N atom of the first tertiary amine compound is simultaneously connected to three R groups, the R groups being alkyl or heteroatom-containing alkyl groups, and the three R groups being the same or different; the second tertiary amine compound is an imidazole tertiary amine compound.

[0022] The specific selection of the saturated anhydride copolymer as the first component and the compound with an anhydride structure as the second component in the "preparation method" provided by this invention has been described in detail in one of the objectives of this invention, and will not be repeated here.

[0023] A third objective of this invention is to provide the use of the aforementioned latent accelerator in the preparation of single-component thermosetting coatings, adhesives, electronic packaging materials, or composite prepregs.

[0024] A fourth objective of this invention is to provide a one-component thermosetting resin composition comprising a thermosetting resin and the aforementioned latent accelerator, wherein the mass ratio of the latent accelerator to the thermosetting resin is 1 to 70:100. That is, in a system without the use of other curing agents, the latent accelerator enables the resin composition to cure rapidly at relatively low temperatures.

[0025] In some embodiments, the thermosetting resin includes epoxy resin.

[0026] The fifth objective of this invention is to provide a single-component thermosetting resin composition comprising a thermosetting resin, a curing agent, and an accelerator, wherein the mass ratio of the curing agent to the thermosetting resin is 6-140:100, and the mass ratio of the accelerator to the thermosetting resin is 1-70:100, wherein the accelerator includes the latent accelerator described above.

[0027] In some embodiments, the thermosetting resin includes epoxy resin.

[0028] In some embodiments, the curing agent includes one or more combinations of anhydride curing agents, phenolic curing agents, dicyandiamide curing agents, thiol curing agents, phenolic curing agents, hydrazide curing agents, and 4,4'-diaminodiphenyl sulfone. That is, the latent accelerator can be used to lower the curing temperature of epoxy-anhydride systems, epoxy-phenolic systems, epoxy-dicyandiamide systems, epoxy-thiols, and epoxy-4,4'-diaminodiphenyl sulfone systems, allowing them to cure at lower temperatures and extending their shelf life at room temperature.

[0029] In some embodiments, the mass ratio of the latent accelerator to the epoxy resin is 1 to 10:100.

[0030] Compared with the prior art, the present invention has at least the following beneficial effects:

[0031] (1) The latent accelerator provided by this invention has a dynamic anhydride-tertiary amine ion pair in its structure. On the one hand, the dynamic anhydride-tertiary amine ion pair reduces the activity of the tertiary amine. On the other hand, the anhydride in the ion pair is on the unsaturated anhydride copolymer chain. The dynamic anhydride-tertiary amine ion pair fixes or embeds the tertiary amine compound in the unsaturated anhydride copolymer, making it difficult for the tertiary amine structure to contact the epoxy resin when mixed with it, thus exhibiting low or no activity. Therefore, the activity of the accelerator is suppressed under relatively low temperature (e.g., room temperature) conditions, resulting in very low or no activity. It has no promoting activity. Under relatively high temperature conditions, the dynamic ion pair structure of the anhydride-tertiary amine in it breaks down, and the highly active tertiary amine is released and comes into contact with the epoxy resin, thus exhibiting high promoting activity. Therefore, using it as a latent accelerator for thermosetting resins can effectively inhibit and control the reactivity of the highly active accelerator, enabling long-term storage and rapid cross-linking of single-component thermosetting materials. This allows single-component thermosetting materials to balance long-term storage at room temperature and rapid curing at medium and low temperatures, and has broad application prospects in single-component coatings, adhesives, electronic packaging materials, and composite prepregs.

[0032] (2) The latent accelerator described herein can reduce the curing temperature of epoxy-anhydride system, epoxy-phenolic system, epoxy-dicyandiamide system, epoxy-thiol system, epoxy-hydrazide system, and epoxy-4,4′-diaminodiphenyl sulfone system, so that it can achieve rapid curing at 90 to 130°C, solving the problems of high curing temperature and incomplete reaction of epoxy resin system in the prior art, and also enabling it to have a long storage period (e.g., more than 6 months) at a low temperature (e.g., room temperature);

[0033] (3) The method for preparing the latent accelerator provided by the present invention is simple, easy to operate, well controllable, and easy to implement, and is suitable for large-scale industrial production. Attached Figure Description

[0034] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0035] Figure 1This is a photograph of the latent accelerator prepared in Example 1 of this invention;

[0036] Figure 2 This is the infrared spectrum of the latent accelerator prepared in Example 1 of the present invention. Detailed Implementation

[0037] The technical solutions of the present invention will be described in detail below with reference to specific embodiments, so that those skilled in the art can better understand and implement the technical solutions of the present invention. The specific functional details disclosed herein should not be construed as limiting, but are merely intended to form the basis of the claims and to teach those skilled in the art to employ the representative basis of the invention in different ways in any suitable detailed embodiment.

[0038] In addition, unless otherwise specified, all raw materials used in the following embodiments can be purchased from the market or other sources, and all production and testing equipment used are known in the art.

[0039] The reagents and testing methods used in the following examples are as follows:

[0040] Reagents: Styrene-maleic anhydride copolymer SMA3000 / SMA2000 / SMA1000 (Kreville), Bisphenol A epoxy resin E-51 (Baling Petrochemical), Tetraglycidylamine epoxy resin AG-80 (Shanghai Huayi Resin), Bisphenol F epoxy resin NPEF-170 (Nanya), Bisphenol A epoxy resin (DER-331) (Dow), Bisphenol A epoxy resin NPEL-127 (Nanya), Thiol 405 (Guangzhou Geling New Materials), 2,4,6-Tris(dimethylaminomethyl)phenol (DMP-30) (Evonik ANCAMINE K54).

[0041] Rheological experiments: The viscosity of the samples was measured by using a rheometer (MCR) 302e (Anton Paar, Austria) on a 25 mm sample tray with a parallel plate geometry. The shear strain ranged from 0.01% to 10% (the specific shear strain value was determined based on the test value in the linear elastic region), the frequency was 1 Hz, the temperature was 25 °C, and the time was 10 min.

[0042] Differential scanning calorimetry (DSC): A Mettler-Toledo Star3 DSC (Mettler-Toledo, USA) was used in a nitrogen atmosphere at a rate of 50 mL / min. -1 The flow rate, and the heating rate from 25 to 180°C, is 10°C / min. -1 Record the DSC curve to measure the glass transition temperature.

[0043] Tensile test: A general-purpose testing machine UTM4000 (Shenzhen Sansi Zongheng Technology Co., Ltd., China) was used. The gauge length of the specimen was 40 mm, and the dimensions were 80 mm (length) × 6 mm (width) × 0.3 mm (thickness). The test was conducted at 10 mm min. -1 Tests were conducted at various speeds.

[0044] The partially unsaturated anhydride copolymers used in the following specific embodiments were prepared by the following method: Taking Example 2 as an example, butyl methacrylate and itaconic anhydride copolymer were mixed in a 1:1 molar ratio, and 1.2% (by mass) of azobisisobutyronitrile (AIBN) initiator was added using butanone as a solvent. The mixture was reacted at 75°C for 6 hours, and then precipitated four times with petroleum ether to obtain a copolymer with a molecular weight of 13,000-14,000. The copolymer preparation methods of other embodiments are basically the same as those of Example 2, except that the selection of unsaturated anhydrides and comonomers and their molar ratios are varied. The specific selection of monomers, molar ratios, and molecular weights of copolymers have been specified in the corresponding embodiments.

[0045] Example 1

[0046] 150 parts (unless otherwise specified, all parts by weight) of styrene-maleic anhydride copolymer (SMA3000) and 300 parts of butanone were dissolved in a round-bottom flask. 100 parts of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was stirred and reacted at 50°C for 3.5 hours. After the reaction was complete, the solvent was removed, and the mixture was pulverized into a fine powder to obtain the target product, i.e., the latent accelerator, which is in powder form, such as... Figure 1 As shown. The infrared spectrum of this latent accelerator is as follows. Figure 2 As shown, at 1715cm -1 It is -C(O)N + Characteristic peak, 1500-1600 cm⁻¹ -1 The presence of characteristic peaks for -COO indicates that the product has been successfully synthesized.

[0047] Two parts of the latent accelerator prepared in this embodiment were uniformly mixed with six parts of dicyandiamide and 100 parts of bisphenol A epoxy resin (E-51) to obtain a resin composition. The viscosity of the resin composition was then monitored using a rheometer at room temperature, and it was found that the viscosity after six months was 1.05 times the initial viscosity. The resin composition was cured by heating at 100°C for 2.5 hours, and its glass transition temperature was measured to be 135°C and its tensile strength to be 70 MPa.

[0048] Comparative Example 1

[0049] 150 parts of styrene-maleic anhydride copolymer (SMA3000) and 300 parts of butanone were dissolved in a round-bottom flask. 100 parts of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was stirred and reacted at -5°C for 3.5 h. The solvent was removed, and the product was pulverized into a fine powder to obtain the final product. The resin composition was prepared and tested according to the same method as in Example 1.

[0050] Comparative Example 2

[0051] Comparative Example 2 used 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) as an accelerator. The resin composition was prepared and tested according to the same method as in Example 1.

[0052] Comparative Example 3

[0053] The preparation method of the latent curing agent provided in this comparative example is basically the same as that in Example 1, except that 500 parts of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were used. The rest of the procedures were the same as in Example 1. The resin composition was prepared and tested according to the same method as in Example 1.

[0054] Comparative Example 4

[0055] The preparation method of the latent curing agent provided in this comparative example is basically the same as that in Example 1, except that 1 part of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) was used. The rest was carried out in the same manner as in Example 1. The resin composition was prepared and tested according to the same method as in Example 1.

[0056] Comparative Example 5

[0057] The preparation method of the latent curing agent provided in this comparative example is basically the same as that in Example 1, except that the reaction temperature is set to -10°C. The resin composition was prepared and tested according to the same method as in Example 1.

[0058] Comparative Example 6

[0059] The preparation method of the latent curing agent provided in this comparative example is basically the same as that in Example 1, except that the reaction temperature is set to 150°C. The resin composition was prepared and tested according to the same method as in Example 1.

[0060] Table 1. Relevant process parameters for preparing latent accelerators in Example 1 and Comparative Examples 1-5.

[0061]

[0062] Resin compositions were formulated using the latent accelerators prepared in Examples 1 and 1-6, and the viscosity of the resin compositions was monitored using a rheometer at room temperature. The resin compositions were then cured at a specific temperature for a specific time, and the glass transition temperature and tensile strength were tested. The viscosity test results, curing temperature, time, glass transition temperature, and tensile strength are detailed in Table 2.

[0063] Table 2. Composition and properties of resin compositions formulated using the latent accelerators of Example 1 and Comparative Examples 1-6.

[0064]

[0065] Example 2

[0066] 150 parts of n-butyl methacrylate and itaconic anhydride copolymer (monomer molar ratio 1:1, molecular weight 13000-14000) and 300 parts of butanone were dissolved in a round-bottom flask. 70 parts of 2-(dimethylaminomethyl)phenol were added, and the mixture was stirred with a stirrer and reacted at 50°C for 3.5 h. The solvent was removed, and the mixture was pulverized into micro powder to obtain the target product, i.e., the latent accelerator.

[0067] Example 3

[0068] 150 parts of isooctyl methacrylate and itaconic anhydride copolymer (monomer molar ratio 1.5:1, molecular weight 14000-15000) and 300 parts of acetone were dissolved in a round-bottom flask. 50 parts of N,N-dimethylbenzylamine were added, and the mixture was stirred with a stirrer and reacted at 0°C for 72 hours. The mixture was then pulverized into a fine powder, and the solvent was removed to obtain the target product, i.e., the latent accelerator.

[0069] Example 4

[0070] 150 parts of styrene-maleic anhydride copolymer (SMA2000) and 300 parts of butanone were dissolved in a round-bottom flask. 70 parts of 2-(dimethylaminomethyl)phenol were added, and the mixture was stirred and reacted at 80°C for 0.3 h. The solvent was removed, and the mixture was pulverized into micro powder to obtain the target product, i.e., the latent accelerator.

[0071] Example 5

[0072] 150 parts of styrene-maleic anhydride copolymer (SMA2000) and 300 parts of butanone were dissolved in a round-bottom flask. 40 parts of N,N-dimethylpiperazine were added, and the mixture was stirred and reacted at 50°C for 3.5 h. The solvent was removed, and the mixture was pulverized into a fine powder to obtain the target product, i.e., the latent accelerator.

[0073] Example 6

[0074] 150 parts of styrene-maleic anhydride copolymer (SMA1000) and 300 parts of butanone were dissolved in a round-bottom flask. 90 parts of bis(dimethylaminoethyl) ether were added, and the mixture was stirred and reacted at 50°C for 3.5 h. The solvent was removed, and the mixture was pulverized into micro powder to obtain the target product, i.e., the latent accelerator.

[0075] Example 7

[0076] 150 parts of styrene-maleic anhydride copolymer (SMA1000) and 300 parts of N-methylpyrrolidone were dissolved in a round-bottom flask. 90 parts of 2-(dimethylaminomethyl)phenol were added, and the mixture was stirred with a stirrer and reacted at 50°C for 3.5 h. The solvent was removed, and the mixture was pulverized into micro powder to obtain the target product, i.e., the latent accelerator.

[0077] Example 8

[0078] 168 parts of isooctyl methacrylate and itaconic anhydride copolymer (monomer molar ratio 1.2:1, molecular weight 14000-15000) and 132 parts of butanone were dissolved in a round-bottom flask. 60 parts of 2-(dimethylaminomethyl)phenol were added, and the mixture was stirred with a stirrer and reacted at 50°C for 3.5 h. The mixture was then pulverized into a fine powder to obtain the target product, i.e., the latent accelerator.

[0079] Example 9

[0080] 112 parts of butyl methacrylate and itaconic anhydride copolymer (monomer molar ratio 1:2, molecular weight 13000-14000) and 150 parts of chloroform were dissolved in a round-bottom flask. 80 parts of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) and 15 parts of imidazole were added. The mixture was stirred and reacted at 50°C for 3.5 h. The solvent was removed, the mixture was dried, and pulverized into a fine powder to obtain the target product, i.e., the latent accelerator.

[0081] Example 10

[0082] 700 parts of methyl methacrylate and itaconic anhydride copolymer (monomer molar ratio 2:1, molecular weight 13000-14000) and 150 parts of N,N-dimethylformamide were dissolved in a round-bottom flask. 10 parts of 2-(dimethylaminomethyl)phenol were added, and the mixture was stirred and reacted at 50°C for 3.5 h. The solvent was removed, and the mixture was pulverized into micro powder to obtain the target product, i.e., the latent accelerator.

[0083] Example 11

[0084] 150 parts of a copolymer of dimethyl itaconic acid and itaconic anhydride (monomer molar ratio 1:1, molecular weight 8000-10000) and 300 parts of tetrahydrofuran were dissolved in a round-bottom flask. 72 parts of N,N-dimethyl-p-toluidine were added, and the mixture was stirred and reacted at 50°C for 3.5 h. The solvent was removed, and the mixture was pulverized into micro powder to obtain the target product, i.e., the latent promoter.

[0085] Example 12

[0086] 150 parts of styrene-maleic anhydride copolymer (SMA3000) and 300 parts of butanone were dissolved in a round-bottom flask. 30 parts of N,N-dimethylethanolamine were added, and the mixture was stirred and reacted at 80°C for 3.5 h. The solvent was removed, and the mixture was pulverized into micro powder to obtain the target product, i.e., the latent accelerator.

[0087] Example 13

[0088] 150 parts of styrene-citric acid anhydride copolymer (monomer molar ratio 1.2:1, molecular weight 7000-8000) and 300 parts of butanone were dissolved in a round-bottom flask. 100 parts of tripentylamine were added, and the mixture was stirred and reacted at 0°C for 72 hours. The solvent was removed to obtain the target product, which was then pulverized into micro powder, i.e., the latent accelerator.

[0089] Example 14

[0090] 150 parts of styrene-citric acid anhydride copolymer (monomer molar ratio 1.5:1, molecular weight 8000-10000) and 100 parts of chloroform were dissolved in a round-bottom flask. 34 parts of triethylamine were added, and the mixture was stirred and reacted at 50°C for 3.5 h. The solvent was removed, and the mixture was pulverized into micro powder to obtain the target product, i.e., the latent accelerator.

[0091] Example 15

[0092] 159 parts of butyl methacrylate and itaconic anhydride copolymer (monomer molar ratio 1:3, molecular weight 10000-11000) and 300 parts of butanone were dissolved in a round-bottom flask. 265 parts of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was stirred and reacted at 50°C for 3.5 h. The solvent was removed, and the mixture was pulverized into micro powder to obtain the target product, i.e., the latent accelerator.

[0093] Example 16

[0094] 154 parts of n-butyl methacrylate and itaconic anhydride copolymer (monomer molar ratio 1:2, molecular weight 13000-14000) and 100 parts of dimethyl sulfoxide were dissolved in a round-bottom flask. 125 parts of 2-(dimethylaminomethyl)phenol were added, and the mixture was stirred and reacted at 30°C for 12 hours. The solvent was removed, and the mixture was pulverized into micro powder to obtain the target product, i.e., the latent accelerator.

[0095] Example 17

[0096] 218 parts of styrene-citric acid anhydride copolymer (monomer molar ratio 1:1, molecular weight 8000-10000) and 300 parts of acetone were dissolved in a round-bottom flask. 265 parts of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was stirred and reacted at 50°C for 12 hours. The solvent was removed to obtain the target product, which was then pulverized into micro powder, i.e., the latent accelerator.

[0097] Example 18

[0098] 154 parts of lauryl methacrylate and itaconic anhydride copolymer (monomer molar ratio 1:1.8, molecular weight 9000-10000) were dissolved in a round-bottom flask, and 90 parts of 2-(dimethylaminomethyl)phenol were added. The mixture was stirred with a stirrer and reacted at 30°C for 12 hours. The solvent was removed, and the mixture was pulverized into micro powder to obtain the target product, i.e., the latent accelerator.

[0099] Example 19

[0100] 150 parts of methyl methacrylate and itaconic anhydride copolymer (monomer molar ratio 0.3:1, molecular weight 3000-4000) and 132 parts of N,N-dimethylformamide were dissolved in a round-bottom flask. 264 parts of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was stirred and reacted at 80°C for 3 hours. The solvent was removed to obtain the target product, i.e., the latent accelerator.

[0101] Example 20

[0102] 700 parts of styrene-maleic anhydride copolymer (SMA3000) and 700 parts of butanone were dissolved in a round-bottom flask. 10 parts of pyridine were added, and the mixture was stirred and reacted at 50°C for 72 hours. The solvent was removed, and the mixture was pulverized into micro powder to obtain the target product, i.e., the latent accelerator.

[0103] Example 21

[0104] 100 parts of styrene-maleic anhydride copolymer (SMA3000) and 100 parts of butanone were dissolved in a round-bottom flask. 16 parts of imidazole were added, and the mixture was stirred and reacted at 50°C for 4 hours. The solvent was removed, and the mixture was pulverized into a fine powder to obtain the target product, i.e., the latent accelerator.

[0105] Example 22

[0106] 100 parts of n-butyl methacrylate and itaconic anhydride copolymer (monomer molar ratio 1:1, molecular weight 13000-14000) and 300 parts of butanone were dissolved in a round-bottom flask. 18 parts of imidazole were added, and the mixture was stirred with a stirrer and reacted at 50°C for 4 hours. The solvent was removed, and the mixture was pulverized into micro powder to obtain the target product, i.e., the latent promoter.

[0107] Example 23

[0108] 100 parts of styrene-maleic anhydride copolymer (SMA3000) and 100 parts of butanone were dissolved in a round-bottom flask. 21 parts of 2-methylimidazole were added, and the mixture was stirred and reacted at 70°C for 3 hours. The solvent was removed, and the mixture was pulverized into a fine powder to obtain the target product, i.e., the latent accelerator.

[0109] Example 24

[0110] 100 parts of a terpolymer of methyl methacrylate, n-butyl acrylate and itaconic anhydride (monomer molar ratio 1:0.3:1, molecular weight 5000-6000) and 300 parts of N,N-dimethylformamide were dissolved in a round-bottom flask. 45 parts of N,N'-carbonyldiimidazole were added, and the mixture was stirred and reacted at 60°C for 3 hours. The solvent was removed to obtain the target product, i.e., the latent promoter.

[0111] Example 25

[0112] 150 parts of styrene-citric acid anhydride copolymer (monomer molar ratio 1.5:1, molecular weight 8000-10000) and 100 parts of chloroform were dissolved in a round-bottom flask. 55 parts of benzimidazole were added, and the mixture was stirred and reacted at 50°C for 3.5 h. The solvent was removed, and the mixture was pulverized into micro powder to obtain the target product, i.e., the latent accelerator.

[0113] Comparative Example 7

[0114] 168 parts of methylhexahydrophthalic anhydride and 265 parts of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were mixed in a round-bottom flask, stirred with a stirrer, and reacted at 50°C for 3.5 h to obtain the target product.

[0115] It was found that, compared with the accelerator prepared by unsaturated anhydride copolymer, the target product obtained in Comparative Example 7 forms ion pairs with small molecules, which makes it easier to absorb water during pulverization. However, because the accelerator prepared by unsaturated anhydride copolymer has hydrophobic structures, such as styrene and methacrylates, it is easier to pulverize, thus solving the problem of easy dispersion of latent accelerators.

[0116] Comparative Example 8

[0117] 168 parts of methylhexahydrophthalic anhydride and 265 parts of N,N-dimethylbenzylamine were placed in a round-bottom flask and mixed. The mixture was stirred and reacted at 50°C for 3.5 h to obtain the target product.

[0118] The accelerators used in the preparation of the unsaturated anhydride copolymers of the present invention are all hydrophobic and pulverizable solids. However, the target product of Comparative Example 8 is a liquid and is more prone to absorbing water. The one-component epoxy resin composition prepared with this accelerator has no shelf life.

[0119] The raw materials and reaction conditions used in the preparation of the latent accelerators in Examples 1-20 are summarized in Table 3.

[0120] Table 3. Raw materials and reaction conditions used in the preparation of latent accelerators in Examples 1-20

[0121]

[0122]

[0123] Resin compositions were formulated using the latent accelerators of Examples 1-20 above, and the components and contents of the obtained resin compositions are shown in Table 4. The viscosity, glass transition temperature, and tensile strength of the resin compositions were tested using the same method as in Example 1, and the test results are shown in Table 4.

[0124] Table 4. Composition, content, and related properties of resin compositions

[0125]

[0126]

[0127]

[0128] In addition, the applicant also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the foregoing embodiments, and obtained relatively ideal results in all cases.

[0129] As can be seen from the above embodiments, the latent accelerator of the acid anhydride-tertiary amine dynamic ion pair provided by the present invention can achieve long-term storage and low-to-medium temperature curing of single-component thermosetting materials. In particular, its application to epoxy resin systems such as epoxy-acid anhydride systems, epoxy-phenolic systems, epoxy-dicyandiamide systems, epoxy-thiol systems, epoxy-hydrazide systems, and epoxy-4,4'-diaminodiphenyl sulfone systems not only reduces the curing temperature of these epoxy resin systems but also significantly extends their shelf life. Based on current experimental results, some preferred embodiments are expected to have ultra-long shelf lives, such as several years or more, during which the viscosity does not change significantly. This provides a new, simple, and efficient strategy for developing single-component thermosetting resins. Furthermore, most of the raw materials for preparing the latent accelerator are commercially available substances, which are readily available. The preparation process is simple, easy to operate, well-controllable, and easy to implement, making it suitable for large-scale industrial production.

[0130] All aspects, embodiments, features, and examples of this invention are to be regarded as illustrative in all respects and are not intended to limit the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will become apparent to those skilled in the art without departing from the spirit and scope of the invention as claimed.

[0131] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0132] Although the invention has been described with reference to illustrative embodiments, those skilled in the art will understand that various other changes, omissions, and / or additions can be made without departing from the spirit and scope of the invention, and that elements of the embodiments can be substituted with substantially equivalents. Furthermore, many modifications can be made without departing from the scope of the invention to adapt particular situations or materials to the teachings of the invention. Therefore, this invention is not intended to be limited to the specific embodiments disclosed for carrying out the invention, but rather is intended to encompass all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated otherwise, any use of the terms first, second, etc., does not indicate any order or importance, but is used to distinguish one element from another.

Claims

1. A latent promoter based on anhydride-tertiary amine dynamic ion pair, characterized in that: The latent accelerator is the reaction product of the first component and the second component; the first component is an unsaturated anhydride copolymer, which is a binary or multi-component copolymer of an unsaturated anhydride and a comonomer; wherein the unsaturated anhydride includes one or more of maleic anhydride, itaconic anhydride, and citraconic anhydride; the comonomer includes one or more of methacrylate compounds, acrylate compounds, styrene compounds, or itaconic acid ester compounds; the second component includes a compound having a tertiary amine structure; The latent accelerator has an anhydride-tertiary amine dynamic ion pair, wherein the anhydride in the anhydride-tertiary amine dynamic ion pair is on an unsaturated anhydride copolymer chain; the latent accelerator exhibits no accelerating activity under room temperature conditions, but exhibits high accelerating activity under heating conditions, wherein the anhydride-tertiary amine dynamic ion pair dissociates.

2. The latent accelerator according to claim 1, characterized in that: The second component includes one or more of a first tertiary amine compound and / or a second tertiary amine compound, wherein the N atom of the first tertiary amine compound is simultaneously attached to three R groups, wherein the R groups are alkyl or heteroatom-containing alkyl groups, and the three R groups may be the same or different; the second tertiary amine compound is an imidazole tertiary amine compound.

3. The latent accelerator according to claim 2, characterized in that: The first tertiary amine compounds include 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethylbenzylamine, 3-methoxy-N,N-dimethylbenzylamine, triethylamine, tripentylamine, N,N-dimethylcyclohexylamine, N,N-dimethyl-p-toluidine, N,N-dimethylethylamine, N,N-dimethylethanolamine, N,N-dimethylpropenylamine, N,N,N',N'-tetramethylethylenediamine, pentamethyldivinyltriamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, pyridine, N-methylpiperidine, 2-(dimethylaminomethyl)phenol, N,N-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)-1,3,5-hexahydrotriazine, N,N-dimethyldecylamine, N,N-dimethylbutylamine, N,N-dimethylpropyl-1-amine, and N,N-dimethyl... The mixture comprises one or more of the following: propylamine, N,N-dimethyl-n-octylamine, tris(N,N-dimethylaminopropyl)amine, N,N-dimethyldodecylamine, N,N-dimethylferroceneamine, N,N-dimethylhexadecylamine, N,N-dimethyltetradecylamine, N,N-dimethyl-n-octadecylamine, N,N-dimethylhexylamine, N,N-dimethyl-2-naphthylamine, N,N-dimethylaniline, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,6-di[(dimethylamino)methyl]phenol, 2,4-di[(dimethylamino)methyl]phenol, bis(2-dimethylaminoethyl) ether, 1,8-diazabicyclo[5.4.0]undec-7-ene, triethanolamine, 1,5,7-trizabicyclo[4.4.0]dec-5-ene, and 4-dimethylaminopyridine.

4. The latent accelerator according to claim 2, characterized in that: The second tertiary amine compound includes imidazole, 2-methylimidazolium, 2-ethylimidazolium, 2-phenylimidazolium, benzimidazole, 2-ethyl-4-methylimidazolium, 2,4-dimethylimidazolium, 1,2-dimethylimidazolium, 1-isopropylimidazolium, 1,4,5-trimethyl-1H-imidazolium, 1-ethyl-2-methylimidazolium, 4-phenylimidazolium, 2,2'-biimidazole, N,N'-carbonyldiimidazole, 2-undecylimidazolium, vinylimidazolium, 1-(2-hydroxyethyl)imidazolium, 4-hydroxyimidazolium, 2-aminoimidazolium, 1-(3-aminopropyl)imidazolium, 4-nitroimidazolium, 1-phenylethylimidazolium, 2-formylimidazolium, 4-formylimidazolium, 2-acetylbenzimidazole, Imidazolo[1,2-a]pyridine-6-carboxylic acid, 1H-imidazo[1,2-F]phenanthridine, N-n-heptylimidazolium, 1,2'-bis(2-chlorophenyl)-tetraphenylbiimidazole, 5-chloro-3H-imidazo[4,5-B]pyridine, imidazo-4,5-dicarboxylic acid, astemizole, N-BOC-imidazolium, 1H-imidazo[4,5-B]pyridine-2(3H)one, 2-(1-naphthyl)-1H-benzimidazole, 4-chloromethylimidazolium, (2R)-2,3-dihydro-2-phenylimidazo[2,1-B]benzothiazole, 2-octylbenzimidazole, 2-chloro-4-(1H-2-imidazolyl)pyridine, 2-(3-pyridyl)benzimidazole, imidazo[1 [2-a]pyrazin-3-carboxylic acid ethyl ester, imidazo[1,2-A]pyridin-7-carboxylic acid, imidazo[1,5-a]pyrido[2,3-E]pyrazin-4(5H)-one, 2-(4-fluorophenyl)imidazo[1,2-a]pyridine, imidazo[1,2-a]pyrimidine, imidazodimethylpyridine, 3H-imidazo[4,5-B]pyridine, 2-methyl-3H-imidazo[4,5-b]pyridine, 2-fluoro-6-(1H-imidazo-2-yl)-pyridine, 4,5-dichloroimidazolium, (9CI)-2-(2-oxazolium)-1H-benzimidazole, 1H-benzimidazole-2-sulfonic acid, 3,6-bis(1H-imidazo-L-1-yl)pyridazine, 3-Cyclohexylimidazo[1,5-A]pyrazine, 1H-imidazo[4,5-e]tetrazo[1,5-a]pyridine, 2H-thienozo[2',3':4,5]pyrrolo[1,2-c]imidazolium (9CI), imidazo[1,2-a]pyridine-6-methanol, (9CI)-1-acetyl-1H-imidazo[1,2-b]pyrazole, (6-phenylimidazo[2,1-B]thiazo-5-yl)methanol, (9CI)-1H-benzimidazol-5-acetic acid, 3-[(1-imidazolyl)methyl]piperidine, 3-chloro-5,6,7,8-tetrahydroimidazo[1,2-a]pyrazine, 2H-imidazo[4,5-g]quinoxaline (8CI,9CI), 2-methoxyimidazoline, 5-(difluoromethoxy)-2-mercapto-1H-benzimidazole, 2-mercapto-5-methoxy-1H-benzimidazole, and 5-methoxybenzimidazole, or a combination of one or more of these.

5. The latent accelerator according to claim 1, characterized in that: The comonomers include one or more of the following: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isooctyl methacrylate, lauryl methacrylate, isobutyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isooctyl acrylate, lauryl acrylate, isobutyl acrylate, isobornyl acrylate, styrene, dimethyl itaconic acid, diethyl itaconic acid, dipropyl itaconic acid, dibutyl itaconic acid, and diisooctyl itaconic acid.

6. The method for preparing the latent promoter based on the dynamic ion pair of anhydride-tertiary amine according to any one of claims 1-5, characterized in that, include: A mixed reaction system containing a first component and a second component is reacted at 0~80°C, wherein the mass ratio of the first component to the second component is 0.6~70:1, to obtain a latent promoter with an anhydride-tertiary amine dynamic ion pair.

7. The preparation method according to claim 6, characterized in that: The reaction time is 0.3 to 72 h.

8. The preparation method according to claim 6, characterized in that: The mixed reaction system also includes a solvent, and the mass ratio of the solvent to the second component is 0.5~15:

1.

9. The use of the latent accelerator based on the dynamic ion pair of anhydride-tertiary amine as described in any one of claims 1-5 in the preparation of single-component thermosetting coatings, adhesives, electronic packaging materials or composite prepregs.

10. A one-component thermosetting resin composition, characterized in that, It is composed of a thermosetting resin and a latent accelerator as described in any one of claims 1-5, wherein the mass ratio of the latent accelerator to the thermosetting resin is 1-70:

100.

11. The one-component thermosetting resin composition according to claim 10, characterized in that: The thermosetting resin includes epoxy resin.

12. A one-component thermosetting resin composition, characterized in that, The product comprises a thermosetting resin, a curing agent, and an accelerator, wherein the mass ratio of the curing agent to the thermosetting resin is 6 to 140:100, and the mass ratio of the accelerator to the thermosetting resin is 1 to 70:100, wherein the accelerator includes the latent accelerator according to any one of claims 1-5.

13. The one-component thermosetting resin composition according to claim 12, characterized in that: The thermosetting resin includes epoxy resin.

14. The one-component thermosetting resin composition according to claim 12, characterized in that: The curing agent includes one or a combination of multiple of the following: acid anhydride curing agents, phenolic curing agents, dicyandiamide curing agents, thiol curing agents, acylhydrazine curing agents, and 4,4'-diaminodiphenyl sulfone.

15. The one-component thermosetting resin composition according to claim 12, characterized in that: The mass ratio of the accelerator to the thermosetting resin is 1~10:100.

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