Latent accelerator based on anhydride-tertiary amine dynamic ion pair as well as preparation method and application of latent accelerator

Abstract

The invention provides a latent accelerator based on anhydride-tertiary amine dynamic ion pairs as well as a preparation method and application of the latent accelerator. The latent accelerator 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 accelerator has an acid anhydride-tertiary amine dynamic ion pair. The latent accelerator provided by the invention can realize long-term storage and medium and low temperature curing of a single-component thermosetting material, and is particularly applied to an epoxy-anhydride system, an epoxy-phenolic aldehyde system, an epoxy-dicyandiamide system, an epoxy-mercaptan system, an epoxy-hydrazide system, an epoxy-4, 4 '-dihydroxybenzenesulfonic acid system, a curing agent and a curing agent. When being used in epoxy resin systems such as 4, 4 '-diaminodiphenyl sulfone systems, the curing temperature of the epoxy resin systems can be reduced, and the epoxy resin systems can be stored for a long time.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a latent promoter based on anhydride-tertiary amine dynamic ion pairs, and a preparation method and application thereof. Background Art

[0002] Thermosetting plastics have excellent thermal properties, mechanical properties, chemical stability, dimensional stability, etc. due to their three-dimensional cross-linked network structure. They are widely used in many fields such as electronic packaging materials, coatings, adhesives, composite materials, etc. Two-component thermosetting materials need to mix thermosetting materials (such as epoxy resin, unsaturated polyester, phenolic resin, polyurethane, rubber, etc.) with curing agents before use. They must be prepared and used immediately. Not only are the preparation steps cumbersome and time-consuming, but the quality is also not guaranteed, and sometimes the remaining parts of the processing will cause environmental pollution and waste. The thermosetting materials currently used are mainly two-component. For example, the output of two-component epoxy resin has reached tens of millions of tons. In contrast, single-component thermosetting materials can pre-mix thermosetting resin monomers with cross-linking agents, solving the tediousness of on-site preparation. However, the current single-component thermosetting materials have the problem of high curing temperature. For example, the mixture of dicyandiamide and epoxy needs to be cured at above 200°C. It can be seen that the development of single-component thermosetting materials with low curing temperature and a certain storage period has become the focus of current research. Summary of the invention

[0003] In order to solve all or part of the above technical problems, the present invention provides the following technical solutions:

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

[0005] The latent accelerator is inhibited from being active under relatively low temperature (e.g., room temperature) conditions and exhibits no promoting activity. Under heating conditions, the dynamic structure of the anhydride-tertiary amine therein is unlocked and exhibits high promoting activity. As a latent accelerator for thermosetting resins, it can effectively inhibit and control the release of the reaction activity of highly active accelerators, realize long-term storage of single-component thermosetting materials under room temperature conditions and rapid crosslinking under medium and low temperature conditions (e.g., 90-130° C.), and reduce 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 by using an unsaturated anhydride copolymer and a compound having a tertiary amine structure is a cross-linked network having an anhydride-tertiary amine dynamic 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 methacrylate compounds, acrylate compounds, styrene compounds or itaconate compounds.

[0009] In some embodiments, the comonomer includes one or a combination of two or more of 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 itaconate, diethyl itaconate, dipropyl itaconate, dibutyl itaconate, and diisooctyl itaconate, but is not limited thereto.

[0010] In some embodiments, the second component includes a combination of one or more of the first tertiary amine structure compound and / or the second tertiary amine structure compound, wherein the N atom of the first tertiary amine structure compound is simultaneously connected with three R groups, wherein the R groups are alkyl groups or heteroatom-containing alkyl groups, and the three R groups are the same or different; and the second tertiary amine structure compound is an imidazole tertiary amine compound, wherein the heteroatom in the heteroatom-containing alkyl group can be N, O, S, and other heteroatoms commonly recognized in the art.

[0011] In some embodiments, the first tertiary amine structure 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-dimethylpropyleneamine, N,N,N′,N′-tetramethylethylenediamine, pentamethyldiethylenetriamine, 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-dimethylprop-1-amine, N, N-dimethylisopropylamine, N,N-dimethyloctylamine, tri(N,N-dimethylaminopropyl)amine, N,N-dimethyldodecylamine, N,N-dimethylferrocenylmethylamine, N,N-dimethylhexadecylamine, N,N-dimethyltetradecylamine, N,N-dimethyloctadecylamine, N,N-dimethylhexylamine, N,N-dimethyl-2-naphthylamine, N,N-dimethylaniline, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,6-bis[(dimethylamino)methyl]phenol, 2,4-bis[(dimethylamino)methyl]phenol, bis(2-dimethylaminoethyl)ether, 1,8-diazabicyclo[5.4.0]undec-7-ene, triethanolamine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 4-dimethylaminopyridine or a combination of more thereof.

[0012] In some embodiments, the second tertiary amine structure compound includes imidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, benzimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, 1,2-dimethylimidazole, 1-isopropylimidazole, 1,4,5-trimethyl-1H-imidazole, 1-ethyl-2-methylimidazole, 4-phenylimidazole, 2,2′-biimidazole, N,N′-carbonyldiimidazole, 2-undecylimidazole, vinylimidazole, 1-(2-hydroxyethyl)imidazole, 4-hydroxyimidazole, 2-aminoimidazole, 1-(3-aminopropyl)imidazole, 4-nitroimidazole, 1-phenylethylimidazole, 2-formylimidazole, 4-formylimidazole, 2-acetylimidazole, benzimidazole, imidazo[1,2-a]pyridine-6-carboxylic acid, 1H-imidazo[1,2-F]phenanthridine, N-n-heptyl imidazole, 1,2′-bis(2-chlorophenyl)-tetraphenylbiimidazole, 5-chloro-3H-imidazole[4,5-B]pyridine, imidazole-4,5-dicarboxylic acid, astemizole, N-BOC-imidazole, 1H-imidazo[4,5-B]pyridine-2(3H)one, 2-(1-naphthyl)-1H-benzimidazole, 4-chloromethylimidazole, (2R)-2,3-dihydro-2-phenylimidazo[2,1-B]benzothiazole, 2-octylbenzimidazole, 2-chloro-4-(1H-2-imidazolyl)pyridine, 2-(3-pyridyl)benzimidazole, oxazolo[1,2-a]pyrazine-3-carboxylic acid ethyl ester, imidazo[1,2-A]pyridine-7-carboxylic acid, imidazo[1,5-a]pyrido[2,3-E]pyrazine-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-imidazol-2-yl)-pyridine, 4,5-dichloroimidazole, (9ci)-2-(2-oxazole)-1H-benzimidazole, 1H-benzimidazole-2-sulfonic acid, 3,6-di(1H-imidazo L-1-yl)pyridinium oxazine, 3-cyclohexylimidazo[1,5-a]pyrazine, 1H-imidazo[4,5-e]tetrazo[1,5-a]pyridine, 2H-thieno[2′,3′:4,5]pyrrolo[1,2-c]imidazole (9CI), imidazo[1,2-a]pyridine-6-methanol, (9CI)-1-acetyl-1H-imidazo[1,2-b]pyrazole, (6-phenylimidazo[2,1-b]thiazol-5-yl)methanol, 9CI)-1H-benzimidazole-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, 5-methoxybenzimidazole, or a combination of one or more thereof.

[0013] The second object of the present invention is to provide a method for preparing a latent promoter based on anhydride-tertiary amine dynamic ion pairs, comprising: reacting a mixed reaction system containing a first component and a second component, wherein the first component includes a substance having an anhydride structure, and the second component includes 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 the temperature range, a higher reaction efficiency can be obtained and the reaction can be more thorough. If the reaction temperature is too low or too high, the reaction will be incomplete or impossible, resulting in the inability to form anhydride-tertiary amine dynamic 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 the substance with anhydride structure is low, the storage effect is poor, and if the content of the compound with tertiary amine structure is low, the active ingredient is low, and the content of the added accelerator is high, which exceeds the scope of the general added accelerator content and increases the economic cost.

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

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

[0019] In some embodiments, the preparation method further includes post-processing. For example, the post-processing may include removing the solvent, drying, etc.

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

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

[0022] The specific selection of the saturated anhydride copolymer of the first component and the compound with anhydride structure of the second component in the "preparation method" provided by the present invention has been described in detail in part of the purpose of the present invention and will not be repeated here.

[0023] The third object of the present invention is to provide the use of the latent accelerator in the preparation of single-component thermosetting coatings, adhesives, electronic packaging materials or composite material prepregs.

[0024] The fourth object of the present invention is to provide a one-component thermosetting resin composition, which is composed of a thermosetting resin and the 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 using other curing agents, the latent accelerator can also make the resin composition cure quickly under low temperature conditions.

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

[0026] The fifth object of the present invention is to provide a one-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 to 140:100, and the mass ratio of the accelerator to the thermosetting resin is 1 to 70:100, wherein the accelerator comprises the latent accelerator.

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

[0028] In some embodiments, the curing agent includes one or more 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 reduce the curing temperature of epoxy-anhydride system, epoxy-phenolic system, epoxy-dicyandiamide system, epoxy-thiol, epoxy-4,4'-diaminodiphenyl sulfone system, so that it can be cured at a lower temperature and its storage period at room temperature can be extended.

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

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

[0031] (1) The latent accelerator provided by the present invention has an acid anhydride-tertiary amine dynamic ion pair in its structure. On the one hand, the acid anhydride-tertiary amine dynamic ion pair itself reduces the activity of the tertiary amine. On the other hand, the acid anhydride in the ion pair is on the unsaturated acid anhydride copolymer chain. The acid anhydride-tertiary amine dynamic ion pair fixes or embeds the tertiary amine compound in the unsaturated acid anhydride copolymer, resulting in the tertiary amine structure being difficult to contact with the epoxy resin when mixed with the epoxy resin, and exhibiting low activity or no activity; thus, the activity of the accelerator is suppressed under relatively low temperature conditions (such as room temperature) and exhibits very low or no activity. It has no promoting activity. Under relatively high temperature conditions, the dynamic ion pair structure of anhydride-tertiary amine is untied, and the highly active tertiary amine is released and contacts with epoxy resin to show high promoting activity. Therefore, using it as a latent promoter for thermosetting resin can effectively inhibit and control the reaction activity of the highly active promoter, realize the long-term storage and rapid cross-linking of single-component thermosetting materials, and enable the single-component thermosetting materials to take into account long-term storage at room temperature and rapid curing at medium and low temperatures. It has broad application prospects in the fields of single-component coatings, adhesives, electronic packaging materials, composite prepregs, etc.

[0032] (2) The latent accelerator 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 they can achieve rapid curing at 90-130° C., solving the problems of high curing temperature and incomplete reaction of epoxy resin system in the prior art, and can also have a long storage period (e.g., more than 6 months) at a relatively low temperature (e.g., room temperature);

[0033] (3) The method for preparing the latent promoter provided by the present invention is simple in process, easy to operate, well controllable, and easy to implement, and is suitable for large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

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

[0036] Figure 2 It is the infrared spectrum of the latent accelerator prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0037] The technical solution of the present invention is described in detail below in conjunction with specific embodiments so that those skilled in the art can better understand and implement the technical solution of the present invention. The specific functional details disclosed herein should not be interpreted as limiting, but only as the basis for the claims and as a representative basis for teaching those skilled in the art to adopt the present invention in different ways in any appropriate detailed embodiment.

[0038] In addition, unless otherwise specified, the various raw materials used in the following examples can be purchased from the market and other channels, and the various production and testing equipment used are also equipment known in the art.

[0039] Some of the reagents and test methods used in the following examples are as follows:

[0040] Reagents: styrene and maleic anhydride copolymer SMA3000 / SMA2000 / SMA1000 (Crayville), 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), mercaptan 405 (Guangzhou Green New Materials), 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) (Evonik ANCAMINE K54).

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

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

[0043] Tensile test: A universal testing machine UTM4000 (Shenzhen Sansi Zongheng Technology Co., Ltd., China) was used. The specimen gauge length was 40 mm, and the size was 80 mm (length) × 6 mm (width) × 0.3 mm (thickness) at 10 mm min. -1 Test at speed.

[0044] The partially unsaturated anhydride copolymer used in the following specific embodiments is prepared by the following method: Taking Example 2 as an example, n-butyl methacrylate and itaconic anhydride copolymer are mixed in a molar ratio of 1:1, and butanone is used as a solvent, and 1.2% of the total mass of the initiator azobisisobutyronitrile is added, and the reaction is carried out at 75°C for 6 hours, and petroleum ether is used for precipitation 4 times to obtain a copolymer with a molecular weight of 13000-14000. The preparation method of the copolymers in other embodiments is basically the same as that in Example 2, and the selection and molar ratio of the unsaturated anhydride and the comonomer are changed during the preparation. The selection of specific monomers, the molar ratio and the molecular weight of the copolymer have been described in the corresponding embodiments.

[0045] Example 1

[0046] 150 parts (all parts by mass unless otherwise specified) of styrene and 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, stirred with a stirrer and reacted at 50°C for 3.5 hours. After the reaction, the solvent was removed and the mixture was crushed into fine powder to obtain the target product, i.e., a latent accelerator, which was in powder form, such as Figure 1 The infrared spectrum of the latent promoter is shown in Figure 2 As shown, at 1715cm -1 Yes-C(O)N + Characteristic peaks, 1500-1600cm -1 The characteristic peak of -COO was included, indicating that the product had been successfully synthesized.

[0047] Two parts of the latent accelerator prepared in this embodiment were uniformly mixed with 6 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 by a rheometer at room temperature, and it was found that the viscosity after 6 months was 1.05 times the initial viscosity. The resin composition was heated at 100° C. for 2.5 hours to be cured, and its glass transition temperature was measured to be 135° C. and the tensile strength was 70 MPa.

[0048] Comparative Example 1

[0049] 150 parts of styrene and 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, stirred with a stirrer and reacted at -5°C for 3.5 hours, the solvent was removed, and the mixture was crushed into fine powder to obtain a product. A resin composition was prepared and tested in the same manner as in Example 1.

[0050] Comparative Example 2

[0051] Comparative Example 2 uses 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) as an accelerator. A resin composition was prepared and tested in the same manner as in Example 1.

[0052] Comparative Example 3

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

[0054] Comparative Example 4

[0055] The preparation method of a 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) is used. The rest is the same as in Example 1. A resin composition is prepared and tested in the same manner as in Example 1.

[0056] Comparative Example 5

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

[0058] Comparative Example 6

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

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

[0061]

[0062] The latent accelerators prepared in Example 1 and Comparative Examples 1-6 were used to prepare resin compositions, and then the viscosity of the resin compositions was monitored by a rheometer at room temperature. The resin compositions were heated for a certain time at a certain temperature to be cured, and the glass transition temperature and tensile strength were tested. The viscosity test results, curing temperature, time, glass transition temperature and tensile strength are shown in Table 2.

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

[0064]

[0065] Example 2

[0066] 150 parts of a copolymer of n-butyl methacrylate and itaconic anhydride (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, stirred with a stirrer and reacted at 50°C for 3.5 hours, the solvent was removed, and the mixture was crushed into fine powder to obtain the target product, i.e., a 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 are dissolved in a round-bottom flask, 50 parts of N, N-dimethylbenzylamine are added, stirred with a stirrer and reacted at 0°C for 72 hours, crushed into fine powder, and the solvent is removed to obtain the target product, i.e., a latent accelerator.

[0069] Example 4

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

[0071] Example 5

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

[0073] Example 6

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

[0075] Example 7

[0076] 150 parts of styrene and 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, stirred with a stirrer and reacted at 50°C for 3.5 hours, the solvent was removed, and the mixture was crushed into fine powder to obtain the target product, i.e., a 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, stirred with a stirrer and reacted at 50°C for 3.5 hours, and crushed into fine powder to obtain the target product, i.e., the latent accelerator.

[0079] Example 9

[0080] 112 parts of a copolymer of n-butyl methacrylate and itaconic anhydride (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, stirred with a stirrer and reacted at 50°C for 3.5 hours, the solvent was removed, dried, and crushed into fine powder to obtain the target product, i.e., a 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, stirred with a stirrer and reacted at 50°C for 3.5 hours, the solvent was removed, and the mixture was crushed into fine powder to obtain the target product, i.e., a latent accelerator.

[0083] Embodiment 11

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

[0085] Example 12

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

[0087] Embodiment 13

[0088] 150 parts of styrene and citraconic anhydride copolymer (monomer molar ratio 1.2:1, molecular weight 7000-8000) and 300 parts of butanone are dissolved in a round-bottom flask, 100 parts of triamylamine are added, stirred with a stirrer and reacted at 0°C for 72 hours, the solvent is removed to obtain the target product, which is crushed into fine powder, i.e., the latent accelerator.

[0089] Embodiment 14

[0090] 150 parts of styrene and citraconic anhydride copolymer (monomer molar ratio 1.5:1, molecular weight 8000-10000) and 100 parts of chloroform are dissolved in a round-bottom flask, 34 parts of triethylamine are added, stirred with a stirrer and reacted at 50°C for 3.5 hours, the solvent is removed, and the mixture is crushed into fine powder to obtain the target product, i.e., a latent accelerator.

[0091] Embodiment 15

[0092] 159 parts of a copolymer of n-butyl methacrylate and itaconic anhydride (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, stirred with a stirrer and reacted at 50°C for 3.5 hours, the solvent was removed, and the mixture was crushed into fine powder to obtain the target product, i.e., a latent accelerator.

[0093] Example 16

[0094] 154 parts of a copolymer of n-butyl methacrylate and itaconic anhydride (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, stirred with a stirrer and reacted at 30°C for 12 hours, the solvent was removed, and the mixture was crushed into fine powder to obtain the target product, i.e., a latent accelerator.

[0095] Embodiment 17

[0096] 218 parts of styrene and citraconic anhydride copolymer (monomer molar ratio 1:1, molecular weight 8000-10000) and 300 parts of acetone are placed in a round-bottom flask and dissolved, 265 parts of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) are added, stirred with a stirrer and reacted at 50°C for 12 hours, the solvent is removed to obtain the target product, which is crushed into fine powder, i.e., a latent accelerator.

[0097] Embodiment 18

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

[0099] Embodiment 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, stirred with a stirrer and reacted at 80°C for 3 hours, and the solvent was removed to obtain the target product, i.e., a latent accelerator.

[0101] Embodiment 20

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

[0103] Embodiment 21

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

[0105] Embodiment 22

[0106] 100 parts of a copolymer of n-butyl methacrylate and itaconic anhydride (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, stirred with a stirrer and reacted at 50°C for 4 hours, the solvent was removed, and the mixture was crushed into fine powder to obtain the target product, i.e., a latent accelerator.

[0107] Embodiment 23

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

[0109] Embodiment 24

[0110] 100 parts of a terpolymer of methyl methacrylate, n-butyl acrylate and itaconic anhydride (monomer molar ratio of 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, stirred with a stirrer and reacted at 60°C for 3 hours, and the solvent was removed to obtain the target product, i.e., a latent accelerator.

[0111] Embodiment 25

[0112] 150 parts of styrene and citraconic anhydride copolymer (monomer molar ratio 1.5:1, molecular weight 8000-10000) and 100 parts of chloroform are dissolved in a round-bottom flask, 55 parts of benzimidazole are added, stirred with a stirrer and reacted at 50°C for 3.5 hours, the solvent is removed, and the mixture is crushed into fine powder to obtain the target product, i.e., a latent accelerator.

[0113] Comparative Example 7

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

[0115] It was found that compared with the promoter prepared from the unsaturated acid anhydride copolymer, the target product obtained in Comparative Example 7 formed ion pairs with small molecules and was easier to absorb water when crushed. Since the promoter prepared from the unsaturated acid anhydride copolymer contained hydrophobic structures, such as styrene and methacrylate, it was easier to crush, thus solving the problem of easy dispersion of latent promoters.

[0116] Comparative Example 8

[0117] 168 parts of methyl hexahydrophthalic anhydride and 265 parts of NN-dimethylbenzylamine were placed in a round-bottom flask, mixed, stirred with a stirrer and reacted at 50° C. for 3.5 hours to obtain the target product.

[0118] The accelerators prepared from the unsaturated anhydride copolymers of the present invention are all hydrophobic and crushable solids, whereas the target product of Comparative Example 8 is a liquid and is more susceptible to water absorption; the one-component epoxy resin composition prepared with the accelerator has no shelf life.

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

[0120] Table 3 Raw materials and reaction conditions used in preparing latent accelerators in Examples 1-20

[0121]

[0122]

[0123] The latent accelerators of Examples 1-20 were used to prepare resin compositions, 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 in the same manner as in Example 1, and the test results are shown in Table 4.

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

[0125]

[0126]

[0127]

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

[0129] Based on the above embodiments, it can be seen that the latent promoter of the anhydride-tertiary amine dynamic ion pair provided by the present invention can realize the long-term storage and medium and low temperature curing of single-component thermosetting materials, especially applying it to epoxy-anhydride system, epoxy-phenolic system, epoxy-dicyandiamide system, epoxy-thiol system, epoxy-hydrazide system, epoxy-4,4'-diaminodiphenyl sulfone system and other epoxy resin systems, which can not only reduce the curing temperature of these epoxy resin systems, but also greatly extend their storage period. Based on the current experimental results, it is expected that some preferred embodiments can have an ultra-long storage period, for example, more than a few years, and its viscosity does not change significantly during the ultra-long storage period, which provides a new, simple and efficient strategy for the development of single-component thermosetting resins. And most of the raw materials for preparing the latent promoter are commercial substances, the raw materials are easy to obtain, and the preparation process is simple, easy to operate, controllable, easy to implement, and suitable for large-scale industrial production.

[0130] The various aspects, embodiments, features and examples of the present invention should be considered as illustrative in all aspects and are not intended to limit the present invention, the scope of the present invention is defined only by the claims. Other embodiments, modifications and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.

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

[0132] Although the present invention has been described with reference to illustrative embodiments, it will be appreciated by those skilled in the art that various other changes, omissions and / or additions may be made without departing from the spirit and scope of the present invention and that the elements of the embodiments may be replaced by substantial equivalents. In addition, many modifications may be made without departing from the scope of the present invention to adapt specific circumstances or materials to the teachings of the present invention. Therefore, it is not intended herein to limit the present invention to the disclosed specific embodiments for performing the present invention, but it is intended that the present invention will include all embodiments within the scope of the appended claims. In addition, unless specifically stated, any use of the terms first, second, etc. does not indicate any order or importance, but rather uses the terms first, second, etc. 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 a reaction product of a first component and a second component, wherein the first component includes a substance having an anhydride structure, and the second component includes a compound having a tertiary amine structure, and the latent accelerator has an anhydride-tertiary amine dynamic ion pair.

2. The latent promoter according to claim 1, characterized in that: The first component is an unsaturated acid anhydride copolymer, and the unsaturated acid anhydride copolymer is a binary or multinary copolymer of an unsaturated acid anhydride and a comonomer; And / or, the second component includes a combination of one or more of a first tertiary amine structure compound and / or a second tertiary amine structure compound, three R groups are simultaneously connected to the N atom of the first tertiary amine structure compound, the R groups are alkyl groups or heteroatom-containing alkyl groups, and the three R groups are the same or different; the second tertiary amine structure compound is an imidazole tertiary amine compound.

3. The latent promoter according to claim 2, characterized in that: The first tertiary amine structure 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-dimethylpropyleneamine, N,N,N′,N′-tetramethylethylenediamine, pentamethyldiethylenetriamine, 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-dimethylprop-1-amine, N,N-dimethyl one or more combinations of 1,2-dimethyl-2-nitropropy amine, 1,8-diazabicyclo[5.4.0]11-7-ene, triethanolamine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 4-dimethylaminopyridine; and / or, the second tertiary amine structure compound includes imidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, benzimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, 1,2-dimethylimidazole, 1-isopropylimidazole, 1,4,5-trimethyl-1H-imidazole, 1-ethyl-2-methylimidazole, 4-phenylimidazole, 2,2′-biimidazole, N,N′-carbonyldiimidazole, 2-undecylimidazole, vinylimidazole, 1-(2-hydroxyethyl)imidazole, 4-hydroxyimidazole, 2-aminoimidazole, 1-(3-aminopropyl)imidazole, 4-nitroimidazole, 1-phenylethylimidazole, 2-formylimidazole, 4-formylimidazole, 2-acetylbenzene imidazole, imidazo[1,2-a]pyridine-6-carboxylic acid, 1H-imidazo[1,2-F]phenanthridine, N-n-heptyl imidazole, 1,2′-bis(2-chlorophenyl)-tetraphenylbiimidazole, 5-chloro-3H-imidazole[4,5-B]pyridine, imidazole-4,5-dicarboxylic acid, astemizole, N-BOC-imidazole, 1H-imidazo[4,5-B]pyridine-2(3H)one, 2-(1-naphthyl)-1H-benzimidazole, 4-chloromethylimidazole, (2R)-2,3-dihydro-2-phenylimidazo[2,1-B]benzothiazole, 2-octylbenzimidazole, 2-chloro-4-(1H-2-imidazolyl)pyridine, 2-(3-pyridyl)benzimidazole, imidazole imidazo[1,2-a]pyrazine-3-carboxylic acid ethyl ester, imidazo[1,2-A]pyridine-7-carboxylic acid, imidazo[1,5-a]pyrido[2,3-E]pyrazine-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-imidazol-2-yl)-pyridine, 4,5-dichloroimidazole, (9ci)-2-(2-oxazole)-1H-benzimidazole, 1H-benzimidazole-2-sulfonic acid, 3,6-di(1H-imidazoL-1-yl)pyridinium oxazine, 3-cyclohexylimidazo[1,5-a]pyrazine, 1H-imidazo[4,5-e]tetrazo[1,5-a]pyridine, 2H-thieno[2′,3′:4,5]pyrrolo[1,2-c]imidazole (9CI), imidazo[1,2-a]pyridine-6-methanol, (9CI)-1-acetyl-1H-imidazo[1,2-b]pyrazole, (6-phenylimidazo[2,1-b]thiazol-5-yl)methanol, 9CI)-1H-benzimidazole-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, 5-methoxybenzimidazole, or a combination of one or more thereof.

4. The latent promoter according to claim 2, characterized in that: The unsaturated acid 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 itaconate compounds; Preferably, the comonomer includes one or a combination of two or more of 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 itaconate, diethyl itaconate, dipropyl itaconate, dibutyl itaconate and diisooctyl itaconate.

5. A method for preparing a latent promoter based on anhydride-tertiary amine dynamic ion pair, characterized in that: include: A mixed reaction system containing a first component and a second component is reacted, wherein the first component includes a substance having an anhydride structure and the second component includes a compound having a tertiary amine structure, so as to obtain a latent promoter having an anhydride-tertiary amine dynamic ion pair.

6. The preparation method according to claim 5, characterized in that: The first component is an unsaturated acid anhydride copolymer, and the unsaturated acid anhydride copolymer is a binary or multinary copolymer of an unsaturated acid anhydride and a comonomer; And / or, the second component includes a combination of one or more of a first tertiary amine structure compound and / or a second tertiary amine structure compound, the N atom of the first tertiary amine structure compound is simultaneously connected with three R groups, the R groups are alkyl groups or heteroatom-containing alkyl groups, and the three R groups are the same or different; the second tertiary amine structure compound is an imidazole tertiary amine compound; And / or, the reaction includes one or more of a nucleophilic addition reaction of a tertiary amine and an acid anhydride, an esterification reaction of a phenolic hydroxyl group and an acid anhydride, a salt-forming reaction of a tertiary amine and a carboxyl group, and an amidation reaction of an acid anhydride and a secondary amine.

7. The preparation method according to claim 5, characterized in that: The reaction temperature is 0 to 80°C, and / or the reaction time is 0.3 to 72 hours; And / or, the mass ratio of the first component to the second component is 0.6 to 70:1; And / or, the mixed reaction system further comprises a solvent, and the mass ratio of the solvent to the second component is 0.5 to 15:

1.

8. Use of the latent accelerator based on anhydride-tertiary amine dynamic ion pair according to any one of claims 1 to 4 in the preparation of a single-component thermosetting coating, an adhesive, an electronic packaging material or a composite material prepreg.

9. A one-component thermosetting resin composition, characterized in that: Composed of a thermosetting resin and the latent accelerator according to any one of claims 1 to 4, wherein the mass ratio of the latent accelerator to the thermosetting resin is 1 to 70:100; Preferably, the thermosetting resin comprises epoxy resin.

10. A one-component thermosetting resin composition, characterized in that: The invention 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 promoter comprises the latent promoter according to any one of claims 1 to 4; Preferably, the thermosetting resin comprises epoxy resin; Preferably, the curing agent includes one or a combination of anhydride curing agent, phenolic curing agent, dicyandiamide curing agent, thiol curing agent, hydrazide curing agent, and 4,4′-diaminodiphenyl sulfone; Preferably, the mass ratio of the accelerator to the thermosetting resin is 1 to 10:100.

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