Resin composition, prepreg and laminated board
Technical Field
The invention belongs to the technical field of polymer resin compositions, and particularly relates to a resin composition, a prepreg and a laminated board.
Background
The epoxy resin has the characteristics of high mechanical property, excellent bonding property, small curing shrinkage, excellent process property, good stability and the like, and is one of thermosetting plastics mainly applied to the field of composite materials. The process of preparing the high-strength composite material by impregnating the glass fiber cloth with the epoxy resin glue solution generally comprises the steps of preparing the resin composition, coating the glue solution, drying to prepare a prepreg, and laminating the prepreg and hot pressing. Therefore, the prepared prepreg has the requirements of moderate processing temperature, high curing rate and good normal-temperature storage stability, and is suitable for the processing and molding process.
However, epoxy resin composition/prepreg products in the current market generally need high-temperature curing, have long curing time, consume a large amount of resource cost and cannot improve the production efficiency; and the existing products meeting the requirement of rapid curing react too quickly at normal temperature, the shelf life is generally within 1 week, and the products cannot be stored for a long time or need to be stored in an ice warehouse. At present, there are few related products that can simultaneously meet the requirements of fast cure rate and storage stability. For example, the medium temperature fast curing halogen-free flame retardant formulation disclosed in CN110256812A can satisfy the condition that the curing is complete at 130-150 ℃ for less than 30min, but the normal temperature operation period can only be 7 days. The liquid epoxy resin composition disclosed in CN106589823A can be completely cured at 120 ℃ for 15min, but can be stored only under refrigerated (4 ℃) conditions for one week.
Accordingly, the present invention has been made in view of the above-mentioned problems occurring in the prior art, and it is an object of the present invention to provide a resin composition, a prepreg and a laminate. The prepreg prepared by the resin composition meets the requirement of medium-high temperature rapid curing (specifically 150 ℃ C. and 160 ℃ C., less than 20min), and can be stored at normal temperature for more than 1 month.
Disclosure of Invention
The invention aims to make up for the defects of the prior art and provides a resin composition, a prepreg and a laminated board. The resin composition of the invention is added with three curing agents with different properties, and the prepared prepreg has the advantages of medium-high temperature rapid curing, long normal temperature storage time, high production efficiency, low cost and the like.
The invention provides a resin composition which comprises epoxy resin, a first curing agent, a second curing agent and a third curing agent, wherein the first curing agent is a latent curing agent, the second curing agent is an imidazole curing agent, and the third curing agent is a tertiary amine curing agent.
Preferably, the resin composition comprises the following components in parts by weight: 100 parts of epoxy resin, 1-60 parts of first curing agent, 0.1-3 parts of second curing agent, 0.1-3 parts of third curing agent, and 0.2-5 parts of second curing agent and third curing agent.
The ratio of the components of the resin composition of the present invention has an important influence on the application of the resin composition in a laminate, and particularly, the weight ratio of the three curing agents may cause defective or unmoldable molding of the laminate if the weight ratio of the three curing agents exceeds the above-mentioned range, or may cause a decrease in mechanical and thermal properties of the laminate if the kind ratio of the three curing agents is below the above-mentioned range.
Preferably, the epoxy resin is selected from one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and novolac epoxy resin; more preferably, the epoxy resin is selected from one or more of bisphenol a epoxy resin, bisphenol F epoxy resin and novolac epoxy resin.
Preferably, the first curing agent is selected from one or more of amine-based curing agents, phenolic curing agents, anhydride-based curing agents, and boron trifluoride-amine complexes; more preferably, the first curing agent is selected from one or more of dicyandiamide, diaminodiphenyl sulfone, diaminodiphenylamine, organic acid hydrazide, linear phenol-formaldehyde resin, linear bisphenol a-formaldehyde resin, linear o-cresol-formaldehyde resin, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.
Preferably, the second curing agent is selected from imidazole and modified substances thereof, and the tertiary amine equivalent in the molecular structure is between 80 and 500; more preferably, the second curing agent is imidazole curing agent, including imidazole and its modified substance, which is required to have tertiary amine equivalent in molecular structure between 80-500, wherein 2-methylimidazole (2MZ), 2-ethylimidazole (2 EI), 2-ethyl-4 methylimidazole (2E4MZ), 2-undecylimidazole (C) is preferred11Z), 2-heptadecylimidazole (C)17Z), 2-phenylimidazole (2PZ), 1-benzyl-2-methylimidazole (1B2 MZ).
Preferably, the third curing agent is a tertiary amine curing agent, including modified imidazole and other tertiary amine substances, which is required to have a molecular structure with a tertiary amine equivalent of 25-78, wherein one or more of imidazole, 1, 2-dimethylimidazole, N-acylimidazole, pyridine, 4-dimethylaminopyridine and tetramethylethylenediamine is preferred.
Preferably, the resin composition further comprises an organic solvent, wherein the organic solvent accounts for 20-120 parts by weight; the organic solvent is selected from one or more of alcohols, ketones, ethers, amides and benzene solvents; more preferably, the organic solvent is selected from one or more of N, N-dimethylformamide, butanone, ethanol, propylene glycol methyl ether, ethylene glycol monomethyl ether, and toluene.
Preferably, the resin composition also comprises an inorganic filler, a dispersant and a coupling agent, wherein the inorganic filler accounts for 10-80 parts by weight, the dispersant accounts for 0.01-1 part by weight, and the coupling agent accounts for 0.1-2 parts by weight.
Preferably, the inorganic filler is selected from one or more of silicon-containing inorganic compounds, titanium-containing inorganic compounds, calcium-containing inorganic compounds, aluminum-containing inorganic compounds and magnesium-containing inorganic compounds; more preferably, the inorganic filler is selected from one or more of silica, titanium dioxide, alumina, talc, kaolin and aluminum hydroxide.
Preferably, the dispersant is selected from one or more of fatty acid, fatty amide and lipid dispersants; more preferably, the dispersant is selected from one or both of fatty acid-based and lipid-based dispersants.
Preferably, the coupling agent comprises a silane coupling agent with a chemical general formula of RSiX3Wherein R represents amino, mercapto, vinyl, epoxy, cyano or methacryloxy, and X represents an alkoxy group capable of hydrolysis; more preferably, X represents methoxy or ethoxy.
The invention also provides a prepreg which comprises a reinforcing material and the resin composition attached to the reinforcing material after being coated and dried.
The invention also provides a laminated plate, which comprises the steps of placing the stacked prepreg between two stainless steel plates and covering a release film on the surface of the prepreg, which is in contact with the stainless steel plates.
The invention has the following technical characteristics:
1) according to the invention, three curing agents, namely the latent curing agent, the imidazole curing agent and the tertiary amine curing agent are simultaneously added into the resin composition, and through the compound use of the three curing agents, the prepreg prepared from the resin composition can be rapidly cured (less than 20min) under the medium-high temperature condition (150 ℃ C.) and 160 ℃ C, and can be stored for more than 1 month at normal temperature.
2) The laminated board has good mechanical and thermal properties (the bending strength is 500-700MPa, the bending modulus is 27.0-29.5GPa, and the Tg is 130-145 ℃), improves the production efficiency of the whole process, and saves the process cost by 10-20%.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1
Step 1: adding 3.5 parts of dicyandiamide, 0.9 part of dimethyl imidazole and 1.8 parts of N-acyl imidazole into 60 parts of N, N-dimethylformamide and acetone organic solvent, and adding 100 parts of bisphenol A epoxy resin after completely dissolving to prepare the epoxy resin composition.
Step 2: uniformly coating the epoxy resin composition on electronic-grade glass fiber cloth, baking at 120-180 ℃ for 2-5min, and cooling to room temperature to prepare a prepreg;
and 3, stacking the prepreg 1 to a plurality of layers of prepregs, attaching release films to two surfaces of the prepreg, stacking stainless steel plates up and down, and feeding the prepreg into a stacked hot press for high-temperature and high-pressure molding at the temperature of 160 ℃/0.5-5MPa for 15-30min by 140-.
And 4, storing the prepreg at room temperature for 1 month, and performing hot-press molding according to the process in the step 3 to prepare the thermosetting laminated board ②.
The laminate was observed for formation and tested for glass transition temperature (Tg and △ Tg, where the sheet was not fully cured if △ Tg > 3 ℃) and flexural properties using a universal tensile machine.
Example 2
Step 1: adding 10.3 parts of diaminodiphenyl sulfone, 1.9 parts of 2-ethyl-4-methylimidazole and 1.3 parts of tetramethylethylenediamine into 60 parts of N, N-dimethylformamide and acetone organic solvent, and adding 100 parts of bisphenol A epoxy resin after complete dissolution to prepare the epoxy resin composition.
The preparation and testing were carried out according to the process steps of example 1.
Example 3
Step 1: 39.5 parts of linear phenol formaldehyde resin, 1.4 parts of 2-undecylimidazole (C11Z) imidazole, 2.3 parts of 1, 2-dimethylimidazole are added into 80 parts of N, N-dimethylformamide and propylene glycol methyl ether organic solvent, 100 parts of bisphenol A epoxy resin is added after complete dissolution and mixed evenly, 20 parts of silicon dioxide, 10 parts of titanium dioxide, 5 parts of talcum powder, 0.8 part of silane coupling agent and 0.5 part of fatty acid dispersing agent are added, and the mixture is fully stirred to prepare the epoxy resin composition.
The preparation and testing were carried out according to the procedure of example 1.
Example 4
Step 1: 58 parts of hexahydrophthalic anhydride, 1.6 parts of 2-ethylimidazole (2-EI) and 2.6 parts of pyridine are added into 100 parts of butanone and propylene glycol methyl ether mixed organic solvent, 100 parts of bisphenol A epoxy resin is added after complete dissolution and is uniformly mixed, 40 parts of silicon dioxide, 15 parts of aluminum hydroxide, 5 parts of talcum powder, 1.5 parts of silane coupling agent and 0.8 part of lipid dispersant are added, and the mixture is fully stirred to prepare the epoxy resin composition.
The preparation and testing were carried out according to the procedure of example 1.
Example 5
Step 1: adding 25.4 parts of organic acid hydrazide, 0.4 part of 2-phenylimidazole and 2.8 parts of 4-dimethylaminopyridine into 100 parts of butanone and propylene glycol methyl ether mixed organic solvent, adding 100 parts of bisphenol A epoxy resin after complete dissolution, uniformly mixing, adding 15 parts of titanium dioxide, 10 parts of aluminum hydroxide, 0.5 part of silane coupling agent and 0.5 part of lipid dispersant, and fully stirring to prepare the epoxy resin composition.
The preparation and testing were carried out according to the procedure of example 1.
Comparative example 1
Adding 3.5 parts of dicyandiamide, 1.5 parts of dimethyl imidazole, 3.2 parts of N-acyl imidazole into 60 parts of N, N-dimethylformamide and acetone organic solvent, and adding 100 parts of bisphenol A epoxy resin after completely dissolving to prepare the epoxy resin composition.
The preparation and testing were carried out according to the process steps of example 1.
Comparative example 2
Adding 10.3 parts of diaminodiphenyl sulfone, 3.2 parts of 2-ethyl-4-methylimidazole and 1.5 parts of tetramethylethylenediamine into 60 parts of N, N-dimethylformamide and acetone organic solvent, and adding 100 parts of bisphenol A epoxy resin after complete dissolution to prepare the epoxy resin composition.
The preparation and testing were carried out according to the process steps of example 1.
Comparative example 3
An epoxy resin composition was prepared by adding 39.5 parts of a linear phenol formaldehyde resin, 3.5 parts of 2-undecylimidazole (C11Z) imidazole, and 3.5 parts of 1, 2-dimethylimidazole to 60 parts of N, N-dimethylformamide and acetone organic solvent, and after completely dissolving, adding 100 parts of bisphenol A epoxy resin.
The preparation and testing were carried out according to the process steps of example 1.
Comparative example 4
Adding 3.5 parts of dicyandiamide and 1 part of dimethyl imidazole into 60 parts of N, N-dimethylformamide and acetone organic solvent, and adding 100 parts of bisphenol A epoxy resin after complete dissolution to prepare the epoxy resin composition.
The preparation and testing were carried out according to the process steps of example 1.
Comparative example 5
Adding 10.3 parts of diaminodiphenyl sulfone and 2.0 parts of tetramethylethylenediamine into 60 parts of N, N-dimethylformamide and acetone organic solvent, and adding 100 parts of bisphenol A epoxy resin after complete dissolution to prepare the epoxy resin composition.
The preparation and testing were carried out according to the process steps of example 1.
The results of the tests of examples 1 to 5 and comparative examples 1 to 5 are shown in the following table.
Note that DSC testing of the thermoset Tg shows Tg1/Tg2, △ Tg | -Tg 1-Tg2 | characterizes the degree of cure, and if △ Tg > 3 ℃, the material is not fully cured within the required process conditions and the properties show a different degree of reduction.
As can be seen from the examples 1-5, the prepreg can be molded after the prepreg is prepared and stored at normal temperature for one month, is completely cured and has high mechanical properties by combining the first curing agent, the second curing agent and the third curing agent as required. Solves the problems of rapid molding at medium and high temperature and long-term storage at normal temperature. Meanwhile, different curing systems show certain thermal and mechanical property difference.
It is seen from comparative example 1 and example 1, comparative example 2 and example 2, and comparative example 3 and example 3 that if one component of the second curing agent and the third curing agent exceeds the range or both exceed the ranges, the sheet is formed defectively or cannot be formed, and the performance influence is large.
It can be seen from comparative examples 4 and 5 that if only the first curing agent + the second curing agent or the first curing agent + the third curing agent is used, the sheet can be formed but cannot be completely cured, and the thermal and mechanical properties are reduced to different degrees.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.