CN112679907B - Moisture-heat resistant resin composition, preparation method thereof, prepreg and laminated board - Google Patents
Moisture-heat resistant resin composition, preparation method thereof, prepreg and laminated board Download PDFInfo
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- CN112679907B CN112679907B CN201910987396.6A CN201910987396A CN112679907B CN 112679907 B CN112679907 B CN 112679907B CN 201910987396 A CN201910987396 A CN 201910987396A CN 112679907 B CN112679907 B CN 112679907B
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Abstract
The invention discloses a moisture-heat resistant resin composition, and a prepreg and a laminated board thereof. The moisture-heat resistant resin composition comprises the following blended components: 30-80 parts of epoxy resin, 10-50 parts of benzoxazine resin, 0.1-10 parts of modified silicone oil, 10-80 parts of curing agent and 0.1-5 parts of accelerator. The moisture-heat resistant resin composition and the prepreg thereof have good technological properties, and the laminated board obtained by curing has low moisture-heat water absorption rate, and good mechanical properties and heat resistance after moisture absorption.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a moisture-heat resistant resin composition, a preparation method thereof, prepreg and a laminated board.
Background
The carbon fiber reinforced epoxy resin based composite material has high specific strength/specific rigidity, fatigue resistance, corrosion resistance and excellent mechanical properties. As the composite material is applied to the industrial fields of aerospace and other severe environments in a large number, the influence of environmental factors such as impact, damp heat and the like on the mechanical properties of the composite material is increasingly displayed. In a humid environment, degradation of mechanical properties, mismatch of interfacial expansion and the like of composite materials caused by moisture absorption become common problems in epoxy composite material application. The diffusion of moisture in the epoxy resin is an important link for researching moisture absorption damage, and has important significance for improving the reliability of an epoxy resin system. How to block moisture and reduce the moisture absorption rate of the resin is a difficult problem faced by the technology.
Disclosure of Invention
The invention aims to solve the problem that epoxy resin is not resistant to damp and heat in the prior art, and provides a damp and heat resistant resin composition, and a prepreg and a laminated board thereof. From the aspect of the formulation design of the epoxy matrix, the benzoxazine resin and the modified silicone oil are introduced into an epoxy resin system, and the moisture-heat resistant resin composition is developed. The wet heat resistant resin composition and the prepreg thereof have good technological properties, the laminated board has low wet heat water absorption rate, and good mechanical properties and heat resistance are maintained after moisture absorption.
The invention aims at providing a moisture-heat resistant resin composition which comprises the following blended components in parts by weight:
30-80 parts of epoxy resin; preferably 40 to 70 parts;
10-50 parts of benzoxazine resin; preferably 10 to 40 parts;
0.1 to 10 parts of modified silicone oil; preferably 0.1 to 5 parts.
The epoxy resin is an epoxy compound containing two or more epoxy groups in the molecule, and can be selected from epoxy resins commonly used in the field, preferably at least one of glycidyl ether epoxy resins, glycidyl ester epoxy resins and glycidyl amine epoxy resins. More preferably, the epoxy resin is at least one selected from bisphenol a type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, and the like.
The benzoxazine resin may be selected from at least one of a benzoxazine resin commonly used in the art, preferably from a bisphenol a type benzoxazine resin, a dicyclopentadiene type benzoxazine resin, a bisphenol F type benzoxazine resin, a phenolphthalein type benzoxazine resin, and a 4,4 '-diaminodiphenylmethane type benzoxazine, more preferably from at least one of a bisphenol a type benzoxazine resin and a 4,4' -diaminodiphenylmethane type benzoxazine.
The molecular weight of the modified silicone oil is 500-20000, preferably 1000-10000; the content of the modifying group is 2 to 30wt%, preferably 5 to 20wt%.
The modified silicone oil may be at least one modified silicone oil commonly used in the art, preferably at least one modified silicone oil selected from amino modified silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, alcohol modified silicone oil, phenol modified silicone oil, mercapto modified silicone oil, acryloxy modified silicone oil, methacryloxy modified silicone oil, methyl long-chain alkyl silicone oil, methyl trifluoropropyl silicone oil, polyether modified silicone oil, more preferably at least one modified silicone oil selected from amino modified silicone oil and epoxy modified silicone oil.
The moisture and heat resistant resin composition of the present invention may further comprise at least one of the following components in parts by weight:
10-80 parts of curing agent; preferably 20 to 70 parts;
0.1-5 parts of promoter; preferably 0.1 to 2 parts.
Wherein the curing agent is selected from at least one of aromatic amine, aliphatic amine, alicyclic amine, imide, aromatic anhydride, alicyclic anhydride, aliphatic acid anhydride and halogen-containing anhydride. Specifically, the curing agent may be 4,4' -diaminodiphenylmethane or the like.
The accelerator is selected from accelerators commonly used in the art, preferably at least one of quaternary ammonium salts, tertiary amines, triphenylphosphine, quaternary phosphonium salts, imidazole, boron trifluoride and complexes thereof. Specifically, the accelerator may be boron trifluoride ethylamine complex or the like.
The epoxy resin composition of the invention can be added with various common assistants in the field, such as defoamer, internal mold release agent and the like according to the processing requirement, and the dosage of the epoxy resin composition is conventional or is adjusted according to the actual condition requirement.
The second purpose of the invention is to provide a preparation method of the moisture-heat resistant resin composition, which comprises the following steps:
the components including epoxy resin, benzoxazine resin and modified silicone oil are mixed according to the amounts.
Preferably, the components are mixed and heated to 20-100 ℃ under the protection of nitrogen while stirring, so that the components are completely mutually dissolved and uniformly mixed.
The mixing may be performed by a mixing method and apparatus which are usual in the art, for example, by stirring.
The third object of the present invention is to provide a fiber prepreg comprising the wet heat resistant resin composition and a fiber reinforced sheet.
In the fiber prepreg of the present invention, the fiber-reinforced sheet may be a fiber-reinforced sheet commonly used in the art, and the fiber-reinforced sheet is preferably a unidirectional fiber sheet or a fiber fabric sheet.
In the fiber prepreg of the present invention, the fiber material is not particularly limited, and various fiber materials commonly used in the art, such as carbon fiber, and the like, may be used.
The method for producing the fiber prepreg is not particularly limited, and may be any of various methods commonly used in the art, such as impregnating a fiber-reinforced sheet with a resin composition. The equipment used is also equipment in the prepreg processing in the prior art.
The preparation of the fiber prepreg according to the invention may comprise: the moisture-heat resistant composition of the invention is used for preparing a hot melt resin film by a hot melt film coater; and respectively placing the hot-melt resin films on an upper unreeling station and a lower unreeling station of a hot-melt pre-dipping machine, carrying out hot-roll compounding on the hot-melt resin films and the to-be-pre-dipped fibers led out from a creel, forming a sandwich structure with the resin films at the upper layer and the lower layer and fiber tows arranged in parallel at the middle layer, and then completing the dipping of the moisture-heat resistant resin composition on the fibers through heating, pressurizing and shaping and cooling, and obtaining the prepreg after reeling.
It is a fourth object of the present invention to provide a laminate obtained by curing the prepreg.
The curing process and curing conditions may be those commonly used in the art. The equipment used is also equipment in the processing of the laminated plate in the prior art.
Preferably, the curing temperature is 100 to 180 ℃.
The prepreg prepared from the resin composition has excellent damp-heat resistance, and the laminated board prepared from the prepreg has low damp-heat water absorption rate, and can still keep good mechanical property and heat resistance at high temperature after moisture absorption.
The moisture-heat resistant resin composition, the prepreg and the laminated board provided by the invention have the advantages that:
(1) Composite laminate T g The moisture absorption is saturated, and the moisture absorption is not obviously reduced in a drier state;
(2) The moisture and heat water absorption rate of the laminated board is less than 1.2%, and the laminated board has excellent mechanical properties in a high-temperature and humidity state.
By adopting the technical scheme of the invention, the resin composition has good impregnation effect on the reinforced fiber, wide material sources, simple preparation process, convenience for industrial production and better technical effect.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In the specific embodiment of the present invention, the raw materials are all commercially available.
[ example 1 ]
(1) 70g of 4,4 '-diaminodiphenylmethane epoxy resin (epoxy value: 0.85mol/100 g), 30g of bisphenol A-type benzoxazine resin, 29.5g of 4,4' -diaminodiphenylmethane (DDM), 5g of amino-modified silicone oil (number average molecular weight 2000, amino content: 6 to 7 wt%), and 1g of boron trifluoride ethylamine complex were charged into a three-necked flask, and the mixture was heated to 70℃under nitrogen atmosphere with stirring, so that the components were completely dissolved in each other, to obtain an epoxy resin composition.
(2) The epoxy resin composition after mixing was sampled for viscosity (measured by Brookfield CAP2000+H series cone plate viscometer, rotor model CAP-06, at 100 rpm).
(3) Adding the epoxy resin composition into a resin tank of a hot-melt film coating machine, uniformly coating the resin composition on release paper at a coating temperature of 70 ℃, cooling and rolling to obtain a hot-melt resin film, wherein the coating speed is 5 m/min.
(4) And (3) respectively placing two rolls of the resin film obtained in the step (3) on an upper unreeling station and a lower unreeling station of a hot-melt pre-dipping machine, carrying out unreeling, compositing the resin film with carbon fiber tows (Shanghai petrochemical SCF35 multiplied by 12 k) led out from a creel on a first heating roller to form a sandwich structure with the upper layer and the lower layer of the resin film and the middle layer of the resin film being carbon fiber tows arranged in parallel, and then completing the dipping of the resin on the carbon fibers through a first heating plate, a second heating roller, a second heating plate, a third heating roller, a third heating plate and a cooling plate, and reeling to obtain the prepreg. Specific process parameters of the pre-soaking machine are shown in the following table 1:
table 1 prepreg process parameters
(5) Cutting the prepreg obtained in the step (4), paving the cut prepreg in a mould, and then carrying out compression curing in a hot press. The curing procedure was 120 ℃/2h/0.6MPa+180 ℃/2h/0.6MPa, and the heating rate was 2 ℃/min.
The properties of the laminates were tested according to the following standard test and test methods, the test results are shown in Table 11.
A moisture absorption test method for a HB 7401 resin matrix composite laminate in a wet and hot environment;
ASTM D2344 fiber reinforced plastic short beam method for measuring interlaminar shear strength;
ASTM E1640-2013 Standard test method for determining glass transition temperature with dynamic mechanical analysis.
[ example 2 ]
(1) 70g of 4,4 '-diaminodiphenylmethane epoxy resin (epoxy value: 0.85mol/100 g), 30g of bisphenol A-type benzoxazine resin, 29.5g of 4,4' -diaminodiphenylmethane (DDM), 5g of epoxy-modified silicone oil (number average molecular weight: 4500, epoxy group content: 10-12 wt%), and 1g of boron trifluoride ethylamine complex were added to a three-necked flask, and the mixture was heated to 70℃under nitrogen atmosphere with stirring, so that the components were completely mutually dissolved to obtain an epoxy resin composition.
(2) The epoxy resin composition after mixing was sampled for viscosity (measured by Brookfield CAP2000+H series cone plate viscometer, rotor model CAP-06, at 100 rpm).
(3) Adding the epoxy resin composition into a resin tank of a hot-melt film coating machine, uniformly coating the resin composition on release paper at a coating temperature of 70 ℃, cooling and rolling to obtain a hot-melt resin film, wherein the coating speed is 5 m/min.
(4) And (3) respectively placing two rolls of the resin film obtained in the step (3) on an upper unreeling station and a lower unreeling station of a hot-melt pre-dipping machine, carrying out unreeling, compositing the resin film with carbon fiber tows (Shanghai petrochemical SCF35 multiplied by 12 k) led out from a creel on a first heating roller to form a sandwich structure with the upper layer and the lower layer of the resin film and the middle layer of the resin film being carbon fiber tows arranged in parallel, and then completing the dipping of the resin on the carbon fibers through a first heating plate, a second heating roller, a second heating plate, a third heating roller, a third heating plate and a cooling plate, and reeling to obtain the prepreg. Specific process parameters of the pre-soaking machine are shown in the following table 2:
table 2 prepreg process parameters
(5) Cutting the prepreg obtained in the step (4), paving the cut prepreg in a mould, and then carrying out compression curing in a hot press. The curing procedure was 120 ℃/2h/0.6MPa+180 ℃/2h/0.6MPa, and the heating rate was 2 ℃/min.
The performance of the laminate obtained was measured in the same manner as in example 1, and the measurement results are shown in Table 11.
[ example 3 ]
(1) 70g of 4,4 '-diaminodiphenylmethane epoxy resin (epoxy value: 0.85mol/100 g), 30g of bisphenol A-type benzoxazine resin, 29.5g of 4,4' -diaminodiphenylmethane (DDM), 5g of alcoholic hydroxyl group-modified silicone oil (number average molecular weight: 1500, hydroxyl group content: 8 to 9% by weight), and 1g of boron trifluoride ethylamine complex were added to a three-necked flask, and the mixture was heated to 70℃under nitrogen atmosphere with stirring, so that the components were completely dissolved in each other, to obtain an epoxy resin composition.
(2) The epoxy resin composition after mixing was sampled for viscosity (measured by Brookfield CAP2000+H series cone plate viscometer, rotor model CAP-06, at 100 rpm).
(3) Adding the epoxy resin composition into a resin tank of a hot-melt film coating machine, uniformly coating the resin composition on release paper at a coating temperature of 70 ℃, cooling and rolling to obtain a hot-melt resin film, wherein the coating speed is 5 m/min.
(4) And (3) respectively placing two rolls of the resin film obtained in the step (3) on an upper unreeling station and a lower unreeling station of a hot-melt pre-dipping machine, carrying out unreeling, compositing the resin film with carbon fiber tows (Shanghai petrochemical SCF35 multiplied by 12 k) led out from a creel on a first heating roller to form a sandwich structure with the upper layer and the lower layer of the resin film and the middle layer of the resin film being carbon fiber tows arranged in parallel, and then completing the dipping of the resin on the carbon fibers through a first heating plate, a second heating roller, a second heating plate, a third heating roller, a third heating plate and a cooling plate, and reeling to obtain the prepreg. Specific process parameters of the pre-soaking machine are shown in the following table 3:
table 3 prepreg process parameters
(5) Cutting the prepreg obtained in the step (4), paving the cut prepreg in a mould, and then carrying out compression curing in a hot press. The curing procedure was 120 ℃/2h/0.6MPa+180 ℃/2h/0.6MPa, and the heating rate was 2 ℃/min.
The performance of the laminate obtained was measured in the same manner as in example 1, and the measurement results are shown in Table 11.
[ example 4 ]
(1) 70g of 4,4' -diaminodiphenylmethane epoxy resin (epoxy value: 0.85mol/100 g), 30g of 4,4' -diaminodiphenylmethane benzoxazine resin, 29.5g of 4,4' -diaminodiphenylmethane (DDM), 5g of amino-modified silicone oil (number average molecular weight 2000, amino content: 6 to 7 wt%), and 1g of boron trifluoride ethylamine complex were charged into a three-necked flask, and the mixture was heated to 70℃under nitrogen atmosphere with stirring to completely dissolve the components with each other, to obtain an epoxy resin composition.
(2) The epoxy resin composition after mixing was sampled for viscosity (measured by Brookfield CAP2000+H series cone plate viscometer, rotor model CAP-06, at 100 rpm).
(3) Adding the epoxy resin composition into a resin tank of a hot-melt film coating machine, uniformly coating the resin composition on release paper at a coating temperature of 70 ℃, cooling and rolling to obtain a hot-melt resin film, wherein the coating speed is 5 m/min.
(4) And (3) respectively placing two rolls of the resin film obtained in the step (3) on an upper unreeling station and a lower unreeling station of a hot-melt pre-dipping machine, carrying out unreeling, compositing the resin film with carbon fiber tows (Shanghai petrochemical SCF35 multiplied by 12 k) led out from a creel on a first heating roller to form a sandwich structure with the upper layer and the lower layer of the resin film and the middle layer of the resin film being carbon fiber tows arranged in parallel, and then completing the dipping of the resin on the carbon fibers through a first heating plate, a second heating roller, a second heating plate, a third heating roller, a third heating plate and a cooling plate, and reeling to obtain the prepreg. The specific process parameters of the pre-soaking machine are shown in the following table 4:
table 4 prepreg process parameters
(5) Cutting the prepreg obtained in the step (4), paving the cut prepreg in a mould, and then carrying out compression curing in a hot press. The curing procedure was 120 ℃/2h/0.6MPa+180 ℃/2h/0.6MPa, and the heating rate was 2 ℃/min.
The performance of the laminate obtained was measured in the same manner as in example 1, and the measurement results are shown in Table 11.
[ example 5 ]
(1) 70g of 4,4' -diaminodiphenylmethane epoxy resin (epoxy value: 0.85mol/100 g), 30g of 4,4' -diaminodiphenylmethane type benzoxazine resin, 29.5g of 4,4' -diaminodiphenylmethane (DDM), 5g of epoxy-modified silicone oil (number average molecular weight: 4500, epoxy group content: 10-12% by weight), and 1g of boron trifluoride ethylamine complex were added to a three-necked flask, and the mixture was heated to 70℃under nitrogen atmosphere with stirring, so that the components were completely dissolved in each other, to obtain an epoxy resin composition.
(2) The epoxy resin composition after mixing was sampled for viscosity (measured by Brookfield CAP2000+H series cone plate viscometer, rotor model CAP-06, at 100 rpm).
(3) Adding the epoxy resin composition into a resin tank of a hot-melt film coating machine, uniformly coating the resin composition on release paper at a coating temperature of 70 ℃, cooling and rolling to obtain a hot-melt resin film, wherein the coating speed is 5 m/min.
(4) And (3) respectively placing two rolls of the resin film obtained in the step (3) on an upper unreeling station and a lower unreeling station of a hot-melt pre-dipping machine, carrying out unreeling, compositing the resin film with carbon fiber tows (Shanghai petrochemical SCF35 multiplied by 12 k) led out from a creel on a first heating roller to form a sandwich structure with the upper layer and the lower layer of the resin film and the middle layer of the resin film being carbon fiber tows arranged in parallel, and then completing the dipping of the resin on the carbon fibers through a first heating plate, a second heating roller, a second heating plate, a third heating roller, a third heating plate and a cooling plate, and reeling to obtain the prepreg. The prepreg machine specific process parameters are shown in table 5 below:
table 5 prepreg process parameters
(5) Cutting the prepreg obtained in the step (4), paving the cut prepreg in a mould, and then carrying out compression curing in a hot press. The curing procedure was 120 ℃/2h/0.6MPa+180 ℃/2h/0.6MPa, and the heating rate was 2 ℃/min.
The performance of the laminate obtained was measured in the same manner as in example 1, and the measurement results are shown in Table 11.
[ example 6 ]
(1) 70g of 4,4' -diaminodiphenylmethane epoxy resin (epoxy value: 0.85mol/100 g), 30g of 4,4' -diaminodiphenylmethane type benzoxazine resin, 29.5g of 4,4' -diaminodiphenylmethane (DDM), 5g of alcoholic hydroxyl group-modified silicone oil (number average molecular weight: 1500, hydroxyl group content: 8 to 9% by weight), and 1g of boron trifluoride ethylamine complex were charged into a three-necked flask, and the mixture was heated to 70℃under nitrogen atmosphere with stirring, so that the respective components were completely dissolved in each other, to obtain an epoxy resin composition.
(2) The epoxy resin composition after mixing was sampled for viscosity (measured by Brookfield CAP2000+H series cone plate viscometer, rotor model CAP-06, at 100 rpm).
(3) Adding the epoxy resin composition into a resin tank of a hot-melt film coating machine, uniformly coating the resin composition on release paper at a coating temperature of 70 ℃, cooling and rolling to obtain a hot-melt resin film, wherein the coating speed is 5 m/min.
(4) And (3) respectively placing two rolls of the resin film obtained in the step (3) on an upper unreeling station and a lower unreeling station of a hot-melt pre-dipping machine, carrying out unreeling, compositing the resin film with carbon fiber tows (Shanghai petrochemical SCF35 multiplied by 12 k) led out from a creel on a first heating roller to form a sandwich structure with the upper layer and the lower layer of the resin film and the middle layer of the resin film being carbon fiber tows arranged in parallel, and then completing the dipping of the resin on the carbon fibers through a first heating plate, a second heating roller, a second heating plate, a third heating roller, a third heating plate and a cooling plate, and reeling to obtain the prepreg. Specific process parameters of the pre-soaking machine are shown in the following table 6:
table 6 prepreg process parameters
(5) Cutting the prepreg obtained in the step (4), paving the cut prepreg in a mould, and then carrying out compression curing in a hot press. The curing procedure was 120 ℃/2h/0.6MPa+180 ℃/2h/0.6MPa, and the heating rate was 2 ℃/min.
The performance of the laminate obtained was measured in the same manner as in example 1, and the measurement results are shown in Table 11.
[ example 7 ]
(1) 50g of 4,4 '-diaminodiphenylmethane epoxy resin (epoxy value: 0.85mol/100 g), 50g of bisphenol A-type benzoxazine resin, 21.1g of 4,4' -diaminodiphenylmethane (DDM), 8g of amino-modified silicone oil (number average molecular weight 2000, amino content: 6 to 7% by weight), and 1g of boron trifluoride ethylamine complex were charged into a three-necked flask, and the mixture was heated to 70℃under nitrogen atmosphere with stirring, so that the components were completely dissolved in each other, to obtain an epoxy resin composition.
(2) The epoxy resin composition after mixing was sampled for viscosity (measured by Brookfield CAP2000+H series cone plate viscometer, rotor model CAP-06, at 100 rpm).
(3) Adding the epoxy resin composition into a resin tank of a hot-melt film coating machine, uniformly coating the resin composition on release paper at a coating temperature of 70 ℃, cooling and rolling to obtain a hot-melt resin film, wherein the coating speed is 5 m/min.
(4) And (3) respectively placing two rolls of the resin film obtained in the step (3) on an upper unreeling station and a lower unreeling station of a hot-melt pre-dipping machine, carrying out unreeling, compositing the resin film with carbon fiber tows (Shanghai petrochemical SCF35 multiplied by 12 k) led out from a creel on a first heating roller to form a sandwich structure with the upper layer and the lower layer of the resin film and the middle layer of the resin film being carbon fiber tows arranged in parallel, and then completing the dipping of the resin on the carbon fibers through a first heating plate, a second heating roller, a second heating plate, a third heating roller, a third heating plate and a cooling plate, and reeling to obtain the prepreg. Specific process parameters of the pre-impregnator are shown in the following table 7:
table 7 prepreg process parameters
(5) Cutting the prepreg obtained in the step (4), paving the cut prepreg in a mould, and then carrying out compression curing in a hot press. The curing procedure was 120 ℃/2h/0.6MPa+180 ℃/2h/0.6MPa, and the heating rate was 2 ℃/min.
The performance of the laminate obtained was measured in the same manner as in example 1, and the measurement results are shown in Table 11.
[ comparative example 1 ]
(1) 70g of 4,4 '-diaminodiphenylmethane epoxy resin (epoxy value: 0.85mol/100 g), 29.5g of 4,4' -diaminodiphenylmethane (DDM) and 1g of boron trifluoride ethylamine complex were charged into a three-necked flask, and the mixture was heated to 70℃under nitrogen with stirring to completely dissolve the components with each other, to obtain an epoxy resin composition.
(2) The epoxy resin composition after mixing was sampled for viscosity (measured by Brookfield CAP2000+H series cone plate viscometer, rotor model CAP-06, at 100 rpm).
(3) Adding the epoxy resin composition into a resin tank of a hot-melt film coating machine, uniformly coating the resin composition on release paper at a coating temperature of 70 ℃, cooling and rolling to obtain a hot-melt resin film, wherein the coating speed is 5 m/min.
(4) And (3) respectively placing two rolls of the resin film obtained in the step (3) on an upper unreeling station and a lower unreeling station of a hot-melt pre-dipping machine, carrying out unreeling, compositing the resin film with carbon fiber tows (Shanghai petrochemical SCF35 multiplied by 12 k) led out from a creel on a first heating roller to form a sandwich structure with the upper layer and the lower layer of the resin film and the middle layer of the resin film being carbon fiber tows arranged in parallel, and then completing the dipping of the resin on the carbon fibers through a first heating plate, a second heating roller, a second heating plate, a third heating roller, a third heating plate and a cooling plate, and reeling to obtain the prepreg. The prepreg machine specific process parameters are shown in table 8 below:
table 8 prepreg process parameters
(5) Cutting the prepreg obtained in the step (4), paving the cut prepreg in a mould, and then carrying out compression curing in a hot press. The curing procedure was 120 ℃/2h/0.6MPa+180 ℃/2h/0.6MPa, and the heating rate was 2 ℃/min.
The performance of the laminate obtained was measured in the same manner as in example 1, and the measurement results are shown in Table 11.
[ comparative example 2 ]
(1) 70g of 4,4' -diaminodiphenylmethane epoxy resin (epoxy value: 0.85mol/100 g), 30g of 4,4' -diaminodiphenylmethane benzoxazine resin, 29.5g of 4,4' -diaminodiphenylmethane (DDM) and 1g of boron trifluoride ethylamine complex were added to a three-necked flask, and the temperature was raised to 70℃under nitrogen with stirring, so that the components were completely mutually dissolved to obtain an epoxy resin composition.
(2) The epoxy resin composition after mixing was sampled for viscosity (measured by Brookfield CAP2000+H series cone plate viscometer, rotor model CAP-06, at 100 rpm).
(3) Adding the epoxy resin composition into a resin tank of a hot-melt film coating machine, uniformly coating the resin composition on release paper at a coating temperature of 70 ℃, cooling and rolling to obtain a hot-melt resin film, wherein the coating speed is 5 m/min.
(4) And (3) respectively placing two rolls of the resin film obtained in the step (3) on an upper unreeling station and a lower unreeling station of a hot-melt pre-dipping machine, carrying out unreeling, compositing the resin film with carbon fiber tows (Shanghai petrochemical SCF35 multiplied by 12 k) led out from a creel on a first heating roller to form a sandwich structure with the upper layer and the lower layer of the resin film and the middle layer of the resin film being carbon fiber tows arranged in parallel, and then completing the dipping of the resin on the carbon fibers through a first heating plate, a second heating roller, a second heating plate, a third heating roller, a third heating plate and a cooling plate, and reeling to obtain the prepreg. Specific process parameters of the pre-impregnator are shown in the following table 9:
table 9 prepreg process parameters
(5) Cutting the prepreg obtained in the step (4), paving the cut prepreg in a mould, and then carrying out compression curing in a hot press. The curing procedure was 120 ℃/2h/0.6MPa+180 ℃/2h/0.6MPa, and the heating rate was 2 ℃/min.
The performance of the laminate obtained was measured in the same manner as in example 1, and the measurement results are shown in Table 11.
[ comparative example 3 ]
(1) 70g of 4,4 '-diaminodiphenylmethane epoxy resin (epoxy value: 0.85mol/100 g), 29.5g of 4,4' -diaminodiphenylmethane (DDM), 5g of epoxy-modified silicone oil (number average molecular weight: 4500, epoxy group content: 10% to 12%), and 1g of boron trifluoride ethylamine complex were charged into a three-necked flask, and the mixture was heated to 70℃under stirring under nitrogen atmosphere, so that the components were completely dissolved in each other, to obtain an epoxy resin composition.
(2) The epoxy resin composition after mixing was sampled for viscosity (measured by Brookfield CAP2000+H series cone plate viscometer, rotor model CAP-06, at 100 rpm).
(3) Adding the epoxy resin composition into a resin tank of a hot-melt film coating machine, uniformly coating the resin composition on release paper at a coating temperature of 70 ℃, cooling and rolling to obtain a hot-melt resin film, wherein the coating speed is 5 m/min.
(4) And (3) respectively placing two rolls of the resin film obtained in the step (3) on an upper unreeling station and a lower unreeling station of a hot-melt pre-dipping machine, carrying out unreeling, compositing the resin film with carbon fiber tows (Shanghai petrochemical SCF35 multiplied by 12 k) led out from a creel on a first heating roller to form a sandwich structure with the upper layer and the lower layer of the resin film and the middle layer of the resin film being carbon fiber tows arranged in parallel, and then completing the dipping of the resin on the carbon fibers through a first heating plate, a second heating roller, a second heating plate, a third heating roller, a third heating plate and a cooling plate, and reeling to obtain the prepreg. The prepreg machine specific process parameters are shown in table 10 below:
table 10 prepreg process parameters
(5) Cutting the prepreg obtained in the step (4), paving the cut prepreg in a mould, and then carrying out compression curing in a hot press. The curing procedure was 120 ℃/2h/0.6MPa+180 ℃/2h/0.6MPa, and the heating rate was 2 ℃/min.
The test method for the performance of the obtained laminated board is the same as in example 1, and the test results are shown in Table 11.
Table 11 laminate properties
Claims (10)
1. A moisture-heat resistant resin composition consists of the following blended components in parts by weight:
40-80 parts of epoxy resin;
10-50 parts of benzoxazine resin;
0.1-10 parts of modified silicone oil;
10-80 parts of a curing agent;
0.1-5 parts of an accelerator;
the benzoxazine resin is at least one selected from bisphenol A type benzoxazine resin, dicyclopentadiene type benzoxazine resin, bisphenol F type benzoxazine resin, phenolphthalein type benzoxazine resin and 4,4' -diaminodiphenylmethane type benzoxazine; the molecular weight of the modified silicone oil is 500-20000, and the content of the modified groups is 2-30wt%; the modified silicone oil is at least one selected from amino modified silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, alcohol modified silicone oil, phenol modified silicone oil, mercapto modified silicone oil, acryloxy modified silicone oil, methacryloxy modified silicone oil, methyl long-chain alkyl silicone oil, methyl trifluoropropyl silicone oil and polyether modified silicone oil.
2. The moisture-heat resistant resin composition according to claim 1, wherein:
40-70 parts of epoxy resin;
10-40 parts of benzoxazine resin;
0.1-5 parts of modified silicone oil;
20-70 parts of a curing agent;
0.1-2 parts of an accelerator.
3. The moisture-heat resistant resin composition according to claim 1, wherein:
the epoxy resin is at least one of glycidyl ether epoxy resin, glycidyl ester epoxy resin and glycidyl amino epoxy resin.
4. The moisture-heat resistant resin composition according to claim 3, wherein:
the epoxy resin is at least one selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, glycidyl ester type epoxy resin and glycidyl amine type epoxy resin.
5. The moisture-heat resistant resin composition according to claim 1, wherein:
the molecular weight of the modified silicone oil is 1000-10000; the content of the modifying group is 5-20wt%.
6. The wet heat resistant resin composition according to any one of claims 1 to 5, wherein:
the curing agent is at least one selected from aromatic amine, aliphatic amine, alicyclic amine, imide, aromatic anhydride, alicyclic anhydride, aliphatic anhydride and halogen-containing anhydride; and/or the number of the groups of groups,
the accelerator is at least one selected from quaternary ammonium salt, tertiary amine, triphenylphosphine, quaternary phosphonium salt, imidazole, boron trifluoride and complex thereof.
7. A method for producing the moisture-heat resistant resin composition according to any one of claims 1 to 6, characterized by comprising the steps of: mixing the components in the amounts; the mixing temperature is 20-100 ℃.
8. A fibrous prepreg comprising the wet heat resistant resin composition according to any one of claims 1 to 6 and a fibrous reinforcing sheet.
9. The fibrous prepreg of claim 8, wherein:
the fiber reinforcement sheet is a unidirectional fiber sheet or a fiber fabric sheet.
10. A laminate, characterized in that it is obtained by curing the fibrous prepreg according to claim 8 or 9.
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