CN116003957A - Resin composition and resin material for resin transfer molding process - Google Patents
Resin composition and resin material for resin transfer molding process Download PDFInfo
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- CN116003957A CN116003957A CN202111231882.9A CN202111231882A CN116003957A CN 116003957 A CN116003957 A CN 116003957A CN 202111231882 A CN202111231882 A CN 202111231882A CN 116003957 A CN116003957 A CN 116003957A
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Abstract
The invention provides a resin composition and a resin material for a resin transfer molding process, wherein the resin composition comprises the following components in parts by weight: 10-80 parts of benzoxazine resin; 10-80 parts of bismaleimide resin; 10-80 parts of reactive diluent, wherein the reactive diluent comprises at least one compound with a structure shown in a formula (1). The invention provides a resin composition, which has the advantages that: (1) The viscosity is low at the injection temperature (90 ℃), the pot life is long, and the storage period is long; (2) The cured resin has no bubbles, no defects, and low shrinkage. (3) Resin cured product T g High mechanical property.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a resin composition and a resin material for a resin transfer molding process.
Background
Resin Transfer Moulding (RTM) is a closed moulding technique in which a preform of reinforcing material is placed in a moulding cavity, resin which has been mixed with a curing agent is injected into the cavity and allowed to flow in the preform within the cavity, the preform is impregnated and the resin is then cured by a cross-linking reaction at a temperature to give a composite article. The RTM molding process has high process requirements for matrix resins, both low viscosity and long pot life of the resin during injection and fast reaction rate during curing, and the reaction temperature is as low as possible, with no or little volatile by-products being evolved during curing.
Benzoxazine resin (BOZ) is a thermosetting resin containing O, N six-membered heterocycle, and has low melt viscosity. Long pot life, low curing shrinkage, no release of small molecules during curing, and the like, and is particularly suitable for RTM molding technology. However, it is pointed out in the literature that the presence of volatile components in the RTM molding process can cause defects such as bubbles in the resin, which can affect the properties of the composite material.
The polymerization of bismaleimide resins (BMI) is typically a double bond addition polymerization that causes some cure shrinkage that affects material properties. The shrinkage performance of the modified BMI cured product is a prominent feature of this resin system because the BOZ resin has no shrinkage or slight expansion after curing due to the hydrogen bonding of itself. In addition, the BOZ modified BMI resin has good mechanical property, the bending strength is between 120 and 150MPa, and the tensile elongation tends to be larger along with the increase of the content of the BOZ resin, which indicates that the BOZ resin improves the toughness of the blend resin. DMA tests showed that the BMI content increased and the Tg of the cured blend resin increased from 203 ℃ to 257 ℃ with an increase in the retention of high temperature modulus.
The most critical process properties affecting RTM resins are viscosity and pot life. The invention develops the benzoxazine-bismaleimide resin with low viscosity and long pot life, and solves the problems of bubbles in a resin cured product and high shrinkage rate.
Disclosure of Invention
In view of the above problems in the prior art, it is an object of the present invention to provide a resin composition having low viscosity at injection temperature, long pot life, no bubbles, small shrinkage, and excellent thermal and mechanical properties, which can be used in an RTM molding process for preparing RTM products.
The second object of the present invention is to provide a use of a resin composition corresponding to one of the objects as a raw material for a resin material in a resin transfer molding process.
A third object of the present invention is to provide a resin material for a resin transfer molding process corresponding to the above object.
A fourth object of the present invention is to provide an application of a resin material corresponding to the above object as a resin material applied to a resin transfer molding process.
In order to achieve one of the above purposes, the technical scheme adopted by the invention is as follows:
the resin composition comprises the following components in parts by weight:
10-80 parts of benzoxazine resin, preferably 20-70 parts;
10-80 parts of bismaleimide resin, preferably 20-60 parts;
10 to 80 parts, preferably 20 to 60 parts,
wherein the reactive diluent comprises at least one of the compounds with the structure shown in the formula (1):
in the formula (1), R 1 Selected from the group consisting of substitutionPhenyl substituted or unsubstituted by a substituent, naphthyl substituted or unsubstituted by a substituent and C 1 -C 12 Wherein the substitution means that hydrogen on the aromatic ring is substituted with a substituent selected from the group consisting of C 1 -C 6 Is a hydrocarbon group of (2);
R 2 selected from H and C 1 -C 12 At least one of the hydrocarbon groups of (a).
In some preferred embodiments of the present invention, the resin composition comprises the following components in parts by weight:
30-50 parts of benzoxazine resin;
5-20 parts of bismaleimide resin;
10-40 parts of reactive diluent.
In some preferred embodiments of the present invention, the resin composition comprises the following components in parts by weight:
35-45 parts of benzoxazine resin;
5-20 parts of bismaleimide resin;
15-35 parts of reactive diluent.
In some preferred embodiments of the present invention, the resin composition comprises the following components in parts by weight:
40 parts of benzoxazine resin;
5-20 parts of bismaleimide resin;
15-35 parts of reactive diluent.
In some preferred embodiments of the present invention, the resin composition comprises the following components in parts by weight:
40 parts of benzoxazine resin;
10-15 parts of bismaleimide resin;
20-30 parts of reactive diluent.
In some preferred embodiments of the invention, the substituents are selected from C 1 -C 6 Alkyl, C of (2) 2 -C 6 Alkenyl and C of (C) 2 -C 6 At least one of the alkynyl groups of (a).
In some preferred embodiments of the invention, the substituents are selected from C 1 -C 6 Straight chain alkyl, C 2 -C 6 Straight chain alkenyl and C 2 -C 6 At least one of the straight chain alkynyl groups of (a).
In some preferred embodiments of the invention, the substituents are selected from C 1 -C 4 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl and C 2 -C 4 At least one of the straight chain alkynyl groups of (a).
In some preferred embodiments of the invention, the substituents are selected from C 2 -C 4 At least one of the straight chain alkynyl groups of (a).
In some preferred embodiments of the invention, in formula (1), R 1 Selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, and C 1 -C 6 At least one of the hydrocarbon groups of (a).
In some preferred embodiments of the invention, in formula (1), R 1 Selected from substituted or unsubstituted phenyl, C 1 -C 6 Alkyl, C of (2) 2 -C 6 Alkenyl and C of (C) 2 -C 6 At least one of the alkynyl groups of (a).
In some preferred embodiments of the invention, in formula (1), R 1 Selected from substituted or unsubstituted phenyl, C 1 -C 6 Straight chain alkyl, C 2 -C 6 Straight chain alkenyl and C 2 -C 6 At least one of the straight chain alkynyl groups of (a).
In some preferred embodiments of the invention, in formula (1), R 1 Selected from substituted or unsubstituted phenyl, C 1 -C 4 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl and C 2 -C 4 At least one of the straight chain alkynyl groups of (a).
In some preferred embodiments of the invention, in formula (1), R 1 Selected from substituents substituted or unsubstitutedSubstituted phenyl and C 2 -C 4 At least one of the straight chain alkynyl groups of (a).
In some preferred embodiments of the invention, in formula (1), R 2 Selected from H and C 1 -C 6 At least one of the hydrocarbon groups of (a).
In some preferred embodiments of the invention, in formula (1), R 2 Selected from H, C 1 -C 6 Alkyl, C of (2) 2 -C 6 Alkenyl and C of (C) 2 -C 6 At least one of the alkynyl groups of (a).
In some preferred embodiments of the invention, in formula (1), R 2 Selected from H, C 1 -C 6 Straight chain alkyl, C 2 -C 6 Straight chain alkenyl and C 2 -C 6 At least one of the straight chain alkynyl groups of (a).
In some preferred embodiments of the invention, in formula (1), R 2 Selected from H, C 1 -C 4 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl and C 2 -C 4 At least one of the straight chain alkynyl groups of (a).
In some preferred embodiments of the invention, in formula (1), R 2 Selected from H and C 2 -C 4 At least one of the straight chain alkynyl groups of (a).
In some preferred embodiments of the invention, the reactive diluent is selected from monofunctional benzoxazines.
According to the present invention, the term monofunctional in the monofunctional benzoxazine is selected from at least one of hydroxyl, carboxyl, allyl, alkenyl, alkynyl and amino.
In some preferred embodiments of the invention, the reactive diluent is selected from monofunctional benzoxazines with alkynyl or allyl groups.
In some preferred embodiments of the present invention, the reactive diluent is selected from at least one of 3-ethynylaniline-phenol type benzoxazine (PH-apa), 2-allylphenol-aniline type benzoxazine (P-alp) and allylamine-phenol type benzoxazine (P-ala).
According to the present invention, the structural formula of the above-mentioned reactive diluent is shown below.
According to the present invention, the benzoxazine resin may be a benzoxazine resin commonly used in the art.
In some preferred embodiments of the present invention, the benzoxazine resin is selected from at least one of a diphenylmethane diamine-phenol type benzoxazine resin (MDA-BOZ), a diphenylmethane diamine-p-cresol type benzoxazine resin (MDA-pBOZ), a diphenylether diamine-phenol type benzoxazine resin (PH-BOZ), a bisphenol a-aniline type benzoxazine resin (BA-BOZ), a bisphenol F-aniline type benzoxazine resin (BF-BOZ), and a bisphenol S-aniline type benzoxazine resin (BS-BOZ).
According to the present invention, the structural formula of the above-mentioned benzoxazine resin is shown below.
According to the present invention, the bismaleimide resin may be a benzoxazine resin commonly used in the art.
In some preferred embodiments of the present invention, the bismaleimide resin is selected from at least one of para-phenylene diamine type bismaleimide (HQ-BMI), meta-phenylene diamine type bismaleimide (RS-BMI), diphenylmethane diamine type bismaleimide (MDA-BMI), diphenyl ether type bismaleimide (PH-BMI), diphenyl sulfone type bismaleimide (BS-BMI), diphenyl bisphenol a type bismaleimide (BAP-BMI), diphenyl ether type bismaleimide (BSP-BMI).
According to the present invention, the structural formula of the above-mentioned benzoxazine resin is shown below.
In some preferred embodiments of the present invention, the viscosity of the resin composition at 90℃is 200 to 500 mPas, preferably 200 to 450 mPas.
According to the present invention, it is understood that various auxiliary agents commonly used in the art, such as defoamer, internal lubricant, etc., may be added to the resin composition according to the processing requirements, and the amounts thereof may be conventional amounts, or may be adjusted according to the actual requirements.
In order to achieve the second purpose, the technical scheme adopted by the invention is as follows:
use of the resin composition according to any one of the above embodiments as a raw material for a resin material in a resin transfer molding process.
In order to achieve the third purpose, the technical scheme adopted by the invention is as follows:
a resin material for a resin transfer molding process, comprising: a heat-cured product of a melt containing the resin composition of any of the above embodiments.
In some preferred embodiments of the present invention, a raw material containing the resin composition according to any one of the above embodiments is subjected to a heat treatment to obtain the melt, wherein the heat treatment conditions include: the temperature is 90-140 ℃ and the time is 10-60 min.
According to the present invention, the heat treatment may be performed under nitrogen gas.
In some preferred embodiments of the present invention, the melt is subjected to a heat curing treatment to obtain the heat-cured product, wherein the heat curing treatment conditions include: the temperature is 130-220 ℃ and the time is 0.5-8 h.
In some preferred embodiments of the invention, the resin material has a viscosity doubling time of 160-250 min at 90 ℃; the shrinkage is 0.70% -1.2%; the tensile strength is 75-100 MPa; young's modulus of 4500-5000 MPa; storage modulus inflection point temperature T g 180-250 ℃.
According to the present invention, the process of mixing, curing, etc. the resin composition may employ a thermosetting resin processing process commonly used in the art. The equipment used is also equipment commonly used in the processing of thermosetting resins in the prior art.
In order to achieve the fourth purpose, the technical scheme adopted by the invention is as follows:
the use of a resin material as described in any one of the above embodiments as a resin material for use in a resin transfer molding process.
According to the present invention, in correspondence with the fourth object, a resin transfer molded article made of the resin material provided by the present invention is also within the scope of the present invention.
The resin composition and the resin material (namely the resin condensate) for the resin transfer molding process have the following beneficial effects:
(1) The viscosity is low at the injection temperature (90 ℃), the pot life is long, and the storage period is long.
(2) The cured resin has no bubbles, no defects, and low shrinkage.
(3) Resin cured product T g High mechanical property.
(4) The resin composition has good impregnation effect on the reinforced fibers, wide material sources, simple preparation process, convenient industrial production and good technical effect.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the following description.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products available commercially without the manufacturer's knowledge.
The raw materials used in the following embodiments are all commercially available.
Example 1
(1) 40g of MDA-BOZ, 20g of PH-apa and 10g of MDA-BMI are added into a three-necked flask, and the temperature is raised to 100 ℃ under the protection of nitrogen while stirring, so that all the components are completely mutually dissolved. The mixed resin composition was sampled for viscosity (measured by Brookfield CAP2000+H series cone-plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the mixed resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The viscosity of the sample is measured by Brookfield CAP2000+H series cone plate viscosimeter, and the pot life is the doubling time of the viscosity at 90 ℃. The resin cure shrinkage was tested and performed in accordance with ISO 3521 standard. The resin bars were tested for tensile strength and Young's modulus, as performed with reference to GBT 2568-1995 standard. T (T) g Is determined by the storage modulus inflection point temperature measured by dynamic thermo-mechanical analysis (DMA).
Example 2
(1) 40g of MDA-BOZ, 30g of PH-apa and 10MDA-BMI are added into a three-necked flask, and the temperature is raised to 100 ℃ under the protection of nitrogen while stirring, so that all the components are completely mutually dissolved. The mixed resin composition was sampled for viscosity (measured by Brookfield CAP2000+H series cone-plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the mixed resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The method for testing the properties of the resin was the same as in example 1.
Example 3
(1) 40g of MDA-pBOZ, 20-g P-alp and 10g of HQ-BMI were put into a three-necked flask, and the temperature was raised to 100℃under nitrogen protection with stirring, so that the respective components were completely dissolved in each other. The mixed resin composition was sampled for viscosity (measured by Brookfield CAP2000+H series cone-plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the mixed resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The method for testing the properties of the resin was the same as in example 1.
Example 4
(1) 40g of PH-pBOZ, 20g P-alp and 10g of PH-BMI were put into a three-necked flask, and the temperature was raised to 100℃under nitrogen protection with stirring, so that the respective components were completely dissolved in each other. The mixed resin composition was sampled for viscosity (measured by Brookfield CAP2000+H series cone-plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the mixed resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The method for testing the properties of the resin was the same as in example 1.
Example 5
(1) 40g of BA-BOZ, 20g P-ala and 15g of BAP-BMI were added to a three-necked flask and the temperature was raised to 100℃under nitrogen with stirring to allow complete mutual dissolution of the components. The mixed resin composition was sampled for viscosity (measured by Brookfield CAP2000+H series cone-plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the mixed resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The method for testing the properties of the resin was the same as in example 1.
Example 6
(1) 40g of BF-BOZ, 20g of g P-ala and 15g of BS-BMI are added into a three-necked flask, and the temperature is raised to 100 ℃ under the protection of nitrogen while stirring, so that all the components are completely mutually dissolved. The mixed resin composition was sampled for viscosity (measured by Brookfield CAP2000+H series cone-plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the mixed resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The method for testing the properties of the resin was the same as in example 1.
Example 7
(1) 40g of MDA-BOZ, 30g of PH-apa and 10MDA-BMI are added into a three-necked flask, and the temperature is raised to 100 ℃ under the protection of nitrogen while stirring, so that all the components are completely mutually dissolved. The mixed resin composition was sampled for viscosity (measured by Brookfield CAP2000+H series cone-plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the mixed resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The method for testing the properties of the resin was the same as in example 1.
Example 8
(1) 10g of MDA-BOZ, 20g of PH-apa and 40MDA-BMI are added into a three-neck flask, and the temperature is raised to 100 ℃ under the protection of nitrogen while stirring, so that all the components are completely mutually dissolved. The mixed resin composition was sampled for viscosity (measured by Brookfield CAP2000+H series cone-plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the mixed resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The method for testing the properties of the resin was the same as in example 1.
Example 9
(1) 10g of MDA-BOZ, 40g of PH-apa and 20MDA-BMI are added into a three-necked flask, and the temperature is raised to 100 ℃ under the protection of nitrogen while stirring, so that all the components are completely mutually dissolved. The mixed resin composition was sampled for viscosity (measured by Brookfield CAP2000+H series cone-plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the mixed resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The method for testing the properties of the resin was the same as in example 1.
Example 10
(1) 25g of MDA-BOZ, 25g of PH-apa and 25g of MDA-BMI are added into a three-necked flask, and the temperature is raised to 100 ℃ under the protection of nitrogen while stirring, so that all the components are completely mutually dissolved. The mixed resin composition was sampled for viscosity (measured by Brookfield CAP2000+H series cone-plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the mixed resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The method for testing the properties of the resin was the same as in example 1.
Comparative example 1
(1) 100g of BA-BOZ was added to a three-necked flask and the temperature was raised to 100℃under nitrogen with stirring. The resin was sampled for viscosity (measured by Brookfield CAP2000+H series cone plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The method for testing the properties of the resin was the same as in example 1.
Comparative example 2
(1) 100g P-ala was added to a three-necked flask and the temperature was raised to 80℃under nitrogen with stirring. The resin was sampled for viscosity (measured by Brookfield CAP2000+H series cone plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The method for testing the properties of the resin was the same as in example 1.
Comparative example 3
(1) 100MDA-BMI, 50g of 2,2' -diallyl bisphenol A and 20g of 2-allyl phenol are added into a three-neck flask, and the temperature is raised to 100 ℃ under the protection of nitrogen while stirring, so that all the components are completely mutually dissolved. The mixed resin composition was sampled for viscosity (measured by Brookfield CAP2000+H series cone-plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the mixed resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The method for testing the properties of the resin was the same as in example 1.
Comparative example 4
(1) 40g of MDA-BOZ and 20g of PH-apa are added into a three-necked flask, and the temperature is raised to 100 ℃ under the protection of nitrogen while stirring, so that all the components are completely mutually dissolved. The mixed resin composition was sampled for viscosity (measured by Brookfield CAP2000+H series cone-plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the mixed resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The method for testing the properties of the resin was the same as in example 1.
Comparative example 5
(1) 20g P-alp and 40g MDA-BMI were added to a three-necked flask and heated to 100deg.C under nitrogen with stirring to allow complete miscibility of the components. The mixed resin composition was sampled for viscosity (measured by Brookfield CAP2000+H series cone-plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the mixed resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The method for testing the properties of the resin was the same as in example 1.
Comparative example 6
(1) 40g of MDA-BOZ, 20g of 2-allylphenol and 10g of MDA-BMI are added into a three-necked flask, and the temperature is raised to 100 ℃ under the protection of nitrogen while stirring, so that all the components are completely mutually dissolved. The mixed resin composition was sampled for viscosity (measured by Brookfield CAP2000+H series cone-plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the mixed resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The method for testing the properties of the resin was the same as in example 1.
Comparative example 7
(1) 55g of MDA-BOZ and 25MDA-BMI were added to a three-necked flask, and the temperature was raised to 100℃under nitrogen protection with stirring, so that the respective components were completely mutually dissolved. The mixed resin composition was sampled for viscosity (measured by Brookfield CAP2000+H series cone-plate viscometer, rotor model CAP-06, at 100 rpm).
(2) Pouring the mixed resin into a preheated mold, placing the mold into a blast oven, and performing heat curing according to a curing process of 160 ℃/2h+180 ℃/2h+200 ℃/2 h. After it cooled to room temperature, the resin bars in the mold were removed.
(3) The method for testing the properties of the resin was the same as in example 1.
The test results of the above examples and comparative examples are shown in table 1 below.
TABLE 1
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (10)
1. The resin composition comprises the following components in parts by weight:
10-80 parts of benzoxazine resin, preferably 20-70 parts;
10-80 parts of bismaleimide resin, preferably 20-60 parts;
10 to 80 parts, preferably 20 to 60 parts,
wherein the reactive diluent comprises at least one of the compounds with the structure shown in the formula (1):
in the formula (1), R 1 Selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, and C 1 -C 12 Wherein the substitution means that hydrogen on the aromatic ring is substituted with a substituent selected from the group consisting of C 1 -C 6 At least one hydrocarbon group of (2), preferably selected from C 1 -C 6 Alkyl, C of (2) 2 -C 6 Alkenyl and C of (C) 2 -C 6 At least one, preferably C, of the alkynyl groups of (C) 1 -C 6 Straight chain alkyl, C 2 -C 6 Straight chain alkenyl and C 2 -C 6 At least one, more preferably C, of the linear alkynyl groups of (C) 1 -C 4 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl and C 2 -C 4 At least one of the straight chain alkynyl groups of (2), more preferably C 2 -C 4 At least one of the straight chain alkynyl groups;
R 2 selected from H and C 1 -C 12 At least one of the hydrocarbon groups of (a).
2. The resin composition according to claim 1, wherein in the formula (1), R 1 Selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, and C 1 -C 6 At least one of the hydrocarbon groups of (C) is preferably a phenyl group, C which is substituted or unsubstituted with a substituent 1 -C 6 Alkyl, C of (2) 2 -C 6 Alkenyl and C of (C) 2 -C 6 More preferably phenyl, C, substituted or unsubstituted with a substituent 1 -C 6 Straight chain alkyl, C 2 -C 6 Straight chain alkenyl and C 2 -C 6 Further preferably a phenyl group, C, substituted or unsubstituted by a substituent 1 -C 4 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl and C 2 -C 4 More preferably at least one of a straight chain alkynyl group of (C), a phenyl group substituted or unsubstituted with a substituent and C 2 -C 4 At least one of the straight chain alkynyl groups;
R 2 selected from H and C 1 -C 6 At least one hydrocarbon group of (2), preferably H, C 1 -C 6 Alkyl, C of (2) 2 -C 6 Alkenyl and C of (C) 2 -C 6 More preferably H, C 1 -C 6 Is of (2)Chain alkyl, C 2 -C 6 Straight chain alkenyl and C 2 -C 6 At least one of the straight chain alkynyl groups of (2), more preferably H, C 1 -C 4 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl and C 2 -C 4 At least one of the straight chain alkynyl groups of (2), more preferably H and C 2 -C 4 At least one of the straight chain alkynyl groups of (a).
3. The resin composition according to claim 1 or 2, characterized in that the reactive diluent is selected from monofunctional benzoxazines, preferably monofunctional benzoxazines with alkynyl or allyl groups, more preferably at least one of 3-ethynylaniline-phenol type benzoxazines, 2-allylphenol-aniline type benzoxazines and allylamine-phenol type benzoxazines.
4. The resin composition according to any one of claims 1 to 3, wherein the benzoxazine resin is selected from at least one of a diphenylmethane diamine-phenol type benzoxazine resin, a diphenylmethane diamine-p-cresol type benzoxazine resin, a diphenylether diamine-phenol type benzoxazine resin, a bisphenol a-aniline type benzoxazine resin, a bisphenol F-aniline type benzoxazine resin, and a bisphenol S-aniline type benzoxazine resin.
5. The resin composition according to any one of claims 1 to 4, wherein the bismaleimide resin is at least one selected from the group consisting of p-phenylenediamine type bismaleimide, m-phenylenediamine type bismaleimide, diphenylmethane diamine type bismaleimide, diphenyl ether type bismaleimide, diphenyl sulfone type bismaleimide, diphenyl bisphenol a type bismaleimide and diphenyl ether type bismaleimide.
6. The resin composition according to any one of claims 1 to 5, characterized in that the viscosity of the resin composition at 90 ℃ is 200 to 500 mPa-s, preferably 200 to 450 mPa-s.
7. Use of the resin composition according to any one of claims 1 to 6 as a raw material for resin in a resin transfer molding process.
8. A resin material for a resin transfer molding process, comprising: a heat-cured product of a melt containing the resin composition according to any one of claims 1 to 6, preferably, a raw material containing the resin composition according to any one of claims 1 to 6 is subjected to a heat treatment to obtain the melt, more preferably, the heat treatment conditions include: the temperature is 90-140 ℃ and the time is 10-60 min; and/or subjecting the melt to a heat curing treatment to obtain the heat-cured product, more preferably, the heat curing treatment conditions include: the temperature is 130-220 ℃ and the time is 0.5-8 h.
9. The resin material according to claim 8, wherein the resin material has a viscosity doubling time of 160 to 250 minutes at 90 ℃; the shrinkage is 0.70% -1.2%; the tensile strength is 75-100 MPa; young's modulus of 4500-5000 MPa; storage modulus inflection point temperature T g 180-250 ℃.
10. Use of a resin material as claimed in claim 8 or 9 as a resin material for use in a resin transfer moulding process.
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| CN202111231882.9A CN116003957A (en) | 2021-10-22 | 2021-10-22 | Resin composition and resin material for resin transfer molding process |
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|---|---|---|---|
| CN202111231882.9A CN116003957A (en) | 2021-10-22 | 2021-10-22 | Resin composition and resin material for resin transfer molding process |
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