CN114181439A - Toughening agent of thermosetting resin suitable for hot-melt pre-dipping process and preparation method - Google Patents
Toughening agent of thermosetting resin suitable for hot-melt pre-dipping process and preparation method Download PDFInfo
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Abstract
The invention relates to a toughening agent of thermosetting resin suitable for hot-melt pre-dipping process and a preparation method thereof; comprises 100 portions of rubber, 0.5 to 2.0 portions of cross-linking agent, 1 to 5 portions of silane coupling agent, 0.5 to 2.0 portions of antioxidant and 20 to 300 portions of organic solvent according to the weight portion; wherein the rubber is at least two of butyronitrile-40, carboxyl-terminated butyronitrile rubber, hydroxyl-terminated butyronitrile rubber, unsaturated bond-containing silicon rubber and carboxyl styrene-butadiene rubber; the invention aims to provide a toughening agent of thermosetting resin suitable for a hot-melt pre-dipping process and a preparation method thereof, the toughening agent is suitable for modification preparation of the thermosetting resin, can solve the problems of poor hot-melt manufacturability such as easy brittle fracture, slag removal, over-adhesion and incapability of film formation of a resin adhesive film in the prior art, and can adjust any proportion to improve the applicability of the hot-melt pre-dipping process of a resin system while toughening.
Description
Technical Field
The invention relates to the technical field of a toughening agent of thermosetting resin, in particular to a toughening agent of thermosetting resin suitable for a hot-melt pre-dipping process and a preparation method thereof.
Background
At present, with the gradual rise of national high-end manufacturing, the application ratio of the thermosetting resin gradually inclines from the traditional building material manufacturing field to high-end technical fields such as aerospace, national defense military industry, precision electronic manufacturing and the like. Therefore, at present, high-end industrial manufacturing technologies and application scenes also provide better requirements for comprehensive application performance of thermosetting resins, taking the field of civil aviation manufacturing as an example, civil aircraft composite materials have very high toughness requirements for aviation-grade phenolic resins, epoxy resins, benzoxazine resins and other thermosetting resins, and the toughness requirements of respective material systems can be met only by toughening and modifying corresponding matrix resins.
The preparation method of the thermosetting resin-based prepreg mainly comprises a solution impregnation method and a hot melt adhesive film method. The problems of waste and environmental pollution caused by volatilization of a large amount of solvent in the process of the solution impregnation method are inevitable so far. The hot melt resin matrix is first heated and melted to form a hot melt adhesive film of certain quality, and the hot melt resin adhesive film is then compounded with reinforcing material to form the hot melt prepreg through heating, pressurizing, compounding and other steps. With the continuous improvement of the national development on the environmental protection requirement, the hot-melt method prepreg production process gradually becomes the development direction of the current high-precision prepreg preparation. However, the cycle time for realizing the transition of the prepreg production process is short, and the key point is the research progress of the hot-melt process applicability of the resin matrix used. For the traditional resin system, many resin systems cannot meet the applicability of the hot-melt pre-dipping process, and mainly show the problems that a resin adhesive film is easy to crack, drop slag, be excessively sticky, cannot form a film and the like.
Therefore, the invention provides a toughening agent of thermosetting resin suitable for hot-melt prepreg technology and a preparation method thereof aiming at the problems.
Disclosure of Invention
The invention aims to provide a toughening agent of thermosetting resin suitable for a hot-melt pre-dipping process and a preparation method thereof, and solves the problems of poor hot-melt manufacturability, such as easy brittle fracture, slag falling, over-adhesion, film failure and the like of a resin adhesive film in the prior art, through the preparation of the toughening agent of thermosetting resin suitable for the hot-melt pre-dipping process.
The invention provides a toughening agent of thermosetting resin suitable for a hot-melt pre-dipping process, which comprises 100 parts of rubber, 0.5-2.0 parts of a cross-linking agent, 1-5 parts of a silane coupling agent, 0.5-2.0 parts of an antioxidant and 20-300 parts of an organic solvent in parts by weight; wherein the rubber is at least two of butyronitrile-40, carboxyl-terminated butyronitrile rubber, hydroxyl-terminated butyronitrile rubber, unsaturated bond-containing silicon rubber and carboxyl styrene-butadiene rubber.
Preferably, the rubber composition comprises 100 parts by weight of rubber, 1.5 parts by weight of cross-linking agent, 3 parts by weight of silane coupling agent, 1.5 parts by weight of antioxidant and 100 parts by weight of organic solvent.
Preferably, the rubber is butyronitrile-40, carboxyl-terminated butyronitrile rubber, hydroxyl-terminated butyronitrile rubber, unsaturated bond-containing silicon rubber or carboxyl styrene butadiene rubber, and the Mooney viscosity of the rubber is in the range of 25-85 (ML 1+4 @100 ℃);
the Mooney viscosity range of the rubber of at least two combinations of the rubber of butyronitrile-40, carboxyl-terminated butyronitrile rubber, hydroxyl-terminated butyronitrile rubber, silicon rubber containing unsaturated bonds and carboxyl styrene-butadiene rubber is 40-50 (ML 1+4 @100 ℃).
Preferably, the antioxidant is at least one of antioxidant 264, antioxidant 330, antioxidant 1074, and antioxidant CA.
Preferably, the organic solvent is at least one of ethyl acetate, acetone, butanone, xylene, and n-hexane.
Preferably, the crosslinking agent is at least one of sulfur, dicumyl peroxide, SCA-100, di-tert-butyl peroxide (DTBP) and 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide (bis 25).
Preferably, the silane coupling agent is at least one of KH-550, KH-560, KH-570, KH-792, A171, Z6011, 9116, and KBM-603.
The invention also provides a preparation method of the toughening agent based on the thermosetting resin suitable for the hot-melt pre-dipping process, which comprises the following steps:
selecting rubber according to the modification requirement of thermosetting resin, wherein the thermosetting resin comprises one of phenolic resin, hot-melt epoxy resin, hot-melt benzoxazine resin, hot-melt bismaleimide resin and hot-melt cyanate ester;
dispersing rubber and an antioxidant in an open mill to obtain pre-dispersed rubber;
adding pre-dispersed rubber into a reaction kettle, adding an organic solvent, preserving heat at 45-60 ℃, stirring and dissolving for 2-16h, selecting at least two sampling points for sampling in the stirring and dissolving process, respectively measuring the sampling viscosity, and stopping stirring when the deviation of the selected sampling viscosity is less than 3% to obtain a viscous rubber solution;
and adding a cross-linking agent and a silane coupling agent into the rubber solution, and stirring at a high speed to obtain the toughening agent.
Preferably, the conditions for the open mill mastication are: the roller distance of the thin tube is 0-2 mm, the thin tube is passed for 3-10 times at 40-80 ℃.
Preferably, the toughening agent is stored for 60 days at 15-30 ℃ after being prepared.
Compared with the prior art, the toughening agent of the thermosetting resin suitable for the hot-melt pre-dipping process and the preparation method thereof provided by the invention have the following progress:
1. the preparation method has the advantages that the preparation of the toughening agent of the thermosetting resin suitable for the hot-melt pre-dipping process is realized, and the rubber containing the active carboxyl, hydroxyl or unsaturated bond structure is selected, so that the preparation method has the remarkable effect on improving the toughness of the resin, can improve the ductility, the film forming property and other characteristics of a resin system, and further improves the applicability of the hot-melt process.
2. The toughening agent of the thermosetting resin provided by the invention can be combined and optimized according to the special performance required by a target resin system, and the effective regulation and control of the special performance required by the target resin can be realized by different composition proportions of different types of rubber.
3. The preparation method of the toughening agent of the thermosetting resin suitable for the hot-melt pre-dipping process is simple in process, easy to industrialize and high in practicability.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a toughening agent of thermosetting resin suitable for a hot-melt pre-dipping process, which comprises 100 parts of rubber, 0.5-2.0 parts of a cross-linking agent, 1-5 parts of a silane coupling agent, 0.5-2.0 parts of an antioxidant and 20-300 parts of an organic solvent in parts by weight; wherein the rubber is at least two of butyronitrile-40, carboxyl-terminated butyronitrile rubber, hydroxyl-terminated butyronitrile rubber, unsaturated bond-containing silicon rubber and carboxyl styrene-butadiene rubber.
Specifically, the rubber composition comprises 100 parts by weight of rubber, 1.5 parts by weight of a cross-linking agent, 3 parts by weight of a silane coupling agent, 1.5 parts by weight of an antioxidant and 100 parts by weight of an organic solvent.
Specifically, the rubber is butyronitrile-40, carboxyl-terminated butyronitrile rubber, hydroxyl-terminated butyronitrile rubber, unsaturated bond-containing silicon rubber or carboxyl styrene butadiene rubber, and the Mooney viscosity range of the rubber is 25-85 (ML 1+4 @100 ℃);
the Mooney viscosity range of the rubber of at least two combinations of the rubber of butyronitrile-40, carboxyl-terminated butyronitrile rubber, hydroxyl-terminated butyronitrile rubber, silicon rubber containing unsaturated bonds and carboxyl styrene-butadiene rubber is 40-50 (ML 1+4 @100 ℃).
Specifically, the antioxidant is at least one of antioxidant 264, antioxidant 330, antioxidant 1074 and antioxidant CA.
Specifically, the organic solvent is at least one of ethyl acetate, acetone, butanone, xylene and n-hexane.
Specifically, the crosslinking agent is at least one of sulfur, dicumyl peroxide, SCA-100, di-tert-butyl peroxide (DTBP) and 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide (bis 25).
Specifically, the silane coupling agent is at least one of KH-550, KH-560, KH-570, KH-792, A171, Z6011, 9116 and KBM-603.
The invention also provides a preparation method of the toughening agent based on the thermosetting resin suitable for the hot-melt pre-dipping process, which comprises the following steps:
s1) selecting rubber according to the modification requirement of the thermosetting resin, wherein the thermosetting resin comprises one of phenolic resin, hot-melt epoxy resin, hot-melt benzoxazine resin, hot-melt bismaleimide resin and hot-melt cyanate ester;
s2) putting the rubber and the antioxidant into an open mill for dispersion to obtain pre-dispersed rubber;
s3) adding pre-dispersed rubber into a reaction kettle, adding an organic solvent, preserving heat at 45-60 ℃, stirring and dissolving for 2-16h, selecting at least two sampling points for sampling in the stirring and dissolving process, respectively measuring the sampling viscosity, and stopping stirring when the deviation of the selected sampling viscosity is less than 3%, so as to obtain a viscous rubber solution;
s4) adding a cross-linking agent and a silane coupling agent into the rubber solution, and stirring at high speed to obtain the toughening agent.
Specifically, the conditions of the open mill plastication work are as follows: the roller distance of the thin tube is 0-2 mm, the thin tube is passed for 3-10 times at 40-80 ℃.
Specifically, the toughening agent is stored for 60 days at 15-30 ℃ after being prepared.
Example one
Preparation of toughener (sample 1):
according to the parts by weight, the toughening agent comprises 100 parts of rubber, 0.5 part of a cross-linking agent, 1 part of a silane coupling agent, 0.5 part of an antioxidant and 20 parts of an organic solvent;
adding 100 parts of rubber and 0.5 part of oxidant into an open mill for pre-dispersion according to the parts by weight, wherein the plastication conditions are as follows: the roller distance of the thin through is 0-2 mm, the thin through is carried out for 3-10 times, and the temperature is 40-80 ℃, so as to obtain the pre-dispersed rubber;
adding pre-dispersed rubber into a reaction kettle, adding 20 parts of organic solvent, keeping the temperature at 45-60 ℃, stirring and dissolving for 2-16h, when 3 samples taken out from the upper, middle and lower random parts of the reaction kettle have no obvious blocky insoluble substances, carrying out viscosity test on the samples, and stopping the dissolution reaction when the deviation of the sampled viscosity test result is less than 3%, so as to obtain a viscous rubber solution with uniform solute;
and (3) adding 0.5 part of cross-linking agent and 1 part of silane coupling agent into the rubber solution, and dispersing and stirring for 15-30 min under a high-speed dispersion machine to obtain the toughening agent.
Wherein the rubber is butyronitrile-40 and carboxyl-terminated butyronitrile rubber; selecting butyronitrile-40 and carboxyl-terminated butyronitrile rubber respectively in the range of rubber Mooney viscosity of 25-85 (ML 1+4 @100 ℃), so that the Mooney viscosity of the rubber after mixing the butyronitrile-40 and the carboxyl-terminated butyronitrile rubber is 47 (ML 1+4 @100 ℃);
the nitrile rubber can be copolymerized with phenolic resin, and has good toughening effect. In addition, the rubber contains carboxyl, and can further generate graft or block copolymerization reaction with hydroxymethyl on a phenolic resin chain, and the chemical reactions are favorable for improving the compatibility of the nitrile rubber and the phenolic resin, improving the bonding rate of the rubber and a phenolic resin matrix and further improving the toughening effect.
The antioxidant is antioxidant 264;
the organic solvent is a mixture of ethyl acetate and butanone; the mass ratio of ethyl acetate to butanone is 4: 1;
the cross-linking agent is di-tert-butyl peroxide (DTBP);
the silane coupling agent is KH-550.
Preparing a test sample 1, namely adding 30 parts of a toughening agent (sample 1) into 100 parts of phenolic resin according to parts by weight, heating, stirring at a high speed for dispersion, and fully and uniformly mixing the toughening agent and the resin to obtain modified toughened resin; the modified toughened resin is subjected to hot melting process to prepare a resin adhesive film, the resin adhesive film and the reinforced fiber fabric are subjected to hot pressing compounding through the hot melting process to prepare hot-melt prepreg cloth, and the hot-melt prepreg cloth is subjected to laminating, curing and forming to prepare a plate (test sample 1).
The preparation of the comparison sample 1 includes that phenolic resin (same as the phenolic resin in the test sample 1) is subjected to a hot melting process to prepare a resin adhesive film, the resin adhesive film and a reinforced fiber fabric are subjected to hot pressing compounding through the hot melting process to prepare hot-melt prepreg cloth, and the hot-melt prepreg cloth is subjected to lamination, curing and molding to prepare a plate (the comparison sample 1).
And (2) preparing a comparison sample, namely adding 30 parts of butyronitrile-40 into 100 parts of phenolic resin, heating, stirring at a high speed for dispersion, fully and uniformly mixing a toughening agent and the resin to obtain modified toughened resin, preparing a resin adhesive film through a hot melting process, compounding the resin adhesive film and a reinforcing fiber fabric through hot pressing by the hot melting process to prepare hot-melt prepreg cloth, and preparing the hot-melt prepreg cloth into a plate through lamination, solidification and molding (comparison sample 2).
The reinforced fiber fabrics are all glass fiber cloth, and the plates are all three-layer composite plates.
The properties of the control 1, control 2 and test 1 obtained are shown in Table 1.
Example two
A toughening agent (sample 2) was prepared, and the preparation process of sample 2 was the same as that of sample 1 except that the rubber component was selected differently;
wherein the rubber is butyronitrile-40 and silicon rubber containing unsaturated bonds, and the butyronitrile-40 and the silicon rubber containing unsaturated bonds are respectively selected in the range of the Mooney viscosity of the rubber being 25-85 (ML 1+4 @100 ℃) so that the Mooney viscosity of the mixed rubber is 46 (ML 1+4 @100 ℃).
The rubber containing an unsaturated bond structure is selected, so that the toughness of the resin is improved, the ductility and the film forming property of a resin system can be improved, and the applicability of a hot melting process is improved.
Preparing a test sample 2, namely adding 30 parts of a toughening agent (sample 2) into 100 parts of phenolic resin according to parts by weight, heating, stirring at a high speed for dispersion, and fully and uniformly mixing the toughening agent and the resin to obtain modified toughened resin; the modified toughened resin is subjected to hot melting process to prepare a resin adhesive film, the resin adhesive film and the reinforced fiber fabric are subjected to hot-pressing compounding through the hot melting process to prepare hot-melting prepreg cloth, the hot-melting prepreg cloth is subjected to laminating, curing and forming to prepare a plate (test sample 2), and the performance of the test sample 2 is shown in table 1.
EXAMPLE III
A toughening agent (sample 3) was prepared, the preparation of sample 3 being the same as that of sample 1 except that the rubber was selected differently;
wherein the rubber is butyronitrile-40 and hydroxyl-terminated butyronitrile rubber, and the butyronitrile-40 and the silicon rubber containing unsaturated bonds are respectively selected in the range of the Mooney viscosity of the rubber being 25-85 (ML 1+4 @100 ℃), so that the Mooney viscosity of the rubber after the mixing of the butyronitrile-40 and the silicon rubber is 47 (ML 1+4 @100 ℃).
The rubber containing hydroxyl is selected, so that the toughness of the resin is improved, the ductility and the film forming property of a resin system can be improved, and the applicability of a hot melting process is improved.
Preparing a test sample 3, namely adding 30 parts of a toughening agent (sample 3) into 100 parts of phenolic resin according to parts by weight, heating, stirring at a high speed for dispersion, and fully and uniformly mixing the toughening agent and the resin to obtain modified toughened resin; the modified toughened resin is subjected to hot melting process to prepare a resin adhesive film, the resin adhesive film and the reinforced fiber fabric are subjected to hot-pressing compounding through the hot melting process to prepare hot-melting prepreg cloth, the hot-melting prepreg cloth is subjected to laminating, curing and forming to prepare a plate (test sample 3), and the performance of the test sample 3 is shown in table 1.
Example four
A toughening agent (sample 4) was prepared, the preparation of sample 4 being the same as that of sample 1 except that the rubber was selected differently;
wherein the rubber is butyronitrile-40 and carboxylated styrene-butadiene rubber, and the butyronitrile-40 and the carboxylated styrene-butadiene rubber are respectively selected in the range of the Mooney viscosity of the rubber being 25-85 (ML 1+4 @100 ℃), so that the Mooney viscosity of the rubber after the mixing of the butyronitrile-40 and the carboxylated styrene-butadiene rubber is 40 (ML 1+4 @100 ℃).
Preparing a test sample 4, namely adding 30 parts of a toughening agent (sample 4) into 100 parts of phenolic resin according to parts by weight, heating, stirring at a high speed for dispersion, and fully and uniformly mixing the toughening agent and the resin to obtain modified toughened resin; the modified toughened resin is subjected to hot melting process to prepare a resin adhesive film, the resin adhesive film and the reinforced fiber fabric are subjected to hot-pressing compounding through the hot melting process to prepare hot-melting prepreg cloth, the hot-melting prepreg cloth is subjected to laminating, curing and forming to prepare a plate (test sample 4), and the performance of the test sample 4 are shown in table 1.
EXAMPLE five
Preparing a toughening agent (sample 5), wherein the preparation process of the sample 5 is the same as that of the sample 1, and the difference is only that the rubber is butyronitrile-40 and carboxyl-terminated butyronitrile rubber in different proportions;
wherein the rubber is butyronitrile-40 and hydroxyl-terminated butyronitrile rubber; the nitrile-40 and hydroxyl terminated nitrile rubber are respectively selected in the range of rubber Mooney viscosity of 25-85 (ML 1+4 @100 ℃) so that the Mooney viscosity of the rubber after mixing the nitrile-40 and the hydroxyl terminated nitrile rubber is 50 (ML 1+4 @100 ℃).
Preparing a test sample 5, namely adding 30 parts of a toughening agent (sample 5) into 100 parts of phenolic resin according to parts by weight, heating, stirring at a high speed for dispersion, and fully and uniformly mixing the toughening agent and the resin to obtain modified toughened resin; the modified toughened resin is subjected to hot melting process to prepare a resin adhesive film, the resin adhesive film and the reinforced fiber fabric are subjected to hot-pressing compounding through the hot melting process to prepare hot-melting prepreg cloth, the hot-melting prepreg cloth is subjected to laminating, curing and forming to prepare a plate (test sample 5), and the performance of the test sample 5 is shown in table 1.
The tensile strength, the elongation at break and the impact strength of the test sample 1, the test sample 2, the test sample 3, the test sample 4 and the test sample 5 are greatly improved compared with those of the comparative sample 1, and the toughening effect is obvious.
EXAMPLE six
Selecting the sample 1 prepared in the first embodiment, adding 30 parts of the sample 1 into 100 parts of hot-melt epoxy resin by weight, heating, stirring at a high speed for dispersion, and fully and uniformly mixing the sample 1 and the resin to obtain modified hot-melt epoxy resin; the modified hot-melt epoxy resin is subjected to hot-melt process to prepare a resin adhesive film, the resin adhesive film and the reinforced fiber fabric are subjected to hot-melt process hot-pressing compounding to prepare hot-melt prepreg cloth, the hot-melt prepreg cloth is subjected to laminating, curing and forming to prepare a plate (test sample 6), and the performance of the test sample 6 is shown in table 1.
EXAMPLE seven
Selecting the sample 1 prepared in the first embodiment, adding 30 parts of the sample 1 into 100 parts of hot-melt benzoxazine resin by weight, heating, stirring at a high speed for dispersion, and fully and uniformly mixing the sample 1 and the resin to obtain modified hot-melt benzoxazine resin; the modified hot-melt benzoxazine resin is subjected to a hot-melt process to prepare a resin adhesive film, the resin adhesive film and a reinforced fiber fabric are subjected to hot-melt process hot-pressing compounding to prepare a hot-melt prepreg cloth, the hot-melt prepreg cloth is subjected to laminating, curing and forming to prepare a plate (test sample 7), and the performance of the test sample 7 is shown in table 1.
Example eight
Selecting the sample 1 prepared in the first embodiment, adding 30 parts of the sample 1 into 100 parts of hot-melt bismaleimide resin by weight, heating, stirring at a high speed for dispersion, and fully and uniformly mixing the sample 1 and the resin to obtain modified hot-melt bismaleimide resin; the modified hot-melt bismaleimide resin is subjected to hot-melt process to prepare a resin adhesive film, the resin adhesive film and a reinforced fiber fabric are subjected to hot-melt process hot-pressing compounding to prepare hot-melt prepreg cloth, the hot-melt prepreg cloth is subjected to laminating, curing and forming to prepare a plate (test sample 8), and the performance of the test sample 8 is shown in table 1.
In the sixth embodiment, the seventh embodiment and the eighth embodiment, the performance of the thermosetting resin can be effectively improved by adopting the heat increasing agent of the sample 1, and the toughening agent obtained by the invention can be suitable for improving the performance of the thermosetting resin; the combination optimization can be carried out according to the special performance required by a target resin system, and the effective regulation and control of the special performance required by the target resin can be realized by different composition proportions of different types of rubber.
Table 1 results of performance test of the sheets
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A toughening agent of thermosetting resin suitable for a hot-melt pre-dipping process is characterized in that: comprises 100 portions of rubber, 0.5 to 2.0 portions of cross-linking agent, 1 to 5 portions of silane coupling agent, 0.5 to 2.0 portions of antioxidant and 20 to 300 portions of organic solvent according to the weight portion; wherein the rubber is at least two of butyronitrile-40, carboxyl-terminated butyronitrile rubber, hydroxyl-terminated butyronitrile rubber, unsaturated bond-containing silicon rubber and carboxyl styrene-butadiene rubber.
2. The toughener for thermosetting resins suitable for use in hot melt prepreg process of claim 1, wherein: the rubber composition comprises, by weight, 100 parts of rubber, 1.5 parts of a crosslinking agent, 3 parts of a silane coupling agent, 1.5 parts of an antioxidant and 100 parts of an organic solvent.
3. The toughener for thermosetting resins suitable for use in hot melt prepreg process of claim 1, wherein: the Mooney viscosity range of the rubber is 25-85 (ML 1+4 @100 ℃), wherein the rubber is butyronitrile-40, carboxyl-terminated butyronitrile rubber, hydroxyl-terminated butyronitrile rubber, silicon rubber containing unsaturated bonds or carboxyl butadiene styrene rubber;
the Mooney viscosity range of the rubber of at least two combinations of the rubber of butyronitrile-40, carboxyl-terminated butyronitrile rubber, hydroxyl-terminated butyronitrile rubber, silicon rubber containing unsaturated bonds and carboxyl styrene-butadiene rubber is 40-50 (ML 1+4 @100 ℃).
4. The toughener for thermosetting resins suitable for use in hot melt prepreg process of claim 1, wherein: the antioxidant is at least one of antioxidant 264, antioxidant 330, antioxidant 1074 and antioxidant CA.
5. The toughener for thermosetting resins suitable for use in hot melt prepreg process of claim 1, wherein: the organic solvent is at least one of ethyl acetate, acetone, butanone, xylene and n-hexane.
6. The toughener for thermosetting resins suitable for use in hot melt prepreg process of claim 1, wherein: the cross-linking agent is at least one of sulfur, dicumyl peroxide, SCA-100, di-tert-butyl peroxide (DTBP) and 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide (bis 25).
7. The toughener for thermosetting resins suitable for use in hot melt prepreg process of claim 4, wherein: the silane coupling agent is at least one of KH-550, KH-560, KH-570, KH-792, A171, Z6011, 9116 and KBM-603.
8. A method for preparing a toughening agent based on the thermosetting resin suitable for the hot melt prepreg process according to any one of claims 1 to 7, wherein: the method comprises the following steps:
selecting rubber according to the modification requirement of thermosetting resin, wherein the thermosetting resin comprises one of phenolic resin, hot-melt epoxy resin, hot-melt benzoxazine resin, hot-melt bismaleimide resin and hot-melt cyanate ester;
dispersing rubber and an antioxidant in an open mill to obtain pre-dispersed rubber;
adding pre-dispersed rubber into a reaction kettle, adding an organic solvent, preserving heat at 45-60 ℃, stirring and dissolving for 2-16h, selecting at least two sampling points for sampling in the stirring and dissolving process, respectively measuring the sampling viscosity, and stopping stirring when the deviation of the selected sampling viscosity is less than 3% to obtain a viscous rubber solution;
and adding a cross-linking agent and a silane coupling agent into the rubber solution, and stirring at a high speed to obtain the toughening agent.
9. The method of claim 8, wherein: the conditions of the open mill plastication work are as follows: the roller distance of the thin tube is 0-2 mm, the thin tube is passed for 3-10 times at 40-80 ℃.
10. The method of claim 9, wherein: after the toughening agent is prepared, the mixture is stored for 60 days at the temperature of 15-30 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115368865A (en) * | 2022-07-28 | 2022-11-22 | 浙江澳宇新材料科技有限公司 | Polyester hot melt adhesive particle for spraying and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702683A (en) * | 2012-06-04 | 2012-10-03 | 中国航空工业集团公司北京航空材料研究院 | Epoxy resin for prepreg and preparation method thereof |
| CN113563593A (en) * | 2021-08-14 | 2021-10-29 | 科艾斯化学有限公司 | Core-shell toughening agent, preparation method thereof and toughened nylon applied by core-shell toughening agent |
-
2022
- 2022-02-16 CN CN202210140938.8A patent/CN114181439A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702683A (en) * | 2012-06-04 | 2012-10-03 | 中国航空工业集团公司北京航空材料研究院 | Epoxy resin for prepreg and preparation method thereof |
| CN113563593A (en) * | 2021-08-14 | 2021-10-29 | 科艾斯化学有限公司 | Core-shell toughening agent, preparation method thereof and toughened nylon applied by core-shell toughening agent |
Non-Patent Citations (3)
| Title |
|---|
| A.OZTURK等: "Effects of liquid rubber modification on the behaviour of epoxy resin", 《EUROPEAN POLYMER JOURNAL》 * |
| CEVDET KAYNAK等: "Rubber toughening of phenolic resin by using nitrile rubber and amino silane", 《POLYMER TESTING》 * |
| 宋盛菊等: "环氧树脂增韧方法及增韧剂的研究进展", 《中国印刷与包装研究》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115368865A (en) * | 2022-07-28 | 2022-11-22 | 浙江澳宇新材料科技有限公司 | Polyester hot melt adhesive particle for spraying and preparation method thereof |
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