CN111378247A - Epoxy resin composition for wet winding forming composite material and preparation method thereof - Google Patents
Epoxy resin composition for wet winding forming composite material and preparation method thereof Download PDFInfo
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- CN111378247A CN111378247A CN202010198950.5A CN202010198950A CN111378247A CN 111378247 A CN111378247 A CN 111378247A CN 202010198950 A CN202010198950 A CN 202010198950A CN 111378247 A CN111378247 A CN 111378247A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/36—Epoxy compounds containing three or more epoxy groups together with mono-epoxy compounds
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention discloses an epoxy resin composition for a wet winding molding composite material and a preparation method thereof. The epoxy resin composition for the wet winding molding composite material is prepared by mixing acrylic rubber with epoxy groups, an epoxy resin monomer prepared from 1, 2-epoxycyclohexane-4, 5-dicarboxylic acid and epoxy chloropropane, a polyepoxy epoxy active diluent, primary amine, an epoxy curing agent and an epoxy resin adhesive solution in proportion under the heating condition, and can greatly improve the degree of crosslinking of a polymer and increase the molecular weight of the polymer, thereby improving the mechanical property, the temperature resistance and the aging resistance of the composite material and effectively improving the problem of poor toughness of the epoxy resin. In addition, the preparation method of the epoxy resin composition for the wet winding molding composite material has the advantages of simple process, good repeatability and the like.
Description
Technical Field
The invention relates to the field of wet winding composite materials, in particular to a resin composition for wet winding and a preparation method thereof.
Background
The fiber reinforced resin matrix composite material has the characteristics of light weight, high strength and wide application prospect, and the epoxy resin and the cured product thereof have high mechanical properties, excellent bonding properties, small curing shrinkage and good manufacturability, are common resin matrixes at present, but the cured product of the epoxy resin has brittle physical properties and poor impact resistance and needs toughening modification. The modification of epoxy resin by using rubber particles is a common means, and the problem of compatibility needs to be solved by modifying epoxy resin by using rubber particles, for example, in the preparation of a fiber composite prepreg, a mode of dissolving and mixing rubber particles and epoxy resin by using an organic solvent can be adopted.
The gyrorotor composite material mostly adopts a wet winding process, a resin matrix used cannot contain a volatile solvent, otherwise bubble defects are easily generated in the curing process, the toughening of the composite material mostly adopts a mode of mixing rubber particles in epoxy resin to form a sea-island structure, and the mode has the problem of poor consistency of mechanical properties of a composite material product.
CN109651767A proposes an epoxy resin composition toughened by epoxy liquid rubber, which comprises epoxy resin, epoxy liquid rubber, a curing agent and an accelerator, wherein the epoxy liquid rubber is one or more of epoxy liquid natural rubber, epoxy liquid polyisoprene rubber, epoxy liquid nitrile rubber and epoxy polyacrylate liquid rubber, and the curing agent is one or more of zinc acrylate, magnesium acrylate, aluminum acrylate, zinc methacrylate, aluminum methacrylate, zinc sorbate, butyl acrylate, 1, 6-hexanediol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, butanediol diacrylate and pentaerythritol tetraacrylate. The toughening mechanism is chemical toughening, specifically, under the action of an accelerator, epoxy groups in epoxy liquid rubber and epoxy resin are subjected to ring opening to generate hydroxyl groups, and further, in the curing process, the hydroxyl groups and double bonds on a curing agent are subjected to an oxa-Michael reaction to form forced compatibility in a manner of generating covalent bonds between the epoxy liquid rubber and the epoxy resin. Although the method can make the toughened rubber compatible with the epoxy resin, the epoxy group is firstly subjected to ring opening to form hydroxyl in the reaction process and then is bonded with the curing agent, epoxy group crosslinking reaction does not occur in the reaction process, and meanwhile, a product blocked by the curing agent is easily formed in the curing process, so that the crosslinking density is reduced, and the mechanical property of the epoxy resin composition is influenced.
Disclosure of Invention
The invention aims to solve the problems and provides an epoxy resin composition suitable for a wet winding composite material, which can effectively solve the compatibility of epoxy resin and a toughening agent, has high temperature resistance and ageing resistance, and can effectively improve the toughness on the basis of not reducing the mechanical property of the resin.
The invention aims to realize the purpose that acrylic rubber with epoxy group, epoxy resin monomer prepared from 1, 2-epoxycyclohexane-4, 5-dicarboxylic acid and epichlorohydrin, polyepoxy epoxy active diluent and a proper amount of primary amine are heated and mixed, the epoxy resin monomer and the polyepoxy epoxy active diluent have high polarity, can effectively dissolve the acrylic rubber, have high primary amine activity, initiate the reaction of the epoxy resin monomer to generate epoxy compounds on one hand, and initiate the ring-opening reaction of a small amount of epoxy groups to obtain hydroxyl by controlling the dosage of the primary amine on the other hand. And then adding the mixture and the epoxy curing agent into the epoxy resin glue solution for wet winding, and dissolving to obtain the required resin composition. In the curing process, carboxyl can accelerate the ring-opening crosslinking polymerization of epoxy groups; on the other hand, N atoms and hydroxyl groups in the primary amine reaction product participate in and initiate epoxy group ring-opening reaction, and the reaction processes can greatly improve the crosslinking degree of the polymer and increase the molecular weight of the polymer, so that the mechanical property, the temperature resistance and the aging resistance of the composite material are improved, and the purpose of the invention is realized.
The invention relates to an epoxy resin composition for a wet winding molding composite material, which comprises the following materials in percentage by weight:
15 to 30 parts by mass of glycidyl group-containing acrylic rubber;
10-20 parts by mass of an epoxy resin monomer;
30-40 parts by mass of a polyepoxy reactive diluent;
5-8 parts by mass of primary amine;
60-70 parts of TDE-85 epoxy resin;
30-40 parts of AG-80 epoxy resin;
30-40 parts by mass of an amine epoxy curing agent;
the epoxy resin monomer is a mixture of 1, 2-epoxycyclohexane-4, 5-dicarboxylic acid and epichlorohydrin, wherein the molar ratio of the epoxy resin monomer to the epoxy resin monomer is (1-1.3): 2.
The invention relates to an epoxy resin composition for a wet winding molding composite material, which is characterized by comprising the following components in percentage by weight: the above-mentioned
20-24 parts by mass of acrylic rubber;
12-15 parts by mass of an epoxy resin monomer;
30-35 parts by mass of a polyepoxy reactive diluent.
The invention relates to an epoxy resin composition for a wet winding molding composite material, wherein the molar ratio of 1, 2-epoxycyclohexane-4, 5-dicarboxylic acid to epichlorohydrin in an epoxy resin monomer is (1.1-1.2): 2.
The invention relates to an epoxy resin composition for a wet winding molding composite material, which is characterized by comprising the following components in percentage by weight: the polyepoxy reactive diluent is trimethylolpropane triglycidyl ether or butanediol diglycidyl ether, or a mixture of the two.
The invention relates to an epoxy resin composition for a wet winding molding composite material, which is characterized by comprising the following components in percentage by weight: the primary amine is ethylenediamine or diethylenetriamine.
The invention relates to an epoxy resin composition for a wet winding molding composite material, wherein an amine epoxy curing agent is DDM or DDS.
The invention relates to a preparation method of an epoxy resin composition for a wet winding molding composite material, which comprises the following steps:
1) mixing 1, 2-epoxycyclohexane-4, 5-dicarboxylic acid and epichlorohydrin in a molar ratio of (1-1.3) to (2) to prepare an epoxy resin monomer;
2) weighing 15-30 parts by mass of glycidyl-containing acrylic rubber, 30-40 parts by mass of polyepoxy reactive diluent and 5-8 parts by mass of primary amine, dissolving in 10-20 parts by mass of prepared epoxy resin monomer, heating to 60-70 ℃, and uniformly stirring and mixing to prepare a mixed solution;
3) and keeping the temperature unchanged, continuously adding 60-70 parts by mass of TDE-85 epoxy resin, 30-40 parts by mass of AG-80 epoxy resin and 30-40 parts by mass of amine epoxy curing agent into the prepared mixed solution, and uniformly stirring and mixing to obtain the epoxy resin composition for the wet winding molding composite material.
The invention relates to a preparation method of an epoxy resin composition for a wet winding molding composite material, which is characterized by comprising the following steps: the mixed solution in the step 2) is prepared by dissolving 20-24 parts by mass of glycidyl-containing acrylic rubber, 30-35 parts by mass of polyepoxy reactive diluent and 5-8 parts by mass of primary amine into 12-15 parts by mass of prepared epoxy resin monomer, heating to 60-70 ℃, and uniformly stirring and mixing.
The invention relates to a preparation method of an epoxy resin composition for a wet winding molding composite material, which is characterized by comprising the following steps: the epoxy resin monomer is prepared by mixing 1, 2-epoxycyclohexane-4, 5-dicarboxylic acid and epichlorohydrin according to a molar ratio of (1.1-1.2): 2.
The epoxy resin composition for the wet winding composite material can greatly improve the crosslinking degree of the polymer and increase the molecular weight of the polymer, thereby improving the mechanical property, the temperature resistance and the aging resistance of the composite material and effectively improving the problem of poor toughness of the epoxy resin. In addition, the preparation method of the epoxy resin composition for the wet winding molding composite material has the advantages of simple process, good repeatability and the like.
Detailed Description
The present invention will be further described with reference to the following examples, but the technical solution of the present invention is not limited to the specific embodiments listed below. The invention is not limited to the embodiments described above, but rather, various modifications and changes may be made by those skilled in the art without departing from the scope of the invention. The materials not specifically mentioned are all in parts by mass.
Example one
According to the mol ratio of 1: 2 weighing 1, 2-epoxycyclohexane-4, 5-dimethyl acid solution and epoxy chloropropane solution, placing the solution in a beaker, and stirring the solution for 15min by a glass rod at normal temperature to prepare epoxy resin monomer solution which is uniformly mixed.
10g of the prepared epoxy resin monomer solution, 15g of acrylic rubber, 30g of trimethylolpropane triglycidyl ether and 5g of primary amine were weighed out and added to a beaker in this order. The beaker is placed in a heating sleeve, an electric stirring device is arranged at the opening of the beaker, and the heating temperature of the heating sleeve is set to be 60 ℃.
During the test, the heating sleeve, the ventilation device and the electric stirring device are sequentially started to electrically stir the mixed liquid in the beaker at the speed of 100 revolutions per minute, and when the temperature of the heating sleeve reaches 60 ℃, the mixed liquid is continuously stirred for 20min to prepare the mixed liquid.
And keeping the temperature unchanged, continuously adding 60g of TDE-85 epoxy resin, 30g of 30gAG-80 epoxy resin and 30g of DDM curing agent into the mixed solution, and stirring for 30min to obtain the resin composition.
A resin molded body prepared from the resin composition of this example had a tensile strength of 102MPa, an elongation at break of 4.3% and an impact strength of 16KJ/m2。
Example two
According to a molar ratio of 1.1: 2 weighing 1, 2-epoxycyclohexane-4, 5-dimethyl acid solution and epoxy chloropropane solution, placing the solution in a beaker, and stirring the solution for 15min by a glass rod at normal temperature to prepare the epoxy resin monomer which is uniformly mixed.
13g of the prepared epoxy resin monomer, 20g of acrylic rubber, 33g of butanediol diglycidyl ether, and 6g of primary amine were weighed out and added to a beaker in this order. The beaker is placed in a heating sleeve, an electric stirring device is arranged at the opening of the beaker, and the heating temperature of the heating sleeve is set to be 70 ℃.
During the test, the heating sleeve, the ventilation device and the electric stirring device are sequentially started to electrically stir the mixed liquid in the beaker at the speed of 100 revolutions per minute, and when the temperature of the heating sleeve reaches 70 ℃, the mixed liquid is continuously stirred for 25min to prepare the mixed liquid.
Keeping the temperature unchanged, adding 63g of TDE-85 epoxy resin, 33gAG-80 epoxy resin and 33g of DDS curing agent into the mixed solution, and stirring for 30min to obtain the resin composition.
A resin molded body prepared from the resin composition of this example had a tensile strength of 100MPa, an elongation at break of 4.4% and an impact strength of 15KJ/m2。
EXAMPLE III
According to a molar ratio of 1.2: 2 weighing 1, 2-epoxycyclohexane-4, 5-dimethyl acid solution and epoxy chloropropane solution, placing the solution in a beaker, and stirring the solution for 10min by a glass rod at normal temperature to prepare the epoxy resin monomer which is uniformly mixed.
16g of the prepared epoxy resin monomer, 25g of acrylic rubber, 12g of trimethylolpropane triglycidyl ether, 24g of butanediol diglycidyl ether, and 7g of primary amine were weighed out and added to a beaker in this order. The beaker is placed in a heating sleeve, an electric stirring device is arranged at the opening of the beaker, and the heating temperature of the heating sleeve is set to be 65 ℃.
During the test, the heating sleeve, the ventilation device and the electric stirring device are sequentially started to electrically stir the mixed liquid in the beaker at the speed of 100 revolutions per minute, and when the temperature of the heating sleeve reaches 65 ℃, the mixed liquid is continuously stirred for 20min to prepare the mixed liquid.
And keeping the temperature unchanged, continuously adding 67g of TDE-85 epoxy resin, 36gAG-80 epoxy resin and 36g of DDM curing agent into the mixed solution, and continuously stirring for 25min to obtain the resin composition.
A resin molded body prepared from the resin composition of this example had a tensile strength of 105MPa, an elongation at break of 4.1% and an impact strength of 17KJ/m2。
Example four
According to a molar ratio of 1.3: 2 weighing 1, 2-epoxycyclohexane-4, 5-dimethyl acid solution and epoxy chloropropane solution, placing the solution in a beaker, and stirring the solution for 15min by a glass rod at normal temperature to prepare the epoxy resin monomer which is uniformly mixed.
20g of the prepared epoxy resin monomer, 30g of acrylic rubber, 25g of trimethylolpropane triglycidyl ether, 15g of butanediol diglycidyl ether, and 8g of primary amine were weighed out and added to a beaker in this order. The beaker is placed in a heating sleeve, an electric stirring device is arranged at the opening of the beaker, and the heating temperature of the heating sleeve is set to be 60 ℃.
During the test, the heating sleeve, the ventilation device and the electric stirring device are sequentially started to electrically stir the mixed liquid in the beaker at the speed of 100 revolutions per minute, and when the temperature of the heating sleeve reaches 60 ℃, the mixed liquid is continuously stirred for 30min to prepare the mixed liquid.
And keeping the temperature unchanged, continuously adding 70g of TDE-85 epoxy resin, 40gAG-80 epoxy resin and 40g of DDS curing agent into the mixed solution, and continuously stirring for 30min to obtain the resin composition.
A resin molded body prepared from the resin composition of this example had a tensile strength of 108MPa, an elongation at break of 4.7% and an impact strength of 16KJ/m2。
EXAMPLE five
According to a molar ratio of 1.1: 2 weighing 1, 2-epoxycyclohexane-4, 5-dimethyl acid solution and epoxy chloropropane solution, placing the solution in a beaker, and stirring the solution for 15min by a glass rod at normal temperature to prepare the epoxy resin monomer which is uniformly mixed.
12g of the prepared epoxy resin monomer, 20g of acrylic rubber, 30g of trimethylolpropane triglycidyl ether and 5g of primary amine were weighed out and added to a beaker in this order. The beaker is placed in a heating sleeve, an electric stirring device is arranged at the opening of the beaker, and the heating temperature of the heating sleeve is set to be 65 ℃.
During the test, the heating sleeve, the ventilation device and the electric stirring device are sequentially started to electrically stir the mixed liquid in the beaker at the speed of 100 revolutions per minute, and when the temperature of the heating sleeve reaches 65 ℃, the mixed liquid is continuously stirred for 28min to prepare the mixed liquid.
And keeping the temperature unchanged, continuously adding 62g of TDE-85 epoxy resin, 32gAG-80 epoxy resin and 32g of DDM curing agent into the mixture, and continuously stirring for 30min to obtain the resin composition.
A resin molded body prepared from the resin composition of this example had a tensile strength of 113MPa, an elongation at break of 5.3% and an impact strength of 20KJ/m2。
EXAMPLE six
According to a molar ratio of 1.2: 2 weighing 1, 2-epoxycyclohexane-4, 5-dimethyl acid solution and epoxy chloropropane solution, placing the solution in a beaker, and stirring the solution for 10min by a glass rod at normal temperature to prepare the epoxy resin monomer which is uniformly mixed.
13.5g of the prepared epoxy resin monomer, 22g of acrylic rubber, 32.5g of butanediol diglycidyl ether, and 7g of primary amine were weighed out and added to a beaker in this order. The beaker is placed in a heating sleeve, an electric stirring device is arranged at the opening of the beaker, and the heating temperature of the heating sleeve is set to be 70 ℃.
During the test, the heating sleeve, the ventilation device and the electric stirring device are sequentially started to electrically stir the mixed liquid in the beaker at the speed of 100 revolutions per minute, and when the temperature of the heating sleeve reaches 70 ℃, the mixed liquid is continuously stirred for 24min to prepare the mixed liquid.
And keeping the temperature unchanged, continuously adding 64g of TDE-85 epoxy resin, 34gAG-80 epoxy resin and 35g of DDS curing agent into the mixture, and continuously stirring for 25min to obtain the resin composition.
A resin molded body prepared from the resin composition of this example had a tensile strength of 115MPa, an elongation at break of 5.5% and an impact strength of 21KJ/m2。
EXAMPLE seven
According to a molar ratio of 1.15: 2 weighing 1, 2-epoxycyclohexane-4, 5-dimethyl acid solution and epoxy chloropropane solution, placing the solution in a beaker, and stirring the solution for 10min by a glass rod at normal temperature to prepare the epoxy resin monomer which is uniformly mixed.
15g of the prepared epoxy resin monomer, 24g of acrylic rubber, 17.5g of trimethylolpropane triglycidyl ether, 17.5g of butanediol diglycidyl ether, and 8g of primary amine were weighed out and added to a beaker in this order. The beaker is placed in a heating sleeve, an electric stirring device is arranged at the opening of the beaker, and the heating temperature of the heating sleeve is set to be 70 ℃.
During the test, the heating sleeve, the ventilation device and the electric stirring device are sequentially started to electrically stir the mixed liquid in the beaker at the speed of 100 revolutions per minute, and when the temperature of the heating sleeve reaches 70 ℃, the mixed liquid is continuously stirred for 20min to prepare the mixed liquid.
And keeping the temperature unchanged, continuously adding 68g of TDE-85 epoxy resin, 38gAG-80 epoxy resin and 38g of DDM curing agent into the mixture, and continuously stirring for 25min to obtain the resin composition.
A resin molded body prepared from the resin composition of this example had a tensile strength of 117MPa, an elongation at break of 5.6% and an impact strength of 22KJ/m2。
Example eight
According to a molar ratio of 1.1: 2 weighing 1, 2-epoxycyclohexane-4, 5-dimethyl acid solution and epoxy chloropropane solution, placing the solution in a beaker, and stirring the solution for 10min by a glass rod at normal temperature to prepare the epoxy resin monomer which is uniformly mixed.
13g of the prepared epoxy resin monomer, 21g of acrylic rubber, 37g of butanediol diglycidyl ether, and 5g of primary amine were weighed out and added to a beaker in this order. The beaker is placed in a heating sleeve, an electric stirring device is arranged at the opening of the beaker, and the heating temperature of the heating sleeve is set to be 66 ℃.
During the test, the heating sleeve, the ventilation device and the electric stirring device are sequentially started to electrically stir the mixed liquid in the beaker at the speed of 100 revolutions per minute, and when the temperature of the heating sleeve reaches 66 ℃, the mixed liquid is continuously stirred for 30min to prepare the mixed liquid.
Keeping the temperature unchanged, adding 61g of TDE-85 epoxy resin, 39g of 39gAG-80 epoxy resin and 32g of DDS curing agent into the mixture, and stirring for 30min to obtain the resin composition.
A resin molded body having a tensile strength of 10 was prepared from the resin composition of this example0MPa, elongation at break of 4.1%, and impact strength of 15KJ/m2。
Example nine
According to a molar ratio of 1.2: 2 weighing 1, 2-epoxycyclohexane-4, 5-dimethyl acid solution and epoxy chloropropane solution, placing the solution in a beaker, and stirring the solution for 10min by a glass rod at normal temperature to prepare the epoxy resin monomer which is uniformly mixed.
14g of the prepared epoxy resin monomer, 16g of acrylic rubber, 31g of trimethylolpropane triglycidyl ether and 6g of primary amine were weighed out and added to a beaker in this order. The beaker is placed in a heating sleeve, an electric stirring device is arranged at the opening of the beaker, and the heating temperature of the heating sleeve is set to be 60 ℃.
During the test, the heating sleeve, the ventilation device and the electric stirring device are sequentially started to electrically stir the mixed liquid in the beaker at the speed of 100 revolutions per minute, and when the temperature of the heating sleeve reaches 60 ℃, the mixed liquid is continuously stirred for 30min to prepare the mixed liquid.
And keeping the temperature unchanged, continuously adding 65g of TDE-85 epoxy resin, 35gAG-80 epoxy resin and 35g of DDM curing agent into the mixture, and continuously stirring for 30min to obtain the resin composition.
A resin molded body prepared from the resin composition of this example had a tensile strength of 102MPa, an elongation at break of 4.6% and an impact strength of 17KJ/m2。
Example ten
According to a molar ratio of 1.3: 2 weighing 1, 2-epoxycyclohexane-4, 5-dimethyl acid solution and epoxy chloropropane solution, placing the solution in a beaker, and stirring the solution for 10min by a glass rod at normal temperature to prepare the epoxy resin monomer which is uniformly mixed.
12g of the prepared epoxy resin monomer, 23g of acrylic rubber, 14g of trimethylolpropane triglycidyl ether, 20g of butanediol diglycidyl ether, and 7g of primary amine were weighed out and added to a beaker in this order. The beaker is placed in a heating sleeve, an electric stirring device is arranged at the opening of the beaker, and the heating temperature of the heating sleeve is set to be 65 ℃.
During the test, the heating sleeve, the ventilation device and the electric stirring device are sequentially started to electrically stir the mixed liquid in the beaker at the speed of 100 revolutions per minute, and when the temperature of the heating sleeve reaches 65 ℃, the mixed liquid is continuously stirred for 25min to prepare the mixed liquid.
And keeping the temperature unchanged, continuously adding 67g of TDE-85 epoxy resin, 37g of 37gAG-80 epoxy resin and 39g of DDS curing agent into the mixture, and continuously stirring for 30min to obtain the resin composition.
A resin molded body prepared from the resin composition of this example had a tensile strength of 107MPa, an elongation at break of 4.5% and an impact strength of 16KJ/m2。
Claims (9)
1. An epoxy resin composition for a wet winding molding composite material comprises the following materials in percentage by weight:
15 to 30 parts by mass of glycidyl group-containing acrylic rubber;
10-20 parts by mass of an epoxy resin monomer;
30-40 parts by mass of a polyepoxy reactive diluent;
5-8 parts by mass of primary amine;
60-70 parts of TDE-85 epoxy resin;
30-40 parts of AG-80 epoxy resin;
30-40 parts by mass of an amine epoxy curing agent;
the epoxy resin monomer is a mixture of 1, 2-epoxycyclohexane-4, 5-dicarboxylic acid and epichlorohydrin, wherein the molar ratio of the epoxy resin monomer to the epoxy resin monomer is (1-1.3): 2.
2. The epoxy resin composition for wet winding molding composite material according to claim 1, characterized in that: the above-mentioned
20 to 24 parts by mass of glycidyl group-containing acrylic rubber;
12-15 parts by mass of an epoxy resin monomer;
30-35 parts by mass of a polyepoxy reactive diluent.
3. The epoxy resin composition for wet-laid composites according to claim 1 or 2, wherein: the molar ratio of 1, 2-epoxycyclohexane-4, 5-dicarboxylic acid to epichlorohydrin in the epoxy resin monomer is (1.1-1.2): 2.
4. The epoxy resin composition for wet-laid composites according to claim 1 or 2, wherein: the polyepoxy reactive diluent is trimethylolpropane triglycidyl ether or butanediol diglycidyl ether, or a mixture of the two.
5. The epoxy resin composition for wet-laid composites according to claim 1 or 2, wherein: the primary amine is ethylenediamine or diethylenetriamine.
6. The epoxy resin composition for wet-laid composites according to claim 1 or 2, wherein: the amine epoxy curing agent is DDM or DDS.
7. A method for preparing the epoxy resin composition for wet-winding composite material according to claim 1, comprising the steps of:
1) mixing 1, 2-epoxycyclohexane-4, 5-dicarboxylic acid and epichlorohydrin in a molar ratio of (1-1.3) to (2) to prepare an epoxy resin monomer;
2) weighing 15-30 parts by mass of glycidyl-containing acrylic rubber, 30-40 parts by mass of polyepoxy reactive diluent and 5-8 parts by mass of primary amine, dissolving in 10-20 parts by mass of prepared epoxy resin monomer, heating to 60-70 ℃, and uniformly stirring and mixing to prepare a mixed solution;
3) and keeping the temperature unchanged, continuously adding 60-70 parts by mass of TDE-85 epoxy resin, 30-40 parts by mass of AG-80 epoxy resin and 30-40 parts by mass of amine epoxy curing agent into the prepared mixed solution, and uniformly stirring and mixing to obtain the epoxy resin composition for the wet winding molding composite material.
8. The method for preparing the epoxy resin composition for wet winding molding composite material according to claim 7, characterized in that: the mixed solution in the step 2) is prepared by dissolving 20-24 parts by mass of glycidyl-containing acrylic rubber, 30-35 parts by mass of polyepoxy reactive diluent and 5-8 parts by mass of primary amine into 12-15 parts by mass of prepared epoxy resin monomer, heating to 60-70 ℃, and uniformly stirring and mixing.
9. The method for preparing an epoxy resin composition for wet winding molding composite material according to claim 7 or 8, characterized in that: the epoxy resin monomer is prepared by mixing 1, 2-epoxycyclohexane-4, 5-dicarboxylic acid and epichlorohydrin according to a molar ratio of (1.1-1.2): 2.
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| CN114654829A (en) * | 2022-04-09 | 2022-06-24 | 江西鑫远基电子科技有限公司 | Aluminum-based copper-clad plate with high breakdown voltage and production process thereof |
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