CN112011153A - Epoxy SMC resin composition and preparation method thereof - Google Patents
Epoxy SMC resin composition and preparation method thereof Download PDFInfo
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- CN112011153A CN112011153A CN202010708882.2A CN202010708882A CN112011153A CN 112011153 A CN112011153 A CN 112011153A CN 202010708882 A CN202010708882 A CN 202010708882A CN 112011153 A CN112011153 A CN 112011153A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G59/40—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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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- C08J5/18—Manufacture of films or sheets
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- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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Abstract
The SMC epoxy composition prepared by the invention has low initial viscosity, is beneficial to infiltrating reinforced fiber materials, adopts polyamine compounds containing amino groups to modify and thicken an epoxy resin system, greatly increases the viscosity after curing, and meets the requirement of a sheet molding compound compression molding process. The epoxy composition does not contain solvents and other non-volatile substances, meets the environment-friendly requirement of low VOC of automobile part materials, has the characteristics of rapid forming at 140-160 ℃ for 3-10 min and the like, and has the characteristics of high mechanical strength after forming, good heat resistance and the like.
Description
Technical Field
The invention relates to the field of SMC resin composite materials, in particular to an epoxy SMC resin composition and a preparation method thereof.
Background
The SMC die pressing process is an advanced composite material forming method, and the SMC sheet molding compound has low price and convenient use, can be quickly formed to press products with different specifications, sizes and shapes, and is more and more accepted by the market. At present, the SMC mainly takes unsaturated polyester resin and vinyl resin as matrixes, but the unsaturated polyester resin and the vinyl resin SMC have the defects of poor temperature resistance and heat resistance, low structural strength and modulus and the like, and because a large amount of diluent styrene is added into an unsaturated polyester resin system, the diluent styrene volatilizes a large amount of pungent odor during molding, so that the physical health of a human body is influenced by long-term contact, and the environment is also greatly polluted.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the defects of pollution, poor temperature resistance and heat resistance, low structural strength and modulus and the like of the conventional SMC material, the invention provides an epoxy SMC composition and a preparation method thereof so as to solve the problems and the defects.
In order to solve the technical problems, the invention provides the following technical scheme:
an epoxy SMC composition and a preparation method thereof are prepared from A, B bi-components as follows:
the component A consists of a resin component and a curing agent component, and the components comprise the following materials in parts by weight:
the component B comprises the following materials in parts by weight:
2-15 parts of a thickening agent;
the filler, the curing agent and the accelerator are all solids, the thickener is a mono-amine or polyamine with at least one primary amino group and/or secondary amino group, and the molar ratio of the total active hydrogen of the primary amino group and the secondary amino group in the thickener to the epoxy group of the mixed epoxy resin is more than 0.05 and less than 0.4;
the A, B components are mixed, the initial viscosity is 5-100 Pa.s, the mixture is cured for 1-200 hrs at 20-70 ℃, the viscosity is 10000-1000000 Pa.s at 25 ℃, and the mixture can be rapidly cured and molded at 140-160 ℃ for 3-10 min.
Preferably, the thickener is one or more of aliphatic amines, alicyclic amines and aromatic amines such as ethylenediamine, dipropylenetriamine, diethylenetriamine, triethylenetetramine, m-xylylenediamine, 1, 3-cyclohexyldimethylamine, N-aminoethylpiperazine, isophoronediamine, methylcyclohexanediamine, cyclohexylpropylenediamine, 1, 2-cyclohexanediamine, 3' -dimethyl-4, 4-diaminodicyclohexylmethane, menthanediamine, polyetheramine and diethyltoluenediamine.
Preferably, the mixed epoxy resin is at least one of glycidyl ether type epoxy resin, glycidyl grease type epoxy resin, glycidyl amine type epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, special epoxy resin and modified epoxy resin.
Preferably, the diluent in the A component is composed of one or more than one reactive diluent containing one, two or more than one epoxy functional group,
preferably, the auxiliary agent is at least one of a coupling agent, a viscosity reducer, a wetting agent, a dispersing agent, a defoaming agent, a leveling agent, a toughening agent, a wetting agent, an anti-settling agent and an internal mold release agent, and the diluent is glycidyl ether or glycidyl ester.
Preferably, the filler is one or more of calcium carbonate, kaolin, bentonite, barium sulfate, talcum powder and aluminum hydroxide.
Preferably, the curing agent is at least one of dicyandiamide, organic acid hydrazide, aromatic amine and modified amine.
Preferably, the accelerator is at least one of organic urea, modified organic urea, imidazole and modified imidazole.
A preparation method of the epoxy SMC resin composition comprises the following specific steps:
a. accurately weighing the mixed epoxy resin, the diluent and the auxiliary agent in parts by mass of the resin components, placing the mixed epoxy resin, the diluent and the auxiliary agent in a reaction kettle with the temperature rising to 110 ℃, starting stirring, adding the filler in the reaction kettle in batches after the resin is melted and uniformly mixed, stirring at a high speed of 1500rpm, ensuring that the temperature of the material is lower than 120 ℃, and completely stirring and dispersing to obtain a material I;
b. accurately weighing the curing agent components, namely the liquid epoxy resin, the curing agent and the accelerator in parts by mass, stirring in a reaction kettle at a stirring temperature of not more than 45 ℃, uniformly mixing, and then carrying out three-roll grinding, wherein the particle size of the ground mixture is less than 10 mu m to obtain a material II;
c. reducing the temperature of the material I to be below 50 ℃, adding the material II into the material I, stirring for 0.5-1 h, and performing vacuum defoaming to obtain SMC resin;
d. accurately weighing the thickening agent in parts by mass, adding the thickening agent into SMC resin, starting stirring, stirring for 5-10 min to obtain epoxy SMC resin paste, and putting the mixed resin paste into a drying oven at 35-50 ℃ for curing for 10-20 h.
The invention has the following beneficial effects:
1. the liquid epoxy resin in the curing agent component can play a role in premixing solid particles, so that the solid particles such as the curing agent, the accelerator and the like are uniformly dispersed, and the powder agglomeration is prevented.
2. Volatile pollutants are not adopted and generated in the preparation process, so that the preparation method is friendly to human bodies and environment and has no pollution;
3. the epoxy SMC composition prepared by the invention has the characteristics of good temperature resistance and heat resistance, and higher structural strength and modulus.
4. The A, B components have low initial viscosity after mixing, are beneficial to impregnating glass fibers during preparing SMC sheets, and can quickly increase the viscosity after curing, and can be quickly cured at a proper temperature, thereby being beneficial to subsequent compression molding.
Detailed Description
The following examples are included to provide further detailed description of the present invention and to provide those skilled in the art with a more complete, concise, and exact understanding of the principles and spirit of the invention.
Example 1:
starting 83g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 6g of internal release agent, 0.75g of defoaming agent and 0.75g of impregnating compound in a reaction kettle, stirring, adding a filler into the reaction kettle after the resins are melted and mixed uniformly, stirring at a high speed, ensuring that the temperature of the materials is lower than 120 ℃, and mixing uniformly to obtain a first material; stirring a mixed grinding material consisting of 17g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 7g of dicyandiamide and 1.5g of organic urea in a reaction kettle, wherein the stirring temperature is not more than 45 ℃, uniformly mixing, carrying out three-roll grinding, and obtaining a material II after the grain size of the ground mixture is less than 10 mu m; reducing the temperature of the material I to be below 50 ℃, adding the material II into the material I, stirring for 0.5h, and carrying out vacuum defoaming to obtain SMC resin; finally, 4.4g of alicyclic amine is added and stirred uniformly to obtain epoxy SMC resin paste; and (3) impregnating 25mm disordered chopped glass fibers with the prepared epoxy SMC resin paste, rolling by an SMC sheet machine, and curing in a drying room at 35 ℃ for 20 hours to obtain the epoxy sheet molding compound.
Evaluation and test of properties of epoxy SMC resin composition for sheet molding compound
Performing vacuum degassing on the thickened epoxy SMC resin composition according to the GB/T2567-2008 requirement to obtain a casting body of the cured epoxy resin by drawing and bending a sample bar of casting resin under the curing condition of 135 ℃ multiplied by 1h, measuring the mechanical property of the casting body of the cured epoxy SMC resin based on the measuring method in GB/T2567-2004 using an electronic universal tensile tester, and measuring the glass transition temperature (Tg) of the cured epoxy resin composition based on the measuring method in GB/T19466-2004 using DSC (TADSC Q20);
the epoxy sheet molding compound is rapidly cured and molded in a mold with the size of 500mm x 4mm according to the curing condition of 150 x 5min, and the obtained cured product plate is subjected to cutting, stretching, bending and impact test on a sample strip according to the GB/T15568-2008 standard.
The physical properties of the epoxy SMC resin composition and the mechanical properties of the epoxy sheet molding compound are shown in the table I, the table II and the table III, the properties of the epoxy SMC resin composition and the mechanical properties of the epoxy sheet molding compound in the following examples are tested by the same method as in example 1, and the experimental data are shown in the table I, the table II and the table III.
Example 2
Stirring 78g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 5g of alicyclic glycidyl ester epoxy resin TDE-85, 6g of internal release agent, 0.75g of defoaming agent and 0.75g of impregnating compound in a reaction kettle, adding a filler into the reaction kettle after the resins are melted and mixed uniformly, stirring at a high speed, ensuring that the temperature of the materials is lower than 120 ℃, and mixing uniformly to obtain a first material; stirring a mixed grinding material consisting of 17g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 7g of dicyandiamide and 1.5g of organic urea in a reaction kettle, wherein the stirring temperature is not more than 45 ℃, uniformly mixing, carrying out three-roll grinding, and obtaining a material II after the grain size of the ground mixture is less than 10 mu m; reducing the temperature of the material I to 45 ℃, adding the material II into the material I, stirring for 1h, and carrying out vacuum defoaming to obtain SMC resin; finally, 5g of alicyclic amine is added and stirred uniformly to obtain epoxy SMC resin paste; and (3) impregnating 25mm disordered chopped glass fibers with the prepared epoxy SMC resin paste, rolling by an SMC sheet machine, and curing in a drying room at 35 ℃ for 20 hours to obtain the epoxy sheet molding compound.
Example 3
Starting and stirring 81g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 2g of alicyclic epoxy resin TTA-21, 6g of internal release agent, 0.75g of defoaming agent and 0.75g of impregnating compound in a reaction kettle, adding a filler into the reaction kettle after the resins are melted and uniformly mixed, stirring at a high speed, ensuring that the temperature of the materials is lower than 120 ℃, and uniformly mixing to obtain a first material; stirring a mixed grinding material consisting of 17g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 7g of dicyandiamide and 1.5g of organic urea in a reaction kettle, wherein the stirring temperature is not more than 45 ℃, uniformly mixing, carrying out three-roll grinding, and obtaining a material II after the grain size of the ground mixture is less than 10 mu m; reducing the temperature of the material I to 49 ℃, adding the material II into the material I, stirring for 45min, and carrying out vacuum defoaming to obtain SMC resin; finally, 5g of alicyclic amine is added and stirred uniformly to obtain epoxy SMC resin paste; and (3) impregnating 25mm disordered chopped glass fibers with the prepared epoxy SMC resin paste, rolling by an SMC sheet machine, and curing in a drying room at 35 ℃ for 20 hours to obtain the epoxy sheet molding compound.
Example 4
75g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 5g of trimethylolpropane triglycidyl ether XY-636, 6g of internal release agent, 0.75g of defoaming agent and 0.75g of impregnating compound are put into a reaction kettle and stirred, after the resins are melted and mixed uniformly, the fillers are added into the reaction kettle and stirred at high speed, the temperature of the materials is ensured to be 90-120 ℃, and the materials are mixed uniformly to obtain a first material; stirring a mixed grinding material consisting of 20g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 6.5g of dicyandiamide, 2g of organic acid hydrazide and 1.5g of organic urea in a reaction kettle, wherein the stirring temperature is not more than 45 ℃, uniformly mixing, carrying out three-roll grinding, and obtaining a material II after the grain size of the ground mixture is less than 10 mu m; reducing the temperature of the material I to 40 ℃, adding the material II into the material I, stirring for 1h, and carrying out vacuum defoaming to obtain SMC resin; finally, 5g of alicyclic amine is added and stirred uniformly to obtain epoxy SMC resin paste; and (3) impregnating 25mm disordered chopped glass fibers with the prepared epoxy SMC resin paste, rolling by an SMC sheet machine, and curing for 15 hours in a drying room at 40 ℃ to obtain the epoxy sheet molding compound.
Example 5
Starting and stirring 82g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 6g of internal release agent, 0.75g of defoaming agent and 0.75g of impregnating compound in a reaction kettle, adding a filler into the reaction kettle after the resins are melted and mixed uniformly, stirring at a high speed, ensuring that the temperature of the materials is lower than 120 ℃, and mixing uniformly to obtain a first material; stirring a mixed grinding material consisting of 18g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 6g of dicyandiamide, 2g of organic urea and 1g of imidazole in a reaction kettle, wherein the stirring temperature is not more than 45 ℃, uniformly mixing, carrying out three-roll grinding, and obtaining a material II after the grain size of the ground mixture is less than 10 mu m; reducing the temperature of the material I to 35 ℃, adding the material II into the material I, stirring for 1h, and carrying out vacuum defoaming to obtain SMC resin; finally, 3g of alicyclic amine and 4g of polyether amine are added and uniformly stirred to obtain epoxy SMC resin paste; and (3) impregnating 25mm disordered chopped glass fibers with the prepared epoxy SMC resin paste, rolling by an SMC sheet machine, and curing in a drying room at 35 ℃ for 20 hours to obtain the epoxy sheet molding compound.
Example 6
Starting and stirring 82g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 150g of calcium carbonate, 18g of internal release agent, 0.75g of defoaming agent, 0.75g of impregnating compound and 1.5g of viscosity reducer in a reaction kettle, adding filler into the reaction kettle after the resins are melted and mixed uniformly, stirring at a high speed to ensure that the temperature of the materials is lower than 120 ℃, and mixing uniformly to obtain a first material; stirring a mixed grinding material consisting of 22g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 6g of dicyandiamide, 2g of organic urea and 1g of imidazole in a reaction kettle, wherein the stirring temperature is not more than 45 ℃, uniformly mixing, carrying out three-roll grinding, and obtaining a material II after the grain size of the ground mixture is less than 10 mu m; reducing the temperature of the material I to below 25 ℃, adding the material II into the material I, stirring for 1h, and carrying out vacuum defoaming to obtain SMC resin; finally, adding 6 alicyclic amine, and uniformly stirring to obtain epoxy SMC resin paste; and (3) impregnating 25mm disordered chopped glass fibers with the prepared epoxy SMC resin paste, rolling by an SMC sheet machine, and curing in a drying room at 35 ℃ for 20 hours to obtain the epoxy sheet molding compound.
Example 7
Starting and stirring 65g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 5g of trimethylolpropane triglycidyl ether XY-636, 6g of internal release agent, 0.5g of defoaming agent and 0.5g of impregnating compound in a reaction kettle, adding a filler into the reaction kettle after the resins are melted and mixed uniformly, stirring at a high speed, ensuring that the temperature of the materials is lower than 120 ℃, and mixing uniformly to obtain a first material; stirring a mixed grinding material consisting of 30g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 5g of dicyandiamide, 8g of 4' 4 diaminodiphenyl sulfone DDS and 2g of organic urea in a reaction kettle, wherein the stirring temperature is not more than 45 ℃, uniformly mixing, carrying out three-roll grinding, and obtaining a material II when the particle size of the ground mixture is less than 10 mu m; reducing the temperature of the material I to 48 ℃, adding the material II into the material I, stirring for 1h, and carrying out vacuum defoaming to obtain SMC resin; finally, 4.4g of alicyclic amine is added and stirred uniformly to obtain epoxy SMC resin paste; and (3) impregnating 25mm disordered chopped glass fibers with the prepared epoxy SMC resin paste, rolling by an SMC sheet machine, and curing for 15 hours in a drying room at 40 ℃ to obtain the epoxy sheet molding compound.
Example 8
Starting and stirring 80g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 6g of internal release agent, 0.5g of defoaming agent and 0.5g of impregnating compound in a reaction kettle, adding a filler into the reaction kettle after the resins are melted and mixed uniformly, stirring at a high speed, ensuring that the temperature of the materials is 70-100 ℃, and mixing uniformly to obtain a first material; stirring a mixed grinding material consisting of 20g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 7g of dicyandiamide, 2g of organic urea and 1g of imidazole in a reaction kettle, wherein the stirring temperature is not more than 45 ℃, uniformly mixing, carrying out three-roll grinding, and obtaining a material II after the grain size of the ground mixture is less than 10 mu m; reducing the temperature of the material I to 45 ℃, adding the material II into the material I, stirring for 50min, and carrying out vacuum defoaming to obtain SMC resin; finally, 8g of modified alicyclic amine is added and uniformly stirred, and epoxy SMC resin paste is obtained; and (3) impregnating 25mm disordered chopped glass fibers with the prepared epoxy SMC resin paste, rolling by an SMC sheet machine, and curing for 15 hours in a drying room at 40 ℃ to obtain the epoxy sheet molding compound.
Example 9
82g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 6g of internal release agent, 0.5g of defoaming agent and 0.5g of impregnating compound are put into a reaction kettle and stirred, after the resins are melted and mixed uniformly, the fillers are added into the reaction kettle and stirred at high speed, the temperature of the materials is ensured to be lower than 120 ℃, and the materials are mixed uniformly to obtain a first material; stirring a mixed grinding material consisting of 18g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 7g of dicyandiamide and 2g of organic urea in a reaction kettle, wherein the stirring temperature is not more than 45 ℃, uniformly mixing, carrying out three-roll grinding, and obtaining a material II after the grain diameter of the ground mixture is less than 10 mu m; reducing the temperature of the material I to 40 ℃, adding the material II into the material I, stirring for 1h, and carrying out vacuum defoaming to obtain SMC resin; finally, 5g of aromatic amine is added and stirred for 10min, and epoxy SMC resin paste is obtained; and (3) impregnating 25mm disordered chopped glass fibers with the prepared epoxy SMC resin paste, rolling by an SMC sheet machine, and curing for 15 hours in a drying room at 40 ℃ to obtain the epoxy sheet molding compound.
Example 10
Starting and stirring 63g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 5g of trimethylolpropane triglycidyl ether XY-636, 15g of CTBN modified epoxy resin prepolymer 861340, 6g of internal mold release agent, 0.5g of defoaming agent and 0.5g of impregnating compound in a reaction kettle, adding a filler into the reaction kettle after the resins are melted and uniformly mixed, stirring at a high speed to ensure that the temperature of the materials is lower than 120 ℃, and uniformly mixing to obtain a first material; stirring a mixed grinding material consisting of 17g of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, 7g of dicyandiamide and 1.5g of organic urea in a reaction kettle, wherein the stirring temperature is not more than 45 ℃, uniformly mixing, carrying out three-roll grinding, and obtaining a material II after the grain size of the ground mixture is less than 10 mu m; reducing the temperature of the material I to be below 50 ℃, adding the material II into the material I, stirring for 0.5h, and carrying out vacuum defoaming to obtain SMC resin; finally, 5g of aromatic amine is added and stirred for 5min, and epoxy SMC resin paste is obtained; and (3) impregnating 25mm disordered chopped glass fibers with the prepared epoxy SMC resin paste, rolling by an SMC sheet machine, and curing in a drying room at 50 ℃ for 10 hours to obtain the epoxy sheet molding compound.
Example 11: the rest is the same as example 10 except that:
the thickening agent is a mono-amine or polyamine with at least one primary amino group and/or secondary amino group, and the molar ratio of the total active hydrogen of the primary amino group and the secondary amino group in the thickening agent to the epoxy group of the mixed epoxy resin is more than 0.05 and less than 0.4; the thickener may be equally replaced with one or more of aliphatic, alicyclic and aromatic amines such as ethylenediamine, dipropylenetriamine, diethylenetriamine, triethylenetetramine, m-xylylenediamine, 1, 3-cyclohexyldimethylamine, N-aminoethylpiperazine, isophoronediamine, methylcyclohexanediamine, cyclohexylpropylenediamine, 1, 2-cyclohexanediamine, 3' -dimethyl-4, 4-diaminodicyclohexylmethane, menthanediamine, polyetheramine, diethyltoluenediamine and the like.
The mixed epoxy resin can be equivalently replaced by at least one of glycidyl ether type epoxy resin, glycidyl grease type epoxy resin, glycidyl amine type epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, special epoxy resin and modified epoxy resin.
The diluent in the component A is composed of one or more than one reactive diluent containing one, two or more than one epoxy functional group, preferably glycidyl ether or glycidyl ester.
The auxiliary agent is at least one of coupling agent, viscosity reducer, wetting agent, dispersing agent, defoaming agent, flatting agent, toughening agent, wetting agent, anti-settling agent and internal release agent.
The filler is preferably one or more of calcium carbonate, kaolin, bentonite, barium sulfate, talcum powder and aluminum hydroxide.
The curing agent is at least one of dicyandiamide, organic acid hydrazide, aromatic amine and modified amine.
The accelerator is at least one of organic urea, modified organic urea, imidazole and modified imidazole.
Attached table:
TABLE physical and mechanical Properties of epoxy SMC resin pastes prepared in examples 1-5
TABLE II physical and mechanical properties of epoxy SMC resin pastes prepared in examples 6-10
Mechanical properties of sheet molding compound
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention cannot be limited thereby, and any modification made on the basis of the technical scheme according to the technical idea proposed by the present invention falls within the protection scope of the present invention; the technology not related to the invention can be realized by the prior art.
Claims (9)
1. An epoxy SMC resin composition, which is characterized by being prepared from A, B bi-component as follows:
the component A consists of a resin component and a curing agent component, and the components comprise the following materials in parts by weight:
resin component (c):
curing agent component:
10-40 parts by mass of liquid epoxy resin;
2-20 parts of a curing agent;
1-8 parts of an accelerator;
the component B comprises the following materials in parts by weight:
2-15 parts of a thickening agent;
the filler, the curing agent and the accelerator are all solids, the thickener is a mono-amine or polyamine with at least one primary amino group and/or secondary amino group, and the molar ratio of the total active hydrogen of the primary amino group and the secondary amino group in the thickener to the epoxy group of the mixed epoxy resin is more than 0.05 and less than 0.4;
the A, B components are mixed, the initial viscosity is 5-100 Pa.s, the mixture is cured for 1-200 hrs at 20-70 ℃, the viscosity is 10000-1000000 Pa.s at 25 ℃, and the mixture can be rapidly cured and molded at 140-160 ℃ for 3-10 min.
2. An epoxy SMC resin composition according to claim 1 wherein: the thickening agent is one or more of aliphatic amine, alicyclic amine and aromatic amine such as ethylenediamine, dipropylenetriamine, diethylenetriamine, triethylene tetramine, m-xylylenediamine, 1, 3-cyclohexyldimethylamine, N-aminoethyl piperazine, isophorone diamine, methylcyclohexanediamine, cyclohexylpropylenediamine, 1, 2-cyclohexanediamine, 3' -dimethyl-4, 4-diaminodicyclohexylmethane, menthane diamine, polyether amine, diethyl toluenediamine and the like.
3. An epoxy SMC resin composition according to claim 1 wherein: the mixed epoxy resin is at least one of glycidyl ether type epoxy resin, glycidyl grease type epoxy resin, glycidyl amine type epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, special epoxy resin and modified epoxy resin.
4. An epoxy SMC resin composition according to claim 1 wherein: the diluent in the component A is composed of one or more than one reactive diluent containing one, two or more than one epoxy functional group.
5. An epoxy SMC resin composition according to claim 1 wherein: the auxiliary agent is at least one of a coupling agent, a viscosity reducer, a wetting agent, a dispersing agent, a defoaming agent, a flatting agent, a toughening agent, a wetting agent, an anti-settling agent and an internal mold release agent, and the diluent is glycidyl ether or glycidyl ester.
6. An epoxy SMC resin composition according to claim 1 wherein: the filler is one or more of calcium carbonate, kaolin, bentonite, barium sulfate, talcum powder and aluminum hydroxide.
7. An epoxy SMC resin composition according to claim 1 wherein: the curing agent is at least one of dicyandiamide, organic acid hydrazide, aromatic amine and modified amine.
8. An epoxy SMC resin composition according to claim 1 wherein: the accelerant is at least one of organic urea, modified organic urea, imidazole and modified imidazole.
9. A method for preparing the epoxy SMC resin composition of any of claims 1-8, comprising the steps of:
a. accurately weighing the mixed epoxy resin, the diluent and the auxiliary agent in parts by mass of the resin components, placing the mixed epoxy resin, the diluent and the auxiliary agent in a reaction kettle with the temperature rising to 110 ℃, starting stirring, adding the filler in the reaction kettle in batches after the resin is melted and uniformly mixed, stirring at a high speed of 1500rpm, ensuring that the temperature of the material is lower than 120 ℃, and completely stirring and dispersing to obtain a material I;
b. accurately weighing the curing agent components, namely the liquid epoxy resin, the curing agent and the accelerator in parts by mass, fully stirring in a reaction kettle at a stirring temperature of not more than 45 ℃, uniformly mixing, and then carrying out three-roll grinding, wherein the particle size of the ground mixture is less than 10 mu m to obtain a material II;
c. reducing the temperature of the material I to be below 50 ℃, adding the material II into the material I, stirring for 0.5-1 h, and performing vacuum defoaming to obtain SMC resin;
d. accurately weighing the thickening agent in parts by mass, adding the thickening agent into SMC resin, starting stirring, stirring for 5-10 min to obtain epoxy SMC resin paste, and putting the mixed resin paste into a drying oven at 35-50 ℃ for curing for 10-20 h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112048156A (en) * | 2020-07-28 | 2020-12-08 | 艾达索高新材料芜湖有限公司 | Epoxy SMC resin |
| US20210031440A1 (en) * | 2018-04-05 | 2021-02-04 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Method and assembly for a continuous or semi-continuous additive manufacture of components |
| CN114249967A (en) * | 2022-03-01 | 2022-03-29 | 朗昇高新材料科技(天津)有限公司 | High-temperature-resistant epoxy SMC resin composition and preparation method thereof |
| CN116769277A (en) * | 2023-05-30 | 2023-09-19 | 江苏恒隆通新材料科技有限公司 | Medium-temperature fast-curing high-hardness laminated resin |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096443A (en) * | 2007-07-10 | 2008-01-02 | 武汉理工大学 | Method for preparing epoxy sheet mould plastic |
| CN102337007A (en) * | 2011-07-01 | 2012-02-01 | 蓝星(北京)化工机械有限公司 | High-performance epoxy resin composition for sheet molding compound (SMC) |
| CN103865232A (en) * | 2014-02-27 | 2014-06-18 | 江苏恒神纤维材料有限公司 | High-toughness fire retarding epoxy resin composition and preparation method thereof |
| CN104387565A (en) * | 2014-11-17 | 2015-03-04 | 苏州苏月新材料有限公司 | Composite system of epoxy resin and curing agent for prepreg and preparation method of composite system |
| CN105368010A (en) * | 2015-11-13 | 2016-03-02 | 中航复合材料有限责任公司 | Epoxy resin suitable for long-term storage at room temperature and preparation method thereof |
| CN106893256A (en) * | 2015-12-18 | 2017-06-27 | 比亚迪股份有限公司 | A kind of epoxy resin composition for prepreg and preparation method thereof and prepreg |
| CN106987095A (en) * | 2017-05-16 | 2017-07-28 | 广东博汇新材料科技股份有限公司 | High transparency epoxy resin composition for prepreg and preparation method thereof |
| CN108410130A (en) * | 2018-02-08 | 2018-08-17 | 芜湖天道绿色新材料有限公司 | A kind of sheet molding compound cured epoxy composition and preparation method thereof |
| CN109535660A (en) * | 2018-12-18 | 2019-03-29 | 深圳航天科技创新研究院 | A kind of fire-retardant prepreg resin of the rapid curing that viscosity is controllable and preparation method thereof |
| CN111205596A (en) * | 2020-02-26 | 2020-05-29 | 艾达索高新材料芜湖有限公司 | Epoxy chopped carbon fiber mat prepreg for rapid prototyping and production process thereof |
-
2020
- 2020-07-22 CN CN202010708882.2A patent/CN112011153A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096443A (en) * | 2007-07-10 | 2008-01-02 | 武汉理工大学 | Method for preparing epoxy sheet mould plastic |
| CN102337007A (en) * | 2011-07-01 | 2012-02-01 | 蓝星(北京)化工机械有限公司 | High-performance epoxy resin composition for sheet molding compound (SMC) |
| CN103865232A (en) * | 2014-02-27 | 2014-06-18 | 江苏恒神纤维材料有限公司 | High-toughness fire retarding epoxy resin composition and preparation method thereof |
| CN104387565A (en) * | 2014-11-17 | 2015-03-04 | 苏州苏月新材料有限公司 | Composite system of epoxy resin and curing agent for prepreg and preparation method of composite system |
| CN105368010A (en) * | 2015-11-13 | 2016-03-02 | 中航复合材料有限责任公司 | Epoxy resin suitable for long-term storage at room temperature and preparation method thereof |
| CN106893256A (en) * | 2015-12-18 | 2017-06-27 | 比亚迪股份有限公司 | A kind of epoxy resin composition for prepreg and preparation method thereof and prepreg |
| CN106987095A (en) * | 2017-05-16 | 2017-07-28 | 广东博汇新材料科技股份有限公司 | High transparency epoxy resin composition for prepreg and preparation method thereof |
| CN108410130A (en) * | 2018-02-08 | 2018-08-17 | 芜湖天道绿色新材料有限公司 | A kind of sheet molding compound cured epoxy composition and preparation method thereof |
| CN109535660A (en) * | 2018-12-18 | 2019-03-29 | 深圳航天科技创新研究院 | A kind of fire-retardant prepreg resin of the rapid curing that viscosity is controllable and preparation method thereof |
| CN111205596A (en) * | 2020-02-26 | 2020-05-29 | 艾达索高新材料芜湖有限公司 | Epoxy chopped carbon fiber mat prepreg for rapid prototyping and production process thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210031440A1 (en) * | 2018-04-05 | 2021-02-04 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Method and assembly for a continuous or semi-continuous additive manufacture of components |
| CN112048156A (en) * | 2020-07-28 | 2020-12-08 | 艾达索高新材料芜湖有限公司 | Epoxy SMC resin |
| CN114249967A (en) * | 2022-03-01 | 2022-03-29 | 朗昇高新材料科技(天津)有限公司 | High-temperature-resistant epoxy SMC resin composition and preparation method thereof |
| CN116769277A (en) * | 2023-05-30 | 2023-09-19 | 江苏恒隆通新材料科技有限公司 | Medium-temperature fast-curing high-hardness laminated resin |
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