CN112048153A - Flame-retardant epoxy sheet molding compound and preparation method thereof - Google Patents
Flame-retardant epoxy sheet molding compound and preparation method thereof Download PDFInfo
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- CN112048153A CN112048153A CN202010737254.7A CN202010737254A CN112048153A CN 112048153 A CN112048153 A CN 112048153A CN 202010737254 A CN202010737254 A CN 202010737254A CN 112048153 A CN112048153 A CN 112048153A
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- epoxy resin
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- sheet molding
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- 239000003677 Sheet moulding compound Substances 0.000 title claims abstract description 141
- 239000004593 Epoxy Substances 0.000 title claims abstract description 118
- 239000003063 flame retardant Substances 0.000 title claims abstract description 68
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000003822 epoxy resin Substances 0.000 claims abstract description 72
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 72
- 239000003365 glass fiber Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000002562 thickening agent Substances 0.000 claims abstract description 26
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- 239000003085 diluting agent Substances 0.000 claims abstract description 12
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 7
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 6
- 239000004844 aliphatic epoxy resin Substances 0.000 claims abstract description 5
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 3
- 239000004519 grease Substances 0.000 claims abstract description 3
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims description 82
- 239000011347 resin Substances 0.000 claims description 82
- 238000003756 stirring Methods 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 24
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- -1 alkyl phosphinate Chemical compound 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000005086 pumping Methods 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 9
- 150000004982 aromatic amines Chemical class 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000009736 wetting Methods 0.000 claims description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 238000007790 scraping Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004513 sizing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 54
- 238000005452 bending Methods 0.000 description 23
- 238000003825 pressing Methods 0.000 description 10
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 4
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 4
- ITZGNPZZAICLKA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylate Chemical compound C1C2OC2CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 ITZGNPZZAICLKA-UHFFFAOYSA-N 0.000 description 4
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000010132 sheet moulding compound process Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
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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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- 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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/5205—Salts of P-acids with N-bases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a flame-retardant epoxy sheet molding compound and a preparation method thereof, wherein the flame-retardant epoxy sheet molding compound is prepared from the following raw materials in parts by weight: 85-100 parts of epoxy composition, 0-15 parts of diluent, 30-200 parts of environment-friendly halogen-free flame retardant, 1-15 parts of auxiliary agent, 3-25 parts of curing accelerator, 2-15 parts of thickening agent and 50-150 parts of chopped glass fiber, wherein the thickening agent is liquid amine with primary amino group or secondary amino group; the epoxy composition 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. The flame retardant grade of the invention can reach UL94-V0 grade, the limiting oxygen index can reach more than 32, the material has higher mechanical property, and the material does not contain volatile micromolecular compounds and solvents, thereby meeting the environmental protection requirement of low VOC.
Description
Technical Field
The invention relates to the technical field of preparation of fiber reinforced thermosetting resin composite materials, in particular to a flame-retardant epoxy sheet molding compound 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.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at various problems in the existing SMC composite material and preparation method, the invention provides a flame-retardant epoxy sheet molding compound and a preparation method thereof, and solves the problems.
In order to solve the technical problems, the invention provides the following technical scheme:
the flame-retardant epoxy sheet molding compound is prepared from the following raw materials in parts by weight: 85-100 parts of epoxy composition, 0-15 parts of diluent, 30-200 parts of environment-friendly halogen-free flame retardant, 1-15 parts of auxiliary agent, 3-25 parts of curing accelerator, 2-15 parts of thickening agent and 50-150 parts of chopped glass fiber, wherein the thickening agent is liquid amine with primary amino group or secondary amino group; the epoxy composition 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 is comprised of one or more of reactive diluents containing one or more epoxy functional groups.
Preferably, the environment-friendly halogen-free flame retardant is at least one of a halogen-free phosphorus-nitrogen mixed flame retardant, an ammonium polyphosphate flame retardant, melamine cyanurate, hexaphenoxycyclotriphosphazene, an alkyl phosphinate and aluminum hydroxide.
The auxiliary agent comprises an internal release agent and a wetting dispersant.
Preferably, the curing accelerator is a compound of a component A and a component B, the component A is one or more of dicyandiamide, organic acid hydrazide, aromatic amine and modified amine, and the component B is one or more of organic urea, modified organic urea, imidazole and modified imidazole.
Preferably, the thickening agent is at least one of aliphatic amine, alicyclic amine, aromatic amine, polyether amine, polyamide and modified amine of aliphatic amine, alicyclic amine, aromatic amine, polyether amine and polyamide, and the molar ratio of the total primary amino and secondary amino active hydrogen in the thickening agent to epoxy group in the epoxy composition is more than 0.01 and less than 0.6.
Preferably, the chopped glass fiber is a stranded yarn glass fiber treated by an epoxy sizing agent, and the length of the chopped glass fiber is 10-50 mm.
The preparation method of the flame-retardant epoxy sheet molding compound comprises the following steps:
a. accurately weighing the epoxy composition, the diluent and the auxiliary agent in a reaction kettle, starting stirring, adding the environment-friendly halogen-free flame retardant into the reaction kettle after the resin is melted and uniformly mixed, and performing high-speed dispersion and stirring to ensure that the temperature of the material is lower than 120 ℃, and uniformly mixing to obtain a material A;
b. reducing the temperature of the material A to below 50 ℃, adding a curing accelerator into a resin reaction kettle, stirring for 0.5-1 h, performing vacuum defoaming and discharging to obtain epoxy resin paste;
c. pumping the epoxy resin paste and the amino-containing liquid ammonia thickener into a series mixer by a resin feed pump and a thickener feed pump in proportion, stirring at a high speed, uniformly mixing, and flowing into a resin scraping tank;
d. uniformly coating the epoxy resin paste capable of being thickened rapidly on the upper and lower bearing films by a resin glue groove scraper to form an epoxy resin film;
e. the SMC sheet machine is characterized in that a yarn cutting roller cuts glass fibers, the glass fibers are uniformly doffed, the chopped glass fibers are pasted on a lower bearing film epoxy resin, the chopped glass fibers are covered by an upper bearing film epoxy resin paste, the epoxy resin paste is fully soaked into the glass fibers to form epoxy glass fiber sheets through extrusion and exhaust, and then the epoxy glass fiber sheets are rolled or packaged in a box type;
f. curing the rolled or box-packed epoxy glass fiber sheet in a drying room to quickly thicken the epoxy resin to obtain the flame-retardant epoxy sheet molding compound.
Preferably, the curing temperature is 20-70 ℃ and the curing time is 1-200 hrs.
The invention has the following beneficial effects:
the flame-retardant epoxy sheet molding compound prepared by the invention does not contain volatile micromolecular compounds and solvents, and meets the environment-friendly requirement of low VOC. The fiber reinforced composite material prepared by the flame-retardant epoxy sheet molding compound has good mechanical property, the tensile strength reaches more than 135Mpa, the tensile modulus reaches more than 10Gpa, the bending strength reaches more than 200Mpa, the bending modulus reaches more than 10Gpa, and the impact strength reaches 100KJ/m2Meanwhile, the flame-retardant halogen-free flame-retardant flame-.
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.
The glass fiber raw material used in the present invention:
A. the glass fiber of the Tsinging International ECT-55E-2400TEX twisted yarn is a special glass fiber specially designed and developed for an epoxy sheet molding compound process, and a silane impregnating agent contained in the product can form good impregnation with epoxy resin, so that excellent mechanical properties are provided for the product.
B. The Euvens corning ME1510-4800TEX plied yarn glass fiber is special glass fiber designed and developed for an epoxy sheet molding compound process, and a silane impregnating agent contained in the product can form good impregnation with epoxy resin, so that excellent mechanical properties are provided for the product.
The performance test of the flame-retardant epoxy sheet molding compound is carried out by the following steps:
testing the mechanical property of a composite material product prepared from the flame-retardant epoxy sheet molding compound by adopting a testing method of an electronic universal tensile testing machine based on GB/T1446-; the bending property is tested based on the GB/T1449-; testing the unnotched impact strength of a composite material product prepared by the flame-retardant epoxy sheet molding compound by adopting a unnotched impact performance testing method of a simply supported beam based on GB/T1451-2005 standard; testing the combustion grade based on the GB/T4609 standard; the limiting oxygen index was tested based on the GB/T8924 standard.
In the following examples, parts are by weight.
Example 1
Putting 85 parts of epoxy composition, 5 parts of trimethylolpropane triglycidyl ether XY-636 (serving as a diluent) and 6 parts of internal release agent into a reaction kettle, starting stirring, adding 150 parts of aluminum hydroxide into the reaction kettle after the resin is melted and uniformly mixed, dispersing and stirring at a high speed, ensuring that the temperature of the material is lower than 70 ℃, and uniformly mixing to obtain a material A; reducing the temperature of the material A to below 50 ℃, adding a curing accelerator consisting of 7 parts of dicyandiamide and 1.5 parts of organic urea into a resin reaction kettle, stirring for 0.5h, performing vacuum defoaming and discharging to obtain epoxy resin paste; pumping the epoxy resin paste and 4.4 parts of alicyclic amine into a series mixer in proportion through a resin feed pump and a thickener feed pump, stirring at a high speed, uniformly mixing, and flowing into a resin frictioning tank to obtain epoxy SMC resin paste; soaking 100 parts of 24mm disordered chopped glass fiber in the prepared epoxy SMC resin paste, and uniformly coating the rapidly thickened epoxy resin paste on an upper bearing film and a lower bearing film by a resin glue groove scraper to form an epoxy resin film; the SMC sheet machine is characterized in that a yarn cutting roller cuts glass fibers, the glass fibers are uniformly doffed, the chopped glass fibers are pasted on a lower bearing film epoxy resin, the chopped glass fibers are covered by an upper bearing film epoxy resin paste, the epoxy resin paste is fully soaked into the glass fibers to form epoxy glass fiber sheets through extrusion and exhaust, and then the epoxy glass fiber sheets are rolled or packaged in a box type; curing the mixture in a drying room at 35 ℃ for 20 hours to obtain the flame-retardant epoxy sheet molding compound.
The epoxy composition is bisphenol A glycidyl ether type liquid epoxy resin NPEL-128.
The mechanical property of the flame-retardant epoxy sheet molding compound pressing plate is tested as follows:
the tensile strength of the sheet molding compound is 148MPa and the tensile modulus is 11.3GPa according to the test of GB/T1447; the bending strength of the sheet molding compound is 288MPa according to the test of GB/T1449, and the bending modulus is 10.4 GPa; testing the unnotched impact strength of the sheet molding compound to be 114 KJ/square meter according to GB/T1451-2005; the burning grade of the sheet molding compound is UL94-V0 according to the test of GB/T4609; the oxygen limiting index of the sheet molding compound is 36% according to GB/T8924 test.
Example 2
Putting 95 parts of epoxy composition, 5 parts of alicyclic glycidyl ester epoxy resin TDE-85 (serving as a diluent) and 6 parts of internal mold release agent into a reaction kettle, starting stirring, adding 60 parts of phosphorus-nitrogen flame retardant into the reaction kettle after the resins are melted and uniformly mixed, dispersing and stirring at a high speed, ensuring that the temperature of the materials is lower than 70 ℃, and uniformly mixing to obtain a material A; reducing the temperature of the material A to below 50 ℃, adding a curing accelerator consisting of 7 parts of dicyandiamide and 1.5 parts of organic urea into a resin reaction kettle, stirring for 1 hour, and performing vacuum defoaming discharge to obtain epoxy resin paste; pumping the epoxy resin paste and 5 parts of alicyclic amine into a series mixer in proportion through a resin feed pump and a thickener feed pump, stirring at a high speed, uniformly mixing, and flowing into a resin frictioning tank to obtain epoxy SMC resin paste; the prepared epoxy SMC resin paste is soaked in 110 parts of 24mm disordered chopped glass fibers, the steps are the same as those of example 1, and the epoxy SMC resin paste is rolled and exhausted by an SMC sheet machine, and then is sent into a drying room at 35 ℃ for curing for 20 hours to obtain the flame-retardant epoxy sheet molding compound. The epoxy composition is a diglycidyl phthalate,
the mechanical property of the flame-retardant epoxy sheet molding compound pressing plate is tested as follows:
the tensile strength of the sheet molding compound is 153MPa and the tensile modulus is 11.8GPa according to the test of GB/T1447; testing the bending strength of the sheet molding compound according to GB/T1449 to 281MPa, and the bending modulus to 10.9 GPa; the unnotched impact strength of the sheet molding compound is 121 KJ/square meter according to GB/T1451 test; the burning grade of the sheet molding compound is UL94-V0 according to the test of GB/T4609; the oxygen limiting index of the sheet molding compound is 36% according to GB/T8924 test.
Example 3
Putting 98 parts of epoxy composition, 2 parts of alicyclic epoxy resin TTA-21 (serving as a diluent) and 6 parts of internal mold release agent into a reaction kettle, starting stirring, adding 60g of phosphorus-nitrogen flame retardant into the reaction kettle after the resins are melted and uniformly mixed, dispersing and stirring at a high speed, ensuring that the temperature of the materials is lower than 70 ℃, and uniformly mixing to obtain a material A; reducing the temperature of the material A to below 50 ℃, adding a curing accelerator consisting of 7 parts of dicyandiamide and 1.5 parts of organic urea into a resin reaction kettle, stirring for 45min, performing vacuum defoaming and discharging to obtain epoxy resin paste; pumping the epoxy resin paste and 5 parts of alicyclic amine into a series mixer in proportion through a resin feed pump and a thickener feed pump, stirring at a high speed, uniformly mixing, and flowing into a resin frictioning tank to obtain epoxy SMC resin paste; the prepared flame-retardant epoxy SMC resin paste is soaked in 120 parts of 48mm disordered chopped glass fibers, the steps are the same as those of the embodiment 1, and the flame-retardant epoxy sheet molding compound is obtained after the flame-retardant epoxy SMC resin paste is rolled and exhausted by an SMC sheet machine and is sent into a drying room at 35 ℃ for curing for 20 hours. The epoxy composition is diaminodiphenylmethane tetraglycidyl amine,
the mechanical property of the flame-retardant epoxy sheet molding compound pressing plate is tested as follows:
the tensile strength of the sheet molding compound is 138MPa and the tensile modulus is 10.4GPa according to the test of GB/T1447; the bending strength of the sheet molding compound is 262MPa and the bending modulus is 10.5GPa according to the test of GB/T1449; the unnotched impact strength of the sheet molding compound is 121 KJ/square meter according to GB/T1451 test; the burning grade of the sheet molding compound is UL94-V0 according to the test of GB/T4609; the limiting oxygen index of the sheet molding compound is 35% according to GB/T8924 test.
Example 4
Putting 95 parts of epoxy composition, 5 parts of trimethylolpropane triglycidyl ether XY-636 and 6 parts of internal release agent into a reaction kettle, starting stirring, adding 150 parts of ammonium polyphosphate flame retardant into the reaction kettle after the resin is melted and uniformly mixed, and performing high-speed dispersion stirring to ensure that the temperature of the material is lower than 70 ℃, and uniformly mixing to obtain a material A; reducing the temperature of the material A to below 50 ℃, adding a curing accelerator consisting of 6.5 parts of dicyandiamide, 2 parts of organic acid hydrazide and 1.5 parts of organic urea into a resin reaction kettle, stirring for 50min, performing vacuum defoaming, and discharging to obtain epoxy resin paste; pumping the epoxy resin paste and 5 parts of alicyclic amine into a series mixer in proportion through a resin feed pump and a thickener feed pump, stirring at a high speed, uniformly mixing, and flowing into a resin frictioning tank to obtain epoxy SMC resin paste; and (3) soaking 80 parts of 12mm disordered chopped glass fibers in the prepared epoxy SMC resin paste, rolling the epoxy SMC resin paste by using an SMC sheet machine, and curing the epoxy SMC resin paste for 15 hours in a drying room at 70 ℃ to obtain the flame-retardant epoxy sheet molding compound. The epoxy composition is aliphatic epoxy resin ERL-4221,
the mechanical property of the flame-retardant epoxy sheet molding compound pressing plate is tested as follows:
the tensile strength of the sheet molding compound is 118MPa and the tensile modulus is 11.8GPa according to the test of GB/T1447; testing the bending strength of the sheet molding compound according to GB/T1449 to be 241MPa, and the bending modulus to be 12.6 GPa; testing the unnotched impact strength of the sheet molding compound according to GB/T1451 to be 107 KJ/square meter; the burning grade of the sheet molding compound is UL94-V0 according to the test of GB/T4609; the limiting oxygen index of the sheet molding compound is 40 percent according to the test of GB/T8924.
Example 5
Putting 100 parts of epoxy composition and 6 parts of internal release agent into a reaction kettle, starting stirring, adding 1.25 parts of wetting dispersant and 150g of hexaphenoxycyclotriphosphazene into the reaction kettle after the resin is melted and mixed uniformly, dispersing and stirring at a high speed, ensuring that the temperature of the material is lower than 70 ℃, and mixing uniformly to obtain a material A; reducing the temperature of the material A to below 50 ℃, adding a curing accelerator consisting of 6 parts of dicyandiamide, 2 parts of organic urea and 1 part of imidazole into a resin reaction kettle, stirring for 0.5h, performing vacuum defoaming and discharging to obtain epoxy resin paste; pumping the epoxy resin paste, 3 parts of alicyclic amine and 4 parts of polyether amine into a series mixer in proportion through a resin feed pump and a thickening agent feed pump, stirring at a high speed, uniformly mixing, and flowing into a resin frictioning tank to obtain the flame-retardant epoxy SMC resin paste; the prepared epoxy SMC resin paste is soaked in 100 parts of 24mm disordered chopped glass fibers, the steps are the same as those of the example 1, and the epoxy SMC resin paste is rolled by an SMC sheet machine and then is sent into a drying room at 20 ℃ for curing for 200 hours to obtain the epoxy sheet molding compound. The epoxy composition is a cycloaliphatic epoxy resin CY179,
the mechanical property of the flame-retardant epoxy sheet molding compound pressing plate is tested as follows:
the tensile strength of the sheet molding compound is 114MPa and the tensile modulus is 10.4GPa according to the test of GB/T1447; the bending strength of the sheet molding compound is 258MPa according to the test of GB/T1449, and the bending modulus is 12.0 GPa; testing the unnotched impact strength of the sheet molding compound according to GB/T1451 to be 110 KJ/square meter; the burning grade of the sheet molding compound is UL94-V0 according to the test of GB/T4609; the limiting oxygen index of the sheet molding compound is 40 percent according to the test of GB/T8924.
Example 6
Putting 100g of epoxy composition, 150g of aluminum hydroxide, 80g of phosphorus-nitrogen flame retardant and 18g of internal mold release agent into a reaction kettle, starting stirring, adding 1.5 parts of wetting dispersant into the reaction kettle after the resin is melted and uniformly mixed, performing high-speed dispersion and stirring, ensuring that the temperature of the material is lower than 70 ℃, and uniformly mixing to obtain a material A; reducing the temperature of the material A to below 50 ℃, adding a curing accelerator consisting of 6g of dicyandiamide, 2g of organic urea and 1g of imidazole into a resin reaction kettle, stirring for 1h, performing vacuum defoaming and discharging to obtain epoxy resin paste; pumping the epoxy resin paste and 6 parts of isophorone diamine (IPDA) into a series mixer in proportion through a resin feed pump and a thickening agent feed pump, stirring at a high speed, uniformly mixing, and flowing into a resin glue scraping tank to obtain the flame-retardant epoxy SMC resin paste; the prepared epoxy SMC resin paste is soaked in 150 parts of 24mm disordered chopped glass fibers, the steps are the same as those of example 1, and the epoxy SMC resin paste is rolled by an SMC sheet machine and then is sent into a drying room at 35 ℃ to be cured for 1 hour, so that the epoxy sheet molding compound is obtained. The epoxy composition is special epoxy resin TDE-85
The mechanical property of the flame-retardant epoxy sheet molding compound pressing plate is tested as follows:
the tensile strength of the sheet molding compound is 135MPa and the tensile modulus is 10.8GPa according to the test of GB/T1447; the bending strength of the sheet molding compound is 239MPa and the bending modulus is 12.8GPa according to the test of GB/T1449; testing the unnotched impact strength of the sheet molding compound according to GB/T1451 to be 103 KJ/square meter; the burning grade of the sheet molding compound is UL94-V0 according to the test of GB/T4609; the limiting oxygen index of the sheet moulding compound is 47% according to GB/T8924 test.
Example 7
Putting 95 parts of epoxy composition, 5 parts of trimethylolpropane triglycidyl ether XY-636 and 6 parts of internal release agent into a reaction kettle, starting stirring, adding 100 parts of melamine polyphosphate into the reaction kettle after the resin is melted and uniformly mixed, and performing high-speed dispersion stirring to ensure that the temperature of the material is lower than 70 ℃, and uniformly mixing to obtain a material A; reducing the temperature of the material A to below 50 ℃, adding a curing accelerator consisting of 5 parts of dicyandiamide, 8 parts of 4' 4 diamino diphenyl sulfone DDS and 2 parts of organic urea into a resin reaction kettle, stirring for 1h, and performing vacuum defoaming discharge to obtain epoxy resin paste; pumping the epoxy resin paste and 5 parts of modified amine into a series mixer in proportion through a resin feed pump and a thickening agent feed pump, stirring at a high speed, uniformly mixing, and flowing into a resin frictioning tank to obtain the flame-retardant epoxy SMC resin paste; the prepared flame-retardant epoxy SMC resin paste is soaked in 120 parts of 24mm disordered chopped glass fibers, the steps are the same as those of the example 1, and the mixture is rolled by an SMC sheet machine and then is sent into a drying room at 40 ℃ to be cured for 15 hours, so that the epoxy sheet molding compound is obtained. The epoxy composition is dimer acid modified epoxy resin EPD-172,
the mechanical property of the flame-retardant epoxy sheet molding compound pressing plate is tested as follows:
the tensile strength of the sheet molding compound is 141MPa and the tensile modulus is 10.5GPa according to the test of GB/T1447; the bending strength of the sheet molding compound is 253MPa and the bending modulus is 12.2GPa according to the test of GB/T1449; testing the unnotched impact strength of the sheet molding compound according to GB/T1451 to be 118 KJ/square meter; the burning grade of the sheet molding compound is UL94-V0 according to the test of GB/T4609; the limiting oxygen index of the sheet moulding compound is 38% according to GB/T8924.
Example 8
Putting 100 parts of epoxy composition and 6 parts of internal release agent into a reaction kettle, starting stirring, adding 50 parts of melamine polyphosphate and 150 parts of aluminum hydroxide into the reaction kettle after the resin is melted and uniformly mixed, and performing high-speed dispersion and stirring to ensure that the temperature of the material is lower than 70 ℃, and uniformly mixing to obtain a material A; reducing the temperature of the material A to below 50 ℃, adding a curing accelerator consisting of 7 parts of dicyandiamide, 2 parts of organic urea and 1 part of imidazole into a resin reaction kettle, stirring for 0.5h, performing vacuum defoaming and discharging to obtain epoxy resin paste; pumping the epoxy resin paste and 8 parts of aromatic amine into a series mixer in proportion through a resin feed pump and a thickener feed pump, stirring at a high speed, uniformly mixing, and flowing into a resin frictioning tank to obtain the flame-retardant epoxy SMC resin paste; the prepared epoxy SMC resin paste is soaked in 100 parts of 24mm disordered chopped glass fibers, the steps are the same as those of the example 1, and the epoxy SMC resin paste is rolled by an SMC sheet machine and then is sent into a drying room at 40 ℃ to be cured for 15 hours, so that the flame-retardant epoxy sheet molding compound is obtained. The epoxy composition is a mass mixture of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, diglycidyl phthalate, diaminodiphenylmethane tetraglycidyl amine and the like.
The mechanical property of the flame-retardant epoxy sheet molding compound pressing plate is tested as follows:
the tensile strength of the sheet molding compound is 128MPa and the tensile modulus is 11.3GPa according to the test of GB/T1447; the bending strength of the sheet molding compound is 253MPa and the bending modulus is 12.2GPa according to the test of GB/T1449; testing the unnotched impact strength of the sheet molding compound according to GB/T1451 to be 104 KJ/square meter; the burning grade of the sheet molding compound is UL94-V0 according to the test of GB/T4609; the limiting oxygen index of the sheet molding compound is 45% according to GB/T8924 test.
Example 9
Putting 100 parts of epoxy composition and 6 parts of internal release agent into a reaction kettle, starting stirring, adding 100 parts of melamine polyphosphate into the reaction kettle after the resin is melted and uniformly mixed, and performing high-speed dispersion and stirring to ensure that the temperature of the material is lower than 70 ℃, and uniformly mixing to obtain a material A; reducing the temperature of the material A to below 50 ℃, adding a curing accelerator consisting of 7 parts of dicyandiamide and 2 parts of organic urea into a resin reaction kettle, stirring for 1 hour, and performing vacuum defoaming discharge to obtain epoxy resin paste; pumping the epoxy resin paste and 5 parts of alicyclic amine into a series mixer in proportion through a resin feed pump and a thickener feed pump, stirring at a high speed, uniformly mixing, and flowing into a resin frictioning tank to obtain the flame-retardant epoxy SMC resin paste; the prepared epoxy SMC resin paste is soaked in 100 parts of 24mm disordered chopped glass fibers, the steps are the same as those of the example 1, and the epoxy SMC resin paste is rolled by an SMC sheet machine and then is sent into a drying room at 40 ℃ to be cured for 15 hours, so that the epoxy sheet molding compound is obtained. The epoxy composition is a 1:1:1 mixture of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, aliphatic epoxy resin ERL-4221 and alicyclic epoxy resin CY 179.
The mechanical property of the flame-retardant epoxy sheet molding compound pressing plate is tested as follows:
the tensile strength of the sheet molding compound is 131MPa and the tensile modulus is 11.4GPa according to the test of GB/T1447; the bending strength of the sheet molding compound is 244MPa and the bending modulus is 12.0GPa according to the test of GB/T1449; testing the unnotched impact strength of the sheet molding compound according to GB/T1451 to be 100 KJ/square meter; the burning grade of the sheet molding compound is UL94-V0 according to the test of GB/T4609; the limiting oxygen index of the sheet molding compound is 39% according to GB/T8924 test.
Example 10
Putting 80 parts of epoxy composition, 5 parts of trimethylolpropane triglycidyl ether XY-636, 15 parts of CTBN modified epoxy resin prepolymer 861340 and 6 parts of internal release agent into a reaction kettle, starting stirring, adding 60g of phosphorus-nitrogen flame retardant into the reaction kettle after the resins are melted and uniformly mixed, performing high-speed dispersion and stirring to ensure that the temperature of the materials is lower than 70 ℃, and uniformly mixing to obtain a material A; reducing the temperature of the material A to below 50 ℃, adding a curing accelerator consisting of 7 parts of dicyandiamide and 1.5 parts of organic urea into a resin reaction kettle, stirring for 55min, performing vacuum defoaming and discharging to obtain epoxy resin paste; pumping the epoxy resin paste and 5 parts of alicyclic amine into a series mixer in proportion through a resin feed pump and a thickener feed pump, stirring at a high speed, uniformly mixing, and flowing into a resin frictioning tank to obtain the flame-retardant epoxy SMC resin paste; the prepared epoxy SMC resin paste is soaked in 120 parts of 24mm disordered chopped glass fibers, the steps are the same as those of the example 1, and the epoxy SMC resin paste is rolled by an SMC sheet machine and then is sent into a drying room at 50 ℃ to be cured for 10 hours, so that the epoxy sheet molding compound is obtained. The epoxy composition is a mixture of alicyclic epoxy resin CY179, special epoxy resin TDE-85 and dimer acid modified epoxy resin EPD-172 in equal proportion.
The mechanical property of the flame-retardant epoxy sheet molding compound pressing plate is tested as follows:
the tensile strength of the sheet molding compound is 141MPa and the tensile modulus is 10.2GPa according to the test of GB/T1447; testing the bending strength of the sheet molding compound to be 251MPa and the bending modulus to be 11.4GPa according to GB/T1449; testing the unnotched impact strength of the sheet molding compound according to GB/T1451 to be 126 KJ/square meter; the burning grade of the sheet molding compound is UL94-V0 according to the test of GB/T4609; the limiting oxygen index of the sheet molding compound is 35% according to GB/T8924 test.
Example 11: the rest is the same as example 10 except that:
the thickener can be equivalently replaced with a liquid amine having primary or secondary amino groups; the epoxy composition is a 1:1:2 mixture of bisphenol A glycidyl ether type liquid epoxy resin NPEL-128, special epoxy resin TDE-85 and dimer acid modified epoxy resin EPD-172. The thickener HTDA can be equivalently replaced by at least one of aliphatic amine, alicyclic amine, aromatic amine, polyether amine and polyamide. The environment-friendly halogen-free flame retardant is alkyl phosphinate.
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. The flame-retardant epoxy sheet molding compound is characterized by being prepared from the following raw materials in parts by weight: 85-100 parts of epoxy composition, 0-15 parts of diluent, 30-200 parts of environment-friendly halogen-free flame retardant, 1-15 parts of auxiliary agent, 3-25 parts of curing accelerator, 2-15 parts of thickening agent and 50-150 parts of chopped glass fiber, wherein the thickening agent is liquid amine with primary amino group or secondary amino group; the epoxy composition 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.
2. The flame retardant epoxy sheet molding compound of claim 1, wherein: the diluent is composed of one or more of reactive diluents containing one or more epoxy functional groups.
3. The flame retardant epoxy sheet molding compound of claim 1, wherein: the environment-friendly halogen-free flame retardant is at least one of a halogen-free phosphorus-nitrogen mixed flame retardant, an ammonium polyphosphate flame retardant, melamine cyanurate, hexaphenoxycyclotriphosphazene, an alkyl phosphinate and aluminum hydroxide.
4. The flame retardant epoxy sheet molding compound of claim 1, wherein: the auxiliary agent comprises an internal release agent and a wetting dispersant.
5. The flame retardant epoxy sheet molding compound of claim 1, wherein: the curing accelerator is a compound of a component A and a component B, the component A is one or more of dicyandiamide, organic acid hydrazide, aromatic amine and modified amine, and the component B is one or more of organic urea, modified organic urea, imidazole and modified imidazole.
6. The flame retardant epoxy sheet molding compound of claim 1, wherein said thickener is at least one of aliphatic amine, cycloaliphatic amine, aromatic amine, polyether amine, polyamide and modified amines of aliphatic amine, cycloaliphatic amine, aromatic amine, polyether amine and polyamide, and the molar ratio of the total primary amino secondary amino active hydrogen in the thickener to the epoxy group in the epoxy composition is greater than 0.01 and less than 0.6.
7. The flame retardant epoxy sheet molding compound as claimed in claim 1, wherein said chopped glass fibers are stranded glass fibers treated with epoxy sizing agent, and the length of said chopped glass fibers is 10-50 mm.
8. A method for preparing a flame retardant epoxy sheet molding compound as claimed in any one of claims 1 to 7, comprising the steps of:
a. accurately weighing the epoxy composition, the diluent and the auxiliary agent in a reaction kettle, starting stirring, adding the environment-friendly halogen-free flame retardant into the reaction kettle after the resin is melted and uniformly mixed, and performing high-speed dispersion and stirring to ensure that the temperature of the material is lower than 120 ℃, and uniformly mixing to obtain a material I;
b. reducing the temperature of the first material to below 50 ℃, adding a curing accelerator into a resin reaction kettle, stirring for 0.5-1 h, performing vacuum defoaming, and discharging to obtain epoxy resin paste;
c. pumping the epoxy resin paste and the amino-containing liquid ammonia thickener into a series mixer by a resin feed pump and a thickener feed pump in proportion, stirring at a high speed, uniformly mixing, and flowing into a resin scraping tank;
d. uniformly coating the epoxy resin paste capable of being thickened rapidly on the upper and lower bearing films by a resin glue groove scraper to form an epoxy resin film;
e. the SMC sheet machine is characterized in that a yarn cutting roller cuts glass fibers, the glass fibers are uniformly doffed, the chopped glass fibers are pasted on a lower bearing film epoxy resin, the chopped glass fibers are covered by an upper bearing film epoxy resin paste, the epoxy resin paste is fully soaked into the glass fibers to form epoxy glass fiber sheets through extrusion and exhaust, and then the epoxy glass fiber sheets are rolled or packaged in a box type;
f. curing the rolled or box-packed epoxy glass fiber sheet in a drying room to quickly thicken the epoxy resin to obtain the flame-retardant epoxy sheet molding compound.
9. The method for preparing a flame retardant epoxy sheet molding compound according to claim 8, wherein: the curing temperature is 20-70 ℃ and the curing time is 1-200 hrs.
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| CN114907673A (en) * | 2022-07-01 | 2022-08-16 | 北京新福润达绝缘材料有限责任公司 | Epoxy mould pressing composite material and preparation method thereof |
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| CN114907673B (en) * | 2022-07-01 | 2024-04-09 | 北京新福润达绝缘材料有限责任公司 | Epoxy molding composite material and preparation method thereof |
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