CN116656103B - Sheet molding compound and preparation method thereof - Google Patents
Sheet molding compound and preparation method thereof Download PDFInfo
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- CN116656103B CN116656103B CN202211735787.7A CN202211735787A CN116656103B CN 116656103 B CN116656103 B CN 116656103B CN 202211735787 A CN202211735787 A CN 202211735787A CN 116656103 B CN116656103 B CN 116656103B
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- 239000003677 Sheet moulding compound Substances 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 58
- 239000002562 thickening agent Substances 0.000 claims abstract description 54
- 229920005989 resin Polymers 0.000 claims abstract description 53
- 239000011347 resin Substances 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 29
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 23
- 239000003365 glass fiber Substances 0.000 claims abstract description 22
- 238000007789 sealing Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000003825 pressing Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 41
- 239000000395 magnesium oxide Substances 0.000 claims description 33
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 24
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 17
- 150000002513 isocyanates Chemical class 0.000 claims description 17
- 238000000465 moulding Methods 0.000 claims description 16
- 239000004677 Nylon Substances 0.000 claims description 15
- 239000004698 Polyethylene Substances 0.000 claims description 15
- 229920001778 nylon Polymers 0.000 claims description 15
- 229920000573 polyethylene Polymers 0.000 claims description 15
- 239000003112 inhibitor Substances 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 13
- 239000011118 polyvinyl acetate Substances 0.000 claims description 13
- -1 polyethylene Polymers 0.000 claims description 11
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 11
- 230000002745 absorbent Effects 0.000 claims description 7
- 239000002250 absorbent Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical group [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000002093 peripheral effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical group [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical group CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims 1
- 239000011265 semifinished product Substances 0.000 abstract description 10
- 239000000843 powder Substances 0.000 abstract description 5
- 238000010924 continuous production Methods 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000008719 thickening Effects 0.000 description 41
- 235000012245 magnesium oxide Nutrition 0.000 description 31
- 230000000694 effects Effects 0.000 description 18
- 239000010410 layer Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000000149 penetrating effect Effects 0.000 description 5
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical group CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000012795 verification Methods 0.000 description 4
- 238000006114 decarboxylation reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000007676 flexural strength test Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000010409 ironing Methods 0.000 description 2
- CWPKTBMRVATCBL-UHFFFAOYSA-N 3-[1-[1-[(2-methylphenyl)methyl]piperidin-4-yl]piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound CC1=CC=CC=C1CN1CCC(N2CCC(CC2)N2C(NC3=CC=CC=C32)=O)CC1 CWPKTBMRVATCBL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0261—Polyamide fibres
- B32B2262/0269—Aromatic polyamide 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/06—Unsaturated polyesters
-
- 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
- C08J2431/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
- C08J2431/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
- C08J2431/04—Homopolymers or copolymers of vinyl acetate
-
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K3/16—Halogen-containing 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
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention provides a sheet molding compound and a preparation method thereof, the method comprises the following steps of mixing and stirring 60-70 parts of unsaturated polyester resin and 30-40 parts of low-shrinkage additive according to parts by weight, adding 130-180 parts of calcium carbonate powder while stirring, continuously stirring, adding 1-3 parts of curing agent, stirring to obtain resin paste, adding 4.5-9 parts of thickener into the resin paste, soaking 50-120 parts of glass fibers into the resin paste to prepare an SMC sheet molding compound semi-finished product, placing the SMC sheet molding compound semi-finished product between two layers of bearing films, sealing edges, curing at 50-70 ℃, and cooling and pressing the cured SMC sheet molding compound. According to the invention, the composite thickener and other chemical components are compounded in a certain proportion, so that the curing time of the sheet molding compound is greatly shortened, and the PA+PE carrier film is selected, so that the SMC is quickly heated and cured and then quickly cooled, and the high-efficiency continuous production of the SMC is realized.
Description
Technical Field
The invention relates to the technical field of functional composite material preparation, in particular to a sheet molding compound and a preparation method thereof.
Background
Sheet molding compound (Sheet molding compound) abbreviated as SMC is a sheet molding compound made by impregnating fibers with resin paste or covering the two sides of chopped fiber mat with a polyhexene film, and has the advantages of electric insulation, heat resistance, flame retardance, good mechanical strength and the like, light weight, easy and flexible engineering design and the like, and the mechanical property of the sheet molding compound can be compared with that of partial metal materials, so that the sheet molding compound is widely applied to the industries of transportation vehicles, buildings, electronics, electric and the like.
The traditional SMC sheet is pasty without middle-high temperature curing, and the film cannot be torn for compression molding, so that the final step of SMC production needs to be cured for about 24 hours (or about 35 ℃ for 3-5 days) in a drying room at about 50 ℃, the material is thickened and hardened to be of a processable type, and then the material is fully cooled to room temperature after 3-7 days, so that the compression molded product has higher quality. However, the time required for curing and molding the existing SMC is too long, and the production efficiency of the sheet molding compound is seriously affected.
Disclosure of Invention
The invention aims to solve the technical problem of providing a sheet molding compound with excellent performance and short curing time and a preparation method of the sheet molding compound.
The invention provides a sheet molding compound which comprises an upper layer of bearing film, a lower layer of bearing film and a resin material positioned between the two layers of bearing films, wherein the resin material comprises, by weight, 60-70 parts of unsaturated polyester resin, 30-40 parts of a low shrinkage agent, 130-180 parts of calcium carbonate, 1-5 parts of a water absorbent, 0.1-0.3 part of a polymerization inhibitor, 4.5-9 parts of a composite thickener, 50-120 parts of glass fibers and 1-3 parts of a curing agent, and the composite thickener comprises 3-5 parts of magnesium oxide, 1-3 parts of an isocyanate thickener and 0.5-1 part of lithium chloride.
And edge sealing treatment is carried out on the peripheral edges of the two bearing films to seal the resin material between the two bearing films, wherein the bearing films are nylon and polyethylene composite films.
The type of the magnesium oxide is RA-40, and the isocyanate thickener is toluene diisocyanate.
The unsaturated polyester resin is PS-H1168, the low shrinkage agent is a polyvinyl acetate solution with the solid content of 35-40%, the solvent of the polyvinyl acetate solution is styrene, the water absorbing agent is anhydrous magnesium sulfate, the polymerization inhibitor is 2, 6-di-tert-butyl-p-cresol, and the curing agent is tert-butyl peroxybenzoate.
The sheet molding compound further comprises 1-3 parts by weight of a release agent, wherein the release agent is zinc stearate.
The water content of the calcium carbonate is 0.1% -0.15%, and the particle size of the calcium carbonate is 1-2 mu m.
The invention provides a preparation method of a sheet molding compound for solving the technical problems, which comprises the following steps:
A. mixing and stirring 60-70 parts by weight of unsaturated polyester resin and 30-40 parts by weight of low shrinkage agent;
B. Then adding 130-180 parts by weight of calcium carbonate, 1-5 parts by weight of water absorbent and 0.1-0.3 part by weight of polymerization inhibitor while stirring, and continuing stirring;
C. adding 1-3 parts by weight of a curing agent, and stirring to obtain resin paste;
D. Adding 4.5-9 parts by weight of composite thickener into the resin paste, and soaking 50-120 parts by weight of glass fiber into the resin paste;
E. placing resin paste between two layers of bearing films, wherein the bearing films are nylon and polyethylene composite films, then sealing edges, sealing the resin paste between the two layers of bearing films, curing at 50-70 ℃ for 1-1.5 h, and cooling to normal temperature;
F. And (3) pressing and molding the cured sheet molding compound.
The stirring speed in the step A, B, C is 800-1200 r/min, and the stirring time is 3-5 min.
And D, continuously producing the sheet molding compound by adopting an SMC molding machine set, wherein the speed of the SMC molding machine set is 8m/min, the flow rate of the resin paste base liquid reaches 20.86kg/min, the flow rate of the thickener reaches 0.42kg/min, and the rotating speed of the glass fiber shredding roller is 66rpm.
And F, the upper die temperature of the compression molding is 125-135 ℃, the lower die temperature is 120-130 ℃, the pressure is 1000T/m 2, and the dwell time is 3min.
The invention has the positive effects that:
(1) The invention can make the thickening of the resin more rapid by adjusting the proportion of the resin components, especially using the composite thickening agent with specific components, the resin material has the processable type after thickening and hardening, the curing time of the sheet molding compound can be greatly shortened by about 1 hour, the traditional curing time is 24 hours or longer, and the produced sheet molding compound has excellent mechanical property.
(2) According to the sheet molding compound disclosed by the invention, the isocyanate thickener, the lithium chloride and the magnesium oxide are used in a combined mode, the lithium chloride is added to prevent the isocyanate thickener from decarboxylation reaction with carboxyl in the unsaturated resin in the thickening process, so that the isocyanate thickener preferentially reacts with hydroxyl in the unsaturated resin to thicken, and meanwhile, the magnesium oxide and the carboxyl in the unsaturated polyester resin thicken, so that the later thickening of the whole system is greatly accelerated, the curing time of the sheet molding compound is greatly shortened, and the production efficiency of the sheet molding compound is improved.
(3) The sheet molding compound adopts the nylon and polyethylene composite film carrier film, so that the SMC is quickly heated and cured and then quickly cooled to 25 ℃, high-efficiency continuous production of the SMC is realized, the nylon and polyethylene composite film material is selected to prevent styrene from penetrating, meanwhile, the upper and lower carrier films of the SMC are subjected to edge sealing treatment by a film ironing machine on line to prevent styrene from volatilizing from two sides, and the traditional PP film is basically not prevented from penetrating, so that the SMC is sealed by the traditional PP film outer package by adding a layer of aluminizer, and the nylon and polyethylene composite film disclosed by the invention is not required to be packaged by the aluminizer by combining the edge sealing treatment technology.
Drawings
FIG. 1 is a graph of the effect of magnesium oxide usage on early thickening according to an embodiment of the present invention;
FIG. 2 is a graph of magnesium oxide usage versus post thickening effect for an embodiment of the present invention;
FIG. 3 is a graph comparing thickening properties of different activated magnesium oxides according to an embodiment of the present invention;
FIG. 4 is a graph of verification of thickening performance of resins of different acid numbers for an embodiment of the present invention;
FIG. 5 is a graph of the effect of different shrinking agents on thickening properties according to embodiments of the present invention;
FIG. 6 is a graph of calcium carbonate moisture change for an embodiment of the present invention;
FIG. 7 is a graph showing the comparison of thickening performance before and after drying of calcium carbonate according to an embodiment of the present invention;
FIG. 8 is a graph of a composite thickener effectiveness verification of an embodiment of the present invention;
FIG. 9 is a graph of the effect of temperature on a composite thickener according to an embodiment of the present invention;
FIG. 10 is a graph of temperature versus SMC storage stability study of an embodiment of the present invention;
FIG. 11 is a graph of the barrier effect of a carrier film on styrene in accordance with an embodiment of the present invention;
FIG. 12 is a graph showing the effect of the polymerization inhibitor on the stability of SMC storage properties according to an embodiment of the present invention;
FIG. 13 is a graph showing the effect of a curing agent on SMC storage stability according to an embodiment of the present invention;
FIG. 14 is a graph comparing the rapid temperature rise thickening of a conventional ton package with a continuous production of a single ply material in accordance with an embodiment of the present invention;
FIG. 15 is a graph comparing the rapid cooling thickening of a conventional ton package with the continuous production of a single layer of material in accordance with an embodiment of the present invention;
FIG. 16 is a graph of tensile strength of a sheet molding compound of an embodiment of the present invention versus a conventional sheet molding compound;
FIG. 17 is a graph showing the flexural strength of sheet molding compounds of examples of the present invention versus conventional sheet molding compounds.
Detailed Description
Example 1
The sheet molding compound comprises, by weight, 60 parts of unsaturated polyester resin, 30 parts of a low shrinkage agent, 130 parts of calcium carbonate, 4.5 parts of a composite thickener, 50 parts of glass fibers and 1 part of a curing agent, wherein the composite thickener comprises 3 parts of magnesium oxide, 1 part of an isocyanate thickener and 0.5 part of lithium chloride.
The preparation method of the sheet molding compound comprises the following steps:
A. mixing and stirring 60 parts by weight of unsaturated polyester resin and 30 parts by weight of low shrinkage agent;
B. then adding 130 parts by weight of calcium carbonate powder while stirring, and continuing stirring;
C. adding 1 part by weight of a curing agent, and stirring to obtain resin paste;
D. Adding 4.5 parts by weight of thickener into the resin paste, and soaking 50 parts by weight of glass fiber into the resin paste to prepare an SMC sheet molding compound semi-finished product;
and D, continuously producing the SMC sheet molding compound by adopting an SMC molding unit, wherein the speed of the SMC sheet molding compound is set to 8m/min before the SMC molding unit, the flow rate of resin paste base liquid reaches 20.86kg/min, the flow rate of thickener reaches 0.42kg/min, and the rotating speed of a glass fiber shredding roller is 66rpm.
E. Placing the SMC sheet molding compound semi-finished product between two layers of bearing films, wherein the bearing films are made of nylon and polyethylene composite films, then carrying out edge sealing treatment, and curing at 50 ℃;
F. And cooling, pressing and forming the cured SMC sheet molding compound, wherein the upper die temperature of the pressing and forming is 125 ℃, the lower die temperature is 120 ℃, the pressure is 1000T/m 2, and the dwell time is 3min.
The unsaturated polyester resin is PS-H1168, the low shrinkage agent is polyvinyl acetate solution, the magnesium oxide is RA-40, the isocyanate thickener is toluene diisocyanate, and the curing agent is tert-butyl peroxybenzoate.
Example 2
The sheet molding compound comprises, by weight, 65 parts of unsaturated polyester resin, 35 parts of a low shrinkage agent, 150 parts of calcium carbonate, 6 parts of a composite thickener, 100 parts of glass fibers and 2 parts of a curing agent;
the composite thickener comprises 4 parts by weight of magnesium oxide, 2 parts by weight of isocyanate thickener and 0.8 part by weight of lithium chloride.
The preparation method of the sheet molding compound comprises the following steps:
A. mixing 65 parts by weight of unsaturated polyester resin and 35 parts by weight of a low shrinkage agent;
B. then 150 parts by weight of calcium carbonate powder is added while stirring, and stirring is continued;
C. Adding 2 parts by weight of a curing agent, and stirring to obtain resin paste;
D. Adding 6 parts by weight of thickener into the resin paste, and soaking 100 parts by weight of glass fiber into the resin paste to prepare an SMC sheet molding compound semi-finished product;
and D, continuously producing the SMC sheet molding compound by adopting an SMC molding unit, wherein the speed of the SMC sheet molding compound is set to 8m/min before the SMC molding unit, the flow rate of resin paste base liquid reaches 20.86kg/min, the flow rate of thickener reaches 0.42kg/min, and the rotating speed of a glass fiber shredding roller is 66rpm.
E. Placing the SMC sheet molding compound semi-finished product between two layers of bearing films, wherein the bearing films are made of nylon and polyethylene composite films, then carrying out edge sealing treatment, and curing at 60 ℃;
F. And cooling, pressing and forming the cured SMC sheet molding compound, wherein the upper die temperature of the pressing and forming is 130 ℃, the lower die temperature is 125 ℃, the pressure is 1000T/m 2, and the dwell time is 3min.
The unsaturated polyester resin is PS-H1168, the low shrinkage agent is polyvinyl acetate solution, the magnesium oxide is RA-40, the isocyanate thickener is toluene diisocyanate, and the curing agent is tert-butyl peroxybenzoate.
Example 3
The sheet molding compound of the embodiment comprises the following components in parts by weight:
70 parts of unsaturated polyester resin, 40 parts of low shrinkage agent, 180 parts of calcium carbonate, 9 parts of composite thickener, 120 parts of glass fiber and 3 parts of curing agent;
The composite thickener comprises 5 parts by weight of magnesium oxide, 3 parts by weight of isocyanate thickener and 1 part by weight of lithium chloride.
The preparation method of the sheet molding compound comprises the following steps:
A. Mixing and stirring 70 parts by weight of unsaturated polyester resin and 40 parts by weight of a low shrinkage agent;
B. then 180 parts by weight of calcium carbonate powder is added while stirring, and stirring is continued;
C. adding 3 parts by weight of a curing agent, and stirring to obtain resin paste;
D. adding 9 parts by weight of thickener into the resin paste, and soaking 120 parts by weight of glass fiber into the resin paste to prepare an SMC sheet molding compound semi-finished product;
and D, continuously producing the SMC sheet molding compound by adopting an SMC molding unit, wherein the speed of the SMC sheet molding compound is set to 8m/min before the SMC molding unit, the flow rate of resin paste base liquid reaches 20.86kg/min, the flow rate of thickener reaches 0.42kg/min, and the rotating speed of a glass fiber shredding roller is 66rpm.
E. placing the SMC sheet molding compound semi-finished product between two layers of bearing films, wherein the bearing films are made of nylon and polyethylene composite films, then carrying out edge sealing treatment, and curing at 70 ℃;
F. And cooling, pressing and forming the cured SMC sheet molding compound, wherein the upper die temperature of the pressing and forming is 135 ℃, the lower die temperature is 130 ℃, the pressure is 1000T/m 2, and the dwell time is 3min.
The unsaturated polyester resin is PS-H1168, the low shrinkage agent is polyvinyl acetate solution, the magnesium oxide is RA-40, the isocyanate thickener is toluene diisocyanate, and the curing agent is tert-butyl peroxybenzoate.
Example 4
The sheet molding compound comprises, by weight, 70 parts of unsaturated polyester resin, 40 parts of a low shrinkage agent, 180 parts of calcium carbonate, 9 parts of a composite thickener, 120 parts of glass fibers, 3 parts of a curing agent, 1-3 parts of a water absorbent, 0.1-0.3 part of a polymerization inhibitor and 1-3 parts of a release agent;
The composite thickener comprises 5 parts by weight of magnesium oxide, 3 parts by weight of isocyanate thickener and 1 part by weight of lithium chloride.
The preparation method of the sheet molding compound comprises the following steps:
A. Mixing and stirring 70 parts by weight of unsaturated polyester resin and 40 parts by weight of a low shrinkage agent;
B. then 180 parts by weight of calcium carbonate powder is added while stirring, and stirring is continued, wherein the water content of the calcium carbonate is 0.1%, and in other embodiments, the water content can be 0.12%;
C. adding 3 parts by weight of a curing agent, and stirring to obtain resin paste;
D. 9 parts by weight of thickener, 1-3 parts by weight of water absorbent, 0.1-0.3 parts by weight of polymerization inhibitor and 1-3 parts by weight of release agent are added into the resin paste, and in other embodiments, the polymerization inhibitor can be added, and 120 parts by weight of glass fiber is soaked into the resin paste to prepare an SMC sheet molding compound semi-finished product;
and D, continuously producing the SMC sheet molding compound by adopting an SMC molding unit, wherein the speed of the SMC sheet molding compound is set to 8m/min before the SMC molding unit, the flow rate of resin paste base liquid reaches 20.86kg/min, the flow rate of thickener reaches 0.42kg/min, and the rotating speed of a glass fiber shredding roller is 66rpm.
E. placing the SMC sheet molding compound semi-finished product between two layers of bearing films, wherein the bearing films are made of nylon and polyethylene composite films, then carrying out edge sealing treatment, and curing at 70 ℃;
F. And cooling, pressing and forming the cured SMC sheet molding compound, wherein the upper die temperature of the pressing and forming is 135 ℃, the lower die temperature is 130 ℃, the pressure is 1000T/m 2, and the dwell time is 3min.
The unsaturated polyester resin is PS-H1168, the low shrinkage agent is polyvinyl acetate solution, the magnesium oxide is RA-40, the isocyanate thickener is toluene diisocyanate, the curing agent is tert-butyl peroxybenzoate, the water absorbent is anhydrous magnesium sulfate, and the polymerization inhibitor is 2, 6-di-tert-butyl-p-cresol.
The following is an effect verification experiment of the present invention:
1. How to effectively shorten the curing time of SMC
1.1 Effect of the amount of thickener magnesium oxide on Pre-thickening and post-thickening
Method for testing the effect of early thickening 60 parts of resin, 40 parts of polyvinyl acetate solution, 150 parts of calcium carbonate, 1% -3% MgO,800phr of MgO are stirred for 5min, the viscosity of the resin paste is continuously tested by a brookfield viscometer at a constant temperature of 25 ℃, readings are taken every 10min, and the graph of FIG. 1 is drawn.
Method for testing the effect of post-thickening, 60 parts of resin, 40 parts of polyvinyl acetate solution, 150 parts of calcium carbonate and 1% -3% MgO,800phr of the mixture are stirred for 5min and then thickened in a 50 ℃ oven, one cup of sample is taken out every 5h, the temperature of the water bath at 25 ℃ is kept constant for 30min, and then the viscosity is tested by a brookfield viscometer, so that a curve of FIG. 2 is drawn.
As shown in fig. 3, the effect of the magnesium oxide dosage on the later thickening is that the magnesium oxide dosage is increased to 3% from the curve, the later thickening is obviously improved, but the earlier thickening is that the viscosity reaches 10000m of Long s after 30min, the viscosity is the upper limit of glass fiber infiltration, the dosage is increased to 2% and 3%, the viscosity is obviously increased, and the requirement of fully infiltrating the glass fiber cannot be met, so that the expected effect cannot be achieved by simply increasing the thickener dosage.
The thickening performance of different active magnesium oxides is verified by comparison, and the test method comprises the steps of 60 parts of resin, 40 parts of polyvinyl acetate solution, 150 parts of calcium carbonate, 1% MgO and 800phr of the mixture are stirred for 5min, then thickening in a 50 ℃ oven, taking out one cup of sample every 5h, keeping the temperature in a 25 ℃ water bath for 30min, and then testing the viscosity by using a brookfield viscometer.
As shown in FIG. 4, RA-40 magnesium oxide has the best thickening performance.
1.2 Selection of resins
Test method 60 parts of resin, 40 parts of polyvinyl acetate solution, 150 parts of calcium carbonate, 3% MgO and 800phr of the mixture are stirred for 5min and then thickened in a 50 ℃ oven, one cup of sample is taken out every 5h, and after the temperature is kept for 30min in a 25 ℃ water bath, the viscosity is tested by using a brookfield viscometer.
As shown in FIG. 5, the thickening properties of unsaturated polyester resins of different acid numbers are compared, and the PS-H1168 of which the acid number is the largest is the best in the late thickening properties because the thickening mechanism is the complexation of magnesium oxide with carboxyl groups, and the PS-H1168 of which the acid number is the highest, so that the thickening properties are the best.
1.3 Selection of Low shrinkage Agents
60 Parts of resin, 40 parts of different low shrinkage agents, 150 parts of calcium carbonate, 2% MgO and 800phr of stirring material are stirred for 5min, then thickened in a 50 ℃ oven, one cup of sample is taken out every 5h, and after the temperature is kept for 30min in a 25 ℃ water bath, the viscosity is tested by using a brookfield viscometer.
As shown in fig. 6, using polyvinyl acetate as the low shrinkage agent can greatly promote the thickening performance of the SMC due to its unique carboxyl group, compared to PS and saturated low shrinkage agents.
1.4 Effect of calcium carbonate
The calcium carbonate is dried for 24 hours at the temperature of 50 ℃ before being used, the moisture change curve is shown in fig. 7, the dried calcium carbonate and the dried calcium carbonate are compared with each other in thickening performance, and the result is shown in fig. 8, the dried calcium carbonate can greatly promote the thickening performance of the SMC, and the reason is that moisture accelerates the early thickening of unsaturated resin and magnesium oxide, is unfavorable for the infiltration of glass fibers, and the moisture reduces the later thickening performance and influences the thickening of the SMC.
1.5 Effect of composite thickeners
The two thickening agents of lithium chloride and Toluene Diisocyanate (TDI) and MgO are used in a composite way, the total dosage is 2% of the whole system, the effect of TDI/MgO: liCl=2:2:1 is shown in figure 9, liCl is inorganic salt with extremely strong water absorption, and the purpose of improving thickening performance is achieved by absorbing water molecules in a resin system. The isocyanate thickener TDI preferentially reacts with hydroxyl groups in the thickening process, but cannot be excessive, otherwise decarboxylation reaction can be carried out with carboxyl groups in unsaturated resin, especially under the condition of water, so that the addition of LiCl can prevent the decarboxylation reaction besides the effect. The hydroxyl groups in the TDI and the unsaturated polyester resin are thickened, and the carboxyl groups in the magnesium oxide and the unsaturated polyester resin are thickened, so that the later thickening of the whole system is greatly accelerated. Therefore, using mgo+licl+tdi as a composite thickener can greatly promote the thickening performance of SMC as compared to mgo+licl as a thickener.
1.6 Effect of curing temperature
As shown in fig. 10, the aging temperature is raised to 70 ℃, the thickening time can be shortened to 1h, the post thickening viscosity reaches 44×10 6 mpa·s, and the use requirement of the SMC is met. The curing temperature is further increased to 80 ℃ and the thickening performance is further accelerated, but the curing time of the SMC is reduced by 80 ℃, the service performance and the service life are affected, and as shown in figure 10, a significant attenuation process is carried out after 5 hours, so that the thickening temperature is controlled within 70 ℃ more properly.
1.7 Selection of Carrier film
Test method about 100g of SMC of PP carrier film and nylon/polyethylene carrier film were taken out of the oven at 50 ℃ and the weight of the remaining SMC under test was taken out every 12h, and the graph was recorded as shown in FIG. 11.
As can be seen from fig. 11, the carrier film made of nylon/polyethylene is selected, the carrier film can prevent styrene from penetrating, meanwhile, the carrier films on the upper and lower sides of the SMC are subjected to edge sealing treatment by a film ironing machine on line, styrene is prevented from volatilizing from two sides, the traditional PP film and the nylon/polyethylene film have the following effect on penetrating styrene at 50 ℃, and the traditional PP film is basically not prevented from penetrating styrene, so that the SMC is further sealed by adding an aluminized film to the traditional PP film outer package, and the nylon/polyethylene film is not required to be packaged by the aluminized film.
2. How to ensure the stability of the material during high-temperature curing
2.1 Polymerization inhibitor can improve the stability of the product
As shown in FIG. 12, the addition of 2, 6-di-t-butyl-p-cresol polymerization inhibitor prevents the deterioration of polymerization inhibitor during high temperature aging from decreasing the stability of the product, and the addition amount of 0.1% is as effective as 0.3%, so that 0.1% is sufficient.
2.2 The curing agent can improve the stability of the product
As shown in FIG. 13, the TBPB and TG-05 curing agents have more obvious attenuation, and TG-01 has almost no attenuation in 20 hours, so that the TG-01 curing agent is selected to be more stable.
3. How to realize SMC rapid temperature rise
The traditional ton package is stacked together with the aluminum plating film and the paper box on the outer package, the heat transfer efficiency is very slow, as shown in fig. 14, the temperature of the materials in the traditional ton package box is slowly raised to about 42 ℃ after being placed in a 50 ℃ drying room for 10 hours, and the temperature of the single SMC can be quickly raised to 45 ℃ in the 50 ℃ drying room within 1 hour.
4. How to realize SMC rapid cooling
As shown in fig. 15, the temperature of the material just outside the drying room is reduced from 45 ℃ to 39 ℃ under the constant temperature condition of 25 ℃ under the condition of the same temperature rising curve as the traditional ton package, and the temperature of the material can be reduced to 30 ℃ within 10min, and the single piece of material can be fully cooled to 25 ℃ within 25 min.
5. Mechanical property verification
The test method is to test the performance of the quick thickening material prepared by the method of the invention on tensile strength, bending strength and impact strength with the conventional materials which are currently on the market and use magnesium oxide as a thickening agent.
5.1 Tensile Strength test
Table 1 tensile strength test data sheet
As can be seen from the graph of FIG. 16, the rapid thickening material produced by the method of the present invention has comparable tensile strength to conventional materials on the market.
5.2 Flexural Strength test
Table 2 flexural strength test data sheet
As can be seen from the graph of FIG. 17, the rapid thickening material produced by the method of the present invention has comparable flexural strength to conventional materials on the market.
5.3 Impact Strength
Table 3 table of impact strength test data
The above mechanical property test results indicate that the fast thickening material performs quite as well as a conventional SMC.
Claims (10)
1. The sheet molding compound comprises an upper layer of bearing film, a lower layer of bearing film and a resin material positioned between the two layers of bearing films, and is characterized by comprising, by weight, 60-70 parts of unsaturated polyester resin, 30-40 parts of a low shrinkage agent, 130-180 parts of calcium carbonate, 1-5 parts of a water absorbent, 0.1-0.3 part of a polymerization inhibitor, 4.5-9 parts of a composite thickener, 50-120 parts of glass fibers and 1-3 parts of a curing agent, wherein the composite thickener comprises 3-5 parts of magnesium oxide, 1-3 parts of an isocyanate thickener and 0.5-1 part of lithium chloride.
2. The sheet molding compound according to claim 1, wherein the resin material is sealed between the two carrier films by edge sealing treatment at peripheral edges of the two carrier films, and the carrier films are nylon and polyethylene composite films.
3. The sheet molding compound according to claim 1, wherein said magnesium oxide is RA-40, and said isocyanate-based thickener is toluene diisocyanate.
4. The sheet molding compound according to claim 1, wherein the unsaturated polyester resin is PS-H1168, the low shrinkage agent is a polyvinyl acetate solution having a solid content of 35 to 40%, the solvent of the polyvinyl acetate solution is styrene, the water absorbing agent is anhydrous magnesium sulfate, the polymerization inhibitor is 2, 6-di-t-butyl-p-cresol, and the curing agent is t-butyl peroxybenzoate.
5. The sheet molding compound according to any one of claims 1 to 4, further comprising 1 to 3 parts by weight of a mold release agent, wherein the mold release agent is zinc stearate.
6. The sheet molding compound according to any one of claims 1 to 4, wherein the calcium carbonate has a water content of 0.1 to 0.15%, and a particle diameter of 1 to 2 μm.
7. The preparation method of the sheet molding compound is characterized by comprising the following steps:
A. mixing and stirring 60-70 parts by weight of unsaturated polyester resin and 30-40 parts by weight of low shrinkage agent;
B. Then adding 130-180 parts by weight of calcium carbonate, 1-5 parts by weight of water absorbent and 0.1-0.3 part by weight of polymerization inhibitor while stirring, and continuing stirring;
C. adding 1-3 parts by weight of a curing agent, and stirring to obtain resin paste;
D. adding 4.5-9 parts by weight of a composite thickener into the resin paste, and soaking 50-120 parts by weight of glass fibers into the resin paste, wherein the composite thickener comprises 3-5 parts by weight of magnesium oxide, 1-3 parts by weight of isocyanate thickener and 0.5-1 part by weight of lithium chloride;
E. placing resin paste between two layers of bearing films, wherein the bearing films are nylon and polyethylene composite films, then sealing edges, sealing the resin paste between the two layers of bearing films, curing at 50-70 ℃ for 1-1.5 h, and cooling to normal temperature;
F. And (3) pressing and molding the cured sheet molding compound.
8. The method for preparing a sheet molding compound according to claim 7, wherein the stirring speed in the step A, B, C is 800-1200 r/min and the stirring time is 3-5 min.
9. The method for preparing sheet molding compound according to claim 7, wherein in the step D, the sheet molding compound is continuously produced by an SMC molding machine, the speed of the vehicle is set to 8m/min before the SMC molding machine, the flow rate of the resin paste base liquid reaches 20.86kg/min, the flow rate of the thickener reaches 0.42kg/min, and the rotational speed of the glass fiber shredding roller is 66rpm.
10. The method for preparing sheet molding compound according to claim 7, wherein the upper die temperature for press molding in the step F is 125 ℃ to 135 ℃, the lower die temperature is 120 ℃ to 130 ℃, the pressure is 1000T/m 2, and the dwell time is 3min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH10265660A (en) * | 1997-03-25 | 1998-10-06 | Hitachi Chem Co Ltd | Unsaturated polyester resin composition, sheet molding material, and production thereof |
| CN101397395A (en) * | 2008-06-16 | 2009-04-01 | 北京福润德复合材料有限责任公司 | Unsaturated polyester glass fiber felt plate and production method thereof |
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| DE19533059C2 (en) * | 1995-09-07 | 1999-10-14 | Juchheim Gmbh & Co M K | Reference electrode for electrochemical measurements and process for their production |
| WO2008003499A1 (en) * | 2006-07-06 | 2008-01-10 | Dsm Ip Assets B.V. | Method for radically curing |
| CN110408160A (en) * | 2019-08-21 | 2019-11-05 | 合肥工业大学 | A kind of sheet molding compound for rapid prototyping at room temperature and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH10265660A (en) * | 1997-03-25 | 1998-10-06 | Hitachi Chem Co Ltd | Unsaturated polyester resin composition, sheet molding material, and production thereof |
| CN101397395A (en) * | 2008-06-16 | 2009-04-01 | 北京福润德复合材料有限责任公司 | Unsaturated polyester glass fiber felt plate and production method thereof |
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