CN116769291B - Processing method of SMC sheet - Google Patents
Processing method of SMC sheet Download PDFInfo
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- CN116769291B CN116769291B CN202310732648.7A CN202310732648A CN116769291B CN 116769291 B CN116769291 B CN 116769291B CN 202310732648 A CN202310732648 A CN 202310732648A CN 116769291 B CN116769291 B CN 116769291B
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- hyperbranched polyester
- hydroxyquinoline
- hydroxyl
- coupling agent
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- 238000003672 processing method Methods 0.000 title claims abstract description 6
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 60
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000945 filler Substances 0.000 claims abstract description 34
- 239000000654 additive Substances 0.000 claims abstract description 33
- 230000000996 additive effect Effects 0.000 claims abstract description 30
- 229920002689 polyvinyl acetate Polymers 0.000 claims abstract description 24
- 239000011118 polyvinyl acetate Substances 0.000 claims abstract description 24
- 239000007822 coupling agent Substances 0.000 claims abstract description 22
- 229920002748 Basalt fiber Polymers 0.000 claims abstract description 19
- 239000006229 carbon black Substances 0.000 claims abstract description 19
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical group C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- 239000003365 glass fiber Substances 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 25
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 12
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 11
- 229960001826 dimethylphthalate Drugs 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001723 curing Methods 0.000 claims description 9
- 238000004806 packaging method and process Methods 0.000 claims description 9
- 238000005096 rolling process Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 239000012753 anti-shrinkage agent Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- -1 titanium ions Chemical class 0.000 abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- 239000003677 Sheet moulding compound Substances 0.000 description 25
- 238000000465 moulding Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005507 spraying Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 244000082946 Tarchonanthus camphoratus Species 0.000 description 1
- 235000005701 Tarchonanthus camphoratus Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of SMC materials, and discloses a processing method of an SMC sheet. The invention prepares an additive component which comprises terminal hydroxyquinoline hyperbranched polyester and modified filler in a mass ratio of 1:8; the hyperbranched polyester has large molecular weight and high crosslinking density, can be used as an anti-shrinkage agent of an SMC sheet, has a toughening effect, and is modified by using 5-sulfonyl chloride-8-hydroxyquinoline to obtain the hydroxyquinoline hyperbranched polyester with good stability and excellent mechanical property; the modified filler is basalt fiber and carbon black which are jointly modified by a silane coupling agent and a titanate coupling agent, the modified basalt fiber and carbon black have good dispersibility and carry titanium ions, and can be complexed with the nitrogen atoms of quinoline in the hydroxyquinoline-terminated hyperbranched polyester to form coordination bonds; the SMC sheet prepared from the additive components, the unsaturated polyester resin, the initiator, the polyvinyl acetate and the glass fiber has low shrinkage, good tensile strength and smooth surface.
Description
Technical Field
The invention relates to the technical field of SMC materials, and discloses a processing method of an SMC sheet.
Background
The Chinese name of SMC is sheet molding compound, is one of composite material intermediate materials and is also one of forming processes of thermosetting material glass fiber reinforced plastic, and has the advantages of light weight, high strength, corrosion resistance, flame retardance, flexible design and the like; the raw materials of the SMC are more than ten, and the type, performance, quality and mutual proportion of each raw material have great influence on the performance of the SMC.
SMC materials have high dimensional stability requirements, and low shrinkage additives are used in the prior art to reduce shrinkage during processing and molding, and the most common varieties of low shrinkage additives are: polystyrene, polyvinyl chloride, polyvinyl acetate, polymethyl methacrylate, linear saturated polyester, and the like; however, these additives have poor compatibility with resins, and the shrinkage rate is not obviously reduced when the addition amount is small, and problems such as dishing on the surface of the finished product, stickiness on the surface of the finished product, and reduced tensile property may occur when the addition amount is large, thus adversely affecting the production of SMC materials.
Therefore, the preparation of the SMC sheet with good tensile strength, low shrinkage and good surface finish has great significance.
Disclosure of Invention
The invention aims to provide a processing method of an SMC sheet material, which aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a method of processing an SMC sheet, comprising the steps of: s1: mixing the terminal hydroxyquinoline hyperbranched polyester, the modified filler and the ethanol, heating for reaction, filtering and drying to obtain additive components;
S2: and (3) uniformly stirring unsaturated polyester resin, an initiator, additive components and polyvinyl acetate, compounding with glass fibers, curing, molding, rolling, sealing and packaging to obtain the SMC sheet.
More optimally, the SMC sheet comprises the following raw materials in parts by weight: 40 to 60 parts of unsaturated polyester resin, 1 to 3 parts of initiator, 60 to 80 parts of additive components, 9 to 12 parts of polyvinyl acetate and 20 to 35 parts of glass fiber.
More optimally, the additive components comprise the following raw materials in parts by weight: 4-5 parts of hydroxyl-terminated quinoline hyperbranched polyester, 32-40 parts of modified filler and 40-60 parts of ethanol.
More optimally, the mass ratio of the additive component to the polyvinyl acetate is 20:3; the mass ratio of the terminal hydroxyquinoline hyperbranched polyester to the modified filler is 1:8.
More preferably, the preparation of the hydroxyquinoline terminated hyperbranched polyester comprises the following steps: s1: taking trimethylolpropane, dimethylolpropionic acid and dimethyl phthalate, uniformly stirring, and reacting at 120-150 ℃ for 3-5 hours to obtain hydroxyl-terminated hyperbranched polyester;
S2: and (3) taking hydroxyl-terminated hyperbranched polyester, 5-sulfonyl chloride-8-hydroxyquinoline and pyridine, uniformly mixing, heating to 30-40 ℃ under the protection of nitrogen, reacting for 20-24 hours, cooling to room temperature, settling in ethyl acetate, filtering, and drying in vacuum to obtain the hydroxyl-terminated quinoline hyperbranched polyester.
More optimally, the hydroxyl-terminated hyperbranched polyester comprises the following raw materials in parts by weight: 20-30 parts of trimethylolpropane, 70-80 parts of dimethylolpropionic acid and 20-30 parts of dimethyl phthalate; the hydroxyl-terminated quinoline hyperbranched polyester comprises the following raw materials in parts by weight: 4-6 parts of hydroxyl-terminated hyperbranched polyester, 6-10 parts of 5-sulfonyl chloride-8-hydroxyquinoline and 80-120 parts of pyridine.
More preferably, the preparation of the modified filler comprises the steps of: stirring the coupling agent at 60-80 ℃ for 2-3 hours, adding basalt fiber, carbon black, water and ethanol, performing ultrasonic dispersion for 2-3 hours, centrifuging, washing and drying to obtain the modified filler.
More preferably, the coupling agent comprises a silane coupling agent and a titanate coupling agent, and the mass ratio is 2:3.
More optimally, the modified filler comprises the following raw materials in parts by weight: 8-12 parts of silane coupling agent, 12-18 parts of titanate coupling agent, 25-35 parts of basalt fiber, 15-25 parts of carbon black, 80-120 parts of water and 80-120 parts of ethanol.
Compared with the prior art, the invention has the following beneficial effects: (1) The hyperbranched polyester has high molecular weight and high crosslinking density, and can be used as an anti-shrinkage agent with good compatibility with unsaturated polyester resin; the hyperbranched polyester also has good toughening effect and can improve the tensile strength of unsaturated polyester resin;
(2) The 5-sulfonyl chloride-8-hydroxyquinoline is used for modifying the hydroxyl-terminated hyperbranched polyester, so that the structural stability is improved; after the hydroxyl-terminated quinoline hyperbranched polyester is added, the stability, heat resistance and mechanical properties of the unsaturated polyester resin can be enhanced, meanwhile, quinoline has good coordination property, and nitrogen atoms can form covalent bonds with modified fillers prepared in the subsequent steps to prepare an additive component with good stability and good compatibility with the unsaturated polyester resin;
(3) The preparation method comprises the steps of preparing modified filler, wherein the modified filler comprises a silane coupling agent, a titanate coupling agent, basalt fiber and carbon black, wherein the combination modification of the silane coupling agent and the titanate coupling agent enables the basalt fiber and the carbon black to have good toughness and dispersibility, and the surfaces of the basalt fiber and the carbon black are provided with metal ion titanium ions, so that the modified filler can be complexed with terminal hydroxyquinoline hyperbranched polyester to obtain an additive component with strong stability and good compatibility with unsaturated polyester resin; the use of basalt fibers with carbon black also helps to promote surface finish;
(4) The mass ratio of the additive component to the polyvinyl acetate is 20:3, and the mass ratio of the hydroxyl-terminated quinoline hyperbranched polyester to the modified filler is 1:8, so that the shrinkage resistance of the hydroxyl-terminated quinoline hyperbranched polyester and the polyvinyl acetate in the additive component can have the best effect; when only the terminal hydroxyquinoline hyperbranched polyester is used, the shrinkage resistance effect is required to be improved, and the excessive addition of the polyvinyl acetate can cause the reduction of the surface finish of a finished product.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The following examples include the following materials: trimethylolpropane (CAS: 77-99-6); dimethylolpropionic acid (CAS: 4767-03-7); dimethyl phthalate (CAS: 131-11-3); 5-sulfonyl chloride-8-hydroxyquinoline (CAS: 64641-92-5); pyridine (CAS: 110-86-1); ethyl acetate (CAS: 141-78-6); silane coupling agent (model: KH-602, huaian and metachemical Co., ltd.); titanate coupling agent (model: FT311, nanjing Feiteng New Material technology Co., ltd.); basalt fiber (da yi bang technology limited); carbon black (model: CP6062EX, dongguan camphor wood Ke Ruida plastic commercial part); unsaturated polyester resin (model: FL9506, thousands of chemical); initiator (model: TBEC, jinan Chentaifu chemical Co., ltd.); polyvinyl acetate (molecular weight: 20w, caramar); glass fiber (-26 mm, hubei Senxin automobile parts Co., ltd.);
The following parts are mass parts;
example 1: s1: taking 25 parts of trimethylolpropane, 75 parts of dimethylolpropionic acid and 25 parts of dimethyl phthalate, uniformly stirring, and reacting at 130 ℃ for 4 hours to obtain hydroxyl-terminated hyperbranched polyester;
S2: taking 5 parts of hydroxyl-terminated hyperbranched polyester, 9 parts of 5-sulfonyl chloride-8-hydroxyquinoline and 100 parts of pyridine, uniformly mixing, heating to 35 ℃ under the protection of nitrogen, reacting for 22 hours, cooling to room temperature, settling in ethyl acetate, filtering, and vacuum drying to obtain the hydroxyl-terminated quinoline hyperbranched polyester;
S3: taking 10 parts of silane coupling agent and 15 parts of titanate coupling agent, uniformly mixing, reacting for 2 hours at 70 ℃, adding 30 parts of basalt fiber, 20 parts of carbon black, 100 parts of water and 100 parts of ethanol, performing ultrasonic dispersion for 3 hours, centrifuging, washing and drying to obtain modified filler;
S4: mixing 5 parts of terminal hydroxyquinoline hyperbranched polyester, 40 parts of modified filler and 50 parts of ethanol, heating to 30 ℃, reacting for 1h, filtering and drying to obtain additive components;
S5:50 parts of unsaturated polyester resin, 1 part of initiator, 60 parts of additive components and 9 parts of polyvinyl acetate, stirring uniformly, spraying on a film paved with 30 parts of glass fibers, curing for 35 hours at 40 ℃, heating to 155 ℃, molding for 7 minutes under 12MPa, rolling, sealing and packaging to obtain an SMC sheet.
Example 2: s1: taking 20 parts of trimethylolpropane, 70 parts of dimethylolpropionic acid and 20 parts of dimethyl phthalate, uniformly stirring, and reacting at 130 ℃ for 4 hours to obtain hydroxyl-terminated hyperbranched polyester;
S2: taking 4 parts of hydroxyl-terminated hyperbranched polyester, 6 parts of 5-sulfonyl chloride-8-hydroxyquinoline and 80 parts of pyridine, uniformly mixing, heating to 35 ℃ under the protection of nitrogen, reacting for 22 hours, cooling to room temperature, settling in ethyl acetate, filtering, and vacuum drying to obtain the hydroxyl-terminated quinoline hyperbranched polyester;
s3: taking 8 parts of silane coupling agent and 12 parts of titanate coupling agent, uniformly mixing, reacting for 2 hours at 70 ℃, adding 25 parts of basalt fiber, 15 parts of carbon black, 80 parts of water and 80 parts of ethanol, performing ultrasonic dispersion for 3 hours, centrifuging, washing and drying to obtain modified filler;
S4: mixing 5 parts of terminal hydroxyquinoline hyperbranched polyester, 40 parts of modified filler and 50 parts of ethanol, heating to 30 ℃, reacting for 1h, filtering and drying to obtain additive components;
S5:60 parts of unsaturated polyester resin, 3 parts of initiator, 80 parts of additive component and 12 parts of polyvinyl acetate, uniformly stirring, spraying on a film paved with 35 parts of glass fiber, curing for 35 hours at 40 ℃, heating to 155 ℃, molding for 7 minutes under 12MPa, rolling, sealing and packaging to obtain an SMC sheet.
Example 3: s1: taking 30 parts of trimethylolpropane, 80 parts of dimethylolpropionic acid and 30 parts of dimethyl phthalate, uniformly stirring, and reacting at 130 ℃ for 4 hours to obtain hydroxyl-terminated hyperbranched polyester;
S2: taking 6 parts of hydroxyl-terminated hyperbranched polyester, 10 parts of 5-sulfonyl chloride-8-hydroxyquinoline and 120 parts of pyridine, uniformly mixing, heating to 35 ℃ under the protection of nitrogen, reacting for 22 hours, cooling to room temperature, settling in ethyl acetate, filtering, and vacuum drying to obtain the hydroxyl-terminated quinoline hyperbranched polyester;
S3: taking 12 parts of silane coupling agent and 18 parts of titanate coupling agent, uniformly mixing, reacting for 2 hours at 70 ℃, adding 25-35 parts of basalt fiber, 15-25 parts of carbon black, 80-120 parts of water and 80-120 parts of ethanol, performing ultrasonic dispersion for 3 hours, centrifuging, washing and drying to obtain modified filler;
S4: mixing 5 parts of terminal hydroxyquinoline hyperbranched polyester, 40 parts of modified filler and 50 parts of ethanol, heating to 30 ℃, reacting for 1h, filtering and drying to obtain additive components;
S5:40 parts of unsaturated polyester resin, 1 part of initiator, 60 parts of additive components and 9 parts of polyvinyl acetate, stirring uniformly, spraying on a film paved with 20 parts of glass fibers, curing for 35 hours at 40 ℃, heating to 155 ℃, molding for 7 minutes under 12MPa, rolling, sealing and packaging to obtain an SMC sheet.
Comparative example 1 (without 5-sulfonyl chloride-8-hydroxyquinoline modified terminal hydroxy hyperbranched polyester, the remaining process steps are identical to example 1): s1: taking 25 parts of trimethylolpropane, 75 parts of dimethylolpropionic acid and 25 parts of dimethyl phthalate, uniformly stirring, and reacting at 130 ℃ for 4 hours to obtain hydroxyl-terminated hyperbranched polyester;
S2: taking 10 parts of silane coupling agent and 15 parts of titanate coupling agent, uniformly mixing, reacting for 2 hours at 70 ℃, adding 30 parts of basalt fiber, 20 parts of carbon black, 100 parts of water and 100 parts of ethanol, performing ultrasonic dispersion for 3 hours, centrifuging, washing and drying to obtain modified filler;
s3: mixing 5 parts of terminal hydroxyquinoline hyperbranched polyester, 40 parts of modified filler and 50 parts of ethanol, heating to 30 ℃, reacting for 1h, filtering and drying to obtain additive components;
S4:50 parts of unsaturated polyester resin, 1 part of initiator, 60 parts of additive components and 9 parts of polyvinyl acetate, stirring uniformly, spraying on a film paved with 30 parts of glass fibers, curing for 35 hours at 40 ℃, heating to 155 ℃, molding for 7 minutes under 12MPa, rolling, sealing and packaging to obtain an SMC sheet.
Comparative example 2 (without titanate coupling agent, the remaining process steps are identical to example 1): s1: taking 25 parts of trimethylolpropane, 75 parts of dimethylolpropionic acid and 25 parts of dimethyl phthalate, uniformly stirring, and reacting at 130 ℃ for 4 hours to obtain hydroxyl-terminated hyperbranched polyester;
S2: taking 5 parts of hydroxyl-terminated hyperbranched polyester, 9 parts of 5-sulfonyl chloride-8-hydroxyquinoline and 100 parts of pyridine, uniformly mixing, heating to 35 ℃ under the protection of nitrogen, reacting for 22 hours, cooling to room temperature, settling in ethyl acetate, filtering, and vacuum drying to obtain the hydroxyl-terminated quinoline hyperbranched polyester;
s3: taking 25 parts of silane coupling agent, stirring for 2 hours at 70 ℃, adding 30 parts of basalt fiber, 20 parts of carbon black, 100 parts of water and 100 parts of ethanol, performing ultrasonic dispersion for 3 hours, centrifuging, washing and drying to obtain modified filler;
S4: mixing 5 parts of terminal hydroxyquinoline hyperbranched polyester, 40 parts of modified filler and 50 parts of ethanol, heating to 30 ℃, reacting for 1h, filtering and drying to obtain additive components;
S5:50 parts of unsaturated polyester resin, 1 part of initiator, 60 parts of additive components and 9 parts of polyvinyl acetate, stirring uniformly, spraying on a film paved with 30 parts of glass fibers, curing for 35 hours at 40 ℃, heating to 155 ℃, molding for 7 minutes under 12MPa, rolling, sealing and packaging to obtain an SMC sheet.
Comparative example 3 (varying the amounts of hydroxyquinoline terminated hyperbranched polyester, modified filler, polyvinyl acetate added, the remaining process steps being identical to example 1): s1: taking 25 parts of trimethylolpropane, 75 parts of dimethylolpropionic acid and 25 parts of dimethyl phthalate, uniformly stirring, and reacting at 130 ℃ for 4 hours to obtain hydroxyl-terminated hyperbranched polyester;
S2: taking 5 parts of hydroxyl-terminated hyperbranched polyester, 9 parts of 5-sulfonyl chloride-8-hydroxyquinoline and 100 parts of pyridine, uniformly mixing, heating to 35 ℃ under the protection of nitrogen, reacting for 22 hours, cooling to room temperature, settling in ethyl acetate, filtering, and vacuum drying to obtain the hydroxyl-terminated quinoline hyperbranched polyester;
S3: taking 10 parts of silane coupling agent and 15 parts of titanate coupling agent, uniformly mixing, reacting for 2 hours at 70 ℃, adding 30 parts of basalt fiber, 20 parts of carbon black, 100 parts of water and 100 parts of ethanol, performing ultrasonic dispersion for 3 hours, centrifuging, washing and drying to obtain modified filler;
s4: mixing 10 parts of terminal hydroxyquinoline hyperbranched polyester, 50 parts of modified filler and 50 parts of ethanol, heating to 30 ℃, reacting for 1h, filtering and drying to obtain additive components;
S5:50 parts of unsaturated polyester resin, 1 part of initiator, 60 parts of additive components and 2 parts of polyvinyl acetate, stirring uniformly, spraying on a film paved with 30 parts of glass fibers, curing for 35 hours at 40 ℃, heating to 155 ℃, molding under 12MPa for 7 minutes, rolling, sealing and packaging to obtain an SMC sheet.
Comparative example 4 (no terminal hydroxyquinoline hyperbranched polyester was added, replaced by polyvinyl acetate, the remaining process steps being identical to example 1): s1: taking 10 parts of silane coupling agent and 15 parts of titanate coupling agent, uniformly mixing, reacting for 2 hours at 70 ℃, adding 30 parts of basalt fiber, 20 parts of carbon black, 100 parts of water and 100 parts of ethanol, performing ultrasonic dispersion for 3 hours, centrifuging, washing and drying to obtain modified filler;
s2: mixing 5 parts of polyvinyl acetate and 40 parts of modified filler to obtain an additive component;
S3:50 parts of unsaturated polyester resin, 1 part of initiator, 60 parts of additive components and 9 parts of polyvinyl acetate, stirring uniformly, spraying on a film paved with 30 parts of glass fibers, curing for 35 hours at 40 ℃, heating to 155 ℃, molding for 7 minutes under 12MPa, rolling, sealing and packaging to obtain an SMC sheet.
Experiment: taking SMC sheets prepared in examples 1-3 and comparative examples 1-4, (1) referring to GB/T15568-2008 standard, and testing the molding shrinkage; (2) testing tensile strength with reference to GB/T1447-2005 standard; (3) With reference to the GB8807-1988 standard, a 20℃angular surface gloss was tested; specific data are shown in the following table;
Conclusion: as can be seen from the above table, example 1 is a preferred embodiment; from comparative example 1, it is seen that when 5-sulfonyl chloride-8-hydroxyquinoline modified hydroxyl-terminated hyperbranched polyester is not used, the performance of the obtained SMC sheet is reduced, and thus, the introduction of a quinoline structure has the effect of increasing the crosslinking degree, and can effectively reduce the shrinkage, improve the tensile strength and improve the surface smoothness; from comparative example 2, the importance of adding titanate coupling agent can be seen, the titanate coupling agent can improve the dispersibility and mechanical properties of basalt fiber and carbon black, titanium ions can also form coordination bonds with quinoline to increase stability, and meanwhile, the titanate coupling agent FT311 used in the invention can play a role of a diluent, so that unsaturated polyester resin can infiltrate glass fiber more uniformly, and the surface finish of a finished product is improved; according to the comparative example 3, the addition amount defined by the invention is adjusted, and the shrinkage rate of the obtained SMC sheet is increased, so that the visible terminal hydroxyquinoline hyperbranched polyester and the polyvinyl acetate can achieve the best effect only by being matched and used according to a certain proportion; from comparative example 4, without using a terminal hydroxyquinoline hyperbranched polyester, only using polyvinyl acetate as an anti-shrinkage agent, the obtained finished product was lower in shrinkage rate, but both tensile strength and surface finish were reduced;
in conclusion, the SMC sheet with low shrinkage, good tensile strength and good surface quality can be prepared by the scheme provided by the invention.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (2)
1. A processing method of an SMC sheet is characterized in that: the method comprises the following steps: s1: mixing the terminal hydroxyquinoline hyperbranched polyester, the modified filler and the ethanol, heating for reaction, filtering and drying to obtain additive components;
s2: mixing unsaturated polyester resin, an initiator, additive components and polyvinyl acetate, uniformly stirring, compounding with glass fiber, curing, mould pressing, rolling, sealing and packaging to obtain an SMC sheet;
The SMC sheet comprises the following raw materials in parts by weight: 40-60 parts of unsaturated polyester resin, 1-3 parts of initiator, 60-80 parts of additive components, 9-12 parts of polyvinyl acetate and 20-35 parts of glass fiber;
the additive comprises the following raw materials in parts by weight: 4-5 parts of hydroxyl-terminated quinoline hyperbranched polyester, 32-40 parts of modified filler and 40-60 parts of ethanol;
The mass ratio of the additive component to the polyvinyl acetate is 20:3; the mass ratio of the terminal hydroxyquinoline hyperbranched polyester to the modified filler is 1:8;
The preparation of the hydroxyl-terminated quinoline hyperbranched polyester comprises the following steps: s1: taking trimethylolpropane, dimethylolpropionic acid and dimethyl phthalate, uniformly stirring, and reacting at 120-150 ℃ for 3-5 hours to obtain hydroxyl-terminated hyperbranched polyester;
S2: taking hydroxyl-terminated hyperbranched polyester, 5-sulfonyl chloride-8-hydroxyquinoline and pyridine, uniformly mixing, heating to 30-40 ℃ under the protection of nitrogen, reacting for 20-24 hours, cooling to room temperature, settling in ethyl acetate, filtering, and drying in vacuum to obtain the hydroxyl-terminated quinoline hyperbranched polyester;
The hydroxyl-terminated hyperbranched polyester comprises the following raw materials in parts by weight: 20-30 parts of trimethylolpropane, 70-80 parts of dimethylolpropionic acid and 20-30 parts of dimethyl phthalate; the hydroxyl-terminated quinoline hyperbranched polyester comprises the following raw materials in parts by weight: 4-6 parts of hydroxyl-terminated hyperbranched polyester, 6-10 parts of 5-sulfonyl chloride-8-hydroxyquinoline and 80-120 parts of pyridine;
The preparation of the modified filler comprises the following steps: stirring a coupling agent at 60-80 ℃ for 2-3 hours, adding basalt fiber, carbon black, water and ethanol, performing ultrasonic dispersion for 2-3 hours, centrifuging, washing and drying to obtain modified filler;
The coupling agent comprises a silane coupling agent and a titanate coupling agent, and the mass ratio is 2:3;
the modified filler comprises the following raw materials in parts by weight: 8-12 parts of silane coupling agent, 12-18 parts of titanate coupling agent, 25-35 parts of basalt fiber, 15-25 parts of carbon black, 80-120 parts of water and 80-120 parts of ethanol.
2. An SMC sheet prepared by the method of processing an SMC sheet according to any of claim 1.
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| CN104788667A (en) * | 2015-04-03 | 2015-07-22 | 嘉兴学院 | 8-hydroxyquinoline terminated hyperbranched polyester rare earth complex as well as preparation method and application thereof |
| CN105482399A (en) * | 2015-11-27 | 2016-04-13 | 四川迪弗电工科技有限公司 | Unsaturated polyester resin fiber reinforced sheet-shape molding compound and preparation method thereof |
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| EP0365052A3 (en) * | 1985-10-22 | 1990-08-29 | The Budd Company | Phase stabilized polyester molding material |
| KR100227593B1 (en) * | 1994-06-30 | 1999-11-01 | 나카노 카쯔히코 | Unsaturated polyester resin composition and process for molding said composition |
| JP2005154458A (en) * | 2003-11-20 | 2005-06-16 | Hitachi Housetec Co Ltd | Sheet molding compound |
| CN111500038B (en) * | 2020-03-18 | 2023-10-03 | 浙江龙鑫化工有限公司 | Low-density SMC sheet and preparation method thereof |
| CN111875941B (en) * | 2020-07-31 | 2023-03-21 | 广东百汇达新材料有限公司 | Use of hyperbranched polyester as low-shrinkage additive and toughening agent of polyester molding compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104788667A (en) * | 2015-04-03 | 2015-07-22 | 嘉兴学院 | 8-hydroxyquinoline terminated hyperbranched polyester rare earth complex as well as preparation method and application thereof |
| CN105482399A (en) * | 2015-11-27 | 2016-04-13 | 四川迪弗电工科技有限公司 | Unsaturated polyester resin fiber reinforced sheet-shape molding compound and preparation method thereof |
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