CN111777846B - SMC (sheet molding compound) molding compound for low-temperature low-pressure weather-resistant agricultural machinery and preparation method thereof - Google Patents
SMC (sheet molding compound) molding compound for low-temperature low-pressure weather-resistant agricultural machinery and preparation method thereof Download PDFInfo
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- CN111777846B CN111777846B CN202010631619.8A CN202010631619A CN111777846B CN 111777846 B CN111777846 B CN 111777846B CN 202010631619 A CN202010631619 A CN 202010631619A CN 111777846 B CN111777846 B CN 111777846B
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- 238000000465 moulding Methods 0.000 title claims abstract description 34
- 150000001875 compounds Chemical class 0.000 title claims abstract description 19
- 239000003677 Sheet moulding compound Substances 0.000 title description 26
- 238000002360 preparation method Methods 0.000 title description 8
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 239000003365 glass fiber Substances 0.000 claims abstract description 13
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000004033 plastic Substances 0.000 claims abstract description 4
- 229920003023 plastic Polymers 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004614 Process Aid Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- WHUNEQVNUYXPBW-UHFFFAOYSA-N tert-butyl 6-methylheptaneperoxoate Chemical group CC(C)CCCCC(=O)OOC(C)(C)C WHUNEQVNUYXPBW-UHFFFAOYSA-N 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
- 238000012360 testing method Methods 0.000 description 5
- 238000013329 compounding Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000206 moulding compound Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a low-temperature low-pressure weather-resistant SMC molding compound for agricultural machinery, which comprises the following raw materials in parts by weight: 60-80 parts of unsaturated polyester resin, 20-40 parts of low-shrinkage additive, 160-200 parts of high-fluidity filling material, 1.5-2 parts of No. 1 curing agent, 0.3-1 part of No. 2 curing agent, 0.5-1 part of composite polymerization inhibitor, 2-4 parts of release agent, 5-7 parts of process additive, 3-4 parts of antioxidant and 50-80 parts of glass fiber. The plastic disclosed by the invention greatly reduces the molding temperature and molding pressure, shortens the curing period, and simultaneously maintains the original excellent performance of the material.
Description
Technical Field
The invention relates to the technical field of plastics, in particular to a SMC molding compound for low-temperature low-pressure weather-resistant agricultural machinery and a preparation method thereof.
Background
SMC moulding compounds, mainly comprising Sheet moulding compounds SMC (Sheet moulding Compound), were resin-based composites reinforced with glass fibres developed in the last 60 th century. SMC/BMC molding compounds have been widely used in various industries such as automobile manufacturing, agricultural machinery manufacturing, aviation, transportation, electric appliances, instruments, construction and the like, especially in the agricultural machinery industry, because of their excellent mechanical properties, excellent weather resistance and heat resistance, low shrinkage and good processability. In recent years, many enterprises and research departments at home and abroad have studied the characteristics of resins and fibers in order to obtain high-performance SMC composite materials, and the SMC materials with excellent performance are expected to be obtained. In view of the current state of development of the industry, conventional SMC is mainly produced by using an unsaturated polyester resin as a matrix, filling other materials, and reinforcing chopped glass fibers as main raw materials, and by combining auxiliary raw materials such as a low shrinkage additive, an antioxidant, an initiator, a thickener, a release agent, and the like.
Low-carbon energy conservation has become the mainstream of the world nowadays and is the root for the survival of each enterprise. SMC molding compounds are generallyProcessing and molding at 140-160 deg.C by compression molding or injection molding, with molding pressure of 200kg/cm 2 The faster cure cycle is typically 30S/mm. And the molding temperature and the time period of the molding compound are reduced, which is the key direction of the industry development.
Disclosure of Invention
In order to solve the problems in the prior art, the applicant of the invention provides an SMC molding compound for agricultural machinery with low temperature, low pressure and weather resistance and a preparation method thereof. The plastic disclosed by the invention greatly reduces the molding temperature and molding pressure, shortens the curing period, and simultaneously maintains the original excellent performance of the material.
The technical scheme of the invention is as follows:
the SMC molding compound for the low-temperature low-pressure weather-resistant agricultural machinery comprises the following raw materials in parts by weight:
the unsaturated polyester resin is silicon modified unsaturated polyester resin, the solid content is 50-60%, and the viscosity at 23 ℃ is 2200-2400cps.
The low-profile additive is a colorable polystyrene type low-profile additive WHUT-LPA; the high-fluidity filling material is high-fluidity spherical calcium carbonate powder, and the particle size of the high-fluidity spherical calcium carbonate powder is 1000-3000 meshes.
The No. 1 curing agent is tert-butyl peroxyisooctanoate, the purity is more than 98 percent, and the 10-hour half-life temperature is 70 ℃; the No. 2 curing agent is di-tert-butyl peroxide, the purity is more than 96%, and the 10-hour half-life temperature is 121 ℃.
The compound polymerization inhibitor is RS-421.
The release agent is zinc stearate powder with the particle size of 500 meshes.
The process aid is a mixture of BYK9010 and BYK996, and the mass ratio of the BYK9010 to the BYK996 is 1-1; the antioxidant is basf 1010.
The glass fiber is 400-4800tex glass fiber chopped yarn, and the machine cutting length is 25mm.
A preparation method of the SMC molding compound for the agricultural machinery with low temperature, low pressure and weather resistance comprises the following steps:
firstly, stirring 60-80 parts of unsaturated polyester resin, 20-40 parts of low-shrinkage additive and 5-7 parts of process auxiliary agent for 2min at the rotating speed of 500rpm in a stirring kettle, wherein the temperature is less than or equal to 50 ℃; after being stirred uniformly, 1.5-2 parts of No. 1 curing agent, 0.3-1 part of No. 2 curing agent, 0.5-1 part of composite polymerization inhibitor and 3-4 parts of antioxidant are added, and the mixture is stirred for 1min at the rotating speed of 2000 rpm; then 160-200 parts of high-fluidity filling material and 2-4 parts of release agent are added, stirred for 5min at the rotating speed of 300rpm, then added into an SMC production line and compounded with 50-80 parts of glass fiber, the production of the material is finished, and the material is placed into a curing chamber for curing for 3 days at the temperature of 45 ℃.
The beneficial technical effects of the invention are as follows:
the invention relates to a low-temperature low-pressure weather-resistant SMC molding compound, which is a novel polyester molding compound prepared by adopting a plurality of novel curing systems to mix and match, a novel high-fluidity filler and a novel polymerization inhibitor to assist in controlling curing and storage, adding a special process additive to improve the fluidity of the material after being pressed at a certain temperature, adding an antioxidant to improve the weather resistance and matching with auxiliary raw materials such as a low-shrinkage additive, glass fiber and the like on the main structure of a conventional SMC material. The novel molding compound greatly reduces the molding temperature and the molding pressure, shortens the curing period, and has the molding temperature of only 105-120 ℃ and the molding pressure of only 50kg/cm 2 The curing period is 10-15S/mm, and the material keeps the original excellent performance.
The novel curing system adopted by the invention is mixed and matched, and the novel composite polymerization inhibitor assists in controlling, so that the curing time is shortened, and meanwhile, the fluidity and the storage property of the material are ensured; the matching research of the high-fluidity filling agent, the release agent and the process auxiliary agent improves the high fluidity and the release smoothness of the product during low-temperature and low-pressure molding; through special feeding and mixing sequence and temperature control of mixing equipment, the generation time of free radicals in the material is controlled, and the molding characteristic and the appearance quality of the material are improved.
Detailed Description
The present invention will now be described in detail with reference to the following examples.
The characteristics of the raw materials adopted in the invention are shown in table 1;
TABLE 1
Example 1
A preparation method of the SMC molding compound for the agricultural machinery with low temperature, low pressure and weather resistance comprises the following steps:
firstly, stirring 60 parts of unsaturated polyester resin, 40 parts of low-shrinkage additive and 7 parts of process additive for 2min at the rotating speed of 500rpm in a stirring kettle, wherein the temperature is less than or equal to 50 ℃; after being stirred uniformly, 1.5 parts of No. 1 curing agent, 1 part of No. 2 curing agent, 1 part of composite polymerization inhibitor and 3 parts of antioxidant are added, and the mixture is stirred for 1min at the rotating speed of 2000 rpm; then 160 parts of high-fluidity filling material and 2 parts of release agent are added, the mixture is stirred for 5min at the rotating speed of 300rpm, then the mixture is added into an SMC production line and 80 parts of glass fiber are added for compounding, the production of the material is finished after the material is taken out, and the material is put into a curing chamber for curing for 3 days at the temperature of 45 ℃.
Example 2
A preparation method of the SMC molding compound for the agricultural machinery with low temperature, low pressure and weather resistance comprises the following steps:
firstly, stirring 80 parts of unsaturated polyester resin, 20 parts of low-shrinkage additive and 5 parts of process additive for 2min at the rotating speed of 500rpm in a stirring kettle, wherein the temperature is less than or equal to 50 ℃; after the mixture is uniformly stirred, adding 2 parts of No. 1 curing agent, 0.3 part of No. 2 curing agent, 0.8 part of composite polymerization inhibitor and 4 parts of antioxidant, and stirring for 1min at the rotating speed of 2000 rpm; then 200 parts of high-fluidity filling material and 4 parts of release agent are added, stirring is carried out for 5min at the rotating speed of 300rpm, then 70 parts of glass fiber is added in an SMC production line for compounding, the production of the material is finished after the material is taken out, and the material is put in a curing chamber for curing for 3 days at the temperature of 45 ℃.
Example 3
A preparation method of the SMC molding compound for the agricultural machinery with low temperature, low pressure and weather resistance comprises the following steps:
firstly, stirring 75 parts of unsaturated polyester resin, 25 parts of low-shrinkage additive and 6 parts of process additive for 2min at the rotating speed of 500rpm in a stirring kettle, wherein the temperature is less than or equal to 50 ℃; after being stirred uniformly, 1.8 parts of No. 1 curing agent, 0.6 part of No. 2 curing agent, 0.5 part of composite polymerization inhibitor and 3 parts of antioxidant are added, and the mixture is stirred for 1min at the rotating speed of 2000 rpm; then adding 180 parts of high-fluidity filling material and 3 parts of release agent, stirring for 5min at the rotating speed of 300rpm, adding 50 parts of glass fiber into an SMC production line for compounding, finishing the production of the material after the material is taken out, and putting the material into a curing chamber for curing for 3 days at the temperature of 45 ℃.
Test example:
the products of examples 1 to 3 were molded at a temperature of 110 ℃ and 50kg/cm 2 Molding under molding pressure with a curing period of 10-15S/mm to obtain 2mm sample pieces, and testing at room temperature to obtain the results shown in Table 2. All the test performances can meet the related index requirements.
TABLE 2
| Test items | Unit | Test method | Technical index | Example 1 | Example 2 | Example 3 |
| Specific gravity of molded article | g/cm3 | ISO 1183-2004(E) | 1.75-1.95 | 1.76 | 1.8 | 1.79 |
| Molding shrinkage ratio | ％ | ISO 2577-1984(E) | ＜0.2 | 0.15 | 0.15 | 0.16 |
| Water absorption rate | mg | ISO 62-1999(E) | ＜0.2 | 0.18 | 0.17 | 0.18 |
| Heat distortion temperature | ℃ | ISO 75-1987(E) | ＞200 | 225 | 220 | 222 |
| Bending strength | MPa | ISO 178-2001(E) | ＞200 | 256 | 247 | 262 |
| Bending modulus of elasticity | GPa | ISO 178-2001(E) | ＞20 | 28 | 26 | 29 |
| Impact Strength (Charpy) | KJ/m2 | ISO 179-2000(E) | ＞60 | 77 | 76 | 78 |
| Weather resistance | Florida light test | Color change of less than 2 per year | 1.5 | 1.7 | 1.4 | |
| Flame resistance | UL-94 | HB | HB | HB | HB |
Claims (3)
1. The SMC molding compound for the agricultural machinery with low temperature, low pressure and weather resistance is characterized by comprising the following raw materials in parts by weight:
the unsaturated polyester resin is silicon modified unsaturated polyester resin, the solid content is 50-60%, and the viscosity at 23 ℃ is 2200-2400cps;
the low-shrinkage additive is a colorable polystyrene type low-shrinkage additive WHUT-LPA; the high-fluidity filling material is high-fluidity spherical calcium carbonate powder, and the grain diameter of the high-fluidity spherical calcium carbonate powder is 1000-3000 meshes;
the No. 1 curing agent is tert-butyl peroxyisooctanoate, the purity is more than 98 percent, and the 10-hour half-life temperature is 70 ℃; the No. 2 curing agent is di-tert-butyl peroxide, the purity is more than 96%, and the 10-hour half-life temperature is 121 ℃;
the process aid is a mixture of BYK9010 and BYK996, and the mass ratio of the BYK9010 to the BYK996 is 1-1; the antioxidant is basf 1010;
the glass fiber is 400-4800tex glass fiber chopped yarn, and the machine cutting length is 25mm.
2. The plastic according to claim 1, wherein the release agent is zinc stearate powder with a particle size of 500 mesh.
3. A method for preparing SMC molding compound with low temperature, low pressure and weather resistance for agricultural machinery as claimed in claim 1, wherein the method comprises the following steps:
firstly, stirring 60-80 parts of unsaturated polyester resin, 20-40 parts of low-shrinkage additive and 5-7 parts of process auxiliary agent for 2min at the rotating speed of 500rpm in a stirring kettle, wherein the temperature is less than or equal to 50 ℃; after being stirred uniformly, 1.5-2 parts of No. 1 curing agent, 0.3-1 part of No. 2 curing agent, 0.5-1 part of composite polymerization inhibitor and 3-4 parts of antioxidant are added, and the mixture is stirred for 1min at the rotating speed of 2000 rpm; then 160-200 parts of high-fluidity filling material and 2-4 parts of release agent are added, stirred for 5min at the rotating speed of 300rpm, then added into an SMC production line and compounded with 50-80 parts of glass fiber, the production of the material is finished, and the material is placed into a curing chamber for curing for 3 days at the temperature of 45 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010631619.8A CN111777846B (en) | 2020-07-03 | 2020-07-03 | SMC (sheet molding compound) molding compound for low-temperature low-pressure weather-resistant agricultural machinery and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010631619.8A CN111777846B (en) | 2020-07-03 | 2020-07-03 | SMC (sheet molding compound) molding compound for low-temperature low-pressure weather-resistant agricultural machinery and preparation method thereof |
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| Publication Number | Publication Date |
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| CN111777846A CN111777846A (en) | 2020-10-16 |
| CN111777846B true CN111777846B (en) | 2023-02-03 |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116426104A (en) * | 2023-05-23 | 2023-07-14 | 江西沃土新型材料有限公司 | High-performance glass fiber reinforced plastic composite material and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08295714A (en) * | 1995-04-26 | 1996-11-12 | Showa Highpolymer Co Ltd | Compound for low-pressure molding |
| EP1052273A1 (en) * | 1999-05-12 | 2000-11-15 | Dsm N.V. | Resin composition based on unsaturated polyester |
| JP2001089651A (en) * | 1999-09-21 | 2001-04-03 | Bridgestone Corp | Glass fiber-reinforced plastic composition |
| JPWO2005103152A1 (en) * | 2004-03-31 | 2007-08-16 | 昭和高分子株式会社 | Low specific gravity unsaturated polyester resin composition for lamp reflector and molded product thereof |
| JP2006131759A (en) * | 2004-11-05 | 2006-05-25 | Showa Highpolymer Co Ltd | Sheet molding compound (smc) |
| CN101575445B (en) * | 2009-03-17 | 2012-04-11 | 无锡新宏泰电器科技股份有限公司 | Low-temperature fast curing polyester moulding compound and preparation method thereof |
| CN103159946B (en) * | 2013-03-18 | 2015-02-25 | 肇庆福田化学工业有限公司 | Silicon resin modified unsaturated polyester resin and preparation method thereof |
| CN105885376B (en) * | 2016-06-16 | 2018-06-22 | 无锡新宏泰电器科技股份有限公司 | A kind of sheet molding compound and preparation method thereof |
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Non-Patent Citations (3)
| Title |
|---|
| Influence of initiator on the curing of unsaturated polyester resin at 100℃;Christelle Delaite，等;《Polymer International》;20191120;第69卷(第11期);第1089-1096页 * |
| SMC快速固化体系与模拟仿真研究;李文中;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20071115(第05（2007）期);B020-21 * |
| 主链含硅不饱和聚酯的合成及其热解行为研究;郭清明，等;《热固性树脂》;20150930;第30卷(第5期);第7-13页 * |
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Address after: 214000 No.1 Xichang Road, Pailou Village, Yanqiao Street, Huishan District, Wuxi City, Jiangsu Province Patentee after: Wuxi Puye Polymer Materials Technology Co.,Ltd. Address before: 214000 No.1 Xichang Road, Xizhang Industrial Park, Wuxi City, Jiangsu Province Patentee before: WUXI PERUN RUBBER & PLASTIC Co.,Ltd. |
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Effective date of registration: 20240402 Address after: 214000 1 Xichang Road, pailou village, Yanqiao street, Huishan District, Wuxi City, Jiangsu Province Patentee after: Wuxi shunxiu Rubber Plastic Co.,Ltd. Country or region after: China Address before: 214000 No.1 Xichang Road, Pailou Village, Yanqiao Street, Huishan District, Wuxi City, Jiangsu Province Patentee before: Wuxi Puye Polymer Materials Technology Co.,Ltd. Country or region before: China |