CN102993559A - Glass-fiber reinforced polypropylene composite for automobile brake fluid reservoir and preparation method of composite - Google Patents
Glass-fiber reinforced polypropylene composite for automobile brake fluid reservoir and preparation method of composite Download PDFInfo
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- CN102993559A CN102993559A CN2012103813739A CN201210381373A CN102993559A CN 102993559 A CN102993559 A CN 102993559A CN 2012103813739 A CN2012103813739 A CN 2012103813739A CN 201210381373 A CN201210381373 A CN 201210381373A CN 102993559 A CN102993559 A CN 102993559A
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Abstract
The invention discloses a glass-fiber reinforced polypropylene composite for an automobile brake fluid reservoir, comprising the following components in percentage by weight: homo-polypropylene 24-83%, high melt strength polypropylene 5-30%, compatilizer 2-10%, and chopped glass fiber 10-36%. The preparation method of the glass-fiber reinforced polypropylene composite includes the steps of adding the homo-polypropylene, a heat stabilizer, processing aid, a nucleating agent, the high melt strength polypropylene and the compatilizer into a screw extruder through a main feeding mouth to perform melt blending, so that the chopped glass fiber is added into the screw extruder from a lateral feeding mouth through a weight-loss measurement scale to perform melt blending with other components; and then extruding to granulate. The prepared glass-fiber reinforced polypropylene composite has the characteristics of high rigidity, high heat resistance, and good ageing resistance and weldable property, so as to meet the requirements of the automobile brake fluid reservoir on high rigidity, high heat resistance, and good ageing resistance and weldable property and realizes high cost performance of the automobile brake fluid reservoir material.
Description
Technical field
The invention belongs to macromolecular material and forming process field thereof, be specifically related to a kind of for automobile brake oil can glass fiber reinforced polypropylene compound and preparation method thereof.
Background technology
The automobile brake oil can mainly adopts the preparation of polypropylene material injection molding forming method at present, after injection moulding is finished, two halves adopt ultra-sonic welded or hot plate welding namely to become complete oil can up and down, therefore the automobile brake oil can requires material to have excellent weldability, braking oilcan is bearing the pressure of brake solution because of transmitting torque when brake simultaneously, therefore vehicle oilcan is very high to the requirement of burstpressures, requires material to have excellent resistance toheat and ageing-resistant performance.
Because traditional polypropylene material thermotolerance is not enough, therefore, the braking oilcan material of the welding of exploitation high performance-price ratio, good heat resistance has important market and economic worth.After polypropylene adopts glass to strengthen, its thermotolerance increases considerably, can satisfy the requirement of various braking oilcan materials fully, but because the existence of glass, the welding property of fiber glass reinforced polypropylene is too poor, because polypropylene material is linearity molecular structure, therefore at high temperature melt strength is relatively poor simultaneously, in high cold cycle, cause easily stress cracking or stress deformation, can not satisfy the demand that automobile brake oil can material is pursued high sexual valence.
Summary of the invention
For the shortcoming that overcomes prior art with not enough, primary and foremost purpose of the present invention is to provide the glass fiber reinforced polypropylene compound that is used for the automobile brake oil can of a kind of high rigidity, high heat-resisting, ageing resistance and good welds performance.
Another object of the present invention is to provide the preparation method of above-mentioned glass fiber reinforced polypropylene compound for the automobile brake oil can.
The present invention is achieved by the following technical solutions:
Be used for the glass fiber reinforced polypropylene compound of automobile brake oil can, by weight percentage, comprise following component:
Homo-polypropylene 24 ~ 83%
High melt strength, propylene 5 ~ 30%
Compatilizer 2 ~ 10%
Short glass fiber 10 ~ 36%
Wherein, the melt flow rate (MFR) of described high melt strength, propylene under 230 ℃, load 2.16KG condition is 0.01～1.0g/10min.
Described test melt flow rate (MFR) meets ISO 1133-1-2011 standard, i.e. mensuration-the part 1 of plastics-thermoplastics melt mass flow rate (MFR) and melt volume-flow rate (MVR): standard method.
Described thermo-stabilizer is selected from the mixture class of phenols, amine, phosphorous acid esters, half Hinered phenols, acryl functional group and monothioester and one or more mixtures of calixarene kind.
Described processing aid is selected from one or more mixtures of metal soap, stearic acid complex ester class, amides.
Described nucleator is selected from one or more mixtures of 3000 ~ 8000 order talcum powder, glucitols, organic phosphate.
Described compatilizer is the polar monomer graft polymkeric substance; Wherein, polymeric matrix is selected from one or more mixtures in the multipolymer, polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-butadiene terpolymer, ethylene-acrylate copolymer, ethylene-acrylate-glycidyl methacrylate copolymer of polyethylene, polypropylene, ethene-α-ethylene-octene copolymer, vinylbenzene and divinyl; Polar monomer is selected from one or more mixtures of maleic anhydride, fumaric acid, methylene-succinic acid, citraconic acid, citraconic anhydride, vinyl Succinic anhydried, methacrylic acid, acrylicacidandesters analog derivative.
Described acrylicacidandesters analog derivative is selected from one or more mixtures of methyl acrylate, ethyl propenoate, methyl methacrylate, glytidyl methacrylate.
Described short glass fiber is the alkali-free short glass fiber.
Be used for the preparation method of the glass fiber reinforced polypropylene compound of automobile brake oil can, comprise the steps:
Homo-polypropylene, thermo-stabilizer, processing aid, nucleator, high melt strength, propylene, compatilizer are added screw extrusion press from the main spout that is arranged in screw extrusion press one end, carry out melt blending, make short glass fiber pass through the weight-loss metering scale from the side spout adding screw extrusion press of described main spout 1/3 ~ 2/3 screw extrusion press length, after other components are carried out melt blending, extruding pelletization obtains described glass fiber reinforced polypropylene compound; The length-to-diameter ratio of described screw extrusion press is 36 ~ 48:1, and processing temperature is 190 ~ 240 ℃.
Because the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
The present invention can guarantee effectively to improve the hot strength of common fiber glass reinforced polypropylene in the situation that other mechanical properties of material do not descend and cost of manufacture is lower by add high melt strength, propylene in the processing formula of homo-polypropylene system; Add thermo-stabilizer, the degraded that polypropylene produces in the establishment course of processing, and give the ageing-resistant performance of canister material excellence; Add processing aid, promote the good dispersion between each composition of blend; Add nucleator, improve the crystallization rate in the material injection moulding process, shortening injection molding cycle; Add compatilizer, effectively increase the interface compatibility between polypropylene and the short glass fiber; Product tensile strength of the present invention (23 ℃) 〉=40MPa, tensile strength (120 ℃) 〉=20MPa, modulus in flexure 〉=2000MPa, notched Izod impact strength 〉=5KJ/m
2, weld mark tensile strength 〉=30Mpa, heat-drawn wire (1.80Mpa) 〉=140 ℃, (150 ℃, 1000h) back draft strength retention 〉=95% satisfies the high rigidity, thermotolerance of automobile brake oil can, the requirement of ageing-resistant and weldability to thermo-oxidative ageing.
The preparation method of glass fiber reinforced polypropylene compound of the present invention has simple to operate, the characteristics that material property guarantees easily.
Embodiment
Further specify the present invention below by embodiment, following examples are the better embodiment of the present invention, but embodiments of the present invention are not subjected to the restriction of following embodiment.
Now embodiment and the used starting material of Comparative Examples are done following explanation, but are not limited to these materials:
| The trade mark | Brief introduction, source |
| PP T30S | Common homo-polypropylene |
| PP B1101 | Common homo-polypropylene |
| PP F401 | Common poly-homo-polypropylene |
| ProfaxPF-613 | High melt strength, propylene, Himont company |
| ProfaxSD-613 | High melt strength, propylene, Himont company |
| Inspire112 | High melt strength, propylene, Dow company |
| HMS200F | High melt strength, propylene, Samsung |
| EBS | Ethylene bis stearic acid amide, the worker is beautified in Shanghai, Shanghai |
| EB-FF | Ethylene bis stearic acid amide, Japanese Kao |
| TMP-5 | The special-purpose nucleator of PP, institute of shanxi coal section |
| HPN-20E | The special-purpose nucleator of PP, Mei Liken |
| Millad 3988 | The special-purpose nucleator of PP, Mei Liken |
| Millad NX8000 | The special-purpose nucleator of PP, Mei Liken |
| CA-100 | Maleic anhydride inoculated polypropylene, French A Ke agate |
| Bondyram 1001CN | Maleic anhydride inoculated polypropylene, Israel Polyram |
| Bondyram 1001 | Maleic anhydride inoculated polypropylene, Israel Polyram |
| Phenols thermo-stabilizer 1010 | 2,6--di-tert-butyl-4-methy phenol, refined treasured |
| Monothioester type thermal stabilizing agent 168 | Three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, refined treasured |
| Monothioester type thermal stabilizing agent 627A | Two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites, Chemtura |
| Monothioester type thermal stabilizing agent 412S | Pentaerythritols ten dithio propyl ester, Chemtura |
| 305K | The special-purpose short glass fiber of PP, the Chongqing glass |
| 508K | The special-purpose short glass fiber of PP, the Mount Taishan glass |
| 248A | The special-purpose short glass fiber of PP, PPG |
| 249A | The special-purpose short glass fiber of PP, PPG |
Embodiment 1
With the melt flow rate (MFR) of 82 kilograms of melt flow rate (MFR)s homo-polypropylene PP T30S that is 1.0g/10min, 0.2 kilogram of phenols thermo-stabilizer 1010,0.3 kilogram of phosphorous acid ester type thermal stabilizing agent 168,0.3 kilogram of processing aid EBS, 0.2 kilogram of special-purpose nucleator TMP-5 of polypropylene, 5 kilograms of Himont companies be the high melt strength, propylene ProfaxPF-613 of 1.0g/10min, 2 kilograms of maleic anhydride inoculated polypropylene CA-100 to add length-to-diameter ratio from the main spout that is arranged in screw extrusion press one end be the twin screw extruder of 40:1, carry out melt blending;
Make the chopped alkali free glass fibre 305K of 10 kilograms of Chongqing international corporations, accurately add the twin screw extruder by the weight-loss metering scale from the side spout of main spout 2/3 screw extrusion press length, after carrying out melt blending with other components, 210 ℃ of extruding pelletizations, the test result performance of gained mixture sees Table 2.
Embodiment 2
With 63 kilograms of melt flow rate (MFR)s homo-polypropylene PP B1101 that is 10.0g/10min, 0.5 kilogram phenols thermo-stabilizer 1010,0.5 kilogram phosphorous acid ester type thermal stabilizing agent 627A, 0.5 kilogram processing aid EB-FF, 0.5 the special-purpose nucleator HPN-20E of kilogram polypropylene, the melt flow rate (MFR) of 10 kilograms of Himont companies is the high melt strength, propylene ProfaxSD-613 of 0.8g/10min, it is the twin screw extruder of 40:1 that 5 kilograms of maleic anhydride inoculated polypropylene Bondyram1001CN add length-to-diameter ratio from the main spout that is arranged in screw extrusion press one end, carries out melt blending;
Make the chopped alkali free glass fibre 508K of 20 kilograms of Zhejiang megalith companies, accurately add the twin screw extruder by the weight-loss metering scale from the side spout of main spout 1/3 screw extrusion press length, after carrying out melt blending with other components, 220 ℃ of extruding pelletizations, the test result performance of gained mixture sees Table 2.
Embodiment 3
With the melt flow rate (MFR) of 49.5 kilograms of melt flow rate (MFR)s homo-polypropylene PP B1101 that is 30g/10min, 0.7 kilogram of phenols thermo-stabilizer 1010,0.8 kilogram of monothioester type thermal stabilizing agent 412S, 1 kilogram of processing aid EB-FF, 1 kilogram of special-purpose nucleator Millad3988 of polypropylene, 15 kilograms of Dow companies be the high melt strength, propylene Inspire112 of 0.5g/10min, 7 kilograms of maleic anhydride inoculated polypropylene Bondyram1001 to add length-to-diameter ratio from the main spout that is arranged in screw extrusion press one end be the twin screw extruder of 40:1, carry out melt blending;
Make the chopped alkali free glass fibre 248A of 25 kilograms of Ovens Corning Incorporateds, accurately add the twin screw extruder by the weight-loss metering scale from the side spout of main spout 1/3 screw extrusion press length, after carrying out melt blending with other components, 230 ℃ of extruding pelletizations, the test result performance of gained mixture sees Table 2.
Embodiment 4
With the melt flow rate (MFR) of 35 kilograms of melt flow rate (MFR)s homo-polypropylene PP F401 that is 80.0g/10min, 1 kilogram of phenols thermo-stabilizer 1010,1 kilogram of monothioester type thermal stabilizing agent 412S, 1.5 kilograms of processing aid EB-FF, 1.5 kilograms of special-purpose nucleator MilladNX8000 of polypropylene, 20 kilograms of Samsungs be the high melt strength, propylene HMS200F of 0.3g/10min, 10 kilograms of maleic anhydride inoculated polypropylene Bondyram1001 to add length-to-diameter ratio from the main spout that is arranged in screw extrusion press one end be the twin screw extruder of 48:1, carry out melt blending;
Make 30 kilograms of chopped alkali free glass fibre 249A of Ovens Corning Incorporated, accurately add the twin screw extruder by the weight-loss metering scale from the side spout of main spout 2/3 screw extrusion press length, after carrying out melt blending with other components, 240 ℃ of extruding pelletizations, the test result performance of gained mixture sees Table 2.
Embodiment 5
With the melt flow rate (MFR) of 24 kilograms of melt flow rate (MFR)s homo-polypropylene PP T30S that is 100.0g/10min, 30 kilograms of Himont companies be the high melt strength, propylene ProfaxPF-613 of 0.01g/10min, 10 kilograms of maleic anhydride inoculated polypropylene CA-100 to add length-to-diameter ratio from the main spout that is arranged in screw extrusion press one end be the twin screw extruder of 36:1, carry out melt blending;
Make the chopped alkali free glass fibre 305K of 36 kilograms of Chongqing international corporations, accurately add the twin screw extruder by the weight-loss metering scale from the side spout of main spout 2/3 screw extrusion press length, after carrying out melt blending with other components, 190 ℃ of extruding pelletizations, the test result performance of gained mixture sees Table 2.
Comparative Examples 1
It is suitable with embodiment 1 to fill a prescription, and the melt flow rate (MFR) of high melt strength, propylene is 2g/10min, and performance perameter is as shown in table 2.
Comparative Examples 2
It is suitable with embodiment 2 to fill a prescription, and the melt flow rate (MFR) of high melt strength, propylene is 10 g/10min, and performance perameter is as shown in table 2.
Comparative Examples 3
It is suitable with embodiment 3 to fill a prescription, and the melt flow rate (MFR) of high melt strength, propylene is 30 g/10min, and performance perameter is as shown in table 2.
Table 1 properties testing standard
| Performance | Unit | Testing standard |
| Heat-drawn wire (1.80MPa) | ℃ | ISO75/1-93 |
| Tensile strength (23 ℃) | MPa | ISO527/2-93 |
| Tensile strength (120 ℃) | MPa | ISO527/2-93 |
| Modulus in flexure | MPa | ISO178/2-93 |
| Notched Izod impact strength | KJ/m 2 | ISO179/2-93 |
| The weld mark tensile strength | Mpa | ISO527/2-93 |
| Stretching strength retentivity (150 ℃, 1000h) | % | ISO527/2-93 |
The formula table of table 2 embodiment 1 ~ 5 and Comparative Examples 1 ~ 3 and the performance test results of mixture
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| Homo-polypropylene | 82 | 63 | 49.5 | 35 | 24 | 82 | 63 | 49.5 |
| HMSPP | 5 | 10 | 15 | 20 | 30 | 5 | 10 | 15 |
| Thermo-stabilizer: phenols+phosphorous acid esters | 0.2+0.3 | 0.5+0.5 | 0.7+0.8 | 1.0+1.0 | 0 | 0.2+0.3 | 0.5+0.5 | 0.7+0.8 |
| Processing aid | 0.3 | 0.5 | 1.0 | 1.5 | 0 | 0.3 | 0.5 | 1.0 |
| Nucleator | 0.2 | 0.5 | 1.0 | 1.5 | 0 | 0.2 | 0.5 | 1.0 |
| Compatilizer | 2 | 5 | 7 | 10 | 10 | 2 | 5 | 7 |
| Short glass fiber | 10 | 20 | 25 | 30 | 36 | 10 | 20 | 25 |
| Heat-drawn wire | 143 | 146 | 150 | 152 | 155 | 130 | 140 | 144 |
| 23 ℃ of tensile strengths | 55 | 85 | 95 | 105 | 125 | 40 | 70 | 82 |
| 120 ℃ of tensile strengths | 38 | 53 | 63 | 80 | 100 | 28 | 45 | 54 |
| Modulus in flexure (MP | 2600 | 4500 | 5500 | 6300 | 7500 | 2200 | 3800 | 4500 |
| Notched Izod impact strength | 7 | 12 | 14 | 15 | 15 | 6.5 | 10 | 11 |
| The weld mark tensile strength | 32 | 34.5 | 34.0 | 33.5 | 33 | 31 | 30 | 30 |
| Stretching strength retentivity | 96 | 97 | 98 | 98 | 98 | 95 | 96 | 96 |
Can find out from the performance testing index of above-described embodiment and Comparative Examples: the tensile strength (23 ℃) of the glass fiber reinforced polypropylene compound of preparation gained 〉=55MPa, tensile strength (120 ℃) 〉=38MPa, modulus in flexure 〉=2600MPa, notched Izod impact strength 〉=7KJ/m2, weld mark tensile strength 〉=32Mpa, heat-drawn wire (1.80Mpa) 〉=143 ℃, (150 ℃ of thermo-oxidative ageings, 1000h) back draft strength retention 〉=96% satisfies the high rigidity, thermotolerance of automobile brake oil can, the requirement of ageing-resistant and weldability.
Claims (10)
1. be used for the glass fiber reinforced polypropylene compound of automobile brake oil can, it is characterized in that, by weight percentage, comprise following component:
Homo-polypropylene 24 ~ 83%
High melt strength, propylene 5 ~ 30%
Compatilizer 2 ~ 10%
Short glass fiber 10 ~ 36%
Wherein, the melt flow rate (MFR) of described high melt strength, propylene under 230 ℃, load 2.16KG condition is 0.01～1.0g/10min.
2. the glass fiber reinforced polypropylene compound for the automobile brake oil can according to claim 1 is characterized in that, also comprises 0 ~ 2wt% thermo-stabilizer, 0 ~ 2wt% processing aid, 0 ~ 2wt% nucleator.
3. the glass fiber reinforced polypropylene compound for the automobile brake oil can according to claim 1 is characterized in that, the melt flow rate (MFR) of described homo-polypropylene under 230 ℃, load 2.16KG condition is 0.1～100 g/10min.
4. the glass fiber reinforced polypropylene compound for the automobile brake oil can according to claim 1 and 2; it is characterized in that described thermo-stabilizer is selected from the mixture class of phenols, amine, phosphorous acid esters, acryl functional group and monothioester, one or more mixtures of calixarene kind.
5. the glass fiber reinforced polypropylene compound for the automobile brake oil can according to claim 1 and 2 is characterized in that, described processing aid is selected from one or more mixtures of metal soap, stearic acid complex ester class, amides.
6. the glass fiber reinforced polypropylene compound for the automobile brake oil can according to claim 1 and 2 is characterized in that, described nucleator is selected from one or more mixtures of 800 ~ 2500 order talcum powder, glucitols, organic phosphate.
7. the glass fiber reinforced polypropylene compound for the automobile brake oil can according to claim 1 is characterized in that, described compatilizer is the polar monomer graft polymkeric substance; Wherein, polymeric matrix is selected from one or more mixtures in the multipolymer, polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-butadiene terpolymer, ethylene-acrylate copolymer, ethylene-acrylate-glycidyl methacrylate copolymer of polyethylene, polypropylene, ethene-α-ethylene-octene copolymer, vinylbenzene and divinyl; Polar monomer is selected from one or more mixtures of maleic anhydride, fumaric acid, methylene-succinic acid, citraconic acid, citraconic anhydride, vinyl Succinic anhydried, methacrylic acid, acrylicacidandesters analog derivative.
8. the glass fiber reinforced polypropylene compound for the automobile brake oil can according to claim 7, it is characterized in that described acrylicacidandesters analog derivative is selected from one or more mixtures of methyl acrylate, ethyl propenoate, methyl methacrylate, glytidyl methacrylate.
9. the glass fiber reinforced polypropylene compound for the automobile brake oil can according to claim 1 is characterized in that, described short glass fiber is the alkali-free short glass fiber.
10. the preparation method of each described glass fiber reinforced polypropylene compound for the automobile brake oil can is characterized in that according to claim 1 ~ 9, comprises the steps:
Homo-polypropylene, thermo-stabilizer, processing aid, nucleator, high melt strength, propylene, compatilizer are added screw extrusion press from the main spout that is arranged in screw extrusion press one end, carry out melt blending, make short glass fiber pass through the weight-loss metering scale from the side spout adding screw extrusion press of described main spout 1/3 ~ 2/3 screw extrusion press length, after other components are carried out melt blending, extruding pelletization obtains described glass fiber reinforced polypropylene compound; The length-to-diameter ratio of described screw extrusion press is 36 ~ 48:1, and processing temperature is 190 ~ 240 ℃.
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| CN103665541A (en) * | 2013-11-04 | 2014-03-26 | 惠州新大都合成材料科技有限公司 | Low-after-contraction polypropylene composite material manufactured by controlling fluidity and preparation method thereof |
| CN103756143A (en) * | 2014-01-03 | 2014-04-30 | 天津金发新材料有限公司 | Reinforced polypropylene compound as well as preparation method and application thereof |
| CN104945737A (en) * | 2015-06-27 | 2015-09-30 | 上海俊尔新材料有限公司 | High-performance glass fiber reinforced polypropylene composite material specially used for micro-foaming and preparation method thereof |
| CN105837941A (en) * | 2016-05-16 | 2016-08-10 | 上海日之升科技有限公司 | Low-floating-fiber glass fiber reinforced polypropylene material and preparation method thereof |
| CN107903490A (en) * | 2017-12-16 | 2018-04-13 | 贵州凯科特材料有限公司 | A kind of soft sense of touch modified material and preparation method thereof of low volatile organic, low smell |
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| CN110591224A (en) * | 2019-08-28 | 2019-12-20 | 江苏沃特新材料科技有限公司 | Polypropylene material and preparation method thereof, structural member and manufacturing method thereof |
| CN110845792A (en) * | 2019-10-23 | 2020-02-28 | 上海金发科技发展有限公司 | Polypropylene composition for automobile water chamber and preparation method thereof |
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| CN103665541A (en) * | 2013-11-04 | 2014-03-26 | 惠州新大都合成材料科技有限公司 | Low-after-contraction polypropylene composite material manufactured by controlling fluidity and preparation method thereof |
| CN103665541B (en) * | 2013-11-04 | 2015-10-28 | 惠州新大都合成材料科技有限公司 | A kind of low post shrinkage polypropylene composite material and preparation method thereof controlling mobility and manufacture |
| CN103756143A (en) * | 2014-01-03 | 2014-04-30 | 天津金发新材料有限公司 | Reinforced polypropylene compound as well as preparation method and application thereof |
| CN104945737A (en) * | 2015-06-27 | 2015-09-30 | 上海俊尔新材料有限公司 | High-performance glass fiber reinforced polypropylene composite material specially used for micro-foaming and preparation method thereof |
| CN105837941A (en) * | 2016-05-16 | 2016-08-10 | 上海日之升科技有限公司 | Low-floating-fiber glass fiber reinforced polypropylene material and preparation method thereof |
| CN107903490A (en) * | 2017-12-16 | 2018-04-13 | 贵州凯科特材料有限公司 | A kind of soft sense of touch modified material and preparation method thereof of low volatile organic, low smell |
| CN109306114A (en) * | 2018-08-09 | 2019-02-05 | 南京聚隆科技股份有限公司 | A kind of hollow blow molding automobile inlet manifold material and preparation method thereof |
| CN110591224A (en) * | 2019-08-28 | 2019-12-20 | 江苏沃特新材料科技有限公司 | Polypropylene material and preparation method thereof, structural member and manufacturing method thereof |
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| CN110845792A (en) * | 2019-10-23 | 2020-02-28 | 上海金发科技发展有限公司 | Polypropylene composition for automobile water chamber and preparation method thereof |
| CN112625360A (en) * | 2020-12-15 | 2021-04-09 | 上海普利特复合材料股份有限公司 | Polypropylene material for injection-molded cold-resistant automobile washing kettle and preparation method thereof |
| CN115216092A (en) * | 2022-07-29 | 2022-10-21 | 横店集团得邦工程塑料有限公司 | Low-temperature-resistant reinforced halogen-free flame-retardant PP/HMSPP composite material and preparation method thereof |
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Application publication date: 20130327 |