CN102924805A - Stress-whitening-resisting glass fiber reinforced polypropylene composite and preparation method thereof - Google Patents
Stress-whitening-resisting glass fiber reinforced polypropylene composite and preparation method thereof Download PDFInfo
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- CN102924805A CN102924805A CN2012104588225A CN201210458822A CN102924805A CN 102924805 A CN102924805 A CN 102924805A CN 2012104588225 A CN2012104588225 A CN 2012104588225A CN 201210458822 A CN201210458822 A CN 201210458822A CN 102924805 A CN102924805 A CN 102924805A
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Abstract
The invention discloses a special stress-whitening-resisting glass fiber reinforced polypropylene composite for automotive trims and a preparation method thereof. The special stress-whitening-resisting glass fiber reinforced polypropylene composite for automotive trims is characterized by comprising the following raw materials by weight percentage: 27-83 percent of polypropylene, 0-2 percent of heat stabilizer, 0-2 percent of processing agent, 0-2 percent of light stabilizer, 0-2 percent of special nucleating agent for polypropylene, 5-20 percent of flexibilizer, 2-10 percent of compatilizer, 5-20 percent of ultrafine talcum powder and 5-15 percent of chopped glass fiber. The preparation method comprises the following steps that after the raw materials are mixed, the mixture is added into a double-screw extruder with the length-diameter ratio of (30-60):1 to be molten and dispersed, meanwhile, the chopped glass fiber is fed into the double-screw extruder from a side feeding mouth to be extruded and pelletized, and the product is obtained. The composite has the characteristics of high stiffness, high heat resistance and stress whitening resistance and meets the requirement of the automotive trim material on stress whitening resistance.
Description
Technical field
The present invention relates to special-purpose glass fiber reinforced polypropylene compound of automotive trim of a kind of anti-stress whitening and preparation method thereof, belong to technical field of polymer materials.
Background technology
Present automobile door plate, the interior material such as column and dashboard matrix resin mainly adopts polypropylene, talcum powder is adopted in reinforcing filler, toughening rubber adopts POE (POE) thermoplastic elastomer, prepare by the twin screw extruder blend, this material has excellent toughness and processing characteristics, but in injection moulding ejection device and assembling process owing to stressedly very easily producing molecular rupture and slippage, make the material stress area produce micro-crack, crazing and hole, thereby the stress area refractive index is changed, show on the macroscopic view to be exactly the stress area blushing, affect the outward appearance of inside gadget.
Summary of the invention
The purpose of this invention is to provide glass fiber reinforced polypropylene compound of a kind of anti-stress whitening and preparation method thereof, the defective that exists to overcome prior art satisfies the needs that automotive upholstery develops.
In order to achieve the above object, the invention provides a kind of glass fiber reinforced polypropylene compound of anti-stress whitening, it is characterized in that, made by following raw material by weight percentage:
Polypropylene 27-83%;
Thermo-stabilizer 0-2%;
Processing aid 0-2%;
Illumination stablizer 0-2%;
The special-purpose nucleator 0-2% of polypropylene;
Toughner 5-20%;
Compatilizer 2-10%;
Superfine talcum powder 5-20%;
Short glass fiber 5-15%.
Preferably, described polypropylene is homopolymerization, Co-polypropylene or both mixtures, and its melt flow rate (MFR) is 0.01-100g/10min.
Preferably, described thermo-stabilizer is one or both the mixture in phenols thermo-stabilizer and phosphoric acid ester thermo-stabilizer and the monothioester type thermal stabilizing agent.
More preferably, described phenols thermo-stabilizer is antioxidant Irganox1010.Described phosphorous acid ester type thermal stabilizing agent is antioxidant Ultranox627A or Irganox168.Described monothioester type thermal stabilizing agent is antioxidant 412S.
Preferably, described processing aid is stearic acid complex ester class processing aid.
Preferably, described illumination stablizer is the special-purpose hindered amine light stabilizer of polypropylene.
Preferably, the special-purpose nucleator of described polypropylene is any one or the two or more mixture in superfine talcum powder, Sorbitol Nucleator and the nucleator in organic phosphate class.
Preferably, described toughner is any one or the two or more mixtures in styrene-butadiene-styrene, ethylene-propylene diene copolymer and the urethane of ethylene-octene copolymer, hydrogenation.
Preferably, described compatilizer is the polar monomer graft polymkeric substance.
More preferably, described polar monomer graft polymkeric substance is maleic anhydride inoculated polypropylene, maleic anhydride grafted ethene-α-ethylene-octene copolymer or its mixture.
Preferably, the order number of described superfine talcum powder is not less than 3000.
Preferably, described short glass fiber is the special-purpose alkali-free short glass fiber of polypropylene.
The present invention also provides the preparation method of the glass fiber reinforced polypropylene compound of above-mentioned anti-stress whitening, it is characterized in that, concrete steps are: after polypropylene, thermo-stabilizer, processing aid, illumination stablizer, the special-purpose nucleator of polypropylene, toughner, compatilizer and superfine talcum powder are mixed, the adding length-to-diameter ratio is 30-60: melting disperses in 1 the twin screw extruder, simultaneously short glass fiber is fed twin screw extruder by the weight-loss metering scale from the side spout, extruding pelletization obtains the glass fiber reinforced polypropylene compound of anti-stress whitening.
Preferably, the length-to-diameter ratio of described twin screw extruder is 40: 1, and each section temperature of this twin screw extruder when extruding pelletization is 190-240 ℃.
The present invention also provides the application of glass fiber reinforced polypropylene compound in the preparation automotive trim of above-mentioned anti-stress whitening.
The present invention adopts polypropylene, thermoplastic elastomer, superfine talcum powder, compatilizer, short glass fiber, thermo-stabilizer, the illumination stablizer, the special-purpose nucleator blend of polypropylene has prepared a kind of special-purpose glass fiber reinforced polypropylene compound of automotive trim of anti-stress whitening, this mixture is owing to having adopted short glass fiber Substitute For Partial superfine talcum powder as strongthener, increased the rigidity of material, improved the yield strength of material, molecular rupture and slippage have been reduced, make the material stress area produce micro-crack, the possibility in crazing and hole, alleviated Injection moulded part eject turn white and assembling process in the stress whitening phenomenon.
The present invention adopts short glass fiber to increase rigidity of material, Injection moulded part is ejected and product when assembling, is difficult for stressed surrender and the molecular chain slippage occurs, and causes stress whitening, has solved the stress whitening phenomenon of traditional interior material.
The effect of the thermo-stabilizer among the present invention is to suppress the degraded that polypropylene produces in the course of processing; The effect of processing aid is the good dispersion that promotes between each composition of blend; The effect of illumination stablizer is that visible light, the UV-light that the inhibition automobile window glass is come in thoroughly decomposed the illumination that the high molecular polymers such as polypropylene, toughner, compatilizer produce; The effect of the special-purpose nucleator of polypropylene is the crystallization rate that improves in the material injection moulding process, shortening injection molding cycle; The effect of toughner is to increase the toughness of material under low-temperature condition, guarantees not produce when low temperature damage sharp-pointed fragment; The effect of superfine talcum powder is to improve the dimensional stability of material and reduce material because the anisotropy that the glass orientation produces; The effect of compatilizer is the interface compatibility that increases between polypropylene and short glass fiber, the superfine talcum powder, guarantees can not produce between polypropylene and glass, the superfine talcum powder to be separated.
Therefore, material provided by the invention has high rigidity, height is heat-resisting and the characteristic of anti-stress whitening, satisfies the requirement of automotive interior material antagonism stress whitening.After testing, tensile strength 〉=30MPa, modulus in flexure 〉=1500MPa, (23 ℃) notched Izod impact strength 〉=20KJ/m
2, (30 ℃) notched Izod impact strength 〉=10KJ/m
2, heat-drawn wire (0.45Mpa) 〉=130 ℃, ball falling impact test (80cm, 500g steel ball) non-whitening.
Embodiment
For the present invention is become apparent, hereby with preferred embodiment, be described in detail below.
Embodiment 1
The first step: adopt high mixer fully to mix 82 kilograms of polypropylene PP7033N (melt flow rate (MFR) is 8g/10min), 0.1 kilogram of phenols thermo-stabilizer 1010,0.1 kilogram of phosphorous acid ester type thermal stabilizing agent 168,0.3 kilogram of processing aid EBS, 0.2 kilogram of hindered amine light stabilizer 770, the 0.3 kilogram of special-purpose nucleator TMP-5 of polypropylene, 5 kilograms of POE POE LC670,2 kilograms of maleic anhydride inoculated polypropylene CA-100,5 kilogram of 3000 order talcum powder;
Second step: the mixture that the first step is obtained is transported to length-to-diameter ratio in 30: 1 twin screw extruder take 95 kg/hours speed, melting disperses, rotating speed is 200r/min, respectively distinguishes temperature setting from the feeding section to head and is set to 140 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃; With the international chopped alkali free glass fibre 305K in 5 kilograms of Chongqing, short glass fiber adds from the speed of side spout with 5 kg/hours by the weight-loss metering scale simultaneously, extruding pelletization, and each of forcing machine section temperature is made as 190 ℃, obtains product.After tested, its performance is as follows:
Table 1
| Performance | Unit | Testing standard | Test result |
| Tensile strength | MPa | ISO527/2-93 | 35.5 |
| Elongation at break | ％ | ISO527/2-93 | 8 |
| Modulus in flexure | MPa | ISO178-93 | 2310 |
| 23 ℃ of notched Izod impact strength | KJ/m 2 | ISO180-93 | 22 |
| -30 ℃ of notched Izod impact strength | KJ/m 2 | ISO180-93 | 12.9 |
| Heat-drawn wire (0.45Mpa) | ℃ | ISO75-93 | 138 |
| Ball falling impact test (80cm, 500g steel ball) | -- | PV3966 | Non-whitening |
Embodiment 2
The first step: with 61.5 kilograms of polypropylene PP K9017 (melt flow rate (MFR) is 17g/10min), 0.5 kilogram phenols thermo-stabilizer 1010,0.5 kilogram phosphorous acid ester type thermal stabilizing agent 168,0.5 kilogram processing aid A-C540A, 0.5 kilogram hindered amine light stabilizer 944,0.5 the special-purpose nucleator HPN-20E of kilogram polypropylene, 12 kilograms of POE POE5062,4 kilograms of maleic anhydride inoculated polypropylene Bondyram1001CN, 10 kilogram of 5000 order talcum powder adopts high mixer fully to mix;
Second step: the mixture that the first step is obtained is transported to length-to-diameter ratio melting in 40: 1 the twin screw extruder take 90 kg/hours speed to be disperseed, rotating speed is 220r/min, respectively distinguishes temperature setting from the feeding section to head and is set to 140 ℃, 200 ℃, 210 ℃, 220 ℃, 200 ℃; With 10 kilograms of chopped alkali free glass fibre 508A of Zhejiang megalith, short glass fiber adds from the speed of side spout with 10 kg/hours by the weight-loss metering scale simultaneously, extruding pelletization, and each of forcing machine section temperature is made as 200 ℃, obtains product.After tested, its performance is as follows:
Table 2
| Performance | Unit | Testing standard | Test result |
| Tensile strength | MPa | ISO527/2-93 | 39 |
| Elongation at break | ％ | ISO527/2-93 | 7 |
| Modulus in flexure | MPa | ISO178-93 | 2400 |
| 23 ℃ of notched Izod impact strength | KJ/m 2 | ISO180-93 | 29 |
| -30 ℃ of notched Izod impact strength | KJ/m 2 | ISO180-93 | 14.5 |
[0043]?
| Heat-drawn wire (0.45Mpa) | ℃ | ISO75-93 | 145 |
| Ball falling impact test (80cm, 500g steel ball) | -- | PV3966 | Non-whitening |
Embodiment 3
The first step: adopt high mixer fully to mix 47 kilograms of polypropylene PP K9026 (melt flow rate (MFR) is 22g/10min), 1 kilogram of phenols thermo-stabilizer 1010,1 kilogram of phosphorous acid ester type thermal stabilizing agent 627A, 1 kilogram of processing aid Zinic stearas, 1 kilogram of hindered amine light stabilizer 622, the 1 kilogram of special-purpose nucleator HTPUTRA5 of polypropylene, 16 kilograms of POE POE8130,7 kilograms of maleic anhydride inoculated polypropylene Bondyram1001,15 kilogram of 3000 order talcum powder;
Second step: the mixture that the first step is obtained is transported to length-to-diameter ratio melting in 40: 1 the twin screw extruder take 90 kg/hours speed to be disperseed, rotating speed is 240r/min, respectively distinguishes temperature setting from the feeding section to head and is set to 140 ℃, 200 ℃, 220 ℃, 230 ℃, 200 ℃; With 10 kilograms of chopped alkali free glass fibre 508B of Zhejiang megalith, short glass fiber adds from the speed of side spout with 10 kg/hours by the weight-loss metering scale simultaneously, extruding pelletization, and each of forcing machine section temperature is made as 200 ℃, obtains product.After tested, its performance is as follows:
Table 3
| Performance | Unit | Testing standard | Test result |
| Tensile strength | MPa | ISO527/2-93 | 38.5 |
| Elongation at break | ％ | ISO527/2-93 | 7 |
| Modulus in flexure | MPa | ISO178-93 | 2450 |
| 23 ℃ of notched Izod impact strength | KJ/m 2 | ISO180-93 | 40 |
| -30 ℃ of notched Izod impact strength | KJ/m 2 | ISO180-93 | 16.5 |
| Heat-drawn wire (0.45Mpa) | ℃ | ISO75-93 | 149 |
| Ball falling impact test (80cm, 500g steel ball) | -- | PV3966 | Non-whitening |
Embodiment 4
The first step: with 27 kilograms of polypropylene PP K9026 (melt flow rate (MFR) is 22g/10min), 1 kilogram of phenols thermo-stabilizer 1010,1 kilogram of monothioester type thermal stabilizing agent 412S, 2 kilograms of processing aid Zinic stearass, 2 kilograms of hindered amine light stabilizers 622,2 kilograms of special-purpose nucleator Millad3988 of polypropylene, 20 kilograms of POE POE8130,10 kilograms of maleic anhydride inoculated polypropylene Bondyram1001,20 kilogram of 5000 order talcum powder adopts high mixer fully to mix.
Second step: the mixture that the first step is obtained is transported to length-to-diameter ratio melting in 60: 1 the twin screw extruder take 85 kg/hours speed to be disperseed, rotating speed is 260r/min, respectively distinguishes temperature setting from the feeding section to head and is set to 140 ℃, 200 ℃, 230 ℃, 240 ℃, 200 ℃; Simultaneously 15 kilograms of healthy and free from worry chopped alkali free glass fibre 249A dimensions of Ovens are added from the speed of side spout with 15 kg/hours by the weight-loss metering scale, extruding pelletization, each of forcing machine section temperature is made as 240 ℃, obtains product.After tested, its performance is as follows:
Table 4
| Performance | Unit | Testing standard | Test result |
| Tensile strength | MPa | ISO527/2-93 | 37 |
| Elongation at break | ％ | ISO527/2-93 | 9 |
| Modulus in flexure | MPa | ISO178-93 | 2100 |
| 23 ℃ of notched Izod impact strength | KJ/m 2 | ISO180-93 | 43 |
| -30 ℃ of notched Izod impact strength | KJ/m 2 | ISO180-93 | 17.5 |
| Heat-drawn wire (0.45Mpa) | ℃ | ISO75-93 | 152 |
| Ball falling impact test (80cm, 500g steel ball) | -- | PV3966 | Non-whitening |
Claims (10)
1. the glass fiber reinforced polypropylene compound of an anti-stress whitening is characterized in that, by following with weight percent
The raw material of number meter is made:
Polypropylene 27-83%;
Thermo-stabilizer 0-2%;
Processing aid 0-2%;
Illumination stablizer 0-2%;
The special-purpose nucleator 0-2% of polypropylene;
Toughner 5-20%;
Compatilizer 2-10%;
Superfine talcum powder 5-20%;
Short glass fiber 5-15%.
2. the glass fiber reinforced polypropylene compound of anti-stress whitening as claimed in claim 1 is characterized in that, described polypropylene is homopolymerization, Co-polypropylene or both mixtures, and its melt flow rate (MFR) is 0.01-100g/10min.
3. the glass fiber reinforced polypropylene compound of anti-stress whitening as claimed in claim 1 is characterized in that, described thermo-stabilizer is one or both the mixture in phenols thermo-stabilizer and phosphoric acid ester thermo-stabilizer and the monothioester type thermal stabilizing agent.
4. the glass fiber reinforced polypropylene compound of anti-stress whitening as claimed in claim 1 is characterized in that, described processing aid is stearic acid complex ester class processing aid.
5. the glass fiber reinforced polypropylene compound of anti-stress whitening as claimed in claim 1 is characterized in that, described illumination stablizer is the special-purpose hindered amine light stabilizer of polypropylene.
6. the glass fiber reinforced polypropylene compound of anti-stress whitening as claimed in claim 1, it is characterized in that, the special-purpose nucleator of described polypropylene is any one or the two or more mixture in superfine talcum powder, Sorbitol Nucleator and the nucleator in organic phosphate class.
7. the glass fiber reinforced polypropylene compound of anti-stress whitening as claimed in claim 1, it is characterized in that, described toughner is any one or the two or more mixtures in styrene-butadiene-styrene, ethylene-propylene diene copolymer and the urethane of ethylene-octene copolymer, hydrogenation.
8. the glass fiber reinforced polypropylene compound of anti-stress whitening as claimed in claim 1 is characterized in that, described compatilizer is the polar monomer graft polymkeric substance.
9. the preparation method of the glass fiber reinforced polypropylene compound of anti-stress whitening claimed in claim 1, it is characterized in that, concrete steps are: after polypropylene, thermo-stabilizer, processing aid, illumination stablizer, the special-purpose nucleator of polypropylene, toughner, compatilizer and superfine talcum powder are mixed, the adding length-to-diameter ratio is 30-60: melting disperses in 1 the twin screw extruder, simultaneously short glass fiber is fed twin screw extruder by the weight-loss metering scale from the side spout, extruding pelletization obtains the glass fiber reinforced polypropylene compound of anti-stress whitening.
10. the application of the glass fiber reinforced polypropylene compound of anti-stress whitening claimed in claim 1 in the preparation automotive trim.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104387663A (en) * | 2014-10-31 | 2015-03-04 | 浙江俊尔新材料股份有限公司 | Long glass fiber reinforced polypropylene composite material as well as preparation method and application thereof |
| CN104479216A (en) * | 2014-11-20 | 2015-04-01 | 苏州新区佳合塑胶有限公司 | Automobile diversion plate material |
| CN105504489A (en) * | 2015-12-23 | 2016-04-20 | 浙江品诺新材料有限公司 | Alkali-free glass fiber reinforcing modified polypropylene composite material and preparing method thereof |
| CN105542375A (en) * | 2015-12-30 | 2016-05-04 | 上海普利特复合材料股份有限公司 | High-performance polypropylene composite material applicable to thin-walled part injection molding and preparation method thereof |
| US20160244592A1 (en) * | 2013-12-09 | 2016-08-25 | Adeka Corporation | Substrate with improved coatability |
| CN107868343A (en) * | 2017-11-21 | 2018-04-03 | 天津金发新材料有限公司 | It is a kind of it is low turn white, low temperature toughness reinforcing, modified clear acrylic |
| CN107880399A (en) * | 2017-12-26 | 2018-04-06 | 肖彬 | Automobile decoration piece polypropylene plastics and its production technology |
| CN107955272A (en) * | 2017-11-21 | 2018-04-24 | 天津金发新材料有限公司 | It is a kind of it is low turn white, resistance to oil bath, low temperature toughness reinforcing, fiber glass reinforced polypropylene material |
| CN107987397A (en) * | 2017-11-21 | 2018-05-04 | 天津金发新材料有限公司 | It is a kind of it is low turn white, resistance to oil bath, low temperature toughness reinforcing, modified clear acrylic |
| CN110878159A (en) * | 2019-11-14 | 2020-03-13 | 中广核俊尔（上海）新材料有限公司 | Low-density polypropylene composite material and preparation method thereof |
| CN111925597A (en) * | 2020-09-15 | 2020-11-13 | 江苏金发科技新材料有限公司 | Anti-aging stress whitening-resistant polypropylene composition and preparation method thereof |
| CN115948000A (en) * | 2022-12-30 | 2023-04-11 | 上海日之升科技有限公司 | Stress whitening resistant flame-retardant polypropylene composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160244592A1 (en) * | 2013-12-09 | 2016-08-25 | Adeka Corporation | Substrate with improved coatability |
| CN104387663A (en) * | 2014-10-31 | 2015-03-04 | 浙江俊尔新材料股份有限公司 | Long glass fiber reinforced polypropylene composite material as well as preparation method and application thereof |
| CN104387663B (en) * | 2014-10-31 | 2016-07-06 | 中广核俊尔新材料有限公司 | A kind of long glass fiber reinforced polypropylene composite material and its preparation method and application |
| CN104479216A (en) * | 2014-11-20 | 2015-04-01 | 苏州新区佳合塑胶有限公司 | Automobile diversion plate material |
| CN105504489A (en) * | 2015-12-23 | 2016-04-20 | 浙江品诺新材料有限公司 | Alkali-free glass fiber reinforcing modified polypropylene composite material and preparing method thereof |
| CN105542375A (en) * | 2015-12-30 | 2016-05-04 | 上海普利特复合材料股份有限公司 | High-performance polypropylene composite material applicable to thin-walled part injection molding and preparation method thereof |
| CN107868343A (en) * | 2017-11-21 | 2018-04-03 | 天津金发新材料有限公司 | It is a kind of it is low turn white, low temperature toughness reinforcing, modified clear acrylic |
| CN107955272A (en) * | 2017-11-21 | 2018-04-24 | 天津金发新材料有限公司 | It is a kind of it is low turn white, resistance to oil bath, low temperature toughness reinforcing, fiber glass reinforced polypropylene material |
| CN107987397A (en) * | 2017-11-21 | 2018-05-04 | 天津金发新材料有限公司 | It is a kind of it is low turn white, resistance to oil bath, low temperature toughness reinforcing, modified clear acrylic |
| CN107955272B (en) * | 2017-11-21 | 2021-02-26 | 天津金发新材料有限公司 | Low-blushing, oil-bath-resistant, low-temperature-toughened and glass-fiber-reinforced polypropylene material |
| CN107880399A (en) * | 2017-12-26 | 2018-04-06 | 肖彬 | Automobile decoration piece polypropylene plastics and its production technology |
| CN110878159A (en) * | 2019-11-14 | 2020-03-13 | 中广核俊尔（上海）新材料有限公司 | Low-density polypropylene composite material and preparation method thereof |
| CN111925597A (en) * | 2020-09-15 | 2020-11-13 | 江苏金发科技新材料有限公司 | Anti-aging stress whitening-resistant polypropylene composition and preparation method thereof |
| CN115948000A (en) * | 2022-12-30 | 2023-04-11 | 上海日之升科技有限公司 | Stress whitening resistant flame-retardant polypropylene composite material and preparation method thereof |
| CN115948000B (en) * | 2022-12-30 | 2024-06-21 | 上海日之升科技有限公司 | Stress whitening resistant flame-retardant polypropylene composite material and preparation method thereof |
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Application publication date: 20130213 |