CN103087429A - Low temperature impact resisting glass fiber reinforced polypropylene composite material as well as preparation and application thereof - Google Patents
Low temperature impact resisting glass fiber reinforced polypropylene composite material as well as preparation and application thereof Download PDFInfo
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Abstract
The invention provides a low temperature impact resisting glass fiber reinforced polypropylene composite material as well as preparation and application thereof. The composite material provided by the invention comprises 40-90 parts of co-polypropylene, 2-10 parts of compatilizer, 5-45 parts of glass fiber and 2-10 parts of highly branched chain polyethylene in parts by weight. According to the composite material based on high impact co-polypropylene as a base material and highly branched chain polyethylene with hexane and octylene as branched chains as a crack propagation inhibitor, the good yield is ensured by a common twin screw device, so that the cost is lower. The composite material has better low temperature impact resistance.
Description
Technical field
The present invention relates to protective shield at the bottom of car, be specifically related to a kind of low-temperature impact-resistant glass fiber reinforced polypropylene composite material and the application of protective shield at the bottom of car.
Background technology
At the bottom of car, protective shield is to determine the foot guard device of body design according to various different automobile types, at first be to prevent earth parcel engine, cause engine radiating bad, next is in order to prevent in driving process because rough road surface is caused and clashed into the damage that causes the parts such as engine bottom of car, help in addition the engine bottom to form steady air flow, the noise produced while reducing high-speed cruising, and can capable of saving fuel oil.General automobile bottom backplate is divided into plastics, metal according to the material difference.Plastic bottom backplate price is comparatively cheap; production technique does not simply need the input of substantial contribution and high value equipment, produces this type of backplate entry threshold lower, but this material backplate is easily broken; winter is all the more so, after the damaged fragmentation, can't repair and not have long-term provide protection.
Polypropylene is the kind of consumption maximum in automotive plastic, has the advantages such as density is little, performance good, easy processing.But the shortcomings such as polypropylene material low temperature brittleness cause its goods poor impact resistance, limited its further application on automobile.Protective shield at the bottom of glass fiber reinforced polypropylene composite material making car, introducing due to the glass reinforced effects, make the strength of materials very high, but still there is the low temperature brittleness poor of material, can improve its low temperature brittleness with toughner, but the toughner consumption also exists cost relatively high, the problem that intensity obviously reduces.
A kind of high-impact, low floating fine long glass fiber-reinforced polypropylene materials are disclosed in the Chinese patent application that publication number is CN102070843A, component by following weight per-cent forms, long glass fiber-reinforced polypropylene master batch 10% ~ 80%, high-impact, low floating fine master batch 20% ~ 90%; The formation of described long glass fiber-reinforced polypropylene master batch is: Co-polypropylene 8% ~ 80%, homo-polypropylene 0 ~ 80%, glass 10% ~ 60%, graft polypropylene 1% ~ 10%, oxidation inhibitor 0.1% ~ 2%; The formation of described high-impact, low floating fine master batch is Co-polypropylene 20% ~ 80%, glass 0 ~ 50%, elastomerics 0 ~ 30%, grafting elastomerics 0 ~ 30%, low-viscosity polyamides resin 0 ~ 10%, oxidation inhibitor 0.1 ~ 2%, processing aid 0.2% ~ 5%.Its advantage is, high, the floating fine phenomenon of the polypropylene material surface luster that it prepares is few, and good by the anti-property fallen of the finished product of material manufacture, good processability, can be for replacing the relevant product of engineering plastics.Long glass fiber-reinforced polypropylene materials needs relatively special device fabrication, and because needs glass melt impregnation could reach due performance by good dispersion, so output is not high.
Disclose a kind of fiber glass reinforced polypropylene material of high resistance thermal-oxidative aging property in the Chinese patent application that publication number is CN 1696187A, disclose a kind of heat oxygen aging resistance, ultraviolet glass fiber reinforced polypropylene composite material in the Chinese patent application of publication number CN 101153096A.Both by additive compound, reach the anti-long-term light/heat aging performance of fiber glass reinforced polypropylene.
Therefore, still need and develop the satisfactory glass fiber reinforced polypropylene composite material of a kind of low-temperature impact-resistant in this area, for protective shield at the bottom of car.
Summary of the invention
Protective shield at the bottom of the object of the present invention is to provide a kind of low-temperature impact-resistant glass fiber reinforced polypropylene composite material for car.
Glass fiber reinforced polypropylene composite material provided by the invention comprises following component:
Co-polypropylene 40 weight parts ~ 90 weight parts;
Compatilizer 2 weight parts ~ 10 weight parts;
Glass fibre 5 weight parts ~ 45 weight parts;
Higly branched chain polyethylene 2 weight parts ~ 10 weight parts.
Further, described matrix material also comprises following component:
Oxidation inhibitor 0.1 weight part ~ 1.5 weight parts;
Lubricant 0.1 weight part ~ 0.5 weight part.
According to preference of the present invention, described Co-polypropylene is formed by ethene and copolymerization of propylene, 23 ℃ of simply supported beam notched Izod impact strength>=45kJ/m
2, 230 ℃, 2.16kg melt flow rate (MFR)>=3g/10min.
According to preference of the present invention, described compatilizer is maleic anhydride inoculated polypropylene.
According to preference of the present invention, described glass fibre is that alkali-free short fiber or continuous alkali-free are long fine, and the diameter of described glass fibre is 9-13 μ m.
According to preference of the present invention, described higly branched chain polyethylene, its side chain is hexene and/or octene.
According to preference of the present invention; described oxidation inhibitor is four [β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2; the 4-di-tert-butyl) ester, the two octadecyl esters of thio-2 acid, the two lauryls, 1 of thio-2 acid; 3; 5-tri-(3; the 5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide, 1; 3; 5-tri-(3; the 5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide, N, N'-is two-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) one or more in hexanediamine.
According to preference of the present invention, described lubricant is calcium stearate, Zinic stearas.
According to preference of the present invention, described glass fiber reinforced polypropylene composite material comprises following component:
Co-polypropylene 40 weight parts ~ 75 weight parts;
Compatilizer 2 weight parts ~ 8 weight parts;
Glass fibre 15 weight parts ~ 45 weight parts;
Higly branched chain polyethylene 3 weight parts ~ 10 weight parts.
Oxidation inhibitor 0.1 weight part ~ 0.8 weight part;
Lubricant 0.1 weight part ~ 0.5 weight part.
The preparation method of glass fiber reinforced polypropylene composite material provided by the invention comprises the following steps:
(1) described Co-polypropylene, compatilizer, higly branched chain polyethylene are mixed and obtain mixture;
(2) after the mixture that adopts twin screw extruder that step (1) is obtained and described glass fibre melting, extrude and obtain described matrix material.
According to preference of the present invention, the rest materials except glass is entered to twin screw extruder from main drawing-in device, melting is sheared and is disperseed, and glass is entered to twin screw extruder from venting port or side drawing-in device.
The barrel of described twin screw extruder is ten joint cylindrical shells, and the first segment cylindrical shell connects main drawing-in device, and the 6th saves the cylindrical shell exhaust and add fine mouthful, connection side drawing-in device, and the 9th joint cylindrical shell vacuumizes; Barrel temperature is set to: the first segment cylindrical shell does not heat, 180 ± 5 ℃ of second section cylindrical shells, the 3rd 200 ± 5 ℃ of joint cylindrical shells, the 4th 220 ± 5 ℃ of joint cylindrical shells, the 5th 220 ± 5 ℃ of joint cylindrical shells, the 6th 200 ± 5 ℃ of joint cylindrical shells, the 7th 210 ± 5 ℃ of joint cylindrical shells, the 8th 220 ± 5 ℃ of joint cylindrical shells, the 9th 220 ± 5 ℃ of joint cylindrical shells, 220 ± 5 ℃ of protelum cylindrical shells, 230 ± 5 ℃ of heads; Roving glass fiber adds by adding fine mouthful continuously, and short fiber is added by the side feeding, by regulating roving glass fiber radical, engine speed, main feeding and side rate of feeding, regulates glass fiber content; Extrude that material strip is cooling, dry, pelletizing, packing.
The application of glass fiber reinforced polypropylene composite material provided by the invention, for the preparation of protective shield at the bottom of car.
Compared with prior art, the present invention has following advantage:
The present invention adopts High Impact Polypropylene as base-material, the higly branched chain polyethylene that hexene and octene are side chain is as the inhibitor of crackle diffusion, guarantee good output by the common double screw apparatus, cost is lower, and matrix material has low-temperature impact-resistant performance preferably.
The present invention is by entering twin screw extruder by the rest materials except glass from main drawing-in device, melting is sheared and is disperseed, glass is entered to twin screw extruder from venting port or side drawing-in device, improve the consistency of glass and matrix resin by compatilizer, improve its strengthening action.Adopt and shear stronger blend screw combinations, improve the degree of scatter of higly branched chain polyethylene in matrix, improve material at low temperature fragility.
The blending extrusion modification processing of the raw material by special formulation, make on its basis that keeps high yield and lower cost, promote the low-temperature flexibility of polypropylene material, solve glass fiber reinforced polypropylene composite material low-temperature impact cracking, meet the application requiring of vapour with bottom guard plate.
Glass fiber reinforced polypropylene composite material of the present invention, actual measurement over-all properties and the GB205U of Borealis performance approach, and can be widely used in car foot guard plate.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can combining mutually between specifically described each technical characterictic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tire out and state no longer one by one at this.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for the present invention is described.
Embodiment 1
As shown in table 1, weighing Qilu Petrochemical Co-polypropylene SP179(notched Izod impact strength>=45kJ/m
2), 68.5 weight part, higly branched chain polyethylene LLDPE7042(raises sub-petrochemical industry) 5 weight parts, the maleic anhydride inoculated polypropylene Compatibilizer C MG5001(MAH of Shanghai Zhi Sheng company percentage of grafting>=1%) 5 weight parts, the continuous roving glass fiber 988A(of alkali-free glass diameter is 9-13 μ m) 21 weight parts, antioxidant 1010 (four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester) and irgasfos 168 (three [2, the 4-di-tert-butyl-phenyl] phosphorous acid ester) each 0.1 weight part, processing aid calcium stearate 0.3 weight part, after each component except glass is mixed, put into the forcing machine hopper, by the twin screw extruder melt blending, continuous roving glass fiber is added by venting port or short fiber is added by the side spout, by regulating engine speed, main feeding and roving glass fiber radical or side rate of feeding are regulated glass fiber content, extrude that material strip is cooling, air-dry, pelletizing, equal mixed, packings.
The barrel of described twin screw extruder is ten joint cylindrical shells, and the first segment cylindrical shell connects main drawing-in device, and the 6th saves the cylindrical shell exhaust and add fine mouthful, connection side drawing-in device, and the 9th joint cylindrical shell vacuumizes.Barrel temperature is set to: the first segment cylindrical shell does not heat, 180 ± 5 ℃ of second section cylindrical shells, the 3rd 200 ± 5 ℃ of joint cylindrical shells, the 4th 220 ± 5 ℃ of joint cylindrical shells, the 5th 220 ± 5 ℃ of joint cylindrical shells, the 6th 200 ± 5 ℃ of joint cylindrical shells, the 7th 210 ± 5 ℃ of joint cylindrical shells, the 8th 220 ± 5 ℃ of joint cylindrical shells, the 9th 220 ± 5 ℃ of joint cylindrical shells, 220 ± 5 ℃ of protelum cylindrical shells, 230 ± 5 ℃ of heads.
By the low-temperature impact-resistant Reinforced Polypropylene granules composite material that makes, at air dry oven, 90 ℃ of dryings 1 hour, then by injection moulding machine injection moulding test bars.Density measurement is pressed DIN EN ISO53479 standard and is carried out; Ash content is pressed DIN EN ISO1172 test; The tensile strength test is pressed DIN EN ISO527-2 standard and is carried out, and draw speed is 50mm/min; The bending property test is pressed DIN EN ISO178 standard and is carried out, and speed is 2mm/min; The simply supported beam unnotched impact strength is pressed DIN EN ISO179-1 standard and is carried out.-30 ℃ of simply supported beam unnotched impact strengths are pressed DIN EN ISO179-1 test, and sample is tested after-30 ℃ of cryostates are placed 4h.The low temperature falling sphere: press the PV3905 test, thickness of sample 2mm, diameter 100mm disk, the base plate strip pit, the heavy 500g of ball, height of the fall ball 500mm, sample is tested after-40 ℃ of conditions are transferred 4h, and fall sphere test completes in 10s from taking out cryostat.
The proportioning (weight part) of each component of table 1 low-temperature impact-resistant glass fiber reinforced polypropylene composite material
Embodiment 2
As shown in table 1, weighing Qilu Petrochemical Co-polypropylene SP179(notched Izod impact strength>=45kJ/m
2) 56.5 weight parts, higly branched chain polyethylene LLDPE7042(raises sub-petrochemical industry) 7 weight parts, day rise maleic anhydride inoculated polypropylene Compatibilizer C MG5001(MAH percentage of grafting>=1%) 5 weight parts, the continuous roving glass fiber 988A(of alkali-free glass diameter is 9-13 μ m) 31 weight parts, antioxidant 1010, 168 each 0.1 weight parts, processing aid calcium stearate 0.3 weight part, after each component except glass is mixed, put into the forcing machine hopper, by the twin screw extruder melt blending, continuous roving glass fiber is added by venting port or short fiber is added by the side spout, by regulating engine speed, main feeding and roving glass fiber radical or side rate of feeding are regulated glass fiber content, extrude that material strip is cooling, air-dry, pelletizing, equal mixed, packings.
Processing parameter, batten preparation condition and testing method are with embodiment 1.
Embodiment 3
As shown in table 1, weighing Qilu Petrochemical Co-polypropylene SP179(notched Izod impact strength>=45kJ/m
2) 43.5 weight parts, higly branched chain polyethylene LLDPE7042(raises sub-petrochemical industry) 10 weight parts, day rise maleic anhydride inoculated polypropylene Compatibilizer C MG5001(MAH percentage of grafting>=1%) 5 weight parts, the continuous roving glass fiber 988A(of alkali-free glass diameter is 9-13 μ m) 41 weight parts, antioxidant 1010, 168 each 0.1 weight parts, processing aid calcium stearate 0.3 weight part, after each component except glass is mixed, put into the forcing machine hopper, by the twin screw extruder melt blending, continuous roving glass fiber is added by venting port or short fiber is added by the side spout, by regulating engine speed, main feeding and roving glass fiber radical or side rate of feeding are regulated glass fiber content, extrude that material strip is cooling, air-dry, pelletizing, equal mixed, packings.
Processing parameter, batten preparation condition and testing method are with embodiment 1.
Comparative Examples 1
As shown in table 1, weighing homo-polypropylene T30S(Maoming Petrochemical) 73.5 weight parts, day rise maleic anhydride inoculated polypropylene Compatibilizer C MG5001(MAH percentage of grafting >=1%) 5 weight parts, the continuous roving glass fiber 988A(of alkali-free glass diameter is 9-13 μ m) 21 weight parts, antioxidant 1010, 168 each 0.1 weight parts, processing aid calcium stearate 0.3 weight part, after each component except glass is mixed, put into the forcing machine hopper, by the twin screw extruder melt blending, continuous roving glass fiber is added by venting port or short fiber is added by the side spout, by regulating engine speed, main feeding and roving glass fiber radical or side rate of feeding are regulated glass fiber content, extrude that material strip is cooling, air-dry, pelletizing, equal mixed, packings.
Processing parameter, batten preparation condition and testing method are with embodiment 1.
Comparative Examples 2
As shown in table 1, weighing homo-polypropylene T30S(Maoming Petrochemical) 58.5 weight parts, ethylene-octene copolymer POE8150(Tao Shi) 10 weight parts, few branched polyethylene HDPE5000S(raises sub-petrochemical industry) 5 weight parts, day rise maleic anhydride inoculated polypropylene Compatibilizer C MG5001(MAH percentage of grafting >=1%) 5 weight parts, the continuous roving glass fiber 988A(of alkali-free glass diameter is 9-13 μ m) 21 weight parts, antioxidant 1010, 168 each 0.1 weight parts, processing aid calcium stearate 0.3 weight part, after each component except glass is mixed, put into the forcing machine hopper, by the twin screw extruder melt blending, continuous roving glass fiber is added by venting port or short fiber is added by the side spout, by regulating engine speed, main feeding and roving glass fiber radical or side rate of feeding are regulated glass fiber content, extrude that material strip is cooling, air-dry, pelletizing, equal mixed, packings.
Processing parameter, batten preparation condition and testing method are with embodiment 1.
Comparative Examples 3
As shown in table 1, weighing Qilu Petrochemical Co-polypropylene SP179(notched Izod impact strength>=45kJ/m
2) 73.5 weight parts, day rise maleic anhydride inoculated polypropylene Compatibilizer C MG5001(MAH percentage of grafting>=1%) 5 weight parts, the continuous roving glass fiber 988A(of alkali-free glass diameter is 9-13 μ m) 21 weight parts, antioxidant 1010, 168 each 0.1 weight parts, processing aid calcium stearate 0.3 weight part, after each component except glass is mixed, put into the forcing machine hopper, by the twin screw extruder melt blending, continuous roving glass fiber is added by venting port or short fiber is added by the side spout, by regulating engine speed, main feeding and roving glass fiber radical or side rate of feeding are regulated glass fiber content, extrude that material strip is cooling, air-dry, pelletizing, equal mixed, packings.
Processing parameter, batten preparation condition and testing method are with embodiment 1.
Comparative Examples 4
As shown in table 1, weighing Qilu Petrochemical Co-polypropylene SP179(notched Izod impact strength>=45kJ/m
2) 58.5 weight parts, ethylene-octene copolymer POE8150(Tao Shi) 10 weight parts, few branched polyethylene HDPE5000S(raises sub-petrochemical industry) 5 weight parts, day rise maleic anhydride inoculated polypropylene Compatibilizer C MG5001(MAH percentage of grafting>=1%) 5 weight parts, the continuous roving glass fiber 988A(of alkali-free glass diameter is 9-13 μ m) 21 weight parts, antioxidant 1010, 168 each 0.1 weight parts, processing aid calcium stearate 0.3 weight part, after each component except glass is mixed, put into the forcing machine hopper, by the twin screw extruder melt blending, continuous roving glass fiber is added by venting port or short fiber is added by the side spout, by regulating engine speed, main feeding and roving glass fiber radical or side rate of feeding are regulated glass fiber content, extrude that material strip is cooling, air-dry, pelletizing, equal mixed, packings.
Processing parameter, batten preparation condition and testing method are with embodiment 1.
The performance of matrix material prepared for embodiment and Comparative Examples by table 2.
Each embodiment of table 2, Comparative Examples the performance test results
Comparative example 1-3 and Comparative Examples 1-4 can find out, adopt the prepared fiber glass reinforced polypropylene material of the present invention being better than Comparative Examples aspect the low-temperature impact-resistant performance.From Comparative Examples 4, can find out, Co-polypropylene just has certain low-temperature impact-resistant effect under assisting adding a large amount of ethylene-octene copolymers and few branched polyethylene, but the intensity of material obviously reduces, and the cost of material is also relatively high.
Broken problem after the present invention has overcome prior art and prepares at the bottom of car protective shield and be subject in the winter time stone etc. and impact, guaranteed the material low-temperature impact-resistant simultaneously other performances of material still meet the car gage requirement, and material cost is relatively low.
All documents of mentioning in the present invention are all quoted as a reference in this application, just as each piece of document quoted separately as a reference.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. a glass fiber reinforced polypropylene composite material, is characterized in that, described matrix material comprises following component:
Co-polypropylene 40 weight parts ~ 90 weight parts;
Compatilizer 2 weight parts ~ 10 weight parts;
Glass fibre 5 weight parts ~ 45 weight parts;
Higly branched chain polyethylene 2 weight parts ~ 10 weight parts.
2. glass fiber reinforced polypropylene composite material as claimed in claim 1, is characterized in that, described matrix material also comprises following component:
Oxidation inhibitor 0.1 weight part ~ 1.5 weight parts;
Lubricant 0.1 weight part ~ 0.5 weight part.
3. glass fiber reinforced polypropylene composite material as claimed in claim 1, is characterized in that, described Co-polypropylene is formed by ethene and copolymerization of propylene, 23 ℃ of simply supported beam notched Izod impact strength>=45kJ/m
2, 230 ℃, 2.16kg melt flow rate (MFR)>=3g/10min.
4. glass fiber reinforced polypropylene composite material as claimed in claim 1, is characterized in that, described compatilizer is maleic anhydride inoculated polypropylene.
5. glass fiber reinforced polypropylene composite material as claimed in claim 1, is characterized in that, described glass fibre is that alkali-free short fiber or continuous alkali-free are long fine, and the diameter of described glass fibre is 9-13 μ m.
6. glass fiber reinforced polypropylene composite material as claimed in claim 1, is characterized in that, described higly branched chain polyethylene, and its side chain is hexene and/or octene.
7. glass fiber reinforced polypropylene composite material as claimed in claim 2, it is characterized in that: described oxidation inhibitor is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2, the 4-di-tert-butyl) ester, the two octadecyl esters of thio-2 acid, the two lauryls, 1 of thio-2 acid, 3, one or more in 5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide.
8. glass fiber reinforced polypropylene composite material as claimed in claim 2, it is characterized in that: described lubricant is calcium stearate, Zinic stearas.
9. the preparation method of glass fiber reinforced polypropylene composite material as claimed in claim 1, is characterized in that, comprises the following steps:
(1) described Co-polypropylene, compatilizer, higly branched chain polyethylene are mixed and obtain mixture;
(2) after the mixture that adopts twin screw extruder that step (1) is obtained and described glass fibre melting, extrude and obtain described matrix material.
10. as the application of the described glass fiber reinforced polypropylene composite material of claim 1 ~ 8 any one, it is characterized in that, for the preparation of protective shield at the bottom of car.
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| CN103937093A (en) * | 2014-03-21 | 2014-07-23 | 浙江俊尔新材料股份有限公司 | Long glass fiber reinforced polypropylene composite material and preparation method |
| CN104877231A (en) * | 2015-03-26 | 2015-09-02 | 苏州市德莱尔建材科技有限公司 | Low-temperature impact resistant PP and preparation method thereof |
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| CN101838423A (en) * | 2010-06-10 | 2010-09-22 | 南京聚隆科技股份有限公司 | Modified polypropylene material for thin-wall bumper and preparation method thereof |
| CN102604209A (en) * | 2012-02-20 | 2012-07-25 | 金发科技股份有限公司 | Thermal-oxidizing-aging resisting polypropylene composite |
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| CN101469093A (en) * | 2007-12-25 | 2009-07-01 | 上海普利特复合材料股份有限公司 | Ultralong unit extension glass fiber reinforced polypropylene composite material |
| CN101838423A (en) * | 2010-06-10 | 2010-09-22 | 南京聚隆科技股份有限公司 | Modified polypropylene material for thin-wall bumper and preparation method thereof |
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| CN103937093A (en) * | 2014-03-21 | 2014-07-23 | 浙江俊尔新材料股份有限公司 | Long glass fiber reinforced polypropylene composite material and preparation method |
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| CN104877231A (en) * | 2015-03-26 | 2015-09-02 | 苏州市德莱尔建材科技有限公司 | Low-temperature impact resistant PP and preparation method thereof |
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Address after: Qingpu Songze Avenue Industrial Park of Qingpu District 201700 Shanghai 6638 Lane 5, No. 7 Patentee after: Nakahiro Junl (Shanghai) new material Co., Ltd. Address before: Qingpu Songze Avenue Industrial Park of Qingpu District 201700 Shanghai 6638 Lane 5, No. 7 Patentee before: Shanghai Jun'er New Material Co., Ltd. |