CN101250303A - Mineral/whisker reinforced polypropylene composite material having good spraying property - Google Patents
Mineral/whisker reinforced polypropylene composite material having good spraying property Download PDFInfo
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- CN101250303A CN101250303A CNA2008100198873A CN200810019887A CN101250303A CN 101250303 A CN101250303 A CN 101250303A CN A2008100198873 A CNA2008100198873 A CN A2008100198873A CN 200810019887 A CN200810019887 A CN 200810019887A CN 101250303 A CN101250303 A CN 101250303A
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Abstract
The invention relates to mineral/crystal whisker reinforcement polypropylene composite material which has excellent spraying property, which is mainly comprises the following raw materials with proportioning by weight: 50-70% polypropylene, 15-30% inorganic crystal whisker, 5-15% inorganic mineral, 5-10% polarity modifier, 5-15% toughening agent POE, 0.1-0.4% anti-oxidant and 0.1-3% other auxiliary agent, wherein inorganic mineral and crystal whisker are respectively conducted with surface treatment trough coupling agent, polarity modifier is polyolefine thermoplastic elastomer grafted by maleic anhydride, and the grafting rate is 0.8-1.2%. The product of the invention has excellent spraying property, and high rigidity and strength. The product of the invention can be used as car components such as guard strips and the like, can be also used on household appliances such as laundry machine and the like, and especially is suitable for places which have higher requirement for spraying such as various external decorative elements of cars, etc.
Description
Technical field
The present invention relates to a kind of mineral/whisker reinforced polypropylene composite material with good spraying property.Can be used for household appliances and automobile product aspect.Belong to technical field of plastic.
Background technology
Polypropylene has been widely used on automobile internal and external ornament spare and the various household electrical appliance as a kind of large polyolefine material kind that has the superior and double dominant with low cost of over-all properties concurrently.At present, along with the continuous development of technology, people have proposed more and more higher requirement to every performance (as shock resistance, intensity and rigidity, sprayability, flowability etc.) of plastics, and this has proposed great challenge for the plastics industry.
Although polypropylene has good comprehensive mechanical property, it has a special significant disadvantages: notched Izod impact strength is low, and low-temperature flexibility is relatively poor.Therefore often need to carry out the back blend and improve its shock resistance by adding toughner.Carried out the research of alloy in the polypropylene still recently both at home and abroad again.Than aforesaid method by the back blending toughening, the method for this in-situ flexible has effectively improved toughness reinforcing effect.
Though it is toughness reinforcing that toughner and polyacrylic back blend can be carried out polypropylene, meanwhile, the adding of toughner also often causes the loss of the intensity and the modulus of acrylic resin.For intensity and the modulus that improves acrylic resin, can wait and improve by adding cheap inorganic mineral filler such as talcum powder usually, obtainable by this method modulus in flexure generally is no more than 1.6GPa.Though can strengthen polypropylene by the adding glass fibre and obtain the higher acrylic resin of rigidity, yet the mold filling ability of the high rigidity acrylic resin that obtains like this is not good, defectives such as pore appear in moulded parts easily, and the course of processing is quite serious to the wearing and tearing of equipment.Utilize the inorganic crystal whisker Reinforced Polypropylene then can effectively improve the rigidity of polypropylene material, the problem that occurs when avoiding glass-reinforced polypropylene simultaneously.Chinese patent CN03129167.8 has introduced a kind of polypropylene composite material that contains potassium titanate crystal whisker and glass fibre, Chinese patent CN03115922.2 has introduced the compound enhanced polypropylene composition of a kind of mineral/whisker, and Chinese patent CN03116196.0 has then introduced a kind of magnesium salt whisker and strengthened fire-retardant polypropene composition.Because the non-polar nature of acrylic resin makes that the coating performance (spraying property) of the above-mentioned high rigidity polypropylene composite that obtains is poor, has limited the use range of this high rigidity polypropylene composite.
For the spraying property of Reinforced Polypropylene material, the general method that adopts is to come polypropylene is carried out surface treatment by physico-chemical processes such as plasma radiations, perhaps adopts Chlorinated Polypropylene III that polypropylene is carried out surface-coated.Also can adopt and carry out the spraying property that blending and modifying improves matrix with functional poly propylene.
The maleic anhydride graft thermoplastic polyolefin elastomer is a kind of novel grafts of developing in recent years, just be applied to gradually various polar polymers [as nylon PA, thermoplastic polyester ethylene glycol terephthalate (PET) and mutual-phenenyl two acid bromide two alcohol ester (PBT)], and polycarbonate is toughness reinforcing, also be applied to the increase-volume of (as between nylon and polypropylene) between polarity plastics and the non-polar plastic, also can be used for the increase-volume between mineral filler and the plastics.Associated preparation and application patent can be referring to CN01126712.7, CN200610024089.0, CN99109924.9,200410017173.0 etc.
Summary of the invention
The object of the present invention is to provide a kind of mineral/whisker reinforced polypropylene composite material with good coating performance.
The object of the present invention is achieved like this: a kind of mineral/whisker reinforced polypropylene composite material with good spraying property is characterized in that described matrix material mainly is made up of following materials of weight proportions:
Polypropylene: 50～70%
Inorganic crystal whisker: 15～30%
Inorganic mineral: 5～15%
Polarity modifier: 5～10%
Toughner POE:5～15%
Oxidation inhibitor: 0.1～0.4%
Other auxiliary agents: 0.1～3%.
Described inorganic mineral and whisker carry out surface treatment through coupling agent respectively, and used coupling agent can be silane coupling agent or titanate coupling agent, and be typical in KH-550 (γ-An Jibingjisanyiyangjiguiwan);
Described polypropylene can be homo-polypropylene, block copolymerization polypropylene or atactic copolymerized polypropene.Can be the single trade mark also can be different trade mark blended, its melting index scope is 2.5～27g/10min, tensile strength 〉=18MPa.
Described inorganic crystal whisker can be alkali magnesium sulfate crystal whisker, potassium titanate crystal whisker or calcium carbonate crystal whisker etc., its length-to-diameter ratio L/D 〉=30, diameter≤1 μ m.
Described inorganic mineral can be talcum powder, mica or lime carbonate, and its particle size range is 500～2500 orders.
Described polarity modifier is MPOE (a maleic anhydride graft Thermoplastic Elastomer, Olefinic), and percentage of grafting is 0.8～1.2%, and preferable amount is 7%.
Described toughner is POE (Thermoplastic Elastomer, Olefinic).
Described oxidation inhibitor is a kind of Hinered phenols antioxidant, and is typical in 1010 of Switzerland vapour Bagong department.
According to the needs of product, other auxiliary agents can be thermo-stabilizer, anti UV agent, releasing agent, lubricant, pigment or Masterbatch etc.In order to guarantee good spraying effect, the consumption of releasing agent such as calcium stearate is no more than 0.2%, and preferred 0.1%.
Its preparation process is as follows:
(1) inorganic mineral and whisker carry out surface treatment through coupling agent respectively, and used coupling agent can be silane coupling agent or titanate coupling agent, and be typical in KH-550;
(2) take by weighing each component by proportioning, mixed 3～4 minutes discharging in the high-speed mixer high speed;
(3) mixed raw materials is through the twin screw extruder extruding pelletization, and the rotating speed of twin screw extruder is 200～500 rev/mins, and temperature is 180-240 ℃.
The present invention has utilized through coupling agent and has carried out surface-treated inorganic crystal whisker to polyacrylic enhancement, combined function polarity modifier maleic anhydride graft Thermoplastic Elastomer, Olefinic makes product have good spraying property and high rigidity simultaneously to polyacrylic enhancing sprayability and toughness reinforcing dual function.Because polarity modifier has toughness reinforcing effect simultaneously, therefore can reduce the consumption that adds toughner.
Advantage of the present invention is that product has good spray characteristics, and the rigidity height, the intensity height.Product of the present invention can be done trolley part purposes such as rubbing strip, also can be used for household appliances such as washing machine.Be particularly useful for to spraying demanding occasion, as various car external ornaments etc.
Specific embodiments
Below in conjunction with embodiment, the present invention is described in further detail:
Comparative Examples and embodiment 1～4:
With two kinds of acrylic resins is base-material, with the whisker through surface modification is toughener, and the talcum powder of surface modification is a filler, and the maleic anhydride graft thermoplastic polyolefin elastomer is a polarity modifier, POE (thermoplastic polyolefin elastomer) is a toughner, and charge ratio is as shown in table 1.
Table 1 has the high rigid polypropylene matrix material allocation sheet of good sprayability
| Batching | Comparative Examples | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Polypropylene 1 | 70 | 63 | 55 | 40 | 63 |
| Polypropylene 2 | - | - | - | 23 | - |
| Alkali magnesium sulfate crystal whisker | 29.8 | 29.8 | 29.8 | 29.8 | 19.8 |
| Talcum powder | - | - | - | - | 10 |
| Polarity modifier | - | 7 | 7 | 7 | 7 |
| POE | - | - | 8 | - | - |
| Antioxidant 1010 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Calcium stearate | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
Preparation process of the present invention is as follows:
(1) inorganic mineral and whisker carry out surface treatment through silane resin acceptor kh-550 respectively, and the KH550 consumption is 1.5%;
(2) take by weighing each component by proportioning, mixed 3～4 minutes discharging in the high-speed mixer high speed;
(3) mixed raw materials is through the twin screw extruder extruding pelletization, and the rotating speed of twin screw extruder is 250 rev/mins, and extruder temperature is provided with as shown in table 2.
The parameter setting of table 2 twin screw extruder
| One district | Two districts | Three districts | Four districts | Five districts | Six districts | Seven districts | Head |
| 180℃ | 190℃ | 200℃ | 210℃ | 210℃ | 210℃ | 220℃ | 225℃ |
Behind the twin screw extruder extruding pelletization, be injection molded into batten and carry out Mechanics Performance Testing; Be injection molded into colour table, after spraying paint by hand, utilize cross-hatching evaluation spraying effect.Test result is as shown in table 3.
The test result of table 3 Comparative Examples and embodiment
| Test event | Testing standard | Comparative Examples | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| MFR(g/10min) | ISO 1133， 2.16Kg/230℃ | 19.2 | 5.6 | 4.0 | 4.1 | 4.6 |
| Tensile strength (MPa) | ISO 527 | 26.3 | 25.1 | 20.2 | 23.9 | 22 |
| Extension at break (%) | ISO 527 | 10 | 30 | 34 | 30 | 36 |
| Modulus in flexure (MPa) | ISO 178 | 4324 | 2117 | 1650 | 1810 | 1950 |
| Flexural strength (MPa) | ISO 178 | 43.8 | 29.4 | 21.9 | 27.7 | 25.5 |
| Notched izod is impacted (KJ/m 2) | ISO 180 | 5.3 | 6.7 | 10.5 | 10.8 | 7.7 |
| Film adhesive | ISO 2409 | 2 grades | 1 grade | 1 grade | 1 grade | 1 grade |
Claims (10)
1, a kind of mineral/whisker reinforced polypropylene composite material with good spraying property is characterized in that described matrix material mainly is made up of following materials of weight proportions:
Polypropylene: 50～70%
Inorganic crystal whisker: 15～30%
Inorganic mineral: 5～15%
Polarity modifier: 5～10%
Toughner POE:5～15%
Oxidation inhibitor: 0.1～0.4%
Other auxiliary agents: 0.1～3%.
Described inorganic mineral and whisker carry out surface treatment through coupling agent respectively,
Described polarity modifier is the maleic anhydride graft Thermoplastic Elastomer, Olefinic, and percentage of grafting is 0.8～1.2%.
2, a kind of mineral/whisker reinforced polypropylene composite material with good spraying property according to claim 1 is characterized in that described coupling agent is silane coupling agent or titanate coupling agent.
3, a kind of mineral/whisker reinforced polypropylene composite material according to claim 1 with good spraying property, it is characterized in that described polypropylene is homo-polypropylene, block copolymerization polypropylene or atactic copolymerized polypropene, its melting index scope is 2.5～27g/10min, tensile strength 〉=18MPa.
4, a kind of mineral/whisker reinforced polypropylene composite material according to claim 1 with good spraying property, it is characterized in that described inorganic crystal whisker is alkali magnesium sulfate crystal whisker, potassium titanate crystal whisker or calcium carbonate crystal whisker, its length-to-diameter ratio L/D 〉=30, diameter≤1 μ m.
5, a kind of mineral/whisker reinforced polypropylene composite material with good spraying property according to claim 1 is characterized in that described inorganic mineral is talcum powder, mica or lime carbonate, and its particle size range is 500～2500 orders.
6, a kind of mineral/whisker reinforced polypropylene composite material with good spraying property according to claim 1 is characterized in that described toughner thermoplastic polyolefin elastomer.
7, a kind of mineral/whisker reinforced polypropylene composite material with good spraying property according to claim 1 is characterized in that described oxidation inhibitor is a kind of Hinered phenols antioxidant.
8, a kind of mineral/whisker reinforced polypropylene composite material with good spraying property according to claim 1 is characterized in that described coupling agent is a γ-An Jibingjisanyiyangjiguiwan.
9, a kind of mineral/whisker reinforced polypropylene composite material with good spraying property according to claim 1 is characterized in that described maleic anhydride graft Thermoplastic Elastomer, Olefinic consumption is 7%.
10, a kind of mineral/whisker reinforced polypropylene composite material with good spraying property according to claim 8 is characterized in that described Hinered phenols antioxidant is 1010 of a Switzerland vapour Bagong department.
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|---|---|---|---|
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Cited By (19)
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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 |
| CN101914241A (en) * | 2010-08-04 | 2010-12-15 | 孙卫东 | Formula of special material for cases of electrocars and motorcycles |
| CN102229720A (en) * | 2011-05-12 | 2011-11-02 | 中国科学院长春应用化学研究所 | High impact polypropylene composition and preparation method thereof |
| CN102558665A (en) * | 2010-12-23 | 2012-07-11 | 上海普利特复合材料股份有限公司 | Polypropylene composition for automotive upholstery and preparation method of polypropylene composition |
| CN101747639B (en) * | 2008-12-12 | 2012-12-12 | 比亚迪股份有限公司 | Wood plastic composite composition, wood plastic composite and preparation method thereof |
| CN102952336A (en) * | 2012-11-15 | 2013-03-06 | 合肥会通新材料有限公司 | Active basic magnesium sulfate whisker modified polypropylene composite material and preparation method thereof |
| CN103360680A (en) * | 2013-05-23 | 2013-10-23 | 建德市新裕塑胶材料有限公司 | Calcium carbonate filler master batch for polypropylene and polyethylene and preparation process thereof |
| CN101759931B (en) * | 2008-12-23 | 2013-10-23 | 上海普利特复合材料股份有限公司 | High-lustrousness material filled with modified polypropylene and preparation method thereof |
| CN104231428A (en) * | 2014-08-19 | 2014-12-24 | 佛山市顺德区南凯新材料实业有限公司 | Polypropylene material for automobile engine compartment and preparation method of polypropylene material |
| CN104250396A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Polypropylene composition and polypropylene film |
| CN104311996A (en) * | 2014-09-30 | 2015-01-28 | 苏州润佳工程塑料股份有限公司 | Modified polypropylene composite material with low shrinking percentage and preparation method thereof |
| CN104479193A (en) * | 2014-11-19 | 2015-04-01 | 广东联塑科技实业有限公司 | Nano-whisker modified PE (polyethylene) pipe and preparation method thereof |
| CN104479226A (en) * | 2012-04-16 | 2015-04-01 | 上海韬鸿化工科技有限公司 | Polypropylene plastic filled with coupling agent modified calcium carbonate |
| CN106279972A (en) * | 2016-08-04 | 2017-01-04 | 叶剑 | A kind of polypropylene composite materials dalle and manufacture method thereof |
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2008
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| CN101747639B (en) * | 2008-12-12 | 2012-12-12 | 比亚迪股份有限公司 | Wood plastic composite composition, wood plastic composite and preparation method thereof |
| CN101759931B (en) * | 2008-12-23 | 2013-10-23 | 上海普利特复合材料股份有限公司 | High-lustrousness material filled with modified polypropylene and preparation method thereof |
| 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 |
| CN101914241A (en) * | 2010-08-04 | 2010-12-15 | 孙卫东 | Formula of special material for cases of electrocars and motorcycles |
| CN102558665A (en) * | 2010-12-23 | 2012-07-11 | 上海普利特复合材料股份有限公司 | Polypropylene composition for automotive upholstery and preparation method of polypropylene composition |
| CN102558665B (en) * | 2010-12-23 | 2016-05-18 | 上海普利特复合材料股份有限公司 | Polypropene composition that a kind of automotive upholstery is used and preparation method thereof |
| CN102229720A (en) * | 2011-05-12 | 2011-11-02 | 中国科学院长春应用化学研究所 | High impact polypropylene composition and preparation method thereof |
| CN102229720B (en) * | 2011-05-12 | 2015-05-20 | 中国科学院长春应用化学研究所 | High impact polypropylene composition and preparation method thereof |
| CN104479226A (en) * | 2012-04-16 | 2015-04-01 | 上海韬鸿化工科技有限公司 | Polypropylene plastic filled with coupling agent modified calcium carbonate |
| CN102952336B (en) * | 2012-11-15 | 2015-07-01 | 合肥会通新材料有限公司 | Active basic magnesium sulfate whisker modified polypropylene composite material and preparation method thereof |
| CN102952336A (en) * | 2012-11-15 | 2013-03-06 | 合肥会通新材料有限公司 | Active basic magnesium sulfate whisker modified polypropylene composite material and preparation method thereof |
| CN103360680A (en) * | 2013-05-23 | 2013-10-23 | 建德市新裕塑胶材料有限公司 | Calcium carbonate filler master batch for polypropylene and polyethylene and preparation process thereof |
| CN103360680B (en) * | 2013-05-23 | 2015-09-16 | 建德市新裕塑胶材料有限公司 | Polypropylene and polyethylene Calcium carbonate filler master batch and preparation technology thereof |
| CN104250396A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Polypropylene composition and polypropylene film |
| CN104250396B (en) * | 2013-06-28 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of polypropene composition and polypropylene film |
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| CN110951163A (en) * | 2018-09-26 | 2020-04-03 | 合肥杰事杰新材料股份有限公司 | High-surface-tension low-density polypropylene composite material and preparation method thereof |
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| CN115298256A (en) * | 2020-03-30 | 2022-11-04 | 宇部材料工业株式会社 | Polypropylene resin composition, method for producing polypropylene resin composition, and molded article |
| CN115298256B (en) * | 2020-03-30 | 2024-01-23 | 宇部材料工业株式会社 | Polypropylene resin composition, method for producing polypropylene resin composition, and molded article |
| CN113372651A (en) * | 2021-07-16 | 2021-09-10 | 北海市传创环保科技有限公司 | High-strength and high-toughness polypropylene injection molding material |
| CN113549272A (en) * | 2021-08-13 | 2021-10-26 | 贵州省材料产业技术研究院 | Durable hydrophilic polypropylene separation net material and preparation method thereof |
| CN113549272B (en) * | 2021-08-13 | 2023-08-29 | 贵州省材料产业技术研究院 | Durable hydrophilic polypropylene separation net material and preparation method thereof |
| CN113754969A (en) * | 2021-10-08 | 2021-12-07 | 福建亚通新材料科技股份有限公司 | HDPE/PVC blending modified material |
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Open date: 20080827 |