CN102372874B - Stress whitening resistant and scratch resistant polypropylene composition, and preparation method thereof - Google Patents
Stress whitening resistant and scratch resistant polypropylene composition, and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a stress whitening resistant and scratch resistant polypropylene composition, and a preparation method thereof. The polypropylene composition comprises the following components, wherein the components are blended, and comprise, by weight, 100 parts of a polypropylene resin, 0-50 parts of a mineral filler, 0.05-40 parts of oil-filled fully-vulcanized powdered rubber,0.01-30 parts of polyethylene and 0-30 parts of a toughening agent. The oil-filled fully-vulcanized powdered rubber is the fully-vulcanized powdered rubber filled with a polysiloxane lubricant and/orhydrocarbon lubricating oil, and the average particle size of the full-vulcanized powdered rubber is 20-2000 nm. The polypropylene composition of the present invention has characteristics of good mechanical property, scratch resistance and stress whitening resistance.
Description
Technical field
The present invention relates to a kind of polypropene composition and preparation method thereof.Specifically, relate to a kind ofly have good impact property, proof stress turns white and the polypropylene of damage resistant and preparation method thereof.
Technical background
Polypropylene has the advantages such as price is low, quality light, easily reclaim, processing forming is good, is widely used in a lot of fields.But also there is simultaneously the relatively poor problem of shock resistance in polypropylene, can not satisfy requirement, especially automobile and the field of household appliances of actual use when being applicable to that rigidity-toughness balanced had certain requirements occasion.At present, comparatively the means of raising polypropene impact-resistant commonly used are by blended rubber or elastomeric method, such as ethylene-propylene rubber(EPR), polyolefin elastomer etc.Yet also there is certain limitation in this method, and one of them is exactly that modified polypropene surface property such as scratch resistant etc. are produced detrimentally affect.
As everyone knows, studies on scratch resistance of PP can be relatively poor, is easy under external force be scratched, and the adding of toughner such as rubber, elastomerics etc. is further deteriorated polyacrylic scratch resistance then.Therefore when being applied to field that electric appliance casing, automotive upholstery etc. have relatively high expectations to outward appearance, this type of tenacity-increased profax is subject to certain restrictions, particularly for automotive upholstery, such as dashboard, door-plate, column, glove box etc.People have attempted many methods for this reason.As: US Patent No. 6541568 discloses the interpolation styrene copolymer and has improved polyacrylic scratch resistance, yet the manufacturing of styrene copolymer is expensive, can significantly increase the cost of polypropylene blend.In addition, it is limited to polyacrylic scratch resistance improvement effect.Reducing rubber to aspect the impact of studies on scratch resistance of PP, another kind of method commonly used is to add lubricant in polypropylene composite material.As: publication number is that the patent of CN101173074A is improved polyacrylic scratch resistance by adding the lubricant aliphatic amide; Publication number is the patent of CN1580115A, improves the scratch resistant performance of said composition by adding silicone elastomer; Publication number is that the patent of CN1631960A adopts the method for silicone elastomer and its master batch of preparation to solve the damage resistant problem.Yet this method need to strengthen along with the increase of rubber content the consumption of lubricant.But the simple consumption that passes through to increase lubricant is limited to the improvement of scratch resistance, and increases the appearance that lubricant quantity also can cause some other problems, as lubricant separate out, surfaces of tacky frostization, life-time service lubricant effect variation etc.Present patent does not all provide good solution.
On the other hand, also there is the problem of stress whitening in polypropylene.When being subject to External Force Acting, as Shooting Technique eject link or goods are subject to external force collision etc., material can produce crazing and expand the crazing zone with absorbed energy in the corresponding position, and the crazing zone produces and expansion will cause product to turn white, and affects outward appearance or produces unacceptable product.In addition, when being subject to the external force scraping, stress whitening can further cause the decline of scratch resistant performance.The adding of rubber or filler then may cause the further reduction of anti-stress whitening.
In recent years, along with people in use keep the requirement of good appearance day by day to improve to goods, preparation has favorable comprehensive mechanical property, can in use keep again the polypropylene material of good appearance to become the development trend that polypropylene is used in automobile, field of household appliances simultaneously.Yet, for how to solve toughness reinforcing and improve contradiction between scratch resistance and the stress whitening performance, still do not have at present good method, the prior art above-mentioned properties of weighing apparatus that has much difficulty in healing.
Summary of the invention
The inventor finds by a large amount of experimental studies, adopt oil-filled fully vulcanized powder rubber and polyethylene to come modified polypropylene resin, can not only greatly improve polyacrylic impact property, can significantly reduce polyacrylic stress whitening simultaneously, strengthen its surperficial scratch resistant performance.Can satisfy the goods such as the inside and outside gadget of automobile and electronics, electric appliance casing to the requirement of polypropylene material mechanical property and surface property.
The purpose of this invention is to provide a kind of polypropene composition, it includes the following component of blend: acrylic resin, 100 weight parts; Mineral filler, 0～50 weight part; Oil-filled fully vulcanized powder rubber, 0.05～40 weight part is preferably 1-20 part; Polyethylene, 0.01～30 part, preferred 0.2-20 part; Toughner, 0-30 part.
In the polypropene composition of the present invention, described polypropylene can be homopolymerization or the Co-polypropylene that melting index is 3-60g/10min, or several mixture wherein, and the preferred molten index is the Co-polypropylene of 3-40g/10min.Described mineral filler can be talcum powder, wollastonite or calcium carbonate, and particle diameter is the 300-5000 order.Described toughner can be a kind of in amorphous ethylene-alpha-olefin copolymer and the styrenic based thermoplastic elastomer or their mixture.It is a kind of in 0.2-40g/10min high density polyethylene(HDPE) (HDPE), Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE), the grafted polyethylene or their mixture that described polyethylene can be melting index.
In the polypropene composition of the present invention, oil-filled fully vulcanized powder rubber is fully vulcanized powder rubber, the fully vulcanized powder rubber that is filled with silicone based lubricant that is filled with the hydro carbons lubricant, the fully vulcanized powder rubber that is filled with hydro carbons lubricant and silicone based lubricant or their mixture, the fully vulcanized powder rubber of preferred 100 weight parts of oil-filled ratio is filled with the silicone based lubricant of hydro carbons lubricating oil and/or 1～200 weight part of 1～100 weight part.
The powdered rubber that fully vulcanized powder rubber of the present invention provides for Chinese patent CN1402752A, median size are the 20-2000 nanometer, preferred 30-400 nanometer.The preferred powder styrene butadiene rubber of powdered rubber kind, powder carboxylic styrene-butadiene rubber, Powdered acrylonitrile-butadiene rubber, powder carboxy nitrile rubber, powder polybutadiene rubber, silicon rubber powder or powder acrylic elastomer.Hydro carbons lubricating oil is selected from least a in paraffin oils, naphthenic oil, the aromatic ring hydrocarbon ils, is preferably naphthenic oil.Silicone based lubricant is PES-4 or polyphenyl methyl siloxane etc., preferred line style polymethyl siloxane, and more preferably viscosity is the line style polymethyl siloxane of 300-20000S.
Polypropene composition of the present invention also comprises general Masterbatch, oxidation inhibitor in the existing polypropylene processing technology, and its addition is conventional amount used, or suitably adjusts according to the requirement of practical situation.Oxidation inhibitor is the conventional oxidation inhibitor of polypropylene, and such as antioxidant 1076,1010,168, thioesters class auxiliary antioxidant is DLTP (thio-2 acid bilaurate), DSTP (thio-2 acid 2 stearyl ester) etc.
The present invention further provides the preparation method of above-mentioned polypropene composition.
The preparation method of polypropene composition of the present invention may further comprise the steps:
(1) with fully vulcanized powder rubber, hydro carbons lubricating oil and/or silicone based lubricant 50～80 ℃ of stirrings, blend makes oil-filled fully vulcanized powder rubber.
(2) will include polypropylene, oil-filled fully vulcanized powder rubber obtained above, mineral filler, polyethylene in interior component by described component proportion melt blending.
The blending temperature of material is the processing temperature of polypropylene general in the step (2), selects not only guaranteeing the complete melting of matrix polypropylene but also can not make in the scope of its decomposition.General selection temperature is 190～250 ℃, is preferably 190～230 ℃.Blending equipment used in the present invention is the general blending equipment in the rubber and plastic processing industry, can be that twin screw extruder, BUSS mediate unit, single screw extrusion machine, mill or Banbury mixer etc.
Take oil-filled form of finely divided powder, mehtod styrene-butadiene rubber(SBR) as example, concrete preparation method is: form of finely divided powder, mehtod styrene-butadiene rubber(SBR) is heated to 50-80 ℃, places homogenizer.Under high-speed stirring, add slowly line style polymethyl siloxane liquid lubricant, its viscosity is 300-20000S, stirs 30-50 second, places in normal temperature after emitting and uses in 24-48 hour.The add-on of line style polymethyl siloxane lubricant, take form of finely divided powder, mehtod styrene-butadiene rubber(SBR) as 100 weight parts, its add-on is the 1-200 weight part.
The prepared polypropene composition of the present invention has excellent toughness, scratch resistant performance, and anti-stress whitening can satisfy the goods such as the inside and outside gadget of automobile and electronics, electric appliance casing to the requirement of polypropylene material mechanical property and surface property.
Embodiment
The invention will be further described below in conjunction with specific embodiment.Scope of the present invention is not subjected to the restriction of these embodiment.
Embodiment 1～3:
With polypropylene (Sinopec Beijing Yanshan Petrochemical Co., the trade mark: K9726, melting index: 26g/10min), talcum powder (mining industry company limited of Dalian Fuji, 2500 orders), ethylene-propylene rubber(EPR) (Dow Chemical, the trade mark: NORDEL IP), (weight ratio of form of finely divided powder, mehtod styrene-butadiene rubber(SBR) and linear polymethyl siloxane lubricant (Beijing chemical industry two factories) is 100: 35 to oil-filled form of finely divided powder, mehtod styrene-butadiene rubber(SBR) A, wherein form of finely divided powder, mehtod styrene-butadiene rubber(SBR) is Beijing Chemical Research Institute's self-control, the trade mark: VP101, median size 0.1 μ m), polyethylene (Sinopec Beijing Yanshan Petrochemical Co., the trade mark: 3300J, melting index: 2.5g/10min), oxidation inhibitor (Ciba fine chemicals, the trade mark: B225) stir rear (concrete prescription sees Table 1), use twin screw extruding pelletization under 190～230 ℃ of conditions.Through injector injection sample preparation, carry out the performance tests such as mechanical property, scratch resistant performance, it the results are shown in Table 1.
Embodiment 4～5:
Except oil-filled form of finely divided powder, mehtod styrene-butadiene rubber(SBR) A is changed into the oil-filled form of finely divided powder, mehtod styrene-butadiene rubber(SBR) B (weight ratio of form of finely divided powder, mehtod styrene-butadiene rubber(SBR) and linear polymethyl siloxane lubricant is 100: 90).All the other components and preparation condition are identical with embodiment 1, and specifically prescription and test result see Table 1.
Embodiments of the invention are estimated the damage resistant degree with the damage resistant tester.Scrape a line segment figure with a mechanically operated scraper at the frosting of preparation.Then record the not misalignment of surface scratch with a colourimeter.In same sample zone, scratch front and rear surfaces scattering of light value with the spectral photometric colour measuring other measure sample of scoring, with the quality of scattering of light difference DELTA E tolerance studies on scratch resistance of PP before and after scratching, Δ E value is less, shows that the scratch resistance of goods is better.Test condition is:
Temperature: 23 ± 5 ℃
Anchorage force: 10N
Scuffing speed: 1000mm/min
Stress whitening is measured by visual inspection, concrete grammar is: with one mechanically operated scraper is scraped a line segment figure (actual conditions is tested with scratch resistance) at the frosting of preparation, then with the stress whitening of naked eyes test samples: the result is reported as " A ", and expression seldom or do not have a visual stress whitening; " B " represents perceptible stress whitening; " C " represents moderate stress whitening; " D " represents comparatively serious stress whitening.
Comparative example 1:
With polypropylene (Sinopec Beijing Yanshan Petrochemical Co., the trade mark: K9726, melting index: 26g/10min), talcum powder (mining industry company limited of Dalian Fuji, 2500 orders), oxidation inhibitor (Ciba fine chemicals, the trade mark: B225) stir rear (concrete prescription sees Table 1), use twin screw extruding pelletization under 190～230 ℃ of conditions.Through injector injection sample preparation, carry out the performance tests such as mechanical property, scratch resistant performance, it the results are shown in Table 1.
Comparative example 2:
Add ethylene-propylene rubber(EPR) on the basis of comparative example 1 toughness reinforcing, and all the other components and preparation condition are identical with comparative example 1, and specifically prescription and test result see Table 1.
Table 1
The data of embodiment and Comparative Examples can be found out from table 1, and oil-filled powder styrene butadiene rubber and poly adding can not only improve polyacrylic impact property greatly, can significantly reduce polyacrylic stress whitening simultaneously, strengthen its surperficial scratch resistant performance.
Claims (7)
1. polypropene composition includes the following component of blend: acrylic resin, 100 weight parts; Mineral filler, 0～50 weight part; Oil-filled fully vulcanized powder rubber, 0.05～40 weight part; Polyethylene, 0.01～30 part; Toughner, 0～30 part;
Described oil-filled fully vulcanized powder rubber is the fully vulcanized powder rubber that is filled with silicone based lubricant and/or hydro carbons lubricating oil, and the median size of described fully vulcanized powder rubber is 20～2000nm.
2. polypropene composition according to claim 1 is characterized in that, in the described oil-filled fully vulcanized powder rubber, and fully vulcanized powder rubber 100 weight parts, hydro carbons lubricating oil 1～100 weight part and/or silicone based lubricant 1～200 weight part.
3. polypropene composition according to claim 1 is characterized in that, the median size of described fully vulcanized powder rubber is 30～400nm.
4. polypropene composition according to claim 1, it is characterized in that described fully vulcanized powder rubber is powder styrene butadiene rubber, powder carboxylic styrene-butadiene rubber, Powdered acrylonitrile-butadiene rubber, powder carboxy nitrile rubber, powder polybutadiene rubber, silicon rubber powder or powder acrylic elastomer.
5. polypropene composition according to claim 1 is characterized in that, described hydro carbons lubricating oil is selected from least a in paraffin oils, naphthenic oil and the aromatic ring hydrocarbon ils; Described silicone based lubricant is linear polymethyl siloxane.
6. polypropene composition according to claim 1 is characterized in that, described mineral filler is talcum powder, wollastonite or calcium carbonate, and particle diameter is the 300-5000 order.
7. polypropene composition according to claim 1 is characterized in that, described toughner is a kind of in amorphous ethylene-alpha-olefin copolymer and the styrenic based thermoplastic elastomer or their mixture.
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| CN104558816B (en) * | 2013-10-12 | 2018-01-23 | 中国石油化工股份有限公司 | A kind of polypropene composition and preparation method thereof |
| WO2015074195A1 (en) * | 2013-11-20 | 2015-05-28 | 丹阳博德电子有限公司 | Backrest material of automobile seat and preparation method therefor |
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| CN103910934B (en) * | 2014-04-02 | 2018-07-17 | 合肥杰事杰新材料股份有限公司 | Resistance to stress whiten agent, add the agent PP composite material and its preparation and application |
| CN105440431B (en) * | 2014-08-12 | 2018-01-23 | 中国石油化工股份有限公司 | A kind of polypropene composition and preparation method thereof |
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| CN104610656A (en) * | 2015-01-29 | 2015-05-13 | 宝鸡石油机械有限责任公司 | High and low temperature resin material for plastic coating (impregnating) of steel wire ropes |
| CN104861226A (en) * | 2015-04-29 | 2015-08-26 | 洛阳市河之阳高分子材料有限公司 | Polypropylene material for car dust cover and preparation method thereof |
| CN106024535A (en) * | 2016-07-29 | 2016-10-12 | 李聪 | Low-voltage circuit breaker |
| CN106280000A (en) * | 2016-08-30 | 2017-01-04 | 贝内克-长顺汽车内饰材料（张家港）有限公司 | A kind of automotive interior material with pearlescent appearance being adapted to vacuum forming |
| CN109605882A (en) * | 2018-10-30 | 2019-04-12 | 昆山睿力得软件技术有限公司 | A kind of durability automotive material and its application |
| CN110885517B (en) * | 2019-12-18 | 2021-09-17 | 日丰企业集团有限公司 | Stress whitening resistant hard transparent polyvinyl chloride and preparation method thereof |
| CN116063787A (en) * | 2021-10-30 | 2023-05-05 | 中国石油化工股份有限公司 | Stress whitening resistant thermoplastic composite material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381525A (en) * | 2001-04-18 | 2002-11-27 | 中国石油化工股份有限公司 | Toughened polypropylene and its preparing process |
| CN101270212A (en) * | 2007-03-22 | 2008-09-24 | 中国石油化工股份有限公司 | Polypropelene composition capable of making with laser and preparation method thereof |
Family Cites Families (1)
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| JPH0655868B2 (en) * | 1989-12-26 | 1994-07-27 | 出光石油化学株式会社 | Blow molding resin composition |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381525A (en) * | 2001-04-18 | 2002-11-27 | 中国石油化工股份有限公司 | Toughened polypropylene and its preparing process |
| CN101270212A (en) * | 2007-03-22 | 2008-09-24 | 中国石油化工股份有限公司 | Polypropelene composition capable of making with laser and preparation method thereof |
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|---|
| JP特公平6-55868B 1994.07.27 |
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