CN103073785A - Low-gloss polypropylene composite material and preparation method thereof - Google Patents
Low-gloss polypropylene composite material and preparation method thereof Download PDFInfo
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- CN103073785A CN103073785A CN2011103306068A CN201110330606A CN103073785A CN 103073785 A CN103073785 A CN 103073785A CN 2011103306068 A CN2011103306068 A CN 2011103306068A CN 201110330606 A CN201110330606 A CN 201110330606A CN 103073785 A CN103073785 A CN 103073785A
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Abstract
The invention provides a low-gloss polypropylene composite material and a preparation method thereof. The invention belongs to the field of polypropylene composite materials. The material comprises blended materials of polypropylene, grafted hydrogenated styrene-butadiene-styrene block copolymer, fully vulcanized powder silicone rubber, and an inorganic filling material. Calculated with the weight of polypropylene as 100 parts, the material comprises the components of, by weight, 1-30 parts of the grafted hydrogenated styrene-butadiene-styrene block copolymer, 1-30 parts of fully vulcanized powder silicone rubber, and 10-35 parts of the inorganic filling material. The grafted hydrogenated styrene-butadiene-styrene block copolymer is a maleic anhydride graft with a grafting rate of 1-3%. The fully vulcanized powder silicone rubber has an average particle size of 0.05-1mum and a gel content of 60wt% or higher. The low-gloss polypropylene composite material provided by the invention has the advantages of good extinction performance, good impact resistance, simple preparation technology, easy-to-control conditions, and suitability for fields such as automotive interior decoration parts.
Description
Technical field
The present invention relates to a kind of polypropylene composite material, more particularly, relate to a kind of low-luster polypropylene composite material that can be used for automotive upholstery.
Background technology
Polypropylene has the heat resisting temperature height, fatigue resistance, electrical insulating property, resistance to corrosive chemicals, the advantage that processing forming is good, and price is low, quality light, easily reclaim, and therefore is widely used in fields such as automotive industrys.But common modified polypropylene material has gloss or reflective characteristic more, and this defective not only makes automotive trim Integral decoration class reduce, and more makes the car-driver tired easily, even can affect car-driver's driving safety, increases the traffic accident odds.Also can't satisfy the needs of new automobile usefulness Plastics Development that can be decoration integrated.Therefore, automobile receives publicity day by day with low-luster polypropylene material.
Around the problem of polypropylene material surface dulling, people have carried out many research work.Publication number CN101759919A patent is by adding a kind of mineral filler wollastonite that can effectively reduce the product surface glossiness in the basic components of polypropylene composite material, thereby prepares low-luster polypropylene composite material.Thereby owing to added the comprehensive mechanical property that a large amount of mineral fillers has worsened polypropylene composite material.Publication number CN101173075 patent reduces the glossiness of polypropylene composite material by add 0.5～5 part of silicon-dioxide in polypropylene composite material.Equally, the mechanical property that addition too much can deteriorated polypropylene composite material, addition very little extinction effect is not obvious again, still is difficult at present widespread use in auto industry field.
Publication number CN101313025A utilizes the elastomer copolymer of propylene and ethylene atactic copolymer and propylene and ethene to make than the soft polyolefin light extinction composition, this polymkeric substance has preferably eliminate optical property and mechanical property, is applicable to the sheet material extruding, blows thermoforming field and the fields such as internal decoration of car top layer and film.Be not suitable for the injection structure product.
Publication number CN101121799A patent disclosure a kind of adding peroxide cross-linking agent that the polyethylene molecule is produced is crosslinked, form microgel and be distributed in the polypropylene matrix, this microgel produces tiny projection at product surface and causes the diffuse-reflectance of light to reduce the glossiness on polypropylene blending modified material surface.But extinction effect is not ideal enough.
Summary of the invention
For problems of the prior art, the invention provides a kind of low-luster polypropylene composite material, by adding the composition of a kind of grafting hydrogenated styrene-butadiene-styrene block copolymers (g-SEBS) and a kind of fully sulfurized silicon rubber powder, can effectively reduce the surface gloss of polypropylene composite material, solve well the deficiencies in the prior art.
Composition of the present invention includes following main ingredient: polypropylene, g-SEBS, fully sulfurized silicon rubber powder and mineral filler; Wherein, take polypropylene as 100 weight parts, g-SEBS is 1～30 weight part, preferred 3～30 weight parts; Fully sulfurized silicon rubber powder 1～30 weight part, preferred 3～30 weight parts; Mineral filler 10～35 weight parts, preferred 12～34 weight parts.
Among the present invention, described polypropylene comprises at least a in various homo-polypropylene of the prior art or the Co-polypropylene.
Described grafting hydrogenated styrene-butadiene-styrene block copolymers is maleic anhydride grafts, and maleic anhydride grafting ratio is 1～3%, preferred 1～1.5%.Styrene content is 30～33%wt.
Described fully sulfurized silicon rubber powder, its median size are 0.05～1 μ m, preferred 0.05～0.2 μ m, more preferably 0.05～0.1 μ m; Its gel content is 60wt% or higher, is preferably 75wt% or higher, more preferably 90wt% or higher.Described fully sulfurized silicon rubber powder particle preferably has the fully sulfurized silicon rubber powder of equal phase structure, and namely each particulate in this fully sulfurized silicon rubber powder is homogeneous phase, and single particulate all is homogeneous on forming.Under the observation of existing microtechnique, do not find the phenomenon of layering, minute equal uneven phase in the particulate.This fully sulfurized silicon rubber powder is by fixing corresponding silicone rubber latex cross-linking radiation with the rubber particles particle diameter.Detailed content of fully sulfurized silicon rubber powder of the present invention and preparation method thereof can be referring to Chinese patent CN 1383439A, and its full content is incorporated herein the present invention as a reference.
Described mineral filler is a kind of or mixture in talcum powder, barium sulfate, calcium carbonate and the silicon salt whisker etc. commonly used, and its median size is 1～13 μ m, preferred 5～10 μ m.The Main Function of the mineral filler that adds among the present invention is the comprehensive mechanical property that improves material, to be adapted to the service requirements of trolley part.
Among the present invention, the fully sulfurized silicon rubber powder of adding itself just has good rebound resilience and the effect of delustring, therefore the glossiness that reduces matrix material is played a role; And the small fully sulfurized silicon rubber powder of the SEBS of maleic anhydride graft and particle can be in polypropylene Uniform Dispersion and form small gel, after the moulding product surface form can produce irreflexive uniformly small concavo-convex, thereby effectively reduce the glossiness on polypropylene composite material surface.In addition, as rubber the shock strength of improving the mechanical property of material, particularly matrix material had very large effect.
Also comprise oxidation inhibitor in the matrix material of the present invention, oxidation inhibitor can be selected resin various oxidation inhibitor commonly used in the prior art, and its consumption also is conventional amount used.Comparative optimization, described oxidation inhibitor is selected from Hinered phenols antioxidant, and the mixture of phosphoric acid ester oxidation inhibitor.Total consumption of oxidation inhibitor is 0.1～2 weight part take polypropylene as 100 parts by weight, preferred 0.2～0.5 weight part.The weight ratio of described Hinered phenols antioxidant and phosphoric acid ester oxidation inhibitor is 1: 1～1: 2.Hinered phenols antioxidant preferred four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (anti-oxidant Irganox 1010 of producing such as Ciba fine chemicals) wherein; Phosphoric acid ester oxidation inhibitor preferred three (2,4-di-tert-butylphenol) phosphorous acid ester (such as the oxidation inhibitor Irgafos 168 of Ciba fine chemicals production).
Can also comprise some auxiliary agents commonly used in the acrylic resin course of processing in the matrix material of the present invention, as: dispersion agent, processing thermo-stabilizer, photostabilizer etc., its consumption is conventional amount used, or adjusts according to the requirement of practical situation.
Two of purpose of the present invention is to provide the preparation method of this kind low-luster polypropylene composite material, is achieved through the following technical solutions: comprise that the component that will comprise described polypropylene, g-SEBS, fully sulfurized silicon rubber powder and mineral filler makes described polypropylene composite material by described content melt blending.
More specifically, the preparation method of polypropylene composite material of the present invention comprises: the component that will include described polypropylene, g-SEBS, fully sulfurized silicon rubber powder and mineral filler is fully mixed in mixing equipment evenly by described component proportion, extrude through the blending equipment melt blending, namely make low-luster polypropylene matrix material of the present invention after the granulation.
In the course of processing of polypropylene composite material of the present invention, material melt blending temperature is used blending temperature in the common acrylic resin processing, should select not only guaranteeing the complete melting of matrix resin but also can not make in the scope of its decomposition, be generally 190 ℃～220 ℃, preferred processing temperature is 200～220 ℃.In addition, according to the processing needs, can add in right amount some auxiliary agents commonly used in the acrylic resin course of processing in the blend material, such as dispersion agent, processing thermo-stabilizer, photostabilizer etc., its consumption is conventional amount used, or adjusts according to the requirement of practical situation.
The mixing equipment of mixing of materials can adopt various mixing equipments used in the prior art in the preparation method of the invention described above, such as stirrer, kneading machine etc.Employed melt blending equipment is the general blending equipment in the rubber and plastic processing industry among the preparation method of the present invention, can be twin screw extruder, the mixing unit of BUSS etc.
Compared with prior art, the present invention has following beneficial effect:
Polypropylene composite material of the present invention is added g-SEBS and fully sulfurized silicon rubber powder by adopting, and has obviously reduced the glossiness of matrix material, thereby has prepared the low-luster polypropylene matrix material of excellent combination property.The experiment proved that 60 ° of angle glossiness of the light face of matrix material of the present invention and 20 ° of angle glossiness of light face are compared with original product and all significantly decreased, and this matrix material has good comprehensive mechanical property, solved well the deficiencies in the prior art.
The polypropylene composite material of preparing of the present invention has good eliminate optical property and shock resistance, can be applicable to the fields such as automotive upholstery.And preparation method's technique of the present composition is simple, easy handling, is applicable to suitability for industrialized production.
Embodiment
The present invention will be further described below in conjunction with specific embodiment.But the present invention is not limited in following embodiment.
Embodiment 1～6
With polypropylene (K9020, Sinopec Yanshan Mountain branch office), g-SEBS (FG1901, company is risen by U.S. section, maleic anhydride grafting ratio 1.5%, styrene content 30%), fully sulfurized silicon rubber powder (VP-602, median size 0.1 μ m, gel content 90wt%; The China Petrochemical Industry Beijing Chemical Research Institute), talcum powder (median size 6.5 μ m, Haicheng powder body material company limited), (Irganox 1010 and Irgafos 168 are composite and get with weight ratio 1: 1 for oxidation inhibitor, Ciba fine chemicals) puts into homogenizer, under 300 rev/mins rotating speed, stirred 3 minutes, each component is fully mixed.With extruding pelletization under the condition of the said mixture material process mixing unit of BUSS (MKD-30, Switzerland BUSS company) in 190 ℃～220 ℃ scopes, obtain the low-luster polypropylene matrix material subsequently.Its concrete prescription sees Table 1, and wherein each component concentration is all in parts by weight.
The pellet of extruding is dried 6hr in 95 ℃ of constant temperature ovens, then become the standard batten at 210 ℃～225 ℃ condition hemostasis, the socle girder notched Izod impact strength is according to the ISO180 standard testing; 20 ° of 60 ° of 85 ° of intelligent Grossmeters of JFL-BZ are used in glossiness test, and test condition is: (1) stability: 0.4 gloss unit (Gs)/30 minute; (2) measurement window size: 16 * 48 (mm); (3) the test sample surface is the specular light face.Testing standard is ISO-2813.Specific performance the results are shown in Table 1.
Comparative Examples 1～2
Polypropylene (with embodiment 1), oxidation inhibitor (with embodiment 1), talcum powder (with embodiment 1) are put into homogenizer, under 300 rev/mins rotating speed, stirred 3 minutes, each component is fully mixed.With extruding pelletization under the condition of the said mixture material process mixing unit of BUSS (with embodiment 1) in 190 ℃～220 ℃ scopes, obtain the low-luster polypropylene matrix material subsequently.Its concrete prescription sees Table 1, and wherein each component concentration is all in parts by weight.
The same embodiment of the test process of Comparative Examples material and testing standard.Specific performance the results are shown in Table 1.
The component of table 1 embodiment 1～6 and Comparative Examples 1～2 and Performance Ratio are
As can be seen from Table 1, add the g-SEBS of maleic anhydride graft and the low-luster polypropylene matrix material that fully sulfurized silicon rubber powder is made, not only had excellent eliminate optical property, also had good shock resistance.
Claims (10)
1. low-luster polypropylene composite material includes the following component of blend: polypropylene, g-SEBS, fully sulfurized silicon rubber powder, mineral filler;
Wherein, take polypropylene as 100 weight parts, g-SEBS is 1～30 weight part, and fully sulfurized silicon rubber powder is 1～30 weight part, and mineral filler is 10～35 weight parts;
Described g-SEBS is maleic anhydride grafts, and maleic anhydride grafting ratio is 1～3%; The median size of described fully sulfurized silicon rubber powder is 0.05～1 μ m, and its gel content is 60wt% or higher.
2. polypropylene composite material as claimed in claim 1 is characterized in that:
Take polypropylene as 100 weight parts, g-SEBS is 3～30 weight parts, and fully sulfurized silicon rubber powder is 3～30 weight parts, and mineral filler is 12～34 weight parts.
3. polypropylene composite material as claimed in claim 1 is characterized in that:
Described g-SEBS, its maleic anhydride grafting ratio are 1～1.5%.
4. polypropylene composite material as claimed in claim 1 is characterized in that:
Described g-SEBS, its styrene content are 30～33%wt.
5. polypropylene composite material as claimed in claim 1 is characterized in that:
Described inorganic materials is selected from least a in talcum powder, barium sulfate, calcium carbonate and the silicon salt whisker, and its average particle size range is 1～13 μ m.
6. polypropylene composite material as claimed in claim 1 is characterized in that:
The average particle size range of described fully sulfurized silicon rubber powder is 0.05～0.2 μ m.
7. polypropylene composite material as claimed in claim 1 is characterized in that:
The gel content of described fully sulfurized silicon rubber powder is 75wt% or higher.
8. polypropylene composite material as claimed in claim 1 is characterized in that:
Include take polypropylene as 100 parts by weight the oxidation inhibitor of 0.1～2 parts by weight;
Described oxidation inhibitor is selected from the mixture of Hinered phenols antioxidant and phosphoric acid ester oxidation inhibitor; The weight ratio of Hinered phenols antioxidant and phosphoric acid ester oxidation inhibitor is 1: 1～1: 2.
9. polypropylene composite material as claimed in claim 8 is characterized in that:
Described Hinered phenols antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Described phosphoric acid ester oxidation inhibitor is three (2,4-di-tert-butylphenol) phosphorous acid ester.
10. preparation method who prepares such as each described polypropylene composite material of claim 1～9 is characterized in that:
Comprise that the component that will include described polypropylene, g-SEBS, fully sulfurized silicon rubber powder and mineral filler mixes by described content, melt blending makes described low-luster polypropylene composite material.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348714A (en) * | 2015-11-27 | 2016-02-24 | 苏州润佳工程塑料股份有限公司 | Extinction modified polypropylene composite material |
| CN109111644A (en) * | 2018-10-11 | 2019-01-01 | 安庆市泽烨新材料技术推广服务有限公司 | PP composite material and preparation method thereof |
| CN109337207A (en) * | 2018-10-11 | 2019-02-15 | 安庆市泽烨新材料技术推广服务有限公司 | Polypropylene fire retardant composite material and preparation method |
| CN109467816A (en) * | 2018-10-11 | 2019-03-15 | 安庆市泽烨新材料技术推广服务有限公司 | Wear-resisting polypropene composite material and preparation method thereof |
| CN109721842A (en) * | 2018-12-29 | 2019-05-07 | 浙江普利特新材料有限公司 | A kind of automobile rigid plastic instrument board low gloss, high rigidity, high impact resistance polypropylene composite material and preparation method thereof |
| CN111406094A (en) * | 2017-11-29 | 2020-07-10 | 花王株式会社 | Polypropylene resin composition |
| CN112625358A (en) * | 2020-11-18 | 2021-04-09 | 万华化学(四川)有限公司 | Low-glossiness soft-touch non-woven fabric type polypropylene composite material, and preparation method and application thereof |
| CN112708192A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Polypropylene/thermoplastic elastomer blend and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348714A (en) * | 2015-11-27 | 2016-02-24 | 苏州润佳工程塑料股份有限公司 | Extinction modified polypropylene composite material |
| CN111406094A (en) * | 2017-11-29 | 2020-07-10 | 花王株式会社 | Polypropylene resin composition |
| CN109111644A (en) * | 2018-10-11 | 2019-01-01 | 安庆市泽烨新材料技术推广服务有限公司 | PP composite material and preparation method thereof |
| CN109337207A (en) * | 2018-10-11 | 2019-02-15 | 安庆市泽烨新材料技术推广服务有限公司 | Polypropylene fire retardant composite material and preparation method |
| CN109467816A (en) * | 2018-10-11 | 2019-03-15 | 安庆市泽烨新材料技术推广服务有限公司 | Wear-resisting polypropene composite material and preparation method thereof |
| CN109721842A (en) * | 2018-12-29 | 2019-05-07 | 浙江普利特新材料有限公司 | A kind of automobile rigid plastic instrument board low gloss, high rigidity, high impact resistance polypropylene composite material and preparation method thereof |
| CN112708192A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Polypropylene/thermoplastic elastomer blend and preparation method and application thereof |
| CN112708192B (en) * | 2019-10-25 | 2022-09-20 | 中国石油化工股份有限公司 | Polypropylene/thermoplastic elastomer blend and preparation method and application thereof |
| CN112625358A (en) * | 2020-11-18 | 2021-04-09 | 万华化学(四川)有限公司 | Low-glossiness soft-touch non-woven fabric type polypropylene composite material, and preparation method and application thereof |
| CN112625358B (en) * | 2020-11-18 | 2023-05-26 | 万华化学(四川)有限公司 | Low-glossiness soft-touch non-woven fabric type polypropylene composite material, preparation method and application thereof |
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