CN103073786A - Polypropylene-use matting agent masterbatch, and preparation method and application thereof - Google Patents
Polypropylene-use matting agent masterbatch, and preparation method and application thereof Download PDFInfo
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- CN103073786A CN103073786A CN2011103306246A CN201110330624A CN103073786A CN 103073786 A CN103073786 A CN 103073786A CN 2011103306246 A CN2011103306246 A CN 2011103306246A CN 201110330624 A CN201110330624 A CN 201110330624A CN 103073786 A CN103073786 A CN 103073786A
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Abstract
The invention provides a polypropylene-use matting agent masterbatch, and a preparation method and an application thereof. The invention relates to the field of plastic modification. The masterbatch comprises the blended materials of, by weight: 100 parts of polypropylene, 20-70 parts of functionalized SBS copolymer, 10-50 parts of fully vulcanized powder silicone rubber, and 5-20 parts of silica. The fully vulcanized powder silicone rubber has an average particle size of 0.05-1mum and a gel content of 60wt% or higher. The average particle size of silica is 1-10mum. With the matting agent masterbatch provided in the invention, polypropylene modified material surface gloss can be substantially reduced. During an application process, matting agent masterbatch dose can be flexibly controlled according to different requirements on gloss. The application method is simple and reliable. The masterbatch can be widely applied in fields such as high-end automotive interior parts.
Description
Technical field
The present invention relates to a kind of modifying plastics field, say further, relate to a kind of matting agent master batch for reducing the polypropylene glossiness and its preparation method and application.
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, this defective not only makes automotive trim Integral decoration class reduce, more make the car-driver tired easily, even can affect car-driver's driving safety, increase 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, be applicable to the sheet material extruding, blow thermoforming field and the fields such as internal decoration of car top layer and film, but this composition is 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, forming microgel is 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, one of purpose of the present invention provides a kind of matting agent master batch for reducing the polypropylene glossiness.By adding matting agent master batch provided by the invention, can effectively reduce the surface gloss of modified polypropylene material, solved well the deficiencies in the prior art.
Matting agent master batch of the present invention includes following main ingredient: polypropylene (PP), functionalization styrene-butadiene-styrene block copolymer (function SBS multipolymer), fully sulfurized silicon rubber powder and silicon-dioxide; Wherein, take polypropylene as 100 weight parts, function SBS multipolymer is 20～70 weight parts, is preferably 25～60 weight parts; Fully sulfurized silicon rubber powder is 10～50 weight parts, is preferably 15～40 weight parts; Silicon-dioxide is 5～20 weight parts, is preferably 10～20 weight parts.
Among the present invention, described polypropylene comprises at least a in various homo-polypropylene of the prior art or the Co-polypropylene.Preferred 0.5～the 5.0g/10min of its melting index.
Described function SBS multipolymer is a kind of Tetrablock copolymer, structure can represent with SDSP, wherein S represents polystyrene block, D represents polybutadiene block or polyisoprene blocks, P represents polar block, this polar block is obtained by the polar monomer polymerization that the pyridine of vinyl arsenic and derivative thereof form, and this polar monomer comprises the pyridine of 2-vinyl arsenic, the arsenic pyridine of 4-vinyl and isomer thereof etc.In the SDS segment of function SBS multipolymer, the ratio of S/D is 5%～95%/95%～5%, is 0.1%～50% at the weight content of polymkeric substance Semi-polarity block.The number-average molecular weight of described function SBS is not limit, and is preferably 10,000～300,000; Molecular weight distributing index is not limit, and is preferably 1.02～2.00.
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 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 the 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 silicon-dioxide is commercially available silicon-dioxide, and its particle size range is generally unlimited, can be preferably 1～10 μ m.
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 function SBS multipolymer and small especially fully sulfurized silicon rubber powder can be in polypropylene Uniform Dispersion and form small gel, after the moulding product surface form can produce uniformly irreflexive small concavo-convex, thereby effectively reduce the glossiness on polypropylene composite material surface.Silicon-dioxide is the inorganics of a kind of small particle size, multiple aperture, bigger serface, is dispersed in the polypropylene matrix by mixing facilities, much stays the surface after the moulding, forms small male and fomale(M﹠F), thereby reduces the glossiness of material.
Also comprise oxidation inhibitor in the matting agent master batch of the present invention, oxidation inhibitor can be selected various oxidation inhibitor commonly used in the prior art polypropylene, and its consumption also is conventional amount used.Comparative optimization, described oxidation inhibitor is selected from the mixture of Hinered phenols antioxidant and phosphoric acid ester oxidation inhibitor.Total consumption of oxidation inhibitor is 0.1～0.5 weight part take polypropylene as 100 parts by weight, preferred 0.2～0.4 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 Irgafos 168 of Ciba fine chemicals production).
Can also comprise some auxiliary agents commonly used in the acrylic resin course of processing in the matting agent master batch 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 above polypropylene that says with the preparation method of matting agent master batch, is achieved through the following technical solutions: will comprise described acrylic resin, function SBS, fully sulfurized silicon rubber powder and silicon-dioxide etc. and make described polypropylene matting agent master batch in interior component by described content melt blending.
Further specify the preparation method of this kind matting agent master batch, may further comprise the steps:
The first step: take by weighing various described raw materials by described consumption;
Second step: acrylic resin, function SBS multipolymer, fully sulfurized silicon rubber powder, silicon-dioxide that drying treatment is crossed evenly mix in mixing equipment in each interior component, obtain mixture.
The 3rd step: namely make matting agent master batch of the present invention behind the mixture process blending equipment melt blending extruding pelletization with the step 2 acquisition.
In the course of processing of matting agent master batch 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 in the blend material, add in right amount some auxiliary agents commonly used in the acrylic resin course of processing, 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.
Three of purpose of the present invention is to provide the application of this kind matting agent master batch on low-luster polypropylene is material modified, is achieved through the following technical solutions: will comprise the melt blending extruding pelletizations such as acrylic resin, described matting agent master batch and other conventional components and get final product to get the polypropylene modified material of low-luster.Wherein the consumption of matting agent master batch is 10～40 parts by weight generally take acrylic resin as 100 parts by weight.
Further specify the using method of this kind matting agent master batch, comprise following technological step:
The first step: measure various raw materials by described usefulness;
Second step: acrylic resin, matting agent master batch and other components that drying treatment is crossed are fully mixed in mixing equipment evenly in each interior component, obtain mixture.
The 3rd step: the polypropylene modified material that namely can be made into low-luster behind the mixture process blending equipment melt blending extruding pelletization with the step 2 acquisition.
The processing parameters such as the equipment that uses in more than using and processing temperature are all with the equipment and process parameter that usually adopts in the polypropylene manufacture field.
Compared with prior art, the present invention has following beneficial effect:
Use matting agent master batch of the present invention can reduce significantly the surface gloss of polypropylene modified material.And in use can require according to the difference of glossiness to grasp flexibly matting agent master batch consumption, using method is simple and reliable.Can be widely used in the fields such as high-grade automotive upholstery.
Embodiment
The present invention will be further described below in conjunction with specific embodiment.But the present invention is not limited in following embodiment.
The preparation of matting agent master batch:
With matrix resin PP (K8303, Sinopec Yanshan Mountain branch office, melting index 2.5g/10min), (number-average molecular weight is 8.43 ten thousand to function SBS multipolymer, polar block weight content 3.0%, the S/D weight ratio is 40/60, molecular weight distributing index is 1.2, and polar monomer is the pyridine of vinyl arsenic; The production of Ba Ling petrochemical complex limited liability company), fully sulfurized silicon rubber powder (trade mark VP-602, median size 0.1 μ m, gel content 90wt%; The China Petrochemical Industry Beijing Chemical Research Institute produces) and silicon-dioxide (trade mark C807, particle diameter 7 μ m, pH value 3.3, porosity 2ml/g; U.S. W. R. Grace ﹠ Co), (antioxidant 1010 and irgasfos 168 are composite, weight ratio 1: 1 for oxidation inhibitor; Ciba fine chemicals is produced) put into homogenizer, under 300 rev/mins rotating speed, stirred 3 minutes, each component is fully mixed; Subsequently with the said mixture material through the mixing unit of BUSS in 190 ℃～220 ℃ scopes (MKD-30, Switzerland BUSS company), extruding pelletization obtains the matting agent master batch.Its concrete prescription sees Table 1, and wherein each component concentration is all in parts by weight.
The component proportion of table 1 matting agent master batch
The preparation of low-luster polypropylene material:
Embodiment 1～8
With polypropylene (K9020, Sinopec Yanshan Mountain branch office), (Irganox 1010 and Irgafos 168 are composite and get with weight ratio 1: 1 for matting agent master batch (A-D) and oxidation inhibitor, Ciba fine chemicals) puts into homogenizer, under 300 rev/mins rotating speed, stirred 3 minutes, each component is fully mixed.Subsequently with the said mixture material through the twin-screw extrusion unit in 190 ℃～220 ℃ scopes, extruding pelletization, it is material modified to obtain low-luster polypropylene.Its concrete prescription sees Table 2, 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, carry out the test of eliminate optical property and socle girder notched Izod impact strength.The test of socle girder notched Izod impact strength is tested according to international standard testing method ISO180.JFL-BZ20 ° of 60 ° of 85 ° of intelligent Grossmeters 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.Test result sees Table 2.
Embodiment 9～16
With polypropylene (K9020, Sinopec Yanshan Mountain branch office), matting agent master batch (A-D), superfine talcum powder (median size 6.5 μ m, Haicheng powder body material company limited) and oxidation inhibitor (Irganox 1010 and Irgafos 168 are composite and get with weight ratio 1: 1, Ciba fine chemicals) puts into homogenizer, under 300 rev/mins rotating speed, stirred 3 minutes, each component is fully mixed.Subsequently with the said mixture material through the twin-screw extrusion unit in 190 ℃～220 ℃ scopes, extruding pelletization, it is material modified to obtain low-luster polypropylene.Its concrete prescription sees Table 3, 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, carry out the test of eliminate optical property.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.Its test result sees Table 3.
Comparative Examples 1～3
With polypropylene (with embodiment 1), (Comparative Examples 1 does not add superfine talcum powder, Comparative Examples 2 is with embodiment 9, Comparative Examples 3 is with embodiment 10) and oxidation inhibitor (with embodiment 1) put into homogenizer, under 300 rev/mins rotating speed, stirred 3 minutes, each component is fully mixed.Subsequently with the said mixture material through the twin-screw extrusion unit in 190 ℃～220 ℃ scopes, extruding pelletization, it is material modified to obtain low-luster polypropylene.Its concrete prescription sees Table 2 and table 3, and wherein each component concentration is all in parts by weight.Testing standard is with embodiment 1.
Table 2 embodiment 1～8 compares with component and the eliminate optical property of Comparative Examples 1
Table 3 embodiment 9～16 compares with component and the eliminate optical property of Comparative Examples 2～3
Can find out that from table 2 and table 3 it is material modified to have added the low-luster polypropylene that matt master makes, and not only has excellent eliminate optical property, also has good shock strength.Can be widely used in the fields such as high-grade automotive upholstery.
Claims (11)
1. polypropylene matting agent master batch includes the following component of blend: polypropylene, function SBS multipolymer, fully sulfurized silicon rubber powder and silicon-dioxide; Wherein, take polypropylene as 100 weight parts, function SBS multipolymer is 20～70 weight parts; Fully sulfurized silicon rubber powder is 10～50 weight parts; Silicon-dioxide is 5～20 weight parts;
Described function SBS multipolymer is a kind of Tetrablock copolymer, structure is SDSP, wherein S is polystyrene block, D is polybutadiene block or polyisoprene blocks, P is polar block, and at least a polymerization in the polar monomer that this polar block is comprised of vinyl arsenic pyridine or derivatives thereof obtains;
The median size of described fully sulfurized silicon rubber powder is 0.05～1 μ m, is preferably 0.05～0.2 μ m; Its gel content is 60wt% or higher, is preferably 75wt% or higher.
2. matting agent master batch as claimed in claim 1 is characterized in that:
Take polypropylene as 100 weight parts, function SBS multipolymer is 25～60 weight parts; Fully sulfurized silicon rubber powder is 15～40 weight parts; Silicon-dioxide is 10～20 weight parts.
3. matting agent master batch as claimed in claim 1 is characterized in that:
Described polypropylene comprises at least a of homo-polypropylene and Co-polypropylene resin, and its melting index is 0.5～5.0g/10min.
4. matting agent master batch as claimed in claim 1 is characterized in that:
The number-average molecular weight of described SDSP is preferably 1～300,000; Molecular weight distributing index is preferably 1.02～2.00.
5. matting agent master batch as claimed in claim 1 is characterized in that:
The polar monomer of the polar block of described formation function SBS multipolymer comprises at least a in the pyridine of 2-vinyl arsenic, the arsenic pyridine of 4-vinyl and the isomer thereof.
6. matting agent master batch as claimed in claim 1 is characterized in that:
In the segment of described function SBS multipolymer, the part by weight of S/D is 5%～95%/95%～5%, is 0.1%～50% at the weight content of function SBS multipolymer Semi-polarity block.
7. matting agent master batch as claimed in claim 1 is characterized in that:
The particle size range of described silicon rubber powder is 1～10m.
8. matting agent master batch as claimed in claim 1 is characterized in that:
Include take polypropylene as 100 parts by weight the oxidation inhibitor of 0.1～0.5 weight part;
Described oxidation inhibitor is selected from Hinered phenols antioxidant and phosphoric acid ester antioxidant mixture, and the weight ratio of Hinered phenols antioxidant and phosphoric acid ester oxidation inhibitor is 1: 1～1: 2.
9. matting agent master batch 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 such as each described matting agent master batch of claim 1～9 is characterized in that:
The component that will comprise described polypropylene, function SBS multipolymer, fully sulfurized silicon rubber powder and silicon-dioxide mixes by described content, and melt blending makes described polypropylene matting agent master batch.
11. one kind such as each described matting agent master batch application on low-luster polypropylene is material modified of claim 1～9, comprise the component melts blending extrusion granulation that will contain acrylic resin, described matting agent master batch and the polypropylene modified material of described low-luster; Wherein take acrylic resin as 100 parts by weight, the matting agent master batch is 10～40 parts by weight.
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| CN104031303A (en) * | 2014-04-02 | 2014-09-10 | 南京淳达科技发展有限公司 | Polyethylene master batch compound additive and preparation method thereof |
| CN106009457A (en) * | 2016-07-28 | 2016-10-12 | 广东天保新材料有限责任公司 | PP matte color masterbatch and application thereof |
| PL424164A1 (en) * | 2018-01-03 | 2019-07-15 | Albert Groenwald | Concentrate of thermoplastic polymer matrix polysiloxane and inorganic filler in the form of the premix or granulated product and method for producing the premix and granulated polysiloxane concentrate |
| CN114181452A (en) * | 2021-10-29 | 2022-03-15 | 金发科技股份有限公司 | Polypropylene composition and preparation method and application thereof |
| CN114891356A (en) * | 2022-06-23 | 2022-08-12 | 盛嘉伦橡塑(河源)有限公司 | Thermoplastic elastomer material and preparation method thereof |
| CN115536929A (en) * | 2022-10-27 | 2022-12-30 | 广东美联新材料股份有限公司 | High-haze HDPE (high-density polyethylene) extinction master batch and preparation method thereof |
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| CN104031303A (en) * | 2014-04-02 | 2014-09-10 | 南京淳达科技发展有限公司 | Polyethylene master batch compound additive and preparation method thereof |
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| CN115536929A (en) * | 2022-10-27 | 2022-12-30 | 广东美联新材料股份有限公司 | High-haze HDPE (high-density polyethylene) extinction master batch and preparation method thereof |
| CN115536929B (en) * | 2022-10-27 | 2023-12-08 | 广东美联新材料股份有限公司 | High-haze HDPE extinction master batch and preparation method thereof |
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