CN103073785B - A kind of low-luster polypropylene composite material and preparation method thereof - Google Patents
A kind of low-luster polypropylene composite material and preparation method thereof Download PDFInfo
- Publication number
- CN103073785B CN103073785B CN201110330606.8A CN201110330606A CN103073785B CN 103073785 B CN103073785 B CN 103073785B CN 201110330606 A CN201110330606 A CN 201110330606A CN 103073785 B CN103073785 B CN 103073785B
- Authority
- CN
- China
- Prior art keywords
- composite material
- polypropylene
- polypropylene composite
- silicon rubber
- rubber powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention provides a kind of low-luster polypropylene composite material and preparation method thereof, relate to polypropylene composite material field.It includes blended following component: polypropylene, grafting hydrogenated styrene-butadiene-styrene block copolymers, fully sulfurized silicon rubber powder, mineral filler; Wherein, be 100 parts by weight with polypropylene, grafting hydrogenated styrene-butadiene-styrene block copolymers 1 ~ 30 weight part, fully sulfurized silicon rubber powder 1 ~ 30 weight part, mineral filler 10 ~ 35 weight part; Described grafting hydrogenated styrene-butadiene-styrene block copolymers is maleic anhydride grafts, and percentage of grafting is 1 ~ 3%; Described fully sulfurized silicon rubber powder median size is 0.05 ~ 1 μm, and gel content is 60wt% or higher.Low-luster polypropylene composite material of the present invention has good eliminate optical property and shock resistance, and preparation technology is simple, condition is easy to control, and is applicable to the fields such as automotive upholstery.
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
It is high that polypropylene has heat resisting temperature, the advantage that fatigue resistance, electrical insulating property, resistance to corrosive chemicals, processing forming are good, and price is low, quality gently, easily reclaims, and is therefore widely used in fields such as automotive industrys.But common modifications polypropylene material has gloss or reflective characteristic more, this defect not only makes automotive trim Integral decoration class reduce, and more makes car-driver easily tired, even can affect the driving safety of car-driver, increases traffic accident odds.Also the needs of new automobile Plastics Development that can be decoration integrated cannot be met.Therefore, automobile low-luster polypropylene material receives publicity day by day.
Around the problem of polypropylene material surface dulling, people have carried out many research work.Publication number CN101759919A patent by adding a kind of mineral filler wollastonite that effectively can reduce product surface glossiness in the basic components of polypropylene composite material, thus prepares low-luster polypropylene composite material.Owing to the addition of a large amount of mineral fillers thus being degrading the comprehensive mechanical property of polypropylene composite material.Publication number CN101173075 patent by adding the glossiness that 0.5 ~ 5 part of silicon-dioxide reduces polypropylene composite material in polypropylene composite material.Equally, addition too much can the mechanical property of deteriorated polypropylene composite material, and addition very little extinction effect is not obvious again, is still difficult to widespread use at present in auto industry field.
Publication number CN101313025A utilized the elastomer copolymer of propylene and ethylene atactic copolymer and propylene and ethene to make comparatively soft polyolefin light extinction composition, this polymkeric substance has good eliminate optical property and mechanical property, is applicable to sheet material extruding, blows thermo forming fields and the field such as internal decoration of car top layer and film.Be not suitable for injection structure product.
Publication number CN101121799A patent discloses one and adds peroxide cross-linking agent that polyethylene molecule is produced is crosslinked, forming microgel is distributed in polypropylene matrix, and 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, effectively can reduce the surface gloss of polypropylene composite material, solve the deficiencies in the prior art well.
Composition of the present invention includes following main ingredient: polypropylene, g-SEBS, fully sulfurized silicon rubber powder and mineral filler; Wherein, be 100 parts by weight with polypropylene, g-SEBS is 1 ~ 30 weight part, preferably 3 ~ 30 weight parts; Fully sulfurized silicon rubber powder 1 ~ 30 weight part, preferably 3 ~ 30 weight parts; Mineral filler 10 ~ 35 weight part, preferably 12 ~ 34 weight parts.
In the present invention, described polypropylene comprises at least one in various homo-polypropylene of the prior art or Co-polypropylene.
Described grafting hydrogenated styrene-butadiene-styrene block copolymers is maleic anhydride grafts, and maleic anhydride grafting ratio is 1 ~ 3%, preferably 1 ~ 1.5%.Styrene content is 30 ~ 33%wt.
Described fully sulfurized silicon rubber powder, its median size is 0.05 ~ 1 μm, preferably 0.05 ~ 0.2 μm, is more preferably 0.05 ~ 0.1 μm; Its gel content is 60wt% or higher, is preferably 75wt% or higher, is 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 each particulate namely in this fully sulfurized silicon rubber powder is homogeneous phase, and single particulate is all homogeneous on composition.The phenomenon of layering, point equal uneven phase is not found in particulate under the observation of existing microtechnique.This fully sulfurized silicon rubber powder is by fixing corresponding silicone rubber latex cross-linking radiation rubber particles particle diameter.Detailed content of fully sulfurized silicon rubber powder of the present invention and preparation method thereof, can see Chinese patent CN 1383439A, and its full content is incorporated herein the present invention as a reference.
Described mineral filler is one in conventional talcum powder, barium sulfate, calcium carbonate and silicon salt whisker etc. or mixture, and its median size is 1 ~ 13 μm, preferably 5 ~ 10 μm.The Main Function of the mineral filler added in the present invention is the comprehensive mechanical property improving material, to be adapted to the service requirements of trolley part.
In the present invention, the fully sulfurized silicon rubber powder added inherently has good rebound resilience and the effect of delustring, therefore plays a role to the glossiness reducing matrix material; And the SEBS of maleic anhydride graft and the small fully sulfurized silicon rubber powder of particle can be dispersed and form small gel in polypropylene, formed at product surface after shaping and can produce irreflexive uniform minute asperities, thus effectively reduce the glossiness on polypropylene composite material surface.In addition, as the shock strength of rubber to the mechanical property improving material, particularly matrix material, there is very large effect.
Also comprise oxidation inhibitor in matrix material of the present invention, oxidation inhibitor can select the various oxidation inhibitor that in prior art, resin is conventional, and its consumption is also 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 100 weight parts with polypropylene, is 0.1 ~ 2 weight part, preferably 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.Wherein Hinered phenols antioxidant preferably four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (as the anti-oxidant Irganox 1010 that Ciba fine chemicals produces); Phosphoric acid ester oxidation inhibitor is three (2,4-di-tert-butylphenol) phosphorous acid ester (as the oxidation inhibitor Irgafos 168 that Ciba fine chemicals produces) preferably.
Some auxiliary agents conventional in the acrylic resin course of processing can also be comprised in 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 object of the present invention is the preparation method providing this kind of low-luster polypropylene composite material, is achieved through the following technical solutions: comprise by comprise described polypropylene, g-SEBS, fully sulfurized silicon rubber powder and mineral filler component obtain described polypropylene composite material by described content melt blending.
More specifically, the preparation method of polypropylene composite material of the present invention comprises: by include described polypropylene, g-SEBS, fully sulfurized silicon rubber powder and mineral filler component be fully mixed to evenly in mixing equipment by described component proportion, extrude through blending equipment melt blending, after granulation, namely make low-luster polypropylene matrix material of the present invention.
In the course of processing of polypropylene composite material of the present invention, material melts blending temperature is blending temperature used in the processing of usual acrylic resin, should not only ensureing the complete melting of matrix resin but also can not make to select in its scope of decomposing, be generally 190 DEG C ~ 220 DEG C, preferred processing temperature is 200 ~ 220 DEG C.In addition, according to processing needs, can add some auxiliary agents conventional in the acrylic resin course of processing in blended material in right amount, as dispersion agent, processing thermo-stabilizer, photostabilizer etc., its consumption is conventional amount used, or adjusts according to the requirement of practical situation.
In the preparation method of the invention described above, the mixing equipment of mixing of materials can adopt various mixing equipments used in prior art, as stirrer, kneading machine etc.The melt blending equipment used in preparation method of the present invention is the general blending equipment in rubber and plastic processing industry, 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 adds g-SEBS and fully sulfurized silicon rubber powder by adopting, and significantly reduces the glossiness of matrix material, thus prepares the low-luster polypropylene matrix material of excellent combination property.The experiment proved that, 60 °, the light face angle glossiness of matrix material of the present invention all significantly decreases compared with original product with 20 °, light face angle glossiness, and this matrix material has excellent comprehensive mechanical property, solves the deficiencies in the prior art well.
The polypropylene composite material prepared 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
Below in conjunction with specific embodiment, the present invention will be further described.But the present invention is not limited in following embodiment.
Embodiment 1 ~ 6
By polypropylene (K9020, Sinopec Yanshan Mountain branch office), g-SEBS (FG1901, Ke Teng company of the U.S., maleic anhydride grafting ratio 1.5%, styrene content 30%), fully sulfurized silicon rubber powder (VP-602, median size 0.1 μm, gel content 90wt%; Beijing Chemical Research Institute of China Petrochemical Industry), talcum powder (median size 6.5 μm, Haicheng powder body material company limited), (Irganox 1010 and Irgafos 168 is composite and obtain with weight ratio 1: 1 for oxidation inhibitor, Ciba fine chemicals) put into homogenizer, stir 3 minutes under the rotating speed of 300 revs/min, each component is fully mixed.Subsequently by said mixture material extruding pelletization under the condition of the mixing unit of BUSS (MKD-30, BUSS company of Switzerland) within the scope of 190 DEG C ~ 220 DEG C, obtain low-luster polypropylene matrix material.It is specifically filled a prescription in table 1, and wherein each component concentration is all with weight parts.
The pellet extruded is dried 6hr in 95 DEG C of constant temperature ovens, and then become standard batten at the condition hemostasis of 210 DEG C ~ 225 DEG C, Izod notched impact strength is according to ISO180 standard testing; Glossiness test uses JFL-BZ 20 ° of 60 ° of 85 ° of intelligent Grossmeters, and test condition is: (1) stability: 0.4 gloss unit (Gs)/30 minute; (2) measurement window size: 16 × 48 (mm); (3) test sample surface is specular light face.Testing standard is ISO-2813.Specific performance the results are shown in Table 1.
Comparative example 1 ~ 2
Polypropylene (with embodiment 1), oxidation inhibitor (with embodiment 1), talcum powder (with embodiment 1) are put into homogenizer, stirs 3 minutes under the rotating speed of 300 revs/min, each component is fully mixed.Subsequently by said mixture material extruding pelletization under the condition of the mixing unit of BUSS (with embodiment 1) within the scope of 190 DEG C ~ 220 DEG C, obtain low-luster polypropylene matrix material.It is specifically filled a prescription in table 1, and wherein each component concentration is all with weight parts.
The test process of comparative example material and the same embodiment of testing standard.Specific performance the results are shown in Table 1.
The component of table 1 embodiment 1 ~ 6 and comparative example 1 ~ 2 and Performance comparision
As can be seen from Table 1, with the addition of the low-luster polypropylene matrix material that the g-SEBS of maleic anhydride graft and fully sulfurized silicon rubber powder are made, not only there is excellent eliminate optical property, also there is good shock resistance.
Claims (10)
1. a low-luster polypropylene composite material, is made up of blended following component: polypropylene, g-SEBS, fully sulfurized silicon rubber powder, mineral filler;
Wherein, be 100 parts by weight with polypropylene, g-SEBS is 1 ~ 30 weight part, and fully sulfurized silicon rubber powder is less than or equal to 30 weight parts for being greater than 5 weight parts, 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 μm, and its gel content is 60wt% or higher.
2. polypropylene composite material as claimed in claim 1, is characterized in that:
Be 100 parts by weight with polypropylene, g-SEBS 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 is 1 ~ 1.5%.
4. polypropylene composite material as claimed in claim 1, is characterized in that:
Described g-SEBS, its styrene content is 30 ~ 33%wt.
5. polypropylene composite material as claimed in claim 1, is characterized in that:
Described inorganic materials is selected from least one in talcum powder, barium sulfate, calcium carbonate and silicon salt whisker, and its average particle size range is 1 ~ 13 μm.
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 μm.
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:
Including with polypropylene is the oxidation inhibitor of 100 weight parts, 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. prepare a preparation method for the polypropylene composite material as described in any one of claim 1 ~ 9, it is characterized in that:
Comprise and described polypropylene, g-SEBS, fully sulfurized silicon rubber powder and mineral filler being mixed by described content, melt blending obtains described low-luster polypropylene composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110330606.8A CN103073785B (en) | 2011-10-26 | 2011-10-26 | A kind of low-luster polypropylene composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110330606.8A CN103073785B (en) | 2011-10-26 | 2011-10-26 | A kind of low-luster polypropylene composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103073785A CN103073785A (en) | 2013-05-01 |
| CN103073785B true CN103073785B (en) | 2015-08-19 |
Family
ID=48150496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110330606.8A Active CN103073785B (en) | 2011-10-26 | 2011-10-26 | A kind of low-luster polypropylene composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103073785B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348714B (en) * | 2015-11-27 | 2018-08-31 | 苏州润佳工程塑料股份有限公司 | Delustring modified polypropylene composite material |
| JP2019099807A (en) * | 2017-11-29 | 2019-06-24 | 花王株式会社 | Polypropylene resin composition |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293983A (en) * | 2007-04-28 | 2008-10-29 | 中国石油化工股份有限公司 | Expansion flame-proof polypropelene composition and preparation method thereof |
-
2011
- 2011-10-26 CN CN201110330606.8A patent/CN103073785B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293983A (en) * | 2007-04-28 | 2008-10-29 | 中国石油化工股份有限公司 | Expansion flame-proof polypropelene composition and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物研究进展;杜丽利等;《合成树脂及塑料》;20031231;第20卷(第4期);第70-73页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103073785A (en) | 2013-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103073785B (en) | A kind of low-luster polypropylene composite material and preparation method thereof | |
| CN102807703B (en) | Low gloss polypropylene composition and preparation method thereof | |
| CN103073786B (en) | A kind of polypropylene matting agent master batch and its preparation method and application | |
| CN102993556B (en) | Polypropylene composite, its preparation method and application thereof | |
| CN109651711A (en) | Low smell resistance to stress is whitened scratch-resistant ore filled polypropylene material and preparation method | |
| CN103788471A (en) | Low VOC polypropylene resin composition and preparation method thereof | |
| CN102532703A (en) | Low-odor high-luster modified polypropylene material and preparation method thereof | |
| CN103724923A (en) | Antibacterial ABS (Acrylonitrile Butadiene Styrene) composite material with low smell and low diffusion and preparation method thereof | |
| CN102993757B (en) | Preparation method of stable composite modified asphalt | |
| CN102585324A (en) | Polyethylene composition for improving yellow index and lustrousness and preparation method thereof | |
| CN109354773A (en) | The nucleating agent application tackiness in the precipitation for reducing PP composite material | |
| CN112759848A (en) | Antibacterial antistatic polypropylene composite material and preparation method thereof | |
| CN103709704A (en) | PC/ABS (Polycarbonate/Acrylonitrile-Butadiene-Styrene) alloy with low odor and low emission and preparation method of PC/ABS alloy | |
| CN104558837A (en) | Scratching-resistant low-gloss polypropylene composite material and preparation method thereof | |
| CN104744762A (en) | Toughening modified polyethylene powder and preparation method thereof | |
| CN102731901B (en) | Low VOC polypropylene composite material for vehicle and preparation method thereof | |
| CN103724965A (en) | Fiberglass reinforced PC/ABS (Polycarbonate/Acrylonitrile Butadiene Styrene) composite material with low smell and diffusion and preparation method thereof | |
| CN111777821B (en) | Poly 4-methyl-1-pentene/silicone rubber thermoplastic elastomer and preparation and application thereof | |
| CN112430361A (en) | Polypropylene-metal matrix composite material capable of achieving microwave self-repairing and preparation method thereof | |
| CN109694524A (en) | A kind of polypropylene resin composite and preparation method thereof of the low smell of low VOC | |
| CN105733074A (en) | Automobile air pipe material and preparation method thereof | |
| CN103304893B (en) | Low VOC (Volatile Organic Compound) polypropylene composition and preparation method thereof | |
| CN105885173A (en) | Special master batch for silane crosslinking insulation material and preparation method of special master batch | |
| CN114085451B (en) | Polypropylene composition and preparation method and application thereof | |
| CA3139602C (en) | Polypropylene board and method for preparing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |