CN1300236C - Mineral/ whisker reinforced polypropylene composition - Google Patents
Mineral/ whisker reinforced polypropylene composition Download PDFInfo
- Publication number
- CN1300236C CN1300236C CNB031159222A CN03115922A CN1300236C CN 1300236 C CN1300236 C CN 1300236C CN B031159222 A CNB031159222 A CN B031159222A CN 03115922 A CN03115922 A CN 03115922A CN 1300236 C CN1300236 C CN 1300236C
- Authority
- CN
- China
- Prior art keywords
- mineral
- whisker
- coupling agent
- reinforced polypropylene
- polypropylene
- 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.)
- Expired - Lifetime
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 52
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 44
- -1 polypropylene Polymers 0.000 title claims abstract description 41
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 31
- 239000011707 mineral Substances 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 3
- 239000007822 coupling agent Substances 0.000 claims description 14
- 239000012745 toughening agent Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 230000035939 shock Effects 0.000 abstract description 5
- 238000001746 injection moulding Methods 0.000 abstract description 3
- 239000008187 granular material Substances 0.000 abstract 2
- 239000012744 reinforcing agent Substances 0.000 abstract 2
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 3
- 230000002950 deficient Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Abstract
The present invention relates to a mineral / whisker reinforcing polypropylene composition which is matched with polypropylene, mineral reinforcing agents, toughening master granules, PP grafting compatilizers, antioxidants and other auxiliary agents. The present invention is characterized in that whisker reinforcing agents are added. In the preparation method of the present invention, other components except for magnesium salt whiskers are placed in a high mixing machine to mix for 2 to 3 minutes at high speed, the magnesium salt whiskers are added, materials are discharged after being mixed for about 1 minute at low speed, and then the materials are extruded from a double screw machine combined by special screws to granulate. The processing temperature of double screws is from 170 DEG C to 240 DEG C, and the screw speed is from 180 to 600 revolutions per minute. The present invention has the characteristics of high strength, high rigidity, shock resistance, good size stability, uniform transversal and longitudinal shrinkage ratio, low warpage, etc. The present invention is suitable for injection molding automobile members, such as instrument panels, etc., and is also suitable for injection molding household appliance articles, such as air conditioners, washing machines, etc.
Description
Technical field
The present invention relates to a kind of mineral/whisker reinforced polypropylene composition, can be used for automobile-used product, household electrical appliances product etc., belong to the polypropylene technology field.
Background technology
Polypropylene is as a kind of general-purpose plastics, it has characteristics such as processing characteristics is good, good mechanical property, chemical resistance, in plastics, occupy critical role, but when making engineering part, its intensity, rigidity and thermotolerance far can not meet the demands, and the polypropylene impact property is poor simultaneously, particularly low temperature impact properties is poor, molding shrinkage is big, and particularly aspect ratio is shunk shortcomings such as inhomogeneous during fiber reinforcement, and this has limited the application of polypropylene in engineering part.
European patent EP-A496625 discloses a kind of matrix material of high-crystallinity polypropylene, it reaches the purpose of high rigidity by adding 30% talcum powder, but this causes the shock strength of material to reduce, thereby limited the application of material, the clear 56-149318 of Japanese Patent JP and the clear 61-256920 of Japanese Patent JP, the flat 4-36092 of JP have introduced the method for preparing magnesium salt whisker simultaneously, Chinese patent CN1288860A discloses a kind of preparation method of novel magnesium salt whisker, at superpolymer, particularly the application in polypropylene does not all relate to it.
Summary of the invention
The purpose of this invention is to provide that a kind of to have high rigidity, high strength, shock resistance and shrinking percentage low, laterally vertically shrinking percentage is even, the mineral/whisker reinforced polypropylene composition of low warpage.
For realizing above purpose, technical scheme of the present invention provides a kind of composition of mineral/whisker reinforced polypropylene, it is characterized in that, it comprises that following materials of weight proportions makes:
Polypropylene 50～60
Mineral toughener 15～35
Whisker toughener 4-15
Plasticizing mother particle 15～30
PP grafting compatilizer 3-10
Oxidation inhibitor 0.2～0.8
Other auxiliary agent 0.2～2.5
Described polypropylene can be homo-polypropylene, Co-polypropylene, can be single also can be blended, its melting index is 5～25g/10min, tensile strength 〉=20Mpa.
Described mineral toughener can be mica, talcum powder, kaolin or lime carbonate, and its particle diameter is 25 μ m～50 μ m.
Described whisker toughener is a magnesium salt whisker, its length-to-diameter ratio L/D 〉=30, particle diameter≤1 μ m.
Described plasticizing mother particle is ethylene-octene copolymer (POE) rubber, and its melting index is 0.4～5g/10min.
Described PP grafting compatilizer is the oligopolymer of the graftomer of polypropylene and maleic anhydride, and its melting index is 40～100g/10min.
Described oxidation inhibitor is a kind of Hinered phenols antioxidant, can be four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
Described other auxiliary agent can be thermo-stabilizer, lubricant, anti UV agent or pigment.
Preparation method of the present invention is as follows:
(1) weighs raw material by proportioning;
(2) with mineral surface process coupling agent treatment, this coupling agent can be silane coupling agent homologue or titanate coupling agent homologue;
(3) with whisker surface process coupling agent treatment, this coupling agent can be silane coupling agent homologue or titanate coupling agent homologue;
(4) polypropylene, mineral toughener, plasticizing mother particle, PP grafting compatilizer, oxidation inhibitor, other auxiliary agent were placed high-speed mixer and mixing 2-3 minute together;
(5) added whisker toughener low speed mixing 1-2 minute;
(6) discharging;
(7) raw materials mixed is placed the dual-screw-stem machine extruding pelletization, the rotating speed of dual-screw-stem machine is 180-600 rev/min, and temperature is 170-240 ℃.
The present invention adopts polypropylene as matrix resin, by adopting the compound enhancement techniques of mineral/whisker, both solved that polypropylene is low as the rigidity of engineering part raw material, intensity difference, the not high defective of thermotolerance, simultaneously by this compound enhancement techniques, in conjunction with plasticizing mother particle, the shock strength of material is improved greatly, enlarged the Application Areas of polypropylene as the engineering product, simultaneously, the compound enhancing of mineral/whisker, solved polypropylene articles size instability, horizontal, the vertical uneven defective of shrinking percentage.
Advantage of the present invention is that mineral/whisker reinforced polypropylene has high strength, high rigidity, and shock resistance, fire-retardant, dimensional stabilizing are suitable for all kinds of automobile-used, household electrical appliances engineering plastics spares of injection molding.
Specific embodiments
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment 1-4:
Blend with Co-polypropylene and homo-polypropylene is a basestocks, is toughener with talcum powder/magnesium salt whisker, and PP-g-MAH is a compatilizer, and the POE rubber master batch is a toughner, and its weight proportion is listed in the table 1,
Table one: the weight proportion of mineral/whisker reinforced polypropylene composition component
Preparation method of the present invention is as follows:
(1) talcum powder process coupling agent treatment;
(2) with magnesium salt whisker surface process coupling agent treatment;
(3) will gather polypropylene, Co-polypropylene, talcum powder, POE plasticizing mother particle, PP grafting compatilizer, antioxidant 1010 and place high-speed mixer and mixing together 3 minutes;
(4) added whisker magnesium salt whisker low speed mixing 1 minute;
(5) discharging;
(6) raw materials mixed is placed the dual-screw-stem machine extruding pelletization, the rotating speed of dual-screw-stem machine is 200 rev/mins, and the twin screw complete processing is listed in the table 2:
Table two: twin screw is extruded complete processing
The pellet dry injection is become the standard batten, test performance, performance such as table 3:
Table three: mineral/whisker reinforced polypropylene composition properties test comparison
Comparative example 5-6:
Contrast different amount of talc, other component changes, and its proportioning is listed in table 4, and other operation is identical with embodiment 1, and test performance is listed in table 5:
Table four: the weight proportion of mineral Reinforced Polypropylene composition
The pellet dry injection is become the standard batten, test performance, performance is as showing:
Table five: mineral Reinforced Polypropylene composition properties test comparison
Claims (9)
1, a kind of mineral/whisker reinforced polypropylene composition is characterized in that, it comprises that following materials of weight proportions makes:
Polypropylene 50～60
Mineral toughener 15～35
Whisker toughener 4-15
Plasticizing mother particle 15～30
PP grafting compatilizer 3-10
Oxidation inhibitor 0.2～0.8
Other auxiliary agent 0.2～2.5
2, mineral according to claim 1/whisker reinforced polypropylene composition is characterized in that, described polypropylene can be homo-polypropylene, Co-polypropylene, can be single also can be blended, its melting index is 5～25g/10min, tensile strength 〉=20Mpa.
3, mineral according to claim 1/whisker reinforced polypropylene composition is characterized in that, the mineral toughener can be mica, talcum powder, kaolin or lime carbonate, and its particle diameter is 25 μ m～50 μ m.
4, mineral according to claim 1/whisker reinforced polypropylene composition is characterized in that, the whisker toughener is a magnesium salt whisker, its length-to-diameter ratio L/D 〉=30, particle diameter≤1 μ m.
5, mineral according to claim 1/whisker reinforced polypropylene composition is characterized in that, plasticizing mother particle is ethylene-octene copolymer (POE) rubber, and its melting index is 0.4～5g/10min.
6. mineral according to claim 1/whisker reinforced polypropylene composition is characterized in that, PP grafting compatilizer is the oligopolymer of the graftomer of polypropylene and maleic anhydride, and its melting index is 40～100g/10min.
7. mineral according to claim 1/whisker reinforced polypropylene composition is characterized in that, oxidation inhibitor is a kind of Hinered phenols antioxidant, can be four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters.
8. mineral according to claim 1/whisker reinforced polypropylene composition is characterized in that: according to the goods needs, other auxiliary agent can be thermo-stabilizer, lubricant, anti UV agent or pigment.
9. a kind of mineral according to claim 1/whisker reinforced polypropylene preparation of compositions method, its method is as follows:
(1) weighs raw material by proportioning;
(2) with mineral surface process coupling agent treatment, this coupling agent can be silane coupling agent homologue or titanate coupling agent homologue;
(3) with whisker surface process coupling agent treatment, this coupling agent can be silane coupling agent homologue or titanate coupling agent homologue;
(4) polypropylene, mineral toughener, plasticizing mother particle, PP grafting compatilizer, other auxiliary agent of oxidation inhibitor were placed high-speed mixer and mixing 2-3 minute together;
(5) added whisker toughener low speed mixing 1-2 minute;
(6) discharging;
(5) raw materials mixed is placed the dual-screw-stem machine extruding pelletization, the rotating speed of dual-screw-stem machine is 180-600 rev/min, and temperature is 170-240 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031159222A CN1300236C (en) | 2003-03-21 | 2003-03-21 | Mineral/ whisker reinforced polypropylene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031159222A CN1300236C (en) | 2003-03-21 | 2003-03-21 | Mineral/ whisker reinforced polypropylene composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1532221A CN1532221A (en) | 2004-09-29 |
| CN1300236C true CN1300236C (en) | 2007-02-14 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031159222A Expired - Lifetime CN1300236C (en) | 2003-03-21 | 2003-03-21 | Mineral/ whisker reinforced polypropylene composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1300236C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383184C (en) * | 2004-11-30 | 2008-04-23 | 绵阳市仁智奇微新材料有限公司 | Method for preparing modified polyolefin mother material for buried drain pipe using whisker |
| CN1313529C (en) * | 2005-05-31 | 2007-05-02 | 漯河市森鑫塑业有限公司 | Polypropylene composition and process for preparing modified polypropylene pipes by using same |
| 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 |
| CN101838423B (en) * | 2010-06-10 | 2012-07-04 | 南京聚隆科技股份有限公司 | Modified polypropylene material for thin-wall bumper and preparation method thereof |
| CN103113662A (en) * | 2011-11-17 | 2013-05-22 | 上海金发科技发展有限公司 | Low-odor ultrahigh-toughness polypropylene compound and preparation method thereof |
| CN103571059B (en) * | 2012-08-02 | 2017-12-22 | 辽宁辽杰科技有限公司 | A kind of PP composite material and its production and use |
| CN103497391A (en) * | 2013-10-22 | 2014-01-08 | 四川万润非金属矿物材料有限公司 | Calcium sulfate crystal whisker master batch and method for preparing same |
| CN104788804A (en) * | 2014-01-17 | 2015-07-22 | 汉达精密电子(昆山)有限公司 | Polypropylene resin composition and product thereof |
| CN105017638A (en) * | 2014-04-18 | 2015-11-04 | 汉达精密电子(昆山)有限公司 | High-creep-resistant polypropylene glass fiber reinforced material and product thereof |
| CN104312006A (en) * | 2014-09-24 | 2015-01-28 | 雪龙集团股份有限公司 | Reinforced wear-resistant polypropylene composite material |
| CN105111585A (en) * | 2015-09-10 | 2015-12-02 | 常州塑金高分子科技有限公司 | Polypropylene washing machine powder filling granules for recovery and preparation method thereof |
| CN109337199A (en) * | 2018-09-14 | 2019-02-15 | 君恒咨询有限公司 | A kind of polypropylene building mould additive and preparation method thereof |
| CN110092926A (en) * | 2019-06-11 | 2019-08-06 | 吕智 | The preparation method and applications of alkali magnesium sulfate crystal whisker master batch |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0496625A2 (en) * | 1991-01-25 | 1992-07-29 | Mitsubishi Chemical Corporation | Thermoplastic polymer composition |
| US6150442A (en) * | 1998-12-31 | 2000-11-21 | Ferro Corporation | Flame retardant polypropylene composition |
| CN1328084A (en) * | 2001-07-03 | 2001-12-26 | 成都市华硕实业有限公司 | Composite of microfibre, superfine powder and polypropylene |
-
2003
- 2003-03-21 CN CNB031159222A patent/CN1300236C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0496625A2 (en) * | 1991-01-25 | 1992-07-29 | Mitsubishi Chemical Corporation | Thermoplastic polymer composition |
| US6150442A (en) * | 1998-12-31 | 2000-11-21 | Ferro Corporation | Flame retardant polypropylene composition |
| CN1328084A (en) * | 2001-07-03 | 2001-12-26 | 成都市华硕实业有限公司 | Composite of microfibre, superfine powder and polypropylene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1532221A (en) | 2004-09-29 |
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Effective date of registration: 20190419 Address after: Building-1, 2399 Shengang Road, Songjiang District, Shanghai, 201612 Patentee after: SHANGHAI WOSHI INDUSTRIAL Co.,Ltd. Address before: 2010 108 No. 5000 Yuanjiang Road, Shanghai Patentee before: SHANGHAI WORTH GARDEN PRODUCTS Co.,Ltd. |
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