CN1927932A - Modified polypropylene, preparing process and application thereof - Google Patents
Modified polypropylene, preparing process and application thereof Download PDFInfo
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- CN1927932A CN1927932A CN 200510029555 CN200510029555A CN1927932A CN 1927932 A CN1927932 A CN 1927932A CN 200510029555 CN200510029555 CN 200510029555 CN 200510029555 A CN200510029555 A CN 200510029555A CN 1927932 A CN1927932 A CN 1927932A
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- polypropylene
- modified polypropene
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Abstract
The present invention provides one kind of modified polypropylene material prepared through adding certain amount of toughening agent, intensifier, heat stabilizer, light stabilizer and processing aid into the mixture of high shock resistance polypropylene and high flowability polypropylene. The modified polypropylene material has high shock resistance, very low shrinkage, certain rigidity and excellent processing performance, and may be used in household appliance, automobile ornament, electric tool part and other plastic product with high size stability requirement.
Description
Technical field
The present invention relates to a kind of modified polypropene and its production and application, relate in particular to modified polypropene of the ultralow shrinking percentage of a kind of high impact-resistant and its production and application.
Background technology
Polypropylene is a kind of broad-spectrum general-purpose plastics, is polymerized by propylene monomer, and english abbreviation is PP, and its fusing point is 165～175 ℃, belongs to the hemicrystalline plastics; In the modified plastics field, especially for filling under the condition with higher, its rigidity and toughness are difficult to improve simultaneously; In addition, usually the shrinking percentage of the virgin pp resin of injection grade is 1.6～1.8%, and obviously greater than other amorphism materials such as HIPS, ABS, PC, its shrinking percentage is generally 0.6%.
Acrylic resin mainly is divided into copolymerization, homopolymerization two big classes according to polymerization process and molecule segment spread pattern.Copolymerization PP impelling strength is higher, but rigidity is lower, usually Izod notched Izod impact strength 5.0～50.0KJ/m
2, modulus in flexure 700～1500MPa; And homopolymerization PP impelling strength is relatively poor, and rigidity is then higher, usually Izod notched Izod impact strength 3.0～5.0KJ/m
2, modulus in flexure 1400～2200MPa.
Common PP resin is difficult to satisfy the application requiring of various industries, the range of application of modified polypropylene material is very extensive, but as automobile, industries such as household electrical appliances, state of the art to MODIFIED PP requires to improve day by day, some higher requirements are also proposed simultaneously, on the mechanical property of material, even to reach or near the level of engineering plastics, and in modified polypropylene material through engineering approaches process, one of the most scabrous problem, promptly guaranteeing that material has high toughness, in the time of good outward appearance and excellent processing characteristics, shrinking percentage is difficult to accomplish the level as engineering plastics such as ABS.
Under common method of modifying, the shrinking percentage such as the table one of modified polypropylene material.
The different method of modifying of table one are to the influence of polypropylene shrinking percentage
| Method of modifying | Weighting material | General shrinking percentage % (amount of filling 40%-0%) | Contribution to shrinking percentage | |
| The mineral powder is filled | Spherical | Barium sulfate, lime carbonate etc. | 1.1-1.6％ | The tool isotropy, according to the adding proportion difference, improvement effect is little, and outward appearance is better |
| Sheet | Talcum powder etc. | 0.8-1.6％ | The tool anisotropy, the transverse and longitudinal difference is little, and improvement effect is general, and outward appearance is better | |
| Needle-like | Wollastonite etc. | 0.6-1.6％ | Have anisotropy, according to the adding proportion difference, the good outward appearance of improvement effect is relatively poor | |
| Whisker is filled | Needle-like | Magnesium salt whisker etc. | 0.6-1.6％ | |
| Four jiaos | Zinc salt whisker etc. | 0.6-1.6％ | Isotropy, very good according to the different improvement effects of adding proportion, outward appearance is relatively poor | |
| Fiber filled | Glass fibre etc. | 0.3/0.9-1.6/1.6％ | Anisotropy, laterally vertically difference is very big, and outward appearance is relatively poor | |
| Blend rubber | EPDM, POE etc. | 1.0-1.6％ | Isotropy, improvement effect is better, and outward appearance is better | |
Technology contents
Technical problem to be solved by this invention is to provide a kind of modified polypropene and its production and application, to solve in the prior art rigidity, shock resistance and the shrinking percentage defectives such as weighing apparatus that have much difficulty in healing.
The present invention at first provides a kind of modified polypropene, and this polypropylene comprises following components in weight percentage:
Toughner 0～70%
Toughener 10～30%
Thermo-stabilizer 0.2～1.0%
Photostabilizer 0.1～1.0%
Processing aid 0.1～1.0%
The polypropylene surplus;
Wherein polypropylene is high impact-resistant Co-polypropylene and the high workability Co-polypropylene mixture according to weight ratio 1: 0.25-4.
Described high workability copolymerization PP presses the non-enhancing analog thermoplastic of ISO plastic testing standard, and melting index 〉=30g/10min (230 ℃, 2.16kg); Described high impact-resistant copolymerization PP presses the non-enhancing analog thermoplastic of ISO plastic testing standard, cantilever amount notched Izod impact strength 〉=35KJ/m
2(23 ℃).
Wherein said toughner is one or more in ethylene-propylene-octene terpolymer (POE), ethylene-propylene-butadiene terpolymer (EPDM), styrene-butadiene copolymer (SBS), hydrogenant ethylene-butadiene-styrene multipolymer (SEBS), the propylene-ethylene graft copolymer; The adding of toughner can improve the toughness of system greatly, also has the effect of shrinking percentage properties-correcting agent simultaneously, can adopt the commercially available prod, and the preferred trade mark is HIFAX 7271;
Described toughener is platy talc or talcum master batch, and particle diameter is distributed in 1.0 μ m～4.0 μ m more than 95%;
Described thermo-stabilizer is one or more in the mixture of phenols, phosphorous acid esters, monothioester class; Wherein phenols is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester or 2, and one or both in 6-two (1-phenyl) ethyl-4-nonylphenol, phosphorous acid esters are three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester; The monothioester class is one or both in two (18) esters of thio-2 acid or the thio-2 acid 2 stearyl ester, and its commodity are called Irganox, Naugard, Hostanox, Cyanox etc., and the preferred trade mark is the Irganox 1010 of Ciba company.Thermo-stabilizer can improve the heat aging property of material in processing and use,
Described photostabilizer can improve material light aging resisting property in use, can be hindered amines or UV light absorber; Wherein hindered amines can be two (2,2,6,6-four bases-4-piperidyl) sebate, poly--[6-[(1,1,3, the 3-tetramethyl butyl)-imino-]-1,3,5-triazines-2,4-two bases]-[2-(2,2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6,6-tetramethyl-piperidyl)-imino-]] in one or more; UV light absorber is benzotriazole category 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole, benzophenone (one or more in Octabenzone, the 2-hydroxyl-4-dodecyloxy benzophenone; The preferred photostabilizer trade mark is TINUV 770 (commercially available prod).
In low molecule ester class of described processing aid or the amides one or more; Wherein low molecule ester class is one or more in stearic acid, metallic soap (Cast or Znst) or the stearic acid complex ester, and amides is an erucicamide.
The present invention also provides preparation method of modified polypropylene, and the toughner of polypropylene and 40-60%, talcum powder, thermo-stabilizer, photostabilizer, processing aid as for high mixer, are mixed; The toughner that will remain 40-60% again adds high mixer, mixes; Melting mixing, extruding pelletization under 190～230 ℃ temperature then, promptly.
The modified polypropene that the present invention obtains can be applicable to substitute low-shrinkage plastics such as HIPS, ABS, and can use in the injecting products of having relatively high expectations with household electrical appliances parts, automobile decoration piece, power tool parts or to dimensional stability.
Adopt iso standard to detect to the resulting modified polypropene of the present invention.Test sample, by CJ80NC type injection moulding machine 200～230 ℃ of following injection mouldings.
The testing method of physical and mechanical properties:
1) density
Press ISO1183
2) tensile strength
Press the ISO527 test
Speed: 50mm/min
3) cantilever notched Izod impact strength
Press the ISO180 test
Impact experiment machine model: XJU-22
4) melt flow rate (MFR)
Press the ISO1133 test
Condition: 230 ℃/2.16KG
5) modulus in flexure
Press the ISO178 test
Speed: 2mm/min
6) shrinking percentage
Press the GB15585 method, the molding shrinkage method of calculation are as follows:
Concrete testing method: use 127 * 12.7 * 3.2mm injection mold, and use the same model injection moulding machine, guarantee that identical Shooting Technique prepares exemplar, exemplar is at 23 ± 2 ℃, after regulating 24 ± 2h under the condition of humidity 50 ± 2%, measurement is as the criterion with batten gate end length far away, is accurate to 0.02mm, test at least five exemplars, average and calculate.
Adopt the aforesaid method result to show, said high impact-resistant, the every performance index of ultralow shrinking percentage all meet or exceed predetermined requirement, solved rigidity of material toughness and be difficult to the equilibrated shortcoming, solved the requirement of automobile industry simultaneously high Brinell hardness and low smell material.Material is at 23 ℃, and when the modulus in flexure under the humidity 50% can reach 1450MPa, the socle girder notched Izod impact strength still can reach 45KJ/m
2More than; Molding shrinkage reaches 0.4%, has reached part engineering plastics degree on shock strength and molding shrinkage fully.
Concrete embodiment
Adopt the major equipment of producing product to have:
High-speed mixer: 650～1300 rev/mins of rotating speeds
Twin screw extruder screw speed 250-450rpm, 190～230 ℃ of barrel zone temperatures
Tank water temperature: 20～55 ℃
Dicing machine rotating speed: 600～1000rpm
Embodiment 1
| Title | Consumption |
| The high impact-resistant Co-polypropylene | 7.92％ |
| The high workability Co-polypropylene | 31.68％ |
| SBS | 10％ |
| Platy talc | 20％ |
| Ethylene-propylene-diene terpolymer | 30％ |
| Thiophenols | 0.2％ |
| Benzotriazole | 0.1％ |
| Erucicamide | 0.1％ |
Product to embodiment 1 detects, its result such as table 1:
Table 1
| Performance | Unit | Numerical value |
| Density | g/cm 3 | 1.024 |
| Tensile strength | MPa | 15.6 |
| The socle girder notched Izod impact strength | KJ/m 2 | ≥48 |
| Modulus in flexure | MPa | 1459 |
| Melting index | g/10min | 11 |
| Molding shrinkage | ％ | 0.40 |
Embodiment 2
| Title | Consumption |
| The high impact-resistant Co-polypropylene | 31.68％ |
| The high workability Co-polypropylene | 7.92％ |
| POE | 5％ |
| The talcum master batch | 20％ |
| Ethylene-propylene-octene terpolymer | 35％ |
| Sulfo-amine | 0.2％ |
| Poly--[6-[(1,1,3,3-tetramethyl butyl)-imino-]-1,3,5-triazines-2, the 4-dimethyl] | 0.1％ |
| The stearic acid complex ester | 0.1％ |
Product to embodiment 2 detects, its result such as table 2:
Table 2
| Performance | Unit | Embodiment 1 |
| Density | g/cm 3 | 1.031 |
| Tensile strength | MPa | 16.2 |
| The socle girder notched Izod impact strength | KJ/m 2 | ≥41.9 |
| Modulus in flexure | MPa | 1604 |
| Melting index | g/10min | 12 |
| Molding shrinkage | ％ | 0.44 |
Claims (8)
1. modified polypropene is characterized in that this polypropylene comprises following components in weight percentage:
Toughner 0～70%
Toughener 10～30%
Thermo-stabilizer 0.2～1.0%
Photostabilizer 0.1～1.0%
Processing aid 0.1～1.0%
The polypropylene surplus;
Wherein polypropylene is high impact-resistant Co-polypropylene and the high workability Co-polypropylene mixture according to weight ratio 1: 0.25-4.
2. modified polypropene according to claim 1 is characterized in that described toughner is one or more in ethylene-propylene-octene terpolymer, ethylene-propylene-butadiene terpolymer, styrene-butadiene copolymer, hydrogenant ethylene-butadiene-styrene multipolymer, the propylene-ethylene graft copolymer.
3. modified polypropene according to claim 1 is characterized in that described toughener is platy talc or talcum master batch.
4. modified polypropene according to claim 1 is characterized in that described thermo-stabilizer is one or more in the mixture of phenols, phosphorous acid esters, monothioester class; Wherein phenols is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester or 2, and one or both in 6-two (1-phenyl) ethyl-4-nonylphenol, phosphorous acid esters are three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester; The monothioester class is one or both in two (18) esters of thio-2 acid or the thio-2 acid 2 stearyl ester.
5. modified polypropene according to claim 1 is characterized in that described photostabilizer is hindered amines or UV light absorber; Wherein hindered amines is two (2,2,6,6-four bases-4-piperidyl) sebate, poly--[6-[(1,1,3, the 3-tetramethyl butyl)-imino-]-1,3,5-triazines-2,4-two bases]-[2-(2,2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6,6-tetramethyl-piperidyl)-imino-]] in one or more; UV light absorber is benzotriazole category 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole, benzophenone (one or more in Octabenzone or 2-hydroxyl-4-dodecyloxy benzophenone.
6. modified polypropene according to claim 1 is characterized in that described processing aid is one or more in low molecule ester class or the amides; Wherein low molecule ester class is one or more in stearic acid, metallic soap or the stearic acid complex ester, and amides is an erucicamide.
7. method for preparing each described modified polypropene of claim 1-6 is characterized in that the toughner of polypropylene and 40-60%, talcum powder, thermo-stabilizer, photostabilizer, processing aid mixing as for high mixer; The toughner that will remain 40-60% again adds high mixer, mixes; Melting mixing, extruding pelletization under 190～230 ℃ temperature then, promptly.
One kind as each described modified polypropene of claim 1-6 with household electrical appliances parts, automobile decoration piece, power tool parts or injecting products that dimensional stability is had relatively high expectations in application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510029555 CN1927932A (en) | 2005-09-09 | 2005-09-09 | Modified polypropylene, preparing process and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510029555 CN1927932A (en) | 2005-09-09 | 2005-09-09 | Modified polypropylene, preparing process and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1927932A true CN1927932A (en) | 2007-03-14 |
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ID=37858080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| CN 200510029555 Pending CN1927932A (en) | 2005-09-09 | 2005-09-09 | Modified polypropylene, preparing process and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952342A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Low-shrinkage polypropylene composition and preparation method thereof |
| CN103571043A (en) * | 2012-08-01 | 2014-02-12 | 玉柴重工（常州）有限公司 | Anti-ageing polypropylene for non-bearing accessories of engineering machinery and preparation method of anti-ageing polypropylene |
| CN106009313A (en) * | 2016-07-14 | 2016-10-12 | 武汉顺威赛特工程塑料有限公司 | ABS-substituting high-toughness PP composite material and preparation method thereof |
| CN109777025A (en) * | 2018-12-25 | 2019-05-21 | 浙江普利特新材料有限公司 | A kind of high rigidity, high tenacity, low-shrink polypropylene composite material and preparation method |
| CN110540711A (en) * | 2018-05-29 | 2019-12-06 | 合肥杰事杰新材料股份有限公司 | low-after-shrinkage polypropylene material and preparation method thereof |
| CN110903543A (en) * | 2019-10-14 | 2020-03-24 | 中广核俊尔（上海）新材料有限公司 | Polypropylene material for LFT-D-IM technology and preparation method thereof |
-
2005
- 2005-09-09 CN CN 200510029555 patent/CN1927932A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952342A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Low-shrinkage polypropylene composition and preparation method thereof |
| CN102952342B (en) * | 2011-08-30 | 2015-05-20 | 中国石油化工股份有限公司 | Low-shrinkage polypropylene composition and preparation method thereof |
| CN103571043A (en) * | 2012-08-01 | 2014-02-12 | 玉柴重工（常州）有限公司 | Anti-ageing polypropylene for non-bearing accessories of engineering machinery and preparation method of anti-ageing polypropylene |
| CN103571043B (en) * | 2012-08-01 | 2016-03-30 | 玉柴重工（常州）有限公司 | For the ageing resistance polypropylene and preparation method thereof of engineering machinery non-bearing gadget |
| CN106009313A (en) * | 2016-07-14 | 2016-10-12 | 武汉顺威赛特工程塑料有限公司 | ABS-substituting high-toughness PP composite material and preparation method thereof |
| CN110540711A (en) * | 2018-05-29 | 2019-12-06 | 合肥杰事杰新材料股份有限公司 | low-after-shrinkage polypropylene material and preparation method thereof |
| CN110540711B (en) * | 2018-05-29 | 2022-05-10 | 合肥杰事杰新材料股份有限公司 | Low-after-shrinkage polypropylene material and preparation method thereof |
| CN109777025A (en) * | 2018-12-25 | 2019-05-21 | 浙江普利特新材料有限公司 | A kind of high rigidity, high tenacity, low-shrink polypropylene composite material and preparation method |
| CN110903543A (en) * | 2019-10-14 | 2020-03-24 | 中广核俊尔（上海）新材料有限公司 | Polypropylene material for LFT-D-IM technology and preparation method thereof |
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Open date: 20070314 |