CN102108146A - Polyolefin thermoplastic elastomer (TPE) composition and preparation method thereof - Google Patents
Polyolefin thermoplastic elastomer (TPE) composition and preparation method thereof Download PDFInfo
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- CN102108146A CN102108146A CN 201010137503 CN201010137503A CN102108146A CN 102108146 A CN102108146 A CN 102108146A CN 201010137503 CN201010137503 CN 201010137503 CN 201010137503 A CN201010137503 A CN 201010137503A CN 102108146 A CN102108146 A CN 102108146A
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Abstract
The invention discloses a polyolefin thermoplastic elastomer (TPE) composition and a preparation method thereof. The composition comprises the following components in percentage by weight: 40%-80% of polyethylene (PE) resin, 10%-35% of propylene-ethylene copolymer and 10%-25% of ethylene-vinyl acetate (EVA) copolymer, wherein, the PE resin is prepared from high-density PE granules, and the weight-average molecular weight of the PE resin is 100,000-1,000,000; the propylene-ethylene copolymer is composed of copolymer particles which are produced by utilizing a metallocene catalyst and a solution polymerization process, and the content of the ethylene in the propylene-ethylene copolymer is 12-20wt%; and the content of the vinyl acetate in the EVA copolymer is 15-30wt%. The polyolefin TPE composition prepared by the method has the characteristics of ultrahigh fluidity, low-temperature self-adhesion property and simple and easy preparation process, and can meet the requirements for high-speed extrusion and environmental conservation, thus the composition can be widely applied to the field of manufacturing cars and household appliances.
Description
Technical field
The present invention relates to a kind of composition and method of making the same of Thermoplastic Elastomer, Olefinic, especially a kind of Thermoplastic Elastomer, Olefinic composition and method of making the same with super-high fluidity and low temperature from cementability
Background technology
(Thermoplastic elastomer is the family macromolecule material of physicals between rubber and plastics TPE) to thermoplastic elastomer, and it had both had the elasticity of rubber, had the workability of plastics again.These characteristics have just been found when nineteen twenty-six Waldo Semon research PVC.Along with the progress of copolymerization techniques such as blending technology and block, grafting, investigator all over the world and company have succeeded in developing the macromolecular material that multiclass has this specific character again in succession, are widely used in fields such as automobile, electric, building, medical treatment.Along with the development of new technology, promoted continuing to optimize and promoting of TPE performance, Application Areas is constantly expanded, and especially automobile and medical field are sought-after; Owing to the raising of people's Environmental awareness, salvage material becomes an important factor of selection in addition, and global depleted PVC becomes the major issue of environmental pollution, and external restriction uses the PVC cry surging day by day, has also promoted TPE to consume quick the growth.Suitability for industrialized production TPE mainly is divided into following a few class at present: styrenic (TPS), olefines (TPO), polyvinyl chloride-base (TPVC), ammonia ester class (TPU), polyester (TPEE), amides (TPAE), organic fluorine class (TPF), diene class (TPB, TPI) etc.
Polyolefins thermoplastic elastomer (TPO) is made of rubber and polyolefine, usually rubber components is terpolymer EP rubber (EPDM), paracril (NBR) and isoprene-isobutylene rubber and adopts metallocene catalyst synthesizing ethylene-octene copolymer, and polyolefin component is mainly polypropylene (PP) and polyethylene (PE).The nineties in 20th century, metallocene catalysis system was used for rubber industry production, became one of the most outstanding progress of synthetic rubber.Metallocene catalysis ethylene-propylene rubber(EPR) is compared the relative molecular weight narrowly distributing with product with traditional ethylene-propylene rubber(EPR); The pure color of product is bright, paradigmatic structure is even; Especially can regulate the composition of ethene, propylene and diolefine exactly by changing the metallocene structure, in very large range regulate and control the microtexture of polymkeric substance, have products novel chain structure, different purposes thereby synthesize.From beginning suitability for industrialized production in 1997 so far, global metallocene catalysis ethylene-propylene rubber(EPR) production capacity reaches more than the 200kt/a.Metallocene catalysis synthetic hydrogenated nitrile-butadiene rubber price is synthetic more much lower than traditional method; These metallocene synthetic rubber performances are special, and synthetic based on this TPO has better performance.External in recent years many novel high-performance TPO as cooperative development TPO mixture and alloy new technologies such as E.I.Du Pont Company, DOW chemistry, based on metallocene polyolefin elastomers, and promote compounded technology of new generation in conjunction with the metallocene technology in the world.The thermoplastic elastomer of using this technology can bear comparatively high temps, and has higher melt intensity, excellent machinability and preferable end product use properties.TPO has become the main rubber-plastics material of automobile and field of household appliances at present, and wherein consumption accounts for more than 75% of ultimate production on the automobile, is a fastest-rising kind in the thermoplastic elastomer (TPE).
In extrusion, usually to run into when extruded velocity surpasses a certain threshold value, the extrudate surface quality worsens, and tarnishes gradually, the shark skin shape occurs, and then the surface becomes uneven, and curl, ring shape or the like are melt fracture.Physics, optical property and visual appearance that it has had a strong impact on goods have limited production efficiency, thereby are the major issues in the actual production.The method of industrial elimination melt fracture may be also inequality to differing materials, and have following several substantially: 1. when polymer melt was extruded, the fracture phenomena of Chu Xianing was a shark skin at first, and the formation of shark skin is relevant with the size of mouthful mould.So, when die design, note utilizing the influence that the diameter, length-to-diameter ratio etc. of mouthful mould form shark skin as far as possible.2. select special mouth mold materials, as steel alloy or other material, the counterpart mold materials carries out special processing etc.3. select processing aid (external lubricant, filler) according to polymkeric substance, change the flow boundary condition, can slow down or eliminate melt fracture.4. according to the temperature effective of melt fracture, improve or reduce temperature.5. polymkeric substance is carried out flow modifier, improve the flowability of material, promptly have higher melt flow rate (MFR).Particular case wants the kind of conjugated polymer to determine.
Summary of the invention
First technical problem to be solved by this invention is to provide a kind of composition with low temperature from the Thermoplastic Elastomer, Olefinic of cementability at the above-mentioned state of the art.
Second technical problem to be solved by this invention provides a kind of preparation method with low temperature from the TPO composition for thermoplastic elastomer of cementability.
The technical scheme that the present invention is adopted for above-mentioned first technical problem of solution is: a kind of composition of Thermoplastic Elastomer, Olefinic is characterized in that described composition is to be mixed by following mass percent by following component:
Polyvinyl resin: 40%～80%;
Propylene-ethylene copolymers: 10%～35%;
Ethylene-vinyl acetate copolymer: 10%～25%.
As improvement, the high density polyethylene(HDPE) particle of described polyvinyl resin for adopting low-pressure process to produce, its weight-average molecular weight is 100000～1000000.
As preferably, described propylene-ethylene copolymers is the copolymer pellet that adopts metallocene catalyst and novel solutions polymerization technique to produce, the content of therein ethylene is weight percentage 12～20%, its melt flow index is 50～350g/10min (press ASTM D1238 standard method test, test condition is 230 ℃ of temperature, load 2.16kg).
As preferably, the content of vinyl acetate between to for plastic is weight percentage 15～30% in the described ethylene-vinyl acetate copolymer, the melt flow index of described ethylene-vinyl acetate copolymer is 15～40g/10min (press ASTMD1238 standard method test, test condition is 230 ℃ of temperature, load 2.16kg).
The present invention for above-mentioned second technical scheme that technical problem adopted of solution is: a kind of preparation of compositions method of Thermoplastic Elastomer, Olefinic is characterized in that may further comprise the steps:
1) each component is prepared burden by following weight percent:
Polyethylene: 40～80%;
Propylene-ethylene copolymers: 10～35%;
Ethylene-vinyl acetate copolymer: 10～25%.
2) material that will prepare mixes the back discharging in mixing machine, adopts the forcing machine granulation.
Described polyvinyl resin is the high density polyethylene(HDPE) particle that low-pressure process is produced, and its weight-average molecular weight is 100000～1000000;
Described propylene-ethylene copolymers is the particle that utilizes metallocene catalyst and solution polymerization process to produce, therein ethylene content 12～20% (weight percent), melt flow index is 50～350g/10min (press ASTM D1238 standard method test, test condition is 230 ℃ of temperature, load 2.16kg);
The content of vinyl acetate between to for plastic is 15～30% (weight percents) in the described ethylene-vinyl acetate copolymer, and melt flow index is 15～40g/10min (press ASTM D1238 standard method test, test condition is 230 ℃ of temperature, load 2.16kg).
Compared with prior art, advantage of the present invention is: the prepared Thermoplastic Elastomer, Olefinic composition of the present invention had both had the flowability of superelevation, promptly has higher melt flow rate (MFR), can satisfy the needs of extruding at a high speed, avoid in extrusion, occurring the phenomenon of shark skin shape melt fracture, and material surface temperature (being that material is indeformable) in 80 ℃～110 ℃ scope has again from cementability, preparation technology is simple, easy to operate, this material meets environmental protection requirement simultaneously, can be widely used in the manufacturing field of automobile and field of household appliances.
Embodiment
Come by the following examples to be further described, but the present invention is not confined to these embodiment.Material prescription in embodiment and the comparative example all is weight percentage.
Wherein the flowability of material characterizes with the melt flow rate (MFR) of material, and according to the test of ASTM D1238 melt index testing method, test condition is 230 ℃ of temperature, load 2.16kg;
Material is from the characterizing method of cementability: by proportioning with each component uniform mixing, in forcing machine, carry out granulation, particle is extruded into the circular monofilaments that diameter is 0.5mm by single screw extrusion machine, then monofilament is woven into the reticulated structure of single-warp single-abb, put in the homothermic baking oven, heat and from baking oven, take out after 3 minutes, naturally cool to room temperature, observe the bonding situation of reticulated structure tie up point, with A, B, C, the qualitative sign of D classification, A represents that cementability is fine, and B represents that cementability is better, C represents that cementability is general, and D represents not bonding.
Embodiment 1
50% polyethylene, 25% propylene-ethylene copolymers, 25% ethylene-vinyl acetate copolymer are mixed in mixing machine, in forcing machine, carrying out granulation.The melt flow rate (MFR) of test material and from cementability, test result sees Table 1.
Embodiment 2
50% polyethylene, 30% propylene-ethylene copolymers, 20% ethylene-vinyl acetate copolymer are mixed in mixing machine, in forcing machine, carrying out granulation.The melt flow rate (MFR) of test material and from cementability, test result sees Table 1.
Embodiment 3
50% polyethylene, 35% propylene-ethylene copolymers, 15% ethylene-vinyl acetate copolymer are mixed in mixing machine, in forcing machine, carrying out granulation.The melt flow rate (MFR) of test material and from cementability, test result sees Table 1.
Embodiment 4
60% polyethylene, 20% propylene-ethylene copolymers, 20% ethylene-vinyl acetate copolymer are mixed in mixing machine, in forcing machine, carrying out granulation.The melt flow rate (MFR) of test material and from cementability, test result sees Table 1.
Embodiment 5
60% polyethylene, 25% propylene-ethylene copolymers, 15% ethylene-vinyl acetate copolymer are mixed in mixing machine, in forcing machine, carrying out granulation.The melt flow rate (MFR) of test material and from cementability, test result sees Table 1.
Embodiment 6
60% polyethylene, 30% propylene-ethylene copolymers, 10% ethylene-vinyl acetate copolymer are mixed in mixing machine, in forcing machine, carrying out granulation.The melt flow rate (MFR) of test material and from cementability, test result sees Table 1.
Embodiment 7
70% polyethylene, 10% propylene-ethylene copolymers, 20% ethylene-vinyl acetate copolymer are mixed in mixing machine, in forcing machine, carrying out granulation.The melt flow rate (MFR) of test material and from cementability, test result sees Table 1.
Embodiment 8
70% polyethylene, 15% propylene-ethylene copolymers, 15% ethylene-vinyl acetate copolymer are mixed in mixing machine, in forcing machine, carrying out granulation.The melt flow rate (MFR) of test material and from cementability, test result sees Table 1.
Embodiment 9
75% polyethylene, 15% propylene-ethylene copolymers, 10% ethylene-vinyl acetate copolymer are mixed in mixing machine, in forcing machine, carrying out granulation.The melt flow rate (MFR) of test material and from cementability, test result sees Table 1.
Comparative Examples 1
100% polyethylene, 0% propylene-ethylene copolymers, 0% ethylene-vinyl acetate copolymer are mixed in mixing machine, in forcing machine, carrying out granulation.The melt flow rate (MFR) of test material and from cementability, test result sees Table 1.
Comparative Examples 2
70% polyethylene, 30% propylene-ethylene copolymers, 0% ethylene-vinyl acetate copolymer are mixed in mixing machine, in forcing machine, carrying out granulation.The melt flow rate (MFR) of test material and from cementability, test result sees Table 1.
Comparative Examples 3
60% polyethylene, 35% propylene-ethylene copolymers, 5% ethylene-vinyl acetate copolymer are mixed in mixing machine, in forcing machine, carrying out granulation.The melt flow rate (MFR) of test material and from cementability, test result sees Table 1.
Comparative Examples 4
85% polyethylene, 0% propylene-ethylene copolymers, 15% ethylene-vinyl acetate copolymer are mixed in mixing machine, in forcing machine, carrying out granulation.The melt flow rate (MFR) of test material and from cementability, test result sees Table 1.
The melt flow rate (MFR) of table 1 embodiment and Comparative Examples and from cementability
| Melt flow rate (MFR) (g/10min) | From cementability | |
| Embodiment 1 | 58.9 | A |
| Embodiment 2 | 634 | A |
| Embodiment 3 | 65.8 | B |
| Embodiment 4 | 43.5 | A |
| Embodiment 5 | 48.2 | B |
| Embodiment 6 | 53.4 | C |
| Embodiment 7 | 29.8 | A |
| Embodiment 8 | 32.3 | B |
| Embodiment 9 | 39.7 | C |
| Comparative Examples 1 | 9.6 | D |
| Comparative Examples 2 | 50.1 | D |
| Comparative Examples 3 | 57.6 | D |
| Comparative Examples 4 | 16.7 | B |
As can be seen from Table 1, when the content of ethylene-vinyl acetate copolymer more than or equal to 10% the time, matrix material reflects certain low temperature from cementability, as embodiment 1,2,3,4,5,6,7,8,9 and Comparative Examples 4, and along with its low temperature of increase of the content of ethylene-vinyl acetate copolymer is good more from cementability, when the content of ethylene-vinyl acetate copolymer less than 10% the time (as Comparative Examples 1,2,3), essentially no low temperature is from cementability; Contrast Comparative Examples 2 and embodiment 7,8 can find that ethylene-vinyl acetate copolymer is littler than propylene-ethylene copolymers to the flow contribution of property of matrix material, along with its flowability of increase of the content of propylene-ethylene copolymers is good more.This shows, adopt ethylene-vinyl acetate copolymer and the common modified poly ethylene of propylene-ethylene copolymers to prepare and not only have the flowability of superelevation but also the rubber/polythene thermoplastic elastomer of low temperature from the cementability characteristic arranged.
Claims (5)
1. the composition of a Thermoplastic Elastomer, Olefinic is characterized in that described composition is formed by the certain quality percentage mix by following component:
Polyvinyl resin: 40%～80%
Propylene-ethylene copolymers: 10%～35%
Ethylene-vinyl acetate copolymer: 10%～25%.
2. composition according to claim 1 is characterized in that the high density polyethylene(HDPE) particle of described polyvinyl resin for adopting low-pressure process to produce, and its weight-average molecular weight is 100000～1000000.
3. composition according to claim 1, it is characterized in that described propylene-ethylene copolymers is the copolymer pellet that adopts metallocene catalyst and solution polymerization process to produce, the content of therein ethylene is weight percentage 12～20%, and its melt flow index is 50～350g/10min.
4. composition according to claim 1 is characterized in that the content of vinyl acetate between to for plastic in the described ethylene-vinyl acetate copolymer is weight percentage 15～30%, and the melt flow index of described ethylene-vinyl acetate copolymer is 15～40g/10min.
5. the preparation of compositions method of a Thermoplastic Elastomer, Olefinic is characterized in that may further comprise the steps:
1) following compositions in weight percentage is prepared burden:
Polyvinyl resin: 40～80%
Propylene-ethylene copolymers: 10～35%
Ethylene-vinyl acetate copolymer: 10～25%;
2) material that will prepare mixes the back discharging in mixing machine, adopts the forcing machine granulation;
The high density polyethylene(HDPE) particle of described polyvinyl resin for adopting low-pressure process to produce, its weight-average molecular weight is 100000～1000000;
Described propylene-ethylene copolymers is the copolymer pellet that adopts metallocene catalyst and solution polymerization process to produce, and melt flow index is 50～350g/10min, and the content of therein ethylene is weight percentage 12～20%;
The content of vinyl acetate between to for plastic is weight percentage 15～30% in the described ethylene-vinyl acetate copolymer, and the melt flow index of described ethylene-vinyl acetate copolymer is 15～40g/10min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516621A (en) * | 2011-11-28 | 2012-06-27 | 宁波先锋新材料股份有限公司 | Polyethylene-based thermoplastic elastomer and preparation method and composite plastic thereof |
| CN103374820A (en) * | 2013-07-26 | 2013-10-30 | 浙江鹏远新材料有限公司 | Antiskid woven cloth and preparation method thereof |
| CN111269480A (en) * | 2020-03-21 | 2020-06-12 | 李昌欣 | Super-strong weather-resistant TPE material applied to insulator umbrella cover and preparation method |
| CN111333939A (en) * | 2020-01-18 | 2020-06-26 | 东莞市利鸿橡塑科技有限公司 | Acid-base-resistant low-temperature-resistant flame-retardant TPE material applied to insulator umbrella cover |
| CN112590157A (en) * | 2020-11-05 | 2021-04-02 | 江苏虹驰家居科技有限公司 | POE material-based bionic silkworm cocoon structure processing technology |
| CN114213767A (en) * | 2021-12-09 | 2022-03-22 | 金发科技股份有限公司 | Polypropylene composite material and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102516621A (en) * | 2011-11-28 | 2012-06-27 | 宁波先锋新材料股份有限公司 | Polyethylene-based thermoplastic elastomer and preparation method and composite plastic thereof |
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| CN103374820A (en) * | 2013-07-26 | 2013-10-30 | 浙江鹏远新材料有限公司 | Antiskid woven cloth and preparation method thereof |
| CN111333939A (en) * | 2020-01-18 | 2020-06-26 | 东莞市利鸿橡塑科技有限公司 | Acid-base-resistant low-temperature-resistant flame-retardant TPE material applied to insulator umbrella cover |
| CN111269480A (en) * | 2020-03-21 | 2020-06-12 | 李昌欣 | Super-strong weather-resistant TPE material applied to insulator umbrella cover and preparation method |
| CN112590157A (en) * | 2020-11-05 | 2021-04-02 | 江苏虹驰家居科技有限公司 | POE material-based bionic silkworm cocoon structure processing technology |
| CN114213767A (en) * | 2021-12-09 | 2022-03-22 | 金发科技股份有限公司 | Polypropylene composite material and preparation method and application thereof |
| CN114213767B (en) * | 2021-12-09 | 2023-12-15 | 金发科技股份有限公司 | Polypropylene composite material and preparation method and application thereof |
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