CN1302065C - New type polyolefin thermoplastic elastomer - Google Patents

New type polyolefin thermoplastic elastomer Download PDF

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Publication number
CN1302065C
CN1302065C CNB2004100265723A CN200410026572A CN1302065C CN 1302065 C CN1302065 C CN 1302065C CN B2004100265723 A CNB2004100265723 A CN B2004100265723A CN 200410026572 A CN200410026572 A CN 200410026572A CN 1302065 C CN1302065 C CN 1302065C
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China
Prior art keywords
thermoplastic elastomer
olefinic
styrene
elastomer
polypropylene
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Expired - Fee Related
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CNB2004100265723A
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Chinese (zh)
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CN1563173A (en
Inventor
王传玉
汪加胜
唐舫成
朱东湖
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Guangzhou Lushan New Materials Co Ltd
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HAIPU MATERIAL TECH Co Ltd GUANGZHOU
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Abstract

The present invention relates to a novel thermoplastic polyolefin elastomer, which is characterized in that polypropylene, an ethene-octen copolymerization elastomer and a styrene-butadiene-styrene tribasic block polymer are used as main components, and a vulcanizing agent and an auxiliary crosslinking agent are added in the main components to be dynamically vulcanized and crosslinked by a double-screw machine to form seminific master batch; then, nanometer talcum powder and an auxiliary agent are added in the main components to be extruded and granulated by the double-screw machine to form the novel thermoplastic polyolefin elastomer. The thermoplastic polyolefin elastomer has the advantages of good mechanical performance and processing performance, no product odor and low cost, and is suitable for the field of manufacturing automobile parts or other fields. The novel polyolefin thermoplastic elastomer is a novel elastomeric material with wide purposes.

Description

A kind of Thermoplastic Elastomer, Olefinic
Technical field
The present invention relates to a kind of Thermoplastic Elastomer, Olefinic.
Background technology
Thermoplastic Elastomer, Olefinic (TPO) is high performance thermoplastic elastic material, have excellent elasticity bulk properties and good processing properties and good weathering resistance, it is widely used in fields such as automobile, cable, light textile, building and household electrical appliances as the substitute products of rubber.TPO mainly is made of rubber and polyolefine.Rubber mainly contains terpolymer EP rubber (EPDM), paracril (NBR) and isoprene-isobutylene rubber, polyolefine mainly is polypropylene (PP) and polyethylene (PE), that at present the most frequently used is the TPO of EPDM/PP system, research for this system is many, particularly by dynamic vulcanization the elastomeric over-all properties of EPDM/PP system is improved constantly, the elastomer product of existing various satisfactory mechanical properties, rebound resilience excellence is put on market.But in this system, the broken glue of EPDM has certain difficulty, and processing flowability is good inadequately, has limited its development to a certain extent.
Along with the development of automobile and related industries, also more and more higher to the requirement of its component material therefor, also more and more deep to the research of thermoplastic elastomer, Thermoplastic Elastomer, Olefinic TPO particularly, its output has accounted for 29% of thermoplastic elastomer output at present.It is reported, adopt ethene-octene copolymer elastomerics (POE) to replace EPDM to have tangible advantage because the processing fluidity of POE is better than EPDM rubber, it with the process of PP blend in, be easy to mix with PP, and, do not have the problem of broken glue difficulty.The TPO existing procucts of POE/PP system are put on market, as the Elastmax of Polyone company The TPO series product.The POE/PP system /manufacturing process of TPO can pass through simple blend or dynamic vulcanization process, and the latter is better than the product mechanical property that the former makes, and particularly tensile strength increases.But the POE price is more expensive, makes the TPO product cost of POE/PP system higher, and, because dynamic vulcanization process adopts superoxide as linking agent, in material processing, produce smell, environment there is certain influence.
Summary of the invention
The purpose of this invention is to provide a kind of novel Thermoplastic Elastomer, Olefinic TPO material, main component is POE and PP, form by dynamic vulcanization is crosslinked, the product processing fluidity is good, has excellent mechanical property, cost is lower, and product do not have residual smell, is suitable as the application in automobile component or other field.
The present invention is a kind of new type polyolefin thermoplastic elastomer TPO, with polypropylene (PP), ethene-octene copolymer elastomerics (POE) is basal component, add vinylbenzene-divinyl-polystyrene ternary segmented copolymer (SBS) as another component, add vulcanizing agent, additional crosslinker, the crosslinked seed masterbatch that forms of dynamic vulcanization in twin screw extruder then, add auxiliary agents such as nanomete talc powder, antioxidant and photostabilizer again, form through the twin screw extruder extruding pelletization.Its component contains (weight percent):
Polypropylene (PP) 10-45%
Ethene-octene copolymer elastomerics (POE) 10-65%
Vinylbenzene-divinyl-vinylbenzene (SBS) 2-30%
Vulcanizing agent 0.1-0.4%
Additional crosslinker 0.1-0.3%
Nanomete talc powder 1-5%
Antioxidant 0.1-0.3%
Photostabilizer 0.1-0.2%
Wherein, PP is a homopolymerization PP, the optimal selection melting index be 20g/10min (230 ℃/2.16kg) homopolymerization PP, optimum amount is 25-35%; It is the trade mark of 0.5g/10min that POE selects melting index for use, and optimum amount is 55-65%; SBS preferentially selects star-like model for use, and optimum amount is 4-10%; Vulcanizing agent preferentially selects 2 for use, 5-dimethyl-2, and 5-bis(t-butylperoxy) hexane, code name 101, optimum amount are 0.15%; Additional crosslinker is selected cyanacrylate for use, and code name TAIC, optimum amount are 0.15%; Antioxidant preferred four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, code name 1010; Photostabilizer is selected two (2,2,6,6-tetramethyl--piperidyl) sebates, code name 770 for use.
The present invention uses homopolymerization PP to be raw material, and it forms the external phase of sea-island structure in goods, gives goods good mechanical performance and resistance toheat.The adding of an amount of SBS can improve the crosslinking degree of whole system, it and POE have formed composite toughened system, give system good mechanical performance and rebound resilience, because SBS is easier to be crosslinked than POE, it is more even that it makes rubber phase disperse in mutually at plastics, refinement more.With the POE of SBS instead of part a part, not only can improve the mechanical property of goods, and, can reduce the raw materials cost of product because the SBS price comparison is cheap as rubber phase.Certainly, the adding of SBS is not The more the better, if the amount that adds is too many, can cause over-crosslinked, thus make rubber phase can not be dispersed in well plastics mutually in, can produce like this and be separated, over-all properties is descended on the contrary.Illustrate as the POE among the TPO when some replaces with SBS influence (TPO-1# is the TPO that does not add SBS, and TPO-2# is the TPO that adds SBS) below to mechanical property:
Prescription:
PP POE SBS 101 TAIC talcum powder auxiliary agents
TPO 1# 29.36 8.3 0 0.15 0.15 1.9 0.2
TPO-2# 29.3 58.5 9.8 0.15 0.15 1.9 0.2
Performance compares:
As can be seen from the table, under identical condition, the POE with the SBS instead of part can make the tensile strength of product be significantly improved.
Prepare with dynamic vulcanization process in the process of TPO material of the present invention, must adopt the dual-screw-stem machine that big shearing force screw combinations is arranged, make rubber phase and plastics refinement mutually, and can mix equably, like this, under the effect of vulcanizing agent, the molecular chain of rubber phase is cross-linked with each other with plastics molecular chain mutually and forms the network system.Because the adding of vulcanizing agent can produce smell in the course of processing, therefore, the present invention adds the Nano filling talcum powder, utilizes the dimensional effect of nano material, and high surface energy can be eliminated smell and improve the goods weathering resistance.
Thermoplastic Elastomer, Olefinic of the present invention (TPO) is a kind of novel elastomer material.Its mechanical property and processing characteristics are good, and cost is lower, can be used for automobile and other field, applied range.
Embodiment
Embodiment one weight percent (%)
PPZ30S 29.3
POE8180 58.5
SBS(791) 9.8
Vulcanizing agent 101 0.15
Additional crosslinker TAIC 0.15
Nanomete talc powder 1.9
Antioxidant 1010 0.1
Photostabilizer 770 0.1
Wherein PPZ30S is meant that melting index is (230 ℃/2.16kg) homopolymerization PP of 20g/10min, its trade mark is PPZ30S, POE8180 is meant that melting index is the POE of 0.5g/10min, its trade mark 8180, SBS (791) refers to that the trade mark is 791 star-shaped sbs., vulcanizing agent in the above-mentioned prescription 101 and additional crosslinker TAIC are used earlier acetone solution, add the PPZ30S that has mixed, in the mixture of POE8180 and star-shaped sbs (791) and mixing, after the acetone volatilization, add in the twin screw extruder (temperature 190-200 ℃, 500 rev/mins of dual-screw-stem machine rotating speeds), through the crosslinked seed masterbatch that forms of dynamic vulcanization, add nanomete talc powder and antioxidant 1010 and photostabilizer 770 again, form Thermoplastic Elastomer, Olefinic TPO of the present invention through the dual-screw-stem machine extruding pelletization.Product processing characteristics and good mechanical performance, product does not have smell, and owing to add the higher POE of lower-cost SBS instead of part price, can reduce the manufacturing cost and the price of product, is applicable to automobile component or other field of making.Present embodiment TPO main performance index sees the following form:
Tensile strength MPa Elongation at break (%) Melting index (g/10min) Shore hardness Stress at definite elongation
A D 100% 200% 300%
11.3 558 0.685 85 25 5.8 6.8 8.0
The test condition of melting index is 190 ℃/2.16Kg, down together.
Embodiment two weight per-cents (%)
PPZ30S 29.3
POE8180 63.5
SBS(791) 4.8
Vulcanizing agent 101 0.15
Additional crosslinker TAIC 0.15
Nanomete talc powder 1.9
Antioxidant 1010 0.1
Photostabilizer 770 0.1
The preparation method is identical with embodiment one, and the product main performance index sees the following form:
Tensile strength MPa Elongation at break (%) Melting index (g/10min) Shore hardness Stress at definite elongation
A D 100% 200% 300%
9.7 577 0.7 88 26 5.6 6.5 7.4
Implement three weight per-cents (%)
PPZ30S 29.3
POE8180 48.5
SBS(791) 19.8
Vulcanizing agent 101 0.15
Additional crosslinker TAIC 0.15
Nanomete talc powder 1.9
Antiskid agent 1,010 0.1
Photostabilizer 770 0.1
The preparation method is identical with embodiment one, and the product main performance index sees the following form:
Tensile strength MPa Elongation at break (%) Melting index (g/10min) Shore hardness Stress at definite elongation
A D 100% 200% 300%
8.2 484 0.62 90 26.5 4.9 5.7 6.6
Embodiment quadruple amount per-cent (%)
PPZ30S 39.3
POE8180 28.5
SBS(791) 29.8
Vulcanizing agent 101 0.15
Additional crosslinker TAIC 0.15
Nanomete talc powder 1.9
Antioxidant 1010 0.1
Photostabilizer 770 0.1
The preparation method is identical with embodiment one, and product salient features performance sees the following form:
Tensile strength MPa Elongation at break (%) Melting index (g/10min) Shore hardness Stress at definite elongation
A D 100% 200% 300%
9.7 343 0.83 98 29 6.5 7.5 8.6
Can regulate each proportion of raw materials according to user's requirement, the TPO product of all size that production performance suits the requirements.

Claims (6)

1, a kind of Thermoplastic Elastomer, Olefinic, contain polypropylene and ethylene-octene copolymer, it is characterized in that being main component mainly by polypropylene, ethylene-octene copolymer elastomerics, styrene-butadiene-styrene ternary block polymer, add vulcanizing agent and additional crosslinker, dynamic vulcanization forms the seed masterbatch in twin screw extruder, add nanomete talc powder, antioxidant and photostabilizer then, extruding pelletization forms in dual-screw-stem machine, and the weight percent of its each component is:
Polypropylene 10-45%
Ethylene-octene copolymer elastomer 10-65%
Styrene-butadiene-styrene ternary block polymer 2-30%
Vulcanizing agent 0.1-0.4%
Additional crosslinker 0.1-0.3%
Nanomete talc powder 1-5%
Antioxidant 0.1-0.3%
Photostabilizer 0.1-0.2%
Wherein vulcanizing agent is 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane, additional crosslinker is a cyanacrylate, and antioxidant is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, photostabilizer is two (2,2,6, the 6-tetramethyl-4-piperidyl) sebate.
2, Thermoplastic Elastomer, Olefinic according to claim 1 is characterized in that polypropylene is a homo-polypropylene, and its melting index is 20g/10min.
3, Thermoplastic Elastomer, Olefinic according to claim 1 and 2 is characterized in that polyacrylic content accounts for the 25-35% of gross weight.
4, Thermoplastic Elastomer, Olefinic according to claim 1, the melting index that it is characterized in that the ethylene-octene copolymer elastomer is 0.5g/10min.
5,, it is characterized in that the content of ethylene-octene accounts for the 55-65% of gross weight according to claim 1 or 4 described Thermoplastic Elastomer, Olefinic.
6, Thermoplastic Elastomer, Olefinic according to claim 1 is characterized in that the styrene-butadiene-styrene ternary block polymer adopts star-like model, and its content accounts for the 4-10% of gross weight.
CNB2004100265723A 2004-03-23 2004-03-23 New type polyolefin thermoplastic elastomer Expired - Fee Related CN1302065C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108003542A (en) * 2017-12-15 2018-05-08 深圳恒方大高分子材料科技有限公司 A kind of peristaltic pump polyolefin elastomer and preparation method thereof

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CN100443519C (en) * 2006-09-06 2008-12-17 江苏创源科技新材料有限公司 Fusion graft process for modified polypropylene/acrylic acid polyester ether
CN101307219B (en) * 2007-05-16 2013-09-25 南通江洲工程材料科技有限公司 Multicomponent high molecular composite construction sealing materials and production process thereof
US8604125B2 (en) * 2008-06-25 2013-12-10 Lg Chem, Ltd. Polypropylene-based resin composition and automobile parts using the same
CN101486816B (en) * 2008-12-08 2011-05-11 宁波工程学院 High impact resistance polypropylene composite material and preparation thereof
CN101880432B (en) * 2010-07-02 2012-02-01 深圳市科聚新材料有限公司 Polyhydric graft ethylene-octene copolymer and preparation method thereof
CN102367311B (en) * 2011-09-26 2013-06-12 广州市聚赛龙工程塑料有限公司 Low specific gravity polypropylene composite material for automobile bumper use and its preparation method
CN102443241B (en) * 2011-10-26 2013-05-29 江苏恒峰线缆有限公司 SBS sulfonate prepared by reactive extrusion and addition, and preparation method thereof
CN102786763A (en) * 2012-06-04 2012-11-21 上海日杰弹性体塑胶有限公司 Flexible pipe material for temperature resistant and thermoplastic elastomer and preparation method thereof
CN102816336B (en) * 2012-09-07 2014-10-22 上海第二工业大学 Method for preparing high filling plastic masterbatch for polypropylene woven bag
JP6322651B2 (en) * 2012-12-27 2018-05-09 ダウ グローバル テクノロジーズ エルエルシー Manufacture of TPO roof membrane by different direction rotational extrusion
CN107974024B (en) * 2017-12-20 2020-03-17 石家庄英利体育用品有限公司 Thermoplastic elastomer composition, and preparation method and application thereof

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CN1435442A (en) * 2002-01-28 2003-08-13 四川大学 Tertiary polypropylene/elastomer/inorganic filler composite material and preparing method thereof

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN1385466A (en) * 2001-05-16 2002-12-18 中国石油化工股份有限公司洛阳分公司 Novel thermoplastic elastomer and preparation process thereof
CN1435442A (en) * 2002-01-28 2003-08-13 四川大学 Tertiary polypropylene/elastomer/inorganic filler composite material and preparing method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108003542A (en) * 2017-12-15 2018-05-08 深圳恒方大高分子材料科技有限公司 A kind of peristaltic pump polyolefin elastomer and preparation method thereof

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