CN1302065C - New type polyolefin thermoplastic elastomer - Google Patents

New type polyolefin thermoplastic elastomer Download PDF

Info

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
Authority
CN
China
Prior art keywords
thermoplastic elastomer
styrene
olefinic
elastomer
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 - Fee Related
Application number
CNB2004100265723A
Other languages
Chinese (zh)
Other versions
CN1563173A (en
Inventor
王传玉
汪加胜
唐舫成
朱东湖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangzhou Lushan New Materials Co Ltd
Original Assignee
HAIPU MATERIAL TECH Co Ltd GUANGZHOU
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by HAIPU MATERIAL TECH Co Ltd GUANGZHOU filed Critical HAIPU MATERIAL TECH Co Ltd GUANGZHOU
Priority to CNB2004100265723A priority Critical patent/CN1302065C/en
Publication of CN1563173A publication Critical patent/CN1563173A/en
Application granted granted Critical
Publication of CN1302065C publication Critical patent/CN1302065C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2004100265723A CN1302065C (en) 2004-03-23 2004-03-23 New type polyolefin thermoplastic elastomer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2004100265723A CN1302065C (en) 2004-03-23 2004-03-23 New type polyolefin thermoplastic elastomer

Publications (2)

Publication Number Publication Date
CN1563173A CN1563173A (en) 2005-01-12
CN1302065C true CN1302065C (en) 2007-02-28

Family

ID=34480649

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2004100265723A Expired - Fee Related CN1302065C (en) 2004-03-23 2004-03-23 New type polyolefin thermoplastic elastomer

Country Status (1)

Country Link
CN (1) CN1302065C (en)

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

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (2)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
CN1563173A (en) 2005-01-12

Similar Documents

Publication Publication Date Title
CN105295196B (en) A kind of high fluidity TPV material and preparation method thereof
CN1302065C (en) New type polyolefin thermoplastic elastomer
CN1916055A (en) Method for raising fluidity of thermoplastic cross-linked rubber
CN1944517A (en) Ternary ethylene propylene terpolyer rubber/polypropylene thermoplastic elastomer
CN1155652C (en) Toughened plastics and its preparing process
CN1821301A (en) Sulfurizing system and chlorinated isobutylene rubber/polyolefine thermoplastic elastomer
CN105131500A (en) High- springback TPE thermoplastic elastomer and preparing method thereof
CN110452467A (en) A kind of thermoplastic elastomer (TPE) and preparation method thereof with inierpeneirating network structure
CN109370482A (en) A kind of good TPV thermoplastic elastomer (TPE) of adhesive property and preparation method thereof
CN111053945B (en) Environment-friendly high-strength high-resilience TPE (thermoplastic elastomer) tourniquet material and preparation method thereof
CN1445279A (en) Thermoplastic elastomer made from nylon/ethylene propylene rubber and its preparing method
CN1610720A (en) Thermoplastic elastomer compositions
CN1687218A (en) Method for preparing tribasic ethylene propylene rubber/polypropylene thermoplastic elastomer
CN1227285C (en) Method for preparing thermoplastic cross-linked rubber
CN1317324C (en) Production of thermoplastic elastomer
CN1381523A (en) High-toughness polypropylene plastics and its preparing process
CN1265127A (en) Process for preparing polyacrylate/polyolefin blends
CN1180012C (en) Oil-resisting fully-vulcanized thermoplastic elastic body and its preparation method
CN1154692C (en) Toughened polypropylene and its preparing process
TWI679237B (en) Dynamic crosslinked thermoplastic elastomer and its process
CN103304856A (en) Chemical co-blending method of thermoplastic nitrile butadiene rubber TPNBR
CN1939962A (en) Polyolefine toughening modifier and its production
CN112745588A (en) Composition for preparing ethylene propylene diene monomer/polylactic acid thermoplastic vulcanized rubber, and preparation method and application thereof
CN1188469C (en) Toughening polyamide combination and prepn method
CN1241981C (en) Soft thio polyolefine thermoplastic elastic body and its preparation method

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
PE01 Entry into force of the registration of the contract for pledge of patent right

Effective date of registration: 20091028

Pledge (preservation): Pledge

ASS Succession or assignment of patent right

Owner name: GUANGZHOU LUSHAN NEW MATERIALS CO.,LTD.

Free format text: FORMER OWNER: GUANGZHOU HAIPU MATERIAL TECHNOLOGY CO., LTD.

Effective date: 20100511

C41 Transfer of patent application or patent right or utility model
COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: 510660 ROOM 302, COMPREHENSIVE BUILDING, TIANHECHEPO HUANGZHOU INDUSTRY DISTRICT, GUANGZHOU CITY, GUANGDONG PROVINCE TO: 510530 ROOOM 303, BUILDING 2, NO.22, PUBEI ROAD, YUNPU INDUSTRY DISTRICT, HUANGPU DISTRICT, GUANGZHOU CITY, GUANGDONG PROVINCE

TR01 Transfer of patent right

Effective date of registration: 20100511

Address after: YUNPU Industrial Zone Whampoa District Po Road Guangzhou city Guangdong province 510530 No. 22 Building 2 Room 303

Patentee after: Guangzhou Lushan New Materials Co., Ltd.

Address before: 510660 comprehensive building, Tianhe Huang industrial zone, Tianhe, Guangdong, Guangzhou 302

Patentee before: Haipu Material Tech Co., Ltd., Guangzhou

PC01 Cancellation of the registration of the contract for pledge of patent right

Date of cancellation: 20110118

Granted publication date: 20070228

Pledgee: China Merchants Bank, Limited by Share Ltd, Guangzhou surplus Plaza Branch

Pledgor: Guangzhou Lushan chemical materials Co., Ltd.|Guangzhou Hepalink Mstar Technology Ltd

Registration number: 2009440000632

PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: Polyolefin thermoplastic elastomer (TPE) composition and preparation method thereof

Effective date of registration: 20110118

Granted publication date: 20070228

Pledgee: China Merchants Bank, Limited by Share Ltd, Guangzhou surplus Plaza Branch

Pledgor: Guangzhou Lushan New Materials Co., Ltd.

Registration number: 2011990000011

PC01 Cancellation of the registration of the contract for pledge of patent right

Date of cancellation: 20120620

Granted publication date: 20070228

Pledgee: China Merchants Bank, Limited by Share Ltd, Guangzhou surplus Plaza Branch

Pledgor: Guangzhou Lushan New Materials Co., Ltd.

Registration number: 2011990000011

PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: Polyolefin thermoplastic elastomer (TPE) composition and preparation method thereof

Effective date of registration: 20120620

Granted publication date: 20070228

Pledgee: China Merchants Bank, Limited by Share Ltd, Guangzhou branch

Pledgor: Guangzhou Lushan New Materials Co., Ltd.

Registration number: 2012990000312

PC01 Cancellation of the registration of the contract for pledge of patent right

Date of cancellation: 20140620

Granted publication date: 20070228

Pledgee: China Merchants Bank, Limited by Share Ltd, Guangzhou branch

Pledgor: Guangzhou Lushan New Materials Co., Ltd.

Registration number: 2012990000312

PLDC Enforcement, change and cancellation of contracts on pledge of patent right or utility model
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20070228

Termination date: 20180323