CN1228374C - Composite polyolefine thermoplastic vulcanizate - Google Patents
Composite polyolefine thermoplastic vulcanizate Download PDFInfo
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- CN1228374C CN1228374C CN 02132436 CN02132436A CN1228374C CN 1228374 C CN1228374 C CN 1228374C CN 02132436 CN02132436 CN 02132436 CN 02132436 A CN02132436 A CN 02132436A CN 1228374 C CN1228374 C CN 1228374C
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Abstract
The present invention belongs to a thermoplastic elastomer. The rubber part of the present invention adopts a combination system of double components of unsaturated rubber or ethylene propylene diene monomer (EPDM), and adopts a double-component vulcanizing agent phenolic resin or peroxide and double-component carboxylation polyolefine so as to solve the covulcanization of the unsaturated rubber and the ethylene propylene diene monomer (EPDM) as well as the compatibility problem of the unsaturated rubber and the polyolefin, wherein the unsaturated rubber is styrene-butadiene rubber or polybutadiene rubber or nitrile rubber or natural rubber. The present invention provides composite polyolefine thermoplastic vulcanized rubber which can be used for continuous production in a double-screw extruder and has high performance and low cost.
Description
Invention field
The invention belongs to a kind of thermoplastic elastomer.
Background technology
Thermoplastic elastomer (TPE) kind is many at present, and with respect to the TPE of other non-vulcanization type, Thermoplastic Vulcanizate (TPV) has minimum compression set, and thermotolerance and winter hardiness also belong to superior, and over-all properties comes out at the top in TPE.An its significant advantage be can be in twin screw extruder continuous production, have that investment is little, the characteristics of instant effect, unlike other TPE kind, need throw huge fund and could realize industrialization.
Have abroad with terpolymer EP rubber (EPDM)/polypropylene (PP) system to prepare the report of Thermoplastic Vulcanizate, because its cost is higher, range of application is very little.And adopt two components and use the rubbery system aspect, because being difficult to solve, its covulcanization problem can not get high performance thermoplastic vulcanizate material, so report less.The paper that Gu Qincui, Guo Hongge etc. deliver " performance study of NR/EPDM/PP tertiary blending thermoplastic material " (" Qingtao Chemical Engineering College's journal: " 2000 from section's version, 21 (4), P325-327,347), be reported as the covulcanization problem that solves the NR/EPDM/PP system, take segmentation to add the method for rubber and vulcanizing agent, this method is intermittently to carry out in mill, be not suitable for industrialized continuous production, and this rubber performance is also unsatisfactory.
Summary of the invention
Given this, the invention provides a kind of can be in twin screw extruder continuous production, high-performance, composite polyolefine thermoplastic vulcanizate cheaply.
Composite polyolefine thermoplastic vulcanizate of the present invention comprises rubber segments, plastics section, vulcanizing agent and other auxiliary agent.Rubber segments adopts the two-pack paralled system: unsaturated rubber accounts for the 10-90% of rubber segments weight, and terpolymer EP rubber accounts for 10-90%.Unsaturated rubber such as styrene-butadiene rubber(SBR) (SBR) can reduce cost significantly, terpolymer EP rubber (EPDM) can remedy the deficiency of SBR aspect ageing-resistant, according to different actual needs, unsaturated rubber can be styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, paracril or natural rubber.
Plastics section of the present invention also adopts two component paralled systems: contain the compound of carboxyl or carbonyl and unsaturated carbon-carbon double bond and the graft copolymer of two kinds of polyolefin resines, promptly the carboxylation polyolefin copolymer respectively accounts for the 5-30% of overall weight.Said two kinds of polyolefin resines, wherein a kind of polyolefin resin is an ethylene-alpha-olefin copolymer, alhpa olefin can be octene, butylene or propylene; Another kind of polyolefin resin can be polypropylene, polyethylene or its multipolymer.
The same pair component paralled systems that adopt of vulcanizing agent of the present invention: resol (PFR) accounts for 12.6% of overall weight; Organo-peroxide accounts for 0.1-3%.Because unsaturated rubber such as SBR are different and undesirable with polyolefinic consistency with the vulcanization rate of EPDM, the present invention solves the problems referred to above by vulcanizing agent resol (PFR) and the polyolefinic reaction of carboxylation.Methylol (the CH of PFR
2OH) the active hydrogen reaction dehydration back with SBR and EPDM forms C-C bond.Methylol (CH
2OH) can also (COOH) produce esterification and form carbon-oxygen chemical bond with the carboxyl in the carboxylation polyolefine.This double reaction of PFR has produced the connection of the bridge formation formula between the component, has greatly improved the consistency of system.
The preferred carboxylation polyolefine of the present invention comprises ME-α 0 (ethylene-alpha-olefin copolymer of maleic anhydride graft) and maleic anhydride graft polyolefine such as MPP (maleic anhydride inoculated polypropylene), ME-α 0 is a kind of multipolymer with high alhpa olefin content of utmost point low-crystallinity, unformed area that they are a large amount of and EPDM and unsaturated rubber such as SBR have well interpenetrating property, with MPP good consistency is arranged also, because the pulling function of ME-α 0 and MPP and PFR reaction, make FPR can carry out these equably and interpenetrate the zone and carry out vulcanization reaction, thereby what guaranteed vulcanization reaction evenly is the realization of covulcanization.
It is very effective vulcanizing agent and FLOW IMPROVERS that superoxide is verified in the EPDM/PP system.Superoxide rises on the one hand and helps sulfuration in reaction process, improves liquidity on the other hand, remedies the defective that causes TPV material melt fluidity difference because of the chemical reaction of PFR.
The present invention is by adopting two component vulcanizing agents and two component carboxylation polyolefine to solve covulcanization and SBR and the polyolefinic compatibility problem of unsaturated rubbers such as SBR and EPDM, and gives good rerum natura of material and processibility.
Beneficial effect of the present invention is:
1, the present invention is owing to two component rubbery systems, and under the situation that product properties meets the demands, its material cost is lower by about 1/3 than EPDM/PP system;
2, production unit can be used twin screw extruder, is suitable for large-scale continuous production;
3, want to satisfy the needs of most of rubber items on the material property and have excellent processing forming:
(1) shortened shaping cycle greatly, reduced to 10-50 second by 2-10 minute;
(2) simplified traditional Rubber processing operation, made tooling cost reduce about 50%;
(3) reduction or elimination environmental pollution;
(4) thoroughly change the thermoset of rubber in the past, made leftover bits can reclaim processing again, reduced material cost greatly.
Embodiment:
Embodiment 1
Present embodiment is by constituting following the composition:
(4045) 60 parts of terpolymer EP rubbers
(1502) 40 parts in styrene-butadiene rubber(SBR)
10 parts of maleic anhydride graft ethylene-propylene copolymers (self-control)
8 parts of maleic anhydride grafted ethene-octene copolymers (self-control)
20 parts of tert.-butylbenzene fluosite
6 parts in the inferior tin of neoprene
1.5 parts of dicumyl peroxides
2 parts of vinyl silanes
(80%) 10 part in calcium oxide
1.5 parts of stearic acid
With this mixture in twin screw extruder after carrying out vulcanization reaction under the molten state granulation make.
For the obtained physical properties of articles of present embodiment is compared, ad hoc control group: use (8303) 10 parts of ethylene-propylene copolymers respectively, ethylene-octene copolymer (8003) replaces its maleic anhydride graft copolymer among the embodiment 1, and does not add dicumyl peroxide, and all the other components are identical.
Its physicals comparative result is as follows:
Project implementation example 1 control group
Melting index (230C, 5kg) 4.5 0.2
Tensile strength (MPa) 7.2 6.3
Tensile yield (%) 420 380
Tear strength (KN/m) 43 42
Compression set (70C, 22h) 28 57
Hardness (Shao Shi A) 72 74
Can find out, compare with control group that every physicals of embodiment 1 goods is better than control group mostly, particularly key project compression set differs obvious.
Claims (3)
1, composite polyolefine thermoplastic vulcanizate comprises rubber segments, plastics section, vulcanizing agent and other auxiliary agent, wherein:
A) rubber segments adopts the two-pack paralled system: unsaturated rubber accounts for the 10-90% of rubber segments weight, and terpolymer EP rubber accounts for 10-90%;
B) the plastics section adopts two component paralled systems: contain the compound of carboxyl or carbonyl and unsaturated carbon-carbon double bond and the graft copolymer of two kinds of polyolefin resines, wherein a kind of polyolefin resin is an ethylene-alpha-olefin copolymer, and alhpa olefin is octene, butylene or propylene; Another kind of polyolefin resin is polypropylene, polyethylene or its multipolymer, and the two components of plastics section account for the 5-30% of overall weight respectively;
C) vulcanizing agent adopts two component paralled systems: resol accounts for 12.6% of overall weight; Organo-peroxide accounts for 0.1-3%.
2, according to the composite polyolefine thermoplastic vulcanizate of claim 1, wherein said unsaturated rubber is styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, paracril or natural rubber.
3, according to the composite polyolefine thermoplastic vulcanizate of claim 1, wherein said graft copolymer is a maleic anhydride graft copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02132436 CN1228374C (en) | 2002-06-11 | 2002-06-11 | Composite polyolefine thermoplastic vulcanizate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02132436 CN1228374C (en) | 2002-06-11 | 2002-06-11 | Composite polyolefine thermoplastic vulcanizate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1465614A CN1465614A (en) | 2004-01-07 |
| CN1228374C true CN1228374C (en) | 2005-11-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 02132436 Expired - Fee Related CN1228374C (en) | 2002-06-11 | 2002-06-11 | Composite polyolefine thermoplastic vulcanizate |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643564B (en) * | 2008-08-09 | 2011-11-16 | 比亚迪股份有限公司 | Rubber and preparation method thereof |
| CN101724181B (en) * | 2008-10-21 | 2012-02-15 | 邵毅 | Efficient compound thermoplastic elastomer |
| CN101792557B (en) * | 2010-02-24 | 2011-05-04 | 沈阳军航电源科技有限公司 | Application of thermoplastic elastomer on soft power cable for wind power generation |
| JP4900538B1 (en) * | 2010-03-17 | 2012-03-21 | 横浜ゴム株式会社 | Rubber composition, cross-linked rubber composition, and highly attenuated laminate |
| CN104710692B (en) * | 2015-02-09 | 2017-01-11 | 青岛科技大学 | Solubilizer for improving performance of natural rubber-ethylene propylene rubber co-blended rubber and preparation method thereof |
| CN106243525A (en) * | 2016-08-27 | 2016-12-21 | 潍坊市宏源防水材料有限公司 | High wear-resistance anti-static type EPDM waterproof rolled sheet and preparation method thereof |
| CN115418045B (en) * | 2022-10-08 | 2023-10-20 | 宁波汉吉高分子材料有限公司 | Thermoplastic polyolefin composition and preparation method and application thereof |
| CN115772331B (en) * | 2023-02-13 | 2023-04-25 | 广东粤港澳大湾区黄埔材料研究院 | Rubber processing aid, preparation method thereof and tire rubber composition |
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2002
- 2002-06-11 CN CN 02132436 patent/CN1228374C/en not_active Expired - Fee Related
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| CN1465614A (en) | 2004-01-07 |
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Granted publication date: 20051123 |