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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- Prior art keywords
- rubber
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- thermoplastic vulcanizate
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 title claims abstract description 8
- 229920006342 thermoplastic vulcanizate Polymers 0.000 title claims description 11
- 229920001971 elastomer Polymers 0.000 claims abstract description 30
- 239000005060 rubber Substances 0.000 claims abstract description 30
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 3
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 3
- 229920001194 natural rubber Polymers 0.000 claims abstract description 3
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 229920005672 polyolefin resin Polymers 0.000 claims description 7
- -1 polypropylene Polymers 0.000 claims description 6
- 229920000578 graft copolymer Polymers 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 229920001897 terpolymer Polymers 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 229920003987 resole Polymers 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- 229920013649 Paracril Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 abstract description 14
- 229920002725 thermoplastic elastomer Polymers 0.000 abstract description 7
- 230000021523 carboxylation Effects 0.000 abstract description 6
- 238000006473 carboxylation reaction Methods 0.000 abstract description 6
- 238000010924 continuous production Methods 0.000 abstract description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract 1
- 229920000459 Nitrile rubber Polymers 0.000 abstract 1
- 150000002978 peroxides Chemical class 0.000 abstract 1
- 229920001568 phenolic resin Polymers 0.000 abstract 1
- 239000005011 phenolic resin Substances 0.000 abstract 1
- 229920002857 polybutadiene Polymers 0.000 abstract 1
- 229920001169 thermoplastic Polymers 0.000 abstract 1
- 239000004416 thermosoftening plastic Substances 0.000 abstract 1
- 239000004636 vulcanized rubber Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002174 Styrene-butadiene Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229920006258 high performance thermoplastic Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
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 |
|---|---|---|---|
| CN 02132436 Expired - Fee Related CN1228374C (en) | 2002-06-11 | 2002-06-11 | Composite polyolefine thermoplastic vulcanizate |
Country Status (1)
| Country | Link |
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| CN (1) | CN1228374C (en) |
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 |
| KR101186117B1 (en) * | 2010-03-17 | 2012-09-27 | 요코하마 고무 가부시키가이샤 | Rubber composition, cross-linked rubber composition and high-performance damping 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 |
-
2002
- 2002-06-11 CN CN 02132436 patent/CN1228374C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1465614A (en) | 2004-01-07 |
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