CN1840577A - Thermoplastic elastomer compositions rheology-modified using peroxides and free radical coagents - Google Patents
Thermoplastic elastomer compositions rheology-modified using peroxides and free radical coagents Download PDFInfo
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- CN1840577A CN1840577A CN 200610058410 CN200610058410A CN1840577A CN 1840577 A CN1840577 A CN 1840577A CN 200610058410 CN200610058410 CN 200610058410 CN 200610058410 A CN200610058410 A CN 200610058410A CN 1840577 A CN1840577 A CN 1840577A
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- 239000000203 mixture Substances 0.000 title claims abstract description 153
- 150000003254 radicals Chemical class 0.000 title claims abstract description 29
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 8
- 150000002978 peroxides Chemical class 0.000 title abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 51
- 238000000518 rheometry Methods 0.000 claims abstract description 41
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920001155 polypropylene Polymers 0.000 claims abstract description 34
- -1 polypropylene Polymers 0.000 claims abstract description 31
- 239000004743 Polypropylene Substances 0.000 claims abstract description 26
- 239000005977 Ethylene Substances 0.000 claims abstract description 25
- 239000004711 α-olefin Substances 0.000 claims abstract description 21
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000098 polyolefin Polymers 0.000 claims abstract description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 10
- 230000000051 modifying effect Effects 0.000 claims description 40
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 33
- 230000000694 effects Effects 0.000 claims description 23
- 239000012752 auxiliary agent Substances 0.000 claims description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 13
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 claims description 12
- 229920001519 homopolymer Polymers 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 229920001038 ethylene copolymer Polymers 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- ZYASLVDNDXUOMI-UHFFFAOYSA-N n,n-dimethylmethanamine;prop-2-enoic acid Chemical compound C[NH+](C)C.[O-]C(=O)C=C ZYASLVDNDXUOMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005502 peroxidation Methods 0.000 claims description 6
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 5
- 150000001993 dienes Chemical class 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 4
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 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 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 claims description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 2
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 claims description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 claims description 2
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims description 2
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 claims description 2
- 229950007687 macrogol ester Drugs 0.000 claims description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 2
- BAZXQZYWJSBDRG-UHFFFAOYSA-N pyrrole-2,5-dione;toluene Chemical compound CC1=CC=CC=C1.O=C1NC(=O)C=C1.O=C1NC(=O)C=C1 BAZXQZYWJSBDRG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 239000000155 melt Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000003856 thermoforming Methods 0.000 abstract description 9
- 238000003490 calendering Methods 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 48
- 239000000463 material Substances 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920002959 polymer blend Polymers 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000004927 fusion Effects 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
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- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
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- 210000002615 epidermis Anatomy 0.000 description 2
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
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- 238000005482 strain hardening Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- QEOSCXACXNFJCY-AKHDSKFASA-N (2R,3R,4S,5R)-6-benzyl-7-phenylheptane-1,2,3,4,5,6-hexol Chemical compound C(C1=CC=CC=C1)C(O)([C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO)CC1=CC=CC=C1 QEOSCXACXNFJCY-AKHDSKFASA-N 0.000 description 1
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- XWVQUJDBOICHGH-UHFFFAOYSA-N dioctyl nonanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC XWVQUJDBOICHGH-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Rheology-modified thermoplastic elastomer compositions comprising a melt blend of an ethylene/alpha-olefin polymer and a high melting polymer such as polypropylene or a propylene/alpha-olefin copolymer wherein the rheology modification is induced by a combination of a peroxide and a free radical coagent. The resulting compositions have an elastomeric phase, a non-elastomeric phase and certain physical properties that exceed those of a like composition that is rheology-modified by peroxide alone. The compositions can be used to make a variety of articles of manufacture, such as automotive instrument panel skins, via calendaring and thermoforming procedures.
Description
The application is that application number is 01816123.5, and the applying date is September 21 calendar year 2001, and denomination of invention is divided an application for the Chinese patent application of " carrying out the composition for thermoplastic elastomer of rheology modifying with superoxide and free radical activity auxiliary agent ".
Technical field
The thermoplastic elastomer of relate generally to rheology modifying of the present invention (TPE) composition, it comprises elastomeric ethylene/alpha-olefin (EAO) polymkeric substance or EAO blend polymer and high-melting-point propene polymer, wherein two kinds of compositions all are peroxide modified, the preparation, this based composition that also relates to said composition the goods manufacture craft for example roll and thermoforming in purposes and resulting goods.The present invention relates to such composition particularly, wherein, this rheology modifying is to be brought out by a kind of combination that comprises organo-peroxide and free radical activity auxiliary agent, the preparation method of said composition for example makes the modification of physical blending thing and the purposes of this based composition in calendering operation and thermoforming application of each composition.
Background technology
People such as Heck have described the TPE composition of rheology modifying in WO 98/32795.This rheology modifying can bring out with the various means that comprise superoxide and radiation.It is said that people's such as Heck composition exhibiting goes out to have both four kinds of performances: shear and weaken index (STI), melt strength (MS), solidification value (ST) and use or the service temperature upper limit (UST).Though these compositions can be used for various uses for example automobile component and chuck axle, for calendering operation and thermoforming application, still need improved composition.
Aspect the calendering operation, the composition that the melt toughness is high is desirable.As used herein, the melt toughness is that melt strength and melt ductility are long-pending.Under many circumstances, calendar rolls is with the composition feeding that is the molten rod form.This melt composition must can be on whole calendar rolls drawout.People's such as Heck composition can only be at ground, calendar rolls top drawout.
Use for thermoforming, the composition that the melt toughness is high also is preferably.In addition, use for these, said composition tensile property at high temperature also is important.For example, a kind of manufacture method of dashboard skin material is calendering or extrusion molding embossed sheet.Make the appearance of this sheet material vacuum forming then for this dashboard.A kind of measuring method of compound hot-forming property is assessment its high temperature stress-strain row.Soft polypropylene thermoplasticity (TPO) the sheet material normally temperature below polypropylene phase fusing point is hot formed.Although heat forming technology be a kind of twin shaft to extension process, can come comparative heat to be shaped and the texture retention behavior with the tension test under the forming temperature.The Feng Hegu of embossing texture is the zone that big thickness and less thickness are arranged, and the observation of texture is shown, the paddy district is narrower and glossy still less than peak district.When being shaped a kind of epidermis, thin zone will suffer from bigger stress, and act on big stress concentration on these zones in the elongation of this thinner region.The preferential elongation in these zones, and lose noticeable " defile, broad peak " outward appearance, be called " texture cleanings " unless-this material can design to such an extent that extend more equably.Strain hardening is that thereby the strained material area becomes harder and makes elongation subsequently transfer to the character in unstrained zone still.Therefore, strain hardening makes hot formed epidermis can demonstrate more equally distributed elongation and the cleaning of minimized texture.
A kind of classical way of investigating a kind of material strain sclerosis behavior is the Considere structure, therefore, the actual stress that is defined as the power on whole moment cross-sectional area is mapped to stretch ratio.
The rule stress strain diagrm utilizes the long-pending calculating of initial cross sectional strain, but this cross-sectional area reduces with this sample strain.Usually utilize this Considere to construct and assess cold drawn phenomenon.
This Considere structure can be determined with following agenda:
σ
T＝σ(1+ε)
In the formula: σ
T=actual stress
σ=engineering stress
ε=stretch ratio=(L-Li)/Li
Sample length under the L=deformation
Li=initial sample length
The thermoformable compound also must demonstrate at high temperature can accept elongated features.If should elongation too low, then can tear during this sheet material thermoforming.Therefore, two kinds of significant especially tensile properties are 140 ℃ practical limit tensile strength and 140 ℃ extension at break.Under the extreme stretching condition that some thermoformings are used, people's such as Heck composition has formed the cavity, thereby causes the component breakage.
By reducing the peroxide level that rheology modifying uses, can produce bigger melt ductile composition.Yet lower peroxide level causes lower melt strength and less tensile strength.Therefore, need production that the melt of improvement flexible rheology modifying TPE composition is arranged at present.And then, the present high temperature tensile properties that also needs to improve such thermoforming set of applications compound.
Summary of the invention
Applicant has been found that, by adding the rheology modifying that at least a superoxide and at least a free radical activity auxiliary agent carry out, for example the melt toughness and the high temperature tensile properties of the blend of PP have remarkably influenced at least a elastomerics EAO polymkeric substance or EAO blend polymer and a kind of polyolefine.Rheology modifying composition of the present invention has and only is higher than by adding melt toughness and the high temperature tensile properties that superoxide carries out the corresponding composition of rheology modifying.Therefore, one aspect of the present invention is a kind of rheology modifying, the thermoplastic elastomer of gel-free (TPE) composition in fact, comprise a kind of EAO polymkeric substance or EAO blend polymer and a kind of high-melting-point polymer of one group that is selected from homopolymer polypropylene and propylene/ethylene copolymer composition, wherein, said composition is carried out rheology modifying with at least a superoxide and at least a free radical activity auxiliary agent, and this rheology modifying composition has the melt toughness of at least 600 lis of ox mm/second (cNmm/s), 140 ℃ of practical limit tensile strengths of at least 3 MPas (MPa), 140 ℃ of extension at breaks of at least 400%.This TPE composition can comprise for example filler, stablizer, dispersion agent, pigment and technical oil compounding with usual additive or process auxiliaries.Keeping it from the mixing material of rheology modifying polymer manufacture of the present invention is better than from same polymer manufacture but the processed edge that only carries out the mixing material of rheology modifying with superoxide.
A second aspect of the present invention is a kind of rheology modifying, the TPE preparation of compositions technology of gel-free in fact, this technology comprises: a) add at least a superoxide and at least a free radical activity auxiliary agent in a kind of molten polymer blend, this blend comprises a kind of elastomeric ethylene/alpha-olefinic polymer and a kind of high-melting-point polymer of one group that is selected from homopolymer polypropylene and propylene/ethylene copolymer composition; And b) make this blend polymer keep molten state, make its experience be enough to make this superoxide and coagent to be well-dispersed in shearing condition in this molten polymer blend simultaneously, carry out the rheology modifying of this polymkeric substance and prevent the formation of insoluble polymer gel in fact, fully measuring of rheology modifying is 140 ℃ of practical limit tensile strengths of melt toughness, at least 3 MPas (MPa) of at least 600 lis of ox mm/second (cNmm/s) and 140 ℃ of extension at breaks of at least 400%.This technology randomly comprises a step c), wherein, make the blend polymer of this rheology modifying change into goods, this rheology modifying blend polymer is reclaimed as a kind of solid make this solid change into a kind of intermediate steps that is enough to make the melt state of goods then.Yet, if wish, optional these intermediate steps that comprises of this technology.
A kind of variation of second aspect is a kind of rheology modifying, the TPE preparation of compositions technology of gel-free in fact, this technology comprises: a) add at least a superoxide and at least a free radical activity auxiliary agent in a kind of at least a composition of blend polymer, this blend comprises a kind of elastomeric ethylene/alpha-olefinic polymer and a kind of high-melting-point polymer of one group that is selected from homopolymer polypropylene and propylene/ethylene copolymer composition; And b) make its mixed thing of this polymkeric substance change into a kind of molten polymer blend, this blend is met be enough to and make this superoxide and coagent be well-dispersed in shearing condition in this molten polymer blend, carry out the rheology modifying of this polymkeric substance and prevent the formation of insoluble polymer gel in fact, fully measuring of rheology modifying is 140 ℃ of practical limit tensile strengths of melt toughness, at least 3 MPas (MPa) of at least 600 lis of ox mm/second (cNmm/s) and 140 ℃ of extension at breaks of at least 400%.This technology randomly comprises a step c), wherein, make the blend polymer of this rheology modifying change into goods, this rheology modifying blend polymer is reclaimed as a kind of solid make this solid change into a kind of intermediate steps that is enough to make the melt state of goods then.Yet, if wish, optional these intermediate steps that comprises of this technology.
Second kind of variation of second aspect is a kind of rheology modifying, the preparation technology of the thermoplastic elastomer goods of gel-free in fact, this technology comprises: a) add at least a superoxide and at least a free radical activity auxiliary agent in a kind of molten elastomer ethylene/alpha-olefin polymer or elastomeric ethylene/alpha-olefin polymer blends, a kind of ethylene/alpha-olefin polymerized hydrocarbon or ethylene/alpha-olefin polymer blends of rheology modifying is provided; B) in this rheology modifying polymkeric substance or blend polymer, add a kind of high-melting-point polymer of one group that is selected from homopolymer polypropylene and propylene/ethylene copolymer composition, form a kind of composition polymer blend; And c) make this composition polymer blend change into goods, these goods have 140 ℃ of practical limit tensile strengths of melt toughness, at least 3 MPas (MPa) of at least 600 lis of ox mm/second (cNmm/s) and 140 ℃ of extension at breaks of at least 400%.
A third aspect of the present invention is a kind of goods, and its at least a composition is to make from the TPE composition of first aspect present invention.This TPE composition suitably comprises at least a one group the additive that technical oil, filler and whipping agent are formed that is selected from.These compositions make and use calendering and/or heat forming equipment just can easily form goods.In a related aspect, the TPE composition of this first aspect can be before goods be made with another kind of polymkeric substance, better be one of the polymkeric substance blend that is used for preparing this TPE composition.Such blend can be with any carrying out in various conventional techniques, and wherein a kind of is that the pellet of this TPE composition and the pellet of another kind of polymkeric substance are done blend.
Embodiment
Rheology modifying composition of the present invention comprises a kind of elastomerics EAO polymkeric substance or EAO blend polymer and a kind of high-melting-point polymer.It is the high-melting-point polymer of about 50～about 10wt% that said composition contains EAO polymkeric substance that quantity is about 50～about 90wt% or EAO blend polymer and quantity ideally, and these two percentage all are benchmark with the composition weight.These quantity better are about 65～about 85wt%EAO and about 35～about 15wt% high boiling point polymkeric substance.Select these quantity to make that summation is the 100wt% polymkeric substance.
Be applicable to that EAO polymkeric substance of the present invention (being also referred to as " ethene polymers ") comprises multipolymer and diene modified copolymer.Examples of polymer comprises ethylene/propene (EP) multipolymer, ethylene/butylene (EB) multipolymer, ethylene/octene (EO) multipolymer and ethylene/propene/diene modification (EPDM) multipolymer.Example comprises that (for example Dow Chemical Company makes Attane to extremely-low density linear polyethylene (ULDPE) more specifically
TM), the even line style EAO multipolymer of cladodification (mitsui petrochemical industry company limited system Tafmer for example
TMWith exxon chemical company system Exact
TM) and evenly the EAO of the line style in fact polymkeric substance of cladodification (for example can be available from the Affinity of Dow Chemical Company
TMPolymkeric substance and can be available from the Engage polymkeric substance of Du Pont-Dao elastomerics company).Better the EAO polymkeric substance is the line style of even cladodification and linear ethylene multipolymer in fact, and its density (according to ASTMD-792 mensuration) is about 0.85～about 0.92g/cm
3, especially about 0.85～about 0.90g/cm
3, and its melt index or I
2(measuring under 190 ℃/2.16kg load according to ASTM D-1238) is about 0.01～about 30, better 0.05～10g/10 minute.
Good especially is linear ethylene copolymer or multiple copolymer (being also referred to as " SLEP ") in fact.In addition, various functionalized ethylene copolymers for example EVA (containing the 0.5～about 50wt% that has an appointment) from vinyl-acetic ester deutero-unit also be suitable for.When using the EVA polymkeric substance, be preferably those I
2Be about 0.01～about 500, better 0.05～50g/10 minute person.
" line style in fact " means the main chain that a kind of polymkeric substance has per 1000 main chain carbons to have 0.01～3 long chain branches to replace.
" long chain branches " or " LCB " means a kind of chain length that surpasses the alpha-olefin composition chain length of EAO polymkeric substance or EAO polymers copolymers.Although 13C nuclear magnetic resonance (C-13NMR) spectrometry can't be distinguished during greater than 6 carbon atoms or determines actual carbonatoms in length, can determine or estimate at least the existence of LCB from the molecular weight distribution of EAO polymkeric substance.It also can be from melt flow rate (MFR) (MFR) or via the melt index (I of ASTM D-1238 (190 ℃, 10kg load)
10) and I
2Ratio (I
10/I
2) determine.
" multipolymer " at least 2 kinds of polymer of monomers that meant a kind of polymerization therein.It comprises for example copolymer, terpolymer and tetrapolymer.It especially comprises a kind of by making ethene and at least a comonomer, typically saying a kind of 3～20 carbon atom (C
3-C
20) alpha-olefine polymerizing and the polymkeric substance for preparing.The alpha-olefin example comprises propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and vinylbenzene.This alpha-olefin is a kind of C ideally
3-C
10Alpha-olefin.Multipolymer comprises EP, EB, ethylene/hexene-1 (EH) and EO polymkeric substance preferably.The terpolymer example comprises ethylene/propylene/octene terpolymer and ethene, a kind of C
3-C
20Alpha-olefin and a kind of diene be Dicyclopentadiene (DCPD), 1 for example, the terpolymer of the inclined to one side ethylidene of 4-hexadiene, piperylene or 5--2-norbornylene.
" elastomerics " used herein means a kind of EAO polymkeric substance or EAO blend polymer, its density advantageously be lower than about 0.920g/cc, ideally be lower than about 0.900g/cc, better be lower than about 0.895g/cc, better be lower than about 0.880g/cc, better be lower than about 0.875g/cc even better be lower than about 0.870g/cc again, and its percent crystallinity be lower than about 33%, better be lower than about 29%, better be lower than about 23%.Its density is better greater than about 0.850g/cc.Percent crystallinity is measured with dsc (DSC).
SLEP is a feature with narrow molecular weight distribution (MWD) and narrow short-chain branched distribution (SCBD), and can look like United States Patent (USP) (USP) 5,272,236 and 5,278, prepares like that described in 272, and the relevant portion of these two patents is classified this paper reference as.These SLEP demonstrate outstanding physicals because of its narrow MWD and narrow SCBD and long chain branching (LCB).
USP 5,272,236 (the 5th hurdle the 67th walks to the 6th hurdle the 28th row) have been described via a kind of and have been used at least one reactor but allow many reactors, produce at the polymerization temperature that is enough to produce a kind of SLEP with desired performance and the SLEP of the continuous controlled fusion technology that pressure carries out.Polymerization than good utilisation can limit the shape catalysis technique, via a kind of solution polymerization process, carry out 20 ℃～250 ℃ temperature.The shape the limit catalyzer that is suitable for is disclosed in USP5, and 272,236 the 6th hurdles the 29th row is in the 13rd hurdle the 50th row.
A kind of SLEP preferably has many unique features, and one of these features are ethylene content between between 20～90wt%, better between 30～89wt%, and rest part comprises one or more comonomers.This ethylene content and co-monomer content are benchmark with SLEP weight all, and select to such an extent that to reach total monomer content be 100wt%.For the chain length that can reach 6 carbon atoms, the SLEP co-monomer content can be measured with the C-13NMR spectrometry.
Add some unique SLEP features and comprise I
2With MFR or I
10/ I
2The I of this multiple copolymer
2Be 0.01～30g/10 minute ideally, be 0.05～10g/10 minute better.This SLEP also has I
10/ I
2(ASTM D-1238) 〉=5.63, better 6.5～15, better 7～10.For SLEP, I
10/ I
2Ratio is used to refer to the degree of LCB, therefore, and I
10/ I
2Ratio is big more, and the degree that is equivalent to LCB in this polymkeric substance is high more.
The SLEP that satisfies above benchmark comprises that for example, Dow Chemical Company and road elastomerics company of Du Pont are via the Engage polyolefin elastomer that can limit the shape catalytic production and other polymkeric substance.
The high-melting-point polymer composition of TPE of the present invention is the homopolymer of propylene, or propylene and a kind of alpha-olefin multipolymer of ethene, 1-butylene, 1-hexene or 4-methyl-1-pentene for example, or the blend of a kind of homopolymer and a kind of multipolymer.The blend of this homopolymer, this multipolymer or homopolymer and multipolymer, each can carry out coring.This alpha-olefin better is an ethene.This multipolymer can be the blend of a kind of random copolymers or a kind of segmented copolymer or random copolymers and segmented copolymer.Therefore, this composition better is selected from one group that polypropylene (PP) homopolymer and propylene/ethylene copolymer are formed.The MFR of this composition (230 ℃ and 2.16kg load) is 0.3～60g/10 minute, better 0.8～40g/10 minute, better 1～35g/10 minute.
" coring " used herein means a kind of by adding for example Millad of nucleating agent
TMThe polymkeric substance that can carry out modification available from a kind of dibenzyl Sorbitol Powder of Milliken company.Other usual nucleating agent also can use.
The preparation of polypropylene (PP) relates to as Cecchin USP 4,177, and the Z-type catalyst described in 160 is the use of titanous chloride and diethyl monochlor(in)ate aluminium combination for example.The polymerization technique that is used for producing PP comprises: at about 50～90 ℃ and 0.5～1.5MPa (slurry processs of 5～15atm) operations, and the vapor phase process and the liquid monomer process that must give especially to look after to removing of amorphous polymer.Can in this reaction, add ethene, the polypropylene of ethylene block is arranged with generation.The PP resin also can be by using various metallocenes, single-point and can limitting any in the shape catalyzer to prepare together with its related process.
This superoxide better is a kind of organo-peroxide.The organo-peroxide that is suitable for is 120 ℃ of transformation period that have at least one hour.The superoxide example comprises and contains α that α '-two (tert-butyl peroxy base) di-isopropyl benzo can trade(brand)name VULCUP
TMAvailable from a series of vulcanizing agents and the polymerizing agent of Hercules company, containing dicumyl peroxide also can trade(brand)name Di-cup
TMAvailable from a series of these type of medicaments of Hercules company, and the Lupersol of Elf Atochem North American Corp. manufacturing
TMThe Trigonox that superoxide or Akzo Nobel company make
TMOrgano-peroxide.Lupersol
TMSuperoxide comprises Lupersol
TM101 (2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane), Lupersol
TM130 (2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexin-3) and Lupersol
TM575 (peroxides-2 ethyl hexanoic acid tert-pentyl ester).Other suitable superoxide comprises 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane, di-t-butyl peroxide, peroxidation two tert-pentyls, 2,5-two (uncle's penta peroxy)-2,5-dimethylhexane, 2,5-two (tert-butyl peroxy base)-2,5-phenylbenzene hexane, peroxidation two (α-Jia Jibianji), benzoyl peroxide, t-butylperoxyl benzoate, 3,6,9-triethyl-3,6,9-trimethylammonium-1,4,7-three peroxy nonanes and two (tert-butyl peroxy base) diisopropyl benzene.
In the scope of the suitable amount of this superoxide about 100～about 10,000 weight parts in per 1,000,000 parts by weight polymer.This scope is about 500 in per 1,000,000 parts by weight polymer～about 5,000, better about 1,000～about 3,000 weight parts ideally.
This free radical activity auxiliary agent is a kind of monomer or low-molecular weight polymer that two or more functional groups to the free radical high response are arranged.Say that typically these functional groups are methacrylic acid group, allyl group or vinyl.This free radical activity auxiliary agent has improved the rheology modifying effect of this superoxide by two kinds of mechanism.At first, capture, produce a kind of more low-energy state, more long-life free radical by the allylic hydrogen from this coagent of peroxide-induced.Then, this free radical can be induced the branching of this ethylene elastomer by taking hydrogen by force.Since this free radical than low-energy state, thereby polypropylene or the β-chain rupture of ethylene elastomer phase and disproportionation are unlikely to take place.Secondly, this multifunctional coagent can serve as the bridge formation group between these polymer chains.
The free radical activity auxiliary agent that is suitable for this purposes can comprise diallyl p phthalate, triallyl cyanurate, triallyl isocyanurate, 1,2-polyhutadiene, Vinylstyrene, trimethylammonium vinylformic acid three (methylol) propane ester, dimethacrylate macrogol ester, Ethylene glycol dimethacrylate, pentaerythritol triacrylate, allyl methacrylate(AMA), N, N '-metaphenylene dimaleimide, toluene dimaleimide paraquinonedioxime, oil of mirbane and diphenylguanidine.Coagent is a triallyl cyanurate, 1 preferably, 2-polyhutadiene, Vinylstyrene and trimethylammonium vinylformic acid three (methylol) propane ester.
The suitable amount of this coagent be about 50～about 20, preferred about 100～about 10 in 000ppm (weight) scope, in 000ppm (weight) scope.This scope ideally about 500～about 5,000, better 1,000～3, within the 000ppm (weight).
This superoxide and free radical activity auxiliary agent can add with any usual means.Adding program example comprises: it is absorbed on the polymeric aggregate, when entering the equipment that is mixed, for example it is added in the polymeric aggregate during opening for feed of an extruding machine by pellet, add it to compounding equipment for example in the polymer melt of Haake mixing machine, Ban Buli Banbury mixer, Farrell's continuous mixer or this kneader of cloth or be injected in the extruding machine, with 100% effective constituent (being net phase) or randomly as a kind of oil for example dispersion liquid or the solution in the treated oil inject at this extruding machine content fused time point.Program is that this superoxide and coagent are absorbed on the polymeric aggregate preferably.
The usage quantity of this superoxide and free radical activity auxiliary agent will be enough to provide 140 ℃ of practical limit tensile strengths of melt toughness, at least 3 MPas (MPa) of at least 600 lis of ox mm/second (cNmm/s) and 140 ℃ of extension at breaks of at least 400% and not have substantive gel formation.With wt% is benchmark, coagent and superoxide relatively good in about 1: 10～10: 1 scope.Better ratio range is about 1: 5～5: 1, and best ratio range is about 1: 2～about 2: 1.The optimum ratio of coagent depends on the ethylene/alpha-olefin-polypropylene ratio that uses in this mixing material.With wt% is benchmark, and the scope of application of EAO/PP is 80/20～40/60.Scope is 65/35～75/25wt% preferably.
Melt toughness used herein is that melt strength and melt ductility are long-pending.Melt strength used herein (MS) be to one from the capillary rheometer die head with 33 seconds
-1The polymer melt extruded of constant velocity of shear the fusion monofilament this monofilament by a pair of make this monofilament from the initial velocity of 1cm/ second with 0.24cm/ second
2The maximum stretching force measured when stretching of the nip rolls that quickens of acceleration.This fusion monofilament better produces as follows: the polymkeric substance in the machine barrel of an Instron capillary rheometer of heating 10g threading, make this polymkeric substance 190 ℃ of balances 5 minutes, this polymkeric substance is extruded via the kapillary die head of diameter 0.21cm, length 4.19cm with 2.54cm/ minute velocity of piston.This drawing force better is to install to such an extent that make this nip rolls leave at this monofilament that the Goettfert Rheotens of 10cm measures under that of this kapillary die head with one.Melt ductility used herein (ME) is to make the top speed of needed this nip rolls of this single wire fracture away from Goettfert Rheotens, measures second with cm/.
High temperature limit tensile strength used herein or 140 ℃ of ultimate tensile strengths are by measuring from compression moulding sheet material or extruded sheet cutting ISO37T2 dumbbell specimen.When the test extruded sheet, sample is to cut on the machine direction.Then, the sample of cutting being placed on one is equipped with one and is heated on 140 ℃ the tensile testing machine of environmental chamber.Allow this sample balance 10 minutes, then with 50cm/ minute slip head velocity strain.Record tensile strength and extension at break.
For the existence that detects insoluble gel in the polymer composition rheology modifying composition for example of the present invention and give in ideal conditions quantitatively, as long as said composition was immersed in a kind of suitable solvents for example in the backflow dimethylbenzene described in the ASTM D 2765-90 method B 12 hours.Then, with any soluble part of said composition separate, dry, weigh, and do suitable correction according to the knowledge of said composition.For example, will in this solvent, the weight of soluble non-polymer composition from initial weight, deduct, and will in this solvent, the weight of insoluble non-polymer composition from initial weight and final weight, deduct.The soluble polymkeric substance that reclaims is reported as percent gel content.For the present invention's purpose, " gel-free in fact " but mean percent gel content be lower than ideally about 10%, more desirably be lower than about 8%, better be lower than about 5%, better be lower than about 3%, also better be lower than about 2% in addition better be lower than about 0.5%, be preferably lower than the limit of detection when using dimethylbenzene as solvent.Can stand the terminal use of gel for some, percent gel content can be higher.
Composition of the present invention can with any or multiple material compounding of usually adding in the polymkeric substance.These materials comprise that for example, the EAO of rheology modifying, technical oil, softening agent, special additive do not comprise stablizer, filler (reinforcing filler and non-reinforcing filler) and pigment as yet.These materials can be before this based composition carries out rheology modifying otherwise after with composition compounding of the present invention.The insider can easily select any applicable combination of additive and amount of additives, and the time of compounding, and need not too much experiment.
Technical oil often be used for reducing in a kind of viscosity, hardness, modulus and the cost of composition any one or multinomial.The most frequently used technical oil has specific ASTM title, and this depends on it is categorized as paraffin oil, naphthenic oil or aromatic oil.Usually be familiar with elastomerics processing and can know all that with the value of people in the industry of being familiar with rheology modifying TPE composition processing of the present invention particularly the oil of which kind is the most useful.When this technical oil uses, being benchmark with the composition total weight, is to exist with the quantity in about 0.5～about 50wt% scope ideally.Some low～middle molecular weight ester softening agent also can be used for strengthening low-temperature performance.The example of operable ester comprises isooctyl tallate, the different monooctyl ester of oleic acid, the positive butyl ester of resinous acid, n butyl oleate, butoxyethyl oleate, dioctyl sebacate, sebacic acid two (2-ethylhexyl), dioctyl azelate, dodecanedioic acid di-isooctyl, pentanedioic acid alkyl-alkyl ether diester.
Various specialist additives can be advantageously used in the composition of the present invention.This additive comprises oxidation inhibitor, surface tension modifier, anti, lubricant, biocide for example organometallic compound, isothtazolones (isothiazolones), organosulfur compound and mercaptan compound; Oxidation inhibitor is oxybenzene compound, secondary amine class, phosphite and monothioester class for example; For example quaternary ammonium compound, amine and ethoxylation of static inhibitor, propoxylation or glycerols compound; Filler and toughener be carbon black, glass, metal carbonate for example calcium sulfate, talcum, clay or graphite fibre of lime carbonate, metal sulfate for example for example; Hydrolysis stabilizer; Lubricant is lipid acid, Fatty Alcohol(C12-C14 and C12-C18), ester class, fatty amide, metallic stearate, paraffin and Microcrystalline Wax, silicone and ortho-phosphoric acid ester class for example; Releasing agent is minuteness particle or pulverulent solids, soap class, wax class, silicone, polyethylene glycols and complex ester class three stearic acid three (methylol) propane ester or pentaerythritol tetrastearates for example for example; Pigment, dyes and dyestuffs; Softening agent is ester for example phthalic ester, adipic acid ester and the benzoic ether of diprotic acid (or its acid anhydride) and monohydroxy-alcohol for example; Thermo-stabilizer is monooctyl ester and the carboxylic acid barium or the calcium of organo-tin mercaptide, thioglycolic acid for example; UV light stabilizing agent is hindered amine, salicyl benzotriazole, 2-hydroxyl-4-alkoxyl group benzophenone, salicylate, cyanoacrylate, nickel chelate and inclined to one side toluenyl malonic ester and oxalic dianilide for example.Fortified phenol oxidation inhibitor is can be available from the Irganox of Ciba-Geigy company preferably
TM1076.Each typically is no more than 45wt%, advantageously about 0.001～about 20wt%, better about 0.01～about 15wt%, better about 0.1～about 10wt% with composition total weight as benchmark in the above-mentioned additive when using.
Rheology modifying TPE composition of the present invention can be with any component, sheet material or other form of being made in the numerous usual TPE work program.Said composition also can shaping, spinning or is drawn into film, fiber, laminated multi-layer body or extruded sheet, perhaps can with the compounding on any machine that is applicable to this type of purpose of one or more organic or inorganic materials.Said composition is particularly conducive to for example calendering of high temperature TPE technology, extrusion molding and thermoforming.
TPE composition of the present invention for example for the blend of PP, has the performance of improving surprisingly with respect to the EAO multipolymer that only suffers from the rheology modifying that carries out with superoxide and high-melting-point polymer.The rheology modifying that carries out with superoxide and free radical activity auxiliary agent provides the melt toughness of ideal and improvement and the combination of high temperature tensile properties.
Composition of the present invention can use usual polymkeric substance manufacture craft, and for example above those that confirm are configured as various molding.The portion that the is suitable for molding inventory of limit far away comprises: car body part for example read by dashboard crust, collision bumper lace, vehicle body side rolled-up stock, outer decoration, interior trim, weather strip, air, inlet mouth and wheel cover, and non-automobile application examples such as polymeric film, polymer sheet, tubing, rubbish container, storage vessel, meadow facility ribbon or reticulation, scythe, garden hoses, and other garden electrical component, recreational vehicle component, golf cart component, open cause car component and Sea-plane component.Said composition also can be with waterproof applications waterproof membrane for example.Said composition can also be used to make for example boots main body of industrial work boots especially of article of footwear.The insider need not too much experiment just can easily augment this part inventory.
Following examples explanation but do not express or impliedly limit the present invention.Except as otherwise noted, otherwise all shares and percentage all be with the gross weight benchmark by weight.Embodiments of the invention identify with Arabic numerals, and comparative example is represented with alphabetic(al) letter.
Embodiment and comparative example
Utilize following program, from 9 kinds of compositions of two kinds of different EAO polymer manufacture, wherein 8 kinds to represent the present invention (embodiment 1～8), a kind be comparison (Comparative examples A).All each composition bucket mixes, allows this superoxide and coagent absorb in the pellet, this blend rotates the dual shaft lever extruding machine in the same way with a Werner Pfliederer ZSK 30 and is processed into pellet production then by making for 9 kinds of compositions.Then the partical formulation is processed into sheet material on the single multiple screw extruders of 2 inches Killion of 6 inches wide die heads of an outfit.Produce and test 0.050 inch thick sheet.
The EAO polymkeric substance that uses among these embodiment is EAO-1, a kind of I
2For 0.5g/10 minute, nominal density are ethene/1-octene copolymer (Engage 8180 polyolefin elastics are available from Du Pont-Dao elastomerics company) of 0.863g/cc; EAO-2, a kind of nominal mooney viscosity is 47, nominal density is 0.868g/cc, with the number-average molecular weight of gel permeation chromatography be about 80,000 and molecular weight distribution (MWD) be experiment ethene/1-octene copolymer (producing) of about 2.3 by Du Pont-Dao elastomerics company; And EAO-3, a kind of nominal mooney viscosity is 45, nominal density is 0.870g/cc, with the number-average molecular weight (Mn) of gel permeation chromatography for about 78,000 and molecular weight distribution (MWD) be experiment ethene/butene-1 copolymer (by Du Pont-Dao elastomerics company production) of about 2.0.
The polypropylene that uses among these embodiment (PP) is that melt flow is 0.8 homopolymer polypropylene (Profax PD-191 is available from Montell company).
The superoxide that uses among these embodiment is POX-1,2, and 5-dimethyl-2,5-two (tert-butyl peroxy base) hexane (Lupersol 101, Elf Atochem company); And POX-2, peroxidation two (tert-pentyl) (DTAP, Crompton chemical company).
The free radical activity auxiliary agent that uses among these embodiment is: FRC-1, trimethylammonium vinylformic acid three (methylol) propane ester (SR-350 KD96 (carrier band is on the Calucium Silicate powder of Akron Dispersions company preparation, from the 75%SR-350 of Sartomer company)); FRC-2, trimethylammonium vinylformic acid three (methylol) propane ester (from 100% SR-350 of Sartomer company); FRC-3, triallyl cyanurate (TAC is from Ctytec industrial); And FRC-4,1,2-polyhutadiene (Ricon 152D (carrier band is on the Calucium Silicate powder of Akron Dispersions company preparation, from 68% Ricon 152 of Sartomer company)).Before bucket mixes, make FRC-4 be warming to about 30 ℃ to form a kind of liquid.
Embodiment 1～2 and Comparative examples A
Table I has gathered the data of the composition of embodiment 1～2 and Comparative examples A.Table I has identified EAO polymkeric substance, superoxide and free radical activity auxiliary agent (embodiment 1 and 2), and the wt% of these compositions has been described.
Table I
| Embodiment | EAO-1 | PP | POX-1 | FRC-1 |
| 1 | 68.7 | 30.8 | 0.2 | 0.3 |
| 2 | 68.6 | 30.7 | 0.3 | 0.4 |
| A | 68.6 | 30.7 | 0.7 | 0 |
Measured these embodiment and comparative example composition performance and be reported in the following Table II.Goetfert Rheotens has measured the melt strength (MS) and the melt ductility (ME) of the fusion monofilament of the polymer melt of extruding from the capillary rheometer die head.Melt toughness (MT) is that MS and ME are long-pending.Kept 33 seconds
-1Constant velocity of shear, simultaneously with a pair of nip rolls this monofilament that stretches, make this monofilament from the initial velocity of 1cm/ second with 0.24cm/ second
2Speed quicken.This nip rolls is equipped with the strain table, to measure this fusion monofilament to the strained stress response.High temperature (140 ℃) stress-strain is the stretching test machine determination that is heated to 140 ℃ environmental chamber with an outfit.Actual stress (practical limit tensile strength (TUTS)) is to determine with the Considere equation, and has measured extension at break (ultimate strain (US)).The gel content of said composition described in ASTMD2765-90 by measuring in 12 hours with the backflow xylene extraction.
Table II
| Embodiment | MS (cN) | ME (mm/s) | MT (cNmm/s) | 140℃ TUTS (Mpa) | 140℃ US (％) | Gel (wt％) |
| 1 | 10.58 | 115.6 | 1223 | 0.480 | ＞1200 | 0.9 |
| 2 | 17.36 | 78.1 | 1356 | 0.905 | 523 | 0.6 |
| A | 7.55 | 75.3 | 569 | 0.457 | 344 | 1.0 |
The some points of the data declaration of listing in the Table II.At first, embodiment 1 and 2 demonstrates the melt toughness that is significantly higher than Comparative examples A.These results show, with there being the lower level superoxide of free radical activity auxiliary agent to obtain higher melt toughness.Secondly, the high temperature that embodiment 1 and 2 demonstrates at 140 ℃ has higher tensile property.Compare with Comparative examples A, embodiment 1 has high slightly practical limit tensile strength and remarkable high ultimate stress.Compare with Comparative examples A, embodiment 2 has nearly 2 times ultimate tensile strength and remarkable high ultimate stress.For above disclosed other EAO polymkeric substance, propene polymer, kind rheology modifier or modified technique, all expect similar result.
Embodiment 3～8
Utilize different EAO polymkeric substance, superoxide and/or free radical activity auxiliary agent, use program and the equipment of embodiment 1～2, prepared other six kinds of the present invention combination.Table III has identified EAO polymkeric substance, superoxide and free radical activity auxiliary agent, and the wt% of each composition has been described.
Table III
| Embodiment | EAO-1 | EAO- 2 | EAO-3 | PP | POX- 1 | POX-2 | FRC-2 | FRC-3 | FRC- 4 |
| 3 | 69.79 | 0 | 0 | 29.91 | 0 | 0.15 | 0.15 | 0 | 0 |
| 4 | 69.79 | 0 | 0 | 29.91 | 0.15 | 0 | 0 | 0.15 | 0 |
| 5 | 0 | 69.79 | 0 | 29.91 | 0.15 | 0 | 0.15 | 0 | 0 |
| 6 | 0 | 69.79 | 0 | 29.91 | 0.05 | 0 | 0.05 | 0 | 0 |
| 7 | 0 | 0 | 69.79 | 29.91 | 0.15 | 0 | 0.15 | 0 | 0 |
| 8 | 69.758 5 | 0 | 0 | 29.896 5 | 0.15 | 0 | 0 | 0 | 0.195 |
According to determining the character of the composition of embodiment 3～8 with above embodiment 1～2 and the described same way as of Comparative examples A.They are reported in the following Table IV.
Table IV
| Embodiment | MS (cN) | ME (mm/s) | MT (cNmm/s) | 140℃ TUTS (Mpa) | 140℃ US (％) | Gel (wt％) |
| 3 | 27 | 43 | 1161 | 5.25 | 1367 | 0.9 |
| 4 | 25 | 61 | 1525 | 5.09 | 1287 | 1.4 |
| 5 | 27 | 45.9 | 1239 | 4.26 | 1510 | 1.1 |
| 6 | 13 | 82.6 | 1074 | 7.71 | 1300 | 0.9 |
| 7 | 21 | 65.3 | 1371 | 11.7 | 1324 | 0.16 |
| 8 | 21 | 55.4 | 1163 | 9.6 | 1364 | 0.30 |
Embodiment 3～8 demonstrates the melt toughness (1074～1525cN-mm/s) more much higher than Comparative examples A (569cN-mm/s).And then, comparing with Comparative examples A, embodiment 3～8 demonstrates much higher 140 ℃ of practical limit tensile strengths and remarkable 140 ℃ of higher ultimate strains.For blend or its program and the quantity of other EAO polymkeric substance disclosed herein and EAO polymkeric substance, PP polymkeric substance, superoxide, free radical activity auxiliary agent, all expect similar result.
Claims (20)
1. the gel content of a rheology modifying is lower than 10% composition for thermoplastic elastomer, it comprises at least a elastomeric ethylene/alpha-olefinic polymer or ethylene/alpha-olefin polymer blends and at least a high-melting-point polymer that is selected from homopolymer polypropylene or propylene/ethylene copolymer, wherein this rheology modifying is to be brought out by the combination of superoxide and free radical activity auxiliary agent, wherein said composition have 600cNmm/s at least melt toughness, 140 ℃ at least 3MPa the practical limit tensile strength and at 140 ℃ at least 400% extension at break.
2. the composition of claim 1, wherein, this superoxide is a kind of organo-peroxide.
3. the composition of claim 2, wherein, this organo-peroxide is selected from α, α '-two (tert-butyl peroxy base)-diisopropyl benzene, dicumyl peroxide, peroxidation two (tert-pentyl), 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexin-3,2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane, peroxide-2 ethyl hexanoic acid tert-pentyl ester, di-t-butyl peroxide, 2,5-two (uncle's penta peroxy)-2,5-dimethylhexane, 2,5-two (tert-butyl peroxy base)-2,5-phenylbenzene hexane, peroxidation two (α-Jia Jibianji), t-butylperoxyl benzoate, benzoyl peroxide, 3,6,9-triethyl-3,6,9-trimethylammonium-1,4,7-three peroxidation nonanes and two (tert-butyl peroxy base) diisopropyl benzene.
4. the composition of claim 1, wherein, this free radical activity auxiliary agent is selected from: diallyl p phthalate, triallyl cyanurate, triallyl isocyanurate, 1,2-polyhutadiene, Vinylstyrene, trimethylammonium vinylformic acid three (methylol) propane ester, dimethacrylate macrogol ester, Ethylene glycol dimethacrylate, pentaerythritol triacrylate, allyl methacrylate(AMA), N, N '-metaphenylene dimaleimide, toluene dimaleimide paraquinonedioxime, oil of mirbane and diphenylguanidine.
5. the composition of claim 4, wherein, this free radical activity agent is selected from: triallyl cyanurate, 1,2-polyhutadiene, Vinylstyrene and trimethylammonium vinylformic acid three (methylol) propane ester.
6. the composition of claim 1, wherein, the polymerization therein of this ethylene/alpha-olefin polymer at least a alpha-olefin comonomer, this alpha-olefin contains 3～20 carbon atoms.
7. the composition of claim 6, wherein, this alpha-olefin contains 3～10 former giving of carbon.
8. the composition of claim 1, wherein, this ethylene/alpha-olefin polymer is that a kind of diene is polymer-modified, and this diene is selected from a group of following composition: norbornadiene, Dicyclopentadiene (DCPD), 1, the inclined to one side ethylidene of 4-hexadiene, piperylene or 5--2-norbornylene and composition thereof.
9. the composition of claim 1, wherein, this high-melting-point polymer is a kind of nucleating polymer.
10. the composition of claim 1 further comprises a kind of technical oil, is benchmark with the composition total weight, and its quantity is in greater than 0～0wt% scope.
11. the composition of claim 1 or claim 10 further comprises a kind of filler, is benchmark with the composition total weight, its quantity is in 0～70wt% scope.
12. the composition of claim 1 or claim 10 further comprises a kind of whipping agent, is benchmark with the composition total weight, its quantity is in greater than 0～10wt% scope.
13. the composition of claim 11 further comprises a kind of whipping agent, is benchmark with the composition total weight, its quantity is in greater than 0～10wt% scope.
14. the composition of claim 1, the amount that wherein at least a elastomeric ethylene/alpha-olefinic polymer or ethylene/alpha-olefin polymer blends exist is 50～90wt%, the amount that exists with at least a high-melting-point polymer is the high-melting-point polymer of 50～10wt%, and described percentage all is benchmark with the composition weight.
15. goods, the composition that its at least a composition is Accessory Right requirement 1 is made.
16. the goods of claim 15, wherein, said composition further comprises at least a one group the additive that is selected from following composition: technical oil, filler and whipping agent.
17. the goods of claim 16, wherein, said composition further comprises, and is benchmark with the composition total weight, and amount is greater than the technical oil in 0～50wt% scope.
18. the goods of claim 16, wherein, said composition further comprises and is selected from following filler: glass, silica, carbon black, metal carbonate, metal sulfate, talcum, clay and graphite fibre.
19. the goods of claim 16, wherein, said composition further comprises, and is benchmark with the composition total weight, and amount is greater than the filler in 0～70wt% scope.
20. the goods of claim 16, wherein, said composition further comprises, and is benchmark with the composition total weight, and amount is greater than the whipping agent in the 0-10wt% scope.
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| US23459900P | 2000-09-22 | 2000-09-22 | |
| US60/234599 | 2000-09-22 | ||
| US09/961056 | 2001-01-13 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104583245A (en) * | 2012-08-16 | 2015-04-29 | 埃克森美孚化学专利公司 | Highly branched compositions and processes for the production thereof |
| CN105283502A (en) * | 2012-12-21 | 2016-01-27 | 陶氏环球技术有限责任公司 | Composition, thermoplastic vulcanizates made therefrom and articles formed from the same |
| CN105358621A (en) * | 2013-07-16 | 2016-02-24 | 陶氏环球技术有限责任公司 | Flexible power cable insulation |
| WO2025157303A1 (en) * | 2024-01-26 | 2025-07-31 | Dow Global Technologies Llc | Foamable compositions comprising polyolefin elastomers (poe) |
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2001
- 2001-09-21 CN CN 200610058410 patent/CN1840577A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104583245A (en) * | 2012-08-16 | 2015-04-29 | 埃克森美孚化学专利公司 | Highly branched compositions and processes for the production thereof |
| CN104583245B (en) * | 2012-08-16 | 2017-03-29 | 埃克森美孚化学专利公司 | Highly branched composition and preparation method thereof |
| CN105283502A (en) * | 2012-12-21 | 2016-01-27 | 陶氏环球技术有限责任公司 | Composition, thermoplastic vulcanizates made therefrom and articles formed from the same |
| CN105283502B (en) * | 2012-12-21 | 2017-11-14 | 陶氏环球技术有限责任公司 | Composition, the TPV being made from it and the article formed by it |
| CN105358621A (en) * | 2013-07-16 | 2016-02-24 | 陶氏环球技术有限责任公司 | Flexible power cable insulation |
| WO2025157303A1 (en) * | 2024-01-26 | 2025-07-31 | Dow Global Technologies Llc | Foamable compositions comprising polyolefin elastomers (poe) |
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