CN101501127A - Polymer compositions comprising cyclic olefin copolymers and polyolefin modifiers - Google Patents

Abstract

A polymer composition comprises (a) greater than 50 wt% (based upon the weight of the composition) of a cyclic olefin copolymer comprising at least one acyclic olefin and at least 20 weight % of one or more cyclic olefins (based upon the weight of the cyclic olefin copolymer), wherein at least a portion of the cyclic olefin copolymer has a glass transition temperature of greater than 150 DEG C; and (b) less than 50 wt% (based upon the weight of the composition) of an acyclic olefin polymer modifier, at least a portion of the modifier having a glass transition temperature of less than -30 DEG C; and no portion of the modifier having a softening point greater than +30 DEG C, wherein the Bicerano solubility parameter of the modifier being no more than 0.6 J<0.5>/cm<1.5> less than the Bicerano solubility parameter of the cyclic olefin copolymer. The polymer composition has a notched Izod impact resistance measured at 23 DEG C of greater than 500 J/m and a heat distortion temperature measured using a 0.46 MPa load of greater than 135 DEG C.

Description

The polymer composition that comprises cyclic olefin copolymer and polyolefin modifiers

Technical field

[0001] the present invention relates to comprise the polymer composition of cyclic olefin copolymer and polyolefin modifiers.

Background technology

[0002] cyclic olefin copolymer has high glass-transition temperature and high rigidity, yet there is the defective of the non-constant of impact property in they and is brittle for many application.Carried out a large amount of effort and come to improve their shock resistance, and improved their rigidity by sneaking into reinforce by sneaking into polytype properties-correcting agent.These previous effort all are not very successful, and to a great extent, and cyclic olefin copolymer has been included into the application that only utilizes its optical clarity, moistureproofness and good birefringenct property.

[0003] polyolefine, and those of polyethylene and polypropylene group particularly are cheap low density heat plasticity materials, and it is easy to fusion and chemically-resistant material.These materials therefore as domestic articles and the field of Electrical and Electronic part in many purposes are arranged.Yet polyolefine has relatively poor mechanical property and relative low heat-drawn wire (HDT) usually.For example, typical homopolymer polypropylene has the modulus in flexure of about 1.9GPa, about 126 ℃ heat-drawn wire under 0.46MPa and the notched izod shock resistance of about 48J/m.Therefore these plastics are not suitable for the field of requirement high heat resistance, high mechanical strength and/or high impact properties.

[0004] in order to improve their shock resistance, often homopolymer polypropylene and ethylene-propylene rubber(EPR) (EPR) or ethylene-propylene-diene (EPDM) rubber mix.EPR and EPDM rubber are used for impact modified because they up to its second-order transition temperature of-45 ℃ approximately keep ductility and in addition-29 ℃ routine test temperature under effective tenacity-increased profax.EPR, EPDM and polypropylene have similar polarity, and therefore little rubber areas can be dispersed in the polypropylene well.Shock resistance can also make impact copolymer and improve by the ethylene copolymer with propylene and percentum.Yet the impact property of these improvement has been brought the modulus of reduction and the heat-drawn wire of reduction.Therefore, the general polypropylene impact copolymer that contains EPR has the modulus in flexure of about 1.0GPa, about 92 ℃ heat-drawn wire under 0.46MPa, do not have specimen fracture (approximately 500J/m or higher) to such an extent as to room temperature notched izod shock strength is so high, and only have ductile failure (approximately the energy of 43J is absorbed) in the instrument shock test under-29 ℃ usually.

[0005], polypropylene and ethylene-propylene or ethylene-propylene-diene elastomer and mineral filler such as talcum, mica or glass fibre can be mixed in order to reach equilibrated character more.Talcum and mica reinforcing filler are preferable over glass fibre usually, because the compound polymkeric substance has better surface and flowing property.The example of these materials is AS65KW-1ATM of ExxonMobil, and it has the modulus in flexure of about 2.4GPa, and about 124 ℃ heat-drawn wire under 0.46MPa and the notched izod of about 400J/m are impacted.These polymeric blends have the excellent balance of performance, are used for automotive interior application.Yet, these mixtures can not be used for the structure applications of some automobiles, wherein the available material require have under 0.46MPa at least 140 ℃ and under 1.80MPa at least 120 ℃ heat-drawn wire, have simultaneously the modulus of 2.5GPa at least and at least the room temperature notched izod of 100J/m impact.

[0006] to be better than the polyacrylic equilibrated character of blended in order reaching, also to have proposed cyclic olefin copolymer and polyolefinic mixture.Ethene and norbornylene and with 2, the multipolymer of 3-dihydro Dicyclopentadiene (DCPD) is disclosed in United States Patent(USP) Nos. 2,799,668 (July 16 nineteen fifty-seven) and 2,883,372 (April 21 nineteen fifty-nine).Yet these polymkeric substance use TiCl ₄As catalyzer and by open loop metathesis polymerizable-cyclic olefin ring with ethylene copolymer during open, in main polymer chain, stay remaining two keys.Because open loop, chain become not as the rigidity of addition polymerization cyclic olefin copolymer.Unsaturated these polymkeric substance oxidation instability at high temperature that also makes of remnants in their main chains.Therefore, although these multipolymers have desirable rigidity and transparency, their poor heat resistance.

[0007] United States Patent (USP) 3,494, and 897 disclose the free-radical polymerized incompatible preparation ethylene/cyclic olefin copolymer that high pressure, superoxide cause, but these polymerizations only can be in conjunction with a spot of cyclic olefin.Therefore, polymkeric substance does not have high glass-transition temperature.

[0008] ethene/norbornene copolymer and polyolefinic several mixture are described (DE2731445C3, DD150751, DD203061, DD203059, DD203062, DD205916, DD206783, DD209840, DD214851, DD214849 and DD214850) in early days by the researchist of VEBLeuna-Werke in the 1980's.Yet these mixtures prepared before discovery Z-N vanadium/aluminium or metallocene addition polymerization catalyzer.Ethene/the norbornene copolymer that is used for these mixtures is by opening cyclic rings between polymerization period and causing that the undersaturated catalyzer on main polymer chain makes.The vicat softening temperature of these patent illustrated shows that at 114 to 133 ℃ these polymkeric substance do not have the needed thermostability of vehicle structure purposes.In this respect, when being interpreted as vicat softening temperature usually than high about 10 ℃ of the second-order transition temperature of glassy polymers, and the second-order transition temperature of glassy polymers usually than it high about 10 ℃ of the heat-drawn wire of 0.46MPa.Therefore from 114 to 133 ℃ vicat softening temperature roughly is equivalent to use about 94 to 113 ℃ heat-drawn wire of 0.46MPa load.

[0009] U.S. Patent No. 4,614, and 778 disclose a kind of ethene and 1,4,5,8-two endo-methylene groups-1,2,3,4,4a, 5,8,8a-octahydro naphthalene and the alpha-olefin of choosing wantonly with at least three carbon atoms or the random copolymers of cycloolefin such as norbornylene.From 1,4,5,8-two endo-methylene groups-1,2,3,4,4a, 5,8, the polymerized unit of 8a-octahydro naphthalene be from 3:97 to 95:5 with mole ratio from the polymerized unit of ethene and use Z-N vanadium/Al catalysts with 1,4,5,8-two endo-methylene groups-1,2,3,4,4a, 5,8,8a-octahydro naphthalene is incorporated into the ethene polymers chain.The not open loop during copolymerization of cyclic olefin ring, and the multipolymer that obtains does not comprise the unsaturated part of residue in their main chain.Therefore, these multipolymers have high heat-drawn wire and the second-order transition temperature up to 171 ℃.Yet when being pressed into film, multipolymer is quite brittle, and all is ethene and the multipolymer that comprises the cyclic olefin comonomer of at least four condensed ring.The shortcoming of the comonomer that these are bigger is to require extra diels-alder addition reaction cause ethene and cyclopentadiene to generate, and makes that synthetic they are more expensive than norbornylene or dicyclopentadiene.Do not illustrate blend in this patent.

[0010] U.S. Patent No. 5,087, and 677 have described ethene and the particularly copolymerization of norbornylene of cyclic olefin of using zirconium and hafnium metallocene catalyst.Be described in U.S. Patent No. 4,614,778 vanadium/aluminium polymeric copolymer analog seemingly, the multipolymer of metallocene polymerization does not have the unsaturated part of residue at their main chain, and not open loop of cyclic olefin.Therefore, these metallocene ethylene/cyclic olefin copolymers have high thermal stability and second-order transition temperature, for example for the value of second-order transition temperature illustration up to 163 ℃.Exist and to mention briefly, but the alloying that does not have this multipolymer of illustration and other polymkeric substance such as polyethylene, polypropylene, (ethylene/propene) multipolymer, polybutene, gathers (4-methyl-1-pentene), polyisoprene, polyisobutene and natural rubber.

[0011] U.S. Patent No. 4,918,133 disclose a kind of cyclenes type random copolymer composition, it is said that it demonstrates excellent thermotolerance, chemical-resistant, rigidity and shock resistance, and it comprises that (A) comprises the multipolymer of ethylene component and cyclenes component, it has the limiting viscosity [η] of the 0.05-10dl/g that measures and is not less than 70 ℃ softening temperature (TMA) in naphthane under 135 ℃, (B) one or more are selected from the non-rigid multipolymer of following material: (i) comprise ethylene component, the random copolymers of at least a other alpha-olefin component and cyclenes component, it has measures 0.01-10dl/g limiting viscosity [η] and is lower than 70 ℃ softening temperature (TMA) in naphthane under 135 ℃, (ii) the amorphism that is formed by at least two kinds of alpha-olefins is to low crystallization alpha-olefines type elastocopolymer, the (iii) alpha-olefin that forms by at least two kinds of alpha-olefins and at least a non-conjugated diene-diene type elastocopolymer and (iv) aromatic ethylene base type hydrocarbon-conjugated diene copolymer or its hydrogenated products, and randomly (c) mineral filler or organic filler.The cyclenes component of multipolymer (A) can be many 1 to 4 ring bridge joint cyclic olefins and, although these comprise norbornylene, only illustrational material is 1,4,5,8-two endo-methylene groups-1,2,3,4,4a, 5,8,8a-octahydro naphthalene (DMON) and its methyl substituted form.

[0012] U.S. Patent No. 6,255,396 disclose a kind of blend polymer that can be used for manufacturing the transparent article of medical usage, and it comprises that pass through first component that copolymerization norbornene monomer and vinyl monomer obtain and the 99wt% of 1-99wt% have second component with the ethylene copolymer of the alpha-olefin of 6 carbon atoms to comprising of 1wt%.First component has from 50 ℃ to 180 ℃ second-order transition temperature, but second blend components since its fusing point (softening temperature is a little less than fusing point) or its second-order transition temperature (softening temperature is generally than T _gHigh about 10 ℃) and have and be higher than 30 ℃ softening temperature.In this patent, do not report modulus in flexure or shock strength measuring result, and not illustration mineral filler.

[0013] U.S. Patent No. 6,590, and 033 discloses and is similar to U.S. Patent No. 6,255, and 396 described blend polymers comprise the homopolymer or the multipolymer of the diene with 4 to 12 carbon except second component.Such diene polymer generally has the solubility parameter that is higher than 30 ℃ softening temperature or also is different from compatible with it cyclic olefin copolymer.For example, the Bicerano solubility parameter of poly-(1, the 4-divinyl) is 17.7J ^0.5/ cm ^1.5, cyclic olefin copolymer is 16.88J by contrast ^0.5/ cm ^1.5(numerical value derives from the table 5.2 of Prediction of PolymerProperties, and the third edition from Jozef Bicerano, is published in 2002 by Marcel Dekker).In addition, poly-(1, the 4-divinyl) polarity and can not toughness reinforcing effectively cyclic olefin copolymer too.

[0014] U.S. Patent No. 6,844,059 discloses the length-fiber-enhancing polyolefin structure of length 〉=3 millimeter, it comprises a) at least a b of being different from from 0.1 to 90wt%) polyolefine, b) from 0.1 to 50wt% at least a amorphous cycloolefine polymer such as ethene/norbornene copolymer, c) from 5.0 to 75wt% at least a fortifying fibre, with d) up to other additive of 10.0wt%.Polyolefine a) can obtain by using suitable catalyzer addition polymerization ethene or alpha-olefin such as propylene, and is generally the hypocrystalline homopolymer of alpha-olefin and/or ethene, or the multipolymer that forms each other of these materials.

[0015] at Die Angewandte Makromole kulare Chemie 256 (1998), 101-104 page or leaf, Stricker and Mulhaupt have been described and have been comprised the only blend of the ethene/norbornene copolymer of 40wt.% norbornylene.Do not report the thermostability of this multipolymer, yet, can estimate that second-order transition temperature is less than 60 ℃.The rubber that is used for toughness reinforcing cyclic olefin copolymer is poly-(ethene-be total to-butylene)-b-polystyrene (SEBS) multipolymer of polystyrene-b-.Polystyrene block in the multipolymer has the second-order transition temperature in the 83-100 ℃ of scope, gives the softening temperature of this properties-correcting agent more than 80 ℃.

[0016] at Polymer Engineering and Science, Vol.40 (12), p.2590-2601, December, be entitled as in 2000 in the article of " Rubber Toughened andOpti cally Transparent Blends of Cyclic Olefin Copolymers ", Khanarian has described the not filling blend thing of ethene/norbornene copolymer TOPAS 6013 with thermoplastic elastomer such as styrene-butadiene-styrene (SBS), styrene-ethylene-butadiene-styrene (SEBS) and styrene-ethylene-propylene-styrene (SEPS).TOPAS6013 has 140 ℃ second-order transition temperature, mixes making shock strength be increased to greater than 50J/m (notched izod) according to reports with the elastomerics that is less than 5wt%, and keeps the optics mist degree to be lower than 5%.Use the styrenic block copolymer of high heap(ed) capacity, Khanarian adopts 30wt.% polystyrene-b-polyhutadiene-b-polystyrene to realize the notched izod shock strength up to 520J/m.This properties-correcting agent is higher than 30 ℃ softening temperature owing to the second-order transition temperature of polystyrene block has.Khanarian also illustration some have the blend of ethylene-propylene-diene terpolymer, but the report shock strength only be 188J/m under the 20wt.% heap(ed) capacity.The heat-drawn wire of measuring is unlisted in this article, but considers the lower glass transition temperatures of TOPAS 6013, heat-drawn wire probably under 0.46MPa less than 125 ℃.

[0017] other reference of being considered comprises US4,874,808; US4,992,511; US5,428,098; US5,359,001; US5,574,100; US5,753,755; US5,854,349; US5,863,986; US6,090,888; US6,225,407; US2003/0125464A1; US6,596,810B1; US6,696,524B2; US6,767,966B2; US2004/0236024A1; And US2005/0014898A1.

[0018] according to the present invention, have been found that now the cyclic olefin copolymer of high glass-transition temperature and compatible lower glass transition temperatures polyolefin elastomer bound energy are produced the required bonded polymer composition with high rigidity, impelling strength and thermostability, make this blend be applicable to the vehicle structure purposes.

Summary of the invention

[0019] on the one hand, the invention reside in the polymer composition that comprises following component:

(a) greater than the cyclic olefin copolymer of 50wt% (based on the weight of composition), described cyclic olefin copolymer comprises at least a acyclic olefin and one or more cyclic olefins of 20wt% (based on the weight of cyclic olefin copolymer) at least, and wherein at least a portion cyclic olefin copolymer has the second-order transition temperature greater than 150 ℃;

(b) less than the acyclic olefin polymer modifiers of 50wt% (based on the weight of composition), partially modified at least dose has and is lower than-30 ℃ second-order transition temperature; And properties-correcting agent do not have softening temperature greater than+30 ℃ part, and the Bicerano solubility parameter of properties-correcting agent is no more than 0.6J less than the Bicerano solubility parameter of cyclic olefin copolymer ^0.5/ cm ^1.5

Wherein the notched izod shock resistance that records under 23 ℃ of composition is greater than 500J/m, and the composition heat-drawn wire that use 0.46MPa load records is greater than 135 ℃.

[0020] easily, described cyclic olefin copolymer comprises 30wt% at least, as one or more cyclic olefins of 40wt% at least.

[0021] easily, the described cyclic olefin copolymer of at least a portion has greater than 160 ℃, even greater than 170 ℃ second-order transition temperature.In one embodiment, whole described cyclic olefin copolymers have the second-order transition temperature greater than 150 ℃.

[0022] easily, at least a portion polymer modifiers has less than-40 ℃, as the second-order transition temperature less than-50 ℃.In one embodiment, whole described polymer modifiers have and are lower than-30 ℃ second-order transition temperature.Easily, there is not properties-correcting agent partly to have softening temperature greater than+10 ℃.

[0023] easily, the Bicerano solubility parameter of properties-correcting agent less than the Bicerano solubility parameter of cyclic olefin copolymer between about 0.1 and about 0.5J ^0.5/ cm ^1.5, as between about 0.2 and about 0.4J ^0.5/ cm ^1.5

[0024] easily, polymer composition has in the notched izod shock resistance of 23 ℃ of measurements greater than 550J/m, for example greater than 600J/m, even greater than 700J/m;-18 ℃ of notched izod shock resistances of measuring down greater than 50J/m, as greater than 150J/m, for example greater than 300J/m, even greater than 500J/m; In the instrument impact energy of 23 ℃ of measurements, as greater than 30J greater than 25J;-29 ℃ of instrument impact energys of measuring down greater than 25J are as greater than 30J; Use the 0.46MPa load measurement greater than 150 ℃ heat-drawn wire, as greater than 165 ℃; Use the 1.80MPa load greater than 115 ℃ heat-drawn wire, as greater than 130 ℃, for example greater than 145 ℃; With modulus in flexure (1% sencant method), as greater than 2000MPa, for example greater than 2500MPa greater than 1200MPa.

Description of drawings

[0025] Fig. 1 shows the diagram of different elastomericss to the ballistic influence of room temperature socle girder that comprises the elastomeric Topas6015 compression mold of 20wt% blend.

[0026] Fig. 2 is the diagram of the ballistic influence of room temperature socle girder of the compression molding sample that shows that the consistency between cyclic olefin copolymer and properties-correcting agent makes the blend by Topas 6015 and the various properties-correcting agent of 20wt.%.

[0027] Fig. 3 shows the diagram of various properties-correcting agent to the ballistic influence of room temperature socle girder of the injection-molded blend of the Topas 6015 that comprises 20wt.% properties-correcting agent.

[0028] Fig. 4 shows the diagram to the influence of the room temperature socle girder shock resistance of injection mould Topas 6015 blends that comprise 20wt.% properties-correcting agent of consistency between cyclic olefin copolymer and the properties-correcting agent.

[0029] Fig. 5 shows the diagram of properties-correcting agent heap(ed) capacity to the influence of the room temperature notched izod shock resistance of Topas 6015/Vistalon 8600 blends.

[0030] Fig. 6 is the high impact resistance polypropylene and the diagram of not filling high-impact ethene/norbornene copolymer blend character of the present invention of comparison commodity.

[0031] Fig. 7 is the diagram that shows that unfilled Topas 6015/Vistalon 8600 blend modulus in flexurees (1% secant) descend when more properties-correcting agent is added blend.

Embodiment

[0032] be mentioned when comprising alkene when polymkeric substance or oligopolymer, the alkene that is present in polymkeric substance or oligopolymer is respectively the polymerization or the oligomeric form of alkene.Term polymer means and comprises homopolymer and multipolymer.The term multipolymer is included in any polymkeric substance that has two or more different monomers in the same chain, and comprises random copolymers, statistical copolymer, interpretation and (reality) segmented copolymer.

[0033] the invention provides a kind of polymer composition, it comprises:

(a) greater than 50wt%, for example about 60wt% is to about 80wt%, and 65wt% arrives about 75wt% according to appointment, cyclic olefin first multipolymer of (based on the weight of composition), and its at least a portion has the second-order transition temperature greater than 150 ℃; With

(b) less than 50wt%, for example about 20wt% is to about 40wt%, 25wt% arrives about 35wt% according to appointment, compatible acyclic olefin second polymer modifiers of (based on the weight of composition), and at least a portion of second polymkeric substance has the second-order transition temperature less than-30 ℃; And there is not the second multipolymer part softening temperature greater than+30 ℃.

[0034] blend has the notched izod shock resistance of measuring down greater than 500J/m at 23 ℃ and the heat-drawn wire of using the 0.46MPa load measurement greater than 135 ℃, makes this blend be highly suitable for automotive structural applications.

Cyclic olefin first multipolymer

[0035] cyclic olefin first copolymer component in the polymer composition of the present invention is by making at least a cyclic olefin and at least a acyclic olefin and presumable one or more diene copolymerization.In first multipolymer total amount of all cyclic olefins be multipolymer from about 20 to about 99 weight %.Cyclic olefin copolymer remaining double bond may unreacted or may be hydrogenated, crosslinked or functionalized.Cyclic olefin copolymer may adopt copolymerization in free radical addition reaction or the reactor and grafting.They may be to adopt chain to transmit the segmented copolymer that agent (chainshuttling agents) makes.

[0036] cyclic olefin is defined as herein wherein at least one two key and is contained in alkene in one or more alicyclic rings.Cyclic olefin can also have the two keys of non-annularity in side chain.The suitable cyclic olefin that is used for the cyclic olefin copolymer component comprises norbornylene, tricyclo decene, Dicyclopentadiene (DCPD), tetracyclododecane, six ring heptadecenes, three ring undecylenes, the five rings cetene, ethylidene norbornene (ENB), vinyl norbornene (VNB), norbornadiene, the alkyl norbornylene, cyclopentenes, cyclopropylene, cyclobutene, tetrahydrobenzene, cyclopentadiene (CP), cyclohexadiene, cyclo-octatriene, indenes, cyclopentadiene and acyclic olefin, arbitrary diels-alder adduct of cyclic olefin or diene; And arbitrary diels-alder adduct of divinyl and acyclic olefin, cyclic olefin or diene; Vinyl cyclohexene (VCH); The alkyl derivative of cyclic olefin; Fragrance derivatives with cyclic olefin.

[0037] the suitable acyclic olefin that is used for the cyclic olefin copolymer component comprises alpha-olefin (1-alkene), iso-butylene, 2-butylene and vinyl aromatic compound.The example of such acyclic olefin is ethene, propylene, 1-butylene, iso-butylene, 2-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, vinylbenzene, p-methylstyrene, to t-butyl styrene, to the alkyl derivative of styryl phenyl, 3-Methyl-1-pentene, vinyl cyclohexane, 4-methyl-1-pentene, acyclic olefin and the fragrance derivatives of acyclic olefin.

[0038] diene broadly is defined as at this and comprises the arbitrary alkene that contains the two keys of at least two acyclics.They also can comprise aromatic substituent.If one or more pairs of keys of diene are contained in the alicyclic ring, monomer is classified as cyclic olefin of the present invention.The suitable diene that is used for the cyclic olefin copolymer component is 1, the 4-hexadiene; 1, the 5-hexadiene; 1, the 5-heptadiene; 1, the 6-heptadiene; 1, the 6-octadiene; 1, the 7-octadiene; 1, the 9-decadiene; Divinyl; 1,3-pentadiene; Isoprene; 1, the 3-hexadiene; 1, the 4-pentadiene; Right-Vinylstyrene; The alkyl derivative of diene; Fragrance derivatives with diene.

[0039] the suitable cyclic olefin copolymer as first copolymer component of the present composition comprises ethylene-norbornene copolymer; Ethene-dicyclopentadiene copolymer; Ethylene-norbornene-Dicyclopentadiene (DCPD) terpolymer; Ethylene-norbornene-ethylidene norbornene terpolymer; Ethylene-norbornene-vinyl norbornene terpolymer; Ethylene-norbornene-1,7-octadiene terpolymer; Ethene-cyclopentenes multipolymer; Ethene-indene copolymer; Ethene-tetracyclododecane multipolymer; Ethylene-norbornene-vinyl cyclohexene terpolymer; Ethylene-norbornene-7-methyl isophthalic acid, 6-octadiene terpolymer; Propylene-norbornene copolymer; Propylene-dicyclopentadiene copolymer; Ethylene-norbornene-styrene copolymer; Ethylene-norbornene-p-methylstyrene terpolymer; Functionalized ethene-dicyclopentadiene copolymer; Functionalized propylene-dicyclopentadiene copolymer; Functionalized ethylene-norbornene-diene copolymers; Maleic anhydride grafting cyclic olefin copolymer; Silane grafting cyclic olefin copolymer; Hydrogenation of ethylene-dicyclopentadiene copolymer; Epoxidised ethene-dicyclopentadiene copolymer; Epoxidised ethylene-norbornene-Dicyclopentadiene (DCPD) terpolymer; The grafting cyclic olefin copolymer; Short-chain branched cyclic olefin copolymer; The long chain branching cyclic olefin copolymer; With crosslinked cyclic olefin copolymer.

[0040] the special cyclic olefin copolymer that preferably comprises norbornylene or hydrogenation Dicyclopentadiene (DCPD).Norbornylene is made by the diels-alder addition of cyclopentadiene and ethene.(passing through on the cyclopentadiene industry) by the initial reverse diels-Alder reaction preparation of Dicyclopentadiene (DCPD).Dicyclopentadiene (DCPD) is the heavy feed stock cracked by product of preparation ethene and propylene.Other preferred cyclic olefin is the diels-alder adduct of cyclopentadiene and other alkene, makes alkyl-or aryl-norbornylene, or makes vinyl norbornene and ethylidene norbornene with divinyl.The diels-alder adduct of divinyl and itself makes vinyl cyclohexene, and it is another kind of preferred monomers.The preferred acyclic olefin that is used for cyclic olefin copolymer is an ethene, because ethene-cyclic olefin copolymer has the impact property better slightly than other multipolymer.Ethene and norbornylene and in alicyclic ring the terpolymer of the double bond containing diene of bag also be preferred because they can easily crosslinked, grafting or functionalized.

[0041] at least a portion of cyclic olefin copolymer that is used for first copolymer component of the present composition has the second-order transition temperature greater than 150 ℃.These high glass-transition temperature zones will begin to soften being lower than the about 10-30 of second-order transition temperature ℃, cause that using the 0.45MPa load to be lower than their the about 10-15 of second-order transition temperature ℃ heat-drawn wire down and to use 1.80MPa to load is lower than the about 30-35 of second-order transition temperature ℃ heat-drawn wire.The second-order transition temperature of at least a portion of preferred these cyclic olefin copolymers is greater than 160 ℃ and more preferably greater than 170 ℃.If only the part cyclic olefin copolymer has second-order transition temperature greater than 150 ℃, preferred remainder has and is lower than 30 ℃ softening temperature.Such cyclic olefin copolymer can be to have elastomeric block or graft copolymer.If the part of cyclic olefin copolymer has the softening temperature that is higher than 30 ℃ and is lower than the softening temperature that is associated with the second-order transition temperature that is higher than 150 ℃, tend to reduce the heat-drawn wire and the high-temperature modulus of composition.Preferably wherein All Ranges has cyclic olefin copolymer greater than 100 ℃ second-order transition temperature.

[0042] for wherein the present composition will be by injection-molded automobile application, also preferred cyclic olefin copolymer has high melt flow rate (MFR) when measuring under the injection molding machine processing temperature.Preferably in ISO 1133 tests, be higher than 115 ℃ of melt flow rate (MFR)s of using the 1.80MPa load down of heat-drawn wire greater than 5ml/10min.

[0043] useful ethylene-norbornene copolymer can be bought from Topas AdvancedPolymers and Mitsui Chemicals.Ethene/the norbornene copolymer that is made by metallocene catalyst can be purchased as the TOPAS multipolymer from Topas Advanced Polymers GmbH.The TOPAS trade mark 6015 and 6017 has 160 and 180 ℃ second-order transition temperature respectively according to reports.Their heat-drawn wire (150 and 170 ℃ respectively) and the polymer composition of the preferred heat-drawn wire that satisfies under 0.46MPa at least 130 ℃ can be provided in the heat-drawn wire (135 and 151 ℃ respectively) of 1.8MPa report at 0.46MPa report.

[0044] useful cyclic olefin copolymer can use vanadium, Z-N and metallocene catalyst to make.The example of appropriate catalyst is disclosed in United States Patent(USP) Nos. 4,614, and 778 and 5,087,677.

Acyclic olefin second polymkeric substance

[0045] second polymeric constituent of the present composition comprise that one or more are random, block (blocky) or block polymer.Each polymkeric substance is formed by at least a alkene and presumable at least a diene polymerization.These alkene can be non-annularity or cyclic alkene, as long as the total amount of the cyclic olefin in the multipolymer is less than 20 weight %.Remaining pair of key may unreacted or hydrogenation, functionalized or crosslinked in the polyolefin modifiers.Polyolefin modifiers may adopt copolymerization in free radical addition reaction or the reactor and grafting.They can be to use chain to transmit the segmented copolymer of agent preparation.

[0046] acyclic olefin that is suitable for use as second polymeric constituent comprises alpha-olefin (1-alkene), iso-butylene, 2-butylene and vinyl aromatic compounds.The example of such acyclic olefin is ethene, propylene, 1-butylene, iso-butylene, 2-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, vinylbenzene, p-methylstyrene, to t-butyl styrene, to the alkyl derivative of styryl phenyl, 3-Methyl-1-pentene, vinyl cyclohexane, 4-methyl-1-pentene, acyclic olefin and the fragrance derivatives of acyclic olefin.

[0047] cyclic olefin that is applicable to second polymeric constituent comprises norbornylene, tricyclo decene, Dicyclopentadiene (DCPD), tetracyclododecane, six ring heptadecenes, three ring undecylenes, the five rings cetene, ethylidene norbornene (ENB), vinyl norbornene (VNB), norbornadiene, the alkyl norbornylene, cyclopentenes, cyclopropylene, cyclobutene, tetrahydrobenzene, cyclopentadiene (CP), cyclohexadiene, cyclo-octatriene, indenes, cyclopentadiene and acyclic olefin, arbitrary diels-alder adduct of cyclic olefin or diene; Diels-alder adduct with divinyl and acyclic olefin, cyclic olefin or diene; Vinyl cyclohexene (VCH); The alkyl derivative of cyclic olefin; Fragrance derivatives with cyclic olefin.

[0048] diene that is applicable to second polymeric constituent comprises 1, the 4-hexadiene; 1, the 5-hexadiene; 1, the 5-heptadiene; 1, the 6-heptadiene; 1, the 6-octadiene; 1, the 7-octadiene; 1, the 9-decadiene; Divinyl; 1,3-pentadiene; Isoprene; 1, the 3-hexadiene; 1, the 4-pentadiene; To Vinylstyrene; The alkyl derivative of diene; Fragrance derivatives with diene.

[0049] the suitable acyclic olefin multipolymer as second polymeric constituent of the present composition comprises high density polyethylene(HDPE) (HDPE); New LDPE (film grade) (LDPE); Linear low density polyethylene (LLDPE); Isotatic polypropylene (iPP); Atactic Polypropelene (aPP); Syndiotactic polypropylene (sPP); Poly-(1-butylene); Poly-(iso-butylene); Isoprene-isobutylene rubber; Poly-(divinyl); Poly-(3-Methyl-1-pentene); Poly-(4-methyl-1-pentene); Poly-(1-hexene); The semi-crystalline ethylene-propylene multipolymer; Amorphous ethylene-propylene copolymer; Semicrystalline propylene-ethylene copolymer; The semi-crystalline co-polymers of ethene and alpha-olefin; The semi-crystalline co-polymers of ethene and iso-butylene or 2-butylene; The semi-crystalline co-polymers of ethene and vinyl aromatic compound; Ethene and diene such as hexadiene, vinyl cyclohexene and 7-methyl isophthalic acid, the semi-crystalline co-polymers of 6-octadiene; The semi-crystalline co-polymers of propylene and alpha-olefin; The semi-crystalline co-polymers of propylene and vinyl aromatic compounds; The semi-crystalline co-polymers of propylene and vinyl aromatic compounds; The semi-crystalline co-polymers of propylene and iso-butylene or 2-butylene; The semi-crystalline co-polymers of propylene and diene; Blend in the reactor of isotatic polypropylene and ethylene-propylene rubber(EPR) or ethylene-propylene-diene terpolymer (ICPs); The amorphous ethylene multipolymer of band alpha-olefin, vinyl aromatic compounds, cyclic olefin, iso-butylene, 2-butylene or diene; Ethene, comprise the alpha-olefin of propylene and the terpolymer of diene; The terpolymer of ethene, alpha-olefin and vinyl aromatic compounds; The terpolymer of ethene, alpha-olefin and cyclic olefin; Be grafted to the polyolefine of polystyrene; Be grafted to the polyolefine of cyclic olefin copolymer; Be grafted to other polyolefinic polyolefine; The terpolymer of propylene, another kind of alkene and diene; The amorphous copolymer of iso-butylene and isoprene; The amorphous copolymer of iso-butylene and p-methylstyrene; Has the polyolefine of the two keys of hydrogenant; Polyolefine with epoxidised or hydroxylated pair key; Has polyolefine by the functionalized two keys of electrophilic addition; Any functionalized polyolefin; Polyolefine with short and long-chain branch; By they two keys and crosslinked polyolefine; Pass through functional group and crosslinked polyolefine; And the polyolefine that has adopted the free radical addition reactive grafting.Preferred second multipolymer comprises ethylene-propylene rubber(EPR) (EP rubber).Term " EP rubber " refers to ethene and propylene, and the multipolymer of optional one or more diene monomers (as mentioned above), and therein ethylene content is from 25 to 80wt%, and the diene total content is until 15wt%, and surplus is a propylene.

[0050] at least a portion second polymeric constituent should have and is lower than-30 ℃ second-order transition temperature.These lower glass transition temperatures zones of properties-correcting agent still keep ductility and improve the low temperature notched socle girder shock resistance and the cryogenic equipment impact energy of the present composition when being low to moderate their second-order transition temperature.Preferably, the second-order transition temperature of at least a portion of polyolefin modifiers is for being lower than-40 ℃, more preferably less than-50 ℃.Preferably, all parts of polyolefin modifiers have these lower glass transition temperatures and can be used for toughness reinforcing fragility cyclic olefin copolymer phase.

[0051] in addition, second polymeric constituent will not comprise softening temperature and be higher than 30 ℃ and the part that preferably is higher than 10 ℃.The softening temperature that is higher than 30 ℃ is to be higher than 30 ℃ because second-order transition temperature is higher than the melt temperature of the major portion of 30 ℃ or properties-correcting agent.They are analyzed the unexpected loss of the polyolefin modifiers modulus in (DMTA) experiment as the softening temperature in the transformation in the differential scanning calorimeter (DSC) or peak value, Vicat softening point, the thermo-mechanical analysis (TMA) or differential machinery heat and can detect.They are undesirable, because softening properties-correcting agent also causes the detectable high-temperature modulus that softens and reduce of composition.

[0052] cyclic olefin first multipolymer that is used for the present composition have very high second-order transition temperature and, therefore must in addition higher temperature under process.Second polymer modifiers that is used for said composition must be stablized under these high processing temperatures.Therefore preferred properties-correcting agent is included in one or more antioxidants of effective stable modification agent under these high processing temperatures.Also preferred properties-correcting agent comprises UV stabilizer to prevent the damage during end-use is used.Most preferably be not contained in to be used to mix and to form under the processing temperature of the present composition and be the polyolefin modifiers of reactive group.

[0053] in order to make toughness reinforcing effectively brittle ring-type first multipolymer of second polymer modifiers, the area size of second multipolymer is less than 1-2 μ m, and it is desirable being more preferably less than 1.0 μ m, in mean diameter.When the interfacial energy between second polymkeric substance and fragility cyclic olefin copolymer very little or even when being zero, can realize these zonules.Minimum interfacial energy between the two-phase refers to big zone is destroyed to what have more interfacial areas is that thermodynamics allows than the zonule.Composition with very little or zero interfacial energy can mix and dispersible polyolefin properties-correcting agent effectively by shearing is applied to molten mixture.Toughness reinforcing in order to realize cyclic olefin copolymer, polyolefin modifiers preferably has zero or low interfacial energy with first multipolymer.According to the Polymer Interface and Adhesion of Souheng Wu, Marcel Dekker, 1982, when the polar phase of polyolefin modifiers and cyclic olefin copolymer mates, realize zero or low interface energy.

[0054] in order experimentally to mate polarity, needs to measure the surface energy or the solubility parameter of every kind of polyolefin modifiers and every kind of cyclic olefin copolymer.Surprisingly, have been found that measuring the Bicerano solubility parameter can promptly dwindle the scope that is used for to the polyolefin modifiers selected of the cyclic olefin copolymer that sets the goal.D.W.Van Krevelen is at Properties ofPolymers, Their Correla tion With Chemical Structure; TheirNumerical Estimation and Prediction From Additive GroupContributions, Elsevier has studied in 1990 and has been present in the functional group that exists in the polymer chain and the dependency between its experiment solubility parameter.These dependencys are very suitable, but are confined to only comprise a base polymer of the functional group that is used for original dependency.JozefBicerano is at Prediction of Polymer Properties, and the 3rd edition, MarcelDekker replaces having expanded these dependencys with the dependency of functional group by using with graph theory exponential dependency in 2002.The graph theory index only depends on that polymer repeat unit is the element that how each other exists on bonding and the repeating unit.They can calculate and related with solubility parameter fine any repeating unit.Bicerano has listed the Bicerano solubility parameter of 121 kinds of general polymers in his table 5.2 of book.These equatioies are also programmed input can be from the Cerius of Accelerys acquisition ²The Synthia module of molecular simulation routine package.Use the cyclic olefin copolymer that uses in the subsequent embodiment and these Bicerano solubility parameters of polyolefin modifiers, the composition with the highest room temperature notched izod shock resistance always in the Bicerano of polyolefin modifiers solubility parameter less than the Bicerano solubility parameter 0.0 of cyclic olefin copolymer to 0.6J ^0.5/ cm ^1.5In time, occur.Referring to being used for room temperature notched izod shock resistance Fig. 2 and 4 (marking) as Est.Sol.Param. to the figure line of Bicerano solubility parameter difference.Preferably, the Bicerano solubility parameter of polyolefin modifiers is less than the Bicerano solubility parameter 0.1-0.5J of cyclic olefin copolymer ^0.5/ cm ^1.5, more preferably 0.2-0.4J ^0.5/ cm ^1.5

[0055] preferred polyolefine can be from ExxonMobil Chemical Company with trade(brand)name Vistalon, Exxelor, Exact or Vistamaxx buy, and perhaps their methods that can use vanadium, Z-N or metallocene catalyst to be known by the prior art kind make.

[0056] the preferred EP rubber of second polymkeric substance as composition described herein comprises having one or more those of following character:

1) ethylene content 25 to 80wt% (preferred 30 to 75wt%, preferred 35 to 70wt%, preferred 40 to 65wt%); And/or

2) diene content 15wt% or still less (preferred 12wt% or still less, preferred 9wt% or still less, preferred 6wt% or still less, preferred 3wt% or still less, preferred 0wt%); And/or

3) density 0.87g/cm ³Or lower (preferred 0.865g/cm ³Or lower, preferred 0.86g/cm ³Or lower, preferred 0.855g/cm ³Or it is lower); And/or

4) melting heat (H _f), if record, less than 20J/g (preferably less than 15J/g, preferably less than 10J/g, preferably less than 5J/g, preferred melting heat can not differentiated); And/or

5) ethene or propylene degree of crystallinity are if can measure, less than 10wt% (preferably less than 7.5wt%, preferably less than 5wt%, preferably less than 2.5wt%, preferred degree of crystallinity does not detect); And/or

6) fusing point (T _m, melting peak for the first time), if record, be 60 ℃ or lower (preferred 50 ℃ or lower, preferred 40 ℃ or lower, preferred 35 ℃ or lower); And/or

7) second-order transition temperature (T _g) be-30 ℃ or lower (preferred-40 ℃ or lower, preferred-50 ℃ or lower, preferred-60 ℃ or lower); And/or

8) M _wBe 50 to 3, and 000kg/mol (preferred 100 to 2,000kg/mol, preferred 200 to 1,000kg/mol); And/or

9) M _w/ M _nBe 1.5 to 40 (preferred 1.6 to 30, preferred 1.7 to 20, preferred 1.8 to 10, preferred 1.8 to 5, preferred 1.8 to 3, preferred 1.8 to 2.5); And/or

10) mooney viscosity, (1+4) is 10 to 100 (preferred 15 to 10090, preferred 20 to 85) for @125 ℃ to ML.

[0057] the particularly preferred EP rubber that herein uses does not contain diene (being ethylene-propylene copolymer).If there be (being ethylene-propylene-diene terpolymer) in diene, preferred diene is diene such as the ethylidene norbornene (ENB) derived from norbornylene, vinylidene norbornylene (VNB), or Dicyclopentadiene (DCPD) (DCPD).Diene content is recorded by ASTM D 6047.

[0058] method of manufacturing EP rubber is inessential, if can pass through slurry, solution, gas phase, high pressure or other suitable technology, be suitable for the catalyst system of polyolefin polymerization by use, make as Ziegler-Natta catalyst, metallocene catalyst, other suitable catalyst system or its combination.

[0059] in an especially preferred embodiment, EP rubber used herein uses catalyst body based on vanadium to tie up in solution or the slurry process to make.In another embodiment, EP rubber used herein uses catalyst body based on metallocene to tie up in solution or the slurry process to make.In another embodiment, EP rubber used herein uses any single-site catalyst systems to make in solution or slurry process.Preferably, the EP rubber that makes by vanadium, metallocene or other single-site catalyst systems has 1.8 to 2.5 molecular weight distribution (M _w/ M _n).

[0060] can be used for that EP rubber of the present invention comprises can be from ExxonMobil Chemical (with trade(brand)name Vistalon ^TMSale) those that obtain comprise:

ExxonMobil Chemical Vistalon ^TMEP rubber

The trade mark	Mooney viscosity (ML1+4,125 ℃)	Ethene (wt%)	Diene (wt%)	Molecular weight distribution
					404	28	45	--	Non-constant width
504	25	60	--	Wide
					606	65	54	--	Wide
703	21	73	--	Narrow
					706	42	65	--	Bimodal
707	23	72	--	Non-constant width
					722	16	72	--	Narrow
785	30	49	--	Narrow
					805	33	78	--	Narrow
878	51	60	--	Narrow
					MDV91-9	18	59	--	Narrow
1703P
		25	77	0.9VNB	Non-constant width
2727						44	57	2.0ENB	Wide
	3708	52	70	3.4ENB	Wide
2504						25	58	4.7ENB	Wide
	2727	44	56	2.0ENB	Wide
4600						90	60	4.5ENB	Bimodal
	4709	78	75	4.4ENB	Narrow
5504						25	45	4.7ENB	Medium
	5601	72	68	5.0ENB	Customization
6505						53	57	9.2ENB	Wide
	7000	59	73	5.0ENB	Narrow
7001						60	73	5.0ENB	Customization
	7500	82	56	5.7ENB	Bimodal
7800(P)						20	79	6.0ENB	Bimodal
	8600	81	58	8.9ENB	Bimodal
8609						83	68	8.0ENB	Bimodal
	8800	15	73	10.0ENB	Bimodal
9500						72	60	11.0ENB	Bimodal

Additive

[0061] except that ring-type first copolymer component and acyclic second copolymer component, many additives can be added polymer composition of the present invention.Some additives help the processing of moulding part; Stability or the aesthetic property that add other with the raising moulding part.Useful additive comprises lactone, azanol, phosphoric acid ester (salt), finings, hindered amine antioxidant, the aromatic amine antioxidant, hindered phenol antioxidant, the divalent sulfur antioxidant, the three valent phosphors antioxidant, the metal deactivator antioxidant, thermo-stabilizer, low profile (profile) additive, UV stabilizer, lubricant, releasing agent, odorant agent, static inhibitor, biocide, surface slip agent, release agent, antifoams, whipping agent, antifogging agent, titanic acid ester, fire retardant, dyes and dyestuffs.Antioxidant and titanic acid ester are used for some compositions of the present invention.Preferred antioxidant addn be Irganox 1010, Capow L-12/H and with FS-042 bonded Irgafos 168.Irganox 1010, Irgafos 168 and FS-042 can obtain from Ciba.Capow L-12/H is can be from the titanic acid ester of Kenrich acquisition.

[0062] processing oils can be added compounding to improve the plasticity-of the present composition.Softening agent is added polymkeric substance with the second-order transition temperature that reduces them and improve impact property.For example, processing oils can be added polyolefin modifiers with their second-order transition temperature of further reduction.The useful processing oils and the softening agent that are used for the present composition comprise poly-(1-decene), aliphatics petroleum fractions, aromatic base crude oil cut, alicyclic petroleum fractions, wood by-product, natural oils and synthetic oils.

[0063] in another embodiment, with among softening agent such as those WO 04/014998 the 9th to 28 page, particularly the 16th page of the 14th row is to the 20th page of the 17th row) (those of NFP ' s) add composition of the present invention to be described as non-sense softening agent.

[0064] linking agent can also be added the present composition to vulcanize second copolymer component, between cyclic olefin first multipolymer and second multipolymer, to produce grafting, with the functionalized cyclic olefin copolymer or second multipolymer, and curing composition becomes thermosetting resin.Useful linking agent comprises hydrogen peroxide, alkyl hydroperoxide, diacyl peroxide, dialkyl peroxide, peracid, peresters, has and do not have the sulphur of promotor, uses the promoted zinc of benzothiazole, phenolic resin curative, the silane with Pt catalyzer or radical initiator, quinone derivatives, bismaleimides and metal oxide.

The method for preparing polymer composition

[0065] any that said composition can be by the following method makes:

1. the preformed cyclic olefin copolymer of melt blending (being also referred to as first multipolymer), preformed polyolefin modifiers (being also referred to as second multipolymer) and any other component in mixing tank such as Braebender Plasticorder or Banbury mixer or forcing machine.Preferable methods is the twin screw extruder with high mixture strength.

2. the solution of mixed modifier and cyclic olefin copolymer or suspension, may extrude subsequently or melting mixing to add other component.

3. polymerization in grading reactor, wherein polyolefin modifiers makes in first reactor, cyclic olefin copolymer makes in second reactor, may extrude subsequently or melting mixing to add other component.

4. polymerization in grading reactor, wherein cyclic olefin copolymer makes in first reactor, and polyolefin modifiers makes in second reactor, may extrude subsequently or melting mixing to add other component.

5. polymerization polyolefin modifiers in the solvent that comprises the dissolved cyclic olefin copolymer, may extrude subsequently or melting mixing to add other component.

6. polymerizable cyclic olefin copolymer in the solvent that comprises the dissolved polyolefin modifiers, may extrude subsequently or melting mixing to add other component.

7. use two or more catalyzer polymerization polyolefin modifiers and cyclic olefin copolymer in same reactor, may extrude subsequently or melting mixing to add other component.Can use or not use chain to transmit agent is used for preparing segmented copolymer in this class polymerization.

8. polymerization, wherein second pair of key of the diene in polyolefin modifiers or the cyclic olefin copolymer partly is attached in other chain of the same type by polymerizing catalyst, produces polyolefin modifiers long chain branching or gelation or cyclic olefin copolymer.

9. polymerization, wherein second pair of key with the diene in polyolefin modifiers or the cyclic olefin copolymer is attached in the chain of other type polymer by polymerizing catalyst, produces between the different polyolefin modifiers, between the different cyclic olefin copolymer or the graft copolymer between polyolefin modifiers and the cyclic olefin copolymer.

10. crosslinked, wherein reagent is during mixing added so that the second pair of key and other pair key in the composition of polyolefin modifiers or cyclic olefin copolymer is crosslinked, generally produce between the polyolefin modifiers or cyclic olefin copolymer and/or polyolefin modifiers of long chain branching or gelation, between the cyclic olefin copolymer or the grafts between polyolefin modifiers and the cyclic olefin copolymer.

11. functionalized, wherein the method by one of preparation method 1 to 9 is functionalized with second pair of key of cyclic olefin copolymer or polymer modifiers or the diene in the two after mixing at cyclic olefin copolymer and polymer modifiers.

12. comprise by preparation method 1,2 or the functionalized polyolefin properties-correcting agent of 11 preparations or the composition of cyclic olefin copolymer, wherein as crosslinked as described in the preparation method 8-10, except between the functional group rather than the second pair of key, reacting.

13. arbitrary combination of method described in the preparation method 1-12.

Polymer composition

[0066] polymer composition of the present invention has many significant character, is included in 23 ℃ of following room temperatures (23 ℃) notched izod shock resistance greater than 500J/m, as greater than 550J/m, and for example greater than 600J/m, even greater than 700J/m.Do not observe fracture in these trials.Do not have fracture in the notched izod shock test of said composition under-18 ℃ yet, and under this temperature, demonstrate shock resistance greater than 50J/m, as greater than 150J/m, for example greater than 300J/m, even greater than 500J/m.

[0067] in the instrument shock test, said composition only has ductile fracture under room temperature and-29 ℃, and demonstrate the instrument impact energy of measuring down greater than 25J at 23 ℃ especially, even greater than 30J with-29 ℃ of instrument impact energys of measuring down greater than 25J, even greater than 30J.These impact properties are comparable to polycarbonate, ABS, poly-(methyl methacrylate) and optimum high impact resistance polypropylene blend.

[0068] yet, adopt 0.45 and the 1.80MPa load down, the heat-drawn wire specific energy of the present composition with the tenacity-increased profax blend reach much higher.Especially, polymer composition of the present invention demonstrate use that 0.46MPa records greater than 150 ℃ heat-drawn wire, generally greater than 165 ℃ and with the 1.80MPa load record greater than 115 ℃ heat-drawn wire, generally greater than 130 ℃, even greater than 145 ℃.

[0069] in addition, the modulus in flexure of composition (1% sencant method) is greater than 1200MPa, and as greater than 1600MPa, for example greater than 2000MPa, even greater than 2500MPa, this is significantly higher than the modulus in flexure of present high-impact TPO.(referring to Fig. 6 for the blend of first embodiment more of the present invention and the synoptic diagram of prior art polypropylene TPO).These character are more much better than the blend of the polyolefin modifiers of other report in any document and cyclic olefin copolymer.

The preparation of goods

[0070] goods can use the present composition by injection-molded, compression molding, transfer molding, reaction injection molding(RIM), thermoforming, pressure maniputation, roational molding, blowing, extrude, extrude covering, with other polymkeric substance coextrusion, separately or with other polymer materials pultrusion, form with other polymkeric substance lamination, coating, fiber spinning, sheet blowing, film casting, calendering or casting.Goods can also make by in these methods any, wherein will be retained in two keys in polyolefin modifiers or cyclic olefin copolymer or their functional group and form the back at goods and adopt by the use of thermal means or use a kind of linking agent to carry out crosslinked.

[0071] polymer composition of the present invention is that cyclic olefin copolymer has been opened up many new application.Because the present composition overcomes or relaxed the brittle problem of cyclic olefin copolymer, can use it for the great majority that wherein use other engineering thermoplasties and use.Instruction of the present invention can be used for adopting all types of cyclic olefins to prepare toughness reinforcing, enhanced composition, and has shown the key step progress (forward) of these materials.

[0072] polymer composition described herein is specially adapted to the part processing of automobile, comprising:

1. chassis, machinery and shield cap are used down, comprise gas reservoir; Collision bumper; The buffering energy absorber; The buffering dashboard; The open enhancement layer of grid; The grid opening panel; Front end dashboard and grid; The front group piece installing; The front end supporting member; Bolster; Valve gap; Rocker arm cover; Front cylinder head; Engine shield; The engine splash plate; Engine synchronous belt cover; The engine air clearer; The machine oil tundish; Battery case and pallet; Reservoir; The cooling system assembly comprises cooling fan and coverture and support and radiator bearer and end air chest; The inlet system assembly; Air ducting; Wheel cover; The axletree cover; Wheel rim; Suspend and transmission component; With switch and socket.

2. the internal application that comprises the part of dashboard (IP) comprises IP supporting member and fixer, IP basic building block, IP top, IP bottom and IP instrument group; The air bag shell; Inner step; Inner panel comprises centre portions and overhead panel and panel assembly; The jociey stick shell; The seat member comprises the chair back and centre panel; Interior trim panel comprises column assembly, IP assembly and door assembly panel; The inherent panel of lift gate and hatch; Handle for doors and windows; The HVAC tectum; The heavy burden base plate; The luggage boot wadding; Storage system; Packaging tray; Door heart layer and door heart layer assembly.

3. vehicle body is used and is comprised bottom panel and streamlined; Rocker panel; Running board; The spacious paulin container (pickup boxes) of light station waggon, vertical body panels comprise that splash pan, four opens plate, lift gate and hatch outside plate and external door panel; Laterally body panels comprises shield cap, tailstock luggage, on-deck lid and roof and roof assembly; Spoiler; Hood ventilation blade drift stop, grid and filter screen; Spare wheel container (spare wheel wells); The splash pan wadding; Extraneous adornment; Outer door handle; The signal lamp outer cover; Head and tail lamp outer cover; And mirror housing.

[0073] polymer composition described herein can also be used to make and is similar to the listed parts that are used for automobile, but be used for heavy truck and large-scale passenger stock such as motorbus, train and aircraft, and be used for recreational vehicle such as motor-driven sled, all-terrain vehicle, sailing boat, powerboat and injection ski.Other application of polymer composition described herein comprises manufacturing (a) amusement article such as toy, the helmet, rides wheel, swimming pool facility coverture and racket; (b) be used for the parts of macroconsumer's equipment, as washing machine drum, the inner wadding of refrigerator chamber and device external coverture; (c) be used for the coverture of business machine, manual tool, laboratory apparatus, electronics, small-sized machine and equipment; (d) be used for the parts of furniture; (e) the structure element in dwelling house and commercial building and structure such as exterior panel and curtain wall, window and doorframe, dashboard and bottom surface, window shutter and the HVAC assembly; (f) make large-scale waste management container.

[0074] the invention further relates to:

1. polymer composition comprises:

(a) greater than the cyclic olefin copolymer of 50wt% (based on the weight of composition), described cyclic olefin copolymer comprises one or more cyclic olefins (based on the weight of cyclic olefin copolymer) of at least a acyclic olefin and at least 20 weight %, and wherein the described cyclic olefin copolymer of at least a portion has the second-order transition temperature greater than 150 ℃;

(b) less than the acyclic olefin polymer modifiers of 50wt% (based on the weight of composition), at least a portion properties-correcting agent has and is lower than-30 ℃ second-order transition temperature; And properties-correcting agent do not have softening temperature greater than+30 ℃ part, and the Bicerano solubility parameter of properties-correcting agent is no more than 0.6J less than the Bicerano solubility parameter of cyclic olefin copolymer ^0.5/ cm ^1.5

The composition notched izod shock resistance that wherein records under 23 ℃ is greater than 500J/m and use composition heat-drawn wire that the 0.46MPa load records greater than 135 ℃.

2. the 1st section polymer composition, wherein said cyclic olefin copolymer comprises at least 30 weight %, one or more cyclic olefins of preferred at least 40 weight %.

3. the polymer composition of the 1st section or the 2nd section, wherein the described cyclic olefin copolymer of at least a portion has the second-order transition temperature greater than 160 ℃, is preferably greater than 170 ℃.

4. arbitrary section polymer composition in the 1st to 3 section, wherein a part of described cyclic olefin copolymer has the softening temperature less than 30 ℃.

5. arbitrary section polymer composition in the 1st to 4 section, wherein whole described cyclic olefin copolymers have the second-order transition temperature greater than 150 ℃.

6. arbitrary section polymer composition in the 1st to 5 section, wherein a part of described polymer modifiers has the second-order transition temperature less than-40 ℃, preferably less than-50 ℃.

7. arbitrary section polymer composition in the 1st to 6 section, wherein whole described polymer modifiers have the second-order transition temperature less than-30 ℃.

8. arbitrary section polymer composition in the 1st to 7 section does not wherein have described polymer modifiers part softening temperature greater than 10 ℃.

9. arbitrary section polymer composition in the 1st to 8 section, wherein said polymer modifiers has the Bicerano solubility parameter 0.1-0.5J less than cyclic olefin copolymer ^0.5/ cm ^1.5, preferred 0.2-0.4J ^0.5/ cm ^1.5The Bicerano solubility parameter.

10. arbitrary section polymer composition in the 1st to 9 section comprises about 20wt% to about 40wt%, and preferably 25wt% is to the described polymer modifiers of 35wt%.

11. arbitrary section polymer composition in the 1st to 10 section, the composition notched izod shock resistance that wherein records under 23 ℃ is preferably greater than 600J/m, more preferably greater than 700J/m greater than 550J/m.

12. arbitrary section polymer composition in the 1st to 11 section wherein uses composition heat-drawn wire that 0.46MPa load records greater than 150 ℃, is preferably greater than 165 ℃.

13. arbitrary section polymer composition in the 1st to 12 section wherein uses composition heat-drawn wire that 1.80MPa load records greater than 115 ℃, is preferably greater than 130 ℃, more preferably greater than 145 ℃.

14. arbitrary section polymer composition in the 1st to 13 section, the composition notched izod shock resistance that wherein records under-18 ℃ is preferably greater than 150J/m greater than 50J/m, more preferably greater than 300J/m, most preferably greater than 500J/m.

15. arbitrary section polymer composition in the 1st to 14 section, the composition instrument impact energy that wherein records under 23 ℃ is preferably greater than 30J greater than 25J.

16. arbitrary section polymer composition in the 1st to 15 section, the composition instrument impact energy that wherein records under-29 ℃ is preferably greater than 30J greater than 25J.

17. arbitrary section polymer composition in the 1st to 16 section, the composition modulus in flexure of wherein utilizing the measurement of 1% sencant method is preferably greater than 2000MPa, more preferably greater than 2500MPa greater than 1200MPa.

18. arbitrary section polymer composition in the 1st to 17 section, wherein said polymer modifiers comprise ethene, high alpha-olefin and 5wt% but be less than the multipolymer of the cyclic olefin of 20wt% at least.

19. the 18th section polymer composition, ring system wherein is selected from norbornylene, ethylidene norbornene, vinyl norbornene, vinyl cyclohexene and Dicyclopentadiene (DCPD).

20. the polymer composition of the 18th section or the 19th section, wherein alpha-olefin is selected from propylene, hexene and octene.

21. arbitrary section polymer composition in the 1st to 17 section, wherein said polymer modifiers comprise and comprise ethene, propylene and choose any one kind of them or the polymkeric substance of multiple diene.

22. the 21st section polymer composition, wherein polymkeric substance comprises 25 to the ethene of 80wt%, until one or more diene of 15wt% and the propylene of surplus.

23. arbitrary section polymer composition in the 1st to 17 section, wherein said polymer modifiers comprises ethene and 7-methyl isophthalic acid, the multipolymer of 6-octadiene.

24. arbitrary section polymer composition in the 1st to 23 section, wherein said cyclic olefin copolymer comprises the multipolymer of ethene and norbornylene and/or Dicyclopentadiene (DCPD).

25. arbitrary section polymer composition in the 1st to 24 section is wherein with some or all hydrogenations, the epoxidation and/or functionalized of the remaining double bond of cyclic olefin copolymer.

26. arbitrary section polymer composition in the 1st to 25 section, and comprise the mixture of melts of described cyclic olefin copolymer (a) and described polymer modifiers (b).

27. by arbitrary section the assembly that is used for automobile of polymer composition preparation in the 1st to 26 section.

[0075] in the above description, in embodiment and the claim, adopt following testing method to measure the various parameters of differentiating.

[0076] heat-drawn wire (HDT) uses ASTM method D648-06 and D1525-00 to measure.Before the test, sample is adapted at least 40 hours under 23 ℃ ± 2 ℃ and 50% ± 5% humidity.The ASTM test strip be 0.125 ＂ thick * 5 ＂ are wide * 5 ＂ are long.

[0077] density or proportion use ASTM D972-00 method A to measure.Cut out sample with the banded cutting machine of veneer clipper from standard modulus in flexure sample centre portions.Sample is about the 3-1/2 inch.Before the test, sample is adapted to minimum 40 hours under 23 ± 2 ℃ and 50 ± 5% relative humidity.

[0078] maximum tensile stress, young's modulus in tension and fracture tensile energy use ASTM method D638-03 to measure.At least five samples of each sample test.Before the test, sample is adapted to 40 hours under 23 ℃ ± 2 ℃ and 50% ± 5% relative humidity in bag.

[0079] deflection Young's modulus, 1% tangent modulus in flexure and 1% secant modulus in flexure are collected according to ASTM method D790-03.At least five samples of each sample test.Before the test, sample is adapted to 40 hours under 23 ℃ ± 2 ℃ and 50% ± 5% relative humidity in bag.

[0080] room temperature (23 ℃) and low temperature (18 ℃) notched izod performance are measured according to ASTM method D256-06.Test sample is that 2.5 inches long, 0.5 inch wide and 0.125 inch are thick.Use the banded cutting machine of veneer clipper to cut out at least five samples from the uniform centre of Class1 tensile bars.Sample uses the TMI deficient device to produce otch.With sample in minimum 40 hours of adaptation under 23 ± 2 ℃ and 50 ± 5% relative humidity behind cutting and the otch.For the test that is lower than envrionment temperature, the otch test piece is adapted to minimum one hour before test under specified test temperature.Observed fracture mode mark is as follows in the notched izod shock test:

C represents to rupture fully,

NB represents not rupture,

P is that wherein the top remains on the part fracture of rupture line tops, and

H is that wherein hinged (hinged) partial rupture below rupture line hangs down at the top.

[0081] instrument under the room temperature ,-18 ℃ and-29 ℃ impacts and measures according to ASTM method D3763-02.The standard testing sample is 4.0 inch diameter disks.At least five samples of each sample test under each temperature.Before the test, sample is adapted to minimum 40 hours under 23 ± 2 ℃ and 50 ± 5% relative humidity.If carry out high temperature or low-temperature test, the sample that will test was being tested preadaptation 4 hours.Observed fracture mode mark is as follows in the instrument shock test:

B represents brittle rupture,

BD represents to demonstrate certain ductility mobile brittle rupture,

DB is that wherein polymkeric substance is out of shape outside direction of propulsion but rimose ductile failure,

D is that wherein polymkeric substance is out of shape outside direction of propulsion and does not have rimose to destroy.

[0082] 60 degree gloss measurement adopts ASTM method 523-89.Sample does not have dust, scratch or fingerprint.

[0083] Luo Keweier hardness uses ASTM 785-03 program A and ASTM 618-05 to measure.Sample adapts at least 40 hours under 23 ± 2 ℃ and 50 ± 5% relative humidity.Standard test specimen is for 6mm (1/4 inch) is thick at least.

[0084] measures according to ASTM method D1238-04c in the melt flow rate (MFR) of 230C and 300C.

[0085] Shore A and D hardness use ASTM method D2240-05 to collect.Specimen is for 6mm (0.25 inch) is thick at least.

[0086] all molecular weight are number averages, except as otherwise noted.

[0087] the Bicerano solubility parameter is by being described in the Prediction of Polymer Properties of Jozef Bicerano, and the 3rd edition, Marcel Dekker, the Van Krevelen method of the 5th chapter among the Inc.2002 is measured.The programming version of estimating and measuring method is used for the embodiment form.Can be from Accelrys, the molecular simulation routine package that Inc. obtains, Cerius ², the Polymer Module in 4.0 versions can obtain.

Embodiment

[0088] the present invention more specifically describes referring now to following indefiniteness embodiment.

[0089] following material is used for embodiment:

Material	The source	Character
			Vistalon
8600	ExxonMobil Chemical Company	The ethene that comprises 57wt%, 8.9wt% ethylidene norbornene, the bimodal EPDM of 34.1wt% propylene.Tg does not have further feature (not having softening temperature) for-45.15 ℃ and rubber in that the DSC of its 10 ℃/min trace is in service.
			Vistalon 9500	ExxonMobil Chemical Company	The ethene that comprises 60wt%, 11wt% ethylidene norbornene, the bimodal EPDM of 29wt% propylene.Tg does not have further feature (not having softening temperature) for-41.64 ℃ and rubber in that the DSC of its 10 ℃/min trace is in service.
Vistalon 7001	ExxonMobil Chemical Company	The ethene that comprises 73wt%, 5wt% ethylidene norbornene, the bimodal EPDM based on metallocene of 22wt% propylene.Tg is-39.13 ℃, and rubber has 45 ℃ melting peak on its DSC trace.
			Exxelor PO 1020	ExxonMobil Chemical Company	PP homopolymer with the 0.5-1.0wt% maleic anhydride graft.MPt is 160 ℃.
Exxelor VA 1803	ExxonMobil Chemical Company	Random ethylene multipolymer with the 0.5-1.0wt% maleic anhydride graft.Second-order transition temperature is-57 ℃.
			MDV91-9	ExxonMobil Chemical Company	The ethylene-propylene copolymer that comprises 59.3wt.% ethene
Exact 5061	ExxonMobil Chemical Company	Fusing point is 52.8 ℃ the ethylene-octene copolymer based on metallocene
			PP8231E1	ExxonMobil Chemical Company	The high-impact propylene copolymer is 92 ℃ at the HDT of 0.46MPa
Vector 8508	Dexco Polymer LP	Comprise the cinnamic linear styrene-butadiene-styrene block copolymer of 29wt%
			Kraton G1650	Kraton	Comprise the cinnamic linear styrene-ethylene/butylene of 30wt%-styrene block copolymer, brookfield viscosity is 8000cps
Kraton G1651	Kraton	Comprise the cinnamic linear styrene-ethylene/butylene of 33wt%-styrene block copolymer, brookfield viscosity〉50,000cps
			Kraton G1652	Kraton	Comprise the cinnamic linear styrene-ethylene/butylene of 30wt%-styrene block copolymer, brookfield viscosity is 1800cps
Septon 2004	Kuraray	Comprise the cinnamic styrene-ethylene of 18wt%/propylene-styrene segmented copolymer, soltion viscosity 145cps
			Septon 2007	Kuraray	Comprise the cinnamic styrene-ethylene of 30wt%/propylene-styrene segmented copolymer, soltion viscosity 70cps
Septon HG-252	Kuraray	Comprise the cinnamic styrene-ethylene-ethylene/propene of 28wt%-styrene block copolymer, soltion viscosity 70cps
			Topas 6015	Topas Advanced Polymers	HDT is that 150 ℃ and Tg are 160 ℃ the ethene/norbornene copolymer based on metallocene under 0.46MPa
Topas 6017	Topas Advanced Polymers	HDT is that 170 ℃ and Tg are 180 ℃ the ethene/norbornene copolymer based on metallocene under 0.46MPa

Specimen preparation and measuring method

[0090] sample with compression molding restrains melting mixing in batches at BraebenderPlasticorder with 40 under 230 ℃.Sample is used Wabash press compression molding at 215 ℃.

[0091] with injection-molded blend 230 ℃ of melting mixing in Warner-Pflider WP-30 millimeter twin screw extruder.The opening for feed of ten pounds of total components by forcing machine added.With preceding two pounds of eliminatings.Sample uses the manufacturing of 110 tons of Van Dorn injection molding machines down at 250 ℃.Preceding 15 injection material (shots) are got rid of.

Embodiment 1 and 2 and Comparative Examples 1 to 8

[0092] compression molding deflection bar is by each listed elastomeric mixture preparation in the table 1 of the TOPAS 6015 of 80wt% and 20wt%.Batten is used for flexure test and cutting is used for notched izod shock test under room temperature and-18 ℃ and the heat distortion test under the 1.80MPa.The results are shown in Fig. 1 and table 1 and 2 of this test.

Table 1-is used for the compression molding screening of best rubber

	Ex.1	Ex.2	Comp.Ex.1	Comp.Ex.2	Comp.Ex.3
						Topas?6015(pph)	80	80	80	80	80
Vistalon?8600(pph)	20	20
						Kraton?G1651(pph)					20
Kraton?G1652(pph)				20
						Vistalon?9500(pph)			20
Deflection Young's modulus (MPa)	2010
						Modulus in flexure (1%tan) (MPa)	1937	1924
Modulus in flexure (1%sec) (MPa)	1986	1882
						1.80MPa under HDT (C)		124.8
RTNI(J/m)	501.8		402.5	193.8	388.1
						Fracture mode	7NB		4NB；1P 1H；1C	6P；5C	7NB
NI@-18C(J/m)	271.2
						Fracture mode	5P
Bicerano solubility parameter difference J .5/cm 1.5	.29	.29	0.25	.39. -2.62	.39 -2.62

Table 2-is used for the compression molding screening of best rubber

	Comp. Ex.4	Comp. Ex.5	Comp. Ex.6	Comp. Ex.7	Comp. Ex.8
						Topas?6015(pph)	80	80	80	80	80
Vistalon?7001(pph)	20
						Kraton?G1650(pph)		20	20
Vector?8508(pph)				20
						Exxelor?VA?1803(pph)					20
Deflection Young's modulus (MPa)			2030
						Modulus in flexure (1%tan) (MPa)			1896
Modulus in flexure (1%sec) (MPa)			2006
						RTNI(J/m)	135.6	144.7	136.1	153.2	41.4
Fracture mode	4NP；4P 2C	3NB；1H 8C	1NB；1P 10C	3NB；3P 2H；4C	12C
						NI@-18C(J/m)			42.0
Fracture mode			5C
						Bicerano solubility parameter difference J .5/cm 1.5	.23	.39 -2.62	.39 -2.62	-.32 -2.62

[0093] data show appearance best toughness reinforcing (the highest notched izod is impacted) when adopting Vistalon 8600, and it is the noncrystalline ethylene-propylene-ethylidene norbornene random terpolymer that comprises the 8.9wt.% ethylidene norbornene.In the elastomerics of test, only there is the Vistalon8600 compression molded specimens to have shock resistance above 500J/m.Obviously, the ethene/norbornene copolymer of high glass-transition temperature such as Topas 6015, needing a little, the polar elastomerics obtains good impact property.The slight polarity of Vistalon 8600 is produced by its homodiene content.

[0094] in order to estimate the elastomerics polar effect in the blend with Topas 6015 or Topas 6017, after measured the Bicerano solubility parameter of the most polymers of test in the above-described embodiments.The Bicerano solubility parameter of Topas 6015 and Topas 6017 is used 53 and 58 moles of % norbornylene assays respectively.Two kinds of Topas polymkeric substance all have 16.88J ^.5/ cm ^1.5The Bicerano solubility parameter value.Bicerano solubility parameter difference in the table 1 and 2 is calculated by the Bicerano solubility parameter that deducts elastomer An elastomer from this value.

[0095] in Fig. 2 to the elastomerics of seven tests, make the curve of room temperature notched izod shock resistance to the difference (being designated as Est.Sol.Param.) of Bicerano solubility parameter.Bicerano solubility parameter difference between Topas 6015 and elastomerics is 0.2 and 0.4J ^.5/ cm ^1.5Between the time reach best performance.These scopes mark as broken vertical lines in Fig. 4.

[0096] be summarized in table 1 and 2 and Fig. 1 and 2 in the result show that EPDM elastomerics (Vistalon 8600 and 9500) is than styrenic block copolymer (Kraton G1650, G1651, G1652 and Vector 8508) more effective aspect cyclocopolymer impact modified.Bicerano solubility parameter difference show that polystyrene block (second difference in the Comparative Examples 2,3,5,6 and 7) has very much polarity and can not with the Topas polymer-compatible.Any impact modified ethylene/butylene and butadiene block by these SEBS and SBS triblock copolymer produces.The styrene block of these multipolymers has at least 70 ℃ second-order transition temperature.

[0097] heat-drawn wire (HDT) of sample under 1.80MPa that obtain among the embodiment 2 is significantly higher than and can reaches with 6013 of Topas, because Topas 6015 has the second-order transition temperature higher 20 ℃ than Topas6013.HDT also specific energy with polypropylene blend can reach much higher.

[0098] in Comparative Examples 8, provided the impelling strength of non-constant with the blend of maleic anhydride graft amorphous ethylene multipolymer.Obviously, only the polar phase of the elastomerics polarity of close limit and Topas cyclic olefin copolymer mates, and causes high notched izod shock resistance.Elastomeric Bicerano solubility parameter difference in the Comparative Examples 8 is formed information accurately owing to shortage and can't be calculated.

Embodiment 3 and Comparative Examples 9

[0099] compression molding deflection batten is by the TOPAS 6017 of the 70wt% every kind elastomeric mixture preparation listed with the table 3 of 30wt%.Batten such as embodiment 1 are tested, the result is summarized in the table 3.Can find out that Topas 6017 also uses Vistalon 8600 toughness reinforcing, although this very high the impact modified of second-order transition temperature (180 ℃) material seems difficult more.This blend also has the shock resistance above 500J/m.The minor alteration of elastomerics (Vistalon 7001) causes worse result, although Topas 6015 and 6017 has identical Bicerano solubility parameter difference.Embodiment 3 and Comparative Examples 9 show that the elastomerics that adds high level reduces the modulus in flexure of blend.

Table 3-compression molding-30wt.% elastomerics

	Ex.3	Comp.Ex.9
			Topas?6017(pph)	70	70
Vistalon?8600(pph)	30
			Vistalon?7001(pph)		30
Deflection Young's modulus (MPa)	1228	1193
			Modulus in flexure (1%tan) (MPa)	1193	1175
Modulus in flexure (1%sec) (MPa)	1216	1175
			RTNI(J/m)	512.4	281.6
Fracture mode	5NB	2NB，2P，1H
			Bicerano solubility parameter difference J .5/cm 1.5	.29	.23

Embodiment 4 and 5 and Comparative Examples 10 to 30

[00100] in these embodiments, the elastomerics of employing variable quantity has prepared the blend of Topas 6015 and Topas 6017 with melt-mixed blend with twin screw extruder.Use jet molding to prepare test sample.The result be summarized into table 4 to 8 and Fig. 3 in.

The table 4-injection-molded-screen by elastomer type

	Comp. Ex.10	Comp. Ex.11	Comp. Ex.12	Comp. Ex.13
					Topas?6015(pph)	100	80	80	80
Vistalon?7001(pph)			20
					Kraton?G1650(pph)		10		20
Kraton?G1651(pph)		10
					Density (g/ml)	1.028	1.007	0.993	1.002
Deflection Young's modulus (MPa)	3200	2300	2200	2400
					Modulus in flexure (1%tan) (MPa)	3089	2213	2234	2386
Modulus in flexure (1%sec) (MPa)	3151	2282	2179	2386
					0.46MPa under HDT (C)	144.9	142	141	142.5
1.80MPa under HDT (C)	128.5	122.8	120.1	123.2
					RTNI(J/m)	22.5	289.2	296.6	43.3
Fracture mode	5C	5P	5P	5C
					NI@-18C(J/m)	18.9	115.9	82.5	19.5
Fracture mode	5C	5C	5C	5C
					CLTE (10 by DMTA -5/C)	5.97	7.32	9.97
60 degree gloss		72.3	79.3	90.2
					Instrument impacts @RT (J) 5mph, 117#		42.82	39.90	41.04
Fracture mode		5D	5D	5D
					Instrument impacts @-29C (J) 5mph 117#		19.62	48.12	7.05
Fracture mode		3BD 2DB	5D	4BD 1B
					Maximum tensile stress (MPa)	61.4	46.2	46.2	55.2
Young's modulus in tension (MPa)	3300	2500	2350	2700
					Tensile energy @ rupture (J)	1.76	3.39	5.56	3.80
Tension strain @ rupture (%)	2.7	5.1	7.8	5
					Stretching yield strain (%)		3.4	3.6	3.8
Luo Keweier hardness	125.3	109.5	99.4	105.1
					Rong Rongliudong @230C	0.35	0.179	0.255	0.25
Rong Rongliudong @300C	18.42	7.88	9.35	11.1
					Xiao A hardness	75	70	69	69
Shore D hardness	74	70	67	68
					Bicerano solubility parameter difference J .5/cm 1.5		.39 -2.62	.23	.39 -2.62

Table 5-is injection-molded-press rubber consumption to screen

	Comp. Ex.14	Comp. Ex.15	Comp. Ex.16	Comp. Ex.17
					Topas?6015(pph)	95	90	85	80
Vistalon?8600(pph)	5	10	15	20
					Density (g/ml)	1.02	1.01	1.01	0.99
Deflection Young's modulus (MPa)	2900	2700	2400	2150
					Modulus in flexure (1%tan) (MPa)	2944	2661	2330	2282
Modulus in flexure (1%sec) (MPa)	2868	2661	2434	2137
					0.46MPa under HDT (C)	144.1	142.9	142.8	140.5
1.80MPa under HDT (C)	128.6	125.5	124.3	120.5
					RTNI(J/m)	22.7	30.3	127.3	309.8
Fracture mode	5C	5C	5P	5NB
					NI@-18C(J/m)	20.9	29.5	71.0	152.3
Fracture mode	5C	5C	5C	5P
					CLTE (10 by DMTA -5/C)				7.58
60 degree gloss	76	86.2	81.9	81.8
					Instrument impacts @RT (J) 5mph, 117#	4.51	29.68	39.96	39.96
Fracture mode	5B	5BD	5D	5D
					Instrument impacts @-29C (J) 5mph 117#			37.49	40.31
Fracture mode			2D，2BD 1DB	5D
					Maximum tensile stress (MPa)	61.4	55.8	50.3	44.8
Young's modulus in tension (MPa)	2900	2700	2500	2300
					Tensile energy @ rupture (J)	2.85	2.98	7.05	5.02
Tension strain @ rupture (%)	3.7	4	9	7.4
					Stretching yield strain (%)			3.4	3.3
Luo Keweier hardness	120.5	114.8	108.4	98.8
					Rong Rongliudong @230C	0.31	0.3	0.27	0.21
Rong Rongliudong @300C	17.74	15.22	12.84	7.26
					Xiao A hardness	75	74	72	68
Shore D hardness	74	73	72	66
					Bicerano solubility parameter difference J .5/cm 1.5	.29	.29	.29	.29

The table 6-injection-molded-Gao T _gThe comparison of ethene/norbornylene

	Comp. Ex.18	Comp. Ex.19	Comp. Ex.20	Comp. Ex.21	Comp. Ex.22
						Topas?6015(pph)	89.9	79.9	79.9
Topas?6017(pph)				89.9	79.9
						Vistalon?8600(pph)	10		20	10.0	20.0
MDV91-9(pph)		20
						Irgafos?168	0.1	0.1	0.1	0.1	0.1
Density (g/ml)	1.007	0.99	1.112	1.01	0.993
						Deflection Young's modulus (MPa)	2500	2350	2600	2600	2200
Modulus in flexure (1%tan) (MPa)	2455	2261	2420	2475	2096
						Modulus in flexure (1%sec) (MPa)	2482	2330	2344	2620	2151
0.46MPa under HDT (C)	144.7	143.3	142.9	160	159
						1.80MPa under HDT (C)	126.8	125.1	121.3	142	138
RTNI(J/m)	90.7	41.3	363.5	81.1	191.1
						Fracture mode	5C	5C	5NB	5C	5P
NI@-18C(J/m)	43.8	21.2	137.2	43.4	126.0
						Fracture mode	5C	5C	5C	5C	5H
CLTE(10 -5/ C) flow (30 to 100C)			5.3
						CLTE(10 -5/ C) X-flow (30 to 100C)			7
60 degree gloss	82.4	93.4	57.9	76.5	42.8
						Instrument impacts @RT (J) 15mph, 25#	34.98	39.41	34.26	21.76	34.93
Fracture mode	4DB；1D	5D	5D	5B	3DB；2D
						Instrument impacts @-29C (J) 15mph 25#		19.89	21.67
Fracture mode		3BD；2B	5DB；1B
						Maximum tensile stress (MPa)	51.41	48.42	36.22	52.97	42.66
Young's modulus in tension (MPa)	2662	2600	3147	2711	2394
						Tensile energy @ rupture (J)	4.20	4.75	6.37	4.47	7.19
Tension strain @ rupture (%)	5.5	6.2	10.4	5.6	10
						Stretching yield strain (%)	3.2	3.4	2.9	3.4	3.5
Luo Keweier hardness	114.5	92.7	86.8	116.3	104.6
						Rong Rongliudong @300C	13.1	14.6	4.05	9.2	6.4
Xiao A hardness	78	78	78	84	81
						Shore D hardness	81	74	74	82	77
Bicerano solubility parameter difference J .5/cm 1.5	.29	.38	.29	.29	.29

Table 7-is injection-molded-comparison that change to form

	Ex.4	Ex.5	Comp. Ex.23	Comp. Ex.24
					Topas?6015(pph)	70		69.8	79.8
Topas?6017(pph)		70
					Vistalon?8600(pph)	30	30
Exact?5061(pph)				20
					PP8231E1(pph)			30
Irgafos?168			0.1	0.1
					FS-042			0.1	0.1
Density (g/ml)	0.977	0.978	0.983	0.999
					Deflection Young's modulus (MPa)	1662	1662	2200	2200
Modulus in flexure (1%tan) (MPa)	1613	1606	2124	2172
					Modulus in flexure (1%sec) (MPa)	1662	1662	2124	2179
0.46MPa under HDT (C)	139.2	154	138.4	143.3
					1.80MPa under HDT (C)	117.5	131	113	125.1
RTNI(J/m)	656.5	523.1	32.9	92.9
					Fracture mode	5NB	5NB	5C	5H
NI@-18C(J/m)	458.5	400.3	25.3	29.7
					Fracture mode	5NB	5NB	5C	5C
NI@-29C(J/m)	395.0	368.3
					Fracture mode	5P	5P
60 degree gloss	35	39	93.3	93.5
					Instrument impacts @RT (J) 5mph, 117#			3.35	32.96
Fracture mode			5B	4D；1DB
					Instrument impacts @-29C (J) 5mph 117#	38.46	35.51		9.25
Fracture mode	5D	5D		4BD；1B
					Instrument impacts @RT (J) 15mph, 25#	37.28	33.76
Fracture mode	5D	5D
					Instrument impacts @-29C (J) 15mph 25#	43.93	42.17
Fracture mode	5D	5D
					Maximum tensile stress (MPa)	33.12	33.10	38.61	51.71
Young's modulus in tension (MPa)	1838	1737	2550	2540
					Tensile energy @ rupture (J)	14.91	11.25	2.30	8.68
Tension strain @ rupture (%)	25.6	19.1	4.2	10.9
					Stretching yield strain (%)	3.7	3.5	3.2	3.8
Luo Keweier hardness	81	80	94.5	101.8
					Rong Rongliudong @300C	4.1	3.3
Xiao A hardness	70	69	68	67
					Shore D hardness	66	65	64	66
Bicerano solubility parameter difference J .5/cm 1.5	.29	.29	.82 .28	.17

Table 8-is injection-molded-influence of Septon rubber type

	Comp. Ex.25	Comp. Ex.26	Comp. Ex.27	Comp. Ex.28	Comp. Ex.29	Comp. Ex.30
							Topas?6015	89.8	79.8	89.8	79.8	89.8	79.8
Septon?2007	10	20
							Septon?2004			10	20
Septon?HG-252					10	20
							Irgafos?168	0.1	0.1	0.1	0.1	0.1	0.1
FS-042	0.1	0.1	0.1	0.1	0.1	0.1
							Stretching @ surrenders (MPa)	62.46	51.05	61.12	44.04	61.84	44.67
Strain @ surrenders (%)	4	3.8	4.1	4	4.1	4.7
							Strain @ rupture (%)	4.7	4.4	6.6	6	6	15
Modulus in flexure 1%sec (MPa) @0.05in/min	2772	2282	2689	1965	2730	2075
							Modulus in flexure 1%tan (MPa) @0.05in/min	2689	2330	2654	1958	2620	2199
0.46MPa under HDT (C)	144.5	143.6	144.5	141.7	144.9	141
							1.80MPa under HDT (C)	127.5	124.5	127.7	122.2	127.3	121.5
Que Kouxuanbeiliang @23C (J/m)	32.0	42.7	48.0	106.8	26.7	149.5
							Que Kouxuanbeiliang @-18C (J/m)	26.7	32.0	26.7	32.0	21.4	42.7
Bicerano solubility parameter difference J .5/cm 1.5	.53 -2.62	.53 -2.62	.53 -2.62	.53 -2.62	.48 -2.62	.48 -2.62

[00101] Comparative Examples in the table 4 10 shows the characterization data of pure Topas 6015.Do not add under the elastomeric situation, it only is 22.9J/m that the room temperature notched izod is impacted.These brittle polymers can not be used for automobile certainly and use.The 0.46MPa of Comparative Examples 10 and the heat-drawn wire under the 1.80MPa (HDT) are respectively 144.9 ℃ and 128.5 ℃.Can reach these high HDT is because 160 ℃ Topas 6015 second-order transition temperatures.These heat-drawn wire specific energys with polypropylene blend reach much higher.

[00102] in Comparative Examples 11-13,19-20,24,26,28 and 30, Topas6015 is mixed with the multiple elastomerics of 20wt.%.The room temperature notched izod intensity of these samples is mapped in Fig. 3.In the situation as compression molded specimens, the most effective elastomer blend component of notched izod impact that improves 23 ℃ is Vistalon 8600, comprises the ethylene-propylene-ethylidene norbornene terpolymer of 8.9wt.% ethylidene norbornene.

[00103] among Fig. 3, can find out that Vistalon 7001 is also very effective for toughness reinforcing Topas 6015 (Comparative Examples 12).Vistalon 7001 is ethylene-propylene-ethylidene norbornene terpolymers, and it only contains the 5wt.% ethylidene norbornene.Toughness reinforcing Topas 6015 in compression molded specimens is very ineffective for this elastomerics.It is extruding/and the chances are owing to mix better at twin screw extruder for validity in the injection-molded test specimens.

[00104] styrenic block copolymer (Kraton system and Septon system) improving aspect the room temperature notched izod shock resistance of Topas 6015 all not as Vistalon is.Also note ethene plastomer, Exact 5061, (Comparative Examples 24) and ethylene-propylene rubber(EPR), MDV91-9, (Comparative Examples 19) all obviously is not so good as Vistalon 8600 and 7001 ethylene-propylenes-ethylidene norbornene terpolymer aspect toughness reinforcing Topas 6015 effective.It is unexpected that this result similarly forms based on them.

[00105], measured their Bicerano solubility parameter and in Fig. 4, made the curve of 20wt.% blend room temperature notched izod shock resistance the Bicerano solubility parameter difference between the elastomerics of Topas 6015 and each test in order to explain different elastomeric efficient.The compression molding result who plants with Fig. 2 is similar, and difference is between 0.2 and 0.4J when between Topas 6015 and elastomerics Bicerano solubility parameter ^.5/ cm ^1.5The time, observe the highest room temperature notched izod impact results.Kraton system, Septon system, ethylene-propylene copolymer and ethene plastomer are all effective not as Vistalons aspect toughness reinforcing, because them and Topas6015 consistency relatively poor (Bicerano solubility parameter difference is bigger).

[00106] to such an extent as to so effectively in 23 ℃ notched izod shock test, do not observe fracture for Comparative Examples 17 and 20 so that Vistalon 8600 is toughness reinforcing.Do not have other with elastomerics not fracture in room temperature notched izod shock test that 20wt.% loads, this uses for many automobiles is technical requirements.

[00107] injection-molded specimen also characterizes under several temperature by the instrument shock test.In this test, with projectile body speed emission with 5 or 15 miles per hours on polymer disc.Some automakers are for some application requiring ductile failures.Pure Topas 6015 in the Comparative Examples 10 is fragility even can not test too.Comprise Topas 6015 and 20wt.% elastomerics, Vistalon 8600 (Comparative Examples 17 and 20), Vistalon 7001 (Comparative Examples 12), Kraton G1650/G1651 (Comparative Examples 11), the blend of Kraton G1650 (Comparative Examples 13) and MDV91-9 (Comparative Examples 19) all at room temperature demonstrates ductile failure.Yet only Vistalon 8600 (Comparative Examples 17) and Vistalon 7001 (Comparative Examples 12) also are ductile under-29 ℃.These significant cryogenic equipment impact results are possible, because the ethylene-propylene in Vistalon 8600 and 7001-ethylidene norbornene polymkeric substance has low-down second-order transition temperature and compatible with Topas 6015 and 6017.

[00108] be different from 80 of Comparative Examples 17 as can be seen: 20Topas 6015/Vistalon8600 sample, the sample of Comparative Examples 22 (with 20wt.%Vistalon 8600 blended Topas 6015) just do not demonstrate ductile failure under-29C in the instrument shock test.Observing this difference is because the instrument shock test in the Comparative Examples 22 adopts 15 pound weights to launch with 25m.p.h on polymer disc.These test conditionss are sent to test sample with more energy, make it more be difficult to ductile failure and pass through.

[00109] in embodiment 4 and Comparative Examples 14-17 and 20, use twin screw extruder and injection molding machine to prepare a series of Topas6015 blends with the Vistalon 8600 of different amounts.In Fig. 5, compared the room temperature notched izod impact results of these blends.Unexpectedly and non-linear to heavens toughness reinforcing appearing at comprise 15% or how elastomeric blend.Topas 6015 blends (embodiment 4 of table 7) with 30wt.%Vistalon 8600 have significant toughness.In room temperature and-18 ℃ of izodtests, do not observe fracture.In the instrument shock test of 23 ℃ and-29 ℃, observe and have only ductile failure.When 15 pound weights are launched on sample with 25m.p.h, embodiment 4 even in the instrument shock test, have ductile failure.25.6% breaking strain is that this blend compares how to have the flexible strong evidence with the Topas 6015 of beginning.0.46 and the heat-drawn wire 139.2 of 1.80MPa and 117.5 ℃ are significantly higher than and can reach with polyacrylic high-impact blend.

[00110] Comparative Examples 23 illustrates that not only the elastomerics of high filler loading capacity is that toughness reinforcing Topas6015 is necessary.This Comparative Examples is used the toughness reinforcing cyclic olefin copolymer of high impact resistance polypropylene of 30wt.%.Obtained the only relatively poor room temperature notched izod shock resistance of 32.9J/m.In order to reach the HI high impact modification, that elastomerics also needs is 6015 compatible with Topas (is that Bicerano solubility parameter difference need be between 0 and 0.6, preferably between 0.2 and 0.4J ^.5/ cm ^1.5Between).

[00111] Topas 6017 is ethene/norbornene copolymers of 180 ℃ of second-order transition temperatures.It is slightly more difficult more toughness reinforcing than Topas 6015.Referring to Topas 6015 and 6017 and 10wt.%Vistalon 8600 (Comparative Examples 18 and 21 in the table 6), the comparison between the blend of 20wt.%Vistalon8600 (Comparative Examples 20 and 22 in the table 6) and 30wt.%Vistalon 8600 ( embodiment 4 and 5 in the table 7).The Vistalon of same loading level 8600 times, Topas 6017 blends have the notched izod impact value lower a little than Topas 6015 blends.Yet two kinds of cyclic olefin copolymers all reach the target of 500J/m notched izod shock resistance when filling 30wt.%Vistalon 8600.

[00112] Topas 6017 blends are owing to Topas 6017 high glass transition have at 0.46MPa (for example for 20wt.%Vistalon 8600,159 couples of 142.9C) and 1.80MPa (for example for 20wt%Vistalon 8600,138 couples 121.3) higher thermal denaturation temperature down.

[00113] among Fig. 6, with embodiment 4 in the character of commodity high impact resistance polypropylene (ExxonMobil PP8224E1) and the table 7 and 5 those relatively.The not fracture in room temperature notched izod shock test (not expression among Fig. 6) of whole three kinds of blends.Two kinds of ethene/norbornylenes have and the about identical instrument impact energy of polypropylene specimen, even they are measured at 5m.p.h at 117 pound weights that 25m.p.h rather than report are used for high impact resistance polypropylene with 15 pound weights.The high-speed equipment shock test is strict more usually, shows that embodiment 4 and 5 has the impact property better slightly than polypropylene blend.Embodiment 4 and 5 has the tensile strength significantly higher than commodity polypropylene blend, higher rigidity (modulus in flexure) and higher heat-drawn wire.Three kinds of materials have closely similar density.The high impact resistance polypropylene blend is used for the whole world requires the automobile external of low-temperature flexibility to use as the snubber dashboard.

[00114] All Files described herein comprises that any priority document and/or testing method are hereby incorporated by up to them and the inconsistent degree of this paper.As obvious,, can carry out various changes in situation without departing from the spirit and scope of the present invention though form of the present invention is illustrated and describes from above-mentioned general remark and specific embodiments.Therefore, be not to be intended to limit thus the present invention.

Claims (27)

1. polymer composition comprises:

A) greater than the cyclic olefin copolymer of 50wt% (based on the weight of composition), described cyclic olefin copolymer comprises one or more cyclic olefins (based on the weight of cyclic olefin copolymer) of at least a acyclic olefin and at least 20 weight %, and wherein the described cyclic olefin copolymer of at least a portion has the second-order transition temperature greater than 150 ℃;

B) less than the acyclic olefin polymer modifiers of 50wt% (based on the weight of composition), partially modified at least dose has and is lower than-30 ℃ second-order transition temperature; And properties-correcting agent do not have softening temperature greater than+30 ℃ part, and the Bicerano solubility parameter of properties-correcting agent is no more than 0.6J less than the Bicerano solubility parameter of cyclic olefin copolymer ^0.5/ cm ^1.5

C) the composition notched izod shock resistance that wherein records under 23 ℃ is greater than 500J/m and use composition heat-drawn wire that the 0.46MPa load records greater than 135 ℃.

2. the polymer composition of claim 1, wherein said cyclic olefin copolymer comprises at least 30 weight %, one or more cyclic olefins of preferred at least 40 weight %.

3. claim 1 or 2 polymer composition, wherein the described cyclic olefin copolymer of at least a portion has greater than 160 ℃, is preferably greater than 170 ℃ second-order transition temperature.

4. each polymer composition in the claim 1 to 3, wherein a part of described cyclic olefin copolymer has the softening temperature less than 30 ℃.

5. each polymer composition in the claim 1 to 4, wherein whole described cyclic olefin copolymers have the second-order transition temperature greater than 150 ℃.

6. each polymer composition in the claim 1 to 5, wherein a part of described polymer modifiers has less than-40 ℃, preferably less than-50 ℃ second-order transition temperature.

7. each polymer composition in the claim 1 to 6, wherein whole described polymer modifiers have the second-order transition temperature less than-30 ℃.

8. each polymer composition in the claim 1 to 7 does not wherein have described polymer modifiers part softening temperature greater than 10 ℃.

9. each polymer composition in the claim 1 to 8, wherein said polymer modifiers has the Bicerano solubility parameter 0.1-0.5J less than cyclic olefin copolymer ^0.5/ cm ^1.5, preferred 0.2-0.4J ^0.5/ cm ^1.5The Bicerano solubility parameter.

10. each polymer composition in the claim 1 to 9 comprises about 20wt% to about 40wt%, and preferred 25wt% is to the described polymer modifiers of 35wt%.

11. each polymer composition in the claim 1 to 10, the composition notched izod shock resistance that wherein records under 23 ℃ is preferably greater than 600J/m, more preferably greater than 700J/m greater than 550J/m.

12. each polymer composition in the claim 1 to 11 wherein uses composition heat-drawn wire that 0.46MPa load records greater than 150 ℃, is preferably greater than 165 ℃.

13. the polymer composition of each in the claim 1 to 12 wherein uses composition heat-drawn wire that 1.80MPa load records greater than 115 ℃, is preferably greater than 130 ℃, more preferably greater than 145 ℃.

14. each polymer composition in the claim 1 to 13, the composition notched izod shock resistance that wherein records under-18 ℃ is preferably greater than 150J/m greater than 50J/m, more preferably greater than 300J/m, most preferably greater than 500J/m.

15. each polymer composition in the claim 1 to 14, the composition instrument impact energy that wherein records under 23 ℃ is preferably greater than 30J greater than 25J.

16. each polymer composition in the claim 1 to 15, the composition instrument impact energy that wherein records under-29 ℃ is preferably greater than 30J greater than 25J.

17. each polymer composition in the claim 1 to 16, the composition modulus in flexure of wherein utilizing the measurement of 1% sencant method is preferably greater than 2000MPa, more preferably greater than 2500MPa greater than 1200MPa.

18. each polymer composition in the claim 1 to 17, wherein said polymer modifiers comprise ethene, high alpha-olefin and 5wt% but be less than the multipolymer of the cyclic olefin of 20wt% at least.

19. the polymer composition of claim 18, wherein cyclic olefin is selected from norbornylene, ethylidene norbornene, vinyl norbornene, vinyl cyclohexene and Dicyclopentadiene (DCPD).

20. the polymer composition of claim 18 or 19, wherein alpha-olefin is selected from propylene, hexene and octene.

21. each polymer composition in the claim 1 to 17, wherein said polymer modifiers comprise and contain ethene, propylene and choose any one kind of them or the polymkeric substance of multiple diene.

22. the polymer composition of claim 21, wherein this polymkeric substance comprises 25 to the ethene of 80wt%, until one or more diene of 15wt% and the propylene of surplus.

23. each polymer composition in the claim 1 to 17, wherein said polymer modifiers comprise ethene and 7-methyl isophthalic acid, the multipolymer of 6-octadiene.

24. each polymer composition in the claim 1 to 23, wherein said cyclic olefin copolymer comprises the multipolymer of ethene and norbornylene and/or Dicyclopentadiene (DCPD).

25. each polymer composition in the claim 1 to 24 is wherein with some or all hydrogenations, the epoxidation and/or functionalized of the remaining double bond of cyclic olefin copolymer.

26. each polymer composition in the claim 1 to 25 comprises the mixture of melts of described cyclic olefin copolymer (a) and described polymer modifiers (b).

27. the assembly that is used for automobile by each polymer composition preparation in the claim 1 to 26.

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