CN1357014A - Ethylene and/or alpha-olefin/vinyl or viylidene aromatic interpolymer compsns. - Google Patents

Ethylene and/or alpha-olefin/vinyl or viylidene aromatic interpolymer compsns. Download PDF

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CN1357014A
CN1357014A CN00809296A CN00809296A CN1357014A CN 1357014 A CN1357014 A CN 1357014A CN 00809296 A CN00809296 A CN 00809296A CN 00809296 A CN00809296 A CN 00809296A CN 1357014 A CN1357014 A CN 1357014A
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interpolymer
vinyl
component
alpha
ethene
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S·F·汉恩
O·D·莱德维恩
R·B·杉卡
F·J·提默斯
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Dow Chemical Co
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
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    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
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Abstract

The present invention pertains to an interpolymer comprising; (1) from 5 to 85 mol percent of polymer units derived from one or more vinyl or vinylidene aromatic monomers, (2) from 15 to 95 mol percent of polymer units derived from at least one of ethylene and/or a C3-20 alpha-olefin; and (3) from 0 to 20 mol percent of polymer units derived from one or more of ethylenically unsaturated polymerizable monomers other than those derived from (1) and (2); and wherein said interpolymer contains detectable vinyl or vinylidene aromatic monomer triads.

Description

Ethene and/or alpha-olefin/binyl or vinylidene aromatic copolymer composition
The present invention relates to comprise the composition of the interpolymer of vinyl or vinylidene aromatic monomer and ethene and/or one or more 'alpha '-olefin monomers.Catalyzer [(4,5-methylene radical-phenanthryl) (tertiary butyl amino) dimethylsilane] the dimethyl titanium that is used to prepare these interpolymers has obviously high reactivity to vinyl or vinylidene aromatic monomer.The gained interpolymer comprises successive vinyl or vinylidene aromatic monomer insertion group and therefore can have and surpasses 65% mole vinyl or vinylidene aromatic monomer add-on.
Up to date, the copolyreaction of ethene and vinyl or vinylidene aromatic monomer is not that a kind of commercial available uses the technology based on Ti (III) and the halid traditional Z iegler alpha-olefin polymerization catalyst of Ti (IV).In the past great majority can not obtain the vi-ny l aromatic monomers of remarkable add-on with the trial of the multipolymer of multipolymer, the especially vinylbenzene of these Preparation of Catalyst vi-ny l aromatic monomers and alpha-olefin and ethene, or obtain low-molecular-weight polymkeric substance.Polymer Bulletin, 20,237-241 (1988) discloses a kind of multipolymer of vinylbenzene and ethene, wherein comprises 1% mole vinylbenzene add-on.Polymer yield is said to be 8.3 * 10 -4The used titanium of gram polymkeric substance/mmole.But along with the metallocenyl polymerisation catalysts, the especially appearance of constrained geometry type catalyzer might obtain interpolymer with other vinyl or vinylidene aromatic monomer copolyreaction with ethene and other alpha-olefin and vinylbenzene now.
The ethene and the cinnamic multipolymer that comprise vinylbenzene add-on more than 50% mole have allegedly used a kind of ansa-metallocene catalyzer, Arai for example, T.; Ohutsu, T.; Suzuki, S. are disclosed in Macromolecular Rapid Commun.1988 and Polym.Prepr., and 1998,39 (1), 220-221.
In addition, United States Patent (USP) 5703187 has been described " false random " the ethylene styrene interpolymer that is characterised in that a kind of unique monomers distributes, and does not wherein observe successive styrene monomer insertion group end to end, does not promptly have SS diad or SSS triad.Except styrene monomer insertion group end to end continuously not, therefore the still good dispersion that distributes of the vinylbenzene in the interpolymer is called " false random ".A special outstanding feature of false random copolymers is, all phenyl that replace on main polymer chain or huge steric group be separated by 2 or polymethylene unit more.In polyaddition reaction, if vinyl or vinylidene aromatic monomer embed the polymer chain that increases, next embeds monomer must be (wherein ought normally be embedded as 1 with trans, 2 o'clock trans is meant 2,1 embeds, but those skilled in the art are appreciated that reverse situation can exist and can change description or its performance to interpolymer of the present invention) ethene or vinyl or the vinylidene aromatic monomer that embed.After trans embedding vinyl or vinylidene aromatic monomer, next monomer must be an ethene, because this moment embeds another vinyl or vinylidene aromatic monomer can make the steric hindrance substituting group be close together, rather than above-mentioned minimum is isolated.These kinetics of polymerization reaction cause the catalyst system therefor can be with the vinylbenzene homopolymerization to any acceptable degree, and ethene and the rapid polymerization of cinnamic mixture and can obtain the multipolymer of high-phenylethylene content (the highest 50% mole of vinylbenzene).The direct result of this monomer distribution is that the actual upper bound of vinylbenzene add-on is about 50% mole or 79% weight styrene.
WO98/0999 has described " random basically " ethylene styrene interpolymer, not only comprises above-mentioned false random copolymer, and comprises the interpolymer that uses the luxuriant polymerisation catalysts of special metal to make.The application of the luxuriant initiators for polymerization of these special metals causes forming the interpolymer that is distributed as feature with unique monomers.In this distributes, although being false irregular phenylethylene, the most polymers chain distributes, observe a spot of at two end to end before the vi-ny l aromatic monomers insertion group and the sequence of at least one ethene insertion group arranged afterwards.It is ethylene/styrene/styrene/ethylene four unit group ESSE, and the styrene monomer insertion group of wherein said four unit groups only occurs in 1,2 mode.That is, similar peak when these specific random basically ethylene/styrene interpolymers comprise with false random ethylene/styrene copolymer in NMR spectrum appears at the additional signal of chemical shift range 43.70-44.25ppm but feature also is intensity.The result that this unique monomers distributes is that the vinylbenzene add-on upper limit in the random basically ethylene styrene interpolymer rises to about 65% mole or 87.5% weight styrene.
We shockingly find, catalyzer [(4,5-methylene radical-phenanthryl) (tertiary butyl amino) dimethylsilane] the dimethyl titanium has obviously high reactivity to it, and therefore prepares the new interpolymer that comprises SSS and Geng Gao (for example SSSS, SSSSS etc.) sequence under ethylene/styrene interpolymer situation in the polyreaction of vinyl or vinylidene aromatic monomer and ethene and/or one or more 'alpha '-olefin monomers.Because the reactivity of catalyzer increases, the gained interpolymer can show and surpass 65% mole vinyl or vinylidene aromatic monomer upper content limit.
The present invention relates to a kind of interpolymer, comprise:
(1) polymer unit derived from least a vinyl or vinylidene aromatic monomer of 5-85% mole,
(2) the 15-95% mole derived from least a ethene and/or C 3-20The polymer unit of alpha-olefin; With
(3) polymer unit derived from one or more alkene unsaturated polymerizable monomers except that (1) and (2) of 0-20% mole; With
Described interpolymer comprises detectable vinyl or vinylidene aromatic monomer triad.
All reference papers when this paper relates to the element that belongs to certain family or metal are meant by CRCPress, Inc., and 1989 publish and have the periodic table of elements of copyright.Equally, all reference contents that relate to " family " should be meant " family " given when using IUPAC family naming system in the periodic table of elements.
All numerical value used herein comprise that from than all values of low value to high value, increment is a unit, as long as differ at least 2 units any between than low value and any high value.For example, if the amount of component or process variable such as temperature, pressure, time are stated as for example 1-90, preferred 20-80, more preferably 30-70 means so and has enumerated numerical value such as 15-85,22-68,43-51,30-32 etc. in this manual.For the numerical value that is lower than 1, a unit can be considered to 0.0001,0.001 or 0.1 as required.Therefore these are the example of concrete implication, obtain similar statement in this application any may combinations of values all the thinking between listed Schwellenwert and the maximum.
Term used herein " interpolymer " is meant a kind of like this polymkeric substance, and wherein at least two kinds of different monomer polymerizations form this interpolymer.It comprises multipolymer, terpolymer etc.
Term used herein " detectable vinyl or vinylidene aromatic monomer triad " is meant three the continuous vinyl in this interpolymer or the sequence of vinylidene aromatic monomer insertion group.Under the situation of ethylene/styrene interpolymer, this is corresponding to-SSS-triad.If isolate any random isotactic polystyrene impurity from polymkeric substance, these triad can be by being present in 13A peak in the C NMR spectrum detects, and this peak appears at chemical shift 44.6ppm (ESSSE) and locates, corresponding to the methine carbon in the main polymer chain of ethylene/styrene interpolymer.These triad are the part of the longer sequence of vinyl or vinylidene aromatic monomer insertion group such as SSSS four unit groups, SSSSS five unit groups also.Other peak corresponding to following insertion group also can be present in this interpolymer: 46.0ppm (ESE), 43.75ppm (ESSE) and 41.6ppm (greater than 3 continuous S insertion groups).Those skilled in the art are appreciated that this interpolymer obtains similarly for comprising vinyl except that vinylbenzene or these insertion groups of vinylidene aromatic monomer and the alpha-olefin except that ethene 13C NMR peak, but chemical shift is different slightly.
Interpolymer of the present invention uses catalyzer [(4,5-methylene radical-phenanthryl) (tertiary butyl amino) dimethylsilane] dimethyl titanium to make.
We find shockingly that this catalyzer has obviously high reactivity to it in the polyreaction of vinyl or vinylidene aromatic monomer and ethene and/or one or more 'alpha '-olefin monomers.Therefore prepare the new interpolymer that under ethylene/styrene interpolymer situation, comprises SSS and Geng Gao (for example SSSS, SSSSS etc.) sequence.Because the reactivity of catalyzer increases, the gained interpolymer can show and surpass 65% mole vinyl or vinylidene aromatic monomer upper content limit.
A kind of method for preparing interpolymer of the present invention comprises, under the existence of catalyzer [(4,5-methylene radical-phenanthryl) (tertiary butyl amino) dimethylsilane] dimethyl titanium and suitable activating compounds, the mixture of polymerisable monomer carried out polymerization.By using this catalyzer, interpolymer of the present invention can prepare by being described in the EP-A-0416815 (people such as James C.Stevens) and the method for United States Patent (USP) 5703187 (Francis J.Timmers), incorporates the both into the present invention as a reference at this.The preferred operational condition of these polyreactions is the temperature of normal atmosphere to 3000 an atmospheric pressure and-50 ℃ to 200 ℃.Under the temperature that is higher than on each monomer autopolymerization temperature, carry out polyreaction and remove unreacted monomer causing forming a certain amount of homopolymer polymerisate that derives from Raolical polymerizable.In preparation during interpolymer of the present invention and since vi-ny l aromatic monomers at high temperature homopolymerization and may form a certain amount of atactic vinyl or vinylidene aromatic homopolymer.The existence of aromatic vinyl homopolymer does not generally have harm to the present invention and can allow.The aromatic vinyl homopolymer can separate from this interpolymer by abstraction technique such as liquid chromatography as required, or uses the non-solvent of this interpolymer or vinyl or vinylidene aromatic homopolymer to carry out selective precipitation from solution.
Interpolymer of the present invention comprises the interpolymer of making by the following material of polymerization: i) ethene and/or one or more 'alpha '-olefin monomers and ii) one or more vinyl or vinylidene aromatic monomer and optional iii) other polymerizable ethylenically unsaturated monomer.
Suitable 'alpha '-olefin monomers for example comprises and contain 3 to 20, and is preferred 3 to 12, more preferably the alpha-olefin of 3 to 8 carbon atoms.Specially suitable is the combination of ethene, propylene, butene-1,4-methyl-1-pentene, hexene-1 or octene-1 or ethene and one or more propylene, butene-1,4-methyl-1-pentene, hexene-1 or octene-1.
Other optional polymerizable ethylenically unsaturated monomer comprises norbornylene and C 1-10Alkyl or C 6-10The norbornylene that aryl replaces, wherein the example of interpolymer is ethylene/styrene/norbornene and ethylene/styrene/ethylidene norbornene.
The vinyl or the vinylidene aromatic monomer that are applicable to this interpolymer of preparation comprise, for example with those monomers of following formula representative:
Figure A0080929600101
R wherein 1Be selected from hydrogen atom and the alkyl that contains 1 to 4 carbon atom, preferred hydrogen atom or methyl; Each R 2Be independently selected from hydrogen atom and the alkyl that contains 1 to 4 carbon atom, preferred hydrogen atom or methyl; Ar is phenyl or is selected from halogen, C by 1 to 5 1-4Alkyl and C 1-4The phenyl that substituting group replaced of haloalkyl; And the value of n is 0 to 4, and is preferred 0 to 2, most preferably 0.The example of vi-ny l aromatic monomers comprises vinylbenzene, Vinyl toluene, alpha-methyl styrene, t-butyl styrene, chlorostyrene, comprises all isomer of these compounds.Specially suitable this class monomer comprises vinylbenzene and low alkyl group or halogen substituted derivative.Preferred monomers comprises vinylbenzene, alpha-methyl styrene and low alkyl group-(C 1-4) or the nuclear substituted styrene derivatives of phenyl, for example adjacent-,-and p-methylstyrene, the halogenated vinylbenzene of ring, to Vinyl toluene or its mixture.Preferred aromatic vinyl monomer is a vinylbenzene.
Modification is carried out in the typical grafting that the gained interpolymer can be known by those skilled in the art, hydrogenation, functionalized or other reaction.This polymkeric substance often uses the method that is described in WO99/20691 (incorporating it into the present invention as a reference at this) to carry out sulfonation, carry out chlorination or functionalized according to pending trial Application No. 09/244921 (people such as R.E.Drumright submitted on February 4th, 1999, incorporated it into the present invention as a reference at this) is described.Composition of the present invention also can carry out modification by various cross-linking methods.These methods include, but is not limited to superoxide-, silane-, sulphur-, radiation-or trinitride-Ji curing system.About the detailed description of various cross-linking methods is described in United States Patent (USP) 5869591 and 5977271, incorporate both into the present invention as a reference at this.The dual cure systems of comprehensive utilization heat, moisture-curing and irradiation step also can effectively adopt.For example, may need to be used in combination peroxide cross-linking agent and silane crosslinker, peroxide cross-linking agent and radiation, contain sulfur crosslinking agent and silane crosslinker etc.Dual cure systems is open and requirement in United States Patent (USP) 5911940, incorporates it into the present invention as a reference at this.
Additive such as antioxidant are (for example, sterically hindered phenol, as Irganox  1010, the registered trademark of Ciba Geigy), phosphorous acid ester (for example, Irgafos  168, the registered trademark of Ciba Geigy), ultra-violet stabilizer, cementitious additives (as, polyisobutene), slip(ping)agent (as, stearylamide and/or mustard acid amides), anti-caking agent, tinting material, pigment, tackifier, fire retardant, coupling agent, filler, softening agent also can be used for composition of the present invention.
Various organic and mineral fillers also can be used as potential component and are included in the present composition.The typical example of these fillers comprises organic and inorganic fibre, for example derives from asbestos, boron, graphite, pottery, glass, metal (as, stainless steel) or polymkeric substance (as aramid fiber); Talcum, carbon black, carbon fiber, lime carbonate, three hydrated alumina, glass fibre, marble flour, cement flour, clay, feldspar, silica or glass, pyrogenic silica, alumina, magnesium oxide, magnesium hydroxide, weisspiessglanz, zinc oxide, barium sulfate, pure aluminium silicate, ammonium polyphosphate, Calucium Silicate powder, titanium dioxide, titanate, aluminium nitride, B 2O 3, nickel powder or chalk.
Other representative organic or inorganic fiber or mineral filler comprise carbonate, as barium carbonate, lime carbonate or magnesiumcarbonate; Borate is as magnesium borate or zinc borate; Fluorochemical such as Calcium Fluoride (Fluorspan) or sodium aluminum fluoride; Oxyhydroxide such as aluminium hydroxide; Metal such as aluminium, bronze, lead or zinc; Oxide compound such as aluminum oxide, weisspiessglanz, magnesium oxide or zinc oxide or silicon-dioxide or titanium dioxide; Silicate such as asbestos, mica, clay (kaolin or calcined kaolin), Calucium Silicate powder, feldspar, glass (pulverizing or foliated glass or hollow glass ball or microballoon or pearl, palpus or silk), nepheline, nacrite, pyrophyllite, talcum or wollastonite; Vitriol such as barium sulfate or calcium sulfate; Metallic sulfide; Mierocrystalline cellulose, for example form of wood powder or shell powder; Terephthalic acid calcium; And liquid crystal.Also can use the mixture of more than one these class fillers.
These fillers also can with coupling agent and/or be selected from organo-peroxide, silane, titanate, zirconate, polyfunctional vinyl compound, organic azide, and composition thereof initiator be used in combination.
Other additive comprises sterically hindered amine stabilizer.These stablizers comprise that the steric hindrance triazine is as replacing the reaction product of triazine and triazine.Suitable reaction product comprises the reaction product of triazine and for example diamines and/or cycloaliphatic compounds such as hexanaphthene.Specially suitable sterically hindered amine stabilizer comprises 1,3-propylene diamine, N, N "-1; 2-second two basic bicyclohexane and peroxidation N-butyl-2; 2,6,6-tetramethyl--4-piperylhydrazine-2; 4; reaction product of 6-three chloro-1,3,5-triazines; undertaken by Ciba-Geigy that commerce is made and name is called " CG-116 ", CAS registration number: 191680-81-6.
These additives use with the known function significant quantity of those skilled in the art.For example, the consumption of antioxidant to make can prevent polymkeric substance or blend polymer store and the final temperature of using this polymkeric substance and environment under oxidation takes place.This consumption of antioxidant is generally the 0.01-10% weight based on polymkeric substance or blend polymer weight, preferred 0.05-5% weight, more preferably 0.1-2% weight.Similarly, the consumption of any other listed additive all is the function significant quantity, for example can give polymkeric substance or blend polymer with resistance to blocking, produces required filling adding amount to obtain required result, produces required color by tinting material or pigment.The suitable amounts scope of these additives is the 0.05-50% weight based on polymkeric substance or blend polymer weight, preferred 0.1-35% weight, more preferably 0.2-20% weight.The suitable amounts of filler can be a 1-90% weight.
Polymkeric substance of the present invention can with other polymer blending, comprising (but being not limited to): other interpolymer with different molecular weight and/or vinyl or vinylidene aromatic monomer content; Basically random interpolymer vinyl or vinylidene halide polymkeric substance include, but is not limited to polyvinyl chloride and polyvinylidene dichloride; Polyethylene; With other polyolefine, include, but is not limited to LDPE and HDPE, PP; By homogeneous ethylene/alpha-olefin copolymer that metalloscene catalyst is made, the heterogeneous ethylene/alpha-olefin copolymer that includes, but is not limited to the substantial linear ethylene/alpha-olefin copolymer and make by Ziegler catalyst; Styrene based copolymer includes, but is not limited to polystyrene, SBS multipolymer; Polyethers; Polycarbonate, polyaniline; Pitch; Or its any combination.
Interpolymer of the present invention or its blend can be made into various forms, include, but is not limited to film, fiber, foam materials, sheet material, injection-molded item, film, notes blow-molded article and extruded profile and emulsion.The purposes of interpolymer of the present invention or its blend includes, but is not limited to fire-retardant product, pressure-sensitive film material, coating composition or paint, floor, top ceiling and wall covering, carpet backing, blocking layer, packing ring, lid and dividing plate and the various conductions when adding conductive additive such as carbon black are used, and comprises electronics, conductor shield cap, insulation protective hood and the application of other electric wire and cable.Other application is included in the blend of polystyrene and ethene and/or alpha-olefin homo and multipolymer and is used as expanding material.Also comprise the application of sulfonated derivative, comprise their application in fuel cell membranes, suction application and HVAC device.
It is indefinite that the ethylene/styrene interpolymer of the present invention that uses the NMR analytical procedure to determine is formed.This indeterminate following fact that is derived from: the vinylbenzene insertion group of vinylbenzene triad and Geng Gao order exists 1H and 13All have the peak among the C, can not be different from the peak that is present in the ubiquitous amorphous random isotactic polystyrene homopolymer (aPS) in this interpolymer on a small quantity.But use gradient solvent polar liquid chromatography (LC) method can from aPS, isolate this interpolymer, and the retention time at this interpolymer peak is represented its styrene content.
Copolymer composition of the present invention comprises 5-85, preferred 20-85, the more preferably at least a vinyl of 50-85% mole or vinylidene aromatic monomer and 15-95, preferred 15-80, the more preferably ethene of 15-50% mole and/or at least a aliphatic alpha-olefin with 3-20 carbon atom.
Melt index (the I of interpolymer of the present invention 2) greater than 0.05, preferred 0.5-200, more preferably the 0.5-100 gram is/10 minutes.
The molecular weight distribution of interpolymer of the present invention (Mw/Mn) is 1.5-20, preferred 1.8-10, more preferably 2-5.
Copolymer composition of the present invention comprises detectable vi-ny l aromatic monomers triad.Under the situation of ethylene/styrene interpolymer, this is corresponding to-SSS-triad.These triad are the part of the longer sequence of vinyl or vinylidene aromatic monomer insertion group such as SSSS four unit groups, SSSSS five unit groups also.If isolate any random isotactic polystyrene impurity from polymkeric substance, these triad can be by being present in 13A peak in the C NMR spectrum detects, and this peak appears at chemical shift 44.6ppm (ESSSE) and locates, corresponding to the methine carbon in the main polymer chain of ethylene/styrene interpolymer.
Following examples are used to illustrate the present invention, limit its scope by any way and should not be construed as.
Embodiment
Testing method
The molecular weight of polymer composition of the present invention is fit to use gel permeation chromatography to represent, wherein uses UV and refractive index detector.
In order to measure interpolymer of the present invention 13Following step and condition adopted in the displacement of C nmr chemical.By 50% volume sym.-tetrachloroethane-d 2Preparation 5-10% weight polymer solution in the mixture of forming with 50% volume 0.10M three (vinyl acetone) chromium (1,2, in the 4-trichlorobenzene).NMR spectrum uses down reverse gate decoupling filter fly prefaces, 90 ° of pulse widths and 5 seconds or higher pulse delay and obtains at 130 ℃.This spectrum is used for being positioned at reference to this polymkeric substance the independent methylene signals of 30.000ppm.
Testing of materials
By 150 ℃ of following compression moulding, polymer samples is shaped to the required shape of measuring physical properties, wherein use preheating in 10 minutes, compressions under 10000 ft lbfs 3 minutes and cooling polymer sample immediately.
The dsc of this polymkeric substance (DSC) is analyzed under nitrogen atmosphere and is used DuPont Instruments 910 differential scanning calorimeters to carry out with 5 ℃/minute heating rate.All samples is by carrying out two heating periods influence of thermal history (remove before) and data all write downs in all cases for the second time and scan.
Micro-stretching test uses the little stretching rod of compression moulding to carry out according to ASTM D638 testing scheme.Sample uses Instron 4507 serial instruments at room temperature to stretch with the pinblock speed of 0.1 inch per minute clock and the load of 224.8 ft lbfs.
Plane strain fracture toughness, the monolateral breach geometric sample of compression stretching are compression molded into 1 " * 1 " * 1/8 " square.These square mechanical workouts are obtained side breach and hole, in order to connect test set.Also carry out cracking by cooled with liquid nitrogen, in each sample, form precracking with slasher and hammer.The fracture toughness property test uses Instron 8501 instruments to carry out under the load of 224.8 ft lbfs with the pinblock speed of 0.02 inch per minute clock.
The dynamic mechanical spectroscopic analysis is carried out on rectangular bar, and this rod is 100 ℃ of following compression moulding.Under the setpoint frequency of 1 radian per second, carry out from-100 ℃ to 150 ℃ temperature scanning, wherein use the automatic response function of setting by the DMS instrument.
Density is used the helium pycnometric determination.Rockwell hardness is used ASTM D785-93 assessment.
L.C. analyze
0.100-0.102 is restrained polymkeric substance to be weighed in 30 milliliters of bottles.Add 10 milliliters of THF.Bottle covered and be placed on be heated on the vibrator with sample dissolution.The temperature of vibrator of being heated is 65 ℃.After the dissolving, about 1 ml soln is transferred to HP 1090 LC automatic injector bottles.Hewlett-Packard 1090 LC (series number 2541A00700) that use has diode-array detector collect all chromatographic instrument data.Collect the signal of 254 nanometers and 400 nanometers.The chromatographic instrument data use Grams386 and Excel software to handle.
By liquid chromatography, use two posts to measure the styrene content of resin.The use of each post all at first comprises the mensuration of random isotactic polystyrene content (its peak obviously can be distinguished).This value is subsequently from passing through 13Deduct in total styrene content of the sample that C NMR records, obtain the % weight of co polystyrene.Make the calibration curve at co polystyrene relative retention time (at the 50th percentage ratio place of chromatographic peak) subsequently, and subsequently the gained match is applied to all fresh samples.This analysis uses two kinds of posts to carry out.
First kind is the C18 post that derives from Alltech: 5 microns of Spherisorb ODS II, 250 * 4.60 millimeters.A guard column is arranged on the C18 post.It is 8.5 microns of RP.It below is the instrument condition that on HP 1090, uses with C18 post.
Solvent orange 2 A=acetonitrile 24.00, flow velocity=1.000
Solvent B=THF 24.00, percentage ratio B=100.0, C=
Solvent C=2-propyl alcohol 25.00, flow velocity=1.000
Store flow velocity 1; 25.00, percentage ratio B=1.0, C=0.0
Stand-by time=30.00 30.00, flow velocity=1.000
The back time (post time)=0.00 30.00, percentage ratio B=1.0, C=0.0
The SDS configuration, A=1, B=1, C=1
Peak pressure=400 Stand-by time=system
Minimum pressure=8 Back time=1.00 minute
??B＝1.0，C＝0.0 Self-poise=unlatching
Volume injected=10.0 liter Peak width=0.100
Furnace temperature=50.0 Spectral range=240,600,2
1.00, flow velocity=1.000 ml/min Store spectrum=peak
1.00, percentage ratio B=1.0, C=0.0 Threshold value=1.000
20.00, flow velocity=1.000 Signal A=254,4,550,20
20.00, percentage ratio B=100.0, C=0.0 Signal B=400,4,550,20
Second kind also be a kind of preferably among both be 250 * 4.60 millimeters of the nitro post that derives from Phenomenex: Nucleosil 5 NO2,5 microns, series number 243745.A guard column is arranged on the nitro post.It is 30 * 4.6 millimeters of Phenomenex Nucleosil 5 NO2,5 micron 100 dust, series number 243747G.It below is the instrument condition that on the HP 1090 that adopts Nitro2 method (nitro post), uses.
Solvent orange 2 A=hexane 20.00, flow velocity=1.000
Solvent B=THF 20.00, percentage ratio B=70.0, C=0.0
Solvent C=2-propyl alcohol 23.00, flow velocity=1.000
Store A1; 23.00, percentage ratio B=70.0, C=0.0
Store B1; 24.00, flow velocity=1.000
Store C1; 24.00, percentage ratio B=3.0, C=0.0
Store flow velocity 1; 30.00, flow velocity=1.000
Storing temp 1; 30.00, percentage ratio B=3.0, C=0.0
Stand-by time=30.00 minute
Back time=0.00 minute
The SDS configuration, A=1, B=1, C=1 Stand-by time=system
Flow velocity=1.000 ml/min Back time=1.00 minute
Peak pressure=400 crust Self-poise=unlatching
Minimum pressure=8 Peak width=0.100
Percentage ratio B=3.0, C=0.0 Spectral range=240,600,2
Volume injected=10.0 liter Store spectrum=peak
Furnace temperature=30.0 ℃ Threshold value=1.000
1.00, flow velocity=1.000 Signal A=254,4,550,20
1.00, percentage ratio B=3.0, C=0.0 Signal B=400,4,550,20
On this post, the regression equation that is used to measure styrene content is:
[vinylbenzene] % weight=-the 84.99+10.98* retention time (minute)
The preparation of the embodiment 1-6 of interpolymer of the present invention
1) Preparation of catalysts
General provisions
Synthesize and operate under the inert atmosphere (argon gas) and in glove box, carry out.Solvent is available from Aldrich.Before using, liquid reagent and solvent at first use nitrogen saturated, and the process activated alumina for example is disclosed in Pangborn, A.B. to carry out drying then; Giardello, M.A.; Grubbs, R.H.; Rosen, R.K.; Timmers, the Organometallics of F.J., 1996,15,1518-1520.Before the use, deuterium is also filtered for benzene is dry on sodium/potassium-sodium alloy.The methylene radical phenanthrene is available from Lancaster.The NMR spectrum of part and metal complexes under envrionment conditions on Varian 300 MHz NMR spectrometers record.Multipolymer 13C NMR spectrum is record on Bruker600 MHz NMR spectrometer.
Synthesizing of the luxuriant and rich with fragrance lithium of methylene radical
In 50 milliliters of hexanes 4,5-methylene radical phenanthrene (0.485 gram, 2.55 mmoles) adds 1.6M n-Butyl Lithium hexane solution (1.75 milliliters, 2.80 mmoles).After stirring under envrionment conditions 1 day, this solution occurs darker orange and form a spot of orange throw out.After 14 days, form more throw out.Topple over supernatant liquid it is separated from the solid that adheres to the flask inwall.After drying under reduced pressure, isolate 0.430 gram (86% productive rate).From supernatant liquid, remove volatile matter, obtain orange solids.The proton N MR analysis revealed of this material, it is initial methylene radical phenanthrene.
Synthesizing of (4,5-methylene radical phenanthryl) (tertiary butyl amino) dimethylsilane
(tertiary butyl amino) dimetylsilyl muriate in 30 milliliters of THF (0.436 gram, 2.63 mmoles) adds the bright cherry-red solution of the luxuriant and rich with fragrance lithium of methylene radical (0.430 gram, 2.19 mmoles) in 20 milliliters of THF.This solution stirs at ambient temperature and spends the night.Volatile matter is under reduced pressure removed.Volatile matter is also under reduced pressure removed in solid residue slurrying in 10 milliliters of hexanes.Solid residue is with twice of 30 milliliters of hexane extraction altogether.The extract filtration is also under reduced pressure removed volatile matter from merging filtrate, obtain the orange oil of 0.690 gram (99% productive rate). 1H NMR spectrum is consistent with required product.
Synthesizing of [(4,5-methylene radical phenanthryl) (tertiary butyl amino) dimethylsilane] titanium two (dimethylformamide)
Will be in the solution heating and the stirring under refluxing of titanium four acid amides in 50 milliliters of octanes (0.484 gram, 2.16 mmoles) and (4,5-methylene radical phenanthryl) (tertiary butyl amino) dimethylsilane (0.690 gram, 2.16 mmoles).Reaction process utilizes 1H NMR spectrum by taking out the little aliquots containig of this solution, is under reduced pressure removed volatile matter, and analyzes the resistates among the C6D6 and monitor.Proton N MR analysis revealed changes into required product (for example in 55% conversion after about 48 hours that refluxes) fully.Regularly add several titanium four acid amides.As if after refluxing 7 days, the carrying out of reaction is no more than 82% and transforms.Volatile matter is under reduced pressure removed from cooling mixture.Be dissolved in resistates in 20 milliliters of hexanes and filter the gained mixture.From filtrate, remove volatile matter from reducing pressure down, obtain dark powder (0.950 gram).The proton N MR analysis revealed of product, it is a kind of mixture of required product and initial part, is respectively 82/18% mole (required product of 87% weight).
Synthesizing of [(4,5-methylene radical phenanthryl) (tertiary butyl amino) dimethylsilane] titanium dichloride
Add trimethylsilyl chloride (1.33 milliliters, 10.5 mmoles) to above isolated two (the acid amides)/ligand mixtures (0.83 gram, 1.83 mmoles two (acid amides)) that are dissolved in 40 milliliters of hexanes.This solution was stirred 6 hours under refluxing.Take out the little aliquots containig of cooling solution, and under reduced pressure remove volatile matter.Resistates is dissolved in C 6D 6In and use 1HNMR spectrum is analyzed.Spectrum shows and very fully changes into single muriate-monoamide intermediate.Add 1.3 milliliters of trimethylsilyl chloride in addition and sealed vessel was stirred 8 days at ambient temperature.Subsequently with this vlil 6 hours.Cooling solution is placed in the glove box refrigerator (25 ℃).By vacuum filtration, on the glass glaze, collect formed solid.Solid residue is with the disposable washing of cold hexane (about 10 milliliters) and subsequently this solid drying under reduced pressure is obtained 0.516 gram (65% productive rate).Proton N MR analysis revealed, this material are very clean required products.
Synthesizing of [(4,5-methylene radical phenanthryl) (tertiary butyl amino) dimethylsilane] dimethyl titanium
Titanium dichloride in 30 milliliters of THF (0.516 gram, 1.18 mmoles) adds the methylmagnesium-chloride (0.87 milliliter, 2.6 mmoles) that 3.0M can cause middle colour-change.After placement is spent the night, under reduced pressure remove volatile matter.Volatile matter is also under reduced pressure removed in solid residue slurrying in hexane.Resistates with hexane extraction several times.The extract filtration is also under reduced pressure removed volatile matter from merging filtrate, obtain 0.392 gram bright orange powder.C 6D 6Proton and 13C NMR analysis revealed, isolated required product are 1: 1 affixtures with THF.Suppose that molecular weight is 467.6 gram/moles, isolated yield is 71%.Be dissolved in THF affixture (0.345 gram) in 50 milliliters of toluene and reflux 6 hours.Observe color and become pale brown look by orange.Volatile matter is under reduced pressure removed.The proton N MR analysis revealed of resistates changes into new compound fully.
2.) polyreaction
All transfers of following solvents and solution all use the air cushion (gaseous pad) of anhydrous purification nitrogen or argon gas to carry out.The reinforced post through A-204 alumina and Q5 reactant of the gaseous state of reactor is carried out purifying.Alumina activates with 5% hydrogen (in nitrogen) down at 200 ℃ with nitrogen activation and Q5 reactant under 375 ℃ in advance.Operating in the inert-atmosphere glove box of catalyzer and promotor (three (pentafluorophenyl group) borine) carried out.
The scale semi-batch reactor polyreaction has the electrically heated chuck, is being used for that 2 liters of Parr reactors of serpentine tube and bottom drain valve carry out in the refrigerative.Pressure, temperature and piece valve (blockvalve) are also controlled with computer monitoring.In being adjusted to equilibrated solvent injection jar (shottank), measure Isopar E and vinylbenzene.Gained solution adds reactor by the solvent injection jar subsequently.The content of reactor stirs under 1200rpm.Hydrogen is by the 75 milliliter injections jar adding of differential expansion (about 50psi) by initial 300psig.The content of reactor is heated to required operating temperature (90 ℃) subsequently under required ethylene pressure.
With catalyzer [(4,5-methylene radical phenanthryl) (tertiary butyl amino) dimethylsilane] dimethyl titanium and promotor (three (pentafluorophenyl group) borine) merge (becoming the 0.0050M solution in toluene) in glove box, use 1/16 inch (0.16 centimetre) pipeline to transfer to the catalyst injection jar then, wherein use toluene to help to shift by glove box.Catalyst tank is used nitrogen pressure subsequently.Under required operating temperature, after the stabilization, catalyst solution is expelled in the reactor in that reactor content is different by soaking tub.Make cold ethylene glycol process internal cooling coil to keep temperature.Required time is carried out in reaction, and ethene wherein is provided as required.Prepare the catalyzer of additional injection volume and in operational process, add according to same way as.
The content of reactor is discharged to 4 liters in the container of nitrogen wash and use the Virahol quenching subsequently, is added in 100 milligrams of Iragnox 1010 in the toluene then as antioxidant.Volatile matter is removed from polymkeric substance under 140 ℃ under vacuum oven and is spent the night and be cooled to 50 ℃ from stove before taking out.Reactor condition and polyreaction data provide in Table I.
Table I: reactor condition/service data
Embodiment # Catalyzer (mole) Promotor (mole) Vinylbenzene (gram) Isopar E (gram) Ethene (psig) Time (minute) Output (gram)
1 ??18.0 ??18.0 ??229 ??538 ??500 30 ??3.9
2 ??18.0 ??18.0 ??455 ??358 ??500 39 ??56. ??2
3 ??16.0 ??16.0 ??457 ??360 ??200 30 ??51. ??8
4 ??18.0 ??27.0 ??602 ??- ??200 30 ??56. ??0
5 ??18.0 ??27.0 ??602 ??- ??100 30 ??34. ??2
6 ??18.0 ??27.0 ??602 ??- ??50 30 ??22. ??4
Polymer characterization
Use the LC method from aPS, to isolate interpolymer, and the retention time at interpolymer peak represent that its vinylbenzene refluxes, this method use gradient solvent polarity.Shown in the Table II composition, apparent molecular weight (polystyrene standards) and the density data of polymkeric substance described herein.
Table II: polymkeric substance composition, molecular weight and density data
Embodiment # Vinylbenzene % mole Vinylbenzene % weight The % weight of aPS ??Mw ??Mn ??Mw/Mn Density (gram per centimeter 3)
??1 ????24.7 ????54.9 C ??＜1 ??- ??- ??- ??0.9979
??2 ????45.8 ????75.9 C ??＜1 ??- ??- ??- ??1.028
??3 ?53.8 A(49.0) B ?81.2 A(78.1 B) ??1.7 ??660,000 ??287,000 ??2.30 ??1.028
??4 ?56.6 A(52.5) B ?82.9 A(80.4 B) ??10.3 ??684,000 ??198,000 ??3.45 ??1.031
??5 ?63.5 A(60.2) B ?86.6 A(84.9 B) ??18.3 ??583,000 ??133,000 ??4.38 ??1.037
??6 ?74.6 A(73.1) B ?91.6 A(91.0 B) ??33.5 ??541,000 ??98,500 ??5.49 ??1.038
A is from the LC data with nitro post
B is from the LC data with C18 post
C is from proton N MR data
Because these multipolymers comprise aPS, can specify it 13SSS triad peak in the C NMR spectrum.Very little EEE triad peak shows that this interpolymer has considerably less and short ethene sequence.
These materials all show low-crystallinity or are unbodied.As a result, the density of these polymkeric substance increases along with styrene content and reaches 1.06 grams per milliliters (density of aPS).
Molecular weight data shows that this catalyzer can be produced high-molecular weight polymer.Because in gpc analysis, used dual-detector, can check the ratio of refractive index divided by the response of the UV in molecular weight ranges.It is found that this ratio can be big, show that the composition in the whole molecular weight ranges is consistent relatively; For all samples, find that styrene content has rising slightly under lower molecular weight very.This is consistent with the aPS that exists in these materials.
Material property
The heat deflection data of measuring by DSC provide in Table III.
Table III heat deflection (DSC)
Embodiment Vinylbenzene (% mole) Vinylbenzene (% weight) ??Tg，℃ ??Tm，℃ ??Hf，J/g
??1 ????24.7 C ????54.9 C ??31.9 ??123 ??26.5
??2 ????45.8 C ????75.9 C ??32.5 ??119 ??1.7
??3 ?53.8 A(49.0) B ?81.2 A(78.1 B) ??39.7 ??- ??-
??4 ?56.6 A(52.5) B ?82.9 A(80.4 B) ??44.2 ??- ??-
??5 ?63.5 A(60.2) B ?86.6 A(84.9 B) ??55.5 ??- ??-
??6 ?74.6 A(73.1) B ?91.6 A(91.0 B) ??70.3 ??- ??-
A is from the LC data with nitro post
B is from the LC data with C18 post
C is from proton N MR data
As expection, the Tg of these materials finds to increase along with styrene content.Last two fully outside the compositing range of early false random material, show along with styrene content near 100%Tg rapidly near aPS (about 100 ℃).None shows obvious Tg because of the aPS homopolymer to should also be noted that these materials.But the LC data presentation goes out the aPS in the separate substance.Polymkeric substance with high-crystallinity (minimum styrene content 55% weight S) shows near 120 ℃ peak temperature of fusion with near 32 ℃ Tg.
Carry out little tension test and fracture toughness test to assess the mechanical property of these materials, Table IV.The short-term stretch analysis provided under low tensile pressures high-modulus relative vitreous state response with for the relative linear stress/strain stress relation of all material under the highest about 2% strain.The Young's modulus of all these materials is 350000-430000psi (2.4-3GPa).All these materials experience ductile yield under low strain, wherein yield strain is stably shifted to than low elongation along with the increase of styrene content.To final fracture, all polymkeric substance show slight stretching from yield-point.
Table IV: little stretching, fracture toughness property and hardness data
Embodiment # The % weight styrene Yielding stress (psi) The strain of surrender percentage Rupture stress (psi) The strain of nitrogen percentage Young's modulus psi (sd) Hardness a
??1 ??54.9 ??- ??- ??- ??- ??- ??56
??2 ??75.9 ??- ??- ??- ??- ??- ??86
??3 ??78.1 ??6,870 ??2.7 ??6,720 ??3.1 ??347,000 ??(33,000) ??86
??4 ??80.4 ??6,950 ??2.3 ??6,550 ??2.9 ??365,000 ??(48,000) ??89
??5 ??84.9 ??7,130 ??2.1 ??6,540 ??4.9 ??434,000 ??(36,000) ??100
??6 ??91.0 ??6,320 ??1.9 ??6,250 ??2.5 ??376,000 ??(68,000) ??99
A Rockwell scale
Fracture toughness property uses compacting stretching geometric sample to measure.These experimental designs are used to quantize the patience that polymkeric substance begins and propagates crackle according to institute's application of load.This test is carried out at the square polymkeric substance of compression moulding of breach, and uses slasher to crack at the V of this breach word place.Subsequently tensile loading is applied on the sample as plane stress; The gained sample is preferably enough thick to be twisted into outside the plane of institute's application of load preventing.Gained relation between load and the displacement can be used for determining the required instantaneous stress of propagating crack, is called stress strength factor K 1c.It also can be used for determining extending the required energy of this crackle on given cellar area; This scale is shown G1c (energy-to-break or critical strain can fractional release) and it is related by equation 1 with K1c:
G 1c＝(k 1c 2/E)(l -2)??????????????????????(1)
Wherein E is Young's modulus and is Poisson's ratio.The big more fracture toughness property that means of the numerical value of K1c and G1c is high more.
The fracture toughness property observed value does not show the meaningful difference of these test materials at sample room.Table V has provided the data that 4 sample critical stress intensity factor (K1c) values under high-phenylethylene content and high molecular radical polymerization polystyrene homopolymer obtain under the same test condition.Copolymer sheet reveals obviously higher K1c and G1c value, and the surrender load of multipolymer and breaking load are apparently higher than polystyrene homopolymer.
The improvement toughness of the relative polystyrene of these materials may be derived from add ethylene unit and on the time scale of tearing test, cause the ability of more ductility response adding stress.
Table V: the toughness data of ES multipolymer
Embodiment # % weight, vinylbenzene ????K 1a????(Mpa ????m0.5) Maximum load (ft lbf) Yield-point energy (ft lbf-inch) Energy-to-break (ft lbf-inch) ??G 1c A??(J/m2)
Embodiment 3 ??78.1 ????2.9 ??59.5 ??0.95 ??2.9 ??3,130
Embodiment 4 ??80.4 ????2.8 ??67.6 ??1.3 ??2.8 ??2,770
Embodiment 5 ??84.9 ????3.4 ??56.8 ??0.94 ??2.1 ??3,430
Embodiment 6 ??91 ????2.9 ??46.6 ??0.97 ??2.6 ??2,880
Comparative Examples 1 ??100 B ????2.2 ??28.7 ??0.34 ??0.52 ??1,400 C
Young's modulus that the A use records and 0.33 Poisson's ratio are calculated B free radical aPS, Mn=114720, Mw=282970, Mw/Mn=2.47C uses Young's modulus (3.1GPa) and Poisson's ratio (0.33) published value (polymerization science and the engineering encyclopedia of high molecular PS, 16 volumes, the 2nd edition, John Wiley ﹠amp; Sons, 1989, the 1-246 page or leaf), calculate by K1c
Noncrystalline interpolymer carries out DMS and analyzes with other transformation relevant with these materials with affirmation of the position of definite glass transition.Second-order transition temperature and room temperature-secondary Tg (sub-Tg) storage modulus increases along with the increase of styrene content in the multipolymer.
In the slitter loss modulus of noncrystalline ES multipolymer (G ") response, clearly observe the second-order transition temperature of these materials, and approximately-50 ℃ to observing a wide transformation between the room temperature.In polystyrene, this transformation relaxes to the main chain of following the benzyl ring dislocation contribution.
The physicals of high-phenylethylene content interpolymer of the present invention shows improved anti-breaking property.This shows that these interpolymers can provide unique purposes in some occasion.The amorphous interpolymer of high-phenylethylene content is transparent, thus these interpolymers can be used for that film is used and because toughness is higher relative aPS more favourable.In addition, the foam sheet of these novel polymers can show than the better rebound resilience of aPS sheet material and need be applied to the application of increased durability better.These polymkeric substance also can be used for aPS toughness reinforcing, keep the good transparency simultaneously, as long as can find the composition with consistency.

Claims (17)

1. interpolymer comprises:
(1) polymer unit derived from least a vinyl or vinylidene aromatic monomer of 5-85% mole,
(2) the 15-95% mole derived from least a ethene and/or C 3-20The polymer unit of alpha-olefin; With
(3) polymer unit derived from one or more alkene unsaturated polymerizable monomers except that (1) and (2) of 0-20% mole; With
Described interpolymer comprises detectable vinyl or vinylidene aromatic monomer triad.
2. according to the interpolymer of claim 1, wherein:
(1) component (1) comprise the 20-85% mole derived from the described vinyl of representing by following structural formula or the polymer unit of vinylidene aromatic monomer:
R wherein 1Be selected from hydrogen atom and the alkyl that contains 1 to 4 carbon atom; Each R 2Be independently selected from hydrogen atom and the alkyl that contains 1 to 4 carbon atom; Ar is phenyl or is selected from halogen, C by 1 to 5 1-4Alkyl and C 1-4The phenyl that substituting group replaced of haloalkyl; And the value of n is 0 to 4; Or
(2) polymer unit of 15-80% mole, derived from ethylene and/or comprise at least a described alpha-olefin in propylene, 4-methyl-1-pentene, butene-1, hexene-1 or the octene-1; With
(3) the described alkene unsaturated polymerizable monomer except that (1) and (2) comprises norbornylene or C 1-10Alkyl or C 6-10The norbornylene that aryl replaces.
3. according to the interpolymer of claim 1, wherein:
(1) component (1) comprise the 50-85% mole derived from comprise vinylbenzene, alpha-methyl styrene, neighbour-,-and p-methylstyrene and the described vinyl of ring halogenated styrenes or the polymer unit of vinylidene aromatic monomer; Or
(2) polymer unit of 15-50% mole, derived from ethylene or ethene and comprise the described alpha-olefin of propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1; With
(3) the described alkene unsaturated polymerizable monomer except that (1) and (2) is a norbornylene.
4. according to the interpolymer of claim 3, wherein component (1) is a vinylbenzene (a); And component (2) is an ethene.
5. according to the interpolymer of claim 3, wherein component (1) is a vinylbenzene (a); And component (2) is at least a in ethene and propylene, 4-methyl-1-pentene, butene-1, hexene-1 or the octene-1.
6. interpolymer, it is made by the following material of polymerization under the existence of the catalyzer that comprises [(4,5-methylene radical-phenanthryl) (tertiary butyl amino) dimethylsilane] dimethyl titanium:
(a) at least a vinyl or vinylidene aromatic monomer,
(b) at least a ethene and/or C 3-20Alpha-olefin; With
(c) alkene unsaturated polymerizable monomer of Ren Xuan one or more except that (1) and (2).
7. according to the interpolymer of claim 6, wherein:
(a) described vinyl or vinylidene aromatic monomer are expressed from the next:
R wherein 1Be selected from hydrogen atom and the alkyl that contains 1 to 4 carbon atom; Each R 2Be independently selected from hydrogen atom and the alkyl that contains 1 to 4 carbon atom; Ar is phenyl or is selected from halogen, C by 1 to 5 1-4Alkyl and C 1-4The phenyl that substituting group replaced of haloalkyl; And the value of n is 0 to 4; Or
(b) comprise at least a described alpha-olefin in propylene, 4-methyl-1-pentene, butene-1, hexene-1 or the octene-1;
Described alkene unsaturated polymerizable monomer except that (1) and (2) comprises norbornylene or C 1-10Alkyl or C 6-10The norbornylene that aryl replaces.
8. according to the interpolymer of claim 7, wherein component (a) is a vinylbenzene; And component (c) is an ethene.
9. according to the interpolymer of claim 7, wherein component (a) is a vinylbenzene; And component (c) is at least a in ethene and propylene, 4-methyl-1-pentene, butene-1, hexene-1 or the octene-1.
10. method for preparing multipolymer, it prepares interpolymer by the following material of polymerization under the existence of the catalyzer that comprises [(4,5-methylene radical-phenanthryl) (tertiary butyl amino) dimethylsilane] dimethyl titanium:
(a) at least a vinyl or vinylidene aromatic monomer, or
(b) at least a ethene and/or C 3-20Alpha-olefin; With
(c) alkene unsaturated polymerizable monomer of Ren Xuan one or more except that (1) and (2).
11. according to the method for claim 10, wherein:
(a) described vinyl or vinylidene aromatic monomer are expressed from the next:
Figure A0080929600041
R wherein 1Be selected from hydrogen atom and the alkyl that contains 1 to 4 carbon atom; Each R 2Be independently selected from hydrogen atom and the alkyl that contains 1 to 4 carbon atom; Ar is phenyl or is selected from halogen, C by 1 to 5 1-4Alkyl and C 1-4The phenyl that substituting group replaced of haloalkyl; And the value of n is 0 to 4; Or
(b) comprise at least a described alpha-olefin in propylene, 4-methyl-1-pentene, butene-1, hexene-1 or the octene-1;
(c) the described alkene unsaturated polymerizable monomer except that (1) and (2) comprises norbornylene or C 1-10Alkyl or C 6-10The norbornylene that aryl replaces.
12. according to the method for claim 11, wherein component (a) is a vinylbenzene; And component (c) is an ethene.
13. according to the method for claim 11, wherein component (a) is a vinylbenzene; And component (c) is at least a in ethene and propylene, 4-methyl-1-pentene, butene-1, hexene-1 or the octene-1.
14. a blend comprises:
A) according to the interpolymer of claim 1; With
B) one or more additional polymer components.
15. according to the blend of claim 15, wherein said additional polymer B component is selected from random basically interpolymer, vinyl and vinylidene halide, Alathon, alpha-olefin homo, ethylene/alpha-olefin copolymer, styrenic, polyethers, polycarbonate, polyaniline, pitch or its any combination.
16. transition metal complex [(4,5-methylene radical-phenanthryl) (tertiary butyl amino) dimethylsilane] dimethyl titanium.
17. a catalyst composition comprises [(4,5-methylene radical-phenanthryl) (tertiary butyl amino) dimethylsilane] dimethyl titanium.
CN00809296A 1999-06-22 2000-06-05 Ethylene and/or alpha-olefin/vinyl or viylidene aromatic interpolymer compsns. Pending CN1357014A (en)

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US6239242B1 (en) 1999-08-21 2001-05-29 Nova Chemicals Corporation Vinylaromatic and olefin pseudoblock polymers
FR2876222A1 (en) * 2004-10-06 2006-04-07 Renault Sas NON-FLUORINATED OR PARTIALLY FLUORINATED MEMBRANE FUEL CELL AND PROCESS FOR THE PREPARATION OF SAID MEMBRANE

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NZ235032A (en) * 1989-08-31 1993-04-28 Dow Chemical Co Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component
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