CN1284101A - Seals producted from alpha-olefin/vinylidene aromatic and/or hindered aliphatic vinylidene/interpolymer based materials and sealing systems therefrom - Google Patents

Abstract

The present invention discloses seals including container closure liners, gaskets and barrier membranes, comprising a polymer composition having an oxygen transmission coefficient at a temperature of 25 DEG C of less than about 300 cm<3>.mil/100 in<2>.day.atm. (1.2 cm<3>/cm.day.MPa), wherein the polymer composition comprises at least one substantially random interpolymer (or a blend comprising at least one substantially random interpolymer and at least one other polymer) and from 0 to 80 percent by weight (based on the total weight of the composition) of at least one filler. The present invention also discloses sealing systems which include container closures such as bottle caps comprising these seals. The interpolymers or blends used to produce the seals of the present invention (as well as the novel seals themselves) exhibit a unique balance of properties including low oxygen permeability, low Shore A hardness and excellent tensile strain recovery.

Description

Sealing of making by alpha-olefin/vinylidene aromatic monomer and/or hindered aliphatic vinylidene/interpolymer sill and the sealing system that obtains thus

In many industry, the sealing system of bottle or jar and so on container need use the lid or the bottle cap that comprise sealing or lining (as packing ring, lining or secluding film) could form required complete seal effectively.Concerning many purposes, importantly sealing limits the ability of gas-permeable.For example, oxygen can be caused other adverse effect of food spoilage or the quick content of oxygen by the infiltration of outside.In addition, for example under the situation of soda pop, carbonic acid gas can cause the decline of carbonation from the diffusion of container.

In addition, be decided by the method that the pressure and temperature of container contents and lid and this container mate usually as the character of the material of given sealing.For example, many containers have screw thread when lid closure and unlatching, and this requires sealing material to stand bigger compression when keeping its integrity, but also has enough recoveries of shape.

At last, the character of the required sealing of container normally content is specific, and for example some material may be incompatible with some medical component.Under the corrodibility working conditions, the corrodibility of the necessary anti-this material of packing ring, but still have enough elasticity to form sealing.In the food and drink field, the material that is used to form sealing has similar requirement, but should be able to Food Contact.In addition, filling temperature must be below or above room temperature according to the kind of food and/or liquid contents, and this is higher to seal request.

The sealing that is used for sealing system is made by various structured materials, comprising the polymkeric substance of Ethylene/vinyl acetate (EVA) and polyvinyl chloride (PVC) and so on.For example, United States Patent (USP) 4984703 (Burzynski) discloses the plastic bottle closure with sealed liner, and described lining is made of the blend of Ethylene/vinyl acetate and composition for thermoplastic elastomer.

The various trials that solve performance requriements also comprise the application of oil additive or elastomer additives.For example, United States Patent (USP) 5137164 (Bayer) discloses a kind of method with thermoplastics lining plastic bottle closure, incorporates it into the present invention as a reference at this.This thermoplastics is a kind of noncrosslinking, curable, chloroethylene copolymer compositions, has used the solidifying agent plasticising in addition of epoxidized oil, organic diglycidylether and this ether.

United States Patent (USP) 4807772 (Schloss) and United States Patent (USP) 4846362 (Schloss) disclose polypropylene and polyethylene bottle cap respectively, and they have the movable lining of being made by the blend of polyethylene and thermoplastic elastomer copolymer (as the segmented copolymer of vinylbenzene and divinyl) respectively.This blend allegedly generally comprises the oil of 20-50% weight.

United States Patent (USP) 4872573 (people such as Johnson) discloses the isolation layer that is used for bottle cap that is selected from ethylene/vinyl base alcohol copolymer and polyvinylidene dichloride, and it especially can be used for delaying the migration of oxygen-containing gas.

United States Patent (USP) 5000992 (Kelch) discloses a kind of plastic containers bottle cap of being made by the multilayer foamed film of co-extrusion.This film has the foaming layer of at least one polyethylene blend solid layer and at least one second polyethylene blend.

United States Patent (USP) 3786954 (Shull) discloses the lamination packing ring, comprises the polyethylene foamed thick sheet simultaneously and adheres to air on the described polyethylene and the impervious thin SARANTM of moisture (trade mark of Dow chemical company and by its manufacturing) by new LDPE (film grade) (LDPE) tackiness agent.

United States Patent (USP) 5104710 (Knight) discloses by using the propylene adhesion promoter to improve the adhesivity of packing ring.Knight also discloses LLDPE as a comparison case (LLDPE), and the result shows that it bonds under 200 ℃ temperature not enough.

United States Patent (USP) 4529740 (Trainor) but the foaming structure of being made by styrene-butadiene block copolymer and so on elastomerics, a spot of sulfonated styrene polymer salt and whipping agent is disclosed.

United States Patent (USP) 4744478 (Hahn) discloses the molding bottle cap, and the polymkeric substance of foaming and the Unitarily molded foaming layer of same polymkeric substance do not constitute basically by one deck at least.This polymkeric substance can be ethylene series, polystyrene, polyester, polycarbonate or other suitable engineering resin.Preferred polymkeric substance is the multipolymer of propylene and EDPM rubber.

Polyvinyl chloride (PVC) polymkeric substance has been widely used as the food gasket of bottle lid, but is restricted day by day under environmental stress.Other polymkeric substance; for example ethylene/methacrylic acid or ethylene/acrylic acid copolymer also are applied with its soft character; but these polymkeric substance can have a negative impact to the gentle flavor problem of taste usually, for example when this polymkeric substance packing ring and Food Contact and some composition are filtered this food.

High density polyethylene(HDPE) (HDPE) also openly is used to form packing ring, because the polyethylene of higher density has taste and odor properties preferably.The application of this material does not obtain business success at present as yet, because this polymkeric substance too " firmly ", and is adding oil when reducing hardness, and extractable content increases, and this is unfavorable for the laws and regulations requirement of related food contact.In addition, will good softness although heterogeneous LLDPE (LLDPE) has than HDPE, HDPE or LLDPE (for example, are commonly used for the polypropylene of bottle cap material with some plastic bottle closure, as described in United States Patent (USP) 4807772) adhesivity is bad, causes the polyethylene packing ring lax.

WO95/00599 (Shell oil company) but disclose can be used for making bottle cap and as the improvement polymer composition of reclosing container closure lining, it is made up of the blend of hypocrystalline poly-(1-butylene), ethylene-methyl acrylate, polypropylene random copolymer.This composition is allegedly recyclable, and can not produce environment, health and the smell problem of prior art lining.

WO88/03115 (Permian research company) has proposed a kind of molded polymeric container closure, and the polymkeric substance of foaming and the Unitarily molded foaming layer of same polymkeric substance are not formed basically by one deck at least for it.These bottle caps allegedly have excellent isolation performance, and the easier production economically of prior art bottle cap relatively.

WO90/14945 (Dow chemical company) discloses the multilayer foamed film of the co-extrusion that is used for the plastic containers bottle cap, and this film has first polyolefin blends that comprises LLDPE, new LDPE (film grade) and dispensable high density polyethylene(HDPE) of at least one solid rete; And second polyolefin blends that comprises LLDPE, new LDPE (film grade) and dispensable ethylene vinyl acetate of at least one foaming layer.

WO95/32095 (W.R.Grace﹠Co.) has described hot contractile film and sheet material, is made by alpha-olefin/binyl aromatic monomer multipolymer such as ethylene/styrene multipolymer.Also disclose print film, laminate and comprised and adhered to hot collapsible repairing bag on the hot collapsible bag or comprise rigid container or the packing of flexible cover.

But still need be by the sealing system of forming based on the sealing of polymkeric substance, this polymkeric substance comprehensively has various performances, comprises tension strain answer and stress relaxation, low modulus/Xiao A hardness and the good melt processability (comprising melt rheological property) of low oxygen rate of permeation, excellence.Have now found that, if have the polymer unit derived from vinylidene monomer of specified range, can be used for improving the stopping property of sealing system so based on the material of random alpha-olefin/vinylidene aromatic monomer and/or hindered aliphatic or cycloaliphatic vinylidene monomer interpolymers basically.These materials provide a kind of necessary characteristic of unique scope, comprise the hardness or the snappiness of oxygen isolation performance, tension strain answer, stress relaxation and certain limit, and these all depend on the vinylidene content of this polymkeric substance or blend.Now shockingly find, be used to prepare the best of breed that the random basically interpolymer with narrower intermediate range vinylidene content of the present invention's sealing just has these performances, but these performances have or just attractive inadequately during low vinylidene content at interpolymer higher.

But having, the present invention sealing that comprises random basically vinylidene interpolymers or its blend accepts to seal required performance as the reclosing container closure.These bottle caps can be removed under gratifying mobile moment of torsion from container, and can remove and reclosing in the whole time limit of this container contents.Sealing or lining can produce oxygen isolated property, in transportation with the integral body when storing and temperature stability and be carbonating, even the stopping property under loading at the top when for example be soda pop at the content of this container.The present invention's sealing has also improved and steel or metal cap, for example scribbles the adhesivity of the beer bottle cap of epoxy or acrylic resin usually.They also have good adhesivity with the bottle cap of being made by non-polar substrate such as polypropylene or high density polyethylene(HDPE).

The invention discloses the various sealings that comprise container closure lining, packing ring and secluding film, wherein comprise a kind of oxygen transmission coefficient under 25 ℃ and be lower than 300 centimetres ³Mil/100 inch ²The polymer composition of it normal atmosphere, this polymer composition comprises:

(A) at least a random basically interpolymer comprises:

(1) polymer unit derived from following material of 24-65% mole:

(a) at least a vinylidene aromatic monomer, or

(b) at least a hindered aliphatic or cycloaliphatic vinylidene monomer, or

(c) combination of at least a aromatics vinylidene monomer and at least a hindered aliphatic or cycloaliphatic vinylidene monomer and

(2) the 35-76% mole derived from least a C _2-20The polymer unit of alpha-olefin; Or

(B) a kind of blend comprises:

(1) the component A of 35-99% weight (based on the gross weight of B component 1 and B2); With

(2) polymkeric substance of at least a non-component A of 1-65% weight (based on the gross weight of B component 1 and B2); With

(C) at least a filler of 0-80% weight (based on the gross weight of component A, B and C).

The invention also discloses sealing system, comprise container cover such as bottle cap with these sealings.The composition that is used for production the present invention sealing has the particular performances balance, comprises low oxygen rate of permeation, high tension strain answer and stress relaxation and low Xiao A hardness.

This paper is meant the Press by CRC when mentioning the element that belongs to certain family or metal, Inc., and 1989 publish and have the periodic table of elements of copyright.Should be meant " family " given when in this periodic table of elements, using IUPAC family naming system when relating to equally, " family ".

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 variable value of the amount of component or technology such as temperature, pressure, time etc. 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 " alkyl " is meant that any aliphatic series, cyclic aliphatic, aromatics, aryl replace aliphatic series, aryl substituted ring aliphatic series, aliphatic series replacement aromatics or aliphatic substituted ring aliphatic group.

Term "-oxyl " be meant it with the carbon atom that is connected between have the alkyl of an oxygen.

Term used herein " multipolymer " is meant a kind of like this polymkeric substance, and wherein at least two kinds of different monomer polymerizations form this multipolymer.

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 copolymer, ter-polymers etc.

Term used herein " random basically " (in the random basically interpolymer that comprises derived from the polymer unit of one or more alpha-olefins and one or more vinylidene aromatic monomers and/or hindered aliphatic or cycloaliphatic vinylidene monomer) is meant, the monomer distribution of described interpolymer can be described by the Bai Nuli statistical model or by one-level or secondary Markovian statistical model, for example be described in " the polymer sequence mensuration of J.C.Randall, the 13C nuclear magnetic resonance method " (Polymer Sequence Determination, Carbon-13 NMR Method, Academic Press New York, 1977, the 71-78 page or leaf).In random interpolymer basically, have 3 vinylidene aromatic monomers in the unitary block of above vinylidene aromatic monomer and preferably be no more than 15% of total amount.More preferably, this interpolymer is not to be feature with height isotaxy or syndiotaxy.This means at this basically in the carbon-13 nmr of random interpolymer, represent 75% of the main chain mesomethylene carbon of meso diad sequence or racemize diad sequence and total peak area that the corresponding peak area of methine carbon should be no more than main chain mesomethylene carbon and methine carbon.

Term used herein " sealing system " is meant the system that is used for sealed vessel, has a sealing and a kind of enclosure method that container contents is sealed.Sealing system used herein also comprises and disturbs tangible sealing system, includes (but are not necessarily limited to) for example to carry the sealing system of the containers of ethical goods.In a preferred embodiment, but the sealing system is a kind of sealing or the reclosing plastics or metallic container cover of lining of comprising.This container can have all size or shape, comprises those containers of so-called bottle or jar.For preferred container, promptly the bottle, these lids often are called " bottle cap ".The sealing system is just particularly useful when making by metal or by plastics such as thermoplastic polymer.These bottle caps generally include a ring-type substrate walls, are positioned at sealing or lining and a circumference lateral margin that is extended by this wall on the described substrate walls lower surface downwards, this lateral margin has some device near on one or several aspect of vessel port, for example be designed for the lines of some position of interlock (for example lines of this container), and the interlock of wherein said lines and tightening can make sealing or lining affact the top of this container when tightening bottle cap, so just forms to seal.

Term used herein " sealing " or " lining " are the sealing system elements, and it is by affacting the content that seals this container on the described container.These sealings comprise (but being not limited to) molding flange, sealing pad, be used to delay gas (especially oxygen, carbonic acid gas and water vapour) migration secluding film, extrusion molding individual layer and multilayered structure, be carried on film on the base material (making) by metal, plastics, foam materials, glass or pottery, the lining or the cap of lid that the mold container made by glass, metal or polymkeric substance (comprising polyethylene, polypropylene, polyethylene terephthalate (PET) or polycarbonate) is used.

An embodiment of the present invention's sealing also comprises packing ring.These packing rings can have various shape, comprise " O type ring " and dull and stereotyped sealing (" membranaceous " packing ring that for example, has the specific end use desired thickness).Various packing ring manufacturing technologies are known, comprise the disclosed method of following patent: United States Patent (USP) 5215587 (people such as McConnellogue), United States Patent (USP) 4085186 (Rainer), United States Patent (USP) 4619848 (people such as Knight), United States Patent (USP) 5104710 (Knight), United States Patent (USP) 4981231 (Knight), United States Patent (USP) 4717034 (Mumford), United States Patent (USP) 3786954 (Shell), United States Patent (USP) 3779965 (people such as Lefforge), United States Patent (USP) 3493453 (people such as Ceresa), United States Patent (USP) 3183144 (Caviglia), United States Patent (USP) 3300072 (Caviglia), United States Patent (USP) 4984703 (Burzynski), United States Patent (USP) 3414938 (Caviglia), United States Patent (USP) 4939859 (Bayer), United States Patent (USP) 5137164 (Bayer) and United States Patent (USP) 5000992 (Kelch).Suitable end-use includes, but is not limited to be used for the sealing of metal and plastic cover, and beverage closure lining, heat is irritated fruit juice lid lining, the polypropylene cap lining, steel or aluminium lid lining, high density polyethylene(HDPE) lid lining, the window-glass packing ring, sealed vessel, the bottle cap lid, the packing ring of medical facilities, filter element, the ventilation packing ring, the hot melt packing ring, easy screw capping, the electrochemical cell packing ring, the refrigerator packing ring, the galvanic cell packing ring, the steel-seal type cell packing ring, waterproof sheet, can use packing ring again, synthetic cork stopper shape material, thin battery electrocoating film spacer, the magnetic rubber material, the disk packing ring that is used for the alcoholic beverage bottle cap, the sealing-ring of anti-the refrigerated, the packing ring that is used for the plastics casting, expansion joint and water economizer, corrosion-resistant guide coupling, soft magnetic plastics, pipe seal, whole anti-aging plastic lid and socket hinge, the magnetic surface foaming product, the jar ring, flexible gaskets, glass capsulation, disturb tangible sealed liner, pressure applicator, combined bottle cap and suction-pipe structure, big castor lining, the crown cap that is used for pomace or salad jar, family's can jar, " hat ".

The interpolymer that is used to prepare the present invention's sealing comprises, the interpolymer that one or more alpha-olefins and one or more vinylidene aromatic monomers and/or one or more hindered aliphatics or cycloaliphatic vinylidene monomer polymerization are obtained.

Suitable 'alpha '-olefin monomers for example comprises and contain 2 to about 20, and is preferred 2 to 12, particularly the alpha-olefin of 2 to 8 carbon atoms.Specially suitable is ethene, propylene, butene-1,4-methyl-1-pentene, hexene-1 or octene-1, or with ethene and propylene, butene-1, in 4-methyl-1-pentene, hexene-1 or the octene-1-kind or multiple being used in combination.These alpha-olefins do not contain the aromatics part.

The vinylidene aromatic monomer that is applicable to this interpolymer of preparation comprises, for example by those monomers of the representative of following structural formula:

R wherein ¹Be selected from hydrogen atom and the alkyl that contains 1 to 4 carbon atom, be preferably hydrogen atom or methyl; Each R ²Be independently selected from hydrogen atom and the alkyl that contains 1 to 4 carbon atom, be preferably 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 about 4, is preferably 0 to 2, most preferably 0.

The example of monovinylidene aromatic monomer comprises vinylbenzene, Vinyl toluene, alpha-methyl styrene, t-butyl styrene and chlorostyrene, comprises the isomer that these compounds are all.Specially suitable this class monomer comprises vinylbenzene and low alkyl group or halogen substituted derivative.Preferred monomers comprises vinylbenzene, alpha-methyl styrene, rudimentary (C ₁-C ₄) alkyl-or the nuclear substituted styrene derivatives of phenyl, for example adjacent-,-and p-methylstyrene, ring on halogenated vinylbenzene, to Vinyl toluene or its mixture.Preferred aromatics monovinylidene monomer is a vinylbenzene.

Term " hindered aliphatic or cycloaliphatic vinylidene compound " but be meant vinylidene monomer corresponding to the addition polymerization of following structural formula:

A wherein ¹For containing the sterically hindered big aliphatic series or the cyclic aliphatic substituting group of 20 carbon atoms at the most, R ¹Be selected from hydrogen atom and the alkyl that contains 1 to 4 carbon atom, be preferably hydrogen atom or methyl; Each R ²Be independently selected from hydrogen atom and the alkyl that contains 1 to 4 carbon atom, be preferably hydrogen atom or methyl; Or R ¹And A ¹Also can constitute member ring systems.

Term " sterically hindered big " is meant, has this substituent monomer and carries out the speed of addition polymerization under standard Ziegler-Natta polymerisation catalysts generally the speed than vinyl polymerization is little.Preferred hindered aliphatic or cycloaliphatic vinylidene compound those monomers that to be one of them carbon atom that has an olefinic degree of unsaturation replaced by three grades or level Four.The substituent example of this class comprises that cycloaliphatic radical such as cyclohexyl, cyclohexenyl, cyclooctene base or its ring go up the deriveding group that replaced by alkyl or aryl and the tertiary butyl, norcamphyl.Most preferred hindered aliphatic or cycloaliphatic vinylidene compound are the vinyl substitution in ring derivative and the 5-ethidine-2-norbornylenes of the various isomeries of tetrahydrobenzene and substituted cyclohexene.Specially suitable is 1-, 3-and 4 vinyl cyclohexene.

Basically random interpolymer can carry out modification by typical grafting well known in the art, hydrogenation, functionalized or other reaction.According to existing method, polymkeric substance often produces functional derivative by sulfonation or chlorination.

This random basically interpolymer can carry out modification by various cross-linking methods, comprising (but being not limited to) superoxide-, silane, sulphur-, radiation-or trinitride-Ji curing system.About the detailed description of various cross-linking methods is described in pending trial Application No. 09/921641 and 08/921642 (all submitting on August 27th, 1997).

The dual cure systems of comprehensive utilization heat, moisture-curing and irradiation step also can effectively adopt.The Application No. of submitting September 29 nineteen ninety-five 536022 (the application people is K.L.Walton and S.V.Karande) discloses and has required dual cure systems.For example, may wish 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.

Basically random interpolymer also can carry out modification by various cross-linking methods, these methods include, but is not limited to: in its preparation process, add diene component as the 3rd monomer, undertaken crosslinked by preceding method and other method (comprise for example use sulphur vulcanizes by vinyl as linking agent) subsequently.

A kind of preparation method of random interpolymer basically comprises, in the presence of one or more metalloscene catalysts or constrained geometry catalyzer and various promotors, the mixture of polymerisable monomer carried out polymerization.

Basically random interpolymer can prepare according to people's such as James C.Stevens U.S. Patent application 545403 (submitting July 3 nineteen ninety, corresponding to EP-A-0416815).The preferred operational condition of this polyreaction is the temperature of normal atmosphere to 3000 an atmospheric pressure and-30 ℃ to 200 ℃.Under the temperature that is higher than on each monomer auto-polymerization temperature, carry out polyreaction and remove unreacted monomer causing forming a certain amount of homopolymer polymerisate that obtains by radical polymerization.

Be applicable to preparation basically the example of the Catalyst And Method of random interpolymer be disclosed in the U.S. Patent application of submitting July 3 nineteen ninety 545403 (EP-A-416815), the U.S. Patent application 702475 (EP-A-514828) that on May 20th, 1991 submitted, the U.S. Patent application 876268 (EP-A-520732) that on May 1st, 1992 submitted, the U.S. Patent application 241523 that on May 12nd, 1994 submitted, and U.S. Patent No. 5,055,438,5,057,475,5,096,867,5,064,802,5,132,380,5,189,192,5,321,106,5,347,024,5,350,723,5,374,696, with 5,399,635.

Basically random alpha-olefin/vinylidene aromatic interpolymer also can wherein adopt the compound of being represented by following general formula by JP 07/278230 described method preparation:

Cp wherein ¹And Cp ²Be cyclopentadienyl, indenyl, fluorenyl or its replacement form independently of each other; R ¹And R ²Be hydrogen atom, halogen atom, alkyl, alkoxyl group or aryloxy independently of each other with 1-12 carbon atom; M is an IV family metal, preferred Zr or Hf, most preferably Zr; And R ³Be to be used to connect Cp ¹And Cp ²Alkylidene group or silane two bases.

Basically random alpha-olefin/vinylidene aromatic interpolymer also can be by (W.R.Grace﹠Co.) such as John G.Bradfute at WO 95/32095; R.B.Pannell (Exxon chemical patent company) is at WO 94/00500; And in " plastics technology " (Plastics Technology) in September, 1992, the 25th page of described method is prepared.

The same U.S. Patent application No.08/708 that also has people such as Francis J.Timmers to submit that is suitable on September 4th, 1996, the disclosed random basically interpolymer that contains at least a alpha-olefin/binyl aromatic monomer/vi-ny l aromatic monomers/alpha-olefin four unit groups in 869.These interpolymers contain its peak other signal bigger 3 times than noise peak intensity.The chemical shift of these signals is between 43.70 to 44.25 ppm and 38.0 to 38.5 ppm.Specifically, the chemical shift of main peak is 44.1,43.9 and 38.2 ppm.Proton test nuclear magnetic resonance experiment shows that chemical shift belongs to methine carbon at 43.70 to 44.25ppm signal, and chemical shift belongs to mesomethylene carbon at 38.0 to 38.5ppm signal.

These new signals it is believed that it is owing to inserting the sequence that at least one alpha-olefin forms in the front and back of two head-to-tail vi-ny l aromatic monomers, ethylene/styrene/styrene/ethylene four unit groups for example, wherein styrene monomer only inserts in this Unit four group in the mode of 1,2 (head-to-tail).Those skilled in the art understand, for containing vi-ny l aromatic monomers outside the vinylbenzene and four unit groups of the alpha-olefin outside the ethene, this ethylene/vinyl base aromatic monomer/vi-ny l aromatic monomers/ethene four unit groups can have similar 13C nuclear magnetic resonance peak, but minute differences is arranged in chemical shift.

These interpolymers be approximately-30 ℃ to about 250 ℃ temperature, in the presence of those catalyzer shown in the following structural formula, and optionally but the polyreaction of preferably in the presence of active cocatalyst, carrying out preparation:

Wherein each Cp is the substituted cyclopentadienyl that links to each other with the π key with M respectively independently; E is C or Si; M is an IV family metallic element, is preferably Zr or Hf, most preferably Zr; Each R is hydrogen atom, alkyl, sila alkyl or silicon alkyl alkyl respectively independently, contains about at the most 30, preferred 1 to about 20, more preferably 1 to about 10 carbon atoms or Siliciumatom; Each R' is hydrogen atom, halogen, alkyl,-oxyl, sila alkyl or silicon alkyl alkyl respectively independently, contains about at the most 30, preferred 1 to about 20, more preferably 1 to about 10 carbon atoms or Siliciumatom, or two R' groups can constitute C jointly _1-10The 1,3-butadiene that alkyl replaces; M is 1 or 2, and especially, the substituted cyclopentadienyl that is suitable for comprises those groups shown in the following structural formula:

Wherein each R is hydrogen atom, alkyl, sila alkyl or silicon alkyl alkyl respectively independently, contains 30 at the most, preferred 1 to 20, more preferably 1 to 10 carbon atom or Siliciumatom, or two R bases can constitute the divalence deriveding group of this group jointly.Each R is preferably independently respectively and (comprises all isomer, if suitable) hydrogen atom, methyl, ethyl, propyl group, butyl, amyl group, hexyl, benzyl, phenyl or silyl, or (if suitable) two R groups couple together and constitute a condensed ring system, as indenyl, fluorenyl, tetrahydro indenyl, tetrahydrofluorenyl or octahydrofluorenyl.

Particularly preferred catalyzer for example comprises racemize (dimethyl silyl base)-two-(2-methyl-4-phenyl indenyl) zirconium dichloride, racemize (dimethyl silyl base)-two-(2-methyl-4-phenyl indenyl) 1,4-phenylbenzene-1,3-butadiene zirconium, racemize (dimethyl silyl base)-two-(2-methyl-4-phenyl indenyl) two C _1-4Alkyl zirconium, racemize (dimethyl silyl base)-two-(2-methyl-4-phenyl indenyl) two C _1-4Zirconium alkoxide, or its any combination.

Also can use following titanium base constrained geometry catalyzer: [N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-1,5,6,7-tetrahydrochysene-cyclopenta indenes (indacen)-1-yl] silanamines close (2-)-N] the dimethyl titanium, (1-indenyl) (tertiary butyl amino) dimethyl-silane dimethyl titanium, ((the 3-tertiary butyl) (1,2,3,4,5-η)-the 1-indenyl) (tertiary butyl amino) dimethylsilane dimethyl titanium, ((3-sec.-propyl) (1,2,3,4,5-η)-the 1-indenyl) (tertiary butyl amino) dimethylsilane dimethyl titanium, or its any combination.

Other preparation method of interpolymer of the present invention is existing in the literature to be described.Longo and Grassi (macromolecular chemistry (Makromol.Chem.), nineteen ninety, the 191st volume, the 2387-2396 page or leaf) and (journal of applied such as D'Anniello, nineteen ninety-five, the 58th volume, the 1701-1706 page or leaf) reported and adopted based on methylaluminoxane (MAO) and cyclopentadienyl titanous chloride (CpTiCl ₃) catalyst system prepare ethylene-styrene copolymer.(polymer chemistry branch of American Chemical Society, polymkeric substance is preprinted collection (Div.Polym.Chem.), 1994, the 35th rolled up 686,687 pages for Polymer Preprints, Am.Chem.Soc.) report and is adopted MgCl for Xu and Lin ₂/ TiCl ₄/ NdCl ₃/ Al (iBu) ₃Catalyzer carries out the random copolymers of copolymerization with preparation vinylbenzene and propylene.Lu etc. (journal of applied,, the 53rd volume, 1453-1460 page or leaf in 1994) report adopts TiCl ₄/ NdCl ₃/ MgCl ₂/ Al (Et) ₃Catalyzer carries out copolymerization with ethene and vinylbenzene.Being manufactured in the U.S. Patent No. 5,244,996 that petrochemical industry company limited of Mitsubishi has of alpha-olefin/binyl aromatic monomer interpolymers such as propylene/styrene and butylene/styrene interpolymer has description.

The interpolymer that is used for one or more alpha-olefins of the present invention and one or more monovinylidene aromatic monomers and/or one or more hindered aliphatics or cycloaliphatic vinylidene monomer is random basically polymkeric substance.These interpolymers comprise the 24-65% mole usually, preferred 27-46% mole, the more preferably at least a vinylidene aromatic monomer of 29-37% mole and/or hindered aliphatic or cycloaliphatic vinylidene monomer; And the 35-76% mole, preferred 54-73% mole, the more preferably at least a aliphatic alpha-olefin of 63-71% mole with 2-20 carbon atom.

The number-average molecular weight of these polymkeric substance or interpolymer (Mn) is usually greater than 10000, preferred 20000-1000000, more preferably 50000-500000.

Be applicable to the melt index (I of interpolymer of the present invention ₂) for 0.05-1000 restrains/10 minutes, preferred 0.1-500 gram/10 minutes, more preferably the 0.5-100 gram is/10 minutes.

Preparation this basically during random interpolymer, may form a certain amount of atactic vinylidene aromatic homopolymer owing to vinylidene aromatic monomer homopolymerization at high temperature.The existence of vinylidene aromatic homopolymer is generally harmless to the present invention, therefore can allow.If desired, the vinylidene aromatic homopolymer can pass through extraction process (for example, the non-solvent with interpolymer or this vinylidene aromatic homopolymer carries out selective precipitation from solution) and separates from interpolymer.For the present invention, preferred existence is no more than 20% weight based on the interpolymer gross weight, preferably is lower than the atactic vinylidene aromatic homopolymer of 15% weight.

The present invention also provides the sealing of being made by the blend of random alpha-olefin/vinylidene/interpolymer and one or more other polymeric constituents basically.These other polymeric constituent comprises polystyrene, high-impact polystyrene, polyvinyl chloride, styrol copolymer (comprising multipolymer at least a in vinylbenzene and divinyl, vinyl cyanide, methacrylonitrile, maleic anhydride or the alpha-methyl styrene), aliphatic C ₂-C ₂₀The multipolymer of the homopolymer of alpha-olefin and multipolymer, ethene and vinyl-acetic ester, chlorination alpha-olefinic polymer; Or contain and be lower than about 24% mole of random basically alpha-olefin/vinylidene/interpolymer derived from the polymer unit of the array configuration of at least a vinylidene aromatic monomer or at least a hindered aliphatic or cycloaliphatic vinylidene monomer or at least a vinylidene aromatic monomer and at least a hindered aliphatic or cycloaliphatic vinylidene monomer.

Also comprise unsaturated segmented copolymer, comprise those that represent by following structural formula:

Structural formula I A-B-R (B-A) _nOr

Structural formula II A _x-(BA-) _y-BA

Wherein A is respectively the polymer blocks that comprises monovinylidene aromatic monomer, optimization styrene; And B is respectively and comprises conjugated diolefine, preferred isoprene or divinyl, and the polymer blocks of dispensable monovinylidene aromatic monomer, optimization styrene; R is the resistates of multifunctional coupling agent; N is the integer of 1-5; X is 0 or 1; And y is the real number of 0-4.

The preparation that can be used for segmented copolymer of the present invention is not a theme of the present invention.The preparation method of these segmented copolymers is known in the art.Be applicable to that the catalyzer for preparing useful segmented copolymer with the unsaturated rubber monomer comprises that lithium is catalyst based, especially lithium alkylide.United States Patent (USP) 3595942 has been described and has been applicable to and will has the method that is hydrogenated to the segmented copolymer with saturated rubber monomer units of the segmented copolymer of unsaturated rubber monomeric unit.The structure of this polymkeric substance is determined by its polymerisation process.For example, simple linear polymer obtains like this: if use initiators such as lithium alkylide or two lithium Stilbene, add required rubber monomer in the reaction vessel in proper order; Or come two segmented copolymers of coupling with the difunctionality coupling agent.On the other hand, branched structure can obtain by using suitable coupling agents, this coupling agent have 3 or a higher relevant functionality of the segmented copolymer with having the unsaturated rubber monomeric unit.Coupling can be used multifunctional coupling agent such as dihalo alkane or alkene and Vinylstyrene, and uses the ester of some polar compound such as silicon halide, siloxanes or monohydroxy-alcohol and carboxylic acid to carry out.In order to describe the segmented copolymer that constitutes a present composition part suitably, can ignore any coupling resistates that is present in the polymkeric substance.

Suitable segmented copolymer with unsaturated rubber monomeric unit includes, but is not limited to styrene butadiene (SB), styrene-isoprene (SI), styrene-butadiene-styrene (SBS), styrene-isoprene-phenylethene (SIS), alpha-methyl styrene-divinyl-alpha-methyl styrene and alpha-methyl styrene-isoprene-alpha-methyl styrene.

The polystyrene of this segmented copolymer partly is preferably the homopolymer or the copolymer in combination form of vinylbenzene and analogue and homologue, comprising alpha-methyl styrene and ring substituted phenylethylene, especially encircles-methylate vinylbenzene.Preferred polystyrene material is vinylbenzene and alpha-methyl styrene, special optimization styrene.

Segmented copolymer with unsaturated rubber monomeric unit can comprise the homopolymer of divinyl or isoprene, or they can comprise one or both these class diene and small amounts of styrene is monomeric multipolymer.

Preferred block copolymer with saturated rubber monomer units comprises the segment of the unitary segment of at least one polystyrene and at least one ethene-butylene or ethylene-propylene copolymer.Preferred example with this segmented copolymer of saturated rubber monomer units comprises styrene/ethylene-butylene copolymer, styrene/ethylene-propylene copolymer, styrene/ethylene-butylene/styrene (SEBS) multipolymer, styrene/ethylene-propylene/styrene (SEPS) multipolymer.

Hydrogenation with segmented copolymer of unsaturated rubber monomeric unit preferably uses a kind of catalyzer that comprises the reaction product of alkylaluminium cpd and nickel carboxylate or cobalt or its alcoholate to carry out, its condition makes basically the aliphatic double bond of hydrogenation at least 80% fully, hydrogenation simultaneously be no more than 25% the two keys of polystyrene aromatics.In preferred segmented copolymer, at least 99% aliphatic double bond is hydrogenated and is lower than 5% two keys of aromatics and is hydrogenated.

The ratio of polystyrene block is generally the 8-65% weight of segmented copolymer gross weight.Gross weight with segmented copolymer is a base, and this segmented copolymer preferably comprises the polystyrene block segments of 10-35% weight and the rubber monomer block segments of 90-65% weight.

The molecular-weight average of single block can change in certain limit.In most of the cases, the number-average molecular weight of polystyrene block segments is 5000-125000, preferred 7000-60000, and the molecular-weight average of rubber monomer block segments is 10000-300000, preferred 30000-150000.The total average molecular weight of this segmented copolymer is generally 25000-250000, preferred 35000-200000.

In addition, be applicable to that various segmented copolymer of the present invention can utilize any method well known in the art, introduce a spot of functional group, as maleic anhydride and modification by grafting.

It is commercially available can be used for segmented copolymer of the present invention, for example by Shell chemical company with trade(brand)name KRATON ^TMAltogether should, and by Dexco Polymer Company with trade(brand)name VECTOR ^TMSupply.

The polymer blend compositions that is used to prepare sealing system of the present invention can prepare by the method for any routine, comprise: each component is done mixed, subsequently directly be used for article of manufacture (as, trolley part) molten mixing in forcing machine or the grinding machine, or by independent forcing machine or grinding machine (as, the Banbury mixing tank) the pre-melt in mixes and carries out melt-mixing or melt compounded, or utilizes solution blending, or by compression moulding or by calendering.

The blend that is used to prepare the sealing of sealing system of the present invention comprises:

(A) gross weight with component A and B is a base, 35-99% weight, preferred 40-97% weight, the more preferably random basically interpolymer of one or more alpha-olefins of 40-95% weight and one or more monovinylidene aromatic monomers and/or one or more hindered aliphatics or cycloaliphatic vinylidene monomer wherein comprises:

A) 24-65% mole, about 46% mole of preferably about 27-, more preferably the 29-37% mole derived from the polymer unit of at least a vinylidene aromatic monomer and/or hindered aliphatic or cycloaliphatic vinylidene monomer and

B) 35-76% mole, preferred 54-73% mole, more preferably from about 63-about 71% mole derived from least a polymer unit with aliphatic alpha-olefin of 2-20 carbon atom; With

(B) gross weight with component A and B is a base, 65-1% weight, preferred 60-3% weight, more preferably at least a polymkeric substance of 60-5% weight comprises multipolymer at least a in polystyrene, high-impact polystyrene, polyvinyl chloride, vinylbenzene and vinyl cyanide, methacrylonitrile, maleic anhydride or the alpha-methyl styrene, aliphatic C ₂-C ₂₀The homopolymer of alpha-olefin and multipolymer, the multipolymer of ethene and vinyl-acetic ester, the chlorination alpha-olefinic polymer, or (wherein said polymer unit is derived from least a vinylidene aromatic monomer to contain the random basically alpha-olefin/vinylidene/interpolymer that is lower than about 24% mole of following polymer unit, or at least a hindered aliphatic or cycloaliphatic vinylidene monomer, or the array configuration of at least a vinylidene aromatic monomer and at least a hindered aliphatic or cycloaliphatic vinylidene monomer), or styrene butadiene (SB), styrene-isoprene (SI), styrene-butadiene-styrene (SBS), styrene-isoprene-phenylethene (SIS), or styrene-ethylene/butylene-styrene (SEBS) segmented copolymer.

Be used for interpolymer of the present invention and/or blend, also (for example can comprise additive such as antioxidant, sterically hindered phenol, as Irganox  1010), phosphorous acid ester (for example, Irgafos  168), ultra-violet stabilizer, release additives (as, polyisobutene), anti-caking agent, tinting material, pigment, filler, as long as the improvement sealing property that they do not influence the applicant and are found.The preferred example of filler is talcum, carbon black, carbon fiber, lime carbonate, three hydrated alumina, glass fibre, marble flour, cement flour, clay, feldspar, silica or glass, forges and make silica, alumina, magnesium oxide, magnesium hydroxide, weisspiessglanz, zinc oxide, barium sulfate, pure aluminium silicate, Calucium Silicate powder, titanium dioxide, titanate, glass microsphere or chalk.In these fillers, barium sulfate, talcum, lime carbonate, silica/glass, glass fibre, alumina and titanium dioxide, and composition thereof be preferred.

Most preferred mineral filler is talcum, lime carbonate, barium sulfate, glass fibre or its mixture.The consumption of these fillers can be based on the 0-90% weight of described polymkeric substance or blend polymer weight, preferred 0-80% weight, more preferably 0-70% weight.

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 anti-caking effect, 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.

At the polymer composition that is used for preparing the present invention's sealing, a kind of useful especially additive is a lubricant.This additive is known various more common titles, as if as slippage agent or releasing agent, this depends on the specified property improved action of this additive.For example, lubricant, preferred solid lubricant comprises inorganic materials such as siloxanes, especially dimethylsiloxane polymer, fatty acid amide such as ethylene (stearylamide), oleylamide and mustard acid amides; And the metal-salt of lipid acid, as Zinic stearas, calcium or lead.The suitable inorganic materials that also has talcum, mica, fused silica and Calucium Silicate powder and so on.Gratifying amounts of lubrication is the 0.01-5% weight based on this mixture total weight, more preferably 0.05-4% weight.

The present invention also comprises the sealing of being made by disclosed interpolymer and blend composition, and wherein said composition can be further and softening agent, tackifier (aliphatic series, aromatics, rosin derivative, and composition thereof) and oily compounding.

Can use multiple molded operation to make sealing of the present invention, include (but are not necessarily limited to) solution casting, thermoforming and various Shooting Technique are (for example, be described in modern plastics encyclopedia/89, in mid-October, 1988 distribution, the 65th volume, No11, " the injection moulding introduction " of 264-268 page or leaf and " the injection heat thermoplastic plastic " of 270-271 page or leaf) and blow moulding is (for example, be described in modern plastics encyclopedia/89, in mid-October, 1988 distribution, the 65th volume, No11, " extrusion molding-blowing " of 217-218 page or leaf) and compression moulding, contour extrusion, sheet extrusion, the film curtain coating, coextrusion and multi layer extrusion, injection moulding altogether, lamination, blown film.

The desired sealing of this paper also can be made by extrusion sheet or film, and these sheet materials or film obtain by routine techniques, comprises inflation, curtain coating or extrusion coated film, then by this sheet material or film punching press or cutting sealing system.Multi-layer film structure also is applicable to makes sealing disclosed herein, and prerequisite is that one deck comprises described random basically interpolymer at least.

The foam material structure that comprises the random interpolymer basically of crosslinked or uncrosslinked form also can be used for preparing sealing of the present invention.Foaming composition can be used as the one deck in the single or multiple lift structure.C.P.Park has fabulous description for method for preparing the ethylenic polymer foamy structure and working method thereof, referring to " foam of polymers and technical manual " the 9th chapter " expanded polyolefin " (C.P.Park, " Polyolefin Foam ", Chapter 9, Handbook of Polymer Foams andTechnology, D.Klempner and K.C.Frisch edit, Hanser press, Munich, vienna, New York, Barcelona (1991)).

Foam material structure can be made by the extruded plastic foam technology of routine.Be used to produce the foam material structure that merges wire-form device and and method can be referring to United States Patent (USP) 3573152 and 4824720.Foam material structure of the present invention also can the moulding by United States Patent (USP) 4323528 described storing extrusion moldings.

This foam material structure also may be molded to and is applicable to the foam materials bead that is molded as the present invention's sealing.This method has fine statement in United States Patent (USP) 4379859, United States Patent (USP) 4464484 and United States Patent (USP) 4168353.This foam materials bead can be molded as piece material or moulded products by suitable molding methods known in the art subsequently.(U.S. Patent No. 3,504,068 and 3,953,556 disclose certain methods).C.P.Park has fine narration to above-mentioned technology and molding methods, referring to C.P.Park, quote from the same, 191 pages, 197-199 page or leaf and 227-229 page or leaf.

The whipping agent that is used to prepare foamy structure of the present invention comprises inorganic foaming agent, organic blowing agent and chemical foaming agent.Suitable inorganic foaming agent comprises carbonic acid gas, nitrogen, argon gas, water, air, nitrogen and helium.Organic blowing agent comprises the aliphatic hydrocarbon that contains 1 to 6 carbon atom, contains the Fatty Alcohol(C12-C14 and C12-C18) of 1 to 3 carbon atom and contains the complete and partially halogenated aliphatic hydrocarbon of 1 to 4 carbon atom.Aliphatic hydrocarbon comprises methane, ethane, propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, neopentane etc.Fatty Alcohol(C12-C14 and C12-C18) comprises methyl alcohol, ethanol, n-propyl alcohol and Virahol.Complete and partially halogenated aliphatic hydrocarbon comprises hydrofluoric ether, hydrochloric ether and Chlorofluorocarbons (CFCs).The example of hydrofluoric ether comprises fluoromethane, perfluoromethane, fluoroethane, 1,1-C2H4F2 C2H4F2 (HFC-152a), 1,1,1-Halothane (HFC-143a), 1,1,1,2-Tetrafluoroethane (HFC-134a), pentafluoride ethane, methylene fluoride, R 116,2,2-difluoropropane, 1,1,1-trifluoro propane, perfluoropropane, propylene dichloride, difluoropropane, perfluorinated butane, perfluorocyclobutane.Partially halogenated hydrochloric ether and Chlorofluorocarbons (CFCs) that the present invention adopts comprise methyl chloride, methylene dichloride, monochloroethane, 1,1,1-trichloroethane, 1,1-two chloro-1-fluoroethanes (HCFC-141b), 1-chloro-1,1-C2H4F2 C2H4F2 (HCFC-142b), 1,1-two chloro-2,2,2-Halothane (HCFC-123) and 1-chloro-1,2,2,2-Tetrafluoroethane (HCFC-124).Complete halogenated Chlorofluorocarbons (CFCs) comprises Trichloromonofluoromethane (CFC-11), Refrigerant 12 (CFC-12), Refrigerant R 113 (CFC-113), 1,1,1-Halothane, pentafluoride ethane, dichloro tetrafluoro ethane (CFC-114), a chlorine heptafluoro-propane and a dichlorohexafluoropr.pane.Chemical foaming agent comprises azodicarboamide, Diisopropyl azodicarboxylate, benzol sulfohydrazide, 4,4-oxygen connects benzene sulfonyl semicarbazides, tolysulfonyl semicarbazides, azoformic acid barium, N, N '-dimethyl-N, N '-dinitrosoterephthalamine and three hydrazine triazines.Preferred blowing agent comprises Trimethylmethane, HFC-152a and composition thereof.

For preparation can form the foamy polymer gel, the amount that adds the whipping agent in the random basically interpolymer is every kg of polymer 0.2 to 5 mol, preferred 0.5 to 3 mol, 1 to 2.5 mol most preferably from about.

Various additives can be added in the foam material structure of the present invention, for example stability control agent, nucleator, mineral filler, pigment, antioxidant, sour trapping agent, UV light absorber, fire retardant, processing aid, extrusion aid etc.

Stability control agent can add in the foam materials of the present invention to improve stability in storage.Preferred control agent comprises C ₁₀-C ₂₄The acid amides of lipid acid and ester.These control agents also can be referring to United States Patent (USP) 3644230 and 4214054.Most preferred stability control agent is stearyl stearylamide, Zerol, glycerine list (docosoic acid) ester and sorbitol monostearate.Usually, the consumption of these stability control agents is 0.1-10 part/100 part polymkeric substance.

In addition, can add the size that nucleator comes control foam material abscess.Preferred nucleator comprise inorganic substance such as lime carbonate, talcum, clay, titanium dioxide, silica, barium sulfate, diatomite, citric acid and sodium bicarbonate mixture, etc.The consumption of nucleator is 0.01-5 weight part/100 parts by weight polymer resins.

Many methods that can be used for producing sealing system or lid are arranged, for example be described in United States Patent (USP) 4347939, United States Patent (USP) 4620426, United States Patent (USP) 4988467, United States Patent (USP) 4818577, United States Patent (USP) 4274822 and United States Patent (USP) 4946362.

In one embodiment, sealing or lining can be by making the film (by extrusion molding production) with suitable thickness, cut out disk from this film then with suitable diameter, offer also the premolding lid of making by conventional method such as injection moulding separately, thereby will seal or lining is attached on the container cover.This disk should have suitable diameter, like this lateral margin inside of adaptive this lid closely when pressing to the substrate walls internal surface.By the method for knowing,, this disk is fixed to covers for example by using tackiness agent or heating.Second and usually in the embodiment preferred, sealing or lining are extruded, cut, compression moulding is in lid then.

By sealing system or lining are included on the lower surface of substrate walls, can satisfy bottle cap to having the requirement that minimum threshold moves moment of torsion, gas retention and resealability, this lining can be carried the top that affacts this container when tight at bottle cap like this.

The oxygen permeability of the present invention's sealing is lower than 300 centimetres ³Mil/100 inch ²(1.2 centimetres in it normal atmosphere ³/ centimetre sky MPa), preferably be lower than 200 centimetres ³Mil/100 inch ²(0.8 centimetre in it normal atmosphere ³/ centimetre. day. MPa), more preferably less than 150 centimetres ³Mil/100 inch ²(0.6c centimetre in it normal atmosphere ³/ centimetre sky MPa), can be low to moderate 60 centimetres usually ³Mil/100 inch ²(0.2 centimetre in it normal atmosphere ³/ centimetre sky MPa).

In addition, the tension strain response rate of the present invention's sealing is preferably greater than 80%, more preferably greater than 85%, usually up to 95% greater than 70%.Simultaneously, the stress relaxation of the present invention's sealing is preferably greater than 55% greater than 50%, more preferably greater than 60%, may be up to 85% usually.

In addition, the Xiao A hardness of the present invention's sealing can be lower than 99, preferably is lower than 90, more preferably less than 65, is low to moderate 60 usually.

Embodiment

The molecular weight that is used for polymer composition of the present invention uses the melt index observed value to represent that according to ASTM D-1238, condition 190 ℃/2.16 kilograms (formally are called " condition (E) ", are also referred to as I2) is measured.The molecular weight of melt index and polymkeric substance is inversely proportional to.Therefore, molecular weight is high more, and melt index is low more, but this relation and non-linear.

Interpolymer styrene content and random isotactic polystyrene concentration use proton magnetic resonance (PMR) ( ¹H-NMR) measure.All proton N MR samples are all at sym.-tetrachloroethane-d ₂(TCE-d ₂) middle preparation.The polymer content of gained solution is a 1.6-3.2% weight.Melt index (I ₂) be used to instruct definite sample concentration.Therefore, if I ₂Greater than 2, use 40 milligrams polymkeric substance; I ₂During for 1.5-2, use 30 milligrams polymkeric substance; And work as I ₂Be lower than 1.5 grams in the time of/10 minutes, use 20 milligrams of polymkeric substance.Polymkeric substance directly is weighed in 5 millimeters sample hoses.Add 0.75 milliliter of TCE-d by syringe ₂Aliquots containig, the polyethylene cover with close fitting covers then.Sample is heated in 85 ℃ of water-baths with softening this polymkeric substance.In order to mix, to use hot rifle to make frequently and add a cover back flow of sample.

Proton N MR spectrum is collected on the Varian VXR 300, and wherein the sample probe temperature is 80 ℃, with the TCE-d of 5.99ppm place ₂Remaining proton be reference.Changed time of lag in 1 second, and each sample collection three secondary data.The bulk analysis time of each sample is about 10 minutes, has wherein adopted following instrument condition:

Varian VXR-300, standard ¹H:

Sweep length, 5000 hertz

Acquisition time, 3.002 seconds

Pulse width, 8 microseconds

Frequency, 300MHz

Postpone 1 second

Transient state, 16

At first, obtain polystyrene sample STYRON ^TM680 (available from Dow chemical company, Midland, Michigan) ¹H NMR spectrum, wherein be 1 second time of lag.Proton is " mark " like this: b, branch; α, alpha; O, the neighbour; M; P, right, as shown in Figure 1.

Around Fig. 1 institute target proton, measure integration; " A " represents aPS.Integration A7.1 (aromatics is around 7.1ppm) it is believed that it is three neighbours/contraposition proton; And integration A _6.6(aromatics is around 6.6ppm) is position proton between 2.Two aliphatic proton resonances that are designated as α are in 1.5ppm; And the single proton resonance that is designated as b is in 1.9ppm.The aliphatic series district by about 0.8ppm to 2.5ppm integration, is called A _{Aliphatic series}A _7.1: A _6.6: A _{Aliphatic series}Theoretical ratio be 3: 2: 3, or 1.5: 1: 1.5, with STYRON ^TMThe dependency of the actual measurement ratio during 680 samples very good (for time of lag of 1 second several times).Be used to check integration and confirm that the ratio calculating of peak ownership can be with suitable integration divided by integration A _6.6Carry out.Ratio A _rBe A _7.1/ A _6.6

Zone A _6.6Value be appointed as 1.Ratio A l is integration A _{Aliphatic series}/ A _6.6All collected spectrographic integration ratio (o+p): m: (α+b) all had desired value 1.5: 1: 1.5.Aromatics is 5 to 3 with the ratio of aliphatic proton.According to the proton that is denoted as α and b among Fig. 1, aliphatic ratio is 2 to 1.If separately two aliphatic peaks are carried out integration, also can be observed this ratio.

For the ethylene/styrene interpolymer, be 1 second time of lag ¹H NMR spectrographic integration A _7.1, A _6.6And A _{Aliphatic series}Make that the integration at peak, 7.1ppm place comprises all aromatics protons of this multipolymer and the adjacent ﹠ contraposition proton of aPS.In the spectrum of this interpolymer, the integration in aliphatic series district comprises the aliphatic proton of aPS and interpolymer in addition, and every kind of polymkeric substance does not all have clearly baseline explanation signal.6.6ppm locate peak C _6.6Integration can from other aromatic signal, offer an explanation, this it is believed that and only belongs to aPS homopolymer (between may being position proton).(random isotactic polystyrene is at the peak at 6.6ppm place ownership (integration A _6.6) basis and authentic sample STYRON ^TM680 relatively carry out.) this is a kind of rational hypothesis, because when the random isotactic polystyrene of low levels very, only can observe a very weak signal.Therefore, the phenyl protons of this multipolymer is inevitable irrelevant with this signal.Under this assumption, integration A _6.6Just become the basis of quantitatively determining aPS content.

Use following equation to determine the add-on of vinylbenzene in ethylene/styrene interpolymer sample then:

(C phenyl)=C _7.1+ A _7.1-(1.5 * A _6.6)

(C aliphatic series)=A _{Aliphatic series}-(1.5 * A _6.6)

s _c=(C phenyl)/5

e _c=(C aliphatic series-(3 * s _c))/4

E=e _c/(e _c+s _c)

S _c=s _c/(e _c+s _c)

Use following equation to calculate ethene and the molecular fraction of vinylbenzene in this interpolymer then. $\mathrm{Wt}\%E=\frac{E*28}{(E*28)+(S_c*104)}\left(100\right)$ With $\mathrm{Wt}\%S=\frac{S_c*104}{(E*28)+(S_c*104)}\left(100\right)$

S wherein _cAnd e _cBe respectively vinylbenzene and the mark of ethene proton in this interpolymer, and S _cWith E be respectively styrene monomer and the molar fraction of vinyl monomer in this interpolymer.

The weight percentage of aPS in this interpolymer determined by following equation:

Total styrene content also can be determined by quantitative Fourier transform infrared spectroscopy (FTIR).

Embodiment 1

130 milliliters of continuous loop pipe reactors that use is made up of 2 static mixers, a toothed gear pump (1000 ml/min), the inlet that is used for liquids and gases, viscometer and a pair of thermopair prepare the embodiment of the invention 1.The temperature of this reactor keeps by outer heating zone.Locate monitor force in the liquid inlet, and control by an adjustable valve in exit.Add mixture of forming by the ethene of 100% vinylbenzene of 12.10 ml/min, 0.501 gram/minute, 0.207 milligram/minute hydrogen and the catalyst system of forming by the 0.001M toluene solution of tertiary butyl amino dimethyl (tetramethyl-ring pentadienyl) silane dimethyl titanium and three-(pentafluorophenyl group) borine (both flow velocitys all are 0.20 ml/min) to this reactor.Temperature of reactor is remained on 51.3 ℃, and stable viscosity at about 9 centipoises (cP) (0.009Pas).With the catalyzer deactivator/polymer stabilizing agent solution of resulting polymers solution and 0.05 ml/min (1 liter of toluene, 20 gram Irganox ^TM1010 and 15 milliliters of 2-propyl alcohol) mix, be cooled to envrionment temperature, collected 15 hours 26 minutes.With this solution dried overnight in vacuum oven, obtain the ethylene/styrene multipolymer of 42.1% mole of styrene content of 1223 grams, wherein the content of random isotactic polystyrene is 7.4% weight, and melt index (I ₂) be 0.046 gram/10 minutes.

Embodiment 2

In the semi-continuous batch reactor that 400 gallons of bands stir, prepare interpolymer.Reaction mixture is made up of about 250 gallons mixed solvent and the vinylbenzene that contain cyclohexane (85% weight) and iso-pentane (15% weight).Before adding reactor, solvent, vinylbenzene and ethene all dewater and the purification process of deoxygenation.Stopper in the vinylbenzene also is removed.In container, feed ethene to remove inert substance.Subsequently with ethene with the pressure-controlling of container in set(ting)value.Add hydrogen to regulate molecular weight.The temperature of container is to be controlled at set(ting)value by the temperature that changes water in the container chuck.

Before polymerization, container is heated to required temperature, with the various components of catalyzer: (N-1, the 1-dimethyl ethyl) (1-(1,2,3 for dimethyl, 4,5-η)-2,3,4,5-tetramethyl--2,4-cyclopentadiene-1-base silane amine closes)) (2-) N)-dimethyl titanium [CAS accession number (CAS#) 135072-62-7], three (pentafluorophenyl group) boron [CAS#001109-15-5], 3A type modified methylaluminoxane [CAS#146905-79-5] mixes with 1/3/5 mol ratio dominant discharge and is added in the container.After starting reaction, in reactor, feed ethene keep in the container pressure so that polyreaction continue to carry out.At the upper space that in some cases hydrogen is fed reactor under certain ethylene concentration, to keep the mol ratio of hydrogen and ethene.When reaction finishes, stop to add catalyzer, ethene is removed from reactor, in solution, add 1000 ppm (aim parameter) Irganox subsequently ^TM1010 antioxidants, and polymkeric substance separated from solution.By in container, carrying out steam stripped or the volatile matter forcing machine is removed in utilization, from solution, isolate resulting polymers.For the steam stripped material, need to adopt the equipment that is similar to forcing machine that it is handled to reduce moisture and the cinnamic content of all unreacteds wherein again.

Contrast experiment 1 is a kind of random basically ethylene styrene interpolymer, makes according to the preparation condition of embodiment 2, use table 1 basically, and its performance is summarized in table 2.

Contrast experiment 2 is a kind of random basically ethylene styrene interpolymers, makes according to the preparation condition of embodiment 2, use table 1 basically, and its performance is summarized in table 2.

Contrast experiment 3 is a kind of ethene/1-octene copolymers, and density is 0.87 gram per centimeter ³And melt index (I ₂) be 1.00 grams/10 minutes, derive from DuPont Dow elastomerics company, commodity are called ENGAGE ^TMEG8100.

Contrast experiment 4 is a kind of hydrogenation SEBS styrene block copolymers, derives from Shell chemical company, and commodity are called KRATON ^TMG.

Contrast experiment 5 is oriented polystyrene films, derives from Dow chemical company, and commodity are called TRICITE ^TM

Table 1

Embodiment	Quantity of solvent		The vinylbenzene amount		Pressure			Temperature	H 2Total add-on	Reaction times
											Pound	Kilogram	Pound	Kilogram	Pound/inch 2		KPa	℃	Gram	Hour
	Embodiment 2	839	381	659	299	70		483	60	22											5.2
Embodiment 3											252	114	1320	599	42		290	60	0	2.8
	Embodiment 4	839	381	659	299	70		483	60	35											5.6
Embodiment 5											252	114	1320	599	40		276	60	23	6.5
	Comparative Examples 1	1196	542	225	102	70		483	60	7.5											6.1
Comparative Examples 2											839	381	661	300	105		724	60	53.1	4.8

Table 2

Embodiment	I 2Restrain/10 minutes	Cinnamic molecular fraction in the interpolymer	Talc content, % weight	Separation method
					Embodiment 2	0.87	30.3	0	Steam stripped
Embodiment 3	0.18	43.6	＜2.5	Steam stripped
					Embodiment 4	0.49	28.8	0	Steam stripped
Embodiment 5	1.8	41.8	＜2.0	Steam stripped
					Comparative Examples 1	0.03	9.2	0	Forcing machine
Comparative Examples 2	2.6	17.1	0	Forcing machine

Embodiment 6-8

Embodiment 6-8 is random basically ethylene/styrene interpolymer, uses following catalyzer and polymerisation process to make.

Catalyst A, (dimethyl [N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-1,5,6,7-tetrahydrochysene-3-phenyl-s-cyclopenta indenes-1-yl] silanamines close (2-)-N]-titanium) be prepared as follows.At first, 3,5,6,7-tetrahydrochysene-s-cyclopenta indenes-1 (2H)-ketone is prepared as follows.Under nitrogen gas stream, indane (94.00 grams, 0.7954 mole) and 3-chlorpromazine chloride (100.99 grams, 0.7954 mole) are stirred adding CH down at 0 ℃ ₂Cl ₂In (300 milliliters), slowly add AlCl simultaneously ₃(130.00 grams, 0.9750 mole).Then this mixture was at room temperature stirred 2 hours.Remove volatile matter.This mixture is cooled to 0 ℃, slowly adds dense H then ₂SO ₄(500 milliliters).The solid matter that forms must frequently be smashed with scraper, just can not stir because this step is early stage.At room temperature, this mixture is placed under nitrogen spent the night.With this mixture heating up, reach 90 ℃ then up to temperature reading.These conditions were kept 2 hours, in this process, regularly use scraper to stir this mixture.After reaction period, trash ice is put into this mixture, rotation is shaken then.This mixture is transferred in the beaker, used H ₂Each fraction and merging are filtered in O and diethyl ether washing then.Water (2 * 200 milliliters) washs this mixture.Separate organic layer, and remove volatile matter.By under 0 ℃ from hexane recrystallization isolate required product, be pale yellow crystals (22.36 grams, 16.3% productive rate).

¹H NMR (CDCl ₃) provide: d2.04-2.19 (m, 2H), 2.65 (t, ³JHH=5.7Hz, 2H), 2.84-3.0 (m, 4H), 3.03 (t, ³JHH=5.5Hz, 2H), 7.26 (s, 1H), 7.53 (s, 1H).

¹³C NMR (CDCl ₃) provide: d25.71,26.01,32.19,33.24,36.93,118.90,122.16,135.88,144.06,152.89,154.36,206.50.GC-MS:C ₁₂H ₁₂O calculated value 172.09, measured value 172.05.

1,2,3,5-tetrahydrochysene-7-phenyl-s-cyclopenta indenes is prepared as follows.With 3,5,6,7-tetrahydrochysene-s-cyclopenta indenes-1 (2H)-ketone (12.00 grams, 0.06968 mole) stirs down at 0 ℃ and adds in the diethyl ether (200 milliliters), slowly adds PhMgBr (0.105 mole, 35.00 milliliters 3.0M diethyl ether solution) simultaneously.This mixture at room temperature stirred spend the night.After reaction period, this mixture is poured on ice and quenching.With this mixture of HCl acidifying (pH value=1), vigorous stirring is 2 hours then.Separate organic layer, use H ₂MgSO is used in O (2 * 100 milliliters) washing then ₄Dry.Filter and remove volatile matter, the result isolates required product, is dark oil (14.68 grams, 90.3% productive rate).

¹H NMR (CDCl ₃) provide: d2.0-2.2 (m, 2H), 2.8-3.1 (m, 4H), 6.54 (s, 1H), 7.2-7.6 (m.7H) .GC-MS:C ₁₈H ₁₆Calculated value 232.13, measured value 232.05.1,2,3,5-tetrahydrochysene-7-phenyl-s-cyclopenta indenes dilithium salt is prepared as follows.With 1,2,3,5-tetrahydrochysene-7-phenyl-s-cyclopenta indenes (41.68 grams, 0.06291 mole) stirs and adds in the hexane (150 milliliters), slowly adds n-Butyl Lithium (0.080 mole, 40.00 milliliters 2.0M cyclohexane solution) simultaneously.This mixture stirring is spent the night.After reaction period, collect a kind of yellow solid by suction strainer, use hexane wash, vacuum-drying need not to be further purified or analyzes (12.2075 grams, 81.1% productive rate) and just can use.

Chlorodimethyl (1,5,6,7-tetrahydrochysene-3-phenyl-s-cyclopenta indenes-1-yl) silane is prepared as follows.Under 0 ℃, with 1,2,3 among the THF (50 milliliters), the dilithium salt of 5-tetrahydrochysene-7-phenyl-s-cyclopenta indenes (12.2075 grams, 0.05102 mole) is added drop-wise to the Me among the THF (100 milliliters) ₂SiCl ₂In (19.5010 grams, 0.1511 mole).This mixture stirring is spent the night.After reaction period, remove volatile matter, use hexane extraction resistates and filtration then.Remove hexane, isolate required product, be a kind of yellow oil (15.1492 grams, 91.1% productive rate).

¹H NMR (CDCl ₃) provide: d0.33 (s, 3H), 0.38 (s, 3H), 2.20 (p, ³JHH=7.5Hz, 2H), 2.9-3.1 (m, 4H), 3.84 (s, 1H), 6.69 (d, ³JHH=2.8Hz, 1H), 7.3-7.6 (m, 7H), 7.68 (d, ³JHH=7.4Hz, 2H).

¹³C NMR (CDCl ₃) provide: d0.24,0.38,26.28,33.05,33.18,46.13,116.42,119.71,127.51,128.33,128.64,129.56,136.51,141.31,141.86,142.17,142.41,144.62, GC-MS:C ₂₀H ₂₁ClSi calculated value 324.11, measured value 324.05.

N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-(1,5,6,7-tetrahydrochysene-3-phenyl-s-cyclopenta indenes-1-yl) silanamines are prepared as follows.Under 0 ℃, Chlorodimethyl (1,5,6,7-tetrahydrochysene-3-phenyl-s-cyclopenta indenes-1-yl) silane (10.8277 grams, 0.03322 mole) is stirred in the adding hexane (150 milliliters), add NEt simultaneously ₃(3.5123 grams, 0.03471 mole) and tert-butylamine (2.6074 grams, 0.03565 mole).This mixture was stirred 24 hours.After reaction period, filter this mixture and remove volatile matter, isolate required product, be a kind of reddish yellow viscous crude (10.6551 grams, 88.7% productive rate).

¹H NMR (CDCl ₃) provide: d0.02 (s, 3H), 0.04 (s, 3H), 1.27 (s, 9H), 2.16 (p, 3JHH=7.2Hz, 2H), 2.9-3.0 (m, 4H), 3.68 (s, 1H), 6.69 (s, 1H), 7.3-7.5 (m, 4H), 7.63 (d, ³JHH=7.4Hz, 2H).

¹³C NMR (CDCl ₃) provide: d-0.32 ,-0.09,26.28,33.39,34.11,46.46,47.54,49.81,115.80,119.30,126.92,127.89,128.46,132.99,137.30,140.20,140.81,141.64,142.08,144.83.

N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-(1,5,6,7-tetrahydrochysene-3-phenyl-s-cyclopenta indenes-1-yl) silanamines dilithium salt is prepared as follows.With N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-(1,5,6,7-tetrahydrochysene-3-phenyl-s-cyclopenta indenes-1-yl) silanamines (10.6551 grams, 0.02947 mole) stir and add in the hexane (100 milliliters), slowly add simultaneously n-Butyl Lithium (0.070 mole, 35.00 milliliters 2.0M cyclohexane solution).This mixture stirring is spent the night, in this process, from dark red solution, precipitate any salt.After reaction period, remove volatile matter, use hexane (2 * 50 milliliters) debris rapidly then.Then the scarlet resistates is drained, be need not to be further purified or analyze (9.6517 grams, 87.7% productive rate) and just can use.

[N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-1,5,6,7-tetrahydrochysene-3-phenyl-s-cyclopenta indenes-1-yl] silanamines close (2-)-N] titanium dichloride is prepared as follows.With the N-among the THF (50 milliliters) (1, the 1-dimethyl ethyl)-1, the dilithium salt of 1-dimethyl-1-(1,5,6,7-tetrahydrochysene-3-phenyl-s-cyclopenta indenes-1-yl) silanamines (4.5355 grams, 0.01214 mole) is added drop-wise to TiCl ₃(THF) ₃(4.5005 grams, 0.01214 mole) slurry in THF (100 milliliters).This mixture was stirred 2 hours.Add PbCl then ₂(1.7136 gram, 0.006162 mole), and this mixture of restir 1 hour.After reaction period, remove volatile matter, extract this resistates and filtration with toluene then.Remove toluene, isolate dark resistates.With the slurrying in hexane of this resistates, be cooled to 0 ℃ then.Filter to isolate required product, be a kind of reddish-brown crystalline solid (2.5280 grams, 43.5% productive rate).

¹H NMR (CDCl ₃) provide: d0.71 (s, 3H), 0.97 (s, 3H), 1.37 (s, 9H), 2.0-2.2 (m, 2H), 2.9-3.2 (m, 4H), 6.62 (s, 1H), 7.35-7.45 (m, 1H), 7.50 (t, ³JHH=7.8Hz, 2H) 7.57 (s, 1H), 7.70 (d, ³JHH=7.1Hz, 2H), 7.78 (s, 1H).

¹H NMR (C ₆D ₆) provide: d0.44 (s, 3H), 0.68 (s, 3H), 1.35 (s, 9H), 1.6-1.9 (m, 2H), 2.5-3.9 (m, 4H), 6.65 (s, 1H), 7.1-7.2 (m, 1H), 7.24 (t, ³JHH=7.1Hz, 2H), 7.61 (s, 1H), 7.69 (s, 1H), 7.77-7.8 (m, 2H).

¹³C NMR (CDCl ₃) provide: d1.29,3.89,26.47,32.62,32.84,32.92,63.16,98.25,118.70,121.75,125.62,128.46,128.55,128.79,129.01,134.11,134.53,136.04,146.15,148.93.

¹³C NMR (C ₆D ₆) provide: d0.90,3.57,26.46,32.56,32.78,62.88,98.14,119.19,121.97,125.84,127.15,128.83,129.03,129.55,134.57,135.04,136.41,136.51,147.24,148.96.

Dimethyl [N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-1,5,6,7-tetrahydrochysene-3-phenyl-s-cyclopenta indenes-1-yl] silanamines close (2-)-N titanium and are prepared as follows.With [N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-1,5,6,7-tetrahydrochysene-3-phenyl-s-cyclopenta indenes-1-yl] silanamines close (2-)-N] titanium dichloride (0.4970 gram, 0.001039 mole) stirs and adds in the diethyl ether (50 milliliters), slowly add simultaneously MeMgBr (0.0021 mole, 0.70 milliliter 3.0M diethyl ether solution).This mixture was stirred 1 hour.After reaction period, remove volatile matter, use hexane extraction resistates and filtration then.Remove hexane, isolate required product, be a kind of golden yellow solid (0.4546 gram, 66.7% productive rate).

¹H NMR (C ₆D ₆) provide: d0.071 (s, 3H), 0.49 (s, 3H), 0.70 (s, 3H), 0.73 (s, 3H), 1.49 (s, 9H), 1.7-1.8 (m, 2H), 2.5-2.8 (m, 4H), 6.41 (s, 1H), 7.29 (t, ³JHH=7.4Hz, 2H), 7.48 (s, 1H), 7.72 (d, ³JHH=7.4 Hz, 2H), 7.92 (s, 1H).

¹³C NMR (C ₆D ₆) provide: d2.19,4.61,27.12,32.86,33.00,34.73,58.68,58.82,118.62,121.98,124.26,127.32,128.63,128.98,131.23,134.39,136.38,143.19,144.85.

6 gallons of (22.7 liters) oil jackets, autoclave (reactor of continuously stirring) (CSTR) in, prepare embodiment 6-8.The magnetic force of band Lightning A-320 impeller cooperates agitator to be used for mixing.Reactor is in 475psig (3275kPa) filled with fluid operation down.Technical process is to go out on advancing at the end.Heat-transfer oil cycles through the chuck of reactor, removes some reaction heat.In the outlet of reactor, a fine motion under meter that is used to measure yield point value and solution density is arranged.All pipelines on the reactor outlet are filled with the steam of 50psig (344.4KPa) and isolated mutually.

Under 30psig (207KPa), toluene solvant is added in the reactor.Reinforced can the measurement in reactor by the fine motion mass flowmeter.Use the speed change surge pump to control feed rate.At the exit side of solvent pump, get the logistics of washing away that effluent is used for catalyzer filling line (11b/hr (0.45 kilogram/hour)) and reactor agitator (0.751b/hr (0.34 kilogram/hour)).These logistics can be measured by differential pressure flow meter, and control by manual adjustment miniflow needle-valve.Under 30psig (207KPa), the styrene monomer of removing stopper is added in the reactor.Reinforced can the measurement in reactor by the fine motion mass flowmeter.Use the speed change surge pump to control feed rate.Vinylbenzene liquid stream mixes with residual solvent liquid stream.Under 600psig (4137KPa), ethene is added in the reactor.By being positioned at flowrate control valve fine motion mass flowmeter before, measure the ethene air-flow.In the exit of ethene control valve, use Brooks velocimeter/controller, hydrogen is transported in the ethene air-flow.Ethene/hydrogen mixture at room temperature mixes with solvent/vinylbenzene liquid stream.By having the heat exchanger of-5 ℃ of ethylene glycol in the chuck, the temperature of solvent/monomer when entering reactor reduced to about 5 ℃.This logistics enters the bottom of reactor.Three-way catalyst system and fresh solvent thereof be also from the bottom, but enter reactor by the inlet that is different from monomer stream.Catalyst component prepares in inert-atmosphere glove box.The dilution component is put into the cylinder of nitrogen protection, add the catalyzer operation jar that is arranged in process island then.By these operation jars, use piston pump with the catalyzer supercharging, use fine motion mass flow meter measurement flow velocity then.These logistics mix mutually, and wash away solvent with catalyzer, enter into reactor by single filling line afterwards.

After with fine motion flowmeter survey solution density, in the reactor product pipeline, add catalyst deactivation agent (mixing water) to stop polyreaction with solvent.Can add other polymeric additive with the catalyst deactivation agent.Static mixer on the production line can be dispersed in catalyst deactivation agent and additive in the reactor discharging logistics.This logistics enters in the well heater behind the reactor then, and this well heater can provide additional energy to remove solvent with flash distillation.Flash distillation takes place when the reactor post-heater is left in this logistics, and at this moment the pressure on the reactor pressure control valve is reduced to about 250mm absolute pressure by 475psig (3275KPa).Polymkeric substance after this flash distillation enters in the hot-oil jacket devolatilization device.In the devolatilization device, removed in the polymkeric substance about 85% fugitive constituent.Fugitive constituent leaves from the top of devolatilization device.This logistics of condensing of spent glycol chuck interchanger is aspirated with vacuum pump, is discharged into then in ethylene glycol chuck solvent and the styrene/ethylene separation vessel.Solvent and vinylbenzene are removed from the container bottom, and ethene is then removed from top.Use fine motion mass flow meter measurement ethylene streams, analyze its composition then.By measuring the ethene of discharging and calculating dissolved gases amount in solvent/vinylbenzene liquid stream, calculate the transformation efficiency of ethene.The polymer pump of using toothed gear pump to separate in the devolatilization device is delivered in the ZSK-30 twin screw devolatilization vacuum-extruder.Dry polymeric leaves this forcing machine with single wire-form.This line material is drawn by water-bath to cool off.Blow away excess water on this line material with air, be cut into particle with line material cutting unit then.

Table 3 has gathered various catalyzer, promotor and the processing condition that are used for preparing the various single ethylene styrene interpolymers of embodiment 6-8.

Table 3

Embodiment	Embodiment 6	Embodiment 7	Embodiment 8
				Temperature of reactor, ℃	83.2	81.4	79.8
Solvent flow rate, 1b/hr (kilogram/hour)	37.0(16.8)	37.0(16.8)	41.0(18.6)
				The ethene flow velocity, 1b/hr (kilogram/hour)	1.9(0.9)	1.9(0.9)	2.2(1.0)
Hydrogen flow rate, 1b/hr (kilogram/hour)	1.3(0.6)	10(4.5)	20(9.1)
				The vinylbenzene flow velocity, 1b/hr (kilogram/hour)	7.1(3.2)	7.0(3.2)	21.0(9.5)
C2H4 transformation efficiency percentage ratio	97.0	96.4	97.4
				Promotor	FABb	FABb	FABb
The B/Ti ratio	3.5	3.5	3.5
				The MMAOC/Ti ratio	3.5	3.5	6.0

^aCatalyzer is that [N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-1,5,6,7-tetrahydrochysene-s-cyclopenta indenes-1-yl] silanamines close (2-)-N]-the dimethyl titanium.

^bFAB is three (pentafluorophenyl group) borine.

^cModified methyl aluminium alkane can have been bought with HMAO-3A from Akzo Nobel.

In order to measure oxygen permeability, sample was melted 3 minutes down at 190 ℃, under 190 ℃, other compression moulding is 2 minutes under the pressure of 20000 pounds (9072 kilograms) then.Subsequently, melting material is carried out quenching in the press of equilibrium at room temperature.

The oxygen permeability of gained film uses wet test gas according to ASTM D 3985-95, under 25 ℃, measures on the OXTRAN2/20 system.Oxygen concentration is 21%.Data are proofreaied and correct to 100% oxygen concentration.These data are summarized in table 4.These results show, when the minimum oxygen permeability value appears at middle styrene content in this interpolymer, rather than when low or high-phenylethylene content.

Table 4

Embodiment	Styrene content (molecular fraction)	The O2 transmission rate (centimetre 3Mil/100 inch 2It normal atmosphere O 2) (centimetre 3/ centimetre sky MPa)
			Embodiment 1	42.1	125*(0.49)
Embodiment 2	30.3	90.3(0.35)
			Embodiment 3	43.6	72*(0.28)
The contrast experiment 1	9.2	498(1.93)
			The contrast experiment 2	17.1	520(2.02)
The contrast experiment 3	0	2412(9.37)
			The contrast experiment 4	N/A	3340(12.98)
The contrast experiment 5	100	306(1.19)

* the mean value of 2 numbers.

The tension strain response rate of sample is measured as follows.Use ASTM 1708 to prepare sample, then in INSTRON 1145 drawing machines with 100%/minute strain rate be out of shape up to breaking.After 24 hours, measure the distance between the mark zone on this sample, then and the distortion before same zone between distance compare.This difference is represented with percentage ratio, regards the tension strain response rate as.These data are summarized in table 5.

Tensile stress relaxation is measured as follows.Use Instron 1145 drawing machines to assess uniaxial extension stress relaxation.With the compression moulding film (about 20 mils (0.51 millimeter) are thick) of 10 mils (0.25 millimeter) gauge length with 20 minutes ^-1Strain rate is deformed into 50% strain rate.Monitoring keeps the required power of 50% elongation in 10 minutes.The numerical value of stress relaxation is defined as Sr, this percentage ratio=(f _i-f _f/ f _i) * 100, wherein f _iBe initial force, f _fBe end of a period power.These data are summarized in table 5.

Xiao A hardness is measured according to ASTM-D240 under 23 ℃.These data are summarized in table 5.

The result of table 5 shows that the optimum value of tension strain answer and stress relaxation appears in the specific interpolymer styrene content scope (about 30% mole).These data show that also the Xiao A hardness of this material also changes along with the styrene content of interpolymer.

Claims (27)

1. sealing, it comprises a kind of oxygen transmission coefficient under 25 ℃ and is lower than 300 centimetres ³Mil/100 inch ²(1.2 centimetres in it normal atmosphere ³/ centimetre sky MPa) polymer composition, wherein said polymer composition comprises:

A) at least a random basically interpolymer, it comprises:

(1) the 24-65% mole derived from following polymer of monomers unit:

(ⅰ) at least a vinylidene aromatic monomer, or

(ⅱ) at least a hindered aliphatic or cycloaliphatic vinylidene monomer, or

(ⅲ) array configuration of at least a aromatics vinylidene monomer and at least a hindered aliphatic or cycloaliphatic vinylidene monomer and

(2) the 35-76% mole derived from least a C _2-20The polymer unit of alpha-olefin; Or

B) a kind of blend, it comprises:

(1) the component A of 35-99% weight (based on the gross weight of B component 1 and B2); With

(2) polymkeric substance of at least a non-component A of 1-65% weight (based on the gross weight of B component 1 and B2); With

C) at least a filler of 0-90% weight (based on the gross weight of component A, B and C).

2. according to the sealing of claim 1, its oxygen transmission coefficient under 25 ℃ is lower than 200 centimetres ³Mil/100 inch ²(0.8 centimetre in it normal atmosphere ³/ centimetre sky MPa), and for 100%/minute strain rate under carry out the strained sample, its tension strain response rate is greater than 70%, and wherein said polymer composition comprises:

A) at least a random basically interpolymer, it comprises:

(1) the 27-46% mole derived from following polymer of monomers unit:

(ⅰ) the described vinylidene aromatic monomer of the representative of following structural formula:

R wherein ¹Be selected from hydrogen atom and contain the alkyl of 3 or lower carbon atom, and 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; Or

(ⅱ) hindered aliphatic or the cycloaliphatic vinylidene monomer of representing by following general formula:

A wherein ¹For containing the sterically hindered big aliphatic series or the cyclic aliphatic substituting group of 20 carbon atoms at the most, R ¹Be selected from hydrogen atom and the alkyl that contains 1 to 4 carbon atom, be preferably hydrogen atom or methyl; Each R ²Be independently selected from hydrogen atom and the alkyl that contains 1 to 4 carbon atom, be preferably hydrogen atom or methyl; Or R ¹And A ¹Also can constitute member ring systems; With

(2) polymer unit derived from described alpha-olefin of 54-73% mole, described alpha-olefin comprises ethene, or at least a in ethene and propylene, butene-1,4-methyl-1-pentene, hexene-1 or the octene-1; Or

B) described blend component B, it comprises:

(1) the component A of 40-97% weight (based on the gross weight of B component 1 and B2); With

(2) the described polymkeric substance that removes component A of 60-3% weight (based on the gross weight of B component 1 and B2), comprise one or more following materials: polystyrene, high-impact polystyrene, polyvinyl chloride, at least a multipolymer in vinylbenzene and vinyl cyanide, methacrylonitrile, maleic anhydride or the alpha-methyl styrene, aliphatic C ₂-C ₂₀The homopolymer of alpha-olefin and multipolymer, the multipolymer of ethene and vinyl-acetic ester, the chlorination alpha-olefinic polymer, styrene butadiene (SB), styrene-isoprene (SI), styrene-butadiene-styrene (SBS), styrene-isoprene-phenylethene (SIS) or styrene-ethylene/butylene-styrene (SEBS) segmented copolymer; Or containing the random basically alpha-olefin/vinylidene/interpolymer that is lower than 24% mole of following polymer unit, wherein said polymer unit is derived from the array configuration of at least a vinylidene aromatic monomer or at least a hindered aliphatic or cycloaliphatic vinylidene monomer or at least a vinylidene aromatic monomer and at least a hindered aliphatic or cycloaliphatic vinylidene monomer; With

C) described filler component C, its amount comprises talcum, lime carbonate, three hydrated alumina, carbon black, glass fibre, clay, feldspar, silica or glass, fused silica, alumina, magnesium oxide, magnesium hydroxide, weisspiessglanz, zinc oxide, barium sulfate, pure aluminium silicate, Calucium Silicate powder, titanium dioxide, glass microsphere, chalk or its any mixture for 0-80% weight (based on the gross weight of component A, B and C).

3. according to the sealing of claim 1, its oxygen transmission coefficient under 25 ℃ is lower than 150 centimetres ³Mil/100 inch ²(0.6 centimetre in it normal atmosphere ³/ centimetre sky MPa), and for 100%/minute strain rate under carry out the strained sample, its tension strain response rate is greater than 85%, and wherein said polymer composition comprises:

A) at least a random basically interpolymer, it comprises:

(1) the 29-37% mole derived from following polymer of monomers unit:

ⅰ) described vinylidene aromatic monomer, comprise vinylbenzene, alpha-methyl styrene, neighbour-,-and p-methylstyrene, ring on halogenated styrenes; Or

ⅱ) described hindered aliphatic or cycloaliphatic vinylidene monomer comprise 5-ethidine-2-norbornylene or 1-vinyl cyclohexene, 3-vinyl cyclohexene and 4 vinyl cyclohexene;

(2) polymer unit derived from described alpha-olefin of 63-71% mole, described alpha-olefin comprises ethene, or at least a in ethene and propylene, butene-1,4-methyl-1-pentene, hexene-1 or the octene-1; Or

B) described blend component B, it comprises:

(1) the component A of 40-95% weight (based on the gross weight of B component 1 and B2); With

(2) the described polymkeric substance that removes component A of 60-5% weight (based on the gross weight of B component 1 and B2) comprises one or more following materials: polystyrene, high-impact polystyrene, polyvinyl chloride, aliphatic C ₂-C ₂₀The homopolymer of alpha-olefin and multipolymer, the multipolymer of ethene and vinyl-acetic ester, styrene butadiene (SB), styrene-isoprene (SI), styrene-butadiene-styrene (SBS), styrene-isoprene-phenylethene (SIS) segmented copolymer, or containing the random basically alpha-olefin/vinylidene/interpolymer that is lower than 24% mole of following polymer unit, wherein said polymer unit is derived from least a vinylidene aromatic monomer, or at least a hindered aliphatic or cycloaliphatic vinylidene monomer, or the array configuration of at least a vinylidene aromatic monomer and at least a hindered aliphatic or cycloaliphatic vinylidene monomer; With

C) described filler component C, its amount comprises talcum, lime carbonate, three hydrated alumina, barium sulfate, titanium dioxide or its any mixture for 0-70% weight (based on the gross weight of component A, B and C).

4. according to the sealing of claim 3, wherein said polymer composition comprises the described random basically interpolymer of 100% weight, and wherein said component A1 is vinylbenzene, and component A2 is an ethene.

5. according to the sealing of claim 3, wherein said polymer composition comprises the described random basically interpolymer of 100% weight, and wherein said component A1 is a vinylbenzene, and component A2 is an at least a interpolymer in ethene and propylene, 4-methyl-1-pentene, butene-1, hexene-1 or the octene-1.

6. according to the sealing of claim 1, wherein said random basically interpolymer is crosslinked.

7. according to the sealing of claim 1, its form is packing ring, container cover lining or secluding film.

8. sealing system that comprises the sealing of claim 1.

9. sealing system according to Claim 8, its form is a container cover.

10. container closure of plastic, it comprises:

(a) plastic basis material wall; With

(b) sealed liner, wherein said lining is extruded in described substrate walls inside, cutting and compression moulding, and described lining comprises the sealing of claim 1.

11. a metallic container cover, it comprises:

(a) metal base wall; With

(b) sealed liner, wherein said lining is extruded in described substrate walls inside, cutting and compression moulding, and described lining comprises the sealing of claim 1.

12. according to the container closure of plastic of claim 10, wherein said sealed liner is a kind of foam materials.

13. according to the metallic container cover of claim 11, wherein said sealed liner is a kind of foam materials.

14. according to the container closure of plastic of claim 10, wherein said sealed liner is extruded into a kind of sheet material, and cuts out annular disc by described sheet material, can obtain preformed lid like this, adhesion or heat setting are to the inside of described substrate walls (a) subsequently.

15. according to the metallic container cover of claim 11, wherein said sealed liner is extruded into a kind of sheet material, and cuts out annular disc by described sheet material, can obtain preformed lid like this, adhesion or heat setting are to the inside of described substrate walls (a) subsequently.

16. according to the container closure of plastic of claim 14, wherein said sealed liner is a kind of foam materials.

17. according to the metallic container cover of claim 15, wherein said sealed liner is a kind of foam materials.

18. bottle cap by thermoplastic resin molded one-tenth, described bottle cap comprises the sealing ply that can produce the sealing interlock when described bottle cap affacts on the bottle, described sealing ply comprises a kind of polymer composition, and the oxygen transmission coefficient of this polymer composition under 25 ℃ is lower than 200 centimetres ³Mil/100 inch ²(0.8 centimetre in it normal atmosphere ³/ centimetre sky MPa), and for 100%/minute strain rate under carry out the strained sample, its tension strain response rate is greater than 70%, and wherein said polymer composition comprises:

A) at least a random basically interpolymer, it comprises:

(1) the 27-46% mole derived from following polymer of monomers unit:

(a) at least a vinylidene aromatic monomer, or

(b) at least a hindered aliphatic or cycloaliphatic vinylidene monomer, or

(c) array configuration of at least a aromatics vinylidene monomer and at least a hindered aliphatic or cycloaliphatic vinylidene monomer and

(2) the 54-73% mole derived from least a C _2-20The polymer unit of alpha-olefin; Or

B) a kind of blend, it comprises:

(1) the component A of 35-99% weight (based on the gross weight of B component 1 and B2); With

(2) polymkeric substance of at least a non-component A of 1-65% weight (based on the gross weight of B component 1 and B2); With

C) based on the gross weight of component A, B and C, at least a filler of 0-80% weight.

19. bottle cap that is moulded by metal pattern, described bottle cap comprises the sealing ply that can produce the sealing interlock when described bottle cap affacts on the bottle, described sealing ply comprises a kind of polymer composition, and the oxygen transmission coefficient of this polymer composition under 25 ℃ is lower than 200 centimetres ³Mil/100 inch ²(0.8 centimetre in it normal atmosphere ³/ centimetre sky MPa), and for 100%/minute strain rate under carry out the strained sample, its tension strain response rate is greater than 70%, and wherein said polymer composition comprises:

A) at least a random basically interpolymer, it comprises:

(1) the 27-46% mole derived from following polymer of monomers unit:

(a) at least a vinylidene aromatic monomer, or

(b) at least a hindered aliphatic or cycloaliphatic vinylidene monomer, or

(c) array configuration of at least a aromatics vinylidene monomer and at least a hindered aliphatic or cycloaliphatic vinylidene monomer and

(2) the 54-73% mole derived from least a C _2-20The polymer unit of alpha-olefin; Or

B) a kind of blend, it comprises:

(1) the component A of 35-99% weight (based on the gross weight of B component 1 and B2); With

(2) polymkeric substance of at least a non-component A of 1-65% weight (based on the gross weight of B component 1 and B2); With

C) at least a filler of 0-80% weight (based on the gross weight of component A, B and C).

20. according to the sealing of claim 1, its form is a film.

21. according to the sealing of claim 1, its form is a foam materials.

22. according to the sealing of claim 21, wherein said foam materials comprises crosslinked random basically interpolymer.

23. one kind comprises two-layer at least multilayer film, one deck at least of wherein said layer comprises a kind of oxygen transmission coefficient under 25 ℃ and is lower than 300 centimetres ³Mil/100 inch ²(1.2 centimetres in it normal atmosphere ³/ centimetre sky MPa) polymer composition, described polymer composition comprises:

A) at least a random basically interpolymer, it comprises:

(1) the 24-65% mole derived from following polymer of monomers unit:

(a) at least a vinylidene aromatic monomer, or

(b) at least a hindered aliphatic or cycloaliphatic vinylidene monomer, or

(c) array configuration of at least a aromatics vinylidene monomer and at least a hindered aliphatic or cycloaliphatic vinylidene monomer and

(2) the 35-76% mole derived from least a C _2-20The polymer unit of alpha-olefin; Or

B) a kind of blend, it comprises:

(1) the component A of 35-99% weight (based on the gross weight of B component 1 and B2); With

(2) polymkeric substance of at least a non-component A of 1-65% weight (based on the gross weight of B component 1 and B2); With

C) based on the gross weight of component A, B and C, at least a filler of 0-80% weight;

And wherein at least one other layer comprises the polymer composition except component A or B.

24. according to the bottle cap of claim 18, wherein said sealing ply comprises the multilayer film of claim 23.

25. according to the bottle cap of claim 19, wherein said sealing ply comprises the multilayer film of claim 23.

26. sealing system that comprises the sealing of claim 6.

27. sealing system that comprises the sealing of claim 22.

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