CN1128839C - Blends containing interpolymer of alpha-olefin - Google Patents

Abstract

The present invention relates to a blend containing polymeric materials, which comprises about 1 to 99% by weight of about 1 to 65% by mol of at least one ethenediyl aromatic hydrocarbon monomer, or at least one vinylidene monomer of the steric hindrance fatty group or the ring grease group, or a mixture of at least one aromatic hydrocarbon vinylidene monomer and at least one vinylidene monomer of the steric hindrance fatty group or the ring grease group, about 35 to 99% by mol of at least one copolymer prepared from the monomer components of at least one fatty group alpha-olefin containing about 2 to 20 carbon atoms, and about 1 to 99% by weight of homopolymer or copolymer of at least one or multiple ethenediyl aromatic hydrocarbon monomers and/or one or multiple steric hindrance fatty group vinylidene monomers. Compared with the single polymer phase of the blend, the performance of the blend is improved, and the materials whose process performance is improved and temperature range kept by the performance is expanded are provided.

Description

The blend that contains alpha-olefin interpolymer

The present invention relates to the alpha-olefin/interpolymer of steric hindrance vinylidene monomer and the blend of vinyl aromatic polymer; Their foams and the foams that only obtain by the interpolymer of alpha-olefin/steric hindrance vinylidene monomer.The selection of blend components and their ratio should be able to provide excellent performance and/or processibility.

By the material of the random resulting common species of interpolymer of being essentially of alpha-olefin/steric hindrance vinylidene monomer with comprise that for example the material of the interpolymer of alpha-olefin/vinylidene aromatic monomer is known by those skilled in the art, they can have bigger variation and make it be applicable to different Application Areass aspect the structural performance of material and performance perameter, for example as U.S. Pat No.5,460, the 818 described compatilizers that can be used as polyethylene and polystyrene blend.

(see by described concrete aspects such as D ' Anniello Applied polymer science is assorted Will (Journal of Applied Polymer Science), the 58th volume, 1701-1706 page or leaf, nineteen ninety-five) and be that this type of interpolymer has good elasticity and energy waste characteristic.On the other hand, some interpolymer can be used for adhesive composition, and as the U.S. Pat No.5 of petrochemical industry company limited of Mitsubishi invention, 244,996 is described.

Although these multipolymers itself have many purposes, industry member improves their applicability always at searce way.The raising of this applicability can realize by adding additive, but people more wish to develop some technology with their processibility or performance of raising under the situation that does not need additive, or than adding the obtainable performance raising of additive institute further improvement are arranged.

U.S. Pat No.3,117,945 (W.F.Gorham) disclose so-called " gloss " styrene/ethylene multipolymer, and it has the styrene copolymerized unit of at least 20% (weight), according to the difference of the solvent of selecting for use, it can become several different multipolymer fractions with the solvent classification.

Park etc. disclose a kind of toughness of monomeric homopolymer of monovinylidene aromatic or interpolymer and method of solvent resistance of improving in WO 95/27755, it is by with itself and olefin polymer (as polyethylene or ethylene/octene) blend.But because the uncompatibility of these two kinds of resins needs to use compatilizer, the Park instruction says that compatilizer can be the false random copolymer of aliphatics alpha-olefin and vinylidene aromatic monomer.

Bradfute etc. disclose multilayer film in WO 95/32095, one deck at least wherein is the ethylene/styrene multipolymer.But Bradfute etc. are the basic random copolymer of vinylidene aromatic monomer and 'alpha '-olefin monomers and monomeric homopolymer of monovinylidene aromatic or interpolymer not openly BlendAny example.

Lu etc. in CA 22:240559V, disclose styrene-ethylene copolymers (S-E) and with blends of polystyrene (wherein S-E content is 0-10% (weight)), and be taught under the S-E content of about 10% (weight), the elongation at break of these blends reaches maximum value.

Ikuya etc. disclose cushioning material in JP 08142243, its preparation as described below: at the foam material of the partially filled ethylene-styrene copolymer of epidermis of thermoplastic resin, and this epidermis part is in aggregates with the foams bonding.

But, still need to provide performance characteristic to be better than the material based on alpha-olefin/vinylidene aromatic monomer interpolymer of unmodified polymer, this will further enlarge the application of the interesting material of this class.

The present invention relates to contain the blend of following polymers material:

(A) at least a interpolymer of 35 to 99% (weight), by containing following monomeric monomer component preparation:

(a) at least a vinylidene aromatic monomer of (1) 1 to 65% (mole), or (b) at least a hindered aliphatic vinylidene monomer, or (c) at least a vinylidene aromatic monomer and at least a hindered aliphatic vinylidene monomer combination and

At least a aliphatics alpha-olefin of (2) 35 to 99% (mole) with 2-20 carbon atom; With

(B) 1 to 65% (weight)

(1) homopolymer of at least a one or more vinylidene aromatic monomers, or

(2) interpolymer of at least a one or more vinylidene aromatic monomers and/or one or more hindered aliphatic vinylidene monomers, or

(3) also contain at least a in (1) or (2) of impact modifier, or

(4) combination of two or more (1), (2) or (3) arbitrarily.

The present invention also relates to foamable composition, contain:

(I) at least a whipping agent; With

(I) blend of at least a interpolymer or interpolymer, contain:

(A) at least a interpolymer of 1 to 100% (weight), by containing following monomeric monomer component preparation:

(a) at least a vinylidene aromatic monomer of (1) 1 to 65% (mole), or (b) at least a hindered aliphatic vinylidene monomer, or (c) at least a vinylidene aromatic monomer and at least a hindered aliphatic vinylidene monomer combination and

At least a aliphatics alpha-olefin of (2) 35 to 99% (mole) with 2-20 carbon atom; With

(B) at least a one or more vinylidene aromatic monomers of 0 to 95.5% (weight) and/or the homopolymer of one or more hindered aliphatic vinylidene monomers, or the interpolymer of one or more polymerisable ethylenically unsaturated monomers different of existing of at least a one or more vinylidene aromatic monomers and/or one or more hindered aliphatic vinylidene monomers and can selecting as required with vinylidene aromatic monomer or hindered aliphatic vinylidene monomer.

But blend of the present invention and foam material can " contain " two or more said this class interpolymer arbitrarily herein, also can " be made of (they) basically " or " being made of (they) ".Equally, interpolymer can contain two or more said polymerisable monomer arbitrarily, also can " be made of (they) basically " or " being made of (they) ".

These blends are improved on one or more polymer performances, for example mechanical property and/or melt processable, but be not limited to this.

Here said " interpolymer " is meant a kind of polymkeric substance, and wherein at least two kinds of different monomers form this interpolymer by polymerization.

" random basically " speech, here be used for by alpha-olefin and vinylidene aromatic monomer or hindered aliphatic vinylidene monomer and obtain be essentially random interpolymer, the monomeric distribution that is meant said interpolymer can be described with Bai Nuli statistical model or one-level or secondary Markovian statistical model, referring to " polymer sequence is measured, the 13C nuclear magnetic resonance method " (J.C.Randall, Polymer Sequence Determination, Carbon-13 NMRMethod, Academic Press New York, 1977, the 71-78 pages or leaves).The random interpolymer of being essentially that is obtained by 'alpha '-olefin monomers and vinylidene aromatic monomer preferably is no more than 15% containing the total amount that surpasses the vinylidene aromatic monomer that is contained in the block of 3 vinylidene aromatic monomers.Especially, interpolymer be not with height complete with or be constitutional features with the legislate structure.In other words in being essentially the carbon-13 nmr of random interpolymer, be no more than 75% of the total peak area of main chain mesomethylene carbon and methine carbon with the main chain mesomethylene carbon of representing meso diad sequence or racemize diad sequence and the corresponding peak area of methine carbon.

As long as the gap of at least two units is arranged between any Schwellenwert and any maximum, any quantized numerical value of being mentioned here be included under the unit increment from Schwellenwert to all numerical value between the maximum.For instance, if component concentration that provides or processing parameter are variable as temperature, pressure, time, for example from 1 to 90, preferred 20 to 80, particularly 30 to 70, be meant that in fact for example 15 to 85,22 to 68,43 to 51,30 to 32 numerical range is specifically listed in this manual.For less than 1 numerical value, the unit of this moment then suitably should be 0.0001,0.001,0.01 or 0.1.These are the example of those numerical value of clear and definite indication, for cited from Schwellenwert to all possible combinations of values between the maximum, should think that this specification sheets clearly specifically enumerates in an identical manner.

Be suitable for the interpolymer of component (A) as preparation blend of the present invention comprise by one or more 'alpha '-olefin monomers and one or more vinylidene aromatic monomers and/or one or more hindered aliphatic vinylidene monomers carry out polymerization and obtain be essentially random interpolymer, but be not limited to this.

The 'alpha '-olefin monomers that is suitable for for example comprises that those have 2 to 20, and is preferred 2 to 12, particularly the 'alpha '-olefin monomers of 2 to 8 carbon atoms.The monomer of particularly suitable has ethene, propylene, butene-1,4-methyl-1-pentene, hexene-1 and octene-1.

The vinylidene aromatic monomer that is suitable for comprises, for example by those monomers of following molecular formula I representative: Formula I

R wherein ¹Be selected from H and alkyl, be preferably H or methyl with 1 to 4 carbon atom; Each R ²Be selected from H and alkyl independently of one another, be preferably H or methyl with 1 to 4 carbon atom; Ar is phenyl or has 1 to 5 and be selected from halogen, C _1-4Alkyl and C _1-4The substituent phenyl of haloalkyl; With the value of n be 0 to 6, be preferably 0 to 2, particularly 0.The monomeric example of monovinylidene aromatic has vinylbenzene, Vinyl toluene, alpha-methyl styrene, t-butyl styrene and chlorostyrene, comprises the isomer that these compounds are all.This class monomer of particularly suitable comprises the derivative that vinylbenzene and its low alkyl group or halogen replace.Preferred monomer comprises vinylbenzene, alpha-methyl styrene and low alkyl group or the nuclear substituted styrene derivatives of benzene, for example adjacent, and p-methylstyrene, ring by halogenated vinylbenzene, to Vinyl toluene or their mixture.Particularly preferred aromatic hydrocarbons monovinylidene monomer is a vinylbenzene.

" hindered aliphatic or cycloaliphatic vinylidene monomer " but a speech is meant the vinylidene monomer by the represented addition polymerization of following molecular formula II:

Formula II

A wherein ¹For having the sterically hindered big aliphatics substituting group of 20 carbon atoms at the most, R ¹Be selected from H and alkyl, be preferably H or methyl with 1 to 4 carbon atom; Each R ²Be selected from H and alkyl independently of one another, be preferably H or methyl with 1 to 4 carbon atom; Or R ¹And A ¹Also can constitute member ring systems." sterically hindered big " speech is meant and has this substituent monomer to carry out the speed of addition polymerization under the Ziegler-Natta of standard polymerizing catalyst generally much smaller than the speed of vinyl polymerization.Preferred hindered aliphatic or cycloaliphatic vinylidene monomer have the undersaturated carbon atom of olefinic for those one of them be the monomer that three grades or level Four replace.The substituent example of this class comprises deriveding group, the tertiary butyl or the norcamphyl that alkyl or aryl replaces on cycloaliphatic radical such as cyclohexyl, cyclohexenyl, cyclooctene base or their ring.Particularly preferred hindered aliphatic or cycloaliphatic vinylidene compound are the various isomer of vinyl substituted derivative on the ring of vinyl cyclohexane and tetrahydrobenzene and substituted cyclohexene, and 5-ethylidene-2-norbornene, particularly vinyl cyclohexane.

The interpolymer of one or more 'alpha '-olefin monomers 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 contain at least a vinylidene aromatic monomer of 1 to 65% (mole), preferred 5 to 60% (moles), particularly 10 to 55% (moles) and/or hindered aliphatic or cycloaliphatic vinylidene monomer and 35 to 99% (moles), at least a aliphatics alpha-olefin with 2 to 20 carbon atoms of preferred 40 to 95% (moles), particularly 45 to 90% (moles) usually.

The number-average molecular weight of these interpolymers (Mn) is preferably 5000 to 1000000 usually greater than 1000, and particularly 10000 to 500000.

Blend provided by the invention, the molecular weight of its interpolymer component is that whole molecular weight and composition distribution should be able to provide improved blend performance or processibility with the choice criteria that composition distributes.

Blend of the present invention contains 1 to 99% (weight), preferred 3 to 97% (weight), the particularly component of 5 to 95% (weight) (A) and 99 to 1% (weight), preferred 97 to 3% (weight), the particularly component of 95 to 5% (weight) (B).Contain 35 to 99% (weight), preferred 40 to 97% (weight), the particularly component of 60 to 95% (weight) (A) and 65 to 1% (weight), preferred 60 to 3% (weight), the particularly blend of the component of 40 to 5% (weight) (B) at preferred especially those in some cases, these blends are compared less than those blends of 35% (weight) with component (A) content has improved performance.

When preparation was essentially random interpolymer and is component (A), as following will the narration, because homopolymerization may take place vinylidene aromatic monomer, the homopolymer that therefore has some atactic vinylidene aromatic monomers generated.The general polymerization temperature is high more, and the amount of the homopolymer of generation is just many more.The existence of vinylidene aromatic monomer homopolymer generally can not influence effect of the present invention, therefore is to allow its existence.The homopolymer of vinylidene aromatic monomer can be as required be separated from interpolymer by the method for extracting, and for example optionally precipitates from their solution with one of them precipitation agent of interpolymer or vinylidene aromatic monomer homopolymer.The homopolymer of the preferred vinylidene aromatic monomer of the present invention is no more than 20% of interpolymer gross weight, particularly less than 15%.

Being essentially random interpolymer can modify by typical graft, hydrogenation, the functionalized or known reaction of other those skilled in the art.Polymkeric substance can carry out sulfonation or chlorination to make functionalized derivative easily according to existing technology.

Being essentially random interpolymer can carry out polymerization and prepare in the presence of metallocenes or how much limited catalyzer and promotor, as James C.Stevens etc. at EP-A-0,416,815, Francis J.Timmers is in U.S. Patent No. 5, described in 703,187.The preferred operational condition of this polyreaction is that pressure is from 1 normal atmosphere to 3000 normal atmosphere, and temperature is-30 ℃ to 200 ℃.Under the temperature on the monomer auto-polymerization temperature separately, carry out polyreaction and remove the homopolymer product that unreacted monomer may cause some radical polymerizations to generate.

The example of the catalyzer that is suitable for and preparation are essentially the method for random interpolymer in EP-A-514 828 and U.S. Patent No. 5,055,438,5,057,475,5,096,867,5,064,802,5,132,380,5,189,192,5,321,106,5,347,024,5,350,723,5,374,696,5,399,635,5,470,993,5, in 703,187 and 5,721,185 description is arranged also.

Alpha-olefin/vinylidene aromatic monomer be essentially random interpolymer also can be according to (W.R.Grace ﹠amp such as J0hn G.Bradfute; Co.) at WO 95/32095, R.B.Pannell (Exxon chemical patent company) WO 94/00500 and " plastics technology " ( Plastics Technology) September in 1992 the 25th page of described method be prepared.

The same WO 98/09999 disclosed random interpolymer that is essentially that contains at least a alpha-olefin/binyl aromatic monomer/vinyl aromatic monomer/alpha-olefin four unit group sequences in addition that is suitable for.These interpolymers contain peak intensity other signal bigger 3 times than noise peak.The chemical shift of these signals is between 43.75 to 44.25ppm and 38.0 to 38.5ppm.More particularly, the chemical shift of main peak is 44.1,43.9 and 38.2ppm.(Attached Proton Test APT) shows that chemical shift belongs to methine carbon at 43.75 to 44.25ppm signal to the nmr experiments of subsidiary proton, and chemical shift belongs to mesomethylene carbon at 38.0 to 38.5ppm signal.

For the chemical shift of the carbon-13 nmr of determining described interpolymer, adopt following step and condition.Contain 1,2 of 0.10 mole of tri acetylacetonato chromium with 50% (volume) deuterium for sym.-tetrachloroethane and 50% (volume), the mixed solvent of 4-trichlorobenzene prepares the polymers soln of 5-10% (weight).The nucleus magnetic resonance service temperature is 130 ℃, adopts the counter-rotating frame sequence (inverse gated decoupling sequence) of uncoupling, 90 ° of pulse widths and more than or equal to 5 seconds pulse relaxation.With the isolated methylene signals of polymkeric substance is that 30.000ppm calibrates spectrogram.

New signal is be sure of to belong to follows the sequence of inserting at least one alpha-olefin and forming closely in the front and back of two connected head-to-tail vinyl aromatic monomers, ethylene/styrene/styrene/ethylene four unit groups for example, wherein styrene monomer only inserts in this Unit four group in 1,2 mode (connected head-to-tail mode).Those skilled in the art is understood for containing vinyl aromatic monomer outside the vinylbenzene and four unit groups of the alpha-olefin outside the ethene, this alpha-olefin/binyl aromatic monomer/vinyl aromatic monomer/alpha-olefin four unit groups will have similar 13C nuclear magnetic resonance peak, but small difference will be arranged in chemical shift.

These interpolymers are under about-30 ℃ to 250 ℃ temperature, and in the presence of those catalyzer shown in following molecular formula, and selectivity is used but the polyreaction preparation preferably carried out in the presence of active cocatalyst as required:

Wherein each Cp is the cyclopentadienyl with the replacement of π key and M bonding independently of one another; E is C or Si; M is an IV family metallic element, is preferably Zr or Hf, particularly Zr; Each R independently of one another for H, contain 30 at the most, preferred 1 to 20, particularly alkyl, sila alkyl or the silicon alkyl alkyl of 1 to 10 carbon atom or Siliciumatom; Each R ' independently of one another for H, halogen, contain 30 at the most, preferred 1 to 20, particularly alkyl,-oxyl, sila alkyl, the silicon alkyl alkyl of 1 to 10 carbon atom or Siliciumatom, or two R ' bases can constitute C jointly _1-10The 1,3-butadiene that alkyl replaces; M is 1 or 2.Especially, the cyclopentadienyl of the replacement of Shi Yonging comprises those groups shown in the following molecular formula:

Wherein each R independently of one another for H, contain 30 at the most, preferred 1 to 20, particularly alkyl, sila alkyl or the silicon alkyl alkyl of 1 to 10 carbon atom or Siliciumatom, or two R bases can constitute the divalence deriveding group of this group jointly.Each R base is independently of one another for (to comprise if suitable, whole isomer) H, methyl, ethyl, propyl group, butyl, amyl group, hexyl, benzyl, phenyl or silylation, or (if suitable) two R bases couple together and constitute a condensed ring system, as indenyl, fluorenyl, tetrahydro indenyl, tetrahydrofluorenyl or octahydrofluorenyl, or the deriveding group of the replacement of these condensed ring systems.

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 their arbitrary combination.

The existing in the literature report of other preparation method of interpolymer blend components of the present invention (A).Longo and Grassi ( Macromolecular chemistry (Makromol.Chem.), nineteen ninety, the 191st volume, 2387-2396 page or leaf) and D ' Anniello etc. ( Journal of applied, nineteen ninety-five, the 58th volume, 1701-1706 page or leaf) reported and adopted based on methylaluminoxane (MAO) and cyclopentadienyl titanous chloride (CpTiCl ₃) catalyst system prepare ethylene-styrene copolymer.Xu and Lin ( Polymkeric substance is preprinted collection, American Chemical Society's polymerization materialization The credit meeting (Polvmer Preprints, Am.Chem.Soc., Div.Polym.Chem.), 1994, the 35th volume, 686,687 pages) report employing TiCl ₄/ NdCl ₃/ Al (iBu) ₃Catalyzer carries out the random copolymers of copolymerization with preparation vinylbenzene and propylene.Lu etc. ( Using polymer section Learn magazine, 1994, the 53rd volume, 1453-1460 page or leaf) report employing 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 the interpolymer of alpha-olefin/binyl aromatic monomer such as propylene/styrene and butylene/styrene interpolymer has description.

Comprise the homopolymer of single vinylidene aromatic monomer as the polymkeric substance of the vinylidene aromatic monomer of component (B) in the present invention or by the prepared interpolymer of one or more vinylidene aromatic monomers.Particularly suitable is the monovinylidene aromatic monomer.

The monovinylidene aromatic polymers that is fit to that adopts in the component (B) of blend of the present invention and/or swellable compositions comprises monomeric homopolymer of one or more monovinylidene aromatics or interpolymer, or the monomeric interpolymer of one or more monovinylidene aromatic monomers and one or more copolymerizations with it except that the aliphatics alpha-olefin.The monovinylidene monomer that is suitable for can be by shown in the following molecular formula:

R wherein ¹Be selected from H and have and be phenyl or have 1 to 5 and be selected from halogen, C smaller or equal to the alkyl of 3 carbon atoms and Ar _1-4Alkyl and C _1-4Substituent phenyl in the haloalkyl.The monomeric example of monovinylidene aromatic comprises vinylbenzene, to Vinyl toluene, alpha-methyl styrene, t-butyl styrene and chlorostyrene, comprise the isomer that these compounds are all.For monovinylidene aromatic polymer of monomers of the present invention, vinylbenzene is particularly preferred monovinylidene aromatic monomer.

The example of the copolymerizable comonomer except that the monovinylidene aromatic monomer comprises C ₄-C ₆Conjugated diolefine, particularly divinyl or isoprene, N-phenylmaleimide, N-allyl group maleimide, acrylamide, olefinically unsaturated nitriles monomer such as vinyl cyanide and methacrylonitrile, unsaturated single acid of olefinic and diacid and their derivative be ester for example, with the acid anhydrides when for diacid, vinylformic acid for example, acrylic or methacrylic acid C _1-4Alkyl ester such as butyl acrylate and methyl methacrylate, the mixture of maleic anhydride or their arbitrary combination.In monovinylidene aromatic polymers, may also need a kind of copolymerizable cross-linking monomer such as Vinylstyrene in some cases.

The polymkeric substance of monovinylidene aromatic monomer and other copolymerizable comonomer preferably contains at least 50% (mole), preferred one or more monovinylidene aromatic monomers of at least 60% (mole), particularly at least 70% (mole) by polymerization therein.

B component also can be flame retardant rubber-modified vinylbenzene blend composition.Fire-retardant combination generally prepares by add fire retardant in high-impact polystyrene (HIPS).The adding of fire retardant has reduced the shock strength of HIPS, but shock strength can be returned to required level again by adding impact modifier.Final composition is called as the polystyrene of anti-combustion IRPS.The IRPS composition contains following component usually:

Component R) account for the rubber modified polymers for preparing by vinyl aromatic monomer of total resin combination (R+S+T+U) 50% to 90% (weight), HIPS for example,

Component S) make composition (R+S+T+U) contain the halogen containing flame-retardant of the q.s of 7% to 14% (weight) halogen,

Component T) account for total resin combination (R+S+T+U) 2% to 6% (weight) inorganic fire-retarded synergistic agent and

Component U) accounts for the impact modifier of total resin combination (R+S+T+U) 1% to 8% (weight).

Component R is the vinyl aromatic polymer of modified rubber.The polymkeric substance that is suitable for comprises those polymkeric substance that obtained by the vinyl aromatic monomer shown in the following formula:

Wherein R is H or methyl, and Ar contains 1 to 3 aromatic ring structure that has alkyl, halogen or haloalkyl substituting group or do not have substituent aromatic ring, and wherein alkyl contains 1 to 6 carbon atom, and haloalkyl is meant the alkyl that halogen replaces.Ar is preferably phenyl or alkyl phenyl, particularly phenyl.The typical vinyl aromatic monomer that can select for use comprises: vinylbenzene, alpha-methyl styrene, all isomer of Vinyl toluene are particularly to Vinyl toluene, all isomer of ethyl styrene, propylstyrene, vinyl biphenyl, vinyl naphthalene, vinyl anthracene etc., and their mixture.Vinyl aromatic monomer also can with the common polymerization of other copolymerizable monomer.This class monomer comprises acrylic monomer such as vinyl cyanide, methacrylonitrile, methacrylic acid, methyl methacrylate, vinylformic acid and methyl acrylate, maleic anhydride, maleimide and phenyl maleimide, but be not limited to this.

The vinyl aromatic polymer of modified rubber can carry out polymerization with vinyl aromatic monomer and prepare in the presence of a kind of rubber of dissolved in advance, what obtain is impact-resistant modified or contains the product of graft rubber.The example of this respect can be referring to U.S. Patent No. 3,123, and 655,3,346,420,3,639,522 and 4,409,369.Rubber is generally divinyl or synthetic polyisoprene, is preferably polyhutadiene.The vinyl aromatic polymer of modified rubber is preferably high-impact polystyrene (HIPS).

The consumption of the vinyl aromatic polymer of the modified rubber that adopts in the present composition accounts for 50% to 90% (weight) of total resin composition (R+S+T+U) usually, be preferably 60% to 88% (weight), more preferably 70% to 85% (weight), particularly 72% to 82% (weight).

Component U is the shock strength improving agent, and it can be any polymkeric substance that can improve present composition shock strength.Typical shock strength improving agent comprises the multipolymer of polyhutadiene, polyisoprene and vinyl aromatic monomer and conjugated diolefine, and for example styrene-butadiene copolymer, styrene-isoprene multipolymer comprise diblock and triblock copolymer.Other impact modifier comprises multipolymer, ethylene-acrylic acid copolymer and the ethylene-styrene copolymer of vinyl aromatic monomer and hydrogenated diene hydrocarbon.Impact modifier is preferably the styrene-butadiene-styrene triblock copolymer that the vinylbenzene component concentration is 25% to 40% (weight).When adopting the ethylene/styrene interpolymer as impact modifier, ethylene/styrene interpolymer and blends of polystyrene are blend of the present invention.

The consumption of the impact modifier that adopts in the present composition accounts for 1% to 8% (weight) of total resin composition (R+S+T+U) usually, is preferably 1% to 7% (weight), more preferably 2% to 6% (weight), particularly 2% to 5% (weight).

Component S is a fire retardant, and it is to give the halide-containing of present composition flame retardant properties or the mixture of multiple compound arbitrarily.The fire retardant that is suitable for is known by those skilled in the art, comprise six halogenated diphenyl ether, eight halogenated diphenyl ether, decahalodiphenyl ether, decahalodiphenyl base ethane, 1,2-two (trihalogenated benzene oxygen base) ethane, 1,2-two (phenyl-pentahalide oxygen base) ethane, six halo cyclododecanes, four halogenated bisphenol A, ethylidene (N, N ')-two four halophthalimide, four halophthalic acid acid anhydrides, phenyl-hexahalide, halogenation 1, the 2-indane, Firemaster 836, halogenated paraffin, the polymkeric substance of halogenated polystyrene and halogenation dihydroxyphenyl propane and Epicholorohydrin, or their mixture, but be not limited to this.Fire retardant is preferably the compound of brominated or chlorine.In a preferred embodiment, fire retardant is the mixture of decabromodiphynly oxide or decabromodiphynly oxide and tetrabromo-bisphenol.

The amount of fire retardant depends on the halogen content of selected concrete fire retardant in the present composition.The selection of fire retardant consumption should make the content of halogen in the present composition account for 7% to 14% (weight) of total resin composition (R+S+T+U) usually, be preferably 7% to 13% (weight), more preferably 8% to 12% (weight), particularly 9% to 11% (weight).

Component T is a kind of inorganic fire-retarded synergistic agent of those skilled in the art known raising fire retardant, particularly halogenated fire-retardants flame retardant effect.The example of inorganic fire-retarded synergistic agent comprises metal oxide, as ferric oxide, stannic oxide, zinc oxide, aluminium sesquioxide, aluminum oxide, antimonous oxide and antimony peroxide, bismuth oxide, molybdic oxide and tungstic oxide, boron compound such as zinc borate, silicic acid antimony, ferrocene and their mixture, but be not limited to this.

The consumption of inorganic fire-retarded synergistic agent accounts for 2% to 6% (weight) of total resin composition (R+S+T+U) usually, is preferably 2% to 5% (weight), more preferably 2.5% to 5% (weight), particularly 2.5% to 4% (weight).

Composition of the present invention also can contain a spot of habitual processing aid, for example releasing agent, softening agent, fluidity improver such as wax or mineral oil, pigment, thermo-stabilizer, ultra-violet stabilizer, oxidation inhibitor, filler such as glass fibre, glass microballon.

Composition can prepare by any blend or hybrid technology that can access all the components homodisperse dispersion in products therefrom.Representational equipment comprises Banbury mixing machine, compounding roller, single screw extrusion machine, twin screw extruder or the like.In addition, enter mix/melt extrude machine equipment before, each component of composition can be mixed in the equipment as the dry state blender, or two or more components can be carried out premix and joined in the hot melts of other composition.

Can be used for those polymkeric substance that the homopolymer that is fit to of foam composition of the present invention and interpolymer have been enumerated above comprising, and can select one or more polymerisable ethylenically unsaturated monomers different that exist as required and the interpolymer for preparing with (b) with (a) described those monomers by (a) one or more vinylidene aromatic monomers and/or one or more hindered aliphatic vinylidene monomers.The polymerisable ethylenically unsaturated monomer of this class that is suitable for for example comprises: have 3 to 8 carbon atoms, preferred 3 to 6 carbon atoms, particularly the olefinic unsaturated monocarboxylic of 3 to 4 carbon atoms, have 4 to 10 carbon atoms, preferred 4 to 8 carbon atoms, the particularly acid anhydrides of the ethylenically unsaturated dicarboxylic of 4 to 6 carbon atoms, the ester of olefinic unsaturated monocarboxylic, olefinically unsaturated nitriles, or their mixtures or the like arbitrarily.The monomer of particularly suitable for example comprises vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, maleic anhydride, vinyl cyanide, methacrylonitrile or they mixture arbitrarily.Interpolymer can contain 0 at the most 50%, preferably at the most 40%, this class monomer different of 30% (weight) at the most particularly with monomer (a).

Blend of the present invention can prepare according to the known any appropriate means of those skilled in the art, for example is blended into granular form with required ratio dry state, carries out melt blending then in screw extrusion press or Banbury mixing machine, but is not limited to this.The pellet of dry state blend can become the goods of final solid form by the direct melt-processed of for example injection-molded method.In addition, blend also can directly prepare by polymerization, for example in a reactor, adopt two or more catalyzer, or in two or more reactors of serial or parallel connection, adopt single site catalysts and the component of blend is not carried out isolating polymerization process.

Directly an example for preparing blend by polymerization is as U.S. Patent No. 4,168, the method for the interior blend of 353 described reactors.In the method, styrene monomer is impregnated in the pellet of the interpolymer blend components (A) that is suspended in the suitable liquid medium and carries out graft polymerization.The blend pellet of gained is through cooling and be discharged out container.

Foamy structure of the present invention can adopt the known physical aspect arbitrarily of professional, for example thin slice, sheet or block.Other useful form has expandable or foamable particle, mouldable foam beads, or pearl, and is expanded and/or coalescent and welding and the goods made by those particulate.

C.P.Park is described for method for preparing the vinyl 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)), this chapters and sections content is incorporated this paper in this application as a reference into.

Foamable composite foamed can obtain foams, and foamy structure of the present invention can prepare by habitual extruding-out process.The preparation process of this structure generally is that plastifying or melt polymer material are made in polymer materials heating, then to wherein adding whipping agent making foamable gel, and by a die head gel is extruded to make froth product.Before sneaking into whipping agent, polymer materials is heated to its second-order transition temperature or the temperature on fusing point or this two temperature.Whipping agent can be by the known any way of those skilled in the art as adopting forcing machine, mixing machine, blender or other similar equipment and add or sneaking in the melt polymer material.Whipping agent mixes under higher pressure with melt polymer material, and this pressure is enough to prevent that melt polymer material from actual expansion taking place and be enough to make whipping agent to reach uniform dispersion therein.In addition, nucleator can be sneaked in the polymer melt, or before polymer materials plasticizing or fusing, nucleator be carried out the dry state blend with it.Foamable gel generally is cooled to lower temperature so that the physical features of foamy structure reaches optimum regime.Gel is extruded or is transferred to a zone with lower pressure to form foamy structure by a die head with desired shape then.But the pressure of lower pressure region is lower than the pressure of foamable gel region before being extruded by die head.Lower pressure can be higher than 1 normal atmosphere or be lower than 1 normal atmosphere (vacuum), but preferably remains on 1 atmospheric level.Can obtain thick plate-like, sheet, bar-shaped and tubulose froth product by this technology.

The vinyl polymer material can be made foamy structure of the present invention stranded line material shape by a porous dies.The arrangement of porous position can be so that the adjacent streams that melt extrudes produces contact in foaming process, thereby contact surface forms whole foamy structure so that enough bounding forces are bonding mutually.Leave the shape that melt extrudes streams line taking material or section bar of die head, their through the foaming, stranded and mutual bonding and formation one-piece construction.Each line material that twists together or section bar preferably keep the bonding whole structure that becomes, and produce in the time of can preventing stress that the principal vertical line material runs into like this in foamy preparation, moulding and application and separate.Manufacturing is the equipment of foamy structure of twisted wire material state and method can be referring to U.S. Patent No. 3,573, and 152 and No.4,824,720.

Foamy structure of the present invention also can be come moulding by U.S. Patent No. 4,323,528 described storage material type extrusion methods.In the method, low density foam structure with comparatively large cross-sectional area prepares as follows: 1) pressurization at a certain temperature prepares the gel of vinyl polymer material and whipping agent, and the viscosity that gel has under this temperature is enough to make whipping agent to be remained on when gel expands wherein; 2) gel being expressed into a temperature and pressure maintains and does not make in the anchor clamps that gel foams, these anchor clamps contain an outlet die head, have a perforate of leading to the low pressure zone that gel foams therein on it, and an openable wicket of closing described die head perforate; 3) periodically open wicket; 4) with a mobilizable ram gel is applied mechanical force simultaneously basically gel is entered low pressure area from anchor clamps by die head perforate injection, (gel enters low pressure area) speed is greater than the speed that foams in the generation of die head tapping and less than the speed that forms irregular section and profile at this moment; With 5) gel of injection is being expanded on the one dimension direction at least without restriction, thus form foamy structure.

Foamy structure of the present invention also can be shaped to the noncrosslinking foam ball that is suitable for being molded as goods.In order to prepare the foam ball, discrete resin particle for example is suspended in them through the resin beads of granulation is insoluble to wherein liquid medium basically for example in the water, in autoclave or other pressure vessel, whipping agent is added in the liquid medium, and under higher pressure and temperature, soak resin particle, and fast resin particle is discharged in air or the low pressure area and makes the foam ball to foam with whipping agent.This technology is in U.S. Patent No. 4,379, introduction arranged in 859 and 4,464,484, and these patents are all incorporated this paper into as the application's reference.

Particle foamable or that foamed can prepare by batch process or expressing technique.The batch process of the preparation expandable particles technology with preparation expandable polystyrene (EPS) (EPS) basically is identical.In pressure vessel, the particle of the blend polymer that will prepare by the method for blend in above-mentioned melt blending or the reactor under higher temperature and pressure soaks into whipping agent in water dispersion or under anhydrous state.Subsequently with particle or be discharged rapidly in the low pressure area and make the foam ball to foam, or discharge with its cooling and with the form of the ball that do not foam.The ball that for example adopts water vapor or warm air not to foam by rights heats so that its foaming then.The common foaming extrusion method with above-mentioned is identical basically before the die head perforate for extrusion method.Die head has a plurality of perforates.In order to prepare the not ball of foaming, the foamable polymer line materials flow of leaving the die head perforate is carried out quenching to prevent foaming with cooling bath at once, carry out granulation then.Perhaps, change polymer strands stream into the foam ball by method in die face cutting and foaming thereupon.

The foam ball can adopt the known any method of professional to carry out molding subsequently, for example the foam ball is put into mould, mould is exerted pressure with the die casting ball, and the mode that adopts water vapor for example with the ball heating regulating each other bonding and bonding of ball, thereby the formation goods.Ball can soak with air or other whipping agent under higher pressure and temperature before putting into mould.Ball also can be heated before entering mould in addition.With the known appropriate means of professional the foam ball is molded as lumphy structure or other moulded products 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.The inorganic foaming agent that is suitable for 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 1 to 4 complete and partially halogenated aliphatic hydrocarbon of carbon atom.Aliphatic hydrocarbon comprises methane, ethane, propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane or neopentane.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), 1,1,2,2-Tetrafluoroethane (HFC-134), 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 sodium bicarbonate, sodium bicarbonate and citric acid, azodicarboamide, Diisopropyl azodicarboxylate, benzol sulfohydrazide, 4,4-oxybenzene sulphonyl semicarbazides, tolysulfonyl semicarbazides, azoformic acid barium, N, N '-dimethyl-N, the mixture of N '-dinitrosoterephthalamine and three hydrazine triazines.In order to prepare low density foam by expressing technique, preferred volatile organic blowing agent or carbon dioxide foaming agent.The organic blowing agent of preferred volatile comprises normal butane, Trimethylmethane, Skellysolve A, iso-pentane, HFC-152a and their mixture.In order to prepare foamable ball product, preferred Trimethylmethane, Skellysolve A, iso-pentane and their mixture are as whipping agent.

Be that preparation forms the foamy polymer gel, the amount that adds whipping agent in every kilogram polymer melt material is 0.05 to 5.0, preferred 0.2 to 4.0, particularly 0.5 to 3.0 mol.

In foamy structure of the present invention, can add many different additives, for example nucleator, mineral filler, pigment, oxidation inhibitor, acid scavenger, UV light absorber, fire retardant, processing aid, extrusion aid.

In addition, the size for the control abscess can add nucleator.Preferred nucleator comprises mixture of inorganic substance such as lime carbonate, talcum, clay, titanium dioxide, silicon-dioxide, barium sulfate, diatomite, citric acid and sodium bicarbonate or the like.The consumption of nucleator is per 100 parts of (weight) fluoropolymer resins with 0.01 to 5 part (weight).

Foamy structure is essentially non-crosslinked or does not have crosslinked.Alkenyl aromatic hydrocarbon polymer material with foamy structure is no crosslinked basically.Foamy structure contains and is no more than 5% gel (measuring according to ASTM D-2765-84 method A standard method).There is not following spontaneous lightly crosslinked permission of linking agent or radiating effect.

The density of this foamy structure is less than 450, preferably less than 200, particularly 10 to 80 kilograms per cubic meter.The mean sizes of abscess is 0.02 to 5.0, and is preferred 0.2 to 2.0, particularly 0.3 to 1.8 millimeter (measuring according to ASTM D3576 standard method).

This foamy structure can have the known any physical form of professional, for example the sheet of extrusion moulding, bar-shaped, tabular and material with section bar profile.Foamy structure also can be shaped to above-mentioned arbitrarily shape or other Any shape by foamable ball being carried out molding.

This foamy structure can be obturator-type or open cell type.Foams of the present invention preferably contain 80% or more closed pore (measuring according to ASTM D2856-A standard method).

(for example for example in the interpolymer that interpolymer that the present invention adopts and/or blend of the present invention adopt, can also contain oxidation inhibitor, sterically hindered phenol such as Irganox  1010 (registered trademark of CIBA-GEIGY), phosphite such as Irgafos  168 (registered trademark of CIBA-GEIGY)), the additive of ultra-violet stabilizer, tackifier (as polyisobutene), release additives, tinting material, pigment, filler or the like, do not emphasize those performances of improving as long as the consumption of these additives does not influence the application.

The consumption of additive is as the criterion to play required effect, and this point is known by those skilled in the art.For example, the consumption of oxidation inhibitor should be able to prevent that polymkeric substance or blend polymer under residing temperature and the envrionment conditions oxidation taking place when the storage of polymkeric substance and last the use.At this moment the consumption of oxidation inhibitor is generally and accounts for 0.01% to 10% of polymkeric substance or blend polymer weight, and is preferred 0.05% to 5%, and particularly 0.1% to 2%.

Similarly, the consumption of any additive that other is cited also should reach its required effect, and for example its consumption can prevent that polymkeric substance or blend polymer are clamminess, reach required filler loadings to obtain required result, to provide required color by tinting material or pigment.The suitable consumption of these additives is to account for about 0.05% to about 50%, preferred about 0.1% to about 35%, particularly about 0.2% to about 20% of polymkeric substance or blend polymer weight.But for filler, its consumption may reach and account for about at the most 90% of polymkeric substance or blend polymer weight.

Blend of the present invention can be used to prepare multiple moulded products, for example by sheet material or film are made in blend calendering, casting or blowing, by with blend injection, pressing mold, extrude or goods are made in blowing, perhaps prepare fiber, foams or latex by this blend.Blend of the present invention also can be used in the adhesive formula.

The composition of the present invention that contains the flame-retardant polystyrene of useful ethylene/styrene interpolymer modification can be used in the injection moulding manufacturing of housing of TV set, graphoscope or printer support.

The present invention is described further for following examples.

Testing method

The performance of polymkeric substance and blend is measured according to following test procedure:

Melt flow rate (MFR) (MFR)According to ASTM D-1238 (1979), the standard method of condition E (190 ℃, 2.16 kilograms) is measured.

Tensile strengthAccording to ASTM D-882-91, the standard method of option A test, the change condition is: each blend polymer is parallel does five tests.Clamping is 1 inch (2.54 centimetres) at interval always.The clamping velocity of separation is 5 mm/min always.

ModulusAccording to ASTM D-882-91, the standard method of option A test, the change condition is: each blend polymer is parallel does five tests.Clamping is 1 inch (2.54 centimetres) at interval always.The clamping velocity of separation is 5 mm/min always.

ElongationAccording to ASTM D-882-91, the standard method of option A test, the change condition is: each blend polymer is parallel does five tests.Clamping is 1 inch (2.54 centimetres) at interval always.The clamping velocity of separation is 5 mm/min always.

ToughnessAccording to ASTM D-882-91, the standard method of option A 2.1 test, the change condition is: each blend polymer is parallel does five tests.Clamping is 1 inch (2.54 centimetres) at interval always.The clamping velocity of separation is 5 mm/min always.

The preparation of ethylene/styrene interpolymer A-G

In 2 liters of reactors that have a stirring, add about 500 milliliters of mixed alkanes solvents (ISOPARTME, the registered trademark of Exxon chemical company and by its manufacturing) and about 500 milliliters of styrene copolymerized monomers.By the differential pressure plavini hydrogen is joined in the reactor from 75 milliliters of injection jars then.Reactor is heated to required service temperature, and reactor is saturated to required pressure with ethene.(tetramethyl-ring pentadienyl) (tertiary butyl amino) dimethyl silyl methyltitanium catalyzer and three (pentafluorophenyl group) borine promotor is mixed in a loft drier, and catalyzer and mixing of promotor are the ISOPAR in inert atmosphere glove box ^TMCarry out in the E solvent.The solution of gained is transferred in the catalyzer feed pot, and injection joins in the reactor.Polyreaction is carried out under the condition that continues feeding ethene.Carry out according to circumstances to continue in the process to add the catalyst solution for preparing with the same manner in reaction.After reaction finishes, with polymers soln discharge reactor and with contain 100 milligrams of IRGANOX ^TM10 milliliters of toluene solutions of 1010 mix mutually.Use the propyl alcohol precipitation polymers, in 120 ℃ reduced vacuum (registered trademark of CIBA-GEIGY) baking oven, dry about 20 hours to remove the volatile matter in the polymkeric substance.

Table 1A provides monomeric consumption and polymerizing condition.Productive rate and polymer performance are listed in table 1B.

Table 1A

Interpolymer	Isopar TME (g)	Vinylbenzene (g)	Hydrogen (Δ)		Ethene		Reaction times (min)	Temperature of reaction (℃)	Catalyzer (μ mol)
										psig	kPa	psig	kPa
			A	358	455	0								0	200	1,379	80	80	20
B	361	454					13	90	250	1,724	20	80	5
			C	361	454	11								76	150	1,034	20	80	6
D	361	461					11	76	100	689	20	80	9
			E	365	461	0								0	100	689	30	80	12
F	420	380					0	0	50	345	30	80	25
			G	361	358	12								83	50	345	30	60	15
H	0	768					16	103	50	345	30	60	20
			I	361	461	11								69	300	2,068	20	60	4

Table 1B

Interpolymer	Output (g)	Melt flow rate (MFR) dg/min	Styrene content in the interpolymer		E/S wt% in the interpolymer	Amorphous polystyrene wt%
							mol％	wt％
			A	72.7					0.195	20.1	48.3	96	4
B	69.9	0.40			7.4	22.9	99.6	0.4
			C	57.7					0.74	17.8	44.6	98.1	1.9
D	48.4	3.62			24.9	55.2	97.8	2.2
			E	59.3					1.52	26.5	57.3	97.4	2.6
F	85.6	13.1			343	66.0	94.8	5.2
			G	114.7					1.07	41.0	72.1	98.6	1.4
H	96	0.92			47.3	76.9	94.8	5.2
			I	67					0.14	8.4	25.4	98	2

Embodiment 1

A, ethylene/styrene interpolymer

The ethylene/styrene interpolymer that present embodiment adopts is represented with H in table 1A and table 1B.

The preparation of B, E/S interpolymer and polystyrene blend

Polymer masses is carried out granulation and be about 200000 with weight-average molecular weight, dispersity is that 2.5 general purpose polystyrene (PS) carries out blend.The content of ES interpolymer in blend can be 0 to 40%.Test by the following stated.Under 180 ℃ and nitrogen protection, be that the granular resin mixtures of 40 grams carried out melt blending 15 minutes with gross weight on a Haake Rheocord 90 type mixing machines with 30 rev/mins speed.Blend is pressed into thickness at a constant temperature is about 0.9 millimeter thin slice on 177 ℃ thermocompressor.With Thwing-Albert LDC-50 type cutting machine thin slice is cut into 1/2 inch (1.27 centimetres) wide band.With the tensile property of Instron 1123 stretching test machine determination samples, pinblock speed is 5 mm/min, and the folder distance is 1 inch (2.54 centimetres).Each blend carries out the mensuration of five samples, and the mean value of getting these five data points is with the performance as blend.

Test-results is listed in the table 2.When ES content was lower than 40%, the mechanical tenacity of blend did not significantly improve.At content is 40% o'clock, and these performances of blend are improved significantly.60/40 PS/ES blend can extend 70% on its original length, and has relative higher modulus.Transmission electron microscope photo shows that blend has the successive two phase structure.

Table 2

Test number	ES content (%) (1)	Tensile strength (MPa) (2)	Elongation at break (%) (3)	Toughness (MJ/cu.m) (4)	Modulus (MPa) (5)
						1.1 *	0	39.2	5.4	1.2	924
1.2	10	28.1	4.4	0.6	827
						1.3	20	24.5	3.3	0.5	965
1.4	30	35.7	5.2	1.0	972
						1.5	40	27.6	70.2	18.5	876

^*Non-embodiments of the invention

(1) the ethylene/styrene interpolymer H that carries out blend to represent based on the percentage ratio of blend polymer

Tensile strength when (2) rupturing is represented with MPa

Elongation when (3) rupturing is represented with the percentage ratio based on initial length

(4) toughness of measuring according to the area under the stress strain curve is with megajoule/cubic meter expression

(5) 2% secant moduluss are represented with MPa

Embodiment 2

In the present embodiment, the ES interpolymer that adopts six ethylene/styrene ratios and melting index the to have nothing in common with each other test that comes repetition embodiment 1.The ES interpolymer prepares according to the table described different ethylene/styrene ratio of 1A.All materials all contain a spot of (less than 5.2%) amorphous polystyrene.The same with embodiment 1, each ES interpolymer and 60 parts of polystyrene of 40 parts carry out blend.As shown in table 3, all ES interpolymer materials can both form the flexible blend.The toughness of the ES interpolymer that general styrene content is higher is more better.The ES interpolymer that is adopted in 2.5 tests is an exception.The performance of resin does not meet general rule.This high fusion index (or low viscosity) that may be interpreted as material causes its performance relatively low.

Table 3

	The E/S interpolymer			The tensile property of blend
								Test number	Type	Styrene content % (1)	MFR dg/Min (2)	Fracture tensile strength (MPa) (3)	Elongation at break (%) (4)	Toughness (MJ/m 3) (5)	Modulus (MPa) (6)
2.1	B	7.4	0.40	19.9	21.4	3.5	356
								2.2	I	8.4	0.14	24.3	13.8	2.6	483
2.3	C	17.8	0.74	15.6	57.4	9.4	315
								2.4	E	26.5	1.52	12.1	87.6	11.2	303
2.5	F	34.3	13.1	14.5	30.1	4.2	381
								2.6	G	41.0	1.07	25.1	268.0	61.1	430

(1) cinnamic content in the ES interpolymer is in molecular fraction

(2) melting index of ES interpolymer is measured under 190 ℃/2.16 kilograms according to ASTM D 1238 standard methods

Tensile strength when (3) rupturing is represented with MPa

Elongation when (4) rupturing is represented with the percentage ratio based on initial length

(5) toughness of measuring according to the area under the stress strain curve is with megajoule/cubic meter expression

(6) 2% secant moduluss are represented with MPa

Embodiment 3

In the present embodiment, repeat 2.6 tests, but adopt that weight-average molecular weight is 300000, dispersity is that 2.4 another kind of polystyrene replaces original polystyrene.As shown in table 4, this resin blend has gratifying toughness and relative higher modulus.

Table 4

Test number	ES content (%) (1)	Tensile strength (MPa) (2)	Elongation at break (%) (3)	Toughness (MJ/m 3) (4)	Modulus (MPa) (5)
						3.1	40	17.5	207.0	44.4	382

(1) the ethylene/styrene interpolymer G that carries out blend (41.5 moles of % vinylbenzene, 1.07 melt flow rate (MFR)s) to represent based on the percentage ratio of blend polymer

Tensile strength when (2) rupturing is represented with MPa

Elongation when (3) rupturing is represented with the percentage ratio based on initial length

(4) toughness of measuring according to the area under the stress strain curve is with megajoule/cubic meter expression

(5) 2% secant moduluss are represented with MPa

Embodiment 4

In the present embodiment, contain the cinnamic ES interpolymer of 20.1 moles of % (48.3 weight %) (the interpolymer A among table 1A and the 1B), the polystyrene resin that is adopted among amount with 10% to 20% and the embodiment 1 carries out blend.The ES interpolymer contains about 4% the amorphous polystyrene that accounts for the total polymer amount.As shown in table 5, the content of ES interpolymer in blend reaches 20% fashion at the most and is not enough to obtain to have the flexible blend.

Table 5

Test number	ES content (%) (1)	Tensile strength (MPa) (2)	Elongation at break (%) (3)	Toughness (MJ/cu.m) (4)	Modulus (MPa) (5)
						4.1	10	27.4	4.1	0.6	869
4.2	20	31.6	5.6	1.1	800
						4.3	20	36.2	6.5	1.3	855

(1) the ethylene/styrene interpolymer that carries out blend (20.1 moles of % vinylbenzene, 0.2 melt flow rate (MFR)) to represent based on the percentage ratio of blend polymer

Tensile strength when (2) rupturing is represented with MPa

Elongation when (3) rupturing is represented with the percentage ratio based on initial length

(4) toughness of measuring according to the area under the stress strain curve is with megajoule/cubic meter expression

(5) 2% secant moduluss are represented with MPa

Comparison test A (the non-embodiment of the invention)

In this comparison test, with polystyrene and a kind of commercial styrene-butadiene-styrene triblock copolymer body (the SBS) (VECTOR that adopts among the embodiment 1 ^TM6241-D, the registered trademark of Dexco Polymer Company and by its product) carry out blend.As shown in table 6, the 60/40PS/SBS blend has good elongation and gratifying toughness.But compare the hardness of this blend lower (modulus value is low) with the PS/ES blend.In the great majority of blend polymer were used, high-modulus was very important often.

Table 6

Test number	ES content (%) (1)	Tensile strength (MPa) (2)	Elongation at break (%) (3)	Toughness (MJ/m 3) (4)	Modulus (MPa) (5)
						5.1 *	40	22.5	244.0	44.0	272

^*The non-embodiment of the invention

(1) VECTOR that carries out blend to represent based on the percentage ratio of blend polymer ^TMThe SBS interpolymer of the 6241-D trade mark (registered trademark of Dexco Polymer Company and by its product)

Tensile strength when (2) rupturing is represented with MPa

Elongation when (3) rupturing is represented with the percentage ratio based on initial length

(4) toughness of measuring according to the area under the stress strain curve is with megajoule/cubic meter expression

(5) 2% secant moduluss are represented with MPa

Embodiment 5

The preparation of ES multipolymer

What present embodiment adopted is to be numbered the random ethene-vinylbenzene of being essentially of H (ES) multipolymer among table 1A and the 1B.This ES multipolymer contains the styrene units of 76.9 weight % (47.3 moles of %), and melting index is 0.92 (according to ASTM D-1238 standard method, measuring under 190 ℃/2.16 kilograms).

Expandable test

What present embodiment adopted is blend prepared in embodiment 1.On 180 ℃ the thermocompressor blend in being about the mould of 1 inch (25.4 millimeters) and the degree of depth about 0.1 inch (2.54 millimeters), diameter is being carried out moulded section at an about constant temperature.

Disk sample is placed on uses fluoropolymer Teflon in the pressurized vessel ^TMIn the silk screen dish of lining, each formulation is got 3 disk samples.The silk screen dish hangs with a upholder, so just can be not directly contact with the liquid blowing agent that joins in the container subsequently and be deposited in container bottom.The iso-pentane that in container, adds about 2.8 grams.Cover lid removes wherein air with nitrogen flooding, with oil bath with the temperature of container remain on 60 ℃ about 6 days altogether.Cooling vessel also takes out sample.Sample thickness is that 70 mils (1.8 millimeters) are to 127 mils (3.2 millimeters) after whipping agent soaks.A sample aliquot with each formulation is cut into two parts after a while, and the sample of being cut was exposed to the open air in atmospheric steam 5 minutes.As shown in table 7, for per 100 parts of polymkeric substance (pph, the umber in per 100 parts), the amount that the PS/ES blend absorbs iso-pentane has surpassed 10 parts, and is expanded to rational low density.90/10 PS/ES blend has reached the least density of 44 kilograms per cubic meter.

In contrast, pure polystyrene sample absorbs the amount of iso-pentane less than 3pph, and its density only expand into 94 kilograms per cubic meter.The foam that 60/40 PS/ES blend forms relative higher density may be because the overlong time that exposes to the open air in steam.When taking out from the steam still, blend foam shows certain contraction.

Table 7

PS/ES blend after soaking with iso-pentane expandable

Test number	Prescription is formed (1)	Thickness (mm) (2)	Isopentane content (pph) (3)	Density foam (4) (#/ft 3) (kg/m 3)
						5.1 *	PS	1.8	3.0	5.9	94
5.2	PS/ES 90/10	2.1	14.3	2.7	44
						5.3	PS/ES 80/20	2.8	13.8	3.8	61
5.4	PS/ES 70/30	3.2	11.6	4.8	77
						5.5	PS/ES 60/40	3.0	10.3	8.3	133

^*The non-embodiment of the invention

(1) polystyrene of PS-ordinary meaning, weight-average molecular weight 200000

The ES=ethylene-styrene copolymer contains 76.9 weight % vinylbenzene, melting index 0.92

(2) sample thickness is in millimeter

(3) amount of the iso-pentane that contained after just soaking of sample is in the umber of per 100 parts of polymkeric substance

(4) new sample is exposed to the open air the density of the foam sample that obtains after 5 minutes in normal pressure steam, simultaneously in pound/cubic inch and kilograms per cubic meter

The maintenance of whipping agent

The hold facility of the whipping agent of the above-mentioned sample that has soaked iso-pentane, its measuring method are with the prolongation of the digestion time weight of working sample periodically under 23 ℃ room temperature.Whole tracking test 8 totally months, data are compiled in the table 8.Since the mark of whipping agent loss be inversely proportional to thickness of sample square, so thickness of selecting identical digestion time and being 2 millimeters of relatively should consider between the data.For ease of relatively, the maintenance data of the whipping agent of each sample under different digestion times have been provided in the table 8.Data show that the hold facility of the whipping agent of PS/ES blend is better than pure polystyrene.After 3 months digestion time, the PS/ES blend has kept surpassing the whipping agent of 65% initial amount, and polystyrene sample in all internal losses half of its whipping agent.

Table 8

23 ℃ of following PS/ES blends are to the maintenance dose of iso-pentane

Test number	Prescription is formed (1)	23 ℃ down through the different times that wears out (my god) after the maintenance dose (2) of iso-pentane
									0	7	14	30	60	90	120
		2.1 *	PS	2.8	1.4	1.2	0.9	0.5								0.4	0.3
2.2	PS/ES 90/10								14.9	12.9	11.8	10.9	9.9	9.4	9.0
		2.3	PS/ES 80/20	12.9	11.7	11.2	10.6	9.8								9.4	9.1
2.4	PS/ES 70/30								10.3	9.5	9.1	8.6	8.0	7.7	7.4
		2.5	PS/ES 60/40	10.0	8.7	8.3	7.6	7.0								6.6	6.4

^*The non-embodiment of the invention

(1) polystyrene of PS-ordinary meaning, weight-average molecular weight 200000

The ES=ethylene-styrene copolymer contains 76.9 weight % vinylbenzene, melting index 0.92

(2) 23 ℃ of maintenance doses that descend the iso-pentane of the sample of 2 millimeters thickness behind aging certain hour are in the umber in per 100 parts of polymkeric substance

The ethylene-styrene copolymer for preparing above is molded into disk according to above-mentioned same mode.Disk sample was soaked 8 days down at 60 ℃ with HCFC-141b according to above-mentioned step totally.Sample to the mensuration of whipping agent hold facility adopt under 23 ℃ the room temperature in 6 days aging time the mode of its weight of tracking and measuring periodically.Sample thickness is about 3 millimeters.As shown in table 9, sample is considerably good to the hold facility of HCFC-141b whipping agent.

Table 9

The ethylene/styrene multipolymer is to the maintenance dose of R-141b

	Elapsed time (my god)
						0	1	3	4	6
	23 ° of R-14lb maintenance doses (pph)	3.2	3.0	2.9	2.9						2.9

Embodiment 6-13

The preparation of interpolymer and sign

The preparation of interpolymer J, K and L

Polymkeric substance is to prepare in the semi-continuous batch reactor that stirs of 400 gallons band at a volume.Reaction mixture is made up of about 250 gallons mixed solvent and the vinylbenzene that contain hexanaphthene (85% weight) and iso-pentane (15% weight).Before in 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 and 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-yl) silanamines close)) (2-) N)-the dimethyl titanium, CAS#135072-62-7 (CAS accession number), three (pentafluorophenyl group) boron, CAS#001109-15-5,3A type modified methylaluminoxane, CAS#146905-79-5 flows into the control of 1/3/5 mol ratio, mixes 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 inflow catalyst.Vinylbenzene is removed from reactor, in solution, added 1000ppm Irganox subsequently ^TM1010 (registered trademark of CIBA-GEIGY) oxidation inhibitor, and polymkeric substance separated from solution.Polymkeric substance feeds that steam carries out the steam stripped method of water vapor or volatile matter forcing machine equipment is removed in employing with can adopting separating of solution in container.For through the steam stripped polymer materials of water vapor, need to adopt the equipment that is similar to forcing machine that it is handled to reduce moisture and all unreacted cinnamic content wherein again.

Interpolymer	Quantity of solvent		The vinylbenzene amount		Pressure		Temperature	H 2Total add-on	Reaction times	Polymkeric substance is concentration in solution
											Pound	Kilogram	Pound	Kilogram	Pound/inch 2	KPa	℃	Gram	Hour	Weight %
	(J)	252	114	1320	599	40	276	60	0	6.5											18.0
(K)											839	381	661	300	105	724	60	53.1	4.6	11.6
	(L)	1196	542	225	102	70	483	60	7.5	6.1											7.2

Interpolymer	Melting index I 2	Vinylbenzene gross weight in the polymkeric substance *％	Talcum weight %	Separation method
					(J)	1.83	81.6	＜2.5	The water vapor stripping
(K)	2.6	45.5	0	Forcing machine
					(L)	0.03	29.8	0	Forcing machine

^*Adopt the total weight percentage of vinylbenzene of fourier-transform infrared (FTIR) commercial measurement

The performance of interpolymer and vinyl aromatic polymer is listed in the table 10.Polymkeric substance with non-blend compares test.

Table 10

Interpolymer and vinyl aromatic polymer blend components

	Blend components
					(J)	(K)	(L)	(PS) *2
	Form
The content % (weight) of random isotactic polystyrene in interpolymer 4						8.2	10.3	1	100
	Vinylbenzene % (weight) 4	69.9	43.4	29.3	---
Ethene % (weight)						30.1	56.6	70.7	---
	Vinylbenzene % (mole)	40	17.1	10	---
Ethene % (mole)						60	82.9	90	---
	Molecular weight
Melt flow rate (MFR) (MFR), I 2						1.83	2.62	0.03	---
	Mn，×10 -3	71	66.8	118.1	---
Mw/Mn						2.63	1.89	2.04	---
	Physicals
Density, gram/cubic centimetre						1.0175	0.9626	0.943	---
	Fusing point (Tm), ℃	N.D.	49.6	71.3	---
Degree of crystallinity, %						N.D.	4.8	14.7	---
	Tc (Tc), ℃	N.D.	22.1	58.1	---
Second-order transition temperature (Tg, DSC), ℃						24.7	～-12	-17.2	106.3
	Mechanical property
Xiao A hardness						98	75	88	98
	Tensile modulus, MPa	703.3	6.5	20	1860.3
Modulus in flexure, MPa						620.6	68.8	62.1	3135.8
	Yielding stress, MPa	7.5	1.3	2.4	39.5
Breaking strain, %						248.3	475.3	377.5	1.6
	Rupture stress, MPa	17	22.6	34.3	38.8
Energy-to-break, Newton meter						98.2	102.2	145.5	1.1
	Stress relaxation, % (50%/10 minute)	93.5	38	30.2	CBM 3
The melt rheological property energy
					η×10 -5(0.1 rad/second), pool	1.01	1.05	16.6	4.48
η(100/0.1)	0.14	0.15	0.16 1	0.018
					Tan δ (0.1 rad/second)	9.98	4.2	2.37	2.59

^*Non-embodiments of the invention

The ratio of 1 η (1.6)/η (0.1)

2 Styron ^TM685D (registered trademark of Dow chemical company) is the polystyrene of ordinary meaning, and Dow chemical company produces, Midland, MI

3 energy measurements not

4 adopt the NMR technical measurement

The test of interpolymer and blend thereof and performance data are carried out according to the following steps and are obtained:

Pressing mold: with sample 190 ℃ of fusings 3 minutes, and the pressure dip mold of 190 ℃ and 20000 pounds 2 minutes.Subsequently, with the pressing mold of equilibrium at room temperature under molten materials is quenched.

Density: sample rate carries out according to the standard method of ASTM-D792.

Dsc (DSC): measure the thermal transition temperature of interpolymer and the size of transition heat with the DSC-2020 of Du Pont.In order to eliminate the influence of thermal history in the past, sample at first is heated to 200 ℃.Heat temperature raising and the speed that cools are decided to be 10 ℃/minute.To absorb heat respectively and the peak temperature of exothermic peak is decided to be melt temperature (temperature-rise period for the second time) and Tc.

Melt shear rheology performance: being determined on the RheometricsRMS-800 type rheometer of oscillatory shear rheological energy carried out.Under 190 ℃ of constant temperature, write down rheological property with frequency sweep mode.η is a viscosity.The ratio of the viscosity that η (100/0.1) representative recorded under 100 rad/seconds (rad/sec) and 0.1 rad/second.

Mechanical property test:

Xiao A hardness is measured according to the ASTM-D240 standard method under 23 ℃.

Modulus in flexure is measured according to the ASTM-D790 standard method.

The tensile property of mold pressing sample all is the INSTRON that has tension gage at ^TMCarry out on 1145 tensilometers.The sample that meets ASTM-D638 was at 5 minutes ^-1Strain rate under measure.Get the mean value of four tension tests.The numerical value of stress/strain curves weight break point is got in yielding stress and yield strain.Area below the stress/strain curves is represented energy-to-break.

Tensile stress relaxation: use INSTRON ^TM1145 tensilometers are measured uniaxial extension stress relaxation.The mold pressing film (about 20 mils, 0.0508 cm thick) of 1 inch (2.54 centimetres) length was at 20 minutes ^-1Produce under the strain rate and reach 50% strain.In 10 minutes hour range, measure the size that keeps the required power of 50% elongation.The numerical value of stress relaxation is defined as (f _i-f _f/ f _i), f wherein _iBe starting force, f _fBe end of a period power.

Thermo-mechanical analysis(TMA): thermo-mechanical analysis is measured on Perkin Elmer TMA 7 serial instruments.Being 5 ℃/minute at temperature rise rate is under 1 newton's the condition with load, on the mold pressing sample of 2 mm thick probe measurement is goed deep into 1 millimeter.

Embodiment 6-8

The preparation of blend: is that 90/10,70/30 and 50/50 weight ratio is mixed being furnished with on the Haake mixing machine that Rheomix 3000 alms bowls describe device above-mentioned interpolymer (J) and vinyl aromatic polymer (D) according to (J)/(D), prepares three kinds of blend compositions of embodiment 6,7 and 8.The composition of blend is at first carried out the dry state blend, enter constant temperature then in 190 ℃ mixing machine.Charging and make temperature equilibrium need 3 to 5 minutes.Speed with 40 rev/mins (rpm) is mixed molten materials 10 minutes at 190 ℃.

The performance data of these blends and blend components is listed in the table 11.

Table 11

	Polymer blend or embodiment
						(J) *	(D) *	6	7	8
	Blend composition, (J)/(D) weight ratio	100/0	0/100	90/10	70/30						50/50
Mechanical property
						Xiao A hardness	98	98	96	97	98
Tensile modulus, MPa	703.3	1860.3	654.3	1202.5	1696.9
						Modulus in flexure, MPa	620.6	3135.8	N.D. **	N.D. **	N.D. **
Yielding stress, MPa	7.5	39.5	6.4	9.9	24.5
						Breaking strain, %	248.3	1.6	230.5	184.3	12.7
Rupture stress, MPa	17	38.8	19.4	17.4	26
						Energy-to-break, Newton meter	98.2	1.1	114.6	97.4	11.9
Stress relaxation, % (50%/10 minute)	93.5	CBM 1	90.7	85.7	CBM 1
						TMA 2，℃	66	118	74	84	103
The melt rheological property energy
						η×10 -5(0.1 rad/second), pool	1.01	4.48	1.2	1.37	2.36
η(100/0.1)	0.14	0.018	0.12	0.088	0.049
						Tan δ (0.1 rad/second)	9.98	4.48	9.09	4.66	2.7

^*Non-embodiments of the invention

^*Do not survey

1 energy measurement not

2 depth of probes are the temperature at 1 millimeter place

Olefin polymer shows the consistency very poor with vinyl aromatic polymer usually, therefore in order to obtain good performance, generally needs to adopt some to increase the measure of consistency.Low toughness is general relevant with low consistency.

Yet, the stress during by fracture, strain and total energy-to-break data, table 11 shows that the blend composition of embodiment 6,7 and 8 has good comprehensive mechanical properties under situation about any mechanical property not being exerted an influence.Though its toughness of 50/50 composition is lower than other two kinds of blends, and is higher 10 times than unmodified vinyl aromatic polymer.

Further, these blends unexpectedly show beguine according to the taller stress relaxation of the resulting desired value of the characteristic of component.According to the high-temperature behavior of the shown composition that goes out when thermo-mechanical analysis (TGA) test middle probe penetrates 1 millimeter depths, blend is improving a lot aspect this high-temperature behavior.The penetration-resistant that contains the embodiment 8 of 50% (weight) polystyrene can approach polystyrene.

The melt rheology data of three embodiment 6,7 and 8 blends show, the performance (0.1 rad/second) under low the shearing can be carried out blend and regulates with low viscous blend.Embodiment 7 and embodiment 8 show lower tan δ value under low shear rate.This expression is compared with unmodified interpolymer, and these two kinds of blends have higher melt elasticity, and have higher parts-moulding characteristic under specific melt-processed operational condition.

Embodiment 9-11

The preparation of blend: is that 85/15,70/30 and 50/50 weight ratio is mixed being furnished with on the Haake mixing machine that Rheomix 3000 alms bowls describe device above-mentioned interpolymer (K) and vinyl aromatic polymer (D) according to (K)/(D), prepares three kinds of blend compositions of embodiment 9,10 and 11.The composition of blend is at first carried out the dry state blend, enter constant temperature then in 190 ℃ mixing machine.Charging and make temperature equilibrium need 3 to 5 minutes.Speed with 40 rev/mins (rpm) is mixed molten materials 10 minutes at 190 ℃.

The performance data of these blends and blend components is listed in the table 12.

Table 12

	Polymer blend or embodiment
						(K) *	(PS) *	9	10	11
	Blend composition, (K)/(D) weight ratio	100/0	0/100	85/10	70/30						50/50
Mechanical property
						Xiao A hardness	75	98	76	89	97
Tensile modulus, MPa	6.5	1860.3	13.8	68.9	661.9
						Modulus in flexure, MPa	68.8	3135.8	52.4	111.7	688.8
Yielding stress, MPa	1.3	39.5	2	4.3	9.4
						Breaking strain, %	475.3	1.6	481.3	459.4	4.4
Rupture stress, MPa	22.6	38.8	20.3	10.3	9.5
						Energy-to-break, Newton meter	102.2	1.1	89.1	74.4	1.2
Stress relaxation, % (50%/10 minute)	38	CBM 1	51.2	66.1	CBM 1
						The melt rheological property energy
η×10 -5(0.1 rad/second), pool	1.05	4.48	1.07	1.26	2.1
						η(100/0.1)	0.15	0.018	0.12	0.093	0.057
Tan δ (0.1 rad/second)	4.2	2.59	3.43	3.49	2.91

^*Non-embodiments of the invention

1 energy measurement not

2 do not survey

Compare with each component polymer, the stress during by fracture, strain and total energy-to-break data, table 12 shows that the blend composition of embodiment 9,10 and 11 all has good comprehensive mechanical properties under situation about any mechanical property not being exerted an influence.Though its toughness of 50/50 composition is lower than other two kinds of blends, than unmodified vinyl aromatic polymer height.

Further, embodiment 9 and 10 blend show the stress relaxation higher than component interpolymer.

The melt rheology data of three embodiment 9,10 and 11 blends show, the performance (0.1 rad/second) under low the shearing can be carried out blend and regulates with low viscous blend.

Embodiment 12 and 13

The preparation of blend: is that 75/25 and 50/50 weight ratio is mixed being furnished with on the Haake mixing machine that Rheomix 3000 alms bowls describe device above-mentioned interpolymer (L) and vinyl aromatic polymer (D) according to (L)/(D), prepares two kinds of blend compositions of embodiment 12 and 13.The composition of blend is at first carried out the dry state blend, enter constant temperature then in 190 ℃ mixing machine.Charging and make temperature equilibrium need 3 to 5 minutes.Speed with 40 rev/mins (rpm) is mixed molten materials 10 minutes at 190 ℃.

The performance data of these blends and blend components is listed in the table 13.

Table 13

	Polymer blend or embodiment
					(L) *	(PS) *	12	13
	Blend composition, (L)/(D) weight ratio	100/0	0/100	75/25					50/50
Mechanical property
					Xiao A hardness	88	98	95	97
Tensile modulus, MPa	20	1860.3	194.4	1313.5
					Modulus in flexure, MPa	62.1	3135.8	N.D.	N.D.
Yielding stress, MPa	2.4	39.5	9.8	16.6
					Breaking strain, %	377.5	1.6	199.8	20.6
Rupture stress, MPa	34.3	38.8	14.2	19.5
					Energy-to-break, Newton meter	145.5	1.1	92.6	16.4
Stress relaxation, % (50%/10 minute)	30.2	ND **	46	ND **
					The melt rheological property energy
η×10 -5(0.1 rad/second), pool	16.6	4.48	21.1	11.4
					η(100/0.1)	0.16 *	0.018	0.012	0.023
Tan δ (0.1 rad/second)	2.37	2.59	0.64	1.32

^*Non-embodiments of the invention

^*Energy measurement not

Mechanical performance data shows that embodiment 12 and 13 shows with the high olefin content interpolymer has excellent consistency.Blend has high yielding stress and higher breaking strain performance.Further, (L) compares with interpolymer, and the blend of embodiment 12 unexpectedly has high stress relaxation.

Two blends all have low tan δ value, and this expression is compared with any one blend components, and these two kinds of blends have higher melt elasticity, and have higher parts-moulding characteristic under specific melt-processed operational condition.

Embodiment 14

The preparation of A, ethylene/styrene multipolymer

According to the following steps, adopt (tertiary butyl amino) dimethyl (tetramethyl--η 5-cyclopentadienyl) silicomethane dimethyl titanium (IV) catalyzer and three (pentafluorophenyl group) borine promotor to prepare the ethylene/styrene multipolymer.In 2 liters of reactors that have a stirring, add about 360 gram mixed alkanes solvent (ISOPAR ^TME, the registered trademark of Exxon chemical company and by its product) and about 460 the gram styrene copolymerized monomer.By the differential pressure plavini hydrogen is joined in the reactor from 75 milliliters of injection jars then.Reactor is heated to 80 ℃, and reactor is saturated to required pressure with ethene.Be drawn into the method in the toluene solution of catalyzer by toluene solution and catalyzer and promotor are mixed in a loft drier the promotor of 0.005 mol of aequum.The solution of gained is transferred in the catalyzer feed pot, and injection joins in the reactor.Polyreaction is carried out under the condition that continues feeding ethene.Other catalyzer and promotor periodically join in the reactor.After 20 minutes, polymers soln is taken out from reactor and add Virahol reaction terminating.Position phenol resistance anti-oxidant (Irganox with 100 milligrams ^TM1010, the registered trademark of Ciba Geigy company and by its product) join in the polymkeric substance.In 135 ℃ reduced vacuum baking oven, dry about 20 hours to remove the volatile matter in the polymkeric substance.The ethylene pressure that in preparation ethylene/styrene multipolymer, is adopted and the melting index (I of Δ hydrogen pressure and gained multipolymer ₂) and styrene content list in the following table 14.

Table 14

Interpolymer	Isopar TM E	Vinylbenzene	H 2(Δ)		Ethene		Reaction times	Temperature of reaction	Catalyzer
											(g)	(g)	psig	kpa	psig	kpa	(min)	(℃)	(μmol)
E/S-1	365	465	6	41	150	1034	20	80	9.0
										E/S-2	365	454	16	110	200	1379	20	80	5.0
E/S-3	361	461	21	145	250	1724	20	80	4.5

Table 14 (continuing)

Interpolymer	I 2	Styrene content
							Mole %	Weight %	Weight %
E/S-1	0.37	17.3	43.7	1.5
					E/S-2	0.22	13.9	37.5	Do not survey
E/S-3	0.10	10.4	30.1	1.8

B, the test preparation of injected sample

With the component in the table 15 on 30 millimeters twin screw V30 mixing machines in Baker Perkins MPC corotation transition between 190 ℃ and 210 ℃, and on 38 millimeters single screw extrusion machines of exhaust, mix subsequently.The die head of polymer melt by one two hole cools off polymer strands then and cuts into pellet in water-bath.

Resin is carried out injection moulding is used for performance test with preparation sample being furnished with on the Domag D100-75 type injection moulding machine of 31 mm dia barrels and mould.

Table 15

The component code name	Component	Weight percentage
			U	The polymkeric substance improving agent	2.5
R	HIPS XZ-95198.00 1	79.9
			S	TBBA 2	8.3
S	Sahtex TM 8010 3	6.0
			T	Weisspiessglanz	3.3

1 high-impact polystyrene, Dow chemical company produces, and has following performance: melt flow rate (MFR)=3/10 Fen Zhong @200 ℃/5 kilograms of grams and beam type shock strength are 2.2 ft-lb/inches (12 kilograms-cm/)

2 tetrabromo-bisphenols

3 brominated flame retardants, the registered trademark of Albemarle company is also listed in the table 16 by the The performance test results of the type of anti-combustion polystyrene (IRPS) blend of its product molding.

Table 16

	E/S-1	E/S-2	E/S-3	Kraton 1102 a*
					Instrument dart shock strength in-lb kilogram-centimetre	50 58	65 75	40 46	50 58
Melt flow rate (MFR) (restraining/10 Fen Zhong @200 ℃/5 kilograms)	7.9	7.6	7.5	6
					Vicat softening temperature ℃	202 (94.4)	203 (95)	202 (94.4)	203 (95)
Stretching die octarius/square inch MPa	313,000 2,158	287,000 1,978	302,000 2,082	282,000 1,944
					Tensile yield pound/square inch MPa	3,980 27	3,980 27	3,970 27	3,830 26
Tensile elongation during fracture, %	80	60	80	90
					Gardner shock strength in-lb kilogram-centimetre	157 181	137 158	73 84	90 104
2.0mm the UL-94 flammability rating	V-2 b	V-2 b	V-2 b	V-2 b

^*Non-embodiments of the invention

A70/30 styrene butadiene three block rubber (SBS multipolymer), the registered trademark of Shell company and by its product.Kraton ^TM1102 have following performance: melt flow rate (MFR)=12 restrain/10 Fen Zhong @200 ℃/5 kilograms

This quantification gradation of b is not material or the hazard level of other any material under actual flame combustion state that is used for reflecting here

In the test of Gardner anti-impact, the total energy that the E/S multipolymer is absorbed is 73 to 157 in-lbs (84 to 181 kilograms-centimetre), and in comparison, the total energy that the SBS multipolymer is absorbed is 90 in-lbs (104 kilograms-centimetre).The size of these numerical value shows: the shock strength of (1) flame retardant type HIPS can be improved by adding the ES interpolymer; (2) shock strength of the type of anti-combustion polystyrene (IRPS) is subjected to the influence that the E/S multipolymer is formed; (3) containing the shock strength of the IRPS of interpolymer can be suitable even higher with the shock strength of the IRPS that contains at present commercial general impact modifier SBS.

Claims (19)

1, the goods except that film, contain polymer materials blend composed of the following components:

(A) at least a random substantially interpolymer of 11 to 99% weight, this interpolymer contains following monomer component:

(1) 1 to 65% mole

(a) at least a vinylidene aromatic monomer, or

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

(c) combination of at least a vinylidene aromatic monomer and at least a hindered aliphatic vinylidene monomer and

(2) 35 to 99% mole of at least a aliphatics alpha-olefin with 2 to 20 carbon atoms; With

(B) 1 to 89% weight

(1) homopolymer of at least a vinylidene aromatic monomer, or

(2) interpolymer of at least a one or more vinylidene aromatic monomers and/or one or more hindered aliphatic vinylidene monomers, or

(3) also contain at least a in (1) or (2) of impact modifier, or

(4) combination of two or more (1), (2) or (3) arbitrarily.

2, the polymer materials blend that contains following component:

(A) at least a random basically interpolymer of 1 to 99% weight, this interpolymer contains following monomer component:

(1) 1 to 65% mole polymer unit, its derived from

(a) at least a vinyl or vinylidene aromatic monomer,

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

It is selected from vinyl cyclohexane and 5-ethylidene-2-norbornene,

Or

(c) (a) with (b) combination and

(2) 35 to 99% mole polymer unit, its derived from ethylene and/or at least a aliphatics alpha-olefin with 3 to 20 carbon atoms; With

(B) 1 to 99% weight

(1) homopolymer of at least a vinyl or vinylidene aromatic monomer,

(2) at least a interpolymer of one or more vinyl or vinylidene aromatic monomer and one or more copolymerisable monomers except that ethene and/or aliphatic alpha-olefin, or

(3) also contain at least a in (1) or (2) of impact modifier, or

(4) combination of two or more (1), (2) or (3) arbitrarily.

3, the blend of claim 2, wherein the consumption of component (A) accounts for component (A) and (B) 40 to 97% weight of weight sum; And the consumption of component (B) accounts for component (A) and (B) 60 to 3% weight of weight sum.

4, the blend of claim 2, wherein the consumption of component (A) accounts for component (A) and (B) 40 to 95% weight of weight sum; And the consumption of component (B) accounts for component (A) and (B) 60 to 5% weight of weight sum.

5, each goods or blend in the aforementioned claim, wherein

(i) component (A2) has 2 to 12 carbon atoms;

(ii) the vinyl of component (B) or vinylidene aromatic monomer are represented by following general formula:

R wherein ¹Be selected from H and have and be phenyl or have 1 to 5 and be selected from halogen, C smaller or equal to the alkyl of 3 carbon atoms and Ar _1-4Alkyl and C _1-4The substituent phenyl of haloalkyl.

6, each goods or blend in the aforementioned claim, wherein the copolymerizable monomer of component (B) is selected from alpha-methyl styrene, N-phenylmaleimide, N-alkyl maleimide, acrylamide, vinyl cyanide, methacrylonitrile, maleic anhydride, vinylformic acid, vinylformic acid C _1-4Alkyl ester or methacrylic acid C _1-4Alkyl ester.

7, each goods or blend in the aforementioned claim, wherein component (B) is polystyrene or the polystyrene that contains impact modifier.

8, each goods or blend in the aforementioned claim, wherein component (A1a) is that vinylbenzene and component (A2) are at least a combination in ethene or ethene and propylene, 4-methylpentene, butene-1, hexene-1 or the octene-1.

9, each goods or blend in the aforementioned claim, wherein component (A1a) is a vinylbenzene; Component (A2) is ethene or ethene and propylene, 4-methylpentene, butene-1, at least a combination in alkene-1 or the octene-1; And component (B) is polystyrene or the polystyrene that contains impact modifier.

10, each goods or blend in the aforementioned claim, wherein component (A) is to carry out the polymerization preparation in the presence of limited catalyzer of metallocenes or geometric configuration and promotor.

11, the binder composition that contains each blend among the claim 2-10.

12, sheet material or the film that the blend of claim 1 is obtained through calendering, casting or blowing.

13, the blend of claim 1 injected, pressing mold, extruded or blowing and the goods that obtain.

14, the fiber for preparing by the blend of claim 1, foams or latex.

15, foamable composition, contain:

(I) at least a whipping agent; With

(II) blend of at least a interpolymer or interpolymer, it comprises:

(A) at least a random basically interpolymer of 1 to 99% weight, this interpolymer are derived from the polymer unit of following component:

(1) 1 to 65% mole (a) at least a vinyl or vinylidene aromatic monomer, or (b) at least a hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer, it is selected from vinyl cyclohexane, vinyl cyclohexane and 5-ethylidene-2-norbornene, or (c) (a) and combination (b) and

(2) 35 to 99% mole polymer unit, its derived from ethylene and/or at least aly have 3 aliphatics alpha-olefins to about 20 carbon atoms; With

(B) at least a vinyl or the vinylidene aromatic monomer of 1 to 99% weight, or at least a interpolymer of one or more vinyl or vinylidene aromatic monomer and/or one or more copolymerisable monomers except that ethene and/or aliphatic alpha-olefin.

16, the foamable composition of claim 12 is foamed and the foams that obtain.

17, the expanded bead that comprises each blend among the claim 2-10.

18, the preparation method of the expanded bead of claim 17 is characterized in that, the resin particle of each blend among the claim 2-10 is suspended in them is insoluble to basically in wherein the liquid medium; Flood described resin particle with whipping agent; And described resin particle is discharged into the zone of pressure relief, form foam beads.

19, a kind of binder composition, it comprises the polymer materials blend that contains following component:

(A) at least a interpolymer of 1 to 99% weight, this interpolymer contains following monomer component:

(1) 1 to 99% mole

(a) at least a vinylidene aromatic monomer, or

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

(c) combination of at least a vinylidene aromatic monomer and at least a hindered aliphatic vinylidene monomer and

(2) 35 to 99% mole of at least a aliphatics alpha-olefin with 2 to 20 carbon atoms; With

(B) 1 to 99% weight

(1) homopolymer of at least a vinylidene aromatic monomer, or

(2) interpolymer of at least a one or more vinylidene aromatic monomers and/or one or more hindered aliphatic vinylidene monomers, or

(3) also contain at least a in (1) or (2) of impact modifier, or

(4) combination of two or more (1), (2) or (3) arbitrarily.