CN1430631A

CN1430631A - Substantially random interpolymer grafted with one or more olefinically unsaturated organic monomers

Info

Publication number: CN1430631A
Application number: CN01810152A
Authority: CN
Inventors: G·格特尔; M·E·罗兰德; S·R·贝特索; M·J·格斯特; K·卡特泽; R·韦沃斯; T·T·阿尔古尔; H·P·雷迪
Original assignee: Dow Global Technologies LLC
Current assignee: Dow Global Technologies LLC
Priority date: 2000-05-26
Filing date: 2001-05-24
Publication date: 2003-07-16
Also published as: AU2001263430A1; JP2003535194A; WO2001092357A1; BR0111483A; KR20030005397A

Abstract

A graft polymer according to the invention contains a backbone of one or more substantially random interpolymers, comprising: (1) polymer units derived from: (a) at least one vinyl or vinylidene aromatic monomer, or (b) at least one hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer, or (c) a combination of at least one aromatic vinyl or vinylidene monomer and at least one hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer, and (2) polymer units derived from at least one of ethylene and/or a C3-20 alpha-olefin; and (3) optionally polymer units derived from one or more of ethylenically unsaturated polymerizable monomers other than those derived from (1) and (2); said backbone being grafted with one or more olefinically unsaturated organic monomer(s). In a preferred embodiment such graft polymers were prepared using a reactive extrusion process.

Description

With the random basically interpolymer of one or more olefinically unsaturated organic monomers grafted

Invention field

The present invention relates to the random basically interpolymer of grafting, it has used one or more olefinically unsaturated organic monomers grafting.This random basically interpolymer comprises the polymer unit that is produced by at least a aliphatic olefin hydrocarbon monomer with 2 to 20 carbon atoms, and by at least a vinyl or vinylidene aromatic monomer and/or the polymer unit that produces by at least a hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer.The present invention and then relate to this blend that has one or more to have the graft copolymerization body of grafting or non-grafted alkene or non-olefinic polymkeric substance.The present invention relates to comprise one deck grafted at least basically random interpolymer multilayered structure and comprise the mixture of this interpolymer.The present invention also provides the grafted application of random interpolymer basically, for example moulding and fabricated product, comprise the application in the fiber.

Background of invention

The same type of material that comprises interpolymer can prepare by the following method: the polymerization of ethene and/or alpha-olefin and at least a aromatic series and fat (ring) family's vinyl or vinylidene monomer, it comprises random basically interpolymer, is known in this area.For example record and narrate in EP-A-416815 US-A-5, the random basically ethylene/styrene interpolymer in 703,187 and US-A-5,872,201.

Some relate to the similar content of grafted ethylene/styrene interpolymer and limited reference also can be found in the art.US-A-6,015,625 have related to adhesive resin composition, and it comprises the alpha-olefin/aromatic ethenyl compound random copolymer of at least a portion and graft modification fully, and the weight percent of the grafting amount of unsaturated carboxylic acid or derivatives thereof is 0.01-30 in this interpolymer.

Grafted ethene/alpha-olefin interpolymer has record in following document, as EP-A-428510, and EP-A-439079, EP-A-605952, US-A-4,762,890 and US-A-5,705,565.Polar-modified isotactic polyprophlene is also known.This polar-modified polypropylene can be used as coupling agent and be used for the autohension coated material of metallic surface in the thermoplastic fibre glass composite.In addition, this graftomer has a lot of potential purposes concerning those those skilled in the art.

Blend, for example MALEIC ANHYDRIDE grafted olefin homo and multipolymer and polyolefine can be used to wide application field, for example comprise food packaging film, particularly multilayer film, floor and carpet systems, or pipeline coatings.

Yet the existing known and material that uses particularly carries out reactivity when extruding in its preparation process, show tangible change on molecular wt and molecular weight distribution.This change is undesirable side effect, cause molecular wt to increase and colloid formation (it especially results from ethene and ethylene copolymer) or molecular wt minimizing, corresponding to the increase (it especially results from polypropylene and mainly comprises third rare polypropylene copolymer) of dissolved matter flow velocity.

Although these materials are correctly used, the application that random copolymer is basically more expanded is also constantly sought in industry.In addition, industry also seeks to provide performance to improve and advanced novel copolymerized body.

Various olefin fibres, its fiber forming material is based on the polymkeric substance of ethene, and polypropylene or other olefin unit are known in existing field.The disclosed fiber of EP-A-44295 comprises MALEIC ANHYDRIDE (MAH) grafted linear polyethylene, and more excellent is MAH grafted high density polyethylene _gOr MAH grafted linear low density polyethylene (LLDPE).Because their adhesion property and wetting properties, this fiber it is reported that part is used for the application of adhesive fiber.Result as graft modification it is reported, the melt index of graftomer has significant minimizing than corresponding non-grafting parent material.For example, find that the melt index of HDPE reduces between about 20-about 70, specifically depend on the grafting level.The remarkable minimizing of melt index is relevant with the increase basically of molecular weight.The increase of this molecular weight is for example caused by the crosslinked polymer degree, and the expansion of the molecular weight distribution that is accompanied by, all be polymer graft modification do not expect side effect, this can cause adverse influence to the processing characteristics in the fiber forming process.As everyone knows, traditional in the prior art grafted polyethylene, for example be used for that polyethylene/terephthalic acid polyglycol ester (PET) conjugate fiber uses, limited the fibrous woven processing characteristics, for example produced fibre breakage, the enhancing of die pressure and more common filter change in the spinning nozzle.Therefore, need the new polymers that has strengthened processing characteristics, the shortcoming of existing materials used can be avoided or be reduced at least to its processing characteristics, and make the forming process of fiber that higher manufacturability energy be arranged.

The objective of the invention is to satisfy above-mentioned and other demand.Especially, an object of the present invention is the initial interpolymer of non-grafting than correspondence, provide graftomer superior comparability, processing characteristics and other useful characteristics, it can be produced and not have the remarkable change of molecular weight and molecular weight distribution, and/or does not have the significant increase or the minimizing of melt flow rate (MFR).The grafted that the invention provides advanced novel characteristics is the preparation method of random interpolymer basically.Another object of the present invention provides the application of this graft copolymerization body, and for example, polymer composition and prescription are as blend and multilayer tablet and mould material and fiber, and it has benefited from this interpolymer.The invention provides the random basically interpolymer of grafted in the more application of wide spectrum, it has benefited from advanced novel characteristic, for example the enhancing between system components consistency and associativity.Another object of the present invention is to provide a successive treatment process to the interpolymer modification that utilizes crosslinking technology, and as the result of graft modification, interpolymer molecule weight wherein only changes seldom, even does not have fully.Successive method provided by the invention has comprised high shear force and pyritous uses, and it need use extruding technology.

Summary of the invention

The present invention relates to have one or more as the novel graftomer of defined random basically interpolymer skeleton hereinafter, this polymer backbone is formed by a kind of olefinically unsaturated organic monomers grafting at least.More specifically, the present invention relates to a kind of graft copolymerization body, it comprises: (1) polymer unit derives from:

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

(b) at least a aliphatics or cycloaliphatic vinyl or the vinylidene monomer of being obstructed, or

(c) mixture and (2) polymer unit of at least a aromatic ethenyl or vinylidene monomer and at least a be obstructed aliphatics or cycloaliphatic vinyl or vinylidene monomer derive from and are selected from ethene and C _3-20At least a alkene of alpha-olefin; (3) optional polymer unit derives from the unsaturated monomer that gathers of one or more ethylenic, derives from

(1) and except those of (2),

Wherein the interpolymer skeleton is at least by a kind of olefinically unsaturated organic monomers grafting.Particularly, this graftomer is a kind of random copolymer of grafting basically with a kind of random basically interpolymer graft modification skeleton.The present invention also relates to utilize at least a itself also can be by the blend of grafting or other alkene of non-grafted or non-olefinic polymkeric substance and this novel graftomer.

The invention still further relates to melt processing and prepare this graftomer, particularly utilize reaction extrusion molding and hot melt grafting method to prepare these novel graft copolymerization bodies.

Another aspect of the present invention relates to the purposes of this novel graft copolymerization body and by fabricated product (fabricated article) that they were produced.

One embodiment of the invention relate to a kind of layered composite, and wherein one deck comprises by graft copolymerization body provided by the invention at least, or a kind of polymer blend that comprises this type of graft copolymerization body.

Another embodiment of the invention relates to filamentary material, and it comprises according to the random basically interpolymer of grafted of the present invention, comprises the fiber by random basically interpolymer of grafted and the preparation of a kind of polyolefinic blend, and the fabric that makes of fiber thus.

Summary of the invention:

Definition:

All that the present invention relates to belong to the element or the metal of a specific family and all publish company limited published and had copyright in 1989 the periodic table of elements with reference to CRC.Simultaneously, anyly among the present invention relate to all periodic table of elements unanimities therewith of family or a plurality of family, and use the IUPAC system to come family is numbered.

As long as have 2 unit differences at least between any low value and any high value, then any numerical value of enumerating herein comprises that low value arrives all values between the high value.For example,, as temperature, pressure, time or the like be, as from 1-90 if mention the variate-value of the quantity or a method of a component, preferably from 20-80, more preferably from 30-70, this just means, as 15-85,22-68,43-51, equivalences such as 30-32 are all included.If a value is less than 1, then a unit can be 0.0001,0.001,0.01 or 0.1.Similarly, the combinations of values between Schwellenwert and maximum that might enumerate, in all being contemplated as falling with in this article.

The term of mentioning in the literary composition " multipolymer " refers to a kind of polymkeric substance, and this multipolymer is formed by at least two kinds of different monomer polymerizations.

The term of mentioning in the literary composition " interpolymer " refers to a kind of polymkeric substance, and this interpolymer is prepared by at least two kinds of different monomer polymerizations, and it comprises multipolymer and trimer or the like.

Chemical reaction process when the term of mentioning in the literary composition " reaction is extruded " refers to polymkeric substance and/or can gather monomer extrude continuously.Reactant must be in a kind of physical condition that is suitable for extruding processing.Reaction can be carried out under molten polymer state or liquid monomer state, perhaps to be dissolved or suspended in the solvent or to be carried out under the state of solvent plastifying polymkeric substance.The chemical reaction process of extruding continuously that finger has short retention time is extruded in reaction.By M.Xanthos, Carl Hanser Verlag, Munich, Vienna writes, New York Barcelona in " reaction extrude-principle with actual " book of publishing in 1992 to detailed instruction being arranged about the reaction extrusion.

Term " derives from " and refers to by specific raw material manufacturing or mix, but not necessarily is made up of the simple mixtures of those raw materials.Composition " results from " simple mixtures that specific raw material may be a starting raw material, also may comprise the reaction product of those raw materials, even is made up of the reaction product or the degraded product of starting raw material fully.This comprises, but is not limited to, and those " result from " grafting organic monomer or organic acid monomer product.With regard to the grafting organic acid monomer, acid moieties, produce, extrude or the course of processing in experienced a step or a multistep chemical reaction that can change its structure.Especially, the free carboxylic acid group can react and change into ester, acid anhydrides or hydrochlorate.Equally, when being initial reactant with the acid anhydrides, it can change free acid into, or a kind of ester, or a kind of hydrochlorate.Those skilled in the art will readily recognize that when thermal treatment organic acid graftomer, this is very common phenomenon.Those skilled in the art also can recognize, for example, the maleic acid anhydride component can exist with the form of initial acid anhydrides, free maleic acid, a kind of ester or a kind of metal-salt, they are formed with the polymeric composition react by maleic acid anhydride component and another component, simultaneously, they can recognize that also these all structures are included among the present invention.

Term " comprises " and means " comprising " here.

Unless stated otherwise, all umbers and per-cent are all by weight.

Term " random basically " refers to a kind of random basically interpolymer in this article, comprise and derive from ethene and/or one or more alpha-olefines polymer of monomers unit, also comprise the polymer unit that derives from one or more vinyl or vinylidene aromatic monomer and/or aliphatics or cycloaliphatic vinyl or vinylidene monomer, especially, concerning the ethylene/styrene interpolymer, refer to that then the monomeric distribution of interpolymer described here generally can describe with (Markovian) first progression or the second progression statistical model of Bernoulli (Bernoulli) statistical model or Markov chain, these two kinds of statistical models are in " polymer sequence measure: C-13NMR method " (New York Science Press that J.C.Randall writes, 1977, pp71-78) (J.C.Randall inPOLYMER SEOUENCE DETERMINATION is described in the book, Carbon-13NMR Method, Academic Press New York, 1977, pp71-78).Preferably, random basically interpolymer do not comprise more than 15% whole be all vinyl or the vinylidene aromatic monomer that surpasses 3 unitary vinyl or vinylidene aromatic monomer.More preferably, the feature of this interpolymer does not lie in its high (greater than 50mol%) degree of isotacticity or degree of syndiotacticity.This just means on the C-13NMR spectrogram of random interpolymer basically, with the main chain mesomethylene carbon of representing meso sequence or racemize sequence and the corresponding peak area of methine carbon not the total main chain mesomethylene carbon of should exceed and methine carbon peak area 75%.

Term " fiber " is consistent with its meaning commonly used unless stated otherwise, includes, but not limited to ultimate fibre, refers to that DENIER greater than single thread of 15, is typically greater than 30; Thin denier's fiber or ultimate fibre refer to that DENIER is less than 15 thread; Many ultimate fibres refer to that the thin denier's ultimate fibre that forms simultaneously spins on a bundle fiber, generally comprises at least 3 to several thousand ultimate fibres; Staple fibre refers to be formed or be cut into short, and typically, length is the thin DENIER bundle of 2.5-20cm; O-fiber refers to be embedded into the superfine discontinuous ultimate fibre of an about successive substrates; Multicomponent fibre as conjugate fiber, refers to comprise at least two kinds with the fiber continuous and/or polymkeric substance that disperse phase exists; Multi-component fibre as bi-component fibres, refers to comprise two or more, and every kind exists with external phase, for example, and with shoulder to shoulder or the fiber of the polymeric constituent of sheath core arrangement.

Interpolymer in order to novel graft copolymerization body among production the present invention comprises random basically interpolymer, it is by polymerization i) ethene and/or one or more 'alpha '-olefin monomers, the ii) aliphatics or cycloaliphatic vinyl or the vinylidene that are obstructed of one or more vinyl or vinylidene aromatic monomer and/or one or more spaces and randomly iii) other can gather ethylenically unsaturated monomers.

The alpha-olefin that is fit to comprises, for example, comprises about 20 of 3-, preferably, and about 12 of 3-, more preferably 3 alpha-olefins to about 8 carbon atoms.Particularly suitable one or several the mixture that ethene, propylene, butene-1,4-methyl-1-pentene, hexene-1 or octene-1 or ethene and propylene, butene-1,4-methyl-1-pentene, hexene-1 or octene-1 are arranged.These alpha-olefins do not comprise aromatic portion.

Vinyl or vinylidene aromatic monomer that can being used in the present invention of being fit to produced interpolymer comprise, for example, and by those materials of following molecular formula representative:

R wherein ¹Be selected from hydrogen atom and the alkyl that contains 1-4 carbon atom, be preferably hydrogen atom and methyl; Each R ²Be independently selected from hydrogen atom and the alkyl that contains 1-4 carbon atom, be preferably hydrogen atom and methyl; Ar is that phenyl or one are selected from halogen, C by 1-5 _1-4Alkyl, and C _1-4The phenyl that the haloalkyl substituting group is replaced; The value of n is that 0-is about 4, is preferably 0-2, is most preferably 0.Typically vinyl aromatic monomers comprises all isomer and the analogue of vinylbenzene, Vinyl toluene, alpha-methyl styrene, t-butyl styrene, chlorostyrene and these compounds.Particularly suitable this type of monomer comprises the low alkyl group of vinylbenzene and it-or the derivative of halogen-replacement.Preferred monomer comprises vinylbenzene, alpha-methyl styrene, low alkyl group-(C ₁-C ₄) or the derivative that replaces of cinnamic phenyl ring, for example, the ortho position-, a position-and the contraposition vinyl toluene, encircle halogenated vinylbenzene, to Vinyl toluene or their mixture etc.Most preferred aromatic vinyl monomer is a vinylbenzene.

" being obstructed " aliphatics that is fit to or cycloaliphatic vinyl or vinylidene monomer are to add polyvinyl or vinylidene monomer corresponding to following molecular formula:

A wherein ¹Be the aliphatics or the alicyclic substituting group of paramount 20 carbon atoms of being obstructed, R ¹Be selected from hydrogen atom and the alkyl that contains 1-4 carbon atom, be preferably hydrogen atom and methyl; Each R ²Be independently selected from hydrogen atom and the alkyl that contains 1-4 carbon atom, be preferably hydrogen atom and methyl; Perhaps R selectively ¹And A ¹Form a ring system together.

Term " be obstructed " refer to have this substituent monomer generally can not be by the Ziegler-Narta polymerizing catalyst of standard, to carry out addition polymerization with the comparable speed of vinyl polymerization.This term meaning here is " space large volume " or " being obstructed in the space ".Aliphatics alpha-olefin with simple linear structure comprises, for example, and propylene, butene-1,4-methyl-1-pentene, hexene-1 or octene-1 be not considered to be obstructed aliphatics or cycloaliphatic vinyl or vinylidene monomer.

Preferred aliphatics or cycloaliphatic vinyl or vinylidene compound are that of having in the undersaturated carbon atom of ethylenic is the monomer that tertiary carbon or quaternary carbon replace.The substituent example of this class comprises alicyclic radical, for example, and cyclohexyl, cyclohexenyl, cyclooctene base or cycloalkyl or their aryl substituted derivatives, the tertiary butyl, norborneol alkyl etc.Most preferred aliphatics or cycloaliphatic vinyl or vinylidene compound are the various isomeric vinyl-cyclosubstituted derivatives of the tetrahydrobenzene of tetrahydrobenzene and replacement, and 5-ethylidene-2-norbornene.Particularly suitable is 1-, 3-, and 4 vinyl cyclohexene.

If random basically interpolymer comprises vinyl or vinylidene aromatic monomer and space be obstructed aliphatics or alicyclic monomer with the polymeric form, then the weight ratio between this monomer of two types is not so important just.Preferred this interpolymer comprises and derives from one or more vinyl or vinylidene aromatic monomer, perhaps the polymer unit of one or more aliphatics of being obstructed or alicyclic monomer.Aliphatics that vinyl or vinylidene aromatic monomer are better than being obstructed or alicyclic monomer.

Other optional polymerizable ethylene linkage formula unsaturated monomers comprise the strained cycloolefin, for example, and norbornylene and C ₁-C ₁₀Alkyl or C ₆-C ₁₀Aryl replaces norbornylene.In addition, one or more diene can randomly be incorporated in the interpolymer, and are so that unsaturated functional site to be provided on interpolymer, for example useful when participating in crosslinking reaction.Though perhaps the conjugated diene can be used for this purpose, preferably unconjugated diene as divinyl, 1,3-pentadiene (also being piperylene) or isoprene.Typical non-conjugated diene comprises, open chain non-conjugated diene hydrocarbon for example, and as 1,4-hexadiene (seeing United States Patent (USP) 2933480), 1,9-decadiene and 7-methyl isophthalic acid, 6-octadiene (also being called MOCD); Cyclic diolefine; Bridged ring cyclic diolefine, for example dicyclopentadiene (seeing United States Patent (USP) 3211709); Alkylidene-norbornylene, for example, methene norbornene or vinylidene norbornylene (seeing United States Patent (USP) 3151173).Unconjugated diene is not limited only to have only the diene of two two keys, comprises that also those have the compound of three or more pair key.Diene its weight when introducing random interpolymer basically accounts for the 0-15wt% of interpolymer gross weight.

Basically random interpolymer comprises pseudo-random copolymer, describes in United States Patent (USP) 5703187 at European patent 0416815 and Francis J.Timmers as James C.stevens etc., and the two all is hereby incorporated by.Basically random interpolymer also comprises the interpolymer of ethene, one or more 'alpha '-olefin monomers and at least a vinyl or vinylidene aromatic monomer, as descriptions in United States Patent (USP) 5872201 such as Yunwa W.Cheung, also be hereby incorporated by as a whole.

Because the use of catalyst system comprises a kind of coordination compound with constrained geometry, the preparation of interpolymer be by relative large volume or the monomer that is obstructed in random mode basically, under lower concentration or high density, embed logic in order according to one and merge and prepare.The multipolymer of ethene or alpha-olefin and a kind of be obstructed aliphatic ethylene base or vinylidene monomer or a kind of vinyl or vinylidene fragrant monomer preferably is described to " pseudo--random ".That is to say that this interpolymer lacks the monomer block of qualification, still, each monomer is limited to embed according to certain rule again.These rules can for example, at 75.4MHz, down be used Vatian VXR-300 in 130 ℃ to a polymkeric substance from certain resulting from inferring the interpolymer analysis experimental detail ¹³The C-NMR spectrometer is analyzed.Orthodichlorobenzene and the sym.-tetrachloroethane-d of 200-250mg interpolymer sample dissolution in 15ml heat ₂(volume ratio of the two is about 70/30), its chromium (III) three (acetylacetonate) concentration is about 0.05M, and this solution of part is joined in the NMR pipe of a 10mm.Parameter and condition below using: spectrum width 16500Hz; Acquisition time 0.090s; Pulse width 36; Time of lag, 1.0s uncoupled; FT size 32K; Number of scans＞30000; Live width 3Hz.The spectrogram that is write down is with tetrachloroethane-d ₂(δ 73.77ppm, TSM scale) is reference point.

Therefore, do not retrained by any specific theory, the result of above-mentioned experimental arrangement shows, a special notable attribute of puppet-random copolymers be all on polymer backbone substituted phenyl or space large volume be obstructed group separately by two or more MU (methylene unit).Under not by any specific condition that theory retrained, further above-mentioned experiment and notional result are made an explanation, just can draw, when the catalyzer in using the present invention carries out polyaddition reaction, when if a kind of monomer that is obstructed is embedded in the polymer chain in the growth, the monomer that the next one is embedded into must be that ethene or one is with the monomer of putting upside down or the form of " tail-tail " is embedded into that is obstructed.In polymerization process, ethene at any time can be embedded into.After a monomer that is obstructed that put upside down or " tail-tail " embedded, next monomer must be an ethene, because another monomer that is obstructed that embeds at this point will be placed on the place more close than above-mentioned minimum spacing to the substituting group that is obstructed.There are these polymeric rules to release, there is not homopolystyrene on any significant degree at the catalyzer that the present invention uses, though the multipolymer of ethene and cinnamic mixture rapid polymerization and generation high-phenylethylene content (typically cinnamic content is approximately up to 65mol%).

Under the condition of one or more metalloceness or the existence of constrained geometry catalyzer, can produce essentially no rule interpolymer by polymerization polymerisable monomer and promotor not of the same race.The preferred operational condition of this polyreaction be pressure from normal pressure to 3000 normal atmosphere, temperature is from-30 ℃ to 200 ℃.

U. S. application number is 702475, in the patent of submitting in May, 1991 (European patent A-514828), and United States Patent (USP) 5055438, United States Patent (USP) 5057475, United States Patent (USP) 5096867, United States Patent (USP) 5064802, United States Patent (USP) 5132380, United States Patent (USP) 5189192, United States Patent (USP) 5321106, United States Patent (USP) 5347024, United States Patent (USP) 5350723, United States Patent (USP) 5374696, United States Patent (USP) 5399635, United States Patent (USP) 5470993, disclose the catalyzer that is fit in United States Patent (USP) 5703187 and the United States Patent (USP) 5721185 and produced the method for random interpolymer basically, these all patents and application all are hereby incorporated by.

Basically random alpha-olefin/binyl fragrance interpolymer also can be used disclosed method in the Japanese Patent 07/278230, is prepared with the compound shown in the following molecular formula:

Wherein, C _p ¹And C _p ²Be the substituting group of cyclopentadienyl, indenyl, fluorenyl or these groups independently of each other; R ¹And R ²Be hydrogen atom, halogen atom independently of each other, have alkyl, alkoxyl group or an aryloxy of 1-12 carbon atom; M is an IV family metal, and preferably Zr or Hf most preferably are Zr; R ³Be to be used for commissure C _p ¹And C _p ²Alkylene or disilane base.。

Basically random alpha-olefin/binyl fragrance interpolymer also can be used (W.R Grace such as John G.Brandfute; Co.) in WO 95/32095, R.B.Pannell (Exxon ChemicalPatents, Inc.) in W94/00500, and disclosed method production among the plastics technology p25 (in September, 1992), all these are hereby incorporated by as a whole.

Same what be fit to is that those have Francis J.Timmers etc. disclosed in WO-A-98/09999, comprises at least a four component alpha-olefin/binyl aromatic series/vinyl aromatic/alpha-olefins and goes up random copolymer substantially.These interpolymers are theirs ¹³The intensity of the additional signal that comprises in the C NMR spectrogram is greater than noise between 3 times of peak values.The chemical shift range of these signals appears between 43.70ppm-44.25ppm and the 38.0ppm-38.5ppm.Especially, the main peak chemical shift is at 44.1ppm, 43.9ppm and 38.2ppm. ¹H NMR shows that the signal of chemical shift range between 43.70ppm-44.25ppm is methine carbon, and the signal of chemical shift range between 38.0ppm-38.5ppm is mesomethylene carbon.The appearance of these new signals is considered to owing to comprise that the sequence of two head-to-tail vinyl aromatic monomers insets causes, the front and back of this inset have an alpha-olefin inset at least, for example a kind of four grouping ethylene/styrene/styrene/ethylene, wherein said four grouping styrene monomer insets occur uniquely in the mode of 1,2 (head-to-tail).Those skilled in the art equally also knows, for comprising a kind of vinyl aromatic monomer but not vinylbenzene and a kind of a-alkene but not four groupings of ethene, ethylene/vinyl base fragrant monomer/vinyl aromatic monomer/ethene four groupings will produce similarly ¹³C NMR peak, but chemical shift is slightly different.

These interpolymers can, be approximately-30 ℃ to about 250 ℃ in temperature, and polymerization production and getting under the condition of the catalyzer of following molecular formula representative existence.

Wherein, each C _pThe π key is bonded to the cyclopentadienyl of the replacement on the M independently in each case; E is carbon or silicon; M is an IV family metal, preferred Zr, Ti or Hf, Zr most preferably, each R is hydrogen atom, alkyl, sila alkyl (silahydrocarbyl) or alkyl silyl independently, comprises paramount about 30, more preferably 1 to about 20, more preferably arrive about 10 carbon atoms or Siliciumatom; Under every kind of situation, each R` is hydrogen atom, halogen atom, alkyl,-oxyl, sila alkyl, alkyl silyl independently, comprise paramount about 30, preferred 1 to about 20, and more preferably 1 to about 10 carbon atoms or Siliciumatom, perhaps two R` can be together one by C _1-10Alkyl replace 1, the 3-divinyl; M is 1 or 2; Optional but preferably, under the condition that an active co catalyst exists.Especially, the substituted cyclopentadienyl of Shi Heing comprises the compound that those following molecular formula are represented:

Wherein, each R is hydrogen atom, alkyl, sila alkyl or alkyl silyl in each case independently, described group comprises up to about 30, preferred 1 to about 20, more preferably 1 form the divalent derivative of this group together to about 10 carbon atoms or Siliciumatom or two R groups.Preferably, R is that (comprising all suitable isomer) hydrogen atom, methyl, ethyl, propyl group, butyl, amyl group, hexyl, phenmethyl, phenyl, silyl or (be fit to) two R groups are joined together to form the condensed ring system in each case independently, for example, indenyl, fluorenyl, tetrahydro indenyl, tetrahydrofluorenyl or octahydrofluorenyl.

Concrete preferred catalyzer comprises, for example racemize (dimethylsilane two bases)-two-(2-methyl-4-phenyl indenyl) zirconium dichloride, racemize (dimethylsilane two bases)-two-(2-methyl-4-phenyl indenyl) zirconium 1,4 phenylbenzene-1,3 divinyl, racemize-(dimethylsilane two bases)-two-(2-methyl-4-phenyl indenyl) zirconium two-C ₁-C ₄Alkyl, racemize-(dimethylsilane two bases)-two-(2-methyl-4-phenyl indenyl) zirconium two-C ₁-C ₄Alkoxide or their mixture.

Can also use the catalyzer of following constrained geometry based on titanium, [N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η-)-1,5,6,7-tetrahydrochysene-s-Yin reaches province-1-yl] silane amido (silanaminato) (2-)-N] the titanium dimethyl; (1-indenyl) (tertiary butyl amido) dimethyl-silane titanium dimethyl; ((the 3-tertiary butyl) (1,2,3,4,5-η)-I indenyl) (tertiary butyl amido) dimethylsilane titanium dimethyl; ((3-sec.-propyl) (1,2,3,4,5-η)-1-indenyl) (tertiary butyl amido) dimethylsilane titanium dimethyl or their combination.

The further preparation method of used interpolymer is described in the document among the present invention.Longo and Grassi, Makromol.Chem.191 volumes, 2387-2396 page or leaf (1990), and people such as D ' Anniello, Journal of Applied Polymer Science (journal of applied), the 58th volume, 1701-1706 page or leaf (1995), report is based on methyl alurnoxane (MAO) and cyclopentadienyl-titanium trichloride (CpTiCl ₃) catalyst system prepare ethylene-styrene copolymer .Xu and Lin. Polymer Preprints Am.Chem.Soc.Div.Polym.Chem., the 35th volume, the 686th, 687 page (1994), report uses MgCl ₂/ TiCI ₄/ NdCl ₃/ Al (iBu) ₃Catalyzer carries out the random copolymers that copolyreaction obtains vinylbenzene and propylene.People such as Lu, Journal of Applied Polymer Science (journal of applied), the 53rd volume, 1453-1460 page or leaf (1994) has been described use TiCl ₄/ NdCl ₃/ MgCl ₂/ al (Et) ₃Catalyzer carries out ethene and cinnamic copolyreaction.Sernetz and Mulhaupt, Macromol.Chem.Phys., v.197, pp.1071-1083, (1997) have described polymeric reaction condition to using Me ₂Si (Me ₄Cp) (the n-tertiary butyl) TiCl ₂/ methylaluminoxane Ziegler-Natta catalyst carries out the influence of the copolyreaction of vinylbenzene and ethene.The ethene of producing by the metalloscene catalyst of bridge joint and the method such as following document description: the Arai of styrol copolymer, Toshiaki and Suzuki, Polymer Preprints Am.Chem. Soc., Div.Polym.Chem., the 38th volume, the 349th, 350 (1997) or Denki KagakuKogyo KKr DE-A19711339 and authorize the United States Patent (USP) 5,652,315 of Mitsui Toatsu chemical company.The preparation of alpha-olefin/binyl aromatic monomer interpolymer such as propylene/styrene and butylene/styrene is as describing in following document: the United States Patent (USP) 5,244,996 of authorizing Mitsui petrochemical industry company limited.All above-mentioned methods that prepare interpolymer have been incorporated the present invention into as a reference.And, people's such as Toru Aria Polymer Preprints, the 39th page, the 1st phase, in March, disclosed ethene and cinnamic multipolymer also can be used for the present invention in 1998.

In preparation basically during random interpolymer, because the homopolymerization of vinyl aromatic monomer under the high temperature, form the atactic vinyl aromatic homopolymer of some amount.The existence of vinyl aromatic homopolymer is generally harmless and can be stood to purpose of the present invention.If necessary, can be by abstraction technique as from the solution of the solvent that contains non-interpolymer or vinyl aromatic homopolymer, carrying out selective precipitation, preparation vinyl aromatic homopolymer from described interpolymer.But, be purpose of the present invention, preferably there is 30wt.% at the most, preferably less than the atactic vinyl aromatic homopolymer of 20wt.% (gross weight with interpolymer is a radix).

The random basically interpolymer of a kind of preferred grafting comprises by one or more, be preferably a kind of, the skeleton of random interpolymer basically, it comprises:

(1) polymer unit, it derives from:

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

B) at least a ground aliphatics or cycloaliphatic vinyl or the vinylidene monomer of being obstructed, or

C) combination of at least a aromatic ethenyl or vinylidene monomer and at least a be obstructed aliphatics or cycloaliphatic vinyl or vinylidene monomer and

(2) polymer unit, its derive from ethene and (or) C _3-20At least a in the alpha-olefin; With

(3) optional polymer unit, it derives from the unsaturated monomer that gathers of one or more ethylenic, derives from except those of (1) and (2);

This skeleton is with one or more ethylenic unsaturated organic monomers grafting.

Graftomer among the present invention comprises, and preferably, is made of the melt index (I of this random copolymer basically a kind of skeleton of random basically interpolymer graft modification ₂) be at least 0.01, preferably between about 0.01-about 1000, more preferably approximately between the about 50g/10min of 0.01-, its molecular weight distribution (ratio of weight-average molecular weight and number-average molecular weight; M _w/ M _n) be 1.5-20, comprising:

(1) polymer unit, it derives from:

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

(c) combination of at least a aromatic ethenyl or vinylidene monomer and at least a be obstructed aliphatics or cycloaliphatic vinyl or vinylidene monomer and

This skeleton is with one or more ethylenic unsaturated organic monomers, and preferred ethylenic unsaturated organic acid is monomer-grafted.The selection of the melt index of the random interpolymer basically of graft modification is planted the required satisfied final service requirements of interpolymer thus and is decided.This selection often runs into to one skilled in the art.Melt index (I ₂) measure according to ASTM-1238, its condition determination is 190 ℃/2.16kg.

Another preferred graftomer comprises one or more among the present invention, is preferably a kind of skeleton of random interpolymer basically, and the melt index of this random copolymer is about 0.01 to about 50g/10min, M _w/ M _nFor about 1.5 to about 20, comprising:

(1) approximately 1mol% is to about 65mol%, and preferred 8mol% is to the polymkeric substance of 65mol%

The unit, this polymer unit derives from:

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

(c) at least a aromatic ethenyl or vinylidene monomer and at least a be obstructed aliphatics or cycloaliphatic vinyl or vinylidene monomer combination and

(2) approximately 35mol% is to about 99mol%, and preferred 35mol% is to the polymer unit of 92mol%, and it derives from ethene and/or C _3-20At least a in the alpha-olefin; With

(3) 0mol% is to the polymer unit of 20mol%, and it derives from the unsaturated monomer that gathers of one or more ethylenic, derives from except those of (1) and (2);

Another preferred graftomer among the present invention, the M of the random interpolymer basically of wherein said graft modification _w/ M _nFor about 1.5 to about 20, and comprise:

(1) approximately 5mol% is to about 50mol%, and preferred 10mol% is to the 43mol% polymer unit, and it derives from:

A) by the vinyl or the vinylidene aromatic monomer of following molecular formula representative: R wherein ¹Be selected from hydrogen atom and contain the alkyl of 3 or carbon atom still less, Ar is phenyl or is selected from halogen, C by 1-5 _1-4Alkyl, and C _1-4The phenyl that the haloalkyl substituting group is replaced, or

B) by be obstructed aliphatics or the cycloaliphatic vinyl or the vinylidene monomer of following molecular formula representative:

A wherein ¹Be the aliphatics of 20 carbon atoms at the most of a space large volume or alicyclic

Substituting group, R ¹Be the alkyl that is selected from hydrogen atom and contains 1-4 carbon atom, it is former to be preferably hydrogen

Son and methyl; R ²Be independently selected from hydrogen atom and the alkyl that contains 1-4 carbon atom, excellent

Elect hydrogen atom and methyl as; Perhaps R ¹And A ¹Form a ring system together, or

C) combination (a) and (b), and

(2) approximately 50mol% is to about 95mol%, and preferred 57mol% is to the polymer unit of 90mol%, and it derives from ethene and/or is selected from least a alpha-olefin in propylene, 4-methyl-1-pentene, butene-1, hexene-1 or the octene-1, and

(3) 0mol% is to the unsaturated monomer that gathers of the described ethylenic of 20mol%, derives from except those of (1) and (2), is selected to comprise norbornylene or C _1-10Alkyl or C _6-10The norbornylene that aryl replaces.

Another embodiment preferred is a graftomer among the present invention, the M of wherein said random interpolymer basically _w/ M _nFor about 1.8 to about 20, and comprise:

1) approximately 13mol% is to the polymer unit of about 40mol%, and it derives from:

(a) described vinyl or vinylidene fragrant monomer, comprise vinylbenzene,

Alpha-methyl styrene, ortho position-, a position-and contraposition-vinyl toluene and ring on

Halogenated styrenes, or

(b) described aliphatics or cycloaliphatic vinyl or vinylidene monomer comprise 5-

Ethylidene-2-norbornylene or 1-vinyl cyclohexene, 3-vinyl cyclohexene,

And 4 vinyl cyclohexene, or

(c) combination of a and b and

2) about 60mol% is to the polymer unit of about 87mol%, and it derives from ethene or ethene

With described alpha-olefin, comprise ethene or ethene and propylene, 4-methyl-1-pentene,

At least a in butene-1, hexene-1 or the octene-1, and

3) the unsaturated monomer (derive from (1) and (2) those except) that gathers of described ethylenic is

Norbornylene.

Among the present invention, most preferred graftomer is that wherein the graft modification skeleton is those of random interpolymer basically, and this interpolymer comprises the combination of one or more vinyl aromatic monomers and ethene, perhaps ethene and one or more C ₃-C ₈The combination of 'alpha '-olefin monomers, or ethene and norbornylene composition.This interpolymer comprises and is selected from ethylene/styrene, ethylene/propene/vinylbenzene, ethylene/butylene/vinylbenzene, ethylene/pentene/vinylbenzene, ethylene/hexene/vinylbenzene, or ethylene/octene/cinnamic random basically interpolymer.

Seek out the graftomer among the present invention, one or more random basically interpolymers alkene unsaturated monomer (vinyl that for example, contains reactive monomer, or these monomeric mixtures) carried out chemical modification,, preferably, the free radical grafting that dissociates reaction.(additional) functional group has been introduced in graft modification on the interpolymer skeleton.The olefinically unsaturated organic monomers that is applicable to preparation graftomer of the present invention comprises any unsaturated organic compound, it (for example comprises at least one unsaturated ethylene linkage, at least one two key) and at least one carbonyl (C=O) (it also can be the carbonyl in the carboxyl), and, under the condition that is fit to, can be grafted to compound on the random basically interpolymer skeleton as top defined those.Representational these olefinically unsaturated organic monomers that comprise at least one carbonyl are organic carboxyl acids, comprise the monocarboxylic acid di-carboxylic acid, their acid anhydrides, ester and metal and non-metal salt.Preferably, olefinically unsaturated organic monomers contains a unsaturated ethylene linkage that combines with carbonyl group at least.Preferred organic monomer comprises maleic acid, FUMARIC ACID TECH GRADE, vinylformic acid, methacrylic acid, methylene-succinic acid, Ba Dousuan, tiglic acid and styracin, and their acid anhydride, ester and salt derivative.Vinylformic acid, maleic acid and MALEIC ANHYDRIDE are the preferred olefinically unsaturated organic monomers that contains at least one unsaturated ethylene linkage and at least one carbonyl group, and most preferred monomer is a MALEIC ANHYDRIDE.

Though according to the present invention, can carry out grafting, also can carry out grafting with two or more different grafted monomer with a single class monomer.In a particularly preferred embodiment of the present invention, the skeleton of interpolymer is to use the MALEIC ANHYDRIDE grafted.Therefore, particularly preferred interpolymer is MALEIC ANHYDRIDE (MAH) grafted ethylene/styrene interpolymer among the present invention, or MALEIC ANHYDRIDE grafted ethene/C ₃-C ₈Alpha-olefin/styrene copolymer.

It is favourable quickening the grafting process with superoxide or other free radical initiator.The superoxide that is fit to comprises; but be not limited to; aromatic series diacyl peroxide, aliphatics diacyl peroxide, diprotic acid superoxide, ketone peroxide, alkyl peroxyester, alkyl peroxide, alkyl and dialkyl peroxide; for example; diacyl peroxide, 2,5-two (t-butylperoxy)-2,5-dimethylhexane or 2; 5-dimethyl-2,5-two (t-butylperoxy) hexin-3.

Under molten state,, come the random basically interpolymer skeleton of grafting to extrude acquisition by activity with olefinically unsaturated organic monomers by reacting with solid or liquid polymers.These class methods all have description in United States Patent (USP) 3236917, United States Patent (USP) 4762890 and United States Patent (USP) 5194509, be hereby incorporated by.Graft reaction is the reaction that free free radical causes, and free free radical generates with ultraviolet, chemistry or other technologies.The details of relevant graft reaction has introduction in above-mentioned United States Patent (USP), also have further instruction hereinafter.Grafting method also can be a solid phase grafting method.

For example, in United States Patent (USP) 3236917, polymkeric substance is introduced in a pair of roller mixing machine and mixes down at 60 ℃.Then unsaturated organic compound and a kind of free radical initiator, for example, benzoyl peroxide joins in the mixing machine together, mixes down at 30 ℃, finishes until grafting.Also described similar grafting process in United States Patent (USP) 5194509, difference is that the temperature of reaction in this patent is higher, for example, 210 ℃-300 ℃ and do not use free radical initiator, or used initiator concentration is low.

Instructed another preferred grafting method in United States Patent (USP) 4950541, its disclosed method is hereby incorporated by, and part is used in this invention.According to this preferable methods, basically the device that random interpolymer and olefinically unsaturated organic monomers are being fit to, for example a kind of forcing machine, for example, in a kind of twin screw liquefaction forcing machine, be at reactant under the temperature of molten state or liquid state, under the condition that free radical initiator exists, mix and react.Unsaturated organic monomers can mix in the solvent that be well known to those skilled in the art and dissolving inactive.Preferably, unsaturated organic monomers is injected into the zone that keeps in the forcing machine under pressure.

According to the present invention, graftomer preferably according to the present invention prepares by melt processing, and especially, temperature range is at about 50 ℃-Yue 300 ℃.This melt processing can be batch-wise or successive molten processing technology.In the particularly preferred embodiment in the present invention, utilized a kind of active extruding technology.Utilizing the graft copolymerization body of above-mentioned fusion technology preparation is a selected objective target thing of the present invention.

Utilize the random basically graft copolymerization body of the preparation of preferred manufacturing procedure among the present invention, its molecular weight or molecular weight distribution are extruded or fusion metamorphosis according to their activity, do not have astoundingly or do not change significantly.For example, with similar grafting HDPE or grafting LLDPE polymer phase ratio, the relative stability of interpolymer molecule amount is reflected in, for example the constant basically melt index of random basically graft copolymerization body.Compare with initial not graft copolymerization body, the melt index of product graft copolymerization body remains unchanged basically, even change is arranged, also is that reduction (depending on interpolymer content) is arranged relatively slightly.Select and control grafting method and grafting condition so that functional group be incorporated in the interpolymer be by with the reaction of olefines unsaturated monomer, during polymer backbone have no or significantly not crosslinked at least or fracture.By contrasting the not melt index of graft copolymerization body and graft copolymerization body, these effects of prosecution at an easy rate.Basically the overwhelming majority of random interpolymer, or all physics and/or mechanical characteristics remain unchanged.Compare with the graft copolymerization body of producing by prior art, these improvement have proved their advantage, for example, do not have or reduce gel formation significantly, and/or there are not the increase of (or reduction) flow rate and intensity, impact property, thermal characteristics and a workability.

Yet under some condition, grafting method also may cause the variation of graft copolymerization body molecular weight and molecular weight distribution.If these variable effects the desired properties and the subsequent reaction of graft copolymerization body, those skilled in the art should distinguish out at an easy rate.Although in the present invention, not have obvious variation be favourable and preferred to the molecular weight of interpolymer in the grafting process, and in some cases, change of molecular weight but is good concerning some purposes.Therefore, in the grafting process, the graft copolymerization body that molecular weight changes also is a theme of the present invention.

According to the present invention, the method of the random basically graft copolymerization body of a kind of preferred preparation is to satisfy a kind of active extrusion method of following condition: equipment: anyly can make single screw rod or the multiscrew that processing temperature and time (time length) controlled and make the adding of solid or liquid ingredient to be controlled, for example, twin screw extruder, or any fusion/heat is melted mixing equipment.Temperature: processing temperature must be higher than the fusing point of interpolymer to a certain extent, or if interpolymer is unbodied, then temperature of reaction should make interpolymer operate not shearing degradation easily in employed equipment.The temperature of processing must be higher than the kick off temperature of employed superoxide, but not high to cause all superoxide with just degrade fully before other component is mixed.Time: the time that processing continues should guarantee to make all reactive components fully melt-blended, and will be longer than the superoxide that can make employed 90-99% and decompose the required time (this time can calculate from the transformation period of employed superoxide) fully.Those skilled in the art, experiment that it goes without doing just can estimate the needed suitable condition of the active extrusion of the present invention at an easy rate.Feed component: the component of adding in active extrusion can add in any mode in following three kinds of modes: (1) three kind of component separately adds, add random basically interpolymer earlier, add vinyl acids (VA) then, promptly, the olefines unsaturated monomer adds superoxide (ROOR) at last; (2) add interpolymer earlier, then add the mixture of superoxide and vinyl acids; (3) three kinds of all components add together.Form: generally speaking: interpolymer 99.94wt%-85wt%

Vinyl acids (VA) 0.05wt%-10wt%

Superoxide (ROOR) 0.01wt%-5wt%

VA/ROOR???????10/1-1/10(wt/wt)

VA/ROOR 10/1-1/10 (moles/mole) is preferred: interpolymer 99.9%wt-97wt%

Vinyl acids 0.05%wt-2wt%

Superoxide 0.05%wt-1wt%

VA/ROOR???????10/1-1/1(wt/wt)

VA/ROOR 10/1-1/1 (moles/mole)

For above-mentioned optimum condition, interpolymer is represented any random basically interpolymer of definition herein, those preferred interpolymers of pointing out preferably, for example, the ethylene/styrene interpolymer, ethylene/alpha-olefin/styrene copolymer, the blend of random interpolymer basically, for example, the blend of ethylene/styrene interpolymer and ethylene/alpha-olefin copolymer.It also comprises hydrogenant and partially hydrogenated irregular phenylethylene/divinyl (SB) rubber.Vinyl acids comprises, for example, and the carboxylic acid that has polymerizable double bond or the carboxylate moiety of any replacement or non-replacement.This comprises, but is not limited to maleic acid or maleate, FUMARIC ACID TECH GRADE or fumarate etc.Superoxide comprises any organic peroxy compound.This comprises, but is not limited to dicumyl peroxide, benzoyl peroxide etc.For the present invention, any free radical initiator can use, for example azo-compound.

Therefore, utilize preferable methods to prepare graft copolymerization body among the present invention, promptly have improved, As mentioned above, intensity, outward appearance and other good characteristics, melt process or especially, the resulting random basically interpolymer of active extrusion also is another theme of the present invention (comprising the polymer composition that contains such interpolymer) by heat.The present invention also relates to a kind of graft polymerization compositions, it comprises random basically interpolymer and a kind of alkene unsaturated organic monomers, maleic acid or the MALEIC ANHYDRIDE reaction product under the condition that a free radical initiator (preferred a kind of superoxide) exists for example, it is characterized in that reaction product contains more than about 0.1wt% along the interpolymer skeleton, preferred about 0.5wt% is to about 2wt% or more organic monomer (with the form of covalent linkage), for example, Succinic Acid or Succinic Acid base.

In one embodiment of the invention, this novel random basically graft copolymerization body uses as the expanding material of potting resin product.Product many moldings or that extrude contains weighting material, and for example, tripoli, mica, glass, clay, carbon black etc. are in order to improve intensity and/or other desirable performances are provided.Generally speaking, these weighting materials are only compatible with resinous matrix, and add the amount of the weighting material of resinous matrix, and just, loading level is restricted.Expanding material is used for being coated with or handling weighting material, thereby makes itself and resinous matrix compatible better, and then obtains higher loading level.The random basically interpolymer of graft modification among the present invention is good especially expanding material, because loading level that can be high, just, amount according to the expanding material that adds, be directed in the specific resinous matrix more than a kind of weighting material, or a spot of expanding material just can reach same loading level.In addition, the expanding material among the present invention can also make composition have desirable performance with the form with preprocessing of processing.With the form of processing, intensity and impact property have raising the processing component of random polymkeric substance basically with respect to grafted of no use.With the form of preprocessing, for example bead, plate, uncured wrapping material or the like, the discontinuous or continuous processibility of composition is with respect to not using the grafting among the present invention raising to be arranged the processing component of random polymkeric substance basically.

The random basically interpolymer of grafted of the present invention is not owing to have or reduced gel formation significantly, make final product have excellent outward appearance, visual appearance and transparent particularly, this makes them be particularly suitable for wrapping material, makes the food Package material especially and uses.Similarly, do not have or reduce gel formation significantly and do not increase (or reduction) flow rate basically when reaching other purposes, its advantage also is tangible.

Graft copolymerization body of the present invention owing to its improved adhesiveproperties to polar polymer, also can be used as the chemical coupling agent of thermoplastic fibre glass synthetics, or uses as the polymer coated material of self-adhesion.These coated materials for example, can be used for metal or other surfaces; Other possible purposes is as primer composition or hotmelt.

Grafting among the present invention purposes of random interpolymer basically comprises: but be not limited to, floor system for example, improves weighting material combination and wearing quality; Carpet backing and installation system for example, improves between component, for example, the combination between pet fiber, tynex and polypropylene fibre, improve with base material combine and, for the ease of reclaiming the consistency between the raising carpet components; Building comprises the glass line system, as a kind of coagulation additive, metope insulating covering agent or the like; Electric wire and cable system, particularly those comprise the electric wire and the cable system of weighting material, laminated vessel and membrane structure and those have the goods and the foodstuff products of the packing of controllable pressure especially, for example, comprise polar polymer, for example, ethylene/vinyl acetate, ethylene/vinyl alcohol, ethylene/acrylic acid fat, polymeric amide and polyvinyl chloride homopolymer or multipolymer; Be suitable for painting/polyolefin structure that is suitable for printing, for example, film, plate and model product; Be used for splendid attire fluidic laminar structure, for example, gasoline can and tubing system; Polymkeric substance edge additive; Bituminous composition; Comprise a kind of scrim raw material, for example, nylon or polyethylene terephthalate, as, the laminar structure of artificial feather or tarpaulin for example; Sound and vibration management system; The tackiness agent that is used for yarn fabric and fibrous texture; Coating, tackiness agent and caulking joint composition; Be used for that the surface prevents to damage or corrosion, for example, chemical reagent and etching reagent, the synusia metal construction; Foams and combination foam body structure; Steel pipe coating and caking agent; Bond layer between the woven fabric polymeric amide; Be used for polyolefine, the conjugate fiber caking agent of polyethylene terephthalate and interpolymer; Be used to reclaim the expanding material of polymer composition.

The random basically graft copolymerization body among the present invention and the blend of other polymkeric substance also are themes of the present invention.Interpolymer of the present invention and one or more itself may be very useful after the blend by grafting or non-grafted alkene or non-olefinic polymkeric substance.For example, the example of these polymkeric substance is nylon, polycarbonate, polyethylene and multipolymer, polypropylene and multipolymer, polystyrene and styrol copolymer, styrene butadiene and other rubber or the like.In an embodiment preferred, the random basically interpolymer of graft modification and another thermoplastic polymer's dry blend are molten to be mixed, then molding or extrude goods into moulding.Such thermoplastic polymer comprises any and the random basically interpolymer compatible polymers of grafted, and comprises alkene and non-olefinic polymkeric substance, the non-polymers grafted of grafted.Such examples of polymer, for example, comprise high density polyethylene(HDPE) (HDPE), new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), ultra-low density polyethylene (ULDPE), polypropylene, ethylene-propylene copolymer, ethylene-styrene copolymer, polyisobutene, ethylene-propylene, ethylene-propylene-diene monomers (EPDM) multipolymer, polystyrene, vinylbenzene, acrylonitrile-butadiene-styrene (ABS) polymkeric substance (ABS), ethylene/acrylic acid (EAA), ethylene/vinyl acetate (EVA), ethylene/vinyl alcohol (EVOH), ethene and carbon monoxide (ECO) polymkeric substance, comprise what those were described in United States Patent (USP) 4916208, perhaps ethene, propylene and carbon monoxide (EPCO) polymkeric substance, perhaps ethene, carbon monoxide and vinylformic acid (ECOAA) polymkeric substance etc.Representational non-olefinic polymkeric substance is polyester, polyvinyl chloride (PVC), epoxide, urethane, polycarbonate, polymeric amide etc.Operable in the present invention, the polymeric amide that is fit to comprises the polymeric amide that those are produced by condensation and ring-opening polymerization.They often are named as nylon.Proper raw material comprises, for example, and nylon 6, Ni Long11 and nylon 12.Polymeric amide also can use the method for condensing preparation, for example, and with diamines and diprotic acid (the perhaps derivative of diprotic acid) reaction.The structure of Zhi Bei raw material is carried out the digitizing name by this method, carbonatoms between the nitrogen-atoms in two amine moieties was the carbonatoms of diprotic acid part, for example afterwards before this, polymkeric substance with 1 and hexanodioic acid preparation is described to polyamide 66 or nylon 66.Condensation polyamide comprises, for example, and polymeric amide 46, polyamide 66, polyamide 69, polyamide 6 10, polyamide 6 12.Polymeric amide and MALEIC ANHYDRIDE (MAH) the grafted blend of random interpolymer basically provides good especially processing characteristics.

The random basically graft copolymerization body among the present invention and the blend of another kind of polymkeric substance preferably, comprise one or more the additional polymeric constituents from about 0.1wt% to about 99.9wt%, based on the gross weight of composition.Preferred additional polymer component is Natene or multipolymer or homopolymer polypropylene or multipolymer, and polymeric amide, for example nylon.Blend of the present invention also comprises those compound systems, comprises at least two kinds of dissimilar polymkeric substance and one or more random basically graft copolymerization bodies, and random basically graft copolymerization body wherein plays a kind of expanding material.Basically the amount that random graft copolymerization body uses at multicomponent system, preferably from about 2wt% to about 30wt%.

These blends also can demonstrate advantage in wrapping material use, these wrapping material comprise food and industrial packaging material and other purposes, can give full play to the characteristic after the improvement of polymeric blends wherein, these purposes are known by those of skill in the art.

The blend of the random basically interpolymer of grafted or these graft copolymerization bodies is particularly useful in containing the composition of one or more weighting materials according to the present invention, for example, contains the composition up to one or more weighting materials of 95wt%.Product many moldings or that extrude contains weighting material, and for example, tripoli, mica, glass, clay, carbon black etc. are in order to improve intensity and/or other desirable performance is provided.Basically the random interpolymer of the graft modification compound system component of wishing especially in particular among the present invention, it gives the desirable performance of the composition with the preprocessing form with processing by strengthening weighting material and containing combination between the polymeric matrix of random interpolymer basically of graft modification.The example of these weighting materials has glass, glass fibre, mica, lime carbonate, clay, carbon black, whiting, cement flour, feldspar, tripoli, the tripoli of being fuming, silicate, aluminum oxide, magnesium oxide, weisspiessglanz, zinc oxide, barium sulfate, pure aluminium silicate, Calucium Silicate powder, titanium oxide, glass microsphere, mica, clay, wollastaone and chalk, magnesium hydroxide, calcium hydroxide and aluminium hydroxide and analogue thereof.The composition of graft copolymerization body or interpolymer of the present invention and weighting material and particularly account for the composition of composition 10wt% to the weighting material of 90wt% also are themes of the present invention.

Another theme of the present invention is the layered composite that contains the blend of random basically interpolymer of one deck grafted at least or interpolymer of the present invention.

In these layered composites, additive method might be difficult to bonded or use at least a kind ofly do not wish that in the finished product the material that exists can bonded raw material layer structure carry out combination.Enhanced cementability or compatibility are provided between the aspect of graft copolymerization body of the present invention for different multilayered structures.For example, use graft copolymerization body media layer of the present invention, in conjunction with polyethylene layer and polarity raw material layer, for example nylon or ethylidene vinyl alcohol are possible.Graftomer is with polarity and non-polar polymer characteristic, and therefore can form improved film or multilayered structure.

Material of the present invention may comprise one or more additives, and for example, (for example, fortified phenol is as the Irganox of Ciba Geigy production for antioxidant ^TM1010), phosphite (for example, the Irgafos of CibaGeigy production ^TM168), UV stabilizer, (for example, photostabilizer is as hindered amine for the film additive; Plasticizer is as dioctyl phthalate (DOP) or epoxidised soybean oil; Thermo-stabilizer; Mould separant tackiness agent is as hydrocarbon binders; Paraffin is as polyvinyl paraffin wax; Processing aid, as oil, organic acid, as stearic acid, the organic acid metal-salt; Linking agent is as superoxide or silane; Tinting material or pigment, the add-on of these additives should be controlled at and not hinder desirable physics of the present composition or mechanical property.Those skilled in the art will appreciate that the add-on of above-mentioned additive, in the gross weight of composition, paramount generally speaking about 30wt%, preferably from about 0.01wt% to about 5wt%, more preferably from 0.02wt% to about 1wt%.

Graftomer, the blend of polymkeric substance or layered composite of the present invention can be processed into fabricated product with the method that this area is fit to.For example, by the complete processing of knowing, for example, and calendering, winding-up is cast or is extruded, and comprises complete processings such as coextrusion, and they can processed film forming or the stratiform thing of film or one or more multilayered structures.Injection moulding, compressed moulding is extruded or blow molding also can be made with composition of the present invention with assembly.In addition, composition of the present invention also can be processed into foam article or fibre product.In order to interpolymer and weighting material and arbitrarily additive combination be processed into the processing temperature of fabricated product, be from 100 ℃-300 ℃ generally speaking, preferably from 120 ℃-250 ℃, more preferably from 140 ℃-200 ℃.

Such fabricated product of the present invention also can foam.Foam layer can prepare by extrusion method, also can be from the inflatable particulate that maybe can foam, and moldable foam particles, or, can form sheet material by launching and/or engaging and weld these particulates from some microballons.Can be incorporated into various additives in or not this foamy structure, for example, stability control agent, nucleator, pigment, antioxidant, acid scavenger, ultraviolet sorbent material, fire retardant, processing aid or extrusion aid.Some additives wherein have detailed description hereinbefore.

Graft copolymerization body among the present invention and graft copolymerization body blend and composition can carry out crosslinked with chemistry or radiating method.The free free-radical crosslinking agent that is fit to comprises organo-peroxide, dicumyl peroxide for example, hydrolysising silane, organic azide, or their mixture.In addition, graft copolymerization body or interpolymer mixture or composition also can be grafted on the skeleton by silane moiety is interrupted, and hydrolysising silane makes between the contiguous polymer chain to connect by siloxanes and forms crosslinkedly then, reaches crosslinked purpose.

Graftomer among the present invention or polymer blend can be applied at an easy rate, extrude, or layer are layered on the substrate.Typical substrate comprises glass, metal, pottery, wood, polymeric substrate, natural fiber, unglazed thing, and their mixture.Another material that the present invention plants can be extruded, and mills, and perhaps calendering as no support membrane or film, for example, is used for producing floor tile, wall tile, floor pedal, wall coverings, perhaps the top ceiling overcover.They are specially adapted to as pugging or absorbing energy layer, film, film or plate.The film of all thickness scope, film or plate can be produced and obtain.According to end-use, the thickness range of above-mentioned substance is 0.5mm-20mm generally speaking, preferably, and 1mm-10mm.In addition, injection moulding assembly or winding-up mold goods, for example, and toy, container, material of construction, auto parts machinery and other durable goods can prepare production with composition of the present invention.

Find simultaneously, include novel grafting basically the fiber of random interpolymer benefit from the improvement characteristic of this interpolymer especially, for example, by improved processing characteristics and high productivity, in the fiber forming process, for example, the fiber spinning process (with traditional comprise graft polyolefin rather than grafted basically the fiber of random interpolymer compare).Have clear superiority be applied in the fiber be, obtain by graft modification, do not have or very little degree of crosslinking the random basically interpolymer of the grafting of perhaps higher molecular weight interpolymer.Such interpolymer is characterized in that their melt index changes (reduction) significantly owing to graft modification.

In a preferred embodiment, fiber provided by the invention contains the random basically interpolymer of grafting defined above, particularly the random basically interpolymer of those preferred grafting of above pointing out.Particularly preferably be contain such, preferred with ethylenic unsaturated carboxylic acid or its acid anhydride with di-carboxylic acid or monocarboxylic acid or their acid anhydride, more preferably with maleic acid or the random basically interpolymer of MALEIC ANHYDRIDE grafted, fiber.Basically random interpolymer uses maleic acid or MALEIC ANHYDRIDE grafting can make along the Succinic Acid of interpolymer skeleton or Succinic anhydried not take place or side reaction such as rare crosslinked or chain rupture.Preferably, the grafting melt index of random interpolymer basically is 5 or higher at least, preferably, is 10 or higher, with respect to the not significantly reduction of melt index of the random interpolymer basically before the grafting.Have advantage, one or more functional groups of in the grafting process, introducing, for example, the Succinic Acid group, and/or the content of Succinic anhydried group, account for the random basically interpolymer content of grafting, about at least 0.1wt%, preferably, at least about 0.5wt%, more preferably, about at least 1wt%.The residuals content of responseless ethylenic unsaturated organic monomers should be low as far as possible in interpolymer.

Fiber among the present invention can use known fiber production technology, and for example, melt spinning prepares.In this process, fused polymkeric substance or polymeric blends are extruded by a mould, and then the fused extrudate stretches, the curing of extrudate is by the heat passage realization of fluid medium towards periphery, then on the draw-off godet or on other turnbuckle surfaces, for example belt takes out solid-state extrudate.The extruded film tool can be the conventional film tool, for example, and a typical spinning nozzle that contains three or more holes to hundreds of and several thousand holes.Typical spinning nozzle comprises a filter element, to remove gel and other impurity that may pollute and block spinneret hole.Typically, spinning nozzle also comprises a breaker plate, be used for making the molten polymer flow that provides from extruder or toothed gear pump can equiblibrium mass distribution to the hole of all spinning nozzle.Melt spinning also can comprise cold stretching, thermal treatment and/or fiber or yarn crimp technology.Important aspect is when the polymkeric substance of molten state or polymeric blends leave spinning nozzle in the fiber production process, comes to position to the molecule in the polymkeric substance by stretch processing.The fiber production forming process may comprise that for example, the successive filament forms, and spinning is used staple fibre, netted combination, or air spray process, or melt-blown process.Textile fibres is favourable under high speed.

Preferred fiber comprises not grafted Alathon or not grafted ethene/C among the present invention ₃-C ₂₀Alpha-olefin copolymer and grafted be the blend of random interpolymer basically.Such fiber comprises many groups (multiconstituent), preferred conjugate fiber, and polynary (multicomponent) fiber, preferred bi-component fibres.For example, the conjugate fiber among the present invention can comprise graft copolymerization body or not grafted ethene homopolymer or multipolymer and the external phase of dispersion other components wherein on matrix direction/fine-fibered orientation.With in the polycomponent or conjugate fiber of the arrangement of the sheath/core heart, the random basically interpolymer of one or more grafted is included in shell or core, or in shell and the core, advantageously, with graftomer not, for example, homopolymer polypropylene or multipolymer, polystyrene, polymeric amide, basically random interpolymer or polyterephthalate (PET) mix.Bi-component fibres preferably contains graft copolymerization body and grafted polymer components not in identical external phase.Not polymers grafted and grafted basically the ratio of random interpolymer depend on grafting degree and desirable combination degree usually.Ratio between random basically interpolymer of suitable not graftomer/grafting, for example, should be from about 95/5 in about 80/20 scope.Grafting and not the graft-blending component can use the known method and apparatus of technology people in the field of the present invention, for example, melt and mix or do and mix, before extruding, mix.According to desirable performance and specific purposes, fiber of the present invention, typically, 15 deniers or be lower than the ultra micro filament of decimal DENIER.

Fiber of the present invention has multiple application.

In addition, the fiber of the present invention that relates in one aspect in addition in blend fiber of the present invention for example, additionally contains the fiber of processing.Fiber among the present invention has height flexible fiber, for example, polymeric amide, polyester, cotton, wood, real silk, Mierocrystalline cellulose, the Mierocrystalline cellulose of modification, for example regenerated fiber and regenerated fiber ester, with and analogue etc., be specially adapted to adhesive fiber and use.Fiber among the present invention has special advantage when using as adhesive fiber, because they are to the bonding force and the wetting properties of processing fiber, this bonding force and wetting properties are owing to the functional group in the graft copolymerization body (polarity) is strengthened, with the scope of the graft copolymer composition of relatively low melt temperature or relative and processing fiber.

In yet another aspect, the present invention relates to a fabric that contains among the present invention, non-woven fabric, or woven fabric, or contain the fiber blend of fiber of the present invention.For example, fiber can be formed cotton-wool, and forms fabric at the embossing roller of a heating by calendering thermal treatment.Cotton-wool also can carry out heat bonding by for example using infrared light or ultrasonic wave or similar approach, and then obtains lightweight fabric full of elasticity.These fibers also can be used for the traditional textile process, for example combing, starching, braiding or the like.The woven fabric of using the fiber among the present invention to make also can use heat-treating methods to change the characteristic of fabric.

Following Example has illustrated the present invention, but and any way that differs limit the scope of the invention.

Example:

Testing method

A) melt flow and density measurement

The molecular weight of the random interpolymer basically that uses among the present invention is by a melt index method of masurement, and according to ASTMD-1238,190 ℃/2.16Kg of condition (is called as Condition (E) in the past, is also referred to as I ₂), measure easily.

Melt index is inversely proportional to the molecular weight of polymkeric substance, and therefore, although be not linear relationship, molecular weight is high more, and melt index is low more.

During the molecular weight of the random interpolymer basically that in measuring the present invention, uses, Gottfert melt index (G, cm ³/ 10min) also very useful, the acquisition of Gottfert melt index is measured melt index I with using ASTMD1238 as automatic plastometer ₂Mode similar, fusion density is set at 0.7632, polyethylene fusion density is under 190 ℃.

At 190 ℃, the vinylbenzene of 29.8wt%-81.8wt% is measured fusant density and is used for relation between the cinnamic content of ethene-stupid ethenyl copolymer, as the function for the vinylbenzene total content.The content of random isotactic polystyrene typically is approximately 10% or still less in these samples.Because its content is very low, can think that the random isotactic polystyrene influence is very little in the sample.Simultaneously, the density after the random polystyrene fusion to contain high-load cinnamic sample melted after density be similar.When using the Gottfert melt indexer to measure fusant density, the fusant density parameter setting is 0.7632, and the collection of melt twisted wire is the function of time, works as I ₂In the time of effectively.For each melt twisted wire (melt strand), record weight and time and standardization are as the weight of material of generation in per ten minutes.The I of instrument calculating ₂Melt index values is also noted.Use following formula to calculate actual fusion density:

δ＝δ _0.7632×I ₂/I _2Gottfert

Here δ _0.7632=0.7632, I _2GottfertBe the melt index that shows.

One calculates the linear least square fitting of the fusant density of gained, and the relation of vinylbenzene total content can obtain an equation relatively, and relation conefficient is 0.91, and is as follows:

δ＝0.00299×S+0.723

Wherein, S is the weight percentage of vinylbenzene in polymkeric substance.This relation between vinylbenzene total amount and the fusant density can be used to measure actual melt index values, can use this formula if styrene content is known.

Therefore to a polymkeric substance, its vinylbenzene total content is 73%, and in conjunction with measuring the melt flow (Gottfert number) that obtains, following formula is:

δ＝0.00299*73+0.723＝0.9412

Wherein: 0.9412/0.7632=I ₂The analysis of/G# (measured value)=1.23B) vinylbenzene

The interpolymer styrene content among the ESI (random basically ethylene styrene interpolymer) and the content of random isotactic polystyrene homopolymer impurity can pass through nucleus magnetic resonance ( ¹H NMR) measure, all nuclear magnetic resonance samples all are to prepare in sym.-tetrachloroethane-d2 (tce-d2).Contain 1.6%～about 2.4% (weight percent) interpolymer of having an appointment in the solution that obtains.Directly interpolymer is weighed in the sample hose of 5mm the tce-d of 0.75ml five equilibrium ₂Be expelled in the sample hose closely suitable lid seal of sample hose by the needle cylinder injection device.Sample heats under 85 ℃ of temperature, with softening interpolymer.In order to make the sample mix after the sealing, use the blowing hot wind device to make it keep reflux state frequently.

Under 80 ℃, nuclear magnetic resonance spectrum is accumulated with sample probe, with tce-d ₂In the residual proton amount at 5.99ppm place as reference.The data of each sample are all collected in triplicate.The plant and instrument parameter of using when analyzing the interpolymer sample is: sweep length: 5000 hertz of data acquisition times: 3.002 pulse per second (PPS) width: 8 microsecond frequencies: 300 megahertzes postpone: transition in 1 second: the time that 16 analyze each sample needs is approximately 10 minutes.

At first, need portion 192, the spectrogram of 000Mw polystyrene sample.Polystyrene contains the proton of five kinds of different states, can distinguish by the nuclear magnetic resonance spectrum of proton.Among Fig. 1, the proton of these different states is marked as b: branch, α: α position, o: ortho position, m a: position, p: contraposition.The proton that comprises all repeat modes in the polymkeric substance has branch's proton, two α position protons, two ortho position protons, position proton and a contraposition proton between two.

Fig. 1

The nmr spectrum of polystyrene homopolymer is about the 7.1ppm place in chemical shift and a resonance center occurs, it might be the resonance peak of ortho position, three protons of contraposition, be approximately the 6.6ppm place in chemical shift and another resonance center occurs, may be the resonance peak of position proton between two, three protons of then corresponding α of the resonance peak at 1.5ppm and 1.9ppm place and b position.

The relative strength of resonance of all protons obtains by integral and calculating.7.1ppm the resonance integral result PS that locates _7.1Expression, same, the resonance integral PS at 6.6ppm place _6.6Expression, and aliphatics proton (from 0.8 to 2.5ppm integration) is used PS _AlExpression.Like this, PS _7.1, PS _6.6, PS _AlTheoretical ratio be 3: 2: 3, perhaps 1.5: 2: 1.5.For the random polystyrene homopolymer, all spectrum collected and ideal integration ratio 1.5: 2: 1.5 are in full accord.Among Fig. 1, the integration ratio that aliphatics is numbered the proton of α and b position should be 2: 1.The two states proton is also being obtained such result in the process of integration respectively.Simultaneously, through calculating, aromatic series is 5: 3 with aliphatics proton ratio, also meets theoretical value.

Like this, just obtained the hydrogen-nmr spectrum of ESI interpolymer.The spectrogram that obtains shows that it is 7.1ppm that resonance occurs in chemical shift, 6.6ppm and aliphatics proton resonance zone.Yet, a lot of a little less than the peak of peak, 6.6ppm place than this place in the polystyrene homopolymer in the ESI interpolymer, the appearance of this phenomenon may be because the position proton produces resonance between in the ESI interpolymer at the 7.1ppm place, like this, unique can the 6.6ppm place produce resonance have only as the ESI interpolymer in the random polystyrene homopolymer of impurity between the position proton.In the ESI interpolymer, with 7.1ppm the proton that the peak at center comprises ortho position on the aromatic nucleus, a position and contraposition, also comprise in the polystyrene homopolymer impurity proton at ortho position and contraposition on the aromatic nucleus.The peak in aliphatics zone comprises the aliphatics proton in ESI interpolymer impurity and the polystyrene homopolymer impurity simultaneously.

Explanation again: the relative intensity at peak is measured by integration, the resonance integral result I at 7.1ppm place _7.1Expression, same, the resonance integral I at 6.6ppm place _6.6Expression, and aliphatics proton domain integral result I _AlExpression.

I _7.1Comprise one produce ESI interpolymer aromatic protons aromatic protons component and produce polystyrene homopolymer impurity aromatic ring ortho position and and the component of contraposition proton.Therefore,

I _7.1=I _C7.1+ I _Ps7.1Wherein, I _C7.1Be the strength of resonance of aromatic protons in the 7.1ppm place interpolymer, I _PS7.1It is the strength of resonance of ortho position and a position proton in the 7.1ppm place polystyrene homopolymer.

Calculate theoretically, from the hydrogen-nmr spectrum of polystyrene homopolymer, be verified simultaneously, the strength of resonance (I that the impurity in the polystyrene homopolymer produces at the 7.1ppm place _PS7.1), equal 1.5 times in 6.6ppm place intensity.Therefore from the data that measure, can determine I _C7.1Value:

I _c7.1＝I _7.1-1.5(I _6.6)。

Equally, the relational expression below utilizing, can ESI and the strength of resonance of polystyrene homopolymer impurity calculate I _Al:

I _Al=I _Cal+ I _PsalWherein, I _CalThe strength of resonance that causes for aliphatics proton in the interpolymer, and I _PsalThe strength of resonance that causes for aliphatics proton in the polystyrene homopolymer impurity.Equally, know I by the resonance spectrogram of Theoretical Calculation and random isotactic polystyrene homopolymer _PsalBe I _6.61.5 times.Therefore can calculate I by following formula _Cal:

I _Cal=I _Al-1.5 (I _6.6) ethene and cinnamic molecular fraction can calculate by following in the interpolymer:

s _c＝I _c7.1/5

e _c＝(I _cal-(3×s _c))/4

E＝e _c/(s _c+e _c)

S=s _c/ (s _c+ e _c) wherein, E and S are respectively copolymerization of ethylene and cinnamic molar fraction in the interpolymer.

Ethene and cinnamic weight percentage can calculate by following formula:

Wt％E＝28E/(28E+104S)*100％

2Wt％S＝104S/(28E+104S)*100％

Therefore, in the ESI sample, the weight percentage of polystyrene homopolymer impurity is determined by following equation:

Wt%PS=Wt%S* (I _6.6/ 2S)/{ 100-[Wt%S* (I _6.6/ 2S)] * 100% vinylbenzene total content also can calculate by Fourier's infrared spectra (FTIR).C) molecular weight analyse instrument: 3 sections PL gels of PL-gel osmoticing chromatogram analysis model 210 (Polymer Laboratories company) PL-7.0 version quality software (Polymer Laboratories company) of being furnished with PD2040 light scattering apparatus (Precision Detectors company), (10 μ m MIXED-B parts number 1110-6100DW) (PolymerLaboratories company) material: polystyrene calibrating system S-M-10/44 (Polymer Laboratories company), polystyrene standard: 9.000.000 and 2.160.000 (Wyatt company) 1,2, the 4-trichlorobenzene is used for GPC, 0.2 μ m filters, use BHT (500ppm weight) stabilizing treatment (Fisher Scientific company) step: in the small test tube of a 20ml, add about 27mg sample, add about 15mgBHT, with the 15ml stabilizing treatment cross 1,2,4 trichlorobenzene.Vibrate 90 minutes with sample dissolution at 150 ℃.Five equilibrium 2ml solution joins SEC and adds in the model machine automatically.Condition: elutriant (stabilizing treatment cross 1,2, the 4-trichlorobenzene) the online degassing, solvent flux is 1ml/min; The sample injection rate is 200 μ l, and operating temperature is 140 ℃.For avoiding sample to produce thermal stresses in waiting for notes sample process, small test tube is deposited in 80 ℃ of environment always, is analyzing taking-up in previous hour.Volume correction is to be undertaken by the corrective system of Polymer Laboratories company, and the molecular weight of polystyrene standard is tested by light scattering apparatus.Polystyrene calibration curve is converted into the polystyrene calibration curve that meets the Khn-Mark-Houwink formula: polystyrene: [η]=9,53 * 10 ^-5* M ^0,725Polyethylene: η=40,6 * 10 ^-5* M ^0,725D) grafting content is determined: in interpolymer, the content of grafting maleic acid can be measured by following method: with washed with methanol graft copolymerization body, polymkeric substance after the dry flushing, wherein the carbonyl total content can be according to P A Callais and RT Kazmierczak (1-4 day in May, 1989, in the ANTEC meeting paper) step, measure by Fourier's Infrared spectroscopy.

Embodiment 1:

Ethene-styrene copolymer grafting preparation: ethene-styrene copolymer is according to United States Patent (USP) 5703187 (U. S. application series number US Application Serial Number 09/488,220; On January 19th, 2000, application can be asked for to the Dow chemical company) prepare.

The grafting sample makes preparation with the following method: a mixture of being made up of polymkeric substance, reactive monomer and initiator is joined in the Werner-Pfleiderer ZSK30 twin screw extruder.Wherein, reactive monomer is a MALEIC ANHYDRIDE, initiator is 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, polymkeric substance has the ethene-polystyrene copolymerization body of different styrene contents (30% and 70%, weight percent) and different melt index (1g/10min and 10g/10min).The weight ratio of MALEIC ANHYDRIDE/initiator/polymkeric substance is 1.5/0.05/98.45%.The twin screw extruder operating parameter setting is: bucket temperature (bushing temperature) (1-5 number and mould be respectively): 150 ℃ of helix speeds of 80 ℃, 150 ℃, 200 ℃, 200 ℃, 150 ℃, 150 ℃ (4) 210 ℃ of melt temperatures of melt temperature (mould): 150 rev/mins of products production speed: 8 kilograms/hour

At mould and feeding funnel place the airiness device is set, is necessary to use the free monomer of vacuum removal.

The MALEIC ANHYDRIDE content of melt index and graft modification and unmodified (at first) interpolymer is listed as follows:

The ESI sample	Vinylbenzene wt%	Preceding MI is extruded in reaction	Back MI is extruded in reaction	Grafted MAH content 1) wt%)	????Mw	????Mn
The ESI sample	Vinylbenzene wt%	Preceding MI is extruded in reaction	Back MI is extruded in reaction	Grafted MAH content 1) wt%)	????Mw	????Mn	????1	??30 ²⁾	??1.1	??-	????0	??79900	??31700
????2	??30 ²⁾	??1.1	??1.0	????0.3	??75200	??29700	????1	??30 ²⁾	??1.1	??-	????0	??79900	??31700
????2	??30 ²⁾	??1.1	??1.0	????0.3	??75200	??29700	????3	??30 ²⁾	??10	??-	????0	??51100	??10300
????4	??30 ²⁾	??10	??9.8	????0.2	??48900	??9800	????3	??30 ²⁾	??10	??-	????0	??51100	??10300
????4	??30 ²⁾	??10	??9.8	????0.2	??48900	??9800	????5	??70 ³⁾	??1.6	??-	????0	??-	??-
????6	??70 ³⁾	??1.6	??1.3	????0.3	??-	??-	????5	??70 ³⁾	??1.6	??-	????0	??-	??-

1) after the methanol extraction, total carbonyl compound content can be measured as follows: FTIR/Publication of Elf Atochem, P A Callais and R T Kazmierczak write, 1-4 day in May, 1989, ANTEC meeting 2) solvent of MALEIC ANHYDRIDE is MEK (methyl-ethyl ketone) 3) solvent of MALEIC ANHYDRIDE is that the Virahol data clearly show: there are not tangible polymkeric substance commissure or chain-breaking reaction to take place in the grafting process.

Embodiment 2:1) preparation of interpolymer:

In the recirculation reactor of a continuous operation, prepare random basically ethene-polystyrene copolymerization body (ESI numbering 7) and random basically ethylene-propylene-polystyrene copolymerization body (EPS numbering 1).Use the Ingersoll-Dresser twin-screw pump to reach mixing.Reactor 475psig (3, fill it up with liquid under 275kPa).Use the Kenic static mixer in syringe and the recirculation reactor pipeline in reactor, to add starting material and catalyzer/synergistic catalyst.After fluid is discharged by recycle pump, before coming back to the suction journey of recycle pump, need flow through two-layer shell wall and tubular heat exchanger.After last interchanger comes out, flow through syringe and static mixer of the fluid in the loop turns back in the suction journey of pump again.If possible, can increase and transport monomeric syringe and mixing tank.Circulate temperature in heat exchange oil and the shell side of treated water in interchanger with control loop.From loop reactor, between two interchangers, discharge the liquid product that generates.The flow and the solution density of discharging product can pass through Micro-Motion ^TMMass flowmeter is measured and is obtained.

Being expelled to solvent in the reactor as the part of charging, mainly is in order to guarantee that ethene does not evaporate from solution.Ethene being injected the liquid purpose that distributes from the pressure transferpump before the reaction system is that pump seal to closed circuit reactor partly provides competent flow.The solvent that increases is used for dilute catalyst.The solvent that increases mixes with the polystyrene monomers of free state at suction journey one end of pressure transferpump.The pressure transferpump with about 650psig (4,583kPa) to reactor delivery solvent and polystyrene.Pass through Micro-Motion ^TMMass flowmeter is measured the polystyrene flow that obtains increasing newly, and all solvents, polystyrene flow then are by an independent Micro-Motion ^TMMass flowmeter is measured and is obtained.Ethene with 690psig (4,865kPa) join in the reactor.The ethene flow also is by a Micro-Motion ^TMMass flowmeter is measured and is obtained.A under meter or the flow regulator amount with control transmission hydrogen in the ethene air-flow need be installed at ethene discharge control valve place.Propylene also can join in the system with the high pressure fluid form in solvent pressure transferpump back and go.Before the fluid with solvent/polystyrene composition mixed, ethene/hydrogen mixture was in room temperature state, and before all reaction mixtures entered reactor, temperature should be reduced to about about 2 ℃ by the glycol-cooled device.

Catalyst system is a three-component system, comprises a kind of titanium catalyst, aluminum cocatalyst and boron promotor.Three catalyst components of preparation catalyzer in three different containers, titanium catalyst (1 hydrogen-cyclopenta [1] phenanthrene-2-yl) dimethyl (TERTIARY BUTYL AMINE Mierocrystalline cellulose)-silane titanium 1,4 diphenyl diethylene, the following Table II of preparation process is described.The aluminum cocatalyst composition is the 3A type aluminium trimethide oxyethane (MMAO-3A behind the remodeling; CAS No 146905-79-5); Boron promotor structure is three (pentafluorophenyl group) boron (FAB, CAS No 001109-15-5).In the process of the different interpolymer one-component of preparation, the mol ratio (B/Ti) of employed boron promotor and titanium catalyst and the mol ratio (Al/Ti) of aluminum cocatalyst and titanium catalyst are as shown in table 1 below: the catalyst molar ratio in table 1 preparation ESI1-4 and the EPS-1 process

Polymkeric substance	The mol ratio of B/Ti	The mol ratio of Al/Ti
Polymkeric substance	The mol ratio of B/Ti	The mol ratio of Al/Ti	ESI-7	?5.5	?8.3
EPS-1	?4	?5	ESI-7	?5.5	?8.3

Novel solvent and the spissated material that is pre-mixed that is made of catalyst/co-catalyst/secondary promotor are joined independently and mix in the run tank, join in the reactor by the reinforced surge pump of the pulse of a variable-ratio afterwards.As previously mentioned, the three component catalyst systems suction journey that enters twin-screw pump by a syringe and static mixer joins in the reactor loop and goes.The starting material material also is to join in the reactor loop in the upstream that catalyzer adds a little by a syringe and static mixer, perhaps finishes the work of adding by a reinforced syringe/mixing tank between two interchangers.

Pass through Micro-Motion ^TMMass flowmeter is measured solution density and is characterized level of response, stops polyreaction by add catalyst failure agent (water) in reactive system.Use static mixer to strengthen the degree of mixing of catalyst reactor inefficacy agent and additive, fluid continues to enter the back, is used to the removal of solvents flash that extra energy is provided, in the reactor heaters.These flashes flow out from late phase reaction device well heater as waste water and produce, at reactor pressure control valve place, its absolute pressure from 475psig (3,275kPa) be reduced to about 450mmHg (60kPa).

The polymkeric substance of having removed flash enters the devolatilization cell mesh in the flow process.The volatile component that comes out from the devolatilization flash is equipped with shell side in the interchanger of ethylene glycol and concentrates, and through a vacuum pump, is discharged in the gas/liquid separating tank.In first vacuum system in the stage, when responseless ethene when container top is discharged, solvent/vinylbenzene shifts out as regenerated solvent from the bottom of container.Ethene flow Micro-Motion ^TMMass flowmeter is measured.With dissolved gases calculated amount in the ethene amount solubilizing agent/vinylbenzene fluid of discharging, can calculate the transformation efficiency of ethene.Polymkeric substance and residual solvent use toothed gear pump to pump in the final exhaust chest.The pressure-controlling of secondary exhaust chest in about 10mmHg (1.4kPa) absolute pressure with the residual solvent of flash distillation.Dry polymeric (＜1000ppm total volatile content) pumps into a underwater pelletizer with a toothed gear pump, and Rotary drying is collected.

The preparation condition and the amount of monomer that are used for producing one ethylene/styrene interpolymer are summarised in table 2.Table 2: the preparation condition of preparation ESI-7 and EPS-1

Interpolymer	Temperature of reactor	Solvent flux	The ethene flow	The propylene flow	Hydrogen flowing quantity	The vinylbenzene flow	Conversion of ethylene
Interpolymer	Temperature of reactor	Solvent flux	The ethene flow	The propylene flow	Hydrogen flowing quantity	The vinylbenzene flow	Conversion of ethylene		?℃	?kg/h	?kg/h	?kg/h	?kg/h	?kg/h	?％
ESI-7	?115	?10247	?1427	?0	?0.174	?659	?93.7		?℃	?kg/h	?kg/h	?kg/h	?kg/h	?kg/h	?％
ESI-7	?115	?10247	?1427	?0	?0.174	?659	?93.7	EPS-1	?115	?8543	?1133	?237	?0	?296	?88.8

Table 3 has been listed some attribute of the interpolymer that uses in an embodiment.Interpolymer styrene content, interpolymer propylene content and random isotactic polystyrene content use above-described proton magnetic resonance (PMR) method to measure.The performance of table 3:ESI-7 and EPS-1

Interpolymer	Interpolymer vinylbenzene	The interpolymer polypropylene	Random isotactic polystyrene	Melt index
Interpolymer	Interpolymer vinylbenzene	The interpolymer polypropylene	Random isotactic polystyrene	Melt index		????wt％	????wt％	????wt％	??g/10min
????ESI-7	????30.5	????0	????0.2	??9.68		????wt％	????wt％	????wt％	??g/10min
????ESI-7	????30.5	????0	????0.2	??9.68	????EPS-1	????14.1	????16.5	????0.1	??1.23

II) preparation 1 of the titanium catalyst) preparation of 1H-ring penta [1] phenanthrene-2-base lithium

Be equipped with in the round-bottomed flask of 250ml of the luxuriant and rich with fragrance and 120ml benzene of 1.42g (0.00657mol) 1H-ring penta [1] one and dropwise add 4.2ml, the hexane solution of 1.60M n-Butyl Lithium.This solution stirring is spent the night,,, separate obtaining lithium salts with twice washing of 25ml benzene, vacuum-drying by filtering.The hydrogen nuclear magnetic resonance spectrum analysis shows, the isomer comprises absolute majority of 2 replacements.2) preparation of (1H-encircles penta [1] phenanthrene-2-yl) dimethylchlorosilane

One 4.16g (0.0322mol) dimethyl-dichlorosilane (Me is housed ₂SiCl ₂) and the 500ml round-bottomed flask of 250ml tetrahydrofuran (THF) (THF) in, dropwise add 1.45g (0.0064mol) 1H-ring penta [1] phenanthrene-2-base lithium that is dissolved in the tetrahydrofuran (THF).With about 16 hours of this solution stirring, removal of solvent under reduced pressure stayed an oily solids then, used toluene to extract this oily solids, with super-cell (Celite ^TM) filter, with toluene wash twice, drying under reduced pressure.3) preparation of (1H-encircles penta [1] phenanthrene-2-yl) dimethyl (tertiary butyl amino) silane

Be equipped with in the round-bottomed flask of 500ml of 1.98g (0.0064mol) (1H-encircles penta [1] phenanthrene-2-yl) dimethylchlorosilane and 250ml hexane one and add 2.00ml (0.0160mol) TERTIARY BUTYL AMINE.This reaction mixture is stirred a couple of days, with super-cell (Celite ^TM) filter, with hexane wash twice, under reduced pressure obtain product by removing remaining separated from solvent.4) (1H-encircles penta [1] phenanthrene-2-yl) dimethyl (tertiary butyl amino) silane two lithium compounds

(dilithio(1H-cyclopenta[1]phenanthrene-2-yl)dimethyl(t-butylam

Ido) preparation silane)

Be equipped with in the round-bottomed flask of 250ml of 1.03g (0.0030mol) (1H-encircles penta [1] phenanthrene-2-yl) dimethyl (tertiary butyl amino) silane and 120ml benzene one and dropwise add 3.90ml, the hexane solution of 1.6M n-Butyl Lithium.With about 16 hours of this solution stirring, by filtering, use the benzene washed twice, drying under reduced pressure, separation obtaining product.5) preparation of (1H-encircles penta [1] phenanthrene-2-yl) dimethyl (tertiary butyl amino) silane titanium dichloride

One 1.17g (0.0030mol) TiCl is housed ₃-3THF and approximately 120ml THF be added drop-wise to about 1.08g rapidly and be dissolved in 1H-ring penta [1] phenanthrene-2-base dimethyl (tertiary butyl amino) silane two lithium compounds among the 50mlTHF.This mixture after 1.5 hours, is added 0.55g (0.002mol) solid PbCl in about 20 ℃ of stirrings ₂, continuing to stir after 1.5 hours, vacuum is removed THF, steams excess with the toluene extraction, filters, and drying under reduced pressure obtains a yellow solid.6) (1H-encircles penta [1] phenanthrene-2-yl) dimethyl (tertiary butyl amino) silane titanium 1, the preparation of 4-diphenyl diethylene

Under 70 ℃, at a pulpous state (1H-encircles penta [1] phenanthrene-2-yl) dimethyl (tertiary butyl amino) silane titanium dichloride (3.48g, 0.0075mol) and 1.551g (0.0075mol) be dissolved in 1 in about 80ml toluene, add 9.9ml in the 4-diphenyl diethylene, 1.6M butyllithium (0.0150mol) solution.The blackening immediately of this solution.Temperature rising reflux two hours.This mixture is cooled to approximately-20 ℃, and volatile matter is removed in decompression.In 60ml mixing hexane, under 20 ℃, steam excess and pulled an oar, reacted about 16 hours.With this mixture about 1 hour of about-25 ℃ cooling.By vacuum filtration, on a glass powder, collect and obtain solid, drying under reduced pressure then.This drying solid is placed in the glass fibre sleeve, uses a Soxhlet continuous extraetor, use the hexane continuous extraction.After 6 hours, the crystalline solid thing appears in the crucible that boils.This mixture is cooled to approximately-20 ℃, filtering separation, drying under reduced pressure obtains a black crystalline solid, abandons filtrate.Solid in the stirring extractor, and, obtain extra desirable black needle-like solid product with extra mixing hexane continuous extraction.

The preparation of III.MAH graft modification ESI-7 and EPS-1

Olefinically unsaturated organic monomers is MALEIC ANHYDRIDE (MAH), and radical initiator is 2,5-two (t-butylperoxy)-2,5-dimethylhexane (30% mineral oil solution).When preparation ESI-7, the weight ratio of MAH/ initiator/interpolymer is 1.4/0.32/98.28, and when preparation EPS-1, the weight ratio of MAH/ initiator/interpolymer is 1.4/0.5/98.1.The grafting process of ESI-7 and EPS-1 is similar to embodiment 1.

The melt index of MAH grafting ESI-7 is 7.8, and MAH grafting content is 0.6wt%; The MAH grafting content of MAH grafting EPS-1 is 0.95wt%.The grafting Determination on content is by infrared Fourier transform spectrum (FTIR).During mensuration, press mold thickness is 0.1mm.Free MAH is removed in the press mold process.

IV. the fiber that contains MAH grafting ESI-7 shows excellent spinning performance

Containing MAH grafting ESI-7 fiber forms on a spinning streamline.The MAH grafting ESI-7 of 10wt% and 90wt% ethylene/octene (density: 0.95g/ccm; Melt index: blend 17), use L/D is 28 master screw forcing machine, 180 ℃, compression ratio is 2.5, extrudes.The charging that melt extrudes thing is pumped in the spinning container by a toothed gear pump, and it comprises the three layer filtration chip system of a 0.065/0.030/0.16 micron and has 400 0.31mm holes, the spinning nozzle of L/D6.8.Be drawn as about 11 DENIER with the drawing force fusion filament of 120m/min by downward godet roller, and rolled-up.Maximum spinning speed (fiber drawing) was about 120m/min (this has reflected the equipment limit) before fiber was broken.As a comparison, the fiber of being made up of 100% ethylene/octene has only 90m/min at the maximum spinning speed that similar situation prepares fiber.MAH grafted HDPE by 10% (0.953 density, grafted HDPE melt index is 9.8, melt index is 65 before the grafting; MAH grafting content is 1.17) and the fiber formed of 90% ethylene/octene have only 60m/min at the maximum spinning speed that similar situation prepares fiber.

V. the bi-component fibres that contains MAH grafting ESI-7

The composition that contains MAH grafting ESI-7 is applied to preparing the binary composition fiber.This binary composition fiber has the arrangement of nuclear/shell, and its center is made of polypropylene, and shell is formed by the outer blend of (below-indentified) of identifying of the level that contains MAH grafting ESI-7.

Sample list (composition):

0.930)+10%MAH grafting ESI-7 1) (230 ℃, 2.16kg) (density is the ethylene/octene of homopolymer polypropylene (PP)/90% 20MFR:

2) the random basically ethylene/styrene interpolymer of 20MFR PP/85% (30MI, 10wt% vinylbenzene)+15%MAH grafting ESI-7

The description of fiber and and characteristic be summarized as follows.

Fiber is described and characteristic (target compound):

1) circle cross-section (50/50; Nuclear/shell ratio)

2) every filament 1.5-1.75 denier

3) be higher than the toughness of 2.5gpd

4) 1/8 inch cutting length

5) Goulston 5550 spinning lubricating agent FOY (Finish on Yarn) are 0.2-0.3% fiber physical property (acquisition):

????ID	The denier	Toughness (gpd)	Comment
????ID	The denier	Toughness (gpd)	Comment	Composition #1	????1.68	????3.76	Final lubricated level is 0.20%
Composition #2	????1.69	????3.42	The final lubricated level of finished fiber is 0.34%	Composition #1	????1.68	????3.76	Final lubricated level is 0.20%

Composition #1 spinning and stretching condition

Condition	Observed value
Condition	Observed value	Forcing machine A (shell)
Volume pump, rpm	?32.2	Forcing machine A (shell)
Volume pump, rpm	?32.2	Forcing machine pressure, psi	?1100
Zone 1 temperature, (℃)	165	Forcing machine pressure, psi	?1100
Zone 1 temperature, (℃)	165	Zone 2 temperature, (℃)	175
Zone 3 temperature, (℃)	185	Zone 2 temperature, (℃)	175
Zone 3 temperature, (℃)	185	Zone 4 temperature, (℃)	195

Forcing machine B (nuclear)
Forcing machine B (nuclear)		Volume pump, rpm	?32.2
Forcing machine pressure, psi	?1100	Volume pump, rpm	?32.2
Forcing machine pressure, psi	?1100	Zone 1 temperature, (℃)	?195
Zone 2 temperature, (℃)	?204	Zone 1 temperature, (℃)	?195
Zone 2 temperature, (℃)	?204	Zone 3 temperature, (℃)	?210
Zone 4 temperature, (℃)	?220	Zone 3 temperature, (℃)	?210
Zone 4 temperature, (℃)	?220	A spinning temperature, (℃)	?222
The A pump block, (℃)	?220	A spinning temperature, (℃)	?222
The A pump block, (℃)	?220	The B pump block, (℃)	?221
The quench air temperature, (℃)	?11.2	The B pump block, (℃)	?221
The quench air temperature, (℃)	?11.2	A loads pressure, the psi-left side	?808
A loads pressure, psi-the right	?1045	A loads pressure, the psi-left side	?808
A loads pressure, psi-the right	?1045	B loads pressure, the psi-left side	?1150
B loads pressure, psi-the right	?1063	B loads pressure, the psi-left side	?1150
B loads pressure, psi-the right	?1063	Spinning arrangement speed, rpm	?20
Arrangement type/level	2.5%Goulston 5550 is in water	Spinning arrangement speed, rpm	?20
Arrangement type/level	2.5%Goulston 5550 is in water	DENIER volume speed, m/min	?900
Feeding roller speed, m/min	?940	DENIER volume speed, m/min	?900
Feeding roller speed, m/min	?940	Draw roll speed #1, m/min	?997
Draw roll speed #2, m/min	?1000	Draw roll speed #1, m/min	?997
Draw roll speed #2, m/min	?1000	Winder speed, m/min	?1025
Staple fibre determination of denier value, dpf	?6	Winder speed, m/min	?1025
Staple fibre determination of denier value, dpf	?6	Stretching condition:
The #1 draw roll, m/min	?25.2	Stretching condition:
The #1 draw roll, m/min	?25.2	The #1 roll temperature, (℃)	?40
The #2 roll temperature, (℃)	?45	The #1 roll temperature, (℃)	?40
The #2 roll temperature, (℃)	?45	The #3 roll temperature, (℃)	?50
The #4 roll temperature, (℃)	?60	The #3 roll temperature, (℃)	?50
The #4 roll temperature, (℃)	?60	The #% roll temperature, (℃)	?60
The #2 draw roll, m/min	?100.8	The #% roll temperature, (℃)	?60
The #2 draw roll, m/min	?100.8	The #2 draw roll, m/min	?93.3
Final drawing-off denier, dpf	?1.68	The #2 draw roll, m/min	?93.3

Load (binder fibre) is also used a contactless process, and above-mentioned fiber is mixed with 12wt% with cellulose slurry, and processing obtains nuclear/liner of 100gsm.After contactless nuclear/liner machines, on a platen press, under 275F and 300F, add thermonuclear/liner more than 60 seconds, binder fibre processing is bonded on the cellulose pulp.Next, with 0.5 "/test speed of min, with the upright determinator of a paper 5-6 the tension detection that scales off from each nuclear/liner (with above-mentioned three kinds of binder fibre compositions each) measured with sample.The dry tensile strength of above-mentioned each composition of surveying (or cohesive strength) record is as follows.

The dry tensile strength conclusive table that contains MAH-grafting ESI-7 bondable fibers in the shell.The record of data adds 12% caking agent, bonding 100gsm liner under two kinds of bonding temps.

Composition	Tensile strength during 275F, psi	Tensile strength during 300F, psi
Composition	Tensile strength during 275F, psi	Tensile strength during 300F, psi	Composition #1	????17.5	????15.7
Composition #2	????15.5	????11.7	Composition #1	????17.5	????15.7

Shell that use is made by the ESI by higher grafting percentage composition and/or PET nuclear, can obtain surpassing improving of the above-mentioned performance that records and obtain performance.

Claims

1. grafted copolymer composition, it comprises one or more graft reaction products of random interpolymer basically, described interpolymer comprises: (1) polymer unit, it derives from:

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

(c) at least a aromatic ethenyl or vinylidene monomer and at least a fat that is obstructed

The combination of family or cycloaliphatic vinyl or vinylidene monomer, and (2) polymer unit, it derives from ethene and/or C _3-20At least a in the alhpa olefin; And (3) optional polymer unit, it derives from the unsaturated monomer that gathers of one or more ethylenic, derives from except those of (1) and (2); With one or more olefinically unsaturated organic monomers.

2. the copolymer composition of claim 1, wherein one or more I of random interpolymer basically ₂Be at least 0.01g/10min, comprise: (1) molar percentage is the polymer unit of 1-65, and this polymer unit derives from:

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

(c) at least a aromatic ethenyl or vinylidene monomer and at least a aliphatics of being obstructed

Or the combination of cycloaliphatic vinyl or vinylidene monomer, and (2) molar percentage be 35-99 derive from ethene and/or C _3-20At least a polymer unit in the alhpa olefin; And (3) molar percentage be 0-20 derive from the unsaturated polymer of monomers unit that gathers of one or more ethylenic, derive from except those of (1) and (2); This skeleton is monomer-grafted with one or more olefines unsaturated organic acids.

3. claim 1 or 2 copolymer composition, wherein said random basically interpolymer is ethylene/styrene interpolymer or ethylene/propylene/styrene copolymer.

4. each graft copolymerization body composition of claim 1-3, wherein said one or more olefinically unsaturated organic monomers are selected from organic dicarboxylic acid and acid anhydrides thereof.

5. each graft copolymerization body composition of claim 1-4, wherein said olefinically unsaturated organic monomers is selected from MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE acid anhydride, vinylformic acid, methacrylic acid, methylene-succinic acid, and Ba Dousuan.

6. each graft copolymerization body composition of claim 1-5 comprises MALEIC ANHYDRIDE grafted ethylene/styrene interpolymer or MALEIC ANHYDRIDE grafted ethylene/propylene/styrene copolymer.

7. one kind comprises one or more graft copolymerization body compositions of random interpolymer basically, and it comprises for being the about 300 ℃ reactive reaction product that dissolves process operation of about 50-in temperature range: (1) polymer unit, and it derives from:

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

(c) at least a aromatic ethenyl or vinylidene monomer and at least a ground fat that is obstructed

The combination of family or cycloaliphatic vinyl or vinylidene monomer, and (2) derive from ethene and/or C _3-20At least a polymer unit in the alhpa olefin; And (3) derive from the unsaturated monomeric optional polymer unit that gathers of one or more ethylenic, derives from except those of (1) and (2); And one or more olefinically unsaturated organic monomers.

8. a polymer blend comprises each described graft copolymerization body composition of claim 1-7.

9. the blend of claim 8 comprises that one or more are selected from Natene or multipolymer, the polymkeric substance of homopolymer polypropylene or multipolymer and polymeric amide.

10. each graft copolymerization body composition or blend of claim 1-9 comprises at least a weighting material.

11. a moulding or fabricated product, comprise among the claim 1-10 each graft copolymerization body composition or blend.

12. one kind comprises the multilayer materials of one deck at least, comprises among the claim 1-10 each graft copolymerization body composition or blend.

13. each graft copolymerization body composition or the application of blend in multilayer materials among the claim 1-10, this matrix material is suitable for doing packaging film, as autoadhesion coating or thermosol tackiness agent.

14. each graft copolymerization body composition or blend be at viscose fibre among the claim 1-10, weighting material, substituent or promote between the component of system the especially application in the consistency between polymeric composition.

15. a fiber comprises among the claim 1-10 each graft copolymerization body composition or blend.

16. the fiber of claim 15, it is a kind of multicomponent fibre.

17. the application of fiber in claim 15 or 16, it is a kind of adhesive fiber.

18. the graftomer with hydrogenant or partially hydrogenated irregular phenylethylene-divinyl rubber skeleton, this skeleton is monomer-grafted with one or more olefines unsaturated organic acids.