CN101253207A

CN101253207A - Method for producing thermoplastic elastic material

Info

Publication number: CN101253207A
Application number: CNA2005800514574A
Authority: CN
Inventors: R·舒尔奇斯; E·帕萨利亚; F·恰尔代利; E·雷斯米尼; D·蒂雷利; C·比安基尼
Original assignee: Pirelli and C SpA
Current assignee: Pirelli and C SpA
Priority date: 2005-08-30
Filing date: 2005-08-30
Publication date: 2008-08-27

Abstract

The present invention relates to a process for manufacturing a thermoplastic elastomeric material comprising at least one elastomeric phase and at least one thermoplastic phase, said process comprising the following steps: - surface-treating a vulcanized rubber in a subdivided form with an effective amount of at least one organometallic polymerization catalyst; polymerizing at least one ethylenically unsaturated monomer in the presence of said surface-treated vulcanized rubber in a subdivided form to obtain at least one thermoplastic phase.

Description

Produce the method for thermoplastic elastic material

The present invention relates to a kind of method of producing thermoplastic elastic material.

Particularly, the present invention relates to a kind of method of producing thermoplastic elastic material, described method is included in fractionized vulcanized rubber and has at least a ethylenically unsaturated monomers of catalyzed polymerization down.

In another aspect, the invention still further relates to a kind of goods that comprise described thermoplastic elastic material.

The output of the increase of industrial rubber product has caused the accumulation of common a large amount of Rubber wastes of disposing, the huge reserved area that its main drawback is environmental pollution and need be used to store described refuse in special-purpose landfill yard.

Well known in the prior art be make waste rubber for example the tire depolymerization with the volume that reduces refuse and obtain useful byproduct.Equally, can be with the rubber product desulfurization to reclaim waste rubber.

Except these technology, what use always in the prior art is waste rubber to be ground and utilizes the ground particle that so obtains.Then can be with these ground particles and thermoplastic, polymeric materials compounding so that make the finished product that can be used for multiple application.Described ground particle can be joined thermoplastic basically polymkeric substance for example in polyethylene, polypropylene, polystyrene, polyester, the polymeric amide, with toughness and the shock strength thereof that improves them simultaneously.

Yet, have been found that, above-mentioned ground rubber grain is joined the remarkable deterioration of the mechanical property that often causes products obtained therefrom in the described thermoplastic, polymeric materials merely, and it is mainly owing to insufficient consistency between this ground rubber grain and this thermoplastic polymer.

Many effort have been carried out in the problems referred to above prior art in order to overcome.

For example, at " Journal of Elastomers and Plastics ", D.Tuchman that delivers in volume 10, the 115-128 pages or leaves (1978) and the paper of S.L.Rosen disclose low temperature ground rubber for tire have been joined in the multiple thermoplastic polymer that comprises polypropylene, polyethylene and polystyrene.Particularly, with regard to polystyrene, the author believes that this low temperature ground rubber for tire serves as the good shock resistance toughener of appropriateness when with the polystyrene mechanical blending.The mechanical blend that comprises 20wt% low temperature ground rubber for tire make can be suitable on mechanicalness with medium High Impact Polystyrene (HIPS) material.In addition, the author studied several technology in case with styrene-grafted to low temperature ground rubber for tire.For this purpose, studied different technology, for example the promoted ionic grafting of free radical grafting in the body and mineral acid.According to the author, have in the product of improved shock strength at the product that obtains with respect to obtaining by the direct mechanical blend, it is successful having only the aqueous slurries method of use water soluble starter system.Simultaneously, the tensile strength of products obtained therefrom and modulus remain on quite high level.

United States Patent (USP) 3,042,634 disclose a kind of method for preparing rubber-rosin products, it comprises: under 125 ℃-250 ℃ temperature, the mixture heating up of monomer material that will comprise vulcanized rubber, water and the formation resin of pulverizing, the monomer material that wherein forms resin be for example vinylbenzene, alpha-methyl styrene and vinyl cyanide and composition thereof of monoolefine particularly; And, it can be plasticated to obtain uniform and smooth rubber-resin blend from wherein reclaiming exsiccant rubber resin product.Can comprise peroxide catalyst for example Potassium Persulphate, benzoyl peroxide, cumene hydroperoxide.Above-mentioned rubber-rosin products allegedly comprises from than the firm brittle colloid plastics of the hardened rubbery state product under the low-styrene monomer feed amount under the high-phenylethylene monomer feed amount.Do not mention the mechanical property of gained rubber-rosin products.

Patent application GB 2,022,105 discloses the method that the plastic material of retread rubber is mixed in a kind of preparation, and it comprises: with a certain amount of deficiency so that the saturated monomer of described retread rubber with described retread swell rubber; And make the polymerization of swollen material.Can this polymerization of thermal initiation, perhaps expediently by radical initiator for example benzoyl peroxide cause, it can be expediently and the monomer premix.The monomer that can use expediently is selected from: vinyl aromatic compounds is the vinylbenzene (for example β-bromstyrol, chloro-styrene) of vinylbenzene or replacement for example; Vinyl cyanide; Vinylstyrene; Or its mixture.The plastic material of gained allegedly has good shock strength, tensile strength and elongation at break.

At " Journal of Material Science ", M.Pittolo that delivers in volume 21, the 1769-1774 pages or leaves (1986) and the paper of R.P.Burford disclose the research to the rubber scraps polystyrene modified.Particularly, by the homopolymerization subsequently of swelling in styrene monomer the polyhutadiene and the styrene/butadiene rubbers powder of peroxide crosslinking changed into semi-intercrossing network.Select two kinds of radical initiator types, a kind of bonding (benzoyl peroxide) that causes between polystyrene and the rubber, another kind provide independently polymerization [azo two (isopropyl cyanide)].Then the polystyrene modified powder is mixed in the polystyrene substrate, and measure the tensile property of gained matrix material.Observe the improvement in performance of undressed relatively chip modified composite material, it has the breaking strain owing to be full of cracks of increase.

At " Rubber Chemistry and Technology ", M.Pittolo that delivers in volume 58, the 97-106 pages or leaves (1986) and the paper of R.P.Burford disclose the application of the rubber scraps of recovery as the toughening polystyrene agent.Particularly, handle rubber scraps with styrene monomer and benzoyl peroxide in case with polystyrene graft on the rubber scraps surface.Modified rubber chip with gained mixes in the polystyrene substrate then, obtains matrix material.The toughness of gained matrix material it is said along with improving rubber to the binding property of matrix and reduce the granularity of rubber scraps and increase.In addition, breaking strain and energy-to-break allegedly increase along with the raising of graft(ing) degree, and on the contrary, tensile strength allegedly reduces thereupon.

Yet the use of described radical initiator can demonstrate some shortcomings.At first, the use meeting of described radical initiator is owing to the unstable of described product causes handling and storage problem.In addition, products obtained therefrom does not always show good performance (particularly in shock strength and mechanical properties), and this is mainly owing to monomer-grafted lip-deep than low degree to the sulfuration ground rubber.

The applicant is faced with the problem of the shock strength that improves the thermoplastic elastic material that mixes the sulfuration ground rubber.Especially, the applicant is faced with the problem that improves the shock strength of the thermoplastic elastic material that comprises sulfuration ground rubber and at least a thermoplastic polymer when keeping gratifying mechanical property.

The applicant has now found that, there is the method for at least a ethylenically unsaturated monomers of catalyzed polymerization down by means of being included in the sulfuration ground rubber, described sulfuration ground rubber was carried out surface treatment with at least a organo-metallic polymerizing catalyst, can improve described shock strength and keep gratifying mechanical property simultaneously.Described method produces and can directly use so that make the thermoplastic elastic material that demonstrates improved shock strength of goods.In addition, described thermoplastic elastic material can as with the blend of other polymer materials, particularly to blend, so that improve its shock strength with polymer materials that similar monomer forms.

In addition, described method can obtain to demonstrate the thermoplastic elastic material of gratifying mechanical property, particularly yield tensile strength, elongation at yield rate, rupture stress, elongation at break and tangent modulus.

According to first aspect, the present invention relates to the method that a kind of production comprises at least one elastomerics phase and at least one thermoplasticity thermoplastic elastic material mutually, described method comprises the following steps:

The fractionized vulcanized rubber of at least a organo-metallic polymerizing catalyst surface treatment of-usefulness significant quantity;

-in the presence of described surface-treated fractionized vulcanized rubber at least a ethylenically unsaturated monomers of polymerization to obtain at least one thermoplasticity phase.

For the purpose of this specification sheets and following claim book, in expressing " organo-metallic polymerizing catalyst ", term " organo-metallic " is meant the active substance of described polymerizing catalyst.

According to an embodiment preferred, described organo-metallic polymerizing catalyst can be selected from:

-Ziegler-Natta catalyst;

-metalloscene catalyst.

According to another embodiment, can in the presence of carbon monoxide, carry out described method.

Be that described organo-metallic polymerizing catalyst can be selected from the polymerizing catalyst that comprises following component under the situation of multipolymer of at least a ethylenically unsaturated monomers and carbon monoxide at described thermoplastic elastic material:

(a) metallic compound, described metal belong to periodic table of elements VIIIA family;

(b) pKa is less than 2 the acid or the negatively charged ion of its metal-salt;

(c) bidentate ligand.

For simplicity, the above-mentioned polymerizing catalyst that comprises (a) to (c) component is called " the organo-metallic polymerizing catalyst that contains part " hereinafter.

Should be noted that, purpose for this specification sheets and following claim book, mention that the periodic table of elements is meant " Handbook of Chemistry and Physics " that CRC publishes, the periodictable version of announcing among the 1989-1990, it adopts I UPAC system about each family.

According to an embodiment preferred, with respect to the gross weight of fractionized vulcanized rubber, the consumption of described organo-metallic polymerizing catalyst can be 0.01wt%-5wt%, preferred 0.05wt%-1wt%.

According to an embodiment preferred, can 20 ℃-100 ℃, more preferably under 30 ℃-90 ℃ the temperature, under the pressure of 1 crust-60 crust, preferred 2 crust-45 crust, carry out described polymerization procedure 5 minutes-10 hours, more preferably time of 10 minutes-3 hours.

According to a preferred embodiment, can in the presence of water, carry out described polymerization procedure.

According to a preferred embodiment, can in the presence of at least a inert solvent, carry out described polymerization procedure.

According to an embodiment preferred, described thermoplastic elastic material comprises:

-with respect to the gross weight of described thermoplastic elastic material, at least a thermoplastic polymer of 10wt%-99wt%, preferred 20wt%-95wt%;

-with respect to the gross weight of described thermoplastic elastic material, the fractionized vulcanized rubber of 1wt%-90wt%, preferred 5wt%-80wt%.

For the purpose of this specification sheets and following claim book, unless otherwise mentioned, all numerals of expression contents, quantity, per-cent etc. all should be understood to be modified by term " about " in all cases.In addition, all scopes comprise the arbitrary combination of disclosed maximum point and smallest point and comprise wherein any intermediate range that it may specifically be enumerated or can specifically not enumerate in this article.

Being used for fractionized vulcanized rubber of the present invention can be by for example grinding any source of vulcanized rubber admixtion or pulverize with film, flexible pipe, packing ring etc. and obtain in tire, roof, and preferably adopts any ordinary method to be obtained by regeneration or waste tire.For example, can be by obtaining fractionized vulcanized rubber by mechanical mill at ambient temperature or in the presence of low-temperature refrigerant (being liquid nitrogen).Before using, should from the ground tire, remove any steel or other metal inclusion.Usually, the preferred separation method of routine that adopts is removed for example tire cord fibre of fibrous material from ground rubber.

According to a preferred embodiment, can be used for fractionized vulcanized rubber of the present invention and be granularity and be not more than 10mm, preferably be not more than powder or the particulate form of 5mm.

According to a preferred embodiment, can be used for fractionized vulcanized rubber of the present invention have be not more than 0.5mm, preferably be not more than 0.2mm, more preferably no more than the granularity of 0.1mm.

According to a preferred embodiment, this fractionized vulcanized rubber can comprise at least a crosslinked diene elastomer polymkeric substance or multipolymer, its can be natural origin or can obtain by solution polymerization, letex polymerization or the vapour phase polymerization of one or more conjugated dienes that randomly is no more than at least a comonomer blend that is selected from monovinylarene and/or polar comonomers of 60wt% with content.

Described conjugated diene contains 4-12, preferred 4-8 carbon atom usually, and can for example be selected from: 1,3-divinyl, isoprene, 2,3-dimethyl-1,3-divinyl, 1,3-pentadiene, 1,3-hexadiene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-butadiene or its mixture.

The monovinylarene that can randomly be used as comonomer contains 8-20, preferred 8-12 carbon atom usually, and can for example be selected from: vinylbenzene; The 1-vinyl naphthalene; The 2-vinyl naphthalene; Cinnamic various alkyl, cycloalkyl, aryl, alkaryl or aralkyl derivatives, for example alpha-methyl styrene, 3-vinyl toluene, 4-propylstyrene, 4-phenylcyclohexane ethene, 4-dodecyl vinylbenzene, 2-ethyl-4-benzyl vinylbenzene, 4-right-tolyl vinylbenzene, 4-(4-phenyl butyl) vinylbenzene or its mixture.

The polar comonomers that can choose use wantonly can for example be selected from: vinyl pyridine, vinylquinoline, vinylformic acid and alkyl acrylate, nitrile or its mixture, for example methyl acrylate, ethyl propenoate, methyl methacrylate, Jia Jibingxisuanyizhi, vinyl cyanide or its mixture.

Preferably, diene elastomer polymkeric substance or multipolymer that this is crosslinked can for example be selected from: cis-1,4-polyisoprene (natural or synthetic rubber, preferred natural rubber), 3,4-polyisoprene, polyhutadiene (particularly have high by 1, the polyhutadiene of 4-cis-content), optional halogenated isoprene/isobutylene copolymers, 1,3-butadiene/acrylonitrile copolymer, vinylbenzene/1,3-butadienecopolymer, styrene/isoprene/1,3-butadienecopolymer, vinylbenzene/1,3-butadiene/acrylonitrile copolymer or its mixture.

As selection, this fractionized vulcanized rubber may further include at least a crosslinked elastomer polymer of one or more monoolefines and olefinic comonomer or derivatives thereof.This monoolefine can for example be selected from: ethene and contain the alpha-olefin of 3-12 carbon atom usually, for example propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene or its mixture.Preferred following material: ethene and alpha-olefin, randomly and the multipolymer between the diolefine; The multipolymer of isobutylene homo or itself and a small amount of diolefine, it is halogenation at least in part randomly.The optional diolefine that exists contains 4-20 carbon atom usually and preferably is selected from: 1,3-divinyl, isoprene, 1,4-hexadiene, 1,5-ethylidene-2-norbornene, 5-methylene-2-norbornene, vinyl norbornene or its mixture.Wherein, preferred especially following material: ethylene/propene copolymer (EPR) or ethylene/propylene/diene hydrocarbon copolymer (EPDM); Polyisobutene; Isoprene-isobutylene rubber; Halogenated butyl rubber, particularly chlorinated butyl rubber or brominated butyl rubber; Or its mixture.

According to a preferred embodiment, described Ziegler-Natta catalyst can be selected from those catalyzer that organometallic compound and the compound that belongs to the transition metal of periodic table of elements IVA, VA, VIA or VIIIA family by the metal that will belong to periodic table of elements IA, IIA or IIIB family obtain.

Usually, the organometallic compound that belongs to the metal of periodic table of elements IA, IIA or IIIB family comprises hydride, aluminum alkyls, haloalkyl aluminium, aluminum alkyl halide, Grignard reagent, composite alkali aluminum hydride, alkali metal borohydride, alkalimetal hydride, alkaline earth metal hydride or its mixture.

Preferably, can advantageously use trialkyl aluminium compound so that obtain catalyzer of the present invention.Described trialkyl aluminium compound can be selected from any routine or known trialkyl aluminium compound, for example: trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium; Perhaps do not limit the more high-grade trialkyl aluminium compound of carbonatoms, for example its average group becomes trioctylaluminum or three (dodecyl) aluminium; Or its mixture.Preferred especially trimethyl aluminium, triethyl Its mixture.

The compound that can be advantageously used in the transition metal that belongs to periodic table of elements IVA, VA, VIA or VIIIA family that obtains catalyzer of the present invention can for example be selected from: halogenide is muriate, bromide or fluorochemical for example; Oxide compound or oxyhydroxide; Perhaps for example alkoxide, acetate, benzoate, acetylacetonate of organic compound; Or its mixture.Preferred especially muriate.

Preferably, described transition metal can for example be selected from: titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten or its mixture.Preferred especially titanium.

Preferably, useful especially catalyzer can obtain by trimethyl aluminium or triethyl aluminum are mixed with titanium tetrachloride according to the present invention.

Can be about the more details of above-mentioned Ziegler-Natta catalyst for example in U.S. Pat 3,113,115, find among US 3,257,332 or the US 3,505,301.

According to-individual preferred embodiment, described metalloscene catalyst can for example be selected from has following general formula (III) or compound (IV):

(C ₅R′ _m) _pR” _s(C ₅R′ _m)M(Q) _3-p(III)

R” _s(C ₅R′ _m)M(Q′)(IV)

Wherein:

-C ₅R ' _mRepresent unsubstituted or replacement and/or condensed cyclopentadienyl;

-R ' group can be same to each other or different to each other, and the alkyl that expression contains 1-20 carbon atom is alkyl, thiazolinyl, aryl, alkaryl or aralkyl for example, perhaps is joined together to form C ₄-C ₆Two adjacent carbonss of ring;

-R " two C of expression bridging ₅R ' _mThe C of ring ₁-C ₄Alkylene (alkylene) group, dialkyl Germanium or siloxanes or alkylphosphines or amido;

-M represents to belong to the transition metal of periodic table of elements IVA, VA, VIA or VIIIA family;

-Q group can be same to each other or different to each other, and the alkyl that expression contains 1-20 carbon atom is alkyl, alkoxyl group, thiazolinyl, aryl, alkaryl or aralkyl, perhaps halogen atom for example;

-Q ' expression has alkylidene (alkylidene) group of 1-20 carbon atom;

-p is 0,1 or 2;

-s is 0 or 1;

-n and z are 0, and perhaps the integer of 1-3 comprises end value.

Preferably, p is 0 when s is 0; When s was 1, m was 4, and when s was 0, m was 5.

As R " when representing the alkylphosphines group, described alkylphosphines group can be water miscible or non-water-soluble.

The specific examples of alkyl is: methyl, ethyl, propyl group, butyl, amyl group, isopentyl, isobutyl-, heptyl, octyl group, nonyl, decyl, hexadecyl, 2-ethylhexyl, methoxyl group, oxyethyl group, butoxy, phenyl.

The specific examples of alkano groups is: methylene radical, ethylene, trimethylene.

The specific examples of halogen atom is: chlorine, bromine, iodine, preferred chlorine.

The specific examples of alkylidene group is: methene, ethylidene, propylidene.

Preferably, M represents titanium, zirconium, vanadium, hafnium, more preferably zirconium or titanium.

The specific examples with general formula (III) or compound (IV) that can advantageously use according to the present invention is: tri-chlorination cyclopentadienyltitanium or zirconium, tri-chlorination pentamethyl-cyclopentadienyltitanium or zirconium, trimethoxy pentamethyl-cyclopentadienyltitanium or zirconium, phenylbenzene two (cyclopentadienyl) titanium or zirconium, dimethyl two (cyclopentadienyl) titanium or zirconium, methyl chlorination two (cyclopentadienyl) titanium or zirconium, ethyl chlorination two (cyclopentadienyl) titanium or zirconium, dichloride two (cyclopentadienyl) titanium or zirconium, dichloride two (n-butyl cyclopentadienyl) titanium or zirconium, dichloride two (dodecyl cyclopentadienyl) titanium or zirconium, dichloride ethylene-two (tetrahydro indenyl) titanium or zirconium, ethylene dimethyl-two (tetrahydro indenyl) titanium or zirconium, dichloride ethylene-two (indenyl) titanium or zirconium, ethylene dimethyl-two (indenyl) titanium or zirconium, dichloride dimethylated methylene silylation (silanylene)-two (tetrahydro indenyl) titanium or zirconium, dimethylformamide dimethyl base-silicylene-two (tetrahydro indenyl) titanium or zirconium, dichloride dimethylated methylene silylation-two (indenyl) titanium or zirconium, dimethylformamide dimethyl base silicylene-two (indenyl) titanium or zirconium.Preferred tri-chlorination pentamethyl-cyclopentadienyltitanium, trimethoxy pentamethyl-cyclopentadienyltitanium or dichloride two (cyclopentadienyl) zirconium.

Described have general formula (III) or compound (IV) and be used in combination with promotor, preferred aikyiaiurnirsoxan beta usually, and described aikyiaiurnirsoxan beta is commonly known in the art and it can or be that the general formula of straight chain compound (VI) is represented by the logical formula V of classifying ring compound down as:

(R-Al-O) _n(V)

R(R-Al-O) _nAlR ₂(VI)

Wherein:

-R group can be same to each other or different to each other, expression straight or branched C ₁-C ₅Alkyl, for example methyl, ethyl, propyl group, butyl, amyl group, preferable methyl;

-n is the integer of 1-20, comprises end value.

Special preferable methyl aikyiaiurnirsoxan beta (MAO).

As selection, can be with organoboron compound as promotor.The specific examples of the organoboron compound that can advantageously use according to the present invention is: trifluoroboranes, three (4-fluorophenyl) borine, three (3, the 5-difluorophenyl) borine, three (4-methyl fluoride phenyl) borine, three (3,4, the 5-trifluorophenyl) borine, three (pentafluorophenyl group) borine, three (tolyl) borine, three (3, the 5-3,5-dimethylphenyl) borine or its mixture.

Can be about the more details of above-mentioned metalloscene catalyst for example in U.S. Pat 4,530,914 or US 6,908,876 in find.

According to a preferred embodiment, the described organo-metallic polymerizing catalyst that contains part can comprise:

(a) metallic compound, for example palladium compound, cobalt compound, iron cpd or nickel compound, preferably palladium compound;

(c) have the bidentate ligand of following general formula (VII):

R ¹R ²-M ¹-R ³-M ¹-R ⁴R ⁵(VII)

Wherein:

-R ¹, R ², R ³, R ⁴And R ⁵Can be same to each other or different to each other, expression contains the alkyl of individual, preferred 6-14 the carbon atom of 2-18, preferred aryl groups, more preferably phenyl;

-M ¹Expression phosphorus, arsenic or antimony, preferred phosphorus;

-R ³The divalent organic bridging base group that has at least two carbon atoms in the expression bridge, for example :-(CR ⁶R ⁷) _n-group, wherein R ⁶And R ⁷Representing hydrogen atom or sterically hindered alkyl, preferably hydrogen atom, and n are not provided is the integer of 2-4, comprises end value; Aryl is phenyl, benzene, naphthalene for example; Alicyclic group is the hexanaphthene group for example; Preferably-(CR ⁶R ⁷) _n-group.

Preferably, described metallic compound (a) is selected from the palladium salt of carboxylic acid, for example acid chloride, palladium trifluoroacetate, tosic acid palladium; Perhaps be selected from for example [PdCl (Me) is (cod)] (cod=ring suffering-1,5-diene) of palladium salt, or its mixture.

Preferably, described pKa is selected from the negatively charged ion that comes from following acid or its metal-salt less than 2 the acid or the negatively charged ion (b) of its metal-salt:

The acid of-inorganic proton, it can for example be selected from: sulfuric acid, nitric acid, boric acid, Tetrafluoroboric acid, perchloric acid, sulfonic acid (for example methylsulfonic acid, trifluoromethanesulfonic acid, tosic acid), trichoroacetic acid(TCA), trifluoroacetic acid or its mixture;

-Lewis acid, it can for example be selected from: boron compound is triphenylborane, three (pentafluorophenyl group) borine, (right-chloro-phenyl-) borine, three [3,5-two (trifluoromethyl) phenyl] borine for example; Perhaps be selected from the compound of aluminium, zinc, antimony or titanium with Lewis acid character; Or its mixture; Perhaps their mixture.

Preferably, described bidentate ligand (c) is selected from: 1,3-two (diphenylphosphine) propane, 1,4-two (diphenylphosphine) butane, 2,3-dimethyl-1,4-two (diphenylphosphine) butane, 1,4-two (dicyclohexylphosphontetrafluoroborate) butane, 1,5-two (dinaphthyl phosphine) pentane, 1,2-two (diphenylphosphine) benzene, 1,2-two (diphenylphosphine) hexanaphthene or its mixture.Preferred especially 1,3-two (diphenylphosphine) propane.Described phosphine can be water miscible or non-water-soluble.

Preferably, the above-mentioned metal catalyst that contains part further comprises and is selected from 1,4-quinone for example 1,4-benzoquinones, 1, at least a compound (d) of 4-naphthoquinones or its mixture.

Can be about the more details of the above-mentioned organo-metallic polymerizing catalyst that contains part for example in U.S. Pat 4,970,294 or US 6,670,443 or in European patent application EP 121,965, find.

According to a preferred embodiment, before carrying out above-mentioned surface treatment step, can make described fractionized vulcanized rubber carry out solvent extraction, for example use the ebullient methylbenzene extraction, to remove the low molecular weight compositions that exists usually for example softening agent, promotor, linking agent or other additive that exists usually.

Can following step of carrying out the fractionized vulcanized rubber of above-mentioned surface treatment.

Can random order with the fractionized vulcanized rubber of the different components surface treatment of described organo-metallic polymerizing catalyst.

For example, under the situation of Ziegler-Natta catalyst, described surface treatment step comprises the following steps:

(i) make in advance in the inert solvent at least a organometallic compound of the described fractionized vulcanized rubber of swollen and the metal that belongs to periodic table of elements IA, IIA or IIIB family time of 30 minutes-2 hours, preferred 40 minutes-1.5 hours of reaction under 30 ℃-80 ℃, preferred 50 ℃-70 ℃ temperature in toluene, methyl alcohol or its mixture for example, gross weight with respect to described fractionized vulcanized rubber, the consumption of described organometallic compound is 10wt%-150wt%, preferred 30wt%-100wt%;

The compound that (ii) makes compound that obtains in the step (i) and the transition metal that belongs to periodic table of elements IVA, VA, VIA or VIIIA family is 30 minutes-4 hours, preferred 1 hour-3 hours time of reaction under 40 ℃-100 ℃, preferred 60 ℃-90 ℃ temperature, gross weight with respect to described fractionized vulcanized rubber, the consumption of the compound of the described transition metal that belongs to periodic table of elements IVA, VA, VIA or VIIIA family is 1wt%-10wt%, preferred 2wt%-6wt%.

Preferably, under the situation of metalloscene catalyst, described surface treatment step comprises the following steps:

(i ') make in advance inert solvent for example in toluene, methyl alcohol or its mixture described fractionized vulcanized rubber of swollen with have logical formula V or at least a aikyiaiurnirsoxan beta (VI) in the presence of inert solvent, the preferred toluene under 30 ℃-80 ℃, preferred 50 ℃-70 ℃ temperature 30 minutes-2 hours, preferred 40 minutes-1.5 hours time of reaction, gross weight with respect to described fractionized vulcanized rubber, the consumption of described aikyiaiurnirsoxan beta is 10wt%-1500wt%, preferred 50wt%-1000wt%;

(ii ') makes the compound that obtains in the step (i ') and has general formula (III) or at least a compound (IV) 30 minutes-4 hours, preferred 1 hour-3 hours time of reaction under 40 ℃-100 ℃, preferred 60 ℃-90 ℃ temperature, gross weight with respect to described fractionized vulcanized rubber, described consumption with general formula (III) or compound (IV) is 0.01wt%-5wt%, preferred 0.05wt%-1wt%.

Preferably, under the situation of the organo-metallic catalyst that contains part, described surface treatment comprises to be made in advance at inert solvent toluene for example, in methyl alcohol or its mixture described fractionized vulcanized rubber of swollen with comprise above-mentioned (a) at least a organo-metallic polymerizing catalyst that contains part of (c) component at 10 ℃-50 ℃, reaction is 60 minutes-2 hours under preferred 20 ℃-30 ℃ temperature, preferred 40 minutes-1.5 hours time, gross weight with respect to described fractionized vulcanized rubber, described catalyst consumption is 0.01wt%-1wt%, preferred 0.3wt%-0.6wt%.

According to a preferred embodiment, described at least a ethylenically unsaturated monomers can for example be selected from aliphatic series or aromatics ethylenically unsaturated monomers.

With regard to described aliphatic ethylenically unsaturated monomers, term " aliphatic ethylenically unsaturated monomers " generally is meant the ethylenically unsaturated monomers with general formula (I):

CH ₂＝CH-R(I)

Wherein R represents hydrogen atom; The straight or branched alkyl that contains 1-12 carbon atom;-(R ') _x-COO-R ", wherein R ' expression contains the straight or branched alkylidene group of 1-20 carbon atom, x represent 0 or 1 and R " expression contains the alkyl of straight or branched of 1-12 carbon atom; Or-O-(C=O)-R ", R wherein " and have an above-mentioned identical meanings.

Preferably, the aliphatic ethylenically unsaturated monomers with general formula (I) can be selected from: ethene, propylene, 1-butylene, iso-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-dodecylene, 10-undecylene acetoacetic ester, vinyl-acetic ester, butyl acrylate or its mixture.Special optimal ethylene, propylene, 1-hexene, 1-octene, 10-undecylene acetoacetic ester, vinyl-acetic ester, butyl acrylate or its mixture.

With regard to described aromatics ethylenically unsaturated monomers, term " aromatics ethylenically unsaturated monomers " generally is meant the ethylenically unsaturated monomers with general formula (II):

CH ₂＝CH-(R ₁R ₂C) _x-(C ₆H _5-z) _y(R ₃) _z(II)

R wherein ₁, R ₂And R ₃Can be same to each other or different to each other expression hydrogen atom or contain the straight or branched alkyl of 1-8 carbon atom; Perhaps, R ₃With R ₁And R ₂Difference, expression alkoxyl group, carboxyl, acyloxy, described acyloxy are randomly contained the alkyl of 1-8 carbon atom or hydroxyl or halogen atom and are replaced; X and z are 0 or the integer of 1-5, comprise end value; And y is 1 or 2.

Preferably, the aromatics ethylenically unsaturated monomers with general formula (II) can be selected from: vinylbenzene; Single-or polyalkylbenzene ethene for example 4-vinyl toluene, dimethyl styrene, ethyl styrene, Vinyl toluene; The styrene derivatives that contains functional group is methoxy styrene, phenetole ethene, vinyl benzoic acid, vinyl benzoic acid methyl esters, vinyl acetate base benzyl ester, hydroxy styrenes, chloro-styrene, Vinylstyrene for example; The alkene that phenyl replaces is allyl benzene for example, 4-phenyl butene-1,3-phenyl-butene-1,4-(4-aminomethyl phenyl) butene-1,4-(3-aminomethyl phenyl) butene-1,4-(2-aminomethyl phenyl) butene-1,4-(4-ethylphenyl) butene-1,4-(4-butyl phenyl) butene-1,5-phenyl amylene-1,4-phenyl amylene-1,3-phenyl amylene-1,5-(4-aminomethyl phenyl) amylene-1,4-(2-aminomethyl phenyl) amylene-1,3-(4-aminomethyl phenyl) amylene-1,6-phenyl-hexene-1,5-phenyl hexene-1,4-phenyl hexene-1,3-phenyl-hexene-1,6-(4-aminomethyl phenyl) hexene-1,5-(2-aminomethyl phenyl) hexene-1,4-(4-aminomethyl phenyl) hexene-1,3-(2-aminomethyl phenyl) hexene-1,7-phenyl heptene-1,6-phenyl heptene-1,5-phenyl heptene-1,4-phenyl heptene-1,8-phenyl octene-1,7-phenyl octene-1,6-phenyl octene-1,5-phenyl octene-1,4-phenyl octene-1,3-phenyl octene-1,10-phenyl decylene-1; Or its mixture.Special optimization styrene.

As mentioned above, can in the presence of carbon monoxide, carry out polymerization procedure of the present invention.Preferably, can use described carbon monoxide with stoichiometry with respect to described ethylenically unsaturated monomers.

As mentioned above, can in the presence of water, carry out polymerization procedure of the present invention.Preferably, the amount of water surpasses the amount of described fractionized vulcanized rubber, and more preferably the consumption of water can be 10 times-200 times with respect to the gross weight of fractionized vulcanized rubber, more preferably 50 times-100 times.

As mentioned above, can in the presence of at least a inert solvent, carry out polymerization procedure of the present invention.Described inert solvent can for example be selected from: aromatic hydrocarbons (for example benzene, toluene, ethylbenzene, dimethylbenzene), alicyclic hydrocarbon (for example hexanaphthene), aliphatic hydrocrbon (for example hexane, octane), ketone (for example methylethylketone), ester (for example ethyl acetate), ether (for example 1,4-diox) or its mixture.Preferred especially toluene.

Preferably, the amount of solvent surpasses the amount of described fractionized vulcanized rubber, and more preferably the consumption of described solvent can be 10 times-200 times with respect to the gross weight of fractionized vulcanized rubber.

Can in one or more stages, carry out described method continuously or in batches.

According to a preferred embodiment, with respect to the described fractionized vulcanized rubber and the gross weight of olefinic monomer, the consumption of described ethylenically unsaturated monomers can be 1wt%-1000wt%, preferred 20wt%-400wt%.

End in described method, can reclaim the thermoplastic elastic material that obtains according to any method known in the art, for example, remove unreacted monomer and reclaim with the optional diluting solvent that exists by via solvent extraction or via heating under reduced pressure or via extruding with the forcing machine of removing volatile matter by means of design.By making catalyst deactivation with solvent (for example with the methanol solution that contains 5 volume % hydrochloric acid) washing and removing.Subsequently, can be optionally with the thermoplastic elastic material granulation or the powdered that so obtain.

As selection, can by for example by means of filter or centrifugally separate, water or inert solvent washing, method dry and granulation optionally subsequently or powdered reclaim the thermoplastic elastic material that this obtains.

Can be with pellet or powder packaging to be used for following use or to be used to form the method for goods immediately.

As top disclosed, can pellet or powder be directly formed to goods according to the hot worked technology of the thermoplastic resin composition of being used for known in the art.For example, can use compression moulding, vacuum moulding, injection moulding, calendering, casting, extrude, the combination of long filament winding, lamination, rotational moulding or slush moulding, transfer mould, lay-up moulding or contact moulding, punching press or these methods.

As selection, as top disclosed, pellet or the powder that obtains can be joined in other polymkeric substance as interfacial compatibilizer, preferably join in the polymkeric substance of polymer chain with same type.For example, can with the thermoplastic elastic material of the pellet that obtains or powder type and polyolefine for example polyethylene, polypropylene, polystyrene mix with polyketone or melting mixing with as blend polymer; Perhaps can with its with remove above-mentioned those mixed with polymers or melting mixing to be used as blend polymer, wherein said polymkeric substance for example is selected from: styrene-butadiene rubber(SBR), polyphenylene oxide resin, polycarbonate, polyester, polymeric amide.

Therefore, according on the other hand, the invention still further relates to the thermoplastic elastic material that obtains by means of method of the present invention with the blend of other polymkeric substance in application.

Can in the thermoplastic elastic material that obtains, add conventional additive, stablizer [for example, antioxidant (phenol antioxidant for example, Phosphorus antioxidant), UV light absorber (thermo-stabilizer), fire retardant, lubricant (Zinic stearas for example, calcium stearate, ethylenebisstearamide), die lubricant or releasing agent, static inhibitor, filler, tinting material (titanium oxide for example, red iron oxide, azo-compound perylene, phthalocyanine, the heterocycle series compound), softening agent and spreading agent (polyoxyethylene glycol for example, mineral oil), surface-modifying agent, or its mixture.

According on the other hand, the invention still further relates to a kind of goods that comprise above-mentioned thermoplastic elastic material.

Described thermoplastic elastic material can be molded as sheet-form and design and be suitable for the structure formation of making packaging structure, shell, supporting structure, furniture, moulded product, toy, building decoration thing etc.

In addition, can also use described thermoplastic elastic material preparation example such as belt such as travelling belt, transmission belt or rotating band; Can be used for the health and happiness field, be used for industrial circle, be used to move or surperficial safely floor and walkway; Floor tile; The for example antistatic computer pad of mat, automobile ground cushion; Pad is installed; Vibration damper plate; Sound barrier; Film protection thing; Carpet lining; Bumper; The wheel arch lining; Strip of paper used for sealing is car door or vehicle window strip of paper used for sealing for example; O-shape ring; Packing ring; Waterworks; Pipe or hose material; Flowerpot; Stone; Roof Material; Or the like.

To further specify the present invention by means of a plurality of preparation embodiment below, it only provides rather than any restriction of the present invention for purpose of explanation.

Embodiment 1

By vinyl polymerization (metalloscene catalyst) preparation thermoplastic elastic material

(to remove softening agent, promotor, linking agent and other additive that is present in usually in the vulcanized rubber that obtains by damaged tire, dry till constant weight under vacuum subsequently with ebullient methylbenzene extraction vulcanized rubber from the low temperature ground waste rubber (mean diameter＜0.1mm (140 order)-Applied Cryogenics International AG) of damaged tire.

In the 50ml Glass tubing, the above-mentioned vulcanized rubber that obtains of 0.5g swelling in 10ml toluene is spent the night.Then, add 10ml (15mmol) methylaluminoxane (MAO) and stirred these mixtures 1 hour down at 60 ℃.

Then, add 1ml (1.5 μ mol) dichloride two (cyclopentadienyl) zirconium in toluene 1.5 * 10 ^-3M solution, and under 80 ℃, stirred this mixture 2.5 hours.

Under argon pressure, the above-mentioned surface-treated vulcanized rubber that obtains is joined in the 200ml glass reaction container that contains the new distillatory toluene of 80ml (B ü chi) that mechanical stirrer is housed.Add ethene (purity＞99.9% is from Rivoira) then, stir this mixture and remained on 2 constant pressures of clinging to following 1 hour.Use 10ml HCl/ methanol solution (5 volume %) to make the mixture quencher then.

The gained thermoplastic elastic material is filtered, with methanol wash and dry till constant weight under vacuum subsequently.So the thermoplastic elastic material that obtains demonstrates following composition: 91wt% polyethylene, the fractionized vulcanized rubber of 9wt%.

Embodiment 2

In 50ml Glass tubing flask, the above-mentioned vulcanized rubber that obtains of 1.5g swelling in 10ml toluene is spent the night.Then, add 10ml (15mmol) methylaluminoxane (MAO) and stirred these mixtures 1 hour down at 60 ℃.

Under argon pressure, the above-mentioned surface-treated vulcanized rubber that obtains is joined in the 200ml glass reaction container that contains the new distillatory toluene of 80ml (B ü chi) that mechanical stirrer is housed.Add vinyl monomer (purity＞99.9% is from Rivoira) then, stir this mixture and remained on 2 constant pressures of clinging to following 1 hour.Use 10ml HCl/ methanol solution (5 volume %) to make the mixture quencher then.

The gained thermoplastic elastic material is filtered, with methanol wash and dry till constant weight under vacuum subsequently.So the thermoplastic elastic material that obtains demonstrates following composition: the vulcanized rubber that 65wt% polyethylene and 35wt% are fractionized.

Embodiment 3

In 50ml Glass tubing flask, the above-mentioned vulcanized rubber that obtains of 0.5g swelling in 10ml toluene is spent the night.Then, add 10ml (15mmol) methylaluminoxane (MAO) and stirred these mixtures 1 hour down at 60 ℃.

Then, add 0.33ml (0.5 μ mol) dichloride two (cyclopentadienyl) zirconium in toluene 1.5 * 10 ^-3M solution, and under 80 ℃, stirred this mixture 2.5 hours.

The gained thermoplastic elastic material is filtered, with methanol wash and dry till constant weight under vacuum subsequently.So the thermoplastic elastic material that obtains demonstrates following composition: the vulcanized rubber that 57wt% polyethylene and 43wt% are fractionized.

Embodiment 4

By ethene/10-undecylene acetoacetic ester copolymerization (metalloscene catalyst) preparation thermoplasticity Elastomer material

Under argon pressure, the above-mentioned surface-treated vulcanized rubber that obtains is joined in the 200ml glass reaction container that contains the new distillatory toluene of 80ml (B ü chi) that mechanical stirrer is housed.Add ethene (purity＞99.9% is from Rivoira) then, stir this mixture and remained on 2 constant pressures of clinging to following 5 minutes.Then, interrupt ethene and flow out (flux), make mixture recovery normal pressure and introduce formerly 15 minutes 0.41ml of pre-compounded (1.679mmol) 10-undecylene acetoacetic ester and the solution of 5ml (7.5mmol) methylaluminoxane MAO in toluene.Add ethene (purity＞99.9% is from Rivoira) then, stir this mixture and remained on 2 constant pressures of clinging to following 1 hour.Then make the mixture quencher with 10ml HCl/ methanol solution (5 volume %).

The gained thermoplastic elastic material is filtered, with methanol wash and dry till constant weight under vacuum subsequently.So the thermoplastic elastic material that obtains demonstrates following composition: 58wt% ethene-altogether-undecylene acetoacetic ester multipolymer and the fractionized vulcanized rubber of 42wt%.

Embodiment 5

By vinyl polymerization (Ziegler-Natta catalyst) preparation thermoplastic elastic material

In 50ml Glass tubing flask, the above-mentioned vulcanized rubber that obtains of 0.5g swelling in 10ml toluene is spent the night.Then, add 10ml (20mmol) Al (Et) ₃And stirred this mixture 1 hour down at 60 ℃.

Then, add 0.2ml (200 μ mol) TiCl ₄, and under 80 ℃, stirred this mixture 2.5 hours.

The gained thermoplastic elastic material is filtered, with methanol wash and dry till constant weight under vacuum subsequently.So the thermoplastic elastic material that obtains demonstrates following composition: the vulcanized rubber that 46wt% polyethylene and 54wt% are fractionized.

Embodiment 6

By styrene polymerization (metalloscene catalyst) preparation thermoplastic elastic material

In 50ml Glass tubing flask, the above-mentioned vulcanized rubber that obtains of 0.1g swelling in 25ml toluene is spent the night.Then, add 10ml (15mmol) methylaluminoxane (MAO) and stirred these mixtures 1 hour down at 50 ℃.

Then, add 0.81ml (0.125 μ mol) tri-chlorination pentamethyl-cyclopentadienyltitanium in toluene 15.4 * 10 ^-3M solution and 5ml (0.48mol) vinylbenzene, and under 50 ℃, stirred this mixture 2 hours.Use 10ml HCl/ methanol solution (5 volume %) to make the mixture quencher then.

The gained thermoplastic elastic material is filtered, with methanol wash and dry till constant weight under vacuum subsequently.So the thermoplastic elastic material that obtains demonstrates following composition: the vulcanized rubber that 52wt% syndiotactic polystyrene and 48wt% are fractionized.

Embodiment 7

Then, add 0.81ml (0.125 μ mol) trimethoxy pentamethyl-cyclopentadienyltitanium in toluene 15.4 * 10 ^-3M solution and 5ml (0.48mol) vinylbenzene, and under 80 ℃, stirred this mixture 2 hours.Use 10ml HCl/ methanol solution (5 volume %) to make the mixture quencher then.

The gained thermoplastic elastic material is filtered, with methanol wash and dry till constant weight under vacuum subsequently.So the thermoplastic elastic material that obtains demonstrates following composition: the vulcanized rubber that 92wt% syndiotactic polystyrene and 8wt% are fractionized.

Embodiment 8

By ethene/CO-copolymerization (palladium catalyst) preparation thermoplastic elastic material

(to remove softening agent, promotor, linking agent and other additive that is present in usually in the vulcanized rubber that obtains by damaged tire, dry till constant weight under vacuum subsequently with ebullient acetone extraction vulcanized rubber from the low temperature ground waste rubber (mean diameter＜0.1mm (140 order)-Applied Cryogenics International AG) of damaged tire.

In 250ml Glass tubing flask, the above-mentioned vulcanized rubber that obtains of 1g swelling in 100ml methyl alcohol is spent the night.Remove after the oxygen, add 4.64 * 10 ^-5Mole [(dppp) Pd (OTs) (H ₂O)] OTs (dppp=1, two (the diphenylphosphino propane of 3-; The Ts=tosylate), 6.271 * 10 ^-4Mole tosic acid and 1.7666 * 10 ^-3Mole 1-4 benzoquinones, and at room temperature stirred this mixture 1 hour.

Subsequently, introducing mixture in the stainless steel autoclave and exerting pressure is the ethene and 20 CO that cling to of 20 crust.Under the stirring of 1200rpm, reacted 1.5 hours at 85 ℃.Stopped reaction then, and after discharging the gas that absorbs, be cooled to room temperature suddenly.

The gained thermoplastic elastic material is filtered, with methanol wash and dry till constant weight under vacuum subsequently.So the thermoplastic elastic material that obtains demonstrates following composition: the vulcanized rubber that 88wt% polyketone and 12wt% are fractionized.

Embodiment 9

In 250ml Glass tubing flask, the above-mentioned vulcanized rubber that obtains of 1g swelling in 100ml toluene is spent the night.Remove after the oxygen, add 3.031 * 10 ^-5Mole [(dppp) Pd (CH ₃) (NCCH ₃)] B[(C ₆H ₃) (CF ₃) ₂] ₃(dpPp=1,3-two (diphenylphosphino propane), 2.4802 * 10 ^-3Mole 1-4 benzoquinones, and at room temperature stirred this mixture 1 hour.

Subsequently, introducing mixture in the stainless steel autoclave and exerting pressure is the ethene and 20 CO that cling to of 20 crust.Under the stirring of 1200rpm, reacted 2.5 hours at 85 ℃.Stopped reaction then, and after discharging the gas that absorbs, be cooled to room temperature suddenly.

The gained thermoplastic elastic material is filtered, with methanol wash and dry till constant weight under vacuum subsequently.So the thermoplastic elastic material that obtains demonstrates following composition: the vulcanized rubber that 70wt% polyketone and 30wt% are fractionized.

Embodiment 10

With the following measurement of carrying out mechanical property of the thermoplastic elastic material that obtains in embodiment 1 and 2:

For this purpose, obtain the film of about 200 micron thickness from the thermoplastic material of above-mentioned acquisition.By making this film 180 ℃ of following moldings 10 minutes with postcooling 5 minutes to room temperature.

Obtain dumbbell-shaped specimen by above-mentioned film, and be used for (Tinius-Olsen) the following mechanical property of measurement under the pulling speed of 10mm/min of ergometer (dinamometer instrument): yield tensile strength, elongation at yield rate, rupture stress, elongation at break and tangent modulus according to ASTM standard D638-02a.The results are shown in Table 1 for gained.

In order to compare purpose, make the film (PE contrast) that obtains by polyethylene, this polyethylene is made by means of disclosed identical process among the embodiment 1, and only difference is there is not fractionized vulcanized rubber.

In addition, for purpose relatively, make film (BLEND contrast), it obtains as the fractionized vulcanized rubber mechanical blending that obtains as described in the embodiment 1 by polyethylene that 91wt% is as above obtained and 9wt%.

Table 1

Embodiment	Yield tensile strength (MPa)	Elongation at yield rate (%)	Rupture stress (MPa)	Elongation at break (%)	Tangent modulus (MPa)
Embodiment	Yield tensile strength (MPa)	Elongation at yield rate (%)	Rupture stress (MPa)	Elongation at break (%)	Tangent modulus (MPa)	PE contrasts (*)	23.8	16.6	37.0	1704.3	343
BLEND contrasts (*)	25.3	14.0	25.7	17.3	467	PE contrasts (*)	23.8	16.6	37.0	1704.3	343
BLEND contrasts (*)	25.3	14.0	25.7	17.3	467	Embodiment 1	20.2	18.8	25.4	991.0	304
Embodiment 2	21.0	20.7	21.7	871.3	297	Embodiment 1	20.2	18.8	25.4	991.0	304

(*): contrast

Claims

1. a production comprises at least one elastomerics mutually and the method for at least one thermoplasticity thermoplastic elastic material mutually, and described method comprises the following steps:

2. the process of claim 1 wherein that described organo-metallic polymerizing catalyst is selected from:

-Ziegler-Natta catalyst;

-metalloscene catalyst.

3. the method for claim 1, it carries out in the presence of carbon monoxide.

4. the process of claim 1 wherein that described thermoplastic elastic material is the multipolymer of at least a ethylenically unsaturated monomers and carbon monoxide, and described organo-metallic polymerizing catalyst is selected from the polymerizing catalyst that comprises following component:

(c) bidentate ligand.

5. each method of aforementioned claim, wherein with respect to the gross weight of fractionized vulcanized rubber, the consumption of described organo-metallic polymerizing catalyst is 0.01wt%-5wt%.

6. the method for claim 5, wherein with respect to the gross weight of fractionized vulcanized rubber, the consumption of described organo-metallic polymerizing catalyst is 0.05wt%-1wt%.

7. each method of aforementioned claim is wherein carried out described polymerization procedure under 20 ℃-100 ℃ temperature.

8. the method for claim 7 is wherein carried out described polymerization procedure under 30 ℃-90 ℃ temperature.

9. each method of aforementioned claim is wherein carried out described polymerization procedure under the pressure of 1 crust-60 crust.

10. the method for claim 9 is wherein carried out described polymerization procedure under the pressure of 2 crust-45 crust.

11. each method of aforementioned claim is wherein carried out 5 minutes-10 hours time of described polymerization procedure.

12. the method for claim 11 is wherein carried out 10 minutes-3 hours time of described polymerization procedure.

13. each method of aforementioned claim, wherein said fractionized vulcanized rubber is powder or the particle form that granularity is not more than 10mm.

14. each method of claim 1-12, wherein said fractionized vulcanized rubber is powder or the particle form that granularity is not more than 0.5mm.

15. the method for claim 14, wherein said fractionized vulcanized rubber is powder or the particle form that granularity is not more than 0.2mm.

16. the method for claim 12, wherein said fractionized vulcanized rubber is powder or the particle form that granularity is not more than 0.1mm.

17. each method of aforementioned claim, wherein said fractionized vulcanized rubber comprises at least a crosslinked diene elastomer polymkeric substance or multipolymer, its be natural origin or obtain by solution polymerization, letex polymerization or the vapour phase polymerization of one or more conjugated dienes that randomly is no more than at least a comonomer blend that is selected from monovinylarene and/or polar comonomers of 60wt% with content.

18. the method for claim 17, wherein said crosslinked diene elastomer polymkeric substance or multipolymer are selected from: cis-1,4-polyisoprene, 3,4-polyisoprene, polyhutadiene, optional halogenated isoprene/isobutylene copolymers, 1,3-butadiene/acrylonitrile copolymer, vinylbenzene/1,3-butadienecopolymer, styrene/isoprene/1,3-butadiene multipolymer, vinylbenzene/1,3-butadiene/acrylonitrile copolymer or its mixture.

19. each method of aforementioned claim, wherein said fractionized vulcanized rubber further comprises at least a crosslinked elastomer polymer of one or more monoolefines and olefinic comonomer or derivatives thereof.

20. the method for claim 19, wherein said crosslinked elastomer polymer is selected from: ethylene/propene copolymer (EPR) or ethylene/propylene/diene hydrocarbon copolymer (EPDM); Polyisobutene; Isoprene-isobutylene rubber; Halogenated butyl rubber, particularly chlorinated butyl rubber or brominated butyl rubber; Or its mixture.

21. the method for claim 2, wherein said Ziegler-Natta catalyst are selected from those catalyzer that organometallic compound and the compound that belongs to the transition metal of periodic table of elements IVA, VA, VIA or VIIIA family by the metal that will belong to periodic table of elements IA, IIA or IIIB family obtain.

22. the method for claim 21, the wherein said organometallic compound that belongs to the metal of periodic table of elements IA, IIA or IIIB family comprises hydride, aluminum alkyls, haloalkyl aluminium, aluminum alkyl halide, Grignard reagent, composite alkali aluminum hydride, alkali metal borohydride, alkalimetal hydride, alkaline earth metal hydride or its mixture.

23. the method for claim 21 or 22, the wherein said compound that belongs to the transition metal of periodic table of elements IVA, VA, VIA or VIIIA family is selected from: halogenide is muriate, bromide or fluorochemical for example; Oxide compound or oxyhydroxide; Perhaps for example alkoxide, acetate, benzoate, acetylacetonate of organic compound; Or its mixture.

24. each method of claim 21-23 wherein obtains described Ziegler-Natta catalyst by trimethyl aluminium or triethyl aluminum are mixed with titanium tetrachloride.

25. being selected from, the method for claim 2, wherein said metalloscene catalyst have following general formula (III) or compound (IV):

(C ₅R′ _m) _pR” _s(C ₅R′ _m)M(Q) _3-p(III)

R” _s(C ₅R′ _m)M(Q′)(IV)

Wherein

-R " two C of expression bridging ₅R ' _mThe C of ring ₁-C ₄Alkano groups, dialkyl Germanium or siloxanes or alkylphosphines or amine groups;

-Q ' expression has the alkylidene group of 1-20 carbon atom;

-p is 0,1 or 2;

-s is 0 or 1;

-n and z are 0, and perhaps the integer of 1-3 comprises end value.

26. the method for claim 25, wherein said have general formula (III) or compound (IV) is selected from: tri-chlorination cyclopentadienyltitanium or zirconium, tri-chlorination pentamethyl-cyclopentadienyltitanium or zirconium, trimethoxy pentamethyl-cyclopentadienyltitanium or zirconium, phenylbenzene two (cyclopentadienyl) titanium or zirconium, dimethyl two (cyclopentadienyl) titanium or zirconium, methyl chlorination two (cyclopentadienyl) titanium or zirconium, ethyl chlorination two (cyclopentadienyl) titanium or zirconium, dichloride two (cyclopentadienyl) titanium or zirconium, dichloride two (n-butyl cyclopentadienyl) titanium or zirconium, dichloride two (dodecyl cyclopentadienyl) titanium or zirconium, dichloride ethylene-two (tetrahydro indenyl) titanium or zirconium, ethylene dimethyl-two (tetrahydro indenyl) titanium or zirconium, dichloride ethylene-two (indenyl) titanium or zirconium, ethylene dimethyl-two (indenyl) titanium or zirconium, dichloride dimethylated methylene silylation-two (tetrahydro indenyl) titanium or zirconium, dimethylformamide dimethyl base-silicylene-two (tetrahydro indenyl) titanium or zirconium, dichloride dimethylated methylene silylation-two (indenyl) titanium or zirconium, dimethylformamide dimethyl base silicylene-two (indenyl) titanium or zirconium.

27. the method for claim 26, wherein said have general formula (III) or compound (IV) is selected from: tri-chlorination pentamethyl-cyclopentadienyltitanium, trimethoxy pentamethyl-cyclopentadienyltitanium or dichloride two (cyclopentadienyl) zirconium.

28. each method of claim 25-27, the wherein said promotor that has general formula (III) or compound (IV) and the logical formula V of classifying ring compound down as or represent for the general formula of straight chain compound (VI) is used in combination:

(R-Al-O) _n(V)

R(R-Al-O) _nAlR ₂(VI)

Wherein:

-R group can be same to each other or different to each other, expression straight or branched C ₁-C ₅Alkyl, for example methyl, ethyl, propyl group, butyl, amyl group;

-n is the integer of 1-20, comprises end value.

29. the method for claim 28, wherein said promotor are methylaluminoxane (MAO).

30. each method of claim 25-27, wherein said have general formula (III) or compound (IV) is used in combination with promotor, described promotor is selected from organoboron compound, trifluoroboranes, three (4-fluorophenyl) borine, three (3 for example, the 5-difluorophenyl) borine, three (4-methyl fluoride phenyl) borine, three (3,4,5-trifluorophenyl) borine, three (pentafluorophenyl group) borine, three (tolyl) borine, three (3, the 5-3,5-dimethylphenyl) borine or its mixture.

31. the method for claim 4, the wherein said organo-metallic polymerizing catalyst that contains part comprises:

(a) metallic compound, for example palladium compound, cobalt compound, iron cpd or nickel compound;

(c) have the bidentate ligand of following general formula (VII):

R ¹R ²-M ¹-R ³-M ¹-R ⁴R ⁵(VII)

Wherein:

-R ¹, R ², R ³, R ⁴And R ⁵Can be same to each other or different to each other, expression contains the alkyl of 2-18 carbon atom;

-M ¹Expression phosphorus, arsenic or antimony;

-R ³The divalent organic bridging base group that has at least two carbon atoms in the expression bridge, for example :-(CR ⁶R ⁷) _n-group, wherein R ⁶And R ⁷Expression hydrogen atom or sterically hindered alkyl is not provided, and n is the integer of 2-4, comprises end value; Aryl is phenyl, benzene, naphthalene for example; Alicyclic group is the hexanaphthene group for example.

32. the method for claim 31, wherein said metallic compound (a) is selected from the palladium salt of carboxylic acid, for example acid chloride, palladium trifluoroacetate, tosic acid palladium; Perhaps be selected from for example [PdCl (Me) is (cod)] (cod=ring suffering-1,5-diene) of palladium salt, or its mixture.

33. the method for claim 31 or 32, wherein said pKa is selected from the negatively charged ion that comes from following acid or its metal-salt less than 2 negatively charged ion (b) sour or its metal-salt:

The acid of-inorganic proton, it is selected from: sulfuric acid, nitric acid, boric acid, Tetrafluoroboric acid, perchloric acid, sulfonic acid (for example methylsulfonic acid, trifluoromethanesulfonic acid, tosic acid), trichoroacetic acid(TCA), trifluoroacetic acid or its mixture;

-Lewis acid, it is selected from: boron compound is triphenylborane, three (pentafluorophenyl group) borine, (right-chloro-phenyl-) borine, three [3,5-two (trifluoromethyl) phenyl] borine for example; Perhaps be selected from the compound of aluminium, zinc, antimony or titanium with Lewis acid character; Or its mixture;

Perhaps their mixture.

34. each method of claim 31-33, wherein said bidentate ligand (c) is selected from: 1,3-two (diphenylphosphine) propane, 1,4-two (diphenylphosphine) butane, 2,3-dimethyl-1,4-two (diphenylphosphine) butane, 1,4-two (dicyclohexylphosphontetrafluoroborate) butane, 1,5-two (dinaphthyl phosphine) pentane, 1,2-two (diphenylphosphine) benzene, 1,2-two (diphenylphosphine) hexanaphthene or its mixture.

35. further comprising, each method of claim 31-34, the wherein said metal catalyst that contains part be selected from 1,4-quinone for example 1,4-benzoquinones, 1, at least a compound (d) of 4-naphthoquinones or its mixture.

36. each method of aforementioned claim wherein before carrying out surface treatment step, makes described fractionized vulcanized rubber carry out solvent extraction.

37. each method of aforementioned claim, wherein under the situation of Ziegler-Natta catalyst, described surface treatment step comprises the following steps:

(i) make in advance inert solvent for example in toluene, methyl alcohol or its mixture described fractionized vulcanized rubber of swollen and at least a organometallic compound that belongs to the metal of periodic table of elements IA, IIA or IIIB family under 30 ℃-80 ℃ temperature, react time of 30 minutes-2 hours, with respect to the gross weight of described fractionized vulcanized rubber, the consumption of described organometallic compound is 10wt%-150wt%;

The time that compound that obtains in the step (i) and the compound that belongs to the transition metal of periodic table of elements IVA, VA, VIA or VIIIA family were reacted under 40 ℃-100 ℃ temperature 30 minutes-4 hours, with respect to the gross weight of described fractionized vulcanized rubber, the consumption of the compound of the described transition metal that belongs to periodic table of elements IVA, VA, VIA or VIIIA family is 1wt%-10wt%.

38. each method of claim 1-36, wherein under the situation of metalloscene catalyst, described surface treatment step comprises the following steps:

(i ') make in advance inert solvent for example in toluene, methyl alcohol or its mixture described fractionized vulcanized rubber of swollen with have logical formula V or at least a aikyiaiurnirsoxan beta (VI) inert solvent for example toluene in the presence of under 30 ℃-80 ℃ temperature 30 minutes-2 hours time of reaction, with respect to the gross weight of described fractionized vulcanized rubber, the consumption of described aikyiaiurnirsoxan beta is 10wt%-1500wt%;

(ii ') makes the middle compound that obtains of step (i ') and have the time that general formula (III) or at least a compound (IV) reacted 30 minutes-4 hours under 40 ℃-100 ℃ temperature, gross weight with respect to described fractionized vulcanized rubber, described consumption with general formula (III) or compound (IV) is 0.01wt%-5wt%, preferred 0.05wt%-1wt%.

38. each method of claim 1-36, wherein contain under the situation of organo-metallic catalyst of part at this, described surface treatment comprise make in advance inert solvent for example in toluene, methyl alcohol or its mixture described fractionized vulcanized rubber of swollen and at least a organo-metallic polymerizing catalyst that contains part that claim 4 is described to comprise (a) to (c) component under 10 ℃-50 ℃ temperature, react time of 60 minutes-2 hours, with respect to the gross weight of described fractionized vulcanized rubber, described catalyst consumption is 0.01wt%-1wt%.

39. each method of aforementioned claim, wherein said at least a ethylenically unsaturated monomers are selected from the have general formula aliphatic ethylenically unsaturated monomers of (I):

CH ₂＝CH-R(I)

Wherein R represents hydrogen atom; The straight or branched alkyl that contains 1-12 carbon atom;-(R ') _x-COO-R ", wherein R ' expression contains the straight or branched alkylidene group of 1-20 carbon atom, x represent 0 or 1 and R " expression contains the straight or branched alkyl of 1-12 carbon atom; Or-O-(C=O)-R ", R wherein " and have an above-mentioned identical meanings.

40. the method for claim 39, wherein said aliphatic ethylenically unsaturated monomers with general formula (I) is selected from: ethene, propylene, 1-butylene, iso-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-dodecylene, 10-undecylene acetoacetic ester, vinyl-acetic ester, butyl acrylate or its mixture.

41. each method of claim 1-38, wherein said at least a ethylenically unsaturated monomers are selected from the have general formula aromatics ethylenically unsaturated monomers of (II):

CH ₂＝CH-(R ₁R ₂C) _x-(C ₆H _5-z) _y(R ₃) _z(II)

42. the method for claim 41, wherein said aromatics ethylenically unsaturated monomers with general formula (II) is selected from: vinylbenzene; Single-or polyalkylbenzene ethene for example 4-vinyl toluene, dimethyl styrene, ethyl styrene, Vinyl toluene; The styrene derivatives that contains functional group is methoxy styrene, phenetole ethene, vinyl benzoic acid, vinyl benzoic acid methyl esters, vinyl acetate base benzyl ester, hydroxy styrenes, chloro-styrene, Vinylstyrene for example; The alkene that phenyl replaces is allyl benzene for example, 4-phenyl butene-1,3-phenyl-butene-1,4-(4-aminomethyl phenyl) butene-1,4-(3-aminomethyl phenyl) butene-1,4-(2-aminomethyl phenyl) butene-1,4-(4-ethylphenyl) butene-1,4-(4-butyl phenyl) butene-1,5-phenyl amylene-1,4-phenyl amylene-1,3-phenyl amylene-1,5-(4-aminomethyl phenyl) amylene-1,4-(2-aminomethyl phenyl) amylene-1,3-(4-aminomethyl phenyl) amylene-1,6-phenyl-hexene-1,5-phenyl hexene-1,4-phenyl hexene-1,3-phenyl-hexene-1,6-(4-aminomethyl phenyl) hexene-1,5-(2-aminomethyl phenyl) hexene-1,4-(4-aminomethyl phenyl) hexene-1,3-(2-aminomethyl phenyl) hexene-1,7-phenyl heptene-1,6-phenyl heptene-1,5-phenyl heptene-1,4-phenyl heptene-1,8-phenyl octene-1,7-phenyl octene-1,6-phenyl octene-1,5-phenyl octene-1,4-phenyl octene-1,3-phenyl octene-1,10-phenyl decylene-1; Or its mixture.

43. the method for claim 3 is wherein used described carbon monoxide with respect to described ethylenically unsaturated monomers with stoichiometry.

44. each method of aforementioned claim is wherein carried out described polymerization procedure in the presence of water.

45. each method of claim 1-43 is wherein carried out described polymerization procedure in the presence of at least a inert solvent, described inert solvent is selected from: aromatic hydrocarbons, alicyclic hydrocarbon, aliphatic hydrocrbon, ketone, ester, ether or its mixture.

46. each method of aforementioned claim, wherein with respect to the described fractionized vulcanized rubber and the gross weight of olefinic monomer, the consumption of described ethylenically unsaturated monomers is 1wt%-1000wt%.

47. the method for claim 46, wherein with respect to the described fractionized vulcanized rubber and the gross weight of olefinic monomer, the consumption of described ethylenically unsaturated monomers is 20wt%-400wt%.

48. according to each thermoplastic elastic material that is obtained of aforementioned claim, it comprises:

-with respect to the gross weight of described thermoplastic elastic material, at least a thermoplastic polymer of 10wt%-99wt%;

-with respect to the gross weight of described thermoplastic elastic material, the fractionized vulcanized rubber of 1wt%-90wt%.

49. the thermoplastic elastic material of claim 48 with the blend of polyethylene, polypropylene, polystyrene or polyketone in application.

50. the thermoplastic elastic material of claim 48 with the blend of styrene-butadiene rubber(SBR), polyphenylene oxide resin, polycarbonate, polyester, polymeric amide in application.

51. the goods that the thermoplastic elastic material by molded claim 48 obtains.

52. the goods of claim 51, described goods are selected from: packaging structure, shell, supporting structure, furniture, moulded product, toy, building decoration thing.

53. the goods of claim 51, described goods are selected from: belt, floor and walkway, floor tile, mat, vibration damper plate, sound barrier, film protection thing, carpet lining, bumper, wheel arch lining, strip of paper used for sealing, o-shape ring, packing ring, waterworks, pipe or hose material, flowerpot, stone, roof Material, geomembrane.