CN1337979A

CN1337979A - Thermoplastic rubber composition

Info

Publication number: CN1337979A
Application number: CN99816015A
Authority: CN
Inventors: V·S·潘迪兰杰
Original assignee: SYH TECHNOLOGY HOLDING Co
Current assignee: SYH TECHNOLOGY HOLDING Co
Priority date: 1998-12-04
Filing date: 1999-12-03
Publication date: 2002-02-27
Also published as: CA2353614A1; EP1171524A1; ID29940A; AUPP750598A0; WO2000034383A1; BR9915932A; MXPA01005606A

Abstract

A rubber matrix including a) 10-90 % (v/v) of natural rubber, b) one or more first compatabilisers selected from a group of polymers containing either i) a nitrile group, ii) a halogen, iii) an acetate group, iv) an epoxide, v) a styrene, or vi) an acrylate and c) one or more second compatabilisers which are interfacial copromoters selected from a group comprising either i) polyvinyl acetate, ii) ethylene vinyl acetate, iii) polyacrylonitrile or high nitrile resin, iv) acrylamide or polyacrylamide, v) a phenolic resin, vi) an acrylate polymer, vii) a halogenated polymer, viii) maleic anhydride or polymaleic anhydride, or ix) a bismaleimide. The rubber matrix may be mixed with one or more thermoplastics selected from a group comprising either i) polyurethanes, ii) polyesters, iii) polyamides, iv) acrylates, v) acrylonitrile butadiene styrene, vi) polyolefins, or vii) cellulose esters to form a rubber thermoplastics composite.

Description

Thermoplastic rubber composition

The present invention relates to a kind of rubber matrix composition that comprises natural rubber, can make the thermoplastic composite in the thermoplastics scope.

The background of invention

Natural rubber has been used for various uses for a long time, however its some performance make rubber difficulty be used for commercial run and/or make it be not suitable for some application.These performances comprise high molecular weight, high viscosity, usually are mixed with naturally occurring protein impurities and usually have high foreign matter content.In addition, normally used rubber is crosslinked by sulfuration.These crosslinked being difficult to reverse, and the result uses the recirculation of using rubber product and is difficult to reach gratifying degree.

With plastics and some other rubber phase ratio, natural rubber also has some very useful performance, and these performances comprise toughness, dynamic airtightness, rebound resilience, warp resistance fatigue lifetime, low compression and tensile set and low modulus in flexure and creep.Therefore, wish natural rubber and some thermoplastics blend are got up, make suitable performance but resemble the matrix material that to process and can reprocess the thermoplastics with rubber.

Dropped into quite a large amount of work already,, improved the performance of natural rubber so that natural rubber and various plastic blend are got up.The main difficulty that runs in this blend is that natural rubber is nonpolar on substantially, so can not be effectively and some plastic blend.In addition, the natural rubber of high molecular and various molecular weight makes blend be difficult to reach even.The maximum that obtains successfully is with natural rubber and the limited plastic blend that comprises polypropylene, polyethylene, polystyrene, methyl methacrylate, ethane-acetic acid ethyenyl ester and polyvinyl acetate.Yet, with the general day by day plastic blend that comprises polymeric amide, urethane, polyester and acrylonitrile-butadiene-styrene (ABS) (ABS) time, only obtained limited success.Attempt to make similar blend with synthetic rubber such as divinyl rubber and synthetic polyisoprene.

Blend between several different methods promotion thermoplastics and natural or the synthetic rubber is arranged in the past, its way be added to polar compound natural or synthetic rubber in, a kind of such method is vinyl cyanide to be added to promote this blend in natural rubber and the synthetic rubber.

Known to the contriver, there is not a kind of available system can be reliably with natural rubber and various thermoplastics blend.

The purpose of invention

An object of the present invention is to provide a kind of rubber matrix that can form the matrix material of any or multiple thermoplastics and natural rubber.

The general introduction of invention

By first aspect of the present invention a kind of rubber matrix is provided in broad terms, it comprises:

A) natural rubber 10-90% (v/v),

B) one or more are selected from first kind of compatilizer of the polymkeric substance that comprises following arbitrary material, (compatabilisers),

I) nitrile,

Ii) halogen,

Iii) acetate esters,

Iv) epoxide,

V) vinylbenzene, or

Vi) acrylate,

C) one or more are selected from second kind of compatilizer of the interface secondary accelerator (copromoters) that comprises following arbitrary material,

I) polyvinyl acetate,

Ii) ethane-acetic acid ethyenyl ester,

Iii) polyacrylonitrile or high nitrile resin,

Iv) acrylamide or polyacrylamide,

V) resol,

Vi) acrylic ester polymer,

Vii) halogenated polymer,

Viii) maleic anhydride or poly-maleic anhydride, or

Ix) bismaleimides.

Rubber matrix can be mixed with various thermoplasticss, makes the thermoplastic elastomer matrix material.Thermoplastics can be selected from and include, but are not limited in polyolefine, polymeric amide, polyester, urethane, polystyrene, the acrylonitrile-butadiene-styrene (ABS) one or more, and all these plastics will be described in detail below.

First kind and second kind of compatilizer better are inequality.

An advantage of thermoplastics is their energy recyclings and/or can reprocesses and Reshapable.Similarly, but with rubber matrix of the present invention and thermoplastics mixed the also recycling of thermoplastic elastomer matrix material, reprocessing and/or reshaping.

Natural rubber should be selected from following kind, the natural rubber (DP-NR) that is called deproteinization, oil-extended natural rubber (OE-NR), mould and separate natural rubber, senior processing rubber (SP or PA), Standard Malasian rubber (SMR), it has constant viscosity (SMR-CV), low viscosity (SMR-LV) or general (SMR-GP) rank or ISNR LCV rank.These kinds often have low protein and low foreign matter content.Preferably use SMR or ISNR LCV rank.

The content of natural rubber can be 10-90 phr (umbers in per 100 parts of rubber) in the rubber matrix.For making the natural rubber that is transformed into the finished product have required elastoplasticity performance, rubber matrix should comprise the natural rubber of 35-40phr.If the amount of used natural rubber then often can not intrinsic required natural rubber performance in the finished product less than 10phr in rubber matrix.

Should be with replace accounting for the rubber of rubber total amount from recovery rubber up to 50% including, but not limited to the various sources of doughnut.Also should replace the component of partly plastic at least in the thermoplastic elastomer matrix material with the plastics of graduation, recycling.

The molecular weight height of natural rubber, it is a kind of high viscosity and elastic rubber.The ordinary method that natural rubber and plastic blend is related can reduce the molecular weight of natural rubber, thereby the size of itself and plastics is complementary, so that carry out effective blend.Yet the present invention is considered to can play to small part and prevents that natural rubber (it is the elastic material of a kind of height and can recovers its molecular weight usually) from producing the effect of discontinuous phase between the plastics of blend and natural rubber.In this case, thus think that this problem can produce better essential part (base) between mutually and better matching is overcome at rubber and plastics by adding the polar rubber equally also have lower molecular weight.Lower molecular weight is considered to reduce and stabilising rubber viscosity mutually, and this can improve flowing property.Polar compound also is considered to improve the magnetism between plastics and the rubber phase.In addition, polar group can improve natural rubber oil resistant and polarity petroleum chemistry base fluidic performance.

Look the ratio of each component in used thermoplastics and the final composition, can make the thermoplastic compounds that has different performance separately of certain limit.Can be controlled to be fit to specific application performance.Like this, with rubber matrix with such as polyolefins, polyethylene base class or polyurethanes mutually compounding just can make soft composite material.On the contrary, with rubber matrix with such as polyurethanes, polyamide-based, polyethylene base class or polyester mutually compounding just can make intermediate composite.With rubber matrix with just can make rigid composite material such as polyolefins, polyurethanes or polyamide-based compounding mutually.

When rubber matrix be used for soft composite material as with polyolefins mutually during compounding, the content of natural rubber in rubber matrix better is about 20-70%, preferably being about 40%, is 100 parts in total amount respectively, and rubber matrix is preferably 5-70 part with the relative blending ratio of plastics: 95-30 part.In general, if per 100 parts of matrix material total amounts, the content of rubber matrix is greater than 75 parts, and then the flowability of matrix material will be restricted, and can not form external phase in matrix material.Plastics in this soft composite material can be selected from polypropylene, polyethylene, polyvinyl acetate, ethane-acetic acid ethyenyl ester, ethylene-propylene plastics (Engage; DuPont), urethane or polyvinyl chloride.

First kind of compatilizer selected, made it have good and the performance natural rubber blend, and had the polar group that attracts with second kind of compatilizer.Think that first kind of compatilizer also can stablize the viscosity of natural rubber.Some performance at least of first kind of compatilizer can be transferred in the final composition, and its metastasis degree part is by the amount decision of first kind of compatilizer in final composition.

First kind of compatilizer of itrile group can be selected from: vinyl cyanide-elastoprene such as nitrile-synthetic polyisoprene or paracril; The nitrile natural rubber; Polyacrylonitrile; High nitrile polymer.Be added to of the desired properties decision of the amount of the itrile group compatilizer in the rubber matrix, but it is better greater than 10% of rubber matrix by final composition.

The acrylonitrile content of butyronitrile, nitrile-isoprene and nitrile-natural rubber is preferably greater than 20%.Nitrile content will improve the oil resistant and the fuel of rubber.And when the content of nitrile increased, it is relatively poor that the elasticity of nitrile rubber will become, yet, the polymkeric substance more thermoplasticity that becomes simultaneously, this processing to mixing material is favourable.Along with the increase of nitrile content, can improve with the consistency of polarity plasticizer or polarity plastics.

Also can use nitrile content greater than about 50% high nitrile polymer.For example, Barex210 (B-210) (BPAmerica Inc) is a kind of vinyl cyanide-methyl acrylate that is purchased-divinyl (70: 21: 9 weight parts) polymkeric substance.These polymkeric substance have good barrier property, and can be used for packing various types of solids, liquids and gases.

First kind of compatilizer of halogenation can be the halogenated polymer that is selected from following substances: chlorinated rubber, polyvinyl chloride, sovprene (Neoprene; Dupont), vinylidene fluoride.Chlorinatedpolyethylene or chlorosulfonated polyethylene are (as Hypalon; DuPont) be the slow polymkeric substance of sulfuration, it also is suitable first kind of compatilizer of halogenation when using when combining with sovprene.Perhaps, add halogen source such as N-bromosuccinimide halogenated rubber matrix on the spot.Perhaps, can also add chlorinated paraffinic oil and in composition, introduce halogen.The halogenation compatilizer should combine use with the nitrile compatilizer.

In order to keep some desired properties at least of halogenation compatilizer, the content of halogen-containing polymkeric substance is preferably greater than 15% of rubber matrix.The rubber matrix of halogen-containing basic first kind of compatilizer is particularly suitable for and polyvinyl chloride, polymeric amide, urethane and/or polyester blend.

First kind of compatilizer of epoxide base can be epoxidized natural rubber, and it should react natural rubber and hydrogen peroxide/formic acid/acetate and make.Be preferably, the epoxide content of epoxide based compatilizer is 20-50%, and obtaining epoxide content is the rubber matrix of 10-25%.

The first kind of compatilizer that contains acetic ester can be selected from: polyvinyl acetate, higher ethane-acetic acid ethyenyl ester, the vinyl-acetic ester rubber of vinyl acetate content.The content of acetic ester polymkeric substance is preferably the 20-50% of rubber matrix, and more preferably 30%, the vinyl acetate content of rubber matrix is greater than 20%.

Acrylate-based first kind of compatilizer can be selected from: acrylic rubber such as Vamac (Dupont) or the polymkeric substance that is made by following monomer: ethyl propenoate, methyl acrylate, methyl methacrylate.The acrylate compatilizer should combine use with about ratio that waits with the nitrile compatilizer.The mixture of acrylic acid or the like and first kind of compatilizer of nitrile is particularly suitable for and polymeric amide or esters of acrylic acid blend.

First kind of compatilizer of styryl can be selected from: vinylbenzene natural rubber, styrene butadiene rubbers, styrene isoprene styrene block copolymer (SIS) (SIS) are (as Kraton; Shell), vinylbenzene-ethyl butylene-styrene segmented copolymer (SEBS).The rubber matrix that contains first kind of compatilizer of styryl is particularly suitable for and styrenic thermoplastic plastics such as polystyrene or acrylonitrile-butadiene-styrene (ABS) (ABS) blend.

In rubber matrix, can adopt the combination of more than one first kind of compatilizer, so that rubber matrix has some performance at least of each compatilizer.For example, nitrile rubber can make rubber matrix have to a certain degree swell-resistant, makes final composition have the performance of the oil resistant of raising, fuel and fat.Similarly, halogenated rubber, especially chlorinated rubber are fireproof, therefore they are added to the resistivity against fire and the swell-resistant that can improve the finished product in the rubber matrix.Like this, the better combination of first kind of compatilizer is nitrile rubber and chlorinated rubber, and this combination often can improve final composition fire-resistant and based solvent of anti-petroleum chemistry the and oily performance.

Second kind of compatilizer selected,, be convenient to and thermoplastics blend difficult and first kind of compatilizer blend in the rubber phase of matrix material, to produce bigger polarity or electric density.Selection to second kind of compatilizer is not limited to those could interact and still have polar group with a large amount of non-polar rubbers compound.It is selected, so as can with interact as the polar group of vinyl cyanide, then obtain another and have polar group, thereby enlarge scope with rubber matrix blended plastics than high polarity or electric density.Have found that in many cases, natural rubber be inconsistent such as the blend of nitrile rubber-polar thermoplastic plastics.Yet, add the composition for thermoplastic elastomer that second kind of compatilizer just can add natural rubber and obtain external phase.

When using polyvinyl acetate, ethane-acetic acid ethyenyl ester, acrylamide or polyacrylamide, polyacrylonitrile or high nitrile resin, acrylic ester polymer, halogenated polymer, maleic anhydride or poly-maleic anhydride or bismaleimides, just can reach good compounding with plastics such as polyolefine including, but not limited to polymeric amide, urethane, polyester, the polystyrene that comprises high-impact polystyrene, acrylonitrile-butadiene-styrene (ABS) and easily blend as second kind of compatilizer.

The solution of the present invention comprises and forms two phases, rubber matrix as rubber phase and the thermoplastics component plastics mutually in, the present invention includes like this each component carried out mixing first time, make rubber matrix.Rubber matrix and plastics mixing mutually comprised rubber matrix (rubber phase) and plastics are carried out mixing the second time mutually.Rubber matrix is actually rubber phase, and it is as intermediate.Can customize rubber matrix, so that can mix with in the multiple different thermoplastic plastics any.Rubber phase is relatively good mutually with plastics to be 5: 95-90: 10, however the composition that contains greater than about 75% rubber phase often has high viscosity, so just be difficult for flowing, thereby its application may be restricted.In order in final composition, to obtain thermoplasticity, require composition to have successive plastics phase, so the content of plastics phase should be at least 10% of final composition.These parts must provide enough rubber obtaining elastic composition, and can provide enough plastics to obtain thermoplasticity.Rubber can change in these limits with the ratio of plastics, to make the composition with desired properties.

At first make rubber phase (or rubber matrix), it comprises carries out the blended step with each component of rubber phase, and described each component comprises a) natural rubber, b) first kind of compatilizer, c) second kind of compatilizer and d) any other additive that may need.Make rubber phase with the cold mixing method.This cold mixing method is generally carried out being lower than under about 120 ℃ temperature.Think that granular size that cold mixing can reduce natural rubber to being lower than about 50 μ, so just forms the homogenizing mixture of natural rubber particles dispersed in rubber matrix.After mixing or plasticating, rubber phase is in case just form stable viscosity normally, then can allow its slaking, carries out the aforesaid second time afterwards again and mixes.

First kind of compatilizer be except can be for rubber matrix provides the polarity, especially be considered to can stable matrix in the viscosity of natural rubber, and prevent rubber from recovering its molecular weight and mutually and discontinuous conventional tendency of natural rubber intermediate formation at plastics.Think that second kind of compatilizer can be further for matrix provides polarity, thereby the polar thermoplastic plastics of certain limit and matrix are compatible.

Can adopt any method in currently known methods such as melting mixing or the dynamic vulcanization to carry out the mixing second time.With dynamic vulcanization is good, and it can adopt conventional plasticating equipment such as banbury mixers, Bradley Bender mixing machine, mixing forcing machine or twin screw extruder to carry out.The shear conditions that provides under the dynamic vulcanization condition makes rubber phase disperse mutually with plastics.Like this, reaching between rubber and the plastics under the crosslinked temperature and time condition of required degree, rubber phase is handled with plastics mixture mutually.Plastics phase and rubber phase are mixed, under the temperature that is enough to softening at least plastics, but better under the temperature that is higher than the plastics fusing point, mixture is plasticated, make thermoplastic compounds.In order farthest to reduce the thermal destruction of rubber matrix, better be to make plastic molting being lower than under 205 ℃.Representational temperature can include, but are not limited to: polypropylene is 170 ℃; Polyethylene is 130-150 ℃; Polymeric amide is 180-200 ℃; Thermoplastic polyurethane is 180-200 ℃; Polyester is 200 ℃.The melt temperature of plastics better is to be lower than 205 ℃, because natural rubber tends to degraded when being higher than this temperature.Under these temperature the heating and plasticate be enough to usually take place crosslinked.

Composition of the present invention also can adopt the method except dynamic vulcanization to prepare.Like this, the rubber phase of complete cure can be Powdered and mix mutually with plastics, and condition is that rubber grain is little and the abundant coupling of the size of the size of rubber grain and plastics, so just can make rubber grain and be dispersed in the composition of plastics in mutually well.

Rubber matrix need add vulcanizing agent (curative agent) with plastics mixing mutually, and is crosslinked to form in rubber matrix.Yet what should understand is when using some plastics such as ethane-acetic acid ethyenyl ester or polyethylene, plastics itself and/or can take place with rubber matrix that some is crosslinked.In vulcanization of rubber process, generally can use any vulcanization system.Like this, vulcanization system can be selected from and include, but are not limited to: the hydroxymethyl-phenol system is (as SP1045; Schenctady); Bismaleimide Resin (HVA ₂); Bismaleimides MBTS system; The bismaleimides peroxide systems; Organic peroxide systems; Accelerated sulfur system; Carbamate system (as Novar 924); The borine system; The radiation system.Vulcanizing agent better is linking agent such as superoxide Bismaleimide Resin.Perhaps, or in addition, vulcanizing agent can comprise interface promotor such as phenylene bismaleimides (HVA ₂, Dupont), (Perkalink 401 for ethylene glycol dimethacrylate; Akzo Nobel), (Perkalink 400 for trimethylolpropane trimethacrylate; Akzo Nobel), (Perkalink 300 for triallyl isocyanurate; AkzoNobel) or triallyl cyanurate (Perkalink 301; Akzo Nobel).Interface promotor also can be used as the stablizer in whole superoxide/carbamate cross-linking system.

An advantage of peroxide vulcanizing system is as superoxide and SARET/HVA ₂Combine when using mutually and can produce crosslinkedly between the rubber phase, and use peroxide vulcanizing system to make to have the matrix material that improves tensile strength and improve hot strength at plastics.Yet peroxide vulcanizing system can not be used for directly contacting with polypropylene, because superoxide can play the degraded plastics, yet they can be used for subsequently and polypropylene blended rubber matrix.In addition, peroxide vulcanizing system and maleic anhydride cannot be used in the system of opening wide, have the danger of catching fire because contact with air.Peroxide vulcanizing system should not be used for neoprene, magnesium oxide or zinc oxide and resol should be combined as vulcanizing agent in this case.

Known any peroxide vulcanizing system can use in the present invention in the prior art.Superoxide can be selected from and include, but are not limited to dicumyl peroxide, di-t-butyl peroxide, two (2-tert-butyl hydroperoxide sec.-propyl) benzene.Superoxide can be stated from the inert support.When the total content of rubber in final composition less than 15% the time, peroxide vulcanizing system not too uses usually, unless there is HVA ₂Or SARET.In general, when the total content of rubber in final composition less than 15% the time, HVA ₂Can provide enough crosslinked, and that a spot of superoxide will help will be this crosslinked.If there is not HVA ₂Or SARET, then superoxide probably makes degradation of polypropylene, and composition will lose required performance like this.

The sulfenyl vulcanization system is compared with plastics composition mutually with containing crosslinked rubber phase at plastics mutually and can not produce crosslinkedly between the rubber phase like this, and the composition of gained has lower compression set and tensile property preferably.

In 20% the composition of rubber matrix total amount greater than whole composition, should plasticate, promptly vulcanizing agent is added in the rubber matrix during mix stages for the first time.Be under the situation of 10-20% of whole composition at rubber matrix content, should be with HVA ₂Be added to plastics mutually in, and superoxide is added in the rubber phase.When the content of rubber matrix in whole composition less than 10% the time, should not use superoxide, if the words that need can be used other vulcanizing agent such as accelerated sulfur system or phenolic systems.

Can be added in the performance that additive commonly used in compounding rubber and/or the thermoplastics comes the modified thermoplastic rubber composition.Operable additive comprises thermostabilization agent, fire retardant chemistry agent, peptizing agent, filler, extender, softening agent, pigment, promotor, stablizer, anti degradant such as antioxidant and UV filtering agent, processing aid and extending oil.

When in composition, using halogen-containing group such as tin chloride or chlorinated paraffinic oil, can in composition, add magnesium oxide or toxilic acid as scavenging agent and/or pH stablizer.

Suitable UV filtering agent can be selected from one or more and include, but are not limited to Tinuvan P (CibaGeigy), titanium dioxide or carbon black.Explanation by manufacturers should add Tinuvan P.Per 100 parts of final compositions, titanium dioxide or sooty add-on should be about 2.5 parts.

Suitable manufacturing methods can be selected from one or more and include, but are not limited to aromatics, cycloalkanes and alkane extending oil, phthalate plasticizers, sulphonamide softening agent, adipate plasticizers or phosphate plasticizer.Softening agent is a synourin oil preferably, and its add-on can be the 0.8phr of rubber content, and coumarone and indene resin are highly suitable for composition of the present invention, and its consumption can be up to 5 phr.

Processing aid can comprise internal lubricant, is used for increasing flowing and the raising mixing, especially in the stage of plasticating.Examples of suitable lubricants can comprise zinc or magnesium salts.Lubricant is a Zinic stearas preferably, and it adds in the process of plasticating.Can add that the form of stearic acid (1-5phr according to appointment) adds Zinic stearas at an easy rate by zinc oxide (5-15phr according to appointment).The common maintenance of remaining vulcanization system does not add elastomerics, before just beginning sulfuration.

Reinforcing filler can be selected from and include, but are not limited to carbon black, clay, mineral such as talcum and silica.Filler often can improve the tensile strength of final composition.The add-on of filler can be up to 30phr.Add-on surpasses the flowability that this scope tends to weaken matrix material.Also can add the molding shrinkage that homopolymer polypropylene causes owing to the adding filler with balance.

Thermal stabilization additive can be selected from and include, but are not limited to resol (available from HylamBakelite); Fletol H; Chlorinated rubber.

Suitable antioxidant can be selected from one or more and include, but are not limited to Wingstay L/100 (Goodyear); Two-naphthyl-P-pHENYLENE dI AMINE (Santowhite CI, Monsanto); The phenol of vinylbenzeneization (Montaclere-SE, Monsanto); 2, and 5-two (tert-pentyl) quinhydrones (Santovar-A, Monsanto); 4, and 4 '-butylidene two (the 6-tertiary butyl-meta-cresol) (Santowhite, Monsanto); Tributyl thiourea (Santowhite-TBTU, Monsanto); 6-tertiary butyl meta-cresol/sulfur dichloride (Santowhite-MK, Monsanto); Three nonyl phenylene phosphoric acid ester (TNNP; Ciba Geigy).The add-on of antioxidant in whole composition is preferably 1-2%.

The anti degradant that can add comprises ethylene-propylene-diene terpolymer (EPDM) rubber.Its add-on can account for 5% of whole composition, to improve the weathering resistance of composition.This consumption is higher than 5% may produce adverse influence to sulfuration, because EPDM is the slow rubber of sulfuration.

Peptizing agent can be selected from the prior art known any, for example Renacit 11 (Bayer).The add-on of these peptizing agents in whole composition should be about 0.07%.

We can say that second aspect of the present invention relates to a kind of matrix material of natural rubber thermoplastics, it is that the rubber matrix of first aspect of the present invention is got with being selected from any or multiple thermoplastics blend in polyolefine, urethane, polyester, polymeric amide, esters of acrylic acid, the acrylonitrile-butadiene-styrene (ABS) (ABS).

By the matrix material that a kind of natural rubber thermoplastics is provided in broad terms of second aspect of the present invention, it comprises like this:

A) natural rubber 10-90% (v/v),

B) one or more are selected from first kind of compatilizer of the polymkeric substance that comprises following arbitrary material,

I) nitrile,

Ii) halogen,

Iii) acetate esters,

Iv) epoxide,

V) vinylbenzene, or

Vi) acrylate,

C) one or more are selected from second kind of compatilizer of the interface secondary accelerator that comprises following arbitrary material,

I) polyvinyl acetate,

Ii) ethane-acetic acid ethyenyl ester,

Iii) polyacrylonitrile or high nitrile resin,

Iv) acrylamide or polyacrylamide,

V) resol,

Vi) acrylic ester polymer,

Vii) halogenated polymer,

Viii) maleic anhydride or poly-maleic anhydride, or

Ix) bismaleimides,

D) one or more are selected from the thermoplastics that comprises following arbitrary material,

I) urethane,

Ii) polyester,

Iii) polymeric amide,

Iv) acrylate,

V) acrylonitrile-butadiene-styrene (ABS),

Vi) polyolefine, or

Vii) cellulose ester.

It is big that the polarity of thermoplastics cans be compared to natural rubber most, and this thermoplastics comprises urethane, polyester, polymeric amide, acrylate, acrylonitrile-butadiene-styrene (ABS) or Mierocrystalline cellulose.Think that rubber such as isoprene-isobutylene rubber that some sulfuration is slow are not suitable for practice of the present invention especially owing to its inappropriate curability.And when thermoplastics was selected from polyolefine and first kind of compatilizer and is selected from halogenated polymer, second kind of compatilizer should not be resol or halogenated polymer.

The thermoplastic plastic of portion of hot at least used in the matrix material randomly can be from the thermoplastics of recycling.

Suitable polyolefine can be selected from and include, but are not limited to high density polyethylene(HDPE) (HDPE), LLDPE (LLDPE), homopolymer polypropylene (PPHP), polypropylene copolymer (PPCP), poly-(ethylene-propylene) (PEP).Polyolefine is owing to its high chemical resistant properties, electrical property, high shock strength and low cost are selected for use.

Suitable polyamide thermoplastic comprises crystallization or resinoid high molecular weight copolymer or terpolymer.One or more lactan such as hexanolactam, pyrrolidone, laurolactam can be carried out polymerization or diamines and diacid are carried out condensation and make polymeric amide.Suitable polymeric amide comprises and contains the polymerization acid amides of recurring amide radical group as a main polymer chain part, it can be selected from and comprise, but be not limited to polycaprolactam (nylon-6), nylon 12 (PA-12), polyhexamethylene adipamide (nylon-6,6), poly-azelaoyl hexanediamine (nylon-6,9), polyhexamethylene sebacamide (nylon-6,10), poly-6I hexamethylene isoterephalamide (nylon-6, IP), the condensation product (nylon-11) of 11-aminoundecanoic acid and the reaction product of Viscotrol C and sebacic acid.Suitable polymeric amide also comprises and other monomeric multipolymer.Polymeric amide is owing to its high shock strength, shock resistance, high tensile strength, the ability and/or the flame retardant resistance of absorption moisture are selected for use.

Suitable urethane can include, but are not limited to based on hexanolactam, ethylene glycol or hexanodioic acid ethyl ester or propyl ester and isocyanate reaction and TPU(Thermoplastic polyurethanes), its Xiao A hardness is 80-90.Urethane is owing to the suitable performance of its flexible and wear resistance is selected for use.

Many thermoplastic polyesters that are purchased all are suitable, one or more di-carboxylic acid, acid anhydride or ester and one or more dibasic alcohol can be carried out condensation and make polyester.The Mierocrystalline cellulose polyester is specially adapted to the present invention, and suitable Mierocrystalline cellulose can include, but are not limited to the polymkeric substance of rhodia, acetobutyric acid Mierocrystalline cellulose and cellulose propionate.Suitable polyester also comprises polycarbonate.

Suitable acrylic acid or the like thermoplastics can comprise polymethylmethacrylate, and its adding can improve the thermostability and the tint permanence (coulourability) of final composition.And acrylic acid or the like is highly crystalline often, so when needing the final composition of highly crystalline, it suits.

Press the performance of composition, rubber thermoplastic composition of the present invention can be divided into a kind of in four classes, be i.e. rigidity, toughness reinforcing, half toughness reinforcing or soft natural rubber thermoplastic compounds.

Rubber thermoplastic composition of the present invention can be used as thermoplastic elastomer, and this elastomerics can be processed and can be made parts through the ordinary method that is used for thermoplastic material.Adopt the standard testing method of using in rubber and the thermoplastics to measure the mechanical property of the present composition.

Thermoplastic rubber composition of the present invention can be used for the goods that use in manufacturing machine, automobile, building, weaving, moving articles, irrigation, cable, agricultural, footwear, pipe/flexible pipe and tire and the wheel industry.Goods can through extrude, injection moulding or compression moulding and make.

We can say that the 3rd aspect of the present invention relates to a kind of goods of being made by thermoplastic composite of the present invention, these goods can adopt any appropriate method of using in the thermoplastics to make, described method comprise extrude, injection moulding or compression moulding.

We can say that the 4th aspect of the present invention relates to a kind of method of making the matrix material of natural rubber thermoplastics, it comprises the rubber matrix of making first aspect of the present invention, then under the condition of dynamic vulcanization with rubber matrix and plastics blended step mutually.

Brief description of drawings

In order to understand better, the present invention will be further described with reference to a plurality of embodiment that also represent in the accompanying drawing of this paper.

Fig. 1 illustrated with dsc and measured the weight loss of natural rubber/nitrile rubber/polyolefinic ' soft ' level sample and the relation of temperature,

Fig. 2 illustrated with dsc and measured the heat flux of natural rubber/nitrile rubber/polyolefinic ' soft ' level sample and the relation of temperature,

Fig. 3 has illustrated the out-of-phase modulus of usefulness dynamic mechanical analysis method measurement natural rubber/nitrile rubber/polyolefinic ' soft ' level sample and the relation of temperature,

Fig. 4 illustrated with dsc and measured the weight loss of natural rubber/nitrile rubber/polyolefinic ' centre ' level sample and the relation of temperature,

Fig. 5 illustrated with dsc and measured the heat flux of natural rubber/nitrile rubber/polyolefinic ' centre ' level sample and the relation of temperature,

Fig. 6 has illustrated the out-of-phase modulus of usefulness dynamic mechanical analysis method measurement natural rubber/nitrile rubber/polyolefinic ' centre ' level sample and the relation of temperature,

Fig. 7 illustrated with dsc and measured the weight loss of natural rubber/nitrile rubber/polyolefinic ' rigidity ' level sample and the relation of temperature,

Fig. 8 illustrated with dsc measure the heat flux of natural rubber/nitrile rubber/polyolefinic ' rigidity ' level sample and temperature relation and

Fig. 9 has illustrated with the dynamic mechanical analysis method and has measured the out-of-phase modulus of natural rubber/nitrile rubber/polyolefinic ' rigidity ' level sample and the relation of temperature.

Detailed description of the present invention

Be the multiple composition that makes by the present invention below.What should understand is that these only are exemplary, and the present invention is not limited to any or the summation of these embodiment in them.

Embodiment 1-makes the general step of matrix material

Be the general step of making matrix material of the present invention below.Provide in the consumption of each component specific embodiment below.

Step: in Banbury mixer or mill with natural rubber together with first kind and second kind of compatilizer and peptizing agent (if the words that need) about 5 minutes of preplastication or shorter time, although if adopt mill, this process spends the time more than 10 minutes possibly.Time is depended on the viscosity of rubber.Temperature preferably should be above 120 ℃ in the process of mixing or plasticating.In the process of plasticating, can add any additives such as filler.After the mixing, raw material is stable viscosity normally, section and with it with the polythene strip slaking between each fragment.Curing time can be 6-12 hour.Then rubber matrix is cut into band shape, is added to the Branbury mixing machine of 130-205 ℃ (this depends on the melt temperature of thermoplastics) or mixes in the forcing machine twin screw of measuring system (as have).Then add thermoplastics, under the situation of Branbury mixing machine, mix and add antioxidant after 5 minutes, after 1 minute, under the condition of heating, the matrix material of gained is sent in the forcing machine again, extrude and granulation.Extruded product and on line material cutter or die face cutting machine, carry out granulation then.

Embodiment 2.1-contains the rubber thermoplastic composition of first kind of compatilizer of nitrile and polyamide thermoplastic plastics

Press the step of embodiment 1 and make the listed matrix material of table 1.

Table 1

????NR	??NIR/N ????BR	???PA-6	???PVA	Resol	Tin chloride	Zinic stearas	HVA ₂	???DCP	Antioxidant
????NR	??NIR/N ????BR	???PA-6	???PVA	Resol	Tin chloride	Zinic stearas	HVA ₂	???DCP	Antioxidant	????5	????25	????70	????5	????5	????0.5	????1	??0.75	??0.05	????1
????10	????30	????60	????5	????5	????0.5	????1	??0.75	??0.06	????1	????5	????25	????70	????5	????5	????0.5	????1	??0.75	??0.05	????1
????10	????30	????60	????5	????5	????0.5	????1	??0.75	??0.06	????1	????20	????30	????50	????5	????5	????0.5	????1	??0.75	??0.07	????1
????30	????30	????40	????5	????5	????0.5	????1	??0.75	??0.08	????1	????20	????30	????50	????5	????5	????0.5	????1	??0.75	??0.07	????1
????30	????30	????40	????5	????5	????0.5	????1	??0.75	??0.08	????1	????40	????30	????30	????5	????5	????0.5	????1	??0.75	??0.09	????1

NR natural rubber: SMRCV/ISNRCV or the equivalent NIR/NBR nitrile content that contains low impurity content are that 40% vinyl cyanide-synthetic polyisoprene or nitrile content are 40% acrylic nitrile-butadiene-two

Alkene rubber or both were with 50: 50 ratio blended mixture PA-6 polycaprolactam (nylon-6): mfi3, and Shore hardness is the resol (Hylak that 80APVA polyvinyl acetate resol has thermostability/hardness; Bakelite) tin chloride tin protochloride (II): selecting for use can available rank Zinic stearas commodity rank HVA on the market ₂Bismaleimides (DuPont) DCP dicumyl peroxide (Akzo Perkadox 14S) v antioxidant Wingstay 100 (Goodyear)

If need softening agent, also can add synourin oil (DCO).

Embodiment 2.2-contains the rubber thermoplastic composition of first kind of compatilizer of nitrile and polylefin thermoplatic plastics

Make the matrix material in the table 2 and 3 below.

The soft level of table 2

Shore hardness	??NR	??NBR	??LLDPE	???EVA	??Engage	??HVA ₂	Superoxide	??MBTS	Zinic stearas	Antioxidant
Shore hardness	??NR	??NBR	??LLDPE	???EVA	??Engage	??HVA ₂	Superoxide	??MBTS	Zinic stearas	Antioxidant	??65A	??15	??30	????10	????35	????10	??0.75	??0.07	??0.25	????1	????1
??60A	??15	??30	????10	????30	????15	??0.75	??0.07	??0.25	????1	????1	??65A	??15	??30	????10	????35	????10	??0.75	??0.07	??0.25	????1	????1
??60A	??15	??30	????10	????30	????15	??0.75	??0.07	??0.25	????1	????1	??55A	??15	??30	????5	????25	????20	??0.75	??0.075	??0.25	????1	????1
??50A	??15	??30	????5	????20	????25	??0.75	??0.075	??0.25	????1	????1	??55A	??15	??30	????5	????25	????20	??0.75	??0.075	??0.25	????1	????1
??50A	??15	??30	????5	????20	????25	??0.75	??0.075	??0.25	????1	????1	??45A	??15	??30	????5	????10	????30	??0.75	??0.08	??0.25	????1	????1
??40A	??15	??30	????5	????5	????35	??0.75	??0.08	??0.25	????1	????1	??45A	??15	??30	????5	????10	????30	??0.75	??0.08	??0.25	????1	????1

Table 3 intermediate stage

Shore hardness	??NR	??NIR/ ??NBR	?HDPE	?EVA	?LLDPE	?HVA ₂	Superoxide	???MBTS	Zinic stearas	Antioxidant
Shore hardness	??NR	??NIR/ ??NBR	?HDPE	?EVA	?LLDPE	?HVA ₂	Superoxide	???MBTS	Zinic stearas	Antioxidant	??90A	??15	????25	??40	??20		??0.75	??0.06	??0.25	????1	????1
??85A	??15	????25	??30	??25	??5	??0.75	??0.06	??0.25	????1	????1	??90A	??15	????25	??40	??20		??0.75	??0.06	??0.25	????1	????1
??85A	??15	????25	??30	??25	??5	??0.75	??0.06	??0.25	????1	????1	??80A	??20	????30	??20	??20	??10	??0.75	??0.07	??0.25	????1	????1
??75A	??20	????30	??10	??20	??20	??0.75	??0.07	??0.25	????1	????1	??80A	??20	????30	??20	??20	??10	??0.75	??0.07	??0.25	????1	????1
??75A	??20	????30	??10	??20	??20	??0.75	??0.07	??0.25	????1	????1	??70A	??25	????35	??5	??10	??25	??0.75	??0.08	??0.25	????1	????1
??65A	??25	????35		??10	??30	??0.75	??0.08	??0.25	????1	????1	??70A	??25	????35	??5	??10	??25	??0.75	??0.08	??0.25	????1	????1

NR natural rubber: SMRCV/ISNRCV or the equivalent NIR/NBR nitrile content that contains low impurity content are that 40% vinyl cyanide-synthetic polyisoprene or nitrile content are 40% acrylic nitrile-butadiene-

Elastoprene or both were with 50: 50 ratio blended mixture HDPE high density polyethylene(HDPE)s: melt flow rate (MFR) (mfi) 3: molding graae EVA ethane-acetic acid ethyenyl ester: better rank is 28% vinyl acetate content; Mfi2LLDPE LLDPE: molding graae; Mfi3 (Exxon) Engage ethylene-propylene plastic H VA ₂Bismaleimides (DuPont) superoxide peroxidation isopropyl benzene (EIFATO Therm/AKZO Nobel) antioxidant Wingstay 100 (Goodyear)

Process:

NR, NIR and/or NBR, HDPE and EVA are plasticated with under 80rpm and 100 ℃ in the Barbender mixing machine.With the rubber matrix of plasticating together with LLDPE, HVA ₂, superoxide and Zinic stearas carry out blend together in 180-190 ℃ Banbury mixer (Branbury).Terminal point in the blend process adds antioxidant.Press embodiment 1 described extruded material and granulation.

Embodiment 2.3-contains the listed matrix material of manufacturing table 4 below the rubber thermoplastic composition of first kind of compatilizer of nitrile and polylefin thermoplatic plastics and bismaleimides compatilizer.

Table 4

Shore hardness	Natural rubber	??NIR/ ??NBR	?PPHP	??PPCP	??HMHDPE	?LDPE	??HVA ₂	Superoxide	Zinic stearas	Antioxidant
Shore hardness	Natural rubber	??NIR/ ??NBR	?PPHP	??PPCP	??HMHDPE	?LDPE	??HVA ₂	Superoxide	Zinic stearas	Antioxidant	??60D	????3	????2	????40	????40	????15		??0.75		????1	????1
??55D	????3	????2		????25	????50	????10	??0.75		????1	????1	??60D	????3	????2	????40	????40	????15		??0.75		????1	????1
??55D	????3	????2		????25	????50	????10	??0.75		????1	????1	??50D	????6	????4	????30	????30	????30		??0.75	??0.03	????1	????1
??45D	????9	????6		????30	????30	????25	??0.75	??0.04	????1	????1	??50D	????6	????4	????30	????30	????30		??0.75	??0.03	????1	????1
??45D	????9	????6		????30	????30	????25	??0.75	??0.04	????1	????1	??40D	????12	????8		????30	????30	????20	??0.75	??0.05	????1	????1
??35D	????15	????10		????30	????30	????15	??0.75	??0.06	????1	????1	??40D	????12	????8		????30	????30	????20	??0.75	??0.05	????1	????1
??35D	????15	????10		????30	????30	????15	??0.75	??0.06	????1	????1	??30D	????18	????12		????30	????20	????20	??0.75	??0.07	????1	????1
??25D	????24	????16		????20	????20	????20	??0.75	??0.08	????1	????1	??30D	????18	????12		????30	????20	????20	??0.75	??0.07	????1	????1
??25D	????24	????16		????20	????20	????20	??0.75	??0.08	????1	????1	??20D	????30	????20		????20	????15	????15	??0.75	??0.08	????1	????1

NR natural rubber: SMRLCV or ISNRLCV or equivalent: with lower protein and low impurity

Wei good NIR/NBR nitrile content be that 40% vinyl cyanide-synthetic polyisoprene or nitrile content are 40% acrylic nitrile-butadiene-

Elastoprene or both were with 50: 50 ratio blended mixture PPHP homopolymer polypropylene: mfi3; General (Shell) PPCP polypropylene copolymer: mfi3; General (Shell) HMHDPE HMW (high molecular weight)-high density polyethylene: mfi2 (Exxon) LDPE new LDPE (film grade): general; Mfi2 (Exxon) HVA ₂Bismaleimides (Dupont) superoxide peroxidation isopropyl benzene (Elf Atochem/AKZO Nobel)-should when plasticating, add Zinic stearas to select commodity rank antioxidant Wingstay L/100 (Goodyear) or Santowhite (Monsanto) for use

Can add 2% titanium dioxide, carbon black or Tunivan (P) [Ciba Geigy (Novartis)], so that additional ultraviolet protection is provided.

PPHP-can be replaced by PPCP, and PPHP is used for the balance molding shrinkage.

Can in mixing material, add Vanillin (1-2 phr), to improve smell.

Can add filler such as CaCO up to 30% ₃/ talcum.

Process: rubber is plasticated with 10 parts of paraffin oils, 0.08 part of Renacit-11 (Bayer) and/or 0.04 part of DCO (synourin oil).With the rubber of plasticating together with polyolefine, HVA ₂, superoxide and Zinic stearas blend in 180-190 ℃ Banbury mixer together.Terminal point in the blend process adds antioxidant.Extrude identical material and granulation by embodiment 1.Should allow mass expanded to maximum, to avoid taking place in the future molding shrinkage.

Embodiment 3.1-contains the composition and the performance of the rubber thermoplastic polyamide compoiste material of first kind of compatilizer of nitrile

Component	Consumption (kg)	Consumption (kg)	Source/rank
Component	Consumption (kg)	Consumption (kg)	Source/rank		Natural rubber	????20	????30	SMR-LCV Malaysia
Paracril	????20	????30	JSR-N ACN content 50%; Japan		Natural rubber	????20	????30	SMR-LCV Malaysia
Paracril	????20	????30	JSR-N ACN content 50%; Japan		Polymeric amide-6	????60	????40	Polycaprolactam SRF MFI3
Polyvinyl acetate	????5	????5	Commodity		Polymeric amide-6	????60	????40	Polycaprolactam SRF MFI3
Polyvinyl acetate	????5	????5	Commodity		Hydroxymethyl-phenol	????1	????1	??SP1045：Schenectady ??Chemicals
Tin chloride	????1	????1	Commodity		Hydroxymethyl-phenol	????1	????1	??SP1045：Schenectady ??Chemicals
Tin chloride	????1	????1	Commodity		Zinic stearas	????2	????2	Commodity
Bismaleimides	????1	????1	??HVA ₂：DuPont(USA)		Zinic stearas	????2	????2	Commodity
Bismaleimides	????1	????1	??HVA ₂：DuPont(USA)		Superoxide	????0.4	????0.6	Tertiary butyl isopropyl benzene; (Perkadox 14-40A, Akzo Nobel)
Synourin oil	????0.8	????1.0	??Generic		Superoxide	????0.4	????0.6
Synourin oil	????0.8	????1.0	??Generic		Antioxidant	????2	????2	??Wingstay-100(Goodyear)
Performance			Unit	Testing method	Antioxidant	????2	????2	??Wingstay-100(Goodyear)
Performance			Unit	Testing method	Shore hardness	????70D	????50D	??-	??ASTM?D2240
Density	????1.14	????1.12	??gm/cc	??ASTM?D792	Shore hardness	????70D	????50D	??-	??ASTM?D2240
Density	????1.14	????1.12	??gm/cc	??ASTM?D792	Tensile strength	????780	????670	??kg/cm ²	??ASTM?D638
Extension at break	????350	????380	??％	??ASTM?D638	Tensile strength	????780	????670	??kg/cm ²	??ASTM?D638
Extension at break	????350	????380	??％	??ASTM?D638	Modulus in flexure	????2400	????2000	??kg/cm ²	??ASTM?D638
Brittleness temperature	????-40	????-40	??℃	??ASTM?D746	Modulus in flexure	????2400	????2000	??kg/cm ²	??ASTM?D638
Brittleness temperature	????-40	????-40	??℃	??ASTM?D746	Shock strength	????34	????NB	??kg·cm/cm ²	??ASTM?D256
Heat deflection temperature (HDT) (4.6kg/cm ²)	????＞160	????＞160	??℃	??ASTM?D648	Shock strength	????34	????NB	??kg·cm/cm ²	??ASTM?D256

Embodiment 3.2-contains the composition and the performance of the rubber thermoplastic polyester composite of first kind of compatilizer of nitrile

Component	Consumption (kg)	Consumption (kg)	Source/rank
Component	Consumption (kg)	Consumption (kg)	Source/rank		Natural rubber	????20	????20	SMR-LCV Malaysia
Paracril	????20	????20	JSR-N ACN content 50%; Japan		Natural rubber	????20	????20	SMR-LCV Malaysia
Paracril	????20	????20	JSR-N ACN content 50%; Japan		Ethylene-acrylate rubber	????-	????20	??VAMAC(DuPont)
Polyester (Mierocrystalline cellulose)	????60	????40	??Eastacel(Eastmann?Chemical ??Products，USA)		Ethylene-acrylate rubber	????-	????20	??VAMAC(DuPont)
Polyester (Mierocrystalline cellulose)	????60	????40	??Eastacel(Eastmann?Chemical ??Products，USA)		Polyvinyl acetate	????5	????5	??Generic
Hydroxymethyl-phenol	????1	????1	??SPl045(Schenectady ??Chemicals)		Polyvinyl acetate	????5	????5	??Generic
Hydroxymethyl-phenol	????1	????1	??SPl045(Schenectady ??Chemicals)		Phenolic aldehyde	????3	????3	??Hylak(Hylan?Bakelire)
Tin chloride	????1	????1	Commodity		Phenolic aldehyde	????3	????3	??Hylak(Hylan?Bakelire)
Tin chloride	????1	????1	Commodity		Zinic stearas	????2	????-	Commodity
Bismaleimides	????1	????1	??HVA ₂：DuPont(USA)		Zinic stearas	????2	????-	Commodity
Bismaleimides	????1	????1	??HVA ₂：DuPont(USA)		Zinc oxide	????0.6	????0.5	??Generic
Synourin oil	????0.8	????1.0	??Generic		Zinc oxide	????0.6	????0.5	??Generic
Synourin oil	????0.8	????1.0	??Generic		Antioxidant	????1	????1	??Wingstay-100(Goodyear)
Performance			Unit	Testing method	Antioxidant	????1	????1	??Wingstay-100(Goodyear)
Performance			Unit	Testing method	Shore hardness	????60D	????40D	????-	??ASTM?D2240
Density	????1.20	????1.18	????gm/cc	??ASTM?D792	Shore hardness	????60D	????40D	????-	??ASTM?D2240
Density	????1.20	????1.18	????gm/cc	??ASTM?D792	Tensile strength	????480	????420	????kg/cm ²	??ASTM?D638
Extension at break	????250	????270	????％	??ASTM?D638	Tensile strength	????480	????420	????kg/cm ²	??ASTM?D638
Extension at break	????250	????270	????％	??ASTM?D638	Modulus in flexure	????-	????-	????kg/cm ²	??ASTM?D638
Brittleness temperature	????-30	????-30	????℃	??ASTM?D746	Modulus in flexure	????-	????-	????kg/cm ²	??ASTM?D638
Brittleness temperature	????-30	????-30	????℃	??ASTM?D746	Shock strength	????13.5	????15.5	????kg·cm/cm ²	??ASTM?D256
Heat deflection temperature (HDT) (4.6 kg/cm ²)	????＞180	????＞180	????℃	??ASTM?D648	Shock strength	????13.5	????15.5	????kg·cm/cm ²	??ASTM?D256

Embodiment 3.3-contains the composition and the performance of the rubber thermoplastic compound polyurethane material of first kind of compatilizer of nitrile

Component	Consumption (kg)	Consumption (kg)	Source/rank
Component	Consumption (kg)	Consumption (kg)	Source/rank		Natural rubber	????20	????20	SMR-LCV Malaysia
Paracril	????20	????20	JSR-NACN content 50%; Japan		Natural rubber	????20	????20	SMR-LCV Malaysia
Paracril	????20	????20	JSR-NACN content 50%; Japan		Sovprene	????-	????20	????Neoprene(DuPont)
Thermoplastic polyurethane	????60	????40	Despiopan (Bayer); Hardness 30 Shore D		Sovprene	????-	????20	????Neoprene(DuPont)
Thermoplastic polyurethane	????60	????40	Despiopan (Bayer); Hardness 30 Shore D		Polyvinyl acetate	????5	????-	????Generic
Polyvinyl chloride	????-	????5	Occidental; Stick with paste the level mixing material		Polyvinyl acetate	????5	????-	????Generic
Polyvinyl chloride	????-	????5	Occidental; Stick with paste the level mixing material		Phenolic aldehyde	????3	????3	????Hylak(Hylan?Bakelite)
Hydroxymethyl-phenol	????1	????1	?SP1045(Schenectady?Chemicals)		Phenolic aldehyde	????3	????3	????Hylak(Hylan?Bakelite)
Hydroxymethyl-phenol	????1	????1	?SP1045(Schenectady?Chemicals)		Tin chloride	????1	????-	Commodity
Zinic stearas	????2	????-	Commodity		Tin chloride	????1	????-	Commodity
Zinic stearas	????2	????-	Commodity		Bismaleimides	????1	????1	????HVA ₂；DuPont(USA)
Zinc oxide	????-	????5	Commodity		Bismaleimides	????1	????1	????HVA ₂；DuPont(USA)
Zinc oxide	????-	????5	Commodity		Superoxide	????0.4	????-	Dicumyl peroxide (Akzo Nobel)
Synourin oil	????0.8	????1.0	????Generic		Superoxide	????0.4	????-	Dicumyl peroxide (Akzo Nobel)
Synourin oil	????0.8	????1.0	????Generic		Antioxidant	????2	????2	????Wingstay-100(Goodyear)
Performance			Unit	Testing method	Antioxidant	????2	????2	????Wingstay-100(Goodyear)
Performance			Unit	Testing method	Shore hardness	????90A	????80A	????-	??ASTM?D2240
Density	????1.20	????1.18* ????(1.28)	????gm/cc	??ASTM?D792	Shore hardness	????90A	????80A	????-	??ASTM?D2240
Density	????1.20	????1.18* ????(1.28)	????gm/cc	??ASTM?D792	Tensile strength	????520	????460	????kg/cm ²	??ASTM?D638
Extension at break	????400	????480	????％	??ASTM?D638	Tensile strength	????520	????460	????kg/cm ²	??ASTM?D638
Extension at break	????400	????480	????％	??ASTM?D638	Modulus in flexure	????-	????-	????kg/cm ²	??ASTM?D638
Brittleness temperature	????-50	????-50	????℃	??ASTM?D746	Modulus in flexure	????-	????-	????kg/cm ²	??ASTM?D638
Brittleness temperature	????-50	????-50	????℃	??ASTM?D746	Shock strength	????NB	????NB	????kg·cm/cm ²	??ASTM?D256
Heat deflection temperature (HDT) (4.6 kg/cm ²)	????NA	????NA	????℃	??ASTM?D648	Shock strength	????NB	????NB	????kg·cm/cm ²	??ASTM?D256

NB-does not rupture; NA-can't implement

* the density that provides adopts substitution method to measure, and the value in the bracket is an empirical value

Embodiment 3.4-contains the composition and the performance of the rubber thermoplastic composite polyolefine material of first kind of compatilizer of nitrile

Component	Consumption (kg)	Consumption (kg)	Consumption (kg)	Consumption (kg)	Consumption (kg)	Consumption (kg)	Source/rank
Component	Consumption (kg)	Consumption (kg)	Consumption (kg)	Consumption (kg)	Consumption (kg)	Consumption (kg)	Source/rank		Natural rubber	???3	??9	??18	???25	???30	????15	SMR-LCV Malaysia
Paracril	???-	??2	??6	???20	???20	????15	JSR-N ACN content 50%; Japan		Natural rubber	???3	??9	??18	???25	???30	????15	SMR-LCV Malaysia
Paracril	???-	??2	??6	???20	???20	????15	JSR-N ACN content 50%; Japan		Chlorinatedpolyethylene	???-	??-	??-	???-	???15	????15
EPDM	???1	??2	??3	???-	???-	????-	JSR; Low viscosity; Low ethylene content		Chlorinatedpolyethylene	???-	??-	??-	???-	???15	????15
EPDM	???1	??2	??3	???-	???-	????-	JSR; Low viscosity; Low ethylene content		Magnesium oxide	???-	??-	??-	???-	???5	????5	Commodity
Epoxy natural rubber	???1	??2	??3	???5	???-	????-	Epoxide content 50%; Guthrie (Malaysia)		Magnesium oxide	???-	??-	??-	???-	???5	????5	Commodity
Epoxy natural rubber	???1	??2	??3	???5	???-	????-	Epoxide content 50%; Guthrie (Malaysia)		Homopolymer polypropylene	???40	??-	??-	???-	???-	????-	????Shell；mfi?3
Polypropylene copolymer	???40	??30	??30	???-	???-	????-	????Shell；mfi4		Homopolymer polypropylene	???40	??-	??-	???-	???-	????-	????Shell；mfi?3
Polypropylene copolymer	???40	??30	??30	???-	???-	????-	????Shell；mfi4		New LDPE (film grade)	???-	??25	??20	???-	???-	????-
LLDPE	???-	??-	??-	???20	???10	????5	????Exxon		New LDPE (film grade)	???-	??25	??20	???-	???-	????-
LLDPE	???-	??-	??-	???20	???10	????5	????Exxon		?Engage	???-	??-	??-	???-	???10	????25	????DuPont
Zinic stearas	???2	??2	??2	???3	???3	????3	Commodity		?Engage	???-	??-	??-	???-	???10	????25	????DuPont
Zinic stearas	???2	??2	??2	???3	???3	????3	Commodity		Bismaleimides	???0.75	??0.75	??0.75	??0.75	??0.75	??0.75	????HVA ₂；DuPont(USA)
Superoxide	???-	??0.04	??0.07	???0.08	???0.08	????0.8	????PERKADOX?14-40A ????(Akzo?Nobel)		Bismaleimides	???0.75	??0.75	??0.75	??0.75	??0.75	??0.75	????HVA ₂；DuPont(USA)
Superoxide	???-	??0.04	??0.07	???0.08	???0.08	????0.8	????PERKADOX?14-40A ????(Akzo?Nobel)		Chlorinated paraffinic oil	???-	??2	??4	???7	???7	????5	Commodity
Antioxidant	???2	??2	??3	???3	???3	????3	????Wingstay-100(Goodyear)		Chlorinated paraffinic oil	???-	??2	??4	???7	???7	????5	Commodity
Antioxidant	???2	??2	??3	???3	???3	????3	????Wingstay-100(Goodyear)		Performance							Unit	Testing method
Shore hardness	???60D	??45D	??90A	???75A	???65A	????50A	????-	?ASTM?D2240	Performance							Unit	Testing method
Shore hardness	???60D	??45D	??90A	???75A	???65A	????50A	????-	?ASTM?D2240	Density	???0.91	??0.92	??0.93	???0.97	???0.97	????0.98	????gm/cc	?ASTM?D792
Ultimate tensile strength	???24	??16	??12	???9	???7.9	????4.8	????MPa	?ASTM?D638	Density	???0.91	??0.92	??0.93	???0.97	???0.97	????0.98	????gm/cc	?ASTM?D792
Ultimate tensile strength	???24	??16	??12	???9	???7.9	????4.8	????MPa	?ASTM?D638	Ultimate elongation	???550	??450	??374	???480	???460	????358	????％	?ASTM?D638
Tear strength	???102.6	??76.1	??44.7	???28.3	???32.6	????25.5	????N/mm		Ultimate elongation	???550	??450	??374	???480	???460	????358	????％	?ASTM?D638
Tear strength	???102.6	??76.1	??44.7	???28.3	???32.6	????25.5	????N/mm		100% modulus	???14.1	??11.9	??6.5	???3.1	???3.4	????1.9	????MPa	?ASTM?D638
Brittleness temperature	-52.5	-57.5	-57.5	-57.5	?-60	????-60	????℃	?ASTM?D746	100% modulus	???14.1	??11.9	??6.5	???3.1	???3.4	????1.9	????MPa	?ASTM?D638
Brittleness temperature	-52.5	-57.5	-57.5	-57.5	?-60	????-60	????℃	?ASTM?D746	Wear resistance	???115	??95	??60	???84	???47	????60	????mg/1000rev	The Taibo test
Shock strength	???30	??35	??NA	???NA	???NA	????NA	????kg·cm/cm ²	?ASTM?D256	Wear resistance	???115	??95	??60	???84	???47	????60	????mg/1000rev	The Taibo test
Shock strength	???30	??35	??NA	???NA	???NA	????NA	????kg·cm/cm ²	?ASTM?D256	Heat deflection temperature (HDT) (4.6kg/cm ²)	???130	??130	??120	???NA	???NA	????MA	????℃	?ASTM?D648

Embodiment 4-contains the composition and the performance of the rubber thermoplastic matrix material of nitrile and acrylate-based first kind of compatilizer

Component	Consumption (kg)	Consumption (kg)	Consumption (kg)	Consumption (kg)	Source/rank
Component	Consumption (kg)	Consumption (kg)	Consumption (kg)	Consumption (kg)	Source/rank	Natural rubber	25	?25	????25	????25	SMR-LCV Malaysia
Paracril	15	?15	????15	????-	JSR-N ACN content 50%; Japan	Natural rubber	25	?25	????25	????25	SMR-LCV Malaysia
Paracril	15	?15	????15	????-	JSR-N ACN content 50%; Japan	Ethylene-acrylate rubber	10	?10	????10	????10	????Vamac：DuPont
Sovprene	-	?-	????-	????15	????Neoprene；DuPont	Ethylene-acrylate rubber	10	?10	????10	????10	????Vamac：DuPont
Sovprene	-	?-	????-	????15	????Neoprene；DuPont	Polyvinyl acetate	5	?5	????5	????-	????Generic
Polymeric amide	-	?45	????-	????-	????PA～6；mfi3	Polyvinyl acetate	5	?5	????5	????-	????Generic
Polymeric amide	-	?45	????-	????-	????PA～6；mfi3	Thermoplastic polyurethane	-	?-	????45	????45	Bayer; Hardness 80A
Polymethylmethacrylate	45	?-	????-	????-	PMMA; Molding graae	Thermoplastic polyurethane	-	?-	????45	????45	Bayer; Hardness 80A
Polymethylmethacrylate	45	?-	????-	????-	PMMA; Molding graae	Polyvinyl chloride	-	?-	????-	????5	Mixing material is stuck with paste level; 0ccidental
Synourin oil	2	?2	????2	????-	????Generic	Polyvinyl chloride	-	?-	????-	????5	Mixing material is stuck with paste level; 0ccidental
Synourin oil	2	?2	????2	????-	????Generic	Chlorinated paraffinic oil	-	?-	????-	????3	Commodity
Zinic stearas	2	?2	????2	????2	Commodity	Chlorinated paraffinic oil	-	?-	????-	????3	Commodity
Zinic stearas	2	?2	????2	????2	Commodity	TMTD	0.1	?0.1	????0.1	????0.1	????Thiurad(Monsanto)
Magnesium oxide	4	?4	????4	????4	Commodity	TMTD	0.1	?0.1	????0.1	????0.1	????Thiurad(Monsanto)
Magnesium oxide	4	?4	????4	????4	Commodity	Resol	1	?1	????1	????0.5	????SP1045；Schenectady
Acrylamide	0.5	?0.5	????0.5	????-	Commodity	Resol	1	?1	????1	????0.5	????SP1045；Schenectady
Acrylamide	0.5	?0.5	????0.5	????-	Commodity	Antioxidant	2	?2	????2	????2	????Wingstay-100(Goodyear)
Performance					Unit	Antioxidant	2	?2	????2	????2	????Wingstay-100(Goodyear)
Performance					Unit	Shore hardness	90A	?80A	????60A	????60A	????-
Density	1.01	?1.02	????1.04	????1.24*	????gm/cc	Shore hardness	90A	?80A	????60A	????60A	????-
Density	1.01	?1.02	????1.04	????1.24*	????gm/cc	Tensile strength	410	?430	????380	????380	????kg/cm ²
Extension at break	300	?380	????420	????420	????％	Tensile strength	410	?430	????380	????380	????kg/cm ²
Extension at break	300	?380	????420	????420	????％	Tensile set	33	?31	????29	????28	????％

* empirical value

Embodiment 5-contains the composition and the performance of the rubber thermoplastic matrix material of first kind of compatilizer of chloro

Component	Consumption (kg)	Consumption (kg)	Consumption (kg)	Consumption (kg)	Source/rank
Component	Consumption (kg)	Consumption (kg)	Consumption (kg)	Consumption (kg)	Source/rank	Natural rubber	??25	????25	????25	??25	SMR-LCV Malaysia
Sovprene	??25	????25	????15	??15	????Neoprene；DuPont	Natural rubber	??25	????25	????25	??25	SMR-LCV Malaysia
Sovprene	??25	????25	????15	??15	????Neoprene；DuPont	Chlorinatedpolyethylene	??-	????-	????10	??-	????Bayer?CM
Chlorosulfonated polyethylene	??-	????-	????-	??10	????Hypalon；DuPont	Chlorinatedpolyethylene	??-	????-	????10	??-	????Bayer?CM
Chlorosulfonated polyethylene	??-	????-	????-	??10	????Hypalon；DuPont	Ethane-acetic acid ethyenyl ester	??-	????-	????5	??5	????Mitsui?DuPont
Polyvinyl chloride	??5	????35	????-	??-	Mixing material: 70 Xiao A hardness	Ethane-acetic acid ethyenyl ester	??-	????-	????5	??5	????Mitsui?DuPont
Polyvinyl chloride	??5	????35	????-	??-	Mixing material: 70 Xiao A hardness	Thermoplastic polyurethane	??45	????15	????-	??-	Bayer; 80 Shore A
New LDPE (film grade)	??-	????-	????45	??45	The mfi5 molding graae	Thermoplastic polyurethane	??45	????15	????-	??-	Bayer; 80 Shore A
New LDPE (film grade)	??-	????-	????45	??45	The mfi5 molding graae	Resol	??2	????2	????2	??2	????SP1045；Schenectady
Zinic stearas	??3	????3	????3	??3	Commodity	Resol	??2	????2	????2	??2	????SP1045；Schenectady
Zinic stearas	??3	????3	????3	??3	Commodity	Bismaleimides	??0.3	????0.3	????0.3	??0.3	????HVA ₂；DuPont
Magnesium oxide	??5	????5	????5	??5	Commodity	Bismaleimides	??0.3	????0.3	????0.3	??0.3	????HVA ₂；DuPont
Magnesium oxide	??5	????5	????5	??5	Commodity	Chlorinated paraffinic oil	??3	????3	????3	??3	Commodity
Antioxidant	??2	????2	????2	??2	????Wingstay-100(Goodyear)	Chlorinated paraffinic oil	??3	????3	????3	??3	Commodity
Antioxidant	??2	????2	????2	??2	????Wingstay-100(Goodyear)	Performance					Unit
Shore hardness	??60A	????55A	????80A	??80A	????-	Performance					Unit
Shore hardness	??60A	????55A	????80A	??80A	????-	Density	??1.20*	????1.20*	????1.8*	??1.8*	????gm/cc
Tensile set	??28	????32	????33	??32	????％	Density	??1.20*	????1.20*	????1.8*	??1.8*	????gm/cc
Tensile set	??28	????32	????33	??32	????％	Extension at break	??430	????410	????380	??360	????％

* empirical value

Embodiment 6-contains the composition and the performance of the rubber thermoplastic matrix material of first kind of compatilizer of epoxide base

Component	Consumption (kg)	Consumption (kg)	Consumption (kg)	Source/rank
Component	Consumption (kg)	Consumption (kg)	Consumption (kg)	Source/rank	Natural rubber	??25	????25	??50	SMR-LCV Malaysia
Epoxy natural rubber	??25	????30	??-	Epoxy content is 50% ENR	Natural rubber	??25	????25	??50	SMR-LCV Malaysia
Epoxy natural rubber	??25	????30	??-	Epoxy content is 50% ENR	?EVA	??10	????10	??10	????Mitsui?DuPont
Polypropylene copolymer	??40	????40	??40	????Shell?KMT6100；mfi4	?EVA	??10	????10	??10	????Mitsui?DuPont
Polypropylene copolymer	??40	????40	??40	????Shell?KMT6100；mfi4	Bismaleimides	??1	????1	??1	????HVA ₂；DuPont
Superoxide	??0.06	????0.06	??0.06	????Perkadox?14S ????(Akzo?Nobel)	Bismaleimides	??1	????1	??1	????HVA ₂；DuPont
Superoxide	??0.06	????0.06	??0.06	????Perkadox?14S ????(Akzo?Nobel)	Naphthenic oil (naphthalic oil)	??3	????3	??3	Commodity
Antioxidant	??1	????1	??1	????Wingstay-100 ????(Goodyear)	Naphthenic oil (naphthalic oil)	??3	????3	??3	Commodity
Antioxidant	??1	????1	??1	????Wingstay-100 ????(Goodyear)	Performance				Unit
Shore hardness	??80A	????85A	??80A	????-	Performance				Unit
Shore hardness	??80A	????85A	??80A	????-	Density	??0.93	????0.93	??0.93	????gm/cc
Tensile strength	??490	????510	??490	????kg/cm ²	Density	??0.93	????0.93	??0.93	????gm/cc
Tensile strength	??490	????510	??490	????kg/cm ²	Tensile set	??30	????30	??27	????％
Extension at break	??380	????400	??400	????％	Tensile set	??30	????30	??27	????％

Embodiment 7-contains the performance of the rubber thermoplastic composition of first kind of compatilizer of nitrile and polylefin thermoplatic plastics

' soft ' level composition that comprises following each component is carried out aforesaid thermogravimetric analysis, dsc and dynamic mechanical analysis:

Natural rubber (15 parts),

Paracril (30 parts),

LLDPE (5 parts),

Ethane-acetic acid ethyenyl ester (25 parts),

Engage (20 parts),

HVA ₂(0.75 part),

Superoxide (0.075 part),

MBTS (0.25 part),

Zinic stearas (1 part) and

Antioxidant (1 part).

Method

Thermogravimetric analysis (TGA)

Employing is connected T.A.Instruments TGA2950 on the Thermal Analyst2200 Controller and experimentizes and write down the result.Before each thermogravimetric analysis and in the process with the speed purging system of highly purified nitrogen with 50 ml/min.In case after loading onto sample, reach 600 ℃ with 5 ℃/minute heating lift velocity heated sample.Write down temperature variant weight continuously, for the usefulness of analysis.

Dsc (DSC)

Employing is carried out dsc analysis from the DSC2920 of TA Instruments.From-100 to 400 ℃ temperature is analyzed the sample of weighing with 10 ℃/minute rate of heating in nitrogen gas stream.

Dynamic mechanical analysis (DMA)

The DMA2980 that employing is operated with stretching mode (TA Instruments), from-140 to 100 ℃ temperature, with the strain amplitude of the frequency of 1Hz and 0.08% and carry out DMA with 2 ℃/minute programmed heating speed and analyze.Adopt liquid nitrogen to reach local environmental conditions.Determine the second-order transition temperature (Tg) of sample from tan δ curve.

The result

TGA: Fig. 1 has illustrated the weight loss of sample and the relation of temperature.The result shows the roughly composition that contains 53% rubber (adding PU), 25% plastics, 13% softening agent and 9% other material.

DSC: Fig. 2 has illustrated two fusing points and two wide thermal endothermic decomposition.First fusing point is wide, and at 118 ℃ of temperature places, its melting heat is 3.66J/g.Second fusing point located at 157 ℃, and its melting heat is 6.47J/g.

DMA: select second-order transition temperature as the peak position on the tan δ curve that temperature is mapped.Can observe two sharp-pointed glass transitions from Fig. 3, first glass transition is located at-60 ℃, and second glass transition located at-21 ℃.This curve shows that the storage modulus in the time of 25 ℃ is 18.59MPa.

Embodiment 8-contains the performance of the rubber thermoplastic composition of first kind of compatilizer of nitrile and polylefin thermoplatic plastics

' centre ' level composition that comprises following each component is carried out as embodiment 7 described thermogravimetric analysiss, dsc and dynamic mechanical analysis:

Natural rubber (20 parts),

Paracril (30 parts),

High density polyethylene(HDPE) (10 parts),

Ethane-acetic acid ethyenyl ester (20 parts),

LLDPE (20 parts),

HVA ₂(0.75 part),

Superoxide (0.07 part),

MBTS (0.25 part),

Zinic stearas (1 part) and

Antioxidant (1 part).

The result

TGA: Fig. 4 has illustrated the weight loss of sample and the relation of temperature.The result shows that the weight loss of the natural rubber of the first step is not sharp peak, and its total amount accounts for 26% of natural rubber and other rubber stock.Second step was the decomposition of plastics, and its amount is 71%, residue 3%.

DSC: Fig. 5 has illustrated two fusing points and two wide thermal endothermic decomposition.First fusing point is at 125 ℃ of temperature places, and its melting heat is 15.10J/g.Second fusing point located at 162 ℃, and its melting heat is 36.32J/g.

DMA: select second-order transition temperature as the peak position on the tan δ curve that temperature is mapped.Can observe two sharp-pointed glass transitions from Fig. 6, first has located a sharp peak at-58 ℃, and this shows the natural rubber with consistency and the glass transition of nitrile rubber.Show partially miscible polyolefine at 0.8 ℃ of second wide glass transition locating.This curve shows that the storage modulus in the time of 25 ℃ is 298.85MPa.

Embodiment 9-contains the performance of the rubber thermoplastic composition of first kind of compatilizer of nitrile and polylefin thermoplatic plastics

' rigidity ' level composition that comprises following each component is carried out as embodiment 7 described thermogravimetric analysiss, dsc and dynamic mechanical analysis:

Natural rubber (6 parts),

Paracril (4 parts),

Homopolymer polypropylene (30 parts),

Polypropylene copolymer (30 parts),

HMW (high molecular weight)-high density polyethylene (30 parts),

HVA ₂(0.75 part),

Superoxide (0.03 part),

Zinic stearas (1 part) and

Antioxidant (1 part).

The result

TGA: Fig. 7 has illustrated the weight loss of sample and the relation of temperature.The result shows that the natural rubber of the first step has weight loss, and its amount is 9%.Second step was polypropylene and poly decomposition, and its amount is 90%, residue 1%.

DSC: Fig. 8 has illustrated two fusing points and has had the wide thermal endothermic decomposition of some acromions.First fusing point is at 126 ℃ of temperature places, and its melting heat is 18.61J/g.Second fusing point located at 165 ℃, and its melting heat is 40.93J/g.

DMA: select second-order transition temperature as the peak position on the tan δ curve that temperature is mapped.Can observe two wide glass transitions from Fig. 9, first is located at-52 ℃, and second wide glass transition located at 9.7 ℃, and this shows partially miscible polyolefine.This curve shows that the storage modulus in the time of 25 ℃ is 630MPa.

Claims

1. rubber matrix, it comprises:

A) natural rubber of 10-90% (v/v),

I) nitrile,

Ii) halogen,

Iii) acetate esters,

Iv) epoxide,

V) vinylbenzene, or

Vi) acrylate,

I) polyvinyl acetate,

Ii) ethane-acetic acid ethyenyl ester,

Iii) polyacrylonitrile or high nitrile resin,

Iv) acrylamide or polyacrylamide,

V) resol,

Vi) acrylic ester polymer,

Vii) halogenated polymer,

Viii) maleic anhydride or poly-maleic anhydride, or

Ix) bismaleimides.

2. rubber matrix as claimed in claim 1, wherein first kind of compatilizer is different with second kind of compatilizer.

3. rubber matrix as claimed in claim 2, wherein this rubber matrix is applicable to at least a thermoplastics and mixes, and makes the thermoplastic elastomer matrix material.

4. rubber matrix as claimed in claim 3, wherein thermoplastics is selected from one or more in polyolefine, polymeric amide, polyester, urethane, polystyrene and the acrylonitrile-butadiene-styrene (ABS).

5. rubber matrix as claimed in claim 2, wherein natural rubber has lower protein and low impurity content.

6. rubber matrix as claimed in claim 5, wherein natural rubber be selected from deproteinization natural rubber, oil-extended natural rubber, mould and separate natural rubber, senior processing rubber, standard Malaysia constant viscosity rubber, standard Malaysia low viscosity rubber, standard Malaysia's conventional rubber and other India Standard Natural Rubber latex of constant viscosity level.

7. rubber matrix as claimed in claim 6, wherein natural rubber is Standard Malasian rubber or other India Standard Natural Rubber latex of constant viscosity level.

8. rubber matrix as claimed in claim 6, wherein the content of natural rubber is 10-90 phr in the rubber matrix.

9. rubber matrix as claimed in claim 8, wherein rubber matrix contains the natural rubber of 20-40 phr.

10. rubber matrix as claimed in claim 2, wherein first kind of compatilizer of nitrile is selected from vinyl cyanide-elastoprene, nitrile natural rubber, polyacrylonitrile and high nitrile polymer.

11. rubber matrix as claimed in claim 10, wherein vinyl cyanide-elastoprene is nitrile-synthetic polyisoprene or paracril.

12. rubber matrix as claimed in claim 10, wherein the amount of nitrile compatilizer is greater than 10% of rubber matrix.

13. rubber matrix as claimed in claim 12, wherein the acrylonitrile content of vinyl cyanide-elastoprene and nitrile natural rubber is greater than 20%.

14. rubber matrix as claimed in claim 2, wherein first kind of compatilizer of halogenation is the halogenated polymer that is selected from following substances: chlorinated rubber, polyvinyl chloride, sovprene, chlorinatedpolyethylene/sovprene, chlorosulfonated polyethylene/sovprene and vinylidene fluoride.

15. rubber matrix as claimed in claim 14, wherein first kind of compatilizer of halogenation is with the halogen source halogenated rubber that makes of halogenated rubber matrix on the spot.

16. rubber matrix as claimed in claim 14 wherein adds chlorinated paraffinic oil and makes halogenated rubber in rubber matrix.

17. rubber matrix as claimed in claim 14, wherein the content of halogen-containing polymkeric substance is greater than 15% of rubber matrix.

18. rubber matrix as claimed in claim 2, wherein first kind of compatilizer of epoxide base is epoxidized natural rubber.

19. rubber matrix as claimed in claim 18, wherein epoxy natural rubber is with natural rubber and hydrogen peroxide/formic acid/acetate situ reaction and make.

20. rubber matrix as claimed in claim 19, wherein the epoxide content of epoxide based compatilizer is 20-50%, and obtaining epoxide content is the rubber matrix of 20-25%.

21. rubber matrix as claimed in claim 2, the first kind of compatilizer that wherein contains acetic ester is selected from polyvinyl acetate, ethane-acetic acid ethyenyl ester and vinyl-acetic ester rubber.

22. rubber matrix as claimed in claim 21, wherein the content of acetic ester polymkeric substance is the 30-50% of rubber matrix.

23. rubber matrix as claimed in claim 22, wherein the content of acetic ester polymkeric substance is 30% of rubber matrix.

24. rubber matrix as claimed in claim 21, wherein the vinyl acetate content of rubber matrix is greater than 20%.

25. rubber matrix as claimed in claim 2, wherein acrylate-based first kind of polymkeric substance that compatilizer is selected from acrylic rubber and is made by ethyl propenoate, methyl acrylate or methyl methacrylate.

26. rubber matrix as claimed in claim 2, wherein first kind of compatilizer of styryl is selected from vinylbenzene natural rubber, styrene butadiene rubbers, styrene isoprene styrene block copolymer (SIS) and vinylbenzene-ethyl butylene-styrene segmented copolymer.

27. rubber matrix as claimed in claim 2 is wherein used more than one first kind of compatilizer in rubber matrix.

28. rubber matrix as claimed in claim 27, wherein halogenation compatilizer and nitrile compatilizer combine use.

29. rubber matrix as claimed in claim 27, wherein acrylate compatilizer and nitrile compatilizer combine use.

30. the matrix material of a natural rubber thermoplastics, it comprises:

A) natural rubber of 10-90% (v/v),

I) nitrile,

Ii) halogen,

Iii) acetate esters,

Iv) epoxide,

V) vinylbenzene, or

Vi) acrylate,

I) polyvinyl acetate,

Ii) ethane-acetic acid ethyenyl ester,

Iii) polyacrylonitrile or high nitrile resin,

Iv) acrylamide or polyacrylamide,

V) resol,

Vi) acrylic ester polymer,

Vii) halogenated polymer,

Viii) maleic anhydride or poly-maleic anhydride, or

Ix) bismaleimides,

I) urethane,

Ii) polyester,

Iii) polymeric amide,

Iv) acrylate,

V) acrylonitrile-butadiene-styrene (ABS),

Vi) polyolefine, or

Vii) cellulose ester.

31. the matrix material of natural rubber thermoplastics as claimed in claim 30 wherein forms two phases, comprise a)-c) rubber matrix as rubber phase and the thermoplastics component plastics mutually in, rubber phase is 5 with plastics ratio mutually: 95-90: 10.

32. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein the thermoplastic elastomer matrix material can recycling, reprocessing and/or reshaping.

33. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein with rubber matrix and polyolefins, polyethylene base class or polyurethanes mutually compounding make soft composite material.

34. rubber matrix as claimed in claim 33, wherein plastics are selected from polypropylene, polyethylene, polyvinyl acetate, ethane-acetic acid ethyenyl ester, ethylene-propylene plastics (Engage; DuPont), urethane or polyvinyl chloride.

35. the matrix material of natural rubber thermoplastics as claimed in claim 34, wherein the content of natural rubber in rubber matrix better is about 30-70%, be 100 parts in total amount respectively, rubber matrix is 5-70 part with the relative blending ratio of plastics: 95-30 part.

36. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein with rubber matrix and polyurethanes, polyamide-based, polyethylene base class or polyester mutually compounding make intermediate composite.

37. the matrix material of natural rubber thermoplastics as claimed in claim 31 wherein makes rigid composite material with rubber matrix with polyolefins, polyurethanes or polyamide-based compounding mutually.

38. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein TPO is selected from high density polyethylene(HDPE), LLDPE, homopolymer polypropylene, polypropylene copolymer and gathers (ethylene-propylene).

39. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein polyamide thermoplastic is crystallization or resinoid high molecular weight copolymer or terpolymer.

40. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein polyamide thermoplastic is selected from polycaprolactam (nylon-6), nylon 12 (PA-12), polyhexamethylene adipamide (nylon-6,6), poly-azelaoyl hexanediamine (nylon-6,9), polyhexamethylene sebacamide (nylon-6,10), poly-6I hexamethylene isoterephalamide (nylon-6, IP) and the condensation product (nylon-11) of 11-aminoundecanoic acid.

41. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein thermoplastic polyurethane is based on the TPU(Thermoplastic polyurethanes) of hexanolactam, and its Xiao A hardness is 80-90.

42. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein thermoplastic polyester is one or more di-carboxylic acid, acid anhydride or ester and one or more dibasic alcohol to be carried out condensation and the thermoplastic polyester that makes.

43. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein thermoplastic polyester is the Mierocrystalline cellulose polyester.

44. the matrix material of natural rubber thermoplastics as claimed in claim 43, wherein the Mierocrystalline cellulose polyester is selected from the polymkeric substance of rhodia, acetobutyric acid Mierocrystalline cellulose and cellulose propionate.

45. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein polyester is a polycarbonate.

46. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein rubber matrix comprises first kind of compatilizer of nitrile, second kind of compatilizer of polyvinyl acetate and polyamide thermoplastic plastics.

47. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein rubber matrix comprises first kind of compatilizer of nitrile, second kind of compatilizer of ethane-acetic acid ethyenyl ester and polylefin thermoplatic plastics.

48. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein rubber matrix comprises first kind of compatilizer of nitrile, second kind of compatilizer of chlorinatedpolyethylene and polylefin thermoplatic plastics.

49. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein rubber matrix comprises first kind of compatilizer of nitrile, second kind of compatilizer of polyvinyl acetate and polyester thermoplastics.

50. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein rubber matrix comprises first kind of compatilizer of nitrile, second kind of compatilizer of polyvinyl acetate and polyurethane thermoplastic plastics.

51. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein rubber matrix comprises first kind of compatilizer of nitrile, second kind of compatilizer of polyvinyl chloride and polyurethane thermoplastic plastics.

52. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein rubber matrix comprises first kind of compatilizer of epoxide base, second kind of compatilizer of bismaleimides and polylefin thermoplatic plastics.

53. the matrix material of natural rubber thermoplastics as claimed in claim 31, wherein rubber matrix comprises acrylate-based first kind of compatilizer, second kind of compatilizer of sovprene and polyurethane thermoplastic plastics.

54. the matrix material of natural rubber thermoplastics as claimed in claim 31, the vulcanizing agent that adds when wherein matrix material is included in rubber matrix mixed mutually with plastics.

55. the matrix material of natural rubber thermoplastics as claimed in claim 54, wherein vulcanization system is selected from hydroxymethyl-phenol system, Bismaleimide Resin, bismaleimides MBTS system, bismaleimides peroxide systems, organic peroxide systems, accelerated sulfur system, carbamate system, borine system and radiation system.

56. the matrix material of natural rubber thermoplastics as claimed in claim 54, wherein vulcanizing agent comprises interface promotor.

57. the matrix material of natural rubber thermoplastics as claimed in claim 56, its median surface promotor is selected from phenylene bismaleimides, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, triallyl isocyanurate and triallyl cyanurate.

58. the matrix material of natural rubber thermoplastics as claimed in claim 31 wherein can be by adding the performance that one or more additives come modified composite material.

59. the matrix material of natural rubber thermoplastics as claimed in claim 58, wherein additive is selected from thermally-stabilised chemical agent, fire retardant chemistry agent, peptizing agent, filler, extender, softening agent, pigment, promotor, stablizer, anti degradant, antioxidant, UV filtering agent, processing aid and extending oil.

60. the matrix material of natural rubber thermoplastics as claimed in claim 59, wherein the used thermoplastic plastic of portion of hot at least derives from the thermoplastics of recycling in matrix material.

61. goods, it is made by the matrix material of the described natural rubber thermoplastics of claim 30, wherein these goods through extrude, injection moulding or compression moulding and make.

62. a method of making the matrix material of natural rubber thermoplastics, this method comprises the steps:

The preparation rubber matrix, described matrix comprises:

A) natural rubber of 10-90% (v/v),

I) nitrile,

Ii) halogen,

Iii) acetate esters,

Iv) epoxide,

V) vinylbenzene, or

Vi) acrylate,

I) polyvinyl acetate,

Ii) ethane-acetic acid ethyenyl ester,

Iii) polyacrylonitrile or high nitrile resin,

Iv) acrylamide or polyacrylamide,

V) resol,

Vi) acrylic ester polymer,

Vii) halogenated polymer,

Viii) maleic anhydride or poly-maleic anhydride, or

Ix) bismaleimides,

Rubber matrix is mixed mutually with plastics, and described plastics comprise one or more mutually and are selected from the thermoplastics that comprises following arbitrary material

I) urethane,

Ii) polyester,

Iii) polymeric amide,

Iv) acrylate,

V) acrylonitrile-butadiene-styrene (ABS),

Vi) polyolefine, or

Vii) cellulose ester.

63. the method for the matrix material of manufacturing natural rubber thermoplastics as claimed in claim 62 wherein adds additive in rubber matrix.

64. the method as the matrix material of the described manufacturing natural rubber of claim 63 thermoplastics wherein prepares rubber matrix through the cold mixing method.

65. as the method for the matrix material of the described manufacturing natural rubber of claim 64 thermoplastics, wherein the cold mixing method is carried out being lower than under about 120 ℃ temperature.

66. as the method for the matrix material of the described manufacturing natural rubber of claim 65 thermoplastics, wherein after mixing, rubber phase be stable viscosity and allow its slaking, mix mutually with plastics more afterwards.

67. the method as the matrix material of the described manufacturing natural rubber of claim 66 thermoplastics wherein adopts melting mixing or dynamic vulcanization that rubber matrix is mixed mutually with plastics.

68. as the method for the matrix material of the described manufacturing natural rubber of claim 67 thermoplastics, wherein with plastics mutually and rubber matrix mix, mixture is plasticated being enough to soften at least under the temperature of plastics, make matrix material.

69. as the method for the matrix material of the described manufacturing natural rubber of claim 68 thermoplastics, wherein with plastics mutually and the rubber matrix mixing, under the temperature that is higher than the plastics fusing point, mixture is plasticated, makes thermoplastic compounds.