CN1906218A - Adherent, modified thermoplastic elastomeric blends, articles, and methods - Google Patents
Adherent, modified thermoplastic elastomeric blends, articles, and methods Download PDFInfo
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- CN1906218A CN1906218A CN 200480040490 CN200480040490A CN1906218A CN 1906218 A CN1906218 A CN 1906218A CN 200480040490 CN200480040490 CN 200480040490 CN 200480040490 A CN200480040490 A CN 200480040490A CN 1906218 A CN1906218 A CN 1906218A
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Abstract
A thermoplastic elastomer that is adherent to polar materials may be made from a dynamically vulcanized blend of propylene resin, ethylene/alpha-olefin/non-conjugated diene elastomers, and a bonding agent via a curing system containing a free radical initiator, at least one co-agent including multifunctional acrylates containing at least two acrylate groups, multifunctional maleimides containing at least two imide groups, or mixtures of both, where the elastomer gel content in the modified blend is at least about 97 percent. Reaction mixtures, articles made therefrom, and methods of dynamically vulcanizing are also disclosed.
Description
Technical field
The present invention relates to the composition for thermoplastic elastomer of dynamic vulcanization, it solidifies by the cure system that contains radical initiator and at least a auxiliary agent and by adding at least a tackiness agent modification so that adhere on the polar material.Reaction mixture is also disclosed, by the method for its article that make and dynamic vulcanization.
Background of invention
The thermoplastic elastomer that is formed by curing rubber and polyolefinic mixture is known in this area.The structure of these materials is the substrate forms that contains plastic fraction, and this plastic fraction has the discrete domain of the partially or completely curing elastomer component of imbedding wherein.Olefin-based thermoplastic elastomer has described structure, and its advantage is that it can carry out plastic flow when being higher than polyolefinic softening temperature, and presents the curing elastomer behavior when being lower than softening temperature.Therefore, this material presents thermoplasticity (that is, at high temperature flowing) under processing conditions, also presents the elasticity (that is, distortion recovers basically when removing deformation force) of rubber like simultaneously.
Dynamic vulcanization (dynamic vulcanization) thus be a kind ofly mixture heating up to be sheared simultaneously elastomer portion that this mixture makes thermoplastic elastomer and solidify and form thermoplastic sulfurized rubber (thermoplastic vulcanizate) method (TPV) having under the situation of solidifying agent.Can be used for partially or completely during dynamic vulcanization, the different curings of curing rubber comprise sulfenyl system, superoxide based system, phenylol system and hydrosilication based system.
(that is, be an important factor of the final performance of resulting composite partially or completely), for example United States Patent (USP) 4,130, and lower oil swell and higher ultimate tensile strength are observed in instruction in 535 under high solid state for the degree of cure of elastomerics or rubber phase.In other words, compare with uncured or partly solidified mixture, the mixture that contains completely crued elastomerics phase has the physicals of improvement.This completely crued hardening thing can be used as thermoplastics processing, although their crosslinked degree make that rubber part is almost insoluble or are insoluble to conventional solvent fully.The processing characteristics of completely crued thermoplastic sulfurized rubber (TPV) is just in time opposite with thermoset composition, and thermoset composition keeps dimensional integrity under 200 ℃ or higher processing temperature.
Polar material, for example, base material is generally inorganic substance, and for example metal perhaps is polymkeric substance, for example engineering resin.The industry olefinic thermoplastic elastomer is difficult for sticking on the polar material when for example being shaped with layered composite in the coextrusion process usually.Usually, this bonding weak so that spontaneous layering or long-time after lose viscosity, particularly under wet environment.For ease of being sticked to, thermoplastic sulfurized rubber carried out various trials on the polar material in the prior art.
United States Patent (USP) 4,957,968 relate to a kind of viscous heat thermoplastic elastic composition, it comprise by chemical reactivity functional group for example the carboxylic acid or derivatives thereof comprise at least a polyolefine of acid anhydrides, chloride of acid, isocyanic ester, azoles quinoline, epoxide, amine and oxyhydroxide modification; At least a other polymkeric substance that makes by one or more following materials: ethene, propylene, butylene, iso-butylene, octene-1,4-methylpentene-1, hexene-1 or mixture; And at least a partly solidified olefin elastomer, comprise elastomer ethylene-propylene copolymer, elastomeric ethylene-propylene terpolymers, polyisoprene, polyisobutene, ethylene-propylene copolymer rubber, polyhutadiene, natural rubber, elastomeric polyester, polyurethane elastomer, polyamide elastomer and mixture.
United States Patent (USP) 5,574,105 for example, has been described a kind of thermoplastic elastomer, and it comprises the alloy (DVA) of the dynamic vulcanization of engineering resin, thermoplastic olefin polymer and elastomer copolymer and three mixed things of expanding material.Expanding material be by with nylon-6 be grafted with the polypropylene fusion of 0.1-2.0% weight maleic anhydride mixed.This patent instruction, without expanding material, the mixture of engineering resin and DVA has poor mechanical property and elongation performance owing to lack interfacial adhesion between these components, and may lose efficacy in this weak interface and these components may layering.
United States Patent (USP) 5,695,838 have described a kind of trilaminar at least laminated multi-layer body that has: polyolefin layer, adhesion layer and aramid layer.Adhesion layer contains the acid anhydrides of the propylene that is grafted with unsaturated carboxylic acid or dicarboxylic acid and is grafted with the mixture of the ethylene/alpha-olefin copolymer of unsaturated carboxylic acid.
United States Patent (USP) 5,843,577 have described in the thermoplastic elastomer that reaction product with toxilic acid esterification polypropylene and polymeric amide joins dynamic vulcanization to improve for example viscosity of nylon of TPV and engineering resin.This patent also instructs the maleinization polypropylene of the maleic anhydride graft of grafting on it that will contain the 1.5wt% that has an appointment to join in the mixture of polypropylene and completely crued EPDM and common additives, this common additives has 45 Durometer Shore A hardness (Santoprene 111-45, can be from Advanced Elastomer Systems, USA is commercially available), only high-content (15wt%) show down with polymeric amide undesirable non-in gather bond properties.
United States Patent (USP) 5,962,146 have described and have not used tackiness agent, and with the EPDM or the EPM rubber of film coating, this film contains polymeric amide and is grafted with the olefinic material of unsaturated carboxylic acid or unsaturated dicarboxylic acid or its acid anhydrides.
United States Patent (USP) 6,300,418 have described a kind of composition, and it contains polyolefin resin, rubber for example EPDM or SEBS and with the adhesion promotor of the form of the reaction product of functionalized rubber and polymeric amide.Said composition can be partial cross-linked at least.
Yet, prior art with polar material for example engineering resin to join may be worthless in the elastomer thermoplastic mixtures.The physicals of polar/non-polar mixture may descend, because nylon humidity not for example, and can be impaired because of moist inductive degraded in the course of processing with the non-wet quick property TPV of modified nylon.In addition, polymeric amide is joined in the thermoplastic sulfurized rubber and can negative impact be arranged to the form and the elastic performance of whole composition, for example compression set increases.Therefore, need a kind of elastomer thermoplastic mixtures, it can adhere to or be bonded on the polar substrates always, and does not need independent adhesion layer, mechanical interlock or add unwanted component in polar substrates or thermoplastic sulfurized rubber composition.
Summary of the invention
The present invention includes a kind of elastomer thermoplastic mixtures of adhesivity reaction modifying, by the material that comprises acrylic resin, ethylene/alpha-olefin/nonconjugated diene copolymer elastomer component and tackiness agent (bondingagent), dynamic vulcanization forms in the cure system that comprises following material is arranged: radical initiator; And auxiliary agent, it comprises that one or more contain the multi-functional acrylate of at least two acrylate groups, contain polyfunctional group maleimide or its mixture of at least two imide groups; Wherein the total amount of radical initiator and auxiliary agent is enough to provide at least about the gel content of 97% elastomer blends and provides with the minimum stripping strength at least about 650g/cm and adheres to (adherent) mixture of the present invention to the polar material.
In one embodiment, but tackiness agent comprise with being selected from functionalized alfon of following grafted monomer or multipolymer: unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated monocarboxylic acid acid anhydride, unsaturated dicarboxylic acid acid anhydride and combination thereof.In a preferred embodiment, the adhesion grade of elastomer blends is 1 and to destroy type be cohesive failure.In another preferred embodiment, tackiness agent comprises the alfon or the multipolymer of maleic anhydride graft.
In one embodiment, radical initiator exists with the amount of about 0.001%-2% weight of modified mixture.In another embodiment, auxiliary agent exists with the amount of about 0.1%-10% weight of modified mixture.In a preferred embodiment, auxiliary agent comprises Viscoat 295, ethoxylated trimethylolpropane triacrylate, the propoxylation Viscoat 295, the propoxylated glycerol triacrylate, pentaerythritol triacrylate, cyclohexane dimethanol diacrylate, tetramethylol methane tetraacrylate, the ethoxylation tetramethylol methane tetraacrylate, two-trimethylolpropane tetra-acrylate, N, a N '-phenylenedimaleimide, 4,4 '-two maleimide amino-ditans, 3,3 '-two maleimide amino-ditans, or its combination.In a more preferred, auxiliary agent comprises Viscoat 295, N, a N '-phenylenedimaleimide or its combination.
In an embodiment again, cure system also comprises second kind of different auxiliary agent, and it exists with the amount of about 0.1%-10% weight of modified mixture.In a preferred embodiment, between comprising, this second auxiliary agent advises 1,2-polyhutadiene, random 1,2-polyhutadiene, high-vinyl solution (vinylsolution) styrene butadiene elastomerics or its mixture.In a more preferred, a rule 1, the 2-polyhutadiene has the fusing point at least about 60 ℃.
In one embodiment, modified mixture comprises the ethylene/alpha-olefin/nonconjugated diene elastomer component of the acrylic resin of about 10%-70% weight, about 5%-60% weight and the tackiness agent of about 1%-30% weight.In another embodiment, radical initiator comprises that at least a organo-peroxide and this mixture are not have moisture sensitivity at least basically.In an embodiment again, modified mixture also comprises at least a extending oil of about 5%-65% weight.In yet another embodiment, modified mixture also comprises filler component, and it exists with the amount of about 0.001%-20% weight.
In one embodiment, ethylene/alpha-olefin/nonconjugated diene elastomer component comprises the ethylene/propylene/diene elastomerics.In a preferred embodiment, there is not the ethylene/alpha-olefin/nonconjugated diene elastomer component of oil to have mooney viscosity at least about 100 [ML (@125 ℃ of 1+4)].In another embodiment, modified mixture also comprises one or more organic and mineral dye, thermo-stabilizer, antioxidant, UV light absorber, photostabilizer, fire retardant, antiblocking agent, pore forming material, static inhibitor or antiseptic-germicide or its arbitrary combination.
The present invention also comprises a kind of article, and it comprises top any reaction modifying mixture.And, the present invention includes a kind of preparation method of composition for thermoplastic elastomer of dynamic vulcanization, comprising: the mixture of acrylic resin, ethylene/alpha-olefin/nonconjugated diene elastomer component and tackiness agent is mixed under the temperature of the fusing point that is higher than acrylic resin; Add radical initiator and auxiliary agent to form mixture, this auxiliary agent comprises the multi-functional acrylate of containing at least two acrylate groups, the polyfunctional group maleimide that contains at least two imide groups or its mixture; Then under a temperature with this mixture thorough mixing and shear, have crosslinked at least about 97% gel content to form elastomerics wherein, and the kinetics solidified that adheres on polar material composition for thermoplastic elastomer be provided.In a preferred embodiment, the adhesion grade of elastic composition is 1 and to destroy type be cohesive failure.
The present invention also comprises a kind of thermoplastic elastomer cure system, comprising: radical initiator, and it contains at least a organo-peroxide; Auxiliary agent, it comprises the multi-functional acrylate of containing at least two acrylate groups, the polyfunctional group maleimide that contains at least two imide groups or its mixture; Wherein cure system comprises the radical initiator and the auxiliary agent of capacity, when mixing with acrylic resin, the material that contains ethene and tackiness agent, the gel content that forms modified elastomer is at least about the elastomer thermoplastic mixtures of 97% reaction modifying, and the mixture that adheres on the polar material is provided.In a preferred embodiment, the adhesion grade of elastomer blends is 1 and to destroy type be cohesive failure.
In another embodiment, the present invention includes a kind of thermoplastic elastomer based reaction mixture, it comprises acrylic resin, ethylene/alpha-olefin/nonconjugated diene elastomer component and tackiness agent and above-mentioned thermoplastic elastomer cure system.
But the present invention also comprises a kind of hardenable mixture, it comprises acrylic resin, ethylene/alpha-olefin/nonconjugated diene copolymer elastomer component, tackiness agent and contains radical initiator and the cure system of auxiliary agent, and this auxiliary agent comprises that one or more contain the multi-functional acrylate of at least two acrylate groups, contain polyfunctional group maleimide or its mixture of at least two imide groups.Be understood that top embodiment and preferred embodiment are applicable to all respects of the present invention separately.
Description of Preferred Embodiments
Have now found that according to the present invention, viscous heat thermoplastic elastic (" the TPE ") composition of the reaction modifying mixture of a kind of acrylic resin, ethylene/alpha-olefin/nonconjugated diene elastomer component and tackiness agent can be by containing the cure system dynamic vulcanization of radical initiator and auxiliary agent, and described auxiliary agent is selected from the multi-functional acrylate of containing at least two acrylate groups, the polyfunctional group maleimide that contains at least two imide groups or the mixture of the two.The TPE of this reaction modifying preferably has the viscosity that increases with polar material.
" bonding (adhesion) " (that is, adhere to (adhere)) this paper is used to be meant two kinds of different attractions between two kinds of phases of material when contacting with fixed attention.The scope of magnetism can be from strong chemical bond (about 25-100kcal/mol) to being called the interactional much weak physical force of Van der Waals.Between by bonding two individualities that keep together (that is, adherend, layer, film, base material etc.), form gluing joint (adhesive joint) or glued joint joint (adhesive bonded joint).An adherent key property is essential anti-separation of two kinds of adhesion materials, and preferably is difficult to separate.
Gluingly be tending towards adhere to destroying and cohesive failure in conjunction with two dominant mechanisms of destructive.Adhesion destruction is the interfacial failure between two jointing materials, and viscosity deficiency between weak frictional belt or the layer is not wished in its explanation.Cohesive failure is the internal sabotage in a kind of adhesion material, and the maximum strength of its explanation jointing material is less than the intensity of bond strength between two phases.Often, the destruction of gluing joint neither fully cohesion neither be adhering fully.
Acrylic resin is usually with about 10-70% weight, preferably about 11-60% weight, and more preferably from about there are and comprise one or more following materials in the amount of 12-55% weight: the homopolymer of propylene, propylene and at least a other C of 60mol% at least
2-C
20The multipolymer of alpha-olefin or its mixture.Preferred alpha-olefin comprises ethene, 1-butylene, 1-amylene, 1-hexene, methyl isophthalic acid-butylene, Methyl-1-pentene, 1-octene and 1-decene or its combination in this multipolymer.Acrylic resin typically basically without any functionalized, preferably fully without any functionalized, this is opposite with tackiness agent of the present invention.
The multipolymer of propylene can comprise one or more random or segmented copolymers.The random copolymers of propylene and alpha-olefin when using, generally includes macromolecular chain, wherein the monomer statistical distribution.The propylene content of these random copolymerss is normally at least about 70mol%, preferably at least about 75mol%.Segmented copolymer can comprise the different different blocks of forming; Each block comprises the homopolymer of propylene and the homopolymer of at least a other above-mentioned alpha-olefin.Although the copolymerization process of any appropriate comprises within the scope of the invention, obtain to have the heterophasic copolymer of propylene block by in a plurality of successive stage, carrying out polyreaction usually, wherein prepare different blocks successively.
The melt flow rate (MFR) (MFR) that is used for propene polymer of the present invention is preferably about 0.01-200g/10min (load: 2.16kg is at 230 times, according to ASTM D-1238-01).The alfon of illustration or multipolymer can PROFAX, ADFLEX and HIFAX are from Basell North America, Inc.of Wilmington, Delaware is commercially available, with FORTILENE, ACCTUFF or ACCPRO are from British Petroleum Chemicals ofHouston, Texas is commercially available, and from ExxonMobil Chemicals Company ofHouston, Texas, from Borealis A/S from Lydgby, Denmark, from SunocoChemicals of Pittsburgh, Pennsylvania, with from Dow Chemical Company ofMidland, commercially available dissimilar homopolymer polypropylene of Michigan and multipolymer.
Ethylene-dien terpolymer elastomeric component (ethylene/alpha-olefin/nonconjugated diene) is usually with about 5-60% weight, preferred about 6-55%, more preferably from about the amount of 7-50% weight (not comprising oil) exists, and is selected from the C that contains have an appointment 40-75% weight ethene, about 20-60% weight usually
3-C
20The terpolymer of the non-conjugated diene monomers of alpha-olefin component and about 1-11% weight.The alpha-olefin component comprises one or more C
3-C
20Alpha-olefin, wherein preferred propylene, 1-butylene, 1-hexene and 1-octene, most preferably propylene is used for ethylene elastomer.
The example of suitable non-conjugated diene monomers comprises one or more straight chain hydrocarbon diolefine or has alkene or its combination of the cycloalkenyl group replacement of 6-15 carbon atom.Concrete preferred embodiment comprises one or more types or material, comprising: (a) the straight chain acyclic dienes for example 1,4-hexadiene and 1,6-octadiene; (b) side chain acyclic dienes 5-methyl isophthalic acid for example, the 4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1,7-octadiene; (c) monocycle alicyclic ring diene, for example 1; 1,5-cyclooctadiene and 1,5-encircle 12 carbon diene; (d) many ring greases ring fused rings and bridge joint cyclic diolefine tetrahydroindene for example; Methyl-tetrahydroindene; Dicyclopentadiene (DCPD) (DCPD); Two rings-(2.2.1)-heptan-2, the 5-diene; Thiazolinyl, alkylidene group, cycloalkenyl group and ring alkylidene group norbornylene, for example 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornylene, 5-isopropylidene-2-norbornylene, 5-ethylidene-2-norbornene (ENB), 5-(4-cyclopentenyl)-2-norbornylene, 5-cyclohexylene-2-norbornylene and 5-vinyl-2-norbornylene (VNB); (e) alkene of cycloalkenyl group replacement, for example allyl group tetrahydrobenzene, vinyl cyclooctene, allyl group cyclodecene, vinyl cyclododecene.In these non-conjugated dienes commonly used, preferred diene is a Dicyclopentadiene (DCPD), 1,4-hexadiene, 5-methylene-2-norbornene and 5-ethylidene-2-norbornene or its combination.
In another embodiment, can use one or more to have the cinnamic styrenic elastomer of the highest about 50mol%, replace being used to form the ethylene-dien terpolymer elastomerics of elastomer group phase-splitting of the present invention, perhaps with this terpolymer elastomerics coupling." styrenic elastomer " used herein is meant to have the segmental elastomerics of at least one block, and wherein styrene monomer and hydrogenant or the olefin component that contains at least some degrees of unsaturation (not hydrogenation) combine.This paper can use linearity, radial, diblock or three block type styrenic elastomer.Styrenic elastomer if any, is preferably not functionalized.
Elastomeric vinylbenzene part, if any, preferably cinnamic polymkeric substance and analogue thereof and homologue or its arbitrary combination comprise alpha-methyl styrene and cyclosubstituted vinylbenzene, particularly encircle-methylate vinylbenzene.Preferred styrenic is vinylbenzene and alpha-methyl styrene, wherein special optimization styrene.The olefin component of styrenic elastomer for example can be ethene, divinyl, isoprene, butylene, propylene or its combination.Preferred styrenic elastomer comprises styrene butadiene, styrene-butadiene-styrene, styrene-isoprene, styrene-isoprene-phenylethene, styrene-ethylene/butylene, styrene-ethylene/butylene-styrene, styrene-ethylene/propylene, styrene-ethylene/propylene-styrene, styrene-ethylene/propylene-styrene-ethylene-propylene, vinylbenzene-butylene-butadiene-styrene or its combination.
Measure by ASTMD-1646-00, do not have oil-filled elastomerics typically to have mooney viscosity (ML 1+4,125 ℃) at least about 100.The elastomeric terpolymer of optimal ethylene/propylene/diene (EPDM).The elastomerics of illustration can NORDEL from DuPont Dow ElastomersLLC of Wilmington, Delaware is commercially available, with VISTALON from ExxonMobilChemicals of Houston, Texas is commercially available, with DUTRAL from Polimeri EuropaAmericas of Houston, Texas is commercially available, with BUNA EP from Bayer Corporationof Pittsburgh, Pennsylvania is commercially available, with KELTAN from DSM ElastomersAmerica of Baton Rouge, Louisiana is commercially available, with ROYALENE from Crompton Corporation of Middlebury, Connecticut is commercially available, with TUFTEC from Asahi America Inc.of Malden, Massachusetts is commercially available, perhaps with KRATON from Kraton Polymers LLC of Houston, Texas is commercially available.
Being used for tackiness agent of the present invention promotes when being used to form thermoplastic sulfurized rubber or tackifys.Opposite with tackiness agent, apply tackiness agent and bonding coat separately by surface-coated (application) (for example, lamination) or liquid coating.Tackiness agent of the present invention during it forms as the part of TPE hardening thing mixture.Tackiness agent preferably includes one or more functionalized propylene homopolymer or multipolymers, and usually exists with the amount of the viscosity that is enough to improve reaction modifying TPE hardening thing.Preferably, tackiness agent is with about 1-30% weight, preferably about 2-20% weight, and more preferably from about the amount of 3-15% weight exists.
But the acrylic resin of tackiness agent can be with grafted monomer by the known any technology of those of ordinary skills functionalized (that is, grafting), and for example at United States Patent (USP) 4,950, instruction in 541 adds this paper with its content by specific reference.But have at least a grafted monomer that is selected from the functional group of carbonyl and acid anhydrides and for example can be selected from unsaturated monocarboxylic acid or dicarboxylic acid and derivative thereof and unsaturated monocarboxylic acid acid anhydride or dicarboxylic anhydride and derivative thereof.As representative instance, functional group can comprise: toxilic acid, fumaric acid, methylene-succinic acid, Ba Dousuan, succsinic acid, styracin, citraconic acid, maleic anhydride, itaconic anhydride, crotonic anhydride, citraconic anhydride and arbitrary combination thereof.Preferably, use maleic anhydride, itaconic anhydride or its combination.More preferably, tackiness agent comprises the alfon or the multipolymer of the maleic anhydride graft that contains the residual free toxilic acid that is less than about 100/1000000ths parts (ppm).
Can and afterwards tackiness agent be joined in the elastomer thermoplastic mixtures before sclerosis.Preferably after sclerosis the downstream or TPV after as independent step adding functionalization polypropylene.The functionalized propylene homopolymer of illustration or multipolymer can PRIEX from Solvay, S.A.ofBrussels, Belgium is commercially available, with POLYBOND from Crompton Corporation ofMiddlebury, Connecticut commercially available and with EPOLENE from Eastman ChemicalCompany of Kingsport, Tennessee is commercially available.
Unexpected and the confirmation against expectation of the present invention, some functionalized polymeric is bonding as the success that tackiness agent more effectively is used for thermoplastic sulfurized rubber and polar material, be that some material more increases viscosity than other materials, and some material does not even produce the enough adhesions that are referred to as adhesion material.For example, the functionalization polypropylene of As used herein is ineffective as tackiness agent for maleinization styrene-ethylene-butylene-styrene (SEBS-MA).Therefore, tackiness agent does not preferably have at least basically or does not have fully, SEBS-MA.And, the tackiness agent of one or more functionalization polypropylene materials joined be not enough to obtain optimum among the conventional TPV, illustrate that also be essential for the suitable selection elastomerics of TPV cure system to obtaining ideal viscosity.
The elastomerics cure system contains and at least a auxiliary agent blended radical initiator.Thereby select radical initiator in mixing process, to make the elastomerics completely solidified with the free radical that produces capacity.Radical initiator is with about 0.001-2% weight, preferably about 0.01-1% weight, and most preferably from about the amount of 0.03-0.3% weight exists.Typically, radical initiator can be one or more organo-peroxides, organic azo-compound or its any mixture.
Be used for radical initiator of the present invention, preferably one or more organo-peroxides should have greater than about 1 hour half life of decomposition down at 120 ℃.Operable representative superoxide is a peroxy ketal class for example 1,1-two (t-butylperoxy)-3,3,5-trimethyl-cyclohexane, 1,1-two (uncle's hexyl peroxy)-3,3,5-trimethyl-cyclohexane, 1,1-two (uncle's hexyl peroxy) hexanaphthene, 1,1-two (t-butylperoxy) cyclododecane, 1,1-two (t-butylperoxy) hexanaphthene, 2,2-two (t-butylperoxy) octane, normal-butyl-4,4-two (t-butylperoxy) butane, normal-butyl-4,4-two (t-butylperoxy) valerate, etc.; Dialkyl peroxide, for example ditertiary butyl peroxide, dicumyl peroxide, tertiary butyl cumyl peroxide, α, α '-two (t-butylperoxy--sec.-propyl) benzene, α, α '-two (t-butylperoxy) diisopropyl benzene, 2,5-2,2,5-dimethyl-2,5-two (t-butylperoxy) hexin-3, etc.; Diacyl peroxide, for example acetyl peroxide, peroxidation isobutyryl, peroxidation decoyl, decanoyl peroxide, lauroyl peroxide, peroxidation 3,3,5-trimethyl acetyl; Peroxidation toluoyl, peroxidation 2,4 dichloro benzene formyl, m-toluyl peroxide, etc.; Peroxy ester class, for example peroxide acetic acid butyl ester, peroxidation tert-butyl isobutyrate, peroxide-2-ethyl hexanoic acid tert-butyl, the peroxidation lauric acid tert-butyl ester, peroxidized t-butyl perbenzoate, peroxidation m-phthalic acid di tert butyl carbonate, 2,5-dimethyl-2,5-two (benzoyl peroxy) hexane, the peroxidation toxilic acid tert-butyl ester, tert-butylperoxy isopropyl carbonate, peroxidation acid cumyl ester, etc.; Hydroperoxide type, for example t-butyl hydroperoxide, hydrogen peroxide cumene, hydrogen peroxide diisopropyl benzene, 2,5-two hydroperoxidations-2,5-dimethylhexane, 1,1,3,3-four-methyl butyl superoxide, etc.; Or its arbitrary combination.In these compounds, preferably at the dialkyl peroxide of 120 ℃ of half-life greater than 1 hour.Transformation period is defined as initial peroxide concentration and reduces half required time.
Auxiliary agent in the elastomerics cure system is with about 0.1-10% weight, preferred about 0.5-7% weight, most preferably from about the amount of 0.7-3% weight exists, and can comprise that one or more contain the multi-functional acrylate of at least two acrylate groups, contain polyfunctional group maleimide or its mixture of at least two imide groups.The example that is particularly useful for multi-functional acrylate of the present invention is Viscoat 295 (TMPTA), ethoxylated trimethylolpropane triacrylate, propoxylation Viscoat 295, propoxylated glycerol triacrylate, pentaerythritol triacrylate, cyclohexane dimethanol diacrylate, tetramethylol methane tetraacrylate, ethoxylation tetramethylol methane tetraacrylate and two-trimethylolpropane tetra-acrylate.The example that also can be used for polyfunctional group aminimide of the present invention is phenylene-two-maleimide, N for example, a N '-phenylenedimaleimide and 4,4 '-two maleimide amino-ditans and 3,3 '-two maleimide amino-ditans.At one more preferably in the embodiment, auxiliary agent is the multi-functional acrylate, more preferably comprises the multi-functional acrylate of TMPTA.
Against expectation find, for example trimethylolpropane trimethacrylate (TMPTMA) is when with 1 for methyl acrylic ester, and the 2-polyhutadiene is in conjunction with can not effectively improving compression set and oil swell during dynamic vulcanization EPDM as auxiliary agent under polyacrylic situation is arranged.This result is just in time opposite with standard thermoset EPDM, the wherein known TMPTMA/1 that uses, and 2-polyhutadiene and superoxide sclerosis EPDM can reduce compression set and oil swell.This unusual confirmation is although the document that auxiliary agent is used for thermoset rubber may may run into obvious difference and unpredictability as the guidance of dynamic vulcanization system.Therefore, in one embodiment, auxiliary agent does not have TMPTMA or all methyl acrylic esters at least basically, and does not preferably have TMPTMA or all methyl acrylic esters fully.
Other auxiliary agent can be nonessential with the highest about 10% weight, preferred about 1-7% weight and most preferably from about 2-6% weight the amount existence and can comprise 1, the 2-contents of ethylene is greater than 50% the polymkeric substance that contains diene, comprise random 1,2-polyhutadiene, a rule 1,2-polyhutadiene, high-vinyl solution styrene butadiene elastomerics or its mixture.Random 1,2-polyhutadiene or random high vinyl polybutadiene, the viscous liquid that has the structure of the random setting of side chain vinyl typically.The preparation of random form generally includes the use polarity modifier, and for example the lithium catalyzed polymerization of chelating diamines, oxide ether compound, acetals and ketal class as United States Patent (USP) 4,696, described in 986, adds this paper with it by reference.Can use arbitrarily other suitable formation random 1, the method for 2-polyhutadiene.It is about 1 that random polyhutadiene typically has, 300-130,000 number-average molecular weight (Mn), and can liquid and the solid supported form commercially available.
Between advise 1,2-polyhutadiene (" PBD ") be a kind of solid have rule structure the hypocrystalline thermoplastic resin, wherein the side chain vinyl alternately is positioned at the opposite side about polymer main chain.1 of divinyl, 2-polymerization take place in the mode of head-to-tail and produce new chiral centre.In this syndiotactic polymer, other chiral centre has identical configuration." hypocrystalline " this paper is defined as less than about 90% degree of crystallinity.
Between rule PBD polymkeric substance can use Ziegler-type catalyst to make by comprising solution polymerization, letex polymerization and suspension polymeric any desired manner.As United States Patent (USP) 6,201, can use various coordination catalyst system for example cobalt-based system, ferrum-based catalyst system, catalyst with base of molybdenum system and chromium-based catalysts system described in 080, by reference it is added this paper.
Between physics, machinery and the rheological property of rule PBD form be subjected to the influence of its fusing point, contents of ethylene and degree of crystallinity very big.Fusing point can be as high as 206 ℃, and this depends on used synthetic method.In order to make maximum effect of the present invention, between the PBD polymkeric substance rule content enough height be preferably greater than about 70 ℃ and to provide less than about 205 ℃ crystalline melt point at least about 60 ℃.1, the 2-contents of ethylene is preferably greater than 75% greater than 50%.Between the degree of crystallinity of rule polyhutadiene less than about 50%, 10-45% more preferably from about.The weight-average molecular weight of rule polyhutadiene is typically greater than about 100,000 between preferred.In the present invention, a rule polyhutadiene has than easy processing of random high vinyl polybutadiene and the little advantage of cost.
" high-vinyl solution styrene butadiene " elastomerics is by with conjugated diene monomer, 1,3-butadiene for example, and with vinyl aromatic monomer, vinylbenzene for example, copolymerization forms.It is about 40% that the elastomeric preferred vinyl content of high-vinyl solution styrene butadiene is preferably greater than, more preferably greater than about 50%.At United States Patent (USP) 6,140, the solution polymerization process of preparation high-vinyl styrene butadiene has been described in 434, add this paper thus by reference.
The state of cure of thermoplastic sulfurized rubber depends on various factors, comprises the amount and the solidifying agent type of treatment time, elastomerics solidifying agent.Not exclusively solidify with rubber or partly solidified mixture is compared, completely crued elastomeric component of the present invention makes the TPV mixture have the physicals of improvement, and oil swell is little, compression set is low and the tensile strength performance height.
It is the gel content of elastomerics in mutually that of the state of cure of elastomeric component measures (that is, crosslinked mensuration).If elastomerics is mutually partly solidified, so only part rubber is insoluble to solvent, for example in dimethylbenzene or the hexanaphthene.If elastomerics phase completely solidified is not dissolved at least about 97% elastomerics so.Improvement thermoplastic sulfurized rubber of the present invention is by mixture cures to the contained EPDM rubber agglomerative degree at least about 97% is made.This gel content is meant that the elastomerics of composition contains the rubber that can extract that is not more than 3% weight mutually under 23 ℃ in hexanaphthene, and the elastomerics that preferably is meant composition contains the rubber that can extract less than 1% weight mutually in hexanaphthene under 23 ℃.In general, extractable matter is few more, and performance is good more; Even more preferably under 23 ℃, in hexanaphthene, there is not to extract the curing elastomer of rubber (for example, less than 0.5 weight %) basically." completely solidified " as herein described be meant in gel content, under 23 ℃ in hexanaphthene degree of cure at least about 97%, preferably at least 99%.
Gel content in gel per-cent is by United States Patent (USP) 3,203,937 and United States Patent (USP) 4,948,840 step measurements, it comprises by in hexanaphthene the sample of composition being soaked 48 hours under 23 ℃ and the dried residue of weighing is measured the amount of insoluble polymer, suitably proofreaies and correct with the understanding to composition then.Therefore, by deduct the component except that rubber that is dissolved in the hexanaphthene from initial weight, for example extending oil uses calibrated initial weight and final weight with the weight that is dissolved in other component in the hexanaphthene.From initial and final weight, deduct any insoluble pigment, filler etc.
And the % weight of this oil swell is that elastomerics curing or of crosslinking degree mutually with equal increments oil and different thermoplastic cross-linked rubber (TPV) of polypropylene content is implied and measured.According to the present invention, the oil swell value that elastomeric low cross-linking or partial cross-linked generation are higher will have lower (that is, more preferably) oil swell and have the elastomeric thermoplastic elastomer of highly cross-linked dispersion.Oil swell is according to measuring method ISO 1817 (1999), uses the oily IRM903 of mensuration to measure.The sample of material composition is immersed in this oil and at 125 ℃ of following constant temperature kept 70 hours.Fresh IRM903 oil should be used for each test.It is about 100 ℃ field to guarantee that the TPV material can be used for design temperature that this temperature and time standard is particularly useful for automotive industry.Have the polyolefin-based thermoplastic elastomerics of uncrosslinked or only partial cross-linked polyolefin elastomer, use condition determination as herein described, record 150% to the disadvantageous high oil swell value that surpasses 1000%.Only be close crosslinkedly fully when polyolefin elastomer, gel content was at least about 97 o'clock, and the oil swell value is typically less than about 100% weight.The invention provides a kind of non-phenolic resin curing (non-phenolic, resin-cured) TPV, under condition described herein, hard relatively TPV (70Shore A durometer hardness or bigger at least) oil swell preferably is not more than about 90% weight, and softer relatively TPV (at least 70 Shore A durometer hardness or bigger) oil swell is not more than about 100% weight.
Extending oil or treated oil, any one in the viscosity through being usually used in reducing elastic composition, hardness, modulus and the cost or multiple.With regard to increasing of most of ethylene/alpha-olefin/nonconjugated diene elastomers filled (extension), use saturate oil.Preferred paraffinicity is greater than about 40% saturated extending oil, and it is with method ASTM D-2140-97 mensuration, and more preferably paraffinicity is greater than about 50%.The increment oil viscosity is to guaranteeing that volatility low in the mixing process also is important.The treated oil that can be used for thermoplastic sulfurized rubber composition has under 40 ℃ usually greater than the kinematic viscosity of about 20 centistokes, and this viscosity is to use measuring method ASTMD-445-01 to measure.More preferably, this kinematic viscosity under 40 ℃ is greater than about 40 centistokes.The those of ordinary skill of processing elastomeric field is expected type and the amount to the most useful oil of any given application described herein easily.Extending oil, when using, ideally with about 4-65% weight, preferably about 5-60% weight, most preferably from about the amount of 10-55% weight exists.
This composition can also contain filler component, and it typically comprises one or more appropriate filler materials.Typically, filler component comprises one or more mineral fillers.Be used for representative inorganic filler of the present invention and for example comprise lime carbonate, magnesiumcarbonate, silicon-dioxide, carbon black, glass fibre, titanium oxide, clay, mica, talcum, barium sulfate, magnesium hydroxide or aluminium hydroxide or its arbitrary combination.Typically, thermoplastic elastomer of the present invention contains nonessential filler, and when existing, content is about 0.001-20% filler weight.Other additive that can comprise in the present invention comprises, for example, one or more organic and mineral dye, thermo-stabilizer, antioxidant, UV light absorber, photostabilizer, fire retardant, antiblocking agent, pore forming material, static inhibitor or antiseptic-germicides, add-on separately enough provides required effect (it is heat-resisting stable that for example, the amount of thermo-stabilizer is enough to make elastomerics).
Can use the method for any appropriate to prepare mixture of the present invention.Melting mixing is a preparation preferred method of the present invention.The technology of polymkeric substance and all types of additive melting mixing is known for those of ordinary skills and typically can be used for the present invention.Typically, be used for melting mixing of the present invention, the single component of mixture is being mixed in machine extruder or mixing tank, be heated to the temperature of enough formation polymer melt then and carry out reaction modifying.Mechanical mixer can be continuous or batch mixer.The example of suitable continuous mixing device comprises that single screw extrusion machine, engagement corotation change for example CoperionWerner ﹠amp of twin screw extruder; Pfleiderer ZSK forcing machine, despining twin screw extruder be those and the reciprocal single screw mixer produced of LEISTRITZ BUSS kneader altogether for example for example.The example of batch mixer has horizontal 2-rotor mixing tank, for example BANBURY or BOLING mixing tank.The reaction modifying mixture can mix by the known any technology of those of ordinary skills, for example instructs in the U.S. Patent application 10/448,301 of application on May 30th, 2003, and its content is added this paper by reference.Preferably, further not crosslinked basically after mixture forms goods, more preferably further not crosslinked.
Elastomer thermoplastic mixtures of the present invention forms can put on various polar materials, preferably puts on the material on the polar substrates.Polar material can be for example aluminium, brass, chromium, copper, nickel, steel, stainless steel, titanium or its arbitrary combination or an alloy of metal.Polar material can comprise that also one or more also contain for example polar polymer of nitrogen, oxygen or one or more halogens of one or more atoms except containing hydrogen and carbon.Preferably, halogen comprises fluorine.Mixture of the present invention is specially adapted to be bonded in second-order transition temperature (Tg) or melt temperature (Tm) at least about 150 ℃, preferably at least about 165 ℃, more preferably from about on 175 ℃-325 ℃ the polarity engineering resin.Polar polymer or engineering resin can be used alone or in combination, and be preferably selected from the homopolymer or the multipolymer of polyamide-based, polyimide, polycarbonate-based, polyester, polyacetals, polystyrene, styreneo-acrylonitrile resin, acrylonitrile-butadiene-styrene (ABS) (ABS) resin, polyphenylene oxide and following material: tetrafluoroethylene, vinyl fluoride, vinylidene fluoride or chlorotrifluoroethylene, acrylic acid or the like, methacrylic, fragrant ketone, or its arbitrary combination.Preferred polar polymer comprises polyamide-based.Preferred polyamide-based be nylon-6; Nylon-6,6; Nylon-11; PA-12; Nylon-6,12; And composition thereof or multipolymer.Elastomer thermoplastic mixtures does not preferably have or does not more preferably have fully the polar substrates component at least basically.
Thermoplastic elastomer of the present invention can be used for automobile and other goods, for example liner, weather-resistant glue, cup support and airbag cover.They also can be used for, for example, and machine parts, electric parts, cable, flexible pipe, band and toy.The present invention also comprises goods, it comprise base material and form by this composition wholly or in part one or more layers.Base material can be wholly or in part by one or more layers covering.In one embodiment, the layer that is formed by the TPE mixture of adhesivity reaction modifying of the present invention or comprise this mixture is preferred to be adjoined with the part base material or surrounds base material, and between layer and base material without any other layer.But preferred goods comprise having the engineering base material the goods of the softer feel of needs, for example power tool and manipulative device overlap with handle etc.TPV electric hand handle is used, and for example, can coat shapings (overmold) and put at polymeric amide, and wherein TPV soft touches and vibrate wettability and prove that comfortable the controlling to instrument is useful.These goods can pass through different plastic processings, and for example the injection coating is shaped (injectionovermolding), two emission is injection-molded, embed molding, coextrusion, blowing etc. makes.Elastomer thermoplastic mixtures can be preferably used as the base-material of glass run passage; Can provide low friction with the polymeric amide of its coextrusion.
Term used herein " does not have " to be meant described material basically less than about 5 weight %, preferably less than about 1 weight %, is more preferably less than about 0.5 weight %.In a preferred embodiment, it is meant that described material is less than about 0.1 weight %.Material " does not have " fully or " not having " is meant except any amount that exists with trace impurity do not have fully.
Term used herein " does not have in fact " especially to be meant that material has the actual moisture content less than 0.2 weight %, preferably less than about 0.17 weight % at the moisture sensitivity of material.In a preferred embodiment, moisture content is lower than about 0.15 weight %.
Except as otherwise noted, all wt % is the weight of relative total composition.
Term " about " used herein is interpreted as relating to the endpoints thereof (bothnumbers in a range of numerals) of numerical range usually.And it is very several that all numerical ranges of this paper are understood to include each of integer in this scope.
Embodiment
Describe the present invention by following embodiment, they only are the modes that purpose of description and should not thinking limits the scope of the invention or it can be implemented.
Used material among the embodiment:
The PP/EPDM thermoplastic sulfurized rubber of TPV-1 peroxide cure; Extending oil content 22
Weight %; Cure system: 0.05 weight % superoxide, 2 weight %, three hydroxyl first
The base propane triacrylate
TPV-2 Santoprene
TM101-55 derives from Advanced Elastomer Systems
TPV-3 Santoprene
TM8281-55 derives from Advanced Elastomer Systems
TPV-4 Santoprene
TM8291-55PA derives from Advanced Elastomer Systems
The polypropylene of PP-MA1 maleic anhydride graft, MA content=0.5 weight %
The polypropylene of PP-MA2 maleic anhydride graft, MA content=1 weight %; MFR=110
dg/min
The polypropylene of PP-MA3 maleic anhydride graft, acid number=9mg CH
3The ONa/g polymkeric substance
The polypropylene that PP-AA is acrylic acid-grafted, AA content=6 weight %
The styrene-ethylene-butylene-styrene of SEBS-MA maleic anhydride graft, acid number=10mg
CH
3The ONa/g polymkeric substance
The ethylene-propylene copolymer of EPR-MA maleic anhydride graft; MA content=1.0 weight %;
MER＝3dg/min
Make the performance of measuring mixture in the following method:
100% modulus, 100% tensile modulus, wherein pinblock speed is 500mm/min, with
MPa MPa meter is according to ISO 37 (1994)
UTS, the MPa ultimate tensile strength, wherein pinblock speed is 500mm/min, with million
The handkerchief meter is according to ISO 37 (1994)
Ult.elong.% ultimate elongation %, wherein pinblock speed is 500mm/min, according to ISO
37(1994)
Hardness Shore A durometer hardness, under 15 seconds and room temperature (23 ℃) according to ISO
868 (1985) measure
Compression set, % compression set continues 70 hours at 70 ℃ or 125 ℃, in %, presses
According to ISO 815 (1991)
Oil swell, the wt.% oil swell continues 70 hours down at 125 ℃ or 70 ℃, uses IRM903
Oil is in % weight, according to ISO 1817 (1999)
Viscosity between two surfaces of stripping strength quantitative assay is in gm/cm, 180
Under the angle by method as herein described
Adhere to grade by method as herein described coat be formed on 6 of the nylon can be bonding
The viscosity of TPV is with the value class scoring of 1-4
Destroy the type of type adhesion failure, mark with A-C: the A type: tackiness agent/interface (
Interfacial failure between two base materials); Type B: peel off (not bonding); C
Type: cohesive (internal sabotage of base material)
Thermoplastic sulfurized rubber of the present invention is embossed on the nylon base to estimate coats the bond properties that is formed in the soft TPV of the touching handle that polymeric amide puts.Thickness is inserted into for the nylon-6 sheet of extruding of about 0.6-1mm that to be of a size of 100 * 150mm and molding temperature be in 90 ℃ the thick mould of 3mm.Then under the suitable processing conditions that thermoplastic sulfurized rubber of the present invention is injection-molded to the nylon-6 sheet.Nylon-6 sheet not preheating usually before embedding is injection-molded.
The stripping strength of working sample is as the required power of two-layer coming unstuck (de-bond) of composite sample then.By top coating forming board (plaque) cut lengths is the stripping strength sample of 12.7mm * 101.6mm.Peel off TPV (being about 15mm) that sub-fraction coat to be shaped and increase and fill, feasiblely easily working sample is stuck on the Instron equipment with fiber reinforcement tackiness agent (adhesive).Then this tackiness agent enhanced TPV partly is clipped on the top clip, nylon partly is clipped on the following clip.Then can bonding TPV and the nylon-6 layer with 180 ° of peel angles tractive round about, bonding with the gm/cm record between two-layer break required power and this power show with two-layer between bonding (adhesive bond) intensity directly related.Stripping strength is preferably at least about 650g/cm, more preferably at least about 800g/cm, and 900-10 most preferably from about, 000g/cm.
Also with following value class estimate of the present invention can bonding TPV and the nylon-6 working sample between viscosity:
The explanation of adhesion grade
1 TPV stick on the nylon-6 base material forcefully and when not tearing TPV not
Can peel off
2 TPV stick on the nylon-6 base material and when not tearing TPV and can peel off
3 TPV materials stick on the nylon-6 base material and still can peel off easily
4 TPV do not stick on the nylon-6 base material
Elastomer thermoplastic mixtures of the present invention, called after TPV-1 is used for following embodiment (embodiment 1-13).Said composition comprises homopolymer polypropylene and EPDM elastomerics, and they solidify through superoxide as mentioned above, and the compression set at 125 ℃/70 hours is 35%, and ShoreA hardness is 53, and is 104% 125 ℃/70 hours oil swell.In length-to-diameter ratio (L/D) 52 Coperion Werner ﹠amp; Prepare TPV-1 in the Pfleiderer ZSK 70mm corotation commentaries on classics twin screw extruder.At first feeding section solid matter is added, and liquid adjuvants, if any, in second cylinder, inject.Extending oil, when using, the downstream during curing reaction adds.Extrusion temperature is 205 ℃, and extruded velocity is 400-450rpm.The sample injection molding that will derive from twin screw extruder then is into about the thick plate of 2mm, (1994) 90 ° of angle breach samples of cross cutting ISO 37 (1994) Type C dumbbell specimens and ISO 34-1 are thus measured mechanical property then under the gauge length of the finding speed of 500mm/min, 25mm.
In Table I, TPV-1 mixes under 205 ℃ in single screw rod Haake forcing machine with various functionalized polymerics.Although these functionalized polymerics are increased to viscosity to a certain degree, when coating is formed on the polyamide substrate, to compare with other tackiness agent, maleinization propylene class (PP-MA) is tackified significantly.The C type (cohesive) of embodiment 1 destroys at the interface the bonding strength of explanation between two phases than the bonding strength height in mutually, and so as the unexpected and unexpected result's of the present composition successful proof.
Table I
| Embodiment 1 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | |
| Tackiness agent, type | PP-MA1 | PP-AA | SEBS-MA | EPR-MA | Do not have |
| Tackiness agent, wt.% | 10 | 10 | 10 | 10 | |
| Hardness, Shore A | 70 | 69 | 50 | 48 | 53 |
| UTS，MPa | 4.7 | 5.2 | 3.3 | 2.7 | 4.1 |
| Ult.elong，％ | 272 | 333 | 322 | 276 | 328 |
| 100% modulus, MPa | 3.4 | 3.3 | 1.8 | 1.6 | 2.0 |
| Adhere to grade | 1 | 3 | 2 | 2 | 4 |
| Destroy type | The C type | The A type | The A type | The A type | Type B |
In Table II, the PP-MA of different stage and quantity is mixed with TPV-1, be embossed on the nylon-6 base material then and estimate as mentioned above.Again, cohesive failure is required result.
Table II
| Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| TPV-1，wt.％ | 96 | 93 | 96 | 93 | 90 | 96.5 | 95 |
| PP-MA1，wt.％ | 4 | 7 | -- | -- | -- | -- | -- |
| PP-MA2，wt.％ | -- | -- | 4 | 7 | 10 | -- | -- |
| PP-MA3，wt.％ | -- | -- | -- | -- | -- | 3.5 | 5 |
| Hardness, Shore A | 60 | 64 | 61 | 66 | 71 | 61 | 64 |
| UTS，MPa | 4.3 | 4.7 | 4.7 | 5.2 | -- | 4.9 | 5.0 |
| Ult.elong，％ | 287 | 301 | 288 | 291 | -- | 287 | 305 |
| 100% modulus, MPa | 2.7 | 3.1 | 2.9 | 3.4 | -- | 2.9 | 3.1 |
| Adhere to grade | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Destroy type | The C type | The C type | The C type | The C type | The C type | The C type | The C type |
In Table III, embodiment 9 and Comparative Examples 5-6 mix down in 205 ℃ in the Haake single screw extrusion machine.PP-MA adds in an independent step.Result when embodiment 10 is presented at downstream during the TPV-1 preparation of compositions and adds PP-MA.Comparative Examples 5-6 uses technical grade TPV, and embodiment 9-10 uses TPV of the present invention, confirms that the radically curing system obtains much better result than the TPV curing of other type.
Table III
| Embodiment 9 | Embodiment 10 | Comparative Examples 5 | Comparative Examples 6 | |
| TPV-1，wt.％ | 93 | 93 | ||
| TPV-2，wt.％ | -- | -- | 93 | -- |
| TPV-3，wt.％ | -- | -- | -- | 93 |
| PP-MA2，wt.％ | 7 | 7 | 7 | 7 |
| Curing type | Free radical | Free radical | Resol (phenolic) | Hydrosilication |
| Viscosity is estimated | 1 | 1 | 2 | 2 |
| Destroy type | The C type | The C type | The A type | The A type |
| Stripping strength | 1473 | 1440 | 505 | 546 |
Embodiment 11-13 in the Table IV is mixed down in 205 ℃ in single screw rod Haake forcing machine by the TPV-1 of 92.7 weight % and the PP-MA1 of 7.5 weight %.The result shows of the present inventionly can bonding TPV need drying before handling, and industrial polymeric amide can bonding TPV-4 must be dry before handling.
Table IV
| Embodiment 11 | Embodiment 12 | Embodiment 13 | Comparative Examples 7 | |
| Drying conditions | 90 ℃ of lasting 3-4 of TPV-1 hours | TPV-1 is moist | TPV-1 adds entry (0.5wt.%) | TPV-4 is moist |
| Actual moisture content, wt.% | 0.08 | 0.10 | 0.17 | 0.20 |
| Viscosity is estimated | 1 | 1 | 1 | -- |
| Destroy type | The C type | The C type | The C type | -- |
| Appearance | Excellent | Excellent | Generally | The polymkeric substance severely degrade can not mold pressing |
Be understood that the present invention is not limited to this paper explanation and described accurate structure.Therefore, those of ordinary skills perhaps by routine test, can be easy to obtain all useful improvement by content disclosed herein, and think in the spirit and scope of the invention of appended claims definition.
Claims (13)
1. the elastomer thermoplastic mixtures of an adhesivity reaction modifying, by the material that comprises acrylic resin, ethylene/alpha-olefin/nonconjugated diene copolymer elastomer component and tackiness agent, dynamic vulcanization forms in the cure system that comprises following material is arranged:
One radical initiator; With
One auxiliary agent, it comprises that one or more contain the multi-functional acrylate of at least two acrylate groups, contain polyfunctional group maleimide or its mixture of at least two imide groups;
Wherein the total amount of radical initiator and auxiliary agent is enough to provide at least about the gel content of 97% elastomer blends and provides with the minimum stripping strength at least about 650g/cm and adheres to mixture of the present invention on the polar material.
2. modified mixture as claimed in claim 1, wherein but tackiness agent comprises with being selected from functionalized alfon of following grafted monomer or multipolymer: unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated monocarboxylic acid acid anhydride, unsaturated dicarboxylic acid acid anhydride and combination thereof, and wherein the adhesion grade that has of elastomer blends is 1 and to destroy type be cohesive failure.
3. modified mixture as claimed in claim 2, wherein tackiness agent comprises the alfon or the multipolymer of maleic anhydride graft, and wherein radical initiator exists with the amount of about 0.001%-2% weight of modified mixture, and comprises the not wet at least basically quick property of at least a organo-peroxide and this mixture.
4. modified mixture as claimed in claim 1, wherein there is and comprises Viscoat 295 in auxiliary agent with the amount of about 0.1%-10% weight of modified mixture, ethoxylated trimethylolpropane triacrylate, the propoxylation Viscoat 295, the propoxylated glycerol triacrylate, pentaerythritol triacrylate, cyclohexane dimethanol diacrylate, tetramethylol methane tetraacrylate, the ethoxylation tetramethylol methane tetraacrylate, two-trimethylolpropane tetra-acrylate, N, a N '-phenylenedimaleimide, 4,4 '-two maleimide amino-ditans, 3,3 '-two maleimide amino-ditans, or its combination.
5. modified mixture as claimed in claim 1, wherein auxiliary agent comprises Viscoat 295, N, a N '-phenylenedimaleimide or its combination.
6. modified mixture as claimed in claim 1, also comprise second auxiliary agent, it exists with the amount of about 0.1%-10% weight of modified mixture, advises 1 between wherein second auxiliary agent comprises, 2-polyhutadiene, random 1,2-polyhutadiene, high-vinyl solution styrene butadiene elastomerics or its mixture.
7. modified mixture as claimed in claim 1, wherein modified mixture comprises about 10%-70% weight acrylamide resin, the ethylene/alpha-olefin/nonconjugated diene elastomer component of about 5%-60% weight and about 1%-30% weight adhesive.
8. modified mixture as claimed in claim 1, therein ethylene/alpha-olefin/nonconjugated diene elastomer component have mooney viscosity at least about 100 [ML (@125 ℃ of 1+4)] when not having oil.
9. article comprise the reaction modifying mixture of claim 1.
10. the preparation method of the composition for thermoplastic elastomer of the dynamic vulcanization of claim 1 comprises:
The mixture of acrylic resin, ethylene/alpha-olefin/nonconjugated diene elastomer component and tackiness agent is mixed under the temperature greater than the fusing point of acrylic resin;
Add radical initiator and auxiliary agent to form mixture, this auxiliary agent comprises the multi-functional acrylate of containing at least two acrylate groups, the polyfunctional group maleimide that contains at least two imide groups or its mixture; With
Then under a temperature with this mixture thorough mixing and shear, have crosslinked at least about 97% gel content to form elastomerics wherein, and the composition for thermoplastic elastomer that adheres to the dynamic vulcanization on the polar material be provided.
11. a thermoplastic elastomer cure system comprises:
Radical initiator, it contains at least a organo-peroxide;
Auxiliary agent, it comprises the multi-functional acrylate of containing at least two acrylate groups, the polyfunctional group maleimide that contains at least two imide groups or its mixture;
Wherein cure system comprises the radical initiator and the auxiliary agent of capacity, when mixing with acrylic resin, the material that contains ethene and tackiness agent, the gel content that forms modified elastomer is at least about the elastomer thermoplastic mixtures of 97% reaction modifying, and the mixture that adheres on the polar material is provided.
12. a thermoplastic elastomer based reaction mixture comprises:
Acrylic resin, ethylene/alpha-olefin/nonconjugated diene elastomer component and tackiness agent; With
The thermoplastic elastomer cure system of claim 11.
13. but hardenable mixture, comprise acrylic resin, ethylene/alpha-olefin/nonconjugated diene copolymer elastomer component, tackiness agent and cure system, this cure system comprises: radical initiator and auxiliary agent, described auxiliary agent comprise that one or more contain the multi-functional acrylate of at least two acrylate groups, contain polyfunctional group maleimide or its mixture of at least two imide groups.
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|---|---|---|---|
| US52909903P | 2003-12-15 | 2003-12-15 | |
| US60/529,099 | 2003-12-15 | ||
| US10/877,976 | 2004-06-29 |
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| CN1906218A true CN1906218A (en) | 2007-01-31 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102695726A (en) * | 2010-01-06 | 2012-09-26 | 道康宁公司 | Modified polyolefins |
| CN112805346A (en) * | 2018-09-19 | 2021-05-14 | 康尔福盛303公司 | Method and formulation for bonding dissimilar materials |
| CN115044171A (en) * | 2022-06-30 | 2022-09-13 | 浙江华正新材料股份有限公司 | Resin composition, resin-based composite material and preparation method thereof |
-
2004
- 2004-11-24 CN CN 200480040490 patent/CN1906218A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102695726A (en) * | 2010-01-06 | 2012-09-26 | 道康宁公司 | Modified polyolefins |
| CN102695726B (en) * | 2010-01-06 | 2014-08-13 | 道康宁公司 | Modified polyolefins |
| CN112805346A (en) * | 2018-09-19 | 2021-05-14 | 康尔福盛303公司 | Method and formulation for bonding dissimilar materials |
| US11541649B2 (en) | 2018-09-19 | 2023-01-03 | Carefusion 303, Inc. | Methods and formulations for bonding dissimilar materials |
| CN112805346B (en) * | 2018-09-19 | 2023-08-29 | 康尔福盛303公司 | Method and formulation for bonding dissimilar materials |
| CN115044171A (en) * | 2022-06-30 | 2022-09-13 | 浙江华正新材料股份有限公司 | Resin composition, resin-based composite material and preparation method thereof |
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