CN100335579C - Flexible coatings for elastomer substrates - Google Patents

Abstract

Emissive coatings for flexible substrates, preferably elastomers or elastomers bonded to metal are disclosed. The coating composition is formed by combining parts (a) and (b) where part (a) comprises an organic solution or aqueous dispersion of a functional group containing polymer or copolymer and thermal conductive filler; and part (b) comprises a liquid curing component, for example a poly isocyanate, a carbodiimide, or an amino resin. The coating compounds can be applied to an substrate either before or after the substrate has been vulcanized. The coatings can be cured at ambient temperatures and provide heat dissipation over long term service at elevated temperatures.

Description

The method that is used for the flexible coating and the coating elastomer moulded product of elastomer substrates

Invention field

The present invention relates to be coated in the weather resistant coatings on the flexible substrate article outer surface, especially be coated in elasticity or rubber item or contain coating on the base material of these materials.Except the protective membrane performance can be provided, this coating can reduce heat accumulation (heat dissipation) by heat is derived heat from goods.This coating can be coated on the elastic substrate before or after base material cures.

Background of invention

The engineering Resilient product is designed to deflection and flexure type, distortion and answer type during use and/or comprises damping force type or the repetitive vibrations type that absorbs moment of torsion, and is used for multiple industrial application.For example, elastic material is used for tire, flexible pipe, seal strip, such as shelf, vibroshock and seal etc. of engine mount etc., and is designed to show hysteresis loss, heat-resisting etc., listed several design forms here.These and other goods of making various products have multiple purposes of having established, as are used for industrial machine and vehicle part.The thermo-contact of many elastomer products and various source (as oil engine).Recently the size of the raising of service temperature and vehicle startup unit room reduces and causes that all the part (as rubber hose, plastic housing, belt, various shelf, coverture, seal strip, grommet, packing ring, dividing plate, lid, casing etc.) of thermal source and this moulding is more approaching.In these goods some are subjected to hot sulfurization, and other are in self cure, and some other solidifies by different way and shows special flexibility, ductility, caoutchouc elasticity, thereby as thermoplastics or thermosetting material.

All polymeric materials can be degraded because of contacting with heat, light, oxygen, ozone, solvent, oil and/or fuel.Especially, well-known is that the especially natural and/or synthetic vulcanized rubber of elastic material can be degraded when contacting with these reagent, has therefore carried out research continuously so that the elastomeric article that can resist this degradation factors to be provided in industry.

United States Patent (USP) 6,022,626 disclose the coating that is applicable to the covering engine frame, are subjected to oxygen, ozone and/or UV photodamaged to prevent rubber substrate, especially arrive 220 /104 ℃ or when higher when temperature.This coating of being instructed provides can prevent the polymer barrier layer that chemical substance or UV enter.When contacting with thermal environment, United States Patent (USP) 6,022,626 polymkeric substance of being instructed can provide the blocking layer of anti-block, ozone and UV irradiation, but lack weather resistance for secular repeated deflection.In case bonding invalid or coating is destroyed by the crack, Degradation will be restarted so.The coating of being instructed among the U.S ' 626 can not provide the heat dissipation performance, and heat is turned to.

The title of Roberts etc. is " Rubber Article Having Protective Coating " United States Patent (USP) 5,314,741 relate to polymeric object, it applies with hydrogenation synthetic rubber or polymkeric substance, this polymkeric substance can obtain by the hydrogenation unsaturated polymer, this unsaturated polymer is polymkeric substance and selectable one or more single ethylenic unsaturated polymers of 1,3-butadiene.

Conventional polymerization stabilizer, UV absorption agent etc. can be coated on the rubber item, yet harsher operational condition need improve aging resistance.

Require further improvement it and stand between lower floor's rubber of repeated deflection or extension fully permanent adhesive in the time limit at life-time service.

Well-known Synolac, urethane and enamel metallic paint have the effect that makes metal produce spot, therefore can be widely used on the automobile body.Base material mainly is metal or rigidity plastics part, so deflection is restricted, paint can produce the crack when perhaps being subjected to seriously clashing into.The metallic coating of band spot is formed on the metal master flat board usually, and 1% or metallic pigment still less disperse with tinting pigment and coat with varnish.Similarly, the calorize spray paint is used to apply furniture, metal products etc., therefore yet the very limited coating of the curable formation ductility of used film former matter is not suitable as coating on the flexible substrate (as the engineering rubber item) owing to flex-crack after the coating and bonding soon reason in use are set.Sheet metal paint can be the outward appearance part provides visual aesthetic feeling, but the hot heat dissipation performance of any degree can not be provided for the usage period at the downward farm labourer's journey of thermal environment rubber product.

Making a kind of method of elastic material corrosion resistant substance is that supercoat is coated on the resilient material.The various corrosion-resistant finishess that applied to flexible substrate (for example elastic substrate) and rigid substrate (for example steel, stainless steel, aluminium or plastics) in the past comprise urethane, polysulphide and fluorocarbon elastomer.When applying to rigid substrate, be found and can provide excellent resistivity oil and fuel such as traditional corrosion-resistant finishes of fluorocarbon elastomer etc.Yet when applying to contain natural rubber and/or diene type elastomerics and mixture at interior flexible resilient base material, fluorocarbon elastomer shows relatively poor resistance to fatigue, relatively poor cold property and relatively poor substrate adherence.

Elastomerics based on low-molecular-weight polyolefine or polyisoolefines comprises low-level Chemical bond functional group (as hydroxyl or amine), and known can being mixed in the polyurethane foam.This elasticity physical efficiency is mixed with the polymeric polyisocyanate of block or block not and by its curing.For example, United States Patent (USP) 4,939,184 disclose by the low-molecular-weight polyisobutylene that contains two or three terminal hydroxyls and polymeric polyisocyanate are reacted in the presence of whipping agent and have prepared flexible polyurethane foam.

The United States Patent (USP) 4,136,219 of Odam relates to high concentrations of toluene diisocyanate is coated to two kinds of methods or process on the vulcanized rubber parts.

United States Patent (USP) 4,670,496 disclose the sidewall striped paint as the coloured marking of any color (as pigment), and preferably metallic particles are placed the solution that contains unvulcanised elastoprene and thiofide.Also crosslinked silicone resin and/or modified EPDM can be placed solution.Promotor is used in fact removing sulphur from the vulcanized rubber base material, thus self-vulcanizing coating rubber.Bonding fully for coating is all had in life-time service rubber item, need after curing, to contain the diene polymer degraded and the embrittlement that surpass 10% remaining degree of unsaturation, and far early than losing efficacy before lower floor's substrate failure.

Once the vulcabond that proposed to comprise free isocyanate groups group in EPA 325 997 is used for solidifying iso-butylene and the multipolymer that modified phenylethylene became that contains uncle's amino alcohol group.EPA325 997 discloses the cure polymer of vulcabond, and its molecular weight is 700～200,000, and exemplified weight-average molecular weight (Mw) and reached 30 approximately, 000 and number-average molecular weight MW (Mn) be about 8,600 mixture, this can measure by the gel permeation chromatogram.

The rubber of the cured with isocyanates of various volumes and tackiness agent just have open in the fifties and the sixties.The isocyanate-reactive functional group that is present in the elastomerics is easy to solidify with the NCO group of isocyanic ester.For example, United States Patent (USP) 6,087,454 disclose the method that is used to prepare solidified volume elasticity body, this method be included in be lower than make isocyanic ester under the temperature of block be not with Mw 60,000 or elastomeric polymer bigger and that comprise hydroxyl and/or amine functional group mix with the polymeric polyisocyanate of block.Mixture is not cured polymeric polyisocyanate being heated to be higher than under the temperature conditions of block.This is reflected under the situation of using blocked isocyanate not and can realizes in room temperature.As United States Patent (USP) 4,939, disclose that available polymeric polyisocyanate solidifies the low-molecular-weight polyisobutylene that comprises hydroxy functional group in the presence of whipping agent in 184.

United States Patent (USP) the 4th, 774 discloses the conjugated diolefine and the α of the curing system that comprises active phenol-formaldehyde resin, the hydrogenated copolymer of alpha, beta-unsaturated nitriles No. 288.Its specification sheets relates to a large amount of vulcanized rubbers, it is characterized in that having good compression to adjust under characteristic, good oil-proofness and the oxidizing condition resistance to oxidation aggressiveness good in being easy to the aged high temperature air, yet not mentioned coating can form on the flexible resilient base material that useful quality can be provided such as natural rubber and polyhutadiene etc.

United States Patent (USP) 5,314,955 disclose a kind of coating composition, and it is made up of following material: (a) hydrogenated acrylonitrile-butadienecopolymer, (b) resol, (c) cure component reaches (d) solvent.This coating has solved and a lot of problems of rubber substrate adherent, comprises resistance to fatigue and fuel resistance.A shortcoming of this coating composition is that it needs high temperature to cure solidified coating and improves it and adjacent metal surface bonding.The high temperature condition of curing of coating needs heat to permeate the goods that whole desire applies.Some parts such as helicopter rotors bearing will by high temperature cure damage, thereby such as in that ' coating described in 955 is inapplicable in practice.It also is expensive aborning that high temperature cures, because its increase time and to the additional processing of part.The flexible resilient base material; comprise natural rubber commonly used and/or diene type elastomerics, still need the supercoat improved, it can have resistance to fatigue in than large-temperature range; base material is shown effective binding property, and can at room temperature solidify (if room temperature is the restrictive factor in the coated article).

United States Patent (USP) 6,156,379 disclose the conventional underlying coating layer-Clear coating on the metallic surface, and contain sheet metal in underlying coating layer.Its novel part is the bright pigment that obtained by the steam-spraying metal-powder.This metallic coating composition is applied on the underlying coating layer, and Clear coating is applied on this metallic coating.The metallic coating composition this means that coating composition only contains flaky pigment and solvent, or contains low amounts of resin or additive basically by bright pigment and solvent composition, thereby makes that pigment weight concentration is 95% or higher.Tackiness agent is used in suggestion, as vinylformic acid, polymeric amide, vinyl chloride copolymer, urethane and polyester.This class tackiness agent is not suitable for the coating on the flexible substrate, because they can not show 100% ductility, in use deflection-crack and adhesion loss will occur.

United States Patent (USP) 5,314,741 disclose a kind of coating composition, and it contains the latex of HI SA highly saturated polymkeric substance, as hydrogenated nitrile rubber, HI SA highly saturated styrene/butadiene copolymers, hydrogenated butadiene polymer or hydrogenated styrene/fourth pyrrole/butadiene terpolymer.This coating is applied on the base material and solidifies there, thereby obtains needed coated article, and it was reported can anti-ozone, oxygen and UV light.The suitable solidifying agent of being instructed is zinc-sulfur curable composition.High temperature is to make these coating curings necessary.In addition, the technician knows that conventional vulcanization system has higher sulphur content and lower vulcanization accelerator content, perhaps half effective vulcanization system has an amount of sulphur and vulcanization accelerator, and be disclosed in for example W.Hofmann, Kautschuk-Technologie, Genter Verlag, Stuttgart, among 1980 page 64 and the 254-255, they have several shortcomings.Conventional sulfuration coating makes the vulcanized rubber with good anti-dynamic pressure (deflection phase) to wearing out and replying very responsive.The semi effcient vulcanization system makes vulcanized rubber have relatively poor anti-dynamic pressure (deflection phase) property usually, but conversely to aging and answer more stable (cf.R.N.Datta and W.F.Helt, Rubber World, 1997,24 pages of August, et seq.).

Invention of the present invention observe utilize sulfur vulcanization chemistries based on bonding impaired to base material of the coating of HI SA highly saturated elastomerics, base material for example is natural rubber and the mixture of diene elastomer, especially vehicle tyre, the flexible pipe etc. that is widely used in the rubber item of said products.The flexible resilient base material; comprise natural rubber commonly used and/or diene type elastomerics; still need the supercoat improved; it can have resistance to fatigue in than large-temperature range; base material is shown effective binding property, resistance to deflection and heat dissipation preferably, thereby can reduce the heat that is transferred on the following polymeric substrate.In the life-time service of engineering product, Yin Re and the pressure and time and the temperature correlation that produce.Any increase that any minimizing of thermal absorption and heat discharge in the elastomerics all can obviously prolong the use/function life-span of product.In order to prolong the useful working life of goods, reduce the thermal absorption speed of engineering elastomer product and improve dissipation of heat speed industrial be important.

Summary of the invention

One embodiment of the invention relate to a kind of non-heat dissipation coating composition of the present invention, and it has long-term resistance to fatigue and variable temperatures, and can have excellent binding property to the flexible resilient base material.This coating is in self-vulcanizing.This coating contains membrane-forming agent polymkeric substance (Tg＜0 ℃), and this polymkeric substance has the ethylenic degree of unsaturation less than 10% before curing.In preferred embodiments, coating composition of the present invention contains (A) carboxylic acidifying hydrogenated acrylonitrile-butadienecopolymer, (X-HNBR) (B) cure component, and the group that it contains at least one isocyanate groups and forms cross-link bond reaches (C) solvent.This coating shows at least 100% curing ductility, and also can keep bonding to base material after long-term weathering.Preferred coating composition contains (a) carboxylic acidifying hydrogenated copolymer solid of 3～30 weight %, it contains the repeating unit that comes from conjugated diolefine, unsaturated nitrile and carboxylic monomer, (b) cure component, another group that it contains at least one isocyanate groups and forms cross-link bond reaches (c) solvent.

The present invention provides a kind of method of coating elastomer moulded product simultaneously, described goods randomly are fixed on the formed metal articles, described method comprises solvent based, be filled with metallic pigment, the elasticity film forming coatings of self-vulcanizing, spraying, dip-coating or brush on the surface of described molded elastomeric goods, described coating contains solidifying agent, the heat conduction particle of at least 10 weight % and film-forming polymer, the Tg of described film-forming polymer is less than 0 ℃, wherein be combined with can with the functional group of the solidifying agent reaction that contains active hydrogen, perhaps described functional group is the group that has active hydrogen, and described polymkeric substance comprises the ethylenic degree of unsaturation less than 10%.

A kind of method of coated substrate is provided on the other hand, comprise apply above-mentioned solvent base coating to the surface of the vulcanized rubber base material of melts combine, dry this coating, and the exsiccant coating solidified under the envrionment conditions around, selectively use heating to be cured.Preferably on around the part of the exposing metal around the elastomerics, also provide coating.The present invention provides coating for the elastomer metal complex body, and it has excellent binding property, has excellent corrosion resistant substance and having excellent anti-deflection-fatigability elastomer substrates in temperature range widely.

Another coating embodiment is opaque, metal filled heat dissipation elastic coating, and it does not contain rubber accelerator and can solidify at ambient temperature.This coating is divided into two components, and mixes when being coated to base material.First component contains Tg less than 0 ℃ flexible film-forming polymer and liquid carrier, be combined with in the flexible film-forming polymer or on it can with the functional group of the solidifying agent reaction that contains active hydrogen, perhaps this functional group is the group that has active hydrogen.Second or another component contain curing agent component, liquid carrier; and (a) by the mean particle size of film forming elastomerics 10～100 weight parts of per 100 weight parts be the thermal conductive metal particle of 2～10 μ m or (b) mean particle size of 20～150 weight parts be 20～60 microns heat conduction particle; wherein curing agent component comprises group and the crosslinked group that has active hydrogen, perhaps this curing agent component comprise can with the group of active hydrogen and crosslinked group reaction.

Brief Description Of Drawings

Fig. 1 applies and uncoated block rubber is exposed to the figure of 120 minutes Nei Neiwen of infrared heat source to the time.

Fig. 2 show the heat conducting coating that is coated to 0.001 ' (0.00040cm) on the natural rubber heat conduction pigment with 0,10 and the photothermal condition of 20phr under internally heated effect to gathering.

Fig. 3 show the heat conducting coating that is coated to 0.001 ' (0.00040cm) on the natural rubber heat conduction pigment with 0,10 and the photothermal condition of 20phr under internally heated effect to gathering.

Fig. 4 show the heat conducting coating that is coated to 0.001 ' (0.00040cm) on the natural rubber heat conduction pigment with 0,20 and the photothermal condition of 50phr under internally heated effect to gathering.

Fig. 5 show the heat conducting coating that is coated to 0.001 ' (0.00040cm) on the natural rubber heat conduction pigment with 0,20 and the photothermal condition of 50phr under internally heated effect to gathering.Fig. 6 shows and uses natural rubber piece that three kinds of different heat conducting coatings apply and uncoated piece in radiant heat internally effect of temperature after 10 minutes.

Detailed description of the invention

Coating disclosed herein is solidified under the environmental condition around, and has solvent resistance and fuel resistance, also has ozone resistance. This coating contains the granular metal filler of film forming polymer and scheduled volume. Film forming agent can be provided at the film that solid state has 90% light transmission at least, and contains after curing and be no more than about 90% degree of unsaturation. This 90+% light transmits into membrane matrix can make the heat of sending from reflexive metallic particles filler have low-loss heat reflectivity and heat transmission property.

Coating is so that significantly reflection occurs from the conductive particles of lower finishing coat in heat, and coating permanent adhesive and compression resistance or anti-around crack or become fragile. This coating can with rubber, TPE and plastic products (such as pneumatic tyre, non-pneumatic tyre, flexible pipe, belt, frame, covering, the deflecting plates etc.) good bond of moulding, when particularly being used near hot goods, but during such as the industrial element of cluster engine or other dissipation of heat. The anti-damage of coating and the wearing and tearing of solidifying.

Solidify under the environmental condition around after coating is coated on the flexible substrate, and dry film thickness (DFT) is about 0.5～20mils (mil) (12.7 μ m-508 μ m) usually. Depend on selected curing agent and film forming agent, use or organic carrier are used the liquid form of coating with basically anhydrous solution or aqueous dispersion. The applicability that depends on condition of cure, but under heating condition, use or do not use simultaneously the luminous energy rapid curing. But the rubber industry product that the invention has the advantages that the final assembling with obvious caloic of ambient cure does not need to heat when realizing curing of coatings. The curing physical property of the coated film of metal-filling is included in widely (40 ℃-150 ℃) anti-deflection-fatigue in the operating temperature range, at long term exposure degradation resistant under high temperature and ozone, and the flexible resilient base material is had the cohesive of excellence. Coating composition has the ductility above about 50% after the cold curing, and non-warping (recovering fully), more typically be to prolong 100%, 200% or 300%, and can not damage cohesive also do not have crack, distortion or distortion and separate with elastomer substrates. The heat reflection surface keeps its integrality to repeat deflection, and it is complete so that heat dissipation surface to be provided that heat conduction particle keeps. Coating composition contains at least a film forming agent polymer or prepolymer, and it contains when not using the sulfur vulcanization chemistries material functional group as the cure site of curing agent. Per 100 parts film forming agent polymer uses 5～100 (phr) parts curing agent usually. According to the average-size of metallic particles, the below lists thermal conductive metal particle amount by weight.

This paper is the example of the applicable film forming polymer that contains reactive hydrogen functional group openly. Also disclose contain can with the polymer of the functional group of the curing agent reaction that contains reactive hydrogen. The film forming polymer that is applicable to this paper comprises ethane-acetic acid ethyenyl ester, SB-diblock copolymer, SBS-and the SIBS-triblock copolymer of alpha-olefin elastomer, conjugated diene elastomers, hydrogenated diene elastomer, fluoroelastomer, carboxylic acid second diester, ethylene-propylene-diene elastomer, functionalization and hydrogenated form thereof, acrylic rubber, and polyurethane also is suitable for. By in polymerization, using comonomer or can in film forming agent, providing functional group with conventional means by rear polymerization well known in the art. Chemical crossbond between curing agent and film forming polymer is ambient cure of the present invention, base material is bonding and the substantive characteristics of durability.

In preferred embodiments, hydrogenated acrylonitrile-butadienecopolymer (A) (HNBR of functionalization), solidifying agent (B) that coating composition of the present invention contains functionalization reach (C) organic solvent, this solidifying agent contains at least one isocyanate groups, preferably polymeric polyisocyanate or isocyanic ester-function prepolymer or isocyanato silanes or contain isocyanate groups and form at least one multi-functional compounds, oligopolymer, the prepolymer of the group of cross-link bond.Importance of the present invention is that the solvent of coating composition can be water base or alkyl.Aqueous coating can make the consumption of contained volatile organic compounds (VOC) reduce.

Coating of the present invention can be coated on the elastomer substrates before or after the vulcanized elastomer base material.On the one hand, the invention provides a kind of method of coated substrate, comprise applying coating to unvulcanized rubber substrate surface, and under envrionment temperature or high temperature dry this coating, thereby solidify this coating.

In another aspect of this invention, a kind of method of coated substrate is provided, its comprise the steps: applying coating to itself optionally with the surface of metal ingredient adherent vulcanized rubber base material, dry this coating, and the exsiccant coating solidified under the envrionment conditions around, selectively use heating, light or radiation to be cured.When needing, preferably on around the part of the exposing metal around the elastomerics, also provide coating.

The invention provides the external coating (EC) of moulding or molded polymeric object, as elastic material and elastomer metal complex body, this external coating (EC) has excellent binding property, excellent erosion resistance, excellent heat-resisting characteristic of concentration and the anti-deflection-fatigability with excellence to elastomer substrates in the temperature range widely.

Coating can form by the mixture of two kinds of liquid portions when being coated to base material.Part A contains the liquid solution or the dispersion of functionalized polymer, and part B contains LCM.When this two portions mixed, envrionment temperature curable embodiment common storage period was 30 minutes to 1 hour.The curable coating mix of part A and B contains 2～20% amount of solid.Viscosity can assign to control according to selected one-tenth, and less than 20,000cps (Brookfield), thus coating can be by spraying, brushing or dip-coating.

The polymers function method

Can provide functionalization used herein elastomeric membrane-forming agent by several schemes, as copolymerization and by in the method that in polymkeric substance, makes the film-forming polymer modification after the polymerization in conjunction with various functional groups.Term " functionalization " refers to as the band active hydrogen of ethylenic unsaturated comonomer part part perhaps to be had compound bearing active hydrogen by grafting connection, post polymerization by copolymerization.Comonomer or graft compound become covalently bound polymer architecture, and have can with the group of ambient temperature curing agent reaction.

The routine techniques that use will be added in the functional group of active hydrogen on the polymeric NOT-function elastomerics can be prepared into film, as being in the solution when elastomerics or during molten state, the compound of band functional group is changed into suitable functional group's precursor or directly reacts realization in conjunction with suitable precursor free radical by " alkene ", thereby allylic hydrogen is transferred on the enophile reagent, between two unsaturated end groups, connect then, or realize by the free radical addition of in molten state or solvent dilution, passing carbon-to-carbon double bond.Yet when polymkeric substance was in molten state, use can provide the device (as forcing machine) of high mechanical shearing can influence goal response with the functional group that transforms in conjunction with desire or directly in conjunction with suitable precursor free radical.In conjunction with the functional group that can change into suitable precursor or directly in conjunction with the precursor free radical can be by metallization, carry out with suitable electrophilic reagent reaction then, on the other hand, preferably can realize this combination with the polymkeric substance in the solution.

In these several methods availalbes in conjunction with functional group or functional group's precursor, the method as alkene reaction of body unit elastomer polymer coupling simultaneously minimum before each binding site is in conjunction with single functional group or functional group preferably, and comprise the method for metallization back and electrophilic reagent reaction.When with the functional groups of the suitable precursor of one-tenth to be transformed during to elastomerics, usually functional group change into the precursor free radical also polymkeric substance in solution, realize.Usually, be used for all can influencing these reactions or conversion at any known solvent of this elastomer polymer of solution preparation.

Known multiple post polymerization functionalization technology all can prepare the available NOT-function addition polymer that has link coupled crosslinking curing position in the present invention.Hydroxyl is to be used for suitable functional group with solidifying agent generation crosslinking reaction used herein.United States Patent (USP) 4,118,427 disclose the curable liquid hydrocarbon prepolymer that contains hydroxyl, it is by ozonize high-molecular weight saturated hydrocarbon polymer (as polyisobutene or ethylene-propylene rubber), reduce the material (for example by use reductive agent diisobutyl aluminium hydride) of ozonize then, thereby form the above-mentioned liquid prepolymer that contains hydroxyl, its molecular weight is low more than original copolymer.

(A) comonomer of functionalization

Curable film-forming polymkeric substance used herein can prepare by the comonomer of copolymerization elastomerics formation monomer and functionalization, or prepares by polymkeric substance is reacted with monomer that contains functional group or reactive compounds.Behind the binding reactive group by making cure component as herein described react cure polymer.Curing utilizes linking agent and the band functional group of active hydrogen or the reaction of reactive with active hydrogen group, the functional group of band active hydrogen or reactive with active hydrogen group can with multipolymer on or the respective reactivity functional group that is suspended on the multipolymer crosslinked.Can introduce the comonomer that has functional group easily in the polymerization process of membrane-forming agent polymkeric substance, this point is habitually practised.Various free radical addition copolymerizations, negatively charged ion addition polymerization, free radical grafting, transposition grafting, hydrolysis crosslinking technology are being known in the art.The polymkeric substance or the multipolymer that contain functional group comprise with its main component being the polymkeric substance of feature, as the fluoroelastomer of alpha-olefin elastomerics, diene elastomer, hydrogenated diene elastomerics, functionalization, crosslinked alpha-olefin copolymer elastomerics, acrylate or the methacrylic ester acrylate copolymer and the carboxylic acid second diester etc. of functionalization.

Preferred rubbery copolymer elastomerics example includes but not limited to the alkene elastomerics of anionoid polymerization.The example of the alkene rubber of anionoid polymerization comprise ethylene-propylene rubber, ethylene-propylene-diene monomer rubber, polyisobutene or " isoprene-isobutylene rubber " or any other selectively with the isoolefin polymer of conjugated diolefine (as isoprene) copolymerization, selectively contain and reach 30 weight % or α, the polymkeric substance of β-ethylenic unsaturated nitrile and/or styrene copolymerized monomer (as vinylbenzene and/or alkyl-substituted styrene) etc.Particularly preferred elastomerics comprises isobutylene-isoprene copolymer, iso-butylene-p-methylstyrene multipolymer etc.

Suitable suspension active hydrogen functional group can be by forming amino-functionalization the method for ethylene propylene diene monomer rubber (EPDM) provide, as United States Patent (USP) 4,987,200 described methods.Similarly, the high molecular isobutylene copolymers with hydroxyl functionalization can use the method preparation described in the EPA 325 997.In addition, any commerce available and contain usually be low to moderate 0.5～2.0 mole of % halogen the halogenated isobutylene based polyalcohol can with the combination of alkylamine or amino alcohol, to obtain amine or hydroxy functional group respectively.

Weight-average molecular weight be 1000～200,000 and the elastomerics that contains the functionalization of hydroxyl and/or amine functional group be known.The polyisobutene of terminal hydroxy group can be introduced hydroxyl the end position of the iso-butylene of cationoid polymerisation by dehydrochlorination, hydroboration, chlorine monoxide end group polyisobutene and carry out the routine preparation.It is known obtaining the poly-rare method of isobutyl of chlorine end group by the cationoid polymerisation isobutylene monomer.Referring to Faust and Kennedy " Living Carbocationic Polymerization:III.Demonstration of the Living Polymerization of Isobutylene; " Polym.Bull.15:317-23 (1986) wherein discloses the activated carbon cationic polymerization of iso-butylene and has come the quenching activity reaction with methyl alcohol and other reagent such as amine.

At United States Patent (USP) 5,350, living polymerisation process is disclosed in 819,5,169,914; The preferred method that is prepared into membrane polymer is disclosed in 4,910,321.For example use iso-butylene to realize that the general condition of living polymerization comprises: (1) initiator, as tertiary alkyl halogen, tert-alkyl ether, tertiary alkyl ester etc.; (2) Lewis acid coinitiator, it contains the halogenide of titanium, boron or aluminium usually; (3) proton scavengers and/or electron donor; (4) solvent considers that according to known cationoid polymerisation system and monomer the Lewis acid and the monomer of selection selected its specific inductivity.

The end functionalized polymer

Active hydrogen group or can be added to the end of membrane-forming agent polymkeric substance used herein with the group of active hydrogen group reaction.United States Patent (USP) 5,448,100 disclose the distant pawl polyisobutene of sulfonated, it can cause the carbocationic polymerization of iso-butylene and Lewis acid to form polymkeric substance by " inifer " (initiator-transfer agent), use the terminal quencher of acetyl sulfate ester then, and precipitate with the steam desorption or with methyl alcohol, ethanol, Virahol or acetone and to prepare.Polymerization is preferably carried out in chlorinated solvent, most preferably is to carry out in solvent mixture, as methylene dichloride, methyl chloride or contain the aliphatics or the alicyclic compound of 5～10 carbon atoms.Lewis acid for example can be boron trichloride or titanium tetrachloride or other metal halide (comprising tin tetrachloride, aluminum chloride or aluminum alkyls).Terminal quencher preferably takes place under-90 °～0 ℃ temperature, most preferably takes place under the decomposition temperature of polymerization temperature or title complex.The mol ratio of polyisobutene and acetyl sulfate ester is preferably 1: 1 or is bigger.

Membrane-forming agent polymkeric substance such as polyisobutene etc. can contain hydroxyl and/or the alkoxyl group that end has silane group.These can obtain by following known route: make the polyisobutene polymkeric substance dehydrohalogenation that contains tertiary carbon-cl radical, then with ethylenic unsaturated silane generation addition reaction.For example, the chloroprene rubber that contains tertiary carbon-chlorine key can react to obtain containing the polyisobutene of unsaturated group with allyl trimethyl silane, then in the addition condition of catalyst made from platonic and the silicon hydrocarbon compound reaction of following general formula:

R wherein ²Be hydrogen atom, contain the alkyl of 1～20 carbon atom, the aryl that contains 6～20 carbon atoms, the aralkyl that contains 7～20 carbon atoms or formula (R ') ₃Three organosiloxies shown in the Si-(wherein each R ' represents hydrogen atom independently or contains the replacement or the unsubstituted alkyl of 1～20 carbon atom), each X is representation hydroxy or known hydrolysable group independently, and a is 0,1,2 or 3.Selectively, can use polymeric silicon hydrocarbon-end group siloxanes.Known silicon hydrocarbon compound comprises halogenated silane, as trichlorosilane, dimethyl dichlorosilane (DMCS), dimethylchlorosilane, diphenyl dichlorosilane; Organoalkoxysilane is as Trimethoxy silane, triethoxyl silane, methyldiethoxysilane, methyl dimethoxysilane, phenyl dimethoxy silane etc.; Acyloxy silane is as methyl diacetoxy silane, diethylamino phenyl acyloxy silane etc.; And ketoxime silane, as two (DMKO) methyl-monosilane, two (cyclohexyl ketoxime) methyl-monosilane etc.Its preparation method for example is disclosed among Japanese Kokoku Publication Hei-4-69659, JapaneseKokoku Publication Hei-7-108928, the open Sho-64-22904 of Japanese Kokai Publication Sho-63-254149, Japanese Kokai and the Japanese PatentPublication2539445.

The hydrogenated diene elastomerics of functionalization

The hydrogenated diene multipolymer that is suitable in this article as the functionalization of film-forming polymer is the solvent polymer soluble, and preferably its molecular weight is about 50,000 or higher, be more typically 200,000～500,000, and contain and be no more than 10% conjugated diolefine segment by weight.These polymkeric substance have significant difference with the functionalization oligopolymer of liquid state such as the liquid polymer (for example ATBN and CTBN) of reactive end group functionalization.The unsaturated functionalized polymer that is used to prepare the hydrogenated coatings polymkeric substance generally comprises one or more unconjugated ethylenically unsaturated monomers unit of the conjugated diene monomeric unit of 50～85 weight %, 5～50 weight % and has the function comonomer of 1～20 weight % of reactive crosslink sites or the compound that grafting connects.Preferred conjugated diene monomeric unit is derived from 1, the 3-divinylic monomer, unconjugated ethylenically unsaturated monomers unit is derived from one or more and is selected from following ethylenically unsaturated monomers: undersaturated acrylate, methacrylic ester, nitrile (as vinyl cyanide and methacrylonitrile), monovinyl aromatic hydrocarbon (as vinylbenzene and ring-alkylated styrenes), vinylidene comonomer.Preferably there are not divinyl aromatic hydrocarbons (as Vinylstyrene) and two alkenyl fragrant substances (as di isopropenylbenzene).Other comonomer comprises alkyl (methyl) alkyl acrylate (as methyl acrylate, methyl methacrylate, ethyl propenoate, butyl acrylate, 2-EHA or methacrylic ester), vinyl pyrimidine, vinyl acetate (as vinyl-acetic ester).Preferred function comonomer is selected from undersaturated carboxylic acid and ester thereof, as vinylformic acid, methacrylic acid, butenoic acid, methylene-succinic acid and toxilic acid.Its glass transition temperature of diene elastomer membrane-forming agent of functionalization can not surpass-10 ℃, preferably is lower than-25 ℃, thereby can have acceptable anti-deflection-crack/deflection-fatigability in the coating that heat conduction particle is filled.

By the chain method for splitting can contain-form the C-terminal group on the diene elastomer high polymer of C-CH=CH-C-type degree of unsaturation, wherein form the rubber ozonide, and use superoxide or peracid that the aldehyde end group is oxidized to carboxyl.Selectively, terminal hydroxy group can utilize shortening or reductive agent (metal hydride or hydroborate etc.) to form by reduction technique on the rubber ozonide.For example referring to English Patent 884,448.Similarly, United States Patent (USP) 4,118,427 disclose the curable liquid hydrocarbon prepolymer that contains hydroxyl, it can be by ozonize high-molecular weight saturated hydrocarbon polymer (as polyisobutene or ethylene-propylene rubber), and the material of ozonize of reducing then obtains, for example by using reductive agent (preferred diisobutyl aluminium hydride), form the above-mentioned liquid prepolymer that contains hydroxyl, its molecular weight ratio original copolymer is low.

By coming the modification film-forming polymer can obtain useful membrane-forming agent in the present invention in conjunction with mercaptoalcohol or mercapto-carboxylic ester graft compound.Suitable hydroxy thiol and/or mercapto-carboxylic ester contain hydroxyl.The HS-R-OH compound comprise those wherein R be straight chain, side chain or ring-type C ₁-C ₃₆The compound of alkyl, wherein alkyl is selectively replaced by 6 hydroxyls nearly, maybe can insert nitrogen, oxygen or sulphur atom.The mercapto-carboxylic ester that is suitable for for example is HS-(CHR ₂) N-(C (O) OR ₃OH) _m, R wherein ₂Be hydrogen or C ₁-C ₃₆Alkyl, R ₃Be straight chain, side chain or ring-type C ₂-C ₃₆Alkyl, wherein alkyl is selectively replaced by 6 hydroxyls nearly, maybe can insert nitrogen, oxygen or sulphur atom, preferably-and OH is main, and n is 1～5 integer, and m is 1～2 integer.

Preferred hydroxy thiol is mercaptoethanol, 1-sulfydryl-3-propyl alcohol, 1-sulfydryl-4-butanols, the low polyethylene oxide of alpha-mercapto-ω-hydroxyl, for example copolyether of alpha-mercapto-ω-hydroxyl ethohexadiol or corresponding ethylene oxide/propylene oxide.The low polyethylene oxide of mercaptoethanol and alpha-mercapto-ω-hydroxyl is preferred.The mercapto-carboxylic ester that preferably the contains hydroxyl ester that to be Thiovanic acid, thiohydracrylic acid and sulfydryl butyric acid become with N methyldiethanol amine with ethylene glycol, propylene glycol, butyleneglycol, Diethylene Glycol, triethylene glycol, TEG, ethohexadiol, dipropylene glycol, tripropylene glycol, four propylene glycol.The corresponding ester that preferred especially Thiovanic acid is become with the 3-thiohydracrylic acid.Comprise the polymkeric substance that contains iso-butylene, chloroprene, polyhutadiene, iso-butylene/isoprene, butadiene/acrylonitrile, butadiene-acrylic acid ester copolymer, S-B multipolymer, divinyl-vinylidene chloride-acrylate type multipolymer with the basic polymkeric substance of elastomerics membrane-forming agent of the suitable type of sulfhydryl compound reaction, as long as its degree of unsaturation is 10% or littler.United States Patent (USP) 6,252 discloses the method in conjunction with sulfhydryl compound in 008, and this method is applicable to function membrane-forming agent polymkeric substance, is incorporated herein this patent as a reference.Rubber contains the one-tenth key hydroxyl of 0.1～5 weight %.Solution polymerization also contains by U.S.6, and method described in 252,008 should be in conjunction with its molecular weight of elastoprene of hydroxyl can obtain containing 5～15% solid diluting solns, and is suitable for spraying, brushing or dip-coating, as 10,000～200, and 000M _n(gel permeation chromatography).

Other is known for example to be addition reaction with formaldehyde with OH group the technology in the film-forming polymer used herein of being added to, with reaction of carbon monoxide, hydrogenation then, hydroboration, hydrolysis then.It is appropriate means that the silane that use contains the ethylenic unsaturated group carries out copolymerization.Representational silane comonomer comprises vinyl silanes or the allyl silicane that has reactive silicon group.The example that can mention comprises vinyl trichloro silane, the vinyl dimethyl dichlorosilane (DMCS), vinyl-dimethyl base chlorosilane, the vinyl-dimethyl methoxylsilane, the divinyl dichlorosilane, divinyl dimethoxy silane, allyltrichlorosilane, the allyl methyl dichlorosilane, allyldimethylcholrosilane, the allyl dimethyl methoxylsilane, the diallyl dichlorosilane, diallyl dimethoxy silane, γ-methacryloxypropyl trimethoxy silane, and γ-methacryloxypropyl methyl dimethoxysilane.

Below with the diene elastomer of functionsization, the multipolymer of itself and nitrile is the embodiment of the most preferred membrane-forming agent of the present invention.The butadiene acrylonitrile copolymer of functionalization can provide useful film characteristics, as low temperature resistance to deflection, oil-proofness, fuel resistance, solvent resistance, good wear resistance and water tolerance.

The present invention most preferably is that the hydrogenated nitrile rubber (HNBR) with functionalization is implemented.HNBR can provide the cross-linked coating method for compositions with the reactive functional groups functionalization, and can make with elastomer substrates bonding and reach essential level.As can not be fully bonding with elastomer substrates, coating will show too early deflection-crack and/or layering so.The functional group of HNBR can be divided into usually contains active hydrogen group, ethylenic unsaturated group or hydrolysable group.

Can be cured by adding crosslinked components utilising moisture as herein described, heat (infrared, heat), UV radiation or electron beam irradiation.Depend on the reactive functional groups that is attached in the diene copolymers.The HNBR embodiment of some functionalization hereinafter described can add linking agent and carry out self cure, and all suitable crosslinked compositions among the HNBR that is attached to functionalization that can both utilize are cured, and crosslinked composition for example is but is not limited to dinitrosobenzene, ZnO, γ-POM, resol resin, multifunction amine, polymeric polyisocyanate, polyacrylic ester, Dyhard RU 100, dicarboxylic acid imines and formaldehyde (or UF, MF) resin.

The HNBR of functionalization can prepare by several different methods well known in the art.Functional group can be by following method combination: utilize the compound that contains functional group that contains the comonomer of functional group or utilize grafting to connect, make the NBR functionalization by transposition, then hydrogenation through the NBR of modification to obtain the HBNR of functionalization, or make NBR and methylolated phenol reactant, then hydrogenation through the NBR of modification to obtain the HBNR of functionalization.

In curable radiation coating composition, the functionalization HNBR that contains band active hydrogen functional group is preferred crosslinkable film.The unsaturated group that exists in NBR (being vinyl olefins and disubstituted olefin, nitrile) can provide reaction site, can be connected with reactive functional groups on it, and is used for further crosslinked, post polymerization thing functionalization and graft reaction.These reaction site can change by catalysis or on-catalytic chemistry.This change can be introduced the active hydrogen functional group of any number, obtains epoxide as carrying out epoxidation in the alkene position.Be easy to be converted into other functional group by the ring-opening reaction epoxide.For example,, glycol ether can be got, alcohol can be obtained with carbanion or hydride open loop with alkoxide or phenates open loop by getting ethylene glycol with alkali open ring.In addition, those skilled in the art use chemical process can make epoxide become crosslinkable site.Many other functional groups can be by main chain alkene reaction bonded: hydroformylation (aldehyde, alcohol, carboxylic acid), hydrocarboxylation (carboxylic acid), hydrogenation and esterification (ester), hydrogenation silylanizing (silane), hydrogenation amination (amine), halogenation (halogen), chlorosulfonylation (chlorine, sulfuric acid), hydroboration (borine, alcohol, amine).The example of this conversion is by Tremont (McGrath, M.P.; Sall, E.D.; Tremont, S.J. " Functionaliization of Polymers by Metal-MediatedProcesses, " Chem.Rev.1995,95,381) disclose.The elastomeric nitrile group of NBR also can change into acid amides by make itself and alcohol reaction in acid catalyzed process, changes into carboxylic acid by hydrolysis again.

Also can carry out crosslinked by adding crosslinked composition, moisture, heat, UV radiation or electron beam irradiation.Depend on reactive functional groups that is connected with HNBR and uses thereof, suitable crosslinked composition can join among the HNBR of functionalization, as dinitrosobenzene, ZnO, γ-POM, resol resin, multifunction amine, isocyanic ester, acrylate and Dyhard RU 100.Particularly preferred crosslinked composition is those compositions that are used to obtain with the elastomeric article excellent bonds as known in the art.These compositions comprise DNB, ZnO and QDO, and can add and be used for the binding property of enhancement function HNBR and various elastic materials.

The reactive functional groups that is added on the diene elastomer includes but not limited to as the close diene reagent of phenolic hydroxyl group, aliphatic hydroxyl, amine, isocyanic ester, epoxy group(ing), acrylate, silyl ether, silyl chloride, acid anhydrides, maleimide and Diels-Alder (Diels-Alder).

Being used for the suitable cure component of curing reaction and auxiliary agent is known in the existing document and the patent of the bonding and coatings art that is used for solidifying R.F. of the present invention.For example when the functional group on the polymkeric substance was phenol, isocyanic ester, dicarboxylic acid imines, formaldehyde source and resol resin were suitable solidifying agent, and it can be used for the HNBR of crosslinked phenol functionalization.Similarly, the HNBR of amino-functionalization can carry out crosslinked with isocyanic ester or dicarboxylic acid imines, formaldehyde source and resol resin.The HNBR of epoxy group(ing) functionalization can carry out crosslinked and solidifies with suitable amine and Dyhard RU 100 composition, is known in the bonding and coatings art of this epoxy glue.The HNBR of isocyanate functionization makes us interested especially, because it can be undertaken crosslinked or solidify by moisture or the solidifying agent (as amine or polyol) that adds other.The adding isocyanic ester is special needs as the part of HNBR, because this amount that will reduce free monomer thereby reduce volatile isocyanate, and reduce the health and safety problem that it is in the news.Potential isocyanate function HNBR can prepare by the HNBR (or NBR) of amino-functionalization and the reaction of diaryl carbonate, thereby obtains the HNBR (or NBR) of functional polyurethaneization.The thermo-cracking of urethane can form the HNBR (or NBR) of isocyanate functionization (for example referring to Kothandaraman.K.; Nasar.A.S. " The Thermal Dissociation of Phenol-Blocked TolueneDiisocyanate Crosslinkers " .J.M.S.-Pure Applied Chem.1995, A32,1009; Wicks.D.A.; Wicks.Z.W. " Blocked isocyanates III:Part A.Mechanisms and Chemistry " .Progress in Organic Coatings 1999,36,148; Mohanty, S.; Krishnamurti, N. " Synthesis and thermal Deblocking ofToluene Diisocyanate Adducts, " Eur.Polym.J.1998,34,77).The HNBR of maleimide functionalization can be by adding radical initiator or being undertaken crosslinked by Michael (Michael) addition reaction.Maleimide is known linking agent.Acrylic ester functionalized HNBR can pass through free radical, UV and electrocuring.The anhydride functional group can use the composition in amine or the acid anhydrides-epoxy glue field to be cured.Silyl ether and chlorosilane use the moisture-curing embodiment under the room temperature.The Diels-Alder affixture is self cure or passes through to add metathesis catalyst and solidified.

The above-mentioned details that is used for the method on the film forming elastomerics that functional group is added to is the method for fusion that is fused into the film elasticity body, it contains multi-functional grafting and connects material, as multi-functional acrylate, the polyhutadiene of maleinization and the metal-salt of bifunctional acrylate.For example olefin elastomer such as EPDM can grind with 5 parts of acid scavengers (as zinc oxide), 1 part of stearic acid, antioxidant and superoxide on two rollers grind, and then 5～10 parts of multi-ethylenical unsaturated compounds (as the liquid polybutadiene or the dizinc acrylate resin of three vinylformic acid trishydroxymethyl propyl ester, maleinization) are added on the flux roll.

The HNBR of functionalization can be by transposition, then hydrogenation through the NBR of modification obtaining the HBNR of functionalization, and (2) NBR and methylolated phenol reactant, then hydrogenation through the NBR of modification to obtain the HBNR of functionalization.

The novel method of binding reactive functional pendant groups on the NBR elastomerics (as carboxyl, acid anhydrides, hydroxy functional group) is as follows:

Utilize the olefin metathesis chemistry to realize any suitable unsaturated membrane-forming agent polymkeric substance, the especially direct functionization of NBR used herein.Here the two keys of alkene C=C and catalyzer and monomer reaction.Metathesis reaction under olefin metathesis catalyst must can the catalysis nitrile functionality exist.Monomer can be alkene, alkene or the α that olefin metathesis reactions (for example ring-opening metathesis polymerization [ROMP], cross metathesis, open loop cross metathesis and acyclic dienes metathesis polymerization [ADMET]) can take place any ring, ω-diene.These monomer derived are in the functional group that has group (for example carboxylic acid, acid amides, ester, acid anhydrides, epoxide, isocyanic ester, silyl, halogen, Diels-Alder diene and close diene reagent etc.), thereby cure site are provided or make polymkeric substance have new character for the secondary crosslinking reaction of cured film.From the kinetics angle, metathesis catalyst is possibility attack vinyl C=C key at first, yet because their low consumptions in the HNBR multipolymer also may the two keys of the emulative main chain C=C of attack.Thisly may cause the molecular weight and molecular weight of NBR to the attack of main chain degree of unsaturation, but by the higher NBR of use: catalyst levels can make this degree minimum.Use for example above-mentioned catalytic hydrogenation method reduction behind the NBR of modification, obtain reactive through the HNBR of modification polymkeric substance.The solidifying agent of this polymkeric substance chresard, selection or extra power (UV or electron beam) are carried out crosslinked.The particularly preferred advantage of transposition katalysis is in water or solvent under mild conditions that it can provide and introduces the unique way of reactive functional groups to the NBR.So NBR latex can carry out modification with reactive functional groups, and can not make the latex instability because of metathesis catalyst.This feature makes the NBR polymkeric substance of various commercial known solution or water dispersion and latex (aqueous-based polymers) can carry out functionalization, and hydrogenation makes the HNBR of functionalization then.

Hydrogenant proton group end capping diene polymer

Hydrogenant hydroxyl or carboxy blocking diene polymer can use separately or mix with the film-forming polymer of different high molecular (10,000Mn and more than) and use, and also are suitable in radiation coating of the present invention and are curable membrane-forming agent.Basically saturated polyhydroxylated polydiene polymers is known and can obtains from commercial.These are conjugated diolefines of anionoid polymerization, as divinyl or isoprene, and use lithium initiator, use the OH group end capping.These methods are disclosed in United States Patent (USP) 4,039,593; Re.27,145; In 5,376,745, be incorporated herein the preparation that these patents disclose polyhydroxylated polydiene polymers.This polymkeric substance can use dilithium initiator preparation, prepares this compound as reacting by the diisopropyl benzene that makes 2 moles s-butyl lithium and 1 mole.Can be in the solvent of forming by the ether of the hexanaphthene of 90 weight % and 10 weight % the polymerization divinyl.Two kinds of initiators and monomeric mol ratio have determined the molecular weight of polymkeric substance.This polymkeric substance ethylene oxide-capped with 2 moles, and with 2 moles methyl alcohol end-blocking to obtain dihydroxy polybutadiene.The hydroxylated polydiene polymers of hydrogenation makes all basically carbon-carbon double bonds all by saturated.Hydrogenation can utilize known method to carry out by those skilled in the art, is included in as United States Patent (USP) 5,039, and 755 described catalyzer (as Raney nickel, precious metal such as platinum etc., soluble transition-metal catalyst and titanium catalyst) carry out hydrogenation under existing.Suitable polyhydroxylated polydiene is that the trade mark that the Shell Chemical Company from the U.S. buys is KRATON LIQUID ^POLYMERS, HPVM 2200 series product, also the trade mark that can buy from ATOCHEMIE is POLYBD ^Product.Be suitable for without limits and hydrogenation hydroxyl butadiene polymer blended high-molecular weight polymer, comprise for example above-mentioned carboxy-modified chlorinatedpolyethylene, chlorinatedpolyethylene, Polyglycol 166-450, ethylene-acrylic acid copolymer, SBR, SBS, nitrile rubber (NBR), SIBS, EPDM, EPM, polyacrylic ester, halogenated polyisobutene and poly(propylene oxide).Limit the weight ratio of liquid hydrogenant polybutadiene polyol and high-molecular weight membrane-forming agent, make total degree of unsaturation per-cent in the mixture less than 10%.Therefore if the mixture of hydrogenant polydiene polyvalent alcohol is made up of unsaturated superpolymer (as SBR, NBR etc.), the ratio of unsaturated polymer will be limited to and remain total saturation ratio and be at least 90% so.Chlorinatedpolyolefins through modification can comprise those that usefulness is sour or anhydride modified.Some example through the chlorinatedpolyolefins of modification is disclosed in United States Patent (USP) 4,997,882 (1 hurdle, 26 row～4 hurdles, 63 row); 5,319,032 (1 hurdle, 53 row～2 hurdles, 68 row); And 5,397,602 (1 hurdle, 53 row～2 hurdles, 68 row), be hereby incorporated by.By initial polyolefine weight, the cl content of chlorinatedpolyolefins is preferably about 10～40%, more preferably about 10～30%.Through suitable example of chlorinatedpolyolefins of modification is to be about chlorinatedpolyolefins through modification of 10～about 30% by polyolefine weight cl content, and it can not neutralized by amine, and acid number is about 50～about 100.

The hydrogenant segmented copolymer

Being suitable for membrane-forming agent of the present invention is hydrogenant styrene-butadiene-styrene block copolymer, hydrogenated styrene-isoprene-styrene block copolymer, it is to utilize aforesaid method through chlorinated polyethylene modified, thereby can have on segmented copolymer and the interactional curing of solidifying agent functional group.Some elastic block copolymer that contains carboxyl can commerce obtain.Segmented copolymer with degree of unsaturation can carry out hydrogenation with known method for hydrogenation, comprises the method for reference.

The phenol functional elastomer

Phenol functional group functionalization HNBR can be by mixing methylolated phenol and NBR, and hydrogenation realizes through phenol-modified NBR intermediate then.Methylolated phenol can pass through various documents [A.Knop and L.Pilato with NBR and NBR multipolymer, " Peenolic ResinsChemistry and Applications and Performance " Springer-Verlag, New York1985, Chapter 19 page 288-297] chemical reaction of report forms covalent linkage.

Various known isocyanic ester-reactive functional groups can be added in the elastomerics film-forming polymer of functionalization.Above-mentioned carboxyl-functional, hydroxyl functionalization and the easiest use of elastomerics amino-functionalization.The comonomer of functionalization such as the comonomer of carboxyl-functional are easy to form the multipolymer of carboxylic acidifying hydrogenated nitrile rubber.Be to realize that the present invention, the hydrogenated nitrile rubber of functionalization are restricted to the polymkeric substance of the compound that contains at least one diene monomers, nitrile monomer and have functional group (as comonomer or contain graft compound or its combination of functional group).When using shortenings HNBR,, should be appreciated that this term refers to contain the rubber that diene monomers except that 1,3-butadiene reaches the comonomer except that vinyl cyanide unless refer else.Be important to note that the also polymerization or be grafted on the diene monomers together of other monomer to form the HNBR of functionalization.Other monomer for example can provide at least one to promote crosslinked functional group.

Phenol functional group functionalization HNBR can realize that through adding methylolphenol or ether derivant catalysis is carried out in selectively available suitable Lewis acid under heating condition by using undersaturated unhydrided polymkeric substance or partially hydrogenated XHNBR polymkeric substance (the hydrogenation level of 80-97%).Preferably on the methylolphenol compound, have ether block group, reduce reacted hydrogenation thereby be beneficial to.Addition can form by the ester of nitrile or carboxyl and carry out, or utilizes above-mentioned addition in allylic positions.Preferably, the metathesis reaction that has the ethylenically unsaturated compounds of phenolic groups can carry out in solvent or water.Selectively, have methylolated phenyl ether or phenol alkene can with NBR transposition, hydrogenation then.The NBR of phenol functionalization is hydrogenated subsequently.Hydroxymethylation can utilize the NBR of phenol functionalization or HNBR and formaldehyde to carry out, thereby produces methylolated phenol functional group in NBR or HNBR.Methylolated phenol can form covalent linkage by the chemical reaction of reporting in the document with NBR and NBR multipolymer.Referring to A.Knop and L.Pilato, " Phenolic Resins Chemistry and Applications and Performance " Springer-Verlag, New York 1985, Chapter 19 page 288-297.Below structure iron show with the representational compound that has phenol and carry out functionalization.

Although any methylolated phenol may be combined with NBR, the phenol of monomethylolization is particularly preferred.The phenol of monomethylolization is combined the NBR product that can obtain stable phenol functionalization with the NBR polymkeric substance.After phenol-modified, obtain stable according to method well known in the art (for example catalytic hydrogenation) hydrogenation through phenol-modified HNBR multipolymer.The HNBR multipolymer of phenol functionalization can be crosslinked with the multiple known linking agent that is used for resol, and this linking agent comprises and is selected from dicarboxylic acid imines, isocyanic ester and formaldehyde source (phenol of Paraformaldehyde 96, γ-POM, vulkacit H, resol resin or etherificate).

The nitrile rubber (HBNR) of nitrile rubber of methylolated phenol functionalization (NBR) or hydrogenated form can be by technology preparation well known in the art.The NBR/HNBR of phenol functionalization can prepare by the phenol of monomethylolization or by undersaturated monomer and undersaturated NBR transposition are prepared.NBR/HBNR need utilize methylolated phenol monomer and NBR by the methylolated phenol functionalization of metathesis prepared.These materials not only can be used as coating of the present invention, and utilize curing, film forming, metal adhesion and the consistency of their uniquenesses to can be used as the composition of elastomer metal tackiness agent, autoprecipitation material, RFL immersion liquid and reactive toughner (for example epoxy glue).Methylolated phenol functionalization NBR/HNBR can self cure (promptly not using external solidifying agent).The derivative of methylolated phenol functionalization NBR/HNBR can be enough other coated component solidify, as phenolic varnish, reactive with active hydrogen or contain the linking agent and the agent of rubber/elastomer malleableize of active hydrogen.Methylolated phenol functionalization HNBR can use with known vulcanizer.Vulcanization reaction is based on quinone methide or benzyl carbonium ion, and the benzyl carbonium ion can produce by the thermal activation or the catalytic activation of methylolation phenol.The quinone methide intermediate is by capturing the allylic hydrogen reaction.Selectively, methylolated phenol can produce under the acid catalyzed condition with base material on the reactive benzyl carbonium ion of unsaturated polymer reaction.

When the reactive functional groups on the HNBR was phenol, isocyanic ester, dicarboxylic acid imines, formaldehyde source and resol resin solidifying agent can be used to the HNBR and the elastomer substrates of phenol functionalization crosslinked.Similarly, the HNBR of amino-functionalization for example can use isocyanic ester or dicarboxylic acid imines, formaldehyde source and/or resol resin to carry out crosslinked.The HNBR of epoxy group(ing) functionalization can carry out crosslinked and curing, for example amine, amidoamines and/or Dyhard RU 100, epoxy glue as known in the art with known solidifying agent.

The HNBR of isocyanate functionization can be undertaken crosslinked or solidifies by moisture or the solidifying agent (as amine or polyvalent alcohol) that adds other.Is special needs in conjunction with isocyanic ester as the part of HNBR, because this will reduce free monomeric amount, thus the amount of reduction volatile isocyanate, and reduce the health and safety problem that it is in the news.The HNBR of maleimide functionalization can be undertaken crosslinked by adding radical initiator or Michael addition reaction.The unsaturated acrylic ester functionalized HNBR of ethylenic can be cured by free radical, UV and electron beam.The HNBR of acid anhydrides functionalization can use the composition in amine or the acid anhydrides-epoxy glue field to be cured.Silyl ether and muriate pass through moisture-curing.The Diels-Alder affixture is self cure or passes through to add metathesis catalyst and solidified.

For providing saturation ratio to be at least ethylenic unsaturated nitrile-conjugated diene rubber of 90%, need with ordinary method nitrile rubber hydrogenation.Generally speaking, can use in numerous known method for hydrogenation any, include but not limited to solution hydrogenation and oxidation/reduction hydrogenation.It is saturated that hydrogenation is used for that rubber is at least 90% unsaturated link(age).When saturation ratio less than 90% the time, the thermotolerance of rubber is lower, more preferably the saturation ratio of rubber is 95-99.99%.

The preferred conjugate diene monomer that is used for preparing carboxylic acidifying acrylonitrile butadiene copolymer through hydrogenation is any known conjugated diolefine, comprises the diene that contains 4～about 10 carbon atoms of having an appointment, such as but not limited to 1,3-butadiene; The 2-methyl isophthalic acid, 3-divinyl, 2,3-dimethyl-1,3-butadiene; 1,3-pentadiene; 1, the 3-hexadiene; 2, the 4-hexadiene; 1, the 3-heptadiene; Piperylene; And isoprene, and 1,3-butadiene is preferred at present.

The unsaturated nitrile monomer copolymerization forms the vinyl cyanide-diene copolymers with the following formula corresponding carboxylic acidization usually:

Wherein each A is hydrogen or the alkyl that contains 1～about 10 carbon atoms.The A examples of groups comprises alkyl and cycloalkyl (as methyl, ethyl, sec.-propyl, the tertiary butyl, octyl group, decyl, cyclopentyl, cyclohexyl etc.) and aryl (as phenyl, tolyl, xylyl, ethylphenyl, tert-butyl-phenyl etc.).Vinyl cyanide and methacrylonitrile are at present preferred unsaturated nitriles.

HNBR of the present invention also comprises and contains functional group and can be grouped to the monomer of HNBR main chain or contain functional group and can be grafted to compound or its mixture on the HNBR.

The monomer that contains carboxyl selectively is used in film forming elastomerics of the present invention.Carboxyl can be by containing the α of 3～about 5 carbon atoms, β-unsaturated monocarboxylic acid monomer provides, as vinylformic acid, methacrylic acid and butenoic acid and/or other known monomer that contains carboxyl, such as but not limited to containing 4～about 5, or～α of about 6 carbon atoms, β-unsaturated dicarboxylic acid, for example toxilic acid, fumaric acid, citraconic acid and methylene-succinic acid and acid anhydrides thereof.The bonded unsaturated carboxylic acid can exist by accounting for about 1～about 10% the amount of multipolymer weight, and corresponding to the amount of conjugated diolefine.Preferably, monomer is undersaturated list-or the derivative (for example ester, acid amides etc.) of two-carboxylic acid.The monomeric function that contains carboxyl comprises to be provided crosslink sites and strengthens bonding.

In addition, the copolymerizable main chain that enters the HNBR multipolymer of the comonomer of other functionalization.The ethylenically unsaturated monomers of functionalization can with nitrile monomer and conjugate diene monomer copolymerization, the example is: the ethylenically unsaturated monomers that contains diazanyl (hydrazidyl), have amino ethylenically unsaturated monomers, the ethylenically unsaturated monomers that has thiol, unsaturated carboxylic acid is (as vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid and salt thereof), the alkyl ester of unsaturated carboxylic acid (as various acrylate, for example methyl acrylate and butyl acrylate), the alkoxy alkyl of unsaturated carboxylic acid is (as methoxy acrylate, the vinylformic acid ethoxy ethyl ester, vinylformic acid methoxyl group ethyl ester), acrylamide and Methacrylamide.

In addition, the appropriate functional comonomer is all kinds of monomers, and as N, N-is dibasic-the aminoalkyl acrylate; N, N-is dibasic-the aminoalkyl methacrylic ester; N, N-is dibasic-the aminoalkyl acrylamide; N, N-is dibasic-the aminoalkyl Methacrylamide; Hydroxyl-replacement-alkyl acrylate and hydroxyl-replacement-alkylmethacrylate; The acrylamide that the N-alkanol replaces, as N hydroxymethyl acrylamide, N, N '-dihydroxymethyl acrylamide and N-ethoxylated trimethylol base acrylamide; The Methacrylamide that N-replaces, as the N-methylol methacrylamide, N, N '-dihydroxymethyl Methacrylamide and N-ethoxyl methyl Methacrylamide, can there be the copolymerization that issues living free radical initiation in they at the alkyl thiol compound that contains 12～16 carbon atoms and three tertiary carbon atoms.

Hydroxyl-the replacement that can enumerate-alkyl acrylate and hydroxyl-replacement-example of alkylmethacrylate comonomer is a vinylformic acid hydroxyl methyl esters, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, vinylformic acid 3-hydroxypropyl acrylate, vinylformic acid 3-chloro-2-hydroxypropyl acrylate, vinylformic acid 3-phenoxy group-2-hydroxypropyl acrylate, hydroxy methyl methacrylate, methacrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxypropyl acrylate, methacrylic acid 3-hydroxypropyl acrylate, methacrylic acid 3-chloro-2-hydroxypropyl acrylate and methacrylic acid 3-phenoxy group-2-hydroxypropyl acrylate.Wherein vinylformic acid hydroxyl methyl esters, vinylformic acid 2-hydroxyl ethyl ester, hydroxy methyl methacrylate and methacrylic acid 2-hydroxyl ethyl ester are preferred.

The NBR multipolymer can come polymerization by those skilled in the art's known method by any above-mentioned exemplary conjugated diolefine, unsaturated nitrile and the comonomer that contains unsaturated functional group in the presence of radical initiator.Suitable radical initiator is not within the scope of the invention, normally organic oxygen compound, superoxide, hydroperoxide and azo-compound etc. are as hydrogen peroxide, benzoyl peroxide, cumene hydroperoxide, ditertiary butyl peroxide, ascaridol(e), acetyl peroxide, tert-butyl hydroperoxide, Trimethylamine oxide compound, dimethyl benzene amine oxide, sec.-propyl peroxy dicarbonate, diisobutylene ozonide, peracetic acid, nitrate, oxymuriate, perchlorate, Diisopropyl azodicarboxylate etc.

The hydrogenation of nitrile rubber is being known in the art and is being disclosed in the document.For example, preferred commercial available X-HNBR (carboxylic acidifying-HNBR) can obtain by two step hydrogenations from carboxylic acidifying nitrile-diene copolymers.Be well known that in NBR 1, the two key hydrogenations of the C-C of the butadiene unit of 2-vinyl-configuration are exceedingly fast, then 1, the unit of 4-cis-configuration is hydrogenated.1, the butadiene unit hydrogenation of 4-transconfiguration is relatively slow.Being used for hydrogenant NBR product can be by accounting for 1 of main ratio, and two keys of 4-transconfiguration are discerned.

In known two step method for hydrogenation, carbon-to-carbon double bond at first is reduced, and carbon-nitrogen bond is reduced then.Other technology that is used for hydrogenated acrylonitrile-butadienecopolymer for example is disclosed in the United States Patent (USP) 4,581,417,4,631,315 and 4,795,788, and the content that is incorporated herein these patents as a reference.

Hydrogenant nitrile rubber (HNBR) (DE-OS No. (German prospectus) 2,539,132 is for example also disclosed in a plurality of specification sheetss partially or completely; DE-OS No. (German prospectus) 3,329,974; DE-OS No. (German prospectus) 3,046,008 and 3,046,251; And European patent No.A-111,412).

The hydrocortone of X-HNBR latex is crossed known routine techniques and is carried out.The carboxylic acidifying NBR polymer latex that uses the anion surfactant routine to make mixes (1) oxygenant with following material, it is selected from oxygen, air and hydroperoxide; (2) reductive agent, it is selected from hydrazine and composition thereof; And (3) metal ion activation agent; (b) with mixture from 0 ℃ of reflux temperature that is heated to reaction mixture.This technology is disclosed in No. 4,452,950, United States Patent (USP) authorizing Goodyear Tire and Rubber Co., is hereby incorporated by.

Most preferably be that acrylonitrile butadiene copolymer is hydrogenated to the degree of unsaturation that makes final product is about 1～about 10 moles of %, be preferably about 1～about 5 moles of %.

Suitable carboxylic acidifying hydrogenated nitrile rubber (X-HNBR) is that the trade mark that Bayer makes is " Therban ^" product, for example Therban KA 8889.Its iodine number of X-HNBR is preferably about 50% or still less, and is more preferably about 3～40%, most preferably is about 8～30%.

Linking agent-the reactive functional groups that is provided as film by aforesaid method can carry out before or after hydrogenation.Example as the unsaturated compound that contains functional group can be the cycloolefin that contains the vinyl compound of functional group and contain functional group.Introducing functional group by graft-modification method can be undertaken by HNBR is reacted under organo-peroxide with the unsaturated compound that contains functional group.Be not particularly limited for the unsaturated compound that contains functional group.Yet, contain epoxy group(ing) unsaturated compound, contain carboxyl unsaturated compound, contain the unsaturated compound of hydroxyl, cross-linking density reaches and the binding property of base material owing to improving with lower modification speed to contain the unsaturated compound of silyl, undersaturated silicoorganic compound etc., so should propose especially.

The example that contains the unsaturated compound of epoxy group(ing) or contain the cycloolefin of epoxy group(ing) comprises the glycidyl ester of unsaturated carboxylic acid, as glycidyl acrylate, glycidyl methacrylate with to styryl-carboxylic acid glycidyl ester; The list of unsaturated polyester carboxylic acid or many glycidyl esters, as interior-cis-dicyclo [2,2,1] heptan-5-alkene-2,3-dicarboxylic acid and interior-cis-dicyclo [2,2,1] heptan-5-alkene-2-methyl-2, the 3-dicarboxylic acid; Unsaturated glycidyl ether is as the glycidyl ether of glycidyl allyl ether, 2-methyl-glycidyl allyl ether, o-allyl phenol, the glycidyl ether of a chavicol and the glycidyl ether of p-allylphenol; 2-(adjacent ethenylphenyl) oxyethane, 2-(to ethenylphenyl) oxyethane, 2-(o-allyl base)-oxyethane, 2-(to allyl phenyl) oxyethane, 2-(adjacent ethenylphenyl) propylene oxide, 2-(to ethenylphenyl) propylene oxide, 2-(o-allyl base) propylene oxide, 2-(to allyl phenyl) propylene oxide, to glycidyl vinylbenzene, 3,4-epoxy-1-butylene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-amylene, 3,4-epoxy-3-Methyl-1-pentene, 5,6-epoxy-1-hexene, single oxide compound of vinyl cyclohexene and allyl group-2,3-epoxy group(ing) cyclopentyl ether.These unsaturated compounds that contain epoxy group(ing) can use separately or use in any combination way.

The example that contains the unsaturated compound of carboxyl can be that Japanese patent application intends disclosing the compound described in 271356/1993, and unsaturated carboxylic acid for example is as vinylformic acid, methacrylic acid and α-Yi Jibingxisuan; Unsaturated dicarboxylic acid, as toxilic acid, fumaric acid, methylene-succinic acid, interior-cis-dicyclo-[2.2.1] heptan-5-alkene-2,3-dicarboxylic acid and methyl-Nei-cis-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxylic acid.The another kind of example of olefinically unsaturated carboxylic acid derivatives can be acid anhydrides, ester, halogenide, acid amides and the imide of unsaturated carboxylic acid.Specific examples comprises the acid anhydrides of acid, as maleic anhydride, chloromaleic acid acid anhydride, butenyl succinyl oxide, Tetra Hydro Phthalic Anhydride and citraconic anhydride; Ester is as monomethyl maleate, dimethyl maleate and toxilic acid glycidyl ester; And Malaysia acyl chlorides and maleimide.Unsaturated dicarboxylic acid and acid anhydrides thereof are preferred in above-mentioned, because utilize graft reaction etc. to introduce functional group easily, the acid anhydrides of acid such as maleic anhydride and itaconic anhydride are particularly preferred.

The example that adds the unsaturated compound that contains hydroxyl in the film-forming polymer comprises allyl alcohol, 2-allyl group-6-methoxyphenol, 4-allyloxy-2-Viosorb 110,3-allyloxy-1,2-propylene glycol, 2-allyl group biphenol, 3-butene-1-alcohol, 4-amylene-1-ol and 5-hexen-1-ol.

The example that adds the unsaturated compound that contains silyl in the membrane-forming agent comprises chloro dimethyl vinyl silanes, trimethyl silyl acetylene, 5-trimethyl silyl-1, the 3-cyclopentadiene, 3-trimethyl silyl allyl alcohol, methacrylic acid trimethyl silyl ester, 1-trimethylsiloxy-1,3-butadiene, 1-trimethylsiloxy cyclopentenes, methacrylic acid 2-trimethylsiloxy ethyl ester, 2-trimethylsiloxy furans, 2-trimethylsiloxy propylene, allyloxy-tertiary butyl dimethylsilane and allyloxy trimethyl silane.

The example that is used for the bonded unsaturated organosilicon compounds comprises the tri-alkoxy vinyl silanes, as trimethoxy vinyl silanes, triethoxy vinyl silanes, three (methoxy ethoxy) vinyl silanes.Alkoxyl group hydrolyzable in the unsaturated organosilicon compounds becomes silanol.

The example of unsaturated sulfonic acid or phosphide group comprises 2-(methyl) acrylamido 2-methyl isophthalic acid-propanesulfonic acid, 3-sulfonic acid propyl group (methyl) acrylate, 2-sulfonic acid ethyl (methyl) acrylate and 2-phosphoric acid ethyl (methyl) acrylate.These comonomers can be added to various Tg and be lower than in 0 ℃ vinylformic acid vinyl ester, acrylate or other the flexible polymer as the membrane-forming agent polymkeric substance, and can Resins, epoxy, isocyanic ester, carbodiimide, aminoresin, aminosilane and other can with curing in the presence of the linking agent of acid groups reaction.The multipolymer of flexible, low Tg is at least with the sulphur of about 2 moles of % and/or contain the acid groups of phosphorus, and shows 5～100, is preferably 10～85, most preferably is 10～30 acid number, and it can be used in the membrane-forming agent of the present invention.

The HNBR of grafting-modification of the present invention can obtain by one of above-mentioned ethylenically unsaturated compounds that contains functional group and HNBR graft reaction under the condition that produces free radical.The method that produces free radical can be the method that (i) utilizes organo-peroxide, (ii) utilizes the method for light-initiated free radical generating agent, (iii) utilizes energy-ray radiating method, and (iv) utilizes the method for heating.

(i) utilize the method for organo-peroxide: the preferred organo-peroxide that uses for example is organo-peroxide, organic ester etc. of crossing.The specific examples of organo-peroxide can be a benzoyl peroxide, dichlorobenzoyl peroxide, the peroxidation diisopropyl benzene, ditertiary butyl peroxide, 2,5-dimethyl-2,5-two (peroxide benzoate)-3-hexin, 1, two (tert-butyl hydroperoxide sec.-propyl) benzene of 4-, lauroyl peroxide, tertiary butyl peracetic acid, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide)-3-hexin, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane, t-butyl perbenzoate, cross the phenylacetic acid tertiary butyl ester, cross the isopropylformic acid tertiary butyl ester, cross secondary sad tertiary butyl ester, cross the PIVALIC ACID CRUDE (25) tertiary butyl ester, cross PIVALIC ACID CRUDE (25) cumyl ester and cross the diethylacetic acid tertiary butyl ester.In the present invention, azo-compound also can be used as organo-peroxide.The specific examples of azo-compound can be Diisopropyl azodicarboxylate and azo isopropylformic acid dimethyl esters.Wherein preferred use is benzoyl peroxide and dialkyl peroxide, as diisopropyl benzene superoxide, ditertiary butyl peroxide, 2,5-dimethyl-2,5-two (tert-butyl peroxide)-3-hexin, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane and 1, two (tert-butyl hydroperoxide sec.-propyl) benzene of 4-.

These organo-peroxides can use separately or use with the form of any combination.In the unmodified HNBR of 100 weight parts, the ratio of used organo-peroxide is about 0.001～about 10 weight parts usually, is preferably about 0.01～about 5 weight parts, more preferably about 0.1～about 2.5 weight parts.In the time of in used organo-peroxide is in this scope, the various character that contain the polymkeric substance that contains functional group of the speed of reaction of unsaturated compound of functional group and generation can balance each other at high level.Therefore the preferred organo-peroxide that uses in this scope.

Be not particularly limited the graft modification reaction, this reaction is carried out according to any known method in this area.Graft reaction carries out under 0～400 ℃ temperature usually, is preferably 60～350 ℃.Reaction times is generally 1 minute～and 24 hours, be preferably 30 minutes～10 hours.After reaction is finished, a large amount of solvents (as methyl alcohol) can be added in the reaction system polymkeric substance with formation of deposits, and decompression time after filtration, washing, dry collected polymer.

(ii) utilize the method for light-initiated free radical generating agent: the method for utilizing light-initiated free radical generating agent is a kind of after adding light-initiated free radical generating agent, the mixture that obtains is exposed to the method for UV-light with the generation free radical, and can uses any conventional known method.Light-initiated free radical can be any material, as long as it can activate with ultraviolet radiation.Its specific examples comprises carbonyl compound, as bitter almond oil camphor, benzoin methyl ether, bitter almond oil camphor isopropyl ether, bitter almond oil camphor isobutyl ether, acetoin, butyroin, toluene acyloin, benzyl, benzophenone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, Alpha-hydroxy cyclohexyl-phenyl ketone, p-isopropyl-Alpha-hydroxy isobutyl-benzophenone, α, α-Er Lv-4-Ben Yangjibenyitong, aminomethyl phenyl oxoethanoic acid, ethylphenyl oxoethanoic acid, 4,4-two (dimethylamino benzophenone) and 1-phenyl-1,2-propanedione-2-(adjacent ethoxy carbonyl); Oxime; Sulfide is as tetra methylthiuram list sulfide and tetramethyl thiuram disulfide; Azo-compound, two-2 as Diisopropyl azodicarboxylate and azo, the 4-methyl pentane nitrile; Superoxide is as benzoyl peroxide and two (tertiary butyl) superoxide; Acylphosphine oxide, as 2,4,6-Three methyl Benzene formyl diphenyl phosphine oxide.Used light-initiated free radical generating agent is generally 0.001～about 10 weight parts, is preferably about 0.01～about 5 weight parts, more preferably about 0.1～about 2.5 weight parts.

The radiating method: utilizing energy-ray radiating method is known method, wherein uses active energy beam such as α-ray, beta-rays and gamma-radiation to produce free radical.Especially, need to use UV-light from efficient, practicality, income viewpoint.

The method of heating: can realize by under 100～390 ℃ temperature, heating by the method that adds the thermogenesis free radical.Can use known solution method, fusing kneading method.Wherein the viewpoint fusing kneading method from reaction efficiency is preferred, and its use extrusion machine etc. are through adding the thermogenesis shearing force.

Be not particularly limited the method for on the membrane-forming agent polymkeric substance, introducing functional group.The example comprises the method for (a) oxidation unsaturated link(age), (b) compound that contains at least one functional group in the molecule is added to the preceding method of unsaturated link(age), (c) method of introducing epoxy group(ing) as herein described, carboxyl, hydroxyl, or above-mentioned ethylene linkage that makes NBR or HNBR polymkeric substance and the reaction of undersaturated, preferred monounsaturated carboxylic acid reaction thing, and end group is added to the method for the polymkeric substance that active cation causes.Selectively, can use the compound halogenated polymer that contains chlorine or bromine.Halogenated then polymkeric substance and the reaction of single unsaturated carboxylic acid.Polymkeric substance also can contact at high temperature with single unsaturated carboxylic acid reactant, thereby above-mentioned heat " alkene " reaction takes place.Selectively, single unsaturated carboxylic acid can be by the grafting effect and the polymer reaction of free radical initiation.Functionalization elastomerics of the present invention can be by contacting and functionalization with hydroxy-aromatic compound in the presence of at least a dialkylaminobenzoic acid catalyzer of catalytically effective amount.Alkylating then hydroxy-aromatic compound can further react the formation derivative, and this reaction is that Mannich base (Mannich Base) forms Mannich Base condenses with aldehyde and amine reactant condensation.In other method of functionalized polymer, polymkeric substance can contact in the presence of an acidic catalyst with carbon monoxide, forms the polymkeric substance that replaces with hydroxy-acid group under the Koch reaction conditions.Except the above-mentioned functions method, polymkeric substance of the present invention can come functionalization by atmospheric oxidation, ozone decomposition, hydroformylation, epoxidation and chloramination or other method (for example, Japanese Patent Application Publication 172423/1994).

The fluoroelastomer membrane-forming agent

Fluorocarbon elastomer (fluoroelastomer) as film-forming polymer used herein can be derived from hydrocarbon (comprising vinylidene, R 1216), and can obtain from multiple source commercial.Going through of all kinds fluoroelastomer is included in R.G.Arnold, and A.L.Barney and D.C.Thompson are in the article of delivering in July, 1973 that is entitled as " Rubber Chemistry andTechnology " (46 volumes, 619-652 page or leaf).The basic difference of fluoroelastomer and thermoplastic fluoropolymer is the ductility plastic deformation through whether the fluoroelastomer stress application being had 100%.Fluoroplastics have 100% ductility deformation, thereby are unsuitable for the coated substance as elastic substrate of the present invention.

Representational fluoroelastomer used herein comprises the polymkeric substance that is derived from one or more fluorinated monomers, comprises vinylformic acid 1,1-dihydro perfluor butyl ester; The multipolymer of vinylidene and chloro trifluoro-ethylene; The multipolymer of vinylidene and R 1216; The multipolymer of vinylidene and hydrogen five fluorine propylene; The multipolymer of tetrafluoroethylene and propylene; And the terpolymer of vinylidene, R 1216 and tetrafluoroethylene; The terpolymer of vinylidene, tetrafluoroethylene and perfluoroalkyl vinyl ether; The terpolymer of vinylidene, tetrafluoroethylene and propylene; The terpolymer of vinylidene, hydrogen five fluorine propylene and tetrafluoroethylene.Most preferred the present invention through the fluoroelastomer of modification is commercial can be by Viton ^Trade mark obtains, as the multipolymer of vinylidene and R 1216 or the terpolymer of vinylidene, tetrafluoroethylene and R 1216.Other suitable fluoroelastomer can be from Dyneon with FLOREL ^Trade mark obtains, also can be from Ausimont with TECHNIFLON ^Trade mark obtains.

The membrane-forming agent of the fluoroelastomer embodiment of grafting functionalization used herein is the reaction product of fluoro elastomer copolymer and grafting agent, grafting agent contain can with the grafting linking group of fluoroelastomer covalent bonds and the group that at least one contains active hydrogen (for example hydroxyl, thiol or carboxyl, it can form key with one of reactive group of solidifying agent).The fluoroelastomer of grafting-modification in the storage life of mixture (before the gelation), when the coating elastomer base material, combine with solidifying agent in the mixture.

The grafting agent of fluoroelastomer contains the group of a grafting-linking group and a band active hydrogen.Preferred grafting agent contains primary amine group and a group that contains active hydrogen.The example comprises that azanol, amino isocyanic ester are (as (R ₂) ₂NCH ₂CH ₂NCO, wherein R ₂For example be hydrogen or alkyl), hydroxyalkyl amine, aminocarboxylic acid ester, aminosilane, aminosilane alcohol, amineothiot etc.Other suitable grafting agent that does not contain as grafting-linking group primary amine is the sulfydryl hydroxyl, as mercaptoalcohol and hydrosulphonyl silane alcohol, sulfydryl mercaptan etc.Preferred grafting agent can be grafted on the fluoroelastomer under gentle relatively temperature (＜60 ℃), and but monomer, oligopolymer or polymkeric substance, it comprises at least one group that contains active hydrogen and be no more than a primary amine group, but selectively contains secondary amine or tertiary amine group or can not grafting-connection and other group of crosslinked fluoroelastomer.Selectable secondary amine is considered to improve the speed of primary amine grafting-linking group to the graft reaction of fluoroelastomer.The specific examples of grafting agent comprise various hydroxyalkyl amine (for example 3-amino-1-propyl alcohol), aminoalkylsilane alcohol (for example aminoalkylsilane triol or precursor aminoalkyl-organoalkoxysilane, comprise at least in its each molecule one can alkoxy silane catalyzed group hydrolysis to produce the basic nitrogen of reactive silane triol), amine-N-oxide compound, amino (hydroxyl) carboxylic acid, amido (hydroxyl) amine, polyoxyalkylene polyethers list (primary) amine and amine-end capped polyvalent alcohol.This amine-end capped polyvalent alcohol can be by known amination method with alkylene oxide for example oxyethane, propylene oxide, butylene oxide ring, dodecane oxide compound or styrene oxide, and addition polymerization obtains to amino-initial compound.Generally speaking, the available ammonia of polyvalent alcohol (as polyether glycol) carries out amination under catalyzer (as contain the catalyzer of nickel, for example Ni/Cu/Cr catalyzer) exists.Known method is disclosed in United States Patent (USP) 4,960,942; United States Patent (USP) 4,973,761; United States Patent (USP) 5,003,107; United States Patent (USP) 5,352,835; United States Patent (USP) 5,422,042; And United States Patent (USP) 5,457,147, be incorporated herein these patents as a reference.Used beginning compound is ammonia or the compound that contains amine groups, and will provide in reaction product and be no more than a primary amino, for example aliphatic polyamines such as quadrol, quadrol oligopolymer (Diethylenetriamine for example, three second tetramines or five second hexamines), thanomin, 1,3-propylene diamine, N-(2-hydroxyethyl) quadrol, 1,3-or 1,4-butanediamine, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-hexamethylene-diamine etc.The polyether block of suitable polyethers-monoamine comprises the multipolymer of polyoxyethylene glycol, polypropylene glycol, polyoxyethylene glycol and polypropylene glycol, poly-(1, the 2-butyleneglycol) and poly-(1, the 4-butyleneglycol).

Preferred amino-hydroxyl grafting agent compound be molecular weight less than about 1000, preferred 500, be more preferably less than 250 compound.Preferred amino-hydroxyl grafting agent contains 2～16 carbon atoms.If the molecular weight of grafting agent is greater than about 1000, the resistance to deflection of coating and solvent resistance reduce so.The enforcement of preferred grafting agent comprises 3-amino-1-propyl alcohol, 2-(2-ammonia ethylamino) ethanol and aminoalkylsilane alcohol, for example aminopropyl silantriol.With respect to the weight of fluoroelastomer, the significant quantity of used grafting agent is 1-20%, is preferably 2-10 weight %, more preferably 3-7 weight %.

Although the grafting agent of the fluoroelastomer of the provided hydroxyl functionalization that other is exemplary is not preferred, comprise the ethylenically unsaturated compounds of the grafting hydroxyl functionalization that obtains by the grafting addition reaction.Above-mentioned sulfydryl hydroxyl and sulfydryl carboxylic compound are suitable.The ethylenically unsaturated monomers that contains hydroxyl or carboxyl is suitable, include but not limited to (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 1-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxypropyl acrylate, 2-hydroxyethyl vinyl ether, N-methylol (methyl) acrylamide, methacrylic acid and maleic anhydride, and can be in the presence of radical initiator, be grafted on the fluoroelastomer by technique known in the reactive process field of polymkeric substance, and be widely used in thermoplastics such as the polyolefine.

In other embodiment, fluorocarbon elastomer is by carry out grafting functionalization with hydroxyl (alkyl) mercaptan, amineothiot or the mercaptan carboxylic acid of selectively containing hydroxyl through addition reaction.The suitable mercaptan that can produce the hydroxyl that is added on the fluoroelastomer comprises hydroxy thiol, as mercaptoethanol, hydroxyalkylmercaptan (as 1-sulfydryl-3-propyl alcohol), mercaptoethanolamine, 1-sulfydryl-4-butanols, the low polyethylene oxide of alpha-mercapto-ω-hydroxyl, for example copolyether of alpha-mercapto-ω-hydroxyl ethohexadiol or corresponding ethylene oxide/propylene oxide.The sulfydryl alkoxy compound that can produce hydroxyl through hydrolysis comprises γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane, γ-sulfydryl propyl group methyl dimethoxysilane and γ-sulfydryl propyl group methyldiethoxysilane, has only listed several.Suitable mercaptan carboxylic acid and corresponding ester are above-mentioned Thiovanic acid, ester, thiohydracrylic acid and ester, sulfydryl butyric acid and the ester of Thiovanic acid.The esterification compound that contains hydroxyl comprises ethylene glycol, propylene glycol, butyleneglycol, Diethylene Glycol, triethylene glycol, TEG, ethohexadiol, dipropylene glycol, tripropylene glycol, four propylene glycol and N methyldiethanol amine.

Especially mercaptoalcohol can the significant quantity grafting for sulfydryl-compound-be connected on any suitable olefin elastomer, solidify then.In the fluoroelastomer of preparation functionalization, useful especially is that sulfhydryl compound can add under mild temperature or envrionment temperature.The combination that is grafted to the sulfydryl-compound on the fluoroelastomer selectively realizes with the radical initiator in the solution under being higher than the decomposition temperature of initiator, for example uses azo initiator (as Diisopropyl azodicarboxylate and azo bicyclohexane nitrile), superoxide (as two lauroyl peroxides), benzpinacone silyl ether or the light trigger in the presence of UV or visible light.Diacyl peroxide is suitable, particularly two lauroyl peroxides, didecyl acyl peroxide, two (3,3, the 5-trimethyl acetyl) superoxide, two succinyl-superoxide and diperoxy benzoyl.The significant quantity of radical initiator is 0.5～10 weight % by the weight of sulfydryl-compound.Preferred sulfhydryl compound is a mercaptoalcohol, as mercaptoethanol.The significant quantity of initial sulfydryl-compound is 3%～10% by fluoroelastomer weight, and is enough to 1%～5% constraint hydroxyl bond by weight is incorporated on the fluoroelastomer.

Preferred fluoroelastomer grafting agent is to be grafted on the fluoroelastomer those in room temperature, as 2-(2-ammonia ethylamino) ethanol (NH ₂-CH ₂-CH ₂-NH-CH ₂-CH ₂-OH) (CAS#111-41-1) and aminopropyl silantriol can be by Gelest, and Inc. is with the aqueous solution supply of the 22-25% of SIA0608.0 (CAS#29159-37-3).

Crosslinkable alpha-olefin copolymer elastomerics

Poly-(olefin/propylene acid esters/carboxylicesters) multipolymer film forming elastomerics is by making at least a alpha-olefin and at least a (methyl) vinylformic acid C ₁-C ₁₈Alkyl ester and have the multipolymer that the comonomer of unsaturated functional group is polymerized on a small quantity, wherein comonomer is used for and following substances forms cross-link bond, as polymeric polyisocyanate, carbodiimide and other reagent.The comonomer that has functional group can contain ethylenic unsaturated group and the group that has acid, hydroxyl, epoxide, isocyanic ester, An, oxazoline, diene or other reactive group.When not having the monomer of this functionalization, crosslink sites can result from the multipolymer of alpha-olefin-ester, for example produces by partial hydrolysis side chain ester group.Be applicable to that the elastomeric alpha-olefin of this olefin copolymer film forming of polymerization comprises ethene, propylene, 1-butylene, iso-butylene, amylene, heptene, octene and composition thereof.C ₁-C ₄Alpha-olefin is preferred, and ethene is most preferred.

That the comonomer of functionalization can provide copolymerization and have an alpha-olefinic polymer that active hydrogen, halogen maybe can transform group, as changing into the group of band active hydrogen by transamidation or hydrolysis, or opposite, the comonomer of functionalization contain can with the group of the linking agent reaction that has active hydrogen group.Alkyl or alkoxyl group (methyl) acryllic acid and ester are the comonomers of exemplary functionalization.The specific examples of alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, octyl group, 2-ethylhexyl and decyl; Cycloalkyl is as cyclopentyl and cyclohexyl; Aryl is as phenyl and tolyl; And aralkyl, as benzyl and 2-first-hydrocinnamyl.

The example of alkoxyl group comprises methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, pentyloxy, hexyloxy and octyloxy.

Selectively can comprise methyl acrylate, ethyl propenoate, tert-butyl acrylate, n-butyl acrylate, vinylformic acid 2-second polyhexamethylene, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, vinylformic acid 2-ethyl-own ester, vinylformic acid methoxyl group ester, vinylformic acid ethoxy ethyl ester, vinylformic acid methoxyl group ethyl ester, acrylamide and Methacrylamide etc. or its mixture with suitable alkyl of alpha-olefin bonded or alkoxyl group (methyl) acrylate.Can be with the specific examples of the ethylenically unsaturated monomers of the functionalization of 'alpha '-olefin monomers copolymerization: unsaturated carboxylic acid, as vinylformic acid, methacrylic acid, methylene-succinic acid and toxilic acid and salt thereof; The alkyl ester of unsaturated carboxylic acid is as methyl acrylate and butyl acrylate.

Preferred alpha-olefin-acrylic ester copolymer rubber contains the unsaturated carboxylic acid monomer unit, for example be derived from the acid unit of (methyl) vinylformic acid or toxilic acid, or for example be derived from the acid anhydrides unit of maleic anhydride, or for example be derived from the partial ester unit of ethyl maleate.In preferred embodiments, polymkeric substance is ethene, vinylformic acid C ₁-C ₄The unitary terpolymer of alkyl ester and carboxylic acid monomer; The terpolymer that more preferably contains the ethyl maleate of the ethene of the 30 moles of % that have an appointment, about 10～about 69.5 moles of % at least.In all cases, preferred alpha-olefin acrylic elastomer is amorphous basically, and its glass transition temperature (Tg) is lower than room temperature, promptly is lower than about 20 ℃.

Other comonomer that contains the reactive group that is useful on the acid, hydroxyl, epoxide, isocyanic ester, amine, oxazoline, diene or other reactive functional groups that add functionalization comprises diene monomers, as non-conjugated diene (as alkylidene group norbornylene, alkenyl norbornene, Dicyclopentadiene (DCPD), methyl cyclopentadiene and dimer thereof), conjugated diolefine (as divinyl and isoprene).The example that contains (methyl) acrylate of dihydro dicyclopentadienyl comprises dihydro dicyclopentadienyl (methyl) acrylate and dihydro Dicyclopentadiene (DCPD) oxygen base ethyl (methyl) acrylate.

Other example of the comonomer of functionalization comprises the α that contains 4～10 carbon atoms, the N-alkanol of β-alkene formula unsaturated carboxylic acid and N-alkoxyl group acid amides are (as N methacrylamide, N-ethanol acrylamide, N-propyl alcohol acrylamide, the N-methylol methacrylamide, N-ethanol Methacrylamide, n-butoxy acrylamide and isobutoxy acrylamide, N-methyl maleimide, N-methyl maleinamide, N-methylol Malaysia propylhomoserin, N-methyl Malaysia propylhomoserin ester), the N-alkylolamide of vinyl aromatic acid is as N-methylol-p vinyl benzamide etc.

Having to be the ethylenically unsaturated compounds that contains epoxy group(ing) with other example of the comonomer of the group of reactive with active hydrogen or the functionalization that itself contains active hydrogen group, comprises glycidyl allyl ether, glycidyl methacrylate and glycidyl acrylate.The specific examples that contains the ethylenically unsaturated compounds of reactive halogen comprises vinyl benzyl chloride, vinyl benzyl bromine, 2-chloroethyl vinyl ether, vinyl chloroacetate, chloropropionic acid vinyl acetate, allyl chloroacetate, chloropropionic acid allyl ester, vinylformic acid 2-chloroethene ester, methacrylic acid 2-chloro-ethyl ester, chloromethyl vinyl ketone and 2-chloroethene acyl-oxygen ylmethyl-5-norbornylene.The specific examples that contains the ethylenically unsaturated compounds of common carboxyl comprises vinylformic acid, methacrylic acid, butenoic acid, 2-pentenoic acid, toxilic acid, fumaric acid and methylene-succinic acid.

The example of other ethylenic unsaturated (methyl) acrylate co-monomers comprises Octyl methacrylate; The alkyl ester that (methyl) vinylformic acid cyano group replaces is as 2 cyanoethyl acrylate, vinylformic acid 3-cyano group propyl ester and vinylformic acid 4-cyano group butyl ester; The alkyl ester of (methyl) acrylic-amino-replacement is as the vinylformic acid lignocaine ethyl ester; Fluorine-containing acrylate, as vinylformic acid 1,1, the 1-trifluoro ethyl ester; The alkyl ester of (methyl) vinylformic acid hydroxyl-replacement is as Hydroxyethyl acrylate; Alkyl vinyl ketone is as methyl vinyl ketone; Vinyl or allyl ethers are as EVE and allyl methyl ether; Vinyl aromatic compounds is as vinylbenzene, alpha-methyl styrene, chloro-styrene and Vinyl toluene; Vinylamide is as acrylamide, Methacrylamide and N hydroxymethyl acrylamide; Reach ethene, propylene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene, vinyl-acetic ester, fumaric acid alkyl ester etc.

Acrylic elastomer

If its glass transition temperature of the acrylate elastomer of functionalization is lower than-10 ℃, so also be suitable, and be defined as one or more copolymerizable α that are derived from a large amount of (by total polymer weight greater than 50 weight %), the addition polymer of the β-ethylenic unsaturated ester monomer and the comonomer of the active group of the functionalization position of containing active hydrogen or grafting-be connected on a small quantity, α wherein, β-its formula of ethylenic unsaturated ester monomer is as follows:

R wherein ₁Be hydrogen or methyl; R ₂Represent C ₁-C ₂₀Alkyl, C ₂-C ₇Alkyl, C ₂-C ₇Alkoxyalkyl, C ₂-C ₇Alkyl-thio-alkyl, C ₂-C ₇The cyano group alkyl.Can use the acrylate of the solid, emulsion or the latex form that obtain from various commercial channel.Wherein can contain by the few comonomer that increases to about 35% sclerosis or Tg of total acrylic elastomer weight, for example methyl methacrylate, vinyl cyanide, vinyl-acetic ester, vinylidene chloride and/or vinylbenzene only list several.Be ideally, the comonomer that has a functional group contain active hydrogen or can with the group of the solidifying agent reaction that contains active hydrogen, it is the acid anhydrides of unsaturated monocarboxylic (for example acrylic or methacrylic acid) or poly carboxylic acid (for example methylene-succinic acid, citraconic acid etc.) or poly carboxylic acid.

The specific examples of the suitable acrylic or methacrylic acid mono that can be used singly or in combination comprises methyl acrylate, ethyl propenoate, butyl acrylate, butyl methacrylate, EHA etc.Preferred multipolymer contains the different copolymerizable monomer shown in one or both structures (I), wherein R ₁Be hydrogen; And R ₂Be C ₄-C ₈Alkyl or C ₂-C ₈Alkoxyalkyl, any all can contain primary, the second month in a season or uncle's atom.Preferred vinylformic acid C ₄-C ₈The example of alkyl ester is n-butyl acrylate, isobutyl acrylate, vinylformic acid n-pentyl ester, vinylformic acid isopentyl ester, Ethyl acrylate, vinylformic acid 2-methyl pentyl ester, vinylformic acid n-octyl and 2-EHA; Preferred vinylformic acid C ₄-C ₈Alkoxy alkyl is vinylformic acid methoxyl group ester and vinylformic acid ethoxy ethyl ester; Preferred acrylic acid alkyl alkylthio ester is a vinylformic acid methyl sulfo-ethyl ester; Preferred vinylformic acid C ₂-C ₇The cyano group alkyl ester is vinylformic acid cyano group ethyl ester and vinylformic acid cyano group propyl ester; Also can use aforementioned two or more mixture.

The comonomer that has active hydrogen that is preferred for acrylic elastomer comprises comonomer multiple above-mentioned functionsization and that have active hydrogen, and wherein repeatably comonomer comprises the comonomer of the carboxamide, aldehyde, alkyl and the aryl ketones that contain carboxylic acid anhydride, carboxamide, N-and replace, hydroxyl, chloro allyl group, methylol, maleimide, two maleimide, alkyl N-methylol, phenol methylol, thiol group, amino, isocyanate group, alkoxyalkyl, Oxyranyle etc.α, the acid anhydrides of β-undersaturated hydroxycarboxylic acid or dicarboxylic acid is preferred.If polymkeric substance only is the multipolymer of acrylate and carboxylic acid or acid anhydrides comonomer, preferred its contains the acrylic ester repeat units of the 90～about 98 moles of % that have an appointment, the more preferably from about this ester of 92～about 97 or 98 moles of % and 2～10% carboxylic acid or acid anhydrides, more preferably 3～8% carboxylic acid or acid anhydrides.

But the example of the functionalization comonomer of random incorporation comprises glycidyl methacrylate, vinylformic acid and methacrylic acid, maleic anhydride, N-alkyl maleimide, acrylamide in the addition polymerization of membrane-forming agent polymkeric substance, N-alkoxyalkyl acrylamide (as N-isobutoxy Methacrylamide, N hydroxymethyl acrylamide etc.), methyl vinyl ketone, propenal, vinyl isocyanate, acrylic acid hydroxy alkyl ester (as vinylformic acid 2-hydroxy methacrylate, methacrylic acid 2-hydroxyl ethyl ester etc.) also comprise the monomeric mixture of two or more these functionalization.

In acrylic elastomer, also comprise so-called core-shell polymer.The multipolymer that is used for soft-shell copolymer rubber comprises the monomeric copolymerization composition of functionalization of at least a Acrylic Acid Monomer and second kind of copolymerizable thing, and wherein the Tg of Acrylic Acid Monomer homopolymer is lower than-10 ℃.These monomers are (for example vinylbenzene, vinyl cyanide, methyl methacrylate etc.) and the selected low Tg acrylic comonomers polymerization of certain proportion in the presence of than the aforesaid mono-vinyl monomer or vinylidene monomer of small proportion, thereby the Tg of acrylic copolymer that can not improve generation is to approximately more than-10 ℃.

The shell multipolymer is an addition polymer, its composition can change widely, yet for the purpose of most of multipolymer, its composition comprises at least a rubber monomer of about 99.9～about 95 weight % and second kind of copolymerizable functionalization monomer of about 0.1～about 5 weight %.Preferred shell multipolymer is the multipolymer of alkyl acrylate and methacrylic acid 2-hydroxyl ethyl ester.

Elastic coating of the present invention is based on the addition polymer of the functionalization of successive polymerization, and shows two glass transition temperatures, and one of them is lower than 0 ℃, and another is higher than 0 ℃.The amount of rubber-like shell multipolymer composition and the ratio of hard component and rubber constituent can change, yet for most of purpose, rigid copolymer composition and rubber-like shell multipolymer components in proportions are less than 1, the amount that is rubber constituent accounts for larger proportion (greater than 50 weight %, being preferably 60 weight %～80 weight %).

The vinylformic acid addition polymer of two (halo, carboxyl) functionalization also can be used as the embodiment that the present invention contains the membrane-forming agent of organic solvent, it contains the repeating unit or the monomer mixture of acrylate monomer, and the glass transition temperature in elastomerics is lower than-20 ℃.Functional group provides by about 0.1%～about 30%, the comonomer that contains reactive halogen of preferred 0.2%～about 15% weight and the carboxyl comonomer that contains of about 0.1%～about 20% weight.In the preferable amount of halogen-containing comonomer, content of halogen be functionalization acrylic rubber weight about 0.1%～about 5%.The halogen of halogen-containing comonomer can be chlorine, bromine or iodine.Chloride comonomer is because economic, practical and safe and preferred.

The example of halogen-containing comonomer is a vinyl chloroacetate, the bromoacetic acid vinyl acetate, allyl chloroacetate, the chloropropionic acid vinyl acetate, the chloro-butyric acid vinyl acetate, the bromo-butyric acid vinyl acetate, vinylformic acid 2-chloroethene ester, vinylformic acid 3-chlorine propyl ester, vinylformic acid 4-neoprene ester, methacrylic acid 2-chloroethene ester, vinylformic acid 2-bromine ethyl ester, 2-iodopropylene acetoacetic ester, 2-chloroethyl vinyl ether, the chloromethyl vinyl ketone, vinylformic acid 4-chloro-crotyl ester, vinyl benzyl chloride, 5-chloromethyl-2-norbornylene, 5-α-chloroethene acyl-oxygen ylmethyl)-the 2-norbornylene, 5-(α, β-dichloro propionyl methyl)-2-norbornylene etc.Preferred monomer is vinyl chloroacetate, allyl chloroacetate, vinylformic acid 2-chloroethene ester, 2-chloroethyl vinyl ether, vinyl benzyl chloride, 5-chloromethyl-2-norbornylene and 5-chloroethene acyl-oxygen ylmethyl-2-norbornylene.

The comonomer that has active hydrogen of preferred acrylic rubber is counted about 0.1%～about 20% (by weight) by at least a weight that contains the comonomer of carboxyl, is preferably for 0.2%～about 10% (by weight), and more preferably 2%～about 6%.The carboxyl comonomer is mono carboxylic preferably, but also poly-carboxyl.Preferred carboxyl comonomer contains 3～about 8 carbon atoms.The example of this preferred comonomer is vinylformic acid, methacrylic acid, ethylacrylic acid, β, beta dimethylacrylic acid, butenoic acid, 2-pentenoic acid, 2-hexenoic acid, toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, methylene-succinic acid, 3-butene-1,2,3-tricarboxylic acid etc.Most preferred carboxyl comonomer is a monocarboxylic acid monomer, as vinylformic acid, methacrylic acid, methylene-succinic acid etc.

In the addition polymerization of acrylate elastomer, add the comonomer most convenient that contains functional group.Suspension, emulsion, solution, bulk polymerization are suitable.These polymerizations use radical initiator to cause.Emulsion polymerisation process is preferred.The soap of various routines, emulsifying agent and tensio-active agent are being known in the art and by reported in literature, and they can be used in functionalized acrylic ester rubber synthetic of letex polymerization.The weight-average molecular weight of the acrylate elastomer of difunctionalization generally surpasses 100,000.The acrylic rubber of the functionalization of business level can be from ZeonChemicals with HYTEMP ^Trade mark obtains.

The various α that contain active hydrogen functional group, β-undersaturated C ₂-C ₈Alkyl ester copolymer latex is known, and can obtain from various commercial channel.Preferred acrylic rubber latex can be from Noveon ^With HYCAR trade mark and Rhoplex ^Ex.Rohm and Haas obtain.Its Tg of multipolymer of n-butyl acrylate, vinyl cyanide, N hydroxymethyl acrylamide and methylene-succinic acid letex polymerization is less than 20 ℃, and is preferred vinylformic acid membrane-forming agent used in the aqueous coating embodiment.

Crosslinkable alpha-olefin copolymer

Poly-(olefin/propylene acid esters/carboxylicesters) multipolymer is the thermoplastics of last solid state, and has flexibility.These are by making at least a alpha-olefin and at least a (methyl) vinylformic acid C ₁-C ₁₈Alkyl ester and have the main multipolymer that the comonomer of unsaturated proton functional group is polymerized on a small quantity, wherein comonomer is used for forming cross-link bond with polymeric polyisocyanate, carbodiimide and other solidifying agent.The comonomer that has functional group can contain ethylenic unsaturated group and the group that has acid, hydroxyl, epoxide, isocyanic ester, An, oxazoline, diene or other reactive group.When not having the monomer of this functionalization, crosslink sites can result from the multipolymer of alpha-olefin-ester, for example produces by partial hydrolysis side chain ester group.Be applicable to that the elastomeric alpha-olefin of this olefin copolymer film forming of polymerization comprises ethene, propylene, 1-butylene, iso-butylene, amylene, heptene, octene and composition thereof.C ₂-C ₄Alpha-olefin is preferred, and ethene is most preferred.

Other example that has the functionalization comonomer of active hydrogen group is the ethylenically unsaturated compounds that contains epoxy group(ing), comprises glycidyl allyl ether, glycidyl methacrylate and glycidyl acrylate.The specific examples that contains the ethylenically unsaturated compounds of active halogen comprises vinyl benzyl chloride, vinyl benzyl bromine, 2-chloroethyl vinyl ether, Mono Chloro Acetic Acid vinyl ester, chloropropionic acid vinyl ester, Mono Chloro Acetic Acid allyl ester, chloropropionic acid allyl ester, vinylformic acid 2-chloroethene ester, methacrylic acid 2-chloroethene ester, chloromethyl vinyl ketone and 2-chloroethene acyl-oxygen ylmethyl-5-norbornylene.The specific examples that contains the ethylenically unsaturated compounds of carboxyl comprises vinylformic acid, methacrylic acid, butenoic acid, 2-pentenoic acid, toxilic acid, fumaric acid and methylene-succinic acid.

The example of ethylenic unsaturated (methyl) acrylate co-monomers comprises Octyl methacrylate; The alkyl ester that (methyl) vinylformic acid cyano group replaces is as 2 cyanoethyl acrylate, vinylformic acid 3-cyano group propyl ester and vinylformic acid 4-cyano group butyl ester; The alkyl ester of (methyl) acrylic-amino-replacement is as the vinylformic acid lignocaine ethyl ester; Fluorine-containing acrylate, as vinylformic acid 1,1, the 1-trifluoro ethyl ester; The alkyl ester of (methyl) vinylformic acid hydroxyl-replacement is as Hydroxyethyl acrylate; Alkyl vinyl ketone is as methyl vinyl ketone; Vinyl or allyl ethers are as EVE and allyl methyl ether; Vinyl aromatic compound is as vinylbenzene, alpha-methyl styrene, chloro-styrene and Vinyl toluene; Vinylamide is as acrylamide, Methacrylamide and N hydroxymethyl acrylamide; Reach ethene, propylene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene, vinyl-acetic ester, fumaric acid alkyl ester etc.

Preferred olefin-acrylic ester copolymer rubber contains the unsaturated carboxylic acid monomer unit, for example is derived from the acid unit of (methyl) vinylformic acid or toxilic acid, or for example is derived from the acid anhydrides unit of maleic anhydride, or for example be derived from the partial ester unit of ethyl maleate.In preferred embodiments, polymkeric substance is ethene, vinylformic acid C ₁-C ₄The unitary terpolymer of alkyl ester and carboxylic acid monomer; The terpolymer that more preferably contains the ethyl maleate of the ethene at least about 30 moles of %, about 10～about 69.5 moles of %.In all cases, preferred alpha-olefin acrylic elastomer is amorphous basically, and its glass transition temperature (Tg) is lower than about 20 ℃.Ethene-carboxylate copolymer is commercial can VAMAC ^Trade mark obtains.

When vinylformic acid and acrylate are alpha-olefin copolymer main chain a part of, change the amido reaction and can realize by the melting treatment technology, this is the technology of known preparation pendant hydroxyl group functional group, as using amino alcohol, for example 2-amino-1-ethanol.Further reaction can take place in pendant hydroxyl group, promptly with other acrylate chains generation transesterification reaction, thereby takes place crosslinked and the viscosity of product is increased.

Urethane

The pourable membrane-forming agent that contains curable polyurethane can serve as the film composition.The polymkeric substance of active hydrogen functionalization is saturated prepolymer, and available aliphatic polymeric isocyanate solidifies.The glass transition temperature of urethane cures is limited to and is lower than 0 ℃, and can be by slightly crosslinked in conjunction with alcohol, tetrol or higher OH functionality.Therefore to be limited to glass transition temperature for example be 0 ℃ or lower terminal hydroxy group hydrogenated butadiene polymer polyvalent alcohol homopolymer and multipolymer, poly-THF, polyester glycol, polypropylene glycol etc. to the polyvalent alcohol of chain extension, and this is known for those skilled in the art and can obtains from commercial.Can use conventional solidifying agent and catalyzer.United States Patent (USP) 4,669,517 disclose with the heat dissipation based polyurethane be coated to after the sclerosis vulcanising rubber surface so that urethane by adherent proper method admirably.The method for preparing the postcure surface can be used for applying pourable urethane heat dissipation coating.Contain in coating before the polyurethane reactive mixture of thermal conductive metal particle, tricyanic acid can be coated on the rubber surface that wherein contains polybutadiene polyol.Polyurethane reactive mixture can be solidified at ambient temperature.

Acryloyl urethane

Can expect that the acrylic substance through polyurethane-modified meets the needs of membrane-forming agent as herein described.These can solidify by the activation of moisture, heat or light.This glass transition temperature through polyurethane-modified acrylate is necessary for ℃ or is lower, and by a large amount of C ₂-C ₈Acrylate or methacrylic ester are formed.Be applicable among the present invention preferably example through the acrylic resin of urethane-modification, through the acrylic resin of urethane-modification by formula (I) when representing, be the acrylic copolymer of the methacrylic acid 2-hydroxyl methyl esters gained of the methacrylic acid of vinylformic acid first, the second of 60～70 moles of copolymerizations or butyl ester and 10～50 moles and 30～80 moles.Some or all hydroxyl and carboxyl by with α, β-ethylenic unsaturated isocyanate reacts and by end-blocking, for example by with methacryloxyethyl isocyanic ester (2-isocyanic ester ethyl-methyl acrylate).This material can solidify through moisture-curing and UV by adding conventional light trigger.In the embodiment of moisture-curing acryloyl urethane, make preferably that at least 10 moles of %, preferred at least 50 moles of %'s come from unitary hydroxyl of methacrylic acid 2-hydroxyl ethyl ester and methacryloxyethyl isocyanate reaction.α, β-ethylenic unsaturated isocyanate is preferably with isocyanic ester and contain the monomer of hydroxyl (as N hydroxymethyl acrylamide, the N-methylol methacrylamide, vinylformic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxypropyl acrylate, methacrylic acid 2-hydroxypropyl acrylate, vinylformic acid 4-hydroxy butyl ester and methacrylic acid 4-hydroxy butyl ester) reaction product be the basis, and selectively use the 3-aminopropyl triethoxysilane, the 3-aminopropyl trimethoxysilane, 3-aminopropyl methyl dimethoxysilane or 3-aminopropyl methyldiethoxysilane, brothers amine (as N-(2-aminoethyl)-3-aminopropyl trimethoxysilane), secondary amine (as the N-methyl-or N-phenyl-3-aminopropyl trimethoxysilane), the aminoalkylsilane of condensation is (as two (3-aminopropyl) tetramethoxies or tetraethoxy sily oxide NH ₂(CH ₂) ₃-Si (OCH ₃) ₂-O-(CH ₃O) ₂Si-(CH ₂) ₃NH ₂, through the propyl trimethoxy silicane of aminosilane of polyglycol ether-modification (as selling) and triamino functionalization (as " DynasylanTRIAMO " that can obtain from Huls AG) with trade mark " Dynasylan 121 ".Also can use similar silane with 2 or 3 Siliciumatoms.

The elastic material of maleinization

Various polymeric blends, alloy and kinetics sulfurized mixture based on the maleinization addition polymer of polyethylene can be used as functionalization film forming elastomerics of the present invention, as the polypropylene of maleinization, the styrene-ethylene-butylene-styrene-segmented copolymer of maleinization, the styrene-butadiene-styrene block copolymer of maleinization, ethylene-propylene rubber of maleinization and composition thereof.The elastomerics of maleinization may be dissolved in the suitable organic solvent system, and mixes with thermal conductive metal particle, and wherein thermal conductive metal particle preferably is pre-dispersed in the part of solvent for use.

The ethene vinyl ester copolymers

The ethylene copolymer of the OH functionalization of various other film forming of level, dissolvable agents dissolving is all applicable, and it contains carboxyl or hydroxy functional group, and is suitable as membrane-forming agent as herein described.Usually some in these polymkeric substance are as crosslinkable hotmelt, yet these polymkeric substance are easily as solidified radiation coating film at ambient temperature, even high temperature bond is relatively low.The ethylene-vinyl ester polymer that contains hydroxy functional group can be used in the radiation coating composition, and with the cured with isocyanates of block not, thereby can provide enough performances under some envrionment temperature of mobile being no more than solidified coating.The vinyl-vinyl acetate copolymer that contains the OH group is to comprise the polymkeric substance of ethene and vinyl alcohol monomeric unit and selectable vinyl-acetic ester, and its melt viscosity is preferably 4～40Pa.s under 180 ℃.Ethylene-vinyl alcohol copolymer preferably includes the vinyl alcohol units of at least 5 weight %.The terpolymer (180 ℃ of following viscosity is 20Pa.s, at 125 ℃ of following 325gm (6.4gm/10 minute) load MFR) that example is 10% vinyl alcohol, 88.75% ethene and 1.2 weight % vinyl-acetic esters.Its fusing point is 101.5 ℃ (DSC).Another kind of terpolymer contains 13.7 weight % vinyl alcohols, 82.3% ethene and 4.0 weight % vinyl-acetic esters (180 ℃ of following viscosity is 5.8Pa.s, at 125 ℃ of following 325gm (cf.30.4gm/10 minute) MFR, 91 ℃ of DSC fusing points).

The mixture of membrane-forming agent or the partial function fluidized polymer and the part NOT-function fluidized polymer class that contain interpenetrating(polymer)networks are applicable among the present invention.The alkene rubber polymer can become random or segmented copolymer with the mixed with polymers of functionalization, for example SBS, EBS, EPM and EPDM, hydrogenant polydiene copolymer, acrylic rubber and other above-mentioned membrane-forming agent.As an example, the polymer film-forming agent of NOT-functionization can be pressed the mixed of 10-90 weight %:90-10 weight % with the ethane-acetic acid ethyenyl ester polymkeric substance of partial hydrolysis, and is cured with suitable solidifying agent disclosed herein and Equivalent thereof.

The EPM of functionalization and EPDM elastomerics

The EPM of functionalization and EPDM elastomerics are the suitable film forming elastomericss as membrane-forming agent in the radiation coating.These materials contain two or more can with the α-monoolefine of polyenoid (normally non-conjugated diene comonomer) copolymerization.Useful polyenoid comprises 5-ethylidene-2-norbornene; 1, the 4-hexadiene; 5-methylene-2-norbornene; 1, the 6-octadiene; The 5-methyl isophthalic acid, the 4-hexadiene; 3,7-dimethyl-1,6-octadiene; 1; 1; Dicyclopentadiene (DCPD); 5-vinyl-2-norbornylene etc.; Or its mixture.Being preferred for EPM and the elastomeric polyenoid of EPDM functionalization is 5-vinyl-2-norbornylene, 5-ethylidene-2-norbornene and 1, the 4-hexadiene.Functional group can carry out combination by the method and the metathesis method disclosed herein of above-mentioned routine.

In aspect of the open method of the present invention, provide preparation to contain the useful especially scheme of the polymkeric substance of organic acid functional group (as carboxyl functional group, aliphatics or aromatic hydroxyl functional group etc.) and mineral acid functional group (as sulfuric acid functional group, phosphoric acid functional group etc.).

The scheme that shows a kind of EPM of being used for and EPDM rubber below is used in conjunction with side chain carboxyl group, hydroxyl or non-sterically hindered side chain alkene functional group.

Wherein n represents the conventional numerical value of repetition ethylene unit of the EPDM of commercial sale, m represents the conventional numerical value of propylene repeating unit, o represents the conventional numerical value of diene monomers repeating unit, and p represents the numerical value (1～100) of the Dicyclopentadiene (DCPD) repeating unit of maleinization.

The 4 above-mentioned same quadrat methods that are used for modified epdm are used in conjugated diolefin polymer in conjunction with functional group, as contain the perbutan of vinyl.

(B) curing agent component

The ambient temperature curing agent is multi-functional cure component, it contains any group in following: (1) has at least one group of active hydrogen and crosslinked group, wherein this crosslinked group is identical active hydrogen group or different crosslinked groups, or (2) can with at least one group of active hydrogen group and crosslinked group reaction, wherein this crosslinked group be can with the group of active hydrogen group reaction or different crosslinked groups.Under the urethane or urethane acrylate (acryloyl urethane) situation of cast, solidification occurs on the polyvalent alcohol and the part of the acrylate between polymeric polyisocyanate or polyisocyanate prepolymer and/or the ethylenic unsaturated group that selectively has the co-curing polyamine.Cure component is selected from polymeric polyisocyanate, polymeric isocyanate-polyvalent alcohol affixture, poly-carbodiimide, Duo Gong Neng oxazoline, Duo Gong Neng oxazine, multi-functional tetrahydroglyoxaline, phenolic varnish, resol resin, aminoresin and amino (alkoxyl group) silane of polymeric polyisocyanate, chain extension.Preferred cure component contains at least one isocyanate groups or has group or functional group reactions sexual intercourse symbasis group or its combination of isocyanate groups.The consumption of common cure component, addition polymer by per 100 weight part functionalization calculates, for about 3～about 30 weight parts, be preferably about 5～about 25 weight parts, and more preferably about 10～about 20 weight parts, or the equivalent weight by polyhydroxy reactant uses stoichiometric amount under pourable urethane situation.

Suitable solidifying agent comprises monomeric polyisocyanate, as contains the aliphatics or the aromatic diisocyanate of 2～40 carbon.Exemplary polymeric polyisocyanate comprises ethylene diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1, the 2-vulcabond, ethylidene diisocyanate, cyclopentylidene-1, the 3-vulcabond, 1,2-, 1,3-and 1,4-cyclohexylidene vulcabond, 1,3-and 1, the 4-phenylene vulcabond, diphenylmethanediisocyanate, the polymethylene isocyanic ester, 2,4-and 2, the 6-tolylene diisocyanate, 1,3-and 1, the 4-eylylene diisocyanate, two (4-isocyanate group ethyl) carbonic ether, 1,8-is diisocyanate based-to methane, 1-methyl-2, the diisocyanate based hexanaphthene of 4-, inferior chloro-phenyl-vulcabond, naphthylidene-1,5-vulcabond triphenyl methane-4,4 ' triisocyanate, isopropyl benzene-α-4-vulcabond, 5,6-dicyclo [2.2.1] hept-2-ene" vulcabond, 5, the diisocyanate based butyl dicyclo of 6-[2.2.1] hept-2-ene".Exemplary commerce product are trimethyl hexamethylene diisocyanate, heptadecyl (C17) vulcabond, DDI 1410 (can be from HenkelCorporation of Minneapolis, the aliphatics C-36 vulcabond that Minn obtains) and the Isonate that can obtain from VEBA ^143L vulcabond (the diphenylmethanediisocyanate (MDD) of the modification that can obtain from Upjohn Corp.Other urethane composition is the isophorone vulcabond that can obtain from VEBA and the Desmodur that can obtain from Mobay ^N (aliphatics triisocyanate).Desmodur ^N more particularly is defined as the reaction product of 3 moles hexamethylene diisocyanate and water, and its isocyanic ester equivalent weight is defined as 191.Other polymeric polyisocyanate affixture or prepolymer comprise Desmodur ^L and Mondur ^CB, it is the affixture of inferior cresyl vulcabond (TDI).

The example of alicyclic polymeric isocyanate comprises 1,3-cyclopentenes vulcabond, 1,4-cyclohexyl diisocyanate, 1,3-cyclohexyl diisocyanate, 1-isocyanate group-3,3,5-trimethylammonium-5-isocyanatomethyl-hexanaphthene (isophorone vulcabond, IPDI), 4,4 '-methylene-bis (cyclohexyl isocyanate), methyl-2,4-cyclohexyl diisocyanate, methyl-2,6-cyclohexyl diisocyanate and 1,3-or 1, two (isocyanatomethyl) hexanaphthenes of 4-and polymeric polyisocyanate (for example 1,3,5-triisocyanate basic ring hexane.Polymeric isocyanate is the employed preferred linking agent of curing radiation coating.The liquid polymerization isocyanic ester is preferred and widely-used.Term " liquid state " refers under envrionment temperature or high temperature it is liquid or at the polyisocyanate ester solution of the solvent that is used for polymeric polyisocyanate.The polymeric polyisocyanate that contains 10～50% reactive NCO groups is liquid state at ambient temperature, or can liquefy, or may be dissolved in carrier or the thinner down at about 70 ℃, and is applicable among the present invention.At United States Patent (USP) 3,644, polytype liquid isocyanate is disclosed in 457,3,883,571,4,229,347,4,055,548,4,102,833,4,332,742,4,448,904 and 4,490,301.

The liquid polyisocyanates that is suitable for can prepare by the substance reaction with various hydroxyl functionalizations.These react available organo-metallic or tertiary amine comes catalysis.Useful oxy-compound be contain have an appointment 1～36, be preferably the Fatty Alcohol(C12-C14 and C12-C18) of 4～16 carbon atoms.The Fatty Alcohol(C12-C14 and C12-C18) non-limiting instance is cycloaliphatic alcohol, contain the Fatty Alcohol(C12-C14 and C12-C18) of aromatic group, contain not the Fatty Alcohol(C12-C14 and C12-C18) with the group (for example ether group and halogen such as bromine and chlorine) of isocyanate reaction.The concrete limiting examples of Fatty Alcohol(C12-C14 and C12-C18) is 2-methyl isophthalic acid-propyl alcohol, cetyl alcohol, hexalin, 2-methoxyl group-ethanol and ethylene bromohyrin.Most preferred relative molecular weight reaches 150 branched fatty alcohol.

The exemplary liquid affixture of isocyanate compound comprises solid-state 4,4 '-and/or 2,4 '-diphenylmethanediisocyanate and side chain aliphatics dihydroxy compound are the reaction product of mol ratio of 0.1～0.3 mole dihydroxy compound with every mole of vulcabond.Other exemplary liquid MDI-based compound is MDI and single alcohol, gathers-1, the reaction product of the mixture that 2-propylene ether ethylene glycol is become with triol.Other exemplary liquid polyisocyanates is that average functionality is that about 1.5～about 4, average equivalent is at least the reaction product that about 500 alcohol or mercaptan and every hydroxyl and/or mercaptan equivalent are at least 2 normal organic polymeric polyisocyanates, and wherein about 20% initial urethane or the sulfo-urethane that forms can change into allophanate and/or thiourea carbamate.

The isocyanic ester that is well known that block can be used for forming coating, and heating steps is used for solidified coating.The suitable block agent that is used for reacting with organic list or polymeric polyisocyanate is isocyanic ester-reactive compounds, for example phenol, lactan, oxime, imide, alcohol, pyrazoles etc.The available any method well known in the art of the reaction of organic polymeric polyisocyanate and block agent is carried out.This reaction can be carried out in enormous quantities or for example carry out under about 50-120 ℃ the temperature in inert solvent.For the isocyanic ester of complete block, the equivalence ratio of isocyanic ester-reactive group and isocyanate groups is 1/1-2/1 or higher.The isocyanic ester of block is preferred fully, if still only need the polymeric polyisocyanate of part block, can regulate ratio so.

Containing the functionalization elastomerics uses after making immediately with the coating that is scattered in linking agent wherein.Used polyisocyanate curing agent in the embodiment of water-soluble underlying coating layer, for example used the polymeric polyisocyanate of water dispersible, these materials are known, and are for example having openly in the United States Patent (USP) 5,202,377.' but the exemplary emulsification polymeric polyisocyanate of instructing in 377 patents contains the oligopolymer of wetting ability uncle isocyanate functionization, and it is by reacting and possess hydrophilic property with hydrophilic polyethers.The isocyanic ester that is suitable for other water dispersible of water-soluble basic embodiment of the present invention is known.United States Patent (USP) 4,663,377 have instructed a kind of emulsible mixture of polyisocyanates, and it contains the oligopolymer of (a) hydrophilic isocyanic ester-functionalization, reaches (b) polymeric polyisocyanate.Non-limiting instance is the reaction product of aliphatic polymeric isocyanate and list or poly-hydroxy nonionic polyalkylene ether alcohol, and it contains at least one polyether chain, and this polyether chain contains at least 10 ethylene oxide units.The dispersible isocyanic ester of water is preferred, and based on aliphatics and alicyclic isocyanate.

Coating composition can form by mixing following material: (i) the dispersible linking agent of water, as carbodiimide or polymeric polyisocyanate, (ii) contain the independent aqueous solution, milk sap or the dispersion of the functionalization elastomer polymer of reactive functional groups.Selectively, containing the elastomeric water-soluble composition of functionalization can mix with the independent water-soluble dispersion that contains linking agent, and as United States Patent (USP) 5,466, that is instructed in 745 the vulcabond embodiment is such.Coating can be by mixing elastomerics in the water-soluble medium and water-insoluble emulsible and have not that the polyisocyanate crosslinking agent of block and the composition of surface active isocyanate-reactive materials prepare.When solvent is chosen as volatile organic component (VOC), this selectable method will be introduced some volatile organic compositions, yet can use other solvent except VOC.Carry out known process (i) then with the hydrophobic nature isocyanic ester and the thinner of block do not mix with the mixture of surface-active isocyanic ester-reactive materials and water, form oil and comprise water miscible liquid, (ii) this emulsion is added in proportion under certain condition then and contains in the elastomeric water-soluble medium to convert isocyanate emulsion to O/w emulsion.

The specific examples of commercial vulcabond is 1, and the 6-hexane diisocyanate (commercial for example can trade mark HMDI ^Obtain from Bayer), the isophorone vulcabond (commercial for example can trade mark IPDI ^Obtain from Huls), tetramethylxylene diisocyanate (commercial for example can trade mark m-TMXDI ^Obtain from Cytec), the 2-methyl isophthalic acid, 5-pentane vulcabond, 2,2,4-trimethylammonium-1,6-hexane diisocyanate, 1,12-dodecane vulcabond and methylene-bis (4-cyclohexyl isocyanate) (commercial for example can Desmodur ^W obtains from Bayer), and the isocyanic ester of higher functionalityization, as 1, the biuret of 6-hexane diisocyanate (commercial for example can Desmodur ^N obtains from Bayer), 1, the isocyanuric acid ester of 6-hexane diisocyanate (commercial for example can Desmodur ^N-3390 obtains from Bayer), the isocyanuric acid ester of isophorone vulcabond (commercial for example can Desmodur ^Z-4370 obtains from Bayer), the reaction product of tetramethylxylene diisocyanate and TriMethylolPropane(TMP) (commercial for example can Cythane ^3160 obtain from Cytec), and the reaction product of the tolylene diisocyanate of 1 mole TriMethylolPropane(TMP) and 3 moles (commercial for example can Desmodur ^L obtains from Bayer).The amount of contained two or polymeric polyisocyanate should be 3～30phr.Preferred amounts is 8～15phr.

The crosslinked composition of other class that can be used for solidifying the functionalization membrane-forming agent and form silicone cross-linked key is various known organosilanes.Preferred organosilane is an isocyanato silanes, it contains isocyanate groups and one or more can form the group of cross-link bond with silane and/or membrane-forming agent, reaches and other coreactivity substituting group such as acyloxy, sulfydryl, amino, phenol and the glycidyl of silicon by carbon atom bonding as hydrolyzable group, diazanyl, thiol, halogen, hydroxyl, alkoxyl group.Silane can contain vinyl; The group that contains vinyl; Other isocyanate groups; Other the group that contains isocyanic ester; The uride base; The group that contains the uride base; Imidazolyl; Or contain the group of imidazolyl.These compounds are well known in the art.

Silane-cure agent used herein can provide environment curable radiation coating, wherein contains 25～150 parts silane-cure agent by the membrane-forming agent weight of per 100 weight parts, and wherein membrane-forming agent contains the available solidifying agent solidified functional group that is no more than 10 weight %.But silane-cure agent monomer, tetravalence silane is two or oligomeric adjacent derivative, and it contains at least two siloxane bond groups, and according to functional group selected on film-forming polymer, it is identical or different coreaction group.A curing groups is hydrolyzable group, or can with the interactional group of acid or alkali functional group on the membrane-forming agent polymkeric substance.But the group of siloxanes bonding be with the membrane-forming agent polymkeric substance on the group that has active hydrogen of functional group's coreaction, perhaps the group of siloxanes bonding be with the membrane-forming agent polymkeric substance on the group that has active hydrogen be coreactivity.These organic silane compounds are known and can obtain from multiple commercial channel.

The representational silane general formula that preferably contains hydroxyalkyl is as follows:

Wherein R is divalence aliphatics, cycloaliphatic or the aromatic group that contains 1～20 carbon atom, be preferably contain 1～9, the alkylidene group of 2～4 carbon atoms most preferably; R ¹Be unit price aliphatics, cycloaliphatic or the aromatic group that contains 1～20 carbon atom, be preferably selected from the alkyl that contains 1～4 carbon atom, contain the cycloalkyl of 4～7 ring carbon atoms and contain the aryl of 6,10 or 14 nucleus carbon atoms and selectively one or more contain the substituted alkyl R of 1～4 carbon atom ²Be unit price aliphatics, cycloaliphatic or the aromatic series organic group that contains 1～8 carbon atom, be preferably selected from methyl, ethyl, propyl group, butyl and R ³-O-R ⁴, R wherein ³Be alkylidene group-C=(the O)-R that contains 1～4 carbon atom (methyl, ethyl, propyl group, butyl), R ⁴It is the alkyl that contains 1～4 carbon atom; Reaching a is 0 or 1, is preferably 0.

The silane of amino functional is preferred for the membrane-forming agent that solidifies carboxyl-functional, comprises shown in the following structure (B) those:

Wherein R, R ¹, R ²With a and the identical R of aforementioned definition to (A) ⁵Be selected from hydrogen, contain 1～8 carbon atom the unit price aliphatic group, contain 4～7 ring carbon atoms unit price cycloaliphatic group, phenyl, contain 6 nucleus carbon atoms and contain alkaryl, radicals R with one or more substituted alkyls of 1～4 carbon atom ⁷-NH-R ⁶-, R wherein ⁶Be selected from the divalence aliphatics, cycloaliphatic and the aromatic group that contain 1～20 carbon, preferably at least two carbon atoms are with arbitrary non-conterminous to nitrogen-atoms, R ⁶The alkylidene group of 2～9 carbon atoms preferably; R ⁷With R ⁵Identical and hydrogen preferably.

Mercapto-functionalized silane comprises those shown in the following structure (C):

Wherein R, R ¹, R ²Identical with a with aforementioned definition to (A).

Organic silane compound used herein is included in and contains on the Si atom as those of the substituent organic chain that has 1～20 carbon atom, at least one derivable hydrogen atom preferably is connected in the functional group, by the carbon atom chain of at least 3 interconnection itself and Siliciumatom is isolated.

Preferred organosilane is an isocyanato silanes.The example of the commercial available isocyanate group-organoalkoxysilane that is suitable for comprises that γ-isocyanate group propyl trimethoxy silicane (can Silquest ^Obtain a Witco company (OSi) from OSi Specialties Group) and γ-isocyanate group propyl-triethoxysilicane (can Silquest ^A-1310 obtains from OSi).

The representative title and the popular name that contain the organosilane of active hydrogen group are the hydroxypropyl Trimethoxy silanes, the hydroxypropyl triethoxyl silane, the hydroxybutyl Trimethoxy silane, γ-An Bingjisanjiayangjiguiwan-γ-An Bingjisanyiyangjiguiwan, the methyl aminopropyl trimethoxysilane, γ-aminopropyl tripropoxy silane, gamma-amino isobutyl-triethoxyl silane, γ-aminopropyl methyldiethoxysilane, γ-aminopropyl ethyl diethoxy silane, γ-aminopropyl diethylamino phenyl TMOS, methyltrimethoxy silane, ethyl trimethoxy silane, propyl trimethoxy silicane, butyl trimethoxy silane, the isobutyl-Trimethoxy silane, the hexyl Trimethoxy silane, the octyl group Trimethoxy silane, the decyl Trimethoxy silane, cyclohexyl trimethoxy silane, cyclohexyl methyl Trimethoxy silane etc.

Silicol with (Si-OH key) also is suitable for makes solidifying agent, selectively is part neutral silandiol or silantriol.Silanol preferably contains at least one nucleophilic reagent that is connected with silicon by first linking group.Term used herein " part neutralization " refer at least some silanol be single, two or ternary an alkali metal salt, more particularly lithium, sodium or sylvite.But the neutral degree is the condensation degree that presents in an amount at least sufficient to suppress silanol condensation group is no more than 50%, but can between silane and film-forming polymer, provide enough interaction forming cross structure, but can the gel film-forming polymer when part A and part B mixing.Solidifying agent is by the part neutral silanol shown in the structure D:

Wherein n is 1,2 or 3; M is 0,1 or 2; P is 0 or 1, is preferably 0, and condition is m+n+p=3; R is first linking group; M ⁺It is the metal that forms basic salt; Y is the group that contains the nucleophilic part; R ' is straight chain, side chain or cyclic C ₁-C ₈-alkyl, preferably methyl or ethyl are more preferably methyl.Linking group R among the D is preferably straight chain, side chain or cyclic alkylidene group or arylidene or its combination, and can contain one or more heteroatomss, and itself is nucleophilic.More preferably, X is C ₂-C ₆-alkylidene group or-R '-NH-R '-, wherein each R ' is C independently ₂-C ₄-alkylidene group.

The example of suitable nucleophilic reagent comprises amine, phenol, mercaptan and carboxylicesters, and primary amine and secondary amine and mercaptan are preferred, and primary amine and secondary amine are preferred, and primary amine is most preferred.The specific examples of part neutral aminosilane triol is the potassium or the sodium salt of 3-aminopropyl-silantriol and N-(2-aminoethyl)-3-aminopropyl-silantriol normally.

Preferred organosilane solidifying agent contains the group of at least one siloxanes bonding, its contain replace or unsubstituted and with the alkylamino and the alkoxyl group of siloxanes bonding, thereby can in the condensation of organosilane, form cross-link bond.Amine groups can be the free not form of block or the amino of block.The block of amine groups can provide by the reaction with methyl iso-butyl ketone (MIBK) or Methyl amyl ketone.Can with the preferred group of silane compound reaction C preferably ₁-C ₄Alkoxyl group.The example of cure component includes but not limited to aminosilane, can be aminopropyl-triethoxy or methoxy silane, aminoethyl aminopropyl-triethoxy or methoxy silane, the 3-aminopropyl triethoxysilane, the 3-aminopropyl trimethoxysilane, 3-aminopropyl methyl dimethoxysilane or 3-aminopropyl methyldiethoxysilane, the silane (as N-(2-aminoethyl)-3-aminopropyl trimethoxysilane) that contains brothers amine, secondary amine (as the N-methyl-or N-phenyl-3-aminopropyl trimethoxysilane), the aminoalkylsilane of condensation is (as two (3-aminopropyl) tetramethoxies or tetraethoxy sily oxide NH ₂(CH ₂) ₃-Si (OCH ₃) ₂-O-(CH ₃O) ₂Si-(CH ₂) ₃NH ₂, through the propyl trimethoxy silicane of aminosilane of polyglycol ether-modification (as selling) and triamino functionalization (as " the Dynasylan TRIAMO " that can obtain from Huls AG) with trade mark " Dynasylan 121 ".Also can use similar silane with 2 or 3 Siliciumatoms.

The preferred mixture of aminoalkyl trialkoxy silane and fluoroalkyl trialkoxy silane shows improved colour stability (not flavescence) when the heat aging solidified coating.

Fluoroalkyl silane can be used in the mixture with the another kind of silane that contains active hydrogen, with the mixture of aminosilane solidifying agent of the present invention in formula E most preferably:

R wherein ¹Be the single fluorizated that contains 1～20 carbon atom, low fluorizated or fluoridized alkyl or single fluorizated, low fluorizated or fluoridized aryl, Y is CH ₂, O or S, R ²Be straight chain, side chain or cyclic alkyl or the aryl that contains 1～8 carbon atom, R is straight chain, side chain or cyclic alkyl or the aryl that contains 1～8 carbon atom, y is 0 or 1, m is 0 or 1, the representative specific examples of some fluoroalkyl silane comprises 3,3,3-trifluoro propyl Trimethoxy silane, 3,3,3-trifluoro propyl methyl dimethoxysilane, 3,3,3-trifluoro propyl methyl dimethoxysilane, 3,3,3-trifluoro propyl cyclohexyl dimethoxy silane, 3,3,3-trifluoro propyl diethylamino phenyl TMOS and heptadecyl trifluoro decyl Trimethoxy silane CF ₃(CF ₂) ₇CH ₂CH ₂Si (OCH ₃).

Its amount can be used as cure component less than the aminoresin of membrane-forming agent 10%, wherein uses acid catalyzed heating condition.Aminoresin refers to the material of any reaction based on formaldehyde and urea, trimeric cyanamide, benzo guanamine or acetylguanamine etc. in the big class material.These compounds are known and are disclosed in for example " Kirk-Othmer Encyclopedia Of Chemical Technology ", 3 ^RdEd., Volume 2, Page440-469, and Wiley-Interscience is in 1978.

The solidifying agent that contains at least two ethylenic unsaturated double-bonds (each two key can by adjacent electron-withdrawing group activation and can carry out the Michael addition with the functional group on the film-forming polymer) is suitable and also is known, for example toxilic acid dicarboxylic anhydride and fumaric acid dicarboxylic anhydride.

The example of other suitable cure component is a carbodiimide.The elastomerics that contains functional group that multi-functional carbodiimide and the present invention are used shows suitable reactivity.The N-acyl urea group is formed between the carboxyl position.The carbodiimide key also can be formed between other contained in the elastomerics of carboxyl and functionalization functional group, as diazanyl, amino and/or thiol group.Multi-functional carbodiimide can use as United States Patent (USP) 2,941, and the echothiophate oxide compound described in 966 obtains from polymeric polyisocyanate as catalyzer.The dispersible carbodiimide of water can be by adding hydrophilic polyamine or polyvalent alcohol and containing the carbodiimide of isocyanate groups, make reactant by the catalyzer of reaction mixture weight 0.01～3% (at United States Patent (USP) 4, open in 321,394) existence formation down.Use catalyzer can obtain rearrangement product tin acetate (II) or dibutyltin diacetate down at 25-150 ℃.The compound that contains hydroxyl is hydrophilic radical preferably, and comprises that the polyvalent alcohol that contains 2～8 hydroxyls, particularly molecular weight are 800～10, those of 000.Exemplary polymerized polyalcohol comprises for example polyester, polyethers, polythioether, polyacetal.Hydrophilic multi-functional carbodiimide contains hydrolyzable silane group and multi-functional carbodiimide, and it also is suitable for, particularly for United States Patent (USP) 5,258, and the embodiment of the aqueous coating in 481 inventions of being instructed.

The example that is used for the present invention's suitable carbodiimide compound is N, N '-dicyclohexylcarbodiimide, 1-ethyl-3-(3 '-dimethyl aminopropyl) carbodiimide, N-ethyl-N '-(3-dimethyl aminopropyl)-carbodiimide, N '-di-isopropyl-carbodiimide, N ' N '-di-t-butyl carbodiimide, 1-ring-hexyl-3-(4-diethylin cyclohexyl) carbodiimide, 1,3-two-(4-diethylamino basic ring-hexyl) carbodiimide, 1-cyclohexyl-3-(diethyl aminoethyl) carbodiimide, 1-cyclohexyl-1-cyclohexyl-3-(2-morpholinyl-(4)-ethyl) carbodiimide, 1-cyclohexyl-3-(4-diethyl-aminocyclohexyl) carbodiimide etc.Commercial available solvent is soluble to be had multiple with the dispersible carbodiimide of water.Carbodiimide compound be commercial can be from Union Carbide Corp., USA is with trade mark UCARLNK ^Obtain.

(C) carrier liq

Coating is used in the carrier liq.Carrier liq is one or more organic solvents or water, although a spot of a kind of solution can be contained in the material, cosolvent thing, dispersion agent of other adding etc., thereby carrier can contain than the solvent of small proportion or cosolvent and than the water of small proportion.Coating composition of the present invention preferably is coated on the elastic substrate with the form of one or more organic solvent carrier solns.For the purposes of the present invention, the term solvent may be defined as the carrier that is used for other composition of composition, and wherein solvent can dissolve or keep composition at dispersive state or mixture basically.Preferred solvent comprises water-based latex and/or non-HAP (fatal atmosphere pollutent) or non-VOC or non-HAP, non-VOC organic solvent.

Non-HAP solvent comprises methyl acetate, n-butyl acetate, tert.-butyl acetate, acetone, ethyl acetate, isopropyl acetate, isobutyl acetate, tetrahydrofuran (THF), N-Methyl pyrrolidone, aliphatic hydrocarbon (as hexane), dimethyl formamide, diisobutyl ketone (DIBK), methyl isoamyl ketone, monochloro toluene, p-chloro benzo trifluoride-99 (PCBTF), reaches vm﹠amp; The p petroleum naphtha.The mixture of acetone and DIBK is preferred non-HAP solvent mixture.Independent acetone, methyl acetate and p-chloro benzo trifluoride-99 (PCBTF) or any combination are the coating solvents that preferred HAP and VOC adapt to.The HAP that has photochemical reaction in air is hexane, dimethylbenzene, toluene, MEK and MIBK.When HAP and VOC adaptability did not play a crucial role, toluene, dimethylbenzene, MEK and MIBK were preferred solvents.

The solvent that is used as the carrier of coating composition of the present invention can be organic solvent or other material of any solubilized acrylonitrile butadiene copolymer basically.The representative examples of organic that is used for the present invention comprises ketone such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and diisobutyl ketone; Acetic ester is as butylacetate; Toluene, dimethylbenzene and derivative thereof; Nitropropane; And Ethylene Dichloride.

The organic solvent of solvent base embodiment of the present invention counts about 70%～about 97% by the gross weight of coating composition (HNBR of solvent, functionalization, cure component, heat conduction particle and selectable composition) usually.Preferably solvent is about 85%～95% by weight.Thus, total non-volatile solids amount of coating composition be about 3～about 30%, be preferably about 5～about 15%.

Usually making water is highly preferred as carrier, and helps environment.The present invention can utilize following by the latex polymer of emulsion polymerization prepared and the dispersion of the water-soluble conversion of polymer solids.Solid-state bulk elastomerics membrane-forming agent can change into dispersion by dissolving in suitable organic solvent or ORGANIC SOLVENT MIXTURES.The example of organic solvent includes but not limited to any organic solvent of listing above, preferably methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and methyl isopropyl Ketone.Solvent is solvent mixture also, and lower water solubility is preferably arranged, and selectively solvent surpass about 50% or boiling point be lower than about 95 ℃ and can form azeotrope with water when being lower than the boiling point of water at least.The polymers soln of external phase adds water treatment then through adding tensio-active agent.Hybrid technology well known in the art can be used negatively charged ion, positively charged ion, nonionic or amphoteric emulsifier, comprises mixture.The aqueous organic solvent mixture mixes under high-shear, and undergoes phase transition, and wherein water becomes external phase.Usually the boiling point by being lower than water and be usually less than 95 ℃ down heating remove and desolvate.Preferably before applying, cure component and other composition that needs are added in the latex.

The more suitable open process for preparing water-soluble basic X-HNBR rubber latex is in United States Patent (USP) 4,826, in 721, is incorporated herein this patent as a reference.Rubber constituent is dissolved in the solvent, as 3-chloro-toluene.Also can add emulsifying agent, as rosin (colophony type) acid derivative and westvaco rosin acid derivative.Water also can be added in the composition.With composition emulsification, desolventize with rotary evaporation subsequently, preferably rotary evaporation under the decompression.X-HNBR latex also can obtain from the Nippon Zeon of Japan.The used water-based latex coating composition of the present invention contains 30～50% solid by weight usually.

Radiation coating composition of the present invention solidify to form limpid or transparent basically matrix elastomerics.Thereby for the incident radiant heat is transferred in the thermal conductive metal particle of lower floor heat is reflected by coatingsurface, transparency is important.In the base material that thermal conduction advance is applied, during temperature under detecting product surface, also observe surprising heat reflection.Even the low surface area base material also can be observed heat dissipation character,, the reduction of base material temperature is directly proportional with the ratio of surface-area to lower floor's product volume although also expecting.

The selectable coloring compound of lower level such as dyestuff or pigment dyestuff also can add.Colored film of the present invention can be long-term weathering use outstanding color and coating physical properties is provided.The pigment dyestuff that is fit to add in the tinting material can be at Rubber Blue Book (Lippincott ﹠amp; The PetoPublications publication) find in, this is known for the affiliated technician in the elastomer production field.Usually used organic colorant can play different pigmentations.The organic colorant of non-pigment makes coating transparent, but has color or shade.

(particularly micronized (diameter is 0.5 micron or littler) is 2.0 weight parts in the elastomerics membrane-forming agent of per 100 weight parts to inorganic, metal oxide pigment, for example can use the titanium that can not influence coating heat dissipation character basically.Can use Banbury mixing tank or end runner mill that pigment is mixed with solid polymer.The rubber that contains pigment then is dissolved in the solvent.Selectively, pigment can be dispersed in the liquid solvent, is added to then in the polymeric blends of solvation.This is the preferred method that adds aluminum slice.The exemplary solvent dispersion of kaolin contains 50 parts the kaolin and the mixture of 55 parts of ethylene glycol and 45 parts of ethylene glycol monobutyl ether.

The metallic conductor particle

In the embodiment of the coating with heat dissipation character, for effective heat dissipation character is provided, the surface coverage minimum is necessary in the coating.Term " particle " comprises irregular shape, particulate-type, laminar shape or complicated mixing shape.Heat reflection pigment can be various ways, as the fine-grannular solid in solvent or softening agent (for example mineral essential oil) or laminar, dried powder shape or dispersion or mashed prod.The thin slice that is derived from finely divided vapor deposition film is suitable.Thermal conductive metal particle comprises irregular particle or the laminar particle that copper, titanium, silver or aluminium are finely divided.Preferably the film with the particle/washing of washing is added in thin slice or the non-thin slice aluminium.Thin slice (as thin slice aluminum particulate or thin slice) is commercial can be obtained from the stearic acid that applies, and when being coated to the surface, particle alignment becomes to be parallel to the decussate texture on final radiation coating surface.When in the film of 5mils (0.01cm), pouring into a mould, its mean particle size of used metallic particles is 5～25 μ m, its consumption is 10～100 weight parts in per 100 weight part film forming elastomericss, and can provide effective radiant heat heat dissipation, so that enough anti-deflection-fatigabilities to be provided, thereby do not produce the diaclases in coating.The diaclases makes the heat dissipation performance loss.Mean particle size is that its consumption of metallic particles of 25～100 microns is at least 20 parts～150 weight parts in per 100 weight part membrane-forming agents, so that enough radiant heat heat dissipation to be provided, and does not produce the diaclases.Usually the aluminum slice mean particle size that is suitable for is less than about 300 microns.Maximum diameter with metallic particles of high aspect ratio is uncertain, comprises two principal dimensions (width and length) and a less size (thickness), and it is than two little several magnitude of main size.Determine mean particle size according to specifications for delivery.Preferably, the number average particle size of aluminum slice is about 1～about 100 microns, more preferably 5～60 microns, and more preferably 10～45 microns again.Preferred aluminum particulate is that have 99.9% can be by the thin slice of 325 mesh sieve, and promptly diameter is less than about 45 microns, and most preferably mean particle size is 8～35, particularly 10～20 microns.

Sheet metal can drying slice rather than the form of the mashed prod (as United States Patent (USP) 5,045,114 described kaolins are at least about 40 weight %, and kaolin is 60～70 weight % more preferably from about) of aluminium and solvent add.For having the heat dissipation performance, metallic particles uses with the amount relevant with film-forming polymer.The preferred amounts of metallic particles is to be 15～30 weight parts in per 100 weight part membrane-forming agents.This ratio comprises considers surface additive (for example tensio-active agent) or adhesion promotor (for example silane).

Coating composition of the present invention can contain other selectable composition, as the particle toughener of nitroso compound, ZnO, QDO, maleimide, antioxidant and sub-micron.The total amount of selectable additive should be in the film-forming polymer of per 100 parts of functionalization and is no more than about 15 parts.The specific examples of used particle toughener comprises sedimentary silicon-dioxide and the silicon-dioxide of being fuming among the present invention.Can use the gloss of the matting agent well known in the art of significant quantity with the control solidified coating, it includes but not limited to silicate.Its granularity of selectable silicon-dioxide is more typically 20～200 nanometers less than 700 nanometers.The transparency that the particle toughener of sub-micron can not influence membrane-forming agent is attended the meeting and is reduced the obvious degree of coating heat dissipation character, and its amount is no more than 20 parts for various amounts in the elastomerics film-forming polymer of per 100 weight part functionalization.

Coating composition can be prepared as follows: mix each composition or mechanically mixing or shake with spatula is manually simple.Coating composition can be coated on elastic material and/or other base material by dip-coating, spraying, obliterating, brushing etc. usually, with dry about 30 minutes～2 hours of coating, and preferred about 45 minutes～1 hour.Coating composition applies the drying layer that forms the about 0.1～5mils of thickness (2.54 μ m～127 μ m) at base material usually, preferred about 0.5～1.5mils (12.7-38.1 μ m).When solid state, the supported or supported coating film in end can extend at least 100% of original length, preferably can prolong 200%, more preferably can prolong 300%, and can not produce the crack.

Coating composition can be coated to and cure or not on sulfuration or the base material of uncured base material and co-curing, and uses high temperature when needed.

The gloss of solidified coated substrate (thereby transparency do not have obviously reduce) can be at least by using various amounts of solvent, control vaporator rate and/or add various known pigment and/or matting agent being controlled.Found for the coating of organic carrier base, relatively comparatively fast or fast evaporated, compared the more smooth or less glossy of generation surface with the solidification rate of longer time.Solidified coating of the present invention can make base material have about gloss of 3%～about 70% usually when 60 ° angle, and this can utilize Byk-Gardner Micro TRIGlossmeter to measure according to ASTM D-523 and D-2457.The glossiness of expectation can change according to purposes, and surface color and polish needs low-luster, and decorative coating need be medium to the higher gloss degree.For example, coating composition can make sidewall have the outward appearance of create an aesthetic feeling, as " wire netting " shape.The final gloss of controlling solidified coating effectively can produce needed surface, polishing or outward appearance on base material.

Coating composition can solidify in about 2～24 hours (to comprise room temperature) under ambient air conditions.Quicken by making coatings applications high temperature to solidify, but do not need like this.

(D) flexible substrate

Coating composition of the present invention can apply flexible substrate, as the elastic material of the multiple casting mold under Procuring and curing postcondition.Coating is coated on the entire exterior surface.Coating composition can be applicable to goods moulding or casting mold, as the goods of being made by Thermoplastic Vulcanizate or thermoset rubber.Coating composition of the present invention is specially adapted to apply solidified rubber engine mount equipment, and it is made up of the sulfuration elastic part that is attached on the metal parts.

The engine mount structure comprises the substrate layer that is formed by natural rubber, selectively sticks together with one or more metal frame parts and/or is formed at around it, is used for by screw retention vehicle structure and engine shell.Substrate layer is easy to decompose because of the erosion of heat, oxidation, ozone or ultraviolet radiation.The coating of spraying or dip-coating heat dissipation, and the profile of itself and frame is coincide, its floating coat allows fully to be solidified after being coated to above-mentioned substrate layer, wherein the coating of heat dissipation is applied on the substrate layer, so that the service temperature or the equilibrium temperature of the rubber part inside of frame reduce by 30  (16 ℃) at least during operating conditions, more preferably at least 50  (27 ℃), most preferably at least 75  (41.6 ℃).

When as the coating on the curing elastomer with limited oil-proofness and good solubility-resistence, preferred radiation coating composition is effective especially.This elastomerics comprises the nitrile-divinyl rubber of natural rubber, styrene butadiene ribber, polybutadiene rubber, ethylene, propylene and propylene diene rubber, polyisobutene-different limonene rubber, sovprene, low acrylonitrile content (＜35 weight %) etc.Coating composition also can be used on the rigid substrate, as metal, plastics, pottery and mixture.The example of thermoplasticity and/or thermoset base material includes but not limited to flexible polyvinyl chloride, polyvinyl chloride-elastomer alloy (as the PVC-nitrile); The polyolefine of viscosity enhancing or modification is as polyethylene and polypropylene composite; Flexible polyester (as PBT), flexibility or elastic polyurethane-, polyureas-, the polyureas edge; Fiber strengthened flexiplast, porous ethylene base and urethane.Coating is specially adapted to the bonding flexible and rubber frame rigidity composition of containing.If the ductility of substrate material, can think so that base material is flexible greater than 25%.

Can include but not limited to tire, snubber, wiper blade, concussion separator, rubber frame, rail pad fastener, helical rotor bearing, sole, scrape water frame, packing ring, heel, sole, marking roll, belt, flexible pipe, fuel bath, rubber mold, TPO or TPE mould, gauge plate and flexible engineering rubber product with the present composition other example that apply and common available flexible substrate.Except the heat dissipation performance, coating also can provide oil-proofness, solvent resistance, oxygen resistence, ozone resistance and the photosensitiveness of anti-UV.

Coating composition of the present invention can be coated to a side or all sides of base material.Should be appreciated that sometimes coated side only is effective to the side or the surface of the base material of thermal source for dissipation of heat.As mentioned above, the substrate surface that contacts with light, air, oil and solvent of coating advantageously.Obviously do not need to apply the substrate surface that does not contact with light, air, oil and solvent.Preferably coating is the continuous coated of form of film, thus the surface of covering substrates fully.The thickness of coating needs to cover the protected surface of desire, does not change the mechanical property of base material but can thickly not attend the meeting.

Tire can apply with composition of the present invention.Should be appreciated that available coating composition covers the whole outside surfaces and/or the internal surface of tire.In addition, also can only apply some part in the tire as required, as sidewall, tyre surface etc.Tire generally includes tyre surface, a pair of and sidewall that tyre surface joins in land areas, normally annular fabric enhanced rubber component and one or more stratum reticulare that is used to support tyre surface and sidewall, and the fabric enhanced and the belt between member and tyre surface of the circumference of one or more stratum reticulares.Tire also comprises the pencil wire bead core of a pair of circumference expansion usually, and it is non-extensible basically, and wherein member extends to another bead from a bead, and lateral margin can be around bead.Tire also can comprise a pair of summit element, preferably includes the rigid structure in the bead zone and has the trilobal(cross)section, and a pair of hard interference element that is arranged in the bead zone.The tire component of listing above is conventional element, still be appreciated that also to comprise other part of not listing, and the element of listing above also can omit.Tire also can comprise inner liner, and it is added on the inside tires surface in order to improve the air impenetrability.The all available composition of the present invention of any tyre element applies.Preferably, tyre surface and/or sidewall areas are applied.

The preparation of the elastomer substrates that is used to apply

Elastic surface that desire applies or base material are selectively through the chlorizating agent pre-treatment, as clorox and hydrochloric acid.It is well known in the art using various chlorizating agents to prepare the elastic material that is used for the applying coating composition.An example of chlorizating agent commercial can be from Lord Corporation with CHEMLOK ^Trade mark obtains, as 7701.Chlorizating agent can be coated to the elastic material surface by brushing, dip-coating, spraying, obliterating etc., can be with the chlorizating agent drying after the coating.Chlorizating agent is highly susceptible to volatilization, and usually can be at several seconds or several minutes inner drying.

Coating composition of the present invention has surprising ability separately and aspect the flexible resilient part formation good bond, also can be bonding with hardware, and wherein hardware and elastic part are adjacent.Preferably can on elastomerics and metal, provide elastic coating, thereby the border of elastomerics and metal can be adequately protected by coating composition.The present invention thereby can distinguish mutually with multiple traditional protective coating composition, traditional protective coating composition only has the base material adherent ability with the desire protection.

The following examples are used to illustrate the present invention, limit the scope of the invention but be not used in, and scope of the present invention is defined by the claims.

Embodiment 1

Use Zetpol 2220 (a kind of X-HNBR polymkeric substance of producing by Zeon Chemical, wherein acrylonitrile content is 36%, degree of unsaturation is 5 moles of %) the preparation the following examples.Suitable commercial substitute is Therban ^KA 8889.

Being prepared as follows of elastomer coating solution:

Composition explanation PHR

X-HNBR carboxylic acidifying hydrogenated nitrile-divinyl 100.0

This preparation may be dissolved in the methyl iso-butyl ketone (MIBK) (MIBK, CAS No.108-10-1), and solids content is 12.0 weight %.

Add 53% the xylene solution of two-[isocyanate group phenyl] methane (vulcabond) of 0.1g, 0.5g and 1.0g in the solution to 40 grams.When the 0.1g vulcabond, be less than solution curing in 16 hours under the room temperature.When 0.5g, solution solidified in 30 minutes.

The 3-isocyanate group propyl-triethoxysilicane that in the solution of 40 grams, adds 0.3,0.7,1.0 and 1.3 grams, CAS#24801-88-5.In all consumptions, coating composition began to solidify in 45 minutes～1 hour, and completely solidified was less than in 16 hours.

The fuel resistance test

Using Chemlok ^The 7701 55 hardness natural rubber compounds of handling (A135Q) are gone up testing coating.The coml fluororine-carbon coating PLV-2100 of coating and 5,314,955 instructions of US patent and the control group of coml HNBR SPE XV coating and end coating are compared.

When in being immersed in Jet A fuel under the room temperature, reaching 24 hours, can obtain following volume % expansion results:

192.9% of contrast end coating

Contrast PLV 2,100 0.1%

Contrast HNBR SPE XV 33.6%

The embodiment coating 2.2% that contains two-[isocyanate group phenyl] methane

The embodiment coating 2.3% that contains 3-isocyanate group propyl-triethoxysilicane

The binding property test

By two one inch wide bands are bonded together and pull viscosity under 180 ° with testing rubber.Rubber strip is by using Chemlok ^The 7701 55 hardness natural rubber compounds of handling (A135Q) are made.There are two inches long cross sections coated approximately; Each band and another band contact with each other, and the weight that adds 472g is to guarantee tight contact.Weight was placed 10 minutes.After dry 8 days, each band Tinius Olsen ^Stretching testing machine draws back.Outcome record is in following table.

Types of coatings peel results Lbf

Contrast PLV 2,100 2.03

Contrast HNBR SPE XV 8.52

The embodiment coating 15.5 that contains two-[isocyanate group phenyl] methane

The embodiment coating 21.1 that contains 3-isocyanate group propyl-triethoxysilicane

1 inch wide rubber strip and 1 inch tinsel are passed through 1 square inch

Overlapping linking together to utilize the shearing test metal adhesion.Rubber strip is by using Chemlok ^The 7701 55 hardness natural rubber compounds of handling (Al35Q) are made.Tinsel is 304 stainless steels.Selecting stainless steel is because it is the known base material that is difficult to connect.After the coating, each band and another band contact with each other, and the weight that adds 472g is to guarantee tight contact.Weight was placed 10 minutes.After dry 8 days, each sample Tinius Olsen ^Stretching testing machine draws back.

Types of coatings adhesion results psi

Contrast PLV 2,100 16.78

Contrast HNBR SPE XV 19.23

The embodiment coating 18.2 that contains two-[isocyanate group phenyl] methane

The embodiment coating 18.5 that contains 3-isocyanate group propyl-triethoxysilicane

Ozone resistance

Use the dynamic ozone test machine (ASTM-D3395) in 50pphm ozone to carry out the ozone test down at 104  (40 ℃).

Sample is based on the commercial sulphur-solidified natural rubber/mixed with polybutadiene thing of 55 hardness, and it is subjected to the protection of anti-ozone wax and alkyl-aryl phenylenediamine antiozonidate (M122N).Under dynamic condition, carboxylic acidifying hydrogenated coatings is more effective than HNBR coating SPEXV as the ozone blocking layer.

The used time of crack appears:

Contrast uncoated 6.5 hours

Contrast HNBR SPE XV 6.5 hours

Embodiment 1 coating 28 hours that contains two-[isocyanate group phenyl] methane is the crack not

Embodiment 1 coating 28 hours that contains 3-isocyanate group propyl-triethoxysilicane is the crack not

Except having lower adhesion value, after deflection PLV 2100 coating cracks and with the rubber surface layering.Unpierced DeMattia deflection sample (obtaining from 55 hardness natural rubber compounds) applies with these coatings, and according to ASTM D-813 deflection.Serious crack of PLV-2100 coating and layering, thus the base material cycle index is less than 4000.The HNBR SPE XV that cured does not have tangible layering.When containing the heat-conducting metal of significant quantity, this basic preparation shows good performance, and more a step provides the heat dissipation performance.

Embodiment 2

Use from Bayer AG with Therban ^Therban in the trade mark ^The X-HNBR polymer manufacture the following examples that KA 8889 obtains.

Being prepared as follows of elastomer coating solution:

Composition explanation PHR

X-HNBR carboxylic acidifying hydrogenated nitrile-divinyl 100.0

This preparation may be dissolved in the methyl iso-butyl ketone (MIBK) (MIBK, CAS No.108-10-1), and solids content is 15.0 weight %.

Average particulate diameter is that 16 microns 33phr kaolin is added in the coating solution.

Two-[isocyanate group phenyl] methane (the vulcabond) (Casabond that in the solution of 97.5 wet weight parts, adds 2.5 wet weight parts ^TX is in the dimethylbenzene 53%).

" (7.6cm * 7.6cm * 1.2cm) its hardness A is 65, and is coated to the about 1mil of dry film thickness to solidify blocky natural rubber 3 " * 3 " * 0.5.

Get out a hole at the block center, 1.5 inches (3.8cm), and insert thermopair with detected temperatures.Block placed under 250 watts the infrared lamp, " (20cm) apart from block rubber 8.Contrast piece uncoated.Use Cole-Parmer Dual J-T-E-K Thermocouple ThermometerModel 91100-40 with following timed interval record temperature.

The block rubber that uncoated block rubber applies

Time (minute) temperature (/℃) temperature (/℃)

Beginning 0 ' 73.8/23.2 73.6/23.1

Beginning 0 ' 73.8/23.2 73.6/23.1

10’ 162/172.2 97.3/36.2

20’ 214.9/101.6 118.7/48.1

30’ 238.5/114.7 130.5/54.7

Uncoated sample begins to smolder in initial 10 minutes of contacting with thermal source.

DeMattia deflection sample applies with the coated material of embodiment 2 according to ASTM D-813.77,000 times crack or layering are not observed in the circulation back in coating.If the crack appears in base material, can split in the crack in rubber substrate and the coating so.Binding property is fabulous, only observes fissured this phenomenon and show and obtained maximum coating integrity degree in lower floor's base material.

Result among Fig. 1 represents the sample with embodiment 2 repetitive coatings, dries to sample with low speed apart from 16 (inches), 3 fan speed of sample 9.5 (foot), and infrared lamp is apart from sample 4 (inch).Air movement is with simulated automotive.

The block rubber that uncoated block rubber applies

Time (minute) temperature (/℃) temperature (/℃)

Beginning 0 ' 73/ 73/

4’ 95/ 78/

10’ 131/ 84/

20’ 172/ 92/

35’ 181/ 96/

50’ 189/ 99/

120’ 189/ 99/

The HNBR water-based latex of embodiment 3-functionalization

The HNBR latex of water base functionalization produced according to the present invention.The solid carboxylic acidization of use A 41%-HNBR latex (404EXPLTX005, the latex B that Zeon Chemical sells).Composition below the preparation.

Composition	Prescription 1	Prescription 2	Prescription 3	Prescription 4	Prescription 5	Prescription 6
							41% solid X-HNBR latex	100 grams	100 grams	100 grams	100 grams	100 grams	100 grams
Biphenyl methane diisocyanate prepolymer 1(aromatic series)	1.25 gram	2.5 gram	5.0 gram	-	-	-
							1,6-hexamethylene diisocyanate base polymeric polyisocyanate 2(aliphatics)	-	-	-	2.5 gram	5.0 gram	7.5 gram

¹Desmodur ^XO 672

²Bayhydur ^302 (1,6-HDI), can obtain from Bayer Corporation

With the latex of listing above/isocyanate mixture spraying DeMattia deflection sample.The MIBK obliterating of DeMattia sample, and use Chemlok ^7701 handle, and coating spraying is coated on the sample.All samples are not observed crack or layering through 80,000 circulations.Binding property is fabulous.

Under 104 , in 50pphm ozone, use dynamic ozone test machine (ASTM-D3395) to carry out the ozone test.

Sample is based on the commercial sulphur-solidified natural rubber/mixed with polybutadiene thing of 55 hardness, and it is subjected to the protection of anti-ozone wax and alkyl-aryl phenylenediamine antiozonidate (M122N).Interval with 2 hours is observed.

Observe the time of edge crack

A. uncoated contrast 4.0 hours

B. use Chemisat ^2 hours of applying of LCH7302X (HNBR of NOT-functionization)

C. use Chemisat ^(HNBR of NOT-functionization, per 100 is heavy 4.0 hours for LCH7302X

The Bayhydur of amount part ^302 (1,6-HDI) contain 5.0 parts) apply

The Bayhydur of amount part ^302 (1,6-HDI) contain 5.0 parts) apply

D. 10 hours of usefulness carboxylic acidifying HNBR 404EXPLTX005 coating

E. use carboxylic acidifying Latex 404EXPLTX005 (1 of per 100 weight parts, 22.0 hours HDI of 6-contain 5.0 parts) to apply

Chemisat ^LCH7302X is a kind of HNBR latex, is produced by Zeon Chemical at present, is produced by Goodyear Chemical Company in the past.

Embodiment 4

	4E	4F	4G	4A
					Silvery white 1	Silvery white 2	Silvery white 3	Green
	Therban KA-8889 *	100	100	100					100
Akrochem The E2557 green					-	-	-	2.5
	Alglo 400 aluminium (Al) mashed prod **	10.0	-	-					-
Al Paste 586					-	12.5	-	-
	Stapa Metallux 214 Al mashed prod	-	-	10.0					-

^*Carboxylic acidifying HNBR obtains from Bayer Ag

^*45 microns of mean diameters

Alglo ^400 and aluminium Paste 586 by Toyal America, Inc. supply, Stapa ^Metallux 214 is supplied by Eckart America L.P..Also can use aluminium Paste 565 and Stapa ^Metallux 2156.Various varigrained thin slices or non-laminar aluminium pigment can be used to obtain different visual effects.The blended elastomerics is dissolved in the solvent, and solids content is 10%.They are easy to mix to obtain different painted shades with tinting material according to the known technology in the match colors.On the other hand, the mixture of 90% silvery white 3 and 10% green can obtain being mixed with a bit green silvery white.The copper conductive powder that obtains from Caswell can obtain gold with the mixture of silvery white 2 (embodiment 4F).

Embodiment 5-contrast

Comparative examples is used cured coating, it is according to United States Patent (USP) 5, the zinc that the multipolymer utilization of 314,741 hydrogenant acrylonitrile and butadiene in organic solvent wherein instructed-sulfur curable agent solid, and this coating is coated on the natural rubber base material of peroxide cure.

Coating composition

The composition weight part

HNBR 100

Zinc oxide 4.00

Sulphur 1.75

ZMBT(2) 2.00

Zinc dibutyl dithiocarbamate 0.75

Total 108.50

^*2-mercaptobenzothiazole zinc promotor

Composition except HNBR is by ground and mixed, and being dissolved in then becomes 10% solution in the MIBK solvent.In solvent, dissolve HNBR then by blended solid rubber in end runner mill and make coating composition.Before application composition, with washed with isopropyl alcohol sample (one inch wide sulphur-curing natural rubber sheet).

Coating composition is coated to the surface of natural rubber base material sample.Coat-thickness is about 1mil.Two apply uncured band and put together relative to one another with coated side.Dry coating is 24 hours under the room temperature.Some sample cures 15 minutes with solidified coating in the stove of 307  (152 ℃).It is thick that this feasible product that applies with natural rubber pressure plate (coating is arranged on it) is about 2mil, and be bonded together.The adherent sample is drawn back to be peeled off, and record separates their needed external force.

Uncured coating (dry but do not cure) 0.6Ibs stripping strength

Solidified coating (curing under 307  15 minutes) 1.9Ibs stripping strength

These curing and uncured coating are low to moderate unacceptable degree to the binding property of rubber substrate, and this makes that elastomer substrates produces flexing fatigue and crack when deflection.

Embodiment 6

(TherbanKA-8889 that obtains from Bayer AG) obtains transparent underlying coating layer by dissolving X-HNBR elastomerics in MIBK, and solids content is 5 weight %.Two-[isocyanate group phenyl] methane (vulcabond) (Casabond TX, in the dimethylbenzene 53%) that in the solution of 99.25 wet weight parts, adds 0.75 wet weight part.To be added in the transparent coating solution by the heat conduction aluminium pigment of the various weight percentages of polymer weight.

" (7.6cm * 7.6cm * 1.2cm) its hardness A is 65, and is coated to dry film thickness and is about 1mil (0.0004cm) to solidify blocky natural rubber 3 " * 3 " * 0.5.

Get out a hole at the block center, 1.5 inches (3.8cm), and insert thermopair with detected temperatures.Block placed under 250 watts the infrared lamp, " (10cm) apart from block rubber 4.Contrast piece uncoated.Use Cole-Parmer Dual J-T-E-K Thermocouple ThermometerModel 91100-40 to press the time record temperature.In experiment, do not use fan.

Uncoated block rubber

Time (minute) temperature ()

Beginning 0 ' 72

5’ 96

10’ 115

15’ 130

20’ 145

Embodiment 6A

STAPA ^Metallux ^2156 (Eckart America L.P.), 70% solid, non-thin slice, 16 microns mean diameters

The block rubber that uses STAPA Metallux 2156 to apply

10phr 20phr

Time (minute) temperature () temperature ()

Beginning 0 ' 72 72

5’ 87 79

10’ 106 90

15’ 120 100

20’ 130 108

The result illustrate schematicallys in Fig. 2.

Embodiment 6B

Aluminium Paste 565 (ex.Toyal America) 65% solid, thin slice, 13 microns mean diameters

The block rubber that uses aluminium Paste 565 to apply

10phr 20phr

Time (minute) temperature () temperature ()

Beginning 0 ' 72 72

5’ 84 81

10’ 97 93

15’ 106 101

20’ 116 110

The result illustrate schematicallys in Fig. 3.

Embodiment 6C

Alglo ^400 aluminium Paste (ex.Toyal America), 70% solid, non-thin slice, 45 microns mean diameters

The block rubber that uses Alglo 400 to apply

20phr 50phr

Time (minute) temperature () temperature ()

Beginning 0 ' 72 72

5’ 83 81

10’ 100 93

15’ 112 101

20’ 116 110

The result illustrate schematicallys in Fig. 4.

Embodiment 6D

Spark ^Silvex ^760-20-A (ex.Silberline) 80% solid, non-thin slice, 54 microns

The block rubber that uses Sparkle Silvex 760-20-A to apply

20phr 50phr

Time (minute) temperature () temperature ()

Beginning 0 ' 73 73

5’ 86 82

10’ 101 92

15’ 116 102

20’ 124 108

The result illustrate schematicallys in Fig. 5.

Embodiment 7

Use fluoroelastomer, water base XHNBR latex and urethane to prepare three similar coatings respectively.By mix following preparation then in MIBK dissolving to form solids content be that 30% solution obtains the fluoroelastomer underlying coating layer.

Embodiment 7A

Viton ^A-100(DuPont) 100.0PHR

Magnesium oxide (MAGLITE D) 1.0

Calcium hydroxide, technical grade 2.0

Metallux ^2156(Eckart Americal L.P.) 10.0

Aluminium Paste 586 (Toyal America) 5.0

N-(2-hydroxyethyl) quadrol that in the solvent soln of 120.0 grams, adds 1.8 grams.After 4 hours, the MIBK with 25 grams add with the 5.0 3-isocyanate group propyl-triethoxysilicanes that restrain.

Embodiment 7B

Make XHNBR latex from latex B (being obtained from Zeon Chemical (solids content 41%)).The Sparkle Silex that in 100.0 gram latex B, adds 20.0 grams ^760-20-A (Silberline ^) and the 5.0 dispersible polymeric polyisocyanate Bayhydur of water that restrain ^302 (Bayer).

Embodiment 7C

Be added to 100.0 gram Chemglaze by aluminium Paste 586 (ex.ToyalAmerica) with 7.0 grams (21.8phr on the urethane solid) ^V021 is transparent, make urethane in the urethane of moisture curable, solid weight 32%, and viscosity 115cps solidifies Tg and is lower than 0 ℃, solidifies the about 3000p.s.i. of tensile strength, finally ductility 350%.

" (7.6cm * 7.6cm * 1.2cm) its hardness A is 65, and uses the coating of embodiment A, B and C to be coated to dry film thickness to be about 1mil to solidify blocky natural rubber 3 " * 3 " * 0.5.

Go out a hole at test block center drill, 1.5 inches (3.8cm), and insert thermopair to detect the temperature at block center.Block placed under 250 watts the infrared lamp, " (7.5cm) apart from the upper surface 3 of block rubber.Contrast piece uncoated.Press the time record temperature.Use Omegascope ^Model OS530 Series non-contact infrared thermometer surface measurements temperature.Use Cole-Parmer Dual J-T-E-K Thermocouple Thermometer Model91100-40 to measure internal temperature.In experiment, do not use fan.

Uncoated block rubber

Inner surface

Time (minute) temperature () temperature ()

Beginning 0 ' 69.5 69

1’ 74.0 182

2 ' 91.8 242 (smoldering)

3’ 113.6 268

4’ 135.0 299

5’ 156.0 328

6’ 176.0 333

8’ 209.1 353

10’ 238.0 375

The block rubber that fluoroelastomer (embodiment 7A) applies

Inner surface

Time (minute) temperature () temperature ()

Beginning 0 ' 69.1 69

1’ 73.4 146

2’ 88.2 185

3’ 104.6 207

4’ 120.9 224

5’ 136.7 237

6’ 151.5 257

8 ' 178.8 268 (smoldering)

10’ 202.1 291

The block rubber that XHNBR latex (embodiment 7B) applies

Inner surface

Time (minute) temperature () temperature ()

Beginning 0 ' 69.8 69

1’ 72.2 1157

2’ 82.8 176

3’ 96.1 195

4’ 110.3 203

5’ 124.5 212

6’ 139.8 236

8 ' 163.0 254 (smoldering)

10’ 186.1 264

The block rubber that urethane (embodiment 7C) applies

Inner surface

Time (minute) temperature () temperature ()

Beginning 0 ' 72.0 69

1’ 75.9 127

2’ 90.4 145

3’ 105.2 174

4’ 120.7 182

5’ 135.0 189

6’ 148.5 198

8’ 172.5 210

10 ' 194.4 223 (smokelessly)

Surface temperature comparing result based on the sample of the uncoated control sample of embodiment 7A, 7B and 7C and coating illustrate schematicallys in Fig. 6.

Embodiment 8

The reflective coating formulation preparation of room-temperature-curable is as follows:

DIBK 5.0 5.0

Therban ^KA-8889(X-HNBR) 5.0 5.0

After the polymer dissolution, the composition below adding:

Aminopropyl triethoxysilane 5.0 5.0

Aluminium Paste 586 2.5 2.5

KBM-7803 5.0

KBM 7803 is 17 trifluoro decyl Trimethoxy silane CF ₃(CF ₂) ₇CH ₂CH ₂Si (OCH ₃) ₃, commercial can obtaining from Shinetsu Silicones.Apply 6 " * 6 " * 0.75 with each coating " natural rubber pad (hardness 65).Behind the coating curing, be used in coating top 6 " the infrared lamp irradiation.Use the time interval measurement surface temperature of Cole-Parmer Dual J-T-E-KThermocouple Thermometer Model 91100-40 to show below.After the irradiation, mat heats in the stove of 350  more than 7 minutes to quicken decolouring.

The measurement of surface temperature

The 93-7 that the 93-6 of uncoated coating applies

Time (minute) temperature /℃ temperature /℃ temperature /℃

Beginning 0 ' 82/27.7 81/27.2 81/27.2

1’ 176/80 129/53.8 120/48.8

2’ 235/112 159/70 146/63

3’ 280/137 190/87.7 170/76

4’ 305/151 195/90 185/85

5’ 330/165 204/95 196/91

6’ 340/171 211/99.4 204/95

7’ 345/173.8 216/102 207/97

Decolouring under 350 /175 ℃ is aging serious minimum

But the heat dissipation coating base based on the mixture of hydrolyzable aminoalkyl trialkoxy silane and fluoroalkyl trialkoxy silane is proved fast setting, and the heat aging rear decoloring reduces.

But the heat dissipation coating base based on the mixture of hydrolyzable aminoalkyl trialkoxy silane and fluoroalkyl trialkoxy silane is proved fast setting, and the heat aging rear decoloring reduces.

Although according to patent description best mode and embodiment preferred, scope of the present invention is not limited thereto, but the appending claims limited field.

Claims (25)

1. One kind be applied on the elastic substrate at two curable component liquid coating compositions of envrionment temperature, in a component (a), contain Tg less than 0 ℃ flexible membrane-forming agent and be combined in wherein can with the functional group of the solidifying agent reaction that contains active hydrogen, perhaps described functional group is the group that has active hydrogen, described polymkeric substance contains the ethylenic degree of unsaturation less than 10%, in another component of described two components, contain cure component and liquid carrier, described cure component contains group and the crosslinked group of being with active hydrogen, perhaps described solidifying agent contain can with the group of active hydrogen and crosslinked group reaction.
2. 2. composition as claimed in claim 1; also contain (a) membrane-forming agent by per 100 weight parts, the mean particle size of 10～100 weight parts be the thermal conductive metal particle of 2～10 μ m or (b) mean particle size of 20～150 weight parts be 20～60 microns heat conduction particle.
3. 3. coating composition as claimed in claim 1, wherein said membrane-forming agent are that molecular weight is the random or block diene copolymers of about hydrogenant of 20,000～200,000.
4. 4. coating composition as claimed in claim 1, wherein said membrane-forming agent are carboxylic acidifying HNBR.
5. 5. coating composition as claimed in claim 1, wherein said membrane-forming agent are the acrylic rubbers of functionalization.
6. 6. coating composition as claimed in claim 1, wherein said membrane-forming agent is derived from ethylenically unsaturated monomers and α, beta-unsaturated carboxylic acid.
7. 7. coating composition as claimed in claim 1, wherein the described functional group on described membrane-forming agent is selected from sulfonic acid, sulfonic acid, chlorsulfonic acid, vinyl ether, vinyl acetate, primary amine, secondary amine, tertiary amine, monocarboxylic acid, dicarboxylic acid, is derived from the partial ester or the full ester of monocarboxylic acid, the partial ester that is derived from dicarboxylic acid or full ester, the acid anhydrides of dicarboxylic acid, cyclin imide, its ionomer derivative and the combination thereof of dicarboxylic acid.
8. 8. coating composition as claimed in claim 1, wherein said membrane-forming agent are the hydrogenated diene elastomericss that contains methylol functional group.
9. 9. coating composition as claimed in claim 6, wherein said membrane-forming agent are the hydrogenated diene elastomericss that contains phenol methylol functional group.
10. 10. coating composition as claimed in claim 1, wherein said membrane-forming agent are the reaction product of the thermo-cracking of the HNBR of amino-functionalization and diaryl carbonate.
11. 11. coating composition as claimed in claim 5, wherein said membrane-forming agent comprise ethene, vinylformic acid C ₁-C ₄The unitary terpolymer of alkyl ester and carboxylic acid monomer.
12. 12. coating composition as claimed in claim 5, wherein said membrane-forming agent contain the ethyl maleate of ethene and 10～about 70 moles of % of 30 moles of % at least.
13. 13. coating composition as claimed in claim 1, wherein said membrane-forming agent is that it is selected from hydrogenant styrene-butadiene-styrene block copolymer and hydrogenant styrene isoprene styrene block copolymer (SIS) from elastomeric carboxylic acidifying segmented copolymer.
14. 14. coating composition as claimed in claim 1, wherein said membrane-forming agent are the terpolymers of poly-alpha olefins-acrylate-vinylformic acid carboxylicesters.
15. 15. coating composition as claimed in claim 1, wherein said membrane-forming agent are the hydrogenant nitrile butadiene polymers that contains hydroxyl.
16. 16. coating composition as claimed in claim 1, wherein said membrane-forming agent is hydrogenant hydroxyl divinyl and the mixture that is selected from the membrane-forming agent of carboxy-modified chlorinatedpolyethylene, chlorinatedpolyethylene, Polyglycol 166-450, polyethylene-vinylformic acid, SBR, SBS, NBR, SIBS, EPDM, EPM, polyacrylic ester, halogenated polyisobutene and poly(propylene oxide), and the ratio of total degree of unsaturation is no more than 10% in the wherein said mixture.
17. 17. coating composition as claimed in claim 1, wherein said membrane-forming agent contains hydroxyl, described hydroxyl to form the saturated hydrocarbon polymer of ozonize, reduces the saturated hydrocarbon polymer of ozonize and combined by processing hydrocarbons polymkeric substance under the ozonize condition then.
18. 18. coating composition as claimed in claim 1, wherein said membrane-forming agent contains carboxyl, described carboxyl is by handling saturated hydrocarbon polymer to form the saturated hydrocarbon polymer of ozonize under the ozonize condition, reduce the saturated hydrocarbon polymer of ozonize and combined then.
19. 19. coating composition as claimed in claim 1; wherein said membrane-forming agent contains two or more α-monoene and non-conjugated diene comonomer, is combined with on it to be selected from following functional group: carboxyl, acid anhydrides, epoxy group(ing), phosphoryl, sulfo group, sulfenic acid ester,-sulfinic acid ester, hydroxyl, epoxy group(ing), isocyanic ester, An are Ji oxazolinyl.
20. 20. coating composition as claimed in claim 1, wherein said membrane-forming agent contains hydroxy-end capped polyisobutene, and its end position that hydroxyl is incorporated into the iso-butylene of cationoid polymerisation by dehydrochlorination, hydroboration and oxidation end group chlorine polyisobutene prepares.
21. 21. coating composition as claimed in claim 1, wherein said solidifying agent are the polymeric polyisocyanates that contains under the envrionment temperature for liquid 10～50% reactive NCO groups.
22. 22. coating composition as claimed in claim 1, wherein said solidifying agent are two component systems, it comprises the redox curing system, and described system contains multi-functional ethylenically unsaturated compounds, Oxidizing and Reducing Agents.
23. 23. coating composition as claimed in claim 1, wherein said membrane-forming agent contains the chlorinatedpolyolefins of useful acid or anhydride group modification.
24. 24. the method for a coating elastomer moulded product, described goods randomly are fixed on the formed metal articles, described method comprises solvent based, be filled with metallic pigment, the elasticity film forming coatings of self-vulcanizing, spraying, dip-coating or brush on the surface of described molded elastomeric goods, described coating contains solidifying agent, the heat conduction particle of at least 10 weight % and membrane-forming agent, the Tg of described film-forming polymer is less than 0 ℃, wherein be combined with can with the functional group of the solidifying agent reaction that contains active hydrogen, perhaps described functional group is the group that has active hydrogen, and described polymkeric substance comprises the ethylenic degree of unsaturation less than 10%.
25. 25. method as claimed in claim 25, wherein said elastomeric article contain the elastomerics of the nitrile-divinyl rubber that is selected from natural rubber, styrene butadiene ribber, polybutadiene rubber, ethylene propylene rubber, propylene diene rubber, polyisobutene-synthetic polyisoprene, sovprene and low acrylonitrile content (＜35%).

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