WO1991006580A1 - Polymeres reticulables - Google Patents

Polymeres reticulables Download PDF

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Publication number
WO1991006580A1
WO1991006580A1 PCT/GB1990/001675 GB9001675W WO9106580A1 WO 1991006580 A1 WO1991006580 A1 WO 1991006580A1 GB 9001675 W GB9001675 W GB 9001675W WO 9106580 A1 WO9106580 A1 WO 9106580A1
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WO
WIPO (PCT)
Prior art keywords
silane
adhesive composition
hot melt
polymer
modified polymer
Prior art date
Application number
PCT/GB1990/001675
Other languages
English (en)
Inventor
Leslie Phillip Martin
Michael Edward Slevin
Colin Beveridge
Original Assignee
Swift Adhesives Limited
Aei Cables Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Swift Adhesives Limited, Aei Cables Limited filed Critical Swift Adhesives Limited
Publication of WO1991006580A1 publication Critical patent/WO1991006580A1/fr
Priority to GB9209553A priority Critical patent/GB2254333B/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/04—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to rubbers

Definitions

  • the present invention relates to novel silane grafted unsaturated polymers and to hot melt adhesives, sealants, foam gaskets and moulded articles prepared therefrom.
  • Silane grafted homo- and co-polymers are widely used for the preparation of cable jacketing, wire insulation and piping and have been suggested for use as spacers in laminate ⁇ materials.
  • the preparation of such materials is described in for example US-A-3646155, GB-A-1286460, GB-A-1347426, GB-A-1406680, GB-A-1450934 and GB-A-1542543.
  • US-A-3646155 describes the production of such material by reaction of polyethylene with an unsaturated silane, e.g. vinyl triethoxysilane, in the presence of a peroxide initiator to produce the silane grafted polymer.
  • a catalyst for example dibutyl tin dilaurate, is incorporated into the grafted polymer which is then formed into the desired shape. Catalysed hydrolysis and cross-linking of the silane groups occurs to give the hardened end product.
  • the reaction procedure may thus be represented as follows:-
  • stage (A) above may also be produced by copoly erisation of ethylene with a suitable trialkoxysilyl monomer, e.g. 4-(triethoxysilyl)- but-1-ene.
  • a suitable trialkoxysilyl monomer e.g. 4-(triethoxysilyl)- but-1-ene.
  • References hereinafter to silane-grafted or silane-modified polymers include such silane side chain materials produced by copolymerisation, which are essentially the same as the materials produced by gra ting. While teaching that for storage stability the silanol condensation catalyst should be incorporated into the silane-grafted polymer only when initiation of the cross-linking reaction is desired, Dow Corning Limited have suggested in GB-A-1406680 that silane grafted ethylene-vinyl acetate copolymers may find utility in adhesives.
  • silane-grafted hydrogenated, i.e. saturated, styrene-olefin-styrene block copolymers in sealant compositions and moulded articles, for example in EP-A-240044, JP-A-59102931 and JP-A-58132032.
  • the present invention is based on the recognition that silane modified unsaturated polymers can combine the known desirable characteristics of the basic polymers and the rapid, room temperature or moderately elevated temperature curing properties of silane side chains.
  • the invention provides silane modified (including silane grafted) unsaturated polymers as hereinafter defined. For convenience these materials will be referred to as SGPs.
  • the invention provides crosslinked (e.g. cured) silane modified unsaturated polymers and articles made therefrom.
  • unsaturated polymer designates a polymer having unsaturated carbon - carbon bonds, e.g. double bonds, situated along the polymer backbone or in groups pendant therefrom. Generally at least 0.5% of the carbon-carbon bonds will be carbon-carbon double bonds and preferably at least 1%. However it is preferred that not more than 50%, especially not more than 35%, particularly not more than 25%, of the bonds be double bonds as higher levels will make silane grafting difficult. Where a block copolymer is referred to these figures apply to the relevant block of the copolymer, and not to the polymer molecule as a whole.
  • styrene - isoprene - styrene block copolymer it can be calculated that approximately one in four of the polymer backbone carbon - carbon bonds will be unsaturated, i.e. an overall degree of unsaturation of 20%.
  • Suitable unsaturated rubbers include the following:
  • styrene- conjugated diene - styrene block copolymers such as styrene - isoprene - styrene (SIS) and styrene - butadiene - styrene (SBS) .
  • SIS styrene-isoprene - styrene
  • SBS styrene - butadiene - styrene
  • Typical commercially available materials are Kraton 1107 (SIS) and Kraton 1102 . (SBS) available from Shell. Since a higher degree of chain extension than normally acceptable may occur when SBS is subjected to a silane grafting reaction, it is preferred that a lower molecular weight SBS be used when the final SGP is to be produced by grafting.
  • the chain extension is hindered in polymers such as SIS by the presence of a methyl group adjacent to the double bond; accordingly it is preferred that the styrene- olefin-styrene block copolymer contain an olefin monomer having a nonreacting sterically hindering group, e.g. C,_ 4 alkyl group, present on at least one of the carbon atoms participating in the carbon-carbon double bond.
  • a nonreacting sterically hindering group e.g. C,_ 4 alkyl group
  • This category includes the well known styrene- butadiene random copolymers (SBR) .
  • SBR styrene-butadiene random copolymers
  • These polymers are copolymers of one or more unsaturated nitriles with one or more conjugated dienes.
  • the " diene is commonly butadiene although isoprene, 2- ethyl-butadiene, 2,3-dimethyl-butadiene and piperylene have been used.
  • the nitrile is generally acrylonitrile although again other unsaturated nitriles can be used.
  • a typical example of a butadiene-acrylonitrile rubber is Breox 1442 available from BP.
  • This class of unsaturated polymers comprises polymers of 2-chlorobutadiene such as Neoprene AC available from Du Pont.
  • This class includes copolymers of isobutylene and isoprene, generally with only a small amount of isoprene and typically containing 50 isobutylene units per isoprene unit.
  • the polymer is distinguished from polyisobutylene in that the latter contains substantially no double bonds along the polymer backbone.
  • This class also includes chlorinated butyl rubbers prepared by chlorination of the original butyl rubber. It is preferred that the butyl rubbers for use in the present invention are at least 0.5% unsaturated as defined above, more preferably 1% unsaturated and coveniently not more than 5% unsaturated. It will be seen that, like the polyisoprene block of SIS, butyl rubbers have a nonreactive methyl group adjacent to the double bond which may hinder chain extension.
  • the invention is conveniently applicable to unsaturated polymers prepared from a conjugated diene or containing a conjugated diene as one of the comonomers.
  • the carbon-carbon double bonds will be present in the backbone or, when present in a pendant group, will be separated from the backbone by one carbon-carbon single bond. It is preferred that the unsaturation be present in the polymer backbone and that any pendant groups be saturated.
  • silane side chain is conveniently of general formula (I)
  • A represents an optionally substituted divalent organic radical, preferably an optionally substituted alkylene, alkyleneoxy, alkylene-phenylene, or alkylene-oxy-alkylene chain
  • X represents a leaving group displaceable by hydrolysis, conveniently a halogen atom (e.g. chlorine) or a group R 1O-or.
  • R1COO- where R1 is a C-_ 10 , preferably C ⁇ .., alkyl or alkoxyalkyl group; m is 1, 2 or 3, preferably 2 or 3; and R represents a blocking group not displaceable by hydrolysis, for example a C. . alkyl group.
  • silane side chains may be present in a monomer which is copolymerised to produce the SGP.
  • the SGP component for inclusion in the adhesive compositions of the invention may also be prepared by reacting the polymer (or blend thereof) with an unsaturated silane of formula II
  • a 1 represents an ethylemcally unsaturated organic group corresponding to the divalent group A in formula I and R, m and X are as defined above
  • a catalyst conveniently a peroxide catalyst, for example using the reagents and conditions specified in the literature.
  • IInn ffoormula II A conveniently represents a group of formula
  • R 2 represents hydrogen or C alkyl
  • R 3 represents a C strai.ght, branched or cyclic alkylene group, a phenylene group, a carbonyloxy group, a carbonyloxy(C alkylene) group, a (C alkylene)carbonyloxy group or a ( c 1 _ 10 alkylene)carbonyloxy(C alkylene) group, optionally carrying pendant glycidoxy groups.
  • R 3 represents a C strai.ght, branched or cyclic alkylene group, a phenylene group, a carbonyloxy group, a carbonyloxy(C alkylene) group, a (C alkylene)carbonyloxy group or a ( c 1 _ 10 alkylene)carbonyloxy(C alkylene) group, optionally carrying pendant glycidoxy groups.
  • Such compounds are described by Dart Industries in GB-A-1347426.
  • A represents a C 2 _ c - monoalkenyl group, such as vinyl or allyl, or a (C alkenyl)carbonyloxy(C 2 __ alkylene) group, such as a gamma-methacryloxy propyl group, and.
  • particularly preferred unsaturated silanes of formula II include vinyl trimethoxy silane, vinyl triethoxy silane and gamma-methacryloxypropyl trimethoxy silane.
  • Unsaturated silanes of formula II are known or may be prepared by conventional methods.
  • the silane grafting reaction is conveniently effected at a temperature of at least 140°C, preferably between 150°C and 250 ⁇ C, and may be performed in conventional apparatus such as a Ko-Kneader.
  • the catalyst used in the preparation of the SGPs is preferably a free-radical generating compound such as for example benzoyl peroxide, dicumyl peroxide or other catalysts referred to in the literature, e.g. in US-A- 3646155.
  • the free radical generator may conveniently be used in a concentration of about 0.01 to 3% relative to the weight of polymer used.
  • a third method of producing the SGP may be appropriate when the polymer contains groups or atoms which will prevent the conventional grafting reaction from working effectively, for example the chlorine atoms in polychloroprenes which will generate HC1. This method will involve the use of an aminosilane of general formula III
  • a 2 is an optionally substituted divalent organic radical as defined above for A, and R, X and m are as defined above.
  • Two equivalents of silane will be required for each equivalent of silane to be introduced into the polymer as one equivalent will combine with the HC1 to form
  • the silane side chain need only constitute a minor part by weight of the SGP, e.g. up to 20%, generally 0.1 to 10%, preferably 0.5 to 6% and especially preferably about 4%.
  • the SGPs of the invention may be used in adhesives including for example both hot melt and solvent based adhesive systems.
  • an adhesive composition comprising (a) a silane modified unsaturated polymer as defined above and (b) a catalyst for the condensation of said silane modified unsaturated polymer.
  • a silanol condensation catalyst may be used both in solvent based and hot melt systems.
  • suitable catalysts include, for example, metal carboxylates, e.g. dibutyl tin dilaurate, organometallics, e.g. tetrabutyl titanate, organic bases, e.g.
  • ethyla ine and mineral and ' fatty acids.
  • organotin compounds such as dibutyl tin dilaurate are preferred.
  • the catalyst conveniently makes up from 0.005-0.2%, preferably about 0.02%, of the adhesive composition as a whole.
  • an adhesive according to the invention is to be solvent based it will have the advantage of cross linking at room temperature while nonetheless being a one part formulation.
  • Conventional solvent based adhesives are either cured by heating or must be two part formulations using a chemical curing process.
  • the solvent based adhesive compositions according to the present invention have significant advantages in terms of convenience of application and curing.
  • suitable solvents for polychoroprenes and SBR mention may be made of aromatic or aliphatic hydrocarbons with varying proportions of oxygenated solvents such as ketones and esters, i.e. hexane, toluene, methyl ethyl ketone, acetone or (for non- flammable adhesives) ethylene chloride.
  • Solvents for nitrile adhesives include aromatic hydrocarbons, chlorinated hydrocarbons, ketones, esters and nitroparaffins. Solvent based adhesives may also contain tackifying resins (as up to 90% of the total solids content) , plasticisers (up to 80% of solids) , fillers (up to 80% of solids) and colourants and stabilisers (generally not more than 10% of solids) . Further description of these materials is found hereinafter.
  • the total level of solids in the solvent can conveniently range from about 10% for a sprayable adhesive to about 95% in sealants.
  • Hot melt adhesive systems according to the invention are preferably based on the block or random copolymers of types (1) and (2) referred to above or on butyl rubbers. It is particularly preferred to use silane grafted styrene-isoprene-styrene in these hot melt " adhesives.
  • the hot melt adhesive systems will desirably contain a plasticiser to improve substrate wetting by the hot melt and to improve flexibility in the cured adhesive.
  • the plasticiser may be for example an ester- based plasticizer (e.g. benzoate plasticizers such as glycol dibenzoate and dipropylene glycol dibenzoate (available as Benzoflex 9-881) ) a liquid polyterpene or liquid hydrocarbon plasticizer (such as for example the polyterpene available from Goodyear under the trade name Wingtack 10 and the liquid hydrocarbon available from Exxon under the trade name Escorez 5000) , a polybutene plasticizer, a phthalate plasticiser or a process oil such as Shellflex 451 available from Shell.
  • an ester- based plasticizer e.g. benzoate plasticizers such as glycol dibenzoate and dipropylene glycol dibenzoate (available as Benzoflex 9-881)
  • a liquid polyterpene or liquid hydrocarbon plasticizer such as for example the poly
  • the plasticizer conveniently,constitutes up to 80%, preferably 10-35%, of the hot melt adhesive composition.
  • Polymers having a wide range of molecular weights may be silane grafted to produce the SGPs used for the preparation of the adhesive compositions of the present invention; in general polymers having melt flow indices (MFIs) of from l'to 2500 may be used and MFIs of 2-1000, especially 5-400 and particularly 10-150, are preferred.
  • MFIs melt flow indices
  • 2-1000 melt flow indices
  • grafted polymers having different monomer make-up the performance profile of the final adhesive system, for example in terms of wetting, strength, adhesion, flexibility, and ease of application, may be adjusted to suit its intended end use.
  • the SGP component preferably forms up to 90%, conveniently 10-40%, and especially preferably about 30%, of the hot melt adhesive composition.
  • SGPs having a 3-membered or longer chain linking the silicon atoms with the polymer backbone will result in a cured adhesive having a generally more open structure than that achieved with only a 2- membered linking chain.
  • the open structure may advantageously permit both a high degree of curing and the inclusion of relatively high concentrations of tackifying resin and other components in the uncured adhesive composition. In this way, the viscosity, tack and melting characteristics of the uncured adhesive may be tailored to particular desired levels, for example to permit the use with the new adhesive of conventional hot melt adhesive melting, mixing and application apparatus.
  • the hot melt adhesive composition of the invention conveniently also contains further components selected from: antioxidants; tackifying resins; further polymers; and diluents and modifiers.
  • the tackifying resin component of the hot melt adhesive composition of the present invention may comprise any suitable resin or resin mixture, for example those conventional for hot melt adhesives.
  • the resin or resin mixture should however be selected to achieve the desired balance between compatibility with the SGP and the other components of the adhesive, the melt flow properties of the adhesive as a whole and the specific adhesion to the substrates intended to be bonded with the adhesive.
  • suitable tackifying resins may include: aromatic modified resins such as ⁇ -methyl styrene homopolymers or copolymers, e.g. Krystalex F100 ( ⁇ -methyl styrene polymer) ,
  • Krystalex FR75 (a modified ⁇ -methyl styrene copolymer) or Piccotex (a vinyl toluene- ⁇ -methyl styrene copolymer) , all three available from Hercules Chemical Co.; aliphatic petroleum hydrocarbon resins; styrene-modified hydrocarbon resins; polyterpene resins; terpene phenolic resins; rosin and rosin esters; reactive resins containing for example acid groups, hydroxyl groups or silanol groups; and, particularly preferably, alicyclic hydrocarbon resins, e.g. Escorez 5300 (available from Exxon) .
  • Escorez 5300 available from Exxon
  • the tackifying resin will conveniently comprise up to 80%, preferably 10-40%, and especially preferably about 30%-35%, of the adhesive.
  • the hot melt adhesive of the invention preferably contains at least one antioxidant.
  • conventional adhesives antioxidants such as butylated hydroxytoluene (BHT) may be used.
  • BHT butylated hydroxytoluene
  • a preferred antioxidant is pentaerythritol-tetrakis-3-(3,5- di-tert.butyl-4-hydroxyphenyl)-propionate, which is available under the trade name Irganox 1010 from Ciba-Geigy UK Ltd. of Manchester.
  • the antioxidant will generally be present in the adhesive at about 0.1-2.5%, preferably 0.5-1%.
  • the hot melt adhesive system may if desired be formulated as two compositions which are not mixed until the adhesive is melted for application so as to avoid earlier contact between the SGP and the condensation catalyst.
  • a hot melt adhesive system comprising a first composition comprising at least one SGP as defined above and a second composition comprising a catalyst for the condensation of said SGP, said first and second compositions being packed in separate containers.
  • the hot melt adhesive composition of the invention preferably also comprises a further polymer or polymer mixture.
  • the further polymer or polymer mixture which should not be cross-linkable under the action of the catalyst, will be selected to achieve, inter alia, a balance between co patability with the catalyst and the other components of the adhesive and the viscosity and tack characteristics of the adhesive.
  • the further polymers are preferably selected from homo- and copolymers of apolar monomers, such as for example polyethylene, polypropylene, polybutylene, and SEBS (for example low crystallinity range molecular weight homo-or copolymers, such as that available under the trade name Vestoplast 608 from H ⁇ ls (UK) Limited of Manchester, or low " molecular weight polyethylene, such as polyethylene AC6 or AC8 available from Allied Chemical Corporation International NV SA of Birmingham) or from copolymers containing polar comonomers such as poly(ethylene-vinyl acetate) .
  • Conveniently polymers having MFIs of 1 to 2500, preferably 5-800, more preferably 20-500 and most •preferably 150-400 are used.
  • the further polymer conveniently constitutes up to 15%, preferably 1 to 10%, and especially preferably about 5%, of the adhesive of the invention and generally will be present at about half the concentration of the SGP.
  • the hot melt adhesive composition or system may also contain further components such as diluents or modifiers, conveniently as about 5-40%, preferably about 30%, of the total adhesive. These components may serve to regulate the viscosity and setting speed of the adhesive and may be included to enhance the wicking of the adhesive into the substrates to be bonded.
  • conventional diluents and modifiers for hot melt adhesives such as waxes (e.g. petroleum waxes such as paraffin waxes or macrocrystalline waxes such as Okerin 8981 from Astor Chemicals of West Drayton, Middlesex) , hydrogenated animal or vegetable fats (e.g. hydrogenated castor oil or hydrogenated tallow) , and synthetic waxes, such as Fischer Tropsch waxes may be used.
  • waxes e.g. petroleum waxes such as paraffin waxes or macrocrystalline waxes such as Okerin 8981 from Astor Chemicals of West Drayton, Middlesex
  • hydrogenated animal or vegetable fats e.g.
  • waxes or low molecular weight polyethylenes are used as diluents, they should conveniently have softening temperatures in the range of 50- 120"C.
  • Microcrystalline waxes, Fisher Tropsch waxes and paraffin waxes having softening temperatures in the ranges 65 to 94°C (e.g. 79°C) , 110 to 120°C and 54 to 72°.C respectively are particularly suitable.
  • a mixture of low molecular weight polyethylene, such as polyethylene AC6 or AC8, and a microcrystalline wax having a softening temperature of about 90°C, such as Micro 549 available from Holmes Chemical Company of Uxbridge, may also be particularly suitable, especially where the polyethylene and the wax constitute about 5 and about 15% by weight respectively of the adhesive.
  • the hot melt adhesive is formulated as a two part system, the SGP and the catalyst being separately packaged, the optional components can appear in one or both of the separate' compositions; the SGP- containing composition will however preferably contain the antioxidant and the tackifier and the catalyst-containing composition will preferably contain a further polymer; the plasticizers, diluents and modifiers may be in either or both compositions
  • the catalyst-containing composition particularly conveniently comprises about 99% of polymer compatible with the SGP (e.g. polyethylene, polypropylene or SEBS) and 1% of a catalyst (e.g. dibutyl tin dilaurate) .
  • the hot melt adhesive of the invention is formulated as a single composition it will advantageously be packaged in water-tight containers, for example aluminium cartridges, which containers advantageously will also include a desiccant, for example a sachet of silica gel at the end of a cartridge for a hot melt adhesive applicator.
  • a hot melt adhesive applicator cartridge comprising a water-tight container containing therein a desiccant and a hot-melt adhesive composition, said composition comprising an SGP as hereinbefore defined and a catalyst for the condensation thereof.
  • a colouring agent for example a whitener such as titanium dioxide.
  • the adhesive of the present invention will be heated to melting, generally to 100-200°C preferably about 110-170°C, mixed (e.g. in a cartridge loaded applicator or by the mixing in a mixer head of the two compositions of a two composition system) and applied to the substrates to be bonded, generally in a film thickness of up to about 3 mm, preferably up to about 1 mm, although this can be achieved by applying a larger amount and scraping off the excess.
  • the adhesive characteristics of the system should be sufficient to maintain a bond between the substrates while the curing of the SGP component by hydrolysis and cross-linking occurs.
  • the hot melt adhesives according to the invention may contain further components which gradually release moisture into the system, for example fillers with surface-bound moisture or moisture filled polymer microspheres such as those sold as paint opacifiers by Rohm and Haas Company under the trade name ROPAQUE OP-62 (see EP-A-119054 of Rohm and Haas) .
  • the hot melt adhesive of the invention may be used in most applications where hot melt adhesives have been used and where full bonding strength is not required immediately after the application of the adhesive.
  • the adhesive of the invention is thus particularly suited to use in product assembly (for example in the furniture and automobile industries) , packaging and labelling.
  • the adhesive of the invention is capable of chemically bonding to the surfaces of certain substrates to produce an enhanced adhesive effect.
  • the adhesive of the present invention is particularly suitable for the bonding of cellulosic and silicaceous substrates, for example paper and glass.
  • the SGP and catalyst components in both the hot melt and solvent based adhesive of the present invention may be selected to achieve particular desired characteristics, for example rate or controlability of curing, and by varying the monomer make-up and the MFI of the polymer precursor for the SGP, and by utilizing blends of SGPs, the formulation characteristics (such for the adhesive may be controlled to give a readily processable material.
  • further organic components such as for example fillers, tack and viscosity modifiers, plasticizers and colorants can be bonded onto the cross-linked lattice produced by curing the silane grafted polymer by using for such components compounds containing, or chemically modified to contain, silanol, alcohol, a ine or thiol groups.
  • the use of such compounds is particularly advantageous since although they are unreactive towards the SGP in the adhesive composition before the application of the adhesive, on application they are able to bond to the silanols produced in the hydrolysis reaction and thereafter will be chemically bound into the cured adhesive. In this way where such components are polyfunctional, i.e.
  • the components may act as intermediaries in the cross-linking and by becoming part of the cross-linked lattice may modify the physical properties of the cured composition.
  • the components may bond to the silane grafted polymer so reducing any tendency they may have to leach out of the cured composition even under adverse conditions.
  • glycerol esters of resins, polyamines, diols, polyethylene glycols, hydroxylated waxes and the like " may be made in particular of glycerol esters of resins, polyamines, diols, polyethylene glycols, hydroxylated waxes and the like " .
  • Such reactive compounds may be particularly advantageous in increasing the thermal stability of the cured composition or where the optional component is capable of discoloring or otherwise damaging the substrate or where loss of the component would cause the adhesive bond to be modified undesirably, e.g. where it would deteriorate.
  • the SGPs according to the invention are also of particular use in the formulation of pressure sensitive adhesives, and a further aspect of the invention provides a pressure sensitive adhesive composition,- characterised in that it comprises a cross-linkable, silane modified unsaturated polymer as herein defined.
  • Pressure sensitive adhesives are distinguished by their surface tack levels, which can readily be measured in many ways, for example using the rolling ball or loop tack tests.
  • pressure sensitive adhesives must on curing e.g for 5 to 17 days retain some level of surface tack even if only a relatively low level such as that exhibited by the repositionable notes recently put onto the market by 3M under the trade name POST-IT.
  • a pressure sensitive adhesive would be expected to have a score of less than 10 cm, more usually less than 5cm, e.g. 2 cm, in the rolling ball test.
  • pressure sensitive adhesives would generally score greater than 1 Newtons/25 mm, e.g. about 10 N/25 mm.
  • a pressure sensitive adhesive composition scoring greater than 1 N/25mm in the loop tack (FTM No 9) test and comprising an adhesive composition according to the invention cured to effect cross linking of said silane modified polymer.
  • the SGPs according to the invention are also useful in the production of hot melt foam gaskets. They will be formulated as described above and can be applied using known foam gasket technology, for example the Foammelt available from Nordson Corp.
  • the SGPs according to the invention will also be of use in sealants and moulded articles which would normally require a heat or two part chemical curing process.
  • the silane cross-linking ability of the SGPs allows moisture curing at room temperature while retaining the desirable properties of the base polymer, e.g. fire retardancy (Neoprene) , solvent resistance
  • moulded articles such as tyres, shoe soles, cable sheathing, etc.
  • the article may be removed from the mould and cured elsewhere.rather than heat cured in the mould itself, thus freeing the mould and eliminating a production bottleneck.
  • silane grafted styrene- isoprene-styrene forms a particularly tough and flexible material upon curing. Accordingly the invention also provides moulded articles formed from the silane grafted unsaturated polymers according to the invention, preferably silane grafted styrene-isoprene-styrene.
  • composition is the admixture of the following components:
  • Micro wax (microcrystalline wax) 20.0%
  • composition is homogenized prior to the addition of the catalyst.
  • the catalyst is then mixed in and the composition is filled into aluminium cartridges for a hot melt adhesive applicator.
  • a silica gel sachet is placed in the filled cartridge which is then sealed.
  • Example 3 The compositions of Examples 3 to 9 are mixed and filled into containers as for Example 2.
  • Example 3 The compositions of Examples 3 to 9 are mixed and filled into containers as for Example 2.
  • composition is the admixture of the following components:
  • Irganox 1010 antioxidant
  • Escorez 5300 hydrocarbon - tackifying resin
  • Piccotex 100 ⁇ -methyl styrene-vinyl toluene copolymer - tackifying resin
  • Hyvis 30 polybutene - plasticizer 30.0%
  • composition is the admixture of the following components:
  • composition is the admixture of the following components:
  • composition is the admixture of the following components:
  • Catalyst/polypropylene blend (1% dibutyl tin dilaurate) 1.7%
  • Irganox 1010 antioxidant
  • Escorez 5300 hydrocarbon - tackifying resin
  • 26.0% Wingtack 10 liquid polyterpene
  • Hyvis 30 polybutene - plasticizer 30.0%
  • composition is the admixture of the following components:
  • Catalyst/polypropylene blend (1% dibutyl tin dilaurate) 1.7% Irganox 1010 (antioxidant) 1.0% Escorez 5300 (hydrogenated alicyclic hydrocarbon - tackifying resin) 10.0% Piccotex 100 ( ⁇ -methyl styrene-vinyl toluene copolymer - tackifying resin) 10.0% Shellflex 451 (process oil) 46.0%
  • Example 8 One part adhesive composition
  • composition is the admixture of the following components:
  • Catalyst/polypropylene blend (1% dibutyl tin dilaurate) 1.7%
  • Irganox 1010 antioxidant
  • Escorez 5300 hydrocarbon - tackifying resin
  • Piccotex 100 ⁇ -methyl styrene-vinyl toluene copolymer - tackifying resin
  • Hyvis 30 polybutene - plasticizer 30.0%
  • composition is the admixture of the following components:
  • Irganox 1010 antioxidant
  • Escorez 5300 hydrocarbon - tackifying resin
  • Piccotex 100 ⁇ -methyl styrene-vinyl toluene copolymer - tackifying resin
  • Hyvis 30 polyb ⁇ tene - plasticizer 10.0%
  • the first composition comprises the following components:
  • Wingtack 10 (polyterpene resin) 30 parts
  • the second composition comprises the following components:
  • Dibutyl tin dilaurate 0.017 parts In use, the first and second compositions are melted, mixed in a weight ratio of 2:1 and the mixture is applied to a substrate. • "
  • SGSBR is a silane grafted styrene butadiene rubber
  • Catalyst masterbatch is prepared as a 1% dispersion of dibutyl tin dilaurate in an ethylene-vinyl acetate copolymer carrier and is added to give a final catalyst concentration of 0.017% of total solids.
  • the polymer, rosin and catalyst masterbatch are dispersed in the solvent in a Silverson mixer.
  • the polymer, polyterpene and catalyst masterbatch are dispersed in the solvent in a Silverson mixer.
  • Polymer, resins, plasticiser and catalyst masterbatch are dispersed in the solvent in a Silverson mixer.
  • a silane grafted styrene-butadiene rubber which may be prepared analogously to Example 1.
  • the fillers are mixed with the rubber in a Brabender internal mixer, chopped and then added to the resin, plasticiser, solvents and catalyst masterbatch in a Silverson mixer.
  • the filler is mixed with the rubber in a Brabender internal mixer, chopped and then added to the resin, solvent and catalyst masterbatch in a Silverson mixer.
  • the fillers are mixed with the rubber in a Brabender internal mixer, chopped and then added to the resin, plasticiser, solvents and catalyst masterbatch in a Silve son mixer.
  • a silane grafted styrene-butadiene rubber which may be prepared analogously to Example 1.
  • Ingredients are mixed in an internal mixer and formed to shape by conventional injection or compression moulding.
  • Example 20 Ingredients are mixed in an internal mixer and formed to shape by conventional injection or compression moulding.
  • Example 20 Ingredients are mixed in an internal mixer and formed to shape by conventional injection or compression moulding.
  • a silane grafted styrene-butadiene rubber which may be prepared analogously to Example 1.
  • Ingredients are mixed in an internal mixer and formed to shape by conventional injection or compression moulding.
  • Ingredients are mixed in an internal mixer and formed to shape by conventional injection or compression moulding.
  • Example 2 These may be silane grafted analogously to Example 1. Ingredients are mixed in an internal mixer and formed to shape by conventional injection or compression moulding.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

On décrit des polymères modifiés aux silanes, ainsi que leur utilisation dans des compositions adhésives. Lesdits polymères sont non saturés, c'est-à-dire qu'ils contiennent des liaisons carbone-carbone dans le squelette polymère ou dans les groupes en dépendant.
PCT/GB1990/001675 1989-11-01 1990-11-01 Polymeres reticulables WO1991006580A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB9209553A GB2254333B (en) 1989-11-01 1992-05-01 Crosslinkable polymers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8924619.3 1989-11-01
GB898924619A GB8924619D0 (en) 1989-11-01 1989-11-01 Crosslinkable polymers

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WO1991006580A1 true WO1991006580A1 (fr) 1991-05-16

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PCT/GB1990/001675 WO1991006580A1 (fr) 1989-11-01 1990-11-01 Polymeres reticulables

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GB (1) GB8924619D0 (fr)
WO (1) WO1991006580A1 (fr)

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994004576A1 (fr) * 1992-08-25 1994-03-03 Bostik S.A. Adhesif thermofusible reactif pour l'assemblage de supports amorphes ou impermeables a l'eau
EP1479698A1 (fr) * 2003-05-22 2004-11-24 JSR Corporation Procédé de préparation de polymère diénique modifié et compositions de caoutchouc le comprenant
DE19821355B4 (de) * 1998-05-13 2005-02-24 Chemetall Gmbh Verwendung einer Dichtungsmasse zur Herstellung von Mehrscheibenisolierglas
WO2007040252A1 (fr) * 2005-10-05 2007-04-12 Jsr Corporation Procédé servant à produire un polymère diénique conjugué modifié, polymère diénique conjugué modifié obtenu par le procédé et composition de caoutchouc contenant celui-ci
US7204902B2 (en) 2003-03-11 2007-04-17 H.B. Fuller Licensing & Finance Inc Low-temperature press process for making insulating glass assemblies
EP0906378B2 (fr) † 1996-06-18 2008-03-12 H.B. Fuller Licensing & Financing, Inc. Composition de colle a fusion reactive pour verre isolant
WO2008050851A1 (fr) * 2006-10-25 2008-05-02 Jsr Corporation Procédé de production d'un polymère modifié, polymère modifié obtenu par ce procédé et composition de caoutchouc contenant celui-ci
EP2113545A1 (fr) * 2008-04-28 2009-11-04 Sika Technology AG Adhésifs thermofusibles ayant une durée d'ouverture prolongée
DE102008041281A1 (de) 2008-08-15 2010-02-18 Evonik Degussa Gmbh Silanmodifizierte Polyolefine mit hohem Erweichungspunkt
DE102008041279A1 (de) 2008-08-15 2010-02-18 Evonik Degussa Gmbh Silanmodifizierte Polyolefine mit hohem Funktionalisierungsgrad
DE102008041277A1 (de) 2008-08-15 2010-02-18 Evonik Degussa Gmbh Silanmodifizierte Polyolefine
DE102008041278A1 (de) 2008-08-15 2010-02-18 Evonik Degussa Gmbh Verwendung von Polyolefinen als Haftvermittler für die Herstellung flächiger Laminate
DE102009027445A1 (de) 2009-07-03 2011-01-05 Evonik Degussa Gmbh Modifizierte Polyolefine mit besonderem Eigenschaftsprofil, Verfahren zu deren Herstellung und deren Verwendung
DE102009027446A1 (de) 2009-07-03 2011-01-05 Evonik Degussa Gmbh Modifizierte Polyolefine mit besonderem Eigenschaftsprofil, Verfahren zu deren Herstellung und deren Verwendung
DE102009027447A1 (de) 2009-07-03 2011-01-05 Evonik Degussa Gmbh Modifizierte Polyolefine mit besonderem Eigenschaftsprofil, Verfahren zu deren Herstellung und deren Verwendung
US8080308B2 (en) 2003-03-11 2011-12-20 H.B. Fuller Company One-part moisture curable hot melt silane functional poly-alpha-olefin sealant composition
US8101276B2 (en) 2008-09-16 2012-01-24 Henkel Corporation Pressure sensitive adhesive compositions and articles prepared using such compositions
US8440304B2 (en) 2008-09-16 2013-05-14 Henkel Corporation Acrylic pressure sensitive adhesive formulation and articles comprising same
US9023946B2 (en) 2009-12-22 2015-05-05 Henkel IP & Holding GmbH Moisture cure hot melt adhesives
JP5720082B2 (ja) * 2005-03-18 2015-05-20 Jsr株式会社 変性重合体の製造方法、その方法によって得られた変性重合体とそのゴム組成物
US9212300B2 (en) 2007-08-10 2015-12-15 Henkel Ag & Co. Kgaa Reactive hot melt adhesive
US9365751B2 (en) 2012-07-24 2016-06-14 Henkel IP & Holding GmbH Reactive hot melt adhesive
US9428677B2 (en) 2013-01-24 2016-08-30 Henkel IP & Holding GmbH Reactive hot melt adhesive
WO2017098890A1 (fr) * 2015-12-07 2017-06-15 株式会社Moresco Composition d'adhésif thermofusible ainsi que procédé de fabrication ce celle-ci, matériau de scellement, dispositif électronique, et lampe
WO2017098889A1 (fr) * 2015-12-07 2017-06-15 株式会社Moresco Composition d'adhésif thermofusible ainsi que procédé de fabrication ce celle-ci, matériau de scellement, dispositif électronique, et lampe
US10221346B2 (en) 2014-01-14 2019-03-05 Henkel IP & Holding GmbH Reactive hot melt adhesives with improved adhesion
US20220064354A1 (en) * 2019-01-09 2022-03-03 Showa Denko K.K. Method for producing chloroprene graft copolymer latex, adhesive containing same and adhesion method

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Cited By (47)

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Publication number Priority date Publication date Assignee Title
FR2695132A1 (fr) * 1992-08-25 1994-03-04 Bostik Sa Adhésif thermofusible réactif pour l'assemblage de supports amorphes ou imperméables à l'eau.
WO1994004576A1 (fr) * 1992-08-25 1994-03-03 Bostik S.A. Adhesif thermofusible reactif pour l'assemblage de supports amorphes ou impermeables a l'eau
EP0906378B2 (fr) † 1996-06-18 2008-03-12 H.B. Fuller Licensing & Financing, Inc. Composition de colle a fusion reactive pour verre isolant
DE19821355B4 (de) * 1998-05-13 2005-02-24 Chemetall Gmbh Verwendung einer Dichtungsmasse zur Herstellung von Mehrscheibenisolierglas
US8080308B2 (en) 2003-03-11 2011-12-20 H.B. Fuller Company One-part moisture curable hot melt silane functional poly-alpha-olefin sealant composition
US7414090B2 (en) 2003-03-11 2008-08-19 H.B. Fuller Licensing & Financing, Inc Low-temperature press process for making insulating glass assemblies
US7204902B2 (en) 2003-03-11 2007-04-17 H.B. Fuller Licensing & Finance Inc Low-temperature press process for making insulating glass assemblies
US7202306B2 (en) 2003-05-22 2007-04-10 Jsr Corporation Method for producing modified conjugated diene polymer and rubber composition
EP1479698A1 (fr) * 2003-05-22 2004-11-24 JSR Corporation Procédé de préparation de polymère diénique modifié et compositions de caoutchouc le comprenant
JP5720082B2 (ja) * 2005-03-18 2015-05-20 Jsr株式会社 変性重合体の製造方法、その方法によって得られた変性重合体とそのゴム組成物
WO2007040252A1 (fr) * 2005-10-05 2007-04-12 Jsr Corporation Procédé servant à produire un polymère diénique conjugué modifié, polymère diénique conjugué modifié obtenu par le procédé et composition de caoutchouc contenant celui-ci
US7893153B2 (en) 2005-10-05 2011-02-22 Jsr Corporation Process for producing modified conjugated diene polymer, modified conjugated diene polymer obtained by the process, and rubber composition containing the same
JP5657855B2 (ja) * 2005-10-05 2015-01-21 Jsr株式会社 変性共役ジエン系重合体の製造方法、その方法によって得られた変性共役ジエン系重合体とそのゴム組成物
WO2008050851A1 (fr) * 2006-10-25 2008-05-02 Jsr Corporation Procédé de production d'un polymère modifié, polymère modifié obtenu par ce procédé et composition de caoutchouc contenant celui-ci
JP2008106118A (ja) * 2006-10-25 2008-05-08 Jsr Corp 変性重合体の製造方法、その方法により得られた変性重合体とそのゴム組成物
CN101553522B (zh) * 2006-10-25 2012-09-05 Jsr株式会社 改性聚合物的制造方法、由该方法得到的改性聚合物及其橡胶组合物
US9212300B2 (en) 2007-08-10 2015-12-15 Henkel Ag & Co. Kgaa Reactive hot melt adhesive
US9375895B2 (en) 2008-04-28 2016-06-28 Sika Technology Ag Hotmelt adhesives having an extended open time
RU2526985C2 (ru) * 2008-04-28 2014-08-27 Сикэ Текнолоджи Аг Термоклеи с увеличенным временем выдержки перед склеиванием
WO2009133093A1 (fr) * 2008-04-28 2009-11-05 Sika Technology Ag Colle thermofusible avec temps ouvert prolongé
EP2113545A1 (fr) * 2008-04-28 2009-11-04 Sika Technology AG Adhésifs thermofusibles ayant une durée d'ouverture prolongée
DE102008041278A1 (de) 2008-08-15 2010-02-18 Evonik Degussa Gmbh Verwendung von Polyolefinen als Haftvermittler für die Herstellung flächiger Laminate
DE102008041277A1 (de) 2008-08-15 2010-02-18 Evonik Degussa Gmbh Silanmodifizierte Polyolefine
DE102008041279A1 (de) 2008-08-15 2010-02-18 Evonik Degussa Gmbh Silanmodifizierte Polyolefine mit hohem Funktionalisierungsgrad
DE102008041281A1 (de) 2008-08-15 2010-02-18 Evonik Degussa Gmbh Silanmodifizierte Polyolefine mit hohem Erweichungspunkt
US8440304B2 (en) 2008-09-16 2013-05-14 Henkel Corporation Acrylic pressure sensitive adhesive formulation and articles comprising same
US8101276B2 (en) 2008-09-16 2012-01-24 Henkel Corporation Pressure sensitive adhesive compositions and articles prepared using such compositions
EP2277931A1 (fr) 2009-07-03 2011-01-26 Evonik Degussa GmbH Polyoléfines modifiées dotées d'un profil de propriétés spécifique, leur procédé de fabrication et d'utilisation
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DE102009027446A1 (de) 2009-07-03 2011-01-05 Evonik Degussa Gmbh Modifizierte Polyolefine mit besonderem Eigenschaftsprofil, Verfahren zu deren Herstellung und deren Verwendung
DE102009027445A1 (de) 2009-07-03 2011-01-05 Evonik Degussa Gmbh Modifizierte Polyolefine mit besonderem Eigenschaftsprofil, Verfahren zu deren Herstellung und deren Verwendung
EP2272933A2 (fr) 2009-07-03 2011-01-12 Evonik Degussa GmbH Polyoléfines modifiées dotées d'un profil de propriétés spécifique, leur procédé de fabrication et d'utilisation
US9023946B2 (en) 2009-12-22 2015-05-05 Henkel IP & Holding GmbH Moisture cure hot melt adhesives
US9365751B2 (en) 2012-07-24 2016-06-14 Henkel IP & Holding GmbH Reactive hot melt adhesive
US9428677B2 (en) 2013-01-24 2016-08-30 Henkel IP & Holding GmbH Reactive hot melt adhesive
US10221346B2 (en) 2014-01-14 2019-03-05 Henkel IP & Holding GmbH Reactive hot melt adhesives with improved adhesion
WO2017098890A1 (fr) * 2015-12-07 2017-06-15 株式会社Moresco Composition d'adhésif thermofusible ainsi que procédé de fabrication ce celle-ci, matériau de scellement, dispositif électronique, et lampe
JPWO2017098890A1 (ja) * 2015-12-07 2018-07-12 株式会社Moresco ホットメルト組成物、ホットメルト組成物の製造方法、シール材、電子装置、及び灯具
CN108291092A (zh) * 2015-12-07 2018-07-17 株式会社Moresco 热熔组合物、热熔组合物的制造方法、密封材料、电子装置以及灯具
JPWO2017098889A1 (ja) * 2015-12-07 2018-07-26 株式会社Moresco ホットメルト組成物、ホットメルト組成物の製造方法、シール材、電子装置、及び灯具
WO2017098889A1 (fr) * 2015-12-07 2017-06-15 株式会社Moresco Composition d'adhésif thermofusible ainsi que procédé de fabrication ce celle-ci, matériau de scellement, dispositif électronique, et lampe
EP3369782A4 (fr) * 2015-12-07 2019-06-12 Moresco Corporation Composition d'adhésif thermofusible ainsi que procédé de fabrication ce celle-ci, matériau de scellement, dispositif électronique, et lampe
US10975272B2 (en) 2015-12-07 2021-04-13 Moresco Corporation Hot melt composition, hot melt composition production method, seal material, electronic device, and lamp
US11208578B2 (en) 2015-12-07 2021-12-28 Moresco Corporation Hot melt composition, hot melt composition production method, seal material, electronic device, and lamp
US20220064354A1 (en) * 2019-01-09 2022-03-03 Showa Denko K.K. Method for producing chloroprene graft copolymer latex, adhesive containing same and adhesion method
US12018109B2 (en) * 2019-01-09 2024-06-25 Resonac Corporation Method for producing chloroprene graft copolymer latex, adhesive containing same and adhesion method

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