EP2376552A1 - Réseau transparent semi-interpénétré, comportant une phase d'un polymère de l'isobutène linéaire non réticulé - Google Patents

Réseau transparent semi-interpénétré, comportant une phase d'un polymère de l'isobutène linéaire non réticulé

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Publication number
EP2376552A1
EP2376552A1 EP09799305A EP09799305A EP2376552A1 EP 2376552 A1 EP2376552 A1 EP 2376552A1 EP 09799305 A EP09799305 A EP 09799305A EP 09799305 A EP09799305 A EP 09799305A EP 2376552 A1 EP2376552 A1 EP 2376552A1
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EP
European Patent Office
Prior art keywords
unsaturated monomer
ethylenically unsaturated
semi
polymer
meth
Prior art date
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EP09799305A
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German (de)
English (en)
Inventor
Nicole Hildebrandt
Hannah Maria KÖNIG
Kristin Tiefensee
Benjamin Davion
Cédric VANCAEYZEELE
Odile Fichet
Dominique Teyssie
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BASF SE
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BASF SE
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Priority to EP09799305A priority Critical patent/EP2376552A1/fr
Publication of EP2376552A1 publication Critical patent/EP2376552A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Definitions

  • the invention relates to a semi-interpenetrating network comprising a first phase of a linear uncrosslinked isobutene polymer and a second phase of a crosslinked polymer.
  • Linear polyisobutenes are characterized by special properties, such as high gas and moisture barrier effect and high tackifying effect. It makes the gas and moisture barrier effect of polyisobutene z. B. in sealing compounds to use. Disadvantageously, linear polyisobutenes show a high creep or cold flow, which are undesirable for many applications.
  • the tackifying effect of the polyisobutenes is exploited in adhesives.
  • the adhesives are not fully satisfactory due to the low cohesiveness of the polyisobutenes.
  • this object is achieved by a semi-interpenetrating network comprising a first phase of a linear uncrosslinked isobutene polymer and a second phase of a crosslinked polymer, wherein the crosslinked polymer is obtainable by radical copolymerization of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer, the first ethylenically unsaturated monomer is a cycloalkyl (meth) acrylate and the second ethylenically unsaturated monomer is selected from linear and branched C 1 -C 20 -alkyl (meth) acrylates, preferably among linear and branched C 6 -C 18 -alkyl (meth) acrylates.
  • the ratio of the first ethylenically unsaturated monomer to the second ethylenically unsaturated monomer by varying the ratio of the first ethylenically unsaturated monomer to the second ethylenically unsaturated monomer, one can derive the properties, e.g. As the vibration damping, the semi-interpenetrating network control.
  • the properties of the semi-interpenetrating network can be further adapted to the respective needs.
  • a semi-interpenetrating network is meant a combination of a crosslinked polymer and a linear uncrosslinked polymer, one polymer being synthesized in the presence of the other. There are essentially no covalent bonds between the two polymer constituents.
  • the uncrosslinked polymer permeates the network of crosslinked polymer and causes the two components to be physically barely separable due to entanglements and entanglements.
  • This semi-interpenetrating network allows for the combination of properties of two polymers, even if they are thermodynamically incompatible. Compared to ordinary polymer blends, the semi-interpenetrating networks are characterized by better resistance to segregation and better mechanical properties.
  • the degradation resistance of semi-interpenetrating networks is usually better than that of copolymers in which the incompatible polymers are covalently linked together as blocks.
  • an isobutene polymer is used as the linear uncrosslinked polymer.
  • the semi-interpenetrating network allows the production of (1) materials characterized by high gas and moisture barrier properties without stickiness and cold flow, or (2) stickiness and very low cold flow materials, or (3 ) Materials that are characterized by high gas and moisture barrier effect and tack without cold flow.
  • the weight ratio of the first to the second phase in the molding composition according to the invention is generally 5:95 to 95: 5, preferably 5:95 to 80:20, in particular 30:70 to 70:30.
  • High cross-linked masses of the crosslinked polymer exhibit substantially no stickiness and no cold flow.
  • the gas and moisture barrier effect of the polyisobutene is retained.
  • the compositions are suitable as dimensionally stable sealants or moldings with barrier effect for air and / or water vapor.
  • compositions according to the invention containing a high proportion of the isobutene polymer eg with a weight ratio of the first to the second phase of 60:40 to 90:10, preferably 60:40 to 80:20
  • the tackifying properties of the polyisobutene are largely retained.
  • the masses are largely free of cold flow and exhibit improved cohesiveness over polyisobutene.
  • moldings can also be produced with a high proportion of isobutene polymer.
  • the isobutene polymer comprises at least 80% by weight, especially at least 90% by weight, and more preferably at least 95% by weight and most preferably at least 99% by weight of isobutene units.
  • the isobutene polymer may also contain units of olefinically unsaturated monomers which are copolymerizable with isobutene.
  • the comonomers can be randomly distributed in the polymer or arranged as blocks.
  • Particularly suitable copolymerizable monomers are vinylaromatics, such as styrene, C 1 -C 4 -alkylstyrenes, such as ⁇ -methylstyrene, 3- and 4-methylstyrene, or 4-tert-butylstyrene, and isoolefins with 5 to 10 C atoms, such as 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene-1, 2-ethylhexene-1 and 2-propylheptene-1, or dienes such as isoprene or butadiene, in consideration.
  • the isobutene polymer preferably has a number-average molecular weight of 500 to 500,000, in particular 1,000 to 200,000, particularly preferably 20,000 to 100,000.
  • suitable polyisobutenes and their preparation are z.
  • EP-A-145235 and US-A-5068490 They are usually obtained by cationic polymerization of isobutene. The polymerization proceeds z. B. under boron trifluoride catalysis.
  • Suitable polyisobutenes are available under the name Oppanol® B 10, Oppanol® B 12 or Oppanol® B 15 from BASF Aktiengesellschaft, Ludwigshafen, Germany.
  • the polyisobutene has ethylenic unsaturation due to its production by cationic polymerization at one end of the molecule.
  • this ethylenic unsaturation can not be homo- or copolymerized by radical polymerization. Therefore, in the free-radical polymerization of ethylenically unsaturated monomers in the presence of the isobutene polymer, the isobutene polymer does not substantially participate in the reaction. There are no covalent bonds between the resulting crosslinked polymer and the isobutene polymer.
  • the isobutene polymer preferably has no functional groups (other than an optional terminal ethylenic unsaturation).
  • the second phase of the semi-interpenetrating network of the invention is formed by a crosslinked polymer.
  • the crosslinked polymer is prepared by copolymerizing a first ethylenically unsaturated monomer in the form of a cycloalkyl (meth) acrylate and a second ethylenically unsaturated monomer selected from linear and branched C 1 -C 20 -alkyl (meth) acrylates, preferably linear and branched C6-C18 alkyl (meth) acrylates.
  • the copolymerization of the ethylenically unsaturated monomers can be free-radical, anionic or cationic catalyzed. Radical copolymerization is generally preferred.
  • the weight ratio of the first ethylenically unsaturated monomer to the second ethylenically unsaturated monomer is generally 99: 1 to 1:99, preferably 90:10 to 10:90, in particular 80:20 to 20:80.
  • Cycloalkyl (meth) acrylates contain a mono- or polycyclic cycloalkyl radical which is bonded directly or via a C 1 -C 4 -alkylene group to a (meth) acryloyloxy radical.
  • the cycloalkyl radical may, for. B. carry one to four Ci-C4-alkyl substituents.
  • cyclopentyl acrylate cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 4-methylcyclohexyl acrylate, 4-methylcyclohexyl methacrylate, 2,6-dimethylcyclohexyl acrylate, 2,6-dimethylcyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, adamantyl acrylate, adamantyl methacrylate, 3,5-dimethyl adamantyl acrylate and 3 , 5-dimethyladamantyl.
  • C 1 -C 20 -alkyl (meth) acrylates are alkyl acrylates and methacrylates having 1 to 20 C atoms in the alkyl radical, in particular methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate , Pentyl (meth) acrylate, hexyl (meth) acrylate, tert-butyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth ) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, isododecyl (meth) acrylate, tridecyl (meth) acrylate
  • hexyl methacrylate lauryl methacrylate, isodecyl methacrylate, stearyl methacrylate and mixtures thereof.
  • Water-soluble monomers are, for. B. (meth) acrylic acid, (meth) acrylamide.
  • Hydrophilic monomers are, above all, those which have a hydroxyl and / or amino group, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butanediol mono (meth) acrylate, dimethylaminoethyl (meth) acrylates).
  • the above monoethylenically unsaturated monomers may be polymerized together with polyethylenically unsaturated monomers to obtain a crosslinked polymer.
  • the polyethylenically unsaturated monomers include compounds having at least two non-conjugated, ethylenically unsaturated double bonds, e.g. As the diesters of dihydric alcohols with ⁇ , ß-monoethylenically unsaturated C3-C10 monocarboxylic acids.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, polyethylene glycol di (meth) acrylate , Divinylbenzene, vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, methylenebisacrylamide, cyclopentadienyl acrylate, tricyclodecenyl (meth) acrylate, N, N'-divinylimidazolin-2-one or triallyl cyanurate.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glyco
  • Ethylene glycol diacrylate and 1,4-butanediol diacrylate are preferred polyethylenically unsaturated monomers.
  • crosslinking monomers z may be in the crosslinking monomers z.
  • crosslinking monomers z may be epoxy or urethane ethane (meth) acrylates.
  • Epoxy (meth) acrylates are, for.
  • Urethane (meth) acrylates are, in particular, reaction products of hydroxyalkyl (meth) acrylates with polyisocyanates or diisocyanates (also see R. Holmann, UV and EB Curing Formulation for Printing Inks and Paints, London 1984).
  • the urethane (meth) acrylates also include the reaction products of hydroxyalkyl (meth) acrylates with isocyanurates.
  • Preferred isocyanurates are the isocyanurates of the customary diisocyanates.
  • diisocyanates X (NCO) 2 wherein X is an aliphatic hydrocarbon radical having 4 to 15 carbon atoms, a cycloaliphatic or aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms.
  • diisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,2-bis (4-isocyanatocyclohexyl) -propane, trimethylhexane diisocyanate , 1, 4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanato-diphenylmethane, 2,4'-diisocyanato-diphenylmethane, p-xylylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI), the isomers of bis (4-iso
  • the crosslinking monomers are usually used in an amount of 0.1 to 100 mol%, e.g. B. 0.1 to 30 mol .-%, preferably 1 to 20 mol .-%, in particular 3 to 10 mol .-%, based on the total amount of constituent monomers used.
  • postcrosslinking monomers are used.
  • the crosslinking active sites of the postcrosslinking monomers do not participate in the building reaction, but can be selectively postcrosslinked in a downstream step.
  • Suitable post-crosslinking monomers are, for. Glycidyl methacrylate, acrylamidoglycolic acid, methyl acrylamidoglycolic acid methyl ester, N-methylolacrylamide, N-
  • the amount of crosslinking monomers is chosen so that a desired degree of crosslinking occurs.
  • the degree of crosslinking is defined as the amount of substance (in moles) of crosslinker divided by the molar amount (in moles) of the total monomers present.
  • the degree of crosslinking is preferably 1 to 20%, in particular 3 to 10%.
  • the polymerization is preferably initiated by means of a radical-forming initiator and / or by high-energy radiation such as UV radiation or electron radiation.
  • Redox initiator pairs comprising an oxidizing agent and a reducing agent may also be used.
  • the initiator is usually used in an amount of 0.1 to 2% by weight based on the total amount of the monomers of the crosslinked polymer.
  • Suitable initiators from the class of peroxide compounds, azo Compounds or azoperoxide compounds are known to those skilled in the art and are commercially available.
  • Suitable initiators include di-tert-butyloxypivalate, didecanoyl peroxide, dilauroyl peroxide, diacetyl peroxide, di-tert-butyl peroctoate, dibenzoyl peroxide, tert-butyl peracetate, tert-butyl peroxyisopropyl carbonate, tert-butyl perbenzoate, di-tert-butyl peroxide, 1, 1 Bis- (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (benzoylperoxy) -hexane, 1,4-di- (tert-butylperoxycarbonyl) -cyclohexane, 1, 1- Bis- (tert-butylperoxy) cyclohexane, di-tert-butyldiperoxyazelat, or di-tert-butylperoxycarbonate
  • a suitable azo initiator is z. B. azoisobutyronitrile (AIBN).
  • a photoinitiator is used.
  • the photoinitiator may be z. These are photoinitiators in which a chemical bond is cleaved to form 2 radicals which initiate the further crosslinking or polymerization reactions.
  • H-abstractors which detach a hydrogen atom from the polymer chain
  • these are photoinitiators with a carbonyl group. This carbonyl group slides into a C-H bond to form a C-C-O-H moiety.
  • Both classes of photoinitiators may be used alone or in admixture.
  • the thermal polymerization is usually carried out at elevated temperature, wherein a temperature range of 40 to 180 0 C, preferably 60 to 120 0 C, is suitable.
  • the temperature can also be increased gradually. If the polymerization is initiated by high-energy radiation, lower temperatures are suitable, for. B. ambient temperature.
  • the polymerization can be carried out in different ways. It usually takes place as bulk polymerization, solution polymerization, emulsion polymerization or miniemulsion polymerization. Solvents may optionally be used. At low to medium proportions, z. Example, at weight ratio of the first phase to the second phase up to 70:30, the synthesis can be carried out in the absence of solvent when the isobutene polymer in the precursors of the crosslinked polymer, for. B. the constituent monomers, is soluble. The monomers act as reactive solvents. To reduce the viscosity of the reaction mixture, it may nevertheless be advantageous to use a solvent. At higher first phase to second phase weight ratios than 70:30 or when the isobutene polymer is not or not sufficiently soluble in precursors of the cross-linked polymer, the addition of a solvent is usually unavoidable.
  • saturated or unsaturated aliphatic hydrocarbons such as hexane, pentane, isopentane, cyclohexane, methylcyclohexane, diisobutene, triisobutene, tetraisobutene, pentaisobutene, hexaisobutene or mixtures thereof, aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as dichloromethane or Trichloromethane, or mixtures thereof.
  • the polymerization can also be carried out in the presence of a plasticizer or a plasticizer mixture, such as the phthalates and adipates of aliphatic or aromatic alcohols, for.
  • a plasticizer or a plasticizer mixture such as the phthalates and adipates of aliphatic or aromatic alcohols, for. Di- (2-ethylhexyl) adipate, di (2-ethylhexyl) phthalate, diisononyl adipate or diisononyl phthalate.
  • the procedure is such that the solution or dispersion is converted into a plastically formable state by the addition of fillers and / or thickeners.
  • This mass can then be formed into any desired shape.
  • the molding may conveniently be effected by extrusion through a die. In this way, for example, sealing profiles are easy to produce.
  • the shape of the formed mass is then fixed by initiating the copolymerization.
  • the primary network can then be formed into any desired shape, optionally after the addition of fillers.
  • the shape of the formed mass is then fixed by post-crosslinking.
  • the Post-crosslinking can be achieved by increasing the temperature, high-energy radiation and / or suitable catalysts or the like. Postcrosslinking is facilitated if postcrosslinking monomers are used in the copolymerization, the postcrosslinking sites of which do not participate in the copolymerization and can be selectively postcrosslinked after the copolymerization and shaping.
  • compositions according to the invention may additionally contain customary auxiliaries which are customary for the respective application. These include z. As fillers, thinners or stabilizers.
  • active substances or effect substances are incorporated into the semi-interpenetrating networks according to the invention.
  • Suitable active ingredients are, for example, biocides; suitable effect substances are dyes.
  • the active substances or excipients are generally immiscible with pure polyisobutene but are soluble or dispersible in the semi-interpenetrating network or can be covalently anchored in the crosslinked polymer. The invention therefore shows for the first time a way to combine the properties of isobutene polymers with the properties of the active ingredients and effect substances.
  • Suitable fillers are for.
  • silica colloidal silica, calcium carbonate, carbon black, titanium dioxide, mica, quartz, glass fibers and glass beads and the like.
  • Suitable diluents are for. Polybutene, liquid polybutadiene, hydrogenated polybutadiene, paraffin oil, naphthenates, atactic polypropylene, dialkyl phthalates, reactive diluents, e.g. For example, alcohols and oligoisobutenes.
  • Suitable stabilizers are, for. 2-benzothiazolylsulfide, benzothiazole, thiazole, dimethylacetylenedicarboxylate, diethylacetylenedicarboxylate, butylhydroxytoluene (BHT), butylhydroxyanisole, vitamin E.
  • the semi-interpenetrating network can be prepared as a sheet-like structure, in particular film, applying to a support a composition comprising a linear uncrosslinked isobutene polymer and polyfunctional resin precursors and / or monomers together with at least one crosslinking agent, and initiated copolymerization in the composition.
  • the copolymerization is preferably initiated thermally or by high-energy radiation, in particular by UV light.
  • the composition preferably contains at least one photoinitiator.
  • the coated support is irradiated with high-energy light, preferably UV light, to achieve the desired networking.
  • the radiation energy can z. B. 10 mJ / cm 2 to 1500 mJ / cm 2 irradiated area.
  • the carrier material may be a temporary carrier, from which the sheet-like structure is removed again after production or immediately before use, for example.
  • the application to the carrier can be carried out by known methods, for. B. by roller application, knife coating, dipping or the like.
  • the amount applied can be in particular 10 to 300 g, preferably 10 to 150 g, and usually often 20 to 80 g per square meter carrier.
  • the materials according to the invention are suitable for the following applications.
  • preformed semi-interpenetrating networks eg in the form of films
  • the semi-interpenetrating network is obtained in situ from an uncrosslinked semi-IPN:
  • the inventive semi-interpenetrating network can at higher temperatures than pure PIB in
  • Window sealing area can be used without it comes to sweating.
  • the uncrosslinked semi-IPN is incorporated and polymerized / crosslinked in situ to produce waterproofing compounds with good adhesion to building materials.
  • the sealants inhibit the growth caused by fungi or bacteria. Such compositions could replace moisture-curing silicone systems.
  • Anti-fouling coatings that prevent or reduce the growth of microorganisms, such as bacteria or algae.
  • - Waterproof tarpaulins, z. As for lining of holes and cavities in geological formations in the z. B. combustion residues are spent.
  • Materials or moldings for roofing buildings in the form of film webs or sheets.
  • - Polymer films for glass coating Films from the semi-interpenetrating network according to the invention can be adhesively bonded flat on glass surfaces, in particular glass panes. These films are used for radiation protection or give the glass a color (Autoglastönung).
  • Ultrathin films that are applied to objects such as sculptures, paintings, old books or monuments to protect against moss, algae or mold.
  • the adhesives can be adjusted transparently. They show advantages over dispersion-based adhesives, which can become cloudy on contact with water - adhesives for hydrophobic surfaces, such as plastics,
  • Adhesives for glass surfaces for example double glazing glue / safety glass.
  • Safety glass is constructed from a sandwich set-up glass / polymer film / glass.
  • polyvinyl butyral is conventionally used.
  • the adhesive properties and the mechanical reinforcement can also be achieved with films of semi-interpenetrating networks according to the invention.
  • Adhesives for so-called 100% systems in which the curing of the adhesive is carried out after application by subsequent cross-linking.
  • - Insulator layers for the electronics industry.
  • Semi-interpenetrating networks according to the invention enable the use of PIB in the electronics industry for watertight sealing / packaging of electronic components in order to avoid short circuits, corrosion, etc.
  • Fig. 1 shows the storage modulus as a function of the temperature for semi-1 PN of PIB in crosslinked (co) polymers (weight ratio PIB: (co) polymer 50/50); from left: lauryl methacrylate homopolymer; Lauryl methacrylate-cyclohexyl methacrylate copolymers 25-co-75; 50-co-50; 75-co-25; Cyclohexyl homopolymer;
  • Fig. 2 shows the loss factor (tan ⁇ ) as a function of the temperature for semi-1 PN of PIB in crosslinked (co) polymers (50/50); from left: lauryl methacrylate homopolymer; Lauryl methacrylate-cyclohexyl methacrylate copolymers 25-co-75; 50-co-50; 75-co-25; Cyclohexyl homopolymer.
  • Oppanol B15SFN was used as the polyisobutene. It is a polyisobutene having a molecular weight of 85,000 g / mol (viscosity agent).
  • the semi-IPN shows two mechanical relaxations at - 50 0 C and 58 ° C, the (CHMA-co-HMA 25-co-75) phase are for the P characteristic or PIB.
  • the PIB / P (CHMA-co-HMA 25-co-75) 50/50 semi-IPN has a storage modulus of 73 MPa at 20 ° C and no cold flow even at high temperature (up to 200 ° C).
  • the semi-IPN was synthesized under the same experimental conditions (same molar ratios of crosslinker and initiator, with respect to cyclohexyl methacrylate and hexyl methacrylate) as in the previous example.
  • the semi-IPN exhibits two mechanical relaxations - 50 ° C and 85 ° C, which are characteristic of the PIB and P (CHMA-co-HMA 50-co-50) phases, respectively.
  • the PIB / P (CHMA-co-HMA 50-co-50) 50/50 semi-IPN has a storage modulus of 167 MPa and also at high temperature (up to 200 0 C) no cold flow at 20 0 C.
  • the semi-IPN was synthesized under the same experimental conditions (same molar ratios of crosslinker and initiator with respect to cyclohexyl methacrylate and hexyl methacrylate) as in the previous example.
  • the semi-IPN shows two mechanical relaxations at - 50 0 C and 1 17 ° C, the (75-co-25 CHMA-co-HMA) phases are characteristic of the PIB and P.
  • the PIB / P (CHMA-co-HMA 75-co-25) 50/50 semi-IPN has a storage modulus of 182 MPa and also at high temperature (up to 200 0 C) no cold flow at 20 ° C.
  • the semi-IPN was synthesized under the same experimental conditions (same molar ratios of crosslinker and initiator with respect to cyclohexyl methacrylate and hexyl methacrylate) as in the previous example.
  • the semi-IPN exhibits two mechanical relaxations - 50 ° C and 24 ° C, which are characteristic of the PIB and P (CHMA-co-LMA 25-co-75) phases, respectively.
  • the PIB / P (CHMA-co-LMA 25-co-75) 50/50 semi-IPN has a storage modulus of 6 MPa and at high temperature (up to 200 ° C) no cold flow at 20 0 C.
  • the semi-IPN was synthesized under the same experimental conditions (same molar ratios of crosslinker and initiator with respect to cyclohexyl methacrylate and lauryl methacrylate) as in the previous example.
  • the semi-IPN shows two mechanical relaxations at - 50 0 C and 61 0 C, the (50-co-50 CHMA-co-LMA) phases are characteristic of the PIB and P.
  • the PIB / P (CHMA-co-LMA 50-co-50) 50/50 semi-IPN has a storage modulus of 83 MPa and at high temperature (up to 200 0 C) no cold flow at 20 ° C.
  • the semi-IPN was synthesized under the same experimental conditions (same molar ratios of crosslinker and initiator with respect to cyclohexyl methacrylate and lauryl methacrylate) as in the previous example.
  • the semi-IPN was synthesized under the same experimental conditions (same molar ratios of crosslinker and initiator with respect to cyclohexyl methacrylate and lauryl methacrylate) as in the previous example.
  • the semi-IPN exhibits two mechanical relaxations - 50 ° C and 78 ° C, which are characteristic of the PIB and P (CHMA-co-iDMA 50-co-50) phases, respectively.
  • the PIB / P (CHMA-co-iDMA 50-co-50) 50/50 semi-IPN has a storage modulus of 114 MPa at 20 ° C and no cold flow even at high temperature (up to 200 ° C).
  • the semi-IPN was synthesized under the same experimental conditions (same molar ratios of crosslinker and initiator with respect to cyclohexyl methacrylate and iso-decyl methacrylate) as in the previous example.
  • the semi-IPN shows two mechanical relaxations at - 50 0 C and 58 ° C, the (CHMA-co-SMA 50-co-50) phases are for the P characteristic or PIB.
  • the PIB / P (CHMA-co-SMA 50-co-50) 50/50 semi-IPN has a storage modulus of 38 MPa and at high temperature (up to 160 0 C) no cold flow at 20 0 C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Sealing Material Composition (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Inorganic Chemistry (AREA)

Abstract

L'invention porte sur un réseau transparent semi-interpénétré, qui comprend une première phase d'un polymère de l'isobutène linéaire et non réticulé, et une deuxième phase d'un polymère réticulé. Le polymère réticulé peut être obtenu par copolymérisation d'un premier monomère à insaturation éthylénique et d'un deuxième monomère à insaturation éthylénique, le premier monomère à insaturation éthylénique étant un (méth)acrylate de cycloalkyle, et le deuxième monomère à insaturation éthylénique étant choisi parmi les (méth)acrylates d'alkyle en C1-C20 à chaîne droite et ramifiée. En faisant varier le rapport entre le premier monomère à insaturation éthylénique et le deuxième monomère à insaturation éthylénique, on peut piloter les propriétés, par exemple l'amortissement des vibrations, du réseau semi-interpénétré.
EP09799305A 2008-12-10 2009-12-09 Réseau transparent semi-interpénétré, comportant une phase d'un polymère de l'isobutène linéaire non réticulé Withdrawn EP2376552A1 (fr)

Priority Applications (1)

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EP09799305A EP2376552A1 (fr) 2008-12-10 2009-12-09 Réseau transparent semi-interpénétré, comportant une phase d'un polymère de l'isobutène linéaire non réticulé

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EP08171226 2008-12-10
PCT/EP2009/066767 WO2010066809A1 (fr) 2008-12-10 2009-12-09 Réseau transparent semi-interpénétré, comportant une phase d'un polymère de l'isobutène linéaire non réticulé
EP09799305A EP2376552A1 (fr) 2008-12-10 2009-12-09 Réseau transparent semi-interpénétré, comportant une phase d'un polymère de l'isobutène linéaire non réticulé

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EP2376552A1 true EP2376552A1 (fr) 2011-10-19

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US (1) US20110230621A1 (fr)
EP (1) EP2376552A1 (fr)
JP (1) JP2012511605A (fr)
CN (1) CN102245656A (fr)
WO (1) WO2010066809A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103319662A (zh) * 2013-06-28 2013-09-25 中南大学 一种疏水/亲水性交联聚二乙烯苯/聚丙烯酰多乙烯多胺互贯聚合物网络及其制备方法

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5554933B2 (ja) * 2009-03-04 2014-07-23 ニッタ株式会社 感温性粘着剤
US8349977B2 (en) 2010-02-17 2013-01-08 Basf Se Process for preparing high-reactivity isobutene homo- or copolymers
US9562117B2 (en) 2010-11-30 2017-02-07 Basf Se Preparation of derivatives of isobutene copolymers
US9296841B2 (en) 2010-11-30 2016-03-29 Basf Se Preparation of isobutene homo- or copolymer derivatives
JP2013032500A (ja) * 2011-06-30 2013-02-14 Nitto Denko Corp 粘着剤組成物、粘着剤層、および粘着シート
JP2013173913A (ja) * 2011-11-10 2013-09-05 Nitto Denko Corp 板の剥離方法
JP2013133440A (ja) * 2011-12-27 2013-07-08 Nitto Denko Corp 粘着剤、粘着剤層、および粘着シート
EP3023461B1 (fr) * 2013-07-19 2020-10-21 LG Chem, Ltd. Composition de scellement
JP2018159066A (ja) * 2017-03-22 2018-10-11 三菱ケミカル株式会社 硬化性組成物、硬化シート、画像表示装置
CN110431174A (zh) * 2017-03-22 2019-11-08 三菱化学株式会社 固化性组合物、片、使用其的层叠体、图像显示装置
JP2019014888A (ja) * 2017-07-06 2019-01-31 三菱ケミカル株式会社 樹脂組成物、シート、それを用いた積層体、画像表示装置
FR3069187B1 (fr) * 2017-07-24 2019-08-02 Saint-Gobain Glass France Polymere hybride pour intercalaire plastique viscoelastique
JP2019073691A (ja) * 2017-10-11 2019-05-16 三菱ケミカル株式会社 樹脂組成物、シート、それを用いた積層体、画像表示装置
CN108299829B (zh) * 2018-03-16 2020-07-28 武汉大学 有机硅互穿网络聚合物及其制备方法
WO2020012329A2 (fr) * 2018-07-12 2020-01-16 3M Innovative Properties Company Composition comprenant un copolymère séquencé de styrène-isobutylène et un monomère à insaturation éthylénique
KR102577202B1 (ko) * 2018-11-14 2023-09-11 덴카 주식회사 조성물
JP7516784B2 (ja) * 2020-03-06 2024-07-17 三菱ケミカル株式会社 積層フィルム、それを用いたフィルム積層体
WO2021235406A1 (fr) 2020-05-21 2021-11-25 デンカ株式会社 Composition

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6001936A (en) * 1997-10-24 1999-12-14 3M Innovative Properties Company Dye enhanced durability through controlled dye environment
DE10338245A1 (de) * 2003-08-20 2005-03-24 Basf Ag Formmasse
EP2363443B1 (fr) * 2005-12-15 2020-11-18 Huntsman Advanced Materials Licensing (Switzerland) GmbH Adhésifs acryliques à phases multiples
JP2008163130A (ja) * 2006-12-27 2008-07-17 Jsr Corp 水性エマルジョンの製造方法及び水性エマルジョン
WO2008155395A1 (fr) * 2007-06-19 2008-12-24 Basf Se Réseau semi-interpénétrant avec une phase d'un polymère d'isobutène linéaire non réticulé

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010066809A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103319662A (zh) * 2013-06-28 2013-09-25 中南大学 一种疏水/亲水性交联聚二乙烯苯/聚丙烯酰多乙烯多胺互贯聚合物网络及其制备方法
CN103319662B (zh) * 2013-06-28 2015-07-01 中南大学 一种疏水/亲水性交联聚二乙烯苯/聚丙烯酰多乙烯多胺互贯聚合物网络及其制备方法

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US20110230621A1 (en) 2011-09-22
WO2010066809A1 (fr) 2010-06-17
CN102245656A (zh) 2011-11-16

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