WO2020165135A1 - Capsule de copolymère acrylique conçue pour s'ouvrir à moins 90 de °c pour une libération contrôlée de catalyseur pu/pir de formation in situ - Google Patents

Capsule de copolymère acrylique conçue pour s'ouvrir à moins 90 de °c pour une libération contrôlée de catalyseur pu/pir de formation in situ Download PDF

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Publication number
WO2020165135A1
WO2020165135A1 PCT/EP2020/053414 EP2020053414W WO2020165135A1 WO 2020165135 A1 WO2020165135 A1 WO 2020165135A1 EP 2020053414 W EP2020053414 W EP 2020053414W WO 2020165135 A1 WO2020165135 A1 WO 2020165135A1
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meth
weight
acrylic acid
acrylate
composition
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PCT/EP2020/053414
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English (en)
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Julia LIESE
Li Zhang
Roland Hinrich STAFF
Antoine Maxime Charles Joseph BEZIAU
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/18—In situ polymerisation with all reactants being present in the same phase
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/32—Polymerisation in water-in-oil emulsions
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups

Definitions

  • Acrylic Copolymer Capsule designed to open up at ⁇ 90°C for controlled release of in-situ forming PU/PIR catalyst
  • the present invention relates to a catalyst useful for polyurethane or polyisocyanurate synthesis comprising an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell, wherein the (meth)acrylic copolymer capsule shell is obtained or obtainable by reacting: i) 10 to 90 weight-% of a first (meth)acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol; ii) 90 to 10 weight-% of a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol; wherein the weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%.
  • the invention further relates to a catalytic composition comprising the catalyst and an epoxide composition. Furthermore, the present invention relates to a process for preparation of an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell, and also to an aqueous and/or alcoholic solution of lithium chloride encapsulated in an acrylic copolymer capsule shell obtained or obtainable from the process, as well as to the use of the catalyst or of the aqueous and/or alcoholic solution of lithium chloride encapsulated in an acrylic copolymer capsule shell obtained or obtainable from the process for the preparation of polyurethane or polyisocyanurate.
  • the invention also relates to a polyurethane or polyisocyanurate obtained or obtainable from the reaction of at least: a) a polyisocyanate composition; b) a polyol composition; in the presence of an epoxide composition and a catalyst comprising an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell, wherein the (meth)acrylic copolymer capsule shell is obtained or obtainable by reacting: i) 10 to 90 weight-% of a first (meth)acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol; ii) 90 to 10 weight-% of a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol; wherein the weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%.
  • US 6,224,793 B1 discloses an active agent encapsulated in a crystallizable or thermoplastic polymer wherein the particle size of the encapsulated active agent is 3,000 microns or less, wherein the active agent is not significantly extractable from the particles under ambient conditions.
  • Crystalizable polymer has the disadvantage that the production process is very complex by melting the polymer at 125 °C and spinning the molten polymer at 15 000 rpm to form particles.
  • US 7,338,928 B2 discloses a controlled release system comprising a wide range of effectively encapsulated active ingredients and sensory markers. Release is triggered in response to moisture or over an extended period of time. Moisture release is not applicable for release in polyu- rethane systems for filament winding or pulltrusion.
  • thermolatent catalyst nanocapsules The capsule core consists of isooctane and dimethyltin neodecanoate, the capsule shell of poly(methyl methacrylate-co-butyl methacrylate-co-methacrylic acid, which is crosslinked via butanediol di methacrylate.
  • the capsules are produced by a mini emulsion technique.
  • the only stimulus described for the release of catalyst is the thermal opening triggered by an expansion agent. Disadvantage here is the low shelf stability. After only about two weeks storage of the capsules, the reaction profile has noticeably changed.
  • WO 2013/057070 A1 describes the production of fibre-reinforced polyisocyanurate components, using as catalyst a latent reactive trimerization catalyst. Disadvantages of these components are an open time at room temperature which is still decidedly short.
  • WO 2010/121898 A1 describes a polyisocyanate component which consists in parts of a urea prepolymer (-NH-CO-NH-) which is bidentate in respect of the anion, this prepolymer having been mixed with lithium chloride.
  • this component is mixed with a second component containing epoxide and polyol, and the resulting mixture is heated to > 90°C, a rapid reaction occurs, leading to through-curing of the material.
  • WO 2012/103965 A1 describes an epoxy-based system which is based on the same catalysis as described in WO 2010/121898 A1.
  • the groups needed for catalysis are defined, via the two hydrogen atoms located on the nitrogen, as a carboxamide group (-CO-NH2), bidentate in respect of the anion, with LiCI.
  • this catalyst works at temperatures > 90 °C only.
  • WO 2013/098034 A1 embraces a reactive mixture which as well as lithium halide requires a -(-CO-NH-CO-)- group which is bidentate in respect of the cation.
  • the urea component described in this specification may also contain polydentate biuret groups (-NH-CO-N H-CO-NH-). Catalytic activity is reached at temperatures > 90 °C as well.
  • WO 2013143841 A1 Described in WO 2013143841 A1 is a trimerization catalyst consisting of alkali metal or alkaline earth metal salts in combination with carboxamide groups of the structure -CO-NH2, which are bidentate in respect of the anion, or in combination with groups -(-CO-NH-CO-)-, which are bidentate in respect of the cation. Catalytic activity is reached at temperatures > 90 °C as well.
  • WO 2015/078740 A1 describes a polyisocyanate component which consists in parts of a urethane prepolymer (-NH-CO-), this prepolymer having been mixed with lithium chloride.
  • this catalyst works at temperatures > 90 °C only.
  • a disadvantage of the systems described in WO 2010/121898 A1 , WO 2012/103965 A1 , WO 2013/098034 A1 , WO 2013/143841 A1 and WO 2015/078740 A1 is that the catalyst is only activated at temperatures > 90 °C.
  • this object was solved by a catalyst useful for polyurethane or polyisocyanurate synthesis comprising an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell, wherein the (meth)acrylic copolymer capsule shell is obtained or obtainable by reacting:
  • a first (meth)acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;
  • a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%.
  • (meth)acrylic acid comprises meth acrylic acid and acrylic acid; the same applies to the term“(meth)acrylate”, which comprises methacrylate and acrylate.
  • Such a catalyst could be activated at temperatures ⁇ 90 °C.
  • the use of such a catalyst in polyurethane or polyisocyanurate synthesis resulted in prolonged open times at room temperature (RT) and short curing start times at temperatures ⁇ 90 °C, for example, less than 10 min at 70 °C, and a rather quick reactivity.
  • the (meth)acrylic copolymer capsule shell is obtained or obtainable by reacting:
  • a first acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C10 alkylpolyol;
  • ii) 50 to 70 weight-%, preferably 65 to 55 weight-%, more preferred 62 to 58 weight-% of a second acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C10 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%.
  • the polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol of (i) is preferably a polyester of (meth)acrylic acid with a C2 to C10 alkylpolyol, more preferably selected from the group consisting of polyesters of (meth)acrylic acid with a C4 to C5 alkylpolyol, wherein the alkylpolyol has 2 to four hydroxyl groups, preferably selected from the group consisting of 1 ,4-butandioldiacrylate, pentaerytritol-triacrylate, pentaerytritol-tetraacrylate and mixtures of two or more of these compounds.
  • the monoester of (meth)acrylic acid with a C1 to C24 alkanol of (ii) is preferably a monoester of (meth)acrylic acid with a C1 to C10 alkanol, more preferably selected from the group consisting of C1 to C5 alkylesters of (meth)acrylic acid and mixtures of two or more C1 to C5 alkylesters of (meth)acrylic acid, preferably from the group consisting of methyl(meth)acrylate, butylacrylate and mixtures of two or more of these compounds, more preferred from the group consisting of methylmethacrylate, butylacrylate and mixtures of methylmethacrylate and butylacrylate.
  • the polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol of (i) comprises a mixture of pentaerytritol-triacrylate and pentaerytritol-tetraacrylate (PETIA) and the monoester of (meth)acrylic acid with a C1 to C24 alkanol of (ii) comprises butylacrylate (nBA).
  • PETIA pentaerytritol-triacrylate
  • nBA butylacrylate
  • the weight-ratio PETIA to nBA is in the range of from 0.5 to 0.7, more preferably 0.6.
  • the catalyst is obtained or obtainable by:
  • a first (meth)acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;
  • a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%;
  • LiCI-capsule an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell
  • the aqueous and/or alcoholic solution of lithium chloride comprises 40 to 90 weight-% lithium chloride and 60 to 10 weight-% of a solvent selected from the group consisting of water, C1 to C10 alkyl monools, C1 to C10 alkyl polyols and mixtures of two or more of these solvents, preferably from the group consisting of water, methanol, ethanol, 1 ,2-propylene glycol and mixtures of two or more of these solvents, preferably at least 1 ,2-propylene glycol, wherein the weight-% are based on the overall weight of the aqueous and/or alcoholic solution of lithium chloride.
  • a solvent selected from the group consisting of water, C1 to C10 alkyl monools, C1 to C10 alkyl polyols and mixtures of two or more of these solvents, preferably from the group consisting of water, methanol, ethanol, 1 ,2-propylene glycol and mixtures of two or more of these solvents,
  • the core/shell ratio of the LiCI-capsule is in the range of from 99/1 to 70/30, preferably in the range of from 98/2 to 75/25, more preferred in the range of from 95/5 to 80/20.
  • the core/shell ratio is thus dimensionless.
  • the hydrophobic diluent of (I) has a solubility in water of ⁇ 0.5 g/liter at 20 °C and at normal pressure (1013 mbar) and is preferably selected from the group consisting of cyclohexane, glycerol ester oils, hydrocarbon oils, such as paraffin oil, diisopropylnaphthalene, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in hydrocarbon oils, animal oil, vegetable oils or mineral oils, the distillation start-point of which under atmospheric pressure is 250°C and the distillation end-point of which is 410 °C, such as e.g.
  • esters of saturated or unsaturated fatty acids such as alkyl myristate, e.g. isopropyl myristate, butyl myristate or cetyl myristate, hexadecyl stearate, ethyl palmitate, isopropyl palmitate or cetyl ricinoleate, silicone oils, such as dimethylpolysiloxane, methylphenylpolysiloxan, or silicone glycol copolymer, fatty acids and fatty alcohols or waxes such as carnauba wax, candellila wax, bees wax, microcrystalline wax, ozokerite wax, Ca, Mg and Al oleates, Ca, Mg and Al myristates, Ca, Mg and Al linoleates and Ca, Mg and Al stearate; preferably at least diisopropylnaphthalene.
  • alkyl myristate e.g. isopropyl myristate, but
  • Glycerol ester oils are understood as meaning esters of saturated or unsaturated fatty acids with glycerol. Mono-, di- and triglycerides, and their mixtures are suitable. Preference is given to fatty acid triglycerides. Fatty acids which may be mentioned are, for example, C2-C12-fatty acids such as hexanoic acid, octanoic acid, decanoic acid and dodecanoic acid.
  • Preferred glycerol ester oils are C2-C12-fatty acid triglycerides, in particular octanoic acid and decanoic acid triglycerides, and their mixtures. Such an octanoyl glyceride/decanoyl glyceride mixture is for example Miglyol® 812 from Huls.
  • the invention also relates to a catalytic composition comprising a catalyst according to any of the embodiments described above and an epoxide composition.
  • the epoxide composition comprises a compound having one or more epoxide groups. It is possible to use all epoxide-containing compounds which are customarily used for preparing epoxy resins.
  • the compound comprising one or more epoxide groups is preferably liquid at 25 °C.
  • mixtures of such compounds these mixtures being preferably likewise liquid at 25 °C.
  • Examples of such compounds containing epoxide groups and able to be used for the purposes of the invention are: A) Polyglycidyl and poly([beta ]-methylglycidyl) esters, obtainable by reacting a compound having at least two carboxyl groups in the molecule and in each case epichlorohydrin and [beta]-methylepichlorohydrin. This reaction is advantageously catalyzed by the presence of bases.
  • Aliphatic polycarboxylic acids can be used, for example, as compound having at least two carboxyl groups.
  • aliphatic polycarboxylic acids examples include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and dimerized or trimerized linoleic acid.
  • cyclic aliphatic acids such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid.
  • Aromatic carboxylic acids as well, such as phthalic acid, isophthalic acid or terephthalic acid, and also any desired mixtures of these carboxylic acids, can be used.
  • the glycidyl ethers of this type are derived, for example, from linear alcohols, such as ethylene glycol, diethylene glycol or higher poly(oxyethylene) glycols, propane- 1 ,2-diol or poly( oxypropylene) glycols, propane-1 ,3- diol, butane-1 ,4-diol, poly( oxytetramethylene) glycol, pentane- 1 .5-diol, hexane-1 6-diol, hexane-2, 4, 6-triol, glycerol, 1 ,1 ,1-trimethylolpropane, pentaerythritol or sorbitol, and from polyepichlorohydrins. Further glycidyl ethers of this type are obtainable from cycloaliphatic alcohols, such as
  • the glycidyl ethers may also be based on monocyclic phenols, such as p-tert-butylphenol, resorcinol or hydroquinone, or on polycyclic phenols, such as bis( 4- hydroxyphenyl)methane, 4.4'-dihydroxybiphenyl, bis( 4-hydroxyphenyl) sulfone, 1 , 1 ,2,2-tetrakis( 4-hydroxyphenyl) ethane, 2,2-bis( 4-hydroxyphenyl)propane or 2,2-bis(3,5- dibromo-4-hydroxyphenyl)propane.
  • monocyclic phenols such as p-tert-butylphenol, resorcinol or hydroquinone
  • polycyclic phenols such as bis( 4- hydroxyphenyl)methane, 4.4'-dihydroxybiphenyl, bis( 4-hydroxyphenyl) sulfone, 1 , 1 ,2,2-tetraki
  • novolaks obtainable by condensing aldehydes, such as formaldehyde, acetaldehyde, chloraldehyde or furfuraldehyde, with phenols or bisphenols, which may be unsubstituted or substituted, as for example by chlorine atoms or Cl to C9 alkyl groups, such as phenol, 4-chlorophenol, 2-methylphenol or 4-tert-butyl phenol.
  • the poly(N-glycidyl) compounds also include triglycidyl isocyanurates, N,N’-diglycidyl derivatives of cycloalkyleneureas, such as ethylene urea or 1 ,3-propyleneurea, and diglycidyl derivatives of hydantoins, such as
  • Poly(S-glycidyl) compounds such as di-S-glycidyl derivatives which are obtainable from dithiols, as for example ethane-1 ,2-dithiol or bis(4-mercaptomethylphenyl) ether.
  • Cycloaliphatic epoxy resins such as bis(2,3-epoxycyclo- pentyl) ether, 2,3-epoxycyclopentyl glycidyl ether, 1 ,2-bis (2,3-epoxycyclopentyloxy)ethane or 3,4-epoxycyclohexyl- methyl 3’,4’-epoxycyclohexanecarboxylate.
  • Monofunctional epoxy resins such as (2-ethyl hexyl) glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether or cresyl glycidyl ether.
  • epoxy resins in which the 1 ,2-epoxy group is bonded to different heteroatoms or functional groups.
  • These compounds include N ,N ,0-triglycidyl derivative of 4-aminophenol, the glycidyl ether/glycidyl esters of salicylic acid,
  • Particularly preferred as compounds containing epoxide groups are the compounds of classes (A) and (B), especially those of class (A).
  • the invention also relates to a process for preparation of an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell, comprising the steps of:
  • a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%;
  • LiCI-capsule an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell
  • the (meth)acrylate momonomers comprise:
  • a first acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;
  • ii) 50 to 70 weight-%, preferably 65 to 55 weight-%, more preferred 62 to 58 weight-% of a second acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • the polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol is preferably a polyester of (meth)acrylic acid with a C2 to C10 alkylpolyol, more preferably selected from the group consisting of polyesters of (meth)acrylic acid with a C4 to C5 alkylpolyol, wherein the alkylpolyol has 2 to four hydroxyl groups, preferably selected from the group consisting of 1 ,4-butandioldiacrylate, pentaerytritol-triacrylate, pentaerytritol-tetraacrylate and mixtures of two or more of these compounds.
  • the monoester of (meth)acrylic acid with a C1 to C24 alkanol is preferably a monoester of (meth)acrylic acid with a C1 to C10 alkanol, more preferably selected from the group consisting of C1 to C5 alkylesters of (meth)acrylic and mixtures of two or more C1 to C5 alkylesters of (meth)acrylic, preferably from the group consisting of methyl(meth)acrylate, butylacrylate and mixtures of two or more of these compounds, more preferred from the group consisting of methylmethacrylate, butylacrylate and mixtures of methylmethacrylate and butylacrylate.
  • the aqueous and/or alcoholic solution of lithium chloride comprises 40 to 90 weight-% lithium chloride and 60 to 10 weight-% of a solvent selected from the group consisting of water, C1 to C10 alkyl monools, C1 to C10 alkyl polyols and mixtures of two or more of these solvents, preferably from the group consisting of water, methanol, ethanol, 1 ,2-propylene glycol and mixtures of two or more of these solvents, preferably at least 1 ,2-propylene glycol, wherein the weight-% are based on the overall weight of the aqueous and/or alcoholic solution of lithium chloride.
  • the core/shell ratio of the (meth)acrylic copolymer capsule containing the lithium chloride is in the range of from 99/1 to 70/30, preferably in the range of from 98/2 to 75/25, more preferred in the range of from 95/5 to 80/20.
  • the definition of the term“core/shell ratio” is given above in the section related to the catalyst.
  • the hydrophobic diluent of (I) has a solubility in water of ⁇ 0.5 g/liter at 20 °C and at normal pressure and is preferably selected from the group consisting of cyclohexane, glycerol ester oils, hydrocarbon oils, such as paraffin oil, diisopropylnaphthalene, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in hydrocarbon oils, animal oil, vegetable oils or mineral oils, the distillation start-point of which under atmospheric pressure is 250°C and the distillation end-point of which is 410 °C, such as e.g.
  • esters of saturated or unsaturated fatty acids such as alkyl myristate, e.g. isopropyl myristate, butyl myristate or cetyl myristate, hexadecyl stearate, ethyl palmitate, isopropyl palmitate or cetyl ricinoleate, silicone oils, such as dimethylpolysiloxane, methylphenylpolysiloxan, or silicone glycol copolymer, fatty acids and fatty alcohols or waxes such as carnauba wax, candellila wax, bees wax, microcrystalline wax, ozokerite wax, Ca, Mg and Al oleates, Ca, Mg and Al myristates, Ca, Mg and Al linoleates and Ca, Mg and Al stearate; preferably at least diisopropylnaphthalene.
  • alkyl myristate e.g. isopropyl myristate, but
  • the invention also relates to an aqueous and/or alcoholic solution of lithium chloride encapsulated in an acrylic copolymer capsule shell obtained or obtainable from the process as described above.
  • the invention also relates to the use of the catalyst as disclosed above or of the aqueous and/or alcoholic solution of lithium chloride encapsulated in an acrylic copolymer capsule shell obtained or obtainable from the process as disclosed above for the preparation of polyurethane or polyisocyanurate.
  • the invention also relates to a polyurethane or polyisocyanurate obtained or obtainable from the reaction of at least:
  • a first (meth)acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;
  • a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%.
  • the polyisocyanate composition (a) comprises one or more polyisocyanate(s).
  • Polyisocyanates include all aliphatic, cycloaliphatic, and aromatic isocyanate known for the preparation of polyurethanes. They preferably have an average functionality of less than 2.5.
  • Examples are 2,2'-, 2,4'-, and 4,4'diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates and more highly polycyclic homologs of diphenylmethane diisocyanate (polymeric MDI), isophorone diisocyanate (IPDI) or its oligomers, 2,4- or 2,6-tolylene diisocyanate (TDI) or mixtures thereof, tetramethylene diisocyanate or its oligomers, hexamethylene diisocyanate (HDI) or its oligomers, naphthylene diisocyanate (NDI), or mixtures thereof.
  • polymeric MDI polymeric MDI
  • IPDI isophorone diisocyanate
  • TDI 2,4- or 2,6-tolylene diisocyanate
  • HDI hexamethylene diisocyanate
  • NDI naphthylene diisocyanate
  • polyisocyanates in the polyisocyanate composition (a) is given to monomeric diphenylmethane diisocyanate, as for example 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, or mixtures thereof.
  • Diphenylmethane diisocyanate may also be used here as a mixture with its derivatives.
  • diphenylmethane diisocyanate may more preferably comprise up to 10 weight-%, more preferably still up to 5 weight-%, of carbodiimide, uretdione-, or uretonimine-modified diphenylmethane diisocyanate, especially carbodiimide modified diphenylmethane diisocyanate.
  • Polyisocyanates in the polyisocyanate composition (a) may also be used in the form of polyisocyanate prepolymers. These polymers are obtainable (a-1 )) in excess, at temperatures for example of 30 to 100 °C, preferably at about 80 °C, with polyols (a-2), to give the prepolymer.
  • the NCO content of polyisocyanate prepolymers of the invention is preferably from 5 to 32 weight-% NCO, more preferably from 15 to 28 weight-% NCO.
  • Polyols (a-2) are known to the skilled person and are described for example in "Kunststoffhandbuch, 7, Polyurethane", Carl Hanser-Verlag, 3rd edition 1993, section 3.1 .
  • polyether- or polyesterols such as the polyols described below for the polyol composition (b).
  • polyols (a-2) preferably possess a functionality of 2 to 6, more preferably of 2 to 4, and more particularly 2 to 3.
  • polyols (a-2) comprise polyesterols based on hydrophobic substances.
  • the hydrophobic substances are water-insoluble substances which contain an apolar organic radical and also possess at least one reactive group selected from hydroxyl, carboxylic acid, carboxylic ester or mixtures thereof.
  • the equivalent weight of the hydrophobic substances is preferably between 130 and 1000 g/mol.
  • Use may be made, for example, of fatty acids, such as stearic acid, oleic acid, palmitic acid, lauric acid or linoleic acid, and also fats and oils, such as castor oil, corn oil, sunflower oil, soybean oil, coconut oil, olive oil or tall oil, for example.
  • fatty acids such as stearic acid, oleic acid, palmitic acid, lauric acid or linoleic acid
  • fats and oils such as castor oil, corn oil, sunflower oil, soybean oil, coconut oil, olive oil or tall oil, for example.
  • the fraction of the hydrophobic substances as a proportion of the total monomer content of the polyester alcohol is preferably 1 to 30 mol%, more preferably 4 to 15 mol%.
  • the polyesterols used preferably have a functionality of 1 .5 to 5, more preferably 1.8 - 3.5.
  • the polyol used may also comprise a hydroxyl-functionalized hydrophobic compound, such as a hydroxy-functionalized compound from fat chemistry.
  • hydroxyl-functional compounds from fat chemistry there are a series of hydroxyl-functional compounds from fat chemistry that are known and can be used. Examples are castor oil, hydroxyl-modified oils such as grape seed oil, black cumin oil, pumpkin seed oil, borage seed oil, soybean oil, wheatgerm oil, rapeseed oil, sunflower oil, peanut oil, apricot kernel oil, pistachio kernel oil, almond oil, olive oil, macadamia nut oil, avocado oil, sea buckthorn oil, sesame oil, hazelnut oil, evening primrose oil, wild rose oil, hemp oil, thistle oil, walnut oil, hydroxyl-modified fatty acid esters based on myristoleic acid, palmitoleic acid, oleic acid, vaccinic acid, petroselinic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, stearidonic acid, arachidonic acid, timno
  • a further group of fatty-chemical polyols used with preference may be obtained through ring opening of epoxidized fatty acid esters with simultaneous reaction with alcohols and, optionally, subsequent further transesterification reactions.
  • the incorporation of hydroxyl groups into oils and fats is accomplished primarily by epoxidation of the olefinic double bond present in these products, followed by the reaction of the resultant epoxide groups with a mono- or polyhydric alcohol. This produces, from the epoxide ring, a hydroxyl group or, in the case of polyfunctional alcohols, a structure having a higher number of OH groups.
  • oils and fats are usually glycerol esters, parallel transesterification reactions run additionally during the reactions specified above.
  • the compounds obtained accordingly preferably have a molecular weight in the range between 500 and 1500 g/mol. Products of this kind are available, for example, from BASF under the Sovermole ® product name.
  • chain extenders (a-3) are added to the reaction to give the polyisocyanate prepolymer.
  • Chain extenders (a-3) suitable for the prepolymer are dihydric or trihydric alcohols, as for example dipropylene glycol and/or tripropylene glycol, or the adducts of dipropylene glycol and/or tripropylene glycol with alkylene oxides, preferably dipropylene glycol.
  • Suitable chain extenders are extenders that are known in the context of polyurethane production.
  • Examples of those content rates will include aliphatic, cycloaliphatic and/or araliphatic or aromatic diols having 2 to 14, preferably 2 to 10 carbon atoms, such as ethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,6-hexanediol, 1 ,10-decanediol and bis(2-hydroxyethyl) hydroquinone, 1 ,2-, 1 ,3-, 1 ,4-dihydroxycyclohexane, diethylene glycol, dipropylene glycol, tripropylene glycol, triols, such as 1 ,2,4-, 1 ,3,5-trihydroxycyclohexane, glycerol and trimethylolpropane, and hydroxyl-containing polyalkylene oxides of low molecular weight that are based on ethylene oxide and/or on 1 ,2-propylene oxide and on the aforementioned diol
  • low molecular weight chain extenders and/or crosslinking agents are specified for example in "Kunststoflhandbuch, volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, sections 3.2 and 3.3.2.
  • Suitable polyisocyanate prepolymers are described for example in US 3,883,571 B, WO 02/10250 A1 , and US 4,229,347 B.
  • polyisocyanate in the polyisocyanate composition (a) is diphenylmethane diisocyanate or a polyisocyanate prepolymer based on monomeric 4,4'-diphenylmethane diisocyanate or mixtures of 4,4'-diphenylmethane diisocyanate with its derivatives and polypropylene oxide having a functionality of 2 to 4, and also, optionally, dipropylene glycol or monomeric.
  • the polyol composition comprises one or more polyol(s).
  • Commonly used for the polyol composition (b) are polyetherols and/or polyesterols having 2 to 8 isocyanate-reactive hydrogen atoms.
  • the OH number of these compounds is in the range from 30 to 850 mg KOH/g, preferably in the region of 50 and 600 mg KOH/g.
  • the polyetherols are obtained by known methods, as for example by anionic polymerization of alkylene oxides with addition of at least one starter molecule that contains 2 to 8, preferably 2 to 6, and more preferably 2 to 4 reactive hydrogen atoms in bonded form, in the presence of catalysts.
  • Catalysts used may be alkali metal hydroxides, such as sodium or potassium hydroxide, or alkali metal alkoxides, such as sodium methoxide, sodium or potassium ethoxide or potassium isopropoxide, or, in the case of cationic polymerization, Lewis acids, such as antimony pentachloride, boron trifluoride etherate or bleaching may be used as catalysts.
  • Lewis acids such as antimony pentachloride, boron trifluoride etherate or bleaching
  • catalysts it is possible additionally to use double metal cyanide compounds as well, referred to as DMC catalysts.
  • the catalyst used may also be a tertiary amine, such as imidazole, for example.
  • alkylene oxides preference is given to using one or more compounds having 2 to 4 carbon atoms in the alkylene radical, such as tetrahydrofuran, 1 ,2-propylene oxide, or 1 ,2- and/or 2,3-butylene oxide, in each case alone or in the form of mixtures, and preferably 1 ,2-propylene oxide, 1 ,2-butylene oxide and/or 2,3-butylene oxide, more particularly 1 ,2-propylene oxide.
  • alkylene oxides preference is given to using one or more compounds having 2 to 4 carbon atoms in the alkylene radical, such as tetrahydrofuran, 1 ,2-propylene oxide, or 1 ,2- and/or 2,3-butylene oxide, in each case alone or in the form of mixtures, and preferably 1 ,2-propylene oxide, 1 ,2-butylene oxide and/or 2,3-butylene oxide, more particularly 1 ,2-propylene oxide.
  • starter molecules contemplated include ethylene glycol, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol, sugar derivatives, such as sucrose, hexitol derivatives, such as sorbitol, methylamine, ethylarnine, isopropylamine, butylamine, benzylamine, aniline, toluidine, toluenediamine, naphthylamine, ethylenediamine, diethylenetrianl ine, 4,4'-methylenedianiline, 1 ,3-propanediamine, 1 ,6-hexanediamine, ethanolamine, diethanolamine, triethanolamine, and also other di- or polyhydric alcohols or mono- or polyfunctional amines.
  • the polyester alcohols used are prepared usually by condensation of polyfunctional alcohols having 1 to 12 carbon atoms, such as ethylene glycol, diethylene glycol, butanediol, trimethylolpropane, glycerol or pentaerythritol, with polyfunctional carboxylic acids having 2 to 12 carbon atoms examples being succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, furnaric acid, phthalic acid, isophthalic acid, terephthalic acid, and the isomers of naphthalinedicarboxylic acids, or the anhydrides thereof.
  • polyfunctional alcohols having 1 to 12 carbon atoms such as ethylene glycol, diethylene glycol, butanediol, trimethylolpropane, glycerol or pentaerythritol
  • polyfunctional carboxylic acids having 2 to 12 carbon atoms
  • hydrophobic substances are water-insoluble substances which comprise an apolar organic radical and also possess at least one reactive group, selected from hydroxyl, carboxylic acid, carboxylic ester or mixtures thereof.
  • the equivalent weight of the hydrophobic materials is preferably between 130 and 1000 g/mol.
  • Use may be made, for example, of fatty acids, such as stearic acid, oleic acid, palmitic acid, !auric acid or linoleic acid, and also fats and oils, such as, for example, castor oil, corn oil, sunflower oil, soybean oil, coconut oil, olive oil or tall oil, for example.
  • polyesters comprise hydrophobic substances
  • the fraction of the hydrophobic substances among the total monomer content of the polyester alcohol is preferably 1 to 30 mol%, more preferably 4 to 15 mol%.
  • the polyesterols used preferably have a functionality of 1 .5 to 5, more preferably 1.8-3.5.
  • the polyol used may also comprise a hydroxyl-functionalized hydrophobic compound, such as a hydroxyl-functionalized compound from fat chemistry. A series of hydroxyl-functional compounds from fat chemistry are known that can be used.
  • Examples are castor oil, hydroxyl-modified oils such as grape seed oil, black coumene oil, pumpkin seed oil, borage seed oil, soybean oil, wheat genn oil, rapeseed oil, sunflower oil, peanut oil, apricot kernel oil, pistachio kernel oil, almond oil, olive oil, macadamia nut oil, avocado oil, sea buckthorn oil, sesame oil, hazelnut oil, evening primrose oil, wild rose oil, hemp oil, thistle oil, walnut oil, hydroxyl-modified fatty acid esters based on myristoleic acid palmitoleic acid, oleic acid, vaccenic acid, petroselinic acid, gadoleic acid, emcic acid, nervonic acid, linoleic acid, linolenic acid, stearidonic acid, arachidonic acid, timnodonic acid, clupanodonic acid, cervonic acid.
  • castor oil hydroxyl-modified oils such
  • Latter compmmds are sold for example by Bayer AG under the Desmophen® 1 150 designation.
  • a further group of fatty-chemical polyols used with preference may be obtained through ring opening of epoxidized fatty acid esters with simultaneous reaction of alcohols and, optionally, further transesterification reactions subsequently.
  • the incorporation of hydroxyl groups into oils and fats is accomplished primarily by epoxidation of the olefinic double bond present in these products, followed by the reaction of resultant epoxide groups with the mono- or polyhydric alcohol.
  • oils and fats are usually glycerol esters, parallel transesterification reactions additionally during the reactions stated above.
  • the compounds thus obtained preferably have a molecular weight in the range from between 500 and 1500 g/mol. Products of this kind are available for example from BASF under the product designation Sovemole®.
  • One particularly preferred embodiment of the invention uses castor oil as polyol, more preferably exclusively castor oil.
  • Polyetherol/polyesterol hybrid polyols as well, as described under WO 2013/127647 A1 and WO 2013/1 10512 A1 can be used as polyols.
  • the catalyst is obtained or obtainable by:
  • a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%;
  • LiCI-capsule an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell
  • the (meth)acrylic copolymer capsule shell of the catalyst is obtained or obtainable by reacting:
  • a first acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkyl polyol;
  • ii) 50 to 70 weight-%, preferably 65 to 55 weight-%, more preferred 62 to 58 weight-% of a second acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%.
  • the polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol of (i) is preferably a polyester of (meth)acrylic acid with a C2 to C10 alkylpolyol, more preferably selected from the group consisting of polyesters of (meth)acrylic acid with a C4 to C5 alkylpolyol, wherein the alkylpolyol has 2 to four hydroxyl groups, preferably selected from the group consisting of 1 ,4-butandioldiacrylate, pentaerytritol-triacrylate, pentaerytritol-tetraacrylate and mixtures of two or more of these compounds.
  • the monoester of (meth)acrylic acid with a C1 to C24 alkanol of (ii) is preferably a monoester of (meth)acrylic acid with a C1 to C10 alkanol, more preferably selected from the group consisting of C1 to C5 alkylesters of (meth)acrylic and mixtures of two or more C1 to C5 alkylesters of (meth)acrylic, preferably from the group consisting of methyl(meth)acrylate, butylacrylate and mixtures of two or more of these compounds, more preferred from the group consisting of methylmethacrylate, butylacrylate and mixtures of methylmethacrylate and butylacrylate.
  • the aqueous and/or alcoholic solution of lithium chloride of the catalyst comprises 40 to 90 weight-% lithium chloride and 60 to 10 weight-% of a solvent selected from the group consisting of water, C1 to C10 alkyl monools, C1 to C10 alkyl polyols and mixtures of two or more of these solvents, preferably from the group consisting of water, methanol, ethanol, 1 ,2-propylene glycol and mixtures of two or more of these solvents, preferably at least 1 ,2-propylene glycol, wherein the weight-% are based on the overall weight of the aqueous and/or alcoholic solution of lithium chloride.
  • the core/shell ratio of the LiCI-capsule is in the range of from 99/1 to 70/30, preferably in the range of from 98/2 to 75/25, more preferred in the range of from 95/5 to 80/20.
  • the definition of the term“core/shell ratio” as disclosed in the section above related to the catalyst applies also here.
  • the hydrophobic diluent of (I) has a solubility in water of ⁇ 0.5 g/liter at 20 °C and at normal pressure and is preferably selected from the group consisting of cyclohexane, glycerol ester oils, hydrocarbon oils, such as paraffin oil, diisopropylnaphthalene, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in hydrocarbon oils, animal oil, vegetable oils or mineral oils, the distillation start-point of which under atmospheric pressure is 250°C and the distillation end-point of which is 410 °C, such as e.g.
  • esters of saturated or unsaturated fatty acids such as alkyl myristate, e.g. isopropyl myristate, butyl myristate or cetyl myristate, hexadecyl stearate, ethyl palmitate, isopropyl palmitate or cetyl ricinoleate, silicone oils, such as dimethylpolysiloxane, methylphenylpolysiloxan, or silicone glycol copolymer, fatty acids and fatty alcohols or waxes such as carnauba wax, candellila wax, bees wax, microcrystalline wax, ozokerite wax, Ca, Mg and Al oleates, Ca, Mg and Al myristates, Ca, Mg and Al linoleates and Ca, Mg and Al stearate; preferably at least diisopropylnaphthalene.
  • alkyl myristate e.g. isopropyl myristate, but
  • the amount of lithium ions in the catalyst per urethane group in the a polyisocyanate composition (a) is in the range of from 0.0001 to 3.5, preferably 0.01 to 1.0, more preferably 0.05 to 0.9, and more preferably 0.1 to 0.8, based in each case on the number of lithium ions and urethane groups (per equivalent of urethane groups).
  • epoxide composition comprising a compound having one or more epoxide groups is used in an amount such that the equivalent ratio of epoxide group to isocyanate group of the polyisocyanate composition (a) is in the range of from 0.1 to 2.0, preferably 0.2 to 1.8, and more preferably 0.3 to 1 .0.
  • the amount of lithium ions in the catalyst per epoxy group of the epoxy composition is greater than 0.00001 , preferably in the range of from 0.00005 to 0.3, based in each case on the number of lithium ions and epoxy groups.
  • the invention further relates to a process for the preparation of a polyurethane or polyisocyanurate, wherein at least
  • a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol; wherein the weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%;
  • reaction of at least a), b) and c) in the presence of the catalyst is carried out at a temperature below 100 °C, preferably at a temperature below 90 °C, more preferably below 80°C, more preferably below 75 °C, thereby obtaining the polyurethane or polyisocyanurate.
  • the catalyst is obtained or obtainable by:
  • a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%;
  • LiCI-capsule an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell
  • the (meth)acrylate momonomers comprise:
  • a first acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;
  • ii) 50 to 70 weight-%, preferably 65 to 55 weight-%, more preferred 62 to 58 weight-% of a second acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%.
  • the polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol of (i) is preferably a polyester of (meth)acrylic acid with a C2 to C10 alkylpolyol, more preferably selected from the group consisting of polyesters of (meth)acrylic acid with a C4 to C5 alkylpolyol, wherein the alkylpolyol has 2 to four hydroxyl groups, preferably selected from the group consisting of 1 ,4-butandioldiacrylate, pentaerytritol-triacrylate, pentaerytritol-tetraacrylate and mixtures of two or more of these compounds.
  • the monoester of (meth)acrylic acid with a C1 to C24 alkanol of (ii) is preferably a monoester of (meth)acrylic acid with a C1 to C10 alkanol, more preferably selected from the group consisting of C1 to C5 alkylesters of (meth)acrylic and mixtures of two or more C1 to C5 alkylesters of (meth)acrylic, preferably from the group consisting of methyl(meth)acrylate, butylacrylate and mixtures of two or more of these compounds, more preferred from the group consisting of methylmethacrylate, butylacrylate and mixtures of methylmethacrylate and butylacrylate.
  • the aqueous and/or alcoholic solution of lithium chloride comprises 40 to 90 weight-% lithium chloride and 60 to 10 weight-% of a solvent selected from the group consisting of water, C1 to C10 alkyl monools, C1 to C10 alkyl polyols and mixtures of two or more of these solvents, preferably from the group consisting of water, methanol, ethanol, 1 ,2-propylene glycol and mixtures of two or more of these solvents, preferably at least 1 ,2-propylene glycol, wherein the weight-% are based on the overall weight of the aqueous and/or alcoholic solution of lithium chloride.
  • the core/shell ratio of the LiCI-Capsule is in the range of from 99/1 to 70/30, preferably in the range of from 98/2 to 75/25, more preferred in the range of from 95/5 to 80/20.
  • the definition of the term“core/shell ratio” as given in the section related to the catalyst above applies.
  • the hydrophobic diluent of (I) has a solubility in water of ⁇ 0.5 g/liter at 20 °C and at normal pressure and is preferably selected from the group consisting of cyclohexane, glycerol ester oils, hydrocarbon oils, such as paraffin oil, diisopropylnaphthalene, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in hydrocarbon oils, animal oil, vegetable oils or mineral oils, the distillation start-point of which under atmospheric pressure is 250°C and the distillation end-point of which is 410 °C, such as e.g.
  • esters of saturated or unsaturated fatty acids such as alkyl myristate, e.g. isopropyl myristate, butyl myristate or cetyl myristate, hexadecyl stearate, ethyl palmitate, isopropyl palmitate or cetyl ricinoleate, silicone oils, such as dimethylpolysiloxane, methylphenylpolysiloxan, or silicone glycol copolymer, fatty acids and fatty alcohols or waxes such as carnauba wax, candellila wax, bees wax, microcrystalline wax, ozokerite wax, Ca, Mg and Al oleates, Ca, Mg and Al myristates, Ca, Mg and Al linoleates and Ca, Mg and Al stearate; preferably at least diisopropylnaphthalene.
  • alkyl myristate e.g. isopropyl myristate, but
  • the polyisocyanate composition (a) comprises
  • the catalyst comprising an aqueous and/or alcoholic solution of lithium chloride encapsulated in an acrylic copolymer capsule shell;
  • the polyol composition (b) comprises
  • the amount of lithium ions in the catalyst per urethane group in the polyisocyanate composition (a) is in the range of from 0.0001 to 3.5, preferably from 0.01 to 1.0, more preferably from 0.05 to 0.9, and more preferably from 0.1 to 0.8, based in each case on the number of lithium ions and urethane groups (per equivalent of urethane groups).
  • the epoxide composition comprising a compound having one or more epoxide groups is used in an amount such that the equivalent ratio of epoxide group to isocyanate group of the polyisocyanate composition (a) is in the range of from 0.1 to 2.0, preferably from 0.2 to 1.8, and more preferably from 0.3 to 1.0.
  • the amount of lithium ions in the catalyst per epoxy group of the epoxy composition is greater than 0.00001 , preferably is in the range of from 0.00005 to 0.3, based in each case on the number of lithium ions and epoxy groups.
  • a catalyst useful for polyurethane or polyisocyanurate synthesis comprising an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell, wherein the (meth)acrylic copolymer capsule shell is obtained or obtainable by reacting:
  • a first (meth)acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;
  • a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%.
  • a first acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C10 alkylpolyol;
  • ii) 50 to 70 weight-%, preferably 65 to 55 weight-%, more preferred 62 to 58 weight-% of a second acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C10 alkanol;
  • the weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%.
  • the polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol of (i) is preferably a polyester of (meth)acrylic acid with a C2 to C10 alkylpolyol, more preferably selected from the group consisting of polyesters of (meth)acrylic acid with a C4 to C5 alkylpolyol, wherein the alkylpolyol has 2 to four hydroxyl groups, preferably selected from the group consisting of 1 ,4-butandioldiacrylate, pentaerytritol-triacrylate, pentaerytritol-tetraacrylate and mixtures of two or more of these compounds.
  • the monoester of (meth)acrylic acid with a C1 to C24 alkanol of (ii) is preferably a monoester of (meth)acrylic acid with a C1 to C10 alkanol, more preferably selected from the group consisting of C1 to C5 alkylesters of (meth)acrylic acid and mixtures of two or more C1 to C5 alkylesters of (meth)acrylic acid, preferably from the group consisting of methyl(meth)acrylate, butylacrylate and mixtures of two or more of these compounds, more preferred from the group consisting of methylmethacrylate, butylacrylate and mixtures of methylmethacrylate and butylacrylate.
  • a first (meth)acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;
  • a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%;
  • the aqueous and/or alcoholic solution of lithium chloride comprises 40 to 90 weight-% lithium chloride and 60 to 10 weight-% of a solvent selected from the group consisting of water, C1 to C10 alkyl monools, C1 to C10 alkyl polyols and mixtures of two or more of these solvents, preferably from the group consisting of water, methanol, ethanol, 1 ,2-propylene glycol and mixtures of two or more of these solvents, preferably at least 1 ,2-propylene glycol, wherein the weight-% are based on the overall weight of the aqueous and/or alcoholic solution of lithium chloride.
  • a solvent selected from the group consisting of water, C1 to C10 alkyl monools, C1 to C10 alkyl polyols and mixtures of two or more of these solvents, preferably from the group consisting of water, methanol, ethanol, 1 ,2-propylene glycol and mixtures of two or more of these solvents,
  • hydrophobic diluent of (I) has a solubility in water of ⁇ 0.5 g/liter at 20 °C and at normal pressure and is preferably selected from the group consisting of cyclohexane, glycerol ester oils, hydrocarbon oils, such as paraffin oil, diisopropylnaphthalene, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in hydrocarbon oils, animal oil, vegetable oils or mineral oils, the distillation start-point of which under atmospheric pressure is 250°C and the distillation end-point of which is 410 °C, such as e.g.
  • esters of saturated or unsaturated fatty acids such as alkyl myristate, e.g. isopropyl myristate, butyl myristate or cetyl myristate, hexadecyl stearate, ethyl palmitate, isopropyl palmitate or cetyl ricinoleate, silicone oils, such as dimethylpolysiloxane, methylphenylpolysiloxan, or silicone glycol copolymer, fatty acids and fatty alcohols or waxes such as carnauba wax, candellila wax, bees wax, microcrystalline wax, ozokerite wax, Ca, Mg and Al oleates, Ca, Mg and Al myristates, Ca, Mg and Al linoleates and Ca, Mg and Al stearate; preferably at least diisopropylnaphthalene.
  • alkyl myristate e.g. isopropyl myristate, but
  • a catalytic composition comprising a catalyst according to any of embodiments 1 to 8 and an epoxide composition.
  • a first (meth)acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;
  • a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%;
  • a first acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;
  • ii) 50 to 70 weight-%, preferably 65 to 55 weight-%, more preferred 62 to 58 weight-% of a second acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%.
  • polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol is preferably a polyester of (meth)acrylic acid with a C2 to C10 alkylpolyol, more preferably selected from the group consisting of polyesters of (meth)acrylic acid with a C4 to C5 alkylpolyol, wherein the alkylpolyol has 2 to four hydroxyl groups, preferably selected from the group consisting of 1 ,4-butandioldiacrylate, pentaerytritol-triacrylate, pentaerytritol-tetraacrylate and mixtures of two or more of these compounds.
  • the monoester of (meth)acrylic acid with a C1 to C24 alkanol is preferably a monoester of (meth)acrylic acid with a C1 to C10 alkanol, more preferably selected from the group consisting of C1 to C5 alkylesters of (meth)acrylic and mixtures of two or more C1 to C5 alkylesters of (meth)acrylic, preferably from the group consisting of methyl(meth)acrylate, butylacrylate and mixtures of two or more of these compounds, more preferred from the group consisting of methylmethacrylate, butylacrylate and mixtures of methylmethacrylate and butylacrylate.
  • the aqueous and/or alcoholic solution of lithium chloride comprises 40 to 90 weight-% lithium chloride and 60 to 10 weight-% of a solvent selected from the group consisting of water, C1 to C10 alkyl monools, C1 to C10 alkyl polyols and mixtures of two or more of these solvents, preferably from the group consisting of water, methanol, ethanol, 1 ,2-propylene glycol and mixtures of two or more of these solvents, preferably at least 1 ,2-propylene glycol, wherein the weight-% are based on the overall weight of the aqueous and/or alcoholic solution of lithium chloride.
  • a solvent selected from the group consisting of water, C1 to C10 alkyl monools, C1 to C10 alkyl polyols and mixtures of two or more of these solvents, preferably from the group consisting of water, methanol, ethanol, 1 ,2-propylene glycol and mixtures of two or more of these solvents,
  • hydrophobic diluent of (I) has a solubility in water of ⁇ 0.5 g/liter at 20 °C and at normal pressure and is preferably selected from the group consisting of cyclohexane, glycerol ester oils, hydrocarbon oils, such as paraffin oil, diisopropylnaphthalene, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in hydrocarbon oils, animal oil, vegetable oils or mineral oils, the distillation start-point of which under atmospheric pressure is 250°C and the distillation end-point of which is 410 °C, such as e.g.
  • esters of saturated or unsaturated fatty acids such as alkyl myristate, e.g. isopropyl myristate, butyl myristate or cetyl myristate, hexadecyl stearate, ethyl palmitate, isopropyl palmitate or cetyl ricinoleate, silicone oils, such as dimethylpolysiloxane, methylphenylpolysiloxan, or silicone glycol copolymer, fatty acids and fatty alcohols or waxes such as carnauba wax, candellila wax, bees wax, microcrystalline wax, ozokerite wax, Ca, Mg and Al oleates, Ca, Mg and Al myristates, Ca, Mg and Al linoleates and Ca, Mg and Al stearate; preferably at least diisopropylnaphthalene.
  • alkyl myristate e.g. isopropyl myristate, but
  • Polyurethane or polyisocyanurate obtained or obtainable from the reaction of at least: a) a polyisocyanate composition;
  • a first (meth)acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;
  • a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%.
  • a first (meth)acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;
  • a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%;
  • ii) 50 to 70 weight-%, preferably 65 to 55 weight-%, more preferred 62 to 58 weight-% of a second acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%.
  • polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol of (i) is preferably a polyester of (meth)acrylic acid with a C2 to C10 alkylpolyol, more preferably selected from the group consisting of polyesters of (meth)acrylic acid with a C4 to C5 alkylpolyol, wherein the alkylpolyol has 2 to four hydroxyl groups, preferably selected from the group consisting of 1 ,4-butandioldiacrylate, pentaerytritol-triacrylate, pentaerytritol-tetraacrylate and mixtures of two or more of these compounds.
  • the aqueous and/or alcoholic solution of lithium chloride of the catalyst comprises 40 to 90 weight-% lithium chloride and 60 to 10 weight-% of a solvent selected from the group consisting of water, C1 to C10 alkyl monools, C1 to C10 alkyl polyols and mixtures of two or more of these solvents, preferably from the group consisting of water, methanol, ethanol, 1 ,2-propylene glycol and mixtures of two or more of these solvents, preferably at least 1 ,2-propylene glycol, wherein the weight-% are based on the overall weight of the aqueous and/or alcoholic solution of lithium chloride.
  • polyurethane or polyisocyanurate according to any of embodiments 20 to 25, wherein the core/shell ratio of the LiCI-capsule is in the range of from 99/1 to 70/30, preferably in the range of from 98/2 to 75/25, more preferred in the range of from 95/5 to 80/20.
  • hydrophobic diluent of (I) has a solubility in water of ⁇ 0.5 g/liter at 20 °C and at normal pressure and is preferably selected from the group consisting of cyclohexane, glycerol ester oils, hydrocarbon oils, such as paraffin oil, diisopropylnaphthalene, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in hydrocarbon oils, animal oil, vegetable oils or mineral oils, the distillation start-point of which under atmospheric pressure is 250°C and the distillation end-point of which is 410 °C, such as e.g.
  • esters of saturated or unsaturated fatty acids such as alkyl myristate, e.g. isopropyl myristate, butyl myristate or cetyl myristate, hexadecyl stearate, ethyl palmitate, isopropyl palmitate or cetyl ricinoleate, silicone oils, such as dimethylpolysiloxane, methylphenylpolysiloxan, or silicone glycol copolymer, fatty acids and fatty alcohols or waxes such as carnauba wax, candellila wax, bees wax, microcrystalline wax, ozokerite wax, Ca, Mg and Al oleates, Ca, Mg and Al myristates, Ca, Mg and Al linoleates and Ca, Mg and Al stearate; preferably at least diisopropylnaphthalene.
  • alkyl myristate e.g. isopropyl myristate, but
  • a first (meth)acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;
  • a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol; wherein the weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%;
  • reaction of at least a), b) and c) in the presence of the catalyst is carried out at a temperature below 100 °C, preferably at a temperature below 90 °C, more preferably below 80°C, more preferably below 75 °C, thereby obtaining the polyurethane or polyisocyanurate.
  • a temperature below 100 °C preferably at a temperature below 90 °C, more preferably below 80°C, more preferably below 75 °C, thereby obtaining the polyurethane or polyisocyanurate.
  • a first (meth)acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;
  • a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;
  • weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%;
  • a first acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;
  • ii) 50 to 70 weight-%, preferably 65 to 55 weight-%, more preferred 62 to 58 weight-% of a second acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol; wherein the weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%.
  • polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol of (i) is preferably a polyester of (meth)acrylic acid with a C2 to C10 alkylpolyol, more preferably selected from the group consisting of polyesters of (meth)acrylic acid with a C4 to C5 alkylpolyol, wherein the alkylpolyol has 2 to four hydroxyl groups, preferably selected from the group consisting of 1 ,4-butandioldiacrylate, pentaerytritol-triacrylate, pentaerytritol-tetraacrylate and mixtures of two or more of these compounds.
  • aqueous and/or alcoholic solution of lithium chloride comprises 40 to 90 weight-% lithium chloride and 60 to 10 weight-% of a solvent selected from the group consisting of water, C1 to C10 alkyl monools, C1 to C10 alkyl polyols and mixtures of two or more of these solvents, preferably from the group consisting of water, methanol, ethanol, 1 ,2-propylene glycol and mixtures of two or more of these solvents, preferably at least 1 ,2-propylene glycol, wherein the weight-% are based on the overall weight of the aqueous and/or alcoholic solution of lithium chloride.
  • hydrophobic diluent of (I) has a solubility in water of ⁇ 0.5 g/liter at 20 °C and at normal pressure and is preferably selected from the group consisting of cyclohexane, glycerol ester oils, hydrocarbon oils, such as paraffin oil, diisopropylnaphthalene, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in hydrocarbon oils, animal oil, vegetable oils or mineral oils, the distillation start-point of which under atmospheric pressure is 250°C and the distillation end-point of which is 410 °C, such as e.g.
  • esters of saturated or unsaturated fatty acids such as alkyl myristate, e.g. isopropyl myristate, butyl myristate or cetyl myristate, hexadecyl stearate, ethyl palmitate, isopropyl palmitate or cetyl ricinoleate, silicone oils, such as dimethylpolysiloxane, methylphenylpolysiloxan, or silicone glycol copolymer, fatty acids and fatty alcohols or waxes such as carnauba wax, candellila wax, bees wax, microcrystalline wax, ozokerite wax, Ca, Mg and Al oleates, Ca, Mg and Al myristates, Ca, Mg and Al linoleates and Ca, Mg and Al stearate; preferably at least diisopropylnaphthalene.
  • alkyl myristate e.g. isopropyl myristate, but
  • the catalyst comprising an aqueous and/or alcoholic solution of lithium chloride encapsulated in an acrylic copolymer capsule shell;
  • the present invention is further illustrated by the following reference examples, comparative examples, and examples.
  • the oil phase was introduced at room temperature (25 °C). Feed 1 and feed 2 were added to the oil phase and the mixture was dispersed with a high-speed dissolver stirrer at 26000 rpm for 3 minutes. The emulsion was then filled into the reaction vessel. Feed 3 and feed 4 were added and the emulsion was heated up to 30°C and then hold two hours at 30°C. Then feed 5 was added and the dispersion was hold 1 more hour at 30°C. After that the dispersion was cooled down to room temperature. This gave a dispersion with an average particle size (DO.5) of 48.2 m m (z-average determined by means of light scattering). The capsules dispersion was used directly in the subsequent application.
  • DO.5 average particle size
  • the particle size distribution of the microcapsules was measured using a Malvern Mastersizer 2000, Flydro 2000SM sample dispersion unit, with standard measurement methods, which are documented in the literature.
  • the specified value is the average value i.e. D(0,5).
  • the oil phase was introduced at room temperature. Feed 1 and feed 2 were added to the oil phase and the mixture was dispersed with a high-speed dissolver stirrer at 26000 rpm for 3 minutes. The emulsion was then filled into the reaction vessel. Feed 3 and feed 4 were added and the emulsion was heated up to 30°C and then hold two hours at 30°C. Then feed 5 was added and the dispersion was hold 1 more hour at 30°C. After that the dispersion was cooled down to room temperature. This gave a dispersion with an average particle size (DO.5) of 4.1 m m (z-average determined by means of light scattering). The capsules dispersion is used directly in the subsequent application.
  • DO.5 average particle size
  • the particle size distribution of the microcapsules was measured using a Malvern Mastersizer 2000, Hydro 2000SM sample dispersion unit, with standard measurement methods, which are documented in the literature.
  • the specified value is the average value i.e. D(0,5).
  • Feed 4 1.21 g AA (solution of 17,35 weight- % in water)
  • the oil phase was introduced at room temperature. Feed 1 and feed 2 were added to the oil phase and the mixture was dispersed with a high-speed dissolver stirrer at 26000 rpm for 3 minutes. The emulsion was then filled into the reaction vessel. Feed 3 and feed 4 were added and the emulsion was heated up to 30°C and then hold two hours at 30 °C. Then feed 5 was added and the dispersion was hold 1 more hour at 30 °C. After that the dispersion was cooled down to room temperature. This gave a dispersion with an average particle size (DO.5) of 6.1 m m (z-average determined by means of light scattering). The capsules dispersion is used directly in the subsequent application.
  • DO.5 average particle size
  • the particle size distribution of the microcapsules was measured using a Malvern Mastersizer 2000, Flydro 2000SM sample dispersion unit, with standard measurement methods, which are documented in the literature.
  • the specified value is the average value i.e. D(0,5).
  • the particle size distribution of the microcapsules was measured using a Malvern Mastersizer 2000, Flydro 2000SM sample dispersion unit, with standard measurement methods, which are documented in the literature.
  • the specified value is the average value i.e. D(0,5).
  • the oil phase was introduced at room temperature.
  • Feed 1 and feed 2 were added to the oil phase and the mixture was dispersed with a high-speed dissolver stirrer at 26000 rpm for 3 minutes.
  • the emulsion was then filled into the reaction vessel.
  • Feed 3 and feed 4 were added and the emulsion was heated up to 30°C and then hold two hours at 30°C.
  • feed 5 was added and the dispersion was hold 1 more hour at 30°C. After that the dispersion was cooled down to room temperature. This gave a dispersion with an average particle size (DO.5) of 4.7 m m (z-average determined by means of light scattering).
  • DO.5 average particle size
  • the capsules dispersion is used directly in the subsequent application.
  • the particle size distribution of the microcapsules was measured using a Malvern Mastersizer 2000, Hydro 2000SM sample dispersion unit, with standard measurement methods, which are documented in the literature.
  • the specified value is the average value i.e. D(
  • Table 1 shows the compositions of the capsules of catalysts 5, 6 and catalysts 7, 8 and 9 and the resulting core/wall ratio of the capsules, as well as the catalysts’ numbering.
  • the core/shell ratio is thus dimensionless. 8.
  • a polyol component and an isocyanate component respectively were prepared by mixing the specified components.
  • the quantity figures are in parts by weight, based in each case on the polyol component (A component) or the isocyanate component (B component).
  • the respective polyol and isocyanate components were subsequently mixed at the specified mixing ratio with a speed mixer and the reactivity was tested at room temperature and 70 °C.
  • the open time at room temperature is defined as the time within which the viscosity of PU mixture at RT increases to an extent such that the stirring force required exceeds the given stirring force of the Shyodu gel timer, type 100, version 2012.
  • RT room temperature
  • a 200 g portion of the sample was prepared, mixed in a Speedmixer at 1950 rpm for 1 minute, and 130 g of the sample were stirred at room temperature in a polypropylene plastic beaker with a diameter of 7 cm, using a Shyodu gel timer, type 100, version 2012 and an associated wire stirrer at 20 rpm, until the viscosity and hence the required stirring force exceeded the stirring force of the gel timer.
  • the open times measured are summarized below in Table 3. 10.
  • the curing was carried out on a steel hot plate heated to 70 °C with a metal ring (diameter 7 cm).
  • a 50 g total portion of the sample was prepared, mixed in a Speedmixer at 1950 rpm for 1 minute, and 8 ml of the stirred sample are injected into the ring on the 70 °C heated hot plate with a syringe.
  • the starting time was reached when the mixed sample starts solidifying at the outer ring and the full cure time is reached when all material is solid.
  • Table 3 The results are summarized below in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un catalyseur utile pour la synthèse de polyuréthane ou de polyisocyanurate comprenant une solution aqueuse et/ou alcoolique de chlorure de lithium encapsulée dans une enveloppe de capsule de copolymère (méth)acrylique, l'enveloppe de capsule de copolymère (meth)acrylique étant obtenue ou pouvant être obtenue par réaction : i) de 10 à 90 % en poids d'une première composition de (méth)acrylate comprenant un polyester d'acide (meth)acrylique avec un alkylpolyol en C2 à C24 ; ii) de 90 à 10 % en poids d'une seconde composition de (méth)acrylate comprenant un monoester d'acide (meth)acrylique avec un alcanol en C1 à C24 ; les pourcentages en poids étant basés sur un poids total de tous les (méth)acrylates de 100 % en poids. Dans d'autres aspects, l'invention concerne une composition catalytique comprenant le catalyseur et une composition d'époxyde ; un procédé de préparation d'une solution aqueuse et/ou alcoolique de chlorure de lithium encapsulée dans une enveloppe de capsule de copolymère (meth)acrylique, ainsi qu'une solution aqueuse et/ou alcoolique de chlorure de lithium encapsulée dans une enveloppe de capsule de copolymère acrylique obtenue ou pouvant être obtenue par le procédé, ainsi que l'utilisation du catalyseur ou de la solution aqueuse et/ou alcoolique de chlorure de lithium encapsulée dans une enveloppe de capsule de copolymère acrylique obtenue ou pouvant être obtenue par le procédé de préparation de polyuréthane ou de polyisocyanurate. L'invention concerne également un polyuréthane ou un polyisocyanurate obtenu ou pouvant être obtenu par la réaction d'au moins : a) une composition de polyisocyanate ; b) une composition de polyol ; en présence d'une composition d'époxyde et d'un catalyseur comprenant une solution aqueuse et/ou alcoolique de chlorure de lithium encapsulée dans une enveloppe de capsule de copolymère (méth)acrylique, l'enveloppe de capsule de copolymère (méth)acrylique étant obtenue ou pouvant être obtenue par réaction : i) de 10 à 90 % en poids d'une première composition de (méth)acrylate comprenant un polyester d'acide (méth)acrylique avec un alkylpolyol en C2 à C24 ; ii) de 90 à 10 % en poids d'un second (méth)acrylate comprenant un monoester d'acide (méth)acrylique avec un alcanol en C1 à C24 ; les pourcentages en poids étant basés sur un poids total de tous les (méth)acrylates de 100 % en poids. L'invention concerne en outre un procédé de préparation dudit catalyseur.
PCT/EP2020/053414 2019-02-11 2020-02-11 Capsule de copolymère acrylique conçue pour s'ouvrir à moins 90 de °c pour une libération contrôlée de catalyseur pu/pir de formation in situ WO2020165135A1 (fr)

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