WO2020165135A1

WO2020165135A1 - Acrylic copolymer capsule designed to open up at < 90°c for controlled release of in-situ forming pu/pir catalyst

Info

Publication number: WO2020165135A1
Application number: PCT/EP2020/053414
Authority: WO
Inventors: Julia LIESE; Li Zhang; Roland Hinrich STAFF; Antoine Maxime Charles Joseph BEZIAU
Original assignee: Basf Se
Priority date: 2019-02-11
Filing date: 2020-02-11
Publication date: 2020-08-20

Abstract

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-%. In further aspects, the invention relates to a catalytic composition comprising the catalyst and an epoxide composition; 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-%. Furthermore, the invention relates to a process for the preparation of the polyurethane or polyisocyanurate.

Description

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-%. Furthermore, the invention relates to a process for the preparation of the polyurethane or polyisocyanurate.

Attempts have already been made to encapsulate polyaddition catalysts, thereby delaying the release of the catalysts, with rapid through-curing taking place only when the catalyst is released. Through the nature of the capsules in terms of size, type and thickness of walls, etc., it is possible to define and optimize the time prior to release - that is, the open time.

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.

A.-C. Bijlard et al. (A.-C. Bijlard, A. Hansen, I. Lieberwirth, K. Landfester, A. Taden, Adv. Mater. 2016, Vol. 28, 30, pages 6372-6377) describes the production of 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. When 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. In this case, 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. However, 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.

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. However, 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.

Therefore, it was an object of the present invention to provide a catalyst useful for polyurethane or polyisocyanurate synthesis, which can be activated at temperatures < 90 °C and which provides a convenient open time at room temperature (RT, 25 °C).

According to the present invention, 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:

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 term“(meth)acrylic acid” comprises meth acrylic acid and acrylic acid; the same applies to the term“(meth)acrylate”, which comprises methacrylate and acrylate.

Surprisingly, it could be shown that 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.

According to one embodiment of the catalyst, the (meth)acrylic copolymer capsule shell is obtained or obtainable by reacting:

i) 30 to 50 weight-%, preferably 35 to 45 weight-%, more preferred 38 to 42 weight-%, of 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;

According to one embodiment of the catalyst, 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. According to one embodiment of the catalyst, 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.

In a preferred embodiment, 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). Preferably, the weight-ratio PETIA to nBA is in the range of from 0.5 to 0.7, more preferably 0.6.

According to one embodiment, the catalyst is obtained or obtainable by:

I) providing an oil phase comprising a hydrophobic diluent having a solubility in water of <1 g/liter at 20 °C and at normal pressure (1013 mbar);

II) adding (meth)acrylate monomers and an aqueous and/or alcoholic solution of lithium chloride to the oil phase provided in (I), wherein the (meth)acrylate momonomers comprise:

wherein the weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%;

III) dispersing the (meth)acrylate monomers and the aqueous and/or alcoholic solution of lithium chloride in the oil phase and reacting the (meth)acrylate monomers,

thereby obtaining an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell (LiCI-capsule).

According to one embodiment of the catalyst, 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.

According to one embodiment of the catalyst, 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.

Core/shell ratio: The core ratio“Core” is defined as the weight ratio between the materials present in the core over the total weight of materials present in the core plus the shell (core + shell = 100 weight-%). “Core” is indicated in weight-%.The shell ratio“Shell” is defined as the weight ratio between the materials present in the shell over the total weight of materials present in the core plus the shell (core + shell = 100 weight-%). “Shell” is indicated in weight-%. The core/shell ratio is thus dimensionless.

According to one embodiment of the catalyst, 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. vaseline oil, 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.

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.

Catalytic composition

The invention also relates to a catalytic composition comprising a catalyst according to any of the embodiments described above and an epoxide composition.

According to one embodiment of the catalytic 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. Here it is also possible to use 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. Examples of such aliphatic polycarboxylic acids are oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and dimerized or trimerized linoleic acid. Further it is possible as well to use 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.

B) Polyglycidyl or poly([beta]-methylglycidyl) ethers, obtainable by reaction of a compound having at least two alcohol hydroxyl groups and/or phenolic hydroxyl groups with epichlorohydrin or [beta ]-methylepichlorohydrin under alkaline conditions or in the presence of an acidic catalyst and subsequent treatment with a base. 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

1.4-cyclohexanedimethanol, bis( 4-hydroxycyclohexyl)methane or 2,2-bis( 4-hydroxycyclohexyl) propane, or from alcohols which carry aromatic groups and/or other functional groups, such as N,N-bis(2-hydroxyethyl)aniline or p,p'-bis(2-hydroxyethylamino) diphenylmethane. 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. Further compounds which contain hydroxyl groups and which are suitable for preparing the glycidyl ethers are 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.

C) Poly(N-glycidyl) compounds, obtainable by dehydrochlorination of reaction products of epichlorohydrin with amines which contain at least two amine-bonded hydrogen atoms. Examples of such amines are aniline n-butylamine, bis(4-aminophenyl)methane, m-xylylenediamine or bis(4-methylaminophenyl)methane. 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

5.5-dimethylhydantoin.

D) 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.

E) 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. F) Monofunctional epoxy resins, such as (2-ethyl hexyl) glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether or cresyl glycidyl ether. Within the bounds of the invention it is likewise possible to use 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,

N-glycidyl-N’-(2-glycidyloxypropyl)-5,5-dimethylhydantoin and

2-glycidyloxy-1 ,3-bis(5,5-dimethyl-1 -glycidyl- hydantoin-3-yl)propane.

Particularly preferred as compounds containing epoxide groups are the compounds of classes (A) and (B), especially those of class (A).

Process for preparation of an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell

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:

II) adding (meth)acrylate monomers and an aqueous and/or alcoholic solution of lithium chloride to the oil phase provided in (I), wherein the (meth)acrylate momonomers comprise: i) 10 to 90 weight-% of a first (meth)acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;

According to one embodiment of the process for preparation of an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell, the (meth)acrylate momonomers comprise:

i) 30 to 50 weight-%, preferably 35 to 45 weight-%, more preferred 38 to 42 weight-%, of 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-%. According to one embodiment of the process for preparation of an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell, 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.

According to one embodiment of the process for preparation of an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell, 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.

According to one embodiment of the process for preparation of 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.

According to one embodiment of the process for preparation of an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell, 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.

According to one embodiment of the process for preparation of an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell, 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. vaseline oil, 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.

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.

Use of the catalyst

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.

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:

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. Preference as 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. In that case 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 . As polyols it is accordingly possible, for example, to use polyether- or polyesterols, such as the polyols described below for the polyol composition (b). As polyols (a-2), preference is given to using polyols containing secondary OH groups, such as polypropylene oxide, for example. These polyols (a-2) preferably possess a functionality of 2 to 6, more preferably of 2 to 4, and more particularly 2 to 3. With particular preference the 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. Where polyesters contain hydrophobic substances, 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.

In order to prepare particularly hydrophobic reaction mixtures, as for example when the condensative incorporation of water is to be prevented during the long open time, or when the polyurethane or polyisocyanurate compound of the invention is to be particularly stable towards hydrolysis, the polyol used may also comprise a hydroxyl-functionalized hydrophobic compound, such as a hydroxy-functionalized compound 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, timnodonic acid, clupanodonic acid, cervonic acid. Preference here is given to using castor oil and reaction products thereof with alkylene oxides or ketone-formaldehyde resins. Last-mentioned compounds are sold for example by Bayer AG under the name Desmophen^® 1 150.

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. Since 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.

It is additionally possible, optionally, for chain extenders (a-3) to be 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. These are preferably low molecular weight compounds having at least two isocyanate-reactive groups and used for molecular weights of less than 500 g/mol, more preferably of 60 to less than 400 g/mol, and more particularly 60 to less than 350 g/mol. 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 diols and/or triols as starter molecules. Further possible 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. Particularly preferred for use as 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. As catalysts it is possible additionally to use double metal cyanide compounds as well, referred to as DMC catalysts. For polyetherols with hydroxy numbers > 200 mg KOH/g, the catalyst used may also be a tertiary amine, such as imidazole, for example. Such polyols are described in WO 201 1/107367 A1 , for example. As 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. Examples of 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. As further starting materials in the preparation of the polyesters it is possible to use hydrophobic substances. The 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. Where 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. For the preparation of particularly hydrophobic reaction mixtures, as for example if the intention is to prevent water being condensed in during the long open time, or if the polyurethane of the invention is to be particularly stable toward hydrolysis, 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. Preference is given here to using castor oil and its products of reaction with alkylene oxides or ketoneformaldehyde resins. 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. 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. Since 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.

According to one embodiment of the polyurethane or polyisocyanurate, the catalyst is obtained or obtainable by:

ii) 50 to 70 weight-% of a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;

III) dispersing the (meth)acrylate monomers and the aqueous and/or alcoholic solution of lithium chloride in the oil phase and reacting the acrylate monomers,

According to one embodiment of the polyurethane or polyisocyanurate, the (meth)acrylic copolymer capsule shell of the catalyst is obtained or obtainable by reacting:

i) 30 to 50 weight-%, preferably 35 to 45 weight-%, more preferred 38 to 42 weight-%, of a first acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkyl polyol;

According to one embodiment of the polyurethane or polyisocyanurate, 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.

According to one embodiment of the polyurethane or polyisocyanurate, 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.

According to one embodiment of the polyurethane or polyisocyanurate, 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.

According to one embodiment of the polyurethane or polyisocyanurate, 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.

According to one embodiment of the polyurethane or polyisocyanurate, 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. vaseline oil, 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.

According to one embodiment of the polyurethane or polyisocyanurate, 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).

According to one embodiment of the polyurethane or polyisocyanurate, 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.

According to one embodiment of the polyurethane or polyisocyanurate, 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.

Process for the preparation of a polyurethane or polyisocyanurate

The invention further relates to a process for the preparation of a polyurethane or polyisocyanurate, wherein at least

a) a polyisocyanate composition;

b) a polyol composition;

are reacted 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-%;

wherein the 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.

According to one embodiment of the process for the preparation of a polyurethane or polyisocyanurate, the catalyst is obtained or obtainable by:

I) providing an oil phase comprising a hydrophobic diluent having solubility in water of <1 g/liter at 20 °C and at normal pressure;

ii) 00 to 10 weight-% of a second (meth)acrylate composition comprising a monoester of (meth)acrylic acid with a C1 to C24 alkanol;

III) dispersing the (meth)acrylate monomers and the aqueous and/or alcoholic solution of lithium chloride in the oil phase and reacting the (meth)acrylate monomers;

According to one embodiment of the process for the preparation of a polyurethane or polyisocyanurate, the (meth)acrylate momonomers comprise:

According to one embodiment of the process for the preparation of a polyurethane or polyisocyanurate, 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.

According to one embodiment of the process for the preparation of a polyurethane or polyisocyanurate, 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.

According to one embodiment of the process for the preparation of a polyurethane or polyisocyanurate, 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.

According to one embodiment of the process for the preparation of a polyurethane or polyisocyanurate, 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.

According to one embodiment of the process for the preparation of a polyurethane or polyisocyanurate, 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. vaseline oil, 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.

According to one embodiment of the process for the preparation of a polyurethane or polyisocyanurate, the polyisocyanate composition (a) comprises

a.1 ) at least one polyisocyanate;

a.2) the catalyst comprising an aqueous and/or alcoholic solution of lithium chloride encapsulated in an acrylic copolymer capsule shell;

a.3) optionally further additives.

According to one embodiment of the process for the preparation of a polyurethane or polyisocyanurate, the polyol composition (b) comprises

b.1 ) at least one polyol;

b.2) the epoxide composition;

b.3) optionally further additives.

According to one embodiment of the process for the preparation of a polyurethane or polyisocyanurate, 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).

According to one embodiment of the process for the preparation of a polyurethane or polyisocyanurate, 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.

According to one embodiment of the process for the preparation of a polyurethane or polyisocyanurate, 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.

The present invention is further illustrated by the following embodiments and combinations according to embodiments as indicated by the respective dependencies and back-references. In particular, it is noted that in each instance where a range according to embodiments is mentioned, for example in the context of a term such as "The ... according to any of embodiments 1 to 4", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The ... according to any of embodiments 1 , 2, 3, and 4".

1. 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:

2. The catalyst according to embodiment 1 , wherein the (meth)acrylic copolymer capsule shell is obtained or obtainable by reacting:

wherein the weight-% are based on an overall weight of all (meth)acrylates of 100 weight-%. 3. The catalyst according to embodiment 1 or 2, wherein 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.

4. The catalyst according to any of embodiments 1 to 3, wherein 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.

5. The catalyst according to any of embodiments 1 to 4, obtained or obtainable by:

III) dispersing the (meth)acrylate monomers and the aqueous and/or alcoholic solution of lithium chloride in the oil phase and reacting the (meth)acrylate monomers, thereby obtaining an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell (LiCI-capsule).

6. The catalyst according to any of embodiments 1 to 5, wherein 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 catalyst according to any of embodiments 1 to 6, 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. The catalyst according to any of embodiments 1 to 7, wherein 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. vaseline oil, 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. A catalytic composition comprising a catalyst according to any of embodiments 1 to 8 and an epoxide composition. The catalytic composition according to embodiment 9, wherein the epoxide composition comprises a compound having one or more epoxide groups. 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:

III) dispersing the (meth)acrylate monomers and the aqueous and/or alcoholic solution of lithium chloride in the oil phase and reacting the (meth)acrylate monomers, thereby obtaining an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell (LiCI-capsule). 12. The process according to embodiment 1 1 , wherein the (meth)acrylate momonomers comprise:

13. The process according to embodiment 1 1 or 12, wherein 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.

14. The process according to any of embodiments 1 1 to 13, wherein 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.

15. The process according to any of embodiments 1 1 to 14, wherein 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.

16. The process according to any of embodiments 11 to 15, wherein the core/shell ratio of the (meth)acrylic copolymer capsule containing the ithium 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. 17. The process according to any of embodiments 1 1 to 16, wherein 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. vaseline oil, 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.

18. An aqueous and/or alcoholic solution of lithium chloride encapsulated in an acrylic copolymer capsule shell obtained or obtainable from the process according to any of embodiments 11 to 17.

19. Use of the catalyst according to any of embodiments 1 to 9 or of the aqueous and/or alcoholic solution of lithium chloride encapsulated in an acrylic copolymer capsule shell obtained or obtainable from the process according to any of embodiments 1 1 to 17 for the preparation of polyurethane or polyisocyanurate.

20. Polyurethane or polyisocyanurate obtained or obtainable from the reaction of at least: a) a polyisocyanate composition;

b) a polyol composition;

21. Polyurethane or polyisocyanurate according to embodiment 20 wherein the catalyst is obtained or obtainable by:

III) dispersing the (meth)acrylate monomers and the aqueous and/or alcoholic solution of lithium chloride in the oil phase and reacting the acrylate monomers, thereby obtaining an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell (LiCI-capsule).

22. The polyurethane or polyisocyanurate according to embodiment 20 or 21 , wherein the (meth)acrylic copolymer capsule shell of the catalyst is obtained or obtainable by reacting: i) 30 to 50 weight-%, preferably 35 to 45 weight-%, more preferred 38 to 42 weight-%, of a first acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;

23. The polyurethane or polyisocyanurate according to any of embodiments 20 to 22, wherein 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.

24. The polyurethane or polyisocyanurate according to any of embodiments 20 to 23, wherein 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.

25. The polyurethane or polyisocyanurate according to any of embodiments 20 to 24, wherein 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 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. The polyurethane or polyisocyanurate according to any of embodiments 20 to 26, wherein 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. vaseline oil, 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. The polyurethane or polyisocyanurate according to any of embodiments 20 to 27, wherein 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). The polyurethane or polyisocyanurate according to any of embodiments 20 to 28, wherein 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 polyurethane or polyisocyanurate according to any of embodiments 20 to 29, wherein 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. A process for the preparation of a polyurethane or polyisocyanurate, wherein at least a) a polyisocyanate composition;

b) a polyol composition;

are reacted 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:

wherein the 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 process for the preparation of a polyurethane or polyisocyanurate according to embodiment 31 , wherein the catalyst is obtained or obtainable by:

thereby obtaining an aqueous and/or alcoholic solution of lithium chloride encapsulated in a (meth)acrylic copolymer capsule shell (LiCI-capsule). The process for the preparation of a polyurethane or polyisocyanurate according to embodiment 31 or 32, wherein the (meth)acrylate momonomers comprise:

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-%.

34. The process for the preparation of a polyurethane or polyisocyanurate according to any of embodiments 31 to 33, wherein 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.

35. The process for the preparation of a polyurethane or polyisocyanurate according to any of embodiments 31 to 34, wherein 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.

36. The process for the preparation of a polyurethane or polyisocyanurate according to any of embodiments 31 to 35, wherein 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.

37. The process for the preparation of a polyurethane or polyisocyanurate according to any of embodiments 31 to 36, 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.

38. The process for the preparation of a polyurethane or polyisocyanurate according to any of embodiments 31 to 37, wherein 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. vaseline oil, 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.

39. The process for the preparation of a polyurethane or polyisocyanurate according to any of embodiments 31 to 38 wherein the polyisocyanate composition (a) comprises

a.1 ) at least one polyisocyanate;

a.3) optionally further additives.

40. The process for the preparation of a polyurethane or polyisocyanurateaccording to any of embodiments 31 to 39, wherein the polyol composition (b) comprises

b.1 ) at least one polyol;

b.2) the epoxide composition;

b.3) optionally further additives.

41. The process for the preparation of a polyurethane or polyisocyanurate according to any of embodiments 31 to 40, wherein 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).

42. The process for the preparation of a polyurethane or polyisocyanurate according to any of embodiments 31 to 41 , wherein 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.

43. The process for the preparation of a polyurethane or polyisocyanurate according to any of embodiments 31 to 42, wherein 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.

The present invention is further illustrated by the following reference examples, comparative examples, and examples.

Examples 1. Chemicals

2. Measuring methods OH value DIN 53240

NCO value ASTM D 2572-70 (dibutylamine)

3. Preparation of LiCI encapsulated in an acrylic copolymer capsule Shell - Catalyst 7 Oil phase:

209 g Diisopropylnaphthalene 30 g Stabilizer MUV

Feed 1 :

79.8 g LiCI solution

34, 2g 1 ,2-propylene glycol

Feed 2:

3,6 g MMA

2,4 g 1 ,4-butandioldiacrylate

Feed 3:

0,6 g TBHP (solution of 10 weight- % in water)

Feed 4:

0,84 g AA (solution of 20 weight- % in water)

Feed 5:

0,06 g 2,2'-Azobis(2,4-dimethyl-4-methoxyvaleronitrile

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.

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).

4. Preparation of LiCI encapsulated in an acrylic copolymer capsule Shell - Catalyst 8

Oil phase:

209 g Diisopropylnaphthalene

30 g Stabilizer MUV

Feed 1 :

79.8 g LiCI solution

34.2 g 1 ,2-propylene glycol

Feed 2: 3.6 g MMA

2.4 g PETIA

Feed 3:

0.6 g TBHP (solution of 10 weight- % in water)

Feed 4:

0.84 g AA (solution of 20 weight- % in water)

Feed 5:

0.06 g 2,2'-Azobis(2,4-dimethyl-4-methoxyvaleronitrile

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.

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).

5. Preparation of LiCI encapsulated in an acrylic copolymer capsule Shell - Catalyst 9

Oil phase:

208.6 g Diisopropylnaphthalene

30 g Stabilizer MUV

Feed 1 :

73.5 g LiCI solution

31.5 g 1 ,2-propylene glycol

Feed 2:

11 g MMA

1.5 g PETIA

2.48 g n-butylacrylate

Feed 3:

1.5 g TBH P (solution of 10 weight- % in water)

Feed 4: 1.21 g AA (solution of 17,35 weight- % in water)

Feed 5:

0.15 g 2,2'-Azobis(2,4-dimethyl-4-methoxyvaleronitrile

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.

6. Preparation of LiCI encapsulated in an acrylic copolymer capsule with different capsule formulation - Catalyst 5

Oil phase:

209.5 g Diisopropylnaphthalene

30 g Stabilizer MUV

Feed 1 :

67.2 g LiCI solution

28.8 g 1 ,2-propylene glycol

Feed 2:

11.76 g MMA

4.8g 1 ,4-butandioldiacrylate

7.44 g n-butylacrylate

Feed 3:

2.4 g TBHP (solution of 10% in water)

Feed 4:

1 68g AA (solution of 20% in water)

Feed 5:

0.24 g 2,2'-Azobis(2,4-dimethyl-4-methoxyvaleronitrile 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 15.5 m m (z-average determined by means of light scattering). The capsules dispersion is used directly in the subsequent application.

7. Preparation of LiCI encapsulated in an acrylic copolymer capsule with different capsule formulation - Catalyst 6

Oil phase:

209.5 g Diisopropylnaphthalene

30 g Stabilizer MUV

Feed 1 :

79.8g LiCI solution

34.2 g 1 ,2-propyleneglycol

Feed 2:

4.19 g MMA

1.2 g PETIA

0.61 g n-butylacrylate

Feed 3:

0.6g TBHP (solution of 10% in water)

Feed 4:

0.4g AA (solution of 20% in water)

Feed 5:

0.06 g 2,2'-Azobis(2,4-dimethyl-4-methoxyvaleronitrile

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 4.7 m m (z-average determined by means of light scattering). 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(0,5).

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.

Table 1

^* in dispersion

^** Core/shell ratio: The core ratio“Core” is defined as the weight ratio between the materials present in the core over the total weight of materials present in the core plus the shell (core + shell = 100 weight-%).“Core” is indicated in weight-%.The shell ratio“Shell” is defined as the weight ratio between the materials present in the shell over the total weight of materials present in the core plus the shell (core + shell = 100 weight-%).“Shell” is indicated in weight-%. The core/shell ratio is thus dimensionless. 8. Polyurethane synthesis

In accordance with Table 2, 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.

Table 2

Compositions of Polyurethane synthesis

^*MV = mixing ratio, 100 g A-component to 400 g B-component.

9. Measurement of reactivity at room temperature The open time at room temperature (RT, 25 °C) 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. For this purpose, 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. Measurement of reactivity at 70 °C

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. The results are summarized below in Table 3.

Table 3

Results of open time measurement and reactivity measurments

Samples with open times at RT longer than 40 min, preferably longer than 55 min, and a curing start time at 70 °C of less than 15 min, preferably less than 12 min, more preferred less than 10 min, and a rather quick reactivity at 70 °C < 8.5 min, preferably < 7 min, were identified as especially well suited for application for e.g. adhesives which are cured at 70 °C in big samples (example adhesive between layers in rotor blades for wind energy; reference epoxy systems with 60 min open time).

Cited Literature

US 6,224,793 B1

US 7,338,928B2 A.-C. Bijlard, A. Hansen, I. Lieberwirth, K. Landfester, A. Taden, Adv. Mater.

2016, Vol. 28, 30, pages 6372-6377

WO 2013/057070 A1

WO 2010/121898 A1

WO 2012/103965 A1

WO 2013/098034 A1

WO 2013/143841 A1

WO 2015/078740 A1

Kunststoffhandbuch, 7, Polyurethane", Carl Hanser-Verlag, 3rd edition 1993, section 3.1 "Kunststoffhandbuch, 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, sections 3.2 and 3.3.2

US 3,883,571 B

WO 02/10250 A1

US 4,229,347 B

WO 201 1/107367 A1

WO 2013/127647 A1

WO 2013/1 10512 A1

Claims

2. The catalyst according to claim 1 , wherein the (meth)acrylic copolymer capsule shell is obtained or obtainable by reacting:

3. The catalyst according to claim 1 or 2, wherein the polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol of (i) is a polyester of (meth)acrylic acid with a C2 to C10 alkylpolyol, 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;

and/or

wherein the monoester of (meth)acrylic acid with a C1 to C24 alkanol of (ii) is a monoester of (meth)acrylic acid with a C1 to C10 alkanol, 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, more preferred 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.

4. The catalyst according to any of claims 1 to 3, obtained or obtainable by:

5. The catalyst according to any of claims 1 to 4, 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.

6. A catalytic composition comprising a catalyst according to any of claims 1 to 5 and an epoxide composition.

7. 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:

8. The process according to claim 7, wherein the (meth)acrylate momonomers comprise: i) 30 to 50 weight-%, preferably 35 to 45 weight-%, more preferred 38 to 42 weight-%, of a first acrylate composition comprising a polyester of (meth)acrylic acid with a C2 to C24 alkylpolyol;

9. The process according to claim 7 or 8, wherein 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.

10. An aqueous and/or alcoholic solution of lithium chloride encapsulated in an acrylic copolymer capsule shell obtained or obtainable from the process according to any of claims 7 to 9.

11. Use of the catalyst according to any of claims 1 to 5 or of the aqueous and/or alcoholic solution of lithium chloride encapsulated in an acrylic copolymer capsule shell obtained or obtainable from the process according to any of claims 7 to 9 for the preparation of polyurethane or polyisocyanurate.

12. Polyurethane or polyisocyanurate obtained or obtainable from the reaction of at least: a) a polyisocyanate composition;

b) a polyol composition;

13. Polyurethane or polyisocyanurate according to claim 12, wherein the catalyst is obtained or obtainable by:

14. A process for the preparation of a polyurethane or polyisocyanurate, wherein at least a) a polyisocyanate composition;

b) a polyol composition;

15. The process for the preparation of a polyurethane or polyisocyanurate according to claim 14, wherein the catalyst is obtained or obtainable by: