EP2268688A1 - Mousse de polyisocyanurate contenant de la silicone - Google Patents

Mousse de polyisocyanurate contenant de la silicone

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Publication number
EP2268688A1
EP2268688A1 EP09733925A EP09733925A EP2268688A1 EP 2268688 A1 EP2268688 A1 EP 2268688A1 EP 09733925 A EP09733925 A EP 09733925A EP 09733925 A EP09733925 A EP 09733925A EP 2268688 A1 EP2268688 A1 EP 2268688A1
Authority
EP
European Patent Office
Prior art keywords
optionally
radicals
radical
foams
foamable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09733925A
Other languages
German (de)
English (en)
Inventor
Jens Cremer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
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Filing date
Publication date
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP2268688A1 publication Critical patent/EP2268688A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
    • 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
    • C08G18/61—Polysiloxanes
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid

Definitions

  • the invention relates to foamable preparations based on organosilicon compounds, silicone-containing low-density polyisocyanurate foams, and processes for their preparation.
  • polyisocyanurate chemistry As a relatively successful approach to the preparation of fire-retarded polyurethane foams, polyisocyanurate chemistry has been found. In the preparation of corresponding foams is usually carried out a reaction of polyisocyanates with compounds having isocyanate-reactive hydrogen atoms, e.g. Polypropylene glycols, wherein the isocyanate index is at least 180. In the presence of a trimerization catalyst, in addition to the urethane, it also forms isocyanurate structures. The resulting polyisocyanurate (PIR) foams are typically closed-cell rigid foams which have the best fire retardant properties of all polyurethane foam types.
  • PIR polyisocyanurate
  • These rigid PIR foams are usually made using physical and chemical blowing agents.
  • physical blowing agents for example, fluorine chlorine hydrocarbons (CFCs), hydrofluorocarbons (HFCs), hydrocarbons and liquid carbon dioxide are used, while used as chemical blowing agents mainly water and carboxylic acids.
  • silicone-polyurethane copolymers i. of polysiloxanes, which also contain polyurethane and / or urea units, it is possible to develop such fire-retardant foams, which have new and tailored to the particular application combinations of properties.
  • EP 1485419 Bl which describes the preparation of silicone-polyurethane foams starting from alkylamino- or alkylhydroxy-terminated silicone oils and diisocyanates in the so-called “one-shot process.”
  • DE 102006013416 A1 also describes the preparation from Si licon PU foams from prepolymers which are prepared on the basis of alkylamino- or alkylhydroxy-terminated silicone oils and diisocyanates in a solvent-based process.
  • the silicone polyurethane foams described hitherto have in common that they are prepared on the basis of linear or only very weakly, but statistically branched in the side chains Siimo xanen. Because of this linear siloxane chain, no rapid build-up of molecular weight takes place during the rise phase during the rise phase, so that only a relatively slow increase in viscosity takes place during the rise phase, as a result of which the polymer matrix is generally readily flowable even after the blowing reaction has ended and therefore the fine cell structure before complete curing of the foam can still collapse. Even if only a small part of the cell structure collapses, this leads to an irregular and coarse cell distribution.
  • the struts between the individual foam cells must not fall below a critical diameter during the rising phase. This ensures that the still flowable polymer matrix can counteract the imminent collapse of the foam structure. Will be the desired
  • Hyperbranched polymers are already known and are described, for example, in the review article: C.Gao, D.Yan; Prog. Polym. Sci., 2004, 24, 183-275 for synthesis, properties and applications are discussed in detail. Hyperbranched polymers belong to dendritic macromolecules and have a stronger branching than conventionally branched polymers, which mainly have primary or secondary branches on a linear main chain. So far, divergent synthetic methods have been used for the synthesis of hyperbranched polymers, with a monomer that is just two different types of functional
  • Suitable monomers are those which have a functional group A and two functional groups B, ie an AB 2 monomer.
  • AB x with x> 1 can be used.
  • the use of AB X monomers in a monomolecular polymerization is only possible if the A and B groups react with each other only when it is desired in the polymer synthesis, ie after addition of a catalyst or by an increase in temperature.
  • the synthesis of hyperbranched polymers can also be done with two different monomer types, each having only one kind of functional groups, but in different numbers, such as A 3 and B 2 building blocks.
  • a reaction of these two types of A 3 and B 2 can then be used to obtain in situ A 2 B and AB 2 monomer blocks (di-molecular polymerization: in general with A x and B y , where x> 1 and y> 2 ).
  • Such methods are well known and described, for example, in US-B 6,534,600.
  • the invention provides foamable preparations which contain (A) hyperbranched siloxanes of the formula V- (R 2 ) P - m ([S iR 2 O]! -SiR 2 R 1 U (I),
  • V denotes a p-valent radical
  • R may be the same or different and is a monovalent, optionally substituted hydrocarbon radical
  • R 1 may be the same or different and represents a monovalent organic radical having at least one isocyanate group or a group reactive toward isocyanate radicals
  • R 2 may be the same or different and represents monovalent radicals
  • 1 is an integer greater than or equal to 1, preferably 1 to 1000, particularly preferably 5 to 500, in particular 10 to 100, p is an integer greater than or equal to 3, preferably 3 to 20, particularly preferably 3 or 4, and m is one integer greater than or equal to 3, preferably 3 to 20, more preferably 3 to 4, means, with the proviso that p is greater than or equal to m and in the foamable preparation at least three isocyanate groups are present.
  • R examples are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert.
  • -Pentyl radical hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as 2, 2, 4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical; Alkenyl radicals, such as the vinyl and allyl radicals; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals; Aryl radicals, such as the phenyl and the naphthyl radical; Alkaryl radicals, such as o-, m-,
  • substituted hydrocarbon radicals R are methoxymethylene radicals, ethoxymethylene radicals, dimethylaminomethylene and diethylaminomethylene.
  • Radical R is preferably monohydric, optionally substituted hydrocarbon radicals having 1 to 40 carbon atoms, particularly preferably hydrocarbon radicals having 1 to 30 carbon atoms, in particular hydrocarbon radicals having 1 to 6 carbon atoms.
  • radicals R 1 are preferably those of the formula
  • Y and Z independently of one another are divalent, optionally substituted hydrocarbon radicals which may be interrupted by heteroatoms,
  • A has the meaning of -S-, -O- or -NR 3 - has with R 3 equal to hydrogen atom or monovalent, optionally substituted hydrocarbon radical and a is 0 or 1.
  • radicals R 1 are preferably those of the formula (II)
  • the foamable preparations according to the invention must contain polyisocyanate (B).
  • the foamable preparations according to the invention may comprise polyisocyanate (B), which is preferred.
  • R 3 are hydrogen atom and the examples given for radical R.
  • Radical R is preferably hydrogen.
  • radical A is -O-.
  • radicals Y and Z are each, independently of one another, ethylene, propylene, butylene, pentylene, hexamethylene, meythyloxyethylene, toluolylene, methylene-bis-phenylene, phenylene, naphthylene, cyclohexylene and isophorone residues.
  • Y is preferably a divalent aliphatic hydrocarbon radical which is optionally substituted by -NCO and which may be interrupted by heteroatoms, particularly preferably zugt to propylene and Methyloxyethylenreste, in particular Methyloxyethylenreste.
  • Z is preferably divalent, aromatic, optionally -NCO-substituted, hydrocarbon radicals which may be interrupted by heteroatoms, more preferably toluolylene and methylene-bis-phenylene radicals, in particular methylene-bis-phenylene radicals.
  • a in formula (II) as well as in formula (III) is equal to 1.
  • radicals R 2 are hydrogen atom, organyloxy radicals, such as methoxy, ethoxy and phenoxy radicals, optionally substituted hydrocarbon radicals, for example the radicals mentioned in R, organyloxymethylene radicals, morpholinomethylene radicals, piperazinomethylene radicals, acrylamidomethylene radicals, dimethylaminomethylene radicals, diethylaminomethylene radicals, Dibutylaminomethylene radicals, phenoxymethylene radicals and methylmercaptomethylene radicals, and siloxanyl radicals which can be bonded to V both via oxygen and via silicon.
  • organyloxy radicals such as methoxy, ethoxy and phenoxy radicals
  • hydrocarbon radicals for example the radicals mentioned in R, organyloxymethylene radicals, morpholinomethylene radicals, piperazinomethylene radicals, acrylamidomethylene radicals, dimethylaminomethylene radicals, diethylaminomethylene radicals, Dibutylaminomethylene radicals, phenoxy
  • the radical R 2 is preferably an organyloxymethylene radical, more preferably the methoxymethylene radical.
  • radical V examples are any previously known polyvalent radicals, such as e.g. polyvalent organic radicals, polyvalent silyl radicals and boric acid radicals.
  • radical V is a polyvalent organic radical or a polyvalent silyl radical, more preferably a polyvalent organic radical. If the radical V is polyvalent silyl radicals, SiO.sub.3 / 2 and SiO.sub.4 / 2 are preferred.
  • radical V is a polyvalent organic radical
  • polyvalent hydrocarbon radicals which are optionally substituted by nitrogen and / or oxygen radicals are preferred and those of the formula
  • W is a p-valent hydrocarbon radical which may contain heteroatoms
  • R 4 may be the same or different and is a divalent, optionally substituted hydrocarbon radical
  • R 5 may be the same or different and an optionally substituted hydrocarbon radical, -O- or -NR 3 ' - means R 3' is one of the above for R 3 R
  • R may be identical or different and is an optionally substituted hydrocarbon radical, -O- or -NR 3 " - means with R equal to one of the above R
  • R 7 may be the same or different and a divalent, optionally substituted hydrocarbon radical means that c is 0 or 1 and p and m have one of the meanings given above, with the proviso that p is greater than or equal to m.
  • W is preferably trivalent, aliphatic or aromatic, optionally heteroatom-containing hydrocarbon radicals, particularly preferably aromatic, optionally heteroatom-containing hydrocarbon radicals.
  • radical W are 1, 3, 4-benzene, 1, 3, 5-cyanurate and N, N, N '-Biuretreste.
  • radicals R 4 and R 7 are each independently of one another the radicals indicated for Y and Z.
  • R 4 is preferably divalent, optionally substituted hydrocarbon radicals having 1 to 10 carbon atoms, particularly preferably phenylene radicals, tolylene radicals and hexamethylene radicals, in particular phenylene radicals.
  • R 5 is -NH-.
  • the radical R 6 is preferably -O-.
  • c is equal to 1.
  • the hyperbranched siloxanes (A) used according to the invention have an isocyanate content of preferably 0 to 25% by weight, particularly preferably 0 to 15% by weight.
  • the hyperbranched siloxanes (A) used according to the invention have a viscosity of preferably 100 to 10,000 mPas, more preferably 500 to 5000 mPas, in each case at 25 ° C. and measured in accordance with ASTM D 4283.
  • the hyperbranched siloxanes (A) according to the invention can be prepared by methods customary in silicon chemistry.
  • the hyperbranched siloxanes (A) of the formula (I) used are identical to the organic radical by reaction of linear ⁇ , ⁇ -aminoalkyl-functionalized, ⁇ , ⁇ -hydroxyalkyl-functionalized siloxanes or ⁇ , ⁇ -hydroxy-functionalized Si - Loxanes (Al) prepared with polyisocyanates.
  • hyperbranched siloxanes (A) having radicals R 1 of the formula (II) are obtained.
  • hyperbranched siloxanes (A) with radicals R 1 of the formula (III) are to be obtained, then in a further reaction step the hyperbranched siloxanes having radicals R 1 of the formula (II) are reacted with further polyisocyanate, this being used in an excess is used, so that per mole of aminoalkyl radicals or hydroxyalkyl-functional radicals of the hyperbranched siloxanes having radicals R 1 of the formula (II) at least 1 mol, in particular 2 to 20 mol, isocyanate units.
  • the molar excess of isocyanates is preferably consumed during foaming for the trimerization reaction to isocyanurates.
  • hyperbranched siloxanes (A) used according to the invention are used.
  • Formula (I) with V equal to silyl in a two-step process wherein initially linear ⁇ , ⁇ -hydroxy-terminated siloxanes (A2) with an opposite (A2) reactive silane, such as trimethoxymethylsilane, compared to the siloxanes (A2) in the underside, be implemented.
  • A2 linear ⁇ , ⁇ -hydroxy-terminated siloxanes
  • A3 hyperbranched siloxanes (A3) having radicals R 1 of the formula (II) are obtained.
  • hyperbranched siloxanes (A) with radicals R 1 of the formula (III) are to be obtained, in a further reaction step then the hyperbranched siloxanes having radicals R 1 of the formula (II) are reacted with further polyisocyanate, this being used in an excess, so that per mole of aminoalkyl radicals or hydroxyalkyl-functional radicals of the hyperbranched siloxanes having radicals R 1 of the formula (II) at least 1 mole, in particular 2 to 20 mol, isocyanate units are used.
  • the molar excess of isocyanates is preferably consumed in the foam formation for the trimerization reaction to form isocyanurates.
  • the hyperbranched siloxane (A3) can be functionalized prior to reaction with the polyisocyanate. Preference is given to the functionalization with silane cycles of the formulas
  • polyisocyanates (B) it is possible to use all known organic compounds having two or more isocyanate groups. These may be aliphatic or aromatic isocyanates.
  • Preferred polyisocyanates (B) are those of the general formula
  • Q is a b-functional, optionally substituted hydrocarbon radical and b is an integer of at least 2, preferably from 2 to 10, particularly preferably 2 or 6, in particular 2 to 5, means.
  • Q is optionally substituted hydrocarbon radicals having 4 to 30 carbon atoms, more preferably hydrocarbon radicals having 6 to 25 carbon atoms.
  • polyisocyanates (B) are diisocyanatodiphenylmethane (MDI), both in the form of crude or industrial MDI and in the form of pure 4,4'- or 2,4'-isomers or their preparations, tolylene diisocyanate (TDI) in the form its various regioisomers, diisocyanato naphthalene (NDI), isophorone diisocyanate (IPDI), 1, 3-bis (1-isocyanato-1-methylethyl) benzene (TMXDI) or also of hexamethylene diisocyanate (HDI), polymeric MDI (p-MDI), Triphenylmethane triisocyanate or biuret or Iso- cyanurattrimerisate the above isocyanates.
  • MDI diisocyanatodiphenylmethane
  • TDI tolylene diisocyanate
  • NDI diisocyanato naphthalene
  • polyisocyanates (B) used according to the invention are preferably polymeric MDI of the formula
  • Polymeric MDI is e.g. obtained in the production of diphenylmethane diisocyanate and is generally a mixture of difunctional MDI and various higher molecular weight MDI oligomers having a higher functionality,
  • the polyisocyanates (B) may be the same as those used in the preparation of the siloxanes (A) especially if it is a two-stage process.
  • polyisocyanate is used in excess and the mixture thus obtained is advantageously used further for preparing the preparation according to the invention .
  • preparations according to the invention contain polyisocyanates (B), these are amounts of preferably 0.1 to 150 parts by weight, more preferably 10 to 120 parts by weight, in particular 20 to 100 parts by weight, in each case based on 100 parts by weight of hyperbranched siloxane (A).
  • the preparations according to the invention preferably contain polyisocyanates (B).
  • the preparations according to the invention may contain further substances, such as e.g.
  • Fillers C
  • emulsifiers D
  • physical blowing agents E
  • catalysts that accelerate foaming F
  • chemical blowing agents H
  • additives I
  • fillers (C) can be any non-reinforcing fillers, ie fillers with a
  • hydrophobic as well as hydrophilic fumed silicas represent a preferred filler.
  • a hydrophobic fumed silica is used. whose surface has been modified with trimethylsilyl groups.
  • the fillers (C) used-in particular pyrogenic silicic acids-can perform various functions. So they can be used to adjust the viscosity of the foamable mixture.
  • fillers (C) in particular through the use of fumed silica -
  • filler (C) may also be added with exfoliation graphite.
  • the preparations according to the invention contain fillers (C), they are amounts of preferably 0.1 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, in particular 0.1 to 15 parts by weight, based in each case on 100 parts by weight of siloxane ( A).
  • the preparations according to the invention preferably contain fillers (C).
  • emulsifiers (D) it is advantageous to add emulsifiers (D) to the foamable preparations.
  • suitable emulsifiers (D) which also serve as foam stabilizers, it is possible, for example, to use all commercially available silicone oligomers modified by polyether side chains, which are also used for the preparation of conventional polyurethane foams.
  • emulsifiers (D) are used, they are amounts of preferably up to 6 wt .-%, more preferably of 0.3 to 3 wt .-%, each based on the total weight of the foamable preparations.
  • the preparations according to the invention preferably contain no emulsifiers (D).
  • the formulations may also contain compounds (E) which may serve as physical blowing agents.
  • component (E) it is preferred to use low molecular weight hydrocarbons, e.g. n-propane, n-butane, n-pentane or cyclopentane, dimethyl ether, fluorinated hydrocarbons such as 1, 1-difluoroethane or 1, 1, 1, 2-tetrafluoroethane or CO2 used.
  • the foam production can optionally be carried out exclusively by the physical blowing agent (E). In most cases, however, foaming takes place by an additional reaction of the isocyanate-functional components in the preparation according to the invention with component (H) as chemical blowing agent. This can reduce the amount of physical blowing agent (E) needed to produce lower density foams.
  • Component (E) is particularly preferably low molecular weight hydrocarbons, in particular n-pentane.
  • preparations according to the invention comprise constituent (E), these are amounts of preferably 0.1 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, in particular 0.1 to 15 parts by weight, in each case based on 100 parts by weight of siloxane (A) ,
  • the preparations according to the invention preferably contain physical blowing agent (E). Furthermore, the foamable preparations according to the invention may comprise further catalysts (F) which accelerate the foaming with the chemical blowing agent (H).
  • catalysts (F) inter alia, organotin compounds are suitable. Examples are dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate or dibutyltin bis (dodecylmercaptide).
  • tin-free catalysts (F) such as heavy metal compounds or amines come into question.
  • tin-free catalysts include iron (III) acetylacetonate, zinc (II) octoate, zirconium (IV) acetylacetonate, bismuth (III) neodecanoate.
  • amines are triethylamine, tributylamine, 1,4-diazabicyclo [2,2,2] octane, N, N-bis (N, N-dimethyl-2-aminoethyl) -methylamine, N, N-dimethylcyclohexylamine, N, N-dimethylphenylamine, bis-N, N-dimethylaminoethyl ether, N, N-dimethyl-2-aminoethanol, N, N-dimethylaminopyridine, N, N, N ', N ", N" -pentamethyldiethylene triamine l, 5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, N-ethylmorpholine or N, N'-dimethylaminopyridine.
  • Catalyst (F) is preferably amines, more preferably N, N, N ', N ", N" -pentamethyldiethylenetriamine.
  • the catalysts (F) can be used individually or as a mixture. If appropriate, the catalysts used in the preparation of the siloxanes (A) can simultaneously also serve as catalysts (F) for foaming.
  • catalyst (F) are amounts of preferably 0.1 to 6.0 wt .-%, particularly preferably from 0.3 to 4.0 wt .-%, each based on the total weight of the foamable invention Preparation.
  • the preparations according to the invention preferably contain catalysts (F) if chemical blowing agents (H) are used.
  • the foamable preparations according to the invention contain trimerization catalysts (G) which initiate and accelerate the trimerization of isocyanate groups to isocyanurate groups.
  • trimerization catalysts (G) are ammonium, alkali metal or alkaline earth metal salts of carboxylic acid salts, such as potassium formate, potassium acetate, potassium (2-ethylhexanoate), ammonium formate, ammonium acetate, ammonium (2-ethylhexanoate), [1- (N, N, N-trimethylammonium) propan-2-ol] formate and [1- (N, N, N-trimethylammonium) propan-2-ol] (2-ethylhexanoate).
  • carboxylic acid salts such as potassium formate, potassium acetate, potassium (2-ethylhexanoate), ammonium formate, ammonium acetate, ammonium (2-ethylhexanoate), [1- (N, N, N-trimethylammonium) propan-2-ol] formate and [1- (N, N, N-trimethylammonium) propan-2-ol
  • component (G) Preferably used as component (G) are salts of carboxylic acids, particularly preferably salts of carboxylic acids having 1 to 20 carbon atoms. These may be linear or branched, substituted or unsubstituted, saturated or unsaturated aliphatic or aromatic carboxylic acids
  • trimerization catalyst (G) is carboxylic acid salts
  • potassium salts of carboxylic acids are preferred, especially potassium (2-ethylhexanoate).
  • the catalysts (G) can be used individually or as a mixture. Alternatively, they may be used in admixture with one or more catalysts (F).
  • Catalyst (G) is used in amounts of preferably 0.1 to 10.0
  • both water and all compounds having preferably at least one isocyanate-reactive function can serve as chemical blowing agents (H).
  • constituent (H) are aminoalkyl- or hydroxy-functional siloxanes which are different from component (A), monomeric alcohols, monomeric diols, such as glycol, propanediol and butanediol, monomeric oligools, such as pentaerythritol or trihydroxymethyl, oligomeric or polymeric Alcohols having one, two or more hydroxyl groups, such as ethylene glycols or propylene glycols, water, monomeric amines having one, two or more amine functions, such as ethylenediamine and hexamethylenediamine, and also oligomeric or polymeric amines having one, two or more amine functions.
  • monomeric alcohols monomeric diols, such as glycol, propanediol and butanediol
  • monomeric oligools such as pentaerythritol or trihydroxymethyl
  • oligomeric or polymeric Alcohols having one, two or more hydroxyl groups such as
  • component (H) are preferably hydroxy compounds, with water being particularly preferred.
  • Component (H) may be any type of water, e.g. natural waters and chemical waters, where water (H) may be liquid or gaseous, including atmospheric moisture.
  • component (H) are amounts of preferably 0.1 to 20 parts by weight, more preferably from 0.1 to 15 parts by weight, in particular from 0.1 to 10 parts by weight, based in each case on 100 parts by weight of siloxane (A) ,
  • the compositions of the invention contain component (H).
  • additives (I) are cell regulants, thixotropic agents, plasticizers and dyes.
  • flame retardants can also be added to the foamable preparations, for example phosphorus-containing compounds, especially phosphates and phosphonates, as well as halogenated polyesters and polyols or chloroparaffins.
  • additives (I) are used, these are amounts of preferably 0.1 to 30 parts by weight, more preferably of 0.1 to 20 parts by weight, in particular of 0.1 to 15 parts by weight, based in each case on 100 parts by weight of siloxane ( A).
  • the preparations according to the invention preferably contain additives (I).
  • the components used according to the invention may each be one type of such a component as well as a mixture of at least two types of a respective component.
  • the preparations according to the invention are preferably those comprising (A) siloxanes according to the formula (I), if appropriate (B) polyisocyanates, optionally (C) fillers, if appropriate (D) emulsifiers, optionally
  • the preparations according to the invention preferably contain no further constituents.
  • the preparations according to the invention can now be prepared by any desired methods known per se, such as simple mixing of the individual components, it also being possible to prepare premixes of individual constituents.
  • 1-component systems as well as 2-component systems can be produced.
  • the two components of the foamable preparation according to the invention can contain all constituents in any desired combinations and proportions, with the proviso that one component does not simultaneously contain isocyanate-functional components and trimerization catalyst (G) and chemical blowing agents (H) contains.
  • a mixture comprising constituent (A), optionally constituent (B), optionally constituent (C), optionally component (D), optionally constituent (E) and optionally constituent (I) as component, is preferably used for the preparation of the preparation according to the invention 1 and a component 2 comprising component (G), optionally component (F) and optionally component (H), which are then mixed together to prepare the foam according to the invention.
  • the preparations according to the invention are preferably liquid to viscous and have a viscosity of preferably 250 to 10,000 mPas, more preferably 500 to 5,000 mPas, in each case at 25 ° C. and measured in accordance with ASTM D 4283.
  • the preparations according to the invention are preferably used for the production of foams, more preferably rigid foams.
  • Another object of the present invention is a process for the preparation of silicone-containing PolyisocyanuratShume, characterized in that hyperbranched siloxanes (A), optionally polyisocyanate (B) and trimerization catalyst (G) and at least one blowing agent are mixed and allowed to react.
  • A hyperbranched siloxanes
  • B optionally polyisocyanate
  • G trimerization catalyst
  • hyperbranched siloxane (A), polyisocyanate (B) and trimerization catalyst (G) and at least one propellant mixed and allowed to react.
  • hyperbranched siloxane (A), polyisocyanate (B), physical blowing agent (E), catalyst (F), trimerization catalyst (G) and chemical blowing agent (H) are mixed and allowed to react.
  • firstly hyperbranched siloxane (A), polyisocyanate (B), physical blowing agent (E), optionally fillers (C) and optionally additives (I) are premixed and then mixed with a mixture consisting of catalyst (F ), Trimerization catalyst (G) and chemical blowing agent (H) are mixed and allowed to react.
  • the inventive method is at starting temperatures of preferably 0 to 100 0 C, more preferably 10 to 40 0 C, in particular 15 to 30 0 C, performed.
  • the heat generated during the reaction preferably remains in the system and contributes to the formation of foam.
  • reaction temperatures up to preferably 50 to 150 0 C are reached.
  • the process of the invention is preferably carried out at the pressure of the surrounding atmosphere, that is about 900 to 1100 hPa.
  • the process according to the invention preferably releases gaseous components, such as, for example, CO.sub.2 and gaseous pentane, which are largely responsible for the structure of the foam structure according to the invention.
  • gaseous components such as, for example, CO.sub.2 and gaseous pentane
  • Another object of the invention are foams, which can be prepared by reacting hyperbranched siloxanes (A), optionally polyisocyanate (B) and trimerization catalyst (G) with at least one blowing agent.
  • the foams according to the invention also have isocyanurate structures in addition to urethane.
  • the foams according to the invention are distinguished by a fine, closed-cell foam structure, have excellent mechanical properties and are dimensionally stable and not flexible.
  • the foams of the invention have a density of preferably 10 to 500 kg / m 3 , particularly preferably 15 to 300 kg / m 3 , in particular 20 to 200 kg / m, in each case determined at 25 ° C and 1013 hPa.
  • the foams of the invention can be obtained both closed-cell and open-celled.
  • the foams according to the invention can be used wherever polyisocyanurate foams have hitherto been used. In particular, they are suitable for heat and noise insulation.
  • the foamable preparations according to the invention have the advantage that they can be processed in a very simple manner and with the hitherto known methods from PU technology.
  • the preparations according to the invention have the advantage that they can be prepared with commercially readily available educts. Furthermore, the preparations according to the invention have the advantage that they are easy to process and can be prepared with low viscosity.
  • the preparations according to the invention have the advantage that silicone polyisocyanurate foams of low density can be produced.
  • the process according to the invention for producing polyisocyanate rubber foams has the advantage that it is simple to carry out.
  • the foams of the invention have the advantage that they are rigid and extremely flame retardant.
  • the foams according to the invention also have the advantage that they have high mechanical strengths, in particular in combination with low foam densities.
  • pMDI polymeric MDI having a functionality of 2.9 (commercially available under the name ® Lupranat M70R at BASF
  • Silicone emulsifier polydimethylsiloxane-polyethylene oxide copolymer (commercially available under the name DABCO ® 5598 by Air
  • Amine catalyst N, N, N ', N ", N" -pentamethyldiethylenetriamine
  • Trimerization catalyst potassium (2-ethylhexanoate), 75% by weight in diethylene glycol.
  • reaction mixture was then treated with 20 mg of benzoyl chloride and at a pressure of 10 mbar from
  • Example 3 66.3 g of the hyperbranched siloxane obtained from Example 1 were first processed to a homogeneous emulsion with 33.7 g of pMDI and 14.0 g of n-pentane by means of a high-speed KPG stirrer. Subsequently, a mixture consisting of 0.20 g of water, 0.20 g of amine catalyst and 1.40 g Trimerleiterska- catalytic agent was added quickly and emulsified again by means of a high-speed KPG stirrer to a homogeneous mixture. After approx. 10 seconds, an exothermic reaction with foaming began. Foaming was completed after another approx. 90 seconds. This resulted in a yellow, rigid hard foam with a density of 60 kg / m.
  • 100.0 g of the reaction product thus obtained are processed to a homogeneous emulsion after addition of 1.20 g of silicone emulsifier and 12.0 g of n-pentane with a high-speed KPG stirrer. Subsequently, a mixture consisting of 0.20 g Water, 0.20 g of amine catalyst and 1.40 g Trimerleiterskata- lysator quickly added and emulsified again by means of a high-speed KPG stirrer to a homogeneous mixture. After approx. 10 seconds, an exothermic reaction with foam development commenced. Foaming was completed after another approx. 90 seconds. The result was a yellow, rigid rigid foam with a density of 70 kg / m.
  • Example 7 60.00 g of an anhydrous linear siloxane of the formula HO- [Si (CH 3) 2 O] 14 Si (CH 3) 2 -OH first with 3.20 g (methyl carbamatomethyl) trimethoxysilantrimethoxysilan 30 min at 60 0 C and 10 mbar in the presence of 100 ppm lithium methylate reacted as a catalyst. Subsequently, 7.20 g of 2,2-dimethyl-2-sila-l, 4-dioxacylohexan were added and stirred at 60 0 C for a further 30 min.
  • the hyperbranched siloxane was neutralized with 100 ppm of acetic acid and freed from by-products at 10 mbar and 60 0 C for 15 min and 10 mbar. This was then taken up in 100 ml of absolute acetone and mixed with 40.0 g of pMDI. The reaction mixture thus obtained was then stirred for 30 min at 50 ° C. in the presence of 20 mg of tin (II) - (2-ethylhexanoate) as catalyst, the hydroxyl groups of the organosiloxane completely reacting out. Subsequently, it was mixed with 30 mg of benzoyl chloride and freed from the solvent at a pressure of 10 mbar.
  • an anhydrous linear siloxane of the formula HO- [Si (CH 3) 2 -O] i4Si (CH 3) 2 -OH were first with 3.20 g Methylcar- bamatomethyl) trimethoxysilanmin at 60 0 C and 10 mbar brought in the presence of 100 ppm lithium methylate as a catalyst for the reaction. Then 7.20 g of 2, 2-dimethyl-2-sila-l, 4-dioxacylohexan were added and stirred at 60 0 C for 30 minutes. After the reaction, the hyperbranched siloxane was neutralized with 100 ppm of acetic acid and freed from by-products at 10 mbar and 60 0 C for 15 min and 10 mbar.
  • 60.0 g of the reaction mixture thus obtained were first processed with 40.0 g of pMDI and 1.20 g of silicone emulsifier and 12.0 g of n-pentane by means of a high-speed KPG stirrer to a homogeneous emulsion. Subsequently, a mixture consisting of 0.20 g of water, 0.20 g of amine catalyst and 1.40 g trimerization catalyst was added quickly and again emulsified by means of a high-speed KPG stirrer to a homogeneous mixture. After approx. 10 seconds, an exothermic reaction with foaming began. Foaming was completed after another approx. 90 seconds. The result was a yellow, rigid rigid foam with a density of 100 kg / m.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne des préparations transformables en mousse qui contiennent des siloxanes hyperramifiés de formule V- (R2)p-m( [SiR2O]l-SiR2R1)m (I), éventuellement des polyisocyanates (B) et des catalyseurs de trimérisation (G), les radicaux et les indices ayant les significations énoncées dans la revendication 1, des mousses de polyisocyanurate de faible densité contenant de la silicone, ainsi que des procédés de production correspondants.
EP09733925A 2008-04-25 2009-04-21 Mousse de polyisocyanurate contenant de la silicone Withdrawn EP2268688A1 (fr)

Applications Claiming Priority (2)

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DE102008001384A DE102008001384A1 (de) 2008-04-25 2008-04-25 Siliconhaltiger Polyisocyanuratschaum
PCT/EP2009/054694 WO2009130194A1 (fr) 2008-04-25 2009-04-21 Mousse de polyisocyanurate contenant de la silicone

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GB201106016D0 (en) * 2011-04-08 2011-05-25 Heales Entpr Ltd Polymers
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CN102015805A (zh) 2011-04-13
JP2011518906A (ja) 2011-06-30
WO2009130194A8 (fr) 2010-10-14
DE102008001384A1 (de) 2009-10-29
WO2009130194A1 (fr) 2009-10-29

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