EP3728372A1 - Polyurethane hybrid polymers and process for the production thereof - Google Patents
Polyurethane hybrid polymers and process for the production thereofInfo
- Publication number
- EP3728372A1 EP3728372A1 EP18819103.5A EP18819103A EP3728372A1 EP 3728372 A1 EP3728372 A1 EP 3728372A1 EP 18819103 A EP18819103 A EP 18819103A EP 3728372 A1 EP3728372 A1 EP 3728372A1
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- European Patent Office
- Prior art keywords
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- polyol
- polyols
- groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
- C08G18/2027—Heterocyclic amines; Salts thereof containing one heterocyclic ring having two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
- C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/6262—Polymers of nitriles derived from alpha-beta ethylenically unsaturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
Definitions
- the present invention relates to polyurethane hybrid polymers and a process for their
- the water absorption of the material material used is an important property.
- the water absorption of polyurethanes is strongly influenced by the polyols used; e.g. ethylene oxide-rich polyether polyols have a higher tendency to absorb water than propylene oxide-rich polyether polyols.
- Water absorption leads to material softening, swelling and susceptibility to mechanical damage.
- polyester polyols can reduce water absorption, such products are susceptible to hydrolysis-induced polymer degradation.
- Semi-crystalline hydrocarbon compounds which can react with isocyanates via OH, NH or SH groups and thus help to reduce the water absorption can be helpful
- Polyurethane hybrid material accessible examples of such compounds are known from the literature. These are polyacrylates and / or polystyrenes containing corresponding isocyanate-reactive groups.
- Solvent be reacted with diisocyanate to polyurethane. After removal of the solvent and drying, a polyurethane precipitate is obtained. The solvent is required for the reaction to take place to the polyurethane.
- Solvent prepared by means of polyurethane macroazoinitiatoren (PUMAI).
- these polyurethane macroazo initiators (PUMAI) are prepared from methylenediphenyl diisocyanate (MDI) and azobis (2-cyanopropanol (ACP) in butanone.) The resulting NCO-terminated
- Polymer 46 (2005), pages 11294-11300 describes polyurethane-polystyrene copolymers
- the 2-hydroxyethyl acrylate-terminated isophorone diisocyanate-polytetramethylene glycol NCO prepolymer is prepared by RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization with styrene using 4 - ((benzodithioyl) methyl) benzoic acid as the RAFT agent.
- the Styrolkoniponente is polymerized on the already existing polyurethane.
- the resulting copolymer films show low water absorption (15-18%).
- the films of the polyurethane-polystyrene copolymers show a significantly increased hardness and tensile strength with a greatly reduced elongation at break compared to the pure films made of polyurethane.
- the object of the present invention was to provide polyurethanes which have a low water absorption, which can be prepared simultaneously and without the use of solvents, and in which rapid phase stability of the mixture of the
- Polystyrene polyol compounds with number average molecular weights of> 1000 g / mol and polyacrylonitrile compounds with number average molecular weights of> 3000 g / mol are usually solid, whereby their immediate processibility in the conventional processing technology for the production of polyurethanes is severely limited. For this reason, polystyrene polyols and polyacrylonitrile could previously be used only in solvents.
- the process according to the invention is distinguished, in particular, by preparing NCO prepolymers from polystyrene polyols and / or polyacrylonitrile polyols with polyisocyanates, which are processed in a further step to give polyurethane hybrid polymers.
- the invention provides polyurethane hybrid polymers of polyisocyanates (A) and isocyanate-reactive group-containing compounds (B) in a molar ratio of NCO groups to OH and / or NPI groups of from 0.8 to 1 to 3.5: 1 from the reaction of a) at least one NCO prepolymer as polyisocyanate (A),
- At least one isocyanate-reactive group-containing compound (B) from the group consisting of polyester polyols, polyether polyols, Polyetheresterpolyolen and amino-terminated polyethers and
- the NCO prepolymer has an NCO content of 10 to 40 wt .-% and at least one polyisocyanate (A ') from the group consisting of aliphatic and aromatic polyisocyanates and at least one polyol component (B ') from the group consisting of polystyrene polyol having a number average molecular weight of> 1000 g / mol, preferably> 1500 g / mol, more preferably 2000 g / nolole and polyacrylonitrile polyol having a number average molecular weight of> 2000 g / mol, preferably> 3000 g / mol, and optionally at least one further polyol (B ") is prepared from the group consisting of polyester polyols, polyether polyols and polyetheresterpolyols.
- Another object of the invention is a process for the preparation of polyurethane hybrid polymers, wherein polyisocyanates (A) containing isocyanate-reactive groups
- polyisocyanate (A ') selected from the group consisting of aliphatic and aromatic polyisocyanates and at least one polyol component (B') selected from the group consisting of polystyrene polyol having a number-average molecular weight of> 1000 g / mol, preferably> 1500 g / mol, particularly preferably 2000 g / mol and polyacrylonitrile polyol having a number average molecular weight of> 2000 g / mol, preferably> 3000 g / mol, and optionally at least one further polyol (B ") from the group consisting of polyester polyols, polyether polyols and polyether ester polyols, and ii) as isocyanate-reactive group-containing compound (B) at least one compound from the group consisting of polyester polyols, polyether polyols, polyether ester polyols and amino-terminated polyethers is used.
- the process according to the invention enables the
- polystyrene and polyacrylonitrile polyols used are compounds which have the following formula and are prepared as follows:
- RCH CH 2 + H [0-R '] m is 0-C (0) -R ", -SC (S) -SR' -C (0) -0 [-R'-0] m -H ->
- R is an aromatic radical C6H5 or a nitrile radical CN.
- N, n ', m and m' are each an integer> 1.
- R 'and R are alkylene radicals.
- any compound useful in polyurethane production having at least two isocyanate-reactive groups having hydrogen atoms can be used.
- Polyetherpolyols, polyesterpolyols, polyetheresterpolyols and amino-terminated polyethers or mixtures thereof are preferably used as compounds which are reactive toward isocyanate groups. Particularly preferred are polyether polyols.
- Suitable polyether polyols may be prepared by known methods, for example by anionic polymerization with alkali metal hydroxides, such as sodium or potassium hydroxide, or alkali metal such as sodium, sodium or potassium, or potassium isopropoxide as catalysts and with the addition of at least one starter molecule containing 2 to 8 reactive hydrogen atoms bound, or by cationic polymerization with Lewis acids, such as antimony pentachloride and borofluoride etherate, or bleaching earth as catalysts of one or more alkylene oxides having 2 to 4
- Multimetal cyanide compounds so-called DMC catalysts can be used.
- Suitable alkylene oxides are, for example, tetrahydrofuran, 1, 3-propylene oxide, 1, 2 or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1, 2-propylene oxide.
- the alkylene oxides can be used individually, alternately in succession or as mixtures.
- Suitable starter molecules are, for example: water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid and terephthalic acid, aliphatic and aromatic, optionally N-mono-, N, N and N, N'-dialkyl-substituted diamines having 1 to 4 carbon atoms in the alkyl radical, such as optionally mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1, 2, 1, 3, 1, 4, 1, 5 and 1, 6 Hexamethylenediamine, phenylenediamines, 2,3-, 2,4- and 2,6-toluenediamine and 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane.
- organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid and ter
- alkanolamines such as ethanolamine, diethanolamine, N-methyl and N-ethyl-ethanolamine, N-methyl and N-ethyldiethanolamine and triethanolamine and ammonia.
- polyhydric especially dihydric to polyhydric alcohols, such as ethanediol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerytrite, glucose , Fructose and sucrose.
- the polyether polyols preferably polyoxyethylene, polyoxypropylene, and polyoxypropylene polyoxyethylene polyols, have a number average functionality of from 1.5 to 5.0, preferably from 1.8 to 4.2, and more preferably from 2.0 to 3.5, and number average molecular weights of preferably 32 to 1500, more preferably 60 to 1000 and especially 60 to 800.
- polyester polyols which can be used according to the invention have predominantly hydroxyl end groups.
- Suitable polyester polyols may have molecular weights in the range from 250 Da to 10,000 Da, preferably from 300 Da to 6000 Da.
- the number of hydroxyl end groups in the polyester polyol can be 2 to 6.
- the average functionality of the polyester polyols is preferably> 2 to ⁇ 3.
- Low molecular weight polyols which can be used to prepare the polyesterpolyols are preferably those having hydroxyl functionalities of 2 to 6. In preferred embodiments, they have between 2 and 36, more preferably between 2 and 12, carbon atoms. Preferably, at least 90 mol%, particularly preferably 100 mol%, of all alcohol groups of the alcohol component of which the polyester is synthesized originate from unbranched a, w-diols (based on a total content) Alcohol groups in the alcohol component from which the polyester is built up, from 100 mol%)). Very particular preference is given to polyols from the group:
- Ethylene glycol and diethylene glycol including their higher homologues, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1, 10-decanediol, 1,1,1-undecanediol, 1,12-dodecanediol, including their higher homologs.
- the said polyols preferably contribute at least 90 mol% of all hydroxyl groups.
- Low molecular weight polycarboxylic acid equivalents which can be used to prepare the polyesterpolyols have, in particular, 2 to 36, preferably 2 to 12, carbon atoms.
- the low molecular weight polycarboxylic acid equivalents which can be used to prepare the polyesterpolyols have, in particular, 2 to 36, preferably 2 to 12, carbon atoms.
- Polycarboxylic acid equivalents may be aliphatic or aromatic. They are preferably selected from the group:
- polycarboxylic acids preferably contribute at least 90 mol% of all the carboxyl groups. If hydroxycarboxylic acids, including their internal anhydrides (lactones), are used or co-used, it is preferred to use caprolactone and / or 6-hydroxycaproic acid.
- polyetherester polyols the compounds described in EP1702941A1 can be used.
- polyether polyols for example, the so-called Jeffamine® Huntsman, such as. B. D-230, D-400, D-2000, T-403, T-3000, T-5000, or corresponding products of BASF, such as.
- polyetheramine D230, D400, D200, T403, T5000 or polytetrahydrofuranamines (BASF product: Polytetrahydrofuranamin 1 700) are used.
- chain extenders and / or crosslinkers (C) substances which have at least two isocyanate-reactive groups, wherein the substances have at least one free SH, OH or NH group.
- the following compounds are illustrative: ethylenediamine, 1,2-propanediol, 1,3-propanediol, glycerol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methylpropan-1, 3-diol, 1, 2-pentanediol, l, 3-pentanediol, 1, 4-pentanediol, l, 5-pentanediol, 2,2-dimethyl-propane-l, 3-diol, 2-methyl-butan-l, 4- diol, 2-methylbutan-1,3-diol, monoethylene glycol, 1,1-trimethylolethane, 3-methyl-1,5-pent
- polyisocyanates (A ') preference is given to using aromatic polyisocyanates for the preparation of the prepolymers in the case of the subsequent reaction with polystyrene polyols.
- aromatic polyisocyanates of the general formula R (NCO) z are used, wherein R is a polyvalent organic radical having an aromatic, and z is an integer of at least 2.
- R is a polyvalent organic radical having an aromatic
- z is an integer of at least 2. Examples for this are: 4,4'-diisocyanatobenzene, 1, 3-diisocyanato-o-xylene, 1, 3-diisocyanato-p-xylene, 1, 3-diisocyanato-mxylol, 2,4-diisocyanato-l-chlorobenzene, 2,4-diisocyanato -l-nitrobenzene, 2,5-diisocyanato-1-nitrobenzene, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6
- toluene diisocyanates 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyl methane diisocyanate, Polymethylenpolyphenylenpolyisocyanat, and derivatives, such as modified compounds of these isocyanates in the form of carbodimides, urethyimines, and / or isocyanurates and mixtures thereof.
- polyacrylonitrile polyols preferably contain the known aliphatic
- Exemplary here are l, 6-hexamethylene diisocyanate, isophorone diisocyanate,
- Methyldicyclohexyldiisocyanate H12-MDI
- H12-MDI Methyldicyclohexyldiisocyanate
- modified compounds of these isocyanates in the form of allophanates, biurets and carbodiimides, and dimers and trimers of isocyanates (U. Meier-Westhues, Polyurethanes - Coatings, Adhesives and Sealants, Hannover: Vincentz Network, 2007 (European Coatings Tech Files) ISBN 3-87870-334-1).
- Suitable polyols (B ') for the preparation of the isocyanate-terminated prepolymers are the polyols based on acrylonitrile or styrene accessible via RAFT polymerization.
- catalysts (D) it is possible to use all catalysts customary for polyurethane production. Such catalysts are described, for example, in “Kunststoffhandbuch, Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.4.1.
- organic metal compounds preferably organic tin compounds, such as tin (II) salts of organic carboxylic acids, for example, tin (II) acetate, tin (II) octoate, tin (II) ethylhexanoate and tin (II) laurate, and the dialkyltin (IV) salts of organic carboxylic acids, eg, dibutyltin diacetate , Dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate, as well as bismuth carboxylates such as bismuth (III) neodecanoate, bismuth 2-ethylhexanoate and bismuth octanoate or mixtures.
- Other possible catalysts are strongly basic amine catalysts. Examples of these are amidines, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrim
- Tributylamine dimethylbenzylamine, N-methyl, N-ethyl, N-cyclohexylmorpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N, N ', N' Tetramethylhexanediamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, bis (dimethylaminopropyl) urea, dimethylpiperazine, 1, 2-dimethylimidazole, 1-azabicyclo- (3, 3, 0) -octane and preferably 1, 4- Diazabicyclo (2,2,2) octane and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyl and N-ethyl-diethanolamine and dimethylethanolamine.
- the catalysts can be used singly or as mixtures. If appropriate, mixtures of metal catalysts and basic amine catalysts are used as catalysts (D).
- the catalysts (D) can be used, for example, in a concentration of 0.001 to 5 wt .-%, in particular 0.05 to 2 wt .-% as catalyst or catalyst combination, based on the weight of components (A) to (E) ,
- auxiliaries and / or additives (E) blowing agents additives for thixotropy, fillers, antioxidants, dyes, pigments, release agents, optical brighteners and stabilizers against heat, light and / or UV radiation, plasticizers or surface-active substances can be used.
- Suitable release agents are: reaction products of fatty acid esters with polyisocyanates, salts of polysiloxanes containing amino groups and fatty acids, salts of saturated or unsaturated (cyclo) aliphatic carboxylic acids having at least 8 carbon atoms and tertiary amines and in particular internal release agents such as carboxylic acid esters and / or amides prepared by esterification or amidation of a mixture of montanic acid and at least one aliphatic carboxylic acid having at least 10 C atoms with at least the functional
- blowing agents it is possible to use all blowing agents known for the preparation of polyurethanes. These may include chemical and / or physical blowing agents. Such blowing agents are described, for example, in "Kunststoffhandbuch, Volume 7, Polyurethane", Carl Hanser Verlag, 3.
- Chemical blowing agents are compounds which form gaseous products by reaction with isocyanate. Examples of such propellants are water or carboxylic acids.
- physical blowing agents are meant compounds which are dissolved or emulsified in the starting materials of polyurethane production and evaporate under the conditions of polyurethane formation.
- hydrocarbons for example, hydrocarbons, halogenated hydrocarbons and other compounds, such as fluorinated alkanes (hydrofluorocarbons - eg HFC245fa or HFC365mfc), such as perfluorohexane, chlorofluorocarbons, hydrofluoroolefins (HF01336mzz, HF01233zd)) and ethers, esters, ketones and / or acetals , fluorinated alkanes (hydrofluorocarbons - eg HFC245fa or HFC365mfc), such as perfluorohexane, chlorofluorocarbons, hydrofluoroolefins (HF01336mzz, HF01233zd)) and ethers, esters, ketones and / or acetals ,
- fluorinated alkanes hydrofluorocarbons - eg HFC245fa or HFC365mf
- the polyurethane hybrid polymers can be used for the production of hydrophobic compact coatings and hydrophobic hard and soft foams.
- Reaction temperature increased to l00 ° C and stirred for 6 hours at this temperature.
- the RAFT reagent II may, for example, have the following structure:
- Polystyrene diol III number average molecular weight M w : 2100 g / mol,
- Catalyst Dabco 33LV from Air Products Polyisocyanate 1 4,4'-diphenylmethane diisocyanate having an isocyanate content of 33.6
- Polyisocyanate containing 2 oligomeric uretonimines 4,4 '-Diphenylmethandiisocyanat having an isocyanate content of 29.5 wt .-% (Desmodur® CD-S from Covestro GmbH AG)
- Polyether polyol 1 Gylzerin started polyether polyol from propylene oxide having an OH number of 42 mg KOH / g
- Polyetherpolyol 2 Linear, propylene glycol initiated propylene oxide polyether polyol having an OH number of 56 mg KOH / g polyether polyol 3 glycerol started polyether polyol of propylene oxide and ethylene oxide having an OH number of 35 mg KOH / g
- the polystyrene diol III was crushed, added at 80 ° C to the polyisocyanate component, where it dissolved and was converted to the NCO prepolymer.
- the second NCO prepolymer was treated in the same way with the corresponding liquid
- Both NCO prepolymers could be converted to the polyurethane under the conditions customary in polyurethane chemistry (room temperature, intensive stirring).
- NCO prepolymers were reacted according to the amounts shown in Table 2 to the polyurethane or polyurethane-polystyrene hybrid polymer.
- the catalyst with the polyol was intimately mixed with an Ika stirrer RW20 for 5 minutes. This mixture was added at room temperature to the amount of the respective prepolymer put in a paper cup and slowly stirred with a wooden stick. The mass of about 80g was transferred to a non-tempered aluminum mold (9x9x2cm 3 ) with removable frame. The reaction mixture was cured under these conditions.
- a preparation of polyurethane hybrid polymers via the so-called one-shot process was surprisingly not possible. Even at a processing temperature of 50 ° C, the polystyrene diol apparently does not dissolve sufficiently rapidly in a reaction mixture consisting of polyether polyol, catalyst and diphenylmethane diisocyanate to participate in the reaction. However, it has surprisingly been found that the preparation can be carried out solvent-free, if the preparation is carried out via the Prepolymerweg.
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- Health & Medical Sciences (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
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EP17209216.5A EP3502154A1 (en) | 2017-12-21 | 2017-12-21 | Polyurethane hybrid polymers and method for its production |
PCT/EP2018/084866 WO2019121355A1 (en) | 2017-12-21 | 2018-12-14 | Polyurethane hybrid polymers and process for the production thereof |
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EP17209216.5A Pending EP3502154A1 (en) | 2017-12-21 | 2017-12-21 | Polyurethane hybrid polymers and method for its production |
EP18819103.5A Withdrawn EP3728372A1 (en) | 2017-12-21 | 2018-12-14 | Polyurethane hybrid polymers and process for the production thereof |
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EP17209216.5A Pending EP3502154A1 (en) | 2017-12-21 | 2017-12-21 | Polyurethane hybrid polymers and method for its production |
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US (1) | US10889679B2 (en) |
EP (2) | EP3502154A1 (en) |
CN (1) | CN111527117A (en) |
WO (1) | WO2019121355A1 (en) |
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US3715337A (en) * | 1971-06-01 | 1973-02-06 | Minnesota Mining & Mfg | Preparation of poly(isocyanurate-urethanes) using trithiocarbonates as catalysts |
DE3405875A1 (en) | 1984-02-18 | 1985-08-22 | Basf Ag, 6700 Ludwigshafen | METHOD FOR THE PRODUCTION OF CELLED OR COMPACT POLYURETHANE-POLYHANE MOLDED BODIES WITH IMPROVED DEFLECTING PROPERTIES AND INNER MOLD RELEASE AGENT FOR THE POLYISOCYANATE POLYADDITION METHOD |
DE3607447A1 (en) | 1986-03-07 | 1987-09-10 | Basf Ag | METHOD FOR PRODUCING MOLDED BODIES WITH A CELLED CORE AND A COMPRESSED EDGE ZONE WITH IMPROVED DEFORMING PROPERTIES |
DE3631842A1 (en) | 1986-09-19 | 1988-03-24 | Basf Ag | INNER MOLD RELEASE AGENTS, THE USE THEREOF FOR THE PRODUCTION OF MOLDED BODIES BY THE POLYISOCYANATE POLYADDITIONAL PROCESS AND METHOD FOR THE PRODUCTION OF THE MOLDED BODIES |
DE69228174T2 (en) * | 1991-08-05 | 1999-09-02 | Nippon Catalytic Chem Ind | PREPARATION OF A POLYMER HYDROXILIZED ON BOTH END, THE COMPOSITION CONTAINING IT, THEIR USE, THE POLYMER DERIVED THEREOF AND THEIR USE |
SG71011A1 (en) * | 1996-01-29 | 2000-03-21 | Shell Int Research | Polymer polyol and process for the preparation of polymer polyols |
US6596899B1 (en) * | 2000-02-16 | 2003-07-22 | Noveon Ip Holdings Corp. | S,S′BIS-(α, α′-DISUBSTITUTED-α″-ACETIC ACID)- TRITHIOCARBONATES AND DERIVATIVES AS INITIATOR-CHAIN TRANSFER AGENT-TERMINATOR FOR CONTROLLED RADICAL POLYMERIZATIONS AND THE PROCESS FOR MAKING THE SAME |
US7557235B2 (en) * | 2000-02-16 | 2009-07-07 | Lubrizol Advanced Materials, Inc. | Hydroxyl-terminated thiocarbonate containing compounds, polymers, and copolymers, and polyurethanes and urethane acrylics made therefrom |
DE102005012794A1 (en) | 2005-03-19 | 2006-09-21 | Bayer Materialscience Ag | Poly (ether-ester) polyols and process for their preparation |
US20080071056A1 (en) * | 2006-09-14 | 2008-03-20 | Borst Joseph P | Method of forming a graft polyol and polyurethane article formed from the graft polyol |
DE102006052987A1 (en) * | 2006-11-10 | 2008-05-15 | Bayer Materialscience Ag | Plastic composite elements and a method for their production |
AU2007347458B2 (en) * | 2007-02-23 | 2013-11-14 | Commonwealth Scientific And Industrial Research Organisation | Process for transforming the end groups of polymers |
CN101143916B (en) * | 2007-08-30 | 2010-11-17 | 复旦大学 | Method for preparing three hetero arms asteroid polymer |
CN105199050B (en) * | 2015-09-11 | 2018-06-08 | 湘潭大学 | A kind of polyurethane grafted copolymer and preparation method thereof |
US11041026B2 (en) * | 2017-01-30 | 2021-06-22 | Massachusetts Institute Of Technology | Reactions enabled by thermoresponsive and photoresponsive gels |
US10526484B2 (en) * | 2017-12-20 | 2020-01-07 | Covestro Llc | Dithiocarbonate containing polyols as polymer polyol stabilizers |
EP3502094A1 (en) * | 2017-12-21 | 2019-06-26 | Covestro Deutschland AG | Method for the preparation of telechelic polymers polyols from trithiocarbonates |
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2017
- 2017-12-21 EP EP17209216.5A patent/EP3502154A1/en active Pending
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2018
- 2018-12-14 WO PCT/EP2018/084866 patent/WO2019121355A1/en unknown
- 2018-12-14 CN CN201880081752.1A patent/CN111527117A/en active Pending
- 2018-12-14 EP EP18819103.5A patent/EP3728372A1/en not_active Withdrawn
- 2018-12-14 US US16/764,999 patent/US10889679B2/en active Active
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US10889679B2 (en) | 2021-01-12 |
EP3502154A1 (en) | 2019-06-26 |
US20200308333A1 (en) | 2020-10-01 |
WO2019121355A1 (en) | 2019-06-27 |
CN111527117A (en) | 2020-08-11 |
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