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WO2014060329A2 - Élastomères polyuréthanes et leur production - Google Patents

Élastomères polyuréthanes et leur production Download PDF

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Publication number
WO2014060329A2
WO2014060329A2 PCT/EP2013/071378 EP2013071378W WO2014060329A2 WO 2014060329 A2 WO2014060329 A2 WO 2014060329A2 EP 2013071378 W EP2013071378 W EP 2013071378W WO 2014060329 A2 WO2014060329 A2 WO 2014060329A2
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WIPO (PCT)
Prior art keywords
mol
groups
polyol
polyurethane elastomers
catalysts
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PCT/EP2013/071378
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German (de)
English (en)
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WO2014060329A3 (fr
Inventor
Kai LAEMMERHOLD
Florian HUPKA
Hartmut Nefzger
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Covestro Deutschland AG
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Bayer MaterialScience AG
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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
    • 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
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates

Definitions

  • the invention relates to Polyethercarbonatpolyolen based polyurethane elastomers and a process for their preparation by using based on polyethercarbonate polyols isocyanate (NCO) prepolymers.
  • NCO polyethercarbonate polyols isocyanate
  • Polyurethane (PUR) elastomers are of great industrial importance because of their excellent mechanical properties. By using different chemical components, their mechanical properties can be varied over a wide range.
  • PUR elastomers are built up from linear polyols, usually polyester, polyether or polycarbonate polyols, organic diisocyanates and short-chain compounds with 2 isocyanate-reactive groups (chain extenders). To accelerate the formation reaction, additional catalysts can be added. The molar ratios of the constituent components can be varied over a wide range, which can adjust the properties of the product. Depending on the molar ratios of polyols to chain extenders products result in a wide Shore hardness range.
  • the structure of the polyurethane elastomers is preferably carried out stepwise (Prepolymerv experienced).
  • an isocyanate-containing prepolymer is first prepared from the polyol and the diisocyanate, which is reacted in a second step with the chain extender.
  • the PU elastomers can be prepared continuously or preferably discontinuously.
  • PUR elastomers based on polyethylene oxide and / or polypropylene oxide polyols C2 or C3 polyether polyols
  • C2 or C3 polyether polyols which are prepared by known processes using KOH or multimetal cyanide
  • Catalysis can be prepared by polymerization of ethylene oxide and / or propylene oxide, characterized by a good overall property image.
  • the fast solidification rate, as well as the very good microbial resistance of the resulting use parts are worth mentioning.
  • Such parts need to be improved with regard to the mechanical properties, such.
  • WO 2010/115567 describes the preparation of microcellular elastomers by reacting an NCO-terminated prepolymer (from an isocyanate and a first polyol), wherein the prepolymer is then mixed with a second polyol (molecular weight from 1000 to 10000 g / mol) and a Chain extender (molecular weight of less than 800 g / mol) is reacted.
  • the microcellular structure is created by the use of physical or chemical blowing agents, such as water.
  • Polyols which can be used are polyether carbonate polyols which are prepared by copolymerization of CO 2 and alkylene oxides.
  • the complicated use of a second polyol proves to be disadvantageous. From an application point of view, the use of only one polyol would be desirable.
  • polyurethane resins which are based on polyether carbonate diols, which are obtained by transesterification of carbonate esters, such as.
  • dimethyl carbonate with polyether diols having a molecular weight below 500 g / mol can be prepared.
  • the polyethercarbonate diols are prepared by a complicated, costly two-stage synthesis. It is an object of the present invention to provide cost-effective PU elastomers and a process for the production of cost-effective PU elastomers which have a good overall property profile and, in addition, good mechanical properties and are therefore suitable for a broad range of applications.
  • the PUR elastomers produced should, in addition to a better feedability, have good stability to hydrolysis.
  • This object could be achieved according to the invention by the polyurethane elastomers described in more detail below and by a process for their preparation.
  • the invention relates to polyurethane elastomers obtainable from the reaction of the components from the group consisting of an NC O-terminated prepolymer obtainable from the reaction of the components selected from the group consisting of
  • Groups preferably naphthalene-1, 5-diisocyanate and B) at least one polyol having a number average molecular weight of 500 to 5000 g / mol and a functionality of 2 to 4, preferably 2,
  • Another object of the invention is a process for the preparation of polyurethane elastomers, wherein in a first step i) an NCO-terminated prepolymer consisting of the components consisting of
  • step ii) the prepolymer from step i) exclusively with components from the group consisting of
  • chain extenders and / or crosslinkers having a molecular weight of 60 to 490 g / mol, a functionality of 2 to 3 and excluding OH groups as isocyanate-reactive groups in the molecule in the presence of F) optionally catalysts and / or
  • the component B) at least one Polyethercarbonatepolyol in an amount of at least 20 wt .-%, based on the component B), which by addition of carbon dioxide and alkylene oxides having three or four carbon atoms to H-functional starter substances using catalyst reu.
  • Preferably bimetal cyanide catalysts is obtained.
  • the PUR elastomers produced by the process according to the invention have good mechanical properties.
  • a better processability and a comparable hydrolysis stability than in the case of corresponding PU elastomers based on pure polycarbonate polyols can be observed.
  • Suitable organic polyisocyanates A) are preferably diisocyanates, as described in Justus Liebigs Annalen der Chemie, 562, pp. 75-136.
  • diphenylmethane diisocyanate isomer mixtures having a 4,4'-diphenylmethane diisocyanate content of> 96% by weight and in particular 4,4'-diphenylmethane diisocyanate and 1,5-diisocyanate diisocyanate.
  • the diisocyanates mentioned can be used individually or in the form of mixtures with one another.
  • polyisocyanates for example triphenylmethane-4,4 ', 4 "-triisocyanate or polyphenyl polymethylene polyisocyanates.
  • the organic polyisocyanate A) is naphthalene-1, 5-diisocyanate (NDI).
  • component B) comprises at least one polyethercarbonate polyol which can be obtained by addition of carbon dioxide and alkylene oxides having at least 3 or 4 carbon atoms to H-functional starter substances using catalysts, preferably bimetallic acid catalysts.
  • catalysts preferably bimetallic acid catalysts.
  • H-functional is understood to be a starter compound which has active H atoms in relation to alkoxylation.
  • H-functional initiators using DMC catalysts are known, for example, from EP-A 0222453, WO 2008/013731 and EP-A 21 15032.
  • the polyethercarbonate polyol has one
  • Carbonate groups calculated as CO 2 , from 3 to 30 wt .-%, preferably from 5 to 25 wt .-% and particularly preferably from 10 to 25 wt .-% determined by NMR spectroscopy on.
  • the proportion of incorporated CO 2 in the polyether carbonate polyols is determined by means of 1 l-NM R (Bruker, DPX 400, 400 MHz, pulse program zg30, waiting time dl: 5 s, 100 scans). The sample is in each case dissolved in definite chloroform. As an internal standard, dimethyl therephthalate (2 mg to 2 g CDCl 3 ) is added to the indicated solvent.
  • dimethyl therephthalate (2 mg to 2 g CDCl 3 ) is added to the indicated solvent.
  • Carbonate resulting from carbon dioxide incorporated in the polyethercarbonate polyol (resonances at 5.2 to 4.8 ppm), unreacted PC) with resonance at 2.4 ppm, polyether polyol (ie, no incorporated carbon dioxide) with resonances at 1.2 to 1.0 ppm.
  • the polyethercarbonate polyol has a number average molecular weight of 600 to 4500 g / mol, preferably 700 to 4000 g / mol, more preferably 750 to 3000 g / mol and most preferably 1000 to 2000 g / mol, determined by End group titration and GPC (gel permeation chromatography).
  • a suitable H-functional starter substance compounds with active for the alkoxylation H atoms can be used.
  • alkoxylation active groups with active I I atoms are, for example, OH groups in an amount of 2 to 6, preferably from 2 to 3 per molecule.
  • one or more compounds selected from the group consisting of polyhydric alcohols, polyether polyols, polyester polyols, polyester ether polyols, polyether carbonate polyols and polycarbonate polyols are used as the I-functional starter substance.
  • Polyhydric alcohols suitable as H-functional starter substances are, for example, dihydric alcohols, for example ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol, neopentyl glycol, 1 , 5-pentanediol, methylpentanediols (such as 3-methyl-l, 5-pentanediol), 1,6-hexanediol; 1,8-octanediol, 1,10-decanediol, 1, 12-dodecanediol, bis (hydroxymethyl) cyclohexanes (such as, for example, 1,4-bis (hydroxymethyl) cyclohexane), triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropy
  • the H-functional starter substances may also be selected from the class of polyether polyols, in particular those having a number average molecular weight Mn in the range from 100 to 4000 g / mol, preferably from 400 to 800.
  • Polyether polyols consisting of repeating ethylene oxide and propylene oxide units are preferred are constructed, preferably with a proportion of 35 to 100% propylene oxide, more preferably in a proportion of 50 to 100% propylene oxide units.
  • These may be random copolymers, gradient copolymers, alternating or block copolymers of ethylene oxide and propylene oxide.
  • Suitable polyether polyols made up of repeating ethylene oxide units or propylene oxide and are, for example Desmophen ® -, Acclaim ® -, Arcol ® -, Baycoll ® -, Bayfill ® -,
  • polyether polyols from Bayer MaterialScience AG such as Desmophen ® 3600Z, Desmophen® 1900U ®, Acclaim ® Polyol 2200, Acclaim ® Polyol 40001, Arcol ® Polyol 1004 Arcol ® polyol 1010 Arcol ® polyol 1030 Arcol polyol ® 1070, Baycoll BD ® 1110 Bayfill VPPU ® 0789, Baygal ® K55, PET ® 1004 Poiyether ® S180).
  • suitable homo- polyethylene oxides are the BASF SE example Pluriol ® E-marks suitable homo- polypropylene oxides are, for example Pluriol ® P brands from BASF SE, suitable mixed copolymers of ethylene oxide and propylene oxide such as the Pluronic ® PE or PLURIOL ® RPE Brands of BASF SE.
  • the H-functional starter substances can also be selected from the substance class of the polyesterpolyols, in particular those having a number average molecular weight Mn in the range from 200 to 4500 g / mol.
  • Polyester polyols used are at least difunctional polyesters. Polyester polyols preferably consist of alternating acid and alcohol units. As acid components z.
  • succinic acid maleic acid, maleic anhydride, adipic acid, phthalic anhy drid, phthalic acid, isophthalic acid, T erephthals acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or mixtures of said acids and / or anhydrides used.
  • alcohol components z.
  • polycarbonate polyols for example polycarbonate diols
  • H-functional starter substances in particular those having a number average molecular weight Mn in the range from 150 to 4500 g / mol, preferably 500 to 2500, which are obtained, for example, by reacting phosgene, dimethyl carbonate, Diethyl carbonate or diphenyl carbonate and di- and / or polyfunctional alcohols or polyester polyols or polyether polyols are produced.
  • polycarbonate polyols are found, for. As in EP-A 1359177.
  • Desmophen ® C types of Bayer MaterialScience AG can be used, such as. B. Desmophen ® C 1100 or Desmophen ® C 2200th
  • polyether carbonate polyols can be used as H-functional starter substances.
  • polyether carbonate polyols prepared by the process described herein are used.
  • These polyether carbonate polyols used as H-functional starter substances are prepared beforehand in a separate reaction step for this purpose.
  • the H-functional starter substances generally have a functionality (i.e., number of H atoms per molecule active for the polymerization) of 2 to 6, preferably 2 or 3.
  • the H-functional starter substances are used either individually or as a mixture of at least two H-functional starter substances.
  • Preferred H-functional starter substances are alcohols of the general formula (I),
  • alcohols according to formula (I) are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol.
  • H-functional starter substances are eopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, reaction products of the alcohols of the formula (I) with ⁇ -caprolactone, for example reaction products of trimethylolpropane with ⁇ -caprolactone, reaction products of glycerol with ⁇ -caprolactone, and reaction products of Pentaerythritol with ⁇ -caprolactone.
  • Preference is furthermore given to using water, diethylglycol, dipropylene glycol, castor oil, sorbitol and polyetherpolyols composed of repeating polyalkylene oxide units as H-functional starter substances.
  • the H-functional starter substances are one or more compounds selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-butanediol, Pentanediol, 2-methylpropane-1, 3-diol, neopentyl glycol, 1, 6-hexanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, di- and tri functional polyether polyols, wherein the polyether polyol is composed of a di- or tri-H-functional starter substance and propylene oxide or a di- or tri-H-functional starter substance, propylene oxide and ethylene oxide.
  • the polyether polyols preferably have a number average molecular weight Mn in the range of 62 to 4500 g / mol and a functionality of 2 to 3 and in particular a number average molecular weight Mn in the range of 62 to 3000 g / mol and a functionality of 2 to 3.
  • Catalysts in particular dimetal cyanide (DMC) catalysts, are known in principle from the prior art for the homopolymerization of epoxides (see, for example, US Pat. No. 3,404,109, US Pat. No. 3,829,505, US Pat. No. 3,941,849 and US Pat 158 922).
  • the catalysts used for the preparation are preferably DMC catalysts, e.g. in US Pat. No. 5,470,813, EP-A 700 949, EP-A 743 093, EP-A 761 708, WO 97/40086, WO 98/16310 and WO 00/47649.
  • a typical example is the highly active DMC catalysts described in EP-A 700 949 which, in addition to a double metal cyanide compound (eg zinc hexacyanocobaltate (III)) and an organic complex ligand (eg tert.-butanol), also have a polyether with a molecular weight of average molecular weight contained as 500 g / mol.
  • a double metal cyanide compound eg zinc hexacyanocobaltate (III)
  • an organic complex ligand eg tert.-butanol
  • Suitable double metal chloride compounds a) are zinc hexacyanocobaltate (III), zinc hexacyanoiridate (III), zinc hexacyanoferrate (III) and cobalt (II) hexacyanocobaltate (III). Further examples of suitable double metal cyanide compounds are e.g. US Pat. No. 5,158,922 (column 8, lines 29-66). Zinc hexacyanocobaltate (III) is particularly preferably used.
  • the preparation of the polyethercarbonate polyols preferably takes place in a pressure reactor.
  • the dosage of one or more alkylene oxides and of the carbon dioxide is carried out after the optional drying of a starter substance or the mixture of several starter substances and the addition of the DMC catalyst and the / the additive (s), before or after drying as a solid or in the form of a suspension be added.
  • the metering of one or more alkylene oxides and the carbon dioxide can in principle take place in different ways.
  • the start of dosing can be carried out from the vacuum or at a previously selected form.
  • the admission pressure is preferably set by introducing an inert gas, such as for example nitrogen, the pressure being set between 10 mbar to 5 bar, preferably 3 00 mbar to 3 bar and preferably 500 mbar to 2 bar.
  • the metered addition of one or more alkylene oxides and of the carbon dioxide can be carried out simultaneously or sequentially, with the entire amount of carbon dioxide at once or metered over the reactor. can be added onszeit. Preferably, a dosage of carbon dioxide takes place.
  • the dosage of one or more alkylene oxides is carried out simultaneously or sequentially to the carbon dioxide dosage. If several alkylene oxides are used for the synthesis of the polyether carbonate polyols, then their metered addition can be carried out simultaneously or sequentially via separate dosages or via one or more dosages, with at least two alkylene oxides being metered in as a mixture.
  • By way of the method of metering the alkylene oxides and the carbon dioxide it is possible to synthesize random, alternating, blocky or gradient polyethercarbonate polyols.
  • an excess of carbon dioxide is used, in particular the amount of carbon dioxide is determined by the total pressure under reaction conditions. Due to the inertness of carbon dioxide, an excess of carbon dioxide is an advantage. It has been found that the reaction at 60 to 150 ° C, preferably at 70 to 140 ° C, more preferably at 80 to 130 ° C and pressures of 0 to 100 bar, preferably 1 to 90 bar and more preferably from 3 to 80 bar produces the polyethercarbonate polyols. At temperatures below 60 ° C, the reaction stops. At temperatures above 150 ° C, the amount of unwanted by-products increases sharply.
  • the proportion of polyether carbonate polyols in component B) is preferably 20 to 100% by weight, more preferably 40 to 100% by weight and most preferably 50 to 100% by weight.
  • component B in addition to the abovementioned polyether carbonate polyols, it is possible to use further linear hydroxyl-terminated polyols having a number-average molecular weight Mn of from 500 to 5000 g / mol. For production reasons, these often contain small amounts of nonlinear compounds. Therefore, one often speaks of "substantially linear polyols". Preference is given to polyester, polyether, polycarbonate or mixtures of these.
  • Suitable polyether diols can be prepared by reacting one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical with a starter molecule containing two active hydrogen atoms bound.
  • alkylene oxides which may be mentioned are: ethylene oxide, 1,2-propylene oxide, epichlorohydrin and 1,2-butylene oxide and 2,3-butylene oxide.
  • ethylene oxide, propylene oxide and mixtures of 1, 2-propylene oxide and ethylene oxide are used.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures.
  • starter molecules are: water, amino alcohols, such as N-alkyldiethanolamines, for example N-methyldiethanolamine, and diols, such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol ,
  • Suitable polyether diols are furthermore the hydroxyl groups. Tetrahydrofuran polymerization products. It is also possible to use tri-functional polyethers in proportions of from 0 to 30% by weight, based on the bifunctional polyethers, but at most in such an amount that a thermoplastically processable product is formed.
  • Suitable polyether diols have a number average molecular weight Mn of 500 to 5000 g / mol. They can be used both individually and in the form of mixtures with one another.
  • Suitable polyester diols can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, and polyhydric alcohols.
  • Suitable dicarboxylic acids are, for example: aliphatic dicarboxylic acids, such as succinic acid, maleic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid, and aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acids can be used singly or as mixtures, e.g. in the form of an amber, glutaric and adipic acid mixture.
  • the corresponding dicarboxylic acid derivatives such as carbonic diesters having 1 to 4 carbon atoms in the alcohol radical, carboxylic acid anhydrides or carbonyl chlorides.
  • polyhydric alcohols examples include glycols having 2 to 10, preferably 2 to 6 carbon atoms, such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,12- Dodecanediol, 2,2-dimethyl-l, 3-propanediol, 1,3-propanediol and dipropylene glycol.
  • the polyhydric alcohols may be used alone or optionally mixed with each other.
  • esters of carbonic acid with the diols mentioned in particular those having 4 to 6 carbon atoms, such as 1,4-butanediol or 1,6-hexanediol, condensation products of hydroxycarboxylic acids, for example hydroxycaproic acid and polymerization products of lactones, for example optionally substituted ones caprolactones.
  • Ethanediol polyadipates, 1,4-butanediol polyadipates, ethanediol-1, 4-butanediol polyadipates, 1,6-hexanediol neopentyl glycol polyadipates, 1,6-hexadexiol-1,4-butanediol polyadipates are preferably used as polyester diols and polycaprolactones.
  • the polyester diols have a number average molecular weight Mn of 500 to 5000 g / mol and can be used individually or in the form of mixtures with one another.
  • Components A) and B) are reacted in a first step to produce an urethane-terminated prepolymer according to the prepolymer method for the preparation of the polyurethane elastomer.
  • the amounts of the reaction components for prepolymer formation in the first step are selected such that the molar ratio of the NCO groups from A) to that of the isocyanate-reactive groups in B) is 1.1: 1 to 5: 1, preferably 1 , 1: 1 to 2.5: 1.
  • the components are intimately mixed with each other, and the prepolymer reaction is preferably substantially to complete conversion, based on the polyol component. Complete conversion can be determined by titration of the N CO value.
  • the prepolymer is then reacted exclusively with the component E) chain extender and / or crosslinker at 80 ° to 140 ° C.
  • component E are low molecular weight compounds with oil! And a molecular weight of 60 to 490 g / mol and a functionality of 2 to 3, used.
  • the components contain or consist of E) from diols.
  • Suitable chain extenders are diols such as, for example, ethanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, diesters of terephthalic acid with glycols having 2 to 4 carbon atoms, such as, for example, terephthalic acid-bis-ethylene glycol or terephthalic acid bis-1,4-butanediol, hydroxyalkylene ethers of hydroquinone, such as, for example, 1,4-di (- hydroxyethyl) hydroquinone and ethoxylated bisphenols.
  • diols such as, for example, ethan
  • Preferred chain extenders are aliphatic diols having 2 to 14 carbon atoms, such as, for example, ethanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1, 10-decanediol, 1, 12 -Dodecandiol, diethylene glycol, dipropylene glycol, neopentyl glycol and 1,4-butanediol. Particular preference is given to using 1,4-butanediol as chain extender.
  • reaction components can be reacted in amounts such that the molar ratio of the sum of the NCO groups from A) to the sum of the isocyanate-reactive groups from B) and E) 0.9: 1 to 1 , 2: 1.
  • the PUR elastomers prepared by the process according to the invention can be varied by adjusting the molar ratio of polyol B) to chain extender E) with respect to their Shore hardness in a wide range, for example Shore A 45 to Shore D 90
  • Hills and / or additives (D) and (G) can also be added during the two steps of the process according to the invention.
  • Mention may be made, for example, of lubricants such as fatty acid esters, their metal soaps, fatty acid amides, fatty acid ester amides and silicone compounds, antiblocking agents, inhibitors, hydrolysis stabilizers, light, UV light, heat and discoloration, flame retardants, dyes, pigments, inorganic and / or organic fillers and reinforcing agents.
  • Reinforcing agents are in particular laser-like reinforcing materials, such as.
  • inorganic fibers which are prepared according to the prior art and also be treated with a sizing.
  • the PUR elastomer production can be discontinuous or continuous.
  • the PUR elastomers or the PUR elastomers according to the invention are preferably used in the field of use of cast elastomers.
  • NCO value 40% by weight, naphthalene-1, 5-diisocyanate; eg commercial product Desmodur ® 15 from Bayer MaterialScience AG Analyzes were carried out as follows:
  • the polyethercarbonate polyol B) used was added to the reaction vessel and at 100 ° C for about 30min. dewatered.
  • the polyol was heated to the working temperature ') and then added the isocyanate A).
  • an outlet temperature 2 'of about 127 ° C. was recorded under vacuum.
  • the prepolymer was added at about 110 ° C with Kettenv erinrer E) and poured into preheated molds. Once the castables were demoldable, they were placed in an oven for further 16 hours at 110 ° C for further aging. At room temperature, the samples were then stored for 4 weeks (and 2 more weeks of water storage).
  • Use temperature is defined as the temperature to which the polyol is heated.
  • Duration is defined as the period from addition of the isocyanate to reaching the outlet temperature;
  • Outlet temperature is defined as the maximum temperature reached after the addition of isocyanate due to the exothermic nature of the N ( ' () - ()!
  • prepolymer temperature is defined as the temperature at which crosslinker E) is added to the prepolymer.
  • Casting time is defined as the period after the addition of crosslinker E) until the time at which the reacting melt no longer flows freely.
  • Mold release is determined separately by pouring reacting melt on a 1 10 ° C hot plate and checked for freedom from tack at regular intervals.
  • Table 2 Mechanical values of the elastomers produced
  • Table 2 also shows that the polyurethane elastomers according to the invention (from Examples A-2 and A-3) with the prior art (Al (V)) have comparable mechanical properties to the prior art PUR elastomers (Comparative Experiment A - 1 (V)).

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

Abstract

L'invention concerne des élastomères polyuréthanes et un procédé de production d'un élastomère polyuréthane à base de polyéthercarbonate polyols. Le procédé comprend une première étape, dans laquelle on fait réagir au moins A) un diisocyanate organique et B) un polyol pour obtenir un prépolymère à terminaison NCO. Dans une deuxième étape, on fait réagir le prépolymère exclusivement avec C) au moins un allongeur de chaîne et/ou agent de réticulation. Les composants B) contiennent au moins un polyéthercarbonate polyol pouvant être obtenu par fixation de dioxyde de carbone et d'oxydes d'alkylène à des substances de départ à fonctionnalité H à l'aide de catalyseurs.
PCT/EP2013/071378 2012-10-16 2013-10-14 Élastomères polyuréthanes et leur production Ceased WO2014060329A2 (fr)

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WO2018069350A1 (fr) 2016-10-12 2018-04-19 Covestro Deutschland Ag Procédé de préparation d'un prépolymère comportant des liaisons multiples en tant que précurseur d'élastomère
EP3412695A1 (fr) * 2017-06-08 2018-12-12 Covestro Deutschland AG Bien de consommation jetable à base de polyuréthanes thermoplastiques spéciaux
DE102021101532A1 (de) 2020-11-20 2022-05-25 W. Köpp GmbH & Co. KG Verfahren zur Herstellung eines Elastomer-Werkstoffs unter Verwendung eines CO2-haltigen Rohpolymers
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DK2091990T3 (da) * 2006-11-15 2011-09-26 Basf Se Fremgangsmåde til fremstilling af polyurethan-blødskumstoffer
WO2009119454A1 (fr) * 2008-03-25 2009-10-01 旭硝子株式会社 Composé hydroxy, son procédé de fabrication et prépolymère et polyuréthane comprenant chacun le composé hydroxy
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WO2018069350A1 (fr) 2016-10-12 2018-04-19 Covestro Deutschland Ag Procédé de préparation d'un prépolymère comportant des liaisons multiples en tant que précurseur d'élastomère
CN109790275A (zh) * 2016-10-12 2019-05-21 科思创德国股份有限公司 制备含多重键的预聚物作为弹性体前体的方法
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US11312812B2 (en) 2016-10-12 2022-04-26 Covestro Deutschland Ag Process for producing elastomers
EP3412695A1 (fr) * 2017-06-08 2018-12-12 Covestro Deutschland AG Bien de consommation jetable à base de polyuréthanes thermoplastiques spéciaux
WO2018224456A1 (fr) * 2017-06-08 2018-12-13 Covestro Deutschland Ag Biens de consommation à courte durée de vie à base de polyuréthanes thermoplastiques
DE102021101532A1 (de) 2020-11-20 2022-05-25 W. Köpp GmbH & Co. KG Verfahren zur Herstellung eines Elastomer-Werkstoffs unter Verwendung eines CO2-haltigen Rohpolymers
WO2022106347A1 (fr) 2020-11-20 2022-05-27 W. Köpp GmbH & Co. KG Processus de production d'un matériau élastomère à l'aide de pecus
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WO2022238285A1 (fr) * 2021-05-12 2022-11-17 Covestro Deutschland Ag Élastomères de polyuréthane coulés et leur production

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