EP3649178A1 - Polyester polyols soufrés, leur préparation et leur utilisation - Google Patents

Polyester polyols soufrés, leur préparation et leur utilisation

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Publication number
EP3649178A1
EP3649178A1 EP18737577.9A EP18737577A EP3649178A1 EP 3649178 A1 EP3649178 A1 EP 3649178A1 EP 18737577 A EP18737577 A EP 18737577A EP 3649178 A1 EP3649178 A1 EP 3649178A1
Authority
EP
European Patent Office
Prior art keywords
acid
polyester polyol
diol
dicarboxylic acid
component
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Withdrawn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
EP18737577.9A
Other languages
German (de)
English (en)
Inventor
Martin Ruebenacker
Kathrin COHEN
Sirus Zarbakhsh
Sindhu MENON
Sabrina KRONIG
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3649178A1 publication Critical patent/EP3649178A1/fr
Withdrawn legal-status Critical Current

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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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/14—Manufacture of cellular products
    • 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
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • 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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
    • 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
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6886—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/142—Compounds containing oxygen but no halogen atom
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams

Definitions

  • PESOLs Sulfur-containing polyesterpolyols
  • polyurethane and the abbreviation "PESOL” are used to mean a compound having at least two reactive OH groups and at least two, preferably more than two, ester bonds.
  • poly (thio) ester polyols can be prepared in various ways, for example by condensation of di (hydroxyethyl) polysulfides.
  • US 8,158,726 describes the preparation of hydroxy- and carboxy-functional polyesters, for. By reacting di (hydroxyethyl) disulphide with a monobasic or dibasic carboxylic acid in the presence of a protic acid catalyst. lysators, and their use in polyurethane prepolymers based on the previously named compounds. However, no polysulfidic dicarboxylic acids are used here.
  • a strong acid is preferably used as protic catalyst, such as methanesulfonic acid. This increasingly leads to the formation of unwanted cyclic by-products.
  • Sulfur-containing dicarboxylic acids have the advantage of increased reactivity towards esterification due to the activation of the COOH groups.
  • polyesters produced in the synthesis described, in which transition metal catalysts are used, can be processed by extrusion into materials which have an increased oxygen barrier (US Pat. No. 4,426,512).
  • transition metal catalysts in which transition metal catalysts are used, can be processed by extrusion into materials which have an increased oxygen barrier (US Pat. No. 4,426,512).
  • the structures described are each aromatic thioethers which have an improved barrier property by the combination of sulfur and aromatic carboxylic acids. In the case of aromatic compounds, it is to be expected that the barrier properties will be improved due to the "pi-stacking" effect, but this can not be predicted for aliphatic compounds.
  • disulfidic, aliphatic Q-bonds such as diacids (eg 3,3-dithiodipropionic acid also called 3- (2-carboxyethyl-disulfanyl) propanoic acid (CAS 1 1 19-62-9 ) may also have improved barrier properties by skillful combination, for example with glycols.
  • Sulfur-based foams as described in US Pat. No. 3,892,686, could be prepared by reaction of aromatic dicarboxylic acids or heterocycles with elemental sulfur. Thus, aromatic polysulfides are obtained.
  • dithiodipropionic acid is described in this publication only as an additive. Furthermore, no statements were made about the resulting properties of the foams. Further relevant literature describes the preparation of sulfur-containing polyesters (US Pat. No. 3,459,787) based on monothio and dithiocarboxylic acids by means of catalyzed esterification, with, for example, lead oxide. The use of cyclohexanedimethanol is not disclosed.
  • the resulting polymers are polyesterols having a molecular weight of from 2,000 to 10,000 gmol and have been further processed in part by heating with elemental sulfur and tested for their properties, eg crystallinity and viscosity.
  • elemental sulfur e.g., sulfur-catalyzed silicate
  • properties eg crystallinity and viscosity.
  • the polyester polyols should be as simple as possible, for. Example, without the use of an additional catalyst, be produced, and it should be as few by-products arise.
  • no further catalyst is used.
  • z. B. protic (acid) catalyst By waiving an additional, z. B. protic (acid) catalyst and the number and amount of unwanted by-products in the PESOL product are reduced.
  • An object of the present invention is thus a polyesterpolyol comprising the esterification product of:
  • diol b-1 which is selected from the group consisting of cyclohexanedimethanol and 1, 6 hexanediol
  • the dicarboxylic acid component A) also comprise at least one non-sulfuric dicarboxylic acid a-2.
  • the dicarboxylic acid component A) preferably comprises
  • b 0-50 mol% of a non-sulfur dicarboxylic acid a-2, wherein the sum of the mol% of the components a-1 and a-2 in the dicarboxylic acid component A) is 100 mol%.
  • non-sulfuric dicarboxylic acid a-2 examples are: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acids a-2 can be used both individually and as a mixture with one another. Instead of the free dicarboxylic acids, the corresponding dicarboxylic acid derivatives, such as dicarboxylic acid esters of alcohols having 1 to 4 carbon atoms or dicarboxylic anhydrides such as phthalic anhydride are used.
  • aromatic dicarboxylic acids phthalic acid, terephthalic acid and / or isophthalic acid are preferably used in admixture or alone.
  • the aliphatic dicarboxylic acids used are preferably dicarboxylic acid mixtures of succinic, glutaric and adipic acid.
  • wtfd phthalic acid and terephthalic acid are used as non-sulfuric dicarboxylic acid a-2.
  • At least one, preferably all, of the at least one disulfide-containing dicarboxylic acids a-1) is selected from the group consisting of aliphatic disulfide-containing dicarboxylic acids.
  • at least one of the disulfide-containing dicarboxylic acids is a-1), preferably all of the disulfide-containing dicarboxylic acids a-1) selected from the group consisting of 3,3-dithiodipropionic acid, 2- (carboxymethyldisulfanyl) acetic acid, 3- (2 -Carboxyethyl-disulfanyl) propanoic acid, 4- (3-carboxypropyldisulfanyl) butanoic acid, and their alkyl esters, preferably dimethyl and diethyl esters and mixtures of the above-mentioned dicarboxylic acids.
  • dicarboxylic acid component A) consists of only one disulfide-containing dicarboxylic acid, this disulfide-containing dicarboxylic acid being 3- (2-carboxyethyl-disulfanyl) -propanoic acid (3,3-dithiodipropionic acid).
  • the diol component D may comprise, in addition to the diol b-1) yet another diol b-2.
  • the diol b-2 is selected from the group consisting of ethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, monopropylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 5-pentanediol or mixtures the above components.
  • the diol component D) comprises
  • component b-1 is the sole diol component D.
  • component b-1 is 1,4-cyclohexanedimethanol.
  • polyol component (K) comprises
  • the polyol component (K) particularly preferably comprises the higher-order alcohol C) in an amount of 0.1 to 40 mol%, preferably 0.2 to 30 mol%, particularly preferably 0.5 to 10 mol%, based on the sum of all in the polyol component (K) existing alcohols.
  • the polyhydric alcohol C) is selected from the group of glycerol, trimethylolpropane (TMP), pentaerythritol, mixtures of the abovementioned compounds and alkylene oxides of the abovementioned compounds.
  • TMP trimethylolpropane
  • pentaerythritol mixtures of the abovementioned compounds and alkylene oxides of the abovementioned compounds.
  • Alkylene oxides in the context of the present invention are preferably ethylene oxide, propylene oxide or butylene oxide, preferably ethylene oxide or propylene oxide.
  • the polyhydric alcohol C) is prepared by reacting a polyol selected from the group consisting of the group of glycerol, trimethylolpropane (TMP), pentaerythritol with ethylene oxide and / or propylene oxide, preferably ethylene oxide.
  • TMP trimethylolpropane
  • pentaerythritol ethylene oxide and / or propylene oxide, preferably ethylene oxide.
  • the polyhydric alcohol C) consists of the reaction product of TMP with ethylene oxide. In one embodiment of the present invention, the polyhydric alcohol C) has a
  • OH number in the range of 1800 mg KOH / g to 100 mg KOH / g, preferably 1400 mg KOH / g to 150 mg KOH / g, more preferably 1250 mg KOH / g to 200 mg KOH / g.
  • the polyhydric alcohol C) consists of TMP.
  • the polyhydric alcohol C) consists of the reaction product of trimethylolpropane (TMP) or glycerol with ethylene oxide and / or propylene oxide, preferably ethylene oxide, TMP.
  • TMP trimethylolpropane
  • glycerol ethylene oxide and / or propylene oxide, preferably ethylene oxide, TMP.
  • a particularly preferred embodiment of the invention is a polyester polyol consisting of the esterification product of i) 45-50 mol% of the dicarboxylic acid component (D) comprising 3- (2-carboxyethyl-disulfanyl) propanoic acid and ii) 50-55% of a polyol component (P) comprising 1, 4-cyclohexanedimethanol, wherein the mol% of components i) and ii) add up to 100%.
  • a further preferred embodiment of the invention is a polyester polyol consisting of the esterification product of a) 10 to 70 mol% of 3- (2-carboxyethyl-disulfanyl) propanoic acid and b) 10 to 70 mol% of 1, 4-cyclohexanedimethanol, where the mol% the components i) and ii) add to 100%, and wherein the esterification no additional catalyst is used.
  • a further particularly preferred embodiment of the invention is a polyesterpolyol consisting of the esterification product of i) 45 to 55 mol% of 3- (2-carboxyethyldisulfanyl) propanoic acid, ii) 50 to 55% of a polyol component K, which consists of
  • a further particularly preferred embodiment of the invention is a polyesterpolyol consisting of the esterification product of i) 45 to 55 mol% of 3- (2-carboxyethyldisulfanyl) propanoic acid, ii) 50 to 55% of a polyol component K, which consists of
  • b-1) from 10 to 70 mol% of 1,4-cyclohexanedimethanol; and c) from 0.5 to 20 mol% of trimethylolpropane, wherein the mol% of components a) to c) add up to 100% and in the esterification no additional catalyst is used.
  • a further subject of the present invention is also a process for the preparation of a polyester polyol by reacting the dicarboxylic acid component (D) as defined above in the amounts indicated above with the polyol component (P).
  • the disulfide-containing polycarboxylic acids and / or derivatives and polyhydric alcohols are preferably free from catalyst, advantageously in an atmosphere of inert gas, such as e.g. Nitrogen, carbon monoxide, helium, argon and the like. in the melt at temperatures of 150 to 220 ° C, preferably 160 to 190 ° C, optionally under reduced pressure to the desired acid number, which is advantageously less than 10, preferably less than 2, polycondensed.
  • the esterification mixture at the abovementioned temperatures to an acid number of 80 to 20, preferably 40 to 20, under normal pressure and then under a pressure of less than 500 mbar, preferably 40 to 400 mbar, polycondensed.
  • the polyesterpolyols obtained preferably have a functionality of 1.8 to 4, in particular 2 to 3, and a molecular weight of 300 to 3000, preferably 400 to 2500 and in particular 450 to 2000.
  • a further embodiment of the process comprises a variant in which no additional catalyst is used to prepare a polyester polyol according to the invention.
  • the invention also relates to the use of the polyester polyols according to the invention or to prepare according to the invention for preparing a polyurethane by reaction with at least one di- or polyisocyanate and at least one aliphatic diol and optionally at least one blowing agent.
  • the invention relates to the use of the polyester polyols according to the invention in rigid polyurethane foams.
  • the present invention also includes a process for producing a rigid polyurethane foam by reacting a reaction mixture comprising
  • F one or more propellants
  • reaction mixture in a further embodiment also contains
  • D. optionally polyetherols and / or other compounds having at least two isocyanate-reactive groups and / or
  • chain extenders and / or crosslinking agents and / or
  • auxiliaries and / or additives optionally further auxiliaries and / or additives, and / or
  • the invention particularly relates to the use of the polyester polyols according to the invention in rigid polyurethane foams prepared from:
  • optional foam stabilizers (J) can be used.
  • Suitable organic and / or modified organic polyisocyanates A) are the per se known aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyfunctional isocyanates.
  • alkylenediisocyanates having 4 to 12 carbon atoms in the alkylene radical such as 1,12-dodecanediisocyanate, 2-ethyltetramethylenediisocyanate 1, 4, 2-methylpentamethylene diisocyanate-1, 5, tetramethylene diisocyanate-1, 4, and preferably hexamethylene diiso- cyanate-1, 6;
  • Cycloaliphatic diisocyanates such as cyclohexane-1, 3- and 1, 4-diisocyanate and any mixtures of these isomers, 1 -lsocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4- and 2,6-Hexahydrotoluylendiisocyanat and the corresponding isomer mixtures, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures,
  • the organic di- and polyisocyanates can be used individually or in the form of their mixtures.
  • Preferred diisocyanates and polyisocyanates are tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and, in particular, mixtures of diphenylmethane diisocyanate and polyphenylene polyethylene polyisocyanates (polymeric MDI or PMDI).
  • modified polyvalent isocyanates i. Products obtained by chemical reaction of organic di- and / or polyisocyanates used. Examples include ester, urea, biuret, allophanate, carbodiimide, isocyanurate, uretdione, carbamate, and / or urethane groups-containing di- and / or polyisocyanates.
  • ester urea, biuret, allophanate, carbodiimide, isocyanurate, uretdione, carbamate, and / or urethane groups-containing di- and / or polyisocyanates.
  • polymer MDI for the production of rigid polyurethane foams, very particular preference is given to using polymer MDI.
  • Suitable further polyester polyols C) can be prepared, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aromatic or a mixture of aromatic and aliphatic dicarboxylic acids, and polyhydric alcohols, preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
  • Suitable dicarboxylic acids are, for example: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acids can be used both individually and in admixture with each other.
  • the corresponding dicarboxylic acid derivatives e.g. Dicarboxylic ter of alcohols having 1 to 4 carbon atoms or dicarboxylic anhydrides such as phthalic anhydride are used.
  • aromatic dicarboxylic acids phthalic acid, terephthalic acid and / or isophthalic acid are preferably used in admixture or alone.
  • the aliphatic dicarboxylic acids used are preferably dicarboxylic acid mixtures of succinic, glutaric and adipic acid in proportions of, for example, from 20 to 35:35 to 50:20 to 32 parts by weight, and in particular adipic acid.
  • dihydric and polyhydric alcohols, in particular diols are: ethanediol, diethylene glycol, 1,2-or 1,3-propanediol,
  • Dipropylene glycol 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 10-decanediol, glycerol, trimethylolpropane and pentaerythritol.
  • ethanediol diethylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol or mixtures of at least two of said diols, in particular mixtures of 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol.
  • polyester polyols from lactones, for example ⁇ -caprolactone or hydroxycarboxylic acids, for example ⁇ -hydroxycaproic acid.
  • polyether polyols D which have been prepared by known processes, for example by anionic polymerization with alkali metal hydroxides, e.g. Sodium or potassium hydroxide or alkali alcoholates, e.g. Sodium methylate, sodium or potassium ethylate or potassium isopropylate, as catalysts and with the addition of at least one starter molecule containing 2 to 8, preferably 2 to 6, bonded reactive hydrogen atoms, or by cationic polymerization with Lewis acids such as antimony pentachloride, borofluoride etherate u.a. or bleaching earth, are prepared as catalysts from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical.
  • alkali metal hydroxides e.g. Sodium or potassium hydroxide or alkali alcoholates, e.g. Sodium methylate, sodium or potassium ethylate or potassium isopropylate
  • Lewis acids such as antimony pentachloride, borofluoride etherate
  • 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.
  • Preferred alkylene oxides are propylene oxide and ethylene oxide, particularly preferred is ethylene oxide.
  • 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 ⁇ , ⁇ '-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
  • alkanolamines e.g. Ethanolamine, N-methyl and N-ethylethanolamine
  • dialkanolamines e.g. Diethanolamine, N-methyl- and N-ethyldiethanolamine
  • trialkanolamines e.g. Triethanolamine, and ammonia.
  • dihydric or polyhydric alcohols such as ethanediol, propanediol 1, 2 and 1, 3, diethylene glycol, dipropylene glycol, butanediol 1, 4, hexanediol 1, 6, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose ,
  • the polyether polyols preferably polyoxypropylene polyols and / or polyoxyethylene polyols, have a functionality of preferably 2 to 6 and in particular 2 to 5 and molecular weights of 150 to 3000, preferably 200 to 2000 and in particular 250 to 1000.
  • polyether polyols are polymer-modified polyether polyols, preferably graft polyether polyols, in particular those based on styrene and / or acrylonitrile, which are prepared by in situ polymerization of acrylonitrile, styrene or preferably mixtures of styrene and acrylonitrile, for example in a weight ratio of 90:10 to 10:90 , preferably 70:30 to 30:70, in expediently the abovementioned polyether polyols analogously to the specifications of German Patent Specifications 1,131,194, 12,222,669 (US 3,304,273, 3,383,351, 3,523,093), 1,152,536 (GB 10 40452) and 1 1 52 537 (GB 987.618), and polyetherpolyol dispersions containing as a disperse phase, usually in an amount of 1 to 50 wt .-%, preferably 2 to 25% by weight: eg polyureas, poly
  • the polyether polyols may be used singly or in the form of mixtures. Furthermore, they can be mixed with the graft polyether polyols or polyester polyols and with the hydroxyl-containing polyester amides, polyacetals, polycarbonates and / or polyether polyamines.
  • hydroxyl-containing polyacetals are e.g. the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4'-dihydroxyethoxydiphenyldimethylmethane, hexanediol and formaldehyde. It is also possible to prepare suitable polyacetals by polymerization of cyclic acetals.
  • Suitable hydroxyl-containing polycarbonates are those of the type known per se which can be obtained, for example, by reacting diols, such as propanediol 1, 3, butanediol 1, 4 and / or hexanediol 1, 6, diethylene glycol, triethylene glycol or tetraethylene glycol with diarylcarboxylic acid. boning, eg Diphenyl carbonate, alkylene carbonate or phosgene can be prepared.
  • the polyester amides include e.g.
  • polyether polyamines can be prepared from the above polyether polyols by known methods. Examples include the cyanoalkylation of polyoxyalkylene and subsequent hydrogenation of the nitrile formed (US 3,267,050) or the partial or complete A- mintechnik of polyoxyalkylene with amines or ammonia in the presence of hydrogen and catalysts (DE 12 15 373).
  • the rigid polyurethane foams according to the invention can be prepared with the concomitant use of chain extenders and / or crosslinking agents (E).
  • chain extenders and / or crosslinking agents E
  • crosslinking agents E
  • the addition of chain extenders, crosslinking agents or optionally mixtures thereof may prove advantageous.
  • chain extenders and / or crosslinking agents are used diols and / or triols having molecular weights less than 400, preferably from 60 to 300.
  • Suitable examples include aliphatic, cycloaliphatic and / or araliphatic diols having 2 to 14, preferably 4 to 10 carbon atoms , such as ethylene glycol, propanediol-1, 3, decanediol-1, 10, o-, m-, p-dihydroxycyclohexane, diethylene glycol, dipropylene glycol and preferably butanediol-1, 4, hexanediol-1, 6 and bis (2-hydroxy -ethyl) -hydroquinone, triols such as 1, 2,4-, 1, 3,5-trihydroxycyclohexane, glycerol and trimethylolpropane and low molecular weight hydroxyl-containing polyalkylene oxides based on ethylene and / or 1, 2-propylene
  • Further compounds (D) having at least two isocyanate-reactive groups ie having at least two hydrogen atoms which are reactive toward isocyanate groups, are in particular those which contain two or more reactive groups selected from OH groups, SH groups, NH groups and Groups, NH2 groups and CH-acidic groups, such as ß-diketo groups have.
  • chain extenders, crosslinking agents or mixtures thereof are used for producing the rigid polyurethane foams, these are expediently used in an amount of from 0 to 20% by weight, preferably from 0.5 to 5% by weight, based on the weight of component B), for use.
  • Propellants (F) used to prepare the rigid polyurethane foams preferably include water, formic acid and mixtures thereof. These react with isocyanate groups to form carbon dioxide and in the case of formic acid to carbon dioxide and carbon monoxide.
  • physical blowing agents such as low-boiling hydrocarbons and aromatic and aliphatic halogenated hydrocarbons can be used.
  • Suitable liquids are those which are inert to the organic, optionally modified polyisocyanates and have boiling points below 100 ° C., preferably below 50 ° C. at atmospheric pressure, so that they evaporate under the influence of the exothermic polyaddition reaction.
  • alkanes such as heptane, hexane, n- and iso-pentane, preferably technical mixtures of n- and iso-pentanes, n- and iso-butane and propane, cycloalkanes, such as cyclopentane and / or Cyclohexane, ethers, such as furan, dimethyl ether and diethyl ether, ketones, such as acetone and methyl ethyl ketone, alkyl carboxylates, such as methyl formate, dimethyl oxalate and ethyl acetate, and halogenated hydrocarbons, such as
  • Methylene chloride dichloromonofluoromethane, difluoromethane, trifluoromethane, difluoroethane, tetrafluoroethane, chlorodifluoroethanes, 1,1-dichloro-2,2,2-trifluoroethane, 2,2-dichloro-2-fluoroethane and hepafluoropropane. It is also possible to use mixtures of these low-boiling liquids with one another and / or with other substituted or unsubstituted hydrocarbons. Furthermore, halogenated olefins can be used.
  • organic carboxylic acids e.g. Formic acid, acetic acid, oxalic acid, ricinoleic acid and carboxyl group-containing compounds.
  • blowing agents are either wholly or partially in the polyol component (i.e.
  • B + C + D + E + F + G + H + l are dissolved or are metered in directly before the foaming of the polyol component via a static mixer.
  • the polyol component is in situ pentane, possibly parts of the chemical blowing agent, partially or completely added to the catalysts, but usually this already contains at least parts thereof (with the exception of the pentane).
  • the auxiliaries and additives, as well as the flame retardants are - if present - preferably already in the polyol blend.
  • the amount of blowing agent or propellant mixture used is 1 to 45 wt .-%, preferably 1 to 30 wt .-%, particularly preferably 1, 5 to 20 wt .-%, each based on the sum of components B) to G).
  • the water can be contained separately or in one of the components B, F, C, D, E, H, I, G or J.
  • the addition of water can be done in combination with the use of the other blowing agents described.
  • catalysts (G) for the preparation of rigid polyurethane foams in particular compounds are used which greatly accelerate the reaction of the reactive hydrogen atoms, in particular hydroxyl groups, containing compounds of component B) and optionally C) with the organic, optionally modified polyisocyanates A).
  • basic polyurethane catalysts for example tertiary amines, such as triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyldiaminodiethyl ether, bis (dimethylaminopropyl) urea, N-methyl- or triethylamine N-ethylmorpholine, N-cyclohexylmorpholine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylethylenediamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylbutanediamine, N, N, N ', N'-tetramethylhexanediamine-1, 6 , Pentamethyldiethylenetriamine, dimethylpiperazine, N-dimethylaminoethylpiperidine, 1, 2-d
  • metal salts are also suitable, such as iron (II) chloride, zinc chloride, lead octoate and preferably tin salts, such as tin dioctoate, tin diethylhexoate and dibutyltin dilaurate, and in particular mixtures of tertiary amines and organic tin salts.
  • carboxylates often in the form of their potassium or ammonium salts, such as formate, acetate, octoate, or in zwitterionic form, for example in the form of substituted amino acids.
  • amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine ,. and alkali salts of long-chain fatty acids having 10 to 20 carbon atoms and optionally pendant OH groups.
  • alkali salts of long-chain fatty acids having 10 to 20 carbon atoms and optionally pendant OH groups.
  • Preferably used are 0.001 to 5 wt .-%, in particular 0.05 to 2 wt .-%, catalyst or catalyst combination, based on the weight of components B) to I). It is also possible to run the reactions without catalysis. In this case, the catalytic activity of amines started polyols is exploited.
  • the catalysts for the trimerization reaction are the excess NCO-
  • isocyanurate group-forming catalysts for example ammonium ions or alkali metal salts alone or in combination with tertiary amines.
  • isocyanurate leads to flame-resistant PIR foams, which are preferably used in industrial rigid foam, for example in construction as an insulating board or sandwich elements.
  • auxiliaries and / or additives (H) may also be added to the reaction mixture for the preparation of the rigid polyurethane foams. Mention may be made, for example, of surface-active substances, foam stabilizers, cell regulators, fillers, dyes, pigments, flame retardants, hydrolysis protectants, fungistatic and bacteriostatic substances.
  • surface-active substances are e.g. Compounds which serve to assist the homogenization of the starting materials and, if appropriate, are also suitable for regulating the cell structure of the plastics.
  • emulsifiers such as the sodium salts of castor sulfinates or fatty acids, and salts of fatty acids with amines, e.g. diethylamine, stearic acid diethanolamine, diethanolamine ricinoleic acid, salts of sulfonic acids, e.g.
  • Foam stabilizers such as siloxane-oxalkylene mixed polymers and other organopolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, Turkish red oil and peanut oil, and cell regulators, such as paraffins, fatty alcohols and dimethylpolysiloxanes.
  • the above-described oligomeric acrylates having polyoxyalkylene and fluoroalkane radicals are also suitable as side groups.
  • the surface-active substances are usually used in amounts of from 0.01 to 10% by weight, based on 100% by weight of component B).
  • Fillers, in particular reinforcing fillers are the conventional, customary organic and inorganic fillers, reinforcing agents, weighting agents, agents for improving the abrasion behavior in paints, coating compositions, etc.
  • inorganic fillers such as silicate minerals, for example phyllosilicates such as antigorite, serpentine, hornblende, amphiboles, chrysotile and talc, metal oxides such as kaolin, aluminas, titanium oxides and iron oxides, metal salts such as chalk, barite and inorganic pigments such as cadmium sulfide and zinc sulfide, as well as glass, etc.
  • kaolin China Clay
  • aluminum silicate and coprecipitates of barium sulfate and aluminum silicate and natural and synthetic fibrous minerals such as wollastonite, metal and in particular glass fibers of various 5 length, which may optionally be finished.
  • Suitable organic fillers are, for example: carbon, melamine, rosin, cyclopentadienyl resins and graft polymers and also cellulosic fibers, polyamide, polyacrylonitrile, polyurethane, polyester fibers based on aromatic and / or aliphatic dicarboxylic acid esters and in particular carbon fibers.
  • the inorganic and organic fillers can be used individually or as mixtures and are advantageously added to the reaction mixture in amounts of 0.5 to 50% by weight, preferably 1 to 40% by weight, based on the weight of components A) to C). , but the content of mats, fleeces and fabrics made of natural and synthetic fibers can reach values of up to 80% by weight.
  • Suitable flame retardants are, for example, non-incorporable brominated substances, brominated esters, brominated ethers (xxol), or brominated alcohols such as dibromoneopentyl alcohol, tribromoneopentyl alcohol and PHT-4-diol, and chlorinated phosphates, e.g.
  • phosphates or phosphonates such as diethylethane phosphonate (DEEP), triethyl phosphate (TEP), dimethyl propyl phosphonate (DMPP), diphenyl cresyl phosphate (DPK) and others.
  • DEEP diethylethane phosphonate
  • TEP triethyl phosphate
  • DMPP dimethyl propyl phosphonate
  • DPK diphenyl cresyl phosphate
  • inorganic or organic flame retardants such as red phosphorus, red phosphorus-containing finishes, alumina hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives, e.g. Melamine, or mixtures of at least two flame retardants, e.g. Ammonium polyphosphates and melamine and optionally corn starch or ammonium polyphosphate, melamine and expandable graphite and / or optionally aromatic polyester for flame retardancy of the rigid polyurethane foams can be used.
  • flame retardants e.g. Ammonium polyphosphates and melamine and optionally corn starch or ammonium polyphosphate, melamine and expandable graphite and / or optionally aromatic polyester for flame retardancy of the rigid polyurethane foams
  • the corresponding rigid polyurethane foams for thermal insulation in refrigerators (refrigerators) and in the construction industry can be used.
  • polyurethane rigid foams for use in the construction and rigid polyurethane foams for cooling systems usually contain flame retardants
  • Another object of the invention relates to the use of the polyester polyols according to the invention in thermoplastic polyurethanes by reacting a polyester polyol prepared by the process according to the invention with one or more organic diisocyanates (or polyisocyanates), which have already been described in previous versions.
  • the preparation of the polyurethanes can in principle by the known methods, batchwise or continuously, for example with reaction extruders or the tape method according to "one-shot” or the prepolymer method (also multi-stage prepolymer method, see for example US 6,790,916), but preferably after the "one-shot "Procedures are carried out.
  • the components to be reacted polyesterpolyols, chain extenders, isocyanates and, if appropriate, auxiliaries and additives (in particular UV stabilizers) can be mixed successively or simultaneously with one another, the reaction starting immediately.
  • the polyurethane which is obtained from a polyesterpolyol prepared by the process according to the invention is in particular a thermoplastic polyurethane.
  • Thermoplastic polyurethanes are also referred to below as TPU.
  • TPU The production of TPU can be carried out by the methods known to those skilled in the art.
  • Another object of the present invention relates to a molding, a film, a hose, z.
  • TPU The production of TPU can be carried out by the methods known to those skilled in the art.
  • Polyester polyol comprising the esterification product of
  • Polyester polyol according to embodiment 1 characterized in that the non-sulfur-containing dicarboxylic acid is a-2 terephthalic acid. Polyester polyol according to embodiment 1 or 2, characterized in that the dicarboxylic acid component A)
  • Polyester polyol according to one of embodiments 1 to 4 characterized in that the diol (D) comprises a further diol b-2.
  • Polyesterpolyol according to any one of embodiments 1 to 7, characterized in that the polyol component (K) the diol (D) and at least one higher-grade alcohol C) with a functionality greater than 2 includes. Polyester polyol according to embodiment 8, characterized in that the polyol component (K).
  • Polyester polyol according to embodiment 8 characterized in that the polyol component (K).
  • Polyester polyol according to embodiment 8 characterized in that the polyol component (K).
  • Polyester polyol according to one of embodiments 1 to 1 1, characterized in that it
  • b. is continued at a pressure of less than 500 mbar to an acid number of less than 10 mg KOH / g.
  • step b A process for preparing a polyester polyol according to any one of embodiments 25 to 21, wherein in step b at a pressure of 40 to 400 mbar is used.
  • a process for producing a rigid polyurethane foam by reacting a reaction mixture comprising
  • organic and / or modified organic di- and / or polyisocyanates with b. at least one polyester polyol according to any of embodiments 1 to 19, c. one or more propellants as well
  • reaction mixture further comprises further polyetherols and / or other compounds having at least two isocyanate-reactive groups.
  • the reaction mixture further comprises chain extenders and / or crosslinkers.
  • reaction mixture additionally comprises chain extender and / or flame retardant.
  • Polyurethane rigid foam obtainable by a process according to embodiments 30 to 34.
  • 36. Use Polyester polyol according to one of embodiments 1 to 19 for producing a rigid polyurethane foam.
  • the viscosity of the polyols was determined at 25 ° C. in accordance with DIN EN ISO 3219 (October 1994) using a Rheotec RC 20 rotational viscometer using the spindle CC 25 DIN (spindle diameter: 12.5 mm; : 13.56 mm) at a shear rate of 50 1 / s.
  • hydroxyl numbers were determined by the phthalic anhydride method DIN 53240 (December 1971) and reported in mg KOH / g.
  • the acid number was determined according to DIN EN 1241 (May 1998) and is given in mg KOH / g. Permeability measurement on polyurethane films
  • the permeability of polyurethane films was determined against each 4 gases.
  • the transmissions against nitrogen, methane, and carbon dioxide were measured with a Brugger gas permeability tester according to ASTM D 1434 82 (1982 original, 2015 rev.).
  • the measuring area is 78 cm 2 .
  • the oxygen permeability was determined in a Mocon Oxtran 2/21 according to ASTM D 3985 (2005 orig., 2010 rev.). Here the measuring area is 50 cm 2 .
  • the water permeability was determined according to ASTM F-1249 (2013 original).
  • 1660 g of adipic acid and 1249 g of butanediol are placed in a 41 round-bottomed flask equipped with thermometer, nitrogen inlet, heated mushroom, distillation column and stirrer and heated to 120.degree. After adding 1 ppm of titanium tetrabutoxide as a catalyst, the mixture is stirred and heated to 240 ° C, wherein the released water is continuously distilled off.
  • the polyesterpolyol obtained had a hydroxyl number of 56 mg KOH / g, an acid number of 0.6 mg KOH / g and a viscosity of 670 mPas at 75.degree.
  • TPUs were produced from the polyester polyols prepared in Inventive Example 1 and Comparative Example 2 and made into flat films.
  • the TPU production was carried out by methods known to the person skilled in the art.
  • the flat films were produced on a 30-point bend with a three-zone screw with mixing part (screw ratio 1: 3) and a 250 mm slot die.
  • TPU flat films based on polyesterols without dithio-di-propionic acid have a significantly higher permeability compared to the gases tested.
  • Polyol 1 polyester polyol based on terephthalic acid, diethylene glycol, cis
  • Polyol 2 polyester polyol based on 3,3'-dithiodipropionic acid, cyclohexanedimethanol and trimethylolpropane, OH number 55 mg KOH / g.
  • Polyol 3 Polyester polyol based on 3,3-dithiodipropionic acid, cyclohexanedimethanol and glycerol, OH number 235 mg KOH / g.
  • Polyol 4 polyether polyol based on diethylene glycol and ethylene oxide, OH number
  • Isocyanate Polymeric MDI with an NCO content of 31.5% by weight
  • the thermal conductivity is determined using a ⁇ -meter EP500e from Lambda Messtechnik GmbH Dresden at an average temperature of 10 ° C. on PU test specimens of dimensions 200 ⁇ 200 ⁇ 50 mm, which were taken from the cube foam block described above 24 hours after its production ,
  • a sample body approximately 10 ⁇ 10 ⁇ 10 cm larger is taken from the interior of a cup foam.
  • a clean cut surface perpendicular to the direction of the foam is generated and contrasted with soot spray. Then the cut surface is taken up with a light microscope and the evaluation with the software PORE! SCAN from Goldlücke. This generates over the area a size class distribution of the cells and the arithmetic mean value.
  • the determination of the cell gases is carried out according to the method of M. Svanström and O. Ramnäs described in the Journal of Cellular Plastics, Vol. 31, 1995, pages 375-388, in which from the intak- th cup foams under an inert gas atmosphere with a gas sample from the foam interior a brass syringe is removed.

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne des polyester polyols soufrés, leur préparation et leur utilisation.
EP18737577.9A 2017-07-05 2018-07-03 Polyester polyols soufrés, leur préparation et leur utilisation Withdrawn EP3649178A1 (fr)

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EP3555162B1 (fr) * 2016-12-15 2021-05-19 Dow Global Technologies LLC Produit de polyuréthane possédant un polyol contenant du soufre
WO2018111750A1 (fr) * 2016-12-15 2018-06-21 Dow Global Technologies Llc Produit de polyuréthanne comportant un polyester polyol sulfuré

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CN110753713A (zh) 2020-02-04
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US11578167B2 (en) 2023-02-14
CN110753713B (zh) 2022-06-28
KR20200027977A (ko) 2020-03-13

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