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WO2022175210A1 - Procédé de production d'une mousse de polyuréthane - Google Patents

Procédé de production d'une mousse de polyuréthane Download PDF

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Publication number
WO2022175210A1
WO2022175210A1 PCT/EP2022/053554 EP2022053554W WO2022175210A1 WO 2022175210 A1 WO2022175210 A1 WO 2022175210A1 EP 2022053554 W EP2022053554 W EP 2022053554W WO 2022175210 A1 WO2022175210 A1 WO 2022175210A1
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WO
WIPO (PCT)
Prior art keywords
alkylene oxide
weight
polyol
parts
koh
Prior art date
Application number
PCT/EP2022/053554
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German (de)
English (en)
Inventor
Joerg Hofmann
Veronica-Alina FAERBER
Stefanie Braun
Michael Traving
Original Assignee
Covestro Deutschland Ag
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from EP21157473.6A external-priority patent/EP4043510A1/fr
Application filed by Covestro Deutschland Ag filed Critical Covestro Deutschland Ag
Publication of WO2022175210A1 publication Critical patent/WO2022175210A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—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
    • C08G18/165—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 covered by C08G18/18 and C08G18/24
    • 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
    • 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
    • C08G18/4866—Polyethers having a low unsaturation value
    • 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
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • 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
    • C08G2110/0008—Foam properties flexible
    • 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
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • the present invention relates to a process for producing polyurethane foams, preferably flexible polyurethane foams, by reacting an isocyanate component with an isocyanate-reactive component which comprises at least one polyether carbonate polyol.
  • the invention further relates to polyurethane foams produced by the process according to the invention and their use, as well as the polyether carbonate polyol used according to the invention.
  • CCE-based starting materials for example in the form of polyether carbonate polyols, in relatively large quantities.
  • the production of polyether carbonate polyols by catalytic conversion of alkylene oxides (epoxides) and carbon dioxide in the presence of H-functional starter compounds (“starters”) has been intensively studied for more than 50 years (e.g. Inoue et al, Copolymerization of Carbon Dioxide and Epoxide with Organometallic Compounds; Die Makromolecular Chemie 130, 210-220, 1969).
  • polyurethane foams based on polyether carbonate polyols and isocyanates is known (eg WO 2012/130760 A1, WO 2015/078801).
  • Important when using Such polyurethane foams include resistance to mechanical influences in order to achieve a long service life for the polyurethane foams.
  • the object of the present invention was therefore to provide a process for producing polyurethane foams comprising polyether carbonate polyols, which leads to polyurethane foams having a higher tensile strength and elongation at break.
  • Al compounds with isocyanate-reactive hydrogen atoms containing Al.l polyether carbonate polyol,
  • B di- and/or polyisocyanates are reacted with one another, characterized in that the structure of Al.l is made up of a starter compound S 1 having a molecular weight of 18 to 200 g/mol on which a first, inner alkylene oxide block containing 0.5 up to 30 wt.
  • the preferred subject matter of the invention is a process for producing polyurethane foams, preferably flexible polyurethane foams, characterized in that component A1 has the following composition:
  • polymer polyol A1.4 0 to 40 parts by weight polymer polyol, PHD polyol and/or PIPA polyol,
  • the components A1.1 to A1.5 each refer to “one or more” of those mentioned
  • component contains Al
  • polyether polyols with a hydroxyl number according to DIN 53240-1 (June 2013) of >20 mg KOH/g to ⁇ 250 mg KOH/g and an ethylene oxide content of >0 to ⁇ 60% by weight, the polyether polyols Al.2 free are of carbonate units, with component Al preferably being free from component Al.3 and/or Al.4.
  • component includes Al
  • component includes Al
  • Al.l >40 to ⁇ 100 parts by weight, preferably >60 to ⁇ 100 parts by weight, particularly preferably >80 to ⁇ 100 parts by weight, most preferably >65 to ⁇ 75 parts by weight of one or more Polyethercarbonate polyols, preferably with a hydroxyl number according to DIN 53240-1 (June 2013) from > 20 mg KOH/g to ⁇ 120 mg KOH/g and preferably a CO 2 content of 10 to 25% by weight, and
  • polyether polyols with a hydroxyl number according to DIN 53240-1 (June 2013) of >20 mg KOH/g to ⁇ 250 mg KOH/g and a content of ethylene oxide from >0 to ⁇ 60% by weight, the polyether polyols Al.2 being free from carbonate units,
  • Component A1 includes compounds with isocyanate-reactive hydrogen atoms and, according to the invention, contains at least one polyether carbonate polyol A1.1.
  • the polyether carbonate polyol A1.1 is based on a starter compound S1 with a molecular weight of 18 to 200 g/mol, a first, inner alkylene oxide block containing 0.5 to 30% by weight of ethylene oxide, based on the total mass of alkylene oxide in the first alkylene oxide block, and a second, outer block of carbon dioxide and alkylene oxide.
  • Starter compound S1 with a molecular weight of 18 to 200 g/mol is understood as meaning compounds which have H atoms which are active towards alkoxylation, for example monohydric or polyhydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1, 4-butanediol, 1,5-pentanediol, 2-methylpropane-1,3-diol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, diethylene glycol, dipropylene glycol, glycerine, trimethylolpropane, pentaerythritol and sorbitol. Mixtures of different starter compounds S1 can also be used.
  • a first, inner alkylene oxide block is attached to the starter compound S 1 with a molecular weight of 18 to 200 g/mol.
  • the first, inner alkylene oxide block consists of at least two alkylene oxides and contains 0.5 to 30% by weight of ethylene oxide, preferably 1 to 25% by weight, in particular preferably 5 to 22% by weight, particularly preferably 12 to 22% by weight, based in each case on the total mass of the alkylene oxide used in the first alkylene oxide block.
  • the first, inner alkylene oxide block preferably consists only of ethylene oxide and propylene oxide.
  • a second, outer block of carbon dioxide and alkylene oxide is attached to the first inner alkylene oxide block.
  • the alkylene oxide used for the second block is preferably propylene oxide, ethylene oxide or a mixture of both, particularly preferably at least 90% by weight of propylene oxide, very particularly preferably just propylene oxide.
  • the polyether carbonate polyol A1.1 is obtained, for example, by a process comprising the steps
  • Steps (i) and (ii) are preferably carried out in the presence of a DMC catalyst, such as DMC catalysts based on zinc hexacyanocobaltate(III), zinc hexacyanoiridate(III), zinc hexacyanoferrate(III) and cobalt(II) hexacyanocobaltate(III) .
  • 2) is preferably used.
  • metal complex catalysts based on the metals zinc and/or cobalt can also be used for the copolymerization of alkylene oxide and carbon dioxide in step (ii). This includes in particular so-called zinc glutarate catalysts (described e.g.
  • Steps (i) and (ii) can be carried out directly one after the other or separately from one another.
  • the alkylene oxide polymer obtained from step (i) can be purified before carbon dioxide and alkylene oxide are added to the alkylene oxide polymer in step (ii).
  • a purification step is advantageous, for example, when different catalysts are used in steps (i) and (ii). However, it can also be a DMC Catalyst are used in step (i) and left in the resulting alkylene oxide polymer and function as a catalyst in step (ii).
  • the alkylene oxide polymer resulting from step (i) preferably has a molecular weight of 250 to 2000 g/mol, preferably 400 to 1200 g/mol, particularly preferably 500 to 1000 g/mol.
  • step (ii) is carried out as follows:
  • step (a) the alkylene oxide polymer from step (i) is initially taken and, if appropriate, water and/or other readily volatile compounds are removed by elevated temperature and/or reduced pressure ("drying"), with a catalyst being optionally used before or after drying to give the alkylene oxide polymer from step (i) is added,
  • step (ß) optionally, to activate a DMC catalyst, a portion (based on the total amount of alkylene oxides used in the activation and copolymerization in step (ii)) of alkylene oxide is added to the mixture resulting from step (a), this addition a subset of alkylene oxide can optionally take place in the presence of CO2, and the temperature peak ("hotspot") occurring as a result of the following exothermic chemical reaction and/or a drop in pressure in the reactor is then awaited in each case, and step (ß) for activation also can be done multiple times
  • step (g) Alkylene oxide and carbon dioxide are added to the mixture resulting from step (a) or optionally ( ⁇ ), it being possible for the alkylene oxides used in step ( ⁇ ) to be the same as or different from the alkylene oxides used in step (g).
  • the polyether carbonate polyol Al.1 used according to the invention preferably has a hydroxyl number (OH number) according to DIN 53240-1 (June 2013) from 20 mg KOH/g to 120 mg KOH/g, preferably from 20 mg KOH/g to 100 mg KOH/g g, particularly preferably from 25 mg KOH/g to 90 mg KOH/g.
  • the polyether carbonate polyol Al.l preferably has a CO 2 content of 10 to 25% by weight, preferably 12 to 20% by weight.
  • the functionality of the polyether carbonate polyol Al.l is preferably from 1 to 6, preferably from 1 to 4, particularly preferably from 2 to 3.
  • the proportion of built-in CO2 (“units originating from carbon dioxide”; “C0 2 content”) in a polyether carbonate polyol can be determined from the evaluation of characteristic signals in the 'HN R spectrum.
  • the example below illustrates the determination of the level of carbon dioxide derived units in a CCE/propylene oxide polyethercarbonate polyol initiated on 1,8-octanediol.
  • the proportion of built-in CO2 in a polyether carbonate polyol and the ratio of cyclic carbonate to polyether carbonate polyol can be determined using ⁇ -NMR (a suitable device is from Bruker, DPX 400, 400 MHz; pulse program zg30, waiting time dl: 10 s, 64 scans).
  • ⁇ -NMR a suitable device is from Bruker, DPX 400, 400 MHz; pulse program zg30, waiting time dl: 10 s, 64 scans.
  • the sample is dissolved in deuterated chloroform.
  • Cyclic carbonate (which was formed as a by-product) resonating at 4.5 ppm; carbonate resulting from carbon dioxide incorporated in the polyethercarbonate polyol with resonances at 5.1 to 4.8 ppm; unreacted propylene oxide (PO) resonating at 2.4 ppm; polyether polyol (i.e., without incorporated carbon dioxide) with resonances at 1.2 to 1.0 ppm; the 1.8 octanediol incorporated as a starter molecule (if present) with a resonance at 1.6 to 1.52 ppm.
  • N [F(5,l - 4,8) - F(4,5)]* 102 + F(4,5) * 102 + F(2,4) * 58 + 0.33 * F(l, 2 - 1.0) * 58 + 0.25 * F(l.6 - 1.52) * 146
  • F(4.5) area of resonance at 4.5 ppm for cyclic carbonate (corresponds to an H atom)
  • F(5,1-4.8) area of resonance at 5.1-4.8 ppm for polyethercarbonate polyol and one H for cyclic carbonate.
  • F(1,6-1.52) area of resonance at 1.6 to 1.52 ppm for 1,8 octanediol (initiator) if present.
  • the factor 102 results from the sum of the molar masses of CO2 (molar mass 44 g/mol) and that of propylene oxide (molar mass 58 g/mol), the factor 58 results from the molar mass of propylene oxide and the factor 146 results from the molar mass of the starter used 1,8-octanediol (if available).
  • component A1 can contain other compounds with hydrogen atoms that are reactive toward isocyanates.
  • Component A1.2 comprises polyether polyols with a hydroxyl number according to DIN 53240-1 (June 2013) from 20 mg KOH/g to 250 mg KOH/g, preferably from 20 to 112 mg KOH/g and particularly preferably 20 mg KOH/g 80 mg KOH/g and is free of carbonate units.
  • the compounds according to A1.2 can be prepared by catalytic addition of one or more alkylene oxides onto H-functional starter compounds.
  • Alkylene oxides having 2 to 24 carbon atoms can be used as alkylene oxides (epoxides).
  • the alkylene oxides having 2 to 24 carbon atoms are, for example, one or more compounds selected from the group consisting of ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1-pentene oxide,
  • Ethylene oxide and/or propylene oxide and/or 1,2-butylene oxide are preferably used as alkylene oxides.
  • the alkylene oxides can be added to the reaction mixture individually, as a mixture or in succession. They can be random or block copolymers. If the alkylene oxides are metered in one after the other, the products produced (polyether polyols) contain polyether chains with block structures.
  • the H-functional starter compounds have functionalities from 2 to 6 and are preferably hydroxy-functional (OH-functional).
  • hydroxy-functional starter compounds are propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, hexanediol, pentanediol, 3-methyl-1,5-pentanediol, 1,12- Dodecanediol, glycerin, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, sucrose, hydroquinone, catechol, resorcinol, bisphenol F, bisphenol A, 1,3,5-trihydroxybenzene, methylol-containing condensates of formaldehyde and phenol or melamine or urea. These can also be used in a mixture. 1,2-Propylene glycol and/
  • the polyether polyols of component A1.2 contain from 0 to 60% by weight, preferably from 0 to 40% by weight, particularly preferably from 0 to 25% by weight, of ethylene oxide.
  • Component A1.3 comprises polyether polyols with a hydroxyl number according to DIN 53240-1 (June 2013) from 20 mg KOH/g to 250 mg KOH/g, preferably from 20 to 112 mg KOH/g and particularly preferably 20 mg KOH/g 80 mg KOH/g.
  • component A1.3 is prepared analogously to component A1.2, but with an ethylene oxide content of >60% by weight, preferably >65% by weight, being set in the polyether polyol.
  • Suitable alkylene oxides and H-functional starter compounds are the same as described for component A1.2.
  • suitable H-functional starter compounds are preferably those which have a functionality of 3 to 6, particularly preferably 3, so that polyether triols are formed.
  • Preferred starter compounds with a functionality of 3 are glycerol and/or trimethylolpropane, with glycerol being particularly preferred.
  • component A1.3 is a glycerol-started trifunctional polyether with an ethylene oxide content of 68 to 73% by weight and an OH number of 35 to 40 mg KOH/g.
  • Component A1.4 includes polymer polyols, PHD polyols and PIPA polyols.
  • Polymer polyols are polyols containing proportions of solid polymers produced by free radical polymerization of suitable monomers such as styrene or acrylonitrile in a base polyol such as a polyether polyol and/or polyether carbonate polyol.
  • PHD (polyurea dispersion) polyols are prepared, for example, by in situ polymerization of an isocyanate or an isocyanate mixture with a diamine and/or hydrazine in a polyol, preferably a polyether polyol.
  • the PHD dispersion is preferably prepared by reacting an isocyanate mixture used from a mixture of 75 to 85% by weight of 2,4-tolylene diisocyanate (2,4-TDI) and 15 to 25% by weight of 2,6-tolylene diisocyanate (2.6 TDI) with a Diamine and/or hydrazine in a polyether polyol, preferably a polyether polyol and/or polyether carbonate polyol prepared by alkoxylating a trifunctional starter (such as glycerol and/or trimethylolpropane) in the presence of carbon dioxide in the case of the polyether carbonate polyol.
  • a trifunctional starter such as glycerol and/or trimethylolpropane
  • the PIPA polyols are polyether polyols and/or polyether carbonate polyols modified by polyisocyanate polyaddition with alkanolamines, preferably triethanolamine-modified, the polyether carbonate polyol having a functionality of 2.5 to 4 and a hydroxyl number of 3 mg KOH/g to 112 mg KOH/g (molecular weight 500 to 18,000).
  • the polyether polyol is "EO-capped", i.e. the polyether polyol has terminal ethylene oxide groups.
  • PIPA polyols are described in detail in GB 2 072 204 A, DE 31 03 757 A1 and US Pat. No. 4,374,209.
  • diols e.g. 1,2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol
  • triols e.g. glycerol, trimethylolpropane
  • tetraols e.g. pentaerythritol
  • polyester polyols polythioether polyols or Polyacrylate polyols and polyether polyols, polyether carbonate polyols or polycarbonate polyols which do not fall under the definition of components Al.1 to A1.4.
  • ethylenediamine and triethanolamine started polyethers can also be used.
  • Blowing agents such as chemical and/or physical blowing agents are used as component A2.
  • Water or carboxylic acids and mixtures thereof, for example, are used as the chemical blowing agent A2.1. These react with isocyanate groups to form the propellant gas, for example in the case of water, carbon dioxide is formed and in the case of z.
  • B. formic acid produces carbon dioxide and carbon monoxide. At least one compound selected from the group consisting of formic acid, acetic acid, oxalic acid and ricinoleic acid is preferably used as the carboxylic acid. Water is particularly preferably used as the chemical blowing agent.
  • low-boiling organic compounds such as e.g. B. hydrocarbons, ethers, ketones, carboxylic acid esters, carbonic acid esters, halogenated hydrocarbons.
  • organic compounds which are inert towards the isocyanate component B and have boiling points below 100° C., preferably below 50° C., at atmospheric pressure. These boiling points have the advantage that the organic compounds evaporate under the influence of the exothermic polyaddition reaction.
  • Examples of such preferably used organic compounds are alkanes such as heptane, hexane, n- and isopentane, preferably technical mixtures of n- and isopentanes, n- and isobutane 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, carboxylic acid alkyl esters such as methyl formate, dimethyl oxalate and ethyl acetate and halogenated hydrocarbons such as methylene chloride, dichloromonofluoromethane, difluoromethane, trifluoromethane, difluoroethane, tetrafluoroethane, chlorodifluoroethane, 1,1-dichloro- 2,2,2-trifluoroethane, 2,
  • (hydro)fluorinated olefins such as HFO 1233zd(E) (trans-1-chloro-3,3,3-trifluoro-l-propene) or HFO 1336mzz(Z) (cis-l,l ,l,4,4,4-hexafluoro-2-butene) or additives such as FA 188 from 3M (l,l,l,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)pent- 2-en).
  • HFO 1233zd(E) trans-1-chloro-3,3,3-trifluoro-l-propene
  • HFO 1336mzz(Z) cis-l,l ,l,4,4,4-hexafluoro-2-butene
  • additives such as FA 188 from 3M (l,l,l,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)pent- 2-en).
  • the component contains A2
  • A2.2 0 to 15 parts by weight (based on A 100 parts by weight) of physical blowing agents Particular preference is given to using water as component A2.
  • component A3 a) catalysts (activators), b) surface-active additives (surfactants), such as emulsifiers and foam stabilizers, in particular those with low emissions such as products from the Tegostab ® LF series, c) additives such as reaction retardants (e.g.
  • acidic substances such as hydrochloric acid or organic acid halides
  • cell regulators such as paraffins or fatty alcohols or dimethylpolysiloxanes
  • pigments such as paraffins or fatty alcohols or dimethylpolysiloxanes
  • flame retardants such as tricresyl phosphate
  • stabilizers against aging and weathering plasticizers
  • fungistatic and bacteriostatic substances such as barium sulfate, kieselguhr, soot or whiting
  • fillers such as barium sulfate, kieselguhr, soot or whiting
  • Preferred catalysts are aliphatic tertiary amines (e.g. trimethylamine, tetramethylbutanediamine), cycloaliphatic tertiary amines (e.g.
  • 1,4-diaza(2,2,2)bicyclooctane 1,4-diaza(2,2,2)bicyclooctane
  • aliphatic amino ethers e.g. dimethylaminoethyl ether and N,N,N-trimethyl-N- hydroxyethyl bisaminoethyl ether
  • cycloaliphatic amino ethers e.g. dimethylaminoethyl ether and N,N,N-trimethyl-N- hydroxyethyl bisaminoethyl ether
  • N-ethylmorpholine aliphatic amidines, cycloaliphatic amidines, urea, derivatives of urea (such as aminoalkylureas), in particular (3-dimethylaminopropylamine)urea) and tin catalysts (such as dibutyltin oxide, dibutyltin dilaurate, tin octoate).
  • Particularly preferred catalysts are (i) urea, derivatives of urea and/or (ii) the abovementioned amines and amino ethers, characterized in that the amines and amino ethers contain a functional group which reacts chemically with the isocyanate.
  • the functional group is a hydroxyl group, a primary or secondary amino group.
  • Aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates are used as component B, for example those of the formula (V)
  • n is an integer between 2-4, preferably 2 or 3
  • Q is an aliphatic hydrocarbon radical having 2-18, preferably 6-10 carbon atoms, a cycloaliphatic hydrocarbon radical having 4-15, preferably 6-13 carbon atoms or an araliphatic hydrocarbon radical having 8-15, preferably 8-13 carbon atoms stands.
  • the technically easily accessible polyisocyanates are particularly preferred, e.g.
  • TDI 2,4- and 2,6-tolylene diisocyanate, and any mixtures of these isomers
  • Polyphenylpolymethylene polyisocyanates such as those produced by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI") and polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups
  • modified polyisocyanates in particular those modified polyisocyanates which differ from 2,4- and/or 2,6-tolylene diisocyanate or from 4,4'- and/or 2,4'- diphenylmethane diisocyanate.
  • component B at least one Compound selected from the group consisting of 2,4- and 2,6-tolylene diisocyanate, 4,4'- and 2,4'- and 2,2'-diphenylmethane diisocyanate and polyphenylpolymethylene polyisocyanate ("multi-core MDI") used.
  • a diphenylmethane diisocyanate mixture is very particularly preferably used as component B, consisting of a) 45 to 90% by weight of 4,4'-diphenylmethane diisocyanate and b) 10 to 55% by weight of 2,2'-diphenylmethane diisocyanate and/or 2 ,4'-diphenylmethane diisocyanate and c) 0 to 45 wt. or pMDI-based carbodiimides, uretdiones or uretdionimines.
  • a diphenylmethane diisocyanate mixture is used as component B, consisting of a) 35 to 45% by weight of 4,4'-diphenylmethane diisocyanate and b) 1 to 5% by weight of 2,2'-diphenylmethane diisocyanate and/or 2,4'-diphenylmethane diisocyanate and c) 50 to 64% by weight of polyphenyl polymethylene polyisocyanate ("multi-core MDI”) and/or 2,2'-, 2,4'-, 4,4'-diphenylmethane diisocyanate -, and/or pMDI-based carbodiimides, uretdione or uretdione imines.
  • multi-core MDI polyphenyl polymethylene polyisocyanate
  • pMDI-based carbodiimides uretdione or uretdione imines.
  • a component K can also be used in order to reduce the proportion of cyclic carbonates in the polyurethane foam.
  • components K which can be used are: a) esters of monobasic or polybasic carboxylic acids, the pKa values of the (first) dissociation of the carboxylic acids being 0.5 to 4.0, such as methyl and ethyl esters of oxalic acid and/or malonic acid , b) mono-, di- and polysulfonates of mono- and polyfunctional alcohols, such as para-
  • the polyurethane foams obtained according to the invention are preferably flexible polyurethane foams or semirigid polyurethane foams.
  • the reaction components are reacted by the known one-step process, the prepolymer process or the semiprepolymer process, mechanical equipment often being used.
  • the polyurethane foams can be produced as molded foams or also as block foams, it being possible for the molded foams to be produced in a hot-curing or cold-curing manner.
  • the invention therefore relates to a process for producing the polyurethane foams, the polyurethane foams produced by this process and their use.
  • the polyurethane foams obtainable according to the invention are used, for example, in the following areas: furniture upholstery, textile inserts, mattresses, automobile seats, headrests, armrests, sponges and components, as well as seat and instrument paneling, and can have indexes of 60 to 250, preferably 70 to 120, particularly preferably 75 to 120 and bulk densities of 4 to 600 kg/m 3 , preferably 60 to 120 kg/m 3 (semi-rigid foam) or preferably 15 to 55 kg/m 3 (flexible foam).
  • the isocyanate number (also called number or isocyanate index) is the quotient of the amount of substance [mol] of isocyanate groups actually used and the amount of substance [mol] of isocyanate-reactive groups actually used, multiplied by 100:
  • the NCO value (also: NCO content, isocyanate content) is determined using EN ISO 11909:2007.
  • the preferred flexible polyurethane foams preferably have a bulk density according to DIN EN ISO 3386-1-98 in the range from 15 to 55 kg/m 3 , preferably from 20 to 50 kg/m 3 .
  • the compressive strength of the polyurethane foams was determined according to DIN EN ISO 3386-1 in the September 2010 version in the direction of foaming and the bulk density according to DIN EN ISO 845 in the October 2009 version.
  • the compression set was measured according to DIN EN ISO 1856 in the January 2008 version with 90% compression set at 70°C for 22 hours.
  • OH numbers (hydroxyl numbers) were determined in accordance with the provisions of DIN 53240-1 (June 2013).
  • the emissions in the flexible polyurethane foams were determined in accordance with the LGA Pollutant Tested certification. The emissions were measured after conditioning the sample in the test chamber for 7 days. Test chamber conditions: 23°C ⁇ 1°C, area-specific air flow rate: 0.5 m 3 /(m 2 -h) ⁇ 0.05 m 3 /(m 2 -h) and rel. Humidity 50% ⁇ 3%.
  • AO polymer 1 Alkylene oxide polymer based on a propylene glycol/glycerol mixture and addition of 90% by weight of propylene oxide and 10% by weight of ethylene oxide, based in each case on the total mass of the alkylene oxide used, functionality of 2.8 and molecular weight of 670 g/ mol produced by DMC catalysis
  • AO-Polymer 2 Alkylene oxide polymer based on a propylene glycol/glycerol mixture and addition of 80% by weight of propylene oxide and 20% by weight of ethylene oxide, based in each case on the total mass of the alkylene oxide used, functionality of 2.8 and molecular weight of 670 g/ mol produced by DMC catalysis
  • AO polymer 3 Alkylene oxide polymer based on a propylene glycol/glycerol mixture and addition of 100% by weight of propylene oxide, based on the total mass of the alkylene oxide used, functionality of 2.8 and molecular weight of 670 g/mol, produced by DMC catalysis
  • A3-1 silicone stabilizer (Tegostab BF2370)
  • the flexible polyurethane foams described in Table 1 were produced in a discontinuous process.
  • Components A1-1 to A3-2 are weighed in according to the recipe (see Table 1) and stirred at room temperature for 20 seconds at a speed of 680 rpm. Then the necessary amount of component A3 -3 is added and the mixture is stirred at a speed of 680 rpm for 10 seconds with an agitator.
  • component B1 is added and stirred with a stirrer at a speed of 750 rpm for 10 seconds. The mass is then added to a 1 m 3 mold. The walls of the 1 m 3 form were previously covered on the inside with polyethylene foil.
  • the height of the flexible polyurethane foam blocks was about 74-82 cm.
  • the finished flexible polyurethane foam was stored in the post-reaction store for approx. 20-24 hours before it was sawn into test specimens for testing. Two specimens were analyzed to determine the mechanical properties of the flexible polyurethane foams. Table 1 shows the mean of the measurements in each case. Table 1: Formulations and mechanical properties
  • Comparative Example Table 1 shows the mechanical properties of the polyurethane foams obtained from Examples 1 to 3.
  • a polyether carbonate polyol A1.1 was used in each of Examples 1 and 2.
  • the polyurethane foams from Examples 1 and 2 achieve tensile strength values of 110 kPa and 121 kPa, respectively, and values of 137% and 150%, respectively, for the elongation at break.
  • a polyether carbonate polyol A1.5-1 based on an alkylene oxide polymer with 100% by weight of propylene oxide was used in example 3 (comparison).
  • the resulting polyurethane foam from Example 3 has a tensile strength of only 88 kPa and an elongation at break of 81%.
  • the flexible polyurethane foams produced according to the invention also have low emission values in the measurements according to LGA certification.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un procédé de production de mousses de polyuréthane, les constituants (A) contenant (A1) des composés ayant des atomes d'hydrogène susceptibles de réagir avec les isocyanates, y compris (A1.1) un polyéther carbonate polyol, (A2) un propulseur et, quand cela est approprié, (A3) des adjuvants et des additifs, et (B) des di-isocyanates et/ou des polyisocyanates, étant mis à réagir les uns avec les autres, caractérisé en ce que la structure de A1.1 est obtenue à partir d'un composé de départ S1 ayant une masse moléculaire de 18 à 200 g/mol, sur lequel sont disposés un premier bloc oxyde d'alkylène interne contenant 0,5 à 30 % en poids de motifs structuraux d'oxyde d'éthylène, par rapport à la masse totale de l'oxyde d'alkylène utilisé dans le premier bloc d'oxyde d'alkylène, et un second bloc extérieur de dioxyde de carbone et d'oxyde d'alkylène.
PCT/EP2022/053554 2021-02-16 2022-02-15 Procédé de production d'une mousse de polyuréthane WO2022175210A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4089835A (en) 1975-03-27 1978-05-16 Bayer Aktiengesellschaft Stable polyurethane dispersions and process for production thereof
US4260530A (en) 1976-09-01 1981-04-07 Bayer Aktiengesellschaft Process for the preparation of polyurethane resins using stable dispersions as a starting component
GB2072204A (en) 1980-02-14 1981-09-30 Rowlands J P Polymer-modified polyols useful in polyurethane manufacture
DE3103757A1 (de) 1980-02-14 1981-12-17 Jeffrey Philip Littleover Derby Rowlands Polymer-modifizierte polyalkohole, verfahren zu deren herstellung und verwendung zur herstellung von polyurethan
US4374209A (en) 1980-10-01 1983-02-15 Interchem International S.A. Polymer-modified polyols useful in polyurethane manufacture
US7304172B2 (en) 2004-10-08 2007-12-04 Cornell Research Foundation, Inc. Polycarbonates made using highly selective catalysts
WO2008058913A1 (fr) * 2006-11-15 2008-05-22 Basf Se Procédé de fabrication de mousses souples en polyuréthanne
US20120165549A1 (en) 2008-07-30 2012-06-28 Sk Energy Co., Ltd. Novel coordination complexes and process of producing polycarbonate by copolymerization of carbon dioxide and epoxide using the same as catalyst
WO2012130760A1 (fr) 2011-03-28 2012-10-04 Bayer Materialscience Ag Procédé de production de mousses souples de polyuréthane
WO2015078801A1 (fr) 2013-11-27 2015-06-04 Bayer Materialscience Ag Mélanges de polyéthercarbonatepolyols et de polyétherpolyols pour fabriquer des matières alvéolaires molles en polyuréthane

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4089835A (en) 1975-03-27 1978-05-16 Bayer Aktiengesellschaft Stable polyurethane dispersions and process for production thereof
US4260530A (en) 1976-09-01 1981-04-07 Bayer Aktiengesellschaft Process for the preparation of polyurethane resins using stable dispersions as a starting component
GB2072204A (en) 1980-02-14 1981-09-30 Rowlands J P Polymer-modified polyols useful in polyurethane manufacture
DE3103757A1 (de) 1980-02-14 1981-12-17 Jeffrey Philip Littleover Derby Rowlands Polymer-modifizierte polyalkohole, verfahren zu deren herstellung und verwendung zur herstellung von polyurethan
US4374209A (en) 1980-10-01 1983-02-15 Interchem International S.A. Polymer-modified polyols useful in polyurethane manufacture
US7304172B2 (en) 2004-10-08 2007-12-04 Cornell Research Foundation, Inc. Polycarbonates made using highly selective catalysts
WO2008058913A1 (fr) * 2006-11-15 2008-05-22 Basf Se Procédé de fabrication de mousses souples en polyuréthanne
US20120165549A1 (en) 2008-07-30 2012-06-28 Sk Energy Co., Ltd. Novel coordination complexes and process of producing polycarbonate by copolymerization of carbon dioxide and epoxide using the same as catalyst
WO2012130760A1 (fr) 2011-03-28 2012-10-04 Bayer Materialscience Ag Procédé de production de mousses souples de polyuréthane
WO2015078801A1 (fr) 2013-11-27 2015-06-04 Bayer Materialscience Ag Mélanges de polyéthercarbonatepolyols et de polyétherpolyols pour fabriquer des matières alvéolaires molles en polyuréthane

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