WO2023144058A1 - Production de mousses de polyuréthane souples aliphatiques avec des temps de prise (temps sans pégosité) et des temps de montée réduits - Google Patents

Production de mousses de polyuréthane souples aliphatiques avec des temps de prise (temps sans pégosité) et des temps de montée réduits Download PDF

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WO2023144058A1
WO2023144058A1 PCT/EP2023/051471 EP2023051471W WO2023144058A1 WO 2023144058 A1 WO2023144058 A1 WO 2023144058A1 EP 2023051471 W EP2023051471 W EP 2023051471W WO 2023144058 A1 WO2023144058 A1 WO 2023144058A1
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component
aliphatic
monohydroxy
polyisocyanate
particularly preferably
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PCT/EP2023/051471
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German (de)
English (en)
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Lutz Boehnke
Veronika EILERMANN
Dirk Achten
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Covestro Deutschland Ag
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Publication of WO2023144058A1 publication Critical patent/WO2023144058A1/fr

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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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines containing two hydroxy 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
    • C08G18/44—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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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 the production of aliphatic flexible polyurethane foams using aliphatic oligomeric polyisocyanates and monohydroxy-functional compounds, in particular the rise time and/or the setting time (tack-free time) in the production of the flexible polyurethane foams being shortened and the flexible polyurethane foams preferably have a low compression hardness and/or a low compression set value (CVR).
  • CVR low compression hardness and/or a low compression set value
  • the invention also relates to a, preferably flexible, flexible polyurethane foam which is produced or can be produced by the aforementioned method and has a low compression hardness and/or a low compression set value (DVR), and its use, for example for the production of body-supporting elements such as upholstery, mattresses, furniture, automobile seats and motorcycle seats.
  • DVR low compression hardness and/or a low compression set value
  • the invention also relates to the use of a monohydroxy-functional compound in combination with an aliphatic oligomeric polyisocyanate and optionally a monomeric aliphatic polyisocyanate and/or a dimeric aliphatic polyisocyanate to reduce the compression hardness and/or the compression set value of flexible polyurethane foams and/or to shorten the Rise time and/or setting time in the manufacture of flexible polyurethane foams.
  • Flexible foams account for the largest volume of application for polyurethanes and are the largest category of polymeric cellular materials. They are mainly used for upholstery in the furniture industry, for mattresses, in the automotive industry and in the textile industry.
  • Currently commercially available flexible foams are usually made from petroleum based polyols and aromatic isocyanates, most often from a mixture of toluene 2,4-diisocyanate (2,4-TDI) and toluene 2,6-diisocyanate (2,6-TDI) or diphenylmethane diisocyanate -Mixtures (MDI) manufactured.
  • monomeric diisocyanates to produce polyurethane foams, high demands are made on process reliability and air control with regard to volatile components.
  • the use of low-monomer, oligomeric polyisocyanates instead of the volatile monomeric isocyanates represents a major advantage in terms of occupational safety.
  • EP0006150 B1 discloses the use of HDI-based biurets or of urethane-modified polyisocyanates from aliphatic or cycloaliphatic diisocyanates and low molecular weight alkanediols.
  • EP 3296336 A1 discloses the use of pentamethylene diisocyanate-based (PDI) uretdione for the production of polyurethanes, which can also contain isocyanurates and allophants based on PDI or HDI.
  • PDI pentamethylene diisocyanate-based
  • WO 02/074826 A1 discloses the use of isocyanurates or biurets based on aliphatic isocyanates, such as HDI.
  • Polyurethane foams can be obtained from these polyisocyanates by reaction with long-chain polyether polyols or polyester polyols and crosslinkers, as well as blowing agents and foam stabilizers.
  • An ideal foam system has a long start-up (or dwell) time, and once the reaction has started, the foam should then rise and set quickly.
  • Flexible polyurethane foam systems based on aromatic isocyanates that are customary on the market have short start-up times, but the setting times (tack-free times) and rising times of these foam systems are relatively long.
  • Polyurethane flexible foam systems based on aliphatic It is true that isocyanates generally have significantly longer starting times and comparatively short setting times and rising times. However, it would be advantageous if the setting times and/or the rising times in the production of flexible aliphatic polyurethane foams could be shortened even further and the starting times not changed, if possible, only slightly. Such a wide processing window is generally considered to be very advantageous.
  • the object of the present invention was to provide flexible polyurethane foams based on aliphatic oligomeric polyisocyanates which are suitable for use in typical flexible foam applications such as upholstery, mattresses, furniture, automobile seats and motorcycle seats.
  • the foams should have improved setting times (tack-free time) and/or rise times during production compared to the foams of the prior art and preferably have improved mechanical properties, especially with regard to compression hardness and compression set value (CVR).
  • CVR compression hardness and compression set value
  • starting materials based on CCE and/or based on renewable raw materials should also be able to be used in the production of this flexible foam in order to improve the environmental and CCE balance sheet of these flexible polyurethane foams.
  • component E optionally auxiliaries and additives different from component E).
  • composition comprising the components is to be understood as meaning that the composition contains or consists of components A through F. In a preferred embodiment, the composition consists of components A to F.
  • the invention relates to a flexible polyurethane foam obtained or obtainable by the process according to the invention.
  • the invention also relates to the use of the flexible polyurethane foam according to the invention as or for the production of body-supporting elements, in particular upholstery, mattresses, furniture, automobile seats and motorcycle seats.
  • the invention also relates to the use of a monohydroxy-functional compound in combination with an aliphatic oligomeric polyisocyanate and optionally a monomeric aliphatic polyisocyanate and/or a dimeric aliphatic polyisocyanate with an isocyanate index of at least 70 to reduce the compression hardness and/or the compression set value of polyurethane -flexible foams.
  • the invention also relates to the use of a monohydroxy-functional compound in combination with an aliphatic oligomeric polyisocyanate and optionally a monomeric aliphatic polyisocyanate and/or a dimeric aliphatic polyisocyanate with an isocyanate index of at least 70 to shorten the rise time and/or setting time in the production of polyurethane -flexible foams.
  • aliphatic oligomeric polyisocyanates in particular those of the isocyanurate or iminooxadiazinedione type, in combination with monohydroxy-functional compounds and optionally monomeric aliphatic polyisocyanates and/or dimeric aliphatic polyisocyanates lead to flexible polyurethane foams which meet the stated requirements and which in particular, have a shortened rising time, preferably ⁇ 100 s and/or setting time (tack-free time) of ⁇ 170 s, each based on 450 g ⁇ 5 g of composition during production and preferably have an improved compressive strength (in the 4th cycle, measured according to DIN EN ISO 3386-1), preferably of ⁇ 14.0 kPa and an improved compression set value (measured according to DIN EN ISO 1856-2008), preferably of ⁇ 3.5%.
  • a flexible polyurethane foam is typically understood to mean a foam that is used in the fields of upholstery, mattresses, packaging, automotive applications, and footwear.
  • flexible polyurethane foams are polyaddition products made from polyols and usually diisocyanates, which are produced in an exothermic reaction using the mostly chemically produced blowing agent CO 2 , which is produced from the NCO-water reaction.
  • the gel (NCO-OH reaction) and blowing reaction (NCO-water reaction) can be modified with the use of catalysts, stabilizers and other auxiliaries, resulting in a wide range of different foams.
  • the polyols used are preferably long-chain polyols with a functionality of 2 to 3 to a large extent.
  • the start time, setting time and rise time are defined as follows within the scope of the invention and determined accordingly:
  • Start time Time from the start of the mixing process to a visually perceptible change in the reaction mixture, ie until the reaction mixture rises for the first time.
  • auxiliary lines lines running obliquely upwards
  • setting time is understood to mean the so-called tack-free time.
  • the tack-free time is the period of time from the start of mixing to the state/point in time at which the surface of the foam mass is no longer tacky. It is determined by dabbing the no longer rising foam with a wooden stick. The point in time at which there is no longer any sticking is referred to as the tack-free time.
  • composition according to the invention contains at least one monohydroxy-functional compound and at least one polyol.
  • Primary, secondary and/or tertiary monohydroxy-functional compounds having 1 to 12 carbon atoms, preferably primary monohydroxy-functional compounds, are used as component A1).
  • the carbon chains can be saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or aromatic and contain heteroatoms such as oxygen.
  • hydroxy-functional compounds preferably low-molecular monohydroxy-functional compounds (alcohols) with a molecular weight of 32.04 g/mol to 186.34 g/mol, which in addition to the hydroxy functionality (OH group) preferably have no further functionalities (e.g. ether or Ester functionalities, etc.) have.
  • acyclic and/or cyclic monohydroxy-functional alkanols and/or acyclic and/or cyclic monohydroxy-functional alkenols are preferred.
  • Examples include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, sec-butanol, tert-butanol, pentane-1-ol, pentane-2-ol, pentane-3-ol, 2 -Methyl-butan-1-ol, 2-methyl-butan-2-ol, 3-methyl-butan-1-ol, 3-methyl-butan-2-ol, 2,2-dimethyl-propan-1-ol , hexan-1-ol, hexan-2-ol, hexan-3-ol, 2-methylpentan-1-ol, 3-methylpentan-1-ol, 4-methylpentan-1-ol, 2-methylpentan-2-ol , 3-methylpentan-2-ol, 2,2-dimethylbutan-l-ol, 2,3-dimethylbutan-l-ol, 3,3-dimethylbutan
  • monohydroxy-functional compounds with a melting point of ⁇ 60°C, very particularly preferably ⁇ 40°C and most preferably ⁇ 20°C.
  • low molecular weight primary are monohydroxy functional Compounds are preferred because they react more quickly with the isocyanate groups due to their significantly higher reactivity.
  • polymeric monohydroxy-functional compounds preferably polyether monools, polycarbonate monools, polyester carbonate monools,
  • Polyethercarbonate monools, polyetherestercarbonate monools and/or mixtures thereof are used, the polymeric monohydroxy-functional compound particularly preferably having a primary hydroxyl group.
  • the polymeric monohydroxy-functional compound A2) preferably has a hydroxyl number of 20 to 250 mg KOH/g, preferably 20 to 112 mg KOH/g and particularly preferably 20 to 50 mg KOH/g, measured according to DIN 53240-3:2016-03.
  • 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 comprising or consisting of ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide ( isobutene oxide), 1-pentene oxide, 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2 -Methyl-1,2-pentene oxide, 4-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 1-heptene oxide, 1-octene oxide, 1-nonene oxide, 1-decene oxide, 1-und
  • 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 be supplied one after the other. It 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 proportion of ethylene oxide in the total amount of propylene oxide and ethylene oxide used is >0 and ⁇ 90% by weight, preferably >0 and ⁇ 60% by weight these have a greater reactivity towards isocyanates.
  • H-functional starter compounds are monofunctional for the production of polyether monools.
  • “H-functional” means a starter compound which has H atoms which are active towards alkoxylation.
  • alcohols, amines, thiols and carboxylic acids can be used.
  • Examples of preferred monofunctional alcohols are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 3-buten-1-ol, 3-butyn-1-ol, 2-methyl- 3-buten-2-ol, 2-methyl-3-butyn-2-ol, propagyl alcohol, 2-methyl-2-propanol, 1-tert-butoxy-2-propanol., 1-pentanol, 2-pentanol,
  • Suitable monofunctional amines are: butylamine, tert-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, morpholine.
  • monofunctional thiols ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol, 3-methyl-1-butanethiol, 2-butene-1-thiol, thiophenol.
  • monofunctional carboxylic acids formic acid, acetic acid, propionic acid, butyric acid, fatty acids such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, acrylic acid.
  • starter compounds are compounds from the group of glycol ethers, such as diethylene glycol monoethyl ether.
  • the monofunctional starter compounds are preferably diethylene glycol monobutyl ether (butyldiglycol).
  • the mole fraction of the OH groups in the sum of components A1) and A2) is 25.0 to 90.0 mol %, preferably 35.0 to 85.0 mol %, more preferably 40.0 to 80.0 mol -% is based on the total amount of OH groups of component A).
  • the equivalent ratio of the OH groups in the sum of components A1) and A2) to the NCO groups of components B) is preferably from 0.15 to 0.65, more preferably from 0.20 to 0.55 and particularly preferably from 0.25 to is 0.50.
  • the at least one polyol of component A) is preferably selected from the group comprising or consisting of
  • polyether polyols polyether polyols, polyester polyols, polycarbonate polyols and/or mixtures thereof, the polyol of component A) preferably comprising or consisting of at least one polyether carbonate polyol A3).
  • the polyether carbonate polyols that can be used as component A3) have a hydroxyl number (OH number) according to DIN 53240-3:2016-03 from >20 mg KOH/g to ⁇ 600 mg KOH/g, preferably from >50 mg KOH/g to ⁇ 500 mg KOH/g, particularly preferably from >50 mg KOH/g to ⁇ 300 mg KOH/g.
  • OH number hydroxyl number
  • the same alkylene oxides (epoxides) and the same H-functional starter substances can be used as described below for the production of the polyetherpolyols (see component A4).
  • the copolymerization of carbon dioxide and one or more alkylene oxides preferably takes place in the presence of at least one DMC catalyst (double metal cyanide catalyst).
  • DMC catalyst double metal cyanide catalyst
  • polyethercarbonate polyols includes the following steps by:
  • an H-functional starter substance or a mixture of at least two H-functional starter substances and optionally water and/or other volatile compounds are removed by elevated temperature and/or reduced pressure ("drying"), where the DMC catalyst is added to the H-functional starter substance or to the mixture of at least two H-functional starter substances before or after drying,
  • step (ß) for activation a portion (based on the total amount of the amount of alkylene oxides used in the activation and copolymerization) of one or more Alkylene oxides is added to the mixture resulting from step (a), this addition of a portion of alkylene oxide optionally being able to take place in the presence of CO 2 , and the temperature peak ("hotspot") occurring as a result of the following exothermic chemical reaction and/or a pressure drop in the reactor is awaited in each case, and step (ß) for activation can also be carried out several times,
  • step (Y) one or more of the alkylene oxides and carbon dioxide are added to the mixture resulting from step (ß), where the alkylene oxides used in step (y) can be the same or different from the alkylene oxides used in step (ß), and where after Step (y) is not followed by a further alkoxylation step.
  • DMC catalysts are known in principle from the prior art for the homopolymerization of epoxides (see e.g. US-A 3,404,109, US-A 3,829,505, US-A 3,941,849 and US-A 5,158,922).
  • DMC catalysts e.g. in US-A 5 470 813, EP-A 700 949, EP-A 743 093, EP-A 761 708, WO-A 97/40086, WO-A 98/16310 and WO-A 00 /47649 have very high activity in the homopolymerization of epoxides and allow the production of polyether polyols and/or polyether carbonate polyols at very low catalyst concentrations (25 ppm or less).
  • a typical example are the highly active DMC catalysts described in EP-A 700949, which, in addition to a double metal cyanide compound (e.g. zinc hexacyanocobaltate(III)) and an organic complex ligand (e.g. t-butanol), also contain a polyether with a number-average molecular weight Mn greater than 500 g /mol included.
  • a double metal cyanide compound e.g. zinc hexacyanocobaltate(III)
  • an organic complex ligand e.g. t-butanol
  • the DMC catalyst is usually used in an amount of ⁇ 1% by weight, preferably in an amount of ⁇ 0.5% by weight, particularly preferably in an amount of ⁇ 500 ppm and in particular in an amount of ⁇ 300 ppm. each used based on the weight of the polyether carbonate polyol.
  • the polyether carbonate polyol of component A3) has a content of carbonate groups ("units originating from carbon dioxide"), calculated as CO 2 , of >2.0 and ⁇ 30.0% by weight, preferably >5 .0 and ⁇ 28.0% by weight and particularly preferably >10.0 and ⁇ 25.0% by weight.
  • the polyethercarbonate polyols to be used according to the invention preferably also have ether groups between the carbonate groups, which is shown schematically in formula (I).
  • R ' is an organic radical such as an alkyl, alkylaryl or aryl radical, each of which can also contain heteroatoms such as O, S, Si, etc.
  • the subscripts e and f stand for an integer number.
  • the polyethercarbonate polyol shown in the scheme according to formula (I) should only be understood to mean that blocks with the structure shown can in principle be found in the polyethercarbonate polyol, but the order, number and length of the blocks can vary and not to that shown in formula (I). Polyethercarbonate polyol is limited. With regard to formula (I), this means that the ratio of e/f is preferably from 2:1 to 1:20, particularly preferably from 1.5:1 to 1:10.
  • the proportion of incorporated CO 2 (“units originating from carbon dioxide”) in a polyether carbonate polyol can be determined from the evaluation of characteristic signals in the 1 H NMR spectrum.
  • the following example illustrates the determination of the level of carbon dioxide derived units in a 1,8-octanediol initiated CCE/propylene oxide polyethercarbonate polyol.
  • the proportion of incorporated CO 2 in a polyether carbonate polyol and the ratio of propylene carbonate to polyether carbonate polyol can be determined by means of 'H-NMR (a suitable device is from Bruker, DPX 400, 400 MHz; pulse program zg30, waiting time dl: 10 s, 64 scans). become. In each case, 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 (ie 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.
  • the weight fraction (in % by weight) of polymer-bound carbonate (LC') in the reaction mixture was calculated according to formula (II), formula (II) where the value for N ("denominator" N) is calculated according to formula (III):
  • 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 atom for cyclic carbonate.
  • F(2,4) area of resonance at 2.4 ppm for free, unreacted propylene oxide
  • F(1.2-1.0) area of resonance at 1.2-1.0 ppm for polyether polyol
  • 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 CO 2 (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 used Starter 1,8-octanediol (if available).
  • the weight fraction (in wt%) of cyclic carbonate (CC') in the reaction mixture was calculated according to formula (IV), formula (IV) V 7 where the value for N is calculated according to formula (III).
  • the composition from the values of the composition of the reaction mixture based on the polymer fraction (consisting of polyether polyol, which was built up from starter and propylene oxide during the activation steps taking place under CCh-free conditions, and polyether carbonate polyol, built up from starter, propylene oxide and carbon dioxide during the activation steps taking place in the presence of CO 2 and during the copolymerization), the non-polymer components of the reaction mixture (ie cyclic propylene carbonate and any unreacted propylene oxide present) were eliminated by calculation.
  • the specification of the CCh content in the polyethercarbonate polyol is normalized to the proportion of the polyethercarbonate polyol molecule that was formed during the copolymerization and possibly the activation steps in the presence of CO 2 (ie the proportion of the polyethercarbonate polyol molecule that consists of the starter (1, 8-octanediol, if present) as well as from the reaction of the initiator with epoxide, which was added under CCh-free conditions, were not taken into account here).
  • Polyethercarbonate polyols are commercially available, for example, under the trade name Cardyon® from Covestro Deutschland AG.
  • the polyol of component A) preferably comprises at least one polyether carbonate polyol A3).
  • Component A4) preferably has an average functionality of >1, particularly preferably >2.
  • Suitable polyether polyols are those with a hydroxyl number according to DIN 53240-3:2016-03 from >20 mg KOH/g to ⁇ 550 mg KOH/g, preferably from >20 to ⁇ 250 mg KOH/g and particularly preferably >20 mg KOH /g to ⁇ 80 mg KOH/g.
  • These compounds can be prepared analogously to the preparation of the polyether monools described above under component A2.
  • the alkylene oxides described there can be used as alkylene oxides be used; the same preferred ranges apply.
  • H-functional starter molecules with an average functionality of ⁇ 1 to ⁇ 6, preferably ⁇ 1.5 and ⁇ 6, particularly preferably ⁇ 2 and ⁇ 4, very particularly preferably ⁇ 2 and ⁇ 3, are used to produce the polyether polyols.
  • H-functional starter substances Compounds having H atoms which are active for the alkoxylation can be used as suitable H-functional starter substances.
  • Groups with active H atoms which are active for the alkoxylation are, for example -OH, -NH2 (primary amines), -NH- (secondary amines), -SH and -CO 2 H, preference is given to -OH and -NH2, particular preference is given to - OH.
  • the H-functional starter substance is, for example, one or more compounds selected from the group comprising or consisting of water, polyhydric alcohols, polyhydric amines, polyhydric thiols, amino alcohols, thioalcohols, hydroxy esters, polyether polyols, polyester polyols, polyester ether polyols, polyether carbonate polyols, polycarbonate polyols, polycarbonates , polyethyleneimines, polyetheramines (e.g.
  • Jeffamine® commercially available from Huntsman, such as D-230, D-400, D-2000, T-403, T-3000, T-5000 or corresponding products from BASF , such as polyetheramine D230, D400, D200, T403, T5000), polytetrahydrofurans (e.g.
  • PolyTHF® from BASF such as PolyTHF® 250, 650S, 1000, 1000S, 1400, 1800, 2000) , Polytetrahydrofuranamine (BASF product Polytetrahydrofuranamin 1700), polyether thiols, polyacrylate polyols, castor oil, the mono or diglyceride of ricinoleic acid, monoglycerides of fatty acids, chemically modified mono-, di- and/or triglycerides of fatty acids, and C1-C24 alkyl fatty acid esters, which on average contain at least 2 OH groups per molecule used.
  • the C1-C24 alkyl fatty acid esters which contain on average at least 2 OH groups per molecule, are commercial products such as Lupranol Balance® (BASF AG), Merginol® types (Hobum Oleochemicals GmbH), Sovermol® grades (Cognis Deutschland GmbH & Co. KG) and Soyol®TM grades (USSC Co.).
  • Polyhydric alcohols suitable as H-functional starter substances are, for example, dihydric alcohols (such as 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-1,5-pentanediol), 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, bis- (hydroxymethyl)cyclohexanes (such as 1,4-bis(hydroxymethyl)cyclohexane), triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, tripropylene glycol,
  • the H-functional starter substances can also be selected from the substance class of the polyether polyols, in particular those with a number-average molecular weight Mn in the range from 100 to 4000 g/mol, preferably 250 to 2000 g/mol. Preference is given to polyether polyols which are built up from repeating ethylene oxide and propylene oxide units, preferably with a proportion of 35 to 100% propylene oxide units, particularly preferably with a proportion of 50 to 100% propylene oxide units. These can be random copolymers, gradient copolymers, alternating or block copolymers of ethylene oxide and propylene oxide.
  • Suitable polyether polyols built up from repeating propylene oxide and/or ethylene oxide units are, for example, the Desmophen®, Acclaim®, Arcol®, Baycoll®, Bayfill®, Bayflex®, Baygal®, PET® and polyether polyols from Covestro GmbH 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, Polyether® S180).
  • Covestro Deutschland AG such as Desmophen® 3600Z, Desmophen® 1900U, Acclaim® Polyol 2200, Acclaim® Polyol 40001, Arcol® Polyol 1004, Arcol® Polyol 1010, Arcol® Polyol 1030, Ar
  • suitable homo-polyethylene oxides are, for example, the Pluriol® E brands from BASF SE
  • suitable homo-polypropylene oxides are, for example, the Pluriol® P brands from BASF SE
  • suitable mixed copolymers of ethylene oxide and propylene oxide are, for example, Pluronic® PE or Pluriol® RPE -Brands of BASF SE.
  • the H-functional starter substances can also be selected from the substance class of polyester polyols, in particular those with a number-average molecular weight Mn in the range from 200 to 4500 g/mol, preferably 400 to 2500 g/mol. At least difunctional polyesters are used as polyester polyols. Polyester polyols preferably consist of alternating acid and alcohol units. As acid components z. B. Succinic acid, maleic acid, maleic anhydride, adipic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, Tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or mixtures of the acids and/or anhydrides mentioned are used.
  • alcohol components z. B ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis (hydroxymethyl) -cyclohexane, Di ethyl en glycol, dipropylene glycol, trimethylolpropane, glycerol, pentaerythritol or mixtures of the alcohols mentioned are used.
  • polyester ether polyols are obtained which can also be used as starter substances for the production of the polyether carbonate polyols. If polyether polyols are used to produce the polyester ether polyols, preference is given to polyether polyols having a number-average molecular weight Mn of from 150 to 2000 g/mol.
  • polycarbonate polyols can be used as H-functional starter substances, in particular those with a molecular weight Mn in the range from 150 to 4500 g/mol, preferably 500 to 2500, which are produced, for example, by reacting phosgene, dimethyl carbonate, di ethyl carbonate or diphenyl carbonate and di- and/or polyfunctional alcohols or polyester polyols or polyether polyols.
  • polycarbonate polyols can be found e.g. B. in EP-A 1359177.
  • the Desmophen® C grades from Covestro Germany AG can be used as polycarbonate dioie, such as. B. Desmophen® C 1100 or Desmophen® C 2200.
  • Polyethercarbonate polyols can also be used as H-functional starter substances.
  • polyether carbonate polyols that are produced by the process described above are used.
  • the polyether carbonate polyols used as H-functional starter substances are prepared beforehand in a separate reaction step.
  • Preferred H-functional starter substances are alcohols of the general formula (V),
  • alcohols according to formula (V) are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol.
  • H-functional starter sub substances are neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, reaction products of Alcohols according to formula (V) with E-Caprol acton, for example reaction products of trimethylolpropane with E-Caprol acton, reaction products of glycerol with E-Caprol acton, and reaction products of pentaerythritol with E-caprolactone.
  • Water, diethylene glycol, dipropylene glycol, castor oil, sorbitol and polyether polyols made up of repeating polyalkylene oxide units are also preferably used as H-functional starter substances.
  • the H-functional starter substances are particularly preferably 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- Pentanediol, 2-methylpropane-1,3-diol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, di- and trifunctional polyether polyols, where the polyether polyol consists 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 from 62 to 4500 g/mol and in particular a number-average molecular weight Mn in the range from 62 to 3000 g/mol, very particularly preferably a molecular weight of 62 to 1500 g/mol.
  • the polyether polyols preferably have a functionality of >2 to ⁇ 3.
  • 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, 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl- 1,2-butene oxide, 1-hexene oxide, 2, 3-hexene oxide, 3,4-hexene oxide, 2-methyl- l,2-pentene oxide, 4-methyl-l,2-pentene oxide, 2-ethyl-1,2-butene oxide, 1-heptene oxide, 1-octene oxide, 1-nonene oxide, 1-decene oxide, 1-undecene oxide, 1- dodecene oxide, 4-Methyl-1,2-pentene oxide, buta
  • 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. It 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 proportion of ethylene oxide in the total amount of propylene oxide and ethylene oxide used is >0 and ⁇ 90% by weight, preferably >0 and ⁇ 60% by weight.
  • the polyether polyol is "EO-capped", i.e. the polyether polyol has terminal ethylene oxide groups. The then terminal primary hydroxyl groups have greater reactivity towards isocyanates. (G. Oertel, Polyurethane Handbook, 2nd Edition, page 194 and 219, (1993)).
  • polyester polyols that can also be used as component A4) are in particular those with a number-average molecular weight Mn in the range from 200 to 4500 g/mol, preferably 400 to 3500 g/mol, particularly preferably 800 to 2500 g/mol. At least difunctional polyesters are preferably used as polyester polyols. Polyester polyols preferably consist of alternating acid and alcohol units. As acid components z. B.
  • succinic acid maleic acid, maleic anhydride, adipic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or mixtures of the acids and / or anhydrides mentioned.
  • alcohol components z. B.
  • ethanediol 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis (hydroxymethyl) -cyclohexane, Di ethyl en glycol, dipropylene glycol, trimethylolpropane, glycerol, pentaerythritol or mixtures of the alcohols mentioned are used. It is also possible to use dihydric or polyhydric polyether polyols as the alcohol component. If polyether polyols are used to produce the polyester ether polyols, preference is given to polyether polyols having a number-average molecular weight Mn of from 150 to 2000 g/mol.
  • polycarbonate polyols such as, for example, polycarbonate diols
  • component A4 polycarbonate polyols
  • Mn molecular weight in the range from 150 to 4500 g/mol, preferably 500 to 2500 g/mol be prepared for example by reacting phosgene, dimethyl carbonate, diethyl carbonate or diphenyl carbonate and difunctional and/or polyfunctional alcohols or polyester polyols or polyether polyols.
  • polycarbonate polyols can be found e.g. B. in EP-A 1359177.
  • the Desmophen® C grades from Covestro Germany AG can be used as polycarbonate dioie, such as. B. Desmophen® C 1100 or Desmophen® C 2200.
  • Chain extenders and/or crosslinkers or crosslinkers are used as component A5).
  • the chain extenders and crosslinkers are preferably NCO-reactive compounds with an OH and/or NH functionality of at least 2 and a molecular weight of 62 to 800 g/mol.
  • This can, for example, ethylene glycol, di ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol, monoethanolamine, diethanolamine and the like low molecular weight compounds and mixtures of these.
  • Component B) contains at least one aliphatic oligomeric polyisocyanate and optionally a monomeric aliphatic polyisocyanate and/or dimeric aliphatic polyisocyanate.
  • aliphatic oligomeric polyisocyanates are to be understood as meaning isocyanate-bearing oligomers which are preferably formed from (2n+1) aliphatic polyisocyanates, where n is a natural number from 1 to 10. Accordingly, both symmetrical and asymmetrical trimers, including their higher homologues (such as pentamers, heptamers, etc.) are encompassed by the term “aliphatic oligomeric polyisocyanates”.
  • the aliphatic oligomeric polyisocyanate of component B) preferably consists of at least 90.0% by weight of these isocyanate-bearing oligomers.
  • the aliphatic oligomeric polyisocyanates preferably contain isocyanurate and/or iminooxadiazinedione groups.
  • the aliphatic oligomeric polyisocyanates of component B) are preferably used isocyanate-bearing trimers, component B) containing in particular a mixture of this trimer and at least one other isocyanate-bearing oligomer (formed from (2n+1) aliphatic polyisocyanates), in which n is a natural number from 2 to 10.
  • the aliphatic oligomeric polyisocyanate of component B) preferably consists of at least 30.0% by weight, preferably 30.0 to 80.0% by weight, of these isocyanate-bearing trimers. Particular preference is given to using isocyanate-carrying trimers of the formula (VI) and/or formula (VII), each formed from 3 aliphatic polyisocyanates, where R is independently an aliphatic C1 to C15 carbon chain.
  • the aliphatic oligomeric polyisocyanates are not limited to the aforementioned forms of (2n+1) aliphatic polyisocyanates.
  • dimers and their higher homologues can also fall under the definition of aliphatic oligomeric polyisocyanates.
  • the aliphatic oligomeric polyisocyanates can also uretdione, carbodiimide, uretonimine, urethane. Contain allophanate, biuret and urea groups. Mixed forms, in which several of the above-mentioned structure types occur in one oligomer, also fall under the definition.
  • Typical examples are 1,4-diisocyanatobutane, 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2, 2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis(isocyanatomethyl )-cyclohexane, 1-isocyanato- 3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4'- and 4,4'- diisocyanatodicyclohexylmethane, 1 -isocyanato- 1
  • the aliphatic oligomeric polyisocyanates are prepared from a diisocyanate having from 1 to 15 carbon atoms.
  • the diisocyanate is selected from 1,5-pentamethylene diisocyanate and/or 1,6-hexamethylene diisocyanate.
  • Suitable commercially available polyisocyanates include Desmodur® ultra N3300, Desmodur® ultra N3600, Desmodur® N3200, Desmodur® eco N7300 and Desmodur® N3900 (available from Covestro Deutschland AG)
  • Component B) preferably has an average NCO functionality per molecule of >2.0, preferably from 2.3 to 4.3, particularly preferably from 2.5 to 4.2, very particularly preferably from 2.8 to 4. 1 and most preferably from 3.0 to 4.0.
  • the NCO functionality refers to free NCO groups and not latent NCO groups (such as the NCO groups forming the ring of trimers).
  • the average NCO functionality of component B is determined by means of gel permeation chromatography (GPC). Functionality is an expression of the number of reactive groups per molecule, i.e. the number of potential linkage sites when forming a network.
  • polyisocyanates such as those formed during the trimerization of diisocyanates, do not only consist of a defined type of molecule, but also contain a wide distribution of different molecules with different functionalities.
  • the average functionality is therefore given as the parameter for the polyisocyanates.
  • the average functionality of polyisocyanates is clearly determined by the ratio of number average molecular weight and equivalent weight and is generally calculated from the molecular weight distribution determined using GPC. Accordingly, the average NCO functionality can be calculated after assignment of the individual oligomers in the GPC with the respective functionalities and weighting via their mass fraction.
  • PIC polyisocyanates
  • it can, for example, also be calculated simply via the NCO content of the polyisocyanate using the following formula:
  • NCO functionality (6*NCO content PIC)/[4*NCO content PIC - NCO content monomer)]
  • the NCO functionality must then be determined using the calculation mentioned above.
  • the peaks in the GPC can be ascribed to certain structures, optionally with the aid of further analysis methods such as NMR, IR and/or MS.
  • the average NCO functionality of the mixture of polyisocyanates can then be calculated in the GPC using the NCO functionalities of the determined chemical structures and a weighting via their mass fraction. Since the oligomerization of di- and polyisocyanates does not usually result in pure products, but in compounds with different degrees of oligomerization, i.e.
  • the NCO functionality of the resulting compounds can only be given as an average value and the NCO group content only in relation to the State the total weight of the resulting oligomer mixture.
  • such an oligomer mixture is simply referred to as an “aliphatic oligomeric polyisocyanate”.
  • component B) has a content of free NCO groups of 5.0 to 30.0% by weight, particularly preferably from 10.0 to 27.0% by weight and very particularly preferably from 15.0 to 24.0% by weight, based on the total weight of component B), determined according to DIN EN ISO 11909:2007.
  • the reaction of the composition takes place at an index of at least 70.
  • the isocyanate index is at least 75, preferably from 75 to 115, more preferably from 85 to 110.
  • isocyanate index also index, NCO/ OH index or isocyanate index
  • 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 index indicates the percentage ratio of the amount of isocyanate actually used to the stoichiometric amount of isocyanate, i.e. the amount calculated for the conversion of the OH equivalents.
  • An equivalent amount of NCO groups and NCO-reactive H atoms corresponds to an NCO/OH index of 100.
  • a monomeric aliphatic polyisocyanate can be used in component B) in addition to the at least one aliphatic oligomeric polyisocyanate.
  • the monomeric aliphatic polyisocyanate is selected from the group comprising or consisting of 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanato-methyl-3,5,5-trimethylcyclohexane, dicyclohexylmethane-4,4'-diisocyanate.
  • a dimeric aliphatic polyisocyanate can also be used in component B).
  • This dimeric aliphatic polyisocyanate is preferably composed of dimeric compounds of 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethane-4,4' -diisocyanates or mixed dimers thereof.
  • the dimeric aliphatic polyisocyanates are preferably the corresponding uretdiones of the aforementioned compounds, 1,3-bis(5-isocyanatopentyl)uretdione, 1,3-bis(6-isocyanatohexyl)uretdione or mixtures thereof being particularly preferred.
  • the uretdiones are particularly suitable as an alternative or supplement for the monomeric aliphatic polyisocyanate, since these are again almost completely present as monomers at elevated temperatures, such as those that occur or can prevail during foaming, for example.
  • Blowing agents are used as component C. This includes water and/or physical blowing agents.
  • Carbon dioxide and/or readily volatile organic substances are used as physical blowing agents.
  • These highly volatile physical blowing agents are cyclic hydrocarbons such as cyclopentane and cyclohexane.
  • Non-cyclic hydrocarbons include butane, n-pentane and isopentane.
  • the halogen-containing hydrocarbons are suitable as physical blowing agents. These are fluorocarbons or perfluoro compounds z.
  • Known catalysts such as tin catalysts (e.g. dibutyltin oxide, dibutyltin dilaurate, dimethyltin dineodecanoate, dimethyltin(IV) dimercaptide, tin octoate, tin neodecanoate), bismuth 2-ethylhexanoate, cobalt 2-ethylhexanoate, iron 2-ethylhexanoate, iron (III) chloride, aliphatic tertiary amines (e.g. trimethylamine, tetramethylbutanediamine), cycloaliphatic tertiary amines (e.g.
  • tin catalysts e.g. dibutyltin oxide, dibutyltin dilaurate, dimethyltin dineodecanoate, dimethyltin(IV) dimercaptide, tin octoate, tin neodecan
  • aliphatic amino ethers e.g. bis(2-dimethylaminoethyl) ether, and N,N,N-trimethyl-N-hydroxyethylbisaminoethyl ether
  • Cycloaliphatic amino ethers for example N-ethylmorpholine, 4,4'-(oxydi-2,l-ethanediyl)dimorpholine
  • aliphatic amidines for example N-ethylmorpholine, 4,4'-(oxydi-2,l-ethanediyl)dimorpholine
  • aliphatic amidines cycloaliphatic amidines, urea, derivatives of urea (such as aminoalkylureas, see for example EP-A 0 176 013, in particular (3-dimethylaminopropylamine)urea).
  • the catalysts can be added individually or as a mixture with one another.
  • the catalysts can function as gel and/or blowing catalysts. Many catalysts are not pure gel or blowing catalysts, but can be used for both purposes. However, one of the two characteristics can be more pronounced.
  • the compounds tin octoate or neodecanoate are considered to be almost pure gel catalysts and bis(2-dimethylaminoethyl ether) as a pure blowing catalyst. With aliphatic isocyanates, l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) acts primarily as a blowing catalyst.
  • DBU l,8-diazabicyclo[5.4.0]undec-7-ene
  • dimethyltin dineodecanoate, tin octoate, tin neodecanoate or mixtures of these are preferably used as gel catalysts and DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), tetramethylguanidine or mixtures of these are used as blowing catalysts.
  • Component D) preferably comprises or consists of at least one gel catalyst and/or at least one blowing catalyst.
  • Component E) Furthermore, surface-active additives, in particular silicone surfactants and more preferably siloxane-polyoxyalkylene copolymers and polydimethylsiloxane-polyoxyalkylene copolymers, can be used in the production of the foams. Other surface-active additives such as emulsifiers can also be included. In the case of the foam stabilizers, those with low emissions, such as products from the Tegostab® BF series (company: Evonik Operations GmbH), are particularly suitable.
  • Optional auxiliaries and additives other than component E such as reaction retardants (e.g. acidic substances such as hydrochloric acid or organic acid halides), cell regulators (e.g. paraffins or fatty alcohols or dimethylpolysiloxanes), pigments, dyes, flame retardants (e.g. tricresyl phosphate or ammonium polyphosphate), other stabilizers against Aging and weathering effects, antioxidants, plasticizers, fungistatic and bacteriostatic substances, fillers (such as barium sulfate, kieselguhr, soot chalk or whiting) and release agents can also be used as component F).
  • reaction retardants e.g. acidic substances such as hydrochloric acid or organic acid halides
  • cell regulators e.g. paraffins or fatty alcohols or dimethylpolysiloxanes
  • pigments e.g. paraffins or fatty alcohols or dimethylpolysiloxanes
  • flame retardants e
  • auxiliaries and additives which may also be used, are described, for example, in EP-A 0 000 389, pages 18-21. Further examples of auxiliaries and additives that may also be used according to the invention and details of the use and mode of action of these auxiliaries and additives are in Kunststoff-Handbuch, Volume VII, published by G. Oertel, Carl-Hanser-Verlag, Kunststoff, 3rd edition, 1993 , e.g. on pages 104-127.
  • Aliphatic flexible polyurethane foams based on renewable (bio-based) or sustainable raw materials are used:
  • the components to be used in the method according to the invention can be bio-based or non-bio-based.
  • bio-based is defined in such a way that a component, a compound, a material or the like - such as, for example, aliphatic oligomeric polyisocyanates according to component B) or a starting material for the production of such an aliphatic oligomeric polyisocyanate - from renewable sources (such as from plants, microbes, algae or animals) or prepared therefrom.
  • renewable sources such as from plants, microbes, algae or animals
  • Non-renewable sources include, for example, fossil raw materials that arose from dead living beings in geological prehistory. These are in particular crude oil, lignite, hard coal, peat and natural gas. Compounds and materials obtained or prepared from non-renewable sources are defined as non-biobased or “man-made” for the purposes of the present invention. Bio-based feedstocks can be obtained directly from the above renewable sources, or they can be produced through subsequent reactions from compounds or materials obtained from these sources. Thus, the aliphatic oligomeric polyisocyanates of component B) can be based on di- and polyisocyanates, which in turn have been produced from bio-based diamines. An example of such a diamine is 1,5-diaminopentane (1,5-PDA).
  • CCE-based starting materials in relatively large amounts.
  • the polyether carbonate polyols described under A3) are such starting materials. When these compounds are used, the CCE balance of the flexible polyurethane foams according to the invention can be significantly improved.
  • Flexible polyurethane foams can also be produced when polyester polyols (A4) are used as polyol components (WO 2014/064130).
  • polyester polyols (A4) are used as polyol components (WO 2014/064130).
  • aromatic isocyanates used in WO 2014/064130 with ones based on renewable raw materials such as the l,3,5-tris(6-isocyanatopentyl)-l,3,5-triazine-2,4,6-trione used here (Bl ) and additional bio-based low molecular weight alcohols, such as bioethanol
  • flexible polyurethane foams can be produced with a proportion of renewable raw materials of > 65%, preferably > 75% and particularly preferably > 80%.
  • the polyurethane foams are in the form of flexible polyurethane foams and can be produced as molded or block foams.
  • the subject matter of the invention is therefore a process for the production of the—optionally partially biobased—polyurethane flexible foams.
  • the discoloration-resistant flexible polyurethane foams that can be obtained according to the invention—possibly partly biobased—are used, for example, in the following applications: textile foams (for example in bras, shoulder pads, furniture upholstery, textile inserts), body-supporting elements (for example in upholstery, mattresses, furniture, automobile seats, motorcycle seats, headrests, armrests) , sponges, and foam sheets for use in automotive parts (such as headliners, door quarter panels, and seat pads).
  • the flexible polyurethane foams obtained or obtainable by the process according to the invention have in particular a compression hardness (in the 4th cycle) of ⁇ 14.0 kPa, preferably ⁇ 12.0 kPa, particularly preferably from 2.0 kPa to 8.0 kPa and completely particularly preferably from 3.0 to 7.0 kPa, measured according to DIN EN ISO 3386-1 and/or a compression set value (DVR) of ⁇ 3.5%, preferably ⁇ 3.0%, more preferably ⁇ 2 5% and particularly preferably from 0.1% to 2.0%, measured according to DIN EN ISO 1856-2008.
  • a compression hardness in the 4th cycle
  • ⁇ 12.0 kPa particularly preferably from 2.0 kPa to 8.0 kPa and completely particularly preferably from 3.0 to 7.0 kPa
  • DVR compression set value
  • the rise time is preferably ⁇ 100 s, preferably 40 to 90 s, and/or the setting time is ⁇ 170, preferably 60 to 200 s in the production of the flexible polyurethane foams, each based on 450 g ⁇ 5 g composition and each determined according to the further methods described above.
  • the invention further relates to the use of a monohydroxy functional compound in combination with an aliphatic oligomeric polyisocyanate and optionally a monomeric aliphatic polyisocyanate and/or a dimeric aliphatic polyisocyanate with an isocyanate index of at least 70 to reduce the compression hardness and/or the compression set value of flexible polyurethane foams and/or to shorten the rising time and/or setting time in the production of polyurethane flexible foams.
  • the invention relates to a process for producing flexible polyurethane foams by reacting a composition with the components
  • component E optionally auxiliaries and additives different from component E).
  • the invention relates to a method according to embodiment 1, characterized in that the monohydroxy-functional compound of component A) is selected from the group comprising or consisting of A1) primary, secondary and/or tertiary monohydroxy-functional compounds having 1 to 12 carbon atoms, preferably primary monohydroxy-functional compounds and/or
  • polymeric monohydroxy compound preferably polyether monools, polycarbonate monools, polyester carbonate monools, polyether carbonate monools, polyether ester carbonate monools and/or mixtures thereof, the polymeric monohydroxy functional compound particularly preferably having a primary hydroxyl group.
  • the invention relates to a method according to embodiment 2, characterized in that the monohydroxy-functional compound Al) is selected from the group comprising or consisting of acyclic and/or cyclic monohydroxy-functional alkanols and/or acyclic and/or cyclic monohydroxy-functional alkenols, preferably methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, sec-butanol, tert-butanol, pentane-1-ol, pentane-2-ol, pentane-3-ol, 2-methyl -butan-1-ol, 2-methyl-butan-1-ol, 3-methyl-butan-1-ol, 3-methyl-butan-2-ol, 2,2-dimethyl-propan-1-ol, hexane - l-ol, hexan-2-ol, hexan-3-ol, 2-methylpent
  • the invention relates to a method according to embodiment 2 or 3, characterized in that the polymeric monohydroxy-functional compound A2) has a hydroxyl number of 20 to 250 mg KOH/g, preferably 20 to 112 mg KOH/g and particularly preferably 20 to 50 mg KOH/g, measured according to DIN 53240-3:2016-03.
  • the invention relates to a method according to one of embodiments 2 to 4, characterized in that the equivalent ratio of the OH Groups of the sum of components A1) and A2) to the NCO groups of components B) is 0.15 to 0.65, preferably 0.20 to 0.55 and particularly preferably 0.25 to 0.50.
  • the invention relates to a method according to one of the above embodiments, characterized in that the polyol of component A) is selected from the group comprising or consisting of
  • polyether polyols polyether polyols, polyester polyols, polycarbonate polyols and/or mixtures thereof, the polyol of component A) preferably comprising or consisting of at least one polyether carbonate polyol A3).
  • the invention relates to a method according to one of the above embodiments, characterized in that component A) additionally contains at least one chain extender and/or crosslinking agent selected from the group comprising or consisting of
  • NCO-reactive compound A5) contains NCO-reactive compounds with an OH and/or NH functionality of at least 2 and a molecular weight of 62 to 800 g/mol, where the NCO-reactive compound A5) is preferably selected from the group comprising or consisting of ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, glycerine, 1,1,1-trimethylolpropane, pentaerythritol, monoethanolamine, diethanolamine, or mixtures thereof.
  • the invention relates to a method according to one of the above embodiments, characterized in that the aliphatic oligomeric polyisocyanate of component B) comprises isocyanate-bearing oligomers formed from (2n+1) aliphatic polyisocyanates, where n is a natural number of is 1 to 10 and the aliphatic oligomeric polyisocyanate of component B) consists of at least 90% by weight of these isocyanate-bearing oligomers.
  • the invention relates to a method according to embodiment 8, characterized in that the aliphatic oligomeric polyisocyanate of component B) comprises an isocyanate-bearing trimer, with component B) in particular a mixture of this trimer and at least one other isocyanate-bearing Contains oligomer where n is a natural number from 2 to 10 and the aliphatic oligomeric polyisocyanate of component B) consists of at least 30% by weight, preferably 30 to 80% by weight, of these isocyanate-bearing trimers.
  • the invention relates to a method according to one of the above embodiments, characterized in that the aliphatic oligomeric polyisocyanate of component B) contains isocyanurate and/or iminooxadiazinedione groups.
  • the invention relates to a method according to one of the above embodiments, characterized in that the aliphatic oligomeric polyisocyanate of component B) is an isocyanate-bearing trimer of the formula (VI) and / or formula (VII), each formed from 3 aliphatic Polyisocyanates, where R is independently an aliphatic C1 to C15 carbon chain.
  • the invention relates to a method according to one of the above embodiments, characterized in that the aliphatic oligomeric polyisocyanate of component B) is produced from a diisocyanate having 1 to 15 carbon atoms, the diisocyanate preferably being selected from 1,5-pentamethylene - diisocyanate and/or 1,6-hexamethylene diisocyanate.
  • the invention relates to a method according to one of the above embodiments, characterized in that component B) has an average NCO functionality per molecule of >2.0, preferably from 2.3 to 4.3, particularly preferably from 2 .5 to 4.2, more preferably from 2.8 to 4.1 and most preferably from 3.0 to 4.0.
  • the invention relates to a method according to one of the above embodiments, characterized in that component B) has a content of free NCO groups of 5.0 to 30.0 wt .-%, particularly preferably from 10.0 to 27.0% by weight and very particularly preferably from 15.0 to 24.0% by weight, based on the total weight of component B), determined according to DIN EN ISO 11909:2007.
  • the invention relates to a method according to one of the above embodiments, characterized in that the monomeric aliphatic polyisocyanate of component B) is selected from the group comprising or consisting of 1,5-pentamethylene diisocyanate, 1,6-hexamethylene -Diisocyanate, l-isocyanato-3-isocyanato-methyl-3,5,5-trimethylcyclohexane, dicyclohexylmethane-4,4'-diisocyanates or mixtures thereof and/or the dimeric aliphatic polyisocyanate of component B) is selected from dimeric compounds of 1 ,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanato-methyl-3,5,5-trimethylcyclohexane, dicyclohexylmethane-4,4'-diisocyanates or mixed dimers thereof.
  • the invention relates to a method according to one of the above embodiments, characterized in that component D) comprises or consists of at least one gel catalyst and/or at least one blowing catalyst.
  • the invention relates to a method according to one of the above embodiments, characterized in that the reaction takes place at an isocyanate index of 75 to 115, preferably 85 to 110.
  • the invention relates to a method according to one of the above embodiments, characterized in that the rise time in the production of flexible polyurethane foams is ⁇ 100 s, preferably from 40 to 90 s, based on 450 g ⁇ 5 g composition and determined according to the method indicated in the description.
  • the invention relates to a method according to one of the above embodiments, characterized in that the setting time in the production of flexible polyurethane foams is ⁇ 170 s, preferably from 60 to 200 s, based on 450 g ⁇ 5 g composition and determined according to the method given in the description.
  • the invention relates to a flexible polyurethane foam obtained or obtainable by a process according to any one of embodiments 1 to 19.
  • the invention relates to a flexible polyurethane foam according to embodiment 20, characterized in that the flexible polyurethane foam has a compressive strength (in the 4th cycle) of ⁇ 14.0 kPa, preferably ⁇ 12.0 kPa, particularly preferably 2.0 kPa to 8.0 kPa and very particularly preferably from 3.0 to 7.0 kPa, measured according to DIN EN ISO 3386-1.
  • the invention relates to a flexible polyurethane foam according to embodiment 20 or 21, characterized in that the flexible polyurethane foam has a compression set value (DVR) of ⁇ 3.5%, preferably ⁇ 3.0%, more preferably of ⁇ 2.5% and particularly preferably from 0.1% to 2.0%, measured according to DIN EN ISO 1856-2008.
  • DVR compression set value
  • the invention relates to the use of a flexible polyurethane foam according to one of embodiments 20 to 22 as or for the production of body-supporting elements, in particular upholstery, mattresses, furniture, automobile seats and motorcycle seats.
  • the invention relates to the use of a monohydroxy-functional compound in combination with an aliphatic oligomeric polyisocyanate and optionally a monomeric aliphatic polyisocyanate and/or a dimeric aliphatic polyisocyanate with an isocyanate number of at least 70 to reduce the compression hardness and/or the compression set value of flexible polyurethane foams.
  • the invention relates to the use of a monohydroxy-functional compound in combination with an aliphatic oligomeric polyisocyanate and optionally a monomeric aliphatic polyisocyanate and/or a dimeric aliphatic polyisocyanate with an isocyanate index of at least 70 to shorten the rise time and/or setting time in the Production of flexible polyurethane foams.
  • Desmophen® LB 25 polyether monool, OH number: 25 mg KOH/g (according to DIN 53240-3:2016-03), viscosity: 4600 mPa-s)
  • Cardyon® LC 05 polyether carbonate polyol, OH number: 55 mg KOH/g, typical CO 2 incorporation: 14% by weight
  • Desmodur® eco N 7300 biobased, aliphatic polyisocyanate containing isocyanurate groups based on 1,5-pentamethylene diisocyanate (PDI) with an NCO content of 21.9% by weight (according to DIN EN ISO 11909:2007), an average NCO functionality of > 3.0 (according to GPC), a maximum content of monomeric PDI of 0.3% by weight and a viscosity of 9500 mPa-s (at 23 °C, determined according to DIN EN ISO 3219) )
  • PDI 1,5-pentamethylene diisocyanate
  • Desmodur® ultra N 3600 aliphatic polyisocyanate containing isocyanurate groups and based on 1,6-diisocyanatohexane (HDI) with an NCO content of 23.0% by weight (according to DIN EN ISO 11909:2007), an average NCO functionality of 3.2 (after GPC), a maximum content of monomeric HDI of 0.1% by weight and a viscosity of 1200 mPa-s (23 °C, determined according to DIN EN ISO 3219))
  • HDI 1,6-diisocyanatohexane
  • Fomrez® UL-28 dimethyltin dineodecanoate
  • the compression hardness (CV) is determined according to DIN EN ISO 3386-1. Two or three test specimens with the dimensions 6 cm ⁇ 6 cm ⁇ 3 cm are cut for the measurements. The tests are carried out on the 2.5kN RetroLine device from Zwick/Roell at 22 °C and 47% relative humidity.
  • the measurement geometry consists of a base plate on which the specimen is placed and a pressure plate. At the beginning of the measurement, the distance between the two plates corresponds to the height of the sample.
  • the measurements consist of three pre-cycles and a subsequent measurement cycle, with data being recorded for the first pre-cycle and the measurement cycle.
  • a cycle consists of a deformation with a speed of 100 mm/min in the range from 0 to 70% and a relief up to the measuring plates have reached the original distance again.
  • the compressive stress/compression hardness at various deformations is determined from the measured values. A value that is frequently given is the compression hardness at 40% deformation (CV40), which can be calculated using the following formula.
  • the compression set is determined according to DIN EN ISO 1856-2008. For this purpose, three test specimens each measuring 5 cm ⁇ 5 cm ⁇ 2.5 cm are cut. These are clamped between two plates in such a way that they are compressed by 50% and stored in an oven at 70 °C for 22 h. The foams are then removed from the compression holder and, after storage at 22° C. for 30 minutes, the height of the test specimens is determined. 3 test specimens are examined and the average DVR is given as the result;
  • Viscosity The viscosity of the Desmodur grades (Desmodur ultra N 3600, Desmodur ultra N3300, Desmodur eco N7300) is measured in accordance with DIN EN ISO 3219 using RheolabQC devices from Anton Paar;
  • Start time It is the period from the beginning of the mixing process to a visually perceptible change in the reaction mixture, i.e. until the reaction mixture rises for the first time.
  • auxiliary lines lines running obliquely upwards
  • setting time is understood to mean the so-called tack-free time.
  • the tack-free time is the period of time from the start of mixing to the state/point in time at which the surface of the foam mass is no longer tacky. It is determined by dabbing the no longer rising foam with a wooden stick touched. The point in time at which there is no longer any sticking is referred to as the tack-free time.
  • This mixture was mixed with the oligomeric and/or monomeric polyisocyanate (Desmodur® eco N 7300, Desmodur® ultra N 3600, PDI, HDI, Desmodur® T80) with a stirrer at 2100 rpm for 15 s and poured into a mold .
  • the raw material temperature was 23 °C. Curing took place at ambient temperature.
  • the foam was set according to the setting times given in the table.
  • Comparative Examples 1 and 2 show relatively long starting times and relatively short setting times, but these foams have relatively high compressive strength and are no longer the soft, flexible foams required for mattresses, for example.
  • the use of monomeric aliphatic polyisocyanates (PDI, HDI, IPDI) and aromatic diisocyanates (TDI, MDI) gives flexible foams with significantly lower compressive strength (comparative examples 3, 4 and 5).
  • the starting times are short and the setting times are relatively long.

Abstract

La présente invention concerne un procédé de production de mousses de polyuréthane souples aliphatiques à l'aide de polyisocyanates oligomères aliphatiques et de composés à fonction monohydroxy, le temps de montée et/ou le temps de prise (temps sans pégosité) étant en particulier réduit lors de la production des mousses de polyuréthane souples et les mousses de polyuréthane souples ayant de préférence une faible dureté de compression et/ou une faible valeur de déformation rémanente à la compression (DRC). L'invention concerne également une mousse de polyuréthane souple, qui est de préférence flexible, qui est produite ou peut être produite par le procédé mentionné ci-dessus et présente une faible dureté de compression et/ou une faible valeur de déformation rémanente à la compression (DRC), ainsi que son utilisation, par exemple, pour la production d'éléments de support de corps tels que le rembourrage, des matelas, des meubles, des sièges automobile et des sièges moto. L'invention concerne également l'utilisation d'un composé à fonction monohydroxy en association avec un polyisocyanate oligomère aliphatique et éventuellement un polyisocyanate aliphatique monomère et/ou un polyisocyanate aliphatique dimère pour réduire la dureté de compression et/ou la valeur de déformation rémanente à la compression de mousses de polyuréthane souples et/ou pour réduire le temps de montée et/ou le temps de prise lors de la production de mousses de polyuréthane souples.
PCT/EP2023/051471 2022-01-28 2023-01-23 Production de mousses de polyuréthane souples aliphatiques avec des temps de prise (temps sans pégosité) et des temps de montée réduits WO2023144058A1 (fr)

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