WO2024068268A1 - Procédé de production de copolymères à bloc de polydialkylsiloxane-polyéther linéaires à liaison sioc et leur utilisation - Google Patents

Procédé de production de copolymères à bloc de polydialkylsiloxane-polyéther linéaires à liaison sioc et leur utilisation Download PDF

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WO2024068268A1
WO2024068268A1 PCT/EP2023/075079 EP2023075079W WO2024068268A1 WO 2024068268 A1 WO2024068268 A1 WO 2024068268A1 EP 2023075079 W EP2023075079 W EP 2023075079W WO 2024068268 A1 WO2024068268 A1 WO 2024068268A1
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foam
linear
weight
polydialkylsiloxane
mol
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PCT/EP2023/075079
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German (de)
English (en)
Inventor
Matthias Lobert
Thomas Reibold
Jörg DIENDORF
Sven GAHRENS
Ursula SKRZYPCZYK
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Evonik Operations Gmbh
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Publication of WO2024068268A1 publication Critical patent/WO2024068268A1/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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen

Definitions

  • the present invention lies in the fields of silicone chemistry and polyurethane chemistry and relates to a process for the preparation of SiOC-linked, linear polydialkylsiloxane-polyoxyalkylene block copolymers with repeating (AB) units and their use in the production of polyurethanes (PU for short).
  • the process principle for producing SiOC-linked polydialkylsiloxane-polyoxyalkylene block copolymers by reacting SiH-functional polyorganosiloxanes with alcohols or OH-functional polyoxyalkylene polymers using one or more element compounds of main group III and/or subgroup III as a catalyst is known in principle from EP 1460099 B1.
  • a preferred conversion of at least equimolar up to 3-fold excess of alcohol groups to SiH groups is described there.
  • This process was used to react linear and/or branched polyorganosiloxanes with alcohols and/or OH-functional polyoxyalkylenes.
  • EP 1935922 B1 describes the reaction of linear a,co-(SiH)-functional polydimethylsiloxanes with linear, a,co-(OH)-functional polyetherdiols using one or more element compounds of main group III and/or subgroup 3 as a catalyst.
  • This process which can be carried out neat or in the presence of solvent, is essentially characterized in that the (SiH) functions of the polydimethylsiloxane are used in a molar excess of preferably 1.1 to 2.0 in relation to the (OH) functions of the polyoxyalkylene and the reaction is continued until no more (SiH) groups can be detected by gas volumetry.
  • the invention relates to a process for producing SiOC-linked, linear polydialkylsiloxane-polyoxyalkylene block copolymers with repeating (AB) units, comprising the reaction of a linear, a,co-(SiH)-functional polydialkylsiloxane (a) with a linear a ,co-(OH)-functional polyoxyalkylene (b), using one or more element compounds of III.
  • Reactant (a) in the sense of this invention is: linear a,co-(SiH)-functional polydialkylsiloxane.
  • reactant (b) is: linear a,co-(OH)-functional polyoxyalkylene.
  • the linear a,co-(SiH)-functional polydialkylsiloxane used in the process according to the invention has SiH values between 0.25 and 3.0 mol/kg, preferably between 0.5 and 2.0 mol/kg, in particular between 0.75 and 1.5 mol/kg, then a particularly preferred embodiment of the invention is present.
  • the determination of the amount of SiH units of the linear a,co-(SiH)-functional polydialkylsiloxanes is based on the known method of alkali-catalyzed SiH value determination.
  • Another subject of the invention are the SiOC-linked, linear polydialkylsiloxane-polyether block copolymers with repeating (AB) units, produced according to the process according to the invention.
  • SiOC-linked, linear polydialkylsiloxane-polyether block copolymers and “SiOC-linked, linear polydialkylsiloxane-polyoxyalkylene block copolymers” are used synonymously in the context of this invention.
  • a further object of the invention is the use of the SiOC-linked, linear polydialkylsiloxane-polyether block copolymers with repeating (AB) units produced according to the process according to the invention as surface-active additives, in particular as cell openers, for the production of polyurethane foams (PU foams), preferably from polyurethane Rigid foams, especially rigid polyurethane foams with high open cells.
  • PU foams polyurethane foams
  • a particularly preferred rigid polyurethane foam is one-component PU canned foam (construction foam, assembly foam, one-component foam/OCF).
  • Particularly preferred are rigid polyurethane foams in which a high level of open cells is advantageous, such as open-cell spray foam, packaging foam, headliner foam, pipe insulation foams, floral foam and/or thermoformable rigid foams, etc.
  • a further subject of the invention is a polyurethane foam, preferably a rigid polyurethane foam, in particular a rigid polyurethane foam with high open cell structure, produced using SiOC-linked, linear polydialkylsiloxane-polyether block copolymers according to the invention with repeating (AB) units.
  • a further object of the invention is the use of the polyurethane foam according to the invention, preferably rigid polyurethane foam, in particular rigid polyurethane foam with high open cells, for the production of foam moldings, spray foam, insulating foam, sealants, adhesives, insulating compounds, assembly compounds, and / or filling compounds.
  • FIGS. 1 to 6 Brief description of the figures FIGS. 1 to 6:
  • FIG 1 shows the course of the gas volume released by the reaction progress as a function of the added siloxane mass for Example 1 from the experimental part, each as target and actual conversion.
  • FIG. 2 shows the course of the gas volume released by the progress of the reaction depending on the metered siloxane mass for Example 2 from the experimental part, each as target and actual conversion.
  • FIG 3 shows the course of the gas volume released by the reaction progress as a function of the added siloxane mass for example 3 from the experimental part, each as target and actual conversion.
  • FIG 4 shows the course of the gas volume released by the reaction progress as a function of the added siloxane mass for example 4 from the experimental part, each as target and actual conversion.
  • FIG 5 shows the course of the gas volume released by the reaction progress as a function of the added siloxane mass for example 5 from the experimental part, each as target and actual conversion.
  • FIG 6 shows the deviation of the target from the actual conversion in % depending on the dosed siloxane mass for examples 1 to 5 from the experimental part.
  • the linear a,co-(SiH)-functional polydialkylsiloxanes used in the process according to the invention are known per se. They can be equilibrated in a known manner using any prior art method (preferably acidic).
  • weight-average molecular weights between approximately 650 and 7000 g/mol, preferably between 1000 and 6000 g/mol, in particular between approximately 1500 to 4500 g/mol. This corresponds to a preferred embodiment of the invention.
  • the determination of the average molecular weights is based on the well-known methods of GPC analysis.
  • Linear a,co-(SiH)-functional polydialkylsiloxanes of the general formula (I) are preferably used:
  • R 1 independently of one another identical or different hydrocarbon radicals having 1 - 20 carbon atoms, preferably methyl, ethyl, propyl or butyl, particularly preferably methyl.
  • polyetherdiols used in the process according to the invention
  • polyetherdiols are also known per se. They can be prepared by any prior art process. They preferably correspond to the general formula (II):
  • R 2 independently identical or different hydrocarbon radicals with 1-12 carbon atoms, preferably methyl, ethyl, propyl or butyl, particularly preferably methyl or ethyl.
  • the polyether diols are preferably addition products of at least one alkylene oxide, selected from the group of ethylene oxide, propylene oxide, butylene oxide, dodecene oxide and/or tetrahydrofuran, to difunctional starters such as water, ethylene or propylene glycol.
  • the polyether oxides are preferably composed of at least two monomer units, particularly preferably ethylene oxide and propylene oxide.
  • the polyether diions preferably consist essentially of oxyethylene units or oxypropylene units; mixed oxyethylene and oxypropylene units with an oxyethylene content of approximately 25 to 70% by weight and 70 to 25% by weight of oxypropylene based on the total content of oxyalkylene units are preferred.
  • the oxyethylene units or oxypropylene units can be structured either randomly or in blocks, but are preferably structured in blocks.
  • the weight-average molecular weight Mw of each polyetherdiol is preferably between about 600 and 10,000 g/mol, preferably 1,000 to 5,000 g/mol, particularly preferably 1,500 to 3,500 g/mol.
  • the determination of the average molecular weights is based on the known methods of determining the OH number.
  • the molar ratio of linear a,co-(SiH)-functional polydialkylsiloxane to linear a,co-(OH)-functional polyoxyalkylene preferably used in the process according to the invention is in the equimolar range. This means the use of preferably equimolar amounts of (SiH) functions of the linear, a,co-(SiH)-functional polydialkylsiloxane in relation to the (OH) functions of the linear a,co-(OH)-functional polyoxyalkylene.
  • this ratio specifically includes the range from 0.9 to 1.10, preferably 0.98 to 1.02 from linear a,co-(SiH)-functional polydialkylsiloxane to linear a,co-(OH)-functional polyoxyalkylene.
  • this ratio is exactly equimolar, i.e. 1 to 1.
  • the total siloxane block content (A) in the SiOC-linked, linear polydialkylsiloxane-polyoxyalkylene block copolymer with repeating (AB) units is preferably between 20 and 60% by weight, in particular 40 to 50% by weight, and the proportion of the polyoxyalkylene blocks (B) preferably between 80 and 40% by weight, preferably 60 to 50% by weight. It is preferred if the block copolymer has a weight-average molecular weight Mw of at least 10,000 g/mol to approximately 250,000 g/mol, preferably 15,000 g/mol to approximately 225,000 g/mol, in particular 20,000 g/mol to approximately 200,000 g/mol. mol. The determination of the average molecular weights is based on the well-known methods of GPC analysis.
  • the process can be carried out either in the presence or absence of solvent. If particularly high molecular weight and thus particularly high viscosity SiOC-linked copolymers are to be produced, the use of a solvent is particularly advantageous.
  • Advantageously used solvents include alkanes, isoalkanes, cycloalkanes and/or alkyl aromatics.
  • Alkanes that can be used advantageously are, for example, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane and/or n-dodecane.
  • Cycloalkanes that can be used advantageously are, for example, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane and/or decalin.
  • Alkyl aromatics that can be used advantageously are toluene, xylene, cumene, n-propylbenzene, ethylmethylbenzene, trimethylbenzene, solvent naphtha and/or any industrially available alkylbenzenes.
  • high-boiling solvents with boiling points > 120°C, particularly preferably high-boiling alkylbenzenes.
  • preferably between 40% by weight and 75% by weight of solvent are used in relation to the sum of the amounts of reactants (a), (b) and the amount of solvent (c), particularly preferably between 55% by weight and 65% by weight.
  • the reaction temperature for preparing the block copolymers according to the invention is, in a preferred embodiment of the invention, preferably from 60°C to 140°C, particularly preferably from 100°C to 120°C.
  • the catalysts which can preferably be used in the process according to the invention in the context of a preferred embodiment of the invention are Lewis acidic element compounds of III.
  • Main group in particular elemental compound containing boron and/or aluminum.
  • Lewis acidic element compounds of subgroup 3 scandium-containing, yttrium-containing, lanthanum-containing and/or lanthanide-containing Lewis acids are particularly preferred.
  • the main and/or third subgroup can particularly preferably be used as halides, alkyl compounds, fluorine-containing, cycloaliphatic and/or heterocyclic compounds.
  • a preferred embodiment of the invention provides that fluorinated and/or non-fluorinated organoboron compounds are used as catalysts, in particular those which are selected in particular tris(perfluorotriphenylborane) [1109-15-5], boron trifluoride etherate [109-63-7], borane-triphenylphosphine complex [2049-55-0], triphenylborane [960-71-4], triethylborane [97-94- 9] and boron trichloride [10294-34-5], tris(pentafluorophenyl)-boroxine (9CI) [223440-98-0], 4, 4, 5, 5,-Tetramethyl-2-(pentafluorophenyl)-1,3, 2-Dioxaborolane (9CI) [325142-81-2], 2-(Pentafluorophenyl)-1,3,2-Dioxaborolane (9CI) [336880-93-4], Bis(pentafluoropheny
  • a further preferred embodiment of the invention provides that fluorinated and/or non-fluorinated organoaluminum compounds are used as catalysts, in particular those which are selected from:
  • AlCh [7446-70-0], aluminium acetylacetonate [13963-57-0], AIF3 [7784-18-1], aluminium trifluoromethanesulfonate [74974-61-1], di-/so-butylaluminium chloride [1779-25-5], di-/so-butylaluminium hydride [1 191-15-7] and/or triethylaluminium [97-93-8] and mixtures thereof.
  • a further preferred embodiment of the invention provides that fluorinated and/or non-fluorinated organoscandium compounds are used as catalysts, in particular those which are selected from:
  • a further preferred embodiment of the invention provides that fluorinated and/or non-fluorinated organoyttrium compounds are used as catalysts, in particular those which are selected from: Tris(cyclopentadienyl)yttrium [1294-07-1], yttrium(III) chloride [10361-92-9], yttrium(III) fluoride [13709-49-4], yttrium(III) hexafluoroacetylacetonate [18911-76 -7] and/or yttrium (III) naphthenate [61790-20-3] and mixtures thereof.
  • organoyttrium compounds are used as catalysts, in particular those which are selected from: Tris(cyclopentadienyl)yttrium [1294-07-1], yttrium(III) chloride [10361-92-9], yttrium(III) fluoride [13709-49-4], yttrium(III) hexafluoroace
  • a further preferred embodiment of the invention provides that fluorinated and/or non-fluorinated organolanthanum compounds are used as catalysts, in particular those selected from:
  • a further preferred embodiment of the invention provides that fluorinated and/or non-fluorinated organolanthanoid compounds are used as catalysts, in particular those which are selected from:
  • the catalysts are preferably used in amounts of about 0.01 to about 0.2 wt.%, in particular 0.03 to 0.10 wt.%, based on the sum of the amounts of reactants (a) and (b).
  • the catalyst(s) can be used homogeneously or as heterogeneous catalyst(s).
  • the catalyst(s) can be added dissolved or suspended.
  • the catalyst can be suspended or dissolved in a small part of the solvent or the polyetherdiol and added; it can particularly preferably be added dissolved in the solvent.
  • the polyether diol is introduced and dried in vacuo at elevated temperature, optionally in the presence of the solvent, in order to prevent the potential side reaction of Si-H to Si-OH in the presence of water.
  • This can be done, for example, by vacuum distillation.
  • the dehydrogenative coupling can be promoted by using a weakly acidic medium.
  • diammonium phosphate (DAP; 100 to 500 ppm) can be added before, during or after the distillation.
  • the preferably dried polyether diol (reactant (b)) is heated to the reaction temperature and the catalyst is added and mixed. Then the linear, a,co-(SiH)-functional polydialkylsiloxane (reactant (a)) is metered in with controlled hydrogen evolution.
  • the preferably dried polyether diol (reactant (b)) is heated to the reaction temperature and the catalyst is added and mixed. Then the siloxane (reactant (a)), diluted with a solvent, is metered in with controlled evolution of hydrogen.
  • the preferably dried polyetherdiol (reactant (b)) is heated to reaction temperature, diluted with solvent and the catalyst is added and mixed.
  • the siloxane (reactant (a)) is then metered in with controlled hydrogen evolution.
  • the preferably dried polyetherdiol (reactant (b)) is heated to reaction temperature, diluted with solvent and the catalyst is added and mixed.
  • the siloxane (reactant (a)), diluted with a solvent, is then metered in with controlled hydrogen evolution.
  • the metering is preferably carried out continuously, so that a controlled progress of the reaction is possible, which is noticeable through a corresponding continuous gas release. Once the gas release has ended, the reaction is complete, which can also be proven by taking samples and determining the SiH value externally.
  • the addition of the pure or solvent-diluted siloxane (reactant (a)) in the four embodiments mentioned above can be carried out in intervals instead of continuously.
  • the siloxane (reactant (a)) is then added in intervals. This means that after each dosing interval there is a dosing break, which advantageously lasts until a quantitative SiH conversion of the previously dosed portion is indicated by the lack of hydrogen evolution. The next interval is then added.
  • the dosage amounts and times per interval are preferably kept constant, but the person skilled in the art can make adjustments in the specific application. For example, at the beginning of the synthesis, larger amounts of siloxane can be dosed per interval and towards the end smaller amounts, or vice versa.
  • the reactants (a) and (b) are reacted with controlled hydrogen evolution until the SiH conversion is quantitative.
  • target conversion is understood to mean the amount of hydrogen that can be released with quantitative SiH conversion of the amount of hydrogen siloxane present in the reaction system at any given time.
  • actual conversion is understood to mean the amount of hydrogen actually released at any given time.
  • This controlled hydrogen evolution can be achieved by a controlled dosage of component (a) to component (b). If the deviation between the target and actual conversion is too high, for example, the rate at which component (a) is added can be reduced.
  • a preferred method for controlling hydrogen evolution is described in detail in the examples section.
  • the SiOC-linked, linear polydialkylsiloxane-polyoxyalkylene block copolymers with repeating (AB) units, produced by the process according to the invention, can be used particularly advantageously as surface-active additives, in particular as cell openers, for the production of polyurethanes, preferably polyurethane foams, in particular for the production of rigid polyurethane foams , be used; Particularly preferred are single-component PU canned foam (construction foam, assembly foam, one-component foam/OCF) and/or other rigid polyurethane foams in which a high open-cell structure is advantageous (such as open-cell spray foam, packaging foam, headliner foam, pipe insulation foams, floral floral foam). and/or thermoformable rigid foams, etc.). These uses are therefore also the subject of the present invention.
  • the finished PU foam preferably rigid PU foam
  • This desirable dimensional stability i.e. low shrinkage or low post-expansion, can preferably be achieved through a high open cell density of the foam.
  • the PU foam does not have any serious foam defects in the form of voids due to this open cell structure: the cells of the foam should preferably continue to be fine and not have any coarsening.
  • polyol isocyanate prepolymers when producing such PU foams.
  • a cell opener in addition to the foam stabilizer usually contained (usually a polyethersiloxane), with the SiOC-linked, linear polydialkylsiloxane-polyether block copolymers according to the invention having proven to be particularly efficient for this application.
  • the SiOC-linked, linear polydialkylsiloxane-polyether block copolymers with repeating (AB) units obtainable by the process according to the invention can therefore be used with particular advantage as cell openers in the production of polyurethane foams, in particular rigid polyurethane foams.
  • cell opener is known to those skilled in the art in connection with the production of PU foams.
  • Cell openers are substances that are suitable, or whose function is, during the production of a polyurethane foam, preferably rigid polyurethane foam, which would otherwise usually be largely closed-cell (namely, in the case of rigid PU foam, usually less than 30%, preferred).
  • SiOC-linked, linear polydialkylsiloxane-polyether block copolymers with repeating (AB) units as cell openers, which can be obtained by the process according to the invention, enables the resulting PU foam, in particular rigid PU foam, to be highly open-celled.
  • AB repeating
  • the use concentration of the SiOC-linked, linear polydialkylsiloxane-polyoxyalkylene block copolymers according to the invention with repeating (AB) units as a surface-active additive, in particular as a cell opener, in the polyurethane foam to be produced, preferably rigid polyurethane foam, is preferably between 0.01% by weight and 10% by weight .-%, preferably between 0.05% by weight and 7% by weight, particularly preferably between 0.1% by weight and 5% by weight, in each case based on the overall formulation of the polyurethane foam.
  • polyurethane foam is known to those skilled in the art (see e.g. Adam et al., “Polyurethanes”, Ullmann’s Encyclopedia of Industrial Chemistry - Paragraph 7”, 2012, Wiley VCH-Verlag, Weinheim).
  • a preferred composition according to the invention of a PU foam, preferably rigid polyurethane foam contains the following components: a) SiOC-linked, linear polydialkylsiloxane-polyoxyalkylene block copolymer according to the invention with repeating (AB) units b) polyol component c) (poly)isocyanate component d) catalyst e) optionally foam stabilizer f) blowing agent g) optionally further additives, preferably fillers, liquid or solid flame retardants, dispersing aids, etc.
  • the SiOC-linked, linear polydialkylsiloxane-polyoxyalkylene block copolymer with repeating (AB) units according to the invention is used as a surface-active additive, preferably as a cell opener.
  • polyurethane and polyurethane foam are established technical terms and have long been known to experts.
  • polyurethane (PU) is understood to mean in particular a product obtainable by reacting a polyisocyanate component with a polyol component.
  • PU means both polyurethane and polyisocyanurates, polyureas and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret and/or uretimine groups.
  • polyurethane foam in the context of the present invention is understood to mean a foam that is obtained as a reaction product of a polyisocyanate component and a polyol component.
  • PU foam polyurethane foam
  • other functional groups such as allophanates, biurets, ureas, carbodiimides, uretdiones, isocyanurates or uretimines can also be formed.
  • PU rigid foam (polyurethane rigid foam) is a fixed technical term.
  • the known and fundamental difference between soft foam and rigid foam is that soft foam exhibits elastic behavior and the deformation is therefore reversible.
  • Rigid foam on the other hand, is permanently deformed. More information on polyurethane rigid foams can be found in the "Plastics Handbook, Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd edition 1993, Chapter 6.
  • foam and foamed material are used synonymously in the context of this invention. This also applies to terms based on them, such as rigid foam or rigid foam, etc.
  • Particularly preferred PU foams in the sense of the present invention are rigid polyurethane foams, such as in particular one-component can foam, open-cell spray foam, packaging foam, roof liner foam, pipe insulation foam, floral foam, thermoformable rigid foam and/or other rigid polyurethane foams in which a high degree of open cell density is particularly advantageous.
  • polyol component (b) One or more organic compounds with OH groups, SH groups, NH groups and/or NH2 groups with a functionality of 1.8 to 8 can be used as polyol component (b).
  • the polyol component comprises at least one compound with at least two isocyanate-reactive groups, selected from OH groups, SH groups, NH groups and/or NH2 groups, in particular OH groups.
  • a functionality of, for example, 1.8 can result from mixing at least one compound with a higher functionality, for example greater than or equal to 2, with at least one compound with a functionality of, for example, 1. This can happen in particular if a polyisocyanate component (c) with a functionality greater than 2 or additional crosslinkers are used as optional additives.
  • a polyisocyanate component (c) with a functionality greater than 2 or additional crosslinkers are used as optional additives.
  • Corresponding compounds that can usually be used in the production of PU foams are known to those skilled in the art and are described, for example, in the “Plastics Handbook, Volume 7, Polyurethanes”, Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1. Compounds with OH numbers in the range from 10 to 1200 mg KOH/g are usually used.
  • Particularly preferred compounds are all polyether polyols and polyester polyols commonly used for the production of polyurethane systems, in particular polyurethane foams.
  • polyether polycarbonate polyols such as polyether polycarbonate polyols, natural oil based polyols (NOPs; described in WO 2005/033167, US 2006/0293400, WO 2006/094227, WO 2004/096882, US 2002/0103091, WO 2006/116456, EP 1678232), filler polyols, prepolymer-based polyols and/or recycled polyols can be used.
  • NOPs natural oil based polyols
  • Recycling polyols are polyols obtained from chemical recycling of polyurethanes, for example by solvolysis, such as glycolysis, hydrolysis, acidolysis or aminolysis.
  • solvolysis such as glycolysis, hydrolysis, acidolysis or aminolysis.
  • the use of recycling polyols represents a particularly preferred embodiment of the invention.
  • the polycomponent contains polyol-isocyanate prepolymers, this is a preferred embodiment of the invention.
  • polyisocyanates with two or more isocyanate groups can be used as the isocyanate or polyisocyanate component (c).
  • Suitable polyisocyanates within the meaning of this invention are all organic isocyanates with two or more isocyanate groups, in particular the known aliphatic, cycloaliphatic, arylaliphatic and preferably aromatic polyfunctional isocyanates.
  • alkylene diisocyanates with 4 to 12 carbon atoms in the alkylene radical, such as 1,12-dodecane diisocyanate, 2-ethyl-tetramethylene-1,4-diisocyanate, 2-methyl-pentamethylene-1,5-diisocyanate, tetramethylene-1,4-diisocyanate, pentamethylene diisocyanate (PDI) and preferably hexamethylene-1,6-diisocyanate (HMDI), cycloaliphatic diisocyanates such as cyclohexane-1,3- and -1,4-diisocyanate and the corresponding isomer mixtures, 4,4'-methylene-dicyclohexyl diisocyanate (H12MDI), isophorone diisocyanate (IPDI), 2,4- and 2,6-methylcyclohexyl diisocyanate and the corresponding isomer mixtures and preferably aromatic di- and poly
  • the organic polyisocyanates can be used individually or in the form of their mixtures.
  • Corresponding “oligomers” of the diisocyanates can also be used, such as the IPDI trimer based on isocyanurate, biurets or urethdiones.
  • prepolymers in particular based on the above-mentioned isocyanates, is possible.
  • Particularly suitable is the mixture of MDI and more highly condensed analogues with an average functionality of 2 to 4 known as "polymeric MDI" (also known as "crude MDI"), as well as the various isomers of TDI in pure form or as a mixture of isomers.
  • isocyanates that have been modified by the incorporation of urethane, uretdione, isocyanurate, allophanate and other groups, so-called modified isocyanates.
  • modified isocyanates are also listed, for example, in EP 1712578, EP 1161474, WO 00/58383, US 2007/0072951, EP 1678232 and WO 2005/085310, all of which are incorporated herein by reference.
  • a preferred ratio of polyisocyanate component and polyol component expressed as an index of the formulation, i.e. as the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g. OH groups, NH groups) multiplied by 100, is in the range from 10 to 1000, preferably 40 to 500.
  • An index of 100 represents a molar ratio of the reactive groups of 1 to 1.
  • Suitable catalysts (d) that can be used for the production of polyurethanes, in particular PU foams, are known to the person skilled in the art from the prior art; for the purposes of the present invention, all compounds that are capable of catalyzing the reaction of isocyanate groups with OH, NH or other isocyanate-reactive groups and/or the reaction of isocyanate groups with one another can be used.
  • the usual catalysts known from the prior art can be used here, including, for example, amines (cyclic, acyclic; monoamines, diamines, oligomers with one or more amino groups), ammonium compounds, organometallic compounds and/or metal salts, preferably those of tin, iron, bismuth, potassium and/or zinc. In particular, mixtures of several such compounds can be used as catalysts.
  • Foam stabilizers (e) and their use in the production of PU foams are known to those skilled in the art.
  • the use of foam stabilizers is optional; one or more foam stabilizers are preferably used.
  • Surface-active compounds (surfactants) in particular can be used as foam stabilizers. They can be used to optimize the desired cell structure and the foaming process.
  • Si-containing compounds can be used in particular, which support foam production (stabilization, cell regulation, cell opening, etc.). These compounds are well known from the prior art.
  • Particularly preferably, at least one foam stabilizer based on a polyethersiloxane (polydialkylsiloxane-polyether copolymer) can be used.
  • Si-free surfactants can also be used.
  • EP2295485 A1 the use of lecithin
  • US 3746663 the use of vinyl Pyrrolidone-based structures are described as a foam stabilizer for the production of rigid PU foam.
  • Si-free foam stabilizers are described, for example, in EP 2511328 B1, DE 102001 1007479 A1, DE 3724716 C1, EP 0734404, EP 1985642, DE 2244350 and US 5236961.
  • Blowing agents and their use in the production of PU foams are known to those skilled in the art.
  • blowing agent is optional; blowing agent is preferably used.
  • the use of one or a combination of several blowing agents (f) fundamentally depends on the type of foaming process used, the type of system and the application of the PU foam obtained. Chemical and/or physical blowing agents as well as a combination of both can be used.
  • a high or low density foam is produced.
  • Foams with densities of 3 kg/m 3 to 900 kg/m 3 , preferably 5 to 350, particularly preferably 8 to 200 kg/m 3 , in particular 8 to 250 kg/m 3 can be produced.
  • Physical blowing agents which can be used are preferably one or more of the corresponding compounds with suitable boiling points and mixtures thereof, such as hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclo-, iso-, n-pentane, fluorocarbons (HFC), preferably HFC 245fa, HFC 134a or HFC 365mfc, chlorofluorocarbons (HCFC), preferably HCFC 141 b, hydrofluoroolefins (HFO) or hydrohaloolefins, preferably 1234ze, 1234yf, 1224yd, 1233zd(E) or 1336mzz, esters, preferably methyl formate, ketones, preferably acetone, ethers preferably dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane or 1,2-dichloroethane.
  • HFC fluorocarbons
  • HFC fluorocarbons
  • HFC fluorocarbons
  • gaseous propellants can also preferably be used in pressure cans, whereby all suitable gases under pressure or in pressure-liquefied form are possible, for example hydrocarbons such as butane isomers and propane isomers, dimethyl ether, nitrogen, air and other suitable gases.
  • hydrocarbons such as butane isomers and propane isomers, dimethyl ether, nitrogen, air and other suitable gases.
  • One or more compounds which react with NCO groups to release gases can preferably be used as chemical blowing agents.
  • Optional additives (g) used may be one or more of the substances known from the state of the art which are used in the production of polyurethanes, in particular PU foams, such as crosslinkers, chain extenders, stabilizers against oxidative degradation (so-called antioxidants), flame retardants, biocides, cell-refining additives, nucleating agents, other cell openers, solid fillers, antistatic additives, thickeners, dyes, pigments, color pastes, fragrances and/or emulsifiers, etc.
  • PU foams such as crosslinkers, chain extenders, stabilizers against oxidative degradation (so-called antioxidants), flame retardants, biocides, cell-refining additives, nucleating agents, other cell openers, solid fillers, antistatic additives, thickeners, dyes, pigments, color pastes, fragrances and/or emulsifiers, etc.
  • the composition according to the invention can contain one or more of the known flame retardants suitable for producing PU foams, such as halogen-containing or halogen-free organic phosphorus-containing compounds, such as triethyl phosphate (TEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(2-chloroethyl) phosphate (TCEP), dimethylmethanephosphonate (DMMP), dimethylpropanephosphonate (DMPP), ammonium polyphosphate or red phosphorus, chlorinated paraffins, nitrogen-containing compounds such as melamine, melamine cyanurate or melamine polyphosphate or halogenated compounds such as chlorinated and/or brominated polyether and/or polyester polyols. Mixtures of different flame retardants can also be used.
  • halogen-containing or halogen-free organic phosphorus-containing compounds such as triethyl phosphate (TEP), tris(1-chloro-2-propyl
  • any preferred or particularly preferred embodiment of the invention may be combined with one or more of the other preferred or particularly preferred embodiments of the invention.
  • the process for producing PU foams can be carried out using all known methods, e.g. by hand mixing or preferably with the help of foaming machines. If the process is carried out using foaming machines, high-pressure or low-pressure machines can be used.
  • the process for producing PU foams can be carried out both batchwise and continuously and, for example, 1K, 1, 5K or 2K systems as described in EP 3717538 A1, US 7776934 B2, EP 1400547 B1 or EP 2780384 B2 can be used .
  • One-component PU can foam is well known to the person skilled in the art from the prior art.
  • the term one-component PU can foam includes polyurethane foams which are preferably characterized by the presence of a polyol-isocyanate prepolymer which can be propelled from a pressure can by gases as a blowing agent and thus foamed.
  • Prepolymers that are particularly suitable for this purpose can be obtained, for example, by reacting polyols and (poly)isocyanate with one another using suitable catalysts (for example blowing catalysts such as 2,2'-dimorpholinyl diethyl ether) or without the use of a catalyst.
  • suitable catalysts for example blowing catalysts such as 2,2'-dimorpholinyl diethyl ether
  • the final curing of these prepolymers then takes place under the influence of moisture, for example from the environment.
  • the areas of application for this type of foam are the assembly, bonding and sealing of windows, door frames, pipes, ducts, etc., as well as the filling of gaps in masonry, cavities, cracks and joints.
  • Spray foam is a released foam that is applied by spraying or squirting the liquid reaction components onto a substrate. Processing is usually carried out using a spray foam machine, which can be designed as a high or low pressure machine and brings together and mixes the two components (polyl mixture and (poly) isocyanate).
  • the foam is usually discharged using a static mixer in the form of a spray gun.
  • the raw materials or foam can also be released using gas pressure be discharged into a larger container, similar to the principle of canned foams.
  • the foam is used for insulating and static purposes on walls, roofs, floors and can be open-cell or closed-cell, depending on the application.
  • Packaging foam is used to package, protect and cushion sensitive goods.
  • a low-density, open-cell foam is usually used to tightly enclose the goods to be protected and protect them from damage, impacts, etc.
  • the foam is also foamed directly into the space between the packaging and the goods if necessary.
  • Thermoformable polyurethane rigid foams are polyurethane rigid foams that are mechanically shaped after production, for example by applying heat, water (steam) and pressure. A molded part is produced from the initially block-shaped foam, which is then cut to size if necessary. Examples are roof liner foam (also called headliner foam) and hood liner foam (foam for trunk covers and trim).
  • Floral floral foam which is used for arranging flowers etc., is a polyurethane foam that, thanks to its low density, mechanical properties and high open cells, is suitable for holding flowers and other objects by inserting them into the foam.
  • Pipe insulation foam is a polyurethane foam that is used to insulate pipes. On the one hand, it protects the pipe or its contents from heat or cold losses, and on the other hand from mechanical impact. In particular, in the area of pipes laid in water, in the sea and in the deep sea, a high degree of open cell density is sometimes desired for mechanical reasons.
  • the SiOC-linked, linear polydialkylsiloxane-polyether block copolymers with repeating (AB) units described in this invention can preferably be used as surface-active additives, in particular as cell openers, in particular in all other PU foam, in particular PU rigid foam applications , in which a high level of open cells is desired, which, for example, has a direct positive effect on the dimensional stability of the foam.
  • the measurement of the open cell or closed cell content of a rigid polyurethane foam is trivial for the expert and can be carried out preferably according to DIN ISO 4590:2016-12 “Determination of the volume fraction of open and closed cells in rigid foams”, e.g. with a gas pycnometer.
  • high open cell density means an open cell density of the PU foam, in particular PU rigid foam, of preferably > 30%, more preferably > 50% and in particular > 70% of the cells can be seen.
  • a possible upper limit of open cells can be eg 90% of the cells or eg 80% of the cells or eg 100% of the cells.
  • the measurement of the dimensional stability of a one-component PU canister foam can preferably be carried out according to the method TM 1004:2013 of the FEICA - Association of the European Adhesive & Sealant Industry (“Determination of the Dimensional Stability of an OCF Canister Foam”, Brussels, 19.02.2013).
  • the SiH conversion of the dehydrogenative coupling is determined by butylate-catalyzed release of the residual (SiH) contained in the sample as elemental hydrogen and its quantitative determination.
  • SiH residual
  • a defined amount of the sample to be analyzed (between 0.3 and 10 g of sample depending on the expected SiH value) is weighed on an analytical balance into a reaction vessel containing a magnetic stirrer.
  • the reaction vessel is equipped with a dropping funnel which is filled with approx. 25 mL of a sodium butylate solution (5% in n-butanol).
  • the reaction vessel is connected via a section with a 3-way stopcock to a 50 mL water-filled burette, which in turn is connected to a water-filled expansion vessel via a hose.
  • the reaction vessel stands on a magnetic stirring plate that is at approximately eye level.
  • the 3-way tap must be set so that all three ways are open.
  • the compensating vessel is removed from its holder and brought to the burette.
  • the aim is to bring the two liquid levels (burette & compensating vessel) on top of each other at zero. If this is the case, then the 3-way stopcock is set so that only the path between the burette and the reaction vessel is open.
  • the liquid level is again brought to zero to check the tightness of the apparatus. If there is a leak, the joints must be checked and, if necessary, re-greased in order to create a tight device.
  • the level adjustment must be carried out again at zero. If the experimental setup is tight, the magnetic stirrer is set to a low stirring speed and the butylate solution is added dropwise so that the falling water column in the burette does not break off. From time to time the liquid surfaces are placed on top of each other again. If the displaced liquid volume remains stable, i.e. the volume remains unchanged when the liquid levels are placed on top of each other, the volume achieved is recorded as the maximum gas volume released. Taking into account the pressure of the water vapor according to Landolt-Börnstein, the SiH value can be calculated according to the weighed amount and using the general gas equation.
  • Weight-average and number-average molecular weights are determined in the context of this invention for the SiOC-linked, linear polydialkylsiloxane-polyoxyalkylene block copolymers produced and for the linear a,co-(SiH)-functional polydialkylsiloxanes used, calibrated against a polystyrene standard by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the polydispersity index (PDI) is given as a further characteristic parameter for describing the molecular weight distribution.
  • the GPC was carried out on a PSS SECurity 1260 (Agilent 1260) equipped with an Rl detector and an SDV 1000/10000 ⁇ column combination consisting of a 0.8 cm x 5 cm pre-column and two 0.8 cm x 30 cm main columns at a temperature of 30°C and a flow rate of 1 mL/min (mobile phase: THF).
  • the sample concentration was 10 g/L and the injection volume was 20 pL.
  • iodine number (IZ; DGF C-V 11 a (53); acid number (SZ; DGF C-V 2); OH number (ASTM D 4274 C).
  • the process according to the invention is characterized in that the two reactants (a) and (b) are preferably reacted in equimolar amounts and with controlled hydrogen evolution until quantitative SiH conversion, in particular reactant (b) being introduced and reactant (a) being metered in .
  • controlled hydrogen development provides in particular that the rate of addition of component (a) to (b) is such that the deviation of the actual conversion from the target conversion is preferably in the range of 0 to 10% from 0 to 7.5% and particularly preferably from 0 to 5%.
  • a preferred method for determining hydrogen evolution is as follows:
  • the reaction is carried out in a 1000 ml flat-ground four-neck flask equipped with a stainless steel Sigma stirrer®, internal thermometer and a reflux condenser with gas discharge hose.
  • a standard heating mantle is used as the heating medium, which is controlled by a PID fuzzy logic to set the target temperature.
  • the gas discharge tube of the flat ground flask leads via a transition piece with olive into a gas-tight 4 liter 2-neck flask, which is filled with boiled, gas-free water without any dead volume.
  • the 2-neck flask is also equipped with a gas inlet tube with olive, which reaches just above the bottom of the flask.
  • the 2-neck flask stands on a tared scale.
  • the reaction begins immediately and the resulting gas, which creates a volume expansion in the entire system, is transferred to the two-neck flask. This in turn causes the water contents to be pressed out of the piston via the inlet pipe and collected in another collecting container.
  • the actual gas volume developed can be determined using the mass of the displaced water and the density of the water at a given temperature.
  • the gas volume is converted to standard conditions using the gas laws for ideal gases. In this way, the actual conversion of the respective reaction system can be determined over the entire course of the reaction. Shown as a solid line in FIGS 1 to 5.
  • the speed of the siloxane dosing is selected such that the deviation of the "actual conversion” from the "target conversion” is preferably in the range from 0 to 10%, preferably from 0 to 7.5% and particularly preferably from 0 to 5%.
  • This specification preferably applies from a siloxane dosage amount of 10% of the total amount to be dosed and particularly preferably from 5% of the total amount to be dosed.
  • the expert can quickly set an optimal siloxane dosing speed by simple manual tests and thus achieve optimally controlled hydrogen evolution.
  • Example 1 (according to the invention):
  • 115.8 g of a dried polyoxyalkylene diol with a water content of ⁇ 0.02% are placed in a 1000 ml flat-ground four-neck flask equipped with a stainless steel Sigma stirrer, dosing unit with peristaltic pump, internal thermometer, reflux condenser with gas discharge tube.
  • the polyoxyalkylene diol with a weight-average molecular weight of 2800 g/mol and an ethylene oxide/propylene oxide ratio of approximately 1:1 is combined with 198.0 g of a linear alkylbenzene with a boiling range of approximately 240 to 314°C. The mixture is heated to a temperature of 105°C.
  • 210.9 g of a dried polyoxyalkylene diol with a water content of ⁇ 0.02% are placed in a 1000 ml flat-ground four-neck flask equipped with a stainless steel Sigma stirrer, dosing unit with peristaltic pump, internal thermometer, reflux condenser with gas discharge tube.
  • the polyoxyalkylene diol with a weight-average molecular weight of 2,800 g/mol and an ethylene oxide/propylene oxide ratio of approximately 1:1 is combined with 536.4 g of a linear alkylbenzene with a boiling range of approximately 240 to 314°C. The mixture is heated to a temperature of 105°C.
  • 160.9 g of a dried polyoxyalkylene diol with a water content of ⁇ 0.02% are placed in a 1000 ml flat-faced four-necked flask, equipped with a stainless steel Sigma stirrer, dosing unit with peristaltic pump, internal thermometer, reflux condenser with gas drainage hose.
  • the polyoxyalkylene diol with a weight-average molecular weight of 2,800 g/mol and an ethylene oxide/propylene oxide ratio of approximately 1:1 is combined with 410.6 g of a linear alkylbenzene with a boiling range of approximately 240 to 314 ° C. The mixture is heated to a temperature of 105°C.
  • 115.8 g of a dried polyoxyalkylene diol with a water content of ⁇ 0.02% are placed in a 1000 ml flat-ground four-neck flask equipped with a stainless steel Sigma stirrer, dosing unit with peristaltic pump, internal thermometer, reflux condenser with gas discharge tube.
  • the polyoxyalkylene diol with a weight-average molecular weight of 2,800 g/mol and an ethylene oxide/propylene oxide ratio of approx. 1:1 is combined with 198.0 g of a linear alkylbenzene with a boiling range of approx. 240 to 314°C.
  • the mixture is heated to a temperature of 105°C.
  • FIGS. 1 to 6 illustrate examples 1 to 5 of the invention.
  • Figures FIGS. 1 to 5 show the volume of hydrogen released depending on the amount of hydrogen siloxane added for Examples 1 to 5.
  • the experiments differ in terms of dosage type (continuous or interval) and/or dosage speed as described above.
  • the dashed line shows the target sales.
  • the solid line shows the actual sales.
  • Figure 6 summarizes the influence of the reaction control on the deviation from the target to the actual conversion as a function of the dosed siloxane mass for examples 1 to 5.
  • SiOC-linked, linear polydialkylsiloxane-polyether block copolymers as cell openers in polyurethane formulations:
  • SiOC-linked, linear polydialkylsiloxane-polyether block copolymers which were obtained in the aforementioned example(s) according to the invention (Ex. 1-4) and not according to the invention (Ex. 5), were used as cell openers.
  • the following raw materials were used to produce rigid polyurethane foams:
  • Rokopol® G 1000 Polyether polyol from Rokita
  • Rokopol® D 1002 Polyether polyol from Rokita
  • Desmophen® DE 10WF 15 Polyether polyol from Covestro
  • Voranol® CP 3322 Polyether polyol from Dow
  • TEGOSTAB® foam stabilizers from Evonik Operations GmbH TEGOSTAB® foam stabilizers from Evonik Operations GmbH
  • TEGOSTAB® B 84728 single-component PU can foam
  • TCPP Tris(2-chloroisopropyl) phosphate from Fyrol (flame retardant)
  • MDI Desmodur® 44V20L from Covestro, diphenylmethane-4,4'-diisocyanate (MDI) with isomers and higher functional homologues.
  • the contents of the can are removed after 24 hours using a commercially available foam gun.
  • a foam strand is discharged onto paper and the foam quality is assessed visually using a scale from 1 to 10 after the foam has hardened after 24 hours. To do this, the foam is cut in half.
  • the value 10 represents a perfect foam without internal defects or an extremely fine cell;
  • the dimensional stability test was carried out according to the method TM 1004:2013 of the FEICA - Association of the European Adhesive & Sealant Industry (“Determination of the Dimensional Stability of an OCF Canister Foam”, Brussels, February 19, 2013). To do this, two wooden plates are immersed in water for 30 s to allow the substrate to absorb a defined amount of water. Before applying the foam, the foam cans are shaken by hand for 1 minute and first the contents of the can are poured in (approx. 3-5 minutes). Pressing the foam gun for a second) is discarded. Then 15 g of foam is applied between the wooden panels.
  • the wooden panels are fixed with spacers and wooden clamps so that they are at a constant distance of 2 cm from each other. After 24 hours, the spacers and wooden clamps are removed and the width between the two wooden panels is determined using a caliper. The width measurement is repeated after 2, 3, 7 and 14 days and the deviation compared to the 2 cm as the starting point is determined as a percentage and noted. The lowest possible shrinkage or post-expansion is desirable, which correlates with a high open cell content of the foam.
  • the packaging foam formulation was tested using a hand-mixing method. All components were weighed into a beaker according to the formulation in Table 2, with the exception of the polyisocyanate (MDI), and mixed with a plate stirrer (6 cm diameter) for 30 s at 1000 rpm. The polyisocyanate (MDI) was then added and the reaction mixture was stirred with the stirrer described for 5 s at 3000 rpm and then applied to a box with a base area of 27x27 cm2 . The foam molding is demolded after 10 minutes. After 24 hours, the foam molding is visually assessed for shrinkage behavior. After 24 hours, the degree of internal defects and the pore structure are also visually assessed using a cut surface in the foam on a scale of 1 to 10, with 10 representing an undisturbed foam and 1 representing an extremely severely disturbed foam.
  • MDI polyisocyanate
  • Table 1 (Formulation for one-component PU can foam)
  • Table 2 (Formulation for two-component packaging foam)
  • the cell opener according to the invention effectively prevents shrinkage without showing a negative influence on the pore structure and internal disturbances (e.g.
  • Example 12 which is not according to the invention, a slight shrinkage of the foam molding could be seen after 24 hours, which is caused by insufficient cell opening. At the same time, the pore structure and internal defects are deteriorated compared to Example 11.

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Abstract

L'invention concerne un procédé de production de copolymères à blocs polydialkylsiloxane-polyoxyalkylène linéaires à liaison SiOC et comprenant des unités (AB) répétitives, comprenant la réaction d'un polydialkylsiloxane linéaire à fonction α,ω-(SiH) (a) avec un polyoxyalkylène linéaire à fonction α,ω-(OH) (b), l'utilisation d'un ou plusieurs composés d'éléments du troisième groupe principal et/ou du troisième sous-groupe comme catalyseur (c), les deux réactifs (a) et (b) réagissant de préférence en quantités équimolaires et avec une formation contrôlée d'hydrogène jusqu'à une conversion quantitative du SiH.
PCT/EP2023/075079 2022-09-28 2023-09-13 Procédé de production de copolymères à bloc de polydialkylsiloxane-polyéther linéaires à liaison sioc et leur utilisation WO2024068268A1 (fr)

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