EP3994194A1 - Polyols initiés par une amine en tant que catalyseurs pouvant être intégrés dans de la mousse hr - Google Patents

Polyols initiés par une amine en tant que catalyseurs pouvant être intégrés dans de la mousse hr

Info

Publication number
EP3994194A1
EP3994194A1 EP20734198.3A EP20734198A EP3994194A1 EP 3994194 A1 EP3994194 A1 EP 3994194A1 EP 20734198 A EP20734198 A EP 20734198A EP 3994194 A1 EP3994194 A1 EP 3994194A1
Authority
EP
European Patent Office
Prior art keywords
amine
flexible polyurethane
weight
polyurethane foam
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20734198.3A
Other languages
German (de)
English (en)
Inventor
Stefan Lindner
Klaus Lorenz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Intellectual Property GmbH and Co KG
Original Assignee
Covestro Intellectual Property GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP3994194A1 publication Critical patent/EP3994194A1/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine 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
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0058—≥50 and <150kg/m3
    • 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 method for producing an amine-based polyol by reacting a tertiary amine with various epoxides in several steps.
  • the invention further relates to the amine-based polyol obtained by this process and the use of the amine-based polyol in the production of polyurethanes, the polyurethanes preferably being synthesized on the basis of tolylene diisocyanate (TDI) and preferably being
  • polyurethanes by reacting a reaction mixture of polyisocyanates with polyols, catalysts and optionally with blowing agents, such as water, additives and / or auxiliaries, is generally known.
  • Polyurethanes can be produced as rigid foam or as flexible foam, among other things.
  • Flexible polyurethane foam is understood to mean polyurethane foam that offers a low resistance to compressive stress, which is open-cell, air-permeable and reversibly deformable.
  • Flexible polyurethane foam can, among other things, be produced by polymerizing the reaction mixture in a mold, which is called molded foams. The reaction mixture can cure either with or without external heat input after foaming; depending on the process, one speaks of hot foam or cold foam.
  • TDI-based flexible polyurethane foam especially cold foam, is an essential component of upholstery, for example seat cushions for the automotive industry.
  • Polyurethane foam which is used as padding, should be pleasantly soft to the touch and good
  • the long-term use properties are represented in particular by the compression set after the action of heat and moisture on the foam, the so-called heat-moisture aging.
  • heat-moisture aging When using flexible polyurethane foams as (car seat) cushioning material, low emissions of volatile substances are important.
  • the VDA 278 test is usually used to determine emissions.
  • the VDA 278 test is a thermal desorption process for
  • VOC volatile organic substances
  • the polyurethane foam has to meet certain requirements, but also its production.
  • An economical and safe manufacturing process is desired.
  • the economy of the manufacturing process depends, among other things, on the foaming behavior of the Reaction mixture for the polyurethane foam.
  • the period from the beginning of the mixing of the reaction mixture to the end of the rise process of the polyurethane foam is called the rise time.
  • the rise time is only long enough to fill the entire mold, but otherwise short, i.e. the reaction mixture foams up quickly and only needs to remain in the mold for a relatively short period of time, for example, before the largely hardened cold foam part is released from the mold can.
  • the speed of foam formation can be influenced by catalysts.
  • catalysts especially in the production of polyurethane cold foam, the catalysis of blowing and
  • Low molecular weight catalysts that can be incorporated also influence the properties of the flexible polyurethane foam, in particular they lead to poor thermal moisture aging values of
  • WO 2015/153316 discloses starter molecules for the production of polyurethane foams which are synthesized from a tertiary amine and a polyhydric alcohol, glycidyl ether or epoxide.
  • the tertiary amines have two substituents, each of which has either terminal hydroxyl groups or primary amines. The document does not deal with possible sagging or collapsing of polyurethane foams.
  • EP 1 878 492 B1, EP 1 977 825 B1 and EP 1 977 826 B1 relate to catalysts made from di-aminoethyl ethers which are substituted by ether or ester groups for the production of
  • Polyurethane gels or foams are disclosed which are obtained by reacting N, N, N'-trimethyl bis (aminoethyl) ether with glycidyl ethers or glycidyl esters.
  • the publications do not disclose any emission values for volatile amines of the polyurethane foam.
  • EP 2 104 696 relates to the production of polyurethane products, a mixture of amine-based polyols and urea being used as the catalyst.
  • the catalyst mixture should lead to a reduced emission of volatile substances and at the same time have good catalytic properties.
  • the resulting flexible polyurethane foam should have a core density according to DIN EN ISO 845 from 10/2015 in the range from 25 to 90 kg / m 3 ,
  • the object of the present invention was to provide a built-in catalyst for the production of flexible polyurethane foam which does not delay the foaming behavior of a flexible polyurethane foam and does not lead to the resulting flexible polyurethane foam sagging after foaming.
  • a flexible polyurethane foam containing the amine-based polyol should have low emissions, in particular of low molecular weight amines according to the test standard VDA 278, and good heat-moisture aging properties.
  • Good heat and moisture aging properties should be understood as a humid aged load loess (HALL test) of -10% to 20% and a compression set after humid heat 50% / 22h / 70 ° C (HACS test) test of 0% to 40%.
  • a TDI-based flexible foam containing the polyol according to the invention should have the properties mentioned above.
  • R 1 is a different or the same Ci to Cio alkyl radical and n is an integer from 1 to 10,
  • reaction takes place until at least 90% by weight of the epoxide B used has reacted, so that the amine-based polyol is obtained.
  • the amine-based polyols according to the invention lead to an advantageous foaming behavior of the reaction mixture and that the flexible polyurethane foam obtained does not sag after foaming.
  • the flexible polyurethane foams showed good heat-moisture aging values and low emissions according to the VDA 278 test standard.
  • the amine-based polyol according to the invention is obtained by a polymerization process in which various epoxides are successively combined with an amine of the general formula (I)
  • R ⁇ N - (CH 2 ) n - NH 2 (I) are implemented.
  • R 1 is preferably the same C 1 to C 3 alkyl radical and n is an integer from 2 to 6, more preferably R 1 is in each case a methyl radical.
  • the amine of the general formula (I) is 3-dimethylamino-1-propylamine.
  • step a) of the process according to the invention the amine of the general formula (I) is reacted with an epoxide A, the epoxide A preferably being propylene oxide.
  • the epoxide and the amine of the general formula (I) are preferably reacted in a molar ratio of 20 to 50: 1, more preferably 30 to 50: 1.
  • the reaction takes place until at least 90% by weight, preferably at least 95% by weight, more preferably at least 98% by weight, of the epoxide A used has been converted and an intermediate product is obtained.
  • step b) of the process according to the invention the intermediate product obtained in step a) is reacted with an epoxide B, the epoxide B preferably being ethylene oxide.
  • the epoxide and the intermediate are reacted in a molar ratio of 8 to 40: 1, preferably in a molar ratio of 8 to 35: 1, more preferably 8 to 30: 1.
  • the reaction takes place until at least 90% by weight, preferably at least 95% by weight, more preferably at least 98% by weight, of the epoxide B used has been converted.
  • the conversion rate of the respective epoxide can be assessed in the conversion of educts which are gaseous at the reaction temperature on the basis of the rate of pressure drop in the closed reaction vessel: falls after the end of the metering of an epoxy block during the After-reaction phase, the pressure at a rate of less than 30 mbar / h, it can be safely assumed that at least 90% of the epoxy used has been converted. If a catalyst is used in step a) and / or step b), it is advantageous to pass it through
  • the epoxide A is propylene oxide and the epoxide B is ethylene oxide.
  • the reaction in steps a) and / or b) preferably takes place in the presence of a catalyst and / or in steps a) and / or b) and / or after step b) has ended, a
  • Antioxidant used If a basic catalyst is used, one is added
  • Step b) is considered to have ended when at least 90% by weight of the epoxide B used has reacted.
  • the two hydrogen atoms of the tertiary amine are each replaced by a polyol chain.
  • the polyol chains each have the same structure, i.e. the same length, or the same degree of polymerization. Furthermore, rearrangement reactions on the
  • the amine-based polyol has the general formula (II)
  • R 1 is a different or the same, unsubstituted Ci to Cio alkyl radical
  • n is an integer from 1 to 10
  • -R 2 and -R 3 each consist of structural units which can be traced back to different epoxides, preferably to propylene oxide and ethylene oxide.
  • -R 2 - and -R 3 - are preferably each structural units of the following formula (III)
  • [PO] is a polyether fragment which can be attributed to an epoxide A, preferably im
  • [EO] is preferably a polyol fragment based on an epoxide B, which is different from epoxide A
  • the isocyanate index (also a key figure) indicates the percentage ratio of the amount of isocyanate actually used to the stoichiometric amount of isocyanate groups (amount of NCO) calculated for the conversion of the OH equivalents:
  • the invention further relates to the amine-based polyol which is obtained or can be obtained by the process according to the invention.
  • the invention also relates to the use of the amine-based polyol in the production of flexible polyurethane foam, in particular in the production in a cold foam process.
  • furniture upholstery, textile inserts, mattresses, automobile seats, headrests, armrests, sponges, headliners, door side panels, seat covers or components are preferably produced.
  • the invention relates to a flexible polyurethane foam obtained by or obtainable by reacting a composition containing or consisting of
  • an isocyanate-reactive component Al containing or consisting of compounds with isocyanate-reactive hydrogen atoms and / or a filled polyol;
  • a component A3 containing or consisting of at least one propellant
  • ком ⁇ онент A4 optionally containing a component A4 or consisting of auxiliaries and additives; such as
  • component B containing or consisting of at least one aromatic polyisocyanate; preferably tolylene diisocyanate;
  • composition preferably contains or consists of
  • component Al From 65 to 95 parts by weight of component Al, component Al preferably containing 5 to 60 parts by weight, based on the mass of components Al and A2, of a filled polyol,
  • component A2 From 0.1 to 5 parts by weight of component A2;
  • component A4 such as
  • component B From 20 to 70 parts by weight of component B, component B in particular containing or consisting of tolylene diisocyanate;
  • polyols further compounds containing hydroxyl groups
  • G. Oertel ed.: “Kunststoffhandbuch, Volume 7, Polyurethane”, Hanser Verlag, Kunststoff 1993, pp. 57-75.
  • Polyols used with preference are polyether polyols (in particular poly (oxyalkylene) polyols) and polyester polyols, the polyols used preferably having an OH number according to DIN 53240 in the range from 10 to 40, more preferably in the range from 15 to 35.
  • polyether polyols are prepared by known methods, preferably by base-catalyzed polyaddition of alkylene oxides onto polyfunctional starter compounds containing active hydrogen atoms, such as alcohols or amines. Examples are:
  • Ethylene glycol diethylene glycol, 1,2-propylene glycol, 1,4-butanediol, hexamethylene glycol, bisphenol A, trimethylolpropane, glycerine, pentaerythritol, sorbitol, cane sugar, degraded starch, water, methylamine, ethylamine, propylamine, butylamine, aniline, benzylamine, o- and p-toluidine, a, b-naphthylamine, ammonia, ethylenediamine, propylenediamine, 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and / or 1,6-hexamethylenediamine , o-, m- and p-phenylenediamine, 2,4-, 2,6-tolylenediamine, 2,2-, 2,4- and 4,4'-diaminodiphenylmethane and di
  • Preferred alkylene oxides are ethylene oxide, propylene oxide, butylene oxide and theirs
  • the polyether chains can be built up by alkoxylation using only one monomeric epoxide, but can also be carried out randomly or in blocks using two or three different monomeric epoxides.
  • alkylene oxides to the starter compounds can, for example, also take place with DMC catalysis.
  • polyether carbonate polyols can also be used in any other “simple” polyether polyols.
  • Polyether carbonate polyols can be obtained, for example, by the catalytic conversion of ethylene oxide and propylene oxide, optionally other alkylene oxides, and carbon dioxide in the presence of H-functional starter substances (see, for example, EPA 2046861).
  • Methods for the production of polyester polyols are also well known and are described, for example, in the two literature references mentioned above (“Kunststoffhandbuch, Volume 7, Polyurethane”, “Reaction Polymers“).
  • the polyester polyols are generally polyfunctional by polycondensation
  • Carboxylic acids or their derivatives such as acid chlorides or anhydrides, produced with polyfunctional hydroxyl compounds.
  • polyfunctional carboxylic acids adipic acid
  • Phthalic acid isophthalic acid, terephthalic acid, oxalic acid, succinic acid, glutaric acid, azelaic acid, sebacic acid, fumaric acid or maleic acid.
  • Ethylene glycol diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol,
  • the polyester polyols can also be produced by ring-opening polymerization of lactones (e.g. caprolactone) with diols and / or triols as starters.
  • lactones e.g. caprolactone
  • polyether polyols, polyether carbonate polyols and polyester polyols described above can also be used with the concomitant use of filler-containing polyols such as polymer polyols (containing styrene-acrylonitrile copolymers in dispersed form, so-called SAN-modified polyols) or polyurea dispersion polyols etc. for the production of the polyurethane Soft foams are used.
  • SAN-modified polyols are preferably used, particularly preferably those with a solids content of 20 to 50% by weight, in particular 35 to 45% by weight, based on the modified polyol.
  • Filled polyol preferably has an OH number according to DIN 53240 in the range from 10 to 40, preferably in the range from 15 to 35, more preferably in the range from 20 to 30.
  • a crosslinking component can be added during the production of the polyurethanes according to the invention.
  • Such crosslinkers are, for example, diethanolamine, triethanolamine, glycerine, trimethylolpropane (TMP), adducts of such crosslinking compounds with ethylene oxide and / or propylene oxide with an OH number ⁇ 1,000 or glycols with a number average molecular weight ⁇ 1,000.
  • Triethanolamine, glycerol, TMP or low EO and / or PO adducts thereof are preferred.
  • Diethanolamine is particularly preferred.
  • auxiliaries can optionally be added.
  • auxiliaries are understood to mean, in particular, catalysts and stabilizers known per se.
  • Melamine or TCPP for example, can be used as flame retardants.
  • the following catalysts are preferably used: aliphatic tertiary amines (for example
  • cycloaliphatic amidines, urea and derivatives of urea such as
  • Aminoalkyl ureas see for example EP-A 0 176 013, in particular
  • Tin (II) salts of carboxylic acids can also be used as catalysts, the respective underlying carboxylic acid preferably having from 2 to 20 carbon atoms.
  • the tin (II) salt of 2-ethylhexanoic acid ie tin (II) - (2-ethylhexanoate)
  • the tin (II) salt of 2-butyloctanoic acid the tin (II) salt of 2- Hexyldecanoic acid
  • the tin (II) salt of neodecanoic acid the tin (II) salt of oleic acid
  • the tin (II) salt of ricinoleic acid and
  • Tin (IV) compounds such as dibutyltin oxide,
  • Dioctyltin diacetate can be used as catalysts. Of course, all of the catalysts mentioned can also be used as mixtures.
  • the catalysts are preferably used in amounts of about 0.001 to 10% by weight, based on the total amount of compounds having at least two isocyanate-reactive hydrogen atoms.
  • Further additives which may be used are surface-active additives such as emulsifiers and foam stabilizers.
  • the sodium salts of castor oil sulfonates or salts of malic acids with amines such as oleic acid diethylamine or stearic acid diethanolamine can be used as emulsifiers.
  • Alkali or ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid or dinaphthylmethanedisulfonic acid or of malic acids such as ricinoleic acid or of polymeric malic acids can also be used as surface-active additives.
  • Polyether siloxanes especially water-soluble representatives, are used as foam stabilizers. These compounds are generally structured in such a way that a copolymer of ethylene oxide and propylene oxide is bonded to a polydimethylsiloxane radical.
  • Polysiloxane-polyoxyalkylene copolymers according to DE-A 25 58 523 which are branched via allophanate groups are often of interest.
  • reaction retarders e.g. acidic substances such as hydrochloric acid or organic acid halides, also known cell regulators such as paraffins or fatty alcohols or dimethylpolysiloxanes, as well as pigments or dyes and flame retardants known per se, e.g. tris (2-chloroisopropyl) phosphate, tricresyl phosphate or ammonium phosphate and polyphosphate, also stabilizers against aging and weathering, plasticizers and fungistatic and bacteriostatic substances and fillers such as barium sulfate, kieselguhr, soot or whiting chalk.
  • reaction retarders e.g. acidic substances such as hydrochloric acid or organic acid halides, also known cell regulators such as paraffins or fatty alcohols or dimethylpolysiloxanes, as well as pigments or dyes and flame retardants known per se, e.g. tris (2-chloroisopropyl) phosphate,
  • surface-active additives and foam stabilizers as well as cell regulators, reaction retarders, stabilizers, flame-retardant substances, plasticizers, dyes and fillers, as well as fungistatic and bacteriostatic substances and details of the use and mode of action of these additives are in Vieweg and Höchtlen (ed.): Kunststoff-Handbuch, Volume VII, Carl-Hanser-Verlag, Kunststoff 1966, pp. 103-113.
  • blowing agents known in the manufacture of polyurethane foam can be used as the blowing agent component to be used.
  • Organic blowing agents include acetone, ethyl acetate, alkanes, halogen-substituted alkanes such as methylene chloride, and inorganic blowing agents e.g. Fuft or CO2.
  • a propellant effect can also be achieved by adding compounds that decompose at temperatures above room temperature with the elimination of gases, for example nitrogen, e.g. azo compounds such as azodicarbonamide or azoisobutyronitrile. Water is particularly preferably used as a chemical blowing agent. Further examples of propellants and details about the use of propellants are in Vieweg and Höchtlen (eds.):
  • Component B preferably contains the technically easily accessible polyisocyanates, e.g. 2,4- and 2,6-tolylene diisocyanate, as well as any mixtures of these isomers ("TDI"); or
  • Polyphenylpolymethylene polyisocyanates such as those produced by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI”) and carbodiimide groups,
  • Modified polyisocyanates containing urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups, in particular those modified polyisocyanates which are derived from 2,4- and / or 2,6-tolylene diisocyanate or from 4,4'- and / or 2 Derive, 4'-diphenylmethane diisocyanate.
  • Component B preferably contains or consists of
  • reaction components are reacted by the one-step process known per se, the prepolymer process or the semi-prepolymer process, preferably using mechanical equipment as described in US Pat. No. 2,764,565.
  • the foams according to the invention are molded foams.
  • the foams are manufactured in closed molds.
  • the reaction mixture is introduced into a mold.
  • Metal, e.g. aluminum, steel or plastic, e.g. epoxy resin, can be used as the molding material.
  • the foamable reaction mixture foams up in the mold and forms the molded body.
  • the form foaming can be carried out in such a way that the molded part has a cell structure on its surface. However, it can also be carried out in such a way that the molded part has a compact skin and a cellular core. According to the invention you can in this
  • the flexible polyurethane foam according to the invention preferably has an emission of aliphatic amines when measured according to the VDA 278 test from 2011, heating to determine VOC, of ⁇ 10 mg / kg, preferably ⁇ 5 mg / kg, more preferably ⁇ 1 mg / kg , on.
  • an emission of aliphatic amines when measured according to the VDA 278 test from 2011, heating to determine VOC, of ⁇ 10 mg / kg, preferably ⁇ 5 mg / kg, more preferably ⁇ 1 mg / kg , on.
  • the flexible polyurethane foam has a compression set according to moist heat 50% / 22h / 70 ° C according to DIN EN ISO 1856-2008 of 5 to 25%, preferably from 0 to 10%. Furthermore, the flexible polyurethane foam according to the invention has a humid aged foam foss according to DIN EN ISO 3386-1 of 10/2015 of -10 to 20%. In a further preferred embodiment, the flexible polyurethane foam has a humid aged compression set according to DIN EN 1856 from 2008 after steam autoclaving for 3 hours at 105 ° C. from 0 to 40%. In a first embodiment, the invention relates to a method for producing an amine-based polyol for producing flexible polyurethane foam, comprising the following steps:
  • R 1 is a different or the same Ci to Cio alkyl radical and n is an integer from 1 to 10,
  • reaction takes place until at least 90% by weight of the epoxide B used has reacted, so that the amine-based polyol is obtained.
  • the invention relates to a method according to embodiment 1, characterized in that in the amine of the general formula (I) R 1 is in each case the same Ci to C 3 alkyl radical and n is an integer from 2 to 6, where R 1 is preferably in each case a methyl radical.
  • the invention relates to a method according to one of the
  • Embodiments 1 or 2 characterized in that the amine of the general formula (I) is 3-dimethylamino-1-propylamine.
  • the invention relates to a method according to one of the preceding embodiments, characterized in that the epoxide A is propylene oxide and / or the epoxide B is ethylene oxide.
  • the invention relates to a method according to one of the preceding embodiments, characterized in that the implementation in steps a) and / or b) in Presence of a catalyst takes place and / or in steps a) and / or b) and / or after the end of step b) an antioxidant is used.
  • the invention relates to a method according to one of the preceding embodiments, characterized in that the reaction in step a) takes place until at least 95% by weight, preferably at least 98% by weight, of the epoxide A used has been converted and / or the reaction in step b) takes place until at least 95% by weight, preferably at least 98% by weight, of the epoxide B used has been converted.
  • the invention relates to an amine-based polyol obtained by or obtainable by a method according to one of embodiments 1 to 6.
  • the invention relates to the use of the amine-based polyol according to embodiment 7 as a built-in catalyst in the production of flexible polyurethane foam, in particular in the production in a cold foam process.
  • the invention relates to the use according to embodiment 8, characterized in that furniture upholstery, textile inserts, mattresses, automobile seats, headrests, armrests, sponges, headliners, door side panels, seat pads or components are produced.
  • the invention relates to a flexible polyurethane foam obtained by or obtainable by reacting a composition containing or consisting of
  • an isocyanate-reactive component Al containing or consisting of compounds with isocyanate-reactive hydrogen atoms and / or a filled polyol;
  • a component A3 containing or consisting of at least one propellant
  • ком ⁇ онент A4 optionally containing a component A4 or consisting of auxiliaries and additives; such as
  • component B containing or consisting of at least one aromatic polyisocyanate; preferably tolylene diisocyanate;
  • the invention relates to a flexible polyurethane foam according to embodiment 10, characterized in that the composition contains or consists of
  • component Al preferably contains 5 to 60 parts by weight, based on the mass of components Al and A2, of a filled polyol
  • component A2 From 0.1 to 5 parts by weight of component A2;
  • component A4 such as
  • component B From 20 to 70 parts by weight of component B, component B in particular
  • the parts by weight of components Al and C add up to 100 and the data for the parts by weight of components A2, A3, A4 and B relate to the sum of components Al and C.
  • the invention relates to a flexible polyurethane foam according to one of the embodiments 10 or 11, characterized in that the flexible polyurethane foam emits aliphatic amines when measured according to the VDA 278 test of 2011, heating to determine VOC ⁇ 10 mg / kg, preferably ⁇ 5 mg / kg, more preferably ⁇ 1 mg / kg.
  • the invention relates to a flexible polyurethane foam according to one of embodiments 10 to 12, characterized in that the flexible polyurethane foam has a compression set according to moist heat 50% / 22h / 70 ° C according to DIN EN ISO 1856-2008 from 5 to 25 %, preferably from 0 to 10%.
  • the invention relates to a flexible polyurethane foam according to one of embodiments 10 to 13, characterized in that the flexible polyurethane foam has a humid aged load loess according to DIN EN ISO 3386-1 of 10/2015 of -10 to 20% .
  • the invention relates to a flexible polyurethane foam according to one of embodiments 10 to 14, characterized in that the flexible polyurethane foam is a humid aged compression set according to DIN EN 1856 from 2008 according to
  • Amine I (3-dimethylamino-1-propylamine) - started precursor:
  • Amine-initiated polyol No. 1 according to the invention:
  • the mixture obtained in this way was transferred to a glass flask under a nitrogen blanket, where it was first dehydrated in a water jet vacuum at 80 ° C. and finally baked for a further 3 hours at 110 ° C. under a pressure of 20 mbar (membrane pump).
  • the salt formed was filtered off in a heatable pressure suction filter through a deep filter (T 750).
  • the OH number was 27.2 mg KOH / g.
  • the mixture obtained in this way was transferred to a glass flask under a nitrogen blanket, where it was first dehydrated in a water jet vacuum at 80 ° C. and finally heated for a further 3 h at 110 ° C. under a pressure of 20 mbar.
  • the salt formed was filtered off in a heatable pressure suction filter through a depth filter (T 750).
  • the OH number was 37.4 mg KOH / g.
  • the mixture obtained in this way was transferred to a glass flask under a nitrogen blanket, where it was first dehydrated in a water jet vacuum at 80 ° C. and finally heated for a further 3 h at 110 ° C. under a pressure of 20 mbar.
  • the salt formed was filtered off in a heatable pressure suction filter through a depth filter (T 750).
  • the OH number was 40.4 mg KOH / g.
  • the mixture obtained in this way was transferred to a glass flask under a nitrogen blanket, where it was first dehydrated in a water jet vacuum at 80 ° C. and finally heated for a further 3 h at 110 ° C. under a pressure of 20 mbar.
  • the salt formed was filtered off in a heatable pressure suction filter through a depth filter (T 750).
  • the OH number was 32.1 mg KOH / g.
  • the mixture obtained in this way was transferred to a glass flask under a nitrogen blanket, where it was first dehydrated in a water jet vacuum at 80 ° C. and finally heated for a further 3 h at 110 ° C. under a pressure of 20 mbar.
  • the salt formed was filtered off in a heatable pressure suction filter through a depth filter (T 750).
  • the OH number was 33.7 mg KOH / g.
  • the mixture obtained in this way was transferred to a glass flask under a nitrogen blanket, where it was first dehydrated in a water jet vacuum at 80 ° C. and finally baked for a further 3 hours at 110 ° C. under a pressure of 20 mbar (membrane pump).
  • the salt formed was filtered off in a heatable pressure suction filter through a depth filter (T 750).
  • the OH number was 28.3 mg KOH / g.
  • the amine-based polyols 1, 2, 3, 5 and 6 had an OH number, calculated on the basis of the ratios of the starting materials, of 33 mg KOH / g.
  • the amine-based polyol 4 had one based on
  • Ratios of the starting materials calculated OH number of 35 mg KOH / g.
  • the (measured) OH numbers given in Table 1 were determined in accordance with ASTM D 4274-05. However, the measured OH numbers only offer an orientation as to how many hydroxyl groups are contained in the amine-based polyols, since the measurement result can be falsified by the amine group of the amine-based polyol.
  • PO propylene oxide
  • EO ethylene oxide
  • composition of the flexible polyurethane foams is shown in Table 3.
  • Oxyethylene units Commercial product from Covestro; OH number 37 mg KOH / g
  • the components listed in the examples in Table 3 below are mixed with one another to form a reaction mixture mixed up.
  • the reaction mixture is introduced into a metal mold heated to 60 ° C. and previously coated with a release agent (PURA E1429H NV (Chem-Trend)).
  • PURA E1429H NV Chem-Trend
  • the amount used is selected according to the desired bulk density and the mold volume.
  • a mold with a volume of 9.7 dm 3 was used .
  • the moldings were removed from the mold after 4 minutes and pressed on.
  • the molded parts were sealed in aluminum composite foil after 4 hours.
  • the index given in Table 3 the OH number determined experimentally in accordance with ASTM D 4274-05 was used for the amine-based polyols.
  • Table 3 Composition and properties of MDI-based flexible polyurethane foams
  • the VDA 278 test (Association of the Automotive Industry; status 2011) is a
  • Substances are cryofocused with an inert gas stream in a cold trap and then analyzed. In order to determine the proportion of volatile organic substances (VOC), the sample is heated to 90 ° C. When determining the VOC, volatile amines are also detected.
  • VOC volatile organic substances
  • the detection limit for VOC in the VDA 278 test is 1 mg / kg.
  • the experimental data show that the polyols according to the invention do not adversely affect the mechanical properties of the flexible polyurethane foams obtained.
  • the flexible polyurethane foams according to the invention of Examples 1 and 6 have comparable values for the core density, the compressive strength, the tensile strength and the elongation at break as the polyurethane foam from Reference Example 6A, produced with conventional, non-incorporable catalysts.
  • reference examples 4 and 5 show that not every amine is suitable for the synthesis of an incorporable polyol.
  • the compositions which contained these polyols not according to the invention collapsed during the synthesis, so that no polyurethane foam could be obtained.
  • the catalytic activity of the amine-initiated, incorporable polyols was determined by a
  • Ascending profile measurement determined. For this purpose, the components listed in Table 4 were mixed and the expansion behavior of the foam sample was measured in a suitable vessel immediately after it was poured into the foam mold. The height of the rising foam is measured as a function of time. The sample should show a rapid increase and the height of the foam should then remain as high as possible, otherwise the foam sample will shrink.
  • Table 4 Composition of the MDI-based flexible polyurethane foams for determining the catalytic properties of the amine-initiated polyols
  • the experimental data show that the amine-started polyol 1 according to the invention has an advantageous catalytic effect in the production of MDI-based flexible polyurethane foams.
  • Amine-started polyols 1 according to the invention was produced, reached foam heights of more than 200 mm within a short period of time.
  • foam 7 with the amine-initiated polyol 1 according to the invention foamed to the overall highest maximum foam height of 250 mm within approx. 100 s.
  • composition of the flexible polyurethane foams is shown in Table 5.
  • Polyether polyol Polyether polyol with an OH number of 31.5 mg KOH / g, manufactured in
  • Additive III Tegostab B 8734LF2 (OH number 83 mg KOH / g), product of the company
  • Catalyst non-incorporable catalyst (Niax Catalyst A-400) containing bis (2-dimethylaminoethyl) ether; Momentive product
  • the TDI-based flexible polyurethane foams were produced by the method described above for MDI-based flexible polyurethane foams, the molded parts being removed from the mold after 5 minutes.
  • the index given in Table 5 the OH number determined experimentally in accordance with ASTM D 4274-05 was used for the amine-based polyols.
  • Table 5 Composition and properties of TDI-based flexible polyurethane foams
  • test values were determined according to the same DIN standards and procedures as for the MDI-based polyurethane foams.
  • the experimental data show that the amine-initiated polyols according to the invention are also superior to conventional catalysts in the production of TDI-based flexible polyurethane foam with regard to emissions of highly volatile organic substances (VOC / FOG) from polyurethane foam.
  • the foam from Reference Example 17 produced on the basis of non-installable catalysts, emitted 288 mg / kg of highly volatile components.
  • the emissions from the polyurethane foams with the incorporable polyols according to the invention were also below the limit of quantification of 1 mg / kg.
  • the values of the heat-moisture aging of the flexible polyurethane foam from the Example 12 according to the invention were within the desired ranges, in particular from -10% to 20% in the HALL test and from 0 to 40% in the HACS test.
  • reference examples 15 and 16 show that not every amine is suitable for the synthesis of an incorporable polyol because the
  • the catalytic activity was determined by the method described above for the MDI-based flexible polyurethane foams.
  • Table 6 Composition of the flexible polyurethane foams for determining the catalytic properties of the amine-based polyols
  • the advantageous catalytic action of the amine-initiated polyol 1 according to the invention was even more evident in the production of TDI-based flexible polyurethane foams than in the production of MDI-based flexible polyurethane foams.
  • the TDI-based flexible polyurethane foam from Reference Example 22 expanded to a height of about 220 mm, but then collapsed.
  • the TDI-based flexible polyurethane foam made from Reference example 21 only reached a height of about 160 mm. These two foams were rated as unusable, collapsed foams.

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

Abstract

La présente invention concerne un procédé pour produire un polyol à base d'amine en faisant réagir une amine tertiaire avec différents époxydes en plusieurs étapes. L'invention concerne en outre le polyol à base d'amine obtenu par ce procédé et l'utilisation du polyol à base d'amine dans la production de polyuréthanes, les polyuréthanes étant de préférence synthétisés à base de toluylène diisocyanate (TDI) et l'invention concernant de préférence des mousses moulées.
EP20734198.3A 2019-07-01 2020-06-24 Polyols initiés par une amine en tant que catalyseurs pouvant être intégrés dans de la mousse hr Pending EP3994194A1 (fr)

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EP19183588.3A EP3760659A1 (fr) 2019-07-01 2019-07-01 Polyols amorcés par de l'amine en tant que catalyseurs pouvant être intégrés dans la mousse hr
PCT/EP2020/067632 WO2021001229A1 (fr) 2019-07-01 2020-06-24 Polyols initiés par une amine en tant que catalyseurs pouvant être intégrés dans de la mousse hr

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US3178490A (en) 1961-10-06 1965-04-13 Thiokol Chemical Corp Process for producing a foamed plastic article having a dense skin
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DE1694142C3 (de) 1967-03-25 1975-10-23 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Schaumstoffen
DE1720768A1 (de) 1968-01-02 1971-07-15 Bayer Ag Kunststoffe auf Isocyanatbasis und Verfahren zu ihrer Herstellung
DE2121670C3 (de) 1971-05-03 1979-11-15 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Schaumstoffen
DE2307589C3 (de) 1973-02-16 1984-11-15 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Schaumstoffen mit vorzüglichen Entformungseigenschaften
DE2558523A1 (de) 1975-12-24 1977-07-07 Bayer Ag Verfahren zur herstellung neuer polysiloxan-polyoxyalkylen-copolymerer
DE3435070A1 (de) 1984-09-25 1986-04-03 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von gegebenenfalls geschaeumten polyurethanen, die mit einem anderen werkstoff verbunden oder konfektioniert worden sind
JPH0270718A (ja) * 1988-09-07 1990-03-09 Sanyo Chem Ind Ltd ポリウレタンの製法
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