WO2018234348A1 - Formulation destinée à réduire l'émission de formaldéhyde dans la mousse pu - Google Patents

Formulation destinée à réduire l'émission de formaldéhyde dans la mousse pu Download PDF

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Publication number
WO2018234348A1
WO2018234348A1 PCT/EP2018/066341 EP2018066341W WO2018234348A1 WO 2018234348 A1 WO2018234348 A1 WO 2018234348A1 EP 2018066341 W EP2018066341 W EP 2018066341W WO 2018234348 A1 WO2018234348 A1 WO 2018234348A1
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WO
WIPO (PCT)
Prior art keywords
composition
composition according
foam
polyurethane
isocyanate
Prior art date
Application number
PCT/EP2018/066341
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English (en)
Inventor
Lies BONAMI
Joris Karel Peter Bosman
Ingrid WELVAERT
Pengfei Wu
Yuefan Zhang
Original Assignee
Huntsman International Llc
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 Huntsman International Llc filed Critical Huntsman International Llc
Publication of WO2018234348A1 publication Critical patent/WO2018234348A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—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
    • 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
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • Present invention is related to a composition for the reduction of formaldehyde emission in PU foam.
  • the invention is also related to a method for reducing the reduction of formaldehyde emission in PU foam.
  • Polyurethane and polyurea materials are well known in the art.
  • Polyurethane and polyurea foams in particular so-called flexible polyurethane and polyurea foams, are used in a multitude of applications. More and more, the emission of components, such as in particular aldehyde components and dimethylformamide, is seen as a disadvantage.
  • Various attempts have been made to integrate so-called scavengers in the polyurethane foam.
  • DE10003157A1 discloses polymeric polyethylene imines being dissolved in a solvent, after which the solution is sucked into the foam structure. After drying or evaporation of the solvent, the polymeric molecules remain in the foam structure and act as aldehyde scavengers.
  • Patent application WO2014/026802 describes a foam where the emission of formaldehyde is decreased, when using the VDA 276 test and where the foam was made using a composition comprising an amine component.
  • WO2016/005479 describes compositions that can be used for making polyurethanes which are able to reduce formaldehyde and acetaldehyde emissions.
  • Patent application US2016/0304686 describes compounds that are able to reduce the emission of formaldehyde.
  • the invention is related to a composition
  • the pyridyl derivative according to the invention is bound on the 2, 3, 4 or 5 position to the CH 2 of the R 1 - CH 2 -R 2 formula. Preferably, it is bound on the 3 position.
  • the pyridyl derivative may be substituted e.g. with aliphatic hydrocarbon, araliphatic hydrocarbon or aromatic hydrocarbon, which can also be substituted.
  • aldehyde such as the formaldehyde in polyurethane
  • the inventors found that some of these compounds may be easily soluble in the polyisocyanate and or the isocyanate reactive compound.
  • an isocyanate reactive compound is suitable to react with the isocyanate groups of e.g. polyisocyanate compounds.
  • This reaction results in the formation of polyurea or polyurethane materials, and also modified polyurethanes which can comprise isocyanurate structures, allophanate structures, urea structures, carbodiimide structures, uretonimine structures, biuret structures, and other isocyanate adducts.
  • the polyurethane materials comprise polyisocyanate polyaddition products, for example thermosets, and foams based on polyisocyanate polyaddition products, for example flexible foams, semi rigid foams, rigid foams, and integral foams and also polyurethane coatings and binders.
  • the polyurethane of the invention is preferably used in the interior of means of transport, such as ships, aircraft, trucks, cars or buses.
  • the polyisocyanate components in the composition of the invention comprise any of the polyisocyanates known for the production of polyurethanes. These comprise the aliphatic, cycloaliphatic, and aromatic difunctional or polyfunctional isocyanates known from the prior art, and also any desired mixtures thereof.
  • diphenylmethane 2,2'-, 2,4'-, and 4,4'- diisocyanate examples are diphenylmethane 2,2'-, 2,4'-, and 4,4'- diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates with diphenylmethane diisocyanate homologs having a larger number of rings (polymer MDI), isophorone diisocyanate (IPDI) and its oligomers, tolylene 2,4- and 2,6-diisocyanate (TDI), and mixtures of these, tetramethylene diisocyanate and its oligomers, hexamethylene diisocyanate (HDI) and its oligomers, naphthylene diisocyanate (NDI), and mixtures thereof.
  • polymer MDI polymer MDI
  • IPDI isophorone diisocyanate
  • TDI tolylene 2,4- and 2,6-diisocyan
  • tolylene 2,4- and/or 2,6-diisocynate TDI
  • monomeric diphenylmethane diisocyanates and/or diphenylmethane diisocyanate homologs having a larger number of rings (polymer MDI), and mixtures of these.
  • the polyisocyanate component used can also take the form of a polyisocyanate prepolymer.
  • the isocyanate component is preferably a polyisocyanate and may comprise any number of polyisocyanates, including but not limited to, toluene diisocyanates (TDI), diphenylmethane diisocyanate (MDI) - type isocyanates, and prepolymers of these isocyanates.
  • TDI toluene diisocyanates
  • MDI diphenylmethane diisocyanate
  • prepolymers of these isocyanates prepolymers of these isocyanates.
  • Semi-prepolymers and prepolymers which may be obtained by reacting polyisocyanates with compounds containing isocyanate-reactive hydrogen atoms are also isocyanate components.
  • compounds containing isocyanate-reactive hydrogen atoms include alcohols, glycols or even relatively high molecular weight polyether polyols and polyester polyols, mercaptans, carboxylic acids, amines, urea and amides.
  • suitable prepolymers are reaction products of polyisocyanates with monohydric or polyhydric alcohols.
  • the prepolymers are prepared by conventional methods, e.g. by reacting polyhydroxyl compounds which have a molecular weight of from 400 to 5000, in particular mono- or polyhydroxyl polyethers, optionally mixed with polyhydric alcohols which have a molecular weight below 400, with excess quantities of polyisocyanates, for example aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanates.
  • the composition according to the invention further comprises a polyisocyanate reactive compound.
  • the polyisocyanate reactive compound is selected from the group consisting of polyether polyol, polyester polyol, polyether polyamine and a polyester polyamine.
  • the polyether polyols are polyethylene glycol, polypropylene glycol, polypropylene glycol-ethylene glycol copolymer, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, and polyether polyols obtained by ring-opening copolymerisation of alkylene oxides, such as ethylene oxide and/or propylene oxide, with isocyanate-reactive initiators of functionality 2 to 8.
  • the polyether polyols are based on propylene oxide and/or ethylene oxide.
  • Polyester diols obtained by reacting a polyhydric alcohol and a polybasic acid are given as examples of the polyester polyols.
  • the polyhydric alcohol ethylene glycol, polyethylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, 3-methyl- 1,5-pentanediol, 1,9-nonanediol, 2-methyl-l,8-octanediol, and the like can be given.
  • the polybasic acid phthalic acid, dimer acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, and the like can be given.
  • isocyanate reactive component or “polyisocyanate reactive component” as used herein includes any component with a “isocyanate reactive group(s)” or “isocyanate reactive moiety or moieties”.
  • isocyanate reactive group as use herein includes any group or moiety containing an active hydrogen group or moiety.
  • an active hydrogen containing group refers to a group containing a hydrogen atom which, because of its position in the molecule, displays significant activity according to the Zerewitnoff test described by Wohler in the Journal of the American Chemical Society, Vol. 49, page 3181 (1927).
  • active hydrogen groups are -OH, -NH 2 , and -NH.
  • aldehyde reducing compounds means that the compound is capable of reducing the emission of aldehyde in polyurea or polyurethane materials, and modified polyurethanes compared to polyurea or polyurethane materials, and modified polyurethanes made of a composition not comprising the aldehyde reducing compound.
  • aldehyde reducing compounds are l-(4-pyridyl) acetone, methanesulfonylacetone, methylphenylsulfonylacetate, dimethyl glutaconate, bis(phenylsulfonyl) methane, l-(p-tolylsulfonyl)-2-propanone.
  • the molecular weight of the compound is below 250.
  • the amount of the aldehyde reducing compound is from 0.01 pbw to 2 pbw, preferably from 0.05 pbw to 1.0 pbw, even more preferably between 0.05 pbw and 0.7 pbw calculated on the total weight of the composition.
  • the amount can vary depending on the type of polyurethane that is made and the isocyanate component and the isocyanate reactive component that is used.
  • the amount of the aldehyde reducing compound is an effective amount that is able to reduce the emission of formaldehyde and/or acetaldehyde.
  • the moieties R 3 , R 5 , R 6 , R 7 , R 8 , or R 9 are independently of one another selected from the group consisting of aliphatic hydrocarbons, which are optionally substituted.
  • the aliphatic hydrocarbons have 1 to 15, preferably 2 to 10, carbon atoms, which may have substitution.
  • Substituents in that case are preferably one or more isocyanate-reactive groups, which advantageously comprise isocyanate-reactive hydrogen atoms.
  • Groups of this kind that are isocyanate-reactive may be, for example,— OH,— NH— or— NH 2 groups, with carboxylic acid groups or carboxylic amide groups preferably not being considered to be isocyanate-reactive groups.
  • Particularly preferred as isocyanate-reactive groups are one or more OH groups, more particularly an OH group.
  • the aldehyde reducing compound can first be blend with the polyisocyanate or can first be blend with the isocyanate reactive compound, before it is mixed with the other compounds and then used to make polyurethane foam.
  • the composition further comprises at least a catalyst selected from blowing and/or gelling catalysts, and optionally fire retardants, antioxidants, surfactants, physical or chemical blowing agents, fillers, pigments, or any other typical additives used in polyurethane materials.
  • a catalyst selected from blowing and/or gelling catalysts, and optionally fire retardants, antioxidants, surfactants, physical or chemical blowing agents, fillers, pigments, or any other typical additives used in polyurethane materials.
  • the invention is related to a method for reducing the emission of formaldehyde and/or acetaldehyde from a polyurethane or polyurea foam, the method comprising mixing the composition as described above.
  • the VDA 276 test method (also called VOC chamber test) is an emission measurement method to measure the emissions from a foam sample done in a lm 3 chamber where the foam is exposed to 65°C and 5 RH (relative humidity) for several hours.
  • VDA 276 (Verband Der Automobil Industrie) is a specific automotive emission method used by a host of automotive OEM's (original equipment manufacturers) to specify the permissible emission levels coming from automotive interior parts.
  • Table 1 shows the formulation and results of the foam whereto l-(4-pyridyl)acetone, methanesulfonylacetone, dimethylglutaconate, bis(phenylsulfonyl) methane, and methylphenylsulfonylacetate were added.
  • Table 2 shows the formulation and results of the foam whereto l-(p-tolylsulfonyl)-2-propanone was added. For each formulation about 1 kg foam was made via hand mix foam procedure for the VDA -276 emission test (air sampling after 4 h, at 65°C/5 Rel humidity and an air exchange of 0.4 /hour).
  • Table 1 Polyol formulation and result of the formaldehyde emission. All the components are available from Huntsman International LLC, except for Tegostab B8734 LF-2 which is available from Evonik. (1) Added to the isocyanate; (2) Added to the water/amine blend. REF EXP6
  • Table 2 Polyol formulation and result of the formaldehyde emission. All the components are available from Huntsman International LLC, except for Konix FA-703 and Tegostab B8734 LF-2 which are available from Evonik. (1) Added to the isocyanate;

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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

L'invention concerne une composition comprenant un composé réactif à l'isocyanate, un polyisocyanate et un composé réducteur d'aldéhyde de formule générale R1-CH2-R2, dans laquelle R1 est *- SO2–R3, un dérivé pyridyle, ou *–CH=CHR3; R2 est *- SO2–R3, un dérivé pyridyle, *–CH=CHR2, *–C(O)R4 ou *–CN; R4 est NH, NH-R5, NR6/R7, OR8 ou R9; et dans laquelle R3, R5, R6, R7, R8, ou R9 sont, indépendamment les uns des autres, choisis dans le groupe constitué par un hydrocarbure aliphatique, un hydrocarbure araliphatique et un hydrocarbure aromatique, qui sont éventuellement substitués; * représentant l'emplacement de R1 ou de R2 qui est lié au CH2 de la formule R1-CH2-R2.
PCT/EP2018/066341 2017-06-21 2018-06-20 Formulation destinée à réduire l'émission de formaldéhyde dans la mousse pu WO2018234348A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17177093.6 2017-06-21
EP17177093 2017-06-21

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WO2018234348A1 true WO2018234348A1 (fr) 2018-12-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110964173A (zh) * 2019-12-13 2020-04-07 万华化学（北京）有限公司 用于蜂窝复合材料的聚氨酯组合物及其制备方法、聚氨酯泡沫及其应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10003157A1 (de) 2000-01-26 2001-08-02 Basf Ag Verfahren zur Herstellung von funktionalisierten Polyurethanschaumstoffen
EP2138520A2 (fr) * 2008-06-28 2009-12-30 Bayer MaterialScience AG Procédé de réduction d'émissions d'une mousse de polyuréthane
WO2014026802A1 (fr) 2012-08-16 2014-02-20 Huntsman Petrochemical Llc Composition
WO2016005479A1 (fr) 2014-07-10 2016-01-14 Huntsman Petrochemical Llc Composition pour réduire la quantité d'aldéhydes émis par des mousses de polyuréthane
US20160304686A1 (en) 2013-12-02 2016-10-20 Basf Se Polyurethanes having reduced aldehyde emission

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10003157A1 (de) 2000-01-26 2001-08-02 Basf Ag Verfahren zur Herstellung von funktionalisierten Polyurethanschaumstoffen
EP2138520A2 (fr) * 2008-06-28 2009-12-30 Bayer MaterialScience AG Procédé de réduction d'émissions d'une mousse de polyuréthane
WO2014026802A1 (fr) 2012-08-16 2014-02-20 Huntsman Petrochemical Llc Composition
US20160304686A1 (en) 2013-12-02 2016-10-20 Basf Se Polyurethanes having reduced aldehyde emission
WO2016005479A1 (fr) 2014-07-10 2016-01-14 Huntsman Petrochemical Llc Composition pour réduire la quantité d'aldéhydes émis par des mousses de polyuréthane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WOHLER, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 49, 1927, pages 3181

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110964173A (zh) * 2019-12-13 2020-04-07 万华化学（北京）有限公司 用于蜂窝复合材料的聚氨酯组合物及其制备方法、聚氨酯泡沫及其应用

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