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WO2025093350A1 - Catalyseur thermolatent pour la préparation de polyuréthane - Google Patents

Catalyseur thermolatent pour la préparation de polyuréthane Download PDF

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Publication number
WO2025093350A1
WO2025093350A1 PCT/EP2024/079647 EP2024079647W WO2025093350A1 WO 2025093350 A1 WO2025093350 A1 WO 2025093350A1 EP 2024079647 W EP2024079647 W EP 2024079647W WO 2025093350 A1 WO2025093350 A1 WO 2025093350A1
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WO
WIPO (PCT)
Prior art keywords
group
compound according
glycol
polyurethane
polyol
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
PCT/EP2024/079647
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English (en)
Inventor
Christian Brandl
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Evonik Operations GmbH
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Evonik Operations GmbH
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Publication of WO2025093350A1 publication Critical patent/WO2025093350A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
    • C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
    • 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
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/4829—Polyethers containing at least three 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
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group

Definitions

  • the present invention lies in the field of polyurethanes. It relates to a novel compound for use as (thermolatent) catalyst in a process for preparing a polyurethane, a method of preparing said compound, a catalyst composition for use in the preparation of a polyurethane, a polyol composition for use in the preparation of a polyurethane, a method of preparing a polyurethane, a polyurethane thus obtained and an article comprising such polyurethane.
  • Some manufacturing processes require a delayed cure.
  • some manufacturing processes require a polyurethane-forming mixture to be prepared and then applied to some other material or mold before it is cured.
  • some delay in the initial cure is wanted, to provide enough time that the polyurethane-forming mixture can be applied and manipulated.
  • thermolatent catalysts which will be inert at a chosen temperature, but become active at a higher temperature.
  • thermolatent base catalysts for the synthesis of polyurethanes which are inactive at room temperature, but become active at an elevated temperature. For instance, they are suitable for mold applications where the system's viscosity needs to remain low until the mold is filled, but the polymerization-crosslinking process must commence at a specific higher temperature and be rapid to keep the processing time as brief as feasible.
  • EP 2 050 775 discloses a catalyst composition for producing a polyurethane resin employing as thermolatent catalyst a salt of a tertiary amine and triazole or benzotriazole.
  • An alternative to these triazole / benzotriazole salts are the respective phenolic salts.
  • the phenolic salt of DBU (1 ,8-Diazabicyclo[5.4.0]undec-7-en)
  • the 1 :1 adduct of phenol and DBU is the salt obtained by reacting 1 equivalent of phenol with 1 equivalent of DBU.
  • the phenolic salts of DBU are also of such paramount interest as they allow for an improved curing compared to triazole and benzotriazole.
  • triazole, benzotriazole and phenol pose severe health and environmental risks.
  • articles made from polyurethane that were prepared with e.g. phenolic salts are often susceptible to liberating phenol.
  • phenol - being harmful to humans and the environment - should not be liberated and people must not be exposed to these harmful substances.
  • thermolatent catalyst with at least comparable technical results.
  • thermolatent catalyst having an ecological more benign character compared to the solutions presented in the prior art.
  • R 1 is selected from the group consisting of alkyl group, aryl group and polyoxyalkylene group; and n is an integer selected from the group consisting of 0 to 6.
  • the compound according to the invention allows for a better cure profile, giving a longer pot life time whilst having a fast back end cure (see inventive example 1 vs. comparative example 1).
  • the liberation of malodors and harmful substances is reduced when using the compound according to the invention and formulations comprising the compound according to the invention (e.g. the polyol composition according to the invention and the catalyst composition according to the invention, vide infra) compared to prior art systems, especially those comprising phenol and salts thereof.
  • the compound according to the invention e.g. the polyol composition according to the invention and the catalyst composition according to the invention, vide infra
  • the present invention allows to limit the exposure / liberation of harmful substances from articles made therewith such as phenols.
  • alkyl according to the present invention comprises branched or unbranched alkyl groups comprising cyclic and/or non-cyclic structural elements, wherein cyclic structural elements of the alkyl groups naturally require at least three carbon atoms.
  • C1-CX-alkyl in this specification and in the claims refers to alkyl groups having 1 to X carbon atoms (X being an integer).
  • C1 -C8-alkyl for example includes, among others, methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, tert-pentyl, neo-pentyl, hexyl, heptyl and octyl.
  • Substituted alkyl groups may theoretically be obtained by replacing at least one hydrogen by a functional group.
  • alkyl groups are preferably selected from substituted or unsubstituted C1-C8-alkyl, more preferably from substituted or unsubstituted C1 -C4-alkyl.
  • alkanediyl is the corresponding group having two free valences (bonding sites). Sometimes, it is referred to as “alkylene” in the art. Said residues according to the present invention comprise cyclic and/or non-cyclic structural elements and can be linear and/or branched.
  • C1 -C4-al- kanediyl for example includes, among others, methane-1 ,1-diyl, ethane-1 ,2-diyl, ethane-1 ,1-diyl, propane-1 ,3-diyl, propane-1 ,2-diyl, propane-1 ,1-diyl, butane-1 ,4-diyl, butane-1 ,3-diyl, butane-1 ,2- diyl, butane-1 ,1-diyl, butane-2,3-diyl.
  • alkanediyl groups are preferably selected from substituted or unsubstituted C1 -C8-alkanediyl, more preferably from substituted or unsubstituted C1-C4-alkanediyl.
  • aryl refers to ring-shaped aromatic hydrocarbon residues, for example phenyl or naphthyl where individual ring carbon atoms can be replaced by N, O and/or S, for example benzothiazolyl. Preferably, no carbon atoms are substituted, e.g. by N, O and/or S. Furthermore, aryl groups are optionally substituted by replacing a hydrogen atom in each case by a functional group.
  • C5-CX-aryl refers to aryl groups having 5 to X carbon atoms (optionally replaced by N, O and/or S) in the ring-shaped aromatic group (X naturally being an integer). C5- C6-aryl is preferred unless stated otherwise.
  • each of the residues is selected independently from each other unless stated otherwise hereinafter, meaning they can be selected to be the same members or different members of said group.
  • the bonding sites in some chemical formulas herein may be emphasized by a wavy line (“ - ⁇ w “).
  • the compound according to the invention can be present in the form of its respective salt.
  • the person skilled in the art knows that the compound according to the invention is in a state of equilibrium between the uncharged formula (I) and the ionic form (/.e. the respective salt).
  • the salts of the compound according to the invention shall be included in the scope of the present invention.
  • R 1 is selected from the group consisting of alkyl group, aryl group and polyoxyalkylene group.
  • a polyoxyalkylene group in the context of the present invention is preferably a R 2 -[O-R 3 ]k-group, wherein R 2 is hydrogen, an alkyl group, or an aryl group, R 3 is an alkanediyl group and k is an integer ranging from 1 to 20.
  • R 2 is preferably selected from the group consisting of hydrogen, C1 -C8- alkyl group, and phenyl group, more preferably selected from the group consisting of hydrogen, methyl group and ethyl group.
  • R 3 is preferably a C1 -C8-alkanediyl group, more preferably a C2-C4- alkanediyl group, even more preferably selected from the group consisting of ethane-1 ,2-diyl group and propane-1 ,2-diyl group, yet even more preferably an ethane-1 ,2-diyl group.
  • the integer k preferably ranges from 2 to 15, more preferably from 3 to 10.
  • R 1 is selected from the group consisting of alkyl group and aryl group. It is even more preferred that R 1 is selected from the group consisting of C1 -C4-alkyl group and phenyl group. And it is even more preferred that R 1 is an alkyl group. Yet even more, R 1 is selected from the group consisting of methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group , t- butyl group, and s-butyl group. Most preferably, R 1 is selected from the group consisting of methyl group, ethyl group, n-propyl group, and n-butyl group.
  • R 1 is defined as above with the proviso that it is not methyl.
  • R 1 is preferred that C2-C4-alkyl group and phenyl group.
  • R 1 is an alkyl group with the proviso that R 1 is not a methyl group.
  • R 1 is selected from the group consisting of, ethyl group, n-propyl group, i-propyl group, n-butyl group , t-butyl group, and s-butyl group.
  • R 1 is selected from the group consisting of ethyl group, n-propyl group, and n-butyl group.
  • R 1 is an ethyl group.
  • n is preferably selected from 1 and 3, n more preferably is 3.
  • the compound according to the invention is represented by formula (la) or (lb) wherein R 1 is selected from above-defined groups.
  • the compound according to the invention is represented by formula (la) as it allows for the best properties of a polyurethane to be obtained when used as catalyst in its preparation. If an even more ecologically benign compound or process is desired, the compound according to formula (lb) is preferably selected.
  • the compound according to the invention is more thermally stable compared to solutions of the prior art, in particular when compared to phenolic salts of DBU (see Figure 1 and example section). This also reduces the liberation of toxic compounds and unpleasant odors when using the compound according to the invention.
  • the compound according to the invention is preferably used as catalyst in a process for preparing a polyurethane.
  • the compound according to the invention is preferably used as thermolatent catalyst in said process.
  • Thermolatent means in this regard that a certain temperature threshold is to be reached before the catalytic effect of the catalyst in question sets into operation.
  • the compound according to the invention requires a much lower temperature to be reached compared to catalysts known from the prior art.
  • the present invention further concerns a method of preparing the compound according to the invention, comprising the method steps:
  • M1 providing at least one starting material according to formula (A) wherein n is an integer selected from the group consisting of 0 to 6, preferably selected from 1 and 3, p more preferably is 3;
  • R 1 is selected from the group consisting of alkyl group, aryl group and polyoxyalkylene group
  • the compound according to the invention is formed.
  • Method steps M1 and M2 can be carried out in the order indicated above, simultaneously or in the reverse order.
  • Method step M3 is performed after method step M1 and M2 have been concluded. Further steps can be included in the inventive method before, between or after the aforementioned method steps.
  • the temperature in method step M3 preferably ranges from 15 °C to 120 °C, more preferably from 25 °C to 90 °C, even more preferably from 60 °C to 80 °C.
  • the duration of method step M3 can be widely varied. It can be selected based on routine experiments and depends inter alia on the specific starting materials used and the temperature in method step M3.
  • the method of preparing the compound according to the invention comprises the method step M2a to be included in the method before method step M3 or during method step M3: M2a) Adding at least one solvent.
  • the at least one solvent can be added to one or each of the starting materials or it can be added to the mixture of method step M3.
  • the at least one solvent is preferably selected from those described for the catalyst composition according to the invention described hereinafter.
  • the addition of the at least one solvent facilitates the preparation of the compound according to the invention as the viscosity of the mixture can more be easily controlled.
  • the at least one solvent is optionally removed after method step M3. If the at least one solvent is not removed, the catalyst composition according to the invention is obtained.
  • the removal of the at least one solvent can be accomplished by standard methods such as distillation, preferably under reduced pressure, precipitation of the compound according to the invention from the at least one solvent and the like. The person skilled in the art can select suitable methods by routine experiments if required.
  • the means for mixing the starting materials is not particularly limited.
  • the person skilled in the art can select suitable means based on his knowledge or on routine experiments.
  • a preferred means for mixing is stirring.
  • Another aspect of the present invention pertains to a catalyst composition for use in the preparation of a polyurethane comprising (or preferably consisting of) i) the compound according to the invention; and ii) at least one solvent, the at least one solvent being preferably a polar solvent, wherein the at least one solvent is more preferably selected from the group consisting of glycols and glycol ethers and polyglycol ether.
  • the compound according to the invention is preferably present in in the catalyst composition an amount ranging from 99.9 to 0.1 wt.-% , more preferably from 95 to 10 wt.-%, even more preferably from 90 to 50% wt.-%, still even more preferably from 90 to 70 wt.-%, based on the weight of the overall catalyst composition. If more than one compound according to the invention is used, the total amount of all compounds according to the invention preferably lies in above-defined ranges.
  • the at least one solvent is preferably a polar solvent.
  • a polar solvent in the context of the present invention has a dielectric constant e of at least 10, preferably of at least 20 at 25 °C.
  • the at least one solvent is preferably protic. More preferably, the at least one solvent is polar and protic. Even more preferably, the at least one solvent is selected from the group consisting of glycols and glycol ethers. Still even more preferably, the at least one solvent is a glycol.
  • Preferable glycols are ethane-1 ,2-diol (ethylene glycol), polyethylene glycol poly(ethylene oxide), propane-1 ,2-diol, polypropylene glycol, propane-1 ,3-diol 1 ,3-(propylene glycol), 1 ,3-polypropanediol, butane-1 ,4-diol (butylene glycol) and polytetramethylene ether glycol.
  • Preferable glycol ethers are represented by the following formula (P):
  • each R s is selected from the group consisting of hydrogen and alkyl group
  • R‘ is selected from the group consisting of hydrogen and alkyl group
  • each s is independently selected from 1 , 2, 3 and 4
  • t is an integer ranging from 2 to 50.
  • Each R s is independently preferably selected from the group consisting of hydrogen and methyl group. It is preferred that at most one R s per repeating unit is an alkyl group, preferably a methyl group. At most one means 0 or 1 .
  • the repeating unit is the entity shown in squared brackets in above formula.
  • the preferable glycol ether consists of t repeating units. More preferably, all R s are hydrogen.
  • R‘ is preferably selected from the group consisting of hydrogen and C1 -C4-alkyl group, R‘ is more preferably hydrogen, s is preferably selected from 2 and 3, more preferably 2.
  • t preferably ranges from 2 to 30, more preferably 2 to 20, t even more preferably is 2 to 8.
  • R‘ is selected from the group consisting of hydrogen and C1 -C4-alkyl group, R‘ is most preferably hydrogen, s is selected from 2 and 3, s is most preferably 2, and t ranges from 2 to 30, more preferably 2 to 10, most preferably t is 2 or 3.
  • Much preferred glycol ethers are selected from the group consisting of diethylene glycol (IUPAC name: 2,2'-[Ethane-1 ,2- diylbis(oxy)]di(ethan-1-ol)), triethylene glycol, dipropylene glycol (IUPAC names: 4-Oxa-2,6-heptan- diol and 4-Oxa-1 ,6-heptandiol) and tripropylene glycol (also referred to as [(1 -Methyl-1 ,2- ethanediyl)bis(oxy)]bispropanol).
  • diethylene glycol IUPAC name: 2,2'-[Ethane-1 ,2- diylbis(oxy)]di(ethan-1-ol)
  • triethylene glycol IUPAC names: 4-Oxa-2,6-heptan- diol and 4-Oxa-1 ,6-heptandiol
  • tripropylene glycol also referred to as [(1 -Methyl-1
  • the at least one solvent is particularly preferably selected from the group consisting of ethane-1 ,2- diol, propane-1 ,2-diol, propane-1 ,3-diol and butane-1 ,4-diol, diethylene glycol, dipropylene glycol and tripropylene glycol.
  • the at least one solvent is preferably present in the catalyst composition according to the invention in an amount ranging from 0.1 to 99 wt.-%, more preferably from 5 to 90 wt.-%, even more preferably from 10 to 50 wt.-%, still even more preferably from 10 to 30 wt.-%, based on the weight of the overall catalyst composition. If more than one solvent is used, the total amount of all solvents preferably lies in above-defined ranges.
  • the catalyst composition according to the invention comprises further compounds which can function as a catalyst in a process for preparing a polyurethane. These further compounds might be catalysts generally used in the preparation of a polyurethane.
  • Suitable further catalysts for preparing a polyurethane which, in particular, accelerate the reaction between the NCO groups (isocyanate groups) of the diisocyanates and the hydroxyl groups of the polyol are the customary catalysts known from the prior art, for example tertiary amines such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'- dimethylpiperazine, diazabicyclo[2.2.2]octane and the like, and also, in particular, organic metal compounds such as titanate esters, iron compounds, tin compounds, e.g.
  • tin diacetate tin dioctoate, tin dilaurate or the dialkyltin salts of aliphatic carboxylic acids, e.g. dibutyltin diacetate, dibutyltin dilaurate or the like.
  • the further compound which can function as a catalyst is preferably present in the catalyst composition in an amount ranging from 1 to 10 wt.-%, preferably from 5 to 10 wt.-%, more preferably from 7 to 9.9 wt.-%, based on the weight of the overall catalyst composition. If more than one further compound which can function as a catalyst is used, the total amount of all further compound which can act as a catalyst preferably lies in above-defined ranges.
  • the catalyst composition according to the invention is preferably a solution. Alternatively, it is a dispersion. In the latter case, at least one surfactant is present in the dispersion.
  • One or more suitable surfactants can be selected by routine experiments and based on the general knowledge of the person skilled in the art.
  • the catalyst composition according to the invention can be prepared by various means, notably by mixing the compound according to the invention, the at least one solvent and optionally any one of the aforementioned compounds to be included in the catalyst composition according to the invention. It is also possible to prepare the catalyst composition according to the invention using the above-described method of preparing the compound according to the invention when at least one solvent is added in optional method step M2a.
  • the viscosity of the catalyst composition according to the invention advantageously can be tailored by selecting its components and the amounts thereof such that its dosing can be facilitated.
  • the present invention is directed at a polyol composition
  • a polyol composition comprising (or preferably consisting of) a) at least one polyol; b) the compound according to the invention; and optionally, c) at least one solvent, the at least one solvent being preferably a polar solvent, wherein the at least one solvent is more preferably selected from the group consisting of glycols and glycol ethers.
  • the at least one polyol is not limited. The person skilled in the art can select the at least one polyol based on his general knowledge and the desired properties of the polyurethane to be formed.
  • the at least one polyol is preferably selected from the group consisting of polyether polyol, polyester polyol, polymer polyol, flame-retardant polyol such as a phosphorus-containing polyol or a halogencontaining polyol, phenol-type polyol such as a Mannich base polyol and mixtures of the aforementioned.
  • the at least one polyol comprises 2 to 4 hydroxyl groups capable of reacting with at least one NCO group.
  • diamines that are conventionally used in the manufacturing of polyurethanes (giving urea groups in the polyurethanes or polyureas entirely).
  • no diamines are used in the polyol composition according to the invention.
  • the polyether polyols can be produced, for example, by an addition reaction of an alkylene oxide such as ethylene oxide or propylene oxide to a starting material which is a compound having at least two active hydrogen groups, such as a polyhydric alcohol such as ethylene glycol, propylene glycol, glycerol, trimethylolpropane or pentaerythritol, an aliphatic amine such as ethylenediamine, an aromatic amine such as toluenediamine, an alkanolamine such as ethanolamine or diethanolamine, sorbitol or sucrose, for example, by a method disclosed in "Polyurethane Handbook," edited by Gunter Oertel (1985), Hanser Publishers (Germany), p. 42-53.
  • a polyhydric alcohol such as ethylene glycol, propylene glycol, glycerol, trimethylolpropane or pentaerythritol
  • an aliphatic amine such as ethylenediamine
  • the polyester polyol may, for example, be one obtainable by a reaction of a dibasic acid such as adipic acid with glycol, DMT residue, a polyester polyol obtained from phthalic anhydride as the starting material, waste material from the production of nylon, TMP, waste material of pentaerythritol, waste material of a phthalic acid-type polyester, or a polyester polyol obtained by treatment of waste articles (see e.g. Keiji Iwata (Ed.), "Polyurethane Resin Handbook” (1 st edition, 1987), published by Nikkan Kogyo Shinbunsha, p. 116 - p. 117).
  • a dibasic acid such as adipic acid with glycol, DMT residue
  • a polyester polyol obtained from phthalic anhydride as the starting material
  • waste material from the production of nylon, TMP waste material of pentaerythritol
  • waste material of a phthalic acid-type polyester or
  • the polymer polyol may, for example, be a polymer polyol obtained by reacting the above polyether polyol with an ethylenically unsaturated monomer (such as butadiene, acrylonitrile, or styrene) in the presence of a radical-polymerization catalyst.
  • an ethylenically unsaturated monomer such as butadiene, acrylonitrile, or styrene
  • the flame-retardant polyol may, for example, be a phosphorus-containing polyol obtained by adding an alkylene oxide to a phosphoric acid compound, a halogen-containing polyol obtained by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide, or a phenol-type polyol such as Mannich base polyol.
  • the at least one polyol is selected from the group consisting of polyester polyol and polyether polyol.
  • a preferred polyester polyol is one having a mass average molar mass (Mw) of from 1 ,000 to 2,500 g/mol.
  • a polyester polyol obtained from the reaction of adipic acid with a glycol is preferred.
  • the polyester polyol one having a mass average molar mass (Mw) of from 1 ,000 to 2,500 g/mol and obtained from the reaction of adipic acid with a glycol, is more preferred.
  • the polyether polyol has a mass average molar mass (M w ) of from 1 ,000 to 6,000 g/mol.
  • a polyether polyol obtained by reacting propylene oxide to propylene glycol or glycerol as an initiator, followed by reacting ethylene oxide to the terminal is preferred.
  • the polyether polyol one having a mass average molar mass (Mw) of from 1 ,000 to 6,000 g/mol, obtained by reacting propylene oxide to propylene glycol or glycerol as an initiator, followed by reacting ethylene oxide to the terminal, is more preferred.
  • the mass average molar mass (Mw) in both cases is preferably measured by gel permeation chromatography using a column combination SDV 1000/10000 A (length 65 cm), temperature 30 °C, THF as mobile phase, flow rate 1 ml/min, sample concentration 10 g/l, Rl-Detector, calibration vs. polypropylene glycol standard.
  • the hydroxyl value of such a polyol is within a range of from 20 to 1 ,000 mg KOH/g.
  • the polyester polyol preferably has a hydroxyl value within a range of from 50 to 1 ,000 mg KOH/g
  • the polyether polyol preferably has a hydroxyl value within a range of from 20 to 800 mg KOH/g.
  • the hydroxyl value is measured in accordance with ASTM D4274D.
  • the at least one polyol according to the invention is preferably present in in the polyol composition an amount ranging from 10 to 99.98 wt.-%, preferably from 50 to 99.9 wt.-%, more preferably from 80 to 98 wt.-%, based on the weight of the overall catalyst composition. If more than one polyol is used, the total amount of all polyols preferably lies in above-defined ranges.
  • the compound according to the invention is preferably present in in the polyol composition an amount ranging from 0.02 to 5 wt.-%, preferably from 0.05 to 3 wt.-%, more preferably from 0.1 to 2 wt.-%, based on the weight of the overall catalyst composition. If more than one compound according to the invention is used, the total amount of all compounds according to the invention preferably lies in above-defined ranges.
  • the polyol composition according to the invention optionally comprises water.
  • the amount of water in the polyol composition according to the invention preferably ranges from 0.0001 to 5.0 wt.-%, more preferably 0.001 to 2.0 wt.-% and even more preferably from 0.05 to 0.25 wt.-%, based on the total weight of the polyol composition according to the invention. It is known that phenolic systems of the prior art suffer from age-induced drift of pot life time, i.e. the reactivity reduces over time. This is especially the case if water is present in such a system. In case of the invention, this effect does not occur or is less pronounced.
  • a blowing agent is optionally included in the polyol composition according to the invention when it is desirable to produce a cellular polyurethane foam.
  • Suitable chemical and physical blowing agents are known to the person skilled in the art.
  • the polyol composition according to the invention optionally comprises one or more of conventionally used components selected from the group consisting of filling agents (also referred to as fillers in the art), colorants, odor masks, flame retardants, biocides, antioxidants, UV stabilizers, antistatic agents, viscosity modifiers, drying agents and mixtures of the aforementioned. These components are known in the art and the person skilled in the art can select them based on his knowledge.
  • the compound according to the invention, the catalyst composition according to the invention and/or the polyol composition according to the invention can be used for preparing a polyurethane.
  • the present invention also concerns a method of preparing a polyurethane comprising reacting at least one polyisocyanate with at least one polyol in the presence of the compound according to the invention.
  • Polyurethane (PU) in the context of the present invention is in particular understood as meaning a product obtainable through reaction of at least one polyisocyanate with at least one polyol or compounds having multiple isocyanate-reactive groups, preferably with at least one polyol.
  • further functional groups may also be formed in the reaction, for example uretdi- ones, carbodiimides, isocyanu rates, allophanates, biurets, ureas and/or uretonimines.
  • polyurethane means not just polyurethane but also polyi- socyanurate, polyureas, and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret and/or uretonimine groups. It is, however, preferred that the polyurethane according to the invention is free of such groups including polyisocyanurate, polyureas, and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret and/or uretonimine groups.
  • Suitable polyisocyanates are known to the person skilled in the art.
  • the at least one polyisocyanate is preferably selected from the group consisting of aliphatic, cycloaliphatic, araliphatic and aromatic diisocyanates.
  • Preferred aromatic isocyanates are selected from the group consisting of 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'- diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, urethane-modified liquid 4,4'- diphenylmethane diisocyanates, urethane-modified liquid 2,4-diphenylmethane diisocyanates, 4,4'-diisocyanatodiphenylethane, the mixtures of monomeric methanediphenyl diisocyanates, toluene diisocyanate (TDI), methanediphenyl diisocyanate (MDI), more highly polycyclic homologues of methanediphenyl diisocyanate (polymeric MDI), 1 ,2- naphthylene diisocyanate, 1 ,5-naphthylene diisocyanate
  • Aliphatic diisocyanates used are customarily aliphatic and/or cycloaliphatic diisocyanates, preferably selected from the group consisting of tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2-methylpentamethylene-1 ,5-diisocyanate, 2-ethylbutylene-1 ,4-diisocyanate, 1-isocy- anato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1 ,4-bis(iso- cyanatomethyl)cyclohexane, 1 ,3-bis(isocyanatomethyl)cyclohexane (HXDI), 1 ,4-cyclohexane diisocyanate, 1 -methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,
  • Polyisocyanate prepolymers are obtainable by reacting above described polyisocyanates in excess, at temperatures of 30 to 100°C, for example, preferably at about 80°C, with at least one polyol to give the prepolymer.
  • the at least one polyisocyanate is selected from the group consisting of MDI, polymeric MDI, TDI or prepolymers of the aforementioned.
  • Prepolymers of the aforementioned polyisocyanates are known in the art and can be obtained by reacting the polyisocyanates with at least one polyol wherein the first-mentioned is used in an excess such that a prepolymer is obtained (having reactive isocyanate groups).
  • the present invention is also directed to a process of preparing a polyurethane as disclosed above, wherein the polyisocyanate is selected from the group consisting of MDI, polymeric MDI, and TDI, and derivatives thereof or prepolymers of these polyisocyanates.
  • the at least one polyisocyanate is mixed with at least one polyol in the presence of the compound according to the invention.
  • the thus obtained mixture (hereinafter: PU-forming mixture) is preferably heated to a temperature ranging from 20 to 110 °C, more preferably from 20 to 80 °C, even more preferably from 20 to 50 °C, to activate the compound according to the invention as it is preferably used here as thermolatent catalyst.
  • the means of mixing the at least one polyisocyanate is mixed with at least one polyol in the presence of the compound according to the invention are not particularly limited.
  • suitable means such as stirring.
  • the compound according to the invention is used in catalytically sufficient amounts.
  • a preferable amount of the compound according to the invention is from about 0.02 to about 2 wt.-%, especially from about 0.05 to about 0.5 wt.-%, of the compound according to the invention based on the overall weight of the at least one polyol(s).
  • the polyisocyanate and polyol are preferably reacted at an isocyanate index of from 70 to 500 or more, although a more preferable isocyanate index is from 80 to 130.
  • Isocyanate index is calculated as the number of reactive isocyanate groups provided by the polyisocyanate component divided by the number of isocyanate-reactive groups (in particular hydroxyl groups of the polyol) in the PU-forming mixture (including isocyanate-reactive blowing agents such as water, if present) and multiplying by 100. Water is considered to have two isocyanate-reactive groups per molecule for purposes of calculating isocyanate index. A preferred isocyanate index is from 100 to 125.
  • the PU-forming mixture optionally contains at least one surfactant, whose presence is preferred when a cellular polyurethane is formed.
  • the surfactant helps to stabilize the cells of the composition as gas evolves to form bubbles and expand the foam.
  • Organosili- cone surfactants are generally preferred types.
  • organosilicone surfactants are commercially available, including those sold by Goldschmidt under the Tegostab® name (such as Tegostab B-8462, B8427, B8433 and B-8404 surfactants), as well as various surfactant products commercially available from Dow Chemicals, such as Vorasurf DC-193 Additive, Vorasurf DC- 198 Additive, Vorasurf DC-5000 Additive, Vorasurf DC-5043 Additive and Vorasurf DC-5098 Additive surfactants.
  • Tegostab® name such as Tegostab B-8462, B8427, B8433 and B-8404 surfactants
  • various surfactant products commercially available from Dow Chemicals, such as Vorasurf DC-193 Additive, Vorasurf DC- 198 Additive, Vorasurf DC-5000 Additive, Vorasurf DC-5043 Additive and Vorasurf DC-5098 Additive surfactants.
  • the PU-forming mixture optionally includes one or more auxiliary components, such as fillers, colorants, odor masks, flame retardants, biocides, antioxidants, UV stabilizers, antistatic agents, viscosity modifiers, and the like.
  • auxiliary components such as fillers, colorants, odor masks, flame retardants, biocides, antioxidants, UV stabilizers, antistatic agents, viscosity modifiers, and the like.
  • Suitable flame retardants include phosphorus compounds, halogen containing compounds and melamine.
  • fillers and pigments include calcium carbonate, titanium dioxide, iron oxide, chromium oxide, azo/diazo dyes, phthalocyanines, dioxazines and carbon black.
  • UV stabilizers examples include hydroxybenzotriazoles, zinc dibutyl thiocarbamate, 2,6-diter- tiary butyl catechol, hydroxybenzophenones, hindered amines and phosphites.
  • the foregoing additives are generally used in small amounts, such as from 0.01 percent to 3 weight-% based on the total weight of the PU-forming mixture. Fillers are optionally used in quantities as high as 50 weight-% based on the total weight of the PU-forming mixture.
  • a viscosity modifier may be used in either the polyol (composition) or isocyanate components if needed or desired to bring the viscosity of that component into a particular range.
  • a viscosity modifier will be used most commonly in cases in which the polyol is viscous relative to the polyisocyanate. In such a case, a viscosity modifier can be added to more closely match the viscosity of the polyol component with that of the polyisocyanate.
  • the viscosity modifier preferably is not reactive with the polyol, water or polyisocyanate, although it may perform other functions (such as providing flame retardancy).
  • a viscosity modifier may be blended with one or more of the components in order to bring the viscosity down into that range. Viscosity modifiers are known in the art.
  • the method of preparing the polyurethane comprises the following method steps:
  • Auxiliary components are optionally added to the polyol composition.
  • the temperature in method step P4 preferably lies in above defined ranges.
  • the duration of method step P4 is not particularly limited and depends in particular on the at least one polyol, the at least one polyisocyanate and the temperature used. Useful durations range from 10 to 80 seconds, preferably from 10 to 60 seconds, more preferably from 20 to 40 seconds.
  • the method of preparing a polyurethane comprises the following method step to be carried out in the given order:
  • Auxiliary components are optionally added in one of method steps Q2, Q3 and/or Q4, preferably in Q2.
  • the temperature in method step Q4 preferably lies in above defined ranges.
  • the duration of method step Q4 is not particularly limited and depends in particular on the at least one polyol, the at least one polyisocyanate and the temperature used. Useful durations range from 1 min to 3 h, preferably from 10 min to 2 h, more preferably from 30 min to 1 h.
  • the present invention further concerns a polyurethane obtained from the inventive method of preparing a polyurethane.
  • the polyurethanes obtained according to the present invention are in particular suitable for applications such as coatings, laminating, sealants, adhesives, elastomers, and production of moldings for applications in which components of very high surface area are being produced, such as rotor blades for wind turbines, boat hulls, or plastic vehicle bodies for automobiles.
  • an article preferably an artificial leather, more preferably a 2 component artificial leather, comprising or consisting of the polyurethane according to the invention.
  • Arcol Polyol 1374 (a polyether triol obtained from Covestro AG, Germany) and 1 ,4-butandiol were dried over 3 A molecular sieve. Suprasec 2015 (NCO % 27.4) was obtained from Huntsman Polyurethanes, Belgium.
  • Gel times were measured with a Standard Gel Timer 220v/50Hz from Gardco, USA. The sample was evaluated at room temperature until the rotating hook reached its maximum torque level. This time was defined as “gel time.”
  • Table 1 Preparation of inventive Compounds 2 and 3 and a comparative compound.
  • Arcol Polyol 1374 was mixed with 1 ,4-Butandiol in the amounts given in table 2.
  • the catalyst (compound 1 to 3 or the 1 :1 adduct of phenol and DBU) was added in the amount given in table 2 using a Hausschild Speedmixer DAC 400 for 2 min with 2500 rpm.
  • the polyisocyanate was added and the mixture was blended for 13 seconds at 2750 rpm in the Speedmixer.
  • 70 g of the product obtained were poured into a metal cup and placed in a gel timer at room temperature. A small sample was placed into the rheometer.
  • Table 2 Inventive Example 1 and Comparative Example 1.
  • the substitution of the harmful comparative compound (a 1 :1 adduct of phenol and DBU) by the compound according to the invention in inventive example 1 allowed for at least equally good polyurethanes to be obtained.
  • the gel time was shortened when using the compound according to the invention indicating an improved catalyst effect of the compound according to the invention compared to the prior art catalyst.
  • the TGA was measured from 25 °C to 375 °C with a heating rate of 2K/min. It was measured on a TA Instruments Discovery TGA.

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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 nouveau composé destiné à être utilisé en tant que catalyseur thermolatent dans un procédé de préparation d'un polyuréthane, un procédé de préparation dudit composé, une composition de catalyseur destinée à être utilisée dans la préparation d'un polyuréthane, une composition de polyol destinée à être utilisée dans la préparation d'un polyuréthane, un procédé de préparation d'un polyuréthane, un polyuréthane ainsi obtenu et un article comprenant un tel polyuréthane.
PCT/EP2024/079647 2023-10-31 2024-10-21 Catalyseur thermolatent pour la préparation de polyuréthane Pending WO2025093350A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4582861A (en) 1984-11-13 1986-04-15 Air Products And Chemicals, Inc. Delayed action/enhanced curing catalysis in polyurethane systems
US5212306A (en) 1992-09-18 1993-05-18 Air Products And Chemicals, Inc. Amine-borate and amine-boron halide complexes as catalyst compositions for the production of polyurethanes
JPH05198940A (ja) * 1992-01-21 1993-08-06 Toshiba Chem Corp フレキシブル印刷回路用基板の接着剤組成物
EP0989146A1 (fr) 1998-09-21 2000-03-29 Tosoh Corporation Catalyseur pour la production de polyuréthane
US6727053B2 (en) * 2001-03-29 2004-04-27 Fuji Photo Film Co., Ltd. Dye-forming coupler, silver halide photographic light-sensitive material and azomethine dye compound
EP2050775A1 (fr) 2006-08-11 2009-04-22 Tosoh Corporation Composition de catalyseur pour la production d'une résine de polyuréthane et procédé de production de la résine de polyuréthane
WO2011094244A1 (fr) 2010-01-27 2011-08-04 Dow Global Technologies Llc Catalyseur de polyuréthane à action retardée
US8618014B2 (en) * 2004-05-28 2013-12-31 Air Products And Chemicals, Inc. Fast demold/extended cream time polyurethane formulations

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4582861A (en) 1984-11-13 1986-04-15 Air Products And Chemicals, Inc. Delayed action/enhanced curing catalysis in polyurethane systems
JPH05198940A (ja) * 1992-01-21 1993-08-06 Toshiba Chem Corp フレキシブル印刷回路用基板の接着剤組成物
US5212306A (en) 1992-09-18 1993-05-18 Air Products And Chemicals, Inc. Amine-borate and amine-boron halide complexes as catalyst compositions for the production of polyurethanes
EP0989146A1 (fr) 1998-09-21 2000-03-29 Tosoh Corporation Catalyseur pour la production de polyuréthane
US6727053B2 (en) * 2001-03-29 2004-04-27 Fuji Photo Film Co., Ltd. Dye-forming coupler, silver halide photographic light-sensitive material and azomethine dye compound
US8618014B2 (en) * 2004-05-28 2013-12-31 Air Products And Chemicals, Inc. Fast demold/extended cream time polyurethane formulations
EP2050775A1 (fr) 2006-08-11 2009-04-22 Tosoh Corporation Composition de catalyseur pour la production d'une résine de polyuréthane et procédé de production de la résine de polyuréthane
WO2011094244A1 (fr) 2010-01-27 2011-08-04 Dow Global Technologies Llc Catalyseur de polyuréthane à action retardée

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"Polyurethane Handbook", 1985, HANSER PUBLISHERS, pages: 42 - 53
"Polyurethane Resin Handbook", 1987, NIKKAN KOGYO SHINBUNSHA, pages: 116 - 117
WICKS D A ET AL: "BLOCKED ISOCYANATES III: PART A. MECHANISMS AND CHEMISTRY", PROCESS IN ORGANIC COATINGS, ELSEVIER BV, NL, vol. 36, 1 January 1999 (1999-01-01), pages 148 - 172, XP001065209, ISSN: 0300-9440, DOI: 10.1016/S0300-9440(99)00042-9 *

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