WO2022004509A1 - Procédé de production de composite de composé de titane et d'hydroxyde d'ammonium, procédé de production de composition, procédé de production de composé ester et procédé de production d'hydroxyde d'ammonium - Google Patents

Procédé de production de composite de composé de titane et d'hydroxyde d'ammonium, procédé de production de composition, procédé de production de composé ester et procédé de production d'hydroxyde d'ammonium Download PDF

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WO2022004509A1
WO2022004509A1 PCT/JP2021/023727 JP2021023727W WO2022004509A1 WO 2022004509 A1 WO2022004509 A1 WO 2022004509A1 JP 2021023727 W JP2021023727 W JP 2021023727W WO 2022004509 A1 WO2022004509 A1 WO 2022004509A1
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ammonium hydroxide
producing
hydroxide
titanium compound
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侑哉 中川
和則 難波
春香 吉山
裕士 今田
奈那恵 菊井
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日東化成株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/78—Benzoic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/057—Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups

Definitions

  • the present invention relates to a method for producing a complex of a titanium compound and an ammonium hydroxide, a method for producing a composition, a method for producing an ester compound, and a method for producing an ammonium hydroxide.
  • the one-component moisture-curable rubber composition generally has a high curing rate, and it is not necessary to weigh and mix various additives such as a base polymer, a cross-linking agent, and a catalyst before use, so that the one-component type is a two-component type. It is superior in terms of workability.
  • silicone-based rubbers silicone-based rubbers, modified silicone-based rubbers, urethane-based rubbers, polysulfide-based rubbers, and the like are known.
  • An organopolysiloxane composition is widely used as a one-component moisture-curable rubber composition of a silicone-based rubber, and is cured at room temperature to form a rubber elastic body.
  • the polymer compound of siloxane having a —Si—O— bond as the main chain, which is cross-linked and polymerized by organosiloxane has excellent properties such as water repellency, heat resistance, weather resistance, cold resistance, and electrical insulation. Widely used in fields such as civil engineering, electricity, electronics, and automobile industry.
  • a one-component moisture-curable rubber composition of modified silicone-based rubber there is a composition containing a polymer having a crosslinkable reactive hydrolyzable silicon functional group having a polyether as a main chain.
  • the curable composition of this polymer has better storage stability, weather resistance, foaming resistance and discoloration resistance than those of polyurethane-based rubber, and is superior in curability to surroundings as compared with polysulfide-based ones. It is less contaminated and non-toxic.
  • the reaction mechanism in the process of the silicone-based rubber and the modified silicone-based rubber becoming a cured product is said to be due to the condensation reaction or addition reaction of the reactive hydrolyzable silicon-containing group in the coexistence of water, and the polymerization proceeds. It is believed that a cured polymer with a three-dimensional network structure is formed. Curing catalysts are used in order to accelerate curing in this reaction (Patent Documents 1 to 5).
  • Japanese Unexamined Patent Publication No. 8-41358 Japanese Unexamined Patent Publication No. 60-161457 Special Publication No. 63-42942 Japanese Patent Application Laid-Open No. 2003-147220 Japanese Patent No. 5446265
  • tin carboxylate compounds As a curing catalyst for the curing composition of the silicone-based rubber having the reactive hydrolyzable silicon-containing group and the modified silicone-based rubber, tin carboxylate compounds, alkyl tin salt compounds and the like have been conventionally used, but endocrine disruption is disrupted. Since there is concern about the effect on the living body as a substance, a combined catalyst of carboxylic acid and amine (Patent Document 1) has been proposed as a moisture-curable composition that does not use such a substance, but it is sufficiently cured at the time of construction. There is a problem that speed cannot be obtained.
  • Patent Document 2 and Patent Document 3 it is proposed to use a titanium acid ester compound such as diisopropoxytitanium bis (alkylacetoacetonate) as a catalyst, but it is contained in the additive or filler in the composition. It is easily decomposed by the moisture, and the curing speed varies depending on the humidity at the time of construction, so that there is a problem that a stable cured product cannot be obtained.
  • a titanium acid ester compound such as diisopropoxytitanium bis (alkylacetoacetonate)
  • Patent Document 4 proposes to use a titanium tetracarboxylic dian compound as a catalyst, but there is a problem that practical satisfaction with respect to the curing rate cannot be obtained.
  • Patent Document 5 proposes to use a quaternary ammonium salt as a catalyst, but there is a problem that a sufficient curing rate cannot be obtained at the time of construction.
  • an object of the present invention is to provide a method for producing a substance that is highly safe and can be used as a catalyst having excellent activity.
  • the present invention there is a method for producing a composite of a titanium compound [B1] and an ammonium hydroxide [B2].
  • the titanium compound [B1] is represented by the chemical formula (1).
  • the ammonium hydroxide [B2] is represented by the chemical formula (2).
  • the method comprises a first step and a second step.
  • the ammonium halide [B21] represented by the chemical formula (3) is reacted with an alkali metal hydroxide to produce the ammonium hydroxide [B2].
  • a method for reacting the ammonium hydroxide [B2] with the titanium compound [B1] is provided.
  • a complex of a titanium compound and ammonium hydroxide can be obtained.
  • This complex has excellent catalytic activity when used as a catalyst for various reactions. Since this complex does not contain tin, it is highly safe. In addition, it can be manufactured at low cost.
  • the complex of the present invention is a complex of a titanium compound [B1] and an ammonium hydroxide [B2]. This complex is a reaction product that can be obtained by reacting a titanium compound [B1] with an ammonium hydroxide [B2].
  • the titanium compound [B1] is represented by the chemical formula (1).
  • R 1 represents a substituted or unsubstituted hydrocarbon group, n is 1 to 4, and A represents a ⁇ -diketone group).
  • N is, for example, 1, 1.5, 2, 2.5, 3, 3.5, and 4, and may be within the range between any two of the numerical values exemplified here.
  • a substituted or unsubstituted hydrocarbon group represented by R 1 is a substituted or unsubstituted, aliphatic or aromatic hydrocarbon group, aliphatic hydrocarbon group is preferred.
  • Hydrocarbon groups include alkyl groups (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl) and oxyalkylenes. Group etc. can be mentioned.
  • At least one of R 1 is preferably an alkyl group having 8 or more carbon atoms or an oxyalkylene group. At least one of R 1 is preferably a hydrocarbon group (other hydrocarbon group) that is neither an alkyl group having 8 or more carbon atoms nor an oxyalkylene group.
  • the carbon number of the other hydrocarbon group is, for example, 1 to 7, preferably 1 to 5. Specifically, the number of carbon atoms is, for example, 1, 2, 3, 4, 5, 6, and 7, and may be within the range between any two of the numerical values exemplified here.
  • the other hydrocarbon group is preferably an alkyl group, more preferably a branched alkyl group. The number of other hydrocarbon groups is 0, 1, 2, 3 or 4.
  • the number of carbon atoms of the alkyl group having 8 or more carbon atoms is, for example, 8 to 20, preferably 8 to 15. Specifically, the carbon number is, for example, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, and is between any two of the numerical values exemplified here. It may be within the range of.
  • the oxyalkylene group is represented by the chemical formula (4).
  • the number of atoms in the main chain of the oxyalkylene group is, for example, 4 to 20, more preferably 6 to 14. Specifically, the number of atoms is, for example, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 and is exemplified here. It may be within the range between any two of the given numerical values.
  • R 6- ( OR 7 ) m- (4) In the formula, R 6 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, R 7 is a substituted or unsubstituted hydrocarbon group having 2 to 10 carbon atoms, and m is an integer of 1 to 10).
  • the carbon number of R 6 is preferably 1 to 6, more preferably 1 to 4, the number of carbon atoms of R 7 is preferably 2 to 6, more preferably 2 to 3, and m is preferably 1 to 6 and 1 to 2. More preferred.
  • Examples of the oxyalkylene group include a group obtained by removing the terminal hydroxyl group from the alcohol shown below.
  • examples of such alcohols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monot-butyl ether, and diethylene glycol monomethyl.
  • the oxyalkylene group becomes 2- (2-butoxyethoxy) ethyl and the alcohol is butyl cellosolve (also known as 2-butoxyethanol). ),
  • the oxyalkylene group is 2-butoxyethyl.
  • the ⁇ -diketone group represented by A includes 2,4-pentandione, 2,4-hexanedione, 2,4-pentadecandione, 2,2,6,6-tetramethyl-3,5-heptandione, 1 -Phenyl-1,3-butandione, 1-aryl-1,3-butandione such as 1- (4-methoxyphenyl) -1,3-butandione, 1,3-diphenyl-1,3-propanedione, 1, 1,3-Diaryl-1,3-propanedione such as 3-bis (2-pyridyl) -1,3-propanedione, 1,3-bis (4-methoxyphenyl) -1,3-propanedione, 3 -Diketones such as benzyl-2,4-pentandione, ketoesters such as methylacetate, ethylacetate, butylacetate, t-butylacetate, ethyl-3
  • titanium compound [B1] examples include tetramethoxytitanium, trimethoxyethoxycititanium, trimethoxyisopropoxytitanium, trimethoxybutoxytitanium, dimethoxydiethoxytitanium, dimethoxydiisopropoxytitanium, dimethoxydibutoxytitanium, and methoxytri.
  • Ethoxytitanium methoxytriisopropoxytitanium, methoxytributoxytitanium, tetraethoxytitanium, triethoxyisopropoxytitanium, triethoxybutoxytitanium, diethoxydiisopropoxytitanium, diethoxydibutoxytitanium, ethoxytriisopropoxytitanium, ethoxytri Butoxytitanium, Tetraisopropoxytitanium, Triisopropoxybutoxytitanium, Diisopropoxydibutoxytitanium, Tetrabutoxytitanium, Diisopropoxytitanium bis (acetylacetonate), Isopropoxytrisbutylcarbitol titanium, Diisopropoxybisbutylcarbitol Titanium, triisopropoxybutyl carbitol titanium, tetrakisbutyl carbitol titanium, etc.
  • titanium compound [B1] may be used alone or in combination of two or more.
  • Ammonium hydroxide [B2] is represented by the following formula. (In the formula, R 2 , R 3 , R 4 , and R 5 represent substituted or unsubstituted hydrocarbon groups having 1 to 8 carbon atoms, which are the same or different from each other. X represents a hydroxyl group.)
  • the substituted or unsubstituted hydrocarbon group represented by R 2 , R 3 , R 4 , R 5 is a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and an aliphatic hydrocarbon group is preferable.
  • an aliphatic hydrocarbon group a linear or branched alkyl group is preferable.
  • the hydrocarbon group has 1 to 8 carbon atoms, preferably 1 to 6 and even more preferably 1 to 4. Specifically, the number of carbon atoms is, for example, 1, 2, 3, 4, 5, 6, 7, and 8, and may be within the range between any two of the numerical values exemplified here.
  • Examples of the aliphatic hydrocarbon group include a saturated hydrocarbon group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group and an octyl group, and vinyl.
  • Examples thereof include an unsaturated hydrocarbon group such as a group, an allyl group, a prenyl group, a crotyl group and a cyclopentadienyl group, and a methyl group, an ethyl group and a butyl group are preferable.
  • aromatic hydrocarbon group examples include a phenyl group, a tolyl group, a benzyl group and the like.
  • substituent of the hydrocarbon group examples include a methoxy group, an ethoxy group, a hydroxy group, an acetoxy group and the like.
  • Substituted aliphatic or aromatic hydrocarbon groups include alkoxyalkyl groups such as methoxymethyl group, methoxyethyl group, ethoxymethyl group and ethoxyethyl group, hydroxymethyl group, hydroxyethyl group and 3-hydroxypropyl. Examples thereof include a hydroxyalkyl group such as a group and a 2-acetoxyethyl group.
  • ammonium hydroxide represented by the chemical formula (2) examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, and benzyltriethylammonium hydroxy.
  • a method for producing a complex includes a first step and a second step. Hereinafter, each step will be described.
  • Ammonium halide [B21] is represented by the following formula. (In the formula, R 2 , R 3 , R 4 , and R 5 represent substituted or unsubstituted hydrocarbon groups having 1 to 8 carbon atoms, which are the same or different from each other. X represents a halide.)
  • R 2 , R 3 , R 4 , and R 5 are the same as those described for ammonium hydroxide [B2].
  • the halide examples include iodide, bromide, chloride, and fluoride, and bromide is particularly preferable from the viewpoint of good reactivity. Therefore, the ammonium halide [B21] is preferably ammonium bromide.
  • alkali metal hydroxide examples include sodium hydroxide, potassium hydroxide and the like, and hydroxide is obtained from the viewpoint of good solubility in a solvent such as alcohol and easy removal of by-produced alkali halide. Potassium is preferred.
  • the purity of the alkali metal hydroxide is preferably 80% or more, and more preferably 90% or more, from the viewpoint of suppressing coloration when the ammonium hydroxide [B2] is heated.
  • the solvent to be used include methanol, ethanol, propanol, isopropanol, butanol and the like. Methanol and ethanol are preferable, and methanol is more preferable because ammonium hydroxide can be synthesized at a high concentration.
  • the amount to be used is arbitrarily selected within the range of 0.5 to 20 times by mass with respect to the ammonium halide [B21], and is preferably in the range of 0.5 to 5 times by mass.
  • the reaction temperature of the first step reaction is preferably 0 to 90 ° C, particularly preferably room temperature to 60 ° C.
  • the reaction molar ratio of the alkali metal hydroxide to ammonium halide [B21] is preferably 0.7 to 0.99. 0.7 to 0.9 is more preferable, 0.75 to 0.85 is further preferable, and 0.8 to 0.85 is particularly preferable. Specifically, the reaction molar ratio is, for example, 0.7, 0.75, 0.76, 0.77, 0.78, 0.79, 0.8, 0.81, 0.82, 0.
  • the first step may be recognized as a step included in the method for producing ammonium hydroxide [B2].
  • the ammonium hydroxydo [B2] obtained in the first step may be used in the second step described later, but may be used for other purposes.
  • the ammonium hydroxide [B2] obtained in the first step and the titanium compound [B1] may be mixed to obtain a catalyst composed of a mixture of both.
  • the second step can be carried out by reacting a mixture of ammonium hydroxide [B2] and the titanium compound [B1] at, for example, 20 to 100 ° C. In this step, it is preferable that ammonium hydroxide [B2] is dropped and reacted with the titanium compound [B1] at the above temperature.
  • the temperature is, for example, 20, 30, 40, 50, 60, 70, 80, 90, 100 ° C., and may be in the range between any two of the numerical values exemplified here. ..
  • the molar ratio of the titanium compound [B1] to the ammonium hydroxide [B2] in the mixture is, for example, 0.1 to 100, 0.1, 0.5, 1, 2, 3, 4, 5, 6 , 7, 8, 9, 10, 20, 50, 100, and may be within the range between any two of the numerical values exemplified here.
  • Examples of the method of using the catalyst include a method for producing a moisture-curable composition, a method for producing a urethane resin composition, and a method for producing an ester compound.
  • a method for producing a moisture curable composition comprises a step of mixing a curing catalyst and a polymer [A] having a reactive hydrolyzable silicon-containing group.
  • the curing catalyst the above-mentioned complexes and mixtures can be used.
  • Polymer [A] The polymer [A] has at least one reactive hydrolyzable silicon-containing group per molecule at the terminal or side chain.
  • the reactive hydrolyzable silicon-containing group may be present at the terminal of the polymer [A] molecule, at the side chain, or at both the terminal and the side chain.
  • the number of reactive hydrolyzable silicon-containing groups may be at least one per molecule of the polymer [A], but the number is 1.5 or more per molecule on average in terms of curing rate and cured physical characteristics. Is preferable.
  • a known method can be adopted as a method for binding the reactive hydrolyzable silicon-containing group to the main chain polymer.
  • the polymer [A] is preferably liquid at room temperature.
  • a reactive hydrolyzable silicon-containing group is a group having a silicon atom bonded to a hydrolyzable group (eg, halogen, alkoxy, alkenyloxy, asyloxy, amino, aminooxy, oxime, amide) or a reactive group consisting of a hydroxyl group. It has the property of causing a condensation reaction by using a catalyst or the like as needed in the presence of moisture or a cross-linking agent. Specific examples thereof include a halide silyl group, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximsilyl group, and an amidosilyl group.
  • the number of reactive hydrolyzable groups bonded to one silicon atom is selected from the range of 1 to 3. Further, the reactive hydrolyzable group bonded to one silicon atom may be one kind or a plurality of kinds. Further, the reactive hydrolyzable group and the non-reactive hydrolyzable group may be bonded to one silicon atom, or the hydrolyzable group and the hydroxyl group may be bonded to one silicon atom.
  • the reactive hydrolyzable silicon-containing group an alkoxysilyl group (including a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group) is particularly preferable because it is easy to handle.
  • the trialkoxysilyl group is preferable because it has high activity and good curability can be obtained, and the obtained cured product is excellent in restorability, durability and creep resistance.
  • the dialkoxysilyl group and the monoalkoxysilyl group are preferable because they have excellent storage stability and the obtained cured product has high elongation and high strength.
  • Examples of the polymer [A] include an organic polymer [A1] and an organopolysiloxane [A2].
  • Organic polymer [A1] used in the present invention is one having a carbon atom, for example, an alkylene oxide polymer, a polyester polymer, an ether / ester block copolymer, a polymer of an ethylenically unsaturated compound, or a diene. Examples thereof include polymers of system compounds.
  • the alkylene oxide polymer [CH 2 CH 2 O] n [CH (CH 3 ) CH 2 O] n [CH (C 2 H 5 ) CH 2 O] n [CH 2 CH 2 CH 2 CH 2 O] n
  • n is the same or different integer of 2 or more.
  • These alkylene oxide polymers may be used alone or in combination of two or more. Further, a copolymer containing two or more of the above repeating units can also be used.
  • polyester polymer examples include carboxylic acids such as acetic acid, propionic acid, maleic acid, phthalic acid, citric acid, pyruvate, and lactic acid and their anhydrides, and their intramolecular and / or intermolecular esters and their substitutions. Examples are those having as a repeating unit.
  • ether / ester block copolymer examples include those having both the repeating unit used for the above-mentioned alkylene oxide polymer and the repeating unit used for the above-mentioned polyester polymer as the repeating unit.
  • the polymers of the ethylenically unsaturated compound and the diene compound include ethylene, propylene, acrylic acid ester, methacrylic acid ester, vinyl acetate, acrylonitrile, styrene, isobutylene, butadiene, isoprene, chloroprene and other homopolymers, or Examples thereof include these two or more kinds of copolymers. More specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-butadiene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid.
  • Ester copolymer polyisoprene, styrene-isoprene copolymer, isobutylene-isoprene copolymer, polychloroprene, styrene-chloroprene copolymer, acrylonitrile-chloroprene copolymer, polyisobutylene, polyacrylic acid ester, polymethacrylic acid Esther and the like can be mentioned. These may be used alone or in combination of two or more.
  • an organic polymer having a polar group such as a nitrogen-containing characteristic group in the molecule can also be used.
  • the nitrogen-containing characteristic group include a (thio) urethane group-derived linking group such as a (thio) urethane group, an allophanate group, another N-substituted urethane group, and an N-substituted allophanate group, and a (thio) urea group.
  • Biling group derived from (thio) urea group such as biuret group, other N-substituted urea group, N, N'-substituted urea group, N-substituted biuret group, N, N'-substituted biuret group, amide group
  • Examples include, but are limited to, a binding group derived from an amide group such as an N-substituted amide group, a nitrogen-containing characteristic group represented by a binding group derived from an imino group, a (thio) ester group, a (thio) ether group, and the like. Not done.
  • a nitrogen-containing characteristic group is preferable because of its high curability, and a (thio) urethane group-derived binding group and a (thio) urea-derived binding group are more preferable because of its ease of synthesis. Further, only one nitrogen-containing characteristic group may be contained in the organic polymer [A1], and one or more nitrogen-containing characteristic groups may be further contained.
  • the notations of "(thio)" and "N-substitution" are the same as above.
  • the organic polymer [A1] contains a polar group such as the nitrogen-containing characteristic group
  • the toughness of the cured product is improved, and the curability and the adhesive strength are enhanced.
  • the crosslinkable silicon group is linked to the main chain via a polar group such as a nitrogen-containing characteristic group
  • the curability is further enhanced.
  • the polar groups of the nitrogen-containing characteristic groups are strongly attracted to each other by an interaction such as a hydrogen bond. It is considered that the polar groups of the nitrogen-containing characteristic groups are strongly attracted to each other, so that the molecules of the curable resin are also strongly bound to each other (domain formation), thereby exhibiting toughness in the cured product.
  • the crosslinkable silicon groups are also close to each other when forming a domain between the nitrogen-containing characteristic groups.
  • the contact probability between the crosslinkable silicon groups is also improved, and further, the condensation reactivity between the crosslinkable silicon groups is improved by catalytic curing by the polar group in the nitrogen-containing characteristic group.
  • Such an organic polymer [A1] (modified silicone-based polymer) can be produced by a known method such as the method described in Japanese Patent Publication No. 61-18569, or is commercially available. ..
  • Commercially available products include, for example, Kaneka MS Polymer series (MS Polymer S203, MS Polymer S303, MS Polymer S903, MS Polymer S911, MS Polymer SAX520, etc.) and Cyril Series (Cyril Polymer SAT200, Cyril) manufactured by Kaneka Corporation.
  • Polymer MA430, Cyril Polymer MAX447, etc.), MA series, SA series, OR series; ES series (ES-GX3440ST, etc.) manufactured by Asahi Glass Co., Ltd., ESGX series, etc. are exemplified.
  • the number average molecular weight of the organic polymer [A1] used in the present invention is not particularly limited, but an excessively high polymer has a high viscosity and is difficult to use in the case of a curable composition, so 30,000.
  • the following is desirable.
  • Such an organic polymer can be produced by a known method, but a commercially available product such as the above-mentioned Kaneka MS Polymer manufactured by Kaneka Corporation may be used.
  • the organopolysiloxane [A2] used in the present invention has a main chain composed of a siloxane bond represented by Si—O, and further has an organic group bonded to a silicon atom constituting the siloxane bond.
  • an organic group include an alkyl group such as methyl, ethyl, propyl and butyl; a cycloalkyl group such as cyclohexyl; an alkenyl group such as vinyl, isopropenyl and substituted vinyl; an allyl group, crotyl, methallyl and the like.
  • Substituentally substituted allyl groups aryl groups such as phenyl, toluyl, xylyl; aralkyl groups such as benzyl, phenylethyl; and groups in which all or part of the hydrogen atoms of these organic groups are substituted with halogen atoms, such as chloromethyl groups, Examples thereof include 3,3,3-trifluoropropyl groups.
  • the organopolysiloxane [A2] may be composed of a single main chain, or may be composed of two or more types of main chains.
  • the organopolysiloxane may be linear or branched, including trifunctional (R'SiO 1.5 ) or tetrafunctional (SiO 2). Also, the physical properties and applications of the cured product, difunctional shaped as needed (R may be combined '2 SiO) and 1 functional type (R' a 3 SiO 0.5) (wherein, R 'is an organic radical ). Further, the hydrolyzable silicon-containing group may be bonded to either the end of the molecule or the middle of the molecular chain.
  • the organopolysiloxane is generally represented by Ra SiO 4-a / 2 as an average composition formula (for example, JP-A-2005-194399, JP-A-8-151521, etc.). The above notation followed this.
  • the viscosity of the organopolysiloxane [A2] used in the present invention is not particularly limited, but an excessively high viscosity may reduce workability or impair the physical properties of the obtained cured product. It is desirable that the viscosity at ° C is in the range of 0.025 to 100 Pa ⁇ s.
  • Such organopolysiloxanes can be produced by known methods, but are manufactured by GE Toshiba Silicone Co., Ltd.'s Tosseal series, Shin-Etsu Chemical Co., Ltd.'s sealant series, and Toray Dow Corning Co., Ltd. Commercially available products such as SH series can be used.
  • the moisture curable composition contains a curing catalyst and the polymer [A], and may contain other additives described later, if necessary.
  • the moisture-curable composition of the present invention may be prepared by mixing the two under dry conditions, and the mixing form thereof is not particularly limited. Usually, it may be mixed in an atmosphere of about 15 to 30 ° C. and 60% RH or less.
  • the content of the curing catalyst [B] is 0.1 to 20 parts by weight, more particularly 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer [A]. 3 to 8 parts by weight is preferable. If the content of the curing catalyst [B] is less than 0.1 parts by weight, the curing performance is insufficient, and if it exceeds 20 parts by weight, the restoration rate of the cured product after curing, physical properties such as weather resistance, and stability during storage. May get worse.
  • the content of the curing catalyst [B] is, for example, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, with respect to 100 parts by weight of the polymer [A]. It is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 parts by mass, and may be within the range between any two of the numerical values exemplified here.
  • a filler may be further added to the moisture-curable composition of the present invention.
  • the filler include calcium carbonate, kaolin, talc, fumed silica, precipitated silica, silicic acid anhydride, hydrous silicic acid, clay, calcined clay, glass, bentonite, organic bentonite, silasburn, glass fiber, asbestos, and the like. Examples thereof include glass filament, crushed quartz, diatomaceous earth, aluminum silicate, aluminum hydroxide, zinc oxide, magnesium oxide, titanium dioxide and the like.
  • the filler may be used alone or in combination of two or more.
  • the addition of the filler improves the handling of the moisture-curable composition. It also works as a rubber reinforcing agent for cured products. The biggest merit is that the amount of resin used can be reduced by adding it as a bulking agent, so that the cost can be reduced.
  • calcium carbonate and titanium oxide are preferable from the viewpoint of maintaining excellent surface non-tack, 50% modulus, workability, weather resistance and the like of the curable composition after curing.
  • the ratio thereof is preferably 1 to 200 parts by weight, more preferably 50 to 200 parts by weight, based on 100 parts by weight of the polymer [A]. Within the above range, the characteristics after curing are not impaired.
  • the moisture-curable composition of the present invention other curing catalysts, curing accelerators, colorants, plasticizers, curing retarders, sagging inhibitors, antiaging agents, solvents and the like are usually added to the curable composition. Additives may be added.
  • curing catalysts examples include organic tin compounds such as dibutyltin dilaurate and dibutyltin bis (acetylacetonate), organic aluminum compounds such as aluminumtris (acetylacetonate) and aluminumtris (ethylacetoacetate), and zirconium tetra (acetyl).
  • organic tin compounds such as dibutyltin dilaurate and dibutyltin bis (acetylacetonate)
  • organic aluminum compounds such as aluminumtris (acetylacetonate) and aluminumtris (ethylacetoacetate)
  • zirconium tetra acetyl
  • organic zirconium compounds such as zirconite tetrabutyrate
  • metal curing catalysts such as 1-amino-2-ethylhexane, 3- (trimethoxysilyl) propylamine, N-2-aminoethyl-3-aminopropyl Trimethoxysilane, N, N, N', N'-tetramethyl-N''-[3- (trimethoxysilyl) propyl] guanidine, 1,5,7-triazabicyclo- [4,4,0]
  • Examples thereof include amine compounds such as deca-5-ene and 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine.
  • the curing accelerator for example, various known amino group-substituted alkoxysilane compounds or condensates thereof can be used. Specifically, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, ⁇ -aminobutyl (methyl) diethoxysilane, N, N-bis (tri). Examples thereof include methoxysilylpropyl) ethylenediamine and partial hydrolysis of these, which also have the effect of improving the adhesion to the substrate.
  • iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, etc. are used as the colorant.
  • plasticizer examples include phthalates such as dibutylphthalate, dioctylphthalate, and butylbenzylphthalate; fatty acid carboxylic acid esters such as dioctyl adipate, dioctyl succinate, diisodecyl succinate, and butyl oleate; penta.
  • Glycol esters such as erythritol esters; phosphate esters such as trioctyl phosphate and tricresyl phosphate; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate; chlorinated paraffin and the like are used.
  • hydrogenated castor oil silicic acid anhydride, organic bentonite, colloidal silica, etc. are used as the sagging preventive agent.
  • adhesion-imparting agents such as phenol resins and epoxy resins, ultraviolet absorbers, radical chain inhibitors, peroxide decomposition agents, various antiaging agents, etc. are used.
  • the curable composition of the present invention is sufficiently stable at room temperature and therefore has excellent storability, and when it comes into contact with moisture, the curing reaction spontaneously proceeds by the compounded curing catalyst [B].
  • the snap time (time until semi-gelation and loss of fluidity) and tack free time (time until surface tack disappears) are short, and workability is excellent.
  • the curable composition of the present invention can be used as a one-component sealing material. Specifically, it is suitably used for applications such as sealing materials for vehicles such as buildings, ships, and automobiles, adhesives, sealing agents, and sealing materials for waterproofing.
  • the method for producing a urethane resin composition comprises a step of reacting a polyol component with an isocyanate component in the presence of a catalyst.
  • a catalyst the above-mentioned complex or mixture can be used.
  • the polyol component is a component composed of a compound having a plurality of hydroxyl groups, and examples of the polyol component include polypropylene glycol and Rael.
  • the isocyanate component is a component composed of a compound having an isocyanate group, and is preferably a polyisocyanate compound having two or more isocyanate groups in the molecule.
  • Method for producing ester compound comprises a step of reacting an alcohol component with an ester component in the presence of a catalyst.
  • a catalyst the above-mentioned complex or mixture can be used.
  • the alcohol component is not particularly limited, and is, for example, ethanol, 1-butanol, 2-butanol, tert-butyl alcohol, amyl alcohol, t-amyl alcohol, 1-hexanol, 2-hexanol, 1-octanol, 2-ethyl.
  • -1-hexanol isodecyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butane Diol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl -1,3-Propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, bisphenol A, hydrogenated bisphenol A, ethylene oxide of bisphenol A or Additives of propylene oxide, aliphatic alcohols such as trimethyl
  • Alicyclic alcohols such as cyclopentanol, cyclohexanol, and adamantanol
  • Aromatic alcohols such as benzyl alcohol, methylbenzyl alcohol, 1-phenylethanol, 2-phenylethanol, etc.
  • Dimethylethanolamine, diethylethanolamine, dipropylethanolamine, 6 -Amino alcohols such as aminohexanol, trans-4-aminocyclohexanol and prolinol, and the like can be mentioned.
  • the ester component is not particularly limited and may be appropriately selected depending on the type of ester compound to be produced.
  • carbonate esters such as dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, diphenyl carbonate, dinaphthyl carbonate, etc.
  • Aromatic carboxylic acid esters such as benzoic acid esters and their derivatives, ⁇ , ⁇ -unsaturated carboxylic acid esters such as (meth) acrylic acid esters, Examples thereof include polyvalent carboxylic acid esters such as oxalic acid diester, malonic acid diester, succinic acid diester, glutaric acid diester, and adipic acid diester.
  • Tetrabutylammonium bromide: 100.00 g (98.7%, 0.30616 mol) and methanol: 50.00 g (1.56055 mol) were charged into a 300 mL four-necked round-bottom flask equipped with a nitrogen introduction tube, and the mixture was stirred. After dissolution, a solution prepared by dissolving 15.93 g (purity 96.3%, 0.27336 mol) of potassium hydroxide in 70.77 g (2.2880 mol) of methanol in advance was added dropwise over 1 hour, and the temperature was 30 ° C. at an internal temperature of 30 ° C. Stir for minutes. After cooling to room temperature, the mixture was filtered to obtain 186.58 g of a B2b: TBAH methanol solution as a transparent liquid.
  • Tetrabutylammonium bromide: 100.00 g (98.7%, 0.30616 mol) and methanol: 120.77 g (3.7648 mol) were charged into a 300 mL 4-necked round-bottom flask equipped with a nitrogen introduction tube, and the mixture was stirred. After dissolution, 15.93 g of potassium hydroxide (purity 96.3%, 0.273336 mol) was added, and the mixture was stirred at an internal temperature of 60 ° C. for 30 minutes. After cooling to room temperature, the mixture was filtered to obtain 186.58 g of a B2c: TBAH methanol solution as a transparent liquid.
  • Tetrabutylammonium bromide: 10.00 g (98.3%, 0.03049 mol) and isopropanol: 150.29 g (2.5007 mol) were charged into a 300 mL four-necked round-bottom flask equipped with a nitrogen introduction tube and stirred. After dissolution, 1.58 g of potassium hydroxide (purity 96.3%, 0.02818 mol) was added, and the mixture was stirred at room temperature for 24 hours. After completion of the reaction, filtration was performed to obtain 155.89 g of a B2i: TBAH isopropanol solution as a transparent liquid.
  • Tetraisopropoxytitanium 143.49 g (0.50486 mol) was charged into a 500 mL four-necked round-bottom flask equipped with a nitrogen introduction tube, and while stirring, the B2a: TBAH methanol solution obtained in Production Example 1: 130.00 g. (33.59%, 0.16829 mol) was added dropwise over 30 minutes. After raising the temperature to an internal temperature of 80 ° C., the mixture is concentrated under reduced pressure (final reduced pressure of 10 mmHg) to distill off isopropanol and methanol to obtain 148.42 g of the complex 1 solution, and 37.13 g (0.61780 mol) of isopropanol. Addition gave 185.55 g of an isopropanol solution of complex 1.
  • Examples 2 to 12 The same operation as in Example 1 was carried out except that the B2b to B2l: TBAH solutions obtained in Production Examples 2 to 12 were used instead of the B2a: TBAH methanol solution obtained in Production Example 1, and the complex 2 to 2 to Twelve solutions were obtained.
  • Tetraisopropoxytitanium 143.49 g (0.50486 mol) was charged into a 500 mL four-necked round-bottom flask equipped with a nitrogen introduction tube, and while stirring, the B2a: TBAH methanol solution obtained in Production Example 1: 130.00 g. (33.59%, 0.16829 mol) was added dropwise over 30 minutes. After raising the temperature to an internal temperature of 80 ° C. and concentrating under reduced pressure (final reduced pressure of 10 mmHg), isopropanol and methanol were distilled off to obtain 148.42 g of the complex 13 solution, and 37.13 g (0.22887 mol) of butyl carbitol. ) was added to obtain 185.55 g of a butyl carbitol solution of the complex 13.
  • Tetraisopropoxytitanium: 143.49 g (0.50486 mol) and butyl carbitol: 37.13 g (0.22887 mol) were placed in a 500 mL four-necked round-bottom flask equipped with a nitrogen introduction tube, and the temperature was raised to 80 ° C. After that, the mixture was concentrated under reduced pressure (final reduced pressure was 10 mmHg) to distill off isopropanol: 13.76 g (0.22887 mol) to obtain 166.86 g of a colorless liquid.
  • B2a TBAH methanol solution: 130.00 g (33.59%, 0.16829 mol) obtained in Production Example 1 was added dropwise thereto over 30 minutes, and then the temperature was raised to 80 ° C. and then concentrated under reduced pressure (final). Isopropanol and methanol were distilled off under a reduced pressure of 10 mmHg) to obtain 167.05 g of a solution of the complex 14.
  • Example 15 Tetraisopropoxytitanium: 143.49 g (0.50486 mol), butyl carbitol: 37.13 g (0.22887 mol), B2a obtained in Production Example 1 in a 500 mL four-necked round-bottom flask equipped with a nitrogen introduction tube: TBAH methanol solution: 130.00 g (33.59%, 0.16829 mol) was charged. After raising the temperature to an internal temperature of 80 ° C. and concentrating under reduced pressure (final reduced pressure of 10 mmHg), isopropanol and methanol were distilled off to obtain 167.05 g of a solution of the complex 15.
  • Examples 16 and 17 The operation was carried out in the same manner as in Example 14 except that the B2e to B2f: TBAH solutions obtained in Production Examples 5 to 6 were used instead of the B2a: TBAH methanol solution obtained in Production Example 1, and the complex 16 and 17 solutions were obtained.
  • Tetraisopropoxytitanium 5.68 g (0.01998 mol) was charged into a 50 mL 4-necked round-bottom flask equipped with a nitrogen introduction tube, and the TBAH methanol solution obtained in Production Example 1 was 7.71 g (33) while stirring. .59%, 0.00998 mol) was added dropwise over 5 minutes. After raising the temperature to an internal temperature of 80 ° C., the mixture is concentrated under reduced pressure (final reduced pressure of 10 mmHg) to distill off isopropanol and methanol to obtain 6.84 g of a solution of complex 18, and 1.71 g (0.02845 mol) of isopropanol. Addition was made to obtain 8.55 g of an isopropanol solution of the complex 18.
  • m-xylened isocyanate Polypropylene glycol molecular weight 3200 diol manufactured by Tokyo Chemical Industry Co., Ltd .: Polypropylene glycol molecular weight 4000 triol type manufactured by Fujifilm Wako Pure Chemical Industries, Ltd .: Fujifilm Wako Pure Chemical Industries, Ltd.
  • Carlex 300 Calcium carbonate (manufactured by Maruo Calcium Co., Ltd.)
  • FR-41 Titanium oxide (manufactured by Furukawa Chemicals Co., Ltd.)
  • REOLOSIL PM-20 Fumed Silica (manufactured by Tokuyama Corporation)
  • DINP Plasticizer (J-PLUS Co., Ltd.) Polypropylene glycol (1000): Plasticizer (manufactured by Kishida Chemical Co., Ltd.) Disparon 6500: Anti-sauce agent (manufactured by Kusumoto Chemical Co., Ltd.) Hydrogenated castor oil: anti-sauce agent (manufactured by Itoh Oil Chemicals, Inc.) Songsorb 3260P: UV absorber (manufactured by SONGWON) Sabostab UV70: Light stabilizer (manufactured by SONGWON) Irganox245: Antioxidant (manufactured by BASF Japan Ltd.) KBM-1003: Dehydrating agent (manufactured by Shinetsu Silicone Industry Co., Ltd.) Isocyanic acid p-toluenesulfonyl: manufactured by Tokyo Chemical Industry Co., Ltd.
  • Nocrack NS-6 anti-aging agent (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)
  • Smoyl P-350 Liquid paraffin (manufactured by Muramatsu Petroleum Co., Ltd.)
  • KBM-903 Adhesive-imparting agent (manufactured by Shin-Etsu Silicone Industry Co., Ltd.)
  • TFT tack-free time
  • the results of the tack free time measurement are shown in Tables 1 to 3.
  • the tack free time of Formulation Example 8 was 6 hr.
  • Methyl benzoate Wako Pure Chemical Industries, Ltd.
  • 2-Ethylhexanol Tokyo Chemical Industry Co., Ltd.

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Abstract

L'invention concerne un procédé de production d'une substance très sûre qui peut être utilisée en tant que catalyseur qui présente une excellente activité.　La présente invention concerne un procédé de production d'un composite d'un composé de titane [B1] et d'hydroxyde d'ammonium [B2], le composé de titane [B1] étant représenté par la formule chimique (1), l'hydroxyde d'ammonium [B2] étant représenté par la formule chimique (2) et le procédé comprenant une première étape et une seconde étape, l'hydroxyde d'ammonium [B2] étant généré en faisant réagir un halogénure d'ammonium [B21] représenté par la formule chimique (3) avec un hydroxyde de métal alcalin au cours de la première étape, et le composé de titane [B1] et l'hydroxyde d'ammonium [B2] étant mis à réagir l'un avec l'autre au cours de la seconde étape.
PCT/JP2021/023727 2020-06-29 2021-06-23 Procédé de production de composite de composé de titane et d'hydroxyde d'ammonium, procédé de production de composition, procédé de production de composé ester et procédé de production d'hydroxyde d'ammonium WO2022004509A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4067338A4 (fr) * 2019-11-29 2023-02-08 Nitto Kasei Co., Ltd. Catalyseur de durcissement destiné à être utilisé pour le durcissement d'un polymère, procédé de production dudit catalyseur de durcissement, composition durcissable à l'humidité, et procédé de production d'article durci
WO2024071051A1 (fr) * 2022-09-30 2024-04-04 株式会社カネカ Composition durcissable

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WO2021106943A1 (fr) * 2019-11-29 2021-06-03 日東化成株式会社 Catalyseur de durcissement destiné à être utilisé pour le durcissement d'un polymère, procédé de production dudit catalyseur de durcissement, composition durcissable à l'humidité, et procédé de production d'article durci

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JPH0393752A (ja) * 1989-09-04 1991-04-18 Toyo Gosei Kogyo Kk 高純度４級アンモニウム水酸化物の製造方法
JP2005075933A (ja) * 2003-09-01 2005-03-24 Teijin Fibers Ltd チタン触媒溶液、及びそれを用いたポリエステルの製造方法
US20060199886A1 (en) * 2005-03-02 2006-09-07 Aps Laboratory Metal phosphate sols, metal nanoparticles, metal-chalcogenide nanoparticles, and nanocomposites made therefrom
CN102030665A (zh) * 2009-09-28 2011-04-27 天津市化学试剂研究所 一种四丁基氢氧化铵的制备方法
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4067338A4 (fr) * 2019-11-29 2023-02-08 Nitto Kasei Co., Ltd. Catalyseur de durcissement destiné à être utilisé pour le durcissement d'un polymère, procédé de production dudit catalyseur de durcissement, composition durcissable à l'humidité, et procédé de production d'article durci
WO2024071051A1 (fr) * 2022-09-30 2024-04-04 株式会社カネカ Composition durcissable

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