WO2022024988A1 - Catalyseur de durcissement destiné à être utilisé pour le durcissement d'un polymère et son procédé de production, composition durcissable à l'humidité et procédé de production d'un article durci - Google Patents

Catalyseur de durcissement destiné à être utilisé pour le durcissement d'un polymère et son procédé de production, composition durcissable à l'humidité et procédé de production d'un article durci Download PDF

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WO2022024988A1
WO2022024988A1 PCT/JP2021/027533 JP2021027533W WO2022024988A1 WO 2022024988 A1 WO2022024988 A1 WO 2022024988A1 JP 2021027533 W JP2021027533 W JP 2021027533W WO 2022024988 A1 WO2022024988 A1 WO 2022024988A1
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group
salt
curing catalyst
curing
polymer
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Japanese (ja)
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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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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only
    • 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 curing catalyst used for curing a polymer, a method for producing the same, a moisture-curable composition, and a method for producing a cured product.
  • 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 Unexamined Patent Publication 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. Therefore, it has been desired to develop a curing catalyst having high safety (low toxicity and environmental pollution) and a practical curing rate.
  • an object of the present invention is to provide a curing catalyst having high safety and a practical curing rate.
  • the present invention is a curing catalyst [B] used for curing a polymer [A] having a reactive hydrolyzable silicon-containing group.
  • the curing catalyst [B] contains a complex of a titanium compound [B1] and an organic onium salt [B2].
  • a curing catalyst [B] represented by the chemical formula (1) is provided. (R1 - O) n Ti-A 4-n (1) (In the formula, R 1 is a substituted or unsubstituted hydrocarbon group, n is 1 to 4, and A is a ⁇ -diketone group).
  • the curing catalyst [B] of the present invention is used for curing a polymer [A] having a reactive hydrolyzable silicon-containing group.
  • the polymer [A] is preferably liquid at room temperature.
  • 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.
  • 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] The main chain of the 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.
  • Examples of the polymer of the ethylenically unsaturated compound and the diene compound include homopolymers such as ethylene, propylene, acrylic acid ester, methacrylic acid ester, vinyl acetate, acrylonitrile, styrene, isobutylene, butadiene, isoprene and chloroprene, or Examples thereof include these two or more kinds of copolymers.
  • polybutadiene 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 Examples include esters. 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 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.
  • Substituent allyl groups include aryl groups such as phenyl, toluyl, xylyl; aralkyl groups such as benzyl and 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 ). Further, depending on the physical characteristics and use of the cured product, a bifunctional form ( R'2 SiO) or a monofunctional form ( R'3 SiO 0.5 ) may be combined as needed (where R'is an organic group. ). 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 curing catalyst [B] contains a complex of a titanium compound [B1] and an onium salt [B2]. This complex is a reaction product that can be obtained by reacting a titanium compound [B1] with an onium salt [B2].
  • Ti-A 4-n The titanium compound [B1] is represented by the chemical formula (1).
  • R 1 is a substituted or unsubstituted hydrocarbon group, n is 1 to 4, and A is 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.
  • the substituted or unsubstituted hydrocarbon group represented by R1 is a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and an aliphatic hydrocarbon group is preferable.
  • 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 (3).
  • 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- (3) 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). What is represented, etc.
  • 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 compounds represented by the chemical formula (1) tetraisopropoxytitanium, triisopropoxyoctoxytitanium, and triisopropoxy2- (2-butoxyethoxy) are used in terms of catalytic activity, compound stability, and handleability. Ethoxytitanium triisopropoxy 2-butoxyethoxytitanium is more preferred.
  • the above titanium compound [B1] may be used alone or in combination of two or more.
  • Organic onium salt [B2] is a salt containing organic onium.
  • the organic onium include those in which at least one hydrogen atom of onium is substituted with a hydrocarbon group, and those in which all hydrogen atoms of onium are substituted with a hydrocarbon group are preferable. Hydroxyldo is exemplified as the counter anion of organic onium, but other anions may be used.
  • organic onium salt [B2] Quaternary ammonium salt, quaternary phosphonium salt, quaternary imidazolium salt, quaternary pyrrolidinium salt, quaternary pyridinium salt, quaternary piperidinium salt, quaternary piperidinium salt, as organic onium salt [B2].
  • Pyridinium salt, tertiary sulfonium salt, tertiary oxonium salt and the like can be mentioned.
  • the organic onium salt [B2] is preferably an organic onium salt other than the quaternary ammonium hydroxide, and more preferably a quaternary phosphonium salt.
  • the organic onium salt [B2] is more preferably a quaternary phosphonium hydroxide represented by the following formula (2).
  • R 2 , R 3 , R 4 , and R 5 represent substituted or unsubstituted hydrocarbon groups that 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 preferably has 1 to 16 carbon atoms. Specifically, the carbon number is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, and the numerical values exemplified here. It may be within the range between any two of the above.
  • 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.
  • 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, a butyl group, an octyl group, a dodecyl group and a hexadecyl group are preferable.
  • 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, a butyl group, an octyl group, a dodecyl group and a hexadecyl 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.
  • phosphonium hydroxyd group represented by the chemical formula (2) examples include tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, tetrabutylphosphonium hydroxide, tetraoctylphosphonium hydroxide, and tributyldodecylphosphonium hydroxydo.
  • tributylhexadecylphosphonium hydroxide butyltriphenylphosphonium hydroxide, benzyltriphenylphosphonium hydroxydo, tetraphenylphosphonium hydroxydo, etc., in particular tetrabutylphosphonium hydroxide, tetraoctylphosphonium hydroxide, tributyldodecylphosphonium hydroxydo De, tributylhexadecylphosphonium hydroxide is preferred.
  • the complex of the titanium compound [B1] and the organic onium salt [B2] is, for example, a transparent liquid, and can be obtained by reacting a mixture of both at, for example, 40 to 100 ° C. Specifically, this temperature is, for example, 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 organic onium salt [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.
  • the moisture-curable composition of the present invention contains the above-mentioned curing catalyst [B] and 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.
  • the filler [C] 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 8-diazabicyclo [5,4,0] undecene-7 (DBU), 2-tertiary butyl-1,1,3,3- Examples thereof include amine compounds such as tetramethylguanidine 1,5,7-triazabicyclo [4.4.0] -5-decene, ethylenediamine, diethylenetriamine, 3,3-diaminopropylamine and triethylenetetramine.
  • 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.
  • adhesive-imparting agents such as phenol resin and epoxy resin, ultraviolet absorbers, radical chain inhibitors, peroxide decomposition agents, various antioxidants and the like 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.
  • Complex 1 Tetrabutylphosphonium salt (complex 1)> 6.7874 g (0.02 mol) of tetrabutylphosphonium bromide is dissolved in 20 ml of dehydrated methanol and filled with 20 ml of strongly basic ion exchange resin (Amberlite IRA900 (OH) -HG; Organo's pre-dehydrated methanol replacement). Then,
  • Tetraisopropoxytitanium 8.52 g (0.03 mol) and 17.6% tetrabutylphosphonium hydroxydomethanol solution: 15.69 g (0.01 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then placed in a stirrer. And mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 14 mmHg) to distill off isopropanol and methanol to obtain 8.39 g of a pale yellow solid tetrabutylphosphonium salt (complex 1). Further, 2.1 g of isopropanol was added, and the mixture was heated and dissolved in a water bath at 60 ° C. to obtain 10.39 g of a pale yellow liquid.
  • a strongly basic ion exchange resin Amberlite IRA900 (OH) -HG
  • Organo's pre-dehydrated methanol replacement Organo's pre-dehydrated methanol replacement
  • Tetraisopropoxytitanium 8.52 g (0.03 mol), 11.4% tetraethylphosphonium hydroxydomethanol solution: 14.41 g (0.01 mol) was placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then stirred. It was mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 17 mmHg) to distill off isopropanol and methanol to obtain 7.23 g of a yellow liquid tetraethylphosphonium salt (complex 2). Further, 1.82 g of isopropanol was added, and the mixture was heated and dissolved in a water bath at 60 ° C. to obtain 8.94 g of a yellow liquid.
  • Tetraisopropoxytitanium 8.52 g (0.03 mol) and 25.7% tributylhexadecylphosphonium hydroxydomethanol solution: 17.32 g (0.01 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then stirred. Was thoroughly mixed in. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 17 mmHg) to distill off isopropanol and methanol to obtain 9.92 g of a yellow liquid tributylhexadecylphosphonium salt (complex 5). Further, 2.50 g of isopropanol was added, and the mixture was heated and dissolved in a water bath at 60 ° C. to obtain 12.08 g of a yellow liquid.
  • a strongly basic ion exchange resin Amberlite IRA900 (OH) -HG; Organo's pre-dehydrated methanol was substituted
  • Tetraisopropoxytitanium 8.52 g (0.03 mol), 20.8% butyltriphenylphosphonium hydroxydomethanol solution: 16.17 g (0.01 mol) was placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then stirred. Was thoroughly mixed in. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 18 mmHg) to distill off isopropanol and methanol to obtain 8.40 g of a pale yellow solid butyltriphenylphosphonium salt (complex 6). Further, 2.10 g of isopropanol was added, and the mixture was heated and dissolved in a water bath at 60 ° C. to obtain 10.35 g of a yellow liquid.
  • Tetraisopropoxytitanium: 8.52 g (0.03 mol) and 17.0% tributyldodecylphosphonium hydroxydomethanol solution: 22.88 g (0.01 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then placed in a stirrer. And mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 12 mmHg) to distill off isopropanol and methanol to obtain 8.72 g of a yellow liquid tributyldodecylphosphonium salt (complex 7). Of this, 1.00 g of isopropanol was further added to 4.00 g, and the mixture was heated and dissolved in a water bath at 60 ° C. to obtain 4.70 g of a yellow liquid.
  • Tributyldodecylphosphonium salt (complex 9) The same operation as in Production Example 4 was carried out to obtain a tributyldodecylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 97.5%.
  • Tetraisopropoxytitanium 7.10 g (0.025 mol) and 16.9% tributyldodecylphosphonium hydroxydomethanol solution: 11.47 g (0.005 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then placed in a stirrer. And mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 17 mmHg) to distill off isopropanol and methanol to obtain 6.22 g of a pale yellow liquid tributyldodecylphosphonium salt (complex 9).
  • Tributyldodecylphosphonium salt (complex 10)> The same operation as in Production Example 4 was carried out to obtain a tributyldodecylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 98.8%. The obtained methanol solution was concentrated under reduced pressure at 25 ° C. (final reduced pressure degree: 85 mmHg) to obtain a 16.8% methanol solution (tributyldodecylphosphonium hydroxide: methanol 1:60).
  • Tetraisopropoxytitanium 5.68 g (0.020 mol) and 16.8% tributyldodecylphosphonium hydroxydomethanol solution: 11.57 g (0.005 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then placed in a stirrer. And mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 17 mmHg) to distill off isopropanol and methanol to obtain 5.34 g of a yellow liquid tributyldodecylphosphonium salt (complex 10).
  • Tributyldodecylphosphonium salt (complex 11)> The same operation as in Production Example 4 was carried out to obtain a tributyldodecylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 98.8%. The obtained methanol solution was concentrated under reduced pressure at 25 ° C. (final reduced pressure degree: 85 mmHg) to obtain a 16.8% methanol solution (tributyldodecylphosphonium hydroxide: methanol 1:60).
  • Tetraisopropoxytitanium 5.68 g (0.02 mol) and 16.8% tributyldodecylphosphonium hydroxydomethanol solution: 23.13 g (0.01 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then placed in a stirrer. And mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 11 mmHg) to distill off isopropanol and methanol to obtain 7.04 g of a yellow liquid tributyldodecylphosphonium salt (complex 11).
  • Tributyldodecylphosphonium salt (complex 12)> The same operation as in Production Example 4 was carried out to obtain a tributyldodecylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 97.5%. The obtained methanol solution was concentrated under reduced pressure at 25 ° C. (final reduced pressure degree: 85 mmHg) to obtain a 16.9% methanol solution (tributyldodecylphosphonium hydroxide: methanol 1:60).
  • Tetraisopropoxytitanium 2.84 g (0.01 mol) and 16.9% tributyldodecylphosphonium hydroxydomethanol solution: 22.94 g (0.01 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then placed in a stirrer. And mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 16 mmHg) to distill off isopropanol and methanol to obtain 5.23 g of a yellow liquid tributyldodecylphosphonium salt (complex 12).
  • tack-free time (the time required from the end of kneading to the time when the sample did not adhere to the fingertips by lightly touching three points on the surface with a fingertip cleaned with ethyl alcohol) was measured for the obtained moisture-curable composition. ..
  • the results of the tack free time measurement are shown in Table 1.
  • MS Polymer SAX520 Organic Polymer Containing a Cyril Group (manufactured by Kaneka Corporation)
  • MS Polymer S303 Cyril group-containing organic polymer (manufactured by Kaneka Corporation)
  • STP-E15 Cyril group-containing organic polymer (manufactured by WACKER Chemical Corporation)
  • Tetraisopropoxytitanium manufactured by Tokyo Chemical Industry Co., Ltd.
  • Tetrabutylphosphonium hydroxide 17.6% tetrabutylphosphonium hydroxydomethanol solution, manufactured in Production Example 1.
  • 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.)
  • PPG1000 Plasticizer (manufactured by Kishida Chemical Co., Ltd.)
  • Disparon 6500 Anti-sauce agent (manufactured by Kusumoto Chemical Co., Ltd.)
  • 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.)
  • KBM-903 Adhesive-imparting agent (manufactured by Shin-Etsu Silicone Industry Co., Ltd.)

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le but de la présente invention est de fournir un catalyseur de durcissement qui est hautement sûr et qui permet d'obtenir une vitesse de durcissement pratique.　La présente invention concerne un catalyseur de durcissement [B] destiné à être utilisé pour durcir un polymère [A] ayant un groupe contenant du silicium hydrolysable réactif. Ce catalyseur de durcissement [B] comprend un complexe d'un composé de titane [B1] et d'un sel d'onium organique [B2], ledit composé de titane [B1] étant représenté par la formule chimique (1).　(1) : (R1-O)nTi-A4-n (dans la formule : R1 représente un groupe hydrocarboné éventuellement substitué ; n vaut de 1 à 4 ; et A représente un groupe β-dicétone.)
PCT/JP2021/027533 2020-07-30 2021-07-26 Catalyseur de durcissement destiné à être utilisé pour le durcissement d'un polymère et son procédé de production, composition durcissable à l'humidité et procédé de production d'un article durci WO2022024988A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11148022A (ja) * 1997-11-17 1999-06-02 Dainippon Ink & Chem Inc 硬化性組成物および、それを含有するコーティング剤
JP2002194122A (ja) * 2000-12-25 2002-07-10 Kanegafuchi Chem Ind Co Ltd シルセスキオキサンポリマーおよびポリカルボシラン複合系プリプレグ及びそれを用いた積層板
JP2003064305A (ja) * 2001-08-27 2003-03-05 Jsr Corp 膜形成用組成物の製造方法、膜形成用組成物、膜の形成方法およびシリカ系膜
JP2005314616A (ja) * 2004-04-30 2005-11-10 Shin Etsu Chem Co Ltd シリコーンコーティング組成物及び被覆物品
JP2010047741A (ja) * 2008-07-22 2010-03-04 Hitachi Chem Co Ltd 熱硬化性樹脂組成物、これを用いた光半導体素子搭載用基板及びその製造方法並びに光半導体装置
JP2014114434A (ja) * 2012-11-14 2014-06-26 Kaneka Corp 硬化性組成物
WO2015033801A1 (fr) * 2013-09-03 2015-03-12 東亞合成株式会社 Composition de résine durcissable

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11148022A (ja) * 1997-11-17 1999-06-02 Dainippon Ink & Chem Inc 硬化性組成物および、それを含有するコーティング剤
JP2002194122A (ja) * 2000-12-25 2002-07-10 Kanegafuchi Chem Ind Co Ltd シルセスキオキサンポリマーおよびポリカルボシラン複合系プリプレグ及びそれを用いた積層板
JP2003064305A (ja) * 2001-08-27 2003-03-05 Jsr Corp 膜形成用組成物の製造方法、膜形成用組成物、膜の形成方法およびシリカ系膜
JP2005314616A (ja) * 2004-04-30 2005-11-10 Shin Etsu Chem Co Ltd シリコーンコーティング組成物及び被覆物品
JP2010047741A (ja) * 2008-07-22 2010-03-04 Hitachi Chem Co Ltd 熱硬化性樹脂組成物、これを用いた光半導体素子搭載用基板及びその製造方法並びに光半導体装置
JP2014114434A (ja) * 2012-11-14 2014-06-26 Kaneka Corp 硬化性組成物
WO2015033801A1 (fr) * 2013-09-03 2015-03-12 東亞合成株式会社 Composition de résine durcissable

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