Method for producing polymers having allyl groups or hydrolyzable silicon groups

Abstract

To provide a novel method for producing allyl group-containing organic polymers or hydrolyzable silicon group-containing organic polymers using a simple process. [Solution] An organic polymer (A) having an allyl group and a hydroxyl group is reacted with a compound (B) having at least two vinyl ether groups to obtain an organic polymer (C) having at least two allyl groups by forming an acetal structure through the reaction of the hydroxyl group and the vinyl ether group. Furthermore, the organic polymer (C) is subjected to a hydrosilylation reaction with a hydrolyzable silicon group-containing hydrosilane compound (D) to obtain a hydrolyzable silicon group-containing organic polymer (E).

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polymer having an allyl group, or a method for producing a polymer having a hydrolyzable silicon group. [Background technology]

[0002] Polymers containing hydrolyzable silicon groups are known to crosslink in the presence of moisture through hydrolysis and condensation reactions of the hydrolyzable silicon groups, leading to the formation of siloxane bonds and resulting in a rubbery cured product. Such polymers are already produced industrially and are widely used in applications such as adhesives, sealants, coatings, paints, and tacks.

[0003] One known method for producing such polymers involves adding hydrosilanes to polymers containing allyl groups to convert them into hydrolyzable silicon groups. Therefore, polymers containing allyl groups are important intermediates in the production of polymers containing hydrolyzable silicon groups.

[0004] A known method for producing polymers having such allyl groups involves reacting a polymer having hydroxyl groups with an alkaline component such as an alkali metal, potassium hydroxide, or metal alkoxide to convert the hydroxyl groups into alkoxide groups, and then introducing allyl groups by reacting with an organic halide such as allyl chloride (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 52-73998 [Patent Document 2] Japanese Patent Application Publication No. 4-36312 [Overview of the project] [Problems that the invention aims to solve]

[0006] According to the methods described in Patent Documents 1 and 2, the production of polymers containing allyl groups requires alkoxide formation and reaction with organic halides, which is cumbersome in terms of production. To improve the productivity of polymers containing allyl groups and polymers containing hydrolyzable silicon groups, fewer steps are desirable.

[0007] In view of the above situation, the present invention aims to provide a novel method for producing allyl group-containing organic polymers or hydrolyzable silicon group-containing organic polymers using a simple process. [Means for solving the problem]

[0008] As a result of diligent research to solve the above-mentioned problems, the inventors of the present invention discovered that an organic polymer having at least two allyl groups can be produced by reacting an organic polymer having an allyl group and a hydroxyl group with a compound having at least two vinyl ether groups, leading to the present invention.

[0009] In other words, the present invention relates to a method for producing an organic polymer having an allyl group, comprising the step of reacting an organic polymer (A) having an allyl group and a hydroxyl group with a compound (B) having at least two vinyl ether groups to obtain an organic polymer (C) having at least two allyl groups by forming an acetal structure through the reaction of the hydroxyl group and the vinyl ether group. The present invention also relates to a method for producing a hydrolyzable silicon group-containing organic polymer (E), which includes the step of obtaining an organic polymer (C) having at least two allyl groups by the above-described production method, and then subjecting the organic polymer (C) to a hydrosilylation reaction with a hydrolyzable silicon group-containing hydrosilane compound (D) to obtain a hydrolyzable silicon group-containing organic polymer (E). Furthermore, the present invention also relates to an organic polymer (C) having an organic polymer backbone and having at least two allyl groups and an acetal structure in one molecule. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a novel production method capable of producing an allyl group-containing organic polymer or a hydrolyzable silicon group-containing organic polymer through a simple process.

[0011] According to the present invention, it is possible to produce a novel organic polymer having at least two allyl groups and an acetal structure in one molecule. The organic polymer can be suitably used as an intermediate for producing a hydrolyzable silicon group-containing polymer.

[0012] Further, according to the present invention, it is possible to produce a novel organic polymer having a hydrolyzable silicon group and an acetal structure in one molecule. The organic polymer can be suitably utilized as a curable resin that can form siloxane bonds and cure in the presence of moisture. [Mode for Carrying Out the Invention]

[0013] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the respective embodiments described below, and various modifications are possible within the scope defined in the claims. In addition, the respective configurations described below can be arbitrarily combined, and such combinations can also constitute one aspect of the present invention.

[0014] The production method according to the present disclosure is a method of reacting an organic polymer (A) having an allyl group and a hydroxyl group with a compound (B) having at least two vinyl ether groups, to produce an organic polymer (C) having at least two allyl groups by forming an acetal structure through the reaction between the hydroxyl group and the vinyl ether group.

[0015] <Organic Polymer (A) Having Allyl Group and Hydroxyl Group> The organic polymer (A) has a hydroxyl group and an allyl group. This hydroxyl group reacts with the vinyl ether group of the compound (B) to form an acetal structure.

[0016] The average number of hydroxyl groups per molecule of the organic polymer (A) is not particularly limited, but is preferably 0.5 or more, more preferably 0.8 or more, and even more preferably 0.9 or more. The upper limit is preferably less than 2.0, more preferably 1.5 or less, and even more preferably 1.0 or less.

[0017] The hydroxyl group may be bonded to the polymer skeleton of the organic polymer (A) as a side chain, or may be bonded to the terminal of the polymer skeleton. From the viewpoint of obtaining a linear polymer as the organic polymer (C), the organic polymer (A) preferably has a hydroxyl group at the terminal of the polymer skeleton.

[0018] The allyl group contained in the organic polymer (A) is a monovalent group represented by CH2=CH-CH2-. By reacting with the compound (B), at least two molecules of the organic polymer (A) having an allyl group are bonded to each other, whereby the organic polymer (C) having at least two allyl groups can be obtained.

[0019] The average number of allyl groups per molecule of the organic polymer (A) is not particularly limited, but is preferably 0.5 or more, more preferably 0.8 or more, and even more preferably 0.9 or more. The upper limit is preferably less than 2.0, more preferably 1.5 or less, and even more preferably 1.0 or less.

[0020] The allyl group may be bonded to the polymer skeleton of the organic polymer (A) as a side chain, or may be bonded to the terminal of the polymer skeleton. From the viewpoint of obtaining the organic polymer (C) having an allyl group at the terminal, the organic polymer (A) preferably has an allyl group at the terminal of the polymer skeleton.

[0021] In particular, the organic polymer (A) preferably has an allyl group and a hydroxyl group at the terminal of its polymer skeleton. Among them, it is particularly preferable that the organic polymer (A) has a linear polymer skeleton, has a hydroxyl group at one terminal of the same polymer skeleton, and has an allyl group at the other terminal.

[0022] A polymer skeleton is a repeating structure in which multiple monomers are bonded together by addition, condensation, or other processes, forming a continuous series of monomer units. However, the polymer skeleton may contain only one type of monomer, or multiple types may be bonded together in a mixture.

[0023] The polymer skeleton of organic polymer (A) is not particularly limited and includes polyoxyalkylene polymers, saturated hydrocarbon polymers, (meth)acrylic acid ester polymers, polyester polymers obtained by condensation of dibasic acids such as adipic acid with glycol, or ring-opening polymerization of lactones, vinyl copolymers obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile, and styrene, polysulfide polymers, polyamide polymers, polycarbonate polymers, diallyl phthalate polymers, etc. Among these, those selected from the group consisting of polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester polymers are preferred. Because these polymers have relatively low glass transition temperatures, the resulting cured products can maintain good cold resistance.

[0024] In particular, polyoxyalkylene polymers and (meth)acrylic acid ester polymers are especially preferred because they have high moisture permeability, excellent deep curing properties when used in a one-component curable composition, and also excellent adhesive properties. Both may be used in combination. Polyoxyalkylene polymers are particularly preferred.

[0025] Polyoxyalkylene polymers are -R 2 -O-(wherein, R 2 It is preferable that the polymer has repeating units represented by linear or branched alkylene groups having 1 to 14 carbon atoms. 2 It is more preferable that the alkylene group has 2 to 4 carbon atoms and is linear or branched. -R 2Specific examples of repeating units denoted by -O- include -CH2O-, -CH2CH2O-, -CH2CH(CH3)O-, -CH2CH(C2H5)O-, -CH2C(CH3)(CH3)O-, and -CH2CH2CH2CH2O-. The main chain structure of a polyoxyalkylene polymer may consist of only one type of repeating unit or of two or more types of repeating units.

[0026] Specific examples of polyoxyalkylene polymers include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer.

[0027] In particular, when using the curable composition according to this disclosure as a sealant, adhesive, etc., a polyoxypropylene polymer having oxypropylene repeating units at a concentration of 50% by weight or more, more preferably 80% by weight or more, of the polymer backbone is preferred because it is amorphous and has relatively low viscosity.

[0028] The main chain structure of the polyoxyalkylene polymer may be linear or branched, but from the viewpoint of obtaining a linear polymer as the organic polymer (C), it is preferable that it be linear.

[0029] (Meth)acrylic acid ester polymers can be modified by combining various monomer compositions to improve adhesion, heat resistance and weather resistance, and reduce the water absorption of cured products obtained by curing curable compositions. Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and stearyl (meth)acrylate. Note that (meth)acrylic refers to acrylic and / or methacrylic.

[0030] Examples of saturated hydrocarbon polymers include polyethylene, polypropylene, ethylene-propylene copolymers, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, and hydrogenated polyolefin polymers obtained by hydrogenating copolymers of isobutylene and isoprene, etc.

[0031] The number-average molecular weight of the organic polymer (A) is preferably 2,000 to 100,000, more preferably 5,000 to 50,000, and particularly preferably 8,000 to 35,000, as polystyrene-equivalent molecular weight in GPC. When the number-average molecular weight is within the above range, it is possible to obtain an organic polymer (A) that has an easy-to-handle viscosity and excellent workability while keeping manufacturing costs within a reasonable range.

[0032] The molecular weight distribution (Mw / Mn) of the organic polymer (A) is not particularly limited, but is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, even more preferably 1.4 or less, particularly preferably 1.3 or less, and most preferably 1.2 or less.

[0033] The method for producing the organic polymer (A) is not particularly limited and can be any conventionally known method. Furthermore, a commercially available product may be used as the organic polymer (A). The following describes a specific example of a method for producing an organic polymer (A) in which the polymer backbone is a polyoxyalkylene polymer.

[0034] Polyoxyalkylene polymers can be formed by polymerizing an epoxy compound onto a hydroxyl group-containing initiator using conventionally known methods, thereby obtaining polyoxyalkylene polymers with hydroxyl groups at their terminals. While there are no particular limitations on the specific polymerization method, polymerization methods using complex metal cyanide catalysts such as zinc hexacyanocobaltate glyme complexes are preferred because they yield hydroxyl-terminated polymers with a small molecular weight distribution (Mw / Mn).

[0035] The initiator having a hydroxyl group preferably has an allyl group. This makes it possible to obtain an organic polymer (A) having an allyl group at one end and a hydroxyl group at the other end.

[0036] The initiator having an allyl group and a hydroxyl group is not particularly limited, but examples include allyl alcohol, ethylene glycol monoallyl ether, propylene glycol monoallyl ether, low molecular weight polyoxyethylene monoallyl ether, and low molecular weight polyoxypropylene monoallyl ether.

[0037] The epoxy compound that forms the polymer skeleton is not particularly limited, but examples include alkylene oxides such as ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, and α-methylstyrene oxide, and alkylglycidyl ethers such as methyl glycidyl ether, ethyl glycidyl ether, isopropyl glycidyl ether, and butyl glycidyl ether. Among these, alkylene oxides are preferred, alkylene oxides having 2 to 4 carbon atoms are more preferred, and propylene oxide is particularly preferred.

[0038] <Compound (B) having at least two vinyl ether groups> Compound (B) is a compound having at least two vinyl ether groups in one molecule. A vinyl ether group is a monovalent group represented as CH2=CH-O-.

[0039] Compound (B) may be a compound having two vinyl ether groups in one molecule, or a compound having three or more vinyl ether groups in one molecule. In the former case, the resulting organic polymer (C) may be a linear polymer, and in the latter case, the resulting organic polymer (C) may be a branched polymer.

[0040] The compound having two vinyl ether groups in one molecule can be represented, for example, by the following general formula (1).

[0041] [ka]

[0042] In formula (1), R 1 This represents an organic group having 1 to 20 carbon atoms. The organic group may contain at least one atom selected from the group consisting of oxygen, nitrogen, and sulfur atoms. The number of carbon atoms may be 1 to 12, 1 to 8, or 1 to 4.

[0043] The aforementioned organic group preferably includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, and more preferably an aliphatic hydrocarbon group.

[0044] R 1 Specific examples include, but are not limited to, alkylene groups such as methylene, ethylene, and propylene groups; alkylene groups containing an oxygen atom (specifically, polyoxyalkylene groups such as polyoxyethylene, polyoxypropylene, and polyoxybutylene groups); and arylene groups such as phenylene groups. Among these, alkylene groups or alkylene groups containing an oxygen atom are preferred.

[0045] The amount of compound (B) having at least two vinyl ether groups can be appropriately set according to the number of allyl groups in the resulting organic polymer (C), but it is preferable that the amount used is such that the molar ratio of vinyl ether groups of compound (B) to hydroxyl groups of organic polymer (A) is 0.3 or more, more preferably 0.4 or more, and even more preferably 0.5 or more. Furthermore, the upper limit is preferably 2 or less, more preferably 1.5 or less, and even more preferably 1.2 or less.

[0046] <Production of an organic polymer (C) having at least two allyl groups> According to the manufacturing method described herein, an organic polymer (C) having at least two allyl groups is produced by reacting an organic polymer (A) having an allyl group and a hydroxyl group with a compound (B) having at least two vinyl ether groups.

[0047] In this reaction, an acetal structure is formed by the reaction of a hydroxyl group in organic polymer (A) with a vinyl ether group in compound (B). Since compound (B) has at least two vinyl ether groups, at least two molecules of organic polymer (A) can react with one molecule of compound (B). As a result, the resulting organic polymer (C) has an acetal structure and at least two allyl groups in one molecule. Organic polymer (C) may have one or at least two acetal structures in one molecule. Here, an acetal structure is a structure represented by -COCOC-, in which one carbon atom has two ether bonds.

[0048] In particular, if organic polymer (A) has a linear polymer skeleton, with a hydroxyl group at one end of the polymer skeleton and an allyl group at the other end, and compound (B) is a compound having two vinyl ether groups, then organic polymer (C) having allyl groups at both ends of the linear polymer can be obtained.

[0049] An example of a reaction equation in the manufacturing method relating to this disclosure is shown below. In the following equation, the organic polymer (A) is a polyoxyalkylene polymer having allyl groups and hydroxyl groups at each end of a linear polymer skeleton, and compound (B) is diethylene glycol divinyl ether, but the manufacturing method relating to this disclosure is not limited to this.

[0050] [ka]

[0051] In the above formula, the two hydroxyl groups of two molecules of hydroxyl-containing organic polymer (A) react with the two vinyl ether groups of one molecule of compound (B) to form two acetal structures, generating organic polymer (C) having allyl groups at both ends.

[0052] Organic polymer (C) is formed by the bonding of two molecules of organic polymer (A), with the two polymer skeletons of organic polymer (A) linked via two acetal structures. Organic polymer (C) contains two acetal structures internally and has allyl groups at both ends of its dimerized polymer skeleton, both of which originate from organic polymer (A).

[0053] In the manufacturing method according to this disclosure, an organic polymer (A) having an allyl group and a hydroxyl group and a compound (B) having at least two vinyl ether groups can be mixed and stirred to react the two.

[0054] To suppress side reactions, it is preferable that compound (B) used has had its water removed beforehand. Specifically, it is preferable that the water content of compound (B) be less than 1000 ppm.

[0055] When mixing the two components, compound (B) may be added to the organic polymer (A) all at once, or it may be added continuously or in stages.

[0056] When reacting the two components, it is preferable to use a catalyst to promote the reaction between the hydroxyl group and the vinyl ether group. While known catalysts can be used, acidic catalysts are preferred. Specific examples include pyridinium p-toluenesulfonate, p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, and phosphoric acid.

[0057] A solvent may or may not be used when reacting the two components. If a solvent is used, there are no particular limitations on the solvents that can be used, but examples include dichloromethane, tetrahydrofuran, and diethyl ether.

[0058] The temperature at which the organic polymer (A) and compound (B) react can be set as appropriate, but for example, it is preferably around 20 to 170°C, more preferably 30 to 150°C, and even more preferably 40 to 140°C.

[0059] The reaction time between the organic polymer (A) and compound (B) can be set as appropriate, but for example, it is preferably 10 minutes to 12 hours, more preferably 30 minutes to 10 hours, and even more preferably 1 to 5 hours.

[0060] After the reaction of both components is complete, it is preferable to add a base to the reaction solution to neutralize the acidic catalyst. This can enhance the stability of the resulting organic polymer (C). The type of base is not particularly limited and examples include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, and sodium carbonate. The amount of base added is not particularly limited and should be set appropriately to the amount necessary to neutralize the acidic catalyst.

[0061] <Organic polymer (C) having at least two allyl groups> Through the above steps, an organic polymer (C) having at least two allyl groups and an acetal structure in one molecule can be produced. This organic polymer (C) is a novel polymer with a previously unreported structure and constitutes one aspect of the present invention.

[0062] The average number of allyl groups or acetal structures per molecule of the organic polymer (C) is preferably 1.4 or more, more preferably 1.6 or more, and even more preferably 1.8 or more. The upper limit is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.0 or less.

[0063] The allyl group may be bonded to the polymer backbone of organic polymer (C) as a side chain, or it may be bonded to the end of the polymer backbone. From the viewpoint of obtaining organic polymer (E) having hydrolyzable silicon groups at its termini, it is preferable that the allyl group is bonded to the end of the polymer backbone of organic polymer (C).

[0064] In particular, the organic polymer (C) preferably has a linear polymer skeleton and has allyl groups at both ends of the polymer skeleton.

[0065] The polymer skeleton of organic polymer (C) is the same as that of organic polymer (A) described above. Among these, polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester polymers are preferred because they have relatively low glass transition temperatures. Polyoxyalkylene polymers are particularly preferred. However, the polymer skeleton of organic polymer (C) contains a structure derived from compound (B) internally and has an acetal structure.

[0066] The number-average molecular weight of the organic polymer (C) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and particularly preferably 8,000 to 35,000, as polystyrene-equivalent molecular weight in GPC. When the number-average molecular weight is within these ranges, it is possible to obtain an organic polymer (C) that has a manageable viscosity and excellent workability while keeping manufacturing costs within a reasonable range.

[0067] The molecular weight distribution (Mw / Mn) of the organic polymer (C) is not particularly limited, but is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, even more preferably 1.4 or less, particularly preferably 1.3 or less, and most preferably 1.2 or less.

[0068] <Production of organic polymer (E) containing hydrolyzable silicon groups> The organic polymer (C) having at least two allyl groups produced as described above is subjected to a hydrosilylation reaction with a hydrolyzable silicon group-containing hydrosilane compound (D), whereby an organic polymer (E) having a hydrolyzable silicon group can be produced.

[0069] Examples of the hydrolyzable silicon group-containing hydrosilane compound (D) include those represented by the following formula (2). In the formula, R 3 , X, and a are the same as those explained for formula (3) described later. H-SiR 3 a X 3-a (2)

[0070] Specific examples of hydrolyzable silicon group-containing hydrosilane compounds (D) include halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, and bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane Lan, dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, bis(chloromethyl)methoxysilane, (methoxymethyl)methylmethoxysilane, (methoxymethyl)dimethoxysilane, bis(methoxymethyl)methoxysilane, (methoxymethyl)diethoxysilane, (ethoxymethyl)diethoxysilane, (3,3,3-trifluor (Propropyl)dimethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyloxy]dimethylsilane, [(chloromethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane, [(3,3,3-triph Examples include alkoxysilanes such as [dimethoxysilyloxy]dimethylsilane ([orolhopropyl]dimethoxysilyloxy]dimethylsilane; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane; and isopropenyloxysilanes (deacetone-free type) such as triisopropenyloxysilane, (chloromethyl)diisopropenyloxysilane, and (methoxymethyl)diisopropenyloxysilane.

[0071] The amount of hydrolyzable silicon group-containing hydrosilane compound (D) used should be appropriately determined considering the amount of allyl groups present in the polymer (C) and the desired number of hydrolyzable silicon groups to be introduced. Specifically, the molar ratio of hydrosilane compound (D) to allyl groups present in the organic polymer (C) is preferably 0.05 to 10, and more preferably 0.3 to 2, from the viewpoint of reactivity.

[0072] An example of a hydrosilylation reaction relating to this disclosure is shown below. In the formula below, an example is shown in which the above-mentioned specific polymer is used as the organic polymer (C) and DMS:methyldimethoxysilane is used as the hydrolyzable silicon group-containing hydrosilane compound (D), but the hydrosilylation reaction relating to this disclosure is not limited to this.

[0073] [ka]

[0074] In the above formula, hydrosilane compound (D) hydrosilylates each of the two allyl groups of organic polymer (C), thereby introducing hydrolyzable silicon groups into the organic polymer, and generating organic polymer (E) having hydrolyzable silicon groups at both ends.

[0075] Organic polymer (E) has two polymer skeletons of organic polymer (A) linked together via two acetal structures. Organic polymer (E) contains two acetal structures internally and has hydrolyzable silicon-containing groups at both ends of its dimerized polymer skeleton.

[0076] The above reaction equation shows that all of the allyl groups are consumed by the reaction with the hydrolyzable silicon group-containing hydrosilane compound (D), but is not limited to this, and some of the allyl groups may remain without reacting with the hydrolyzable silicon group-containing hydrosilane compound (D). Therefore, the organic polymer (E) may have allyl groups together with the hydrolyzable silicon groups.

[0077] Hydrosilylation reactions are preferably carried out in the presence of a hydrosilylation catalyst to accelerate the reaction. Known hydrosilylation catalysts include metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium, as well as complexes thereof, and these can be used. Specifically, examples include platinum supported on a carrier such as alumina, silica, or carbon black; chloroplatinic acid; chloroplatinic acid complexes consisting of chloroplatinic acid with alcohols, aldehydes, or ketones; platinum-olefin complexes [e.g., Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2]; platinum-vinylsiloxane complexes [e.g., Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4]; platinum-phosphine complexes [e.g., Ph(PPh3)4, Pt(PBu3)4]; and platinum-phosphine complexes [e.g., Pt{P(OPh)3}4]. From the viewpoint of reaction efficiency, platinum catalysts such as chloroplatinic acid and platinum-vinylsiloxane complexes are preferred.

[0078] The hydrosilylation reaction can also be carried out in the presence of a quinone compound in addition to the hydrosilylation catalyst. The quinone compound can further enhance the acceleration of the hydrosilylation reaction by the hydrosilylation catalyst. Specific examples of quinone compounds include 1,4-benzoquinone, 2-tert-butyl-1,4-benzoquinone, tetramethylbenzoquinone, 2,5-di-tert-butyl-1,4-benzoquinone, 2,6-di-tert-butyl-1,4-benzoquinone, 1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, 2-methoxy-1,4-naphthoquinone, 9,10-anthraquinone, 1-ethylanthraquinone, and 2-(1,2-dimethylpropyl)-9,10-anthraquinone. From the viewpoint of reaction efficiency, 2,5-di-tert-butyl-1,4-benzoquinone and 2,6-di-tert-butyl-1,4-benzoquinone are preferred. Further details regarding the use of the quinone compound can be found in Japanese Patent Application Publication No. 2000-94105.

[0079] Although the hydrosilylation reaction can be carried out without a solvent, an organic solvent may be added to ensure uniform dissolution of the organic polymer (C), the hydrolyzable silicon group-containing hydrosilane compound (D), and the hydrosilylation catalyst, and to facilitate temperature control of the reaction system and addition of the hydrosilylation catalyst.

[0080] The temperature conditions for the hydrosilylation reaction are not particularly limited and can be set appropriately by those skilled in the art. However, to lower the viscosity of the reaction system and improve reactivity, the reaction is preferably carried out under heating conditions. Specifically, a reaction at 50°C to 150°C is more preferable, and a reaction at 70°C to 120°C is even more preferable. The reaction time can also be set appropriately, but it is preferable to adjust the reaction time along with the temperature conditions to prevent unintended condensation reactions between polymers. Specifically, the reaction time is preferably 30 minutes to 5 hours, and more preferably 3 hours or less.

[0081] Furthermore, the hydrosilylation reaction may be carried out in the presence of an orthocarboxylic acid trialkyl ester. This suppresses the thickening during the hydrosilylation reaction and improves the storage stability of the resulting polymer.

[0082] Examples of orthocarboxylic acid trialkyl esters include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, and triethyl orthoacetate. Trimethyl orthoformate and trimethyl orthoacetate are preferred.

[0083] When using orthocarboxylic acid trialkyl esters, the amount used is not particularly limited, but it is preferably about 0.1 to 10 parts by weight, and more preferably about 0.1 to 3 parts by weight, per 100 parts by weight of organic polymer (C).

[0084] By carrying out the hydrosilylation reaction described above, an organic polymer (E) having hydrolyzable silicon groups can be produced with fewer steps compared to conventional methods.

[0085] <Organic polymer (E) containing hydrolyzable silicon groups> The process described above can produce an organic polymer (E) having hydrolyzable silicon groups and acetal structures. The organic polymer (E) may have one or at least two acetal structures in one molecule. This organic polymer (E) is a novel polymer with a previously unreported structure and constitutes one aspect of the present invention.

[0086] Hydrolyzable silicon groups refer to silicon groups that can form siloxane bonds and bond with each other through hydrolysis and dehydration condensation. Organic polymer (E) exhibits curability based on dehydration condensation reaction due to the presence of hydrolyzable silicon groups.

[0087] A hydrolyzable silicon group can be represented, for example, by the following formula (3). -SiR 3 a X 3-a (3)

[0088] In formula (3), R 3 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, either substituted or unsubstituted. 3 If multiple hydrocarbon groups exist, they may be identical or different from one another. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. If the hydrocarbon group has substituents, the substituents are not particularly limited, but examples include halogen groups such as chloro groups, alkoxy groups such as methoxy groups, and amino groups such as N,N-diethylamino groups.

[0089] R 3Examples include unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, 2-ethylhexyl, and n-dodecyl groups; substituted alkyl groups such as chloromethyl, methoxymethyl, and N,N-diethylaminomethyl groups; unsaturated hydrocarbon groups such as vinyl, isopropenyl, and allyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl, toluyl, and 1-naphthyl groups; and aralkyl groups such as benzyl groups. Preferably, it is a substituted or unsubstituted alkyl group, more preferably a methyl, ethyl, chloromethyl, or methoxymethyl group, even more preferably a methyl or methoxymethyl group, and particularly preferably a methyl group. 3 For this purpose, only one type of group may be used, or two or more types of groups may be used in combination.

[0090] In formula (3), X represents a hydroxyl group or a hydrolyzable group. If there are multiple Xs, they may be the same or different from one another. Examples of X include hydroxyl groups, hydrogen, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups, etc. The aforementioned alkoxy groups may have substituents. Alkoxy groups are preferred because they are mildly hydrolyzable and easy to handle, methoxy groups, ethoxy groups, n-propoxy groups, and isopropoxy groups are more preferred, methoxy groups and ethoxy groups are even more preferred, and methoxy groups are particularly preferred. Only one type of group may be used as X, or two or more types of groups may be used in combination.

[0091] In formula (3), a is 0, 1, or 2. From the viewpoint of curability and the mechanical properties of the resulting cured product, a is preferably 0 or 1.

[0092] Examples of hydrolyzable silicon groups represented by formula (3) include trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, methyldimethoxysilyl group, methyldiethoxysilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, and (N,N-diethylaminomethyl)diethoxysilyl group. Among these, methyldimethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, and (N,N-diethylaminomethyl)dimethoxysilyl group are preferred. From the viewpoint of reactivity, trimethoxysilyl group, (chloromethyl)dimethoxysilyl group, and (methoxymethyl)dimethoxysilyl group are more preferred. From a stability standpoint, methyldimethoxysilyl groups and methyldiethoxysilyl groups are more preferred. Furthermore, methyldimethoxysilyl groups are more preferred because they are easy to manufacture.

[0093] The organic polymer (E) may have one hydrolyzable silicon group per molecule, but it is preferable that it has at least two hydrolyzable silicon groups per molecule.

[0094] The average number of hydrolyzable silicon groups contained in one molecule of organic polymer (E) is preferably 1.0 or more, more preferably 1.2 or more, even more preferably 1.4 or more, and particularly preferably 1.6 or more. The upper limit is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.0 or less.

[0095] The hydrolyzable silicon group may be bonded to the polymer backbone of the organic polymer (E) as a side chain, or it may be bonded to the ends of the polymer backbone. To obtain a good rubber-like cured product, it is preferable that the hydrolyzable silicon group is bonded to the ends of the polymer backbone of the organic polymer (E).

[0096] In particular, it is preferable that the organic polymer (E) has a linear polymer skeleton and has hydrolyzable silicon groups at both ends of the polymer skeleton.

[0097] The polymer skeleton of organic polymer (E) having hydrolyzable silicon groups is the same as that of organic polymer (A). Among these, polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester polymers are preferred because they have relatively low glass transition temperatures and the resulting cured products have excellent cold resistance. Polyoxyalkylene polymers are particularly preferred. However, the polymer skeleton of organic polymer (E) contains a structure derived from compound (B) internally and has an acetal structure.

[0098] The number-average molecular weight of the organic polymer (E) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and particularly preferably 10,000 or more and less than 35,000, as polystyrene-equivalent molecular weight in GPC. When the number-average molecular weight is within the above range, the cured product has excellent mechanical properties, and the amount of hydrolyzable silicon groups introduced is appropriate, making it possible to easily obtain an organic polymer (E) that exhibits good curability, has an easy-to-handle viscosity, and has excellent workability while keeping manufacturing costs within a reasonable range.

[0099] The molecular weight distribution (Mw / Mn) of the organic polymer (E) is not particularly limited, but a narrow range is preferred. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, even more preferably 1.4 or less, particularly preferably 1.3 or less, and most preferably 1.2 or less. The molecular weight distribution of the organic polymer (E) can be determined from the number-average molecular weight and weight-average molecular weight obtained by GPC measurement.

[0100] <Curable composition> The hydrolyzable silicon group-containing organic polymer (E) can constitute a major component of a curable composition that can be cured in the presence of moisture. The curable composition preferably contains a silanol condensation catalyst for the purpose of promoting the hydrolysis and condensation reaction of the hydrolyzable silicon group, i.e., the curing reaction.

[0101] Conventional silanol condensation catalysts can be used, specifically organotin compounds, metal carboxylate salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, etc.

[0102] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butylmaleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), reaction products of dibutyltin oxide and silicate compounds, reaction products of dibutyltin oxide and phthalate esters, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethylmaleate), dioctyltin bis(octylmaleate), dioctyltin bis(acetylacetonate), and reaction products of dioctyltin oxide and silicate compounds. Due to the growing environmental concerns in recent years, dioctyltin compounds are preferred.

[0103] Specific examples of metal carboxylate salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and cesium carboxylate. Various metals can be combined with the following carboxylic acids as carboxylate groups.

[0104] Specific examples of amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butyl biguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; amino group-containing silane coupling agents; and ketimine compounds.

[0105] Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

[0106] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate titanium tetrakis (acetylacetonate) and diisopropoxy titanium bis (ethylacetoacetate), aluminum compounds such as aluminum tris (acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis (acetylacetonate).

[0107] Other silanol condensation catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0108] The silanol condensation catalyst may be used in combination with two or more different catalysts. For example, combining the amine compound with a carboxylic acid or an amine compound with an alkoxy metal may improve reactivity.

[0109] The amount of silanol condensation catalyst to be added is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and particularly preferably 0.01 to 10 parts by weight, per 100 parts by weight of organic polymer (E), from the viewpoint of achieving both improved condensation reaction rate and workability during curing. Furthermore, some silanol condensation catalysts may seep out onto the surface of the cured product or contaminate the surface of the cured product after the curable composition has cured. In such cases, by using 0.01 to 3.0 parts by weight of silanol condensation catalyst, it is possible to maintain good surface condition of the cured product while ensuring curability.

[0110] (Other additives) The curable composition containing the organic polymer (E) may also contain other additives such as silicon compounds, adhesion promoters, plasticizers, solvents, diluents, silicates, fillers, anti-sagging agents, antioxidants, light stabilizers, UV absorbers, property modifiers, tackifying resins, compounds containing epoxy groups, photocurable substances, oxygen-curable substances, surface modifiers, epoxy resins, other resins, flame retardants, and foaming agents.

[0111] Furthermore, various additives may be added to the curable composition as needed for the purpose of adjusting the physical properties of the curable composition or the cured product. Examples of such additives include curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, and antifungal agents.

[0112] <Preparation of curable composition> The aforementioned curable composition can be prepared as a one-component type in which all components are pre-mixed and sealed for storage, and then cured by moisture in the air after application. Alternatively, it can be prepared as a two-component type in which components such as a silanol condensation catalyst, filler, plasticizer, and water are separately mixed as a curing agent, and these components are mixed with the organic polymer composition before use. From the viewpoint of workability, the one-component type is preferred.

[0113] When the curable composition is a one-component type, all components are pre-mixed. Therefore, it is preferable to dehydrate and dry any components containing water before use, or to dehydrate them during mixing by reducing pressure. Furthermore, storage stability can be further improved by adding alkoxysilane compounds such as n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane in addition to the dehydration and drying method.

[0114] The amount of dehydrating agent, particularly a silicon compound that can react with water such as vinyltrimethoxysilane, is preferably in the range of 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of organic polymer (E).

[0115] <Application> The curable composition can be used as an adhesive, a sealing material for buildings, ships, automobiles, roads, etc., a waterproofing material, a waterproof coating material, a molding material, a vibration damping material, a soundproofing material, a foaming material, a paint, or a spray material. The cured product obtained by curing the curable composition according to this embodiment has excellent flexibility and adhesion, and can therefore be suitably used as a sealing material or an adhesive.

[0116] The following sections list preferred embodiments of this disclosure, but the present invention is not limited to these sections. [Item 1] A method for producing an organic polymer having an allyl group, comprising the step of reacting an organic polymer (A) having an allyl group and a hydroxyl group with a compound (B) having at least two vinyl ether groups to obtain an organic polymer (C) having at least two allyl groups by forming an acetal structure through the reaction of the hydroxyl group and the vinyl ether group. [Item 2] The method for producing the compound (B) having at least two vinyl ether groups, wherein the water content of the compound is less than 1000 ppm, as described in item 1. [Item 3] The method for producing organic polymer (C) having at least two allyl groups is an organic polymer having allyl groups at both ends, as described in item 1 or 2. [Item 4] A method for producing organic polymer (A) having an allyl group and a hydroxyl group, wherein the organic polymer (A) is an organic polymer having an allyl group and a hydroxyl group at its terminal ends, as described in any of items 1 to 3. [Item 5] Compound (B) having at least two vinyl ether groups is the compound of formula (1) (wherein R 1 The method for producing a compound represented by ) according to any one of items 1 to 4. [Item 6] A manufacturing method according to any one of items 1 to 5, further comprising the step of adding a base to the reaction solution obtained after synthesizing an organic polymer (C) having at least two allyl groups by reacting an organic polymer (A) having an allyl group and a hydroxyl group with a compound (B) having at least two vinyl ether groups. [Item 7] A method for producing an organic polymer (A) and (C) having a polyoxyalkylene skeleton, according to any one of items 1 to 6. [Item 8] A method for producing a hydrolyzable silicon group-containing organic polymer (E), comprising the steps of obtaining an organic polymer (C) having at least two allyl groups by a manufacturing method described in any of items 1 to 7, and then hydrosilylating the organic polymer (C) with a hydrolyzable silicon group-containing hydrosilane compound (D) to obtain a hydrolyzable silicon group-containing organic polymer (E). [Item 9] An organic polymer (C) having an organic polymer backbone and containing at least two allyl groups and an acetal structure in one molecule. [Examples]

[0117] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0118] The number-average molecular weight in the examples is the GPC molecular weight measured under the following conditions. Liquid delivery system: Tosoh HLC-8420GPC Column: Tosoh TSKgel SuperH series Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40℃

[0119] The iodine value was measured in accordance with the provisions of JIS K 0070.

[0120] The hydroxyl value was measured in accordance with the provisions of JIS K 1557-1.

[0121] (Production of organic polymer (C)) To 100 parts by weight of polyoxypropylene glycol monoallyl ether (PK-130, manufactured by NOF Corporation, number average molecular weight 4,390, iodine value: 0.279 mmol / g, hydroxyl value: 0.321 mmol / g) as an organic polymer (A) having allyl and hydroxyl groups, 0.70 parts by weight of pyridinium p-toluenesulfonate was added as an acid catalyst. While stirring under a nitrogen atmosphere, 3.27 parts by weight of diethylene glycol divinyl ether as a compound (B) having at least two vinyl ether groups was added dropwise, and the reaction was carried out at 90°C for 3 hours to obtain a terminal allyl group-containing polyoxypropylene polymer (C). 1 1H NMR analysis confirmed that the hydroxyl groups in the starting material decreased and that an acetal structure was formed.

[0122] Next, sodium bicarbonate solution was added to make the system basic, and the mixture was thoroughly stirred. The organic layer was then extracted three times using an equal volume of toluene as the stirred solution to extract the components soluble in the organic layer. The resulting organic layer was washed once with saline solution and twice with pure water. Sodium sulfate, aluminum silicate, and Celite were added to the washed organic layer and stirred for 2 hours to perform dehydration and adsorption treatment. Impurities were removed by Celite filtration, and then the mixture was concentrated by heating under reduced pressure to remove toluene, thereby purifying the terminal allyl group-containing polyoxypropylene polymer (C). The number-average molecular weight of the terminally allyl group-containing polyoxypropylene polymer (C) was 7,894, the iodine value was 0.274 mmol / g, and the hydroxyl value was 0.060 mmol / g.

[0123] [Table 1]

[0124] (Synthesis of organic polymers (E)) To 100 parts by weight of the obtained terminal allyl group-containing polymer (C), 500 ppm of platinum vinyl disiloxane complex (a solution of isopropyl alcohol at 3% by weight in terms of platinum) was added, and while stirring, 2.59 parts by weight of methyldimethoxysilane was slowly added dropwise as a hydrolyzable silicon group-containing hydrosilane compound (D). The hydrosilylation reaction was carried out at 90°C for 30 minutes, and the unreacted dimethoxymethylsilane was removed by distillation under reduced pressure to obtain a terminal dimethoxymethylsilyl group-containing polyoxypropylene polymer (E) with a number average molecular weight of 8,455. 1 1H NMR analysis confirmed that 75% of the allyl groups (C) in the terminal allyl group-containing polymer were introduced as dimethoxymethylsilyl groups. The results are summarized in Table 2.

[0125] [Table 2]

[0126] (Measurement of the physical properties of cured materials) As shown in Table 3, the terminal silyl group-containing polyoxypropylene polymer (E) obtained above, tin(II) 2-ethylhexanoate, laurylamine, and water were mixed, degassed using a centrifuge, poured into a mold, and cured at 23°C and 50% relative humidity for 1 hour, at 70°C for 20 hours, and then again at 23°C and 50% relative humidity to prepare a cured product. The hardened material was punched into No. 3 dumbbell-shaped test specimens according to JIS K 6251. Tensile tests (tensile speed 200 m / min) were performed using the obtained specimens at 23°C and 50% relative humidity using an autograph. As a result, the stress at 100% elongation (M100) was 0.11 MPa, the stress at fracture (TB) was 0.18 MPa, and the elongation at fracture (EB) was 183%. The results are summarized in Table 3.

[0127] [Table 3]

Claims

1. A method for producing an organic polymer having an allyl group, comprising the step of reacting an organic polymer (A) having an allyl group and a hydroxyl group with a compound (B) having at least two vinyl ether groups to obtain an organic polymer (C) having at least two allyl groups by forming an acetal structure through the reaction of the hydroxyl group and the vinyl ether group.

2. The manufacturing method according to claim 1, wherein the water content of compound (B) having at least two vinyl ether groups is less than 1000 ppm.

3. The method for producing organic polymer (C) having at least two allyl groups is an organic polymer having allyl groups at both ends, according to claim 1.

4. The method for producing organic polymer (A) having an allyl group and a hydroxyl group is an organic polymer having an allyl group and a hydroxyl group at its terminal ends, according to claim 1.

5. Compound (B) having at least two vinyl ether groups is given by formula (1): 【Chemistry 1】 (In the formula, R １ (This represents an organic group having 1 to 20 carbon atoms. The organic group may contain at least one atom selected from oxygen, nitrogen, and sulfur.) The manufacturing method according to claim 1, wherein the compound is represented by [the compound name].

6. The method for producing an organic polymer (C) having at least two allyl groups, further comprising the step of adding a base to the reaction solution obtained after reacting an organic polymer (A) having an allyl group and a hydroxyl group with a compound (B) having at least two vinyl ether groups.

7. The method for producing the organic polymer (A) and (C) according to claim 1, wherein the organic polymers (A) and (C) have a polyoxyalkylene skeleton.

8. A method for producing a hydrolyzable silicon group-containing organic polymer (E), comprising the steps of obtaining an organic polymer (C) having at least two allyl groups by a manufacturing method described in any one of claims 1 to 7, and then subjecting the organic polymer (C) to a hydrosilylation reaction with a hydrolyzable silicon group-containing hydrosilane compound (D) to obtain a hydrolyzable silicon group-containing organic polymer (E).

9. An organic polymer (C) having an organic polymer backbone and containing at least two allyl groups and an acetal structure in one molecule.

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