Method for producing polymer having carbon-carbon unsaturated bond or reactive silicon group

Abstract

According to the present invention, a polymer (C) is obtained by adding a metal methoxide to a polymer (B) that has a hydroxyl group, and subsequently devolatilizing the methanol. A polymer (D) is obtained by reacting an epoxy compound (G1) that has a carbon-carbon unsaturated bond. No metal methoxide is added after the step for obtaining the polymer (D). Subsequently, a halogenated hydrocarbon compound (G2) that has a carbon-carbon unsaturated bond is reacted so as to obtain a polymer (A). The addition amount of the metal methoxide is 1.05-1.35 equivalents with respect to the hydroxyl group of the polymer (B), and the addition amount of the compound (G2) is 4.0 equivalents or less with respect to the hydroxyl group of the polymer (B). A hydrosilane compound that has a reactive silicon group may be additionally reacted with the polymer (A).

Description

Method for producing polymers having carbon-carbon unsaturated bonds or reactive silicon groups

[0001] The present invention relates to a method for producing a polymer having a carbon-carbon unsaturated bond, and a method for producing a polymer having a reactive silicon group.

[0002] Polymers containing reactive silicon groups are known as moisture-reactive polymers and are found in many industrial products such as adhesives, sealants, coatings, paints, and pressure-sensitive adhesives, and are used in a wide range of fields.

[0003] Known examples of the main chain skeleton of such polymers include polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester polymers. In particular, polyoxyalkylene polymers having reactive silicon groups have a wide range of applications due to their relatively low viscosity at room temperature and ease of handling, and the cured product obtained after the reaction also exhibits good elasticity.

[0004] One known method for producing such a polymer involves reacting a polymer having hydroxyl groups with an alkali component such as an alkali metal, potassium hydroxide, or a metal alkoxide to convert the hydroxyl groups into alkoxy groups, followed by reaction with an organic halide having a carbon-carbon double bond such as allyl chloride to obtain a polymer having a carbon-carbon double bond, which is then converted into a reactive silicon group by addition reaction with a hydrosilane (see, for example, Patent Documents 1 and 2).

[0005] Furthermore, Patent Document 3 describes that a polymer containing a structure having two or more carbon-carbon double bonds can be obtained by converting hydroxyl groups in a polymer to alkoxy groups, followed by reaction with an epoxy compound having a carbon-carbon double bond such as allyl glycidyl ether, and then reaction with an organic halide having a carbon-carbon double bond such as allyl chloride, and further describes that a polymer containing a structure having two or more reactive silicon groups can be obtained by addition reaction of the polymer with hydrosilanes.

[0006] This method can produce a polymer having two or more reactive silicon groups introduced at one end. Such reactive silicon group-containing polymers are highly advantageous in that they can achieve excellent strength and elasticity after curing.

[0007] The document describes a specific method for producing the polymer, in which 1.0 equivalent of sodium methoxide is reacted with the hydroxyl groups of the polymer, methanol is distilled off, the polymer is reacted with an epoxy compound, sodium methoxide is then added again, methanol is removed again, and the polymer is reacted with an organic halide (see Synthesis Examples 1 to 6).

[0008] JP-A-52-73998 JP-A-4-36312 International Publication No. 2013 / 180203

[0009] In Patent Document 3, in order to sufficiently react the hydroxyl groups of the polymer, sodium methoxide is added and then methanol is distilled off before the addition of the epoxy compound and before the addition of the organic halide. This production method requires repeating the same operation twice, which is extremely cumbersome in terms of production. To improve productivity, it is desirable to reduce the number of steps.

[0010] In view of the above-described current situation, a first aspect of the present invention aims to provide a method for producing a carbon-carbon unsaturated bond-containing polymer, which can introduce two or more carbon-carbon unsaturated bonds into one terminal structure of a polymer by sequentially reacting a polymer having a hydroxyl group with an epoxy compound having a carbon-carbon unsaturated bond and an organic halide having a carbon-carbon unsaturated bond, and which can efficiently introduce carbon-carbon unsaturated bonds while reducing the number of steps.

[0011] A second aspect of the present invention is a method for producing a reactive silicon group-containing polymer, which allows two or more reactive silicon groups to be introduced into one terminal structure of a polymer by sequentially reacting a polymer having a hydroxyl group with an epoxy compound having a carbon-carbon unsaturated bond and an organic halide having a carbon-carbon unsaturated bond, and then reacting the polymer with a hydrosilane compound, and the object of the present invention is to provide a production method that allows reactive silicon groups to be introduced efficiently while reducing the number of steps.

[0012] In order to reduce the number of steps in the above-mentioned production method, the present inventors attempted a process in which the addition of a metal methoxide such as sodium methoxide and the subsequent distillation off of methanol were carried out only once, and these steps were carried out before the addition of the epoxy compound but not before the addition of allyl chloride.

[0013] In this case, it was found that if the amount of metal methoxide added is equivalent to the amount of hydroxyl groups in the polymer, the reaction does not proceed sufficiently, whereas if the amount of metal methoxide added is too large relative to the amount of hydroxyl groups in the polymer, impurities derived from the metal methoxide will bleed out onto the surface of the cured product.

[0014] However, the present inventors have found that, when the amount of metal methoxide added is controlled within an appropriate range, adding the metal methoxide and then distilling off the methanol once before adding the epoxy compound can efficiently introduce carbon-carbon unsaturated bonds into the polymer and also suppress the leaching of impurities onto the surface of the cured product, which led to the present invention.

[0015] That is, the present invention relates to a method for producing a polymer (A) having a carbon-carbon unsaturated bond, comprising: step (1) of adding a metal methoxide to a polymer (B) having hydroxyl groups, and then devolatilizing the methanol to cause the metal methoxide to act on the hydroxyl groups of the polymer (B) to obtain a polymer (C); step (2) of reacting the polymer (C) with an epoxy compound (G1) having a carbon-carbon unsaturated bond to obtain a polymer (D); and step (3) of reacting the polymer (D) with a halogenated hydrocarbon compound (G2) having a carbon-carbon unsaturated bond to obtain a polymer (A), wherein the amount of the metal methoxide added in step (1) is 1.05 to 1.35 equivalents relative to the hydroxyl groups of the polymer (B); the amount of the halogenated hydrocarbon compound (G2) added in step (3) is 4.0 equivalents or less relative to the hydroxyl groups of the polymer (B); and no metal methoxide is added after step (2). The present invention also relates to a method for producing a polymer (E) having a reactive silicon group, the method comprising: producing a polymer (A) having a carbon-carbon unsaturated bond by the above-mentioned production method; and reacting the polymer (A) with a hydrosilane compound having a reactive silicon group.

[0016] According to a first aspect of the present invention, there is provided a method for producing a carbon-carbon unsaturated bond-containing polymer, which allows two or more carbon-carbon unsaturated bonds to be introduced into one terminal structure of a polymer by sequentially reacting a polymer having a hydroxyl group with an epoxy compound having a carbon-carbon unsaturated bond and an organic halide having a carbon-carbon unsaturated bond, and which allows for efficient introduction of carbon-carbon unsaturated bonds while reducing the number of steps.

[0017] According to a second aspect of the present invention, there is provided a method for producing a reactive silicon group-containing polymer, which allows two or more reactive silicon groups to be introduced into one terminal structure of a polymer by sequentially reacting a polymer having a hydroxyl group with an epoxy compound having a carbon-carbon unsaturated bond and an organic halide having a carbon-carbon unsaturated bond, and then reacting the polymer with a hydrosilane compound, thereby providing a production method that allows reactive silicon groups to be introduced efficiently while reducing the number of steps.

[0018] The production method of the present invention can achieve a relatively high introduction rate of carbon-carbon unsaturated bonds or reactive silicon groups despite the small number of steps, and does not require the use of a large amount of a halogenated hydrocarbon compound.

[0019] The reactive silicon group-containing polymer obtained by the production method according to the second aspect of the present invention can give a cured product having physical properties comparable to those of polymers produced by conventional methods, and can also suppress the exudation of impurities derived from metal methoxide onto the surface of the cured product.

[0020] Furthermore, the carbon-carbon unsaturated bond-containing polymer obtained by the production method according to the first aspect of the present invention can be used as an intermediate for producing the reactive silicon group-containing polymer.

[0021] The following describes in detail embodiments of the present invention. However, the present invention is not limited to the embodiments described below, and various modifications are possible within the scope of the claims. Furthermore, the configurations described below can be combined in any manner, and such combinations can also be an aspect of the present invention.

[0022] [First Aspect] The first aspect of the present invention relates to a method for producing a polymer (A) having a carbon-carbon unsaturated bond. First, the polymer (A) will be described.

[0023] The carbon-carbon unsaturated bond in the polymer (A) may be either a carbon-carbon double bond or a carbon-carbon triple bond, but is preferably a carbon-carbon double bond in view of ease of introduction reaction into the polymer.

[0024] The structure of the carbon-carbon double bond contained in the polymer (A) is not particularly limited, but from the viewpoint of reactivity with a hydrosilane compound described later, it is particularly preferably represented by the following formula (1): -R １ -C(R ２ ) = CH ２ (1)

[0025] In formula (1), R １represents a direct bond or a divalent hydrocarbon group having 1 to 6 carbon atoms which may have an oxygen atom. The hydrocarbon group preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and even more preferably 1 carbon atom. R １ is preferably a direct bond or a divalent hydrocarbon group having 1 to 6 carbon atoms, and ２ - or -CH ２ CH ２ - is more preferred, a direct bond or -CH ２ - is more preferred, and -CH ２ In addition, when a plurality of R groups are present in the polymer, R groups are particularly preferred. １ may be the same as or different from each other.

[0026] In formula (1), R ２ represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The aryl group preferably has 6 to 8 carbon atoms, more preferably 6 to 7 carbon atoms. The aralkyl group more preferably has 7 to 8 carbon atoms.

[0027] When the alkyl group, aryl group, or aralkyl group has a substituent, the substituent is not particularly limited, and examples of the substituent include a halogen group such as a chloro group, an alkoxy group such as a methoxy group, and an amino group such as an N,N-diethylamino group.

[0028] R ２ Specific examples of R include hydrogen, alkyl groups such as methyl, ethyl, propyl, and butyl groups, aryl groups such as phenyl groups, and aralkyl groups such as benzyl groups. In particular, hydrogen or an alkyl group is preferred, hydrogen, a methyl group, or an ethyl group is more preferred, and hydrogen or a methyl group is even more preferred. In addition, when a plurality of R exists in the polymer, ２ may be the same as or different from each other.

[0029] According to the production method of this embodiment, a structure having two or more carbon-carbon unsaturated bonds can be introduced into a polymer. Such a structure can be represented, for example, by the following formula (2). That is, the polymer (A) may contain a structure represented by the following formula (2).

[0030]

[0031] In formula (2), R １ and R ２ is the same as defined in the formula (1). ３ represents a direct bond or a divalent hydrocarbon group having 1 to 6 carbon atoms which may have an oxygen atom. The hydrocarbon group preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and even more preferably 2 carbon atoms. R ３ is -CH ２ OCH ２ -, -CH ２ O-, -CH ２ - is preferred, and -CH ２ OCH ２ - is particularly preferred. ３ may be the same as or different from each other.

[0032] In formula (2), R ４ represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The aryl group preferably has 6 to 8 carbon atoms, more preferably 6 to 7 carbon atoms. The aralkyl group more preferably has 7 to 8 carbon atoms.

[0033] When the alkyl group, aryl group, or aralkyl group has a substituent, the substituent is not particularly limited, and examples of the substituent include a halogen group such as a chloro group, an alkoxy group such as a methoxy group, and an amino group such as an N,N-diethylamino group.

[0034] R ４Specific examples of R include hydrogen, alkyl groups such as methyl, ethyl, propyl, and butyl groups, aryl groups such as phenyl groups, and aralkyl groups such as benzyl groups. In particular, hydrogen or an alkyl group is preferred, hydrogen, a methyl group, or an ethyl group is more preferred, and hydrogen or a methyl group is even more preferred. ４ may be the same as or different from each other.

[0035] In a particularly preferred embodiment of formula (2), R １ Ga-CH ２ - and R ３ Ga-CH ２ OCH ２ - and R ２ and R ４ are hydrogen atoms.

[0036] In formula (2), n is an integer of 1 or more. There is no particular upper limit, but it may be, for example, 10 or less. It is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2. However, the value of n is not limited to one value, and multiple values ​​may be mixed.

[0037] The average number of n is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. The upper limit is preferably 5 or less, and more preferably 3 or less.

[0038] The structure represented by the formula (2) may be bonded to the main chain skeleton of the polymer (A) as a side chain or may be bonded to the terminal of the main chain skeleton. When the main chain skeleton of the polymer (A) is a polyoxyalkylene-based skeleton, it is preferably bonded to the terminal of the main chain skeleton.

[0039] The average number of structures represented by formula (2) contained in one molecule of polymer (A) is preferably 0.5 or more, more preferably 1 or more, and is preferably 4 or less, more preferably 3 or less.

[0040] The type of main chain skeleton of the polymer (A) is not particularly limited, and examples thereof include saturated hydrocarbon polymers such as polyoxyalkylene polymers, ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, polybutadiene, copolymers of isoprene or butadiene with acrylonitrile, styrene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; polyester polymers; vinyl polymers such as (meth)acrylic acid ester polymers obtained by radical polymerization of (meth)acrylic acid ester monomers such as ethyl (meth)acrylate and butyl (meth)acrylate, and polymers obtained by radical polymerization of vinyl monomers such as (meth)acrylic acid monomers, vinyl acetate, acrylonitrile, and styrene; graft polymers obtained by polymerizing the aforementioned vinyl monomers; polyamide polymers; polycarbonate polymers; diallyl phthalate polymers; and other organic polymers. The above polymers may be mixed in block or graft form.

[0041] The polymer (A) may be a polymer having any one of the polymer backbones described above, or a mixture of polymers having two or more polymer backbones. The mixture may be a mixture of polymers produced separately, or a mixture of polymers produced simultaneously to obtain an arbitrary blend composition.

[0042] Among these, polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester polymers are preferred because they have a relatively low glass transition temperature and the resulting cured product has excellent cold resistance, with polyoxyalkylene polymers being particularly preferred.

[0043] The polyoxyalkylene polymer refers to a polymer having a polymer skeleton composed of oxyalkylene repeating units. The polymer skeleton may be linear or branched. The polymer skeleton is preferably composed solely of oxyalkylene repeating units, or a polymer skeleton containing, in addition to oxyalkylene repeating units, a structure derived from the initiator used during polymerization, and composed solely of these. Here, the oxyalkylene repeating unit refers to a repeating unit constituting a polyether, and is, for example, an oxyalkylene unit having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

[0044] The polyoxyalkylene polymer is not particularly limited, and examples thereof include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Polyoxypropylene polymers are particularly preferred.

[0045] The polymer backbone of the polyoxyalkylene polymer can be formed by polymerizing an epoxy compound with an initiator having a hydroxyl group by a conventionally known method, thereby obtaining a polyoxyalkylene polymer having a hydroxyl group at its terminal. Although the specific polymerization method is not particularly limited, a polymerization method using a composite metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex is preferred because it can produce a hydroxyl-terminated polymer with a narrow molecular weight distribution (Mw / Mn).

[0046] The initiator having a hydroxyl group is not particularly limited, and examples of initiators having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, low molecular weight polyoxypropylene diol, low molecular weight polyoxypropylene triol, glycerin, trimethylolpropane, triethylolethane, sorbitol, and pentaerythritol.

[0047] As the initiator having one hydroxyl group, a monohydric alcohol can be used, such as methanol, ethanol, 2-propanol, n-butanol, iso-butanol, 2-butanol, t-butanol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, oleyl alcohol, etc. Further examples include low-molecular-weight polyoxypropylene monoalkyl ethers.

[0048] The epoxy compound is not particularly limited, and examples thereof 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 alkyl glycidyl 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.

[0049] The number average molecular weight of the polymer (A), as measured by GPC in terms of polystyrene, is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and particularly preferably 10,000 or more but less than 35,000. When the number average molecular weight is within the above range, the polymer (A) can be easily obtained, having a viscosity that is easy to handle and excellent in workability, while keeping the production cost within an appropriate range.

[0050] The molecular weight distribution (Mw / Mn) of the 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. The molecular weight distribution of the polymer (A) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.

[0051] [Method for Producing Polymer (A)] The polymer (A) having a carbon-carbon unsaturated bond can be produced by sequentially carrying out at least steps (1) to (3). Each step will be described below in order.

[0052] [Step (1)] In step (1), a metal methoxide is added to a polymer (B) having hydroxyl groups, and then the methanol is volatilized off, thereby allowing the metal methoxide to react with the hydroxyl groups of the polymer (B) to obtain a polymer (C).

[0053] The main chain skeleton of the polymer (B) having a hydroxyl group is the same as that of the polymer (A). The hydroxyl group may be bonded to the terminal of the main chain skeleton of the polymer (B), or may be bonded as a side chain at a position other than the terminal. The number of hydroxyl groups possessed by the polymer (B) is not particularly limited and may be one or two or more.

[0054] The number average molecular weight of polymer (B), as polystyrene-equivalent molecular weight measured by GPC, 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. When the number average molecular weight is within the above range, polymer (B) having a viscosity that is easy to handle and excellent workability can be easily obtained, while keeping production costs within an appropriate range.

[0055] As the number-average molecular weight of polymer (B) increases, the introduction rate of carbon-carbon unsaturated bonds tends to decrease significantly if metal methoxide is not added after step (2) and the amount of metal methoxide used in step (1) is less than 1.05 equivalents relative to the hydroxyl groups of polymer (B). However, according to the production method of the present disclosure, even if the number-average molecular weight of polymer (B) is large, the introduction reaction of carbon-carbon unsaturated bonds proceeds efficiently in each of steps (2) and (3), and the introduction rate of carbon-carbon unsaturated bonds in polymer (A) can be increased. From this perspective, when the number-average molecular weight of polymer (B) is 20,000 or more, the significance of adopting the production method of the present disclosure becomes particularly great.

[0056] The hydroxyl group-containing polymer (B) can be produced by a conventional method. In particular, the method for producing the polymer (B) when the main chain skeleton is polyoxyalkylene-based is as described above.

[0057] As the metal methoxide, an alkali metal methoxide can be used. Examples of the alkali metal methoxide include sodium methoxide, potassium methoxide, lithium methoxide, and cesium methoxide. Among these, sodium methoxide and potassium methoxide are preferred, with sodium methoxide being particularly preferred, from the viewpoints of ease of handling and solubility.

[0058] The metal methoxide may be added to the polymer (B) alone or in a state of being dissolved in a solvent, which is preferably an alcohol, and particularly preferably methanol.

[0059] Before adding the metal methoxide to the polymer (B), it is preferable to remove water and substances having hydroxyl groups other than the polymer (B) from the polymer (B). This allows the reaction between the metal methoxide and the polymer (B) to proceed efficiently. For the removal, known methods can be used, such as thermal evaporation, reduced pressure devolatilization, spray evaporation, thin film evaporation, and azeotropic devolatilization.

[0060] The amount of metal methoxide added in step (1) is set to 1.05 to 1.35 equivalents relative to the hydroxyl groups in polymer (B). In this application, "equivalent" refers to a molar ratio. In this example, it is expressed as the number of moles of metal methoxide / the number of moles of hydroxyl groups in polymer (B).

[0061] By setting the amount of metal methoxide used in step (1) to 1.05 equivalents or more relative to the hydroxyl groups in polymer (B), the reactions for introducing carbon-carbon unsaturated bonds proceed efficiently in each of steps (2) and (3), even though metal methoxide is not added after step (2), and the introduction rate of carbon-carbon unsaturated bonds in polymer (A) can be increased. Furthermore, by reacting polymer (A) with a hydrosilane compound, the introduction rate of reactive silicon groups in polymer (E) can be increased.

[0062] The amount of metal methoxide used in step (1) is preferably 1.10 equivalents or more, more preferably 1.15 equivalents or more, relative to the hydroxyl groups of the polymer (B).

[0063] On the other hand, by limiting the amount of metal methoxide used in step (1) to 1.35 equivalents or less relative to the hydroxyl groups of polymer (B), it is possible to suppress the exudation of impurities derived from the metal methoxide to the surface of the cured product. The amount of metal methoxide used in step (1) is preferably 1.30 equivalents or less, and more preferably 1.25 equivalents or less.

[0064] Since the reaction between the hydroxyl groups of the polymer (B) and the metal methoxide is an equilibrium reaction that is unfavorable to the product, in this embodiment, after adding the metal methoxide to the polymer (B), a step of devolatilizing the methanol produced as a by-product is carried out, which allows the reaction between the metal methoxide and the hydroxyl groups of the polymer (B) to proceed efficiently, converting the hydroxyl groups to alkoxy groups, thereby obtaining the polymer (C) having alkoxy groups.

[0065] The method for devolatilizing methanol is not particularly limited, and may be thermal evaporation, vacuum devolatilization, spray evaporation, thin film evaporation, azeotropic devolatilization, etc. These methods may also be combined as appropriate.

[0066] The reaction temperature when reacting the metal methoxide with the polymer (B) is not particularly limited, and may be, for example, in the range of 20° C. to 150° C. The reaction time for reacting the metal methoxide with the polymer (B) is preferably 10 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0067] [Step (2)] Step (2) is the first step for introducing a carbon-carbon unsaturated bond. In this step, an epoxy compound (G1) having a carbon-carbon unsaturated bond is reacted with the polymer (C) obtained in step (1). The epoxy group of the epoxy compound (G1) reacts with the alkoxy group of the polymer (C), and an ether bond is formed by a ring-opening addition reaction of the epoxy group. This results in a polymer (D) having a carbon-carbon unsaturated bond derived from the epoxy compound (G1). The produced polymer (D) has an alkoxy group as well as a carbon-carbon unsaturated bond.

[0068] In the ring-opening addition reaction, one or more epoxy compounds (G1) can be added to one alkoxy group by adjusting the amount of the epoxy compound (G1) used and the reaction conditions.

[0069] The epoxy compound (G1) having a carbon-carbon unsaturated bond can be represented, for example, by the following formula (3).

[0070]

[0071] In formula (3), R ３ and R ４ is the same as defined in the above formula (2).

[0072] Specific examples of the epoxy compound (G1) include allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide, 1,4-cyclopentadiene monoepoxide, 1-vinyl-2,3-epoxycyclohexane, 1-vinyl-3,4-epoxycyclohexane, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, etc. In terms of reactivity, allyl glycidyl ether is particularly preferred.

[0073] The amount of epoxy compound (G1) added in step (2) can be set in consideration of the number of carbon-carbon unsaturated bonds introduced into the polymer and the reactivity. However, from the viewpoint of increasing the number of carbon-carbon unsaturated bonds introduced, the amount of epoxy compound (G1) added is preferably 0.2 equivalents or more relative to the hydroxyl groups of polymer (B). According to this embodiment, by using 0.2 equivalents or more of epoxy compound (G1), carbon-carbon unsaturated bonds can be efficiently introduced into polymer (C).

[0074] The amount of the epoxy compound (G1) added is preferably 1.0 equivalent or more, more preferably 1.2 equivalents or more, relative to the hydroxyl groups of the polymer (B), and the upper limit is preferably 5.0 equivalents or less, more preferably 3.0 equivalents or less, and even more preferably 2.0 equivalents or less.

[0075] In view of reaction efficiency, the reaction temperature when reacting the polymer (C) with the epoxy compound (G1) in step (2) is preferably from 60° C. to 150° C., more preferably from 110° C. to 140° C. The reaction time is preferably from 10 minutes to 5 hours, more preferably from 30 minutes to 3 hours.

[0076] [Step (3)] Step (3) is the second step for introducing a carbon-carbon unsaturated bond. In this step, the polymer (D) obtained in step (2) is reacted with a halogenated hydrocarbon compound (G2) having a carbon-carbon unsaturated bond. The halogenated hydrocarbon compound (G2) reacts with the alkoxy group in the polymer (D) through a halogen substitution reaction to form an ether bond, thereby introducing the carbon-carbon unsaturated bond in the halogenated hydrocarbon compound (G2) into the polymer. This allows the polymer (A) to be obtained.

[0077] In this embodiment, after step (2), a step of adding metal methoxide again is not carried out, and the halogenated hydrocarbon compound (G2) is added to the polymer (D), and then step (3) is carried out. Therefore, there is no need to carry out a step of distilling off methanol after step (2). This reduces the number of steps required to produce the polymer (A) or the polymer (E), and improves productivity.

[0078] The halogenated hydrocarbon compound (G2) having a carbon-carbon unsaturated bond can be represented, for example, by the following formula (4): Z-R １ -C(R ２ ) = CH ２ (4) In formula (4), R １ and R ２ is the same as defined in the formula (1). Z represents a halogen atom. As the halogen atom, chlorine, bromine, and iodine are preferred, and chlorine is particularly preferred.

[0079] Specific examples of the halogenated hydrocarbon compound (G2) include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Allyl chloride and methallyl chloride are preferred because of ease of handling. Furthermore, methallyl chloride, methallyl bromide, and methallyl iodide are preferred because they increase the number of reactive silicon groups introduced, as described below.

[0080] The amount of the halogenated hydrocarbon compound (G2) added in step (3) is 4.0 equivalents or less relative to the hydroxyl groups in the polymer (D). According to this embodiment, even though the amount of the halogenated hydrocarbon compound (G2) added is limited to 4.0 equivalents or less, carbon-carbon unsaturated bonds derived from (G2) can be efficiently introduced. Therefore, the amount of the halogenated hydrocarbon compound (G2) used can be reduced.

[0081] The amount of the halogenated hydrocarbon compound (G2) added is preferably 3.0 equivalents or less, more preferably 2.0 equivalents or less, relative to the hydroxyl groups of the polymer (B). From the viewpoint of increasing the number of carbon-carbon unsaturated bonds introduced from the halogenated hydrocarbon compound (G2), the lower limit is preferably 1.0 equivalent or more, more preferably 1.3 equivalents or more.

[0082] The reaction temperature when reacting the polymer (D) with the halogenated hydrocarbon compound (G2) in step (3) is preferably from 50° C. to 150° C., more preferably from 110° C. to 140° C. The reaction time is preferably from 10 minutes to 5 hours, more preferably from 30 minutes to 3 hours.

[0083] By carrying out the steps (1) to (3) described above, a polymer (A) having both a carbon-carbon unsaturated bond derived from an epoxy compound (G1) and a carbon-carbon unsaturated bond derived from a halogenated hydrocarbon compound (G2) introduced therein can be obtained with fewer steps than in conventional methods. The polymer (A) can have a structure containing multiple carbon-carbon unsaturated bonds as represented by the formula (2) above. Despite being produced with a fewer number of steps, the polymer (A) has a relatively high number of carbon-carbon unsaturated bonds introduced therein.

[0084] [Second Aspect] The second aspect of the present invention relates to a method for producing a polymer (E) having a reactive silicon group. First, the polymer (E) will be described.

[0085] The reactive silicon groups contained in the polymer (E) refer to silicon groups that can be bonded to each other by forming siloxane bonds through hydrolysis and dehydration condensation. The reactive silicon groups in the polymer (E) allow the polymer (E) to exhibit curability based on a dehydration condensation reaction.

[0086] The reactive silicon group can be represented, for example, by the following formula (5): —SiR ５ ａ X ３－ａ (5)

[0087] In formula (5), R ５ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. ５ When a plurality of groups are present, they may be the same or different. 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, still more preferably 1 to 3, and particularly preferably 1 or 2. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include a halogen group such as a chloro group, an alkoxy group such as a methoxy group, and an amino group such as an N,N-diethylamino group.

[0088] R ５Examples of R include unsubstituted alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, 2-ethylhexyl, and n-dodecyl; substituted alkyl groups such as chloromethyl, methoxymethyl, and N,N-diethylaminomethyl; unsaturated hydrocarbon groups such as vinyl, isopropenyl, and allyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, toluoyl, and 1-naphthyl; and aralkyl groups such as benzyl. Preferred are substituted or unsubstituted alkyl groups, more preferably methyl, ethyl, chloromethyl, and methoxymethyl groups, even more preferably methyl and methoxymethyl groups, and particularly preferably methyl. ５ As the alkyl group, only one type of group may be used, or two or more types of groups may be used in combination.

[0089] In formula (5), X represents a hydroxyl group or a hydrolyzable group. When multiple Xs are present, they may be the same or different. Examples of X include a hydroxyl group, hydrogen, halogen, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. The alkoxy group and the like may have a substituent. Because of their mild hydrolysis and ease of handling, an alkoxy group is preferred, a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group are more preferred, a methoxy group and an ethoxy group are even more preferred, and a methoxy group is particularly preferred. As X, only one type of group may be used, or two or more types of groups may be used in combination.

[0090] In formula (5), 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.

[0091] Examples of the reactive silicon group represented by formula (5) include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, a methyldimethoxysilyl group, a methyldiethoxysilyl group, a dimethoxyethylsilyl group, a (chloromethyl)dimethoxysilyl group, a (chloromethyl)diethoxysilyl group, a (methoxymethyl)dimethoxysilyl group, a (methoxymethyl)diethoxysilyl group, an (N,N-diethylaminomethyl)dimethoxysilyl group, and an (N,N-diethylaminomethyl)diethoxysilyl group. Among these, a methyldimethoxysilyl group, a (chloromethyl)dimethoxysilyl group, a (methoxymethyl)dimethoxysilyl group, a (methoxymethyl)diethoxysilyl group, and an (N,N-diethylaminomethyl)dimethoxysilyl group are preferred. From the viewpoint of reactivity, a trimethoxysilyl group, a (chloromethyl)dimethoxysilyl group, and a (methoxymethyl)dimethoxysilyl group are more preferred. From the viewpoint of stability, methyldimethoxysilyl group and methyldiethoxysilyl group are more preferred, and methyldimethoxysilyl group is more preferred because it is easy to produce.

[0092] According to the production method of this embodiment, a structure having two or more reactive silicon groups can be introduced into a polymer. Such a structure can be represented, for example, by the following formula (6). That is, the polymer (E) may contain a structure represented by the following formula (6).

[0093]

[0094] In formula (6), R １ and R ２ is the same as defined in the formula (1). ３ , R ４ , and n are the same as defined in the formula (2). ５ , X, and a are the same as defined in formula (5).

[0095] The structure represented by the formula (6) may be bonded to the main chain skeleton of the polymer (E) as a side chain or may be bonded to the terminal of the main chain skeleton. When the main chain skeleton of the polymer (E) is a polyoxyalkylene-based skeleton, it is preferably bonded to the terminal of the main chain skeleton.

[0096] The average number of structures represented by formula (6) contained in one molecule of polymer (E) is preferably 0.5 or more, more preferably 1 or more, and is preferably 4 or less, more preferably 3 or less.

[0097] The main chain skeleton of the polymer (E) having a reactive silicon group is the same as that of the polymer (A). Among them, polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester polymers are preferred because they have a relatively low glass transition temperature and the resulting cured product has excellent cold resistance. Polyoxyalkylene polymers are particularly preferred.

[0098] The number average molecular weight of polymer (E), as measured by GPC in terms of polystyrene, 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. When the number average molecular weight is within the above range, polymer (E) having a viscosity that is easy to handle and excellent workability can be easily obtained, while keeping production costs within an appropriate range.

[0099] The molecular weight distribution (Mw / Mn) of the polymer (E) 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. The molecular weight distribution of the polymer (E) can be determined from the number average molecular weight and weight average molecular weight obtained by GPC measurement.

[0100] [Method for Producing Polymer (E)] The polymer (E) having a reactive silicon group can be produced by producing the polymer (A) having a carbon-carbon unsaturated bond by sequentially carrying out the above-mentioned steps (1) to (3), and then subjecting the polymer (A) to a hydrosilylation reaction with the hydrosilane compound (H) having a reactive silicon group.

[0101] Specific examples of the hydrosilane compound (H) having a reactive silicon group 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, and diethoxymethylsilane; Silane, 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-trifluoromethyl)silane (chloropropyl)dimethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyloxy]dimethylsilane, [(chloromethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(methoxymethyl)diethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane, [(3,3,3-trifluoromethyl)dimethoxysilyloxy]dimethylsilane alkoxysilanes such as (chloromethyl)diisopropenyloxy]dimethylsilane; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane; and isopropenyloxysilanes (deacetone type) such as triisopropenyloxysilane, (chloromethyl)diisopropenyloxysilane, and (methoxymethyl)diisopropenyloxysilane.

[0102] The amount of the hydrosilane compound (H) having a reactive silicon group used can be appropriately determined taking into consideration the number of carbon-carbon unsaturated bonds in the polymer (A) and the desired number of reactive silicon groups to be introduced.

[0103] The hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst to promote 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. Specific examples of the hydrosilylation catalyst include platinum supported on a support such as alumina, silica, or carbon black; chloroplatinic acid; chloroplatinic acid complexes composed of chloroplatinic acid and alcohols, aldehydes, ketones, or the like; platinum-olefin complexes [e.g., Pt(CH ２ =CH ２ ) ２ (PPh ３ ), Pt(CH ２ =CH ２ ) ２ Cl ２ ]; platinum-vinylsiloxane complexes [e.g., Pt{(vinyl)Me ２ SiOSiMe ２ (vinyl)}, Pt{Me(vinyl)SiO} ４ platinum-phosphine complexes [e.g., Ph(PPh ３ ) ４ , Pt(PBu ３ ) ４ ]; platinum-phosphite complexes [e.g., Pt{P(OPh) ３} ４ In terms of reaction efficiency, platinum catalysts such as chloroplatinic acid and platinum vinylsiloxane complexes are preferred.

[0104] 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 promotion 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. Details of the use of the quinone compounds can be found in JP-A-2000-94105.

[0105] The hydrosilylation reaction can be carried out without using a solvent; however, the reaction may be carried out with the addition of an organic solvent in order to uniformly dissolve the polymer (A), the hydrosilane compound (H), and the hydrosilylation catalyst, and to easily control the temperature of the reaction system and add the hydrosilylation catalyst.

[0106] The temperature conditions for the hydrosilylation reaction are not particularly limited and can be set appropriately by a person skilled in the art. However, for the purpose of reducing the viscosity of the reaction system and improving reactivity, the reaction is preferably carried out under heated conditions. Specifically, the reaction is more preferably carried out at 50°C to 150°C, and even more preferably at 70°C to 120°C. The reaction time may also be set appropriately, but it is preferable to adjust the reaction time together with the temperature conditions so as not to allow an unintended condensation reaction between polymers to proceed. Specifically, the reaction time is preferably from 30 minutes to 5 hours, and more preferably 3 hours or less.

[0107] The hydrosilylation reaction may also be carried out in the presence of a trialkyl orthocarboxylic acid ester, which can suppress thickening during the hydrosilylation reaction and improve the storage stability of the resulting polymer.

[0108] Examples of the orthocarboxylic acid trialkyl ester include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, etc. Preferred are trimethyl orthoformate and trimethyl orthoacetate.

[0109] When a trialkyl orthocarboxylic acid ester is used, the amount used is not particularly limited, but is preferably about 0.1 to 10 parts by weight, more preferably about 0.1 to 3 parts by weight, per 100 parts by weight of polymer (A).

[0110] By carrying out the hydrosilylation reaction described above, polymer (E) having a structure containing multiple reactive silicon groups as represented by formula (6) can be obtained with fewer steps than conventional methods. Despite being produced with fewer steps, polymer (E) has a relatively high number of reactive silicon groups introduced, and can provide a cured product with physical properties comparable to those of polymers produced by conventional methods. In addition, it is possible to suppress the seepage of impurities derived from metal methoxide onto the surface of the cured product.

[0111] <Curable Composition> The polymer (E) having reactive silicon groups can constitute the main 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 reactive silicon groups, i.e., the curing reaction.

[0112] As the silanol condensation catalyst, any known catalyst can be used, and specifically, an organic tin compound, a metal carboxylate, an amine compound, a carboxylic acid, an alkoxy metal, an inorganic acid, etc. can be used.

[0113] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), a reaction product of dibutyltin oxide with a silicate compound, a reaction product of dibutyltin oxide with a phthalate ester, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate), a reaction product of dioctyltin oxide with a silicate compound, etc. In view of the growing concern about the environment in recent years, dioctyltin compounds are preferred.

[0114] Specific examples of metal carboxylates include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, cesium carboxylate, etc. The carboxylic acid group can be a combination of the following carboxylic acids with various metals.

[0115] Specific examples of the amine compound 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 butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; amino group-containing silane coupling agents; and ketimine compounds.

[0116] 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.

[0117] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate titanium tetrakis(acetylacetonate) and diisopropoxytitanium bis(ethylacetoacetate), aluminum compounds such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis(acetylacetonate).

[0118] Other silanol condensation catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0119] The silanol condensation catalyst may be a combination of two or more different catalysts. For example, the combination of the above-mentioned amine compound and carboxylic acid, or the combination of an amine compound and an alkoxy metal may provide an effect of improving reactivity.

[0120] 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 polymer (E), from the viewpoint of achieving both an improved condensation reaction rate and workability during curing. Furthermore, some silanol condensation catalysts may ooze onto the surface of the cured product after the curable composition has cured, or may contaminate the surface of the cured product. In such cases, by using 0.01 to 3.0 parts by weight of the silanol condensation catalyst, it is possible to maintain good surface condition of the cured product while ensuring curability.

[0121] (Other Additives) The curable composition containing the polymer (E) may contain other additives, such as a silicon compound, an adhesion promoter, a plasticizer, a solvent, a diluent, a silicate, a filler, an anti-sagging agent, an antioxidant, a light stabilizer, an ultraviolet absorber, a physical property adjuster, a tackifying resin, a compound containing an epoxy group, a photocurable substance, an oxygen-curable substance, a surface property improver, an epoxy resin, other resins, a flame retardant, or a foaming agent.

[0122] Furthermore, various additives may be added to the curable composition as needed for the purpose of adjusting various physical properties of the curable composition or the cured product, such as a curability adjuster, a radical inhibitor, a metal deactivator, an antiozonant, a phosphorus-based peroxide decomposer, a lubricant, a pigment, and a fungicide.

[0123] <<Preparation of Curable Composition>> The curable composition can be prepared as a one-component type in which all of the ingredients are mixed in advance and stored in a sealed container, and then cured by moisture in the air after application, or as a two-component type in which ingredients such as a silanol condensation catalyst, a filler, a plasticizer, and water are separately mixed as a curing agent, and then the ingredients and the organic polymer composition are mixed before use. From the viewpoint of workability, the one-component type is preferred.

[0124] When the curable composition is a one-component type, all of the components are blended in advance, and therefore, it is preferable to dehydrate and dry the components containing water before use, or to dehydrate them under reduced pressure during blending and kneading. In addition to the dehydration and drying method, the storage stability can be further improved by adding an alkoxysilane compound such as n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, or γ-glycidoxypropyltrimethoxysilane.

[0125] The amount of the dehydrating agent, particularly a silicon compound capable of reacting with water such as vinyltrimethoxysilane, used is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymer (E).

[0126] <Applications> The curable composition can be used as a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a waterproofing material, a waterproof coating material, a mold release agent, an anti-vibration material, a vibration-damping material, a sound-proofing material, a foam material, a paint, or a spray material. The cured product obtained by curing the curable composition according to this embodiment has excellent flexibility and adhesiveness, and therefore can be suitably used as a sealant or adhesive.

[0127] The following items are preferred embodiments of the present disclosure, but the present invention is not limited to them. [Item 1] A method for producing a polymer (A) having a carbon-carbon unsaturated bond, comprising: step (1) of adding a metal methoxide to a polymer (B) having hydroxyl groups, and then devolatilizing the methanol to cause the metal methoxide to act on the hydroxyl groups of the polymer (B) to obtain a polymer (C); step (2) of reacting the polymer (C) with an epoxy compound (G1) having a carbon-carbon unsaturated bond to obtain a polymer (D); and step (3) of reacting the polymer (D) with a halogenated hydrocarbon compound (G2) having a carbon-carbon unsaturated bond to obtain a polymer (A), wherein the amount of the metal methoxide added in step (1) is 1.05 to 1.35 equivalents relative to the hydroxyl groups of the polymer (B), and the amount of the halogenated hydrocarbon compound (G2) added in step (3) is 4.0 equivalents or less relative to the hydroxyl groups of the polymer (B), and wherein no metal methoxide is added after step (2). [Item 2] A method for producing polymer (A) according to item 1, wherein the amount of epoxy compound (G1) added in step (2) is 0.2 equivalents or more relative to the hydroxyl groups of polymer (B). [Item 3] A method for producing polymer (A) according to item 1 or 2, wherein the amount of epoxy compound (G1) added in step (2) is 1.0 equivalents or more and 3.0 equivalents or less relative to the hydroxyl groups of polymer (B). [Item 4] A method for producing polymer (A) according to any of items 1 to 3, wherein the reaction temperature when reacting polymer (C) with epoxy compound (G1) in step (2) is 60 to 150°C. [Item 5] A method for producing polymer (A) according to any of items 1 to 4, wherein the amount of halogenated hydrocarbon compound (G2) added in step (3) is 1.0 equivalents or more relative to the hydroxyl groups of polymer (B). [Item 6] The method for producing polymer (A) according to any one of items 1 to 5, wherein the reaction temperature when polymer (D) is reacted with halogenated hydrocarbon compound (G2) in step (3) is 50 to 150° C. [Item 7] The carbon-carbon unsaturated bond is represented by the following formula (1): -R １ -C(R ２ ) = CH ２ (1) (wherein, R １represents a direct bond or a divalent hydrocarbon group having 1 to 6 carbon atoms which may have an oxygen atom; R ２ represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms. [Item 8] A method for producing polymer (A) according to any one of items 1 to 7, wherein polymer (A) has a polyoxyalkylene main chain skeleton. [Item 9] A method for producing polymer (A) according to any one of items 1 to 8, wherein polymer (A) has a number average molecular weight of 10,000 or more and less than 35,000. [Item 10] A method for producing polymer (E) having a reactive silicon group, comprising: a step of producing polymer (A) having a carbon-carbon unsaturated bond by the production method according to any one of items 1 to 9; and a step of reacting polymer (A) with a hydrosilane compound having a reactive silicon group.

[0128] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0129] The number average molecular weight is a GPC molecular weight measured under the following conditions: Solution delivery system: HLC-8420GPC manufactured by Tosoh Corporation Column: TSKgel Super H series manufactured by Tosoh Corporation Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40°C

[0130] The reaction rate of the terminal hydroxyl groups of polymer (B) was calculated using the total number of terminal hydroxyl groups contained in polymer (B) and the total number of terminal hydroxyl groups contained in polymer (A) according to the following formula: (number of terminal hydroxyl groups of polymer (B) - number of terminal hydroxyl groups of polymer (A)) / number of terminal hydroxyl groups of polymer (B). Note that the "number of terminal hydroxyl groups" mentioned above all means the number of terminal hydroxyl groups in a unit weight of polymer.

[0131] Example 1 Using polyoxypropylene glycol having a number-average molecular weight of approximately 3,000 as an initiator, propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (B-1) having a number-average molecular weight of 26,400 and hydroxyl groups at both ends. Subsequently, 1.20 molar equivalents of sodium methoxide were added as a 28% methanol solution relative to the hydroxyl groups of this hydroxyl-terminated polyoxypropylene (B-1). Methanol was distilled off at 140°C by vacuum devolatilization to obtain polymer (C), and then 1.30 molar equivalents of allyl glycidyl ether relative to the hydroxyl groups of polymer (B-1) was added to polymer (C) and the reaction was continued at 140°C for 2 hours to obtain polymer (D). Subsequently, 1.60 molar equivalents of allyl chloride relative to the hydroxyl groups of polymer (B-1) were added to polymer (D) at 130°C to convert the terminal hydroxyl groups to allyl groups, resulting in polymer (A). Unreacted allyl chloride was removed by devolatilization under reduced pressure. 100 parts by weight of the resulting unpurified allyl group-terminated polyoxypropylene was mixed and stirred with 300 parts by weight of n-hexane and 300 parts by weight of water, and the mixture was then centrifuged to remove the water. 300 parts by weight of water was then added to the resulting hexane solution and mixed and stirred, and the water was again removed by centrifugation, after which the hexane was removed by devolatilization under reduced pressure. This yielded polyoxypropylene (A-1) having a number average molecular weight of approximately 26,700 and containing polymer molecules having two or more carbon-carbon unsaturated bonds in one terminal structure.

[0132] Comparative Example 1 To the hydroxyl-terminated polyoxypropylene (B-1) obtained in Example 1, 1.02 molar equivalents of sodium methoxide were added as a 28% methanol solution relative to the hydroxyl groups. After distilling off the methanol by vacuum devolatilization at 140°C, 1.80 molar equivalents of allyl glycidyl ether relative to the hydroxyl groups of the polymer (B-1) was added, and the reaction was carried out at 140°C for 2 hours. Subsequently, 1.50 molar equivalents of allyl chloride were added at 130°C to convert the terminal hydroxyl groups to allyl groups. Unreacted allyl chloride was removed by devolatilization under reduced pressure. The purification procedure was then the same as in Example 1. As a result, polyoxypropylene (A-2) was obtained, which contained polymer molecules having two or more carbon-carbon unsaturated bonds in one terminal structure and had a number-average molecular weight of approximately 27,000.

[0133] Reference Example 1: To the hydroxyl-terminated polyoxypropylene (B-1) obtained in Example 1, 1.02 molar equivalents of sodium methoxide were added as a 28% methanol solution relative to the hydroxyl groups. After distilling off the methanol by vacuum devolatilization at 140°C, 1.10 molar equivalents of allyl glycidyl ether relative to the hydroxyl groups of the polymer (B-1) were added, and the reaction was carried out at 140°C for 2 hours. Subsequently, 1.10 molar equivalents of allyl chloride were added at 130°C to convert the terminal hydroxyl groups to allyl groups. Furthermore, 0.28 molar equivalents of a methanol solution of sodium methoxide was added, and the methanol was removed at 130°C. Subsequently, 0.80 molar equivalents of allyl chloride were added at 130°C to convert the remaining terminal hydroxyl groups to allyl groups. The purification procedure was then the same as in Example 1. As a result, polyoxypropylene (A-3) was obtained, which contained polymer molecules having two or more carbon-carbon unsaturated bonds in one terminal structure and had a number-average molecular weight of approximately 26,900.

[0134] For the carbon-carbon unsaturated bond polymers (A-1) to (A-3) obtained as above, the reaction rates of the terminal hydroxyl groups were calculated by the above-mentioned method using the raw material hydroxyl group-containing polymer (B-1) as the standard, and the results are shown in Table 1.

[0135]

[0136] The results shown in Table 1 show that when the amount of metal methoxide added in step (1) is within the range of 1.05 to 1.35 equivalents relative to the hydroxyl groups of polymer (B), carbon-carbon unsaturated bonds can be efficiently introduced without adding metal methoxide after step (2). A comparison of Example 1 and Reference Example 1 shows that by employing the production method according to the present disclosure, it is possible to achieve an introduction rate of carbon-carbon unsaturated bonds similar to that achieved by the conventional two-stage production method (Reference Example 1).

[0137] Example 2 To 300 g of the polymer (A-1) obtained in Example 1, 0.03 g of a platinum divinyldisiloxane complex (a 2-propanol solution containing 3% by weight of platinum) was added, and 6.75 g of dimethoxymethylsilane was slowly added dropwise while stirring. The resulting mixture was reacted at 90°C for 2 hours, and then the unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain a reactive silicon group-containing polyoxypropylene (E-1) having an average of 1.8 dimethoxymethylsilyl groups at its terminals and a number-average molecular weight of approximately 27,800.

[0138] (Comparative Example 2) To 450 g of the polymer (A-2) obtained in Comparative Example 1, 0.05 g of platinum divinyldisiloxane complex (a 3 wt% 2-propanol solution calculated as platinum) was added, and 10.17 g of dimethoxymethylsilane was slowly added dropwise while stirring. The resulting mixture was reacted at 90°C for 2 hours, and the unreacted dimethoxymethylsilane was then distilled off under reduced pressure to obtain a reactive silicon-containing polyoxypropylene (E-2) having an average of 2.0 dimethoxymethylsilyl groups at the terminals and a number-average molecular weight of approximately 27,800. Note that in Comparative Examples 1 and 2, the amounts of allyl glycidyl ether, allyl chloride, or dimethoxymethylsilane added differ from those in Examples 1 and 2; this is a measure to ensure that the stress at 100% elongation values ​​described below are comparable.

[0139] (Reference Example 2) To 450 g of the polymer (A-3) obtained in Reference Example 1, 0.05 g of a platinum divinyldisiloxane complex (a 3 wt% 2-propanol solution calculated as platinum) was added, and 8.46 g of dimethoxymethylsilane was slowly added dropwise while stirring. The resulting mixture was reacted at 90°C for 2 hours, and the unreacted dimethoxymethylsilane was then distilled off under reduced pressure to obtain a reactive silicon-containing polyoxypropylene (E-3) having an average of 1.7 dimethoxymethylsilyl groups at the terminals and a number-average molecular weight of approximately 27,900. Note that in Reference Examples 1 and 2, the amounts of allyl glycidyl ether, allyl chloride, or dimethoxymethylsilane added differ from those in Examples 1 and 2, but this is a measure to ensure that the stress at 100% elongation values ​​described below are comparable.

[0140] The following evaluations were performed using each of the polymers (E-1) to (E-3) produced in each Synthesis Example. <Method for Evaluating Composition Properties> Among the various additives shown below, a plasticizer, a filler, titanium oxide, an anti-sagging agent, a light stabilizer, and an ultraviolet absorber were thoroughly mixed and kneaded, and then the mixture was dispersed by passing through a three-roll paint roller. Thereafter, the mixture was subjected to vacuum dehydration at 120°C for 2 hours using a planetary mixer. After cooling to 50°C or below, a dehydrating agent was added and kneaded in a state substantially free of moisture. After vacuum degassing, the mixture was sealed in a moisture-proof cartridge to obtain a masterbatch composition. Then, each of the polymers (E-1) to (E-3), an adhesion promoter, and a silanol condensation catalyst were added to the masterbatch composition and thoroughly mixed, followed by uniform kneading and degassing using a planetary mixer to prepare each curable composition. Using each of the prepared curable compositions, various test specimens were prepared in a constant temperature and humidity atmosphere of 23°C and 50% relative humidity, and various evaluations were performed.

[0141] (Various additives used in evaluation of composition properties) The following additives were used in evaluation of the composition properties of all Examples and Comparative Examples. The blending amounts are in parts by weight per 100 parts by weight of each of the polymers (E-1) to (E-3) which are the base polymers. Plasticizer: diisononyl phthalate (DINP, manufactured by J-Plus Corporation), 90 parts by weight Filler: (i) fatty acid-treated precipitated calcium carbonate (Shiraenka CCR, manufactured by Shiraishi Kogyo Co., Ltd.), 160 parts by weight (ii) heavy calcium carbonate (Whiten SB Red, manufactured by Shiraishi Calcium Co., Ltd.), 54 parts by weight Titanium oxide: Tipaque R-820, manufactured by Ishihara Sangyo Kaisha, Ltd., 5 parts by weight Anti-sagging agent: fatty acid amide wax (Disparlon #6500, manufactured by Kusumoto Chemicals Co., Ltd.), 2 parts by weight Light stabilizer: bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin 770, manufactured by BASF), 1 part by weight UV absorber: 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol (Tinuvin 326, manufactured by BASF), 1 part by weight Dehydrating agent: vinyltrimethoxysilane (A-171, manufactured by Momentive Co., Ltd.), 2 parts by weight Adhesion promoter: 3-(N-2-aminoethylamino)propyltrimethoxysilane (A-1120, manufactured by Momentive Co., Ltd.), 3 parts by weight Silanol condensation catalyst: dibutyltin bis(acetoacetate) (U-220H, manufactured by Nitto Kasei Co., Ltd.), 2 parts by weight

[0142] (Dumbbell Properties) The curable composition was filled into a 3 mm thick sheet mold at 23°C and 50% relative humidity. After curing for 3 days at 23°C and 50% relative humidity, the composition was aged in a dryer at 50°C for 4 days to obtain a sheet-like cured product. The resulting cured product was punched into a No. 3 dumbbell-shaped test piece in accordance with JIS K 6251. Using the resulting test piece, a tensile test (tensile speed: 200 mm / min) was performed using an autograph at 23°C and 50% relative humidity to measure the stress at 100% elongation, stress at break, and elongation at break. The results are shown in Table 2.

[0143] (Tear Properties) The curable composition was filled into a 3 mm thick sheet mold at 23°C and 50% relative humidity. After curing for 3 days at 23°C and 50% relative humidity, the composition was aged in a dryer at 50°C for 4 days to obtain a sheet-like cured product. The resulting cured product was punched into a dumbbell shape (JIS Type A) for tear testing to obtain a test piece. Using the resulting test piece, a tear test (tensile speed 200 mm / min) was performed using an autograph at 23°C and 50% relative humidity to measure the stress at break. The results are shown in Table 2.

[0144] (Exudation of impurities onto the surface of the composition) The surface condition of the sheet-like cured product after curing was visually inspected to check for exudation of liquid components onto the surface of the composition. The results are shown in Table 2.

[0145]

[0146] In Example 2, the addition of sodium methoxide and the removal of methanol were carried out only once before the addition of the epoxy compound (G1), and the amount of sodium methoxide added was within the range of 1.05 to 1.35 equivalents relative to the hydroxyl groups of the polymer (B).

[0147] In Comparative Example 2, the addition of sodium methoxide and the removal of methanol were carried out only once before the addition of the epoxy compound (G1) as in Example 2, but the amount of sodium methoxide added was 1.02 equivalents relative to the hydroxyl groups of the polymer (B).

[0148] In Reference Example 2, as in the conventional method, the addition of sodium methoxide and the removal of methanol were carried out before the addition of the epoxy compound (G1) and before the addition of the halogenated hydrocarbon compound (G2), respectively. This example has a greater number of steps in the production process than Example 2 and Comparative Example 2, which is disadvantageous in terms of productivity.

[0149] The following can be seen from Table 2: In Comparative Example 2, the reaction rate of the terminal hydroxyl groups of the polymer (B) was significantly lower than in Reference Example 2. Furthermore, with regard to the physical properties of the cured product obtained by curing the curable composition containing the reactive silicon group-containing polymer (E), the stress at 100% elongation was similar, but the elongation at break and tear properties were lower than in Reference Example 2.

[0150] In contrast, the reaction rate of the terminal hydroxyl groups of the polymer (B) in Example 2 was higher than that in Comparative Example 2. Furthermore, with regard to the elongation at break and tear properties, although the stress at 100% elongation was similar, the elongation at break and tear properties were improved compared to Comparative Example 2 and were at the same level as Reference Example 2.

[0151] From the above, it can be seen that Example 2 has fewer steps than Reference Example 2 and is therefore advantageous in terms of production, and that the physical properties of the cured product obtained by curing the curable composition containing the reactive silicon group-containing polymer (E) are comparable to those of Reference Example 2.

[0152] Example 3 Using polyoxypropylene triol having a number average molecular weight of approximately 4,000 as an initiator, propylene oxide was polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (B-2) having a number average molecular weight of 16,000 and hydroxyl groups at each end. Subsequently, 1.30 molar equivalents of sodium methoxide were added as a 28% methanol solution relative to the hydroxyl groups of this hydroxyl-terminated polyoxypropylene (B-2). Methanol was distilled off at 140°C by vacuum devolatilization to obtain polymer (C), and then 0.60 molar equivalents of allyl glycidyl ether relative to the hydroxyl groups of polymer (B-2) was added to polymer (C) and the reaction was carried out at 140°C for 2 hours to obtain polymer (D). Subsequently, 1.50 molar equivalents of allyl chloride relative to the hydroxyl groups of polymer (B-2) were added to polymer (D) at 130°C to convert the terminal hydroxyl groups to allyl groups, resulting in polymer (A). Unreacted allyl chloride was removed by devolatilization under reduced pressure. 100 parts by weight of the resulting unpurified allyl group-terminated polyoxypropylene was mixed and stirred with 300 parts by weight of n-hexane and 300 parts by weight of water, and the mixture was then centrifuged to remove the water. 300 parts by weight of water was then mixed and stirred with the resulting hexane solution, and the water was again removed by centrifugation, after which the hexane was then removed by devolatilization under reduced pressure. This yielded polyoxypropylene (A-4) having a number average molecular weight of approximately 16,500 and containing polymer molecules having two or more carbon-carbon unsaturated bonds in one terminal structure.

[0153] Comparative Example 3 The same procedure as in Example 3 was carried out, except that the amount of sodium methoxide used was changed from 1.30 molar equivalents to 1.00 molar equivalents relative to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene (B-2), to obtain polyoxypropylene (A-5) having a number-average molecular weight of about 16,500 and containing polymer molecules having two or more carbon-carbon unsaturated bonds in one terminal structure.

[0154] Example 4 Using polyoxypropylene triol having a number average molecular weight of approximately 4,000 as an initiator, propylene oxide was polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (B-3) having a number average molecular weight of 30,500 and hydroxyl groups at each end. Subsequently, 1.15 molar equivalents of sodium methoxide were added as a 28% methanol solution relative to the hydroxyl groups of this hydroxyl-terminated polyoxypropylene (B-3). Methanol was distilled off at 140°C by vacuum devolatilization to obtain polymer (C), and then 0.70 molar equivalents of allyl glycidyl ether relative to the hydroxyl groups of polymer (B-3) was added to polymer (C) and the reaction was carried out at 140°C for 2 hours to obtain polymer (D). Subsequently, 1.50 molar equivalents of allyl chloride relative to the hydroxyl groups of polymer (B-3) were added to polymer (D) at 130°C to convert the terminal hydroxyl groups to allyl groups, resulting in polymer (A). Unreacted allyl chloride was removed by devolatilization under reduced pressure. 100 parts by weight of the resulting unpurified allyl group-terminated polyoxypropylene were mixed and stirred with 300 parts by weight of n-hexane and 300 parts by weight of water, and the mixture was then centrifuged to remove the water. 300 parts by weight of water was then mixed and stirred with the resulting hexane solution, and the water was again removed by centrifugation, after which the hexane was then removed by devolatilization under reduced pressure. This yielded polyoxypropylene (A-6) having a number average molecular weight of approximately 31,000 and containing polymer molecules having two or more carbon-carbon unsaturated bonds in one terminal structure.

[0155] Example 5 The same procedure as in Example 4 was carried out, except that the amount of sodium methoxide used was changed from 1.15 molar equivalents to 1.05 molar equivalents relative to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene (B-3), to obtain polyoxypropylene (A-7) having a number-average molecular weight of approximately 31,000 and containing polymer molecules having two or more carbon-carbon unsaturated bonds in one terminal structure.

[0156] Comparative Example 4 The same procedure as in Example 4 was carried out, except that the amount of sodium methoxide used was changed from 1.15 molar equivalents to 0.95 molar equivalents relative to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene (B-3), to obtain polyoxypropylene (A-8) having a number-average molecular weight of about 31,000 and containing polymer molecules having two or more carbon-carbon unsaturated bonds in one terminal structure.

[0157] Example 6 Using polyoxypropylene glycol having a number average molecular weight of approximately 3,000 as an initiator, propylene oxide was polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (B-4) having a number average molecular weight of 20,500 and hydroxyl groups at both ends. Subsequently, 1.30 molar equivalents of sodium methoxide were added as a 28% methanol solution relative to the hydroxyl groups of this hydroxyl-terminated polyoxypropylene (B-4). Methanol was distilled off by vacuum devolatilization at 140°C to obtain polymer (C), and then 0.30 molar equivalents of allyl glycidyl ether relative to the hydroxyl groups of polymer (B-3) was added to polymer (C) and the reaction was carried out at 140°C for 2 hours to obtain polymer (D). Subsequently, 1.90 molar equivalents of allyl chloride relative to the hydroxyl groups of polymer (B-4) were added to polymer (D) at 130°C to convert the terminal hydroxyl groups to allyl groups, resulting in polymer (A). Unreacted allyl chloride was removed by devolatilization under reduced pressure. 100 parts by weight of the resulting unpurified allyl group-terminated polyoxypropylene were mixed and stirred with 300 parts by weight of n-hexane and 300 parts by weight of water, and the mixture was then centrifuged to remove the water. 300 parts by weight of water was then mixed and stirred with the resulting hexane solution, and the water was again removed by centrifugation, after which the hexane was then removed by devolatilization under reduced pressure. This yielded polyoxypropylene (A-9) having a number average molecular weight of approximately 20,800 and containing polymer molecules having two or more carbon-carbon unsaturated bonds in one terminal structure.

[0158] Comparative Example 5 The same procedure as in Example 6 was carried out, except that the amount of sodium methoxide used was changed from 1.30 molar equivalents to 1.00 molar equivalents relative to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene (B-4), to obtain polyoxypropylene (A-10) having a number average molecular weight of about 20,800 and containing polymer molecules having two or more carbon-carbon unsaturated bonds in one terminal structure.

[0159] Reference Example 3: To the hydroxyl-terminated polyoxypropylene (B-4) obtained in Example 6, 1.00 molar equivalents of sodium methoxide were added as a 28% methanol solution relative to the hydroxyl groups. After distilling off the methanol by vacuum devolatilization at 140°C, 0.30 molar equivalents of allyl glycidyl ether relative to the hydroxyl groups of the polymer (B-1) was added and the reaction was carried out at 140°C for 2 hours. Subsequently, 1.10 molar equivalents of allyl chloride were added at 130°C to convert the terminal hydroxyl groups to allyl groups. Furthermore, 0.30 molar equivalents of a methanol solution of sodium methoxide was added, and the methanol was removed at 130°C. Subsequently, 0.80 molar equivalents of allyl chloride were added at 130°C to convert the remaining terminal hydroxyl groups to allyl groups. The purification procedure was then the same as in Example 4. As a result of the above, polyoxypropylene (A-11) containing polymer molecules having two or more carbon-carbon unsaturated bonds in one terminal structure and having a number average molecular weight of about 20,800 was obtained.

[0160] For the carbon-carbon unsaturated bond polymers (A-4) to (A-11) obtained as above, the reaction rates of the terminal hydroxyl groups were calculated by the above-mentioned method using the hydroxyl group-containing polymers (B-2) to (B-4) used as raw materials as the standard, and the results are shown in Table 3.

[0161]

[0162] The results shown in Table 3 show that when the amount of metal methoxide added in step (1) is within the range of 1.05 to 1.35 equivalents relative to the hydroxyl groups of polymer (B), carbon-carbon unsaturated bonds can be efficiently introduced without adding metal methoxide after step (2). In particular, a comparison between Example 6 and Reference Example 3 shows that by employing the production method according to the present disclosure, it is possible to achieve an introduction rate of carbon-carbon unsaturated bonds similar to that achieved by the conventional two-stage production method (Reference Example 3).

Claims

1. A method for producing a polymer (A) having a carbon-carbon unsaturated bond, comprising: step (1) of adding a metal methoxide to a polymer (B) having hydroxyl groups, and then devolatilizing the methanol to allow the metal methoxide to act on the hydroxyl groups of the polymer (B) to obtain a polymer (C); step (2) of reacting the polymer (C) with an epoxy compound (G1) having a carbon-carbon unsaturated bond to obtain a polymer (D); and step (3) of reacting the polymer (D) with a halogenated hydrocarbon compound (G2) having a carbon-carbon unsaturated bond to obtain a polymer (A); wherein the amount of the metal methoxide added in step (1) is 1.05 to 1.35 equivalents relative to the hydroxyl groups of the polymer (B); the amount of the halogenated hydrocarbon compound (G2) added in step (3) is 4.0 equivalents or less relative to the hydroxyl groups of the polymer (B); and no metal methoxide is added after step (2).

2. The method for producing polymer (A) according to claim 1, wherein the amount of epoxy compound (G1) added in step (2) is 0.2 equivalents or more relative to the hydroxyl groups of polymer (B).

3. The method for producing polymer (A) according to claim 1, wherein the amount of epoxy compound (G1) added in step (2) is 1.0 equivalent or more and 3.0 equivalents or less relative to the hydroxyl groups of polymer (B).

4. The method for producing polymer (A) according to claim 1 or 2, wherein the reaction temperature when polymer (C) is reacted with epoxy compound (G1) in step (2) is 60 to 150°C.

5. The method for producing polymer (A) according to claim 1 or 2, wherein the amount of halogenated hydrocarbon compound (G2) added in step (3) is 1.0 equivalent or more relative to the hydroxyl groups of polymer (B).

6. The method for producing polymer (A) according to claim 1 or 2, wherein the reaction temperature when polymer (D) is reacted with halogenated hydrocarbon compound (G2) in step (3) is 50 to 150°C.

7. The carbon-carbon unsaturated bond is represented by the following formula (1): -R １ -C(R ２ ) = CH ２ (1) (wherein, R １ represents a direct bond or a divalent hydrocarbon group having 1 to 6 carbon atoms which may have an oxygen atom; R ２ represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms.

8. The method for producing polymer (A) according to claim 1 or 2, wherein polymer (A) has a polyoxyalkylene-based main chain skeleton.

9. The method for producing polymer (A) according to claim 1 or 2, wherein the number average molecular weight of polymer (A) is 10,000 or more but less than 35,000.

10. A method for producing a polymer (E) having a reactive silicon group, comprising: producing a polymer (A) having a carbon-carbon unsaturated bond by the production method described in claim 1 or 2; and reacting the polymer (A) with a hydrosilane compound having a reactive silicon group.

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