JP2020105439A - Method for producing organic polymer containing terminal unsaturated bond, or method for producing organic polymer containing hydrolyzable silyl group - Google Patents

Abstract

To provide a method for producing an organic polymer containing a terminal unsaturated bond, which can introduce an unsaturated bond at a high rate without performing a step of distilling off a byproduct of a metal oxidization reaction, when converting a hydroxyl group of the organic polymer to a group containing a terminal unsaturated bond via a metal oxy group, and moreover, in which the terminal unsaturated bond resists progress of isomerization even at high temperature.SOLUTION: An organic polymer (B) having a hydroxyl group is reacted with a sodium salt (C) of tertiary alkoxide and an electrophilic agent (D) having a terminal unsaturated bond, and thereby, the hydroxyl group in the organic polymer (B) is converted into the group containing the terminal unsaturated bond.SELECTED DRAWING: None

Description

The present invention relates to a method for producing an organic polymer having a terminal unsaturated bond and a method for producing an organic polymer having a hydrolyzable silyl group.

An organic polymer in which an unsaturated bond is bonded to the main chain is a polymer exhibiting curability and can be used as a curable material, and is also a precursor for producing an organic polymer having a hydrolyzable silyl group. It is a very useful polymer that can be used as a body.

As a method for synthesizing such an unsaturated bond-containing organic polymer, a method of producing an organic polymer having a hydroxyl group and then converting the hydroxyl group into an unsaturated bond-containing group is known. Among them, after forming a polyoxyalkylene polymer having a hydroxyl group by a polymerization reaction, after reacting the hydroxyl group with an alkali metal alkoxide to metal oxylate, an electrophile having an unsaturated bond such as allyl chloride is formed. A method of making a polymer having an unsaturated bond by reacting is widely used (see, for example, Patent Documents 1 and 2).
As the alkali metal alkoxide used in this method, sodium methoxide and potassium alkoxide are known.

JP-A-7-97440 JP 2000-302981 A

The reaction of reacting sodium methoxide with a hydroxyl group of an organic polymer to form a hydroxyl group into a sodium oxy group is an equilibrium reaction that is disadvantageous to the product. A process of distilling off some methanol under heating and reduced pressure is required. That is, natriurim methoxide was added to the organic polymer, and then methanol was distilled off under heating and reduced pressure to advance the sodium oxidization reaction, and then an electrophilic agent having an unsaturated bond was added to the sodium oxymide. It was necessary to introduce an unsaturated bond by reacting with a group.

Moreover, since the viscosity of the reaction system rapidly increases with the progress of the sodium oxidization reaction and the reaction is inhibited, a sufficiently high unsaturated bond introduction rate cannot be achieved in a single process. In order to increase the introduction rate, it was necessary to repeat the processes of adding sodium methoxide, sodium oxidation reaction accompanied by distillation of by-products, addition of electrophile, and unsaturated bond introduction reaction.

On the other hand, when the metal oxylation reaction is performed at a high temperature using potassium alkoxide as the metal alkoxide, the isomerization reaction of the terminal unsaturated bond proceeds, and the terminal unsaturated bond is converted to the internal unsaturated bond. Tend to end up. The internal unsaturated bond tends to have lower reactivity than the terminal unsaturated bond, such as a lower introduction rate of hydrolyzed silyl groups in the hydrosilylation reaction, and thus suppresses the isomerization reaction of the terminal unsaturated bond. Is desirable.

In view of the above-mentioned present situation, the present invention performs a step of distilling a by-product of a metaloxylation reaction when converting a hydroxyl group of an organic polymer into a terminal unsaturated bond-containing group via a metaloxy group. Even without, it is possible to achieve a high unsaturated bond introduction rate, moreover, isomerization of the terminal unsaturated bond is difficult to proceed even at high temperature, a method for producing a terminal unsaturated bond-containing organic polymer, and obtained. Another object of the present invention is to provide a method for producing a hydrolyzable silyl group-containing organic polymer using the terminal unsaturated bond-containing organic polymer.

The present inventors have conducted extensive studies in order to solve the above problems, and as a metal alkoxide used when metal-oxidizing a hydroxyl group of an organic polymer, not a sodium methoxide or a potassium alkoxide, but a tertiary alkoxide. It is possible to introduce unsaturated bonds without using the step of distilling off the by-products of the metal oxidation reaction by using the sodium salt of, and it is also possible to use a simple process to achieve a high unsaturated bond introduction rate. The present invention has been completed, and it was found that the isomerization of the terminal unsaturated bond is difficult to proceed even at high temperature, and the present invention has been completed.

That is, the first aspect of the present invention is a method for producing an organic polymer (A) having a terminal unsaturated bond, wherein a sodium salt (C) of a tertiary alkoxide is added to an organic polymer (B) having a hydroxyl group. ), and an electrophilic agent (D) having a terminal unsaturated bond are reacted to convert the hydroxyl group in the organic polymer (B) into a terminal unsaturated bond-containing group, the organic polymer (A). Manufacturing method.
Preferably, the organic polymer (A) and the organic polymer (B) are at least one main chain skeleton selected from the group consisting of a polyoxyalkylene main chain skeleton and a polyolefin main chain skeleton. Have.
Preferably, the step is carried out at a temperature of 60°C or higher.
Preferably, the terminal unsaturated bond-containing group has the following formula (1):
^{-O-R 1 -C (R 2} ) = CH 2 (1)
(In the formula, R ¹ represents a divalent hydrocarbon group having 1 to 4 carbon atoms, and R ² represents hydrogen or an alkyl group having 1 to 6 carbon atoms). .. Preferably R ² represents a methyl group.
Preferably, the sodium salt (C) of the tertiary alkoxide is sodium tert-butoxide.
The second aspect of the present invention is to produce an organic polymer (A) having a terminal unsaturated bond by the production method of the first aspect of the present invention, and then add a hydrolyzate to the terminal unsaturated bond of the organic polymer (A). The present invention relates to a method for producing an organic polymer (E) having a hydrolyzable silyl group, which comprises a step of reacting a hydrosilane compound having a decomposable silyl group.

According to the present invention, when converting the hydroxyl group of the organic polymer to the terminal unsaturated bond-containing group via the metaloxy group, the step of distilling off the by-product of the metaloxylation reaction is not necessary. It is possible to provide a method for producing an organic polymer containing a terminal unsaturated bond, which can achieve a high unsaturated bond introduction rate and is less likely to cause isomerization of the terminal unsaturated bond even at high temperature.

That is, according to the production method of the present invention, a terminal unsaturated bond-containing organic polymer having a high unsaturated bond introduction rate and a low terminal unsaturated bond isomerization rate is produced by a simple process with few steps. can do. Since the unsaturated bond-introducing reaction proceeds without carrying out the step of distilling off the by-product, the addition of the alkoxide salt and the addition of the electrophile can be carried out continuously. Since the unsaturated bond is introduced even if the order of is changed, the degree of freedom in process design is increased. Further, since the isomerization of the terminal unsaturated bond does not easily proceed even at high temperature, the reaction can be carried out at high temperature, and as a result, the reaction solution can be easily stirred.

When the terminal unsaturated bond of the organic polymer produced as described above is reacted with a hydrolyzable silyl group-containing hydrosilane compound, the introduction rate of the hydrolyzable silyl group into the polymer is improved, and thus the obtained hydrolyzed silyl group is obtained. An organic polymer having a decomposable silyl group can form a cured product having a high modulus value.

Embodiments of the present invention will be described in detail below.

INDUSTRIAL APPLICABILITY The present invention uses an organic polymer (B) having a hydroxyl group as a precursor and converts the hydroxyl group of the organic polymer (B) into a terminal unsaturated bond-containing group to give a terminal unsaturated bond-containing organic polymer ( A) relates to a method of manufacturing.

In the present application, the terminal unsaturated bond, having a methylidene group (= CH ₂₎ - refers to carbon double bond. Although not particularly limited, specifically, the terminal unsaturated bond is represented by the following general formula (2):
_{^{-C (R 2) = CH 2}} (2)
Can be expressed as In the formula (2), R ² represents hydrogen or an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms is not particularly limited, and specific examples thereof include hydrogen, a methyl group, an ethyl group, a propyl group, a butyl group, etc., and a hydrogen atom, a methyl group, an ethyl group is preferable, and a hydrogen atom is preferable. , And a methyl group is more preferable. In particular, hydrogen is preferable because it facilitates the introduction of a hydrolyzable silyl group, and a methyl group is preferable because it improves the rate of introduction of terminal unsaturated bonds.

When the terminal unsaturated bond is isomerized, an internal unsaturated bond is formed. When the polymer has an internal unsaturated bond, the introduction rate of hydrolyzed silyl groups by the hydrosilylation reaction described below is reduced, which is not desirable. The internal unsaturated bond means a carbon-carbon double bond having no methylidene group, and is not particularly limited, and for example, the following general formula (3):
_{^{-CH = C (R 2) -CH}} 3 (3)
Can be expressed as In formula (3), R ² represents hydrogen or an alkyl group having 1 to 6 carbon atoms, like R ² in formula (2).

In the present invention, the main chain skeleton of the organic polymer (A) and the organic polymer (B) is not particularly limited, and examples thereof include polyoxyalkylene-based, polyolefin-based, (meth)acrylic-based, polyester-based main-chain skeletons. And so on. Among them, a polyoxyalkylene-based main chain skeleton or a polyolefin-based main chain skeleton is preferable because the stability during the reaction in the production method of the present invention is good. A polyoxyalkylene-based main chain skeleton is more preferable because a high terminal unsaturated bond introduction rate can be achieved. Further, the organic polymer (A) and the organic polymer (B) may have a main chain skeleton formed by bonding different kinds of main chain skeletons, or may have different main chain skeletons. It may be a mixture.

The main chain skeleton of the polyoxyalkylene is not particularly limited, but for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene- Examples thereof include polyoxybutylene copolymer. Preferred is polyoxypropylene. The main chain skeleton may be linear or may contain a branched structure.

The polyolefin-based main chain skeleton is not particularly limited, and examples thereof include polyethylene, polypropylene, ethylene-propylene copolymers, polyisobutylene; copolymers of isobutylene and isoprene, etc.; polychloroprene, polyisoprene; isoprene and butadiene. , Copolymers with acrylonitrile, styrene and the like; polybutadiene; polyolefin-based polymers obtained by hydrogenating polybutadiene; polyolefin-based polymers obtained by hydrogenating isoprene or a copolymer of butadiene and acrylonitrile, styrene, etc. , And the like. Preferred is polybutadiene or a polyolefin-based polymer obtained by hydrogenating polybutadiene. The main chain skeleton may be linear or may contain a branched structure.

The organic polymer (B) used as a precursor in the present invention is not particularly limited as long as it is a polymer having a main chain skeleton and a hydroxyl group as described above, but in a particularly preferred embodiment of the present invention The method for producing the organic polymer (B) having a polyoxyalkylene-based main chain skeleton will be described in detail below.

The organic polymer (B) having a main chain skeleton of polyoxyalkylene and having a hydroxyl group can be obtained, for example, by ring-opening polymerization of a monoepoxide in the presence of an initiator having a hydroxyl group and a catalyst. ..

The initiator having a hydroxyl group is not particularly limited, for example, ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, low molecular weight polyoxypropylene triol, allyl alcohol, low molecular weight polyoxypropylene. Examples thereof include organic compounds having one or more hydroxyl groups such as monoallyl ether and low molecular weight polyoxypropylene monoalkyl ether.

The monoepoxide is not particularly limited, for example, ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, alkylene oxides such as α-methylstyrene oxide, and methylglycidyl. Examples thereof include alkyl glycidyl ethers such as ether, ethyl glycidyl ether, isopropyl glycidyl ether and butyl glycidyl ether, allyl glycidyl ethers and aryl glycidyl ethers. Propylene oxide is preferred.

The catalyst is not particularly limited, but examples thereof include alkali catalysts such as KOH and NaOH, acidic catalysts such as trifluoroborane-etherate, and complex metal cyanide complex catalysts such as aluminoporphyrin metal complex and cobalt zinc cyanide-glyme complex catalyst. Known catalysts can be used. Among them, the double metal cyanide complex catalyst is preferable because it has less chain transfer reaction and a polymer having a high molecular weight and a narrow molecular weight distribution can be obtained. Further, a basic compound such as KOH, NaOH, KOCH ₃ , NaOCH ₃ or the like is allowed to act on a polyoxyalkylene polymer having a small number average molecular weight, and a bifunctional or higher alkyl halide such as CH ₂ BrCl or CH is added. _A high molecular weight polyoxyalkylene polymer can also be obtained by a chain extension reaction by reacting ₂ Cl ₂ , CH ₂ Br _2, or the like.

The number average molecular weight of the organic polymer (B) having a hydroxyl group is not particularly limited, but it is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, further preferably still more preferably 3,000 to 100,000 in terms of polystyrene-reduced molecular weight in GPC. Is 3,000 to 40,000, and more preferably 3,000 to 30,000. The polystyrene-equivalent molecular weight in GPC was measured by using Tosoh HLC-8220GPC as a liquid delivery system, using a Tosoh TSKgel SuperH series as a column, and using THF as a solvent, and so on.

In the organic polymer (B), the hydroxyl group may be bonded to the terminal of the main chain skeleton or may be bonded to the main chain skeleton as a side chain. Further, the number of hydroxyl groups contained in the organic polymer (B) is not particularly limited, and may be 1 or 2 or more.

In the present invention, the organic polymer (B) having a hydroxyl group is reacted with the sodium salt of a tertiary alkoxide (C) and the electrophile (D) having a terminal unsaturated bond. As a result, the hydroxyl group of the organic polymer (B) is converted into a terminal unsaturated bond-containing group via the sodium oxy group, whereby the organic polymer (A) having a terminal unsaturated bond can be produced. ..

In the present invention, a sodium salt of a tertiary alkoxide (C) is used as a base used for converting a hydroxyl group of the organic polymer (B) into a sodium oxy group. According to this, the reaction of converting the hydroxyl group of the organic polymer (B) into a terminal unsaturated bond-containing group can proceed without performing the step of distilling off the by-product of the sodium oxidization reaction. it can. In addition, even if the above reaction is carried out at a high temperature, it is possible to suppress a side reaction in which the terminal unsaturated bond is isomerized to become an internal unsaturated bond.

The tertiary alkoxide means one in which a carbon atom bonded to an oxygen atom constituting the alkoxide is bonded to three carbon atoms. Specifically, the sodium salt (C) of the tertiary alkoxide is represented by the following general formula (3):

Can be expressed as In formula (3), R ^{3 to} R ⁵ are the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms. Specific examples of the sodium salt of tertiary alkoxide (C) are not particularly limited, but sodium tert-butoxide, sodium tert-pentoxide (also known as tert-amyloxide, or 2-methyl-2-butoxide), sodium tert-hexyloxide. (Alias: 2,4-dimethyl-2-butoxide), sodium tert-octyloxide (alias: 2,4,4-trimethyl-2-pentoxide), sodium=1,1-dimethylhexyloxide and the like. Among these, sodium tert-butoxide and sodium tert-pentoxide are preferable because they have a relatively small molecular weight and the amount used can be suppressed, and sodium tert-butoxide is more preferable from the viewpoint of easy availability. The sodium salt of tertiary alkoxide (C) may be added to the reaction system in a state of being dissolved in a solvent.

The amount of the sodium salt (C) of the tertiary alkoxide used is not particularly limited and can be appropriately determined in consideration of the target terminal unsaturated bond introduction ratio. For example, the hydroxyl group of the organic polymer (B) Is preferably 0.5 or more, more preferably 0.6 or more, still more preferably 0.7 or more, still more preferably 0.8 or more. The molar ratio is preferably 2.0 or less, more preferably 1.8 or less. If the amount of the sodium salt (C) of the tertiary alkoxide used is too small, the reaction may not proceed sufficiently. On the other hand, if the amount used is too large, the sodium salt (C) of the tertiary alkoxide may remain as an impurity and the side reaction may proceed. As will be described later, the sodium salt of the tertiary alkoxide (C) can be added in a plurality of divided portions. In that case, the amount of the sodium salt of the tertiary alkoxide (C) used is , Refers to the total amount used.

In the present invention, the electrophile (D) having a terminal unsaturated bond is used in order to convert the hydroxyl group of the organic polymer (B) into a terminal unsaturated bond-containing group via a sodium oxy group.

As the electrophile (D) having a terminal unsaturated bond, a compound that reacts with a sodium oxy group in which a hydroxyl group of the organic polymer (B) is converted and can introduce a terminal unsaturated bond into the organic polymer is particularly preferable. Although not limited, examples thereof include organic halides having a terminal unsaturated bond, epoxy compounds having a terminal unsaturated bond, and the like.

The organic halide having a terminal unsaturated bond can introduce a terminal unsaturated bond-containing group into the polymer by reacting with the sodium oxy group of the polymer by a halogen substitution reaction to form an ether bond. .. The organic halide having a terminal unsaturated bond includes, but is not limited to, the following general formula (4):
^{X-R 1 -C (R 2} ) = CH 2 (4)
Can be expressed as In formula (4), R ¹ represents a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms, R ² represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and X represents a halogen atom. Represents. As R ¹ , an alkylene group having 1 to 4 carbon atoms is preferable, and a methylene group, an ethylene group, a propylene group or a butylene group can be used, but a methylene group is particularly preferable. Examples of R ² include hydrogen, a methyl group, an ethyl group, a propyl group, a butyl group and the like, preferably a hydrogen atom, a methyl group and an ethyl group, more preferably a hydrogen atom and a methyl group. In particular, a methyl group is preferable because the introduction rate of terminal unsaturated bonds is improved.

Specific examples of the organic halide having a terminal unsaturated bond are not particularly limited, but include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and iodine. Methallyl chloride and the like. Allyl chloride and methallyl chloride are preferred from the viewpoint of easy handling.

The epoxy compound having a terminal unsaturated bond is capable of introducing a terminal unsaturated bond-containing group into the polymer by reacting with the sodium oxy group of the polymer to form an ether bond by a ring-opening addition reaction of the epoxy group. You can The epoxy compound having a terminal unsaturated bond is not limited to the following general formula (5):

Can be expressed as In formula (5), R ⁶ represents a direct bond, —C(═O)—, or a divalent hydrocarbon group having 1 to 4 carbon atoms, and R ¹ and R ² are each related to formula (4). This is the same as R ¹ and R ² described above. As R ⁶ , an alkylene group having 1 to 4 carbon atoms is preferable, and a methylene group, an ethylene group, a propylene group or a butylene group can be used, but a methylene group is particularly preferable.

Specific examples of the epoxy compound having a terminal unsaturated bond are not particularly limited, and examples of the epoxy compound represented by the formula (5) include allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate. Examples of the epoxy compound having a structure other than the formula (5) include butadiene monooxide and 1,4-cyclopentadiene monoepoxide. Among them, allyl glycidyl ether is particularly preferable.

As the electrophile (D) having a terminal unsaturated bond, a sodium oxy group of the polymer is reacted with an epoxy compound having a terminal unsaturated bond, and then an organic halogen having a terminal unsaturated bond. The compound may be reacted. According to this reaction, both a terminal unsaturated bond derived from an epoxy compound having a terminal unsaturated bond and a terminal unsaturated bond derived from an organic halide having a terminal unsaturated bond are introduced into the polymer. You can

The amount of the electrophile (D) having a terminal unsaturated bond is not particularly limited, and can be appropriately determined in consideration of the reactivity of the electrophile used and the terminal unsaturated bond introduction rate. Specifically, when an organic halide having a terminal unsaturated bond is used as the electrophile (D) having a terminal unsaturated bond, the amount of the organic halide used is not particularly limited, but is not limited to The molar ratio of the compound (B) to the hydroxyl group is preferably 0.7 or more, more preferably 1.0 or more. The molar ratio is preferably 5.0 or less, more preferably 2.0 or less.

When an epoxy compound having a terminal unsaturated bond is used as the electrophile (D) having a terminal unsaturated bond, the amount of the epoxy compound used is not particularly limited, but the organic polymer (B) has The molar ratio to the hydroxyl group is preferably 0.1 or more, more preferably 0.3 or more, further preferably 0.5 or more, particularly preferably 1.0 or more, and most preferably 1.5 or more. The molar ratio is preferably 9 or less, more preferably 7 or less, further preferably 5 or less, and particularly preferably 4 or less.

When the organic halide represented by the general formula (4) and/or the epoxy compound represented by the general formula (5) is used as the electrophile (D) having a terminal unsaturated bond, the following general formula is used. Formula (1):
^{-O-R 1 -C (R 2} ) = CH 2 (1)
The organic polymer (A) having a terminal unsaturated bond-containing group represented by can be produced. In the formula (1), R ¹ and R ² are selected from the groups described for the formulas (4) and (5), and the same applies to the preferable groups, but in particular, R ¹ has 1 to 1 carbon atoms. It is preferable that R ⁴ represents a divalent hydrocarbon group of 4 and R ² represents hydrogen or an alkyl group having 1 to 6 carbon atoms.

In the conventional production method using sodium methoxide as a base, sodium methoxide is added to an organic polymer (B) having a hydroxyl group, and then methanol, which is a by-product, is distilled off under heating and reduced pressure to remove sodium oxyoxide. It was necessary to add the electrophile (D) having a terminal unsaturated bond after allowing the chemical reaction to proceed sufficiently. However, according to the production method of the present invention in which the sodium salt of a tertiary alkoxide (C) is used as a base, the sodium oxydation reaction proceeds even without carrying out the step of distilling the by-product, and The subsequent unsaturated bond introduction reaction also proceeds.

Further, in the production method of the present invention, unlike the conventional production method using sodium methoxide, the addition order of the sodium salt of a tertiary alkoxide (C) and the electrophile (D) having a terminal unsaturated bond is limited. Alternatively, the reactants can be added in any order. For example, to the organic polymer (B) having a hydroxyl group, after adding the sodium salt (C) of a tertiary alkoxide, the electrophile (D) having a terminal unsaturated bond may be added, or After adding the electrophile (D) having a terminal unsaturated bond to the organic polymer (B) having a hydroxyl group, the sodium salt (C) of a tertiary alkoxide may be added. Further, the sodium salt of tertiary alkoxide (C) and the electrophile (D) having a terminal unsaturated bond may be added at the same time. Further, the sodium salt of a tertiary alkoxide (C) and/or the electrophile (D) having a terminal unsaturated bond may be divided and added twice or more. The order of addition is not particularly limited even in divided addition. For example, after adding a part of the sodium salt (C), the electrophile (D) is added, and the rest of the sodium salt (C) is added. Alternatively, after adding a part of the electrophile (D), the sodium salt (C) may be added, and the rest of the electrophile (D) may be added. The organic polymer (A) having a terminal unsaturated bond can be produced by any addition order.

As described above, in the present invention, it is not necessary to carry out the step of distilling off the by-product, and the addition of the sodium salt of the tertiary alkoxide (C) and the electrophile (D) having a terminal unsaturated bond is performed. Since the order is not limited, there is an advantage that the degree of freedom in process design is increased.

In the present invention, those skilled in the art can appropriately select the temperature for reacting the organic polymer (B) with the sodium salt of a tertiary alkoxide (C) and the electrophile (D) having a terminal unsaturated bond. The temperature can be set and is not particularly limited, but may be, for example, 50 to 150°C. When a potassium alkoxide is used as a base instead of a sodium salt (C) of a tertiary alkoxide and the reaction is carried out at a high temperature, an isomerization reaction of a terminal unsaturated bond proceeds and an internal unsaturated bond tends to be formed. Since the sodium salt (C) of the tertiary alkoxide is used in the present invention, the formation of internal unsaturated bond can be suppressed even if the reaction is carried out at high temperature. It is preferable that the reaction can be carried out at a high temperature because the viscosity of the reaction liquid containing the polymer is lowered and the reaction liquid can be easily stirred with a small amount of power. From this viewpoint, the reaction temperature in the present invention is preferably 60° C. or higher, more preferably 80° C. or higher, even more preferably 90° C. or higher. On the other hand, if the temperature is too high, the main chain structure of the polymer may deteriorate, so that the reaction temperature in the present invention is preferably 140°C or lower, more preferably 130°C or lower, and further preferably 115°C or lower. ..

The reaction time is not particularly limited and can be appropriately set by those skilled in the art, but may be, for example, 10 minutes or more and 5 hours or less, and preferably 1 hour or more and 4 hours or less.

The organic polymer (A) having a terminal unsaturated bond produced as described above can be used as a curable material together with a curing agent or a curing catalyst. Further, as described below, it can also be used as a precursor when producing an organic polymer having a hydrolyzable silyl machine.

(Method for producing organic polymer (E) having hydrolyzable silyl group)
A hydrosilane compound having a hydrolyzable silyl group is hydrosilylated to the organic polymer (A) having a terminal unsaturated bond obtained by the production method of the present invention to introduce a hydrolyzable silyl group into the polymer. By doing so, the organic polymer (E) having a hydrolyzable silyl group can be produced. Since the organic polymer (A) having a terminal unsaturated bond obtained by the production method of the present invention has a high introduction rate of a terminal unsaturated bond, it is necessary to increase the introduction rate of a hydrolyzable silyl group by the above hydrosilylation reaction. The obtained organic polymer (E) having a hydrolyzable silyl group can form a cured product having a high modulus value.

The hydrosilane compound having a hydrolyzable silyl group is not particularly limited, but the following general formula (6):
^{_{HSiR 7 3-a Y a (}} 6)
Can be expressed as In the formula (6), R ⁷ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms or a triorganosiloxy group represented by (R′) ₃ SiO—. Y represents a hydroxyl group or a hydrolyzable group. a represents 1, 2 or 3.

Examples of R ⁷ include alkyl groups such as methyl group, ethyl group, chloromethyl group, methoxymethyl group, N,N-diethylaminomethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, and benzyl group. An aralkyl group such as R', and a triorganosiloxy group represented by (R') ₃ SiO- in which R'is a methyl group, a phenyl group or the like (wherein R'is a substituted or unsubstituted monovalent group having 1 to 20 carbon atoms). Represents a hydrocarbon group of) and the like. R ⁷ is preferably a substituted or unsubstituted alkyl group, more preferably a methyl group, an ethyl group, a chloromethyl group or a methoxymethyl group, further preferably a methyl group or an ethyl group, particularly preferably Is a methyl group. When a plurality of R ^7's are present, they may be the same or different from each other.

Examples of Y 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. Y is preferably an alkoxy group, more preferably a methoxy group, an ethoxy group, an n-propoxy group and an isopropoxy group, more preferably a methoxy group and an ethoxy group, and particularly preferably a methoxy group, since they have mild hydrolyzability and are easy to handle. .. As Y, only one type of group may be used, or two or more types of groups may be used in combination.

Specific examples of the hydrosilane compound having a hydrolyzable silyl group include trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, and bis(chloromethyl)chlorosilane. Halogenated silanes such as, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, ethyl Dimethoxysilane, 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-trifluoropropyl)dimethoxysilane, (N,N- Diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyloxy]dimethylsilane, [(chloromethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyl Oxy]dimethylsilane, [(methoxymethyl)diemethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane, [(3,3,3-trifluoropropyl)dimethoxysilyloxy]dimethylsilane, etc. Alkoxysilanes; Acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; Ketoxymate silanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane, triisopropenyloxysilane And isopropenyloxysilanes (deacetone type) such as (chloromethyl)diisopropenyloxysilane and (methoxymethyl)diisopropenyloxysilane.

The amount of the hydrosilane compound having a hydrolyzable silyl group may be appropriately set in consideration of the amount of terminal unsaturated bond contained in the organic polymer (A). Specifically, the molar ratio of the hydrosilane compound to the terminal unsaturated bond of the organic polymer (A) is preferably 0.05 or more and 10 or less, and more preferably 0.3 or more and 3 or less from the viewpoint of reactivity. From the viewpoint of increasing the modulus value of the cured product of the obtained organic polymer (E), the molar ratio is more preferably 0.5 or more, particularly preferably 0.7 or more. On the other hand, from the viewpoint of economy, the molar ratio is more preferably 2.5 or less, and particularly preferably 2 or less.

The hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst in order to accelerate the reaction. The hydrosilylation catalyst is not particularly limited, but a metal such as cobalt, nickel, iridium, platinum, palladium, rhodium, ruthenium, or a complex thereof can be used. Specifically, platinum supported on a carrier such as alumina, silica, or carbon black, chloroplatinic acid; chloroplatinic acid complex composed of chloroplatinic acid and alcohol, aldehyde, ketone, or the like; platinum-olefin complex [eg, _{Pt (CH 2 = CH 2)} 2 (PPh 3), Pt (CH 2 = CH 2) 2 Cl 2]; platinum - vinylsiloxane complex [e.g. _{Pt {(vinyl) Me 2 SiOSiMe} 2 (vinyl)}, Pt { Me(vinyl)SiO} ₄ ]; platinum-phosphine complex [for example Ph(PPh ₃ ) ₄ , Pt(PBu ₃ ) ₄ ]; platinum-phosphite complex [for example Pt{P(OPh) ₃ } ₄ ] and the like. To be From the viewpoint of reaction efficiency, a platinum catalyst such as chloroplatinic acid or a platinum vinyl siloxane complex is preferable. It is also preferable to add sulfur in order to maintain the activity of the platinum catalyst for a long time. Sulfur may be added in a state of being dissolved in an organic solvent such as hexane.

The temperature condition of the hydrosilylation reaction is not particularly limited and can be appropriately set by those skilled in the art, but for the purpose of lowering the viscosity of the reaction system or improving the reactivity, the reaction under heating conditions is preferable, and specifically, The reaction at 50°C to 150°C is more preferable, and the reaction at 70°C to 120°C is further preferable. The reaction time may be appropriately set, but specifically, the reaction time is preferably 30 minutes or more and 15 hours or less, more preferably 3 hours or more and 12 hours or less.

In addition, the hydrosilylation reaction may be carried out in the presence of an orthocarboxylic acid trialkyl ester. This can suppress thickening during the hydrosilylation reaction and improve the storage stability of the resulting polymer. Examples of the orthocarboxylic acid trialkyl ester include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate and the like. Preferred are trimethyl orthoformate and trimethyl orthoacetate. 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, relative to 100 parts by weight of the organic polymer (A) having a terminal unsaturated bond.

The organic polymer (E) having a hydrolyzable silyl group produced as described above can be used as a curable resin utilizing the reaction of hydrolyzing and condensing the hydrolyzable silyl group. At that time, a silanol condensation catalyst or the like can be added.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

<Calculation method of ratio of terminal unsaturated bond>
The ratio of the terminal unsaturated bond described below, the ratio of the internal unsaturated bond produced by the isomerization of the terminal unsaturated bond, and the ratio of the hydroxyl terminal, respectively, a terminal unsaturated bond, an internal unsaturated bond, and It is the ratio to the total of hydroxyl end groups. The proportion of each is
It was calculated by determining the integral ratio of signals corresponding to each group by ¹ H NMR.

<abbreviation>
tBuONa: sodium tert-butoxide MeONa: sodium methoxide tBuOK: potassium tert-butoxide ACL: 3-chloro-1-propene (allyl chloride)
MAC: 3-chloro-2-methyl-1-propene (methallyl chloride)
AGE: allyl glycidyl ether

(Synthesis example 1)
Using a polyoxypropylene diol having a number average molecular weight of about 5,000 as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a hydroxyl group-terminated polyoxypropylene (B- having a number average molecular weight of about 29,000 (B- 1) was obtained.

(Synthesis example 2)
Polyoxypropylene diol having a number average molecular weight of about 5,000 was used as an initiator to polymerize propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst, and a hydroxyl group-terminated polyoxypropylene (B- 2) was obtained.

(Synthesis example 3)
Using a polyoxypropylene diol having a number average molecular weight of about 5,000 as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a hydroxyl group-terminated polyoxypropylene (B- having a number average molecular weight of about 37,000 (B- 3) was obtained.

(Synthesis example 4)
Polymerization of propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst using a hydroxyl terminated polybutadiene (B-4) having a number average molecular weight of about 4,000 as an initiator, and a hydroxyl terminated polybutadiene having a number average molecular weight of about 15,000. -A block copolymer of polyoxypropylene (B-5) was obtained.

(Example 1)
A pressure-resistant autoclave container having an internal volume of 1 L was filled with 250 g of the polymer (B-1) and 5 g of hexane, and the inside was replaced with nitrogen and then sealed. Then, it heated to 100 degreeC, stirring and decompressing, and distilling hexane off and removing the contained water. While maintaining the temperature of the reaction system at 100° C., 1.3 equivalents of sodium t-butoxide (25 wt% THF solution, about 2.5 mol/L) was added to the hydroxyl group of the polymer (B-1). Then, the mixture was reacted for 10 minutes. Next, 1.8 equivalents of 3-chloro-1-propene was added to the hydroxyl group of the polymer (B-1), and the mixture was reacted for 90 minutes. After that, excess 3-chloro-1-propene and the like were removed by vacuum devolatilization. The obtained reaction product was diluted with hexane, and the residual by-product salts were adsorbed on synthetic aluminum silicate (Kyowaad 700 SEN-S, manufactured by Kyowa Chemical Industry Co., Ltd.), and then hexane was removed by an evaporator to obtain a polymer. (A-1) was obtained. The ratio of the terminal unsaturated bond of the polymer (A-1) was 96%, the ratio of the internal unsaturated bond was 0%, and the ratio of the hydroxyl terminal was 4%.

(Example 2)
A pressure-resistant autoclave container having an internal volume of 1 L was filled with 250 g of the polymer (B-1) and 5 g of hexane, and the inside was replaced with nitrogen and then sealed. Then, it heated to 100 degreeC, stirring and decompressing, and distilling hexane off and removing the contained water. While maintaining the temperature of the reaction system at 100° C., 1.3 equivalents of sodium t-butoxide (25 wt% THF solution, about 2.5 mol/L) was added to the hydroxyl group of the polymer (B-1). Then, the mixture was reacted for 10 minutes. Next, 2.0 equivalents of 3-chloro-1-propene was added to the hydroxyl group of the polymer (B-1), and the mixture was reacted for 60 minutes. Then, 0.3 equivalent of sodium t-butoxide (25 wt% THF solution) was added to the hydroxyl group of the polymer (B-1), and the reaction was carried out for 30 minutes. After that, excess 3-chloro-1-propene and the like were removed by vacuum devolatilization. The obtained reaction product was diluted with hexane, and the residual by-product salts were adsorbed on synthetic aluminum silicate (Kyowaad 700 SEN-S, manufactured by Kyowa Chemical Industry Co., Ltd.), and then hexane was removed by an evaporator to obtain a polymer. (A-2) was obtained. The ratio of the terminal unsaturated bond of the polymer (A-2) was 99%, the ratio of the internal unsaturated bond was 0%, and the ratio of the hydroxyl terminal was 1%.

(Example 3)
A polymer (A-3) was obtained by the same procedure as in Example 1 except that the polymer (B-2) was used instead of the polymer (B-1). The ratio of the terminal unsaturated bond of the polymer (A-3) was 98%, the ratio of the internal unsaturated bond was 0%, and the ratio of the hydroxyl terminal was 2%.

(Example 4)
A pressure-resistant autoclave container having an internal volume of 1 L was filled with 250 g of the polymer (B-2) and 5 g of hexane, and the inside was replaced with nitrogen and then sealed. Then, it heated to 110 degreeC, stirring and decompressing, and distilling hexane off and removing the contained water. While maintaining the temperature of the reaction system at 110° C., 1.2 equivalents of sodium t-butoxide (25 wt% THF solution, about 2.5 mol/L) was added to the hydroxyl group of the polymer (B-2). And allowed to react for 15 minutes. Next, 2.0 equivalents of allyl glycidyl ether was added to the hydroxyl group of the polymer (B-2), and the mixture was reacted for 150 minutes. Subsequently, 1.4 equivalents of 3-chloro-1-propene was added to the hydroxyl group of the polymer (B-2), and the mixture was reacted for 60 minutes. After that, excess 3-chloro-1-propene and the like were removed by vacuum devolatilization. The obtained reaction product was diluted with hexane, and the residual by-product salts were adsorbed on synthetic aluminum silicate (Kyowaad 700 SEN-S, manufactured by Kyowa Chemical Industry Co., Ltd.), and then hexane was removed by an evaporator to obtain a polymer. (A-4) was obtained. The ratio of the terminal unsaturated bond of the polymer (A-4) was 97%, the ratio of the internal unsaturated bond was 0%, and the ratio of the hydroxyl terminal was 3%. Moreover, 95% or more of the unsaturated bond derived from allyl glycidyl ether was introduced into the polymer (A-4) with respect to the amount of allyl glycidyl ether used. The ratio of the terminal unsaturated bond of the polymer (A-4) is a numerical value calculated by combining the terminal unsaturated bond derived from allyl chloride and the terminal unsaturated bond derived from allyl glycidyl ether.

(Example 5)
A polymer (A-5) was obtained by the same procedure as in Example 2 except that the polymer (B-3) was used instead of the polymer (B-1). The ratio of the terminal unsaturated bond of the polymer (A-5) was 99%, the ratio of the internal unsaturated bond was 1%, and the ratio of the hydroxyl terminal was 0%.

(Example 6)
A polymer (A-6) was obtained by the same procedure as in Example 1 except that the polymer (B-4) was used instead of the polymer (B-1). The ratio of the terminal unsaturated bond of the polymer (A-6) was 89%, the ratio of the internal unsaturated bond was 0%, and the ratio of the hydroxyl terminal was 11%.

(Example 7)
A polymer (A-7) was obtained by the same procedure as in Example 1 except that the polymer (B-5) was used instead of the polymer (B-1). The ratio of the terminal unsaturated bond of the polymer (A-7) was 96%, the ratio of the internal unsaturated bond was 0%, and the ratio of the hydroxyl terminal was 4%.

(Comparative Example 1)
The procedure of Example 1 was repeated except that sodium methoxide (28% by weight methanol solution, about 5.2 mol/L) was used instead of sodium t-butoxide, to give a polymer (A-8). Got The ratio of the terminal unsaturated bond of the polymer (A-8) was 29%, the ratio of the internal unsaturated bond was 0%, and the ratio of the hydroxyl group terminal was 71%.

(Example 8)
A polymer (A-9) was obtained by the same procedure as in Example 1 except that 3-chloro-2-methyl-1-propene was used instead of 3-chloro-1-propene. The ratio of the terminal unsaturated bond of the polymer (A-9) was 99%, the ratio of the internal unsaturated bond was 0%, and the ratio of the hydroxyl terminal was 1%.

(Example 9)
A pressure-resistant autoclave container having an internal volume of 1 L was filled with 250 g of the polymer (B-1) and 5 g of hexane, and the inside was replaced with nitrogen and then sealed. Then, it heated to 90 degreeC, stirring and decompressing, and distilling hexane off and removing the contained water. While maintaining the temperature of the reaction system at 90° C., 4.4 equivalents of 3-chloro-2-methyl-1-propene was added to the hydroxyl group of the polymer (B-1). Next, 1.3 equivalents of sodium t-butoxide (30 wt% THF solution, about 3.0 mol/L) was added to the hydroxyl group of the polymer (B-1), and the mixture was reacted for 60 minutes. After that, excess 3-chloro-2-methyl-1-propene and the like were removed by vacuum devolatilization. The obtained reaction product was diluted with hexane, and the residual by-product salts were adsorbed on synthetic aluminum silicate (Kyowaad 700 SEN-S, manufactured by Kyowa Chemical Industry Co., Ltd.), and then hexane was removed by an evaporator to obtain a polymer. (A-10) was obtained. The ratio of the terminal unsaturated bond of the polymer (A-10) was 99%, the ratio of the internal unsaturated bond was 0%, and the ratio of the hydroxyl terminal was 1%.

(Comparative example 2)
Similar to Example 8 except that potassium t-butoxide (12 wt% THF solution, about 1.0 mol/L) was used instead of sodium t-butoxide, and the reaction temperature of 100° C. was changed to 85° C. The polymer (A-11) was obtained by going through the procedure. The ratio of the terminal unsaturated bond of the polymer (A-11) was 66%, the ratio of the internal unsaturated bond was 33%, and the ratio of the hydroxyl terminal was 1%.

(Comparative example 3)
A polymer (A-12) was obtained by the same procedure as in Comparative Example 2 except that the reaction temperature of 85°C was changed to 60°C. The ratio of the terminal unsaturated bond of the polymer (A-12) was 94%, the ratio of the internal unsaturated bond was 5%, and the ratio of the hydroxyl terminal was 1%.

The above results are summarized in Tables 1 and 2.

In each of Examples 1 to 7, when converting the hydroxyl group of the organic polymer to a terminal unsaturated bond-containing group via a sodium oxy group, a step of distilling a by-product of the sodium oxidization reaction is carried out. Although it has not been carried out, the terminal unsaturated bond-containing organic polymer (A) can be produced with a high unsaturated bond introduction rate, and further, the isomerization of the terminal unsaturated bond proceeds even at a high temperature reaction. It was difficult and the ratio of internal unsaturated bonds was zero or small.

In Examples 2 and 5, after adding the sodium salt of the tertiary alkoxide, the electrophilic agent 3-chloro-1-propene was added, and the sodium salt of the tertiary alkoxide was added again. As a result, it can be seen that the terminal unsaturated bond introduction rate is improved as compared with Example 1.

From Example 4, it can be seen that even if allyl glycidyl ether is added before 3-chloro-1-propene as an electrophile, a high terminal unsaturated bond introduction rate can be achieved. Further, from Examples 6 and 7, it can be seen that even when the main chain skeleton of the organic polymer is polyolefin or the copolymer of polyoxyalkylene and polyolefin, a relatively high terminal unsaturated bond introduction rate can be achieved.

On the other hand, in Comparative Example 1 in which the production of an organic polymer containing a terminal unsaturated bond was attempted under the same conditions as in Example 1 by using sodium methoxide instead of the sodium salt of a tertiary alkoxide, The group introduction reaction did not proceed sufficiently, and the terminal unsaturated bond introduction rate was extremely low.

Also in Example 8 using 3-chloro-2-methyl-1-propene as the electrophile, the terminal unsaturated bond-containing organic polymer can be produced at a high introduction rate, and the terminal unsaturated bond is obtained even at high temperature. The bond isomerization did not easily proceed, and almost no internal unsaturated bond was formed. From this example, when 3-chloro-2-methyl-1-propene is used as the electrophile, the terminal unsaturated bond introduction ratio is improved as compared with Example 1 using 3-chloro-1-propene. I know what to do. Example 9 was prepared by adding the electrophilic agent 3-chloro-2-methyl-1-propene in the reverse order of addition and then adding the sodium salt of the tertiary alkoxide. It can be seen that an equivalent terminal unsaturated bond introduction rate can be achieved.

On the other hand, in Comparative Example 2 in which a terminal unsaturated bond-containing organic polymer was produced by the same procedure as in Example 8 using a potassium salt of a tertiary alkoxide instead of a sodium salt of a tertiary alkoxide, The isomerization reaction proceeded and the ratio of internal unsaturated bonds became high. Further, in Comparative Example 3 in which the reaction temperature was lower than in Comparative Example 2, the proportion of internal unsaturated bonds could be made lower than in Comparative Example 2, but a certain amount of residual remained. Further, since the reaction temperature is low, the viscosity of the reaction liquid becomes high, and the stirring efficiency is lowered, so that the reaction may be hindered or the equipment may be troubled because the load on the equipment is increased.

(Reference example)
A pressure-resistant autoclave container having an internal volume of 1 L was filled with 250 g of the polymer (B-1) and 5 g of hexane, and the inside was replaced with nitrogen and then sealed. Then, it heated to 100 degreeC, stirring and decompressing, and distilling hexane off and removing the contained water. After allowing to cool to 60° C. or lower, 0.9 equivalent of sodium methoxide (28 wt% methanol solution, about 5.2 mol/L) was added to the hydroxyl group of the polymer (B-1), and 130° C. The temperature was raised to 50 Torr and the pressure was reduced to 5 Torr or less, and the reaction was carried out for 120 minutes while removing by-product methanol. Next, 1.2 equivalents of 3-chloro-2-methyl-1-propene was added to the hydroxyl group of the polymer (B-1), and the mixture was reacted for 60 minutes. After cooling to 60° C. or less once, 0.4 equivalent of sodium methoxide (28% by weight methanol solution) and 0.8 equivalent of 3-chloro-2-based on the hydroxyl group of the polymer (B-1). The reaction was carried out again with the same procedure using methyl-1-propene. After that, excess 3-chloro-2-methyl-1-propene and the like were removed by vacuum devolatilization. The obtained reaction product was diluted with hexane, and the residual by-product salts were adsorbed on synthetic aluminum silicate (Kyowaad 700 SEN-S, manufactured by Kyowa Chemical Industry Co., Ltd.), and then hexane was removed by an evaporator to obtain a polymer. (A-13) was obtained. The ratio of the terminal unsaturated bond of the polymer (A-13) was 95%, the ratio of the internal unsaturated bond was 0%, and the ratio of the hydroxyl terminal was 5%.

This reference example shows a conventional method using sodium methoxide, which includes addition of sodium methoxide, sodium oxidation reaction accompanied by distillation of by-products, addition of electrophile, and unsaturated bond introduction reaction. This process is repeated twice. The ratio of the terminal unsaturated bond was 95%, but in order to achieve this terminal unsaturated bond introduction rate, a step of distilling off the by-product methanol under heating and reduced pressure is required, and the process for a long time is required. Had to be repeated twice.

(Example 10)
A glass flask having an internal volume of 500 mL was charged with 150 g of the polymer (A-9) having a methallyl group at the molecular chain end obtained in Example 8, and a mechanical stirrer, a reflux tube, and a rubber septum were connected to the reflux tube. I connected a balloon to. After substituting the inside with nitrogen, 3 g of hexane was added through a rubber septum, and the mixture was heated to 100° C. while stirring and reducing the pressure.

Next, 100 ppm of a platinum divinyldisiloxane complex solution (an isopropyl alcohol solution having a concentration of 3% by mass in terms of platinum), 100 ppm of a sulfur solution (a hexane solution having a concentration of 0.25% by weight) and 2.3 parts by weight of methyldimethoxysilane were added, The reaction was continued at 100° C. until the residual amount of methallyl group was less than 1% before the start of the reaction. The polymer (E-1) having a methyldimethoxysilyl group at the terminal as a hydrolyzable silyl group was obtained by removing excess methyldimethoxysilane and the like by devolatilization under reduced pressure.

(Comparative Example 4)
By using the same procedure as in Example 10 except that the polymer (A-13) having a methallyl group at the molecular chain end obtained in Reference Example is used instead of the polymer (A-9), A polymer (E-2) having a methyldimethoxysilyl group as a hydrolyzable silyl group was obtained.

A mixture of the polymer (E)/tin(II) octylate/laurylamine/distilled water=50/1.5/0.25/0.30 (weight ratio) obtained in Example 10 or Comparative Example 4 was added. Each of them was filled in a sheet-like mold having a thickness of 3 mm. After storing at 23° C. and 50% relative humidity for 1 hour or more, it was cured in a dryer at 70° C. for 20 hours to obtain a sheet-shaped cured product.

The obtained cured product was punched out into a No. 3 dumbbell mold according to JIS K 6251 to obtain a test piece. Using the obtained test piece, a tensile test (pulling speed: 200 mm/min) was performed using an autograph at 23° C. and a relative humidity of 50% to measure a stress at 100% elongation (100% modulus value).

As a result, the 100% elongation stress of the cured product of the polymer (E-1) was 0.57 MPa, and the 100% elongation stress of the cured product of the polymer (E-2) was 0.52 MPa. From this, the hydrolyzable silyl group-containing organic polymer (E) produced according to the present invention has a high proportion of terminal unsaturated bonds in the terminal unsaturated bond-containing organic polymer (A) of the precursor. It is understood that a large amount of decomposable silyl groups are introduced, and a cured product with less cross-linking defects can be formed.

Claims (7)

A method for producing an organic polymer (A) having a terminal unsaturated bond,
In the organic polymer (B), a hydroxyl group-containing organic polymer (B) is reacted with a sodium salt of a tertiary alkoxide (C) and an electrophile (D) having a terminal unsaturated bond. The method for producing an organic polymer (A), which comprises the step of converting the hydroxyl group of 1 to a terminal unsaturated bond-containing group. The organic polymer (A) and the organic polymer (B) have at least one main chain skeleton selected from the group consisting of a polyoxyalkylene-based main chain skeleton and a polyolefin-based main chain skeleton. The method for producing the organic polymer (A) according to claim 1. The method for producing an organic polymer (A) according to claim 1 or 2, wherein the step is carried out at a temperature of 60°C or higher. The terminal unsaturated bond-containing group has the following formula (1):
^{-O-R 1 -C (R 2} ) = CH 2 (1)
(In the formula, R ¹ represents a divalent hydrocarbon group having 1 to 4 carbon atoms, and R ² represents hydrogen or an alkyl group having 1 to 6 carbon atoms). The method for producing the organic polymer (A) according to any one of claims 1 to 3. The method for producing an organic polymer (A) according to claim 4, wherein R ² represents a methyl group. The method for producing an organic polymer (A) according to claim 1, wherein the sodium salt (C) of the tertiary alkoxide is sodium tert-butoxide. After producing the organic polymer (A) having a terminal unsaturated bond by the production method according to any one of claims 1 to 6, the terminal unsaturated bond of the organic polymer (A) is hydrolyzed. A method for producing an organic polymer (E) having a hydrolyzable silyl group, comprising a step of reacting a hydrosilane compound having a decomposable silyl group.