WO2020171155A1

WO2020171155A1 - Production method for organic polymer having carbon-carbon triple bond

Info

Publication number: WO2020171155A1
Application number: PCT/JP2020/006681
Authority: WO
Inventors: 達郎春増
Original assignee: 株式会社カネカ
Priority date: 2019-02-20
Filing date: 2020-02-20
Publication date: 2020-08-27
Also published as: JPWO2020171155A1

Abstract

A production method for an organic polymer (A) having a carbon-carbon triple bond, said production method including: a step in which an organic polymer (B) having a hydroxyl group is subjected to the action of an alkali metal salt as a basic compound to form an organic polymer (C) having an alkali-metal oxy group; and a step in which a brominated hydrocarbon compound having a carbon-carbon triple bond is added to the system including the organic polymer (C) and is reacted therewith.

Description

Method for producing organic polymer having carbon-carbon triple bond

The present invention relates to a method for producing an organic polymer having a carbon-carbon triple bond.

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 also 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, by reacting an electrophilic agent having an unsaturated bond, A method of using a polymer having an unsaturated bond is widely used (see, for example, Patent Document 1).

In the example of Patent Document 1, after sodium methoxide is added to a hydroxyl group-containing polyoxyalkylene, methanol is distilled off at 130° C. under reduced pressure to metal-oxylate the hydroxyl group, and then allyl chloride is used as an electrophile. It has been shown that polyoxyalkylene having an allyl group was produced by adding the above to allyl etherify the hydroxyl group.

Japanese Unexamined Patent Publication No. 7-97440

In the examples of the above-mentioned documents, allyl chloride was used as the electrophile to introduce a carbon-carbon double bond as an unsaturated bond into the organic polymer. However, no attempt has been made so far to introduce a carbon-carbon triple bond into an organic polymer.

The present inventors attempted a reaction for converting a hydroxyl group of an organic polymer into a carbon-carbon triple bond by using propargyl chloride instead of allyl chloride, and during the reaction, a carbon-carbon triple bond was contained. A side reaction in which a group (for example, HC≡C-CH ₂ -) is isomerized to an allene group (for example, H ₂ C=C=CH-) proceeds, and the content ratio of carbon-carbon triple bond in the polymer decreases. It turned out to be.

Further, when the organic polymer having a carbon-carbon triple bond contains a large amount of an isomerized organic polymer having an allene group as a by-product, it is hydrolyzable with respect to the carbon-carbon triple bond of the polymer. It was found that when a silyl group-containing hydrosilane compound was reacted to produce an organic polymer having a hydrolyzable silyl group, the physical properties of a cured product of the obtained polymer were not sufficient.

In view of the above situation, an object of the present invention is to suppress the isomerization reaction of a carbon-carbon triple bond and efficiently produce an organic polymer having a carbon-carbon triple bond from an organic polymer having a hydroxyl group. ..

Another object of the present invention is to produce an organic polymer having a hydrolyzable silyl group, which exhibits good physical properties in a cured product, from an organic polymer having a carbon-carbon triple bond.

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, after adding an alkali metal salt to a hydroxyl group-containing organic polymer to metaloxylate the hydroxyl group, a polymer having a carbon-carbon triple bond was found In producing an organic polymer having a carbon-carbon triple bond by adding and reacting an electron agent, by using a brominated hydrocarbon compound having a carbon-carbon triple bond as an electrophile, carbon-carbon It was found that the isomerization reaction of the triple bond is suppressed and an organic polymer having a carbon-carbon triple bond can be efficiently produced.

Further, the organic polymer having a hydrolyzable silyl group produced by reacting the organic polymer having a carbon-carbon triple bond obtained above with a hydrosilane compound containing a hydrolyzable silyl group is a cured product. Has also been found to exhibit good physical properties, leading to the present invention.

That is, the present invention is a method for producing an organic polymer (A) having a carbon-carbon triple bond, in which an alkali metal salt as a basic compound is allowed to act on an organic polymer (B) having a hydroxyl group to obtain an alkali metal salt. A step of forming an organic polymer (C) having a metal oxy group, and a step of adding a brominated hydrocarbon compound having a carbon-carbon triple bond to a system containing the organic polymer (C) and reacting it. , A method for producing an organic polymer (A). In the production method, a system containing the organic polymer (C) is formed after the organic polymer (C) having an alkali metal oxy group is formed and before the brominated hydrocarbon compound having a carbon-carbon triple bond is added. The step of lowering the temperature of can be further included. Preferably, the organic polymer (A) has a polyoxyalkylene-based main chain skeleton. Preferably, the alkali metal salt is an alkali metal alkoxide.
The present invention also includes a step of producing an organic polymer (A) having a carbon-carbon triple bond by the above production method, and then reacting the organic polymer (A) with a hydrosilane compound having a hydrolyzable silyl group. It also relates to a method for producing an organic polymer (D) having a hydrolyzable silyl group.

According to the present invention, an isomerization reaction of a carbon-carbon triple bond can be suppressed, and an organic polymer having a carbon-carbon triple bond can be efficiently produced from an organic polymer having a hydroxyl group.

Further, from the organic polymer having a carbon-carbon triple bond, an organic polymer having a hydrolyzable silyl group, which shows a cured product having good physical properties, can be produced.

The embodiments of the present invention will be described in detail below.

In the present invention, an organic polymer (B) having a hydroxyl group is used as a precursor, and the hydroxyl group of the organic polymer (B) is converted to a carbon-carbon triple bond-containing group via an alkali metal oxy group. The present invention relates to a method for producing an organic polymer (A) having a carbon-carbon triple bond.

(Organic polymer having carbon-carbon triple bond (A))
The structure of the carbon-carbon triple bond is not particularly limited, and among the two carbon atoms forming the carbon-carbon triple bond, a terminal alkyne group having no substituent on one carbon atom (HC≡C-), and Of the two carbon atoms forming the carbon-carbon triple bond, any of an internal alkyne group (RC≡C-) having a substituent on any of the carbon atoms may be used. Here, R is a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms. The hydrocarbon group is preferably an alkyl group. From the viewpoint of reactivity, the carbon-carbon triple bond is preferably a terminal alkyne group.

The carbon-carbon triple bond may be directly bonded to an oxygen atom to be contained in the organic polymer (A), but may be bonded to an oxygen atom via a divalent hydrocarbon group to form the organic polymer (A). Is preferably contained in. The carbon number of the divalent hydrocarbon group is preferably 1 to 8, more preferably 1 to 5, still more preferably 1 to 3, still more preferably 1 to 2, and particularly preferably 1. In the present invention, it is particularly preferable that a propargyl group (HC≡C—CH ₂ —) is contained in the organic polymer (A) by bonding to an oxygen atom.

The number of carbon-carbon triple bonds contained in the organic polymer (A) is not particularly limited, but it is preferable that one molecule of the organic polymer (A) has an average of 0.1 to 10 carbon-carbon triple bonds. It is preferably 0.5 to 6, and more preferably 0.5 to 6. The position of the carbon-carbon triple bond in the organic polymer (A) is not particularly limited, and it may be bonded to the terminal of the main chain skeleton or may be bonded to the main chain skeleton as a side chain.

The main chain skeleton of the organic polymer (A) may be linear or may have a branched chain. The type of the main chain skeleton is not particularly limited, but examples thereof include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene. Polyoxyalkylene polymers such as copolymers; ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, etc., polychloroprene, polyisoprene, isoprene or butadiene and acrylonitrile and/or styrene, etc. A copolymer of polybutadiene, isoprene or butadiene with acrylonitrile, styrene and the like, and a saturated hydrocarbon polymer such as a hydrogenated polyolefin polymer obtained by hydrogenating these polyolefin polymers; Polyester-based polymer: (meth)acrylic acid ester-based polymer obtained by radical polymerization of (meth)acrylic acid ester-based monomer such as ethyl (meth)acrylate and butyl (meth)acrylate, and (meth)acrylic acid-based polymer Vinyl-based polymers such as polymers obtained by radically polymerizing monomers such as monomers, vinyl acetate, acrylonitrile and styrene; graft polymers obtained by polymerizing vinyl monomers in the above-mentioned polymers; polyamide-based polymers Examples thereof include organic polymers such as coalesce; polycarbonate-based polymers; diallylphthalate-based polymers; The above polymers may be mixed in a block form, a graft form or the like. Among these, polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester polymers have a relatively low glass transition temperature, and the resulting cured product has excellent cold resistance. A polyoxyalkylene polymer is more preferable.

The organic polymer (A) may be a polymer having any one of the above main chain skeletons, or may be a mixture of polymers having different main chain skeletons. Further, the mixture may be a mixture of polymers produced separately, or may be a mixture in which each polymer is produced simultaneously so as to have an arbitrary mixed composition.

(Organic polymer having hydroxyl group (B))
The organic polymer (B) having a hydroxyl group used as a precursor in the present invention is not particularly limited as long as it has the same main chain skeleton as the organic polymer (A) and has a hydroxyl group. The position at which the hydroxyl group is bonded is not particularly limited, and it may be bonded to the end of the main chain skeleton or may be bonded to the main chain skeleton as a side chain. The number of hydroxyl groups contained in the organic polymer (B) is not particularly limited, and may be one or two or more.

The number average molecular weight of the organic polymer (B) is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000 in terms of polystyrene equivalent molecular weight in GPC. When the number average molecular weight is within the above range, it is easy to obtain an organic polymer (B) having a viscosity that is easy to handle and excellent workability, while suppressing the production cost within an appropriate range.

Regarding the molecular weight of the organic polymer (B), the hydroxyl group concentration can be directly determined by titration analysis based on the principle of the hydroxyl value measurement method of JIS K 1557 and the iodine value measurement method specified in JIS K0070. It can also be indicated by the molecular weight converted to the end group, which is measured and taken into consideration the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). The terminal group-equivalent molecular weight of the organic polymer (B) is obtained by GPC of the organic polymer (B) by preparing a calibration curve of the number average molecular weight obtained by general GPC measurement of the polymer and the terminal group-equivalent molecular weight. It is also possible to calculate the number average molecular weight by converting it into the molecular weight converted to the end group.

The molecular weight distribution (Mw/Mn) of the organic polymer (B) is not particularly limited, but it is preferable that the molecular weight distribution (Mw/Mn) is narrow because it can lower the viscosity. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, further preferably 1.5 or less, particularly preferably 1.4 or less, most preferably 1.3 or less. Further, from the viewpoint of improving various mechanical properties such as improving durability and elongation of the cured product, 1.2 or less is preferable. The molecular weight distribution of the organic polymer (B) can be determined from the number average molecular weight and the weight average molecular weight obtained by GPC measurement.

The production method of the organic polymer (B) is not particularly limited, and a known synthesis method can be used. However, the main chain skeleton of the organic polymer (B) is a polyoxyalkylene-based polymer having a preferable main chain skeleton. In the case of a polymer, a saturated hydrocarbon-based polymer, or a (meth)acrylic acid ester-based polymer, the manufacturing method thereof will be described below.

(Polyoxyalkylene polymer)
When the main chain skeleton of the organic polymer (B) is a polyoxyalkylene polymer, the organic polymer (B) is obtained by ring-opening polymerization of a monoepoxide in the presence of an initiator having a hydroxyl group and a catalyst. Can be obtained by

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, methanol, ethanol, propanol, Organic compounds having one or more hydroxyl groups such as butanol, pentanol, hexanol, low molecular weight polyoxypropylene monoallyl ether, and low molecular weight polyoxypropylene monoalkyl ether can be mentioned.

The monoepoxide 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 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 a small 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.

(Saturated hydrocarbon polymer)
When the main chain skeleton of the organic polymer (B) is a saturated hydrocarbon polymer, a method for producing the organic polymer (B) includes ethylene, propylene, 1-butene, isobutylene and the like having 2 to 2 carbon atoms. Examples include a method of polymerizing the olefin compound of 6 as a main monomer to obtain a polymer, and then introducing a hydroxyl group at the terminal of the molecular chain of the obtained polymer.

((Meth)acrylic acid ester-based polymer)
When the main chain skeleton of the organic polymer (B) is a (meth)acrylic acid ester-based polymer, a method for producing the organic polymer (B) includes a compound having a polymerizable unsaturated group and a hydroxyl group (for example, acryl 2-hydroxyethyl acid) may be used together with a (meth)acrylic acid ester monomer. As another method, a method of polymerizing a (meth)acrylic acid ester-based monomer by a living radical polymerization method such as atom transfer radical polymerization to obtain a polymer, and then introducing a hydroxyl group at the end of the molecular chain of the obtained polymer And so on.

(Metal oxidation reaction)
In the present invention, first, an organic polymer (C) having an alkali metal oxy group (—OM) is prepared by reacting an alkali metal salt as a basic compound with an organic polymer (B) having a hydroxyl group (—OH). To form.

The alkali metal salt is not particularly limited as long as it is a basic compound having a function of converting a hydroxyl group of the organic polymer (B) into an alkali metal oxy group, and examples thereof include an alkali metal hydroxide or an alkali metal alkoxide. Is mentioned. Specific examples include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. From the viewpoint of easy handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium t-butoxide are preferable, and sodium methoxide and More preferred is potassium methoxide. Sodium methoxide is particularly preferable in terms of availability. The alkali metal salt may be used in a state of being dissolved in a solvent.

The amount of the alkali metal salt used is not particularly limited and can be appropriately determined in consideration of the target carbon-carbon triple bond introduction rate. For example, as a molar ratio to the hydroxyl group of the organic polymer (B), 0.5 or more is preferable, 0.6 or more is more preferable, 0.7 or more is further preferable, and 0.8 or more is further more preferable. The molar ratio is preferably 2.0 or less, more preferably 1.8 or less. If the amount of the alkali metal salt used is too small, the reaction may not proceed sufficiently. On the other hand, if the amount used is too large, the alkali metal salt may remain as an impurity and the side reaction may proceed.

The reaction temperature when the alkali metal salt acts on the organic polymer (B) is the first temperature. The first temperature can be appropriately set by those skilled in the art in consideration of the reactivity between the hydroxyl group of the polymer and the alkali metal salt and is not particularly limited, but may be, for example, 100° C. or higher and 180° C. or lower. From the viewpoint of promptly proceeding the reaction of converting the hydroxyl group of the organic polymer (B) into an alkali metal oxy group, 110°C or higher is preferable, 120°C or higher is more preferable, 125°C or higher is further preferable, and 130°C or higher is Even more preferable. Further, from the viewpoint of suppressing decomposition of the organic polymer (B), the first temperature is preferably 170°C or lower, more preferably 160°C or lower, further preferably 150°C or lower, still more preferably 140°C or lower.

Since the conversion of a hydroxyl group to an alkali metal oxy group is an equilibrium reaction, it is preferable to carry out the conversion reaction while distilling off by-products such as alcohol generated by the conversion. In order to efficiently distill off the alcohol, it is preferable to carry out the conversion reaction under reduced pressure.

(Cooling process)
In the present invention, after forming the organic polymer (C) having an alkali metal oxy group as described above, the electrophilic agent is added to the system while maintaining the temperature of the system at that time to carry out the carbon-carbon triple bond introduction reaction. You can go. However, according to a preferred embodiment of the present invention, after forming the organic polymer (C) having an alkali metal oxy group, the temperature of the system containing the organic polymer (C) is changed from the first temperature to the second temperature. Lower. The second temperature may be lower than the first temperature, but is preferably 5° C. or more lower than the first temperature, more preferably 10° C. or more lower temperature, further preferably 30° C. or more lower temperature. .. By carrying out the following carbon-carbon triple bond introduction reaction at a relatively low second temperature, the isomerization reaction of the carbon-carbon triple bond is further suppressed, and an organic polymer having a carbon-carbon triple bond is obtained. It becomes possible to manufacture more efficiently.

In addition, a solvent may be added before or during this step in order to mitigate the increase in viscosity in the low temperature step. The solvent is not particularly limited, and examples thereof include acetone, acetonitrile, benzene, t-butyl alcohol, t-butyl methyl ether, chloroform, cyclohexane, 1,2-dichloroethane, diethyl ether, diglyme, 1,2-dimethoxyethane, dimethyl. Examples thereof include acetamide, dimethyl sulfoxide, dioxane, ethyl methyl ketone, n-hexane, n-heptane, toluene and tetrahydrofuran. Of these, diethyl ether, n-hexane, n-heptane, and tetrahydrofuran are particularly preferable because they are easy to handle.

The second temperature is lower than the first temperature during the metal oxidization reaction, and a person skilled in the art can appropriately set the temperature at which the isomerization reaction of the side reaction can be suppressed while the carbon-carbon triple bond introduction reaction proceeds. Good. Specifically, the range of 30°C or higher and 120°C or lower is preferable. The second temperature is preferably 40° C. or higher, more preferably 50° C. or higher, even more preferably 60° C. or higher, from the viewpoint of efficiently advancing the carbon-carbon triple bond introduction reaction while suppressing the isomerization reaction of the side reaction. 70° C. or higher is even more preferable. Further, from the viewpoint of sufficiently suppressing the isomerization reaction of the side reaction, the second temperature is preferably 110°C or lower, more preferably 100°C or lower.

(Carbon-carbon triple bond introduction reaction)
According to the present invention, the temperature of the system containing the organic polymer (C) is maintained at the first temperature or after the temperature is decreased from the first temperature to the second temperature, carbon-carbon is used as the electrophile. A carbon-carbon compound is obtained by adding a brominated hydrocarbon compound having a triple bond to the system and allowing the reaction between the organic polymer (C) and the brominated hydrocarbon compound to proceed at a first temperature or a second temperature. An organic polymer (A) having a triple bond is formed.

The brominated hydrocarbon compound having a carbon-carbon triple bond is not particularly limited, and examples thereof include propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, 1-bromo-2-octyne, 1-bromo-2-pentyne, 1,4-dibromo-2-butyne, 5-bromo-1-pentyne, 6-bromo-1-hexyne and the like can be mentioned. Of these, propargyl bromide is preferred. In addition to a brominated hydrocarbon compound having a carbon-carbon triple bond, vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, methallyl iodide. A halogenated hydrocarbon compound having a carbon-carbon double bond or the like may be added and reacted.

The amount of the brominated hydrocarbon compound having a carbon-carbon triple bond used is not particularly limited, and is appropriately determined in consideration of the reactivity of the brominated hydrocarbon compound used and the target carbon-carbon triple bond introduction rate. be able to. Specifically, the amount of the brominated hydrocarbon compound used is preferably 0.6 or more, more preferably 0.7 or more, and more preferably 0.9 or more as a molar ratio with respect to the hydroxyl group of the organic polymer (B). More preferably, 1.0 or more is particularly preferable. The molar ratio is preferably 5.0 or less, more preferably 3.0 or less, still more preferably 2.0 or less, still more preferably 1.5 or less.

The reaction time of the carbon-carbon triple bond introduction reaction is not particularly limited and can be appropriately set by a person skilled in the art. For example, it may be 10 minutes or more and 5 hours or less, and preferably 30 minutes or more and 4 hours or less. More preferably, it is not less than 4 hours and not more than 4 hours.

By the above reaction, the hydrogen atom of the hydroxyl group of the organic polymer (B) is converted into a carbon-carbon triple bond-containing group, and the organic polymer (A) having a carbon-carbon triple bond can be produced. .. According to the present invention, by using a brominated hydrocarbon compound as the electrophile having a carbon-carbon triple bond, instead of the chlorinated hydrocarbon compound used in Patent Document 1, a carbon-carbon triple bond can be obtained. The isomerization reaction from the containing group (eg, HC≡C—CH ₂ —) to the allene group (eg, H ₂ C═C═CH—) is suppressed, the isomerization rate to the allene group is low, and the carbon-carbon triple bond It is possible to obtain an organic polymer having a high content ratio.

The organic polymer (A) having a carbon-carbon triple 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 group.

(Production of Organic Polymer (D) Having Hydrolyzable Silyl Group)
A hydrosilane compound having a hydrolyzable silyl group is hydrosilylated to the organic polymer (A) having a carbon-carbon triple bond obtained by the production method of the present invention to convert the hydrolyzable silyl group into a polymer. By introducing it, the organic polymer (D) having a hydrolyzable silyl group can be produced.

(Hydrosilane compound having a hydrolyzable silyl group)
The hydrosilane compound having a hydrolyzable silyl group is not particularly limited, but the following general formula (1):
H-Si(R ¹ ) _3-a (X) _a (1)
Can be expressed as In the formula (1), R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a triorganosiloxy group represented by (R′) ₃ SiO—. The hydrocarbon group may have a hetero-containing group. R'is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. a is 1, 2, or 3.

Examples of R ¹ include a hydrogen atom; an alkyl group such as a methyl group and an ethyl group; an alkyl group having a hetero-containing group such as a chloromethyl group and a methoxymethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl such as a phenyl group Group; an aralkyl group such as a benzyl group; and a triorganosiloxy group represented by (R') ₃ SiO- in which R'is a methyl group, a phenyl group or the like. An alkyl group is preferable, a methyl group, an ethyl group, a chloromethyl group, and a methoxymethyl group are more preferable, a methyl group and an ethyl group are still more preferable, and a methyl group is particularly preferable. When a plurality of R ^1's are present, they may be the same or different from each other.

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. X 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 X, only one type of group may be used, or two or more types of groups may be used in combination.

A is 1, 2, or 3. As a, 2 or 3 is preferable.

Specific examples of the hydrosilane compound having a hydrolyzable silyl group include, for example, trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, and bis(chloromethyl). ) Halogenated silanes such as chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane , Ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, bis(chloromethyl)methoxysilane, (methoxymethyl)methylmethoxy Silane, (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) Dimethoxysilyloxy]dimethylsilane, [(methoxymethyl)diemethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane, [(3,3,3-trifluoropropyl)dimethoxysilyloxy]dimethylsilane Alkoxysilanes such as; acetoxymethylsilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; ketoximatesilanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane; triisopropenyl Examples thereof include isopropenyloxysilanes (deacetone type) such as roxysilane, (chloromethyl)diisopropenyloxysilane, and (methoxymethyl)diisopropenyloxysilane. Among them, dimethoxymethylsilane, trimethoxysilane, triethoxysilane, or methoxymethyldimethoxysilane is preferable.

The amount of the hydrosilane compound having a hydrolyzable silyl group may be appropriately set in consideration of the amount of carbon-carbon triple bond contained in the organic polymer (A). Specifically, the molar ratio of the hydrosilane compound to the carbon-carbon triple bond of the organic polymer (A) is preferably 0.05 or more and 10 or less, and more preferably 0.3 or more and 2 or less from the viewpoint of reactivity.

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 metals such as cobalt, nickel, iridium, platinum, palladium, rhodium and ruthenium, and complexes thereof can be used. Specifically, platinum supported on a carrier such as alumina, silica, 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 [eg Ph(PPh ₃ ) ₄ , Pt(PBu ₃ ) ₄ ]; platinum-phosphite complex [eg Pt{P(OPh) ₃ } ₄ ] and the like. To be From the viewpoint of reaction efficiency, platinum catalysts such as chloroplatinic acid and platinum vinyl siloxane complex are 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 hydrosilylation reaction temperature 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 and improving the reactivity, a temperature higher than room temperature is preferable, and specifically, 50°C to 150° C. is more preferable, and 70° C. to 120° C. is further preferable. Particularly, a hydrosilylation reaction temperature of 70° C. or higher is preferable from the viewpoint of reaction efficiency of the hydrosilylation reaction. Further, the temperature is preferably 40 to 70° C. for the purpose of suppressing the generation of foreign matter when adding the platinum catalyst. The temperature may be changed during the hydrosilylation reaction.

The reaction time of the hydrosilylation reaction may be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that the unintended condensation reaction of the polymer does not proceed. Specifically, 30 minutes or more and 15 hours or less are preferable, and 30 minutes or more and 8 hours or less are more preferable.

Also, 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, based on 100 parts by weight of the organic polymer (A) having a carbon-carbon triple bond. ..

Through the above steps, the hydrosilylation reaction of the organic polymer (A) having a carbon-carbon triple bond proceeds, and one or two molecules of the hydrosilane compound are added to one carbon-carbon triple bond, whereby The organic polymer (D) having a degradable silyl group can be produced.

The organic polymer (D) 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. The organic polymer (D) having a hydrolyzable silyl group produced according to the present invention can give a cured product having excellent physical properties such as toughness by the hydrolysis/condensation reaction of the hydrolyzable silyl group.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, "part" is based on weight.

The number average molecular weight in the examples is the GPC molecular weight measured under the following conditions.
Liquid transfer system: Tosoh HLC-8220GPC
Column: Tosoh TSKgel Super H series Solvent: THF
Molecular weight: polystyrene conversion Measurement temperature: 40°C

The terminal group-equivalent molecular weights in the examples are obtained by measuring the hydroxyl value by the measuring method of JIS K 1557 and the iodine value by the measuring method of JIS K0070, and determining the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). This is the molecular weight determined in consideration.

(Synthesis example 1)
Polyoxypropylene glycol having a terminal group-converted molecular weight of about 2,000 was used as an initiator to polymerize propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst to give a hydroxyl group at both terminals of a number average molecular weight of 27,900 (terminal group). A polyoxypropylene (P-1) having a converted molecular weight of 17,700) and a molecular weight distribution Mw/Mn=1.21 was obtained. The viscosity of the polymer (P-1) was 39.3 Pa·s as a result of measurement with an E-type viscometer (Tokyo Keiki, measuring cone: 3°C×R14).

(Example 1)
1.05 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (P-1) obtained in Synthesis Example 1. Methanol was distilled off by vacuum devolatilization at 130° C. to convert the hydroxyl group of the polymer into an alkali metal oxy group. Then, the temperature of the system is lowered to 100° C., and at this temperature (second temperature), 1.16 molar equivalents of propargyl bromide to the hydroxyl group of the polymer (P-1) are added to give an alkali metal oxy group. A propargyl group was introduced into the polymer by reacting with the polymer for 2 hours. Unreacted propargyl bromide was removed by vacuum devolatilization. The resulting unpurified propargyl-terminated polyoxypropylene was mixed and stirred with n-hexane and water, then water was removed by centrifugation, and hexane was removed from the obtained hexane solution under reduced pressure to remove metal in the polymer. The salt was removed. As described above, polyoxypropylene (Q-1) having a propargyl group at the terminal was obtained. The viscosity of the polymer (Q-1) was measured with an E-type viscometer (Tokyo Keiki, measuring cone: 3°C×R14), and the thickening rate was calculated from the viscosities before and after the reaction. Further, the molar ratio of the alkyne group and the allene group introduced into the polymer was calculated by ¹ H NMR analysis of the polymer (Q-1). The results are shown in Table 1.

(Comparative Example 1)
1.05 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (P-1) obtained in Synthesis Example 1. The methanol was distilled off by vacuum devolatilization at 130° C. to convert the hydroxyl groups contained in the polymer into alkali metal oxy groups. Next, the temperature of the system is lowered to 100° C., and at this temperature (second temperature), 1.16 molar equivalents of propargyl chloride with respect to the hydroxyl groups of the polymer (P-1) are added to give an alkali metal oxy group. A propargyl group was introduced into the polymer by reacting for 2 hours. Unreacted propargyl chloride was removed by vacuum devolatilization. The resulting unpurified propargyl-terminated polyoxypropylene was mixed and stirred with n-hexane and water, then water was removed by centrifugation, and hexane was removed from the obtained hexane solution under reduced pressure to remove metal in the polymer. The salt was removed. As described above, polyoxypropylene (Q-2) having a propargyl group at the terminal was obtained. The viscosity of the polymer (Q-2) was measured with an E-type viscometer (Tokyo Keiki, measuring cone: 3°C×R14), and the thickening rate was calculated from the viscosities before and after the reaction. Further, the molar ratio of the alkyne group and the allene group introduced into the polymer was calculated by ¹ H NMR analysis of the polymer (Q-2). The results are shown in Table 1.

(Comparative example 2)
1.05 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (P-1) obtained in Synthesis Example 1. The methanol was distilled off by vacuum devolatilization at 130° C. to convert the hydroxyl groups contained in the polymer into alkali metal oxy groups. Next, while maintaining the temperature of the system at 130° C. (second temperature), 1.16 molar equivalents of propargyl chloride to the hydroxyl group of the polymer (P-1) were added, and the reaction was performed with the alkali metal oxy group for 2 hours. By doing so, a propargyl group was introduced into the polymer. Unreacted propargyl chloride was removed by vacuum devolatilization. The resulting unpurified propargyl-terminated polyoxypropylene was mixed and stirred with n-hexane and water, then water was removed by centrifugation, and hexane was removed from the obtained hexane solution under reduced pressure to remove metal in the polymer. The salt was removed. Thus, polyoxypropylene (Q-3) having a propargyl group at the terminal was obtained. The viscosity of the polymer (Q-3) was measured with an E-type viscometer (Tokyo Keiki, measuring cone: 3°C×R14), and the thickening rate was calculated from the viscosities before and after the reaction. Further, the molar ratio of the alkyne group and the allene group introduced into the polymer was calculated by ¹ H NMR analysis of the polymer (Q-3). The results are shown in Table 1.

As is clear from Table 1, in Example 1, as compared with Comparative Examples 1 and 2, the molar ratio of the arene group was decreased and the molar ratio of the alkyne group was significantly increased. From this, the carbon-carbon triple bond introduction reaction is carried out by using a brominated hydrocarbon compound having a carbon-carbon triple bond, not a chlorohydrocarbon compound having a carbon-carbon triple bond, as the electrophile. Thus, it is understood that the isomerization reaction of the carbon-carbon triple bond can be suppressed and the organic polymer having the carbon-carbon triple bond can be efficiently produced. In addition, Example 1 has a smaller viscosity increase after the reaction as compared with Comparative Examples 1 and 2, and it can be seen that the use of the brominated hydrocarbon compound can suppress an increase in viscosity due to a side reaction.

(Example 2)
To 500 g of the polymer (Q-1) obtained in Example 1, 150 μL of platinum divinyldisiloxane complex (3% by weight of isopropanol solution in terms of platinum) and 8.37 g of trimethoxysilane were added to carry out hydrosilylation. The reaction was carried out. After reacting at 90° C. for 2 hours, unreacted trimethoxysilane was distilled off under reduced pressure to obtain a polyoxypropylene polymer (R-1) having a trimethoxysilyl group at the terminal. The viscosity of the polymer before and after the silylation reaction was measured with an E-type viscometer (Tokyo Keiki, measuring cone: 3°C×R14) to calculate the viscosity increase rate.
Further, 0.75 parts of tin octylate, 0.125 parts of laurylamine, and 0.6 parts of water are mixed with 100 parts of the polymer (R-1) to prevent air bubbles from entering the polyethylene mold. And was cured at 23° C. and 50% RH for 1 hour and further at 70° C. for 20 hours to prepare a sheet having a thickness of about 3 mm. The sheet was punched into a No. 3 dumbbell mold and subjected to a tensile strength test at 23° C. and 50% RH to measure 100% modulus (M100) and strength at break (TB). The tensile strength was measured with an autograph (AGS-J) manufactured by Shimadzu Corporation at a pulling speed of 200 mm/min. The results are shown in Table 2.

(Comparative example 3)
To 500 g of the polymer (Q-2) obtained in Comparative Example 1, 150 μL of platinum divinyldisiloxane complex (3% by weight of platinum in isopropanol solution) and 8.37 g of trimethoxysilane were added, and hydrosilylation was performed. The reaction was carried out. After reacting for 2 hours at 90° C., unreacted trimethoxysilane was distilled off under reduced pressure to obtain a polyoxypropylene polymer (R-2) having a trimethoxysilyl group at the terminal. The viscosity of the polymer before and after the silylation reaction was measured with an E-type viscometer (Tokyo Keiki, measuring cone: 3°C×R14), and the viscosity increase rate was calculated.
Furthermore, 0.75 parts of tin octylate, 0.125 parts of laurylamine, and 0.6 parts of water are mixed with 100 parts of the polymer (R-2) to prevent bubbles from entering the polyethylene mold. And was cured at 23° C. and 50% RH for 1 hour and further at 70° C. for 20 hours to prepare a sheet having a thickness of about 3 mm. The sheet was punched into a No. 3 dumbbell mold and subjected to a tensile strength test at 23° C. and 50% RH, and 100% modulus (M100) and strength at break (TB) were measured. The tensile strength was measured with an autograph (AGS-J) manufactured by Shimadzu Corporation at a pulling speed of 200 mm/min. The results are shown in Table 2.

As is clear from Table 2, the polymer of Example 2 obtained by introducing a hydrolyzable silyl group into the polymer of Example 1 having a high alkyne group content has a comparatively low alkyne group content. It can be seen that, as compared with the polymer of Comparative Example 3 obtained by introducing a hydrolyzable silyl group into the polymer of Example 1, it has a low viscosity and high mechanical strength after curing.

Claims

A process for producing an organic polymer (A) having a carbon-carbon triple bond,
A step of acting an alkali metal salt as a basic compound on the organic polymer (B) having a hydroxyl group to form an organic polymer (C) having an alkali metal oxy group,
A method for producing an organic polymer (A), which comprises a step of adding a brominated hydrocarbon compound having a carbon-carbon triple bond to a system containing the organic polymer (C) and reacting the compound.
After forming the organic polymer (C) having an alkali metal oxy group, and before adding the brominated hydrocarbon compound having a carbon-carbon triple bond, the temperature of the system containing the organic polymer (C) is lowered. The method for producing the organic polymer (A) according to claim 1, further comprising a step.
The method for producing the organic polymer (A) according to claim 1 or 2, wherein the organic polymer (A) has a polyoxyalkylene-based main chain skeleton.
The method for producing the organic polymer (A) according to any one of claims 1 to 3, wherein the alkali metal salt is an alkali metal alkoxide.
After producing an organic polymer (A) having a carbon-carbon triple bond by the production method according to any one of claims 1 to 4, the organic polymer (A) has a hydrolyzable silyl group. A method for producing an organic polymer (D) having a hydrolyzable silyl group, comprising the step of reacting a hydrosilane compound.