阅读说明：本技术 具有碳-碳三键的有机聚合物的制造方法 (Method for producing organic polymer having carbon-carbon triple bond ) 是由 春增达郎 N.久保田 于 2020-02-20 设计创作，主要内容包括：本发明涉及具有碳-碳三键的有机聚合物(A)的制造方法,该方法包括：在第一温度下使作为碱性化合物的碱金属盐作用于具有羟基的有机聚合物(B)而形成具有碱金属氧基的有机聚合物(C)的工序；使包含上述有机聚合物(C)的体系的温度从上述第一温度降低至第二温度的工序；以及在上述体系中添加具有碳-碳三键的卤代烃化合物,并在上述第二温度下使其与上述有机聚合物(C)进行反应的工序。(The present invention relates to a method for producing an organic polymer (a) having a carbon-carbon triple bond, comprising: a step of allowing an alkali metal salt as a basic compound to act on the organic polymer (B) having a hydroxyl group at a first temperature to form an organic polymer (C) having an alkali metal oxy group; a step of lowering the temperature of the system containing the organic polymer (C) from the first temperature to a second temperature; and a step of adding a halogenated hydrocarbon compound having a carbon-carbon triple bond to the system and reacting the halogenated hydrocarbon compound with the organic polymer (C) at the second temperature.)

1. A method for producing an organic polymer (a) having a carbon-carbon triple bond, comprising:

a step of allowing an alkali metal salt as a basic compound to act on the organic polymer (B) having a hydroxyl group at a first temperature to form an organic polymer (C) having an alkali metal oxy group;

a step of lowering the temperature of a system containing the organic polymer (C) from the first temperature to a second temperature; and

and (C) adding a halogenated hydrocarbon compound having a carbon-carbon triple bond to the system, and reacting the halogenated hydrocarbon compound with the organic polymer (C) at the second temperature.

2. The method for producing the organic polymer (A) according to claim 1,

the second temperature is a temperature of 120 ℃ or less.

3. The method for producing the organic polymer (A) according to claim 1 or 2,

the organic polymer (A) has a polyoxyalkylene main chain skeleton.

4. The method for producing the organic polymer (A) according to any one of claims 1 to 3, wherein,

the first temperature is a temperature of 125 ℃ or higher.

5. The method for producing the organic polymer (A) according to any one of claims 1 to 4, wherein,

the alkali metal salt is an alkali metal alkoxide.

6. A method for producing an organic polymer (D) having a hydrolyzable silyl group, comprising:

a step of reacting a hydrosilane compound having a hydrolyzable silyl group with the organic polymer (A) after the organic polymer (A) having a carbon-carbon triple bond is produced by the production method according to any one of claims 1 to 5.

Technical Field

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

Background

The organic polymer having an unsaturated bond bonded to the main chain is a polymer exhibiting curability, and is useful as a curable material and also as a precursor for producing an organic polymer having a hydrolyzable silyl group.

As a method for synthesizing such an unsaturated bond-containing organic polymer, a method is known in which an organic polymer having a hydroxyl group is produced, and then the hydroxyl group is converted into an unsaturated bond-containing group. Among them, the following methods are widely used: a method of forming a polyoxyalkylene polymer having a hydroxyl group by polymerization, reacting an alkali metal alkoxide with the hydroxyl group to perform metal oxidation, and then reacting an electrophile having an unsaturated bond to produce a polymer having an unsaturated bond (see, for example, patent document 1).

In the examples of patent document 1, it is shown that a polyoxyalkylene having an allyl group is produced by adding sodium methoxide to a polyoxyalkylene having a hydroxyl group, distilling off methanol at 130 ℃ under reduced pressure, oxidizing the hydroxyl group with a metal, and then adding allyl chloride as an electrophile to etherify the hydroxyl group with an allyl group.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 7-97440

Disclosure of Invention

Problems to be solved by the invention

The examples of the above documents introduce a carbon-carbon double bond as an unsaturated bond to an organic polymer by using allyl chloride as an electrophile. However, no attempt has been made to introduce a carbon-carbon triple bond into an organic polymer.

The present inventors have attempted a reaction for converting a hydroxyl group of an organic polymer into a carbon-carbon triple bond, and found that: under the existing reaction conditions for introducing a carbon-carbon double bond, a carbon-carbon triple bond-containing group (e.g., HC ≡ C-CH) is reacted₂-) isomerization to allenyl (e.g., H)₂A side reaction of C ═ CH —), and the content ratio of carbon-carbon triple bonds in the polymer decreases.

In view of the above-described situation, an object of the present invention is to produce an organic polymer having a carbon-carbon triple bond from an organic polymer having a hydroxyl group with good efficiency by suppressing an isomerization reaction of the carbon-carbon triple bond.

Means for solving the problems

As a result of intensive studies to solve the above problems, the present inventors have found that when an alkali metal salt is added to a hydroxyl group-containing organic polymer, a hydroxyl group is metal-oxidized at a high temperature, and then an electrophile having a carbon-carbon triple bond is added to the resultant mixture to carry out a reaction, the isomerization reaction of the carbon-carbon triple bond can be suppressed by setting the temperature of the system to be lower than that in the metal oxidation reaction, and an organic polymer having a carbon-carbon triple bond can be efficiently produced, thereby completing the present invention.

That is, the present invention relates to a method for producing an organic polymer (a) having a carbon-carbon triple bond, the method comprising: a step of allowing an alkali metal salt as a basic compound to act on the organic polymer (B) having a hydroxyl group at a first temperature to form an organic polymer (C) having an alkali metal oxy group; a step of lowering the temperature of the system containing the organic polymer (C) from the first temperature to a second temperature; and a step of adding a halogenated hydrocarbon compound having a carbon-carbon triple bond to the system and reacting the halogenated hydrocarbon compound with the organic polymer (C) at the second temperature. The second temperature is preferably 120 ℃ or lower. The organic polymer (a) preferably has a main chain skeleton of a polyoxyalkylene system. The first temperature is preferably 125 ℃ or higher. Preferably, the alkali metal salt is an alkali metal alkoxide.

The present invention also relates to a method for producing an organic polymer (D) having a hydrolyzable silyl group, the method including: a step of reacting a hydrosilane compound having a hydrolyzable silyl group with the organic polymer (A) after the organic polymer (A) having a carbon-carbon triple bond is produced by the above-mentioned production method.

ADVANTAGEOUS EFFECTS OF INVENTION

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

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

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail.

The present invention relates to a method for producing an organic polymer (A) having a carbon-carbon triple bond, which comprises using an organic polymer (B) having a hydroxyl group as a precursor and converting the hydroxyl group of the organic polymer (B) into a group having a carbon-carbon triple bond via an alkali metal oxy group.

(organic Polymer (A) having a carbon-carbon triple bond)

The structure of the carbon-carbon triple bond is not particularly limited, and may be any of the following structures: a terminal alkynyl group having no substituent on 1 carbon atom of 2 carbon atoms constituting a carbon-carbon triple bond (HC ≡ C-); and an internal alkynyl group (RC ≡ C-) having a substituent on any carbon atom of 2 carbon atoms constituting the carbon-carbon triple bond. Here, R is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and the number of carbon atoms is preferably 1 to 4, more preferably 1 to 2. In addition, the hydrocarbon group is preferably an alkyl group. From the viewpoint of reactivity, the carbon-carbon triple bond is preferably a terminal alkynyl group.

The carbon-carbon triple bond may be directly bonded to an oxygen atom to be contained in the organic polymer (a), and is preferably bonded to an oxygen atom via a 2-valent hydrocarbon group to be contained in the organic polymer (a). The number of carbon atoms of the 2-valent hydrocarbon group is preferably 1 to 8, more preferably 1 to 5, further preferably 1 to 3, further preferably 1 to 2, and particularly preferably 1. In the present invention, propargyl (HC ≡ C-CH) is particularly preferable₂-) is bonded to an oxygen atom and contained in the organic polymer (A).

The number of carbon-carbon triple bonds of the organic polymer (A) is not particularly limited, and the organic polymer (A) preferably has an average of 0.1 to 10 carbon-carbon triple bonds, more preferably 0.5 to 6 carbon-carbon triple bonds per 1 molecule of the organic polymer (A). The position of the carbon-carbon triple bond in the organic polymer (a) is not particularly limited, and 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 branched. The kind of the main chain skeleton is not particularly limited, and examples thereof include: polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polytetrahydrofuran, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer; saturated hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene or the like, polychloroprene, polyisoprene, copolymers of isoprene or butadiene and acrylonitrile and/or styrene or the like, polybutadiene, copolymers of isoprene or butadiene and acrylonitrile and styrene or the like, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; polyester-based polymers; vinyl polymers such as (meth) acrylate polymers obtained by radical polymerization of (meth) acrylate monomers such as ethyl (meth) acrylate and butyl (meth) acrylate, and polymers obtained by radical polymerization of (meth) acrylic monomers and monomers such as vinyl acetate, acrylonitrile, and styrene; a graft polymer obtained by polymerizing a vinyl monomer in the above polymer; a polyamide-based polymer; a polycarbonate-series polymer; diallyl phthalate-based polymers; and the like. The above-mentioned polymers may be present in a mixture in the form of blocks, grafts, or the like. Among these, polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth) acrylate polymers are preferred because of their low glass transition temperature and excellent cold resistance of the resulting cured product, and polyoxyalkylene polymers are more preferred.

The organic polymer (a) may be a polymer having any of the above-described various main chain skeletons, or may be a mixture of polymers having different main chain skeletons. The mixture may be a mixture of polymers produced individually or a mixture obtained by producing each polymer simultaneously so as to have an arbitrary mixture composition.

(organic Polymer (B) having hydroxyl group)

In the present invention, the organic polymer (B) having a hydroxyl group used as a precursor is not particularly limited as long as it has the same main chain skeleton as the organic polymer (a) and is a polymer having a hydroxyl group. The position at which the hydroxyl group is bonded is not particularly limited, and 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. The number of hydroxyl groups of the organic polymer (B) is not particularly limited, and may be 1, or 2 or more.

The number average molecular weight of the organic polymer (B) is preferably 3000 to 100000, more preferably 3000 to 50000, and particularly preferably 3000 to 30000, in terms of a molecular weight in terms of polystyrene in GPC. When the number average molecular weight is within the above range, the organic polymer (B) having a viscosity that is easy to handle and excellent in handling property can be easily obtained while the production cost is suppressed within an appropriate range.

The molecular weight of the organic polymer (B) may be represented by an end group-converted molecular weight obtained by directly measuring the hydroxyl group concentration by titration analysis based on the principles of the hydroxyl group value measurement method according to JIS K1557 and the iodine value measurement method according to JIS K0070, taking into consideration the structure of the organic polymer (the degree of branching determined according to the polymerization initiator used). The molecular weight of the organic polymer (B) in terms of the terminal group can also be determined as follows: a calibration curve of the number average molecular weight of the polymer determined by a conventional GPC measurement and the terminal group-equivalent molecular weight described above was prepared, and the number average molecular weight determined by GPC of the organic polymer (B) was converted into the terminal group-equivalent molecular weight.

The molecular weight distribution (Mw/Mn) of the organic polymer (B) is not particularly limited, but a narrow range is preferred because a low viscosity can be achieved. 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, and most preferably 1.3 or less. Further, from the viewpoint of improving various mechanical properties such as durability and elongation of the cured product, it is preferably 1.2 or less. 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 method for producing the organic polymer (B) is not particularly limited, and a known synthesis method can be used, and the following description will be made of a method for producing a polyoxyalkylene polymer, a saturated hydrocarbon polymer, or a (meth) acrylate polymer, in which the main chain skeleton of the organic polymer (B) is a preferable main chain skeleton.

(polyoxyalkylene polymer)

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

The initiator having a hydroxyl group is not particularly limited, and examples thereof include: organic compounds having 1 or more hydroxyl groups such as ethylene glycol, propylene glycol, glycerol, pentaerythritol, polyoxypropylene glycol having a low molecular weight, polyoxypropylene triol having a low molecular weight, allyl alcohol, methanol, ethanol, propanol, butanol, pentanol, hexanol, polyoxypropylene monoallyl ether having a low molecular weight, polyoxypropylene monoalkyl ether having a low molecular weight, and the like.

The monoepoxide is not particularly limited, and examples thereof include: alkylene oxides such as ethylene oxide, propylene oxide, α -butylene oxide, β -butylene oxide, hexylene oxide, cyclohexylene oxide, styrene oxide and α -methylstyrene oxide, alkyl glycidyl ethers such as methyl glycidyl ether, ethyl glycidyl ether, isopropyl glycidyl ether and butyl glycidyl ether, allyl glycidyl ether and aryl glycidyl ether. Propylene oxide is preferred.

The catalyst is not particularly limited, and for example: known catalysts include basic catalysts such as KOH and NaOH, acidic catalysts such as boron trifluoride-diethyl ether, and complex metal cyanide complex catalysts such as aluminum porphyrin metal complex and cobalt zinc cyanide-glyme complex catalysts. Among them, the double metal cyanide complex catalyst is preferable because it is less in chain transfer reaction and can give a polymer having a high molecular weight and a narrow molecular weight distribution. In addition, by reacting basic compounds, e.g. KOH, NaOH, KOCH₃、NaOCH₃Acting on a polyoxyalkylene polymer having a small number average molecular weight, and further reacting a halogenated alkyl group having 2 or more functions, for example, CH₂BrCl、CH₂Cl₂、CH₂Br₂And the like, and a high molecular weight polyoxyalkylene polymer can be obtained by a chain extension reaction.

(saturated hydrocarbon Polymer)

When the main chain skeleton of the organic polymer (B) is a saturated hydrocarbon polymer, examples of the method for producing the organic polymer (B) include: a method in which an olefin compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene, isobutylene or the like is polymerized as a main monomer to obtain a polymer, and then a hydroxyl group is introduced into the molecular chain terminal of the obtained polymer.

((meth) acrylic acid ester polymer)

When the main chain skeleton of the organic polymer (B) is a (meth) acrylate polymer, examples of the method for producing the organic polymer (B) include: a method of copolymerizing a compound having a polymerizable unsaturated group and a hydroxyl group (for example, 2-hydroxyethyl acrylate) with a (meth) acrylate monomer. Other methods include a method in which a (meth) acrylate monomer is polymerized by a living radical polymerization method such as atom transfer radical polymerization to obtain a polymer, and then a hydroxyl group is introduced into the molecular chain terminal of the obtained polymer.

(Metal Oxidation reaction)

In the present invention, first, an alkali metal salt as a basic compound is allowed to act on an organic polymer (B) having a hydroxyl group (-OH) to form an organic polymer (C) having an alkali metal oxy (-OM).

The alkali metal salt is not particularly limited as long as it is a basic compound having an action of converting a hydroxyl group of the organic polymer (B) into an alkali metal oxy group, and examples thereof include: alkali metal hydroxides or alkali metal alkoxides. Specific examples thereof include: sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, cesium alkoxide, and the like. From the viewpoint of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred, and sodium methoxide and potassium methoxide are more preferred. Sodium methoxide is particularly preferable from the viewpoint of availability. The alkali metal salt may be used in a state dissolved in a solvent,

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

The reaction temperature when the alkali metal salt is allowed to act on the organic polymer (B) is set to a first temperature. The first temperature is not particularly limited, and may be set as appropriate by those skilled in the art in consideration of reactivity of the hydroxyl group of the polymer with the alkali metal salt, and may be, for example, 100 ℃ to 180 ℃. From the viewpoint of rapidly advancing the reaction for converting the hydroxyl group of the organic polymer (B) into the alkali metal oxy group, it is preferably 110 ℃ or higher, more preferably 120 ℃ or higher, still more preferably 125 ℃ or higher, and still more preferably 130 ℃ or higher. From the viewpoint of suppressing decomposition of the organic polymer (B), the first temperature is preferably 170 ℃ or lower, more preferably 160 ℃ or lower, still more preferably 150 ℃ or lower, and still more preferably 140 ℃ or lower.

Since the conversion from 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 a by-product such as an alcohol produced by the conversion. In order to efficiently distill off the alcohol, the above-mentioned conversion reaction is preferably carried out under reduced pressure.

(temperature lowering step)

In the present invention, after the organic polymer (C) having an alkali metal oxy group is formed by the above operation, the temperature of the system containing the organic polymer (C) is lowered from the above first temperature to the second temperature. The second temperature may be lower than the first temperature, and is preferably lower than the first temperature by 5 ℃ or more, more preferably lower than the first temperature by 10 ℃ or more, still more preferably lower than the first temperature by 30 ℃ or more, and still more preferably lower than the first temperature by 50 ℃ or more. In this way, by performing the subsequent carbon-carbon triple bond introduction reaction at a relatively low second temperature, 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, a solvent may be added before or during the step of lowering the temperature in order to alleviate the increase in viscosity in the step of lowering the temperature. The solvent is not particularly limited, and examples thereof include: acetone, acetonitrile, benzene, tert-butanol, tert-butyl methyl ether, chloroform, cyclohexane, 1, 2-dichloroethane, diethyl ether, diglyme, 1, 2-dimethoxyethane, dimethylacetamide, dimethyl sulfoxide, and diethylene glycolAlkyl, ethyl methyl ketone, n-hexane, n-heptane, toluene, tetrahydrofuran, and the like. Among these, diethyl ether, n-hexane, n-heptane, and tetrahydrofuran are preferable because of ease of handling.

In addition, according to the conventional method described in patent document 1, the carbon-carbon double bond introduction reaction is performed at a temperature at which the alkali metal salt is allowed to act on the organic polymer having a hydroxyl group, while maintaining the temperature. In the introduction of the carbon-carbon double bond, the isomerization reaction according to the present invention does not proceed, and the two-stage reaction at the same temperature does not cause a particular problem. In contrast, the present inventors have found that the carbon-carbon triple bond introduction reaction is accompanied by the isomerization reaction, and as a method for suppressing the isomerization reaction, it is effective to lower the temperature at the time of the carbon-carbon triple bond introduction reaction.

As the second temperature, those skilled in the art may set a temperature lower than the first temperature in the metal oxidation reaction and capable of suppressing the isomerization reaction of the side reaction while performing the carbon-carbon triple bond introduction reaction, as appropriate. Specifically, it is preferably in the range of 30 ℃ to 120 ℃. The second temperature is preferably 40 ℃ or higher, more preferably 50 ℃ or higher, even more preferably 60 ℃ or higher, and even more preferably 70 ℃ or higher, from the viewpoint of suppressing the isomerization reaction, which is a side reaction, and also performing the carbon-carbon triple bond introduction reaction with good efficiency. From the viewpoint of sufficiently suppressing the isomerization reaction which is a side reaction, the second temperature is preferably 110 ℃ or lower, more preferably 100 ℃ or lower, further preferably 90 ℃ or lower, further preferably 80 ℃ or lower, and particularly preferably 70 ℃ or lower.

(carbon-carbon triple bond introduction reaction)

According to the present invention, as described above, the temperature of the system containing the organic polymer (C) is lowered from the first temperature to the second temperature, and then a halogenated hydrocarbon compound having a carbon-carbon triple bond is added as an electrophile to the system, and the reaction between the organic polymer (C) and the halogenated hydrocarbon compound proceeds at the second temperature, thereby forming the organic polymer (a) having a carbon-carbon triple bond.

The halogenated hydrocarbon compound having a carbon-carbon triple bond is not particularly limited, and includes: propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentyne, 1, 4-dichloro-2-butyne, 5-chloro-1-pentyne, 6-chloro-1-hexyne, 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, propargyl iodide, 1-iodo-2-butyne, 4-iodo-1-butyne, 1-iodo-2-octyne, 1-iodo-2-pentyne, 1, 4-diiodo-2-butyne, 5-iodo-1-pentyne, and 6-iodo-1-hexyne, and the like. Of these, propargyl chloride, propargyl bromide, and propargyl iodide are preferred. In addition to the hydrocarbon halide compound having a carbon-carbon triple bond, a hydrocarbon halide compound having a carbon-carbon double bond such as vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, propylene bromide, methallyl bromide, vinyl iodide, allyl iodide, methallyl iodide, and the like may be added to carry out the reaction.

The amount of the halogenated hydrocarbon compound having a carbon-carbon triple bond to be used is not particularly limited, and may be suitably determined in consideration of the reactivity of the halogenated hydrocarbon compound to be used and the target carbon-carbon triple bond introduction rate. Specifically, the amount of the halogenated hydrocarbon compound to be used is preferably 0.6 or more, more preferably 0.7 or more, still more preferably 0.9 or more, and still more preferably 1.0 or more in terms of a molar ratio to the hydroxyl group of the organic polymer (B). The molar ratio is preferably 5.0 or less, more preferably 3.0 or less, still more preferably 2.0 or less, and 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, and may be, for example, 10 minutes to 5 hours, preferably 30 minutes to 4 hours, and more preferably 1 hour to 4 hours.

By the above reaction, the hydrogen atom of the hydroxyl group of the organic polymer (B) can be converted into a group containing a carbon-carbon triple bond, thereby producing the organic polymer (a) having a carbon-carbon triple bond. According to the invention, it is possible to inhibit the formation of carbon-carbon triple bond-containing groups (e.g. HC ≡ C-CH)₂-) to allenyl (e.g. H₂Isomerization of C ═ CH —) gives an organic polymer having a low isomerization rate to allene groups and a high content of carbon-carbon triple bonds.

The organic polymer (a) having a carbon-carbon triple bond produced by the above-described operation can be used as a curable material together with a curing agent and a curing catalyst. As described below, the hydrolyzable silyl group-containing organic polymer can also be used as a precursor for producing an organic polymer having a hydrolyzable silyl group.

(preparation of organic Polymer (D) having hydrolyzable silyl group)

The hydrosilyl group can be introduced into the polymer by subjecting a hydrosilyl compound having a hydrolyzable silyl group to a hydrosilylation reaction with the organic polymer (a) having a carbon-carbon triple bond obtained by the production method of the present invention, whereby an organic polymer (D) having a hydrolyzable silyl group can be produced.

(hydrosilane Compound having hydrolyzable silyl group)

The hydrosilane compound having a hydrolyzable silyl group is not particularly limited, and may be represented by the following general formula (1):

H-Si(R¹)_3-a(X)_a (1)。

in the formula (1), R¹Represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms or (R')₃SiO-watchThe triorganosiloxy groups shown. The above hydrocarbon group optionally has a hetero atom-containing group. R' are the same or different and represent 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.

As R¹Examples thereof include: a hydrogen atom; alkyl groups such as methyl and ethyl; an alkyl group having a hetero atom-containing group such as chloromethyl group and methoxymethyl group; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl; aralkyl groups such as benzyl; r 'is methyl, phenyl, etc. (R')₃Triorganosiloxy group represented by SiO-and the like. The alkyl group is preferably a methyl group, an ethyl group, a chloromethyl group, or a methoxymethyl group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. In the presence of a plurality of R¹In the case of (2), they may be the same or different from each other.

Examples of X include: hydroxyl, hydrogen, halogen, alkoxy, acyloxy, ketoximino (ketoximate group), amino, amide, acid amide, aminoxy, mercapto, alkenyloxy, and the like. In view of stable hydrolyzability and easy handling, X is preferably an alkoxy group, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, still more preferably a methoxy group, an ethoxy group, and yet still more preferably a methoxy group. As X, only one kind of group may be used, or two or more kinds 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: halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorosilance, (chloromethyl) dichlorosilane, (dichloromethyl) dichlorosilane, bis (chloromethyl) chlorosilane, (methoxymethyl) dichlorosilane, (dimethoxymethyl) dichlorosilane, and bis (methoxymethyl) chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl) methylmethoxysilane, (chloromethyl) dimethoxysilane, (chloromethyl) diethoxysilane, bis (chloromethyl) methoxysilane, (methoxymethyl) methylmethoxysilane, (methoxymethyl) dimethoxysilane, bis (methoxymethyl) methoxysilane, (methoxymethyl) diethoxysilane, (ethoxymethyl) diethoxysilane, (3,3, 3-trifluoropropyl) dimethoxysilane, (N, N-diethylaminomethyl) diethoxysilane, [ (chloromethyl) dimethoxysiloxy ] dimethylsilane, dimethoxymethylsilane, and a mixture thereof, Alkoxysilanes such as [ (chloromethyl) diethoxysilyloxy ] dimethylsilane, [ (methoxymethyl) dimethoxysiloxy ] dimethylsilane, [ (diethylaminomethyl) dimethoxysiloxy ] dimethylsilane, [ (3,3, 3-trifluoropropyl) dimethoxysiloxy ] dimethylsilane and the like; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; ketoximidosilanes such as bis (dimethylketoximidoyl) methylsilane and bis (cyclohexylketoximidoyl) methylsilane, and isopropenyloxysilanes (deacetonized) such as triisopropenoxysilane, (chloromethyl) diisopropenoxysilane, and (methoxymethyl) diisopropenoxysilane. 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 the carbon-carbon triple bond of the organic polymer (a). Specifically, from the viewpoint of reactivity, 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.

To promote the reaction, it is preferable that the hydrosilylation reaction is carried out in the presence of a hydrosilylation catalyst. The hydrosilylation catalyst is not particularly limited, and metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium, and complexes thereof can be used. Specific examples thereof include: a catalyst in which platinum is supported on a carrier such as alumina, silica, or carbon black, or chloroplatinic acid; chloroplatinic acid complexation comprising chloroplatinic acid and alcohols, aldehydes, ketones, and the likeAn agent; platinum-olefin complexes [ e.g. Pt (CH)₂＝CH₂)₂(PPh₃)、Pt(CH₂＝CH₂)₂Cl₂](ii) a Platinum-vinyl siloxane complexes [ e.g. Pt { (vinyl) Me₂SiOSiMe₂(vinyl)}、Pt{Me(vinyl)SiO}₄](ii) a Platinum-phosphine complexes [ e.g. Ph (PPh)₃)₄、Pt(PBu₃)₄](ii) a Platinum-phosphite complexes [ e.g. Pt { P (OPh)₃}₄]And the like. From the viewpoint of reaction efficiency, a platinum catalyst such as chloroplatinic acid or a platinum vinylsiloxane complex is preferable. In addition, sulfur is also preferably added in order to maintain the activity of the platinum catalyst for a long time. The sulfur may be added in a state dissolved in an organic solvent such as hexane.

The hydrosilylation reaction temperature is not particularly limited, and can be set as appropriate by those skilled in the art, and is preferably higher than normal temperature for the purpose of reducing the viscosity of the reaction system and improving the reactivity, and specifically, is preferably 50 to 150 ℃, and more preferably 70 to 120 ℃. From the viewpoint of the reaction efficiency of the hydrosilylation reaction, a hydrosilylation reaction temperature of 70 ℃ or higher is particularly preferable. Further, for the purpose of suppressing the generation of impurities when the platinum catalyst is added, it is preferably 40 to 70 ℃. The temperature can be varied during the hydrosilylation reaction.

The reaction time of the hydrosilylation reaction may be appropriately set, and it is preferable to adjust the reaction time together with the temperature condition so as not to cause an unexpected condensation reaction of the polymer. Specifically, it is preferably 30 minutes to 15 hours, more preferably 30 minutes to 8 hours.

In addition, the hydrosilylation reaction may be carried out in the presence of a trialkyl orthocarboxylate. 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. Trimethyl orthoformate and trimethyl orthoacetate are preferred. The amount of the organic polymer (a) 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-described steps, the hydrosilylation reaction of the organic polymer (a) having a carbon-carbon triple bond is performed, and 1 or 2 molecules of the hydrosilane compound are added to 1 carbon-carbon triple bond, whereby the organic polymer (D) having a hydrolyzable silyl group can be produced.

The organic polymer (D) having a hydrolyzable silyl group produced by the above-described procedure can be used as a curable resin utilizing hydrolysis/condensation reaction of a hydrolyzable silyl group. In this case, a silanol condensing catalyst or the like may be added. The organic polymer (D) having a hydrolyzable silyl group produced by the present invention can obtain a cured product having excellent physical properties such as toughness through hydrolysis/condensation reaction of the hydrolyzable silyl group.

Examples

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

The number average molecular weight in the examples is a GPC molecular weight measured under the following conditions.

A liquid delivery system: HLC-8220GPC made by Tosoh

A chromatographic column: TSKgel SuperH series made by Tosoh

Solvent: THF (tetrahydrofuran)

Molecular weight: conversion to polystyrene

Measuring temperature: 40 deg.C

The molecular weight in terms of terminal group in the examples is a molecular weight obtained by obtaining a hydroxyl value by the measurement method of JIS K1557 and an iodine value by the measurement method of JIS K0070, taking into account the structure of the organic polymer (branching degree determined according to the polymerization initiator used).

(Synthesis example 1)

Propylene oxide was polymerized using polypropylene oxide having an end group equivalent molecular weight of about 2000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (P-1) having a number average molecular weight 27900 (end group equivalent molecular weight 17700) and a molecular weight distribution Mw/Mn of 1.21, which had hydroxyl groups at both ends. The viscosity of the polymer (P-1) was measured with an E-type viscometer (Tokyo counter, measurement cone: 3 ℃ C.. times.R 14), and found to be 39.3 pas.

(example 1)

1.05 molar equivalents of sodium methoxide were added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (P-1) obtained in Synthesis example 1 as a 28% methanol solution. Methanol was distilled off by vacuum devolatilization at 130 deg.C (first temperature) to convert the hydroxyl groups possessed by the polymer into alkali metal oxy groups. Then, the temperature of the system was lowered to 70 ℃ (second temperature), and at this temperature, 1.16 molar equivalents of propargyl chloride was added to the hydroxyl groups of the polymer (P-1), and the polymer was reacted with an alkali metal oxy group for 2 hours, thereby introducing propargyl groups into the polymer. Unreacted propargyl chloride was removed by devolatilization under reduced pressure. After the obtained unpurified propargyl-terminated polyoxypropylene was mixed with n-hexane and water and stirred, water was removed by centrifugation, and hexane was devolatilized from the resulting hexane solution under reduced pressure to remove the metal salt in the polymer. Through the above operation, 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 counter, measurement cone: 3 ℃ C.. times.R 14), and the thickening ratio was calculated from the viscosities before and after the reaction. Further, by the polymer (Q-1)¹H NMR analysis calculated the molar ratio of alkynyl group and allenyl group introduced into the polymer. The results are shown in Table 1.

(example 2)

1.05 molar equivalents of sodium methoxide were added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (P-1) obtained in Synthesis example 1 as a 28% methanol solution. Methanol was distilled off by vacuum devolatilization at 130 deg.C (first temperature) to convert the hydroxyl groups possessed by the polymer into alkali metal oxy groups. Next, the temperature of the system was lowered to 100 ℃ (second temperature), and at this temperature, 1.16 molar equivalents of propargyl chloride was added to the hydroxyl groups of the polymer (P-1), and the polymer was reacted with an alkali metal oxy group for 2 hours, thereby introducing propargyl groups into the polymer. Unreacted propargyl chloride was removed by devolatilization under reduced pressure. The obtained unpurified propargyl-terminated polyoxypropylene was mixed with n-hexane and water, stirred, and then subjected to dissociationThe water was removed by centrifugation, and hexane was devolatilized from the resulting hexane solution under reduced pressure, whereby the metal salts in the polymer were removed. By the above procedure, 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 counter, measurement cone: 3 ℃ C.. times.R 14), and the thickening ratio was calculated from the viscosities before and after the reaction. Further, by the polymer (Q-2)¹H NMR analysis calculated the molar ratio of alkynyl group and allenyl group introduced into the polymer. The results are shown in Table 1.

(example 3)

1.05 molar equivalents of sodium methoxide were added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (P-1) obtained in Synthesis example 1 as a 28% methanol solution. Methanol was distilled off by vacuum devolatilization at 130 deg.C (first temperature) to convert the hydroxyl groups possessed by the polymer into alkali metal oxy groups. Next, the temperature of the system was lowered to 120 ℃ (second temperature), and at this temperature, 1.16 molar equivalents of propargyl chloride was added to the hydroxyl groups of the polymer (P-1), and the polymer was reacted with an alkali metal oxy group for 2 hours, thereby introducing propargyl groups into the polymer. Unreacted propargyl chloride was removed by devolatilization under reduced pressure. After the obtained unpurified propargyl-terminated polyoxypropylene was mixed with n-hexane and water and stirred, water was removed by centrifugation, and hexane was devolatilized from the resulting hexane solution under reduced pressure to remove the metal salt in the polymer. By the above procedure, 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 counter, measurement cone: 3 ℃ C.. times.R 14), and the thickening ratio was calculated from the viscosities before and after the reaction. Further, by the polymer (Q-3)¹H NMR analysis calculated the molar ratio of alkynyl group and allenyl group introduced into the polymer. The results are shown in Table 1.

Comparative example 1

1.05 molar equivalents of sodium methoxide were added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (P-1) obtained in Synthesis example 1 as a 28% methanol solution. Methanol was distilled off by vacuum devolatilization at 130 deg.C (first temperature) to convert the hydroxyl groups possessed by the polymer into alkali metal oxy groups. Then, the body is putPropargyl group was introduced into the polymer by adding 1.16 molar equivalents of propargyl chloride to the hydroxyl group of the polymer (P-1) and reacting the resultant with an alkali metal oxy group for 2 hours while maintaining the temperature of 130 ℃. Unreacted propargyl chloride was removed by devolatilization under reduced pressure. After the obtained unpurified propargyl-terminated polyoxypropylene was mixed with n-hexane and water and stirred, water was removed by centrifugation, and hexane was devolatilized from the resulting hexane solution under reduced pressure to remove the metal salt in the polymer. By the above procedure, polyoxypropylene (Q-4) having a propargyl group at the terminal was obtained. The viscosity of the polymer (Q-4) was measured with an E-type viscometer (Tokyo counter, measurement cone: 3 ℃ C.. times.R 14), and the thickening ratio was calculated from the viscosities before and after the reaction. Further, by the polymer (Q-4)¹H NMR analysis calculated the molar ratio of alkynyl group and allenyl group introduced into the polymer. The results are shown in Table 1.

[ Table 1]

As is clear from table 1, in examples 1 to 3, the molar ratio of allenyl groups decreased and the molar ratio of alkynyl groups increased significantly as compared with comparative example 1. From this, it is found that by lowering the reaction temperature at the time of converting the hydroxyl group of the polymer into the alkali metal oxy group and then performing the carbon-carbon triple bond introduction reaction at the second temperature, the isomerization reaction of the carbon-carbon triple bond can be suppressed, and the organic polymer having the carbon-carbon triple bond can be produced with good efficiency. In examples 1 to 3, the thickening ratio after the reaction was smaller than that of comparative example 1, and the thickening ratio after the reaction was smaller as the reaction temperature (second temperature) at which the alkali metal oxy group of the polymer and the halogenated hydrocarbon compound having a carbon-carbon triple bond were reacted was lower. That is, by lowering the reaction temperature at the time of converting the hydroxyl group of the polymer into the alkali metal oxy group and then performing the carbon-carbon triple bond introduction reaction at the second temperature, the increase in viscosity due to the side reaction can be suppressed.

(example 4)

150. mu.L of a divinyldisiloxane platinum complex (an isopropyl alcohol solution of 3 wt% in terms of platinum) and 5.5g of trimethoxysilane were added to 500g of the polyoxypropylene (Q-2) having a propargyl group at the terminal obtained in example 2 to carry out a hydrosilation reaction. After the mixed solution was reacted at 90 ℃ for 2 hours, unreacted trimethoxysilane was distilled off under reduced pressure, whereby polyoxypropylene having a number average molecular weight of 28500 having a trimethoxysilyl group at the terminal was obtained.