JP2020094105A - Method for producing organic polymer and curable composition - Google Patents

Abstract

To provide a novel method for producing an organic polymer with excellent production efficiency.SOLUTION: A method for producing an organic polymer has: a step 1 for starting a hydrosilylation reaction in which a silicon hydride compound (A) having a specific structure, an organic polymer (B) and a catalyst (C), are mixed in a reaction container, and the silicon hydride compound (A) is added to the organic polymer (B); and a step 2 in which a quinone compound (D) is added to a reaction mixture in the step 1.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a method for producing an organic polymer and a curable composition containing the organic polymer obtained by the production method.

A reaction in which a silicon hydride compound having a Si-H group is added to a carbon-carbon unsaturated bond is generally called a hydrosilylation reaction.

In industrially utilizing the hydrosilylation reaction, a major problem is to suppress a decrease in the reaction rate or a termination of the reaction, which is caused by a reason such as a decrease in the activity of the catalyst during the reaction.

Therefore, various methods and additives have been conventionally proposed for suppressing the decrease in the reaction rate of the hydrosilylation reaction.

For example, Patent Document 1 discloses a hydrosilylation reaction method of a silicon compound and a polymer containing an alkenyl group, which is carried out in the presence of a catalyst and a quinone compound. Patent Document 2 discloses a method for producing an organic polymer having a reactive silicon group, which uses a quinone compound in addition to a catalyst.

JP 2001-206908 A JP, 2008-195822, A

However, the above-described conventional technology has room for further improvement in terms of production efficiency.

One embodiment of the present invention has been made in view of the above problems, and an object thereof is to provide a novel method for producing an organic polymer, which is excellent in production efficiency.

The present inventors, as a result of intensive studies to solve the above problems, by adding a quinone compound after the start of the hydrosilylation reaction, it is possible to significantly increase the reaction rate, and therefore excellent in production efficiency, It has been found that a novel method for producing an organic polymer can be provided, and the present invention has been completed.

That is, one embodiment of the present invention includes the following configurations.
[1] A silicon hydride compound (A), an organic polymer (B) and a catalyst (C) are mixed in a reaction vessel, and the silicon hydride compound (A) is mixed with the organic polymer (B). ) Is added to the reaction mixture of step 1 and the quinone compound (D) is added to the reaction mixture of step 1, and the silicon hydride compound (A) has the following general formula (A): 1),
R _a X _b H _c Si ··· formula (1)
(In the general formula (1), a R's are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a triorganosiloxy group having 1 to 20 carbon atoms, and b X independently of each other is a halogen atom or a hydrolyzable group, a or b is an integer of 0 to 3, c is an integer of 1 to 3, and a+b+c=4).
The organic polymer (B) has an unsaturated group, and the catalyst (C) contains at least one transition metal selected from the group consisting of Group 8, Group 9 and Group 10, Method for producing organic polymer.
[2] The method for producing an organic polymer according to [1], wherein the quinone compound (D) is a compound represented by the following general formula (2), (3) or (4):

(In the general formulas (2) to (4), R ^{1 to} R ¹⁸ are each independently a hydrogen element, a hydroxyl group, or a functional group having at least one carbon element).
[3] The main chain skeleton of the organic polymer (B) is at least one polymer selected from the group consisting of polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic polymers. The method for producing an organic polymer according to [1] or [2], which comprises a polymer unit consisting of
[4] The method for producing an organic polymer according to any one of [1] to [3], wherein the unsaturated group is a 2-methylallyl group.
[5] The method for producing an organic polymer according to any one of [1] to [4], wherein the molecular weight distribution of the organic polymer (B) is 1.0 or more and less than 1.8.
[6] The method for producing an organic polymer according to any one of [1] to [5], wherein an end of the main chain or side chain of the organic polymer (B) is an unsaturated group.
[7] In step 1, an antioxidant and oxygen are further added to the reaction vessel, and the amount of oxygen added is 0.1 when the volume of the gas phase in the reaction vessel is 100% by volume. The method for producing an organic polymer according to any one of [1] to [6], wherein the organic polymer is 20% by volume.
[8] A curable composition containing the organic polymer produced by the method for producing an organic polymer according to any one of [1] to [7].

According to one embodiment of the present invention, there is an effect that it is possible to provide a method for producing an organic polymer, which is excellent in production efficiency.

One embodiment of the present invention will be described below, but the present invention is not limited to this. The present invention is not limited to each configuration described below, and various modifications can be made within the scope of the claims. Further, embodiments or examples obtained by appropriately combining the technical means disclosed in the different embodiments or examples are also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each of the embodiments. In addition, all the academic documents and patent documents described in this specification are incorporated as a reference in this specification. Unless otherwise specified in this specification, “A to B” representing a numerical range means “A or more (including A and larger than A) and B or less (including B and smaller than B)”.

[1. Technical idea according to an embodiment of the present invention]
The inventor of the present invention considered that there is room for further improvement in the techniques described in Patent Documents 1 and 2 from the viewpoint of production efficiency, and conducted extensive studies. As a result, the present inventors have uniquely found that, by adding the quinone compound after the initiation of the hydrosilylation reaction, it is possible to surprisingly significantly increase the reaction rate. The reason for this is considered as follows, but one embodiment of the present invention is not limited to the following principle.

In the hydrosilylation reaction carried out by mixing the silicon hydride compound (A), the organic polymer (B), the catalyst (C) and the quinone compound (D), the silicon hydride compound (a) is added to the quinone compound (D). The reaction between A) and the organic polymer (B) is promoted, and (b) a side reaction (a reaction other than the intended hydrosilylation reaction) between the quinone compound (D) and the silicon hydride compound (A) occurs, Side reaction products are produced. As the side reaction between the quinone compound (D) and the silicon hydride compound (A) occurs and a side reaction product is produced, the amount of the quinone compound (D) that can accelerate the hydrosilylation reaction decreases.

In the techniques described in Patent Documents 1 and 2, a large number of side reactions occur between the quinone compound (D) and the silicon hydride compound (A) in the early stage after the initiation of the hydrosilylation reaction, and a large amount of side reaction occurs in the early stage after the initiation of the reaction. It is speculated that a side reaction product is produced. As a result, in the techniques described in Patent Documents 1 and 2, the amount of the quinone compound (D) capable of promoting the hydrosilylation reaction is reduced, and it is speculated that the promotion of the hydrosilylation reaction by the quinone compound is not sufficient.

On the other hand, in the method for producing an organic polymer according to one embodiment of the present invention, a silicon hydride compound (A), an organic polymer (B), and a catalyst (C) are mixed to start a hydrosilylation reaction, and then , Quinone compound (D) is added. Therefore, in the method for producing an organic polymer according to one embodiment of the present invention, the side reaction between the quinone compound (D) and the silicon hydride compound (A) is compared to the techniques described in Patent Documents 1 and 2. It is presumed that the hydrosilylation reaction occurs slowly in the late stage after the initiation of the hydrosilylation reaction and a small amount of side reaction product is produced in the early stage after the initiation of the reaction. As a result, in the method for producing an organic polymer according to one embodiment of the present invention, the amount of the quinone compound (D) capable of promoting the hydrosilylation reaction is sufficient compared to the techniques described in Patent Documents 1 and 2. Since it exists, it is speculated that the hydrosilylation reaction is sufficiently promoted by the quinone compound.

[2. Method for producing organic polymer]
In the method for producing an organic polymer according to one embodiment of the present invention, the silicon hydride compound (A), the organic polymer (B) and the catalyst (C) are mixed in a reaction vessel to obtain the organic polymer. Step 1 of initiating a hydrosilylation reaction of adding the silicon hydride compound (A) to (B), and Step 2 of adding the quinone compound (D) to the reaction mixture of Step 1; The silicon hydride compound (A) is represented by the following general formula (1),
R _a X _b H _c Si ··· formula (1)
(In the general formula (1), a R's are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a triorganosiloxy group having 1 to 20 carbon atoms, and b X independently of each other is a halogen atom or a hydrolyzable group, a or b is an integer of 0 to 3, c is an integer of 1 to 3, and a+b+c=4).
The organic polymer (B) has an unsaturated group, and the catalyst (C) contains at least one transition metal selected from the group consisting of Group 8, Group 9 and Group 10.

The method for producing an organic polymer according to one embodiment of the present invention is also simply referred to as the present production method. The term "the present production method" refers to one aspect of the method for producing the organic polymer of the present invention.

Since the present production method has the above-mentioned constitution, the reaction rate of the hydrosilylation reaction in the present production method is remarkably faster than the reaction rate of the hydrosilylation reaction in the conventional production method (hereinafter also referred to as conventional method). Have. Further, in the present production method, as described above, as compared with the conventional method, the reaction rate of the hydrosilylation reaction is higher than that in the conventional method even when the amount of the silicon hydride compound (A) used is reduced. Has the advantage of being fast. Therefore, the present manufacturing method has an advantage of excellent production efficiency as compared with the conventional method.

The organic polymer obtained by the present production method is also within the scope of the present invention. The organic polymer obtained by this production method has a reactive silicon group. In the present specification, the reactive silicon group means an organic group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom. The organic polymer having a reactive silicon group obtained by the present production method has a characteristic that a siloxane bond is formed by a reaction accelerated by a silanol condensation catalyst and crosslinked. Therefore, the organic polymer obtained by this manufacturing method can provide a curable composition. The curable composition can provide a cured product by curing the curable composition. That is, it can be said that the organic polymer obtained by the present production method can provide a cured product.

Examples of the reactive silicon group include silicon groups represented by the following general formula (5):
-SiR _a X _b H _c ··· formula (5)
(In the general formula (5), a R's each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a triorganosiloxy group having 1 to 20 carbon atoms, and b X are independently a halogen atom or a hydrolyzable group, a and b are integers of 0 to 3, c is an integer of 0 to 2, and a+b+c=3.).

(2-1. Step 1)
Step 1 is a step of mixing the silicon hydride compound (A), the organic polymer (B) and the catalyst (C) in the reaction vessel. Thereby, the hydrosilylation reaction of adding the silicon hydride compound (A) represented by the general formula (1) to the organic polymer (B) having an unsaturated group can be started. A substance obtained by mixing the silicon hydride compound (A), the organic polymer (B) and the catalyst (C) is referred to as a reaction mixture.

The silicon hydride compound (A) plays a role of introducing a reactive silicon group into the organic polymer (B) by being added to the organic polymer (B) having an unsaturated group. It can be said that the addition reaction of the silicon hydride compound (A) to the organic polymer (B) is a hydrosilylation reaction of the organic polymer (B).

In the general formula (1), it is preferable that each a R is independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a triorganosiloxy group having 1 to 20 carbon atoms. More preferably, it is an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 15 carbon atoms or a triorganosiloxy group having 1 to 15 carbon atoms, and an alkyl group having 1 to 10 carbon atoms and 6 to 10 carbon atoms. Is more preferably an aryl group having 1 to 10 carbon atoms or a triorganosiloxy group having 1 to 10 carbon atoms, and an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 8 carbon atoms or a triorganosiloxy group having 1 to 3 carbon atoms. It is particularly preferable that

In the general formula (1), b Xs are each independently a halogen atom or a hydrolyzable group. The hydrolyzable group is a group having hydrolysis reactivity and is not particularly limited, and examples thereof include an alkoxy group, an acyloxy group, and a hydroxyl group.

In the general formula (1), c is preferably 1.

The silicon hydride compound (A) is not particularly limited, and known compounds can be mentioned. Examples of the silicon hydride compound (A) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and trimethylsiloxydichlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, methoxydimethylsilane, dimethoxy. Alkoxysilanes such as phenylsilane, 1,3,3,5,5,7,7-heptamethyl-1,1-dimethoxytetrasiloxane; Acyloxysilanes such as methyldiacetoxysilane and trimethylsiloxymethylacetoxysilane; Dimethyl Hydrosilanes having two or more Si-H bonds in the molecule such as silane, trimethylsiloxymethylsilane, 1,1,3,3-tetramethyldisiloxane, and 1,3,5-trimethylcyclotrisiloxane; methyldi( Examples thereof include alkenyloxysilanes such as isopropenyloxy)silane. Among these, methyldichlorosilane, dimethoxymethylsilane, diethoxymethylsilane, trimethoxysilane, and triethoxysilane are preferable. As the silicon hydride compound (A), only one type of compound may be used, or two or more types of compounds may be used in combination.

As the amount of the silicon hydride compound (A) used, the ratio (molar ratio) to the unsaturated group in the organic polymer (B) used is important. The molar ratio of the silicon hydride compound (A) to the unsaturated group in the organic polymer (B) used (the number of moles of the unsaturated group in the organic polymer (B)/the mole of the silicon hydride compound (A)) The number is preferably 0.1 to 20, and more preferably 0.5 to 3. Further, this production method has an advantage that the molar ratio of the silicon hydride compound (A) to the unsaturated group in the organic polymer (B) used can be made smaller than that in the conventional method. For example, in the present production method, when the molar ratio is 1.1, the production efficiency (reaction rate) equivalent to that in the conventional method when the molar ratio is 1.5 can be achieved. From this viewpoint, it can be said that the molar ratio is preferably less than 1.5, more preferably 1.3 or less, and further preferably 1.2 or less. The molar ratio is preferably 1.1 or more.

The term “usage” of a substance (ingredient) means the total amount of the substance (ingredient) used in the production method. When the usage amount of the substance (component) is used at one time, the usage amount can be said to be the addition amount.

The unsaturated group contained in the organic polymer (B) is an unsaturated group capable of addition reaction (that is, hydrosilylation reaction) of the silicon hydride group (A). The unsaturated group may be referred to as an unsaturated group having hydrosilylation activity.

The organic polymer (B) has at least one unsaturated group having hydrosilylation activity in the molecule. In the present specification, a structural unit other than the unsaturated group having hydrosilylation activity in the organic polymer (B) is referred to as a main chain skeleton. In other words, the organic polymer (B) has a main chain skeleton and at least one unsaturated group having hydrosilylation activity. The structure of the main chain skeleton is not particularly limited, and the main chain skeleton includes polymer units made of various known polymers.

The structure of the main chain skeleton of the organic polymer (B) is not particularly limited and may be a linear structure or a branched structure.

The structure of the main chain skeleton is not particularly limited, and the main chain skeleton includes polymer units made of various known polymers. The polymer unit that can be contained in the main chain skeleton of the organic polymer (B) is not particularly limited, and examples thereof include polyoxyalkylene-based polymers, ethylene-propylene-based copolymers, hydrocarbon-based polymers, and polyester-based polymers. Examples of the polymer unit include a polymer, a (meth)acrylic polymer, a vinyl polymer, a polysulfide polymer, a polyamide polymer, a polycarbonate polymer, and a diallylphthalate polymer. .. The polymer unit that can be contained in the main chain skeleton of the organic polymer (B) is a polymer unit composed of a graft polymer obtained by polymerizing a vinyl compound in the above-mentioned polymer or copolymer. Good.

As used herein, the term "(meth)acrylic" refers to acrylic and/or methacrylic.

Examples of the polyoxyalkylene polymer include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer and the like. Can be mentioned. “Polyoxypropylene” is also referred to as “polypropylene oxide”.

Examples of the hydrocarbon-based polymer include a polyolefin-based polymer, and a hydrogenated polyolefin-based polymer obtained by hydrogenating a polyolefin-based polymer. As the polyolefin-based polymer, polyisobutylene, a copolymer of isobutylene and isoprene, etc., polychloroprene, polyisoprene, polybutadiene, isoprene or a copolymer of butadiene and acrylonitrile or styrene, etc., isoprene or butadiene and acrylonitrile and styrene. And the like. Hydrocarbon-based polymers having no carbon-carbon double bond in the molecule, such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, are also referred to as saturated hydrocarbon polymers.

The polyester polymer can be obtained by condensation of a dibasic acid such as adipic acid and glycol, or ring-opening polymerization of lactones.

The (meth)acrylic polymer can be obtained by radical polymerization of compounds such as (meth)acrylic acid, sodium (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate.

The vinyl polymer can be obtained by radical polymerization of compounds such as vinyl acetate, acrylonitrile and styrene.

The polyamide-based polymer is obtained by polycondensation of polyamide 6 obtained by ring-opening polymerization of ε-caprolactam, polycondensation of hexamethylenediamine and adipic acid, and polycondensation of hexamethylenediamine and sebacic acid. Examples thereof include polyamide 6/10, polyamide 11 obtained by polycondensation of ε-aminoundecanoic acid, polyamide 12 obtained by ring-opening polymerization of ε-aminolaurolactam, and copolyamides composed of a plurality of these polyamides.

Examples of the polycarbonate-based polymer include polycarbonate obtained by polycondensation of bisphenol A and carbonyl chloride.

The main chain skeleton of the organic polymer (B) is a polymer composed of at least one polymer selected from the group consisting of polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic polymers. It is preferable that the unit contains a unit. According to the above structure, the organic polymer (B) has a relatively low glass transition temperature. As a result, the obtained organic polymer can provide a cured product having excellent cold resistance. Further, according to the above-mentioned constitution, the cured product which can be provided by the obtained organic polymer also has an advantage that in a use as an adhesive and a sealing material, migration (contamination) of a low molecular weight component to an adherend is small. ..

It is more preferable that the main chain skeleton of the organic polymer (B) contains a polymer unit composed of at least one polymer selected from the group consisting of polyoxyalkylene polymers and (meth)acrylic polymers. It is more preferable that it contains a polymer unit composed of a polyoxyalkylene polymer. According to the said structure, an organic polymer with high moisture permeability can be obtained. Therefore, the curable resin composition that can be provided by the obtained organic polymer is excellent in deep-part curability when used as a main component such as a one-pack type adhesive and a sealing material. As a result, the obtained cured product has an advantage of excellent adhesiveness.

The unsaturated group having hydrosilylation activity that the organic polymer (B) has is not particularly limited, and examples thereof include an allyl group, a 2-methylallyl group, and a methacryloyl group. When the unsaturated group is a 2-methylallyl group, the effect of promoting the hydrosilylation reaction by the addition of the quinone compound (D) is greater than when the unsaturated group is an allyl group. Therefore, the unsaturated group having a hydrosilylation activity contained in the organic polymer (B) is preferably a 2-methylallyl group.

The unsaturated group having hydrosilylation activity contained in the organic polymer (B) is preferably present at the terminal of the main chain or side chain of the organic polymer (B). In other words, the terminal of the main chain or side chain of the organic polymer (B) is preferably an unsaturated group. According to the above constitution, the efficiency of the addition of the silicon hydride compound (A) to the organic polymer (B), that is, the hydrosilylation reaction is improved. Examples of the embodiment in which the terminal of the main chain or side chain of the organic polymer (B) is an unsaturated group include, for example, any one of the following (a) to (d) or a combination thereof: (a ) A mode in which the terminal of the main chain skeleton of the organic polymer (B) is substituted with an unsaturated group, (b) a part of the functional groups of the main chain skeleton of the organic polymer (B) is substituted with an unsaturated group And (c) the main chain skeleton of the organic polymer (B) has a branched structure (including a graft structure), and an end of the branched chain (for example, a graft chain) is substituted with an unsaturated group, And (d) an embodiment in which the main chain skeleton of the organic polymer (B) has a branched structure (including a graft structure), and a part of the functional groups of the branched chain (for example, the graft chain) is substituted with an unsaturated group ..

In the organic polymer (B), the number of unsaturated groups having hydrosilylation activity present in one molecule is at least 1 or more, preferably 1.1 to 10.0, and 1.1. It is more preferable that the number is 5.0 to 5.0, and further preferable that the number is 1.1 to 3.0. The organic polymer (B) referred to here is an aggregate of organic polymer (B) molecules having one or more unsaturated groups having hydrosilylation activity per molecule. All of the heavy-duty polymer (B) molecules contained in the organic polymer (B) (aggregate) used in the present production method may have the same or different number of unsaturated groups.

The organic polymer (B) is preferably an organic polymer having at least one organic group represented by the following general formula (6):
^{_{H 2 C = C (R 19}} ) -R 20 - ··· formula (6)
(In the general formula (6), R ¹⁹ is a hydrogen element or a hydrocarbon group having 1 to 10 carbon atoms, and R ²⁰ is at least one element selected from the group consisting of a hydrogen element, an oxygen element and a nitrogen element. Is a divalent organic group having 1 to 20 carbon atoms.

The organic polymer (B) may have a plurality of organic groups represented by the general formula (6). When the organic polymer (B) has a plurality of organic groups represented by the general formula (6), a plurality of R ¹⁹ and R ²⁰ may be the same or different. R ²⁰ in the general formula (6) may form at least a part of the main chain skeleton in the organic polymer (B) having the organic group represented by the general formula (6). In the organic polymer (B) having an organic group represented by the general formula (6), H ₂ which is an organic group having a side chain (hydrogen element or hydrocarbon group represented by R ¹⁹ ) and a carbon-carbon unsaturated bond ^{C = C (R 19) -} , ^{_{or, H 2 C = C (R}} 19) - organic group consisting of a part of the ^{R 20} may be an unsaturated group which hydrosilation activity.

When the organic polymer (B) is the organic polymer represented by the general formula (6), it is possible to increase the introduction rate of the reactive silicon group by the hydrosilylation reaction. A cured product made of an organic polymer having a high introduction rate of a reactive silicon group has an advantage of having excellent physical properties.

The unsaturated group having hydrosilylation activity described in the general formula (6) is not particularly limited, and examples thereof include an allyl group, a 2-methylallyl group and a methacryloyl group. These unsaturated groups are preferably present at the ends of the main chain and side chains.

The glass transition temperature of the organic polymer (B) is not particularly limited and is preferably 20° C. or lower, more preferably 0° C. or lower, and particularly preferably −20° C. or lower. When the glass transition temperature of the organic polymer (B) is 20° C. or lower, the curable composition that can be provided by the obtained organic polymer does not have a high viscosity in the winter or the cold regions, and the winter or the cold regions. Also, the workability is improved. As a result, the curable composition can provide a cured product having good flexibility and elongation. The glass transition temperature of the organic polymer (B) can be determined by DSC measurement according to the measuring method specified in JIS K7121.

The number average molecular weight of the organic polymer (B) is preferably 500 to 200,000, and preferably 1,000 to 100, in terms of a value obtained by converting the measured value of GPC using tetrahydrofuran (also referred to as THF) as a mobile phase in terms of polystyrene. 000 is more preferable, and 5,000 to 50,000 is particularly preferable. In the present specification, the number average molecular weight of the organic polymer (B) is a value obtained by measurement of gel permeation chromatography (GPC) using THF as a mobile phase, which is a value converted into polystyrene. ..

The molecular weight distribution of the organic polymer (B) is preferably 1.0 or more and less than 1.8.

The method for producing the organic polymer (B) is not particularly limited, and known production methods can be mentioned.

The at least one transition metal selected from the group consisting of Group 8, Group 9 and Group 10 contained in the catalyst (C) is, for example, cobalt, nickel, ruthenium, rhodium, palladium, iridium or platinum. (Platinum) and the like.

As the catalyst (C), a metal simple substance of at least one transition metal selected from the group consisting of Group 8, Group 9 and Group 10, a metal salt of the transition metal, or the transition metal and an organic compound The complex of is mentioned. As the catalyst (C), for example, a substance obtained by supporting platinum on a carrier such as alumina, silica or carbon black; chloroplatinic acid; a chloroplatinic acid complex composed of chloroplatinic acid and an alcohol, an aldehyde or a ketone; platinum - olefin complexes _{[e.g., Pt (CH 2 = CH 2} ) 2 (PPh 3) and _{Pt (CH 2 = CH 2)} 2 Cl 2]; platinum - vinylsiloxane complex [for _{example, Pt {(vinyl) Me 2} SiOSiMe ₂ (vinyl)} and Pt{Me(vinyl)SiO} ₄ ]; platinum-phosphine complex [eg Ph(PPh ₃ ) ₄ and Pt(PBu ₃ ) ₄ ]; platinum-phosphite complex [eg Pt{P (OPh) ₃ } ₄ ]; Platinum-acetylacetonate complex [for example, Pt(C ₅ H ₇ O ₂ ) ₂ ] and the like are preferable. Incidentally, in the illustrated above, "vinyl" indicates a vinyl group _(CH 2 = CH-), "Me" represents a methyl group - shows a (CH _3).

Examples of catalysts (C) include dicarbonyldichloroplatinum, platinum-hydrocarbon complexes described in Ashby US Pat. Nos. 3,159,601 and 3,159,662, and Lamoreaux US Pat. No. 3,220,972. The platinum-alcoholate catalysts described in 1. are also preferred.

As the catalyst (C), a platinum chloride-olefin composite described in Modic US Pat. No. 3,516,946 is also preferable.

As the catalyst (C), chloroplatinic acid, a platinum-olefin complex, a platinum-acetylacetonate complex, and a platinum-vinylsiloxane complex are more preferable among the above because they have a relatively high reaction activity.

As the catalyst (C), only one kind may be used, or a plurality of kinds may be used in combination.

As the amount of the catalyst (C) used, the ratio (molar ratio) to the unsaturated group in the organic polymer (B) used is important. The molar ratio of the catalyst (C) and the unsaturated group in the organic polymer (B) (the number of moles of the catalyst (C)/the number of moles of the unsaturated group in the organic polymer (B)) is 10 ^−8. It is preferably from 10 to 10 ^-1 , more preferably from 10 ^-6 to 10 ^-3 . When the above molar ratio (the number of moles of the catalyst (C)/the number of moles of the unsaturated group in the organic polymer (B)) is 10 ⁻⁸ or more, there is an advantage that the hydrosilylation reaction can proceed sufficiently. When the molar ratio (the number of moles of the catalyst (C)/the number of moles of the unsaturated group in the organic polymer (B)) is 10 ⁻¹ or less, the raw material cost can be suppressed to a low level, and the obtained organic material can be obtained. The amount of catalyst residue contained in the polymer is very small. As a result, the organic polymer can provide a cured product that is free of catalyst-derived coloring and has good transparency.

The method of adding the catalyst (C) is not particularly limited, but a method of adding the catalyst (C) after dissolving the catalyst (C) in an arbitrary solvent can stabilize the catalyst and is easy to handle. preferable. The solvent used when the catalyst (C) is dissolved in a solvent and added is not particularly limited, and examples thereof include hydrocarbon solvents such as benzene, toluene, xylene; halogenated hydrocarbons; alcohols; glycols; ethers. Ester, etc. are mentioned.

The hydrosilylation reaction according to one embodiment of the present invention (in other words, the present production method) can be carried out even in a solvent-free system, or can be carried out in the presence of a solvent. The solvent used when carrying out the hydrosilylation reaction in the presence of a solvent is not particularly limited, and examples thereof include hydrocarbons; halogenated hydrocarbons; ethers; esters and the like. As the solvent, heptane, hexane, benzene, toluene, xylene and the like are preferable.

The hydrosilylation reaction according to one embodiment of the present invention (in other words, the present production method) can be carried out under an inert gas such as nitrogen and helium in order to ensure safety in handling a combustible substance. In the present production method, in order to further accelerate the hydrosilylation reaction, it is preferable to add oxygen into the reaction vessel in step 1. The amount of oxygen added is preferably such that the gas phase composition in the reaction vessel does not eventually become an explosive mixed composition. Therefore, the amount of oxygen added is preferably 0.1 to 20% by volume, and more preferably 0.5 to 15.0% by volume, when the volume of the gas phase in the reaction vessel is 100% by volume. It is more preferably 1.0 to 10.0% by volume, and particularly preferably 2.0 to 6.0% by volume. According to the said structure, while being excellent in safety, it becomes possible to further accelerate a hydrosilylation reaction.

In step 1, it is preferable to further add an antioxidant into the reaction vessel. When oxygen is added to the reaction vessel in step 1, it is particularly preferable to add an antioxidant to the reaction vessel. According to the above configuration, it is possible to suppress deterioration due to oxidation of the main chain skeleton of the polymer during the hydrosilylation reaction.

The antioxidant is not particularly limited, and examples thereof include a phenolic antioxidant having a function of a radical chain inhibitor, and more specifically, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,2′-methylenebis(4-methyl-6-tert-butylphenol), 4,4′-butylidenebis(3-methyl) -6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), tetrakis{methylene-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}methane , 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane and the like.

In step 1, when oxygen is added to the reaction vessel, it is preferable to further add a radical chain inhibitor to the reaction vessel. The radical chain inhibitor is not particularly limited, and examples thereof include amine-based antioxidants, and more specifically, phenyl-β-naphthylamine, α-naphthylamine, N,N′-di-sec-butyl- Examples thereof include p-phenylenediamine, phenothiazine, N,N′-diphenyl-p-phenylenediamine.

In Step 1, in order to further accelerate the hydrosilylation reaction, it is preferable to further add sulfur into the reaction vessel. In other words, in the present production method, it is preferable to carry out the hydrosilylation reaction in the presence of sulfur. The amount of sulfur added is not particularly limited. For example, when the catalyst (C) is a platinum catalyst containing platinum as a transition metal, the amount of sulfur added is 0.0003 mg to 0.0063 mg with respect to 1 mg of the platinum catalyst (3 wt% isopropanol solution in terms of platinum). The amount is preferably 0.0008 mg to 0.0045 mg, more preferably 0.0015 mg to 0.0038 mg mol, and particularly preferably 0.002 mg to 0.003 mg mol.

The method for adding sulfur is not particularly limited, but a method of adding sulfur after dissolving it in an arbitrary solvent is preferable because it is easy to handle. The solvent used when sulfur is dissolved in a solvent and added is not particularly limited, and examples thereof include hydrocarbon solvents such as benzene, toluene and xylene; halogenated hydrocarbons; alcohols; glycols; ethers; esters. And so on.

In step 1, the temperature in the reaction vessel may be raised in order to further accelerate the hydrosilylation reaction. The reaction temperature of the hydrosilylation reaction according to one embodiment of the present invention is preferably 30°C to 200°C, more preferably 50°C to 150°C.

(2-2. Step 2)
Step 2 is a step of adding the quinone compound (D) to the reaction mixture of Step 1. This can further accelerate the hydrosilylation reaction. That is, by adding the quinone compound (D), the hydrosilylation reaction was difficult in the reaction system of (a) the addition of a small amount of oxygen or without oxygen, and (b) the catalyst (C) alone. The reaction can proceed at various reaction rates. Furthermore, by adding the quinone compound (D), the generation of side reaction products due to the reaction between the (c) silicon hydride compounds (A) is suppressed, and the addition amount of the (d) catalyst (C) is reduced. It is possible to reduce.

It is presumed that the quinone compound (D) is used in combination with the catalyst (C), and can further improve the promotion of the hydrosilylation reaction by the catalyst (C). Therefore, the quinone compound (D) can be said to be a cocatalyst.

The quinone compound (D) has (a) less acute toxicity, less environmental pollution and less adverse effects on the human body during manufacturing and construction, and/or (b) 2 described in JP-A-2001-206908. It is preferable to have an effect of promoting the hydroxylation reaction which is almost equal to that of -methyl-1,4-naphthoquinone.

The quinone compound (D) is a compound capable of suppressing coloring such as red discoloration, which is considered to be caused by a reaction between the quinone compound (D) and a curing catalyst, in a cured product which can be provided by the obtained organic polymer as low as possible. Is preferred.

The quinone compound (D) is preferably a compound represented by the general formula (2), (3) or (4).

In the general formulas (2) to (4), it is preferable that R ^{1 to} R ¹⁸ each independently represent a hydrogen element, a hydroxyl group, or a functional group having at least one carbon element. Examples of the functional group include an alkyl group, an alkoxy group, and an aryl group. The alkyl group is preferably an alkyl group having 1 to 50 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, and further preferably an alkyl group having 1 to 10 carbon atoms, An alkyl group having 1 to 4 carbon atoms is particularly preferable. The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms, and further preferably an alkoxy group having 1 to 6 carbon atoms, An alkoxy group having 1 to 3 carbon atoms is particularly preferable. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and further preferably an aryl group having 6 to 12 carbon atoms, An aryl group having 6 to 10 carbon atoms is particularly preferable.

When the quinone compound (D) is the compound represented by the general formula (2), (3) or (4), it has an advantage that the hydrosilylation reaction can be further accelerated.

Examples of the quinone compound (D) include 1,4-benzoquinone, 2-tert-1,4-benzoquinone, tetramethylbenzoquinone, 2,5-di-tert-butyl-1,4-benzoquinone and 2,6-di-. tert-Butyl-1,4-benzoquinone, 1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, 2-methoxy-1,4-naphthoquinone, 9,10-anthraquinone, 1-ethylanthraquinone, and 2- Examples include (1,2-dimethylpropyl)-9,10-anthraquinone. Among these, as the quinone compound (D), 1,4-benzoquinone and 2-tert-1 have the advantage that a cured product using an organic polymer obtained by a hydrosilylation reaction is not colored by the quinone compound. ,4-benzoquinone, tetramethylbenzoquinone, 2,5-di-tert-butyl-1,4-benzoquinone, and 2,6-di-tert-butyl-1,4-benzoquinone are preferable, and tert- in one molecule. 2,5-di-tert-butyl-1,4-benzoquinone and 2,6-di-tert-butyl-1,4-benzoquinone having two or more butyl groups are more preferable.

The quinone compound (D) may be used alone or in combination of two or more.

As the amount of the quinone compound (D) used, the ratio (molar ratio) to the amount of the catalyst (C) used is important. The molar ratio of the quinone compound (D) to the catalyst (C) (the number of moles of the quinone compound (D)/the number of moles of the catalyst (C)) is preferably ⁵ to 5×10 ⁵ , and 5 to 5 It is more preferably ×10 ⁴ , more preferably 5 to 5×10 ³ , and particularly preferably 5 to 5×10 ² . When the molar ratio (the number of moles of the quinone compound (D)/the number of moles of the catalyst (C)) is 5 or more, it becomes possible to sufficiently accelerate the hydrosilylation reaction, and as a result, the reaction rate of the hydrosilylation reaction. Will be faster. When the molar ratio (the number of moles of the quinone compound (D)/the number of moles of the catalyst (C)) is 5×10 ⁵ or less, the effect of promoting the hydrosilylation reaction is obtained in proportion to the amount of the quinone compound (D) used. That is, it is cost-effective.

As disclosed by Jean Fisher et al. (Chem. Eur. J., 4, 2008-2017, (1998)), when a quinone compound (D) in an equimolar amount to the catalyst (C) is used, The amount of the quinone compound (D) used relative to (C) is so small that the effect according to one embodiment of the present invention may not be sufficiently achieved.

As the amount of the quinone compound (D) used, the ratio (molar ratio) to the unsaturated group in the organic polymer (B) used is also important. The molar ratio of the quinone compound (D) to the unsaturated group in the organic polymer (B) (the number of moles of the quinone compound (D)/the number of moles of the unsaturated group in the organic polymer (B)) is 0. It is preferably 0.0001 to 100, more preferably 0.0001 to 10, and further preferably 0.001 to 1.

The method for adding the quinone compound (D) to the reaction mixture is not particularly limited, and the quinone compound may be added as it is. As a method for adding the quinone compound (D), the quinone compound can be dissolved in an arbitrary solvent to form a uniform diluted solution because it is easy to handle and can be uniformly dispersed in the entire reaction mixture. After that, the method of adding is preferred. The addition method of the quinone compound (D) is as follows: (a) adding all of the used amount at once, (b) dividing the used amount into several parts and adding in several times, (c) little by little Examples include a method of continuously adding all of the used amounts.

The solvent used when the quinone compound (D) is diluted with a solvent and added is not particularly limited, and examples thereof include hydrocarbon solvents such as benzene, toluene, xylene, halogenated hydrocarbons, alcohols, glycols, Examples thereof include ethers and esters.

The organic polymer obtained by the present production method can be suitably used mainly as a main component of a curable composition.

[3. Curable composition]
The curable composition according to one embodiment of the present invention has the above-mentioned [2. The method for producing an organic polymer] includes an organic polymer produced by the production method described in the above section.

The curable composition according to one embodiment of the present invention is also simply referred to as a main curable composition. The term "curable composition" refers to one aspect of the curable composition of the invention.

The curable composition can provide a cured product by curing the curable composition. Since the present curable composition has the above-mentioned constitution, it is possible to provide a cured product having excellent flexibility and tackiness.

The curable composition may further contain other optional components. Other optional components include curing agents, colorants such as pigments and dyes, extender pigments, ultraviolet absorbers, antioxidants, heat stabilizers (antigelling agents), plasticizers, leveling agents, defoamers, Examples thereof include a silane coupling agent, an antistatic agent, a flame retardant, a lubricant, a viscosity reducing agent, a low shrinkage agent, an inorganic filler, an organic filler, a thermoplastic resin, a drying agent, and a dispersant.

The present curable composition is used as an adhesive; a sealing material for buildings, ships, automobiles, roads, etc.; an adhesive; a mold agent; a vibration damping material; a vibration damping material; a sound insulating material; a foaming material; a paint; It can be preferably used. Since the curable composition can provide a cured product having excellent flexibility and tackiness, it is more preferably used as a sealing material or an adhesive.

Hereinafter, one embodiment of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Method for measuring number average molecular weight of organic polymer (B) The organic polymer (B) obtained by the method described in (Preparation of organic polymer (B)) described below was subjected to GPC. A value obtained by converting the obtained value with polystyrene was used as the number average molecular weight of the organic polymer (B). The conditions of GPC are as follows.
・Liquid transfer system: Tosoh HLC-8120GPC
・Column: Tosoh TSK-GEL H type ・Mobile phase: THF
・Molecular weight: polystyrene equivalent ・Measurement temperature: 40°C
(Example)
(Preparation of organic polymer (B))
Polymerization of propylene oxide was performed using polypropylene glycol as an initiator and a zinc hexacyanocobaltate glyme complex to obtain a polypropylene oxide having a hydroxyl group terminal.

Then, to the obtained polypropylene oxide, 1.2 times equivalent of a methanol solution of sodium methoxide (NaOMe) was added to 1 equivalent of the hydroxyl group in the polypropylene oxide. Methanol was distilled off from the resulting mixture. Then, 3-chloro-2-methyl-1-propene is further added to the mixture to convert the hydroxyl group at the terminal of polypropylene oxide into a 2-methylallyl group, and the polypropylene oxide having a 2-methylallyl group at the terminal (organic polymer). Coalescence (B)) was obtained. The number of unsaturated groups present in one molecule of the obtained organic polymer (B) was 1.97. The number average molecular weight of the obtained organic polymer (B) was 27,300 when measured by the method described above.

(Method for producing organic polymer having reactive silicon group)
To the obtained organic polymer (B), 2000 ppm of 2,6-di-tert-butyl-p-cresol was added as an antioxidant to the organic polymer (B).

Next, 300 g of the organic polymer (B) and 6 g of hexane were added to a 1.0 L glass reactor equipped with a stirrer, and azeotropic dehydration was performed at 100°C. Hexane was distilled off under reduced pressure, and the gas phase in the glass reactor was replaced with nitrogen. With the inside of the glass reactor at 100° C., 30 mg of platinum-vinyl catalyst (3 wt% isopropanol solution in terms of platinum), which is a platinum-olefin complex, and 0.25% sulfur/hexane solution were used as catalyst (C). 30 mg was added to the glass reactor. After stirring the mixture in the glass reactor for 5 minutes, 5.0 g of DMS (dimethoxymethylsilane) as a silicon hydride compound (A) was added into the glass reactor over 0.5 minutes to start the hydrosilylation reaction. .. The time when the addition of the silicon hydride compound (A) was completed was used as the starting point of the hydrosilylation reaction.

After the initiation of the hydrosilylation reaction, 0.35 g of 2,5-di-tert-butyl-1,4-benzoquinone was added as a quinone compound (D). Four hours after the initiation of the hydrosilylation reaction, an organic polymer having a reactive silicon group was obtained. ^The rate of silyl group (reactive silicon group) introduction into the organic polymer (B) based on the hydrosilylation reaction was followed by ¹ H-NMR. The results are shown in Table 1.

(Comparative example)
(Preparation of organic polymer (B))
The organic polymer (B) was prepared by the same method as in the example.

(Method for producing organic polymer having reactive silicon group)
In the same manner as in Example except that the quinone compound (D) (2,5-di-tert-butyl-1,4-benzoquinone) was added before the silicon hydride compound (A) (DMS). A hydrosilylation reaction was carried out to obtain an organic polymer having a reactive silicon group. ^The rate of silyl group (reactive silicon group) introduction into the organic polymer (B) based on the hydrosilylation reaction was followed by ¹ H-NMR. The results are shown in Table 1.

From Table 1, in the example, as a result of reaction tracing, the introduction rate of silyl group was 88.3% after 1 hour, 96.6% after 2 hours, 99.7% after 3 hours, and 99.7% after 4 hours. there were. In the comparative example, as a result of tracking the reaction, the silyl group introduction rate was 85.1% after 1 hour, 88.5% after 2 hours, 94.6% after 3 hours, and 96.6% after 4 hours. That is, it can be seen that the present production method is superior in production efficiency as compared with the conventional production method of an organic polymer.

According to one embodiment of the present invention, it is possible to provide a method for producing an organic polymer having excellent production efficiency, and the obtained organic polymer can be suitably used mainly as a main component of a curable composition. A curable composition according to an embodiment of the present invention includes a pressure-sensitive adhesive; a sealing material for buildings, ships, automobiles, roads, etc.; an adhesive; a mold agent; a vibration damping material; a vibration damping material; It can be suitably used for paints, spray materials and the like.

Claims (8)

The silicon hydride compound (A), the organic polymer (B) and the catalyst (C) are mixed in a reaction vessel to add the silicon hydride compound (A) to the organic polymer (B). A step 1 of initiating a hydrosilylation reaction
Step 2 of adding the quinone compound (D) to the reaction mixture of Step 1 above,
The silicon hydride compound (A) is represented by the following general formula (1),
R _a X _b H _c Si ··· formula (1)
(In the general formula (1), a R's are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a triorganosiloxy group having 1 to 20 carbon atoms, and b X independently of each other is a halogen atom or a hydrolyzable group, a or b is an integer of 0 to 3, c is an integer of 1 to 3, and a+b+c=4).
The organic polymer (B) has an unsaturated group,
The method for producing an organic polymer, wherein the catalyst (C) contains at least one transition metal selected from the group consisting of Group 8, Group 9 and Group 10. The method for producing an organic polymer according to claim 1, wherein the quinone compound (D) is a compound represented by the following general formula (2), (3) or (4):

(In the general formulas (2) to (4), R ^{1 to} R ¹⁸ are each independently a hydrogen element, a hydroxyl group, or a functional group having at least one carbon element). The main chain skeleton of the organic polymer (B) is a polymer composed of at least one polymer selected from the group consisting of polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic polymers. The method for producing an organic polymer according to claim 1 or 2, which comprises a unit. The method for producing an organic polymer according to claim 1, wherein the unsaturated group is a 2-methylallyl group. The method for producing an organic polymer according to any one of claims 1 to 4, wherein the organic polymer (B) has a molecular weight distribution of 1.0 or more and less than 1.8. The method for producing an organic polymer according to claim 1, wherein the terminal of the main chain or the side chain of the organic polymer (B) is an unsaturated group. In the step 1, an antioxidant and oxygen are further added to the reaction vessel, and the addition amount of oxygen is 0.1 to 20 volume when the volume of the gas phase in the reaction vessel is 100% by volume. %, The method for producing an organic polymer according to any one of claims 1 to 6, which is %. A curable composition comprising the organic polymer produced by the method for producing an organic polymer according to claim 1.