JP2022075628A - Method for producing curable composition - Google Patents

Abstract

To provide a method for producing a curable composition that allows a polyoxyalkylene polymer having a reactive silyl group to be well compatible with an alkyl methacrylate polymer having a reactive silyl group and that gives a cured product including these polymers and having excellent tensile characteristics.SOLUTION: The present invention discloses a method for producing a curable composition that includes a polyoxyalkylene polymer having a reactive silyl group (A), and an alkyl methacrylate polymer having a reactive silyl group (B), subjected to living radical polymerization under predetermined conditions.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a curable composition containing a polymer having a reactive silyl group capable of forming a crosslinked structure.

Since a polyoxyalkylene polymer having a reactive silyl group can be obtained as a cured product having excellent flexibility, tensile properties, coating workability, etc., it is widely used in curable compositions for sealants, adhesives, paints, and the like. It is used. It is known that a curable composition containing a polyoxyalkylene polymer having a reactive silyl group can improve the weather resistance of the cured product by adding a (meth) acrylic acid alkyl ester polymer having a reactive silyl group. There is.

The (meth) acrylic acid alkyl ester polymer having a reactive silyl group has been conventionally produced by a method using a radical polymerization initiator having a reactive silyl group, a chain transfer agent, or the like. In such a production method, a reactive silyl group is likely to be irregularly introduced into the side chain of the main chain skeleton of the carbon-carbon bond chain of the (meth) acrylic acid alkyl ester polymer, and the obtained polymer is obtained. It was inferior in tensile properties to the polyoxyalkylene polymer having a reactive silyl group.

In recent years, in order to improve such physical properties, it has been studied to control the introduction of a reactive silyl group into a (meth) acrylic acid alkyl ester polymer by using a living radical polymerization method.

For example, Patent Document 1 describes Reversible chain Transfer Catalyzed Polymerization (RTCP) in which nitrogen such as N-succinateimide is used as a central element and a compound containing a halogen atom bonded to the central element is used as a catalyst. A method of living radical polymerization is described. According to this RTCP method of living radical polymerization method, a polymer having a terminal halogen is obtained, and by modifying the terminal halogen, a vinyl-based polymer having a hydrolyzed silyl group (reactive silyl group) at the molecular end is obtained. It is stated that ((meth) acrylic acid alkyl ester polymer) can be obtained.

Further, Patent Document 2 describes atom transfer radical polymerization (ATRP: Atom Transfer Radical Polymerization) using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex such as a copper bromide-pentamethyldiethylenetriamine complex as a catalyst. ) Method of living radical polymerization is described. A polymer having a terminal halogen can also be obtained by this ATRP method of living radical polymerization, and a vinyl-based polymer having a crosslinkable silyl group (reactive silyl group) at the molecular terminal by the conversion reaction of the terminal halogen ((meth)). It is described that an acrylic acid alkyl ester polymer) can be obtained.

Japanese Unexamined Patent Publication No. 2011-74325 International Publication No. 2005/095492

By the way, the curable composition is also required to have excellent workability when used in the above-mentioned applications. From the viewpoint of such workability, it is desirable that the mixed state is uniform. Further, it is desirable that the cured product obtained from the curable composition is homogeneous in order to exhibit excellent tensile properties.
Therefore, it is required that the polyoxyalkylene polymer having a reactive silyl group and the (meth) acrylic acid alkyl ester polymer having a reactive silyl group have good compatibility in the curable composition.

It is said that the RTCP-type living radical polymerization as described in Patent Document 1 can always sufficiently control the introduction position of the reactive silyl group with respect to the main chain skeleton of the (meth) acrylic acid alkyl ester polymer. I could not say. The (meth) acrylic acid alkyl ester polymer having a reactive silyl group obtained by the living radical polymerization of the RTCP method was inferior in compatibility with the polyoxyalkylene polymer having a reactive silyl group.

On the other hand, the living radical polymerization of the ATRP method as described in Patent Document 2 reacts with the terminal of the main chain skeleton of the carbon-carbon bond chain of the (meth) acrylic acid alkyl ester polymer as compared with the case of the RTCP method. It is excellent in controllability of the introduction position by introducing a sex silyl group. However, the (meth) acrylic acid alkyl ester polymer having a reactive silyl group obtained by the living radical polymerization of the ATRP method is also a phase with the polyoxyalkylene polymer having a reactive silyl group, for unknown reasons. It was inferior in solubility.

The present invention has been made to solve the above problems, and comprises a polyoxyalkylene polymer having a reactive silyl group and a (meth) acrylic acid alkyl ester polymer having a reactive silyl group. It is an object of the present invention to provide a method for producing a curable composition which has good compatibility and contains these polymers and can obtain a cured product having excellent tensile properties.

In the present invention, a (meth) acrylic acid alkyl ester polymer having a predetermined reactive silyl group, which is obtained by living radical polymerization of the Reversible Coordination Mediated Polymerization (RCMP) method, is a reactive silyl. It is based on the finding that the compatibility with the polyoxyalkylene polymer having a group is good.

The present invention provides the following means.
[1] A method for producing a curable composition containing the polymer (A) and the polymer (B), wherein the polymer (A) has an average of 1.0 or more reactive silyl groups per molecule. It is a polyoxyalkylene polymer having a number average molecular weight of 4000 to 35000, and the polymer (B) has an average of 0.5 or more reactive silyl groups per molecule and is a monomer (b1). ) And the monomer composition containing the monomer (b2) were subjected to living radical polymerization in the presence of a halogenated quaternary ammonium salt and reacted with a silylating agent to obtain (meth) acrylic. It is an acid alkyl ester polymer, the monomer (b1) is a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 8 carbon atoms, and the monomer (b2) has 9 to 9 carbon atoms. It is a (meth) acrylic acid alkyl ester having 20 alkyl groups, and the content of the monomer (b1) in the monomer composition is the monomer (b1) and the monomer (b2). A method for producing a curable composition, which is 10 to 90 parts by mass with respect to 100 parts by mass in total.

[2] The method for producing a curable composition according to [1], wherein the polymer (B) contains at least two or more of the monomers (b2).
[3] The silylating agent is added in an amount of 0.5 to 10.0 parts by mass based on 100 parts by mass of the monomer (b1) and the monomer (b2) in total, [1] or [ 2] A method for producing a curable composition.
[4] The method for producing a curable composition according to any one of [1] to [3], wherein the living radical polymerization is a reversible coordination-mediated polymerization.
[5] The method for producing a curable composition according to any one of [1] to [4], wherein the halogenated quaternary ammonium salt is an iodide quaternary ammonium salt.
[6] The method for producing a curable composition according to [5], wherein the quaternary ammonium salt iodide is a compound represented by the following formula (1).
R ₄ N ⁺ I- ⁽ 1)
(In the formula (1), R is an alkyl group having 1 to 8 carbon atoms independently.)
[7] The curability of [5] or [6], wherein the quaternary ammonium iodide salt is one or more selected from tetramethylammonium iodide, tetrabutylammonium iodide, and tetraoctylammonium iodide. Method for producing the composition.
[8] The method for producing a curable composition according to any one of [1] to [7], which uses an organic iodine compound as an initiator in the living radical polymerization.
[9] The organic iodine compound is 1,4-diiodooctafluorobutane, bis (2-iodoisobutyric acid) ethylene glycol, 2,5-diiodoadipic acid diethyl, 1,4-bis (1'-iodoethyl). The method for producing a curable composition according to [8], which is one or more selected from benzene and bis (2-iodo-2-phenylacetic acid) ethylene glycol.

[10] The method for producing a curable composition according to any one of [1] to [9], wherein the polymer (B) has an average of 1.0 to 6.0 reactive silyl groups per molecule.
[11] The method for producing a curable composition according to any one of [1] to [10], wherein the polymer (B) has a number average molecular weight of 6000 to 300,000.

[12] The method for producing a curable composition according to any one of [1] to [11], wherein the mass compounding ratio of the polymer (A) to the polymer (B) is 10/90 to 90/10. ..
[13] The method for producing a curable composition according to any one of [1] to [12], wherein the curable composition is a sealant composition.

According to the method for producing a curable composition of the present invention, the compatibility between the polyoxyalkylene polymer having a reactive silyl group and the (meth) acrylic acid alkyl ester polymer having a reactive silyl group is good. , A curable composition containing these can be obtained.
According to the curable composition, a cured product having good workability and excellent tensile properties can be obtained.

The definitions and meanings of terms and notations in the present specification are shown below.
The "polyoxyalkylene polymer" means a polymer having a polyoxyalkylene chain produced by ring-opening addition polymerization of an alkylene oxide monomer in the main chain skeleton.
The "(meth) acrylic acid alkyl ester polymer" means a polymer having a carbon-carbon bond chain produced by vinyl polymerization of a (meth) acrylic acid alkyl ester monomer in the main chain skeleton. "(Meta) acrylic acid" means one or both of acrylic acid and methacrylic acid.
The notation of the numerical range of "x to y" means that it is x or more and y or less.

The "reactive silyl group" means a group in which a hydroxyl group or a hydrolyzable group is bonded to a silicon atom and a crosslinked structure can be formed by a siloxane bond. The reaction to form a siloxane bond is promoted by a curing catalyst.
The "reactive silyl group" referred to in the present invention is preferably a group represented by the following formula (2).
-SiX _{a R} ^1-3a (2)

In formula (2), X is a hydrogen atom, a halogen atom, a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group and an alkenyloxy group. Of these, an alkoxy group is preferable because it is mildly hydrolyzable and easy to handle. Examples of the alkoxy group include a methoxy group, an ethoxy group, and an isopropoxy group. The curable composition is cured by rapid formation of a crosslinked structure by a siloxane bond, and a cured product having good physical properties can be easily obtained. Therefore, a methoxy group or an ethoxy group is preferable.

R ¹ is a monovalent organic group having 1 to 20 carbon atoms and does not contain a hydrolyzable group. The organic group is preferably one or more selected from an alkyl group, a cycloalkyl group, an aryl group, a benzyl group, an α-chloroalkyl group and a triorganosyloxy group. Specific examples thereof include a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, an α-chloromethyl group, a trimethylsiloxy group, a triethylsiloxy group, a triphenylsiloxy group and the like. .. Of these, a methyl group or an ethyl group is preferable from the viewpoint of the balance between curability and stability of the polymer having a reactive silyl group. Further, the α-chloromethyl group is preferable from the viewpoint of high curing rate. From the viewpoint of availability, a methyl group is preferable.
a is an integer of 1 to 3. When a is ¹ , the two R1s may be the same as or different from each other. When a is 2 or 3, a plurality of Xs may be the same as or different from each other. a is preferably 1 or 2, more preferably 2.

Specific examples of the reactive silyl group include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, tris (2-propenyloxy) silyl group, triacetoxysilyl group, dimethoxymethylsilyl group and diethoxymethylsilyl group. Examples thereof include a group, a dimethoxyethylsilyl group, a diisopropoxymethylsilyl group, a (α-chloromethyl) dimethoxysilyl group, a (α-chloromethyl) diethoxysilyl group and the like. Of these, a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group and a diethoxymethylsilyl group are preferable, and a dimethoxymethylsilyl group or a trimethoxysilyl group is preferable from the viewpoint of high reactivity and good curability. Groups are more preferred.

The "average number of reactive silyl groups per molecule" is a number average of the concentration [mol / g] of the reactive silyl groups in the polymer determined by proton nuclear magnetic resonance ( ¹ H-NMR) spectral measurement. It is a value calculated by multiplying the molecular weight.
"Number average molecular weight" (hereinafter referred to as "Mn") and "weight average molecular weight" (hereinafter referred to as "Mw") are polystyrene-equivalent molecular weights determined by gel permeation chromatography (GPC) measurement. be. The molecular weight distribution is the ratio of Mw to Mn (Mw / Mn). Specifically, it is measured by the method described in Examples described later.
The "active hydrogen-containing group" refers to one or more groups selected from a hydroxyl group, a carboxy group, a primary amino group, a secondary amino group, a hydrazide group and a mercapto group. The hydrogen atom contained in these groups is "active hydrogen".
By "silylating agent" is meant a compound used to introduce a reactive silyl group into a polymer.

The method for producing a curable composition of the present invention is a method for producing a curable composition in which a predetermined polymer (A) and the polymer (B) are blended.
The curable composition may contain components other than the polymer (A) and the polymer (B). For example, as the polymer other than the polymer (A) and the polymer (B), a polyoxyalkylene polymer having an average of less than 1.0 reactive silyl groups per molecule may be contained. Further, the curable composition may contain components other than these polymers, as will be described later.

[Polymer (A)]
The polymer (A) is a polyoxyalkylene polymer having an average of 1.0 or more reactive silyl groups per molecule and an Mn of 4000 to 35000.
The polymer (A) blended in the curable composition may be used alone or in combination of two or more. Further, it may be linear or branched.
The polymer (A) has a polyoxyalkylene chain produced by the polymerization of one or more alkylene oxide monomers in the main chain skeleton. When the main chain skeleton of the polymer (A) is formed by the copolymerization of two or more kinds of alkylene oxide monomers, the copolymerization is not particularly limited in the arrangement of the monomers and is random. It may be a copolymerization, an alternating copolymerization, or a block copolymerization.

The main chain skeleton of the polymer (A) includes, for example, a polymerization of an ethylene oxide monomer, a polymerization of a propylene oxide monomer, a polymerization of a butylene oxide monomer, and a tetramethylene oxide monomer. Examples thereof include those by polymerization, those by copolymerization of ethylene oxide monomer and propylene oxide monomer, those by polymerization of propylene oxide monomer and butylene oxide monomer, and the like. Of these, the one obtained by polymerizing a propylene oxide monomer is preferable in view of physical properties such as the tensile properties of the cured product of the curable composition.

The main clavicle of the polymer (A) preferably has 2 to 8 ends, more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 2 or 3. be. From the viewpoint of compatibility with the polymer (B) and the tensile properties of the cured product of the curable composition, the number is particularly preferably two. The polymer (A) is linear when it has two ends, and branched when it has three or more ends.

The polymer (A) has an average of 1.0 or more reactive silyl groups per molecule. The average number of reactive silyl groups per molecule is more than 1.0 and 8.0 or less from the viewpoint of compatibility with the polymer (B) and the tensile properties of the cured product of the curable composition. The number is preferably 1.1 to 6.0, more preferably 1.2 to 4.0.

The polymer (A) preferably has an average of more than 0.5 reactive silyl groups per terminal. The average number of reactive silyl groups per terminal is preferably more than 0.5 and 4.0 or less, more preferably 0, from the viewpoint of the tensile properties of the cured product of the curable composition. The number is 6 to 3.0, more preferably 0.7 to 2.0.

The Mn of the polymer (A) is 4000 to 35000, preferably 5000 to 30000, and more preferably 10000 to 25000.
When Mn is less than 4000, the amount of the reactive silyl group introduced per mass of the polymer (A) becomes too large, and it is difficult to obtain good tensile properties of the cured product of the curable composition. On the other hand, when Mn exceeds 35,000, the viscosity of the polymer (A) tends to be high, and it becomes difficult to obtain good compatibility with the polymer (B).
The molecular weight distribution (Mw / Mn) of the polymer (A) is preferably 1.8 or less, more preferably 1.5 or less, still more preferably 1.2 or less, from the viewpoint of keeping the viscosity low.

<Method for producing polymer (A)>
The polymer (A) is preferably produced by introducing a reactive silyl group into the terminal of the main chain skeleton of the polyoxyalkylene polymer which is a precursor polymer. For example, an unsaturated bond is introduced at the end of the main chain skeleton of a polyoxyalkylene polymer which is a precursor polymer, and then a silylating agent is reacted with the unsaturated bond to introduce a reactive silyl group at the end. can do.

The precursor polymer is an oxyalkylene polymer obtained by ring-opening addition polymerization of an alkylene oxide monomer to active hydrogen of an initiator having an active hydrogen-containing group in the presence of a catalyst. It is preferable that the active hydrogen-containing group is a hydroxyl group and the precursor polymer has a hydroxyl group at the end of the main chain skeleton. The initiator may be used alone or in combination of two or more.
When the initiator has two or more active hydrogens, the number of active hydrogens is usually the same as the number of ends of the main clavicle of the precursor polymer.

The initiator is preferably a compound having 2 to 8 hydroxyl groups, and the number of hydroxyl groups is more preferably 2 to 6, still more preferably 2 to 4, particularly preferably 2 or 3. be. When obtaining the linear polymer (A), it is preferable to use an initiator having two active hydrogen-containing groups, and it is more preferable that the two active hydrogen-containing groups are hydroxyl groups.
Examples of the initiator having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol. Examples thereof include low molecular weight polyoxypropylene glycol.
Examples of the initiator having three or more hydroxyl groups include glycerin, trimethylolpropane, trimethylolethane, sorbitol, pentaerythritol, and low molecular weight polyoxypropylene triol.

As the catalyst, a known catalyst can be used, for example, an alkali catalyst such as potassium hydroxide, a transition metal compound such as a complex obtained by reacting an organic aluminum compound with porphyrin-porphyrin complex catalyst, and a composite metal cyanide. Examples thereof include a compound complex catalyst and a catalyst composed of a phosphazenic compound. Of these, the composite metal cyanide complex catalyst is preferable because it narrows the molecular weight distribution of the precursor polymer and suppresses the viscosity of the curable composition to a low level.
As the complex metal cyanide complex, a known compound can be used, and examples thereof include a zinc hexacyanocobaltate complex having tert-butanol as a ligand. As a method for producing a polyoxyalkylene polymer using a composite metal cyanide complex catalyst, a known method can be adopted. For example, International Publication No. 2003/062301, International Publication No. 2004/067633, JP-A-2004-269767, JP-A-2005-15786, International Publication No. 2013/06582, JP-A-2015-01162 The manufacturing method using the catalyst disclosed in the above can be adopted.

As a method for producing the polymer (A) from the precursor polymer, a known method can be used, for example, Japanese Patent Application Laid-Open No. 45-36319, Japanese Patent Application Laid-Open No. 50-156599, Japanese Patent Application Laid-Open No. 61-197631. Japanese Patent Application Laid-Open No. 3-72527, Japanese Patent Application Laid-Open No. 8-231007, Japanese Patent Application Laid-Open No. 2015-105322, Japanese Patent Application Laid-Open No. 2015-105323, Japanese Patent Application Laid-Open No. 2015-105324, Japanese Patent Application Laid-Open No. 2015-105293, Japanese Patent Application Laid-Open No. 2016-216633, Japanese Patent Application Laid-Open No. 2017-39782, US Pat. No. 3,632,557, US Pat. No. 4,960,844, International Publication No. 2013/180203, International Publication No. 2014/192842, International Publication No. 2015 The methods disclosed in / 080067, International Publication No. 2015/105122, International Publication No. 2015/111577, International Publication No. 2016/002907, etc. can be used.

As a method of introducing an unsaturated bond into the terminal of the main chain skeleton of the polyoxyalkylene polymer which is a precursor polymer, for example, an alkali metal having an excess amount with respect to the terminal hydroxyl group in the precursor polymer having a hydroxyl group at the terminal. After reacting the alkoxide, a method of reacting the terminal hydroxyl group with a halogenated unsaturated hydrocarbon compound having an unsaturated bond such as an excess equivalent of allyl chloride is preferable.
Further, the precursor polymer having a hydroxyl group at the terminal is reacted with an alkali metal alkoxide in an excessive amount with respect to the hydroxyl group at the terminal, and then an epoxy compound having an unsaturated bond is reacted, and then the hydroxyl group at the terminal after the reaction is reacted. A method of reacting a halogenated unsaturated hydrocarbon compound having an unsaturated bond such as an excess amount of allyl chloride with the reaction is also preferable. In this case, the number of unsaturated bonds introduced at the ends of the main chain skeleton of the precursor polymer can be increased more than the number of hydroxyl groups that are the active hydrogen-containing groups of the initiator for obtaining the precursor polymer. The number of terminals into which the reactive silyl group is introduced can be increased.

Next, a silylating agent can be reacted by a hydrosilylation reaction with respect to the unsaturated bond introduced at the end of the main chain skeleton of the precursor polymer, and a reactive silyl group can be introduced at the end.
Examples of the silylating agent include a hydrosilane compound (for example, a compound in which a group represented by the above formula (2) is bonded to a hydrogen atom), a reactive silyl group, and an unsaturated bond to form a bond. Examples thereof include compounds having a group that can be formed (for example, a mercapto group). Specifically, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris (2-propenyloxy) silane, triacetoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, diisopropoxymethylsilane, Examples thereof include (α-chloromethyl) dimethoxysilane, (α-chloromethyl) diethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane. The silylating agent may be used alone or in combination of two or more. Of these, trimethoxysilane, triethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane are preferable, and dimethoxymethylsilane or trimethoxysilane is more preferable, from the viewpoint of high reactivity and good curability.

As described above, the average number of reactive silyl groups per molecule of the polymer (A) is one or more.
The silylation rate of the polymer (A) is preferably more than 50 mol% and 100 mol% or less, more preferably 60 to 97 mol%, still more preferably 65 to 95 mol%. When the polymer (A) is composed of two or more kinds, the silylation rate is the average value of the silylation rates of each polymer.
For example, when the polymer (A) is linear and has two ends of the main clavicle, if the silylation rate is 50 mol% or more, the reactivity of the polymer (A) per molecule. The average number of silyl groups is 1 or more.
The silylation rate can be controlled by adjusting the amount of the silylating agent that reacts with the unsaturated bond introduced at the end of the main clavicle of the precursor polymer. The silylation rate may be expressed as the equivalent amount of the silylating agent to the number of terminals of the main clavicle of the precursor polymer.

The content ratio of the polymer (A) in the curable composition is 1 to 80% by mass with respect to 100% by mass of the curable composition from the viewpoint of good tensile properties of the cured product of the curable composition. It is preferable, more preferably 3 to 75% by mass, still more preferably 5 to 70% by mass.

[Polymer (B)]
The polymer (B) has an average of 0.5 or more reactive silyl groups per molecule, and a monomer composition containing the monomer (b1) and the monomer (b2) is subjected to the fourth halogenated composition. It is a (meth) acrylic acid alkyl ester polymer obtained by subjecting it to living radical polymerization in the presence of a tertiary ammonium salt and reacting it with a silylating agent.
The polymer (B) blended in the curable composition may be used alone or in combination of two or more. Further, it may be linear or branched.
The polymer (B) has a carbon-carbon bond chain produced by vinyl polymerization of one or more (meth) acrylic acid alkyl ester monomers in the main chain skeleton. The main chain skeleton of the polymer (B) is formed by the copolymerization of two or more kinds of monomers, and the copolymerization is a random copolymerization without particular limitation on the arrangement of the monomers. It may be an alternating copolymerization or a block copolymerization.

The total amount of the monomers (b1) and the monomer (b2) is preferably 50 parts by mass or more, more preferably, with respect to 100 parts by mass of all the monomers in the monomer composition. Is 70 parts by mass or more, and may be 100 parts by mass.
When the monomer composition contains a monomer other than the monomers (b1) and (b2), the monomer is preferably a vinyl-based polymer, for example, acrylonitrile, styrene, or a fluorine-containing vinyl-based monomer. Examples thereof include monomers and silicon-containing vinyl-based monomers. The silicon-containing vinyl-based monomer referred to here does not include the reactive silyl group-containing vinyl-based monomer.

The monomer (b1) is a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 8 carbon atoms. The alkyl group may be linear or branched. Specific examples of the monomer (b1) include butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, and octyl (meth) acrylate. Can be mentioned. The monomer (b1) may be used alone or in combination of two or more.

The monomer (b2) is a (meth) acrylic acid alkyl ester having an alkyl group having 9 to 20 carbon atoms. The alkyl group may be linear or branched, and may be linear from the viewpoint of ease of copolymerization with the monomer (b1), availability, and the like. Is preferable. Examples of the monomer (b2) include nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, and stearyl (meth) acrylate. The monomer (b2) may be used alone or in combination of two or more, and is more preferably at least two from the viewpoint of good tensile properties of the cured product. When two or more kinds of monomers (b2) are used in combination, (meth) acrylic acid having an alkyl group having 9 to 14 carbon atoms is used from the viewpoint of good tensile properties and availability of the cured product of the curable composition. It is preferable to contain an alkyl ester and a (meth) acrylic acid alkyl ester having an alkyl group having 16 to 20 carbon atoms, and more preferably to contain a (meth) lauryl acrylate and a stearyl (meth) acrylate. It is more preferable that b2) is lauryl (meth) acrylate and stearyl (meth) acrylate.

The number of carbon atoms of the alkyl group of the (meth) acrylic acid alkyl ester of the monomer (b1) and the alkyl group of the (meth) acrylic acid alkyl ester of the monomer (b2) in the monomer composition. The difference is preferably 2 to 16 from the viewpoint of good compatibility of the polymer (B) with the polymer (A) and good tensile properties of the cured product of the curable composition, more preferably. Is 4 to 15, more preferably 6 to 14.

The content of the monomer (b1) in the monomer composition is 10 to 90 parts by mass, preferably 10 to 90 parts by mass, based on 100 parts by mass of the total of the monomer (b1) and the monomer (b2). It is 30 to 85 parts by mass, more preferably 50 to 80 parts by mass.
If the amount of the monomer (b1) is less than 10 parts by mass, the polymer (B) having good compatibility with the polymer (A) cannot be obtained. When the monomer (b1) exceeds 90 parts by mass, the viscosity of the polymer (B) becomes too high, and in this case as well, the polymer (B) having good compatibility with the polymer (A) is obtained. In addition, it is difficult to obtain good tensile properties of the cured product of the curable composition.

The polymer (B) has an average of 0.5 or more reactive silyl groups per molecule. The average number of reactive silyl groups per molecule shall be 1.0 to 6.0 from the viewpoint of compatibility with the polymer (A) and the tensile properties of the cured product of the curable composition. Is preferable, and more preferably 1.1 to 5.0 pieces.

The Mn of the polymer (B) is preferably 6000 to 300,000, more preferably 8,000 to 100,000, and even more preferably 10,000 to 50,000.
When Mn is 6000 or more, good tensile properties of the cured product of the curable composition can be easily obtained. Further, when Mn is 300,000 or less, the viscosity of the polymer (B) can be suppressed to a low level, and good compatibility with the polymer (A) can be easily obtained.
The molecular weight distribution (Mw / Mn) of the polymer (B) is preferably 4.0 or less, more preferably 3 from the viewpoint of keeping the viscosity low and obtaining good compatibility with the polymer (A). It is 0.0 or less, more preferably 2.0 or less.

<Method for producing polymer (B)>
The polymer (B) is obtained by subjecting the monomer composition containing the monomer (b1) and the monomer (b2) to a living radical polymerization in the presence of a halogenated quaternary ammonium salt and silylation. It is obtained by reacting the agent. That is, the main chain skeleton of the polymer (B) is formed by living radical polymerization using a halogenated quaternary ammonium salt as a catalyst. Such living radical polymerization is preferably a reversible coordination-mediated polymerization (RCMP) method.
According to the RCMP method of living radical polymerization, it is easy to control the molecular weight of the polymer, and it is easy to arbitrarily control the introduction of the reactive silyl group in the progress of the polymerization reaction, and further, it is easy to control the introduction of the reactive silyl group with the polymer (A). A (meth) acrylic acid alkyl ester polymer having a reactive silyl group with good compatibility can be obtained.
The (meth) acrylic acid alkyl ester polymer having a reactive silyl group produced by the living radical polymerization as described above has a phase with the polymer (A), unlike the case where it is produced by the ATRP method, the RTCP method or the like. Has excellent solubility. The reason is not clear, but the polymer (B) is due to the amphipathic nature of the halogenated quaternary ammonium salt used as a catalyst for living radical polymerization to obtain the polymer (B). It is considered that the compatibility between the polymer (A) and the polymer (A) is improved.

The halogenated quaternary ammonium salt used as a catalyst for the living radical polymerization may be used alone or in combination of two or more.
As the halogenated quaternary ammonium salt, a quaternary ammonium iodide salt or a quaternary ammonium bromide salt is preferable, and a quaternary ammonium iodide salt is more preferable from the viewpoint of ease of handling and catalytic activity. ..

The quaternary ammonium salt iodide is preferably a compound represented by the following formula (1).
R ₄ N ⁺ I- ⁽ 1)
In formula (1), R is an alkyl group having 1 to 8 carbon atoms independently. The alkyl group may be linear or branched. From the viewpoint of availability and the like, it is preferable that the four Rs are the same alkyl group.
Specific examples of the quaternary ammonium salt iodide include tetramethylammonium iodide, tetrabutylammonium iodide, and tetraoctylammonium iodide. Of these, tetrabutylammonium iodide is preferable from the viewpoint of easy availability and compatibility with monomers.

The amount of the quaternary ammonium salt halide added as a catalyst in the living radical polymerization is 100 parts by mass in total of all the monomers in the monomer composition from the viewpoint of controlling the progress of the polymerization reaction. , 0.1 to 15.0 parts by mass, more preferably 0.2 to 10.0 parts by mass, still more preferably 0.5 to 8.0 parts by mass.

In the living radical polymerization, it is preferable to use an organic iodine compound as an initiator. The initiator may be used alone or in combination of two or more.
When the number of iodine atoms in the initiator is two or more, the number of iodine atoms is usually the same as the number of terminals of the main chain skeleton of the polymer (B).

The initiator is preferably a compound having 1 to 8 iodine atoms, and the number of iodine atoms is more preferably 1 to 6 and even more preferably 1 to 3. When the linear polymer (B) is obtained, it is preferable to use a compound having 1 or 2 iodine atoms as an initiator, and a diiodot compound having 2 iodine atoms is more preferable.
Specific examples of the organic iodine compound include 2-iodo-2-methylpropionitrile, 2-iodo-2-methylbutylnitrile, ethyl 2-iodoisobutyrate, 1,4-diiodooctafluorobutane, and bis. Examples thereof include (2-iodoisobutyric acid) ethylene glycol, 2,5-diiodoadipate diethyl, 1,4-bis (1'-iodoethyl) benzene, and bis (2-iodo-2-phenylacetic acid) ethylene glycol. .. Of these, 1,4-diiodooctafluorobutane is preferable from the viewpoint of easy availability and controllability of the polymerization reaction.

The amount of the initiator added in the living radical polymerization is 0.1 to 15.0 with respect to 100 parts by mass of all the monomers in the monomer composition from the viewpoint of controlling the progress of the polymerization reaction. It is preferably parts by mass, more preferably 0.2 to 10.0 parts by mass, and even more preferably 0.5 to 8.0 parts by mass.

Living radical polymerization may be carried out in a solvent-free manner or in a solvent. When a solvent is used, the solvent may be, for example, cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbon compounds such as benzene, toluene and xylene; esters such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone and cyclohexanone and the like. Ketones; alcohols such as methanol, ethanol and isopropanol and the like can be mentioned. Of these, cyclic ethers, aromatic hydrocarbon compounds, esters and ketones are preferable. These may be used alone or in combination of two or more.

The polymerization temperature in the living radical polymerization is preferably 50 to 180 ° C., more preferably 60 to 160 ° C., still more preferably 70 to 140 ° C. from the viewpoint of the efficiency of the polymerization reaction and the like.

As a method for obtaining a (meth) acrylic acid alkyl ester polymer having a reactive silyl group by subjecting the monomer composition to a living radical polymerization and reacting with a silylating agent, for example, the following <1> and The method shown in <2> can be mentioned.
<1> The iodine atom at the end of the main chain skeleton of the (meth) acrylic acid alkyl ester polymer obtained by subjecting the monomer composition containing the monomer (b1) and the monomer (b2) to living radical polymerization. Is converted into a reactive silyl group by, for example, a silylating agent such as a reactive silyl group and a compound having an amino group or a mercapto group.
<2> Living radical polymerization of the monomer composition containing the monomer (b1) and the monomer (b2) is started, and a compound having a reactive silyl group and a vinyl group is used as a silylating agent during the polymerization. A method of adding and copolymerizing a monomer (b1) and a monomer (b2) and a silylating agent.

The compound used as the silylating agent differs between the methods <1> and <2> above, but in each case, the (meth) acrylic acid alkyl ester having an average of 0.5 or more reactive silyl groups per molecule. Use the amount that gives the polymer. The amount of the silylating agent added is 0. It is preferably 5 to 10.0 parts by mass, more preferably 1.0 to 8.0 parts by mass, still more preferably 1.5 to 7.0 parts by mass, and particularly preferably 2.0 to 6.0 parts by mass. It is a department.

According to the method of <1>, a reactive silyl group can be efficiently introduced into the terminal of the main chain skeleton of the (meth) acrylic acid alkyl ester polymer by a substitution reaction.
Examples of the silylating agent in the method <1> include 3-aminopropyldimethoxymethylsilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyl. Examples thereof include trimethoxysilane. These may be used alone or in combination of two or more. Of these, 3-aminopropyldimethoxymethylsilane or 3-mercaptopropylmethyldimethoxysilane is preferable.

In the method of <1>, the substitution reaction with a silylating agent is preferably carried out in a solvent. The solvent used is not particularly limited and can be selected from the same solvents as those used in the above-mentioned living radical polymerization.
The reaction temperature of the substitution reaction is not particularly limited, but is usually preferably 0 to 85 ° C, more preferably 15 to 80 ° C, still more preferably 25 to 75 ° C.

According to the method of <2>, it is possible to control the introduction of the reactive silyl group to any position without being limited to the terminal of the main chain skeleton of the (meth) acrylic acid alkyl ester polymer.
Examples of the silylating agent in the method <2> include 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. , Vinyl trimethoxysilane and the like. These may be used alone or in combination of two or more. Of these, 3-methacryloxypropylmethyldimethoxysilane or 3-acryloxypropylmethyldimethoxysilanene is preferable.

In the method of <2>, in the living radical polymerization of the monomer composition containing the monomer (b1) and the monomer (b2), the silylating agent is used at an arbitrary timing from the start to the end of the reaction. Can be added, and the reaction temperature after the addition does not have to be changed.

After reacting the silylating agent as described above, the unreacted silylating agent remaining in the reaction system is removed and dried to obtain the polymer (B).
The unreacted silylating agent can be removed by a known method such as solvent extraction. Drying can also be performed by a known method under conditions such as heating and depressurization, if necessary.

[Cursable composition]
The curable composition is obtained by blending the polymer (A) and the polymer (B).
The polymer (A) and the polymer (B) have good compatibility, and even after one week has passed by mixing and stirring the two, the polymer (A) and the polymer (B) undergo phase separation. A uniform liquid state is maintained without becoming cloudy.
Therefore, the workability when using the curable composition is good, and a homogeneous cured product having excellent tensile properties can be obtained.

The mass mixing ratio of the polymer (A) and the polymer (B) in the curable composition is 10 / from the viewpoint of effectively exhibiting the desired tensile properties in the cured product of the curable composition. It is preferably 90 to 90/10, more preferably 20/80 to 80/20, and even more preferably 30/70 to 70/30.

Uses of the curable composition include sealants (for example, elastic sealants for buildings, sealants for multi-layer glass, rustproof / waterproof sealants at the edges of glass, backside sealants for solar cells, sealants for buildings, etc. Sealing materials for ships, sealing materials for automobiles, sealing materials for roads), electrical insulating materials (insulating coating materials for electric wires / cables), adhesives, paints and the like are suitable. In particular, it is suitable for applications that require good tensile properties of the cured product.
Therefore, the curable composition of the present invention is preferably used for sealants, adhesives, paints, etc., and is particularly suitable as a sealant composition.

The curable composition of the present invention may contain other components other than the polymer (A) and the polymer (B). For example, when the curable composition is a composition for a sealant, other components include a filler, a plasticizer, a stabilizer, a rocking agent, a dehydrating agent, an adhesive-imparting agent, an oxygen-curable compound, and a photocurable. Examples include compounds and curing catalysts.
Specific examples of the other components include International Publication No. 2013/180203, International Publication No. 2014/192842, International Publication No. 2016/002907, JP-A-2014-88481, JP-A-2015-10162, It can be appropriately selected from the known ones described in JP-A-2015-105293A, JP-A-2017-21541, and the like, and used in any combination.

Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to the following Examples.

First, a polyoxyalkylene polymer and a (meth) acrylic acid alkyl ester polymer were produced by the following synthetic examples.
The methods for measuring various physical properties in the following synthetic examples are shown below.

[Measuring method]
[Number average molecular weight (Mn) and weight average molecular weight (Mw)]
Mn and Mw of various polymers were measured by gel permeation chromatography (GPC) under the following conditions (in terms of polystyrene), and the molecular weight distribution (Mw / Mn) was calculated from these values.
<Measurement conditions>
-Equipment used: "HLC-8220GPC", manufactured by Tosoh Corporation-Data processing equipment: "SC-8020", manufactured by Tosoh Corporation-Columns used: The following two types of columns are connected in series "TSKgel (registered trademark) SuperHZ4000" , Tosoh Co., Ltd., 2 pieces "TSKgel (registered trademark) SuperHZ2500", Tosoh Co., Ltd., 2 pieces ・ Column temperature: 40 ° C
-Detector: Differential refractometer (RI)
・ Eluent: Tetrahydrofuran ・ Flow rate: 0.35 mL / min ・ Sample concentration: 0.5% by mass
・ Sample injection amount: 20 μL
-Standard sample for preparing calibration curve: Polystyrene; "EasiCal (registered trademark) PS-2", manufactured by Agilent Technologies, Inc.

[Polymerization reaction rate]
The reaction solution during the reaction in the synthesis of various polymers was collected, and the proton nuclear magnetic resonance ( ¹ H-NMR) spectrum was measured under the following conditions. From the integrated value _IM of the signal derived from the _unreacted monomer and the integrated value IP of the signal derived from the target polymer in the obtained NMR chart, the polymerization reaction rate was calculated by the following formula. ..
Polymerization reaction rate [%] = IP / ( _{IM + IP} ) x 100
<Measurement conditions>
-Equipment used: "JNM-ECZ400S FT-NMR", manufactured by JEOL Ltd.-Solvent: Deuterated chloroform-Polymer concentration in the measurement sample: 1 to 10% by mass
・ Cumulative number: 8 times

[Average number of reactive silyl groups per molecule]
It was calculated by multiplying the concentration [molar / g] of the reactive silyl group in the polymer obtained from the ¹ H-NMR spectrum measured for various polymers by Mn.
In the ¹ H-NMR spectrum, the number of integrations is 512 times, and the other measurement conditions are the same as the measurement conditions in the above-mentioned [Polymerization reaction rate] section.

[Synthesis of polyoxyalkylene polymer (polymer (A))]
[Raw material compound]
The details of the raw material compounds used in the following synthesis examples 1 and 2 are as follows.
<Initiator>
-PPG: Polypropylene glycol obtained by ring-opening addition polymerization of propylene oxide to propylene glycol; hydroxyl group equivalent (molecular weight per hydroxyl group) 1000
<Monomer>
・ PO: Propylene oxide <catalyst>
-TBA-DMC catalyst: Zinc hexacyanocobaltate complex with tert-butanol as a ligand <silylating agent>
-DMMS: Dimethoxymethylsilane

(Synthesis Example 1)
Using 64.1 g of PPG as an initiator, react with PO: 705.0 g in the presence of TBA-DMC catalyst: 0.03 g at 120 ° C. until the pressure of the reaction system does not decrease, and then carry out a polyoxypropylene chain. A precursor polymer (2) having two hydroxyl groups per molecule at the terminal of the above was obtained (Mw: 25900, Mn: 24000, Mw / Mn: 1.08).
A methanol solution containing 1.05 times the molar equivalent of sodium methoxide with respect to the hydroxyl group of the precursor polymer (2) was added to the precursor polymer (2) to make it alkoxide, and then heated under reduced pressure to retain methanol. I left. Then, an excess molar equivalent of allyl chloride was added to the hydroxyl group of the precursor polymer (2) and reacted to obtain a precursor polymer (2) having an allyl group at all ends of the polyoxypropylene chain.
Next, in the presence of platinum chloride hexahydrate, 0.75 times the molar equivalent (syllation rate 75 mol%) of DMMS was added to the allyl group of the precursor polymer (2), and the temperature was 70 ° C. The reaction was carried out for a period of time to obtain a polymer A1 having a reactive silyl group at the end of the polyoxypropylene chain.

(Synthesis Example 2)
In Synthesis Example 1, PO was changed to 449.0 g, and other than that, the precursor polymer (2) (Mw17100, Mn16000, Mw / Mn1.07) was obtained in the same manner as in Synthesis Example 1, and then polyoxypropylene. A polymer A2 having a reactive silyl group at the end of the chain was obtained (silylation rate 75 mol%).

Table 1 shows the Mw, Mn, Mw / Mn of the polymers A1 and A2 obtained in Synthesis Examples 1 and 2 and the average number of reactive silyl groups per molecule.

[Synthesis of (meth) acrylic acid alkyl ester polymer (polymer (B))]
[Raw material compound]
The details of the raw material compounds used in the following synthesis examples 3 to 16 are as follows.
<Monomer (b1)>
-BA: n-butyl acrylate-HA: n-hexyl acrylate <monomer (b2)>
・ LA: lauryl acrylate ・ LMA: lauryl methacrylate ・ StA: stearyl acrylate <silylating agent>
-KBM-502: 3-methacryloxypropylmethyldimethoxysilane; "KBM-502", manufactured by Shin-Etsu Chemical Co., Ltd.-KBM-5102: 3-acryloxypropylmethyldimethoxysilane; "KBM-5102", Shin-Etsu Chemical Co., Ltd. Made by the company ・ KBM-902: 3-aminopropyldimethoxymethylsilane; “KBM-902”, manufactured by Shin-Etsu Chemical Co., Ltd. ・ DMMS: Dimethoxymethylsilane ・ KBM-903: 3-aminopropyltriethoxysilane; “KBM-903” , Made by Shin-Etsu Chemical Co., Ltd. <Catalyst>
-BNI: Tetrabutylammonium iodide-CuBr-PMDT: Copper bromide-pentamethyldiethylenetriamine complex-NIS: N-iodosuccinate imide <Initiator>
-DIFB: 1,4-diiodooctafluorobutane-DBrADE: diethyl 2,5-dibromoadipate-DIX: 1,4-bis (iodomethyl) benzene-BPO: benzoyl peroxide

(Synthesis Example 3)
BA: 65.37 g (70.0 parts by mass), LA: 28.01 g (30.0 parts by mass), DIFB: 1.90 g (2.0 parts by mass) in a 300 mL flask equipped with a stirrer and a thermometer. , And BNI: 5.27 g (5.6 parts by mass) were charged. The inside of the flask was bubbled with nitrogen gas to sufficiently degas, and the liquid temperature was maintained at 125 ° C. with stirring to start the polymerization reaction and react for 13 hours (polymerization reaction rate 90%).
The reaction system was cooled to 70 ° C., KBM-902: 3.16 g (3.4 parts by mass) was added as a silylating agent, and toluene: 100 g was added as a solvent, and the liquid temperature was maintained at 70 ° C. for 5 hours. rice field.
The reaction system was cooled to 25 ° C., methanol was added, and the unreacted silylating agent was removed by a liquid separation operation, and then dried under reduced pressure at 0.3 kPa and 80 ° C. for 5 hours to obtain a polymer B1.

(Synthesis Example 4)
The polymerization reaction was started in the same manner as in Synthesis Example 3 and reacted for 8 hours (polymerization reaction rate 65%).
Further, KBM-5102: 3.17 g (3.4 parts by mass) was added as a silylating agent, and the mixture was reacted for 5 hours (polymerization reaction rate other than the silylating agent: 90%).
Then, in the same manner as in Synthesis Example 3, the unreacted silylating agent was removed and then dried under reduced pressure to obtain polymer B2.

(Synthesis Example 5)
The polymerization reaction was started in the same manner as in Synthesis Example 3 and reacted for 8 hours (polymerization reaction rate 65%).
Further, KBM-502: 3.17 g (3.4 parts by mass) was added as a silylating agent, and the mixture was reacted for 5 hours (polymerization reaction rate other than the silylating agent: 90%).
Then, in the same manner as in Synthesis Example 3, the unreacted silylating agent was removed and then dried under reduced pressure to obtain a polymer B3.

(Synthesis Example 6)
In Synthesis Example 3, the DIFB was changed to 3.17 g (3.4 parts by mass), and the polymerization reaction was started in the same manner as in Synthesis Example 3 except for that, and the reaction was carried out for 8 hours (polymerization reaction rate 65%).
Further, KBM-5102: 5.28 g (5.7 parts by mass) was added as a silylating agent, and the mixture was reacted for 5 hours (polymerization reaction rate other than the silylating agent: 90%).
Then, in the same manner as in Synthesis Example 3, the unreacted silylating agent was removed and then dried under reduced pressure to obtain a polymer B4.

(Synthesis Examples 7 and 8)
In Synthesis Example 4, the types of monomers were changed as shown in Table 2, and the polymerization reaction was started in the same manner as in Synthesis Example 4 except for the above, and the reaction was carried out for 8 hours (polymerization reaction rate was 65% in each case). ).
Further, in the same manner as in Synthesis Example 4, a silylating agent was added and reacted for 5 hours (the polymerization reaction rate other than the silylating agent was 90%), the unreacted silylating agent was removed, and then drying under reduced pressure was performed. Then, polymers B5 and B6 were obtained, respectively.

(Synthesis Examples 9 and 10)
In Synthesis Example 6, the types of monomers were changed as shown in Table 2, and the polymerization reaction was started in the same manner as in Synthesis Example 6 except for the above, and the reaction was carried out for 8 hours (polymerization reaction rate was 65% in each case). ).
Further, KBM-5102: 5.28 g (5.7 parts by mass) was added as a silylating agent and reacted for 5 hours (polymerization reaction rates other than the silylating agent were all 90%), and unreacted silylation. After removing the agent, the mixture was dried under reduced pressure to obtain polymers B7 and B8, respectively.

(Synthesis Examples 11 and 12)
The polymerization reaction was started in the same manner as in Synthesis Example 5 and reacted for 8 hours (polymerization reaction rate 65%).
Further, the amount of KBM-502 as a silylating agent was changed as shown in Table 2, and the other reactions were carried out in the same manner as in Synthesis Example 5 (polymerization reaction rates other than the silylating agent were 90%), and the reaction was not performed. After removing the silylating agent for the reaction, the mixture was dried under reduced pressure to obtain polymers B9 and B10, respectively.

(Synthesis Example 13)
In Synthesis Example 3, the monomer was 93.38 g (100 parts by mass) of BA only, and the polymerization reaction was started in the same manner as in Synthesis Example 3 except for that, and the reaction was carried out for 13 hours (polymerization reaction rate 90%).
Then, in the same manner as in Synthesis Example 3, the reaction system was cooled, a silylating agent and a solvent were added to react, and after removing the unreacted silylating agent, the mixture was dried under reduced pressure to obtain the polymer B11. rice field.

(Synthesis Example 14)
A (meth) acrylic acid alkyl ester-based polymer was produced by ATRP-type living radical polymerization, and a reactive silyl group was introduced at the end of the main chain skeleton of the polymer.
First, in a 1 L reactor equipped with a stirrer and a thermometer, BA: 269.1 g (70.0 parts by mass), LA: 115.32 g (30.0 parts by mass), CuBr: 2. 80 g (0.78 parts by mass), acetonitrile: 34.5 g, and DBrADE: 5.85 g (1.5 parts by mass) were charged. The inside of the reactor is bubbled with nitrogen gas to sufficiently degas, the liquid temperature is maintained at 70 to 80 ° C. with stirring, and the mixture is stirred for 30 minutes. Then, PMDT is added as a ligand of CuBr and polymerization is carried out. The reaction was started. The liquid temperature was maintained at 70 to 90 ° C. with stirring, and PMDT was added to a total of 0.564 g on the way, and the mixture was reacted for about 3 hours.
The reaction system was heated and stirred at 0.3 kPa at 80 ° C. to remove volatile components, and then acrylonitrile: 139 g, 1,7-octadiene: 35.8 g, and PMDT: 1.13 g were added and stirred while stirring. The reaction was carried out for 8 hours.
The reaction system was heated and stirred at 0.3 kPa at 80 ° C. to remove volatile components, and then toluene was added to dissolve the polymer, and diatomaceous soil was added as a filtration aid, and aluminum silicate and hydrotalcite were added as adsorbents. Then, the mixture was heated and stirred at a liquid temperature of 100 ° C. under an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6% by volume).
After filtering the stirred liquid and heating and stirring the filtrate at 0.3 kPa at 100 ° C. to remove volatile components, aluminum silicate and hydrotalcite as adsorbents, and a heat deterioration inhibitor (“Smilizer”) (Registered trademark) GS ”, manufactured by Sumitomo Chemical Co., Ltd.) was added, and the mixture was heated and stirred at 1.3 kPa or less and 175 ° C. Furthermore, aluminum silicate and hydrotalcite are added, and an antioxidant (“Irganox (registered trademark) 245”, manufactured by BASF Japan Ltd.) is added under an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6% by volume). , The mixture was heated and stirred at a liquid temperature of 150 ° C.
Toluene was added to the stirred solution to dissolve the polymer, and the mixture was filtered. The filtrate was heated and stirred at 0.3 kPa at 100 ° C. to remove volatile components, and a precursor polymer having an octenyl group was obtained.

This precursor polymer: 300 g, DMMS: 4.39 g (1.1 parts by mass, 2.0 mol equivalent with respect to octenyl group), methyl orthostate: 2.20 g (1.0 mol equivalent with respect to octenyl group) , And a xylene solution (concentration 20% by mass) of a bis (1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex as a catalyst: 0.028 g (3.34 mg as platinum) is mixed. Then, the mixture was heated and stirred at 100 ° C. under a nitrogen gas atmosphere, and reacted until the octenyl group disappeared.
The reaction system was dried under reduced pressure at 0.3 kPa at 100 ° C. to obtain a polymer B12.

(Synthesis Example 15)
In Synthesis Example 14, BA was changed to 300 g (78.0 parts by mass), LA was changed to StA: 84.4 g (22.0 parts by mass), and other than that, the ATRP method was carried out in the same manner as in Synthesis Example 14. The polymer B13 was obtained by the living radical polymerization of.

(Synthesis Example 16)
A (meth) acrylic acid alkyl ester-based polymer was produced by RTCP-type living radical polymerization, and a reactive silyl group was introduced at the end of the main chain skeleton of the polymer.
First, in a 1 L reactor equipped with a stirrer and a thermometer, BA: 46.0 g (12.8 parts by mass), LMA: 314.0 g (87.2 parts by mass), DIX: 3.7 g (1.0). (Mass parts), NIS: 0.03 g (0.008 parts by mass), BPO: 1.2 g (0.3 parts by mass), and methyl orthoacetate: 154.0 g. The inside of the reactor was bubbled with nitrogen gas to sufficiently degas, and the liquid temperature was maintained at 70 ° C. with stirring to start the polymerization reaction and react for 3 hours (polymerization reaction rate 70%).
Further, KBM-903: 5.5 g (1.5 parts by mass) was added as a silylating agent, and the mixture was reacted for 1 hour (polymerization reaction rate 75%).
Then, in the same manner as in Synthesis Example 3, the unreacted silylating agent was removed and then dried under reduced pressure to obtain a polymer B14.

Table 2 shows the Mw, Mn, Mw / Mn of the polymers B1 to B14 obtained in Synthesis Examples 3 to 16 and the average number of reactive silyl groups per molecule.

[Manufacturing of curable composition (2)]
The polymers A1, A2 and B1 to B14 obtained in the above synthesis examples 1 to 16 were mixed in the formulations shown in Examples 1 to 26 in Table 3 to prepare each curable composition.
The compatibility of each curable composition was evaluated as follows.

[Compatibility evaluation]
10 g of the curable composition mixed by stirring was placed in a 20 mL vial, and the mixture was allowed to stand at room temperature (25 ± 5 ° C.), and after 1 week, the state of the contents was visually observed and evaluated. Table 3 shows the evaluation results based on the following evaluation criteria.
<Evaluation criteria>
◯: Good compatibility (the contents are transparent and uniform liquid)
X: Poor compatibility (contents are cloudy or phase separated)

[Manufacturing of curable composition (2)]
Using the polyoxyalkylene polymer (A1 or A2) and the (meth) acrylic acid alkyl ester polymer (any of B1 to B14) obtained in the above synthesis examples 1 to 16, a total of 100 parts by mass of both was used. , The additive was blended with the composition of any one of Formulations 1 to 9 in Table 4, and the mixture was uniformly mixed with a planetary stirrer to produce each curable composition.

〔Additive〕
Details of the various additives shown in Table 4 are as follows.
<Filling agent>
・ Viscolite EL-20: Glue Calcium Carbonate; “Viscolite® EL-20”, manufactured by Shiraishi Kogyo Co., Ltd. ・ Whiten SB: Heavy Calcium Carbonate; “Whiten® SB”, Shiraishi Calcium Co., Ltd.・ R-820: Titanium oxide; "R-820", manufactured by Ishihara Sangyo Co., Ltd. ・ Balloon 80GCA: Organic balloon; "Matsumoto Microsphere (registered trademark) MFL-80GCA", manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd. <Plastic agent ＞
-Exenol 3020: Polypropylene glycol; "Exenol (registered trademark) 3020", manufactured by AGC Co., Ltd.-Alfon UP-1110: Acrylic polymer; "Alfon (registered trademark) UP-1110", manufactured by Toa Synthetic Co., Ltd.-Polymer Q : Synthesized in Synthesis Example 15 below; DINP: Diisononyl phthalate; "Vinisizer (registered trademark) 90", manufactured by Kao Co., Ltd. ・ N-12D: n-dodecane, purity 98.0% by mass; "Cactus normal paraffin N" -12D ", manufactured by JXTG Energy Co., Ltd.-Sunsosizer E-PS: 4,5-epoxycyclohexane-1,2-dicarboxylic acid-di-2-ethylhexyl;" Sunsosizer (registered trademark) E-PS ", New Japan Made by Rika Co., Ltd. <Stabilizer>
-Irganox 1135: Antioxidant; "Irganox® 1135", manufactured by BASF Japan Ltd.-Tinuvin 326: UV absorber; "Tinuvin® 326", manufactured by BASF Japan Ltd.-Tinuvin 765: Light stabilizer; " Tinuvin (registered trademark) 765 ”, manufactured by BASF Japan Ltd. ・ ADEKA STAB LA-63P: Light stabilizer;“ ADEKA STAB (registered trademark) LA-63P ”, manufactured by ADEKA Corporation <Shaking agent>
-Disparon 6500: "Disparon (registered trademark) 6500", manufactured by Kusumoto Kasei Co., Ltd. <Dehydrating agent>
KBM-1003: Vinyltrimethoxysilane; "KBM-1003", manufactured by Shin-Etsu Chemical Co., Ltd. <Adhesive imparting agent>
-KBM-403: 3-glycidoxypropyltrimethoxysilane; "KBM-403", manufactured by Shin-Etsu Chemical Co., Ltd.-KBM-603: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane; "KBM" -603 ", manufactured by Shin-Etsu Chemical Co., Ltd. <Amine compound>
・ Laurylamine: Reagent, manufactured by Junsei Chemical Co., Ltd. ・ Fermin CS: Coconutamine; “Farmin (registered trademark) CS”, manufactured by Kao Co., Ltd. ・ Adeka Hardener EH-235R-2: Ketimine compound; EH-235R-2 ", manufactured by ADEKA CORPORATION <oxygen curable compound>
・ Tung oil: manufactured by Kimura Shoji Co., Ltd. <photocurable compound>
-Aronix M-309: Trimethylolpropane triacrylate; "Aronix (registered trademark) M-309", manufactured by Toagosei Co., Ltd. <Cure catalyst>
-SCAT-32A: "SCAT-32A", manufactured by Nitto Kasei Co., Ltd.

An example of synthesis of the polymer Q used as a plasticizer is shown below. The PO, TBA-DMC catalyst and DMMS in the description of Synthesis Example 15 are the same as those used in Synthesis Example 1 described above.
(Synthesis Example 17)
Polyoxypropylene monool (hydroxyl equivalent (molecular weight per hydroxyl group) 2000) obtained by ring-opening addition polymerization of PO to n-butanol was used as an initiator.
Initiator: 384 g and PO: 594 g are reacted in the presence of TBA-DMC catalyst: 0.05 g at 120 ° C. until the pressure of the reaction system does not decrease, and one hydroxyl group is added to the end of the polyoxypropylene chain. A precursor polymer (1') having one per unit was obtained (Mw8100, Mn6900, Mw / Mn1.10.).
A methanol solution containing 1.05 times mol of sodium methoxide with respect to the hydroxyl group of the precursor polymer (1') is added to the precursor polymer (1') to make it alkoxide, and then heated and depressurized to add methanol. Distilled away. Then, an excess molar equivalent of allyl chloride is added to the hydroxyl group of the precursor polymer (1') to cause a reaction, and the precursor polymer (2') having one allyl group at the end of the polyoxypropylene chain per molecule. Got
Next, in the presence of platinum chloride hexahydrate, 0.85 times the molar equivalent (silylation rate 85 mol%) of DMMS was added to the allyl group of the precursor polymer (2'), and the temperature was 70 ° C. The reaction was carried out for 5 hours to obtain a polymer Q having a reactive silyl group at one end of the polyoxypropylene chain (average number of reactive silyl groups 0.85 per molecule).

[Evaluation of tensile properties of cured product]
Each curable composition was used as a filling sample, and a test piece of a sealant (sealant) was prepared based on "5.3 Tensile property test" of JIS A 1439: 2016.
As the adherend in the tensile property test, an aluminum adherend coated with an anodic oxide film was treated with a primer (“MP-2000”, manufactured by Cemedine Co., Ltd.) and used.
The test piece was cured at a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5% RH for 7 days, then at a temperature of 50 ± 2 ° C. and a humidity of 65 ± 5% RH for 7 days, and then at a temperature of 90. It was carried out by curing at ± 2 ° C. and humidity of 65 ± 5% RH for 7 days.

Tensile tests were conducted on each test piece with a Tensilon tester at a temperature of 23 ± ² ° C. and a tensile speed of 50 mm / min. , 50% tensile stress M50 [N / mm ² ] was measured.
The larger the value of Tmax, the higher the tensile strength. If the Tmax is 0.40 N / mm ² or more, it can be said that the tensile strength is sufficiently high.
The larger the value of Emax, the better the elongation. If Emax is 370% or more, it can be said that the elongation is sufficient, if it is 400% or more, it is good, and if it is 500% or more, it is good. It can be said that it is very good.
If the value of M50 is 0.20 N / mm ² or less, it can be said that it has sufficient flexibility. On the other hand, if the value of M50 is too small, it indicates that tack (stickiness) is caused by insufficient curing, so that M50 is 0.070 N / mm ² or more. It is preferable, more preferably 0.080 N / mm ² or more, still more preferably 0.090 N / mm ² or more.
It was confirmed that each of the test pieces after the tensile test had agglomeration fracture.
Table 5 shows representative examples of the evaluation results of the tensile property test for each curable composition.

In the formulation of the polyoxyalkylene polymer of Examples 27 to 33 in Table 5 and the (meth) acrylic acid alkyl ester polymer, the additive was changed to the formulation 2 to 9 in Table 4 to prepare each curable composition. In all cases, the curable compositions corresponding to Example 34 in each of the additive formulations 2 to 9 (when the (meth) acrylic acid alkyl ester polymer is B11) are all good. It was found that it showed sufficient elongation and tensile strength and had sufficient flexibility.

Claims (13)

A method for producing a curable composition containing the polymer (A) and the polymer (B).
The polymer (A) is a polyoxyalkylene polymer having an average of 1.0 or more reactive silyl groups per molecule and a number average molecular weight of 4000 to 35000.
The polymer (B) has an average of 0.5 or more reactive silyl groups per molecule, and a monomer composition containing the monomer (b1) and the monomer (b2) is obtained by halogenating the polymer (B). It is a (meth) acrylic acid alkyl ester polymer obtained by subjecting it to living radical polymerization in the presence of a quaternary ammonium salt and reacting it with a silylating agent.
The monomer (b1) is a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 8 carbon atoms.
The monomer (b2) is a (meth) acrylic acid alkyl ester having an alkyl group having 9 to 20 carbon atoms.
The content of the monomer (b1) in the monomer composition is 10 to 90 parts by mass with respect to 100 parts by mass in total of the monomer (b1) and the monomer (b2). A method for producing a curable composition. The method for producing a curable composition according to claim 1, wherein the polymer (B) contains at least two or more of the monomers (b2). The silylating agent according to claim 1 or 2, wherein 0.5 to 10.0 parts by mass of the silylating agent is added to a total of 100 parts by mass of the monomer (b1) and the monomer (b2). A method for producing a curable composition. The method for producing a curable composition according to any one of claims 1 to 3, wherein the living radical polymerization is a reversible coordination-mediated polymerization. The method for producing a curable composition according to any one of claims 1 to 4, wherein the halogenated quaternary ammonium salt is an iodide quaternary ammonium salt. The method for producing a curable composition according to claim 5, wherein the quaternary ammonium iodide salt is a compound represented by the following formula (1).
R ₄ N ⁺ I- ⁽ 1)
(In the formula (1), R is an alkyl group having 1 to 8 carbon atoms independently.) The curable composition according to claim 5 or 6, wherein the quaternary ammonium iodide salt is at least one selected from tetramethylammonium iodide, tetrabutylammonium iodide, and tetraoctylammonium iodide. Production method. The method for producing a curable composition according to any one of claims 1 to 7, wherein an organic iodine compound is used as an initiator in the living radical polymerization. The organic iodine compounds include 1,4-diiodooctafluorobutane, bis (2-iodoisobutyric acid) ethylene glycol, 2,5-diiodoadipate diethyl, 1,4-bis (1'-iodoethyl) benzene, and The method for producing a curable composition according to claim 8, wherein the curable composition is one or more selected from bis (2-iodo-2-phenylacetic acid) ethylene glycol. The method for producing a curable composition according to any one of claims 1 to 9, wherein the polymer (B) has an average of 1.0 to 6.0 reactive silyl groups per molecule. The method for producing a curable composition according to any one of claims 1 to 10, wherein the polymer (B) has a number average molecular weight of 6000 to 300,000. The method for producing a curable composition according to any one of claims 1 to 11, wherein the mass blending ratio of the polymer (A) to the polymer (B) is 10/90 to 90/10. The method for producing a curable composition according to any one of claims 1 to 12, wherein the curable composition is a sealant composition.