JP2022064564A - Oxyalkylene polymer, curable composition comprising oxyalkylene polymer, and method for producing oxyalkylene polymer - Google Patents

Abstract

To provide an oxyalkylene polymer serving as a raw material of a cured product having excellent strength, a curable composition comprising the oxyalkylene polymer and a method for producing the oxyalkylene polymer.SOLUTION: There is provided an oxyalkylene polymer (A) having more than 1.0 reactive silicone groups represented by -SiXaR3-a and unsaturated groups in total on average per one terminal group and a urethane bond in the main chain. R is a monovalent organic group having 1 to 20 carbon atoms and represents an organic group other than a hydrolyzable group, X represents a hydroxy group, a halogen atom or a hydrolyzable group and a represents an integer of 1 to 3, when a is 1, R may be the same or different and when a is 2 or 3, X may be the same or different.SELECTED DRAWING: None

Description

The present invention relates to an oxyalkylene polymer, a curable composition containing an oxyalkylene polymer, and a method for producing an oxyalkylene polymer.

The oxyalkylene polymer having a reactive silicon group is cured by a hydrolysis reaction to form a flexible rubber-like cured product, which is used for sealing materials, adhesives and the like.

Patent Document 1 discloses an oxyalkylene polymer having an average of more than 1.0 reactive silicon groups per terminal group. It is described that the polymer has an average of more than 1.0 reactive silicon groups per terminal group, which makes it a raw material for a cured product having excellent elasticity and strength.

International Publication No. 2013/180203

In adhesive applications, the strength of the cured product is required to be excellent.
The strength of the cured product obtained by using the polymer described in Patent Document 1 as a raw material is not sufficient.

The present invention has been made in view of the above circumstances, and a method for producing an oxyalkylene polymer as a raw material for a cured product having excellent strength, a curable composition containing the oxyalkylene polymer, and the oxyalkylene polymer. The challenge is to provide.

The present invention is the following [1] to [12].
[1] A polymer having a reactive silicon group, an unsaturated group, a urethane bond and a polyoxyalkylene chain represented by the following formula 1, wherein the reactive silicon group and the above are averaged per one terminal group. An oxyalkylene polymer (A) having a total of more than 1.0 unsaturated groups and having a urethane bond in the main chain.
-SiX _a R _3-a formula 1
In the above formula 1, R is a monovalent organic group having 1 to 20 carbon atoms and represents an organic group other than a hydrolyzable group, X represents a hydroxyl group, a halogen atom, or a hydrolyzable group, and a is. It indicates an integer of 1 to 3, and when a is 1, R may be the same or different from each other, and when a is 2 or 3, X may be the same or different from each other.
[2] The main chain contains a residue obtained by removing an isocyanate group from a polyisocyanate, a polyoxyalkylene chain, and a urethane bond connecting the residue and the polyoxyalkylene chain, and the terminal group comprises. The oxyalkylene polymer (A) according to [1], which is a terminal group containing an oxygen atom closest to the molecular terminal of the oxyalkylene polymer (A) among the oxygen atoms of the polyoxyalkylene chain.
[3] The oxyalkylene polymer (A) according to [1] or [2], which has a number average molecular weight of 3,000 to 100,000.
[4] The oxyalkylene polymer (A) according to any one of [1] to [3], which has a molecular weight distribution of 2.0 or less.
[5] The oxyalkylene polymer (A) according to any one of [1] to [4], which has an average of more than 1.0 reactive silicon groups per terminal group.
[6] A curable composition comprising the oxyalkylene polymer (A) according to any one of [1] to [5] and a curing catalyst.
[7] The active hydrogen-containing group at the other terminal group of the oxyalkylene polymer (B) below is reacted with a polyisocyanate having a molecular weight of 100 to 20,000 to obtain the oxyalkylene polymer (C) below. Next, the oxyalkylene polymer according to [5], wherein the unsaturated group at the terminal group of the oxyalkylene polymer (C) is reacted with the silylating agent having a reactive silicon group represented by the above formula 1. A) Manufacturing method.
Oxyalkylene polymer (B): A polymer having an unsaturated group, an active hydrogen-containing group and a polyoxyalkylene chain, and having an average of 1.0 or more unsaturated groups at one terminal group. An oxyalkylene polymer having an average of more than 0 and 1.0 or less active hydrogen-containing groups in the other terminal group.
Oxyalkylene polymer (C): A polymer having an unsaturated group and a polyoxyalkylene chain, which has an average of 1.0 or more unsaturated groups per terminal group.
[8] The oxyalkylene polymer (B) is an oxyalkylene polymer obtained by subjecting a cyclic ether to a ring-opening addition polymerization reaction with an initiator, and the initiator has two or more unsaturated groups in one molecule. The method for producing an oxyalkylene polymer (A) according to [7], which is a compound having the above and having one active hydrogen-containing group in one molecule.
[9] The oxyalkylene according to [8], wherein the cyclic ether comprises at least one cyclic ether selected from the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide. A method for producing the polymer (A).
[10] The method for producing an oxyalkylene polymer (A) according to [8] or [9], wherein the initiator is a compound represented by the following formula 2.

前記式２中、Ｒ^１は活性水素含有基、Ｒ^２は水素原子又はメチル基であり、Ｒ^４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、Ｒ^６は酸素原子若しくは窒素原子を含んでもよく、酸素原子若しくは窒素原子と隣接する原子は炭素原子である炭素数１～２０の１価の炭化水素基、水素原子、又は－Ｒ^６２－ＣＲ^６１＝ＣＨ_２で表される基であり、Ｒ^６１は水素原子又はメチル基であり、Ｒ^６２は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、複数のＲ^２、Ｒ^４はそれぞれ互いに同一でも異なってもよく、ｎは０～１０の整数である。
［１１］ 前記開環付加重合反応は、複合金属シアン化錯体触媒の存在下で行われる、［８］～［１０］のいずれか一項に記載のオキシアルキレン重合体（Ａ）の製造方法。
［１２］ 前記オキシアルキレン重合体（Ｃ）の数平均分子量が３，０００～１００，０００である、［７］～［１１］のいずれか一項に記載のオキシアルキレン重合体（Ａ）の製造方法。

In the above formula 2, R ¹ is an active hydrogen-containing group, R ² is a hydrogen atom or a methyl group, R ⁴ may contain an oxygen atom or a nitrogen atom, and an atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom. A divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, R ⁶ may contain an oxygen atom or a nitrogen atom, and an oxygen atom or an atom adjacent to the nitrogen atom is a carbon atom having 1 to 20 carbon atoms. A monovalent hydrocarbon group of 20, a hydrogen atom, or a group represented by -R ⁶² -CR ⁶¹ = CH ₂ , R ⁶¹ is a hydrogen atom or a methyl group, and R ⁶² is an oxygen atom or a nitrogen atom. It may be contained, and the atom adjacent to the oxygen atom or the nitrogen atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom, and a plurality of R ² and R ⁴ are the same or different from each other. Often, n is an integer from 0 to 10.
[11] The method for producing an oxyalkylene polymer (A) according to any one of [8] to [10], wherein the ring-opening addition polymerization reaction is carried out in the presence of a composite metal cyanide complex catalyst.
[12] The production of the oxyalkylene polymer (A) according to any one of [7] to [11], wherein the oxyalkylene polymer (C) has a number average molecular weight of 3,000 to 100,000. Method.

According to the present invention, it is possible to provide an oxyalkylene polymer as a raw material for a cured product having excellent strength, and a method for producing the oxyalkylene polymer.

The meanings and definitions of the terms in the present specification are as follows.
The numerical range represented by "-" means a numerical range in which the numerical values before and after "-" are the lower limit value and the upper limit value.
The "polymer" means a substance having a number average molecular weight of 1,000 or more.
By "compound" is meant a substance having a number average molecular weight of less than 1,000. The molecular weight of the compound is the number average molecular weight in the gel permeation chromatography (hereinafter referred to as GPC) measurement described later. The molecular weight of a substance having no molecular weight distribution in GPC measurement is the formula weight of the compound.
The "oxyalkylene polymer" means a polymer having a polyoxyalkylene chain formed from a unit based on a cyclic ether.
The "active hydrogen-containing group" is at least one selected from the group consisting of a hydroxyl group bonded to a carbon atom, a carboxy group, an amino group, a monovalent functional group obtained by removing one hydrogen atom from a primary amine, and a sulfanyl group. It is the basis of the seed.
The "active hydrogen" is a hydrogen atom based on the active hydrogen-containing group and a hydrogen atom based on a hydroxyl group of water.
The "silylating agent" is a compound capable of reacting with an unsaturated group to introduce a reactive silicon group.

The "silylation rate" of an oxyalkylene polymer having a reactive silicon group is the ratio of the number of reactive silicon groups to the total number of reactive silicon groups and unsaturated groups contained in the terminal groups of the polymer.
The number of reactive silicon groups contained in the terminal groups of the polymer can be measured by the internal standard method of ¹ H-NMR.
The number of unsaturated groups contained in the terminal groups of the polymer can be measured by iodine value titration according to JIS K0070: 1992.
The number of hydroxyl groups contained in the terminal group of the polymer can be measured by a titration method using a sodium hydroxide (NaOH) solution after esterifying the hydroxyl groups with a pyridine solution of phthalic anhydride (based on JIS K1557: 2007).
The number of active hydrogen-containing groups other than hydroxyl groups contained in the terminal groups of the polymer can be measured by the internal standard method of ¹ H-NMR.

The number average molecular weight (hereinafter referred to as “Mn”) and the mass average molecular weight (hereinafter referred to as “Mw”) are polystyrene-equivalent molecular weights obtained by GPC measurement. The molecular weight distribution is a value calculated from Mw and Mn, and is a ratio of Mw to Mn (hereinafter, referred to as “Mw / Mn”).

The oxyalkylene polymer of the present embodiment (hereinafter referred to as "polymer (A)") is a polymer having a reactive silicon group, an unsaturated group, a urethane bond and a polyoxyalkylene chain represented by the following formula 1. Is. The polymer (A) has an average of more than 1.0 of the reactive silicon groups and the unsaturated groups per terminal group, and has a urethane bond in the main chain.

<Reactive silicon group>
The reactive silicon group is represented by the following formula 1.
-SiX _a R _3-a formula 1
In the above formula 1, R represents a monovalent organic group having 1 to 20 carbon atoms. R does not contain hydrolytic groups.
Examples of R include a hydrocarbon group, a halohydrocarbon group and a triorganosyloxy group.

As R, an alkyl group, a cycloalkyl group, an aryl group, a 1-chloroalkyl group and a triorganosyloxy group are preferable. At least one selected from the group consisting of a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, a 1-chloromethyl group, a trimethylsiloxy group, a triethylsiloxy group and a triphenylsiloxy group. Is more preferable. A methyl group or an ethyl group is preferable from the viewpoint of good curability of the polymer having a reactive silicon group and stability of the curable composition. A 1-chloromethyl group is preferable because the curing rate of the cured product is high. Methyl groups are particularly preferred because they are readily available.

In the above formula 1, X represents a hydroxyl group, a halogen atom or a hydrolyzable group. A hydrolyzable group is a group that can react with water to form a silanol 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 sulfanyl group and an alkenyloxy group.
As X, an alkoxy group is preferable because it is mildly hydrolyzable and easy to handle. The alkoxy group is preferably a methoxy group, an ethoxy group, or an isopropoxy group, and more preferably a methoxy group or an ethoxy group. When the alkoxy group is a methoxy group or an ethoxy group, a siloxane bond is rapidly formed, a crosslinked structure is easily formed in the cured product, and the physical properties of the cured product become better.

In the above equation 1, a represents an integer of 1 to 3. When a is 1, R may be the same or different from each other. When a is 2 or more, X may be the same as or different from each other.
a is preferably 1 or 2, and a is more preferably 2.

Examples of the reactive silicon group represented by the above formula 1 include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group and a dimethoxymethylsilyl group. Examples thereof include a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a diisopropoxymethylsilyl group, a chloromethyldimethoxysilyl group and a chloromethyldiethoxysilyl group. From the viewpoint of high activity and good curability, a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group and a diethoxymethylsilyl group are preferable, and a dimethoxymethylsilyl group and a trimethoxysilyl group are more preferable.

<Polymer (A)>
The polymer (A) consists of a main chain and a terminal group. The main chain of the polymer (A) contains a residue obtained by removing the isocyanate group from the polyisocyanate, a polyoxyalkylene chain, and a urethane bond connecting the residue and the polyoxyalkylene chain, and the terminal group is , A terminal group containing an oxygen atom closest to the molecular terminal of the polymer (A) among the oxygen atoms of the polyoxyalkylene chain.
Examples of the cyclic ether include alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide, and cyclic ethers other than alkylene oxides such as tetrahydrofuran. As the cyclic ether, alkylene oxide is preferable, ethylene oxide and propylene oxide are more preferable, and propylene oxide is particularly preferable.
The polyoxyalkylene chain may be a copolymer chain having two or more kinds of oxyalkylene groups, and in that case, the copolymer chain may be a block copolymer chain or a random copolymer chain.
Examples of the polyoxyalkylene chain contained in the polymer (A) include a polyoxypropylene chain, a polyoxyethylene chain, a poly (oxy-2-ethylethylene) chain, a poly (oxy-1,2-dimethylethylene) chain, and a poly (. Examples thereof include an oxytetramethylene) chain, a poly (oxyethylene / oxypropylene) chain, and a poly (oxypropylene / oxy-2-ethylethylene) chain. As the polyoxyalkylene chain, a polyoxypropylene chain and a poly (oxyethylene / oxypropylene) chain are preferable, and a polyoxypropylene chain is particularly preferable.

The Mn of the polymer (A) is preferably 3,000 to 100,000, more preferably 3,500 to 75,000, and even more preferably 4,000 to 60,000. When Mn is at least the lower limit of the above range, the amount of reactive silicon groups introduced can be suppressed, which is advantageous in terms of manufacturing cost, and when it is at least the upper limit, the viscosity can be suppressed, which is convenient in terms of workability. Tends to be good.
The molecular weight distribution of the polymer (A) is not particularly limited, but is preferably narrow, more preferably 2.0 or less, further preferably 1.5 or less, and particularly preferably 1.4 or less. When the molecular weight distribution is not more than the upper limit value, the stretchable physical properties of the cured product are likely to be improved.
The viscosity of the polymer (A) at 25 ° C. is preferably 0.1 to 100,000 Pa · s, more preferably 0.3 to 10,000 Pa · s, still more preferably 0.4 to 100 Pa · s. If it is within the above range, the workability is better.

The polymer (A) has an average of more than 1.0 reactive silicon groups and unsaturated groups per terminal group. The average number of the total number of the reactive silicon groups and unsaturated groups in one terminal group of the polymer (A) is preferably 1.2 to 8.0 from the viewpoint of improving the strength of the cured product. More preferably, 1.5 to 3.0 pieces.

The number of terminal groups of the polymer (A) is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6.

The polymer (A) has a urethane bond in the main chain, and the content of the urethane bond with respect to the total amount of the polymer (A) is 0.1 to 10 mass by mass from the viewpoint of improving the strength of the cured product. % Is preferable, and 0.5 to 5% by mass is more preferable.
The position of the urethane bond in the polymer (A) can be clarified by using GPC, NMR or the like after dissociating the urethane bond by the analysis method described in JP-A-2000-227430 or JP-A-2001-141726. .. The urethane bond content with respect to the total amount of the polymer (A) is the isocyanate group contained in the polyisocyanate when the type and amount of the polyisocyanate used in producing the polymer (A) are known. It can be calculated by the following formulas A and B, assuming that all of them form a urethane bond (molecular weight 59).

Urethane bond content (unit: mass%) = W (U) / W (A) × 100 ... Formula A
W (U) = (Mi × 59) + (R (U) × W (P)) ... Equation B
Mi: Total number of moles of isocyanate groups present in the polyisocyanate used to produce the polymer (A) (unit: mol)
R (U): Ratio of urethane bonds to the total amount of polyisocyanate used in the production of the polymer (A) (unit: mass%)
W (P): Mass of polyisocyanate used for producing the polymer (A) (unit: g)
W (A): Total mass of polymer (A) (unit: g)

When two or more kinds of polyisocyanates are used for the production of the polymer (A), W (U) is calculated from the above formula B for each polyisocyanate, and the sum thereof is taken as W (U). Therefore, the content of urethane bonds can be calculated.

The polymer (A) is an oxyalkylene polymer having an average of 1.0 or more of the reactive silicon groups per terminal group and having a urethane bond in the main chain (hereinafter, "heavy"). It is referred to as "combined (D)"), does not have the reactive silicon group per terminal group, has an average of more than 1.0 unsaturated groups, and has a urethane bond in the main chain. An oxyalkylene polymer (hereinafter referred to as “polymer (C)”) can be exemplified.

<Polymer (D)>
The polymer (D) has an average of more than 1.0 reactive silicon groups per terminal group. The average number of the reactive silicon groups per terminal group of the polymer (D) is preferably 1.2 to 8.0, preferably 1.5 to 3, from the viewpoint of improving the strength of the cured product. .0 is more preferable.
When the polymer (D) has an unsaturated group at the terminal group, the average number of unsaturated groups per terminal group of the polymer (D) is 0. The number is preferably 02 to 1.6, more preferably 0.03 to 1.2.

As the polymer (D), a polymer represented by the following formula 3-1 or 3-2 is preferable.

R ^20- (X) _s -expression 3-1
In the above formula 3-1 X is a monovalent group represented by the following formula 4 or 5, and R ²⁰ is a residue obtained by removing s isocyanate groups from a polyisocyanate having Mn of 100 to 20,000. Yes, s is an integer of 2-4, and the plurality of Xs may be the same or different from each other.

X-R ²¹ -AX type 3-2
In the above formula 3-2, X is a monovalent group represented by the following formula 4 or 5, and R ²¹ is a residue obtained by removing two isocyanate groups from a polyisocyanate having a Mn of 100 to 20,000. A is a divalent group represented by-[NHC (= O)-(OR ⁵⁰ ) _t -OC (= O) NH-R ²¹ ] _u- , and R ⁵⁰ has 2 carbon atoms. It represents an alkylene group of ~ 4, u is an integer of 1 to 5, t is an integer of 10 to 900, and a plurality of Xs may be the same or different from each other. (OR ⁵⁰ ) is, for example, a polyoxyalkylene chain formed by ring-opening polymerization of cyclic ether.

u is preferably 1 to 3, more preferably 1 or 2. t is preferably 20 to 650, more preferably 30 to 500.

^In R20, for example, a residue obtained by removing s isocyanate groups from a polyisocyanate having Mn of 100 or more and less than 1,000, and s isocyanate groups removed from a polyisocyanate having Mn of 1,000 to 20,000. It is a residue. s is preferably 2 to 4, more preferably 2 to 3, and even more preferably 2.
Examples of the polyisocyanate having Mn of 100 or more and less than 1,000 include aromatic polyisocyanate, aralkyl polyisocyanate, aliphatic polydiisocyanate, alicyclic polyisocyanate, and various modified products (having two isocyanate groups) of these polyisocyanates. Denatured product). Two or more kinds of polyisocyanates can be used in combination.
Examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate (MDI), 2,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 3,5-tolylene diisocyanate. Examples thereof include p-phenylenediocyanate, 1,5-naphthalenediocyanate, and polymethylene polyphenylene polyisocyanate (crude MDI).
Examples of the aralkyl polyisocyanate include xylylene diisocyanate and tetramethylxylylene diisocyanate.
Examples of the aliphatic polydiisocyanate include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate.
Examples of the alicyclic polydiisocyanate include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate and the like.
Examples of the polyisocyanate having an Mn of 1,000 or more include an isocyanate-terminated urethane prepolymer obtained by reacting a polyoxyalkylene polyol and a polyisocyanate with an index of more than 100 and an index of 200 or less. The number average molecular weight of the isocyanate-terminated urethane prepolymer can be adjusted by adjusting the index, which is the ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyoxyalkylene polyol, and the index is preferably more than 100 and 120 or less.
As the polyoxyalkylene chain in the polyoxyalkylene polyol, the same as the above-mentioned polymer (A) can be exemplified, and the preferred embodiment is also the same. The Mn of the polyoxyalkylene polyol used for a polyisocyanate having a Mn of 1,000 or more is preferably 100 to 20,000, preferably 200 to 10,000, in that the viscosity of the obtained polymer can be easily adjusted in an appropriate range. Is more preferable. The Mw / Mn of the polyoxyalkylene polyol used for the polyisocyanate having Mn of 1,000 or more is not particularly limited, but is preferably narrow, more preferably 2.0 or less, still more preferably 1.5 or less, and 1 0.4 or less is particularly preferable. When the molecular weight distribution is not more than the upper limit value, the stretchable physical properties of the obtained cured product are likely to be improved.
Examples of the polyisocyanate having Mn of 1,000 or more include urethane prepolymers described in paragraphs 0016 to 0030 of International Publication No. 2019-240046 and paragraphs 0125 to 0130 of JP-A-2017-2060602.

R ²¹ is the same as R ²⁰ except that s is 2.

前記式４中、Ｒ^１１は酸素原子、硫黄原子、前記式４中の－（ＣＨ_２）_ｍ―と結合する原子が炭素原子である－Ｃ（＝Ｏ）Ｏ－で表される２価の基、又は－Ｎ（Ｒ^１０）－で表される２価の基であり、Ｒ^１０は水素原子又は炭素数１～１０の１価の炭化水素基であり、Ｒ^１２は水素原子又はメチル基であり、Ｒ^１４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、Ｒ^１５は酸素原子若しくは窒素原子を含んでもよく、酸素原子若しくは窒素原子と隣接する原子は炭素原子である炭素数１～２０の１価の炭化水素基、水素原子、又は－Ｒ^１７－ＣＨＲ^１８－ＣＨ_２－^ｒＳｉで表される基であり、Ｒ^１８は水素原子又はメチル基であり、Ｒ^１７は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、Ｒ^５０は前記式３－２と同様であり、^ｒＳｉは反応性ケイ素基を示し、複数のＲ^１２、Ｒ^１４、Ｒ^５０、^ｒＳｉはそれぞれ互いに同一でも異なってもよく、ｍは０～１０の整数であり、ｑは１０～９００の整数である。

In the above formula 4, R ¹¹ is an oxygen atom, a sulfur atom, and the atom bonded to- (CH ₂ ) _m -in the above formula 4 is a carbon atom-C (= O) O-, which is a divalent atom. A group or a divalent group represented by -N (R ¹⁰ )-, R ¹⁰ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ¹² is a hydrogen atom or a methyl group. R ¹⁴ may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom, and R ¹⁵ May contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom, which is a monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or -R ¹⁷ -CHR ¹⁸ -CH. A group represented by ₂ - ^rSi , R ¹⁸ is a hydrogen atom or a methyl group, R ¹⁷ may contain an oxygen atom or a nitrogen atom, and an atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom. It is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, R ⁵⁰ is the same as that of the above formula 3-2, ^r Si is a reactive silicon group, and a plurality of R ¹² , R ¹⁴ , R. ⁵⁰ and ^rSi may be the same or different from each other, and m is an integer of 0 to 10 and q is an integer of 10 to 900.

m is preferably 0 to 8, more preferably 1 to 7, and even more preferably 1 to 6.
The carbon number of R ¹⁰ includes the carbon number of the substituent when R ¹⁰ has a substituent having a carbon atom. The monovalent hydrocarbon group of R ¹⁰ has preferably 1 to 9 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.
As R ¹¹ , a divalent group represented by an oxygen atom or a divalent group represented by —C (= O) O— in which the atom bonded to − (CH ₂ ) _m— in the above formula 4 is a carbon atom is preferable, and an oxygen atom. Is more preferable.

The carbon number of R ¹⁵ includes the carbon number of the substituent when R ¹⁵ has a substituent having a carbon atom.
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of R ¹⁵ include an alkyl group, a cycloalkyl group, an alkenyl group and an aryl group. The alkyl group and alkenyl group may be linear or branched.

As the alkyl group, an alkyl group having 1 to 18 carbon atoms is preferable.
The linear alkyl group includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group and n. Examples thereof include a decyl group, an n-undecyl group, a lauryl group and a stearyl group, and a methyl group and an ethyl group are preferable. The branched alkyl group has a structure in which a hydrogen atom in the linear alkyl group (excluding the hydrogen atom in the terminal carbon) is substituted with an alkyl group. Examples of the alkyl group as the substituent include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group and an n-heptyl. The group can be exemplified, and a methyl group, an ethyl group, and an n-propyl group are preferable.
The alkyl group may be an alkyl group having a cycloalkane structure. Examples of the alkyl group having a cycloalkane structure include a monovalent group in which the methylene group in the linear or branched alkyl group is replaced with a cycloalkylene group. As the cycloalkylene group, a divalent group obtained by removing one hydrogen atom from the cycloalkyl group described later can be exemplified.

Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group and a cyclodecyl group, and a cyclohexyl group and a cyclopentyl group are preferable. It may have a structure in which a hydrogen atom in a cycloalkyl group is substituted with an alkyl group. The alkyl group as a substituent includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group and an n-heptyl group. Can be exemplified, and a methyl group, an ethyl group, and an n-propyl group are preferable.

Examples of the alkenyl group include those in which the single bond between any one carbon atom of the alkyl group is replaced with a double bond.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, and an anthryl group. It may have a structure in which a hydrogen atom in an aryl group is substituted with an alkyl group. The alkyl group as a substituent includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group and an n-heptyl group. Can be exemplified, and a methyl group, an ethyl group, and an n-propyl group are preferable.

The total number of oxygen atoms and nitrogen atoms in R15 is preferably ⁵ or less, more preferably 3 or less, and even more preferably 1 or less. The atom in R ¹⁵ that is directly bonded to the carbon atom adjacent to R ¹⁴ and R ¹⁵ in the above formula 4 is preferably a carbon atom.

The monovalent hydrocarbon group having ¹ to 20 carbon atoms containing the oxygen atom of R15 has an alkoxy group, a monovalent group in which the hydrogen atom in the alkyl group is replaced with an alkoxy group, and the cycloalkane structure. Examples thereof include monovalent groups in which the hydrogen atom in the alkyl group is substituted with an alkoxy group, and specifically, -OCH ₃ , -O-CH ₂ -CH ₃ , -O- (CH ₂ ) ₂ -CH ₃ , -O- (CH ₂ ) ₃ -CH ₃ , -OCH (CH ₃ ) ₂ , -CH ₂ -O-CH ₃ ,-(CH ₂ ) ₂ -O-CH ₃ ,-(CH ₂ ) ₃ -O -CH ₃ , -CH (CH ₃ ) CH ₂ -O-CH ₃ ,-(CH ₂ ) ₄ -O-CH ₃ , -C (CH ₃ ) ₂ CH ₂ -O-CH ₃ ,-(CH ₂ ) ₅ -O-CH ₃ ,-(CH ₂ ) ₆ -O-CH ₃ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-CH ₃ , -CH ₂ -O-CH ₂ -CH ₃ ,-( CH ₂ ) ₂ -O-CH ₂ -CH ₃ ,-(CH ₂ ) ₃ -O-CH ₂ -CH ₃ , -CH (CH ₃ ) CH ₂ -O-CH ₂ -CH ₃ ,-(CH ₂ ) ₄ -O-CH ₂ -CH ₃ , -C (CH ₃ ) ₂ CH ₂ -O-CH ₂ -CH ₃ ,-(CH ₂ ) ₅ -O-CH ₂ -CH ₃ ,-(CH ₂ ) _6- Examples thereof include O-CH ₂ -CH ₃ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-CH ₂ -CH ₃ , and the like. In the above example, -C ₆ H _10- means a cyclohexylene group, and so on.

Examples of the monovalent hydrocarbon group having 1 to ²⁰ carbon atoms containing the nitrogen atom of R15 include -CH ₂ -NH-CH ₃ and -CH ₂ -N (CH ₃ ) ₂ .

As ^R15 , a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent group represented by _−CH2 -O—CH ₃ is preferable, and a hydrogen atom and a linear alkyl having 1 to 18 carbon atoms are preferable. A group, a branched alkyl group having 1 to 18 carbon atoms, or a monovalent group represented by _−CH2 -O—CH ₃ is more preferable, and a hydrogen atom or a linear alkyl group having 1 to 18 carbon atoms is further preferable. Preferably, a linear alkyl group having 1 to 6 carbon atoms is more preferable, a linear alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group, an ethyl group or a propyl group is particularly preferable.

R ¹⁸ is a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms of R ¹⁷ include an alkylene group, a cycloalkylene group, an alkaneylene group and an arylene group. Examples of the alkylene group, cycloalkylene group, ^alkenylene group, and arylene group include a linear alkyl group, a cycloalkyl group, a linear alkenyl group, and a divalent group obtained by removing one hydrogen atom from an aryl group. Can be exemplified. The alkylene group and the alkenylene group may be linear or branched.

R ¹⁷ may have a substituent, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms. The carbon number of R ¹⁷ includes the carbon number of the substituent when R ¹⁷ has a substituent having a carbon atom.

R ¹⁷ may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom. The total number of oxygen atoms and nitrogen atoms in R ¹⁷ is preferably 5 or less, more preferably 3 or less, and even more preferably 1 or less. The atom in R ¹⁷ that directly bonds to the carbon atom adjacent to R ¹⁵ and R ¹⁴ in the above formula 4 is preferably a carbon atom.

As the divalent hydrocarbon group having 1 to 20 carbon atoms containing the oxygen atom of R ¹⁷ , one hydrogen atom is removed from the monovalent hydrocarbon group having 1 to 20 carbon atoms including the oxygen atom exemplified in R ¹⁵ . An example is a divalent group.
As the divalent hydrocarbon group having 1 to 20 carbon atoms containing the nitrogen atom of R ¹⁷ , one hydrogen atom is removed from the monovalent hydrocarbon group having 1 to 20 carbon atoms including the nitrogen atom exemplified in R ¹⁵ . An example is a divalent group.

As R ¹⁷ , an alkylene group having 1 to 18 carbon atoms, an alkylene group having 1 to 18 carbon atoms including an oxygen atom, and a cycloalkylene group having 1 to 18 carbon atoms are preferable, and an alkylene group having 1 to 10 carbon atoms or an oxygen atom. An alkylene group having 1 to 10 carbon atoms including the above is more preferable, and an alkylene group having 1 to 6 carbon atoms or an alkylene group having 1 to 6 carbon atoms containing one oxygen atom is further preferable.

The groups represented by -R ¹⁷ -CHR ¹⁸ -CH ₂ - ^r Si are -OCH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -O- (CH ₂ ) ₃ - ^r Si, -O. -(CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -O- (CH ₂ ) ₄ - ^r Si, -O- (CH ₂ ) ₃ -CH (CH ₃ ) -CH ₂ - ^r Si _, -O- (CH ₂ ) ₅ - ^r Si, -O- (CH ₂ ) ₄ -CH (CH ₃ ) -CH ₂ - ^r Si, -O- (CH ₂ ) ₆ - ^r Si, -OC ( CH ₃ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -OC (CH ₃ ) _2- (CH ₂ ) ₂ - ^r Si, -CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH ₂ -O- (CH ₂ ) ₃ -- ^r Si,-(CH ₂ ) ₂ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₂ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₃ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₃ -O- (CH ₂ ) ₃ ^-R Si, -CH (CH ₃ ) CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ₃ - ^r Si, -(CH ₂ ) ₄ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₄ -O- (CH ₂ ) ₃ - ^r Si, -C (CH ₃ ) ₂ CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₅ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₅ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₆ -O-CH ₂ -CH (CH ₃ )- CH ₂ - ^r Si,-(CH ₂ ) ₆ -O- (CH ₂ ) ₃ - ^r Si, -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH _2- ^r Si, -CH ₂ -C ₆ H ₁₀ -CH ₂ -O- (CH ₂ ) ₃ - ^r Si, -CH ₂ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH ₂ -O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ) ₂ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₂ -O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₃ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₃ -O- (CH ₂ ) ₄ - ^r Si, -CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₄ -O- (CH ₂ ) _2- CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₄ -O- (CH ₂ ) ₄ - ^r Si, -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₂ -CH (CH 2) CH ₃ ) -CH ₂ - ^r Si, -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₅ -O- (CH ₂ ) ₂ -CH (CH ₃ ) ) -CH ₂ - ^r Si,-(CH ₂ ) ₅ -O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₆ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH _2- ^r Si,-(CH ₂ ) ₆ -O- (CH ₂ ) ₄ - ^r Si, -CH ₂ -C ₆ H ₁₀ -CH ₂ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH _2- ^r Si, -CH ₂ -C ₆ H ₁₀ -CH ₂ -O- (CH ₂ ) ₄ - ^r Si can be exemplified, -CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH _2- ^r Si, -(CH ₂ ) ₂ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₃ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH ₂ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₂ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₃ -O- (CH ₂ ) ₃ - ^r Si are preferable. , -CH ₂ -O- (CH ₂ ) ₃ - ^r Si or-(CH ₂ ) ) ₂ -O- (CH ₂ ) ₃ - ^rSi is more preferable.

R ¹² is the same as R ¹⁸ described above, and the preferred embodiment is also the same.
R ¹⁴ is the same as R ¹⁷ described above, and the preferred embodiment is also the same.
The group represented by -R ¹⁴ -CHR ¹² -CH ₂ - ^r Si is the same as the group represented by -R ¹⁷ -CHR ¹⁸ -CH ₂ - ^r Si described above, and the preferred embodiment is also the same.

q is preferably 10 to 900, more preferably 20 to 650, and even more preferably 30 to 500.

前記式５中、Ｒ^３２は水素原子又はメチル基であり、Ｒ^３４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、Ｒ^５０、^ｒＳｉ、ｑは前記式４と同様であり、複数のＲ^３２、Ｒ^３４、Ｒ^５０、^ｒＳｉはそれぞれ互いに同一でも異なってもよい。

In the above formula 5, R ³² is a hydrogen atom or a methyl group, R ³⁴ may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom having 1 to 20 carbon atoms. It is a valent hydrocarbon group or a single bond, and R ⁵⁰ , ^r Si, and q are the same as in the above formula 4, and a plurality of R ³² , R ³⁴ , R ⁵⁰ , and ^r Si may be the same or different from each other.

The carbon number of the divalent hydrocarbon group of R ³⁴ is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less. The carbon number of R ³⁴ includes the carbon number of the substituent when R ³⁴ has a substituent having a carbon atom.

Examples of the divalent hydrocarbon group of R ³⁴ include an alkylene group, a cycloalkylene group, an alkenylene group and an arylene group, and an alkylene group and a cycloalkylene group are preferable, and an alkylene group is more preferable. The alkylene group and the alkenylene group are linear or branched.

Examples of the alkylene group, the cycloalkylene group, the alkenylene group, and the arylene group are the same as those of ^R17 .

The total number of oxygen atoms and nitrogen atoms in R ³⁴ is preferably 5 or less, more preferably 3 or less, and even more preferably 1 or less. The atom in R ³⁴ that directly bonds with the nitrogen atom in the above formula 5 is preferably a carbon atom.

The groups represented by -R ³⁴ CHR ³² -CH ₂ - ^r Si are -CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH ₂ -O- (CH ₂ ). ₃ - ^r Si,-(CH ₂ ) ₂ -O-CH ₂ -CH (CH ₃ ) -CH _2- ^r Si,-(CH ₂ ) ₂ -O- (CH ₂ ) ₃ -- ^r Si,-(CH) ₂ ) ₃ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₃ -O- (CH ₂ ) ₃ - ^r Si, -CH (CH ₃ ) CH ₂ -O- CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₄ -O-CH ₂ -CH (CH) ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₄ -O- (CH ₂ ) ₃ - ^r Si, -C (CH ₃ ) ₂ CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH ₂ ^-R Si, -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₅ -O-CH ₂ -CH (CH ₃ ) -CH _2- ^r Si,- (CH ₂ ) ₅ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₆ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₆ -O- (CH ₂ ) ₃ - ^r Si, -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH _2- ^r Si, -CH ₂ -C ₆ H ₁₀ -CH _2- O- (CH ₂ ) ₃ - ^r Si, -CH ₂ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH ₂ -O- (CH ₂ ) ₄ - ^r Si, -(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₂ -O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₃ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₃ -O- (CH ₂ ) ₄ - ^r Si, -CH (CH ₃ ) CH ₂ -O -(CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₄ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH 2) ₂ ) ₄ -O- (CH ₂ ) ₄ - ^r Si, -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -C (CH ₃ ) ) ₂ CH ₂ -O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₅ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) _5- O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₆ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₆ -O- (CH ₂ ) ) ₄ - ^r Si, -CH ₂ -C ₆ H ₁₀ -CH ₂ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH ₂ -C ₆ H ₁₀ -CH _2- O- (CH ₂ ) ₄ - ^r Si can be exemplified, -CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₂ -O-CH ₂ -CH (CH). ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₃ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH ₂ -O- (CH ₂ ) ₃ -- ^r Si,-( CH ₂ ) ₂ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₃ -O- (CH ₂ ) ₃ - ^r Si is preferable, and -CH ₂ -O- (CH ₂ ) ₃ - ^r Si is preferable. Alternatively,-(CH ₂ ) ₂ -O- (CH ₂ ) ₃ - ^rSi is more preferable.

<Polymer (C)>
The polymer (C) has an average of more than 1.0 unsaturated groups per terminal group. The average number of unsaturated groups per terminal group of the polymer (C) is preferably 1.2 to 8.0, more preferably 1.5 to 3.0, from the viewpoint of reactivity.

As the polymer (C), the polymer in which X is represented by the following formula 6 or 7 in the above formula 3-1 or 3-2 is preferable.

前記式６中、Ｒ^１１、Ｒ^１２、Ｒ^１４、Ｒ^５０、ｍ、ｑは、前記式４と同様であり、Ｒ^１６は酸素原子若しくは窒素原子を含んでもよく、酸素原子若しくは窒素原子と隣接する原子は炭素原子である炭素数１～２０の１価の炭化水素基、水素原子、又は－Ｒ^６４－ＣＲ^６３＝ＣＨ_２で表される基であり、Ｒ^６３は水素原子又はメチル基であり、Ｒ^６４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、複数のＲ^１２、Ｒ^１４、Ｒ^５０はそれぞれ互いに同一でも異なってもよい。

In the above formula 6, R ¹¹ , R ¹² , R ¹⁴ , R ⁵⁰ , m, and q are the same as those in the above formula 4, and R ¹⁶ may contain an oxygen atom or a nitrogen atom and is adjacent to the oxygen atom or the nitrogen atom. The atom is a carbon atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a group represented by -R ⁶⁴ -CR ⁶³ = CH ₂ , and R ⁶³ is a hydrogen atom or a methyl group. Yes, R ⁶⁴ may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom, and a plurality of R's are present. ¹² , R ¹⁴ and R ⁵⁰ may be the same or different from each other.

The carbon number of R ¹⁶ includes the carbon number of the substituent when R ¹⁶ has a substituent having a carbon atom.
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of R ¹⁶ include an alkyl group, a cycloalkyl group, an alkenyl group and an aryl group. The alkyl group and alkenyl group may be linear or branched.

Examples of the alkyl group, the cycloalkyl group, the alkenyl group, and the aryl group are the same as those of ^R15 including the substituent.

The monovalent hydrocarbon group having 1 to 20 carbon atoms containing the oxygen atom of R ¹⁵ is the same as that of R ¹⁶ , and the preferred embodiment is also the same.
The monovalent hydrocarbon group having 1 to 20 carbon atoms containing a nitrogen atom of R ¹⁵ is the same as that of R ¹⁶ , and the preferred embodiment is also the same.

R ⁶³ is the same as R ¹⁸ , and the preferred embodiment is also the same.
R ⁶⁴ is the same as R ¹⁷ , and the preferred embodiment is also the same.

The groups represented by -R ¹⁴ -CR ¹² = CH ₂ and -R ⁶⁴ -CR ⁶³ = CH ₂ are independently -OCH ₂ -C (CH ₃ ) = CH ₂ and -OCH ₂ -CH = CH, respectively. ₂ , -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ , -O- (CH ₂ ) ₂ -CH = CH ₂ , -O- (CH ₂ ) ₃ -C (CH ₃ ) = CH _2, -O- (CH ₂ ) ₃ -CH = CH ₂ , -O- (CH ₂ ) ₄ -C (CH ₃ ) = CH ₂ , -O- (CH ₂ ) ₄ -CH = CH ₂ , -OC (CH ₃ ) ₂ -C (CH ₃ ) = CH ₂ , -OC (CH ₃ ) ₂ -CH = CH ₂ , -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH _2- O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -CH = CH ₂ ,-( CH ₂ ) ₃ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₃ -O-CH ₂ -CH = CH ₂ , -CH (CH ₃ ) CH ₂ -O-CH _2- C (CH ₃ ) = CH ₂ , -CH (CH ₃ ) CH ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₄ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,- (CH ₂ ) ₄ -O-CH ₂ -CH = CH ₂ , -C (CH ₃ ) ₂ CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -C (CH ₃ ) ₂ CH _2- O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₅ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₅ -O-CH ₂ -CH = CH ₂ ,-(CH 2) CH ₂ ) ₆ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₆ -O-CH ₂ -CH = CH ₂ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O- CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-CH ₂ -CH = CH ₂ , -CH ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) ) = CH ₂ , -CH ₂ -O- (CH ₂ ) ₂ -CH = CH ₂ ,-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -CH = CH ₂ ,-(CH ₂ ) ₃ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₃ -O- (CH ₂ ) ₂ -CH = CH ₂ , -CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ , -CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ₂ -CH = CH ₂ ,-(CH ₂ ) ₄ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ) ₄ -O- (CH ₂ ) ₂ -CH = CH ₂ , -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ , -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₂ -CH = CH ₂ ,-(CH ₂ ) ₅ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₅ -O- ( CH ₂ ) ₂ -CH = CH ₂ ,-(CH ₂ ) ₆ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₆ -O- (CH ₂ ) ₂ -CH = CH ₂ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O- (CH ₂ ) ) ₂ -CH = CH ₂ can be exemplified, -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -(CH ₂ ) ₃ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₃ -O-CH ₂ -CH = CH ₂ is preferable, -CH ₂ -O-CH ₂ -CH = CH ₂ or-(CH ₂ ) ₂ -O-CH ₂ -CH = CH ₂ is more preferable.

前記式７中、Ｒ^３２、Ｒ^３４、Ｒ^５０、ｑは、前記式５と同様であり、複数のＲ^３２、Ｒ^３４、Ｒ^５０はそれぞれ互いに同一でも異なってもよい。

In the above formula 7, R ³² , R ³⁴ , R ⁵⁰ , and q are the same as those in the above formula 5, and the plurality of R ³² , R ³⁴ , and R ⁵⁰ may be the same or different from each other.

The groups represented by -R ³⁴ -CR ³² = CH ₂ are -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -O-CH ₂ -CH = CH ₂ , and-. (CH ₂ ) ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₃ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₃ -O-CH ₂ -CH = CH ₂ , -CH (CH ₃ ) CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH (CH ₃ ) CH ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₄ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₄ -O-CH _2- CH = CH ₂ , -C (CH ₃ ) ₂ CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -C (CH ₃ ) ₂ CH ₂ -O-CH ₂ -CH = CH ₂ ,- (CH ₂ ) ₅ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₅ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₆ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₆ -O-CH ₂ -CH = CH ₂ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-CH ₂ -CH = CH ₂ , -CH ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -O- (CH ₂ ) ₂ -CH = CH ₂ ,-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O- (CH ₂ ) _2- CH = CH ₂ ,-(CH ₂ ) ₃ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₃ -O- (CH ₂ ) ₂ -CH = CH ₂ ,- CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ , -CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ₂ -CH = CH ₂ ,-(CH) ₂ ) ₄ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₄ -O- (CH ₂ ) ₂ -CH = C H ₂ , -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ , -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₂ -CH = CH ₂ ,-(CH ₂ ) ₅ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₅ -O- (CH ₂ ) ₂ -CH = CH ₂ ,-(CH) ₂ ) ₆ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₆ -O- (CH ₂ ) ₂ -CH = CH ₂ , -CH ₂ -C ₆ H _10- CH ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O- (CH ₂ ) ₂ -CH = CH ₂ can be exemplified, and -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₃ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₃ -O-CH ₂ -CH = CH ₂ is preferable, and -CH ₂ -O-CH ₂ -CH = CH ₂ or-(CH ₂ ) ₂ -O-CH ₂ -CH = CH ₂ is more preferable.

<Method for producing polymer (D)>
In the method for producing the oxyalkylene polymer (D) of the present embodiment, the active hydrogen-containing group at the other terminal group of the following oxyalkylene polymer (B) is reacted with a polyisocyanate having a molecular weight of 100 to 20,000. Then, the following oxyalkylene polymer (C) is obtained, and then the unsaturated group at the terminal group of the oxyalkylene polymer (C) is reacted with the silylating agent having a reactive silicon group represented by the above formula 1. This is a method for producing the oxyalkylene polymer (C).
Oxyalkylene polymer (B): A polymer having an unsaturated group, an active hydrogen-containing group and a polyoxyalkylene chain, and having an average of 1.0 or more unsaturated groups at one terminal group. An oxyalkylene polymer having an average of more than 0 and 1.0 or less active hydrogen-containing groups in the other terminal group.
Oxyalkylene polymer (C): A polymer having an unsaturated group and a polyoxyalkylene chain, which has an average of 1.0 or more unsaturated groups per terminal group.

<Polymer (B)>
The polymer (B) has a main chain containing a polyoxyalkylene chain, one terminal group containing an oxygen atom at one end of the polyoxyalkylene chain and a residue obtained by removing active hydrogen from the initiator, and the polyoxy. A linear polymer consisting of the other terminal group containing an oxygen atom at the other end of the alkylene chain. The other terminal group is a hydroxyl group.
Examples of the polyoxyalkylene chain possessed by the polymer (B) are the same as those of the polymer (A).

The hydroxyl group-equivalent molecular weight of the polymer (B) obtained by using an initiator having a hydroxyl group as an active hydrogen-containing group is preferably 2,000 to 35,000, more preferably 2,500 to 17,000, and 3, More preferably 000 to 10,000. When the molecular weight converted to hydroxyl groups is at least the lower limit of the above range, the amount of reactive silicon groups introduced can be suppressed in the subsequent reaction, which is advantageous in terms of manufacturing cost, and when it is at least the upper limit, the viscosity is suppressed. , Tends to be convenient in terms of workability.
The Mn of the polymer (B) is preferably 2,200 to 50,000, more preferably 2,500 to 25,000, and even more preferably 3,000 to 15,000. When Mn is at least the lower limit of the above range, the amount of reactive silicon groups introduced can be suppressed in the subsequent reaction, which is advantageous in terms of manufacturing cost, and when it is at least the upper limit, the viscosity is suppressed and the work is performed. It tends to be convenient in terms of sex.
The molecular weight distribution of the polymer (B) is preferably 2.0 or less, more preferably 1.5 or less, further preferably 1.4 or less, and particularly preferably 1.2 or less. The molecular weight distribution of the polymer (A) is preferably 1.0 or more. When the molecular weight distribution is not more than the upper limit value, the stretchable physical properties of the cured product are likely to be improved.
The viscosity of the polymer (B) at 25 ° C. is preferably 0.05 to 100,000 Pa · s, more preferably 0.1 to 10,000 Pa · s, still more preferably 0.3 to 100 Pa · s. If it is within the above range, the workability is better.

The polymer (B) has an average of more than 1.0 unsaturated groups at one end group. The average number of unsaturated groups in one end group of the polymer (B) is preferably 1.2 to 8.0, preferably 1.5 to 3.0, from the viewpoint of improving the strength of the cured product. Is more preferable. The polymer (B) has an average of more than 0 and 1.0 or less active hydrogen-containing groups in the other terminal group. The average number of active hydrogen-containing groups in the other terminal group of the polymer (B) is preferably 0.5 to 1.0, more preferably 1.0, from the viewpoint of reactivity.

As the residue obtained by removing the active hydrogen from the initiator contained in one of the terminal groups of the polymer (B), a monovalent group represented by the following formula 8 or 9 is preferable.

前記式８中、Ｒ^１１、Ｒ^１２、Ｒ^１４、Ｒ^１６、ｍは前記式６と同様であり、複数のＲ^１２、Ｒ^１４はそれぞれ互いに同一でも異なってもよい。

In the above formula 8, R ¹¹ , R ¹² , R ¹⁴ , R ¹⁶ and m are the same as those in the above formula 6, and the plurality of R ¹² and R ¹⁴ may be the same or different from each other.

As the residues obtained by removing the active hydrogen from the initiator represented by the above formula 8, R ¹¹ is an oxygen atom, m is 1 to 3, and R ¹⁴ is -CH ₂ -O-CH ₂ -,-. (CH ₂ ) ₂ -O-CH ₂ -,-(CH ₂ ) ₃ -O-CH _2- is a divalent group, R ¹² is a hydrogen atom or a methyl group, and R ¹⁶ is oxygen. Alkyl group with 1 to 2 carbon atoms containing no atoms and nitrogen atoms, or -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -C (CH) ₃ ) = CH ₂ ,-(CH ₂ ) ₃ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₂ -O- A monovalent group represented by CH ₂ -CH = CH ₂ or-(CH ₂ ) ₃ -O-CH ₂ -CH = CH ₂ is preferable.

As the residue obtained by removing the active hydrogen from the initiator represented by the above formula 8, R ¹¹ is an oxygen atom, m is 1, and R ¹⁴ is represented by _{−CH2 -} O—CH2-. It is a divalent group, R ¹² is a hydrogen atom or a methyl group, and a plurality of R ^16s are an alkyl group having 1 to 2 carbon atoms containing no oxygen atom and a nitrogen atom, or -CH ₂ -O-CH _2- . A monovalent group represented by C (CH ₃ ) = CH ₂ or-(CH ₂ ) -O-CH ₂ -CH = CH ₂ is preferable.

前記式９中、Ｒ^３２、Ｒ^３４は前記式７と同様であり、複数のＲ^３２、Ｒ^３４はそれぞれ互いに同一でも異なってもよい。

In the formula 9, R ³² and R ³⁴ are the same as those in the formula 7, and the plurality of R ³² and R ³⁴ may be the same or different from each other.

As the residue obtained by removing the active hydrogen from the initiator represented by the above formula 9, R ³² is a hydrogen atom or a methyl group, and R ³⁴ is an alkylene group having 1 to 2 carbon atoms and does not contain an oxygen atom or a nitrogen atom. A monovalent group is preferred.

(Method for producing polymer (B))
The polymer (B) initiates a compound having two or more unsaturated groups in one molecule and one active hydrogen-containing group in one molecule (hereinafter referred to as “compound a”). As an agent, it is obtained by subjecting a cyclic ether to a ring-opening addition polymerization reaction.
Examples of the cyclic ether include alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide, and cyclic ethers other than alkylene oxides such as tetrahydrofuran. As the cyclic ether, alkylene oxide is preferable, ethylene oxide and propylene oxide are more preferable, and propylene oxide is particularly preferable.

The number of unsaturated groups in one molecule of compound a is preferably 2 to 5, preferably 2 to 4, more preferably 2 or 3, and even more preferably 2.
The unsaturated group in compound a is preferably an unsaturated group at the end of the molecule.

The molecular weight of the compound a is preferably less than 1,000, more preferably 60 or more and less than 900, further preferably 70 to 500, and particularly preferably 70 to 300, from the viewpoint of reactivity with the cyclic ether.

As the compound a, the compounds represented by the following formulas 2 and 10 are preferable.

前記式２中、Ｒ^１は活性水素含有基、Ｒ^２は水素原子又はメチル基であり、Ｒ^４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、Ｒ^６は酸素原子若しくは窒素原子を含んでもよく、酸素原子若しくは窒素原子と隣接する原子は炭素原子である炭素数１～２０の１価の炭化水素基、水素原子、又は－Ｒ^６２－ＣＲ^６１＝ＣＨ_２で表される基であり、Ｒ^６１は水素原子又はメチル基であり、Ｒ^６２は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、複数のＲ^２、Ｒ^４はそれぞれ互いに同一でも異なってもよく、ｎは０～１０の整数である。

In the above formula 2, R ¹ is an active hydrogen-containing group, R ² is a hydrogen atom or a methyl group, R ⁴ may contain an oxygen atom or a nitrogen atom, and an atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom. A divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, R ⁶ may contain an oxygen atom or a nitrogen atom, and an oxygen atom or an atom adjacent to the nitrogen atom is a carbon atom having 1 to 20 carbon atoms. A monovalent hydrocarbon group of 20, a hydrogen atom, or a group represented by -R ⁶² -CR ⁶¹ = CH ₂ , R ⁶¹ is a hydrogen atom or a methyl group, and R ⁶² is an oxygen atom or a nitrogen atom. It may be contained, and the atom adjacent to the oxygen atom or the nitrogen atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom, and a plurality of R ² and R ⁴ are the same or different from each other. Often, n is an integer from 0 to 10.

n is preferably 0 to 8, more preferably 1 to 7, and even more preferably 1 to 6.

R ¹ is an active hydrogen-containing group, and a hydroxyl group, a carboxy group, an amino group, a monovalent functional group obtained by removing a hydrogen atom from a primary amine and a sulfanyl group are preferable, and a hydroxyl group, a carbonyl group or an amino group is more preferable.
^R2 is a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
The carbon number of R ⁴ includes the carbon number of the substituent when R ⁴ has a substituent having a carbon atom.
Examples of the divalent hydrocarbon group in ^R4 include an alkylene group, a cycloalkylene group, an alkenylene group and an arylene group. The alkylene group and the alkenylene group may be linear or branched.

Examples of the alkylene group, the cycloalkylene group, the alkenylene group, and the arylene group are the same as those of ^R14 including the substituent.

The divalent hydrocarbon group having 1 to 20 carbon atoms containing the oxygen atom of R ⁴ is the same as that of R ¹⁴ , and the preferred embodiment is also the same.
The divalent hydrocarbon group having 1 to 20 carbon atoms containing the nitrogen atom of R ⁴ is the same as that of R ¹⁴ , and the preferred embodiment is also the same.

The group represented by -R ⁴ -CR ² = CH ₂ is the same as the group represented by -R ¹⁴ -CR ¹² = CH ₂ , and the preferred embodiment is also the same.

The carbon number of R ⁶ includes the carbon number of the substituent when R ⁶ has a substituent having a carbon atom.
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of R ⁶ include an alkyl group, a cycloalkyl group, an alkenyl group and an aryl group. The alkyl group and alkenyl group may be linear or branched.

Examples of the alkyl group, cycloalkyl group, alkenyl group, and aryl group are the same as those of ^R16 including the substituent.

The monovalent hydrocarbon group having 1 to 20 carbon atoms containing the oxygen atom of R ⁶ is the same as that of R ¹⁶ , and the preferred embodiment is also the same.
The monovalent hydrocarbon group having 1 to 20 carbon atoms containing the nitrogen atom of R ⁶ is the same as that of R ¹⁶ , and the preferred embodiment is also the same.

R ⁶¹ is the same as R ² , and the preferred embodiment is also the same.
R ⁶² is the same as R ⁴ , and the preferred embodiment is also the same.

The group represented by -R ⁶² -CR ⁶¹ = CH ₂ is the same as the group represented by -R ⁴ -CR ² = CH ₂ , and the preferred embodiment is also the same.

As the compound a represented by the above formula 2, R ¹ is a hydroxyl group, n is 1 to 3, and R ⁴ is -CH ₂ -O-CH ₂ -,-(CH ₂ ) ₂ -O-CH. ₂ -,-(CH ₂ ) ₃ -A divalent group represented by -O-CH _2- , R ² is a hydrogen atom or a methyl group, and R ⁶ is the number of carbon atoms free of oxygen and nitrogen atoms. 1-2 alkyl groups, or -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH) ₂ ) ₃ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -CH = CH ₂ , or -(CH ₂ ) ₃ -O-CH ₂ -A monovalent group represented by CH = CH ₂ is preferable.

As the compound a represented by the above formula 2, R ¹ is a hydroxyl group, n is 1, and R ⁴ is a divalent group represented by −CH ₂ -O—CH _2- , and R ² Is a hydrogen atom or a methyl group, and R ⁶ is an alkyl group having 1 to 2 carbon atoms which does not contain an oxygen atom and a nitrogen atom, or -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ or-( A monovalent group represented by CH ₂ ) -O-CH ₂ -CH = CH ₂ is preferable.

前記式１０中、Ｒ^２２は水素原子又はメチル基であり、Ｒ^２４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、複数のＲ^２２、Ｒ^２４はそれぞれ互いに同一でも異なってもよい。Ｒ^２４の炭素数は、Ｒ^２４が炭素原子を有する置換基を有する場合は、置換基の炭素数を含む。

In the above formula 10, R ²² is a hydrogen atom or a methyl group, R ²⁴ may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom having 1 to 20 carbon atoms. It is a valent hydrocarbon group or a single bond, and the plurality of R ²² and R ²⁴ may be the same or different from each other. The carbon number of R ²⁴ includes the carbon number of the substituent when R ²⁴ has a substituent having a carbon atom.

R ²² is preferably a hydrogen atom. Examples of the divalent hydrocarbon group in R ²⁴ include an alkylene group, a cycloalkylene group, an alkenylene group and an arylene group.

Examples of the alkylene group, the cycloalkylene group, the alkenyl group, and the aryl group are the same as those of ^R34 including the substituent. The alkylene group and the alkenylene group may be linear or branched.

The divalent hydrocarbon group having 1 to 20 carbon atoms containing the oxygen atom of R ²⁴ is independently the same as that of R ³⁴ , and the preferred embodiment is also the same.
The divalent hydrocarbon group having 1 to 20 carbon atoms containing the nitrogen atom of R ²⁴ is independently the same as that of R ³⁴ , and the preferred embodiment is also the same.

As the compound a represented by the formula 10, a compound a in which one of the plurality of R ^24s is a methylene group is preferable, and a compound a in which both of the plurality of R ^24s are a methylene group is more preferable.

A conventionally known catalyst can be used as the ring-opening addition polymerization catalyst when the cyclic ether is reacted with the initiator as the ring-opening addition polymerization reaction. For example, an alkali catalyst (KOH or the like), a transition metal compound-porphyrin complex catalyst (organic) Examples thereof include a complex obtained by reacting an aluminum compound with porphyrin), a composite metal cyanation complex catalyst, and a catalyst composed of a phosphazene compound.

A composite metal cyanide complex catalyst is preferable because the molecular weight distribution of the polymer (B) can be narrowed and a curable composition having a low viscosity can be easily obtained. As the composite metal cyanide complex catalyst, a conventionally known compound can be used, and a known method can also be adopted as a method for producing a polymer using the composite metal cyanide complex. 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 compounds and production methods disclosed in the publication can be used.

(Method for producing compound a)
The compound a is a group having x-1 active hydrogen-containing groups in a compound having x active hydrogen-containing groups (where x is an integer of 3 or more) in one molecule and an unsaturated group. Can be manufactured by converting to. As a method for converting an active hydrogen-containing group into a group having an unsaturated group, a method of reacting an alkali metal hydroxide with a halogenated hydrocarbon having an unsaturated group is preferable.
x is preferably 3 to 6, more preferably 3 to 5, and even more preferably 3 or 4.

Compounds having three or more active hydrogen-containing groups in one molecule include trimethylolpropane, glycerin, butanetriol, pentantriol, hexanetriol, trimethylolethane, benzenetriol, pentaerythritol, sorbitol, and dipentaerythritol. It can be exemplified. Trimethylolpropane, glycerin, pentaerythritol, and sorbitol are preferable because they are easily available.

As a method for converting an active hydrogen-containing group into a group having an unsaturated group, a conventionally known method can be used, and examples thereof include the method proposed in Tokusho 60-231625.

When the active hydrogen-containing group is converted into a group having an unsaturated group, a mixture of compounds in which 1 to x active hydrogen-containing groups are converted into a group having an unsaturated group is obtained. Purification of this mixture by distillation gives compound a in which x-1 active hydrogen-containing groups are converted into groups having unsaturated groups.

(Method for producing polymer (D) from polymer (B))
The active hydrogen-containing group at the other terminal group of the polymer (B) is reacted with the polyisocyanate to obtain the polymer (C).

The polymer (C) is obtained by reacting the active hydrogen-containing group at the other terminal group of the polymer (B) with the active hydrogen-containing group at the terminal group of the polyooxyalkylene polymer (F) described later with the polyisocyanate. May be obtained.
The polymer (F) is composed of a polyoxyalkylene chain formed by a ring-opening addition polymerization addition reaction of a cyclic ether and a terminal group containing an oxygen atom at the end of the polyoxyalkylene chain, and the terminal group is active hydrogen. It is an oxyalkylene polymer having a contained group.

The average number of active hydrogen-containing groups per terminal group of the polymer (F) is preferably 1 to 2 and more preferably 1 from the viewpoint of the viscosity of the polymer to be synthesized.
The number of terminal groups in one molecule of the polymer (F) is preferably 2 to 6, more preferably 2 to 3.

The Mn of the polymer (F) is preferably 2,200 to 100,000, more preferably 2,500 to 50,000, and even more preferably 3,000 to 30,000.
The molecular weight distribution of the polymer (F) is preferably 2.0 or less, more preferably 1.5 or less, further preferably 1.4 or less, and particularly preferably 1.2 or less.
The viscosity of the polymer (F) at 25 ° C. is preferably 0.05 to 100,000 Pa · s, more preferably 0.1 to 10,000 Pa · s, still more preferably 0.3 to 100 Pa · s.

The polymer (F) is obtained by subjecting a cyclic ether to a ring-opening addition polymerization reaction with an initiator compound having an active hydrogen-containing group in the molecule.

Initiator compounds include water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, and low molecular weight poly. Examples thereof include oxypropylene glycol, glycerin, trimethylolpropane, trimethylolethane, low molecular weight polyoxypropylene triol, pentaerythritol, sorbitol, and sucrose.

The conditions of the cyclic ether and the ring-opening addition polymerization reaction are the same as those described in the above-mentioned method for producing the polymer (B).

Examples of the polyisocyanate include polyisocyanates obtained by adding s isocyanate groups to the above-mentioned ^R20 .

Examples of such a polyisocyanate include the polyisocyanate described in R20, hexamethylene diisocyanate (HDI), diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexamethylene diisocyanate ( ^H12MDI ). , Xylylene diisocyanate (XDI), dimethylcyclohexane diisocyanate, trizine diisocyanate, naphthalene diisocyanate, pentamethylene diisocyanate, paraphenylenedi isocyanate, lysine diisocyanate, tetramethylximethylene diisocyanate, triphenylmethane triisocyanate, triisocyanate triphenylthiophosphate, dimerate diisocyanate. , Norbornen diisocyanate is preferable, hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexamethylene diisocyanate are more preferable, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate are further preferable.

A catalyst may be used for the reaction, and it can be appropriately selected depending on the polyisocyanate used. Examples of catalysts include organic tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and tin 2-ethylhexanoate (tin octylate), iron compounds such as iron acetylacetonate and iron chloride, and octylic acid. Examples thereof include lead compounds such as lead, bismuth compounds such as bismuth octylate, tertiary amine-based catalysts such as triethylamine and triethylenediamine, and preferred examples are organic tin compounds, lead octylate and bismuth octylate.

The reaction temperature and reaction time can be appropriately selected depending on the polyisocyanate used, but the reaction temperature may be 0 to 130 ° C., preferably 20 to 90 ° C., and the reaction time is preferably 0.5 to 24 hours.

The unsaturated group at the terminal group of the polymer (C) is reacted with a silylating agent having a reactive silicon group represented by the above formula 1 to obtain the polymer (D).
As the silylating agent, a compound having both a group capable of reacting with an unsaturated group (for example, a sulfanyl group) and the above-mentioned reactive silicon group, a hydrosilane compound (for example, HSiX _a R _3-a , but X) , R and a are the same as those in the above formula 1). Specifically, for example, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris (2-propenyloxy) silane, triacetoxysilane, methyldimethoxysilane, methyldiethoxysilane, ethyldimethoxysilane, methyldiisopropoxy. Examples thereof include silane, (α-chloromethyl) dimethoxysilane, and (α-chloromethyl) diethoxysilane. Trimethoxysilane, triethoxysilane, methyldimethoxysilane, and methyldiethoxysilane are preferable, and methyldimethoxysilane or trimethoxysilane is more preferable, from the viewpoint of high activity and good curability.

As a method for reacting the unsaturated group at the terminal group of the polymer (C) with the silylating agent, a conventionally known method can be used. , JP-A-61-197631, JP-A-3-72527, JP-A-8-231707, JP-A-2011-178955, US Pat. No. 3,632,557, and US Pat. No. 4,960,844. ..
The silylation rate is preferably more than 50 mol% and 100 mol% or less, more preferably 55 to 98 mol%, still more preferably 60 to 97 mol%.

[Cursable composition]
The curable composition of the present embodiment contains the polymer (A) and a curing catalyst. The polymer (A) preferably contains the polymer (D). The curable composition is obtained by adding, if necessary, components to the polymer (A) and mixing them.
When the curable composition contains the polymer (D), the content ratio of the polymer (D) to the total mass of the curable composition is preferably 5 to 70% by mass, more preferably 8 to 60% by mass, and 10%. It is more preferably ~ 50% by mass. When the content ratio of the polymer (D) is within the above range, the strength and elongation of the cured product are more excellent.
The curable composition of the present embodiment may contain a polymer (B) and a polymer (C). When the curable composition contains one or more of the polymer (B) and the polymer (C), the total content ratio of the polymer (B) and the polymer (C) to the total mass of the curable composition is It may be 2 to 50% by mass, or 5 to 40% by mass.
Examples of the curing catalyst contained in the curable composition of the present embodiment include the curing catalysts described in other components described later. The content of the curing catalyst is preferably 0.01 to 20.0 parts by mass, more preferably 0.1 to 10.0 parts by mass with respect to 100 parts by mass of the total of the polymer (D) and the polymer (C). preferable. When it is 0.01 part by mass or more, the curing reaction easily proceeds sufficiently, and when it is 20.0 parts by mass or less, the strength of the cured product is more excellent.

The stress (M50) at 50% elongation, measured by the tensile test shown in the examples below of the cured product obtained from the curable composition of the present embodiment, tends to exceed 0.75 N / mm ² . Furthermore, it tends to be 0.8 N / mm ² or more. If it exceeds 0.75 N / mm ² , good strength can be obtained and it is suitable for adhesive use.

The maximum point cohesive force (Tmax) measured by the tensile test shown in Examples described later of the cured product obtained from the curable composition of the present embodiment is likely to be 1.25 N / mm ² or more, and further 1 It tends to be .30 N / mm ² or more. If it is 1.25 N / mm ² or more, good strength can be obtained and it is suitable for adhesive use.

The maximum point elongation measured by the tensile test shown in the examples below of the cured product obtained from the curable composition of the present embodiment is likely to be 60% or more, further 100% or more, and particularly 150%. It is easy to become the above. If it is 60% or more, good elongation can be obtained, which is suitable for adhesive use.

[Other ingredients]
The curable composition is an oxyalkylene polymer having a reactive silicon group represented by the above formula 1, which does not correspond to the polymer (D), the polymer (B), or the polymer (C), and is represented by the above formula 1. It contains a polymer other than the oxyalkylene polymer having a reactive silicon group, a polymer (B) and a polymer (C) which does not have a reactive silicon group represented by the above formula 1. You may be. Examples of the polymer other than the oxyalkylene polymer include vinyl-based polymers such as acrylic acid-based polymers and methacrylic acid-based polymers, saturated hydrocarbon-based polymers, polyester-based polymers, polysulfide-based polymers, and polyamide-based polymers. , Polycarbonate-based polymer, diallyl phthalate-based polymer, and the like.
The curable composition may contain other components. Examples of other components include additives depending on the use of the curable composition, such as fillers, plasticizers, chicosis-imparting agents, antioxidants, ultraviolet absorbers, light stabilizers, dehydrating agents, and adhesive-imparting agents. Examples thereof include agents, amine compounds, oxygen curable compounds, and photocurable compounds.
The curing catalyst and other components are described in International Publication No. 2013/180203, International Publication No. 2014/192842, International Publication No. 2016/002907, JP-A-2014-88481, JP-A-2015-10162, JP-A-2015. Conventionally known substances described in JP-A-2015-105293A, JP-A-2017-039728, JP-A-2017-214541 and the like can be used in combination without limitation.
Two or more kinds of each component may be used in combination.

The curable composition may be a one-component type in which all the compounding components are premixed, sealed and stored, and cured by the humidity in the air after construction, and the main composition containing at least a component having a reactive silicon group and at least A two-component type may be used in which the curing agent composition containing the curing catalyst is stored separately and the curing agent composition and the main agent composition are mixed before use. A one-component curable composition is preferred because it is easy to install.

The one-component curable composition preferably does not contain water. It is preferable to dehydrate and dry the compounding component containing water in advance, or to dehydrate by reducing the pressure during compounding and kneading.
In the two-component curable composition, the curing agent composition may contain water. Although the main ingredient composition is difficult to gel even if it contains a small amount of water, it is preferable to dehydrate and dry the compounding components in advance from the viewpoint of storage stability.
In order to improve storage stability, a dehydrating agent may be added to the one-component curable composition or the two-component main composition.

The curable composition is used as a sealing material (for example, an elastic sealing material for construction, a sealing material for double glazing, a sealing material for rust prevention / waterproofing at the end of glass, a sealing material for the back surface of a solar cell, and a sealing material for buildings. Materials, sealing materials for ships, sealing materials for automobiles, sealing materials for roads), electrical insulating materials (insulating coating materials for electric wires / cables), adhesives, and potting materials are suitable.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following description.

<Measurement method / evaluation method>
[Molecular weight equivalent to hydroxyl group of polymer]
The molecular weight (hereinafter referred to as "hydroxyl-equivalent molecular weight") of an oxyalkylene polymer (polymer (B1) and polymer (B2)) obtained by polymerizing an alkylene oxide with an initiator having a hydroxyl group is JIS K 1557 (2007). ), The hydroxyl value was calculated based on the formula "56100 / (polymer hydroxyl value) x number of active hydrogens of the initiator".

[Mn and molecular weight distribution]
Mw, Mn and Mw / Mn were determined using HLC-8220GPC (product name of Tosoh Corporation).

[Measurement of average number of unsaturated groups, reactive silicon groups and hydroxyl groups contained in the polymer]
The number of reactive silicon groups contained in the polymer was measured by ¹ H-NMR internal standard method.
The number of unsaturated groups contained in the polymer was measured by iodine value titration according to JIS K0070: 1992.
The number of hydroxyl groups contained in the polymer was measured by a titration method using a sodium hydroxide (NaOH) solution (based on JIS K1557: 2007) after esterifying the hydroxyl groups with a pyridine solution of phthalic anhydride.

[Calculation of urethane bond content with respect to the total amount of polymer]
From the formula A and the formula B, the content of urethane bond with respect to the total amount of the polymer was calculated.

[Tensile test]
The curable composition to be measured was filled in a mold having a thickness of 2 mm, cured at a temperature of 23 ° C. and a humidity of 50% for 3 days, and further cured at a temperature of 50 ° C. and a humidity of 65 ° C. for 4 days. The obtained cured product was punched out with a dumbbell mold to obtain a test piece. A tensile test was performed on this test piece at a tensile speed of 500 mm / min, and the stress (M50, unit: N / mm ² ), maximum point cohesive force (Tmax, unit: N / mm ² ), and maximum point when stretched by 50%. The tensile properties of elongation (unit:%) were measured.

[Production Example 1: Production of compound (a1)]
A flask equipped with a stirrer, a reflux condenser, a thermometer, and two dropping funnels was charged with 1 mol equivalent of trimethylolpropane and heated to 90 ° C. under a nitrogen stream. While stirring at 90 ° C., a 40 mass% sodium hydroxide aqueous solution was simultaneously added dropwise to trimethylolpropane in an equivalent amount of 2 mol and allyl chloride in an equivalent amount of 2 mol to trimethylolpropane using separate dropping funnels. The aqueous sodium hydroxide solution was added dropwise over 2 hours, and the allyl chloride solution was added dropwise over 3 hours. After completion of the reaction, water was added to dissolve the precipitated sodium chloride, and the mixture was allowed to cool. When the organic layer of the solution after the reaction of the two layers consisting of the organic layer and the aqueous layer was separated and analyzed by gas chromatography, it has three allyl groups in one molecule represented by the following formula 11. , A compound having no active hydrogen-containing group, a compound having two allyl groups in one molecule represented by the following formula 12 and having one active hydrogen-containing group, and one represented by the following formula 13. A compound having one allyl group in the molecule and two active hydrogen-containing groups was confirmed.

The compound represented by the formula 11 with respect to the total peak area of the compound represented by the formula 11, the compound represented by the formula 12, and the compound represented by the formula 13 in the gas chromatography in the organic layer. The ratio was 5%, the ratio of the compound represented by the formula 12 was 88%, and the ratio of the compound represented by the formula 13 was 7%.

When the organic layer was precision distilled, the ratio of the peak area derived from the compound represented by the formula 12 to the total peak area of gas chromatography in the obtained purified liquid was 98%.

[Production Example 2: Production of compound (a2)]
A flask equipped with a stirrer, a reflux condenser, a thermometer, and two dropping funnels was charged with 1 mol equivalent of pentaerythritol and heated to 90 ° C. under a nitrogen stream. While stirring at 90 ° C., a 40 mass% sodium hydroxide aqueous solution was simultaneously added dropwise to pentaerythritol in an equivalent amount of 3 mol and allyl chloride in an equivalent amount of 3 mol to pentaerythritol using separate dropping funnels. The aqueous sodium hydroxide solution was added dropwise over 2 hours, and the allyl chloride solution was added dropwise over 3 hours. After completion of the reaction, water was added to dissolve the precipitated sodium chloride, and the mixture was allowed to cool. When the organic layer of the solution after the reaction of the two layers consisting of the organic layer and the aqueous layer was separated and analyzed by gas chromatography, it has four allyl groups in one molecule represented by the following formula 14. , A compound having no active hydrogen-containing group, a compound having three allyl groups in one molecule represented by the following formula 15, and one having one active hydrogen-containing group, and one represented by the following formula 16. A compound having two allyl groups in the molecule and two active hydrogen-containing groups was confirmed.

The compound represented by the formula 14 with respect to the total peak area of the compound represented by the formula 14, the compound represented by the formula 15 and the compound represented by the formula 16 in the gas chromatography in the organic layer. The ratio was 8%, the ratio of the compound represented by the formula 15 was 82%, and the ratio of the compound represented by the formula 16 was 10%.

When the organic layer was precision distilled, the ratio of the peak area derived from the compound represented by the formula 15 to the total peak area of gas chromatography in the obtained purified liquid was 98%.

[Production Example 3: Production of Polymer (B1)]
A zinc hexacyanocobaltate complex in which the ligand is t-butyl alcohol, using a compound having two allyl groups in one molecule represented by the above formula 12 and having one active hydrogen-containing group as an initiator. Hereinafter, a propylene oxide is polymerized using a "TBA-DMC catalyst") as a catalyst, and a component derived from the initiator (B1-1) and a component derived from water contained in the propylene oxide (hereinafter referred to as "TBA-DMC catalyst") are used. A polymer (B1) containing B1-2) was obtained. The component (B1-1) has 2.0 unsaturated groups and 0 hydroxyl groups in one terminal group, and has 0 unsaturated groups and 1.0 hydroxyl group in the other terminal group. , The number of hydroxyl groups and the number of unsaturated groups in the polymer (B1) obtained by the above measurement method are based on the premise that the component (B1-2) has 2.0 hydroxyl groups in one molecule. The components (B1-1) and the component (B1-2) contained in the polymer (B1) were distributed to the component (B1-1) and the component (B1-2) according to the ratio of the peak area of GPC. As a result, the average number of unsaturated groups in one molecule of the component (B1-1) is 2.0, and the average number of hydroxyl groups is 1.0, indicating that the polymer (B) of the present invention is used. confirmed. Table 1 shows the hydroxyl group-equivalent molecular weight obtained by the above method from the Mn of the component (B1-1) and the component (B1-2), the peak ratio of GPC, and the hydroxyl value of the polymer (B1) (hereinafter, similarly). show).

[Production Example 4: Polymer (B2)]
A compound having two allyl groups in one molecule represented by the above formula 12 and having one active hydrogen-containing group was used as an initiator to polymerize propylene oxide using a TBA-DMC catalyst. A polymer (B2) containing an initiator-derived component (B2-1) and a water-derived component (B2-2) contained in propylene oxide was obtained. The component (B2-1) has 2.0 unsaturated groups and 0 hydroxyl groups in one terminal group, and has 0 unsaturated groups and 1.0 hydroxyl group in the other terminal group. , The number of hydroxyl groups and the number of unsaturated groups in the polymer (B2) obtained by the above measurement method are based on the premise that the component (B2-2) has 2.0 hydroxyl groups in one molecule. The components (B2-1) and the component (B2-2) contained in the polymer (B2) were distributed to the component (B2-1) and the component (B2-2) according to the ratio of the peak area of GPC. As a result, the average number of unsaturated groups in one molecule of the component (B2-1) is 2.0, and the average number of hydroxyl groups is 1.0, indicating that the polymer (B) of the present invention is used. confirmed.

[Production Example 5: Production of Polymer (B3)]
A compound having three allyl groups in one molecule represented by the formula 15 and having one active hydrogen-containing group was used as an initiator to polymerize propylene oxide using a TBA-DMC catalyst. A polymer (B3) containing an initiator-derived component (B3-1) and a water-derived component (B3-2) contained in propylene oxide was obtained. The component (B3-1) has 3.0 unsaturated groups and 0 hydroxyl groups in one terminal group, and has 0 unsaturated groups and 1.0 hydroxyl group in the other terminal group. , The number of hydroxyl groups and the number of unsaturated groups in the polymer (B3) obtained by the above measurement method are based on the premise that the component (B3-2) has 2.0 hydroxyl groups in one molecule. The components (B3-1) and the component (B3-2) contained in the polymer (B3) were distributed to the component (B3-1) and the component (B3-2) according to the ratio of the peak area of GPC. As a result, the average number of unsaturated groups in one molecule of the component (B3-1) is 3.0, and the average number of hydroxyl groups is 1.0, indicating that the polymer (B) of the present invention is used. confirmed.

[Production Example 6: Production of Polymer (D1)]
The polymer (B1) obtained in Production Example 3 was dehydrated under reduced pressure. Then, tin octylate (II) (Nikka octix tin, product name of Nihon Kagaku Sangyo Co., Ltd.) is added, and hexamethylene diisocyanate having an index of 100% with respect to the hydroxyl group of the polymer (B1) (hereinafter referred to as "HDI"). ) Was added at room temperature and heated at 85 ° C. for 2 hours. After confirming that there is no residual HDI in the reaction solution by infrared spectroscopy analysis (hereinafter referred to as "IR analysis"), 1% by mass of methanol is added to the total amount of the reaction solution, and the mixture is stirred for 0.5 hours. After that, methanol was removed by degassing under reduced pressure. The reaction solution was analyzed by GPC to confirm that the molecular weight was increased, and it was confirmed that the coupling was surely progressing.
Next, 2% by mass of water was added to the total amount of the obtained reaction solution, the mixture was stirred at 85 ° C. for 0.5 hour, and then water was removed by degassing under reduced pressure. In the presence of the platinum divinyl disiloxane complex, 0.80 mol equivalent of dimethoxymethylsilane was added as a silylating agent to the unsaturated group of the polymer contained in the reaction solution, and the mixture was reacted at 85 ° C. for 3 hours. , The unreacted dimethoxymethylsilane is removed under reduced pressure, and the component (D1-1) derived from the component produced by the coupling reaction of the two molecules of the component (B1-1), and the component (B1-). A polymer (D1) containing a component (D1-2) derived from a component produced by a coupling reaction between two molecules of 1) and one molecule of the above component (B1-2) was obtained. The component (D1-1) and the component (D1-2) have two terminal groups, 1.6 reactive silicon groups and 0.4 unsaturated groups per terminal group. The polymer (D1) contains the number of reactive silicon groups, the number of unsaturated groups, and the number of hydroxyl groups in the polymer (D1) obtained by the above measurement method on the premise that it has 0 hydroxyl groups. The components (D1-1) and (D1-2) were distributed to the components (D1-1) and (D1-2) according to the ratio of the peak areas of GPCs of the components (D1-1) and (D1-2). As a result, both the component (D1-1) and the component (D1-2) have an average number of reactive silicon groups of 3.2 in one molecule and an average number of unsaturated groups of 0.8. It was confirmed that the polymer (D) of the present invention had an average number of hydroxyl groups of 0.
Component (D1-1), Mn of component (D1-2), peak ratio of GPC, number of reactive silicon groups in one molecule, and Mn, Mw / Mn of polymer (D1), concentration of reactive silicon groups, And the urethane bond content is shown in Table 2 (hereinafter, similarly shown).

[Production Example 7: Production of Polymer (D2)]
The polymer (B2) obtained in Production Example 4 was dehydrated under reduced pressure. Then, tin octylate (II) (Nikka octix tin, product name of Nihon Kagaku Sangyo Co., Ltd.) was added, HDI having an index of 100% was added to the hydroxyl group of the polymer (B2) at room temperature, and 2 at 85 ° C. Heated for hours. After confirming that there was no residual HDI in the reaction solution by IR analysis, 1% by mass of methanol was added to the total amount of the reaction solution, the mixture was stirred for 0.5 hours, and then methanol was removed by degassing under reduced pressure. The reaction solution was analyzed by GPC to confirm that the molecular weight was increased, and it was confirmed that the coupling was surely progressing. (Hereinafter, in Production Examples 8 to 10, the progress of coupling was confirmed by the same method).
Next, 2% by mass of water was added to the total amount of the obtained reaction solution, the mixture was stirred at 85 ° C. for 0.5 hour, and then water was removed by degassing under reduced pressure. In the presence of the platinum divinyl disiloxane complex, 0.80 mol equivalent of dimethoxymethylsilane was added as a silylating agent to the unsaturated group of the polymer contained in the reaction solution, and the mixture was reacted at 85 ° C. for 3 hours. , The unreacted dimethoxymethylsilane is removed under reduced pressure, and the component (D2-1) derived from the component produced by the coupling reaction of the two molecules of the component (B2-1), and the component (B2-). A polymer (D2) containing a component (D2-2) derived from a component produced by a coupling reaction between two molecules of 1) and one molecule of the above component (B2-2) was obtained. The component (D2-1) and the component (D2-2) have two terminal groups, 1.6 reactive silicon groups and 0.4 unsaturated groups per terminal group. The polymer (D2) contains the number of reactive silicon groups, the number of unsaturated groups, and the number of hydroxyl groups in the polymer (D2) obtained by the above measurement method on the premise that it has 0 hydroxyl groups. The components (D2-1) and the component (D2-2) were allocated to the component (D2-1) and the component (D2-2) according to the ratio of the peak area of the GPC. As a result, both the component (D2-1) and the component (D2-2) have an average number of reactive silicon groups of 3.2 in one molecule and an average number of unsaturated groups of 0.8. It was confirmed that the polymer (D) of the present invention had an average number of hydroxyl groups of 0.

[Production Example 8: Production of Polymer (D3)]
The polymer (B2) obtained in Production Example 4 was dehydrated under reduced pressure, and diphenylmethane diisocyanate (hereinafter referred to as “MDI”) having an index of 100% was added to the hydroxyl group of the polymer (B2) at 85 ° C. to 85. It was heated at ° C. for 20 hours. After confirming that there was no residual MDI in the reaction solution by IR analysis, 1% by mass of methanol was added to the total amount of the reaction solution, the mixture was stirred for 0.5 hours, and then methanol was removed by degassing under reduced pressure. The reaction solution was analyzed by GPC to confirm the progress of coupling.
Next, in the presence of the platinum divinyl disiloxane complex, 0.80 mol equivalent of dimethoxymethylsilane was added as a silylating agent to the unsaturated group of the polymer contained in the reaction solution, and the reaction was carried out at 85 ° C. for 3 hours. Then, the unreacted dimethoxymethylsilane is removed under reduced pressure, and the component (D3-1) derived from the component produced by the coupling reaction of the two molecules of the component (B2-1) and the component. A polymer (D3) containing a component (D3-2) derived from a component produced by a coupling reaction between two molecules of (B2-1) and one molecule of the above component (B2-2) was obtained. The component (D3-1) and the component (D3-2) have two terminal groups, 1.6 reactive silicon groups and 0.4 unsaturated groups per terminal group. The polymer (D3) contains the number of reactive silicon groups, the number of unsaturated groups, and the number of hydroxyl groups in the polymer (D3) obtained by the above measurement method on the premise that it has 0 hydroxyl groups. The components (D3-1) and the component (D3-2) were allocated to the component (D3-1) and the component (D3-2) according to the ratio of the peak area of the GPC of the component (D3-1). As a result, both the component (D3-1) and the component (D3-2) have an average number of reactive silicon groups of 3.2 in one molecule and an average number of unsaturated groups of 0.8. It was confirmed that the polymer (D) of the present invention had an average number of hydroxyl groups of 0.

[Production Example 9: Production of Polymer (D4)]
The polymer (B2) obtained in Production Example 4 was dehydrated under reduced pressure. Then, tin octylate (II) (Nikka octix tin, product name of Nihon Kagaku Sangyo Co., Ltd.) was added, and isophorone diisocyanate having an index of 100% with respect to the hydroxyl group of the polymer (B2) (hereinafter referred to as "IPDI"). Was added at room temperature and heated at 85 ° C. for 2 hours. After confirming that there was no residual IPDI in the reaction solution by IR analysis, 1% by mass of methanol was added to the total amount of the reaction solution, the mixture was stirred for 0.5 hours, and then methanol was removed by degassing under reduced pressure. The reaction solution was analyzed by GPC to confirm the progress of coupling.
Next, 2% by mass of water was added to the total amount of the obtained reaction solution, the mixture was stirred at 85 ° C. for 0.5 hour, and then water was removed by degassing under reduced pressure. In the presence of the platinum divinyl disiloxane complex, 0.80 mol equivalent of dimethoxymethylsilane was added as a silylating agent to the unsaturated group of the polymer contained in the reaction solution, and the mixture was reacted at 85 ° C. for 3 hours. , The unreacted dimethoxymethylsilane is removed under reduced pressure, and the component (D4-1) derived from the component produced by the coupling reaction of the two molecules of the component (B2-1), and the component (B2-). A polymer (D4) containing a component (D4-2) derived from a component produced by a coupling reaction between two molecules of 1) and one molecule of the above component (B2-2) was obtained. The component (D4-1) and the component (D4-2) have two terminal groups, 1.6 reactive silicon groups and 0.4 unsaturated groups per terminal group. The polymer (D4) contains the number of reactive silicon groups, the number of unsaturated groups, and the number of hydroxyl groups in the polymer (D4) obtained by the above measurement method on the premise that it has 0 hydroxyl groups. The components (D4-1) and (D4-2) were allocated to the component (D4-1) and the component (D4-2) according to the ratio of the peak area of GPC. As a result, both the component (D4-1) and the component (D4-2) have an average number of reactive silicon groups of 3.2 in one molecule and an average number of unsaturated groups of 0.8. It was confirmed that the polymer (D) of the present invention had an average number of hydroxyl groups of 0.

[Production Example 10: Production of Polymer (D5)]
The polymer (B2) obtained in Production Example 4 was dehydrated under reduced pressure. Then, tin octylate (II) (Nikka octix tin, product name of Nihon Kagaku Sangyo Co., Ltd.) is added, and the index is 100% with respect to the hydroxyl group of the polymer (B2), which is referred to as "H12MDI". ) Was added at room temperature and heated at 85 ° C. for 2 hours. After confirming that there was no residual H12MDI in the reaction solution by IR analysis, 1% by mass of methanol was added to the total amount of the reaction solution, the mixture was stirred for 0.5 hours, and then methanol was removed by degassing under reduced pressure. The reaction solution was analyzed by GPC to confirm the progress of coupling.
Next, 2% by mass of water was added to the total amount of the obtained reaction solution, the mixture was stirred at 85 ° C. for 0.5 hour, and then water was removed by degassing under reduced pressure. In the presence of the platinum divinyl disiloxane complex, 0.80 mol equivalent of dimethoxymethylsilane was added as a silylating agent to the unsaturated group of the polymer contained in the reaction solution, and the mixture was reacted at 85 ° C. for 3 hours. , The unreacted dimethoxymethylsilane is removed under reduced pressure, and the component (D5-1) derived from the component produced by the coupling reaction of the two molecules of the component (B2-1), and the component (B2-). A polymer (D5) containing a component (D5-2) derived from a component produced by a coupling reaction between two molecules of 1) and one molecule of the above component (B2-2) was obtained. The component (D5-1) and the component (D5-2) have two terminal groups, 1.6 reactive silicon groups and 0.4 unsaturated groups per terminal group. The polymer (D5) contains the number of reactive silicon groups, the number of unsaturated groups, and the number of hydroxyl groups in the polymer (D5) obtained by the above measurement method on the premise that it has 0 hydroxyl groups. The components (D5-1) and the component (D5-2) were allocated to the component (D5-1) and the component (D5-2) according to the ratio of the peak area of the GPC of the component (D5-1) and the component (D5-2). As a result, both the component (D5-1) and the component (D5-2) have an average number of reactive silicon groups of 3.2 in one molecule and an average number of unsaturated groups of 0.8. It was confirmed that the polymer (D) of the present invention had an average number of hydroxyl groups of 0.

[Production Example 11: Production of Polymer (D6)]
The polymer (B3) obtained in Production Example 5 was dehydrated under reduced pressure. Then, tin octylate (II) (Nikka octix tin, product name of Nihon Kagaku Sangyo Co., Ltd.) was added, HDI having an index of 100% was added to the hydroxyl group of the polymer (B3) at room temperature, and 2 at 85 ° C. Heated for hours. After confirming that there was no residual HDI in the reaction solution by IR analysis, 1% by mass of methanol was added to the total amount of the reaction solution, the mixture was stirred for 0.5 hours, and then methanol was removed by degassing under reduced pressure. The reaction solution was analyzed by GPC to confirm the progress of coupling.
Next, 2% by mass of water was added to the total amount of the obtained reaction solution, the mixture was stirred at 85 ° C. for 0.5 hour, and then water was removed by degassing under reduced pressure. In the presence of the platinum divinyl disiloxane complex, 0.80 mol equivalent of dimethoxymethylsilane was added as a silylating agent to the unsaturated group of the polymer contained in the reaction solution, and the mixture was reacted at 85 ° C. for 3 hours. , The unreacted dimethoxymethylsilane is removed under reduced pressure, and the component (D6-1) derived from the component produced by the coupling reaction of the two molecules of the component (B3-1) and the component (B3-). A polymer (D6) containing a component (D6-2) derived from a component produced by a coupling reaction between two molecules of 1) and one molecule of the above component (B3-2) was obtained. The component (D6-1) and the component (D6-2) have two terminal groups, 2.4 reactive silicon groups and 0.6 unsaturated groups per terminal group. The polymer (D6) contains the number of reactive silicon groups, the number of unsaturated groups, and the number of hydroxyl groups in the polymer (D6) obtained by the above measurement method on the premise that it has 0 hydroxyl groups. The components (D6-1) and the component (D6-2) were allocated to the component (D6-1) and the component (D6-2) according to the ratio of the peak area of GPC. As a result, both the component (D6-1) and the component (D6-2) have an average number of reactive silicon groups of 4.8 in one molecule and an average number of unsaturated groups of 1.2. It was confirmed that the polymer (D) of the present invention had an average number of hydroxyl groups of 0.

[Production Example 12: Production of Polymer (E1)]
Propylene oxide was polymerized using glycerin as an initiator and a TBA-DMC catalyst to obtain a precursor polymer having a molecular weight in terms of hydroxyl group of 10,000. Then, 1.15 mol equivalents of sodium methoxide in methanol was added to the hydroxyl group of the precursor polymer to alcorate the precursor polymer. Next, methanol was distilled off by heating and reducing pressure, and an excess amount of allyl chloride was added to the amount of hydroxyl groups of the precursor polymer to introduce an allyloxy group into the terminal group. Next, in the presence of platinum chloride hexahydrate, 0.65 molar equivalent of dimethoxymethylsilane was added as a silylating agent to the converted allyloxy group of the precursor polymer, and the reaction was carried out at 85 ° C. for 3 hours. Then, a linear oxypropylene polymer (E1) in which a reactive silicon group was introduced into the terminal group was obtained. The Mn of the polymer (E1) was 15,000, and the average number of reactive silicon groups per molecule was 2.0.

[Production Example 13: Production of Polymer (E2)]
An oxypropylene polymer having Mn of about 2,000, having two terminal groups and having a hydroxyl group as the terminal group is used as an initiator, and a TBA-DMC catalyst is used as a catalyst to polymerize propylene oxide, which is converted into a hydroxyl group. A precursor polymer having a molecular weight of 12,000 was obtained. Then, 1.0 mol equivalent of a methanol solution of sodium methoxide was added to the hydroxyl group of the precursor polymer to alcorate the precursor polymer. Next, methanol was distilled off by heating and reducing pressure, 1.0 molar equivalent of allyl glycidyl ether was added to the amount of hydroxyl groups of the precursor polymer, and the reaction was carried out at 130 ° C. for 2 hours, followed by 0.28 molar equivalents. Sodium methoxide in methanol was added to remove methanol, 1.79 mol equivalent of allyl chloride was added, and after the reaction, unreacted allyl chloride was removed under reduced pressure, and an allyl group was introduced into the terminal group. The oxypropylene polymer (polymer Q1) was obtained. The average number of allyl groups introduced into one terminal group of the polymer Q1 was 2.0. Next, 0.85 mol equivalent of dimethoxymethylsilane was added as a silylating agent to the allyl group of the polymer Q1 in the presence of the platinum divinyldisiloxane complex, and the mixture was reacted at 85 ° C. for 3 hours before being reacted. The dimethoxymethylsilane of the reaction was removed under reduced pressure to obtain a polymer (polymer (E2)) in which more than 1.0 dimethoxymethylsilyl groups were introduced into one terminal group on average as reactive silicon groups. rice field.

<Other ingredients>
The additives listed in Table 3 are as follows.
Whiten SB: Heavy calcium carbonate, product name of Shiraishi Kogyo Co., Ltd.
CCR: White glossy CCR Colloidal calcium carbonate, product name of Shiraishi Kogyo Co., Ltd.
R-820: Titanium oxide, product name of Ishihara Sangyo Co., Ltd.
Balloon 81GCA: Organic balloon, product name of Matsumoto Oil & Fats Co., Ltd.
Printex30: Carbon Black, Orion Engineered Carbons Product name.
CML35: Calcium oxide, product name of Shiraishi Kogyo Co., Ltd.
DINP: Diisononyl phthalate.
UP-1171: ARUFON UP-1711, Mw3,000 acrylic polymer, Toagosei product name.
S4012: Preminol S4012, a high molecular weight polyol having two hydroxyl groups per molecule and an Mn of 10,000 per hydroxyl group, a product name of AGC Inc.
DINCH: 1,2-Cyclohexanedicarboxylic acid-diisononyl ester.
Polymer Q: Polymer Q synthesized by the method described below.
N-12D: n-dodecane, purity 98.0%, Cactus normal paraffin N-12D, JXTG Energy product.
Sunsocizer EPS: 4,5-epoxycyclohexane-1,2-dicarboxylic acid-di-2-ethylhexyl, product name of Shin Nihon Rika Co., Ltd.
Disparon # 6500: Hydrogenated castor oil-based thixotropic agent, Kusumoto Kaseisha product name.
IRGANOX1135: Hindered phenolic antioxidant, BASF product name.
TINUVIN326: Benzotriazole-based UV absorber, product name of BASF.
TINUVIN765: A hindered amine-based light stabilizer containing a tertiary amine, a product name of BASF.
LA-63P: ADEKA STAB LA-63P, ADEKA product name.
KBM-1003: Vinyl trimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd.
KBM-403: 3-glycidyloxypropyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd.
KBM-603: 3- (2-aminoethylamino) propyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd.
Laurylamine: Reagent, manufactured by Junsei Chemical Co., Ltd.
Fermin CS: Coconut amine, Kao product name.
DEAPA: 3-diethylaminopropylamine, manufactured by Tokyo Chemical Industry Co., Ltd.
TMP-3TMS: Tritrimethylsilyl form of trimethylolpropane.
Tung oil: Air oxidative curable compound, manufactured by Kimura.
M-309: Aronix M-309, Toagosei product name.
DBTDL: Dibutyl phthalate, manufactured by Tokyo Chemical Industry Co., Ltd.
U-220H: Tin catalyst, product name of Nitto Kaseisha.
TC750: Titanium diisopropoxybis (ethylacetacetate), Organix TC750, Matsumoto Fine Chemical Co., Ltd. Product name.
Neodecanoic acid: manufactured by Strem Chemicals.
Catalyst composition: 4 parts by mass of a mixture of stannoct (stantic octylate, product name of Yoshitomi Pharmaceutical Co., Ltd.) and laurylamine (reagent, manufactured by Genuine Chemical Co., Ltd.) so as to have a mass ratio of 6: 1. Sizer DINP (diisononyl phthalate, product name of Shin Nihon Rika Co., Ltd.) 6 parts by mass, Whiten SB (heavy calcium carbonate, product name of Shiraishi Calcium Industry Co., Ltd.) 15 parts by mass and Glomax LL (baked kaolin, product name of Takehara Chemical Industry Co., Ltd.) ) A composition obtained by mixing 5 parts by mass.

(Synthesis of Polymer Q)
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 0.05 g of TBA-DMC at 120 ° C. until the pressure of the reaction system does not decrease, and each molecule has one hydroxyl group at the end of the polyoxypropylene chain. A precursor polymer (1') 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 under reduced pressure 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 methyldimethoxylan was added to the allyl group of the precursor polymer (2'), and 85 The reaction was carried out at ° C. for 3 hours to obtain a polymer Q having a reactive silyl group at one end of the polyoxypropylene chain. The Mn of the polymer Q was 7,000, and the average number of reactive silicon groups per molecule was 0.80.

<Manufacturing of curable composition>
Examples 1 to 6 are examples, and examples 7 and 8 are comparative examples.

(Examples 1 to 8)
A curable composition was produced by mixing the polymer (D) and the polymer (E) having the formulations shown in Table 4 (unit: parts by mass) and the additive 1 having the formulations shown in Table 3. The formulations shown in Table 3 are values (unit: parts by mass) with respect to 100 parts by mass of the polymer.
The cured product of the obtained curable composition was evaluated for M50, Tmax, and maximum point elongation by the above method. The results are shown in Table 4.

In Examples 1 to 6, the values of M50 and Tmax of the cured product were high, and the strength was excellent.

Even when the curable compositions were produced by changing the additives to the additives 2 to 16 in Table 3 in Examples 1 to 6, the values of M50 and Tmax of the cured product were high and the strength was excellent in each of the examples. Was there.

Claims (12)

A polymer having a reactive silicon group, an unsaturated group, a urethane bond and a polyoxyalkylene chain represented by the following formula 1, and the reactive silicon group and the unsaturated group on average per one terminal group. An oxyalkylene polymer (A) having a total of more than 1.0 and having a urethane bond in the main chain.
-SiX _a R _3-a formula 1
In the above formula 1, R is a monovalent organic group having 1 to 20 carbon atoms and represents an organic group other than a hydrolyzable group, X represents a hydroxyl group, a halogen atom, or a hydrolyzable group, and a is. It indicates an integer of 1 to 3, and when a is 1, R may be the same or different from each other, and when a is 2 or 3, X may be the same or different from each other. The main chain contains a residue obtained by removing an isocyanate group from a polyisocyanate, a polyoxyalkylene chain, and a urethane bond connecting the residue and the polyoxyalkylene chain, and the terminal group is the polyoxy. The oxyalkylene polymer (A) according to claim 1, which is a terminal group containing an oxygen atom closest to the molecular terminal of the oxyalkylene polymer (A) among the oxygen atoms of the alkylene chain. The oxyalkylene polymer (A) according to claim 1 or 2, wherein the number average molecular weight is 3,000 to 100,000. The oxyalkylene polymer (A) according to any one of claims 1 to 3, wherein the molecular weight distribution is 2.0 or less. The oxyalkylene polymer (A) according to any one of claims 1 to 4, which has an average of more than 1.0 reactive silicon groups per terminal group. A curable composition comprising the oxyalkylene polymer (A) according to any one of claims 1 to 5 and a curing catalyst. The active hydrogen-containing group at the other terminal group of the oxyalkylene polymer (B) below is reacted with a polyisocyanate having a molecular weight of 100 to 20,000 to obtain the oxyalkylene polymer (C) below, and then the oxy. The oxyalkylene polymer (A) according to claim 5, wherein the unsaturated group at the terminal group of the alkylene polymer (C) is reacted with the silylating agent having a reactive silicon group represented by the above formula 1. Production method.
Oxyalkylene polymer (B): A polymer having an unsaturated group, an active hydrogen-containing group and a polyoxyalkylene chain, and having an average of 1.0 or more unsaturated groups at one terminal group. An oxyalkylene polymer having an average of more than 0 and 1.0 or less active hydrogen-containing groups in the other terminal group.
Oxyalkylene polymer (C): A polymer having an unsaturated group and a polyoxyalkylene chain, which has an average of 1.0 or more unsaturated groups per terminal group. The oxyalkylene polymer (B) is an oxyalkylene polymer obtained by subjecting a cyclic ether to a ring-opening addition polymerization reaction with an initiator, and the initiator has two or more unsaturated groups in one molecule. The method for producing an oxyalkylene polymer (A) according to claim 7, which is a compound having one active hydrogen-containing group in one molecule. The oxyalkylene polymer according to claim 8, wherein the cyclic ether comprises at least one cyclic ether selected from the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide. A) Manufacturing method. The method for producing an oxyalkylene polymer (A) according to claim 8 or 9, wherein the initiator is a compound represented by the following formula 2.

In the above formula 2, R ¹ is an active hydrogen-containing group, R ² is a hydrogen atom or a methyl group, R ⁴ may contain an oxygen atom or a nitrogen atom, and an atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom. A divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, R ⁶ may contain an oxygen atom or a nitrogen atom, and an oxygen atom or an atom adjacent to the nitrogen atom is a carbon atom having 1 to 20 carbon atoms. A monovalent hydrocarbon group of 20, a hydrogen atom, or a group represented by -R ⁶² -CR ⁶¹ = CH ₂ , R ⁶¹ is a hydrogen atom or a methyl group, and R ⁶² is an oxygen atom or a nitrogen atom. It may be contained, and the atom adjacent to the oxygen atom or the nitrogen atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom, and a plurality of R ² and R ⁴ are the same or different from each other. Often, n is an integer from 0 to 10. The method for producing an oxyalkylene polymer (A) according to any one of claims 8 to 10, wherein the ring-opening addition polymerization reaction is carried out in the presence of a composite metal cyanation complex catalyst. The method for producing an oxyalkylene polymer (A) according to any one of claims 7 to 11, wherein the oxyalkylene polymer (C) has a number average molecular weight of 3,000 to 100,000.