JP2021059722A - Curable material, curable composition, cured product, method for producing polycarbonate polymer, and polycarbonate polymer - Google Patents

Abstract

To provide a curable material composed of a polycarbonate polymer which achieves improved elongation without causing decrease in the strength of a cured product.SOLUTION: A curable material is composed of a polycarbonate polymer that has, in one molecule, a reactive silicon group represented by -SiXaR13-a (R1 is a C1-20 monovalent organic group to denote an organic group that is not a hydrolyzable group, X is a hydroxy group or a hydrolyzable group, and a is an integer of 1-3), a carbonate group, and an alkylene oxide-based unit, and has a number average molecular weight of 4,000-50,000.SELECTED DRAWING: None

Description

The present invention relates to a curable material made of a polycarbonate polymer, a curable composition containing the curable material, a cured product of the curable composition, a method for producing a polycarbonate polymer, and a polycarbonate polymer.

The polymer having a reactive silicon group is cured by a hydrolysis reaction to form a flexible rubber-like cured product, and is used for applications such as a sealant and an adhesive. For the polymer having a reactive silicon group and other components in the curable composition in order to optimize the curability of the curable composition containing the polymer having a reactive silicon group and the physical characteristics of the cured product. It is under consideration.

As a polymer having a reactive silicon group, Patent Document 1 describes a polymer in which a reactive silicon group is linked to the end of a polyoxyalkylene chain derived from a polyoxyalkylene polyol via a urethane bond. ..

Japanese Unexamined Patent Publication No. 3-157424

In the use of adhesives and sealing materials, it is required to have excellent strength and elongation of the cured product. However, in general, there is a trade-off relationship between strength and elongation, and it is difficult to achieve both.
The present invention relates to a polycarbonate polymer having good strength and elongation of a cured product and a method for producing the same, a curable material made of the polycarbonate polymer, a curable composition containing the curable material, and the curable composition. Provide a cured product.

The present invention has the following aspects.
[1] A polycarbonate polymer having a unit based on a reactive silicon group, a carbonate group, and an alkylene oxide represented by the following formula 1 in one molecule and having a number average molecular weight of 4,000 to 50,000. Curable material consisting of.
−SiX _a R ¹ _3-a formula 1
In formula 1, R ¹ 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 or a hydrolyzable group, and a is 1-3. It indicates an integer, and when a is 1, R ¹ 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 curable material according to [1], wherein the unit based on alkylene oxide includes a unit based on propylene oxide.
[3] The curable material according to [1] or [2], wherein the number of carbonate groups per molecule of the polycarbonate polymer is 3.0 or more.
[4] Any of [1] to [3], wherein the carbonate group / alkylene oxide unit is 0.01 to 1, which represents the molar ratio of the content of the carbonate group to the content of the unit based on the alkylene oxide. Curable material.
[5] The curable material according to any one of [1] to [4], wherein the number of the reactive silicon groups present in the polycarbonate polymer is more than 0.5 on average per molecule.
[6] The curable material according to any one of [1] to [5], which has a molecular weight distribution of 1.0 to 3.0.
[7] A curable composition containing the curable material according to any one of [1] to [6] and a curing catalyst.
[8] A cured product of the curable composition of the above [7].
[9] The cured product of [8] for a sealing material.
[10] The cured product of [8] for adhesives.

[11] A precursor having two or more carbonate groups, a unit based on an alkylene oxide, and an active hydrogen-containing group capable of reacting with a silylating agent at the terminal, and having a number average molecular weight of 4,000 to 50,000. The polymer or a derivative in which a reactive end group capable of reacting with a silylating agent is introduced at the end of the precursor polymer, and the reactive silicon group represented by the following formula 1 and the active hydrogen-containing group or the above-mentioned active hydrogen-containing group or A method for producing a polycarbonate polymer, wherein the reactive end group is reacted with a silylating agent having a group capable of reacting with the reactive terminal group.
−SiX _a R ¹ _3-a formula 1
In formula 1, R ¹ 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 or a hydrolyzable group, and a is 1-3. It indicates an integer, and when a is 1, R ¹ 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.
[12] The method for producing a polycarbonate polymer according to [11], wherein the precursor polymer is obtained by addition polymerization of an alkylene oxide to a hydroxyl group of a polycarbonate polyol.
[13] The method for producing a polycarbonate polymer according to [11], wherein the precursor polymer is obtained by addition polymerization of an alkylene oxide and carbon dioxide to a hydroxyl group of a polycarbonate polyol.
[14] The polycarbonate polymer of [12] or [13], wherein the polycarbonate polyol is a polycarbonate diol obtained by polycondensing a diol compound represented by the following formula 2 and a carbonate compound represented by the following formula 3. Production method.
HO-R ^2- OH formula 2
In Formula 2, R ² represents a substituted or unsubstituted divalent hydrocarbon group having 3 to 20 carbon atoms.
R ^3- OC (O) -OR ⁴ formula 3
In formula 3, R ³ and R ⁴ are independently alkyl or phenyl groups having 1 to 20 carbon atoms, or R ³ and R ⁴ are bonded to each other to form a ring.
[15] The diol compound is 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1 , 10-Decandiol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, and isosorbide, which is one or more of the polycarbonate polymers of [14]. Production method.
[16] The method for producing a polycarbonate polymer according to [14] or [15], wherein the polycarbonate diol has a number average molecular weight of 250 to 10,000.
[17] The method for producing a polycarbonate polymer according to [11], wherein the precursor polymer is obtained by addition polymerization of an alkylene oxide and carbon dioxide to a polyol containing no carbonate group.
[18] A polycarbonate polymer having a unit based on a reactive silicon group, a carbonate group, and an alkylene oxide represented by the following formula 1 in one molecule and having a number average molecular weight of 4,000 to 50,000. ..
−SiX _a R ¹ _3-a formula 1
In formula 1, R ¹ 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 or a hydrolyzable group, and a is 1-3. It indicates an integer, and when a is 1, R ¹ 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.
[19] One molecule has a repeating unit based on a reactive silicon group represented by the following formula 10, two or more carbonate groups, and an alkylene oxide, and has a number average molecular weight of 4,000 to 50,000. There is a polycarbonate polymer.
−SiX ¹⁰ _a R ¹⁰ _3-a formula 10
In formula 10, R ¹⁰ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halo hydrocarbon group having 1 to 20 carbon atoms, and X ¹⁰ represents a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms. Shown, a represents an integer from 1 to 3, and when a is 1, R ¹⁰ may be the same or different from each other, and when a is 2 or 3, X ¹⁰ may be the same or different from each other.
[20] One molecule has one or more reactive silicon groups, two or more carbonate groups, and a repeating unit based on an alkylene oxide, and has a number average molecular weight of 4,000 to 50,000. , Polycarbonate polymer represented by the following formula 11.
X ¹⁰ _a R ¹⁰ _3-a Si-Q-[(OR ¹¹ ) _n (OR ^11- OC (O)) _m (OR ^2- OC (O)) _t ] ^{-OR 21-} O −Q−SiX ¹⁰ _a R ¹⁰ _3-a formula 11
In formula 11, X ¹⁰ represents a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and R ¹⁰ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halo hydrocarbon group having 1 to 20 carbon atoms. shows, Q is a divalent hydrocarbon group having a substituted or unsubstituted 1 to 6 carbon atoms, or -NHC (O) ^{-R 31} - ^{indicates, R 31} is 2 substituted or unsubstituted 1 to 6 carbon atoms It shows a valent hydrocarbon group, one of which is bonded to a silicon atom, R ¹¹ shows a substituted or unsubstituted divalent hydrocarbon group having 2 to 4 carbon atoms, and R ² and R ²¹ are respectively. Independently indicates a substituted or unsubstituted divalent hydrocarbon group having 3 to 20 carbon atoms, n is an integer of 1 to 900, t is an integer of 0 to 50, and m is an integer of 0 to 500. And n + t + m is an integer of 3 or more. a is an integer of 1 to 3, and when a is 1, R ¹⁰ may be the same or different from each other, and when a is 2 or 3, X ¹⁰ may be the same or different from each other.

The curable material of the present invention has good strength and elongation of a cured product obtained by curing the curable material.
The curable composition of the present invention can be obtained as a cured product having good strength and elongation.
The cured product of the present invention has good strength and elongation.
The polycarbonate polymer of the present invention has good strength and elongation of a cured product obtained by curing the polymer.

The definitions of the following terms in the specification and claims are as follows.
The "unit" constituting the polymer means an atomic group formed by polymerization of a monomer.
For the number average molecular weight (hereinafter referred to as "Mn") and the weight average molecular weight (hereinafter referred to as "Mw"), gel permeation chromatography (GPC) was used to obtain an oxyalkylene polymer having a known molecular weight in terms of hydroxyl group. It is an oxyalkylene polymer equivalent molecular weight measured by preparing a calibration line using the above. 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 "hydroxyl-equivalent molecular weight" is a hydroxyl value calculated based on JIS K 1557 (2007) in an oxyalkylene polymer containing a repeating unit based on an alkylene oxide monomer, and is defined as "56,100 × (in the molecule). The molecular weight is calculated by using the value obtained by applying the formula (number of hydroxyl groups) / (hydroxyl value).

The "precursor polymer" is a polymer before the introduction of a reactive silicon group, has a carbonate group and a unit based on an alkylene oxide (hereinafter, also referred to as an "alkylene oxide unit"), and has an active hydrogen at the terminal. It means a polymer having an containing group.
The “derivative of the precursor polymer” means a polymer in which a reactive end group is introduced into the end of the precursor polymer via a linking group. The reactive end group can react with the silylating agent described below.
The "reactive terminal group" means a terminal group that reacts with a silylating agent when a reactive silicon group is introduced into a precursor polymer or a derivative thereof. Examples of the reactive terminal group include an alkenyloxy group such as an allyloxy group and a hydroxyl group. The number of alkenyloxy groups present in the polymer is calculated by a method of measuring the unsaturated group concentration by titration analysis based on the principle of the method for measuring the raw material as defined in JIS K 0070 (1992). can do.
The "silylating agent" means a compound capable of reacting with an active hydrogen-containing group or the reactive terminal group to form a terminal group having a reactive silicon group.
By "non-reactive end group" is meant an end group that does not react with the silylating agent.

As used herein, the "silylation rate" of a polycarbonate polymer is the total number of reactive silicon groups, reactive end groups, and non-reactive end groups present in the polycarbonate polymer. It is a ratio of numbers. The value of the silylation rate can be measured by NMR analysis. When the reactive end group in the polycarbonate polymer is an active hydrogen-containing group, the number of reactive end groups is the number of active hydrogen. The total number of reactive silicon groups, reactive end groups, and non-reactive end groups is also referred to as the total number of end groups.
The number of total end groups in the polycarbonate polymer is the same as the total number of reactive and non-reactive end groups in the precursor polymer or its derivatives. For example, when a derivative in which an unsaturated group is introduced as a reactive end group is used in the precursor polymer, isomerization of the unsaturated group occurs when an unsaturated group (for example, an allyl group) is introduced into the precursor polymer. There may be non-reactive end groups produced (eg, 1-propenyl groups).

<Polycarbonate polymer>
The polycarbonate polymer of the present embodiment has a reactive silicon group represented by the following formula 1, a carbonate group, and an alkylene oxide unit in one molecule.

The reactive silicon group has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and can form a siloxane bond for cross-linking. The reaction to form a siloxane bond is promoted by a curing catalyst. A hydrolyzable group is a group that can react with water to form a silanol group. The reactive silicon group in the polymer A is represented by the following formula 1.
−SiX _a R ¹ _3-a formula 1

In the above formula 1, R ¹ represents a monovalent organic group having 1 to 20 carbon atoms. R ¹ does not contain hydrolyzable groups.
R ¹ is preferably at least one selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a halo hydrocarbon group and a triorganosyloxy group, and is preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms and carbon. At least one selected from the group consisting of monovalent halohydrocarbon groups having a number of 1 to 20 is more preferable, and from a monovalent hydrocarbon group having 1 to 3 carbon atoms and a halo hydrocarbon group having 1 to 3 carbon atoms. At least one selected from the group is particularly preferred.

R ¹ is preferably an alkyl group, a cycloalkyl group, an aryl group, a 1-chloroalkyl group or a triorganosyloxy group. A linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, a 1-chloroalkyl group, a trimethylsiloxy group, a triethylsiloxy group or a triphenylsiloxy group is more preferable. Alkyl groups of 1 to 3 or 1-chloroalkyl groups having 1 to 3 carbon atoms are particularly 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 from the viewpoint of a high curing rate of the cured product. A methyl group is particularly preferred because it is readily available.

In the above formula 1, X represents a hydroxyl group or a hydrolyzable group.
Examples of the hydrolyzable group include a halogen atom, 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. The number of carbon atoms of the alkyl group or alkenyl group that can be present in these groups is preferably 1 to 6, and particularly preferably 1 to 3.
An alkoxy group is preferable from the viewpoint of mild hydrolysis and easy handling, and an alkoxy group having 1 to 3 carbon atoms is more preferable. 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 property value of the cured product becomes better.

In the above formula 1, a represents an integer of 1 to 3. When a is 1, R ¹ may be the same or different from each other. When a is 2 or more, X may be the same 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 methyldimethoxysilyl group and a methyldiethoxysilyl group are preferable, and a dimethoxymethylsilyl group and a trimethoxysilyl group are more preferable.
As the reactive silicon group represented by the formula 1, the group represented by the following formula 10 is preferable.
−SiX ¹⁰ _a R ¹⁰ _3-a formula 10
In formula 10, R ¹⁰ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halo hydrocarbon group having 1 to 20 carbon atoms, and X ¹⁰ represents a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms. Shown, a represents an integer from 1 to 3, and when a is 1, R ¹⁰ may be the same or different from each other, and when a is 2 or 3, X ¹⁰ may be the same or different from each other.
R ¹⁰ is a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, a 1-chloroalkyl group, a trimethylsiloxy group, a triethylsiloxy group or a triphenylsiloxy group. Preferably, an alkyl group having 1 to 3 carbon atoms or a 1-chloroalkyl group having 1 to 3 carbon atoms is particularly 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 from the viewpoint of a high curing rate of the cured product. A methyl group is particularly preferred because it is readily available.
The alkoxy group X ^10, a methoxy group, preferably an ethoxy group or isopropoxy group, a methoxy group or an ethoxy group is more preferable. 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 property value of the cured product becomes better.
a is preferably 1 or 2, and a is more preferably 2.
As the reactive silicon group represented by the formula 10, a trimethoxysilyl group, a triethoxysilyl group, a methyldimethoxysilyl group or a methyldiethoxysilyl group is preferable, and a dimethoxymethylsilyl group or a trimethoxysilyl group is more preferable.

The number of reactive silicon groups present in the polycarbonate polymer is preferably more than 0.5 and 6.0 or less, more preferably 1.2 to 3.8, and 1.4 per molecule on average. ~ 2.0 pieces are more preferable. When it is at least the lower limit of the above range, the strength of the cured product of the curable composition becomes better, and when it is at least the upper limit value, the elongation of the cured product of the curable composition becomes better.

The alkylene oxide unit is preferably a unit based on at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and tetramethylene oxide. It is preferable that the alkylene oxide unit contains a unit based on propylene oxide in that the curable composition has a lower viscosity and is easier to handle, and the cured product becomes more flexible.

The Mn of the polycarbonate polymer of the present invention is 4,000 to 50,000, preferably 5,000 to 30,000, and more preferably 6,000 to 25,000. Within the above range, the elongation of the cured product becomes better, and the curable composition has a lower viscosity, so that it is easy to handle.
The Mw / Mn of the polycarbonate polymer of the present embodiment is preferably 1.0 to 3.0, more preferably 1.01 to 2.50, and 1.02 from the viewpoint of lowering the viscosity of the curable composition. ~ 2.20 is more preferable, and 1.03 to 2.00 is particularly preferable.

The number of carbonate groups present in the polycarbonate polymer is 2 or more, and an average of 3 or more per molecule is preferable, and 4 or more is more preferable. When it is at least the above lower limit value, the strength of the cured product of the curable composition becomes better. The upper limit of the number of carbonate groups is preferably 50 or less, more preferably 40 or less, from the viewpoint of the viscosity of the polymer.
The number of carbonate groups per molecule of the polycarbonate polymer can be calculated by NMR analysis.

In the polycarbonate polymer of the present embodiment, the carbonate group / alkylene oxide unit, which represents the molar ratio of the carbonate group content to the alkylene oxide unit content, is preferably 0.01 to 1, preferably 0.02 to 0.5. Is more preferable, and 0.03 to 0.4 is even more preferable. When it is at least the lower limit of the above range, the strength of the cured product of the curable composition becomes better, and when it is at least the upper limit, the curable composition has a lower viscosity, so that it is easy to handle and cures. It is preferable in that the strength of the cured product of the sex composition becomes better.

The terminal group of the polycarbonate polymer of the present embodiment is any of a reactive silicon group, a reactive terminal group, and a non-reactive terminal group. Examples of the reactive terminal group include an unsaturated group, an active hydrogen-containing group, and an isocyanate group existing at the terminal. The terminal groups present in a plurality of molecules in one molecule may be the same or different from each other.
The silylation rate is preferably more than 50 mol% and 100 mol% or less, more preferably 55 to 99 mol%, still more preferably 60 to 98 mol%.

<Manufacturing method>
The polycarbonate polymer of the present embodiment is a precursor polymer having a carbonate group and an alkylene oxide unit and having an active hydrogen-containing group at the terminal, or a derivative of the precursor polymer, and a silylating agent having a reactive silicon group. It can be manufactured by a method of reacting with.
Examples of the active hydrogen-containing group include a hydroxyl group, a carboxy group, an amino group, a monovalent functional group obtained by removing a hydrogen atom from a primary amine, a hydrazide group and a sulfanyl group. As the active hydrogen-containing group, a monovalent functional group obtained by removing one hydrogen atom bonded to a nitrogen atom in a hydroxyl group, an amino group, or a primary amine is preferable, and a hydroxyl group is more preferable.

The Mn of the precursor polymer is preferably 4,000 to 50,000, more preferably 5,000 to 30,000, and even more preferably 6,000 to 25,000.
The Mw / Mn of the precursor polymer is preferably 1.0 to 3.0, more preferably 1.01 to 2.50, and 1.02 to 2.20 from the viewpoint of further improving the elongation of the cured product. More preferably, 1.03 to 2.00 is particularly preferable.
The viscosity of the precursor polymer at 25 ° C. is preferably 100 to 100,000 mPa · s, more preferably 1,000 to 80,000 mPa · s, and even more preferably 2,800 to 60,000 mPa · s. When it is at least the lower limit of the above range, it is preferable that the curable composition is easy to handle, and when it is at least the upper limit, the strength of the cured product becomes better.

The precursor polymer having an active hydrogen-containing group at the terminal can be produced by a method of addition-polymerizing the monomer described below to the active hydrogen-containing group of the initiator described below.
The derivative of the precursor polymer is obtained by introducing one or more reactive end groups into the terminal of the precursor polymer. The number of reactive end groups present in the precursor polymer or its derivative is preferably 1 to 4, more preferably 1 to 2.

As a method for reacting the precursor polymer or its derivative with the silylating agent, a known method can be used.
For example, a method of reacting a derivative in which one or more unsaturated groups are introduced at the terminal of the precursor polymer with a silylating agent having a functional group that reacts with the unsaturated group is preferable.
Alternatively, a method of urethanizing the active hydrogen-containing group of the precursor polymer with the silylating agent by using a silylating agent having an isocyanate group which is a functional group that reacts with the active hydrogen-containing group is preferable.

The silylating agent having a functional group reactive with the unsaturated groups, for example, a compound having a reactive silicon group and sulfanyl group, hydrosilane compounds (e.g. HSiX a R 1 ^_3-a, except, X, R ¹ and a Is the same as in the above formula 1). Specifically, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris (2-propenyloxy) silane, triacetoxysilane, methyldimethoxysilane, methyldiethoxysilane, ethyldimethoxysilane, methyldiisopropoxysilane, Examples thereof include (α-chloromethyl) dimethoxysilane and (α-chloromethyl) diethoxysilane. From the viewpoint of high activity and good curability, trimethoxysilane, triethoxysilane, methyldimethoxysilane and methyldiethoxysilane are preferable, and methyldimethoxysilane or trimethoxysilane is more preferable.
Examples of the silylating agent having an isocyanate group include isocyanate silane compounds described in JP-A-2011-178955, and specifically, 1-isocyanate methyl dimethoxymethyl silane and 1-isocyanate methyl diethoxyethyl. Examples thereof include silane, 1-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, and 3-isocyanatepropylethyldiethoxysilane. 1-Isocyanatemethyldimethoxymethylsilane and 1-isocyanatepropylmethyldimethoxysilane are preferable.

A method in which one unsaturated group is introduced into one terminal of the precursor polymer and then the unsaturated group is reacted with a silylating agent, or an active hydrogen-containing group of the precursor polymer and an isocyanate silane compound are urethanized. Conventionally known methods can be used as the method for causing the compound, and for example, JP-A-45-363319, JP-A-50-156599, JP-A-61-197631, JP-A-3-72527, JP-A-8- Examples thereof include the methods proposed in 231707, Japanese Patent Application Laid-Open No. 2011-178955, US Pat. No. 3,362,557, and US Pat. No. 4,960,844.
As a method of introducing two unsaturated groups into one end of the precursor polymer, the precursor polymer is allowed to act on an alkali metal salt, then an epoxy compound having an unsaturated group is reacted, and then the unsaturated group is reacted. A method of reacting a halogenated hydrocarbon compound having a group is preferable.

As a method for introducing more than one unsaturated group into one end of the precursor polymer, a known method can be used without particular limitation. For example, International Publication No. 2013/180203, International Publication No. 2014, International Publication No. 2014 / 192842, JP2015-105293, JP2015-105322, JP2015-105323, JP2015-105324, International Publication No. 2015/080067, International Publication No. 2015/105122 , 2015/111577, International Publication 2016/002907, 2016-216633, 2017-39782 can be used.

As a method for producing the polycarbonate polymer of the present invention, the following aspects 1 to 3 are preferable.
[Aspect 1]
In aspect 1, a polycarbonate polyol is used as the initiator.
The number of hydroxyl groups of the polycarbonate polyol is 2 or more, preferably 2 to 5, and more preferably 2.0 to 3.5.
As the polycarbonate polyol, the polycarbonate diol represented by the following formula 4 is preferable. Further, as the polycarbonate polyol, an oligomer (polycarbonate polyol) in which alkylene oxide and carbon dioxide are added to the polyol can also be used.

The polycarbonate diol represented by the following formula 4 is a polycondensation polymer of the diol compound represented by the following formula 2 and the carbonate compound represented by the following formula 3. That is, the polycarbonate diol represented by the following formula 4 is a unit based on the diol compound represented by the following formula 2 (hereinafter, also referred to as “diol unit”) and a unit based on the carbonate compound represented by the following formula 3. Consists of. The diol unit present in the polycarbonate diol may be one type or two or more types. In terms of lower viscosity of the curable composition and higher maximum point cohesive force of the cured product, 2 to 5 types are preferable, and 2 or 3 types are more preferable.

HO-R ^2- OH formula 2
In Formula 2, R ² represents a substituted or unsubstituted divalent hydrocarbon group having 3 to 20 carbon atoms.
R ^3- OC (O) -OR ⁴ formula 3
In formula 3, R ³ and R ⁴ are independently alkyl or phenyl groups having 1 to 20 carbon atoms, or R ³ and R ⁴ are bonded to each other to form a ring.
_{^{H- [O-R 2 -O-}} C (O)] a -O-R 2 -OH Formula 4
In Equation 4, R ² is the same ^{as R 2 in Equation 2.} a is an integer of 1.0 or more, preferably 3.0 or more.

In Formula 2, R ² may be a substituted or unsubstituted chain hydrocarbon group or a substituted or unsubstituted cyclic hydrocarbon group. When R ² is composed of two or more kinds of hydrocarbon groups ^{, the sequence of − [OR 2-} OC (O)] − in the formula 4 may be random, block, or a combination of both.
The chain hydrocarbon group is more preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cyclic hydrocarbon group is, for example, a group represented by ^{-R 5-} R ^6- R ^5-. R ⁵ represents a single bond or an alkylene group having 1 to 6 carbon atoms. R ⁶ is an alicyclic hydrocarbon group having 3 to 9 carbon atoms having a substituted or unsubstituted monocyclic structure, an alicyclic hydrocarbon group having 4 to 16 carbon atoms having a substituted or unsubstituted polycyclic structure, or an alicyclic hydrocarbon group having 4 to 16 carbon atoms. Represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms. In the alicyclic hydrocarbon group, one or more carbon atoms forming a ring may be substituted with oxygen atoms. However, adjacent carbon atoms are not replaced with oxygen atoms at the same time.
The alkylene group having 1 to 6 carbon atoms of R ^{5 may be linear or branched.} When R ⁵ is an alkylene group having 1 to 6 carbon atoms, the carbon number is preferably 1 to 4, more preferably 1 or 2. The R ^5, a single bond, a methylene group, an ethylene group, n- propylene, n- butylene, n- pentylene, n- hexylene group, isopropylene group, isobutylene group, t Buchiren group and the like, a single bond , Methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group and t-butylene group are preferable, and single bond, methylene group and ethylene group are more preferable.
When R ⁶ is a divalent alicyclic saturated hydrocarbon group having 3 to 9 carbon atoms having an unsubstituted monocyclic structure, the carbon number of R ⁶ is 4 because it is more stable to heat and light. ~ 8 is preferable, 5-8 is more preferable, and 5 or 6 is further preferable. Examples of the divalent alicyclic saturated hydrocarbon group having 3 to 9 carbon atoms having an unsubstituted monocyclic structure of R ⁶ include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group and a cycloheptylene group. Cyclooctylene group and cyclononylene group are exemplified, and cyclopentylene group and cyclohexylene group are preferable.
When R ⁶ is a divalent alicyclic saturated hydrocarbon group having 4 to 16 carbon atoms having an unsubstituted polycyclic structure, the carbon number of R ⁶ is higher because the hardness and chemical resistance of the cured product are more excellent. 4 to 15 is preferable, and 6 to 12 is more preferable. R ⁶ is preferably a group having two or three ring structures, and more preferably a group having two ring structures.
When R ⁶ is an unsubstituted divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, the hardness and chemical resistance of the cured product are more excellent. Therefore, ^{the carbon number of R 6} is preferably 6 to 14. 6 to 12 are more preferable. Examples of the unsubstituted divalent aromatic hydrocarbon group having 6 to 18 carbon atoms include a phenylene group and a biphenylene group, and a phenylene group is preferable because the hardness and chemical resistance of the cured product are more excellent.
When R ⁶ is a divalent alicyclic saturated hydrocarbon group having 3 to 9 carbon atoms having a monocyclic structure having a substituent, the monocyclic structure has the carbon number of carbon atoms having the above-mentioned unsaturated monocyclic structure. It is the same as the divalent alicyclic saturated hydrocarbon group of 3 to 9.
When R ⁶ is a divalent alicyclic saturated hydrocarbon group having 4 to 16 carbon atoms having a polycyclic structure having a substituent, the polycyclic structure has the above-mentioned unsubstituted polycyclic structure. It is the same as the divalent alicyclic saturated hydrocarbon group of 4 to 16.
When R ⁶ is a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms having a substituent, the aromatic hydrocarbon group is the above-mentioned unsubstituted divalent aromatic hydrocarbon having 6 to 18 carbon atoms. The same is true for the hydrocarbon group.
The carbon number of R ⁶ indicates only the number of carbon atoms constituting the ring, and does not include the carbon number of the substituent. Examples of the substituent include a halogen atom, an alkyl group, and an alkoxy group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. Will be done. As the substituent, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a methoxy group, an ethoxy group and a halogen atom are preferable, and a methyl group, an ethyl group and a t-butyl group are used. , A methoxy group, an ethoxy group, and a chlorine atom are more preferable. The number of substituents is preferably 0 to 4, more preferably 0 to 2.
When R ⁶ is an alicyclic saturated hydrocarbon group having a monocyclic structure or a polycyclic structure and one or more carbon atoms constituting the ring are substituted with oxygen atoms, all the atoms constituting the ring are substituted. The ratio of the number of oxygen atoms to the number is preferably 5 to 50%, more preferably 10 to 30%.

Examples of the diol compound represented by the formula 2 include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1 , 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, , 16-Hexadecanediol, 1,18-octadecandiol, 1,20-eicosanediol and other diols without side chains; 2-methyl-1,8-octanediol, 2,2-dimethyl-1,3 -Propanediol (neopentyl glycol), 2-ethyl-1,3-hexanediol, 2-methyl-1,4-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5- Diols having side chains such as pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol; 1 , 3-Cyclohexanediol, 1,3-Cyclohexanedimethanol, 1,4-Cyclohexanediol, 1,4-Cyclohexanedimethanol, Isosorbide, 2-Bis (4-hydroxycyclohexyl) -propane, 2,3-Norbornanediol, Cyclic diols such as tetrahydrofuran-2,2-dimethanol, 5,5-bis (hydroxymethyl) -2-phenyl-1,3-dioxane; p-xylene glycol, p-tetrachloroxylenediol, 1,4-bis Examples thereof include diols having an aromatic ring such as (hydroxyethoxy) benzene and 2,2-bis [(4-hydroxyethoxy) phenyl] propane. These may be used alone or in combination of two or more.
Of these, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,7 are obtained in that the viscosity of the curable composition becomes lower and the strength of the cured product becomes better. −Heptanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1,8-octanediol, 2,2-dimethyl-1 , 3-Propanediol (neopentyl glycol), 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl- 1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,3-cyclohexanediol, 1,3-cyclohexanedimethanol, 1, 4-Cyclohexanediol, 1,4-Cyclohexanedimethanol, 2-bis (4-hydroxycyclohexyl) -propane2,7-norbornandiol, tetrahydrofurandimethanol, 2,5-bis (hydroxymethyl) -1,4-dioxane And isosorbide, more preferably 1,4-butanediol, 1,10-decanediol, 2-ethyl-1,6-hexanediol, 1,4-cyclohexanedimethanol, and isosorbide, 1,4-butanediol. , 1,10-decanediol and isosorbide are more preferred.

In formula 3, R ³ and R ⁴ are independently alkyl or phenyl groups having 1 to 20 carbon atoms. When R ³ and ^{R 4} are bonded to each other to form a ^{ring, (- O-R 3 -R} 4 -O-) of ^R 3, ^{R 4} are each independently an alkylene group having 1 to 3 carbon atoms Alternatively, it is an alkylene group having 1 to 3 carbon atoms in which at least one hydrogen atom is substituted with an alkyl group having 1 to 4 carbon atoms.
Examples of the carbonate compound represented by the formula 3 include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, ethylene carbonate, trimethylene carbonate, propylene carbonate, 1,2-butylene carbonate, and neopentylene carbonate. it can.
Of these, dimethyl carbonate, diethyl carbonate, diphenyl carbonate and ethylene carbonate are preferable in that the viscosity of the curable composition becomes lower and the strength of the cured product becomes better. Since the boiling point of the compound desorbed during the reaction is low, dimethyl carbonate and diethyl carbonate are preferable in that the equilibrium reaction tends to be inclined to the target compound, and the difference in boiling point between the compound desorbed by the reaction and the target compound is large. Diphenyl carbonate is preferable in that the compound can be easily separated.
Methods for producing a polycarbonate diol represented by the formula 4 by polycondensing the diol compound represented by the formula 2 and the carbonate compound represented by the formula 3 are described in, for example, JP-A-2012-77280 and JP-A-2014. The methods described in Japanese Patent Application Laid-Open No. 080590, Japanese Patent Application Laid-Open No. 2015-911937, Japanese Patent No. 3724561, Japanese Patent No. 5532592, Japanese Patent No. 1822688, Japanese Patent Application Laid-Open No. 4-2390234 and the like can be used.

The Mn of the polycarbonate diol represented by the formula 4 is preferably 250 to 10,000, more preferably 300 to 5,000. If it is at least the lower limit of the above range, the weather resistance and chemical resistance of the cured product are likely to be good, and if it is at least the upper limit, the curable composition has a lower viscosity and is easy to handle.
The Mw / Mn of the polycarbonate diol represented by the formula 4 is preferably 3.0 or less, more preferably 2.5 or less, and even more preferably 2.0 or less. When it is not more than the upper limit value, the curable composition has a lower viscosity and is easy to handle.

The oligomer (polycarbonate polyol) has at least a structure represented by the following formula 5. That is, it contains a carbonate group. In formula 5, -AO- represents the unit in which the alkylene oxide is ring-opened.
-[AO-C (O) O] -Equation 5
The oligomer (polycarbonate polyol) is preferably an oligomer (polycarbonate diol) in which an alkylene oxide and carbon dioxide are added to a diol compound.
In the oligomer (polycarbonate diol), the diol compound is preferably the diol compound represented by the above formula 2.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide. In particular, propylene oxide is preferable. The sequences of the units based on alkylene oxide and the units based on carbon dioxide may be random, block, or a combination of both.
A method for addition-polymerizing an alkylene oxide and carbon dioxide to a hydroxyl group of a diol compound in the presence of a ring-opening polymerization catalyst is described in, for example, Japanese Patent Application Laid-Open No. 2009-544801, US Patent Application Publication No. 2012/0289732, International Publication. The methods described in No. 2013/034750, Japanese Patent Application Laid-Open No. 2011-52091, and Japanese Patent Application Laid-Open No. 2012-500867 can be used.
The Mn of the oligomer (polycarbonate diol) is preferably 100 to 5,000, more preferably 150 to 3,000, from the viewpoint of good reactivity with the alkylene oxide when forming the oligomer.
The Mw / Mn of the oligomer (polycarbonate diol) is preferably 3.0 or less, more preferably 2.5 or less, still more preferably 2.0 or less, from the viewpoint of better elongation of the cured product.

In the first aspect, the alkylene oxide is subjected to ring-opening addition polymerization in the presence of a ring-opening polymerization catalyst on the hydroxyl group (active hydrogen-containing group) of the polycarbonate polyol which is the initiator. As a result, a precursor polymer having a polyoxyalkylene chain composed of alkylene oxide units and having a hydroxyl group at the end (hereinafter, also referred to as “precursor polymer a1”) is obtained. The number of hydroxyl groups of the polycarbonate polyol and the number of active hydrogen-containing groups of the precursor polymer a1 are the same.
A polycarbonate polymer A1 is obtained by reacting the precursor polymer a1 or a derivative in which one or more reactive end groups are introduced at the ends of the precursor polymer a1 with a silylating agent.

In the first aspect, the ring-opening addition polymerization catalyst for ring-opening addition polymerization of the alkylene oxide as an initiator is not particularly limited, and is, for example, a composite metal cyanide complex catalyst; sodium hydroxide, potassium hydroxide, and cesium hydroxide. Alkali catalysts such as; Chigranatta catalysts composed of organic aluminum compounds and transition metal compounds; Metal porphyrin catalysts as complexes obtained by reacting porphyrins; Phosphazen catalysts; Imino group-containing phosphazenium salts; Tris (pentafluorophenyl) borane; Preferred examples include a catalyst composed of a salen complex; a catalyst composed of a redened Robson's type Macrochemical rigid and the like. These may be used alone or in combination of two or more. A composite metal cyanide complex catalyst is preferable because a precursor polymer a1 having a narrow Mw / Mn and a low viscosity can be easily obtained. Examples of the ligand of the composite metal cyanide complex catalyst include t-butyl alcohol, ethylene glycol dimethyl ether (glyme), and diethylene glycol dimethyl ether (diglyme), and a precursor polymer a1 having a narrow Mw / Mn and a low viscosity is more obtained. T-butyl alcohol is preferable because it is easily obtained.
The composite metal cyanide complex catalyst is not particularly limited, and conventionally known compounds can be used, and a known method can be adopted as a method for producing a polymer using the composite metal cyanide complex, including the amount of addition. .. For example, International Publication No. 2003/062301, International Publication No. 2004/067633, JP-A-2004-2697776, JP-A-2005-15786, International Publication No. 2013/065802, JP-A-2015-01162 The compounds and production methods disclosed in the publication can be used.

The alkylene oxide unit constituting the polyoxyalkylene chain of the precursor polymer a1 may be one kind or two or more kinds. When the polyoxyalkylene chain has two or more kinds of alkylene oxide units, their sequences may be random, blocks, or a combination of both.

The Mn of the precursor polymer a1 is preferably 4,000 to 50,000, more preferably 5,000 to 30,000, and even more preferably 6,000 to 25,000.
The Mw / Mn of the precursor polymer a1 is preferably 1.0 to 3.0, more preferably 1.01 to 2.50, further preferably 1.02 to 2.20, and particularly 1.03 to 2.00. preferable.
The precursor polymer a1 may be a solid, and when it is a solid, it is preferably liquid when heated to 90 ° C. When the precursor polymer a1 is liquid at 25 ° C, the viscosity of the precursor polymer a1 at 25 ° C is preferably 100 to 100,000 mPa · s, more preferably 1,000 to 80,000 mPa · s, and 2,800. ~ 60,000 mPa · s is more preferable. When it is at least the lower limit of the above range, it is preferable that the curable composition is easy to handle, and when it is at least the upper limit, the strength of the cured product becomes better.

In the polycarbonate polymer A1, the molar ratio of the carbonate group / alkylene oxide unit is preferably 0.01 to 1.00, preferably 0.02 to 0.50, from the viewpoint of easy handling because the curable composition has a lower viscosity. More preferred.
The Mn of the polycarbonate polymer A1 is preferably 4,000 to 50,000, more preferably 5,000 to 30,000, and 6,000 to 25,000 from the viewpoint of improving the elongation and strength of the cured product. More preferred.
The Mw / Mn of the polycarbonate polymer A1 is preferably 1.0 to 3.0, more preferably 1.01 to 2.50, and further preferably 1.02 to 2.20 from the viewpoint of improving the elongation of the cured product. Preferably, 1.03 to 2.00 is particularly preferable.
The number of carbonate groups per molecule of the polycarbonate polymer A1 is preferably 2 to 50 on average, more preferably 3 to 30, from the viewpoint of improving the strength of the cured product.

[Aspect 2]
In the second aspect, as in the first aspect, the above-mentioned polycarbonate polyol is used as the initiator.
In the second aspect, alkylene oxide and carbon dioxide are addition-polymerized to the hydroxyl group (active hydrogen-containing group) of the polycarbonate polyol which is the initiator in the presence of a ring-opening polymerization catalyst. As a result, a precursor polymer having a copolymer chain (polycarbonate diol chain) composed of a unit based on alkylene oxide and a unit based on carbon dioxide and having a hydroxyl group at the end (hereinafter, also referred to as “precursor polymer a2”) is obtained. .. The number of hydroxyl groups of the polycarbonate polyol and the number of active hydrogen-containing groups of the precursor polymer a2 are the same.
A polycarbonate polymer A2 is obtained by reacting the precursor polymer a2 or a derivative in which one or more reactive end groups are introduced at the ends of the precursor polymer a2 with a silylating agent.

In aspect 2, the initiator polycarbonate polyol is similar to aspect 1. The ring-opening polymerization catalyst is the same as in aspect 1.
In the second aspect, a method for addition-polymerizing alkylene oxide and carbon dioxide to the hydroxyl group of the initiator in the presence of a ring-opening polymerization catalyst is described in, for example, Japanese Patent Application Laid-Open No. 2009-544801, US Patent Application Publication No. 2012/0289732. The methods described in the book, International Publication No. 2013/034750, Japanese Patent Publication No. 2011-52091, and Japanese Patent Publication No. 2012-500867 can be used.

The arrangement of the alkylene oxide unit and the carbon dioxide-based unit constituting the polycarbonate diol chain of the precursor polymer a2 may be random, may be a block, or may be a combination of both. The polycarbonate diol chain has at least a structure represented by the formula 5. That is, the polycarbonate diol chain contains a carbonate group. In formula 5, -AO- represents the unit in which the alkylene oxide is ring-opened.
-[AO-C (O) O] -Equation 5
In the second aspect, the alkylene oxide unit may be one kind or two or more kinds.

The Mn of the precursor polymer a2 is preferably 4,000 to 50,000, more preferably 5,000 to 30,000, and even more preferably 6,000 to 25,000.
The Mw / Mn of the precursor polymer a2 is preferably 1.0 to 3.0, more preferably 1.01 to 2.50, further preferably 1.02 to 2.20, and particularly preferably 1.03 to 2.00. preferable.
The precursor polymer a2 may be a solid, and when it is a solid, it is preferably liquid when heated to 90 ° C. When the precursor polymer a2 is liquid at 25 ° C., the viscosity of the precursor polymer a2 at 25 ° C. is preferably 100 to 100,000 mPa · s, more preferably 1,000 to 60,000 mPa · s, and 2,800 to ~. 60,000 mPa · s is even more preferable. When it is at least the lower limit of the above range, it is preferable that the curable composition is easy to handle, and when it is at least the upper limit, the strength of the cured product becomes better.

In the polycarbonate polymer A2, the molar ratio of the carbonate group / alkylene oxide unit is preferably 0.01 to 1.00 from the viewpoint that the curable composition has a lower viscosity and is easy to handle, and the strength of the cured product becomes better. , 0.02 to 0.50 is more preferable.
The Mn of the polycarbonate polymer A2 is preferably 4,000 to 50,000, more preferably 5,000 to 30,000, and 6,000 to 25,000 from the viewpoint of improving the elongation and strength of the cured product. More preferred.
The Mw / Mn of the polycarbonate polymer A2 is preferably 1.0 to 3.0, more preferably 1.01 to 2.50, and 1.02 to 2.20 from the viewpoint of better elongation of the cured product. More preferably, 1.03 to 2.00 is particularly preferable.
The average number of carbonate groups per molecule of the polycarbonate polymer A2 is preferably 2 to 50, more preferably 3 to 30.

[Aspect 3]
In embodiment 3, a carbonate-free polyol is used as the initiator.
The number of hydroxyl groups of the polyol containing no carbonate group is 2 or more, preferably 2 to 6, more preferably 2 to 4, further preferably 2 to 3, and particularly preferably 2. As the polyol, an oligomer (polyether polyol) in which an alkylene oxide is added to the polyol can also be used.
There may be two or more types of polyols. When two or more types of polyols are used in combination, the average number of hydroxyl groups per molecule is defined as the number of hydroxyl groups of the polyol.
Examples of the polyol having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), and 1,4. Examples thereof include -butanediol, 1,6-hexanediol, and low molecular weight polyoxypropylene glycol.
Examples of the polyol having three hydroxyl groups include glycerin, trimethylolpropane, trimethylolethane, and low molecular weight polyoxypropylene triol.
Examples of the polyol having four or more hydroxyl groups include sorbitol and pentaerythritol.
The Mn of the polyol containing no carbonate group is preferably less than 300, more preferably 62 to 250, and even more preferably 70 to 200, from the viewpoint of good reactivity with alkylene oxide.
The Mn of the oligomer (polyether polyol) is preferably 100 to 5,000, more preferably 150 to 3,000, and more preferably 300 to 3, from the viewpoint of good reactivity with the alkylene oxide when forming the oligomer. 000 is more preferable.
The Mw / Mn of the oligomer (polyether polyol) is preferably 1.0 to 3.0, more preferably 1.01 to 2.50, because the obtained curable composition has a lower viscosity. 02 to 2.20 is more preferable, and 1.03 to 2.00 is particularly preferable.

In the third aspect, alkylene oxide and carbon dioxide are addition-polymerized to the hydroxyl group (active hydrogen-containing group) of the polyol as the initiator in the presence of a ring-opening polymerization catalyst. As a result, a precursor polymer having a polycarbonate diol chain composed of an alkylene oxide unit and a unit based on carbon dioxide and having a hydroxyl group at the end (hereinafter, also referred to as “precursor polymer a3”) is obtained. The number of hydroxyl groups of the polyol used as the initiator and the number of active hydrogen-containing groups of the precursor polymer a3 are the same.
A polycarbonate polymer A3 is obtained by reacting the precursor polymer a3 or a derivative in which one or more reactive end groups are introduced at the ends of the precursor polymer a3 with a silylating agent.

In aspect 3, the ring-opening polymerization catalyst is the same as in aspect 1.
In the third aspect, the method of addition-polymerizing the alkylene oxide and carbon dioxide to the hydroxyl group of the polyol as the initiator in the presence of a ring-opening polymerization catalyst is the same as that of the second aspect.

The Mn of the precursor polymer a3 is preferably 4,000 to 50,000, more preferably 5,000 to 30,000, and even more preferably 6,000 to 25,000.
The Mw / Mn of the precursor polymer a3 is preferably 1.0 to 3.0, more preferably 1.01 to 2.50, further preferably 1.02 to 2.20, and particularly 1.03 to 2.00. preferable.
The precursor polymer a3 is preferably liquid at 25 ° C., and the viscosity of the precursor polymer a3 at 25 ° C. is preferably 100 to 100,000 mPa · s, more preferably 1,000 to 80,000 mPa · s, 2, 800 to 60,000 mPa · s is more preferable. When it is at least the lower limit of the above range, it is preferable that the curable composition is easy to handle, and when it is at least the upper limit, the strength of the cured product becomes better.

In the polycarbonate polymer A3, the molar ratio of carbonate group / alkylene oxide unit is preferably 0.01 to 1.00 from the viewpoint that the curable composition has a low viscosity and is easy to handle, and the strength of the cured product becomes better. , 0.02 to 0.50 is more preferable.
The Mn of the polycarbonate polymer A3 is preferably 4,000 to 50,000, more preferably 5,000 to 30,000, and 6,000 to 25,000 from the viewpoint of improving the elongation and strength of the cured product. More preferred.
Mw / Mn is preferably 1.0 to 3.0, more preferably 1.01 to 2.50, and 1.02 to 2.20 from the viewpoint of better elongation of the cured product of the polycarbonate polymer A3. More preferably, 1.03 to 2.00 is particularly preferable.
The number of carbonate groups per molecule of the polycarbonate polymer A3 is preferably 2 to 50 on average, more preferably 3 to 30, from the viewpoint of better elongation of the cured product.
The carbonate polymer of the present invention has one or more reactive silicon groups, two or more carbonate groups, and a repeating unit based on alkylene oxide in one molecule, and has a Mn of 4,000 to 50, A polycarbonate polymer represented by the following formula 11, which is 000, is preferable.
X ¹⁰ _a R ¹⁰ _3-a Si-Q-[(OR ¹¹ ) _n (OR ^11- OC (O)) _m (OR ^2- OC (O)) _t ] ^{-OR 21-} O −Q−SiX ¹⁰ _a R ¹⁰ _3-a formula 11
In formula 11, X ¹⁰ represents a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and R ¹⁰ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halo hydrocarbon group having 1 to 20 carbon atoms. shows, Q is a divalent hydrocarbon group having a substituted or unsubstituted 1 to 6 carbon atoms, or -NHC (O) ^{-R 31} - ^{indicates, R 31} is 2 substituted or unsubstituted 1 to 6 carbon atoms It shows a valent hydrocarbon group, one of which is bonded to a silicon atom, R ¹¹ shows a substituted or unsubstituted divalent hydrocarbon group having 2 to 4 carbon atoms, and R ² and R ²¹ are respectively. Independently indicates a substituted or unsubstituted divalent hydrocarbon group having 3 to 20 carbon atoms, n is an integer of 1 to 900, t is an integer of 0 to 50, and m is an integer of 0 to 500. And n + t + m is an integer of 3 or more. a is an integer of 1 to 3, and when a is 1, R ¹⁰ may be the same or different from each other, and when a is 2 or 3, X ¹⁰ may be the same or different from each other.
X ¹⁰ and ^{R 10} are the same as ^{X 10} and ^{R 10} in the formula 10, preferable embodiments thereof are also the same.
Q is a divalent hydrocarbon group of a substituted or unsubstituted 1 to 6 carbon atoms, or -NHC (O) ^{-R 31} - shows the. As the substituted or unsubstituted divalent hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted divalent chain hydrocarbon group having 1 to 6 carbon atoms is preferable, and an unsubstituted or unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms is preferable. The divalent chain hydrocarbon group of No. 1 is more preferable.
R ³¹ represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 6 carbon atoms, and one of the bonds is bonded to a silicon atom. As the substituted or unsubstituted divalent hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted divalent chain hydrocarbon group having 1 to 6 carbon atoms is preferable, and an unsubstituted or unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms is preferable. The divalent chain hydrocarbon group of No. 1 is more preferable.
(OR ¹¹ ) represents a unit in which the alkylene oxide is ring-opened. The alkylene oxide is preferably a cyclic ether having 2 to 4 carbon atoms, and examples thereof include ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide. In particular, propylene oxide is preferable. The sequences of the units based on alkylene oxide and the units based on carbon dioxide may be random, block, or a combination of both.
R ² and R ^{21 are the same as R 2} in the above formula 2, and the preferred embodiment is also the same.
The unit represented by [(OR ¹¹ ) _n (OR ^11- OC (O)) _m (OR ^2- OC (O)) _t ] is the repeating unit represented by ^{(OR 11), (OR 11).} It ^{means that it consists of a repeating unit represented by OR 11-} OC (O)) and a repeating unit represented by (OR ^2- OC (O)), and the order of joining each repeating unit is particularly limited. However, each repeating unit may be arranged in a random manner or in a block shape.
n is an integer of 1 to 900, t is an integer of 0 to 50, and m is an integer of 0 to 500. n + t + m is preferably 3 to 900, more preferably 20 to 800, further preferably 50 to 600, and particularly preferably 60 to 500.
a is an integer of 1 to 3, and when a is 1, R ¹⁰ may be the same or different from each other, and when a is 2 or 3, X ¹⁰ may be the same or different from each other. a is preferably 1 or 2, more preferably 2.
The Mn of the polymer represented by the formula 11 is preferably 4,000 to 50,000, more preferably 5,000 to 30,000, and more preferably 6,000 to 6,000 to improve the elongation and strength of the cured product. 25,000 is even more preferred.
Mw / Mn is preferably 1.0 to 3.0, more preferably 1.01 to 2.50, and 1.02 to 1.02, from the viewpoint of better elongation of the cured product of the polymer represented by the formula 11. 2.20 is more preferable, and 1.03 to 2.00 is particularly preferable.
The number of carbonate groups per molecule of the polymer represented by the formula 11 is preferably 2 to 50 on average, more preferably 3 to 30, from the viewpoint of better elongation of the cured product.

<Curable composition>
The polycarbonate polymer of the present invention is a polymer useful as a curable material. Examples of the curable material include those for sealing materials and those for adhesives. When the polycarbonate polymer of the present invention is used as a curable material, it is usually preferable to use it as a curable composition.
The curable composition comprises the polycarbonate polymer of the present embodiment. The curable composition is usually a composition containing a polycarbonate polymer and a curing catalyst described later.
The content ratio of the polycarbonate polymer with respect to the total mass of the curable composition is preferably 3 to 50% by mass, more preferably 5 to 45% by mass, still more preferably 10 to 40% by mass. When the content ratio of the polycarbonate polymer is within the above range, the strength and elongation of the cured product are more excellent.
The curable composition may contain one or more of the curing catalysts. When the curable composition contains the curing catalyst, the content is preferably 0.01 to 15.0 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polycarbonate polymer. When it is 0.1 part by mass or more, the curing reaction easily proceeds sufficiently, and when it is 20 parts by mass or less, local heat generation and foaming do not occur at the time of curing, and a good cured product can be easily obtained.

[Other ingredients]
The curable composition contains other components other than the polycarbonate polymer. Examples of other components include additives depending on the use of the curable composition, such as an organic polymer having no reactive silicon group represented by the above formula 1, a filler, a plasticizer, and a thixophilic imparting agent. , Antioxidants, UV absorbers, light stabilizers, dehydrating agents, adhesive imparting agents, amine compounds, oxygen curable compounds, photocurable compounds, and curing catalysts (silanol condensation catalysts) can be exemplified.
Other components include International Publication No. 2013/180203, International Publication No. 2014/192842, International Publication No. 2016/002907, JP-A-2014-88481, JP-A-2015-10162, JP-A-2015-105293. No., 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 such as the polycarbonate polymer and the above additives are premixed, sealed and stored, and cured by the humidity in the air after construction, and has at least a reactive silicon group. A two-component type may be used in which the main agent composition containing the components and the curing agent composition containing at least the curing catalyst are stored separately, and the curing agent composition and the main agent composition are mixed before use. A one-component curable composition is preferable 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 ingredients in advance from the viewpoint of storage stability.
A dehydrating agent may be added to the one-component curable composition or the two-component main composition to improve storage stability.

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.
In particular, it is suitable for applications that require excellent strength and elongation, and for example, a sealant and an adhesive that are applied outdoors are suitable.

The stress (M50) of the cured product obtained from the curable composition as measured by the tensile test shown in Examples described later when stretched by 50% ^{tends to be 0.5 N / mm 2} or more, and further 0. It tends to be 8N / mm ^{2 or more.} When it is at least the above lower limit value, good strength is obtained, and it is suitable as a sealing material and an adhesive.

The maximum point cohesive force of the cured product obtained from the curable composition as measured by the tensile test shown in Examples described later is ^{likely to be 1.0 N / mm 2} or more, and further 1.2 N / mm ² or more. Cheap. When it is at least the above lower limit value, good strength is obtained, and it is suitable as a sealing material and an adhesive.

The maximum point elongation of the cured product obtained from the curable composition, as measured by the tensile test shown in Examples described later, tends to be 175% or more, and further tends to be 180% or more. When it is at least the above lower limit value, good elongation is obtained, and it is suitable as a sealant and an adhesive.
Since the cured product obtained from the curable composition tends to suppress cracks caused by immersion in water due to the hydrophobicity of the cured product, the weather resistance measured by the weather resistance test shown in Examples described later is 400 hours or more. It tends to be more than 500 hours. When it is at least the above lower limit value, the weather resistance is good and it is suitable as a sealing material and an adhesive, and particularly suitable for a sealing material used outdoors and an adhesive for buildings and vehicles.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
<Measurement method / evaluation method>
[Mn and molecular weight distribution (Mw / Mn)]
Using HLC-8320GPC (product name of Tosoh Corporation) and using tetrahydrofuran as a developing solvent, the number average molecular weight (Mn), mass average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of polyoxypropylene diol were determined.
[Copolymerization composition ratio of polymer]
The polymer obtained in the synthesis example described later was dissolved in deuterated chloroform so as to have a concentration of 10 wt%, and ¹ H-NMR was measured at a resolution of 400 MHz (JNM-ECZ400SJNM, product name of JEOL Ltd.). From the obtained results, a peak based on the diol unit and a peak based on the alkylene oxide unit present in the polycarbonate diol were specified, and the copolymerization composition ratio in the polymer was calculated from the area.

[viscosity]
The viscosity of the precursor polymer obtained in the synthetic example described later at 25 ° C. was measured with an E-type viscometer VISCOMETER TV-22 (Toki Sangyo product name).
[Number of reactive silicon in polymer (silylation rate)]
In the method of introducing a reactive silicon group by reacting 1-isocyanatepropylmethyldimethoxysilane with the hydroxyl group at the end of the precursor polymer, the molar ratio of the amount of 1-isocyanatepropylmethyldimethoxysilane charged to the amount of hydroxyl group of the precursor polymer. Was defined as the silylation rate.
[Number of carbonate groups per molecule]
The polymer obtained in the synthetic example described later was dissolved in deuterated chloroform to which an internal standard substance was added, and ^{1 1} H-NMR measurement was carried out. From the sum of the area of the proton bonded to the carbon atom adjacent to the carbonate group and the area of the proton of the methyl group bonded to the carbon atom adjacent to the carbonate group and the area ratio of the proton of the internal standard substance, carbonate per unit weight The number of groups was calculated, and further multiplied by Mn obtained from GPC to calculate the number of carbonate groups per molecule.
[Mole ratio of carbonate group / alkylene oxide unit]
The polymer obtained in the synthetic example described later was dissolved in deuterated chloroform and ¹ H-NMR was measured. The sum of the area of the proton bonded to the carbon atom adjacent to the carbonate group (Y _c ) and the area of the proton of the methyl group bonded to the carbon atom adjacent to the carbonate group (Y _cm ), and the ether oxygen of the alkylene oxide The ratio of the sum of the area of the proton of the methyl group bonded to the adjacent carbon atom ( _Yem ) and the area of the proton of the methyl group bonded to the carbon atom adjacent to the carbonate group (Y _{cm ) ((Y c} + Y _cm). ) / ( _Yem + Y _cm )), the molar ratio of carbonate group / alkylene oxide unit was calculated.

[State of cured product]
30 g of the curable composition obtained in the examples described later was filled in a mold having a length of 300 mm, a width of 25 mm, and a thickness of 2 mm, cured at a temperature of 23 ° C. and a humidity of 50% for 3 days, and further at a temperature of 50 ° C. , Cured at 65% humidity for 4 days. The presence of air bubbles in the obtained cured product was confirmed and evaluated according to the following criteria. If many bubbles are present in the cured product, correct values cannot be obtained in the tensile test described later.
〇: There are no bubbles in the cured product.
Δ: There are bubbles in the cured product, and the volume of the bubbles is less than 10% of the volume of the cured product.
X: There are bubbles in the cured product, and the volume of the bubbles is 10% or more of the volume of the cured product.
[Tensile test]
The curable composition obtained in the examples described later was filled in a mold having a length of 300 mm, a width of 25 mm, and a thickness of 2 mm, cured at a temperature of 23 ° C. and a humidity of 50% for 3 days, and further at a temperature of 50 ° C. and a humidity of 65%. It was cured for 4 days. The obtained cured product having a thickness of 2 mm was punched out with a dumbbell mold to obtain a test piece. Using this test piece, a tensile test was performed at a tensile speed of 500 mm / min, and the stress (M50, unit: N / mm ² ), maximum point cohesive force (unit: N / mm ² ), and maximum when stretched by 50%. The tensile characteristics of point elongation (unit:%) were measured.
[Weather resistance test]
The curable composition obtained in the examples described later was filled in a mold having a length of 25 mm, a width of 25 mm, and a thickness of 5 mm, and cured at a temperature of 23 ° C. and a humidity of 50% for 3 days, and further, a temperature of 50 ° C. and a humidity of 65%. It was cured for 4 days. The obtained cured product having a thickness of 2 mm was used as a sample, and a test was carried out according to the evaluation criteria of JIS A1439. The test was carried out with a sunshine weather meter (product name of Suga Test Instruments Co., Ltd.) under the conditions of a black panel temperature of 63 ° C., a humidity of 50%, and water sprinkling every 120 minutes for 2 minutes, and the time until cracks occurred in the sample was measured.

<Synthesis of polymer>
(Synthesis Example 1: Polymer A1-1)
450 g of 1,4-butanediol (hereinafter referred to as "1,4-BD"), 2,2-dimethyl-1,3-propane in a reactor equipped with a stirrer, a distillate trap and a pressure regulator. 620 g of diol (neopentyl glycol) (hereinafter referred to as "NPG"), 2140 g of diphenyl carbonate (hereinafter referred to as "DPC"), and 50 mg of magnesium acetate tetrahydrate were added, and the inside of the reaction tube was replaced with nitrogen. did. The raw materials were heated and dissolved in an oil bath set at 200 ° C. and reacted for 30 minutes.
Then, the distilled phenol and the unreacted diol were removed while lowering the pressure to 0.4 KPa over 5 hours and 30 minutes. Then, in order to increase the molecular weight of the polycarbonate diol, the polycarbonate diol was kept at 200 ° C. and 0.4 KPa and reacted for 30 minutes to distill off by-products. The Mn of the obtained polycarbonate diol was 1,700. ¹ By 1 H-NMR, the peak area of 4.10-4.20 ppm based on two protons bonded to the methylene group of 1,4-BD adjacent to the carbonate group and the methylene group of NPG adjacent to the carbonate group were obtained. The peak area of 3.90-4.00 ppm based on the two bonded protons was calculated, and the copolymer composition ratio of 1,4-BD / NPG was 54/46 (molar ratio) from these ratios. ..
The obtained polycarbonate diol is referred to as propylene oxide (hereinafter referred to as "PO") using a zinc hexacyanocobaltate complex having a ligand of t-butyl alcohol (hereinafter referred to as "TBA-DMC catalyst") as a catalyst. ) Was added to obtain a precursor polymer a1-1.
97 mol% of 1-isocyanatepropylmethyldimethoxysilane with respect to the amount (molar) of the hydroxyl group which is the terminal group of the precursor polymer a1-1, and 50 mass ppm of the organotin compound with respect to the precursor polymer a1-1 ( U-860 Nitto Kasei Co., Ltd. product name) was added. The hydroxyl group and 1-isocyanatepropylmethyldimethoxysilane are reacted at 80 ° C. for 3 hours until the disappearance of the peak based on the isocyanate group can be confirmed by FT-IR (ATR method, SPECTRUM100, PerkinElmer product name). The polymer A1-1 was obtained.
According to the above method, the number of carbonate groups per molecule and the molar ratio of carbonate groups / alkylene oxide units were calculated. Mn, Mw / Mn, and viscosity of the precursor polymer, as well as the number of all terminal groups in the polymer, Mn, Mw / Mn, silylation ratio, number of carbonate groups per molecule, and molars of carbonate group / alkylene oxide units. The ratios are shown in Table 1. Each value was calculated in the same manner for the following synthesis examples, and the results are shown in Table 1.

(Synthesis Example 2: Polymer A1-2)
In the same manner as in Synthesis Example 1, a precursor composite a1-2 having Mn of 11,200 was obtained. In the same manner as in Synthesis Example 1, 1-isocyanatepropylmethyldimethoxysilane was reacted with the hydroxyl group which is the terminal group of the precursor polymer a1-2 to obtain the polymer A1-2.

(Synthesis Example 3: Polymer A1-3)
In a reactor equipped with a stirrer, distillate trap and pressure regulator, 637 g of 1,4-BD, 1033 g of isosorbide (hereinafter referred to as "iSB"), 2331 g of DPC, 61 mg of magnesium acetate tetrahydrate. After replacing the inside of the reactor with nitrogen, the internal temperature was raised to 160 ° C. to heat and dissolve the contents. Then, the pressure was lowered to 23 kPa over 5 minutes, and then the reaction was carried out for 90 minutes while distilling and removing phenol. Then, the pressure was lowered to 9.3 kPa over 90 minutes, further lowered to 0.7 kPa over 30 minutes, and then the temperature was raised to 170 ° C. for 60 minutes while distilling and removing phenol and unreacted diol. The reaction was carried out to obtain a polycarbonate diol.
The Mn of the polycarbonate diol is 800, and ¹ H-NMR shows a peak area of 4.10-4.20 ppm based on two protons bonded to the methylene group of 1,4-BD adjacent to the carbonate group, and carbonate. The peak area of 4.90-5.05 ppm based on one proton attached to the methyl group of iSB adjacent to the group was calculated. From these ratios, the copolymerization composition ratio of 1,4-BD / iSB was 55/45 (molar ratio).
PO was addition-polymerized to the polycarbonate diol obtained in the same manner as in Synthesis Example 1 to obtain a precursor polymer a1-3.
In the same manner as in Synthesis Example 1, 1-isocyanatepropylmethyldimethoxysilane was reacted with the hydroxyl group which is the terminal group of the precursor polymer a1-3 to obtain the polymer A1-3.

(Synthesis Example 4: Polymer A1-4)
In a reactor equipped with a stirrer, distillate trap and pressure regulator, 433 g of 1,10-decanediol (hereinafter referred to as "1,10-DD"), 773 g of 1,4-BD, and 1794 g of DPC. , 4.7 mL (concentration: 8.4 g / L, magnesium acetate tetrahydrate: 40 mg) of the magnesium acetate tetrahydrate aqueous solution was added, and the reaction was carried out in the same manner as in Synthesis Example 1 to carry out the polycarbonate diol. Got
The Mn of the polycarbonate diol was 2,000. ¹ By 1 H-NMR, a peak area of 4.10-4.20 ppm based on two protons bonded to the methylene group of 1,4-BD adjacent to the carbonate group and 1,10-DD adjacent to the carbonate group The peak area of 4.00-4.05 ppm based on the two protons bonded to the methyl group of was calculated, and the copolymer composition ratio of 1,4-BD / 1,10-DD was calculated from the ratio of these areas. Was 47/53 (molar ratio).
PO was addition-polymerized to the polycarbonate diol obtained in the same manner as in Synthesis Example 1 to obtain a precursor polymer a1-4.
In the same manner as in Synthesis Example 1, 1-isocyanatepropylmethyldimethoxysilane was reacted with the hydroxyl group which is the terminal group of the precursor polymer a1-4 to obtain the polymer A1-4.

(Synthesis Example 5: Polymer A1-5)
In a reactor equipped with a stirrer, distillate trap and pressure regulator, 830 g of 1,6-hexanediol (hereinafter referred to as "1,6-HD"), 771 g of diethyl carbonate, and 0. 05 g was added and the inside of the reactor was replaced with nitrogen. The temperature is gradually raised to 190 ° C. under a nitrogen stream, and when the top temperature of the distillation column becomes 50 ° C. or lower, the reaction temperature remains 190 ° C. and the reaction is gradually reduced to 1.3 KPa. , A polycarbonate diol consisting of 1,6-HD was obtained. The Mn of the obtained polycarbonate diol was 2,000.
PO was addition-polymerized to the polycarbonate diol obtained in the same manner as in Synthesis Example 1 to obtain a precursor polymer a1-5.
After heating the precursor polymer a1-5 at 80 ° C. for 3 hours to make it liquid, 1-isocyanatepropylmethyldimethoxysilane is reacted with the hydroxyl group which is the terminal group of the precursor polymer a1-5 in the same manner as in Synthesis Example 1. The mixture was allowed to obtain polymer A1-5.

(Synthesis Example 6: Polymer A1-6)
Polypropylene glycol of Mn 1,000 (hereinafter referred to as "PPG") was placed in the reactor, and the gas phase in the reactor was replaced with carbon dioxide in a state where the carbon dioxide cylinder and the inside of the reactor were connected. Then, while always pressurizing the inside of the reactor with carbon dioxide so as to be 2.0 MPa, PO and dioxide were used using the cobalt complex described in paragraphs [0434] to [0436] of JP2015-28182. Carbon was addition polymerized. The Mn of the obtained polycarbonate diol was 2,100. Using a TBA-DMC catalyst, PO was addition-polymerized to the obtained polycarbonate diol to obtain a precursor polymer a1-6.
Then, in the same manner as in Synthesis Example 1, 1-isocyanatepropylmethyldimethoxysilane was reacted with the hydroxyl group which is the terminal group of the precursor polymer a1-6 to obtain the polymer A1-6.

(Synthesis Example 7: Polymer A2-1)
In a reactor equipped with a stirrer, distillate trap and pressure regulator, 637 g of 1,4-BD, 1033 g of iSB, 2331 g of DPC and 61 mg of magnesium acetate tetrahydrate were placed and the inside of the reactor was filled with nitrogen. After the substitution, the internal temperature was raised to 160 ° C. to heat and dissolve the contents. Then, the pressure was lowered to 23 kPa over 5 minutes, and then the reaction was carried out for 90 minutes while distilling and removing phenol. Then, the pressure was lowered to 9.3 kPa over 90 minutes, further lowered to 0.7 kPa over 30 minutes, and then the temperature was raised to 170 ° C. for 60 minutes while distilling and removing phenol and unreacted diol. The reaction was carried out to obtain a polycarbonate diol.
The Mn of the polycarbonate diol was 800, and the copolymer composition ratio of 1,4-BD / iSB calculated by the same method as in Synthesis Example 3 was 55/45 (molar ratio).
The above polycarbonate diol was placed in a reactor, and the gas phase in the reactor was replaced with carbon dioxide in a state where the carbon dioxide cylinder and the inside of the reactor were connected. Next, PO and carbon dioxide were addition-polymerized using a TBA-DMC catalyst and terrorahydrofuran as a solvent while constantly pressurizing the inside of the reactor with carbon dioxide so as to be 1.5 MPa. After the polymerization, tetrahydrofuran was degassed and removed to obtain a polycarbonate diol as a precursor polymer a2-1.
In the same manner as in Synthesis Example 1, 1-isocyanatepropylmethyldimethoxysilane was reacted with the hydroxyl group which is the terminal group of the precursor polymer a2-1 to obtain the polymer A2-1.

(Synthesis Example 8: Polymer A3-1)
PPG of Mn 1,000 was put into the reactor, and the gas phase in the reactor was replaced with carbon dioxide in a state where the carbon dioxide cylinder and the inside of the reactor were connected. Next, PO and carbon dioxide were addition-polymerized using a TBA-DMC catalyst while the inside of the reactor was always pressurized with carbon dioxide so as to be 1.5 MPa, and the polycarbonate diol as the precursor polymer a3-1 was obtained. Obtained.
In the same manner as in Synthesis Example 1, 1-isocyanatepropylmethyldimethoxysilane was reacted with the hydroxyl group which is the terminal group of the precursor polymer a3-1 to obtain the polymer A3-1.

(Synthesis Example 9: Polymer C1)
PO was addition-polymerized to the PPG in the same manner as in the case of obtaining the precursor polymer a1-1 in Synthesis Example 1, except that the polycarbonate diol having an Mn of 1,700 in Synthesis Example 1 was used as a PPG having Mn 1,000. , Precursor polymer c1 was obtained. In the same manner as in Synthesis Example 1 except that the precursor polymer a1-1 in Synthesis Example 1 is used as the precursor polymer c1, 1-isocyanatepropylmethyldimethoxysilane is reacted with the hydroxyl group which is the terminal group of the precursor polymer c1. Polymer C1 was obtained.
(Synthesis Example 10: Polymer C2)
In the same manner as in Synthesis Example 1, 1-isocyanatepropylmethyldimethoxysilane is reacted with the hydroxyl group of the polycarbonate diol having Mn of 1,700 produced as the raw material of the precursor polymer a1-1 in Synthesis Example 1 to form a polymer. I got C2.

<Manufacturing of curable composition>
(Examples 1 to 8)
Examples 1 to 6 are Examples, and Examples 7 and 8 are Comparative Examples.
The polymers A1-1, A1-3, A1-4, A1-5, A1-6, A3-1, C1 and C2 obtained in Synthesis Examples 1, 3 to 6, 8 to 10 are shown in Table 2. Additive 1 of the formulation (unit: parts by mass) was used, and these were mixed in the formulation shown in Table 3 to prepare a curable composition.
With respect to the cured product of the obtained curable composition, M50, maximum point cohesive force, and maximum point elongation were measured by the above method. Further, the moldability and weather resistance were evaluated by the above method. The results are shown in Table 3.

<Other ingredients>
The additives listed in Table 2 are as follows.
DINP: Diisononyl phthalate, Sansosizer DINP, New Japan Chemical Co., Ltd. product name.
Whiten SB: Heavy calcium carbonate, product name of Shiraishi Kogyo Co., Ltd.
CCR: Glue calcium carbonate, white gloss CCR, product name of Shiraishi Kogyo Co., Ltd.
Disparon # 6500: Hydrogenated castor oil-based chixo-imparting agent, Kusumoto Kaseisha 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.
TINUVIN326: Benzotriazole-based UV absorber, product name of BASF.
IRGANOX1010: Hindered phenolic antioxidant, BASF product name.
U-220H: Dibutyl tin bis (acetylacetonate), product name of Nitto Kaseisha.

In Examples 1, 2, 5, 6 and 7, the M50 of the cured product is almost the same.
In Example 1 using the polymer containing a carbonate group, the maximum point cohesive force and the maximum point elongation were improved as compared with Example 7 in which the polymer containing no carbonate group was used. The weather resistance was comparable. In Example 2 using the polymer containing a carbonate group, the maximum point cohesive force was the same as in Example 7, and the maximum point elongation was improved. The weather resistance has also improved. In Example 5 using the polymer containing a carbonate group, the maximum point elongation was improved as compared with Example 7. In Example 6 using the polymer containing a carbonate group, the maximum point cohesive force and the maximum point elongation were improved as compared with Example 7.
In Examples 3 and 4 using the polymer containing a carbonate group, the M50 of the cured product, the maximum point cohesive force, and the maximum point elongation were improved as compared with Example 7.
In Example 8 in which a polymer containing no unit based on alkylene oxide was used, the curable composition had poor moldability, and the cured product was not evaluated.

Claims (20)

A cured product made of a polycarbonate polymer having a unit based on a reactive silicon group, a carbonate group, and an alkylene oxide represented by the following formula 1 in one molecule and having a number average molecular weight of 4,000 to 50,000. Sex material.
−SiX _a R ¹ _3-a formula 1
In formula 1, R ¹ 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 or a hydrolyzable group, and a is 1-3. It indicates an integer, and when a is 1, R ¹ 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 curable material according to claim 1, wherein the unit based on alkylene oxide includes a unit based on propylene oxide. The curable material according to claim 1 or 2, wherein the number of carbonate groups per molecule of the polycarbonate polymer is 3.0 or more. The invention according to any one of claims 1 to 3, wherein the carbonate group / alkylene oxide unit is 0.01 to 1, which represents the molar ratio of the content of the carbonate group to the content of the unit based on the alkylene oxide. Curable material. The curable material according to any one of claims 1 to 4, wherein the number of the reactive silicon groups present in the polycarbonate polymer is more than 0.5 on average per molecule. The curable material according to any one of claims 1 to 5, which has a molecular weight distribution of 1.0 to 3.0. A curable composition comprising the curable material according to any one of claims 1 to 6 and a curing catalyst. A cured product of the curable composition according to claim 7. The cured product according to claim 8, which is for a sealing material. The cured product according to claim 8, which is for an adhesive. A precursor polymer or a precursor polymer having two or more carbonate groups, a unit based on an alkylene oxide, and an active hydrogen-containing group capable of reacting with a silylating agent at the terminal, and having a number average molecular weight of 4,000 to 50,000. A derivative having a reactive end group capable of reacting with a silylating agent introduced into the terminal of the precursor polymer and a reactive silicon group represented by the following formula 1 and having the active hydrogen-containing group or the reactivity. A method for producing a polycarbonate polymer, which comprises reacting a terminal group with a silylating agent having a group capable of reacting with the terminal group.
−SiX _a R ¹ _3-a formula 1
In formula 1, R ¹ 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 or a hydrolyzable group, and a is 1-3. It indicates an integer, and when a is 1, R ¹ 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 method for producing a polycarbonate polymer according to claim 11, wherein the precursor polymer is obtained by addition polymerization of an alkylene oxide to a hydroxyl group of a polycarbonate polyol. The method for producing a polycarbonate polymer according to claim 11, wherein the precursor polymer is obtained by addition polymerization of an alkylene oxide and carbon dioxide to a hydroxyl group of a polycarbonate polyol. The method for producing a polycarbonate polymer according to claim 12 or 13, wherein the polycarbonate polyol is a polycarbonate diol obtained by polycondensing a diol compound represented by the following formula 2 and a carbonate compound represented by the following formula 3.
HO-R ^2- OH formula 2
In Formula 2, R ² represents a substituted or unsubstituted divalent hydrocarbon group having 3 to 20 carbon atoms.
R ^3- OC (O) -OR ⁴ formula 3
In formula 3, R ³ and R ⁴ are independently alkyl or phenyl groups having 1 to 20 carbon atoms, or R ³ and R ⁴ are bonded to each other to form a ring. The diol compounds are 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, and 1,10-. The production of the polycarbonate polymer according to claim 14, which is one or more selected from the group consisting of decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, and isosorbide. Method. The method for producing a polycarbonate polymer according to claim 14 or 15, wherein the polycarbonate diol has a number average molecular weight of 250 to 10,000. The method for producing a polycarbonate polymer according to claim 11, wherein the precursor polymer is obtained by addition polymerization of an alkylene oxide and carbon dioxide to a polyol containing no carbonate group. A polycarbonate polymer having a unit based on a reactive silicon group, a carbonate group, and an alkylene oxide represented by the following formula 1 in one molecule and having a number average molecular weight of 4,000 to 50,000.
−SiX _a R ¹ _3-a formula 1
In formula 1, R ¹ 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 or a hydrolyzable group, and a is 1-3. It indicates an integer, and when a is 1, R ¹ 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. Polycarbonate having a reactive silicon group represented by the following formula 10, two or more carbonate groups, and a repeating unit based on an alkylene oxide in one molecule and having a number average molecular weight of 4,000 to 50,000. Polymer.
−SiX ¹⁰ _a R ¹⁰ _3-a formula 10
In formula 10, R ¹⁰ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halo hydrocarbon group having 1 to 20 carbon atoms, and X ¹⁰ represents a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms. Shown, a represents an integer from 1 to 3, and when a is 1, R ¹⁰ may be the same or different from each other, and when a is 2 or 3, X ¹⁰ may be the same or different from each other. The following formula has one or more reactive silicon groups, two or more carbonate groups, and a repeating unit based on alkylene oxide in one molecule, and has a number average molecular weight of 4,000 to 50,000. Polycarbonate polymer represented by 11.
X ¹⁰ _a R ¹⁰ _3-a Si-Q-[(OR ¹¹ ) _n (OR ^11- OC (O)) _m (OR ^2- OC (O)) _t ] ^{-OR 21-} O −Q−SiX ¹⁰ _a R ¹⁰ _3-a formula 11
In formula 11, X ¹⁰ represents a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and R ¹⁰ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halo hydrocarbon group having 1 to 20 carbon atoms. shows, Q is a divalent hydrocarbon group having a substituted or unsubstituted 1 to 6 carbon atoms, or -NHC (O) ^{-R 31} - ^{indicates, R 31} is 2 substituted or unsubstituted 1 to 6 carbon atoms It shows a valent hydrocarbon group, one of which is bonded to a silicon atom, R ¹¹ shows a substituted or unsubstituted divalent hydrocarbon group having 2 to 4 carbon atoms, and R ² and R ²¹ are respectively. Independently indicates a substituted or unsubstituted divalent hydrocarbon group having 3 to 20 carbon atoms, n is an integer of 1 to 900, t is an integer of 0 to 50, and m is an integer of 0 to 500. And n + t + m is an integer of 3 or more. a is an integer of 1 to 3, and when a is 1, R ¹⁰ may be the same or different from each other, and when a is 2 or 3, X ¹⁰ may be the same or different from each other.