JP5338661B2 - Method for producing oxyalkylene polymer - Google Patents

Abstract

Storage stability of an oxyalkylene polymer (P), wherein a reactive silicon group is bound to a polyoxyalkylene chain by a urethane bond, is improved. Specifically, an oxyalkylene polymer (P) is produced by urethanizing a hydroxy group-containing polymer (pP) having a polyoxyalkylene chain and a hydroxy group with an isocyanate group-containing compound (U) represented by the general formula (1) below in the presence of a tetravalent monoalkyl tin catalyst (S). (Si(-X1)a(-R1)3-a)-Q1-NCO (1) In the formula (1), X1 represents an alkoxy group having 1-6 carbon atoms; R1 represents an optionally substituted monovalent organic group having 1-20 carbon atoms; Q1 represents a divalent organic group having 1-20 carbon atoms; and a represents an integer of 1-3.

Description

  The present invention relates to a method for producing an oxyalkylene polymer in which a reactive silicon group is bonded to a polyoxyalkylene chain via a urethane bond.

A curable composition having a polymer having a reactive silicon group at the terminal of a polyoxyalkylene chain (also referred to as a modified silicone polymer) as a curing component is cured by moisture to form a cured product having excellent rubber elasticity. Therefore, the curable composition is widely used as an adhesive, a coating agent, and a sealing material. Among them, a curable composition containing a modified silicone polymer having a methyldimethoxysilyl group at the end of a polyoxyalkylene chain as a curing component is widely accepted as a sealing material due to its excellent elongation property (patent) Reference 1).
In addition, a curable composition containing a polymer having a polyoxyalkylene chain and a trialkoxysilyl group as a curing component has a high curing speed and a high crosslinking density, so that it can be used as a fast-curing adhesive, coating agent, or sealing material. Useful (see Patent Document 2).

Patent Document 3 below describes a polymer in which a trialkoxysilyl group is bonded to the end of a polyoxyalkylene chain via a urethane bond. As one of the methods for producing the polymer, a method of urethanizing a polyoxypropylene polyol and an isocyanate-substituted trialkoxysilane compound having one isocyanate group in the molecule is described. It is described that a urethane polymerization catalyst such as dibutyltin dilaurate may be used.
General examples of the urethane polymerization catalyst include organic tin compounds such as dibutyltin dilaurate and dioctyltin dilaurate (for example, Patent Document 4 below), organic amines such as triethylenediamine and triethylamine, and other salts. Furthermore, other urethane polymerization catalysts include metal salt compounds such as bismuth, cobalt, and iron.

In Patent Document 5 below, as a curing catalyst for an organic polymer having a hydrolyzable silicon-containing group, tin (II) carboxylate such as tin 2-ethylhexanoate and tin n-octylate, and dibutyltin dilaurate and dibutyltin malate It is described that organotin (IV) compounds such as are excellent in curing speed and cured physical properties.
Japanese Patent Laid-Open No. 03-072527 Japanese Unexamined Patent Publication No. 03-047825 JP-A-10-245482 JP 2003-87742 A Japanese Patent No. 3779953

  According to the knowledge of the present inventors, using dibutyltin dilaurate as a catalyst, a polymer obtained by producing a “polymer having a reactive silicon group bonded to a polyoxyalkylene chain via a urethane bond” was obtained. May have poor storage stability. As a cause of poor storage stability, as described in Patent Document 5, dibutyltin dilaurate is a “polymer in which a reactive silicon group is bonded to a polyoxyalkylene chain via a urethane bond”. Since a compound that can be used as a curing catalyst of the polymer, if there is even a small amount of water, the reaction between the reactive silicon group of the polymer and moisture occurs due to the action of dibutyltin dilaurate contained as a residual catalyst in the polymer. This is thought to be due to the increased viscosity. As a method for improving the storage stability, generally, there is a method of reducing the amount of catalyst, using a less active catalyst, etc., but in this method, the urethanization reaction does not proceed sufficiently, Or there is a problem that the reaction takes too long. Therefore, improvement of the storage stability of the polymer which has a reactive silicon group through the urethane bond in the polyoxyalkylene chain is calculated | required.

  The present invention has been made in view of the above circumstances, and it is possible to improve the storage stability of an oxyalkylene polymer in which a reactive silicon group is bonded to a polyoxyalkylene chain via a urethane bond. A method for producing a coalescence is provided.

That is, the present invention has the following gist.
(1) A method for producing an oxyalkylene polymer (P) in which a reactive silicon group is bonded to a polyoxyalkylene chain via a urethane bond,
A hydroxyl group-containing polymer (pP) having a polyoxyalkylene chain and a hydroxyl group and an isocyanate group-containing compound (U) represented by the following general formula (1) are present in the presence of a tetravalent monoalkyltin catalyst (S). A process for producing an oxyalkylene polymer, comprising the step of urethanization reaction.
^{_{(Si (-X 1) a (}} -R 1) 3-a) -Q 1 -NCO ··· (1)
(Wherein, X ¹ represents an alkoxy group having 1 to 6 carbon atoms, and R ¹ represents a monovalent organic group having 1 to 20 carbon atoms which may have a substituent (excluding an alkoxy group). , Q ¹ represents a divalent organic group having 1 to 20 carbon atoms, a is an integer of 1-3. However, a plurality of R ¹ when R ¹ there are a plurality may be the same or different from each other , a plurality of X ¹ may be the same or different when X ¹ is more present.)
(2) The tetravalent monoalkyltin catalyst (S) is represented by the following general formula (I):
R ¹¹ Sn (OCOR ¹² ) ₃ (I)
(In the formula, R ¹¹ represents an alkyl group having 4 to 8 carbon atoms, and R ¹² represents an alkyl group having 2 to 17 carbon atoms. Three R ¹² existing in one molecule may be the same or different from each other. May be good.)
A first tin catalyst (S1) represented by the general formula (II):
R ¹³ Sn (SR ¹⁴ ) ₃ (II)
(In the formula, R ¹³ represents an alkyl group having 1 to 8 carbon atoms. R ¹⁴ represents an alkyl group having 8 to 18 carbon atoms. Three R ¹⁴ existing in one molecule are the same or different from each other. May be.)
The manufacturing method of the oxyalkylene polymer as described in said (1) which is a 2nd tin catalyst (S2) represented by these.
(3) The manufacturing method of the oxyalkylene polymer as described in said (1) or (2) whose reaction temperature of the said urethanation reaction is 50-200 degreeC.
(4) The method for producing an oxyalkylene polymer according to any one of (1) to (3), wherein the urethanization reaction is performed in an inert gas atmosphere.
(5) In any one of the above (1) to (4), the amount of the tetravalent monoalkyltin catalyst (S) used is 1 ppm to 100 ppm on a mass basis with respect to the hydroxyl group-containing polymer (pP). The manufacturing method of the oxyalkylene polymer of description.
(6) The manufacturing method of the oxyalkylene polymer in any one of said (1)-(5) whose a in the said General formula (1) is 3.
(7) In the case of the general formula (1) a in the 2, Q ¹ is a methylene group, the (1) to (5) The method of producing oxyalkylene polymer according to any one of.
( 8 ) The molar ratio (isocyanate group / hydroxyl group) of the total number of isocyanate groups of the isocyanate group-containing compound (U) to the total number of hydroxyl groups of the hydroxyl group-containing polymer (pP) is 0.80 to 1.10. (1) The manufacturing method of the oxyalkylene polymer in any one of ( 7 ).
( 9 ) The method for producing an oxyalkylene polymer according to any one of the above (1) to ( 8 ), wherein the hydroxyl group-containing polymer (pP) has a number average molecular weight per hydroxyl group of 1000 to 30000.
( 10 ) Production of the oxyalkylene polymer according to any one of (1) to ( 9 ), wherein the hydroxyl group-containing polymer (pP) has a hydroxyl value of 1.6 to 60.0 mgKOH / g. Method.
( 11 ) The hydroxyl group-containing polymer (pP-1) is a hydroxyl group-containing polymer (pP-1) obtained by ring-opening polymerization of an alkylene oxide to a compound having an active hydrogen atom in the presence of a double metal cyanide complex. The manufacturing method of the oxyalkylene polymer in any one of said (1)-( 10 ).
(12) While containing the oxyalkylene polymer obtained by the manufacturing method in any one of said (1)-(11) as a hardening component, the tetravalent monoalkyl tin catalyst (S) which is a reaction catalyst residue is contained. A curable composition included.

  The oxyalkylene polymer in which the reactive silicon group is bonded to the polyoxyalkylene chain obtained by the production method of the present invention via a urethane bond can improve the storage stability.

<Hydroxyl-containing polymer (pP)>
The hydroxyl group-containing polymer (pP) used in the present invention is a polymer having a polyoxyalkylene chain and a hydroxyl group.
The polyoxyalkylene chain in the hydroxyl group-containing polymer (pP) is preferably composed of oxyalkylene polymer units formed by ring-opening polymerization of an alkylene oxide having 2 to 6 carbon atoms. Specifically, it is more preferably composed of oxyalkylene polymer units formed by ring-opening polymerization of one or more alkylene oxides selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and hexylene oxide. It is particularly preferable that the polymer consists of oxyalkylene polymer units formed by ring-opening polymerization of propylene oxide. When the polyoxyalkylene chain is composed of two or more oxyalkylene polymer units, the arrangement of the two or more oxyalkylene polymer units may be block or random.
The hydroxyl value of the hydroxyl group-containing polymer (pP) is preferably 1.6 to 60.0 mgKOH / g, more preferably 3.0 to 15.0 mgKOH / g, and particularly preferably 5.0 to 12 mgKOH / g.

The number average molecular weight per hydroxyl group of the hydroxyl group-containing polymer (pP) is preferably 1000 to 30000, more preferably 3000 to 20000.
The number average molecular weight (Mn) in the present invention means a number average molecular weight (Mn) in terms of standard polystyrene measured by tetrahydrofuran as a mobile phase by gel permeation chromatography (GPC).
When the number average molecular weight of the hydroxyl group-containing polymer (pP) is in the above range, the molecular weight of the obtained oxyalkylene polymer (P) is in a good range in terms of viscosity and mechanical properties of the cured product.

As the hydroxyl group-containing polymer (pP), a hydroxyl group-containing polymer (pP-1) obtained by ring-opening polymerization of alkylene oxide on a compound having an active hydrogen atom in the presence of a double metal cyanide complex is preferable.
The double metal cyanide complex is preferably a double metal cyanide complex having an organic ligand. The organic ligand is preferably an ether ligand or an alcohol ligand. Specific examples of the ether-based ligand include ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), and triethylene glycol dimethyl ether. Specific examples of the alcohol-based ligand include tert-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, and ethylene glycol mono-tert-butyl ether. It is done.
As the double metal cyanide complex, zinc hexacyanocobaltate is particularly preferable.

The compound having an active hydrogen atom is preferably an organic compound having an active hydrogen atom, more preferably a compound having a hydroxy group or an amino group, and particularly preferably a compound having 1 to 4 hydroxy groups. 1 type may be used for the compound which has an active hydrogen atom, and 2 or more types may be used for it.
Specific examples of the organic compound having an active hydrogen atom include ethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexamethylene glycol, hydrogenated bisphenol A, neopentyl glycol, polybutadiene glycol, diethylene glycol, triethylene glycol, polyethylene glycol. , Allyl alcohol, methallyl alcohol, glycerin, trimethylol methane, trimethylol propane, pentaerythritol and other alcohols; polyoxypropylene monool, polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene monool, polyoxyethylene One or more polymeric alcohols selected from the group consisting of diols and polyoxyethylenetriols Le, and the like. The number average molecular weight per hydroxyl group of the polymeric alcohol is preferably 300-1500.
1 type may be used for the compound which has an active hydrogen atom, and 2 or more types may be used for it. When a compound having two or more active hydrogen atoms is used, it is preferable to use a polymer alcohol having two hydroxy groups and a polymer alcohol having three hydroxy groups.

  In the present invention, when the hydroxyl group-containing polymer (pP-1) is used, after purifying and removing the composite metal cyanide complex contained as a polymerization residue, it may be urethanated with the isocyanate group-containing compound (U). You may make a urethanation reaction with an isocyanate group containing compound (U), without refining and removing a double metal cyanide complex.

<Isocyanate group-containing compound (U)>
The isocyanate group-containing compound (U) used in the present invention is a compound represented by the following general formula (1). A in a formula is an integer of 1-3.
^{_{(Si (-X 1) a (}} -R 1) 3-a) -Q 1 -NCO ··· (1)
In the formula (1), R ¹ is a monovalent organic group having 1 to 20 carbon atoms that may have a substituent.
However, R ¹ is not an alkoxy group.
R ¹ is preferably an alkyl group having 8 or less carbon atoms, a fluoroalkyl group having 8 or less carbon atoms, or a phenyl group, and is a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, or a phenyl group. More preferably. When a plurality of R ¹ are present in the same molecule, the plurality of R ¹ may be the same as or different from each other.

In the above formula (1), ^{X 1} represents an alkoxy group having 1 to 6 carbon atoms. Specific examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. A methoxy group is particularly preferred. Incidentally, when the X ¹ there are a plurality in the same molecule, the plurality of X ¹ may be the same or different from each other.
Wherein ^{(1), Q} 1 represents a divalent organic group having 1 to 20 carbon atoms. A C1-C10 alkylene group is preferable and a trimethylene group and a methylene group are more preferable from a viewpoint of availability.

The isocyanate group-containing compound (U) is preferably an isocyanate group-containing compound (U-1) in which a in the general formula (1) is 3. The isocyanate group-containing compound (U-1) is represented by the following general formula (2).
_{^{(Si (-X 1) 3)}} -Q 1 -NCO ··· (2)
X ¹ and Q ¹ in the general formula (2) are the same as those in the general formula (1), including preferred embodiments thereof.
In addition, as the isocyanate group-containing compound (U-2), those in which a in the general formula (1) is 2 and Q ¹ is a methylene group are also preferable.
When the isocyanate group-containing compounds (U-1) and (U-2) are used, an oxyalkylene polymer (P) excellent in fast curability can be obtained.
Specific examples of the isocyanate group-containing compound (U-1) include 1-isocyanate methyltrimethoxysilane, 2-isocyanateethyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatebutyltrimethoxysilane, 3-isocyanate. Examples include pentyltrimethoxysilane, 1-isocyanatomethyltriethoxysilane, 2-isocyanatoethyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, 1-isocyanatopropyltrimethoxysilane, and 1-isocyanatopropyltriethoxysilane.
Specific examples of the isocyanate group-containing compound (U-2) include 1-isocyanatomethyldimethoxymethylsilane.

<Urethaneization polymerization catalyst>
In the present invention, when producing an oxyalkylene polymer (P) in which a reactive silicon group is bonded to a polyoxyalkylene chain via a urethane bond, a tetravalent monoalkyltin catalyst (S) (hereinafter, simply referred to as a “polyalkylene chain”). Tin catalyst (S) may be used). The “tetravalent monoalkyltin catalyst (S)” in the present specification is a compound in which an organic group is bonded to tetravalent tin, and the alkyl group directly bonded to tin (Sn) is 1 Compounds.

As the tin catalyst (S), a first tin catalyst (S1) represented by the following general formula (I) or a second tin catalyst (S2) represented by the following general formula (II) is preferable. The first tin catalyst (S1) and the second tin catalyst (S2) may be used in combination.
R ¹¹ Sn (OCOR ¹² ) ₃ (I)
In the above formula ^{(I), R 11} represents an alkyl group of 4-8 carbon ^{atoms, R 12} represents an alkyl group having 2 to 17 carbon atoms. Three R ¹² present in one molecule may be the same or different from each other.
R ¹³ Sn (SR ¹⁴ ) ₃ (II)
In the formula ^{(II), R 13} represents an alkyl group having 1 to 8 carbon atoms. R ¹⁴ represents an alkyl group having 8 to 18 carbon atoms. Three R ¹⁴ existing in one molecule may be the same as or different from each other.

In the above formula (I), R ¹¹ is an alkyl group having 4 to 8 carbon atoms, and may be linear or include a branched structure. _{Preferably, -n-C 4 H 9,} -n-C 6 H 13, a _{-n-C 8 H 17.} Particularly _-n-C 4 _{H 9} is preferred.
In the above formula (I), R ¹² is an alkyl group having 2 to 17 carbon atoms, and may be linear or include a branched structure. _{Preferably, -C 2 H 5, -n-} C 5 H 11, -n-C 7 H 15, -n-C 9 H 19, is a _-n-C 11 _{H 23} or _-n-C 17 _{H 35} . Particularly _{-n-C 7 H 15} are preferable.
In particular, the first tin catalyst (S1) in which R ¹¹ in the above formula (I) is —nC ₄ H ₉ and R ¹² is —nC ₇ H ₁₅ , such as SCAT-24 (product name) , Manufactured by Sansha Co., Ltd.).
A 1st tin catalyst (S1) may be used individually by 1 type, and may be used in combination of 2 or more type.

In the above formula (II), R ¹³ is an alkyl group having 1 to 8 carbon atoms, and may be linear or include a branched structure. Preferred examples include methyl group, butyl group, octyl group and the like.
In the above formula (II), R ¹⁴ is an alkyl group having 8 to 18 carbon atoms and may be linear or include a branched structure. Preferred examples include octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group and the like.

Examples of the second tin catalyst (S2) when R ¹³ is a methyl group include monomethyltin tri (octylsulfanyl), monomethyltin tri (dodecylsulfanyl), monomethyltin tri (stearylsulfanyl) and the like. it can. Monomethyltin tri (dodecylsulfanyl) is preferred.
Examples of the second tin catalyst (S2) when R ¹³ is a butyl group include monobutyltin tri (octylsulfanyl), monobutyltin tri (dodecylsulfanyl), and monobutyltin tri (stearylsulfanyl). . Monobutyltin tri (dodecylsulfanyl) is preferable.
Examples of the second tin catalyst (S2) when R ¹³ is an octyl group include monooctyltin tri (octylsulfanyl), monooctyltintri (dodecylsulfanyl), and monooctyltintri (stearylsulfanyl). be able to. Monooctyltin tri (dodecylsulfanyl) is preferable.
In particular, the second tin catalyst (S2) in which R ¹³ in the above formula (II) is -nC ₄ H ₉ and R ¹⁴ is -nC ₁₂ H ₂₅ , for example, SCAT-9A (product name , Manufactured by Sansha Co., Ltd.).
A 2nd tin catalyst (S2) may be used individually by 1 type, and may be used in combination of 2 or more type.

<Method for producing oxyalkylene polymer (P)>
The method for producing the oxyalkylene polymer (P) of the present invention is a step of subjecting the hydroxyl group-containing polymer (pP) and the isocyanate group-containing compound (U) to a urethanization reaction in the presence of a tin catalyst (S). Have For example, the tin catalyst (S) is added to the hydroxyl group-containing polymer (pP) and stirred, and then the isocyanate group-containing compound (U) is added and maintained at the reaction temperature for urethanization reaction.
Alternatively, the isocyanate group-containing compound (U) may be added to the hydroxyl group-containing polymer (pP) and stirred, and then a tin catalyst (S) may be added and maintained at a predetermined reaction temperature for urethanization reaction.
The reaction temperature of the urethanization reaction is preferably 50 to 200 ° C, particularly preferably 70 to 150 ° C. When the reaction temperature of the urethanization reaction is within the above range, good catalytic activity of the tin catalyst (S) can be obtained when the urethanization reaction is performed.
The urethanization reaction is preferably performed in an inert gas atmosphere, preferably in a nitrogen gas atmosphere.

An oxyalkylene polymer (P) is obtained by the urethanization reaction. Specifically, “an oxyalkylene polymer (P) in which a reactive silicon group is introduced into a polyoxyalkylene chain of a hydroxyl group-containing polymer (pP) via a urethane bond” is obtained. The reactive silicon group is a group corresponding to “—Si (—X ¹ ) _a (—R ¹ ) _3-a ” of the isocyanate group-containing compound (U). Specifically, “(Si (—X ¹ ) _a (—R ¹ ) _3-a ) -Q ¹ —NHCOO—” derived from the isocyanate group-containing compound (U) is bonded to the polyoxyalkylene chain. An oxyalkylene polymer (P) is obtained.
The oxyalkylene polymer (P) has a reactive silicon group as a substituent in the side chain or terminal. More preferably, the substituent at the terminal has a reactive silicon group.

The amount of the tetravalent monoalkyltin catalyst (S) used is preferably from 1 ppm to 100 ppm, more preferably from 10 to 50 ppm, based on the hydroxyl group-containing polymer (pP) (mass basis, the same shall apply hereinafter). When the amount of the tin catalyst (S) used is 1 ppm or more, the urethanization reaction proceeds well, and when it is 100 ppm or less, good storage stability of the oxyalkylene polymer (P) is obtained.
Moreover, when using the said hydroxyl-containing polymer (pP-1) as a hydroxyl-containing polymer (pP), the usage-amount of the composite metal cyanide complex used in manufacture of this hydroxyl-containing polymer (pP-1) is 100 ppm or more. If so, the amount of the tin catalyst (S) used is preferably 1 to 50 ppm, more preferably 1 to 20 ppm. Moreover, when the usage-amount of this composite metal cyanide complex is less than 100 ppm, the usage-amount of a tin catalyst (S) is preferable 20-100 ppm, and 20-50 ppm is more preferable.

According to the present invention, excellent storage stability is achieved by urethanating a hydroxyl group-containing polymer (pP) and an isocyanate group-containing compound (U) in the presence of a tetravalent monoalkyltin catalyst (S). In addition, an “oxyalkylene polymer (P) having a reactive silicon group in the polyoxyalkylene chain via a urethane bond” is obtained.
The oxyalkylene polymer (P) obtained has good curability, and in particular, in the general formula (1), the isocyanate group-containing compound (U-1) in which a is 3, or the general formula (1) The oxyalkylene polymer (P) obtained by using an isocyanate group-containing compound (U-2) in which a is 2 and Q ¹ is a methylene group is excellent in fast curability.
Thus, the oxyalkylene polymer (P) which has favorable sclerosis | hardenability and storage stability is obtained by using a tetravalent monoalkyl tin catalyst (S) as a catalyst of a urethanation reaction. The reason for this is not clear, but the tin catalyst (S) exhibits a good catalytic activity at the reaction temperature of the urethanization reaction, and has characteristics as a metal-based temperature-sensitive catalyst that does not exhibit a catalytic activity when stored at room temperature. I guess that.

In the urethanization reaction between the hydroxyl group-containing polymer (pP) and the isocyanate group-containing compound (U), the total number of isocyanate groups of the isocyanate group-containing compound (U) relative to the total number of hydroxyl groups of the hydroxyl group-containing polymer (pP) used. The molar ratio (isocyanate group / hydroxyl group) is preferably 0.80 to 1.10, and more preferably 0.85 to 1.05.
When the value of the “isocyanate group / hydroxyl group” is within the above range, the storage stability of the resulting oxyalkylene polymer (P) becomes better. The reason is that when the value of “isocyanate group / hydroxyl group” is within the above range, even if a hydroxyl group remains in the obtained oxyalkylene polymer (P), the hydroxyl group and the oxyalkylene polymer (P) This is thought to be because the crosslinking reaction with the reactive silicon group is suppressed, and the thickening during storage is suppressed. In addition, side reactions in the urethanization reaction (Allophanation reaction, Isocyanuration reaction, etc.) are suppressed, and generation of reactive silicon groups due to the side reaction is unlikely to occur. It is thought that stickiness is difficult to occur.

<Curable composition>
The oxyalkylene polymer (P) obtained by the production method of the present invention is suitably used as a component of the curable composition. The curable composition comprising the oxyalkylene polymer (P) as a curing component is capable of obtaining a cured product having a high crosslinking density because of rapid hydrolysis and crosslinking reaction of hydrolyzable silicon groups due to moisture in the air at room temperature. And has excellent storage stability.
The oxyalkylene polymer (P) can be used without removing the tetravalent monoalkyltin catalyst (S) contained as a reaction catalyst residue.
In addition to the oxyalkylene polymer (P), the curable composition may appropriately contain a curing catalyst, a filler, a plasticizer, an adhesion-imparting agent, a dehydrating agent, a thixotropic agent, an anti-aging agent, and the like. . In addition to the oxyalkylene polymer (P), a component having a reactive silicon group may be used in combination.
The curable composition may contain a curing catalyst in advance and be stored under dehydrating conditions, and may be a one-component type that reacts with moisture in the atmosphere at the time of curing, or the curing catalyst is mixed immediately before curing. Further, it may be a two-component type that is cured by moisture in the mixture and in the atmosphere.

(Curing catalyst)
The curing catalyst is a compound that promotes a hydrolysis reaction and / or a crosslinking reaction in the reactive silicon group of the oxyalkylene polymer (P). Specific examples include organotin (IV) carboxylates such as dibutyltin diacetate and dibutyltin dilaurate; (nC ₄ H ₉ ) ₂ Sn (SCH ₂ COO) ₂ , (nC ₈ H ₁₇ ) ₂ Sn (SCH ₂ COO) ₂ , (n-C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COO) ₂ , (n-C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOCH ₂ CH ₂ OCOCH ₂ S) ₂ , ( _{n-C 4 H 9) 2} Sn (SCH 2 COO (iso-C 8 H 17)) 2, (n-C 8 H 17) 2 Sn (SCH 2 COO (iso-C 8 H 17)) 2, ( _{n-C 8 H 17) 2} Sn (SCH 2 COO (n-C 8 H 17)) 2, (n-C 4 H 9) sulfur-containing organic tin compounds such as _{2 SnS; (n-C 4} H 9) ₂ SnO, (n-C ₈ H ₁₇ ) Organotin oxide such as ₂ SnO; selected from the group consisting of said organotin oxide and, for example, ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, etc. the reaction product of one or more ester _{compounds; (n-C 4 H 9} ) 2 Sn (acac) 2, (n-C 8 H 17) 2 Sn (acac) 2, (n-C 4 H 9 ) ₂ Sn (OC ₈ H ₁₇ ) (acac), (n-C ₄ H ₉ ) ₂ Sn (OC (CH ₃ ) CHCO ₂ C ₂ H ₅ ) ₂ , (n-C ₈ H ₁₇ ) ₂ Sn (OC _{(CH 3) CHCO 2 C 2} H 5) 2, (n-C 4 H 9) 2 Sn (OC 8 H 17) (OC (CH 3) CHCO 2 C 2 H 5) or the like sharpness of Tosuzu compound (provided that the acac represents an acetylacetonato _{ligand, OC (CH 3) CHCO 2} C 2 H 5 represents ethyl acetoacetate ligand.); And the Kiretosuzu compound, for example tetramethoxysilane, the reaction product of one or more alkoxysilane selected from the group consisting of tetraethoxysilane, and tetrapropoxysilane and the like; _{and, (n-C 4 H 9} ) 2 (CH 3 COO) SnOSn (OCOCH 3) (n _{-C 4 H 9) 2, (} n-C 4 H 9) 2 (CH 3 O) SnOSn (OCH 3) (n-C 4 H 9) 4 -valent such -SnOSn--containing organic tin compounds ₂ such as Of the tin compound.

In addition, as a curing catalyst, divalent tin carboxylates such as bis (2-ethylhexanoic acid) tin, di (n-octylic acid) tin, dinaphthenic acid tin and tin distearate; octylic acid, phosphoric acid, p-toluenesulfone Acid compounds such as acid and phthalic acid; Aliphatic monoamines such as butylamine, hexylamine, octylamine, decylamine, and laurylamine; Aliphatic diamines such as ethylenediamine and hexanediamine; Diethylenetriamine, triethylenetetramine, and tetraethylenepentamine Aliphatic polyamines such as piperidine, piperazine and other heterocyclic amines; Metaphenylenediamine and other aromatic amines; Monoethanolamine, diethanolamine and triethanolamine and other alkanolamines; Triethylamine and other trials Amine compounds such as various modified amines used as curing agents for epoxy resins; containing amino groups such as N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane Amine compounds to be used.
These compounds may be used alone or in combination of two or more. When using 2 or more types together, the combined use of the organotin (IV) compound from which activity differs, or the combined use of an organotin (IV) compound and an amine compound is preferable, for example.

It is preferable to use 0.001-10 mass parts for a curing catalyst with respect to 100 mass parts of oxyalkylene polymers (P), and it is more preferable to use 0.1-5.0 mass parts. By making the usage-amount of a curing catalyst 0.001 mass part or more, the cure rate of a curable composition can be accelerated | stimulated effectively, and a mechanical physical property and a weather resistance fall can be prevented by making it 10 mass parts or less.
When the curable composition contains other curing components having a reactive silicon group other than the oxyalkylene polymer (P), the amount of the curing catalyst used is the same as that of the oxyalkylene polymer (P). It is preferable to set it as said range with respect to 100 mass parts of total of a hardening component.

(filler)
Examples of the filler include calcium carbonate surface-treated with a fatty acid or a resin acid organic substance, colloidal calcium carbonate having an average particle diameter of 1 μm or less obtained by further finely powdering the calcium carbonate, and an average particle diameter of 1 to 3 μm manufactured by a precipitation method. Light calcium carbonate, heavy calcium carbonate with an average particle size of 1 to 20 μm, other calcium carbonates, fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black, magnesium carbonate, diatomaceous earth, calcined clay, Clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, glass balloon, glass balloon, organic resin balloon, wood flour, pulp, cotton chips, mica, walnut flour, rice flour, Powdery fillers such as graphite, fine aluminum powder, flint powder, etc. Fibers, glass filaments, carbon fibers, Kevlar fibers, fibrous fillers such as polyethylene fiber and the like.
In particular, when the glass balloon or the organic resin balloon is used, the specific gravity of the curable composition can be significantly reduced.
When the filler is used, the amount thereof used is preferably 1000 parts by mass or less, particularly 50 to 250, with respect to 100 parts by mass of the oxyalkylene polymer (P) (the total including the other curing components). Part by mass is preferred. Only 1 type may be used for a filler and it may use 2 or more types together.

(Plasticizer)
Known plasticizers can be used as the plasticizer, for example, phthalates such as dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate; dioctyl adipate, bis (2-methylnonyl) succinate, dibutyl sebacate, Aliphatic carboxylic acid esters such as butyl oleate; Alcohol esters such as pentaerythritol ester; Phosphate esters such as trioctyl phosphate and tricresyl phosphate; Epoxidized soybean oil, Dioctyl 4,5-epoxyhexahydrophthalate , Epoxy plasticizers such as epoxy benzyl stearate; chlorinated paraffins; polyester plasticizers such as polyesters obtained by reacting dibasic acids with dihydric alcohols; polyethers such as polyoxypropylene glycol and its derivatives Poly-α-methyl Styrene, styrene oligomers such as polystyrene; polybutadiene, butadiene - acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, hydrogenated polybutene, polymeric plasticizers such oligomers such as epoxidized polybutadiene, and the like. Only one type of plasticizer may be used, or two or more types may be used in combination.
When a plasticizer is used, the amount used thereof is preferably 1000 parts by mass or less, and 1 to 200 parts by mass with respect to 100 parts by mass of the oxyalkylene polymer (P) (a total including other curable components). Part is more preferred.
In particular, when the curable composition is used for applications such as an adhesive, it is preferable not to use a plasticizer because the amount of bleeding out (a liquid component that oozes out) from the cured product can be reduced and the coating film is less contaminated.

(Adhesiveness imparting agent)
By using an adhesiveness imparting agent, the adhesiveness between the curable composition and the substrate can be improved. Adhesive agents are known as so-called silane coupling agents such as (meth) acryloyloxy group-containing silanes, amino group-containing silanes, mercapto group-containing silanes, epoxy group-containing silanes, and carboxyl group-containing silanes. Compounds. These adhesiveness imparting agents may be used alone or in combination of two or more.
When using these adhesion-imparting agents, the amount used thereof is preferably 30 parts by mass or less with respect to 100 parts by mass of the oxyalkylene polymer (P) (the total including the other curing components). 0.1-10 mass parts is more preferable. When the usage-amount of an adhesive provision agent exceeds 30 mass parts, a curable composition may be hard and a softness | flexibility may become small too much.
Moreover, you may use together an epoxy resin or an epoxy resin and an epoxy resin hardening | curing agent depending on necessity as an adhesive provision agent. When the epoxy resin is added to the curable composition, the amount used thereof is 100 parts by mass or less with respect to 100 parts by mass of the oxyalkylene polymer (P) (a total including the other curing components). Preferably, 1-100 mass parts is more preferable. When the usage-amount of an epoxy resin exceeds 100 mass parts, the hardness of the hardened | cured material obtained may be high and a softness | flexibility may become small too much.

(Dehydrating agent)
By using a dehydrating agent, the storage stability of the curable composition can be enhanced. In particular, a dehydrating agent is preferably used when the curable composition is a so-called one-component composition, that is, a composition in which the curing component is cured by moisture in the atmosphere only by being put out from the sealed container.
Examples of the dehydrating agent include alkyl orthoformates; alkyl orthoacetates; hydrolyzable organosilicon compounds such as methyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane; hydrolyzable organotitanium compounds It is done.
When a dehydrating agent is added to the curable composition, the amount used is preferably 30 parts by mass or less with respect to 100 parts by mass of the oxyalkylene polymer (P) (the total including other curing components). 0.1 to 10 parts by mass is more preferable. When the usage-amount of a dehydrating agent exceeds 30 mass parts, hardening of a curable composition may become too late.

(Thixotropic agent)
Sagging can be prevented by adding a thixotropic agent. The thixotropic agent is not particularly limited, and examples thereof include hydrogenated castor oil and fatty acid amide. When the thixotropic agent is added to the curable composition, the amount of the desired sag-preventing property can be appropriately selected.

(Anti-aging agent)
By adding an anti-aging agent, weather resistance and light resistance can be improved. The anti-aging agent is not particularly limited, and one or more anti-aging agents selected from the group consisting of antioxidants, ultraviolet absorbers, light stabilizers and the like, which are generally added to polyurethane resins and the like, can be used. Specifically, as the anti-aging agent, various anti-aging agents such as hindered amine, benzotriazole, benzophenone, benzoate, cyanoacrylate, acrylate, hindered phenol, phosphorus and sulfur are known. From these, a preferable compound can be appropriately selected and added to the curable composition of the present invention. The amount used in the case of adding an anti-aging agent can be appropriately selected in such an amount that desired anti-aging properties can be obtained.

(Other additives)
In addition to the above-described additives, desired additives can be appropriately added to the curable composition. For example, inorganic pigments such as iron oxide, chromium oxide, and titanium oxide; organic pigments such as phthalocyanine blue and phthalocyanine green; fungicides; and foaming agents may be added. Oxyalkylene polymer (P) according to the present invention The curable composition containing is useful as a coating / sealing curable composition, as a building sealant, waterproof material, adhesive, and coating agent.
In particular, curability containing an oxyalkylene polymer (P) obtained by using an isocyanate group-containing compound (U-1) in which a in the general formula (1) is 3 as the isocyanate group-containing compound (U). The composition is excellent in rapid curability and is useful as an adhesive.

The present invention will be described in more detail with reference to the following examples, but the present invention should not be construed as being limited to these examples.
(Synthesis Example 1)
In the presence of zinc hexacyanocobaltate catalyst (264 mg) whose ligand is tert-butyl alcohol, polyoxypropylene diol (number average molecular weight per hydroxyl group is 500) (300 g) and propylene oxide (30 g) at 140 ° C. After ring-opening polymerization with propylene oxide (2970 g), polyoxyalkylene diol (number average molecular weight per hydroxyl group is 5000, hydroxyl value 11.2 mgKOH / g) (hereinafter referred to as hydroxyl-containing polymer) Combined (referred to as pP1)). The total remaining amount of cobalt atoms and zinc atoms in the zinc hexacyanocobaltate catalyst was about 10 ppm.
(Synthesis Example 2)
In the presence of zinc hexacyanocobaltate catalyst (456 mg) whose ligand is tert-butyl alcohol, polyoxypropylene diol (number average molecular weight per hydroxyl group is 500) (300 g) and propylene oxide (30 g) at 140 ° C. And then ring-opening polymerization of propylene oxide (5350 g) at 140 ° C. to give a polyoxyalkylenediol (number average molecular weight per hydroxyl group of 9000, hydroxyl value of 6.3 mgKOH / g) (hereinafter, A hydroxyl group-containing polymer (referred to as pP2) was obtained. The total remaining amount of cobalt atoms and zinc atoms in the zinc hexacyanocobaltate catalyst was about 10 ppm.

Example 1
Using the hydroxyl group-containing polymer (pP1) obtained in Synthesis Example 1, an oxyalkylene polymer was produced with the formulation shown in Table 1. The unit of the blending amount in Table 1 is “g”.
That is, 3000 g of the hydroxyl group-containing polymer (pP1) was placed in a pressure resistant reactor (internal volume 5 L) and dehydrated under reduced pressure while maintaining the internal temperature at 110 ° C. Next, the atmosphere in the reactor was replaced with nitrogen gas, and while maintaining the internal temperature at 50 ° C., as a tetravalent monoalkyltin catalyst (S), SCAT-24 (product name, above) 0.15 g (about 50 ppm with respect to pP1) of R ¹¹ in the general formula (I), which is -nC ₄ H ₉ and R ¹² is -nC ₇ H ₁₅ , is added, After stirring, 125.2 g of an isocyanate group-containing compound (U1) (purity 95%) represented by the following formula (3) was added so that NCO / OH was 0.97.
_{Si (-OCH 3) 3 -CH 2} CH 2 CH 2 NCO ··· (3)
Subsequently, the internal temperature was maintained at 80 ° C. for 8 hours, and the hydroxyl group-containing polymer (pP1) and the isocyanate group-containing compound (U1) were subjected to a urethanization reaction. As a result of analyzing the reactor contents after completion of the reaction, an oxyalkylene polymer having a substituent represented by an oxypropylene chain and “(Si (—OCH ₃ ) ₃ ) —CH ₂ CH ₂ CH ₂ NHCOO—” ( Formation of P1) was confirmed.

(Example 2)
In Example 1, the reaction was carried out in the same manner as in Example 1 except that the amount of the tetravalent monoalkyltin catalyst (S) was changed to 0.09 g (about 30 ppm with respect to pP1). And an oxyalkylene polymer (P2) having a substituent represented by “(Si (—OCH ₃ ) ₃ ) —CH ₂ CH ₂ CH ₂ NHCOO—”.

(Example 3)
In Example 2, the hydroxyl group-containing polymer (pP2) obtained in Synthesis Example 2 was used in place of the hydroxyl group-containing polymer (pP1), and the blending amount of the isocyanate group-containing compound (U1) was changed to 70.4 g. Is reacted in the same manner as in Example 2, and an oxyalkylene polymer having a substituent represented by “(Si (—OCH ₃ ) ₃ ) —CH ₂ CH ₂ CH ₂ NHCOO—” and an oxypropylene chain ( P3) was obtained.

(Comparative Examples 1-5)
Oxyalkylene polymers (P4, P5, P6, P7, P8) were produced with the formulations shown in Table 1 using a conventional urethane polymerization catalyst.
That is, instead of the tetravalent monoalkyltin catalyst (S) in Example 1, dibutyltin dilaurate (reagent) was used in Comparative Examples 1 and 2, and dioctyltin maleate (product name: SCAT-51) in Comparative Example 3. In Comparative Example 4, bismuth octylate (reagent) was used, and in Comparative Example 5, dioctylic acid fatty acid salt (product name: SCAT-52A, manufactured by Sanshare Machine Synthesis Co., Ltd.) was used. . The amount of the catalyst is as shown in Table 1. The other steps were the same as in Example 1.

(Evaluation of curability)
For each of the oxyalkylene polymers P1 to P8 obtained in Examples 1 to 3 and Comparative Examples 1 to 5, curability was evaluated by the following method.
That is, 30 g of polymer, 20 g of dioctyl phthalate, 0.15 g of ion exchange water, 10 g of heavy calcium carbonate (product name: Whiten SB: manufactured by Shiroishi Calcium Co., Ltd.), organotin catalyst (dibutyltin oxide and dioctyl phthalate) 0.75 g of No. 918, manufactured by No. 918, manufactured by Sansha Co., Ltd.) was mixed well to obtain a curable composition. The obtained curable composition was put into a stainless steel container and bubbled by flowing nitrogen, then left in an oven at 100 ° C. and cured for 30 minutes to obtain a cured product having a thickness of 9 mm. Thereafter, the cured body was cooled at room temperature for about 15 minutes, and the hardness of the surface of the cured body was measured. The measurement of hardness was performed by a method of measuring five points using a digital hardness meter DD2-C type (manufactured by Kobunshi Keiki Co., Ltd .: Asuka-C2 type) and calculating an average value. The measurement results are shown in Table 1.

(Evaluation of storage stability)
For each of the oxyalkylene polymers P1 to P8 obtained in Examples 1 to 3 and Comparative Examples 1 to 5, the storage stability was evaluated by the following method.
That is, to the oxyalkylene polymer, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (product name: Irganox 1010, manufactured by Ciba Specialty Chemicals Co., Ltd.) ) Was added to 0.5% by mass, and the sample that had been heated and uniformly dissolved was transferred to a 100 ml glass container, and a storage stability test was conducted.
In the test, first, the initial viscosity (25 ° C.) of the sample was measured, then the sample was heated to 50 ° C., and the viscosity of the sample (viscosity after storage) was measured after 2 weeks and 4 weeks, respectively, while maintaining the temperature at 50 ° C. It was measured. The viscosity was measured using an E-type viscometer (product name: VISCONIC EHD type, manufactured by Tokimec Co., Ltd., rotor No. 4). The viscosity was measured at 25 ° C., and a part of the sample stored at 50 ° C. was taken out and cooled to 25 ° C. and used for viscosity measurement.
From the obtained value of the initial viscosity and the value of the viscosity after storage, the thickening rate (unit:%) was determined by the following formula (A). The results are shown in Table 1. The smaller the degree of increase in the viscosity increase with time, the better the storage stability.
Thickening rate (%) = (viscosity after storage−initial viscosity) / initial viscosity × 100 (A)

  As shown in the results of Table 1, the oxyalkylene polymers (P1) to (P3) produced in Examples 1 to 3 according to the present invention are the oxyalkylene polymers (P4) produced in Comparative Examples 1 to 5. Compared with ~ (P8), the hardness of the cured product was equivalent, and the storage stability was greatly improved. From this, it is recognized that the storage stability can be greatly improved without impairing the curability by producing the oxyalkylene polymer (P) using the tetravalent monoalkyltin catalyst (S) in the present invention. It was.

Hereinafter, the example (manufacture examples 1-3) which manufactured the curable composition using the oxyalkylene polymer (P1) manufactured in Example 1 is shown.
(Production Example 1)
100 g of the polymer (P1) produced in Example 1, 75 g of heavy calcium carbonate (product name: Whiten SB, manufactured by Shiraishi Calcium Co., Ltd.), surface-treated calcium carbonate (product name: Shiraka Hana CCR, manufactured by Shiraishi Kogyo Co., Ltd.) ), 20 g of dioctyl phthalate as a plasticizer, 3 g of fatty acid amide (product name: Disparon # 6500, manufactured by Enomoto Kasei Co., Ltd.) as a thixotropic agent, and an aminosilane coupling agent (N- (2- 2 g of aminoethyl) -3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and 1 g of epoxy silane coupling agent (3-glycidyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), vinyltrile as a dehydrating agent 3 g of methoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), ethylene bis (oxy) as an anti-aging agent 1 g of tylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (product name: Irganox 245, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added, and uniform with 3 rolls. Made a mixture.
Thereafter, 2 g of a heated reaction product of dibutyltin oxide and dioctyl phthalate (product name: No918, manufactured by Sansha Co., Ltd.) was added as a tin catalyst to the mixture, and mixed by stirring to obtain a curable composition.
Immediately thereafter, an H-type test body described in JIS A5787 was prepared and cured for 7 days at room temperature and then for 7 days at 50 ° C. Thereafter, a tensile test was performed and the tensile physical properties were measured. As a result, good physical properties were obtained.

(Production Example 2)
100 g of the polymer (P1) produced in Example 1, 75 g of heavy calcium carbonate (product name: Super S, manufactured by Maruo Calcium Co., Ltd.), surface-treated calcium carbonate (product name: Calfine 200M, manufactured by Maruo Calcium Co., Ltd.) 40 g of an acrylic polymer having a molecular weight of 3000 (product name: UP1000, manufactured by Toa Gosei Co., Ltd.) as an acrylic plasticizer, 3 g of the same thixotropic agent as in Production Example 1, titanium oxide (product name: R820, Ishihara Sangyo Co., Ltd.) 1 g of the same aminosilane coupling agent as in Production Example 1 and 1 g of the same epoxysilane coupling agent as in Production Example 1, 3 g of the same dehydrating agent as in Production Example 1, and the same as in Production Example 1 1 g of anti-aging agent, 1 g of talc (product name: T talc, manufactured by Takehara Chemical Co., Ltd.), polyacrylonitrile-based organic resin balloon (product) : MFL-100SCA, were added 3g, manufactured by Matsumoto Yushi-Seiyaku Co.), and the homogeneous mixture in three rolls.
2 g of dibutyltin beer acetylacetonate (product name: Neostan U220, manufactured by Nitto Kasei Co., Ltd.) was added as a tin catalyst to the mixture, and mixed by stirring to obtain a curable composition.
About the obtained curable composition, when the tensile test was implemented similarly to manufacture example 1 and the tensile physical property was measured, the favorable physical property was obtained.

(Production Example 3)
To 100 g of the polymer (P1) produced in Example 1, 20 g of the same heavy calcium carbonate as in Production Example 1, 120 g of the same surface-treated calcium carbonate as in Production Example 1, 40 g of molecular weight 3000 polyoxypropylene diol as a plasticizer, 3 g of hydrogenated castor oil (product name: Disparon # 305, manufactured by Enomoto Kasei Co., Ltd.) as a thixotropic agent, 3 g of ethyl silicate (reagent) as a dehydrating agent, and pentaerythritol tetrakis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate] (product name: Irganox 1010, manufactured by Ciba Specialty Chemicals) and bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Product name: Tinuvin 770, manufactured by Ciba Specialty Chemicals) Squid: 0.5 g of (MK-200 Co-op Chemical Co., Ltd.), were added 3g of the same organic resin balloon as in Preparation Example 2, it was a uniform mixture by three rolls.
To this mixture, 4 g of a solution prepared by previously mixing 3 g of bis (2-ethylhexanoic acid) tin and 1 g of laurylamine was added as a curing catalyst, and stirred to obtain a curable composition.
About the obtained curable composition, when the tensile test was implemented similarly to manufacture example 1 and the tensile physical property was measured, the favorable physical property was obtained.

The oxyalkylene polymer in which the reactive silicon group is bonded to the polyoxyalkylene chain obtained by the present invention via a urethane bond is excellent in storage stability, and the curable composition containing the oxyalkylene polymer is Moisture cures to form a cured product having excellent rubber elasticity, and is useful as a waterproofing agent, adhesive, coating agent, sealing material, and the like.

It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2007-141705 filed on May 29, 2007 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (12)

A method for producing an oxyalkylene polymer (P) in which a reactive silicon group is bonded to a polyoxyalkylene chain via a urethane bond,
A hydroxyl group-containing polymer (pP) having a polyoxyalkylene chain and a hydroxyl group and an isocyanate group-containing compound (U) represented by the following general formula (1) are present in the presence of a tetravalent monoalkyltin catalyst (S). A process for producing an oxyalkylene polymer, comprising the step of urethanization reaction.
^{_{(Si (-X 1) a (}} -R 1) 3-a) -Q 1 -NCO ··· (1)
(Wherein, X ¹ represents an alkoxy group having 1 to 6 carbon atoms, and R ¹ represents a monovalent organic group having 1 to 20 carbon atoms which may have a substituent (excluding an alkoxy group). , Q ¹ represents a divalent organic group having 1 to 20 carbon atoms, a is an integer of 1-3. However, a plurality of R ¹ when R ¹ there are a plurality may be the same or different from each other , a plurality of X ¹ may be the same or different when X ¹ is more present.) The tetravalent monoalkyltin catalyst (S) is represented by the following general formula (I):
R ¹¹ Sn (OCOR ¹² ) ₃ (I)
(In the formula, R ¹¹ represents an alkyl group having 4 to 8 carbon atoms, and R ¹² represents an alkyl group having 2 to 17 carbon atoms. Three R ¹² existing in one molecule may be the same or different from each other. May be good.)
A first tin catalyst (S1) represented by the general formula (II):
R ¹³ Sn (SR ¹⁴ ) ₃ (II)
(In the formula, R ¹³ represents an alkyl group having 1 to 8 carbon atoms. R ¹⁴ represents an alkyl group having 8 to 18 carbon atoms. Three R ¹⁴ existing in one molecule are the same or different from each other. The manufacturing method of the oxyalkylene polymer of Claim 1 which is a 2nd tin catalyst (S2) represented by this.   The manufacturing method of the oxyalkylene polymer of Claim 1 or 2 whose reaction temperature of the said urethanation reaction is 50-200 degreeC.   The manufacturing method of the oxyalkylene polymer as described in any one of Claims 1-3 which performs the said urethanation reaction in inert gas atmosphere.   The oxyalkylene according to any one of claims 1 to 4, wherein a use amount of the tetravalent monoalkyltin catalyst (S) is 1 ppm to 100 ppm on a mass basis with respect to the hydroxyl group-containing polymer (pP). A method for producing a polymer.   The manufacturing method of the oxyalkylene polymer as described in any one of Claims 1-5 whose a in the said General formula (1) is 3.   A in the general formula (1) is 2, and Q ¹ The manufacturing method of the oxyalkylene polymer as described in any one of Claims 1-5 whose is a methylene group. The molar ratio (isocyanate group / hydroxyl group) of the total number of isocyanate groups of the isocyanate group-containing compound (U) to the total number of hydroxyl groups of the hydroxyl group-containing polymer (pP) is 0.80 to 1.10. The method for producing an oxyalkylene polymer according to claim 7 . The method for producing an oxyalkylene polymer according to any one of claims 1 to 8 , wherein the hydroxyl group-containing polymer (pP) has a number average molecular weight per hydroxyl group of 1000 to 30000. The hydroxyl group-containing polymer (pP), a hydroxyl value of 1.6~60.0mgKOH / g, the method of manufacturing the oxyalkylene polymer according to any one of claims 1-9. The hydroxyl group-containing polymer (pP) is a hydroxyl group-containing polymer (pP-1) obtained by ring-opening polymerization of an alkylene oxide to a compound having an active hydrogen atom in the presence of a double metal cyanide complex. method for producing an oxyalkylene polymer according to any one of 1-10.   While containing the oxyalkylene polymer obtained by the manufacturing method as described in any one of Claims 1-11 as a hardening component, the tetravalent monoalkyl tin catalyst (S) which is a reaction catalyst residue is contained. Curable composition.