JP2015214607A - Method for producing terminal unsaturated group-containing polyether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently producing terminal unsaturated group-containing polyether.SOLUTION: Provided is a method for producing terminal unsaturated group-containing polyether including a step for reacting, in the presence of a plasticizer, a hydroxyl group-containing polyether (I) comprising cyclic ether compound-derived polyether chain and hydroxyl group, and an alkali metal or alkali metal compound, followed by reacting the same with unsaturated group-containing halogen compound to introduce unsaturated group into the terminal of the hydroxyl group-containing polyether (I). The plasticizer has a weight average molecular weight less than that of hydroxyl group-containing polyether (I), and preferably has a hydroxyl value of 2.0 or less, and is one or more selected from the group consisting of cyclohexanedicarboxylic acid esters, phthalic acid esters, epoxy plasticizers, polyester plasticizers, polyether plasticizers, polyvinyl polymers, aliphatic hydrocarbon compounds having 8 to 18 carbon atoms, chlorinated paraffins having 10 to 30 carbon atoms.

Description

  The present invention relates to a method for producing a terminal unsaturated group-containing polyether.

A curable composition comprising a polyether having a hydrolyzable silyl group at the end of a polyoxyalkylene chain (hydrolyzable silyl group-containing polyether) as a curing component is a moisture-cured cured product having excellent rubber elasticity. Form. Therefore, the curable composition is widely used as an adhesive, a coating agent, and a sealing material.
A plurality of methods are known as a method for introducing a hydrolyzable silyl group into the terminal of a polyoxyalkylene chain. As one of them, in Patent Document 1 below, firstly, a polyether having an unsaturated group at a terminal (terminal unsaturated group-containing polyether) is prepared, and a hydrosilane compound and the terminal unsaturated group-containing polyether are prepared. Methods for reacting are known. Such a terminal unsaturated group-containing polyether is, for example, converted to —OM (M is an alkali metal) by reacting the terminal hydroxyl group of the hydroxyl group-containing polyether with an alkali metal or an alkali metal compound, and then unsaturated group. It can be produced by a method in which an unsaturated group is introduced into the terminal of the hydroxyl group-containing polyether by reacting with a halogen compound having.

Japanese Patent Laid-Open No. 03-072527

From the viewpoint of the physical properties of the cured product of the curable composition, the molecular weight of the hydrolyzable silyl group-containing polyether is increased by producing a terminal unsaturated group-containing polyether using a high molecular weight hydroxyl group-containing polyether. It is desirable.
However, according to the knowledge of the present inventors, the higher the molecular weight of the hydroxyl group-containing polyether, the longer the time required for the reaction for converting the terminal hydroxyl group of the hydroxyl group-containing polyether into —OM, and the terminal unsaturated group-containing polyether. There is a problem that the manufacturing efficiency of the is deteriorated.

  The present invention is a method in which a hydroxyl group-containing polyether is reacted with an alkali metal or an alkali metal compound and then an unsaturated group is introduced into the terminal of the halogenated compound having an unsaturated group and the reactive hydroxyl group-containing polyether. An object is to enable efficient production of a saturated group-containing polyether.

The present invention includes the following [1] to [9].
[1] Unsaturation after reacting a polyether chain derived from a cyclic ether compound and a hydroxyl group-containing polyether (I) having a hydroxyl group with an alkali metal or an alkali metal compound in the presence of a plasticizer (Z) Reacting with a halogen compound having a group to introduce an unsaturated group into the terminal of the hydroxyl group-containing polyether (I),
The plasticizer (Z) is the following plasticizer (Za), and the hydroxyl group-containing polyether (I) is synthesized in the absence of the plasticizer (Z), containing terminal unsaturated groups A method for producing a polyether.
Plasticizer (Za): a compound having a weight average molecular weight smaller than that of the hydroxyl group-containing polyether (I), cyclohexanedicarboxylic acid esters, phthalic acid esters, epoxy plasticizer, polyester plasticizer, poly One or more compounds selected from the group consisting of ether plasticizers, polyvinyl polymers, aliphatic hydrocarbon compounds having 8 to 18 carbon atoms, and chlorinated paraffins having 10 to 30 carbon atoms.

[2] Unsaturation after reacting a polyether chain derived from a cyclic ether compound and a hydroxyl group-containing polyether (I) having a hydroxyl group with an alkali metal or an alkali metal compound in the presence of a plasticizer (Z) Reacting with a halogen compound having a group to introduce an unsaturated group into the terminal of the hydroxyl group-containing polyether (I),
The hydroxyl group-containing polyether (I) is synthesized in the presence of a part or all of the plasticizer (Z), and the plasticizer (Z) is the following plasticizer (Zb). A method for producing an unsaturated group-containing polyether.
Plasticizer (Zb): a compound having a hydroxyl value of 2.0 or less and a weight average molecular weight smaller than that of the hydroxyl group-containing polyether (I), cyclohexanedicarboxylic acid esters, phthalic acid esters , Epoxy plasticizer, polyester plasticizer, polyether plasticizer, polyvinyl polymer, aliphatic hydrocarbon compound having 8 to 18 carbon atoms, and chlorinated paraffin having 10 to 30 carbon atoms. One or more compounds.

[3] The terminal unsaturated group according to [1] or [2], wherein the plasticizer (Z) is present in an amount of 10 to 300% by mass based on the total of the hydroxyl group-containing polyether (I) and the plasticizer (Z). A process for producing the polyether containing.
[4] The terminal defect according to any one of [1] to [3], wherein the plasticizer (Z) is a polyoxyalkylene compound (Z ′) having a polyoxyalkylene chain derived from an alkylene oxide. A method for producing a saturated group-containing polyether.
[5] The polyoxyalkylene compound (Z ′) is a polyoxyalkylene compound having one or more terminal groups selected from the group consisting of an alkoxy group and an acyloxy group at the terminal of the polyoxyalkylene chain. [4] The manufacturing method of terminal unsaturated group containing polyether as described in any one of.

[6] The method for producing a terminal unsaturated group-containing polyether according to [5], wherein the alkoxy group has 1 to 8 carbon atoms and the acyloxy group has 2 to 8 carbon atoms.
[7] A polyoxyalkylene compound (Z ′) obtained by converting the hydroxyl group of the following hydroxyl group-containing polyoxyalkylene compound (z1) into an alkoxy group, having a molecular weight of 100 to 2000 per terminal group The method for producing a terminal unsaturated group-containing polyether according to [5], which is an alkylene compound.
Hydroxyl group-containing polyoxyalkylene compound (z1): A hydroxyl group-containing polyoxyalkylene compound having a polyoxyalkylene chain derived from an alkylene oxide having 2 to 4 carbon atoms and having 1 to 3 hydroxyl groups.
[8] The method for producing a terminal unsaturated group-containing polyether according to any one of [5] to [7], wherein all terminal groups of the polyoxyalkylene compound (Z ′) are methoxy groups.

  [9] The terminal unsaturated group-containing polyoxy according to any one of [4] to [8], wherein the alkylene oxide in the polyoxyalkylene compound (Z ′) is one or both of propylene oxide and ethylene oxide. A method for producing ether.

  According to the present invention, after reacting a hydroxyl group-containing polyether with an alkali metal or an alkali metal compound, a halogen compound having an unsaturated group and a method of introducing an unsaturated group at the terminal of the reactive hydroxyl group-containing polyether, A terminal unsaturated group-containing polyether can be produced efficiently.

In this specification, unless otherwise specified, average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) are determined by gel permeation chromatography (GPC) using a polystyrene polymer as a reference. This is based on the so-called molecular weight in terms of polystyrene.
In this specification, unless otherwise specified, the hydroxyl value (OHV, the unit is mgKOH / g) is a value measured according to JIS K1557 (2007 edition).

The method for producing a terminal unsaturated group-containing polyether of the present invention comprises reacting a hydroxyl group-containing polyether (I) (also simply referred to as a hydroxyl group-containing polyether) with an alkali metal or an alkali metal compound to produce a hydroxyl group-containing polyether. A step of converting a terminal hydroxyl group into a group represented by -OM (M is an alkali metal) (also referred to as an alcoholate reaction step);
By reacting a polyether having an -OM group introduced at the terminal with a halogen compound having an unsaturated group, the terminal M (alkali metal) is substituted with a residue obtained by removing a halogen atom from the halogen compound. A step of obtaining a terminal unsaturated group-containing polyether having an unsaturated group introduced at the terminal (also referred to as an unsaturated group introduction reaction step).
The ratio of the hydroxyl group of the hydroxyl group-containing polyether (I) that has been converted to a group containing an unsaturated group is referred to as terminal conversion rate.

The hydroxyl group-containing polyether (I) in the present specification means a polyether monool and a polyether polyol. The hydroxyl group-containing polyether (I) has a hydroxyl group and a polyether chain derived from a cyclic ether compound.
In this specification, the cyclic ether compound is a compound having a heterocycle composed of a carbon atom and one or two oxygen atoms, and the bond between the carbon atom and the oxygen atom is broken to open the ring. And a compound capable of causing a polymerization reaction (that is, a ring-opening addition reaction) by sequentially repeating a reaction of addition to an active hydrogen-containing group such as a hydroxyl group. Hereinafter, the cyclic ether compound is also referred to as a cyclic ether.
The polyether chain in this specification refers to a structure in which structural units containing an ether bond are linked in a chain. The polyether monool has one hydroxyl group, and the polyether polyol has two or more hydroxyl groups.

The plasticizer (Z) may be present in the alcoholate reaction step.
For example, the hydroxyl group-containing polyether (I) is synthesized in the presence of the plasticizer (Z) to obtain a raw material composition containing the plasticizer (Z) and the hydroxyl group-containing polyether (I). The method used in the reaction with a metal or alkali metal compound (first embodiment) may be used, and the hydroxyl group-containing polyether (I) obtained by synthesizing the hydroxyl group-containing polyether (I) without using the plasticizer (Z). The plasticizer (Z) may be added to the reaction system (second embodiment) after adding the plasticizer (Z) to the reaction system for synthesizing the hydroxyl group-containing polyether (I). ) To obtain a raw material composition containing a plasticizer (Z) and a hydroxyl group-containing polyether (I), and after adding the remainder of the plasticizer (Z) to the raw material composition, an alkali metal or An alkali metal compound It may be a method (third embodiment).
In any method, the production efficiency of the terminal unsaturated group-containing polyether can be effectively improved.

In the first or third embodiment, the timing of adding the plasticizer (Z) to the reaction system for synthesizing the hydroxyl group-containing polyether (I) is 1 until the polymerization step of the hydroxyl group-containing polyether is completed. Can be added once or multiple times. From the viewpoint of production efficiency, it is preferable to add the entire amount of the plasticizer (Z) together with the initiator and the DMC catalyst before starting the reaction.
In the second or third embodiment, after the polymerization step of the hydroxyl group-containing polyether is completed, the total amount of the plasticizer (Z) is added to the hydroxyl group-containing polyether before contacting with the alkali metal or the alkali metal compound. It is preferable.

<Plasticizer (Z)>
When the plasticizer (Z) is not included in the hydroxyl group-containing polyether (I) as in the second embodiment, the following plasticizer (Za) is used as the plasticizer (Z).
When the plasticizer (Z) is contained in the hydroxyl group-containing polyether (I) as in the first and third embodiments, the following plasticizer (Zb) is used as the plasticizer (Z). The plasticizer (Zb) is a compound having a hydroxyl value of 2.0 or less among the plasticizers (Za). By using a compound having a hydroxyl value of 2.0 or less, the cyclic ether compound used in the production of the hydroxyl group-containing polyether (I) reacts with the monool component in the plasticizer (Z), thereby resulting in a low molecular weight. It is possible to suppress the by-production of the polyether monool. When such a by-product is produced in the step of producing a terminal unsaturated group-containing polyether, the cause of uncured polyether having a hydrolyzable silyl group produced using the terminal unsaturated group-containing polyether It becomes.

The plasticizer (Za) is a compound having a weight average molecular weight smaller than that of the hydroxyl group-containing polyether used in the alcoholate reaction step, and is a cyclohexanedicarboxylic acid ester, a phthalic acid ester, an epoxy plasticizer, a polyester It is at least one compound selected from the group consisting of a plasticizer, a polyether plasticizer, a polyvinyl polymer, an aliphatic hydrocarbon compound having 8 to 18 carbon atoms, and a chlorinated paraffin having 10 to 30 carbon atoms.
The plasticizer (Z-a) is (1) a compound having no hydroxyl group (hydroxyl value is zero), or (2) a part or all of the hydroxyl group of the compound having a hydroxyl group is an inert organic group (hereinafter referred to as “a hydroxyl group”). , Also referred to as an inert group).
In the case of (2), inert means that the plasticizer (Z) does not react with the components that coexist in the reaction solution. In the present invention, the plasticizer (Z) is present in the alcoholation reaction step in which the hydroxyl group-containing polyether (I) is reacted with an alkali metal or an alkali metal compound. Therefore, an organic group that does not react with an alkali metal or an alkali metal compound is used as an inert group. The hydroxyl value of the plasticizer (Za) is preferably 4.1 or less, and more preferably 2.0 or less.
Examples of the inert group include an alkoxy group, an acyloxy group, a group containing a urethane bond (a group generated by a reaction between a monoisocyanate compound and a hydroxyl group), a group containing a halogen atom (a halogenating agent such as phosphorus trichloride, a hydroxyl group, and the like. Group generated by the above reaction) and the like.

The plasticizer (Zb) is a compound having a hydroxyl value of 2.0 or less and a weight average molecular weight smaller than that of the hydroxyl group-containing polyether used in the alcoholate reaction step, and having a cyclohexanedicarboxylic acid ester Phthalates, phthalates, epoxy plasticizers, polyester plasticizers, polyether plasticizers, polyvinyl polymers, aliphatic hydrocarbon compounds having 8 to 18 carbon atoms, chlorinated paraffins having 10 to 30 carbon atoms One or more compounds selected from the group consisting of:
The plasticizer (Zb) is (1) a compound having no hydroxyl group (hydroxyl value is zero), or (2) a part or all of the hydroxyl group of the compound having a hydroxyl group, having a hydroxyl value of 2.0. What converted into the inactive organic group (inert group) is preferable so that it may become the following.
In the case of (2), in Embodiments 1 and 3, the plasticizer (Z) is present not only in the alcoholation reaction step but also in the reaction system for synthesizing the hydroxyl group-containing polyether (I). Therefore, an organic group that does not react with an alkali metal or an alkali metal compound and does not react with a cyclic ether that is a raw material of the hydroxyl group-containing polyether (I) is used as an inert group.
Examples of the inert group include an alkoxy group, an acyloxy group, a group containing a urethane bond (a group generated by a reaction between a monoisocyanate compound and a hydroxyl group), a group containing a halogen atom (a halogenating agent such as phosphorus trichloride, a hydroxyl group, and the like. Group generated by the above reaction) and the like.

Hereinafter, the plasticizer (Z) and the plasticizer (Zb) are referred to as a plasticizer (Z) when it is not necessary to divide them into cases.
The boiling point or flash point of the plasticizer (Z) is preferably 180 ° C. or higher, and more preferably 200 ° C. or higher.
When a compound whose weight average molecular weight is smaller than the hydroxyl group-containing polyether used in the alcoholate reaction step is used as the plasticizer (Z), the viscosity of the reaction solution in the alcoholate reaction step is likely to be sufficiently reduced. It is considered that the reaction of converting the terminal hydroxyl group of the hydroxyl group-containing polyether to -OM is facilitated by the decrease in the viscosity of the reaction solution.
The difference between the weight average molecular weight of the plasticizer (Z) and the weight average molecular weight of the hydroxyl group-containing polyether used in the alcoholation reaction step is preferably 5,000 or more, and more preferably 10,000 or more.
In addition, as for the compound comprised only from the molecule | numerator of the same molecular weight, such as a phthalate ester, let the molecular weight calculated | required from chemical formula be a weight average molecular weight.
The lower limit of the weight average molecular weight of the compound used as the plasticizer (Z) is, for example, preferably 100 or more, and more preferably 150 or more.

Examples of the cyclohexane dicarboxylic acid esters include diisononyl cyclohexane dicarboxylate, dioctyl cyclohexane dicarboxylate, diisodecyl cyclohexane dicarboxylate, dibutyl cyclohexane dicarboxylate, dibutyl benzyl cyclohexane dicarboxylate, and the like. These hydroxyl values are almost zero.
Examples of the phthalic acid esters include dioctyl phthalate, diisodecyl phthalate, dibutyl phthalate, and butyl benzyl phthalate. These hydroxyl values are almost zero.
Examples of the epoxy plasticizer include epoxidized soybean oil, epoxidized linseed oil, and epoxy benzyl stearate. These hydroxyl values are almost zero.
Examples of the polyester plasticizer include polyester obtained by a reaction between a dibasic acid and a dihydric alcohol. An acid-terminated polyester (having a hydroxyl value of almost zero) can be used. Alternatively, a polyester having a hydroxyl group terminal in which a terminal hydroxyl group is converted to the inactive group can be used.
Examples of the polyether plasticizer include a polyoxyalkylene compound (Z ′) described later.
Examples of the polyvinyl polymer include polystyrene, polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene and the like. These have no hydroxyl group and the hydroxyl value is zero.
Examples of the aliphatic hydrocarbon compound having 8 to 18 carbon atoms include paraffin hydrocarbons, olefin hydrocarbons, diolefin hydrocarbons, polyolefin hydrocarbons, and acetylene hydrocarbons having 8 to 18 carbon atoms. These have no hydroxyl group and the hydroxyl value is zero.
Examples of 10-30 chlorinated paraffins include short chain chlorinated paraffin, medium chain chlorinated paraffin, and long chain chlorinated paraffin. These have no hydroxyl group and the hydroxyl value is zero.

The amount of the plasticizer (Z) used (the total amount used when two or more are used) is preferably 10 to 300% by mass with respect to the total amount of the hydroxyl group-containing polyether and plasticizer used in the alcoholate reaction step. In the present invention, the total amount of the initiator and the cyclic ether compound used for the synthesis reaction of the hydroxyl group-containing polyether can be regarded as the total amount of the hydroxyl group-containing polyether.
When the usage-amount of a plasticizer (Z) is more than the lower limit of the said range, the effect of the viscosity reduction of a reaction liquid by using a plasticizer (Z) is fully acquired. In the hydrolyzable silyl group-containing polyether produced by using a terminal unsaturated group-containing polyether, the desired physical properties are sufficiently high when the ratio is not more than the upper limit of the above range, and the proportion of the plasticizer (Z) is not too high. can get.
The amount of the plasticizer (Z) used is preferably 5 to 100% by mass, more preferably 10 to 80% by mass, and further preferably 15 to 40% by mass.

<Polyoxyalkylene compound (Z ′)>
A polyoxyalkylene compound (Z ′) is preferred as the plasticizer (Z).
The polyoxyalkylene compound (Z ′) in the present invention has a polyoxyalkylene chain derived from alkylene oxide, and is a compound that satisfies the conditions of the hydroxyl value and the weight average molecular weight of the plasticizer (Z) in the present invention.
The polyoxyalkylene compound (Z ′) preferably has at least one inactive group selected from the group consisting of an alkoxy group and an acyloxy group as a terminal group of the polyoxyalkylene chain.
The polyoxyalkylene compound (Z ′) is a compound obtained by converting the hydroxyl group at the terminal of the hydroxyl group-containing polyoxyalkylene compound (z1) to an inert group so that the hydroxyl value is 2.0 or less. Is preferred.

In the present specification, the hydroxyl group-containing polyoxyalkylene compound (z1) means a polyoxyalkylene monool or a polyoxyalkylene polyol.
The polyoxyalkylene chain in the hydroxyl group-containing polyoxyalkylene compound (z1) is composed of a chain of oxyalkylene groups formed by a ring-opening addition reaction of alkylene oxide.

The polyoxyalkylene compound (Z ′) has a polyoxyalkylene chain derived from an alkylene oxide having 2 to 4 carbon atoms, and the hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) having 1 to 3 hydroxyl groups. A compound obtained by converting into an inert group is preferred.
The conversion method to such an inert group includes conversion to an alkoxy group by alkyl halide (alkoxylation); monocarboxylic acid (such as acetic acid), monocarboxylic acid anhydride (such as acetic anhydride), acyl halide (such as acetyl chloride) ) Such as monocarboxylic acids and reactive derivatives thereof (esterification); conversion to inactive groups containing urethane bonds by monoisocyanate compounds (urethanization); non-halogen atoms containing phosphorus trichloride Conversion to an active group (halogenation); and the like. Two or more of these conversion methods may be used in combination. Considering the influence during the production of the hydroxyl group-containing polyether, the number of carbon atoms of the alkyl halide, monocarboxylic acid, or monoisocyanate compound used for the conversion is preferably 8 or less.
Considering the influence at the time of production of hydroxyl group-containing polyether and production efficiency, a method of converting a hydroxyl group to an alkoxy group by alkoxylation, an acyloxy group (—O—C (O ) -R ′; R ′ is an alkyl group or the like), or a combination of these methods is preferred.

  When the hydroxyl group-containing polyoxyalkylene compound (z1) has two or more hydroxyl groups, each hydroxyl group may be converted into a different inert group. In this case, it is preferable that a part of the hydroxyl group is converted into an alkoxy group and the other hydroxyl group is converted into an acyl group and / or an acyloxy group. When using alkoxylation and esterification together, it is preferable that the total number of moles of esterified terminal hydroxyl groups is 50 mol% or less with respect to the number of moles of alkoxylated terminal hydroxyl groups.

When the inert group at the terminal of the polyoxyalkylene compound (Z ′) is an alkoxy group (—OR ¹⁰ and R ¹⁰ are alkyl groups), the alkoxy group has 1 to 8 carbon atoms (the carbon number of R ¹⁰ ). Preferably, 1-4 is more preferable, and 1-2 is still more preferable.
When the inactive group at the terminal of the polyoxyalkylene compound (Z ′) is an acyloxy group, the acyloxy group preferably has 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms, and still more preferably 2.
It is preferable that the alkoxy group or the acyloxy group has 8 or less carbon atoms in that a thickening suppressing effect can be sufficiently obtained by performing the alcoholate reaction step in the presence of the polyoxyalkylene compound (Z ′). In particular, when the number of carbon atoms is 4 or less, the oxyalkylene group content in the polyoxyalkylene compound (Z ′) is preferable.
In particular, it is preferable that the terminal inactive group of the polyoxyalkylene compound (Z ′) is a methoxy group because the oxyalkylene group content in the polyoxyalkylene compound (Z ′) is high. The higher the oxyalkylene group content, the better the compatibility between the polyoxyalkylene compound (Z ′) and the hydroxyl group-containing polyether.
It is preferable that all terminal groups of the polyoxyalkylene compound (Z ′) are methoxy groups.

When the hydroxyl group-containing polyoxyalkylene compound (z1) has one hydroxyl group, the terminal having no hydroxyl group in the polyoxyalkylene chain may be an inert organic group such as an alkoxy group or an alkoxycarbonyl group. For example, a polyoxyalkylene monool obtained by polymerizing a cyclic ether with an alkane monool using an alkane monool as an initiator has a hydroxyl group at one end and an alkoxy group at the other end. Similarly, a polyoxyalkylene monool obtained by polymerizing a cyclic ether with a monocarboxylic acid has a hydroxyl group at one end and an acyloxy group at the other end.
The inactive terminal group of the polyoxyalkylene compound (Z ′) is a hydroxyl group-containing polyoxyalkylene compound (z1) in addition to the inactive organic group generated by inactivating the hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1). It contains an inert organic group that had. Therefore, the terminal group of the polyoxyalkylene compound (Z ′) is both an inactive organic group possessed by the hydroxyl group-containing polyoxyalkylene compound (z1) and an inactive organic group obtained by converting the hydroxyl group. Means. Therefore, the number of inactive end groups of the polyoxyalkylene compound (Z ′) is 2 or more.

The hydroxyl group-containing polyoxyalkylene compound (z1) obtained by using a hydroxyl group-containing compound having one or two hydroxyl groups as an initiator is a linear structure compound having one or two hydroxyl groups. The polyoxyalkylene compound (Z ′) obtained from the hydroxyl group-containing polyoxyalkylene compound (z1) is a compound having a linear structure having two inactive end groups. Regardless of the difference in the number of hydroxyl groups (one or two) of the hydroxyl group-containing polyoxyalkylene compound (z1), the number of terminal groups of these compounds having a linear structure in the present invention is 2.
When the number of hydroxyl groups in the initiator is 3 or more, the resulting hydroxyl group-containing polyoxyalkylene compound (z1) has the same number of end groups as the number of hydroxyl groups in the initiator.

  The molecular weight per terminal group of the polyoxyalkylene compound (Z ′) is preferably 100 to 2,000, more preferably 100 to 1,000, and even more preferably 150 to 800. When the molecular weight is 100 or more, the volatility of the polyoxyalkylene compound (Z ′) tends to be sufficiently low. If it is 2,000 or less, the dilution effect is increased. Particularly when the viscosity is 1,000 or less, the viscosity of the reaction solution tends to be sufficiently low.

The hydroxyl group-containing polyoxyalkylene compound (z1) used for the synthesis of the polyoxyalkylene compound (Z ′) is obtained by ring-opening addition of an alkylene oxide having 2 to 4 carbon atoms to an initiator having 1 to 3 hydroxyl groups. A hydroxyl group-containing polyoxyalkylene compound obtained by the above is preferable.
Among the compounds that can be used as the initiator of the hydroxyl group-containing polyether described later, those having no polyoxyalkylene chain and having 1 to 3 hydroxyl groups can be used as the initiator.
Of the compounds that can be used as an initiator for a hydroxyl group-containing polyether described later, the polyoxyalkylene chain has a polyoxyalkylene chain, and the polyoxyalkylene chain is derived from an alkylene oxide having 2 to 4 carbon atoms, and The initiator having 1 to 3 hydroxyl groups can be used as an initiator for synthesizing the hydroxyl group-containing polyoxyalkylene compound (z1) or the hydroxyl group-containing polyoxyalkylene compound (z1) itself.
The molecular weight of the initiator for synthesizing the hydroxyl group-containing polyoxyalkylene compound (z1) is 18 or more, preferably 32 or more. The upper limit of the molecular weight of the initiator for synthesizing the hydroxyl group-containing polyoxyalkylene compound (z1) is preferably 1,000 or less and more preferably 300 or less because the oxyalkylene group content in the hydroxyl group-containing polyoxyalkylene compound (z1) is high. preferable.

Examples of the initiator having 1 hydroxyl group include methanol, ethanol, 2-propanol, n-butanol, iso-butanol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, and oleyl alcohol. Monohydric alcohols are preferred. When a monohydric alcohol (R ¹¹ —OH) is used as an initiator, an alkoxy group (R ¹¹ O—) derived from the monohydric alcohol is present at the terminal group of the resulting polyoxyalkylene compound (Z ′). Exists. Therefore, the number of carbon atoms of the monohydric alcohol (R ¹¹ —OH) as the initiator is preferably 1 to 4, and more preferably 1.
As described above, a compound obtained by alkoxylating a terminal hydroxyl group of a polyoxyalkylene monool obtained by ring-opening addition of an alkylene oxide to an initiator having one hydroxyl group has an alkoxy group (inactive at both ends of one molecule). Group).

  Examples of the initiator having 2 hydroxyl groups include water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-cyclohexanediol, 1,3-butanediol, 1,4- Dihydric alcohols such as butanediol, 1,6-hexanediol and 1,4-cyclohexanediol are preferred. Of these, water, ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol having a relatively low molecular weight of the initiator are more preferable, and propylene glycol and dipropylene glycol are particularly preferable in that the ether group content can be increased.

As the initiator having 3 hydroxyl groups, trihydric alcohols such as glycerin and trimethylolpropane are preferable. Of these, glycerin having a relatively low molecular weight of the initiator is particularly preferred in that the ether group content can be increased.
Examples of the initiator having 4 or more hydroxyl groups include tetrahydric or higher polyhydric alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, diglycerin, polyglycerin; glucose, sorbitol, dextrose, fructose, sucrose, methyl Saccharides such as glucoside and trehalose or derivatives thereof are preferred.

The alkylene oxide used for the synthesis of the hydroxyl group-containing polyoxyalkylene compound (z1) is preferably an alkylene oxide having 2 to 4 carbon atoms.
The alkylene oxide used in the synthesis of the hydroxyl group-containing polyoxyalkylene compound (z1) is more preferably the same alkylene oxide as the cyclic ether used in the production of the hydroxyl group-containing polyether, specifically, ethylene oxide, propylene oxide, One or more selected from the group consisting of 1,2-butylene oxide and 2,3-butylene oxide are used.
Among these, it is preferable to use one or both of ethylene oxide and propylene oxide because the oxyalkylene group content can be increased.

The polyoxyalkylene compound (Z ′) has a polyoxyalkylene chain derived from an alkylene oxide having 2 to 4 carbon atoms, and the hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) having 1 to 3 hydroxyl groups. Alkoxylated compounds are preferred.
In particular, the molecular weight per terminal group of the polyoxyalkylene compound (Z ′) is preferably 100 to 1,000, and more preferably 150 to 800.
In particular, the amount of the polyoxyalkylene compound (Z ′) used is preferably 10 to 80 parts by mass, more preferably 10 to 50 parts by mass, and more preferably 15 to 40 parts by mass with respect to 100 parts by mass of the hydroxyl group-containing polyether produced. Further preferred.

[Production Method of Polyoxyalkylene Compound (Z ′)]
The step of ring-opening addition of alkylene oxide to the initiator to obtain the hydroxyl group-containing polyoxyalkylene compound (z1) can be performed using a known method. Usually, a catalyst is used. A catalyst is not specifically limited, A well-known catalyst can be used suitably. An alkali catalyst such as KOH or a DMC catalyst described later may be used.

The method for producing the polyoxyalkylene compound (Z ′) by alkoxylating the hydroxyl group at the terminal of the hydroxyl group-containing polyoxyalkylene compound (z1) is preferably performed by a method having the following steps (A) and (B). .
First, the terminal hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) having 1 to 3 hydroxyl groups is reacted with an alkali metal or an alkali metal compound to convert the terminal hydroxyl group to -OM (M is an alkali metal) ( (Alcoholation) (step (A)).
Next, the terminal -OM is reacted with an alkyl halide to convert it to an alkoxy group (step (B)). That is, the terminal —OM is converted to an alkoxy group (—OR ¹⁰ ) by reacting with an alkyl halide (R ¹⁰ —X: X is a halogen atom).
The molar ratio of the alkali metal or alkali metal compound to the terminal hydroxyl group of the hydroxyl group-containing polyoxyalkylene compound (z1) in step (A) (based on the alkali metal atom), and the halogen to —OM at the terminal in step (B) One of the molar ratios of alkyl halides (based on halogen atoms) is preferably 1.2 molar equivalents or more, and the other is preferably 1.5 molar equivalents or more. It is more preferable that both are 1.5 molar equivalents or more.
By reacting at such a molar ratio, a polyoxyalkylene compound (Z ′) having a hydroxyl value of 2.0 or less, preferably 1.3 or less can be obtained efficiently.
The upper limit of the molar ratio is not particularly limited, but is preferably 2.0 equivalents or less in both steps (A) and (B) from the viewpoint of production cost.

As an alkali metal used at a process (A), sodium or potassium is preferable. Examples of alkali metal compounds include alkali metal hydrides such as NaH; metal alkoxides represented by NaOR (R represents an alkyl group such as methyl, ethyl, propyl, isopropyl, or butyl); sodium hydroxide or potassium hydroxide Alkali metal hydroxides are preferred.
In the step (A), it is preferable to add a lower alcohol having 1 to 5 carbon atoms as a solvent in order to uniformly dissolve these alkali metals or alkali metal compounds in the system and promote the reaction. Methanol is particularly preferable. 1-40 mass parts is preferable with respect to 100 mass parts of hydroxyl-containing polyoxyalkylene compounds (z1), and, as for the usage-amount of this solvent, 5-30 mass parts is more preferable, and 10-20 mass parts is further more preferable.
As the halogen used in the step (B), chlorine or bromine is preferable. As the alkyl halide, methyl chloride is preferred.

The reaction time in the step (A) is preferably set to a time during which the terminal hydroxyl group is sufficiently alcoholated. For example, it is preferably 3 hours or longer, more preferably 5 hours or longer, and even more preferably 10 hours or longer. The upper limit of the reaction time is not particularly limited, but is preferably 15 hours or less and more preferably 13 hours or less from the viewpoint of production efficiency.
The reaction time in the step (B) is preferably set to a time during which the terminal hydroxyl group is sufficiently alcoholated. For example, 2 hours or more are preferable, and 3 hours or more are more preferable. The upper limit of the reaction time is not particularly limited, but is preferably 5 hours or less from the viewpoint of production efficiency, and more preferably 4 hours or less.

It is preferable to remove by-products and unreacted substances generated in each step (A) and (B) in each step or after steps (A) and (B) are completed.
In the step (A), for example, water (H ₂ O) is by-produced by a reaction between a terminal hydroxyl group and sodium hydroxide. In this case, in step (A), it is preferable to remove the by-produced water and the lower alcohol of the solvent by performing degassing under reduced pressure, and to proceed the reaction between the terminal hydroxyl group and sodium hydroxide.
In the step (B), an unreacted alkyl halide used in excess is preferably removed by degassing after completion of the reaction between the terminal -OM and the alkyl halide.
Finally, the alkali metal or alkali metal compound unreacted used excessively in the step (A) and the alkali metal halide by-produced in the step (B) are preferably removed by extraction with water.

In order to set the hydroxyl value of the polyoxyalkylene compound (Z ′) to 2.0 or less, preferably 1.3 or less, the content of the solvent (lower alcohol) contained in the reaction product obtained in the step (A) is changed. It is preferable to carry out the reaction so that the value (residual solvent amount) measured by the following method is 3500 ppm or less. More preferably, it is 3000 ppm or less. The amount of residual solvent can be controlled by, for example, the reaction time in step (A).
The amount of the residual solvent is preferably as small as possible, and the lower limit is not particularly limited, but is preferably 1000 ppm or more from the viewpoint of production efficiency.
<Measurement method of residual solvent (methanol) content>
Using a gas chromatography method, the content of a solvent (for example, methanol) was measured under the following conditions.
Apparatus: SHIMADZU GC-2014 (product name, manufactured by Shimadzu Corporation).
Column: PEG-20M (product name, manufactured by GL Sciences Inc.).
Sample preparation method: 2 g of a sample was dissolved in 2 g of an internal standard solution (a solution obtained by dissolving 0.2 g of ethylbenzene in 100 g of dimethylformamide) and 6 g of dimethylformamide.
Data analysis method: The peak area ratio of ethylbenzene and methanol was converted to a weight ratio, and the methanol content in the sample was calculated.

<Hydroxyl-containing polyether (I)>
The hydroxyl group-containing polyether (I) is obtained by subjecting an initiator having a hydroxyl group to a ring-opening addition reaction of the cyclic ether. In the ring-opening addition reaction, a hydroxyl group-containing polyether having a polymer chain (polyether chain) composed of a structural unit in which the cyclic ether is opened and having a hydroxyl group at the terminal is generated.
In this specification, the ring-opening addition reaction may be simply referred to as polymerization. The number of hydroxyl groups of the hydroxyl group-containing polyether obtained by such polymerization is equal to the number of hydroxyl groups of the initiator. When a mixture of two or more kinds of initiators having different numbers of hydroxyl groups is used, the average number of hydroxyl groups per molecule of the initiator mixture (also simply referred to as the average number of hydroxyl groups) is the average per molecule of the resulting hydroxyl group-containing polyether. The number of hydroxyl groups (sometimes simply referred to as the average number of hydroxyl groups).

The hydroxyl group-containing polyether (I) is preferably produced by a method in which a cyclic ether compound is subjected to a ring-opening addition reaction with an initiator having at least one hydroxyl group per molecule in the presence of a double metal cyanide complex catalyst.
The weight average molecular weight (Mw) of the hydroxyl group-containing polyether is preferably 5,000 to 500,000, and more preferably 10,000 to 500,000.
It is preferable that the Mw of the hydroxyl group-containing polyether is 5,000 or more because an effect of improving physical properties such as strength and elongation can be obtained.
More preferably, the weight average molecular weight (Mw) of the hydroxyl group-containing polyether is 15,000 to 500,000, more preferably 20,000 to 300,000, and particularly preferably 25,000 to 100,000. When Mw is 15,000 or more, it is preferable because an effect of improving physical properties such as strength and elongation is obtained, and when it is 500,000 or less, viscosity in use can be suppressed low.
The molecular weight distribution (Mw / Mn) of the hydroxyl group-containing polyether is preferably less than 1.15. The lower limit of the molecular weight distribution is preferably as small as possible, but it becomes difficult to produce. Therefore, in reality, it is more preferably 1.01 or more and less than 1.15, and particularly preferably 1.01 or more and less than 1.14.
The hydroxyl value of the hydroxyl group-containing polyether is preferably 11 mgKOH / g or less, more preferably 6 mgKOH / g or less, and particularly preferably 4 mgKOH / g or less. The lower limit is preferably 0.22 mgKOH / g or more, more preferably 1 mgKOH / g or more, and further preferably 2 mgKOH / g or more in order to keep the viscosity of the hydroxyl group-containing polyether low. The smaller the molecular weight per hydroxyl group, the smaller the molecular weight distribution.

<Double metal cyanide complex catalyst (DMC catalyst)>
A known DMC catalyst can be used. Typically, it is represented by the following formula (11).
M ¹ _a [M ² _b (CN) _c ] _de (M ³ _f X _g ) h (H ₂ O) i (L) (11)
(In formula (11), M ^{1 to} M ³ are metals, X is a halogen atom, L is an organic ligand, a, b, c, d, e, f, g, h, i are metals. (The numbers that can vary depending on the valence and the coordination number of the organic ligand are shown.)

In the formula, M ¹ or M ³ represents Zn (II), Fe (II), Fe (III), Co (II), Ni (II), Mo (IV), Mo (VI), Al (III), Selected from the group consisting of V (V), Sr (II), W (IV), W (VI), Mn (II), Cr (III), Cu (II), Sn (II), and Pb (II) And at least one metal atom, preferably Zn (II) or Fe (II). The Roman numeral in parentheses following the atomic symbol of the metal represents the valence, and so on. M ¹ and M ^{3 in} one molecule may be the same as or different from each other. Preferably they are the same as each other.

M ² is Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), Ni (II), V It is at least one metal atom selected from the group consisting of (IV) and V (V), and is preferably Co (III) or Fe (III). X is a halogen atom. L represents an organic ligand.

As the organic ligand, alcohol, ether, ketone, ester, amine, amide and the like can be used, and alcohol is more preferable. Preferred organic ligands are water-soluble, and specific examples include tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, N, N-dimethylacetamide, One or two selected from ethylene glycol dimethyl ether (also referred to as glyme), diethylene glycol dimethyl ether (also referred to as diglyme), triethylene glycol dimethyl ether (also referred to as triglyme), ethylene glycol mono-tert-butyl ether, iso-propyl alcohol, and dioxane. The above compounds are mentioned. Dioxane may be 1,4-dioxane or 1,3-dioxane, and 1,4-dioxane is preferred.
Particularly preferred organic ligands are tert-butyl alcohol, tert-pentyl alcohol, ethylene glycol mono-tert-butyl ether, or a combination of tert-butyl alcohol and ethylene glycol mono-tert-butyl ether. When such an organic ligand is used, a particularly high catalytic activity is obtained, which is preferable in terms of narrowing the molecular weight distribution of the hydroxyl group-containing polyether.

Specifically, such a DMC catalyst has the same formula (11) in which M ¹ and M ³ are the same as each other, Zn (II) or Fe (II), and M ² is Co (III) or Fe (III). Wherein X is halogen, L is tert-butyl alcohol or ethylene glycol mono-tert-butyl ether, M ¹ and M ³ are Zn (II), M ² is Co (III), and X is What potassium and L are tert- butyl alcohol is especially preferable at the point which can reduce a by-product.

The manufacturing method of a DMC catalyst is not specifically limited, A well-known method can be used suitably. For example, (a) an organic ligand is coordinated to a reaction product obtained by reacting a metal halide salt with a cyanometalate acid and / or an alkali metal cyanometalate in an aqueous solution, and then formed. A method in which the solid component is separated and the separated solid component is further washed with an aqueous organic ligand solution, or (b) a halogenated metal salt, a cyanometallate and / or an alkali metal cyanometa in the organic ligand solution. The reaction product (solid component) obtained by reacting with the rate is separated, and the cake (solid component) obtained by the method of washing the separated solid component with an organic ligand aqueous solution is filtered and further separated. The method of making it dry can be mentioned. The metal constituting the cyanometalate of the alkali metal cyanometalate used in the production of the DMC catalyst corresponds to M2 in the formula (11). As the cyanometalate or alkali metal cyanometalate used as a raw material for producing the DMC catalyst of the present invention, H ₃ [Co (CN) ₆ ], Na ₃ [Co (CN) ₆ ], or K ₃ [Co (CN ₆ ] is preferred, and Na ₃ [Co (CN) ₆ ] or K ₃ [Co (CN) ₆ ] is particularly preferred.

The use amount of the DMC catalyst is set to a required amount or more according to the target molecular weight of the hydroxyl group-containing polyether to be produced. On the other hand, it is preferable to use the DMC catalyst as little as possible to reduce the DMC catalyst remaining in the obtained hydroxyl group-containing polyether and the metal compound derived from the DMC catalyst. This can reduce the influence of the residual DMC catalyst on the reaction rate between the hydroxyl group-containing polyether and the polyisocyanate compound and the physical properties of polyurethane products or functional oils produced using the hydroxyl group-containing polyether as a raw material. it can.
Usually, after the cyclic ether is polymerized with the initiator, an operation of removing the DMC catalyst from the obtained hydroxyl group-containing polyether is performed. However, if the amount of DMC catalyst remaining in the hydroxyl group-containing polyether is small and does not adversely affect the subsequent reaction with the polyisocyanate compound and the properties of the final product, the hydroxyl group-containing polyether is used without removing the DMC catalyst. Therefore, the production efficiency of the hydroxyl group-containing polyether can be increased.
Specifically, the total amount of metals (for example, Zn and Co) derived from the DMC catalyst contained in the hydroxyl group-containing polyether at the end of the polymerization reaction is 1 to 30 ppm with respect to 100 parts by mass of the hydroxyl group-containing polyether. It is preferable that the amount is 10 ppm or less, particularly preferably because excellent storage stability can be obtained when a urethane prepolymer or a hydrolyzable silyl group-containing polyether is obtained. When the total amount of metals derived from the DMC catalyst is 30 ppm or less, removal of the remaining catalyst from the obtained hydroxyl group-containing polyether tends to be unnecessary.

<Initiator>
The initiator used for the production of the hydroxyl group-containing polyether (I) is a compound having at least one hydroxyl group in one molecule. Specifically, a compound having 1 to 12 hydroxyl groups and having a number average molecular weight (Mn) of 18 to 20,000 is preferable. In addition, when it is comprised only from the molecule | numerator of the same molecular weight, such as the low molecular alcohol as an initiator, let the molecular weight calculated | required from chemical formula be a number average molecular weight (Mn).
Specific examples of the initiator include monovalent compounds such as methanol, ethanol, 2-propanol, n-butanol, iso-butanol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, and oleyl alcohol. Alcohols; water; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-cyclohexanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexane Dihydric alcohols such as diol and 1,4-cyclohexanediol; glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc. Trihydric or higher polyhydric alcohols; sugars such as glucose, sorbitol, dextrose, fructose, sucrose, methylglucoside, trehalose or derivatives thereof; phenols such as bisphenol A, bisphenol F, bisphenol S, novolac, resole, resorcin, Examples include fatty acid triglycerides having a hydroxyl group such as castor oil and castor oil condensate, and condensates thereof.
These compounds can be used alone or in combination of two or more.

Further, a hydroxyl group-containing polyether or polyoxytetramethylene glycol obtained by polymerizing alkylene oxide with these compounds by a known method can also be used as an initiator. These compounds having a polyether chain preferably have a number average molecular weight (Mn) of 300 to 20,000 and a hydroxyl group number of 1 to 12 per molecule.
Further, the hydroxyl value of these compounds is preferably 187 mgKOH / g or less. Furthermore, the compound having a hydroxyl value of 30 mgKOH / g or more higher than the hydroxyl value of the target hydroxyl group-containing polyether is preferable, and a compound having a hydroxyl value of 40 mgKOH / g or more is particularly preferable.

In the present invention, the number average molecular weight (Mn) of the initiator is preferably 300 or more, more preferably 300 to 10,000, more preferably 600 in that the time until the polymerization reaction starts in the presence of a DMC catalyst can be easily shortened. ˜5,000 is particularly preferred.
On the other hand, it is preferable to use an initiator having a number average molecular weight (Mn) of 20,000 or less because the viscosity is not too high when the initiator is charged into the reaction vessel.
The number average molecular weight (Mn) of the initiator is lower than the number average molecular weight (Mn) of the hydroxyl group-containing polyether obtained by using the initiator. The difference between the number average molecular weight of the initiator and the number average molecular weight of the hydroxyl group-containing polyether obtained by using the initiator (that is, the amount of units in which the cyclic ether is opened) is preferably 500 or more, and 1,000 or more. Particularly preferred. When the difference in number average molecular weight is 500 or more, the amount of polymerization in the presence of the DMC catalyst increases, so that a merit that the effect of reducing by-products by polymerization in the presence of the DMC catalyst can be increased can be obtained. Cheap.
Generally, the number average molecular weight of the hydroxyl group-containing polyether to be produced is 1.5 times or more and 30 times or less of the number average molecular weight of the initiator used for producing it in relation to the capacity of the stirring tank. Is preferred.
When the plasticizer (Z) is added together with the initiator before the ring-opening addition reaction of the cyclic ether, it is difficult to be restricted by the capacity of the stirring tank, and the hydroxyl group-containing polyether having a number average molecular weight of 30 times or more of the initiator Manufacture is also easy.

  1-12 are preferable, as for the number of hydroxyl groups of an initiator, 1-8 are more preferable, and 1-4 are especially preferable. When an initiator having a hydroxyl number of not more than the upper limit of the above range is used, the molecular weight distribution of the resulting hydroxyl group-containing polyether tends to be narrow. When using 2 or more types of compounds together as an initiator, the average number of hydroxyl groups per molecule is preferably 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 4. preferable.

<Cyclic ether compound>
As the cyclic ether, a compound having an epoxy ring, an oxetane ring or an oxolane ring is preferable. In particular, a compound having one epoxy ring is preferable.
As the cyclic ether, alkylene oxide is preferable. Examples of the compound having one epoxy ring other than alkylene oxide include halogen-containing alkylene oxide, cycloalkene oxide such as cyclopentene oxide and cyclohexene oxide, aryl-substituted alkylene oxide such as styrene oxide, glycidyl compound such as glycidyl alkyl ether and glycidyl alkyl ester, Etc. The compound having an oxetane ring includes oxetane, and the compound having an oxolane ring includes tetrahydrofuran.
As the cyclic ether, an alkylene oxide is preferable, and an alkylene oxide having 2 to 20 carbon atoms is particularly preferable. Examples of the alkylene oxide used in the present invention include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, α-olefin oxide having 5 to 20 carbon atoms, One or more selected from the group consisting of these can be used.

Among these alkylene oxides, alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide are preferable, and ethylene oxide and propylene oxide are particularly preferable.
The cyclic ether can be determined depending on the target physical properties of the final product using a hydroxyl group-containing polyether as a raw material. However, in the case of using an adhesive, a sealing agent or the like, it is preferable to use only propylene oxide from the viewpoint of water resistance.

In the polymerization step, the cyclic ether may be used alone or in combination of two or more. When two or more kinds of cyclic ethers are subjected to ring-opening addition polymerization to the initiator, a mixture of two or more kinds of cyclic ethers may be subjected to ring-opening addition polymerization to form a random polymer chain, and two or more kinds of cyclic ethers may be separated. May be sequentially subjected to ring-opening addition polymerization to form a block polymer chain. Further, formation of random polymer chains and formation of block polymer chains may be combined.
In the method for producing a hydroxyl group-containing polyether described later, the types of cyclic ethers used in the initial step (a) and the polymerization step (b) may be different. This kind of cyclic ether means not only the kind of cyclic ether but also cyclic ethers having different mixing ratios in the case of a mixture of two or more kinds of cyclic ether compounds.

<Method for producing hydroxyl group-containing polyether>
A preferred method for producing the hydroxyl group-containing polyether of the present invention is a part of a cyclic ether that causes the initiator to undergo a ring-opening addition reaction to a reaction solution containing an initiator and a DMC catalyst (hereinafter sometimes referred to as a cyclic ether for an initial step). ) In an amount of 5 to 20 parts by mass with respect to 100 parts by mass of the initiator contained in the reaction solution, and after the initial step (a), a cyclic ether is added. And a polymerization step (b) in which an additional supply is performed to cause a polymerization reaction.
This method is preferably carried out batchwise, but may be a continuous method. Specifically, it can be carried out as follows.

The mixing means in the initial step (a) of the production method of the present invention is not particularly limited as long as it is a means capable of sufficiently mixing the DMC catalyst and the initiator (including other components used as necessary). Usually, a stirring means is used as the mixing means.
Specific examples of the stirring means in the initial step (a) include stirring blades, bubbling with an inert gas such as nitrogen gas, stirring by electromagnetic waves, ultrasonic waves, and the like, but stirring by stirring blades is preferable.
The shape and material of the pressure-resistant reaction vessel used in the initial step (a) are not particularly limited, but the material is preferably a heat-resistant glass or metal vessel.

First, an initiator, a DMC catalyst, and preferably a plasticizer (Z) are supplied into a pressure-resistant reaction vessel, and before supplying the cyclic ether for the initial step, the gas phase in the pressure-resistant reaction vessel is changed to nitrogen or a cyclic ether for polymerization. It is preferable to substitute with. Thereby, oxygen in the reaction solution is removed.
Next, the reaction liquid is heated while being stirred, and then heated, and then the initial stage cyclic ether is supplied and reacted in a state where the temperature of the reaction liquid is at a predetermined initial temperature. The initial temperature in this specification refers to the temperature of the reaction liquid at the start of the supply of the cyclic ether for the initial step. The initial temperature of the reaction solution is 120 to 165 ° C, preferably 125 to 150 ° C, particularly preferably 130 to 140 ° C. When the initial temperature is not less than the lower limit of the above range, the catalytic activity is remarkably improved, and when it is not more than the upper limit of the above range, there is no fear that the components contained in the reaction solution are thermally decomposed.
Specifically, it is preferable that the temperature of the reaction liquid is increased to the initial temperature while stirring, and the supply of the cyclic ether is started in a state where the temperature of the reaction liquid is maintained. For example, when the reaction liquid reaches a predetermined initial temperature, the heating is stopped, and the supply of cyclic ether is started before the temperature of the reaction liquid starts to drop.

  The cyclic ether for the initial step is a cyclic ether that is polymerized to an initiator in the production of a hydroxyl group-containing polyether. If the supply amount of the cyclic ether for the initial step is too small, the activation of the DMC catalyst becomes insufficient, and if it is too large, a runaway reaction occurs. Therefore, it is 5-20 mass parts with respect to 100 mass parts of the initiator contained in a reaction liquid. 8-15 mass parts is preferable and 10-12 mass parts is especially preferable.

  The cyclic ether for the initial process is supplied in a state where the pressure-resistant reaction vessel is sealed. When the cyclic ether is supplied to the reaction solution, immediately after that, the internal pressure of the pressure-resistant reaction vessel rises as the unreacted cyclic ether is vaporized. Next, when the DMC catalyst is initially activated, a reaction between the cyclic ether and the initiator occurs, and the internal pressure of the pressure-resistant reaction vessel begins to decrease, and at the same time, the temperature of the reaction solution rises due to reaction heat. When the total amount of the supplied cyclic ether has been reacted, the internal pressure of the pressure-resistant reaction vessel is reduced to the same level as before the supply, and the temperature of the reaction liquid is not increased by the reaction heat. Depending on the amount of the organic solvent, there is almost no increase in the temperature of the reaction solution due to the heat of reaction, and an increase in internal pressure may be observed. The initial step (a) in the present specification refers to a step from the start of the supply of the cyclic ether for the initial step to the end of the reaction of the cyclic ether. Completion of the reaction of the cyclic ether for the initial step can be confirmed by a decrease in the internal pressure of the pressure resistant reaction vessel. That is, the end of the initial step (a) refers to the time when the internal pressure of the pressure-resistant reaction vessel is reduced to the same level as before the cyclic ether supply.

Polymerization step (b)
After completion of the initial step, the cyclic ether is newly supplied to the reaction system, the temperature of the reaction solution is adjusted to a predetermined polymerization temperature, and the polymerization reaction is carried out with stirring to obtain the target hydroxyl group-containing polyether.
As the heat-resistant reaction vessel used in the polymerization step (b), a pressure-resistant autoclave vessel is preferably used. However, when the boiling point of the cyclic ether, the plasticizer (Z) or the like is high, the pressure-resistant autoclave vessel may not be high pressure resistant. The material is not particularly limited. As the reaction vessel, the vessel used in the initial step (a) can be used as it is.

  In the polymerization step (b) of the production method of the present invention, in the presence of a DMC catalyst, when the product of the initial step (a) (a compound obtained by reacting a cyclic ether with an initiator) and the cyclic ether are reacted, As in (a), it is preferable to stir the reaction solution. Propeller blades, paddle blades, Max Blend (registered trademark) blades (manufactured by Sumitomo Heavy Industries Process Equipment Co., Ltd.), full zone (registered trademark) blades (manufactured by Shinko Environmental Solution Company), disk turbines, and reaction vessels In order to uniformly mix the inside, a large blade such as a Max Blend blade or a full zone blade is preferable. In addition, dispersers, homomixers, colloid mills, nauter mixers, and the like used for emulsification and dispersion can also be used. Moreover, you may use the mixing by an ultrasonic wave without using a stirring blade. These stirring methods may be used in combination. When using a general stirring method using a stirring blade, increase the rotation speed of the stirring blade as much as possible so long as the gas in the gas phase of the reaction vessel is not taken into the reaction liquid and the stirring efficiency does not decrease. It is preferable to do.

  The polymerization method in the polymerization step (b) is preferably a batch method, but the addition of a mixture containing the cyclic ether and the product of the initial step (a) and the DMC catalyst and the hydroxyl group which is the product of the polymerization step (b) It can also be carried out by a continuous process in which the contained polyether is extracted simultaneously. In particular, when the plasticizer (Z) is used, the continuous method is preferable because the entire system can be reduced in viscosity. When the average molecular weight of the initiator is 300 or less, it is preferable to increase the productivity by using a continuous method.

  125-180 degreeC is preferable and, as for the temperature (polymerization temperature) of the reaction liquid at the time of making cyclic ether react in a superposition | polymerization process (b), 125-160 degreeC is especially preferable. When the polymerization temperature is not less than the lower limit of the above range, an appropriate reaction rate can be obtained, and the remaining amount of unreacted product in the final product can be lowered. Moreover, the high activity of a DMC catalyst is appropriately maintained as it is below the upper limit of the said range, and molecular weight distribution can be made small. After the reaction of the cyclic ether in the polymerization step (b) is completed, it is preferable to cool the reaction solution and purify the reaction product.

  The feed rate of the cyclic ether in the polymerization step (b) is preferably as slow as possible because the molecular weight distribution of the resulting polymer can be narrowed. However, since production efficiency is lowered, it is preferable to compare them. As a specific supply rate, 1 to 200% by mass / hour is preferable with respect to the total mass of the hydroxyl group-containing polyether planned as the final product. The supply rate during the polymerization reaction may be changed gradually.

In addition, you may perform the removal process of a DMC catalyst, and the deactivation process of a DMC catalyst as needed from the reaction liquid obtained after finishing a polymerization process (b). As the method, for example, an adsorption method using an adsorbent selected from synthetic silicate (magnesium silicate, aluminum silicate, etc.), ion exchange resin, activated clay, amine, alkali metal hydroxide, phosphoric acid, A neutralization method using an organic acid such as lactic acid, succinic acid, adipic acid, or acetic acid or a salt thereof, or an inorganic acid such as sulfuric acid, nitric acid, or hydrochloric acid, or a method that uses a neutralization method and an adsorption method together can be used. When primary hydroxylation using the alkali metal catalyst is performed, the alkali metal catalyst can be similarly deactivated and removed.
Moreover, in order to prevent deterioration during long-term storage, a stabilizer may be added as necessary. Examples of the stabilizer include hindered phenol antioxidants such as BHT (dibutylhydroxyltoluene) and octadecyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

<Method for producing terminal unsaturated group-containing polyether>
[Alcoholization reaction process]
In the alcoholate reaction step, the hydroxyl group-containing polyether (I) is reacted with an alkali metal or an alkali metal compound. Thereby, the terminal hydroxyl group of the hydroxyl group-containing polyether is converted into a group represented by -OM (M is an alkali metal). In the present invention, the alcoholate reaction step is performed in the presence of the plasticizer (Z).
The alkali metal or alkali metal compound used in this step is the same as the alkali metal or alkali metal compound used in step (A) in the method for producing the polyoxyalkylene compound (Z ′), including preferred embodiments.

In this step, the molar ratio of the alkali metal or alkali metal compound (based on the alkali metal atom) to the hydroxyl group at the terminal of the hydroxyl group-containing polyether (I) is preferably 1.05 to 1.5 molar equivalents, 1.10 to 1 More preferred is 3 molar equivalents.
When the molar ratio is not less than the lower limit of the above range, alcoholation is sufficiently advanced, and is preferable in that deterioration of storage stability due to remaining unreacted hydroxyl group-containing polyether is avoided, and is not more than the upper limit. From the viewpoint of manufacturing cost.

120-150 degreeC is preferable and, as for the reaction temperature in an alcoholation reaction process, 125-140 degreeC is more preferable.
The reaction time in the alcoholate reaction step is preferably a time for converting all of the terminal hydroxyl groups of the hydroxyl group-containing polyether (I) to -OM. In the present invention, the time required for the alcoholation reaction can be reduced by performing the alcoholation reaction step in the presence of the plasticizer (Z).
The reaction time in the alcoholate reaction step is, for example, preferably 3 hours or more, more preferably 6 hours or more, and further preferably 10 hours or more. Although the upper limit of this reaction time is not specifically limited, 20 hours or less are preferable from the point of production efficiency, and 15 hours or less are more preferable.

  The by-product generated in the alcoholate reaction step is preferably removed by a known method. For example, when sodium alkoxide is used as the alkali metal compound, the hydroxyl group at the end of the hydroxyl group-containing polyether (I) is converted to -ONa group, and methanol is by-produced. Such by-products can be removed by a method of distilling off under reduced pressure.

[Unsaturated group introduction reaction step]
In the unsaturated group introduction reaction step, the polyether obtained in the alcoholate reaction step (polyether having an —OM group introduced at the terminal) is reacted with a halogen compound having an unsaturated group. As a result, a terminal M (alkali metal) is substituted with a residue obtained by removing a halogen atom from the halogen compound, and a polyether having an unsaturated group introduced at the terminal (terminal unsaturated group-containing polyether) is obtained.
Although an unsaturated group is not specifically limited, For example, an alkenyl group is preferable. The alkenyl group is preferably an alkenyl group having 6 or less carbon atoms such as an allyl group, an isopropenyl group, a 1-butenyl group, or a methallyl group, and more preferably an allyl group (—CH ₂ —CH═CH ₂ ) or a methallyl group.
As the halogen of the halogen compound having an unsaturated group, chlorine or bromine is preferable. As the halogen compound having an unsaturated group at the terminal, alkenyl halides are preferable, and alkenyl chlorides such as allyl chloride and methallyl chloride are more preferable.

In this step, the molar ratio of the halogen compound having an unsaturated group to the hydroxyl group at the terminal of the hydroxyl group-containing polyether (I) (based on the halogen atom) is preferably 1.1 to 1.5 molar equivalents, and 1.15 to 1 More preferred is 3 molar equivalents.
When the molar ratio is not less than the lower limit of the above range, it is preferable from the viewpoint of avoiding coloring due to the remaining polyether having an -OM group introduced at the terminal, and is preferably not more than the upper limit from the viewpoint of production cost.

90-120 degreeC is preferable and, as for the reaction temperature in an unsaturated group introduction | transduction reaction process, 100-110 degreeC is more preferable.
The reaction time in the unsaturated group introduction reaction step is preferably a time required for converting all of the —OM groups of the polyether obtained in the alcoholation reaction step into groups containing unsaturated groups.
The reaction time in the unsaturated group introduction reaction step is, for example, preferably 2 hours or more, more preferably 3 hours or more, and further preferably 4 hours or more. The upper limit of the reaction time is not particularly limited, but is preferably 10 hours or less from the viewpoint of production efficiency, and more preferably 5 hours or less.

By-products generated in the unsaturated group introduction reaction step are preferably removed by a known method. For example, when sodium alkoxide is used in the alcoholate reaction step and allyl chloride is used in the unsaturated group introduction reaction step, Na of the -ONa group is converted to an allyl group and sodium chloride (NaCl) is by-produced.
It is preferable to obtain the desired terminal unsaturated group-containing polyether from a reaction product containing a by-product salt such as sodium chloride through a purification step of removing the by-product salt by purification.

  In the purification process, for example, water and a surfactant are added to a terminal unsaturated group-containing polyether (reaction product) containing an alkali metal halide as a by-product salt, and dehydrated to precipitate crystals of the by-product salt. After the formation (crystallization step), the by-product salt can be removed by a method of removing the crystals by solid-liquid separation.

As the surfactant, those generally known as nonionic surfactants can be used. In particular, a compound having 5% by mass or more of oxyethylene group (—O—C ₂ H ₄ —) in the molecule is preferable.
Nonionic surfactants include, for example, polyoxyethylene aliphatic alkyl ether, polyoxyethylene polyoxypropylene aliphatic alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene monoaliphatic carboxylic acid ester, sorbitan mono or polyoxyethylene. Aliphatic ester, polyoxyethylene sorbitan mono fatty acid ester, polyoxyethylene oxypropylene block copolymer, oxyethylene or polyoxyethylene aliphatic amine, fatty acid dialkanolamide, glycerol mono fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, Examples include pentaerythritol fatty acid esters.
The molecular weight of the surfactant is preferably 1,000 to 10,000, and more preferably 4,000 to 6,000. 5-50 mass% is preferable and, as for content of the oxyethylene group in surfactant, 10-30 mass% is more preferable.
The amount of the surfactant used is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the terminal unsaturated group-containing polyether (reaction product containing by-product salt), and 0.1 to 1 part by mass. Is more preferable. When the surfactant is 0.01 part by mass or more, the alkali metal halide in the unpurified terminal unsaturated group-containing polyether is easily extracted into water, and the extracted alkali metal halide is easily precipitated. . When the surfactant is 5 parts by mass or less, the surfactant remaining in the terminal unsaturated group-containing polyether after purification is likely to be sufficiently reduced.

  1-50 mass parts is preferable with respect to 100 mass parts of terminal unsaturated group containing polyether (reaction product containing byproduct salt), and, as for the usage-amount of water, 2-10 mass parts is more preferable. If the amount of water used is 1 part by mass or more, the salt crystals that precipitate after dehydration tend to be sufficiently large. When the amount of water used is 50 parts by mass or less, it takes less time and heat for the dehydration step, which is economically preferable.

<Hydrolysable silyl group-containing polyether>
A hydrolyzable silyl group-containing polyether can be produced by reacting the terminal unsaturated group of the terminal unsaturated group-containing polyether thus obtained with a hydrosilane compound having a hydrolyzable group. The reaction can be performed by a known method, and preferably a catalyst is used.

The hydrosilane compound is preferably a compound represented by the following formula (1).
HSiX ′ _(3-k) R ′ _k (1)
In the formula (1), R ′ is a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group, X ′ is a hydrolyzable group, and k is 0, 1 or 2. When k is 1, two X ′ may be the same as or different from each other. When k is 2, two R ′ may be the same as or different from each other.

The hydrocarbon group as R ′ is preferably an alkyl group or an aryl group, more preferably an alkyl group having 6 or less carbon atoms, and particularly preferably an alkyl group having 3 or less carbon atoms.
The halogenated hydrocarbon group as R ′ is preferably an alkyl group having at least one chlorine atom or fluorine atom, and the alkyl group preferably has 6 or less carbon atoms, more preferably 3 or less.
The hydrolyzable group as X ′ is preferably a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminooxy group, or a ketoximate group. Preferred X ′ is an alkoxy group having 4 or less carbon atoms such as a methoxy group or an ethoxy group; an acyloxy group such as an acetoxy group; a ketoximate group such as an acetoxymate group or a dimethylketoximate group; an N, N-dimethylamino group; -Methylacetamide group; and the like. Particularly preferred is a methoxy group or an ethoxy group.

  It is preferable to use a Group VIII transition metal catalyst as the catalyst. Examples of the Group VIII transition metal catalyst include metals such as platinum, palladium and rhodium, metal compounds such as chloroplatinic acid, and metal complex compounds such as platinum-olefin complexes.

<Curable composition>
In the hydrolyzable silyl group-containing polyether, the hydrolyzable silyl group reacts with moisture to cause a curing reaction.
The hydrolyzable silyl group-containing polyether can be suitably used as a curing component of a curable composition (for example, a curable composition for a sealing material).
The curable composition containing a hydrolyzable silyl group-containing polyether (hereinafter also referred to as polymer (A)) includes a (meth) acrylic acid ester copolymer having a hydrolyzable silyl group (hereinafter referred to as polymer ( C)), a known additive such as a curing catalyst, a cocatalyst, a filler, a plasticizer, a thixotropic agent, an air oxidation curable compound, a stabilizer, an adhesiveness imparting agent, a modulus modifier, and the like. Can do. Specific examples are given below.

<(Meth) acrylic acid ester copolymer having hydrolyzable silyl group (polymer (C))>
The curable composition in this invention may contain a polymer (C) other than a polymer (A).
The repeating unit in the main chain of the polymer (C) contains a (meth) acrylic acid alkyl ester monomer unit and does not contain an alkylene oxide monomer unit. Such a polymer contributes to improving the mechanical strength of the cured product and improving the weather resistance of the curable composition and the cured product. For example, it is effective in suppressing the occurrence of cracks (fine cracks) on the surface when the cured product is exposed to ultraviolet rays for a long time, such as when applied to a sealant used outdoors.

The polymer (C) is a copolymer containing a constitutional unit derived from a (meth) acrylic acid alkyl ester represented by the following general formula (x), and is a water represented by the following general formula (y). A polymer having a decomposable silyl group at the end of the main chain or at the side chain.
CH ₂ = CR ¹² COOR ¹³ (x)
(In the formula, R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents an alkyl group having 1 to 30 carbon atoms.)
-SiX ¹ _b R ¹⁴ _(3-b) (y)
[Wherein, R ¹⁴ represents an optionally substituted monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group), and X ¹ represents a hydroxyl group or a hydrolyzable group. Two X ¹ may be the same or different from each other. b is an integer of 1 to 3. ]
The polymer (C) is a homopolymer or copolymer composed of structural units derived from one or more of the (meth) acrylic acid alkyl ester monomers represented by the general formula (x). There may be a structural unit derived from one or more of the (meth) acrylic acid alkyl ester monomers represented by the general formula (y), and an unsaturated group other than the monomer. The copolymer which consists of a structural unit based on 1 type, or 2 or more types of a monomer may be sufficient.
The number average molecular weight (Mn) of the polymer (C) is preferably 500 to 50,000, more preferably 1,000 to 30,000, and still more preferably 2,000 to 20,000. Alternatively, the mass average molecular weight (Mw) is preferably 600 to 100,000, more preferably 1,200 to 60,000, and further preferably 2,400 to 40,000.

The polymer (C) can be produced by polymerizing the above monomers in the presence of the polymer (A) among the components of the curable composition. Or after superposing | polymerizing and synthesizing the said monomer in presence of the structural component of a curable composition, you may mix with a polymer (A) etc. The monomer may be polymerized in the absence of the constituent components of the curable composition. In this case, it can be polymerized in esters, ketones or aromatic organic solvents and mixed with the polymer (A) or the like. At that time, the solvent used in the synthesis may be removed by vacuum degassing or the like before mixing, or may be removed after mixing with the polymer (A) or the like. It is preferable to deaerate after mixing from the viewpoint of easy handling.
A commercially available polymer (C) can also be used. As such a commercial product, for example, product name: ARUFUON US-6000 series (for example, US-6120, US-6110, etc., both of which are product names) manufactured by Toa Gosei Co., Ltd. can be used.

When the curable composition of this invention contains a polymer (A) and a polymer (C), the ratio of both content is a polymer (C) with respect to 100 mass parts of a polymer (A). Is preferably 5 to 100 parts by mass, and more preferably 5 to 50 parts by mass.
When the content of the polymer (C) is not less than the lower limit of the above range, the effect of addition is easily obtained. When it is at most the upper limit of the above range, workability and a decrease in elongation of the cured product obtained by curing the curable composition can be suppressed.

<Curing catalyst / co-catalyst>
The following compounds can be used as the curing catalyst.
Metal salts such as alkyl titanates, organosilicon titanates, bismuth tris-2-ethylhexoate; acidic compounds such as phosphoric acid, p-toluenesulfonic acid, phthalic acid; butylamine, hexylamine, octylamine, decylamine Aliphatic diamines such as ethylenediamine and hexanediamine; aliphatic polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine; heterocyclic amines such as piperidine and piperazine; metaphenylene Amine compounds such as aromatic amines such as diamines; ethanolamines; various modified amines used as curing agents for triethylamine and epoxy resins.
A mixture of divalent tin such as tin dioctylate (bis (2-ethylhexanoate) tin), tin dinaphthenate and tin distearate and the above amines as a co-catalyst.

Dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate and the following carboxylic acid type organic tin compounds; a mixture of these carboxylic acid type organic tin compounds and the above amines.
_{(N-C 4 H 9)} 2 Sn (OCOCH = CHCOOCH 3) 2,
_{(N-C 4 H 9)} 2 Sn (OCOCH = CHCOOC 4 H 9 -n) 2,
_{(N-C 8 H 17)} 2 Sn (OCOCH = CHCOOCH 3) 2,
_{(N-C 8 H 17)} 2 Sn (OCOCH = CHCOOC 4 H 9 -n) 2,
_{(N-C 8 H 17)} 2 Sn (OCOCH = CHCOOC 8 H 17 -iso) 2.

The following sulfur-containing organotin compounds.
_{(N-C 4 H 9)} 2 Sn (SCH 2 COO),
_{(N-C 8 H 17)} 2 Sn (SCH 2 COO),
_{(N-C 8 H 17)} 2 Sn (SCH 2 CH 2 COO),
_{(N-C 8 H 17)} 2 Sn (SCH 2 COOCH 2 CH 2 OCOCH 2 S),
_{(N-C 4 H 9)} 2 Sn (SCH 2 COOC 8 H 17 -iso) 2,
_{(N-C 8 H 17)} 2 Sn (SCH 2 COOC 8 H 17 -iso) 2,
_{(N-C 8 H 17)} 2 Sn (SCH 2 COOC 8 H 17 -n) 2,
_{(N-C 8 H 17)} 2 SnS.

_{(N-C 4 H 9)} 2 SnO, (n-C 8 H 17) 2 organotin oxide SnO or the like; and these organic tin oxide and ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl maleate, phthalic Reaction products with ester compounds such as dimethyl acid, diethyl phthalate and dioctyl phthalate.

The following chelated tin compounds and reaction products of these tin compounds and alkoxysilanes (where acac is an acetylacetonato ligand).
_{(N-C 4 H 9)} 2 Sn (acac) 2,
_{(N-C 8 H 17)} 2 Sn (acac) 2,
_{(N-C 4 H 9)} 2 (C 8 H 17 O) Sn (acac).

The following tin compounds.
_{(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) 2.

An organometallic compound containing tin or lead can be used in combination with a quaternary ammonium salt and an organometallic compound containing no tin or lead as a catalyst.
<Quaternary ammonium salt>
A quaternary ammonium salt is a compound in which an NH ₄ ⁺ ion (which may be substituted with a hydrogen atom) and a monovalent anion are combined in a form that neutralizes the charge. The compounds shown are preferred.

[Wherein, R ^{5 to} R ⁸ each independently represents a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 25 carbon atoms. X ² represents an organic acid ion, an inorganic acid ion, or a hydroxide ion (OH ⁻ ). ]
<Organic metal compounds that do not contain tin or lead>
Examples of organometallic compounds that do not contain tin or lead include organotitanate compounds, metal chelates such as organoaluminum chelates, and metal carboxylates such as bismuth salts of organic carboxylic acids.

<Filler>
As the filler, heavy calcium carbonate having an average particle diameter of 1 to 20 μm, light calcium carbonate having an average particle diameter of 1 to 3 μm produced by a precipitation method, colloidal calcium carbonate whose surface is treated with a fatty acid or a resin acid organic substance, Fumed silica; precipitated silica; surface silicone-treated silica fine powder; silicic anhydride; hydrous silicic acid; carbon black; magnesium carbonate; diatomaceous earth; calcined clay; clay; talc; Bentonite; Ferric oxide; Zinc oxide; Active zinc white; Shirasu balloon, Perlite, Glass balloon, Silica balloon, Fly ash balloon, Alumina balloon, Zirconia balloon, Carbon balloon and other inorganic hollow bodies; Phenol resin balloon, Epoxy resin Balloon, urea resin balloon, sa Organic resin hollow bodies such as orchid balloons, polystyrene balloons, polymethacrylate balloons, polyvinyl alcohol balloons, styrene-acrylic resin balloons, polyacrylonitrile balloons; resin beads, wood flour, pulp, cotton chips, mica, walnut flour, rice flour, Examples thereof include powdery fillers such as graphite, fine aluminum powder, and flint powder; and fibrous fillers such as glass fiber, glass filament, carbon fiber, Kevlar fiber, and polyethylene fiber.

  These fillers may be used alone or in combination of two or more. Among these, it is preferable to use calcium carbonate, and it is particularly preferable to use heavy calcium carbonate and colloidal calcium carbonate in combination. By using a hollow body (balloon), the curable composition and its cured product can be reduced in weight. In addition, by using a hollow body, it is possible to improve the workability by improving the stringiness of the composition. The hollow body may be used alone or in combination with other fillers such as calcium carbonate. 1-1000 mass parts is preferable with respect to 100 mass parts of a polymer (A), and, as for the usage-amount of the filler in this invention, 50-250 mass parts is more preferable.

<Plasticizer>
As the plasticizer, those mentioned as the plasticizer (Z) can be used. When the terminal unsaturated group-containing polyether is produced using the plasticizer (Z) by the method of the present invention, and the hydrolyzable silyl group-containing polyether is produced using this, the hydrolyzable silyl group-containing polyether and the plastic are produced. A hydrolyzable silyl group-containing polyether composition containing the agent (Z) is obtained.
When producing a curable composition using the obtained hydrolyzable silyl group-containing polyether composition, a plasticizer can be further added as necessary. The plasticizer added when producing the curable composition may be the same as or different from the plasticizer (Z) used during the production of the terminal unsaturated group-containing polyether.

<Thixotropic agent>
The sagging property of the curable composition is improved by the addition of the thixotropic agent. Examples of the thixotropic agent include hydrogenated castor oil, fatty acid amide, calcium stearate, zinc stearate, fine powder silica, and organic acid-treated calcium carbonate.
The thixotropic agent is preferably added in an amount of 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer (A).

[Air oxidation curable compound]
By adding an air oxidation curable compound to the curable composition, the weather resistance of the cured product and the adhesion of dust are improved.
Examples of air oxidative curable compounds include drying oils such as tung oil and linseed oil, alkyd resins obtained by modifying drying oils, acrylic polymers modified with drying oils, silicone resins, polybutadiene, and dienes having 5 to 8 carbon atoms. And diene polymers such as polymers and copolymers, modified products of these polymers and copolymers (maleinization modification, boiled oil modification, etc.), air curable polyester compounds, and the like. These may be used alone or in combination.
As for the usage-amount of an air oxidation curable compound, 0.1-50 mass parts is preferable with respect to 100 mass parts of a polymer (A).

<Stabilizer>
Stabilizers (anti-aging agents) include antioxidants, UV absorbers, light stabilizers, and hindered amines, benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, hindered phenols Phosphorus and sulfur compounds can be used. In particular, it is preferable to use a combination of two or more of light stabilizers, antioxidants, and ultraviolet absorbers. By using such a method, the anti-aging effect can be improved as a whole by making use of the respective characteristics.
Specifically, it is particularly effective to combine two or more selected from tertiary and secondary hindered amine light stabilizers, benzotriazole ultraviolet absorbers, hindered phenols, and phosphite antioxidants. is there.
Products commercially available as antioxidants, ultraviolet absorbers, or light stabilizers can be used as appropriate.
It is preferable that the usage-amount of antioxidant, a ultraviolet absorber, and a light stabilizer is 0.1-10 mass parts, respectively with respect to 100 mass parts of a polymer (A). If the amount is less than 0.1 parts by mass, the anti-aging effect is not sufficiently exhibited, and if it exceeds 10 parts by mass, it is economically disadvantageous.

<Adhesive agent>
In the present technology, an adhesion-imparting agent may be used to improve adhesion. Specific examples of the adhesiveness-imparting agent include organic silane coupling agents such as silane having a (meth) acryloyloxy group, silane having an amino group, silane having an epoxy group, and silane having a carboxyl group; Organometallic coupling agents such as aminoethyl-aminoethyl) propyltrimethoxytitanate, 3-mercaptopropyltrimethotitanate; and epoxy resins.
Specific examples of the silane having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy. Silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, N- (N-vinyl) Benzyl-2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane.

Specific examples of the epoxy resin include bisphenol A-diglycidyl ether type epoxy resin, bisphenol F-diglycidyl ether type epoxy resin, tetrabromobisphenol A-glycidyl ether type epoxy resin, novolac type epoxy resin, hydrogenated bisphenol A type epoxy. Resin, glycidyl ether type epoxy resin of bisphenol A-propylene oxide adduct, glycidyl 4-glycidyloxybenzoate, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl ester epoxy resin, m-aminophenol Epoxy resin, diaminodiphenylmethane epoxy resin, urethane-modified epoxy resin, N, N-diglycidylaniline, N, N-diglycidyl-o- Toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ethers of polyhydric alcohols (such as glycerin), hydantoin type epoxy resins, unsaturated polymer (petroleum resin) epoxy resin.
When adding the said organosilane coupling agent to a curable composition, it is preferable that the addition amount is 0.1-30 mass parts with respect to 100 mass parts of a polymer (A).
When adding the said epoxy resin to a curable composition, the addition amount is 100 mass parts or less with respect to 100 mass parts of a polymer (A), and 10-80 mass parts is more preferable.

  Specific examples of the epoxy resin curing agent include, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine, oleylamine, and the like. Aliphatic amines; mensendiamine, isophoronediamine, norbornanediamine, piperidine, N, N′-dimethylpiperazine, N-aminoethylpiperazine, 1,2-diaminocyclohexane, bis (4-amino-3-methylcyclohexyl) methane Alicyclic amines such as bis (4-aminocyclohexyl) methane, polycyclohexylpolyamine, DBU; metaphenylenediamine, 4,4′-diaminodiphenylme , Aromatic amines such as 4,4′-diaminodiphenylsulfone; m-xylylenediamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, etc. Aliphatic aromatic amines: 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (ATU), morpholine, N-methylmorpholine, polyoxypropylene Amines having an ether bond such as diamine, polyoxypropylene triamine, polyoxyethylenediamine; hydroxyl-containing amines such as diethanolamine and triethanolamine; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride Acid, no dodecyl Acid anhydrides such as succinic acid; polyamides obtained by reacting diamine acids with polyamines such as diethylenetriamine and triethylenetetramine; polyamidoamines such as polyamides using polycarboxylic acids other than dimer acids; 2-ethyl-4 -Imidazoles such as methylimidazole; Dicyandiamide; Polyoxypropylene amines such as polyoxypropylene diamine and polyoxypropylene triamine; Phenols; Epoxy-modified amine obtained by reacting the above amines with an epoxy compound, Modified amines such as Mannich-modified amine, Michael addition-modified amine, ketimine and aldimine obtained by reacting amines with formalin and phenols; 2-ethylhexyl of 2,4,6-tris (dimethylaminomethyl) phenol Examples thereof include amine salts such as sanates. These curing agents may be used alone or in combination of two or more.

  These epoxy resin curing agents are usually used in the range of 0.001 to 100 parts by weight, preferably in the range of 0.01 to 90 parts by weight with respect to 100 parts by weight of the polymer (A). . If the amount of the curing agent for epoxy resin used is less than 0.001 part by weight, curing of the epoxy resin becomes insufficient, and if it exceeds 90 parts by weight, the adhesiveness may decrease due to bleeding to the interface, etc., which is not preferable.

<Modulus modifier>
As other additives, a modulus adjusting agent may be used. The modulus modifier refers to a compound that can generate trimethylsilanol by hydrolysis. For example, a compound containing a trimethylsilyloxy group in the molecule. Trimethylsilanol generated by the hydrolysis of the modulus modifier reacts with the polymer (A), and therefore the mechanical properties of the curable composition can be changed.
Specific examples of the modulus regulator include phenoxytrimethylsilane, trimethylolpropane tristrimethylsilyl (also referred to as TMP-3TMS), and the like. 1 type may be used independently and 2 or more types may be used together.
The modulus modifier is not particularly limited as long as it has a functional group capable of generating trimethylsilanol, such as a trimethylsilyloxy group, but a compound having a molecular weight of 2,000 or less is preferable, and a compound having a molecular weight of 500 or less is more preferable. In addition, the average number of functional groups capable of generating trimethylsilanol is preferably 0.5 to 8.0 or less, and more preferably 0.9 to 4.0 on average.

Examples of the modulus regulator include monohydric alcohols such as methanol, ethanol, 2-ethylhexanol, and phenol; polyhydric alcohols such as ethylene glycol, propanediol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol; A compound obtained by trimethylsilyloxylation of is preferred. Examples of the compound to be trimethylsilyloxylated include 1,1,1,3,3,3-hexamethyldisilazane and trimethylchlorosilane.
Although the trimethylsilyloxylation rate in all the hydroxyl groups of a polyhydric alcohol can be adjusted arbitrarily, 50% or more is preferable and 80% or more is more preferable. Most preferably, substantially all hydroxyl groups are trimethylsilyloxylated.
The usage-amount of a modulus regulator is not specifically limited, A usage-amount can be freely set according to the physical property of the target hardened | cured material. Usually, 0.1-10.0 mass parts is preferable with respect to 100 mass parts of a polymer (A), and 0.1-5.0 mass parts is more preferable. In addition, for the purpose of adjusting the curing speed, several types of modulus adjusting agents may be used in combination.
Moreover, a modulus regulator may be added to the polymer (A) in advance, or may be added when producing the curable composition.

<Curable composition>
The curable composition of the present invention can be prepared as a one-component type in which all the ingredients are pre-blended and stored in a sealed state and cured by moisture in the air after construction. Separately from the main component, it may be prepared as a two-component type in which components such as a curing catalyst, a filler, and water are blended as a curing agent composition, and the curing agent composition and the main component are mixed before use. it can.

In the case of the one-component type, since all the blended components are blended in advance, it is preferable that the blended components containing moisture be used after being dehydrated and dried in advance or dehydrated under reduced pressure during blending and kneading.
In the case of the two-component type, there is no need to blend a curing catalyst in the main agent containing a polymer having a hydrolyzable silyl group, so there is little concern about gelation even if some water is contained in the main agent. When long-term storage stability is required, it is preferable to perform dehydration drying.
As the dehydration and drying method, a heat drying method is preferable in the case of a solid substance such as a powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel or the like is preferable in the case of a liquid material. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ -Storage stability is further improved by adding an alkoxysilane compound such as glycidoxypropyltrimethoxysilane.
The amount of the silicon compound capable of reacting with water such as dehydrating agent, especially vinyltrimethoxysilane, is preferably 0.1 to 20.0 parts by mass with respect to 100 parts by mass of the total amount of the polymer (A). 5-10.0 mass parts is more preferable.

  The curable composition of the present invention comprises a sealing material (such as an elastic sealing material sealant for construction and a sealing material for double-glazed glass), a sealing agent (a sealing agent for rust prevention and waterproofing at the glass edge, a solar cell back surface sealing). It is useful as an adhesive used in the fields of electrical insulating materials (insulating coatings for electric wires and cables) and the like. Moreover, the curable composition of this invention can be used also for uses, such as an adhesive, a coating material, a film material, a gasket material, a casting material.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.
<Measurement method>
[Hydroxyl value]
The hydroxyl group of the object to be measured was esterified with a pyridine solution of phthalic anhydride and measured by a titration method using a sodium hydroxide (NaOH) solution (based on JIS K1557 (2007 edition)).

[Number average molecular weight (Mn) and weight average molecular weight (Mw)]
The number average molecular weight (Mn) and the weight average molecular weight (Mw) in the following examples are measured by gel permeation chromatography (GPC) under the following conditions using a calibration curve prepared using a standard polystyrene sample with a known molecular weight. The molecular weight in terms of polystyrene obtained by
[GPC measurement conditions]
Model used: HLC-8220GPC (manufactured by Tosoh Corporation),
Data processing device: SC-8020 (manufactured by Tosoh Corporation),
Column used: TSG gel G2500H (manufactured by Tosoh Corporation),
Column temperature: 40 ° C., detector: RI,
Solvent: Tetrohydrofuran, flow rate 0.6 ml / min,
Sample concentration: 0.5% by mass, injection volume: 10 μl,
Standard sample for preparing a calibration curve: polystyrene ([Easical] PS-2 [Polystyrene Standards], manufactured by Polymer Laboratories).
[viscosity]
1 mL of a sample was taken, and using an E type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: RE80 type) The viscosity was measured under the condition of 4. JS14000 (manufactured by Nippon Grease Co., Ltd.) was used as the calibration standard solution. The measurement temperature was measured at 25 ° C. unless otherwise specified.

[Unsaturation]
The iodine value was measured by a known Wis method, and the value obtained by converting the obtained iodine value into a vinyl equivalent was defined as the degree of unsaturation.
In the Wiis method, a sample is reacted with a Wis solution (iodine monochloride in acetic acid) and left in the dark, after which excess iodine monochloride is reduced to iodine and the iodine content is titrated with sodium thiosulfate to give an iodine value. Was calculated.

<Production of DMC catalyst>
[Reference Example 1: Production of DMC catalyst slurry (slurry catalyst (s))]
The polyol X used in this example was produced by subjecting propylene oxide to ring-opening addition reaction to propylene glycol using a potassium hydroxide (KOH) catalyst, and further purifying it by a known method. Polyoxypropylene diol having a molecular weight (Mn) of 1,000 and a hydroxyl value of 112 mgKOH / g.

First, an aqueous zinc chloride solution consisting of 10.2 g of zinc chloride and 10 g of ion-exchanged water was prepared in a 500 mL flask and stirred at 300 rpm while keeping the temperature at 40 ° C. To this, an aqueous solution composed of 4.2 g of potassium hexacyanocobaltate [K ₃ Co (CN) ₆ ] and 75 g of ion-exchanged water was dropped over 30 minutes. After completion of the dropwise addition, the mixture was further stirred for 30 minutes, and then a mixture comprising 80 g of tert-butyl alcohol (hereinafter abbreviated as TBA), 80 g of ion-exchanged water, and 0.6 g of polyol X was added, and the mixture was stirred at 40 ° C. for 30 minutes The mixture was further stirred at 60 ° C. for 60 minutes. The obtained mixture was filtered under pressure (0.25 MPa) using a circular filter plate having a diameter of 125 mm and a quantitative filter paper for fine particles (No. 5C manufactured by ADVANTEC), and the composite metal cyanide complex was obtained in 50 minutes. A solid (cake) containing was obtained.

  Next, the obtained cake was transferred to a flask, a mixed solution consisting of 36 g of TBA and 84 g of ion-exchanged water was added and stirred for 30 minutes, and then pressure filtration was performed for 15 minutes under the same conditions as above, and the cake was again obtained. Got. The cake was transferred to a flask, and a mixed solution composed of 108 g of TBA and 12 g of ion-exchanged water was added and stirred for 30 minutes to obtain a slurry containing a double metal cyanide complex.

To this slurry, 100 g of polyol X was added and dried under reduced pressure at 80 ° C. for 3 hours and further at 115 ° C. for 4 hours, and a slurry of a composite metal cyanide complex catalyst having TBA as an organic ligand (slurry catalyst (s) ) The concentration of the double metal cyanide complex catalyst in the slurry catalyst (s) was 4.1% by mass. In the formula (11), M ¹ and M ³ are Zn, M ² is Co, and L is TBA.

<Manufacture of plasticizer (Z)>
[Production Example 1: Production of polyoxyalkylene compound (Z-1)]
A pressure resistant reaction vessel (capacity 5 L) made of stainless steel (JIS-SUS-316) equipped with a stirrer and capable of controlling the temperature of the reaction solution was used. Specifically, the pressure-resistant reaction vessel includes a stirrer to which one set of anchor blades and two sets of 45 ° inclined two-blade paddle blades are attached, and a heating tank through which a heat medium flows is provided around the vessel. A cooling pipe through which cooling water flows is provided inside the container. The temperature of the reaction solution was measured by a method of measuring the solution temperature with a thermometer installed at the lower part inside the pressure resistant reaction vessel.

(Ring-opening addition reaction process)
First, 96 g of methanol as an initiator and 11 g of solid potassium hydroxide as a catalyst for the ring-opening addition reaction of alkylene oxide were charged into a pressure-resistant reaction vessel. Next, after replacing the inside of the pressure resistant reactor with nitrogen, the reaction solution was heated with stirring. When the temperature reached 105 ° C., the heating was stopped, the liquid temperature was maintained at 105 ° C., and while stirring, a mixture of 3180 g of propylene oxide and 324 g of ethylene oxide was fed over 7 hours to react, and polyoxyalkylene monool (theoretical production) Amount 3600 g).
(Alcoholization process)
Subsequently, the hydroxyl group at the terminal of the polyoxyalkylene monool was alcoholated. That is, after the supply of propylene oxide and ethylene oxide was completed, it was confirmed that the pressure in the pressure resistant reactor had sufficiently decreased, and then the liquid temperature was lowered to 60 ° C. 1.5 equivalents), and 540 g of methanol as a solvent (15 parts by mass with respect to 100 parts by mass of polyoxyalkylene monool) were added, and the liquid temperature was again heated to 130 ° C. (reaction temperature), and a pressure-resistant reaction vessel The inner pressure was reduced to 10 kPa or less (decompression degree), and the reaction was carried out while dehydrating while maintaining for 11 hours (reaction time) to replace the terminal hydroxyl group with -ONa.
The methanol content (residual solvent amount) in the reaction product after alcoholation (in this example, when the reaction was completed for 11 hours) was measured by the above-mentioned method and found to be 2900 ppm.

(Methylation process)
Then, after returning the pressure to normal pressure with nitrogen gas, the liquid temperature was lowered to 100 ° C. (reaction temperature), and then 239 g of methyl chloride (1.6 equivalents relative to the theoretical hydroxyl terminal) was supplied over 1 hour. . After completion of the supply, by performing aging for 2 hours, to replace the -ONa end to -OCH _3. Then, after removing unreacted methyl chloride by degassing under reduced pressure, the product was taken out from the pressure resistant reactor.

(Neutralization and purification process)
3000 g of the obtained product was transferred to a 5 L separable flask, and 1000 g of distilled water and 25 g of phosphoric acid as a neutralizing agent for residual alkali were added. The separable flask was heated to 90 ° C., stirred, and neutralized for 1 hour. After confirming that the pH of the system was 7 or less, stirring was stopped. The resulting reaction solution was separated into two layers, and the upper aqueous layer containing neutralized salt (NaCl) was removed. Thereafter, 60 g of Kyowad 600S (magnesium silicate-based adsorbent) and 60 g of Kyowado 1000 (hydrotalcite-based adsorbent) (both manufactured by Kyowa Chemical Industry Co., Ltd.) were added as adsorbents for the neutralized salt remaining on the product side. did. The mixture was heated to 120 ° C., stirred, adsorbed while being degassed under reduced pressure for 2 hours, and then filtered to obtain the desired polyoxyalkylene compound (Z-1). The obtained polyoxyalkylene compound (Z-1) had a polystyrene equivalent molecular weight (number average molecular weight Mn) of 1,200 and a weight average molecular weight of 1,270 as measured by GPC. The hydroxyl value of the polyoxyalkylene compound (Z-1) was 0.2 mgKOH / g.

<Production of unsaturated group-containing polyether>
[Example 1]
In this example, a hydroxyl group-containing polyether (polyether polyol) is synthesized in the presence of a plasticizer (Z) to obtain a raw material composition containing the plasticizer (Z) and the hydroxyl group-containing polyether. A hydrolyzable silyl group-containing polyether was produced by reacting the isocyanate group-containing compound (U).
The initiator (1) used in this example is a polyoxy having a number average molecular weight (Mn) of 2,000 produced using the slurry catalyst (s) produced in Reference Example 1 and a hydroxyl value of 56.1 mgKOH / g. Propylene diol.
In this example, the polyoxyalkylene compound (Z-1) produced in Production Example 1 was used as the plasticizer (Z). The slurry catalyst (s) produced in Reference Example 1 was used as the DMC catalyst. Moreover, the pressure | voltage resistant reaction container (capacity 10L) similar to manufacture example 1 was used.

First, 444 g of initiator (1), 2400 g of polyoxyalkylene compound (Z-1) (hydroxyl value is 0.2 mgKOH / g), and slurry catalyst (s) are charged into a pressure-resistant reaction vessel. It was.
The addition amount of the polyoxyalkylene compound (Z-1) was 30% by mass with respect to the total of the initiator, the total PO and the polyoxyalkylene compound (Z-1), that is, the raw material composition.
The amount of the slurry catalyst (s) used was such that the concentration converted to the DMC catalyst was 50 ppm. The content of the metal derived from the slurry catalyst (s) DMC catalyst is 7 ppm for Zn and 3 ppm for Co. In this example, the concentration of the slurry catalyst (s) is a concentration relative to 100 parts by mass of the initiator used for the production of the hydroxyl group-containing polyether and the total PO (amount of the hydroxyl group-containing polyether produced). The same applies to the following examples.

Next, after replacing the inside of the pressure resistant reactor with nitrogen, the reaction solution was heated with stirring. When the temperature reached 130 ° C. (initial temperature), the heating was stopped, and 44 g (10 parts by mass with respect to 100 parts by mass of the initiator) of PO was supplied into the pressure-resistant reaction vessel while the stirring was continued.
When PO was supplied into the pressure-resistant reaction vessel (start of the initial process), the internal pressure of the pressure-resistant reaction vessel once increased. Thereafter, the pressure gradually decreased, and it was confirmed that the pressure was the same as the internal pressure of the pressure-resistant reaction container immediately before supplying PO (end of the initial step). During this time, when the internal pressure began to decrease, the temperature of the reaction solution once increased, and then gradually decreased.
After the completion of the initial step, 5156 g of PO was fed into the pressure-resistant reaction vessel at a feed rate of 360 g / hour, and a ring-opening addition reaction was performed at a polymerization temperature of 130 ° C. It was confirmed that the internal pressure did not change and the reaction was completed. In this way, polyether polyol (I-1) (polyether diol) was produced.
The obtained reaction product contains polyether polyol (I-1) and polyoxyalkylene compound (Z-1) which is a plasticizer. The reaction product was used as a raw material composition.

The GPC spectrum of the obtained raw material composition is the spectrum of the produced hydroxyl group-containing polyether (polyether polyol (I-1)) and the plasticizer (polyoxyalkylene compound (Z-1)) having a lower molecular weight than this spectrum. ) Showed two separate spectra. The weight average molecular weight (Mw) of the spectrum derived from the high molecular weight hydroxyl group-containing polyether (polyether polyol (I-1)) was determined. In addition, when the polyether monool which is a by-product is contained, the peak of this polyether monool shall be contained in the spectrum by polyether polyol.
The hydroxyl value of the raw material composition was measured by the above titration method (JIS K1557). The hydroxyl value of the hydroxyl group-containing polyether (polyether polyol (I-1)) is a value calculated using the following formula from the hydroxyl value of the raw material composition and the ratio (mass%) of the plasticizer in the raw material composition. It is.
“Hydroxyl value of hydroxyl group-containing polyether” = “Hydroxyl value of raw material composition” ÷ {1− (ratio of plasticizer ÷ 100)}
Moreover, the viscosity of the raw material composition was measured. These values are shown in the table (hereinafter the same).

An unsaturated group-containing polyether was produced by introducing an unsaturated group into the obtained raw material composition.
Into a pressure-resistant reaction vessel (internal volume 5 L (liter)), 3000 g of the raw material composition obtained above was added, and a methanol solution of sodium methoxide (concentration 28 mass%) was added in a nitrogen atmosphere. Reacted for hours. The amount of sodium methoxide added was 1.15 equivalents relative to the hydroxyl group (calculated value from the charged amount) of the hydroxyl group-containing polyether (polyether polyol (I-1)). By this reaction, the terminal hydroxyl group of the polyether polyol (I-1) is converted to -ONa group, and methanol is by-produced.
Subsequently, after distilling off methanol under reduced pressure, allyl chloride was added and reacted at 100 ° C. for 4 hours. The addition amount of allyl chloride was 1.20 equivalents relative to the hydroxyl group (calculated value from the charged amount) of the hydroxyl group-containing polyether (polyether polyol (I-1)). By this reaction, the terminal —ONa group is converted to —O—CH ₂ CH═CH ₂ group, and NaCl is by-produced.
Subsequently, unreacted allyl chloride was removed under reduced pressure to obtain an unsaturated group-containing polyether (reaction product) containing NaCl as a by-product salt.

After adding 1 part by mass of a polyoxyethyleneoxypropylene block copolymer and 3 parts by mass of water as a surfactant to 100 parts by mass of the obtained unsaturated group-containing polyether (a reaction product containing a by-product salt) The water was gradually evaporated to precipitate salt crystals.
Next, the mixture was transferred to a filter equipped with a filter paper to obtain an unsaturated group-containing polyether from which by-product salt (NaCl) was removed.
The unsaturated group-containing polyether obtained had an unsaturation degree of 0.082 mmol / g and a viscosity at 25 ° C. of 6 Pa · s.
Furthermore, the terminal conversion rate of the unsaturated group-containing polyether obtained from the following formula was 100%.
Terminal conversion rate of unsaturated group-containing polyether = Unsaturation degree of unsaturated group-containing polyether ÷ (Hydroxyl value of hydroxyl group-containing polyether ÷ Molecular weight of potassium hydroxide 56.1) × 100 (%)
In the same manner as in Example 1, the degree of unsaturation, terminal conversion, and viscosity of the obtained unsaturated group-containing polyether were measured. The results are shown in Table 1. Table 1 also describes the main manufacturing conditions (hereinafter the same).

[Example 2]
The difference between this example and Example 1 is that there is no plasticizer (Z) when synthesizing the hydroxyl group-containing polyether (polyether polyol), and the plasticizer (Z) is added after synthesizing the hydroxyl group-containing polyether. The raw material composition and the PO supply rate were slowed down.
That is, in Example 1, the initiator (1) was subjected to a ring-opening addition reaction in the same manner except that the polyoxyalkylene compound (Z-1) was not added and the PO feed rate was changed to 120 g / hour. Thus, polyether polyol (I-2) (polyether diol) was produced.
What added the polyoxyalkylene compound (Z-1) to the obtained reaction product was made into the raw material composition. The addition amount of the polyoxyalkylene compound (Z-1) was 30% by mass with respect to the total of the initiator, the total PO and the polyoxyalkylene compound (Z-1), that is, the raw material composition.
Unsaturated groups were introduced into the obtained raw material composition in the same manner as in Example 1 to produce unsaturated group-containing polyethers.

[Example 3]
This example is significantly different from Example 1 in that the weight average molecular weight of the hydroxyl group-containing polyether (polyether polyol) is larger than that of Example 1.
That is, in Example 1, the initiator and PO supply amounts were changed to 255 g and 5345 g, respectively. Others were carried out similarly to Example 1, and produced | generated polyether polyol (I-3) (polyether diol). The obtained reaction product contains polyether polyol (I-3) and polyoxyalkylene compound (Z-1) which is a plasticizer. The reaction product was used as a raw material composition.
Unsaturated groups were introduced into the obtained raw material composition in the same manner as in Example 1 to produce unsaturated group-containing polyethers.

[Example 4]
The difference between this example and Example 3 is that there is no plasticizer (Z) when synthesizing the hydroxyl group-containing polyether (polyether polyol), and the plasticizer (Z) is added after synthesizing the hydroxyl group-containing polyether. The raw material composition and the PO supply rate were slowed.
That is, in Example 3, the initiator (1) was subjected to a ring-opening addition reaction in the same manner except that the polyoxyalkylene compound (Z-1) was not added and the PO feed rate was changed to 120 g / hour. Thus, polyether polyol (I-4) (polyether diol) was produced.
What added the polyoxyalkylene compound (Z-1) to the obtained reaction product was made into the raw material composition. The addition amount of the polyoxyalkylene compound (Z-1) was 30% by mass with respect to the total of the initiator, the total PO and the polyoxyalkylene compound (Z-1), that is, the raw material composition.
Unsaturated groups were introduced into the obtained raw material composition in the same manner as in Example 1 to produce unsaturated group-containing polyethers.

[Comparative Example 1]
As in Example 2, the initiator (1) was subjected to a ring-opening addition reaction of PO without adding the polyoxyalkylene compound (Z-1) to produce a polyether polyol (I-5) (polyether diol). did. A raw material composition was prepared without adding the polyoxyalkylene compound (Z-1) to the obtained reaction product.
Unsaturated groups were introduced into the obtained raw material composition in the same manner as in Example 1 to produce unsaturated group-containing polyethers.
[Comparative Examples 2 and 3]
In Comparative Example 1, the reaction time in the alcoholate reaction step was 12 hours, but in Comparative Example 2, this was 18 hours, and in Comparative Example 3, it was 2 hours. Others were the same as in Comparative Example 1.

[Comparative Example 4]
As in Example 4, the initiator (1) was subjected to a ring-opening addition reaction of PO without adding the polyoxyalkylene compound (Z-1) to produce a polyether polyol (I-6) (polyether diol). did. A raw material composition was prepared without adding the polyoxyalkylene compound (Z-1) to the obtained reaction product.
Unsaturated groups were introduced into the obtained raw material composition in the same manner as in Example 1 to produce unsaturated group-containing polyethers.
[Comparative Examples 5 and 6]
In Comparative Example 4, the reaction time in the alcoholate reaction step was 24 hours, but in Comparative Example 5, this was 38 hours, and in Comparative Example 6, it was 40 hours. Others were the same as in Comparative Example 4.

As shown in the results of Table 1, in Examples 1 and 2 in which the alcoholation reaction step was performed in the presence of the plasticizer (Z), the reaction time in the alcoholation reaction step was 12 hours. The terminal conversion rate of ether was 100%.
On the other hand, in Comparative Examples 1 to 3 in which the plasticizer (Z) was not used, the reaction time in the alcoholate reaction step was 12 hours (Comparative Example 1) as in Examples 1 and 2, and the unsaturated group-containing poly The terminal conversion rate of ether was as low as 60%, reaching only 94% even in 18 hours (Comparative Example 2), and reached 100% when reacted for 20 hours (Comparative Example 3).

Further, in Examples 3 and 4 in which the alcoholation reaction step was performed in the presence of the plasticizer (Z) even in a system in which the hydroxyl group-containing polyether had a high weight average molecular weight, the reaction time in the alcoholation reaction step was 24 hours. The terminal conversion rate of the unsaturated group-containing polyether was 100%.
On the other hand, in Comparative Examples 4 to 6 in which the plasticizer (Z) was not used, the reaction time in the alcoholate reaction step was 24 hours (Comparative Example 4), which was the same as in Examples 4 and 5. The terminal conversion rate of ether was as low as 55%, reaching only 93% even at 38 hours (Comparative Example 5), and reached 100% when reacted for 40 hours (Comparative Example 6).

From these results, an unsaturated group-containing polyether having a terminal conversion rate of 100% is obtained by carrying out an alcoholation reaction step in the presence of a plasticizer (Z) to produce a terminal unsaturated group-containing polyether. It can be seen that the reaction time required in the alcoholate reaction step is shortened.
Therefore, the terminal conversion rate of the unsaturated group-containing polyether can be improved when the reaction time is the same. Further, an unsaturated group-containing polyether having a terminal conversion rate of 100% can be efficiently produced in a shorter time.

Claims (9)

It has an unsaturated group after reacting a polyether chain derived from a cyclic ether compound and a hydroxyl group-containing polyether (I) having a hydroxyl group with an alkali metal or an alkali metal compound in the presence of a plasticizer (Z). Reacting with a halogen compound to introduce an unsaturated group into the terminal of the hydroxyl group-containing polyether (I),
The plasticizer (Z) is the following plasticizer (Za), and the hydroxyl group-containing polyether (I) is synthesized in the absence of the plasticizer (Z), containing terminal unsaturated groups A method for producing a polyether.
Plasticizer (Za): a compound having a weight average molecular weight smaller than that of the hydroxyl group-containing polyether (I), cyclohexanedicarboxylic acid esters, phthalic acid esters, epoxy plasticizer, polyester plasticizer, poly One or more compounds selected from the group consisting of ether plasticizers, polyvinyl polymers, aliphatic hydrocarbon compounds having 8 to 18 carbon atoms, and chlorinated paraffins having 10 to 30 carbon atoms. It has an unsaturated group after reacting a polyether chain derived from a cyclic ether compound and a hydroxyl group-containing polyether (I) having a hydroxyl group with an alkali metal or an alkali metal compound in the presence of a plasticizer (Z). Reacting with a halogen compound to introduce an unsaturated group into the terminal of the hydroxyl group-containing polyether (I),
The hydroxyl group-containing polyether (I) is synthesized in the presence of a part or all of the plasticizer (Z), and the plasticizer (Z) is the following plasticizer (Zb). A method for producing an unsaturated group-containing polyether.
Plasticizer (Zb): a compound having a hydroxyl value of 2.0 or less and a weight average molecular weight smaller than that of the hydroxyl group-containing polyether (I), cyclohexanedicarboxylic acid esters, phthalic acid esters , Epoxy plasticizer, polyester plasticizer, polyether plasticizer, polyvinyl polymer, aliphatic hydrocarbon compound having 8 to 18 carbon atoms, and chlorinated paraffin having 10 to 30 carbon atoms. One or more compounds.   The manufacturing method of the terminal unsaturated group containing polyether of Claim 1 or 2 which makes the said plasticizer (Z) exist 10-300 mass% with respect to the sum total of hydroxyl-containing polyether (I) and this plasticizer. .   The terminal unsaturated group-containing polyether according to any one of claims 1 to 3, wherein the plasticizer (Z) is a polyoxyalkylene compound (Z ') having a polyoxyalkylene chain derived from an alkylene oxide. Manufacturing method.   The polyoxyalkylene compound (Z ') is a polyoxyalkylene compound having one or more terminal groups selected from the group consisting of an alkoxy group and an acyloxy group at the terminal of the polyoxyalkylene chain. A method for producing a terminal unsaturated group-containing polyether.   The method for producing a terminal unsaturated group-containing polyether according to claim 5, wherein the alkoxy group has 1 to 8 carbon atoms and the acyloxy group has 2 to 8 carbon atoms. The polyoxyalkylene compound (Z ′) is a polyoxyalkylene compound having a molecular weight of 100 to 2000 per terminal group obtained by converting the hydroxyl group of the following hydroxyl group-containing polyoxyalkylene compound (z1) to an alkoxy group. The manufacturing method of the terminal unsaturated group containing polyether of Claim 5 which exists.
Hydroxyl group-containing polyoxyalkylene compound (z1): A hydroxyl group-containing polyoxyalkylene compound having a polyoxyalkylene chain derived from an alkylene oxide having 2 to 4 carbon atoms and having 1 to 3 hydroxyl groups.   The method for producing a terminal unsaturated group-containing polyether according to any one of claims 5 to 7, wherein all terminal groups of the polyoxyalkylene compound (Z ') are methoxy groups.   The method for producing a terminal unsaturated group-containing polyether according to any one of claims 4 to 8, wherein the alkylene oxide in the polyoxyalkylene compound (Z ') is one or both of propylene oxide and ethylene oxide.