WO2019203234A1

WO2019203234A1 - Method for producing polyether

Info

Publication number: WO2019203234A1
Application number: PCT/JP2019/016334
Authority: WO
Inventors: 優長岡
Original assignee: 株式会社カネカ
Priority date: 2018-04-18
Filing date: 2019-04-16
Publication date: 2019-10-24
Also published as: JP7393330B2; JPWO2019203234A1

Abstract

Provided are a method for producing a purified polyether capable of efficiently removing impurities from the polyether without using water, and a method for producing a reactive silicon group-containing polyether. A crude polyether containing a water-soluble compound and an aprotic polar organic solvent, or a crude polyether and a protic polar organic solvent and a nonpolar organic solvent, are mixed, and the precipitated solid is subsequently separated by standing, centrifugation, or filtration to remove the water-soluble compound which is an impurity.

Description

Method for producing polyether

The present invention relates to a method for producing a polyether.

The reactive silicon group-containing polyether can be crosslinked even at room temperature by forming a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture or the like. It is known that a reactive silicon group-containing polyether has a property of giving a rubber-like cured product by such a crosslinking reaction.

Reactive silicon group-containing polyether has already been industrially produced. Reactive silicon-containing polyethers are widely used in applications such as sealants, adhesives, and paints.

As an example of a method for producing such a reactive silicon group-containing polyether, a ring-opening polymerization of alkylene oxide is carried out using an alkali metal such as KOH or a double metal cyanide complex as a catalyst to produce a polyether having a hydroxyl group at the terminal. And the method of converting the terminal hydroxyl group which the said polyether has into an olefin, and obtaining the unsaturated group containing polyether which has an unsaturated group at the terminal is known (refer patent document 1). A method for producing a reactive silicon group-containing polyether by hydrosilylation reaction between an unsaturated group at the terminal of an unsaturated group-containing polyether obtained by the method described in Patent Document 1 and a hydrosilane compound having a reactive silicon group Is known and has already been industrially put into practical use.

However, in the above method, if an alkaline component is present in the unsaturated group-containing polyether or a metal impurity derived from a polymerization catalyst such as a double metal cyanide complex and / or its residue compound is present, the subsequent hydrosilylation The reaction may be inhibited. Further, if a large amount of salt is present in the unsaturated group-containing polyether, it causes turbidity.

In order to prevent reaction inhibition and turbidity, vigorously stir the unsaturated group-containing polyether and washing water to which an acidic component has been added to remove the aqueous phase, or wash the unsaturated group-containing polyether and organic solvent. By vigorously stirring water and removing the aqueous phase, it is possible to reduce the alkaline component, the metal impurities derived from the polymerization catalyst, and the salt in the unsaturated group-containing polyether. (See Patent Document 2 and Patent Document 3)

However, since the above purification method uses water, drainage facilities are required, the process is complicated, and mixing of polyether and washing water requires vigorous stirring or vigorous stirring. Then, the system tends to be emulsified, and it may take a long time to separate the polyether and water after stirring, and the hydrosilylation may be inhibited by insufficient impurity removal. was there.

JP-A-4-36312 International Publication No. 2006/049088 JP 2002-249580 A

The present invention has been made in view of the above problems, and includes a crude polyether containing a water-soluble compound and an aprotic polar organic solvent, or a crude polyether, a protic polar organic solvent, and a nonpolar organic solvent. And then separating the precipitated solids by stationary separation, centrifugation or filtration, thereby producing a purified polyether that can efficiently remove impurities from the polyether without using water It aims to provide a method.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.

That is, the present invention relates to the following.
[1] A method for producing a polyether comprising a step of removing the water-soluble compound from a crude polyether containing a water-soluble compound,
Step (1) mixing the crude polyether and the organic solvent, and
Step (2) a step of removing solids precipitated in the mixed liquid of the crude polyether and the organic solvent,
Including
A method for producing a polyether, wherein the organic solvent is an aprotic polar organic solvent or a combination of a protic polar organic solvent and a nonpolar organic solvent.
[2] The method for producing a polyether according to [1], wherein the organic solvent is an aprotic polar organic solvent.
[3] The method for producing a polyether according to [1], wherein the organic solvent is a combination of a protic polar organic solvent and a nonpolar organic solvent.
[4] The method for producing a polyether according to [1] or [2], wherein the aprotic polar organic solvent is any one of a ketone solvent and an amide solvent.
[5] The method for producing a polyether according to [4], wherein the aprotic polar organic solvent is a ketone solvent.
[6] The method for producing a polyether according to [5], wherein the aprotic polar organic solvent is acetone.
[7] The method for producing a polyether according to [1] or [3], wherein the protic polar organic solvent is an alcohol solvent.
[8] The method for producing a polyether according to [7], wherein the protic polar organic solvent is an alcohol solvent having 1 to 3 carbon atoms.
[9] The method for producing a polyether according to [8], wherein the protic polar organic solvent is methanol.
[10] Any one of [1] to [9], in which 100 parts by weight of a crude polyether and 1 to 1000 parts by weight of an aprotic polar organic solvent or 1 to 1000 parts by weight of a protic polar organic solvent are mixed. A method for producing the polyether described in 1.
[11] The polyether according to [1], [3], [7], [8], [9], or [10], wherein the nonpolar organic solvent is a chain or cyclic saturated hydrocarbon Production method.
[12] The method for producing a polyether according to [11], wherein the nonpolar organic solvent is hexane and / or cyclohexane.
[13] The weight ratio of the weight of the protic polar organic solvent to the nonpolar organic solvent is 1/1 to 1/100 as the weight of the protic polar organic solvent / the weight of the nonpolar organic solvent. [1] , [3], [7], [8], [9], [10], [11], or [12].
[14] Liquid-liquid phase separation of a homogeneous solution containing a polyether during mixing of the crude polyether and organic solvent in step (1) to removal of solids in step (2), [1]-[ [13] The method for producing a polyether according to any one of [13].
[15] The method for producing a polyether according to [14], wherein liquid-liquid phase separation is caused by changing the temperature of the homogeneous solution.
[16] The method for producing a polyether according to any one of [1] to [15], wherein the temperature at which the crude polyether and the organic solvent are mixed is 0 to 140 ° C.
[17] The method for producing a polyether according to any one of [1] to [16], wherein the temperature at which the solid is precipitated in the mixed solution is 0 to 140 ° C.
[18] The method for producing a polyether according to any one of [1] to [17], wherein the operation for removing the solid matter is an operation including at least one of stationary separation, centrifugation, and filtration.
[19] The method for producing a polyether according to any one of [1] to [18], wherein the step (2) is performed a plurality of times.
[20] Any one of [1] to [19], wherein the crude polyether is any one selected from the group consisting of a hydroxyl group-terminated polyether, an unsaturated group-containing polyether and a reactive silicon group-containing polyether. A method for producing the polyether according to 1.
[21] The method for producing a polyether according to any one of [1] to [20], wherein the water-soluble compound is a compound derived from an alkali metal compound or a double metal cyanide complex catalyst.
[22] As a step of removing the water-soluble compound from the crude unsaturated group-containing polyether containing a water-soluble compound Step (1A): a step of mixing the crude unsaturated group-containing polyether and an organic solvent, and
Step (2A): a step of removing the solid matter precipitated in the mixed liquid of the crude unsaturated group-containing polyether and the organic solvent,
Including,
Step (3A): Hydrosilylation of the unsaturated group of the purified unsaturated group-containing polyether obtained through Step (1A) and Step (2A) with a silane compound represented by the following general formula (1) And obtaining a reactive silicon group-containing polyether,
A method for producing a reactive silicon group-containing polyether, wherein the organic solvent is an aprotic polar organic solvent or a combination of a protic polar organic solvent and a nonpolar organic solvent.
^{_{_{_{H- (SiR 2 2-b X}}}} b O) m -Si (R 1) 3-a X a (1)
(In General Formula (1), R ¹ and R ² are the same or different alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) _3. Represents a triorganosiloxy group represented by SiO—, and when two or more R ¹ or R ² are present, they may be the same or different, and R ′ is one having 1 to 20 carbon atoms. And R 3 may be the same or different, X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, they are the same Or may be different, a represents 0, 1, 2, or 3, b represents 0, 1, or 2, and m — (SiR ² _2-b X _b O) — When m is an integer of 2 or more in the group represented by May also be, may be different, m represents an integer of 0 to 19, where, a and b satisfy the a + Σb ≧ 1.)

The present invention also relates to the following.
[23] A method for producing a polyether, comprising a step of removing the water-soluble compound from a polyether containing a water-soluble compound (hereinafter referred to as crude polyether),
Step (1): A step of mixing an aprotic polar solvent with a crude polyether Step (2): A method for producing a polyether comprising at least a step of removing precipitated solids.
[24] A method for producing a polyether comprising a step of removing the water-soluble compound from a polyether containing a water-soluble compound (hereinafter referred to as crude polyether),
Step (1): Step of mixing a protic polar solvent (excluding water) and a non-polar solvent with a crude polyether Step (2): A polyether comprising at least a step of removing precipitated solids Production method.
[25] The water-soluble compound is removed from the unsaturated group-containing polyether containing the water-soluble compound (hereinafter referred to as crude unsaturated group-containing polyether).
Step (1): Step of mixing an aprotic polar solvent with a crude unsaturated group-containing polyether Step (2): At least a step of removing the precipitated solid, and then represented by the following general formula (1) A method for producing a reactive silicon group-containing polyether obtained by hydrosilylation with a silane compound.
H- (SiR ² _2-b X _b O) _m -Si (R ¹ _3-a ) X _a (1)
Wherein R ¹ and R ² are the same or different alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO—. When two or more R ¹ or R ² are present, they may be the same or different, where R ′ is a monovalent monovalent carbon having 1 to 20 carbon atoms. And three R's may be the same or different, and X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they are the same. A may be 0, 1, 2 or 3, and b may be 0, 1, or 2. In addition, m — (SiR ² _2-b X _b O) — groups They may be the same or different for b in .m is an integer of 0 to 19. However, it is assumed that satisfies a + Σb ≧ 1.)
[26] removing the water-soluble compound from the unsaturated group-containing polyether containing the water-soluble compound (hereinafter referred to as crude unsaturated group-containing polyether).
Step (1): Step of mixing a polar unsaturated solvent-containing polyether with a protic polar solvent (excluding water) and a nonpolar solvent Step (2): including at least a step of removing a precipitated solid, A method for producing a reactive silicon group-containing polyether obtained by hydrosilylation with a silane compound represented by the general formula (1).
H- (SiR ² _2-b X _b O) _m -Si (R ¹ _3-a ) X _a (1)
Wherein R ¹ and R ² are the same or different alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO—. When two or more R ¹ or R ² are present, they may be the same or different, where R ′ is a monovalent monovalent carbon having 1 to 20 carbon atoms. And three R's may be the same or different, and X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they are the same. A may be 0, 1, 2 or 3, and b may be 0, 1, or 2. In addition, m — (SiR ² _2-b X _b O) — groups They may be the same or different for b in .m is an integer of 0 to 19. However, it is assumed that satisfies a + Σb ≧ 1.)

According to the present invention, in removing the water-soluble compound from the crude polyether containing the water-soluble compound, the crude polyether and the aprotic polar organic solvent are mixed, or the crude polyether and the protic polar organic are mixed. Solvent and nonpolar organic solvent are mixed, and then the precipitated solid is separated by standing separation, centrifugation or filtration, so that water-soluble compounds can be efficiently removed from the polyether without vigorous stirring and use of water. In addition, it is possible to provide a method for producing a polyether from which a polyether with low turbidity can be obtained.

(Polyether production method)
The method for producing the polyether is not particularly limited, and a known method can be used. The crude polyether used in the method for producing a polyether is not particularly limited as long as it is a polyether containing a water-soluble compound as an impurity. As the crude polyether, for example, a polyether selected from the group consisting of a hydroxyl-terminated polyether, an unsaturated group-containing polyether and a reactive silicon group-containing polyether can be used.

As a manufacturing method of polyether, the manufacturing method of patent document 1 is preferable, for example.
In the production method described in Patent Document 1, after hydroxylating a terminal hydroxyl group of a polyether with a metal alkoxide, an unsaturated group-containing halide having a carbon-carbon unsaturated group is reacted to form a carbon- Introduce a carbon unsaturated group.

The method for producing the hydroxyl-terminated polyether is not particularly limited, and a known method can be used.

As a general production method, for example, a polymerization reaction using a double metal cyanide complex as a catalyst can be mentioned.

The main chain structure of the hydroxyl-terminated polyether is preferably a repeating unit represented by —RO—.

Here, R is a divalent organic group having 1 to 20 carbon atoms, which may contain heteroatoms such as oxygen, nitrogen, sulfur, silicon, phosphorus and halogen atoms. A plurality of R in the main chain may be the same group or two or more different groups.

R is preferably an alkylene group. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

As the repeating unit represented by —R—O—, —CH ₂ CH ₂ O—, —CH (CH ₃ ) CH ₂ O—, —CH (C ₂ H ₅ ) CH ₂ O—, —C (CH ₃₎ _₂ CH ₂ O-, and _-CH 2 _{_CH} 2 _CH 2 CH2O- like can be _{_{exemplified, -CH 2 CH 2 O -,}} - CH (CH 3) CH 2 O- are preferable, -CH ( CH ₃ ) CH ₂ O— is particularly preferred.

Further, the main chain of the hydroxyl group-terminated polyether may be branched or crosslinked.

The hydroxyl-terminated polyether is preferably produced by ring-opening polymerization of alkylene oxide as an initiator in the presence of a double metal cyanide complex catalyst.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, and α-methylstyrene oxide.

In addition to the above alkylene oxides, substituted or unsubstituted glycidyl ethers having 2 to 12 carbon atoms such as methyl glycidyl ether, ethyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, and phenyl glycidyl ether, etc. Can also be used.

Examples of the initiator include methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, Monohydric alcohols such as 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol and 2,2-dimethyl-1-propanol, ethylene glycol, Propylene glycol, butanediol, hexamethylene glycol, methallyl alcohol, hydrogenated bisphenol A, neopentyl glycol, polybutadiene diol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol Le, polypropylene triol, polypropylene tetraol, dipropylene glycol, glycerin, trimethylol methane, may be mentioned trimethylolpropane, and divalent or polyhydric alcohols such as pentaerythritol, and the various polymers, etc. having a hydroxyl group.

The thus obtained hydroxyl-terminated polyether is then converted to a polyether having a terminal group represented by -OM (M is an alkali metal) by reaction with a metal alkoxide (alkoxideation reaction).

The metal alkoxide is not particularly limited as long as it is a compound that can replace the hydrogen atom in the terminal hydroxyl group (—OH) of the hydroxyl-terminated polyether with an alkali metal atom.

As the metal alkoxide, an alkali metal alkoxide having 1 to 4 carbon atoms is used.

As the alkali metal alkoxide, sodium methoxide, potassium methoxide, sodium ethoxide and potassium ethoxide are preferable, sodium methoxide and potassium methoxide are more preferable, and sodium methoxide is particularly preferable in view of availability.

Two or more kinds of metal alkoxides can be used in combination, but it is preferable to use one kind alone.

Next, the polyether having a terminal group represented by -OM is converted into an unsaturated group-containing polyether containing metal impurities before purification by reaction with a halide (allylation reaction).

As the unsaturated group-containing halide, a compound represented by the following formula is preferred.
H (R ⁵ ) C═C (R ⁴ ) —R ³ —Y
(In the above formula, R ³ is a divalent organic group having 1 to 20 carbon atoms which may contain heteroatoms such as oxygen, nitrogen, sulfur, silicon, phosphorus and halogen atoms, and R ⁴ , R ⁵ Is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and Y is a halogen atom.)
As the unsaturated group-containing halide, allyl chloride and methallyl chloride (3-chloro-2-methyl-1-propene) are preferable from the viewpoint of availability.

Two or more kinds of unsaturated group-containing halides can be used in combination, but it is preferable to use one kind alone.

By allowing a metal alkoxide to act on the hydroxyl-terminated polyether (alkoxideation reaction), reacting with an epoxy compound having a carbon-carbon unsaturated bond, and further reacting with the halide (for example, allylation reaction), It is also possible to obtain unsaturated group-containing polyethers having more than one unsaturated group at one end. The epoxy compound having a carbon-carbon unsaturated bond is preferably allyl glycidyl ether.

By continuing stirring even after the reaction between the polyether and the unsaturated group-containing halide is completed, the metal alkoxide or the alkaline impurity in the metal alkoxide is consumed by reacting with the unsaturated group-containing halide. By adding at least one selected from alcohols having 1 to 3 carbon atoms or water after the addition of the unsaturated group-containing halide, the solubility of these alkaline components is increased, and the alkaline component and the unsaturated group-containing halide are added. The reaction of is promoted. As a result, the consumption rate of the alkaline component can be increased. Examples of the alcohol having 1 to 3 carbon atoms include methanol, ethanol, 1-propanol, and 2-propanol, and methanol and ethanol are more preferable. Among these alcohols, methanol is particularly preferred because it is a better solvent for the alkaline component and can dissolve the alkaline component with a small number of added parts.
However, the alcohol is not limited thereto, and the number of hydroxyl groups in the molecule may be two or more, and the molecule may contain atoms other than carbon, hydrogen, and oxygen. When an alcohol having 4 or more carbon atoms is used, the solubility of the alkaline component is insufficient and the effect is limited. Also, alcohols having 4 or more carbon atoms have a high boiling point and are difficult to remove after the reaction.

Two or more kinds of alcohols having 1 to 3 carbon atoms or water can be used in combination, but one kind is preferably used alone.

The number of added alcohol or water having 1 to 3 carbon atoms is not particularly limited, but is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the unsaturated group-containing polyether. preferable. If the number of added parts is too small, the alkali component is not sufficiently dissolved, and the effect of adding alcohol or water may be limited. In addition, if the number of added parts is excessive, an increase in pressure at the time of adding alcohol or water becomes large, which may cause inconveniences such as difficulty in addition.

The stirring time after addition of alcohol or water is not particularly limited, but is preferably within 8 hours, and more preferably within 4 hours. Even if the stirring time is excessively long, it is not possible to obtain an alkaline component removal effect that is commensurate with a decrease in production efficiency.

The unsaturated group-containing polyether obtained by the above method contains metal impurities and salts. Examples of water-soluble compounds to be removed in the subsequent purification step include compounds derived from alkali metal compounds or double metal cyanide complex catalysts such as zinc salts, cobalt salts and / or alkali metal salts.

(Purification of polyether)
The method for producing the purified polyether is a method including a step of removing the water-soluble compound from the crude polyether containing the water-soluble compound.
The above manufacturing method is
Step (1) mixing the crude polyether and the organic solvent, and
Step (2) a step of removing solids precipitated in the mixed liquid of the crude polyether and the organic solvent,
including. The organic solvent used in step (1) and step (2) is an aprotic polar organic solvent or a combination of a protic polar organic solvent and a nonpolar organic solvent.

That is, in the method for purifying a polyether, the purification is performed by mixing a crude polyether containing a water-soluble compound and an aprotic polar organic solvent, or a crude polyether, a protic polar organic solvent, and a nonpolar organic solvent, respectively. Thereafter, the precipitated solid is separated by stationary separation, centrifugation or filtration.

In this specification, the aprotic polar organic solvent is an organic solvent having no dissociative H having a relative dielectric constant of 10 or more. The protic polar organic solvent is an organic solvent having a dissociative H having a relative dielectric constant of 10 or more. A nonpolar organic solvent is an organic solvent having a relative dielectric constant of less than 10.

The aprotic polar organic solvent is not particularly limited. Examples of the aprotic polar organic solvent include ketone solvents such as acetone, acetylacetone, methyl ethyl ketone, and methyl isobutyl ketone; nitrile solvents such as acetonitrile, propionitrile, and benzonitrile; formamide, N, N-dimethylformamide, Amide solvents such as N, N-dimethylacetamide are preferred, ketone solvents such as acetone, acetylacetone, methyl ethyl ketone, and methyl isobutyl ketone; amide solvents such as formamide, N, N-dimethylformamide, and N, N-dimethylacetamide are preferred. More preferred are ketone solvents such as acetone, acetylacetone, methyl ethyl ketone, and methyl isobutyl ketone.
Further, as the ketone solvent, acetone and methyl ethyl ketone are more preferable, and acetone is particularly preferable.

The protic polar organic solvent is not particularly limited. Examples of the protic polar organic solvent include alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, and 1-hexanol; formic acid, acetic acid, phenol and the like are preferable, and methanol, ethanol Alcohol solvents such as propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol and 1-hexanol are particularly preferred. Further, the alcohol solvent is preferably an alcohol having 1 to 3 carbon atoms. Examples of the alcohol having 1 to 3 carbon atoms include methanol, ethanol, 1-propanol, 2-propanol, etc., methanol and ethanol are more preferable, and methanol is particularly preferable. The number of hydroxyl groups in the molecule may be two or more, and atoms other than carbon, hydrogen, and oxygen may be contained in the molecule.

The amount of the aprotic polar organic solvent or the protic polar organic solvent mixed with the polyether is preferably 1 to 1000 parts by weight and more preferably 5 to 500 parts by weight with respect to 100 parts by weight of the crude polyether. .

The nonpolar organic solvent is not particularly limited. Examples of the nonpolar organic solvent include ethers such as diethyl ether; chain or cyclic saturated hydrocarbons such as hexane, octane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; ethyl acetate and butyl acetate. , Esters such as propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; aldehydes such as acetaldehyde and propionaldehyde are preferred, chain or cyclic saturated hydrocarbons, aromatic hydrocarbons are more preferred, chain or cyclic Saturated hydrocarbons are particularly preferred. Further, the chain or cyclic saturated hydrocarbon is preferably hexane or cyclohexane.

The mixing ratio as a weight ratio of the protic polar organic solvent / non-polar organic solvent is preferably 1/1 to 1/100, more preferably 1/1 to 1/30. When a protic polar organic solvent and a nonpolar organic solvent are used at a mixing ratio within such a range, it is easy to obtain the desired effect by the combined use of both, and it is not necessary to use an excessively large apparatus, and after purification It is easy to remove the solvent in a short time.
The state after adding the organic solvent is not particularly limited. It is preferable that the polyether and the organic solvent become a homogeneous solution. In addition, what is necessary is just that the polyether and the organic solvent form the uniform solution that it is a uniform solution. Even if solids are precipitated after the addition of the organic solvent, if the polyether and the organic solvent form a uniform solution, the polyether and the organic solvent form a uniform solution in this state. Suppose you are.
When the polyether and the organic solvent form a homogeneous solution, during the mixing of the crude polyether and the organic solvent in step (1) to the removal of the solids in step (2), Liquid-liquid phase separation is preferred.
In this case, the high-concentration water-soluble compound is extracted while extracting the high-concentration water-soluble compound in one of the two liquid phases formed after the liquid-liquid separation. By precipitating the water-soluble compound as a solid in the phase in which the compound is present, the polyether can be purified efficiently.
The method of phase separation is not particularly limited. The method of phase separation is preferably temperature change, pH change, and salting out, more preferably temperature change and pH change, and particularly preferably temperature change.
As a method of phase separation, a method of changing the temperature of the homogeneous solution is preferable. The temperature change is not particularly limited as long as liquid-liquid phase separation is possible, and it may be a temperature rise or cooling, and cooling is preferred.
More specifically, when the organic solvent is an aprotic polar organic solvent, the liquid-liquid phase separation is separated into a phase mainly composed of polyether and a phase mainly composed of organic solvent. When the organic solvent is a combination of a protic polar organic solvent and a nonpolar organic solvent, a phase mainly composed of polyether and aprotic polar organic solvent, and a phase mainly composed of polyether and apolar organic solvent And to separate.

The temperature at which the polyether and the organic solvent are mixed is not particularly limited. The temperature at which the polyether and the solvent are mixed is preferably 0 ° C. or higher. However, if the temperature exceeds 140 ° C., the polymer may be deteriorated. In particular, it is preferable to mix the polyether and the organic solvent at a temperature at which a uniform solution is obtained.

The method for mixing the polyether and the organic solvent is not particularly limited. As a mixing method, a method using a shaker or a stirrer is preferable.

The temperature at which the solid is precipitated is not particularly limited. The temperature at which the solid is precipitated is preferably 0 ° C. or higher. However, if the temperature exceeds 140 ° C., the polymer may be deteriorated, and therefore 0 to 140 ° C. is preferable for practical use. In particular, the temperature is preferably such that the polyether and the organic solvent are phase separated.

The operation for separating the solid is not particularly limited. The separation operation is preferably an operation including at least one of stationary separation, centrifugation or filtration, and more preferably centrifugation or filtration. When removing impurities by filtration, the polyether containing solid matter may be supplied to the filtration device as it is. In order to enhance the filterability and the removal of solids, it is preferable to body-feed a slurry obtained by adding a filter aid to a pre-purification polyether containing solids to a filtration device.
The filter aid can be dispersed in purified polyether and used as a body feed, but it can also be used by pre-coating it on a filtration device prior to feeding the purified polyether.
When there is a concern about clogging of fine solids on filter cloth, etc., after pre-coating, purified polyether containing impurities can be supplied as it is, and purification with dispersed filter aid Polyether can also be fed in body feed.
As the filter aid, known filter aids such as celite and perlite can be used. For example, various grades of filter aid products with different particle sizes are available, such as Radiolite made by Showa Chemical Co., Ltd. and Topco made by Toko Perlite Industry.
As the filter aid, depending on the type of impurities to be removed, it can be used alone or in combination of a plurality of types.
In addition, when a filter aid having an extremely small particle size is used, filterability (filtration rate) may be deteriorated. Conversely, when a filter aid having an extremely large particle size is used, filterability is good. Thus, the impurity removal efficiency tends to deteriorate.
From the above viewpoint, the average particle diameter (laser method) of the filter aid used in the impurity removal step is preferably about 30 μm, for example, 20 μm to 40 μm.
The average particle diameter (scattering intensity) of the precipitated solid is preferably 600 nm or more, more preferably 800 nm or more, and particularly preferably 1000 nm or more from the viewpoint of high impurity removal efficiency in the solid separation step.
Moreover, you may include operation | movement which deposits and isolate | separates a solid substance in multiple times. However, productivity increases when the number of times is large. Therefore, the step of depositing and separating the solid is preferably 10 times or less, more preferably 5 times or less, particularly preferably 3 times or less, and most preferably 1 time.

When depositing the solid, an inorganic acid, an organic acid, an alkali, an inorganic salt, an organic salt, or the like may or may not be added.

(Hydrosilylation of unsaturated group-containing polyether)
A reactive silicon group-containing polyether can be obtained by hydrosilylating the terminal unsaturated group of the unsaturated group-containing polyether after purification by a known method to introduce a reactive silicon group-containing polyether.

Hydrosilylation of the unsaturated group-containing polyether is not particularly limited, and a known method can be used.

The polyether having an unsaturated group and the silane compound for hydrosilylation may be a compound having one or more Si—H groups in the molecule. Typical examples include compounds represented by the following general formula (1).

^{_{_{_{H- (SiR 2 2-b X}}}} b O) m -Si (R 1) 3-a X a (1)
(In General Formula (1), R ¹ and R ² are the same or different alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) _3. Represents a triorganosiloxy group represented by SiO—, and when two or more R ¹ or R ² are present, they may be the same or different, and R ′ is one having 1 to 20 carbon atoms. The three R's may be the same or different, X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they are the same Or may be different, a represents 0, 1, 2, or 3, b represents 0, 1, or 2. m- (SiR ² _2-b X _b O) In the group represented by-, when m is an integer of 2 or more, 2 or more of b May be the same or different, m represents an integer of 0 to 19, where, a and b satisfy the a + Σb ≧ 1.)
Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3. In the general formula (1), (a + Σb) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different.

In particular, a compound represented by the following general formula (2) is preferable because it is easily available.
H-SiR ¹ _3-c X _c (2)
(In general formula (2), R ¹ and X are the same as described above. C represents ¹ , 2 or 3.)

Specifically, halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyldichlorosilane, trimethylsiloxymethylchlorosilane; trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane Alkoxysilanes such as phenyldimethoxysilane, trimethylsiloxymethylmethoxysilane and trimethylsiloxydiethoxysilane; methyldiacetoxysilane, phenyldiacetoxysilane, triacetoxysilane, trimethylsiloxymethylacetoxysilane, trimethylsiloxydiacetoxysilane and the like Siloxysilanes: bis (dimethylketoximate) methylsilane, bis (cyclohexylketoximate) methylsilane, bis (diethylketoxy) Over G) trimethylsiloxy silane, bis (methyl ethyl ketone carboxylate formate) methylsilane, tris (keto carboxylate formate silanes such as acetoxy formate) silane; alkenyloxy silanes such as methyl isopropenyloxy silane and the like. Of these, alkoxysilanes are particularly preferable, and a methoxy group is particularly preferable among the alkoxy groups.

The hydrosilylation reaction is usually carried out in the range of usually 10 to 140 ° C., more preferably 20 to 120 ° C., most preferably 40 to 100 ° C. An organic solvent such as benzene, toluene, xylene, tetrahydrofuran, methylene chloride, pentane, hexane, or heptane can be used as needed for adjusting the reaction temperature and adjusting the viscosity of the reaction system.

As a catalyst used in a hydrosilylation reaction between a polyether having an unsaturated bond and a compound having a hydrolyzable silicon group, a metal complex catalyst selected from group VIII transition metal elements such as platinum, rhodium and the like is effective. used. As the metal complex catalyst, for example, a compound such as H ₂ PtCl ₆ .6H ₂ O, platinum-vinylsiloxane complex, platinum-olefin complex, RhCl (PPh ₃ ) ₃ , etc. can be used. From the viewpoint of reactivity of the _{_{_{hydrosilylation, H 2 PtCl 6 · 6H 2}}} O, platinum - vinylsiloxane complexes, are particularly preferred. The platinum-vinylsiloxane complex here is a general term for compounds in which a siloxane, polysiloxane, or cyclic siloxane is coordinated with a platinum atom as a ligand in the molecule. Specific examples of the ligand include 1,1,3,3-tetramethyl 1,3-divinyldisiloxane. The amount of the catalyst used is not particularly limited, but it is usually preferable to use 10 ^-1 to 10 ^-8 mol of platinum catalyst with respect to 1 mol of alkenyl group.

The reactive silicon group-containing polyether thus synthesized is cured at room temperature with moisture in the atmosphere in the presence of a curing catalyst, and gives a coating film having good adhesion to metals, glass, etc. It is useful as a coating composition for automobiles, sealing compositions, coating compositions, and adhesive compositions. As the curing catalyst, a conventionally known silanol condensation catalyst can be used. These catalysts may be used alone or in combination of two or more.

(Method for producing reactive silicon group-containing polyether)
The following method for producing a reactive silicon group-containing polyether is also provided.
Specifically, the method for producing a reactive silicon group-containing polyether is as a step of removing the water-soluble compound from the crude unsaturated group-containing polyether containing a water-soluble compound. Step (1A): Crude unsaturated group-containing polyether Mixing an ether and an organic solvent, and
Step (2A): a step of removing the solid matter precipitated in the mixed liquid of the crude unsaturated group-containing polyether and the organic solvent,
Including,
Step (3A): The unsaturated group of the purified unsaturated group-containing polyether obtained through Step (1A) and Step (2A) is hydrosilylated with the silane compound represented by the above general formula (1). And obtaining a reactive silicon group-containing polyether.
The organic solvent used in the step (1A) and the step (2A) is an aprotic polar organic solvent or a combination of a protic polar organic solvent and a nonpolar organic solvent.
Step (1A) and step (2A) are performed according to the method described above as the method for producing a polyether.
Step (3A) is performed according to the method described above for the hydrosilylation of the unsaturated group-containing polyether.
According to such a production method, it is possible to produce a purified reaction-molded silicon group-containing polyether that can efficiently remove impurities without using water.
Moreover, according to said manufacturing method, inhibition of the hydrosilylation reaction by the water-soluble compound which is an impurity is suppressed.

Hereinafter, in order to further clarify the present invention, specific examples will be described. However, the present invention is not limited to these examples.

(PH measurement)
The pH of the unsaturated group-containing polyether was measured by the method described in JIS K 1557-5 (test method: pH (reference)).
The pH meter used was S220-Kit manufactured by METTLER TOLEDO.

(Turbidity measurement)
The unsaturated group-containing polyether or reactive silicon group-containing polyether is transferred to a spectrophotometer cell (2-478-05, manufactured by ASONE Co., Ltd.) and removed using a pelger (PC-250K, manufactured by Sampleratech Co., Ltd.). Foam treatment was performed. The defoaming treatment was performed using a diaphragm pump to reduce the pressure until the bubbles disappeared visually. A660 (absorbance at 660 nm) was measured for the defoamed cell using a spectrophotometer (U-1800, manufactured by Hitachi High-Tech Science Co., Ltd.). Ion exchange water was used to adjust the zero point of the spectrophotometer.

(Synthesis Example 1)
A number average molecular weight of about 15000, comprising polypropylene triol having a number average molecular weight of 300 as an initiator, ring-opening polymerization of propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst, and containing a metal compound as a catalyst and / or its residue as an impurity. To obtain a hydroxyl group-terminated polyether.

(Synthesis Example 2)
A 30% methanol solution of sodium methoxide equivalent to 1.0 times the hydroxyl group of the hydroxyl group-terminated polyether obtained in Synthesis Example 1 was added to distill off the methanol. Thereafter, 1.8 times equivalent of allyl chloride was added to the hydroxyl group to convert the terminal hydroxyl group into an allyl group. One hour after the addition of allyl chloride, 0.5 part of methanol was added, and the mixture was further stirred for 3 hours. Thereafter, allyl chloride and methanol were distilled off to obtain an unsaturated group-containing polyether (a1). It was 8.4 when pH of the unsaturated group containing polyether (a1) was measured.

Example 1
50 g of unsaturated group-containing polyether (a1) obtained in Synthesis Example 2 and 50 g of acetone were placed in a glass container. The liquid in the glass container was heated to 60 ° C. and mixed for 10 minutes with a shaker. The temperature after mixing was 15 ° C. Then, it filtered with a 0.5 micrometer membrane filter. The filtered liquid was devolatilized under reduced pressure at 110 ° C. The turbidity (A660) of the unsaturated group-containing polyether obtained after devolatilization was measured. The results are shown in Table 1.

(Example 2)
50 g of unsaturated group-containing polyether (a1) obtained in Synthesis Example 2, 2.5 g of methanol, and 2.5 g of hexane were placed in a glass container. The liquid in the glass container was heated to 60 ° C. and mixed for 10 minutes with a shaker. The temperature after mixing was 15 ° C. Thereafter, solid-liquid separation was performed with a centrifuge. The liquid after solid-liquid separation was devolatilized under reduced pressure at 110 ° C. The turbidity (A660) of the unsaturated group-containing polyether obtained after devolatilization was measured. The results are shown in Table 1.

(Example 3)
50 g of unsaturated group-containing polyether (a1) obtained in Synthesis Example 2, 5 g of methanol, and 45 g of hexane were placed in a glass container. The liquid in the glass container was heated to 60 ° C. and mixed for 10 minutes with a shaker. The temperature after mixing was 15 ° C. Thereafter, solid-liquid separation was performed with a centrifuge. The liquid after solid-liquid separation was devolatilized under reduced pressure at 110 ° C. The turbidity (A660) of the unsaturated group-containing polyether obtained after devolatilization was measured. The results are shown in Table 1.

Example 4
50 g of unsaturated group-containing polyether (a1) obtained in Synthesis Example 2, 5 g of methanol, and 45 g of cyclohexane were placed in a glass container. The liquid in the glass container was heated to 60 ° C. and mixed for 10 minutes with a shaker. The temperature after mixing was 15 ° C. Thereafter, solid-liquid separation was performed with a centrifuge. The liquid after solid-liquid separation was devolatilized under reduced pressure at 110 ° C. The turbidity (A660) of the unsaturated group-containing polyether obtained after devolatilization was measured. The results are shown in Table 1.

(Comparative Example 1)
50 g of unsaturated group-containing polyether (a1) obtained in Synthesis Example 2 and 25 g of methanol were placed in a glass container. The liquid in the glass container was heated to 60 ° C. and mixed for 10 minutes with a shaker. The temperature after mixing was 15 ° C. Then, it filtered with a 0.5 micrometer membrane filter. The filtered liquid was devolatilized under reduced pressure at 110 ° C. The turbidity (A660) of the unsaturated group-containing polyether obtained after devolatilization was measured. The results are shown in Table 1.

(Comparative Example 2)
50 g of the unsaturated group-containing polyether (a1) obtained in Synthesis Example 2 and 25 g of hexane were placed in a glass container. The liquid in the glass container was heated to 60 ° C. and mixed for 10 minutes with a shaker. The temperature after mixing was 15 ° C. Then, it filtered with a 0.5 micrometer membrane filter. The filtered liquid was devolatilized under reduced pressure at 110 ° C. The turbidity (A660) of the unsaturated group-containing polyether obtained after devolatilization was measured. The results are shown in Table 1.

(Example 5)
50 g of unsaturated group-containing polyether obtained in Example 3, 1 g of hexane, and 0.0225 g of ascorbic acid were added to a 200 mL four-necked flask and devolatilized at 90 ° C. under reduced pressure. Thereafter, the liquid in the flask was stirred for 1 hour. Next, the inside of the flask was replaced with N ₂ , 23 μL of platinum-vinylsiloxane complex (Pt 1 wt% / isopropanol (hereinafter, IPA)) was added and stirred, and 1.2 g of dimethoxymethylsilane was slowly added dropwise. The mixed solution was reacted at 90 ° C. for 1 hour, and then devolatilized under reduced pressure at 110 ° C. to obtain a reactive silicon group-containing polyether. As a result of measuring the residual allyl group ratio of the polymer obtained by NMR, the unreacted allyl group ratio was 1%.

(Comparative Example 3)
50 g of unsaturated group-containing polyether obtained in Comparative Example 2, 1 g of hexane, and 0.0225 g of ascorbic acid were added to a 200 mL four-necked flask and subjected to vacuum devolatilization at 90 ° C. Thereafter, the liquid in the flask was stirred for 1 hour. Next, the inside of the flask was replaced with N ₂ , 23 μL of platinum-vinylsiloxane complex (Pt 1 wt% / isopropanol (hereinafter, IPA)) was added and stirred, and 1.2 g of dimethoxymethylsilane was slowly added dropwise. The mixed solution was reacted at 90 ° C. for 1 hour, and then devolatilized under reduced pressure at 110 ° C. to obtain a reactive silicon group-containing polyether. As a result of measuring the residual allyl group ratio of the polymer obtained by NMR, the unreacted allyl group ratio was 70%. The results are shown in Table 2.

Claims

A method for producing a polyether comprising a step of removing the water-soluble compound from a crude polyether containing a water-soluble compound,
Step (1) mixing the crude polyether with an organic solvent, and
Step (2) a step of removing solids precipitated in the mixed liquid of the crude polyether and the organic solvent;
Including
A method for producing a polyether, wherein the organic solvent is an aprotic polar organic solvent or a combination of a protic polar organic solvent and a nonpolar organic solvent.
The method for producing a polyether according to claim 1, wherein the organic solvent is the aprotic polar organic solvent.
The method for producing a polyether according to claim 1, wherein the organic solvent is a combination of the protic polar organic solvent and the nonpolar organic solvent.
The method for producing a polyether according to claim 1 or 2, wherein the aprotic polar organic solvent is one of a ketone solvent and an amide solvent.
The method for producing a polyether according to claim 4, wherein the aprotic polar organic solvent is a ketone solvent.
The method for producing a polyether according to claim 5, wherein the aprotic polar organic solvent is acetone.
The method for producing a polyether according to claim 1 or 3, wherein the protic polar organic solvent is an alcohol solvent.
The method for producing a polyether according to claim 7, wherein the protic polar organic solvent is an alcohol solvent having 1 to 3 carbon atoms.
The method for producing a polyether according to claim 8, wherein the protic polar organic solvent is methanol.
The mixture according to any one of claims 1 to 9, wherein 100 parts by weight of the crude polyether and 1 to 1000 parts by weight of the aprotic polar organic solvent or 1 to 1000 parts by weight of the protic polar organic solvent are mixed. A process for producing the described polyether.
The method for producing a polyether according to claim 1, 3, 7, 8, 9, or 10, wherein the nonpolar organic solvent is a chain or cyclic saturated hydrocarbon.
The method for producing a polyether according to claim 11, wherein the nonpolar organic solvent is hexane and / or cyclohexane.
The weight ratio of the weight of the protic polar organic solvent to the nonpolar organic solvent is 1/1 to 1/100 as the weight of the protic polar organic solvent / the weight of the nonpolar organic solvent. The method for producing a polyether according to 3, 7, 8, 9, 10, 11, or 12.
The liquid-liquid phase separation is performed on the homogeneous solution containing the polyether during the mixing of the crude polyether and the organic solvent in the step (1) to the removal of the solid in the step (2). 14. The method for producing a polyether according to any one of 1 to 13.
15. The method for producing a polyether according to claim 14, wherein liquid-liquid phase separation is caused by changing the temperature of the homogeneous solution.
The method for producing a polyether according to any one of claims 1 to 15, wherein a temperature at which the crude polyether and the organic solvent are mixed is 0 to 140 ° C.
The method for producing a polyether according to any one of claims 1 to 16, wherein a temperature at which the solid matter is precipitated in the mixed solution is 0 to 140 ° C.
The method for producing a polyether according to any one of claims 1 to 17, wherein the operation for removing the solid matter is an operation including at least one of stationary separation, centrifugation, and filtration.
The method for producing a polyether according to any one of claims 1 to 18, wherein the step (2) is carried out a plurality of times.
The poly ether according to any one of claims 1 to 19, wherein the crude polyether is selected from the group consisting of a hydroxyl group-terminated polyether, an unsaturated group-containing polyether and a reactive silicon group-containing polyether. A method for producing ether.
The method for producing a polyether according to any one of claims 1 to 20, wherein the water-soluble compound is a compound derived from an alkali metal compound or a double metal cyanide complex catalyst.
As a step of removing the water-soluble compound from the crude unsaturated group-containing polyether containing a water-soluble compound Step (1A): a step of mixing the crude unsaturated group-containing polyether and an organic solvent, and
Step (2A): a step of removing solids precipitated in the mixed liquid of the crude unsaturated group-containing polyether and the organic solvent,
Including,
Step (3A): The unsaturated group of the purified unsaturated group-containing polyether obtained through the step (1A) and the step (2A) is converted into a silane compound represented by the following general formula (1). Comprising hydrosilylation to obtain a reactive silicon group-containing polyether,
A method for producing a reactive silicon group-containing polyether, wherein the organic solvent is an aprotic polar organic solvent or a combination of a protic polar organic solvent and a nonpolar organic solvent.
H- (SiR 2 2-b X b O) m -Si (R 1) 3-a X a (1)
(In General Formula (1), R 1 and R 2 are the same or different alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) 3. Represents a triorganosiloxy group represented by SiO—, and when two or more R 1 or R 2 are present, they may be the same or different, and R ′ is one having 1 to 20 carbon atoms. The three R's may be the same or different, X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they are the same Or may be different, a represents 0, 1, 2, or 3, b represents 0, 1, or 2, and m — (SiR 2 2-b X b O) — When m is an integer of 2 or more in the group represented by May also be, may be different, m represents an integer of 0 to 19, where, a and b satisfy the a + Σb ≧ 1.)