WO2019203233A1 - Méthode de production de polyéther - Google Patents

Méthode de production de polyéther Download PDF

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Publication number
WO2019203233A1
WO2019203233A1 PCT/JP2019/016333 JP2019016333W WO2019203233A1 WO 2019203233 A1 WO2019203233 A1 WO 2019203233A1 JP 2019016333 W JP2019016333 W JP 2019016333W WO 2019203233 A1 WO2019203233 A1 WO 2019203233A1
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Prior art keywords
unsaturated group
containing polyether
group
polyether
ascorbic acid
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PCT/JP2019/016333
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English (en)
Japanese (ja)
Inventor
優 長岡
翔大 神谷
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株式会社カネカ
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Priority to JP2020514395A priority Critical patent/JP7285248B2/ja
Publication of WO2019203233A1 publication Critical patent/WO2019203233A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon

Definitions

  • the present invention relates to a method for producing a polyether and a method for reducing turbidity.
  • 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 rubbery 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.
  • Examples of the method for producing such reactive silicon group-containing polyether include the following methods. First, ring opening polymerization of alkylene oxide is performed 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 terminal hydroxyl group of the polyether is converted to an olefin, A method for obtaining an unsaturated group-containing polyether having an unsaturated group is known (see Patent Document 1).
  • the unsaturated group-containing polyether is washed with washing water in which water and an acidic component such as ascorbic acid are mixed, or the unsaturated group-containing polyether is dissolved in a solvent incompatible with water.
  • the unsaturated group-containing polyether purified by such a method is converted into a reactive silicon group-containing polyether through a hydrosilylation reaction with a hydrosilane compound having a reactive silicon group.
  • Methods for producing such reactive silicon group-containing polyethers are widely known and have already been put into practical use industrially.
  • the present invention has been made in view of the above problems, and removes an alkaline component, a metal impurity derived from a polymerization catalyst, and a salt in an unsaturated group-containing polyether or a reactive silicon group-containing polyether, Production method capable of obtaining low turbidity polyether by making ascorbic acid metal salt contained in saturated group-containing polyether or reactive silicon group-containing polyether 0.001 to 10 ppm by weight The purpose is to provide.
  • the present invention (1) reacting the terminal hydroxyl group of the polyether with a metal alkoxide to alkoxide; It contains a crude unsaturated group by reacting an unsaturated group-containing halide having a carbon-carbon unsaturated group at the end of the alkoxideized polyether and introducing a carbon-carbon unsaturated group at the end of the polyether.
  • a method for producing a purified unsaturated group-containing polyether comprising adding ascorbic acid to the unsaturated group-containing polyether after the treatment for removing impurities, The manufacturing method of the unsaturated group containing polyether whose amount of ascorbic acid metal salt in the obtained refined unsaturated group containing polyether is 0.001 weight ppm or more and less than 10 weight ppm.
  • a group in which the metal salt of ascorbic acid is composed of a metal salt derived from sodium methoxide, a metal salt derived from sodium sulfate, a metal salt derived from sodium chloride, and a metal salt derived from a composite metal cyanide complex compound catalyst.
  • the metal salt of ascorbic acid is derived from ascorbic acid added to the unsaturated group-containing polyether after the treatment for removing impurities is performed, according to any one of (1) to (3) A method for producing a purified unsaturated group-containing polyether.
  • the process of removing impurities from the crude unsaturated group-containing polyether is a process of mixing the crude unsaturated group-containing polyether and water at least once, any one of (1) to (5)
  • purified unsaturated group containing polyether as described in (6) which repeats the process which mixes a crude unsaturated group containing polyether and water twice or more.
  • the ascorbic acid is added to the unsaturated group-containing polyether having A660 of 0.000 or less after the treatment for removing impurities is performed, according to any one of (1) to (10) A method for producing a purified unsaturated group-containing polyether.
  • the refined product according to any one of (1) to (11), wherein the unsaturated group-containing polyether to which ascorbic acid is added after the treatment for removing impurities does not contain an organic solvent A method for producing an unsaturated group-containing polyether.
  • Obtaining a reactive silicon group-containing polyether comprising obtaining a group-containing polyether, The manufacturing method of the reactive silicon group containing polyether whose amount of ascorbic acid metal salt in the obtained reactive silicon group containing polyether is 0.001 weight ppm or more and less than 10 weight ppm.
  • 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.
  • 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.
  • A may be 0, 1, 2, or 3
  • b may be 0, 1, or 2
  • m represents an integer of 0 to 19, where, a and b satisfy the a + ⁇ b ⁇ 1.
  • the process of removing impurities from the crude unsaturated group-containing polyether is a process of mixing the crude unsaturated group-containing polyether and water at least once, any one of (13) to (17) A method for producing a purified reactive silicon group-containing polyether as described in 1.
  • (20) The purification according to (18) or (19), wherein acidic water is used as water in at least one of the one or more treatments of mixing the crude unsaturated group-containing polyether and water. Process for producing a reactive silicon group-containing polyether.
  • ascorbic acid is added to the unsaturated group-containing polyether containing no organic solvent, and the unsaturated group-containing polyether to which ascorbic acid is added is subjected to hydrosilylation.
  • a polyether having low turbidity can be obtained by setting the ascorbic acid metal salt contained in the unsaturated group-containing polyether or the reactive silicon group-containing polyether to 0.001 wtppm or more and less than 10 wtppm. Can be acquired. Thereby, impurities contained in the unsaturated group-containing polyether or the reactive silicon group-containing polyether can be reduced, and the quality of the polyether can be improved.
  • the method for producing the unsaturated group-containing polyether is: Reacting a hydroxyl group at the terminal of polyoxyalkylene, which is a polyether, with a metal alkoxide to alkoxide; It contains a crude unsaturated group by reacting an unsaturated group-containing halide having a carbon-carbon unsaturated group at the terminal of the alkoxide-ized polyether and introducing a carbon-carbon unsaturated group at the terminal of the polyether. Obtaining a polyether.
  • Hydroxyl-terminated polyethers are used as raw materials for producing unsaturated group-containing polyethers.
  • the manufacturing method of a hydroxyl-terminated polyether is not specifically limited, A well-known method can be used.
  • a general production method for example, it can be obtained by a polymerization reaction using a double metal cyanide complex as a catalyst.
  • the main chain structure of the hydroxyl-terminated polyether is preferably a repeating unit represented by —RO—.
  • 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.
  • repeating unit represented by —R—O— 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—, —CH 2 CH 2 CH 2 CH 2 O— and the like.
  • —CH 2 CH 2 O— and —CH (CH 3 ) CH 2 O— are preferable, and —CH (CH 3 ) CH 2 O— is particularly preferable.
  • the main chain of the hydroxyl-terminated polyether may be branched or cross-linked.
  • 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.
  • alkylene oxide examples include ethylene oxide, propylene oxide, ⁇ -butylene oxide, ⁇ -butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, and ⁇ -methylstyrene oxide.
  • 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.
  • Initiators include methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pen Monohydric alcohols such as butanol, 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
  • 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).
  • M is an alkali metal
  • 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.
  • an alkali metal alkoxide having 1 to 4 carbon atoms is used as the metal alkoxide.
  • 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.
  • 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).
  • R 3 is a divalent organic group having 1 to 20 carbon atoms which may contain heteroatoms such as oxygen, nitrogen, sulfur, silicon, phosphorus, halogen atoms, etc.
  • R 4 , R 5 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • Y is a halogen atom.
  • allyl chloride and methallyl chloride (3-chloro-2-methyl-1-propene) are preferable from the viewpoint of availability.
  • Two or more types of halides can be used in combination, but it is preferable to use one type alone.
  • the epoxy compound having a carbon-carbon unsaturated bond is preferably allyl glycidyl ether.
  • the metal alkoxide or the alkaline impurity in the metal alkoxide is consumed by reacting with 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, 2-propanol and the like, and methanol and ethanol are more preferable.
  • 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.
  • 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.
  • an alcohol having 4 or more carbon atoms is used, the solubility of the alkaline component is insufficient and the effect is limited.
  • 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 may be limited. Moreover, when there are more addition parts than 20 weight part, the raise of the pressure at the time of alcohol or water addition will become large, and inconveniences, such as addition being difficult, may arise.
  • the stirring time after addition of alcohol or water is not particularly limited, but is preferably 5 minutes to 8 hours, more preferably 5 minutes to 4 hours. If the stirring time is excessively short, it may be difficult to obtain the desired alkaline component removal effect. 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 pH of the obtained crude unsaturated group-containing polyether is preferably 9.0 or less.
  • the pH is higher than 9.0, the alkaline component is not sufficiently removed.
  • the wash water may be taken up by being dissolved or finely dispersed in the oil phase, and it may be difficult to separate the wash water from the oil phase.
  • the washing water and the oil phase are emulsified, it is particularly difficult to separate the washing water from the oil phase.
  • the pH of the crude unsaturated group-containing polyether is higher than 9.0, the removal efficiency of metal impurities and salts decreases.
  • the crude unsaturated group-containing polyether obtained by the above-mentioned method contains metal impurities and salts, and the water-soluble compounds to be removed in the subsequent purification step include zinc salts, cobalt salts and alkalis. Examples thereof include compounds derived from alkali metal compounds or double metal cyanide complex catalysts such as one or more salts such as metal salts.
  • the crude unsaturated group-containing polyether obtained by the above method is subjected to a treatment for removing at least one impurity, thereby purifying the crude unsaturated gold-containing polyether.
  • the treatment for removing impurities from the crude unsaturated group-containing polyether is preferably carried out repeatedly twice or more.
  • the purification method of the crude unsaturated group containing polyether containing a metal impurity is not specifically limited, A well-known method can be used.
  • a purification method a crude unsaturated group-containing polyether containing metal impurities is dissolved in an organic solvent, and then an organic solvent solution of the crude unsaturated group-containing polyether is mixed with water (see Patent Document 3).
  • a method of mixing a crude unsaturated group-containing polyether containing metal impurities and water (see Patent Document 2), and dissolving a crude unsaturated group-containing polyether containing metal impurities in an organic solvent and filtering. And a method of dissolving a crude unsaturated group-containing polyether containing metal impurities in a specific organic solvent to precipitate and remove the metal impurities.
  • a method of mixing a crude unsaturated group-containing polyether containing a metal impurity and water is particularly preferable because the operation is easy and the purification effect is high.
  • Examples of the purification method of mixing the crude unsaturated group-containing polyether containing metal impurities with water include a method including a removal operation of extracting the water-soluble compound contained in the crude unsaturated group-containing polyether with water. It is done.
  • the removal operation includes, for example, at least an operation of separating the polyether phase and the aqueous phase at a temperature of 50 ° C. or higher. By such a removing operation, the alkaline component, the metal impurities derived from the polymerization catalyst, and the salt can be extracted into the aqueous phase. Extraction with water is performed any number of times of one or more.
  • the treatment of mixing the crude unsaturated group-containing polyether containing metal impurities with water is preferably performed twice or more in view of the balance with the purification effect of the unsaturated group-containing polyether.
  • By washing the crude unsaturated group-containing polyether with acidic water it is easy to efficiently remove impurities such as alkaline components, metal impurities derived from the polymerization catalyst, and salts.
  • the pH of the wash water after the last treatment of the one or more treatments in which the crude unsaturated group-containing polyether and water are mixed is preferably 4.5 to 8, and preferably 5 to 6.5. More preferably, it is particularly preferably 5.5 to 6.2.
  • the pH of the wash water after any treatment is preferably 4.5 to 8. It is more preferably 6.5, and particularly preferably 5.5 to 6.2.
  • the acidic component added to the acidic water is preferably at least one selected from the group consisting of ascorbic acid, citric acid and sulfuric acid from the viewpoint of the effect of removing impurities, and is preferably ascorbic acid and / or sulfuric acid. More preferably, it is ascorbic acid.
  • Ascorbic acid refers to L-ascorbic acid; isoascorbic acid; ester derivatives of L-ascorbic acid or isoascorbic acid; L-ascorbic acid or phosphoric acid ester derivatives of isoascorbic acid; ethers of L-ascorbic acid or isoascorbic acid Derivatives, more preferably L-ascorbic acid and isoascorbic acid.
  • Isoascorbic acid is a structural isomer of L-ascorbic acid.
  • ester derivatives include L-ascorbyl palmitate, L-ascorbyl stearate, L-ascorbyl 2-ethylhexanoate, isoascorbyl palmitate, isoascorbyl stearate, and isoascorbyl 2-ethylhexanoate. Can be mentioned.
  • phosphoric acid ester derivatives include L-ascorbic acid monophosphate, L-ascorbic acid diphosphate, L-ascorbic acid triphosphate, isoascorbic acid monophosphate, isoascorbic acid diphosphate, And isoascorbic acid triphosphate.
  • ether derivative examples include L-ascorbic acid-2-glucoside or isoascorbic acid-2-glucoside.
  • the temperature at which the unsaturated group-containing polyether phase and the aqueous phase are separated is preferably 50 ° C. or higher. From the viewpoint of separability, it is more preferably 60 ° C. or higher, more preferably 80 ° C. or higher. However, if it exceeds 140 ° C., the polymer may be deteriorated, and therefore, from 60 to 140 ° C. is preferable for practical use.
  • the mixing ratio of the crude unsaturated group-containing polyether and water is not particularly limited as long as the unsaturated phase-containing polyether phase and the aqueous phase can be separated. If the amount of water is too small, it may be difficult to separate the aqueous phase and the polyether phase, and it may be difficult to extract metal impurities. If the amount of water is too large, there is a problem that a large apparatus is required. For this reason, the amount of water is preferably 10 to 1000 parts by weight, more preferably 20 to 500 parts by weight, based on 100 parts by weight of the crude unsaturated group-containing polyether.
  • the number of times that the water-soluble compound is extracted into the aqueous phase is not particularly limited. If the frequency is too small, the water-soluble compound may remain in the unsaturated group-containing polyether. If the number is too large, the productivity will deteriorate. Therefore, the number of extractions is preferably 1 to 10 times, more preferably 2 to 6 times, and particularly preferably 2 to 3 times.
  • a crude unsaturated group-containing polyether is dissolved in a solvent incompatible with water, and a mixture containing the solution and water is stirred. It is possible to use a purification method in which the alkaline component, the metal impurities derived from the polymerization catalyst, and the salt are extracted into the aqueous phase by stirring in the aqueous phase.
  • a purification method following extraction, an oil phase and a water phase, which are solutions of unsaturated group-containing polyethers, are separated.
  • the oil phase and aqueous phase are preferably continuously centrifuged.
  • Examples of the solvent incompatible with water include aliphatic, alicyclic or aromatic hydrocarbon solvents, ether solvents, and halides thereof. Specific examples of these solvents include butane, pentane, hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, cyclopentane, benzene, toluene, xylene, butanol, pentanol, methyl ether, ethyl ether, isopropyl ether.
  • halobenzene-based solvent examples include benzene substituted with one or more halogen atoms selected from a chlorine atom, a bromine atom, and an iodine atom, such as chlorobenzene, dichlorobenzene, and bromobenzene.
  • a crude unsaturated group-containing polyether containing metal impurities is dissolved in a specific organic solvent to precipitate and remove the metal impurities.
  • the A660 of the unsaturated group-containing polyether after the treatment for removing impurities is preferably less than 0.008, more preferably 0.006 or less, particularly preferably 0.003 or less, Preferably it is 0.000 or less.
  • Low A660 after washing means that there are few impurities contained in the unsaturated group-containing polyether, and the hydrosilylation reaction for using the unsaturated group-containing polyether becomes transparent. There is merit that it is hard to be obstructed.
  • the unsaturated group-containing polyether after the treatment for removing impurities as described above does not contain an organic solvent.
  • the unsaturated group-containing polyether does not contain an organic solvent does not exclude the inevitable inclusion of the organic solvent in the unsaturated group-containing polyether.
  • the unsaturated group-containing polyether not containing an organic solvent contains a very small amount of an organic solvent of about 0.5 wt% or less, preferably 0.1 wt% or less, more preferably about 0.01 wt% or less. You may go out.
  • Ascorbic acid is added to the unsaturated group-containing polyether after the treatment for removing impurities as described above.
  • the unsaturated group-containing polyether after the treatment for removing impurities is hydrosilylated with a silane compound represented by the following general formula (1) in the presence of ascorbic acid and / or ascorbic acid metal salt.
  • a silane compound represented by the following general formula (1) Subject to reaction. Through such a hydrosilylation reaction, a reactive silicon group-containing polyether is obtained.
  • a reactive silicon group is introduced into an unsaturated group at the terminal of an unsaturated group-containing polyether after adding ascorbic acid by a known method, thereby reacting reactive silicon.
  • a group-containing polyether is produced.
  • the unsaturated group-containing polyether that has been subjected to a treatment for removing impurities and to which ascorbic acid has been added after the treatment is obtained by a hydrosilylation reaction in a method such as the method described in Patent Document 4. It is suitably used as a raw material for producing the containing polyether.
  • the turbidity index A660 is 0.008 or more when the ascorbic acid metal salt content generated after adding ascorbic acid is 10 ppm by weight or more, and turbidity is confirmed visually. Is done. Therefore, the amount of the metal ascorbate contained in the unsaturated group-containing polyether is 0.001 ppm to 10 ppm, preferably 0.001 to 8 ppm, preferably 0.001 ppm. More preferably, it is more preferably less than 6 ppm by weight, and particularly preferably more than 0.001 ppm by weight and less than 4 ppm by weight.
  • the unsaturated group containing polyether whose amount of ascorbic acid metal salt is 0.001 weight ppm or more and less than 10 weight ppm is a mixture of unsaturated group containing polyether whose A660 is 0.000 or less and ascorbic acid.
  • the unsaturated group-containing polyether is preferably used. Further, the difference between A660 of the unsaturated group-containing polyether before mixing with ascorbic acid and A660 of the unsaturated group-containing polyether after mixing with ascorbic acid is 0.001 or more and less than 0.008. Is preferred.
  • Ascorbic acid added to the unsaturated group-containing polyether is L-ascorbic acid; isoascorbic acid; L-ascorbic acid or an ester derivative of isoascorbic acid; L-ascorbic acid or a phosphoric acid ester derivative of isoascorbic acid; It is an ether derivative of L-ascorbic acid or isoascorbic acid, more preferably L-ascorbic acid and isoascorbic acid.
  • Isoascorbic acid is a structural isomer of L-ascorbic acid.
  • ester derivatives include L-ascorbyl lutinate, L-ascorbyl stearate, L-ascorbyl 2-ethylhexanoate, isoascorbyl palmitate, isoascorbyl stearate, and isoascorbyl 2-ethylhexanoate. Can be mentioned.
  • phosphoric acid ester derivatives include L-ascorbic acid monophosphate, L-ascorbic acid diphosphate, L-ascorbic acid triphosphate, isoascorbic acid monophosphate, isoascorbic acid diphosphate, And isoascorbic acid triphosphate.
  • ether derivative examples include L-ascorbic acid-2-glucoside and isoascorbic acid-2-glucoside.
  • Examples of the method for adding ascorbic acid described above include a method of adding it by dissolving it in water or a solvent such as an organic solvent such as methanol or ethanol, a method of adding it as a solid, and the like.
  • the amount of ascorbic acid added varies depending on the amount of impurities such as catalyst residues in the unsaturated group-containing polyether, but is preferably 10 to 100 ppm by weight, more preferably 20 to 80 ppm by weight. If the amount of ascorbic acid added is excessive, turbidity may occur in the unsaturated group-containing polyether. If the amount of ascorbic acid added is too small, an adverse effect on the hydrosilylation reaction may occur when the hydrosilylation reaction is carried out using an unsaturated group-containing polyether.
  • the time for stirring the unsaturated group-containing polyether and ascorbic acid is not particularly limited.
  • the stirring time is preferably 5 minutes to 5 hours, more preferably 10 minutes to 3 hours. If the stirring time is excessively long, the production efficiency will deteriorate.
  • the temperature at which the unsaturated group-containing polyether and ascorbic acid are stirred is not particularly limited.
  • the temperature at the time of stirring is preferably 20 to 140 ° C, more preferably 40 to 120 ° C.
  • the ascorbic acid metal salt contained in the unsaturated gold-containing polyether is preferably derived from ascorbic acid added to the unsaturated group-containing polyether after the treatment for removing impurities.
  • Metal components such as Na and Zn derived from metal alkoxide, composite metal cyanide complex compound catalyst, sodium sulfate, etc. remaining in the unsaturated group-containing polyether after the removal of impurities are added to the unsaturated group-containing polyether.
  • Ascorbic acid metal salt is formed by binding with ascorbic acid.
  • Ascorbic acid metal salts generated after the addition of ascorbic acid include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium, calcium and barium; and various metal salts such as aluminum and zinc And metal salts thereof.
  • the purified unsaturated group-containing polyether to which ascorbic acid is added preferably contains sodium ascorbate and / or zinc ascorbate as the metal ascorbate.
  • the type of metal ascorbate is not particularly limited.
  • Ascorbic acid metal salts include metal salts derived from metal alkoxides, metal salts derived from polymerization catalysts, metal salts generated from methods for producing unsaturated group-containing polyethers, and unsaturated group-containing polyethers.
  • the amount of peroxide in the unsaturated group-containing polyether before the addition of ascorbic acid is not particularly limited, but is preferably 30 ppm by weight or less.
  • the amount of peroxide is determined by iodine-thiosulfate titration.
  • the silane compound used in the hydrosilylation reaction of the unsaturated group-containing polyether may be a hydrosilane compound having one or more Si—H groups in the molecule.
  • a typical hydrosilane compound for example, a compound represented by the following general formula (1) may be mentioned.
  • 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.
  • 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.
  • A may be 0, 1, 2, or 3
  • b may be 0, 1, or 2, and may be represented by m — (SiR 2 2-b X b O) —.
  • m represents an integer of 0 to 19, where, a and b satisfy the a + ⁇ b ⁇ 1.
  • Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3.
  • (a + ⁇ b) is preferably in the range of 1 to 5.
  • two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different.
  • hydrosilane compound a compound represented by the following general formula (2) is particularly preferable because it is easily available.
  • hydrosilane compounds include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyldichlorosilane, and trimethylsiloxymethylchlorosilane; trimethoxysilane, triethoxysilane, and methyldiethoxy.
  • halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyldichlorosilane, and trimethylsiloxymethylchlorosilane; trimethoxysilane, triethoxysilane, and methyldiethoxy.
  • Alkoxysilanes such as silane, methyldimethoxysilane, phenyldimethoxysilane, trimethylsiloxymethylmethoxysilane, trimethylsiloxydiethoxysilane; methyldiacetoxysilane, phenyldiacetoxysilane, triacetoxysilane, trimethylsiloxymethylacetoxysilane, trimethylsiloxydi Acyloxysilanes such as acetoxysilane; bis (dimethylketoximate) methylsilane, bis (cyclohexylketoximate) methyl Examples include lanthanum, bis (diethylketoximate) trimethylsiloxysilane, bis (methylethylketoximate) methylsilane, tris (acetoxymate) silane and other ketoximate silanes; methylisopropenyloxysilane and other alkenyloxysilanes. . Of these, alkoxys
  • the kind of ascorbic acid metal salt contained in the reactive silicon group-containing polyether is the same as the kind of ascorbic acid metal salt contained in the purified unsaturated group-containing polyether.
  • Ascorbic acid metal salt in reactive silicon group-containing polyether is derived from ascorbic acid and / or ascorbic acid metal salt subjected to hydrosilylation together with unsaturated group-containing polyether after treatment to remove impurities Is preferred.
  • the amount of ascorbic acid metal salt contained in the reactive silicon group-containing polyether obtained through the hydrosilylation reaction is also preferably 0.001 ppm by weight or more and less than 10 ppm by weight. Reactive silicon group-containing polyethers containing an ascorbic acid metal salt in such a range are clear without turbidity.
  • 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)). As a pH meter, S220-Kit manufactured by METTLER TOLEDO was used.
  • the polyether from which the volatile components have been removed is transferred to a spectrophotometer cell (2-478-05 manufactured by As One Co., Ltd.), and then the polyether is used using Perger (PC-250K manufactured by Samplertech Co., Ltd.).
  • the cell containing the sample was defoamed.
  • 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 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.
  • Example 1 687 g of the unsaturated group-containing polyether (a1) obtained in Synthesis Example 2 was placed in a stirring vessel and heated to 90 ° C. After adding 0.137 g of ascorbic acid (200 ppm with respect to the unsaturated group-containing polyether (a1)) and 344 g of ion-exchanged water to the heated unsaturated group-containing polyether (a1), the mixture is allowed to stand for 5 minutes. Separated into organic and aqueous phases. The mixture was stirred at a rotation speed of 700 rpm for 1 hour and then at a rotation speed of 50 rpm for 15 minutes, and then allowed to stand for 25 minutes to separate the organic phase and the aqueous phase, and the aqueous phase was removed.
  • the pH of the wash water was 5.5. Subsequently, ascorbic acid was not added next, 344 g of ion-exchanged water was added to the organic layer, and then allowed to stand for 5 minutes to separate the organic phase and the aqueous phase. The mixture was stirred at a rotation speed of 700 rpm for 1 hour and then at a rotation speed of 50 rpm for 15 minutes, and then allowed to stand for 25 minutes to separate the organic phase and the aqueous phase, and the aqueous phase was removed.
  • Example 2 687 g of the unsaturated group-containing polyether (a1) obtained in Synthesis Example 2 was placed in a stirring vessel and heated to 90 ° C. After adding 0.131 g of ascorbic acid (190 ppm with respect to the unsaturated group-containing polyether (a1)) and 344 g of ion-exchanged water to the heated unsaturated group-containing polyether (a1), the mixture is allowed to stand for 5 minutes. Separated into organic and aqueous phases. The mixture was stirred at a rotation speed of 700 rpm for 1 hour and then at a rotation speed of 50 rpm for 15 minutes, and then allowed to stand for 25 minutes to separate the organic phase and the aqueous phase, and the aqueous phase was removed.
  • the pH of the wash water was 5.8. Subsequently, ascorbic acid was not added next, 344 g of ion-exchanged water was added to the organic phase, and then allowed to stand for 5 minutes to separate the organic phase and the aqueous phase. The mixture was stirred at a rotation speed of 700 rpm for 1 hour and then at a rotation speed of 50 rpm for 15 minutes, and then allowed to stand for 25 minutes to separate the organic phase and the aqueous phase, and the aqueous phase was removed.
  • Example 3 687 g of the unsaturated group-containing polyether (a1) obtained in Synthesis Example 2 was placed in a stirring vessel and heated to 90 ° C. After adding 0.124 g of ascorbic acid (180 ppm with respect to the unsaturated group-containing polyether (a1)) and 344 g of ion-exchanged water to the heated unsaturated group-containing polyether (a1), the mixture is allowed to stand for 5 minutes. Separated into organic and aqueous phases. The mixture was stirred at a rotation speed of 700 rpm for 1 hour and then at a rotation speed of 50 rpm for 15 minutes, and then allowed to stand for 25 minutes to separate the organic phase and the aqueous phase, and the aqueous phase was removed.
  • the pH of the washing water was 6.1. Subsequently, ascorbic acid was not added next, 344 g of ion-exchanged water was added to the organic phase, and then allowed to stand for 5 minutes to separate the organic phase and the aqueous phase. The mixture was stirred at a rotation speed of 700 rpm for 1 hour and then at a rotation speed of 50 rpm for 15 minutes, and then allowed to stand for 25 minutes to separate the organic phase and the aqueous phase, and the aqueous phase was removed.
  • the pH of the washing water was 6.3. Subsequently, ascorbic acid was not added next, 344 g of ion-exchanged water was added to the organic phase, and then allowed to stand for 5 minutes to separate the organic phase and the aqueous phase. The mixture was stirred at a rotation speed of 700 rpm for 1 hour and then at a rotation speed of 50 rpm for 15 minutes, and then allowed to stand for 25 minutes to separate the organic phase and the aqueous phase, and the aqueous phase was removed.
  • Example 4 50 g of the unsaturated group-containing polyether (a1) obtained in Example 3 and 1 g of hexane were added to a 200 mL four-necked flask and devolatilized at 90 ° C., followed by stirring for 1 hour. Thereafter, the inside of the flask was replaced with N 2 . Next, 23 ⁇ L of platinum-vinylsiloxane complex (Pt 1 wt% / isopropanol (hereinafter, IPA)) was added to the flask, and then stirred. Thereafter, 1.2 g of dimethoxymethylsilane was slowly dropped into the flask. After the dropwise addition, the mixed solution was reacted at 90 ° C.
  • Pt 1 wt% / isopropanol hereinafter, IPA
  • Comparative Example 2 50 g of unsaturated group-containing polyether (a1) obtained in Comparative Example 1 and 1 g of hexane were added to a 200-mL four-necked flask, devolatilized at 90 ° C., and stirred for 1 hour. Thereafter, the inside of the flask was replaced with N 2 . Next, 23 ⁇ L of platinum-vinylsiloxane complex (Pt 1 wt% / isopropanol (hereinafter, IPA)) was added to the flask, and then stirred. Thereafter, 1.2 g of dimethoxymethylsilane was slowly dropped into the flask. After the dropwise addition, the mixed solution was reacted at 90 ° C.
  • Pt 1 wt% / isopropanol hereinafter, IPA

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Abstract

La présente invention concerne un procédé de production d'un polyéther contenant un groupe insaturé qui permet la production d'un polyéther contenant un groupe insaturé ayant une faible turbidité ; et un procédé de production d'un polyéther contenant un groupe silicium réactif qui permet la production d'un polyéther contenant un groupe silicium réactif ayant une faible turbidité. Ces procédés de production d'un polyéther sont caractérisés en ce que la concentration d'un sel métallique d'acide ascorbique dans un polyéther contenant un groupe insaturé ou un polyéther contenant un groupe silicium réactif est fixée à 0,001-10 ppm.
PCT/JP2019/016333 2018-04-16 2019-04-16 Méthode de production de polyéther WO2019203233A1 (fr)

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JP7393330B2 (ja) 2018-04-18 2023-12-06 株式会社カネカ ポリエーテルの製造方法

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JPH0436312A (ja) * 1990-05-31 1992-02-06 Kanegafuchi Chem Ind Co Ltd オレフィン末端ポリオキシテトラメチレンの製造方法
JPH10212349A (ja) * 1996-11-18 1998-08-11 Kenrick M Lewis ヒドロシリル化前のポリエーテルの処理方法
WO2006049087A1 (fr) * 2004-11-01 2006-05-11 Kaneka Corporation Procédé de synthèse de polyéthers et préparations contenant lesdits polyéthers
JP2006124621A (ja) * 2004-11-01 2006-05-18 Kaneka Corp 硬化性組成物
JP2007204701A (ja) * 2006-02-06 2007-08-16 Nof Corp アルケニル基含有ポリオキシアルキレン誘導体及びその製造方法
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JP4600397B2 (ja) * 2004-11-01 2010-12-15 株式会社カネカ ポリエーテルの製造方法および重合体
JP7068874B2 (ja) * 2018-03-16 2022-05-17 株式会社カネカ 不飽和基含有ポリオキシアルキレン系重合体の製造方法
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JPH0436312A (ja) * 1990-05-31 1992-02-06 Kanegafuchi Chem Ind Co Ltd オレフィン末端ポリオキシテトラメチレンの製造方法
JPH10212349A (ja) * 1996-11-18 1998-08-11 Kenrick M Lewis ヒドロシリル化前のポリエーテルの処理方法
WO2006049087A1 (fr) * 2004-11-01 2006-05-11 Kaneka Corporation Procédé de synthèse de polyéthers et préparations contenant lesdits polyéthers
JP2006124621A (ja) * 2004-11-01 2006-05-18 Kaneka Corp 硬化性組成物
JP2007204701A (ja) * 2006-02-06 2007-08-16 Nof Corp アルケニル基含有ポリオキシアルキレン誘導体及びその製造方法
JP2008285585A (ja) * 2007-05-17 2008-11-27 Kaneka Corp トリメトキシシリル基を末端に有する有機重合体の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7393330B2 (ja) 2018-04-18 2023-12-06 株式会社カネカ ポリエーテルの製造方法

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