JP2023133187A - Manufacturing method of organic polymer - Google Patents

Abstract

To provide a purification method having a high recovering rate of a polymer and capable of suppressing decrease of polymer viscosity, while reducing an amount of impurities in the polymer, in a method of purifying an organic polymer containing halogen atoms as the impurity with an absorption agent.SOLUTION: An organic polymer (A2) is obtained from an organic polymer (A1) containing halogen atoms as an impurity through a purification step. The purification process comprises steps of: adding a non-polar solvent (S1), a polar solvent (S2), and an adsorbent (I) to the organic polymer (A1) to obtain a mixed solution (M1); removing the adsorbent (I) from the mixed solution (M1) to obtain a mixed solution (M2); and removing the non-polar solvent (S1) and the polar solvent (S2) from the mixed solution (M2) to obtain the organic polymer (A2). A weight ratio (S1):(S2)=100:1 to 1:1. A total amount of halogen atoms contained in the organic polymer (A2) is smaller than the total amount of halogen atoms contained in the organic polymer (A1).SELECTED DRAWING: None

Description

The present invention relates to a method for producing an organic polymer including a purification step.

A reactive silicon group-containing polyoxyalkylene polymer can be crosslinked by formation of a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture and a dehydration condensation reaction. It is known that reactive silicon group-containing polyoxyalkylene polymers have the property of providing a rubber-like cured product through such a crosslinking reaction.
Reactive silicon group-containing polyoxyalkylene polymers have already been produced industrially and 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 polyoxyalkylene polymer, ring-opening polymerization of alkylene oxide is carried out using an alkali metal such as KOH or a multi-metal cyanide complex as a catalyst, and the polymer has a hydroxyl group at the terminal. After producing a polyoxyalkylene polymer and converting the terminal hydroxyl group of the polyoxyalkylene polymer into an unsaturated group, the terminal unsaturated group is subjected to a hydrosilylation reaction with a hydrosilane compound having a reactive silicon group. Therefore, a method of introducing reactive silicon groups into polyoxyalkylene polymers is known.

However, if the unsaturated group-containing polyoxyalkylene polymer contains impurities derived from the manufacturing process (e.g., alkali components, metal impurities such as multimetal cyanide complexes and/or their residual compounds), the polymer This may cause turbidity during coalescence or inhibit the subsequent hydrosilylation reaction.

One method for removing such impurities and obtaining a purified polymer is to precipitate the impurities by mixing a specific solvent with the polyoxyalkylene polymer, and then remove the precipitated impurities from the polymer. Methods are known (see, for example, Patent Documents 1 and 2).

Another known method is to add an inorganic adsorbent to a polymer and allow the adsorbent to adsorb impurities.
For example, Patent Document 3 describes a purification method in which an inorganic adsorbent is added to a polyoxyalkylene polymer to adsorb a metal derived from a composite metal cyanide complex as an impurity, and then the inorganic adsorbent is separated from the polymer. It is stated that the filtration rate can be increased by performing adsorption with an inorganic adsorbent in the presence of 0.1 to 10% by weight of water (paragraph 0040).

Furthermore, in Patent Document 4, as a method for reducing impurities having a different number of hydroxyl groups (for example, a diol form contained in a small amount in a monool form) from a polyoxyalkylene derivative, the derivative is mixed with an aprotic organic A method is described in which, after dissolving in a solvent (preferably a low polar solvent, especially toluene), an inorganic adsorbent is added to form a slurry, and the derivative is recovered from the slurry.

International Publication No. 2019/203234 JP2020-84025A International Publication No. 2008/026657 JP2010-254978A

Polymer purification methods using inorganic adsorbents disclosed in Patent Documents 3 and 4 include a method in which impurities are precipitated, and a method in which impurities are removed by dissolving them in a large amount of water and separating the water. It has the advantage that impurities can be reduced easily and in a short time. However, in the purification process, a portion of the polyoxyalkylene polymer is adsorbed onto the inorganic adsorbent, resulting in a problem that the recovery rate of the polymer decreases and the viscosity of the polymer decreases.
This decrease in polymer viscosity is thought to be due to the fact that high molecular weight components in the polymer are preferentially adsorbed onto the inorganic adsorbent.

In addition, the unsaturated group-containing polyoxyalkylene polymer may contain halogen atoms as impurities due to the reaction at the time of introducing the unsaturated group. Patent Document 3 describes that metals derived from multimetal cyanide complexes can be removed, and Patent Document 4 describes that impurities with different numbers of hydroxyl groups (for example, diols contained in small amounts in monools) can be removed. There is no mention of removal.

In view of the above-mentioned current situation, the present invention is a method for purifying organic polymers containing halogen atoms as impurities using an adsorbent, which reduces the amount of impurities in the polymer while increasing the recovery rate of the polymer. It is an object of the present invention to provide a purification method capable of suppressing a decrease in polymer viscosity.

As a result of extensive studies, the present inventors found that when an organic polymer containing halogen atoms as an impurity is purified using an adsorbent, two types of specific solvents and an adsorbent are added to the polymer to obtain a mixed solution. The inventors have discovered that the above-mentioned problems can be solved by doing so, and have arrived at the present invention. Furthermore, we have also discovered that the adsorbent is not limited to inorganic adsorbents such as those disclosed in Patent Documents 3 and 4, but also organic resin-based adsorbents can be used.

That is, the present invention is a method for producing an organic polymer (A2), which includes obtaining an organic polymer (A2) from an organic polymer (A1) containing a halogen atom as an impurity through a purification step,
The purification step is
Adding a non-polar solvent (S1), a polar solvent (S2), and an adsorbent (I) to the organic polymer (A1) to obtain a mixed solution (M1),
A step of removing the adsorbent (I) from the mixed solution (M1) to obtain a mixed solution (M2), and a step of removing the non-polar solvent (S1) and the polar solvent (S2) from the mixed solution (M2) to obtain an organic polymer. (A2),
The weight ratio of the non-polar solvent (S1) and the polar solvent (S2) is (S1):(S2)=100:1 to 1:1,
The total amount of halogen atoms contained in the organic polymer (A2) is less than the total amount of halogen atoms contained in the organic polymer (A1).

According to the present invention, there is provided a method for purifying an organic polymer containing halogen atoms as an impurity using an adsorbent, and the recovery rate of the polymer is high while reducing the amount of impurities in the polymer. It is possible to provide a purification method that can suppress a decrease in the combined viscosity.

Embodiments of the present invention will be specifically described below, but the present invention is not limited to these embodiments.

The method for producing an organic polymer (A2) according to the present embodiment is to obtain an organic polymer (A2) from an organic polymer (A1) containing a halogen atom as an impurity through a purification step, and the purification step includes: A step of adding a non-polar solvent (S1), a polar solvent (S2), and an adsorbent (I) to an organic polymer (A1) to obtain a mixed solution (M1); ) to obtain a mixed solution (M2), and a step of removing a non-polar solvent (S1) and a polar solvent (S2) from the mixed solution (M2) to obtain an organic polymer (A2). .

The types of organic polymers (A1) and (A2) are not particularly limited, but for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxy Polyoxyalkylene polymers such as propylene-polyoxybutylene copolymers; ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, polybutadiene, isoprene, or butadiene; Saturated hydrocarbon polymers such as copolymers with acrylonitrile, styrene, etc., and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; polyester polymers; ethyl (meth)acrylate; (Meth)acrylic acid ester polymers obtained by radical polymerization of (meth)acrylic acid ester monomers such as butyl (meth)acrylate, as well as (meth)acrylic acid monomers such as vinyl acetate, acrylonitrile, and styrene. Vinyl polymers such as those obtained by radical polymerization of vinyl monomers; Graft polymers obtained by polymerizing the aforementioned vinyl monomers; Polyamide polymers; Polycarbonate polymers; Diaryl phthalate polymers; Examples include organic polymers. Each of the above polymers may be mixed in a block form, a graft form, or the like. Among these, polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester polymers have relatively low glass transition temperatures and the resulting cured products have excellent cold resistance. preferred. Polyoxyalkylene polymers are particularly preferred.

The organic polymers (A1) and (A2) may be a polymer having any one type of polymer skeleton among the various polymer skeletons described above, or may be a mixture of polymers having different polymer skeletons. Further, the mixture may be a mixture of polymers manufactured separately, or a mixture of polymers manufactured simultaneously to have an arbitrary mixture composition.

The polyoxyalkylene polymer, which is a preferred embodiment of the organic polymers (A1) and (A2), refers to one having a polymer skeleton composed of oxyalkylene repeating units. The polymer skeleton may be linear or branched. The polymer skeleton is a polymer skeleton composed only of oxyalkylene repeating units, or contains a structure derived from an initiator used during polymerization in addition to the oxyalkylene repeating units, and is composed only of these. It is preferable that the polymer skeleton is

The oxyalkylene repeating unit refers to a repeating unit constituting a polyether, and refers to, for example, an oxyalkylene unit having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.
The type of polymer skeleton of the polyoxyalkylene polymer is not particularly limited and includes those mentioned above, but polyoxypropylene is particularly preferred.

The organic polymers (A1) and (A2) may have no functional group, or may have one. The functional group is not particularly limited, and includes, for example, an unsaturated group, a reactive silicon group, and the like. In particular, it is preferable to have an unsaturated group. Although the organic polymer (A1) may contain halogen atoms as impurities due to the reaction of introducing unsaturated groups into the polymer skeleton, according to this embodiment, the halogen atoms can be efficiently removed.
Note that the unsaturated group refers to a group containing a carbon-carbon double bond or a group containing a carbon-carbon triple bond.

The method for producing the organic polymer (A1) is not particularly limited, and any known synthesis method can be used. For example, when the organic polymer (A1) is a polyoxyalkylene polymer having an unsaturated group, for example, in the presence of an initiator having a hydroxyl group and a polymerization catalyst such as a multimetal cyanide complex, monomer After ring-opening addition polymerization of epoxide to obtain a hydroxyl group-containing polyoxyalkylene polymer, the hydroxyl group of the polymer is converted to an unsaturated group to obtain a polyoxyalkylene polymer having an unsaturated group. can be manufactured.

In the polyoxyalkylene polymer having unsaturated groups, the ratio of the number of unsaturated groups to the total number of hydroxyl groups and unsaturated groups is preferably 50% or more, more preferably 70% or more, and furthermore 80% or more. Preferably, 85% or more is particularly preferable. The ratio can be determined from the integral ratio of signals corresponding to hydroxyl groups and unsaturated groups using, for example, ¹ H NMR.

The monoepoxide is not particularly limited, and examples thereof include ethylene oxide, propylene oxide, butylene oxide (eg, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide), and styrene oxide. Only one type may be used, or two or more types may be used in combination. From the viewpoint of availability and physical properties of the resulting polymer, ethylene oxide and propylene oxide are preferred, and propylene oxide is particularly preferred.

The initiator having a hydroxyl group is not particularly limited, but includes, for example, ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, neopentyl glycol, glycerin, pentaerythritol, diethylene glycol, triethylene glycol, and low molecular weight polyoxypropylene diol. , low molecular weight polyoxypropylene triol, allyl alcohol, methallyl alcohol, low molecular weight polyoxypropylene monoallyl ether, low molecular weight polyoxypropylene monoalkyl ether, and other organic compounds having one or more hydroxyl groups.

Examples of the polymerization catalyst include metal porphyrins such as complexes obtained by reacting porphyrins with transition metal compounds such as multimetal cyanide complexes, alkali metal catalysts, and organoaluminum compounds, and phosphazenes. Multimetal cyanide complexes are preferred because they yield polymers with a small molecular weight distribution (Mw/Mn) and low viscosity. Further, according to the manufacturing method of this embodiment, impurities derived from the multimetal cyanide complex can be efficiently removed from the organic polymer.

As the composite metal cyanide complex, conventionally known compounds can be used, including but not limited to, Zn ₃ [Fe(CN) ₆ ] ₂ , Zn ₃ [Co(CN) ₆ ] ₂ , Fe[Fe( CN) ₆ ], and Fe[Co(CN) ₆ ]. Among these, Zn ₃ [Co(CN) ₆ ] ₂ (ie, zinc hexacyanocobaltate complex) is preferred.

Further, the multimetal cyanide complex may be one in which an organic ligand is coordinated. The organic ligand is preferably alcohol and/or ether.
Examples of the alcohol include tert-butyl alcohol, ethanol, sec-butyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-pentyl alcohol, isopentyl alcohol, and isopropyl alcohol. Examples of the ether include glyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), dioxane, and polyethers having a number average molecular weight of 150 to 5,000. Among these organic ligands, tert-butyl alcohol and glyme are particularly preferred.

Conditions for carrying out ring-opening addition polymerization of monoepoxide can be appropriately selected from conventionally known conditions. Through this polymerization reaction, a polyoxyalkylene polymer having a hydroxyl group at the end of the polymer skeleton can be produced.

Next, by converting the hydroxyl groups of the hydroxyl group-containing polyoxyalkylene polymer into unsaturated ones, a polyoxyalkylene polymer having unsaturated groups can be obtained.
More specifically, the hydroxyl groups of the hydroxyl group-containing polyoxyalkylene polymer can be converted to unsaturated groups by reacting them with an alkali metal salt and then reacting them with an unsaturated group-containing organic halide. . This will be explained in detail below.

(Reaction with alkali metal salt)
First, it is preferable that an alkali metal salt is applied to the hydroxyl group-containing polyoxyalkylene polymer to convert the hydroxyl groups contained in the polymer into metaloxy groups. Moreover, a multimetal cyanide complex catalyst can also be used instead of an alkali metal salt. Through the above steps, a metaloxy group-containing polyoxyalkylene polymer is formed.

The alkali metal salt is not particularly limited, but includes, for example, sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, cesium alkoxide, and the like. In terms of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred, and sodium methoxide and sodium tert-butoxide are preferred. -Butoxide is more preferred. In terms of availability, sodium methoxide is particularly preferred, and in terms of reactivity, sodium tert-butoxide is particularly preferred. The alkali metal salt may be subjected to the reaction in a state dissolved in a solvent.
Conventionally known conditions can be appropriately adopted as the conditions for the action of the alkali metal salt.

(Reaction with unsaturated group-containing organic halide)
Next, the polyoxyalkylene polymer having metaloxy groups is reacted with an unsaturated group-containing organic halide to convert the metaloxy groups contained in the polymer into unsaturated groups. The unsaturated group-containing organic halide reacts with the metaloxy group through a halogen substitution reaction to form an ether bond. As a result, a polyoxyalkylene polymer having unsaturated groups is formed.

As the unsaturated group-containing organic halide, an organic halide containing a carbon-carbon double bond or an organic halide containing a carbon-carbon triple bond can be used.
Specific examples of organic halides containing carbon-carbon double bonds include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, methallyl iodide, etc. Can be mentioned. Among these, allyl chloride and methallyl chloride are preferred.
Specific examples of organic halides containing carbon-carbon triple bonds include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentyne, 1,4-dichloro-2-butyne, 5-chloro-1-pentyne, 6-chloro-1-hexyne, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, 1-bromo- 2-octyne, 1-bromo-2-pentyne, 1,4-dibromo-2-butyne, 5-bromo-1-pentyne, 6-bromo-1-hexyne, propargyl iodide, 1-iodo-2-butyne, 4-iodo-1-butyne, 1-iodo-2-octyne, 1-iodo-2-pentyne, 1,4-diiodo-2-butyne, 5-iodo-1-pentyne, and 6-iodo-1-hexyne etc. Among these, propargyl chloride, propargyl bromide, and propargyl iodide are preferred, and propargyl bromide is particularly preferred.

As the conditions for reacting the unsaturated group-containing organic halide, conventionally known conditions can be appropriately adopted.

Further, the metaloxy group-containing polyoxyalkylene polymer is first reacted with an epoxy compound having an unsaturated group (for example, allyl glycidyl ether), and then the above-mentioned unsaturated group-containing organic halide is reacted with the polyoxyalkylene polymer. It is also possible to form a polyoxyalkylene polymer having two or more unsaturated groups at one end.

The polyoxyalkylene polymer produced as described above contains impurities such as halogen derived from the unsaturated group-containing organic halide, metal impurities derived from the polymerization catalyst (multimetal cyanide complex or alkali metal catalyst and and/or residual compounds thereof, particularly zinc, cobalt, etc.), impurities derived from the alkali metal salts, and the like.

The impurities contained in the organic polymer (A1) are not limited to the above description, but include at least a halogen atom. In addition to halogen atoms, metals derived from the multimetal cyanide complex, particularly cobalt atoms and/or zinc atoms, may be contained as impurities.

According to the manufacturing method according to the present embodiment, the amount of impurities, particularly halogen atoms, contained in the organic polymer (A1) can be reduced. Furthermore, in addition to halogen atoms, it is also possible to reduce the amount of cobalt atoms and/or zinc atoms.

(Adsorbent (I))
The production method according to the present embodiment is to obtain an organic polymer (A2) with reduced impurities by adsorbing impurities contained in the organic polymer (A1) onto the adsorbent (I).
The adsorbent (I) is not particularly limited and any conventionally known adsorbent can be used. Agent: Examples include organic resin-based adsorbents such as styrene-based and (meth)acrylic-based adsorbents. Among these, inorganic adsorbents containing magnesium, aluminum, and/or silicon are preferred because they have a high ability to reduce impurities.

Specifically, the inorganic adsorbents include silicon dioxide; magnesium oxide; aluminum oxide; magnesium silicate; silica gel; silica/alumina, aluminum silicate; activated alumina; clay-based adsorbents such as acid clay and activated clay; aluminum silicate. Examples include zeolite-based adsorbents, which are collectively referred to as a group of hydrous aluminosilicate minerals such as sodium; dawsonite compounds; hydrotalcite compounds, and the like. Furthermore, the inorganic adsorbent may be a composition containing at least one of the substances, adsorbents, and compounds exemplified above. As the adsorbent (I), only one type may be used, or two or more types may be used in combination.

Among them, synthetic aluminum silicate, synthetic alumina magnesia (solid solution of MgO and AlO), synthetic hydrotalcite, synthetic magnesium silicate, and silica/magnesia-based preparations are preferable because they have high impurity adsorption performance. type formulations are more preferred, and synthetic aluminum silicate is particularly preferred.

The amount of adsorbent (I) to be used can be determined as appropriate in consideration of the amount of impurities to be removed; Usually, 10 to 70 parts by weight is preferred, and 20 to 50 parts by weight is more preferred.

(Non-polar solvent (S1) and polar solvent (S2))
In the manufacturing method according to the present embodiment, a nonpolar solvent (S1), a polar solvent (S2), and an adsorbent (I) are added to an organic polymer (A1) to prepare a mixed solution (M1). By using a solvent, it becomes possible to uniformly mix the organic polymer (A1) and the adsorbent (I), and impurities can be efficiently removed from the organic polymer (A1).

From the viewpoint of improving impurity removal efficiency or usability of the solvent, it is preferable that the non-polar solvent (S1) and the polar solvent (S2) each dissolve the organic polymer (A1). The polar solvent (S2) may not dissolve the organic polymer (A1).

In addition, from the viewpoint of improving impurity removal efficiency or usability of the solvent, it is preferable that the non-polar solvent (S1) and the polar solvent (S2) be made compatible to form a uniform mixed solvent. ) and the polar solvent (S2) may be separated into two layers without being made compatible.

The non-polar solvent (S1) refers to a solvent with a dielectric constant of 4 or less (preferably 3 or less), such as aliphatic hydrocarbon solvents such as pentane, hexane, octane, and cyclohexane; benzene, toluene, xylene, etc. aromatic hydrocarbon solvents. Only one type of these may be used, or two or more types may be used in combination. Alternatively, a mixture of two or more types may be used.

The nonpolar solvent (S1) is preferably an aliphatic hydrocarbon solvent or an aromatic hydrocarbon solvent, more preferably an aliphatic hydrocarbon solvent, and even more preferably an aliphatic hydrocarbon solvent having 5 to 8 carbon atoms. , aliphatic hydrocarbon solvents having 6 carbon atoms are particularly preferred.
Further, since it is easy to volatilize and remove, the nonpolar solvent (S1) preferably has a boiling point of 150°C or lower at 1 atmosphere, more preferably 120°C or lower, and even more preferably 100°C or lower.

The polar solvent (S2) refers to a solvent with a dielectric constant exceeding 4, such as alcoholic solvents such as methanol, ethanol, propanol, 2-propanol, n-butyl alcohol, tert-butyl alcohol, and 1-hexanol; acetone. , acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, and other ketone solvents; tetrahydrofuran and other cyclic ether solvents; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and other ester solvents; acetonitrile, propionitrile , nitrile solvents such as benzonitrile; amide solvents such as formamide, N,N-dimethylformamide and N,N-dimethylacetamide; water; carboxylic acids such as formic acid and acetic acid; phenol and the like. Only one type of these may be used, or two or more types may be used in combination. Alternatively, a mixture of two or more types of solvents may be used.

As the polar solvent (S2), an aprotic polar solvent containing no hetero elements other than oxygen, an alcoholic solvent, and water are preferable. Among these, aprotic polar solvents and alcohol solvents that do not contain heteroelements other than oxygen are more preferable because they have good compatibility with the nonpolar solvent (S1). An aprotic polar solvent that does not contain any hetero elements other than oxygen is particularly preferable because it improves the efficiency of removing impurities.

Aprotic polar solvents that do not contain heteroelements other than oxygen refer to aprotic polar solvents that are composed only of carbon, hydrogen, and oxygen, and specifically include ketone solvents, ester solvents, and cyclic ether solvents. Solvents are preferred. Among these, ketone solvents and cyclic ether solvents are more preferable, ketone solvents are even more preferable, and acetone is particularly preferable, since the recovery rate of the polymer is higher and the effect of suppressing a decrease in polymer viscosity is better.

Further, since it is easy to volatilize and remove, the polar solvent (S2) preferably has a boiling point of 150°C or lower at 1 atmosphere, more preferably 120°C or lower, and even more preferably 100°C or lower.

In this embodiment, both a nonpolar solvent (S1) and a polar solvent (S2) are used. If only the nonpolar solvent (S1) is used as a solvent, impurities in the organic polymer (A1) can be removed, but the recovery rate of the polymer is low and the viscosity of the polymer is significantly reduced. On the other hand, if only the polar solvent (S2) is used as a solvent, it becomes difficult to sufficiently remove impurities containing halogen.

The ratio of non-polar solvent (S1) to polar solvent (S2) used is (S1):(S2)=100:1 to 1:1 by weight. By using both solvents together in such a ratio, it is possible to reduce the amount of impurities in the polymer, increase the recovery rate of the polymer, and suppress a decrease in the viscosity of the polymer. The usage ratio is preferably 20:1 to 1:1, more preferably 10:1 to 1:1, and 5:1 to 1:1 from the viewpoint of polymer recovery rate and suppression of decrease in polymer viscosity. More preferably, 4:1 to 1:1 is particularly preferred, and 3:1 to 1:1 is most preferred. Further, from the viewpoint of removing impurities, the usage ratio is preferably 100:1 to 1.5:1, more preferably 100:1 to 2:1, and particularly preferably 100:1 to 3:1. Further, the usage ratio is preferably 10:1 to 1.5:1, more preferably 4:1 to 2:1, from the viewpoint of polymer recovery rate, suppression of decrease in polymer viscosity, and removal of impurities.

The total amount of the non-polar solvent (S1) and the polar solvent (S2) used is preferably an amount sufficient to uniformly dissolve or disperse the organic polymer (A1), and specifically, for example, With respect to 100 parts by weight of (A1), the total amount of the non-polar solvent (S1) and polar solvent (S2) is preferably 10 to 1000 parts by weight, more preferably 50 to 800 parts by weight, and even more preferably 100 to 500 parts by weight. Preferably, 150 to 400 parts by weight is particularly preferable.

Next, the procedure for purifying the organic polymer (A1) according to the present embodiment will be specifically explained.
First, a nonpolar solvent (S1), a polar solvent (S2), and an adsorbent (I) are added to an organic polymer (A1) to obtain a mixed solution (M1).

The order of adding the non-polar solvent (S1), the polar solvent (S2), and the adsorbent (I) is not particularly limited, and they can be added in any order. According to a particularly preferred embodiment, the organic polymer (A1) and the adsorbent (I) can be mixed uniformly and impurities can be efficiently removed from the organic polymer (A1). ) is preferably added with a non-polar solvent (S1) and a polar solvent (S2) to obtain a mixed solution (M0), and then the adsorbent (I) is added.

The order of addition of the non-polar solvent (S1) and the polar solvent (S2) is not particularly limited, and the polar solvent (S2) may be added after the non-polar solvent (S1), or vice versa. Alternatively, the non-polar solvent (S1) and the polar solvent (S2) may be added at the same time, or a mixed solvent (S) prepared by mixing the non-polar solvent (S1) and the polar solvent (S2) in advance may be added. It's okay. It is preferable to add a mixed solvent (S) because more uniform mixing is possible and impurity removal efficiency is improved. When adding a non-polar solvent (S1), a polar solvent (S2), or a mixed solvent (S), each solvent may be added at once, or may be added in two or more portions.

In the mixed solution (M0), the organic polymer (A1) is preferably uniformly dispersed or dissolved in the nonpolar solvent (S1) and the polar solvent (S2), and is particularly preferably dissolved. To achieve such dispersion or dissolution, common machinery such as shakers or stirrers may be used.

Further, the temperature when preparing the mixed solution (M0) is not particularly limited, but is preferably 0 to 140°C, and 10 to 140°C so as to achieve uniform dispersion or dissolution of the organic polymer while suppressing deterioration of the organic polymer. ~100°C is preferred. It may be at room temperature.

Next, the adsorbent (I) was added to the mixed solution (M0) containing the organic polymer (A1), the non-polar solvent (S1) and the polar solvent (S2) obtained above, and the mixed solution (M1) was Obtainable. However, the mixed solution (M1) may be obtained without preparing the mixed solution (M0). For example, the mixture (M1) may be obtained by adding the adsorbent (I) to the organic polymer (A1) and then adding the nonpolar solvent (S1) and the polar solvent (S2). In addition, after adding one of the non-polar solvent (S1) and the polar solvent (S2) to the organic polymer (A1), the adsorbent (I) is added, and then the remaining solvent is added to form a mixed solution. (M1) may also be obtained.

Regardless of whether a mixed solution (M0) is prepared or not, when adding the adsorbent (I), the adsorbent may be added at once or may be added in two or more parts. .

In the mixed solution (M1), impurities contained in the organic polymer (A1) are adsorbed onto the adsorbent (I). In order to allow this adsorption to proceed sufficiently, it is preferable to stir the mixed liquid (M1) for a predetermined period of time. This stirring can be carried out using, for example, a stirrer.

The time for stirring the mixed solution (M1) may be determined as appropriate from the viewpoint of adsorption and removal of impurities, and may be, for example, about 10 minutes to 10 hours, preferably about 30 minutes to 5 hours. Further, the temperature of the mixed liquid (M1) during stirring may be about 0 to 140°C, preferably about 10 to 100°C. It may be at room temperature.

Next, the adsorbent (I) is removed from the liquid mixture (M1) containing the organic polymer, the non-polar solvent (S1), the polar solvent (S2), and the adsorbent (I) obtained above. A mixed solution (M2) containing a polymer, a nonpolar solvent (S1), and a polar solvent (S2) is obtained.

The method for separating the adsorbent (I) from the mixed liquid (M1) is not particularly limited, and static separation, centrifugation, filtration, etc. can be used, but the filtration method is preferred because it is simple and efficient. preferable. In the filtration method, filters commonly used in industry can be used as filter media, such as filter paper, filter cloth, metal mesh, etc. When performing filtration, pressure may be applied as appropriate to increase the filtration rate. Additionally, a filter aid such as diatomaceous earth or perlite may be used.

After separating the adsorbent (I) from the mixed solution (M1) by filtration or the like, the separated adsorbent (I) may be washed in order to increase the recovery rate of the polymer. For the cleaning, a cleaning solvent may be used as appropriate. As such a cleaning solvent, a nonpolar solvent (S1), a polar solvent (S2), or a mixed solvent (S) can be used, and it is preferable to use a mixed solvent (S).

Then, by removing the non-polar solvent (S1) and the polar solvent (S2) from the mixed liquid (M2) containing the organic polymer, the non-polar solvent (S1) and the polar solvent (S2) obtained above, An organic polymer (A2) with at least a reduced halogen atomic weight can be obtained. In order to remove the non-polar solvent (S1) and the polar solvent (S2) from the mixed solution (M2), it is preferable to evaporate and remove the non-polar solvent (S1) and the polar solvent (S2) at room temperature or under reduced pressure. . The temperature at that time may be appropriately set in consideration of the boiling points of the non-polar solvent (S1) and the polar solvent (S2), and is not particularly limited, but may be, for example, about 10 to 140°C, or about 20 to 120°C. The temperature is preferably about 60 to 110°C, more preferably about 60 to 110°C.

By going through each of the steps described above, it is possible to obtain an organic polymer (A2) in which at least the halogen atomic weight is lower than that of the organic polymer (A1). According to this embodiment, by adsorbing impurities to the adsorbent (I) in the presence of a non-polar solvent (S1) and a polar solvent (S2), the amount of impurities in the polymer can be reduced while recovering the polymer. The ratio is high, and it is possible to suppress a decrease in polymer viscosity.

According to a preferred embodiment, for example, from an organic polymer (A1) in which the total amount of halogen atoms exceeds 1,000 ppm, preferably the total amount of halogen atoms is 150 ppm or less, more preferably 120 ppm or less, still more preferably 100 ppm or less, especially It is possible to obtain an organic polymer (A2) having a concentration of preferably 70 ppm or less, most preferably 50 ppm or less.

Here, the total amount of halogen atoms refers to the total content of fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The halogen atoms contained in the organic polymer (A1) are usually derived from by-products generated during the production process of the organic polymer (A1) or from the catalyst used. For example, when allyl chloride is used as the above-mentioned unsaturated group-containing organic halide, the organic polymer (A1) may contain chlorine atoms as impurities.

In addition, when the above-mentioned multimetal cyanide complex is used in the polymerization reaction of the organic polymer (A1), the organic polymer (A1) contains impurities such as zinc atoms and/or cobalt atoms derived from the multimetal cyanide complex. may be included as.

According to a preferred embodiment, for example, from an organic polymer (A1) having a zinc atom content of more than 15 ppm, a zinc atom content of 15 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 1 ppm or less It is also possible to obtain certain organic polymers (A2).

Further, for example, from an organic polymer (A1) having a cobalt atom content of more than 5 ppm, a cobalt atom content of 1 ppm or less, preferably 0.5 ppm or less, more preferably 0.2 ppm or less, and still more preferably 0.1 ppm. It is possible to obtain the following organic polymer (A2).

According to this embodiment, there is little loss of polymer during the purification process, and the recovery rate can be increased. The recovery rate (%) of the polymer can be defined as the weight of the organic polymer (A2) recovered from the purification process/the weight of the organic polymer (A1) used in the purification process x 100. The closer this value is to 100%, the less loss of polymer during the purification process and the higher the recovery rate. The recovery rate that can be achieved by this embodiment is not particularly limited, but may be, for example, 93% or more, preferably 94% or more, more preferably 95% or more, even more preferably 96% or more, and 97% or more. Particularly preferred.

Furthermore, according to this embodiment, it is possible to suppress a decrease in polymer viscosity caused by the purification process. Conventionally, when an organic polymer is purified using an inorganic adsorbent, the viscosity of the organic polymer tends to decrease significantly. This is thought to be because the high molecular weight components in the organic polymer are preferentially adsorbed by the inorganic adsorbent over the low molecular weight components, resulting in a decrease in the content ratio of high molecular weight components in the organic polymer. . However, according to the present embodiment, it is possible to suppress the decrease in the viscosity of the polymer due to the purification process, that is, it is possible to suppress changes in the physical properties of the polymer (in addition to viscosity, molecular weight distribution, etc.) caused by the purification process. It becomes possible.

<Hydrosilylation of unsaturated group-containing organic polymer>
When the organic polymer (A2) has an unsaturated group, the hydrosilylation reaction for the unsaturated group can be carried out satisfactorily. This is because the organic polymer (A2) contains fewer impurities that inhibit the progress of the hydrosilylation reaction.

Typically, a reactive silicon group-containing organic polymer can be produced by subjecting an unsaturated group of the organic polymer (A2) to a hydrosilylation reaction with a reactive silicon group-containing hydrosilane compound.

The reactive silicon group-containing hydrosilane compound is not particularly limited, but includes, for example, halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, and (methoxymethyl)dichlorosilane; Methoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, methoxydimethylsilane, (chloromethyl)methylmethoxysilane, bis(chloromethyl)methoxysilane, (methoxymethyl)dimethoxysilane, bis(methoxy) Alkoxysilanes such as methyl)methoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane; diacetoxymethylsilane, Acyloxysilanes such as diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane, bis(cyclohexylketoximate)methylsilane, triisopropenyloxysilane, (methoxymethyl)diisopropenyloxy Examples include isopropenyloxysilanes (deacetone type) such as silane.

The hydrosilylation reaction can be carried out in the presence of a hydrosilylation catalyst such as a platinum catalyst to promote the reaction. Further, the conditions for carrying out the hydrosilylation reaction are not particularly limited, and may be known conditions.

(Curable composition)
An unsaturated group-containing organic polymer or a reactive silicon group-containing organic polymer can be suitably used as a curing component of a curable composition.
The organic polymer (A2) that can be produced according to this embodiment is clear because impurities have been successfully removed. Therefore, according to this embodiment, a curable composition with excellent transparency can be obtained.

The composition of the curable composition is not particularly limited. Examples of the curable composition containing an unsaturated group-containing organic polymer include a composition containing an unsaturated group-containing organic polymer, a curing agent having at least two hydrosilyl groups in one molecule, and a hydrosilylation catalyst. Things can be mentioned. The composition exhibits curability based on a hydrosilylation reaction.

Further, examples of the curable composition containing a reactive silicon group-containing organic polymer include a composition containing a reactive silicon group-containing organic polymer and a curing catalyst. The reactive silicon group-containing organic polymer is cured by moisture in the presence of a curing catalyst at room temperature or under heating, and can form a coating film with good adhesion to metals, glass, resins, and the like. Curable compositions containing reactive silicon group-containing organic polymers can be used as coating compositions, sealant compositions, coating compositions, adhesive compositions, coating film compositions, etc. in the manufacturing process of buildings, aircraft, automobiles, etc. Useful. As the curing catalyst, conventionally known silanol condensation catalysts can be used.

In each of the following items, preferred embodiments of the present disclosure are listed, but the present invention is not limited to the following items.
[Item 1]
A method for producing an organic polymer (A2), the method comprising obtaining an organic polymer (A2) from an organic polymer (A1) containing halogen atoms as an impurity through a purification step,
The purification step is
Adding a non-polar solvent (S1), a polar solvent (S2), and an adsorbent (I) to the organic polymer (A1) to obtain a mixed solution (M1),
A step of removing the adsorbent (I) from the mixed solution (M1) to obtain a mixed solution (M2), and a step of removing the non-polar solvent (S1) and the polar solvent (S2) from the mixed solution (M2) to obtain an organic polymer. (A2),
The weight ratio of the non-polar solvent (S1) and the polar solvent (S2) is (S1):(S2)=100:1 to 1:1,
A method for producing an organic polymer (A2), wherein the total amount of halogen atoms contained in the organic polymer (A2) is less than the total amount of halogen atoms contained in the organic polymer (A1).
[Item 2]
The manufacturing method according to item 1, wherein the organic polymers (A1) and (A2) are polyoxyalkylene polymers.
[Item 3]
The manufacturing method according to item 1 or 2, wherein the organic polymers (A1) and (A2) have an unsaturated group.
[Item 4]
The manufacturing method according to any one of items 1 to 3, wherein the total amount of halogen atoms contained in the organic polymer (A2) is 150 ppm or less.
[Item 5]
The manufacturing method according to any one of items 1 to 4, wherein the total amount of halogen atoms contained in the organic polymer (A1) exceeds 1,000 ppm.
[Item 6]
After reacting an alkali metal salt with a hydroxyl group-terminated polyoxyalkylene polymer, an unsaturated group-containing organic halide is reacted to produce a polyoxyalkylene polymer having an unsaturated group as an organic polymer (A1). The manufacturing method according to any one of items 1 to 5, comprising the step of obtaining.
[Item 7]
The manufacturing method according to any one of items 1 to 6, wherein the cobalt atomic weight contained in the organic polymer (A2) is 1 ppm or less.
[Item 8]
The manufacturing method according to any one of items 1 to 7, wherein the organic polymer (A2) has a zinc atomic weight of 1 ppm or less.
[Item 9]
The production method according to any one of items 1 to 8, wherein the adsorbent (I) is an inorganic adsorbent containing magnesium, aluminum, and/or silicon.
[Item 10]
Any one of items 1 to 9, wherein the adsorbent (I) is at least one selected from the group consisting of synthetic aluminum silicate, synthetic alumina magnesia, synthetic hydrotalcite, synthetic magnesium silicate, and silica/magnesia-based preparations. The manufacturing method described in.
[Item 11]
The non-polar solvent (S1) is an aliphatic or aromatic hydrocarbon solvent and has a boiling point at 1 atm of 150°C or less,
The manufacturing method according to any one of items 1 to 10, wherein the polar solvent (S2) is an aprotic polar solvent that does not contain a hetero element other than oxygen, and has a boiling point at 1 atm of 150° C. or less.
[Item 12]
The production method according to any one of items 1 to 11, wherein the halogen atom contained in the organic polymer (A1) contains a chlorine atom.
[Item 13]
After producing the organic polymer (A2) by the production method described in any one of items 1 to 12, a reactive silicon group-containing hydrosilane compound is added to the unsaturated group of the obtained organic polymer (A2) to hydrosilyl. A method for producing a reactive silicon group-containing organic polymer by carrying out a chemical reaction.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.

The number average molecular weight is a GPC molecular weight measured under the following conditions.
Liquid feeding system: Tosoh HLC-8420GPC
Column: Tosoh TSKgel SuperH series Solvent: THF
Molecular weight: polystyrene equivalent Measurement temperature: 40°C
Detector: RI

The viscosity is the viscosity measured at 23° C. with an E-type viscometer (RE-85U manufactured by Tokyo Keiki Co., Ltd., measurement cone: 3°×R14).

Each atomic weight in the polymer is a value measured using an energy dispersive X-ray fluorescence spectrometer (EDX-7000 manufactured by Shimadzu Corporation) after preparing a calibration curve for each atom.

The organic solvents used in the following Examples and Comparative Examples were all special grade reagents manufactured by Fuji Film Wako Pure Chemical Industries.

(Synthesis example 1-1)
Using polyoxypropylene triol (commercially available) with a number average molecular weight of about 4,000 as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to form a branched chain with a number average molecular weight of about 13,000. A hydroxyl-terminated polyoxypropylene (E-1) was obtained.

(Synthesis example 1-2)
Polyoxypropylene diol (commercially available) with a number average molecular weight of about 3,500 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to form a linear chain with a number average molecular weight of about 27,000. A hydroxyl-terminated polyoxypropylene (E-2) was obtained.

(Synthesis example 2-1)
A methanol solution of sodium methoxide in an amount of 1.2 equivalents to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene (E-1) obtained by the procedure of Synthesis Example 1-1 was added, and methanol was distilled off at 130°C. Subsequently, by adding 1.5 equivalents of 3-chloro-1-propene (allyl chloride) at 130°C, a compound having an allyl group at the end and containing mainly sodium chloride as an impurity and having a number average molecular weight of 13 ,000 polyoxypropylene polymer (A1-1) was obtained. In the polyoxypropylene polymer (A1-1), the zinc atom content was 20 ppm, the cobalt atom content was 10 ppm, and the chlorine atom content was 14,000 ppm. Further, the ratio of the number of unsaturated groups to the total number of hydroxyl groups and unsaturated groups in the polymer (A1-1) was 98%.
In addition, as shown in Synthesis Examples 1-1 and 2-1, the polymer (A1-1) does not intentionally use a reactant containing a halogen atom other than a chlorine atom in its manufacturing process. Therefore, the content of halogen atoms other than chlorine atoms in the polymer (A1-1) is considered to be substantially zero. Therefore, the chlorine atom content in the polymer (A1-1) can be regarded as the total amount of halogen atoms in the polymer (A1-1).

(Synthesis example 2-2)
A methanol solution of sodium methoxide in an amount of 1.0 equivalent to the hydroxyl group of the hydroxyl-terminated polyoxypropylene (E-2) obtained by the procedure of Synthesis Example 1-2 was added, and methanol was distilled off at 140°C. Subsequently, 1.0 equivalent of allyl glycidyl ether was added at 140°C and reacted for 2 hours to introduce an unsaturated bond, and 1.3 equivalent of 3-chloro-2-methyl-1-propene ( Methallyl chloride) was added to convert the terminal hydroxyl group to a methallyl group. Furthermore, a methanol solution of 0.3 equivalents of sodium methoxide was added to the hydroxyl group of (E-2), methanol was distilled off at 130°C, and then 0.8 equivalents of 3-chloro- By adding 1-propene (allyl chloride), a polyoxypropylene polymer (A1- 2) was obtained. In the polyoxypropylene polymer (A1-2), the zinc atom content was 23 ppm, the cobalt atom content was 11 ppm, and the chlorine atom content was 5,000 ppm. Further, the ratio of the number of unsaturated groups to the total number of hydroxyl groups and unsaturated groups in the polymer (A1-2) was 97%.
As shown in Synthesis Examples 1-2 and 2-2, polymer (A1-2) does not intentionally use a reactant containing halogen atoms other than chlorine atoms in its manufacturing process. Therefore, the content of halogen atoms other than chlorine atoms in the polymer (A1-2) is considered to be substantially zero. Therefore, the chlorine atom content in the polymer (A1-2) can be regarded as the total amount of halogen atoms in the polymer (A1-2).

(Reference Example 1) Water Purification 100 parts by weight of polyoxypropylene polymer (A1-1) obtained by the procedure of Synthesis Example 2-1, 300 parts by weight of n-hexane, and 300 parts by weight of water (deionized water) After mixing and stirring, water was removed by centrifugation. Further, 300 parts by weight of water was mixed and stirred into the obtained n-hexane solution, water was removed by centrifugation again, and then the n-hexane was removed by concentration using an evaporator to obtain a polymer (A2-0). Ta. The viscosity of the polymer was 3.7 Pa·s. In the polyoxypropylene polymer (A2-0), the zinc atom content was less than 0.1 ppm, the cobalt atom content was less than 0.1 ppm, and the chlorine atom content was 40 ppm.
In this reference example, impurities were removed by dissolving them in a large amount of water and separating the water without using an adsorbent. It can be seen that according to such a method, impurities containing halogen atoms are sufficiently removed, and a decrease in polymer viscosity during the purification process can be suppressed. Comparing the results of this reference example with the results of comparative example 1 or 2 described later, it is found that the purification method of comparative example 1 or 2 using an adsorbent has no effect on impurity removal effect, recovery rate, or polymer viscosity. It turns out that this is insufficient.

(Example 1)
To 100 parts by weight of the polyoxypropylene polymer (A1-1) obtained by the procedure of Synthesis Example 2-1, n-hexane as a non-polar solvent (S1): acetone as a polar solvent (S2) = 10: 1 (weight ratio) of 200 parts by weight of a mixed solvent was added and stirred. Furthermore, 30 parts by weight of synthetic aluminum silicate (Kyowa Chemical Industry Co., Ltd., Kyoward 700 SEN-S) as adsorbent (I) was added and stirred, and the mixture was stopped after 60 minutes. Synthetic aluminum silicate was removed by vacuum suction filtration in a Kiriyama funnel lined with filter paper and lined with Celite-545RVS (manufactured by Nacalai Tesque) and Standard Super Cell (manufactured by Nacalai Tesque), and the residue on the Kiriyama funnel was mixed with the above mixture. After washing with a solvent, the filtrate was concentrated using an evaporator to remove the mixed solvent, thereby obtaining a polymer (A2-1). The recovery rate of the polymer was 94%, and the viscosity was 3.5 Pa·s. In the polyoxypropylene polymer (A2-1), the zinc atom content was less than 0.1 ppm, the cobalt atom content was less than 0.1 ppm, and the chlorine atom content was 40 ppm. Similar to the polymer (A1-1), the chlorine atom content in (A2-1) can be regarded as the total amount of halogen atoms in the polymer (A2-1). The same applies to the polymers obtained in the following Examples and Comparative Examples.

(Examples 2 to 6)
Polymers (A2-2) to (A2-6) were obtained by following the same procedure as in Example 1 except for changing the mixing ratio of n-hexane and acetone. The results of the mixing ratio, recovery rate, etc. are shown in Table 1.

(Comparative Examples 1 and 2)
Polymer (A2- 7) and (A2-8) were obtained. The results such as recovery rate are shown in Table 1.

(Examples 7 to 9)
The same procedure as in Example 1 was carried out, except that another polar solvent was used instead of acetone as the polar solvent (S2), and the mixing ratio was n-hexane:polar solvent (S2) = 3:1 (weight ratio). By going through the procedure, polymers (A2-9) to (A2-11) were obtained. The polar solvent (S2) used and the results such as recovery rate are shown in Table 2.

From the results shown in Tables 1 and 2, in Examples 1 to 9 where the weight ratio of nonpolar solvent (S1) to polar solvent (S2) was (S1):(S2) = 100:1 to 1:1, It can be seen that impurities containing halogen atoms are sufficiently removed, a high recovery rate is exhibited, and a decrease in polymer viscosity during the purification process can be suppressed.
On the other hand, in Comparative Example 1 in which only the non-polar solvent (S1) was used, although impurities could be removed, the recovery rate was low and the polymer viscosity significantly decreased. In Comparative Example 2 in which only the polar solvent (S2) was used, impurities, especially zinc and chlorine, were not sufficiently removed.

(Example 10)
Water (deionized water) was used as the polar solvent (S2), and the mixing ratio was n-hexane:water = 20:1 (weight ratio), except that n-hexane was used alone to wash the residue. A polymer (A2-12) was obtained through the same procedure as in Example 1. The recovery rate of the polymer was 96%, and the viscosity was 3.6 Pa·s. In the polyoxypropylene polymer (A2-12), the zinc atom content was less than 0.1 ppm, the cobalt atom content was less than 0.1 ppm, and the chlorine atom content was 60 ppm.
Note that since water is not compatible with the non-polar solvent (S1), it was difficult to use a mixed solvent when washing the residue, so n-hexane was used alone instead.

From the results of Example 10, even when water is used as the polar solvent (S2), impurities containing halogen atoms are sufficiently removed, a high recovery rate is exhibited, and the decrease in polymer viscosity during the purification process can be suppressed. I can see that

(Example 11)
To 100 parts by weight of polyoxypropylene polymer (A1-2) obtained by the procedure of Synthesis Example 2-2, 150 parts by weight of n-hexane, which is a nonpolar solvent (S1), was added and stirred for 30 minutes. Next, 50 parts by weight of acetone as a polar solvent (S2) was added and stirred for 5 minutes. Furthermore, 30 parts by weight of synthetic aluminum silicate (Kyowa Chemical Industry Co., Ltd., Kyoward 700 SEN-S) as adsorbent (I) was added and stirred, and the mixture was stopped after 60 minutes. Synthetic aluminum silicate was removed by vacuum suction filtration in a Kiriyama funnel lined with filter paper and lined with Celite-545RVS (manufactured by Nacalai Tesque) and Standard Super Cell (manufactured by Nacalai Tesque), and the residue on the Kiriyama funnel was mixed with the above mixture. After washing with a solvent, the filtrate was concentrated using an evaporator to remove the mixed solvent, thereby obtaining a polymer (A2-13). The recovery rate of the polymer was 96%, and the viscosity was 41 Pa·s. In the polyoxypropylene polymer (A2-13), the zinc atom content was 0.2 ppm, the cobalt atom content was 0.2 ppm, and the chlorine atom content was 30 ppm.

(Example 12)
To 100 parts by weight of polyoxypropylene polymer (A1-2) obtained by the procedure of Synthesis Example 2-2, n-hexane as a non-polar solvent (S1): acetone as a polar solvent (S2) = 3: 1 (weight ratio) of 200 parts by weight of a mixed solvent was added and stirred. Furthermore, 30 parts by weight of synthetic aluminum silicate (Kyowa Chemical Industry Co., Ltd., Kyoward 700 SEN-S) as adsorbent (I) was added and stirred, and the mixture was stopped after 60 minutes. Aluminum silicate was removed by vacuum suction filtration in a Kiriyama funnel lined with filter paper and lined with Celite-545RVS (manufactured by Nacalai Tesque) and Standard Super Cell (manufactured by Nacalai Tesque), and the residue on the Kiriyama funnel was mixed with the above mixture. After washing with a solvent, the filtrate was concentrated using an evaporator to remove the mixed solvent, thereby obtaining a polymer (A2-14). The recovery rate of the polymer was 97%, and the viscosity was 40 Pa·s. In the polyoxypropylene polymer (A2-14), the zinc atom content was less than 0.1 ppm, the cobalt atom content was 0.1 ppm, and the chlorine atom content was 30 ppm.

(Comparative example 3)
Polymer (A2-15) was obtained by following the same procedure as in Example 12, except that 200 parts by weight of n-hexane was used alone instead of 200 parts by weight of the mixed solvent of n-hexane and acetone. . The recovery rate of the polymer was 91%, and the viscosity was 36 Pa·s. In the polyoxypropylene polymer (A2-15), the zinc atom content was less than 0.1 ppm, the cobalt atom content was less than 0.1 ppm, and the chlorine atom content was 20 ppm.
The results of Examples 11 and 12 and Comparative Example 3 are summarized and shown in Table 3.

From the results shown in Table 3, it is clear that when the non-polar solvent (S1) and the polar solvent (S2) are individually added to the organic polymer (A1) (Example 11), when the non-polar solvent (S1) and the polar solvent ( In both cases where the mixed solvent (S) pre-mixed with S2) was added to the organic polymer (A1) (Example 12), compared to the case where only the non-polar solvent (S1) was added (Comparative Example 3), It can be seen that a high recovery rate was exhibited, a decrease in polymer viscosity during the purification process could be suppressed, and impurities containing halogen atoms were similarly sufficiently removed.

(Examples 13 and 14)
Except for using a silica/magnesia-based preparation (Mizuka Life F-1G, manufactured by Mizusawa Chemical Industry Co., Ltd.) or a styrene-based ion exchange resin (manufactured by Organo, Amberlyst 15DRY) in place of synthetic aluminum silicate as the adsorbent (I). Polymers (A2-15) and (A2-16) were obtained through the same procedure as in Example 4. The adsorbent (I) used and the results such as recovery rate are shown in Table 4.

(Comparative example 4)
Polymer (A2-17) was obtained by following the same procedure as in Example 4 except that adsorbent (I) was not used. The results such as recovery rate are shown in Table 4.

From the results shown in Table 4, it can be seen that halogen atoms are sufficiently removed when using any adsorbent, a high recovery rate is exhibited, and the decrease in polymer viscosity during the purification process is suppressed. . Furthermore, as the adsorbent (I), a comparison between Example 14 and other examples shows that an inorganic adsorbent is preferable from the viewpoint of removing zinc and cobalt, and a comparison between Example 13 and Example 4 shows that an inorganic adsorbent is preferable. It can be seen that among the agents, synthetic aluminum silicate is particularly preferable from the viewpoint of recovery rate.

Claims (13)

A method for producing an organic polymer (A2), the method comprising obtaining an organic polymer (A2) from an organic polymer (A1) containing halogen atoms as an impurity through a purification step,
The purification step is
Adding a non-polar solvent (S1), a polar solvent (S2), and an adsorbent (I) to the organic polymer (A1) to obtain a mixed solution (M1),
A step of removing the adsorbent (I) from the mixed solution (M1) to obtain a mixed solution (M2), and a step of removing the non-polar solvent (S1) and the polar solvent (S2) from the mixed solution (M2) to obtain an organic polymer. (A2),
The weight ratio of the non-polar solvent (S1) and the polar solvent (S2) is (S1):(S2)=100:1 to 1:1,
A method for producing an organic polymer (A2), wherein the total amount of halogen atoms contained in the organic polymer (A2) is less than the total amount of halogen atoms contained in the organic polymer (A1). The manufacturing method according to claim 1, wherein the organic polymers (A1) and (A2) are polyoxyalkylene polymers. The manufacturing method according to claim 1 or 2, wherein the organic polymers (A1) and (A2) have an unsaturated group. The manufacturing method according to claim 1 or 2, wherein the total amount of halogen atoms contained in the organic polymer (A2) is 150 ppm or less. The manufacturing method according to claim 1 or 2, wherein the total amount of halogen atoms contained in the organic polymer (A1) exceeds 1,000 ppm. After reacting an alkali metal salt with a hydroxyl group-terminated polyoxyalkylene polymer, an unsaturated group-containing organic halide is reacted to produce a polyoxyalkylene polymer having an unsaturated group as an organic polymer (A1). The manufacturing method according to claim 2, comprising the step of obtaining. The manufacturing method according to claim 1 or 2, wherein the cobalt atomic weight contained in the organic polymer (A2) is 1 ppm or less. The manufacturing method according to claim 1 or 2, wherein the zinc atomic weight contained in the organic polymer (A2) is 1 ppm or less. The manufacturing method according to claim 1 or 2, wherein the adsorbent (I) is an inorganic adsorbent containing magnesium, aluminum, and/or silicon. Claim 1 or 2, wherein the adsorbent (I) is at least one selected from the group consisting of synthetic aluminum silicate, synthetic alumina magnesia, synthetic hydrotalcite, synthetic magnesium silicate, and silica-magnesia-based preparations. manufacturing method. The non-polar solvent (S1) is an aliphatic or aromatic hydrocarbon solvent and has a boiling point at 1 atm of 150°C or less,
The manufacturing method according to claim 1 or 2, wherein the polar solvent (S2) is an aprotic polar solvent that does not contain a hetero element other than oxygen and has a boiling point of 150° C. or lower at 1 atm. The manufacturing method according to claim 1 or 2, wherein the halogen atom contained in the organic polymer (A1) contains a chlorine atom. After producing the organic polymer (A2) by the production method according to claim 3, the unsaturated groups of the obtained organic polymer (A2) are subjected to a hydrosilylation reaction with a reactive silicon group-containing hydrosilane compound. A method for producing a reactive silicon group-containing organic polymer.