JP5918628B2 - Method for producing vinyl polymer - Google Patents

Description

  The present invention relates to a method for producing a vinyl polymer and a purification method for removing halogen and metal complexes.

  A living polymerization method is generally known as a precision synthesis method for vinyl polymers. In the living polymerization, not only the molecular weight and molecular weight distribution can be controlled, but also a polymer having a clear terminal structure can be obtained. Therefore, living polymerization can be cited as one effective method for introducing a functional group to the polymer terminal. Recently, also in radical polymerization, a polymerization system capable of living polymerization has been found, and research on living radical polymerization has been actively conducted. By utilizing living radical polymerization, a vinyl polymer having a narrow molecular weight distribution can be obtained. As an example of living radical polymerization, there is a polymerization system using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a group 8 element, group 9, group 10, or group 11 element as a central metal as a catalyst. Can be mentioned.

  However, since a halogen or a transition metal complex as a polymerization catalyst remains in a vinyl polymer produced by living radical polymerization, the coloration and physical properties of the polymer are affected. For example, when a vinyl polymer having a silyl group is synthesized by a hydrosilylation reaction between a vinyl polymer having an alkenyl group at the terminal and a compound having a hydrylsilyl group, which is produced using a living radical polymerization method, Since the remaining catalyst or the like acts as a catalyst poison for the hydrosilylation reaction, if a large amount of these remains, the hydrosilylation reaction is inhibited, and a problem arises that a large amount of expensive hydrosilylation catalyst is required. Therefore, in practice, after the polymerization reaction is carried out, it is necessary to remove halogen and residual catalyst from the polymer.

  Examples of the dehalogenation method include Patent Document 1, Patent Document 2, and Patent Document 3, which include a method of dehalogenating by heating a halogen-containing vinyl polymer. Patent Document 4 describes a method of dehalogenating by treating a halogen-containing vinyl polymer with an oxyanion compound. However, in the methods of Patent Document 1, Patent Document 2, and Patent Document 3, an additive such as an adsorbent, an oxygen radical scavenger, or a carbon radical scavenger at the time of dehalogenation is necessary, or dehalogenation. Occasionally, it is necessary to replace the solvent from a polar solvent to a low polarity solvent, which raises problems of cost increase and productivity reduction. In the method of Patent Document 4, since an oxyanion compound is necessary, it is necessary to remove the oxyanion compound in addition to the halogen and the remaining catalyst, which increases the purification load. Patent Document 5 also reports a method of extracting and removing halogen and residual catalyst in water. However, the method disclosed in Patent Document 5 has many operation steps, and the operation in the dehalogenation step is also described. Since the time is long, productivity and coloring of the polymer are problems.

JP 2005-015577 A JP 2003-327620 A WO2006 / 093283 JP 2000-344831 A JP 2011-231235 A

  The present invention provides a method for producing a vinyl polymer that can economically and efficiently remove halogens and metal complexes in the vinyl polymer.

  The present inventors have found that halogens and metal complexes in vinyl polymers can be efficiently removed by dissolving a vinyl polymer having a halogen group obtained by living radical polymerization in a polar solvent and heating. The present invention has been completed.

  That is, the present invention relates to a method for producing a vinyl polymer (b), which is dehalogenated by heating a vinyl polymer (a) having a halogen group obtained by living radical polymerization, The present invention relates to a method for producing a vinyl polymer, which comprises heating a vinyl polymer (A) having a hydrogen atom in a polar solvent.

  The polar solvent is preferably an alcohol, and more preferably an alcohol having 6 or less carbon atoms.

  The content of the vinyl polymer (a) having a halogen group dissolved in the polar solvent in the solution is preferably 1 wt% or more and 90 wt% or less.

  The heating temperature of the vinyl polymer (a) having a halogen group is preferably 100 ° C. or higher and 250 ° C. or lower.

  It is preferable that the vinyl polymer (A) having a halogen group has at least one alkenyl group in the molecule.

  The alkenyl group is preferably present at the end of the molecular chain of the vinyl polymer (a) having a halogen group.

  After heating the vinyl polymer (a) having a halogen group in a polar solvent, the halogen compound is removed by bringing the mixed solution of the obtained vinyl polymer (b) and the halogen compound into contact with an adsorbent or water. It is preferable to do.

  The adsorbent is preferably activated carbon or an inorganic adsorbent.

  The water is preferably pure water or water containing a salt.

  It is preferable that the salt contained in water is sodium sulfate.

  The central metal of the transition metal complex which is a polymerization catalyst for living radical polymerization is preferably an element of Group 8, 9, 10, or 11 of the periodic table, and more preferably iron, nickel, ruthenium or copper. Preferably, it is copper.

  A crosslinkable silyl group obtained by reacting a vinyl polymer having at least one alkenyl group in the molecule obtained by the production method described above with a silane compound having both a crosslinkable silyl group and a hydrosilyl group, The present invention relates to a method for producing a vinyl polymer.

  The present invention relates to a hydrosilylation-reactive composition containing a vinyl polymer having at least one alkenyl group in the molecule and a silane compound having a hydrosilyl group, obtained by the production method described above.

  The present invention relates to a method for removing halogen from a vinyl polymer having a halogen group which undergoes a step of heating a vinyl polymer (a) having a halogen group produced by living radical polymerization in a polar solvent.

  Mixing a vinyl polymer (b) and a halogen compound obtained by heating a vinyl polymer (a) containing a polymerization catalyst residue and having a halogenated group produced by living radical polymerization in a polar solvent. The present invention relates to a purification method in which a halogen compound and a polymerization catalyst are simultaneously removed by bringing a solution into contact with an adsorbent or water.

  According to the method for producing a vinyl polymer of the present invention, it is possible to easily obtain a vinyl polymer for a hydrosilylation-reactive composition in which the content of the metal complex and halogen used for polymerization is significantly reduced. Compared with dehalogenation in, it is possible to simplify the process, reduce the coloration of the polymer, and shorten the time required for dehalogenation. As a result, it is possible to provide a production process advantageous in terms of equipment cost while improving productivity, and its industrial value is very large.

  The present invention relates to a method for producing a vinyl polymer (b) in which dehalogenation is carried out by heating a vinyl polymer (a) having a halogen group obtained by living radical polymerization. It is a method for producing a vinyl polymer, characterized in that the vinyl polymer (i) having the above is heated in a polar solvent.

<< Living radical polymerization >>
First, living radical polymerization will be described in detail. Although it does not specifically limit as living radical polymerization, For example, the method of superposing | polymerizing a vinyl-type monomer using a transition metal complex as a catalyst is mentioned, Atom transfer radical polymerization: ATRP (J. Am. Chem. Soc. 1995, 117, 5614, Macromolecules. 1995, 28, 1721) and Single Electron Transfer Polymerization: SET-LRP (J. Am. Chem. Soc. 2006, 128, 14156, JP Chem Chem 2007, 45). Two interpretations are considered.

  In ATRP, for example, when a copper complex is used as the transition metal complex, the monovalent copper complex pulls out the halogen at the end of the polymer to generate radicals to become a divalent copper complex. The divalent copper complex returns a halogen to the radical at the polymerization end to become a monovalent copper complex. Living radical polymerization consisting of these equilibrium is ATRP.

  On the other hand, when a copper complex is used as the transition metal complex, SET-LRP becomes a divalent copper complex by generating a radical by extracting a halogen at a polymer terminal from a zero-valent metal copper or copper complex. The divalent copper complex returns a halogen to the radical at the polymerization terminal to become a zero-valent copper complex. The monovalent copper complex is disproportionated to become zero-valent and divalent copper complexes. Living radical polymerization consisting of these equilibrium is SET-LRP.

  In addition, by reducing the number of highly oxidized transition metal complexes that cause polymerization delay and termination using a reducing agent, the polymerization reaction can be rapidly advanced to a high reaction rate even under low catalyst conditions with few transition metal complexes. Activators Regenerated by Electron Transfer: ARGET (Macromolecules. 2006, 39, 39) has been reported as an improved formulation of ATRP.

  As the living radical polymerization of the present invention, living radical polymerization using a transition metal or a transition metal compound and a ligand as a catalyst, such as the above-mentioned ATRP, SET-LRP, ARGET and the like is preferable.

  The living radical polymerization using a transition metal or a transition metal compound and a ligand is described below.

<Polymerization catalyst>
The polymerization catalyst is preferably a transition metal complex in which the central metal is a Group 8, 9, 10, or 11 element of the periodic table, and the central metal is iron, nickel, ruthenium or copper. More preferably, it is copper. As copper, a copper complex composed of metallic copper or a copper compound and a ligand is used. In the present invention, it is preferable to use a polydentate amine (A) for this ligand.

(Copper metal or copper compound)
Metallic copper is a simple copper substance such as powdered copper or copper foil.

  Examples of the copper compound include chlorides, bromides, iodides, cyanides, oxides, hydroxides, acetates, sulfates, and nitrates, but are not limited thereto.

  The copper atom can have a valence of 0, 1, or 2 depending on the electronic state, but the valence is not limited.

  The weight of the copper atom is preferably 5 to 4000 ppm with respect to the total charged weight of the vinyl-based monomer. If the amount of copper can be reduced, it can be easily removed, and the polydentate amine ( Since the amount of A) is also reduced, 5 to 100 ppm is more preferable, 5 to 50 ppm is more preferable, and 5 to 30 ppm is particularly preferable. However, if it is less than 5 ppm, it is not preferable because it is necessary to proceed the polymerization over a very long time in order to obtain a polymer having a narrow molecular weight distribution.

  Since metallic copper and a copper compound are solid, it is difficult to charge them into the reaction system. Therefore, it is preferable to mix with a solvent and a polydentate amine (A) in advance and charge in a dissolved solution state. In this respect, monovalent and divalent copper are more preferable than zero-valent copper, and divalent copper is more preferable than monovalent copper because it is easier to dissolve in various solvents.

(Multidentate amine (A))
Although the polydentate amine used as a ligand is illustrated below, it is not restricted to these.

Bidentate polydentate amines: 2,2-bipyridine, 4,4′-di- (5-nonyl) -2,2′-bipyridine, N- (n-propyl) pyridylmethanimine, N- (n -Octyl) pyridylmethanimine Tridentate polydentate amines: N, N, N ', N ", N" -pentamethyldiethylenetriamine, N-propyl-N, N-di (2-pyridylmethyl) amine Tetradentate polydentate amine: hexamethyltris (2-aminoethyl) amine, N, N-bis (2-dimethylaminoethyl) -N, N′-dimethylethylenediamine, 2,5,9,12-tetramethyl -2,5,9,12-tetraazatetradecane, 2,6,9,13-tetramethyl-2,6,9,13-tetraazatetradecane, 4,11-dimethyl-1,4,8,11- Tetraazabicyclohexadecane, N ', N ″ -dimethyl-N ′, N ″ -bis ((pyridin-2-yl) methyl) ethane-1,2-diamine, tris [(2-pyridyl) methyl] amine, 2,5,8 , 12-tetramethyl-2,5,8,12-tetraazatetradecane pentadentate polydentate amine: N, N, N ′, N ″, N ′ ″, N ″ ″, N ′ '''-Heptamethyltetraethylenetetramine Hexadentate polydentate amine: N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine Polyamine: Polyethyleneimine

  However, in order to obtain a polymer having a narrow molecular weight distribution by allowing the polymerization to proceed at a sufficient reaction rate under low concentration catalyst conditions where the total weight of transition metal atoms is 30 ppm or less with respect to the total weight of the vinyl monomer charged. Is preferably a polydentate amine (A) represented by general formula (1) or general formula (4). When other polydentate amines are polymerized over a long period of time, it is possible to obtain a polymer having a narrow molecular weight distribution, but when the polymerization is advanced in a short time, the molecular weight distribution of the polymer is widened, which is not preferable.

(In the formula, R ¹ , R ² and R ³ each independently represent General Formula (2) or General Formula (3)).

(In the formula, R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

(In the formula, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

(In the formula, R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ^17. Each independently represents general formula (2) or general formula (3), and n represents an integer of 0 or more.)

  When other polydentate amines are polymerized over a long period of time, it is possible to obtain a polymer having a narrow molecular weight distribution, but when the polymerization is advanced in a short time, the molecular weight distribution of the polymer is widened, which is not preferable.

  Among the many polydentate amines, the specific polydentate amine (A) represented by the general formula (1) and the general formula (4) is difficult to obtain industrially, so that the amount used is limited. That is, the amount of the polydentate amine (A) used is preferably 7 mmol% or less, more preferably 4 mmol% or less, still more preferably 2 mmol% or less, more preferably 1 mmol%, based on the total amount of the vinyl monomer. The following are particularly preferred: Moreover, 150 mol% or less is preferable with respect to the total amount of copper atoms, 120 mol% or less is more preferable, 110 mol% or less is more preferable, and 100 mol% or less is especially preferable.

<Base (B)>
In the living radical polymerization of the present invention, a base (B) may be added in order to neutralize the acid present in the polymerization system or the generated acid and prevent acid accumulation. By adding a base (B), the present inventors ammonium-converts a polydentate amine (A), which is useful for reaction control, to disrupt the structure of the copper complex, resulting in sufficient polymerization. It is speculated that it prevents the achievement of speed, polymerization at high monomer conversion, and obtaining a polymer with a narrow molecular weight distribution. In fact, although it is a system in which a large amount of copper catalyst is present, it has been reported so far that accumulation of acid causes a decrease in polymerization rate (Japanese Patent Laid-Open No. 2007-148507). However, there is no description that the molecular weight distribution is widened, and it can be said that the reaction system is almost different in the above reported example because the amount of copper and polydentate amine are 100 times that of the present invention. In fact, in a system using 100 times as much copper and polydentate amine, it is possible to obtain a polymer having a high monomer conversion rate and a narrow molecular weight distribution in a short time, which is a problem, without using a base. The present invention is strongly conscious of the industrial use of living radical polymerization. In the case of industrialization, various raw materials are used without purification, and the solvent and unreacted monomer are recycled several tens of times. Therefore, there is a very high possibility that an acid is mixed into the polymerization system due to decomposition or the like. In particular, in the case of ATRP, since a halide initiator and copper halide are used, not a little hydrogen halide is mixed in the raw material. When a hydride reducing agent such as ascorbic acid is used as the reducing agent, hydrogen halide is generated with the reduction of the copper complex, so that the combined use of the base (B) is more effective.

  Base (B) fits the Bronsted base definition, a compound that accepts protons, or the Lewis base definition, has an unshared electron pair and can give it a coordination bond Any compound may be used as long as it has a property to be produced, and it is exemplified below but is not limited thereto.

  Monoamine type: Monoamine is a compound having only one site acting as a base as defined above in one molecule, and is exemplified below, but is not limited thereto. Examples include primary amines such as methylamine, aniline and lysine, secondary amines such as dimethylamine and piperidine, tertiary amines such as trimethylamine and triethylamine, aromatics such as pyridine and pyrrole, and ammonia.

  Polyamines: Examples include diamines such as ethylenediamine and tetramethylethylenediamine, triamines such as diethylenetriamine and pentamethyldiethylenetriamine, tetramines such as triethylenetetramine, hexamethyltriethylenetetramine and hexamethylenetetramine, and polyethyleneimine.

  Inorganic base: An inorganic base represents a simple substance or a compound of Groups 1 and 2 of the periodic table, and is exemplified below, but is not limited thereto. A simple group of groups 1 and 2 of the periodic table, such as lithium, sodium, and calcium. Sodium methoxide, potassium ethoxide, methyl lithium, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium bicarbonate, ammonium bicarbonate, trisodium phosphate, disodium hydrogen phosphate, tripotassium phosphate, dihydrogen phosphate Compounds of Groups 1 and 2 of the periodic table such as potassium, sodium acetate, potassium acetate, sodium oxalate, potassium oxalate, phenoxy sodium, phenoxy potassium, sodium ascorbate, and potassium ascorbate. Examples include salts of weak ammonium hydroxide and strong base.

  These may be used alone or in combination.

  The base (B) may be added directly to the reaction system or may be generated in the reaction system.

  Among these, since the polydentate amine (A) is difficult to obtain, a base other than the polydentate amine (A) represented by the general formula (1) or the general formula (4) is preferable for the base (B). Illustrative examples include, but are not limited to, monoamines, inorganic bases and amines represented by general formula (5).

(In the formula, R ²⁴ , R ²⁵ , R ²⁷ and R ²⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ²² , R ²³ , R ²⁶ , R ²⁹ and R ^30. Each independently represents general formula (2) or general formula (3), l represents an integer of 0 or more, and m represents an integer of 0 or more.)

  When the amine represented by the general formula (5) is used as the base (B), if the amount of the polydentate amine (A) is not sufficient relative to the amount of copper atoms, copper and the polydentate amine (A) The purity of the complex consisting of decreases and the molecular weight distribution of the polymer widens. Therefore, when the amine represented by the general formula (5) is used for the base (B), the polydentate amine (A) is preferably used in an amount of 80 to 150 mol% with respect to the transition metal atom present in the system. 90-120 mol% is more preferable, 95-110 mol% is further more preferable, and 100 mol% is especially preferable. On the other hand, when a base (B) other than the general formula (5), specifically, a monoamine and an inorganic base are used, the base-copper complex affects the polymerization control because of its low coordination property. Absent. A polymer with a narrow molecular weight is obtained. Therefore, when a monoamine and an inorganic base are used for the base (B), the amount of the polydentate amine (A) may not be less than the amount of the copper atom.

  Further, when the base (B) is used as the amine represented by the general formula (5), it can be removed by devolatilization or oil-water separation because of its high boiling point or high affinity with the polymer and the organic solvent. It becomes difficult to remove. Therefore, the base (B) is more preferably a monoamine having a lower boiling point than the amine represented by the general formula (5) or a hydrophilic inorganic base.

Since the base (B) is used to protect the polydentate amine (A) from acid, its basicity is preferably the same or stronger than that of the polydentate amine (A). The base dissociation constant (pK _b ) of _B ) is preferably not more than the pK _{b of the} polydentate amine (A).

  The base (B) may be charged all at once before starting the reaction, or may be gradually added during the reaction.

  The order in which the polydentate amine (A) and the base (B) are added to the copper metal or copper compound is not particularly limited, but the metal is used when the base (B) uses an amine represented by the general formula (5). It is preferable to mix polydentate amine (A) and base (B) in this order with respect to copper or a copper compound. If the order is reversed, a polymer having a narrow molecular weight distribution cannot be obtained. This is because the base (B) represented by the general formula (5) forms a complex with copper and lowers the purity of the complex formed from the effective polydentate amine (A) and copper. On the other hand, when a base other than the general formula (5), specifically, a monoamine or an inorganic base is used, it is difficult to form a complex due to its low coordination property, so that a polydentate amine (A) and a base ( The mixing order of B) is not limited.

  Since the effect is reduced by the solubility of the base, when a base that is difficult to dissolve in the polymerization solvent is used, it is preferable that the base be dissolved in a good solvent and added in solution.

  Regarding the amount of the base (B), in order to protect the polydentate amine (A), it is preferable that an excessive amount is added to the polydentate amine.

<Reducing agent (C)>
In living radical polymerization using a copper complex as a catalyst, it has been found that the use of a reducing agent in combination requires an excess ligand, but the activity is improved (ARGET ATRP). This ARGET ATRP is thought to improve its activity by reducing and reducing highly oxidized transition metal complexes that are caused by coupling of radicals during polymerization and causing reaction delay and termination. It is possible to reduce the necessary transition metal catalyst to several tens of ppm to several tens to several hundred ppm. In the present invention, a reducing agent (C) may be added.

Although the reducing agent used by this invention is illustrated below, these reducing agents are not limited.
(Reducing agent that does not generate acid when reducing copper complex)
metal. Specific examples include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium and barium; aluminum; typical metals such as zinc; transition metals such as copper, nickel, ruthenium and iron Etc. These metals may be in the state of an alloy (amalgam) with mercury.

Metal compound. Examples include salts of typical metals or transition metals, salts with typical elements, and complexes in which carbon monoxide, olefins, nitrogen-containing compounds, oxygen-containing compounds, phosphorus-containing compounds, sulfur-containing compounds and the like are coordinated. Specifically, compounds of metal and ammonia / amine, titanium trichloride, titanium alkoxide, chromium chloride, chromium sulfate, chromium acetate, iron chloride, copper chloride, copper bromide, tin chloride, zinc acetate, zinc hydroxide, Carbonyl complexes such as Ni (CO) ₄ and Co ₂ CO ₈ , and olefin complexes such as [Ni (cod) ₂ ], [RuCl ₂ (cod)] and [PtCl ₂ (cod)] (where cod is cyclooctadiene) ), [RhCl (P (C ₆ H ₅ ) ₃ ) ₃ ], [RuCl ₂ (P (C ₆ H ₅ ) ₃ ) ₂ ], [PtCl ₂ (P (C ₆ H ₅ ) ₃ ) ₂ ], etc. And phosphine complexes.

  Organotin compounds. Specific examples include tin octylate, tin 2-ethylhexylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiocarboxylate and the like.

  Phosphorus or phosphorus compound. Specific examples include phosphorus, trimethylphosphine, triethylphosphine, triphenylphosphine, trimethylphosphite, triethylphosphite, triphenylphosphite, hexamethylphosphorustriamide, hexaethylphosphorustriamide, and the like.

Sulfur or sulfur compounds. Specifically, sulfur, Rongalite, hydrosulfite, thiourea dioxide and the like can be mentioned. Rongalite is a formaldehyde derivative of sulfoxylate and is represented by MSO ₂ .CH ₂ O (M represents Na or Zn). Specific examples include sodium formaldehyde sulfoxylate and zinc formaldehyde sulfoxylate. Hydrosulfite is a general term for sodium hyposulfite and formaldehyde derivatives of sodium hyposulfite.

(Reducing agent that generates acid when reducing copper complex (hydride reducing agent))
Metal hydride. Specific examples include sodium hydride; germanium hydride; tungsten hydride; diisobutylaluminum hydride, lithium aluminum hydride, sodium aluminum hydride, sodium triethoxyaluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, etc. And aluminum hydrides such as triphenyltin hydride, tri-n-butyltin hydride, diphenyltin hydride, di-n-butyltin hydride, triethyltin hydride, and trimethyltin hydride. .

  Silicon hydride. Specific examples include trichlorosilane, trimethylsilane, triethylsilane, diphenylsilane, phenylsilane, polymethylhydrosiloxane, and the like.

  Boron hydride. Specifically, borane, diborane, sodium borohydride, sodium trimethoxyborate, sodium borohydride, sodium cyanoborohydride, lithium borohydride, lithium borohydride, lithium triethylborohydride, hydrogen Tri-s-butyl boron hydride, lithium tri-t-butyl boron hydride, calcium borohydride, potassium borohydride, zinc borohydride, tetra-n-butylammonium borohydride and the like.

  Nitrogen hydride. Specific examples include hydrazine and diimide.

  Phosphorus or phosphorus compound. Specific examples include phosphine and diazaphospholene.

  Sulfur or sulfur compounds. Specifically, hydrogen sulfide etc. are mentioned.

  hydrogen.

  An organic compound that exhibits a reducing action. Specific examples include alcohols, aldehydes, phenols, and organic acid compounds. Examples of the alcohol include methanol, ethanol, propanol, and isopropanol. Examples of the aldehyde include formaldehyde, acetaldehyde, benzaldehyde, formic acid and the like. Examples of phenols include phenol, hydroquinone, dibutylhydroxytoluene, tocopherol and the like. Examples of the organic acid compound include citric acid, oxalic acid, ascorbic acid, ascorbate, ascorbate ester and the like.

  Among them, a hydride reducing agent that generates an acid when reducing a copper complex causes a decrease in polymerization rate and a broadening of molecular weight distribution due to deterioration in polymerization control when the base (B) is not used in combination. Is more effective. This is presumed to be because the generated acid causes ammonium chloride of the polydentate amine that forms the transition metal complex and destroys the complex structure.

  The stronger the reducing power of the reducing agent (C), the faster the polymerization can proceed. That is, the example using an amine as a reducing agent (US2009 / 0156771) is not a sufficient reaction rate because the reducing ability is too low. Therefore, a reducing agent having a higher reducing ability than that of an amine, that is, a reducing agent that can easily donate electrons is preferable. Of these, metals, organotin compounds, ascorbic acid, ascorbic acid esters, ascorbate, and hydrazine are preferred because of their strong reducing power.

  In addition, considering the industrialization, the reducing agent (C) must be removed from the polymer after the polymerization, so that the oxide is easily removed by volatilization and removal, such as hydrazine and oxalic acid. Sodium, hydrazine, citric acid, oxalic acid, ascorbic acid, ascorbate, ascorbate and the like are preferable.

  Therefore, ascorbic acid, ascorbate, ascorbate, and hydrazine are more preferable, and ascorbic acid, ascorbate, and ascorbate are particularly preferable.

  These reducing agents (C) may be used alone or in combination of two or more.

  Further, the reducing agent (C) may be added directly to the reaction system or may be generated in the reaction system. The latter includes electrolytic reduction. In electrolytic reduction, it is known that electrons generated at the cathode exhibit a reducing action immediately or once solvated. That is, the reducing agent (C) produced by electrolysis can also be used.

  When the amount of the reducing agent (C) added is too small, it is not preferable because sufficient polymerization activity cannot be expected, and when it is too much, it is not preferable because removal from the obtained polymer becomes difficult. That is, it is preferably 10 to 100,000 ppm, more preferably 10 to 10,000 ppm, still more preferably 10 to 1000 ppm, and particularly preferably 10 to 500 ppm with respect to the total charged amount of the (meth) acrylate monomer.

  Moreover, when the reducing agent (C) is solid at room temperature, it is preferable to add the reducing agent (C) as a solution dissolved in a good solvent because the effect can be further exhibited.

  As can be seen from the mechanism of ARGET ATRP, when an excessive amount of reducing agent (C) is added at one time, the divalent copper complex for controlling radicals is insufficient, and the molecular weight distribution is widened by coupling or the like. Therefore, the reducing agent (C) is preferably added little by little as the polymerization proceeds, and specifically, it is preferably added at 10 to 1000 mol% / Hr with respect to the copper complex, and added at 20 to 700 mol% / Hr. It is more preferable to add at 30 to 500 mol% / Hr.

  The order in which the base (B) and the reducing agent (C) are added to the copper metal or copper compound is not particularly limited, but when a hydride reducing agent is used as the reducing agent (C), the reducing agent (C), the base When mixed with the transition metal atom in the order of (B), the polymerization rate is lowered and the molecular weight distribution of the polymer is widened. Therefore, it is preferable to mix the base (B) and the reducing agent (C) in the order or simultaneously. This is presumably because hydrogen halide is generated when the reducing agent (C) reduces the transition metal atom, and the polydentate amine (A) is ammonium chlorided. On the other hand, when a base other than the hydride reducing agent is used, no acid is generated during the reduction, and the order is not limited. However, “simultaneous” as used herein indicates mixing at approximately the same timing, and is not exact. In particular, when ascorbic acid is used as the reducing agent (C), mixing with the base (B) in advance improves solubility in an organic solvent and improves operability. Therefore, the base (B) and the reducing agent (C ) Are preferably added simultaneously.

  In addition, when a hydride reducing agent is used as the reducing agent (C), the reducing agent (C) is moved by the reducing agent (C) because the added reducing agent (C) generates hydrogen halide when the transition metal atom is reduced. The amount of the base (B) is always 100 mol% or more with respect to the electrons, more preferably 150 mol% or more, more preferably 200 mol% or more, and further preferably 300 mol% or more. However, when the amine represented by the general formula (5) is used for the base (B), it is difficult to remove the base (B) and its acid salt, so that the color of the polymer is remarkably deteriorated. Therefore, it is not preferable to add in a large excess amount. Specifically, it is preferably 2% by weight or less, more preferably 1% by weight or less, and more preferably 0.5% by weight or less based on the total amount of (meth) acrylic monomers. Is more preferable, and 0.1% by weight or less is particularly preferable. However, when a monoamine or an inorganic base is used for the base (B), it can be extracted by vacuum devolatilization or oil-water separation, so there is no limit to using it excessively.

<Vinyl monomer>
The vinyl monomer used in the living radical polymerization of the present invention is a conventionally known monomer used in radical polymerization. For example, (meth) acrylic acid; methyl (meth) acrylate, (meth ) Ethyl acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-tert-butyl, ( (Meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic 2-ethylhexyl acid, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic acid Nyl, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ( (Meth) acrylic acid-2-hydroxypropyl, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, (meth) acrylic acid Ethylene oxide adduct, trifluoromethyl methyl (meth) acrylate, 2-trifluoromethyl ethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate 2-perfluorobutyl ethyl, 2-methacrylic acid (meth) acrylate Fluoroethyl, perfluoromethyl (meth) acrylate, diperfluoromethyl methyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl (meth) acrylate, 2-perfluorohexyl (meth) acrylate (Meth) acrylic acid ester monomers such as ethyl, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate; styrene, vinyltoluene, α-methylstyrene, chlorostyrene, Styrene monomers such as styrenesulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride , Lemonic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearyl Maleimide monomers such as maleimide, phenylmaleimide and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate and vinyl pivalate , Vinyl esters such as vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene, isoprene, etc. And conjugated dienes such as vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These may be used alone or a plurality of these may be copolymerized. Of these, styrene monomers and (meth) acrylic monomers such as (meth) acrylic acid and (meth) acrylic acid ester monomers are preferred from the physical properties of the product. More preferred are (meth) acrylic acid ester monomers, particularly preferred are acrylic acid ester monomers, and further preferred are butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

<Initiator>
The polymerization initiator used for the living radical polymerization of the present invention is preferably an organic halide having a highly reactive carbon-halogen bond. For example, a carbonyl compound having a halogen at the α-position, a compound having a halogen at the benzyl-position, or a halogenated sulfonyl compound is exemplified. Specifically,
_{C 6 H 5 -CH 2 X,} C 6 H 5 -C (H) (X) CH 3, C 6 H 5 -C (X) (CH 3) 2
(However, in the above chemical formula, C ₆ H ₅ is a phenyl group, X is chlorine, bromine, or iodine)
^{R 31 -C (H) (X} ) -CO 2 R 32, R 31 -C (CH 3) (X) -CO 2 R 32, R 31 -C (H) (X) -C (O) R 32 R ³¹ —C (CH ₃ ) (X) —C (O) R ³² ,
(Wherein R ³¹ and R ³² are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine)
R ³¹ —C ₆ H ₄ —SO ₂ X
(Wherein R ³¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine).

  An organic halide having two or more starting points or a sulfonyl halide compound may be used as an initiator.

  It is a feature of living radical polymerization that the desired polymer molecular weight can be set by adjusting the ratio of the monomer and the initiator amount.

<Solvent>
Although it illustrates below about a solvent, when using this living radical polymerization method, it does not specifically limit.

High polar aprotic solvent: dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone, etc. Carbonate solvent: Ethylene carbonate, propylene carbonate, etc. Alcohol solvent: Methanol, Ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, etc. Nitrile solvents: acetonitrile, propionitrile, benzonitrile, etc. Ketone solvents: acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ether solvents: diethyl ether, tetrahydrofuran, etc. Halogenated carbon solvents: methylene chloride, chloroform, etc. Ester solvents: ethyl acetate, butyl acetate, etc. Hydrocarbon solvents: pentane, hexane, Rohekisan, octane, decane, benzene, toluene and the like, and ionic liquids, water and the like.
A supercritical fluid may also be used.

  The said solvent can be used individually or in mixture of 2 or more types.

  Furthermore, the reaction control is that the transition metal or transition metal compound, polydentate amine (A), base (B), reducing agent (C), vinyl monomer and initiator are uniform in the reaction system. From the viewpoint of polymerization reaction rate, ease of preparation, and scale-up risk, it is preferable to select a solvent that dissolves them. For example, when ascorbic acid is used as the reducing agent, its solubility greatly affects its reducing power. Therefore, a solvent capable of dissolving ascorbic acid or a salt or ester thereof, such as methanol, ethanol, propanol, isopropanol, n- Alcohol solvents such as butyl alcohol and tert-butyl alcohol, highly polar aprotic solvents such as dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone, and water Is preferred. It is also useful to improve the solubility of ascorbic acid by mixing them with other solvents.

<< About the vinyl polymer (a) having a halogen group >>
Next, the vinyl polymer (a) having a halogen group in the present invention will be described in detail.

  The vinyl polymer (A) having a halogen group is not particularly limited, but is produced by living radical polymerization of a vinyl monomer using an organic halide as an initiator. Such vinyl monomers are not particularly limited, and those already exemplified can be used. In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in that case, these preferred monomers are preferably contained in a weight ratio of 40% or more. .

  The molecular weight distribution of the vinyl polymer (a) having a halogen group, that is, the ratio of the weight average molecular weight (Mn) to the number average molecular weight (Mw) measured by gel permeation chromatography is 1.1 to 1.8. However, it is preferably 1.1 to 1.7, more preferably 1.1 to 1.5, and still more preferably 1.1 to 1.3. In the GPC measurement of the present invention, chloroform is usually used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

  The number average molecular weight of the vinyl polymer (a) having a halogen group is not particularly limited, but is preferably in the range of 500 to 1,000,000, more preferably in the range of 1000 to 500,000, still more preferably in the range of 3000 to 300000, 5000 to 300,000 is particularly preferred.

  The main chain of the vinyl polymer (a) having a halogen group obtained by the production method of the present invention may be linear or branched.

  The dehalogenation of the present invention may be carried out immediately after the polymerization of the vinyl polymer (a) having a halogen group, but is reactive within the molecule of the vinyl polymer (a) having a halogen group after polymerization. You may carry out after attaching a functional group. When it has a reactive functional group in the molecule, it may be present at either the side chain or the molecular chain terminal, but it is preferably present at the molecular chain terminal. Although it does not specifically limit as a reactive functional group, For example, although an alkenyl group, a hydroxyl group, an amino group, a crosslinkable silyl group, a polymeric carbon-carbon double bond group etc. are mentioned, what has at least 1 alkenyl group is mentioned. preferable.

Furthermore, the method for introducing the functional group is not particularly limited, and various methods are used. For example, the following methods are exemplified.
(1) A method of copolymerizing a vinyl monomer having a functional group with a predetermined vinyl monomer under living radical polymerization conditions,
(2) A method in which an olefin compound having a low radical polymerizability having a functional group is reacted with a terminal halogen group of a vinyl polymer under living radical polymerization conditions,
A reactive functional group can also be converted to another suitable functional group in one or several steps. For example, also in the present invention, a vinyl polymer having at least one alkenyl group is synthesized by converting a reactive functional group such as a hydroxyl group.

  Among them, when hydrosilylation is performed, it is preferable to obtain a vinyl polymer having an alkenyl group at the terminal by the method (2). The method (2) will be described below. A vinyl polymer obtained by living radical polymerization of a vinyl monomer is reacted with a compound having at least two alkenyl groups having low polymerizability (hereinafter referred to as “diene compound”).

At least two alkenyl groups of the diene compound may be the same or different from each other. The alkenyl group is a terminal alkenyl group [CH ₂ ═C (R) —R ′; R is hydrogen or an organic group having 1 to 20 carbon atoms, R ′ is an organic group having 1 to 20 carbon atoms, and R and R ′ May be bonded to each other to have a cyclic structure. Or an internal alkenyl group [R′—C (R) ═C (R) —R ′; R is hydrogen or an organic group having 1 to 20 carbon atoms, R ′ is an organic group having 1 to 20 carbon atoms; Two R (or two R ′) may be the same or different from each other. Any two of the two substituents of two R and two R ′ may be bonded to each other to have a cyclic structure. ], But a terminal alkenyl group is more preferable. R is hydrogen or an organic group having 1 to 20 carbon atoms. Examples of the organic group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 7 carbon atoms. Twenty aralkyl groups are preferred. Among these, as R, hydrogen or a methyl group is particularly preferable.

  Of the alkenyl groups of the diene compound, at least two alkenyl groups may be conjugated.

  Specific examples of the diene compound include isoprene, piperylene, butadiene, myrcene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, and the like. 5-hexadiene, 1,7-octadiene and 1,9-decadiene are preferred.

<< Dehalogenation process >>
Since the vinyl polymer (a) having a halogen group obtained by polymerization contains a halogen that acts as a catalyst poison for the hydrosilylation reaction, the vinyl polymer is used in the case where the hydrosilylation reaction is performed in a subsequent step. It is necessary to separate the halogen from In the present invention, dehalogenation is performed by dissolving a vinyl polymer (a) having a halogen group in a polar solvent and heating. This dehalogenation eliminates the need for purification and solvent replacement prior to dehalogenation and simplifies the process, reduces the coloration of the polymer, shortens the time required for dehalogenation, etc. The effect can also be expected.

  Examples of polar solvents include alcohol solvents such as methanol, ethanol, n-propanol, n-butanol, n-pentanol, and n-hexanol: ketone solvents such as acetone, acetylacetone, methyl ethyl ketone, and methyl isobutyl ketone: acetonitrile, pro Nitrile solvents such as pionitrile, benzonitrile; amide solvents such as formamide, N, N-dimethylformamide, N, N-dimethylacetamide; methyl chloride, 1,2-dichloroethane, acetic acid, nitrobenzene, phenol and the like . These may be used alone or in combination of two or more. Among these, a preferable solvent is an alcohol solvent. An alcohol having 6 or less carbon atoms is preferable from the operation surface, and more preferably n-butanol.

  The amount of the solvent used is not particularly limited. Usually, it is preferable to add a solvent so that the vinyl polymer (a) having a halogen group is in the range of 1 wt% or more and 90 wt% or less. B) is preferably in the range of 30 wt% to 90 wt%.

  The processing temperature of the purification operation of the present invention is not particularly limited. Higher temperatures are preferable for shortening the treatment time, but if the temperature is too high, the vinyl polymer will decompose, so the vinyl polymer will be heated in a temperature range where the vinyl polymer will not significantly decompose. It is preferable to process. Specifically, it is preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 250 ° C. or lower, more preferably 140 ° C. or higher and 250 ° C. or lower, and particularly preferably 170 ° C. or higher and 240 ° C. or lower in terms of economy and operation.

  Further, the heat treatment is preferably performed under pressure.

  The dehalogenation time may be any number of hours as long as it is 1 hour or longer, but is preferably 1 hour or longer and 15 hours or shorter from the viewpoint of production.

<< Purification process >>
As a method for removing the halogen compound and the metal complex from the mixture containing the vinyl polymer (b), the halogen compound and the metal complex obtained by the dehalogenation step, for example, the following two methods are preferable.
(A) Adsorption purification method: Halogen and a metal complex are adsorbed on an adsorbent to remove impurities.
(B) Water purification method: Extracting halogen and metal complex into water to remove impurities.
Hereinafter, (a) and (b) will be described in detail.

(A) Adsorption purification method The adsorption purification method is a method in which a halogen compound and a metal complex are removed by an adsorbent from a mixture containing a vinyl polymer (b), a halogen compound and a metal complex, obtained by a dehalogenation step. It is.

  In the present invention, an inorganic adsorbent such as synthetic hydrotalcite, aluminum silicate, magnesium oxide or activated carbon is preferably used as the adsorbent.

  Representative inorganic adsorbents include those containing aluminum, magnesium, silicon or the like as a main component or a combination thereof. For example, silicon dioxide; magnesium oxide; silica gel; silica-alumina, aluminum silicate; activated alumina; clay-based adsorbent such as acid clay and activated clay; zeolite-based adsorbent collectively called hydrous aluminosilicate mineral group such as sodium aluminum silicate A dosonite compound; a hydrotalcite compound. Among these, aluminum silicate and hydrotalcite compounds are particularly preferable.

  Aluminum silicate is obtained by replacing a part of silicon of silicate with aluminum, and pumice, fly ash, kaolin, bentonite, activated clay, diatomaceous earth and the like are known. Among these, synthetic aluminum silicate has a large specific surface area and high adsorption capacity. Examples of the synthetic aluminum silicate include, but are not limited to, the Kyoward 700 series (manufactured by Kyowa Chemical).

Hydrotalcite compounds are divalent metals (Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ^2+, etc.) and trivalent metals (Al ^{3 +} , Fe ³⁺ , Cr ³⁺ , Co ³⁺ , In ^3+, etc.) or some of the hydroxyl groups of the hydroxide are halogen ions, NO ₃ ⁻ , CO ₃ ²⁻ , SO ₄ ^{2 -} , Fe (CN) ₆ ³⁻ , CH ₃ CO ₂ ⁻ , exchanged with anions such as oxalate ion and salicylate ion. Of these, hydrotalcite in which the divalent metal is Mg ²⁺ and the trivalent metal is Al ³⁺ and a part of the hydroxyl group is replaced with CO ₃ ^2- is preferable. Series and KYOWARD 1000 series (both manufactured by Kyowa Chemical Co., Ltd.) can be mentioned, but are not limited thereto. An adsorbent obtained by firing the hydrotalcite is also preferably used. Among them, MgO—AlO ₃ solid solution obtained by firing hydrotalcites in which the divalent metal is Mg ²⁺ and the trivalent metal is Al ³⁺ is preferable, for example, Kyoward 2000 (Kyowa Chemical Co., Ltd.). ))), But is not limited thereto. In the present invention, the fired products of hydrotalcites are also classified as hydrotalcites. The adsorbents exemplified above may be used alone or in combination. Moreover, although the usage-amount of adsorption agent is 0.1-10 weight part normally with respect to 100 weight part of polymers, it is preferable that it is 0.1-5 weight part from economical efficiency and an operation surface.

  Most of the activated carbon is carbonaceous charcoal. For example, wood, lignite, peat, etc. are used as an activator and treated with zinc chloride or phosphoric acid to dry distillation, or charcoal or the like is activated with steam to form a powder. Any shape or granular shape can be used, but is not limited thereto.

  The purification step may be performed after the dehalogenation step, and another treatment may be performed between the dehalogenation step and the purification step, but the purification step may be performed subsequent to the dehalogenation step. preferable. The purification step is preferably performed by separating and removing by a solid-liquid separation method existing in the vinyl polymer. The solid-liquid separation method is not particularly limited, and a general separation method such as a filtration method or a sedimentation method is used.

  Examples of the filtration method include a vacuum filtration method using Nutsche and the like, and a pressure filtration method such as a filter press method. When the amount of insoluble components is small and filterability is good, simple filtration with a cartridge filter, bag filter, etc., sand filtration, etc. are convenient.

  Examples of the sedimentation method include a stationary separation method, a decanter, a centrifugal sedimentation method using a separator-type centrifugal sedimentator, and the like. Examples of a method combining filtration and sedimentation include a centrifugal filtration method using a basket type centrifugal filter, a sedimentation filtration method using a horizontal plate type filter, and the like. In the filtration method, a filter aid may be used depending on the particle system and amount of insoluble components. Although it does not specifically limit as a filter aid, Common things, such as diatomaceous earth, may be used.

  If the vinyl polymer has a high viscosity and the solid-liquid separation operability is poor, it may be diluted with a solvent. The diluent solvent is not particularly limited. In order to adjust the polarity of the solvent, two or more solvents may be mixed and used. Solid-liquid separation treatment may be performed by heating a vinyl polymer or a mixture thereof.

  Various embodiments are possible for the solid-liquid contact between the inorganic adsorbent and the vinyl polymer or polymer solution, but in addition to the batch method in which stirring and mixing and solid-liquid separation are performed by batch operation, the adsorbent is put in a container. A fixed bed system in which the polymer solution is filled and liquid is passed, a moving bed system in which the liquid is passed through the moving bed of the adsorbent, a fluidized bed system in which the adsorbent is fluidized with a liquid, and the like are used. Furthermore, in addition to mixing and dispersing by stirring, various operations for improving the dispersion efficiency such as shaking of the container and use of ultrasonic waves can be incorporated as necessary. After contacting the polymer or polymer solution with the adsorbent, the adsorbent is removed by a method such as filtration, centrifugation, sedimentation separation, etc., and if necessary, diluted and washed with water. Get coalesced.

(B) Water purification method The water purification method is a method in which a halogen compound and a metal complex are removed with water from a mixture containing a vinyl polymer (b), a halogen compound and a metal complex, obtained by a dehalogenation step. is there.

  When the water purification method is used, it is preferable to use an aqueous solution containing a water-insoluble solvent and a salt component.

  Examples of water-insoluble solvents include saturated hydrocarbon solvents such as n-hexane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and anisole; methylene chloride, carbon tetrachloride, chloroform, and the like. Halogenated hydrocarbon solvents; ester solvents such as ethyl acetate, butyl acetate, and isoamyl acetate; alcohol solvents such as methanol, ethanol, n-propanol, n-butanol, n-pentanol, and n-hexanol. . These may be used alone or in combination of two or more. Among these, a preferable solvent is an alcohol solvent. Of these, alcohols having 4 or more carbon atoms are preferable, and n-butanol is more preferable.

  The amount of the solvent used is not particularly limited. Usually, it is preferable to add a solvent so that the vinyl polymer is in the range of 5 wt% to 90 wt%, and the vinyl polymer is preferably in the range of 10 to 50 wt% from the viewpoint of economy and operation.

  There is no selection condition for water to be used other than considering prevention of contamination of the polymer. Water through a filter of 50 μm or less is preferable, and pure water treated with an ion exchange resin is more preferable.

  In the present invention, in order to remove the metal complex in the polymer solution, it is preferable to mix a salt component with water. Examples of salt components that dissolve in water are sodium chloride, sodium sulfate, sodium acetate, sodium acrylate, sodium phosphate, sodium citrate, sodium tartrate, sodium benzoate, sodium sorbate, sodium phthalate, sodium acrylate and Sodium methacrylate. These sodium salts may be potassium salts or ammonium salts. Among these, sodium sulfate and sodium chloride are preferable, and sodium sulfate is more preferable because it is easily available and is a neutral salt and has a low load in wastewater treatment.

  Although the content of the salt component added to water is not particularly limited, it is necessary to completely dissolve the salt component. Therefore, it is preferable to adjust the addition amount corresponding to the solubility of the salt component. In order to promote the separability after mixing the mixed aqueous solution of the salt component and water and the polymer solution, it is preferable to add the salt component in an amount of 0.1 to 15 wt%, thereby reducing the wastewater treatment load. Therefore, the content is preferably 0.1 to 10 wt%.

  The amount of water used when bringing the aqueous solution in which the acid is dissolved into contact with the polymer solution is not particularly limited, but water is preferably in the range of 10 to 2000 parts by weight with respect to 100 parts by weight of the vinyl polymer. More preferably, it is 100 to 300 parts by weight from the viewpoint of economy and operation.

  Various embodiments are possible for the liquid-liquid contact between the aqueous solution in which the salt is dissolved and the polymer solution. However, in addition to the batch system in which stirring and mixing and liquid-liquid separation are performed in a batch operation, water and the polymer are counterflowed. An extraction tower system or a spray tower system for passing through the container can also be used. Furthermore, in addition to mixing and dispersing by stirring, various operations for improving the dispersion efficiency such as shaking of the container and use of ultrasonic waves can be incorporated as necessary. Examples of methods that do not require a driving force for mixing the two phases include methods called flow mixers such as spray towers, packed towers, baffle towers, perforated plate extraction towers, orifice towers, and static mixers. Examples of the method that requires a driving force include a pulsating packed tower, a pulsating perforated plate tower, a vibrating plate tower, a centrifugal extraction device such as a Podovirniak extractor and a Lewesta extractor. There are various types of apparatuses using a stirring system as a driving force, such as a mixer-settler extraction apparatus, a Seibel tower, a rotating disk extraction tower, an Old shoe-Rushton tower, and an ARD tower.

  The temperature at which the aqueous solution in which water or a salt component is dissolved and the polymer solution are brought into contact with each other is not particularly limited, and may generally be 0 to 200 ° C. Preferably it is 20-100 degreeC, More preferably, it is 30-80 degreeC. A higher temperature is preferable because the viscosity of the polymer solution decreases and the number of dispersed oil droplets decreases, so that the contact area with water increases and the extraction of the metal catalyst is promoted. However, if it is too high, the quality of the vinyl polymer may be deteriorated.

  The time for performing the contact is not particularly limited as long as the object of the present invention can be achieved. There are also combinations in which purification is completed by mixing and stirring for about 1 minute by limiting the types of water-insoluble solvents, acids, and inorganic salts that dissolve the polymer. Other combinations can be usually performed in about 5 to 300 minutes.

  For oil-water separation between an aqueous solution in which water, acid, or salt components are dissolved, and a polymer solution, centrifugal separation or static separation utilizing a specific gravity difference, or electrostatic oil purification utilizing a difference in electrical properties is used. I can do it. The time for performing the oil / water separation is not particularly limited as long as the object of the present invention can be achieved. Usually, it can be performed in about 1 to 300 minutes.

  The number of times of contact and oil-water separation between the aqueous solution in which the acid component is dissolved and the polymer solution is not particularly limited, and it may be performed once or several times.

  By the above purification treatment, the content of the transition metal component in the polymer of the present invention can be reduced to 1 mg or less with respect to 1 kg of the polymer.

  In the above, the method according to the present invention can be widely applied in the production of vinyl polymers by living radical polymerization.

<< Hydrosilylation Reaction >>
The vinyl polymer having at least one alkenyl group in the molecule subjected to the above purification treatment can be used for the hydrosilylation reaction, and a rubber-like cured product is obtained by crosslinking.

Examples of a method for obtaining a rubber-like cured product using a hydrosilylation reaction include the following two points.
(I) A hydrosilylation reactive composition containing a vinyl polymer having at least one alkenyl group in the molecule and a silane compound having a hydrosilyl group is prepared, and a cured product is obtained by performing a hydrosilylation reaction. Method.
(II) A vinyl polymer having a crosslinkable silyl group by a hydrosilylation reaction of a vinyl polymer having at least one alkenyl group in the molecule and a silane compound having both a crosslinkable silyl group and a hydrosilyl group. A method for producing a cured product by producing a composition containing a vinyl polymer having a crosslinkable silyl group produced and crosslinking the crosslinkable silyl groups.

<Method (I)>
The hydrosilyl group-containing compound used in the method (I) preferably has at least 1.1 hydrosilyl groups in the molecule in order to give a cured product by a hydrosilylation reaction. Although it does not specifically limit as a compound which has at least 1.1 hydrosilyl group in such a molecule, For example, linear polysiloxane represented by General formula (22) or (23);
_{^{R 51 3 SiO- [Si (R}} 51) 2 O] a - [Si (H) (R 52) O] b - [Si (R 52) (R 53) O] c -SiR 51 3 (22)
HR ⁵¹ ₂ SiO— [Si (R ⁵¹ ) ₂ O] _a — [Si (H) (R ⁵² ) O] _b — [Si (R ⁵² ) (R ⁵³ ) O] _c —SiR ⁵¹ ₂ H (23)
(In the formula, R ⁵¹ and R ⁵² represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ⁵³ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group. A represents 0 ≦ a ≦ 100, b Represents an integer satisfying 2 ≦ b ≦ 100 and c satisfying 0 ≦ c ≦ 100.)
A cyclic siloxane represented by the general formula (24);

(In the formula, R ⁵⁴ and R ⁵⁵ represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ⁵⁶ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group. D represents 0 ≦ d ≦ 8, e Represents an integer of 2 ≦ e ≦ 10, f represents an integer of 0 ≦ f ≦ 8, and satisfies 3 ≦ d + e + f ≦ 10.)
Etc. can be used.

These may be used alone or in combination of two or more. Among these siloxanes, from the viewpoint of compatibility with (meth) acrylic polymers, chain siloxanes represented by the following general formulas (25) and (26) having a phenyl group, and general formulas (27), ( The cyclic siloxane represented by 28) is preferred.
_{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (C 6 H 5) 2 O] h -Si (CH 3) 3 (25)
_{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (CH 3) {CH 2 C (H) (R 56) C 6 H 5} O] h -Si (CH 3 ₃ (26)
(In the formula, R ⁵⁶ represents hydrogen or a methyl group. G represents an integer of 2 ≦ g ≦ 100 and h represents an integer of 0 ≦ h ≦ 100. C ₆ H ₅ represents a phenyl group.)

(In the formula, R ⁵⁷ represents hydrogen or a methyl group. I represents an integer satisfying 2 ≦ i ≦ 10 and j satisfying 0 ≦ j ≦ 8 and 3 ≦ i + j ≦ 10.)

  As a compound having at least 1.1 hydrosilyl groups, a hydrosilyl group-containing compound represented by the general formulas (22) to (28) is further used for a low molecular compound having two or more alkenyl groups in the molecule. A compound obtained by addition reaction such that a part of the hydrosilyl group remains after the reaction can also be used. Various compounds can be used as the compound having two or more alkenyl groups in the molecule. For example, hydrocarbon compounds such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, O, O Ether compounds such as' -diallyl bisphenol A, 3,3'-diallyl bisphenol A, ester compounds such as diallyl phthalate, diallyl isophthalate, triallyl trimellitate, tetraallyl pyromellitate, carbonates such as diethylene glycol diallyl carbonate System compounds.

  The compound can be obtained by slowly dropping the above-mentioned alkenyl group-containing compound in the presence of a hydrosilylation catalyst with respect to the excessive amount of the hydrosilyl group-containing compound represented by the general formulas (22) to (28). it can. Of these compounds, the following are preferred in view of the availability of raw materials, the ease of removal of excessive siloxane, and the compatibility with vinyl polymers.

  The vinyl polymer having at least one alkenyl group in the molecule and the hydrosilyl group-containing compound can be mixed at an arbitrary ratio, but from the viewpoint of curability, the molar ratio of the alkenyl group to the hydrosilyl group is 5 to 0. Is preferably in the range of .2 and more preferably in the range of 2.5 to 0.4. When the molar ratio is 5 or more, curing is insufficient and only a cured product having low tackiness and a low strength can be obtained. When the molar ratio is less than 0.2, a large amount of active hydrosilyl groups remain in the cured product even after curing. Cracks and voids are generated, and a uniform and strong cured product cannot be obtained.

  The curing reaction between the vinyl polymer having at least one alkenyl group in the molecule and the hydrosilyl group-containing compound proceeds by mixing and heating the two components. A catalyst can be added. Such hydrosilylation catalyst is not particularly limited, and examples thereof include radical initiators such as organic peroxides and azo compounds, and transition metal catalysts.

  The radical initiator is not particularly limited, and examples thereof include di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di ( t-butylperoxy) -3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, dialkyl peroxides such as α, α′-bis (t-butylperoxy) isopropylbenzene, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxides such as lauroyl peroxide, peracid esters such as t-butyl perbenzoate, diisopropyl percarbonate, di-2-ethylhexyl percarbonate Peroxydicarbonate such as 1,1 May be mentioned di (t-butylperoxy) cyclohexane, 1,1-di peroxy ketals such as (t-butylperoxy) -3,3,5-trimethylcyclohexane and the like.

Also, it is not particularly limited as a transition metal catalyst, for example, platinum simple substance, alumina, silica, carbon black or the like dispersed in a platinum solid, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone, etc. Complex, platinum-olefin complex, and platinum (0) -divinyltetramethyldisiloxane complex. Examples of the catalyst other than platinum _{compounds, RhCl (PPh 3) 3,} RhCl 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · H 2 O, NiCl 2, TiCl 4 , and the like. These catalysts may be used alone or in combination of two or more. Although there is no restriction | limiting in particular as catalyst amount, It is good to use in the range of 10 ^{< -1} > ^-10 <^-8> mol with respect to 1 mol of alkenyl groups of (A) component, Preferably it is the range of 10 ^{< -3} > ^-10 <^-6> mol. It is good to use. If it is less than 10 ⁻⁸ mol, curing does not proceed sufficiently. In addition, the hydrosilylation catalyst is generally expensive and corrosive, and a large amount of hydrogen gas may be generated and the cured product may foam. Therefore, it is preferable not to use 10 ⁻¹ mol or more.

  Although there is no restriction | limiting in particular about hardening temperature, Generally it is good to make it harden | cure at 0 to 200 degreeC, Preferably it is 30 to 150 degreeC, More preferably, it is 80 to 150 degreeC. Thereby, a curable composition can be obtained in a short time.

<Method (II)>
Although there is no restriction | limiting in particular as a silane compound which has a crosslinkable silyl group and hydrosilyl group used for the method of (II), When a typical thing is shown, the compound shown by General formula (29) will be illustrated.
_{^{H- [Si (R 58) 2}} -b (Y) b O] m -Si (R 59) 3-a (Y) a (29)
{In the formula, R ⁵⁸ and R ⁵⁹ are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different), and represents a triorganosiloxy group represented by R ⁵⁸ or When two or more R ⁵⁹ are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }
Examples of the hydrolyzable group include commonly used groups such as a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, an alkoxy group, an amide group, and an aminooxy group are preferable, but an alkoxy group is particularly preferable in terms of mild hydrolyzability and easy handling.

  Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and (a + Σb) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different. The number of silicon atoms forming the crosslinkable silyl group is one or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less.

Among these hydrosilane compounds, in particular, the general formula (30)
H-Si (R ⁵⁹ ) _3-a (Y) _a (30)
(Wherein R ⁵⁹ , Y and a are the same as above)
The compound which has a crosslinkable group shown by is preferable from a point with easy acquisition.

  A vinyl polymer having a crosslinkable silyl group in the molecule can be obtained by hydrosilylation reaction of the above hydrosilane compound and a vinyl polymer having at least one alkenyl group in the molecule.

  The vinyl polymer having a crosslinkable silyl group in the molecule is crosslinked to give a cured product.

  When a rubber-like property is particularly required for a cured product obtained by curing a vinyl polymer having a crosslinkable silyl group, the molecular weight between crosslink points that greatly affects rubber elasticity can be increased. At least one of the groups is preferably at the end of the molecular chain. More preferably, it has all functional groups at the molecular chain ends.

  The proportion of the vinyl polymer having an alkenyl group in the molecule and the silane compound having both a crosslinkable silyl group and a hydrosilyl group is not particularly limited, but the hydrosilyl group is preferably equivalent to or more than the alkenyl group.

  A hydrosilylation catalyst can be added to advance the hydrosilylation reaction more rapidly. As such a hydrosilylation catalyst, those already exemplified may be used.

  Although there is no restriction | limiting in particular about reaction temperature, Generally it is 0 to 200 degreeC, Preferably it is 30 to 150 degreeC, More preferably, it is 80 to 150 degreeC.

  In curing a curable composition containing a vinyl polymer having a crosslinkable silyl group, a condensation catalyst may or may not be used. Condensation catalysts include titanates such as tetrabutyl titanate and tetrapropyl titanate; organic compounds such as dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dimethoxide, tin octylate and tin naphthenate Tin compound; lead octylate, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, Triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine , N-methylmorpholine, amine compounds such as 1,3-diazabicyclo (5,4,6) undecene-7 or their carboxylates; amine compounds such as a reaction product or mixture of laurylamine and tin octylate Reaction product and mixture of silane and organotin compound; low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; silane coupling agent having amino group, for example, γ- One type or two or more types of known silanol catalysts such as aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane may be used as necessary. The amount used is preferably 0 to 10% by weight based on the vinyl polymer having a crosslinkable silyl group at the terminal. When an alkoxy group is used as the hydrolyzable group Y, it is preferable to use a curing catalyst because the curing rate is slow only with this polymer.

  EXAMPLES Although this invention is demonstrated further in detail based on an Example, this invention is not limited only to these Examples.

[Production Example 1]
Charge 100 parts of n-butyl acrylate, 80 parts by volume of methanol (MeOH), 1.76 parts of diethyl 2,5-dibromoadipate, and 955 ppm of N, N, N ′, N′-pentamethyldiethylenetriamine (PMDETA), It stirred at 55 degreeC under nitrogen stream. To this, copper bromide (II) (CuBr ₂ ) 107 ppm (Cu content = 30 ppm) hexamethyltris (2-aminoethyl) amine (Me ₆ TREN) 109 ppm (equivalent to Cu) with a purity of 96%, A solution prepared by dissolving 0.54 parts by volume of N, N-dimethylacetamide and a solution prepared by dissolving 17 ppm of ascorbic acid (VC) in 0.12 parts by volume of methanol are added separately, and the reaction is started by adding them. did. In the middle of the reaction, heating and stirring were continued so that the temperature of the reaction solution became 50 ° C. to 60 ° C. while appropriately adding a solution obtained by dissolving ascorbic acid in methanol. 160 minutes after the start of polymerization, when the reaction rate of n-butyl acrylate reached 92 mol%, 1,7-octadiene and ascorbic acid (VC) were added and stirring was continued for 14 hours, and the pressure in the reaction vessel was reduced. The volatile matter was removed to obtain [Polymer 1]. When [Polymer 1] at this time was subjected to GPC analysis (system: GPC system manufactured by Waters, column: Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK), the number average molecular weight was 23400, The molecular weight distribution was 1.40.

[Example 1]
400 g of [Polymer 1] obtained in Production Example 1 and 150 g of n-butanol were added to obtain [Polymer Solution 1]. In a 3LSUS tank, the temperature was raised to 180 ° C., and the mixture was stirred for 3 hours for dehalogenation. After the stirring was stopped, 650 g of n-butanol and 1200 g of a 0.1% aqueous sodium sulfate solution were added to [Polymer solution 1] and stirred for 5 minutes. After the stirring was stopped, the oil phase and the aqueous phase were promptly separated, and after standing for 20 minutes, the aqueous phase was recovered. After repeating 4 times, the solvent and water | moisture content were depressurizingly distilled for the oil phase using the rotary evaporator, and the vinyl polymer [polymer 2] which has an alkenyl terminal was obtained. When the color difference of [Polymer 2] was measured using a spectroscopic colorimeter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), ΔE * was 27.
A 300 ml four-necked flask was charged with 100 g of [Polymer 2], stirred, and heated and decompressed at 115 ° C. After pressure-reducing with nitrogen, 0.851 ml of methyl orthoformate and 0.011 ml of xylene solution of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zerovalent platinum under nitrogen flow After mixing, 2.880 ml of DMS (dimethoxymethylsilane) was added, heated and stirred at 115 ° C. for 2 to 5 hours, and devolatilized to obtain a vinyl polymer having an alkoxysilyl group. When the alkenyl group in the vinyl polymer was measured by NMR analysis (JMN-LA400 manufactured by JEOL Ltd.), the residual rate was 1% or less.

[Example 2]
400 g of [Polymer 1] obtained in Production Example 1 and 150 g of n-butanol were added to obtain [Polymer Solution 2]. In a 3LSUS tank, the temperature was raised to 180 ° C., and the mixture was stirred for 3 hours for dehalogenation. To [Polymer solution 2], 250 g of n-butanol, KW500SH: 8 g, KW700SL: 4 g (both manufactured by Kyowa Chemical Co., Ltd.) were added and stirred for 30 minutes. After stopping the stirring, the [polymer solution 2] was filtered, and the solvent was distilled off under reduced pressure using a rotary evaporator to obtain a vinyl polymer [polymer 3] having an alkenyl terminal. When the color difference of [Polymer 3] was measured using a spectroscopic colorimeter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), ΔE * was 28.
In a 300 ml four-necked flask, 100 g of [Polymer 3] was charged, stirred, and heated and decompressed at 115 ° C. After pressure-reducing with nitrogen, 0.851 ml of methyl orthoformate and 0.011 ml of xylene solution of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zerovalent platinum under nitrogen flow After mixing, 2.880 ml of DMS (dimethoxymethylsilane) was added, heated and stirred at 115 ° C. for 2 to 5 hours, and devolatilized to obtain a vinyl polymer having an alkoxysilyl group. When the alkenyl group in the vinyl polymer was measured by NMR analysis (JMN-LA400 manufactured by JEOL Ltd.), the residual rate was 1% or less.

[Comparative Example 1]
400 g of [Polymer 1] obtained in Production Example 1 was heated to 180 ° C. in a 3 LSUS tank, stirred for 3 hours, and dehalogenated to obtain [Polymer 4]. After the stirring was stopped, 800 g of n-butanol and 1200 g of a 0.1% aqueous sodium sulfate solution were added to [Polymer 4] and stirred for 5 minutes. After the stirring was stopped, the oil phase and the aqueous phase were promptly separated, and after standing for 20 minutes, the aqueous phase was recovered. After repeating 4 times, the solvent and water | moisture content were depressurizingly distilled for the oil phase using the rotary evaporator, and the vinyl polymer [polymer 5] which has an alkenyl terminal was obtained. When the color difference of [Polymer 5] was measured using a spectroscopic colorimeter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), ΔE * was 99.

[Comparative Example 2]
400 g of [Polymer 1] obtained in Production Example 1 was heated to 180 ° C. in a 3 LSUS tank, stirred for 3 hours, and dehalogenated to obtain [Polymer 6]. 350 g of n-butanol was added to [Polymer 6] to obtain [Polymer solution 3]. KW500SH: 8 g, KW700SL: 4 g (both manufactured by Kyowa Chemical Co., Ltd.) were added to [Polymer solution 3], and the mixture was stirred for 30 minutes. After the stirring was stopped, the [polymer solution 3] was filtered, and the solvent was distilled off under reduced pressure using a rotary evaporator to obtain a vinyl polymer [polymer 7] having an alkenyl terminal. When the color difference of [Polymer 7] was measured using a spectroscopic colorimeter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), ΔE * was 99.

[Comparative Example 3]
400 g of [Polymer 1] obtained in Production Example 1 and 150 g of butyl acetate were added to obtain [Polymer Solution 4]. In a 3LSUS tank, the temperature was raised to 180 ° C., and the mixture was stirred for 3 hours for dehalogenation. To [Polymer solution 4], 250 g of butyl acetate, KW500SH: 8 g, and KW700SL: 4 g (both manufactured by Kyowa Chemical Co., Ltd.) were added and stirred for 30 minutes. After the stirring was stopped, the [polymer solution 4] was filtered, and the solvent was distilled off under reduced pressure using a rotary evaporator to obtain a vinyl polymer [polymer 8] having an alkenyl terminal. When the color difference of [Polymer 8] was measured using a spectroscopic colorimeter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), ΔE * was 99.

[Comparative Example 4]
400 g of [Polymer 1] obtained in Production Example 1 and 150 g of toluene were added to obtain [Polymer Solution 5]. In a 3LSUS tank, the temperature was raised to 180 ° C., and the mixture was stirred for 3 hours for dehalogenation. 250 g of toluene, KW500SH: 8 g, and KW700SL: 4 g (both manufactured by Kyowa Chemical Co., Ltd.) were added to [Polymer solution 5], and the mixture was stirred for 30 minutes. After stopping the stirring, the [polymer solution 5] was filtered, and the solvent was distilled off under reduced pressure using a rotary evaporator to obtain a vinyl polymer [polymer 9] having an alkenyl terminal. When the color difference of [Polymer 9] was measured using a spectroscopic colorimeter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), ΔE * was 99.

[Comparative Example 5]
[Polymer solution 6] was obtained by adding 200 g of n-butanol to 100 g of [Polymer 1] obtained in Production Example 1, followed by stirring. A 1 L separable flask (with a stirrer and jacket) was charged with 200 g of 0.1 wt% sulfuric acid aqueous solution as washing water, heated to 45 ° C., and [Polymer solution 6] was dropped. Stirring was performed. After the stirring was stopped, the oil phase and the aqueous phase were quickly separated, and the oil phase turned pale yellow and the aqueous phase turned blue. After standing for 20 minutes, the oil phase was recovered, and 200 g of water was further added, followed by stirring for 5 minutes. After the stirring was stopped, the oil phase and the aqueous phase were promptly separated, and after standing for 20 minutes, the oil phase was recovered. The solvent and water | moisture content were depressurizingly distilled for the oil phase using the rotary evaporator. Next, as a dehalogenation step, 0.1 g of Sumilizer GS was added, and the mixture was stirred at 180 ° C. for 8 hours under vacuum conditions. Thereafter, as a purification step, 200 g of n-butanol and 200 g of pure water were added, mixed at 45 ° C. for 10 minutes, allowed to stand for 20 minutes, separated into two phases of an oil phase and an aqueous phase, and the oil phase was recovered. After repeating this purification step twice, the solvent and water were distilled off under reduced pressure at 100 ° C. under vacuum to obtain a vinyl polymer [polymer 10] having an alkenyl terminal. The color difference of [Polymer 10] was measured using a spectroscopic colorimeter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), and ΔE * was 40.
A 300 ml four-necked flask was charged with 100 g of [Polymer 10], stirred, and heated and decompressed at 115 ° C. After pressure-reducing with nitrogen, 0.851 ml of methyl orthoformate and 0.011 ml of xylene solution of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zerovalent platinum under nitrogen flow After mixing, 2.880 ml of DMS (dimethoxymethylsilane) was added, heated and stirred at 115 ° C. for 2 to 5 hours, and devolatilized to obtain a vinyl polymer having an alkoxysilyl group. When the alkenyl group in the vinyl polymer was measured by NMR analysis (JMN-LA400 manufactured by JEOL Ltd.), the residual rate was 20%.

Claims (15)

A method for producing a vinyl polymer (b) in which dehalogenation is carried out by heating a vinyl polymer (a) having a halogen group obtained by living radical polymerization,
A method for producing a vinyl polymer , comprising heating a vinyl polymer (a) having a halogen group in an alcohol solvent at a heating temperature of 100 ° C. or more and 250 ° C. or less . The method for producing a vinyl polymer according to claim 1 , wherein the alcohol solvent has 6 or less carbon atoms. The method for producing a vinyl polymer according to claim 1 or 2 , wherein a content of the vinyl polymer (a) having a halogen group dissolved in an alcohol solvent in a solution is 1 wt% or more and 90 wt% or less. . The method for producing a vinyl polymer according to any one of claims 1 to 3 , wherein the vinyl polymer (A) having a halogen group has at least one alkenyl group in the molecule. The method for producing a vinyl polymer according to claim 4 , wherein the alkenyl group is present at the terminal of the molecular chain of the vinyl polymer (a) having a halogen group. After heating the vinyl polymer (a) having a halogen group in the alcohol solvent , the resulting halogenated compound is brought into contact with an adsorbent or water by bringing the mixed solution of the vinyl polymer (b) and the halogen compound into contact with an adsorbent or water. The method for producing a vinyl polymer according to any one of claims 1 to 5 , wherein the polymer is removed. The method for producing a vinyl polymer according to claim 6 , wherein the adsorbent is activated carbon or an inorganic adsorbent. The method for producing a vinyl polymer according to claim 6 or 7 , wherein the water is pure water or water containing a salt. The method for producing a vinyl polymer according to claim 8 , wherein the salt contained in water is sodium sulfate. The vinyl-based heavy metal according to any one of claims 1 to 9 , wherein the central metal of the transition metal complex which is a polymerization catalyst for living radical polymerization is an element of Group 8, 9, 10, or 11 of the periodic table. Manufacturing method of coalescence. The method for producing a vinyl polymer according to claim 10 , wherein the central metal of the transition metal complex is iron, nickel, ruthenium or copper. The method for producing a vinyl polymer according to claim 11 , wherein the central metal of the transition metal complex is copper. A reaction between a vinyl polymer having at least one alkenyl group in the molecule obtained by the production method according to any one of claims 4 to 12 and a silane compound having both a crosslinkable silyl group and a hydrosilyl group. A method for producing a vinyl-based polymer having a crosslinkable silyl group obtained by the method. Halogen is removed from a vinyl polymer having a halogen group, which undergoes a step of heating a vinyl polymer (a) having a halogen group produced by living radical polymerization in an alcohol solvent at a heating temperature of 100 ° C. to 250 ° C. how to. A vinyl polymer produced by living radical polymerization and containing a polymerization catalyst residue and having a halogen group is heated in an alcohol solvent at a heating temperature of 100 ° C. or more and 250 ° C. or less. A purification method in which a mixed solution of a polymer (b) and a halogen compound is brought into contact with an adsorbent or water to simultaneously remove the halogen compound and the polymerization catalyst.