JP2018095775A - Production method of polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of polymer, the method materializing high yield of block polymer and production of polymer through a simplified and environmentally friendly step.SOLUTION: The production method of block polymer including the following steps 1 to 4 is provided. Step 1: polymerizing a radical-polymerizable monomer (hereinafter, referred to as a first monomer) under the presence of thiocarboxylic acid and a polymerization initiator in an organic solvent having a ketone structure to obtain a reaction mixture containing a polymer having thiocarboxylic acid ester at a terminal, step 2: reducing a residual amount of the first monomer in the reaction mixture obtained in the step 1 to 40 mol% or lower relative to the polymer having thiocarboxylic acid ester at terminal, step 3; decomposing the thiocarboxylic acid ester groups of the polymer in the reaction mixture obtained in the step (2) to thiol groups to obtain a reaction mixture containing polymer having the thiol group at a terminal, and step 4: reacting the reaction mixture obtained in the step 3 with a further radically-polymerizable second monomer to obtain block polymer.SELECTED DRAWING: None

Description

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

In a radical polymerization reaction used when producing a polymer, a thiol compound may be used as a reaction control agent.
For example, in Patent Document 1, a thiol compound is used as a functional group-introducing agent at the polymer terminal, and in Patent Document 2 as a molecular weight distribution adjusting agent. Patent Document 3 describes a method for producing a block polymer having a molecular chain composed of the same kind of structural unit in a polymer using thiocarboxylic acid which is a kind of thiol compound.
Regarding the method for producing such a block polymer, the conversion of monomers is improved by changing the type of thiocarboxylic acid in Patent Document 4, changing the type of base in Patent Document 5, and adding an acid during polymerization in Patent Document 6. Is mentioned.

  On the other hand, it is known to use a polymer having a polymer segment derived from a hydrophobic unsaturated monomer and a polymer segment derived from a monomer having a betaine group as a hydrophilic treatment agent (Patent Document) 7-9).

JP-A-10-212305 Special table 2013-516529 gazette JP 59-189114 A Japanese Patent No. 3256544 JP-A-3-41109 JP-A-9-3108 JP-A-2015-105313 JP2015-108054A JP 2016-113471 A

Depending on the application of the polymer, a block-structured polymer may be desirable. In general, in order to improve the yield of polymer with the desired structure, purification such as recrystallization (a method in which the temperature of the saturated solution of the polymer is lowered and left for a long time to grow the polymer crystal to remove impurities) The process is necessary and complicated, and in order to improve the yield, the purification process must be repeated, and the amount of the solvent to be discarded each time is a problem.
The present invention provides a method for producing a block polymer with a high yield of block polymer in a simple and low environmental load process.
In particular, the present invention provides a production method for obtaining a block polymer in a process that is simple and has a low environmental burden when producing a block polymer by a radical polymerization reaction.

The present invention relates to a method for producing a block polymer including the following steps 1 to 4.
Step 1: A monomer capable of radical polymerization (hereinafter referred to as a first monomer) is polymerized in an organic solvent having a ketone structure in the presence of a thiocarboxylic acid and a polymerization initiator, and includes a polymer having a thiocarboxylic acid ester at the terminal. Step 2 for obtaining a reaction mixture Step 2: Step 3 for reducing the residual amount of the first monomer in the reaction mixture obtained in Step 1 to 40 mol% or less with respect to the polymer having a terminal thiocarboxylic acid ester. Decomposing the thiocarboxylic acid ester group of the polymer in the reaction mixture obtained in step 2 into a thiol group to obtain a reaction mixture containing a polymer having a thiol group at the end Step 4: Reaction obtained in step 3 A process for obtaining a block polymer by reacting the mixture with a further radically polymerizable monomer (hereinafter referred to as a second monomer).

By using the production method of the present invention, it is possible to produce a polymer having a high block polymer ratio by increasing the yield of the block polymer in a simple and low environmental load process.
In addition, the improvement of the block polymer ratio in the polymer increases the adhesion of the polymer to the solid surface when the surface treatment agent containing the polymer is used on the solid surface, and decreases the contact angle of the solid surface, etc. There is an effect.

  The block polymer ratio of the present invention is the mass ratio of the block polymer in the reaction end product to the by-produced random polymer, and can be measured by the measuring method shown in the examples.

  The block polymer of the present invention is a polymer containing a portion composed of the first monomer in the polymer.

  In the present invention, a polymer containing a block polymer segment of a first monomer is produced in an organic solvent having a ketone structure in the presence of thiocarboxylic acid, and the amount of the remaining first monomer is changed to thiocarboxylic acid ester. It has been found that the block polymer ratio can be easily improved by reducing it to 40 mol% or less with respect to the polymer at the end. The reason why such an effect is obtained in the present invention is not clear, but by using an organic solvent having a ketone structure as a reaction medium, it is possible to suppress the dissociation of the thiocarboxylic acid group generated at the polymer terminal and to activate the radical. It is thought that it can be kept.

<Method for producing polymer>
(Process 1)
Step 1 is a step of polymerizing the first monomer in an organic solvent having a ketone structure in the presence of a thiocarboxylic acid and a polymerization initiator to obtain a reaction mixture containing a polymer having a thiocarboxylic acid ester at the terminal.

The first monomer is a radical polymerizable monomer.
Examples of the first monomer include a monomer represented by the following general formula (1) and a monomer represented by the following general formula (2). The first monomer is preferably a monomer represented by the following general formula (1).

[Where,
R ^{1 to} R ³ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ⁴ : a hydrocarbon group having 1 to 22 carbon atoms Y ¹ : O or NR ¹¹ , R ¹¹ is a hydrogen atom Or a C1-C4 hydrocarbon group is shown. ]

[Wherein, R ^{5 to} R ^{7 are the} same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ⁸ : an alkylene group having 1 to 4 carbon atoms R ⁹ , R ¹⁰ : the same or different, carbon The hydrocarbon group X ¹ having a number of 1 or more and 4 or less is O ¹ or NR ¹² , and R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]

In the general formula (1), from the viewpoint of availability of the monomer, the viewpoint of polymerizability of the monomer, the viewpoint of lowering the contact angle, the adsorptivity and the solubility, and the viewpoint of imparting an appropriate dynamic friction coefficient, R ¹ And R ² is preferably a hydrogen atom. From the same viewpoint, R ³ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. Y ¹ is preferably O from the same viewpoint. From the same viewpoint, R ⁴ is preferably a hydrocarbon group having 1 to 18 carbon atoms, more preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 7 carbon atoms. Examples of the hydrocarbon group for R ⁴ include an alkyl group and an alkenyl group. Examples of R ⁴ include a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, preferably a linear or branched alkyl group or alkenyl group having 1 to 12 carbon atoms, More preferably, it is a linear alkyl group having 1 to 6 carbon atoms.

  Specific examples of the monomer represented by the general formula (1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, ( T-butyl (meth) acrylate, n-hexyl (meth) acrylate, (cyclohexyl)-(meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n- (meth) acrylate (Meth) acrylate esters such as decyl, lauryl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate, and N-ethyl (Meth) acrylamide, N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N, N- Ethyl (meth) acrylamide, (meth) acrylamide.

In the general formula (2), from the viewpoint of availability of the monomer, the viewpoint of the polymerizability of the monomer, the viewpoint of reducing the contact angle, the viewpoint of improving the adsorptivity and solubility, and the viewpoint of imparting an appropriate dynamic friction coefficient, R ⁵ and R ⁶ is preferably a hydrogen atom. From the same viewpoint, R ⁷ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. X ¹ is preferably O from the same viewpoint. From the same viewpoint, R ⁸ is preferably an alkylene group having 2 or 3 carbon atoms, and is preferably a dimethylene group having 2 carbon atoms. From the same viewpoint, R ⁹ and R ¹⁰ are preferably a methyl group or an ethyl group, and more preferably a methyl group.
Specific examples of the monomer represented by the general formula (2) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, N, N-dimethylamino. Examples thereof include ethyl (meth) acrylamide and N, N-dimethylaminopropyl (meth) acrylamide.

Examples of the first monomer include esters or amides of alcohols or amines having an alkyl group having 2 to 22 carbon atoms and (meth) acrylic acid from the viewpoint of reactivity. The first monomer is preferably an ester or amide of an alcohol or amine having an alkyl group having 2 to 12 carbon atoms and (meth) acrylic acid, and an alcohol or amine having an alkyl group having 3 to 8 carbon atoms; An ester or amide with (meth) acrylic acid is more preferred. Here, (meth) acrylic acid refers to acrylic acid or methacrylic acid.
The first monomer is preferably a monomer selected from acrylic acid esters, methacrylic acid esters, acrylic acid amides, and methacrylic acid amides. These may be an ester or amide with an alcohol or amine having an alkyl group having 2 to 22 carbon atoms.
The first monomer is more preferably a methacrylic acid ester, more preferably an ester of an alcohol having an alkyl group having 2 to 22 carbon atoms and methacrylic acid, and an alcohol having an alkyl group having 2 to 12 carbon atoms and methacrylic acid. An ester with an acid is still more preferred, an ester of an alcohol having an alkyl group having 3 to 8 carbon atoms and methacrylic acid is more preferred, and butyl methacrylate is still more preferred.

  The thiocarboxylic acid is a component used to introduce a functional group that can be converted into an SH group at the terminal of the polymer obtained in Step 1. The thiocarboxylic acid is preferably an organic thiocarboxylic acid having a —COSH group from the viewpoint of decomposability of the thiocarboxylic acid ester group in Step 3. From the same viewpoint, the thiocarboxylic acid is preferably a thiocarboxylic acid having 1 to 10 carbon atoms. From the same viewpoint, the thiocarboxylic acid is preferably a thiocarboxylic acid selected from thioacetic acid, thiopropionic acid, thiobutyric acid, and thiovaleric acid, and more preferably thioacetic acid.

  The thiocarboxylic acid is preferably 500% by mass or more, more preferably 800% by mass or more, and preferably 10,000% by mass or less, more preferably from the viewpoint of reactivity, from the viewpoint of reaction selectivity with respect to the polymerization initiator. 850 mass% or less is used.

As the polymerization initiator, (1) 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) Azo polymerization initiators such as (2), peroxide polymerization initiators such as lauroyl peroxide and benzoyl peroxide, and (3) persulfuric polymerization initiators such as ammonium persulfate. From the viewpoints of reactivity, availability, and safety, an azo polymerization initiator is preferred.
The polymerization initiator is preferably 0.65% by mass or more, more preferably 1.3% by mass or more with respect to the first monomer from the viewpoint of reactivity, and the first monomer from the viewpoint of economy. The amount is preferably 100% by mass or less, more preferably 30% by mass or less.

  Examples of the organic solvent having a ketone structure include ketones having 3 to 10 carbon atoms. The organic solvent having a ketone structure is preferably a ketone having 3 to 10 carbon atoms having a linear, branched, or cyclic alkyl group from the viewpoint of reactivity and removability, and a linear, branched, or cyclic alkyl group. More preferred are ketones having 3 to 8 carbon atoms, more preferred are ketones having 3 to 6 carbon atoms having a linear alkyl group, still more preferred are ketones selected from acetone and methyl ethyl ketone, and even more preferred is acetone. These ketones may be used alone or in combination of two or more. The linear alkyl group preferably has 1 to 10 carbon atoms. The number of carbon atoms of the branched alkyl group is preferably 3 or more and 10 or less. The number of carbon atoms in the cyclic alkyl group is preferably 3 or more and 10 or less.

The method for polymerizing the first monomer is not particularly limited as long as it is a method using an organic solvent having a ketone structure, and a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or the like can be adopted. The solution polymerization method is preferable from the viewpoints of thickness and reaction selectivity.
The polymerization temperature of the first monomer can be appropriately selected depending on the polymerization initiator to be used, the type of solvent, etc., but is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, from the viewpoint of reaction selectivity. 120 degrees C or less is preferable, 110 degrees C or less is more preferable, and 100 degrees C or less is still more preferable.

In step 1, the first monomer is polymerized in an organic solvent having a ketone structure in the presence of a thiocarboxylic acid and a polymerization initiator to obtain a reaction mixture containing a polymer having a thiocarboxylic acid ester at the terminal. The polymerization can be terminated when the content of the polymerization initiator in the reaction mixture becomes half of the added amount. Further, it can be confirmed by ¹ H-NMR that the polymer has a thiocarboxylic acid ester at the terminal (see Examples for the conditions of ¹ H-NMR).

  The polymer having a thiocarboxylic acid ester at the terminal obtained in Step 1 can function as a hydrophobic segment in the finally obtained block polymer when the first monomer as a constituent component is hydrophobic. That is, it can be a segment that contributes to the adsorptivity to the hydrophobic surface.

(Process 2)
Step 2 is a step of reducing the residual amount of the first monomer in the reaction mixture obtained in Step 1 to 40 mol% or less with respect to the polymer having a thiocarboxylic acid ester at the terminal.

The method for reducing the residual amount of the first monomer may be a general method as long as it is a method for reducing the content of unreacted substances. For example, reprecipitation (adding a poor solvent to the solution containing the polymer, Such as polymer removal as a precipitate), membrane purification (a method for increasing the purity by using the difference in permeability of the membrane depending on the molecular size), vacuum drying (a method for increasing the purity by using the difference in boiling point), overrun, etc. From the viewpoint of simplicity of the process, drying under reduced pressure or overrun is preferable, and overrun is more preferable. These methods may be performed once or twice or one kind or a combination of two or more kinds. Note that the overrun is a method of reducing the amount of unreacted substances by adding a reaction initiator and / or increasing the temperature to advance the reaction of the unreacted first monomer. Examples of the overrun include a method in which a polymerization initiator is added to the reaction mixture in Step 1 and mixed and heated to further react with the unreacted first monomer in the mixture. The amount of the polymerization initiator to be added is preferably 0.5 to 3 times the amount of the polymerization initiator used in Step 1. The heating time is preferably 1 hour or more and 20 hours or less. The temperature of the heated reaction system is preferably 40 ° C or higher and 80 ° C or lower.
In addition, when drying under reduced pressure, when the low-boiling point solvent is first distilled off from the reaction mixture containing the first monomer and it is difficult to reduce the first monomer, the high-boiling point that dissolves the polymer further. For example, anisole may be added as a solvent, and the first monomer may be reduced by azeotropy.

In Step 2, from the viewpoint of improving the block polymer ratio, the residual amount of the first monomer in the reaction mixture is 40 mol% or less, preferably 20 mol% or less, more preferably, based on the polymer having a thiocarboxylic acid ester at the terminal. Is 5 mol% or less, more preferably 1 mol% or less, still more preferably 0.5 mol% or less, and preferably 0 mol% or more. It is also preferable to reduce to 0 mol%.
The amount of the polymer having a thiocarboxylic acid ester at the end in the reaction mixture can be confirmed by ¹ H-NMR.
The remaining amount of the ^first monomer in the reaction mixture can be confirmed by the method shown in Examples using ¹ H-NMR. ^When the residual amount of the first monomer is below the detection limit by the method of the example using ¹ H-NMR, it may be considered that the amount is reduced to 0 mol%.

(Process 3)
Step 3 is a step in which the thiocarboxylic acid ester group of the polymer in the reaction mixture obtained in Step 2 is decomposed into thiol groups to obtain a reaction mixture containing a polymer having a thiol group at the terminal.
Specifically, the thiocarboxylic acid ester group of the polymer is decomposed into thiol groups as follows.
A solvent is added to the reaction mixture in Step 2, and the mixture is heated and stirred under alkaline conditions, and then neutralized with an organic acid. The pH at the time of heating and stirring is preferably 7 or more from the viewpoint of reaction speed, more preferably 8 or more, further preferably 9 or more, from the viewpoint of reaction selectivity, preferably 13 or less, more preferably 12.5 or less, 12 or less is more preferable. Although the temperature at the time of a heating will not be specifically limited if it is a temperature which does not dissociate a thiol group, 30 degreeC or more is preferable, 35 degreeC or more is more preferable, 80 degreeC or less is preferable, and 60 degreeC or less is more preferable. The solvent is not particularly limited as long as it does not dissociate thiol groups. Specifically, one or more selected from methanol, ethanol, linear or branched propanol, ethyl acetate, acetone, methyl ethyl ketone, and tetrahydrofuran are preferable, and methanol, ethanol, and linear or branched propanol 1 type or 2 types or more chosen from are more preferable.

The decomposition rate of thiocarboxylic acid ester can be confirmed using ¹ H-NMR. For example, the decomposition rate of thioacetic acid ester can be confirmed by the method shown in Examples using ¹ H-NMR. When the decomposition rate of the thiocarboxylic acid ester is 80% or more, preferably 100%, the thiocarboxylic acid ester group of the polymer is decomposed into thiol groups, and a reaction mixture containing a polymer having a thiol group at the terminal is obtained. I can judge.

(Process 4)
Step 4 is a step of obtaining a block polymer by reacting the reaction mixture obtained in Step 3 with a further radical polymerizable monomer (second monomer).
Specifically, a block polymer is obtained as follows.
A solvent is added to the reaction mixture in Step 3, and the second monomer and the polymerization initiator are added dropwise together with the solvent while heating and stirring at reflux temperature, and reacted. The solvent at this time is not particularly limited as long as it does not dissociate the thiol group. Specifically, one or more selected from methanol, ethanol, linear or branched propanol, ethyl acetate, acetone, methyl ethyl ketone, and tetrahydrofuran are preferable, and from methanol, ethanol, and linear or branched propanol. One or more selected are more preferable. Moreover, what was illustrated at the process 1 can be used for a polymerization initiator. When a polymerization initiator is used in step 4, the polymerization initiator is preferably 0.1% by mass or more, more preferably 0.25% by mass or more, and more preferably 0.25% by mass or more with respect to the second monomer, from the viewpoint of conversion rate. From the viewpoint of the block polymer ratio, the amount of the polymer obtained in step 1 is preferably 1% by mass or less, more preferably 0.3% by mass or less.

The second monomer may be the same as or different from the first monomer. Further, it may be a mixture of different monomers. As the second monomer, those mentioned as the first monomer can be used. From the viewpoint of reactivity and the viewpoint of improving the hydrophilicity of the generated block polymer, the monomer represented by the general formula (2) is preferable. Furthermore, among the monomers represented by the general formula (2), dialkylaminoalkyl (meth) acrylate or dialkylaminoalkyl (meth) acrylamide is preferable.
Two or more kinds of second monomers can be used.
The second monomer preferably includes at least one monomer different from the first monomer.

  As the structure of the block polymer, a polymer part having a thiol group obtained through Steps 1 to 3 at the terminal is represented by A, and a polymer part polymerized in Step 4 is represented by B. AB, AB- A and B-A-B structures are mentioned, and from the viewpoint of ease of production, any of the structures AB, A-B-A, and B-A-B is preferable, and the structure of A-B is more preferable. preferable. The block polymer is preferably composed of one or two A and one or two B, and more preferably composed of one A and one B. The polymer part A is preferably a homopolymer block. The polymer part B is preferably a random polymer block of two or more monomers.

(Process 5)
When the second monomer is an unsaturated monomer having an amino group, the method for producing a polymer of the present invention can include the following step 5.
Step 5: Step of reacting the block polymer obtained in Step 4 with a betaine agent

Step 5 is a step of reacting an amino group on the side chain of the block polymer with a betaine agent to change to a betaine group to obtain a betaine polymer.
A known method can be used as a production method for reacting an amino group with a betaine agent to convert it into a betaine group, and examples thereof include the method described in JP-T-2006-514150.

The betaine agent also functions as a quaternizing agent for amino groups. The betaine agent is preferably at least one selected from 1,3-propane sultone, 1,4-butane sultone and sodium 3-chloro-2-hydroxy-1-propanesulfonate from the viewpoint of reactivity.
Step 5 can be performed in a suitable solvent. The solvent is not particularly limited as long as it dissolves the block polymer. A solvent can be used individually or in combination of 2 or more types. Specific examples include 2,2,2-trifluoroethanol.

  The betaine polymer obtained in Step 5 is suitable as a hydrophilizing agent, in particular, as a hydrophilizing agent for hard surfaces, and further as a hydrophilizing agent for hydrophobic hard surfaces.

  An outline of an example of the production method of the present invention is as follows. In the following, n-butyl methacrylate (BMA) as the first monomer, 2- (dimethylamino) ethyl methacrylate (DMAEMA) and n-butyl methacrylate (BMA) as the second monomer, thioacetic acid as the thiocarboxylic acid, 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65B) is used as the polymerization initiator.

  A specific procedure of the above method will be described. Acetone, which is a ketone solvent, is placed in a reaction vessel, heated to a predetermined temperature, for example, 80 ° C. with stirring, and a mixed solution of BMA, V-65B, thioacetic acid and acetone is added dropwise. Stir at that temperature for a predetermined time to polymerize the BMA and perform step 1. Thereafter, BMA remaining in the reaction mixture is reduced by, for example, follow-up (Step 2). The reaction mixture after step 2 is placed in a reaction vessel, heated with stirring, an alkaline agent, for example, an ethanol solution of NaOH, is added and stirred with heating. After heating, a neutralizing agent, for example, an ethanol solution of citric acid is added to neutralize (step 3). Ethanol is put into a reaction vessel, heated to a predetermined temperature while stirring, and DMAEMA, BMA, V-65B, the reaction mixture obtained in Step 3 and a mixed solution containing ethanol are added dropwise. A block polymer is obtained by reacting at a predetermined temperature for a predetermined time (step 4). In the above example, after the step 4, the step 5 is further performed to make the block polymer betaine to obtain a betaine polymer.

Of the block polymer finally obtained, the molar ratio occupied by the first monomer segment used in Step 1 is preferably 0.5 mol% or more from the viewpoint of improving the adsorptivity of the block polymer to the solid surface, 1 mol% or more is more preferable, 2 mol% or more is further preferable, 3 mol% or more is more preferable, 5 mol% or more is further more preferable, and 95 mol% from the viewpoint of solubility when a block polymer is used as a surface treatment agent. The following is preferable, 80 mol% or less is more preferable, 50 mol% or less is further preferable, 30 mol% or less is further preferable, and 20 mol% or less is still more preferable.
In addition, in the finally obtained block polymer, the molar ratio of the first monomer segment used in step 1 and the second monomer segment used in step 4 is preferably 50 mol% or more, and more than 70 mol%. Is more preferable, 80 mol% or more is more preferable, 100 mol% or less is preferable, and 100 mol% may be sufficient.

  In addition, the block polymer finally obtained includes the first monomer segment used in step 1 and the second monomer segment used in step 4 to the extent that the effect of the block polymer of the present invention is not hindered. A third monomer can be included. Examples of the third monomer include monomers that can be polymerized with the first monomer and / or the second monomer by a method other than radical polymerization. The third monomer may be the same monomer or a combination of two or more different monomers. The molar ratio of the third monomer contained in the finally obtained block polymer is preferably 50 mol% or less, more preferably 30 mol%, further preferably 20 mol%, and still more preferably 0 mol%.

<Surface treatment method>
The present invention provides a surface treatment method for a solid surface, wherein the solid surface is brought into contact with a treatment agent (hereinafter, treatment agent A) containing the block polymer obtained by the present invention, preferably a betainized polymer.
Here, the “solid” of the “solid surface” is not particularly limited, and glass, ceramic, porcelain, glazed, tile, ceramics; metals such as aluminum, stainless steel, brass; polyethylene, polypropylene, melamine resin, polyamide resin, ABS Synthetic resins such as resin and FRP; natural fibers such as cotton, silk and wool; synthetic fibers such as polyester, nylon and rayon; solids such as hair, nails and teeth.
Suitable solid surfaces to which the treatment agent A can be applied include a hydrophobic hard surface, and one or more hydrophobic hard surfaces selected from ceramics, metals, and synthetic resins. In the present invention, the hydrophobic hard surface means that the static contact angle to water exceeds 70 °, and the hydrophilic hard surface means 70 ° or less. In addition, a static contact angle can be measured by the method as described in an Example.
The treating agent A is preferably an aqueous solution from the viewpoint of handling stability.

The method for contacting the solid surface with the treatment agent A is not particularly limited. For example, the following methods (i) to (iii) may be mentioned.
(I) Method of immersing the solid in the treatment agent A (ii) Method of spraying or applying the treatment agent A to the solid (iii) Method of washing the solid surface with the treatment agent A according to a conventional method Solid surface is hydrophilic with the treatment agent A The temperature for the chemical treatment is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, more preferably 15 ° C. or higher, from the viewpoint of enhancing the hydrophilization performance of the processing agent A and the ease of the processing method. 50 ° C. or lower, more preferably 40 ° C. or lower, more preferably 30 ° C. or lower.
In the method (i), the immersion time is preferably 0.5 minutes or more, more preferably 1 minute or more, and preferably 60 minutes from the viewpoint of enhancing the hydrophilization performance of the treatment agent A and from the viewpoint of economy. Min or less, more preferably 50 min or less.
In the method (ii), the method of spraying or applying the treatment agent A onto the solid surface can be appropriately selected according to the width (area) of the hard surface. A method is preferred in which the treatment agent A is sprayed onto the solid surface by spraying and then dried. If necessary, rinse with water after spraying. Further, after spraying, it may be thinly applied using a sponge or the like.
The amount of the treatment agent A sprayed or applied to the solid surface is preferably 0.01 mL or more and 0.1 mL or less per 10 cm ^{2 in} the case of the treatment agent A having a polymer content of 0.3% by mass, for example. is there.
In the method (iii), it is preferably used in the form of a detergent composition containing the polymer obtained by the present invention and a surfactant and brought into contact with a solid surface. In the case of the form of such a detergent composition, the pH is preferably 4 or more, preferably 10 or less, more preferably 8 or less, from the viewpoint of handling safety and prevention of damage to the solid surface.
A general thing can be used as surfactant.

The static contact angle with respect to water of the solid surface hydrophilized with the processing agent A is preferably 70 ° or less, more preferably 69 ° or less.
Moreover, it is preferable that the solid surface hydrophilized with the processing agent A is processed uniformly from a viewpoint of improving the hydrophilization performance. The uniformity of the surface treatment can be judged by visually observing the solid surface after the treatment.

<Measurement of physical properties>
(1) Block polymer ratio The peak area is measured by liquid chromatography (LC) under the following conditions, and the block polymer ratio is determined by the following formula.
Block polymer ratio = S1 / S2
S1: The area of the separable peak derived from the block polymer S2: The area of the separable peak derived from the random polymer by-produced in the third step In the examples and comparative examples, S1 represents a BMA polymer segment and a random The total of BMA and DMAEMA polymer segments, with an area of 10.5 to 16 minutes. S2 is a random polymer segment of BMA and DMAEMA, and has an area of 7 minutes to 10.5 minutes.
[LC analysis conditions]
Column: ODS-P (manufactured by Chemicals Evaluation Research Organization)
Eluent: A 0.1% by mass trifluoroacetic acid (TFA) (manufactured by Wako Pure Chemical Industries) / water, B 0.1% by mass TFA / isopropyl alcohol (IPA) (manufactured by Wako Pure Chemical Industries)
A / B = 100/0 (0 min)-0/100 (15 min), 0/100 (25 min)
Flow rate: 1.2 mL / min
Column temperature: 40 ° C
Detector: CAD
Sample: 0.1 wt% IPA solution, 100 μL

(2) Residual amount of monomer with respect to polymer having thioacetic acid ester at the terminal (residual monomer amount)
From the measurement result of ¹ H-NMR under the following conditions, it is determined from the integral ratio of the methyl group (2.29-2.35 ppm) of thioacetate and the adjacent methylene group (4.0-4.2 ppm) of the oxygen atom of butyl methacrylate.
[NMR measurement conditions]
Nuclear magnetic resonance (NMR) apparatus: “Mercury400” (Agilent)
Sample: Polymer 2 mass% deuterated chloroform solution Measurement mode: Proton 1D
Measurement temperature: 25 ℃
Integration count: 32 times

(3) Decomposition rate of polymer having thioacetate ester at the end From the measurement result of ¹ H-NMR in the reaction mixture in step 3 (conditions are the same as in (2) above), Based on the methyl group (2.29-2.35 ppm) and BMA (4 ppm) of thioacetate, the decomposition rate is determined by the disappearance of the methyl group (2.29-3.35 ppm) of thioacetate. Specifically, the decomposition rate is obtained by the following formula.

<Raw materials used for polymer production>
2- (dimethylamino) ethyl methacrylate (DMAEMA): manufactured by Wako Pure Chemical Industries, Ltd. n-butyl methacrylate (BMA): manufactured by Wako Pure Chemical Industries, Ltd. Thioacetic acid: manufactured by Wako Pure Chemical Industries, Ltd.
2,2'-Azobis (2,4-dimethylvaleronitrile) (V-65B): Wako Pure Chemical Industries, Ltd. Sodium hydroxide (NaOH): Wako Pure Chemical Industries, Ltd.
Sodium 3-chloro-2-hydroxy-1-propanesulfonate (CHPS): manufactured by Aldrich Sodium bicarbonate: manufactured by Wako Pure Chemical Industries, Ltd.
2-butanone (MEK): Wako Pure Chemical Industries, Ltd. Ethanol: Wako Pure Chemical Industries, Ltd. Methanol: Wako Pure Chemical Industries, Ltd. Acetone: Wako Pure Chemical Industries, Ltd. Anisole: Wako Pure Chemical Industries, Ltd. Trifluoroethanol (TFE): Tokyo Chemical Industry Co., Ltd.

<Example 1>
47.0 g of acetone was placed in the reaction vessel and heated to 56 ° C., the reflux temperature, with stirring. When the reflux temperature was reached, a mixed solution of 94.9 g of BMA, 0.62 g of V-65B, 5.1 g of thioacetic acid, and 20.1 g of acetone was added dropwise over 3 hours. After the dropping, the mixture was stirred at reflux temperature for 3 hours (Step 1).
Thereafter, a follow-up operation of adding 0.62 g of V-65B and continuously stirring the reflux temperature for 3 hours was repeated twice. The amount of residual BMA monomer with respect to the polymer having a thioacetate ester at the end (hereinafter referred to as a terminal thioacetate polymer) in the obtained solution was 4.4 mol% (0.044 mol / mol) (Step 2).
13.8 g of this solution and 4.2 g of ethanol were placed in a reaction vessel and heated at 40 ° C. with stirring. NaOH ethanol solution (NaOH 0.15 g, ethanol 2 g) was added thereto, and the mixture was heated and stirred at 40 ° C. for 1 hour. After heating, an ethanol solution of citric acid (citric acid 0.2384 g, ethanol 2 g) was added for neutralization (step 3). The decomposition rate of the terminal thioacetic acid ester polymer was determined by the above method, and it was confirmed that it was 100%, that is, a solution that was a reaction mixture containing a polymer having a thiol group at the terminal was obtained.
The reaction vessel was charged with 46.6 g of ethanol and heated at 82 ° C. with stirring. When the reflux temperature was reached, a mixed solution of DMAEMA 52.5 g, BMA 38.0 g, V-65B 0.24 g, the resulting solution 22.39 g, and ethanol 8 g was added dropwise over 1 hour. During this time, the internal temperature was kept at 80 ° C. After completion of dropping, the mixture was heated and stirred at 80 ° C. for 1 hour to obtain a solution containing a block polymer (Step 4).
When the obtained solution was dried and analyzed using LC, the block polymer ratio was 1.09 wt / wt.

<Example 2>
47.0 g of acetone was placed in the reaction vessel and heated to 56 ° C., the reflux temperature, with stirring. When the reflux temperature was reached, a mixed solution of 94.9 g of BMA, 0.62 g of V-65B, 5.1 g of thioacetic acid, and 20.1 g of acetone was added dropwise over 3 hours. After the dropping, the mixture was stirred at reflux temperature for 3 hours (Step 1).
Thereafter, about 100 g of anisole was added, followed by vacuum drying at 80 ° C. and 1 kPa or less for 16 hours. The amount of residual BMA monomer relative to the terminal thioacetate polymer in the obtained solid was 0.80 mol% (0.0080 mol / mol) (step 2).
10 g of the obtained solid, 8 g of ethanol, and a stirrer chip were placed in a reaction vessel and heated at 40 ° C. NaOH ethanol solution (NaOH 0.15 g, ethanol 2 g) was added thereto, and the mixture was heated and stirred at 40 ° C. for 1 hour. After heating, an ethanol solution of citric acid (citric acid 0.2384 g, ethanol 2 g) was added for neutralization (step 3). The decomposition rate of the terminal thioacetic acid ester polymer was determined by the above method, and it was confirmed that it was 100%, that is, a solution that was a reaction mixture containing a polymer having a thiol group at the terminal was obtained.
The reaction vessel was charged with 46.6 g of ethanol and heated at 82 ° C. with stirring. When the reflux temperature was reached, a mixed solution of DMAEMA 52.5 g, BMA 38.0 g, V-65B 0.24 g, the resulting solution 22.39 g, and ethanol 8 g was added dropwise over 1 hour. During this time, the internal temperature was kept at 80 ° C. After completion of dropping, the mixture was heated and stirred at 80 ° C. for 1 hour to obtain a solution containing a block polymer (Step 4).
When the obtained solution was dried and analyzed using LC, the block polymer ratio was 1.22 wt / wt.

<Example 3>
47.0 g of acetone was placed in the reaction vessel and heated to 56 ° C., the reflux temperature, with stirring. When the reflux temperature was reached, a mixed solution of 94.9 g of BMA, 0.62 g of V-65B, 5.1 g of thioacetic acid, and 20.1 g of acetone was added dropwise over 3 hours. After the dropping, the mixture was stirred at reflux temperature for 3 hours (Step 1).
Thereafter, this solution was added dropwise to 20 times by volume of methanol and reprecipitated. The amount of residual BMA monomer with respect to the terminal thioacetate polymer in the obtained solid was below the detection limit (step 2).
The obtained solid 10 g and ethanol 8 g were put in a reaction vessel and heated at 40 ° C. NaOH ethanol solution (NaOH 0.15 g, ethanol 2 g) was added thereto, and the mixture was heated and stirred at 40 ° C. for 1 hour. After heating, an ethanol solution of citric acid (citric acid 0.2384 g, ethanol 2 g) was added for neutralization (step 3). The decomposition rate of the terminal thioacetic acid ester polymer was determined by the above method, and it was confirmed that it was 100%, that is, a solution that was a reaction mixture containing a polymer having a thiol group at the terminal was obtained.
The reaction vessel was charged with 46.6 g of ethanol and heated at 82 ° C. with stirring. When the reflux temperature was reached, a mixed solution of DMAEMA 52.5 g, BMA 38.0 g, V-65B 0.24 g, the resulting solution 22.39 g, and ethanol 8 g was added dropwise over 1 hour. During this time, the internal temperature was kept at 80 ° C. After completion of dropping, the mixture was heated and stirred at 80 ° C. for 1 hour to obtain a solution containing a block polymer (Step 4).
When the obtained solution was dried and analyzed using LC, the block polymer ratio was 1.18 wt / wt.

<Comparative Example 1>
47.0 g of acetone was placed in the reaction vessel and heated to 56 ° C., the reflux temperature, with stirring. When the reflux temperature was reached, a mixed solution of 94.9 g of BMA, 0.62 g of V-65B, 5.1 g of thioacetic acid, and 20.1 g of acetone was added dropwise over 3 hours. After the dropping, the mixture was stirred at reflux temperature for 3 hours (Step 1). The amount of residual BMA monomer relative to the terminal thioacetate polymer in the obtained solution was 690 mol% (6.9 mol / mol). In order to reduce the amount of residual BMA monomer in the obtained solution to 40 mol% or less by a general crystallization operation, three operations were required.
A solution of 13.8 g without crystallization operation and 4.2 g of ethanol were placed in a reaction vessel and heated at 40 ° C. NaOH ethanol solution (NaOH 0.15 g, ethanol 2 g) was added thereto, and the mixture was heated and stirred at 40 ° C. for 1 hour. After heating, an ethanol solution of citric acid (citric acid 0.2384 g, ethanol 2 g) was added for neutralization (step 3). The decomposition rate of the terminal thioacetic acid ester polymer was determined by the above method, and it was confirmed that it was 100%, that is, a solution that was a reaction mixture containing a polymer having a thiol group at the terminal was obtained.
The reaction vessel was charged with 46.6 g of ethanol and heated at 82 ° C. with stirring. When the reflux temperature was reached, a mixed solution of DMAEMA 52.5 g, BMA 38.0 g, V-65B 0.24 g, the resulting solution 22.39 g, and ethanol 8 g was added dropwise over 1 hour. During this time, the internal temperature was kept at 80 ° C. After completion of dropping, the mixture was heated and stirred at 80 ° C. for 1 hour to obtain a solution containing a block polymer (Step 4).
When the obtained solution was dried and analyzed using LC, the block polymer ratio was 0.67 wt / wt.

<Comparative Example 2>
47.0 g of acetone was placed in the reaction vessel and heated to 56 ° C., the reflux temperature, with stirring. When the reflux temperature was reached, a mixed solution of 94.9 g of BMA, 0.62 g of V-65B, 5.1 g of thioacetic acid, and 20.1 g of acetone was added dropwise over 3 hours. After dropping, the mixture was stirred at reflux temperature for 3 hours (Step 1).
Then, it dried under reduced pressure at 80 degreeC for 6 hours. The amount of residual BMA monomer with respect to the terminal thioacetate polymer in the obtained solid was 42 mol% (0.42 mol / mol) (step 2).
The obtained solid 10 g and ethanol 8 g were put in a reaction vessel and heated at 40 ° C. NaOH ethanol solution (NaOH 0.15 g, ethanol 2 g) was added thereto, and the mixture was heated and stirred at 40 ° C. for 1 hour. After heating, an ethanol solution of citric acid (citric acid 0.2384 g, ethanol 2 g) was added for neutralization (step 3). The decomposition rate of the terminal thioacetic acid ester polymer was determined by the above method, and it was confirmed that it was 100%, that is, a solution that was a reaction mixture containing a polymer having a thiol group at the terminal was obtained.
The reaction vessel was charged with 46.6 g of ethanol and heated at 82 ° C. with stirring. When the reflux temperature was reached, a mixed solution of DMAEMA 52.5 g, BMA 38.0 g, V-65B 0.24 g, the resulting solution 22.39 g, and ethanol 8 g was added dropwise over 1 hour. During this time, the internal temperature was kept at 80 ° C. After completion of dropping, the mixture was heated and stirred at 80 ° C. for 1 hour to obtain a solution containing a block polymer (Step 4).
When the obtained solution was dried and analyzed using LC, the block polymer ratio was 0.93 wt / wt.

<Comparative Example 3>
A solution was obtained in the same manner as in Example 1 except that the acetone solvent in Example 1 was changed to ethanol. When the obtained solution was dried and analyzed using LC, the block polymer ratio was 0.63 wt / wt.

[Test Example 1: Static contact angle evaluation]
Each polymer was betaned by the following method, and then the contact angle was measured.
(Betaine)
A reaction vessel was charged with 5.2 g of CHPS, 6.0 g of the polymer of Example or Comparative Example, 24 g of TFE, and 12 g of ion-exchanged water, and heated at 82 ° C. for 10 hours with stirring. Thereafter, 0.95 g of CHPS and 0.39 g of sodium carbonate were added and heated at 82 ° C. for 10 hours. After completion of the reaction, the solution was dropped into acetone and reprecipitated, and then dried under reduced pressure at 80 ° C. for 12 hours to obtain a betaine test polymer.

(Contact angle measurement)
Each component was blended according to the following formulation, and stirred at 25 ° C. for 30 minutes to prepare a test polymer treatment solution. About the compounding quantity of the following test component, the compounding quantity as each effective part is shown. Apply the test polymer treatment solution onto a polyvinyl chloride substrate (PVC) (1.0 × 25 × 75 mm, manufactured by Engineering Test Service) that has been washed with ethanol and dried, and then left for 20 seconds, and then rinsed with ion-exchanged water for 20 seconds. It is. After thoroughly drying with a nitrogen flow, the static contact angle was measured with a contact angle measuring device (fully automatic contact angle meter DM-701, manufactured by Kyowa Interface Chemical Co., Ltd.). The static contact angle was measured at 10 points with different contact angles after 3, 4, 5, 6 and 7 seconds of 1 μL of water (θ / 2 method), and all average values were taken as contact angle values.

Test polymer treatment liquid formulation Test polymer: 0.3% by mass
Polyoxyethylene (2) ammonium lauryl ether sulfate ^(*) : 0.03 mass%
Diethylene glycol monobutyl ether ^(**) : 2.5% by mass
Ion-exchanged water: remainder (total): 100% by mass
(*) ES-125A: manufactured by Kao Corporation, effective 25% by mass, ethylene oxide average added mole number 2
(**) BDG-NS: Nippon Emulsifier Co., Ltd., effective content 99.71% by mass
Table 1 summarizes the conditions of the examples and comparative examples and the measurement results of the contact angles.

  From the results in Table 1, a polymer having a high block polymer ratio is obtained by the production method of the present invention in which the reaction is carried out in an organic solvent having a ketone structure and the residual monomer is reduced. It can be seen that the performance of reducing the target contact angle is excellent.

Claims (5)

The manufacturing method of a block polymer including the following processes 1-4.
Step 1: A monomer capable of radical polymerization (hereinafter referred to as a first monomer) is polymerized in an organic solvent having a ketone structure in the presence of a thiocarboxylic acid and a polymerization initiator, and includes a polymer having a thiocarboxylic acid ester at the terminal. Step 2 for obtaining a reaction mixture Step 2: Step 3 for reducing the residual amount of the first monomer in the reaction mixture obtained in Step 1 to 40 mol% or less with respect to the polymer having a terminal thiocarboxylic acid ester. Decomposing the thiocarboxylic acid ester group of the polymer in the reaction mixture obtained in step 2 into a thiol group to obtain a reaction mixture containing a polymer having a thiol group at the end Step 4: Reaction obtained in step 3 A process for obtaining a block polymer by reacting the mixture with a further radically polymerizable monomer (hereinafter referred to as a second monomer).   The method for producing a block polymer according to claim 1, wherein the first monomer is a monomer selected from acrylic acid esters, methacrylic acid esters, acrylic acid amides, and methacrylic acid amides.   The method for producing a block polymer according to claim 1 or 2, wherein the organic solvent having a ketone structure is an organic solvent selected from acetone and methyl ethyl ketone.   The method for producing a block polymer according to any one of claims 1 to 3, wherein the remaining amount of the first monomer in the reaction mixture obtained in Step 1 is reduced by drying under reduced pressure or by passing off in Step 2. . The method for producing a polymer according to any one of claims 1 to 4, wherein the second monomer is an unsaturated monomer having an amino group and includes the following step 5.
Step 5: Step of reacting the block polymer obtained in Step 4 with a betaine agent