JPH05230149A - Vinyl copolymer - Google Patents

Abstract

PURPOSE:To provide the title copolymer which includes the units from an uncrosslinkable vinyl monomer and specific units, has excellent antimicrobial activity and high safety of high durability and dissolves in an organic solvent. CONSTITUTION:The objective copolymer includes (A) the units derived from an uncrosslinkable vinyl monomer (for example, styrene or methyl methacrylate) and (B) the units of the formula (R<1> is H, methyl; A is phenylene; R<2> is 1 to 4 C alkylene; Y, Z are anions; R<3> is 6 to 18C alkyl; R<4> is 4 to 10 C alkylene; R<5> to r<8> are 1 to 3 C alkyl). The copolymer is preferably prepared by copolymerization of a 1-2C-haloalkylstyrene and an uncrosslinkable monomer which is copolymerizable with the haloalkyl-styrene followed by reaction of the halogen atoms in the haloalkyl groups with a quaternary ammonium compound. The 1 to 2C haloalkylstyrene is preferably p-chloromethylstyrene.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl-based copolymer having excellent bactericidal activity, high safety, and long-lasting efficacy, such as tap water, cooling water, Slime control, pool, fishing net, ship bottom, underwater structure, food packaging, building materials, agricultural materials, medical products, oral materials (toothbrush, toothpaste, etc.), eyeglass frames, cosmetics, clothing and household items, etc. Can be used.

[0002]

2. Description of the Related Art Among conventional antibacterial compounds, low molecular weight compounds are used by being mixed with materials constituting various products, so that the active ingredient having antibacterial property is eluted to the outside,
Along with this, there are problems such as a decrease in antibacterial activity and toxicity to a living body in contact with the product.

On the other hand, development of polymers having antibacterial properties has been under way to solve these problems. Examples of known antibacterial polymers include polymers represented by the general formula [Chemical Formula 2] (JP-A-61-100254). However, the antibacterial property of the polymer is not sufficiently satisfactory, and there is a problem that the production of the polymer is difficult and thus the production cost is high.

[0004]

[Chemical 2]

[In the formula, X _{1 s} are the same or different and each represents a methyl group or an ethyl group. X ₂ represents an alkyl group having 3 to 30 carbon atoms. A represents a phenylene group. ]

A homopolymer of a monomer represented by the general formula [Chemical Formula 3] or a copolymer of the monomer and divinylbenzene which is a crosslinkable monomer is also known as an antibacterial polymer (Japanese Patent Laid-Open No. 64-26610). .. However, since the polymer is insoluble in an organic solvent, there is a problem in that the inherent performance of the polymer is not sufficiently exhibited because it is not uniformly dispersed and / or agglomerates during processing such as film forming. Furthermore, the polymer (especially homopolymer) has many chlorine atoms remaining in its molecule,
It was found that there are problems with respect to human safety and stability of the polymer itself.

[0007]

[Chemical 3]

[In the formula, A is the same as above, R ⁹ is carbon number 6
~ 18 alkyl group, R ¹⁰ represents an alkylene group having 2 to 10 carbon atoms. Y ₁ and Y ₂ may be the same or different anions, and Y ₁ and Y ₂ may each be a monovalent anion or (Y ₁ , Y ₂ ) may be a divalent anion. ]

[0009]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a vinyl-based copolymer which has excellent antibacterial activity and safety, can maintain its effect for a long period of time, and can be dissolved in an organic solvent. To provide a coalesce.

[0010]

The present invention relates to a vinyl-based copolymer containing a structural unit derived from a non-crosslinkable vinyl monomer and a structural unit represented by the general formula [Chemical Formula 1].

[0011]

[Chemical 1]

[Wherein R ¹ represents a hydrogen atom or a methyl group,
Represents a phenylene group, R ² represents an alkylene group having 1 to ² carbon atoms, Y and Z may be the same or different anions, and Y and Z are each a monovalent anion or (Y, Z).
May be one divalent anion. R ³ has 6 carbon atoms
To 18 alkyl groups, R ⁴ is an alkylene group having 4 to 10 carbon atoms, and R ^{5 to} R ⁸ may be the same or different and have 1 carbon atom.
To 3 alkyl groups, and each may contain a substituent. ]

The present invention will be described in detail below.

In the general formula (I) of the present invention, the alkyl group represented by R ³ has a carbon number of 6-18.
From the viewpoint of antibacterial activity, 10, 12, 14 are more preferable. Further, in the general formula (I) of the present invention, the alkylene group of R ⁴ preferably has 4 to 6 carbon atoms from the viewpoint of antibacterial activity.
The anion is not particularly limited, and Br ⁻ , Cl ⁻ ,
Including I ⁻ , NO ₃ ⁻ , CH ₃ COO ^−, SO ₄ ^{2− and the} like.

The number average molecular weight Mn of the copolymer of the present invention is 2,0.
00 to 1,000,000, preferably 5,000 to 100,000, Mw / Mn
= 1.1 to 2.0 (Mw is a weight average molecular weight) is desirable.

The content of the structural unit (I) in the polymer compound of the present invention is 0.001 to 99.0 mol%, preferably 1 to 50 mol%, and particularly preferably 10 to 30 mol%.

The copolymer of the present invention is obtained by copolymerizing a halo (C _1-2 ) alkylstyrene with a non-crosslinkable vinyl monomer which can be copolymerized to form a copolymer, and then the halogen atom of the haloalkyl group. By introducing the quaternary ammonium salt.

As the halo (C _1-2 ) alkylstyrenes used in the present invention, p-chloromethylstyrene is preferable, but it is a halo (C _1-2 ) alkylstyrene derivative having another substituent. You can buy it.

The constitutional unit derived from the non-crosslinkable vinyl monomer used in the present invention is halo (C _1-2 ).
The monomer is not particularly limited as long as it is a monomer copolymerizable with the alkylstyrenes, and known ones can be used. For example, those represented by the general formula [Chemical Formula 4] can be mentioned.

[0020]

[Chemical 4]

[In the formula, R ¹¹ is a hydrogen atom, a halogen atom,
A methyl group or a cyano group is shown. B is a hydrogen atom and has 1 carbon atom
~ 3 alkyl group, cyano group, halogen atom, phenyl group which may have a halogen atom, group -COR ¹² (wherein R ¹² is a hydrogen atom, a hydroxyl group, a halogen atom, a carbon number of 1 to 1).
5 represents an alkoxy group, a phenoxy group, an amino group or a phenyl group), a group —OCOR ¹³ (wherein R ¹³ is a hydrogen atom,
A hydrogen atom of an alkyl group represents an alkyl group or a phenyl group having 1 to 5 carbon atoms which may be substituted with one or more halogen atoms), —O—R ¹⁴ (wherein R ¹⁴ has 1 to 5 carbon atoms). an alkyl group), group -S-R ¹⁴ (wherein R ¹⁴ is the same), - a N = C = O or a nitrogen atom showing a heterocyclic group containing at least one. ]

Specific examples of the non-crosslinkable vinyl monomer from which the structural unit is derived include styrene, p-methylstyrene, p-bromostyrene, p-chlorostyrene,
Styrene-based monomers such as α-chlorostyrene and α-bromostyrene; acrylic ester-based monomers such as methyl acrylate, ethyl acrylate, lauryl acrylate, and α-chloromethyl acrylate; methyl methacrylate, ethyl methacrylate, methacryl Methacrylate ester monomers such as propyl acid, butyl methacrylate, lauryl methacrylate; vinyl ester monomers such as vinyl acetate, vinyl trifluoroacetate, vinyl butyrate, vinyl benzoate; vinyl chloride, vinyl fluoride, vinylidene chloride, and foot Vinyl halide monomers such as vinylidene chloride; vinyl ether monomers such as isobutyl vinyl ether and n-butyl vinyl ether; N-methyl acrylamide, N-ethyl acrylamide, N-methyl methacrylamide, N-ethyl N-alkyl-substituted (meth) acrylamides such as tacrylamide; nitrile-based monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; olefin-based monomers such as ethylene, propylene and isobutylene; alkyl vinyl sulfides and the like. Vinyl sulfide-based monomers; nitrogen-containing heterocyclic monomers such as N-vinylcarbazole, 4-vinylpyridine, N-vinylpyrrolidone; vinylketone-based monomers such as methyl vinyl ketone, phenyl vinyl ketone; acrolein, acrylic acid chloride, vinyl isocyanate, etc. Is mentioned. These monomers can be used alone or in combination of two or more.

Examples of constitutional units other than the above include, for example, maleic acid, maleic anhydride, cyclohexene, acenaphthylene, norbornene, sulfur dioxide, ethylene oxide, epichlorohydrin, allene, butadiene, isoprene, chloroprene, 2,5-dimethyl-2, Mention may be made of constitutional units derived from non-crosslinkable vinyl monomers such as 4-hexadiene.

The blending molar ratio for copolymerizing the haloalkylstyrene and the non-crosslinkable copolymerized vinyl monomer is usually
0.001 to 99.0: 99.999 to 1.00, preferably 1 to 50: 9
It is about 9 to 50.

As the copolymerization method, conventionally known bulk polymerization, solution polymerization, suspension polymerization and the like can be used.

Next, an example of a method for producing the copolymer of the present invention is shown by a reaction formula. In the formula, X represents a halogen atom.

[0027]

[Chemical 5]

[0028]

[Chemical 6]

[0029]

[Chemical 7]

The polymerization of the above [Chemical formula 5] can be carried out by ordinary methods such as suspension polymerization, solution polymerization and bulk polymerization, and the obtained polymer (PCS) is purified by a method such as reprecipitation and washing. You can In [Chemical Formula 6], the compound (TEMD
A) is usually reacted in an amount of about 1.0 to 2.5 times, preferably about 1.1 to 2.1 times the molar amount of the compound (H). The reaction is preferably carried out in an organic solvent, generally a reaction temperature of about 60 to 110 ° C. being suitable. The product (TQ) is washed, filtered,
It can be purified by a method such as extraction or centrifugation. In the reaction of [Chemical Formula 7], the amount of the compound (TQ) is usually about 1 equivalent to 1 equivalent of the chloromethyl group of the polymer (PCS).
It is preferable to react 0.1 to 2.0 equivalents, preferably about 1.0 to 1.2 equivalents. The reaction is preferably carried out in an organic solvent, generally a reaction temperature of about 60-100 ° C is suitable. Product (P
S-TD) can be purified by a method such as reprecipitation and washing.

The alkyl halide has 6 to 18 carbon atoms.
Alkyl halides such as chlorine, bromine or iodine are used.

As the alkyldiamine, for example, N, N,
N ', N'-tetramethylethylenediamine, N, N, N',
N'-tetramethyl-1,3-propanediamine, N, N,
N ', N'-tetramethyl-1,4-butanediamine, N, N,
N ', N'-tetramethyl-1,5-pentanediamine, N,
N, N ', N'-tetramethyl-1,6-hexanediamine,
N, N, N ', N'-tetraethylethylenediamine, N,
N, N ', N'-tetramethyl-1,3-propanediamine,
N, N, N ', N'-tetraethyl-1,4-butanediamine,
N, N, N ', N'-tetraethyl-1,5-pentanediamine, N, N, N', N'-tetraethyl-1,6-hexanediamine and the like are used.

The obtained copolymer is subjected to ion exchange in accordance with a known method, and the counter anions are Cl ⁻ , Br ⁻ ,
It can be I ⁻ , NO ₃ ⁻ , NO ₂ ⁻ , SO ₄ ²⁻ , CH ₃ COO ^−, or the like.

Since the copolymer of the present invention uses a copolymer of chloroalkylstyrenes and a non-crosslinkable vinyl monomer as a raw material, it is superior to the one using a homopolymer of chloroalkylstyrenes in the following points. There is.

That is, when the quaternary ammonium salt is introduced by using the copolymer, the unreacted chloroalkyl residue is smaller than that in the case of using the homopolymer, so that the physical properties are stable and the human body is safe. It has excellent properties. Moreover, by copolymerizing with a non-crosslinkable vinyl monomer that is cheaper than chloroalkylstyrenes,
The manufacturing cost can be reduced.

When the copolymer of the present invention is used, one or more of the above-mentioned active ingredient polymers may be mixed and used.

The copolymer of the present invention can be in the form of powder, granules, fibers, films or the like depending on the method for producing the polymer.

When the copolymer of the present invention is used, for example, as an active ingredient of an antibacterial composition, its use is as tap water, cooling water, slime control, pool, fishing net, ship bottom, underwater structure, food packaging material, It is widely used in building materials, agricultural materials, medical products, oral materials (toothbrush, toothpaste, etc.), eyeglass frames, cosmetics, clothing and household items.

In using the above-mentioned antibacterial composition, a known method can be used. For example, when the surface of an object is subjected to antibacterial treatment, one or more of the above polymers may be dissolved in a suitable solvent and treated by a dipping method or a spray method. At that time, a known polymer may be mixed and used.

The object for which the antibacterial composition can be used is, specifically, a synthetic polymer in any form,
For example polypropylene, polyethylene, polystyrene,
Natural polymers such as polyester, polyamide, polyacrylate, polyurethane, polyvinyl chloride, etc., such as cotton, wool, feathers, hemp, silk, paper, rubber, etc.
Further, wood, glass, metal, ceramic products and the like can be mentioned.

The form of these objects may be a molded product or a raw material. For example, the antibacterial treatment can be carried out in a thread shape, a fiber shape, a film shape, a sheet shape, a granular shape, a powder shape, or the like.

The copolymer of the present invention can impart antibacterial properties to these substances with high safety and excellent antibacterial activity for a long period of time.

When the antibacterial composition is used, it is generally methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, N, N-dimethylformamide, N, N-dimethylacetamide. It is preferably dissolved in dimethylsulfoxide or the like, or dissolved in a mixed solvent of these solvents and acetone, tetrahydrofuran, benzene, toluene, xylene and the like for use. It is dissolved so that the concentration is 0.01 to 2.0% by weight, preferably 0.1 to 1.0% by weight. The substance to be imparted with antibacterial property is dipped in this solution, or the solution is applied to the surface by a method such as spraying the substance and then dried to remove the solvent. The drying temperature is 0 to 80 ° C, preferably
It is desirable to dry in a drying room at 20 to 60 ° C for 10 to 48 hours.

Further, the antibacterial composition is also excellent in antifouling property in water. When the antibacterial composition is used for antifouling in water, it can be mixed and used with a known film-forming composition, and at that time, a known antifouling component-containing substance can be added.

When the antibacterial composition is used for antifouling underwater, specifically, it can be used for, for example, fishing nets, ship bottoms, cooling water pipes, buoys, dam gates, water tanks for aquaculture facilities, underwater structures, etc. It has an excellent effect of preventing the adhesion of Aonori, Hiraaoori, Aosanori, and barnacles.

When the antibacterial composition is used for antifouling in water, as a solvent, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, N, N-dimethylformamide, dimethyl sulfoxide are generally used. It is desirable to dissolve them in, or to use them in a mixed solvent system of these solvents and benzene, toluene, xylene and the like. As a method of use, a known method can be used.

The known antifouling component-containing substance that can be used as a mixture with the antibacterial composition is not particularly limited, and examples thereof include a copper compound, a dithiocarbamate compound, a phenolsazine compound and a quaternary compound. Examples thereof include ammonium salt compounds. Further, a cross-linking agent having antifouling activity, a filler, a monomer, a polymer and the like can be used in mixture.

Any known coating film-forming composition that can be used in combination with the antibacterial composition may be used, for example, acrylic acid resin-based, phthalic acid resin-based, aminoalkyd resin-based compositions. , Synthetic resin emulsion type and lacquer.

[0049]

Industrial Applicability According to the present invention, it is possible to provide a copolymer which is highly safe, has excellent antibacterial properties, and can maintain its effect over a long period of time.

The present invention can be applied to tap water, cooling water, slime control, pool, fishing net, ship bottom, underwater structure, food packaging material, building material, agricultural material, medical product, oral material (toothbrush,
It can be used in a wide range of applications such as toothpaste), eyeglass frames, cosmetics, clothing and household items.

[0051]

[Examples] Hereinafter, examples and test examples will be described in detail.

Example 1 230.8 g (1.6 mol) of N, N, N ', N'-tetramethyl-1,4-diaminobutane (hereinafter abbreviated as TMB) was charged into a 1-liter four-necked flask. To this, 342.6 g (1.3 mol) of lauryl bromide (hereinafter abbreviated as LB) was added dropwise from a dropping funnel under stirring at 75 ° C. over 1 hour, and the reaction was further continued under the same conditions for 1 hour. After completion of the reaction, the white wax-like reaction mixture was washed with n-hexane three times, and unreacted TMB was removed by decantation. The white precipitate layer was separated by a centrifuge to obtain a white paste. From TLC and ¹ H-NMR,
N, N, N ', N'-tetramethyl-1,4-diaminobutane-
N- lauryl bromide (hereinafter abbreviated as TMQ-C ₄₎ and N, N, N ', N'- tetramethyl-1,4-diaminobutane -
N, N′-dilauryl dibromide (hereinafter TMQQ-C ₄
Abbreviated).

After heating and drying the mixture under vacuum, 380 g of a white waxy substance was obtained. From ¹ H-NMR, this product was TMQ-C ₄ / TMQQ-C ₄ = 26.3 wt% / 73.7 wt%.

Then, p-chloromethylstyrene (abbreviated as CS) and styrene (abbreviated as ST) were prepared by solution polymerization according to a conventional method.
A copolymer (hereinafter abbreviated as PCS) through a copolymerization reaction with
Was generated. The obtained PCS was reprecipitated with tetrahydrofuran / methanol to remove unreacted monomers.

Next, the total halogen quantitative analysis and elemental analysis were carried out on the PCS by the oxygen flask combustion method, and as a result, CS / ST in PCS was 3/7 (molar ratio).

8.4 g of the obtained PCS was dissolved in THF,
Charge into a 00 ml four-necked flask and add TMQ- from the dropping funnel.
A solution of 35.9 g of C ₄ / TMQQ-C ₄ mixture in acetone was added to
The solution was added dropwise at -50 ° C with stirring for 1 hour.

After the addition, the reaction was continued for 20 hours under the same conditions, and the reaction mixture was reprecipitated in water. Then, the obtained polymer was dissolved in methanol, and reprecipitation was repeated twice in water.

After re-precipitation, heating and vacuum drying were performed to obtain 12.6 g of a white powdery polymer (hereinafter referred to as PCS-1).

The PCS-1 was confirmed to be the desired product by elemental analysis, TLC, IR and ¹ H-NMR.

GP containing polystyrene as a standard substance
When the number average molecular weight of PCS-1 was determined by C, Mn was 20000 and the polydispersity was Mw / Mn = 1.45.

From the total halogen content by oxygen flask combustion method (analysis chemistry handbook) and N% by elemental analysis method, PC
Content of quaternary ammonium salt compound in S-1 (hereinafter referred to as Q
AC) and residual chloromethyl groups, that is, the content of unreacted CS (hereinafter abbreviated as UCS),
C = 28.99 mol%, UCS <0.01 mol%.

Examples 2 to 3 In place of LB of Example 1, 251.1 g of n-octyl bromide (hereinafter abbreviated as OB) or 432.8 g of stearyl bromide (hereinafter abbreviated as SB) was used, respectively. Method, N, N, N ′, N′-tetramethyl-1,4
-Diaminobutane-N-octyl bromide (hereinafter TM
Abbreviated as O-C ₄₎ and N, N, N ', N'- tetramethyl-1,4
- diaminobutane -N, mixture 290g and N N'- dioctyl dibromide (hereinafter referred to as TMOO-C _4), N,
N ′, N′-tetramethyl-1,4-diaminobutane-N-stearyl bromide (hereinafter abbreviated as TMS-C ₄ ) and N,
N, N ', N'-tetramethyl-1,4-diaminobutane-N,
N'- distearyl dibromide to obtain a mixture 411g (hereinafter referred to as TMSS-C _4).

The mixture ratio of each mixture was determined in the same manner as in Example 1. TMO-C ₄ / TMOO-C ₄ = 49.5 wt% / 50.5 wt% TMS-C ₄ / TMSS-C ₄ = It was 31.0 wt% / 69.0 wt%.

Next, TMQ-C ₄ / TMQQ-of the first embodiment
Instead of the C ₄ mixture, it is reacted with _{TMO-C 4 / TMOO-C} 4 mixture 8.9g and _{TMS-C 4 / TMSS-C} 4 mixture 20.0g as in Example 1 using a PCS, a white powder polymer 9.7 g and 14.8 g were obtained (hereinafter referred to as PCS-2 and PCS-3, respectively).

The PCS-2 and PCS-3 are the same as those in Example 1.
It was confirmed to be the target product by the same method as described in.

The number average molecular weight and polydispersity were PCS-2 Mn = 21000 Mw / Mn = 1.22 PCS-3 Mn = 26000 Mw / Mn = 1.27, respectively.

Further, when QAC and UCS were determined by the same method as in Example 1, it was found that PCS-2 QAC = 29.14 mol% CS <0.01 mol% PCS-3 QAC = 28.92 mol% CS <0.01 mol% It was

Examples 4 to 5 275.7 g (1.6 mol) of N, N, N ', N'-tetramethyl-1,6-diaminohexane (hereinafter abbreviated as TMH) or N, N in place of TMB in Example 1 N, N ', N'-tetramethyl-1,10-diaminodecane (hereinafter abbreviated as TMD) 36
Using 4.8 g (1.6 mol), synthesis was carried out in the same manner as in Example 1 to obtain 267.2 g of a white waxy substance and
353.6 g was obtained. ^{From 1} H-NMR, these substances show that N,
N, N ', N'-tetramethyl-1,6-diaminohexane-
And N- lauryl bromide _{(TMQ-C 6), N} , N,
N ', N'-tetramethyl-1,6-diaminohexane-N,
Mixture of N'- dilauryl dibromide (TMQQ-C ₆₎ or N, N, N ', N'- tetramethyl-1,10-diaminodecane -N- lauryl bromide (TMQ-C ₁₀₎
And N, N, N ′, N′-tetramethyl-1,10-diaminodecane-N, N′-dilauryl dibromide (TMQQ-C
_{It was} a mixture of ₁₀ ).

[0069] Each composition ratio of the mixture _{TMQ-C 6 / TMQQ-C} 6 = 53.7wt% / 46.3wt% TMQ-C 10 / TMQQ-C 10 = 40.8wt% / Atsuta at 59.2wt%.

In Example 1, TMQ-C ₄ / TMQ
Instead of Q-C _{4 mixture, TMQ-C 6 / TMQQ-} C 6
21.0 g of the mixture or 39.0 g of TMQ-C ₁₀ / TMQQ-C ₁₀ mixture was used and reacted with PCS in the same manner as in Example 1. As a result, a white powdery polymer (hereinafter PCS-4 and P
CS-5) was obtained in an amount of 20.6 g and 33.1 g, respectively.

The number average molecular weight and polydispersity index of the polymer were PCS-4 Mn = 22000 Mw / Mn = 1.55 PCS-5 Mn = 19000 Mw / Mn = 1.43.

Both PCS-4 and PCS-5 are
By the same method as in Example 1, it was confirmed to be the target product.

In addition, QAC and U are processed in the same manner as in the first embodiment.
When CS was calculated, PCS-4 QAC = 28.88 mol% UCS <0.01 mol% PCS-5 QAC = 29.01 mol% UCS <0.01 mol%.

Example 6 In a reaction for obtaining a copolymer from CS and ST by a conventional solution polymerization, 4.5 g (0.03 mol) of CS and 80.1 g (0.77
(Mol) in THF with 0.6 g (0.004 mol) of AIBN as an initiator and stirring at 60 ° C. for 16 hours in an N ₂ atmosphere with stirring, and then reprecipitating with THF / methanol to give a white powder polymer. (Hereinafter referred to as PCS-M) 72.2g
Got

PCS-M was analyzed in the same manner as in Example 1. As a result, the copolymerization composition of PCS-M was CS / ST = 4.
It was 3 / 95.7 (molar ratio).

For the PCS-M, the molecular weight was determined by the same measurement method as in Example 1. The number average molecular weight Mn = 1300
The polydispersity was Mw / Mn = 1.65.

12.5 g of PCS-M and the T obtained in Example 1
9.0 g of the MQ-C ₄ / TMQQ-C ₄ mixture was reacted in 400 ml of THF at 80 ° C. for 21 hours with stirring. After completion of the reaction, the reaction mixture was repeatedly reprecipitated 3 times in water and then dried under heating and vacuum.

15.6 g (PCS of the obtained white powder polymer)
It was confirmed by the same method as in Example 1 that the product was designated as -6).

PCS-6 has Mn = 192000 and Mw / Mn =
It was 1.51. Further, in the same manner as in the first embodiment, QAC and U
When CS was calculated, QAC = 3.02 mol%, UCS <0.01
It was mol%.

Example 7 In the conventional reaction for obtaining a copolymer from CS and ST, C
S 76.3g (0.50mol) and ST 156.0g (1.50mol) T
In HF, using AIBN 0.3 g (0.002 mol) as an initiator
After reacting at 50 ° C. for 24 hours under N ₂ atmosphere while stirring, the reaction product was reprecipitated with THF / methanol to obtain 185.8 g of a white powder polymer (PCS-H).

PCS-H was analyzed by the same method as in Example 1, and as a result, the copolymer composition was CS / ST = 29/71 (molar ratio).

The molecular weight of PCS-H was determined by the same measurement method as in Example 1. The number average molecular weight Mn = 8800.
The polydispersity was 00 and the polydispersity was Mw / Mn = 1.73.

Instead of PCS-M of Example 6, PCS-
As a result of carrying out the same conditions as in Example 5 below using 12.9 g of H, 14.9 g of a white powder polymer (referred to as PCS-7) was obtained.

It was confirmed that the PCS-7 was the desired product in the same manner as in Example 1. PCS-7 has Mn = 95
It was 0000 and Mw / Mn = 1.72. Further, when QAC and UCS were obtained by the same method as in Example 1, QAC = 27.8
9 mol%, UCS <0.01 mol%.

Example 8 White powder polymer PCS-1 (10.
0 g) was dissolved in 2 liters of a mixed solvent of methanol / water = 1/4 (volume ratio), 200 g of anhydrous sodium acetate was added, and the mixture was stirred at room temperature for 2
Stirring was continued for 4 hours. The colorless transparent homogeneous solution was concentrated and dried, and the obtained white powder polymer was dissolved in 300 ml of chloroform, and the sodium salt was filtered off. The chloroform solution of the filtrate was concentrated, heated and dried under vacuum overnight, and crushed in a mortar. The white powder polymer thus obtained (hereinafter PCS-
8)) 10.2 g is the result of ¹ H-NMR, IR, elemental analysis and total halogen quantitative analysis by oxygen flask combustion method showing that the counter ion of the quaternary ammonium salt was replaced with CH ₃ COO ⁻ from the halogen ion. I confirmed that.
The replacement rate of halogen ions to CH ₃ COO ⁻ is 95.6.
% (Equivalent conversion).

Example 9 In Example 1, ethyl acrylate (EA) was used in place of styrene to carry out a copolymerization reaction with CS to obtain a copolymer PCE.

Instead of PCS in Example 1, PCE
The procedure of Example 1 was repeated except that 8.3 g was used to obtain 11.9 g of a white powder polymer (PCS-9).

It was confirmed that PCS-9 was the desired product by the same method as in Example 1. PCS-9 had a number average molecular weight Mn of 28,000 and a polydispersity Mw / Mn of 1.29. When QAC and UCS were determined by the same method as in Example 1, QAC = 28.88 mol% and UCS <0.01 mol%.

Claims (1)

[Claims] 1. A vinyl copolymer containing a constitutional unit derived from a non-crosslinkable vinyl monomer and a constitutional unit represented by the general formula [Chemical Formula 1]. [Chemical 1] [Wherein R ¹ represents a hydrogen atom or a methyl group, A represents a phenylene group, R ² represents an alkylene group having 1 to ² carbon atoms, Y,
Z is an anion which may be the same or different, and Y and Z may each be a monovalent anion, or (Y, Z) may be one divalent anion. R ³ is an alkyl group having 6 to 18 carbon atoms, R ⁴ is an alkylene group having 4 to 10 carbon atoms, R ^{5 to} R ⁸ may be the same or different, and represent an alkyl group having 1 to 3 carbon atoms, Both may contain a substituent. ]