JP5274269B2 - Method for producing polymer having sulfonic acid group and amide group - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for reducing a production amount of phenol produced as a decomposed product of triphenyl phosphite used as a condensation agent in the production of a polymer having a sulfonic acid group and an amide group. <P>SOLUTION: In the method for producing the polymer including a unit represented by chemical formula (1):-CONH-B1-SO<SB>3</SB>H, a polymer including a unit represented by chemical formula (2):-COOH and at least one amine compound including a sulfonic acid group represented by chemical formula (3): H<SB>2</SB>N-B1-SO<SB>3</SB>H are used together with a triphenyl phosphite and trialkyl phosphite (alkyl is selected from methyl, ethyl and propyl). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a polymer having a sulfonic acid group and an amide group.

  A polymer having a sulfonic acid group is expected to be applied to various uses. And the synthesis | combination of the polymer containing a sulfonic acid group is generally restricted to what uses the specific vinyl monomer containing a sulfonic acid functional group. Specific examples of the monomer include sulfonated styrene or AMPS (2-acrylamido-2-methylpropanesulfonic acid). For example, Patent Document 1 discloses a copolymer of acrylamidomethylpropane sulfonate and another vinyl monomer copolymerizable therewith, or acrylamidomethylpropane sulfonic acid and another copolymerizable with this. A charge control agent comprising a copolymer obtained by treating a copolymer with a vinyl monomer with an alkali agent, and a negatively charged toner for electrophotography using the same are disclosed.

  In addition, the present applicants provide a method for producing a polymer having a sulfonic acid group, a polymer having a sulfonic acid group and an amide group, and a method for producing the same for the purpose of providing a polymer having a sulfonic acid group. And filed a patent application earlier (Patent Document 2). The polymer having a sulfonic acid and an amide group in Patent Document 2 is produced by amidating (condensation reaction) a polymer having a carboxyl group and an amine compound containing a sulfonic acid group with a condensing agent. However, in the above production, triphenyl phosphite used as a condensing agent in the condensation reaction generates phenol as a decomposition product as the reaction proceeds. Since phenol has a boiling point of 181.8 ° C., it is difficult to remove it from the resin using distillation or the like. Therefore, in order to remove phenol from the polymer, a purification step is required using a large amount of an alcohol solvent such as ethanol or methanol. As a result, there was a problem that it took time and cost.

JP 2002-351147 A JP 2005-350667 A

  The present invention has been made in order to solve the above-described problems in the prior art. That is, an object of the present invention is to provide a method for reducing the amount of phenol generated as a decomposition product of triphenyl phosphite used as a condensing agent in producing a polymer having a sulfonic acid group and an amide group. It is to be.

  In order to solve the above-described problems in the prior art, the present inventors diligently studied a method for producing a polymer having a sulfonic acid group and an amide group. As a result, by using a combination of triphenyl phosphite and phosphite triester (the ester is selected from methyl, ethyl, and propyl) as a condensing agent, The inventors have found that a polymer can be produced with a reaction efficiency equivalent to that when triphenyl phosphite is used alone while reducing the amount of generation, and the present invention has been completed.

That is, the present invention provides (i) the following chemical formula ( 2 )

で示される構造を含む重合体と、
（ｉｉ）下記化学式（３）

A polymer having a structure represented by :
(Ii) The following chemical formula ( 3 )

（式中、Ｂ１は置換基を有していてもよい炭素数１又は２のアルキレン構造もしくは置換基を有していてもよい芳香族環を表し、該アルキレン構造における置換基は、水酸基、炭素数１乃至１２のアルキル基、アリール基又はアルコキシ基であり、芳香族環における置換基は、水酸基、炭素数１乃至１２のアルキル基、アリール基又はアルコキシ基であり、また、隣接する炭素を含めて５員環又は６員環の芳香族環を形成していてもよい。）
で示される構造を有するスルホン酸基を含有するアミン化合物とを、
縮合剤として亜リン酸トリフェニルと亜リン酸トリエステル（エステルは、メチル、エチル、プロピルから選択される）とを併用して反応させ、下記化学式（１）

(In the formula, B1 represents an alkylene structure having 1 or 2 carbon atoms which may have a substituent or an aromatic ring which may have a substituent, and the substituent in the alkylene structure is a hydroxyl group or a carbon. The substituent in the aromatic ring is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group or an alkoxy group, including an adjacent carbon. And may form a 5-membered or 6-membered aromatic ring.)
In an amine compound containing a sulfonic acid group with INDICATED the structure,
As a condensing agent, triphenyl phosphite and phosphite triester (the ester is selected from methyl, ethyl, and propyl) are reacted together to give the following chemical formula ( 1 )

（式中、Ｂ１は、化学式（３）におけるＢ１に準ずる。）
で示される構造を有する重合体を得ることを特徴とする重合体の製造方法に関するものである。

(In the formula, B1 conforms to B1 in chemical formula (3).)
It is related with the manufacturing method of the polymer characterized by obtaining the polymer which has a structure shown by these.

  According to the present invention, in the production of a polymer having a sulfonic acid group and an amide group, a polymer containing a carboxyl group and an amine compound containing a sulfonic acid group are used as a condensing agent, triphenyl phosphite and triphosphite. By using in combination with an ester (the ester is selected from methyl, ethyl, propyl), the amount of phenol produced as a decomposition product is reduced and triphenyl phosphite is used alone. The condensation reaction can proceed with a reaction efficiency equivalent to that of Since the amount of triphenyl phosphite used can be reduced as compared with the conventional method, the amount of phenol generated as a decomposition product can be reduced. Therefore, the operation for removing phenol from the polymer can be reduced. Since it can manufacture without a complicated operation in the washing process, the manufacturing cost is greatly reduced, and the manufacturing method is highly useful.

  The present invention is described in detail below.

  The method for producing a polymer having a sulfonic acid group and an amide group according to the present invention has a wide range of chemical formulas (2) below.

で示すユニットを含む重合体に適用することができる。詳しくは、ビニル系重合体、エステル系重合体、エーテル系重合体、アミド系重合体、ウレタン系重合体やウレア系重合体に適用可能である。本発明に適用できる重合体の分子量としては、数平均分子量で１０００乃至１００００００の範囲である。数平均分子量で１０００より小さい場合、重合体中の組成分布が広くなる。そのため重合体中の組成に偏りができるため、反応並びに精製時において再現性がとりにくくなるため、好ましくない。また、数平均分子量で１００００００より大きい場合には、一般に反応時において溶媒に溶解しにくくなるため、好ましくない。

It can apply to the polymer containing the unit shown by. Specifically, the present invention is applicable to vinyl polymers, ester polymers, ether polymers, amide polymers, urethane polymers, and urea polymers. The molecular weight of the polymer applicable to the present invention is in the range of 1,000 to 1,000,000 in terms of number average molecular weight. When the number average molecular weight is less than 1000, the composition distribution in the polymer becomes wide. Therefore, since the composition in the polymer can be biased, it is difficult to obtain reproducibility during reaction and purification, which is not preferable. Moreover, when the number average molecular weight is larger than 1,000,000, it is generally not preferable because it is difficult to dissolve in a solvent during the reaction.

  When the polymer is a vinyl polymer, examples of the unit having a carboxyl group represented by the chemical formula (2) include acrylic acid and methacrylic acid. The polymer in this case may be a homopolymer or a copolymer. When the vinyl polymer containing a unit having a carboxyl group represented by the chemical formula (2) is a copolymer, it is preferably a copolymer with the following vinyl monomer.

  Specifically, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, p Styrene and its derivatives such as n-dodecylstyrene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl acetate , Vinyl ester acids such as vinyl propionate and vinyl benzoate; methacryl Methyl, ethyl methacrylate, propyl methacrylate, methacrylate-n-butyl, isobutyl methacrylate, methacrylate-n-octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethyl methacrylate Α-methylene aliphatic monocarboxylic acid esters such as aminoethyl, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, acrylic acid-n-butyl, acrylic acid-isobutyl, acrylic acid-propyl, acrylic acid-n-octyl, Acrylic esters such as dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether, vinyl ethyl ether Vinyl ethers such as vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone. Compounds; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

  In the case where the polymer is an ester polymer, the ester polymer containing a unit having a carboxyl group represented by the chemical formula (2) includes a polyhydric alcohol component and a polycarboxylic acid component. An ester polymer produced by condensation can be used. The following are mentioned as a polyhydric alcohol component which comprises the polymer containing the said ester structure. Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2 -Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Opentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene It is done.

  Examples of the polyvalent carboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; Examples thereof include succinic acid substituted with an alkyl group having 6 to 12 carbon atoms or anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid, or anhydrides thereof.

  In the method for producing a polymer of the present invention, triphenyl phosphite and phosphite triester (as a condensing agent) using a polymer containing a unit represented by the chemical formula (2) and an amine compound containing a sulfonic acid group. Ester is selected from methyl, ethyl, and propyl)

（式中、Ｂ１は置換基を有していてもよい炭素数１又は２のアルキレン構造もしくは置換基を有していてもよい芳香族環を表し、アルキレン構造における置換基としては、水酸基、炭素数１乃至１２のアルキル基、アリール基又はアルコキシ基であり、芳香族環における置換基としては、水酸基、炭素数１乃至１２のアルキル基、アリール基又はアルコキシ基であり、また、隣接する炭素を含めて５員環又は６員環の芳香族環を形成していてもよい。）
で示すユニットを含む重合体が製造される。

(In the formula, B1 represents an optionally substituted alkylene structure having 1 or 2 carbon atoms or an optionally substituted aromatic ring, and the substituent in the alkylene structure includes a hydroxyl group, carbon An alkyl group, an aryl group or an alkoxy group having 1 to 12 carbon atoms, and the substituent in the aromatic ring is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group or an alkoxy group; Including a 5-membered or 6-membered aromatic ring may be formed.)
The polymer containing the unit shown by is manufactured.

  In the method for producing a polymer of the present invention, an amine compound containing a sulfonic acid group (hereinafter sometimes referred to as an amine compound) used when forming an amide bond is represented by the following chemical formula (3).

（式中、Ｂ１は置換基を有していてもよい炭素数１又は２のアルキレン構造もしくは置喚基を有していてもよい芳香族環を表し、アルキレン構造における置換基としては、水酸基、炭素数１〜１２のアルキル基、アリール基又はアルコキシ基であり、芳香族環における置喚基としては、水酸基、炭素数１乃至１２のアルキル基、アリール基又はアルコキシ基であり、また、隣接する炭素を含めて５員環又は６員環の芳香族環を形成していてもよい。）
で示す化合物が適用できる。具体的には、２−アミノエタンスルホン酸（別称としてタウリンと呼ばれることがある）、２−アミノ−２−メチルプロパンスルホン酸やｐ−アミノベンゼンスルホン酸（別称としてスルファニル酸と呼ばれることがある）、ｍ−アミノベンゼンスルホン酸、ｏ−アミノベンゼンスルホン酸、ｍ−トルイジン−４−スルホン酸、ｐ−トルイジン−２−スルホン酸、４−メトキシアニリン−２−スルホン酸、ｏ−アニシジン−５−スルホン酸、ｐ−アニシジン−３−スルホン酸、２，４−ジメチルアニリン−６−スルホン酸、３，４−ジメチルアニリン−５−スルホン酸、４−イソプロピルアニリン−６−スルホン酸のアミノベンゼンスルホン酸誘導体、１−ナフチルアミン−４−スルホン酸、１−ナフチルアミン−５−スルホン酸、１−ナフチルアミン−６−スルホン酸、１−ナフチルアミン−７−スルホン酸、１−ナフチルアミン−８−スルホン酸、２−ナフチルアミン−１−スルホン酸、２−ナフチルアミン−５−スルホン酸等のナフチルアミンスルホン酸誘導体が挙げられる。これらアミン化合物は単独で使用しても、また複数使用してもよい。アミン化合物の使用量は、所望する化学式（１）のユニット量にもよるが、化学式（２）に示すユニットに対して、０．１乃至５．０倍モル量の範囲である。より好ましくは０．１乃至２．０倍モル量の範囲である。更に好ましくは０．１乃至１．２倍モル量の範囲である。

(In the formula, B1 represents an optionally substituted alkylene group having 1 or 2 carbon atoms or an aromatic ring optionally having a substituent, and the substituent in the alkylene structure includes a hydroxyl group, An alkyl group having 1 to 12 carbon atoms, an aryl group or an alkoxy group, and the anchoring group in the aromatic ring is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group or an alkoxy group, and is adjacent thereto. (It may form a 5-membered or 6-membered aromatic ring including carbon.)
The compound shown by can be applied. Specifically, 2-aminoethanesulfonic acid (sometimes called taurine), 2-amino-2-methylpropanesulfonic acid or p-aminobenzenesulfonic acid (sometimes called sulfanilic acid) , M-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-toluidine-4-sulfonic acid, p-toluidine-2-sulfonic acid, 4-methoxyaniline-2-sulfonic acid, o-anisidine-5-sulfone Aminobenzenesulfonic acid derivatives of acids, p-anisidine-3-sulfonic acid, 2,4-dimethylaniline-6-sulfonic acid, 3,4-dimethylaniline-5-sulfonic acid, 4-isopropylaniline-6-sulfonic acid 1-naphthylamine-4-sulfonic acid, 1-naphthylamine-5-sulfonic acid, 1-naphth And naphthylamine sulfonic acid derivatives such as 1-naphthylamine-7-sulfonic acid, 1-naphthylamine-8-sulfonic acid, 2-naphthylamine-1-sulfonic acid, 2-naphthylamine-5-sulfonic acid, and the like. It is done. These amine compounds may be used alone or in combination. The amount of the amine compound used depends on the desired unit amount of the chemical formula (1) but is in the range of 0.1 to 5.0 times the molar amount relative to the unit represented by the chemical formula (2). More preferably, it is in the range of 0.1 to 2.0 times the molar amount. More preferably, it is in the range of 0.1 to 1.2 times the molar amount.

  In the method for producing a polymer of the present invention, triphenyl phosphite and phosphite triester (ester is selected from methyl, ethyl, propyl) are used as a condensing agent for forming an amide bond. It is used in combination.

  The total amount of triphenyl phosphite and phosphite triester (the ester is selected from methyl, ethyl, propyl) is 0.1 to 10 times the molar amount relative to the unit represented by the chemical formula (2) Range. More preferably, it is in the range of 0.1 to 5.0 times the molar amount. More preferably, it is in the range of 0.1 to 1.2 times the molar amount. The ratio of triphenyl phosphite and phosphite triester (the ester is selected from methyl, ethyl, propyl) is 1 <mole amount of triphenyl phosphite / phosphorous acid in terms of molar amount. The molar amount of acid triester is preferably in the range (ester is selected from methyl, ethyl, propyl). If the amount of triphenyl phosphite used is reduced, the amount of phenol generated is reduced. The amount can be reduced. However, if it is less than 1, the reaction rate is greatly reduced, and the desired polymer may not be obtained, which is not preferable.

  In the method for producing a polymer of the present invention, a solvent can be used as necessary. Solvents used include hydrocarbons such as hexane, cyclohexane and heptane, ketones such as acetone and methyl ethyl ketone, ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and the like. Examples include halogenated hydrocarbons, aromatic hydrocarbons such as benzene and toluene, aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, and N, N-dimethylacetamide, and pyridine derivatives. Particularly preferably, N, N-dimethylacetamide and pyridine are used.

  In the method for producing a polymer of the present invention, the amide bond is preferably formed under an inert atmosphere such as nitrogen.

  In the method for producing a polymer of the present invention, the reaction temperature at the time of forming an amide bond is not particularly limited, but it is usually carried out in the range of 0 ° C. to the boiling point temperature of the solvent. In the method of the present invention, the reaction time is usually in the range of 1 to 48 hours, preferably in the range of 1 to 10 hours. An excessively long reaction time is not preferable because it reduces the production efficiency.

  In the method for producing a polymer of the present invention, the reaction mixture containing the produced polymer having a unit represented by the chemical formula (1) includes water, alcohols such as methanol and ethanol, ethers such as dimethyl ether, diethyl ether, and tetrahydrofuran. It can be recovered and purified by mixing with a solvent that is uniform in the reaction solution and insoluble in the produced polymer, and reprecipitating using a solvent such as.

  According to the present invention, triphenyl phosphite and phosphite triester (the ester is selected from methyl, ethyl, propyl) are used in combination as a condensing agent to produce a decomposition product. Reduces the amount of phenol generated. Therefore, the amount of phenol contained in the recovered and purified polymer can be reduced under the same washing conditions as compared with the case of using conventional triphenyl phosphite alone. Therefore, since it can manufacture without complicated operation in a washing | cleaning process, the manufacturing cost is reduced significantly and it is a highly useful manufacturing method.

  EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In addition, all the parts used in an Example show a mass part.

  The measurement method used in the present invention will be described below.

<Molecular weight of polymer>
The molecular weight and molecular weight distribution of the polymer produced according to the present invention can be calculated and calculated in terms of polystyrene by gel permeation chromatography (GPC).

  The polymer is added to THF (tetrahydrofuran), and the solution which is allowed to stand at room temperature for 24 hours is filtered through a solvent-resistant membrane filter having a pore diameter of 0.2 μm to obtain a sample solution, which is measured under the following conditions. In addition, sample preparation adjusts the quantity of THF so that the density | concentration of a polymer may be 0.4-0.6 mass%.

Apparatus: High-speed GPC HLC8120 GPC (manufactured by Tosoh Corporation)
Column: Shodex KF-801, 802, 803, 804,
Seven series of 805, 806, 807 (made by Showa Denko KK)
Eluent: Tetrahydrofuran Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the polymer, a standard polystyrene resin (TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F, manufactured by Tosoh Corporation) was used. -10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500) are used.

<Acid value of polymer>
The acid value of the polymer produced according to the present invention is determined by the following method.
Basic operation is based on JIS K-0070.
1) Weigh precisely 0.5 to 2.0 g of the pulverized polymer. The mass at this time is defined as W (g).
2) Put the sample in a 300 ml beaker, and add 150 ml of a toluene / ethanol (4/1) mixture to dissolve.
3) Perform titration using a 0.1 mol / l ethanol solution of KOH using a potentiometric titrator (for example, a potentiometric titrator AT-400 (winworkstation) manufactured by Kyoto Electronics Co., Ltd.) and an ABP-410 electric burette. Automatic titration using can be used.)
4) The amount of KOH solution used at this time is S (ml). At the same time, a blank is measured, and the amount of KOH used at this time is defined as B (ml).
5) Calculate the acid value according to the following formula. f is a factor of KOH.
Acid value (mgKOH / g) = {(SB) × f × 5.61} / W

<Composition analysis>
The structure of the polymer produced according to the present invention was determined using the following apparatus.
¹ H-NMR, ¹³ C-NMR
FT-NMR JNM-EX400 manufactured by JEOL (solvent: heavy chloroform)

<Quantification of phenol content>
The amount of phenol remaining in the polymer produced according to the present invention is measured by gas chromatography (GC) as follows.

  About 500 mg of the polymer composition is accurately weighed and placed in a sample bottle. To this, about 15 g of acetone precisely weighed is added, the lid is capped, and then mixed well to dissolve uniformly. Thereafter, filtration is performed using a solvent-resistant membrane filter “Maesori Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm, and 2 μl of the filtrate is analyzed by gas chromatography. Then, the residual amount of residual phenol is calculated using a calibration curve prepared in advance using phenol.

The measurement apparatus and measurement conditions are as follows.
GC: HP 6890GC
Column: HP INNOWax (200 μm × 0.40 μm × 25 m)
Carrier gas: He (constant pressure mode: 20 psi)
Oven: (1) Hold at 50 ° C. for 10 minutes, (2) Temperature rise to 200 ° C. at 10 ° C./minute, (3) Hold at 200 ° C. for 5 minutes Inlet: 200 ° C., pulsed splitless mode (20 → 40 psi, until 0.5 min)
Split ratio: 5.0: 1.0
Detector: 250 ° C. (FID)

<Method for producing polymer as raw material>
Preparation Example 1
Production of styrene acrylic acid copolymer (resin A) which is a vinyl polymer:
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 50 parts of methanol and 200 parts of tetrahydrofuran were charged and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

<Monomer composition, mixing ratio>
・ 95 parts of styrene ・ 5 parts of acrylic acid

  To this monomer mixture, 3 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was further mixed and added dropwise to the reaction vessel with stirring for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a styrene acrylic acid copolymer (resin A) which is a vinyl polymer.

The molecular weight of the obtained resin A was measured by the method described above, the number average molecular weight (may be described as Mn) was 4500, and the weight average molecular weight (may be described as Mw) was 16600. there were. The acid value of the obtained resin A was measured by the method described above, and was 40.2 (mgKOH / g). The unit amount of acrylic acid contained in the resin A was 0.72 (mmol / g). Moreover, the composition analysis of the obtained resin A was carried out using ¹ H-NMR and ¹³ C-NMR, and as a result of measurement by the method described above, styrene acrylic acid copolymer (styrene unit: 93 mol% acrylic acid unit). : 7 mol%).

Preparation Example 2
Production of styrene-acrylic acid butyl acrylic acid copolymer (resin B), which is a vinyl polymer:
<Monomer composition, mixing ratio>
・ Styrene 75 parts ・ Butyl acrylate 20 parts ・ Acrylic acid 5 parts Except for the monomer composition and mixing ratio, styrene butyl acrylate acrylic acid copolymer (resin B), which is a vinyl polymer, was prepared in the same manner as in Preparation Example 1. ) The molecular weight of the obtained resin B was measured by the method described above, the number average molecular weight was 4,700, and the weight average molecular weight was 12,200. The acid value of the obtained resin B was 36.9 (mgKOH / g) measured by the method described above, and the unit amount of acrylic acid contained in the resin B was 0.66 (mmol / g). In addition, the composition analysis of the obtained resin B was carried out using ¹ H-NMR and ¹³ C-NMR, and as a result of measurement by the method described above, styrene, butyl acrylate, acrylic acid copolymer (styrene unit: 74 mol%, butyl acrylate unit: 19 mol%, acrylic acid unit: 7 mol%).

Preparation Example 3
Production of styrene-methacrylic acid copolymer (resin C) which is a vinyl polymer:
<Monomer composition, mixing ratio>
-Styrene 93 parts-Methacrylic acid 7 parts By the method similar to the preparation example 1 except the monomer composition and mixing ratio, the styrene-methacrylic acid copolymer (resin C) which is a vinyl-type polymer was obtained. The molecular weight of the obtained resin C was measured by the method described above, the number average molecular weight was 4900, and the weight average molecular weight was 13100. The acid value of the obtained resin C was 39.0 (mg KOH / g) as measured by the method described above, and the unit amount of methacrylic acid contained in the resin C was 0.70 (mmol / g). Moreover, the composition analysis of the obtained resin C was carried out using ¹ H-NMR and ¹³ C-NMR, and as a result of measurement by the method described above, styrene-methacrylic acid copolymer (styrene unit: 93 mol%, methacrylic acid). (Unit: 7 mol%).

[Example 1]
100 parts of the styrene acrylic acid copolymer (styrene unit: 93 mol%, acrylic acid unit: 7 mol%) obtained in Preparation Example 1 in a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube. added. Next, 18 parts of 4-methoxyaniline-2-sulfonic acid was added, 100 parts of dimethylacetamide and 6 parts of pyridine were added and stirred, and then 22.2 parts of triphenyl phosphite (1. 0 mol%) and 2.4 parts of triethyl phosphite (0.2 mol% with respect to the acrylic acid unit) were added and heated at 120 ° C. for 6 hours.

  After completion of the reaction, it was recovered by reprecipitation in 1200 parts of 1N hydrochloric acid. The obtained polymer was washed with 1200 parts of 2N hydrochloric acid, then washed twice with 200 parts of water, and dried under reduced pressure, whereby vinyl containing a sulfonic acid unit represented by chemical formula (4) was obtained. A copolymer was obtained.

The obtained polymer was subjected to molecular weight measurement in the same manner as in Preparation Example 1, and the number average molecular weight was 4900 and the weight average molecular weight was 17000. Moreover, the composition analysis of the obtained polymer measured using the method of the said description using < ¹ > H-NMR and < ¹³ > C-NMR. As a result, it was confirmed that this was a vinyl copolymer containing 7 mol% of the sulfonic acid unit represented by the chemical formula (4).

  Further, the amount of phenol remaining in the obtained polymer was measured by the method described above using gas chromatography, and as a result, it was confirmed that 1.2% by mass remained.

[Example 2]
In Example 1, it is changed to 17.8 parts of triphenyl phosphite (0.8 mol% with respect to the acrylic acid unit) and 4.8 parts of triethyl phosphite (0.4 mol% with respect to the acrylic acid unit). A vinyl copolymer containing a sulfonic acid unit represented by the chemical formula (4) was obtained by carrying out the same method as in Example 1 except that. The obtained polymer was subjected to molecular weight measurement in the same manner as in Preparation Example 1, and the number average molecular weight was 4,800 and the weight average molecular weight was 16,800. Moreover, the composition analysis of the obtained polymer measured using the method of the said description using < ¹ > H-NMR and < ¹³ > C-NMR. As a result, it was confirmed to be a vinyl copolymer containing 7 mol% of the sulfonic acid unit represented by the chemical formula (4).

  Further, the amount of phenol remaining in the obtained polymer was measured by the method described above using gas chromatography, and as a result, it was confirmed that 0.9% by mass remained.

Example 3
In Example 1, except that 18 parts of 4-methoxyaniline-2-sulfonic acid was changed to 15 parts of 2-aminobenzenesulfonic acid, the sulfone represented by the chemical formula (5) was obtained by performing the same method as in Example 1. A vinyl copolymer containing acid units was obtained.

The obtained polymer was subjected to molecular weight measurement in the same manner as in Preparation Example 1, the number average molecular weight was 4,900, and the weight average molecular weight was 17,200. Moreover, the composition analysis of the obtained polymer measured using the method of the said description using < ¹ > H-NMR and < ¹³ > C-NMR. As a result, it was confirmed to be a vinyl copolymer containing 7 mol% of the sulfonic acid unit represented by the chemical formula (5).

  Further, the amount of phenol remaining in the obtained polymer was measured by the method described above using gas chromatography, and as a result, it was confirmed that 1.1% by mass remained.

Example 4
In Example 1, except that 18 parts of 4-methoxyaniline-2-sulfonic acid was changed to 13 parts of 2-amino-2-methylpropanesulfonic acid, the same procedure as in Example 1 was carried out to obtain the chemical formula (6) The vinyl copolymer containing the sulfonic acid unit shown by this was obtained.

The obtained polymer was subjected to molecular weight measurement in the same manner as in Preparation Example 1, and the number average molecular weight was 4,700 and the weight average molecular weight was 17,000. Moreover, the composition analysis of the obtained polymer measured using the method of the said description using < ¹ > H-NMR and < ¹³ > C-NMR. As a result, it was confirmed to be a vinyl copolymer containing 3 mol% of the sulfonic acid unit represented by the chemical formula (6).

  Further, the amount of phenol remaining in the obtained polymer was measured by the method described above using gas chromatography, and as a result, it was confirmed that 1.2% by mass remained.

Example 5
In a reaction vessel equipped with a cooling pipe, a stirrer, a thermometer and a nitrogen introduction pipe, the styrene butyl acrylate acrylate copolymer obtained in Preparation Example 2 (styrene unit: 74 mol%, butyl acrylate unit: 19 mol%) 100 parts of acrylic acid unit: 7 mol%) was added. Next, 18 parts of 2-amino-1-naphthalenesulfonic acid was added, 100 parts of dimethylacetamide and 6 parts of pyridine were added and stirred, and then 20.4 parts of triphenyl phosphite (1. 0 mol%) and 2.2 parts of triethyl phosphite (0.2 mol% with respect to the acrylic acid unit) were added and heated at 120 ° C. for 6 hours.

  After completion of the reaction, it was recovered by reprecipitation in 1200 parts of 1N hydrochloric acid. The obtained polymer was washed with 1200 parts of 2N hydrochloric acid, then washed twice with 200 parts of water, and dried under reduced pressure, whereby vinyl containing a sulfonic acid unit represented by chemical formula (7) was obtained. A copolymer was obtained.

The obtained polymer was subjected to molecular weight measurement in the same manner as in Preparation Example 1, and the number average molecular weight was 4,500 and the weight average molecular weight was 12,300. Moreover, the composition analysis of the obtained polymer measured using the method of the said description using < ¹ > H-NMR and < ¹³ > C-NMR. As a result, it was confirmed to be a vinyl copolymer containing 3 mol% of the sulfonic acid unit represented by the chemical formula (7).

  Further, the amount of phenol remaining in the obtained polymer was measured by the method described above using gas chromatography, and as a result, it was confirmed that 1.0% by mass remained.

Example 6
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of the styrene-methacrylic acid copolymer (styrene unit: 93 mol%, methacrylic acid unit: 7 mol%) obtained in Preparation Example 3 was added. added. Next, 17 parts of 4-methoxyaniline-2-sulfonic acid was added, 100 parts of dimethylacetamide and 6 parts of pyridine were added and stirred, and then 22.2 parts of triphenyl phosphite (1. 0 mol%) and 2.4 parts of triethyl phosphite (0.2 mol% with respect to the acrylic acid unit) were added and heated at 120 ° C. for 6 hours. Heated at 120 ° C. for 6 hours.

  After completion of the reaction, it was recovered by reprecipitation in 1200 parts of 1N hydrochloric acid. The obtained polymer was washed with 1200 parts of 2N hydrochloric acid, then washed twice with 200 parts of water, and dried under reduced pressure, whereby vinyl containing a sulfonic acid unit represented by the chemical formula (8) was obtained. A copolymer was obtained.

The obtained polymer was subjected to molecular weight measurement in the same manner as in Preparation Example 1, and the number average molecular weight was 5,200 and the weight average molecular weight was 14,000. Moreover, the composition analysis of the obtained polymer measured using the method of the said description using < ¹ > H-NMR and < ¹³ > C-NMR. As a result, it was confirmed to be a vinyl copolymer containing 7 mol% of the sulfonic acid unit represented by the chemical formula (8).

  Further, the amount of phenol remaining in the obtained polymer was measured by the method described above using gas chromatography, and as a result, it was confirmed that 1.1% by mass remained.

[Comparative Example 1] (Comparative Example for Examples 1 and 2)
In Example 1, the same method as in Example 1 except that triphenyl phosphite is not used and only 14.3 parts of triethyl phosphite (1.2 mol% with respect to the acrylic acid unit) is used. Went. The composition analysis of the obtained polymer was measured by the method described above using ¹ H-NMR and ¹³ C-NMR. As a result, it was confirmed that the reaction hardly proceeded.

[Comparative Example 2] (Comparative Example for Examples 1 and 2)
In Example 1, the same method as in Example 1 except that triethyl phosphite is not used and only 26.7 parts of triphenyl phosphite (1.2 mol% with respect to the acrylic acid unit) is used. As a result, a vinyl copolymer containing a sulfonic acid unit represented by the chemical formula (4) was obtained. The obtained polymer was subjected to molecular weight measurement in the same manner as in Preparation Example 1. The number average molecular weight was 4,900, and the weight average molecular weight was 17,300. Moreover, the composition analysis of the obtained polymer measured using the method of the said description using < ¹ > H-NMR and < ¹³ > C-NMR. As a result, it was confirmed to be a vinyl copolymer containing 7 mol% of the sulfonic acid unit represented by the chemical formula (4).

  Further, the amount of phenol remaining in the obtained polymer was measured by the method described above using gas chromatography, and as a result, it was confirmed that 1.6% by mass remained.

[Comparative Example 3] (Comparative Example to Example 3)
In Example 3, the same method as in Example 1 except that triethyl phosphite is not used and only 26.7 parts of triphenyl phosphite (1.2 mol% with respect to the acrylic acid unit) is used. As a result, a vinyl copolymer containing a sulfonic acid unit represented by the chemical formula (5) was obtained. The obtained polymer was subjected to molecular weight measurement in the same manner as in Preparation Example 1, the number average molecular weight was 5000, and the weight average molecular weight was 17300. Moreover, the composition analysis of the obtained polymer measured using the method of the said description using < ¹ > H-NMR and < ¹³ > C-NMR. As a result, it was confirmed to be a vinyl copolymer containing 7 mol% of the sulfonic acid unit represented by the chemical formula (5).

  Further, the amount of phenol remaining in the obtained polymer was measured by the method described above using gas chromatography, and as a result, it was confirmed that 1.6% by mass remained.

[Comparative Example 4] (Comparative Example to Example 4)
In Example 4, the same method as in Example 1 except that triethyl phosphite is not used and only 26.7 parts of triphenyl phosphite (1.2 mol% with respect to the acrylic acid unit) is used. As a result, a vinyl copolymer containing a sulfonic acid unit represented by the chemical formula (6) was obtained. The obtained polymer was subjected to molecular weight measurement in the same manner as in Preparation Example 1, and the number average molecular weight was 4,800 and the weight average molecular weight was 17,100. Moreover, the composition analysis of the obtained polymer measured using the method of the said description using < ¹ > H-NMR and < ¹³ > C-NMR. As a result, it was confirmed to be a vinyl copolymer containing 3 mol% of the sulfonic acid unit represented by the chemical formula (6).

  Further, the amount of phenol remaining in the obtained polymer was measured by the method described above using gas chromatography, and as a result, it was confirmed that 1.6% by mass remained.

[Comparative Example 5] (Comparative Example to Example 5)
In Example 5, the same method as in Example 1 except that triethyl phosphite is not used and only 24.5 parts of triphenyl phosphite (1.2 mol% with respect to the acrylic acid unit) is used. As a result, a vinyl copolymer containing a sulfonic acid unit represented by the chemical formula (7) was obtained. The obtained polymer was subjected to molecular weight measurement in the same manner as in Preparation Example 1, and the number average molecular weight was 4,400 and the weight average molecular weight was 12,100. Moreover, the composition analysis of the obtained polymer measured using the method of the said description using < ¹ > H-NMR and < ¹³ > C-NMR. As a result, it was confirmed to be a vinyl copolymer containing 3 mol% of the sulfonic acid unit represented by the chemical formula (7).

  Further, the amount of phenol remaining in the obtained polymer was measured by the method described above using gas chromatography, and as a result, it was confirmed that 1.5% by mass remained.

[Comparative Example 6] (Comparative Example to Example 6)
In Example 6, the same method as in Example 1 except that triethyl phosphite was not used and only 25.9 parts of triphenyl phosphite (1.2 mol% with respect to the acrylic acid unit) was used. As a result, a vinyl copolymer containing a sulfonic acid unit represented by the chemical formula (8) was obtained. The obtained polymer was subjected to molecular weight measurement in the same manner as in Preparation Example 1, the number average molecular weight was 5,400, and the weight average molecular weight was 14,200. Moreover, the composition analysis of the obtained polymer measured using the method of the said description using < ¹ > H-NMR and < ¹³ > C-NMR. As a result, it was confirmed to be a vinyl copolymer containing 7 mol% of the sulfonic acid unit represented by the chemical formula (8).

  Further, the amount of phenol remaining in the obtained polymer was measured by the method described above using gas chromatography, and as a result, it was confirmed that 1.6% by mass remained.

  From the results of Examples and Comparative Examples, by using triphenyl phosphite and phosphite triester in combination as a condensing agent, while reducing the amount of generated phenol, and triphosphite A polymer could be produced with the same reaction efficiency as when phenyl alone was used. Since the amount of triphenyl phosphite used can be reduced, the amount of phenol generated as a decomposition product can be reduced. Therefore, it was confirmed that the amount of phenol remaining in the polymer was reduced under the same washing conditions.

Claims (2)

(I) The following chemical formula (2)

A polymer containing INDICATED the structure in,
(Ii) The following chemical formula (3)

(In the formula, B1 represents an alkylene structure having 1 or 2 carbon atoms which may have a substituent or an aromatic ring which may have a substituent, and the substituent in the alkylene structure is a hydroxyl group or a carbon. The substituent in the aromatic ring is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group or an alkoxy group, including an adjacent carbon. And may form a 5-membered or 6-membered aromatic ring .)
In an amine compound containing a sulfonic acid group with INDICATED the structure,
Triphenyl phosphite and phosphite triester as condensation agent (esters are methyl, ethyl, propyls) and combination by reacting the following chemical formula (1)

(In the formula, B1 conforms to B1 in chemical formula (3).)
A method for producing a polymer, comprising obtaining a polymer having a structure represented by the formula: The method for producing a polymer according to claim 1, wherein the polymer including the structure represented by the chemical formula (1) is a vinyl polymer.