JP5946094B2 - High-purity sodium parastyrene sulfonate with excellent hue, polystyrene sodium sulfonate with excellent hue using the same, dispersant using the sodium polystyrene sulfonate, and synthetic paste for clothing finishing - Google Patents

Description

  The present invention relates to a high-purity sodium parastyrene sulfonate having an excellent hue, a polystyrene sulfonate having an excellent hue using the same, a dispersant using the sodium polystyrene sulfonate, and a synthetic paste for clothing finishing.

  Parastyrene sulfonic acid (salt) represented by sodium parastyrene sulfonate has a radical polymerizable vinyl group, a hydrophobic benzene ring having π electrons, and a sulfonic acid (salt) group that is a strong electrolyte in the molecule. It is a functional monomer and is used extensively in various industrial fields. For example, in emulsion polymerization, it is used as a reactive emulsifier in order to improve the stability of the emulsion and the water resistance and cationic dye dyeability of the (emulsion) polymer. Polymers and copolymers of sodium parastyrene sulfonate include pigments, antioxidants, various polymers (tackifier resins, chloroprene rubber, polyacrylate esters, polyesters, styrene-butadiene copolymers, polyvinyl chloride, Polyacrylonitrile, polysilicone, conductive polymer, etc.), nanocarbon materials, hot forging release agents and silica particles for abrasives, battery electrode materials (carbon, lithium iron phosphate, lithium manganese phosphate, etc.), for photography It is used as a dispersant for producing various aqueous dispersions such as silver halide. In addition, polymers of sodium parastyrene sulfonate are used for synthetic finishing pastes such as ironing agents, hair care products, antistatic agents, resist acid generators, water treatment agents, allergen supplements, ion exchange resins, and plating solution additions. It is used as an additive for cleaning agents, semiconductor and hard disk manufacturing fluids, and shale oil mining fluids.

  In the above field of application, various improvements are required for sodium parastyrene sulfonate and its (co) polymer. Of these, the need for improvement common to many applications is hue. In particular, for applications such as adhesives, polymer emulsions for paints, synthetic pastes for garment finishing such as ironing agents, antistatic agents, and photographic silver halide emulsions, sodium parastyrenesulfonate and its (co) polymers The hue of is an important factor that directly affects the product value. That is, the industrially available conventional sodium parastyrene sulfonate and its (co) polymer have a light yellow to light tan color and are strongly required to be lightened or colorless.

  About the hue of sodium parastyrene sulfonate, the influence of an impurity is suggested (for example, patent document 1). However, as for the important impurities, only metal halides are mentioned, and no other specific hues are mentioned. Moreover, about the hue of sodium parastyrene sulfonate (co) polymer, the influence of a polymerization initiator is suggested (for example, patent document 2). However, no mention is made of the iron content and other impurities contained in the raw material sodium parastyrene sulfonate and their influence on the hue.

  Moreover, a chloroprene rubber adhesive has been used as a universal adhesive since ancient times. Methods for producing chloroprene rubber are known. For example, chloroprene or chloroprene and a radical polymerizable monomer copolymerizable therewith, an alkali metal salt of disproportionated rosin acid (acting as an emulsifier) and an alkali of a naphthalenesulfonic acid formalin condensate. It emulsifies in water using a metal salt (acting as a dispersant), and a radical polymerization initiator is added to carry out emulsion polymerization. Unreacted monomers in the obtained chloroprene rubber emulsion are removed by a steam distillation method. Finally, solid chloroprene rubber can be produced by removing chloroprene rubber from the emulsion by a method such as freeze coagulation, washing with water and drying (for example, Non-Patent Document 1). A chloroprene rubber adhesive is produced by dissolving the above chloroprene rubber and compounding agents such as tackifier resin, metal oxide, and crosslinking agent in an organic solvent such as toluene, methylcyclohexane, n-hexane, methyl ethyl ketone, and acetate. Has been. When a chloroprene rubber adhesive is used for the production of footwear or sports equipment, an excellent hue (as close to colorless as possible) is required.

Therefore, as a method for improving the hue of the adhesive, a method is proposed in which an alkali metal salt of a styrene sulfonic acid (co) polymer, which is hardly discolored, is used as a dispersant instead of the alkali metal salt of the naphthalene sulfonic acid formalin condensate. (For example, Patent Document 3). Although the hue is certainly improved, it is not always satisfactory and further improvements are required. Moreover, nothing is mentioned about the hue of the sodium polystyrene sulfonate (co) polymer used.
In addition, sodium polystyrene sulfonate is known as a synthetic paste used in clothing finishing agents such as ironing agents (Patent Document 4). The hue is extremely important in this application, and there is a demand for further colorlessness of the synthetic paste, but there is no description regarding the hue of sodium polystyrene sulfonate.

Japanese Patent Laid-Open No. 51-138645 JP-A-11-181004 Japanese Patent No. 3601136 Japanese Patent No. 2808205

Adhesion Technology, Vol. 21, No. 4, pp. 14-19, 2002, published by the Adhesion Society of Japan

  The present invention has been made in view of the above problems, and its purpose is to provide a high-purity paraffin excellent in hue useful for producing polymer emulsions such as chloroprene rubber excellent in hue and synthetic paste for clothing finishing. An object of the present invention is to provide sodium styrenesulfonate and a sodium styrenesulfonate (co) polymer (hereinafter also referred to as “PSS sodium” or “sodium polystyrene sulfonate”).

  As a result of intensive studies to solve the above problems, the present inventors have found that high-purity sodium parastyrene sulfonate having reduced iron content and specific impurities, and sodium parastyrene sulfonate produced using the same (both) The present inventors have found that the polymer is excellent in hue and becomes sodium parastyrene sulfonate and sodium PSS which are useful for producing polymer emulsions such as chloroprene rubber and synthetic pastes for garment finishing. .

The present invention has an iron content in sodium parastyrene sulfonate of less than 3.00 μg / g and sodium bromide of less than 2.50 wt%, (a) sodium orthostyrene sulfonate, (b) β-bromoethylbenzene sulfonic acid The peak area ratios obtained by high performance liquid chromatography (HPLC) of sodium, (c) sodium metastyrene sulfonate, (d) sodium bromostyrene sulfonate, and (e) sodium β-hydroxyethylbenzenesulfonate are respectively (a) ≦ 0.40%, (b) ≦ 4.00%, (c) ≦ 8.00%, (d) ≦ 0.10%, and (e) ≦ 0.80 (with sodium parastyrene sulfonate and (A) to (e) High purity sodium parastyrene sulfonate (hereinafter referred to as “high purity”) having an excellent hue of 100). Also called La sodium styrene sulfonate ") on.
Here, the high-purity sodium parastyrenesulfonate excellent in hue of the present invention has an iron content of less than 3.00 μg / g and sodium bromide of less than 2.50 wt% in the sodium parastyrenesulfonate (a). High-performance liquid chromatography of sodium orthostyrenesulfonate, (b) sodium β-bromoethylbenzenesulfonate, (c) sodium metastyrenesulfonate, (d) sodium bromostyrenesulfonate, (e) sodium β-hydroxyethylbenzenesulfonate The peak area ratios determined by chromatography (hereinafter referred to as HPLC) are (a) ≦ 0.20%, (b) ≦ 0.50%, (c) ≦ 3.00%, (d) ≦ 0. 10%, and (e) ≦ 0.20% (however, the sum of sodium parastyrene sulfonate and (a) to (e) peak area is 1) It is preferably 0).
Next, the present invention provides a sodium polystyrene sulfonate having excellent hue with the following repeating structural unit A, or the following repeating structural unit A and the following repeating structural unit B, produced using the above-described high-purity sodium parastyrene sulfonate. About.

[In repeating structural units A and B, M represents a sodium cation, Q represents a radical polymerizable monomer residue, n represents an integer of 1 or more, and m represents an integer of 0 or more. ]
Here, the weight average molecular weight determined by gel permeation chromatography (hereinafter referred to as GPC) of sodium PSS of the present invention is preferably 2,000 to 1,000,000.
Q in the above repeating structural unit B includes (meth) acrylic acid residue, (meth) acrylic acid ester residue, maleic anhydride residue, maleic acid residue, maleimide residue, (meth) acrylamide residue It is preferably one or more radically polymerizable monomer residues selected from the group consisting of a group, a styrene residue, and a styrene derivative residue.
Next, the present invention relates to a dispersant comprising the above-mentioned PSS sodium as an active ingredient, or a garment iron finish produced using PSS sodium as a synthetic paste.

  The high-purity sodium parastyrene sulfonate of the present invention and the sodium parastyrene sulfonate (co) polymer produced by using the same are excellent in hue due to low iron content and other impurities, and various aqueous such as chloroprene rubber. It is useful for improving the hue of dispersions and synthetic pastes for clothing finishing.

It is HPLC chromatography of the high purity sodium parastyrene sulfonate of Example 1, In FIG. 1, a vertical axis | shaft shows peak intensity | strength (it is the absorption intensity of a detector, a unit is arbitrary), and a horizontal axis is elution time (unit). Indicates minutes). (A), (b), (c), (d), and (e) in FIG. 1 are (a) sodium orthostyrenesulfonate, (b) sodium β-bromoethylbenzenesulfonate, and (c) meta. The strengths of sodium styrenesulfonate, (d) sodium bromostyrenesulfonate, and (e) sodium β-hydroxyethylbenzenesulfonate are shown. 2 is an HPLC chromatography of low purity sodium parastyrene sulfonate of Comparative Example 1. Others are the same as the description of FIG. It is a block diagram of the angle of repose measuring apparatus used for the angle of repose measurement of an Example, a protractor used for this, and an electronic pan balance.

The present invention has an iron content in sodium parastyrene sulfonate of less than 3.00 μg / g and sodium bromide of less than 2.50 wt%, (a) sodium orthostyrene sulfonate, (b) β-bromoethylbenzene sulfonic acid The peak area ratios obtained by high performance liquid chromatography (HPLC) of sodium, (c) sodium metastyrene sulfonate, (d) sodium bromostyrene sulfonate, and (e) sodium β-hydroxyethylbenzenesulfonate are respectively (a) ≦ 0.40%, (b) ≦ 4.00%, (c) ≦ 8.00%, (d) ≦ 0.10%, and (e) ≦ 0.80% (however, sodium parastyrene sulfonate And (a) to (e) a high-purity sodium parastyrenesulfonate having an excellent hue of 100) The repeating structural units A produced using, or PSS sodium hue excellent having the repeating structural units A and (B).
Here, “excellent hue” means that there is no coloration and is close to white or colorless and transparent, but in the present invention, it means that yellowness is particularly low. Specifically, in the case of high purity sodium parastyrene sulfonate, the yellowness (YI value) of the crystal powder obtained by a color difference meter is small and the whiteness (WI value) is high, and the APHA value of the aqueous solution is small. In the case of PSS sodium, it means that the APHA value, yellowness (YI value), and b value of the PSS sodium aqueous solution obtained with a color difference meter are small.

  In the present invention, the iron content in sodium parastyrenesulfonate is less than 3.00 μg / g, the sodium bromide content is less than 2.50 wt%, (a) sodium orthostyrenesulfonate, (b) sodium β-bromoethylbenzenesulfonate. , (C) sodium metastyrene sulfonate, (d) sodium bromostyrene sulfonate, and (e) sodium β-hydroxyethylbenzenesulfonate, the peak area ratios determined by HPLC were (a) ≦ 0.20%, (B) ≦ 0.50%, (c) ≦ 3.00%, (d) ≦ 0.10%, and (e) ≦ 0.20% (ie, sodium parastyrenesulfonate and (a)-( e) High purity sodium parastyrene sulfonate having a total peak area of 100), and the above repeating structural unit A produced using the same Or is preferably PSS sodium having the repeating structural units A and (B).

  The sodium PSS of the present invention is not limited to a homopolymer of sodium parastyrene sulfonate, that is, it is not particularly limited as long as it has the repeating structural unit A or the repeating structural units A and B. Alternatively, a random copolymer, a block copolymer, or a graft copolymer may be used. The block copolymer here means that a PSS parastyrene sulfonate sodium chain (the above repeating structural unit A) and a polymer chain different from PSS sodium parastyrene sulfonate (the above repeating structural unit B) are bonded via a covalent bond. Are connected in a block form, and include diblock, triblock, and multiblock types. In addition, the graft copolymer is a polymer chain (different from PSS sodium) or a branch of a polymer chain (repeated structural unit B) different from PSS sodium at the trunk of PSS sodium (repeated structural unit A). A branch of PSS sodium (repeated structural unit A) is bonded to the trunk of the recurring structural unit B) via a covalent bond.

The feature of the present invention is that the monomer (sodium parastyrene sulfonate) used for the production of PSS sodium is highly purified, which will be described below.
Commercially available sodium parastyrene sulfonate usually contains 5.0 to 10.0 wt% of water (crystal water and adhering water). This moisture is the largest impurity contained in sodium parastyrene sulfonate. The point of the present invention is that, as can be seen from the general production method of parastyrene sulfonate below, in addition to sodium bromide (in the case of M = sodium in the following formula), which is the main impurity next to water, unreacted bromine Found that chemical intermediates, organic isomers, and iron are contained as impurities, and that by reducing these impurities, the hue of sodium parastyrene sulfonate was greatly improved. is there.

  As a result of detailed analysis of impurities other than water contained in sodium parastyrenesulfonate, in addition to sodium bromide, which is the main impurity, a small amount of iron, (a) sodium orthostyrenesulfonate, (b) β-bromoethylbenzene It was found that sodium sulfonate, (c) sodium metastyrene sulfonate, (d) sodium bromostyrene sulfonate, and (e) sodium β-hydroxyethylbenzenesulfonate.

  The present inventors have controlled the production conditions such as a method of partially dissolving sodium parastyrenesulfonate containing the above impurities in an aqueous solvent and recrystallizing, a method of washing with pure water, or a reaction temperature, to thereby improve the iron content. Less than 0.000 μg / g, less than 2.50 wt% sodium bromide, (a) sodium orthostyrenesulfonate, (b) sodium β-bromoethylbenzenesulfonate, (c) sodium metastyrenesulfonate, (d) The peak area ratios of sodium bromostyrenesulfonate and (e) sodium β-hydroxyethylbenzenesulfonate determined by high performance liquid chromatography (HPLC) were (a) ≦ 0.40% and (b) ≦ 4.00%, respectively. , (C) ≦ 8.00%, (d) ≦ 0.10%, and (e) ≦ 0.80% When the sum of sodium acid with (a) ~ (e) peak areas to produce a high purity para-styrene sulfonic acid sodium 100), it found that the hue of sodium p-styrene sulfonate is significantly improved. Further, the impurities (a) to (e) are respectively (a) ≦ 0.20%, (b) ≦ 0.50%, (c) ≦ 3.00%, (d) ≦ 0.10%, ( e) ≦ 0.20% (however, the sum of sodium parastyrene sulfonate and (a) to (e) peak area is 100), it was found that the color of sodium parastyrene sulfonate is further improved. .

  Furthermore, when the high purity PSS sodium was manufactured by using the conventional radical polymerization method using this, it was found that the hue of PSS sodium was remarkably improved. Since the high-purity sodium parastyrene sulfonate and PSS sodium are extremely excellent in hue, the utility value in various industrial fields described above is extremely high. For example, when chloroprene rubber (chloroprene rubber emulsion and chloroprene rubber) was produced using the PSS sodium as a dispersant, it was found that the hue of chloroprene rubber was further improved as compared with the case of using conventional PSS sodium. . Moreover, when the said PSS sodium was used as a synthetic paste for clothes iron finish agents, it discovered that the hue of the fabric which gave PSS sodium improved further compared with the case where the conventional PSS sodium was given.

  The reason why the color of sodium parastyrene sulfonate has improved is not necessarily clear, but it is thought to be a synergistic effect due to the reduction of iron and other impurities. This is probably because the chemical stability of sodium PSS was improved by the reduction of isomers such as isomers and sodium β-haloethylbenzenesulfonate.

Although there is no restriction | limiting in the weight average molecular weight calculated | required by GPC of the PSS sodium of this invention, When using as a dispersing agent in emulsion polymerization, such as chloroprene, when considering an emulsion viscosity, stability, etc. A relatively low molecular weight is preferable, for example, 2,000 to 50,000 is preferable. On the other hand, in applications other than emulsion polymerization, for example, when used as a synthetic paste for clothing finishing, it is preferably a high molecular weight in terms of viscosity and water resistance after drying. 600,000 is preferable.
This weight average molecular weight can be easily adjusted by the amount of polymerization initiator or chain transfer agent added to the monomer.

  Other monomers other than sodium parastyrene sulfonate used in the PSS sodium of the present invention are those in which radical polymerization proceeds by a PSS sodium radical, or a radical that can be a radical polymerization initiator for sodium parastyrene sulfonate. If it is a thing (in other words, what can be radical copolymerized with sodium parastyrene sulfonate), there will be no restriction | limiting in particular. For example, styrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, fluorostyrene, trifluorostyrene, nitrostyrene, cyanostyrene, α-methylstyrene, p-chloromethylstyrene, p-cyanostyrene, p-acetoxystyrene, P-styrenesulfonyl chloride, ethyl p-styrenesulfonyl, methyl p-styrenesulfonyl, propyl p-styrenesulfonyl, p-butoxystyrene, 4-vinylbenzoic acid, 3-isopropenyl-α, α'-dimethylbenzyl isocyanate, vinyl Styrenes such as benzyltrimethylammonium chloride, isobutyl vinyl ether, ethyl vinyl ether, 2-phenyl vinyl alkyl ether, nitrophenyl vinyl ether, cyanophenyl vinyl ether Ter, chlorophenyl vinyl ether, vinyl ethers such as chloroethyl vinyl ether, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, decyl acrylate, lauryl acrylate, octyl acrylate, acrylic Dodecyl acid, stearyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, bornyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2-hydroxyethyl acrylate, tetrahydrofurfuryl acrylate, acrylic acid Methoxyethylene glycol, ethyl carbitol acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3- (trimethoxy acrylate) Ril) propyl, polyethylene glycol acrylate, glycidyl acrylate, 2- (acryloyloxy) ethyl phosphate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,2-trifluoroethyl acrylate, acrylic acid Acrylic acid esters such as 2,2,3,3,3-pentafluoropropyl, acrylic acid 2,2,3,4,4,4-hexafluorobutyl, methyl methacrylate, t-butyl methacrylate, methacrylic acid sec-butyl, i-butyl methacrylate, i-propyl methacrylate, decyl methacrylate, lauryl methacrylate, octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, bornyl methacrylate, benzyl methacrylate, methacrylic acid Phenyl , Glycidyl methacrylate, polyethylene glycol methacrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, methoxyethylene glycol methacrylate, ethyl carbitol methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2- (Methacryloyloxy) ethyl phosphate, 2- (dimethylamino) ethyl methacrylate, 2- (diethylamino) ethyl methacrylate, 3- (dimethylamino) propyl methacrylate, 2- (isocyanato) ethyl methacrylate, methacrylic acid 2 , 4,6-tribromophenyl, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-methyl methacrylate Methacrylic acid esters such as tafluoropropyl, methacrylic acid 2,2,3,4,4,4-hexafluorobutyl, diacetone methacrylate, isoprenesulfonic acid, 1,3-butadiene, 2-methyl-1,3- Butadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 2-cyano-1,3-butadiene, 1-chloro-1,3-butadiene, 2- (N-piperidyl) Methyl) -1,3-butadiene, 2-triethoxymethyl-1,3-butadiene, 2- (N, N-dimethylamino) -1,3-butadiene, N- (2-methylene-3-butenoyl) morpholine 1,3-butadienes such as diethyl 2-methylene-3-butenylphosphonate, N-phenylmaleimide, N- (chlorophenyl) maleimide, N- (me Tilphenyl) maleimide, N- (isopropylphenyl) maleimide, N- (sulfophenyl) maleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N- (nitrophenyl) maleimide, N-benzylmaleimide, N- (4-acetoxy-1-naphthyl) maleimide, N- (4-oxy-1-naphthyl) maleimide, N- (3- Fluoranthyl) maleimide, N- (5-fluoresceinyl) maleimide, N- (1-pyrenyl) maleimide, N- (2,3-xylyl) maleimide, N- (2,4-xylyl) maleimide, N- (2,6 -Xylyl) maleimide, N- (aminopheny M) maleimide, N- (tribromophenyl) maleimide, N- [4- (2-benzimidazolyl) phenyl] maleimide, N- (3,5-dinitrophenyl) maleimide, N- (9-acridinyl) maleimide, maleimide, Maleimides such as N- (sulfophenyl) maleimide, N-cyclohexylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-methoxyphenylmaleimide, dibutyl fumarate, dipropyl fumarate, diethyl fumarate, dicyclohexyl fumarate, etc. Diesters of fumaric acid, monoesters of fumaric acid such as butyl fumarate, propyl fumarate, ethyl fumarate, maleic diesters such as dibutyl maleate, dipropyl maleate, diethyl maleate, butyl maleate, maleic acid Maleic acid monoesters such as propyl, ethyl maleate, dicyclohexyl maleate, acid anhydrides such as maleic anhydride, citraconic anhydride, acrylamide, N-methylacrylamide, N-ethylacrylamide, 2-hydroxyethylacrylamide, N, N-diethylacrylamide, acryloylmorpholine, N, N-dimethylaminopropylacrylamide, isopropylacrylamide, N-methylolacrylimide, sulfophenylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-1-methylsulfone Acrylamides such as acids, diacetone acrylamide, acrylamide alkyl trialkyl ammonium chloride, methacrylamide, N-methyl methacrylate N-ethylmethacrylamide, 2-hydroxyethylmethacrylamide, N, N-diethylmethacrylamide, N, N-dimethylmethacrylamide, N-methylolmethacrylamide, methacryloylmorpholine, N, N-dimethylaminopropylmethacrylamide, Methacrylamide such as isopropylmethacrylamide, 2-methacrylamide-2-methylpropanesulfonic acid, methacrylamide alkyltrialkylammonium chloride, others, vinylpyrrolidone, sulfophenylitaconimide, acrylonitrile, methacrylonitrile, fumaronitrile, α- Cyanoethyl acrylate, citraconic acid, citraconic anhydride, vinyl acetic acid, vinyl propionate, vinyl pivalate, vinyl versamic acid, crotonic acid , Itaconic acid, fumaric acid, maleic acid, mono 2- (methacryloyloxy) ethyl phthalate, mono 2- (methacryloyloxy) ethyl succinate, mono 2- (acryloyloxy) ethyl succinate, methacryloxypropyltrimethoxysilane, methacrylic acid Roxypropyldimethoxysilane, acrolein, vinylmethylketone, N-vinylacetamide, N-vinylformamide, vinylethylketone, vinylsulfonic acid, allylsulfonic acid, dehydroalanine, sulfur dioxide, isobutene, N-vinylcarbazole, vinylidene dicyanide , Paraquinodimethane, chlorotrifluoroethylene, tetrafluoroethylene, norbornene, N-vinylcarbazole, acrylic acid, methacrylic acid and the like. Among these, in view of copolymerizability and availability with parastyrene sulfonic acid (salt), methacrylic acid, methyl methacrylate, 2-hydroxyethyl methacrylate, maleic anhydride, maleic acid, N-phenylmaleimide N-cyclohexylmaleimide, methacrylamide, methacryloylmorpholine, styrene and styrene derivatives are preferred.

  The use ratio of the other monomers is 99 wt% or less, preferably about 10 to 90 wt% in all monomers. If it exceeds 99 wt%, depending on the application, it is possible to impart the characteristics of sodium parastyrene sulfonate to the polymer by copolymerizing a very small amount of sodium parastyrene sulfonate. When used as a dispersant, the characteristics of sodium parastyrene sulfonate are difficult to be exhibited, which is not preferable.

Next, the manufacturing method of the high purity sodium parastyrene sulfonate of this invention is demonstrated.
(1) As a method for removing iron, which is the most important trace impurity in the present invention, (i) by treating β-bromoethylbenzenesulfonic acid, which is a precursor of parastyrenesulfonic acid, with a strong acid type cation exchange resin. , A method of removing iron ions, (ii) a method of filtering water-soluble ferrous hydroxide from sodium parastyrene sulfonate obtained by reaction crystallization of β-bromoethylbenzenesulfonic acid and sodium hydroxide, (Iii) There are methods in which air is blown into an alkaline aqueous solution of sodium parastyrenesulfonate or an oxidizing agent is added to precipitate water-insoluble ferric hydroxide, followed by filtration.

In the case of the purification method (i), the iron removal method is more specifically described. For example, a sulfonic acid type cation exchange resin regenerated with hydrochloric acid is converted into a β-bromoethylbenzenesulfonic acid aqueous solution (ion exchange capacity of the cation exchange resin). 70 to 80%), and after slowly stirring at room temperature for 3 to 6 hours, the iron ions can be removed by filtering off β-bromoethylbenzenesulfonic acid.
The obtained high-purity β-bromoethylbenzene is then vinylated by a conventional method according to the above chemical reaction formula to obtain sodium parastyrenesulfonate. That is, as the conditions for vinylation at this time, for example, in a stainless steel reaction kettle with a stirrer equipped with a jacket, β-bromoethylbenzenesulfonic acid and β-bromoethylbenzenesulfonic acid are 2.0 to 3.0 times moles. For example, a method of vinylating at 60 to 110 ° C. while simultaneously feeding 2 moles of sodium hydroxide over 2 to 5 hours can be mentioned.

  In addition, a specific example of the purification method of (ii) is that solid-liquid separation of a slurry containing sodium parastyrene sulfonate crystals and water-soluble impurities such as ferrous hydroxide and sodium bromide by centrifugal filtration. Can be used to remove impurities such as iron and sodium bromide from parastyrene sulfonic acid crystals.

  Furthermore, a specific example of the purification method of (iii) is as follows. By blowing air into an alkaline aqueous solution of sodium parastyrene sulfonate, water-soluble ferrous hydroxide is precipitated on water-insoluble ferric hydroxide. After that, by centrifuging, a sodium parastyrenesulfonate crystal having a large specific gravity is precipitated, and colloidal ferric hydroxide is suspended. Impurities such as ferric hydroxide suspended by decantation and sodium bromide dissolved in water can be removed.

  (2) The method for removing impurities other than iron is not particularly limited. For example, commercially available sodium parastyrenesulfonate is mixed with pure water or a water-soluble solvent such as acetone, methanol, isopropanol and water. The mixture is heated at 40 to 70 ° C. for 30 to 1 hour, stirred and partially dissolved, and then cooled to 30 ° C. or less over 30 minutes to 2 hours to wash or recrystallize sodium parastyrene sulfonate. This can reduce major impurities such as sodium bromide, isomers, and sodium β-haloethylbenzenesulfonate. By repeating this operation, impurities other than iron can be reduced. This recrystallization operation is performed once or more, preferably 1 to 3 times in consideration of productivity and cost.

  More specifically, the purification method of (2) above is described. For example, sodium parastyrenesulfonate is dissolved in methanol at a concentration of 5 to 6 wt% (usually at 40 to 50 ° C. for about 10 to 60 minutes) and slowly High-purity sodium parastyrene sulfonate can be obtained by precipitating sodium parastyrene sulfonate crystals by cooling to room temperature to about 10 ° C., followed by filtration and drying.

  High purity sodium parastyrene sulfonate obtained by the above purification method (1) may be further purified according to the above purification method (2). By this treatment, impurities such as iron and sodium bromide, particularly (a) sodium orthostyrene sulfonate, (b) β-bromoethylbenzene sulfonate, (c) sodium metastyrene sulfonate, (d) bromostyrene sulfonate The amount of sodium, (e) sodium β-hydroxyethylbenzenesulfonate can be further reduced.

In the present invention, when synthesizing sodium parastyrenesulfonate from sodium hydroxide and sodium β-bromoethylbenzenesulfonate, the following production method is preferably employed.
That is, when sodium hydroxide and β-bromoethylbenzenesulfonic acid are simultaneously fed to the reaction kettle at a constant rate to produce sodium parastyrene sulfonate, the sodium hydroxide concentration in the reaction kettle (the weight of the total sodium hydroxide fed) / Total reaction liquid weight in reaction kettle × 100) is maintained at 10.00 to 20.00 wt%, and β-bromoethylbenzenesulfonic acid concentration (weight of fed total β-bromoethylbenzenesulfonic acid / in reaction kettle The total reaction liquid weight × 100) was controlled to increase from 0.00 wt% to 30.00 to 50.00 wt% over 1 to 7 hours, and reacted and crystallized at 60 to 110 ° C. for 1 to 7 hours. The wet cake obtained by solid-liquid separation is forced to flow.

  The method for producing sodium parastyrene sulfonate of the present invention will be described more specifically. For example, the sodium hydroxide concentration in the reaction vessel (weight of total sodium hydroxide fed / total reaction solution weight in reaction vessel × 100) is kept at 10.00 to 20.00 wt%, and β-bromoethylbenzenesulfone Increase the acid concentration (weight of total fed β-bromoethylbenzenesulfonic acid / weight of total reaction solution in reaction kettle × 100) from 0.00 wt% to 30.00-50.00 wt% over 1-7 hours. The reaction is crystallized at 60 to 110 ° C. for 1 to 7 hours while feeding. The produced slurry of sodium parastyrene sulfonate is cooled to 10 to 40 ° C. and then separated by a centrifugal filter to obtain a wet cake of sodium parastyrene sulfonate. By forcibly flowing the wet cake at 20 to 40 ° C. for 5 to 30 minutes using a uniaxial screw blender, the sodium paraparastyrene sulfonate hemihydrate of the present invention can be produced.

  When, for example, β-bromoethylbenzene sulfonic acid having a concentration of 70 wt% is fed to an aqueous sodium hydroxide solution having a concentration of more than 20 wt% in the total reaction solution (for example, Patent 36001222), the resulting sodium parastyrene sulfonate crystals are obtained. Since it becomes too small, a sodium parastyrene sulfonate hemihydrate with much moisture and poor fluidity can be obtained. In addition, when washing or recrystallization purification is performed using an aqueous solvent, the solid-liquid separability is lowered and the purification efficiency is deteriorated. On the other hand, if the feed rate of β-bromoethylbenzenesulfonic acid is too high (Patent No. 3890642) even if the sodium hydroxide concentration in the total reaction solution is 20 wt% or less, for example, the total reaction within 1 hour of the start of feed If the concentration of β-bromoethylbenzenesulfonic acid in the liquid exceeds 40 wt%, the resulting sodium parastyrenesulfonate crystals will be too large, resulting in a sodium parastyrenesulfonate hemihydrate with good fluidity but poor solubility. It is done.

  The sodium parastyrene sulfonate produced in the present invention can be controlled in particle size by improving the reaction crystallization conditions. For example, the median diameter measured by a laser diffraction / scattering particle size analyzer is 25.00. A product having a small particle of less than 150.00 μm and less than 10.00 μm of particles of 10.00% or less, a water content of 10.00 wt% or less, and an angle of repose of 55 degrees or less is obtained. Since such sodium parastyrene sulfonate has improved fluidity while maintaining excellent solubility, it is easy to handle, and moreover, high-purity sodium parastyrene sulfonate can be efficiently produced. The utility value is high in the above industrial fields.

The sodium parastyrenesulfonate of the present invention has an angle of repose defined by the following description of 55 degrees or less, preferably 50 degrees or less. When it exceeds 55 degrees, fluidity will be inferior. When the angle of repose is 55 degrees or less, it is excellent in fluidity, and troubles such as clogging in a hopper are solved when used in a large amount in a factory. In order to reduce the angle of repose, the fluidity of the powder may be increased. Although the relationship between fluidity and the structure and composition of sodium parastyrene sulfonate powder is not necessarily clear, it is considered that the influence of moisture in the powder is large. That is, it is considered that as the particle size of the powder is smaller, the water content increases due to the increase in the total surface area, resulting in a decrease in fluidity, and the water content can be adjusted by controlling the particle size described above.
The solubility of the sodium parastyrenesulfonate of the present invention in water (see “Measurement of dissolution rate” below) is preferably 200 seconds or less, and more preferably 160 seconds or less. Although there is no harmful effect due to too high solubility, if it exceeds 200 seconds, when using a large amount of sodium parastyrene sulfonate as a chemical raw material in a factory, problems such as decreased productivity and clogging of the strainer occur. It tends to occur and is not preferable. This solubility can be adjusted by controlling the particle size described above.

Next, the manufacturing method of the PSS sodium of this invention is demonstrated.
Although the manufacturing method of PSS sodium is not specifically limited, The method by general radical polymerization is illustrated as a 1st example. For example, a reaction vessel is charged with a homogeneous solution of water or an aqueous solvent and sodium parastyrene sulfonate, and if necessary, a mixture of other monomers capable of radical copolymerization with sodium parastyrene sulfonate, and if necessary, a molecular weight regulator And deoxidizing the system, heating to a predetermined temperature, and then polymerizing while adding a radical polymerization initiator. At this time, in order to avoid abrupt polymerization and to consider the controllability of the molecular weight in the low molecular weight region, instead of first charging all the monomer mixture into the reaction vessel, each monomer is adjusted to a polymerization initiator or molecular weight control. It is preferable to add it little by little to the reaction vessel together with the agent. Also, PSS sodium can be produced by finely dispersing or emulsifying an aqueous solution of a water-soluble monomer such as sodium parastyrene sulfonate in oil, followed by polymerization (so-called reverse phase emulsion polymerization) while adding a radical polymerization initiator. it can.

The reaction solvent is not particularly limited, but the solubility of sodium parastyrene sulfonate and other copolymerizable monomers (comonomer), use as a dispersant in emulsion polymerization, use as a synthetic paste in clothing finishes In view of the above, a mixture of water and a water-soluble solvent is preferable. The water-soluble solvent is not limited as long as it is a composition in which a mixture of sodium parastyrene sulfonate and a comonomer is dissolved. For example, acetone, tetrahydrofuran, dioxane, methanol, ethanol, n-propanol, isopropanol, methoxyethanol, 2- Examples thereof include ethoxyethanol, 2-butoxyethanol, butanol, ethylene glycol, propylene glycol, glycerin, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone and the like. Acetone, ethanol, isopropanol, tetrahydrofuran, dioxane, dimethyl sulfoxide, N-methylpyrrolidone, and dimethylformamide are preferred.
The amount of water or aqueous solvent used as the reaction solvent is usually 150 to 2,000 parts by weight with respect to 100 parts by weight of the total amount of monomers.

The molecular weight regulator is not particularly limited. For example, diisopropylxanthogen disulfide, diethylxanthogen disulfide, diethylthiuram disulfide, 2,2′-dithiodipropionic acid, 3,3′-dithiodipropionic acid, 4,4 Disulfides such as' -dithiodibutanoic acid, 2,2'-dithiobisbenzoic acid, n-dodecyl mercaptan, octyl mercaptan, t-butyl mercaptan, thioglycolic acid, thiomalic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, Thiosalicylic acid, 3-mercaptobenzoic acid, 4-mercaptobenzoic acid, thiomalonic acid, dithiosuccinic acid, thiomaleic acid, thiomaleic anhydride, dithiomaleic acid, thioglutaric acid, cysteine, homocysteine, 5-mercaptoteto Razole acetic acid, 3-mercapto-1-propanesulfonic acid, 3-mercaptopropane-1,2-diol, mercaptoethanol, 1,2-dimethylmercaptoethane, 2-mercaptoethylamine hydrochloride, 6-mercapto-1-hexanol, Mercaptans such as 2-mercapto-1-imidazole, 3-mercapto-1,2,4-triazole, cysteine, N-acylcysteine, glutathione, N-butylaminoethanethiol, N, N-diethylaminoethanethiol, iodoform, etc. Halogenated hydrocarbons, diphenylethylene, p-chlorodiphenylethylene, p-cyanodiphenylethylene, α-methylstyrene dimer, benzyldithiobenzoate, 2-cyanoprop-2-yldithiobenzoate, organic telluride Things, sulfur, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, potassium metabisulfite and the like.
The usage-amount of a molecular weight regulator is 0.1-10 weight part normally with respect to 100 weight part of monomer whole quantity.

Examples of the radical polymerization initiator include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide. 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate, t -Butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropyl carbonate, cumylperoxyoct Ate, persulfate , Peroxides such as ammonium persulfate, hydrogen peroxide, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1 -Cyano-1-methylethyl) azo] formamide, dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis ( 2,4,4-trimethylpentane), 2,2′-azobis {2-methyl-N- [1,1′-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2, '-Azobis {2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis {2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2 '-Azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl) propane]} dihydrochloride, 2,2'-azobis (1-imino-1-pyrrolidino-2-methylpropane) ) Azo such as dihydrochloride, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate Compounds and the like. Moreover, you may use together reducing agents, such as ascorbic acid, erythorbic acid, aniline, a tertiary amine, longgarite, hydrosulfite, sodium sulfite, sodium thiosulfate, as needed.
The usage-amount of a radical polymerization initiator is 0.1-10 weight part normally with respect to 100 weight part of monomer whole quantity.

  The polymerization conditions are not particularly limited, and may be heated in an inert gas atmosphere at 20 to 120 ° C. for 4 to 50 hours, and may be appropriately adjusted depending on the polymerization solvent, the monomer composition, and the polymerization initiator species.

The PSS sodium of the present invention can be produced by the above-mentioned general radical polymerization, but if a living polymerization method is applied, the molecular weight distribution can be narrowed or a block copolymer can be produced.
For polar monomers such as sodium parastyrene sulfonate, the living radical polymerization method is more preferred.
Examples of the living radical polymerization method include an atom transfer polymerization method, a stable nitroxyl-mediated polymerization method, a reversible addition-cleavage transfer polymerization method, and an organic tellurium-mediated polymerization method (Polymer Papers, vol. 64, No. 6, pp. 199). 329, 2007), iodine transfer polymerization method (Japanese Patent Laid-Open No. 2007-92014; collection of polymer papers, vol. 59, No. 10, 798, 2010; catalyst, vol. 54, No. 4, 257) 2012), a polymerization method using a complex of phosphine and carbon disulfide (Japanese Patent Laid-Open No. 2006-233012), a method using trialkylborane (adhesion, 50, 4, No. 23, 2006), α- Examples include methods using methylstyrene dimer (Japanese Patent Laid-Open No. 2000-169531), and these methods can also be applied to the present invention.

As a specific example of living radical polymerization, after living radical polymerization of a radical polymerizable monomer other than sodium parastyrene sulfonate in an aqueous solvent, the sodium parastyrene sulfonate of the present invention is added, and further living radical polymerization is continued, or After living radical polymerization of sodium parastyrene sulfonate in an aqueous solvent, another radical polymerizable monomer is added and the living radical polymerization is continued. For example, a PSS block copolymer can be produced by performing such living radical polymerization.
The PSS sodium of the present invention may be randomly copolymerized with a monomer capable of radical copolymerization with sodium parastyrene sulfonate, if necessary. Although there is no restriction | limiting in particular, For example, the monomer described by description of the PSS sodium block copolymer is mention | raise | lifted.

Next, a method for producing chloroprene rubber will be described. These production methods are not particularly limited, and known methods can be applied (for example, the above-mentioned Japanese Patent No. 3601136).
For example, a reactor equipped with a stirrer and a temperature control jacket is charged with water, monomers such as chloroprene, emulsifiers, dispersants, molecular weight regulators, and pH adjusters as necessary to remove oxygen in the system. After sufficiently emulsifying the monomer, polymerization may be performed at a predetermined temperature while adding a radical initiator. In order to increase the crystallinity and cohesive strength of chloroprene, a radical initiator and a reducing agent may be used in combination and polymerized at a low temperature. Polymerization is carried out at 10 to 50 ° C. for 3 to 10 hours. When a desired polymerization conversion rate is reached, a polymerization inhibitor is added to stop the polymerization. As the molecular weight regulator, the polymerization initiator, and the reducing agent, those used in the production of PSS sodium can be used. Furthermore, a hard component such as polymethyl methacrylate may be graft-polymerized to impart polarity and cohesive strength to the chloroprene rubber obtained above.

  The emulsifier is not particularly limited. Examples of the anionic emulsifier include rosinate, fatty acid salt, alkenyl succinate, alkyl ether carboxylate, alkyl diphenyl ether disulfonate, alkane sulfonate. , Alkyl succinate sulfonate, polyoxyethylene polycyclic phenyl ether sulfate, α-olefin sulfonate, alkyl benzene sulfonate, polyacrylate acrylic acid copolymer, polymethacrylate methacrylic acid copolymer Polymer, polyacrylamide acrylic acid copolymer, polymethacrylamide methacrylic acid copolymer, alkyl sulfosuccinate, alkyl sulfate ester salt, alkyl ether sulfate ester salt, alkylpropenylphenol polyethylene oxide Sulfuric acid ester salts of allyl alkylphenol polyethylene oxide adducts, alkyl phosphoric acid ester salts, polyoxyethylene alkyl ether phosphoric acid ester salts, sulfonic acid salts of higher fatty acid amides, sulfuric acid esters of higher fatty acid alkylolamides Examples of nonionic emulsifiers include polyoxyalkylene alkylamines, alkylalkanolamides, amine oxide nonionic emulsifiers, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyalkylene polycyclic phenyls. Ether, alkylpropenylphenol polyethylene oxide adduct, allylalkylphenol polyethylene oxide adduct, polyoxyethylene fatty acid ester, poly Oxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, alkylpolyglucoxide, sucrose fatty acid ester, polyoxyethylene polyoxypropylene glycol, polyvinyl alcohol, carboxymethylcellulose, polyvinylpyrrolidone, hydroxyethylcellulose, polyacrylamide, polymethacrylamide , Polydimethylaminoethyl methacrylate, polydimethylaminoethyl acrylate, polydiethylaminoethyl methacrylate, polydiethylaminoethyl acrylate, poly-t-butylethylaminoethyl methacrylate, poly-t-butylaminoethyl acrylate, polydimethylaminoethyl methacrylate / methyl methacrylate copolymer Coalesced, polydimethylamino Examples include cationic amines such as alkylamine salts, alkyl acrylates, methyl methacrylate copolymers, polydimethylaminoethyl methacrylate / butyl acrylate copolymers, and polydimethylaminoethyl acrylate / ethyl acrylate copolymers. Type quaternary ammonium salts, fatty acid amidoamine salts, alkylamino acid salts and the like. Examples of amphoteric emulsifiers include alkyldimethylaminoacetic acid betaine, alkyldimethylaminosulfobetaine, and alkylsulfobetaine.

  Examples of the dispersant include naphthalene sulfonate formalin condensate, taurine derivative, polystyrene sulfonic acid (salt), polystyrene sulfonic acid / methacrylic acid copolymer (salt), polystyrene sulfonic acid / acrylic acid copolymer (salt). ), Polystyrene sulfonic acid / acrylic acid ester copolymer (salt), styrene sulfonic acid / maleic acid copolymer (salt), styrene sulfonic acid / acrylamide copolymer (salt), styrene sulfonic acid / methacrylamide copolymer (Salt), styrene sulfonic acid / 2-hydroxyethyl methacrylate copolymer (salt), styrene sulfonic acid / vinyl pyrrolidone copolymer (salt), polyvinyl phosphonic acid copolymer (salt), polyvinyl sulfonic acid copolymer ( Salt), polyisoprene sulfonic acid copolymer (salt), etc. Particularly preferably a high-purity PSS sodium present invention.

The high-purity sodium parastyrene sulfonate of the present invention has a significantly superior hue compared to conventional products. Therefore, the high-purity sodium parastyrene sulfonate and the PSS sodium obtained using the same are produced in polymer emulsions such as chloroprene rubber. Is a very useful reactive emulsifier and dispersant.
The PSS sodium with excellent hue produced in the present invention can be used as a dispersant for producing the polymer emulsion such as chloroprene rubber described above, as well as a synthetic glue for clothing iron finishing in which hue is important, personal care It is extremely useful as a dispersant for producing various aqueous dispersions such as articles, antistatic agents, and pigments. Here, when used as a synthetic paste in a garment iron finish, the specific embodiments thereof include a silicone polymer (functioning as a smoothing agent) and propylene glycol (functioning as a stabilizer) in the PPS sodium aqueous solution of the present invention. ), Preservatives, fragrances and the like.

The following examples further illustrate the present invention, but the present invention is not limited to these examples.
In the following examples, analysis and evaluation of β-haloethylbenzene sulfonic acid, sodium parastyrene sulfonate, sodium PSS, and chloroprene rubber were performed under the following conditions.

<Quantification of iron content in β-haloethylbenzenesulfonic acid and sodium parastyrene sulfonate by ICP-MS>
About 0.1 g of a sample was precisely weighed into a 25 ml polymesh flask, 1 ml of 68% high-purity nitric acid was added, and after measuring up, the iron content was quantified with an inductively coupled plasma mass spectrometer NexION300S manufactured by PerkinElmer.

<Measurement of concentration of β-bromoethylbenzenesulfone aqueous solution by HPLC>
The sample was dissolved in the following eluent A to prepare a solution having a concentration of 1.2 to 1.5 mg / ml, and HPLC analysis was performed. The measurement conditions are as follows. A calibration curve was prepared using 70 wt% β-bromoethylbenzenesulfone aqueous solution as a standard.
Model = LC-8020 manufactured by Tosoh Corporation
(Degasser: SD-8022, pump: CCPM-II, column oven: CO-8020, UV-visible detector: UV-8020)
Column = TSKgel ODS-80TsQA (4.6 mm × 25 cm)
Eluent = A solution) Water / acetonitrile volume ratio = 95/5 + 0.1 wt% trifluoroacetic acid
B liquid) Water / acetonitrile volume ratio = 80/20 + 0.1 wt% trifluoroacetic acid Gradient condition = A liquid 100% up to 55 minutes, B liquid 100% from 55 minutes to 95 minutes
Flow rate = 0.8 ml / min, UV detection condition = 230 nm, column temperature = room temperature, injection amount = 20 μl

<Quantitative determination of water in sodium parastyrene sulfonate>
2 g of the sample was weighed in a weighing bottle (diameter 55 mm × height 30 mm) to the order of 0.1 mg and dried for 90 minutes with a dryer (105 ± 5 ° C.). Immediately after moving to a desiccator and cooling to room temperature, the mass was measured to the order of 0.1 mg, and moisture was calculated from the following equation.
Moisture (wt%) = 100 × (ab) / S
a = weight of the sample and weighing bottle before drying (g), b = weight of the sample and weighing bottle after drying (g), S = sample amount (g)

<Quantification of sodium styrenesulfonate content (pure content) in sample>
The active double bond was quantified by the oxidation-reduction titration method, and the content of sodium styrenesulfonate in the sample (that is, including the ortho and meta forms in addition to the para form) was determined.
(1) Instrument and device 1) Weighing bottle: diameter 50 mm, depth 70 mm
2) 500 ml, 1000 ml measuring flask 3) Erlenmeyer flask with 500 ml stopper 3) Electrochemical balance (2) Reagent 1) Bromine solution: 22.00 g of potassium bromide (KBr), 3.00 g of potassium bromate (KBrO ₃ ) The whole was dissolved in pure water to make 1000 ml.
2) Aqueous sulfuric acid solution (concentrated sulfuric acid / pure water volume ratio = 1/1)
3) Potassium iodide aqueous solution (200 g / L)
4) 0.1 mol / L sodium thiosulfate aqueous solution 5) Starch aqueous solution: 6.00 g of starch was dissolved in pure water to make 1000 ml as a whole.
(3) Operation 1) Weigh 20 g of sample to the order of 0.1 mg in a weighing bottle.
2) Rinse into a 500 ml volumetric flask with pure water to make the liquid volume about 400 ml.
3) Put a magnetic rotor and stir to dissolve the sample.
4) Take out the rotor, align the mark with pure water and shake to make the test solution.
5) Add 25 ml of bromine solution to a 500 ml conical stoppered flask containing 200 ml of pure water.
6) Add 5 ml of the test solution, add 10 ml of sulfuric acid aqueous solution, seal tightly and leave for 20 minutes.
7) Add 10 ml of potassium iodide aqueous solution quickly and leave for 10 minutes.
8) Titrate with an aqueous sodium thiosulfate solution, and after the solution becomes light yellow, add 1 ml of starch solution as an indicator, and titrate until the blue color of the resulting iodine starch disappears.
9) Separately, as a blank test, add 200 ml of pure water, add 25 ml of bromine solution to a conical flask with a stopper, quickly add 10 ml of potassium iodide aqueous solution and 10 ml of sulfuric acid aqueous solution, and perform the operation of 8).
(4) Calculation The sodium styrenesulfonate content is calculated by the following formula.
A = 100 × [0.01031 × (ab) × f] / (S × 5/500)
A: Sodium styrenesulfonate content (%)
a: Sodium thiosulfate aqueous solution (ml) required for the blank test
b: Sodium thiosulfate aqueous solution (ml) required for this test
f: Potency of sodium thiosulfate aqueous solution S: Sample amount (g)

<Quantification of sodium bromide in sodium parastyrene sulfonate>
(1) Preparation of sample 20 g of sample was weighed in a weighing bottle (50 mmφ × 70 mm) to the order of 0.1 mg, washed with pure water into a 500 ml volumetric flask, and the liquid volume was about 400 ml. After stirring and dissolving with a magnetic stirring bar, the stirring bar was taken out, and pure water was added to the marked line and shaken. 5 ml of the solution was correctly collected in a 100 ml volumetric flask, and pure water was added up to the marked line to obtain a sample solution.
Ion the sample solution and mixed standard solution (prepared using Kanto Chemical Co., Ltd. standard solution so that Br = 5,000 μg / 100 ml, Cl = 500 μg / 100 ml, SO ₄ = 2,000 μg / 100 ml) The sample was injected into the chromatograph, and the amount of sodium bromide in the sample was calculated from each peak area.
(2) Measurement conditions Model = Tosoh Corporation, ion chromatography system 8020
Column = TSK-Gel IC-Anion-PW
Column temperature = 40 ° C
Sample injection volume = 100 μl
Flow rate = 0.7ml
Eluent: 5 g of potassium hydrogen phthalate and 300 ml of acetonitrile were added pure water to prepare a total of 3000 ml.
(3) Calculation The content of sodium bromide (NaBr) was calculated by the following formula.
A = [[(5,000 μg × 1.288 × a / b) + (500 μg × 2.899 × c / d)] / (S × 5/500)] × 10 ⁻⁴
A: Content of sodium bromide (NaBr) (%)
a: Sample area (Br)
b: Standard area (Br)
c: Sample area (Cl)
d: Standard area (Cl)
S: Sample amount (g)

<Analysis of impurities in sodium parastyrene sulfonate by HPLC>
The measurement conditions are the same as the measurement of the concentration of the β-bromoethylbenzenesulfone aqueous solution. A sodium parastyrenesulfonate (solid sample containing crystal water and adhering water) sample was dissolved in the eluent A to prepare a solution having a concentration of 0.5 mg / ml, and HPLC analysis was performed. The content rate of each impurity (a)-(e) is an area ratio which set the sum total of the HPLC peak area of sodium parastyrenesulfonate and (a)-(e) detected on these conditions to 100.
Each peak detected by HPLC was previously identified by the following method.
After separating each component detected by HPLC and treating with cation exchange resin to convert parastyrene sulfonate to sulfonic acid type, methyl ester of sulfonic acid group with diazomethane, gas chromatograph mass spectrometry (Hitachi, Ltd.) M-80B), Fourier transform infrared analysis (Perkin Elmer, System 2000), organic element analysis (Yanaco, CHN coder MT-3), and nuclear magnetic resonance analysis (Varian, VXR-300) And the structure was determined.

<Measurement of particle size distribution>
0.55 g of sample and 15.0 g of isopropanol were collected in a 30 ml glass sample bottle, treated with an ultrasonic cleaner for 4 minutes to prepare a slurry, and then laser diffraction / scattering particle size analyzer Microtrac HRA (manufactured by Nikkiso Co., Ltd.) The particle size (median diameter) distribution was measured under the following conditions.
Particle Transparency = Transp
Physical Particles = No
Particle Refractive Index = 1.55
Fluid Refractive Index = 1.38

<Measurement of repose angle>
(1) Instrument and apparatus 1) The angle of repose measurement apparatus, 2) Protractor, and 3) The electronic pan balance were configured as shown in FIG.
(2) Operation 1) The sample 80g is naturally dropped on the petri dish through the funnel of the apparatus.
2) Read the apex angle (a) of the cone on the petri dish to an integer number with a protractor.
3) Repeat this operation three times to obtain the average value of the apex angle (a) of the cone.
(3) Calculation Calculate the angle of repose according to the following formula. The smaller the angle of repose, the better the fluidity.
A = (180−a) / 2
Where A: angle of repose (degrees), a: apex angle of the cone (degrees)

<Measurement of dissolution rate [solubility in water]>
In a constant temperature room at 25 ° C., 1.00 g of sodium parastyrenesulfonate powder (solid containing impurities and moisture) is precisely weighed in a 20 ml glass sample bottle (outer diameter 27 mm × depth 55 mm), and then ion-exchanged water. 9.00 g was added quickly. Thereafter, the upper and lower sides of the sample bottle were reversed at a cycle of 1 cycle per second, and the time until the sodium parastyrene sulfonate was dissolved was visually determined.

<Measurement of whiteness and yellowness of sodium parastyrene sulfonate by color difference meter>
After the color difference meter (Nippon Denshoku Industries Co., Ltd., C-106) was turned on and stabilized for 30 minutes, a light projection lens (30 mmφ) and a sample stage (30 mmφ) were attached and standard alignment was performed. A sample (3.0 g) was weighed in a cell and a 1 KG weight was placed for 30 seconds. Measured with a color difference meter, whiteness (WI value) and yellowness (YI value) were read.

<Measurement of APHA value of sodium parastyrene sulfonate and sodium polystyrene sulfonate aqueous solution>
After the color difference meter (Nippon Denshoku Industries Co., Ltd., C-106) was turned on and stabilized for 30 minutes, the measurement method was changed to transmission, and a projection lens (30 mmφ) and sample stage (30 mmφ) were attached. A white plate and a 0-CAL plate were set and zero calibration was performed. After performing standard calibration by putting water in the square cell, a 15 wt% sodium parastyrene sulfonate and 15 wt% sodium polystyrene sulfonate aqueous solution sample was transferred to the square cell and set, and the APHA value was read (standard of APHA 0 to 500). Converted from a calibration curve created using the solution).

<Hue evaluation as a synthetic paste for clothing iron finishes>
A commercially available polyester cotton blend white fabric cut into a circle having a diameter of 5 cm was immersed in a 15 wt% aqueous solution of sodium polystyrene sulfonate (in terms of pure content). After the aqueous solution was acclimated to the whole dough, it was pulled up with tweezers, the excess aqueous solution was shaken off, and then dried with an iron at 180 ° C. for 3 minutes (the iron was fixed without moving) to prepare a test piece. The hue of the test piece was analyzed visually and with the above colorimeter.
After the color difference meter (Nippon Denshoku Industries Co., Ltd., C-106) was turned on and stabilized for 30 minutes, a light projection lens (30 mmφ) and a sample stage (30 mmφ) were attached and standard alignment was performed. After fixing the sample fabric on the back of the sample stage, a black box was put on the sample stage to block light from the outside, and the hue was measured. From the YI value representing yellowness and the b value representing yellowness and blueness, the performance as a synthetic paste for a garment iron finish was simply determined.

<Evaluation of hue of chloroprene rubber solution>
A 5 wt% toluene solution of chloroprene rubber was prepared, and the hue (yellowness) was evaluated by measuring the absorbance at a wavelength of 440 nm using an absorptiometer U-1500 manufactured by Hitachi, Ltd. The smaller the value, the lighter the color.
<Evaluation of heat aging resistance of hue>
After heating the chloroprene rubber in a gear oven at 70 ° C. for 3 days, the hue of the solution was evaluated by the above method.

<Measurement of GPC molecular weight and monomer polymerization conversion>
The monomer polymerization conversion rate and the molecular weight of PSS sodium were measured under the following conditions.
Model = Tosoh Corporation, LC-8020
(Degasser: SD-8022, pump: DP-8020, column oven: CO-8020, UV-visible detector: UV-8020)
Column = TSK guardcolumn α + TSK gel α-6000 + TSK gel α-3000
Eluent = phosphate buffer solution (pH = 7) and acetonitrile volume ratio 9: 1 solution (The above phosphate buffer solution is pure 0.08 mol KH ₂ PO ₄ and 0.12 mol Na ₂ HPO ₄ . It was dissolved in water to make a total volume of 1 L.)
Column temperature = 40 ° C., flow rate = 0.6 ml / min
Detector = UV detector (wavelength 230 nm), injection amount = 100 μl
Calibration curve was prepared from the peak top molecular weight and elution time of monodisperse sodium sulfonate (3K, 15K, 41K, 300K, 1000K, 2350K, 5000K) manufactured by Soka Kagaku.

Example 1 (Production of high-purity sodium parastyrene sulfonate, sodium PSS, and evaluation example 1 as a synthetic paste for a garment ironing agent)
(Production of β-bromoethylbenzenesulfonic acid with reduced iron content)
600 ml of cation exchange resin [manufactured by Organo, Amberlite RB-120 (regenerated with hydrochloric acid)] and 400 g of 73 wt% β-bromoethylbenzenesulfonic acid aqueous solution were collected in a polypropylene beaker and made of Teflon (polytetrafluoroethylene). The mixture was slowly stirred at room temperature for 5 hours using a stirring blade. Thereafter, the ion exchange resin was filtered off with a glass filter, and the concentration of the filtrate was adjusted with a rotary evaporator to obtain 350 g of a 70 wt% β-bromoethylbenzenesulfonic acid aqueous solution. The iron content in the aqueous solution was 0.34 μg / g.
In addition, the beta-bromoethylbenzenesulfonic acid used the intermediate product obtained by the manufacturing process of sodium parastyrene sulfonate.

(Production of high-purity sodium parastyrene sulfonate)
A stainless steel reactor equipped with a stirrer equipped with a jacket was charged with 390 parts by weight of a 12% aqueous sodium hydroxide solution and 1.2 parts by weight of sodium nitrite, and the temperature was raised to 70 ° C. while stirring. While maintaining this at 90 ° C., 660 parts by weight of a 48% sodium hydroxide aqueous solution and 1,012 parts by weight of the 70 wt% β-bromoethylbenzenesulfonic acid aqueous solution obtained above were added dropwise over 3 hours under stirring and nitrogen atmosphere. . The obtained slurry of sodium parastyrene sulfonate crystals was cooled to 30 ° C. and then solid-liquid separated with a centrifugal separator to obtain 446 parts by weight of a wet cake of sodium parastyrene sulfonate.
The purity of the sodium parastyrene sulfonate is 88.8 wt%, the water content is 6.5 wt%, the iron content is 0.56 μg / g, the sodium bromide content is 2.00 wt%, and the organic impurities such as isomers are (a) 0.16%, (b) 0.43%, (c) 2.65%, (d) 0.04%, (e) 0.15% (the HPLC chart is shown in FIG. 1).
The median diameter of the sodium parastyrene sulfonate was 81%, 0.5% of granules smaller than 10,000 μm, the angle of repose was 46 degrees, and the dissolution time in water was 165 seconds.
The sodium parastyrene sulfonate has a WI value of 95.7, a YI value of 5.8, and a 15 wt% aqueous solution with an APHA value of 30, which is clearly superior to the conventional product (Comparative Example 1). Indicated.

(Production of high-purity sodium polystyrene sulfonate)
A 1 L glass flask equipped with a reflux condenser, a nitrogen inlet tube, and a paddle type stirrer was charged with 100.00 g of pure water and heated in an oil bath at 85 ° C. in a nitrogen atmosphere. A separately prepared sodium parastyrenesulfonate aqueous solution (240.00 g of the high purity sodium parastyrenesulfonate obtained above was dissolved in pure water 824.00) was added for 86 minutes, and an aqueous initiator solution (ammonium persulfate 2. 00 g dissolved in pure water 121.00 g) was dropped over 220 minutes to carry out polymerization. Three hours after the start of polymerization, the oil bath temperature was raised to 90 ° C., and the polymerization was further continued for 3 hours to obtain an aqueous polystyrene sulfone sodium solution.
The number average molecular weight Mn of polystyrene sulfone sodium determined by GPC was 170,000, and the weight average molecular weight Mw was 360,000. The polymer was PSS-1.
The APHA value of the 15 wt% aqueous solution of PSS-1 was 50, which clearly showed a hue superior to that of the conventional product (Comparative Example 1). The difference in hue was obvious even by visual observation.

(Evaluation as a synthetic paste for clothing iron finishes)
The hue of the dough impregnated with a 15 wt% aqueous solution of PSS-1 and iron-dried was slightly better than Comparative Example 1 in visual evaluation. The b value of the fabric is -5.4 (b value of the original fabric is -6.8) and the YI value is -11.1 (YI value of the original fabric is -13.7), not yellow Although the result showed the degree of blue, the hue apparently close to that of the original fabric was shown in comparison with Comparative Example 1. That is, even with a small coating amount, the superiority of the hue over the conventional product (Comparative Example 1) is clear. The above evaluation results are summarized in Table 1.

Example 2 (Production of high-purity sodium parastyrene sulfonate, sodium PSS, and evaluation example 2 as a synthetic paste for a garment iron finish)
(Production of high-purity sodium parastyrene sulfonate)
A stainless steel reactor equipped with a stirrer equipped with a jacket was charged with 1,000 g of high-purity sodium parastyrenesulfonate obtained in Example 1, 1 g of sodium nitrite, 20 g of caustic soda, and 950 g of pure water. For 1 hour. Then, after cooling to room temperature over 3 hours, it was subjected to solid-liquid separation with a centrifugal separator to obtain 899 g of a wet cake of high-purity sodium parastyrenesulfonate.
The purity of the above high-purity sodium parastyrene sulfonate is 89.1 wt%, moisture is 8.2 wt%, iron content is 0.58 μg / g, sodium bromide content is 0.20 wt%, and organic impurities such as isomers are ( a) 0.05%, (b) 0.00%, (c) 1.34%, (d) 0.01%, (e) 0.01%.
The median diameter of the sodium parastyrene sulfonate was 63%, the small particles of less than 10,000 μm were 2.0%, the angle of repose was 49 degrees, and the dissolution time in water was 155 seconds.
The sodium parastyrene sulfonate has a WI value of 95.5, a YI value of 2.9, and a 15 wt% aqueous solution with an APHA value of 15, which is clearly superior to the conventional product (Comparative Example 1). Indicated. Furthermore, although the reason is not clear, even if the iron content is the same level as in Example 1, it is clear that the hue is further improved by reducing impurities such as sodium bromide and isomers.

(Production of high-purity sodium polystyrene sulfonate)
A 1 L glass flask equipped with a reflux condenser, a nitrogen inlet tube, and a paddle type stirrer was charged with 100.00 g of pure water and heated in an oil bath at 85 ° C. in a nitrogen atmosphere. Here, a separately prepared sodium parastyrene sulfonate aqueous solution (240.00 g of sodium parastyrene sulfonate obtained above was dissolved in 824.00 pure water) was added for 86 minutes to an aqueous initiator solution (2,2′-azobis). -(2-Amidinopropane) dihydrochloride (2.00 g) dissolved in 120.00 g of pure water) was added dropwise over 220 minutes to carry out polymerization. Three hours after the start of the polymerization, the oil bath temperature was raised to 90 ° C., and the polymerization was further continued for 3 hours to obtain a sodium polystyrenesulfonate aqueous solution.
The number average molecular weight Mn of polystyrene sulfonate sodium determined by GPC was 160,000, and the weight average molecular weight Mw was 350,000. The polymer was PSS-2.
The APHA value of the 15 wt% aqueous solution of PSS-2 is 10, which clearly shows that the hue is superior to that of the conventional product (Comparative Example 1).

(Evaluation as a synthetic paste for clothing iron finishes)
The hue of the dough impregnated with a 15 wt% aqueous solution of PSS-2 and iron-dried was slightly better than Comparative Example 1 in visual evaluation. The b value of the fabric is -6.0 (the b value of the original fabric is -6.8), the YI value is -12.2 (the YI value of the original fabric is -13.7), not yellow Although the result showed the degree of blue, the hue apparently close to that of the original fabric was shown in comparison with Comparative Example 1. That is, even with a small coating amount, the superiority of the hue over the conventional product (Comparative Example 1) is clear. The above evaluation results are summarized in Table 1.

Example 3 (Production and Evaluation Example 1 of PSS Sodium and Chloroprene Rubber)
(Production of sodium polystyrene sulfonate)
A 1 L glass flask equipped with a reflux condenser, a nitrogen inlet tube, and a paddle type stirrer was charged with 84.00 g of pure water and heated in an oil bath at 85 ° C. in a nitrogen atmosphere. Here, a separately prepared sodium parastyrenesulfonate aqueous solution (1933.00 g sodium parastyrenesulfonate obtained in Example 1 and 8.56 g thioglycerol dissolved in 700.00 pure water) was started for 73 minutes. Aqueous agent aqueous solution (5,10 'of 2,2'-azobis- (2-amidinopropane) dihydrochloride dissolved in 104.00 g of pure water) was added dropwise over 130 minutes to carry out polymerization. Three hours after the start of the polymerization, the oil bath temperature was raised to 90 ° C., and the polymerization was further continued for 3 hours to obtain a sodium polystyrenesulfonate aqueous solution.
The number average molecular weight Mn of polystyrene sulfonate sodium determined by GPC was 4,000, and the weight average molecular weight Mw was 5,200. The polymer was PSS-3.
The APHA value of the 15 wt% aqueous solution of PSS-3 is 15, which clearly shows that the hue is superior to that of the conventional product (Comparative Example 1).

(Manufacture of chloroprene rubber)
In a 10 L stainless steel reactor equipped with a stirrer equipped with a jacket, 100 parts by weight of chloroprene, 0.12 parts by weight of n-dodecyl mercaptan, 3.00 parts by weight of disproportionated potassium rosinate, and 2.00 parts by weight of the above sodium polystyrene sulfonate Parts, 0.20 parts by weight of sodium hydroxide, 0.005 parts by weight of hydrosulfite sodium, and 100 parts by weight of pure water, stirring was started under a nitrogen atmosphere, and a 0.35 wt% potassium persulfate aqueous solution was continuously added. Polymerization was started at 12 ° C. while dropping. When the polymerization conversion reached 70%, 0.05 part by weight of 2,2′-methylenebis- (4-ethyl-6-t-butylphenol) was added as a polymerization terminator to terminate the polymerization. No aggregates were observed in the emulsion.
Unreacted chloroprene was removed by a steam stripping method, the pH of the emulsion was adjusted to 6 with dilute acetic acid, freeze-coagulated, washed with water, and dried with hot air to obtain 71 parts by weight of solid chloroprene rubber.
(Evaluation of chloroprene rubber)
The absorbance (hue) of the chloroprene rubber solution was 0.03, and the absorbance after heat aging was 0.04, which was clearly superior to Comparative Example 5. The above evaluation results are summarized in Table 1.

Example 4 (Production and Evaluation Example 2 of PSS Sodium and Chloroprene Rubber)
(Production of sodium polystyrene sulfonate)
A 1 L glass flask equipped with a reflux condenser, a nitrogen inlet tube, and a paddle type stirrer was charged with 120.00 g of pure water and heated in an oil bath at 85 ° C. in a nitrogen atmosphere. Here, separately prepared sodium parastyrenesulfonate aqueous solution [210.00 g sodium parastyrenesulfonate obtained in Example 2, 19.98 g methacrylic acid, 6.21 g thioglycerol, and 39.45 wt% sodium hydroxide aqueous solution 23 .98 g dissolved in pure water 850.00], 85 minutes, initiator aqueous solution (2,2′-azobis- (2-amidinopropane) dihydrochloride 3.33 g dissolved in pure water 120.00 g ) Was added dropwise over 140 minutes to carry out polymerization. Three hours after the start of the polymerization, the oil bath temperature was raised to 90 ° C., and the polymerization was further continued for 3 hours to obtain an aqueous polystyrene sulfonate / sodium methacrylate copolymer aqueous solution as PSS sodium.
The number average molecular weight Mn of the polystyrene sulfonate sodium / sodium methacrylate copolymer determined by GPC was 5,600, and the weight average molecular weight Mw was 8,900. The polymer was PSS-4.
The APHA value of the 15 wt% aqueous solution of PSS-4 is 10, which clearly shows that the hue is superior to that of the conventional product (Comparative Example 1). Furthermore, although the reason is not clear, even if the iron content is the same level as in Example 3, it is clear that the hue is further improved by reducing impurities such as sodium bromide and isomers.

(Manufacture of chloroprene rubber)
A 10 L stainless steel reactor equipped with a stirrer equipped with a jacket was charged with 100 parts by weight of chloroprene, 0.12 parts by weight of n-dodecyl mercaptan, 3.00 parts by weight of disproportionated potassium rosinate, and the polystyrene sodium sulfonate / methacrylic acid copolymer. Polymer sodium copolymer 2.00 parts by weight, sodium hydroxide 0.20 parts by weight, hydrosulfite sodium 0.005 parts by weight and pure water 100 parts by weight were charged, and stirring was started in a nitrogen atmosphere. Polymerization was started at 12 ° C. while continuously dropping a 35 wt% potassium persulfate aqueous solution. When the polymerization conversion reached 70%, 0.05 part by weight of 2,2′-methylenebis- (4-ethyl-6-t-butylphenol) was added as a polymerization terminator to terminate the polymerization. No aggregates were observed in the emulsion.
Unreacted chloroprene was removed by a steam stripping method, the pH of the emulsion was adjusted to 6 with dilute acetic acid, freeze-coagulated, washed with water, and dried with hot air to obtain 71 parts by weight of solid chloroprene rubber.
(Evaluation of chloroprene rubber)
The absorbance (hue) of the chloroprene rubber solution was 0.03, and the absorbance after heat aging was 0.04, which is clearly superior to Comparative Example 5. The above evaluation results are summarized in Table 1.

Example 5 (Production of high-purity sodium parastyrene sulfonate, sodium PSS, and evaluation example 3 as a synthetic paste for a garment iron finish)
(Production of high-purity sodium parastyrene sulfonate)
To a stainless steel reactor equipped with a stirrer equipped with a jacket, commercially available sodium parastyrenesulfonate (moisture content is 10.4 wt%, iron content is 5.12 μg / g, sodium bromide is 2.30 wt%, organic compounds such as isomers) Impurities are (a) 0.38%, (b) 3.87%, (c) 7.77%, (d) 0.06%, (e) 0.73%) (1,000 g) 1 g of sodium nitrate, 20 g of caustic soda and 950 g of pure water were charged and stirred at 40 ° C. for 1 hour in a nitrogen atmosphere. Then, after cooling to room temperature in 30 minutes, solid-liquid separation was performed with a centrifugal separator to obtain 900 g of a wet cake of high-purity sodium parastyrenesulfonate.
The purity of the high-purity sodium parastyrene sulfonate is 83.4 wt%, moisture is 10.2 wt%, iron content is 1.03 μg / g, sodium bromide content is 2.00 wt%, and organic impurities such as isomers are ( a) 0.30%, (b) 3.20%, (c) 6.40%, (d) 0.04%, (e) 0.39%.
The median diameter of the sodium parastyrene sulfonate was 18.6 μm, the small particles of less than 10,000 μm was 14.3%, the angle of repose was 59 degrees, and the dissolution time in water was 130 seconds.
The sodium parastyrene sulfonate had a WI value of 95.0, a YI value of 7.5, and a 15 wt% aqueous solution with an APHA value of 80, which was inferior to those of Examples 1 and 2, but the conventional product (Comparative Example 1). ) Was clearly superior to that of). Furthermore, although the reason is not clear, even if the iron content is equivalent to that of Comparative Example 5, it is clear that the hue is further improved by reducing impurities such as sodium bromide and isomers.

(Production of high-purity sodium polystyrene sulfonate)
A 1 L glass flask equipped with a reflux condenser, a nitrogen inlet tube, and a paddle type stirrer was charged with 100.00 g of pure water and heated in an oil bath at 85 ° C. in a nitrogen atmosphere. Here, a separately prepared sodium parastyrenesulfonate aqueous solution (240.00 g of sodium parastyrenesulfonate obtained above dissolved in pure water 824.00) was added for 86 minutes, and an aqueous initiator solution (2.00 g of ammonium persulfate was added). Polymer dissolved in 121.00 g of pure water) was added dropwise over 220 minutes. Three hours after the start of the polymerization, the oil bath temperature was raised to 90 ° C., and the polymerization was further continued for 3 hours to obtain a sodium polystyrenesulfonate aqueous solution.
The number average molecular weight Mn of polystyrene sulfonate sodium determined by GPC was 160,000, and the weight average molecular weight Mw was 340,000. The polymer was PSS-5.
The APHA value of the 15 wt% aqueous solution of PSS-5 is 100, and it is clear that it has an excellent hue as compared with Comparative Example 1.

(Evaluation as a synthetic paste for clothing iron finishes)
The hue of the dough impregnated with a 15 wt% aqueous solution of PSS-5 and iron-dried was slightly superior to Comparative Example 1 in visual evaluation. The b value of the dough is -4.9 (the b value of the original dough is -6.8), the YI value is -10.0 (the YI value of the original dough is -13.7), not yellow Although the result showed the degree of blue, the hue apparently close to that of the original fabric was shown in comparison with Comparative Example 1. That is, even with a small coating amount, the superiority of the hue with respect to Comparative Example 1 is clear. The above evaluation results are summarized in Table 1.

Comparative Example 1 (Production of PSS Sodium and Evaluation Example 4 as Synthetic Paste for Clothes Ironing Agent)
(Production of sodium polystyrene sulfonate)
As a result of analysis of commercially available sodium parastyrene sulfonate A, the purity was 82.9 wt%, the moisture content was 10.4 wt%, the iron content was 5.12 μg / g, the sodium bromide was 2.30 wt%, and organic impurities such as isomers. (A) 0.38%, (b) 3.87%, (c) 7.77%, (d) 0.06%, (e) 0.62% (FIG. 2 shows the HPLC chart) showed that). The WI value was 90.2, the YI value was 16.5, and the APHA value of the 15 wt% aqueous solution was 220. The hue was clearly inferior to that of the high-purity sodium parastyrenesulfonate of Example 1.
The median diameter of the sodium parastyrene sulfonate was 22.6 μm, small particles of less than 10,000 μm were 12.6%, the angle of repose was 60 degrees, and the dissolution time in water was 132 seconds.
Sodium polystyrene sulfonate was synthesized under the same conditions as in Example 1 using the sodium parastyrene sulfonate. The number average molecular weight Mn determined by GPC was 160,000, and the weight average molecular weight Mw was 350,000. The polymer was PSS-6.
The APHA value of the 15 wt% aqueous solution of PSS-6 was 250, and the hue was clearly inferior to that of the raw material sodium parastyrene sulfonate and sodium polystyrene sulfonate of Example 1.
The hue of the dough impregnated with a 15 wt% aqueous solution of PSS-6 and iron-dried was slightly inferior to Example 1 in visual evaluation. The b value of the dough is -3.8 (the b value of the original dough is -6.8), the YI value is -8.3 (the YI value of the original dough is -13.7), not yellow Although the result showed the degree of blue, the hue clearly separated from the original fabric as compared with Example 1. That is, the inferiority of the hue with respect to Example 1 is apparent even with a small coating amount. The above evaluation results are summarized in Table 1.

Comparative Example 2 (Production of PSS sodium and evaluation 5 as a synthetic paste for garment ironing agent)
Sodium polystyrene sulfonate was synthesized under the same conditions as in Example 2 using the same commercially available sodium parastyrene sulfonate A as in Comparative Example 1. The number average molecular weight Mn determined by GPC was 150,000, and the weight average molecular weight Mw was 340,000. The polymer was PSS-7.
The APHA value of the 15 wt% aqueous solution of PSS-7 was 210, and the hue was clearly inferior compared with the raw material sodium parastyrene sulfonate and sodium polystyrene sulfonate of Example 2. Here, the azo initiator 2,2′-azobis- (2-amidinopropane) dihydrochloride, which is reported to have no adverse effect on the hue of sodium polystyrene sulfonate, ie to obtain a good hue (for example, special Even when using Kaihei 11-181004), it is clear that a sufficient hue cannot be obtained if the raw material parastyrene sulfonate contains specific impurities.
The hue of the fabric impregnated with a 15 wt% aqueous solution of PSS-7 and iron-dried was slightly inferior to that of Example 2 by visual evaluation. The b value of the fabric is -4.2 (the b value of the original fabric is -6.8), the YI value is -8.8 (the YI value of the original fabric is -13.7), not yellow Although the result showed the degree of blue, the hue clearly separated from the original fabric as compared with Example 2. That is, even with a small coating amount, the inferiority of the hue with respect to Example 2 is clear. The above evaluation results are summarized in Table 1.

Comparative Example 3 (Production of PSS Sodium and Evaluation Example 6 as a Synthetic Paste for Clothing Iron)
(Production of sodium parastyrene sulfonate)
A stainless steel reactor equipped with a stirrer equipped with a jacket was charged with 1,500 g of commercially available sodium parastyrenesulfonate, 3.0 g of sodium nitrite, and 10,800 g of isopropanol as in Comparative Examples 1 and 2, and stirred and dispersed. Then, 2,700 g of pure water was added, and the mixture was stirred at 70 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, after cooling to room temperature over 4 hours, Nutsche filtration was performed, and the solvent was removed with a centrifuge to obtain 1,370 g of a wet cake of sodium parastyrenesulfonate.
As a result of analysis of the purified sodium parastyrene sulfonate, the purity was 85.5 wt%, the moisture was 10.8 wt%, the iron content was 5.10 μg / g, the sodium bromide was 0.45 wt%, and the organic impurities such as isomers were (A) 0.01%, (b) 0.01%, (c) 1.60%, (d) 0.03%, (e) 0.03%. As a result of measuring the hue, the WI value was 93.5, the YI value was 12.5, and the APHA value of the 15 wt% aqueous solution was 150, which was clearly inferior to the high-purity sodium parastyrene sulfonate of Example 1. . That is, it is clear that even if the amount of organic impurities such as sodium bromide and isomers is reduced, a sufficient hue cannot be obtained when the amount of iron is large.
The median diameter of the sodium parastyrenesulfonate was 12.1% for small particles less than 10,000 μm, the repose angle was 59 degrees, and the dissolution time in water was 123 seconds.
Sodium polystyrene sulfonate was synthesized under the same conditions as in Example 1 using the sodium parastyrene sulfonate. The number average molecular weight Mn determined by GPC was 180,000, and the weight average molecular weight Mw was 380,000. The polymer was PSS-8.
The APHA value of the 15 wt% aqueous solution of PSS-8 was 170, and the hue was clearly inferior to that of sodium polystyrene sulfonate of Example 1. Further, when the iron content in the sodium parastyrene sulfonate is large, it is apparent that the increase in APHA after conversion to a polymer is also large.
(Evaluation as a synthetic paste for clothing iron finishes)
The hue of the fabric impregnated with a 15 wt% aqueous solution of PSS-8 and iron-dried was slightly inferior to that of Example 1 by visual evaluation. The b value of the fabric is -4.5 (b value of the original fabric is -6.8), and the YI value is -8.9 (YI value of the original fabric is -13.7). Although the result showed the degree of blue, the hue clearly separated from the original fabric as compared with Example 1. That is, the inferiority of the hue with respect to Example 1 is apparent even with a small coating amount. The above evaluation results are summarized in Table 1.

Comparative Example 4 (Evaluation Example 7 as Synthetic Paste for Sodium Parastyrenesulfonate, Sodium PSS, and Clothing Iron)
(Production of sodium parastyrene sulfonate)
A stainless steel reactor equipped with a stirrer equipped with a jacket was charged with 1,054 parts by weight of 35% aqueous sodium hydroxide solution and 1.2 parts by weight of sodium nitrite, and the temperature was raised to 105 ° C. while stirring. While maintaining this at 105 ° C., 1,012 parts by weight of the 70 wt% β-bromoethylbenzenesulfonic acid aqueous solution obtained in Example 1 was added dropwise over 1 hour under stirring and in a nitrogen atmosphere. The obtained slurry of sodium parastyrene sulfonate crystals was cooled to 30 ° C., and then solid-liquid separated with a centrifugal separator to obtain 451 parts by weight of a wet cake of sodium parastyrene sulfonate.
As a result of analyzing the sodium parastyrene sulfonate, the purity was 82.7 wt%, the moisture was 10.5 wt%, the iron content was 1.05 μg / g, the sodium bromide was 2.51 wt%, and the organic impurities such as isomers were (A) 0.40%, (b) 4.20%, (c) 8.20%, (d) 0.10%, (e) 0.72%. The WI value was 93.0, the YI value was 10.1, and the APHA value of the 15 wt% aqueous solution was 120. The hue was clearly inferior to the high-purity sodium parastyrenesulfonate of Example 1. That is, it is clear that even if the iron content in sodium parastyrene sulfonate is less than 3.00 μg / g, a sufficient hue cannot be obtained when there are many organic impurities such as sodium bromide and isomers.
The median diameter of the sodium parastyrene sulfonate was 20.6 μm, the particles smaller than 10,000 μm were 14.3%, the angle of repose was 60 degrees, and the dissolution time in water was 126 seconds.

(Production of sodium polystyrene sulfonate)
Sodium polystyrene sulfonate was synthesized under the same conditions as in Example 1 using the sodium parastyrene sulfonate. The number average molecular weight Mn determined by GPC was 160,000, and the weight average molecular weight Mw was 350,000. The polymer was PSS-9.
The APHA value of the 15 wt% aqueous solution of PSS-9 was 150, and the hue was clearly inferior to that of sodium polystyrene sulfonate of Example 1. Further, when there are many organic impurities such as sodium bromide and isomers contained in sodium parastyrenesulfonate, it is apparent that the increase in APHA after conversion to a polymer is also large.
(Evaluation as a synthetic paste for clothing iron finishes)
The hue of the dough impregnated with a 15 wt% aqueous solution of PSS-9 and iron-dried was slightly inferior to that of Example 1 by visual evaluation. The b value of the fabric is -4.3 (b value of the original fabric is -6.8), the YI value is -8.7 (YI value of the original fabric is -13.7), not yellow Although the result showed the degree of blue, the hue clearly separated from the original fabric as compared with Example 1. That is, the inferiority of the hue with respect to Example 1 is apparent even with a small coating amount. The above evaluation results are summarized in Table 1.

Comparative Example 5 (Production of PSS sodium and chloroprene rubber and Evaluation Example 3)
(Production of sodium polystyrene sulfonate)
In Example 4, in place of the high-purity sodium parastyrene sulfonate, the commercially available sodium parastyrene sulfonate used in Comparative Example 1 was used. A copolymer aqueous solution was synthesized.
The number average molecular weight Mn of polystyrene sodium sulfonate / sodium methacrylate copolymer determined by GPC was 5,300, and the weight average molecular weight Mw was 9,100. The polymer was PSS-10.
The APHA value of the 15 wt% aqueous solution of PSS-10 was 210, and the hue was clearly inferior as compared with the sodium polystyrene sulfonate / sodium methacrylate copolymer of Example 4.
(Manufacture of chloroprene rubber)
In Example 4, chloroprene rubber was used under the same conditions as in Example 4 except that the polystyrenesulfonic acid / methacrylic acid copolymer sodium salt obtained above was used instead of the polystyrenesulfonic acid / methacrylic acid copolymer sodium salt. 71 parts by weight were obtained.
(Evaluation of chloroprene rubber)
The absorbance (hue) of the chloroprene rubber solution was 0.15, and the absorbance after heat aging was 0.19, which was clearly inferior to Example 4. The above evaluation results are summarized in Table 1.

Comparative Example 6 (Production of PSS Sodium and Evaluation Example 8 as Synthetic Paste for Clothes Ironing Agent)
(Production of sodium polystyrene sulfonate)
As a result of analysis of commercially available sodium parastyrene sulfonate B, purity was 82.3 wt%, moisture was 10.3 wt%, iron content was 2.90 μg / g, sodium bromide was 2.40 wt%, and organic impurities such as isomers. Were (a) 0.35%, (b) 4.20%, (c) 7.90%, (d) 0.05%, and (e) 0.61%. The WI value was 91.0, the YI value was 16.0, and the APHA value of the 15 wt% aqueous solution was 200. The hue was clearly inferior to the high-purity sodium parastyrenesulfonate of Example 1.
The median diameter of the sodium parastyrene sulfonate was 21.3 μm, 12.7% of small particles less than 10,000 μm, the angle of repose was 59 degrees, and the dissolution time in water was 122 seconds.
Sodium polystyrene sulfonate was synthesized under the same conditions as in Example 1 using the sodium parastyrene sulfonate. The number average molecular weight Mn determined by GPC was 160,000, and the weight average molecular weight Mw was 350,000. The polymer was designated PSS-11.
The APHA value of the 15 wt% aqueous solution of PSS-11 was 230, and the hue was clearly inferior compared with the raw material sodium parastyrene sulfonate and sodium polystyrene sulfonate of Example 1.
The hue of the dough impregnated with a 15 wt% aqueous solution of PSS-11 and iron-dried was slightly inferior to Example 1 in visual evaluation. The b value of the fabric is -4.2 (the b value of the original fabric is -6.8), the YI value is -8.8 (the YI value of the original fabric is -13.7), not yellow Although the result showed the degree of blue, the hue clearly separated from the original fabric as compared with Example 1. That is, the inferiority of the hue with respect to Example 1 is apparent even with a small coating amount. The above evaluation results are summarized in Table 1.

  High purity sodium parastyrene sulfonate having improved hue according to the present invention and sodium polystyrene sulfonate produced using the same are excellent in hue, so that a dispersant for producing a pigment dispersion or a polymer emulsion, clothes washing It is useful for applications such as synthetic pastes for ironing, personal care products, antistatic agents and the like.

(A): Absorption peak of sodium orthostyrenesulfonate (b): Absorption peak of sodium β-bromoethylbenzenesulfonate (c): Absorption peak of sodium metastyrenesulfonate (d): Absorption peak of sodium bromostyrenesulfonate (E): Absorption peak of sodium β-hydroxyethylbenzenesulfonate NaSS (para form): Absorption peak of sodium parastyrenesulfonate
elution solvent: Absorption peak derived from eluent

Claims (8)

  Iron content in sodium parastyrene sulfonate is less than 3.00 μg / g, sodium bromide is less than 2.50 wt%, (a) sodium orthostyrene sulfonate, (b) sodium β-bromoethylbenzene sulfonate, (c The peak area ratios obtained by high performance liquid chromatography (HPLC) of () sodium metastyrene sulfonate, (d) sodium bromostyrene sulfonate, and (e) sodium β-hydroxyethylbenzenesulfonate are (a) ≦ 0.40. %, (B) ≦ 4.00%, (c) ≦ 8.00%, (d) ≦ 0.10%, and (e) ≦ 0.80% (provided that sodium parastyrenesulfonate and (a) (E) High-purity sodium parastyrene sulfonate having an excellent hue of 100).   Iron content in sodium parastyrene sulfonate is less than 3.00 μg / g, sodium bromide is less than 2.50 wt%, (a) sodium orthostyrene sulfonate, (b) sodium β-bromoethylbenzene sulfonate, (c The peak area ratios determined by high performance liquid chromatography (HPLC) of sodium metastyrene sulfonate, (d) sodium bromostyrene sulfonate, and (e) sodium β-hydroxyethylbenzene sulfonate are (a) ≦ 0.20, respectively. %, (B) ≦ 0.50%, (c) ≦ 3.00%, (d) ≦ 0.10%, (e) ≦ 0.20% and (wherein sodium parastyrenesulfonate and (a) (E) The sum of peak areas is 100) The high purity sodium parastyrene sulfonate having excellent hue according to claim 1. The manufacturing method of the high purity sodium parastyrenesulfonate excellent in the hue of Claim 1 or 2 by any one of following (i)-(iii).
(I) When producing sodium parastyrene sulfonate by reaction crystallization of β-bromoethylbenzene sulfonic acid and sodium hydroxide, β-bromoethyl benzene sulfonic acid, which is a precursor of sodium parastyrene sulfonate, is converted with a cation exchange resin. A method of removing iron ions by processing.
(Ii) Filtering off water-soluble ferrous hydroxide from sodium parastyrene sulfonate obtained by reaction crystallization of β-bromoethylbenzene sulfonic acid and sodium hydroxide, or further obtaining parastyrene sulfonic acid obtained A method of washing or crystallizing sodium.
(Iii) A method in which air is blown into an alkaline aqueous solution of sodium parastyrenesulfonate or an oxidizing agent is added to precipitate water-insoluble ferric hydroxide, followed by filtration. A polystyrene polystyrene sulfonate having excellent hue, comprising the following repeating structural unit A, or the following repeating structural unit A and the following repeating structural unit B, produced using the high-purity sodium parastyrene sulfonate of claim 1 or 2.


[In repeating structural units A and B, M represents a sodium cation, Q represents another radical polymerizable monomer residue, n represents an integer of 1 or more, and m represents an integer of 0 or more. ] The polystyrene sulfonate with excellent hue according to claim 4 , wherein the weight average molecular weight determined by gel permeation chromatography is 2,000 to 1,000,000. Q is a (meth) acrylic acid residue, (meth) acrylic acid ester residue, (meth) acrylamide residue, maleic anhydride residue, maleic acid residue, N-phenylmaleimide residue, N-cyclohexylmaleimide residue 6. A polystyrene sulfonic acid having excellent hue according to claim 4 , wherein the radical polymerizable monomer residue is a radically polymerizable monomer residue selected from the group consisting of styrene residues and styrene derivative residues. sodium. A dispersant comprising sodium polystyrenesulfonate having an excellent hue according to any one of claims 4 to 6 as an active ingredient. An iron finishing agent for clothing produced by using sodium polystyrene sulfonate having excellent hue according to any one of claims 4 to 6 as a synthetic paste.