JP2018030909A - Ultra high molecular weight polystyrene sulfonic acid or a salt thereof, production method thereof and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-soluble ultrahigh molecular weight polystyrene sulfonic acid or a salt thereof having a high molecular weight or a high solution viscosity and a low content of a styrene sulfonic acid monomer, a method for producing the same, and the ultrahigh molecular weight polystyrene sulfonic acid or a salt thereof. Provide applications such as thickeners or dispersants. A water-soluble polymer containing a styrene sulfonic acid structural unit and a divinylbenzene sulfonic acid structural unit, wherein the weight average molecular weight of the water-soluble polymer exceeds 900,000 daltons (Da) obtained by gel permeation chromatography. And / or a method for producing an ultrahigh molecular weight polystyrene sulfonic acid or a salt thereof having a viscosity measured as a 5 wt% aqueous solution (30 ° C.) exceeding 100 mPa · s, and a divinylbenzene sulfonic acid or a salt thereof as a comonomer. , And its uses. [Selection diagram] None

Description

  The present invention relates to an ultra high molecular weight polystyrene sulfonic acid or salt thereof usable as an aqueous solution, a production method using divinylbenzene sulfonic acid or salt thereof as a comonomer, and a thickening containing the ultra high molecular weight polystyrene sulfonic acid or salt thereof. The present invention relates to the use of an agent or a dispersant.

  Hundreds of molecular weight such as natural polymers such as guar gum, xanthan gum, hydroxypropyl cellulose, carboxymethyl cellulose, synthetic polymers such as polyvinylpyrrolidone, polyacrylamide, polyacrylate, poly-2-acrylamide-2-methylpropanesulfonate Over 10,000 water-soluble or water-swellable polymers are used in applications such as synthetic glues, cosmetics, toiletries, tablets, polymer flocculants, soil modifiers, fire extinguishers, and oil mining. Yes. However, depending on the application, heat resistance and chemical stability are insufficient, and improvement is strongly demanded.

  For example, in enhanced oil recovery (EOR) in conventional oil fields and shale gas (oil) mining in non-conventional oil fields, aqueous fluids thickened with water-soluble or water-swellable polymers are used. As the mining depth increases, the heat resistance required for water-soluble or water-swellable polymers is increasing. In addition, depending on the formation, a large amount of acid or alkali may be injected or active oxygen radicals may be generated, so that chemical stability against these is required. For example, it may be necessary to maintain the viscosity of an aqueous fluid over several years, ie, the polymer molecular weight. However, since conventional polymers have insufficient heat resistance and chemical stability, and molecular weight tends to decrease in harsh environments, improvements are strongly demanded. For example, the natural polymer having an ether bond in the main chain is said to decompose at a temperature exceeding 50 ° C. in the presence of alkali (see, for example, Non-Patent Document 1), while the synthetic polymer is Although it exhibits superior heat resistance compared to natural polymers, it is said to be easily decomposed by active oxygen (see, for example, Non-Patent Document 2). Furthermore, weak acid polymers such as the above polyacrylates have the disadvantage that they are easily aggregated by polyvalent cations such as calcium and magnesium. On the other hand, polyvinylpyrrolidone, polyacrylamide, and poly-2-acrylamide have excellent stability against polyvalent cations. Since a polymer such as -2-methylpropane sulfonate has an amide bond, it has a drawback that it is easily hydrolyzed with an acid or an alkali (see, for example, Non-Patent Document 3).

  On the other hand, polystyrene sulfonates that do not contain ethers, amides, and ester bonds are water-soluble polymers with extremely high heat resistance and chemical stability and extremely low toxicity. It is used in applications such as agents, and is expected to be applied to the above applications. However, the molecular weight of polystyrene sulfonate usable as an aqueous solution has an upper limit of about one million, and could not meet the above requirements.

  In general, when producing a high molecular weight polymer, the polymerization amount may be reduced by reducing the amount of the polymerization initiator added to the monomer or by increasing the monomer concentration. For example, the above-mentioned acrylic polymer or acrylamide polymer is extremely high. Molecular weight bodies have been produced (see, for example, Non-Patent Document 4, Non-Patent Document 5, and Patent Document 1).

  On the other hand, since styrene sulfonate is a solid monomer at least at 400 ° C. or less and has low solubility in a solvent, it is industrially polymerized by radical polymerization using an aqueous monomer solution of about 20% by weight ( Manufactured as an aqueous solution of polystyrene sulfonate. In the case of styrene sulfonate, there is a limit to increasing the monomer concentration during polymerization, and even if the polymerization initiator is reduced, the molecular weight is not easily increased compared to acrylic acid and acrylamide, and unreacted monomers remain. There was a problem that it was easy.

  Further, it is difficult to remove styrene sulfonate by a simple method such as distillation under reduced pressure, and there are applications in which the polymer cannot be applied even if the amount of residual monomer is small. For example, when polystyrene sulfonate is used as a thickening and dispersion stabilizer and a monomer with low conjugation such as vinyl acetate is dispersed or emulsion polymerized in water, styrene sulfonate with high conjugation (high radical reactivity) Acts as a polymerization inhibitor for vinyl acetate, and there is a problem that vinyl acetate cannot be polymerized (for example, see Non-Patent Document 6).

  For uses that do not require solubility in water or thickening effect, ultrahigh molecular weight polystyrene sulfonates containing divinylbenzenesulfonic acid polymerization residues are known (see, for example, Patent Document 2 and Patent Document 3). However, these relate to three-dimensionally cross-linked ion exchange membranes, and there is no description regarding an ultra-high molecular weight styrene sulfonic acid or a salt thereof which is water-soluble and can be used as an aqueous solution, and a production method thereof.

  Further, as another industrial production method of polystyrene sulfonate, a method of sulfonating polystyrene in a halogenated solvent is known (for example, see Non-Patent Document 7 and Non-Patent Document 8). However, considering the solubility of ultra-high molecular weight polystyrene in halogenated solvent, solution viscosity, excess acid content after sulfonation and removability of halogenated solvent, ultra-high molecular weight polystyrene exceeding 1 million which can be produced industrially It was still difficult to get.

JP 2005-139462 A Japanese Patent No. 5089917 International Publication No. 2015/125597

SPE Reservoir Evaluation & Engineering (Feb.), 23-34 pages, 1988 Enhanced Oil Recovery-Polymer Flooding, 1-77 pages (Petoleum Industry Press, 2006) Chemical Industry and Engineering Progress, vol. 22, no. 3, 271-274 pages, 2003 Toa Gosei Research Annual Report TREND, p. 46-51, 1998 Revised Chemistry of Polymer Synthesis, Takayuki Otsu, pp. 53-55, 1985, published by Kagaku Dojin Revised Chemistry of Polymer Synthesis, Takayuki Otsu, 112, 118, 1985, published by Chemical Dojin Co., Ltd. Journal of Polymer Science, Part-A, vol. 51, 2416-2424 pages, 2013 Journal of Brazilian Chemical Society, vol. 14, 797-802 pages, 2003

  The present invention has been made in view of the above-mentioned problems, and its object is to achieve a water-soluble ultrahigh molecular weight polystyrene sulfone having a high molecular weight or a high solution viscosity, which has been difficult in the past, and a low styrene sulfonic acid monomer content. The present invention provides an acid or a salt thereof, a production method thereof, and uses such as a thickener or a dispersant containing the ultrahigh molecular weight polystyrene sulfonic acid or a salt thereof.

  In order to increase the molecular weight of styrene sulfonic acid or a salt thereof (hereinafter, styrene sulfonic acid or a salt thereof may be referred to as “SS”) as a result of intensive studies to solve the above-mentioned problems. In the radical polymerization of styrene sulfonic acid or a salt thereof by reducing the amount of the polymerization initiator used for the high molecular weight reaction, a small amount of divinylbenzene sulfonic acid or a salt is added, and radical copolymerization is performed. Polystyrene sulfonic acid or a salt thereof, which is an ultra-high molecular weight and water-soluble polymer, which has been difficult in the past (hereinafter, polystyrene sulfonic acid or a salt thereof is referred to as “PSS”, and ultra high molecular weight polystyrene sulfonic acid or a salt thereof is referred to as “ultra high molecular weight PSS” Has been found to be able to be produced with a high polymerization conversion rate, in other words, a low residual monomer amount, and has led to the completion of the present invention.

That is, the present invention is a water-soluble polymer containing the following repeating structural units (A) and (B),
The water-soluble polymer has a weight average molecular weight determined by gel permeation chromatography (hereinafter, gel permeation chromatography may be referred to as “GPC”) exceeding 900,000 daltons (Da) and / or 5% by weight ( wt%) an ultra-high molecular weight polystyrene sulfonic acid or salt thereof having a viscosity measured as an aqueous solution (30 ° C.) exceeding 100 mPa · s.

[In the repeating structural units (A) and (B), M represents a proton, sodium ion, potassium ion, lithium ion, ammonium ion, quaternary ammonium cation or quaternary phosphonium cation. Here, when x is the number of repeating structural units (A) contained in the water-soluble polymer and y is the number of repeating structural units (B) contained in the water-soluble polymer, 70.00 ≦ 100x / (x + y) ≦ 99.95, 0.05 ≦ 100y / (x + y) ≦ 30.00. ]
Furthermore, the present invention relates to an ultrahigh molecular weight polystyrene sulfonic acid or a salt thereof containing the following repeating structural unit (C) in addition to the repeating structural units (A) and (B) contained in the water-soluble polymer.

[Q in the repeating structural unit (C) represents a radical polymerizable monomer residue. ]

  In addition, the present invention provides a monomer mixture containing the following (D) and (E) when radical polymerization is carried out in water or an aqueous solvent by adding a radical polymerization initiator, and the monomer mixture concentration in the polymerization solution is 60% by weight. The present invention relates to a method for producing the above-described water-soluble ultra-high molecular weight PSS that undergoes radical polymerization below.

(D) Styrenesulfonic acid or salt thereof (E) Divinylbenzenesulfonic acid or salt thereof However, (D) is 99.95-90.00 mol%, and (E) is 0.05-10.00 mol%. is there.

Furthermore, the present invention provides a monomer mixture according to the method for producing the water-soluble ultrahigh molecular weight PSS, wherein (D) and (E), in addition to the following radical polymerizable monomer, an ultrahigh molecular weight polystyrene sulfonic acid or a salt thereof: Related to manufacturing method.
(F) A radically polymerizable monomer that is copolymerizable different from (D) and (E)

  The present invention also relates to a thickener or dispersant containing the ultra high molecular weight polystyrene sulfonic acid or salt thereof.

  The method of using the ultrahigh molecular weight PSS of the present invention as a thickener is not particularly limited. For example, when used in the above-described aqueous fluid for oil mining, the ultrahigh molecular weight PSS is adjusted so that the aqueous fluid has a desired viscosity. What is necessary is just to adjust the addition amount of PSS. At this time, for the purpose of increasing the viscosity or adjusting the viscosity, a general ultra-high molecular weight water-soluble polymer, associative polymer, cationic surfactant, nonionic surfactant, anionic surfactant, or amphoteric interface An activator may be added.

  In addition, when used as a dispersant for inorganic pigment dispersion, emulsion polymerization, or dispersion polymerization, the amount of ultrahigh molecular weight PSS added may be adjusted so that the dispersion or emulsion has a desired viscosity. At this time, in order to assist dispersibility, a general dispersant may be added, or an antifoaming agent, a foaming inhibitor, or the like may be added.

  The ultra high molecular weight polystyrene sulfonic acid or a salt thereof of the present invention is a water-soluble polymer having a high molecular weight or solution viscosity that has not been conventionally used, and the amount of residual styrene sulfonic acid monomer can be greatly reduced. It is extremely useful industrially as a thickener in fields such as petroleum mining, which require high performance and low environmental impact, and as a dispersant in dispersion and emulsion polymerization.

  The present invention relates to a water-soluble polymer having a specific repeating structure, and the water-soluble polymer has a weight average molecular weight determined by gel permeation chromatography of more than 900,000 daltons (Da) and / or a 5% by weight aqueous solution. (30 ° C.) water-soluble ultra-high molecular weight polystyrene sulfonic acid or a salt thereof, divinylbenzene sulfonic acid or a salt thereof as a comonomer, and a thickener or It relates to uses such as dispersants. In the present invention, the viscosity of the water-soluble polymer means that measured by a Brookfield rotary viscometer in principle.

  In the present invention, the polymerization initiator is reduced in weight (in order to increase the molecular weight) and styrene sulfonic acid or a salt thereof (hereinafter, styrene sulfonic acid or a salt thereof may be referred to as “SS”) in water or an aqueous solvent. It is also characterized by radical copolymerization by adding a small amount of divinylbenzenesulfonic acid or a salt thereof (hereinafter, divinylbenzenesulfonic acid or a salt thereof may be referred to as “DVBS”) during radical polymerization.

  One embodiment of the method for producing the ultrahigh molecular weight PSS of the present invention includes a general solution radical polymerization method. For example, a polymerization vessel, styrene sulfonic acid or a salt thereof and divinylbenzene sulfonic acid or a salt thereof, and other monomers capable of radical copolymerization are charged into a reaction vessel, and a molecular weight regulator is added as necessary to deoxidize the system. Then, the polymerization may be performed while heating to a predetermined temperature and adding a radical polymerization initiator. At this time, in order to avoid rapid polymerization, not all monomers are initially charged in the reaction vessel, but each monomer may be continuously added to the reaction vessel together with the polymerization initiator.

  The reaction solvent is not particularly limited, but water having a high dielectric constant is preferable in consideration of solubility of the monomer mixture, polymerization reactivity, and utilization as a thickener. For example, the surface activity and viscosity of PSS are preferred. For the purpose of adjusting characteristics and the like, when a comonomer having poor water solubility is copolymerized, a water-soluble organic solvent may be used in combination.

  The water-soluble organic solvent, that is, the aqueous solvent is not particularly limited as long as the above monomer mixture can be radically copolymerized. For example, acetone, tetrahydrofuran, dioxane, methanol, ethanol, n-propanol, isopropanol, methoxy Examples include ethanol, 2-ethoxyethanol, 2-butoxyethanol, butanol, ethylene glycol, propylene glycol, glycerin, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone and the like.

  Among these, acetone, ethanol, isopropanol, n-propanol, n-butanol, sec-butanol, t-butanol, tetrahydrofuran, acetonitrile, dioxane, dimethyl sulfoxide, N-methylpyrrolidone, and dimethylformamide are preferable.

  These solvents may be used in combination of two or more, and may be a mixed solvent with water.

  The amount of the polymerization reaction solvent used is usually 50 parts by weight to 2,000 parts by weight with respect to 100 parts by weight of the total amount of monomers. The smaller the amount of the polymerization reaction solvent, that is, the higher the monomer concentration, the higher the molecular weight of the produced PSS. Therefore, when polymerizing at a high monomer concentration, DVBS prevents the polymer from curing due to three-dimensional crosslinking. And the addition amount of the polymerization initiator may be appropriately adjusted. In order to avoid the risk of curing the polymerization solution, the polymerization reaction solvent is preferably 66 parts by weight or more (thus, the monomer concentration in the polymerization solution is 60% by weight or less).

  Regarding the molecular weight of the ultrahigh molecular weight PSS of the present invention, the water-soluble polymer has a weight average molecular weight determined by gel permeation chromatography exceeding 900,000 daltons (Da) and / or measured as a 5 wt% aqueous solution (30 ° C.). The viscosity is not particularly limited as long as the viscosity exceeds 100 mPa · s. As described above, in the present invention, the viscosity of the water-soluble polymer is in principle measured by a Brookfield rotational viscometer.

  In the ultrahigh molecular weight PSS of the present invention, the repeating structural units (A) and (B) can have various arrangements. For example, in the case of two repeating structural units (A) and (B), the repetition of “(A) (B)”, “(A) (A) (A) (B) (B) (B ) "To a certain extent, and (A) and (B) may be randomly arranged. The same applies when (C) having a different structure from (A) and (B) is added.

  When the weight average molecular weight of the ultrahigh molecular weight PSS of the present invention is 900,000 daltons (Da) or less and the viscosity measured as a 5% by weight aqueous solution is 100 mP · a or less, a sufficient thickening effect cannot be expected.

  In addition, the amount of unreacted styrene sulfonic acid or a salt thereof contained in the ultrahigh molecular weight PSS is preferably as small as possible from the viewpoint of environmental impact or from the viewpoint of use as a dispersant in dispersion and emulsion polymerization. However, from the viewpoint of productivity, it is preferably 2.0% by weight or less (for example, 0.1% by weight or less in terms of 5% by weight aqueous solution) in the ultrahigh molecular weight PSS. The 5% by weight aqueous solution mentioned here means the polymer concentration excluding unreacted monomers.

  As the styrene sulfonic acid used for the production of the ultrahigh molecular weight PSS of the present invention, all isomers or a mixture thereof can be used. Among them, p-styrene sulfonic acid is preferable, and a sodium salt which is generally distributed, In addition to lithium salts and ammonium salts, quaternary ammonium salts, amine salts, quaternary phosphonium salts, and the like can be used depending on the application.

  The divinylbenzene sulfonic acid or salt thereof used in the production of the ultrahigh molecular weight PSS of the present invention has all isomers as long as it has two or more radical polymerizable vinyl groups and one or more sulfonic acid groups in the benzene ring. Or a mixture of them, in addition to sodium salts generally distributed, lithium salts, ammonium salts, quaternary ammonium salts, amine salts, quaternary phosphonium salts, etc. Can be used.

  The amount of divinylbenzenesulfonic acid or a salt thereof used is preferably 0.05 mol% to 10.00 mol% in all monomers. If it is less than 0.05 mol%, the high molecular weight of PSS may be insufficient, and if it exceeds 10.00 mol%, the above-mentioned patent document (for example, paragraph 0162 of International Publication No. 2015/125597) states “ The mass average molecular weight of the polymer having the structural unit represented by the general formula (I-1) constituting the ion exchange membrane that is the polymer cured product of the invention is several hundred thousand or more because three-dimensional crosslinking is formed. As it is described, “It is generally regarded as infinite.”, The three-dimensional cross-linking of PSS proceeds, so that it is used as an aqueous solution, that is, as a thickener. Use may be difficult. When increasing the copolymerization amount of DVBS, the polymerization reaction solvent and the polymerization initiator may be increased or a molecular weight regulator may be added so that the PSS is not cured by three-dimensional crosslinking.

  The monomer other than styrene sulfonic acid or a salt thereof and divinylbenzene sulfonic acid or a salt thereof is not particularly limited as long as it can be radically copolymerized with these monomers. For example, styrene, chlorostyrene, p-aminostyrene, dichlorostyrene, bromofluorostyrene, trifluorostyrene, nitrostyrene, cyanostyrene, α-methylstyrene, p-chloromethylstyrene, p-cyanostyrene, p-acetoxystyrene, p-t-butoxystyrene, p-p-styrenesulfonyl chloride, ethyl p-styrenesulfonyl, methyl p-styrenesulfonyl, propyl p-styrenesulfonyl, 4-vinylbenzoic acid, p-trimethoxysilylstyrene, 3-isopropenyl -Styrenes such as α, α'-dimethylbenzyl isocyanate and vinylbenzyltrimethylammonium chloride, isobutyl vinyl ether, ethyl vinyl ether, 2-phenyl vinyl alkyl ether, nitrophenyl vinyl ester Ter, cyanophenyl vinyl ether, 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, acrylic Octyl acid, dodecyl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, bornyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2-hydroxyethyl acrylate, tetrahydrofurate acrylate Furyl, methoxyethylene glycol acrylate, ethyl carbitol acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3- (trimethoxysilyl) propyl acrylate, polyethylene glycol acrylate, glycidyl acrylate, 2- (acryloyloxy) ethyl phosphate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,2 acrylate -Acrylic esters such as trifluoroethyl, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, methyl methacrylate, methacryl T-butyl acid, sec-butyl methacrylate, i-butyl methacrylate, i-propyl methacrylate, decyl methacrylate, lauryl methacrylate, octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, bornyl methacrylate , Methacrylic acid , Phenyl methacrylate, glycidyl methacrylate, polyethylene glycol methacrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, methoxyethylene glycol methacrylate, ethyl carbitol methacrylate, 2-hydroxypropyl methacrylate, 4-methacrylic acid 4- Hydroxybutyl, 2- (methacryloyloxy) ethyl phosphate, 2- (dimethylamino) ethyl methacrylate, 2- (diethylamino) ethyl methacrylate, 3- (dimethylamino) propyl methacrylate, 2- (isocyanate) methacrylate Ethyl, 2,4,6-tribromophenyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, meta Methacrylic acid esters such as 2,2,3,3,3-pentafluoropropyl silylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, diacetone methacrylate, isoprene sulfonic 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-piperidylmethyl) -1,3-butadiene, 2-triethoxymethyl-1,3-butadiene, 2- (N, N-dimethylamino) -1,3-butadiene, 1,3-butadienes such as N- (2-methylene-3-butenoyl) morpholine, diethyl 2-methylene-3-butenylphosphonate, N-phenylmaleimide, N- (chloro Phenyl) maleimide, N- (methylphenyl) maleimide, N- (isopropylphenyl) maleimide, N- (sulfophenyl) maleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, N-naphthylmaleimide, N-hydroxyphenyl Maleimide, 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) Reimide, N- (aminophenyl) maleimide, N- (tribromophenyl) maleimide, N- [4- (2-benzimidazolyl) phenyl] maleimide, N- (3,5-dinitrophenyl) maleimide, N- (9- Acridinyl) maleimide, maleimide, N- (sulfophenyl) maleimide, N-cyclohexylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-methoxyphenylmaleimide and other maleimides, dibutyl fumarate, dipropyl fumarate, fumaric acid Diesters such as diethyl, dicyclohexyl fumarate, bis-2-ethylhexyl fumarate, dodecyl fumarate, fumaric acid monoesters such as butyl fumarate, propyl fumarate, ethyl fumarate, dibutyl maleate, dipropiyl maleate Maleic acid diesters such as diethyl maleate, maleic acid monoesters such as butyl maleate, propyl maleate, ethyl maleate and dicyclohexyl maleate, acid anhydrides such as maleic anhydride and citraconic anhydride, acrylamide, N -Methylacrylamide, N-ethylacrylamide, 2-hydroxyethylacrylamide, N, N-diethylacrylamide, acryloylmorpholine, N, N-dimethylaminopropylacrylamide, isopropylacrylamide, N-methylolacrylimide, sulfophenylacrylamide, 2- Acrylamide-2-methylpropanesulfonic acid, 2-acrylamido-1-methylsulfonic acid, diacetone acrylamide, acrylamide alkyltrialkylammo Acrylamides such as umchloride, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, 2-hydroxyethylmethacrylamide, N, N-diethylmethacrylamide, N, N-dimethylmethacrylamide, N-methylolmethacrylamide And methacrylamide such as methacryloylmorpholine, N, N-dimethylaminopropylmethacrylamide, isopropylmethacrylamide, 2-methacrylamide-2-methylpropanesulfonic acid, methacrylamide alkyltrialkylammonium chloride, and the like.

  In addition, vinylpyrrolidone, sulfophenylitaconimide, acrylonitrile, methacrylonitrile, fumaronitrile, α-cyanoethyl acrylate, citraconic acid, citraconic anhydride, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatic 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, vinyl methyl ketone, N-vinylacetamide, N-vinylformamide, vinyl ethyl ketone, vinyl sulfonic acid, allyl sulfonic acid Dehydroalanine, sulfur dioxide, vinyl chloride, isobutene, N- vinylcarbazole, vinylidene di-cyanide, Parakinojimetan, chlorotrifluoroethylene, tetrafluoroethylene, norbornene, N- vinylcarbazole, acrylic acid, and methacrylic acid.

Of these, acrylic acid, methacrylic acid, maleic acid, N-vinyl pyrrolidone, and the like, in view of copolymerization with styrene sulfonic acid or a salt thereof, heat resistance and chemical stability of ultra-high molecular weight PSS, etc. A combination of two or more of these is preferred.
When the above-mentioned monomers are produced as the ultrahigh molecular weight PSS of the present invention, for example, in the case of acrylic acid, methacrylic acid, maleic acid, N-vinylpyrrolidone, acrylic acid residue, methacrylic acid residue, malein It becomes a radically polymerizable monomer residue that is one or a combination of two or more selected from the group consisting of acid residues and N-vinylpyrrolidone residues.

  The use ratio of the above-described styrene sulfonic acid or a salt thereof and other monomers other than divinylbenzene sulfonic acid or a salt thereof is preferably 29.95 mol% or less in all monomers, and more preferably 0.0 mol% to 29. 95 mol%. If it exceeds 29.95 mol%, the polymer can be imparted with surface-active properties or viscosity properties such as pseudoplasticity and dilatancy, but when used in a thickener or dispersant as the main application of the present invention, it has heat resistance. And chemical stability may be reduced.

Since the object of the present invention is to provide a method for producing ultra-high molecular weight PSS, it is not always necessary to use a molecular weight regulator. However, in order to adjust the molecular weight distribution and the distribution of branch points to suppress three-dimensional crosslinking. May be used.
Examples of the molecular weight regulator include diisopropyl xanthogen disulfide, diethyl xanthogen disulfide, diethyl thiuram disulfide, 2,2′-dithiodipropionic acid, 3,3′-dithiodipropionic acid, 4,4′-dithiodibutanoic acid, 2, Disulfides such as 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 Acid, 4-mercaptobenzoic acid, thiomalonic acid, dithiosuccinic acid, thiomaleic acid, thiomaleic anhydride, dithiomaleic acid, thioglutaric acid, cysteine, homocysteine, 5-mercaptotetrazole acetic acid, 3-mer Capto-1-propanesulfonic acid, methallylsulfonic acid, 3-mercaptopropane-1,2-diol, mercaptoethanol, 1,2-dimethylmercaptoethane, 2-mercaptoethylamine hydrochloride, 6-mercapto-1-hexanol, 2- Mercaptans such as mercapto-1-imidazole, 3-mercapto-1,2,4-triazole, cysteine, N-acylcysteine, glutathione, N-butylaminoethanethiol, N, N-diethylaminoethanethiol, and halogens such as iodoform Hydrocarbon, diphenylethylene, p-chlorodiphenylethylene, p-cyanodiphenylethylene, α-methylstyrene dimer, benzyldithiobenzoate, 2-cyanoprop-2-yldithiobenzoate, organic tellurium compound Sulfur, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, potassium metabisulfite and the like.

  The amount of the molecular weight regulator used is usually 10 parts by weight or less with respect to 100 parts by weight of the total amount of monomers used for the production of the ultrahigh molecular weight PSS.

  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 Peroxide compounds such as ammonium, 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] pro Onamide}, 2,2′-azobis {2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis {2- (2-imidazolin-2-yl) propane] disulfate disulfate Hydrate, 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl) propane]} dihydrochloride, 2,2′-azobis (1-imino-1- Pyrrolidino-2-methylpropane) dihydrochloride, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] Tetrahydrate, 1,1′-azobis (1-acetoxy-1-phenylmethane), 4,4′-diazendiylbis (4- And azo compounds such as cyanopentanoic acid) .alpha.-hydro-.omega.-hydroxypoly (oxyethylene) polycondensates.

  If necessary, a reducing agent such as ascorbic acid, erythorbic acid, aniline, tertiary amine, longalite, hydrosulfite, sodium sulfite, sodium bisulfite, sodium thiosulfate, sodium hypophosphite, etc. It may be used in combination with an initiator.

  The usage-amount of a radical polymerization initiator is 0.1 weight part-10 weight part normally with respect to 100 weight part of total monomers used for manufacture of ultra high molecular weight PSS. Furthermore, 0.1 weight part-5 weight part are preferable, and 0.1 weight part-2 weight part are especially more preferable.

  The polymerization conversion rate is preferably 95.0% or more, more preferably 98.0% or more, and further preferably 99.9% or more. Increasing the amount of the polymerization initiator improves the polymerization conversion, but the molecular weight of the polymer decreases. Decreasing the amount of the polymerization initiator increases the molecular weight but decreases the polymerization conversion in the polymerization reaction. In particular, when the monomer concentration during polymerization is high and the amount of DVBS copolymerized is large, PSS is easy to cure by three-dimensional crosslinking, so adjustments such as increasing the polymerization initiator or adding a molecular weight regulator are necessary. It may become. Here, the polymerization conversion rate refers to the amount of monomer consumed in the polymerization reaction relative to the amount of monomer used during the polymerization reaction.

  The polymerization conditions are not particularly limited, but may be heated at 20 ° C. to 120 ° C. for 4 hours to 30 hours in an inert gas atmosphere such as nitrogen gas. The polymerization reaction solvent, the monomer composition, and the polymerization initiator What is necessary is to adjust suitably according to a kind.

  The ultra-high molecular weight polystyrene sulfonic acid copolymer of the present invention can be produced by the above-mentioned general solution radical polymerization, but as a second method, known as reverse phase emulsion polymerization (for example, Polymer International, vol. 59, 78). -84, 2010; Polymer Bulletin, vol. 65, 565-576, 2010) can also be applied.

  For example, an aqueous monomer solution containing styrene sulfonic acid or a salt thereof is emulsified and dispersed in an oil phase using an appropriate emulsifier, and then degassed and added with a radical polymerization initiator in the same manner as in the above solution radical polymerization. However, polymerization may be performed.

  The surfactant used for emulsifying and dispersing is not particularly limited. For example, rosin acid salt, fatty acid salt, alkenyl succinate, alkyl ether carboxylate, alkyl diphenyl ether disulfonate, alkane sulfonate , Alkyl succinate sulfonate, polyoxyethylene polycyclic phenyl ether sulfate ester, α-olefin sulfonate, alkylbenzene sulfonate, naphthalene sulfonate formalin condensate, taurine derivative, polystyrene sulfonate, polystyrene sulfonate Styrene copolymer, polystyrenesulfonic acid N-vinylpyrrolidone copolymer, polystyrenesulfonic acid N-substituted maleimide copolymer, polystyrenesulfonic acid methacrylic acid copolymer, polystyrenesulfonic acid acrylic acid copolymer Body, polystyrene sulfonic acid acrylic acid ester copolymer, styrene sulfonic acid maleic acid copolymer, styrene sulfonic acid acrylamide copolymer, styrene sulfonic acid methacrylamide copolymer, styrene sulfonic acid 2-hydroxyethyl methacrylate copolymer, Polyvinyl phosphonic acid copolymer, polyvinyl sulfonic acid copolymer, polyisoprene sulfonic acid copolymer, polyacrylic acid ester acrylic acid copolymer, polymethacrylic acid ester methacrylic acid copolymer, polyacrylamide acrylic acid copolymer, Polymethacrylamide methacrylic acid copolymer, alkyl sulfosuccinate, alkyl sulfate ester, alkyl ether sulfate ester, sulfate salt of alkyl propenyl phenol polyethylene oxide adduct, allyl Anionic emulsifiers such as sulfate esters of alkylphenol polyethylene oxide adducts, alkyl phosphate esters, polyoxyethylene alkyl ether phosphate esters, sulfonates of higher fatty acid amides, sulfates of higher fatty acid alkylolamides, etc. , Polyoxyalkylene alkylamine, alkyl alkanolamide, amine oxide nonionic emulsifier, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyalkylene polycyclic phenyl ether, alkyl propenyl phenol polyethylene oxide adduct, allyl alkyl phenol polyethylene Oxide adduct, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan Fatty acid ester, glycerin fatty acid ester, alkyl polyglucooxide, 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, polydimethylaminoethyl Acrylate / methyl methacrylate copolymer, Nonionic emulsifiers such as redimethylaminoethyl methacrylate / butyl acrylate copolymer, polydimethylaminoethyl acrylate / ethyl acrylate copolymer, for example, amphoteric emulsifiers such as alkyldimethylaminoacetic acid betaine, alkyldimethylaminosulfobetaine, alkylsulfobetaine Etc.

  In addition, what is necessary is just to use the usage-amount of these emulsifiers in the range of 0.1 weight%-30 weight% with respect to the PSS component of the said invention.

  The polymerization initiator, the reducing agent, and the molecular weight regulator in the reverse emulsion polymerization are the same as those in the solution radical polymerization described above. In addition, pH buffering agents such as sodium carbonate, sodium hydrogen carbonate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate may be added.

  In the reversed-phase emulsion polymerization, the oil phase is a matrix for dispersing the micelles of the monomer and the droplets of the aqueous monomer solution, and is not particularly limited as long as it meets this purpose, but toluene, chlorobenzene, etc. In addition to aromatic hydrocarbons, aliphatic hydrocarbons such as hexane, cyclohexane, methylcyclohexane, and heptane, mineral oil, synthetic oil, vegetable oil, silicone oil, and the like can be used.

  Since the water-soluble ultra-high molecular weight PSS of the present invention has a high polymerization conversion rate and therefore a small amount of residual monomer, it can be used as a solution after polymerization. Moreover, it can also be used after making it into dry powder by equipment such as a spray dryer or an extrusion dryer.

  The water-soluble ultra-high molecular weight PSS of the present invention is excellent in heat resistance and chemical stability and has a small amount of residual monomer, so that it is emulsified and dispersed in the oil mining field where high durability and low environmental load are required. It is extremely useful industrially as a thickener, a flocculant, and a soil modifier in polymerization dispersants, cosmetics and toiletries.

  The following examples further illustrate the present invention, but the present invention is not limited to these examples.

<Purity measurement of sodium parastyrene sulfonate>
The active double bond was quantified by the oxidation-reduction titration method to obtain the sodium styrenesulfonate content in the sample.
(1) Instrument and device 1) Weighing bottle: diameter 50 mm, depth 70 mm
2) 500 ml, 1000 ml volumetric flask 3) 500 ml Erlenmeyer flask with a stopper 4) 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)

<Purity measurement of divinylbenzene sulfonate>
Purity was measured by nuclear magnetic resonance spectrum.
(1) Preparation of sample 0.02 g of sample and 0.01 g of triethylamine or methyl isobutyl ketone as an internal standard substance are weighed in a weighing bottle (50 mmφ × 70 mm) to the order of 0.1 mg, and a total amount of heavy water or heavy acetone is 0.6 g. The sample was added until dissolved to prepare an NMR measurement sample.
(2) Measuring equipment Model = Bruker AV-400M
Integration count = 16
(3) Calculation of purity The purity of the product was calculated by the following formula.

Purity (% by weight) = (B / M _b ) × (a / a _H ) / (b / b _H ) × M _a / S × 100
a: integral value of any of the object peak b: integral value of any of the internal standard substance a _H: number of hydrogens of any product peak selected in _a b _H: any number of hydrogens of product peaks selected in _b M _a : Molecular weight of target substance M _b : Molecular weight of internal standard substance B: Amount of collected internal standard (g)
S: Amount of sample collected (g)

<Measurement of molecular weight and monomer polymerization conversion by GPC>
The polymerization conversion of styrene sulfonate and divinylbenzene sulfonate and the molecular weight of polystyrene sulfonate were measured under the following conditions.

Model: Tosoh Corporation, HLC-8320GPC
Column: TSK guardcolumn AW-H / TSK AW-3000 / TSK AW-6000
Eluent: Sodium sulfate buffer (0.05 mol / L): Acetonitrile = 90: 10 (volume ratio) solution Column temperature: 40 ° C.
Flow rate: 0.6ml / min
Detector: UV detector (wavelength 230 nm), injection amount: 10 μl
Calibration curve: Sodium monodisperse polystyrene sulfonate (3 KDa (3000 Dalton), 15 KDa, 41 KDa, 300 KDa, 1000 KDa, 2350 KDa, 5000 KDa) manufactured by Soka Kagaku Co., Ltd. was used for the preparation of the calibration curve. A calibration curve was prepared from the molecular weight.

<Measurement of aqueous solution viscosity>
A 5% by weight polymer aqueous solution was allowed to stand in a constant temperature bath at 30 ° C. for 4 hours, and then measured using a Brookfield rotary viscometer under the following conditions.

Model: Shibaura System Co., Ltd., Bismetron VDA-2
Rotor: No. 2, rotation speed: 12rpm

<Evaluation of hydrogen peroxide resistance of polymer>
100 g of 5% polymer aqueous solution and 2 g of hydrogen peroxide solution (made by Wako Pure Chemical Industries, Ltd., special grade) are collected in 250 ml polybin (Nippon Medical Science Co., Ltd., Eyeboy), shaken and flushed with nitrogen. And sealed and then aged for 4 days in a thermostatic bath at 50 ° C. Thereafter, GPC was measured under the above-described conditions to examine changes in molecular weight.

<Evaluation of heat resistance of polymer>
The thermal decomposition behavior of the vacuum-dried polymer was analyzed with a differential high-temperature differential thermobalance under the following conditions. The temperature at which weight loss suddenly started was defined as the decomposition temperature.
Model: TG-DTA2000, manufactured by Mac Science Co., Ltd.
Sample amount: 5mg (platinum open pan)
Standard sample: Aluminum oxide Al ₂ O ₃ , 5 mg (platinum open pan)
Temperature increase rate: 10 ° C / min (room temperature to 600 ° C)
Atmosphere: nitrogen flow 50 ml / min.

Example 1 (implemented at 0.47 mol% DVBS)
In a 2 L glass flask reactor equipped with a reflux condenser and a nitrogen introduction tube, 393.57 g of ion-exchanged water, 37.51 g of sodium styrenesulfonate (Tosoh Organic Chemical Co., Ltd., purity 88.0%), sodium divinylbenzenesulfonate (Tosoh Organic Chemical Co., Ltd., purity 84.0%) 0.2099 g and azo initiator V-50 (Wako Pure Chemical Industries, Ltd.) 0.4601 g were charged and then stirred under a mechanical stirrer (150 rpm) under nitrogen. Gas (0.2 L / min) was degassed by flowing for 10 minutes. Thereafter, the reactor was immersed in a 60 ° C. hot water bath and polymerized for 10 hours. From the charged composition and polymerization conversion rate, the PSS concentration in the polymerization solution was 7.69% by weight, and ion exchange water was added thereto to adjust the PSS concentration to 5.00% by weight.

  As shown in Table 1, as compared with Comparative Examples 1 to 5 and Comparative Example 9 described later, a PSS solution having a clearly high viscosity and a high weight average molecular weight was obtained, and the polymerization progressed to a high conversion rate. Residual SS in a 5 wt% aqueous solution was not detected. Further, it is apparent that the durability and heat resistance (thermal decomposition temperature) of the PSS with respect to hydrogen peroxide are remarkably superior to the commercially available polymers described in Comparative Examples 7 and 8.

  In this example, the polymerization was carried out at a monomer concentration as low as 5% by weight due to problems in experimental equipment such as stirring, but it is considered that if the polymerization is carried out at a high monomer concentration, the molecular weight or viscosity can be further increased.

Example 2 (implemented at DVBS 0.47 mol%, MAA 9.6 mol%)
In a 2 L glass flask reactor equipped with a reflux condenser and a nitrogen inlet tube, 393.60 g of ion-exchanged water, 37.50 g of sodium styrenesulfonate (manufactured by Tosoh Organic Chemical Co., Ltd., purity 88.0%), sodium divinylbenzenesulfonate (Tosoh Organic Chemical Co., Ltd., purity 84.0%) 0.2300 g, methacrylic acid (Wako Pure Chemical Industries, Ltd., special grade) 1.50 g, 5 wt% sodium hydroxide aqueous solution 13.20 g, and azo initiator After charging 0.4642 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.), nitrogen gas (0.2 L / min) was allowed to flow for 10 minutes while stirring with a mechanical stirrer (150 rpm). Thereafter, the reactor was immersed in a 60 ° C. hot water bath and polymerized for 10 hours. From the charged composition and the polymerization conversion rate, the PSS concentration in the polymerization solution was 7.85% by weight, and ion exchange water was added thereto to adjust the PSS concentration to 5.00% by weight.

  As shown in Table 1, as compared with Comparative Examples 1 to 6 which will be described later, a PSS aqueous solution having a clearly high viscosity and a high weight average molecular weight was obtained, and the polymerization progressed to a high conversion rate. Residual SS was not detected. Further, it is apparent that the durability and heat resistance (thermal decomposition temperature) of the PSS with respect to hydrogen peroxide are remarkably superior to the commercially available polymers described in Comparative Examples 7 and 8.

Example 3 (implemented with DVBS 0.24 mol%, reduced initiator weight)
Other than reducing the amount to sodium divinylbenzenesulfonate (Tosoh Organic Chemical Co., Ltd., purity 84.0%) 0.1050 g, and azo initiator V-50 (Wako Pure Chemical Industries, Ltd.) 0.2300 g Polymerization was carried out for 10 hours under the same conditions as in Example 1. From the charged composition and polymerization conversion rate, the PSS concentration in the polymerization solution was 7.69% by weight, and ion exchange water was added thereto to adjust the PSS concentration to 5.00% by weight.

  As shown in Table 1, as compared with Comparative Examples 1 to 6 which will be described later, a PSS aqueous solution having a clearly high viscosity and a high weight average molecular weight was obtained, and the polymerization progressed to a high conversion rate. Residual SS was not detected. Further, it is apparent that the durability and heat resistance (thermal decomposition temperature) of the PSS with respect to hydrogen peroxide are remarkably superior to the commercially available polymers described in Comparative Examples 7 and 8.

Example 4 (implemented at DVBS 0.89 mol%, AA 11.20 mol%, water doubling)
In a 2 L glass flask reactor equipped with a reflux condenser and a nitrogen inlet tube, 626.00 g of ion-exchanged water, 37.51 g of sodium styrenesulfonate (manufactured by Tosoh Organic Chemical Co., Ltd., purity 88.0%), sodium divinylbenzenesulfonate (Tosoh Organic Chemical Co., Ltd., purity 84.0%) 0.4495 g, acrylic acid (Wako Pure Chemical Industries, Ltd., special grade), 5 wt% aqueous sodium hydroxide solution 16.20 g and azo initiator V-50 ( After charging 0.4642 g (manufactured by Wako Pure Chemical Industries, Ltd.), the mixture was deaerated by flowing nitrogen gas (0.2 L / min) for 10 minutes while stirring with a mechanical stirrer (150 rpm). Thereafter, the reactor was immersed in a 60 ° C. hot water bath and polymerized for 10 hours. From the charged composition and the polymerization conversion rate, the PSS concentration in the polymerization solution was 5.18 wt%, and ion exchange water was added thereto to adjust the PSS concentration to 5.00 wt%. As shown in Table 1, as compared with Comparative Examples 1 to 6 which will be described later, a PSS aqueous solution having a clearly high viscosity and a high weight average molecular weight was obtained, and the polymerization progressed to a high conversion rate. Residual SS was not detected. Further, it is apparent that the durability and heat resistance (thermal decomposition temperature) of the PSS with respect to hydrogen peroxide are remarkably superior to the commercially available polymers described in Comparative Examples 7 and 8.

Example 5 (DVBS 2.00 mol%, carried out with double water)
Polymerization was carried out for 10 hours under the same conditions as in Example 1 except that the amount was increased to 0.9010 g of sodium divinylbenzenesulfonate (Tosoh Organic Chemical Co., Ltd., purity 84.0%) and 626.00 g of ion-exchanged water. From the charged composition and the polymerization conversion rate, the PSS concentration in the polymerization solution was 5.00% by weight, and was used for the analysis as it was.

  As shown in Table 1, as compared with Comparative Examples 1 to 6 which will be described later, a PSS aqueous solution having a clearly high viscosity and a high weight average molecular weight was obtained, and the polymerization progressed to a high conversion rate. Residual SS was not detected. Further, it is apparent that the durability and heat resistance (thermal decomposition temperature) of the PSS with respect to hydrogen peroxide are remarkably superior to the commercially available polymers described in Comparative Examples 7 and 8.

Comparative Example 1 (Study without DVBS of Example 5)
Polymerization was carried out for 10 hours under the same conditions as in Example 5 except that sodium divinylbenzenesulfonate (manufactured by Tosoh Organic Chemical Co., Ltd., purity 84.0%) was not added.
As shown in Table 1, the polymerization proceeded to a high conversion rate, but the viscosity and weight average molecular weight of the PSS aqueous solution were clearly lower than those of Examples 1-5. That is, the use of DVBS is essential to achieve high viscosity, high weight average molecular weight, and high polymerization conversion.

Comparative Example 2 (Study by reducing initiator in Comparative Example 1)
Polymerization was conducted for 10 hours under the same conditions as in Comparative Example 1 except that the amount of the azo initiator V-50 was reduced to 0.1531 g.
As shown in Table 1, a high viscosity and high weight average molecular weight PSS solution was obtained, but the polymerization conversion was low and the residual monomer concentration exceeded 0.1% (2.00% by weight in terms of solid PSS). It was. That is, the use of DVBS is essential to achieve high viscosity, high weight average molecular weight, and high polymerization conversion.

Comparative Example 3 (Study with initiator variant and weight loss of Comparative Example 1)
10 except that 0.1500 g of ammonium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.1500 g was added instead of 0.4590 g of the azo initiator V-50 (manufactured by Wako Pure Chemical Industries, Ltd.). Polymerized for hours.
As shown in Table 1, a high viscosity and high weight average molecular weight PSS solution was obtained, but the polymerization conversion was low and the residual monomer concentration exceeded 0.1% (2.00% by weight in terms of solid PSS). It was. That is, the use of DVBS is essential to achieve high viscosity, high weight average molecular weight, and high polymerization conversion.

Comparative example 4 (considering using EG-DMA instead of DBVS)
Polymerization was carried out for 10 hours under the same conditions as in Example 5 except that 0.6706 g of ethylene glycol dimethacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., special grade) was used instead of sodium divinylbenzenesulfonate. From the charged composition and the polymerization conversion rate, the PSS concentration in the polymerization solution was 5.00% by weight, and was used in the analysis as it was. As shown in Table 1, the polymerization proceeded to a high conversion rate, but the viscosity and weight average molecular weight of the PSS aqueous solution were clearly lower than those of Examples 1-5. That is, in order to achieve high viscosity, high weight average molecular weight, and high polymerization conversion rate, it is essential to use DVBS as a polyfunctional vinyl monomer.

Comparative example 5 (considering using MBAM instead of DBVS)
Polymerization was carried out for 10 hours under the same conditions as in Example 5 except that 0.5210 g of N, N′-methylenebisacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd., special use) was used instead of sodium divinylbenzenesulfonate. From the charged composition and the polymerization conversion rate, the PSS concentration in the polymerization solution was 5.00% by weight, and was used in the analysis as it was.

  As shown in Table 1, the polymerization proceeded to a high conversion rate, but the viscosity and weight average molecular weight of the PSS aqueous solution were clearly lower than those of Examples 1-5. That is, in order to achieve high viscosity, high weight average molecular weight, and high polymerization conversion rate, it is essential to use DVBS as a polyfunctional vinyl monomer.

Comparative Example 6
Polymerization was carried out for 10 hours under the same conditions as in Example 5 except that sodium divinylbenzenesulfonate was increased to 3.5000 g and ion-exchanged water was increased to 675.00 g.

  During the polymerization, the solution gelled and stirring and analysis were difficult.

Comparative Example 7 (examined by AMPS)
To a commercially available aqueous solution of poly (2-acrylamido-2-methyl-1-propanesulfonic acid) (manufactured by Sigma-Aldrich Japan Co., Ltd., 15% by weight aqueous solution), 39.5% by weight aqueous sodium hydroxide and ion-exchanged water were added. A 5% by weight aqueous solution (pH = 7.23) of poly (2-acrylamido-2-methyl-1-propanesulfonate) was prepared.

  As shown in Table 1, the polymer exhibited a high viscosity and a high weight average molecular weight equivalent to those of Examples 1 to 5, but the hydrogen peroxide resistance and heat resistance (thermal decomposition temperature) were as described in Example 1. Greatly inferior to PSS of ~ 5.

Comparative Example 8 (examined by PAM)
Ion exchange water was added to a commercially available polyacrylamide aqueous solution (manufactured by Tokyo Chemical Industry Co., Ltd., 10 wt% aqueous solution) to prepare a 5 wt% aqueous solution.

  As shown in Table 1, the polymer exhibited a high viscosity equivalent to that of Examples 1 to 5 while lowering the weight average molecular weight of the polymer. However, hydrogen peroxide resistance and heat resistance (thermal decomposition temperature) were greatly inferior to PSS.

Comparative Example 9 (examined with commercially available PSS)
Ion-exchanged water was added to a commercially available high molecular weight sodium polystyrenesulfonate aqueous solution (Tosoh Organic Chemical Co., Ltd., 21 wt% aqueous solution) to prepare a 5 wt% aqueous solution.

  The solution viscosity and weight average molecular weight of the polymer were both inferior to Examples 1-5.

  The ultra-high molecular weight, water-soluble polystyrene sulfonic acid or salt thereof of the present invention is excellent in heat resistance and chemical stability, and also has a small amount of residual monomer, so that it has a high durability and low environmental impact, and is in the oil mining field. In addition, it is very useful industrially as a dispersant for emulsion and dispersion polymerization, a thickener and a flocculant in cosmetics and toiletries.

Claims (12)

A water-soluble polymer comprising the following repeating structural units (A) and (B),
The water-soluble polymer has a weight average molecular weight determined by gel permeation chromatography exceeding 900,000 daltons (Da) and / or a viscosity measured as a 5% by weight aqueous solution (30 ° C.) exceeding 100 mPa · s. High molecular weight polystyrene sulfonic acid or salt thereof.

[In the repeating structural units (A) and (B), M represents a proton, sodium ion, potassium ion, lithium ion, ammonium ion, quaternary ammonium cation or quaternary phosphonium cation. Here, when x is the number of repeating structural units (A) contained in the water-soluble polymer and y is the number of repeating structural units (B) contained in the water-soluble polymer, 70.00 ≦ 100x / (x + y) ≦ 99.95, 0.05 ≦ 100y / (x + y) ≦ 30.00. ] The ultrahigh molecular weight polystyrene sulfonic acid or salt thereof according to claim 1, comprising the following repeating structural units (C) in addition to the repeating structural units (A) and (B) contained in the water-soluble polymer.

[Q in the repeating structural unit (C) represents a radical polymerizable monomer residue. ]   Q is a radically polymerizable monomer residue that is one or a combination of two or more selected from the group consisting of an acrylic acid residue, a methacrylic acid residue, a maleic acid residue, and an N-vinylpyrrolidone residue. The ultrahigh molecular weight polystyrene sulfonic acid or salt thereof according to claim 1 or 2.   The ultrahigh molecular weight polystyrene sulfonic acid or a salt thereof according to any one of claims 1 to 3, wherein the content of the styrene sulfonic acid monomer or a salt thereof is 2.0% by weight or less. When the monomer mixture containing the following (D) and (E) is radically polymerized in water or an aqueous solvent by adding a radical polymerization initiator, the monomer mixture in the polymerization solution is radically polymerized at a concentration of 60% by weight or less. The manufacturing method of the ultra high molecular weight polystyrene sulfonic acid of any one of Claims 1-4, or its salt.
(D) Styrenesulfonic acid or a salt thereof (E) Divinylbenzenesulfonic acid or a salt thereof (However, (D) is 99.95 to 90.00 mol%, and (E) is 0.05 to 10.00 mol%. It is. ] The method for producing an ultrahigh molecular weight styrene sulfonic acid or a salt thereof according to claim 5, comprising the following radical polymerizable monomer in addition to (D) and (E).
(F) A radically polymerizable monomer that is copolymerizable different from (D) and (E)   The ultrahigh molecular weight styrene sulfonic acid according to claim 6, wherein (F) is one or more radically polymerizable monomers selected from the group consisting of acrylic acid, methacrylic acid, maleic acid and N-vinylpyrrolidone. Method for producing salt.   The method for producing an ultrahigh molecular weight styrene sulfonic acid or a salt thereof according to any one of claims 5 to 7, wherein the radical polymerization initiator is a peroxide compound or an azo compound.   The production of ultrahigh molecular weight styrene sulfonic acid or a salt thereof according to any one of claims 5 to 8, wherein the radical polymerization initiator is 0.1 to 2 parts by weight based on 100 parts by weight of the total amount of monomers. Method.   The method for producing an ultrahigh molecular weight styrene sulfonic acid or a salt thereof according to claim 9, wherein the polymerization conversion rate is 98.0% or more.   A thickener comprising the ultrahigh molecular weight polystyrene sulfonic acid or salt thereof according to any one of claims 1 to 4.   The dispersing agent containing the ultra high molecular weight polystyrene sulfonic acid or its salt as described in any one of Claims 1-4.