JP2015105315A - Styrenesulfonic acid lithium copolymer having high solubility in organic solvent, and excellent heat resistance, and antistatic agent using the styrenesulfonic acid lithium copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a styrenesulfonic acid lithium copolymer having high solubility in organic solvent, and excellent heat resistance, useful as an antistatic agent for plastic and fiber, and a dispersant for pigment, resin, conductive polymer or the like.SOLUTION: This invention provides a styrenesulfonic acid lithium copolymer having high solubility in organic solvent, and excellent heat resistance, made using parastyrenesulfonic acid lithium, and also provides an antistatic agent, a hydrophilic coating agent, and a dispersant, using the copolymer.

Description

  The present invention relates to a lithium styrene sulfonate copolymer excellent in solubility in an organic solvent and heat resistance, and an antistatic agent using the lithium styrene sulfonate copolymer.

As antistatic agents for plastics, fibers, paper, etc., low molecular antistatic agents (generally low molecular surfactants), polymer antistatic agents, carbon black and the like are used industrially.
However, the method of applying or kneading a low molecular weight antistatic agent to a substrate such as plastic has a drawback that the antistatic effect is low in durability and the antistatic effect is highly dependent on humidity. In the method of adding carbon black, these disadvantages are improved. However, since it is necessary to add a considerably large amount of carbon black of 20 to 30 wt%, other disadvantages such as deterioration of physical properties of the substrate and poor appearance are caused. There is.

  The polymer type antistatic agent is generally referred to as a permanent antistatic agent because it is less likely to fall off from the substrate than the low molecular weight type antistatic agent. The polymer antistatic agent is usually a polymer having a hydrophilic group, and is classified into nonionic, cationic, anionic, and amphoteric depending on the type of the hydrophilic group. Of these, nonionic polymers are most frequently used as antistatic agents, such as polyether ester amide, polyethylene oxide-epichlorohydrin copolymer, and ethylene-vinyl acetate copolymer graft-modified with polyethylene oxide. Ethylene oxide-propylene oxide copolymers are used industrially. In addition, cationic polymers are also widely used, and many cationic polymers such as quaternary ammonium base-containing copolymers using methyl chloride salts of dimethylaminoethyl methacrylate as a cationic monomer have been put into practical use. ing. On the other hand, anionic polymers have few practical examples as antistatic agents, and only a few ethylene-potassium methacrylate copolymers and polystyrene sulfonates are known. As for amphoteric, low molecular surfactants having a betaine structure are famous, but polymer types are hardly known.

  Regardless of the low molecular type or the polymer type, it is generally said that the antistatic effect is the highest in cationicity, followed by amphoteric and anionic, followed by the lowest nonionicity. On the other hand, it is said that heat resistance is the highest in anionicity, followed by nonionicity and amphotericity, and lowest in cationicity (for example, Patent Document 1 and Non-Patent Document 1). In fact, some anionic antistatic agents with excellent heat resistance are used as antistatic agents for engineering plastics such as polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide, and polyphenylene ether, which have high melting points and high processing temperatures. It is used. However, most of them are low molecular weight anionic surfactants such as sodium alkylbenzene sulfonate and sodium alkyl sulfonate, and there is a problem in sustaining the antistatic effect. Therefore, there has been a strong demand for a polymer-type antistatic agent that can be applied to engineering plastics and has both antistatic effect durability and heat resistance.

  The reason why it is difficult to apply the anionic polymer type antistatic agent to the plastic is that the compatibility between the anionic polymer and the plastic is poor. A general anionic polymer has strong water solubility, poor solubility in an organic solvent, and poor compatibility with plastics, so that it is difficult to disperse in plastics with high hydrophobicity or uniformly apply to surfaces.

  As a typical anionic polymer, there is a polystyrene sulfonate (hereinafter, “polystyrene sulfonate” may be referred to as “PSS”, and “polystyrene sulfonate” may be referred to as “PSS salt”). PSS salts are made by radical polymerization of styrene sulfonates in water or sulfonation of polystyrene in halogenated solvents. PSS salts are synthetic pastes, dispersants (for dispersing pigments, resins, carbon materials, abrasive particles, silica particles, conductive polymers, photographic silver halides, etc.), detergents, scale inhibitors, conductive polymer dopants. In addition to being used as a rheology control agent and an ion exchange resin, its use as an antistatic agent has been known for a long time. For example, it is known that an aqueous solution of sodium PSS can be used as an antistatic agent for paper that is easily compatible with water (Patent Document 2). However, PSS sodium is difficult to use as an antistatic agent for plastics due to compatibility problems. For example, it is necessary to improve the compatibility with plastics by converting PSS sodium salt to a higher amine salt of PSS. (For example, Patent Documents 3 and 4). However, the process of converting PSS sodium salt to PSS higher amine salt is cumbersome and increases the cost, and further, there is a problem that the heat resistance of the polymer is remarkably lowered by conversion to an amine salt (cation exchange method). A method for producing a PSS amine salt by sulfonated polystyrene in a halogenated solvent to produce styrene sulfonic acid and then neutralizing with amine is not as expensive as the cation exchange method described above. Since a large amount of halogenated solvent such as sulfuric acid is used, there is a problem that the load on the environment and safety is large.

  On the other hand, as an antistatic agent for a polyester film, a coating agent containing PSS ammonium salt, PSS sodium salt, PSS lithium salt, or PSS phosphonium salt is known (for example, Patent Document 5). However, the coating agent is mainly composed of a water-soluble polyester resin having a hydrophilic group such as a sulfonate, and the PSS salt is a minor component. In addition, since the main solvent of the coating agent is water with poor wettability to plastic, it is necessary to add a fluorosurfactant or to make the polyester film as a base material hydrophilic by pre-corona treatment. . Further, this document does not mention any composition and solubility of the PSS copolymer (salt) or the PSS lithium salt.

  Further, a method for preventing charging of polyolefin by kneading a PSS salt into polyolefin is known (for example, Patent Document 6). However, in order to develop the antistatic effect, it is necessary to knead a nonionic polymer such as polyether ester amide in an amount of 1 to 500 times that of the PSS salt. In addition to PSS sodium salt and PSS ammonium salt, it is described that PSS copolymer salt can be used, but the composition and solubility of PSS copolymer (salt) or PSS lithium salt are not mentioned at all. It has not been.

JP 2003-226866 A Japanese Examined Patent Publication No. 45-25326 Japanese Patent Publication No.51-981 JP-A-8-104787 Japanese Patent No. 4403479 JP-A-5-39388

Industrial Materials, Vol. 60, No. 12, pp. 60-66, 2012

  The present invention has been made in view of the above-described problems, and the object thereof is to provide a lithium styrene sulfonate copolymer (hereinafter referred to as “PSS”) that is useful as an antistatic agent and has excellent solubility in organic solvents and heat resistance. It is also referred to as a “lithium copolymer”.

  As a result of intensive studies to solve the above problems, the present inventors have found that a lithium parastyrene sulfonate copolymer is excellent in solubility in an organic solvent and heat resistance and is useful as an antistatic agent. The present invention has been completed.

  The present invention relates to a lithium styrene sulfonate copolymer that is produced using lithium parastyrene sulfonate and has excellent solubility and heat resistance in an organic solvent having the following repeating structural unit A and the following repeating structural unit B.

[In the repeating structural units A and B, M represents a lithium cation, Q represents a radical polymerizable monomer residue or radical reactive polymer residue, n represents an integer of 1 or more, and m represents an integer of 1 or more. ]
Here, the solubility [(weight of copolymer / weight of solution) × 100] in ethanol of the PSS lithium copolymer of the present invention is 10 wt% or more, and thermal decomposition obtained by simultaneous differential thermal-thermogravimetric measurement. The temperature is 300 ° C. or higher.
The weight average molecular weight determined by gel permeation chromatography (hereinafter referred to as GPC) of the PSS lithium copolymer of the present invention is preferably 2,000 to 1,000,000.
Q in the above repeating structural unit B includes methacrylic acid ester residue, N-substituted maleimide residue, fumaric acid diester residue, styrene residue, styrene derivative residue, polymer azo polymerization initiator residue, thiol A radical reactive polymer residue such as a terminal polymer residue is preferred. The methacrylic acid ester residue is preferably a radical polymerizable monomer residue such as glycidyl methacrylate, butyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc. As the N-substituted maleimide residue, radical polymerizable monomer residues such as N-phenylmaleimide and N-cyclohexylmaleimide are preferable, and as the fumarate ester residue, diethyl fumarate, dibutyl fumarate, bis fumarate A radical polymerizable monomer residue such as 2-ethylhexyl is preferred.
Next, the present invention relates to an antistatic agent, a hydrophilic coating agent and a dispersant using the PSS lithium copolymer.

  The lithium parastyrene sulfonate copolymer produced using the lithium para styrene sulfonate of the present invention is excellent in solubility in organic solvents and heat resistance, and is therefore useful as an antistatic agent for plastics and fibers.

The present invention relates to a lithium styrene sulfonate copolymer excellent in solubility and heat resistance in an organic solvent having a repeating structural unit A and a repeating structural unit B, produced using lithium parastyrene sulfonate.
Here, “excellent solubility in organic solvents” means methanol, ethanol, propanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol, 1 Alcohol solvents such as methoxy-2-propanol, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 4-hydroxy-4-methyl-2-pentanone, and these alcohols It means that the solubility at room temperature in an aqueous solvent composed of a system solvent and 30 wt% or less of water is 5 wt% or more. More specifically, for example, as an indicator of solubility, the solubility [(copolymer weight / solution weight) × 100] in ethanol at room temperature is 10 wt% or more, or 1-methoxy-2-propanol 70 wt. % / Ethanol 30 wt% mixed solvent at normal temperature [(copolymer weight / solution weight) × 100] is 5 wt% or more. In particular, there is no limit to the upper limit of solubility, and the higher the better.
“Excellent heat resistance” means that the thermal decomposition temperature (original sample weight is the same as that determined by differential thermal-thermogravimetric measurement (TG-DTA) under a nitrogen atmosphere and a heating rate of 10 ° C./min. The temperature is reduced by 5 wt% and is also referred to as Td5), which is preferably higher, but means at least 300 ° C. or higher.

  The PSS lithium copolymer of the present invention is not particularly limited as long as it has repeating structural units A and B, and may be a random copolymer, a block copolymer, or a graft copolymer. . The block copolymer referred to here is a PSS lithium chain (the above repeating structural unit A) and a polymer chain different from PSS lithium (the above repeating structural unit B) bonded together in a block form through a covalent bond. And include diblock, triblock, and multiblock types. In addition, the graft copolymer is a polymer chain different from PSS lithium or a branch of a polymer chain different from PSS lithium (the above repeating structural unit B) on the trunk of PSS lithium (the above repeating structural unit A). A branch of PSS lithium (the repeating structural unit A) is bonded to a trunk of the repeating structural unit B) in a branch (graft) form through a covalent bond.

A feature of the present invention is that lithium parastyrene sulfonate was used as a monomer when producing a polystyrene sulfonic acid copolymer salt, which will be described below.
Industrially available parastyrene sulfonates are sodium parastyrene sulfonate and lithium parastyrene sulfonate. Although ammonium parastyrene sulfonate and amine para styrene sulfonate are known as research reagents, the production process is extremely complicated and it is difficult to obtain them industrially. Parastyrene sulfonate has a radical polymerizability equivalent to that of styrene, and can be copolymerized with various radically polymerizable monomers. However, the copolymer obtained using sodium parastyrene sulfonate has extremely poor solubility in organic solvents. The point of the present invention is that by using lithium parastyrene sulfonate, various PSS lithium copolymers can be easily produced, and the copolymer has extremely high solubility and heat resistance in organic solvents. It has been found that it is excellent.
Although the reason why the solubility of the lithium parastyrene sulfonate copolymer in the organic solvent is not necessarily clear, it is considered that the lithium cation is smaller in size than the sodium cation.

Although there is no restriction | limiting in the weight average molecular weight calculated | required by GPC of the PSS lithium copolymer of this invention, 2000-1 million are preferable, and the intensity | strength of a coating film when apply | coating or kneading to a plastic base material, a base material Considering the influence on the mechanical properties and the handleability, 5,000 to 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.

  As a monomer other than the lithium parastyrene sulfonate used in the production of the PSS lithium copolymer of the present invention, a monomer that undergoes radical polymerization by a PSS lithium radical, or can be a radical polymerization initiator for lithium parastyrene sulfonate. There is no particular limitation as long as it generates radicals (in other words, can be radical copolymerized with lithium parastyrene sulfonate). For example, styrene, chlorostyrene, p-aminostyrene, dichlorostyrene, bromostyrene, dibromostyrene, fluorostyrene, 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 Styrenes such as 3-isopropenyl-α, α′-dimethylbenzyl isocyanate and vinylbenzyltrimethylammonium chloride, isobutyl vinyl ether, ethyl vinyl ether, 2-phenyl vinyl alkyl ether , Vinyl ethers such as nitrophenyl vinyl ether, cyanophenyl vinyl ether, chlorophenyl vinyl ether, chloroethyl vinyl ether, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, decyl acrylate, acrylic Lauryl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, bornyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2-hydroxyethyl acrylate, Tetrahydrofurfuryl acrylate, methoxyethylene glycol acrylate, ethyl carbitol acrylate, 2-hydroxypropyl acrylate, acrylic 4-hydroxybutyl toluate, 3- (trimethoxysilyl) propyl acrylate, polyethylene glycol acrylate, glycidyl acrylate, 2- (acryloyloxy) ethyl phosphate, 2,2,3,3-tetrafluoropropyl acrylate, Acrylic acid esters such as 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, and 2,2,3,4,4,4-hexafluorobutyl acrylate , Methyl methacrylate, t-butyl methacrylate, sec-butyl methacrylate, i-butyl methacrylate, i-propyl methacrylate, decyl methacrylate, lauryl methacrylate, octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, Cyclohexyl methacrylate, methacrylate Bornyl phosphate, benzyl methacrylate, phenyl methacrylate, glycidyl methacrylate, polyethylene glycol methacrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, methoxyethylene glycol methacrylate, ethyl carbitol methacrylate, 2-hydroxy methacrylate Propyl, 4-hydroxybutyl methacrylate, 2- (methacryloyloxy) ethyl phosphate, 2- (dimethylamino) ethyl methacrylate, 2- (diethylamino) ethyl methacrylate, 3- (dimethylamino) propyl methacrylate, methacrylic acid 2- (isocyanato) ethyl, 2,4,6-tribromophenyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2 methacrylate Methacrylic acid esters such as 2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 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 Butadiene, 1-chloro-1,3-butadiene, 2- (N-piperidylmethyl) -1,3-butadiene, 2-triethoxymethyl-1,3-butadiene, 2- (N, N-dimethylamino)- 1,3-butadienes such as 1,3-butadiene, N- (2-methylene-3-butenoyl) morpholine, diethyl 2-methylene-3-butenylphosphonate; Enylmaleimide, N- (chlorophenyl) maleimide, N- (methylphenyl) maleimide, N- (isopropylphenyl) maleimide, N- (sulfophenyl) maleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, N-naphthyl Maleimide, 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) maleimi N- (2,6-xylyl) maleimide, N- (aminophenyl) maleimide, N- (tribromophenyl) maleimide, N- [4- (2-benzimidazolyl) phenyl] maleimide, N- (3,5- Maleimides such as dinitrophenyl) maleimide, N- (9-acridinyl) maleimide, maleimide, N- (sulfophenyl) maleimide, N-cyclohexylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-methoxyphenylmaleimide, Fumarate diesters such as dibutyl fumarate, dipropyl fumarate, diethyl fumarate, dicyclohexyl fumarate, bis-2-ethylhexyl fumarate, dodecyl fumarate, fumaric acid monoesters such as butyl fumarate, propyl fumarate, ethyl fumarate , Maleic acid Maleic acid diesters such as butyl, dipropyl maleate and 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 Product, acrylamide, N-methylacrylamide, N-ethylacrylamide, 2-hydroxyethylacrylamide, N, N-diethylacrylamide, acryloylmorpholine, N, N-dimethylaminopropylacrylamide, isopropylacrylamide, N-methylolacrylimide, sulfo Phenylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-1-methylsulfonic acid, diacetone acrylamide, acrylic Acrylamides such as alkyltrialkylammonium chloride, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, 2-hydroxyethylmethacrylamide, N, N-diethylmethacrylamide, N, N-dimethylmethacrylamide, N- Methacrylol methacrylamide, methacryloylmorpholine, N, N-dimethylaminopropyl methacrylamide, isopropyl methacrylamide, 2-methacrylamide-2-methylpropane sulfonic acid, methacrylamide such as methacrylamide alkyltrialkylammonium chloride, and others, vinylpyrrolidone , Sulfophenylitaconimide, acrylonitrile, methacrylonitrile, fumaronitrile, α-cyanoethyl acrylate, citrate Acid, citraconic anhydride, vinyl acetic acid, 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, methacryloxypropyldimethoxysilane, acrolein, vinyl methyl ketone, N-vinylacetamide, N-vinylformamide, vinyl ethyl ketone, vinyl Sulfonic acid, allyl sulfonic acid, dehydroalanine, sulfur dioxide, isobutene, N-vinylcarbazole, vinylidene dicyanide, paraquinodimethane, chlorotrifluoroethylene, tetrafluoro Styrene, norbornene, N- vinylcarbazole, acrylic acid, and methacrylic acid. Among these, in consideration of copolymerization and availability with lithium parastyrene sulfonate, methyl methacrylate, 2,2,2-trifluoroethyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate 2-ethylhexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, N-phenylmaleimide, N-cyclohexylmaleimide, dibutyl fumarate, diethyl fumarate, 2-ethylhexyl fumarate, styrene and styrene derivatives are preferred.

  The proportion of other monomers other than the above-described lithium parastyrene sulfonate is 99 wt% or less, preferably about 10 to 90 wt%, more preferably about 30 to 90 wt% in all monomers. If it exceeds 99 wt%, depending on the application, it is possible to impart the characteristics of lithium parastyrene sulfonate to the polymer by copolymerization of a very small amount of lithium parastyrene sulfonate, but in the antistatic agent that is the main application of the present invention, When it uses, the characteristic of lithium parastyrene sulfonate becomes difficult to express and is not preferable. If other monomers (including other polymers described later) are less than 10 wt%, the solubility and compatibility with plastic are insufficient, which is not preferable.

Next, the manufacturing method of the PSS lithium copolymer of this invention is demonstrated.
Although the manufacturing method of a PSS lithium copolymer is not specifically limited, The method by general radical polymerization is illustrated as a 1st example. For example, after charging a reaction vessel with a homogeneous solution of a polar solvent or aqueous solvent and a mixture of other monomers capable of radical copolymerization with lithium parastyrene sulfonate, adding a molecular weight regulator as necessary, and deoxidizing the system The polymerization may be performed while heating to a predetermined temperature and 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.

The reaction solvent is not particularly limited, but considering the solubility of lithium parastyrene sulfonate and other copolymerizable monomer (comonomer) and its use as an antistatic agent, the organic solvent or water and the organic solvent Mixtures are preferred. The organic solvent is not limited as long as it is a composition in which a mixture of lithium parastyrene sulfonate and a comonomer is dissolved. For example, acetone, tetrahydrofuran, dioxane, methanol, ethanol, n-propanol, isopropanol, methoxyethanol, 2-ethoxy Examples include ethanol, 2-butoxyethanol, butanol, ethylene glycol, propylene glycol, glycerin, dimethyl sulfoxide, dimethylformamide, and N-methylpyrrolidone. Acetone, ethanol, isopropanol, n-propanol, n-butanol, sec-butanol, t-butanol, tetrahydrofuran, acetonitrile, dioxane, dimethyl sulfoxide, N-methylpyrrolidone, and dimethylformamide are preferable.
The amount of the organic solvent 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) ) 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-cyanopentanoic acid) · α-hydro Azo compounds such as ω- hydroxy poly (oxyethylene) polycondensate 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 lithium copolymer of the present invention can be produced by the above general radical polymerization, but if the living polymerization method is applied, the molecular weight distribution can be narrowed or a block copolymer can be produced.
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 lithium parastyrene sulfonate in an aqueous solvent, the lithium parastyrene sulfonate of the present invention is added, and further, living radical polymerization is continued, or After living radical polymerization of lithium parastyrene sulfonate in an aqueous solvent, another radical polymerizable monomer is added, and the living radical polymerization is continued. For example, a PSS lithium block copolymer can be produced by performing such living radical polymerization.

  Furthermore, in addition to the above-described method, the PSS lithium copolymer of the present invention can also be produced by a polymer reaction. For example, by radical polymerization of lithium parastyrene sulfonate using a polymer-type azo polymerization initiator, the polymer derived from the azo initiator (B of the above repeating structural unit) and the PSS lithium (A of the above repeating structural unit) are blocked. So-called block copolymers are obtained which are bonded together. The polymer azo initiator is not particularly limited, and for example, VPS series and VPE series manufactured by Wako Pure Chemical Industries, Ltd. can be used.

  Further, if a mercapto-terminated polymer (B of the above repeating structural unit) is used as a chain transfer agent and lithium parastyrenesulfonate is radically polymerized, PSS lithium (A of the above repeating structural unit) and a polymer derived from the chain transfer agent ( A block copolymer in which the above repeating structural units B) are bonded in a block manner through sulfide bonds is obtained. For example, after living anion polymerization of styrene or the like using an alkyl lithium compound as an initiator, the anion end is capped with ethylene sulfide, and finally an active hydrogen-containing compound such as alcohol is added to deactivate the anion polymerization growth end. Thus, mercapto-terminated polystyrene can be obtained. Alternatively, after thioacetic acid is used as a chain transfer agent and vinyl acetate is radically polymerized, the terminal and the main chain of the polymer are hydrolyzed with alkali or the like, so that mercapto-terminated polyvinyl alcohol or mercapto-terminated vinyl acetate / vinyl alcohol copolymer Coalescence can be obtained. The PSS lithium copolymer of the present invention is extremely effective as an antistatic agent for plastics and fibers because it is superior in solubility in organic solvents and heat resistance compared to conventional PSS salts.

  Examples of the polymer material to which the PSS lithium copolymer of the present invention can be applied include rubber and thermosetting resin in addition to plastic and fiber. Plastics include polymethacrylate, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, polyvinyl butylene, acetylated cellulose, polyester, polyacrylonitrile, polycarbonate, polypropylene, polyethylene, acrylonitrile / butadiene / styrene copolymer ( ABS resin), polyamide, polyetherimide, polyphenylene ether / polystyrene blend, and the like. Examples of the rubber include styrene / butadiene copolymer, acrylonitrile / butazine copolymer, polybutadiene, polyisoprene, polyurethane, polychloroprene, acrylic rubber, chlorosulfonated polyethylene, chlorinated polyethylene, and polyepichlorohydrin. Examples of the thermosetting resin include an epoxy resin, a phenol resin, a melamine resin, a polyurethane, and a polyimide resin.

As a method for adding the PSS lithium copolymer of the present invention to the polymer material, a known method can be used. For example, the PSS lithium copolymer of the present invention is made into a solution or powder, and a liquid, pellet, or powdery polymer material is uniformly mixed, or the solution of the PSS lithium copolymer of the present invention is formed into a film or the like. The antistatic property can be imparted to the polymer material by applying to the surface of the molded polymer material and drying.
The addition amount of the PSS lithium copolymer of this invention is 0.1-20 weight part normally with respect to 100 weight part of polymeric materials, Preferably it is 0.5-10 weight part. If the amount is less than 0.1 parts by weight, sufficient antistatic properties cannot be obtained. On the other hand, if the amount exceeds 20 parts by weight, performance such as mechanical properties of the polymer material is deteriorated.

  Moreover, you may use together the PSS lithium copolymer of this invention, and the conventional antistatic agent as needed. For example, high molecular weight antistatic agent such as polyether ester amide, polyether / polyolefin block copolymer, ethylene oxide / propylene oxide / allyl glycidyl ether copolymer, low molecular weight type such as dodecylbenzene sulfonate, alkyldiethanolamine, etc. An antistatic agent, an ionic metal salt such as n-butyl-4-methylpyridinium hexafluorophosphate, bis (fluorosulfonylimide) potassium, bis (trifluoromethanesulfoniumimide) lithium, or a carbon material is used as the PSS of the present invention. You may use together to 100 weight part with respect to 100 weight part of lithium copolymers. When the amount of the conventional antistatic agent added exceeds 100 parts by weight, the effect of adding the PSS lithium copolymer is diminished.

Since the polymer material to which the PSS lithium copolymer of the present invention is added or applied is excellent in antistatic property and heat resistance, electrical and electronic parts (optical materials, transparent materials for image display such as display screens, various films, etc. Sheet), fiber, clean room, etc., and can be used in applications that require countermeasures against static electricity.
Furthermore, since the PSS lithium copolymer of the present invention has a structure (so-called surfactant) having a sulfonic acid group which is a strong electrolyte in a main chain skeleton having a strong affinity with an organic compound, Expected to be used as a dispersant for silica, resin, conductive polymer, carbon nanomaterial, plating solution modifier, binder and modifier for secondary battery and capacitor electrode materials, hydrophilic coating agent, ion exchange resin Is done.
Further, the PSS lithium copolymer of the present invention can be used after being converted from a lithium salt to an ammonium salt, an amine salt, a phosphonium salt, or a proton type depending on the application. For example, the PSS lithium salt is treated with a strongly acidic cation exchange resin and converted to the proton type, and then neutralized with ammonia or amine, and the PSS lithium copolymer and tetraalkylphosphonium bromide are mixed to exchange the cation. It can be prepared by a method.

The following examples further illustrate the present invention, but the present invention is not limited to these examples.
<Measurement of GPC molecular weight and monomer polymerization conversion>
The monomer polymerization conversion rate and the molecular weight of the PSS lithium copolymer were measured under the following conditions.
Model = Tosoh HLC-8320GPC
Column = TSK guardcolumn AW-H / TSK AW-3000 / TSK AW-6000
Eluent = Sodium sulfate buffer (0.05 mol / L) and acetonitrile volume ratio 65:35 wt% solution Column temperature = 40 ° C., flow rate = 0.6 ml / min
Detector = UV detector [wavelength 230 nm (however, methacrylate monomer is analyzed at 215 nm)], injection amount = 10 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.

<Evaluation of solubility in organic solvents>
After collecting the vacuum-dried copolymer sample in a 30 ml glass sample bottle, various solvents were added so that the copolymer concentration was 5 wt% or 10 wt%, and the solubility was visually observed while gently shaking by hand. .
<Evaluation of heat resistance>
The thermal decomposition temperature Td5 (° C.) of the copolymer (temperature at which the weight decreases by 5 wt% due to the decomposition of the copolymer) was measured under the following conditions.
Model = Mac Science TG-DTA2000
Analysis sample = 5.0 mg collected in platinum open pan Standard sample = 5.0 mg Al ₂ O ₃ collected in platinum open pan Temperature rising rate = 10 ° C / min (from room temperature to 800 ° C)
Nitrogen flow rate = 50 ml / min

<Evaluation of compatibility and antistatic properties>
(1) Preparation of coating composition 4.00 g of polymethyl methacrylate (molecular weight 120,000) manufactured by Aldrich was mixed with water and ethanol in a mixed solution [volume ratio ethanol / (ethanol + water) = 80%] 96.00 g. In addition, the mixture was stirred and dissolved at 60 ° C.
Further, 0.40 g of the PSS lithium copolymer of the present invention was added to 100.00 g of the aqueous ethanol solution, and the mixture was stirred and dissolved at 60 ° C. to obtain a coating composition (the addition amount of the PSS lithium copolymer was polymethacrylic acid). 10 parts by weight per 100 parts by weight of methyl acid).
(2) Compatibility The coating composition was visually observed and the compatibility was evaluated from the transparency (or turbidity).
(3) Measurement of surface resistivity After heating a corona-treated polyester film (PETURA Chemicals PET film) to 50 ° C and applying the coating composition heated to 50 ° C using a bar coater (A solid content coating amount of 100 mg / m ² ) was dried in a hot air oven at 60 ° C. for 1 hour to prepare a test piece.
The test piece was allowed to stand for 24 hours in an atmosphere of 25 ° C. and 50% relative humidity, and then 1 minute after applying a voltage of 500 V in an atmosphere of 25 ° C. and 50% relative humidity using a Hiresta UP (MCP-HT450) manufactured by Mitsubishi Chemical. The surface specific resistivity of was measured.

Example 1
(Synthesis Example 1 of lithium parastyrene sulfonate / N-phenylmaleimide copolymer)
A 500 ml glass flask equipped with a reflux condenser and a nitrogen introduction tube was charged with 230.00 g of ethanol, 20.48 g of lithium parastyrene sulfonate (product of Tosoh Organic Chemical Co., Ltd., purity 88.7%), and 15.69 g of N-phenylmaleimide. While stirring with a magnetic stirrer, the mixture was deaerated at room temperature while flowing a small amount of nitrogen. Thereafter, heating was started in a 70 ° C. oil bath, and at the same time, a separately prepared polymerization initiator solution consisting of 1.56 g of azo initiator V-65 (manufactured by Wako Pure Chemical Industries) and 94.00 g of ethanol was added dropwise over 10 hours. Then, polymerization was performed. Thereafter, heating was continued at 70 ° C. for another 5 hours. When the polymerization conversion of lithium parastyrene sulfonate and N-phenylmaleimide was monitored using GPC, each monomer was consumed at almost the same rate as the polymerization time, and the final polymerization conversion was 98.4% and 99 respectively. It was 1%. From the polymerization behavior, it was judged that the copolymerization proceeded well.
After the polymerization solution cooled to room temperature was filtered through a quantitative filter paper (5 types C), about 200 g of ethanol was distilled off from the filtrate using a rotary evaporator and concentrated. The concentrated solution was gradually added to 900 ml of acetone while stirring to precipitate a polymer, which was separated by filtration with quantitative filter paper (5 types C). The recovered wet polymer was vacuum-dried at 100 ° C. for 3 hours to obtain 31.3 g of a white powdery PSS lithium / N-phenylmaleimide copolymer.
The number average molecular weight Mn of the copolymer determined by GPC was 9,800, and the weight average molecular weight Mw was 28,500. The copolymer was designated as PSS-1.

(Evaluation of physical properties of copolymer)
As shown in Table 1, the solubility of the PSS-1 is clearly superior to the copolymers of Comparative Examples 2-6 and Comparative Examples 7-8, and the heat resistance is Comparative Examples 5 and 6. It was clearly superior to the copolymer. Furthermore, since the compatibility of PSS-1 and polymethyl methacrylate is superior to the copolymers of Comparative Examples 2 to 6 and the polymers of Comparative Examples 7 to 8, a coating composition containing PSS-1 was applied. The surface resistivity of the PET film is lower than those of Comparative Examples 2 to 8, and it is clear that the antistatic property is excellent.

Example 2
(Synthesis Example 1 of lithium parastyrene sulfonate / styrene copolymer)
A 500 ml glass flask equipped with a reflux condenser and a nitrogen introduction tube was charged with 80.20 g of ethanol, 4.31 g of lithium parastyrene sulfonate (manufactured by Tosoh Organic Chemical Co., Ltd.), and 18.18 g of styrene. Deaerated at room temperature while flowing nitrogen. Thereafter, heating in an oil bath at 70 ° C. was started, and at the same time, a polymerization initiator solution consisting of 0.86 g of separately prepared azo initiator V-601 (manufactured by Wako Pure Chemical Industries) and 103.50 g of ethanol was dropped over 12 hours. Then, polymerization was performed. Thereafter, heating was continued at 70 ° C. for another 7 hours. When the polymerization conversion of lithium parastyrene sulfonate and styrene was tracked using GPC, each monomer was consumed at almost the same rate as the polymerization time, and the final polymerization conversion was 99.1% and 97.3%, respectively. was. From the polymerization behavior, it was judged that the copolymerization proceeded well.
After the polymerization solution cooled to room temperature was filtered through a quantitative filter paper (5 types C), about 120 g of ethanol was distilled off from the filtrate using a rotary evaporator and concentrated. The concentrated solution was gradually added to 900 ml of isopropanol while stirring to precipitate a polymer, which was separated by filtration with a quantitative filter paper (5 types C). The collected wet polymer was vacuum-dried at 100 ° C. for 3 hours to obtain 16.53 g of a white powdery PSS lithium / styrene copolymer.
The number average molecular weight Mn of the copolymer determined by GPC was 9,700, and the weight average molecular weight Mw was 21,400. The copolymer was designated as PSS-2.

(Evaluation of physical properties of copolymer)
As shown in Table 1, the solubility of PSS-2 is clearly superior to the copolymers of Comparative Examples 2-6 and Comparative Examples 7-8, and the heat resistance is Comparative Examples 5 and 6. It was clearly superior to the copolymer. Furthermore, since the compatibility of PSS-2 and polymethyl methacrylate is superior to the copolymer of Comparative Examples 2-6 and the polymers of Comparative Examples 7-8, the coating composition containing PSS-2 was applied. The surface resistivity of the PET film is lower than those of Comparative Examples 2 to 8, and it is clear that the antistatic property is excellent.

Example 3
(Synthesis Example 2 of lithium parastyrene sulfonate / styrene copolymer)
A 500 ml glass flask equipped with a reflux condenser and a nitrogen inlet tube was charged with 95.12 g of ethanol, 16.53 g of lithium parastyrene sulfonate (manufactured by Tosoh Organic Chemical Co., Ltd.), and 8.00 g of styrene. Deaerated at room temperature while flowing nitrogen. Thereafter, heating was started in an oil bath at 70 ° C., and at the same time, a polymerization initiator solution consisting of 0.65 g of separately prepared azo initiator V-60 (manufactured by Wako Pure Chemical Industries) and 100.80 g of ethanol was dropped over 11 hours. Then, polymerization was performed. Thereafter, heating was continued at 70 ° C. for another 4 hours. When the polymerization conversion of lithium parastyrene sulfonate and styrene was tracked using GPC, each monomer was consumed at almost the same rate as the polymerization time, and the final polymerization conversion was 99.4% and 99.6%, respectively. was. From the polymerization behavior, it was judged that the copolymerization proceeded well.
The polymerization solution cooled to room temperature is filtered through a quantitative filter paper (5 types C), lithium carbonate contained in lithium parastyrene sulfonate is filtered off, and about 130 g of ethanol is distilled off from the filtrate using a rotary evaporator and concentrated. did. The concentrated solution was gradually added to 900 ml of acetone while stirring to precipitate a polymer, which was separated by filtration with quantitative filter paper (5 types C). The recovered wet polymer was vacuum-dried at 100 ° C. for 3 hours to obtain 19.54 g of a white powdery PSS lithium / styrene copolymer.
The number average molecular weight Mn of the copolymer determined by GPC was 9,300, and the weight average molecular weight Mw was 74,300. The copolymer was designated as PSS-3.

(Evaluation of physical properties of copolymer)
As shown in Table 1, the solubility of the PSS-3 is clearly superior to the copolymers of Comparative Examples 2-6 and Comparative Examples 7-8, and the heat resistance is Comparative Examples 5 and 6. It was clearly superior to the copolymer. Furthermore, since the compatibility of PSS-3 and polymethyl methacrylate is superior to the copolymers of Comparative Examples 2-6 and Comparative Examples 7-8, a coating composition containing PSS-3 was applied. The surface resistivity of the PET film is lower than those of Comparative Examples 2 to 8, and it is clear that the antistatic property is excellent.

Example 4
(Synthesis example 1 of lithium parastyrene sulfonate / diethyl fumarate copolymer)
A 500 ml glass flask equipped with a reflux condenser and a nitrogen introduction tube was charged with 109.48 g of ethanol, 8.04 g of lithium parastyrene sulfonate (manufactured by Tosoh Organic Chemical), and 6.30 g of diethyl fumarate, and stirred with a magnetic stirrer. Deaerated at room temperature while flowing a small amount of nitrogen. Thereafter, heating in an oil bath at 70 ° C. was started, and at the same time, a polymerization initiator solution consisting of 0.45 g of separately prepared azo initiator V-60 (manufactured by Wako Pure Chemical Industries) and 101.28 g of ethanol was dropped over 11 hours. Then, polymerization was performed. Thereafter, heating was continued at 70 ° C. for another 4 hours. When the polymerization conversion of lithium parastyrene sulfonate and diethyl fumarate was monitored using GPC, each monomer was consumed at almost the same rate as the polymerization time, and the final polymerization conversion was 99.7% and 96.96%, respectively. It was 2%. From the polymerization behavior, it was judged that the copolymerization proceeded well.
The polymerization solution cooled to room temperature was filtered through a quantitative filter paper (5 types C), and about 130 g of ethanol was distilled off from the filtrate using a rotary evaporator and concentrated. The concentrated solution was gradually added to 900 ml of acetone while stirring to precipitate a polymer, which was separated by filtration with quantitative filter paper (5 types C). The recovered wet polymer was vacuum dried at 100 ° C. for 3 hours to obtain 10.47 g of a white powdery PSS lithium / diethyl fumarate copolymer.
The number average molecular weight Mn of the copolymer determined by GPC was 5,900, and the weight average molecular weight Mw was 21,400. The copolymer was designated as PSS-4.

(Evaluation of physical properties of copolymer)
As shown in Table 1, the solubility of the PSS-4 was clearly superior to the copolymers of Comparative Examples 2-6 and Comparative Examples 7-8, and the heat resistance was Comparative Examples 5 and 6. It was clearly superior to the copolymer. Furthermore, since the compatibility of PSS-4 and polymethyl methacrylate is superior to the copolymers of Comparative Examples 2 to 6 and the polymers of Comparative Examples 7 to 8, a coating composition containing PSS-4 was applied. The surface resistivity of the PET film is lower than those of Comparative Examples 2 to 8, and it is clear that the antistatic property is excellent.

Example 5
(Synthesis example 1 of lithium parastyrene sulfonate / methacrylic acid 2,2,2, -trifluoroethyl copolymer)
In a 500 ml glass flask equipped with a reflux condenser and a nitrogen inlet tube, 109.48 g of ethanol, 8.08 g of lithium parastyrene sulfonate (manufactured by Tosoh Organic Chemical), 6.30 g of 2,2,2, -trifluoroethyl methacrylate Was deaerated at room temperature while flowing a small amount of nitrogen under stirring with a magnetic stirrer. Thereafter, heating in an oil bath at 70 ° C. was started, and at the same time, a polymerization initiator solution consisting of 0.56 g of separately prepared azo initiator V-65 (manufactured by Wako Pure Chemical Industries) and 100.00 g of ethanol was dropped over 11 hours. Then, polymerization was performed. Thereafter, heating was continued at 70 ° C. for another 3 hours. When the polymerization conversion rate of lithium parastyrene sulfonate and 2,2,2, -trifluoroethyl methacrylate was traced using GPC, each monomer was consumed at almost the same rate as the polymerization time, and the final polymerization conversion rate Were 98.2% and 95.4%, respectively. From the polymerization behavior, it was judged that the copolymerization proceeded well.
The polymerization solution cooled to room temperature was filtered through a quantitative filter paper (5 types C), and about 130 g of ethanol was distilled off from the filtrate using a rotary evaporator and concentrated. The concentrated solution was gradually added to 900 ml of acetone while stirring to precipitate a polymer, which was separated by filtration with quantitative filter paper (5 types A). The recovered wet polymer was vacuum-dried at 100 ° C. for 3 hours to obtain 10.07 g of a white powdery PSS lithium / methacrylic acid 2,2,2, -trifluoroethyl copolymer.
The number average molecular weight Mn of the copolymer determined by GPC was 11,700, and the weight average molecular weight Mw was 49,800. The copolymer was designated as PSS-5.

(Evaluation of physical properties of copolymer)
As shown in Table 1, the solubility of PSS-5 is clearly superior to the copolymers of Comparative Examples 2-6 and Comparative Examples 7-8, and the heat resistance is Comparative Examples 5 and 6. It was clearly superior to the copolymer. Furthermore, since the compatibility of PSS-5 and polymethyl methacrylate is superior to the copolymers of Comparative Examples 2-6 and Comparative Examples 7-8, a coating composition containing PSS-5 was applied. The surface resistivity of the PET film is lower than those of Comparative Examples 2 to 8, and it is clear that the antistatic property is excellent.

Example 6
(Synthesis example 2 of lithium parastyrene sulfonate / methacrylic acid 2,2,2, -trifluoroethyl copolymer)
In a 500 ml glass flask equipped with a reflux condenser and a nitrogen inlet tube, 60.21 g of ethanol, 4.00 g of lithium parastyrene sulfonate (manufactured by Tosoh Organic Chemical), 8.30 g of 2,2,2, -trifluoroethyl methacrylate Was deaerated at room temperature while flowing a small amount of nitrogen under stirring with a magnetic stirrer. Thereafter, heating in an oil bath at 70 ° C. was started, and at the same time, a polymerization initiator solution consisting of 0.48 g of separately prepared azo initiator V-65 (manufactured by Wako Pure Chemical Industries) and 100.00 g of ethanol was dropped over 11 hours. Then, polymerization was performed. Thereafter, heating was continued at 70 ° C. for another 3 hours. When the polymerization conversion rate of lithium parastyrene sulfonate and 2,2,2, -trifluoroethyl methacrylate was traced using GPC, each monomer was consumed at almost the same rate as the polymerization time, and the final polymerization conversion rate Were 99.3% and 97.1%, respectively. From the polymerization behavior, it was judged that the copolymerization proceeded well.
The polymerization solution cooled to room temperature was filtered through a quantitative filter paper (5 types C), and about 100 g of ethanol was distilled off from the filtrate using a rotary evaporator and concentrated. The concentrated solution was gradually added to 900 ml of isopropanol while stirring to precipitate a polymer, which was separated by filtration with a quantitative filter paper (5 types A). The recovered wet polymer was vacuum-dried at 100 ° C. for 3 hours to obtain 10.51 g of a white powdery PSS lithium / methacrylic acid 2,2,2, -trifluoroethyl copolymer.
The number average molecular weight Mn of the copolymer determined by GPC was 16,300, and the weight average molecular weight Mw was 68,300. The copolymer was designated as PSS-6.

(Evaluation of physical properties of copolymer)
As shown in Table 1, the solubility of PSS-6 was clearly superior to the copolymers of Comparative Examples 2-6 and Comparative Examples 7-8, and the heat resistance was Comparative Examples 5 and 6. It was clearly superior to the copolymer. Furthermore, since the compatibility of PSS-6 and polymethyl methacrylate is superior to the copolymers of Comparative Examples 2-6 and Comparative Examples 7-8, a coating composition containing PSS-6 was applied. The surface resistivity of the PET film is lower than those of Comparative Examples 2 to 8, and it is clear that the antistatic property is excellent.

Example 7
(Synthesis Example 1 of lithium parastyrene sulfonate / dodecyl methacrylate copolymer)
A 500 ml glass flask equipped with a reflux condenser and a nitrogen inlet tube was charged with 72.10 g of ethanol, 50 mg of 10 wt% ethanol acetate solution, 4.00 g of lithium parastyrene sulfonate (manufactured by Tosoh Organic Chemical), and 6.30 g of dodecyl methacrylate. While stirring with a magnetic stirrer, the mixture was deaerated at room temperature while flowing a small amount of nitrogen. Thereafter, heating in an oil bath at 70 ° C. was started, and at the same time, a polymerization initiator solution consisting of 0.48 g of separately prepared azo initiator V-60 (manufactured by Wako Pure Chemical Industries) and 100.00 g of ethanol was dropped over 14 hours. Then, polymerization was performed. Thereafter, heating was continued at 70 ° C. for another 6 hours. The polymerization conversion of lithium parastyrene sulfonate measured by GPC was almost 100%. The polymerization conversion rate of dodecyl methacrylate could not be measured under the GPC conditions.
The polymerization solution cooled to room temperature was filtered through a quantitative filter paper (5 types C), and about 100 g of ethanol was distilled off from the filtrate using a rotary evaporator and concentrated. The concentrated solution was gradually added to 900 ml of acetone while stirring to precipitate a polymer, which was separated by filtration with quantitative filter paper (5 types A). The recovered wet polymer was vacuum dried at 100 ° C. for 3 hours to obtain 8.41 g of a white powdery PSS lithium / dodecyl methacrylate copolymer. The result of elemental analysis is carbon / hydrogen / sulfur content = 62.4 / 9.1 / 6.0 wt%, and the polymer is PSS lithium / dodecyl methacrylate = 43/57 molar ratio = 36/64 weight ratio It was judged that this was a copolymer.
The number average molecular weight Mn of the copolymer determined by GPC was 14,400, and the weight average molecular weight Mw was 57,600. The copolymer was designated as PSS-7.

(Evaluation of physical properties of copolymer)
As shown in Table 1, the solubility of PSS-7 was clearly superior to the copolymers of Comparative Examples 2-6 and Comparative Examples 7-8, and the heat resistance was Comparative Examples 5 and 6. It was clearly superior to the copolymer. Furthermore, since the compatibility of PSS-7 and polymethyl methacrylate is superior to the copolymers of Comparative Examples 2-6 and Comparative Examples 7-8, a coating composition containing PSS-7 was applied. The surface resistivity of the PET film is lower than those of Comparative Examples 2 to 8, and it is clear that the antistatic property is excellent.

Example 8
(Synthesis Example 1 of lithium parastyrene sulfonate / PEO copolymer)
In a 500 ml glass flask equipped with a reflux condenser and a nitrogen introduction tube, ethanol 25.00 g, pure water 25.10 g, 10 wt% ethanol acetate solution 50 mg, lithium parastyrene sulfonate (manufactured by Tosoh Organic Chemical) 4.00 g, polyethylene oxide 2.00 g of a macro-azo initiator VPE-0201 (manufactured by Wako Pure Chemical Industries, Ltd.) was charged, and deaerated at room temperature while flowing a small amount of nitrogen under magnetic stirring. Thereafter, heating was continued in an oil bath at 60 ° C. for 12 hours. The polymerization conversion of lithium parastyrene sulfonate measured by GPC was almost 100%.
After the polymerization solution cooled to room temperature was filtered through a quantitative filter paper (5 types C), about 35 g of the solvent was distilled off from the filtrate using a rotary evaporator and concentrated. The concentrated solution was gradually added to 900 ml of acetone while stirring to precipitate a polymer, which was separated by filtration with quantitative filter paper (5 types A). The recovered wet polymer was vacuum-dried at 90 ° C. for 6 hours to obtain 3.26 g of a white powdery PSS lithium / polyethylene oxide copolymer. From the sulfur content of the copolymer determined by elemental analysis = 12.2 wt%, the polymer was judged to be a copolymer of PSS lithium / polyethylene oxide = 73/27 weight ratio.
The number average molecular weight Mn of the copolymer determined by GPC was 27,000, and the weight average molecular weight Mw was 91,800. The copolymer was designated as PSS-8.

(Evaluation of physical properties of copolymer)
As shown in Table 1, the solubility of PSS-8 is clearly superior to the copolymers of Comparative Examples 2-6 and Comparative Examples 7-8, and the heat resistance is Comparative Examples 5 and 6. It was clearly superior to the copolymer. Furthermore, since the compatibility of PSS-8 and polymethyl methacrylate is superior to the copolymers of Comparative Examples 2-6 and Comparative Examples 7-8, a coating composition containing PSS-8 was applied. The surface resistivity of the PET film is lower than those of Comparative Examples 2 to 8, and it is clear that the antistatic property is excellent.

Comparative Example 1
Add 4.00 g of polymethyl methacrylate (molecular weight 120,000) made by Aldrich to 96.00 g of a mixed solution of water and ethanol [volume ratio ethanol / (ethanol + water) = 80%], and stir and dissolve at 60 ° C. Thus, a coating composition was obtained.
After a corona-treated polyester film (PETURA Chemicals PET film) is heated to 50 ° C. and the above-mentioned coating composition heated to 50 ° C. is applied using a bar coater (solid content coating amount 100 mg / m ² ), and dried in a hot air oven at 60 ° C. for 1 hour to prepare a test piece. As shown in Table 1, the surface resistivity is 2 × 10 ¹⁵ Ω / □, which is clearly higher than that of the example.

Comparative Example 2
(Synthesis Example 1 of sodium parastyrenesulfonate / N-phenylmaleimide copolymer)
In a 300 ml glass flask equipped with a reflux condenser and a nitrogen inlet, 65.14 g of pure water, 65.00 g of acetone, 3.17 g of sodium parastyrene sulfonate (manufactured by Tosoh Organic Chemical), 2.31 g of N-phenylmaleimide, α -0.08 g of methylstyrene dimer was charged and degassed at room temperature while flowing a small amount of nitrogen under stirring with a magnetic stirrer. Thereafter, heating was started in an oil bath at 60 ° C., and at the same time, a polymerization initiator solution comprising 0.29 g of separately prepared azo initiator V-50 (manufactured by Wako Pure Chemical Industries), 40.00 g of pure water, and 40.00 g of acetone. Was dropped over 3 hours to carry out polymerization. Thereafter, heating was continued at 60 ° C. for another 7 hours. When GPC was used to monitor the polymerization conversion of sodium parastyrenesulfonate and N-phenylmaleimide, each monomer was consumed at almost the same rate as the polymerization time, and the final polymerization conversion was 96.3% and 100 respectively. %was. From the polymerization behavior, it was judged that the copolymerization proceeded well.
About 150 g of the solvent was distilled off from the polymerization solution using a rotary evaporator and concentrated. The concentrated solution was gradually added to 900 ml of acetone while stirring to precipitate a polymer, which was separated by filtration with quantitative filter paper (5 types C). The recovered wet polymer was vacuum-dried at 100 ° C. for 3 hours to obtain 4.13 g of white powdery PSS sodium / N-phenylmaleimide copolymer.
The number average molecular weight Mn of the copolymer determined by GPC was 9,200, and the weight average molecular weight Mw was 20,100. The copolymer was designated as PSS-9.

(Evaluation of physical properties of copolymer)
As shown in Table 1, the solubility of the PSS-9 was clearly inferior to the copolymers of the examples. Furthermore, since the compatibility of PSS-9 and polymethyl methacrylate is inferior to the copolymer of an Example, the surface resistivity of the PET film which coated the coating composition containing PSS-9 is more than an Example. It is clearly low and the antistatic property is inferior.

Comparative Example 3
(Synthesis example 1 of sodium parastyrene sulfonate / styrene copolymer)
In a 300 ml glass flask equipped with a reflux condenser and a nitrogen inlet, 65.00 g of pure water, 65.00 g of acetone, 3.20 g of sodium parastyrene sulfonate (manufactured by Tosoh Organic Chemical), 1.40 g of styrene, α-methylstyrene Dimer 0.08g was charged, and deaerated at room temperature while flowing a small amount of nitrogen under stirring with a magnetic stirrer. Thereafter, heating was started in an oil bath at 60 ° C., and at the same time, a polymerization initiator solution consisting of 0.30 g of an azo initiator V-50 (manufactured by Wako Pure Chemical Industries), 40.00 g of pure water and 40.00 g of acetone. Was added dropwise over 10 hours to carry out polymerization. Thereafter, heating was continued at 60 ° C. for another 10 hours. When GPC was used to monitor the polymerization conversion of sodium parastyrenesulfonate and styrene, each monomer was consumed at almost the same rate as the polymerization time, and the final polymerization conversion was 99.5% and 95.3%, respectively. was. From the polymerization behavior, it was judged that the copolymerization proceeded well.
About 150 g of the solvent was distilled off from the polymerization solution using a rotary evaporator and concentrated. The concentrated solution was gradually added to 900 ml of isopropanol while stirring to precipitate a polymer, which was separated by filtration with a quantitative filter paper (5 types C). The collected wet polymer was vacuum-dried at 100 ° C. for 3 hours to obtain 3.40 g of a white powdery PSS sodium / styrene copolymer.
The number average molecular weight Mn of the copolymer determined by GPC was 8,700, and the weight average molecular weight Mw was 18,200. The copolymer was designated as PSS-10.

(Evaluation of physical properties of copolymer)
As shown in Table 1, the solubility of the PSS-10 was clearly inferior to the copolymers of the examples. Furthermore, since the compatibility of PSS-10 and polymethyl methacrylate is inferior to the copolymer of an Example, the surface resistivity of the PET film which coated the coating composition containing PSS-10 is more than an Example. It is clearly low and the antistatic property is inferior.

Comparative Example 4
(Synthesis Example 1 of sodium parastyrenesulfonate / 2,2,2, -trifluoroethyl methacrylate copolymer)
In a 300 ml glass flask equipped with a reflux condenser and a nitrogen inlet tube, 36.00 g of pure water, 56.20 g of acetone, 7.28 g of sodium parastyrene sulfonate (manufactured by Tosoh Organic Chemical), 2,2,2, -methacrylic acid Trifluoroethyl (5.12 g) and thioglycerol (0.08 g) were charged, and the mixture was deaerated at room temperature while flowing a small amount of nitrogen under stirring with a magnetic stirrer. Thereafter, heating was started in an oil bath at 60 ° C., and at the same time, a polymerization initiator solution comprising 0.66 g of separately prepared azo initiator V-50 (manufactured by Wako Pure Chemical Industries), 27.00 g of pure water and 40.00 g of acetone. Was added dropwise over 10 hours to carry out polymerization. Thereafter, heating was continued at 60 ° C. for another 6 hours. When the polymerization conversion rate of sodium parastyrene sulfonate and 2,2,2, -trifluoroethyl methacrylate was traced using GPC, each monomer was consumed at almost the same rate as the polymerization time, and the final polymerization conversion rate Were 99.1% and 98.2%, respectively. From the polymerization behavior, it was judged that the copolymerization proceeded well.
About 100 g of the solvent was distilled off from the polymerization solution using a rotary evaporator and concentrated. The concentrated solution was gradually added to 900 ml of isopropanol while stirring to precipitate a polymer, which was separated by filtration with a quantitative filter paper (5 types C). The recovered wet polymer was vacuum dried at 100 ° C. for 3 hours to obtain 9.5 g of a white powdery PSS sodium / 2,2,2, -trifluoroethyl methacrylate copolymer.
The number average molecular weight Mn of the copolymer determined by GPC was 11,000, and the weight average molecular weight Mw was 38,000. The copolymer was designated as PSS-11.

(Evaluation of physical properties of copolymer)
As shown in Table 1, the solubility of the PSS-11 was clearly inferior to the copolymers of the examples. Furthermore, since the compatibility of PSS-11 and polymethyl methacrylate is inferior to the copolymer of an Example, the surface resistivity of the PET film which coated the coating composition containing PSS-11 is more than an Example. It is clearly low and the antistatic property is inferior.

Comparative Example 5
(Synthesis Example 1 of ammonium parastyrenesulfonate / 2,2,2, -trifluoroethyl methacrylate copolymer)
Through a glass column packed with 1000 ml of a strongly acidic cation exchange resin (organo, Amberlite IR-120B) regenerated with hydrochloric acid, 625 g of an aqueous solution of 16 wt% sodium parastyrene sulfonate (manufactured by Tosoh Organic Chemical) was passed through to give styrene sulfone. The aqueous acid solution was recovered. The solution was quickly neutralized with ammonia to obtain an aqueous solution of ammonium styrenesulfonate. The aqueous solution was concentrated with a rotary evaporator and then poured into a large amount of acetone to recover crystals of ammonium styrenesulfonate (purity 94.0%).
In a 300 ml glass flask equipped with a reflux condenser and a nitrogen inlet tube, 35.00 g of pure water, 55.00 g of acetone, 6.65 g of ammonium parastyrenesulfonate, 2,2,2, -trifluoroethyl methacrylate, and 5. 11 g and 0.08 g of thioglycerol were charged, and the mixture was deaerated at room temperature while flowing a small amount of nitrogen under stirring with a magnetic stirrer. Thereafter, heating was started in an oil bath at 60 ° C., and at the same time, a polymerization initiator solution comprising 0.66 g of separately prepared azo initiator V-50 (manufactured by Wako Pure Chemical Industries), 27.00 g of pure water and 40.00 g of acetone. Was added dropwise over 10 hours to carry out polymerization. Thereafter, heating was continued at 60 ° C. for another 6 hours. When the polymerization conversion of ammonium parastyrenesulfonate and 2,2,2, -trifluoroethyl methacrylate was traced using GPC, each monomer was consumed at almost the same rate as the polymerization time, and the final polymerization conversion Were 99.5% and 98.0%, respectively. From the polymerization behavior, it was judged that the copolymerization proceeded well.
About 100 g of the solvent was distilled off from the polymerization solution using a rotary evaporator and concentrated. The concentrated solution was gradually added to 900 ml of isopropanol while stirring to precipitate a polymer, which was separated by filtration with a quantitative filter paper (5 types C). The collected wet polymer was vacuum-dried at 90 ° C. for 3 hours to obtain 9.6 g of a white powdery PSS ammonium / methacrylic acid 2,2,2, -trifluoroethyl copolymer.
The number average molecular weight Mn of the copolymer determined by GPC was 11,000, and the weight average molecular weight Mw was 39,000. The copolymer was designated as PSS-12.

(Evaluation of physical properties of copolymer)
As shown in Table 1, the solubility and heat resistance of the PSS-12 were clearly inferior to the copolymers of the examples. Furthermore, since the compatibility of PSS-12 and polymethyl methacrylate is inferior to the copolymer of the Example, the surface resistivity of the PET film coated with the coating composition containing PSS-12 is higher than that of the Example. It is clearly low and the antistatic property is inferior.

Comparative Example 6
(Synthesis example 1 of vinylbenzyltrimethylammonium chloride / styrene copolymer)
In a 300 ml glass flask equipped with a reflux condenser and a nitrogen introduction tube, pure water 65.00 g, acetone 65.00 g, vinylbenzyltrimethylammonium chloride (manufactured by Aldrich, purity 99.9%) 2.88 g, and styrene 1.40 g were added. The mixture was deaerated at room temperature while flowing a small amount of nitrogen while stirring with a magnetic stirrer. Thereafter, heating was started in an oil bath at 60 ° C., and at the same time, a polymerization initiator solution consisting of 0.30 g of an azo initiator V-50 (manufactured by Wako Pure Chemical Industries), 40.00 g of pure water and 40.00 g of acetone. Was added dropwise over 10 hours to carry out polymerization. Thereafter, heating was continued at 60 ° C. for another 10 hours. When GPC was used to monitor the polymerization conversion of sodium parastyrenesulfonate and styrene, each monomer was consumed at approximately the same rate as the polymerization time, and the final polymerization conversion was 99.3% and 96.3%, respectively. was. From the polymerization behavior, it was judged that the copolymerization proceeded well.
About 150 g of the solvent was distilled off from the polymerization solution using a rotary evaporator and concentrated. The concentrated solution was gradually added to 900 ml of isopropanol while stirring to precipitate a polymer, which was separated by filtration with a quantitative filter paper (5 types C). The recovered wet polymer was vacuum dried at 100 ° C. for 3 hours to obtain 2.98 g of a light yellow powdery vinylbenzyltrimethylammonium chloride / styrene copolymer.
The number average molecular weight Mn of the copolymer determined by GPC was 9,800, and the weight average molecular weight Mw was 20,100. The copolymer was designated as PSS-13.

(Evaluation of physical properties of copolymer)
As shown in Table 1, the solubility of the PSS-13 in the 1-methoxy-2-propanol / ethanol mixed solvent was equivalent to that of the example, but the heat resistance was clearly inferior. Furthermore, since the compatibility of PSS-13 and polymethyl methacrylate is inferior to the copolymer of the Example, the surface resistivity of the PET film coated with the coating composition containing PSS-13 is higher than that of the Example. It is clearly low and the antistatic property is inferior.

Comparative Example 7
(Synthesis Example 1 of lithium polyparastyrene sulfonate)
A 500 ml glass flask equipped with a reflux condenser and a nitrogen introduction tube was charged with 300.07 g of pure water and 10.01 g of lithium parastyrene sulfonate (manufactured by Tosoh Organic Chemical Co., Ltd., purity 88.7%) and stirred with a magnetic stirrer. Deaerated at room temperature while flowing a small amount of nitrogen. Thereafter, heating in an oil bath at 80 ° C. was started, and at the same time, a polymerization initiator solution consisting of 1.00 g of separately prepared azo initiator V-50 (manufactured by Wako Pure Chemical Industries) and 30.02 g of pure water was taken over 3 hours. It dripped and superposed | polymerized. Thereafter, heating was continued at 80 ° C. for another 3 hours. The polymerization conversion rate of lithium parastyrene sulfonate measured by GPC was 99.4%.
The polymer solution cooled to room temperature was filtered through a quantitative filter paper (5 types C), collected in a glass petri dish, and vacuum-dried at 100 ° C. for 3 hours to obtain white powdered PSS lithium.
The number average molecular weight Mn of the copolymer determined by GPC was 43,000, and the weight average molecular weight Mw was 120,500. The copolymer was designated as PSS-14.

(Evaluation of physical properties of copolymer)
As shown in Table 1, the heat resistance of the PSS-14 was excellent, but the solubility was inferior to the copolymers of the examples. Furthermore, since the compatibility of PSS-14 and polymethyl methacrylate is inferior to the copolymer of an Example, the surface resistivity of the PET film which coated the coating composition containing PSS-14 is more than an Example. It is clearly low and the antistatic property is inferior.

Comparative Example 8
(Synthesis example 1 of sodium polyparastyrene sulfonate)
A 500 ml glass flask equipped with a reflux condenser and a nitrogen introduction tube was charged with 300.00 g of pure water and 11.01 g of sodium parastyrene sulfonate (manufactured by Tosoh Organic Chemical Co., Ltd.) while flowing a small amount of nitrogen while stirring with a magnetic stirrer. Degassed at room temperature. Thereafter, heating was started in an oil bath at 80 ° C., and at the same time, a polymerization initiator solution consisting of 1.00 g of separately prepared azo initiator V-50 (manufactured by Wako Pure Chemical Industries) and 30.05 g of pure water was taken over 3 hours. It dripped and superposed | polymerized. Thereafter, heating was continued at 80 ° C. for another 3 hours. The polymerization conversion rate of sodium parastyrene sulfonate measured by GPC was 99.5%.
The polymerization solution was collected in a glass petri dish and vacuum-dried at 100 ° C. for 3 hours to obtain white powdered PSS sodium.
The number average molecular weight Mn of the copolymer determined by GPC was 53,000, and the weight average molecular weight Mw was 159,000. The copolymer was designated as PSS-15.

(Evaluation of physical properties of copolymer)
As shown in Table 1, the heat resistance of the PSS-15 was excellent, but the solubility was clearly inferior to the copolymers of the examples. Furthermore, since the compatibility of PSS-15 and polymethyl methacrylate is inferior to the copolymer of an Example, the surface resistivity of the PET film which coated the coating composition containing PSS-15 is more than an Example. It is clearly low and the antistatic property is inferior.

  Since the lithium styrene sulfonate copolymer of the present invention is excellent in solubility in organic solvents and heat resistance, in addition to antistatic agents for plastics and fibers, dispersants such as pigments, resins, conductive polymers, carbon nanomaterials, etc. It is also expected to be used as a plating solution modifier, a binder or modifier for secondary batteries and capacitor electrode materials, and a hydrophilic coating agent.

Claims (8)

Lithium styrene sulfonate copolymer having the following repeating structural unit A and the following repeating structural unit B having excellent solubility and heat resistance in an organic solvent and having a weight average molecular weight of 2,000 to 1,000,000 determined by gel permeation chromatography .
[In repeating structural units A and B, M represents a lithium cation, Q represents another radical polymerizable monomer residue or radical reactive polymer residue, n represents an integer of 1 or more, and m represents an integer of 1 or more. Represent. ]   2. The organic solvent according to claim 1, wherein the solubility in ethanol (weight of copolymer / weight of solution × 100) is 10 wt% or more, and the thermal decomposition temperature determined by simultaneous differential thermal-thermogravimetric measurement is 300 ° C. or higher. A lithium styrene sulfonate copolymer with excellent solubility in solvents and heat resistance.   Radical polymerizable monomer in which Q is one or a combination of two or more selected from the group consisting of a methacrylic acid ester residue, an N-substituted maleimide residue, a fumaric acid diester residue, a styrene residue and a styrene derivative residue The lithium styrene sulfonate copolymer excellent in solubility in an organic solvent and heat resistance according to claim 1, which is a residue.   Q is glycidyl methacrylate, butyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, 2,2,2-trifluoroethyl methacrylate, N-phenylmaleimide, N-cyclohexylmaleimide, diethyl fumarate, dibutyl fumarate It is a radically polymerizable monomer residue that is one or a combination of two or more selected from bis-2-ethylhexyl fumarate and styrene, and has solubility and heat resistance in an organic solvent according to claim 1. Excellent lithium styrene sulfonate copolymer.   The organic solvent according to claim 1, wherein Q is a radical reactive polymer residue that is a combination of one or more selected from a polymer azo polymerization initiator residue and a thiol-terminated polymer residue. Styrene sulfonate copolymer with excellent solubility and heat resistance.   An antistatic agent comprising a lithium styrene sulfonate copolymer excellent in solubility in an organic solvent and heat resistance according to any one of claims 1 to 5.   The hydrophilic coating agent containing the polystyrene sulfonate lithium copolymer excellent in the solubility to the organic solvent of any one of Claims 1-5, and heat resistance.   The dispersing agent containing the polystyrene sulfonate lithium copolymer excellent in the solubility to the organic solvent of any one of Claims 1-5, and heat resistance.