KR102583331B1 - Ionic copolymer having antistatic properties and method for preparing antistatic composition using the same - Google Patents

Abstract

The present invention relates to a method for producing an ionic copolymer and an antistatic composition, including a boranization step of polyolefin, a functionalization step of polyolefin, a polymer initiator preparation step, a copolymer preparation step, an ionic copolymer preparation step, and an antistatic agent composition. It relates to an ionic copolymer that does not lose transparency through the manufacturing process, has little migration, maintains antistatic properties for a long period of time, and has excellent mechanical properties, processability, and weather resistance, and a method of manufacturing an antistatic composition using the same.

Description

Ionic copolymer having antistatic properties and method for producing an antistatic composition using the same {Ionic copolymer having antistatic properties and method for preparing antistatic composition using the same}

The present invention relates to a method for producing an ionic copolymer and an antistatic composition, and more specifically, to an antistatic composition that does not impair transparency, has little migration, maintains antistatic properties for a long period of time, and has excellent mechanical properties, processability, and weather resistance. It relates to an ionic copolymer having properties and a method for producing an antistatic composition using the same.

Polymer resin is inexpensive, lightweight compared to other materials, does not corrode, and has the characteristics of being relatively free to form, so it has recently been widely used as an advanced electronic material, replacing traditional materials such as wood, metal, and stone. It is being used.

This polymer-related industry developed rapidly along with the development of the petrochemical industry in the 1950s, and now occupies an indispensable position in industrial development in all fields as well as our daily lives.

Most polymer materials have difficulty in the flow of electricity, so they are widely used as electrical insulators. Due to this characteristic, it is easy to develop static electricity, which is a phenomenon that occurs when objects with different polarities are charged with the same amount of charge on both sides when they come in contact with each other, rub against each other, or separate.

In other words, the movement of electrons between two materials occurs, causing one surface to lack electrons and the other surface to have an excess of electrons, resulting in a charging phenomenon in which charge separation occurs. Such charging occurs in polymer resins. When this phenomenon occurs, the movement of electric charges does not occur and static electricity is generated. This phenomenon can be seen all around us.

Factors that affect this charging phenomenon include the chemical structure of the polymer material, charging sequence and size depending on the dielectric constant, contact area, contact time, friction speed, and pressure between contact materials.

However, such static electricity can act as one of the factors causing problems in all industrial fields.

For example, it acts as a factor that reduces productivity during the polymer molding process, and in the textile industry, static electricity causes fibers to stick to each other or repel each other, making use or processing difficult, and the transport of flammable paints, solvents, and fine powder. Alternatively, if static electricity is generated during spraying, a discharged spark may cause a fire or explosion.

In addition, in the semiconductor manufacturing process, electrostatic discharge can damage circuits and cause malfunctions in precision electronic products such as communication devices and major measuring instruments, which can cause major accidents. In particular, with the development of electronic communication technology, the devices used therein can be damaged. As parts have become increasingly smaller, it has often occurred that the fine structure inside the device is damaged by static electricity, stopping the operation of the product.

Therefore, in the case of polymer resin molding or synthetic fiber processing, the grounding method is most widely used, but since the method of grounding the polar conductor in the electrical part does not prevent charging, the area where friction occurs must be moved to a place where there is less charge. An anti-static effect can be achieved by using materials, etc. There is also a method of removing static electricity by generating a high frequency or high voltage to ionize the air around the polymer material by generating a corona discharge between the electrodes, thereby attaching and neutralizing charges of the opposite polarity. This can be used during the production process, but the product in use There are usage restrictions that prevent it from being used.

Next, there is a method to exhibit an antistatic effect by molding graphite or conductive metal powder with synthetic resin to give conductivity, but it is expensive and has a large amount of addition, which increases the cost and tends to affect the physical properties of the final product. In addition, there are various restrictions on color, such as not being able to be used for transparent purposes. However, it is partially used in semiconductor packaging materials that require conductive materials.

In addition, since it was known that the phenomenon of a rapid increase in electrical conductivity when polyacetylene film was doped with a halogen element, when special antistatic effect, that is, conductivity, was required, polyacetylene, polyaniline, and polypyrrole with conjugated double bonds were used. Conductive polymers such as polypyrrole and polythiophene are attracting attention and have been developed and are partially used, but problems include poor stability, low solubility, and difficulty in processing.

Currently, various antistatic agents are available to suit different purposes by incorporating low-molecular-type antistatic agents into the polymer resin or applying them thinly on the surface to increase the hygroscopicity or ionicity of the surface to facilitate leakage of electric charges and to exhibit antistatic effects. Methods for controlling static electricity are widely used.

However, if the conventional antistatic agent is removed from the surface for any reason such as washing or friction, the antistatic effect is lost. In addition, if too much of the antistatic agent is expressed on the surface, it contaminates the object in contact or reduces physical properties by showing printability and stickiness, and even if the antistatic agent is added, it does not come out to the surface of the polymer material or if the amount is small, the antistatic agent is prevented. It has disadvantages such as the fact that it is not effective.

In order to improve these characteristics, the prior art and patent documents that have been developed and patented so far are examined as follows.

Republic of Korea Patent No. 101567450 provides an antistatic composition containing polydecamethylene terephthalamide resin and a compound imparted with an antistatic function. The antistatic composition according to the invention includes polydecamethylene terephthalamide; and a carbon nanotube to which a polysiloxane-poly(ethylene/propylene glycol) graft copolymer has been added. Republic of Korea Patent No. 101209195 is a water-dispersible polyether polyurethane dispersion of an anion containing at least one functional group selected from the group consisting of a hydroxyl group, an amine group, an alkyl group, and a carboxyl group, based on 100 parts by weight of a conductive polymer resin. 100 to 1,000 parts by weight of polyurethane resin, 100 to 1,000 parts by weight of any crosslinking agent resin selected from the group consisting of isocyanate-based, carbonylimide-based, oxazoline-based, epoxy-based and melamine-based, and 10 to 100 parts by weight of fluorine resin. An antistatic coating composition further containing 0.001 to 1 part by weight of an acetylene diol-based surfactant is provided based on 100 parts by weight of the antistatic coating composition. In addition, by applying the antistatic coating composition according to the above invention to a polyester film using an in-line coating method, it has excellent transparency, antistatic properties, peeling power from adhesive tape, antifouling performance, and coating properties, and is easy to control coating defects, especially at the interface. An antistatic polyester film for protecting polarizers with little deterioration in physical properties due to the characteristics of the activator is provided. Republic of Korea Patent No. 101090494 forms an adhesive layer by applying an adhesive composition containing 0.01 to 10 parts by weight of a multifunctional curing agent based on 100 parts by weight of a (meth)acrylic copolymer containing an ionic monomer on the first release film. , It is an antistatic adhesive film in which a second release film is laminated on an adhesive layer. It has excellent stability over time and has excellent antistatic performance by securing a peeling voltage of less than 0.5kV and a surface resistance of 106~1011Ω/cm, and is an adhesive composition. An antistatic adhesive film and a composition for manufacturing an antistatic adhesive film are provided in which the problem of adhesive components sticking to the adherend due to the bleed out phenomenon is improved. Republic of Korea Patent No. 101241280 is an ultraviolet curable antifouling antistatic hard coating composition that is cured by ultraviolet irradiation to form a hard coating layer, comprising 3 to 30 parts by weight of ultraviolet curable resin and fluorine-modified multifunctional acrylic for 100 parts by weight of the total composition. The composition for an ultraviolet curable antifouling antistatic hard coating comprising 0.01 to 3 parts by weight of a late compound, 5 to 30 parts by weight of an aqueous conductive polymer solution, 0.1 to 5 parts by weight of a photopolymerization initiator, and 30 to 90 parts by weight of a polar organic solvent with affinity for the conductive polymer. The hard coating layer cured by ultraviolet irradiation has a hardness greater than or equal to 3H, a surface resistance of 106~108Ω/cm, a water contact angle greater than or equal to 95°, a visible light transmittance greater than or equal to 92%, and a surface resistance greater than or equal to 0.5%. Disclosed is a composition for an ultraviolet curable antifouling antistatic hard coating characterized by having a haze value. According to the above invention, a hard coating layer for anti-fouling and anti-static properties can be formed on a plastic panel with a single coating, so the process is simple and the production cost is low, as well as adhesion to the plastic panel, transparency, scratch resistance, and anti-static properties. It has the advantage of excellent prevention and contamination resistance. Republic of Korea Patent No. 101773204 discloses a wholly aromatic liquid crystal polyester resin compound and article. The disclosed wholly aromatic liquid crystal polyester resin compound is characterized by comprising a wholly aromatic liquid crystal polyester resin and an electrically conductive filler. Republic of Korea Patent No. 101793757 provides an antistatic agent that maintains antistatic properties over a long period of time and does not damage its appearance or transparency even when placed in a resin, and a resin composition containing the same. In addition, the above invention is obtained from a reaction product of (a) a polyolefin whose one end is acid-modified and (b) a diol and/or diamine having a polyoxyalkylene chain, and some or all of the acid groups remaining in the reaction product are alkaline. An antistatic agent made of a block copolymer neutralized by a substance, a thermoplastic resin composition containing the same, and films and sheets made of the thermoplastic resin composition are provided. Republic of Korea Patent No. 101808633 includes 100 parts by weight of an antistatic polyester resin, 5 to 15 parts by weight of a sulfonate-based anionic surfactant, and 1 to 10 parts by weight of polyalkylene glycol or a derivative thereof with a molecular weight in the range of 300 to 20,000. An antistatic composition for powder coating is provided. Using the antistatic agent composition of the above invention as a component of a powder coating composition has the advantage of being able to obtain a powder coating with good color and low surface resistance of the coating film. Republic of Korea Patent No. 101336838 discloses a colorless antistatic agent for electronic materials composed of a mixture of a surfactant, a neutralizer, and a fluorine-based lithium organic compound, a pH stabilization step of adding a neutralizer to the surfactant, and an interface that has undergone the pH stabilization step. A method for producing an antistatic agent comprising the steps of adding a fluorine-based lithium organic compound to an activator and mixing it by stirring at a constant temperature and a constant stirring speed, the antistatic agent, a multifunctional oligomer or monomer, a leveling agent, and a diluting solvent. An ultraviolet curable antistatic coating composed of a mixture of a phosphorus organic solvent and a photoinitiator and a material manufactured using the same are provided. Republic of Korea Patent No. 100502558 discloses an ion-compressed antistatic agent composed of a cation-ion conductive material and an anion-ion conductive material formed by coordination as a conductivity providing material, and an ion-compressed conductive polymer resin (ion- complex conducting polymer). Republic of Korea Patent No. 100905959 provides an antistatic agent that is excellent in preventing fogging or film loss in chemically amplified resist, and an antistatic film and coating article using the antistatic agent. According to the above invention, an antistatic agent containing a water-soluble conductive polymer, a solvent, and a water-soluble polymer. By using a specific water-soluble polymer, especially a water-soluble polymer compound having a polypeptide bond or a specific water-soluble polymer having a polyvinyl structure, in combination with a water-soluble conductive polymer, a surfactant can be used that is inexpensive and can easily provide coating properties to the resist. , while maintaining applicability, the influence on the resist (fogging of the resist or film thinning phenomenon that occurs as a result of dissolution of the resist or development of the resist) can be suppressed. Antistatic agents that improve applicability by containing a surfactant are effective in suppressing mixing with chemically amplified resists and non-chemically amplified resists. Republic of Korea Patent No. 101630590 provides a donor-acceptor antistatic agent that can prevent charging of insulating polymer materials with better reproducibility and durability. The antistatic agent according to the present invention is a donor-acceptor system that can be obtained by mixing and melting a semi-polar organic boron compound (donor component) at the top and an alkaline nitrogen compound (acceptor component) at the bottom to react. An antistatic agent for insulating polymer materials consisting of a molecular compound is characterized. Republic of Korea Patent No. 102204102 is an antistatic agent for polyolefin made of a block copolymer containing hydrophilic blocks and hydrophobic blocks linked by ether or ester bonds at a weight ratio of 1:0.1 to 100 and having a weight average molecular weight of 10 to 100 kDa, and an antistatic agent containing the same. An antistatic polyethylene film is provided. The antistatic polyethylene film according to the invention has a very high degree of cleanliness with minimal bleed-out or mobility, has the desired antistatic effect even without the use of additional additives, and is similar to polyolefin, which is a base resin. It has physical properties and processability. Republic of Korea Patent No. 100885896 consists of an inner layer laminated by mixing polypropylene and a permanent antistatic agent, a middle layer laminated with polypropylene on the inner layer, and an outer layer laminated on the middle layer by mixing polypropylene and a permanent antistatic agent. According to the above-mentioned invention, the antistatic agent does not transfer to the surface of the adherend in a high temperature and high humidity environment and has the advantage of excellent slipperiness. In addition, the stiffness of the material is not too hard or too soft, so it does not cause scratches, etc., and at the same time, there is no folding of the film when attached to the screen of the adherend, and it is a product for LCD protection made by mixing permanent antistatic agent with polypropylene, which has excellent productivity. There is an advantage in providing a triple extruded film. Republic of Korea Patent No. 100184731 relates to a bifunctional antistatic agent containing a quaternary ammonium salt and a method for manufacturing the same. More specifically, the antistatic agent is reactive, so it cures quickly during the curing process while maintaining permanent antistatic properties. Not only is this possible, but because it is functional, it does not cause significant changes in the photocurable resin composition compared to non-functional antistatic agents, does not cause yellowing during UV curing, does not use solvents in the manufacturing process, and has weather resistance without generating waste water. Disclosed is an excellent photocurable antistatic agent and a method for manufacturing the same. Republic of Korea Patent Publication No. 1019970074890 provides a novel reactive permanent antistatic agent and a photocurable resin composition containing the same. The permanent antistatic agent according to the above invention has trimethoxy siloxy morpholinium salt, so unlike conventional permanent antistatic agents, once hardened, it does not fall off easily even after washing with water or abrasion, and can provide a permanent antistatic effect. In addition, because it contains a trimethyl siloxy group, it is possible to obtain a coating film with improved water resistance, so it has excellent effects such as an antistatic effect without deteriorating the various original physical properties of the resin.

Therefore, the technical problem to be achieved by the present invention was created to solve the above-mentioned need. By mixing an ionic copolymer into an antistatic composition, transparency is not impaired, migration is small, and antistatic properties are maintained for a long period of time, while maintaining mechanical properties, processability, and weather resistance. The purpose of the present invention is to provide an ionic copolymer with excellent antistatic properties and a method for producing an antistatic composition using the same.

In order to achieve the above object, the present invention purges an inert gas into a reactor equipped with gas purging equipment, a stirrer, and a thermostat, thereby purging the polymerization solvent. After administering 10,000 parts by weight of solvent and 10 to 300 parts by weight of chain transfer agent, monomer is supplied to maintain the pressure at 1 to 2 atm and the reactor temperature is raised to 20 to 100°C. 5 to 40 parts by weight of a catalyst, which is a zirconium compound, and 10 to 60 parts by weight of a co-catalyst selected from alkylaluminoxane were added to the reactor and the reactor was reacted at a speed of 50 to 500 RPM. Polymerization is initiated while stirring, and the polymerization reaction proceeds for 1 to 24 hours while maintaining the reactor pressure at 1 to 2 atmospheres and the temperature at 20 to 100°C by continuously supplying monomers. After the reaction was completed, 10 to 100 parts by weight of alcohol was added to the polymerization reaction liquid extracted from the bottom of the reactor to terminate the reaction, and the reaction mixture was subjected to steam stripping to separate the copolymer from the solvent, and then A boranization step of polyolefin to produce borane-terminated polyolefin by drying under reduced pressure at ~100°C for 12 to 48 hours;

While purging an inert gas in a reactor equipped with gas purging equipment, a dropper, a stirrer, and a temperature controller, 100,000 parts by weight of a reaction solvent and 20,000 to 40,000 parts by weight of the borane-terminated polyolefin prepared in the boranization step of polyolefin were sequentially added. After administration, while stirring at a speed of 50 to 500 RPM, add 20,000 to 40,000 parts by weight of distilled water, 2,000 to 8,000 parts by weight of a base such as sodium hydroxide or potassium hydroxide, and alcohol. After adding 2,000 to 8,000 parts by weight, the reaction temperature was lowered to -10 to 0°C, and 15,000 to 40,000 parts by weight of hydrogen peroxide aqueous solution (10 to 30 wt% of hydrogen peroxide: 90 to 70 wt% of water content) was added to 30%. After adding dropwise for ~60 minutes, the reaction temperature was raised to 30~60℃ and the reaction proceeded for a further 4~12 hours while stirring at a speed of 50~500RPM. Then, the resulting reactant was filtered/washed and stored at 50~100℃. A functionalization step of polyolefin to produce hydroxy-terminated polyolefin by drying under reduced pressure for 12 to 48 hours;

While purging an inert gas in a reactor equipped with gas purging equipment, a stirrer, and temperature controller, 100,000 parts by weight of the reaction solvent and 20,000 to 40,000 parts by weight of the hydroxy-terminated polyolefin prepared in the functionalization step of the polyolefin were added, and then the reactor temperature was adjusted. Raise the temperature to 30~60℃ and stir at a speed of 50~500RPM for 6~24 hours, then add sodium naphthalenide, lithium naphthalenide, or potassium naphthalenide to the reactor. ), maintain the reaction temperature at 30~60℃ by administering 1,000~10,000 parts by weight of reducing agent selected from ), stir at a speed of 50~500RPM for 3~12 hours, filter/wash the resulting mixture, and store at 50~100℃. A polymer initiator preparation step of preparing a polymer initiator by drying under reduced pressure for 12 to 48 hours;

While purging an inert gas in a reactor equipped with gas purging equipment, a stirrer, and temperature controller, 100,000 parts by weight of the reaction solvent, 20,000 to 40,000 parts by weight of the polymer initiator prepared in the polymer initiator manufacturing step, and 10,000 to 90,000 parts by weight of alkene oxide. After adding 100 to 1,000 parts by weight of metal hydride, the temperature of the reactor was raised to 60 to 100°C and reaction was performed at a rate of 50 to 500 RPM for 24 to 60 hours, and then 1,000 to 2,000 parts by weight of alcohol was added for reaction. A copolymer preparation step of filtering and washing the resulting mixture and then drying it under reduced pressure at 50-100°C for 12-60 hours to produce a polyolefin-polyalkenoxide copolymer;

100,000 parts by weight of the dispersion solvent and 20,000 to 40,000 parts by weight of the polyolefin-polyalkenoxide copolymer prepared in the copolymer production step were added to a reactor equipped with a stirrer and a temperature controller, then the reactor temperature was raised to 20 to 60 ° C. and the temperature of the reactor was raised to 50 to 50 ° C. After stirring for 1 to 6 hours at a speed of 500 RPM, 200 to 600 parts by weight of ionic liquid was added to the reactor to maintain the reactor temperature at 20 to 60 ° C. and stirred at a speed of 50 to 500 RPM for 1 to 6 hours. An ionic copolymer preparation step of preparing an ionic copolymer by filtering, washing, and drying the stirred reactant at 50 to 100° C. for 12 to 24 hours;

100,000 weight of polymer selected from polyolefin resin, ethylene copolymer, and synthetic rubber in a mixing mixer such as Kneader, Hensel, Banbury, etc. 100 to 500 parts by weight of electrically conductive filler, 20,000 to 40,000 parts by weight of ionic copolymer prepared in the ionic copolymer manufacturing stage, 50 to 200 parts by weight of antioxidant used alone or in combination of two or more of the sulfur compounds, and fatty acid. 100 to 1,400 parts by weight of a lubricant selected from fatty acid metal salts is sequentially administered and kneaded for 5 to 60 minutes at a temperature of 80 to 200°C. The lump dough is then extruded using a single screw or twin screw extruder. Extruder) and go through the antistatic agent composition manufacturing step of producing antistatic agent composition pellets of 3 to 5mm in size through extrusion molding; Ionic copolymers with antistatic properties and compositions using them can be easily manufactured.

As described above, the present invention relates to an ionic copolymer having antistatic properties with excellent mechanical properties, processability, and weather resistance that exhibits low migration and long-term antistatic properties without compromising transparency, and an antistatic composition using the same. It has the effect of making it easy to manufacture.

1 is a process flow diagram illustrating a method of implementing the present invention.

The present invention purges an inert gas into a reactor equipped with gas purging equipment, a stirrer, and a thermostat, while purging 10,000 parts by weight of a polymerization solvent and a chain. After administering 10 to 300 parts by weight of a chain transfer agent, monomer is supplied to maintain the pressure at 1 to 2 atm, and the reactor temperature is raised to 20 to 100°C. 5 to 40 parts by weight of a catalyst selected from zirconium compounds and 10 to 60 parts by weight of a co-catalyst selected from alkylaluminoxane were added to the reactor at 50 to 500 RPM. The polymerization is initiated while stirring at a speed of , and the polymerization reaction proceeds for 1 to 24 hours while maintaining the reactor pressure at 1 to 2 atm by continuously supplying monomers and the temperature at 20 to 100°C. After the reaction was completed, 10 to 100 parts by weight of alcohol was added to the polymerization reaction liquid extracted from the bottom of the reactor to terminate the reaction. The reaction mixture was subjected to steam stripping to separate the copolymer from the solvent, and then the copolymer was separated from the solvent. A boranization step of polyolefin to produce borane-terminated polyolefin by drying under reduced pressure at 100°C for 12 to 48 hours;

While purging an inert gas in a reactor equipped with gas purging equipment, a dropper, a stirrer, and a temperature controller, 100,000 parts by weight of a reaction solvent and 20,000 to 40,000 parts by weight of the borane-terminated polyolefin prepared in the boranization step of polyolefin were sequentially added. After administration, while stirring at a speed of 50 to 500 RPM, add 20,000 to 40,000 parts by weight of distilled water, 2,000 to 8,000 parts by weight of a base such as sodium hydroxide or potassium hydroxide, and alcohol. After adding 2,000 to 8,000 parts by weight, lower the reaction temperature to -10 to 0℃, and add 15,000 to 40,000 parts by weight of hydrogen peroxide aqueous solution (10 to 30 wt% of hydrogen peroxide: 90 to 70 wt% of water content). After adding dropwise for 60 minutes, the reaction temperature was raised to 30~60℃ and the reaction proceeded for a further 4~12 hours while stirring at a speed of 50~500RPM. The resulting reactant was filtered, washed, and incubated at 50~100℃ for 12 hours. Functionalizing the polyolefin to produce a hydroxy-terminated polyolefin by drying under reduced pressure for ~48 hours;

While purging an inert gas, 100,000 parts by weight of the reaction solvent and 20,000 to 40,000 parts by weight of the hydroxy-terminated polyolefin prepared in the functionalization step of the polyolefin were added to a reactor equipped with gas purging equipment, a stirrer, and a temperature controller, and the reactor temperature was adjusted to 30~40%. Raise the temperature to 60℃ and stir at a speed of 50~500RPM for 6~24 hours, then add sodium naphthalenide, lithium naphthalenide, potassium naphthalenide, etc. to the reactor. 1,000 to 10,000 parts by weight of the reducing agent was administered to maintain the reaction temperature at 30 to 60°C and stirred at a speed of 50 to 500 RPM for 3 to 12 hours. The resulting mixture was filtered and washed and stirred at 50 to 100°C for 12 to 12 hours. A polymer initiator preparation step of preparing a polymer initiator by drying under reduced pressure for 48 hours;

By purging inert gas into a reactor equipped with gas purging equipment, stirrer, and temperature controller,

After adding 100,000 parts by weight of the reaction solvent, 20,000 to 40,000 parts by weight of the polymer initiator prepared in the polymer initiator production step, 10,000 to 90,000 parts by weight of alkene oxide, and 100 to 1,000 parts by weight of metal hydride, the reactor temperature Raise the temperature to 60-100℃ and react at a speed of 50-500RPM for 24-60 hours. Then, 1,000-2,000 parts by weight of alcohol is added to complete the reaction. The mixture is filtered and washed, and then reacted at 50-100℃ for 12-60 hours. A copolymer preparation step of preparing a polyolefin-polyalkenoxide copolymer by drying under reduced pressure for a period of time;

100,000 parts by weight of the dispersion solvent and 20,000 to 40,000 parts by weight of the polyolefin-polyalkene oxide copolymer prepared in the copolymer production step were added to a reactor equipped with a stirrer and temperature controller, then the reactor temperature was raised to 20 to 60 ° C. and 50 ° C. After stirring for 1 to 6 hours at a speed of ~500 RPM, 200 to 600 parts by weight of ionic liquid was added to the reactor to maintain the reactor temperature at 20 to 60°C and stirred at a speed of 50 to 500 RPM for 1 to 6 hours. An ionic copolymer preparation step of preparing an ionic copolymer by filtering, washing, and drying the reactant stirred for a period of time at 50 to 100° C. for 12 to 24 hours;

100,000 weight of polymer selected from polyolefin resin, ethylene copolymer, and synthetic rubber in a mixing mixer such as Kneader, Hensel, Banbury, etc. 100 to 500 parts by weight of an electrically conductive filler, 20,000 to 40,000 parts by weight of the ionic copolymer prepared in the ionic copolymer manufacturing step, 50 to 200 parts by weight of an antioxidant used alone or in combination of two or more of the sulfur compounds, and fatty acids. 100 to 1,400 parts by weight of a lubricant selected from fatty acid metal salts is sequentially administered, and the lump dough is kneaded for 5 to 60 minutes at a temperature of 80 to 200°C and extruded using a single screw or twin screw extruder. Going through the antistatic agent composition manufacturing step of producing antistatic agent composition pellets of 3 to 5mm in size through extrusion molding by transferring them to a screw extruder; Ionic copolymers and antistatic compositions can be easily prepared.

The present invention will be described in detail with reference to Figure 1 as an embodiment as follows.

An inert gas selected from nitrogen, argon, neon, etc. is supplied to a reactor equipped with gas purging equipment, stirrer, and thermostat. ) while purging organic solvents such as pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene ( 10,000 parts by weight of polymerization solvent selected from organic solvent and triethylborane, tripropylborane, dimesitylborane, or 9-borabicylcononane ), 10 to 300 parts by weight of a chain transfer agent selected from borane compounds such as boron dipyromethene, thexylborane, and disiamylborane, and then added with ethylene. ) or monomers selected from monomers such as propylene, butene, cyclopentene, 4-methyl-1-pentene, etc. (monomer) is supplied, the pressure is maintained at 1 to 2 atm, and the reactor temperature is raised to 20 to 100°C.

In the reactor, racemic-dimethylsilylbis(1-indenyl)zirconium dichloride [rac-dimethylsilylbis(1-indenyl)zirconium dichloride], racemic-dimethylsilylbis[1-(2-methyl-4,5-benzo) indenyl)] zirconium dichloride Ly[rac-dimethylsilylbis(2-ethyl-4-phenylindenyl)zirconium dichloride], racemic-dimethylsilylbis[1-(2-n-propyl-4-(1-naphthyl)indenyl)]zirconium dichloride { rac-dimethylsilyl-bis[l-(2-n-propyl-4-(1-naphthyl)indenyl)]zirconium dichloride}, racemic-dimethylsilylbis[1-(2-ethyl-4-(9-phenanthryl) ) indenyl)] zirconium dichloride {rac-dimethylsilylbis[1-(2-ethyl-4-(9-phenanthryl)indenyl)]zirconium dichloride}, racemic-dimethylsilylbis[1-(2-n-propyl- 4-(9-phenanthryl)indenyl)]zirconium dichloride {rac-dimethylsilylbis[l-(2-n-propyl-4-(9-phenanthryl)indenyl)]zirconium dichloride}, which is selected from zirconium compounds such as 5 to 40 parts by weight of catalyst and methylaluminoxane or 2,6-di-tert-butyl-4-methylphenol modified methylaluminoxane Polymerization is initiated by adding 10 to 60 parts by weight of a co-catalyst selected from aluminoxane such as modified methylaluminoxane and polymethylaluminoxane and stirring at a speed of 50 to 500 RPM. The reactor pressure is adjusted to the monomer pressure. (monomer) is continuously supplied and the polymerization reaction proceeds for 1 to 24 hours while maintaining the pressure at 1 to 2 atmospheres and the temperature at 20 to 100°C.

After the reaction is completed, 10 to 100 parts by weight of alcohol selected from methanol, ethanol, propanol, isopropyl alcohol, etc. is added to the polymerization reaction solution extracted from the bottom of the reactor. After the reaction is completed, the reaction mixture is subjected to steam stripping to separate the copolymer from the solvent, and then dried under reduced pressure at 50 to 100°C for 12 to 48 hours to produce borane-terminated polyolefin. The boranization step of;

While purging an inert gas in a reactor equipped with gas purging equipment, dropper, stirrer, and temperature controller, diethyl ether, ethyl acetate, tetrahydrofuran, or methyl ethyl ketone ), 100,000 parts by weight of a reaction solvent selected from the group consisting of etc., and 20,000 to 40,000 parts by weight of borane-terminated polyolefin prepared in the boranization step of polyolefin were sequentially added, followed by adding 20,000 to 20,000 parts of distilled water while stirring at a speed of 50 to 500 RPM. After adding 40,000 parts by weight, 2,000 to 8,000 parts by weight of base such as sodium hydroxide or potassium hydroxide, and 2,000 to 8,000 parts by weight of alcohol, the reaction temperature was -10 to 0°C. , add 15,000 to 40,000 parts by weight of hydrogen peroxide aqueous solution (10 to 30% by weight of hydrogen peroxide: 90 to 70% by weight of water) dropwise for 30 to 60 minutes, then raise the reaction temperature to 30 to 60°C. After the reaction proceeded for an additional 4 to 12 hours while stirring at a speed of 50 to 500 RPM, the resulting reactant was filtered, washed, and dried under reduced pressure at 50 to 100°C for 12 to 48 hours to produce hydroxy-terminated polyolefin. a functionalization step of polyolefin to produce polyolefin;

Select from diethyl ether, ethyl acetate, tetrahydrofuran, or methyl ethyl ketone while purging an inert gas in a reactor equipped with gas purging equipment, stirrer, and temperature controller. After adding 100,000 parts by weight of the reaction solvent and 20,000 to 40,000 parts by weight of the hydroxy-terminated polyolefin prepared in the functionalization step of the polyolefin, the temperature of the reactor was raised to 30 to 60 ° C. and the reactor was heated at a speed of 50 to 500 RPM. After stirring for 6 to 24 hours, 1,000 to 10,000 parts by weight of a reducing agent selected from sodium naphthalenide, lithium naphthalenide, potassium naphthalenide, etc. is added to the reactor. The reaction temperature was maintained at 30-60℃ and stirred at a speed of 50-500RPM for 3-12 hours. The resulting mixture was filtered, washed, and dried under reduced pressure at 50-100℃ for 12-48 hours to add a polymer initiator ( A polymer initiator manufacturing step of producing an initiator);

While purging an inert gas in a reactor equipped with gas purging equipment, a stirrer, and temperature controller, 100,000 parts by weight of the reaction solvent, 20,000 to 40,000 parts by weight of the polymer initiator prepared in the polymer initiator production step, ethylene oxide, or propylene oxide. 10,000 to 90,000 parts by weight of alkene oxide such as propylene oxide, butylene oxide, octene oxide, beryllium hydride, calcium hydride, titanium After adding 100 to 1,000 parts by weight of a metal hydride selected from titanium hydride, etc., the temperature of the reactor was raised to 60 to 100°C and reacted at a speed of 50 to 500 RPM for 24 to 60 hours. A copolymer preparation step of preparing a polyolefin-polyalkenoxide copolymer by filtering and washing the mixture in which 1,000 to 2,000 parts by weight of alcohol was added to terminate the reaction, and then drying it under reduced pressure at 50 to 100°C for 12 to 60 hours;

In a reactor equipped with a stirrer and temperature controller, 100,000 parts by weight of a dispersion solvent selected from ether, ketone, alcohol, etc. and 20,000 ~ 20,000 parts by weight of the polyolefin-polyalkene oxide copolymer prepared in the copolymer production step. After administering 40,000 parts by weight, raising the temperature of the reactor to 20-60°C and stirring for 1-6 hours at a speed of 50-500 RPM, sodium thiocyanate or potassium thiocyanate is added to the reactor. ), 1-ethyl 3-methylimidazolium, thiocyanate, 1-butyl-3-methylimidazolium thiocyanate, It is selected from 1-butyl-1-methylpyrrolidinium thiocyanate, 1-ethyl-1-methylpiperidinium thiocyanate, etc. 200 to 600 parts by weight of ionic liquid was administered to maintain the reactor temperature at 20 to 60°C, and the reactant was stirred at a speed of 50 to 500 RPM for 1 to 6 hours, filtered, washed, and stirred for 12 hours at 50 to 100°C. An ionic copolymer preparation step of preparing an ionic copolymer by drying for ~24 hours;

Add polyolefin resin such as polyethylene, polypropylene, or polymethylpentene to a mixing mixer such as Kneader, Hensel, or Banbury, or ethylene- Vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-ethyl acrylate copolymer (ethylene) -ethylene copolymer such as ethylacrylate copolymer, butadiene rubber, nitrile butadiene rubber, chloroprene rubber, isobutylene rubber, styrene butadiene 100,000 parts by weight of a polymer selected from synthetic rubber such as styrene butadiene rubber, graphene, carbon black, graphite, and electrically conductive mica. 100 to 500 parts by weight of an electrically conductive filler selected from conductive mica, indium tin oxide, tin dioxide, zinc oxide, antimony-doped tin oxide, etc. , 20,000 to 40,000 parts by weight of the ionic copolymer prepared in the ionic copolymer production step, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate][thiodiethylene bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodipropionic acid dioctadecylester, distearyl thiodipropionate ), 50 to 200 parts by weight of antioxidants used alone or in combination of two or more sulfur compounds such as 3-mercaptopropionic acid, calcium stearate, and magnesium stearate. ), 100 to 1,400 parts by weight of a lubricant selected from fatty acid metal salts such as aluminum stearate and lithium stearate are sequentially administered and treated at a temperature of 80 to 200°C. The antistatic agent composition manufacturing step is to transfer the lump dough kneaded for 5 to 60 minutes to a single screw or twin screw extruder and produce antistatic agent composition pellets of 3 to 5 mm in size through extrusion molding; An ionic copolymer and antistatic composition were prepared.

In the boranization step of the polyolefin, the chain transfer agent introduces a borane group at the end of the polymer and adds triethylborane, tripropylborane, dimethylborane, 9-boravisylcononane, boron dipyrromethene, thexylborane, and disiamylborane. etc. are preferable and 10 to 300 parts by weight are used.

At this time, if the chain transfer agent is less than 10 parts by weight, reactivity is low, and if it is more than 300 parts by weight, economic feasibility is low.

In the boranization step of the polyolefin, the monomer forms a polymer, and alkene compounds such as ethylene, propylene, butene, cyclopentane, and 4-methyl-1-pentene are used singly or in combination of two or more, but the present invention is not limited thereto. no.

At this time, if the pressure of the monomer is less than 1 atm, the yield decreases, and if the pressure is more than 2 atm, the molecular weight increases.

In the boranization step of the polyolefin, the catalyst used as a polymerization reaction catalyst is racemic-dimethylsilylbis(1-indenyl)zirconium dichloride, racemic-dimethylsilylbis[1-(2-methyl-4,5-benzoindenyl) )] zirconium dichloride, racemic-dimethylsilylbis(2-ethyl-4-phenylindenyl)zirconium dichloride, racemic-dimethylsilylbis[1-(2-n-propyl-4-(1-naph) Tyl)indenyl)]zirconium dichloride, racemic-dimethylsilylbis[1-(2-ethyl-4-(9-phenanthryl)indenyl)]zirconium dichloride, racemic-dimethylsilylbis[1-( 5 to 40 parts by weight of zirconium compounds such as 2-n-propyl-4-(9-phenanthryl)indenyl)]zirconium dichloride are used, but the present invention is not limited thereto.

At this time, if the catalyst is less than 5 parts by weight, the reaction yield decreases, and if it is more than 40 parts by weight, economic feasibility decreases.

In the boranization step of the polyolefin, the cocatalyst improves the reaction activity of the catalyst and is an alkyl aluminoxane such as methylaluminoxane, 2,6-di-tert-butyl-4-methylphenol-modified methylaluminoxane, and polymethylaluminoxane. 10 to 60 parts by weight are used.

At this time, if the cocatalyst is less than 10 parts by weight, the reaction yield decreases, and if it is more than 60 parts by weight, catalyst residue increases.

In the boranization step of the polyolefin, 10 to 100 parts by weight of alcohol, such as methanol, ethanol, propanol, or isopropyl alcohol, is used as a heavy reaction terminating agent, but the present invention is not limited thereto.

In the polymer initiator manufacturing step, 1,000 to 10,000 parts by weight of metal naphthalide, such as sodium naphthalide, lithium naphthalide, or potassium naphthalide, is used as a reducing agent, but the present invention is not limited thereto.

At this time, if the metal naphthalide is less than 1,000 parts by weight, polymerization reactivity is low, and if it is more than 10,000 parts by weight, economic feasibility is poor.

The manufacturing method of the ionic copolymer and antistatic composition according to the present invention will be examined in more detail, and examples thereof will be described as follows.

The present invention will be described in more detail through examples below.

However, the scope of the present invention is not limited to the illustrative examples.

Example 1

While purging argon into the reactor, 10,000 g of hexane and 200 g of 9-boravisilcononane were added, and then ethylene was supplied to maintain the pressure at 1 atm and raise the reactor temperature to 60°C. In the reactor, 20 g of racemic-dimethylsilylbis[1-(2-methyl-4,5-benzoindenyl)]zirconium dichloride and 30 g of 2,6-di-tert-butyl-4-methylphenol-modified methylaluminoxane were added to the reactor. is added and the polymerization is initiated while stirring at a speed of 100 RPM. The reactor pressure is set to 1 atm by continuously supplying monomers, and the polymerization reaction proceeds for 2 hours while maintaining the temperature at 60°C. After the reaction was completed, 50 g of methanol was added to the polymerization product extracted from the bottom of the reactor to terminate the reaction. The reaction mixture was subjected to steam stripping to separate the copolymer from the solvent, and then dried in a vacuum oven at 50-60°C for 24 hours to obtain borane. -Terminated polyolefin was prepared.

While purging argon into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of borane-terminated polyolefin were sequentially added, and then 25,000 g of distilled water, 2,500 g of sodium hydroxide, and 3,000 g of methanol were added while stirring at a speed of 50 RPM. The reactor temperature was lowered to -5°C, and 20,000 g of hydrogen peroxide aqueous solution (30% by weight of hydrogen peroxide) was added dropwise over 60 minutes. Then, the reaction temperature was raised to 40°C and stirred at a speed of 100 RPM for an additional 8 hours. After the reaction proceeded, the resulting reactant was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare hydroxy-terminated polyolefin.

While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of hydroxy-terminated polyolefin were added, the temperature of the reactor was raised to 50°C and stirred at a speed of 100 RPM for 10 hours, and 4,000 g of potassium naphthalide was added to the reactor. g was administered and stirred for 8 hours at a speed of 100 RPM while maintaining the reaction temperature at 50°C, and then the resulting mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polymer initiator.

While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran, 25,000 g of polymer initiator, 50,000 g of ethylene oxide, and 200 g of calcium hydride were added. The reactor temperature was raised to 80°C and reacted at a rate of 100 RPM for 50 hours, followed by methanol. The reaction was terminated by adding 1,500 g, and the mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polyolefin-polyalkenoxide copolymer.

100,000 g of ethanol and 25,000 g of polyolefin-polyalkenoxide copolymer were added to the reactor, the temperature of the reactor was raised to 40°C and stirred for 1 hour at a speed of 100 RPM, and then 500 g of 1-butyl-1-methylpyrrolidinium thiocyanate was added. was administered and stirred for 2 hours at a speed of 100 RPM while maintaining the temperature at 40°C. The reaction product was filtered, washed, and dried in a vacuum oven at 60°C for 12 hours to prepare an ionic copolymer.

In a kneader mixer, 100,000g of polyethylene, 300g of antimony tin oxide, 25,000g of ionic copolymer, 150g of thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, calcium After administering 400 g of stearate, the lump dough kneaded for 20 minutes at a temperature of 120° C. was transferred to a twin-screw extruder and extruded to produce antistatic agent composition pellets with a size of 3 to 5 mm.

Example 2

While purging argon into the reactor, 10,000 g of Hexac and 200 g of tripropylborane were added, and then ethylene was supplied to maintain the pressure at 1 atm and raise the reactor temperature to 60°C. 20 g of racemic-dimethylsilylbis(1-indenyl)zirconium dichloride and 30 g of methylaluminoxane were added to the reactor to initiate polymerization while stirring at a speed of 100 RPM, and the reactor pressure was adjusted to 1 atm by continuously supplying monomers. , the polymerization reaction proceeds for 2 hours while maintaining the temperature at 60°C. After the reaction was completed, 50 g of methanol was added to the polymerization product extracted from the bottom of the reactor to terminate the reaction. The reaction mixture was subjected to steam stripping to separate the copolymer from the solvent, and then dried in a vacuum oven at 50-60°C for 24 hours to obtain borane. -Terminated polyolefin was prepared.

While purging argon into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of borane-terminated polyolefin were sequentially added, and then 25,000 g of distilled water, 2,500 g of sodium hydroxide, and 3,000 g of methanol were added while stirring at a speed of 50 RPM. The reactor temperature was lowered to -5°C, and 20,000 g of hydrogen peroxide aqueous solution (30% by weight of hydrogen peroxide) was added dropwise over 60 minutes. Then, the reaction temperature was raised to 40°C and stirred at a speed of 100 RPM for an additional 8 hours. After the reaction proceeded, the resulting reactant was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare hydroxy-terminated polyolefin.

While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of hydroxy-terminated polyolefin were added, the temperature of the reactor was raised to 50°C, the reactor was stirred at a speed of 100 RPM for 10 hours, and 4,000 g of sodium naphthalide was added to the reactor. g was administered to maintain the reaction temperature at 50°C and stir at a speed of 100 RPM for 8 hours. Then, the resulting mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polymer initiator.

While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran, 25,000 g of polymer initiator, 50,000 g of ethylene oxide, and 200 g of calcium hydride were added, then the reactor temperature was raised to 80°C and reacted at a speed of 100 RPM for 50 hours. The reaction was terminated by adding 1,500 g of methanol, and the mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polyolefin-polyalkenoxide copolymer.

100,000 g of ethanol and 25,000 g of polyolefin-polyalkenoxide copolymer were added to the reactor to raise the temperature of the reactor to 40°C and stirred for 1 hour at a speed of 100 RPM. Then, 500 g of potassium thiocyanate was added to maintain the temperature at 40°C and the temperature was maintained at 100 RPM. The reaction product was stirred at high speed for 2 hours, filtered, washed, and dried in a vacuum oven at 60°C for 12 hours to prepare an ionic copolymer.

In a kneader mixer, add 100,000g of polyethylene, 300g of graphene, 25,000g of ionic copolymer, 150g of thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and calcium stearate. After administering 400 g, the kneaded dough for 20 minutes at a temperature of 120°C was transferred to a twin-screw extruder and extruded to produce antistatic agent composition pellets of 3 to 5 mm in size.

Example 3

While purging argon into the reactor, 10,000 g of heptane and 200 g of dimethylborane were added, propylene was supplied to maintain the pressure at 1 atm, and the temperature of the reactor was raised to 60°C.

In the reactor, 20 g of racemic-dimethylsilylbis[1-(2-methyl-4,5-benzoindenyl)]zirconium dichloride and 30 g of 2,6-di-tert-butyl-4-methylphenol-modified methylaluminoxane were added to the reactor. The polymerization is initiated while stirring at a speed of 100 RPM. The reactor pressure is set to 1 atm by continuously supplying monomers, and the polymerization reaction proceeds for 2 hours while maintaining the temperature at 60°C.

After the reaction was completed, 50 g of methanol was added to the polymerization product extracted from the bottom of the reactor to terminate the reaction. The reaction mixture was subjected to steam stripping to separate the copolymer from the solvent, and then dried in a vacuum oven at 50-60°C for 24 hours to produce borane- A terminal polyolefin was prepared.

While purging argon into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of borane-terminated polyolefin were sequentially added, and then 25,000 g of distilled water, 2,500 g of sodium hydroxide, and 3,000 g of methanol were added while stirring at a speed of 50 RPM, and then added to the reactor. Lower the temperature to -5℃, add 20,000g of hydrogen peroxide aqueous solution (30% by weight of hydrogen peroxide) dropwise over 60 minutes, then raise the reaction temperature to 40℃ and react for another 8 hours while stirring at a speed of 100RPM. After proceeding, the resulting reactant was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare hydroxy-terminated polyolefin.

While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of hydroxy-terminated polyolefin were added, the temperature of the reactor was raised to 50°C, stirred at a speed of 100 RPM for 10 hours, and 4,000 g of lithium naphthalide was added to the reactor. was administered to maintain the reaction temperature at 50°C and stirred at a speed of 100 RPM for 8 hours. Then, the resulting mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polymer initiator.

While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran, 25,000 g of polymer initiator, 50,000 g of propylene oxide, and 200 g of calcium hydride were added, the temperature of the reactor was raised to 80°C, and reaction was performed at a speed of 100 RPM for 50 hours. The reaction was terminated by adding 1,500 g of methanol, and the mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polyolefin-polyalkenoxide copolymer.

100,000 g of ethanol and 25,000 g of polyolefin-polyalkenoxide copolymer were added to the reactor to raise the temperature of the reactor to 40°C. After stirring for 1 hour at a speed of 100 RPM, 500 g of 1-ethyl-3-methylimidazolium thiocyanate was added. The reactant was administered, maintained at 40°C, and stirred at a speed of 100 RPM for 2 hours, then filtered, washed, and dried in a 60°C vacuum oven for 12 hours to prepare an ionic copolymer.

In a kneader mixer, add 100,000g of polypropylene, 300g of tin oxide, 25,000g of ionic copolymer, 150g of thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and calcium. After administering 400 g of stearate, the dough was kneaded at 160°C for 20 minutes and transferred to a twin-screw extruder to produce antistatic agent composition pellets of 3 to 5 mm in size through extrusion molding.

Example 4

While purging argon into the reactor, 10,000 g of toluene and 200 g of 9-boravisilcononane were added, then 4-methyl-1-pentene was supplied to maintain the pressure at 1 atm, and the reactor temperature was raised to 60°C.

Polymerization was initiated by adding 20 g of racemic-dimethylsilylbis(2-ethyl-4-phenylindenyl)zirconium dichloride and 30 g of polymethylaluminoxane to the reactor and stirring at a speed of 100 RPM, and the reactor pressure was used to continuously separate the monomers. The polymerization reaction proceeds for 2 hours while maintaining the temperature at 60°C at 1 atm.

After the reaction was completed, 50 g of methanol was added to the polymerization product extracted from the bottom of the reactor to terminate the reaction. The reaction mixture was subjected to steam stripping to separate the copolymer from the solvent and then dried in a vacuum oven at 50-60°C for 24 hours to remove borane-terminated residues. Polyolefin was prepared.

While purging argon into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of borane-terminated polyolefin were sequentially added, and then 25,000 g of distilled water, 2,500 g of sodium hydroxide, and 3,000 g of methanol were added while stirring at a speed of 50 RPM, and the reactor temperature was adjusted to Lowered to -5℃, added 20,000g of hydrogen peroxide aqueous solution (30% by weight of hydrogen peroxide, 70% by weight of water) dropwise over 60 minutes, then raised the reaction temperature to 40℃ and stirred at 100RPM for 8 minutes. After the reaction proceeded for an additional time, the resulting reactant was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare hydroxy-terminated polyolefin.

While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of hydroxy-terminated polyolefin were added, the temperature of the reactor was raised to 50°C and stirred at a speed of 100 RPM for 10 hours, and 4,000 g of potassium naphthalide was added to the reactor. g was administered to maintain the reaction temperature at 50°C and stirred at a speed of 100 RPM for 8 hours, and then the resulting mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polymer starter.

While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran, 25,000 g of polymer initiator, 50,000 g of ethylene oxide, and 200 g of calcium hydride were added. The reactor temperature was raised to 80°C and reacted at a rate of 100 RPM for 50 hours, followed by methanol. The reaction was terminated by adding 1,500 g, and the mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polyolefin-polyalkenoxide copolymer.

Add 100,000 g of ethanol and 25,000 g of polyolefin-polyalkenoxide copolymer to the reactor to raise the temperature of the reactor to 40°C. After stirring for 1 hour at a speed of 100 RPM, 500 g of 1-butyl-1-methylpyrrolidinium thiocyanate was added. The reactant was administered, maintained at 40°C, and stirred at a speed of 100 RPM for 2 hours, then filtered, washed, and dried in a 60°C vacuum oven for 12 hours to prepare an ionic copolymer.

In a kneader mixer, 100,000g of polymethylpentene, 300g of zinc oxide, 25,000g of ionic copolymer, 150g of thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, calcium After administering 400 g of stearate, the lump dough kneaded for 20 minutes at a temperature of 80 to 200° C. was transferred to a twin-screw extruder and extruded to produce antistatic agent composition pellets of 3 to 5 mm in size.

Example 5

While purging argon into the reactor, 10,000 g of toluene and 200 g of 9-boravisylcononane were added, and then ethylene and propylene were supplied to maintain the pressure at 1 atm and raise the reactor temperature to 60°C.

In the reactor, 20 g of racemic-dimethylsilylbis[1-(2-methyl-4,5-benzoindenyl)]zirconium dichloride and 30 g of methylaluminoxane were added and polymerization was initiated while stirring at a speed of 100 RPM, and the reactor pressure was increased. The silver monomer is continuously supplied and the polymerization reaction proceeds for 2 hours while maintaining a pressure of 1 atm and a temperature of 60°C.

After the reaction was completed, 50 g of methanol was added to the polymerization product extracted from the bottom of the reactor to terminate the reaction. The reaction mixture was subjected to steam stripping to separate the copolymer from the solvent, and then dried in a vacuum oven at 50-60°C for 24 hours to produce borane- A terminal polyolefin was prepared.

While purging argon into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of borane-terminated polyolefin were sequentially added, and then 25,000 g of distilled water, 2,500 g of sodium hydroxide, and 3,000 g of methanol were added while stirring at a speed of 50 RPM, and the temperature of the reactor was adjusted to Lower the temperature to -5℃, add 20,000g of hydrogen peroxide aqueous solution (30% by weight of hydrogen peroxide: 70% by weight of water) dropwise over 60 minutes, then raise the reaction temperature to 40℃ and stir at 100RPM for 8 minutes. After the reaction proceeded for an additional time, the resulting reactant was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare hydroxy-terminated polyolefin.

While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of hydroxy-terminated polyolefin were added, the temperature of the reactor was raised to 50°C and stirred at a speed of 100 RPM for 10 hours, and 4,000 g of potassium naphthalide was added to the reactor. g was administered to maintain the reaction temperature at 50°C and stirred at a speed of 100 RPM for 8 hours. The resulting mixture was filtered, washed, and dried in a 60°C vacuum oven for 24 hours to prepare a polymer initiator.

While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran, 25,000 g of polymer initiator, 50,000 g of ethylene oxide, and 200 g of calcium hydride were added, the temperature of the reactor was raised to 80°C, reaction was performed at a rate of 100 RPM for 50 hours, and then 1,500 g of methanol was added. The mixture where the reaction was terminated by adding g was filtered and washed, and then dried in a vacuum oven at 60°C for 24 hours to prepare a polyolefin-polyalkenoxide copolymer.

100,000 g of ethanol and 25,000 g of polyolefin-polyalkenoxide copolymer were added to the reactor, the temperature of the reactor was raised to 40°C and stirred for 1 hour at a speed of 100 RPM, and then 500 g of 1-butyl-1-methylpyrrolidinium thiocyanate was added. The reactant was administered, maintained at 40°C, and stirred at a speed of 100 RPM for 2 hours, then filtered, washed, and dried in a 60°C vacuum oven for 12 hours to prepare an ionic copolymer.

In a kneader mixer, 100,000 g of ethylene-propylene copolymer, 300 g of antimony tin oxide, 25,000 g of ionic copolymer, and thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propio. After administering 150 g of nate and 400 g of calcium stearate, the dough was kneaded at 100°C for 20 minutes and transferred to a twin-screw extruder to produce antistatic agent composition pellets of 3 to 5 mm in size through extrusion molding.

Example 6

An antistatic agent composition was prepared in the same manner as in Example 5 except that the preparation of the antistatic agent composition in Example 5 was changed as follows.

In a kneader mixer, 100,000 g of ethylene-vinylacetate copolymer, 300 g of carbon black, 25,000 g of ionic copolymer, and thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. After administering 150 g of calcium stearate and 400 g of calcium stearate, the lump dough kneaded at 100°C for 20 minutes was transferred to a twin-screw extruder and extruded to produce antistatic agent composition pellets of 3 to 5 mm in size.

Example 7

An antistatic agent composition was prepared in the same manner as in Example 5 except that the preparation of the antistatic agent composition in Example 5 was changed as follows.

In a kneader mixer, 100,000 g of polyethylene ethylene-vinylacetate copolymer, 300 g of graphite, 25,000 g of ionic copolymer, and thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. After administering 150 g of calcium stearate and 400 g of calcium stearate, the lump dough kneaded for 20 minutes at a temperature of 80 to 200 ° C was transferred to a twin-screw extruder and extruded to produce antistatic composition pellets of 3 to 5 mm in size.

Comparative Example 1-1

The preparation of the antistatic agent was completed in the same manner as in Example 1, except that the ionic copolymer was not used in the preparation of the antistatic agent composition of Example 1.

Comparative Example 1-2

While purging argon into the reactor, 10,000 g of hexane and 200 g of 9-boravisilcononane were added, and then ethylene was supplied to maintain the pressure at 1 atm and raise the reactor temperature to 60°C.

In the reactor, 20 g of racemic-dimethylsilylbis[1-(2-methyl-4,5-benzoindenyl)]zirconium dichloride and 30 g of 2,6-di-tert-butyl-4-methylphenol-modified methylaluminoxane were added to the reactor. The polymerization is initiated while stirring at a speed of 100 RPM. The reactor pressure is set to 1 atm by continuously supplying monomers, and the polymerization reaction proceeds for 2 hours while maintaining the temperature at 60°C.

After the reaction was completed, 50 g of methanol was added to the polymerization product extracted from the bottom of the reactor to terminate the reaction. The reaction mixture was subjected to steam stripping to separate the copolymer from the solvent and then dried in a vacuum oven at 50-60°C for 24 hours to remove borane-terminated residues. Polyolefin was prepared.

While purging argon into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of borane-terminated polyolefin were sequentially added, and then 25,000 g of distilled water, 2,500 g of sodium hydroxide, and 3,000 g of methanol were added while stirring at a speed of 50 RPM, and the reactor temperature was adjusted to Lowered to -5℃, added 20,000g of hydrogen peroxide aqueous solution (30% by weight of hydrogen peroxide: 70% by weight of water) dropwise over 60 minutes, then raised the reaction temperature to 40℃ and stirred at a speed of 100RPM. After the reaction proceeded for another 8 hours, the resulting reactant was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare hydroxy-terminated polyolefin.

While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of hydroxy-terminated polyolefin were added, the temperature of the reactor was raised to 50°C, stirred at a speed of 100 RPM for 10 hours, and 4,000 g of potassium naphthalide was added to the reactor. was administered to maintain the reaction temperature at 50°C and stirred at a speed of 100 RPM for 8 hours, and then the resulting mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polymer initiator.

While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran, 25,000 g of polymer initiator, 50,000 g of ethylene oxide, and 200 g of calcium hydride were added, the temperature of the reactor was raised to 80°C, reaction was performed at a speed of 100 RPM for 50 hours, and methanol was added. The reaction was terminated by adding 1,500 g, and the mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polyolefin-polyalkene oxide copolymer.

In a kneader mixer, add 100,000 g of polyethylene, 300 g of antimony tin oxide, 25,000 g of polyolefin-polyalkenoxide copolymer, and thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. After administering 150 g of calcium stearate and 400 g of calcium stearate, the lump dough kneaded at 120°C for 20 minutes was transferred to a twin-screw extruder and extruded to produce antistatic agent composition pellets of 3 to 5 mm in size.

Comparative Example 1-3

The preparation of the antistatic agent was completed in the same manner as Comparative Example 1-2, except that antimony tin oxide was not used in the preparation of the antistatic agent composition of Comparative Example 1-2.

The thermoplastic elastomer composition prepared in this way was manufactured into a 1.5 mm thick specimen at 170~220°C using a hot press, and surface resistance and paper piece adhesion tests were performed. The results are shown in Table 1.

The surface resistance of the specimen was left in a drying oven maintained at 25°C for 1 day and then measured using a super dielectric meter under the same conditions. Surface resistance after washing was measured by immersing the test piece in hot water at 80°C for 30 minutes and wiping the surface with a clean cloth.

Measurement results of each experiment according to the examples Test Items Example 1 Example 2 Example 3 Comparative Example 1-1 Comparative Example 1-2 Comparative Example 2-1 surface resistance 10 ⁹ 10 ⁹ 10 ⁹ 10 ¹¹ 10 ¹⁰ 10 ¹¹ Surface resistance (after cleaning) 10 ⁹ 10 ⁹ 10 ⁹ 10 ¹¹ 10 ¹¹ 10 ¹¹ Attaching a piece of paper doesn't exist doesn't exist doesn't exist has exist has exist has exist

As shown in Table 1, the surface resistance of the example according to the present invention is low, there is no change after washing, and there is no adhesion to paper pieces, so it can be confirmed that the antistatic effect is superior to the comparative example.

The manufacturing method of the ionic copolymer and antistatic composition of the present invention facilitates the production of an ionic copolymer and an antistatic composition using the same that do not impair transparency, have little migration, and maintain antistatic properties for a long period of time while maintaining excellent mechanical properties, processability, and weather resistance. It has great industrial value as it has the effect of being easily manufactured.

Claims (4)

While purging an inert gas in a reactor equipped with gas purging equipment, a stirrer, and a thermostat, 10,000 parts by weight of a polymerization solvent and a chain transfer agent are added. (chain transfer agent) was administered at 10 to 300 parts by weight, monomer was supplied to maintain the pressure at 1 to 2 atm, the reactor temperature was raised to 20 to 100°C, a catalyst (5 to 40 parts by weight) and crude Polymerization is initiated by adding 10 to 60 parts by weight of a co-catalyst and stirring at a speed of 50 to 500 RPM. Monomers are continuously supplied so that the reactor pressure is 1 to 2 atmospheres and the temperature is 20 to 100°C. After the polymerization reaction was completed for 1 to 24 hours while maintaining , 10 to 100 parts by weight of alcohol was added to the polymerization reaction liquid extracted from the bottom of the reactor to terminate the reaction, and the reaction mixture was steam stripped. ) treatment to separate the copolymer from the solvent, followed by drying at 50 to 100°C for 12 to 48 hours to produce borane-terminated polyolefin;
While purging an inert gas in a reactor equipped with gas purging equipment, a dropper, a stirrer, and a temperature controller, 100,000 parts by weight of a reaction solvent and 20,000 to 40,000 parts by weight of the borane-terminated polyolefin prepared in the borane-terminated polyolefin production step are added. Dosing sequentially, adding 20,000 to 40,000 parts by weight of distilled water, 2,000 to 8,000 parts by weight of base, and 2,000 to 8,000 parts by weight of alcohol while stirring at a speed of 50 to 500 RPM, then lowering the reaction temperature to -10 to 0°C. , Add 15,000 to 40,000 parts by weight of hydrogen peroxide aqueous solution (10 to 30% by weight of hydrogen peroxide: 90 to 70% by weight of water) dropwise over 30 to 60 minutes, then raise the reaction temperature to 30 to 60°C to 50 to 500 RPM. After the reaction proceeded for a further 4 to 12 hours while stirring at a speed of A hydroxy-terminated polyolefin production step for producing;
While purging an inert gas in a reactor equipped with gas purging equipment, a stirrer, and temperature controller, 100,000 parts by weight of reaction solvent and 20,000 to 40,000 parts by weight of hydroxy-terminated polyolefin prepared in the hydroxy-terminated polyolefin production step were administered. Then, the reactor temperature was raised to 30-60°C and stirred at a speed of 50-500RPM for 6-24 hours, and then 1,000-10,000 parts by weight of reducing agent was added to the reactor to maintain the reaction temperature at 30-60°C and 50°C. A polymer initiator preparation step of preparing a polymer initiator by filtering/washing the resulting mixture by stirring for 3 to 12 hours at a speed of ~500 RPM and drying it at 50 to 100°C for 12 to 48 hours;
While purging an inert gas in a reactor equipped with gas purging equipment, a stirrer, and temperature controller, 100,000 parts by weight of reaction solvent, 20,000 to 40,000 parts by weight of polymer initiator prepared in the polymer initiator manufacturing step, and 10,000 to 90,000 parts by weight of alkene oxide. , 100 to 1,000 parts by weight of metal hydride was administered, the reactor temperature was raised to 60 to 100°C and reaction was performed at a rate of 50 to 500 RPM for 24 to 60 hours, and then 1,000 to 2,000 parts by weight of alcohol was added for reaction. A copolymer production step of filtering and washing the resulting mixture and drying it at 50 to 100°C for 12 to 60 hours to produce a polyolefin-polyalkenoxide copolymer;
100,000 parts by weight of the dispersion solvent and 20,000 to 40,000 parts by weight of the polyolefin-polyalkenoxide copolymer prepared in the copolymer production step were added to a reactor equipped with a stirrer and a temperature controller, and the temperature of the reactor was raised to 20 to 60 ° C. After stirring for 1 to 6 hours at a speed of 500 RPM, 200 to 600 parts by weight of ionic liquid was added to maintain the reactor temperature at 20 to 60°C and stirred for 1 to 6 hours at a speed of 50 to 500 RPM. An ionic copolymer preparation step of preparing an ionic copolymer by filtering/washing the reactant and drying it at 5-100°C for 12-24 hours;
100,000 parts by weight of a polymer selected from ethylene copolymer and synthetic rubber in a mixing mixer made by Kneader, Hensel, or Banbury, and an electrically conductive 100 to 500 parts by weight of filler, 20,000 to 40,000 parts by weight of ionic copolymer prepared in the ionic copolymer manufacturing step, 50 to 200 parts by weight of antioxidant, and 100 to 1,400 parts by weight of lubricant are sequentially administered, and Antistatic agent composition manufacturing step in which the lump dough kneaded at 200°C for 5 to 60 minutes is transferred to a single screw or twin screw extruder to produce antistatic agent composition pellets of 3 to 5 mm in size through extrusion molding. A method for producing an antistatic composition using an ionic copolymer with antistatic properties, characterized in that it consists of. According to paragraph 1,
In the boranization step of the polyolefin, the inert gas is selected from nitrogen, argon, and neon, and the polymerization solvent is pentane or hexane ( selected from the group consisting of hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene, and the chain transfer agent (Chain transfer agent) is triethylborane, tripropylborane, dimesitylborane, 9-borabicylcononane, and boron dipyromethene. , thexylborane, and disiamylborane, and the monomer is ethylene, propylene, butene, or cyclopentene. , 4-methyl-1-pentene, one alkene is selected alone or two or more types are selected, and the catalyst is racemic-dimethylsilylbis (1-). Nyl) zirconium dichloride [rac-dimethylsilylbis(1-indenyl)zirconium dichloride], racemic-dimethylsilylbis[1-(2-methyl-4,5-benzoindenyl)]zirconium dichloride {rac-dimethylsilylbis[1 -(2-methyl-4,5-benzoindenyl)]zirconium dichloride}, racemic-dimethylsilylbis(2-ethyl-4-phenylindenyl)zirconium dichloride[rac-dimethylsilylbis(2-ethyl-4-phenylindenyl) )zirconium dichloride], racemic-dimethylsilylbis[1-(2-n-propyl-4-(1-naphthyl)indenyl)]zirconium dichloride {rac-dimethylsilyl-bis[l-(2-n- propyl-4-(1-naphthyl)indenyl)]zirconium dichloride}, racemic-dimethylsilylbis[1-(2-ethyl-4-(9-phenanthryl)indenyl)]zirconium dichloride{rac-dimethylsilylbis[ 1-(2-ethyl-4-(9-phenanthryl)indenyl)]zirconium dichloride}, racemic-dimethylsilylbis[1-(2-n-propyl-4-(9-phenanthryl)indenyl)]zirconium Dichloride {rac-dimethylsilylbis[l-(2-n-propyl-4-(9-phenanthryl)indenyl)]zirconium dichloride} is selected from one zirconium compound, and the co-catalyst is methylaluminum. Among methylaluminoxane, 2,6-di-tert-butyl-4-methylphenol modified methylaluminoxane, and polymethylaluminoxane One aluminoxane is selected, and the alcohol is selected from methanol, ethanol, propanol, or isopropyl alcohol;
In the functionalization step of the polyolefin, the reaction solvent is selected from diethyl ether, ethyl acetate, tetrahydrofuran, and methyl ethyl ketone. , the base is either sodium hydroxide or potassium hydroxide;
In the polymer initiator preparation step, the reaction solvent is selected from diethyl ether, ethyl acetate, tetrahydrofuran, and methyl ethyl ketone, The reducing agent is selected from sodium naphthalenide, lithium naphthalenide, and potassium naphthalenide;
In the copolymer manufacturing step, the alkene oxide is one of ethylene oxide, propylene oxide, butylene oxide, and octene oxide, and the metal oxide Metal hydride is selected from beryllium hydride, calcium hydride, and titanium hydride;
In the ionic copolymer manufacturing step, the dispersion solvent is selected from ether, ketone, or alcohol, and the ionic liquid is sodium thiocyanate. Na potassium thiocyanate, 1-ethyl 3-methylimidazolium, thiocyanate, 1-butyl-3-methylimidazolium thiocyanate (1- butyl-3-methylimidazolium thiocyanate), 1-butyl-1-methylpyrrolidinium thiocyanate, 1-ethyl-1-methylpiperidinium thiocyanate (1-ethyl- 1-methylpiperidinium thiocyanate);
In the antistatic agent composition manufacturing step, the polymer is a polyolefin resin such as polyethylene, polypropylene, or polymethylpentene, or an ethylene-vinyl acetate copolymer. ) or, one of ethylene-propylene copolymer, ethylene-propylene-diene copolymer, and ethylene-ethylacrylate copolymer. (ethylene copolymer), butadiene rubber, nitrile butadiene rubber, chloroprene rubber, isobutylene rubber, or styrene butadiene rubber. It is selected from synthetic rubber, and the electrically conductive filler is graphene, carbon black, graphite, electro-conductive mica, or indium tin oxide. It is selected from one of tin oxide, tin dioxide, zinc oxide, and antimony-doped tin oxide, and the antioxidant is thiodiethylene bis [3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate] [thiodiethylene bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] or thiodipropionic acid di It is used alone or in combination of two or more sulfur compounds among octadecyl ester (thiodipropionic acid dioctadecylester), distearyl thiodipropionate, and 3-mercaptopropionic acid. The lubricant is a fatty acid metal salt of calcium stearate, magnesium stearate, aluminum stearate, or lithium stearate. A method for producing an antistatic composition using an ionic copolymer with antistatic properties, characterized in that the selected. While purging an inert gas, 10,000 parts by weight of a polymerization solvent selected from an organic solvent and 10 to 300 parts by weight of a chain transfer agent selected from a borane compound. 5 to 40 parts by weight of a catalyst selected from a zirconium compound and 10 to 60 parts by weight of a co-catalyst selected from aluminoxane are stirred, and an alkene is added alone or two or more types. A borane-terminated polyolefin prepared by supplying a selected monomer and adding 10 to 100 parts by weight of alcohol to the polymerization reaction solution in which the polymerization reaction was performed;
While stirring 100,000 parts by weight of a reaction solvent and 20,000 to 40,000 parts by weight of the borane-terminated polyolefin, 20,000 to 40,000 parts by weight of distilled water, 2,000 to 8,000 parts by weight of a base, and 2,000 to 8,000 parts by weight of alcohol were added, and hydro A hydroxy-terminated polyolefin obtained by dropwise adding 15,000 to 40,000 parts by weight of an aqueous solution of hydrogen peroxide (10 to 30% by weight of hydrogen peroxide: 90 to 70% by weight of water);
A polymer initiator obtained by stirring 100,000 parts by weight of a reaction solvent and 20,000 to 40,000 parts by weight of the hydroxy-terminated polyolefin while purging an inert gas, and adding 1,000 to 10,000 parts by weight of a reducing agent;
Stir and react 100,000 parts by weight of reaction solvent, 20,000 to 40,000 parts by weight of polymer initiator, 10,000 to 90,000 parts by weight of alkene oxide, and 100 to 1,000 parts by weight of metal hydride, then add 1,000 to 2,000 parts by weight of alcohol. The reaction is terminated to obtain a polyolefin-polyalkenoxide copolymer,
An ionic copolymer with antistatic properties obtained by stirring 100,000 parts by weight of a dispersion solvent and 20,000 to 40,000 parts by weight of the polyolefin-polyalkenoxide copolymer and adding 200 to 600 parts by weight of an ionic liquid. . 100,000 parts by weight of polymer, 100-500 parts by weight of electrically conductive filler, 20,000-40,000 parts by weight of ionic copolymer, 50-200 parts by weight of antioxidant used alone or in combination of two or more of the sulfur compounds, fatty acid metal salt An ionic copolymer antistatic composition having antistatic properties, which is obtained by sequentially administering 100 to 1,400 parts by weight of a lubricant selected from the group consisting of salt, kneading, and extrusion molding.