KR101476317B1 - Low density polyethylene master batch including Polyurushiol and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a low density polyethylene master batch including polyurushiol and a method for manufacturing the same and, more specifically, to a method for manufacturing a polyethylene master batch by mixing polyurushiol with low density polyethylene and silica as a way of solving a problem of allergy of urushiol which is a main component of a lacquer extract. The low density polyethylene master batch including polyurushiol and a method for manufacturing the same according to the present invention provides a method for manufacturing low density polyethylene master batch including urushiol which is a main component of lacquer to have an effect of providing a polyethylene product showing an antibacterial activity, an insect repelling property, an antiseptic effect, an anti-fungal effect, and an atopic dermatitis caring effect of urushiol.

Description

TECHNICAL FIELD The present invention relates to a low density polyethylene master batch containing polyurusol and a production method thereof,

The present invention relates to a low density polyethylene master batch containing polyurusol and a method for preparing the same. More specifically, the present invention relates to a method for preparing polyurusiol, which is a method for solving the allergy problem of urushiol, To a process for producing a low density polyethylene master batch.

Rhus verniciflua or Rhus vernicifera ) is a deciduous arboreous tree belonging to Anacardiaceae . It is originated from the Middle Asia Highland and the Himalayas. It is widely distributed in the subtropical and temperate regions around the world. It is used as a natural paint in crafts and household goods in East Asia. In addition, lacquer has been used in oriental medicine for the treatment of hemorrhagic tumors for thousands of years. Raw lacquer or rhubarb extract collected from lacquer trees promotes blood circulation in one room and is known to be effective against various diseases such as insecticide and fungicide such as insecticide, abdominal pain, tuberculosis, constipation, constipation, diabetes and schizophrenia. Lacquer, and lacquer are used in medicinal dishes such as duck. Recently, the scientific research on the efficacy of lacquer has revealed the antioxidant function of lacquer.

Urushi is made up of urushiol, water, rubber, lacase and nitrogenous substance. Of these, urushiol is the main component which accounts for about 70% of the rusk liquor, and it is a 3-substitution with C15-alkyl or alkenyl group (8'Z, 11'E, 13'Z-pentadecatrienyl) catechol (3- (8'Z, 11'Z-pentadecatrienyl) E, 13'Z-pentadecatrienyl) catechol). Up to now, 13 components of 3-substituted alkyl catechins having double bonds of 0, 1, 2 or 3 in the C15 side chain have been found, and urushiol has been found to be a polymer in which monomers are naturally polymerized by these monomers and la- (polymer) are mixed.

In particular, recent studies have shown that Urushiol, a major component of lacquer, is highly effective in killing cancer cells at a concentration of 4PPM. In addition, the flavonoid component of Rhus verniciflua suppresses the growth of cancer cells by 80%, and it turns into a round shaped normal organ of cancer cells by converting specific genes of cancer cell differentiation. In addition, the anticancer effect of urushiol extract, And the effect of inhibiting neovascularization, the effect of transforming mutant genes of cancer cells into normal cells, and the like.

Ursiol, which is a major constituent of lacquer, was reported to cause an allergic reaction in the early stage. However, since strong antioxidant power, antibacterial power, waterproofing, chemical resistance, insecticide and preservative effect have been revealed, traditionally, the durability Chemically proven.

Therefore, in the present invention, it is intended to apply variously to the injection and extrusion polyethylene products which are prepared by masterbatches of the powdered alumina powder in which the allergy problem of urushiol is solved, and exhibit antibacterial, insect repellent, antifungal and atopic care effects.

Patent application number 10-2010-0063248 Process for producing polyurusol nanosized aqueous solution, polyurusiol powder using the same and use thereof

An object of the present invention is to provide a method for producing a product having antioxidant ability, antimicrobial activity, antiseptic effect and antiseptic effect of urushiol, which is a component of the powdered lacquer, by solving the elements capable of causing allergy in the lacquer powder, And silica to prepare a master batch, thereby providing a polyethylene product having the effect of urushiol.

The above object of the present invention can be achieved by a method for producing a polyurusol nanofiber, comprising the steps of: drying a polyurus nano-aqueous liquid to obtain a polyurusiol powder; mixing the obtained polyurusol powder with low density polyethylene and silica; And a step of producing a master batch.

Further, the polyurusiol powder is characterized by using a polyurusol nanosized aqueous solution, dried with a spray drier, and using polyurusiol powder recovered in a bag filter.

The polyurusol mixture in the polyurusol mixture is mixed in an amount of 5 to 25 parts by weight based on 100 parts by weight of the low-density polyethylene.

The silica mixed amount of the polyurusol mixture is 3 to 5 parts by weight based on 100 parts by weight of the low-density polyethylene.

The mixing of the polyurusol mixture is characterized in that a vacuum pump is connected to the closed container and the mixture is heated under reduced pressure.

The mixing of the polyurusol mixture is carried out at a reduced pressure of 0.1 to 0.5 atm and at an internal temperature of 60 to 80 ° C for 2 to 4 hours.

The extrusion of the polyurusol mixture is performed at a temperature of 150 to 180 DEG C at a revolution speed of 150 to 250 rpm.

Further, the polyurusiol mixture is extruded in a twin extruder.

The low-density polyethylene master batch containing polyurusol according to the present invention and the preparation method thereof can provide an optimal preparation method of a low-density polyethylene master batch containing urushiol, which is a main constituent of lacquer, to provide an antimicrobial power, insecticide, It is possible to provide a polyethylene product which can exhibit the antifungal and atopic care effects without an allergic reaction.

Figure 1. Low density polyethylene master batch containing bullet polyurusol
2. Low-density polyethylene mixture containing polyurusiol powder 5PHR
Figure 3. Low-density polyethylene mixture containing 10PHR of polyurusiol powder
Figure 4. Low density polyethylene master batch containing 25PHR of polyurusiol powder
Figure 5. Bag filter analysis of polyurusiol powder
Figure 6. Cyclone analysis results of polyurusiol powder

The present invention relates to a process for preparing a master batch, comprising the steps of drying a polyurus nano-aqueous liquid to obtain a powder, mixing the obtained polyurusol powder with low density polyethylene and silica, and extruding the mixed polyurusol mixture .

In the method for producing a low density polyethylene master batch containing polyurusol according to the present invention, first, a hydrophilic monomer and an oxidizing agent are added to urushiol to prepare a first polymer through polymerization reaction. At this time, urushiol is polymerized with a hydrophilic monomer by an oxidizing agent to produce a first polymer. In the present invention, urushiol is obtained by extracting pure urushiol except for water, rubber quality, and Lacase enzyme using ethanol in a raw lacquer component derived from a lacquer tree, centrifuging and distillation under reduced pressure to obtain a purified Use raw materials. When the purity of urushiol is low, the degree of polymerization during the polymerization reaction is lowered, causing allergies or large particle size, which is a problem in stability. Further, a hydrophilic monomer is required for producing polyurusol according to the present invention. The hydrophilic monomer may have a functional group containing a polymerizable unsaturated bond in the bond. For example, as a monomer having an anionic hydrophilic functional group containing an unsaturated bond, the polymerization reaction of the present invention can be more easily performed. Examples of the anionic hydrophilic functional group include -SO ₃ M, -COOM, -PO ₃ M ₂ (M is a hydrogen atom, an alkaline earth metal atom or an ammonium salt), and PO ₃ AH (A May be selected from the group consisting of alkaline earth metal atoms or ammonium salts). Examples thereof include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, aconitic acid, maleic acid or an anhydride thereof, monomethyl maleate, monomethyl fumarate, monomethyl itaconate, vinylsulfonic acid and vinyl phosphate . In this case, the hydrophilic monomer is preferably used in an amount of 1 to 99 parts by weight based on 100 parts by weight of urushiol. When the hydrophilic monomer is used in an amount of less than 1 part by weight, the hydrophilic content is low, so that the phase transition to the o / w phase does not occur sufficiently in water dispersion, that is, oil in water, w emulsion becomes somewhat difficult. When the amount of the hydrophilic monomer used exceeds 100 parts by weight, it is difficult to control the reaction by the viscosity increase. On the other hand, in the method for producing the first polymer of the present invention, a peroxide may be used as the oxidizing agent. For example, they may be selected from the group consisting of ketone peroxide, hydroperoxide, diacyl peroxide, peroxyketal, peroxy ester, peroxydicarbonate, and mixtures thereof. More preferably, hydroperoxide can be used as the oxidizing agent. Examples thereof include t-butyl hydroperoxide, t-ethyl hydroperoxide, and hydrogen peroxide. The amount of the oxidizing agent used is preferably from 0.1 to 30 parts by weight based on 100 parts by weight of urushiol when the first polymer is produced. When the amount is less than 0.1 part by weight, polymerization is difficult. When the amount is more than 30 parts by weight, viscosity control becomes difficult. In the reaction for preparing the first polymer, a redox active catalyst may be further added to promote the oxidation reaction, and the use of the redox active catalyst may result in a more satisfactory polymerization reaction of urushiol. As the redox active catalyst that can be used in the present invention, metal salts, metal complexes, hydrophilic amines, and at least one of them may be selected and used as a mixture. The metal salt may be a metal salt such as sodium or calcium having a monovalent or higher valence, and a metal complex such as nickel, cobalt, manganese, iron or copper having a monovalent or higher valence may be used, and a hydrophilic amine is preferably a tertiary amine. At this time, the amount of the oxidative active catalyst to be used is preferably 0.01 to 1 part by weight per 100 parts by weight of urushiol, because the reaction can be controlled uniformly by controlling the reaction rate. When the amount exceeds the above range, the reaction occurs even when 1 part by weight or more is used, but the rate of the reaction is increased and it becomes difficult to control the reaction by a uniform reaction. The temperature during the polymerization of the first polymer thus mixed is preferably 0 to 80 ° C. If the mixing temperature is lower than the above range, the reaction may be slowed down and the accuracy of the reaction may be decreased. .

The first polymer thus prepared is neutralized by adding a neutralizing agent such as an inorganic base, an organic base or a mixture thereof to prepare a hydrophilic salt. In the neutralizing agent for neutralizing the first polymer, examples of the organic base include tertiary amines such as triethylamine, triethanolamine, dimethylethanolamine and the like. Examples of inorganic bases include sodium hydroxide and sodium carbonate. When water is slowly added to the neutralized first polymer and stirring is performed, the phase transition is carried out on the w / o phase to the o / w phase, wherein the hydrophilic salt is prepared from an o / w emulsion having nanoparticles.

When an additional oxidizing agent is added so that the urushiol reactant that has not yet reacted in the step of preparing the first polymer can be polymerized, a secondary polymerization reaction takes place in the particle, so that the polymerized polyurusol nanoparticle, that is, the second polymer can be prepared have. In the production of the second polymer, the amount of the oxidizing agent is preferably 50 to 500 parts by weight per 100 parts by weight of urushiol. When an oxidizing agent is used in an amount of less than 50 parts by weight, the degree of polymerization may be lowered and allergen may be caused. If the amount of the oxidizing agent exceeds 500 parts by weight, unreacted oxidizing agent may remain. The temperature of the polymerization reaction for preparing the second polymer is preferably from 50 to 100 캜. When the temperature is lowered below the lower limit of the temperature, the reaction may be slowed down and the accuracy of the reaction may be decreased. When the upper limit is exceeded, it becomes difficult to control the temperature of the reaction.

The second polymer produced by the above process is dried with a spray dryer to prepare a polyurusiol powder. A vacuum closed space portion capable of maintaining a temperature of 200 ° C is provided on the inner side thereof and a mist closing portion is formed on the upper side of the mist storage portion by supplying a mist of aqueous solution from a storage tank capable of holding a predetermined amount of polyurusiol aqueous solution, And a hot air supply unit for applying a heat amount of about 40 to 60 kcal / hr and a hot air of about 15 to 20 m ³ / min to the nozzle and the mist nozzle unit. The outlet is formed in the lower center of the hopper, A powder processing tank in which a visible window for visually observing the vacuum closed space portion is formed; An air feeder connected to the storage tank of the powder processing tank so as to transmit a pneumatic pressure of about 15 to 25 kg / hr, and a powder suction collecting tank connected to the discharge port of the powder processing tank; And a control box for the operator to input and adjust the intensity of the heat and heat sensation sensor, the mist nozzle and the hot air supply, the air supply and the powder suction collection tank on / off, and the air pressure and the hot air. At this time, dried powder collected in the bag filter (Fig. 5) and collected in the ciclon (Fig. 6) are collected separately and only powder collected in the bag filter is used. In order to maximize the efficacy, it is well dispersed and attached to the surface of the resin using a small particle size powder, and the surface area is widened.

The process of mixing the polyurusol powder thus prepared with the low density polyethylene and the silica is performed by melting the surface of the low density polyethylene by heating under reduced pressure by connecting a vacuum pump to the closed container to form the polyurusiol powder on the surface of the low density polyethylene The polyurusol powder does not scatter in the next step, maintains a certain amount of content, adheres to the surface and is dispersed well, and evaporation of volatile substances such as water can be suppressed to suppress the occurrence of bubbles in the next step There is an effect. A mixture of polyurusiol powder and polyethylene only has a low heat resistance, causing carbonization (Fig. 1). In the present invention, silica is added together (FIG. 3) in order to solve this problem. The sillica used herein is a chemical compound of silicon and oxygen (SiO ₂ ), which is amorphous gel type silica powder having an amorphous crystal structure and a particle size of 2 to 20 micrometers (탆). Silica is used for a variety of purposes, including plastic film release agents, paints and quenching agents for inks. The mixing amount of silica is preferably 5 to 3 parts by weight based on 100 parts by weight of urushiol. If it is used in an amount of 3 parts by weight or less, improvement in heat resistance is less effective, and if it is used in an amount of 5 parts by weight or more, there may be a problem of deterioration of impact resistance. The mixing process of the polyurusiol powder, the polyethylene and the silica is preferably performed under a pressure of 0.1 to 0.5 atm or lower, and when a reduced pressure of 0.5 or more is applied, there is a problem that evaporation of volatile substances is not performed well. Also, the internal temperature is 60 to 80 占 폚, and the temperature of the fruit is 120 占 폚. The mixing time is suitably from 2 to 4 hours, and when mixing is performed for 2 hours or less, a part of the polyurusiol powder does not adhere to the polyethylene surface and is scattered in a post-process. As the mixing ratio, the polyurusiol powder is preferably 5 to 25 PHR (part per hundred resin). When it is manufactured at 5 PHR or less, the function as a master batch is disadvantageous because of a rise in the processing cost and a decrease in physical properties due to thermal deformation of the resin. In the case of manufacturing at 25 PHR or more, the surface of the master batch is not smooth, do. The polyurusiol powder, low density polyethylene and silica mixture are extruded at an extrusion temperature of 150 to 180 DEG C and an extrusion speed of 150 to 250 rpm, and then pulverized by a cutter to be packaged. At this time, a twin extruder is suitable for the extruder to be used. The twin extruder is advantageous in that the polyurusol powder is well dispersed by rotating the two screws and extruding them.

Hereinafter, the present invention will be described in detail with reference to examples.

EXAMPLES Example 1 Preparation method of polyurusiol nanosized aqueous solution.

5 kg of purified urushiol and 900 g of maleic acid were mixed in a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and 15 g of cobalt octoate (10% solution) was added. Thereafter, 15 g of hydrogen peroxide (30% solution) was added dropwise at 40 占 폚 over 30 minutes, the temperature was raised to 80 占 폚 and maintained for 1 hour and then cooled to room temperature to prepare a first polymer.

Then, 25 g of triethylamine was added dropwise over 15 minutes to neutralize, and then 4.5 kg of pure water was added dropwise with stirring over 1 hour while water was dispersed to prepare an emulsion of the hydrophilic salt.

The emulsion was heated to 50 占 폚 and 4.5 kg of hydrogen peroxide was added dropwise over 3 hours, and the mixture was allowed to stand at 80 占 폚 for 2 hours and then cooled to room temperature to prepare 14.5 kg of a second polymer.

145 kg manufactured by repeating this method 10 times were injected at a pneumatic pressure of 20 kg / hr. At this time, hot air was supplied at a heating rate of 55 kcal / hr and 20 m ³ / min air volume, To produce 22.5 kg of lacquer powder. At this time, the average particle diameter of the bag filter was 12.50 mu m and the average particle diameter of the chamber was 32.74 mu m.

Example 2 Preparation of a low density polyethylene master batch containing 5PHR of polyurusiol powder (5 parts by weight of a polyurusol-containing masterbatch for 100 parts by weight of polyethylene)

The polyethylene used in the present invention was low density polyethylene (LDPE), and low density polyethylene having a low branching ratio and low crystallinity was used. It has a low mechanical strength but excellent workability. Low-density polyethylene has good water resistance, moisture-proofing property and cold-proof property and is used for packaging container, wire covering, pipe, fiber, packaging material.

2 kg of the polyurusol powder of the filter, 40 kg of low density polyethylene (LDPE) and 2 kg of silica were charged into a vacuum conical mixer, the vacuum pump was operated to reduce the pressure to 0.3 atm, Was maintained at 70 캜 and mixed for 4 hours to obtain a mixture of 46.8 kg of polyurusiol powder, low density polyethylene and silica (Fig. 2). The mixture was poured into a twin extruder and extruded to produce 32 kg of a polyurusol powder master batch of 5 PHR.

Example 3 Production method of low density polyethylene master batch containing 10PHR of polyurusiol powder (10 parts by weight of polyurusol-containing master batch production method per 100 parts by weight of low density polyethylene)

4 kg of the polyurusol powder of the bag filter (FIG. 5), 40 kg of low density polyethylene (LDPE) and 2 kg of silica were charged into a vacuum conical mixer and the vacuum pump was operated to reduce the pressure to 0.3 atm. , Maintaining the internal temperature of the mixer tank at 70 캜 and mixing for 4 hours to obtain 42.4 kg of polyurusiol powder, low density polyethylene and silica mixture (Fig. 3). The mixture was poured into a twin extruder and extruded to produce 33 kg of polyurusol powder master batch of 10 PHR.

Example 4 Production method of low density polyethylene master batch containing polyurusiol powder 25PHR (25 parts by weight of polyurusol-containing masterbatch production method with respect to 100 parts by weight of low density polyethylene)

10 kg of polyurusol powder as a bag filter, 40 kg of low density polyethylene (LDPE) and 2 kg of silica were charged into a vacuum conical mixer, the vacuum pump was operated to reduce the pressure to 0.3 atm, The temperature was maintained at 70 캜 and mixed for 4 hours to obtain 46.8 kg of a polyurusiol powder, a low density polyethylene and a silica mixture. The mixture was poured into a twin extruder and extruded to produce 35 kg of polyurusol powder master batch of 20 PHR (FIG. 4).

Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

As described above, the present invention can be applied to a variety of injection and extrusion polyethylene products that exhibit antibacterial, insect repellent, antifungal and atopic care effects by preparing a polyurusiol powder that resolves the allergy problem of urushiol by a master batch Effect can be provided.

Claims (9)

Drying the polyurus nanolate aqueous solution to obtain a polyurusiol powder;
Mixing the obtained polyurusiol powder with low density polyethylene and silica; And
Extruding the mixed polyurusol mixture to produce a master batch;
≪ / RTI > wherein the low molecular weight polyethylene masterbatch comprises polyurusol. The method according to claim 1,
Wherein the polyurusol powder is dried from a polyurus nano-aqueous liquid by a spray drier, and the polyurusol powder recovered in the bag filter is used. The method according to claim 1,
Wherein the polyurusol mixture in the polyurusol mixture is mixed in an amount of 5 to 25 parts by weight based on 100 parts by weight of the low-density polyethylene. The method according to claim 1,
Wherein the amount of silica in the polyurusol mixture is 3 to 5 parts by weight based on 100 parts by weight of the low-density polyethylene. The method according to claim 1,
Wherein the mixing of the polyurusol mixture is carried out by connecting a vacuum pump to a sealed container and heating under reduced pressure. The method according to claim 1,
Wherein the mixing of the polyurusol mixture is carried out at a reduced pressure of 0.1 to 0.5 atm and proceeding at an internal temperature of 60 to 80 占 폚 for 2 to 4 hours. The method according to claim 1,
Wherein the extrusion of the polyurusol mixture is carried out at a temperature of from 150 to 180 DEG C at a revolution speed of from 150 to 250 rpm. The method according to claim 1,
Wherein the polyurusol mixture is extruded in a twin extruder. ≪ RTI ID = 0.0 > 8. < / RTI > A low density polyethylene master batch comprising polyurusol prepared by the process of any one of claims 1 to 8.

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