KR101776999B1 - Pellet available to complex degrade and rapidly become low-molecular substance for containing double bond and its preparing method - Google Patents
Pellet available to complex degrade and rapidly become low-molecular substance for containing double bond and its preparing method Download PDFInfo
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- KR101776999B1 KR101776999B1 KR1020150084076A KR20150084076A KR101776999B1 KR 101776999 B1 KR101776999 B1 KR 101776999B1 KR 1020150084076 A KR1020150084076 A KR 1020150084076A KR 20150084076 A KR20150084076 A KR 20150084076A KR 101776999 B1 KR101776999 B1 KR 101776999B1
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Abstract
The present invention relates to a composite decomposing raw material pellet having improved oxidative decomposition, biodegradability and mechanical properties, and a method for producing the same. More particularly, the present invention relates to a method for producing a decomposable raw material pellet by oxidative decomposition and biodegradation using a raw material containing a double bond, To produce the raw pellets to be changed. The present invention relates to a composite decomposable raw material pellet, which increases the physical properties such as strength and gives a final decomposition period control function to reduce the occurrence of a claim due to decomposition during use and distribution, and a manufacturing method thereof will be.
Description
The present invention relates to a complex additive for rapidly decomposing a polymer by using an oxidizing agent using biomass, a metal ion salt, and a double bond structure, and a raw material pellet having a rapid degradability using the same, and more particularly, The present invention relates to a composite decomposable raw material pellet capable of rapidly decomposing a polymer by using a metal ion salt such as biomass and ferric sodium edetate, an autoxidizing agent having a double bond structure, and a binder polymer.
UAE, Pakistan, France, Italy, and New York State have passed or are pushing legislation to distribute products made of degradable plastic to packaging materials or products. As of January 1, 2014, the UAE replaced all packaging materials in the UAE area with biodegradable plastic, a type of degradable plastic, that imposes a penalty of about 8.5 million won in violation. UAE oxidized biodegradable plastics are UAE S 5009 based on ASTM D 6954 and the final decomposition period is 36 months. In New York State, the US legislature was enacted on January 1, 2015 to encourage the use of degradable plastics, with a six-month grace period. In New York State, it is recommended to use degradable plastics with a degradation period of 12 months shorter than that of UAE, with decomposition period of degradable plastics within 2 years.
Generally, degradable plastics can be divided into biodegradation, oxidative biodegradation, photodegradation or photodegradation depending on the decomposition period. Biodegradable plastics should be degraded more than 90% of the standard cellulite within 6 months under industrial composting conditions, and oxidized biodegradable plastics should be decomposed by more than 90% within 36 months. Photodegradation and photodegradation Plastics can be excluded from the category of degradable plastics because they require more than 50 years to decompose into water and carbon dioxide, while the form of the product is lost. Therefore, biodegradable plastic or oxidized biodegradable plastic should be used to meet international standards or product sales standards.
Biodegradable plastics are more expensive than general plastics, have a limited range of use, and relatively inexpensive biodegradable plastics have problems in their properties. In the case of oxidative biodegradable plastic, it is inexpensive because it is produced by adding a small amount of oxidative biodegradation additive to a general polymer, but it is advantageous that physical properties are not different from general polymers. In addition, biodegradable plastics have the advantage of controlling the decomposition period according to the ratio of the additive to be added, the degree of concentration, and the amount of the antioxidant.
However, the amount of additives to be biodegraded in conventional biodegradable biodegradable plastics is inevitably increased, and if the amount of the additive is increased, the physical properties may deteriorate, the transparency may decrease, and the unit price may increase.
Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above problems of the prior art, and its object is to provide a biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biomass, It is intended to produce a product capable of responding to international regulations by reducing the final biodegradation period by lowering molecular weight faster than conventional oxidative biodegradable plastics by using PLA or TPS as a metal ion salt or binder polymer.
In order to accomplish the above object, the present invention provides a method for producing a microorganism which comprises 5 to 50% by weight of macroalgae biomass; 1 to 5% by weight of a sodium based plasticizer; 0.2 to 5% by weight of an autoxidizer; 0.01 to 5% by weight of a metal ion salt; From 0.2 to 5% by weight of a metal ion activator; And 40 to 90% by weight of a binder polymer, wherein the macro algae biomass is at least one selected from brown algae and red algae. The sodium plasticizer is selected from the group consisting of sodium hydrogensulfite (NaHSO 3 ), sodium percarbonate , 2Na 2 CO 3), bicarbonate (sodium bicarbonate, NaHCO 3), sodium chloride (sodium chloride, NaCl), meta-sodium silicate (Na 2 SiO 3), Na 2 B ( tetraborate, sodium 4 O 7 · 10H 2 O) And soda ash (Na 2 CO 3 ), wherein the automatic oxidizer is at least one selected from the group consisting of alpha-linolenic acid, gamma linolenic acid, and unsaturated fatty acid, and the metal ion salt is at least one selected from the group consisting of iron, And nickel, at least one metal ion selected from the group consisting of acetylacetonate, tetrabutylammonium acetate, acetic anhydride, ammonium sulfate metal salt, metal naphthenate, metal sulfur Wherein the metal ion activator is at least one selected from the group consisting of propionic acid, p-nitrilobenzoic acid, citric acid, malic acid, and maleic acid, and the metal ion activator is at least one selected from the group consisting of salts, metal silicates and sulfonium salts and ferric sodium edetate, , The binder polymer may be selected from the group consisting of poly lactic acid (PLA), polyhydroxyalkanoate (PHA), poly-hydroxybutyrate (PHB), poly-hydroxyvalerate ), Thermoplastics starch (TPS), polycaprolactone (PCL), ethylene propylene diene monomer (EPDM), high density polyethylene (HDPE), medium density polyethylene middle density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) Acetate provides a (ethylene vinyl acetate, EVA), polypropylene (polypropylene, PP) and polyethylene (PE) and poly one, compound decomposition starting pellets, characterized in that at least from the group consisting of a copolymer of propylene (PP).
The present invention also provides a composite decomposing raw material pellet further comprising 0.05 to 10 wt% of wax.
Further comprising 0.1 to 5% by weight of an antioxidant, wherein the antioxidant is at least one selected from the group consisting of a phenol-based primary antioxidant, a phosphite-based secondary antioxidant and a yellowing- The raw pellets are provided.
According to another aspect of the present invention, there is also provided a method for producing a biomass powder, comprising the steps of: (A) pulverizing a large algal biomass into fine particles having a size of 100 to 400 mesh to produce a biomass powder; (B) drying the biomass powder at 70 to 100 DEG C for 1 to 20 hours to have a water content of 10% by weight or less; (C) adding wax to the dried biomass powder and stirring the mixture at 500 rpm to coat the surface of the biomass powder; (D) incorporating a sodium based plasticizer into the coated biomass powder to produce a plasticized biomass mixture; (E) incorporating an autoxidizer, a metal ion salt, a metal ion activator, an antioxidant and a binder polymer into the plasticized biomass mixture; And (F) introducing the mixed mixture into a twin-screw extruder at 100 to 300 DEG C and 30 to 800 rpm to effect plasticization of the macroparasite biomass and binder polymer-macroalgae biomass grafting , And cooling the strand obtained from the discharge port and cutting the strand to a predetermined size.
The present invention also provides a method for producing a composite decomposing raw material pellet, wherein the step (D) and the step (E) are simultaneously performed.
According to another aspect of the present invention, there is provided a composite decomposing film produced by mixing the composite decomposing raw material pellet and the polymer resin as described above.
Also provided is a composite decomposition film characterized by having a molecular weight of 5,000 Da or less after treatment with ultraviolet rays of 340 nm at a temperature of 50 캜 for 300 hours.
The present invention also provides a composite decomposition film characterized by having a molecular weight of 5,000 Da or less after treatment with ultraviolet light of 340 nm at a temperature of 50 캜 for 400 hours.
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The complex decomposition raw material pellet according to the present invention uses a metal ion salt including iron and sodium ion such as ferric sodium edetate and substitutes a marine biomass component using a sodium based plasticizer. By using mass, the biodegradation rate can be increased.
Generally, in the case of red algae and brown algae, lignin which strongly attracts ultraviolet rays generated from carbon is contained, so that it absorbs ultraviolet rays which accelerate decomposition of the polymer and may interfere with decomposition or may cause carbonization during the manufacturing process. However, Sodium ions can be used to replace lignin in marine biomass to enhance degradability and to mask dark colors due to lignin.
The metal ion activator and the oxidizing oxidizer of the double bond structure are suitably mixed with the substituted and plasticized biomass to react with the trivalent iron ions in the ferric sodium edetate to progress the low molecular weight, and the final biodegradation period of the polymer film Can be shortened. In addition, the present invention can reduce the process steps by composing the mixture while plasticizing the biomass, which leads to cost savings.
The present invention can reduce environmental pollution by using biomass that threatens marine ecosystems such as red algae, brown algae, etc., and can reduce cost, reduce the environmental burden of plastics by rapidly decomposing general polymers, and cope with international environmental regulations.
FIG. 1 is a flow chart of a process for producing a complex decomposition raw material pellet of the present invention.
FIG. 2 is a schematic view showing a decomposition mechanism when using the composite decomposition raw material pellets. FIG.
FIG. 3 is a schematic diagram showing a decomposition mechanism when a film is produced using a composite decomposing additive. FIG.
4 is an explanatory view showing the principle of improvement of mechanical properties according to the present invention.
FIG. 5 shows the composite decomposition film prepared according to the present invention before and after pretreatment.
6 is a component analysis data of the composite decomposing film produced according to the present invention.
7 is a biodegradation measurement data of the composite decomposing film produced according to the present invention.
Figure 8 is a composite cracked feed pellet prepared according to the present invention
Hereinafter, the present invention will be described in detail.
Compound decomposition raw material pellet additive
The present invention relates to a redox reaction of peroxides with an oxidizing agent of a double bond structure; 3 Drying fine powdered red algae using sodium ion in ferric sodium edetate, which has both iron ion and sodium ion, prevention of carbonization and plasticization of brown algae; Promoting the radical reaction of polymers using trivalent ions in ferric sodium edetate; A metal ion activator is used to promote the radical reaction and to activate the crosslinking of the biomass with the binder polymer.
The biomass is dried and finely pulverized into a multicellular macroalgae (red algae) and a green algae (brown algae) derived from water. The red algae used in the present invention include Phacelocarpus japonicus, Zanardinula cornea and Lomentaria catenata, and most of them have a total carbohydrate content of 53 to 70% and polysaccharides such as agarose, carrageenan and porphyran , And cellulose contains 5 to 13%. The brown algae are mainly Dictyota maxima, Chordaria flagelliformis, Scytosiphon lomentaria, Undaria pinnatifida and Laminaria japonica, and most of them have a total carbohydrate content of 45-60% and alginate , fucoidan, laminaran and mannitol, and 5 to 10% of cellulose.
Such aquatic derived biomass can secure large quantity of raw materials with excellent growth rate and production rate of algae, and it is easy to cultivate without using wide land because it uses abundantly obtained algae from river, lake, and sea water Lt; / RTI > It can also be recycled and has an enormous amount of biomass, which is a non-edible resource. In addition, since it is basically a biomaterial having a low molecular weight, there is an advantage that the decomposition rate of the product produced by applying the compound decomposing raw material pellets and the raw material pellets can be rapidly performed.
The red algae and brown algae used in the present invention are finely ground using a powder machine so as to have a particle size of about 100 to 400 mesh, and at the same time, they are dried at a temperature of 70 to 100 ° C for 1 hour to 20 hours to a moisture content of 10% In order to increase the dispersibility, it is necessary to narrow the particle size of the powder, so it is necessary to adjust the particle size distribution by adding a polarizer to the powder phase
The biomass is preferably contained in an amount of 5.0 to 50.0% by weight based on the total weight of the composition, if the biodegradation effect can be expected to be improved. If the amount is less than 5.0 wt%, the effect of rapid biodegradation is small. If the amount is more than 50.0 wt%, the properties of the final product may be deteriorated.
If the final product is a transparent product, the biomass should not be added when producing the raw pellets of the present invention.
The biomass can be wax-coated to prevent reabsorption of moisture after powder and drying, thereby improving physical properties. In addition, since wax has low molecular weight and low melting point characteristic, it acts as a lubricant aid and has advantages of easy biodegradability because it is a low molecular substance.
Examples of the wax include those commonly used in the art such as paraffin wax, liquid paraffin wax, wax, mold wax, emulsifying wax, candelilla wax, PE wax, and PP wax.
The wax is preferably used in an amount of 1 to 20 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the biomass powder. When the content of the wax is less than 1 part by weight, the function of the coating function and the lubrication aid may be insufficient. If the amount of the wax is more than 20 parts by weight, debris such as foreign matters may be generated in the production facility dice.
To the above biomass or coated biomass, sodium hydrogensulfite (NaHSO 3 ), sodium percarbonate (2Na 2 CO 3 ), sodium bicarbonate (NaHCO 3 ), sodium chloride sodium sulphate (sodium chloride, NaCl), sodium metasilicate (Na 2 SiO 3 ), sodium tetraborate (Na 2 B 4 O 7 · 10H 2 O) and soda ash (Na 2 CO 3 ) .
The plasticizer may further increase the oxidation effect of sodium contained in the plasticizer, and the amount of the plasticizer is preferably 1.0 to 5.0% by weight based on the composition. If the plasticizer content is less than 1.0 wt%, plasticization may be difficult, and if the plasticizer content is more than 5.0 wt%, it may cause deterioration of properties such as carbonization.
Said biomass and plasticizer composition; Auto oxidizer; Metal ion salts; Metal ion activators; The binder polymer is mixed and extruded to produce a composite decomposition raw material pellet.
The autoxidizer is a low-molecular substance including a double bond, and at least one selected from ALA (alpha-linolenic acid), GLA (gamma-linolenic acid) and unsaturated fatty acids having three double bonds at 18 carbon atoms is used, The amount to be used is preferably 0.2 to 5.0% by weight based on the composition. If it is less than 0.2% by weight, it is difficult to expect an automatic oxidation function, and if it exceeds 5.0% by weight, the cost increases. ALA and GLA are shown in the following
[Structural formula 1]
ALA (α-Linolenic acid, 18: 3)
GLA (γ-Linolenic acid, 18: 3)
The autoxidizer ALA and GLA can be used alone or in combination and have three C = C structures, so that the polymer can be oxidized rapidly. In addition, when unsaturated fatty acids such as myristoleic acid, oleic acid, linoleic acid, arachidonic acid and palmitoleic acid are additionally used, heat and light catalyze to break the double bond to generate energy, It accelerates decomposition and accelerates pyrolysis, photolysis and oxidative decomposition. The autoxidizer is preferably used in an amount of 0.2 to 5.0% by weight based on the total weight of the composite decomposition additive. When the amount of the oxidizing agent is less than 0.2% by weight, the decomposition rate of the polymer may be slowed down. If the amount of the oxidizing agent is more than 5.0% by weight, the physical properties and productivity of the product may be lowered.
The metal ion salt may be at least one selected from the group consisting of ferric sodium edetate, acetylacetonate, tetrabutylammonium acetate, acetic acid anhydride ammonium metal sulfate, metal naphthenate, metal sulfate, metal silicate and sulfonium salt.
The metal ions contained in the regular metal ion salt repeatedly generate peroxides and redox reactions to generate energy, and this energy causes a radical reaction. This reaction causes the carbon chain of the polymer to be cleaved and oxidative decomposition to occur, so that the molecular weight of the polymer is reduced. The low molecular weight oxidized low molecular weight material is finally decomposed and absorbed by the microorganisms in the natural environment and converted into water and carbon dioxide, and the decomposition can be completed.
The metal ion salt is preferably contained in an amount of 0.01 to 5.0% by weight, and if it is less than 0.01% by weight, the oxidative decomposition function of the plastic resin may be weakened, and if it exceeds 5.0% by weight, .
The metal ion of the metal salt may be at least one selected from the group consisting of iron, sodium, copper and nickel.
Among these, ferric sodium edetate contains both trivalent iron ions and sodium ions, and has the formula C 10 H 12 FeN 2 NaO 8 .3H 2 O, and the structural formula thereof is shown in the following
[Structural formula 2]
Ferric sodium edetate replaces lignin of marine biomass with sodium ion, and the trivalent ion contained in it reacts with HPO, carbonyl group to accelerate decomposition.
The metal ion activator induces crosslinking between the biomass and the binder polymer and reacts with the metal ion to accelerate the decomposition of the polymer. In the present invention, at least one selected from propionic acid, p-nitrilobenzoic acid and citric acid is used, and malic acid and maleic acid, which are generally known, can be used. The metal ion activator is suitably used in an amount of 0.2 to 5.0% by weight based on the total composition. If the metal ion activator is less than 0.2 wt%, the crosslinking ability of the polymer resin with the biomass may be weakened. If the metal ion activator is more than 5.0 wt%, the unnecessary cost may be increased.
The antioxidant may further include an antioxidant to retard degradation, yellowing, and oxidative degradation of the product due to premature oxidative decomposition upon promotion of the oxidation reaction of the complex decomposing polymer, thereby prolonging the oxidative biodegradation period and preventing color change, This long product can reduce claims due to changes in circulation.
The above antioxidant may be used alone or in combination with a primary antioxidant functioning as a radical scavenger that reacts with radicals generated in the plastic to stabilize the plastic and a secondary antioxidant that performs a peroxide releasing function .
The primary antioxidants include phenol-based antioxidants such as Tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane, Octadecyl 3- (3'5'-di- propionate, 2,2'-Ethylidenebis [4,6-di-t-butylphenol], 1,3,5-tris (4-tert.- 3-t-butyl-4-hydroxy-5-methylphenyl) propionate], N, N'-hexamethylene bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionamide] may be used.
As the second antioxidant, Tris (2,4-di-t-butylphenyl) phosphite is used as a phosphite antioxidant and thioester thiodipropionate is used as an antioxidant to prevent further color change due to yellowing. It is preferable to use 0.1 to 5.0% by weight based on the composition. When the content of the antioxidant is less than 0.1 wt%, it is difficult to prevent oxidation and yellowing. When the content of the antioxidant is more than 5.0 wt%, the final oxidation biodegradation period is excessively extended due to the antioxidant function.
On the other hand, antioxidants may not be included in the case of rapid oxidative decomposition.
The binder polymer includes biodegradable polymers such as polylactic acid (PLA), polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), thermoplastics starch (TPS) ethylene propylene diene monomer), HDPE (high density polyethylene), LLDPE (low density polyethylene), LDPE (low density polyethylene), EVA (ethylene vinyl acetate), PP (polypropylene), PE and PP copolymers, MDPE (middle density polyethylene) can be used for one or more of them. The binder polymer is preferably contained in an amount of 40.0 to 98.0% by weight, and if the binder polymer is less than 40.0% by weight, there is a fear that the pellet is broken or the powder is formed due to insufficient binding force. If it exceeds 98.0% by weight, The decomposition function of the complex decomposition additive can be lowered.
In addition, inorganic fillers and compatibilizers, which are general additives used in the production of finished products such as bioplastics, should be appropriately added.
Method of manufacturing composite decomposition raw material pellet additive
According to another aspect of the present invention
(A) The biomass includes Phacelocarpus japonicus, Zanardinula cornea and Lomentaria catenata, and most of them have a total carbohydrate content of 53 to 70% and polysaccharides such as agarose, carrageenan and porphyran , And cellulose contains 5 to 13%. The brown algae are selected from at least one of Dictyota maxima, Chordaria flagelliformis, Scytosiphon lomentaria, Undaria pinnatifida, Laminaria japonica and their byproducts, and 100-400 mesh fine particles ≪ / RTI > to produce a biomass powder;
In this step, the biomass is pulverized into fine particles of 100 to 400 mesh. When the size is less than 100 mesh, the average particle size of the fine particles is not less than 150 占 퐉 and the particles become too large, The surface roughness and the strength and elongation of the product may be lowered. When it is more than 400 mesh, it takes too long for the grinding process, resulting in a decrease in the overall productivity, an increase in the manufacturing cost, Can be adversely affected in terms of the dispersibility of cellulose due to the property of the fine particles of the particles binding to each other.
(B) drying the biomass powder at 70 to 120 ° C for 1.0 to 20.0 hours to remove moisture;
In this step, the water content is adjusted to 10% by weight or less by drying for 1.0 to 20.0 hours while heating and stirring at 70 to 120 ° C using a conventional drying apparatus. If the drying temperature is lower than 70 ° C, sufficient drying may not be performed or the drying time may become longer. If the drying temperature is higher than 150 ° C, the possibility of carbonization of the biomass or the like may increase and the quality of the product may deteriorate. If the drying time is less than 1.0 hour, drying may not be sufficient and the product quality may be lowered due to moisture problem when the product is manufactured by applying the finished product. If the drying time is more than 20 hours, energy is wasted without additional drying effect, It can fall.
(C) Sodium hydrogensulfite (NaHSO 3 ), sodium percarbonate (2Na 2 CO 3 ), sodium bicarbonate (NaHCO 3 ), sodium chloride (NaHCO 3 ), and the like are added to the dried biomass powder using at least one of sodium chloride, NaCl), meta-sodium silicate (Na 2 SiO 3), Na 2 B ( tetraborate, sodium 4 O 7 · 10H 2 O) , soda ash (soda ash, Na 2 CO 3 ), in And stirring to produce a plasticized biomass mixture;
(D) adding an autoxidizer, a metal ion salt, a metal ion activator, an antioxidant and a binder polymer to the biomass and the plasticizer composition, and stirring the mixture to produce a mixture; And
The steps (C) and (D) may be performed sequentially or simultaneously.
(E) The mixture is subjected to a biomass plasticization reaction and a binder polymer-plasticized biomass graft bond using a twin-screw extruder, and discharged through a discharge port. The discharged strand is cooled, Thereby forming a complex decomposition raw material pellet which can be rapidly and low-molecular-weighted by containing a double bond.
Particularly, when the reaction is carried out at a reaction temperature of 100 to 300 ° C through extruder and a screw rotating speed of 300 to 800 RPM, the coupling reaction is smoothly performed. If the reaction temperature is less than 100 ° C., the added materials may not be melted and the reaction may not proceed. If the temperature exceeds 300 ° C., carbonization may occur or the temperature may be too high to melt the resin as water, . In addition, if the screw rotational speed is less than 300 RPM, productivity may be poor, and sufficient mixing and reaction may become difficult. If the screw rotation speed is higher than 800 RPM, the internal pressure of screw may be increased and carbonization of biomass may occur due to pressure increase.
In addition, in order to improve processability, product stability, product performance, etc., various known components that can be used as additives for the production of plastics may be added in predetermined amounts to produce the composite decomposing additive pellets of the present invention. For example, a surface treatment agent may be added in a predetermined amount to enhance the bonding force and reduce the repulsive force. Also, in order to maintain the physical and chemical properties of the resin during use of the plastic product, Can be added.
Further, in order to prevent deformation, carbonization and premature oxidative decomposition of the compound to maintain mechanical properties and processing stability, addition of a linear organic thermal stabilizer and an antioxidant having a molecular weight of less than 2,000, desirable.
Example 1: Production of composite decomposition additive raw material pellets using brown algae
The large biotite brown biomass brown algae were pulverized to about 300 mesh and heated and dried at 100 ° C for 30 minutes to produce 50 wt% of powder (based on the total decomposition additive raw material pellets). 1.5 wt% (based on the total composition) of ELISA Wax 102N (manufactured by Lion Chemical Co., Ltd.) was added to the dried brown algae powder, and the powder surface was coated at 500 RPM with high speed stirring. Further, 2.5 wt% of ferric sodium edetate, 1.0% by weight of ammonium metal salt, 1% by weight of sodium bicarbonate, 1.0% by weight of citric acid as a metal ion activator, 1.5% by weight of an oxidizing agent of alpha-linolenic acid and the remainder as EPDM (ethylene propylene diene monomer) as a binder polymer. A decomposition additive composition is formulated. Subsequently, a composite decomposition additive material pellet was prepared using a twin-single extruder.
Example 2: Production of complex decomposition additive raw material pellets using red algae
The pheasant tail of marine biomass red algae was pulverized to about 300 mesh and heated and dried at 100 ° C. for 30 minutes to produce brown algae powder at 50 wt% (based on the total decomposition additive raw material pellet). 1.5 wt% (based on the total composition) of ELISA Wax 102N (manufactured by Lion Chemical Co., Ltd.) was added to the dried powder, and the powder surface was coated with high speed stirring at 500 RPM. Further, 2.5 wt% of ferric sodium edetate, 1.0% by weight of citric acid as a metal ion activator, 1.5% by weight of an autoxidizing agent of alpha-linolenic acid, and the remainder as EPDM (ethylene propylene diene monomer) as a binder polymer and stirring at a speed of 400RPM to prepare a composite decomposition additive composition. Subsequently, a composite decomposition additive material pellet was prepared using a twin-single extruder.
Example 3: Production of composite decomposition film using raw material pellets applied to brown algae
2% by weight of the complex decomposition additive pellets prepared in Example 1, and 98% by weight of a high molecular weight resin (LDPE) (Lotte Chemical) were mixed and then a composite decomposition plastic film was produced using a conventional film production facility.
Example 4: Production of composite decomposition film using raw pellets of red algae
2% by weight of the composite decomposition additive pellets prepared in Example 2, and 98% by weight of a high molecular weight resin (LDPE) (Lotte Chemical) were mixed, and then a composite decomposition plastic film was prepared using a conventional film production facility.
Example 5: Production of composite decomposition film using raw pellets for applying brown algae
2% by weight of the complex decomposition additive pellets prepared in Example 1, 1% by weight of thioester thiodipropionate (TAULEX, AO 180T) and 97% by weight of a polymer resin (LDPE) (Lotte Chemical) A composite decomposition plastic film was prepared using a film manufacturing facility.
Example 6: Production of composite decomposition film using raw pellets of red algae
2% by weight of the complex decomposition additive pellets prepared in Example 2, 1% by weight of thioester thiodipropionate (TAULEX, AO 180T) and 97% by weight of a polymer resin (LDPE) (Lotte Chemical) A composite decomposition plastic film was prepared using a film manufacturing facility.
Experimental Example: Evaluation of mechanical properties of prepared films and evaluation of mechanical properties after ultraviolet ray treatment
For the mechanical properties test of the films prepared according to Examples 3 to 6, the tensile strength and elongation were measured for each sample cut to 25 X 102 mm according to ASTM D 3826 according to ASTM D 3826-98. The number of samples per film was measured 10 times for each measurement item to reduce the error per film, and the average value except the maximum and minimum values was taken. The load cell was 50 kg, the UTM (Universal Testing Machine, Daekyung Tech, Korea) machine was used, and the tensile speed of the machine was set at 50 mm / min. The results are shown in Table 1 below.
In addition, tensile strength and elongation after ultraviolet pretreatment were measured at Korea Apparel Testing and Research Institute according to the test method provided in ASTM D 6954, the international standard for degradable plastics. As the pretreatment method, ASTM D 6954
Experimental Example 1: Evaluation of molecular weight reduction of the produced film
The molecular weight changes of the composite decomposing films prepared in Examples 3 to 6 were measured. Globally, countries that have certification standards for degradable films include the United States, Sweden, the United Kingdom, Korea, Singapore, and the UAE. Other countries that have the above certification criteria, except UK, undergoing sensory testing, conduct molecular weight evaluation, biodegradation evaluation, gel residue test, deterioration of physical properties and heavy metal test according to the method of ASTM D 6954. In Sweden and Singapore, the molecular weight is below 10,000 Da according to ASTM D 6954
According to ASTM D 6954
When a film was prepared with the same amount of the general oxidative biodegradation additive of the present invention and the additives of foreign companies (UK Wells) in the same amount as the complex decomposition additive of the present invention, it took about 1,400 hours for the test analysis and the molecular weight decreased to 5,010 Da It can be said that it has a molecular weight reduction effect.
Experimental Example 2: FT-IR and GC-mass evaluation of the prepared film
The films prepared according to Examples 3 and 4 can cut CC bonds of a polymer resin by a radical reaction using a metal ion as a composite decomposition film and have a carbonyl group and have a CC bond It has a complex decomposition structure that can be cut.
FIG. 6 shows FT-IR and GC-mass measurement results of the films prepared in Examples 3 and 4. The analysis data in FIG. 6 shows that there are pyrolysis, a substance inducing photodegradation, and a double bond substance.
Experimental Example 3: Evaluation of biodegradation of the produced film
For evaluation of the biodegradability of the film of Example 3 obtained the lowest molecular weight in Experimental Example 1, the test was conducted according to ASTM D 6954, an evaluation method of oxidative biodegradation plastic. The biodegradation of ASTM D 6954 is first tested by ASTM D 6954
The biodegradability of the composite decomposition film of Example 3 was 51% at 45 days as shown in FIG.
Experimental Example 4: Assessment of human hazards of the produced film
In order to examine the human hazards of the composite film produced by Examples 3 to 6, the analysis was commissioned to the Korea Clothing Inspection & Research Institute. The contents of heavy metals such as Zn, Cu, Ni, Cd, Pb, Hg, CrVl, Mo, Se and As were measured by EPA 3051A-2007 method. In order to measure the content of halogen, the analysis was commissioned by Korea Clothing Testing Institute and the test was conducted according to KS M 0180: 2009 (C-IC) method.
The composite decomposition additive of the present invention is excellent in oxidative decomposability and mechanical properties, and is used as a base material for environment-friendly plastics in a variety of products requiring films such as films, articles, sheets, containers, industrial products, packaging materials, . In addition, the existing facility can be used as it is, and the productivity is excellent, which makes it possible to mass-produce the product easily. Especially, it is more suitable for thin film products and labs that have excellent physical properties, and is suitable for international standards such as UAE and USA.
Claims (11)
1 to 5% by weight of a sodium based plasticizer;
0.2 to 5% by weight of an autoxidizer;
0.01 to 5% by weight of a metal ion salt;
From 0.2 to 5% by weight of a metal ion activator; And
And 40 to 90% by weight of a binder polymer,
Wherein the large algal biomass is at least one selected from brown algae and red algae,
The sodium based plasticizer may be selected from the group consisting of sodium hydrogensulfite (NaHSO 3 ), sodium percarbonate (2Na 2 CO 3 ), sodium bicarbonate (NaHCO 3 ), sodium chloride (NaCl), sodium metasilicate (Na 2 SiO 3 ), sodium tetraborate (Na 2 B 4 O 7 .10H 2 O) and soda ash (Na 2 CO 3 )
Wherein the autoxidizing agent is at least one selected from alpha linolenic acid, gamma linolenic acid and unsaturated fatty acid,
The metal ion salt may be at least one selected from the group consisting of acetylacetonate, tetrabutylammonium acetate, acetic anhydride acid ammonium sulfate metal salt, metal naphthenate salt, metal sulfate, metal silicate and sulfonium salt containing at least one metal ion among iron, sodium, copper and nickel And < RTI ID = 0.0 > ferric sodium edetate, < / RTI >
Wherein the metal ion activator is at least one selected from the group consisting of propionic acid, p-nitrilobenzoic acid, citric acid, malic acid, and maleic acid,
The binder polymer may be selected from the group consisting of poly lactic acid (PLA), polyhydroxyalkanoate (PHA), poly-hydroxybutyrate (PHB), polyhydroxyvalerate (PHV) , Thermoplastics starch (TPS), poly-carprolactone (PCL), ethylene propylene diene monomer (EPDM), high density polyethylene (HDPE), middle density polyethylene density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene vinyl acetate (EVA), polypropylene ) And a copolymer of polypropylene (PP).
Compound decomposition pellets.
Further comprising 0.05 to 10% by weight of a wax.
And 0.1 to 5% by weight of an antioxidant, wherein the antioxidant is at least one selected from the group consisting of a phenol-based primary antioxidant, a phosphite-based secondary antioxidant, and a yellowing-preventing antioxidant. .
(B) drying the biomass powder at 70 to 100 DEG C for 1 to 20 hours to have a water content of 10% by weight or less;
(C) adding wax to the dried biomass powder and stirring the mixture at 500 rpm to coat the surface of the biomass powder;
(D) incorporating a sodium based plasticizer into the coated biomass powder to produce a plasticized biomass mixture;
(E) incorporating an autoxidizer, a metal ion salt, a metal ion activator, an antioxidant and a binder polymer into the plasticized biomass mixture; And
(F) The mixed mixture is fed into a twin-screw extruder at 100 to 300 ° C and 30 to 800 rpm to effect plasticization of the macroparasite biomass and binder polymer-macroalgae biomass grafting, Cooling the strand obtained from the discharge port and cutting the strand into a predetermined size;
A method for producing a composite decomposition raw material pellet.
Wherein the step (D) and the step (E) are performed simultaneously.
And a molecular weight of 5,000 Da or less after treatment with ultraviolet rays of 340 nm at a temperature of 50 캜 for 300 hours.
And a molecular weight of 5,000 Da or less after treatment with ultraviolet light of 340 nm at a temperature of 50 캜 for 400 hours.
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| KR102031224B1 (en) | 2018-02-06 | 2019-10-11 | 주식회사 테코플러스 | Pellet for manufacturing plastic products using waste paper and manufacturing method thereof |
| KR102201536B1 (en) | 2019-08-05 | 2021-01-13 | 주식회사 테코플러스 | Bioplastic composition comprising biomass resins and room temperature decomposition additive material and bioplastic pellet using therefrom |
| KR102647812B1 (en) * | 2022-02-15 | 2024-03-13 | 한림대학교 산학협력단 | Biodegradable material containing natural product and polymer support, and lock containing same |
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| JP2010005948A (en) | 2008-06-27 | 2010-01-14 | Sharp Corp | Method for manufacturing biomass-based plastic molded form and biomass-based plastic molded form |
| KR101407691B1 (en) | 2013-01-07 | 2014-06-16 | 한국기술교육대학교 산학협력단 | Bioplastic composition and method for preparing the same |
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| JP2010005948A (en) | 2008-06-27 | 2010-01-14 | Sharp Corp | Method for manufacturing biomass-based plastic molded form and biomass-based plastic molded form |
| KR101407691B1 (en) | 2013-01-07 | 2014-06-16 | 한국기술교육대학교 산학협력단 | Bioplastic composition and method for preparing the same |
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