WO2018199494A1 - Composition de résine à base de polyoléfine multi-dégradable et son procédé de préparation - Google Patents

Composition de résine à base de polyoléfine multi-dégradable et son procédé de préparation Download PDF

Info

Publication number
WO2018199494A1
WO2018199494A1 PCT/KR2018/003909 KR2018003909W WO2018199494A1 WO 2018199494 A1 WO2018199494 A1 WO 2018199494A1 KR 2018003909 W KR2018003909 W KR 2018003909W WO 2018199494 A1 WO2018199494 A1 WO 2018199494A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyolefin
polyvinyl alcohol
weight
resin composition
density polyethylene
Prior art date
Application number
PCT/KR2018/003909
Other languages
English (en)
Korean (ko)
Inventor
송경재
Original Assignee
송경재
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180037121A external-priority patent/KR102204708B1/ko
Application filed by 송경재 filed Critical 송경재
Publication of WO2018199494A1 publication Critical patent/WO2018199494A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene

Definitions

  • the present invention relates to a polydegradable polyolefin resin composition and a method for manufacturing the same, and more particularly, to a method for preparing a biodegradable homogeneous pellet by adding a small amount of a dehumidifying agent such as a photodegrading agent, an oxidizing agent and the like to a polyolefin resin.
  • a dehumidifying agent such as a photodegrading agent, an oxidizing agent and the like
  • the biodegradable resins thus far developed are polylactic acid (PLA) resins synthesized from starch, corn, milk powder, etc., polycaprolactone (PCL) resins synthesized chemically from epsilon caprolactone monomers, and diols ( Aliphatic polyester-based resins of dihydric alcohol) -dibasic acid (dicarboxylic acid) series, and polyhydroxybutylate (PHB) produced by in vivo synthesis of other microorganisms.
  • PHA polylactic acid
  • PCL polycaprolactone
  • diols Aliphatic polyester-based resins of dihydric alcohol) -dibasic acid (dicarboxylic acid) series
  • PHB polyhydroxybutylate
  • Polylactic acid-based resin is less than half the price of aliphatic polyester and has good transparency and high hardness, so it is suitable for use as a packaging container, but its elongation rate is low and breakage due to impact occurs easily and blow molding for film production There is a problem in that a hole is formed in the thin portion in the process. In addition, there are many limitations in producing a film by blow molding because of low thermal deformation temperature and poor bubble stability due to a slow cooling rate.
  • Polycaprolactone-based resins have a disadvantage of low workability due to their low melting point, and aliphatic polyester-based resins have considerable advantages in terms of physical properties because they are more flexible, elongate, and have a higher heat-resistant operating temperature than PLA. Although the price is very expensive, the practical use is being delayed.
  • Photodegradable additives, biodegradable resins, thermal decomposition agents, complex decomposition additives and the like are used for plastic decomposition, and among these, interest is increasing about complex decomposition decomposed by one or more mechanisms.
  • Republic of Korea Patent No. 10-1013453 prepared a composite degradable material using starch, it is impossible to use the properties of the starch directly as a plastic product, it is mainly necessary to blend or modify with other materials.
  • an expensive reactive extrusion (REX) is required.
  • Korean Patent Registration No. 062323 discloses a composite degradable thermoplastic polymer composition.
  • the amount required for the entire composition in order to cause a sufficient decomposition effect of the plastic products has a problem of increasing the manufacturing cost, and also because they are difficult to be molded by using a mass production molding machine used in the existing, such as the introduction of new equipment
  • a biodegradable film, etc. there is also a limit in producing a biodegradable film, etc., with the enormous additional costs incurred as a main component thereof.
  • Korean Patent Application No. 1996-64953 discloses a bio / photodegradable mulching film composition for agricultural use, but the composition has low decomposition rate and can be regarded as decay rather than degradable, and also has a polymer material such as polycaflolactone or polylactic acid. It is difficult to industrialize due to high manufacturing costs due to its mainly use.
  • US Patent No. 3941759 discloses a plastic composition which can be photolyzed by ultraviolet rays by adding a photosensitizer, which is an organic compound
  • US Patent No. 3992487 is a mixture of a thermoplastic polymer and a polymer containing metal ions. It provides a plastic composition that can be photolyzed by.
  • the plastic compositions described in these patents have limitations such as a long decomposition period and embedding in soil, which do not decompose in the absence of light.
  • the component consists of 55% calcium carbonate, 24% synthetic resin, 10% by weight polyvinyl alcohol and the remaining 10% by weight It consists of 20 kinds of additives. Therefore, since the addition amount of each additive is mixed at a temperature of 80 ° C. while being added in a small amount of 1% by weight or less, reproducibility is not secured when materials having low decomposition temperatures are volatilized or scattered.
  • Patent Document 1 Republic of Korea Patent No. 10-0602385
  • Patent Document 2 Republic of Korea Patent No. 10-1013453
  • An object of the present invention is to use a small amount of additives such as photodegradants, oxidative decomposers and microbial decomposers to polyolefin resins without using expensive bio-biodegradable raw materials such as starch or aliphatic polyesters.
  • additives such as photodegradants, oxidative decomposers and microbial decomposers to polyolefin resins without using expensive bio-biodegradable raw materials such as starch or aliphatic polyesters.
  • molded products such as films, sheets, bottles, injection molded articles, etc., which are decomposed by extrusion molding, inflation molding, injection molding, blow molding, etc. using the provided composition. It is to provide a method for producing.
  • the present invention is a polyolefin resin, grafted polyolefin resin, powdered calcium carbonate, pellet calcium carbonate, dehumidifying agent, photodegrading agent, initiator, polyvinyl alcohol, biodegrading agent or biodegrading agent,
  • a polydegradable polyolefin resin composition comprising a polyvinyl alcohol plasticizer, an anionic surfactant, a lubricant, and borax.
  • the polyolefin resin is a polydegradable polyolefin resin composition, characterized in that at least one mixture selected from the group consisting of low density polyethylene, linear low density polyethylene, polypropylene.
  • the grafted polyolefin resin is a composite characterized in that at least one mixture selected from the group consisting of grafted low density polyethylene, grafted high density polyethylene, grafted linear low density polyethylene, grafted polypropylene It is a decomposable polyolefin resin composition.
  • the dehumidifying agent is characterized in that at least one mixture selected from the group consisting of zeolite, bentonite, diatomaceous earth, silica gel, activated carbon, superabsorbent resin.
  • a compound compound decomposable polyolefin resin composition further comprising 200 to 600 parts by weight of a high density polyethylene resin with respect to 100 parts by weight of the polyolefin resin composition.
  • the multi-decomposable polyolefin-based resin composition molded article is molded by at least one method of extrusion molding, inflation molding, injection molding and blow molding using the compound. To provide.
  • biodegradable raw materials such as starch or polyester
  • the manufacturing cost of the composite degradable plastics can be reduced, thereby activating the biodegradable market and contributing to many environmental problems, thereby expanding the market demand.
  • the biodegradable agent of the present invention it can be produced at a low price of about 40% compared to the biodegradable agent using general polyethylene raw materials and starch.
  • extrusion can be enabled by using a dehumidifying agent, pelleted calcium carbonate, graft low density polyethylene and plasticized polyvinyl alcohol instead of starch.
  • 1 is a (a) cumulative carbon dioxide generation curve, (b) biodegradation curve of the standard (cellulose).
  • Figure 2 is a (a) cumulative carbon dioxide generation curve, (b) biodegradation curve of the biodegradable envelope.
  • the complex decomposition process of the composite degradable plastic of the present invention goes through the following steps.
  • a polyolefin resin composition composed of a long chain carbon-carbon bond composed of a long chain carbon-carbon bond.
  • Stearic acid components react with the carbon-carbon bonds of the exposed polyolefinic polymer component, some of which are transferred to calcium stearate and some of which partially decompose to form peroxides or hydroperoxides.
  • the iron stearate and magnesium stearate contained in the composition serve as an initiator to help initiate the reaction of the stearic acid component, and then the iron stearate, magnesium stearate, and calcium stearate serve as an oxidation reaction accelerator, resulting in a peroxide.
  • the redox reaction is repeated to generate free radicals with high reactivity, and auto oxidizes, thereby starting radical reaction using light or heat as reaction energy.
  • Acetyl acetonite, dimethyldithiocarbamic acid, and iron chloride components also react with light to generate free radicals, acting as photocatalytic accelerators, to initiate radical reactions.
  • Low molecular weight polyolefin resin The polymer is present in the form of carboxylic acid, ketones, aldehydes, carboxylic acids and the like which are easily decomposed.
  • Oxidation reaction aids such as calcium carbonate and polyvinyl alcohol, which are contained in the composition, absorb moisture under external conditions and provide a humid environment in which microorganisms can be actively active, thereby converting them into water, carbon dioxide and biomass. Has been disassembled.
  • biodegradable raw materials in order to produce a composite degradable plastic molded article capable of exhibiting oxidation, automatic oxidation, photodegradation, and microbial degradation, biodegradable raw materials, oxidative raw materials, initiators (oxidation reaction accelerators), photodegradants, oxidation reaction promoters, etc. It can be seen that the raw materials should be included.
  • starches selected from the group consisting of starch, modified starch and starch derivatives, complex biodegradable biodegradable without using expensive bio-biodegradable raw materials such as PLA, PCL and aliphatic polyester based by chemical synthesis It was confirmed that biodegradation is possible by using a small amount of additives such as photodegradants, oxidative decomposers and microbial decomposers in polyolefins to manufacture plastics. It was confirmed that homogeneous pellet production was possible by continuously using a melt extruder after obtaining a homogeneous mixture by mixing the stirrer non-heating at room temperature without using.
  • the present invention is a polyolefin resin, grafted polyolefin resin, powdered calcium carbonate, pellet calcium carbonate, dehumidifying agent, photodegrading agent, initiator, polyvinyl alcohol, biodegrading agent or biodegrading agent, It provides a polyvinyl alcohol plasticizer, an anionic surfactant, a lubricant, borax, characterized in that it comprises a polydegradable polyolefin resin composition.
  • the present invention is 10.0 to 17.2% by weight of polyolefin resin, 3.7 to 6.1% by weight of grafted polyolefin resin, 22.4 to 41.6% by weight of powdered calcium carbonate, 14 to 26% by weight of pellet type calcium carbonate, 1.4 to dehumidifying agent 2.6% by weight, photodegradant 0.96-1.78%, initiator 3.52-6.54%, polyvinyl alcohol 6.32-11.59%, biodegradable or biodegradable 3.93-7.30%, polyvinyl alcohol plasticizer 1.22-2.16% It provides a polydegradable polyolefin resin composition comprising 0.21 to 0.39% by weight of anionic surfactant, 2.1 to 3.9% by weight of lubricant, and 0.07 to 0.13% by weight of borax.
  • the polyolefin resin may be one or a mixture of two or more selected from the group consisting of low density polyethylene, linear low density polyethylene, and polypropylene. Preferably from 10 to 17.2% by weight, but most preferably 14% by weight.
  • the polyolefin resin is a first low density polyethylene having a melt index of 1.5 to 2.5 g / 10 min, preferably a melt index of 2.0 g / 10 min.
  • the density has a density of 0.9 to 1 g / cc, preferably 0.910 to 0.925 g / cc, more preferably 0.921 g / cc.
  • Polypropylene is approximately 0.9 to 0.91 g / cc.
  • the grafted polyolefin resin may be one or a mixture of two or more selected from the group consisting of grafted low density polyethylene, grafted high density polyethylene, grafted linear low density polyethylene, grafted polypropylene. Preferably from 3.7 to 6.1% by weight of grafted low density polyethylene can be used, more preferably from 5% by weight.
  • the grafted polyolefin resin is preferably low density polyethylene grafted with maleic anhydride, and has a melt index of 3.8 to 6.5 g / 10 min, preferably a melt index of 5.0 g / 10 min. This is because the melt index, density and material properties of each of the resin is difficult to homogeneous mixing, the addition of low-density polyethylene resin grafted with maleic anhydride allows for improved mixing and physical properties of the resin.
  • Films containing 6.1 wt% or more of low density polyethylene grafted with maleic anhydride are degraded due to a decrease in elongation, and when not added, film formation is not smooth.
  • Maleic anhydride LDPE used in the present invention improves the compatibility of polyvinyl alcohol and polyolefin resins.
  • the use of improving the compatibility between resins for example, there is an effect of improving the compatibility with calcium carbonate as well as low density polyethylene and high density polyethylene and polypropylene resins.
  • the calcium carbonate filler used in the present invention is used for reducing the manufacturing cost of the composite decomposition plastic, increasing strength, promoting biodegradability due to the collapse of the calcium carbonate matrix during biodegradation.
  • 22.4 to 41.6 wt% of powdered calcium carbonate and 14 to 26 wt% of pelleted calcium carbonate were used.
  • 32 wt% of powdered calcium carbonate and 20 wt% of pelletized calcium carbonate were used.
  • the 20% by weight of the pellet type calcium carbonate (Pellet CaCO3) comprises 14% by weight of calcium carbonate relative to the total polyolefin-based resin composition, so the total amount of calcium carbonate added in the present invention means about 46% by weight. If the total amount of calcium carbonate used is less than about 30% by weight compared to the resin composition, the cost reduction effect is insignificant. If the amount of the calcium carbonate exceeds about 60% by weight, the resin content is insufficient due to the insufficient resin content and poor dispersibility. Treated calcium carbonate or dispersant should be used additionally.
  • the powdered calcium carbonate particle size used in the present invention is preferably 0.2 to 5 ⁇ m, more preferably 0.5 to 3 ⁇ m.
  • the particles are precipitated, which adversely affects physical properties such as tensile strength, and when the particles are too fine, may cause a cost increase, and the shearing force is increased during mixing, and thus dispersibility may be lowered due to cohesion of the particles.
  • the pellet-type calcium carbonate is produced in pellet form by separately mixing the weight ratio of calcium carbonate and low density polyethylene to 6 to 8: 2 to 4, preferably 7: 3.
  • the low density polyethylene is separate from the low density polyethylene in the polydegradable polyolefin resin composition, and may be referred to as a second low density polyethylene.
  • the present invention was able to replace expensive starch using dehumidifying agents, pelleted calcium carbonate, graft low density polyethylene and plasticized polyvinyl alcohol, and a high speed stirrer maintained at 80 ° C. to produce products containing starch conventionally.
  • a homogeneous mixed composition was made possible by stirring a Henkel mixer or the like at room temperature without using.
  • the dehumidifying agent include zeolite, bentonite, diatomaceous earth, silica gel, activated carbon, quicklime, and super absorbent polymer.
  • a nonuniform mixture composition can be produced.
  • a zeolite is used that can utilize simple physical adsorption of fine and many pores formed during the reaction.
  • the zeolite was used by adding 1.4 to 2.6 wt%, preferably 2 wt%.
  • Zeolites are capillary pores whose pore structure can be stored in the pores without draining water due to capillary action. It is also a chemically stable natural substance that does not react with other raw materials and is a powder or granular product with high specific surface area and uniform pores. The product has a very low secondary cohesion and shows high dispersibility in the mixture and can be used at high temperatures such as 700 ° C. with high thermal stability. As a result, about 25 kinds of raw materials can be mixed at room temperature without applying heat, and a uniform mixture composition can be obtained, as well as reproducibility problems due to decomposition temperature differences can be solved.
  • the polymer chain becomes a low molecular hydrophilic compound by photodegradants. Due to the hygroscopic action of hydrophilic polyvinyl alcohol, glycerin, carboxymethylcellulose and calcium carbonate fillers, the plastic composition can maintain a humid environment suitable for mold growth. Hydrophilic polymer materials react with water to dissolve and initially transfer to a wet gel state, but over time they become hard gels and thus cannot be optimized for mold. Thus, when zeolite is used, it can react with water to adsorb water in the millions of nano-sized capillary pores, thereby preserving it, not discharging it, and thus maintaining a humid environment.
  • the photodegradants include acetylacetonate, dimethyldithiocarbamic acid and iron chloride.
  • Acetylacetonate reacts with light to generate free radicals to act as a photolysis accelerator, and in the present invention, ferric stearate or magnesium stearate using 0.02% by weight of cobalt triAcetylAcetonate When combined with a transition metal such as), it exhibited a ligand function that acts as a crosslinking promoter by the catalytic effect of oxidation reaction.
  • Dimethyldithiocarbamic acid was preferably 0.94% by weight as a photolysis accelerator having a bad odor and having an unsuitable color for producing a transparent film.
  • Iron chloride used 0.41% by weight. In the present invention, they react with light to generate free radicals, which act as photocatalytic promoters, thereby triggering radical reactions.
  • iron stearate, magnesium stearate, stearic acid were used as an initiator.
  • Iron stearate or magnesium stearate serves as an initiator to help initiate the reaction of the stearic acid component.
  • iron stearate, magnesium stearate, and calcium stearate serve as an oxidation promoter.
  • the initiator generates free radicals by repeating the peroxide and redox reactions, and has an autooxidation action due to these highly reactive free radicals.
  • the automatic oxidation allows light or heat to be used as the reaction energy to initiate a radical reaction.
  • the resin composition of the present invention preferably contains 2.83% by weight of iron stearate and 1.9% by weight of magnesium stearate. Magnesium stearate also serves as a dispersant for calcium carbonate.
  • Stearic acid is a typical fatty acid glyceride, while the melting temperature is low as about 72 °C to produce a metal stearate, such as iron stearate, calcium stearate, zinc stearate to control the photodegradability.
  • the surface of the calcium carbonate hydrophilic particles are converted to hydrophobicity and used as lubricants and biodegradants at the same time.
  • the resin composition of this invention contains a polyvinyl alcohol and a polyvinyl alcohol plasticizer.
  • a polyvinyl alcohol plasticizer glycerin, glycerol, benzoyl peroxide (initiator), and carboxymethyl cellulose are used.
  • the glycerin, glycerol, benzoyl peroxide, carboxymethyl cellulose is a raw material used to plasticize polyvinyl alcohol and exhibits properties as a biodegradable or biodegradable agent.
  • Glycerol can preserve the composite decomposable resin composition in a gel state, but, due to its unique viscosity, it was preferably able to complete plasticization at 0.4 wt%. Glycerin was used at an increased amount of 2.8% by weight for optimum polyvinyl alcohol plasticization. Benzoyl peroxide (BPO) comprises 0.013% by weight as a representative peroxide.
  • Benzoyl peroxide primarily serves to activate polyvinyl alcohol plasticizers and, when mixed with polyolefin resins, initiates grafting of maleic anhydride.
  • Peroxides may be selected from benzoyl peroxide, di-tributyl peroxide, tributyl hydroperoxide, nikumylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxide) hexane, or 1,3-Bis (t-butylperoxy-isopropyl) benzene etc. are mentioned, This invention is not limited to these.
  • Biodegradants or biodegradants of the resin composition of the present invention include PE wax, sorbitol, sodium alginate, glycerin, glycerol, polyethylene glycol, carboxymethylcellulose, methyl salicylic acid, stearic acid.
  • a biodegradable raw material that can be decomposed by itself
  • 0.1 wt% of sorbitol and 0.1 wt% of methyl salicylic acid were used in the present invention.
  • Carboxymethyl cellulose is also used for biodegradation or biodegradation, and 0.1 wt% of CMC-Na is used.
  • Alginic acid is widely used in the form of water-soluble sodium alginate because it is insoluble in water, and microorganisms are decomposed using 0.06% by weight.
  • polyethylene glycol is used as a yeast culture agent in the present invention was used 0.4% by weight.
  • the present invention does not perform a polymerization reaction including an esterification reaction and a polycondensation reaction separately using the microbial decomposer raw materials, and separately weighs the microbial decomposer raw materials in a raw state. Since it is a simple manufacturing method that is used by mixing and then extruded, no expensive cost is generated and in this process, the microbial decomposers are used for emulsifiers, stabilizers, thickeners, crosslinking agents, crosslinking accelerators and polyvinyl alcohol plasticizers.
  • the PE wax has the advantage of low melting point and when the composition is prepared using an extruder used a lubricant 6% by weight because it also has a function of biodegrading itself at low molecular weight.
  • the role of lubricant is PE wax, stearic acid, magnesium stearate, etc.
  • fatty acid-based lubricant When using fatty acid-based lubricant, it has the advantage of showing affinity with inorganic materials such as calcium carbonate, and has the advantage of surface modification by coating hydrophilic inorganic surface. It serves to facilitate the mixing of the additives.
  • Lubricant is an additive used to reduce and smooth the friction between composition materials in raw material mixing process or melt extrusion process. When many inorganic materials such as calcium carbonate are added, the temperature is increased due to frictional heat with screws. The organic additives are carbonized and pressed to the surface of the screw to eliminate the occurrence of defects. Another method is to use antioxidants to solve this problem.
  • Borax is a material that can be used to modify polyvinyl alcohol hydrophobicly, which acts as an emulsifier in the present invention and is well soluble in glycerin and the addition amount is 0.1% by weight.
  • Anionic surfactants include sodium lauryl sulfate and lauryl benzene sulfonic acid sodium.
  • Representative anionic surfactants commonly used as emulsifiers and dispersants are adsorbed at the interface between hydrophilic and hydrophobic raw materials to reduce their surface tension and allow them to be mixed to enhance compatibility.
  • sodium lauryl sulfate was added 0.2% by weight, and the amount of sodium lauryl benzene sulfonate added was 0.1% by weight.
  • composition according to the present invention may preferably further comprise a decomposition period adjusting agent which can control the decomposition period according to the use, the amount is preferably 0.001 to 5 parts by weight based on 100% by weight of the matrix resin. If it is less than 0.001 parts by weight, there is little photolysis control effect, and if it exceeds 5 parts by weight, there is a disadvantage in that photolysis does not proceed sufficiently within one year.
  • Raw material preparation step of measuring and preparing the master batch composition of the present invention Polyvinyl alcohol, benzoyl peroxide, glycerin, glycerol, and carboxymethyl cellulose raw materials are added together to the stirrer, followed by mixing for 4 to 6 minutes and preferably 5 minutes at 1 to 30 ° C. at 600 to 1000 RPM for plasticizing modified polyvinyl.
  • Polyvinyl alcohol plasticization step of obtaining an alcohol mixture Mixing step of uniformly mixing all of the remaining raw materials into the plasticized modified polyvinyl alcohol mixture sequentially;
  • the mixture obtained through the mixing step is continuously controlled to a temperature of 100 to 170 °C and added to the extruder and melt kneading and then slowly cooled at 1 to 30 °C or quenched in a cooling tank of 1 to 10 °C 2 to 3 mm pellets Prepare masterbatches in form.
  • polyvinyl alcohol resin unlike the general thermoplastic resin, melting point and pyrolysis temperature are very similar, so film forming by simple heat melting method is impossible.
  • the particles deposited on the surface of the film extracted in the inflation process were analyzed with polyvinyl alcohol and plasticization is required to remove them.
  • polyvinyl alcohol has low tensile strength and hydrophilicity, compatibility with polyolefin resins is very weak, and polyvinyl alcohol is added after plasticization due to strong hygroscopicity of calcium carbonate added together.
  • plasticization and melt kneading can be simultaneously performed in a batch process without pre-plasticizing in a stirrer. That is, by using an extruder having a plurality of inlet in series along the advancing direction of the extruder, polyvinyl alcohol and polyvinyl alcohol plasticizer are introduced through the first inlet to plasticize the polyvinyl alcohol. By injecting the remaining components of the resin composition through another inlet downstream after plasticization, the mixing and thermal fusion and kneading between the components can be done simultaneously.
  • the polyvinyl alcohol plasticizer is selected from the group consisting of glycerin, glycerol, benzoyl peroxide, carboxymethyl cellulose, one or two or more.
  • the plasticizer and polyvinyl alcohol can be added together and mixed for 4 to 6 minutes, preferably 5 minutes, to obtain plasticized polyvinyl alcohol.
  • the polyvinyl alcohol may be plasticized in advance to obtain a homogeneous mixed composition between the polyvinyl alcohol and the remaining raw materials of the resin composition and to increase mutual melting and bonding strength.
  • the polyolefin has poor compatibility with polyvinyl alcohol, so that when the polyolefin and polyvinyl alcohol are mixed, a separate interface is formed at the interface of each raw material, thereby deteriorating the mechanical properties of the molded article. Therefore, in order to improve the compatibility of polyvinyl alcohol and polyolefin, a material having both nonpolar functional groups compatible with polyolefin and polar functional groups compatible with polyvinyl alcohol in one molecular unit may be used as a compatibilizer.
  • low density polyethylene (LDPE-g-MA, melt index: 5g / 10min) grafted with maleic anhydride is added through an inlet during the melt extrusion process.
  • a low density polyethylene grafted with maleic anhydride is added to melt kneading, followed by cooling to prepare a masterbatch in pellet form.
  • Films containing 6.1 wt% or more of low density polyethylene grafted with maleic anhydride are degraded due to a decrease in elongation, and when not added, film formation is not smooth.
  • 200 to 600 parts by weight, preferably 400 parts by weight of a high density polyethylene resin is further mixed and melt-extruded and then cooled to prepare a compound batch in pellet form based on 100 parts by weight of the masterbatch composition. This is a range in which the amount of compound decomposition can be exhibited well. If more than 200 parts by weight of the compound is decomposed, the amount of compound decomposition is less than 600 parts by weight.
  • the high density polyethylene may have a melt index of 0.04 to 0.05 g / 10 min and a density of 0.9 to 1 g / cc. More preferably the high density polyethylene resin has a melt index of 0.045 g / 10 min and a density of 0.941 to 0.970 g / cc, in particular 0.956 g / cc. If the melt index is high, the injection moldability is excellent, and if it has a low index, it is advantageous for extrusion, so 0.04 to 100g / 10min may be selected according to the molding method and raw materials such as extrusion and injection.
  • films, sheets, bottles, injection molded articles, etc. may be conventionally formed by extrusion molding, inflation molding, injection molding, blow molding, or the like.
  • various molded products may be manufactured using molding machines manufactured in the art.
  • the composition of the present invention is for disposable plastic bags, plastic shopping bags, mulching film, food waste composting bags and the like, which can be produced by extrusion blow method, disposable cups, trays, which can be produced by injection method, It is suitable for manufacture of forks and the like.
  • the composite-degradable polyolefin resin composition of the present invention is a low density polyethylene (LDPE) 14% by weight, grafted LDPE (LDPE-g-MA) 5% by weight, calcium carbonate 32% by weight, pellet calcium carbonate (Pellet CaCO) 20 % By weight, 0.5% by weight white pigment, 6% by weight PE wax, 0.02% by weight acetylacetonate, 0.94% by weight dimethyldithiocarbamic acid, 0.41% by weight iron chloride, ferric stearate 2.83 % By weight, 1.9% by weight of magnesium stearate, 0.6% by weight of stearic acid, 9.4% by weight of polyvinyl alcohol (PVA), 2.8% by weight of glycerine, 0.4% by weight of Glyceryl Monostearate, polyethylene 0.4% by weight of glycol (PEG), 0.1% by weight of sorbitol, 0.1% by weight of borax, 0.1% by weight of carboxymethyl cellulose (CM
  • 20 wt% of pellet type calcium carbonate (Pellet CaCO3) in the polyolefin-based resin composition includes 6 wt% of low density polyethylene, so that the total amount of low density polyethylene means 20 wt%.
  • 5% by weight of low density polyethylene (LDPE-g-MA) modified with maleic anhydride is added.
  • Polyvinyl alcohol 940gr, benzoyl peroxide 1.3gr, glycerin 280gr, glycerol 40gr, carboxymethylcellulose 10gr was added to the stirrer and then mixed at room temperature at 600 to 1000 RPM for about 5 minutes to obtain a plasticized modified polyvinyl alcohol mixture.
  • Low Density Polyethylene (Hanhwa 830, Melt Index: 2g / 10min, Density: 0.921g / cc) 1400gr, Calcium Carbonate (FC-1) 3200gr, Pellets Calcium Carbonate 2000gr, Pigment (R 996 / R) 50gr, PE Wax 600gr, cobaltacetylacetonate 2gr, dimethyldithiocarbamic acid 94gr, iron chloride 41gr, iron stearate 283gr, magnesium stearate 190gr, stearic acid 60gr, Polyethylene glycol4000 40gr, sorbitol 10gr, borax 10gr, sodium lauryl sulfate 20gr, sodium laurylbenzenesulfonate 10gr, Mixes 1.3 gr of benzoyl peroxide, 6 gr of sodium alginate, 1 gr of methyl salicylic acid, 200 gr of zeolite (APNC 20) and 500 gr
  • Example 2 Using 50 kg of the compound batch prepared in Example 2 to prepare a plastic bag using a conventional film molding machine.
  • the biodegradable plastic bag which is a completed molded product, was commissioned by FITI tester to analyze the biodegradability.
  • KS M ISO 14855-1 Determination of aerobic biodegradability of plastic materials under composting conditions: method by carbon dioxide analysis- Part 1 The biodegradability of the samples was determined by titration as a general method.
  • the aerobic biodegradability was measured by measuring the amount of carbon dioxide generated in the composting conditions by titration method.
  • the biodegradability of the test substance compared to the standard material is shown in Table 2, FIG. 1, and FIG. 2, respectively.
  • Table 2 demonstrates that the biodegradable bags have a good biodegradability of 41.87% compared to the standard.
  • 1 is a (a) cumulative carbon dioxide generation curve
  • Figure 2 is (a) carbon dioxide accumulation curve
  • (b) biodegradation curve of the biodegradable envelope It can be seen that about 45% of this standard is biodegradable.
  • High density polyethylene pellet type resin (Lotte FL7100, Melt index: 0.045 g / 10min, Density: 0.096 g / cc) purchased in new form on the market 1.5kg recycled bag using at least one commercially available HDPE bag in addition to 8kg Kg and 0.5 Kg of a biodegradable plastic bag, which is a molded product of Example 3, were mixed to prepare a plastic bag using a conventional film molding machine.
  • the result of the measurement of the tensile strength, the elongation rate and the tear strength after aging according to KPS M 1013 and KPS M 1015 was obtained by requesting the FITI tester for the finished plastic bag.
  • the commercially available HDPE general plastic bag 8Kg was remelted and extruded using a conventional film molding machine to prepare a plastic bag, and the physical properties thereof were measured in the same manner as in Example 4.
  • Table 3 demonstrates that the recyclability of the biodegradable plastic bags according to the present invention is excellent.
  • Comparative Example 1 when the PLA recycled bag is added to the existing high-density polyethylene bag, re-melt extrusion is impossible and cannot be recycled. This causes a problem in that a separate biodegradable separator is additionally installed in the home separator. .
  • Example 4 the physical property results of Example 4, despite the recycled plastic bags in which the biodegradable plastic bags of the present invention is added to the conventional commercialized plastic bags, is similar to the physical properties of the general plastic bags of Comparative Example 2 will be no problem in commercialization Judging.
  • the multi-degradable polyolefin-based biodegradable plastic bag according to the present invention can be remelted to produce a finished molded article, it is possible to solve the problem of recycling existing biodegradable plastic and cost reduction effect occurs.

Abstract

La présente invention concerne une résine à base de polyoléfine multi-dégradable. Sans faire appel à des matières premières biodégradables à coût élevé telles que des amidons ou des matériaux à base de polyester aliphatique et analogues, une petite quantité d'additifs, tels qu'un agent photolytique, un agent de dégradation oxydative, ou un agent de dégradation de micro-organisme et analogues, est ajoutée aux résines à base de polyoléfine et un agent de déshumidification est utilisé, et par mélange, non chauffé, à température ambiante sans faire appel à un agitateur à grande vitesse maintenu à 80 °C, un mélange homogène est obtenu, puis une extrudeuse à fusion peut être utilisée en continu afin de fournir un mélange-maître multi-dégradable sous forme de pastilles homogènes et une composition de composé.
PCT/KR2018/003909 2017-04-25 2018-04-03 Composition de résine à base de polyoléfine multi-dégradable et son procédé de préparation WO2018199494A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20170052808 2017-04-25
KR10-2017-0052808 2017-04-25
KR1020180037121A KR102204708B1 (ko) 2017-04-25 2018-03-30 복합분해성 폴리올레핀계 수지 조성물 및 이의 제조방법
KR10-2018-0037121 2018-03-30

Publications (1)

Publication Number Publication Date
WO2018199494A1 true WO2018199494A1 (fr) 2018-11-01

Family

ID=63918937

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/003909 WO2018199494A1 (fr) 2017-04-25 2018-04-03 Composition de résine à base de polyoléfine multi-dégradable et son procédé de préparation

Country Status (1)

Country Link
WO (1) WO2018199494A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113308060A (zh) * 2020-02-27 2021-08-27 安徽中浩医用塑业有限公司 一种可降解塑料桶生产工艺
CN113429751A (zh) * 2021-06-16 2021-09-24 山西兰花华明纳米材料股份有限公司 一种生物降解功能粒料及其制备方法
CN114381066A (zh) * 2021-12-29 2022-04-22 广东顺威赛特工程塑料开发有限公司 一种超亲水聚丙烯复合材料及其制备方法
CN116178832A (zh) * 2023-03-14 2023-05-30 东莞意可新材料有限公司 一种可降解型高分子材料及其制备方法和应用

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR960022751U (ko) * 1994-12-23 1996-07-20 전자동 세탁기
US20040062884A1 (en) * 2000-12-06 2004-04-01 Benzhong Hao Compositions for photodegradable and biodegradable plastic product and use thereof
KR20050007872A (ko) * 2003-07-11 2005-01-21 주식회사 엠씨씨 복합분해성 열가소성 중합체 조성물 및 이로부터 제조되는복합분해성 열가소성 중합체 제품 및 그의 제조 방법
JP2007177083A (ja) * 2005-12-28 2007-07-12 Choru Chu Na 光分解性樹脂組成物の製造方法および該組成物からなる使い捨て容器
KR20080033620A (ko) * 2006-10-12 2008-04-17 (주)네오엠씨씨 폴리올레핀계 열가소성 중합체의 자연 분해용 첨가제조성물
KR101013453B1 (ko) * 2010-08-20 2011-02-14 김영구 프라스틱 복합 분해 촉진제 및 이의 제조방법
KR20110108461A (ko) * 2010-03-29 2011-10-06 주식회사 에코렐코리아 복합 분해 촉진제 및 이의 제조방법
KR101210301B1 (ko) * 2012-11-02 2012-12-11 주식회사 에코머스 식물 섬유 분말을 이용한 자연 분해성 식품 용기의 제조 방법
KR101365509B1 (ko) * 2012-06-14 2014-02-20 김종목 합성수지용 첨가제를 포함하는 복합 분해성 수지 조성물 및 그 제조방법

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR960022751U (ko) * 1994-12-23 1996-07-20 전자동 세탁기
US20040062884A1 (en) * 2000-12-06 2004-04-01 Benzhong Hao Compositions for photodegradable and biodegradable plastic product and use thereof
KR20050007872A (ko) * 2003-07-11 2005-01-21 주식회사 엠씨씨 복합분해성 열가소성 중합체 조성물 및 이로부터 제조되는복합분해성 열가소성 중합체 제품 및 그의 제조 방법
JP2007177083A (ja) * 2005-12-28 2007-07-12 Choru Chu Na 光分解性樹脂組成物の製造方法および該組成物からなる使い捨て容器
KR20080033620A (ko) * 2006-10-12 2008-04-17 (주)네오엠씨씨 폴리올레핀계 열가소성 중합체의 자연 분해용 첨가제조성물
KR20110108461A (ko) * 2010-03-29 2011-10-06 주식회사 에코렐코리아 복합 분해 촉진제 및 이의 제조방법
KR101013453B1 (ko) * 2010-08-20 2011-02-14 김영구 프라스틱 복합 분해 촉진제 및 이의 제조방법
KR101365509B1 (ko) * 2012-06-14 2014-02-20 김종목 합성수지용 첨가제를 포함하는 복합 분해성 수지 조성물 및 그 제조방법
KR101210301B1 (ko) * 2012-11-02 2012-12-11 주식회사 에코머스 식물 섬유 분말을 이용한 자연 분해성 식품 용기의 제조 방법

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113308060A (zh) * 2020-02-27 2021-08-27 安徽中浩医用塑业有限公司 一种可降解塑料桶生产工艺
CN113308060B (zh) * 2020-02-27 2022-05-27 安徽中浩医用塑业有限公司 一种可降解塑料桶生产工艺
CN113429751A (zh) * 2021-06-16 2021-09-24 山西兰花华明纳米材料股份有限公司 一种生物降解功能粒料及其制备方法
CN114381066A (zh) * 2021-12-29 2022-04-22 广东顺威赛特工程塑料开发有限公司 一种超亲水聚丙烯复合材料及其制备方法
CN116178832A (zh) * 2023-03-14 2023-05-30 东莞意可新材料有限公司 一种可降解型高分子材料及其制备方法和应用
CN116178832B (zh) * 2023-03-14 2024-02-27 东莞意可新材料有限公司 一种可降解型高分子材料及其制备方法和应用

Similar Documents

Publication Publication Date Title
WO2018199494A1 (fr) Composition de résine à base de polyoléfine multi-dégradable et son procédé de préparation
KR100197899B1 (ko) 전분이 매트릭스 수지에 화학결합된 생분해성 플라스틱 조성물과 이의 제조방법 및 이로부터 제조된 성형물
KR960012445B1 (ko) 전분이 화학결합된 생분해성 폴리에틸렌 조성물 및 그 제조방법
KR960012444B1 (ko) 전분이 화학 결합된 생분해성 폴리에틸렌 조성물 및 그 제조방법
KR101000749B1 (ko) 생분해성 수지 조성물, 그의 제조방법 및 그로부터 제조되는 생분해성 필름
KR101365615B1 (ko) 초기 기계적 강도가 우수한 산화생분해성 필름용 수지 조성물 및 이의 제조방법과 이로부터 제조되는 산화생분해성 필름
JP2003073539A (ja) 高強度生分解性樹脂組成物及び成形品
CN101717537B (zh) 一种聚烯烃薄膜及其制造方法
CN111154244A (zh) 一种全生物降解气球底托及制备方法
KR20190067320A (ko) 친환경 분해성 고분자 수지 조성물 및 이를 이용하여 제조된 필름
CN109988400B (zh) 一种环保型可降解包装复合膜及其制备方法
CN115433441A (zh) 一种全生物降解材料及其制备方法
CN110229497B (zh) 生物基聚氨酯/聚乳酸合金吹膜材料及其制备方法
CN101792539B (zh) 一种制备全淀粉生物全降解热塑性塑料的方法
CN114573933A (zh) 一种聚乙烯醇薄膜及其制备方法
EP0781807A2 (fr) Composition biodégradable, procédé et équipement pour la préparer
CN112812518A (zh) 一种热塑性生物降解塑料及其制备方法
KR102204708B1 (ko) 복합분해성 폴리올레핀계 수지 조성물 및 이의 제조방법
KR102377749B1 (ko) 목분을 사용한 생분해성 고분자 복합체 및 그 제조방법
KR100484721B1 (ko) 생분해성 마스터배치 수지 조성물과 그 제조방법, 및 이를포함하는 생붕괴성 필름
KR20030022914A (ko) 전분함유 폴리에틸렌 생붕괴성 수지 조성물 및 그 제조방법
CN1297599C (zh) 可完全生物降解的包装膜及地膜
KR101766791B1 (ko) 이중결합을 함유하여 신속 저분자화가 가능한 생분해성 연질 바이오 원료 조성물, 및 이의 압출성형품
CN111423703A (zh) 一种用于高填充PBAT生物降解薄膜的CaCO3表面处理方法及薄膜的制备
KR20190076451A (ko) 산화생분해성 필름용 수지 조성물, 이의 제조방법 및 이에 의해 제조되는 통기성의 산화생분해성 필름

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18791010

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18791010

Country of ref document: EP

Kind code of ref document: A1