CN106117775A - A kind of toothpaste sheet material high transparency polyethylene coating materials and preparation method thereof - Google Patents

A kind of toothpaste sheet material high transparency polyethylene coating materials and preparation method thereof Download PDF

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CN106117775A
CN106117775A CN201610579145.0A CN201610579145A CN106117775A CN 106117775 A CN106117775 A CN 106117775A CN 201610579145 A CN201610579145 A CN 201610579145A CN 106117775 A CN106117775 A CN 106117775A
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calcium carbonate
parts
density polyethylene
low density
coating materials
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谢明海
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Hefei Zhiyuan Packaging Technology Co Ltd
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Hefei Zhiyuan Packaging Technology Co Ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
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    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/08Copolymers of ethene
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04Homopolymers or copolymers of ethene
    • C08J2423/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2201/00Properties
    • C08L2201/06Biodegradable
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/10Transparent films; Clear coatings; Transparent materials
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
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    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/14Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16Fibres; Fibrils
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/066LDPE (radical process)

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a kind of toothpaste sheet material high transparency polyethylene coating materials, be made up of the raw material of following weight portion: linear low density polyethylene 40 50 parts, metallocene linear-low density polyethylene 20 30 parts, wax corn starch 8 15 parts, 8 15 parts of Plant fiber's powder, silane coupler 36 parts, degradation-type calcium carbonate master batch 25 35 parts, vinyl-terminated silicone oil 10 18 parts, containing hydrogen silicone oil 0.3 0.8 parts, sulfuric acid solution is appropriate, and platinum catalyst is appropriate, polyphthalamide 38 parts, SEBS 36 parts.The polyethylene coating materials of the present invention is after using, it is possible to be decomposed into water and carbon dioxide in 6 18 months under field conditions (factors), and biodegradation rate is fast, without producing white pollution, meets the requirement of environmental protection;Additionally by SEBS, the interpolation of metallocene linear-low density polyethylene, the polyethylene film obtained has the preferable transparency, has higher mechanical property simultaneously.

Description

A kind of toothpaste sheet material high transparency polyethylene coating materials and preparation method thereof
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of toothpaste sheet material high transparency polyethylene coating materials and Its preparation method.
Background technology
What dentifrice tube packaging was currently mainly used is multiple tube packaging, and the feature of a highly significant of composite soft tube is Its body material is composite sheet, and composite sheet is that the coating materials produced by multiple different materials by the way of compound is multiple It is combined.Its production technology is flexible, as can also be combined by extrusion with dry type is compound, can be combined in flakes after printing Material tubulation, it is also possible to carrying out printing tubulation after producing into sheet material;Draw materials extensively, can be polyolefin, polyamides for material Amine, polyester, aluminium foil, paper etc., can be blown film, casting films, co-extrusion film, biaxial stretching film, vacuum for the type of coating materials Aluminizer, coated film etc..This makes composite sheet all have the highest at aspects such as barrier property, physical and mechanical properties, outward appearances Motility.
At present, composite sheet packaging material market being used on toothpaste are mainly plastic-aluminum combined sheet material (ABL) and overall plastic Composite sheet (PBL), this two classes composite sheet almost occupies whole toothpaste packing market.
The problem of most popular plastic-aluminum sheet material maximum is exactly to be difficult to be recycled after it uses.Aluminium foil is multiple with plastics Simple approach delamination cannot be passed through, although occurred much reclaiming way after conjunction, but mostly in order to separate aluminium foil and plastics Acid, alkali or organic solvent can be used, the most costly, and environment is produced secondary pollution.And environmental protection composite sheet packaging Material, because it has low cost, reclaiming pollution-free, easy, the feature such as degradable, will become the master of following environment-friendly package material Stream.
Wang Mingsheng, Sun Heng have delivered advantage and application one literary composition of an environmental protection composite hose sheet material, describe composite soft tube Present situation and the development trend of environmental protection flexible pipe, just add the environment-friendlythin thin film of pearl filler in mechanical property, deflection, environmental protection, fall The aspects such as solution are analyzed and have been discussed.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of toothpaste sheet material high transparency polyethylene coating materials and preparation thereof Method, the problem solving polyethylene coating materials environment-friendly degradable, ensure again meet the mechanical property of dimerization product and use requirement.
A kind of toothpaste sheet material high transparency polyethylene coating materials, is made up of the raw material of following weight portion: linear low density polyethylene Alkene 40-50 part, metallocene linear-low density polyethylene 20-30 part, wax corn starch 8-15 part, Plant fiber powder 8-15 Part, silane coupler 3-6 part, degradation-type calcium carbonate master batch 25-35 part, vinyl-terminated silicone oil 10-18 part, containing hydrogen silicone oil 0.3- 0.8 part, sulfuric acid solution is appropriate, and platinum catalyst is appropriate, polyphthalamide 3-8 part, SEBS 3-6 part;
Described environment-friendly degradable type calcium carbonate master batch is composed of the following raw materials by weight: Low Density Polyethylene 10-30 part, n-octyl Ferrocene 10-15 part, polylactic acid 0.2-0.5 part, Tissuemat E 1-2 part, titanate coupling agent 0.5-2.5 part, nano-calcium carbonate 25-35 part, paraffin oil is appropriate.
Specifically comprise the following steps that
(1) preparation of degradation-type calcium carbonate master batch:
1. high speed mixing smelting machine high-speed rotation, then the titanate coupling agent diluted by paraffin oil, spray are put into, in advance by nano-calcium carbonate Entering in calcium carbonate material, heat up discharging after stirring 10-30 minute, obtains surface-treated calcium carbonate after drying;
2., with through surface-treated calcium carbonate for master batch core, same to Low Density Polyethylene, octyl ferrocene, polylactic acid, poly- Ethylene waxes puts in homogenizer, and it is blended uniform in 60-100 DEG C to control temperature, after mix homogeneously, puts into mixed on low speed Machine combination cooling, is subsequently adding double screw extruder extruding pelletization as environment-friendly degradable type calcium carbonate master batch;
(2) preparation of organosilicone elastic microsphere:
1., wax corn starch is joined in sulfuric acid solution, in the thermostatical oil bath of 35-45 DEG C, with 100-200 rev/min After the speed of clock stirs 5-7 days, product is centrifuged repeatedly and is washed to neutrality, be vacuum dried to obtain nanometer starch crystal solid powder End;
2., nanometer starch crystal pressed powder, Plant fiber's powder are added in deionized water, ultrasonic disperse 3-10 minute, then will Pour in the aqueous dispersions of nanometer starch crystal after vinyl-terminated silicone oil and containing hydrogen silicone oil mix homogeneously, 8000-on homogenizer Under the conditions of 12000 revs/min, homogenizing 3-15 minute, adds platinum catalyst, is the most under agitation warmed up to 40-60 DEG C of reaction 1- 3 hours, after reaction terminates, being performing centrifugal separation on, the organosilicone elastic that vacuum drying obtains nanometer starch crystal-Plant fiber's coating is micro- Ball;
(3) elastic microsphere step (2) obtained adds in the high-speed mixer that rotating speed is 800-1000 rev/min, adds silicon Alkane coupling agent is mixed with uniformly, is subsequently adding linear low density polyethylene, metallocene linear-low density polyethylene, three pears sugar Alcohol, polyphthalamide, control temperature and be blended within 60-100 DEG C uniformly, after mix homogeneously, puts into low speed mixer and mixes Close cooling, be subsequently adding double screw extruder extruding pelletization;
(4) calcium carbonate master batch step (1) obtained obtains plastic pellet with step (3) and mixs homogeneously in high-speed mixer, Then through steps such as pellet conveying, fusion plastification, extrusion, inflation, corona, rollings on film blowing device, a kind of tooth-paste sheet is prepared Material high transparency polyethylene coating materials.
Described platinum catalyst is the aqueous isopropanol of chloroplatinic acid, and its content is for accounting for vinyl-terminated silicone oil and hydrogeneous with Pt The 4-6ppm of silicon oil mixture total amount.
The present invention compared with prior art has the advantage that
(1) the polyethylene coating materials that the present invention is prepared by adding environment-friendly degradable type calcium carbonate master batch is after using, it is possible at 6- Being decomposed into water and carbon dioxide in 18 months under field conditions (factors), biodegradation rate is fast, without producing white pollution, meets The requirement of environmental protection.
(2) present invention utilizes nanometer starch crystal, Plant fiber's powder emulsifying vinyl-terminated silicone oil and containing hydrogen silicone oil, passes through Si-H addition reaction prepares organosilicone elastic microsphere.This organosilicone elastic microsphere surface is adsorbed with that degradable starch is nanocrystalline and plant Fiber powder, has the mobility of excellence, dispersibility, has toughness and the intensity of excellence simultaneously, improves the deflection of coating materials.
(3) additionally by SEBS, the interpolation of metallocene linear-low density polyethylene, melted coextrusion film blowing machine is utilized to produce To polyethylene film there is the preferable transparency, there is higher mechanical property simultaneously.
Detailed description of the invention
A kind of toothpaste sheet material high transparency polyethylene coating materials, is made up of the raw material of following weight portion (kilogram): linear low close Degree polyethylene 70, wax corn starch 10, Plant fiber's powder 10, silane coupler 4, degradation-type calcium carbonate master batch 30, ethylene Base end-blocking silicone oil 15 parts, containing hydrogen silicone oil 0.5 part, sulfuric acid solution is appropriate, and platinum catalyst is appropriate, polyphthalamide 5, SEBS 5;
Described environment-friendly degradable type calcium carbonate master batch is composed of the following raw materials by weight: Low Density Polyethylene 25 parts, n-octyl two Cyclopentadienyl ferrum 12 parts, polylactic acid 0.4 part, Tissuemat E 1 part, titanate coupling agent 1.5 parts, nano-calcium carbonate 30 parts, paraffin oil is appropriate.
Described platinum catalyst is the aqueous isopropanol of chloroplatinic acid, and its content is for accounting for vinyl-terminated silicone oil and hydrogeneous with Pt The 5ppm of silicon oil mixture total amount.
Specifically comprise the following steps that
(1) preparation of degradation-type calcium carbonate master batch:
1. high speed mixing smelting machine high-speed rotation, then the titanate coupling agent diluted by paraffin oil, spray are put into, in advance by nano-calcium carbonate Entering in calcium carbonate material, heat up discharging after stirring 20 minutes, obtains surface-treated calcium carbonate after drying;
2., with through surface-treated calcium carbonate for master batch core, same to Low Density Polyethylene, octyl ferrocene, polylactic acid, poly- Ethylene waxes puts in homogenizer, and it is blended uniform in 80 DEG C to control temperature, after mix homogeneously, puts into low speed mixer and mixes Close cooling, be subsequently adding double screw extruder extruding pelletization as environment-friendly degradable type calcium carbonate master batch;
(2) preparation of organosilicone elastic microsphere:
1., wax corn starch is joined in sulfuric acid solution, in the thermostatical oil bath of 40 DEG C, with the speed of 150 revs/min After stirring 6 days, product is centrifuged repeatedly and is washed to neutrality, be vacuum dried to obtain nanometer starch crystal pressed powder;
2., nanometer starch crystal pressed powder, Plant fiber's powder are added in deionized water, ultrasonic disperse 8 minutes, then by ethylene Pour into after base end-blocking silicone oil and containing hydrogen silicone oil mix homogeneously in the aqueous dispersions of nanometer starch crystal, on homogenizer 10000 revs/min Under the conditions of clock, homogenizing 10 minutes, add platinum catalyst, are the most under agitation warmed up to 50 DEG C and react 2 hours, after reaction terminates, Being performing centrifugal separation on, vacuum drying obtains the organosilicone elastic microsphere of nanometer starch crystal-Plant fiber's coating;
(3) elastic microsphere step (2) obtained adds in the high-speed mixer that rotating speed is 1000 revs/min, adds silane even Connection agent is mixed with uniformly, is subsequently adding linear low density polyethylene, metallocene linear-low density polyethylene, minashi sugar alcohol, gathers Phthalic amide, controls temperature and is blended uniformly within 70 DEG C, after mix homogeneously, put into low speed mixer combination cooling, so Rear addition double screw extruder extruding pelletization;
(4) calcium carbonate master batch step (1) obtained obtains plastic pellet with step (3) and mixs homogeneously in high-speed mixer, Then through steps such as pellet conveying, fusion plastification, extrusion, inflation, corona, rollings on film blowing device, a kind of tooth-paste sheet is prepared Material high transparency polyethylene coating materials.
Data after tested: hot strength (MPa): horizontal 22, longitudinal 25;Elongation at break (MPa): horizontal 875, longitudinally 835;Deflection (N): horizontal 3.2, longitudinal 4.1.

Claims (3)

1. a toothpaste sheet material high transparency polyethylene coating materials, it is characterised in that be made up of the raw material of following weight portion: the lowest Density polyethylene 40-50 part, metallocene linear-low density polyethylene 20-30 part, wax corn starch 8-15 part, plant fiber powder End 8-15 part, silane coupler 3-6 part, degradation-type calcium carbonate master batch 25-35 part, vinyl-terminated silicone oil 10-18 part, Silicon Containing Hydrogen Oil 0.3-0.8 part, sulfuric acid solution is appropriate, and platinum catalyst is appropriate, polyphthalamide 3-8 part, SEBS 3-6 part;
Described environment-friendly degradable type calcium carbonate master batch is composed of the following raw materials by weight: Low Density Polyethylene 10-30 part, n-octyl Ferrocene 10-15 part, polylactic acid 0.2-0.5 part, Tissuemat E 1-2 part, titanate coupling agent 0.5-2.5 part, nano-calcium carbonate 25-35 part, paraffin oil is appropriate.
2., according to the preparation method of a kind of toothpaste sheet material high transparency polyethylene coating materials described in claims 1, its feature exists In, specifically comprise the following steps that
(1) preparation of degradation-type calcium carbonate master batch:
1. high speed mixing smelting machine high-speed rotation, then the titanate coupling agent diluted by paraffin oil, spray are put into, in advance by nano-calcium carbonate Entering in calcium carbonate material, heat up discharging after stirring 10-30 minute, obtains surface-treated calcium carbonate after drying;
2., with through surface-treated calcium carbonate for master batch core, same to Low Density Polyethylene, octyl ferrocene, polylactic acid, poly- Ethylene waxes puts in homogenizer, and it is blended uniform in 60-100 DEG C to control temperature, after mix homogeneously, puts into mixed on low speed Machine combination cooling, is subsequently adding double screw extruder extruding pelletization as environment-friendly degradable type calcium carbonate master batch;
(2) preparation of organosilicone elastic microsphere:
1., wax corn starch is joined in sulfuric acid solution, in the thermostatical oil bath of 35-45 DEG C, with 100-200 rev/min After the speed of clock stirs 5-7 days, product is centrifuged repeatedly and is washed to neutrality, be vacuum dried to obtain nanometer starch crystal solid powder End;
2., nanometer starch crystal pressed powder, Plant fiber's powder are added in deionized water, ultrasonic disperse 3-10 minute, then will Pour in the aqueous dispersions of nanometer starch crystal after vinyl-terminated silicone oil and containing hydrogen silicone oil mix homogeneously, 8000-on homogenizer Under the conditions of 12000 revs/min, homogenizing 3-15 minute, adds platinum catalyst, is the most under agitation warmed up to 40-60 DEG C of reaction 1- 3 hours, after reaction terminates, being performing centrifugal separation on, the organosilicone elastic that vacuum drying obtains nanometer starch crystal-Plant fiber's coating is micro- Ball;
(3) elastic microsphere step (2) obtained adds in the high-speed mixer that rotating speed is 800-1000 rev/min, adds silicon Alkane coupling agent is mixed with uniformly, is subsequently adding linear low density polyethylene, metallocene linear-low density polyethylene, three pears sugar Alcohol, polyphthalamide, control temperature and be blended within 60-100 DEG C uniformly, after mix homogeneously, puts into low speed mixer and mixes Close cooling, be subsequently adding double screw extruder extruding pelletization;
(4) calcium carbonate master batch step (1) obtained obtains plastic pellet with step (3) and mixs homogeneously in high-speed mixer, Then through steps such as pellet conveying, fusion plastification, extrusion, inflation, corona, rollings on film blowing device, a kind of tooth-paste sheet is prepared Material high transparency polyethylene coating materials.
3. according to the preparation method of a kind of toothpaste sheet material high transparency polyethylene coating materials described in claims 1,2, its feature Being, platinum catalyst is the aqueous isopropanol of chloroplatinic acid, and its content is for accounting for vinyl-terminated silicone oil and containing hydrogen silicone oil mixing with Pt The 4-6ppm of thing total amount.
CN201610579145.0A 2016-07-21 2016-07-21 A kind of toothpaste sheet material high transparency polyethylene coating materials and preparation method thereof Pending CN106117775A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109233077A (en) * 2018-07-24 2019-01-18 桐城市正阳包装有限公司 A kind of biodegradable plastic film
CN110845767A (en) * 2019-11-08 2020-02-28 南通龙达生物新材料科技有限公司 Starch plastic composition and preparation method and application thereof

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CN104817749A (en) * 2015-04-17 2015-08-05 柳州蔚园塑料彩印包装有限责任公司 Plastic packaging bag

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109233077A (en) * 2018-07-24 2019-01-18 桐城市正阳包装有限公司 A kind of biodegradable plastic film
CN110845767A (en) * 2019-11-08 2020-02-28 南通龙达生物新材料科技有限公司 Starch plastic composition and preparation method and application thereof

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Application publication date: 20161116