CN106046522A - High-hydrolyzable polyethylene film material for toothpaste sheeting and preparation method thereof - Google Patents

High-hydrolyzable polyethylene film material for toothpaste sheeting and preparation method thereof Download PDF

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CN106046522A
CN106046522A CN201610579101.8A CN201610579101A CN106046522A CN 106046522 A CN106046522 A CN 106046522A CN 201610579101 A CN201610579101 A CN 201610579101A CN 106046522 A CN106046522 A CN 106046522A
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calcium carbonate
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silicone oil
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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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    • 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
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
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    • C08B31/00—Preparation of derivatives of starch
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    • C08B31/063—Starch sulfates
    • 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
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised 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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised 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
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer 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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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
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Abstract

The invention discloses a high-hydrolyzable polyethylene film material for toothpaste sheeting, made from the following materials according to parts by weight: 60-70 parts of linear low-density polyethylene, 10-15 parts of epoxy resin, 8-15 parts of waxy corn starch, 8-15 parts of plant fiber powder, 3-6 parts of a silane coupling agent, 25-35 parts of degradable calcium carbonate master batch, 10-18 parts of vinyl-terminated silicone oil, 0.3-0.8 part of hydrogen-containing silicone oil, suitable sulfuric acid solution, suitable platinum catalyst, and 6-10 parts of diethyl phthalate. After using, the polyethylene film material of the invention can be degraded into water and carbon dioxide under natural conditions within 6-18 months, the biodegradation speed is high, no white pollution is caused, and the requirement for environmental protection is met; the added epoxy resin and diethyl phthalate enable effectively improved hydrolyzability of film, improving stability of the film and prolonging its service life.

Description

A kind of toothpaste sheet material apparatus has high water-disintegrable polyethylene coating materials and preparation method thereof
Technical field
The invention belongs to technical field of polymer materials, being specifically related to a kind of toothpaste sheet material apparatus has high water-disintegrable polyethylene Coating materials and preparation method thereof.
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 apparatus have high water-disintegrable polyethylene coating materials and Its preparation 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 apparatus has high water-disintegrable polyethylene coating materials, is made up of the raw material of following weight portion: linear low close Degree polyethylene 60-70 part, epoxy resin 10-15 part, wax corn starch 8-15 part, Plant fiber's powder 8-15 part, silane is even Connection agent 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, sulfur Acid solution is appropriate, and platinum catalyst is appropriate, diethyl phthalate 6-10 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, epoxy resin and diethyl phthalate, controls Temperature is blended uniformly within 60-100 DEG C, after mix homogeneously, puts into low speed mixer combination cooling, is subsequently adding twin screw and squeezes Go out machine 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 is with having high water-disintegrable 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) epoxy resin added and diethyl phthalate can make the water-disintegrable raising of thin film effectively, improve thin The stability of film, extends service life.
Detailed description of the invention
A kind of toothpaste sheet material apparatus has high water-disintegrable polyethylene coating materials, is made up of the raw material of following weight portion (kilogram): line Property Low Density Polyethylene 70, epoxy resin 13, wax corn starch 10, Plant fiber's powder 10, silane coupler 4, degradation-type Calcium carbonate master batch 30, vinyl-terminated silicone oil 15 parts, containing hydrogen silicone oil 0.5 part, sulfuric acid solution is appropriate, and platinum catalyst is appropriate, adjacent benzene Dicarboxylate 8；
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, epoxy resin and diethyl phthalate, controls temperature It is blended uniformly within 70 DEG C, after mix homogeneously, puts into low speed mixer combination cooling, be subsequently adding double screw extruder extrusion Pelletize；
(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 is with having high water-disintegrable polyethylene coating materials.
Data after tested: hot strength (MPa): horizontal 23, longitudinal 25；Elongation at break (MPa): horizontal 880, longitudinally 840；Deflection (N): horizontal 3.3, longitudinal 4.2.

Claims (3)

1. a toothpaste sheet material apparatus has high water-disintegrable polyethylene coating materials, it is characterised in that be made up of the raw material of following weight portion: Linear low density polyethylene 60-70 part, epoxy resin 10-15 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, diethyl phthalate 6-10 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. the preparation method of high water-disintegrable polyethylene coating materials is had according to a kind of toothpaste sheet material apparatus described in claims 1, its It is characterised by, specifically comprises 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, epoxy resin and diethyl phthalate, controls Temperature is blended uniformly within 60-100 DEG C, after mix homogeneously, puts into low speed mixer combination cooling, is subsequently adding twin screw and squeezes Go out machine 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 is with having high water-disintegrable polyethylene coating materials.
3. the preparation method of high water-disintegrable polyethylene coating materials is had according to a kind of toothpaste sheet material apparatus described in claims 1,2, It is characterized in that, platinum catalyst is the aqueous isopropanol of chloroplatinic acid, and its content is for account for vinyl-terminated silicone oil and Silicon Containing Hydrogen with Pt The 4-6ppm of oil mixture total amount.
CN201610579101.8A 2016-07-21 2016-07-21 High-hydrolyzable polyethylene film material for toothpaste sheeting and preparation method thereof Pending CN106046522A (en)

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CN107629282A (en) * 2017-04-24 2018-01-26 湖南龙瑞纳米超分子材料有限公司 A kind of environment-friendly degradable film

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN107629282A (en) * 2017-04-24 2018-01-26 湖南龙瑞纳米超分子材料有限公司 A kind of environment-friendly degradable film
CN107082937A (en) * 2017-06-12 2017-08-22 太仓雅奥塑业有限公司 A kind of environment-friendly type plastic film
CN107163342A (en) * 2017-06-12 2017-09-15 太仓雅奥塑业有限公司 A kind of environment-friendly type plastic pocket

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Application publication date: 20161026