CN106699976A - Polyglycerol-fatty-acid-ester-containing antifogging degradable plastic film composite material and preparation method thereof - Google Patents

Polyglycerol-fatty-acid-ester-containing antifogging degradable plastic film composite material and preparation method thereof Download PDF

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Publication number
CN106699976A
CN106699976A CN201611180529.1A CN201611180529A CN106699976A CN 106699976 A CN106699976 A CN 106699976A CN 201611180529 A CN201611180529 A CN 201611180529A CN 106699976 A CN106699976 A CN 106699976A
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adds
fatty acid
acid ester
liquid
stirring
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丁自峰
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Anhui Fuyang Guotai Color Printing Packing Co Ltd
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Anhui Fuyang Guotai Color Printing Packing Co Ltd
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    • 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
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
    • 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
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/02—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides
    • 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
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/08—Cellulose derivatives
    • C08J2401/26—Cellulose ethers
    • C08J2401/28—Alkyl ethers
    • 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
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • 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
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C08L2205/03—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

Abstract

The invention discloses a polyglycerol-fatty-acid-ester-containing antifogging degradable plastic film composite material and a preparation method thereof. The invention is characterized in that the composite material is prepared from starch, polyvinyl alcohol, urea, glycerol, L-proline, NaOH, nano TiO2, manganese stearate, kaolin, chitosan, sodium carboxymethyl cellulose, attapulgite, graphene oxide, polyethyleneimine, vinyl acetate, acrylic acid, hydroxyethyl methacrylate, polyglycerol fatty acid ester and the like. Proline sodium is utilized to modify the nano TiO2 to prepare the composite catalyst; the kaolin is used as a bioactivator; and the manganese stearate is used as a degradation accelerator, thereby preparing the biodegradable composite film. The sodium carboxymethyl cellulose is added and blended with the attapulgite and chitosan to prepare the composite material. The vinyl acetate is utilized to modify the starch, and electrostatic bonding force exists between the graphene oxide and polyethyleneimine, thereby enhancing the barrier property of the composite film, and lowering the oxygen permeability.

Description

A kind of antifog degradable plastic sheeting composite containing polyglyceryl fatty acid ester and Its preparation method
Technical field
The present invention relates to field of compound material, and in particular to a kind of antifog degradable plastics containing polyglyceryl fatty acid ester Film composite material, and its preparation technology.
Background technology
For environmental protection, alleviate the problem of petroleum resources shortage, should reduce the use of petroleum-based plastics material, exploitation and Using bio-based degradable environment-friendly plastic material, Biodegradable material has excellent biocompatibility and environment-friendly Property, into the research emphasis in packaging material field.
Cong Hongjie is in its Master degree candidate's academic dissertation《The preparation and kinetics of thermal decomposition research of degradable plastic film》 In one text, with starch (St), polyvinyl alcohol (PVA) as primary raw material, urea (crosslinking agent), glycerine (plasticizer) are added, led to After first dissolving, rear gelatinization blending, the thin film preparation process process being crosslinked again, St/PVA complete biodegradable plastics are prepared for thin Film.Optimum reaction condition is：Reaction time 1h, 40 DEG C of reaction temperature, m (St):m(PVA)=6:4th, amount of urea 0.5%, the third three Alcohol consumption 4%.PVA is dissolved in pure water, 40 DEG C of stirring and dissolving 30min are warming up to, starch and glycerine is added, gelatinization is about 30min, is subsequently adding urea, is stirred continuously reaction 1h and obtains final product coating liquid, and coating liquid is poured in crystallising dish while hot, allows it to flow Prolong film forming, natural air drying, dried for standby.But it is not enough to there is mechanical property.
The present invention obtains Sodium proline with L-PROLINE, NaOH as raw material reaction, for modified Nano TiO2, it is prepared for multiple Catalyst is closed, the addition of Sodium proline improves TiO2Dispersiveness in the polymer；With kaolin as bioactivator, with hard Resin acid manganese is degradation of promoter, is prepared for biodegradable compound film.There is sodium carboxymethylcellulose water-retaining property, film forming to be molded Property, the advantage of dispersion stabilization, add sodium carboxymethylcellulose in the composite, can improve the resistance to of polyvinyl alcohol composite material Aqueous energy；Attapulgite includes natural 1-dimention nano fiber, enhancing effect, dispersiveness and the more preferable enhancement filling of mobility Agent；Shitosan is biodegradable, with good film forming, composite material film is prepared for being blended, with good machinery Performance, water resistance and mechanical property.Vinyl acetate is water-soluble big, with good biodegradable properties, can be applied to starch It is modified, biodegradable plastics, good mechanical properties are prepared for by graft copolymerization；Graphene oxide and polyethyleneimine it Between there is electrostatical binding power, improve the barrier property of laminated film, reduce oxygen permeability.
The content of the invention
The present invention solves the technical problem of a kind of antifog degradable plastics containing polyglyceryl fatty acid ester of offer Film composite material and its preparation technology, according to the technique make composite have biodegradability, mechanical property it is good, Anti-fog performance is strong.
The technical problems to be solved by the invention are realized using following technical scheme：
Starch 34-41, polyvinyl alcohol 22-32, urea 0.1-0.5, glycerine 2-3, L-PROLINE 4-6, NaOH 1-3, nanometer TiO24-7, manganese stearate 3-6, kaolin 4-8, shitosan 2-5, sodium carboxymethylcellulose 3-6, attapulgite 4-9, aoxidize stone Black alkene 2-4, polyethyleneimine 2-3, vinyl acetate 4-9, acrylic acid 3-7, hydroxyethyl methacrylate 2-6, ammonium persulfate 2-3, N,N,- methylene-bisacrylamide 1-3, polyglyceryl fatty acid ester 2-4, acetic acid, appropriate deionized water.
A kind of preparation method of the antifog degradable plastic sheeting composite containing polyglyceryl fatty acid ester, its feature exists In carrying out according to the following steps：
A. by L-PROLINE 1:30-40 is dissolved in deionized water, adds NaOH stirring reactions 1-2h to obtain A liquid, by nanometer TiO2 1:20-25 disperses in deionized water, and ultrasonic 1-2h obtains B liquid, A drops is added in B liquid under magnetic agitation, 70-80 DEG C Stirring 1-2h, is warming up to 90-100 DEG C and is evaporated, and is placed in after drying 3-5h in 100-110 DEG C of baking oven, grind into powder and stearic acid Manganese, kaolin uniformly mix, and through twin screw extruder extruding pelletization, obtain Degradable master batch；
B. by shitosan 1:3-6 stirs 20-40min, 1 in adding acetic acid:10-15 adds sodium carboxymethylcellulose, deionization Water, is sufficiently stirred for, and adds attapulgite, ultrasonically treated 1-2h；
C. in starch 1:15-20 adds water, stirs, and tune pH is 7-8, is warming up to 80-90 DEG C of constant temperature gelatinization 1-2h, adjusts To 50-60 DEG C of addition vinyl acetate, constant temperature stirring 1-2h obtains A liquid；To in graphene oxide 1:5-10 adds water, sonic oscillation Dispersion 1-2h, adds polyethyleneimine and A liquid, is well mixed；
D. by acrylic acid, hydroxyethyl methacrylate, N, N,- methylene-bisacrylamide and deionized water mixing and stirring, Logical nitrogen 10-30min, is warming up to 60-80 DEG C of water bath with thermostatic control, is added dropwise ammonium persulfate, insulation reaction 3-4h, be cooled to after room temperature with Polyglyceryl fatty acid ester is well mixed, stand-by；
E. by polyvinyl alcohol 1:10-20 is dissolved in deionized water, is warming up to 40-60 DEG C of stirring and dissolving 30-50min, adds the third three Resulting material in alcohol, urea and a, b, c, d, is stirred continuously reaction 1-2h and obtains coating liquid, and it is poured in crystallising dish while hot, Its casting film-forming, natural air drying is allowed to obtain a kind of antifog degradable plastic sheeting composite containing polyglyceryl fatty acid ester.
Reaction mechanism of the invention is as follows：
（1）The present invention obtains Sodium proline with L-PROLINE, NaOH as raw material reaction, for modified Nano TiO2, it is prepared for multiple Catalyst is closed, the addition of Sodium proline improves TiO2Dispersiveness in the polymer；With kaolin as bioactivator, with hard Resin acid manganese is degradation of promoter, is prepared for biodegradable compound film.
（2）Sodium carboxymethylcellulose has the advantages that water-retaining property, film forming mouldability, dispersion stabilization, in the composite Addition sodium carboxymethylcellulose, can improve the water resistance of polyvinyl alcohol composite material；Attapulgite includes natural 1-dimention nano Fiber, enhancing effect, dispersiveness and the more preferable enhancement filler of mobility；Shitosan is biodegradable, with it is good into Film, composite material film is prepared for being blended, with good mechanical performance, water resistance and mechanical property.
（3）Vinyl acetate is water-soluble big, with good biodegradable properties, can be applied to the modified of starch, passes through Graft copolymerization is prepared for biodegradable plastics, good mechanical properties；There is electrostatic between graphene oxide and polyethyleneimine Adhesion, improves the barrier property of laminated film, reduces oxygen permeability.
（4）With acrylic acid, hydroxyethyl methacrylate as raw material, ammonium persulfate is initiator, N, N,- methylene bisacrylamide Acid amides is crosslinking agent, has synthesized the copolymer with water resistance；It is right with surfactant polyglyceryl fatty acid ester as antifoggant Film carries out surface and is modified, and reduces film surface tension force, makes it have antifogging action.
Specific embodiment
In order that technological means, creation characteristic, reached purpose and effect that the present invention is realized are easy to understand, tie below Specific embodiment is closed, the present invention is expanded on further.
Embodiment
A kind of antifog degradable plastic sheeting composite containing polyglyceryl fatty acid ester, by following weight parts (g) Raw material is obtained：
Starch 41, polyvinyl alcohol 32, urea 0.5, glycerine 3, L-PROLINE 6, NaOH 3, nano-TiO27, manganese stearate 6, Kaolin 8, shitosan 5, sodium carboxymethylcellulose 6, attapulgite 9, graphene oxide 4, polyethyleneimine 3, vinyl acetate 9, Acrylic acid 7, hydroxyethyl methacrylate 6, ammonium persulfate 3, N, N,- methylene-bisacrylamide 3, polyglyceryl fatty acid ester 4, second Acid, appropriate deionized water.
A kind of preparation method of the antifog degradable plastic sheeting composite containing polyglyceryl fatty acid ester, its feature exists In carrying out according to the following steps：
A. by L-PROLINE 1:30 are dissolved in deionized water, add NaOH stirring reactions 1h to obtain A liquid, by nano-TiO2 1:20 In deionized water, ultrasonic 1h obtains B liquid, and A drops are added in B liquid under magnetic agitation for dispersion, 70-80 DEG C of stirring 1h, is warming up to 90-100 DEG C is evaporated, and is placed in after drying 5h in 100-110 DEG C of baking oven, and grind into powder uniformly mixes with manganese stearate, kaolin, Through twin screw extruder extruding pelletization, Degradable master batch is obtained；
B. by shitosan 1:40min, 1 are stirred in 6 addition acetic acid:15 add sodium carboxymethylcellulose, deionized water, fully stir Mix, add attapulgite, ultrasonically treated 2h；
C. in starch 1:20 add water, stir, and tune pH is 7-8, are warming up to 80-90 DEG C of constant temperature gelatinization 1h, are adjusted to 50- 60 DEG C of addition vinyl acetates, constant temperature stirring 1h, obtain A liquid；To in graphene oxide 1:10 add water, sonic oscillation to disperse 2h, plus Enter polyethyleneimine and A liquid, be well mixed；
D. by acrylic acid, hydroxyethyl methacrylate, N, N,- methylene-bisacrylamide and deionized water mixing and stirring, Logical nitrogen 30min, is warming up to 70-80 DEG C of water bath with thermostatic control, is added dropwise ammonium persulfate, insulation reaction 3h, is cooled to sweet with poly- after room temperature Oil and fat acid esters is well mixed, stand-by；
E. by polyvinyl alcohol 1:20 are dissolved in deionized water, are warming up to 40-50 DEG C of stirring and dissolving 40min, add glycerine, urine Resulting material in element and a, b, c, d, is stirred continuously reaction 2h and obtains coating liquid, and it is poured in crystallising dish while hot, allows it to flow Prolong film forming, natural air drying obtains a kind of antifog degradable plastic sheeting composite containing polyglyceryl fatty acid ester.
A kind of antifog degradable plastic sheeting composite containing polyglyceryl fatty acid ester prepared by above-described embodiment Performance test results are as follows：
Tensile strength >=35.7MPa, elongation at break >=301.2 %, soil bury 30 days after degradation of plastic film rate >=92%.

Claims (2)

1. a kind of antifog degradable plastic sheeting composite containing polyglyceryl fatty acid ester, it is characterised in that by following heavy The raw material for measuring part is obtained：
Starch 34-41, polyvinyl alcohol 22-32, urea 0.1-0.5, glycerine 2-3, L-PROLINE 4-6, NaOH 1-3, nanometer TiO24-7, manganese stearate 3-6, kaolin 4-8, shitosan 2-5, sodium carboxymethylcellulose 3-6, attapulgite 4-9, aoxidize stone Black alkene 2-4, polyethyleneimine 2-3, vinyl acetate 4-9, acrylic acid 3-7, hydroxyethyl methacrylate 2-6, ammonium persulfate 2-3, N,N,- methylene-bisacrylamide 1-3, polyglyceryl fatty acid ester 2-4, acetic acid, appropriate deionized water.
2. a kind of antifog degradable plastic sheeting composite containing polyglyceryl fatty acid ester according to claim 1 Preparation method, it is characterised in that carry out according to the following steps：
A. by L-PROLINE 1:30-40 is dissolved in deionized water, adds NaOH stirring reactions 1-2h to obtain A liquid, by nano-TiO2 1:20-25 disperses in deionized water, and ultrasonic 1-2h obtains B liquid, and A drops are added in B liquid under magnetic agitation, 70-80 DEG C of stirring 1-2h, is warming up to 90-100 DEG C and is evaporated, and is placed in after drying 3-5h in 100-110 DEG C of baking oven, grind into powder and manganese stearate, height The uniform mixing of ridge soil, through twin screw extruder extruding pelletization, obtains Degradable master batch；
B. by shitosan 1:3-6 stirs 20-40min, 1 in adding acetic acid:10-15 adds sodium carboxymethylcellulose, deionization Water, is sufficiently stirred for, and adds attapulgite, ultrasonically treated 1-2h；
C. in starch 1:15-20 adds water, stirs, and tune pH is 7-8, is warming up to 80-90 DEG C of constant temperature gelatinization 1-2h, adjusts To 50-60 DEG C of addition vinyl acetate, constant temperature stirring 1-2h obtains A liquid；To in graphene oxide 1:5-10 adds water, sonic oscillation Dispersion 1-2h, adds polyethyleneimine and A liquid, is well mixed；
D. by acrylic acid, hydroxyethyl methacrylate, N, N,- methylene-bisacrylamide and deionized water mixing and stirring, Logical nitrogen 10-30min, is warming up to 60-80 DEG C of water bath with thermostatic control, is added dropwise ammonium persulfate, insulation reaction 3-4h, be cooled to after room temperature with Polyglyceryl fatty acid ester is well mixed, stand-by；
E. by polyvinyl alcohol 1:10-20 is dissolved in deionized water, is warming up to 40-60 DEG C of stirring and dissolving 30-50min, adds the third three Resulting material in alcohol, urea and a, b, c, d, is stirred continuously reaction 1-2h and obtains coating liquid, and it is poured in crystallising dish while hot, Its casting film-forming, natural air drying is allowed to obtain a kind of antifog degradable plastic sheeting composite containing polyglyceryl fatty acid ester.
CN201611180529.1A 2016-12-20 2016-12-20 Polyglycerol-fatty-acid-ester-containing antifogging degradable plastic film composite material and preparation method thereof Pending CN106699976A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107880317A (en) * 2017-11-13 2018-04-06 郑州诚合信息技术有限公司 A kind of anti-fog thin film and preparation method thereof
CN108485162A (en) * 2018-03-30 2018-09-04 吕莉 A kind of preparation method of automobile-used ageing-resistant antifog film

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104098792A (en) * 2014-06-30 2014-10-15 安徽巢湖南方膜业有限责任公司 Corn starch degradable plastic film and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104098792A (en) * 2014-06-30 2014-10-15 安徽巢湖南方膜业有限责任公司 Corn starch degradable plastic film and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107880317A (en) * 2017-11-13 2018-04-06 郑州诚合信息技术有限公司 A kind of anti-fog thin film and preparation method thereof
CN108485162A (en) * 2018-03-30 2018-09-04 吕莉 A kind of preparation method of automobile-used ageing-resistant antifog film

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