CN106751333A - A kind of degradable plastic sheeting composite of microcapsule red phosphorus inflaming retarding and preparation method thereof - Google Patents

A kind of degradable plastic sheeting composite of microcapsule red phosphorus inflaming retarding and preparation method thereof Download PDF

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Publication number
CN106751333A
CN106751333A CN201611180618.6A CN201611180618A CN106751333A CN 106751333 A CN106751333 A CN 106751333A CN 201611180618 A CN201611180618 A CN 201611180618A CN 106751333 A CN106751333 A CN 106751333A
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red phosphorus
composite
adds
plastic sheeting
liquid
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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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    • 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
    • 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
    • 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
    • C08J3/223—Packed additives
    • 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
    • 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
    • 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
    • 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
    • C08L2201/02—Flame or fire retardant/resistant
    • 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
    • C08L2201/00—Properties
    • C08L2201/14—Gas barrier composition
    • 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

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

The invention discloses a kind of degradable plastic sheeting composite of microcapsule red phosphorus inflaming retarding, and its preparation technology, it is characterised in that with starch, polyvinyl alcohol, urea, glycerine, L proline, NaOH, nano-TiO2, manganese stearate, kaolin, shitosan, sodium carboxymethylcellulose, attapulgite, graphene oxide, polyethyleneimine, vinyl acetate, phenol, formaldehyde, OP 10, red phosphorus, carbon black, EVA etc. be raw material.Present invention Sodium proline modified Nano TiO2, composite catalyst is prepared for, with kaolin as bioactivator, with manganese stearate as degradation of promoter；Addition sodium carboxymethylcellulose prepares composite with attapulgite, chitosan blend；Vinyl acetate modified starch is used, biodegradable composite is prepared for by graft copolymerization；There is electrostatical binding power between graphene oxide and polyethyleneimine, improve the barrier property of laminated film, reduce oxygen permeability.

Description

A kind of degradable plastic sheeting composite of microcapsule red phosphorus inflaming retarding and its preparation Method
Technical field
The present invention relates to field of compound material, and in particular to a kind of degradable plastic sheeting of microcapsule red phosphorus inflaming retarding is answered Condensation 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.With phenol, formaldehyde as raw material, prepare Phenolic resin, with it as cyst wall, with red phosphorus as capsule-core, is prepared for microencapsulated red phosphorus flame retardant, with carbon black, EVA composite flame-proofs Plastic sheeting, the fire-retardant performance of gained composite is good.
The content of the invention
Answered the present invention solves the technical problem of a kind of degradable plastic sheeting of microcapsule red phosphorus inflaming retarding is provided Condensation material and its preparation technology, the composite made according to the technique have that biodegradability, mechanical property be good, anti-flammability Can be strong.
The technical problems to be solved by the invention are realized using following technical scheme：
Starch 35-40, polyvinyl alcohol 25-30, urea 0.1-0.5, glycerine 1-3, L-PROLINE 3-5, NaOH 1-2, nanometer TiO24-6, manganese stearate 3-5, kaolin 4-7, shitosan 2-4, sodium carboxymethylcellulose 3-6, attapulgite 6-9, aoxidize stone Black alkene 2-4, polyethyleneimine 1-2, vinyl acetate 5-7, phenol 2-3, formaldehyde 2-4, OP-10 1-2, red phosphorus 3-5, carbon black 2-3, EVA 2-4, acetic acid, appropriate deionized water.
The preparation method of the degradable plastic sheeting composite of a kind of microcapsule red phosphorus inflaming retarding, it is characterised in that press Following steps are carried out：
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. phenol, formaldehyde are mixed, tune pH is 8-9, in 70-80 DEG C of stirring reaction 1-2h, adjusts pH to neutrality, added after cooling Dispersant OP-10, red phosphorus, tune pH are 2-4, and 2-3h is reacted at 75-85 DEG C, adjust pH to neutrality, filtering, washing 3-5 times, in 100- After 110 DEG C dry 3-5h, it is well mixed with carbon black, EVA；
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 degradable plastic sheeting composite of microcapsule red phosphorus inflaming retarding.
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 phenol, formaldehyde as raw material, phenolic resin is prepared for, with it as cyst wall, with red phosphorus as capsule-core, be prepared for micro- Capsule red phosphorus fire retardant, with carbon black, EVA composite flame-proof plastic sheetings, the fire-retardant performance of gained composite is good.
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
The degradable plastic sheeting composite of a kind of microcapsule red phosphorus inflaming retarding, by the raw material system of following weight parts (g) ：
Starch 35, polyvinyl alcohol 25, urea 0.1, glycerine 3, L-PROLINE 5, NaOH 2, nano-TiO26, manganese stearate 5, Kaolin 7, shitosan 4, sodium carboxymethylcellulose 6, attapulgite 9, graphene oxide 4, polyethyleneimine 2, vinyl acetate 7, Phenol 3, formaldehyde 4, OP-10 1, red phosphorus 5, carbon black 3, EVA 4, acetic acid, appropriate deionized water.
The preparation method of the degradable plastic sheeting composite of a kind of microcapsule red phosphorus inflaming retarding, it is characterised in that press Following steps are carried out：
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. phenol, formaldehyde are mixed, tune pH is 8-9, in 70-80 DEG C of stirring reaction 1h, adjusts pH to neutrality, added after cooling and divided Powder OP-10, red phosphorus, it is 3 to adjust pH, and 2h is reacted at 75-85 DEG C, adjusts pH to neutrality, and filtering, washing 3 times are dry in 100-110 DEG C After dry 5h, it is well mixed with carbon black, EVA；
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 degradable plastic sheeting composite of microcapsule red phosphorus inflaming retarding.
A kind of performance inspection of the degradable plastic sheeting composite of microcapsule red phosphorus inflaming retarding prepared by above-described embodiment Survey result as follows：
Tensile strength >=35.7MPa, elongation at break >=301.2 %, oxygen index (OI) >=32%, fire-retardant rank is V-0 grades, and soil is covered Degradation of plastic film rate >=92% after burying 30 days.

Claims (2)

1. the degradable plastic sheeting composite of a kind of microcapsule red phosphorus inflaming retarding, it is characterised in that by following weight parts Raw material is obtained：
Starch 35-40, polyvinyl alcohol 25-30, urea 0.1-0.5, glycerine 1-3, L-PROLINE 3-5, NaOH 1-2, nanometer TiO24-6, manganese stearate 3-5, kaolin 4-7, shitosan 2-4, sodium carboxymethylcellulose 3-6, attapulgite 6-9, aoxidize stone Black alkene 2-4, polyethyleneimine 1-2, vinyl acetate 5-7, phenol 2-3, formaldehyde 2-4, OP-10 1-2, red phosphorus 3-5, carbon black 2-3, EVA 2-4, acetic acid, appropriate deionized water.
2. the preparation side of the degradable plastic sheeting composite of a kind of microcapsule red phosphorus inflaming retarding according to claim 1 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. phenol, formaldehyde are mixed, tune pH is 8-9, in 70-80 DEG C of stirring reaction 1-2h, adjusts pH to neutrality, added after cooling Dispersant OP-10, red phosphorus, tune pH are 2-4, and 2-3h is reacted at 75-85 DEG C, adjust pH to neutrality, filtering, washing 3-5 times, in 100- After 110 DEG C dry 3-5h, it is well mixed with carbon black, EVA；
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 degradable plastic sheeting composite of microcapsule red phosphorus inflaming retarding.
CN201611180618.6A 2016-12-20 2016-12-20 A kind of degradable plastic sheeting composite of microcapsule red phosphorus inflaming retarding and preparation method thereof Pending CN106751333A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107523249A (en) * 2017-07-11 2017-12-29 英杰惠能（北京）能源新技术有限公司 Multiphase composite flame-proof resin and preparation method thereof
CN112382829A (en) * 2020-10-14 2021-02-19 江西银汇新能源有限公司 Functionalized flexible membrane and preparation method and application thereof
CN114797500A (en) * 2022-03-18 2022-07-29 厦门富桂通科技有限公司 Fireproof composite film and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104893212A (en) * 2015-06-02 2015-09-09 铜陵方正塑业科技有限公司 Air-permeable full-degradable plastic film and manufacturing method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104893212A (en) * 2015-06-02 2015-09-09 铜陵方正塑业科技有限公司 Air-permeable full-degradable plastic film and manufacturing method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107523249A (en) * 2017-07-11 2017-12-29 英杰惠能（北京）能源新技术有限公司 Multiphase composite flame-proof resin and preparation method thereof
CN107523249B (en) * 2017-07-11 2020-10-30 英杰惠能（北京）能源新技术有限公司 Multiphase composite flame-retardant resin and preparation method thereof
CN112382829A (en) * 2020-10-14 2021-02-19 江西银汇新能源有限公司 Functionalized flexible membrane and preparation method and application thereof
CN112382829B (en) * 2020-10-14 2023-01-17 江西银汇新能源有限公司 Functional flexible membrane and preparation method and application thereof
CN114797500A (en) * 2022-03-18 2022-07-29 厦门富桂通科技有限公司 Fireproof composite film and preparation method thereof

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Application publication date: 20170531