CN106810808A - A kind of degradable plastic sheeting composite of Tea Polyphenols antibacterial and preparation method thereof - Google Patents
A kind of degradable plastic sheeting composite of Tea Polyphenols antibacterial and preparation method thereof Download PDFInfo
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- 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
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- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
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- 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
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- 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
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- 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
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
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- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/018—Additives for biodegradable polymeric composition
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- 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 kind of degradable plastic sheeting composite of Tea Polyphenols antibacterial, 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, Tea Polyphenols, calcium propionate, to Ethyl formate of hydroxyl third 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, it is prepared for biodegradable laminated film.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
Technical field
The present invention relates to field of compound material, and in particular to a kind of degradable plastic sheeting composite wood of Tea Polyphenols antibacterial
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 degradable plastic sheeting composite wood of Tea Polyphenols antibacterial of offer
Material and its preparation technology, the composite made according to the technique have that biodegradability, mechanical property be good, anti-microbial property
It is good.
The technical problems to be solved by the invention are realized using following technical scheme：
Starch 31-42, polyvinyl alcohol 22-31, urea 0.1-0.5, glycerine 1-3, L-PROLINE 4-6, NaOH 2-4, nanometer
TiO2 3-7, manganese stearate 3-6, kaolin 4-8, shitosan 3-6, sodium carboxymethylcellulose 4-9, attapulgite 6-12, aoxidize stone
Black alkene 2-4, polyethyleneimine 3-5, vinyl acetate 4-8, Tea Polyphenols 2-5, calcium propionate 2-4, to hydroxyl the third Ethyl formate 1-3, second
Acid, appropriate deionized water.
The preparation method of the degradable plastic sheeting composite of a kind of Tea Polyphenols antibacterial, it is characterised in that by following
Step is 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. 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, is added remaining
Resulting material in material and a, b, c, is stirred continuously reaction 1-2h 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 Tea Polyphenols antibacterial.
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.
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 degradable plastic sheeting composite of Tea Polyphenols antibacterial, is obtained by the raw material of following weight parts (g)：
Starch 42, polyvinyl alcohol 31, urea 0.5, glycerine 3, L-PROLINE 6, NaOH 4, nano-TiO2 7, manganese stearate 6,
Kaolin 8, shitosan 6, sodium carboxymethylcellulose 9, attapulgite 12, graphene oxide 4, polyethyleneimine 5, vinyl acetate 8,
Tea Polyphenols 5, calcium propionate 4, to the third Ethyl formate of hydroxyl 3, acetic acid, appropriate deionized water.
The preparation method of the degradable plastic sheeting composite of a kind of Tea Polyphenols antibacterial, it is characterised in that by following
Step is 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. by polyvinyl alcohol 1:20 are dissolved in deionized water, are warming up to 40-50 DEG C of stirring and dissolving 40min, add leftover materials and
Resulting material in a, b, c, is stirred continuously reaction 2h and obtains coating liquid, and it is poured in crystallising dish while hot, allows its casting film-forming, from
So air-dry, obtain a kind of degradable plastic sheeting composite of Tea Polyphenols antibacterial.
A kind of performance detection knot of the degradable plastic sheeting composite of Tea Polyphenols antibacterial prepared by above-described embodiment
It is really 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. the degradable plastic sheeting composite of a kind of Tea Polyphenols antibacterial, it is characterised in that by the raw material of following weight parts
It is obtained：
Starch 31-42, polyvinyl alcohol 22-31, urea 0.1-0.5, glycerine 1-3, L-PROLINE 4-6, NaOH 2-4, nanometer
TiO2 3-7, manganese stearate 3-6, kaolin 4-8, shitosan 3-6, sodium carboxymethylcellulose 4-9, attapulgite 6-12, aoxidize stone
Black alkene 2-4, polyethyleneimine 3-5, vinyl acetate 4-8, Tea Polyphenols 2-5, calcium propionate 2-4, to hydroxyl the third Ethyl formate 1-3, second
Acid, appropriate deionized water.
2. the preparation method of the degradable plastic sheeting composite of a kind of Tea Polyphenols antibacterial according to claim 1,
Characterized in that, 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 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 polyvinyl alcohol 1:10-20 is dissolved in deionized water, is warming up to 40-60 DEG C of stirring and dissolving 30-50min, is added remaining
Resulting material in material and a, b, c, is stirred continuously reaction 1-2h 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 Tea Polyphenols antibacterial.
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Cited By (7)
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|---|---|---|---|---|
| CN108760732A (en) * | 2018-06-06 | 2018-11-06 | 吉林农业大学 | A kind of antimicrobial form food freshness instruction material of detectable carbon dioxide and preparation method thereof |
| CN108976680A (en) * | 2018-06-26 | 2018-12-11 | 铜陵市明科包装技术有限公司 | A kind of preparation process being sustained oxidation-resistant film |
| CN109836622A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院化学研究所 | A kind of organic-inorganic hybrid nanometer anti-biotic material and its preparation method and application |
| CN112795042A (en) * | 2021-01-29 | 2021-05-14 | 赵春富 | Preparation method of corn straw cellulose antibacterial film |
| CN112980121A (en) * | 2021-03-22 | 2021-06-18 | 杭州拜迪戈雷生物材料有限公司 | Antibacterial and mildewproof material and preparation method thereof |
| WO2022043679A1 (en) * | 2020-08-28 | 2022-03-03 | Symphony Environmental Ltd | Additive composition |
| CN115109286A (en) * | 2022-06-24 | 2022-09-27 | 大连工业大学 | Preparation method of degradable multifunctional food fresh-keeping packaging film |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109836622A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院化学研究所 | A kind of organic-inorganic hybrid nanometer anti-biotic material and its preparation method and application |
| CN109836622B (en) * | 2017-11-28 | 2020-08-21 | 中国科学院化学研究所 | Organic-inorganic hybrid nano antibacterial material and preparation method and application thereof |
| CN108760732A (en) * | 2018-06-06 | 2018-11-06 | 吉林农业大学 | A kind of antimicrobial form food freshness instruction material of detectable carbon dioxide and preparation method thereof |
| CN108760732B (en) * | 2018-06-06 | 2021-06-18 | 吉林农业大学 | Antibacterial food freshness indicating material capable of detecting carbon dioxide and preparation method thereof |
| CN108976680A (en) * | 2018-06-26 | 2018-12-11 | 铜陵市明科包装技术有限公司 | A kind of preparation process being sustained oxidation-resistant film |
| WO2022043679A1 (en) * | 2020-08-28 | 2022-03-03 | Symphony Environmental Ltd | Additive composition |
| CN112795042A (en) * | 2021-01-29 | 2021-05-14 | 赵春富 | Preparation method of corn straw cellulose antibacterial film |
| CN112980121A (en) * | 2021-03-22 | 2021-06-18 | 杭州拜迪戈雷生物材料有限公司 | Antibacterial and mildewproof material and preparation method thereof |
| CN115109286A (en) * | 2022-06-24 | 2022-09-27 | 大连工业大学 | Preparation method of degradable multifunctional food fresh-keeping packaging film |
| CN115109286B (en) * | 2022-06-24 | 2023-04-18 | 大连工业大学 | Preparation method of degradable multifunctional food fresh-keeping packaging film |
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