CN106699975A - Degradable plastic film composite material of butyl acrylate grafted modified starch and preparation method thereof - Google Patents
Degradable plastic film composite material of butyl acrylate grafted modified starch and preparation method thereof Download PDFInfo
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- CN106699975A CN106699975A CN201611180527.2A CN201611180527A CN106699975A CN 106699975 A CN106699975 A CN 106699975A CN 201611180527 A CN201611180527 A CN 201611180527A CN 106699975 A CN106699975 A CN 106699975A
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- 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
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- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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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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- 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
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- 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
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- 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
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- 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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- 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
- C08J2423/08—Copolymers of ethene
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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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/06—Biodegradable
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- C08L2203/16—Applications used for films
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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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Abstract
The invention discloses a degradable plastic film composite material of butyl acrylate grafted modified starch and a preparation process thereof. The degradable plastic film composite material is characterized in that starch, polyvinyl alcohol, urea, glycerol, L-proline, NaOH, nanometer TiO2, manganese stearate, kaolin, chitosan, sodium carboxymethylcellulose, attapulgite, graphene oxide, polyethyleneimine, vinyl acetate, butyl acrylate, ammonium persulfate, EVA, maleic anhydride and the like are used as raw materials. According to the degradable plastic film composite material, a composite catalyst is prepared by modifying the nanometer TiO2 with sodium proline, and a biodegradable composite film is prepared by using the kaolin as a bioactivator and the manganese stearate as a degradable accelerator. The sodium carboxymethylcellulose is added and mixed with the attapulgite and the chitosan so as to prepare the composite material. The starch is modified with the vinyl acetate, and electrostatic bonding force exists between the graphene oxide and the polyethyleneimine, so that the barrier property of the composite film is increased, and the oxygen permeability is reduced.
Description
Technical field
The present invention relates to field of compound material, and in particular to a kind of degradable shape of butyl acrylate graft modification starch
Material 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 degradable shape of butyl acrylate graft modification starch of offer
Material film composite material and its preparation technology, the composite made according to the technique have biodegradability, mechanical property
Good, good stability.
The technical problems to be solved by the invention are realized using following technical scheme:
Starch 34-41, polyvinyl alcohol 23-32, urea 0.1-0.5, glycerine 1-3, L-PROLINE 3-6, NaOH1-3, nanometer
TiO2 3-7, manganese stearate 4-7, kaolin 5-8, shitosan 3-5, sodium carboxymethylcellulose 3-6, attapulgite 5-12, aoxidize stone
Black alkene 1-3, polyethyleneimine 2-3, vinyl acetate 4-7, butyl acrylate 3-5, ammonium persulfate 2-4, EVA 3-6, maleic anhydride
2-5, ethanol, acetic acid, appropriate deionized water.
A kind of preparation method of the degradable plastic sheeting composite of butyl acrylate graft modification starch, its feature
It is to 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 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 1:3-5 adds ethanol, deionized water, starts agitator, leads to nitrogen, and water bath with thermostatic control is heated to 70-80
DEG C, butyl acrylate, ammonium persulfate are added dropwise over, 1-2h is reacted, it is down to room temperature, alcohol and washes 3-5 times, filters, dries to constant weight;
D. by resulting material 1 in c:15-20 is added to the water, and stirs, and tune pH is 7-8, is warming up to 80-90 DEG C of constant temperature gelatinization
1-2h, is adjusted to 50-60 DEG C of addition vinyl acetate, and constant temperature stirring 1-2h obtains A liquid;To in graphene oxide 1:5-10 adds water, surpasses
Sound oscillation disperses 1-2h, adds polyethyleneimine and A liquid, is well mixed;
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, is added remaining
Resulting material in material and a, b, d, 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 butyl acrylate graft modification starch.
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)Butyl acrylate graft modification starch is used, copolymer is prepared, modified starch is obtained with the compatibility of matrix
To raising, the water imbibition of co-mixing system can be improved, add EVA, maleic anhydride to improve the mechanical property of material.
(4)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
The degradable plastic sheeting composite of a kind of butyl acrylate graft modification starch, by following weight parts (g)
Raw material be obtained:
Starch 34, polyvinyl alcohol 32, urea 0.5, glycerine 3, L-PROLINE 6, NaOH 3, nano-TiO2 7, manganese stearate 4,
Kaolin 8, shitosan 5, sodium carboxymethylcellulose 6, attapulgite 12, graphene oxide 3, polyethyleneimine 3, vinyl acetate 7,
Butyl acrylate 5, ammonium persulfate 4, EVA 6, maleic anhydride 5, ethanol, acetic acid, appropriate deionized water.
A kind of preparation method of the degradable plastic sheeting composite of butyl acrylate graft modification starch, its feature
It is to carry 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 1:5 add ethanol, deionized water, start agitator, lead to nitrogen, and water bath with thermostatic control is heated to 70-80 DEG C,
Butyl acrylate, ammonium persulfate are added dropwise over, 2h is reacted, room temperature, alcohol are down to and are washed 3 times, filters, dries to constant weight;
D. by resulting material 1 in c:20 are added to the water, and stir, and tune pH is 7-8, are warming up to 80-90 DEG C of constant temperature gelatinization 1h,
50-60 DEG C of addition vinyl acetate is adjusted to, constant temperature stirring 1h obtains A liquid;To in graphene oxide 1:10 add water, sonic oscillation point
2h is dissipated, polyethyleneimine and A liquid is added, is well mixed;
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 leftover materials and
Resulting material in a, b, d, 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 butyl acrylate graft modification starch.
A kind of degradable plastic sheeting composite of butyl acrylate graft modification starch prepared by above-described embodiment
Performance test results it is 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 butyl acrylate graft modification starch, it is characterised in that by following
The raw material of weight portion is obtained:
Starch 34-41, polyvinyl alcohol 23-32, urea 0.1-0.5, glycerine 1-3, L-PROLINE 3-6, NaOH1-3, nanometer
TiO2 3-7, manganese stearate 4-7, kaolin 5-8, shitosan 3-5, sodium carboxymethylcellulose 3-6, attapulgite 5-12, aoxidize stone
Black alkene 1-3, polyethyleneimine 2-3, vinyl acetate 4-7, butyl acrylate 3-5, ammonium persulfate 2-4, EVA 3-6, maleic anhydride
2-5, ethanol, acetic acid, appropriate deionized water.
2. the degradable plastic sheeting composite of a kind of butyl acrylate graft modification starch 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 1:3-5 adds ethanol, deionized water, starts agitator, leads to nitrogen, and water bath with thermostatic control is heated to 70-80
DEG C, butyl acrylate, ammonium persulfate are added dropwise over, 1-2h is reacted, it is down to room temperature, alcohol and washes 3-5 times, filters, dries to constant weight;
D. by resulting material 1 in c:15-20 is added to the water, and stirs, and tune pH is 7-8, is warming up to 80-90 DEG C of constant temperature gelatinization
1-2h, is adjusted to 50-60 DEG C of addition vinyl acetate, and constant temperature stirring 1-2h obtains A liquid;To in graphene oxide 1:5-10 adds water, surpasses
Sound oscillation disperses 1-2h, adds polyethyleneimine and A liquid, is well mixed;
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, is added remaining
Resulting material in material and a, b, d, 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 butyl acrylate graft modification starch.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109912917A (en) * | 2019-01-24 | 2019-06-21 | 鲍可可 | A kind of soil remediation isolation overlay film and preparation method thereof |
CN110041569A (en) * | 2019-05-08 | 2019-07-23 | 含山县领创新材料科技有限公司 | A kind of degradation plastic and preparation method thereof |
CN113072787A (en) * | 2021-04-06 | 2021-07-06 | 郑州润尚环保科技有限公司 | PVA biodegradable film |
CN114015125A (en) * | 2021-10-20 | 2022-02-08 | 界首市天鸿新材料股份有限公司 | Preparation method of antistatic biodegradable packaging film |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN104892998A (en) * | 2015-05-22 | 2015-09-09 | 铜陵方正塑业科技有限公司 | Impact-resistant full-degradable plastic film and preparation method thereof |
CN105254979A (en) * | 2015-11-14 | 2016-01-20 | 李康 | Preparation method of degradable modified vinyl plastic |
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2016
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104892998A (en) * | 2015-05-22 | 2015-09-09 | 铜陵方正塑业科技有限公司 | Impact-resistant full-degradable plastic film and preparation method thereof |
CN105254979A (en) * | 2015-11-14 | 2016-01-20 | 李康 | Preparation method of degradable modified vinyl plastic |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109912917A (en) * | 2019-01-24 | 2019-06-21 | 鲍可可 | A kind of soil remediation isolation overlay film and preparation method thereof |
CN109912917B (en) * | 2019-01-24 | 2021-09-17 | 杭州益壤环境科技集团有限公司 | Isolation tectorial membrane for soil restoration and preparation method thereof |
CN110041569A (en) * | 2019-05-08 | 2019-07-23 | 含山县领创新材料科技有限公司 | A kind of degradation plastic and preparation method thereof |
CN113072787A (en) * | 2021-04-06 | 2021-07-06 | 郑州润尚环保科技有限公司 | PVA biodegradable film |
CN114015125A (en) * | 2021-10-20 | 2022-02-08 | 界首市天鸿新材料股份有限公司 | Preparation method of antistatic biodegradable packaging film |
CN114015125B (en) * | 2021-10-20 | 2022-09-09 | 界首市天鸿新材料股份有限公司 | Preparation method of antistatic biodegradable packaging film |
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Application publication date: 20170524 |