CN106751332A - A kind of high conductivity degradable plastic sheeting composite of carbon nanotubes and preparation method thereof - Google Patents
A kind of high conductivity degradable plastic sheeting composite of carbon nanotubes 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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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a kind of high conductivity degradable plastic sheeting composite of carbon nanotubes, 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, multi-walled carbon nano-tubes, silver acetate 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, 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 high conductivity degradable plastics of carbon nanotubes are thin
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 providing, a kind of high conductivity degradable plastics of carbon nanotubes are thin
Film composite material and its preparation technology, the composite made according to the technique have that biodegradability, mechanical property be good, electricity
Conductance is high.
The technical problems to be solved by the invention are realized using following technical scheme:
Starch 34-42, polyvinyl alcohol 23-31, urea 0.1-0.4, glycerine 1-3, L-PROLINE 2-5, NaOH1-3, nanometer
TiO2 3-6, manganese stearate 2-4, kaolin 3-7, shitosan 3-6, sodium carboxymethylcellulose 2-4, attapulgite 7-11, aoxidize stone
Black alkene 3-6, polyethyleneimine 2-3, vinyl acetate 5-8, multi-walled carbon nano-tubes 3-6, silver acetate 2-5, acetic acid, deionized water, ammonia
Water, appropriate concentrated nitric acid.
A kind of preparation method of the high conductivity degradable plastic sheeting composite of carbon nanotubes, 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 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. in multi-walled carbon nano-tubes 1:2-3 adds concentrated nitric acid, is warming up to 80-90 DEG C of water bath with thermostatic control stirring 3-5h, mistake after cooling
Filter, is washed to neutrality, mixes with silver acetate, 1:3-5 adds deionized water and ammoniacal liquor, ultrasonic disperse 1-2h, centrifugation, in nitrogen
2-3h is heated in 280-320 DEG C under gas shielded, it is 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 high conductivity degradable plastic sheeting composite of carbon nanotubes.
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)Carry out functionalization to multi-walled carbon nano-tubes with concentrated nitric acid, then it is modified with silver, obtained silver/
Carbon nano tube compound material, the film that mechanical property is good, electrical conductivity is high is prepared with polyvinyl alcohol blending.
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 high conductivity degradable plastic sheeting composite of a kind of carbon nanotubes, by the original of following weight parts (g)
Material is obtained:
Starch 42, polyvinyl alcohol 31, urea 0.4, glycerine 3, L-PROLINE 5, NaOH3, nano-TiO26, manganese stearate 4 is high
Ridge soil 7, shitosan 6, sodium carboxymethylcellulose 4, attapulgite 11, graphene oxide 6, polyethyleneimine 3, vinyl acetate 8 is more
Wall carbon nano tube 6, silver acetate 5, acetic acid, deionized water, ammoniacal liquor, appropriate concentrated nitric acid.
A kind of preparation method of the high conductivity degradable plastic sheeting composite of carbon nanotubes, 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-TiO21:20 points
Dissipate in deionized water, ultrasonic 1h obtains B liquid, and A drops are added in B liquid under magnetic agitation, 70-80 DEG C of stirring 1h is warming up to 90-
100 DEG C are evaporated, and are placed in after drying 5h in 100-110 DEG C of baking oven, and grind into powder uniformly mixes with manganese stearate, kaolin, warp
Twin screw extruder extruding pelletization, obtains Degradable master batch;
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. in multi-walled carbon nano-tubes 1:3 add concentrated nitric acids, are warming up to 80-90 DEG C of water bath with thermostatic control stirring 5h, cooled and filtered,
Neutrality is washed to, is mixed with silver acetate, 1:5 add deionized water and ammoniacal liquor, ultrasonic disperse 2h, centrifugation, in nitrogen protection
Under in 290-310 DEG C heat 2h, it is 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, is stirred continuously reaction 2h and obtains coating liquid, and it is poured in crystallising dish while hot, allows it to be cast
Film forming, natural air drying obtains a kind of high conductivity degradable plastic sheeting composite of carbon nanotubes.
A kind of property of the high conductivity degradable plastic sheeting composite of carbon nanotubes prepared by above-described embodiment
Energy testing result 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 high conductivity degradable plastic sheeting composite of a kind of carbon nanotubes, it is characterised in that by following weight
The raw material of part is obtained:
Starch 34-42, polyvinyl alcohol 23-31, urea 0.1-0.4, glycerine 1-3, L-PROLINE 2-5, NaOH1-3, nanometer
TiO2 3-6, manganese stearate 2-4, kaolin 3-7, shitosan 3-6, sodium carboxymethylcellulose 2-4, attapulgite 7-11, aoxidize stone
Black alkene 3-6, polyethyleneimine 2-3, vinyl acetate 5-8, multi-walled carbon nano-tubes 3-6, silver acetate 2-5, acetic acid, deionized water, ammonia
Water, appropriate concentrated nitric acid.
2. the system of the high conductivity degradable plastic sheeting composite of a kind of carbon nanotubes 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. in multi-walled carbon nano-tubes 1:2-3 adds concentrated nitric acid, is warming up to 80-90 DEG C of water bath with thermostatic control stirring 3-5h, mistake after cooling
Filter, is washed to neutrality, mixes with silver acetate, 1:3-5 adds deionized water and ammoniacal liquor, ultrasonic disperse 1-2h, centrifugation, in nitrogen
2-3h is heated in 280-320 DEG C under gas shielded, it is 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 high conductivity degradable plastic sheeting composite of carbon nanotubes.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108047618A (en) * | 2017-11-23 | 2018-05-18 | 当涂县瑞龙果树种植专业合作社 | A kind of mineral-filled degradable polyvinyl alcohol preservative film and preparation method thereof |
CN108912626A (en) * | 2018-04-11 | 2018-11-30 | 西安理工大学 | Functional graphene oxide/lactic acid composite material air blocking thin film preparation method |
CN109134906A (en) * | 2018-08-29 | 2019-01-04 | 佛山皖和新能源科技有限公司 | A kind of preparation method of nano composite environmental protection resistance oxygen tubing |
Citations (1)
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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 |
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2016
- 2016-12-20 CN CN201611180565.8A patent/CN106751332A/en active Pending
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Publication number | Priority date | Publication date | Assignee | Title |
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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 (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108047618A (en) * | 2017-11-23 | 2018-05-18 | 当涂县瑞龙果树种植专业合作社 | A kind of mineral-filled degradable polyvinyl alcohol preservative film and preparation method thereof |
CN108912626A (en) * | 2018-04-11 | 2018-11-30 | 西安理工大学 | Functional graphene oxide/lactic acid composite material air blocking thin film preparation method |
CN108912626B (en) * | 2018-04-11 | 2021-01-15 | 西安理工大学 | Preparation method of functionalized graphene oxide/polylactic acid composite gas barrier film |
CN109134906A (en) * | 2018-08-29 | 2019-01-04 | 佛山皖和新能源科技有限公司 | A kind of preparation method of nano composite environmental protection resistance oxygen tubing |
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