CN104098881A - Polyhydroxyalkanoate composite film and preparation method thereof - Google Patents
Polyhydroxyalkanoate composite film and preparation method thereof Download PDFInfo
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- CN104098881A CN104098881A CN201410322975.6A CN201410322975A CN104098881A CN 104098881 A CN104098881 A CN 104098881A CN 201410322975 A CN201410322975 A CN 201410322975A CN 104098881 A CN104098881 A CN 104098881A
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Abstract
The invention discloses a polyhydroxyalkanoate composite film. The polyhydroxyalkanoate composite film comprises the following components in parts by weight: 5-15 parts of graphene slurry, 5-25 parts of tri-n-butyl citrate, 100 parts of polyhydroxyalkanoate powder, 0.2-1 part pf calcium stearate, 0.1-1 part of erucicamide and 0.2-1 part of an anti-oxidant. After being subjected to filling modification of graphene, the polyhydroxyalkanoate composite film is high in strength and tear-resistant and can realize complete biodegradation, the performance is far superior to the polyhydroxyalkanoate films manufactured by other modified filling agents, and the polyhydroxyalkanoate composite film provided by the invention can be widely used in the fields of food package, agricultural mulching films and the like. The invention also provides a preparation method of the polyhydroxyalkanoate composite film, and the method is simple in process; the formed polyhydroxyalkanoate composite film is low in shrinkage percentage, excellent in heat dissipation, improved in dimensional stability and easy for industrial production.
Description
Technical field
The invention belongs to thin film technique field, relate in particular to a kind of PHA laminated film and preparation method thereof.
Background technology
PHA is the natural biological macromolecular material developing rapidly over nearly more than 20 years, and it is polyester in the synthetic cell of a kind of a variety of microorganism, and fully biodegradable can thoroughly solve the white pollution problems of current serious; Often be applied to food product pack, agricultural film field; But this material exists the series of problems such as crystallization rate is slow, melt strength is low, molding shrinkage is large, film decoiling is difficult in application process; Seriously restricting its widespread use.
Adopt traditional inorganic materials, as nanometer grade calcium carbonate particle, barium sulfate particle or nano-silicon dioxide particle carry out filling-modified to its poly (hydroxyalkanoate) ester film, although can play the effect of nucleator raising crystallization rate, but the defect that still have that this kind of PHA laminated film product strength is poor, heat release is slow, shrinking percentage is large after moulding, thereby cause the drawback of PHA laminated film poor dimensional stability.
Graphene, as the thinnest in known materials, material that intensity is maximum in the world up to now, possesses extremely wide industry application space and economic society and is worth with its fabulous electroconductibility, thermal conductivity and light transmission.Testing data shows: on rubber, applying carbon black filled modification can improve rubbery intensity 2 times, and using mineral carbon alkene is filling-modified can improve 7 times by its intensity; But Graphene is applied but and existed and be difficult to homodisperse problem in laminated film, because Graphene is a kind of laminated structure, enabling to be uniformly dispersed also to form external phase, and brings into play due performance; Show on laminated film, can not play antistatic, gain in strength and fire-retardant texts.
For this reason, how by simple method, by a kind of antistatic to Graphene and the preparation of polyhydroxyalkanoate Material cladding, intensity is high, shrinking percentage is little, perfect heat-dissipating, and can realize a kind of PHA laminated film of the good combination properties such as complete biodegradable and preparation method thereof, to improve the scope of application of product, become a great problem of the present invention.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, and a kind of PHA laminated film and preparation method thereof is provided, and to improve the dimensional stability of this PHA laminated film, improves the scope of application of product.
The present invention solves the technical scheme that its technical problem takes: a kind of PHA laminated film, comprise following component, all in weight part: Graphene slurries 5-15 part, tri-n-butyl citrate 5-25 part, 100 parts of PHA powders, calcium stearate 0.2-1 part, erucicamide 0.1-1 part, oxidation inhibitor 0.2-1 part.
A preparation method for PHA laminated film, comprises following steps:
A. according to above-mentioned weight part ratio, Graphene slurries, tri-n-butyl citrate, PHA powder, calcium stearate, erucicamide and oxidation inhibitor are added to high speed agitator, stir 5-10min, the each component of above-mentioned material is mixed, and temperature is controlled at 70-90 DEG C;
B. the mixture being stirred is added to forcing machine, manufacture plastic pellet, barrel zone temperature is controlled at 80-140 DEG C;
C. plastic pellet is transferred to baking machine, storing temperature 80-100 DEG C, baking time 30-50min;
D. after drying, add to inflation film manufacturing machine, temperature is controlled at 120-150 DEG C; Be blow molded into PHA laminated film.
Described Graphene slurries are prepared and are obtained by following step:
(1) utilize nitric acid to carry out acidification to Graphene surface;
(2) graphene powder after acidifying is dissolved in coupling agent, stirs;
(3) in above-mentioned solution, add tri-n-butyl citrate, stir, under Ultrasonic Conditions, carry out ultrasonic point
Loose, graphene powder is dispersed in solution uniformly; Obtain Graphene slurries.
Described coupling agent is the long-chain organism of 18 carbon, and this coupling agent is preferably bromination octadecyl Trimethylamine 99 or octadecanalkoxyl poly sodium acrylate.
Beneficial effect of the present invention:
(1) PHA laminated film of the present invention is after Graphene is filling-modified: intensity is high, anti tear, can realize complete biodegradable; Its performance, considerably beyond the poly (hydroxyalkanoate) ester film that makes of other modified fillers therefor, can be widely used in the field such as food product pack, agricultural film.
(2) preparation method's technique of the present invention is simple; PHA laminated film shrinking percentage after moulding is little, and perfect heat-dissipating has been improved the dimensional stability of PHA laminated film, is easy to suitability for industrialized production.
embodiment:
Further illustrate technical scheme of the present invention below by specific embodiment.
embodiment 1
A kind of poly (hydroxyalkanoate) ester film, comprises following component, all in weight part: 5 parts, Graphene slurries, 5 parts of tri-n-butyl citrates, 100 parts of PHA powders, 0.2 part of calcium stearate, 0.1 part of erucicamide, 0.2 part, oxidation inhibitor.
The present invention for the preparation of the method for poly (hydroxyalkanoate) ester film is:
(1) according to above-mentioned weight part ratio, Graphene slurries, tri-n-butyl citrate, PHA powder, calcium stearate, erucicamide and oxidation inhibitor are added to high speed agitator, stir 5min, the each component of above-mentioned material is mixed, and temperature is controlled at 70 DEG C;
(2) mixture being stirred is added to forcing machine, manufacture plastic pellet, barrel zone temperature is controlled at 80-140 DEG C;
(3) plastic pellet is transferred to baking machine, 80 DEG C of storing temperatures, baking time 30min;
(4) after oven dry, add to inflation film manufacturing machine, temperature is controlled at 120 DEG C; Be blow molded into PHA laminated film.
Described Graphene slurries are prepared and are obtained by following step:
A. utilize nitric acid treatment Graphene surface;
B. tri-n-butyl citrate is dissolved in coupling agent, stirs;
C. under agitation condition, add the graphene powder of acidification, ultrasonic agitation, makes graphene uniform
Be dispersed in solution; Obtain Graphene slurries.
The Graphene slurries that make by above-mentioned steps are added in poly (hydroxyalkanoate) ester material and can play the effect of gaining in strength, improving antistatic and heat dispersion.
Described coupling agent is the long-chain organism of 18 carbon, and this coupling agent is preferably bromination octadecyl Trimethylamine 99 or octadecanalkoxyl poly sodium acrylate.
The PHA laminated film intensity that makes by the method is high, anti tear, can realize complete biodegradable, its over-all properties, considerably beyond the poly (hydroxyalkanoate) ester film that makes of other modification addition material, can be widely used in the field such as food product pack, agricultural film; In addition, PHA laminated film of the present invention in process of production speed of cooling is relatively very fast, and opening is better, has given full play to grapheme material perfect heat-dissipating, the characteristic that intensity is large.
embodiment 2
A kind of poly (hydroxyalkanoate) ester film, comprises following component, all in weight part: 10 parts, Graphene slurries, 15 parts of tri-n-butyl citrates, 100 parts of PHA powders, 0.5 part of calcium stearate, 0.5 part of erucicamide, 0.5 part, oxidation inhibitor.
The present invention for the preparation of the method for poly (hydroxyalkanoate) ester film is:
(1) according to above-mentioned weight part ratio, Graphene slurries, tri-n-butyl citrate, PHA powder, calcium stearate, erucicamide and oxidation inhibitor are added to high speed agitator, stir 7min, the each component of above-mentioned material is mixed, and temperature is controlled at 80 DEG C;
(2) mixture being stirred is added to forcing machine, manufacture plastic pellet, barrel zone temperature is controlled at 80-140 DEG C;
(3) plastic pellet is transferred to baking machine, 9 DEG C of storing temperatures, baking time 40min;
(4) after oven dry, add to inflation film manufacturing machine, temperature is controlled at 135 DEG C; Be blow molded into PHA laminated film.
The preparation process of described Graphene slurries is with embodiment 1.
embodiment 3
A kind of poly (hydroxyalkanoate) ester film, comprises following component, all in weight part: 15 parts, Graphene slurries, 25 parts of tri-n-butyl citrates, 100 parts of PHA powders, 1 part of calcium stearate, 1 part of erucicamide, 1 part, oxidation inhibitor.
The present invention for the preparation of the method for poly (hydroxyalkanoate) ester film is:
(1) according to above-mentioned weight part ratio, Graphene slurries, tri-n-butyl citrate, PHA powder, calcium stearate, erucicamide and oxidation inhibitor are added to high speed agitator, stir 10min, the each component of above-mentioned material is mixed, and temperature is controlled at 90 DEG C;
(2) mixture being stirred is added to forcing machine, manufacture plastic pellet, barrel zone temperature is controlled at 80-140 DEG C;
(3) plastic pellet is transferred to baking machine, 100 DEG C of storing temperatures, baking time 50min;
(4) after oven dry, add to inflation film manufacturing machine, temperature is controlled at 150 DEG C; Be blow molded into PHA laminated film.
The preparation process of described Graphene slurries is with embodiment 1.
Except technical characterictic described in specification sheets, be those skilled in the art known technology.
Claims (5)
1. a PHA laminated film, is characterized in that: comprise following component, all in weight part: Graphene slurries 5-15 part, tri-n-butyl citrate 5-25 part, 100 parts of PHA matrixes, calcium stearate 0.2-1 part, erucicamide 0.1-1 part, oxidation inhibitor 0.2-1 part.
2. a preparation method for PHA laminated film, comprises following steps:
A. according to above-mentioned weight part ratio, Graphene slurries, tri-n-butyl citrate, PHA matrix, calcium stearate, erucicamide and oxidation inhibitor are added to high speed agitator, temperature is controlled at 70-90 DEG C, stirs 5-10min;
B. the mixture being stirred is added to forcing machine and manufacture plastic pellet, barrel zone temperature is controlled at 80-140 DEG C;
C. plastic pellet is transferred to baking machine, baking machine temperature is controlled at 80-100 DEG C; Baking time 30-50min;
D. after drying, add to inflation film manufacturing machine, temperature is controlled at 120-150 DEG C; Be blow molded into poly (hydroxyalkanoate) ester film.
3. the preparation method of a kind of PHA laminated film according to claim 2, is characterized in that: described Graphene slurries are prepared and obtained by following step:
(1) utilize nitric acid to carry out acidification to Graphene surface;
(2) graphene powder after acidifying is dissolved in coupling agent, stirs;
(3) in above-mentioned solution, add tri-n-butyl citrate, stir, under Ultrasonic Conditions, carry out ultrasonic point
Loose, graphene powder is dispersed in solution uniformly; Obtain Graphene slurries.
4. the preparation method of a kind of PHA laminated film according to claim 3, is characterized in that: described coupling agent is the long-chain organism of 18 carbon.
5. the preparation method of a kind of PHA laminated film according to claim 3, is characterized in that: described coupling agent is bromination octadecyl Trimethylamine 99 or octadecanalkoxyl poly sodium acrylate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107556507A (en) * | 2017-07-19 | 2018-01-09 | 常州第六元素材料科技股份有限公司 | A kind of graphene oxide stoste modified plastics particle and preparation method thereof |
Citations (4)
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| CN101558457A (en) * | 2006-10-06 | 2009-10-14 | 普林斯顿大学理事会 | Functional graphene-polymer nanocomposites for gas barrier applications |
| US20110162955A1 (en) * | 2010-01-06 | 2011-07-07 | Peter Butzloff | Hybrid polymer compositions with enhanced bio-degradability |
| CN103319864A (en) * | 2013-06-01 | 2013-09-25 | 青岛中科昊泰新材料科技有限公司 | Biaxially stretched polylactic acid/graphene composite membrane |
| CN103772975A (en) * | 2012-10-25 | 2014-05-07 | 黑龙江鑫达企业集团有限公司 | Graphene/polymer conductive composite material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101558457A (en) * | 2006-10-06 | 2009-10-14 | 普林斯顿大学理事会 | Functional graphene-polymer nanocomposites for gas barrier applications |
| US20110162955A1 (en) * | 2010-01-06 | 2011-07-07 | Peter Butzloff | Hybrid polymer compositions with enhanced bio-degradability |
| CN103772975A (en) * | 2012-10-25 | 2014-05-07 | 黑龙江鑫达企业集团有限公司 | Graphene/polymer conductive composite material |
| CN103319864A (en) * | 2013-06-01 | 2013-09-25 | 青岛中科昊泰新材料科技有限公司 | Biaxially stretched polylactic acid/graphene composite membrane |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107556507A (en) * | 2017-07-19 | 2018-01-09 | 常州第六元素材料科技股份有限公司 | A kind of graphene oxide stoste modified plastics particle and preparation method thereof |
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Granted publication date: 20151209 Termination date: 20170709 |