CN105968743A - Antibacterial polylactic acid and starch compound fully-degradable plastic film and manufacturing method thereof - Google Patents
Antibacterial polylactic acid and starch compound fully-degradable plastic film and manufacturing method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
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- 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
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
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Abstract
The invention discloses an antibacterial polylactic acid and starch compound fully-degradable plastic film, which is characterized by being made from the following raw materials, by weight part, 80-85 of polylactic acid, 20-25 of corn starch, a proper amount of a sodium hydroxide solution with the concentration being 1 mol/L, a proper amount of hydrochloric acid with the concentration being 1 mol/L, 25-30 of hemp fibers, 0.8-1 of a silane coupling agent kh-550, a proper amount of distilled water, 12-14 of glycerin, 1.6-2 of epichlorohydrin, 3-4 of nanometer zinc oxide, 1-1.5 of chitosan, 0.4-0.6 of OP-10, 2-3 of castor oil, and 2-3 of ultrafine zeolite powder. Components, such as nanometer zinc oxide, chitosan and castor oil, have a synergistic effect and can improve antibacterial properties of the plastic film. The plastic film has biodegradability, is good in thermostability, and is excellent in toughness, mechanical properties, and use performance. The plastic film is safe and eco-friendly, and can meet the environment-protection requirements.
Description
Technical field
The present invention relates to plastic sheeting technical field, particularly a kind of antimicrobial form polylactic acid and compound fully degraded plastic sheeting of starch and preparation method thereof.
Background technology
In order to reduce the use of petroleum-based plastics material, protecting environment, the problem alleviating the most increasingly serious petroleum resources shortage, development and utilization bio-based degradable environment-friendly plastic material has become the research emphasis in packaging material field.
Poly-lactic acid material is one of degradation plastic material of being most widely used at present, as packing film material, PLA has good transparency, mechanical performance and biocompatibility, high intensity, thermoplasticity, hydrophobicity, processing and forming easily, can be degradable, catabolite is harmless to human non-toxic, derive from Renewable resource, it is easy to the advantages such as recycling, but the defective effect of polylactic acid fragility expensive, high, low toughness its in the application of wide range of areas.The degradation material that polylactic acid synthesizes as single monomer is in mechanical performance, the society's extensive requirement to material property can not be reached in processing characteristics and other functional characteristics, so Biodegradable material to be taked certain methods to be modified by we, the performance of its deficiency is carried out reinforcement, so that the environmentally friendly Biodegradable material scope of application is more extensive.
The research of natural fiber is the most concerned in the recent period, compared with carbon fiber, glass fibre, natural fiber (such as the wood fiber, flaxen fiber, bamboo fibre etc.) is low owing to having price, renewable, the series of advantages such as degradable and be used widely strengthening in composite, and the compound mechanical property that both can strengthen Biodegradable material of natural fiber and Biodegradable material in turn ensure that the renewable degradability of composite.Wherein flaxen fiber is owing to content of cellulose is high, intensity is high, therefore can prepare composite as good enhancement component.In flaxen fiber, china-hemp fibers has the mechanical properties such as higher specific strength and specific modulus, and the Fructus Cannabis yield of China occupies first of the world simultaneously, has potential industrial application value.
The present invention plans Fructus Cannabis-starch-polylactic acid blend and makes degradable plastic film, combine the high-performance of polylactic acid, the low cost of starch, the toughness advantages of higher of Fructus Cannabis, it is not only able to part and substitutes conventional petroleum base plastics, more solve the defect that simple polylactic acid exists, be the novel degradable plastic product of a kind of great DEVELOPMENT PROSPECT.
Summary of the invention
It is an object of the invention to provide a kind of antimicrobial form polylactic acid and compound fully degraded plastic sheeting of starch and preparation method thereof.The present invention includes the natural antibacterial ingredient such as nano zine oxide, Oleum Ricini, adds in the internal mixing pass of polylactic acid, and the product made has the composition that safety is antibacterial, it is possible to make food stage packaging bag.
In order to realize the purpose of the present invention, the present invention is implemented by below scheme:
A kind of antimicrobial form polylactic acid and the compound fully degraded plastic sheeting of starch, be made up of the raw material of following weight portion: polylactic acid 80-85, corn starch 20-25,1mol/L sodium hydroxide solution hydrochloric acid appropriate, 1mol/L is appropriate, china-hemp fibers 25-30, silane coupler kh-550 0.8-1, distilled water in right amount, glycerol 12-14, epoxychloropropane 1.6-2, nano zine oxide 3-4, chitosan 1-1.5, OP-10 0.4-0.6, Oleum Ricini 2-3, ultrafine zeolite powder 2-3；
A kind of antimicrobial form polylactic acid of the present invention and the compound fully degraded plastic sheeting of starch, be made up of step in detail below:
(1) china-hemp fibers is put in the sodium hydroxide solution of 1mol/L of times amount, under normal pressure, it is heated to 100 DEG C, steaming and decocting 2.5-3 hour, cold go after take out and be washed till neutrality with the hydrochloric acid of 1mol/L, put into and after baking oven is dried, put into that to be ground into 200 mesh powder in pulverizer stand-by；Silane coupler kh-550 is dissolved in distilled water, form the silane coupler kh-550 aqueous solution that concentration is 1%, the china-hemp fibers being ground into 200 mesh is soaked wherein, it is heated to 40-50 DEG C, precipitate is filtered out after soaking 40-60 minute, then allow in baking oven, within dry 3-4 hour, i.e. obtain, with 90-100 DEG C, the china-hemp fibers powder that surface processes；
(2) corn starch is dissolved in the distilled water of 3 times amount, instill the sodium hydroxide solution of 1mol/L while stirring, until pH value is 9.5, then being slowly dropped into epoxychloropropane under water bath condition, controlling bath temperature is 50 DEG C, after stirring is reacted 4-5 hour, with the salt acid for adjusting pH value of 1mol/L to 6.5, abandoning supernatant after standing 30 minutes, with distilled water wash, put into baking oven is dried stand-by；
(3) corn starch after the drying that the china-hemp fibers powder that surface step (1) obtained processes obtains with step (2) mixes with glycerol after mixing, put in kneader, extrude after mediating 30-40 minute under conditions of 100-120 DEG C, then the mixture of extrusion is put into ball milling 6-8 hour in ball mill, being then placed in baking oven, under the conditions of 130-140 DEG C, drying strengthens masterbatch；
(4) nano zine oxide is mixed homogeneously with ultrafine zeolite powder, put in baking oven with the temperature of 100-150 DEG C heat 60-80 minute stand-by, chitosan is dissolved in the distilled water of 5-7 times amount, then the mixed-powder after heating is added thereto, first ultrasonic disperse 10-15 minute, place in ball mill, ball milling was poured out after 40-60 minute, adds OP-10 and Oleum Ricini, puts in blender, stir 30 minutes with the speed of 600-800 rev/min, obtain mixed slurry；
(5) polylactic acid is added in banbury, plasticate 3-5 minute with the temperature of 150 DEG C, it is subsequently adding enhancing masterbatch that step (3) obtains and the mixed slurry that step (4) obtains, after continuing mixing 15-18 minute, carries out hot-melt extruded Blown Film, last qualitative rolling, pack and get final product.
The invention has the beneficial effects as follows: the present invention adds glycerol and is modified corn starch with epoxychloropropane, it is possible to solve the problem that starch is bad with describing property of polylactic acid, improve intensity and the toughness of composite simultaneously, the holistic cost of product can be reduced simultaneously；Utilize KH550 silane coupler that china-hemp fibers carries out pretreatment, thus improve interface contact and the compatibility, it is possible to increase the mechanical performance of material.
The present invention is also added with the compositions such as nano zine oxide, chitosan, Oleum Ricini, synergism, it is possible to increase the anti-microbial property of product；The biodegradability of product the most of the present invention, Heat stability is good, there is good toughness and mechanical property, serviceability is good, and safety and environmental protection meets environmental requirement.
Specific embodiments
Below by instantiation, the present invention is described in detail.
A kind of antimicrobial form polylactic acid and the compound fully degraded plastic sheeting of starch, be made up of the raw material of following weight portion (kilogram): polylactic acid 80, corn starch 20,1mol/L sodium hydroxide solution hydrochloric acid appropriate, 1mol/L is appropriate, china-hemp fibers 25, silane coupler kh-550 0.8, distilled water in right amount, glycerol 12, epoxychloropropane 1.6, nano zine oxide 3, chitosan 1, OP-10 0.4, Oleum Ricini 2, ultrafine zeolite powder 2；
A kind of antimicrobial form polylactic acid of the present invention and the compound fully degraded plastic sheeting of starch, be made up of step in detail below:
(1) china-hemp fibers is put in the sodium hydroxide solution of 1mol/L of times amount, under normal pressure, is heated to 100 DEG C, steaming and decocting 2.5 hours, cold go after take out and be washed till neutrality with the hydrochloric acid of 1mol/L, put into and after baking oven is dried, put into that to be ground into 200 mesh powder in pulverizer stand-by；Silane coupler kh-550 is dissolved in distilled water, form the silane coupler kh-550 aqueous solution that concentration is 1%, the china-hemp fibers being ground into 200 mesh is soaked wherein, it is heated to 40-50 DEG C, precipitate is filtered out after soaking 40 minutes, then allow in baking oven, be dried with 90-100 DEG C and within 3 hours, i.e. obtain the china-hemp fibers powder that surface processes；
(2) corn starch is dissolved in the distilled water of 3 times amount, instill the sodium hydroxide solution of 1mol/L while stirring, until pH value is 9.5, then being slowly dropped into epoxychloropropane under water bath condition, controlling bath temperature is 50 DEG C, after stirring is reacted 4 hours, with the salt acid for adjusting pH value of 1mol/L to 6.5, abandoning supernatant after standing 30 minutes, with distilled water wash, put into baking oven is dried stand-by；
(3) corn starch after the drying that the china-hemp fibers powder that surface step (1) obtained processes obtains with step (2) mixes with glycerol after mixing, put in kneader, extrude after mediating 30 minutes under conditions of 100-120 DEG C, then the mixture of extrusion is put into ball milling 6 hours in ball mill, being then placed in baking oven, under the conditions of 130-140 DEG C, drying strengthens masterbatch；
(4) nano zine oxide is mixed homogeneously with ultrafine zeolite powder, put in baking oven with the temperature of 100-150 DEG C heat 60-80 minute stand-by, chitosan is dissolved in the distilled water of 5-7 times amount, then the mixed-powder after heating is added thereto, first ultrasonic disperse 10-15 minute, place in ball mill, ball milling was poured out after 40-60 minute, adds OP-10 and Oleum Ricini, puts in blender, stir 30 minutes with the speed of 600 revs/min, obtain mixed slurry；
(5) polylactic acid is added in banbury, plasticate 3-5 minute with the temperature of 150 DEG C, it is subsequently adding enhancing masterbatch that step (3) obtains and the mixed slurry that step (4) obtains, after continuing mixing 15 minutes, carries out hot-melt extruded Blown Film, last qualitative rolling, pack and get final product.
Product of the present invention is carried out compost experiment, and result shows, the biological decomposition rate 60% after 81 days.According to
GB/T 1040.3-2006 carries out Mechanics Performance Testing, and cross directional stretch load is 4.31N, and transverse breakage percentage elongation is 859.3%；Longitudinal stretching load is 4.08N, and longitudinal elongation at break rate is 664.1%, and testing result illustrates that product of the present invention has reached the requirement of common plastics film, and index of correlation is better than country's regulation requirement to Biodegradable material.
Claims (2)
1. an antimicrobial form polylactic acid and the compound fully degraded plastic sheeting of starch, it is characterized in that, be made up of the raw material of following weight portion: polylactic acid 80-85, corn starch 20-25,1mol/L sodium hydroxide solution hydrochloric acid appropriate, 1mol/L appropriate, china-hemp fibers 25-30, silane coupler kh-550 0.8-1, distilled water are appropriate, glycerol 12-14, epoxychloropropane 1.6-2, nano zine oxide 3-4, chitosan 1-1.5, OP-10 0.4-0.6, Oleum Ricini 2-3, ultrafine zeolite powder 2-3.
A kind of antimicrobial form polylactic acid and the compound fully degraded plastic sheeting of starch, it is characterised in that be made up of step in detail below:
(1) china-hemp fibers is put in the sodium hydroxide solution of 1mol/L of times amount, under normal pressure, it is heated to 100 DEG C, steaming and decocting 2.5-3 hour, cold go after take out and be washed till neutrality with the hydrochloric acid of 1mol/L, put into and after baking oven is dried, put into that to be ground into 200 mesh powder in pulverizer stand-by；Silane coupler kh-550 is dissolved in distilled water, form the silane coupler kh-550 aqueous solution that concentration is 1%, the china-hemp fibers being ground into 200 mesh is soaked wherein, it is heated to 40-50 DEG C, precipitate is filtered out after soaking 40-60 minute, then allow in baking oven, within dry 3-4 hour, i.e. obtain, with 90-100 DEG C, the china-hemp fibers powder that surface processes；
(2) corn starch is dissolved in the distilled water of 3 times amount, instill the sodium hydroxide solution of 1mol/L while stirring, until pH value is 9.5, then being slowly dropped into epoxychloropropane under water bath condition, controlling bath temperature is 50 DEG C, after stirring is reacted 4-5 hour, with the salt acid for adjusting pH value of 1mol/L to 6.5, abandoning supernatant after standing 30 minutes, with distilled water wash, put into baking oven is dried stand-by；
(3) corn starch after the drying that the china-hemp fibers powder that surface step (1) obtained processes obtains with step (2) mixes with glycerol after mixing, put in kneader, extrude after mediating 30-40 minute under conditions of 100-120 DEG C, then the mixture of extrusion is put into ball milling 6-8 hour in ball mill, being then placed in baking oven, under the conditions of 130-140 DEG C, drying strengthens masterbatch；
(4) nano zine oxide is mixed homogeneously with ultrafine zeolite powder, put in baking oven with the temperature of 100-150 DEG C heat 60-80 minute stand-by, chitosan is dissolved in the distilled water of 5-7 times amount, then the mixed-powder after heating is added thereto, first ultrasonic disperse 10-15 minute, place in ball mill, ball milling was poured out after 40-60 minute, adds OP-10 and Oleum Ricini, puts in blender, stir 30 minutes with the speed of 600-800 rev/min, obtain mixed slurry；
(5) polylactic acid is added in banbury, plasticate 3-5 minute with the temperature of 150 DEG C, it is subsequently adding enhancing masterbatch that step (3) obtains and the mixed slurry that step (4) obtains, after continuing mixing 15-18 minute, carries out hot-melt extruded Blown Film, last qualitative rolling, pack and get final product.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107057308A (en) * | 2017-06-26 | 2017-08-18 | 淮安市冰青建设工程管理有限公司 | A kind of thin-film material |
| CN107118529A (en) * | 2017-06-26 | 2017-09-01 | 淮安市冰青建设工程管理有限公司 | A kind of preparation method of antimicrobial form polylactic acid film material |
| CN107828086A (en) * | 2017-11-03 | 2018-03-23 | 苏州甫众塑胶有限公司 | A kind of antimicrobial form Active Packaging Materials and its preparation technology |
| WO2018106191A1 (en) * | 2016-12-09 | 2018-06-14 | National University Of Singapore | A packaging material and method of preparation thereof |
| CN108707321A (en) * | 2018-04-20 | 2018-10-26 | 苏州凌科特新材料有限公司 | A kind of preparation method of compound light blocking film |
| CN109224633A (en) * | 2018-11-06 | 2019-01-18 | 江苏三元环保科技有限公司 | A kind of environment-friendly type filter bag of doping vario-property starch and preparation method thereof |
| CN109608700A (en) * | 2018-11-29 | 2019-04-12 | 烟台八方文化传媒有限公司 | A kind of prepackaged food antibiotic packaging material and preparation method thereof |
| CN110845832A (en) * | 2019-10-21 | 2020-02-28 | 刘辉 | Biodegradable film for inner package of sanitary product |
| CN110964300A (en) * | 2018-09-28 | 2020-04-07 | 句容市飞达箱包有限公司 | Biodegradable composite material with antibacterial property and preparation method thereof |
| CN112341771A (en) * | 2019-08-09 | 2021-02-09 | 上海茵派化妆品有限公司 | Environment-friendly degradable mask packaging material and preparation method thereof |
| IT202200016212A1 (en) * | 2022-07-29 | 2024-01-29 | Planet Bioplastic S R L | POLYMERIC FORMULATIONS OF NATURALLY ORIGINATED HOT GLUES FOR APPLICATIONS SUCH AS COATINGS CONTAINING ACTIVE BIOMOLECULES |
| CN117551294A (en) * | 2024-01-11 | 2024-02-13 | 汕头市雅仕达包装材料有限公司 | High-strength PE film and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018106191A1 (en) * | 2016-12-09 | 2018-06-14 | National University Of Singapore | A packaging material and method of preparation thereof |
| CN107118529A (en) * | 2017-06-26 | 2017-09-01 | 淮安市冰青建设工程管理有限公司 | A kind of preparation method of antimicrobial form polylactic acid film material |
| CN107057308A (en) * | 2017-06-26 | 2017-08-18 | 淮安市冰青建设工程管理有限公司 | A kind of thin-film material |
| CN107828086A (en) * | 2017-11-03 | 2018-03-23 | 苏州甫众塑胶有限公司 | A kind of antimicrobial form Active Packaging Materials and its preparation technology |
| CN108707321A (en) * | 2018-04-20 | 2018-10-26 | 苏州凌科特新材料有限公司 | A kind of preparation method of compound light blocking film |
| CN110964300A (en) * | 2018-09-28 | 2020-04-07 | 句容市飞达箱包有限公司 | Biodegradable composite material with antibacterial property and preparation method thereof |
| CN109224633A (en) * | 2018-11-06 | 2019-01-18 | 江苏三元环保科技有限公司 | A kind of environment-friendly type filter bag of doping vario-property starch and preparation method thereof |
| CN109608700A (en) * | 2018-11-29 | 2019-04-12 | 烟台八方文化传媒有限公司 | A kind of prepackaged food antibiotic packaging material and preparation method thereof |
| CN112341771A (en) * | 2019-08-09 | 2021-02-09 | 上海茵派化妆品有限公司 | Environment-friendly degradable mask packaging material and preparation method thereof |
| CN110845832A (en) * | 2019-10-21 | 2020-02-28 | 刘辉 | Biodegradable film for inner package of sanitary product |
| IT202200016212A1 (en) * | 2022-07-29 | 2024-01-29 | Planet Bioplastic S R L | POLYMERIC FORMULATIONS OF NATURALLY ORIGINATED HOT GLUES FOR APPLICATIONS SUCH AS COATINGS CONTAINING ACTIVE BIOMOLECULES |
| WO2024023795A1 (en) | 2022-07-29 | 2024-02-01 | Università Di Pisa | Hot-melt biobased polymeric formulations for coating applications containing active biomolecules |
| CN117551294A (en) * | 2024-01-11 | 2024-02-13 | 汕头市雅仕达包装材料有限公司 | High-strength PE film and preparation method thereof |
| CN117551294B (en) * | 2024-01-11 | 2024-03-22 | 汕头市雅仕达包装材料有限公司 | High-strength PE film and preparation method thereof |
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