CN104292479A - Preparation method of potato starch-based degradable plastic film - Google Patents
Preparation method of potato starch-based degradable plastic film Download PDFInfo
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- CN104292479A CN104292479A CN201410507965.XA CN201410507965A CN104292479A CN 104292479 A CN104292479 A CN 104292479A CN 201410507965 A CN201410507965 A CN 201410507965A CN 104292479 A CN104292479 A CN 104292479A
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Abstract
The invention discloses a preparation method of a potato starch-based degradable plastic film. The preparation method of the potato starch-based degradable plastic film comprises the following steps: mixing 60-80 parts of potato starch and 300-400 parts of deionized water to form a starch aqueous solution, and pasting at the temperature of 85-90 DEG C; at the temperature of 60-70 DEG C, adding 3-4 parts by weight of an initiating agent, stirring for 15 minutes, and then adding 120-180 parts of vinyl acetate and 8-12 parts of acrylic amide and reacting for 2-2.5 hours to obtain grafted copolymer emulsion; then adding 30-40 parts of a 10% poly(vinyl alcohol) solution and 10-20 parts of a 4% epoxy chloropropane solution into the grafted copolymer emulsion, reacting at the temperature of 60-70 DEG C for 1.5-2 hours, carrying out suction filtration at reduced pressure, and drying to obtain a solid mixture, carrying out hot melting extrusion-blown molding on the solid mixture by virtue of a single screw extrusion film blowing machine to obtain a plastic film, and finally cutting, carrying out roll dividing, and packaging. The prepared plastic film has good water resistance and biodegradability.
Description
Technical field
The present invention relates to biodegradable material technical field, especially a kind of the preparation method that modification obtains degradable plastic film is carried out to yam starch.
Background technology
Along with developing rapidly of plastics industry technology, increasing plastics bring the disaster being close to and destroying to environment; A large amount of plastic garbage abandoneds is in social environment, and manufactured " white pollution " has become the current various countries most thorny issue.But administer " white pollution " from consumption terminal to produce little effect, fundamentally will solve the problem of environmental pollution of plastic waste, just should replace the plastics of existing shape with the plastics can degraded, easily degrade.
Aliphatic polyester in degradable plastics and multipolymer thereof have good biodegradability properties and excellent mechanical strength, but its production cost is high, and therefore its practical application is restricted.
Starch-based polymer in degradable plastics is a kind of plastics of starch through modification, graft reaction post-treatment, has biodegradation rate fast, feature free from environmental pollution.It belongs to can thermoplastic processed-type plastics, can process with common plastics thermoplastic processing machine.Industrially the plastics such as polystyrene can be replaced.Product hardness can change according to the difference of percentage of grafting and after-processing technology, be current production cost closest to common plastics, the degradation material that market outlook are best.But it is quite responsive to humidity change, easily absorbs water, and after water suction, the mechanical property of goods obviously reduces, and therefore range of application is restricted.
Yam starch has abundance, low-cost advantage.Compared with cassava, corn and other starches, there is good film forming properties; There is very strong cohesiveness compared with the starch such as wheat, sweet potato; Yam starch also has the features such as thickening effectiveness is good, water-absorbent is strong, is therefore reacted by copolymerzation with cross-linking, can improve the shear ability of starch, strengthen its stability.Vinyl acetate (VAc), containing double bond, belongs to vinyl monomer, and it is water-soluble larger, there is good biodegradability, can with starch generation graft copolymerization, its multipolymer had both had the feature of starch size, had again the performance of synthetic slurry and biodegradable.More domestic researchists have made achievement at many starch as W-Gum, tapioca (flour) etc. are prepared in the research of macromolecular material with vinyl acetate graft copolymerization, successfully produce biodegradable and products such as tackiness agent of good performance, but it is very few to be directed to yam starch-vinyl acetate graft copolymerization aspect research.
Summary of the invention
Goal of the invention of the present invention is: for above-mentioned Problems existing, there is provided a kind of method of being produced plastics film by yam starch and vinyl acetate graft copolymerization, gained plastics film has that water tolerance is high, good mechanical properties, nontoxic, biodegradable advantage.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for yam starch base degradable plastic film, comprises the following steps:
(1) 60-80 part yam starch is added in a kettle. and 300-400 part deionized water is configured to amidin, gelatinization 30min at 85-90 DEG C of temperature;
(2) starch solution after gelatinization is cooled to 60-70 DEG C, adds 3-4 weight part initiator and stir 15min; Then slowly add 120-180 part vinyl acetate and 8-12 part acrylamide carries out graft copolymerization, controlling the joining day is that 2-2.5h obtains graft copolymer emulsion;
(3) in graft copolymer emulsion, adding 30-40 part mass concentration is the polyvinyl alcohol solution of 10%, and 10-20 part mass concentration is the epoxy chloropropane solution of 4%, obtains the graft starch mixed solution of crosslinking Treatment at 60-70 DEG C of reaction 1.5-2h;
(4) mixed solution that step (3) obtains is carried out decompress filter and carries out drying obtain solid mixture, gained is fixed mixture under 175 ~ 190 DEG C of processing temperatures, to carry out hot-melt extruded by Single screw extrusion inflation film manufacturing machine and be blow molded into plastic film, finally cuts, bundling packing.
Preferably, described initiator to be mass concentration be 10% ammonium persulphate or potassium persulfate solution.
Preferably, the compound method of described polyvinyl alcohol solution, for add deionized water in a reservoir, starts stirrer, then drops into polyvinyl alcohol, and the weight ratio of described polyvinyl alcohol and water is 1:9, is warming up to 90-95 DEG C of insulation reaction 1-1.5h, is cooled to room temperature and get final product.
Preferably, the polymerization degree >=1700 of selected polyvinyl alcohol, alcoholysis degree is 99%.Alcoholysis degree and the polymerization degree higher, then the tensile strength of film is larger, in graft copolymerization, play softening agent.
Preferably; vinyl acetate emulsion used is self-control; initiator is ammonium persulphate; protective colloid is polyvinyl alcohol, emulsifying agent is anionic emulsifier sodium lauryl sulphate and nonionic emulsifying agent tween-80 paralled system; reaction product oyster white; solid content 25% ~ 30%, viscosity 600 ~ 700mpas.
Here is that the present invention improves the mechanical property of yam starch base degradable plastic film and the principle of water tolerance:
Linking agent made by the preferred epoxy chloropropane of the present invention, epoxy chloropropane is a kind of ring-type oxygenatedchemicals, easily and graft starch molecule generation crosslinking reaction, make to be bonded to each other between chemical bond and form one cancellated high polymers seemingly, and make cross-linking set segment have better ductility, flexibility, therefore its mechanical property is better, and due to epoxy chloropropane crosslinking reaction mild condition, be easy to control, its chemical stability is high, gained cross-linking products is antiacid, alkali, anti-shearing effect stability higher.
The optimum temperature of reaction of making method of the present invention is 60 DEG C, when temperature is lower than 60 DEG C, initiator activity is not high, the Starch Free Radicals obtained thus is also few, the starch graft copolymer formed and the speed of linking agent generation crosslinking reaction slower, the reticulated structure formed is few, causes the tension intensity of material not high.When temperature is greater than 60 DEG C, can there are some homopolymerizations in graft copolymerization, and linking agent epoxy chloropropane has certain hydrolysis, and these are all unfavorable for crosslinking reaction, and tension intensity is reduced gradually.
The present invention also introduces the good amide group of water tolerance, between starch molecular chain, even importing combines firmly chemical bond in right amount, by the bonding force of these chemical bonds between molecular chain, its space side chain is more lengthened, also again the starch after grafting is cross-linked simultaneously, macromolecular starch molecule is made to form complicated space cross-linked three D structure, in structural adhesive layer with a small amount of chemical bond for core, a large amount of hydrogen bonds is aided with around each chemical bond, thus stop entering of water molecules, the structure of common formation treated starch water-resistant layer, its water tolerance is significantly strengthened.
The present invention carries out modification by specific composition and engineering to yam starch, improve its tensile strength, water tolerance, relative to existing plastics film technology, main formula composition of the present invention is yam starch, vinyl acetate, polyvinyl alcohol, and starch is biodegradable at occurring in nature.Vinyl acetate can be hydrolyzed under certain condition, and then can come out having the hydroxyl of certain hydrophilicity, and in physical environment, this hydroxyl can play hydrophilic interaction, merges very well with environment, the degradation property shown.And polyvinyl alcohol can be decomposed by hydrolysis and biological degradation two kinds of approach at nature, final degradation production is H
2o and CO
2, its water solubles is colourless, tasteless, nontoxic, harmless, infiltrates soil and also can be used as soil improvement agent, revolutionize conventional plastic wrapping material and existing degradable package material to the destruction of environment and impact; Applied range of the present invention, can be used for the changing food waste bag of refuse classification and biogas/compost treatment, the shopping bag requiring complete biodegradable, dried food and nuts packing bag, book and newpaper bag, bullshit bag, clothes and industrial packaging material etc.
Embodiment
By the following examples, the invention will be further described:
Comparative example 1
The starch plastics film of this comparative example, its preparation process is as follows:
The yam starch of 80 weight parts and 400 parts of deionized waters are configured to amidin, gelatinization 30min at 85-90 DEG C of temperature; Starch solution after gelatinization is cooled to 60-70 DEG C, and adding 30 parts of mass concentrations is the polyvinyl alcohol solution of 10%, and 10 parts of mass concentrations are the epoxy chloropropane solution of 4%, obtains the graft starch mixed solution of crosslinking Treatment at 60-70 DEG C of reaction 1.5h; The mixed solution obtained is carried out decompress filter and carries out drying obtaining solid mixture, gained is fixed mixture and under 175 DEG C of processing temperatures, carry out hot-melt extruded by Single screw extrusion inflation film manufacturing machine and be blow molded into plastic film, finally cut, bundling packing.
Wherein the compound method of polyvinyl alcohol solution is identical with embodiment 2 with embodiment 1.
Embodiment 1
Aqueous polyvinyl acetate emulsion is got out in advance: the initiator preparing vinyl acetate emulsion employing is ammonium persulphate, and protective colloid is polyvinyl alcohol, emulsifying agent is anionic emulsifier sodium lauryl sulphate and nonionic emulsifying agent tween-80 paralled system according to method of the present invention.Stir while react obtained and be creamy white at the temperature of 70-80 DEG C, solid content 25% ~ 30%, the product of viscosity 600 ~ 700mpas.
Polyvinyl alcohol solution is got out in advance: add deionized water in a reservoir according to the inventive method, start stirrer, dropping into the polymerization degree is again 1700, alcoholysis degree is the polyvinyl alcohol of 99%, the weight ratio of described polyvinyl alcohol and water is 1:9, be warming up to 90-95 DEG C of insulation reaction 1h, be cooled to room temperature and get final product.
The detailed process preparing yam starch base degradable plastic film is: add 60 parts of yam starchs in a kettle. and 300 parts of deionized waters are configured to amidin, gelatinization 30min at 85-90 DEG C of temperature; Starch solution after gelatinization is cooled to 60-70 DEG C, and adding 3 parts of mass concentrations is the ammonium persulphate of 10%, stirs 15min; Then slowly add 120 parts of vinyl acetates and 8 parts of acrylamides carry out graft copolymerization, controlling the joining day is 2 obtain graft copolymer emulsion; In graft copolymer emulsion, add 30 parts of mass concentrations is the polyvinyl alcohol solution of 10%, and 10 parts of mass concentrations are the epoxy chloropropane solution of 4%, 60-70 DEG C of reaction 1.5 the graft starch mixed solution of crosslinking Treatment; The mixed solution obtained is carried out decompress filter and carries out drying obtaining solid mixture, gained is fixed mixture and under 175 DEG C of processing temperatures, carry out hot-melt extruded by Single screw extrusion inflation film manufacturing machine and be blow molded into plastic film, finally cut, bundling packing.
Embodiment 2
Aqueous polyvinyl acetate emulsion is got out in advance: the initiator preparing vinyl acetate emulsion employing is ammonium persulphate, and protective colloid is polyvinyl alcohol, emulsifying agent is anionic emulsifier sodium lauryl sulphate and nonionic emulsifying agent tween-80 paralled system according to method of the present invention.Stir while react obtained and be creamy white at the temperature of 70-80 DEG C, solid content 25% ~ 30%, the product of viscosity 600 ~ 700mpas.
Polyvinyl alcohol solution is got out in advance: add deionized water in a reservoir according to the inventive method, start stirrer, drop into polymerization degree > 1700 again, alcoholysis degree is the polyvinyl alcohol of 99%, the weight ratio of described polyvinyl alcohol and water is 1:9, be warming up to 90-95 DEG C of insulation reaction 1.5h, be cooled to room temperature and get final product.
The detailed process preparing yam starch base degradable plastic film is: add 80 parts of yam starchs in a kettle. and 400 parts of deionized waters are configured to amidin, gelatinization 30min at 85-90 DEG C of temperature; Starch solution after gelatinization is cooled to 60-70 DEG C, add 4 parts of mass concentrations be 10% Potassium Persulphate easily stir 15min; Then slowly add 180 parts of vinyl acetates and 12 parts of acrylamides carry out graft copolymerization, controlling the joining day is that 2.5h obtains graft copolymer emulsion; In graft copolymer emulsion, add 40 parts of mass concentrations is the polyvinyl alcohol solution of 10%, and 20 parts of mass concentrations are the epoxy chloropropane solution of 4%, obtains the graft starch mixed solution of crosslinking Treatment at 60-70 DEG C of reaction 2h; The mixed solution obtained is carried out decompress filter and carries out drying obtaining solid mixture, gained is fixed mixture and under 190 DEG C of processing temperatures, carry out hot-melt extruded by Single screw extrusion inflation film manufacturing machine and be blow molded into plastic film, finally cut, bundling packing.
Embodiment 3 performance test
Respectively stretch capability and water resistance test are done to the plastics film obtained by embodiment 1 and 2:
(1) water resistance test
Water tolerance is reacted by the water-intake rate of plastics film, the lower water tolerance of water-intake rate is better, and the testing method of water-intake rate is: clip is of a size of the sample of 50cm × 50cm size, is weighed as m1, soak 24h under being placed in clean tap water normal temperature, sample taking-up filter paper is dried and is weighed as m2.Each testing sample gets 3 sample measurements, results averaged.The calculation formula of water-intake rate η is:
(2) stretch capability test
Adopt GB/T 1040-1992 plastic tensile performance test method, the tension intensity of test material.The experimental principle of this method is that detected sample is used specific cutting machine, cuts into the little bar of same width, by the specimen holder that cuts on tension testing machine, with constant speed tensile, until during sample breakage, and the power that sample can bear.
Comparative example 1, water-absorbent and the stretch capability test result of embodiment 1 and 2 are as shown in table 1:
Table 1 the performance test results
| ? | Comparative example 1 | Embodiment 1 | Embodiment 2 |
| Water-intake rate | 100.48 | 29.3 | 28.6 |
| Tensile strength N/mm | 43.2 | 87.6 | 90.3 |
As can be seen from test result, the present invention by carrying out graft copolymerization by starch and vinyl acetate between to for plastic, acrylamide under appropriate initiator effect, greatly can improve water resistance and the tensile strength of starch plastics film, thus solve traditional starch plastics goods to humidity sensitive, easily inhale water problem.
Embodiment 4 degradation capability is tested
Degradation property test is carried out according to GB/T 20197-2006, and it the results are shown in Table 2.
Table 2 degradation capability test result
As can be seen from the data of degradation experiment, along with the prolongation of degradation time, degradation rate increases gradually, and during 30 to 180 days, degradation rate increases obviously, reaches the rate of weight loss of nearly 41.1% at about 180 days.
Claims (5)
1. a preparation method for yam starch base degradable plastic film, is characterized in that comprising the following steps:
(1) 60-80 part yam starch is added in a kettle. and 300-400 part deionized water is configured to amidin, gelatinization 30min at 85-90 DEG C of temperature;
(2) starch solution after gelatinization is cooled to 60-70 DEG C, adds 3-4 weight part initiator and stir 15min; Then slowly add 120-180 part vinyl acetate and 8-12 part acrylamide carries out graft copolymerization, controlling the joining day is that 2-2.5h obtains graft copolymer emulsion;
(3) in graft copolymer emulsion, adding 30-40 part mass concentration is the polyvinyl alcohol solution of 10%, and 10-20 part mass concentration is the epoxy chloropropane solution of 4%, obtains the graft starch mixed solution of crosslinking Treatment at 60-70 DEG C of reaction 1.5-2h;
(4) mixed solution that step (3) obtains is carried out decompress filter and carries out drying obtain solid mixture, gained is fixed mixture under 175 ~ 190 DEG C of processing temperatures, to carry out hot-melt extruded by Single screw extrusion inflation film manufacturing machine and be blow molded into plastic film, finally cuts, bundling packing.
2. the preparation method of a kind of yam starch base degradable plastic film according to claim 1, is characterized in that: described initiator to be mass concentration be 10% ammonium persulphate or potassium persulfate solution.
3. the preparation method of a kind of yam starch base degradable plastic film according to claim 2, it is characterized in that: the compound method of described polyvinyl alcohol solution is for add deionized water in a reservoir, start stirrer, drop into polyvinyl alcohol again, the weight ratio of described polyvinyl alcohol and water is 1:9, be warming up to 90-95 DEG C of insulation reaction 1-1.5h, be cooled to room temperature and get final product.
4. the preparation method of a kind of yam starch base degradable plastic film according to claim 3, it is characterized in that: the polymerization degree >=1700 of selected polyvinyl alcohol, alcoholysis degree is 97%.
5. the preparation method of a kind of yam starch base degradable plastic film according to claim 4; it is characterized in that: the initiator that the preparation of vinyl acetate used adopts is ammonium persulphate; protective colloid is polyvinyl alcohol; emulsifying agent is anionic emulsifier sodium lauryl sulphate and nonionic emulsifying agent tween-80 paralled system; temperature of reaction is 75 DEG C; reaction product oyster white, solid content 25% ~ 30%, viscosity 600 ~ 700mpas.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104893009A (en) * | 2015-06-26 | 2015-09-09 | 江南大学 | Starch-based composite and preparation method thereof |
| CN105885111A (en) * | 2016-05-30 | 2016-08-24 | 蚌埠市维光塑胶制品有限公司 | Plastic bag easy to degrade |
| CN106243407A (en) * | 2016-07-28 | 2016-12-21 | 马鞍山市五谷禽业专业合作社 | A kind of degradable starch based agricultural mulching film adding bamboo fibre |
| CN107189310A (en) * | 2017-05-23 | 2017-09-22 | 界首市海钰塑化有限公司 | A kind of degradable photosensitive colour-changing packing rope preparation technology of high tenacity |
| CN107522939A (en) * | 2017-10-13 | 2017-12-29 | 安徽嘉美包装有限公司 | A kind of environment friendly non-halogen plastic bag material and preparation method thereof |
| CN107540926A (en) * | 2017-10-13 | 2018-01-05 | 安徽嘉美包装有限公司 | A kind of inexpensive toughened plastics bag material and preparation method thereof |
| 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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| CN102167647A (en) * | 2011-05-09 | 2011-08-31 | 湖北富邦科技股份有限公司 | Degradable composite coating material and preparation method and application thereof in controlled release fertilizer |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102167647A (en) * | 2011-05-09 | 2011-08-31 | 湖北富邦科技股份有限公司 | Degradable composite coating material and preparation method and application thereof in controlled release fertilizer |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104893009A (en) * | 2015-06-26 | 2015-09-09 | 江南大学 | Starch-based composite and preparation method thereof |
| CN104893009B (en) * | 2015-06-26 | 2019-03-08 | 江南大学 | A kind of starch-based composite material and preparation method |
| CN105885111A (en) * | 2016-05-30 | 2016-08-24 | 蚌埠市维光塑胶制品有限公司 | Plastic bag easy to degrade |
| CN106243407A (en) * | 2016-07-28 | 2016-12-21 | 马鞍山市五谷禽业专业合作社 | A kind of degradable starch based agricultural mulching film adding bamboo fibre |
| CN107189310A (en) * | 2017-05-23 | 2017-09-22 | 界首市海钰塑化有限公司 | A kind of degradable photosensitive colour-changing packing rope preparation technology of high tenacity |
| CN107522939A (en) * | 2017-10-13 | 2017-12-29 | 安徽嘉美包装有限公司 | A kind of environment friendly non-halogen plastic bag material and preparation method thereof |
| CN107540926A (en) * | 2017-10-13 | 2018-01-05 | 安徽嘉美包装有限公司 | A kind of inexpensive toughened plastics bag material and preparation method thereof |
| 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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