CN101143936B - Preparation method for completely biodegraded high amylose starches base thin film - Google Patents
Preparation method for completely biodegraded high amylose starches base thin film Download PDFInfo
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- CN101143936B CN101143936B CN200710072749A CN200710072749A CN101143936B CN 101143936 B CN101143936 B CN 101143936B CN 200710072749 A CN200710072749 A CN 200710072749A CN 200710072749 A CN200710072749 A CN 200710072749A CN 101143936 B CN101143936 B CN 101143936B
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Abstract
The invention relates to a preparation method of a fully biodegraded high-amylose based film. The invention resolves the problem that the present plastic film cannot be fully biodegraded. The preparation method of the fully biodegraded high-amylose based film includes following steps: (1) Gelatinization; (2) Blending; (3) Plasticization and Crosslinking; (4) Degasification and Drying, and the fully biodegraded high-amylose based film can be obtained by the preparation method. The products produced by the invention are characterized in safety, nontoxicity, full biodegradation, etc., thus having good use performance and degradation performance.
Description
Technical field
That the present invention relates to is a kind of preparation method of film of energy complete biodegradable.
Background technology
Plastics are since coming out last century, because of it has characteristics such as proportion is little, production technique is simple, product category is various, both artistic and practical, be penetrated into every field such as industry, agricultural, national defence and daily life, by volume calculated, plastics have become the material of output and consumption maximum.When plastics were widely used, its existing problem also manifested day by day.On the one hand because the plastics stable performance, generally can not die away at short notice, and because plastic prod uses the back recovery difficult big, the processing cost height, the waste accumulating rate is fast, become the major reason of contaminate environment, serious threat becomes worldwide public hazards day by day to human and vegeto-animal living environment.On the other hand, the starting material of most plastic prods derive from petrochemical complex, and oil is a kind of Nonrenewable resources.Therefore, especially be that the biodegradable plastic of raw material has become the hot fields that competitively research and develop countries in the world with natural polymer with starch.
China is started in the photodegradable plastics film of the seventies in 20th century to the research of degradable plastic film, and the emphasis of research and development is photodegradation, calcium carbonate-filled photodegradation and starch filled plastic film, but the said products all can not be degraded fully.Developing focus to degradation plastic film shifts to the full biodegradation plastic film field at present.
Summary of the invention
The objective of the invention is to solve the problem that present plastics film can not complete biodegradable, and a kind of preparation method of high amylose starches base thin film of complete biodegradable is provided.
A kind of high amylose starches base thin film of complete biodegradable is to be prepared as follows: one, be 13%～17% starch milk with high amylose starch water furnishing mass concentration, regulating starch milk pH value with the sodium hydroxide of 0.3～0.5mol/L again is 8.5～9.5, then starch milk is heated to 90 ℃～110 ℃, gelatinization 20～40min under the stirring velocity of 300～400r/min; Two, with mass concentration be 7%～9% polyvinyl alcohol water solution, with the starch milk blend, wherein the mass ratio of polyvinyl alcohol and high amylose starch is 4: 6 under 100～140r/min stirring velocity; Three, adding mass concentration again is 15～30% aqueous glycerin solution, plasticizing reaction 20～40min under 100～105 ℃ condition, qualities of glycerin is 20% of starch and a polyvinyl alcohol gross weight, cool the temperature to 85 ℃～90 ℃ then, pH value with the hydrochloric acid regulation system of 0.5～1mol/L is 2～5, drip oxalic dialdehyde crosslinking reaction 30～50min, the oxalic dialdehyde quality is 10% of starch and a polyvinyl alcohol gross weight, add water tolerance auxiliary agent urea reaction 15～25min of 2% of starch and polyvinyl alcohol gross weight, form film liquid; Four, with film liquid vacuum outgas 10～20min, vacuum tightness is 0.06～0.09MPa, again with film liquid curtain coating in the synthetic glass mould, after under 60 ℃～80 ℃ the condition dry 3～5 hours, take off film; Promptly obtain the high amylose starches base thin film of complete biodegradable.
The amylose content of amylomaize of the present invention is 80%～82%.Drip glyoxal water solution and be in order to allow oxalic dialdehyde fully react, participate in crosslinkedly fully, the vacuum outgas of film liquid is the bubble of introducing in the whipping process in order to remove.
The product that the present invention produced, through scanning electron microscopic observation, the section structure densification also has the space reticulated structure; Has certain crystalline texture through X-ray diffraction analysis; It is stable to analyze its thermal characteristics through differential scanning calorimeter, can normally use under 50 ℃; Through Infrared spectroscopy, the linking agent oxalic dialdehyde has participated in crosslinking reaction fully and not have surplus remaining, the monomer auxiliary agent can not take place in use separate out.Simultaneously other auxiliary agents of the present invention are material nontoxic and can complete biodegradable, feature such as have free from environmental pollution, safety non-toxic when therefore product uses as various wrapping material, can degrade fully, its use properties has reached the conventional polyolefins plastics film and apparently higher than common starch base degradable film, its biodegradability obviously is better than employed environmental protection type packing material in the present large supermarket.The various performances of measuring product are as follows: tensile strength 32.8MPa, elongation at break 135%, transmittance 42.1%, water-intake rate 41.7%, oil absorbency 0%, normal temperature, soil pH value be under 7.5～8.5 the condition degraded in the time of 50 days rate of weight loss can reach 68.2%, 70～90 days and can degrade fully.The present invention has widened the raw material range of preparation complete biodegradable film, and product has good use properties and degradation property.
Embodiment
Embodiment one: the high amylose starches base thin film of a kind of complete biodegradable of present embodiment be prepared one as follows, be 13%～17% starch milk with high amylose starch water furnishing mass concentration, regulating starch milk pH value with the sodium hydroxide of 0.3～0.5mol/L again is 8.5～9.5, then starch milk is heated to 90 ℃～110 ℃, gelatinization 20～40min under the stirring velocity of 300～400r/min; Two, with mass concentration be 7%～9% polyvinyl alcohol water solution, with the starch milk blend, wherein the mass ratio of polyvinyl alcohol and high amylose starch is 4: 6 under 100～140r/min stirring velocity; Three, adding mass concentration again is 15～30% aqueous glycerin solution, plasticizing reaction 20～40min under 100～105 ℃ condition, qualities of glycerin is 20% of starch and a polyvinyl alcohol gross weight, cool the temperature to 85 ℃～90 ℃ then, pH value with the hydrochloric acid regulation system of 0.5～1mol/L is 2～5, drip oxalic dialdehyde crosslinking reaction 30～50min, the oxalic dialdehyde quality is 10% of starch and a polyvinyl alcohol gross weight, add water tolerance auxiliary agent urea reaction 15～25min of 2% of starch and polyvinyl alcohol gross weight, form film liquid; Four, with film liquid vacuum outgas 10～20min, vacuum tightness is 0.06～0.09MPa, again with film liquid curtain coating in the synthetic glass mould, after under 60 ℃～80 ℃ the condition dry 3～5 hours, take off film; Promptly obtain the high amylose starches base thin film of complete biodegradable.
Embodiment two: the difference of present embodiment and embodiment one is: with the starch milk of high amylose starch water furnishing 14%～16%, regulating starch milk pH value with the sodium hydroxide of 0.4mol/L again is 9.0 in the step 1.Other step and parameter are identical with embodiment one.
Embodiment three: the difference of present embodiment and embodiment one is: in the step 1 with the starch milk of high amylose starch water furnishing 15%.Other step and parameter are identical with embodiment one.
Embodiment four: the difference of present embodiment and embodiment one is: in the step 1 starch milk is heated to 95 ℃～105 ℃, gelatinization 25～35min under the stirring velocity of 320～380r/min.Other step and parameter are identical with embodiment one.
Embodiment five: the difference of present embodiment and embodiment one is: in the step 1 starch milk is heated to 100 ℃, gelatinization 30min under the stirring velocity of 350r/min.Other step and parameter are identical with embodiment one.
Embodiment six: the difference of present embodiment and embodiment one is: in the step 2 be 8% polyvinyl alcohol water solution with mass concentration, under the stirring velocity of 120r/min with the starch milk blend.Other step and parameter are identical with embodiment one.
In the present embodiment polyvinyl alcohol is put into the water heating for dissolving and form transparent liquid.
Embodiment seven: the difference of present embodiment and embodiment one is: adding mass concentration in the step 3 is 20% aqueous glycerin solution plasticizing reaction 30min under 102 ℃ condition.Other step and parameter are identical with embodiment one.
Embodiment eight: the difference of present embodiment and embodiment one is: cooling the temperature to 88 ℃ in the step 3, is 2～3 with the pH value of 0.9mol/L hydrochloric acid regulation system.Other step and parameter are identical with embodiment one.
Embodiment nine: the difference of present embodiment and embodiment one is: the pH value with 0.8mol/L hydrochloric acid regulation system in the step 3 is 2.5.Other step and parameter are identical with embodiment one.
Embodiment ten: the difference of present embodiment and embodiment one is: drip oxalic dialdehyde crosslinking reaction 35～45min in the step 3.Other step and parameter are identical with embodiment one.
Embodiment 11: the difference of present embodiment and embodiment one is: drip oxalic dialdehyde crosslinking reaction 40min in the step 3.Other step and parameter are identical with embodiment one.
Embodiment 12: the difference of present embodiment and embodiment one is: add water tolerance auxiliary agent urea reaction 20min in the step 3.Other step and parameter are identical with embodiment one.
Embodiment 13: the difference of present embodiment and embodiment one is: with film liquid vacuum outgas 14～16min, vacuum tightness is 0.07～0.08MPa in the step 4.Other step and parameter are identical with embodiment one.
Embodiment 14: the difference of present embodiment and embodiment one is: with film liquid vacuum outgas 15min, vacuum tightness is 0.075MPa in the step 4.Other step and parameter are identical with embodiment one.
Embodiment 15: the difference of present embodiment and embodiment one is: dry under 65 ℃～75 ℃ condition in the step 4.Other step and parameter are identical with embodiment one.
Embodiment 16: the difference of present embodiment and embodiment one is: in the step 4 under 70 ℃ condition dry 4 hours.Other step and parameter are identical with embodiment one.
Embodiment 17: the difference of present embodiment and embodiment one is: the dropping mass concentration is 30% glyoxal water solution in the step 3.Other step and parameter are identical with embodiment one.
Embodiment 18: the high amylose starches base thin film of a kind of complete biodegradable of present embodiment is to be prepared as follows: one, be 15% starch milk with high amylose starch water furnishing mass concentration, regulating starch milk pH value with the sodium hydroxide of 0.5mol/L again is 9, starch milk is heated to 100 ℃ then, gelatinization 30min under the stirring velocity of 350r/min; Two, with mass concentration be 8% transparent polyethylene alcohol solution, with the starch milk blend, wherein the mass ratio of polyvinyl alcohol and high amylose starch is 4: 6 under the stirring velocity of 120r/min; Three, adding mass concentration again is 20% aqueous glycerin solution plasticizing reaction 30min, qualities of glycerin is 20% of starch and a polyvinyl alcohol butt gross weight, cool the temperature to 90 ℃ then, pH value with the hydrochloric acid regulation system of 1mol/L is 2, dripping mass concentration again is 30% glyoxal water solution crosslinking reaction 40min, the oxalic dialdehyde quality is 10% of starch and a polyvinyl alcohol butt gross weight, add 2% water tolerance auxiliary agent urea reaction 20min of starch and polyvinyl alcohol butt gross weight, form film liquid; Four, with film liquid vacuum outgas 15min, vacuum tightness is 0.08MPa, again with film liquid curtain coating in the synthetic glass mould, after under 70 ℃ the condition dry 4 hours, take off film; Promptly obtain a kind of high amylose starches base thin film of complete biodegradable.
It is as follows that the high amylose starches base thin film of the prepared complete biodegradable of present embodiment is measured its various performances: tensile strength 32.8MPa, elongation at break 135%, transmittance 42.1%, water-intake rate 41.7%, oil absorbency 0%, at normal temperature, soil pH value is degraded rate of weight loss degraded fully that can reach 68.2%, 85 day in the time of 50 days under 7.5～8.5 the condition.
Claims (10)
1. the preparation method of the high amylose starches base thin film of a complete biodegradable, the high amylose starches base thin film that it is characterized in that a kind of complete biodegradable is to be prepared as follows: one, be 13%～17% starch milk with high amylose starch water furnishing mass concentration, regulating starch milk pH value with the sodium hydroxide of 0.3～0.5mol/L again is 8.5～9.5, then starch milk is heated to 90 ℃～110 ℃, gelatinization 20～40min under the stirring velocity of 300～400r/min; Two, with mass concentration be 7%～9% polyvinyl alcohol water solution, with the starch milk blend, wherein the mass ratio of polyvinyl alcohol and high amylose starch is 4: 6 under 100～140r/min stirring velocity; Three, adding mass concentration again is 15～30% aqueous glycerin solution, plasticizing reaction 20～40min under 100～105 ℃ condition, qualities of glycerin is 20% of starch and a polyvinyl alcohol gross weight, cool the temperature to 85 ℃～90 ℃ then, pH value with the hydrochloric acid regulation system of 0.5～1mol/L is 2～5, drip oxalic dialdehyde crosslinking reaction 30～50min, the oxalic dialdehyde quality is 10% of starch and a polyvinyl alcohol gross weight, add water tolerance auxiliary agent urea reaction 15～25min of 2% of starch and polyvinyl alcohol gross weight, form film liquid; Four, with film liquid vacuum outgas 10～20min, vacuum tightness is 0.06～0.09MPa, again with film liquid curtain coating in the synthetic glass mould, after under 60 ℃～80 ℃ the condition dry 3～5 hours, take off film; Promptly obtain the high amylose starches base thin film of complete biodegradable; High amylose starch is an amylomaize in the step 1, and wherein amylose content is 80%～82%.
2. the preparation method of the high amylose starches base thin film of a kind of complete biodegradable according to claim 1, it is characterized in that in the step 1 starch milk with high amylose starch water furnishing 14%～16%, regulating starch milk pH value with the sodium hydroxide of 0.4mol/L again is 9.0.
3. the preparation method of the high amylose starches base thin film of a kind of complete biodegradable according to claim 1 is characterized in that in the step 1 starch milk being heated to 95 ℃～105 ℃, gelatinization 25～35min under the stirring velocity of 320～380r/min.
4. the preparation method of the high amylose starches base thin film of a kind of complete biodegradable according to claim 1 is characterized in that in the step 2 with mass concentration being 8% polyvinyl alcohol water solution, under the stirring velocity of 120r/min with the starch milk blend.
5. the preparation method of the high amylose starches base thin film of a kind of complete biodegradable according to claim 1 is characterized in that adding mass concentration in the step 3 is 20% aqueous glycerin solution plasticizing reaction 30min under 102 ℃ condition.
6. the preparation method of the high amylose starches base thin film of a kind of complete biodegradable according to claim 1 is characterized in that cooling the temperature in the step 3 88 ℃, is 2～3 with the pH value of 0.9mol/L hydrochloric acid regulation system.
7. the preparation method of the high amylose starches base thin film of a kind of complete biodegradable according to claim 1 is characterized in that dripping in the step 3 oxalic dialdehyde crosslinking reaction 35～45min.
8. the preparation method of the high amylose starches base thin film of a kind of complete biodegradable according to claim 1 is characterized in that adding in the step 3 water tolerance auxiliary agent urea reaction 20min.
9. the preparation method of the high amylose starches base thin film of a kind of complete biodegradable according to claim 1 is characterized in that in the step 4 that with film liquid vacuum outgas 14～16min, vacuum tightness is 0.07～0.08MPa.
10. the preparation method of the high amylose starches base thin film of a kind of complete biodegradable according to claim 1 is characterized in that in the step 4 dry under 65 ℃～75 ℃ condition.
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| CN200710072749A CN101143936B (en) | 2007-09-05 | 2007-09-05 | Preparation method for completely biodegraded high amylose starches base thin film |
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| CN200710072749A CN101143936B (en) | 2007-09-05 | 2007-09-05 | Preparation method for completely biodegraded high amylose starches base thin film |
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| CN101143936B true CN101143936B (en) | 2010-05-26 |
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Families Citing this family (11)
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| CN101353430B (en) * | 2008-07-15 | 2011-03-30 | 中山大学 | Method for preparing amylose water solution |
| CN101886356B (en) * | 2010-07-16 | 2011-09-07 | 江南大学 | Preparation method for bacteriostatic starch packaging paper |
| CN102924614B (en) * | 2012-11-15 | 2015-08-26 | 中国农业大学 | A kind of High amylase corn starch paste and preparation method thereof |
| CN103254454A (en) * | 2013-05-14 | 2013-08-21 | 桂林电子科技大学 | Method for preparing synthetic macromolecular reinforcement modified starch film through utilizing tape casting method |
| CN104098792A (en) * | 2014-06-30 | 2014-10-15 | 安徽巢湖南方膜业有限责任公司 | Corn starch degradable plastic film and preparation method thereof |
| CN104893221A (en) * | 2015-05-22 | 2015-09-09 | 铜陵方正塑业科技有限公司 | Wood pulp cellulose modified full-degradable plastics film and preparation method thereof |
| CN106317470A (en) * | 2015-06-19 | 2017-01-11 | 大连瑞贤达塑胶有限公司 | Method for preparing high-strength starch-based completely biodegraded plastic film by solution blending method |
| CN104974398B (en) * | 2015-07-01 | 2017-04-12 | 柳州蔚园塑料彩印包装有限责任公司 | Mulching film degraded via light-microorganism synergetic degradation, and preparation method thereof |
| CN105001568B (en) * | 2015-07-01 | 2017-12-12 | 柳州蔚园塑料彩印包装有限责任公司 | A kind of degradable mulch and preparation method thereof |
| CN107254130B (en) * | 2017-07-03 | 2018-06-29 | 界首市菁华科技信息咨询服务有限公司 | A kind of degradable agricultural film |
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