CN1104656A - Biodegradable films and their production - Google Patents
Biodegradable films and their production Download PDFInfo
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- CN1104656A CN1104656A CN 93115307 CN93115307A CN1104656A CN 1104656 A CN1104656 A CN 1104656A CN 93115307 CN93115307 CN 93115307 CN 93115307 A CN93115307 A CN 93115307A CN 1104656 A CN1104656 A CN 1104656A
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Abstract
The fully biodegradable film use as ground-covering film or packing material is prepared with degradable components such as polyvinyl alcohol, starch, plasticizer, strengthening agent and modifier through blending reaction and doctor-blade casting process. The film has the same mechanical performance as polyethylene film and may be basically decomposed within one year.
Description
The present invention relates to film of a kind of fully biodegradable and preparation method thereof.
Seek degradable mulch film and wrapping material people, during the pollution of the plastic refuse that is on the rise with redemption, initial exploration is exactly biodegradable starch and organic acid to be incorporated in the common polyethylene film go.So the polyethylene type, poly-(the ethylene-acrylic acid)-polyethylene degradative membrane of starch one is come out one after another, but recent findings, and this class film only starch can be degraded, and polyethylene can not be by microbiological degradation, so this class film is lowered the temperature day by day.
U.S. F.H.Otey etc. has developed the film (Ind.Eng.Chem.Prod.Res.Dev.1980 of a kind of polyvinyl alcohol-starch-polyvinyl chloride type, 19,592-595), this film contains starch 60%, about polyvinyl alcohol 15%, polyvinyl chloride colloidal sol coated is improved the hydrophobic ability of film on polyvinyl alcohol-starch film, this film is under the situation of coated polyvinyl chloride not, almost there is not wet tenacity, and polyvinyl chloride be introduced in that people have a kind of guards psychological when the mulch film because the seedling rot phenomenon once took place in polyvinyl chloride when carrying out the mulch film breeding.Italy Ferruxxi company use the Biodegradable films that the modified polyvinyl alcohol of 70% modified starch and 30% prepares (MPI 1991, NO.9, P7), its degradation property is good, but price comparison is expensive.
The objective of the invention is to overcome biological degradation in the prior art insufficient, have side effects, shortcoming that price is high, and provide a kind of film at the short-term fully biodegradable and preparation method thereof.
The present invention realizes by following measure:
Prescription of the present invention contains polyvinyl alcohol, starch, softening agent, strengthening agent, properties-correcting agent, urea etc.It is support that the present invention adopts polyvinyl alcohol, as biodegradable inductor, and by degradation time and speed that its content in film comes controlling diaphragm, is aided with nutrients such as urea with starch, and adds softening agent and strengthening agent improves film strength and toughness.
Concrete prescription of the present invention contains (weight percentage):
Polyvinyl alcohol 40-75% starch 8-43%
Softening agent 6-20% strengthening agent 0-4%
Properties-correcting agent 0-16% urea 0-17%
Starch is the natural degradable polymer, but pure starch film insufficient strength; Polyvinyl alcohol has biodegradability, and can be used as soil improvement agent, film toughness, but price is more expensive; The common polythene mulch film not only can not be degraded, and is " poor film ", can't introduce nutrient, and starch and polyvinyl alcohol film then can be introduced nutrients such as urea as mulch film the time; Biodegradable films must possess certain wetting ability in order to degrade, but must have certain intensity in wet environment, in dried environment certain toughness is arranged, therefore must be at PVA, add an amount of softening agent and strengthening agent on the basis of starch.
The used plasticising material stuff of the present invention is a polyol, as glycerine, Triethylene glycol, polypropylene glycol etc.
The strengthening agent that the present invention adopts is gelatin, alginates, chitin etc.
The properties-correcting agent that the present invention selects for use is mainly organic acid and aldehydes, specifically is vinylformic acid, acetic acid, formaldehyde, acetaldehyde etc.
The present invention prepares by comprising following method:
Adding content earlier in polyvinyl alcohol is to be enough to make its moistening water, heating for dissolving, and heating makes material dissolution then; Add materials such as softening agent, strengthening agent, properties-correcting agent, urea, starch again 80-120 ℃ of following blend (gelatinization) reaction 5-30 minute; Stir evenly, filter the back 95 ± 5 ℃ of following film forming.Generally preferable with the casting method film forming.
Film of the present invention is when the 17-20 micron thickness, and mechanical property is: tensile strength>10MPa, extension at break>100%, straight iron tear strength>30KN/m.
The present invention can be used as degradable mulch and wrapping material.As mulch film the time, the insulation of this film, water retention is identical with common ground film or be better than common ground film, and the effect of increasing production of crop is better than common ground film usually, general amount of increase in production is at 20-30%, particularly to grape, can increase production 60%, every mu is increased production nearly 1600 jin, good economic benefits is arranged, and cost is comparatively cheap.It has the characteristic of complete biodegradable, can in 1 year, decompose substantially at the topped after date of plant growth through about about two months, and by changing starch content may command degradation time in the film.Overcome the common polythene mulch film and used the residual film in back to leave over the soil pollution environment, influenced crop root and grow, and then cause the shortcoming of crop failure, helped the benign cycle of farmland ecological environment.As degradable wrapping material (not adding urea), resemble feedbag, refuse bag, fast food lunch-box, have no side effect, its economic benefit is better, is a kind of rising biological degradation mould material.
Table 1 is that the mechanical property of dissimilar films compares:
Table 1
The mechanical property film type | Tensile strength (MPa) | Extension at break (%) | Thickness (μ) |
The present invention | 30.9 | 239 | 26 |
U.S.'s starch-poly-(ethylene-acrylic acid)-polyethylene film | 22.1 | 85 | 25 |
U.S.'s starch-poly-(ethylene-acrylic acid)-polyvinyl alcohol film | 23.2 | 40 | - |
English Country 3-hydroxybutyric acid-3-hydroxyl pentanoate copolymer (PHB) type film | 40.0 | 108 | 25 |
Table 2 is the comparison of Biodegradable films and common ground film production-increasing function:
The embodiment of the invention is:
Example 1: in the reactor of carrying vapour thermal jacket, add 59 parts of polyvinyl alcohol, it is an amount of to add water, and heating makes its dissolving then, add 10 parts of glycerine, 31 parts of potato starches reacted 10 minutes down at 85 ℃, so that starch pasting is filtered, to 95 ℃ of following drying and forming-films of casting machine.
Example 2: softening agent is selected 8 parts of polypropylene glycols for use, adds 1 part in gelatin, and 1 part in formaldehyde, other reaction conditionss react back film forming (90 ℃) with example 1.
Example 3:, in the opening reactor that band stirs, add 45 parts of polyvinyl alcohol and suitable quantity of water with the oil bath heating, heating for dissolving, add 15 parts, 1 part gelatin of Triethylene glycol, 15 parts, 25 parts potato starches of urea 80 ℃ of following gelatinizations 30 minutes, stir evenly, to casting machine film forming (90 ℃).
Example 4: with the oil bath heating, in the reactor that band stirs, add 50 parts of polyvinyl alcohol, add the water heating for dissolving, add 15 parts of acetic acid again, 8 parts of glycerine, 13 parts in urea.Stir evenly, add 15 parts of W-Gums again, at 100 ℃ of following gelatinization reactions 12 minutes, casting film-forming (95 ℃).
Example 5: with the oil bath heating, in the reactor that band stirs, add 60 parts of polyvinyl alcohol, 8 parts of glycerine, 32 parts of amylomaizes are at 100 ℃ of following gelatinization reactions 5 minutes, casting film-forming (95 ℃).
Example 6: in reactor, add 40 parts of polyvinyl alcohol and suitable quantity of water heating for dissolving, add 25 parts of 10 parts in vinylformic acid, 10 parts in urea, 15 parts of glycerine and W-Gums, made starch pasting 10 minutes at about 95 ℃, casting film-forming (95 ℃).
Example 7: in reactor, add 60 parts of polyvinyl alcohol and water heating for dissolving, add 15 parts in acetaldehyde, 10 parts, 15 parts potato starches of polypropylene glycol,, stir evenly casting film-forming (100 ℃) 98 ℃ of following gelatinizations 15 minutes.
Example 8: in the reactor of carrying vapour heating jacket, add 50 parts of polyvinyl alcohol and an amount of water, heating for dissolving, and then add 15 parts of glycerine, 15 parts in urea, starch are heated to 90 ℃ for 20 parts, and gelatinization 15 minutes is to 95 ℃ of following drying and forming-films of casting machine, rolling, packing.
Example 9: in the reactor of carrying vapour chuck, add 65 parts of polyvinyl alcohol and an amount of water, heating for dissolving, add 10 parts of glycerine again, 14 parts of 10 parts in urea and W-Gums, 1 part of sodium alginate were in 90 ℃ of following gelatinization reactions 25 minutes, stir evenly, to casting machine film forming (90 ℃), rolling.
Example 10: heat with oil bath, in the reactor that band stirs, add 60 parts of polyvinyl alcohol and water heating for dissolving, add two and contract 9 parts of three oxalic acids, 5 parts, 4 parts chitins of urea and 22 parts of potato starches in 95 ℃ of following gelatinization reactions 5 minutes, to casting machine film forming (100 ℃).
Example 11: get 20 parts of polyvinyl alcohol, 10 parts of high direct current W-Gums, 20 parts of glycerine, its preparation condition is with example 5, film forming.
Claims (6)
1, a kind of film of fully biodegradable, its prescription contains (weight percentage):
Polyvinyl alcohol 40-75% starch 8-43%
Softening agent 6-20% strengthening agent 0-4%
Properties-correcting agent 0-16% urea 0-17%
2,, it is characterized in that starch is W-Gum, potato starch or the amylomaize that makes through enzyme process as the said method of claim 1.
3,, it is characterized in that softening agent is glycerine, Triethylene glycol, polypropylene glycol as the said method of claim 1.
4,, it is characterized in that strengthening agent is gelatin, alginates, chitin as the said method of claim 1.
5,, it is characterized in that properties-correcting agent is vinylformic acid, acetic acid, formaldehyde, acetaldehyde as the said method of claim 1.
6, as the preparation method of the said Biodegradable films of claim 1, comprising:
A, in polyvinyl alcohol, add content and be enough to make its moistening water, heating for dissolving;
B, adding softening agent, strengthening agent, properties-correcting agent, urea, starch carry out blend (gelatinization) reaction;
C, stir evenly, filter the back film forming;
It is characterized in that temperature of reaction 80-120 ℃ of blend (gelatinization), reaction times 5-30 minute, 95 ± 5 ℃ of following film forming.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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CN 93115307 CN1104656A (en) | 1993-12-31 | 1993-12-31 | Biodegradable films and their production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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CN 93115307 CN1104656A (en) | 1993-12-31 | 1993-12-31 | Biodegradable films and their production |
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CN1104656A true CN1104656A (en) | 1995-07-05 |
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CN 93115307 Pending CN1104656A (en) | 1993-12-31 | 1993-12-31 | Biodegradable films and their production |
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Cited By (41)
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CN1090649C (en) * | 1996-05-10 | 2002-09-11 | 宁文芳 | Full degradation, non-pollution, leak-proof artificial plastic material and its manufacturing method |
CN1092219C (en) * | 1998-01-16 | 2002-10-09 | 田应官 | Farm land mulch filma nd preparation process thereof |
CN1129644C (en) * | 1999-06-30 | 2003-12-03 | 北京清大亚太科技研究中心 | Multiple degrading composition mother particle |
CN1294192C (en) * | 2002-12-30 | 2007-01-10 | 沈阳农业大学 | Manihot powder compound degradable material and its preparing method and use |
CN1297601C (en) * | 1998-09-30 | 2007-01-31 | 沃纳-兰伯特公司 | Modified starch film compositions |
WO2007033598A1 (en) * | 2005-09-21 | 2007-03-29 | Xiaolu Li | Water soluble biodegradable material |
CN1321794C (en) * | 2000-03-01 | 2007-06-20 | Pvaxx研究和开发有限公司 | Method and apparatus for blowmolding capsules of polyvinylalcohol and blowmolded polyvinylalcohol capsules |
CN101828495A (en) * | 2010-04-09 | 2010-09-15 | 常州百利基生物材料科技有限公司 | Biodegradable mulch with compound function |
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CN102295934A (en) * | 2011-07-01 | 2011-12-28 | 岳效国 | Liquid agricultural mulching film and production method thereof |
CN102558589A (en) * | 2012-01-20 | 2012-07-11 | 河南科技大学 | Preparation method of formaldehyde cross-linked gelatin/polyvinyl alcohol(PVA) composite membrane |
CN104004230A (en) * | 2014-06-10 | 2014-08-27 | 杨云 | Degradable mulching film and preparation method thereof |
CN104788217A (en) * | 2015-04-24 | 2015-07-22 | 合肥康龄养生科技有限公司 | Liquid fertilizer mulching film for increasing soil fertility for corn and preparation method of liquid fertilizer mulching film |
CN104788863A (en) * | 2015-03-31 | 2015-07-22 | 太仓市晨洲塑业有限公司 | Novel biodegradation plastic film |
CN104892997A (en) * | 2015-04-24 | 2015-09-09 | 安徽颍美彩印包装有限公司 | Tear resistant full degradable film and preparation method thereof |
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CN104892995A (en) * | 2015-04-24 | 2015-09-09 | 安徽颍美彩印包装有限公司 | Antibacterial type full degradable film and preparation method thereof |
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-
1993
- 1993-12-31 CN CN 93115307 patent/CN1104656A/en active Pending
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CN105001568A (en) * | 2015-07-01 | 2015-10-28 | 柳州蔚园塑料彩印包装有限责任公司 | Biodegradable mulch film and preparation method thereof |
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CN105713620A (en) * | 2016-01-25 | 2016-06-29 | 陈一坚 | Liquid fertilizer mulching film with high water retention and method for preparing liquid fertilizer mulching film |
CN107383436A (en) * | 2017-06-22 | 2017-11-24 | 陕西理工大学 | A kind of Biodegradable mulch |
CN107383724A (en) * | 2017-07-12 | 2017-11-24 | 马鞍山科信网络科技有限公司 | Degradable composite membrane that a kind of packaging material is blended with chitosan attapulgite and preparation method thereof |
CN107286547A (en) * | 2017-07-31 | 2017-10-24 | 海南大学 | A kind of preparation method of chitin liquefaction products/polyvinyl alcohol blending film |
CN107471694A (en) * | 2017-09-13 | 2017-12-15 | 安徽鼎正包装材料有限公司 | A kind of film forming preparation technology of PVA film |
CN107868285A (en) * | 2017-12-21 | 2018-04-03 | 苏州星火丰盈环保包装有限公司 | A kind of compound high intensity biodegradation refuse bag |
CN108329710A (en) * | 2018-01-10 | 2018-07-27 | 合肥盛鼎包装材料有限公司 | A kind of degradable packaging film |
CN110540725A (en) * | 2018-05-29 | 2019-12-06 | 合肥杰事杰新材料股份有限公司 | degradable halogen-free flame-retardant foaming material and preparation method thereof |
CN109836741A (en) * | 2019-02-26 | 2019-06-04 | 朱延朋 | A kind of preparation method of degradable mulch |
CN111303572A (en) * | 2020-05-10 | 2020-06-19 | 黑龙江省农业科学院土壤肥料与环境资源研究所 | Polyvinyl alcohol-based biodegradable agricultural environment-friendly mulching film |
US11505687B2 (en) | 2020-08-05 | 2022-11-22 | Nano And Advanced Materials Institute Limited | Environmentally degradable foamed master batch composition and using thereof |
CN112852172A (en) * | 2021-01-12 | 2021-05-28 | 陕西科技大学 | Full-biodegradable multi-crosslinked gelatin-based agricultural mulching film and preparation method thereof |
CN112852172B (en) * | 2021-01-12 | 2022-04-26 | 陕西科技大学 | Full-biodegradable multi-crosslinked gelatin-based agricultural mulching film and preparation method thereof |
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