CN1405230A - Hydrolytic biodegradable plastic shaping material and preparation method thereof - Google Patents
Hydrolytic biodegradable plastic shaping material and preparation method thereof Download PDFInfo
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- CN1405230A CN1405230A CN 01131081 CN01131081A CN1405230A CN 1405230 A CN1405230 A CN 1405230A CN 01131081 CN01131081 CN 01131081 CN 01131081 A CN01131081 A CN 01131081A CN 1405230 A CN1405230 A CN 1405230A
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Abstract
There is a kind of plastic molding materials which is absolute water soluble, without contamination, and can be degraded biologically in short term, the weight proportion of this material is: poval 40-80 shares, propyl triaocohol 6-30 shares, dipept diethanol 1-10 shares, shanli alcohol 1-20 shares, borax 0-2 shares, formaldehyde 0-1 shares.
Description
The present invention relates to plastic shaping material of a kind of hydrolytic biodegradable and preparation method thereof, especially a kind of water-soluble hydrolytic biodegradable plastics film that can be water-soluble fully and preparation method thereof.
Because " white pollution " serious day by day, people is seeking always can natural degradation plastics film, with the pollution problem of solution environment.At present, adopt starch filled mode to prepare degradable polyolefin film in the prior art mostly.But found in recent years that this type of film only was that wherein contained starch can be degraded, and polyolefine can only be broken, can not degrade, so this so-called degradable film still can not be got rid of the pollution that soil and the mankind and animals and plants living environment are caused.Therefore, the application of this class degradable polyolefin film is lowered the temperature already.
The nineties later stage, the scholar of states such as the U.S., Japan, Italy is just making great efforts to seek, develop the latest generation plastics film, its concrete thinking is: this ideal plastics film should be able to be water-soluble earlier, join then in the systemic circulation of nature biotechnology chain, in the biologic chain systemic circulation, can be hydrolyzed and natural degradation.This ideal film article is made with water-soluble high-molecular material, after these goods such as packing bag, food bag etc. use and discard, it can be abandoned in outdoor, through rain drop erosion several times, these goods just can dissolve fully, and flow away with rainwater, go thereby join in the systemic circulation of whole biology, natural degradation finally is hydrolyzed.This type of research at present is detected in abroad, and domestic almost do not have to report.
Described a kind of Biodegradable high-molecular film and manufacture method and purposes in the disclosed CN1048221A of Chinese patent application, wherein this polymeric composition is made up of starch, polyvinyl alcohol, polyoxyethylene glycol, polyvalent alcohol organic aldehyde compound, urea, ammonium chloride; The casting method manufacturing of its film article can be used for the mulch film of mulch farming thing or the base material of agricultural medicine film, is characterized in: this film can break and biodegrade after using as mulch film voluntarily; The physical and mechanical properties of film is near the performance index of agricultural polyethylene film; Film also has good hydrophilicity except that biodegradable, but moisture absorption and light transmission.But this biodegradable film can not be dissolved in the lower water of temperature at short notice fully, thereby can't add smoothly in the systemic circulation of organic sphere, is not the ideal product of our desired acquisition.
A kind of water-soluble biodegradable films is disclosed in european patent application disclosed series of patents application EP0546538A and EP0545278A, comprise chemical modification or unmodified amylose starch or starch, wherein these films of being obtained of invention can be partially soluble in 60-80 ℃ the water and form aaerosol solution.Though this film can be dissolved in the water, this dissolving is higher to the temperature requirement of water, and its dissolution degree is unsatisfactory.
This shows that in the prior art, the solubility property in the water-soluble biodegradable films that the is obtained water that especially temperature is lower in water is relatively poor, and raw materials used cost is higher, is unfavorable for promoting widely.
In order to solve these problems of the prior art, the applicant finds through long term studies, obtained of the present invention can be soluble in water fully at short notice, particularly can be dissolved in hydrolyzable and Biodegradable film and manufacture method thereof in the cold water fully.
The object of the invention be to provide a kind of just can be water-soluble fully in very short time, the biodegradable plastic formed material of no any pollution and preparation method thereof, especially plastics film of making by this material and preparation method thereof.
The present invention implements by following approach: a kind of water-soluble fully, pollution-free, short-term is the plastic shaping material of degradable, this material has following components by weight percent proportioning: polyvinyl alcohol 40-80 part, glycerol 6-30 part, Diethylene Glycol 1-10 part, sorbyl alcohol 1-20 part, borax 0-10 part, formaldehyde 0-5 part, and other well known to a person skilled in the art any additive that can improve film performance.
In the water-soluble hydrolyzable Biodegradable film of the present invention, the effect of said components is respectively: polyvinyl alcohol is water soluble, the macromole with biodegradation character, after water-soluble, may penetrate in the soil, also can be used as soil improvement agent, be particularly suitable for sand improvement, in thin-film material as main film forming substance; Glycerol or glycerine are as softening agent, they can help polyvinyl alcohol to reduce plasticization temperature, polyvinyl alcohol is owing to have the poly-hydroxy feature, plasticization temperature is near its decomposition temperature, so difficulty of processing is well-known, add this softening agent and can improve its processing characteristics, reduce plasticization temperature, prevent that polyvinyl alcohol from decomposing in the course of processing.Owing to have above-mentioned main ingredient, thus can make polyvinyl alcohol at blown film, extrude, injection moulding etc. generally is processed into desired product under the processing conditions, the goods that obtained especially membrane product have higher-strength, the higher transparency and water dissolution performance.In addition, the polyvalent alcohol that contains in the water-soluble biodegradable material of the present invention (as film etc.), Diethylene Glycol, sorbitol etc. have played the effect of secondary plasticizer, and the borax that contains, formaldehyde have played the linking agent effect.
In the water-soluble hydrolyzable Biodegradable film of the present invention, also can add and be selected from the following component one or more, comprising: fiber 0.5-2 part, white carbon black 1-2 part, ultrafine calcium 0-20 part, treated starch 2-40 part.The performance of the material that obtains can be further improved in the adding of above each component in the goods of the present invention, reduces the production cost of goods.In water-soluble biodegradable film of the present invention, the fiber that is added is as weighting agent, film article has been played the effect of reinforcement; The white carbon black that is added can increase the toughness of film, and helps reducing cost; The treated starch that is added helps reducing cost, and helps film forming and improve degradation speed, and the ultrafine calcium that is added is as weighting agent, has also played the effect that reduces cost.In sum, add one or more subsidiary material that are selected from the above-mentioned component after, help improving the performance of film and reduce cost.
The present invention prepares by the following method: add sorbyl alcohol, the glycerol of capacity in the polyvinyl alcohol raw material, at high temperature stir, after making it fully wetting, add an amount of secondary plasticizer, linking agent, strengthening agent, properties-correcting agent, filler etc.Then, said mixture at 25-65 ℃ of following blending reaction 5-50 minute, is added the gained material and carries out granulation in single screw rod or the twin screw extruder, and can be in 150-250 ℃ temperature range blown film.Generally speaking, the film thickness that employing the present invention blows out is between 17 microns to 1 millimeter, and the mechanical property of resulting product is: tensile strength 〉=15Mpa, extension at break 〉=100%, transparence＞90%.
The application of the plastic shaping material that the present invention obtained is very extensive, for example can use method and apparatus well known in the art it is processed as plastic master batch, film, foam materials and other formed materials.
As described in the object of the invention, the water-soluble hydrolyzable Biodegradable film that the present invention obtained has fundamentally changed in the prior art plastics non-degradable or has had only the thinking that starch contained therein can be degraded, polymkeric substance can not be degraded, simple " degraded " changed into " dissolving and degraded ", hydrophobic polyphosphazene polymer collective is become single polymer after the dissolving, greatly increased the aggregate contact area of polymer and microorganism in other words, accelerated macromole and become the small molecules process.In addition, the water-soluble biodegradable film that the present invention obtained is colourless, tasteless, nontoxic, harmless after water-soluble, this has fundamentally overcome common plastic film after using, abandoning, can not degrade throughout the year, thereby be retained in problem of environment pollution caused in the soil, this goods will bring huge interests to the Human's production life.
In order to measure the performance of product that the present invention obtains, the applicant explains the performance of material that the present invention obtains by the temperature and time that measurement material that the present invention obtains is dissolved in the water under whipped state, and the physicalies such as tensile strength of water-soluble biodegradable film of the present invention have been measured, shown in the table 1 specific as follows.Material of the present invention is dissolved under the whipped state in water, and specifically test-results is---when water temperature was T=25 ℃, dissolution time was t=14min; When water temperature was T=45 ℃, dissolution time was t=8min; When water temperature was T=60 ℃, dissolution time was t=6min; When water temperature was T=78 ℃, dissolution time was t=4min.
The performance of the dissimilar plastics films of table 1 relatively
Further set forth the present invention below according to a particular embodiment of the invention:
Embodiment 1: in the reactor that band stirs, add 80 parts of polyvinyl alcohol, add 10 parts of glycerine, with the said mixture high-speed stirring after 50 minutes, discharging to single screw rod extrude and inflation film manufacturing machine on carry out blown film.
Embodiment 2: except softening agent is selected 10 parts of sorbitols for use, and add outside 1 part in the formaldehyde, other reaction conditionss are with embodiment 1.
Embodiment 3: in high-speed stirring, adds 60 parts of polyvinyl alcohol, adds 20 parts of Triethylene glycols, and 1 part of borax, 15 parts of starch stir and reacted 20 minutes, and discharging is to the forcing machine blown film.
Embodiment 4: in homogenizer, add 55 parts of polyvinyl alcohol, 10 parts of Mierocrystalline celluloses, 30 parts of treated starches, 1 part of white carbon black, 30 parts of sorbitols, reaction is 20 minutes in stirrer, discharging is carried out blown film, rolling then, packing to forcing machine under 220 ℃ temperature.
Embodiment 5: in homogenizer, add 80 parts of polyvinyl alcohol, and 15 parts of glycerine, 10 parts of sorbitols, 20 parts of starch after reacting in stirrer, join and react blown film in the forcing machine.
Embodiment 6: in homogenizer, add 80 parts of polyvinyl alcohol, and 15 parts of glycerine, 5 parts of sorbitols, 2 parts of whipping agents after reacting in stirrer, join and carry out extrusion foaming in the forcing machine, make various water-soluble foaming products.
Yet water-soluble biodegradable film of the present invention and other materials are not limited in the foregoing description.
The water-soluble hydrolyzable Biodegradable film that the present invention obtained and other goods can be widely used in uses various places, for example foodstuffs industry wrapping material and agriculture greenhouse film, medical protection film, anti-vibration protected foam material and different shape water-soluble articles material or the like.The goods of making by the water-soluble hydrolyzable biodegradable material of the present invention finish using abandon after, can not form current headachy white pollution for example being dissolved in the water fully after the rain drop erosion through water, can thoroughly solve white pollution problems; And industry and civilian wrapping material, dry crop heat and moisture preserving film, medical protection film and litter bag etc.; for example pack chemical fertilizer, agricultural chemicals, pigment; Dispoable medical goods packing; hospital waste bag, laundry bag; the packing of products such as TV washing machine and cushioning material etc. after these goods are finished using and abandoned, are just can be dissolved in the water fully through rain drop erosion equally; can not form headachy " white pollution ", can effectively prevent diffusion problem poisonous, nuisance yet.
To those skilled in the art; according among aforementioned specification and the embodiment some improvement being carried out in elaboration of the present invention is conspicuous; the improvement of under the situation that does not deviate from of the present invention purport definite by following claim and scope the present invention being carried out all should be within protection scope of the present invention.
Claims (10)
- One kind complete water-soluble, pollution-free and be hydrolyzable biodegradable plastics formed materials in a short time, it is characterized in that described material has following components in portion by weight: polyvinyl alcohol 40-80 part, glycerol 6-30 part, Diethylene Glycol 1-10 part, sorbyl alcohol 1-20 part, borax 0-2 part, formaldehyde 0-2 part.
- 2. material according to claim 1 is characterized in that also having the component that one or more are selected from following component in this material: fiber 0.5-2 part, white carbon black 1-2 part, ultrafine calcium 0-2 part, treated starch 2-5 part.
- 3. material according to claim 1 is characterized in that also having the component that one or more are selected from following component in this material: AC whipping agent 0.1-4 part, sulfohydrazide type blowing agent 0.1-5 part, blowing promotor 0.1-2 part.
- 4. material as claimed in claim 1 or 2, the thickness that it is characterized in that the film article made by this material is between 17 microns to 1 millimeter.
- 5. material according to claim 1 is characterized in that the tensile strength 〉=15Mpa of the film article made by this material, extension at break 〉=100%, transparence＞90%.
- 6. one kind prepares water-soluble fully, pollution-free according to claim 1 and short-term is the method for hydrolyzable biodegradable plastics formed material, it is characterized in that this method comprises the steps: to add the glycerol of 1-30 part in the polyvinyl alcohol raw material, at high temperature stir, add an amount of secondary plasticizer, linking agent, strengthening agent, properties-correcting agent, filler etc. again after making it fully wetting; Then, under 25-65 ℃ temperature range blending reaction 5-50 minute, the gained material is joined carry out granulation in single screw rod or the twin screw extruder again, and can blown film, foaming, moulding in 150-250 ℃ temperature range.
- 7. as method as described in the claim 6, it is characterized in that also having the component that one or more are selected from following component in the formed material by described method preparation: fiber 0.5-2 part, white carbon black 1-2 part, ultrafine calcium 0-2 part, treated starch 2-5 part.
- 8. as method as described in the claim 6, the thickness that it is characterized in that the film for preparing in this way is between 17 microns to 1 millimeter.
- 9. as method as described in arbitrary among the claim 5-7, it is characterized in that tensile strength 〉=15Mpa, extension at break 〉=100%, transparence＞90% by the film of this method preparation.
- 10. the purposes of plastic shaping material according to claim 1 is characterized in that this material being used to prepare plastic master batch, film, foam materials and other formed materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB011310812A CN1157438C (en) | 2001-09-20 | 2001-09-20 | Hydrolytic biodegradable plastic shaping material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011310812A CN1157438C (en) | 2001-09-20 | 2001-09-20 | Hydrolytic biodegradable plastic shaping material and preparation method thereof |
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| CN1405230A true CN1405230A (en) | 2003-03-26 |
| CN1157438C CN1157438C (en) | 2004-07-14 |
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| CNB011310812A Expired - Fee Related CN1157438C (en) | 2001-09-20 | 2001-09-20 | Hydrolytic biodegradable plastic shaping material and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296428C (en) * | 2004-04-30 | 2007-01-24 | 甘肃省科学院生物研究所 | Polyvinyl alcohol composite gel and its synthesis process |
| WO2007033598A1 (en) | 2005-09-21 | 2007-03-29 | Xiaolu Li | Water soluble biodegradable material |
| CN1935882B (en) * | 2005-09-21 | 2011-07-27 | 李小鲁 | Water-soluble biodegradable material, and its preparing method and sheet-like shaped product |
| CN1935886B (en) * | 2005-09-21 | 2011-09-28 | 李小鲁 | Water-soluble biodegradable material, and its preparing method and injection moulded product |
| CN102234405A (en) * | 2010-04-30 | 2011-11-09 | 常州百佳磁卡有限公司 | Water-resistant polyvinyl alcohol (PVA) film composition as well as fusion preparation method thereof |
| CN102311597A (en) * | 2011-08-05 | 2012-01-11 | 大连方盛塑料有限公司 | Hydrolysable and biodegradable plastic |
| CN104497456A (en) * | 2014-12-10 | 2015-04-08 | 淄博龙沙高分子材料科技有限公司 | Polyvinyl alcohol water-soluble film and preparation method thereof |
| CN105482326A (en) * | 2015-12-25 | 2016-04-13 | 佛山市博维环保材料有限公司 | Thin film used for laundry bag of dirty articles and preparation method thereof |
| CN105504615A (en) * | 2015-12-25 | 2016-04-20 | 佛山市博维环保材料有限公司 | Quick-cold-water-soluble embroidery bottom liner film with excellent weatherability and preparation method thereof |
| CN105585803A (en) * | 2015-12-25 | 2016-05-18 | 佛山市博维环保材料有限公司 | Breathable fresh-keeping film with degrading capability and preparation method of breathable fresh-keeping film |
| CN108624020A (en) * | 2018-06-05 | 2018-10-09 | 中国科学院理化技术研究所 | A kind of service life and the adjustable seawater degradable material of degradation cycle and preparation method thereof |
| CN109883402A (en) * | 2019-03-01 | 2019-06-14 | 浙江星天海洋科学技术有限公司 | Enter water from shedding mechanism and its water-soluble bottom cover and water-soluble connector processing method |
| WO2019239183A1 (en) * | 2018-06-13 | 2019-12-19 | Yaghoubi Ebrahim | Produce of polyvinyl alcohol biodegradable films soluble in water at different temperature (biolon) |
| CN111635564A (en) * | 2020-05-28 | 2020-09-08 | 佛山市爱地球环保新材料科技有限公司 | Novel material capable of being dissolved after damp-heat sterilization for protective clothing and preparation method |
-
2001
- 2001-09-20 CN CNB011310812A patent/CN1157438C/en not_active Expired - Fee Related
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296428C (en) * | 2004-04-30 | 2007-01-24 | 甘肃省科学院生物研究所 | Polyvinyl alcohol composite gel and its synthesis process |
| WO2007033598A1 (en) | 2005-09-21 | 2007-03-29 | Xiaolu Li | Water soluble biodegradable material |
| CN1935882B (en) * | 2005-09-21 | 2011-07-27 | 李小鲁 | Water-soluble biodegradable material, and its preparing method and sheet-like shaped product |
| CN1935886B (en) * | 2005-09-21 | 2011-09-28 | 李小鲁 | Water-soluble biodegradable material, and its preparing method and injection moulded product |
| CN1935881B (en) * | 2005-09-21 | 2012-05-09 | 李小鲁 | Water-soluble biodegradable material, and its preparing method and foamed product |
| CN102234405A (en) * | 2010-04-30 | 2011-11-09 | 常州百佳磁卡有限公司 | Water-resistant polyvinyl alcohol (PVA) film composition as well as fusion preparation method thereof |
| CN102234405B (en) * | 2010-04-30 | 2013-06-12 | 常州百佳磁卡有限公司 | Water-resistant polyvinyl alcohol (PVA) film composition as well as fusion preparation method thereof |
| CN102311597A (en) * | 2011-08-05 | 2012-01-11 | 大连方盛塑料有限公司 | Hydrolysable and biodegradable plastic |
| CN104497456A (en) * | 2014-12-10 | 2015-04-08 | 淄博龙沙高分子材料科技有限公司 | Polyvinyl alcohol water-soluble film and preparation method thereof |
| CN105482326A (en) * | 2015-12-25 | 2016-04-13 | 佛山市博维环保材料有限公司 | Thin film used for laundry bag of dirty articles and preparation method thereof |
| CN105504615A (en) * | 2015-12-25 | 2016-04-20 | 佛山市博维环保材料有限公司 | Quick-cold-water-soluble embroidery bottom liner film with excellent weatherability and preparation method thereof |
| CN105585803A (en) * | 2015-12-25 | 2016-05-18 | 佛山市博维环保材料有限公司 | Breathable fresh-keeping film with degrading capability and preparation method of breathable fresh-keeping film |
| CN105504615B (en) * | 2015-12-25 | 2018-03-02 | 佛山市博维环保材料有限公司 | Molten embroidery end liner film of the excellent Rapid cooling of a kind of weatherability and preparation method thereof |
| CN108624020A (en) * | 2018-06-05 | 2018-10-09 | 中国科学院理化技术研究所 | A kind of service life and the adjustable seawater degradable material of degradation cycle and preparation method thereof |
| CN108624020B (en) * | 2018-06-05 | 2020-12-11 | 中国科学院理化技术研究所 | Seawater degradation material with adjustable use period and degradation period and preparation method thereof |
| WO2019239183A1 (en) * | 2018-06-13 | 2019-12-19 | Yaghoubi Ebrahim | Produce of polyvinyl alcohol biodegradable films soluble in water at different temperature (biolon) |
| US20210238386A1 (en) * | 2018-06-13 | 2021-08-05 | Bio Future World Llc | Produce of polyvinyl alcohol biodegradable films soluble in water at different temperatures (biolon) |
| CN109883402A (en) * | 2019-03-01 | 2019-06-14 | 浙江星天海洋科学技术有限公司 | Enter water from shedding mechanism and its water-soluble bottom cover and water-soluble connector processing method |
| CN111635564A (en) * | 2020-05-28 | 2020-09-08 | 佛山市爱地球环保新材料科技有限公司 | Novel material capable of being dissolved after damp-heat sterilization for protective clothing and preparation method |
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| CN1157438C (en) | 2004-07-14 |
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