CN101173055A - Surface crosslinke processing method for thermoplasticity starch or its products - Google Patents
Surface crosslinke processing method for thermoplasticity starch or its products Download PDFInfo
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Abstract
The invention provides a crosslinking method for the surface of the thermoplastic starch or the product thereof, and relates to a method of forming the crosslinking layer on the surface of the thermoplastic starch caused by the radiation of ultraviolet light, and belongs to the technical filed of an improved method for the surface of a solid material. The thermoplastic starch or the product is firstly prepared, the surface layer of the thermoplastic starch or the product is induced with photosensitizer which is decomposed under the irradiation of the ultraviolet light; the decomposition product generates crosslinking reaction with the hydroxyl on starch molecule, and a crosslinking network is formed amongst the bonds of the starch molecule on the surface of the material and the product. By the use of the solid crosslinking reaction, the moderate crosslinking is only performed to the hydrophilic hydroxyl on the surface layer of the thermoplastic starch; under the condition of not changing the processing property of the thermoplastic starch and not remarkably influencing the physical property and the mechanical property of the product, the invention decreases the sensitivity of the thermoplastic starch to the environmental moisture, and improves the hydrolytic resistance of the thermoplastic starch product. Without the necessity of any other solvent, the invention has the advantages of simple technology, high crosslinking efficiency and low cost, no pollution, and no solvent except water, etc.
Description
Technical field
The present invention relates to a kind of surface cross-linking treatment method, particularly relate to the formation method that a kind of ultraviolet light irradiation causes the surface-crosslinked layer of thermoplastic starch, belong to solid material surface method of modifying technical field thermoplastic starch or its goods.
Background technology
Thermoplastic starch generally is meant under the condition that has water or other softening agent to exist, by ative starch being applied the hydrogen bond between heat energy and mechanical energy destruction starch molecule, make the crystalline texture in the ative starch particle disintegrate the disordering external phase of the final starch molecular chain that forms through fusion and shearing action.At this moment, the starch material that obtains has the behavior of thermoplastics, and can further be processed into various goods by enough traditional device of plastic processing.
Advantage such as though thermoplastic starch has biodegradable and raw material is renewable, its goods in some field particularly packaging field successfully replaced some synthetic plastic products (as the loose packing material of the polystyrene foam that is used for buffering package, be used for the plastic pallet of fruit packaging etc.), but the weakness of its poor water resistance, promptly meet easy swelling of water and mechanical property and change problems such as (reason are that the water content in the material changes with ambient moisture) greatly, greatly limited it and used widely with ambient moisture.Improve the water resistance of thermoplastic starch or reduce the susceptibility of its mechanical property, existing many reports ambient moisture.Conclusion is got up, and the method for employing roughly comprises: with biodegradable synthesized polymer material or natural macromolecular material blend; At the biodegradable water-proof coating of thermoplastic starch surface-coated; Thermoplastic starch is carried out whole crosslinking Treatment and material surface is carried out modifying and decorating.
Know that each glucose unit in the starch molecule all has three hydroxyls (respectively at C
2, C
3And C
6The position), they are to cause the hydrophilic major cause of thermoplastic starch.Because the water-wet behavior of thermoplastic starch, consistency is poor when making it and hydrophobic polymeric material blend, causes blend to be in the phase-splitting state, the mechanical properties decrease of material.Though hydrophobic polymeric material is carried out chemical modification (as grafting) or uses expanding material can increase affinity between thermoplastic starch and the synthetic macromolecule, and this certainly will cause the rising of the complicated and production cost of complete processing.At the degradable water-proof coating of thermoplastic starch product surface-coated, be a kind of simple method, but also exist solve the boundary strength problem of coating and matrix, as be coated in the lip-deep zein of thermoplastic starch and just be easy to come off.Crosslinking Treatment promptly uses the hydroxyl on polynary functional compounds (linking agent) and the starch molecule to react, and makes two or more starch molecules crosslinked together, is the effective way that improves the thermoplastic starch water resistance.Mostly the method that adopts is reaction reagent (linking agent or light trigger) is joined in the starch milk that contains softening agent at present, behind the starch milk casting film-forming with gelatinization, by heating or ultraviolet light irradiation crosslinking reaction is finished in whole starch film.These class methods only are suitable for preparing with starch paste the casting method technology of starch film, are difficult in to extrude, use in the working method such as injection moulding and mold pressing, because follow-up forming process will be destroyed established cross-linked network in the thermoplastic starch.In addition, whole crosslinked thermoplastic starch, significant variation (hardening becomes fragile) also can take place in its processing characteristics and mechanical property, thereby influences the moulding and the use of goods.To reduce its susceptibility to ambient moisture be a kind of up-and-coming novel method by the surface of thermoplastic starch being carried out chemically modified and modification.Its basic ideas are to introduce the hydrophilic hydroxyl groups that hydrophobic grouping replaces the thermoplastic starch surface by chemical reaction, improve the hydrophobic purpose of material thereby reach.This method changes the component and the performance of thermoplastic starch body hardly, compares with bulk modified, can save chemical reagent significantly.But, the method for present report, majority is to carry out in organic solvent medium, and reaction conditions is comparatively harsh, and the industrializing implementation difficulty is big and cost is high.Therefore, explore and develop the water resistance of new raising thermoplastic starch and goods thereof and reduce its technology the susceptibility of ambient moisture, particularly those are easy to carry out on the surface of thermoplastic starch product the technology of industrializing implementation, have important use and are worth.
Solid-state crosslinked being meant under the effect of UV-light of UV-light, the molecular chain of polymkeric substance (comprising monomer) form the process of network through crosslinking reaction under solid conditions.The UV-light solid-state light is crosslinked have that but pollution-free, energy-conservation normal temperature reacts and efficient than advantages such as height, greatly simplified technology, avoided that multistep is rapid in the traditional method, energy consumption is high, shortcomings such as pollution are arranged, be a kind of eco-friendly green technology.
Summary of the invention
The object of the present invention is to provide a kind of surface-crosslinked modification, green and economic a kind of surface cross-linking treatment method that can be used for various thermoplastic starchs or its goods to thermoplastic starch or its goods.
Above-mentioned purpose of the present invention is achieved in that
A kind of surface cross-linking treatment method to thermoplastic starch or its goods, by introducing photosensitizers at upper layer and through ultraviolet light irradiation, forming the cross-linked network of starch molecular chain on the surface of thermoplastic starch or its goods, concrete steps are as follows:
(1) preparation of thermoplastic starch and goods thereof:
Thermoplastic starch makes the ative starch plasticizing by extrusion equipment, and its goods available heat plastic starch makes through mold pressing, injection moulding, plastic uptake, blow moiding method; Also can make the thermoplastic starch film through casting method by with the starch milk gelatinization; It is a kind of in water, glycerine, sorbyl alcohol, low molecular weight polyethylene alcohol, N.F,USP MANNITOL, the urea that thermoplastic starch prepares used softening agent, also above-mentioned several combinations;
(2) the surface-crosslinked processing of thermoplastic starch and goods thereof:
A) introducing of photosensitizers: photosensitizers is dissolved in the water, make concentration and be 0.1 ~ 10% the photosensitizers aqueous solution, with the photosensitizers aqueous solution that makes thermoplastic starch product is soaked, also can be to thermoplastic starch product top coat, spray, soak time is: 10 seconds ~ 30 minutes, it is 11 ~ 95% environment that the thermoplastic starch product that then surface is contained the photosensitizers aqueous solution places relative humidity, makes water-content in the goods reach equilibrium water content under this relative humidity; Adopt coating, spraying method that the photosensitizers aqueous solution of thermoplastic starch product surface attachment is evenly distributed;
B) photo-crosslinking: the sample that will introduce photosensitizers and adjust water content is exposed under the UV-light and causes crosslinking reaction, make starch molecular chain form cross-linked network on the test specimen surface, the wavelength region of used UV-light is between 254 ~ 365nm, and the irradiation of used UV-light is 3 ~ 150J/cm
2, ultraviolet light irradiation carries out in temperature is 15 ~ 60 ℃ environment, and ultraviolet ray generating apparatus such as the available high voltage mercury lamp of said ultraviolet ray, low-pressure mercury bright lamp, deuterium lamp, xenon lamp, laser produce.
Said photosensitizers is a kind of of Sodium Benzoate, sodium salicylate or their any mixed thing.
The wavelength region of used UV-light is between 254-365nm.
The irradiation of used UV-light is 3-150J/cm
2
Ultraviolet light irradiation carries out in temperature is 15-60 ℃ environment.
This method adopts the method for ultraviolet light irradiation that thermoplastic starch or its goods are carried out surface-crosslinked modification processing.By in the upper layer of thermoplastic starch or its goods, introducing photosensitizers, photosensitizers is decomposed, and make hydroxyl generation crosslinking reaction on degradation production and the starch molecule, form the water resistance that cross-linked network improves material at the starch molecule interchain of material or product surface layer.The reaction reagent of selecting for use and the processing method of employing are prerequisite to be easy to carrying out industrializing implementation on the surface of thermoplastic starch product.Whole crosslinked different with other surface modifying method with starch film, the present invention utilizes the water-wet behavior of thermoplastic starch, adopts the method for surface diffusion, only introduces photosensitizers at the upper layer of thermoplastic starch or its goods.Therefore, the consumption of photosensitizers reduces significantly, and crosslinking reaction is easier to be finished.The present invention only carries out the crosslinking Treatment of appropriateness to the hydrophilic hydroxyl groups of thermoplastic starch upper layer, under the condition of the processing characteristics that does not change thermoplastic starch and its goods body rerum natura of not remarkably influenced and mechanical property, reduce the susceptibility of thermoplastic starch, improve the water resistance of thermoplastic starch product ambient moisture.
Effect of the present invention:
Utilize the solid-state crosslinking technological of above-mentioned UV-light, can make thermoplastic starch or its goods have the upper layer of various different thickness and different crosslinking degrees.The crosslinking reaction that UV-light causes only occurs in surface tens to thousands of dust thickness ranges, can keep the body rerum natura of material and mechanical property constant substantially.The contact angle measurement measuring result shows that the hydrophobic properties of the surface of thermoplastic starch or goods significantly improve, bring up to the most about 93 ° through the surface of ultraviolet light cross-linking processing and the contact angle of water by about 55, and can in this scope, regulate to adapt to different purposes.After the surface-crosslinked processing of UV-light, thermoplastic starch significantly descends to the susceptibility of ambient moisture, and in 95% relative humidity environment, its equilibrium water content about 49% is reduced to about 27%; In boiling water, boiled the broken time and brought up to 22 minutes by 8 minutes; Anti-solvent solubility also significantly improves, and becomes insoluble by dissolving in dimethyl sulfoxide (DMSO).
The present invention has that technology is simple, cross-linking efficiency is high, the outer characteristics such as other solvent, pollution-free and cost are low that need not that dewater, and the surface-crosslinked modification that can be used for various thermoplastic starchs or its goods is handled, and is a kind of very green and economic method.
Embodiment
Ative starch, water and softening agent etc. are sent into forcing machine by required mass content, and obtain thermoplastic starch by the processing requirement plasticizing.With methods such as mold pressing, injection moulding, plastic uptake or blowings thermoplastic starch is made goods.Or ative starch, water and softening agent etc. are made starch milk by required quality, with casting method the starch milk of gelatinization is made starch film.
Thermoplastic starch product is placed the photosensitizers aqueous solution of different concns, and soak the different time, in the different thick layer in thermoplastic starch product surface, introduce the photosensitizers of different quantities.The thermoplastic starch product that the surface is contained photosensitizers places under the irradiation of UV-light, and the degradation production of photosensitizers and the hydroxyl on the starch molecular chain are reacted, and forms the cross-linked layer of different thickness and different crosslinking degrees at product surface.
Embodiment 1:
W-Gum and water are sent into twin screw extruder (the screw diameter 35mm that barrel zone temperature is set to 60 ℃/80 ℃/100 ℃/120 ℃/100 ℃/85 ℃ by 65/35 mass ratio with the speed of 6kg/h, length-to-diameter ratio L/d=38), be under the condition of 100rpm material to be extruded through the circular hole die head of φ=3mm at screw speed, and depress to the thin slice that thickness is about 0.2mm at 80 ℃ with thermocompressor.
Water content is about 12% thermoplastic starch thin slice, and to put into concentration be that 0.1% the Sodium Benzoate aqueous solution soaked 90 seconds, drains surface water liquid after pulling out, and placing relative humidity is 57% environment, makes its moisture content reach balance.The thermoplastic starch thin slice that upper layer is contained Sodium Benzoate is exposed under the UV-light, and light source master emission wavelength is 254nm, and the irradiation metering is 20J/cm
2, obtain surface-crosslinked thermoplastic starch thin slice.
Embodiment 2:
With embodiment 1, difference is that the thermoplastic starch thin slice is put into concentration is that 2% the Sodium Benzoate aqueous solution soaked 30 seconds, and placing relative humidity then is 95% environment, makes its moisture content reach balance.The thermoplastic starch thin slice that upper layer is contained Sodium Benzoate is exposed under the UV-light, and light source master emission wavelength is 254nm, and the irradiation metering is 6J/cm
2, obtain surface-crosslinked thermoplastic starch thin slice.
Embodiment 3:
With embodiment 1, difference is that the thermoplastic starch thin slice is put into concentration is that 1% the sodium salicylate aqueous solution soaked 60 seconds, the thermoplastic starch thin slice that upper layer is contained sodium salicylate is exposed under the UV-light, and light source master emission wavelength is 254nm, and the irradiation metering is 80J/cm
2, obtain surface-crosslinked thermoplastic starch thin slice.
Embodiment 4:
With embodiment 1, difference is that the thermoplastic starch thin slice is put into concentration is that 5% the sodium salicylate aqueous solution soaked 300 seconds, and placing relative humidity then is 11% environment, makes its moisture content reach balance.The thermoplastic starch thin slice that upper layer is contained sodium salicylate is exposed under the UV-light, and light source master emission wavelength is 365nm, and the irradiation metering is 60J/cm
2, obtain surface-crosslinked thermoplastic starch thin slice.
Embodiment 5:
With embodiment 1, difference is that the thermoplastic starch thin slice is put into concentration is that the mixed aqueous solution of the sodium salicylate of 0.5% Sodium Benzoate and 0.5% soaked 60 seconds, placing relative humidity then is 75% environment, the thermoplastic starch thin slice that upper layer is contained Sodium Benzoate and sodium salicylate is exposed under the UV-light, light source master emission wavelength is 312nm, and the irradiation metering is 30J/cm
2, obtain surface-crosslinked thermoplastic starch thin slice.
Embodiment 6:
Mass ratio is that the mixture of W-Gum/glycerine of 85/15 and water (mixture quality 28%) are sent into twin screw extruder (the screw diameter 35mm that barrel zone temperature is set to 60 ℃/80 ℃/100 ℃/120 ℃/100 ℃/85 ℃ with the speed of 6kg/h, length-to-diameter ratio L/d=38), be under the condition of 100rpm material to be extruded through the slot die of 50mm * 10mm at screw speed, and depress to the thermoplastic starch thin plate that thickness is about 3mm at 80 ℃ with thermocompressor.
Water-content is about 12% thermoplastic starch thin plate and soaked 30 minutes in concentration is 10% the Sodium Benzoate aqueous solution, placing relative humidity then is 57% environment, makes its moisture content reach balance.The thermoplastic starch thin plate that upper layer is contained Sodium Benzoate is exposed under the UV-light, and light source master emission wavelength is 254nm, and the irradiation metering is 150J/cm
2, obtain surface-crosslinked thermoplastic starch thin plate.
Embodiment 7:
With embodiment 6, difference is that the thermoplastic starch thin plate is put into concentration is that the mixed aqueous solution of the sodium salicylate of 1% Sodium Benzoate and 1% soaked 20 seconds, the thermoplastic starch thin slice that upper layer is contained Sodium Benzoate and sodium salicylate is exposed under the UV-light, light source master emission wavelength is 254nm, and the irradiation metering is 40J/cm
2, obtain surface-crosslinked thermoplastic starch thin plate.
Embodiment 8:
With example 6, difference is that the mixture of sending into forcing machine adopts following the composition: the mass ratio of starch/glycerol/sorbyl alcohol is 83/15/2, and be to soak 120 seconds in 2% the sodium salicylate aqueous solution in concentration, the thermoplastic starch thin plate that upper layer is contained sodium salicylate is exposed under the UV-light, light source master emission wavelength is 365nm, and the irradiation metering is 60J/cm
2, obtain surface-crosslinked thermoplastic starch thin plate.
Embodiment 9:
With example 6, difference is that the mixture of sending into forcing machine adopts following the composition: the mass ratio of starch/glycerol/polyvinyl alcohol is 80/10/10, the extruder barrel temperature is set to 60 ℃/80 ℃/110 ℃/140 ℃/120 ℃/95 ℃, depress to the thermoplastic starch thin plate that thickness is about 5mm with thermocompressor at 120 ℃, and be to soak 60 seconds in 1% the Sodium Benzoate aqueous solution in concentration, the thermoplastic starch thin plate that upper layer is contained Sodium Benzoate is exposed under the UV-light, light source master emission wavelength is 254nm, and the irradiation metering is 100J/cm
2, obtain surface-crosslinked thermoplastic starch thin plate.
Embodiment 10:
With the water of mass ratio 95/5 and the mixture furnishing pulpous state of starch, do not stop to stir 90 ℃ of temperature and make the complete gelatinization of starch milk, be incubated 30 minutes, under pressure is about the condition of 0.09MPa, the bubble in the paste liquid is deviate from.With the paste liquid casting film-forming on polypropylene board that obtains, the about 0.08mm of thickness.
Water-content is about 12% thermoplastic starch film, and to put into concentration be that 0.5% the Sodium Benzoate aqueous solution soaked 10 seconds, drains surface water liquid after pulling out, and placing relative humidity then is 57% environment, makes its moisture content reach balance.The thermoplastic starch film that upper layer is contained Sodium Benzoate is exposed under the UV-light, and light source master emission wavelength is 254nm, and the irradiation metering is 10J/cm
2, obtain surface-crosslinked thermoplastic starch film.
Embodiment 11:
With example 10, difference is the mixture of the water that consists of mass ratio 95/4/1, starch and the glycerine of starch milk.With the thermoplastic starch film concentration be 0.75% Sodium Benzoate and concentration be 0.25% sodium salicylate mixed aqueous solution in soaked 20 seconds, the thermoplastic starch film that upper layer is contained Sodium Benzoate and sodium salicylate is exposed under the UV-light, light source master emission wavelength is 254nm, and the irradiation metering is 20J/cm
2, obtain surface-crosslinked thermoplastic starch film.
Embodiment 12:
With example 10, difference is the mixture of the water that consists of mass ratio 95/3.2/1/0.8, starch, polyvinyl alcohol and the glycerine of starch milk.And be to soak 30 seconds in 1% the Sodium Benzoate aqueous solution in concentration, the thermoplastic starch film that upper layer is contained Sodium Benzoate is exposed under the UV-light, and light source master emission wavelength is 365nm, and the irradiation metering is 3J/cm
2, obtain surface-crosslinked thermoplastic starch film.
Embodiment 13:
With example 10, difference is after treating the complete gelatinization of starch milk, adds the polyvinyl alcohol of starch quality 20% and constantly stirs, and treats that polyvinyl alcohol is all after the dissolving, according to the method casting film-forming of example 10.To in being the mixed aqueous solution of 1% sodium salicylate, concentration soak 60 seconds at the film of balance moisture content under the 57% relative humidity condition, the thermoplastic starch film that upper layer is contained sodium salicylate is exposed under the UV-light, light source master emission wavelength is 312nm, and the irradiation metering is 60J/cm
2, obtain surface-crosslinked thermoplastic starch film.
Claims (5)
1. the surface cross-linking treatment method to thermoplastic starch or its goods is characterized in that forming the cross-linked network of starch molecular chain on the surface of thermoplastic starch or its goods by at upper layer introducing photosensitizers and through ultraviolet light irradiation, and concrete steps are as follows:
(1) preparation of thermoplastic starch and goods thereof:
Thermoplastic starch makes the ative starch plasticizing by extrusion equipment, and its goods available heat plastic starch makes through mold pressing, injection moulding, plastic uptake, blow moiding method; Also can make the thermoplastic starch film through casting method by with the starch milk gelatinization; It is a kind of in water, glycerine, sorbyl alcohol, low molecular weight polyethylene alcohol, N.F,USP MANNITOL, the urea that thermoplastic starch prepares used softening agent, also above-mentioned several combinations;
(2) the surface-crosslinked processing of thermoplastic starch and goods thereof:
A) introducing of photosensitizers: photosensitizers is dissolved in the water, make concentration and be 0.1 ~ 10% the photosensitizers aqueous solution, with the photosensitizers aqueous solution that makes thermoplastic starch product is soaked, also can be to thermoplastic starch product top coat, spray, soak time is: 10 seconds ~ 30 minutes, it is 11 ~ 95% environment that the thermoplastic starch product that then surface is contained the photosensitizers aqueous solution places relative humidity, makes water-content in the goods reach equilibrium water content under this relative humidity; Also can adopt coating, spraying method that the photosensitizers aqueous solution of thermoplastic starch product surface attachment is evenly distributed;
B) photo-crosslinking: the sample that will introduce photosensitizers and adjust water content is exposed under the UV-light and causes crosslinking reaction, makes starch molecular chain form cross-linked network on the test specimen surface.
The wavelength region of used UV-light is between 254 ~ 365nm, and the irradiation of used UV-light is 3 ~ 150J/cm
2, ultraviolet light irradiation carries out in temperature is 15 ~ 60 ℃ environment.
2. a kind of surface cross-linking treatment method to thermoplastic starch or its goods according to claim 1 is characterized in that, said photosensitizers is a kind of of Sodium Benzoate, sodium salicylate or their any mixed thing.
3. a kind of surface cross-linking treatment method to thermoplastic starch or its goods according to claim 1 is characterized in that the wavelength region of used UV-light is between 254-365nm.
4. a kind of surface cross-linking treatment method to thermoplastic starch or its goods according to claim 1 is characterized in that the irradiation of used UV-light is 3-150J/cm
2
5. a kind of surface cross-linking treatment method to thermoplastic starch or its goods according to claim 1 is characterized in that, ultraviolet light irradiation carries out in temperature is 15-60 ℃ environment.
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| CN200710056227A CN101173055B (en) | 2007-10-29 | 2007-10-29 | Surface crosslinke processing method for thermoplasticity starch or its products |
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|---|---|---|---|
| CN200710056227A CN101173055B (en) | 2007-10-29 | 2007-10-29 | Surface crosslinke processing method for thermoplasticity starch or its products |
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| CN101173055A true CN101173055A (en) | 2008-05-07 |
| CN101173055B CN101173055B (en) | 2010-05-19 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928403A (en) * | 2010-05-21 | 2010-12-29 | 吉林大学 | Surface cross-linking treatment method for thermoplastic starch products |
| CN101418081B (en) * | 2008-10-30 | 2011-02-16 | 吉林大学 | Surface esterification treatment method for thermoplastic starch product |
| CN102212201A (en) * | 2011-05-10 | 2011-10-12 | 吉林大学 | Surface cross-linking modification method for starch nanocrystals |
| CN109232956A (en) * | 2018-09-29 | 2019-01-18 | 南京林业大学 | A kind of method on surface and noumenon synergistic UV crosslinking starch plastic |
| CN114605710A (en) * | 2022-04-11 | 2022-06-10 | 江苏多上新材料科技有限公司 | Ultraviolet light cross-linked completely biodegradable plastic bag material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5140076A (en) * | 1990-04-02 | 1992-08-18 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method of treating the surface of an absorbent resin |
| TW362100B (en) * | 1995-07-21 | 1999-06-21 | Novartis Ag | The preparation and use of photochemically cross-linked polysaccharide derivatives having no photopolymerisable functional groups |
| CN1057538C (en) * | 1996-12-03 | 2000-10-18 | 中国科学院广州化学研究所 | Preparation of chelated resin using cassava starch as primary material |
| US6391451B1 (en) * | 1999-09-07 | 2002-05-21 | Basf Aktiengesellschaft | Surface-treated superabsorbent polymer particles |
| CN1876699A (en) * | 2005-06-10 | 2006-12-13 | 杨军现 | Microwave radioradiation crosslinked complete biodegradable material and its processing method |
| CN100389145C (en) * | 2006-09-29 | 2008-05-21 | 北京大学 | Water gel containing natural high molecule and its radiation preparing method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418081B (en) * | 2008-10-30 | 2011-02-16 | 吉林大学 | Surface esterification treatment method for thermoplastic starch product |
| CN101928403A (en) * | 2010-05-21 | 2010-12-29 | 吉林大学 | Surface cross-linking treatment method for thermoplastic starch products |
| CN101928403B (en) * | 2010-05-21 | 2012-01-25 | 吉林大学 | Surface cross-linking treatment method for thermoplastic starch products |
| CN102212201A (en) * | 2011-05-10 | 2011-10-12 | 吉林大学 | Surface cross-linking modification method for starch nanocrystals |
| CN102212201B (en) * | 2011-05-10 | 2012-10-03 | 吉林大学 | Surface cross-linking modification method for starch nanocrystals |
| CN109232956A (en) * | 2018-09-29 | 2019-01-18 | 南京林业大学 | A kind of method on surface and noumenon synergistic UV crosslinking starch plastic |
| CN114605710A (en) * | 2022-04-11 | 2022-06-10 | 江苏多上新材料科技有限公司 | Ultraviolet light cross-linked completely biodegradable plastic bag material and preparation method thereof |
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