CN1415629A - Method for preparing degradable biological material - Google Patents
Method for preparing degradable biological material Download PDFInfo
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- CN1415629A CN1415629A CN 02155319 CN02155319A CN1415629A CN 1415629 A CN1415629 A CN 1415629A CN 02155319 CN02155319 CN 02155319 CN 02155319 A CN02155319 A CN 02155319A CN 1415629 A CN1415629 A CN 1415629A
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- toluene
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- caprolactone
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Abstract
A process for preparing fully biodegradable material from industrial starch includes such steps as grafting reaction with mixed cyclolactone (epsilon-hexalactone and lactide), azeotropic dewatering by toluene or benzene, and grafting reaction of starch and fatty cyclolactone under the catalysis of stannous octoate (or chloride) or obtain polyester. It can be further processed to become plate, sheet, or film with a certain mechanical strength, toughness and water-proof nature.
Description
Affiliated field
The invention belongs to the totally biodegradable preparation methods.
Background technology
In the research of starch-grafted fats polyester; more existing report; as United StatesPatent 5; 616; 671 (1997); its technical process is all complicated; the operation that starch dewaters in advance all is to carry out being higher than under 100 ℃ the condition; or under vacuum condition, dewater more than the 20h; the fats monomer also need carry out special meticulous drying and dewater; rectifying is sealed up for safekeeping again, or polyreaction is carried out in protection under the nitrogen of 99.99% purity, and giving on a large scale, preparation results in hand cramps and increases many technical process.Report also in the data that in the catalytic system of stannous octoate, when the weight ratio of starch and 6-caprolactone was 1: 1, the insolubles content that records its graft product was 53-57%, soluble homopolymer is 47-43%.Insolubles content is high more, shows that graft effect is good more; Otherwise, if solubles content is high more, illustrate that then the homopolymer composition of cyclic lactone is many more, for the grafts of starch, be unfavorable.
Summary of the invention
The purpose of this invention is to provide a kind of Wholly-degradable preparation methods.
With the technical grade W-Gum, potato starch is a base-material, its structure comprises amylopectin and amylose starch, at first do azeotropy dehydrant and carry out azeotropic dehydration with toluene or benzene, add organo-metallic catalyst again,, make the hydroxyl of catalyzer and starch form chain carrier as stannous octoate etc., add technical grade cycloaliphatic ring lactone at last again, the lactone water content should be less than 0.5%; The adding of cycloaliphatic ring lactone can be taked to add once, also can take the working method that drips, can directly carry out the suspended state polymerization, or toluene or benzene steamed carries out mass polymerization, and controlled temperature stirs, and can reach the rheid of certain viscosity.The product melt temperature is between 50-170 ℃.Can suppress film forming, the blowing film forming also can be processed into sheet material or sheet material, or with other plastic macromolecule material blend machine-shaping.
The processing method that the present invention prepares material is as follows: industrial corn starch or potato starch and hybrid ring lactone were flooded 0-24 hour; The weight ratio of starch and hybrid ring lactone is 80-20: 20-80; The hybrid ring lactone comprises 6-caprolactone and rac-Lactide, and the weight ratio of 6-caprolactone and rac-Lactide is 99-1: 1-99; Mixture adding after will flooding then has in the reactor of stirring, adds toluene, and heat temperature raising is to the azeotropic dehydration temperature simultaneously; After 2-6 hour, the system interior moisture content of making is lower than 100ppm, adds stannous octoate catalyst then, and catalyst levels is the 0.05-1.0% of total reactant weight, in advance stannous octoate is mixed with toluene solution, and weight percent concentration is 0.5-1.3%; Temperature control 90-150 ℃, drip the hybrid ring lactone, the time of dropping carried out suspension polymerization 24-150 hour at 3-20 hour again, obtained starch-grafted product; When adopting mass polymerization, the reaction times kept 24-50 hour, and the effect of mass polymerization is better than suspension polymerization more significantly, can shorten the reaction times widely, can finish in 50h usually; For starch and the caprolactone graft product by weight 1: 1, its tensile strength is 12Mpa, and elongation at break is about 2%, and its insolubles content reaches 54-63%, and solubles content is 46-37%.The medium-resistance aspect is compared with native starch, and obvious variation has also taken place its acidproof, alkaline-resisting and water resistance.If blend press mold with polycaprolactone and starch, it is immersed respectively in the hydrochloric acid of water and 0.5N, soak after 24 hours, membrane sample produces tangible swelling, increase weight 23.1% and 27.2% respectively, the starch that shows not graft modification has very high water-absorbent, and the acidproof water tolerance of graft product obviously improves.
The present invention prepares the method for totally biodegradable material, and technology is simple, need not to fill nitrogen and drives away oxygen or nitrogen protection, and directly azeotropic dehydration makes lactone ring opening polymerization produce the starch-grafted macromolecular material with polyester side chains.
The mensuration of medium-resistance:
The sample film of given weight is immersed respectively in the hydrochloric acid of water and 0.5N, and room temperature is placed and to be taken out in 24 hours, blots the water of film surface adsorption with filter paper, weighs, and measures the per-cent that immerses the weight increase and decrease before and after the medium.
The mensuration of insolubles and solubles content: the sample of given weight is immersed in the toluene, the polymkeric substance that contains rac-Lactide is made solvent with chloroform, stirring at room was filtered in 24 hours, dry, weighing precipitates part and dissolving part respectively, the precipitation part comprises graft product and residual starch, and soluble part is the homopolymer of polycaprolactone or polylactide.
The material of the present invention's preparation can be used for the wrapping material of medicine, food, also can be used for fields such as mulch film and damping material.
Embodiment
Embodiment 1:
In azeotropic dehydration reflux, water trap and three mouthfuls of reaction flasks of condenser are housed, add technical grade W-Gum 30g, add 6-caprolactone 30g and toluene 60ml again, heating under agitation makes to reach azeotropic temperature in the system and begin dehydration.Begin in the water trap muddy phlegma to occur, behind the 30min., liquid begins phase-splitting, lower floor is water clearly, and it is limpid that the phlegma on upper strata also becomes gradually, behind the 2h upper strata liquid transparent fully till, the toluene solution of 0.18g stannous octoate is added reaction system, and make and reach 118 ℃ in the system, under agitation keep suspension reaction 70h, stopped reaction, steam toluene, in the flowable state heavy-gravity white product that has a down dip out, drying gets 59.1g., and yield 98%. products are at 50-65 ℃ of melting.Water-intake rate in 0.5N hydrochloric acid and water is respectively 1.4% and 2.6%.Insolubles and solvend are respectively 62% and 38%.
Embodiment 2:
Weighing technical grade W-Gum 10g joins in three mouthfuls of reaction flasks, adds rac-Lactide 10g again, toluene 40ml dewaters by the azeotropic mode of example 1, and is complete when transparent until upper strata liquid, the toluene solution of the stannous octoate of reactant weight 0.15% is added reaction system, keep stirring suspension polymerization 92h under 130 ℃, stopped reaction also steams toluene, in the flowable state heavy-gravity white product that has a down dip out, get product 19g., yield 95% after the drying.Product needs to carry out press mold at 160-170 ℃.Insolubles and solvend are respectively 69% and 31%.
Embodiment 3:
Weighing technical grade W-Gum 250g mixes with 6-caprolactone 250g, and preimpregnation 24h joins mixture in the reactor again, add toluene 600ml, by the azeotropic dehydration mode of example 1, behind the 4h azeotropic dehydration, the toluene solution of the stannous octoate of reactant weight 0.3% is added reaction system, under 111 ℃, keep stirring 150h in interior temperature, stopped reaction steams toluene, in the flowable state heavy-gravity white product that has a down dip out, drying gets product 491g., yield 98%.Water-intake rate in 0.5N hydrochloric acid and water is respectively 1.2% and 2.5%.Insolubles and solvend are respectively 59% and 41%.
Embodiment 4:
Weighing technical grade W-Gum 250g joins in the reactor, adds 6-caprolactone 250g again, benzene 600ml, azeotropic mode by example 1 is dewatered, and is complete when transparent until the upper strata of separating tube liquid, and the toluene solution of the stannous octoate of reactant weight 0.05% is added in the reactor, steam toluene and benzene simultaneously, keep to stir under 150 ℃ and carry out mass polymerization 132h, stopped reaction is in the flowable state heavy-gravity white product that has a down dip out, get product 495g, yield 99% after the drying.
Water-intake rate in 0.5N hydrochloric acid and water is respectively 4.7% and 6.6%.Insolubles and solvend are respectively 54% and 46%.
Embodiment 5:
Weighing technical grade potato starch 80g joins in three mouthfuls of reaction flasks, adds toluene 100ml; azeotropic mode by example 1 is dewatered, nitrogen-less protection, and the toluene solution with the stannous octoate of reactant weight 0.3% behind the 2h adds reaction system; under 130 ℃, keep 1h; add 6-caprolactone 20g again, stir 144h suspension polymerization, stopped reaction; steam toluene; in the flowable state heavy-gravity white product that has a down dip out, 98.2g., yield 98%.
Water-intake rate in 0.5N hydrochloric acid and water is respectively 14.7% and 9.7%.Insolubles and solvend are respectively 82% and 18%.
Embodiment 6:
Weighing technical grade W-Gum 10g joins in three mouthfuls of reaction flasks, adds 6-caprolactone 40g again, toluene 40ml by the azeotropic mode of example 1 3h that dewaters, adds reaction system with the toluene solution of the tin protochloride of reactant weight 0.15%, under 130 ℃, keep stirring, suspension polymerization 88h, stopped reaction, steam toluene, in the flowable state heavy-gravity white product that has a down dip out, 49.2g., yield 98%
Water-intake rate in 0.5N hydrochloric acid and water is respectively 1.1% and 0.8%.Insolubles and solvend are respectively 17% and 83%.
Embodiment 7:
Weighing technical grade W-Gum 20g joins in three mouthfuls of reaction flasks toluene 60ml, by the azeotropic mode of example 1 4h that dewaters, add 6-caprolactone 20g again, 90 ℃ of following hot dipping 3h are with the stannous octoate toluene solution adding reaction system of reactant weight 1.0%, under 140 ℃, keep and stir 48h, stopped reaction steams toluene, in the flowable state heavy-gravity white product that has a down dip out, get 39.1g., yield 98%.
Water-intake rate in 0.5N hydrochloric acid and water is respectively 2.5% and 4.0%.Insolubles and solvend are respectively 57% and 43%.
Embodiment 8:
Weighing technical grade potato starch 15g joins in three mouthfuls of reaction flasks toluene 60ml, by the azeotropic mode of example 1 2h that dewaters, the toluene solution of the stannous octoate of reactant weight 0.3% is added reaction system, keep 16h after, in 2h, drip 6-caprolactone 15g, under 140 ℃, keep and stir 24h, stopped reaction steams toluene, in the flowable state heavy-gravity white product that has a down dip out, get 29.0g., yield 97%.
Water-intake rate in 0.5N hydrochloric acid and water is respectively 4.2% and 4.4%.Insolubles and solvend are respectively 55% and 45%.
Embodiment 9:
Weighing industrial corn starch 35g, join in three mouthfuls of reaction flasks, toluene 80ml, behind the azeotropic dehydration, the toluene solution of the stannous octoate of reactant weight 0.3% is added reaction system, keep 4h, and in 20h, drip the 6-caprolactone of 15g, continue reaction 10h down at 90 ℃, get heavy-gravity white product 49.6g., yield 99%.
Embodiment 10:
Weighing native corn starch 15g joins in three mouthfuls of reaction flasks toluene 60ml, by the azeotropic mode of example 1 6h that dewaters, the toluene solution of the stannous octoate of reactant weight 0.3% is added reaction system, keep 6h, steam toluene, in 15min, at first drip the 6-caprolactone of 1g, under 140 ℃, kept 16 hours, and in 3h, dripped the 6-caprolactone 14g of surplus again, continue to stir and keep bulk polymerization 24h, get heavy-gravity white product 29.8g., yield 99%.
Water-intake rate in 0.5N hydrochloric acid and water is respectively 6.0% and 8.1%.Insolubles and solvend are respectively 63% and 37%.
Embodiment 11:
Weighing native corn starch 15g joins in three mouthfuls of reaction flasks toluene 80ml, by the azeotropic mode of example 1 4h that dewaters, toluene solution with the stannous octoate of reactant weight 0.3% adds reaction system again, keeps 19h, adds the mixture 15g of rac-Lactide and caprolactone again, its weight ratio is 99: 1, steam toluene, under 130 ℃ envrionment temperature, stir 50h, get white thickness body product, dry back 29g, yield 97%.
Embodiment 12:
Weighing native corn starch 20g joins in three mouthfuls of reaction flasks toluene 60ml, by the azeotropic mode of example 1 4h that dewaters, toluene solution with the stannous octoate of reactant weight 0.1% adds reaction system again, keeps 19h, adds the mixture 20g of rac-Lactide and caprolactone again, its weight ratio is 1: 99, steam toluene, under 130 ℃ envrionment temperature, stir 45h, get white thickness body product, dry back 38.5g, yield 96%.
Water-intake rate in 0.5N hydrochloric acid and water is respectively 5.1% and 4.9%.Insolubles and solvend are respectively 61% and 39%.
Claims (3)
1. totally biodegradable preparation methods, the weight ratio of starch and hybrid ring lactone is 80-20: 20-80; The adding of mixture behind the dipping is had in the reactor of stirring, add toluene, heat temperature raising is to the azeotropic dehydration temperature simultaneously; After 2-6 hour, the system interior moisture content of making is lower than 100ppm, adds stannous octoate catalyst then, and catalyst levels is the 0.05-1.0% of total reactant weight, in advance stannous octoate is mixed with toluene solution, and weight percent concentration is 0.5-1.3%; Temperature control 90-150 ℃, drip the hybrid ring lactone, the time of dropping directly carried out suspension polymerization 24-150 hour at 3-20 hour, obtained starch-grafted product.
2. preparation method as claimed in claim 1, wherein said hybrid ring lactone is 6-caprolactone and rac-Lactide, the weight ratio of 6-caprolactone and rac-Lactide is 99-1: 1-99.
3. according to the preparation method of claim 1 and 2, when adopting mass polymerization, the reaction times is controlled 24-50 hour.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02155319 CN1415629A (en) | 2002-12-10 | 2002-12-10 | Method for preparing degradable biological material |
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| CN 02155319 CN1415629A (en) | 2002-12-10 | 2002-12-10 | Method for preparing degradable biological material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030892A (en) * | 2010-11-25 | 2011-04-27 | 沈阳工业大学 | Preparation method of glutinous rice flour grafted polycaprolactone thermoplastic material |
| CN101298512B (en) * | 2007-04-30 | 2011-07-27 | 刘原珊 | PVA-PCL-starch blending material and preparation thereof |
| CN105017537A (en) * | 2014-04-30 | 2015-11-04 | 北京化工大学 | Gelatin and polyester copolymerized composite biological material and preparation method thereof |
-
2002
- 2002-12-10 CN CN 02155319 patent/CN1415629A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298512B (en) * | 2007-04-30 | 2011-07-27 | 刘原珊 | PVA-PCL-starch blending material and preparation thereof |
| CN102030892A (en) * | 2010-11-25 | 2011-04-27 | 沈阳工业大学 | Preparation method of glutinous rice flour grafted polycaprolactone thermoplastic material |
| CN102030892B (en) * | 2010-11-25 | 2012-09-05 | 沈阳工业大学 | Preparation method of glutinous rice flour grafted polycaprolactone thermoplastic material |
| CN105017537A (en) * | 2014-04-30 | 2015-11-04 | 北京化工大学 | Gelatin and polyester copolymerized composite biological material and preparation method thereof |
| CN105017537B (en) * | 2014-04-30 | 2017-08-25 | 北京化工大学 | A kind of gelatin/polyethylene terephthalate copolymer composite biological material and preparation method thereof |
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