CN100469836C - Biodegradable polymer - Google Patents
Biodegradable polymer Download PDFInfo
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- CN100469836C CN100469836C CNB03135999XA CN03135999A CN100469836C CN 100469836 C CN100469836 C CN 100469836C CN B03135999X A CNB03135999X A CN B03135999XA CN 03135999 A CN03135999 A CN 03135999A CN 100469836 C CN100469836 C CN 100469836C
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Abstract
This invention relates to a high molecular polymer that is degradable pollutant, especially relates to heat waxiness and bio degradable polymer that consisted by poly lactic acid and starch. This invention further relates to production method of the polymer said above and the application of the polymer in producing agricultural use plastic membrane and food package materials.
Description
Field that the present invention belongs to
The present invention relates to biodegradable high molecular polymer, particularly relate to the hot plastic and biodegradable polymer of forming by poly(lactic acid) and starch basically.The invention further relates to the method for producing said polymkeric substance, and the application of said polymkeric substance in producing agripast film and packaging material for food.
The background of invention
Plastics (synthetic resins) are widely used in every field as a kind of important materials.Only with regard to daily life field, the plastics usage quantity that is used for food, general merchandise and family and industrial refuse packing in recent years constantly increases, and causes big city periphery garbage bury to produce the place shortage, and has therefore caused serious social concern.Packing plastics commonly used at present mainly comprises polyethylene, polypropylene, polystyrene, polyvinyl chloride etc.After these plastics are dropped since its very strong stability and can long-term existence in physical environment, cause the havoc of environment for human survival and natural landscape.
In recent years, many research-and-development activitys are all attempting to use the degradable plastics that can not produce above-mentioned these problems to prepare wrapping material.For example United States Patent (USP) 6,211, disclose for No. 325 a kind ofly to use poly(lactic acid) to be connected with starch or copolymeric material production highstrenghtpiston's method.Japanese Patent is open to be disclosed for 52-21530 number and a kind of nondegradable plastics such as polyethylene, polypropylene have been mixed method with the biodegradability of improving product with starch.
Though the plastics that use the preparation of these technology are easier to subside because of the degraded of starch, undegradable polymer segments remains complete, and still can cause environmental pollution.On the other hand, though after adding starch film toughness is reduced, even cause plastics behind the starch degradation still to keep the problem of original form because of the add-on of starch is less.
Several years ago, poly(lactic acid) (PLA), polycaprolactone biodegradable synthetic polymers such as (PCL) have just been arranged on the market.Wherein, lactic acid polymer can be degraded fully and produces harmless products such as lactic acid, carbonic acid gas and water through time several months in animal body.If under wet environment (as in soil and seawater), polymkeric substance can decompose in several weeks and disappear in about 1 year.Different with other degradable synthetic polymers, the PLA performance has mechanical characteristics preferably, therefore at present how selected surrogate as disposable and biodegradable plastic.Yet the higher relatively and degradation rate compare this polymkeric substance with the refuse stackeding speed of the production cost of PLA still shows slower.In addition, (greater than 60 ℃) PLA is easy to deliquescing (elasticity reduces by 85% approximately) under comparatively high temps, thereby has limited its application.
As the raw material of production poly(lactic acid), lactic acid is produced by cheap roughage such as fermented maize starch, maize treacle, perhaps also can be made by petrochemicals (as ethene).
Lactic acid polymer is normally made by the cyclodimerisation body (being so-called rac-Lactide) of lactic acid.Preparing under the multipolymer situation by the oxyacetic acid copolymerization, generally be with rac-Lactide with finish ring-opening polymerization (referring to United States Patent (USP) 1,995,970 and 2,683,136) after glycollide (dimer of oxyacetic acid) is mixed.When direct mixture dehydrating condensation by lactic acid or lactic acid and oxyacetic acid prepares polymkeric substance, generally be difficult to obtain high-molecular weight polymer.But then, the straight chain polyester that is made by the mixture ring opening copolymer of rac-Lactide or rac-Lactide and glycollide then has the molecular weight than rough sketch.
In general, under weather and agricultural practice condition preferably, the per hectare soil is expected to produce about 14,000 kilograms of corns.If the starch with these corns is raw material, use good fermentation system fermenting lactic acid, then the output of lactic acid is expected to reach the 3000-4000 pound.As seen, being raw material production with the W-Gum will have very high environment and economic benefit based on the degradable polymer (plastics) of lactic acid.
Starch is the renewable and degradable biological polymkeric substance that can be obtained by multiple source.But since starch itself water-soluble character determined, when it was used as plastic components, it is molten and be out of shape that starch can be met bulking after the moulded section.In order to reduce the interaction with water, usually starch is mixed with hydrophilic polymer to improve the biodegradability of polymer product.Though can (PHB) wait synthetic polymer to mix starch and polycaprolactone (PCL) and poly-(butyric ester), the present high strength biodegradable polymer of forming by the multipolymer of poly(lactic acid) or lactic acid and starch or treated starch that still successfully do not make basically.
The Northeast in China, corn is a kind of traditional farm crop of high yield.In order to develop corn, set up some corn deep processing enterprises in recent years in succession, and to produce W-Gum, the elementary corn product of corn wet goods.Though having many uses of these products, their economic worth is still limited.For this reason, it at first is that raw material is produced lactic acid through fermentation using bacteria with the W-Gum that the present invention attempts to set up a kind of, then with the ring-opening polymerization method of routine by lactic acid monomer production poly(lactic acid), and then be the method that raw material production has been improved the biodegradable polymer of physical properties with poly(lactic acid) and starch again.
The purpose of invention
An object of the present invention is to provide the biodegradable polymer of forming by the multipolymer and the starch of poly(lactic acid) or lactic acid basically.
According to a preferred embodiment of the invention, wherein the multipolymer of said lactic acid is the multipolymer of lactic acid and oxyacetic acid.
According to a preferred embodiment of the invention, wherein the molecular-weight average of poly(lactic acid) is 60,000-120,000 dalton.
According to a preferred embodiment of the invention, wherein starch is selected from W-Gum, sorghum starch, yam starch, wheat starch and tapioca (flour).
According to a preferred embodiment of the invention, wherein the weight ratio of starch and poly(lactic acid) is about 20:80-80:20.
Another object of the present invention provides the method for the biodegradable polymer that production is made up of the multipolymer and the starch of poly(lactic acid) or lactic acid basically, said method comprises at first in starch: the ratio that the poly(lactic acid) weight ratio is about 30:70 adds starch powder in pre-warmed poly(lactic acid), and heating and machinery are mixed resulting mixture in the presence of coupling group then.
According to a preferred embodiment of the invention, the temperature that wherein heats the mixture of poly(lactic acid) and starch is about 150-230 ℃.
The time of wherein heating according to a preferred embodiment of the invention, and mixing the mixture of poly(lactic acid) and starch is about 0.5-1 hour.
According to a preferred embodiment of the invention, wherein said coupling group is provided by MDI.
A further object of the present invention provides the application of biodegradable polymer in producing disposable plastic film and various casting film moulded plastic products of being made up of poly(lactic acid) or its multipolymer and starch basically that is defined as above.
The detailed description of invention
The present invention relates to biodegradable high molecular polymer, particularly relate to the hot plastic polymkeric substance of forming by poly(lactic acid) and starch or derivatives thereof basically.The invention further relates to the method for producing said polymkeric substance, and the application of said polymkeric substance in producing agricultural plastic film, packaging material for food and various casting mold plastics.
More particularly, the invention provides the new polymkeric substance of forming by poly(lactic acid) and starch, its production method and application.Wherein under the condition that has softening agent and heating, starch is by coupling group and poly(lactic acid) reaction, with the biodegradable polymer of the physical properties that improved.
The starch that is used for the inventive method includes but are not limited to W-Gum, sorghum starch, yam starch, wheat starch, rice starch and tapioca (flour).
Be used for the multipolymer that polymer materials of the present invention can be poly(lactic acid), poly(lactic acid) and other hydroxycarboxylic acids, or poly(lactic acid) and other hydroxycarboxylic acid mixture of polymers.Other hydroxycarboxylic acids that are suitable for comprise oxyacetic acid, hydroxybutyric acid etc.
As the monomeric compound of synthesizing polylactic acid, lactic acid is the natural molecule of widespread use in a kind of foodstuffs industry (for example as sanitas and seasonings).Though also can obtain by chemical synthesis process, lactic acid all is to produce with the method for microorganism (milk-acid bacteria) sugar fermentation raw material (glucose and hexose) basically in the practice.Sugar generally can be derived from cheap raw materials such as W-Gum, maize treacle.Preferred L-lactic-acid-producing strain comprises thermophilic lacto-bacilli and lactobacterium casei (thousand junket subspecies).Preferred milk-acid bacteria substratum should contain wheat germ and/or starch hydrolysate, yeast autolysate, amylolytic enzyme and proteolytic ferment and salt and water.
Lactic acid has oh group and carboxylic group, therefore can change into polymkeric substance at an easy rate.Because lactic acid exists with the form of two kinds of steric isomers basically, therefore can produce the lactic acid polymer of several different structure forms: D-poly(lactic acid), L-poly(lactic acid), D, L-poly(lactic acid) (the above two mix the racemize polymkeric substance that obtains) and meso poly(lactic acid) etc.
Can directly prepare these polymkeric substance through the dehydration polycondensation by lactic acid or other hydroxycarboxylic acids or their multipolymer, perhaps also can prepare required polymkeric substance through ring-opening polymerization by these sour cyclodimerisation bodies.Molecular weight to resulting polymkeric substance does not have particular restriction, but preferred molecular weight ranges is 60, and 000-120 is between 000 dalton.Molecular weight is less than the intensity of this scope possibility impact polymer product, and for example the undercapacity of resulting plastics film is to be used as winter protection or packaging material for food.Molecular weight then can make melting viscosity increase greater than this scope and cause processing difficulties.
In the composition that contains starch and poly(lactic acid), starch:: the weight ratio of poly(lactic acid) can be 20:80 to 80:20, but preferred part by weight is 30:70.
In the method for the invention, starch can be controlled by the starch content that changes in the composition with: the degradation speed of the formed composition of poly(lactic acid).Can improve degradation rate when for example, increasing contents of starch.When needs aggregate combinations Tetramune has high strength, then should suitably reduce contents of starch.
In order to prepare composition of the present invention, at first, in pre-warmed container, add starch powder and coupling agent then approximately heating polylactic resin under 150-230 ℃ the temperature, and under same temperature or lesser temps in pulverizing mill the about 0.5-1 of hot fusion hour.Perhaps, also can earlier poly(lactic acid) be mixed with linking group, and then to wherein adding starch and remaining poly(lactic acid).
In the inventive method employed coupling group should comprise at least one, best two isocyanate moieties, and preferred coupling group is a MDI.In the miscellany that contains starch, poly(lactic acid) and coupling group, the weight of coupling group should account for the 0.2-4% of composition total weight, preferably accounts for 0.4-3%.
Can use known additives (as stablizer, antioxidant and tinting material etc.) and softening agent (for example epoxidised soybean oil), according to known casting film moulding process composition of the present invention is made the plastics of different shape and structure, as food product containers or package packing supplies.Perhaps, also can be in solvent with composition dissolves of the present invention, and then the packing bag of casting film and food prepared therefrom, rubbish or other article.The polymeric composition that the inventive method is produced is because of having reduced the consumption of poly(lactic acid), so greatly reduce production cost.Particularly, the plastics of producing according to the inventive method not only have good biodegradability, and have the obvious physical properties of having improved (as tensile strength and thermoplastic behavior etc.).
Embodiment
Embodiment 1:
In the mixing tank of sealing, be that 100,000 daltonian poly(lactic acid) are admixed about 5 minutes with the mixture of about 2.5g MDI in 200 ℃ of machineries with the 100g molecular-weight average.In this miscellany, add the about 30g of starch then, and continue about 15 minutes of blending down in about 170 ℃.
During the first set reaction, reactive isocyanate is with part PLA " activation ".Continue after the reaction period second time between, activatory PLA interacts with the starch that newly mixes, makes the consistency raising of starch and PLA, finally causes the biodegradability of whole composition and physical strength to improve.
Embodiment 2:
In the mixing tank of sealing, at first 27g starch is mixed about 10 minutes of also machinery blending at normal temperatures with 70g PLA.In the mixture of starch and PLA, add about 3.0g MDI then.After the three mixed, the temperature of the mixing tank that raises gradually also kept about 12 minutes down at 180 ℃, simultaneously mixture was carried out machinery constantly and admixed.
During the normal temperature blending, the consistency between starch and the PLA is improved.Continue after high temperature under the blending during, the isocyanic acid coupling group that is provided by MDI interacts with hydroxyl and the carboxyl from PLA and starch respectively, with form chemically bound form, form polymeric composition by poly carboxylic acid and starch molecule.
Embodiment 3:
In the mixing tank of sealing, be 80,000 daltonian poly lactic coglycolic acids (50:50), 25g Zulkovsky starch, 8g ethyl oleate and 2.0g MDI uniform mixing with the 70g molecular-weight average and mixed about 8 minutes at 185 ℃ of following machineries.Agglomerate is extruded and is formed in pressurization then.
Under 180 ℃, the polymer clump that as above obtains is hot pressed into the semitransparent thin film of the about 30 μ m of thickness, surface smoothing.
Prepared film is embedded in the rubbish of accumulation the test of under 35 ℃, degrading.The result as seen, rear film went to pieces and completely dissolve after 70 days in 16 days.
Claims (7)
1. produce basically the method for the biodegradable polymer of forming by the multipolymer and the starch of poly(lactic acid) or lactic acid, said method comprises at first in starch: the poly(lactic acid) weight ratio is that the ratio of 30:70 adds starch powder in pre-warmed poly(lactic acid), mixes resulting mixture 0.5-1 hour in 150-230 ℃ of heating and machinery in the presence of coupling group then.
2. according to the process of claim 1 wherein that the multipolymer of said lactic acid is the multipolymer of lactic acid and oxyacetic acid.
3. according to the process of claim 1 wherein that starch is selected from W-Gum, sorghum starch, yam starch, wheat starch and tapioca (flour).
4. according to the process of claim 1 wherein that the molecular-weight average of poly(lactic acid) is 60,000-120,000 dalton.
5. according to the process of claim 1 wherein that the weight ratio of starch and poly(lactic acid) is 20:80-80:20.
6. according to the process of claim 1 wherein that said coupling group is provided by MDI.
7. the application of biodegradable polymer in production disposable plastic film and various casting film moulded plastic products of forming by poly(lactic acid) or its multipolymer and starch of producing according to the method for claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03135999XA CN100469836C (en) | 2003-09-29 | 2003-09-29 | Biodegradable polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03135999XA CN100469836C (en) | 2003-09-29 | 2003-09-29 | Biodegradable polymer |
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| Publication Number | Publication Date |
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| CN1603361A CN1603361A (en) | 2005-04-06 |
| CN100469836C true CN100469836C (en) | 2009-03-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB03135999XA Expired - Fee Related CN100469836C (en) | 2003-09-29 | 2003-09-29 | Biodegradable polymer |
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| CN1315927C (en) * | 2005-07-21 | 2007-05-16 | 同济大学 | Green degradable resin and production thereof |
| CN1919926B (en) * | 2006-09-12 | 2010-05-12 | 华南农业大学 | Polylactic acid-starch foaming material and preparation method thereof |
| JP4117900B2 (en) * | 2006-11-30 | 2008-07-16 | 聖子 佐藤 | Biodegradable natural materials derived from plants |
| CN100519488C (en) * | 2007-02-05 | 2009-07-29 | 中国科学院长春应用化学研究所 | Method for preparing slow-release fertilizer of carbamide |
| CN102250359B (en) * | 2011-06-14 | 2013-04-03 | 武汉华丽环保科技有限公司 | Grafting copolymer of starch and polylactic acid and preparation method thereof |
| CN103242626A (en) * | 2012-02-13 | 2013-08-14 | 刘松原 | Novel biodegradable material |
| CN103122133B (en) * | 2013-03-19 | 2015-02-11 | 宁波家塑生物材料科技有限公司 | Polylactic acid/plant polysaccharide environmentally-friendly composite material and preparation method thereof |
| CN103289339A (en) * | 2013-06-24 | 2013-09-11 | 苏州新区佳合塑胶有限公司 | Biodegradable plastic |
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| US11359088B2 (en) | 2015-06-30 | 2022-06-14 | BiologiQ, Inc. | Polymeric articles comprising blends of PBAT, PLA and a carbohydrate-based polymeric material |
| US11879058B2 (en) | 2015-06-30 | 2024-01-23 | Biologiq, Inc | Yarn materials and fibers including starch-based polymeric materials |
| US11046840B2 (en) | 2015-06-30 | 2021-06-29 | BiologiQ, Inc. | Methods for lending biodegradability to non-biodegradable plastic materials |
| US11926929B2 (en) | 2015-06-30 | 2024-03-12 | Biologiq, Inc | Melt blown nonwoven materials and fibers including starch-based polymeric materials |
| CN106263496A (en) * | 2016-08-29 | 2017-01-04 | 杜创洁 | The production technology of a kind of toothbrush and toothbrush |
| CN107641330A (en) * | 2017-09-26 | 2018-01-30 | 苏州市木包装材料有限公司 | A kind of degradable high tenacity wood moulding packaging material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6011092A (en) * | 1995-07-12 | 2000-01-04 | Valtion Teknillinen Tutkimuskeskus | Thermoplasticized starch component and process for the preparation thereof |
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2003
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6011092A (en) * | 1995-07-12 | 2000-01-04 | Valtion Teknillinen Tutkimuskeskus | Thermoplasticized starch component and process for the preparation thereof |
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| CN1603361A (en) | 2005-04-06 |
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