CN102775644B - Nanocomposite starch micro-foaming biodegradable material - Google Patents
Nanocomposite starch micro-foaming biodegradable material Download PDFInfo
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- CN102775644B CN102775644B CN201210068834.7A CN201210068834A CN102775644B CN 102775644 B CN102775644 B CN 102775644B CN 201210068834 A CN201210068834 A CN 201210068834A CN 102775644 B CN102775644 B CN 102775644B
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Abstract
The invention discloses a nanocomposite starch micro-foaming biodegradable material which comprises 40-70wt% of starch, 0.5-1wt% of biological enzyme, 1-2.5% of polyol ester, 0.5-1wt% of amino fatty acid, 2-5wt% of modified nano-calcium, 25-55% of modified ethylene-vinyl acetate copolymer and 1-2wt% of foaming agent. The starch base material processing is simplified, the material specific gravity is reduced, and the production cost and price are lowered; compared with the existing resin degradation material, the nanocomposite starch micro-foaming biodegradable material has the advantages that the price is reduced by more than 40-50%, the performances such as wear resistance, toughness, rigidity, foaminess and the like of the biodegradable material are improved, the material processing temperature is reduced, a finished product can be obtained by direct processing, and the pigmenting property of the material can be improved; all the raw materials are biodegradable materials, do not contain polyolefin materials such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC) and the like, can be completely degraded in nature and do not cause environmental pollution; meanwhile, the nanocomposite starch micro-foaming biodegradable material can be conveniently recycled, thus being widely used for a disposable product, articles for daily life, pharmaceutical packaging, a toy, a membrane product and industrial product cushion packaging material.
Description
Technical field
The present invention relates to a kind of novel high polymer material, especially relate to biodegradated polymer materal.
Background technology
At present, a large amount of white pollutions (plastics) of existing of nature and black pollution (rubber item) etc. are all caused by broad-spectrum macromolecular material.Day by day serious along with environmental pollution, development be not only conducive to environment protection, but also the type material-degradable high polymer material with the various performance of macromolecular material be inexorable trend.At present, degradable high polymer material is in research and development and Partial Conversion stage, it mainly contains microbiological deterioration material, biodegradable material, photodegradation material and chemical degradation material, wherein both to have the excellent use properties of macromolecular material, can dissolve again with inorganization and high-molecular biologic degradable material that is that become Carbon cycle is attached most importance to after discarded completely, the degradable plastics mulch film with W-Gum fermentative production used as the U.S. and Japan and the auto parts machinery made with sweet potato starch researched and developed in the recent period and the computer casing made with W-Gum.Although the U.S. and Japan have have researched and developed and have employed biodegradated polymer materal, but there is following problem in actual use in them: one is that degradable plastics mulch film production cost is high, expensive, biodegradable material actual output and consumption are all little, promote the use of and there is difficulty; Two is that biodegradable material manufacturing process formula and control techniques are also little ripe, causes the various performances such as biodegradable material thermotolerance, wear resistance, shape stability and rigidity high not enough.Do not meet biodegradable material towards high-performance, low consumption, recycling, recirculation and the development trend of degrading voluntarily.Think by analysis, biodegradable material is caused to there is the problems referred to above major cause: although one be starch is a kind of abundant renewable polymeric materials, but because containing great amount of hydroxy group in starch molecular chain, intermolecular interaction is large in power, make decomposition temperature lower than its fusing point, cause that starch viscosity is high, processing fluidity is lower, needing to carry out thermoplastification process to starch could machine-shaping; Two is that hydroxyl hydrophilic in starch molecular chain is high, causes its water tolerance poor.How to carry out thermoplastification and solve water tolerance poor, one is that the method for conventional plasticising is to prepare thermoplastic starch, to solve thermoplastification problem so that machine-shaping in the prior art.Two is to adopt with the coupling agent such as Aluminate, titanic acid ester and polyolefine or its copolymer blended processing method to improve the consistency of starch matrix, solves water tolerance poor.But because in prior art, thermoplastification effect is not high, add that technology controlling and process is also accurately enough, cause the various performances of biodegradable material still to can not get significantly improving, thus limit biodegradable material and apply widely.
Summary of the invention
For the problem existing for the biodegradable material adopting Starch Production in above-mentioned prior art, the invention provides one and both can significantly improve various performance, can decompose completely again after discarded with inorganization and become the nano combined starch fretting map biodegradable material of Carbon cycle.
The technical scheme that the technical problem to be solved in the present invention is taked is: described nano combined starch fretting map biodegradable material by 40-70%wt starch, 0.5-1%wt biological enzyme, 1-2.5%wt polyol resin, the amino lipid acid of 0.5-1%wt, 2-5%wt modified Nano calcium, 25-55%wt ethene improved-whipping agent of vinyl acetate copolymer and 1-2%wt forms, and is prepared from by following preparation method's step:
(1), through 60-100 DEG C, add biological enzyme, polyol resin, the mixing of amino lipid acid in the dry starch of 10-15 minute, when temperature rises to 110-120 DEG C, add again through polyol resin and the modified Namigai of amino lipid acid and ethylene-vinyl acetate copolymer blended, and then add whipping agent, treated starch base-material can be obtained, for subsequent use after cooling;
(2), treated starch base-material is put in the same way vented twin screw equipment through low temperature high-shear, one-step synthesis is the nano combined starch fretting map biodegradable material of sheet material, or put into the nano combined starch fretting map biodegradable material that fretting map equipment makes fretting map sheet material, or put into the nano combined starch fretting map biodegradable material that exhaust granulating equipment makes granular.
The nano combined starch fretting map biodegradable material of described sheet material can in all kinds of Blister product processing or industrial goods buffering package; Granular nano combined starch fretting map biodegradable material can in injection molding or blown film processing.
Described starch is W-Gum, potato starch etc.; Described biological enzyme is amylase, lipase, proteolytic enzyme etc.; Described polyol resin is the lipid that in prior art, glycerine, Polyglycerine, sorbyl alcohol, anhydrous sorbitol, sucrose etc. and lipid acid generate, the Sorbitan alcohol ester that single glyceride that preferably glycerine and lipid acid generate or anhydrous sorbitol and lipid acid generate.
Described ethylene-vinyl acetate copolymer (EVA) is degradable material, does not damage environment, nontoxic, and its chemical stability is high, anti-aging, miscibility, color forming property and molding processibility good.Also ethylene-vinyl acetate copolymer can be replaced with vinyl-vinyl acetate copolymer.
Described whipping agent preferred BIH series, non-azo foaming agent series or conventional food grade food product pack special environment protection whipping agent.
Technology mechanism of the present invention is: in the starch of drying, add biological enzyme agent, through the combined action of the physical force of polyol resin, modification is carried out to starch, shorten existing starch conversion technique, thus reduce starch viscosity, improve processing fluidity, the plastic processibility of starch composite biodegradable material and foaminess are improved significantly, greatly improve thermoplastification effect, amino lipid acid and modified Nano calcium is added again in treated starch, carry out chemical reaction by the multipoint adsorption of similar anchor formula simultaneously, reach surface chemical reaction completely coated, filling surface is organised, improve affinity and the consistency of substrate macromolecule material, substantially increase the water tolerance of starch, whole composite system is formed threadly mutually to be intertwined, form a large amount of crazing structure, the mechanical property of goods is improved significantly, enhance adhesivity and the film-forming properties of starch base-material, improve the thermotolerance of goods, wear resistance, the performance such as shape stability and rigidity, compared with existing similar articles, density have dropped less than 10%, low-temperature performance drops to-40 degree by-10 degree, thermal stability improves more than 25%, toughness improves more than 30%, and goods cost can be reduced, improve processing effect
Rate, makes the variation of nano combined starch fretting map biodegradable material purposes.
Technique effect of the present invention is:
1, this invention simplifies starch base-material complete processing,
2, present invention reduces material proportion and production cost and price, compared with existing resin degradation material, prices more than 40-50%,
3, the various performances such as biodegradable material wear resistance, toughness, rigidity and foaminess are significantly improved,
4, materials processing temperature is reduced, can direct processed finished products, improve material tinctorial property,
5, raw material is all biodegradable material, not containing polyolefine materials such as PE, PP, PS, PVC, can be degradable at occurring in nature, free from environmental pollution, be convenient to again recycle simultaneously, disposable product, daily necessities, medical packaging, toy, membrane product and industrial goods amortizing packaging material can be widely used in.
Embodiment
Embodiment 1, described nano combined starch fretting map biodegradable material
By 55%wt W-Gum, 0.5%wt amylase, the mono-glyceride of 2%wt, 0.5%wt amino lipid acid, 5%wt
Modified Nano calcium, 35%wt be ethene improved-the BIH series whipping agent composition of vinyl acetate copolymer (EVA) and 2%wt, and be prepared from by following preparation method's step:
(1), through 60-100 DEG C, add amylase, single glyceride, the mixing of amino lipid acid in the dry starch of 10-15 minute, when temperature rises to 110-120 DEG C, add again through polyol resin and the modified Namigai of amino lipid acid and ethylene-vinyl acetate copolymer blended, add BIH series whipping agent again, obtain treated starch base-material, for subsequent use after cooling;
(2), above-mentioned treated starch base-material is put into fretting map equipment foam, namely can be made into the nano combined starch fretting map biodegradable material of fretting map sheet material.
Embodiment 2, described nano combined starch fretting map biodegradable material by 44%wt sweet potato starch, 1%wt lipase, 1%wt Sorbitan alcohol ester, the amino lipid acid of 1%wt, 2%wt modified Nano calcium, 50%wt ethene improved-the non-azo foaming agent of vinyl acetate copolymer and 1%wt forms, step is prepared from as follows:
(1), through 60-100 DEG C, add biological enzyme, Sorbitan alcohol ester, the mixing of amino lipid acid in the dry starch of 10-15 minute, when temperature rises to 110-120 DEG C, add again through polyol resin and the modified Namigai of amino lipid acid and ethylene-vinyl acetate copolymer blended, add non-azo foaming agent again, obtain treated starch base-material, for subsequent use after cooling;
(2), by above-mentioned treated starch base-material put in the same way that vented twin screw equipment is through low temperature high-shear, one-step synthesis is the nano combined starch fretting map biodegradable material of sheet material.
Embodiment 3, described nano combined starch fretting map biodegradable material by 66%wt W-Gum, 0.5%wt proteolytic enzyme, 1%wt Sorbitan alcohol ester, the amino lipid acid of 0.5%wt, 2%wt modified Nano calcium, 29%wt ethene improved-the food grade environment-friendly foaming agent of vinyl acetate copolymer and 1%wt forms, and step is prepared from as follows:
(1), through 60-100 DEG C, add proteolytic enzyme, Sorbitan alcohol ester, the mixing of amino lipid acid in the dry starch of 10-15 minute, when temperature rises to 110-120 DEG C, add again through polyol resin and the modified Namigai of amino lipid acid and vinyl-vinyl acetate copolymer blended, then the agent of food grade environment-friendly foaming is added, obtain treated starch base-material, for subsequent use after cooling;
(2), above-mentioned treated starch base-material is put into exhaust granulating equipment carry out granulation, namely can be made into the nano combined starch fretting map biodegradable material of granular.
Claims (2)
1. nano combined starch fretting map biodegradable material, it is characterized in that: it by 40-70%wt starch, 0.5-1%wt biological enzyme, 1-2.5%wt polyol resin, the amino lipid acid of 0.5-1%wt, 2-5%wt modified Nano calcium, 25-55%wt ethene improved-whipping agent of vinyl acetate copolymer and 1-2%wt forms, and is prepared from by following preparation method's step:
(1), through 60-100 DEG C, add biological enzyme, polyol resin, the mixing of amino lipid acid in the dry starch of 10-15 minute, when temperature rises to 110-120 DEG C, add again through polyol resin and the modified Namigai of amino lipid acid and ethylene-vinyl acetate copolymer blended, and then add whipping agent, treated starch base-material can be obtained, for subsequent use after cooling;
(2), treated starch base-material is put in the same way vented twin screw equipment through low temperature high-shear, one-step synthesis is the nano combined starch fretting map biodegradable material of sheet material, or put into the nano combined starch fretting map biodegradable material that fretting map equipment makes fretting map sheet material, or put into the nano combined starch fretting map biodegradable material that exhaust granulating equipment makes granular.
2. nano combined starch fretting map biodegradable material according to claim 1, is characterized in that: described polyol resin is the Sorbitan alcohol ester that single glyceride of generating of glycerine and lipid acid or anhydrous sorbitol and lipid acid generate.
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| CN201210068834.7A CN102775644B (en) | 2012-03-16 | 2012-03-16 | Nanocomposite starch micro-foaming biodegradable material |
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| CN201210068834.7A CN102775644B (en) | 2012-03-16 | 2012-03-16 | Nanocomposite starch micro-foaming biodegradable material |
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| CN102775644B true CN102775644B (en) | 2015-04-22 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105254930A (en) * | 2015-10-19 | 2016-01-20 | 界首市佳宝包装材料有限公司 | Biodegradable foaming meal box |
| CN106638143A (en) * | 2016-12-15 | 2017-05-10 | 钦州市钦南区科学技术情报研究所 | Weaving-paper hardening coating and preparing method thereof |
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| GB1121131A (en) * | 1964-07-20 | 1968-07-24 | Marius Berghgracht | Starch hydrolyzates and process for their manufacture |
| CN1916062A (en) * | 2005-08-15 | 2007-02-21 | 李小鲁 | Biodegradable composition of resin containing starch, products and prepartion method |
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| CN102019705A (en) * | 2009-09-21 | 2011-04-20 | 逢甲大学 | Method for manufacturing biobased macromolecule shoe material |
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2012
- 2012-03-16 CN CN201210068834.7A patent/CN102775644B/en active Active
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|---|---|---|---|---|
| GB1121131A (en) * | 1964-07-20 | 1968-07-24 | Marius Berghgracht | Starch hydrolyzates and process for their manufacture |
| CN1916062A (en) * | 2005-08-15 | 2007-02-21 | 李小鲁 | Biodegradable composition of resin containing starch, products and prepartion method |
| CN1970611A (en) * | 2006-08-02 | 2007-05-30 | 福州大学 | Process for preparing EVA/PE/starch composite foam material |
| CN101506291A (en) * | 2006-08-04 | 2009-08-12 | 普朗蒂克科技有限公司 | Mouldable biodegradable polymer |
| CN101597388A (en) * | 2008-06-02 | 2009-12-09 | 逢甲大学 | Biochemical shoe material and manufacture method thereof |
| CN102019705A (en) * | 2009-09-21 | 2011-04-20 | 逢甲大学 | Method for manufacturing biobased macromolecule shoe material |
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| 于文杰等.常见无机填料表面处理剂.《塑料助剂与配方设计技术》.化学工业出版社,2010,(第3版),342-343页. * |
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