CN100441620C - All biodegradable branched starch master granulars - Google Patents
All biodegradable branched starch master granulars Download PDFInfo
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- CN100441620C CN100441620C CNB2006100250089A CN200610025008A CN100441620C CN 100441620 C CN100441620 C CN 100441620C CN B2006100250089 A CNB2006100250089 A CN B2006100250089A CN 200610025008 A CN200610025008 A CN 200610025008A CN 100441620 C CN100441620 C CN 100441620C
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Abstract
The present invention relates to all biodegradable grafting starch master granules which comprise the components of original corn starch, polytetramethylene azelaate ester, polylactic acid and natural rubber which are used as principal raw materials, a small amount of compatible agents are added, maleic acid (maleic acid anhydride) is used as a functional synthetic polymer, and diisopropyl benzene peroxide (DCP) is used as an initiating agent. The components are used for completing a grafting chemical reaction in a high-speed heating / cooling SRL type mixing machine, and master granules are mixed and manufactured in a corotating double screw extruder which is used for forming granules in the way of hot cutting a die surface. Compared with other kinds of modified starch, obtained biodegradable grafting starch master granules have favorable mechanical, thermal and biodegradable properties, and have the advantages of favorable compatibility with other biodegradable polymers, low cost and practical value of popularization and application.
Description
Technical field
The present invention relates to a kind of branched starch master granulars of complete biodegradable.
Background technology
Starch distributes very wide at occurring in nature, be component common in the higher plant, also is the principal mode of carbohydrate storage.W-Gum belongs to cereal starch, and it just is developed as far back as the seventies in 20th century as starch plastic.Because native starch is a kind of strong polarity crystalline polymer, intermolecularly there is an extremely strong hydrogen bond, its thermoplasticity extreme difference, and contain a large amount of hydroxyls in the starch again, very easily suction, therefore wetting ability and strong polarity make its can not with other resin compatible, can not get community preferably, be difficult to realize conventional plasticizing processing.For this reason, must carry out modification to the starch that is used for Biodegradable resin.The method of modification is the chemical modifications such as grafting of surface physics modification and starch, and its purpose is: the thermostability that improves starch; Improve the processing characteristics of starch, make starch increase plasticity-; Improve the hydrophobicity of starch, increase consistency with other resin.
The eighties in 20th century, people begin starch is carried out a large amount of study on the modification work, although on starch is handled action spot brains, all there is following common drawback in the starch plastic product of developing during this: 1. the adhesion of starch and polyolefine resins for universal use is bad, influences the mechanical property of finished product; 2. starch is difficult to be uniformly dispersed in mixing material; 3. the wetting ability of starch is harmful to the dimensional stability of finished product, and intensity reduces rapidly after the moisture absorption, and influence is used; 4. the starch thermostability is not strong, and processing temperature can not be higher than more than 200 ℃; 5. add the starch comparatively small amt, generally have only 7～15%, and cost is more expensive more than 25% than general-purpose plastics.
In view of starch is not had thermoplasticity, a flowability, can not melt molding, its intensity is extremely low again, thereby brings difficulty for the application of starch plastic.People are in order to improve treated starch plastics deficiency, the applying starch graft copolymer, as starch-grafted polyolefine, starch-grafted methyl methacrylate etc. to give the certain mechanical property of starch-resin, consistency and processibility.These products are compared with general treated starch plastics, though various aspects of performance makes moderate progress, because the intervention of petroleum resin, make the biological degradation of material can not be complete.
Summary of the invention
The objective of the invention is to produce with starch-grafted technology the starch master batch of energy complete biodegradable, it has more practical value, impels people to use this material more when design complete biodegradable product.
Embodiment of the present invention are as follows: make starch and MALEIC ANHYDRIDE (maleic anhydride) finish the grafting chemical reaction in heated at high speed/cooling SRL type mixing machine, self can degrade and can promote the component of degraded to finish master batch blend granulation in corotation twin screw extruder (the fervent mode granulating with die face) various again, its specifically fill a prescription (by weight percentage) is as follows:
Corn ative starch 45～80%
Poly butylene succinate (PBS) 10～30%
Toughner: natural rubber (NR) 2～4%
Initiator: dicumyl peroxide (DCP) 0.1～0.2%
Grafting agent: MALEIC ANHYDRIDE (MA) 0.45～0.8%
Softening agent: mono stearate glyceryl ester (GMS) 1～8%
Promoting agent: stearic acid (HSt) 0.5～1%
Inside and outside lubricant agent: low-molecular-weight wax and paraffin 3～10%.
Its specifically fill a prescription (by weight percentage) can also be:
Corn ative starch 32～50%
Poly butylene succinate (PBS) 20～30%
Poly(lactic acid) (PLA) 10～20%
Toughner: natural rubber (NR) 3～5%
Initiator: dicumyl peroxide (DCP) 0.1～0.2%
Grafting agent: MALEIC ANHYDRIDE (MA) 0.45～0.8%
Softening agent: mono stearate glyceryl ester (GMS) 1～8%
Promoting agent: stearic acid (HSt) 0.5～1%
Inside and outside lubricant agent: low-molecular-weight wax and paraffin 5～10%.
Below various components are done the schematic explanation:
The natural polymers that starch wherein is made up of D-glucose, its molecular weight can reach hundreds thousand of more than, the W-Gum of selecting for use northeast to produce during use, mean diameter: 10-15 μ m, density: 1.5g/cm
3, specific surface area: 300m
2/ kg;
Poly-succinic acid-butanediol fat (PBS) vitrifying commentaries on classics degree temperature wherein :-30～-46 ℃, fusing point: 92～115 ℃, melting index: 1～30g/10min;
Poly(lactic acid) wherein (PLA) second-order transition temperature: 48～58 ℃, fusing point: 150～160 ℃, melting index, 2～15g/10min;
Natural rubber wherein (NR) second-order transition temperature :-72 ℃, flow temperature: 130 ℃.
In process of grafting, use MALEIC ANHYDRIDE (MA) as functional polymer, produce chemical reaction with the hydroxyl in the starch, promptly utilize dicumyl peroxide (DCP) to make initiator, MALEIC ANHYDRIDE moved meet (graft) in polymkeric substance, the function of the polymkeric substance after the grafting is achieved.The grafting chemistry is reflected in heated at high speed/cooling SRL type mixing machine and finishes, and temperature of reaction 115-125 ℃, pressure is normal pressure.
Complete biodegradable graft starch functional polymer chemical reaction and granulation equipment used are the corotation twin screw extruder, and with the fervent mode granulating of die face, processing temperature is 150-185 ℃.
Embodiment
Describe the present invention in detail below by preferred embodiment, but do not limit the scope of the invention.The ordinary skill of this area is according to content of the present invention, and some nonessential improvement and adjustment to the present invention has done still belong to protection scope of the present invention.
Embodiment 1: all biodegradable branched starch master granulars 1# fill a prescription (mass fraction)
Starch 80 PBS 2 0DCP 0.15
MA 1 GMS 8 HSt 1
NR 3 paraffin+low-molecular-weight wax 10
Graft reaction is finished in heated at high speed/cooling SRL mixing machine, and graft starch is granulated and finished in the corotation twin screw extruder; Tensile strength 15MPa after tested, elongation 90%, degradation rate 〉=90%.
Embodiment 2: all biodegradable branched starch master granulars 2# fill a prescription (mass fraction)
Starch 70 PBS 30 DCP 0.15
MA 1 GMS 8 HSt 1
NR 5 paraffin+low-molecular-weight wax 10
Graft reaction is finished in heated at high speed/cooling SRL mixing machine, and graft starch is granulated and finish granulation in the corotation twin screw extruder; Tensile strength 20MPa after tested, elongation 100%, degradation rate 〉=90%.
Embodiment 3: all biodegradable branched starch master granulars 3# fill a prescription (mass fraction)
Starch 50 PBS 30 PLA 20
NR 5 DCP 0.2 MA 1
GMS 5 HSt 1 paraffin+low-molecular-weight wax 10
Graft reaction is finished in heated at high speed/cooling SRL mixing machine, and graft starch is granulated and finished in the corotation twin screw extruder; Tensile strength 25MPa after tested, elongation 200%, degradation rate 〉=90%.
Comparative example: the non-branched starch master granulars prescription (mass fraction) of degrading fully
Starch 70 new LDPE (film grade)s (LDPE) 20
MA 1 high density polyethylene(HDPE) (HDPE) 10
GMS 4 paraffin+low-molecular-weight wax 10
Ethylene acrylic acid co polymer (EAA) 5
Graft reaction is finished in heated at high speed/cooling SRL mixing machine, and graft starch is granulated and finished in the corotation twin screw extruder; Tensile strength 8MPa after tested, elongation 43%, degradation rate≤60%.
Show a pair of the present invention and other non-graft starch of degrading fully compares in the difference aspect mechanical property, thermal characteristics and the biodegradability.
Table one: the performance difference of the present invention and other non-graft starch of degrading fully
Contrast from table one as can be seen, test index of the present invention is compared better general with the non-graft starch index of degrading fully, particularly biological degradation rate is higher, better with the aliphatic polyester consistency, doping level can reach 50-70%, reduce complete biodegradable resin cost, had more the practical value of applying.
Claims (2)
1, a kind of all biodegradable branched starch master granulars is characterized in that: formed by the grafting of following weight percent composition, mixing granulation, it is 100% that various composition weight are counted sum:
Corn ative starch 45～80%
Poly butylene succinate 10～30%
Toughner: natural rubber 2～4%
Initiator: dicumyl peroxide 0.1～0.2%
Grafting agent: MALEIC ANHYDRIDE 0.45～0.8%
Softening agent: mono stearate glyceryl ester 1～8%
Promoting agent: stearic acid 0.5～1%
Inside and outside lubricant agent: low-molecular-weight wax and paraffin 3～10%.
2, a kind of all biodegradable branched starch master granulars is characterized in that: formed by the grafting of following weight percent composition, mixing granulation:
Corn ative starch 32～50%
Poly butylene succinate 20～30%
Poly(lactic acid) 10～20%
Toughner: natural rubber 3～5%
Initiator: dicumyl peroxide 0.1～0.2%
Grafting agent: MALEIC ANHYDRIDE 0.45～0.8%
Softening agent: mono stearate glyceryl ester 1～8%
Promoting agent: stearic acid 0.5～1%
Inside and outside lubricant agent: low-molecular-weight wax and paraffin 5～10%.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100250089A CN100441620C (en) | 2006-03-23 | 2006-03-23 | All biodegradable branched starch master granulars |
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| CNB2006100250089A CN100441620C (en) | 2006-03-23 | 2006-03-23 | All biodegradable branched starch master granulars |
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| CN1834139A CN1834139A (en) | 2006-09-20 |
| CN100441620C true CN100441620C (en) | 2008-12-10 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2918383B1 (en) * | 2007-07-05 | 2009-10-16 | Ct Valorisation Ind Agro Resso | USE OF FUNCTIONALIZED POLYLACTIC ACID AS A COMPATIBLE AGENT |
| CN102040713B (en) * | 2009-10-23 | 2013-11-06 | 中国科学院上海应用物理研究所 | Graft modified polymer material and preparation method thereof |
| CN101870774B (en) * | 2010-05-10 | 2013-05-08 | 梁雄辉 | Biological starch degradable plastic master batches, production method and degradable plastic thereof |
| CN102477216B (en) * | 2010-11-26 | 2013-11-20 | 上海华明高技术（集团）有限公司 | Polybutylene succinate fully biodegradable material and preparation process thereof |
| JP5980444B2 (en) | 2012-12-05 | 2016-08-31 | アクゾ ノーベル ケミカルズ インターナショナル ベスローテン フエンノートシャップＡｋｚｏ Ｎｏｂｅｌ Ｃｈｅｍｉｃａｌｓ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｂ．Ｖ． | Peroxide masterbatch based on bioresin |
| CN103242629B (en) * | 2013-05-14 | 2015-07-08 | 深圳市虹彩新材料科技有限公司 | Starch full-biodegradable resin and continuous preparation method thereof |
| CN105440606A (en) * | 2014-09-02 | 2016-03-30 | 允友成(宿迁)复合新材料有限公司 | Preparation method of fully biodegradable starch/polylactic acid base resin |
| CN108610739B (en) * | 2018-05-02 | 2021-05-07 | 广东佳景科技股份有限公司 | Modified amylopectin starch material, preparation method thereof and water-based ink containing modified amylopectin starch material |
| CN111019601B (en) * | 2019-12-26 | 2021-06-04 | 绿芸加(上海)环保科技有限公司 | Low-cost biodegradable hot melt adhesive special for paper packaging and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1354196A (en) * | 2001-12-17 | 2002-06-19 | 武汉华丽环保科技有限公司 | Starch-based biodegradable material and its preparation method |
| CN1415651A (en) * | 2002-12-10 | 2003-05-07 | 中国科学院长春应用化学研究所 | Method for preparing amylaceous fully degradable plastic |
| CN1597752A (en) * | 2004-08-23 | 2005-03-23 | 成都新柯力化工科技有限公司 | Biodegradation starch resin masterbatch |
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2006
- 2006-03-23 CN CNB2006100250089A patent/CN100441620C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1354196A (en) * | 2001-12-17 | 2002-06-19 | 武汉华丽环保科技有限公司 | Starch-based biodegradable material and its preparation method |
| CN1415651A (en) * | 2002-12-10 | 2003-05-07 | 中国科学院长春应用化学研究所 | Method for preparing amylaceous fully degradable plastic |
| CN1597752A (en) * | 2004-08-23 | 2005-03-23 | 成都新柯力化工科技有限公司 | Biodegradation starch resin masterbatch |
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