CN102276877B - Plastication modified fully-degradable waterproof starch plastic and preparation method thereof - Google Patents
Plastication modified fully-degradable waterproof starch plastic and preparation method thereof Download PDFInfo
- Publication number
- CN102276877B CN102276877B CN 201110191797 CN201110191797A CN102276877B CN 102276877 B CN102276877 B CN 102276877B CN 201110191797 CN201110191797 CN 201110191797 CN 201110191797 A CN201110191797 A CN 201110191797A CN 102276877 B CN102276877 B CN 102276877B
- Authority
- CN
- China
- Prior art keywords
- starch
- 10min
- butylene succinate
- poly butylene
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to a plastication modified fully-degradable waterproof starch plastic and a preparation method thereof. The starch plastic comprises 5-90% of natural starch, 5-90% of poly(butylene succinate), 1-50% of plasticizer, 1-50% of compatibilizer, and 0.1-10% of auxiliary agents. The method comprises the steps of: mixing the starch and plasticiser uniformly in advance according to the above mass percent, disposing the mixture for 1-24h, and mixing poly(butylene succinate), the compatibilizer and the auxiliary agents with the mixture uniformly, adding the obtained mixture into a Haake for melt blending; or mixing the components well according to the ratio with a high speed mixer, conducting extrusion in an extruder so as to obtain a blending; and finally carrying out hot pressing to the blending first under a pressure of 1-30MPa and at a temperature of 100-200DEG C for 1-10min, and then conducting cold pressing for 1-10min for moulding at a pressure of 10MPa. The plasticof the invention has low cost and can prepare alloys with good compatibility between two ingredients. And finally the mechanical property and water proofness of the alloys are obviously improved. Meanwhile, as starch and the plastic are fully-degradable, thus the alloys obtained are environmental friendly.
Description
Technical field
The present invention relates to a kind of high-fall solution water tolerance plasticizing treated starch plastics and preparation method thereof.Specifically, relating to a kind of is that thermoplastic starch (TPS) and poly butylene succinate (PBS) are the water resistant starch plastics of main raw material with the starch after the plasticizing.
Technical background
At present, plastics have replaced the wider metallic substance of former this application etc. rapidly because it has simple, the easy advantages such as suitability for industrialized production, water-fast, resistance to chemical attack of production technique.But along with plastic prod uses on a large scale, become the significant problem that the whole world is paid close attention to by its environmental pollution that causes.How to handle these plastics and then be subjected to common concern.Although each country has all taked Corresponding Countermeasures to handle, not only can not fundamentally address this problem, also cause secondary pollution easily.In addition, because petroleum resources are in short supply day by day, thereby degradable high polymer material just obtains people's attention.
Starch is because cheap, and wide material sources have good degradability simultaneously, thereby become one of biodegradable natural polymer that is most widely used.But because the starch after the plasticizing of process fluidizer is that thermoplastic starch mechanical property and water tolerance are relatively poor, thereby limited its application to a great extent.Improving a kind of effective means of thermoplastic starch mechanical property and hydrophobicity is exactly and the degradable polymer blend, poly butylene succinate is a kind of aliphatic polyester that can degrade fully, have excellent biological compatibility and Bioabsorbable, performance is between polyethylene and polypropylene simultaneously, although its price is higher than starch, but compare with other degradable plasticss such as poly(lactic acid), polycaprolactones, price is still relatively low.Yet hydrophilic starch and hydrophobic poly butylene succinate can not be compatible, although the thermoplastic starch that obtains with the fluidizer plasticizing has certain consistency with poly butylene succinate, but still can not be compatible fully, thereby can improve both consistencies by adding compatilizer, further improve mechanical property and the water resistance of starch/poly butylene succinate starch plastic.
Summary of the invention
The objective of the invention is to address the deficiencies of the prior art, provide a kind of cost low, the group partition inter-capacitive excellence, high-fall solution, water tolerance has high-fall solution water tolerance plasticizing treated starch plastics of bigger improvement and preparation method thereof, by adding the expanding material acid anhydrides, glycidyl methacrylate graft POE (POE-g-GMA) (Ningbo NengZhiGuang New Materials Science Co., Ltd provides) and maleic anhydride grafted ethene octene copolymer (POE-g-MAH) (Nanjing moral bar chemical industry company limited), to improve the consistency of starch and polymeric matrix in the starch plastic, further improve the mechanical property of material, water resistance etc., can be enough in the production, reduce cost, and environmental protection.
The present invention is achieved by the following technical solutions:
A kind of high-fall solution water tolerance plasticizing treated starch plastics is characterized in that component and mass percent that described starch plastic comprises are as follows:
Its total amount satisfies 100%;
Wherein, described native starch is a kind of in W-Gum, tapioca (flour), the yam starch, preferred W-Gum,
Described poly butylene succinate is that melt flow rate (MFR) is a kind of in the poly butylene succinate of 1.5g/10min or 25g/10min, and the melt flow rate (MFR) of preferred poly butylene succinate is 1.5g/10min,
Described fluidizer is one or more in glycerol, methane amide, the water,
Described expanding material is one or more in acid anhydrides, glycidyl methacrylate graft POE, the maleic anhydride grafted ethene octene copolymer, and wherein, described acid anhydrides is one or more in Succinic anhydried, the maleic anhydride,
Described auxiliary agent is lubricant and dispersion agent, wherein lubricant preferably polyethylene wax and/or stearic acid, the preferred ethylene bis stearic acid amide of dispersion agent.
The present invention also proposes a kind of preparation method of high-fall solution water tolerance plasticizing treated starch plastics, it is characterized in that described method comprises the steps:
(1) preparation blend: starch, fluidizer are pre-mixed into even batch mixing by above-mentioned mass percent in room temperature (20～30 ℃), place 1～24h, make fluidizer fully penetrate in the starch molecule; Poly butylene succinate, expanding material and auxiliary agent are mixed with above-mentioned even batch mixing again, join melt blending in the Haake torque rheometer again, mixing temperature is 100～200 ℃, and rotating speed is 60rpm, obtains blend;
Perhaps with high-speed mixer that native starch, poly butylene succinate, fluidizer, expanding material and auxiliary agent is even by described mixed, in forcing machine, extrude then and obtain blend, each of forcing machine section processing temperature is 80 ℃, 100 ℃, 120 ℃, 150 ℃, rotating speed 150～300rpm;
(2) blend that step (1) is obtained is in 1～30MPa, 100～200 ℃ of following hot pressing 1～10min, and 1～10min moulding of colding pressing under the 10MPa namely makes described high-fall solution water tolerance plasticizing treated starch plastics.
High-fall solution water tolerance plasticizing treated starch plastics of the present invention can be processed as film by various moulding processs, sheet material, and sheet material and various moulded products, the resulting product tensile strength is 10～50MPa, shock strength is 2～10KJ/m
2, heat-drawn wire is 80～120 ℃, the coefficient of softening of material reaches more than 0.85, and the water tolerance excellence, degradation rate is more than 90% in three months simultaneously.
The present invention is by adding fluidizer, make the interaction that produces between itself and the starch, obtain plasticized starch, then with poly butylene succinate in the presence of expanding material, prepare two component compatibilities starch plastic preferably by Haake torque rheometer or forcing machine, thereby improve mechanical property and the water resistance of alloy.Starch is cheap, with the poly butylene succinate hybrid process after, can significantly improve its mechanical property and water tolerance, reduced the cost of poly butylene succinate plastics simultaneously, in addition, starch and poly butylene succinate all are a kind of polymkeric substance that can degrade fully, and that resulting starch plastic alloy has is with low cost, easy-formation processing, biological degradability height, advantages of environment protection can be used in the articles for daily use such as disposable tableware, wrapping material.
Embodiment
Feature of the present invention and advantage will be elaborated by embodiment, but described embodiment only is used for the present invention rather than restriction the present invention.
Embodiment 1
Accurately take by weighing 15 parts of starch, 5 parts of glycerine are pre-mixed, sealing is preserved, place 24h after, and then with 70 parts of poly butylene succinates, 5 parts of Succinic anhydrieds, 2 parts of polyethylene waxs, 1 part of stearic acid, 2 parts of ethylene bis stearic acid amides mix, join banburying in the Haake torque rheometer, temperature is set at 130 ℃, and rotating speed is 60rpm, melt blending 10min, obtain starch/polybutylene succinate polyblend, under 10MPa pressure, 140 ℃ of following hot pressing 5min are under the 10MPa pressure again, the 3min moulding of colding pressing, be cut into various standard battens by the ASTM standard at last and carry out performance test, its tensile strength is 36.6MPa, and shock strength is 5.0KJ/m
2, heat-drawn wire is 108 ℃, coefficient of softening is that 0.91, three month degradation rate reaches 90%.
Embodiment 2
Accurately take by weighing 15 parts of starch, 5 parts of glycerine are pre-mixed, sealing is preserved, place 24h after, and then with 70 parts of poly butylene succinates, 5 parts of maleic anhydrides, 2 parts of polyethylene waxs, 1 part of stearic acid, 2 parts of ethylene bis stearic acid amides mix, join banburying in the Haake torque rheometer, temperature is set at 130 ℃, and rotating speed is 60rpm, melt blending 10min, obtain starch/polybutylene succinate polyblend, under 10MPa pressure, 140 ℃ of following hot pressing 5min are under the 10MPa pressure again, the 3min moulding of colding pressing, be cut into various standard battens by the ASTM standard at last and carry out performance test, its tensile strength is 38.3MPa, and shock strength is 4.6KJ/m
2, heat-drawn wire is 99 ℃, coefficient of softening is that 0.88, three month degradation rate reaches 91%.
Embodiment 3
Accurately take by weighing 15 parts of starch, 5 parts of glycerine, be pre-mixed, sealing is preserved, place 24h after, and then with 70 parts of poly butylene succinates, 5 parts of glytidyl methacrylate grafted ethene-octene copolymers, 2 parts of polyethylene waxs, 1 part of stearic acid, 2 parts of ethylene bis stearic acid amides mix, join banburying in the Haake torque rheometer, temperature is set at 130 ℃, and rotating speed is 60rpm, melt blending 10min, obtain starch/polybutylene succinate polyblend, under 10MPa pressure, 140 ℃ of following hot pressing 5min are under the 10MPa pressure again, the 3min moulding of colding pressing, be cut into various standard battens by the ASTM standard at last and carry out performance test, its tensile strength is 41.1MPa, and shock strength is 4.3KJ/m
2, heat-drawn wire is 103 ℃, coefficient of softening is that 0.89, three month degradation rate reaches 94%.
Embodiment 4
Accurately take by weighing 15 parts of starch, 5 parts of glycerine, be pre-mixed, sealing is preserved, place 24h after, and then with 70 parts of poly butylene succinates, 5 parts of maleic anhydride grafted ethene octene copolymers, 2 parts of polyethylene waxs, 1 part of stearic acid, 2 parts of ethylene bis stearic acid amides mix, join banburying in the Haake torque rheometer, temperature is set at 130 ℃, and rotating speed is 60rpm, melt blending 10min, obtain starch/polybutylene succinate polyblend, under 10MPa pressure, 140 ℃ of following hot pressing 5min are under the 10MPa pressure again, the 3min moulding of colding pressing, be cut into various standard battens by the ASTM standard at last and carry out performance test, its tensile strength is 39.1MPa, and shock strength is 4.3KJ/m
2, heat-drawn wire is 100 ℃, coefficient of softening is that 0.88, three month degradation rate reaches 93%.
Embodiment 5
Accurately take by weighing 30 parts of starch, 10 parts of glycerine are pre-mixed, sealing is preserved, after placing 24h, and then with 50 parts of poly butylene succinates, 5 parts of glytidyl methacrylate grafted ethene-octene copolymers, 2 parts of polyethylene waxs, the banburying in the Haake torque rheometer of 1 part of stearic acid, 2 parts of ethylene bis stearic acid amides, temperature is set at 130 ℃, rotating speed is 60rpm, melt blending 10min obtains starch/polybutylene succinate polyblend, again under 10MPa pressure, 140 ℃ of following hot pressing 5min, under the 10MPa pressure, the 3min moulding of colding pressing is cut into various standard battens by the ASTM standard at last and carries out performance test, its tensile strength is 20.5MPa, and shock strength is 3.8KJ/m
2, heat-drawn wire is 92 ℃, coefficient of softening is that 0.85, three month degradation rate reaches 95%.
Embodiment 6
Accurately take by weighing 30 parts of starch, 10 parts of glycerine are pre-mixed, sealing is preserved, after placing 24h, add 50 parts of poly butylene succinates then, 5 parts of maleic anhydride grafted ethene octene copolymers, 2 parts of polyethylene waxs, the banburying in the Haake torque rheometer of 1 part of stearic acid, 2 parts of ethylene bis stearic acid amides, temperature is set at 130 ℃, rotating speed is 60rpm, melt blending 10min obtains starch/polybutylene succinate polyblend, again under 10MPa pressure, 140 ℃ of following hot pressing 5min, under the 10MPa pressure, the 3min moulding of colding pressing is cut into various standard battens by the ASTM standard at last and carries out performance test, its tensile strength is 22.5MPa, and shock strength is 3.3KJ/m
2, heat-drawn wire is 94 ℃, coefficient of softening is that 0.85, three month degradation rate reaches 95%.
Claims (4)
1. a high-fall solution water tolerance plastifies the treated starch plastics, it is characterized in that the composition of described starch plastic is made up of following mass ratio:
Its total amount satisfies 100%;
Wherein, described native starch is a kind of in W-Gum, tapioca (flour), the yam starch,
Described poly butylene succinate is that melt flow rate (MFR) is a kind of in the poly butylene succinate of 1.5g/10min or 25g/10min,
Described fluidizer is one or more in glycerol, methane amide, the water,
Described expanding material is one or both in glycidyl methacrylate graft POE, the maleic anhydride grafted ethene octene copolymer,
Described auxiliary agent is lubricant and dispersion agent.
2. high-fall solution water tolerance plasticizing treated starch plastics as claimed in claim 1 is characterized in that the melt flow rate (MFR) of described poly butylene succinate is 1.5g/10min.
3. high-fall solution water tolerance plasticizing treated starch plastics as claimed in claim 1 is characterized in that described lubricant is polyethylene wax and/or stearic acid, and dispersion agent is ethylene bis stearic acid amide.
4. the preparation method of high-fall solution water tolerance plasticizing treated starch plastics as claimed in claim 1 is characterized in that described preparation method comprises the steps:
(1) preparation blend: starch, fluidizer are pre-mixed into even batch mixing by above-mentioned mass ratio in 20～30 ℃, place 1～24h, make fluidizer fully penetrate in the starch molecule; Poly butylene succinate, expanding material and auxiliary agent are mixed with above-mentioned even batch mixing again, join melt blending in the Haake torque rheometer again, mixing temperature is 100～200 ℃, and rotating speed is 60rpm, obtains blend;
Perhaps with high-speed mixer that native starch, poly butylene succinate, fluidizer, expanding material and auxiliary agent is even by described mixed, in forcing machine, extrude then, obtain blend, each of forcing machine section processing temperature is 80 ℃, 100 ℃, 120 ℃, 150 ℃, rotating speed 150～300rpm;
(2) blend that step (1) is obtained is in 1～10MPa, 100～200 ℃ of following hot pressing 1～10min, and 1～10min moulding of colding pressing under the 10MPa namely makes described high-fall solution water tolerance plasticizing treated starch plastics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110191797 CN102276877B (en) | 2011-07-11 | 2011-07-11 | Plastication modified fully-degradable waterproof starch plastic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110191797 CN102276877B (en) | 2011-07-11 | 2011-07-11 | Plastication modified fully-degradable waterproof starch plastic and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102276877A CN102276877A (en) | 2011-12-14 |
| CN102276877B true CN102276877B (en) | 2013-10-02 |
Family
ID=45102639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110191797 Expired - Fee Related CN102276877B (en) | 2011-07-11 | 2011-07-11 | Plastication modified fully-degradable waterproof starch plastic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102276877B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731840A (en) * | 2012-06-29 | 2012-10-17 | 华东理工大学 | High-filling degradable starch plastic used in disposable tableware |
| GB201217207D0 (en) * | 2012-09-26 | 2012-11-07 | Biome Bioplastics Ltd | Bio-resins |
| CN102924885B (en) * | 2012-11-23 | 2015-01-21 | 宁夏青林盛华科技有限公司 | Nano cyclic phenyl hydroxide modified starch/PBS biology base degradation dedicated material and preparation method thereof |
| CN103992517B (en) * | 2014-06-10 | 2016-06-15 | 华东理工大学 | One can be continuously produced fully-degradable starch base plastic alloy and preparation method thereof |
| CN104650389A (en) * | 2015-02-02 | 2015-05-27 | 安徽玉堂雨具有限公司 | Water-resistant biodegradable plastic and preparation method thereof |
| CN105037817A (en) * | 2015-08-11 | 2015-11-11 | 安徽鑫科生物环保有限公司 | Disposable tableware capable of being completely degraded |
| CN106749705A (en) * | 2016-11-24 | 2017-05-31 | 安徽瑞研新材料技术研究院有限公司 | A kind of non-staple food grain complex denaturation hydrophobic starch preparation method of biomembrane list |
| CN106589852A (en) * | 2016-12-15 | 2017-04-26 | 中国科学院理化技术研究所 | Water degradation material with adjustable degradation period and preparation method thereof |
| CN109535671B (en) * | 2018-12-12 | 2020-11-13 | 怀化学院 | Polybutylene succinate composite material and preparation method thereof |
| CN110819087A (en) * | 2019-12-08 | 2020-02-21 | 怀化学院 | Full-biodegradable mulching film and preparation method thereof |
| CN111849035A (en) * | 2020-07-17 | 2020-10-30 | 李庆芳 | Method for manufacturing disposable product |
| CN113754990A (en) * | 2021-08-26 | 2021-12-07 | 江苏诚盟装备股份有限公司 | Starch-based full-biodegradable material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2770973A1 (en) * | 2009-08-18 | 2011-02-24 | National Research Council Of Canada | Process of producing thermoplastic starch/polymer blends |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240086B (en) * | 2008-03-14 | 2011-08-17 | 上海悦仕生物材料有限公司 | Total-biodegradation plastic film and preparation method thereof |
-
2011
- 2011-07-11 CN CN 201110191797 patent/CN102276877B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2770973A1 (en) * | 2009-08-18 | 2011-02-24 | National Research Council Of Canada | Process of producing thermoplastic starch/polymer blends |
Non-Patent Citations (2)
| Title |
|---|
| PBS-g-MAH及MAH对PBS/淀粉合金力学性能的影响;酒永斌等;《化工新型材料》;20060430;第34卷(第4期);第37页第2栏第5-6行，第38页第1栏第22-25行和第39页表2体系组成3 * |
| 酒永斌等.PBS-g-MAH及MAH对PBS/淀粉合金力学性能的影响.《化工新型材料》.2006,第34卷(第4期), |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102276877A (en) | 2011-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102276877B (en) | Plastication modified fully-degradable waterproof starch plastic and preparation method thereof | |
| CN107556536B (en) | Low-cost bio-based fully-degradable film and preparation method thereof | |
| CN103992517B (en) | One can be continuously produced fully-degradable starch base plastic alloy and preparation method thereof | |
| CN103159984B (en) | All-degradable thermoplastic starch/polylactic acid blend material and preparation method thereof | |
| CN112111133A (en) | Preparation method of polybutylene terephthalate adipate/polylactic acid/starch ternary blending film blowing resin | |
| CN103360674A (en) | Wood powder composite foam material and preparation method thereof | |
| CN102477216B (en) | Polybutylene succinate fully biodegradable material and preparation process thereof | |
| CN106366596A (en) | Polylactic acid/chemically modified natural rubber blend material and preparing method thereof | |
| CN102702705A (en) | Toughened polylactic acid/polyolefin elastomer composite material and preparation method thereof | |
| CN103589125B (en) | A kind of Polylactic acid/polypropylene blend and preparation method thereof | |
| CN101525487A (en) | Composite material degraded by environment and preparation method thereof | |
| CN102321354A (en) | A kind of plasticizing polylactic acid/composite polyethylene material and preparation method thereof | |
| CN109535490B (en) | Starch master batch for filling modified degradable high polymer material and preparation method thereof | |
| CN108530854B (en) | Preparation method of straw powder-PLA wood-plastic composite material | |
| CN103012856A (en) | Microcrystalline cellulose and polyvinyl alcohol reinforced starch-based full-biodegradable blending material and preparation method thereof | |
| CN102250389B (en) | Biodegradable polymer material compatibilized and blended by lignocellulose and preparation method thereof | |
| CN101293994B (en) | Multi-component totally degradable polymer composite and its preparation method | |
| CN102229720B (en) | High impact polypropylene composition and preparation method thereof | |
| CN105602214A (en) | Plasticized and toughened modified polylactic acid and preparation method thereof | |
| CN114891331A (en) | Toughened polylactic acid/starch blending material and preparation method thereof | |
| CN102702655B (en) | Polyvinyl alcohol/high amylose biodegradable material and melting preparation method thereof | |
| CN111484673B (en) | Modified polypropylene plastic | |
| CN111234484B (en) | Full-bio-based degradable polylactic acid/starch composite material and preparation method thereof | |
| CN103102657B (en) | Biodegradable blend and preparation method and application thereof | |
| CN116144187B (en) | Polylactic acid composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131002 Termination date: 20170711 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |