CN1315928C - Aliphatic polyester/starch/clay ternary degradable resin and production thereof - Google Patents
Aliphatic polyester/starch/clay ternary degradable resin and production thereof Download PDFInfo
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- CN1315928C CN1315928C CNB2005100279699A CN200510027969A CN1315928C CN 1315928 C CN1315928 C CN 1315928C CN B2005100279699 A CNB2005100279699 A CN B2005100279699A CN 200510027969 A CN200510027969 A CN 200510027969A CN 1315928 C CN1315928 C CN 1315928C
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Abstract
The present invention specifically relates to aliphatic polyester/starch/clay ternary full degradable resin and a preparation method thereof, which belongs to the technical field of high molecular materials. The degradable resin is composed of plant starch, aliphatic polyester, clay mineral type raw materials, a gelatinization accelerating agent, a plasticizing agent, an antioxidant, a lubricating agent and a compatibilizer. The raw materials are accurately weighed according to the proportion of the raw materials; then, the plant starch, the plasticizing agent and the gelatinization accelerating agent are sufficiently mixed and stirred for 5 to 30 minutes by a high-speed mixer; then, the mixed materials are placed for 1 to 2 days, and thus, the mixed materials are preplasticized; the preplasticized mixed materials, the aliphatic polyester and the clay mineral type raw materials, the antioxidant, the lubricating agent, etc. are added into a double screw extruder and melted and mixed by the double screw extruder; finally, the required product is obtained by a reaction extrusion. The degradable resin obtained by the present invention has excellent biodegradability, and thus, the degradable resin can effectively avoid 'white pollution'; besides, the present invention meets environment protecting requirements and is favorable to human beings; the present invention has a simple, flexible and effective preparation method, and the obtained material can be formed by many methods.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of aliphatic polyester/starch powder/clay ternary degradable resin and preparation method thereof.
Background technology
Plastics have become material most widely used on the our times, and various plastics have related to social production and various fields in life.But consequent resource-constrained has become two hang-ups of plastics circle with problem of environmental pollution.For head it off, people have proposed the development and application to degradative plastics.
The maximum degradative plastics of report is a starch plastics at present.But also have a certain proportion of polyolefin plastics (polyethylene, polypropylene, polystyrene) in most of goods, can not degrade fully after it is discarded, can not solve white pollution problems, and its mechanical property is again not as traditional macromolecular material ideal.Starch content only accounts for 30-60% in the patent report of publication number 12375963A, 1296988A and CN1415651A, and polyolefine has still accounted for about 40%.
Aliphatic polyester is present fully biodegradable plastics with fastest developing speed.Owing to contain the ester bond of facile hydrolysis on its main chain, so have good degradation property, aliphatic structure makes it have the good mechanical performance again simultaneously.But, be only limited to now at field of medicaments and use because it costs an arm and a leg.Therefore with starch and aliphatic polyester blend, can reduce its cost, and have biological degradability completely, be genuine degradative plastics.Report is also arranged in recent years both at home and abroad more.The Mater-Bi series product of Italy Novamont company are to prepare gained with polycaprolactone and thermoplastic starch.(Bastioli，C.Polym.Degrad.Stab.1998，59(1-3)，263-272)。But because the fusing point of polycaprolactone has only 60 ℃, its range of application is restricted.People such as the Xiuzhi Sun of Kansas State University study poly(lactic acid) and native starch blend, but consistency is relatively poor, and performance is stable inadequately.(Sun?X?Z；SeibP.J.Appl.Polym.Sci.2002，84，1257-1262)。Publication number is to adopt reactive compatibilizer to improve the consistency of starch and aliphatic polyester in the patent report of 1354196A, but need to prepare earlier the mixture of grafted monomer and acid anhydrides and derivative thereof, technology is complicated, and mechanical property is general, has limited its range of application.
Summary of the invention
The objective of the invention is to propose a kind of aliphatic polyester/starch powder/clay ternary degradable resin and preparation method thereof.
Aliphatic polyester/starch powder/clay ternary degradable resin that the present invention proposes, be made up of plant amylum, aliphatic polyester, clay mineral type raw material, gelation promotor, softening agent, oxidation inhibitor, lubricant, expanding material, the weight percent of its component is as follows:
Plant amylum 5-90%
Aliphatic polyester 5-90%
Clay mineral type raw material 0.5-20%
Gelation promotor 1-10%
Softening agent 1-15%
Oxidation inhibitor 1-5%
Lubricant 1-5%
Expanding material 0.5-10%.
Among the present invention, described plant amylum is to two kind in W-Gum, wheat starch, potato starch, sweet potato starch or the tapioca (flour) etc.
Among the present invention, described aliphatic polyester is: in poly(lactic acid) (PLA), poly-(lactic acid-ethanol) multipolymer (PLGA), poly-(lactic acid-ethylene glycol) multipolymer (PLA-PEG) or the polycaprolactone (PCL) etc. one to two kind.
Among the present invention, described gelation promotor is to two kind in urea or the oxyhydroxide.Described oxyhydroxide such as potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, aluminium hydroxide, manganous hydroxide, zinc hydroxide etc.
Among the present invention, described softening agent is in water, glycerine, sorbyl alcohol, ethylene glycol, propylene glycol, butyleneglycol, polyoxyethylene glycol, acetate sorbitol ester or the ethyl cellulose one to two kind.
Among the present invention, described oxidation inhibitor is nontoxic phosphite antioxidant class phosphorous acid ester three (2,4-di-tert-butyl phenyl) to two kind in the dimer of ester, pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) ester or many alkyl dihydroxyphenyl propane phosphorous acid ester, the trimer compositions etc.
Among the present invention, described lubricant is in ferrous etc. one to two kind of stearic acid, calcium stearate, Zinic stearas, Magnesium Stearate or stearic acid.
Among the present invention, described expanding material is to two kind in Resins, epoxy or the isocyanic ester etc.
The preparation method of a kind of aliphatic polyester/starch powder/clay ternary degradable resin that the present invention proposes, its concrete steps are: accurately take by weighing various raw materials by proportioning raw materials, with plant amylum, softening agent, gelation promotor through the high-speed mixer thorough mixing, stirred 5-30 minute, compound is placed 1-2 days then, made compound finish preplasticizing; Compound, aliphatic polyester, clay mineral type raw material, oxidation inhibitor, lubricant, the expanding material of finishing preplasticizing are joined twin screw extruder, use the twin screw extruder melt blending, react and extrude, extrusion temperature is 100-200 ℃, screw speed is 50-250 rev/min, and the residence time of material is 4-10 minute.
Among the present invention, described clay mineral type raw material can be selected existing clay mineral for use, if you would take off to two kind in soil, kaolinite, illite, sepiolite, chlorite and the modified montmorillonoid etc.Clay mineral type raw material also can adopt mother material to prepare, its concrete steps are: clay mineral, aliphatic polyester and softening agent are joined twin screw extruder in proportion, use the twin screw extruder melt blending, react and extrude, extrusion temperature is 150-200 ℃, screw speed is 50-150 rev/min, and the weight percent of wherein forming clay mineral type raw material is as follows:
Clay mineral 10-30%
Aliphatic polyester 60-80%
Softening agent 1-15%
Described clay mineral is to two kind in polynite, kaolinite, illite, sepiolite, chlorite or the modified montmorillonoid etc.;
Described aliphatic polyester is: in poly(lactic acid) (PLA), poly-(lactic acid-ethanol) multipolymer (PLGA), poly-(lactic acid-ethylene glycol) multipolymer (PLA-PEG), the polycaprolactone (PCL) etc. one to two kind;
Described softening agent is to two kind in glycerine, sorbyl alcohol, ethylene glycol, propylene glycol, butyleneglycol, polyoxyethylene glycol, acetate sorbitol ester or the ethyl cellulose etc.
The invention has the advantages that:
(1) selected for use biodegradable macromolecule resin and plant amylum compound, resulting product has excellent biological degradability, can effectively solve " white pollution " problem, satisfies environmental requirement, promotes the well-being of mankind;
(2) added gelation promotor, made the crystal of starch and grain pattern produce further destruction, thereby improved the Thermoplasticity of Starch processing characteristics;
(3) added clay novel inorganic filler,, on microcosmic, can form nanometer and strengthen a (see figure 1), improved the mechanical property of material with polymer formation fusion intercalation structure; Adopt clay mineral type raw material extrusion molding, improved the dispersing uniformity of clay in polymeric matrix;
(4) adopted big L/D ratio, have the twin screw extruder of exhaust and high-shear mixing plasticizing effect, guaranteed the quality of resin;
(5) preparation method is simple, flexible, effective, and the gained material can use the several different methods moulding.
Description of drawings
Fig. 1 is the transmission electron microscope picture of trielement composite material, and black part is divided into montmorillonite layer among the figure, and delamination occurs, is dispersed in the matrix, has formed nanocomposite.
Embodiment
Embodiment 1
50 gram W-Gums, 15 gram glycerine and 5 gram urea were stirred in high-speed mixer 15 minutes, mix, place and compound carried out pre-plasticising in 1 day.Then compound and 50 gram poly(lactic acid), 4 gram polynites, 1 are restrained oxidation inhibitor phosphorous acid ester three (2,4-di-tert-butyl phenyl) ester, 1 gram stearic acid, 1 gram Resins, epoxy mix the back in twin screw extruder in 130-170 ℃ of following high-temperature mixing, screw speed is 250 rev/mins, residence time of material is 4 minutes, extrude, granulation, moulding.Performance sees Table 1.
Embodiment 2
30 gram potato starches, 10 gram polyoxyethylene glycol and 1 gram sodium hydroxide were stirred in high-speed mixer 15 minutes, mix, place and compound carried out pre-plasticising in 1 day.Then compound and 70 gram poly(lactic acid), 10 gram modified montmorillonoids, 2 are restrained oxidation inhibitor phosphorous acid esters three (2,4-di-tert-butyl phenyl) ester, 1 gram stearic acid, 1 gram calcium stearate, 4 gram Resins, epoxy mix the back in twin screw extruder in 150-180 ℃ of following high-temperature mixing, screw speed is 200 rev/mins, residence time of material is 6 minutes, extrude, granulation, moulding.Performance sees Table 1.
Embodiment 3
With 70 gram poly(lactic acid), 30 gram polynites and 10 gram polyoxyethylene glycol in twin screw extruder in 150-170 ℃ of following mixing extruding, screw speed is 130 rev/mins, clay mineral type raw material.50 gram W-Gums and 15 gram glycerine and 1 gram potassium hydroxide were stirred in high-speed mixer 15 minutes, mix, place and compound carried out pre-plasticising in 1 day.Then compound and 40 gram poly(lactic acid), 20 gram clay mineral type raw materials, 1 are restrained oxidation inhibitor pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) ester, 1 gram calcium stearate, 3 gram isocyanic ester mix the back in twin screw extruder in 130-160 ℃ of following high-temperature mixing, screw speed is 50 rev/mins, the residence time of material is 10 minutes, extrude, granulation, moulding.Performance sees Table 1.
Embodiment 4
With 65 gram poly(lactic acid), 30 gram kaolinites and 15 gram butyleneglycols in twin screw extruder in 150-170 ℃ of following mixing extruding, screw speed is 150 rev/mins, clay mineral type raw material.The pure and mild 5 gram magnesium hydroxides of 35 gram wheat starches, 10 Keshan pears were stirred in high-speed mixer 10 minutes, mix, place and compound carried out pre-plasticising in 2 days.Then compound and poly-(lactic acid-ethanol) multipolymer of 50 grams, 15 gram clay mineral type raw materials, 1 are restrained oxidation inhibitor pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) ester, 1 gram stearic acid, 1 gram calcium stearate and 2 gram Resins, epoxy mix the back in twin screw extruder in 150-180 ℃ of following high-temperature mixing, screw speed is 250 rev/mins, residence time of material is 4 minutes, extrude, granulation, moulding.Performance sees Table 1.
Embodiment 5
With poly-(lactic acid-ethanol) multipolymer of 80 grams, 20 gram polynites and 10 gram glycerine in twin screw extruder in 180-200 ℃ of mixing extruding down, screw speed is 50 rev/mins, clay mineral type raw material.50 gram W-Gums, 10 gram glycerine and 1 gram sodium hydroxide were stirred in high-speed mixer 15 minutes, mix, place and carried out pre-plasticising in 1.5 days.Then with compound and 40 gram poly(lactic acid), 10 gram polycaprolactones, 10 gram clay mineral type raw materials, 2 gram oxidation inhibitor pentaerythritol bis-phosphites two (2,4-di-tert-butyl phenyl) ester, 1 gram Magnesium Stearate, 1 gram Zinic stearas and 7 gram isocyanic ester mix the back in twin screw extruder in 140-170 ℃ of following high-temperature mixing, screw speed is 150 rev/mins, residence time of material is 8 minutes, extrude granulation, moulding.Performance sees Table 1.
Embodiment 6
With 70 gram poly(lactic acid), 30 gram modified montmorillonoids, 10 gram glycerine and 5 gram ethylene glycol in twin screw extruder in 180-200 ℃ of following mixing extruding, screw speed is 100 rev/mins, clay mineral type raw material.To stir 20 minutes in 50 gram sweet potato starch, 15 gram propylene glycol and the 5 gram urea high-speed mixers, mix, place and carried out pre-plasticising in 2 days, then compound and 60 gram polycaprolactones, 15 gram clay mineral type raw materials, 4 are restrained oxidation inhibitor pentaerythritol bis-phosphites two (2,4-di-tert-butyl phenyl) ester, 3 gram stearic acid and 5 gram Resins, epoxy mix the back in twin screw extruder in 120-140 ℃ of following high-temperature mixing, screw speed is 120 rev/mins, the residence time of material is 9 minutes, extrude, granulation, moulding. performance sees Table 1.
Embodiment 7
With poly-(lactic acid-ethylene glycol) multipolymer of 80 grams, 30 gram polynites and 10 gram acetate sorbitol esters in twin screw extruder in 180-200 ℃ of mixing extruding down, screw speed is 150 rev/mins, clay mineral type raw material.40 gram potato starches, 5 gram butyleneglycols and 1 gram calcium hydroxide were stirred in high-speed mixer 10 minutes, mix, place and carried out pre-plasticising in 1-2 days.Then with starch and 50 gram polycaprolactones, 10 gram poly(lactic acid), 15 gram clay mineral type raw materials, 2 gram oxidation inhibitor, 1 gram Magnesium Stearate, 1 gram calcium stearate and 6 gram isocyanic ester mix the back in twin screw extruder in 120-150 ℃ of following high-temperature mixing, screw speed is 150 rev/mins, the residence time of material is 8 minutes, extrude, granulation, moulding.Performance sees Table 1.
The mechanical property of table 1 aliphatic polyester/starch powder/clay ternary matrix material
| Poly(lactic acid) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Tensile strength (MPa) | 55.08 | ?26.73 | ?45.25 | ?30.57 | ?32.18 | ?29.84 | ?28.49 | ?31.87 |
| Elongation at break (%) | 4.73 | ?4.63 | ?10.49 | ?6.75 | ?5.42 | ?9.71 | ?12.68 | ?11.29 |
| Flexural strength (MPa) | 87.16 | ?50.67 | ?69.84 | ?55.95 | ?58.36 | ?53.48 | ?56.45 | ?58.72 |
Claims (9)
1, a kind of aliphatic polyester/starch powder/clay ternary degradable resin, it is characterized in that being made up of plant amylum, aliphatic polyester, clay mineral type raw material, gelation promotor, softening agent, oxidation inhibitor, lubricant, expanding material, the weight percent of its component is as follows:
Plant amylum 5-90%
Aliphatic polyester 5-90%
Clay mineral type raw material 0.5-20%
Gelation promotor 1-10%
Softening agent 1-15%
Oxidation inhibitor 1-5%
Lubricant 1-5%
Expanding material 0.5-10%,
Wherein, gelation promotor is that one of potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, aluminium hydroxide, manganous hydroxide or zinc hydroxide are to two kinds.
2, aliphatic polyester/starch powder/clay ternary degradable resin according to claim 1 is characterized in that described plant amylum is to two kind in W-Gum, wheat starch, potato starch, sweet potato starch or the tapioca (flour).
3, aliphatic polyester/starch powder/clay ternary degradable resin according to claim 1 is characterized in that described aliphatic polyester is to two kind in poly(lactic acid), poly-(lactic acid-ethanol) multipolymer, poly-(lactic acid-ethylene glycol) multipolymer or the polycaprolactone.
4, aliphatic polyester/starch powder/clay ternary degradable resin according to claim 1 is characterized in that described softening agent is in water, glycerine, sorbyl alcohol, ethylene glycol, propylene glycol, butyleneglycol, polyoxyethylene glycol, acetate sorbitol ester or the ethyl cellulose one to two kind.
5, aliphatic polyester/starch powder/clay ternary degradable resin according to claim 1, it is characterized in that described oxidation inhibitor is nontoxic phosphite antioxidant class phosphorous acid ester three (2,4-di-tert-butyl phenyl) to two kind in the dimer of ester, pentaerythritol bis-phosphite two (2,4-di-tert-butyl phenyl) ester or many alkyl dihydroxyphenyl propane phosphorous acid ester, the trimer compositions.
6, aliphatic polyester/starch powder/clay ternary degradable resin according to claim 1 is characterized in that described lubricant is in ferrous one to two kind of stearic acid, calcium stearate, Zinic stearas, Magnesium Stearate or stearic acid.
7, aliphatic polyester/starch powder/clay ternary degradable resin according to claim 1 is characterized in that described expanding material is in Resins, epoxy or the isocyanic ester one to two kind.
8, a kind of preparation method of aliphatic polyester/starch powder/clay ternary degradable resin as claimed in claim 1, it is characterized in that concrete steps are: accurately take by weighing various raw materials by proportioning raw materials, with plant amylum, softening agent, gelation promotor through the high-speed mixer thorough mixing, stirred 5-30 minute, compound is placed 1-2 days then, made compound finish preplasticizing; Compound, aliphatic polyester, clay mineral type raw material, oxidation inhibitor, lubricant, the expanding material of finishing preplasticizing are joined twin screw extruder, use the twin screw extruder melt blending, react and extrude, extrusion temperature is 100-200 ℃, screw speed is 50-250 rev/min, and the residence time of material is 4-10 minute.
9, the preparation method of aliphatic polyester/starch powder/clay ternary degradable resin according to claim 8, the preparation method's concrete steps that it is characterized in that clay mineral type raw material are: clay mineral, aliphatic polyester and softening agent are joined twin screw extruder in proportion, use the twin screw extruder melt blending, react and extrude, extrusion temperature is 150-200 ℃, screw speed is 50-150 rev/min, and the weight percent of wherein forming clay mineral type raw material is as follows:
Clay mineral 10-30%
Aliphatic polyester 60-80%
Softening agent 1-15%
Described clay mineral is to two kind in polynite, kaolinite, illite, sepiolite, chlorite or the modified montmorillonoid;
Described aliphatic polyester is to two kind in poly(lactic acid), poly-(lactic acid-ethanol) multipolymer, poly-(lactic acid-ethylene glycol) multipolymer or the polycaprolactone;
Described softening agent is in glycerine, sorbyl alcohol, ethylene glycol, propylene glycol, butyleneglycol, polyoxyethylene glycol, acetate sorbitol ester or the ethyl cellulose one to two kind.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100584884C (en) * | 2006-08-28 | 2010-01-27 | 上海绿塑生物科技有限公司 | Preparation method of composite inorganic material reinforced high temperature resistant biodegradable agglomerate |
| CN102079820B (en) * | 2010-10-22 | 2012-07-04 | 曾广胜 | Completely biodegradable food packing material and preparation method thereof |
| CN104861600A (en) * | 2015-05-13 | 2015-08-26 | 常州龙骏天纯环保科技有限公司 | Polylactic acid degradable composite material and preparation method thereof |
| CN109337128A (en) * | 2018-09-05 | 2019-02-15 | 安徽新翔包装材料有限公司 | A kind of decomposable environmentally-friendly plastic packaging bag of high tenacity |
| CN109776878A (en) * | 2019-01-23 | 2019-05-21 | 侯萍 | A kind of garbage degradation material and its biodegrading process |
| CN112029154A (en) * | 2019-12-31 | 2020-12-04 | 锐保新材料科技(上海)有限公司 | Biodegradable material and preparation method thereof |
| CN116694051B (en) * | 2023-06-30 | 2024-08-06 | 福建康莱宝运动用品有限公司 | Low-cost thermal-stability completely biodegradable plastic and preparation method thereof |
| CN117089121A (en) * | 2023-08-17 | 2023-11-21 | 佛山市南海区百兴玩具有限公司 | Environment-friendly nontoxic starch plastic for toy |
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| JPH04146953A (en) * | 1990-10-09 | 1992-05-20 | Agency Of Ind Science & Technol | Method for controlling biodegradability of plastics |
| EP0530987A1 (en) * | 1991-08-08 | 1993-03-10 | MITSUI TOATSU CHEMICALS, Inc. | Degradable polymer composition |
| WO2002083784A1 (en) * | 2001-04-18 | 2002-10-24 | Food & Packaging Centre Management Limited | Biodegradable polymer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04146953A (en) * | 1990-10-09 | 1992-05-20 | Agency Of Ind Science & Technol | Method for controlling biodegradability of plastics |
| EP0530987A1 (en) * | 1991-08-08 | 1993-03-10 | MITSUI TOATSU CHEMICALS, Inc. | Degradable polymer composition |
| WO2002083784A1 (en) * | 2001-04-18 | 2002-10-24 | Food & Packaging Centre Management Limited | Biodegradable polymer |
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Assignee: Shanghai Green Plastic Bio-Technology Co., Ltd. Assignor: Tongji University Contract fulfillment period: 2009.11.1 to 2019.11.30 contract change Contract record no.: 2010310000001 Denomination of invention: Aliphatic polyester/starch/clay ternary degradable resin and production thereof Granted publication date: 20070516 License type: General permission Record date: 2010.1.4 |
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