CN1315927C - Green degradable resin and production thereof - Google Patents
Green degradable resin and production thereof Download PDFInfo
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- CN1315927C CN1315927C CNB2005100279684A CN200510027968A CN1315927C CN 1315927 C CN1315927 C CN 1315927C CN B2005100279684 A CNB2005100279684 A CN B2005100279684A CN 200510027968 A CN200510027968 A CN 200510027968A CN 1315927 C CN1315927 C CN 1315927C
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Abstract
The present invention specifically relates to green complete degradable resin and a preparation method thereof, which belongs to the technical field of high molecular resin. The green complete degradable resin is composed of plant starch, aliphatic polyester, a plasticizing agent, a compatibilizer, an antioxidant and a lubricating agent. The material is directly prepared by a reaction extruding method. The method specifically comprises: the plant starch and the plasticizing agent are sufficiently mixed and stirred for 10 to 20 minutes by a high speed mixer; then, the mixed materials are placed for 1 to 2 days, and thus, the mixed materials are preplasticized; subsequently, the preplasticized mixed materials, the aliphatic polyester, the compatibilizer, the antioxidant and the lubricating agent are added into a double screw extruder and melted and mixed by the double crew extruder; finally, the required product is obtained by a reaction extrusion. The present invention has the advantages of simple technology, convenient and easy realization, favorable product performance and no environment pollution and is suitable for industrialization production. The green complete degradable resin can be widely used for preparing disposable tableware, agricultural land membranes, shopping bags, etc. Owing to all the nontoxic raw materials, the present invention is especially suitable the production of outer package for food. The complete degradable material of the present invention can be completely degraded in natural environment after being used and discarded, or can be treated as compost without generating toxic substances. Therefore, the green complete degradable resin belongs to the environmental-friendly products.
Description
Technical field
The invention belongs to the macromolecule resin technical field, be specifically related to a kind of green degradable resin and preparation method thereof.
Background technology
The develop rapidly of development of modern industry, particularly petrochemical complex is for industrial and agricultural production and daily life provide a large amount of excellent performances, cheap synthetic resins and plastics.Yet the waste after using is discarded in places such as field, river, hill, street arbitrarily owing to deal with improperly, severe contamination existent environment of people, caused " white pollution ".At present, strict measure has all been formulated in countries in the world, limits the use of disposable plastic goods, simultaneously, advocates and support the research and development of degradation material energetically.Degradative plastics has become the research and development focus of extremely paying close attention to the world today as high-tech product and environmentfriendly products, its development has not only enlarged the function of plastics, and alleviated the contradiction of environment to a certain extent, exhausted day by day petroleum resources are one again replenish.Wherein, the compound Biodegradable resin of starch and aliphatic polyester is an important research direction.
Now the biodegradable plastic on the domestic market mainly is the biological damage plastic, is to be matrix with general-purpose plastics such as polyethylene, polypropylene, polystyrene, the biodegradable plastic that makes with degradable high polymer material blend such as starch.As publication number is the patent application of CN1115771A, CN1289792A and CN1280246A, CN1280146A, discloses following method in asking in its patent: earlier starch is carried out pre-treatment such as miniaturization, plasticising, make treated starch; Treated starch, general-purpose plastics, photosensitizers, prooxidant, coupling agent etc. are mixed extruding pelletization in high-speed mixer.Its shortcoming is starch pre-treatment more complicated, and general-purpose plastics can not biological degradation.This class Biodegradable resin has just solved visual pollution, does not tackle the problem at its root.
Aliphatic polyester is a class superpolymer of fully biodegradable at present with fastest developing speed.Because also have ester bond on its main chain, hydrolysis easily is so have good degradation property.Aliphatic structure makes it have the good mechanical performance again simultaneously.But, be only limited at present at field of medicaments and use because it costs an arm and a leg.If in its matrix, introduce cheap materials such as starch, can substitute the biological damage plastic that contains general-purpose plastics fully.A lot of these type of research reports are arranged in recent years, as the Mater-Bi series product of Italian Novamont company be exactly with polycaprolactone and thermoplastic starch preparation (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.Poly(lactic acid) is the material that has higher melt in the aliphatic polyester series, has excellent biocompatibility, biological degradability and mechanical property, is considered to the most promising wrapping material of 21 century.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；Seib P.J.Appl.Polym.Sci.2002，84，1257-1262)。
Summary of the invention
But the objective of the invention is to propose a kind of continuous production, easily-controlled operation, green degradable resin that quality product and biodegradability are good and preparation method thereof.
The present invention proposes a kind of green degradable resin, is made up of plant amylum, aliphatic polyester, softening agent, expanding material, oxidation inhibitor, lubricant, and the weight percent of its component is as follows:
Plant amylum 5-90%
Aliphatic polyester 5-90%
Softening agent 1-15%
Expanding material 0.5-10%
Oxidation inhibitor 1-5%
Lubricant 1-5%.
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 to two kind in poly(lactic acid) (PLA), poly-(lactic acid-ethanol) multipolymer (PLGA), poly-(lactic acid-ethylene glycol) multipolymer (PLA-PEG) or the polycaprolactone (PCL) etc.
Among the present invention, described softening agent is to two kind in water, glycerine, sorbyl alcohol, ethylene glycol, propylene glycol, butyleneglycol, polyoxyethylene glycol, acetate sorbitol ester, the ethyl cellulose etc.
Among the present invention, described expanding material is a Resins, epoxy.
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, stearic acid.
The preparation method of a kind of green degradable resin that the present invention proposes, its concrete steps are:
Accurately take by weighing various raw materials by proportioning raw materials, plant amylum, softening agent through the high-speed mixer thorough mixing, were stirred 10-20 minute, compound is placed 1-2 days then, make compound finish preplasticizing; Compound, aliphatic polyester, expanding material, oxidation inhibitor, lubricant are joined twin screw extruder, use the twin screw extruder melt blending, react and extrude, extrusion temperature is 120-200 ℃, screw speed is 50-200 rev/min, and the residence time of material is 4-10 minute.
Among the present invention, the twin screw extruder that is adopted, its screw slenderness ratio is 40: 1, has exhaust and high-shear mixing plasticizing effect.
The invention has the advantages that:
(1) selected for use biodegradable macromolecule resin and starch compound, resulting product has excellent biological degradability, can effectively solve " white pollution " problem, satisfies environmental requirement, promotes the well-being of mankind;
(2) add multiple properties-correcting agent, improved starch dispersed in matrix and with the consistency of matrix resin, improved the content of starch in resin and goods;
(3) adopted big L/D ratio, have the twin screw extruder of exhaust and high-shear mixing plasticizing effect, guaranteed the quality of resin;
(4) preparation method is simple, flexible, effective, and the gained material can use the several different methods moulding.
The present invention adopts the reaction extrusion molding directly to prepare material, and technology is simple, and is convenient and easy, and product performance are good, and environmentally safe is suitable for suitability for industrialized production.Product can be widely used in preparation disposable tableware, agricultural mulching, shopping bag etc.Because raw material is nontoxic material, is particularly suitable for the production of food outer packaging.Can in physical environment, degrade fully after Wholly-degradable material of the present invention uses and discards, or make composting, not produce toxic substance, belong to the environmental friendliness based article.
Embodiment
Further specify content of the present invention below in conjunction with embodiment.
Embodiment 1
50 gram W-Gums and 15 gram glycerine were stirred in high-speed mixer 15 minutes, mix, place and starch carried out pre-plasticising in 1 day, obtain compound.Then compound and 50 gram poly(lactic acid), 1 gram Resins, epoxy, 1 are restrained phosphorous acid ester three (2,4-di-tert-butyl phenyl) ester, 1 gram stearic acid mix the back in twin screw extruder in 150-170 ℃ of following high-temperature mixing, extrude, granulation, moulding, the rotating speed of twin screw extruder is 50 rev/mins, and residence time of material is 10 minutes.Performance sees Table 1.
Embodiment 2
30 gram potato starches and 10 gram polyoxyethylene glycol were stirred in high-speed mixer 15 minutes, mix, place and starch carried out pre-plasticising in 1 day, obtain compound.Then compound and 70 gram poly(lactic acid), 4 gram Resins, epoxy, 2 are restrained phosphorous acid esters three (2,4-di-tert-butyl phenyl) ester, 1 gram stearic acid, 1 gram calcium stearate mix the back in twin screw extruder in 160-180 ℃ of following high-temperature mixing, extrude, granulation, moulding, the rotating speed of twin screw extruder is 150 rev/mins, and residence time of material is 5 minutes.Performance sees Table 1.
Embodiment 3
50 gram W-Gums and 15 gram glycerine were stirred in high-speed mixer 15 minutes, mix, place and starch carried out pre-plasticising in 1 day, obtain compound.Then compound and 50 gram poly(lactic acid), 0.5 gram isocyanic ester, 1 are restrained phosphorous acid ester three (2,4-di-tert-butyl phenyl) ester, 1 gram calcium stearate mix the back in twin screw extruder in 140-160 ℃ of following high-temperature mixing, extrude, granulation, moulding, the rotating speed of twin screw extruder is 150 rev/mins, and residence time of material is 5 minutes.Performance sees Table 1.
Embodiment 4
The pure and mild 5 gram water of 35 gram wheat starches, 10 Keshan pears were stirred in high-speed mixer 10 minutes, mix, place and starch carried out pre-plasticising in 1.5 days, obtain compound.After then compound and poly-(lactic acid-ethylene glycol) multipolymer of 50 grams, 2 gram Resins, epoxy, 1 gram PL-34,1 gram stearic acid and 1 gram calcium stearate being mixed in twin screw extruder in 150-170 ℃ of following high-temperature mixing, extrude, granulation, moulding, the rotating speed of twin screw extruder is 200 rev/mins, and residence time of material is 4 minutes.Performance sees Table 1.
Embodiment 5
50 gram W-Gums and 10 gram glycerine were stirred in high-speed mixer 15 minutes, mix, place and carried out pre-plasticising in 1-2 days, obtain compound.Then with compound and 40 gram poly(lactic acid), 10 gram polycaprolactones, 3 gram Resins, epoxy, 2 gram pentaerythritol bis-phosphites two (2,4-di-tert-butyl phenyl) ester, 1 gram Magnesium Stearate, 1 gram Zinic stearas mix the back in twin screw extruder in 140-170 ℃ of following high-temperature mixing, extrude, granulation, moulding, the rotating speed of twin screw extruder are 120 rev/mins, and residence time of material is 7 minutes.Performance sees Table 1.
Embodiment 6
50 gram tapioca (flour)s, 10 gram propylene glycol and 1 gram ethyl cellulose were stirred in high-speed mixer 15 minutes, mix, place and carried out pre-plasticising in 1-2 days, obtain compound.Then compound and poly-(lactic acid-ethanol) multipolymer of 40 grams, 2 gram Resins, epoxy, 2 are restrained pentaerythritol bis-phosphites two (2,4-di-tert-butyl phenyl) ester, 1 gram stearic acid, 1 gram calcium stearate mix the back in twin screw extruder in 140-170 ℃ of following high-temperature mixing, extrude, granulation, moulding, the rotating speed of twin screw extruder is 180 rev/mins, and residence time of material is 4 minutes.Performance sees Table 1.
The mechanical property of table 1 fully bio-degradable resin
| Poly(lactic acid) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Tensile strength (MPa) | 55.08 | 23.65 | 43.81 | 21.96 | 37.19 | 25.47 | 30.54 |
| Elongation at break (%) | 4.73 | 5.63 | 16.49 | 4.62 | 12.48 | 8.57 | 5.47 |
| Flexural strength (MPa) | 87.16 | 41.23 | 63.57 | 38.73 | 56.96 | 55.48 | 46.81 |
Claims (7)
1, a kind of green degradable resin is characterized in that being made up of plant amylum, aliphatic polyester, softening agent, expanding material, oxidation inhibitor, lubricant, and the weight percent of its component is as follows:
Plant amylum 5-90%
Aliphatic polyester 5-90%
Softening agent 1-15%
Expanding material 0.5-10%
Oxidation inhibitor 1-5%
Lubricant 1-5%,
Wherein, expanding material is a Resins, epoxy.
2, green 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, green 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), poly-(lactic acid-ethylene glycol) or the polycaprolactone.
4, green degradable resin according to claim 1 is characterized in that described softening agent is to two kind in water, glycerine, sorbyl alcohol, ethylene glycol, propylene glycol, butyleneglycol, polyoxyethylene glycol, acetate sorbitol ester or the ethyl cellulose.
5, green 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, green 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, a kind of preparation method of green degradable resin as claimed in claim 1, its concrete steps are: accurately take by weighing various raw materials by proportioning raw materials, with plant amylum, softening agent through the high-speed mixer thorough mixing, stirred 10-20 minute, compound is placed 1-2 days then, made compound finish preplasticizing; Compound, aliphatic polyester, expanding material, oxidation inhibitor, the lubricant of finishing preplasticizing are joined twin screw extruder, use the twin screw extruder melt blending, react and extrude, extrusion temperature is 120-200 ℃, screw speed is 50-200 rev/min, and the residence time of material is 4-10 minute.
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| CNB2005100279684A CN1315927C (en) | 2005-07-21 | 2005-07-21 | Green degradable resin and production thereof |
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| CNB2005100279684A CN1315927C (en) | 2005-07-21 | 2005-07-21 | Green degradable resin and production thereof |
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| CN1315927C true CN1315927C (en) | 2007-05-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7232367B1 (en) | 2022-03-29 | 2023-03-02 | 東洋インキＳｃホールディングス株式会社 | Thermoplastic resin composition for agricultural materials and agricultural materials |
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| CN101942117B (en) * | 2010-09-25 | 2012-11-14 | 梁靖 | Starch-based fully degraded packaging material and preparation method thereof |
| CN102558795B (en) * | 2010-12-17 | 2014-09-10 | 上海杰事杰新材料(集团)股份有限公司 | Polylactic acid-starch blended material and preparation method thereof |
| CN103525098B (en) * | 2012-07-07 | 2016-03-30 | 广东广信电气科技有限公司 | A kind of degradable natural resin composite materials being applicable to the insulated shell of batch meter |
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| 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 |
| CN105368020B (en) * | 2015-08-28 | 2018-09-14 | 大禹节水（天津）有限公司 | Anti- drip irrigation zone, which is burnt, uses degradable mulch |
| CN110734625A (en) * | 2019-10-24 | 2020-01-31 | 樊刚 | plastic film materials and preparation method thereof |
| CN111057274A (en) * | 2019-11-29 | 2020-04-24 | 湖南工业大学 | High-filling starch-based thermoplastic composite material and preparation method thereof |
| CN111423706A (en) * | 2020-04-28 | 2020-07-17 | 睿泊(中国)环保科技有限公司 | Degradable material, tableware and preparation method thereof |
| CN113121969A (en) * | 2021-04-15 | 2021-07-16 | 天津科技大学 | Degradable antibacterial plastic sheet and preparation |
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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.: 2010310000005 Denomination of invention: Green degradable resin and production thereof Granted publication date: 20070516 License type: General permission Record date: 2010.1.5 |
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Free format text: COMMON LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.11.1 TO 2019.11.30; CHANGE OF CONTRACT Name of requester: SHANGHAI GREEN PLASTIC BIO-TECHNOLOGY CO., LTD. Effective date: 20100105 |