CN1074433C - Polyester type starch plastic - Google Patents

Polyester type starch plastic Download PDF

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Publication number
CN1074433C
CN1074433C CN97115212A CN97115212A CN1074433C CN 1074433 C CN1074433 C CN 1074433C CN 97115212 A CN97115212 A CN 97115212A CN 97115212 A CN97115212 A CN 97115212A CN 1074433 C CN1074433 C CN 1074433C
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China
Prior art keywords
starch
plastic
polyester type
plastic cement
type starch
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Expired - Fee Related
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CN97115212A
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CN1208743A (en
Inventor
王振宏
王屹南
李之强
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Qinghua Ziguang (group) General Co
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Qinghua Ziguang (group) General Co
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Priority to CN97115212A priority Critical patent/CN1074433C/en
Publication of CN1208743A publication Critical patent/CN1208743A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

The present invention relates to polyester type starch plastic rubber which is characterized in that a composition comprises the components of starch, glycerol, 1, 2-propanediol, fatty acid, sorbitol, an alkaline substance, a gelatin solution and white carbon black, and the required plastic rubber can be obtained by extruding the components by a double-screw extruder. Plastic rubber products can be degraded and have no toxicity; the discarded materials can be directly used as animals' fodder or be used with the other fodder after being recovered and pulverized as well as can be mixed with polyethylene, polypropylene, polystyrene plastics, natural rubber, cispolybutadiene rubber, nitrile rubber, styrene-butadiene rubber, etc. so as to prepare degradable thin films, sheets and foaming products.

Description

Polyester type starch plastic and its production and application
The present invention relates to biodegradable starch base plastic cement composition and preparation method thereof.
As everyone knows, since plastics come out,, used increasingly extensive because of characteristics such as its light weight, product are both artistic and practical.But the rapid increase of consequent plastic garbage, seriously contaminate environment.For addressing this problem, people study various treating methods, and important method is is wherein researched and developed exactly and caused burden little to environment, uses back easy to handle material, as the various biodegradable plastics of development and application.For example publication number is the patent application of CN1050390A, CN1049854A and CN1112143A, all be to propose to prepare biodegradable plastic with the way of starch and polymer blending, but also there is complex process in this class degradative plastics, intermiscibility is poor, dispersed bad, cost is than problems such as height, and the polymkeric substance that the starch composition stays after being decomposed is difficult to continue degraded.
The objective of the invention is to overcome the shortcoming of prior art, it is simple to propose a kind of technology, is uniformly dispersed and does not contain degradable starch base plastic cement composition of polymkeric substance and preparation method thereof.
Order of the present invention is to realize by following proposal: the certain proportion of starch, softening agent, ultra-fine white carbon black, higher aliphatic acid, auxiliary agent, gelatin water composition is mixed, be squeezed into required plastic cement by twin screw extruder.
Plastic cement composition of the present invention comprises starch, glycerol, 1,2-propylene glycol, lipid acid, sorbyl alcohol, alkaline matter, gelatin water, white carbon black.Composition levels:
Starch accounts for the 60-80% of composition weight, other each component is a benchmark with starch weight, concrete content: glycerol 15-30%, 1,2-propylene glycol 8-15%, lipid acid 0.5-3.5%, sorbyl alcohol 0.5-10%, alkaline matter 5-25%, gelatin water 10-50%, white carbon black 1-20%.
Above-mentioned composition also can add vegetables oil, and its amount is the 5-30% of starch total amount.
The preparation process of plastic cement of the present invention comprises:
(1) gelatin soaks 0.5-2h and obtains gelatin water in 30-50 ℃ of water, adds alkaline matter then, and heating is dissolved it fully, adds glycerol, 1 again, and the 2-propylene glycol is or/and vegetables oil obtains mixture A, and described gelatin and water weight ratio are 1: 10-30;
(2) starch, sorbyl alcohol, white carbon black, lipid acid are added in the container of belt stirrer in proportion, obtain mixture B at 70 ℃ of following high-speed stirring 5-10min;
(3) mixture A transports in the screw extrusion press with the flow velocity of 140-400 Grams Per Minute, mixture B is added in the forcing machine hopper with the speed of 800-1800 Grams Per Minute, two kinds of mixtures are finished vibration, stirring, shearing, reaction process in forcing machine, to reach gel polymerisation, its main-machine screw rotating speed is 80-180r/min, temperature is 60-150 ℃, head pressure 2-8Mpa.
Above-mentioned steps (1) glycerol or/and vegetables oil also can in step (2), add.Described starch comprises corn, potato, rice, cassava, beans, starch or mat powder, preferably is selected from medical starch, green starch or mat powder.
White carbon black of the present invention is the strengthening agent of plastic cement, to the intensity of plastic cement, and transparency, anti tear, performance important influence such as hardness, the used white carbon black of the present invention is the superfine white carbon black of a kind of particle diameter＜20nm, its commercial disignation is TS-3.
Lipid acid of the present invention is the lubricant of plastic cement, can make the plastic cement smooth surface, increases light transmission.Lipid acid of the present invention comprises C 10-C 20Lipid acid or its esters.
Glycerol of the present invention, 1,2-propylene glycol, sorbyl alcohol all are commercially available prod, they play plastification to plastic cement, and can keep it that enough intensity is arranged.
Vegetables oil of the present invention comprises soya-bean oil, peanut oil, salad oil, Semen Maydis oil.In making anti-water pref, need to add vegetables oil in the plastic cement composition.
Alkaline matter of the present invention comprises bicarbonate of ammonia, urea, potassium aluminium sulfate.
The physicals of plastic cement of the present invention: tensile strength 0.78-20Mpa, elongation at break 125-150%, low temperature brittleness temperature-12～-35 ℃, oxygen index 25-35, hardness 50-85.
Extruded stock-plastic cement of the present invention can take common calendering process to produce to can be used for comprising various products and the disposable tableware and the medical outer packaging of food, medicine, chemical industry, packaging field.Also can adopt the common free of contamination toy of injecting method direct production and other product.
Plastic cement of the present invention also can mix with certain proportion with the polymkeric substance that comprises polyethylene, polypropylene, polystyrene, by commonly used extrude, methods such as injection, blowing, mold pressing, calendering make degradable film, sheet material and foaming product, plastic cement: polymkeric substance=15-40: 60-85 during the preparation film; Plastic cement during the preparation sheet material: polymkeric substance 15-50: 50-85; Plastic cement during the preparation foaming product: polymkeric substance 30-80: 20-70.Plastic cement of the present invention also can add in the sizing material that comprises natural rubber, styrene-butadiene rubber(SBR), replaces filler to make different goods, and addition is plastic cement: sizing material=50-80: 20-50.
Major advantage of the present invention:
Plastic cement preparation method of the present invention is simple, and composition is extruded through general twin screw extruder and promptly obtained required product, and the intensity of product, hardness, elongation at break can be adjusted in a big way according to purposes; The amount of starch of plastic cement of the present invention reaches 60-80%, and its cost significantly is lower than the degradative plastics product that contains superpolymer at present; Plasthetics of the present invention is except degradable, and it is nontoxic, behind the product abandonment that the disposable short-term that makes by methods such as calenderings commonly used is used, can directly make the animal feed or mix use with other feed through reclaiming to pulverize, so can reduce or eliminate environmental pollution; Plastic cement of the present invention can also be made various degradable films, sheet material, foaming product with blending such as polyethylene, polypropylene, polystyrene, rubber, the film made from the polyethylene blending is better than domestic filled-type starch plastic at present, has good light transmittance.
Further specify characteristics of the present invention with example below.
Example 1
This example is starch-containing 70.4% plastic cement.
Gelatin and water are descended to soak to obtain in 1 hour gelatin water with 1: 15 weight ratio at 40 ℃.Take out 2.8kg gelatin water and put in another container, and then add 3.5kg urea, heating is dissolved it, adds 5.6kg glycerol, 10.6kg1 subsequently, and 2-propylene glycol, 3.5kg salad oil obtain mixture A through thorough mixing; 70.4kg starch, 0.7kg sorbyl alcohol, 2.1kg white carbon black, 0.1kg stearic acid are added in the belt stirrer container, stirred 8 minutes, obtain mixture B at 70 ℃; Then mixture A and B are added in the screw extrusion press with flow 300 Grams Per Minutes and 1500 Grams Per Minutes respectively, promptly obtain desired product through the extruding blend.The longitudinal tensile strength 14.7Mpa of product, longitudinal fracture elongation 434%, transverse tensile strength 13.8Mpa, transverse breakage elongation 480%, low temperature brittleness-20 ℃, hardness 60.
Example 2-4
Example 2-4 is respectively the plastic cement that contains 80%, 60.2%, 74% starch.Preparation process is with example 1.Component concentration sees Table 1.
Example 5
This example is polyethylene is mixed with 75: 25 weight ratio with example 4 products and to make film by usual method.The physicals of film: machine direction tear 66.4N/mm, longitudinal fracture elongation 573%, transverse tensile strength 8.9Mpa, longitudinal tensile strength 10.7Mpa transverse breakage elongation 587%, cross direction tear strength 77.7N/mm.
Example 6
This example is the film toxicity test that invention example 4 plastic cement and example 5 make.
Testing apparatus: FTIR-Compute, Ms-Dp-Computer.
Sense environmental conditions: 25 ℃, relative humidity 70%.
Mixing and disaggregating treatment through Fourier transform infrared spectroscopy and organic mass spectrometry and computer spectrogram comprise difference spectrum technology, carry out spectrum elucidation and comparative analysis, binding compounds chemical property and synthesis mechanism analysis.Detect conclusion: plastic cement of the present invention and plastic cement and polyethylene are joined the product after the refining, except that producing minute quantity (being lower than 1%) carbamate (nontoxic), do not find objectionable impuritiess such as formaldehyde, nitroso-group, poly cyanic acid (ester) class.
Example 7
This example is example 5 product film biodegradation tests.
One, soil burial test
1. 20 * the 10cm and 8 of the examination films of weighing are imbedded farmland tillaging layer 10cm place, take out 2 after 26 days, flush away earth dries again weighs.Weigh every getting two 1-2 week later on, detect film in degraded in soil speed.
2. with above-mentioned same method, the 5 * 8cm and 18 of the examination films of weighing are imbedded in the basin that fertile table soil is housed, place the incubator of 30 ℃ and relative humidity 75%, take out 2 every certain hour and clean and dry, weigh.
Test-results sees Table 2.
Two, During High-Temperature Composting test
Orchard soil is mixed with 2: 1 with horsehit, add NPK chemical fertilizer and bacterial manure, add 9 big flowerpot (the back cut diameter 30cm that pack into after water stirs evenly, high 15cm) stack retting, every basin is imbedded 20 * 10cm examination film of weighing in advance, wherein six is without the examination film that shone, and other has two through 20W ultraviolet lamp Continuous irradiation 72 hours.Flowerpot is placed room temperature at night＞25 ℃, in the greenhouse of daytime＞35 ℃.Test-results sees Table 3.
As shown in Table 3, do not shine Biodegradable films nearly one month through the high temperature stack retting, its degradation rate almost with general in field or incubator the degradation rate of soil burial test identical, at 44-45%, through radiation treatment, even the stack retting time has only the former half, its degradation rate but reaches 47%, and the spot that many pale red or sap green microbiological corrosions are arranged on the film meanwhile, does not almost change through the common polyethylene film of irradiation.Table 1
The example component Example 1 Example 2 Example 3 Example 4
Starch *，kg 70.4 80 60.2 74
Glycerol, kg 5.6 6.4 6 7.4
1.2-propylene glycol, kg 10.6 4 6 7.4
Gelatin water, kg 2.8 9 3
Sorbyl alcohol, kg 0.7 0.8 1.8 0.7
Salad oil, kg 3.5
Ammonium bicarbonate food grade, kg 2.4 1.5
Urea, kg 3.5 10.2 3.7
Potassium aluminium sulfate, kg 2.4
White carbon black, kg 2.1 2.4 6 1.9
Hard ester acid, kg 0.7 1.6 0.6 0.4
*Example 1-example 3 is a Powder Phaseoli radiati, and example 4 is a medical starch.
Table 2
Project Incubator soil box buries film Corn field 10cm buried at the place film 26 days
Buried soil 21 days Buried soil 35 days
Original weight, g 0.2489 0.2575 0.2568 0.2551 0.2913 0.2968 1.6300 1.6207
Now heavy, g 0.1386 0.1423 0.1434 0.1404 0.1612 0.1648 0.9569 0.9247
Weightlessness, g 0.1103 0.1152 0.1134 0.1147 0.1301 0.1320 0.6731 0.6260
Degradation rate, % 44.3 44.7 44.2 45.0 44.7 44.5 41.3 38.6
Average degradation rate, % 44.4 44.7 40.0
Table 3
Project Irradiation examination membrane stack was not macerated 29 days Through 20W ultra-violet lamp Continuous irradiation 72 hours, stack retting 17 days
The examination film Polyethylene film
Original weight, g 1.9609 1.8672 0.2155
Now heavy, g 1.0813 0.9816 0.2138
Weightlessness, g 0.8796 0.8856 0.0017
Degradation rate, % 44.8 47.4 0.8

Claims (10)

1. polyester type starch plastic, it is waited to levy and is that the composition composition comprises starch, glycerol, 1,2-propylene glycol, lipid acid, sorbyl alcohol, gelatin water, white carbon black and be selected from any one or two kinds of mixtures in urea, Ammonium bicarbonate food grade, the potassium aluminium sulfate, their content: starch accounts for the 60%-80% of composition weight, other component is a benchmark with starch weight, and content is respectively: 15-30%, 8-15%, 0.5-3.5%, 0.5-10%, 10-50%, 1-20%, 5-25%.
2. according to the described polyester type starch plastic of claim 1, it is characterized in that adding in the composition vegetables oil that comprises soya-bean oil, Semen Maydis oil, peanut oil, salad oil, its amount is the 5-30% of starch weight.
3. according to the described polyester type starch plastic of claim 1, it is characterized in that described starch comprises corn, potato, rice, cassava, legume starch or lotus root starch.
4. according to the described polyester type starch plastic of claim 1, it is characterized in that described starch is medical starch, Powder Phaseoli radiati or lotus root starch.
5. according to the described polyester type starch plastic of claim 1, it is characterized in that described white carbon black is the ultra-fine white carbon black of particle diameter＜20 nanometers, described lipid acid comprises C 10-C 20Lipid acid or its esters.
6. the preparation method of the described polyester type starch plastic of claim 1 is characterized in that preparation process comprises:
(1) gelatin soaks in 30-50 ℃ of water and obtained gelatin water in 0.5-2 hour, add one or both mixtures in urea, Ammonium bicarbonate food grade, the potassium aluminium sulfate then, heating is dissolved it, add glycerol, 1 again, the 2-propylene glycol is or/and vegetables oil, obtain mixture A, the weight ratio of described gelatin and water is 1: 10-30;
(2) starch, sorbyl alcohol, white carbon black, lipid acid are added in the container in proportion, stirred 5-10 minute down, obtain mixture B at 70 ℃;
(3) mixture A transports in the screw extrusion press with the flow velocity of 140-400 Grams Per Minute, mixture B is added in the forcing machine hopper with the speed of 800-1800 Grams Per Minute, two kinds of mixtures promptly obtain required plastic cement through the extruding blend, the screw speed 80-180 of described screw extrusion press rev/min, temperature 60-150 ℃, head pressure 2-8 MPa.
7. in accordance with the method for claim 6, it is characterized in that step (1) glycerol, 1,2 propylene glycol in step (2) or/and vegetables oil adds.
8. the application of the described polyester type starch plastic of claim 1 is characterized in that taking calendering process production to comprise disposable tableware, medical outer packaging, or adopts injecting method to produce pollution-free toy.
9. the application of the described polyester type starch plastic of claim 1, it is characterized in that with comprise the polymkeric substance blending of polyethylene, polypropylene, polystyrene, phenylethylene-dialkene-styrene triblock copolymer after make degradable film, sheet material and foaming product, during the preparation film, plastic cement: polymer weight ratio is 15-40: 60-85, the plastic cement of preparation sheet material: polymer weight ratio is 15-50: 50-85, and plastic cement during the preparation foaming product: polymer weight ratio is 30-80: 20-70.
10. the application of the described polyester type starch plastic of claim 1 is characterized in that plastic cement replaces filler to be added in the sizing material that comprises natural rubber, styrene-butadiene rubber(SBR), and to make different goods, addition is a plastic cement: the sizing material weight ratio is 50-80: 20-50.
CN97115212A 1997-08-18 1997-08-18 Polyester type starch plastic Expired - Fee Related CN1074433C (en)

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CN1074433C true CN1074433C (en) 2001-11-07

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1129644C (en) * 1999-06-30 2003-12-03 北京清大亚太科技研究中心 Multiple degrading composition mother particle
MY145899A (en) * 2009-05-21 2012-05-15 Univ Sains Malaysia Extraction and purification of polyester granules
CN103408829A (en) * 2013-07-08 2013-11-27 陈志冲 Composite board used for buildings
CN108794816A (en) * 2018-07-03 2018-11-13 寿光金远东变性淀粉有限公司 A kind of biomass thermal plastic composite materials and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988006609A1 (en) * 1987-02-27 1988-09-07 Amrotex Ag Degradable synthetic compositions
CN1031314A (en) * 1987-08-18 1989-03-01 沃纳-兰伯特公司 Molded article by the pre-processed starch manufacturing
CN1049854A (en) * 1989-08-07 1991-03-13 蝴蝶有限公司 Be used for polymer composition of biodegradable plastics production of articles and preparation method thereof
CN1050390A (en) * 1989-05-30 1991-04-03 蝴蝶有限公司 Prepare the method for destructurized starch-based composition and the composition that makes thus
CN1112143A (en) * 1994-02-09 1995-11-22 诺瓦蒙特股份公司 Expanded articles of biodegradable plastic material and a process for the preparation thereof
JPH1112379A (en) * 1997-06-25 1999-01-19 Toyo Purasuto:Kk Biodegradable resin foam

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988006609A1 (en) * 1987-02-27 1988-09-07 Amrotex Ag Degradable synthetic compositions
CN1031314A (en) * 1987-08-18 1989-03-01 沃纳-兰伯特公司 Molded article by the pre-processed starch manufacturing
CN1050390A (en) * 1989-05-30 1991-04-03 蝴蝶有限公司 Prepare the method for destructurized starch-based composition and the composition that makes thus
CN1049854A (en) * 1989-08-07 1991-03-13 蝴蝶有限公司 Be used for polymer composition of biodegradable plastics production of articles and preparation method thereof
CN1112143A (en) * 1994-02-09 1995-11-22 诺瓦蒙特股份公司 Expanded articles of biodegradable plastic material and a process for the preparation thereof
JPH1112379A (en) * 1997-06-25 1999-01-19 Toyo Purasuto:Kk Biodegradable resin foam

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