CN101805463B - Starch filled biodegradable polypropylene and preparation method thereof - Google Patents

Starch filled biodegradable polypropylene and preparation method thereof Download PDF

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CN101805463B
CN101805463B CN 201010153392 CN201010153392A CN101805463B CN 101805463 B CN101805463 B CN 101805463B CN 201010153392 CN201010153392 CN 201010153392 CN 201010153392 A CN201010153392 A CN 201010153392A CN 101805463 B CN101805463 B CN 101805463B
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starch
polypropylene
filled biodegradable
starch filled
biodegradable polypropylene
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CN101805463A (en
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徐东
徐永
叶展杰
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Polymer Science Anhui New Material Co Ltd
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Polymer Science Anhui New Material Co Ltd
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Abstract

The invention discloses starch filled biodegradable polypropylene and a preparation method thereof. The starch filled biodegradable polypropylene comprises the following components in percentage by weight: 30%-70% of starch, 5%-15% of plasticizer, 10%-50% of polypropylene, 0.5-1% of dispersant, 5-8% of toughening agent and 0.5-1% of photo degradable additive. The material of the invention has the advantages of excellent mechanical property, good biodegradability and low cost. The material of the invention can be greatly popularized, and be widely used in fields such as packing bags, agricultural mulching films, disposable table wares and the like.

Description

A kind of starch filled biodegradable polypropylene and preparation method thereof
[technical field]
The present invention relates to technical field of polymer materials, relate in particular to a kind of starch filled biodegradable polypropylene and preparation method thereof.
[background technology]
Plastics industry develops rapidly, and its purposes has been penetrated into the every field of national economy, and purposes is very extensive.The annual waste plastic amount that produces of China is about about 5,000,000 tons, because plastic raw materials belongs to the chemosynthesis raw material, therefore can not natural decomposition, disposable plastic packaging waste, plastics farm-oriented mulch are arbitrarily abandoned by people and the visual pollution that causes, and plastic waste potential hazard that environment is caused, caused the common concern of relevant government department and society.Bio-degradable plastics will provide new thinking for people solve this " white pollution ".Although bio-degradable plastics is understood by people and used, there is mechanical property defective on the low side in existing biological degradation polypropylene.As only having 19.8MPa with the flexural strength of 60% starch filled biodegradable polypropylene, shock strength only has 47.6KJ/m 2
[summary of the invention]
The technical problem to be solved in the present invention provides preferably starch filled biodegradable polypropylene and preparation method thereof of a kind of mechanical property.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is that a kind of starch filled biodegradable polypropylene is comprised of following component by weight percentage:
Starch 30%-70%
Softening agent 5%-15%
Polypropylene 10%-50%
Dispersion agent 0.5-1%
Toughner 5-8%
Photodegradable aid 0.5-1%.
Wherein, described starch filled biodegradable polypropylene, described starch are the acetylize W-Gum.Described softening agent is sorbyl alcohol, polyvinyl alcohol, a kind of in the glycerine.Described dispersion agent is the amides lubrication dispersing agent.Described polypropylene is the homo-polypropylene powder.Described toughner is maleic anhydride inoculated polypropylene or maleic anhydride graft EVA.Described photodegradable aid is cerium stearate.
Above-described starch filled biodegradable polypropylene can be comprised of following component by weight percentage:
Starch 45%-55%
Softening agent 12%-14%
Polypropylene 20%-30%
Dispersion agent 0.5-1%
Toughner 5-6%
Photodegradable aid 0.5-1%.
A kind of preparation method of above-mentioned starch filled biodegradable polypropylene comprises following processing step: take by weighing raw material by above-mentioned weight proportion, place 115 ℃ to 125 ℃ high-speed mixer to mix 20 to 25 minutes whole raw materials.Then enter in the plastics extruder, temperature is controlled at 130-150 ℃, carries out extruding pelletization.
Material of the present invention possesses excellent mechanical property, good biodegradable, and possess advantage with low cost, can be on market large-scale popularization, be widely used in packing bag, agricultural mulching, the fields such as disposable tableware.
[embodiment]
Below by embodiment the present invention is further set forth:
Wherein, the acetylize W-Gum is selected great achievement modified starch Industrial Co., Ltd. or the crosslinked acetylated starch of refreshing continent starch Science and Technology Ltd. corn.Softening agent is selected Tianjin Xing Tong Fine Chemical Co., Ltd glycerine, all can by massfraction 95%-98% saponification value.Dispersion agent is selected the refined chemical industry TAS-2A of company limited in source, Guangzhou, or Malaysian ethylene bis stearic acid amide EBS-SF.The homo-polypropylene powder is selected Maoming Petrochemical 075 powder or 140 powder.Toughner is maleic anhydride inoculated polypropylene, the four-dimensional superpolymer plastic cement in optional Shenyang company limited, and model SWJ-1B, perhaps, the South Sea, Foshan City Bai Chen polymer novel material company limited, model PC-1.Photodegradable aid is cerium stearate, and optional Canada can reach the equal trade mark of high silver-colored scientific and technological development company of chemical company limited or Shanghai, analytical pure level.Embodiment:
(1) prescription: 30% acetylated starch (percentage of grafting 0.8%), 55% polypropylene (PP140 powder), 8% glycerine, 5% maleic anhydride graft EVA (percentage of grafting 0.8%), 1%TAS-2A, 1% photodegradable aid cerium stearate (IV).
Preparation method: with mixing of materials, be positioned in 120 ℃ the high-speed mixer and mix 20min.Afterwards extruding pelletization in forcing machine is disposed.
(2) prescription: 40% acetylated starch (percentage of grafting 0.8%), 40% polypropylene (PP140 powder), 13% glycerine, 5% maleic anhydride graft EVA (percentage of grafting 0.8%), 1%TAS-2A, 1% photodegradable aid cerium stearate (IV).
Preparation method: with mixing of materials, be positioned in 120 ℃ the high-speed mixer and mix 20min.Afterwards extruding pelletization in forcing machine is disposed.
(3) prescription: 50% acetylated starch (percentage of grafting 0.8%), 30% polypropylene (PP140 powder), 13% glycerine, 5% maleic anhydride graft EVA (percentage of grafting 0.8%), 1%TAS-2A, 1% photodegradable aid cerium stearate (IV).
Preparation method: with mixing of materials, be positioned in 120 ℃ the high-speed mixer and mix 20min.Afterwards extruding pelletization in forcing machine is disposed.
(4) prescription: 60% acetylated starch (percentage of grafting 0.8%), 20% polypropylene (PP140 powder), 13% glycerine, 5% maleic anhydride graft EVA (percentage of grafting 0.8%), 1%TAS-2A, 1% photodegradable aid cerium stearate (IV).
Preparation method: with mixing of materials, be positioned in 120 ℃ the high-speed mixer and mix 20min.Afterwards extruding pelletization in forcing machine is disposed.
(5) prescription: 70% acetylated starch (percentage of grafting 0.8%), 8% polypropylene (PP140 powder), 15% glycerine, 5% maleic anhydride graft EVA (percentage of grafting 0.8%), 1%TAS-2A, 1% photodegradable aid cerium stearate (IV).
Preparation method: with mixing of materials, be positioned in 120 ℃ the high-speed mixer and mix 20min.Afterwards extruding pelletization in forcing machine is disposed.
Processing temperature: district's temperature: 130 ℃; Two district's temperature: 140 ℃; Three district's temperature: 140 ℃; Four district's temperature: 140 ℃; Five district's temperature: 140 ℃; Six district's temperature: 140 ℃; Seven district's temperature: 150 ℃; Eight district's temperature: 150 ℃; Head temperature: 140 ℃.
Performance test:
Tensile strength is tested by ASTM D-638 standard.Specimen types is the I type, batten size (mm): (176 ± 2) (length) * (12.6 ± 0.2) (end width) * (3.05 ± 0.2) (thickness), and draw speed is 50mm/min;
Flexural strength and modulus in flexure are tested by ASTM D-790 standard.Specimen types is specimen size (mm): (128 ± 2) * (12.67 ± 0.2) * (3.11 ± 0.2), rate of bending are 20mm/min;
The socle girder notched Izod impact strength is tested by ASTM D-256 standard.Specimen types is the I type, specimen size (mm): (63 ± 2) * (12.45 ± 0.2) * (3.1 ± 0.2); The breach type is category-A, and the breach residual thickness is 1.9mm;
Other tests: density is according to ASTM D792 test, and melting index is tested according to ASTM D1238.The starch filled polyacrylic mechanical property of table 1
Component concentration (% by weight) Testing standard Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Starch content 30 40 50 60 70
Softening agent 8 13 13 13 15
Polypropylene 55 40 30 20 8
Dispersion agent 1 1 1 1 1
Toughner 5 5 5 5 5
Photodegradable aid 1 1 1 1 1
Tensile strength (MPa) ASTMD-628 21.2 17.4 21.05 13.9 12.17
Elongation at break (%) ASTMD-628 7.4 4.9 24.65 4.9 4.77
Flexural strength (MPa) ASTMD-790 30.4 27.0 24.9 21.72 19.04
Modulus in flexure (MPa) ASTMD-790 856 883.4 731.36 634.4 562.02
Notched Izod impact strength (KJ/m2) ASTMD-256 58.6 42.5 58.3 56.55 51.02
Melting index (g/10min) ASTM D-1238 22.8 16.63 13.6 9.76 9.3
Proportion (g/cm3) ASTM D-792 1.021 1.074 1.097 1.152 1.209
To degradation property, according to natural climate exposure test evaluation of result, this check be according to standard method GB 3681-83 with test block by Exposure to Sunlight, wind, drench with rain and degraded that the etch of microorganism is carried out.The result is as follows: 1, appearance change, expose the colour-change that all has in various degree to the open air through three months, and change procedure is: milky white-pale yellow-pale brown-brown, surface peeling then, embrittlement, mouldy, degrade to efflorescence.2, tan by the sun front and back cutlery box thickness of sample and change, after the degraded cutlery box sample surfaces delamination of embodiment 1-5, the sample attenuation, its variation in thickness sees Table 2
The cutlery box thickness of sample changed (unit: mm) before and after table 2 tanned by the sun
The sample classification Original thickness (mm) Three months thickness (mm) Thickness minimizing value (mm) Thickness decrement %
Prior art 3 3 0 0
Embodiment 1-5 3 1.8 1.2 40.0
Know from the test result of mechanical property, its tensile property of the starch filled biodegradable polypropylene of gained, bending property and impact property have all significantly surpassed the standard of the like product Hybrid Resins 101 of Cereplast company production.Because this product possesses excellent mechanical property, good biodegradable, and possess advantage with low cost, therefore can be on market large-scale popularization, be widely used in packing bag, agricultural mulching, the fields such as disposable tableware.

Claims (6)

1. a starch filled biodegradable polypropylene is characterized in that, is comprised of following component by weight percentage:
Figure FSB00001001694000011
Described starch is acetylated starch, percentage of grafting 0.8%; Polypropylene is the PP140 powder; Softening agent is glycerine.
2. starch filled biodegradable polypropylene according to claim 1 is characterized in that, described starch is the acetylize W-Gum.
3. starch filled biodegradable polypropylene according to claim 1 is characterized in that, described dispersion agent is the amides lubrication dispersing agent.
4. starch filled biodegradable polypropylene according to claim 1 is characterized in that, described toughner is maleic anhydride inoculated polypropylene or maleic anhydride graft EVA.
5. starch filled biodegradable polypropylene according to claim 1 is characterized in that, described photodegradable aid is cerium stearate.
6. the preparation method of a starch filled biodegradable polypropylene claimed in claim 1, it is characterized in that, comprise following processing step: the weight proportion by claim 1 takes by weighing raw material, place 115 ℃ to 125 ℃ high-speed mixer to mix 20 to 25 minutes whole raw materials, then enter in the plastics extruder, temperature is controlled at 130-150 ℃, carries out extruding pelletization.
CN 201010153392 2010-04-16 2010-04-16 Starch filled biodegradable polypropylene and preparation method thereof Expired - Fee Related CN101805463B (en)

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FR2966769B1 (en) * 2010-10-27 2014-02-07 Roquette Freres MULTILAYER STRUCTURE COMPRISING AN ADHESIVE COMPOSITION BASED ON AMYLACEOUS MATERIAL
CN103589178B (en) * 2012-08-17 2016-06-01 杭州康赛环保科技有限公司 A kind of sponge and its preparation method
CN103937036A (en) * 2014-04-23 2014-07-23 苏州羽帆新材料科技有限公司 Environment-friendly plastic containing modified starch
CN104830000A (en) * 2015-04-29 2015-08-12 安徽松泰包装材料有限公司 Production method of food package material
CN106279787A (en) * 2016-08-10 2017-01-04 欧小宇 modified starch composite mulching film
CN107540948A (en) * 2017-09-19 2018-01-05 四川大学 Degraded film formulation
CN107488303B (en) * 2017-09-19 2020-03-31 四川大学 Degradable film
CN108676200A (en) * 2018-06-07 2018-10-19 苏州汉丰新材料股份有限公司 Biodegradable plastic base material and preparation method thereof
CN108976592A (en) * 2018-06-11 2018-12-11 全椒祥瑞塑胶有限公司 A kind of plastics that environmental protection is degradable
CN109265937A (en) * 2018-09-21 2019-01-25 袁志平 The method for preparing the dedicated agricultural mulching of peanut using automobile-used acoustical cotton corner dead meal
CN109776875A (en) * 2018-12-17 2019-05-21 合肥信达膜科技有限公司 A kind of ceramic membrane environmental protection package formula and its production technology
CN113150396A (en) * 2021-03-31 2021-07-23 方龙 Preparation method of packaging bag capable of being rapidly degraded

Citations (3)

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CN1205346A (en) * 1998-02-25 1999-01-20 李嘉琛 Controllable light biological whole degradation plastic
CN1280146A (en) * 2000-07-13 2001-01-17 天津丹海股份有限公司 Biologically degradable fibre level resin composition and its producing method
CN1563172A (en) * 2004-04-20 2005-01-12 杨凌沃林国际降解树脂发展有限公司 Packing materials of starch-polypropylene foam, an preparation method

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FR2910692A1 (en) * 2006-12-26 2008-06-27 Nexans Sa COMPOSITION FOR ENERGY CABLE AND / OR TELECOMMUNICATION BASED ON BIOPOLYMER

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
CN1205346A (en) * 1998-02-25 1999-01-20 李嘉琛 Controllable light biological whole degradation plastic
CN1280146A (en) * 2000-07-13 2001-01-17 天津丹海股份有限公司 Biologically degradable fibre level resin composition and its producing method
CN1563172A (en) * 2004-04-20 2005-01-12 杨凌沃林国际降解树脂发展有限公司 Packing materials of starch-polypropylene foam, an preparation method

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