CN1308398C - Soya protein plastic with water polyurethane modification and preparing method thereof - Google Patents
Soya protein plastic with water polyurethane modification and preparing method thereof Download PDFInfo
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- CN1308398C CN1308398C CNB2004100131979A CN200410013197A CN1308398C CN 1308398 C CN1308398 C CN 1308398C CN B2004100131979 A CNB2004100131979 A CN B2004100131979A CN 200410013197 A CN200410013197 A CN 200410013197A CN 1308398 C CN1308398 C CN 1308398C
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Abstract
本发明涉及一种改性大豆蛋白塑料，它是由35～40%阴离子水性聚氨酯乳液、65～60%大豆蛋白质与占上述两组份总质量1～4%的乙二醇二缩水甘油醚通过反应交联所得，其制备方法为：将阴离子水性聚氨酯乳液与大豆分离蛋白按一定比例机械混合，按计量加入乙二醇二缩水甘油醚后继续搅拌0.5h，然后将混合液倒入聚四氟乙烯模具，放进烘箱50℃加热固化24h得到固态混合物。该固态混合物经乙酸水溶液处理后在115～120℃和20MPa条件下热压5～10min制成试片。该蛋白质材料不仅生产工艺简单、无污染，而且具有良好的力学性能和较低的吸水率。因此该蛋白质复合材料是一种具有发展潜力的新型可生物降解绿色材料。The invention relates to a modified soybean protein plastic, which is composed of 35-40% anionic water-based polyurethane emulsion, 65-60% soybean protein and ethylene glycol diglycidyl ether accounting for 1-4% of the total mass of the above two components. It is obtained by reaction cross-linking, and its preparation method is: mechanically mix anionic water-based polyurethane emulsion and soybean protein isolate in a certain proportion, add ethylene glycol diglycidyl ether according to the meter, continue stirring for 0.5h, and then pour the mixed solution into polytetrafluoroethylene Vinyl mold, put into an oven at 50°C to heat and cure for 24 hours to obtain a solid mixture. After the solid mixture is treated with aqueous acetic acid, it is hot-pressed at 115-120° C. and 20 MPa for 5-10 minutes to prepare a test piece. The protein material not only has a simple production process and no pollution, but also has good mechanical properties and low water absorption. Therefore, the protein composite material is a new type of biodegradable green material with development potential.
Description
Technical field
The present invention relates to have the method and the purposes of bio-degradable plastics, belong to the high polymer material chemical field, also belong to the ecotope field with renewable resources-soy-protein preparation.
Background technology
Owing to non-renewable petroleum resources consume day by day and cause environmental pollution serious day by day based on being extensive use of of the synthesized polymer material finished product of petrochemical materials, so the development and utilization of renewable resources-natural polymer more and more is subject to people's attention.In recent years, be that emerging " the industrial albumen plastics industry " of raw material is noticeable day by day by the soybean separate soybean protein.Its main research and development concentrate on by hot-forming preparation plastic of soybean protein (Jacob John and Mrinal Bhattacharya Polymer International48:1165-1172 (1999)).But, plastic of soybean protein because itself enbrittle greatly, not water-proof shortcoming, its practical application is restricted.Usually adopt in order to solve this shortcoming that acid is transferred, method of modifying such as crosslinked, filling or blend.Many active groups of soybean protein itself are easy to take place cross-linking modified, adopt formaldehyde or the crosslinked water-absorbent that can suppress material effectively of oxalic dialdehyde.[Zhang J，Mungara P，Jane J：“Mechanical andThermal Properties of Extruded Soy Protein Sheets”.Polymer，2001，42：2569.]
Summary of the invention
The purpose of this invention is to provide cross-linking aqueous urethane/soy protein plastic of a kind of spent glycol diglycidylether and preparation method thereof, this plastics should have mechanical property (tensile strength and elongation at break) and water resisting property preferably.
Technical scheme provided by the invention is: a kind of modified soybean protein plastics, it is to pass through the cross-linking reaction gained by 35～40% anion aqueous polyurethane emulsions, 65～60% soy-proteins and 1～4% ethylene glycol diglycidylether, and above per-cent is mass percent.
A kind of method for preparing above-mentioned modified soybean protein plastics: with anion aqueous polyurethane emulsion and soybean protein isolate in 35～40: 65～60 ratio mechanically mixing, continue to stir 0.5h behind above-mentioned two component total masses, 1～4% ethylene glycol diglycidylether by being metered into to account for, to mix liquid then and pour the tetrafluoroethylene mould into, and put the 20～30h that is heating and curing under 50 ± 10 ℃ in the baking oven into and obtain solid mixt.Place 0.4～0.5M acetic acid aqueous solution to soak 24h solid mixt, dry back room temperature under the saturated common salt water vapor is deposited a week, and it is the 0.3mm test piece that solid mixt hot pressing 5～10min under 115-120 ℃ and 10～20MPa makes thickness.
Above-mentioned modified soybean protein plastics can be used for biodegradable green material such as disposable tableware, food product pack, industrial matrix material.
Modified soybean protein plastics of the present invention utilize these renewable resource of aqueous polyurethane and soybean protein isolates, make by simple process, and have biodegradable, help environmental protection; Simultaneously can increase aqueous polyurethane and soybean protein isolates value-added content of product, have important economic worth.The present invention can obtain the material of different mechanical properties by the content of regulating aqueous polyurethane, the content of ethylene glycol diglycidylether, and it is high in technological content, has novelty.The soy protein plastic that contains the suitable quantity of water based polyurethane of the present invention is improved simultaneously in tensile strength and two mechanical performance indexs of elongation at break, has practicality.Waterborne polyurethane modified soy protein plastic of the present invention has flexible, lower preferably water-absorbent and good water resisting property, has solved the difficult problem of long-term puzzlement plastic of soybean protein practical application thus, and therefore significant technical progress is arranged.
Embodiment
Embodiment 1: a kind of modified plastic of soybean protein, it be by 40% anion aqueous polyurethane emulsion, 60% soybean protein isolates and the ethylene glycol diglycidylether that accounts for above-mentioned two component total masses 2% by the cross-linking reaction gained, above per-cent is mass percent.
Embodiment 2: a kind of modified plastic of soybean protein, it be by 40% anion aqueous polyurethane emulsion, 60% soybean protein isolates and the ethylene glycol diglycidylether that accounts for above-mentioned two component total masses 3% by the cross-linking reaction gained, above per-cent is mass percent.
Embodiment 3: a kind of modified plastic of soybean protein, it be by 35% anion aqueous polyurethane emulsion, 65% soybean protein isolates and the ethylene glycol diglycidylether that accounts for above-mentioned two component total masses 4% by the cross-linking reaction gained, above per-cent is mass percent.
Embodiment 4: a kind of modified plastic of soybean protein, it be by 38% anion aqueous polyurethane emulsion, 62% soybean protein isolates and the ethylene glycol diglycidylether that accounts for above-mentioned two component total masses 1% by the cross-linking reaction gained, above per-cent is mass percent.
With anion aqueous polyurethane (20wt%, shore hardness 10～20 degree of film, Laohekou Pi Hua company) with soybean protein isolates (Hubei Province's Yunmeng dragon cloud protein food product company limited) mechanically mixing in proportion, after being metered into ethylene glycol diglycidylether, continue to stir 0.5h, to mix liquid then and pour the tetrafluoroethylene mould into, and put 50 ± 10 ℃ of 24h that are heating and curing of baking oven into and obtain solid mixt.Place 0.4～0.5M acetate (HOAc) aqueous solution to soak 24h solid mixt, in 25 ℃ of air, place 24h then.It is 0.3mm that solid mixt hot pressing 10min under 115-120 ℃ and 20MPa condition makes thickness.Simultaneously use pure aqueous polyurethane (WPU) and pure soybean protein isolates (SPI) to make test piece reference as a comparison respectively under the same conditions.The performance of test piece sees attached list 1.
The mechanical property and the water-absorbent of subordinate list 1 waterborne polyurethane modified soybean protein isolates plastics
| Numbering | Ethylene glycol diglycidylether consumption (%) | Mechanical property | Water-absorbent (%) | |
| Tensile strength (MPa) | Elongation at break (%) | |||
| E0 | 0 | 10±2 | 70±10 | 26±4 |
| E2 | 2 | 14±2 | 50±10 | 26±4 |
| E3 | 3 | 18±2 | 25±10 | 26±4 |
| SPI | 0 | - | - | 38.7±4 |
| WPU | 0 | 5±1 | 1700±100 | 14.6±0.5 |
The test of above data is as follows: mechanical property thinks carefully newly in Shenzhen with reference to ISO6239-1986 (E) standard on the CMT6503 instrument of testing tool company and records that rate of extension is 50mm/min; Water-absorbent test is the ratio that contains quality and initial dry state quality of sheet material after 24 hours.
Claims (2)
1. waterborne polyurethane modified soy protein plastic, it is characterized in that it is to pass through cross-linking reaction by 35～40% anion aqueous polyurethane emulsions, 65～60% soy-proteins and the ethylene glycol diglycidylether that accounts for above-mentioned two component total masses 1～4%, cross-linking agent places 0.4～0.5M acetic acid aqueous solution to soak 24h, dry back promptly gets waterborne polyurethane modified soy protein plastic after room temperature is deposited a week under the saturated common salt water vapor, above per-cent is mass percent.
2. method for preparing the described waterborne polyurethane modified soy protein plastic of claim 1, it is characterized in that: be 35～40: 65～60 ratio mechanically mixing with anion aqueous polyurethane emulsion and soybean protein isolates in mass ratio, continue to stir 0.5h behind above-mentioned two component total masses, 1～4% ethylene glycol diglycidylether by being metered into to account for, to mix liquid then and pour the tetrafluoroethylene mould into, put the 20～30h that is heating and curing under 50 ± 10 ℃ in the baking oven into and obtain solid mixt, place 0.4～0.5M acetic acid aqueous solution to soak 24h solid mixt, dry back room temperature under the saturated common salt water vapor is deposited a week, and it is the 0.3mm test piece that solid mixt hot pressing 5～10min under 115-120 ℃ and 10～20MPa makes thickness.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100131979A CN1308398C (en) | 2004-05-24 | 2004-05-24 | Soya protein plastic with water polyurethane modification and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100131979A CN1308398C (en) | 2004-05-24 | 2004-05-24 | Soya protein plastic with water polyurethane modification and preparing method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1583885A CN1583885A (en) | 2005-02-23 |
| CN1308398C true CN1308398C (en) | 2007-04-04 |
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| CNB2004100131979A Expired - Fee Related CN1308398C (en) | 2004-05-24 | 2004-05-24 | Soya protein plastic with water polyurethane modification and preparing method thereof |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8182918B2 (en) * | 2005-05-23 | 2012-05-22 | Cornell Research Foundation, Inc | Cured soy protein with green strengthening additive and fabrication of such into green composite |
| CN102492109A (en) * | 2011-11-28 | 2012-06-13 | 西安科技大学 | Biodegradable high-resilience flexible polyurethane foam plastics and its preparation method |
| MX2022013186A (en) * | 2020-05-01 | 2022-11-14 | Modern Meadow Inc | POLYURETHANE AND PROTEIN ALLOYS AND LAYERED MATERIALS INCLUDING SAME. |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329109A (en) * | 2001-07-13 | 2002-01-02 | 冯季强 | Far infrared film and its production method |
| CN1417261A (en) * | 2002-12-18 | 2003-05-14 | 中国农业大学 | Prepn of biodegradable material |
| JP2003261598A (en) * | 2002-03-05 | 2003-09-19 | Dainippon Ink & Chem Inc | Modified soy protein, method for producing the same, and molded article using the same |
| JP2003261771A (en) * | 2002-03-07 | 2003-09-19 | Dainippon Ink & Chem Inc | Biodegradable resin composition, method for producing the same, and biodegradable molded product |
| CN1462770A (en) * | 2003-05-26 | 2003-12-24 | 武汉大学 | Composite material and itd preparation method |
-
2004
- 2004-05-24 CN CNB2004100131979A patent/CN1308398C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329109A (en) * | 2001-07-13 | 2002-01-02 | 冯季强 | Far infrared film and its production method |
| JP2003261598A (en) * | 2002-03-05 | 2003-09-19 | Dainippon Ink & Chem Inc | Modified soy protein, method for producing the same, and molded article using the same |
| JP2003261771A (en) * | 2002-03-07 | 2003-09-19 | Dainippon Ink & Chem Inc | Biodegradable resin composition, method for producing the same, and biodegradable molded product |
| CN1417261A (en) * | 2002-12-18 | 2003-05-14 | 中国农业大学 | Prepn of biodegradable material |
| CN1462770A (en) * | 2003-05-26 | 2003-12-24 | 武汉大学 | Composite material and itd preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 大豆蛋白质塑料研究进展 汪浩，西部粮油科技，第26卷第5期 2001 * |
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| CN1583885A (en) | 2005-02-23 |
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