CN100365067C - Nanometer composite materials with soya protein and montmorillonite, its production and use - Google Patents
Nanometer composite materials with soya protein and montmorillonite, its production and use Download PDFInfo
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- CN100365067C CN100365067C CNB2006100185198A CN200610018519A CN100365067C CN 100365067 C CN100365067 C CN 100365067C CN B2006100185198 A CNB2006100185198 A CN B2006100185198A CN 200610018519 A CN200610018519 A CN 200610018519A CN 100365067 C CN100365067 C CN 100365067C
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Abstract
The present invention relates to a nanometer composite material of soybean protein and montmorillonite, and a preparation method and the application thereof. The material is mainly prepared from 1 to 24 wt% of montmorillonite and 76 to 99 wt% of soybean protein; the material also contains a definite quantity of glycerol. Montmorillonite and soybean protein are respectively dispersed in water in a required proportion, and the two kinds of suspension liquid are stirred, mixed and dried to obtain a nanometer composition of soybean protein and montmorillonite; a certain amount of glycerol is added to the composition, and the mixture is put in an extruding machine for mix so as to obtain plastic sheets by hot press. The present invention has a simple preparation method and a technology with environmental protection; the soybean protein plastic with montmorillonite has favorable mechanical property, thermal property, and ultraviolet absorbance and penetration property; compared with soybean protein plastic with single glycerol plasticization, the composite material has high tensile strength, young's modulus and thermal degradation temperature; consequently, the nanometer composite material is a novel biodegradable green material for optical selection and biodegradation.
Description
Technical field
The present invention relates to a kind of biodegradable modified soybean protein material---nanometer composite materials with soya protein and montmorillonite and its production and use, belong to polymeric material field, also belong to technical field of environmental science.
Background technology
Polynite is a kind of layered silicate, can improve the mechanical property and the thermostability of material, is widely used in polymeric material field as reinforcing filler.Meng Tuoshi can be by solution intercalation, fusion intercalation and method such as in-situ polymerization intercalated with intercalation with form such as peel off and be distributed to (Ray, S.S. in the polymeric matrix; Okamoto, M.; Prog.Polym.Sci., 2003,28,1539-1641.).Usually needs are through the modification of organic intercalation agent before compound with polymkeric substance in the polynite that is used for polymer nanocomposites, and that is to say needs a large amount of organic solvents and comparatively complicated technology, and cost is too high and cause environmental pollution easily.Soil science and biological result of study show that protein and polynite have very high affinity, and protein can enter the polynite of modifying without organic intercalation agent.
Soy-protein is the byproduct after the soybean extract oil, and is cheap, is mainly used in field of food at present.In recent years, because the growing tension of petroleum resources, the crude oil price of continuous rise and the problem of environmental pollution that petroleum-based macromolecular material caused are based on the research and development of the natural macromolecular material of renewable resources and the extensive attention that application obtains people.Emerging " the industrial protein plastics industry " that with the soybean protein isolates is raw material is in the ascendant, and the emphasis of its research mainly concentrates on soybean protein material (Kumar, the R. that practical use is arranged by physics and chemical modification preparation; Choudhary, V.; Varma, I.K.; Mattiason, B., Ind.Crops Prod., 2002,16,155-172.).But soybean protein matter flowability is poor, fusing point is high, is difficult to adapt to traditional complete processing, and its material fragility of preparing is big, does not almost have actual application value (Zhang, J.; Mungara, P.; Jane, J.Polymer, 2001,42,2569.).In order to overcome these shortcomings, in soy-protein, add softening agent such as glycerine or water usually to improve its processing characteristics and tensile property.The adding of softening agent also reduces the tensile strength and the water tolerance of its material greatly when having alleviated soy proteinaceous shortcoming.Therefore, soy-protein physics and chemical modification become the important topic of soybean protein material development and application.
Summary of the invention
For making full use of the two advantage of soy-protein, polynite, the invention provides a kind of imvite modified soybean protein material---nanometer composite materials with soya protein and montmorillonite and its production and use, this material has good mechanical performance, thermal characteristics and anti-ultraviolet function, preparation technology is simple, process environmental protection, low production cost, product performance are good, and material is biodegradable.
The technical solution adopted in the present invention is: the essentially consist of this material is that mass percent is 1～24wt% polynite and 76～99wt% soy-protein.
This material also can add 25～40wt%[qualities of glycerin/(glycerine+soy-protein quality)] glycerine.
The concrete steps of preparation nanometer composite materials with soya protein and montmorillonite are as follows: polynite and soy-protein are dispersed in respectively in the water, and being made into concentration is the polynite aqueous solution of 1wt% to 10wt% and the soy-protein aqueous solution that concentration is 1wt% to 8wt%; In the ratio of polynite quality and soy-protein quality is that 1: 99 to 24: 76 ratio mixes two suspension, and it is 20 ~ 80 ℃ that two solution mix the temperature of carrying out solution intercalation, and the time is 0.5 ~ 4h.Mixture solution is through the centrifugal thick yellow solid washing with acetone that obtains, and drying obtains the soya protein and montmorillonite nano-complex.Then according to the soy-protein quality: qualities of glycerin is 75: 25 to 60: 40 ratio and by single screw extrusion machine this mixture is mixed with glycerine.Screw speed is 30 ~ 120rpm during mixing, and the three section temperature of single screw extrusion machine from the opening for feed to the extrusion mould-outlet are respectively 60 ~ 100,90 ~ 120 and 110 ~ 140 ℃.Hot pressing 4～10min obtains imvite modified soy protein plastic sheet material under 120 ~ 150 ℃, 5 ~ 25MPa at last.
The present invention utilizes the high-affinity between protein and the polynite, uses the reinforcing filler of polynite as soybean protein material first, the biodegradable high performance material that preparation has nanostructure, and it is high in technological content, has tangible novelty.It is that medium carries out solution intercalation that the present invention adopts water, used polynite need not through the modification of organic intercalation agent montmorillonite layer is dispersed in the soy protein matrix with intercalation or exfoliated nanostructure, technology is simple, production cost is low, and use is free of contamination aqueous systems.And the present invention adopts the first solution intercalation advanced technologies of fusion intercalation again, in with single screw extrusion machine mixing plastifying process, the further uniform mixing of polynite and protein, interlamellar spacing further enlarges, the further random distribution that helps the montmorillonite-based nano lamella, make the tensile strength of material improve about 1 times, and Young's modulus improves 2 times, degradation temperature improves 30 ℃.
Because this material produce is with low cost, product performance are good, material is biodegradable; have broad application prospects in the degradable fields such as articles for use and apparatus, disposable tableware, food product pack of moulding; help improving soy proteinaceous added value of product, alleviate oil crisis and problem of environmental pollution.Meanwhile, this material has good absorptive character in the UV-light zone, and has high perviousness in the visible region, can be used for optics and selects, and preparation has the utensil that uvioresistant requires.
Description of drawings
Accompanying drawing is the transmission electron microscope photo of the soy-protein nano composite material structure of 8wt% for polynite content.
Embodiment
Embodiment 1: polynite and soy-protein are dispersed in respectively in the water, and the concentration of the polynite aqueous solution is 2wt%, and the concentration of the soy-protein aqueous solution is 5wt%.Then two solution are mixed and carry out solution intercalation, polynite quality: the soy-protein quality is 8: 92, and temperature of reaction is 25 ℃, and the time is 2h.The centrifugal thick yellow solid washing with acetone that obtains, drying obtains the soya protein and montmorillonite nano-complex.By single screw extrusion machine, according to glycerine/soy-protein mass ratio 3: 7 mixed glycerine and soya protein and montmorillonite nano-complex.Extruder screw rotating speed: 100rpm, single screw extrusion machine three sections temperature settings from the opening for feed to the extrusion mould-outlet: 80,100 and 120 ℃.At 140 ℃, hot pressing 10min obtains imvite modified soy protein plastic sheet material under the 20MPa, is numbered MS-1 at last.Its structure is taken and is shown in the accompanying drawing 1 by transmission electron microscope.
Embodiment 2: polynite and soy-protein are dispersed in respectively in the water, and the concentration of the polynite aqueous solution is 3wt%, and the concentration of the soy-protein aqueous solution is 4wt%.Then two solution are mixed and carry out solution intercalation, polynite quality: the soy-protein quality is 16: 84, and temperature of reaction is 60 ℃, and the time is 4h.The centrifugal thick yellow solid washing with acetone that obtains, drying obtains the soya protein and montmorillonite nano-complex.By single screw extrusion machine, according to glycerine/soy-protein mass ratio 3: 7 mixed glycerine and soya protein and montmorillonite nano-complex.Extruder screw rotating speed: 60rpm, single screw extrusion machine three sections temperature settings from the opening for feed to the extrusion mould-outlet: 90,110 and 140 ℃.At 140 ℃, hot pressing 8min obtains imvite modified soy protein plastic sheet material under the 20MPa, is numbered MS-2 at last.
Embodiment 3: polynite and soy-protein are dispersed in respectively in the water, and the concentration of the Meng Tuoshi aqueous solution is 4wt%, and the concentration of the soy-protein aqueous solution is 3wt%.Then two solution are mixed and carry out solution intercalation, polynite quality: the soy-protein quality is 20: 80, and temperature of reaction is 60 ℃, and the time is 4h.The centrifugal thick yellow solid washing with acetone that obtains, drying obtains the soya protein and montmorillonite nano-complex.By single screw extrusion machine, according to glycerine/soy-protein mass ratio 4: 6 mixed glycerine and soya protein and montmorillonite nano-complex.Extruder screw rotating speed: 30rpm, single screw extrusion machine three sections temperature settings from the opening for feed to the extrusion mould-outlet: 90,110 and 140 ℃.At 140 ℃, hot pressing 8min obtains imvite modified soy protein plastic sheet material under the 20MPa, is numbered MS-3 at last.
Tensile strength (the σ of the plastics sheet that records by electronic tension tester
b), elongation at break (ε
b) and Young's modulus (E) and what recorded by ultraviolet-visible spectrometer is that the transmittance at 300nm and 800nm place comes together in the subordinate list 1 at wavelength.By data in the table as seen, nanometer composite materials with soya protein and montmorillonite has good mechanical performance and optical selective, promptly can shield UV-light and white light is had good perviousness, and its performance obviously is better than not adding the protein plastic of polynite.
Subordinate list 1: the mechanical property of nanometer composite materials with soya protein and montmorillonite and light transmission
| Numbering | Mechanical property | Light transmission (%) | |||
| σ b(MPa) | ε b(％) | E(MPa) | 300nm | 800nm | |
| MS-1 | 12.5 | 15.3 | 340 | 0.5 | 70 |
| MS-2 | 17.4 | 12.8 | 550 | 0.2 | 68 |
| MS-3 | 14.3 | 10.1 | 580 | 0 | 50 |
Claims (7)
1. nanometer composite materials with soya protein and montmorillonite, it is characterized in that basic composition is of it: mass percent is 1～24wt% polynite and 76～99wt% soy-protein.
2. nanometer composite materials with soya protein and montmorillonite according to claim 1 is characterized in that: be added with glycerine in the material, qualities of glycerin/(glycerine+soy-protein quality) is 25～40wt%.
3. the preparation method of the described nanometer composite materials with soya protein and montmorillonite of claim 1, it is characterized in that adopting following steps: be dispersed in polynite and soy-protein in the water respectively earlier, and in the polynite quality: the soy-protein quality is that 1: 99 to 24: 76 ratio mixes two suspension, the centrifugal thick yellow solid that obtains, use washing with acetone, drying obtains the soya protein and montmorillonite nano-complex.
4. the preparation method of nanometer composite materials with soya protein and montmorillonite according to claim 3, it is characterized by: in gained soya protein and montmorillonite nano-complex according to the soy-protein quality: qualities of glycerin is that 75: 25 to 60: 40 ratio adds glycerine, itself and soya protein and montmorillonite nano-complex are mixed, and mix by single screw extrusion machine, hot pressing 4～10min obtains imvite modified soy protein plastic sheet material, i.e. nanometer composite materials with soya protein and montmorillonite under 120 ~ 150 ℃, 5 ~ 25MPa at last.
5. the preparation method of nanometer composite materials with soya protein and montmorillonite according to claim 3, it is characterized by: wherein the concentration of Pei Zhi the polynite aqueous solution is 1wt% to 10wt%, the concentration of the soy-protein aqueous solution is 1wt% to 8wt%; It is 20～80 ℃ that two solution mix the temperature of carrying out solution intercalation, and the time is 0.5～4h.
6. the preparation method of nanometer composite materials with soya protein and montmorillonite according to claim 4, it is characterized by: when glycerine is mixed with the soya protein and montmorillonite nano-complex, the soy-protein quality: qualities of glycerin is 75: 25 to 60: 40, the screw speed of single screw extrusion machine is between 30 ~ 120rpm, and the three section temperature of single screw extrusion machine from the opening for feed to the extrusion mould-outlet are arranged at 60～100 ℃, 90～120 ℃ and 110～140 ℃.
7. the purposes of the described nanometer composite materials with soya protein and montmorillonite of claim 1 is characterized in that: be used for optics and select and be used as Biodegradable material.
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| CNB2006100185198A CN100365067C (en) | 2006-03-10 | 2006-03-10 | Nanometer composite materials with soya protein and montmorillonite, its production and use |
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| CNB2006100185198A CN100365067C (en) | 2006-03-10 | 2006-03-10 | Nanometer composite materials with soya protein and montmorillonite, its production and use |
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| CN1817967A CN1817967A (en) | 2006-08-16 |
| CN100365067C true CN100365067C (en) | 2008-01-30 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268092A (en) * | 2011-05-23 | 2011-12-07 | 天津大学 | Bovine serum albumin-montmorillonite nano composite material and preparation method thereof |
| CN103007894B (en) * | 2012-12-13 | 2014-12-10 | 南京信息工程大学 | Soybean protein micro sphere material and preparation method and application of material in treating waste water containing heavy metal ion |
| CN104017244B (en) * | 2014-01-08 | 2016-06-22 | 天津科技大学 | A kind of montmorillonite intercalation nano composite membrane and its preparation method and application |
| CN104861662B (en) * | 2015-06-08 | 2017-03-22 | 四川大学 | Nano composite soy protein plastic and preparation method thereof |
| CN116574390B (en) * | 2023-06-14 | 2024-05-03 | 东北林业大学 | Inorganic hybridization reinforced straw-based biomass composite material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1687287A (en) * | 2005-04-07 | 2005-10-26 | 华南理工大学 | Method for preparing water-resisting glue for pasting labels in high speed from composite insertion layers between casein and montorillonite clay |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1687287A (en) * | 2005-04-07 | 2005-10-26 | 华南理工大学 | Method for preparing water-resisting glue for pasting labels in high speed from composite insertion layers between casein and montorillonite clay |
Non-Patent Citations (1)
| Title |
|---|
| 小分子模拟明胶－蒙脱土插层的相互作用. 张红磊等.天津师范大学学报（自然科学版），第23卷第4期. 2003 * |
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