CN101407565A - Soy protein / emulsion polymerization high polymer nano composite material, and preparation and use thereof - Google Patents
Soy protein / emulsion polymerization high polymer nano composite material, and preparation and use thereof Download PDFInfo
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- CN101407565A CN101407565A CNA2008101984233A CN200810198423A CN101407565A CN 101407565 A CN101407565 A CN 101407565A CN A2008101984233 A CNA2008101984233 A CN A2008101984233A CN 200810198423 A CN200810198423 A CN 200810198423A CN 101407565 A CN101407565 A CN 101407565A
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Abstract
The invention discloses a soybean protein/emulsion polymerization macromolecule nanometer complex material, which comprises soybean protein, a polymer monomer and an emulsifier. In addition, the invention also discloses a preparation method of the complex material, which comprises the following steps: a mixing liquid of soybean protein/polymer monomer is prepared; complex emulsion is obtained after polymerization; and after cooling, the soybean protein/emulsion polymerization macromolecule nanometer complex material can be produced. The invention also discloses that the nanometer complex material can be applied to a tackiness agent of wood matrix or to the preparation of nanometer complex plastic. The synthesized macromolecules are distributed in protein matrix uniformly by the form of nanometer microspheres; the protein and the synthesized macromolecules are combined into a core-shell structure through an additional emulsifier; and the invention solves the problem of poor compatibility in mixing synthesized macromolecules and natural polymers. The preparation method has the advantages of application of carrying out all reactions in water system, no organic solvent, being friendly to environment and having low cost and broad application prospect.
Description
Technical field
The present invention relates to a kind of soy protein/emulsion polymerization high polymer nano composite material and preparation method thereof, belong to field of polymer technology, also belong to field of nanometer material technology.
Background technology
Along with the exhaustion of Nonrenewable resources such as oil, the problem of environmental pollution of energy dilemma, crude oil price continuous rise and non-degradative plastics goods is based on the research of the natural macromolecular material of renewable resources with use extremely and pay attention to.Soy-protein is the byproduct of soya-bean oil industry, its wide material sources and output are abundant, cheap, and have good biological activity and biodegradability, it can be applicable to fields such as packaging material for food, degradable plastic product, environmental protection tamanori and foodstuffs industry.The preparation method of present soybean protein material mainly is by it is carried out physics or chemical modification, increase flowability, kindliness (the Macromol Mater Engin 2006 that protein is processed by adding small molecules softening agent such as glycerine, water, acid amides by chemical bond or hydrogen bond action, 291,820-828; J ApplPolym Sci 2007,106,130-137.).But usually cause the mechanical properties decrease of material, water-absorbent to increase.Introduce nano particle can improve effectively the protein material performance (Macromol Biosci2008,8,401-409).In recent years the functional microsphere that existing report obtains with letex polymerizations such as vinylbenzene, acrylate, acetates with micro nano structure, can be used on catalyst cupport, bone filling, medicament slow release, (Macromolecules 2005 for solvent absorbing, 38,9100-9109).Can improve the mechanical property and the water tolerance of material effectively when mixture with other polymer formation nucleocapsid structure, but because synthetic macromolecules such as polystyrene are difficult to biological degradation, biocompatibility is relatively poor, and with rise in oil price, cost strengthens, thereby limits its application widely.Therefore, synthetic macromolecule and renewable biomass resource-protein bound are got up to form the demand that the matrix material with superperformance meets the strategy of sustainable development and actual production.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, provide that a kind of consistency is good, good stability, processibility are good, the soy protein/emulsion polymerization high polymer nano composite material of good waterproof performance and applied range.
Another object of the present invention provides the preparation method of above-mentioned matrix material.
A further object of the invention provides the application of above-mentioned matrix material.
A kind of soy protein/emulsion polymerization high polymer nano composite material comprises soy-protein, polymer monomer and emulsifying agent; The weight ratio of described soy-protein and polymer monomer is 1: 0.1～9; The weight ratio of described polymer monomer and emulsifying agent is 10: 1～2.
Described soy-protein is soybean protein isolates or soybean protein concentrate matter.
Described polymer monomer is vinylbenzene, acrylic ester compound or acetic acid alkene ester compound.
Described acrylic ester compound is one or more a mixture in methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate or other acrylate homologues.
Described acetic acid alkene ester compound is one or more a mixture in vinyl acetate, acetic acid third rare ester, acetic acid butene esters or other acetic acid alkene ester homologues.。
Described emulsifying agent is one or more a mixture in sodium laurylsulfate salt, potassium laurate or the sodium lauryl sulphate.
The preparation method of above-mentioned matrix material comprises the steps:
(1) soy-protein is scattered in the water that to form weight percent concentration be 2%～90% soy-protein suspension, add polymer monomer and emulsifying agent behind the mixing, mixing is warming up to 20～90 ℃ and obtains finely dispersed protein/polymer monomer mixed solution;
(2) be that the initiator of polymer monomer 1 ‰～10 ‰ adds trigger monomer polymerization in the mixed solution with weight, 60～90 ℃ of reaction final vacuum deaerations in 3～12 hours down, obtain composite emulsion, be soy protein/emulsion polymerization high polymer nano composite material after the cooling.
Initiator described in the above-mentioned steps (2) is that persulphates such as Sodium Persulfate, Potassium Persulphate or persulphate and other salt are compound etc.
Above-mentioned soy protein/emulsion polymerization high polymer nano composite material needs in low-temperature storage.
Above-mentioned nano composite material can be applicable to the sizing agent of wood matrix.
Above-mentioned nano composite material also can be applicable to prepare nano composite plastics.
Describedly being applied to prepare nano composite plastics, is under 20～80 ℃ of temperature nano composite material curtain coating in vacuum drying oven promptly to be obtained transparent nano composite plastics sheet after 8～48 hours.
Describedly being applied to prepare nano composite plastics, can also be to put into extrusion moulding in the single screw extrusion machine after composite emulsion is concentrated into 50～90% solid content, and the segmentation temperature of adjusting screw(rod) obtains nano composite plastics at 80～150 ℃ after the extrusion moulding.
In the described nano composite plastics, the percentage that soy-protein accounts for the nano composite plastics gross weight is 10～90%.
The preparation method of soy protein/emulsion polymerization high polymer nano composite material provided by the invention, its principle is to be matrix with the renewable natural polymer-soy-protein with certain emulsifying capacity, introduce synthetic macromolecules such as polystyrene, polyacrylic ester or poly-acetates by the emulsion polymerization original position, size (10～300nm) via protein microemulsion regulation and control emulsion particle, synthetic is that nuclear, protein macromolecule are shell with the macromolecule emulsion particle, has the novel nano soy protein/emulsion polymerization high polymer nano composite material of nucleocapsid structure.The particle size of emulsion polymerization high polymer all can be controlled in below 300 nanometers, and the size of diameter is subjected to the influence of reaction conditions; The molecular weight of the polystyrene of letex polymerization, polyacrylic ester and poly-acetic acid alkene ester is subjected to the influence of initiator and emulsifying agent, as the molecular weight of polystyrene 10
3～10
6In the scope.
Ester classes such as soy-protein, acetic acid alkene ester can be as the sizing agent of timber, and both are formed water-repellancy and the bonding strength that NEW TYPE OF COMPOSITE latex has strengthened the agent of traditional protein gluing after by letex polymerization.The feature of environmental protection of sizing agent is strengthened simultaneously.
Water and emulsifying agent and synthetic macromolecule increase flowability and plasticity-in the materials processing as soy proteinaceous softening agent in the screw extrusion molding.The plastic sheet intensity outline that casting method obtains is less than extruding the plastic material that pressure sintering obtains.The performance of the section bar that two kinds of methods obtain is subjected to the influence of processing temperature, moment of torsion.
Compare with technology is arranged now, the present invention has following beneficial effect:
(1) the present invention is by soy proteinaceous microemulsion, polymer such as original position polymerizing styrene in matrix, and the molecular weight of synthetic macromolecules such as polystyrene and size can be controlled.Simultaneously, adding emulsifying agent is a kind of proteinic properties-correcting agent, can promote proteinic workability, so synthetic method has very strong novelty.
(2) synthetic macromolecule of the present invention is dispersed in the protein matrix with the form of Nano microsphere, protein and synthetic macromolecule combine the formation nucleocapsid structure by adding emulsifying agent, and it has solved the difficult problem of synthetic macromolecule and natural polymer blended middle consistency difference.
(3) protein/polyester (acrylate and acetic acid alkene ester) composite emulsion of making of the present invention has good stability, can obtain biological degradability sizing agent and plastics preferably by different processing modes.Because the introducing of the synthetic macromolecule that water-repellancy and processibility are good has promoted soy-protein greatly in the performance aspect this.As: plastics have good processibility and water-repellancy, and the tensile strength of test piece all more than 10MPa, shows the good mechanical performance after moisture absorption under the 75% relative humidity condition.
(4) preparation method provided by the invention, institute responds and all carries out under aqueous systems, and organic solvent-free is environmentally friendly, and can matrix material of the present invention be processed with traditional Process Technology of Polymer means, so process automation is easy and cost is low.
(5) the present invention can save petroleum resources effectively, and can reduce the consumption and the cost of raw material by the nanometer reinforcing effect, is expected to substitute synthetic macromolecule.Therefore the present invention is with a wide range of applications.
Description of drawings
The stereoscan photograph (SEM) of soy-protein/polystyrene nano composite material that Fig. 1 obtains for embodiment 2.
The transmission electron microscope photo (TEM) of soy-protein/polystyrene nano composite material that Fig. 2 obtains for embodiment 2.
The formation synoptic diagram that Fig. 3 obtains for embodiment 2 with nucleocapsid structure soy-protein/polystyrene nano composite material.Arrow is depicted as emulsion polymerization (Emulsion polymerization) direction among the figure, promptly by a to b; Polypeptide chain is the soybean protein polypeptide chain; SDS is a sodium lauryl sulphate; Styrene is a vinylbenzene.
Embodiment
Characterize:
The pulling force size: balance is after two weeks under the sheet material room temperature of the about 0.3mm * 10mm of size * 100mm, and according to ASTM D882-81 standard testing, draw speed is 50mm/min.Clamp distance is 50mm.Quadruplication records tensile strength and elongation at break.
Molecular weight test: sample is obtained isozygotying into macromolecule polysterol, polyacrylic ester or poly-acetic ester after the organic solvent extracting.Sample obtains molecular weight after the GPC test.
Scanning electron microscope characterizes: freezing in the sample liquid nitrogen, and behind the section metal spraying after fractureing, be placed on sample table and observe.
Transmission electron microscope: fish for mixed emulsion with copper mesh, carry out transmission electron microscope observing after remaining in the sample metal spraying on the copper mesh.
Experiment material:
Soybean protein isolates and soybean protein concentrate are buied from Yunmeng company limited of Hubei Du Pont, and reagent such as vinylbenzene, acrylate, acetic ester, emulsifying agent, initiator are all purchased in Shanghai reagent company.
Embodiment 1
Soybean protein isolate is pre-dissolved in the water, obtains weight percent and be 35% the soy-protein aqueous solution, stir after 10 minutes, add vinylbenzene and emulsifier sodium lauryl sulfate, control vinylbenzene and sodium lauryl sulphate weight ratio are 9: 1.High-speed stirring is warming up to 90 ℃ after 40 minutes, form to disperse emulsion preferably.Then, add Potassium Persulphate to emulsion, initiator is 8.5 ‰ of a styrene monomer weight, after reacting 4 hours under 90 ℃, emulsion is at room temperature cooled off, pour into after the vacuum defoamation in the glassware, 50 ℃ of following curtain coatings obtained transparent protein and polystyrene composite Nano plastics after 24 hours in vacuum drying oven.
Embodiment 2
Soy-protein is pre-dissolved in the water, obtains weight percent and be 50% the soy-protein aqueous solution, stir after 40 minutes, add vinylbenzene and emulsifying agent Sodium dodecylbenzene sulfonate, control vinylbenzene and Sodium dodecylbenzene sulfonate weight ratio are 4: 1.High-speed stirring is warming up to 50 ℃ after 50 minutes, form to disperse emulsion preferably.Then, add Sodium Persulfate to emulsion, initiator is 5.5 ‰ of a styrene monomer weight, reaction is after 10 hours down at 60 ℃, and emulsion is at room temperature cooled off, and pours into after the vacuum defoamation in the glassware, 80 ℃ of following curtain coatings are after 48 hours in vacuum drying oven, obtain transparent protein and polystyrene composite Nano plastics, its stereoscan photograph as shown in Figure 1, transmission electron microscope photo is as shown in Figure 2.It forms synoptic diagram and sees Fig. 3.
Embodiment 3
Soy-protein is pre-dissolved in the water, obtains weight percent and be 16% the soy-protein aqueous solution, stir after 30 minutes, add vinylbenzene and emulsifying agent sodium laurate, control vinylbenzene and sodium laurate weight ratio are 8: 1.High-speed stirring is warming up to 70 ℃ after 1 hour, continue to stir after 50 minutes, forms and disperses emulsion preferably.Then, add Potassium Persulphate to emulsion, initiator is 6.5 ‰ of a styrene monomer weight, after reacting 10 hours under 70 ℃, emulsion is at room temperature cooled off, vacuum defoamation, and protein/polystyrene mixed emulsion is put into extrusion moulding in the single screw extrusion machine after being concentrated into 90% solid content, the sectional temperature of adjusting screw(rod) is respectively 80 ℃, 120 ℃, 150 ℃, obtains nano composite plastics.
Embodiment 4
Soy-protein is pre-dissolved in the water, obtains weight percent and be 20% the soy-protein aqueous solution, stir after 60 minutes, add vinylbenzene and emulsifying agent, control vinylbenzene and potassium laurate weight ratio are 6: 1.High-speed stirring is warming up to 50 ℃ after 45 minutes, form to disperse emulsion preferably.Then, add initiator potassium persulfate/hydrogen peroxide to emulsion, initiator is 10 ‰ of a styrene monomer weight, after reacting 10 hours under 65 ℃, emulsion is at room temperature cooled off, pour into after the vacuum defoamation in the glassware, 80 ℃ of following curtain coatings obtained the protein nano composite plastic after 18 hours in vacuum drying oven.
Embodiment 5
Soy-protein is pre-dissolved in the water, obtains weight percent and be 30% the soy-protein aqueous solution, stir after 25 minutes, add vinylbenzene and emulsifying agent, control vinylbenzene and emulsifying agent sodium laurate weight ratio are 8: 1.High-speed stirring is warming up to 70 ℃ after 1 hour, continue to stir after 50 minutes, forms and disperses emulsion preferably.Then, add initiator potassium persulfate to emulsion, initiator is 7 ‰ of a styrene monomer weight, after reacting 10 hours under 80 ℃, emulsion is at room temperature cooled off, vacuum defoamation, and protein/polystyrene mixed emulsion is put into extrusion moulding in the single screw extrusion machine after being concentrated into 50% solid content, the sectional temperature of adjusting screw(rod) is respectively 100 ℃, 150 ℃, 140 ℃, obtains transparent nano composite plastics.
Embodiment 6
Soybean protein isolate is pre-dissolved in the water, obtains weight percent and be 50% the soy-protein aqueous solution, stir after 30 minutes, add vinylbenzene and emulsifying agent potassium laurate and control vinylbenzene and the emulsifying agent weight ratio is 15: 1.High-speed stirring is warming up to 50 ℃ after 1 hour, form to disperse emulsion preferably.Then, add the initiator Sodium Persulfate to emulsion, initiator accounts for styrene monomer content 4.5 ‰, after reacting 6 hours under 90 ℃, emulsion is at room temperature cooled off, pour into after the vacuum defoamation in the tetrafluoroethylene vessel, 40 ℃ of following curtain coatings obtained transparent nano composite plastics after 36 hours in vacuum drying oven.
Embodiment 7
Soy-protein is pre-dissolved in the water, obtains weight percent and be 40% the soy-protein aqueous solution, stir after 30 minutes, add vinylbenzene and emulsifying agent sodium laurylsulfonate, control vinylbenzene and emulsifying agent weight ratio are 2: 1.High-speed stirring is warming up to 70 ℃ after 1 hour, continue to stir after 80 minutes, forms and disperses emulsion preferably.Then, add initiator Sodium Persulfate/hydrogen peroxide to emulsion, initiator is 8 ‰ of a styrene monomer weight, after reacting 3 hours under 70 ℃, emulsion is at room temperature cooled off, vacuum defoamation, and protein/polystyrene mixed emulsion is put into extrusion moulding in the single screw extrusion machine after being concentrated into 80% solid content, the sectional temperature of adjusting screw(rod) is respectively 110 ℃, 110 ℃, 130 ℃, obtains transparent nano composite plastics.
Embodiment 8
Soy-protein is pre-dissolved in the water, obtain weight percent and be 40% the soy-protein aqueous solution, stir after 30 minutes, add methyl acrylate and blending emulsifiers sodium lauryl sulphate/sodium laurate, control methyl acrylate and emulsifying agent weight ratio are 5: 1.Be warming up to 70 ℃ after stirring, continue to stir after 80 minutes, form and disperse emulsion preferably.Then, add the initiator Sodium Persulfate to emulsion, initiator is 9 ‰ of a methacrylate monomer weight, and reaction is after 3 hours down at 70 ℃, and emulsion is at room temperature cooled off, and vacuum defoamation is used for the gummed experiment of timber.
Embodiment 9
Soy-protein is pre-dissolved in the water, obtain weight percent and be 60% the soy-protein aqueous solution, stir after 30 minutes, add ethyl propenoate and blending emulsifiers sodium lauryl sulphate/sodium laurate, control ethyl propenoate and emulsifying agent weight ratio are 3: 1.Be warming up to 70 ℃ after stirring, continue to stir after 80 minutes, form and disperse emulsion preferably.Then, add initiator potassium persulfate to emulsion, initiator is 7 ‰ of an ethyl propenoate monomer weight, and reaction is after 3 hours down at 70 ℃, and emulsion is at room temperature cooled off, vacuum defoamation, protein/polyethyl acrylate mixed emulsion.Emulsion is at room temperature cooled off, and pours into after the vacuum defoamation in the tetrafluoroethylene vessel, and 40 ℃ of following curtain coatings obtained transparent nano composite plastics after 36 hours in vacuum drying oven.
Embodiment 10
Soy-protein is pre-dissolved in the water, obtains weight percent and be 40% the soy-protein aqueous solution, stir after 30 minutes, add butyl acrylate and emulsifying agent Sodium dodecylbenzene sulfonate, control butyl acrylate and emulsifying agent weight ratio are 2: 1.Be warming up to 70 ℃ after stirring, continue to stir after 80 minutes, form and disperse emulsion preferably.Then, add initiator to emulsion, initiator potassium persulfate is 5 ‰ of a Butyl Acrylate Monomer weight, after reacting 3 hours under 70 ℃, emulsion is at room temperature cooled off, vacuum defoamation, and protein/butyl polyacrylate mixed emulsion is put into extrusion moulding in the single screw extrusion machine after being concentrated into 80% solid content, the sectional temperature of adjusting screw(rod) is respectively 120 ℃, 130 ℃, 120 ℃, obtains transparent nano composite plastics.
Embodiment 11
Soy-protein is pre-dissolved in the water, obtains weight percent and be 40% the soy-protein aqueous solution, stir after 30 minutes, add acetic acid butene esters and emulsifying agent Sodium dodecylbenzene sulfonate, control acetic acid butene esters and emulsifying agent weight ratio are 4: 1.Be warming up to 70 ℃ after stirring, continue to stir after 80 minutes, form and disperse emulsion preferably.Then, add initiator potassium persulfate/hydrogen peroxide to emulsion, initiator is 7 ‰ of an acetic acid butene esters monomer weight, and reaction is after 3 hours down at 70 ℃, and emulsion is at room temperature cooled off, and vacuum defoamation is used for the gummed experiment of timber.
Embodiment 12
Soy-protein is pre-dissolved in the water, obtains weight percent and be 30% the soy-protein aqueous solution, stir after 30 minutes, add vinyl acetate and emulsifying agent sodium laurate, control vinyl acetate and emulsifying agent weight ratio are 6: 1.Be warming up to 70 ℃ after stirring, continue to stir after 80 minutes, form and disperse emulsion preferably.Then, add initiator potassium persulfate to emulsion, initiator is 3 ‰ of a Vinyl Acetate Monomer weight, and reaction is after 3 hours down at 80 ℃, and emulsion is at room temperature cooled off, and vacuum defoamation is used for the gummed experiment of timber.
Embodiment 13
Soy-protein is pre-dissolved in the water, obtains weight percent and be 50% the soy-protein aqueous solution, stir after 30 minutes, add allyl acetate and emulsifying agent sodium laurate, control allyl acetate and emulsifying agent weight ratio are 3: 1.Be warming up to 70 ℃ after stirring, continue to stir after 80 minutes, form and disperse emulsion preferably.Then, add initiator potassium persulfate/hydrogen peroxide to emulsion, initiator is 4 ‰ of an acetic acid allyl ester monomer weight, and reaction is after 3 hours down at 60 ℃, and emulsion is at room temperature cooled off, and vacuum defoamation is used for the gummed experiment of timber.
Claims (10)
1. a soy protein/emulsion polymerization high polymer nano composite material is characterized in that comprising soy-protein, polymer monomer and emulsifying agent; The weight ratio of described soy-protein and polymer monomer is 1: 0.1～9; The weight ratio of described polymer monomer and emulsifying agent is 10: 1～2.
2. nano composite material as claimed in claim 1 is characterized in that described soy-protein is soybean protein isolates or soybean protein concentrate matter.
3. nano composite material as claimed in claim 1 is characterized in that described polymer monomer is vinylbenzene, acrylic ester compound or acetic acid alkene ester compound.
4. nano composite material as claimed in claim 3 is characterized in that described acrylic ester compound is methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate or other acrylate homologues; Described acetic acid alkene ester compound is vinyl acetate, acetic acid third rare ester, acetic acid butene esters or other acetic acid alkene ester homologues.
5. nano composite material as claimed in claim 1 is characterized in that described emulsifying agent is one or more a mixture in sodium laurylsulfate salt, potassium laurate or the sodium lauryl sulphate.
6. the preparation method of the described nano composite material of claim 1 is characterized in that comprising the steps:
(1) soy-protein is scattered in the water that to form weight percent concentration be 2%～90% soy-protein suspension, add polymer monomer and emulsifying agent behind the mixing, mixing is warming up to 20～90 ℃ and obtains finely dispersed protein/polymer monomer mixed solution;
(2) be that the initiator of polymer monomer 1 ‰～10 ‰ adds trigger monomer polymerization in the mixed solution with weight, 60～90 ℃ of reaction final vacuum deaerations in 3～12 hours down, obtain composite emulsion, be soy protein/emulsion polymerization high polymer nano composite material after the cooling.
7. the preparation method of matrix material as claimed in claim 6 is characterized in that used initiator is a persulphate.
8. the application of the described nano composite material of claim 1 is characterized in that being applied to as the sizing agent of wood matrix or is applied to prepare nano composite plastics.
9. application as claimed in claim 8, it is characterized in that the described nano composite plastics that is applied to prepare, be under 20～80 ℃ of temperature, nano composite material curtain coating in vacuum drying oven promptly to be obtained transparent nano composite plastics sheet after 8～48 hours, or nano composite material is concentrated into extrusion moulding behind 50～90% the solid content, obtain nano composite plastics.
10. use as claimed in claim 8 or 9, it is characterized in that in the described nano composite plastics, soy-protein accounts for 10～90% of nano composite plastics gross weight.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103012692A (en) * | 2012-12-10 | 2013-04-03 | 浙江大学 | Method for preparing soybean protein copolymer emulsion |
| CN103007894A (en) * | 2012-12-13 | 2013-04-03 | 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 |
| CN106317666A (en) * | 2016-08-19 | 2017-01-11 | 常泰坤 | Method for preparing composite polystyrene material for computer |
| CN106543928A (en) * | 2016-10-28 | 2017-03-29 | 天长市永泰密封材料有限公司 | A kind of low temperature resistant cracking resistance container aqueous sealant and preparation method thereof |
| CN106700982A (en) * | 2016-11-24 | 2017-05-24 | 北华大学 | Single-component compound adhesive and preparation method thereof |
| CN106987173A (en) * | 2017-03-30 | 2017-07-28 | 天长市天达纸箱纸品厂 | A kind of preparation method of Environment-friendlywear-resistant wear-resistant water-based ink |
| CN109551605A (en) * | 2018-12-11 | 2019-04-02 | 山东新港环保材料科技有限公司 | Production technology without aldehyde particieboard |
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2008
- 2008-09-09 CN CNA2008101984233A patent/CN101407565A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012692A (en) * | 2012-12-10 | 2013-04-03 | 浙江大学 | Method for preparing soybean protein copolymer emulsion |
| CN103012692B (en) * | 2012-12-10 | 2014-08-27 | 浙江大学 | Method for preparing soybean protein copolymer emulsion |
| CN103007894A (en) * | 2012-12-13 | 2013-04-03 | 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 |
| 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 |
| CN106317666A (en) * | 2016-08-19 | 2017-01-11 | 常泰坤 | Method for preparing composite polystyrene material for computer |
| CN106543928A (en) * | 2016-10-28 | 2017-03-29 | 天长市永泰密封材料有限公司 | A kind of low temperature resistant cracking resistance container aqueous sealant and preparation method thereof |
| CN106700982A (en) * | 2016-11-24 | 2017-05-24 | 北华大学 | Single-component compound adhesive and preparation method thereof |
| CN106987173A (en) * | 2017-03-30 | 2017-07-28 | 天长市天达纸箱纸品厂 | A kind of preparation method of Environment-friendlywear-resistant wear-resistant water-based ink |
| CN109551605A (en) * | 2018-12-11 | 2019-04-02 | 山东新港环保材料科技有限公司 | Production technology without aldehyde particieboard |
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Open date: 20090415 |