CN1243602C - Cross-blending membrane, preparation method and application - Google Patents
Cross-blending membrane, preparation method and application Download PDFInfo
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- CN1243602C CN1243602C CN 200410012845 CN200410012845A CN1243602C CN 1243602 C CN1243602 C CN 1243602C CN 200410012845 CN200410012845 CN 200410012845 CN 200410012845 A CN200410012845 A CN 200410012845A CN 1243602 C CN1243602 C CN 1243602C
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Abstract
The present invention discloses a blending film with poly-4-7 vinyl pyridine, and natural lignin and derivant thereof. The blending film comprises the base components of 30% to 99% of poly-4-7 vinyl pyridine and 1% to 30% of lignin and derivant thereof. The blending film is prepared by that poly-4-7 vinyl pyridine is uniformly mixed with a solution of lignin and derivant thereof; then the mixture is treated through tape casting, desiccation and defilming. The film has favorable intermiscibility, mechanical properties, biodegradability, separating capability for permselective gas, selective permeability for alcohol solutions, acid solutions and vapour, purification treatment capability for organic waste water and air pollution, simple and convenient production processes, and can be used as a gas permselective film, a permselective film for alcohol solutions, acid solutions and vapour, and a separating film for purification treatment of organic waste water and air pollution.
Description
Technical field
The present invention relates to gather (4-vinylpridine) (P4VP) with natural lignin's or derivatives thereof blend film and its production and use, belong to the functional polymer chemical field, also belong to the natural polymer field.
Background technology
The polyvinyl pyridine resin is the special functional resin of a class, compares advantage and the function with many uniquenesses with common polystyrene resins.Japan Patent [JP 744-127930] reported with acetone and ethanol in the P4VP resin adsorption recycle-water solution, and can add the resin that contains different crosslinking agents and pore dosage it is adsorbed respectively by regulating; Nariyoshi professor [Kawabata Nariyishi, et al, Biotechnol Bioeng.1989,34 (8), 1045-1049] studies show that: P4VP is used for the Aerobic Process for Treatment of sewage, finds that the removing amount of COD can reach more than 60%; Japan Koei company discovers that P4VP can adsorb organic acid [JP 80-73343; DE 3043766], can from alcohol, adsorb Sodium Benzoate [Patel RM, et al, Am Lab, 1990,22 (3), 92,94-99].The Lee of U.S. Purdue university is used for lactic fermentation and separates that [The 3 for Lee S, et al with Tsao
RdChem Conggress of North Am, Toronto, Canada, June, 1988,5-10], the result shows that P4VP can adsorb lactic acid and make its separation, and the pH value that can regulate zymotic fluid automatically, overcome the toxic action of Lactic Acid from Fermentation Broth to bacterial classification, limited the adverse effect of concentration of substrate.The existence that China Zhejiang University finds inorganic salts in the zymotic fluid is adsorbed with facilitation to lactic acid on the P4VP resin, the pH value of liquid phase has a significant impact equilibrium adsorption, and maximal absorptive capacity is just in the pH of the solution of lactic acid value own.Because the nitrogen-atoms on the pyridine ring has only electrophilic ability, be the fragrant heterocycle of short of electricity of a standard, be not vulnerable to the attack of oxidant, therefore in the environment of strong oxidizer, tangible oxidation resistance is arranged.U.S. Arco chemical industry technology company studies show that P4VP can remove the ability of impurity phenol in process for prepairng hydrogen peroxide by anthraquinone [US 4975266].P4VP also has good radioresistance stability except that good heat endurance is arranged, can be used for the production of nuclear fuel and the absorption of radioactive element.P4VP is applied to go out in the waste liquid that power station, Britain Portsmouth produces
235U and
99Tc has obtained very satisfied effect [Bostick W D, et al, ACS Symp Ser, 1989,442,345-367].
The JYH-Jeng Shieh of Singapore etc. has studied P4VP to all gases (O
2, N
2, CO
2, CH
4, H
2) the diffusivity of selective power, gas of selective permeation and film to the solvability [JYH-Jeng Shieh, et al, JPolym Sci Part B:PP.1999,37:2851] of gas.Japan Sumita etc. has studied P4VP the selection of oxygen, nitrogen has been seen through ability [Sumita, I., Japan Open Patent 51-7297,1976].Lai and Wei studied the 4VP radiation grafting in poly-methyl 1-amylene film to O
2/ N
2Separation [Lai, J.Y.; Wei, S.L. J Appl Polym Sci.1986,32,5763]; Yoshikawa etc. have synthesized 4VP and acrylonitrile copolymer to CO
2Selection performance [Yoshikawa, M.et al J Appl Polym Sci.1988,35,145]; Chung etc. have studied P4VP and hollow fiber composite membrane to all gases (O
2, N
2, CO
2, CH
4, H
2) selection see through ability [Chung, T.S.et al J Appl Polym Sci.1994,53,701; J Membr Sci.1993,152,211]; Yet the fragility that P4VP is intrinsic is easy to be adsorbed on the surface of solid, is difficult for peeling off forming no support membrane, has limited its application.At the intrinsic defective of P4VP, Xin-Gui Li etc. have improved the mechanical property of film to P4VP and ethyl cellulose blend, are easy to from the surface of solids peel off, and have studied gas O
2, N
2, CO
2, CH
4, H
2The influence [Xin-Gui Li, et al Polymer 2001,42,6859] of selective power.Simultaneously, Eizo Oikawa etc. has studied P4VP and the different compositions of the interpenetrating network membrane (ipn) of bunching glycerine methacrylic acid and polyvinyl alcohol and the mechanical property and [the Eizo Oikawa of the relation between the separation factor of film, et al J Appl Polym Sci.1998,67,1953; 2001,82,2729].
Lignin is second largest natural polymer, is mainly derived from the byproduct of paper industry black liquor.Lignin belongs to renewable resource, and its utilization comes into one's own day by day with exploitation.The research of lignin macromolecular material has considerable report, as; Lignin phenol formaldehyde resin [Danielson B, et al, J.Adhe.Sci.Technol.1998,12,923], lignin polyurethane [Evtuguin D V, et al, Eur.Polym.J., 1998,34,1163], lignin exchanger resin [Zoumpoulakis L, et al, Polum.Int., 2001,50,277] etc.The high polymer blend has become the most important and most economical method of exploitation high polymer new material, and low-cost and many active lignin are expected to by blend and the filling-modified cost that lowers macromolecular material, keep even improve the performance of material.The basic structure of the existing aromatic rings rigidity of lignin not only has submissive side chain, existing numerous reaction active groups but also the inferior polymer substance of subparticle shape of a lot of Large ratio surfaces is arranged, thereby is widely used for substituting carbon black and as the filling-modified rubber of good reinforcing agent.Lignin and derivative thereof can with polyethylene (PE) and polypropylene (PP) [Kharade A Y, et al, J.Appl.Polym.Sci., 1999,72,1321.], polyvinyl chloride (PVC) [FelDman D, et al, J.Macromol.Sci.-Pure Appl.Chem., 1994, A31,555.], polymethyl methacrylate (PMMA) [Ciemniecki S L, etal, Polymer, 1988,29,102.], polyvinyl alcohol (PVA) [Ciemniecki S L, et al, Polymer, 1988,29,1031.], ethylene-vinyl acetate copolymer [Glasser W G, et al, J.Wood Chem.Technol., 1988,8,221.], polyaniline [Rodrigues P C, et al, Eur.Polym.J., 2001,37,2217.] etc. synthetic high polymer carries out blend.Lignin plays a part rigid particles and strengthens in co-mixing system, and the performances such as thermally-stabilised, light degradation to material have certain influence simultaneously.
Summary of the invention
Problem to be solved by this invention provides a kind of blend film and its production and use, and the film that makes has the separating power of good intermiscibility, mechanical property, biological degradability and selective permeation gas; To alcohol, acid solution steam selective permeation and pair organic wastewater is arranged and air-polluting purified treatment ability, and the preparation method simple, convenient, be easy to peel off from the surface of solids.Can be used as gas and select the permeability film; Alcohol, acid solution steam selective permeation film and organic wastewater and air-polluting purified treatment diffusion barrier.
Technical scheme provided by the invention is: a kind of blend film, it basic composition is: the viscosity average molecular weigh of 70-99wt% is poly-(4-vinylpridine) of 30000-200000g/mol, the lignin of 1-30wt%.
Above-mentioned lignin is natural lignin or the derivative that obtained by halogenation, nitrated, carboxy methylation or phenolate by natural lignin.
The present invention also provides the preparation method of above-mentioned blend film, with viscosity average molecular weigh is that poly-(4-vinylpridine) of 30000-200000g/mol is dissolved in nitromethane, oxolane, methyl alcohol, ethanol or N, in the dinethylformamide, make the solution of 0.5-8wt%; Natural lignin's or derivatives thereof is dissolved in the identical organic solvent, makes the solution of 0.5-8wt%; With above-mentioned poly-(4-vinylpridine) solution 70-99wt%, lignin liquor 1-30wt% is after raw material mixes, and through curtain coating, drying, demoulding, gets required blend film.
Above-mentioned poly-(4-vinylpridine) makes as follows: in the 4-vinylpridine monomer, add the methyl alcohol of 0-200% volume ratio and the α of 0.1-1 grams per liter, α '-azobisisobutyronitrile is after being mixed, under inert gas conditions, in 50-80 ℃ react become sticky to system thick; Add methyl alcohol then in reaction becomes sticky thick system, make the product dissolving that obtains, pour in the absolute ether then and precipitate, must gather (4-vinylpridine), its viscosity average molecular weigh is 30000-200000g/mol.
Lignin derivative can be obtained by halogenation, nitrated, carboxy methylation, phenolate or graft copolymerization etc. by natural lignin.
The blend film that the present invention makes can be used as biodegradable composite; Select the permeability film as gas; Alcohol, acid solution steam selective permeation film and organic wastewater and air-polluting purified treatment diffusion barrier.
Poly-(4-vinylpyridine) and natural lignin and derivative blended membrane thereof that the present invention makes have the separating power of good mechanical performance (as good mechanical strength, hot strength), biological degradability and selective permeation gas; To alcohol, acid solution steam selective permeation and pair organic wastewater is arranged and air-polluting purified treatment ability, and production process is simple, convenient, product is easy to peel off from the surface of solids.Can be used as gas and select the permeability film; Alcohol, acid solution steam selective permeation film and organic wastewater and air-polluting purified treatment diffusion barrier.Novelty of the present invention is to have made full use of high molecular blending and modifying theory, given full play to the cooperative effect that produces after two kinds of polyblends, the advantage of two kinds of polymer is all given full play of, make it better physics and biological function be arranged, enlarged the scope of application of two kinds of macromolecular materials effectively than two kinds of single polymers.
The specific embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described:
Embodiment 1
Embodiment 1
To inject double-neck flask by the 4-vinylpridine monomer 12.0mL that decompression distillation is purified, the methyl alcohol and the 0.012g α that add 12.0mL, α '-azobisisobutyronitrile (initator), after being mixed, reinstall stream condenser pipe, liquid sealing pipe, slowly feed nitrogen, vacuumize three times, to eliminate the influence of oxygen.Become sticky thick in 50-80 ℃ of following isothermal reaction to system.After the reaction,, pour into then in the absolute ether, get white products to wherein adding methyl alcohol, make the crude product dissolving that obtains.Repeat aforesaid operations, get pure product, dry in vacuum desiccator, get 6.5g white products poly-(4-vinylpridine).Recording its viscosity average molecular weigh is M
η=3.0-20.0 * 10
4G/mol (Ubbelohde viscometer, 25 ℃, ethanol).
Taking by weighing 1 gram poly-(4-vinylpridine) is dissolved in the nitromethane of 20mL, the natural lignin that takes by weighing 0.04 gram is dissolved among the identical organic solvent 10mL, treat to dissolve fully the back two kinds of solution are mixed, on the surface of solids,, get required blend film P4VP/LIG-1 through curtain coating, drying, demoulding.
Taking by weighing 1 gram poly-(4-vinylpridine) is dissolved in the oxolane of 20mL, the natural lignin that takes by weighing 0.09 gram is dissolved among the identical organic solvent 10mL, treat to dissolve fully the back two kinds of solution are mixed, on the surface of solids,, get required blend film P4VP/LIG-2 through curtain coating, drying, demoulding.
Take by weighing 1 gram and gather nitromethane, oxolane, methyl alcohol, ethanol, the N that (4-vinylpridine) is dissolved in 20mL, in the dinethylformamide, the natural lignin that takes by weighing 0.11 gram is dissolved among the identical organic solvent 10mL, treating to dissolve fully the back is mixed two kinds of solution, on the surface of solids,, get required blend film P4VP/LIG-3 through curtain coating, drying, demoulding.
Take by weighing 1 gram and gather nitromethane, oxolane, methyl alcohol, ethanol, the N that (4-vinylpridine) is dissolved in 20mL, in the dinethylformamide, the natural lignin that takes by weighing 0.18 gram is dissolved among the identical organic solvent 10mL, treating to dissolve fully the back is mixed two kinds of solution, on the surface of solids,, get required blend film P4VP/LIG-4 through curtain coating, drying, demoulding.
Taking by weighing 1 gram poly-(4-vinylpridine) is dissolved in the ethanol of 20mL, the natural lignin that takes by weighing 0.11 gram is dissolved among the identical organic solvent 10mL, treat to dissolve fully the back two kinds of solution are mixed, on the surface of solids,, get required blend film P4VP/LIG-3 through curtain coating, drying, demoulding.
Take by weighing 1 gram and gather the N that (4-vinylpridine) is dissolved in 20mL, in the dinethylformamide, the natural lignin that takes by weighing 0.18 gram is dissolved among the identical organic solvent 10mL, treating to dissolve fully the back is mixed two kinds of solution, on the surface of solids,, get required blend film P4VP/LIG-4 through curtain coating, drying, demoulding.
Taking by weighing 1 gram poly-(4-vinylpridine) is dissolved in the ethanol of 20mL, the natural lignin that takes by weighing predetermined 0.25 gram is dissolved among the identical organic solvent 10mL, treat to dissolve fully the back two kinds of solution are mixed, on the surface of solids,, get required blend film P4VP/LIG-5 through curtain coating, drying, demoulding.
The mechanical property of gained blend film sees attached list 1.
The mechanical property contrast of subordinate list 1. poly-(4-vinyl) pyridine P4VP and blend film
| Numbering | P4VP | P4VP/LIG-1 | P4VP/LIG-2 | P4VP/LIG-3 | P4VP/LIG-4 | P4VP/LIG-5 |
| Hot strength σ b(MPa) | 15.64 | 17.35 | 20.08 | 26.88 | 33.03 | 19.99 |
| Ultimate elongation rate ε b(％) | 2.64 | 5.55 | 6.00 | 9.03 | 1.55 | 1.09 |
Embodiment 2
To inject double-neck flask, 0.01g α, α '-azobisisobutyronitrile (initator) by the 4-vinylpridine monomer 12.0mL that decompression distillation is purified, after being mixed, reinstall stream condenser pipe, liquid sealing pipe, slowly feed nitrogen, vacuumize three times, to eliminate the influence of oxygen.Become sticky thick in 50-80 ℃ of following isothermal reaction to system.After the reaction,, pour into then in the absolute ether, get white products to wherein adding methyl alcohol, make the crude product dissolving that obtains.Repeat aforesaid operations, get pure product, dry in vacuum desiccator, get 6.4g white products poly-(4-vinylpridine).Recording its viscosity average molecular weigh is M
η=3.0-20.0 * 10
4G/mol (Ubbelohde viscometer, 25 ℃, ethanol).
The preparation of nitration of lignin: back dropping 22.5mL acetic anhydride is mixed in 20g natural lignin and 35g fuming nitric aicd, and continuous stirring reaction is 16 hours in the cryosel water-bath.Product is shifted out in 1 * 10
4The solid sediment that super centrifugal sedimentation 20min obtains under the rpm speed is also extremely neutral with the frozen water cyclic washing, and vacuum drying obtained the nitro lignin of rufous in 7 days then.
Take by weighing 1 gram and gather nitromethane, oxolane, methyl alcohol, ethanol or the N that (4-vinylpridine) is dissolved in 20mL, in the dinethylformamide, the nitro lignin that takes by weighing 0.24 gram is dissolved among the identical organic solvent 10mL, treating to dissolve fully the back is mixed two kinds of solution, on the surface of solids,, get required blend film through curtain coating, drying, demoulding.
With reference to embodiment 1, can make poly-(4-vinylpridine) and other lignin (being prior art products, the lignin that obtains by copolymerization such as halogenation, nitrated, carboxy methylation, phenolate or grafting by natural lignin) blend film.
Claims (8)
1. blend film, it basic composition is: the viscosity average molecular weigh of 70-99wt% is poly-(4-vinylpridine) of 30000-200000g/mol, the lignin of 1-30wt%.
2. blend film according to claim 1 is characterized in that: lignin is natural lignin or the derivative that obtained by halogenation, nitrated, carboxy methylation or phenolate by natural lignin.
3. the preparation method of the described blend film of claim 1, it is characterized in that: with viscosity average molecular weigh is that poly-(4-vinylpridine) of 30000-200000g/mol is dissolved in nitromethane, oxolane, methyl alcohol, ethanol or N, in the dinethylformamide, make the solution of 0.5-8wt%; Natural lignin or be dissolved in the identical organic solvent by the derivative that halogenation, nitrated, carboxy methylation or phenolate obtain by natural lignin makes the solution of 0.5-8wt%; With above-mentioned poly-(4-vinylpridine) solution 70-99wt%, lignin liquor 1-30wt% is after raw material mixes, and through curtain coating, drying, demoulding, gets required blend film.
4. preparation method according to claim 3, it is characterized in that: above-mentioned poly-(4-vinylpridine) makes as follows: in the 4-vinylpridine monomer, add the methyl alcohol of 0-200% volume ratio and the α of 0.1-1 grams per liter, α '-azobisisobutyronitrile, after being mixed, under inert gas conditions, in 50-80 ℃ react become sticky to system thick; Add methyl alcohol then in reaction becomes sticky thick system, make the product dissolving that obtains, pour in the absolute ether then and precipitate, must gather (4-vinylpridine), its viscosity average molecular weigh is 30000-200000g/mol.
5. the described blend film of claim 1 is as the application of biodegradable composite.
6. the described blend film of claim 1 is as the application of gas-selectively permeability film.
7. the described blend film of claim 1 is as the application of alcohol, acid solution steam selective permeation film.
8. the described blend film of claim 1 is as the application of diffusion barrier in organic wastewater or air-polluting purified treatment.
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