CN1482164A - Chitosan poly-(4-vinylpyridine) quaternary amine salt blending film and preparation method and use thereof - Google Patents
Chitosan poly-(4-vinylpyridine) quaternary amine salt blending film and preparation method and use thereof Download PDFInfo
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- CN1482164A CN1482164A CNA031283292A CN03128329A CN1482164A CN 1482164 A CN1482164 A CN 1482164A CN A031283292 A CNA031283292 A CN A031283292A CN 03128329 A CN03128329 A CN 03128329A CN 1482164 A CN1482164 A CN 1482164A
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Abstract
The blended film has the basic composition of chitosan 60-95 wt% and poly(4-vinyl-N-alkylpyridyl) quaternary ammonium salt 5-40 wt%. It is prepared through mixing chitosan and poly(4-vinyl-N-alkylpyridyl) quaternary ammonium salt, curtain coating, drying and separating. It has excellent mechanical performance and biodegradation performance and high bactericidal capacity. It may be used in food freshness maintenance, biological sterilization, antibacterial material and controlled medicine release in food, medicine, agriculture, daily use article and other fields.
Description
Technical field
The present invention relates to a kind of chitosan and poly-(4-vinylpridine) quaternary amine blend film and its production and use.Belong to the functional polymer chemical field, also belong to the natural polymer field.
Background technology
Chitosan is natural alkaline polysaccharide, contains-NH
2,-OH functional group, easily modification forms various derivatives, and chitosan and derivative thereof cause that people pay close attention to and are: the good biocompatibility of (1) chitosan, and can be by biological degradation, degraded product is nontoxic; (2) chitosan and derivative thereof have the character of many uniquenesses, as germ resistance, microbial resistance, chelating, antiviral property, the cancer resistance to heavy metal ion, healing of promotion wound etc.Therefore, be widely used in fields such as medical science, pharmacy, papermaking, fabric, functional membrane parting material, environmental wastewater processing and biochemistry.
People such as Sashiwa have reported the sialic part of grafting on chitosan, are expected to become human erythrocyte's agglomerative inhibitor [Sashiwa H, Makimura Y, Shigemasa Y, et al.Chem Commun, 2000,11:909.].Its germ resistance may derive from: on (1) chitosan-and NH
2Positive charge with after the negative charge (as sialic acid) of the liposome of cell surface combines, suppressed the mobility of cell, thereby suppressed the growth of bacterium; (2) chitosan of oligomer energy penetration cell wall enters in the cell of bacterium, suppresses the formation of mRNA in its cell, thereby suppresses the growth of bacterium.2-methacrylic acid oxygen ethyl phosphonic acid and sodium vinyl sulfonate are grafted on the chitosan, obtain having derivative zwitterionic character, high-molecular weight, water-soluble chitosan, its germ resistance is than chitosan [the Jung B O that is significantly improved, Kim C H, Choi K S, et al.J ApplPolym Sci, 2000,77:2314.].Selectivity grafting sugar side chain on the C6 of chitosan obtains having the unique immunocompetent branch of promotion polysaccharide [Kurita K, Kojima T, Nishiyama Y, et al.Macromolecules, 2000,33:4711.], the polysaccharide of the sugared side chain of α (1-6) is promptly arranged on main chain α (1-4).Graft modification has improved the affinity of chitosan to solvent, also improved germ resistance and immunocompetence simultaneously, but enzymolysis is than chitosan difference.
Reported already that quaternary ammoniated poly-(4-vinylpyridine) salt had intensive sterilization, absorption microbial function: the systematic study of Japanese Viliene company poly-(4-vinylpyridine) resin with C4-C18 alkane and the reaction of benzyl haloalkane, find that they all have intensive sterilization, absorption microbial function; The class that the said firm produces is through phCH
2Be dissolved in the film of quaternary ammoniated poly-(4-vinylpyridine) salts solution in the ethanol after the Br modification, with one week of plant of this film cover-seeding, can prevent, suppress the viral communication [JP 04-234986, JP 05-58807] that causes by microorganisms such as bacterium, mould, virus in the soil.Professor Osama of Britain waits and will gather (4-vinylpyridine) resin and can the bacterium in 1 hour internal adsorption water reach 99.9%[ItabashiOssamn, et al.Chem Ind (London), (12), 450-451 (19920) after with the bromooctane modification].
Yet, the film-forming properties and the bad mechanical property of quaternary ammoniated poly-(4-vinylpyridine) salt, and cost an arm and a leg, limited its practical application.Chitosan is a kind of alkaline polysaccharide, ABUNDANT NATUREAL RESOURSES, outstanding advantage such as nontoxic, degradability, biocompatibility, little to the damage of medicine are arranged, be very suitable for the release of medicine etc., but poorly soluble, bad mechanical property is also arranged and shortcomings such as the pH dependency are too big.
Summary of the invention
The present invention provides a kind of chitosan and poly-(4-vinylpridine) quaternary amine blend film and its production and use at the problems referred to above, prepared blend film has good mechanical performance, biological degradability and antibiotic and sterilizing ability, and production process is simple, convenient.Can be used as food fresh keeping, biological antibiotic and anti-biotic material.
Technical scheme provided by the invention is: a kind of chitosan and poly-(4-vinylpridine) quaternary amine blend film, and it basic composition is: poly-(4-ethene-N-alkyl pyridine) quaternary amine of the chitosan of 60%-95%, 5%-40%; Above per-cent is mass percent.
Alkyl in above-mentioned poly-(4-ethene-N-alkyl pyridine) quaternary amine is C
4-C
7Alkyl or benzyl.
The present invention also provides the preparation method of above-mentioned chitosan with poly-(4-vinylpridine) quaternary amine blend film, and it is soluble in water to gather (4-ethene-N-alkyl pyridine) quaternary amine, makes the solution of 0.5-8wt%; Chitosan is dissolved in the acetic acid aqueous solution of 1-36wt%, makes the solution of 0.5-8wt%; After two kinds of solution that make are mixed, through curtain coating, drying, demoulding, required blend film.
Above-mentioned poly-(4-ethene-N-alkyl pyridine) quaternary amine can make as follows: in the 4-vinylpridine monomer, add the methyl alcohol of 0-200% volume ratio (with the monomeric volumeter of 4-vinylpridine) and the α of 0.1-1 ‰ weightmeasurement ratio (with the monomeric volumeter of 4-vinylpridine), α '-azobisisobutyronitrile, after being mixed, under inert gas conditions, in 50-80 ℃ react become sticky to system thick; Reaction adds methyl alcohol after finishing in polymkeric substance, make the product dissolving that obtains, and pours in the ether then and precipitates, and must gather (4-ethene-N-alkyl pyridine); Get poly-(4-vinylpridine) and be dissolved in the Nitromethane 99Min., add the doubly halogenated alkane of poly-(4-vinylpridine) weight of 1-5,, solution poured in the ether must gather (4-ethene-N-alkyl pyridine) quaternary amine in 30-78 ℃ of reaction after 10-72 hour down.
The blend film that the present invention makes is as biodegradable matrix material or as food fresh keeping, biological antibiotic, antibiotic and controlled delivery of pharmaceutical agents releasable material.
Poly-(4-vinylpyridine) quaternary amine and chitosan mixed film that the present invention makes have good mechanical performance, biological degradability and antibiotic and sterilizing ability, and production process is simple, convenient.Can be used as food fresh keeping, biological antibiotic and anti-biotic material.Therefore can be widely used in fields such as food, medical science, agricultural, daily necessities.Novelty of the present invention is to have made full use of high molecular blending and modifying theory, given full play to the synergistic effect that produces after two kinds of polymer blendings, the advantage of two kinds of polymkeric substance is all given full play of, make it better physics and biological function be arranged, enlarged the use range of two kinds of macromolecular materials effectively than two kinds of single polymers.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described:
Embodiment 1
To inject double-neck flask by the 4-vinylpridine monomer 12.0mL that underpressure distillation is purified, the methyl alcohol and the 0.012g α that add 12.0mL, α '-azobisisobutyronitrile (initiator), after being mixed, reinstall and heat up in a steamer prolong, liquid sealing pipe, slowly feed nitrogen, vacuumize three times, to eliminate the influence of oxygen.Become sticky thick in 60 ℃ of following isothermal reaction to systems.After the reaction, in polymkeric substance, add methyl alcohol, make the crude product dissolving that obtains, pour into then in the ether, get white products poly-(4-vinylpridine).Repeat aforesaid operations, get purified poly-(4-vinylpridine), dry in vacuum drier, get 6.5g poly-(4-vinylpridine).Recording its viscosity-average molecular weight is M
η=3.1 * 10
4(Ubbelohde viscometer, 25 ℃, ethanol).Get poly-(4-vinylpridine) 3 gram and be dissolved in the 60mL Nitromethane 99Min., add 15mL 1-n-butyl bromide,, solution poured in the ether must gather (4-ethene N-alkyl pyridine) salt 6.3g in 75-78 ℃ of reaction after 72 hours down.Through ultimate analysis, quaternary ammoniated degree is 0.96.
Chitosan is dissolved in the acetic acid aqueous solution of 2wt%, makes the solution (I) of 4wt%; Poly-(4-ethene-N-butyl-pyridinium) quaternary amine is dissolved in the distilled water, makes the solution (II) of 2wt%.After solution (I) and (II) mixing, curtain coating on sheet glass after under the room temperature dry 72 hours, is taken off from sheet glass, must contain poly-(4-ethene-N-butyl-pyridinium) quaternary amine blend film of 5-40wt%.Its thickness is 30 μ m.
For thickness is that the chitosan of 30 μ m and the mechanical property of gathering the blend film of (4-ethene-N-butyl-pyridinium) quaternary amine are compared to subordinate list.
The mechanical property of subordinate list blend film
Blend film
(per-cent is poly-(4-ethene-N-fourth to the tensile strength elongation at break
(MPa) percentage composition of quaternary amine (%) yl pyridines))
CH-0(0％) 48.3 8.72
CH-1(5％) 54.63 11.07
CH-2(10％) 56.34 18.62
CH-3(15％) 54.08 14.59
CH-3(20％) 42.34 5.75
CH-4 (40%) 37.17 2.30 (annotate: the mechanical property of all films records on all newly thinking carefully the CMT6503 instrument of testing tool company in Shenzhen)
Embodiment 2
To inject double-neck flask by the 4-vinylpridine monomer 12.0mL that underpressure distillation is purified, add 0.012g α, α '-azobisisobutyronitrile (initiator), after being mixed, reinstalling and heat up in a steamer prolong, liquid sealing pipe, slowly feed nitrogen, vacuumize three times, to eliminate the influence of oxygen.Become sticky thick in 60 ℃ of following isothermal reaction to systems.After the reaction, in polymkeric substance, add methyl alcohol, make its dissolving, pour into then in the ether, get white products poly-(4-vinylpridine).Repeat aforesaid operations, get purified poly-(4-vinylpridine), dry in vacuum drier, get 6.7g poly-(4-vinylpridine).Recording its viscosity-average molecular weight is M
η=8.7 * 10
4(Ubbelohde viscometer, 25 ℃, ethanol).Get poly-(4-vinylpridine) 3 gram and be dissolved in the 60mL Nitromethane 99Min., add the 15mL hexyl bromide 1 bromohexane,, solution poured in the ether must gather (4-ethene-N-hexyl pyridine) salt 6.6g in 75-78 ℃ of reaction after 54 hours down.Through ultimate analysis, quaternary ammoniated degree is 0.86.
Chitosan is dissolved in the acetic acid aqueous solution of 1wt%, makes the solution (I) of 8wt%; Poly-(4-ethene-N-hexyl pyridine) quaternary amine is dissolved in the distilled water, makes the solution (II) of 4wt%.After solution (I) and (II) mixing, curtain coating on sheet glass after under the room temperature dry 60 hours, is taken off from sheet glass, must contain poly-(4-ethene-N-hexyl pyridine) quaternary amine blend film of 5-40wt%.Its thickness is 50 μ m.
Embodiment 3
To inject double-neck flask by the 4-vinylpridine monomer 12.0mL that underpressure distillation is purified, the methyl alcohol and the 0.006g α that add 24.0mL, α '-azobisisobutyronitrile (initiator), after being mixed, reinstall and heat up in a steamer prolong, liquid sealing pipe, slowly feed nitrogen, vacuumize three times, to eliminate the influence of oxygen.Become sticky thick in 60 ℃ of following isothermal reaction to systems.After the reaction, in polymkeric substance, add methyl alcohol, make the crude product dissolving that obtains, pour into then in the ether, get white products poly-(4-vinylpridine).Repeat aforesaid operations, get purified poly-(4-vinylpridine), dry in vacuum drier, get 7.8g poly-(4-vinylpridine).Recording its viscosity-average molecular weight is M
η=9.4 * 10
4(Ubbelohde viscometer, 25 ℃, ethanol).Get poly-(4-vinylpridine) 3 gram and be dissolved in the 60mL Nitromethane 99Min., add the 10mL benzyl chloride,, solution poured in the ether must gather (4-ethene-N-benzyl-pyridine) quaternary amine 5.6g in 75-78 ℃ of reaction after 72 hours down.Through ultimate analysis, quaternary ammoniated degree is 0.67.
Chitosan is dissolved in the acetic acid aqueous solution of 3wt%, makes the solution (I) of 6wt%; Poly-(4-ethene-N-benzyl-pyridine) quaternary amine is dissolved in the distilled water, makes the solution (II) of 3wt%.After solution (I) and (II) mixing, curtain coating on sheet glass after under the room temperature dry 72 hours, is taken off from sheet glass, must contain poly-(4-ethene-N-benzyl-pyridine) quaternary amine blend film of 5-40wt%.Its thickness is 40 μ m.
Claims (6)
1. a chitosan and poly-(4-vinylpridine) quaternary amine blend film, it basic composition is: poly-(4-ethene-N-alkyl pyridine) quaternary amine of the chitosan of 60%-95%, 5%-40%; Above per-cent is mass percent.
2. blend film according to claim 1 is characterized in that: the alkyl in poly-(4-ethene-N-alkyl pyridine) quaternary amine is C
4-C
7Alkyl or benzyl.
3. the preparation method of the described chitosan of claim 1 and poly-(4-vinylpridine) quaternary amine blend film, it is characterized in that: it is soluble in water to gather (4-ethene-N-alkyl pyridine) quaternary amine, makes the solution of 0.5-8wt%; Chitosan is dissolved in the acetic acid aqueous solution of 1-36wt%, makes the solution of 0.5-8wt%; After two kinds of solution that make are mixed, through curtain coating, drying, demoulding, required blend film.
4. preparation method according to claim 3, it is characterized in that: in the 4-vinylpridine monomer, add the methyl alcohol of 0-200% volume ratio and the α of 0.1-1 ‰ weightmeasurement ratio, α '-azobisisobutyronitrile, after being mixed, under inert gas conditions, in 50-80 ℃ react become sticky to system thick; Reaction adds methyl alcohol after finishing in polymkeric substance, make the product dissolving that obtains, and pours in the ether then and precipitates, and must gather (4-ethene-N-alkyl pyridine); Get poly-(4-vinylpridine) and be dissolved in the Nitromethane 99Min., add the doubly halogenated alkane of poly-(4-vinylpridine) weight of 1-5,, solution poured in the ether must gather (4-ethene-N-alkyl pyridine) quaternary amine in 30-78 ℃ of reaction after 10-72 hour down.
5. the described chitosan of claim 1 is used as biodegradable matrix material with poly-(4-vinylpridine) quaternary amine blend film.
6. the described chitosan of claim 1 is used as food fresh keeping, biological antibiotic, antibiotic and controlled delivery of pharmaceutical agents releasable material with poly-(4-vinylpridine) quaternary amine blend film.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183752A (en) * | 2019-06-20 | 2019-08-30 | 中原工学院 | A kind of preparation method of carboxy nitrile rubber/carboxyl chitosan composite conductive film |
| CN116813825A (en) * | 2023-06-29 | 2023-09-29 | 征鸿诺瓦医疗科技(深圳)有限公司 | Crosslinkable cationic polymer and synthetic method and application thereof |
-
2003
- 2003-07-15 CN CN 03128329 patent/CN1273530C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183752A (en) * | 2019-06-20 | 2019-08-30 | 中原工学院 | A kind of preparation method of carboxy nitrile rubber/carboxyl chitosan composite conductive film |
| CN110183752B (en) * | 2019-06-20 | 2021-05-04 | 中原工学院 | Preparation method of carboxyl nitrile rubber/carboxylated chitosan composite conductive film |
| CN116813825A (en) * | 2023-06-29 | 2023-09-29 | 征鸿诺瓦医疗科技(深圳)有限公司 | Crosslinkable cationic polymer and synthetic method and application thereof |
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