CN1587281A - Process for preparing chitosan quaternary ammonium salt - Google Patents
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- CN1587281A CN1587281A CN 200410052654 CN200410052654A CN1587281A CN 1587281 A CN1587281 A CN 1587281A CN 200410052654 CN200410052654 CN 200410052654 CN 200410052654 A CN200410052654 A CN 200410052654A CN 1587281 A CN1587281 A CN 1587281A
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- quaternary ammonium
- ammonium salt
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Abstract
The present invention relates to the preparation process of quaternary ammonium salt of chitosan. The quaternary ammonium salt of chitosan contains halogen ion Cl, B or I, has chitosan deacetylating degree of 75-98 %, and viscosity average molecular weight of 15-210 KD. The synthesis process is simple and high in substitution degree, and the quaternary ammonium salt of chitosan has high water solubility and high bacteriostasis and antibacterial activity, and is suitable to be environmental safe biological bactericide.
Description
Technical field
The present invention relates to the preparation method of relevant chitosan quaternary ammonium salt.Be meant that more specifically deacetylation is the preparation method of the chitosan aliphatics of 75%-98% and aromatic series chlorination, bromination, iodate quaternary ammonium salt.
Background technology
Chitin or chitosan derivatives have anti-microbial activity.Can make flavacin reduce more than 90% as N-cm-chitosan (N-CM-Chitosan), it is over half to reduce fungal growth, can suppress the formation of spore-germination and fungus body spore, to responsive especially (the Muzzarelli R.A.A. of oral cavity bacterium especially decayed tooth bacterium; Tarsi R, et al.Antibacterial action ofamphoteric and biopolymers, Prod.Chitin Aerosol Sel.1987,28 (3): 13; Muzzarelli R A A, Carboxymethylated chitins and chitosans.Carbohydrate Polymer, 1988,8:1-12).O-cm-chitosan (O-CM-Chitosan) and N, (N O-CM-Chitosan) has anti-microbial activity to O-two cm-chitosan.(Muzzarelli?R?A?A,Tarsi?R.et?al,Antimicrobial?properties?of?N-Carboxybutyl?chitosan.Antimicrobial?Agents?and?Chemotherapy?1990,34(10):2019-2023)。
Carry out relatively (Kim J.H. of germ resistance; Lee Y.M.Synthesis and properties of diethylaminoethylchitosan.Polymer, 1993,34 (9): 1952-1957), Kim finds diethylaminoethyl-(DEAE) group is linked into the C of chitin
6Form diethylaminoethyl-chitin (DEAE-chitin) on the hydroxyl of position, then with ethyl halogenide with its quaternized TEAE triethyl aminoethyl chitin (TEAE-chitin) that obtains.In addition DEAE-chitin is taken off acetyl and get DEAE-chitosan, relatively the anti-microbial activity of its Chinese People's Anti-Japanese Military and Political College enterobacteria and streptococcus aureus finds that its anti-microbial activity descending order is followed successively by TEAE-chitin>DEAE-chitosan>DEAE-chitin.(Tsurugai such as Tsurugai K., K.et al.Preparation andantibacterial activity of N-trimethylammonium salts of chitosan.Sen-i Gakkaishi 1994,50 (5), 215-20) find N, N, N-trimethyl chitin quaternary ammonium salt has the activity of enterobacteria ATCC of the Chinese People's Anti-Japanese Military and Political College 25922 and Staphylococcus ATCC 149909.The quaternary ammonium salt that contains the N-chain alkyl chitosan to the moon pityrosporion ovale, intestinal bacteria have anti-microbial effect (Yu Yisong, a kind of natural macromolecular material----chitin and derivative thereof, chemical and bonding, 1992,1:50-54).Chitosan and methyl iodide in triethylamine, react resulting quaternary ammonium salt to gram-positive microorganism have very strong restraining effect (HiranoS., Matsuda N.et al, Carbohydr.Res.1987,3:13-16).Kim (Kim C.H., Choi J.W.et al, Synthesis of chitosan derivatives with quaternary ammonium salt and their antibacterialactivity, Polymer Bulletin, 1997,38 (4), 387-393.) wait of the increase of discovery alkyl chitosan quaternary ammonium salt along with alkyl chain length, its anti-microbial activity also increases, and shows the length of alkyl chain and the anti-microbial activity that the positive charge substituting group affects chitosan derivatives consumingly.
Relevant with the structure of product from last visible germ resistance, the quaternary ammonium salt germ resistance is greater than chitosan and chitin.Because the structure of chitosan quaternary ammonium salt and water-soluble to chitosan quaternary ammonium salt anti-microbial activity and use very big influence arranged, the water-soluble chitosan quaternary ammonium salt of therefore synthetic various structures is chitosan quaternary ammonium salt keys as the biological species sterilant of environmental safety.The synthetic method of chitosan quaternary ammonium salt mainly contains:
Muzzarelli Tanfanni (Muzzarelli R A A, Tanfani, F., Carbohydrate Polymers, 1985,5:297-307) reported the synthetic method of iodate N-trimethyl chitin, be about to N-dimethyl chitosan and iodomethane reaction generation chitosan quaternary ammonium salt, but this method synthetic chitosan quaternary ammonium salt has been water-fast; Domard (Domard, A., et al, New method for the quaternization of chitosan.Int.J.Biol.Macromol, 1986,8:105-107; Domard, A.; Rinando M.and Tanfani, F., Carbohydrate Polym, (1985), reported used methyl iodide 5:297) that directly from the synthetic quaternary ammonium salt of chitosan, but chitosan iodine is good not as the chloro quaternary ammonium salt for the stability of quaternary ammonium salt in N-N-methyl-2-2-pyrrolidone N-solvent, so iodate N-trimethyl chitin is water-soluble, and can make the transition by ion exchange resin is chlorination N-trimethyl chitin.Toahihiro (Seo, the Toahihiro of Japan; Nasashi et al, Synthesis and properties of N-alkylsubstituted chitison and their quartemized derivatives.Kichin, KitosanKenkyu, 1995,1 (2), 168-169) with the N-alkyl chitosan quaternized after, quaternary ammonium salt has had bigger soluble end, equal solubilized in the aqueous solution of pH1~11.Xu Chen (Xu Chen, Lu Canhui etc., the synthetic and structural characterization of chitosan quaternary ammonium salt, functional polymer journal, 1997,10 (1): 51-55), pass through C with chitosan and glycidyl trimethylammonium chloride reaction
2The introducing of quaternary ammonium salt group makes chitosan quaternary ammonium salt on the position.Kim (Kim C.H.; Kim S.Y.et al., Synthesis andantibacterial activity of water-soluble derivatives.Polym.Adv.Technol.1997,8 (5), 319-325.) by the Schiff's base intermediate, alkyl is received on the amino of chitosan, resulting N-alkyl shell 2 polysaccharid derivatives use methyl iodide quaternized again, obtain chitosan iodate quaternary ammonium salt, water-soluble enhancing greatly.
The synthetic method of the chitosan quaternary ammonium salt of above bibliographical information is technical mainly to have solved the water-soluble of chitosan quaternary ammonium salt.And only synthesized a few aliphatics chitosan quaternary ammonium salt.But at synthetic different substituents, particularly close the aryl chitosan quaternary ammonium salt, synthetic technology does not also have versatility, and the synthetic operation step is loaded down with trivial details, the substitution value of chitosan quaternary ammonium salt is low, and product separates from reacted viscous solution and problem such as sizable difficulty of purifying.
Summary of the invention
The present invention is in order to overcome the loaded down with trivial details of synthetic chitosan quaternary ammonium salt operation, and the chitosan quaternary ammonium salt substitution value is low, and product separates from reacted viscous solution and problem such as the difficulty of purifying.Provide a kind of easy, cost is low, good water solubility, the chitosan quaternary ammonium salt chemical synthesis process that substitution value is high.
Chemical equation of the present invention is as follows:
X=Cl, Br, I R
1=alkyl or aryl R
2=methyl, ethyl
Described R
1Be alkyl or aryl, R
2Be methyl, ethyl.The halide anion that forms chitosan quaternary ammonium salt is chlorine, bromine, iodine.Deacetylating degree of chitosan is 75%~98%, molecular weight is 1.5 ten thousand~21.0 ten thousand (viscosity-average molecular weight), the warp of raw materials of chitosan is refining, dissolving, condensating reductive, replacement, separation, purifying preparation process, obtains various N-alkylation of the present invention or N-arylation chitosan quaternary ammonium salt.
The process for purification of chitosan of the present invention is as follows; Chitosan through the various molecular weight of hydrogen peroxide degraded, be dissolved in 0.2~2% the acetic acid solution, remove impurity, NaOH with 30-50% neutralizes up to precipitation no longer occurring, and with the distilled water wash precipitation, regulating the pH value is neutrality, soaked 24~48 hours with acetone, filter,, must make with extra care chitosan in 40~60 ℃ of dryings.Measuring deacetylating degree of chitosan is 75%~98%, and molecular weight is 1.5 ten thousand~21.0 ten thousand (viscosity-average molecular weight).
The preparation process of chitosan quaternary ammonium salt of the present invention is:
1. dissolving: will make with extra care the chitosan solution (W/V) that chitosan is dissolved in formation 0.5%~3.0% in acetate (0.5%-2.5%)~sodium acetate (0.5%-2.5%) mixing solutions (W/V).
2. condensating reductive: the aldehyde solution of 0.3-0.6 mole is in room temperature-35 ℃, stirs down to be added in the above-mentioned chitosan solution, continue to stir 30-60 minute, with NaOH (1-2mol/L) accent pH to 4.5-6.0.Add reductive agent NaBH under in above-mentioned chitosan solution, stirring
4(10%-15%); After reduction reaction 2-4 hour, transfer pH to 8-9, get the chitosan derivatives of N-alkylation or N-arylation with NaOH (1-2mol/L).
3. replace, separate: the chitosan derivatives of washing N-alkylation or N-arylation with aquae destillata is to neutral, use ethanol and ether immersion 4 hours successively or use ethanol and ether Soxhlet to extract successively 4 hours, got the chitosan derivatives of N-alkylation or arylation at 40-60 ℃ of vacuum-drying 20-48 hour.
With the N-alkylation of acquisition or the chitosan derivatives of arylation, be dispersed in an amount of N-alkyl-2-Pyrrolidone solvent, after 12-20 hour, add NaOH (1-2mol/L) and CH in the room temperature swelling
3X or CH
3CH
2X (3-10 of the chitosan derivatives mole number of N-alkylation or arylation doubly) adds catalyst n aI again in reactant system, making its concentration is 0.1-0.4mol/L.After 40 ℃ of-60 ℃ of following stirring reaction 10-20 hours, in reactant system, add acetone, do not have precipitation until solution and generate, N-alkylation that is precipitated out or N-arylation chitosan quaternary ammonium salt are used acetone washing by soaking 3-5 time.
4. purifying: N-alkylation or N-arylation chitosan quaternary ammonium salt are removed inorganic salt and micromolecular compound with aquae destillata semi-permeable membranes dialysis purifying.N-alkylation or N-arylation chitosan quaternary ammonium salt after 40-60 ℃ of vacuum-drying 20-48 hour, obtain various N-alkylations or arylation chitosan quaternary ammonium salt.
Various N-alkylations or N-arylation chitosan quaternary ammonium salt be through infrared spectra, nuclear magnetic resonance spectrum, hydrocarbon analysis conclusive evidence.Substitution value calculates through carbon/nitrogen ratio of product.As shown in the formula:
C
1/N
1·(1-X)+C
2/N
2·X=C
3/N
3·Y%
C
1/ N
1It is carbon/nitrogen ratio that the chitosan raw material calculates.C
2/ N
2Carbon/nitrogen ratio that chitosan quaternary ammonium salt calculates.C
3/ N
3Carbon/the nitrogen of chitosan quaternary ammonium salt ultimate analysis is the substitution value of chitosan quaternary ammonium salt than .X.Y% is an actual measurement deacetylation (75%-95%).
Synthetic method of the present invention is comparatively easy, and cost is low, can synthesize chitosan aliphatics and aromatic series chlorination, bromination, iodate quaternary ammonium salt with this method product.Chitosan quaternary ammonium salt separates from viscous solution easily and purifies.Synthetic chitosan quaternary ammonium salt good water solubility, the substitution value height.
Embodiment
Embodiment 1
N, N-dimethyl-N-alkyl or the preparation of N-aryl chitosan iodate quaternary ammonium salt
Through the chitosan of the various molecular weight of hydrogen peroxide degraded (preparation method sees: Tsuguhei k, Tatsusaki Y., JP 09031104,1997,02-04; The Luoping, He Bobing etc., chemical research and application, 12 (5), 2000; Lu Fengqi, Cao Zongshun etc., Chinese biochemical drug magazine, 18 (4), 1997) be dissolved in 0.2~2% the acetic acid solution, remove impurity, NaOH with 30-50% neutralizes up to precipitation no longer occurring, precipitate 1~2 time with distilled water wash, it is neutral regulating the pH value, again with repeatedly washing precipitation of distilled water, soaked 24~48 hours with acetone, filter,, must make with extra care chitosan in 40~60 ℃ of dryings.Measuring deacetylating degree of chitosan is 75%~98%, and molecular weight is 1.5 ten thousand~21.0 ten thousand (viscosity-average molecular weight).
Get the refining chitosan of 10.5 grams, in acetate (1.0%)~sodium acetate (0.5%) mixing solutions (W/V), form 1.0% chitosan solution (W/V).0.64mol acetaldehyde solution in room temperature, stir down and be added in the above-mentioned chitosan solution, continue to stir 30 minutes, with NaOH (1mol/L) accent pH to 4.5.Add NaBH under in above-mentioned chitosan solution, stirring
4(15%; W/V), continue to stir after 1.5 hours, above-mentioned reacted solution is transferred pH to 9, obtains the chitosan derivatives of N-alkyl or N-arylation.The chitosan derivatives of washing N-alkyl or N-arylation with a large amount of aquae destillatas is to neutral, the chitosan derivatives that extracts N-alkyl or N-arylation with ethanol and ether Soxhlet is after each one day, 55 ℃ of vacuum-dryings 25 hours the chitosan derivatives of N-alkyl or N-arylation.
15 chitosan derivatives that restrain N-alkyl or N-arylation that obtain are dispersed in N-alkyl-2-Pyrrolidone of 630ml, after 12 hours, add NaOH (1.3mol/L) and CH in the room temperature swelling
3I (0.3mol), adding NaI in reactant system again, to make its concentration be 0.2mol/L.At 50 ℃ of following stirring reactions after 12 hours, in reactant system, add acetone, not having precipitation until solution generates, acetone washing by soaking 4 times of N-alkyl that is precipitated out or N-aryl chitosan quaternary ammonium salt, N-alkyl or N-aryl chitosan quaternary ammonium salt are removed inorganic salt and micromolecular compound with the dialysis of aquae destillata semi-permeable membranes.N-alkyl chitosan quaternary ammonium salt after 48 hours, obtains various N 50 ℃ of vacuum-dryings, N-dimethyl-N-alkyl or N-aryl chitosan iodate quaternary ammonium salt.N, N-dimethyl-N-alkyl chitosan iodate quaternary ammonium salt productive rate is 70%-90%.Substitution value is 0.70-0.95.N-aryl chitosan iodate quaternary ammonium salt productive rate is 60%-90%.Substitution value is 0.40-0.85.
Embodiment 2
N, N-diethyl-N-alkyl chitosan chlorination or bromination quaternary ammonium salt and N, N-diethyl-N-aryl chitosan chlorination or the preparation of bromination quaternary ammonium salt.
The preparation process of the chitosan derivatives preparation of N-alkyl or N-arylation is identical with embodiment 1.N, N-diethyl-N-alkyl chitosan chlorination or bromination quaternary ammonium salt and N, N-diethyl-N-aryl chitosan chlorination or bromination quaternary ammonium salt preparation process are: the 15 gram N-alkyl that will obtain or the chitosan derivatives of N-arylation are dispersed in N-alkyl-2-Pyrrolidone of 630ml, after 12 hours, add NaOH (1.3mol/L) and CH in the room temperature swelling
3CH
2Cl or CH
3CH
2I (0.3mol), adding NaI in reactant system again, to make its concentration be 0.2mol/L.At 50 ℃ of following stirring reactions after 15 hours, in reactant system, add acetone, not having precipitation until solution generates, the N that is precipitated out, N-diethyl-N-alkyl chitosan chlorination or bromination quaternary ammonium salt and N, N-diethyl-chitosan chlorination of N-aryl or bromination quaternary ammonium salt, with acetone washing by soaking 4 times, N, N-diethyl-N-alkyl chitosan chlorination or bromination quaternary ammonium salt and N, N-diethyl-chitosan chlorination of N-aryl or bromination quaternary ammonium salt removed inorganic salt and micromolecular compound with the dialysis of aquae destillata semi-permeable membranes.N, N-diethyl-N-alkyl chitosan chlorination or bromination quaternary ammonium salt and N, N-diethyl-chitosan chlorination of N-aryl or bromination quaternary ammonium salt, 50 ℃ of vacuum-dryings after 48 hours, obtain various N, N-diethyl-N-alkyl chitosan chlorination or bromination quaternary ammonium salt and N, N-diethyl-chitosan chlorination of N-aryl or bromination quaternary ammonium salt.N, N-diethyl-N-alkyl chitosan chlorination or bromination quaternary ammonium salt productive rate are 50%-90%.Substitution value is 0.60-0.95.N, N-diethyl-N-aryl chitosan chlorination or bromination quaternary ammonium productive rate are 40%-90%.Substitution value is 0.40-0.90.
Claims (6)
1, a kind of preparation method of chitosan quaternary ammonium salt, chemical equation is as follows:
X=Cl, Br, I R
1=alkyl or aryl R
2=methyl, ethyl
Described R
1Be alkyl or aryl, R
2Be methyl, ethyl, the halide anion that forms chitosan quaternary ammonium salt is chlorine, bromine, iodine, it is characterized in that: deacetylating degree of chitosan is 75%~98%, viscosity-average molecular weight is 1.5 ten thousand~21.0 ten thousand, raw materials of chitosan obtains various N-alkylation of the present invention or N-arylation chitosan quaternary ammonium salt through refining, dissolving, condensating reductive, replacement, separation, purifying preparation process.
2, the preparation method of chitosan quaternary ammonium salt according to claim 1, the process for purification that it is characterized in that described raw materials of chitosan is: raw materials of chitosan is dissolved in 0.2~2% the acetic acid solution, remove impurity, with the NaOH neutralization of 30-50%, with the distilled water wash precipitation, it is neutral regulating the pH value, soaked 24~48 hours with acetone, filter,, must make with extra care chitosan in 40~60 ℃ of dryings.
3, the preparation method of chitosan quaternary ammonium salt according to claim 1 and 2 is characterized in that described chitosan dissolving method is:, will make with extra care the chitosan concentration of ordinary dissolution is in acetate-sodium acetate mixing solutions of 0.5%-2.5% (W/V).
4, according to the preparation method of claim 1 or 3 described chitosan quaternary ammonium salts, it is characterized in that described chitosan condensation, method of reducing are: in concentration is in acetate-sodium acetate mixing solutions of 0.5%-2.5% (W/V), and adding people's concentration is 10%-15% (W/V) NaBH
4Reductive agent, the recovery time is 2-4 hour, the chitosan derivatives of N-alkylation or N-arylation.
5, preparation method according to claim 1 or 4 described chitosan quaternary ammonium salts, it is characterized in that described chitosan replaces, separation method is: will reduce the N-alkylation that obtains or the chitosan derivatives of N-arylation, wash neutrality with aquae destillata, soak or the Soxhlet extraction with ethanol and ether successively, got the chitosan derivatives of N-alkylation or arylation at 40-60 ℃ of vacuum-drying 20-48 hour, the N-alkylation of acquisition or the chitosan derivatives of arylation are dispersed in the N-alkyl-2-Pyrrolidone solvent of 25-40 times (W/W), in the room temperature swelling after 12-20 hour, adding NaOH and concentration is the NaI catalyzer of 0.1-0.4mol/L, after 40 ℃ of-60 ℃ of following stirring reaction 10-20 hours, in reactant, add acetone, not having precipitation until solution generates, N-alkylation that is precipitated out or N-arylation chitosan quaternary ammonium salt are used the acetone washing by soaking.
6, according to the preparation method of claim 1 and 5 described chitosan quaternary ammonium salts, it is characterized in that described chitosan quaternary ammonium salt purification process is: with N-alkylation or the N-arylation chitosan quaternary ammonium salt that is precipitated out, remove inorganic salt and micromolecular compound with the dialysis of aquae destillata semi-permeable membranes, after 40-60 ℃ of vacuum-drying 20-48 hour, obtain various N-alkylations or arylation chitosan quaternary ammonium salt.
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