CN110330577A - A kind of quaternary ammonium type modification of chitosan and its to rabbit hair fabric method for sorting - Google Patents
A kind of quaternary ammonium type modification of chitosan and its to rabbit hair fabric method for sorting Download PDFInfo
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- CN110330577A CN110330577A CN201910593199.6A CN201910593199A CN110330577A CN 110330577 A CN110330577 A CN 110330577A CN 201910593199 A CN201910593199 A CN 201910593199A CN 110330577 A CN110330577 A CN 110330577A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
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- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/10—Animal fibres
- D06M2101/12—Keratin fibres or silk
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Abstract
The present invention discloses a kind of novel quaternary ammonium type modification of chitosan and preparation method thereof, and the material quality of the modification of chitosan forms number are as follows: 2 parts of chitin；98 parts of triethylamine；80 parts of epoxychloropropane；55 parts of dehydrated alcohol；15 parts of sodium hydroxide；(36.5%) 36 part of concentrated hydrochloric acid；80 parts of carbon tetrachloride；120 parts of distilled water.The preparation method uses following processing step: (1) synthesis of etherifying agent；(2) 2g chitin, 30ml distilled water, 0.12gNaOH the preparation of modified chitin: are put into three-necked flask, being stirred continuously at 45 DEG C of bath temperature makes pH=13, it is slowly added dropwise after 3.2g etherifying agent is dissolved in 10ml distilled water, pH=8 is adjusted with hydrochloric acid solution after reaction 4h, product is poured into beaker and is cooled to room temperature, absolute ethyl alcohol and stirring is added, it stands, it is filtered after product precipitates completely, it is washed with 50% ethanol solution, centrifugation, is repeated 3 times, is subsequently placed in and is dried to obtain Solid Modified chitin in 50 DEG C of vacuum ovens；(3) preparation of quaternary ammonium type modification of chitosan.
Description
Technical field
The present invention relates to the chitin modified technology of weaving antibacterial, specially a kind of quaternary ammonium type modification of chitosan and its right
Rabbit hair fabric method for sorting.
Background technique
With the improvement of people's quality of the life, function textile is gradually pursued and is liked by everybody.Wool fabric due to
The features such as comfortable warming, fine and smooth novel and it is well received.For the rabbit hair as precious protein fiber, application is very extensive, but
Easily cause the growth and breeding of bacterium, mould under appropriate conditions, and wool fabric is mostly used for high-grade textile product,
Thus improving woolen anti-microbial property is very necessary (referring to Liu Di, development and application research [D] of rabbit hair finishing agent
Tianjin Polytechnic University, 2018.).
Chitin/chitosan is a kind of natural biological polysaccharide polymer material of value that is widely used, most of more
Sugar is all neutral under acidic environment or with negative electrical charge, and chitosan is allowed to the property of positive charge compared to other
Polysaccharide has more particularity, due to the excellent performances such as possessed biological functional group's property and compatibility, safety, microbial degradation,
It has been widely used in the fields such as medicine, agricultural, food, papermaking, printing and dyeing and daily use chemicals at present.Although the dissolubility phase of chitosan
It is improved compared with chitin, but chitosan is still difficult to be dissolved in water, ethyl alcohol or common organic solvent, makes
Chitosan is obtained to be not fully utilized in the anti-microbial property to rabbit fur fibre improves.Fortunately, active amino, hydroxyl
Upper diversified functional side group can be connected in the presence of chitosan is made under certain condition, chitosan derivatives obtained are not only
Physicochemical characteristic is improved, and according to the difference of connection side group, also has different functionality, therefore be to the modification of chitosan
Very necessary.(referring to solution ice, the preparation of chitosan derivatives and its composite material and anti-microbial property study Beijing University in [D]
It learns, 2018.).
Goal of the invention
In view of the deficiencies of the prior art, the technical issues of present invention intends to solve is: providing a kind of quaternary ammonium type modification of chitosan
And preparation method thereof.The modification of chitosan has many advantages, such as to may be dissolved under mild acid conditions, anti-microbial property is strong,.The modification shell is poly-
The preparation method of sugar has easy to operate, and grafting rate, grafting efficiency are high, and process is easy to control, the high feature of repeatability.
Summary of the invention
The technical solution that the present invention solves the chitosan technical problem is to design a kind of quaternary ammonium type modification of chitosan,
It is characterized in that the material quality group component number of the modification of chitosan, 2 parts of chitin；98.15 parts of triethylamine；Epoxychloropropane
80.78 parts；54.60 parts of dehydrated alcohol；15.12 parts of sodium hydroxide；(36.5%) 35.7 part of concentrated hydrochloric acid；Carbon tetrachloride 79.75
Part；120 parts of distilled water.
The technical solution that the present invention solves the method for preparing chitosan technical problem is to design a kind of quaternary ammonium type modification
The preparation method of chitosan, the preparation method use quaternary ammonium type modification of chitosan of the present invention material quality form and with
Lower processing step:
(1) 30ml the synthesis of etherifying agent: is added in the three-necked flask equipped with electric stirring, dropping funel and thermometer
Concentrated hydrochloric acid (36.5%) weighs the triethylamine of 135ml in dropping funel, is slowly added dropwise.Flask is placed in 30 DEG C of water-baths, to anti-
Ph=8 should be adjusted after the completion, and bath temperature is set as 35 DEG C, 68.5ml epichlorohydrin reaction 4h is slowly added dropwise, and obtains colourless viscous
Thick liquid.Twice with 50ml carbon tetrachloride extraction, 20ml distilled water is added to rotate to obtain viscous liquid.
(2) preparation of modified chitin: being put into 2g chitin, 30ml distilled water, 0.12gNaOH in three-necked flask, and
It is stirred continuously, makes pH=13, bath temperature controls at 45 DEG C, 3.2gCHPTAC- ethyl is dissolved in after 10ml distilled water and is slowly dripped
Add, react 4h, adjust pH=8 with 25% hydrochloric acid solution after reaction, the product in three-necked flask is poured into cooling in beaker
To room temperature, the dehydrated alcohol of 40ml is added into beaker and is stirred continuously, staticly settles.It is taken out after product precipitates completely
Filter, is washed with 20m150% ethanol solution, and 10min is centrifuged under 8000rpm, is washed repeatedly 3 times, is subsequently placed in 50 DEG C very
It is dried to obtain white solid modified chitin in empty drying box.
(3) preparation of quaternary ammonium type modification of chitosan: taking 15ml distilled water to pour into three-necked flask, and 7.5g solid hydrogen is added
Sodium oxide molybdena and 1g modified chitin, 140 DEG C of oil bath heating, magnetic agitation seal, reflux, stop adding after deacetylation 8h
Heat and stirring, filter.Be repeated more than once step, be finally washed to neutrality, be placed in 50 DEG C of vacuum ovens be dried to obtain compared with
High deacetylized chitosan.
Invention effect
The structural characterization and minimum inhibitory concentration of quaternary ammonium type modification of chitosan of the present invention are analyzed referring to Fig. 1, Fig. 2.
(1) infrared spectrum analysis
Fig. 1 is chitin, Fourier transform infrared spectroscopy (FTIR) spectrum of modified chitin and modification of chitosan.?
Fig. 1 (a), in 1060cm-1Neighbouring absorption peak corresponds to the C-O stretching vibration of the primary alconol in chitin, changes to correspond to
1030-1One absorption peak (Fig. 1 (b)) of neighbouring dialkyl ether, this shows the hydroxyl in chitin through alkalization and glycidyl
Triethyl ammonium chloride nucleophilic addition forms ehter bond.1560cm in Fig. 1 (b)-1And 1630cm-1Two peaks at place correspond to modified first
Peak in shell element secondary amide at NH in-plane bending vibration 1670cm-1 corresponds to the stretching vibration of secondary amide carbonyl, becomes changing
Property chitosan in primary amine, correspond to Fig. 1 (c) in 1590cm-1And 1650cm-1Two peaks at place.This shows modified chitin
In secondary amide become primary amine after alkali heating is deacetylated, i.e., finally synthesized quaternary ammonium cation modification of chitosan.
(2) measurement of quaternary ammonium type modification of chitosan minimum inhibitory concentration
Using minimum bacteriostatic method (agar dilution), this experiment is experimental material with Escherichia coli 8099 for experiment.
It weighs 0.2g modification of chitosan to be dissolved in the sterilizing acetum that 40ml volume fraction is 0.5%, simultaneously will
The sterilizing acetum of volume fraction 0.5% is as a control group.By 18mL culture medium and 2mL sample solution (concentration 5g/L)
It is added in plate simultaneously, front and back even action rocks plate immediately, so that sample liquid and culture medium are abundant before culture medium solidification
It is uniformly mixed, No. 1 plate is made, concentration 0.5g/L is similar
18.4mL culture medium+1.6mL sample liquid is mixed to prepare No. 2 plates, concentration 0.4g/L；
18.8mL culture medium+1.2mL sample liquid is mixed to prepare No. 3 plates, concentration 0.3g/L；
19.2mL culture medium+0.8mL sample liquid is mixed to prepare No. 4 plates, concentration 0.2g/L；
19.4mL culture medium+0.6mL sample liquid is mixed to prepare No. 5 plates, concentration 0.15g/L；
19.6mL culture medium+0.4mL sample liquid is mixed to prepare No. 6 plates, concentration 0.1g/L；
19.8mL culture medium+0.2mL sample liquid is mixed to prepare No. 7 plates, concentration 0.05g/L；
20mL culture medium is poured into plate, No. 0 plate of control group, concentration 0g/L is made.
Take 1-2ml Escherichia coli bacteria suspension (bacterium amount is about 106cfu/ml) drop in plate after solidification.
Inoculated plate is put into incubator, is inverted culture 24 hours.Observe the growing state of bacterium.Complete inhibition
The test solution concentration of bacterium colony growth is minimum inhibitory concentration (MIC) of this sample to subject bacterium.
Fig. 2 is anti-microbial property of the various concentration modification of chitosan to Escherichia coli.Ordinate be under each concentration clump count with
The percent value of Standard Plate number.Ratio is greater than 100, indicates that the concentration promotes the growth and breeding of bacterium, ratio is less than 100, table
Show that the concentration inhibits the growth and breeding of bacterium, ratio, which is 0, indicates bacterial death.By Fig. 2 this it appears that modification of chitosan
To the result of the promotion of Escherichia coli, inhibition and bacterial death.
The modification of chitosan is to the growth of Escherichia coli without apparent facilitation.When concentration is greater than 0.2g/L
Escherichia coli can be killed；And when concentration is between 0.05-0.15g/L, percentage dramatic decrease, it may be said that it is bright its
Anti-microbial property significantly increases.
Compared with prior art, in terms of innovative point of the invention mainly has following two:
(1) a kind of quaternary ammonium type chitosan derivatives are developed, it is chloro- as Material synthesis 3- using triethylamine and epoxychloropropane
2- hydroxypropyl triethylammonium chloride.Chitin is reacted with product again and has synthesized quaternary ammonium type modified chitin.Then add with alkali
Thermal method has synthesized quaternary ammonium type modification of chitosan for modified chitin is deacetylated, makes chitosan on the basis of retaining itself amino
The antibacterial group of quaternary amine type is introduced, the molecular structure of chitosan antimicrobial agent is optimized to the full extent, improves suppression
Bacterium property and water solubility.This structure has no report, is a kind of new type natural macromolecule bacteriostatic agent.This is first of the invention
Innovative point.
(2) develop it is a kind of for rabbit hair fabric antibacterial finish method, by 2g quaternary ammonium type modification of chitosan, 3g citric acid,
3g sodium hypophosphite is dissolved in 200mL distilled water, and 3g fabric is added, takes out after 50 DEG C of immersion 15min, extrudes surplus liquid,
Hydraulic fluid rate is controlled 70%, is repeated twice.In 80 DEG C of preliminary drying 5min, 120 DEG C bake 2min, cold water again after 50 DEG C of washings
Washing, dries at 50 DEG C, obtains the fabric through antibiotic finish.This is second innovative point of the invention.
(3) a kind of long-acting bacteriostatic method for sorting for rabbit hair fabric is developed, the fabric after antibiotic finish is by whole
Still there is good anti-microbial property after washing and the washing of antibacterial tests sample (being equivalent to 5 washings) step after reason.Due to
Using the new type natural macromolecule bacteriostatic agent, fabric is not only washable but also safe and environment-friendly, compatible to human body for textile finishing
Property it is high.This is third innovative point of the invention.
Detailed description of the invention
Fig. 1 is chitin, Fourier transform infrared spectroscopy (FTIR) spectrum of modified chitin and modification of chitosan.Its
In, a- chitin；B- modified chitin；C- quaternary ammonium type modification of chitosan；
Fig. 2 is anti-microbial property of the various concentration modification of chitosan to Escherichia coli；
Fig. 3 is blank group (a), chitin (b), modified chitin (c) and suppression of the modification of chitosan (d) to Escherichia coli
Bacterium
The rabbit hair that Fig. 4 is blank group (a, A), untrimmed rabbit hair fabric (b, B), citric acid are arranged as finishing agent
Fabric (c, C)) and the rabbit hair fabric (d, D) that is arranged as finishing agent of butane tetracarboxylic acid to Escherichia coli it is antibacterial (wherein a, b,
C, d test fluid dilutes 10 times；A, B, C, D test fluid dilution 102Times)
Specific embodiment:
The present invention is further discussed below below with reference to example and attached drawing.
The quaternary ammonium type modification of chitosan that the present invention designs (referring to Fig. 1-4), it is characterised in that the raw material of the modification of chitosan
Quality group component number are as follows: 2 parts of chitin；98.15 parts of triethylamine；80.78 parts of epoxychloropropane；54.6 parts of dehydrated alcohol；Hydrogen-oxygen
Change 15.12 parts of sodium；(36.5%) 35.7 part of concentrated hydrochloric acid；79.75 parts of carbon tetrachloride；120 parts of distilled water.
The present invention devises the preparation method (hereinafter referred to as preparation method) of quaternary ammonium type modification of chitosan, the preparation simultaneously
Method is using the material quality composition of quaternary ammonium type modification of chitosan of the present invention and following processing step:
(1) 30ml the synthesis of etherifying agent: is added in the three-necked flask equipped with electric stirring, dropping funel and thermometer
Concentrated hydrochloric acid (36.5%) weighs the triethylamine of 135ml in dropping funel, is slowly added dropwise.Flask is placed in 30 DEG C of water-baths, to anti-
Ph=8 should be adjusted after the completion, and bath temperature is set as 35 DEG C, 68.5ml epichlorohydrin reaction 4h is slowly added dropwise, and obtains colourless viscous
Thick liquid.Twice with 50ml carbon tetrachloride extraction, 20ml distilled water is added to rotate to obtain viscous liquid.
(2) preparation of modified chitin: being put into 2g chitin, 30ml distilled water, 0.12gNaOH in three-necked flask, and
It is stirred continuously, makes pH=13, bath temperature controls at 45 DEG C, 3.2gCHPTAC- ethyl is dissolved in after 10ml distilled water and is slowly dripped
Add, react 4h, adjust pH=8 with 25% hydrochloric acid solution after reaction, the product in three-necked flask is poured into cooling in beaker
To room temperature, the dehydrated alcohol of 40ml is added into beaker and is stirred continuously, staticly settles.It is taken out after product precipitates completely
Filter, is washed with 20ml50% ethanol solution, and 10min is centrifuged under 8000rpm, is washed repeatedly 3 times, is subsequently placed in 50 DEG C very
It is dried to obtain white solid modified chitin in empty drying box.
(3) preparation of quaternary ammonium type modification of chitosan: taking 15ml distilled water to pour into three-necked flask, and 7.5g solid hydrogen is added
Sodium oxide molybdena and 1g modified chitin, 140 DEG C of oil bath heating, magnetic agitation seal, reflux, stop adding after deacetylation 8h
Heat and stirring, filter.Be repeated more than once step, be finally washed to neutrality, be placed in 50 DEG C of vacuum ovens be dried to obtain compared with
High deacetylized chitosan.
Quaternary ammonium type modification of chitosan preparation method experimental instrument and equipment of the present invention includes: that DF-101S type heat collecting type constant temperature adds
Pyromagnetic force blender, RE-2000B rotary evaporator, DHG electric heating constant-temperature blowing drying box, TGL-16M high speed freezing centrifuge,
SHI-D (111) multiplex vavuum pump of circulating water type, EL204 electronic balance.Instrument and equipment used in preparation method of the present invention is normal
Instrument and equipment is advised, at low cost, easy to operate, technology maturation is suitable for industrial application.
Specific embodiments of the present invention are given below.Specific embodiment is merely to present invention be described in more detail, no
Limit claim of the invention.
Example 1
30ml concentrated hydrochloric acid (36.5%) is added in the three-necked flask equipped with electric stirring, dropping funel and thermometer, claims
It takes the triethylamine of 135ml in dropping funel, is slowly added dropwise.Flask is placed in 30 DEG C of water-baths, to adjust ph=8 after the reaction was completed,
Bath temperature is set as 35 DEG C, and 68.5ml epichlorohydrin reaction 4h is slowly added dropwise, and obtains colorless viscous shape liquid.With 50ml tetra-
Chlorination carbon is extracted twice, and 20ml distilled water is added to rotate to obtain viscous liquid.
It is put into 2g chitin, 30ml distilled water, 0.12gNaOH in three-necked flask, and is stirred continuously, makes pH=13, water
Bath temperature is controlled at 45 DEG C, is slowly added dropwise after 3.2g etherifying agent is dissolved in 10ml distilled water, is reacted 4h, is used after reaction
25% hydrochloric acid solution adjusts pH=8, and the product in three-necked flask is poured into beaker and is cooled to room temperature, is added into beaker
The dehydrated alcohol of 40ml is simultaneously stirred continuously, and is staticly settled.It is filtered after product precipitates completely, it is molten with 20ml50% ethyl alcohol
Liquid is washed, and 10min is centrifuged under 8000rpm, is washed repeatedly 3 times, is subsequently placed in 50 DEG C of vacuum ovens and is dried
To white solid modified chitin.
It takes 15ml distilled water to pour into three-necked flask, 7.5g solid sodium hydroxide and 1g modified chitin, oil bath is added
140 DEG C of heating, magnetic agitation seal, reflux, stop heating and stirring after deacetylation 8h, filter.Be repeated once with
Upper step, is finally washed to neutrality, is placed in 50 DEG C of vacuum ovens and is dried to obtain more high deacetylized chitosan.
0.2g quaternary ammonium type modification of chitosan is weighed to be dissolved in the sterilizing acetum that 40ml volume fraction is 0.5%,
As a control group by the sterilizing acetum of volume fraction 0.5% simultaneously.19.2mL culture medium and 0.8mL sample solution is (dense
Degree is 0.2g/L) it is added in plate simultaneously, front and back even action rocks plate immediately, so that sample liquid and culture medium are being cultivated
It is sufficiently mixed before base solidification uniformly, plate, concentration 0.2g/L is made.1-2ml Escherichia coli bacteria suspension (bacterium amount is taken after solidification
About 106Cfu/ml) drop is in plate.Inoculated plate is put into incubator, is inverted culture 24 hours.Observe bacterium
Growing state.As a result referring to Fig. 3 (d).
Comparison 1
30ml concentrated hydrochloric acid (36.5%) is added in the three-necked flask equipped with electric stirring, dropping funel and thermometer, claims
It takes the triethylamine of 135ml in dropping funel, is slowly added dropwise.Flask is placed in 30 DEG C of water-baths, to adjust ph=8 after the reaction was completed,
Bath temperature is set as 35 DEG C, and 68.5ml epichlorohydrin reaction 4h is slowly added dropwise, and obtains colorless viscous shape liquid.With 50ml tetra-
Chlorination carbon is extracted twice, and 20ml distilled water is added to rotate to obtain viscous liquid.
It is put into 2g chitin, 30ml distilled water, 0.12gNaOH in three-necked flask, and is stirred continuously, makes pH=13, water
Bath temperature is controlled at 45 DEG C, is slowly added dropwise after 3.2g etherifying agent is dissolved in 10ml distilled water, is reacted 4h, is used after reaction
25% hydrochloric acid solution adjusts pH=8, and the product in three-necked flask is poured into beaker and is cooled to room temperature, is added into beaker
The dehydrated alcohol of 40ml is simultaneously stirred continuously, and is staticly settled.It is filtered after product precipitates completely, it is molten with 20ml50% ethyl alcohol
Liquid is washed, and 10min is centrifuged under 8000rpm, is washed repeatedly 3 times, is subsequently placed in 50 DEG C of vacuum ovens and is dried
To white solid modified chitin.
It weighs 0.2g modified chitin to be dissolved in the sterilizing acetum that 40ml volume fraction is 0.5%, simultaneously will
The sterilizing acetum of volume fraction 0.5% is as a control group.By 19.2mL culture medium and 0.8mL sample solution, (concentration is
It 0.2g/L) is added in plate simultaneously, front and back even action rocks plate immediately, so that sample liquid and culture medium are solidifying in culture medium
It is sufficiently mixed before Gu uniformly, plate, concentration 0.2g/L is made.1-2ml Escherichia coli bacteria suspension is taken after solidification, and (bacterium amount is about
106cfu/ml) drop is in plate.Inoculated plate is put into incubator, is inverted culture 24 hours.Observe the growth of bacterium
Situation.As a result referring to Fig. 3 (c).
Comparative example 2
It weighs 0.2g chitin to be dissolved in the sterilizing acetum that 40ml volume fraction is 0.5%, while by volume
The sterilizing acetum of score 0.5% is as a control group.By 19.2mL culture medium and 0.8mL sample solution (concentration 0.2g/
L it) is added in plate simultaneously, front and back even action rocks plate immediately, so that sample liquid and culture medium are filled before culture medium solidification
Divide and be uniformly mixed, plate, concentration 0.2g/L is made.1-2ml Escherichia coli bacteria suspension is taken after solidification, and (bacterium amount is about 106cfu/
Ml) drop is in plate.Inoculated plate is put into incubator, is inverted culture 24 hours.Observe the growing state of bacterium.Knot
Fruit is referring to Fig. 3 (b).
When can be seen that sample concentration 0.2g/L according to the growing state of Escherichia coli in Fig. 3, chitin is to large intestine bar
The growth unrestraint of bacterium acts on, and etherified dose of modified chitin has certain inhibiting effect to the growth of Escherichia coli, and
Quaternary ammonium type modification of chitosan can achieve the effect that complete inhibition to Escherichia coli.So quaternary ammonium type modification of chitosan tool of the present invention
There is good bacteriostasis property.
Embodiment 2
By 2g quaternary ammonium type modification of chitosan, 3g citric acid, 3g sodium hypophosphite is dissolved in 200mL distilled water, and 3g is added and knits
Object takes out after 50 DEG C of immersion 15min, extrudes surplus liquid, and hydraulic fluid rate controls 70%, repeats twice.It is pre- in 80 DEG C
5min is dried, 120 DEG C bake 2min, and cold water washs again after 50 DEG C of washings, dries at 50 DEG C, obtains the fabric through antibiotic finish.
The antibacterial activity of rabbit hair fabric using succusion to modification of chitosan before and after the processing has carried out quantitative assessment.This
Method aims at the specimen design of non-releasing micro antibacterials processing under the conditions of dynamic Contact, has selected large intestine common in human body
Bacillus is as test organisms.One typical step is: 0.75g sample cloth being cut into the small pieces of about 0.5cm × 0.5cm, is put into dress
In the flask for having 70mL0.5mM potassium dihydrogen phosphate (PBS) culture solution, cell concentration is 1.0-1.5 × 104/mL.Then it will burn
Bottle shakes 1h on 37 DEG C of rotor-vibrating screens with the revolving speed of 250rpm.Front and back is shaken up, 1mL test fluid is taken, is applied to agar after dilution
On plate.It is incubated for for 24 hours for 37 DEG C afterwards, the clump count formed on Count Agar plate calculates living bacterial cells number before and after shaking flask.According to
It repeats test result and determines antibacterial effect.As a result referring to fig. 4.Bacterium bacteriostasis rate is calculated as follows:
R is bacterium bacteriostasis rate in formula, and B, A are living bacterial cells number before and after shaking flask.
Comparative example 3
By 2g quaternary ammonium type modification of chitosan, 3g butane tetracarboxylic acid, 3g sodium hypophosphite is dissolved in 200mL distilled water, is added
3g fabric takes out after 50 DEG C of immersion 15min, extrudes surplus liquid, and hydraulic fluid rate controls 70%, repeats twice.In 80
DEG C preliminary drying 5min, 120 DEG C bake 2min, and cold water washs again after 50 DEG C of washings, dries, is obtained through antibiotic finish at 50 DEG C
Fabric.
The antibacterial activity of rabbit hair fabric using succusion to modification of chitosan before and after the processing has carried out quantitative assessment.This
Method aims at the specimen design of non-releasing micro antibacterials processing under the conditions of dynamic Contact, has selected large intestine common in human body
Bacillus is as test organisms.One typical step is: 0.75g sample cloth being cut into the small pieces of about 0.5cm × 0.5cm, is put into dress
In the flask for having 70mL0.5mM potassium dihydrogen phosphate (PBS) culture solution, cell concentration is 1.0-1.5 × 104/mL.Then it will burn
Bottle shakes 1h on 37 DEG C of rotor-vibrating screens with the revolving speed of 250rpm.Front and back is shaken up, 1mL test fluid is taken, is applied to agar after dilution
On plate.It is incubated for for 24 hours for 37 DEG C afterwards, the clump count formed on Count Agar plate calculates living bacterial cells number before and after shaking flask.According to
It repeats test result and determines antibacterial effect.As a result referring to fig. 4.Bacterium bacteriostasis rate is calculated as follows:
R is bacterium bacteriostasis rate in formula, and B, A are living bacterial cells number before and after shaking flask.
According to the growing state of Escherichia coli in Fig. 4, the clump count of c, C are respectively 18,6 in figure, the clump count point of d, D
Not Wei 48,9, it can thus be seen that finishing agent using Citric Acid Finishing rabbit hair fabric antibacterial effect more preferably, it is contemplated that antibacterial finish
Therefore finishing agent selects citric acid for effect, economic benefit and industrialization etc.；By repeatedly washing, finishing agent is respectively adopted
The rabbit hair fabric that citric acid and butane tetracarboxylic acid arrange, is computed bacteriostasis rate and reaches 99.9% or more, this shows the quaternary ammonium type
Modification of chitosan is a kind of long-acting excellent woolen antibacterial finishing agent, and good answer will be had in woolen antibiotic finish
Use prospect.
Claims (4)
1. a kind of quaternary ammonium type modification of chitosan, it is characterised in that the material quality of the modification of chitosan forms number are as follows: chitin
2-3 parts；97-99 parts of triethylamine；80-82 parts of epoxychloropropane；54-56 parts of dehydrated alcohol；15-17 parts of sodium hydroxide；Concentrated hydrochloric acid
(36.5%) 35-37 parts；79-81 parts of carbon tetrachloride；120 parts of distilled water.
2. quaternary ammonium type modification of chitosan according to claim 1, it is characterised in that the material quality of the modification of chitosan forms
Number are as follows: 2-3 parts of chitin；97-99 parts of triethylamine；80-82 parts of epoxychloropropane；54-56 parts of dehydrated alcohol；Sodium hydroxide
15-17 parts；35-37 parts of concentrated hydrochloric acid (36.5%)；79-81 parts of carbon tetrachloride；120 parts of distilled water.
3. a kind of preparation method of quaternary ammonium type modification of chitosan described in claim 1, which uses claim 1 institute
The material quality for stating quaternary ammonium type modification of chitosan forms and following processing step:
(1) 30ml concentrated hydrochloric acid the synthesis of etherifying agent: is added in the three-necked flask equipped with electric stirring, dropping funel and thermometer
(36.5%), the triethylamine of 135ml is weighed in dropping funel, is slowly added dropwise.Flask is placed in 30 DEG C of water-baths, to after the reaction was completed
Ph=8 is adjusted, bath temperature is set as 35-40 DEG C, 68-70ml epichlorohydrin reaction 4h is slowly added dropwise, obtains colorless viscous shape
Liquid twice with carbon tetrachloride extraction adds distilled water to rotate to obtain viscous liquid；
(2) preparation of modified chitin: 2g chitin, 30ml distilled water, 0.12gNaOH are put into three-necked flask, and constantly
Stirring, makes pH=13, and bath temperature controls at 45-50 DEG C, 3-4gCHPTAC- ethyl is dissolved in after 10ml distilled water and is slowly dripped
Add, react 4-5h, adjusts pH=8 with 25% hydrochloric acid solution after reaction, the product in three-necked flask is poured into cold in beaker
But to room temperature, dehydrated alcohol is added into beaker and is stirred continuously, staticly settles, is filtered after product precipitates completely, used
50% ethanol solution is washed, centrifugation, wash repeatedly 3 times, be subsequently placed in 50 DEG C of vacuum ovens be dried to obtain it is white
The Solid Modified chitin of color；
(3) preparation of quaternary ammonium type modification of chitosan: taking 15ml distilled water to pour into three-necked flask, and 7-8g solid sodium hydroxide is added
With 1g modified chitin, 135-140 DEG C of oil bath heating, magnetic agitation is sealed, reflux, stops heating after deacetylation 8h
And stirring, filter, be repeated more than once step, be finally washed to neutrality, be placed in 50 DEG C of vacuum ovens be dried to obtain it is higher
The chitosan of deacetylation.
4. a kind of method that quaternary ammonium type modification of chitosan arranges rabbit hair fabric, it is characterised in that by 2g quaternary ammonium type modification of chitosan,
3-4g citric acid, 3g sodium hypophosphite are dissolved in 200mL distilled water, and 3-4g fabric is added, takes out after 50 DEG C of immersion 15min,
Surplus liquid is extruded, hydraulic fluid rate is controlled 70%, is repeated twice, and in 80 DEG C of preliminary drying 5min, 120 DEG C bake 2min, and 50 DEG C
Cold water washs again after washing, dries at 50 DEG C, obtains the fabric through antibiotic finish.
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| CN105622780A (en) * | 2016-03-15 | 2016-06-01 | 武汉大学 | Homogeneous phase preparation method for quaternized chitin |
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| CN105622780A (en) * | 2016-03-15 | 2016-06-01 | 武汉大学 | Homogeneous phase preparation method for quaternized chitin |
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| 1WALY, A.I. ET AL: "Preparation of Quaternized Chitosan Nano- Particle and Its Antimicrobial Activity on Polyester, Cotton and Polyester/Cotton Blend Treated Fabrics" * |
| 张伟等: "壳聚糖季铵盐在桑蚕丝织物抗菌整理中的应用" * |
| 张毅等: "一种阳离子型接枝改性壳聚糖的制备及其对毛织物长效抗菌整理的研究" * |
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| CN112194870A (en) * | 2020-10-09 | 2021-01-08 | 骆家宽 | Process for preparing blown film |
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