CN109629026A - A kind of cellulose melt spun fibre and preparation method thereof with durable antibiotic performance - Google Patents
A kind of cellulose melt spun fibre and preparation method thereof with durable antibiotic performance Download PDFInfo
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- CN109629026A CN109629026A CN201811503376.9A CN201811503376A CN109629026A CN 109629026 A CN109629026 A CN 109629026A CN 201811503376 A CN201811503376 A CN 201811503376A CN 109629026 A CN109629026 A CN 109629026A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
- D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
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- Artificial Filaments (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及一种具有持久抗菌性能的纤维素熔纺纤维及其制备方法，所述纤维由接枝胍盐类抗菌剂的酰化纤维素经熔融纺丝制备而得。本发明具有一定的细度、强度及断裂伸长率，可用于纺织产业加工；另外，对革兰氏阴性和阳性细菌均具有优良的抗菌效果，在多次洗涤后仍具有98％左右的抑菌率，具有良好的市场应用前景。
The invention relates to a cellulose melt-spun fiber with durable antibacterial properties and a preparation method thereof. The fiber is prepared by melt spinning of cellulose acylate grafted with a guanidine salt antibacterial agent. The invention has certain fineness, strength and elongation at break, and can be used in textile industry processing; in addition, it has excellent antibacterial effect on both Gram-negative and positive bacteria, and still has about 98% inhibition after repeated washing. Bacteria rate, has a good market application prospects.
Description
Technical field
The invention belongs to cellulose melt spinning field, in particular to a kind of cellulose melt-spun with durable antibiotic performance
Fiber and preparation method thereof.
Background technique
Cellulose is a kind of nature renewable resource extremely abundant, accounts for about the 1.59 × 10 of annual yield of biomass12
Ton, compared with other synthetic fibers such as polyamide, polyester and polyurethane fiber, cellulose itself have good hygroscopicity, resist it is quiet
Electrically strong, good permeability, it is comfortable and easy to wear, be easy to the excellent performances such as textile process, biodegradable, have certain chemical fibres difficult
The characteristics of to compare.The preparation method of industrialization at present is mostly wet spinning, or is done using volatile organic solvent
Method spinning, not only spinning speed is slow for both methods, but also a large amount of reagents for using of preparation process will cause the pollution of environment.
And melt spinning forming pertains only to the cooling of high polymer molten, there was only material geometry and physics shape before and after spinning
Variation in state and change without composition, process flow is short compared with dry-wet spinning, pollution is few, and spinning speed is very fast, is a kind of high
The production method of effect.Meanwhile shrinking small when the fibre forming of melt-spun, the fibre section uniformity is high, and high power drawing can be used in when spinning
It stretches to improve the performance of fiber, therefore the research of cellulose melt spinning was never interrupted since last century.
A large amount of hydroxyl in cellulose macromolecule easily forms intramolecular and intermolecular hydrogen bonding, can decompose under high temperature
Rather than melt, not directly carry out melt spinning production.Also it is made it have just because of the hydroxyl in cellulose good anti-
Activity is answered, intermolecular hydrogen bonding theoretically can be destroyed by chemical modification or graft reaction, reduce intermolecular active force, from
And it is effectively reduced fusing point.
In addition, textile because of its loose porous characteristic, easily becomes numerous bacteriums during daily use and passes
The carrier broadcast.The bacterium bred on textile can not only cause fibre that discoloration, mouldy, brittle degradation etc., Er Qiehui occurs
Abnormal stimulation is generated to human skin and may induce skin disease, largely effects on the health of human body.With science and technology
Progressive and people's living standard improvement, more stringent requirements are proposed for anti-microbial property of the people to textile.Has antibacterial at present
The textile of performance, application field are being gradually expanded, and mainly include medical textile (such as operation suture thread, mask, operation
Gloves etc.), household textiles (such as mattress, carpet, curtain) and fabrics for industrial use (such as filter cloth, automobile interior decoration, national defence work
Industry lining etc.).Therefore, antimicrobial natural plant fiber is prepared, there is very important reality meaning preparing textile material field
Adopted and wide application prospect.
In numerous antibacterial agents, guanidine salt class antibacterial agent is a kind of preferable antibacterial agent of current application, it has good peace
Full property and durability, guanidino group therein have very strong electropositive, easily attract the cell of electronegative bacterium and fungi
Film, so that membranolysis is destroyed, to kill bacterium.Therefore, guanidine salt class antibacterial agent is applied in various fields, such as cures
Medicine, daily necessities etc..
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of cellulose melt spun fibre with durable antibiotic performance and
Preparation method, the fiber have certain fineness, intensity and elongation at break, can be used for textile industry processing；In addition, to leather
Lan Shi feminine gender and positive bacteria all have excellent antibacterial effect, still have 98% or so bacteriostasis rate, tool after 50 washings
There is good market application prospect.
The present invention provides a kind of cellulose melt spun fibres with durable antibiotic performance, and the fiber is by grafted guanidine salt class
The acylated cellulose of antibacterial agent is prepared through melt spinning.
The acylated cellulose is obtained by cellulose graft acyl chlorides reagent；The degree of substitution DS of acylated cellulose is in 2.80-
Between 2.95.
The glass transition temperature of the acylated cellulose is between 90-140 DEG C, and fusing point is between 160-260 DEG C.
The acyl chlorides reagent is 2- phenylbutyryl chloride, benzene valeric chloride, 3- cyclopentylpropionyl chloride, cyclopentylacetyl chloride, ring penta
One or more of base formyl chloride, cyclobutylmethyl acyl chlorides, cyclohexyl chloroacetic chloride, cyclopropyl formyl chloride, chloroacetic chloride.Acyl chlorides reagent makes
The hydroxyl unfolded on the cellulose macromolecule chain of dispersion is sufficiently acylated, to prevent the recombination of hydrogen bond in cellulose derivative, reduces
In cellulosic molecule and intermolecular hydrogen bond action so that cellulose derivative be made to obtain thermoplasticity changes the calorifics of cellulose
Performance realizes the melt spinning of cellulose.
The guanidine salt class antibacterial agent be poly (hexamethylene) hydrochloride PHMG, relative molecular mass 900-1200 it
Between.Material prepared by the present invention belongs to non-stripping property antibacterial, has the characteristics that safe and efficient durable antibiotic, and PHMG is a kind of wide
Spectrality and antibacterial agent resistant to high temperature.
The guanidine salt class antibacterial agent is in the DS on acylated cellulose between 0.05-0.20.
By cyclic acid anhydride or diisocyanate on acylated cellulose macromolecular chain grafted guanidine salt class antibacterial agent.It will be acylated
The degree of substitution DS of cellulose is controlled between 2.80-2.95, on the basis of guaranteeing that cellulose derivative can realize melt-spun, is used
Cyclic acid anhydride or diisocyanate are reacted with the amino on the hydroxyl and PHMG on cellulose respectively, to realize big in cellulose
Antibacterial agent is grafted on strand.
The cyclic acid anhydride is one of phthalic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride or several
Kind；The diisocyanate is toluene di-isocyanate(TDI) TDI, isophorone diisocyanate IPDI, two isocyanide of diphenyl methane
Acid esters MDI, dicyclohexyl methyl hydride diisocyanate HMDI, hexamethylene diisocyanate HDI, lysine diisocyanate LDI
One or more of.
The present invention also provides a kind of preparation methods of cellulose melt spun fibre with durable antibiotic performance, comprising:
(1) cellulose is dissolved in DMAc/LiCl mixed solvent, obtains DMAc/LiCl/ cellulose homogeneous-phase system；Addition is urged
After agent, then acyl chlorides reagent is added dropwise and the mixed solution of DMAc is reacted, reaction product is post-processed, obtains acylated fibre
Dimension element；
(2) acylated cellulose is dissolved in the DMSO that purifying removed water, cyclic acid anhydride is added, and (addition rubs relative to AGU
0.2-0.8 times of cyclic acid anhydride of your number, i.e. n (AGU): n (cyclic acid anhydride)=1:0.2-0.8), and catalyst is added, in 50-
12-24h is reacted at 80 DEG C；Activator activation is added after reaction, adds excessive guanidine salt class antibacterial agent and is reacting at room temperature
6-12h is precipitated after reaction, and is filtered, washed, room temperature in vacuo drying, and the acylated cellobiose of grafted guanidine salt class antibacterial agent is obtained
Element；
Or acylated cellulose is dissolved in the DMSO that purifying removed water, diisocyanate is added, and (addition rubs relative to AGU
0.2-0.8 times of diisocyanate of your number, i.e. n (AGU): n (diisocyanate)=1:0.2-0.8), and catalyst is added,
12-24h is reacted at 40-60 DEG C；Excessive guanidine salt class antibacterial agent is added after reaction, reaction temperature is 60-80 DEG C, reaction
Time is 2-4h；It precipitates, and is filtered, washed, room temperature in vacuo drying after reaction, obtain the acylation of grafted guanidine salt class antibacterial agent
Cellulose；
(3) acylated cellulose of grafted guanidine salt class antibacterial agent is finally subjected to melt spinning, it is rolled lasting up to having
The cellulose melt spun fibre of anti-microbial property.
3.0-6.0 times of molal quantity relative to cellulose repeating unit (AGU) of acyl chlorides reagent in the step (1),
That is n (AGU): n (acyl chlorides)=1:3.0-6.0.
Catalyst (while playing the role of acid binding agent) in the step (1) be pyridine, 4-dimethylaminopyridine DMAP,
One or more of triethylamine TEA and diisopropylethylamine DIEA.
(according to a variety of acyl chlorides reagents, time for adding is controlled within 1h for time for adding control in the step (1)
Within 1h)；Reaction time is 5-15h；Reaction temperature is 25-80 DEG C.
Post-processing in the step (1) specifically: use isopropanol or methanol extraction, reuse dimethyl sulfoxide
(DMSO) lysate is then proceeded to use isopropanol or methanol extraction, and is repeatedly washed using isopropanol and deionized water, to fill
Divide the unreacted reagent of removal and other small molecules, product 60 DEG C of drying in vacuum drying oven.
The catalyst that cyclic acid anhydride addition is added in the step (2) is triethylamine, and additive amount is cyclic acid anhydride molal quantity
1-2 times, i.e. n (cyclic acid anhydride): n (triethylamine)=1:1-2；The catalyst that diisocyanate addition is added is urged for organic tin
Agent, such as stannous octoate or dibutyl tin dilaurate, additive amount is the 0.5-5% of diisocyanate weight fraction.
Activator in the step (2) is n-hydroxysuccinimide (NHS) and 1- (3- dimethylamino-propyl) -3- second
Base carbodiimide hydrochloride (EDC) activates 6-12h under condition of ice bath.Wherein the additive amount of EDC is cyclic acid anhydride molal quantity
1.2-1.5 times, the additive amount of NHS is the EDC of equimolar number, i.e. n (NHS): n (EDC)=1.
Excessive guanidine salt class antibacterial agent in the step (2) is for the minimum inhibitory concentration of antibacterial agent.
Melt spinning in the step (2) specifically: the melt spinning at 170-280 DEG C, be arranged suitable spinneret,
Draw roll and work beam parameter, winding tension is in 0.1-2.5mN/dtex.
Beneficial effect
(1) present invention is modified by natural cellulosic material, and the method for melt spinning is used while obtaining antibiotic property
Cellulose-based fiber is prepared, fineness is between 5.0-15.0dtex, and intensity is between 0.5-5.0cN/dtex, elongation at break
Between 5.0%-15.0%, it can be used for textile industry processing；
(2) present invention is using the hydroxyl on a large amount of substituted celluloses of acyl chlorides reagent, destroys in cellulose molecular chain and molecule
The hydrogen bond of interchain makes cellulose derivative obtain thermoplasticity and realizes the melting of cellulose to change the thermal property of cellulose
Spinning；
(3) safe and non-toxic and inexpensive guanidine salt class antibacterial agent is grafted on the unreacted hydroxyl of thermoplastic cellulose by the present invention
On base, being grafted a small amount of antibacterial agent can reach fungistatic effect；
(4) present invention utilizes a remaining carboxyl end group after the ring-opening reaction of cyclic acid anhydride or the Zhong Yi in diisocyanate
Cyanic acid ester group is reacted with the amino on guanidine salt class antibacterial agent, and successfully guanidine salt class antibacterial agent is grafted on cellulose molecular chain, system
For non-stripping property anti-bacterial fibre.According to GB_T 20944.3-2008, antibiotic property is carried out to prepared fiber using concussion method
Test, the fiber prepared as the result is shown all have excellent antibacterial effect to Gram-negative and positive bacteria, are repeatedly washing
Still there is 98% or so bacteriostasis rate afterwards.
Detailed description of the invention
Fig. 1 is the schematic diagram that the present invention prepares acylation modification cellulose；
Fig. 2 is the composition principle figure of PHMG used in the present invention；
Fig. 3 is the schematic diagram that the present invention is grafted PHMG using cyclic acid anhydride；
Fig. 4 is the schematic diagram that the present invention is grafted PHMG using IPDI；
Fig. 5 is the acylated cellulose of the grafting PHMG prepared in the embodiment of the present invention 5 to golden staphylococci (A) and large intestine bar
The antibacterial effect figure of bacterium (B).
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
(1) cellulosic material that the degree of polymerization is 600-800 is placed in vacuum drying oven, uses phosphorus pentoxide (P2O5) dry
6h.Cellulose 1g (AGU, 6.17mmol, 1eq.) after weighing drying is placed in three-necked flask, adds 40mL DMAc
The mixed solution of (0.43mol, 69.69eq.) and 2.4g LiCl (56.6mmol, 9.17eq.), setting heating temperature are 140
DEG C, cool down after heating 2h, continues to stir after being cooled to room temperature up to dissolving, it is completely black using visual field when polarized light microscope observing, and
Course of dissolution is continually fed into nitrogen.DMAc/LiCl/ cellulose homogeneous-phase system is obtained after dissolution cellulose, 2.2g pyridine is added
8mL DMAc and 5.078g is added dropwise using constant pressure funnel after magnetic agitation 5min in (2.24mL, 27.8mmol, 4.5eq.)
The mixed solution of 2- phenylbutyryl chloride (27.8mmol, 4.5eq.), time for adding control in 1h, continue to be added dropwise after being added dropwise to complete
The mixed solution of 5mL DMAc and 0.485g chloroacetic chloride (0.44mL, 6.17mmol, 1eq.), time for adding control is in 30min, originally
Process leads to nitrogen, and reaction temperature is 40 DEG C, continues magnetic agitation after being added dropwise to complete and reacts 5h.After reaction under fast stirring
It with being filtered after isopropanol precipitating, reuses and continues after DMSO lysate with isopropanol precipitating, filtering, when filtering uses isopropanol
It is repeatedly washed with deionized water, sufficiently removes unreacted reagent and other small molecules, the product of filtering is 60 in vacuum drying oven
DEG C dry 10h, obtains acylated cellulose.
(2) acylated cellulose is dissolved in the DMSO that 30mL purifying removed water, 0.457g phthalic anhydride is added
(3.08mmol, 0.5eq.), and 0.374g triethylamine (0.514mL, 3.70mmol, 0.6eq.) is added, it is reacted at 60 DEG C
18h；0.4g NHS and 0.7g EDC activated carboxyl 12h under condition of ice bath are added, 0.5g PHMG is added and is reacting at room temperature
12h.Isopropanol precipitating is used after reaction, is filtered, washed rear room temperature vacuum drying for 24 hours, obtains the acylated fine of grafting PHMG
Dimension element.
(3) fusing point of the acylated cellulose of test grafting PHMG is 200 DEG C, and decomposition starting temperature is 280 DEG C, melting viscosity
For 100Pasec.Spinning is carried out to product using the melt spinning machine of Japanese ABE company, spinning temperature is set as 220 DEG C, spinning
Speed is set as 800m/min, is finally collected with the winding tension of 0.15cN/dtex.
Prepared fibre fineness is 8.0-10.0dtex, breaking strength 0.7-1.3cN/dtex, and elongation at break is
9.0-14.0%.
The acylated cellulose fiber of the grafting PHMG of preparation is resisted according to the concussion method in GB_T 20944.3-2008
The test of bacterium property has preferable fungistatic effect, antibacterial band H gold glucose to Escherichia coli and golden glucose coccus as the result is shown
Sugar ball bacterium is up to 13mm；Escherichia coli are up to 9mm.
The survey of antibacterial washability is carried out according to FZ_T 73023-2006 to the acylated cellulose fiber of the grafting PHMG of preparation
Examination, antibacterial rank are AAA grades.
Embodiment 2
(1) cellulosic material that the degree of polymerization is 600-800 is placed in vacuum drying oven, uses phosphorus pentoxide (P2O5) dry
6h.Cellulose 1g (AGU, 6.17mmol, 1eq.) after weighing drying is placed in three-necked flask, adds 40mL DMAc
The mixed solution of (0.43mol, 69.69eq.) and 2.4g LiCl (56.6mmol, 9.17eq.), setting heating temperature are 140
DEG C, cool down after heating 2h, continues to stir after being cooled to room temperature up to dissolving, it is completely black using visual field when polarized light microscope observing, and
Course of dissolution is continually fed into nitrogen.DMAc/LiCl/ cellulose homogeneous-phase system is obtained after dissolution cellulose, 2.2g pyridine is added
8mL DMAc and 5.078g is added dropwise using constant pressure funnel after magnetic agitation 5min in (2.24mL, 27.8mmol, 4.5eq.)
The mixed solution of 2- phenylbutyryl chloride (27.8mmol, 4.5eq.), time for adding control in 1h, continue to be added dropwise after being added dropwise to complete
The mixed solution of 5mL DMAc and 0.485g chloroacetic chloride (0.44mL, 6.17mmol, 1eq.), time for adding control is in 30min, originally
Process leads to nitrogen, and reaction temperature is 40 DEG C, continues magnetic agitation after being added dropwise to complete and reacts 5h.After reaction under fast stirring
It with being filtered after isopropanol precipitating, reuses and continues after DMSO lysate with isopropanol precipitating, filtering, when filtering uses isopropanol
It is repeatedly washed with deionized water, sufficiently removes unreacted reagent and other small molecules, the product of filtering is 60 in vacuum drying oven
DEG C dry 10h, obtains acylated cellulose.
(2) acylated cellulose is dissolved in the DMSO that 30mL purifying removed water, addition 0.685g IPDI (3.08mmol,
0.5eq.), and 6 μ L stannous octoates are added as catalyst, reacts 15h at 50 DEG C；It is anti-at 60 DEG C to add 0.5g PHMG
Answer 4h.Methanol extraction is used after reaction, is filtered, washed rear room temperature vacuum drying for 24 hours, is obtained the acylated cellobiose of grafting PHMG
Element.
(3) fusing point of the acylated cellulose of test grafting PHMG is 220 DEG C, and decomposition starting temperature is 290 DEG C, melting viscosity
For 120Pasec.Spinning is carried out to product using the melt spinning machine of Japanese ABE company, spinning temperature is set as 240 DEG C, spinning
Speed is set as 800m/min, is finally collected with the winding tension of 0.15cN/dtex.
Prepared fibre fineness is 9.0-13.0dtex, breaking strength 0.6-1.5cN/dtex, and elongation at break is
10.0-15.0%.
The acylated cellulose fiber of the grafting PHMG of preparation is resisted according to the concussion method in GB_T 20944.3-2008
The test of bacterium property has preferable fungistatic effect, antibacterial band H gold glucose to Escherichia coli and golden glucose coccus as the result is shown
Sugar ball bacterium is up to 14mm；Escherichia coli are up to 10mm.
The survey of antibacterial washability is carried out according to FZ_T 73023-2006 to the acylated cellulose fiber of the grafting PHMG of preparation
Examination, antibacterial rank are AAA grades.
Embodiment 3
(1) cellulosic material that the degree of polymerization is 600-800 is placed in vacuum drying oven, uses phosphorus pentoxide (P2O5) dry
6h.Cellulose 1g (AGU, 6.17mmol, 1eq.) after weighing drying is placed in three-necked flask, adds 40mL DMAc
The mixed solution of (0.43mol, 69.69eq.) and 2.4g LiCl (56.6mmol, 9.17eq.), setting heating temperature are 140
DEG C, cool down after heating 2h, continues to stir after being cooled to room temperature up to dissolving, it is completely black using visual field when polarized light microscope observing, and
Course of dissolution is continually fed into nitrogen.DMAc/LiCl/ cellulose homogeneous-phase system is obtained after dissolution cellulose, 2.2g pyridine is added
8mL DMAc and 2.712g ring is added dropwise using constant pressure funnel after magnetic agitation 5min in (2.24mL, 27.8mmol, 4.5eq.)
The mixed solution of amyl chloroacetic chloride (18.5mmol, 3.0eq.), time for adding are controlled in 1h, continue that 5mL is added dropwise after being added dropwise to complete
The mixed solution of DMAc and 0.485g chloroacetic chloride (0.44mL, 6.17mmol, 1eq.), time for adding are controlled in 30min, this process
Logical nitrogen, reaction temperature are 40 DEG C, continue magnetic agitation after being added dropwise to complete and react 5h.After reaction under fast stirring with different
It is filtered after propyl alcohol precipitating, reuses and continue after DMSO lysate with isopropanol precipitating, filtering, using isopropanol and gone when filtering
Ionized water repeatedly washs, and sufficiently removes unreacted reagent and other small molecules, and the product of filtering is done for 60 DEG C in vacuum drying oven
Dry 10h.
(2) acylated cellulose is dissolved in the DMSO that 30mL purifying removed water, 0.457g phthalic anhydride is added
(3.08mmol, 0.5eq.), and 0.374g triethylamine (0.514mL, 3.70mmol, 0.6eq.) is added, it is reacted at 60 DEG C
18h；0.4g NHS and 0.7g EDC activated carboxyl 12h under condition of ice bath are added, 0.5g PHMG is added and is reacting at room temperature
12h.Isopropanol precipitating is used after reaction, is filtered, washed rear room temperature vacuum drying for 24 hours, obtains the acylated fine of grafting PHMG
Dimension element.
(3) fusing point of the acylated cellulose of test grafting PHMG is 210 DEG C, and decomposition starting temperature is 280 DEG C, melting viscosity
For 110Pasec.Spinning is carried out to product using the melt spinning machine of Japanese ABE company, spinning temperature is set as 230 DEG C, spinning
Speed is set as 800m/min, is finally collected with the winding tension of 0.15cN/dtex.
Prepared fibre fineness is 6.0-11.0dtex, breaking strength 0.5-1.0cN/dtex, and elongation at break is
8.0-12.0%.
The acylated cellulose fiber of the grafting PHMG of preparation is resisted according to the concussion method in GB_T 20944.3-2008
The test of bacterium property has preferable fungistatic effect, antibacterial band H gold glucose to Escherichia coli and golden glucose coccus as the result is shown
Sugar ball bacterium is up to 9mm；Escherichia coli are up to 7mm.
The survey of antibacterial washability is carried out according to FZ_T 73023-2006 to the acylated cellulose fiber of the grafting PHMG of preparation
Examination, antibacterial rank are AAA grades.
Embodiment 4
(1) cellulosic material that the degree of polymerization is 600-800 is placed in vacuum drying oven, uses phosphorus pentoxide (P2O5) dry
6h.Cellulose 1g (AGU, 6.17mmol, 1eq.) after weighing drying is placed in three-necked flask, adds 40mL DMAc
The mixed solution of (0.43mol, 69.69eq.) and 2.4g LiCl (56.6mmol, 9.17eq.), setting heating temperature are 140
DEG C, cool down after heating 2h, continues to stir after being cooled to room temperature up to dissolving, it is completely black using visual field when polarized light microscope observing, and
Course of dissolution is continually fed into nitrogen.DMAc/LiCl/ cellulose homogeneous-phase system is obtained after dissolution cellulose, 2.2g pyridine is added
8mL DMAc and 2.712g ring is added dropwise using constant pressure funnel after magnetic agitation 5min in (2.24mL, 27.8mmol, 4.5eq.)
The mixed solution of amyl chloroacetic chloride (18.5mmol, 3.0eq.), time for adding are controlled in 1h, continue that 5mL is added dropwise after being added dropwise to complete
The mixed solution of DMAc and 0.485g chloroacetic chloride (0.44mL, 6.17mmol, 1eq.), time for adding are controlled in 30min, this process
Logical nitrogen, reaction temperature are 40 DEG C, continue magnetic agitation after being added dropwise to complete and react 5h.After reaction under fast stirring with different
It is filtered after propyl alcohol precipitating, reuses and continue after DMSO lysate with isopropanol precipitating, filtering, using isopropanol and gone when filtering
Ionized water repeatedly washs, and sufficiently removes unreacted reagent and other small molecules, and the product of filtering is done for 60 DEG C in vacuum drying oven
Dry 10h.
(2) acylated cellulose is dissolved in the DMSO that 30mL purifying removed water, addition 0.685g IPDI (3.08mmol,
0.5eq.), and 6 μ L stannous octoates are added as catalyst, reacts 15h at 50 DEG C；It is anti-at 60 DEG C to add 0.5g PHMG
Answer 4h.Methanol extraction is used after reaction, is filtered, washed rear room temperature vacuum drying for 24 hours, is obtained the acylated cellobiose of grafting PHMG
Element.
(3) fusing point of the acylated cellulose of test grafting PHMG is 207 DEG C, and decomposition starting temperature is 285 DEG C, melting viscosity
For 115Pasec.Spinning is carried out to product using the melt spinning machine of Japanese ABE company, spinning temperature is set as 230 DEG C, spinning
Speed is set as 800m/min, is finally collected with the winding tension of 0.15cN/dtex.
Prepared fibre fineness is 7.0-10.0dtex, breaking strength 0.6-1.2cN/dtex, and elongation at break is
7.5-13.0%.
The acylated cellulose fiber of the grafting PHMG of preparation is resisted according to the concussion method in GB_T 20944.3-2008
The test of bacterium property has preferable fungistatic effect, antibacterial band H gold glucose to Escherichia coli and golden glucose coccus as the result is shown
Sugar ball bacterium is up to 11mm；Escherichia coli are up to 8mm.
The survey of antibacterial washability is carried out according to FZ_T 73023-2006 to the acylated cellulose fiber of the grafting PHMG of preparation
Examination, antibacterial rank are AAA grades.
Embodiment 5
(1) cellulosic material that the degree of polymerization is 600-800 is placed in vacuum drying oven, uses phosphorus pentoxide (P2O5) dry
6h.Cellulose 1g (AGU, 6.17mmol, 1eq.) after weighing drying is placed in three-necked flask, adds 40mL DMAc
The mixed solution of (0.43mol, 69.69eq.) and 2.4g LiCl (56.6mmol, 9.17eq.), setting heating temperature are 140
DEG C, cool down after heating 2h, continues to stir after being cooled to room temperature up to dissolving, it is completely black using visual field when polarized light microscope observing, and
Course of dissolution is continually fed into nitrogen.DMAc/LiCl/ cellulose homogeneous-phase system is obtained after dissolution cellulose, 2.2g pyridine is added
8mL DMAc and 3.97g 3- is added dropwise using constant pressure funnel after magnetic agitation 5min in (2.24mL, 27.8mmol, 4.5eq.)
The mixed solution of cyclopentylpropionyl chloride (24.7mmol, 4.0eq.), time for adding control in 1h, continue to be added dropwise after being added dropwise to complete
The mixed solution of 5mL DMAc and 0.485g chloroacetic chloride (0.44mL, 6.17mmol, 1eq.), time for adding control is in 30min, originally
Process leads to nitrogen, and reaction temperature is 40 DEG C, continues magnetic agitation after being added dropwise to complete and reacts 5h.After reaction under fast stirring
It with being filtered after isopropanol precipitating, reuses and continues after DMSO lysate with isopropanol precipitating, filtering, when filtering uses isopropanol
It is repeatedly washed with deionized water, sufficiently removes unreacted reagent and other small molecules, the product of filtering is 60 in vacuum drying oven
DEG C dry 10h.
(2) acylated cellulose is dissolved in the DMSO that 30mL purifying removed water, addition 0.685g IPDI (3.08mmol,
0.5eq.), and 6 μ L stannous octoates are added as catalyst, reacts 15h at 50 DEG C；It is anti-at 60 DEG C to add 0.5g PHMG
Answer 4h.Methanol extraction is used after reaction, is filtered, washed rear room temperature vacuum drying for 24 hours, is obtained the acylated cellobiose of grafting PHMG
Element.
(3) fusing point of the acylated cellulose of test grafting PHMG is 190 DEG C, and decomposition starting temperature is 275 DEG C, melting viscosity
For 90Pasec.Spinning is carried out to product using the melt spinning machine of Japanese ABE company, spinning temperature is set as 215 DEG C, spinning
Speed is set as 800m/min, is finally collected with the winding tension of 0.15cN/dtex.
Prepared fibre fineness is 6.5-11.0dtex, breaking strength 0.6-1.5cN/dtex, and elongation at break is
8.5-15.0%.
The acylated cellulose fiber of the grafting PHMG of preparation is resisted according to the concussion method in GB_T 20944.3-2008
The test of bacterium property as the result is shown has preferable fungistatic effect (as shown in Figure 5) Escherichia coli and golden glucose coccus, antibacterial
Band H gold glucose sugar ball bacterium is up to 13mm；Escherichia coli are up to 10mm.
The survey of antibacterial washability is carried out according to FZ_T 73023-2006 to the acylated cellulose fiber of the grafting PHMG of preparation
Examination, antibacterial rank are AAA grades.
Claims (10)
1. a kind of cellulose melt spun fibre with durable antibiotic performance, it is characterised in that: the fiber is resisted by grafted guanidine salt class
The acylated cellulose of microbial inoculum is prepared through melt spinning.
2. a kind of cellulose melt spun fibre with durable antibiotic performance according to claim 1, it is characterised in that: described
Acylated cellulose is obtained by cellulose graft acyl chlorides reagent；The degree of substitution DS of acylated cellulose is between 2.80-2.95.
3. a kind of cellulose melt spun fibre with durable antibiotic performance according to claim 2, it is characterised in that: described
Acyl chlorides reagent is 2- phenylbutyryl chloride, benzene valeric chloride, 3- cyclopentylpropionyl chloride, cyclopentylacetyl chloride, cyclopenta formyl chloride, ring fourth
One or more of base formyl chloride, cyclohexyl chloroacetic chloride, cyclopropyl formyl chloride, chloroacetic chloride.
4. a kind of cellulose melt spun fibre with durable antibiotic performance according to claim 1, it is characterised in that: described
Guanidine salt class antibacterial agent is poly (hexamethylene) hydrochloride PHMG, and relative molecular mass is between 900-1200.
5. a kind of cellulose melt spun fibre with durable antibiotic performance according to claim 1 or 4, it is characterised in that:
The guanidine salt class antibacterial agent is in the degree of substitution DS on acylated cellulose between 0.05-0.20.
6. a kind of cellulose melt spun fibre with durable antibiotic performance according to claim 1, it is characterised in that: pass through
Cyclic acid anhydride or diisocyanate the grafted guanidine salt class antibacterial agent on acylated cellulose macromolecular chain.
7. a kind of cellulose melt spun fibre with durable antibiotic performance according to claim 6, it is characterised in that: described
Cyclic acid anhydride is one or more of phthalic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride；Described two is different
Cyanate is toluene di-isocyanate(TDI) TDI, isophorone diisocyanate IPDI, methyl diphenylene diisocyanate MDI, two rings
One of hexyl methane diisocyanate HMDI, hexamethylene diisocyanate HDI, lysine diisocyanate LDI or several
Kind.
8. a kind of preparation method of the cellulose melt spun fibre with durable antibiotic performance, comprising:
(1) cellulose is dissolved in DMAc/LiCl mixed solvent, obtains DMAc/LiCl/ cellulose homogeneous-phase system；Catalyst is added
Afterwards, then acyl chlorides reagent is added dropwise and the mixed solution of DMAc is reacted, reaction product is post-processed, acylated cellobiose is obtained
Element；
(2) acylated cellulose is dissolved in the DMSO that purifying removed water, cyclic acid anhydride is added, and add catalyst, in 50-80
12-24h is reacted at DEG C；Activator activation is added after reaction, adds excessive guanidine salt class antibacterial agent in room temperature reaction 6-
12h is precipitated after reaction, and is filtered, washed, room temperature in vacuo drying, and the acylated cellulose of grafted guanidine salt class antibacterial agent is obtained；
Or acylated cellulose is dissolved in the DMSO that purifying removed water, and diisocyanate is added, and add catalyst, in 40-
12-24h is reacted at 60 DEG C；Excessive guanidine salt class antibacterial agent is added after reaction, reaction temperature is 60-80 DEG C, the reaction time
For 2-4h；It precipitates, and is filtered, washed, room temperature in vacuo drying after reaction, obtain the acylated cellobiose of grafted guanidine salt class antibacterial agent
Element；
(3) acylated cellulose of grafted guanidine salt class antibacterial agent is finally subjected to melt spinning, it is rolled up to durable antibiotic
The cellulose melt spun fibre of performance.
9. a kind of preparation method of cellulose melt spun fibre with durable antibiotic performance according to claim 8, special
Sign is: the catalyst in the step (1) is pyridine, 4-dimethylaminopyridine DMAP, triethylamine TEA and diisopropylethylamine
One or more of DIEA.
10. a kind of preparation method of cellulose melt spun fibre with durable antibiotic performance according to claim 8, special
Sign is: the catalyst that cyclic acid anhydride addition is added in the step (2) is triethylamine；The catalysis of diisocyanate addition is added
Agent is organic tin catalyst.
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