CN103422339B - A kind of preparation method of functional antibacterial fibre cellulose fiber - Google Patents
A kind of preparation method of functional antibacterial fibre cellulose fiber Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of functional antibacterial fibre cellulose fiber, use crosslinking agent to be grafted on cellulose fibre by chemical reaction by cyclodextrin, then utilize the cyclodextrin on fiber to carry out inclusion to antibacterials; In preparation process, to comprise cyclodextrin, crosslinking agent, catalyst, cellulose fibre reaction system carry out ultrasonic preliminary treatment.Instant invention overcomes the immobilized inefficient shortcoming of prior art cyclodextrin, preparation time is short, and efficiency is high, can make antibacterial, the anti-infective functional fibre and paper products thereof with sustained release performance, have good market prospects.
Description
Technical field
The present invention relates to the preparation method of anti-bacterial fibre, particularly a kind of preparation method of functional antibacterial fibre cellulose fiber.
Background technology
In life, people inevitably touch the microorganisms such as various bacterium, fungi, and these microorganisms, under suitable external condition, are spread disease by modes such as contacts, thus affect the healthy of people and normal work, studying and living.Therefore, along with the development of science and technology and the raising of people's living standard, the research of anti-bacterial fibre, development and production are more and more come into one's own.
Anti-bacterial fibre adopts the method for physics or chemistry the material of bacteria growing inhibiting can introduce fiber surface and innerly to make.Physical method mainly contains co-blended spinning method, composite spinning method and finishing method.Chemical method, mainly by the method for MOLECULE DESIGN, utilizes the means such as copolymerization, grafting, macromolecular reaction to change the chemical constitution of fiber, generates antibacterial group, thus gives fiber with antibacterial activity.Compared with Physical, to there is on good anti-bacterial effect, lasting, good hand touch, fiber with the anti-bacterial fibre that fibre chemistry modification legal system is standby the advantages such as non-cohesive resin.But by chemical method graft copolymerization to mainly halogen compound class, quaternary ammonium salt, isothiazole class and the guanidine salt etc. of the material on fiber, these materials directly contact with positions such as skins and problems can be caused to occur: on the one hand, because the skin of different people is different to the sensitivity of chemicals, the antiseptic being attached to fiber surface allows those skins produce sense of discomfort to chemicals than more sensitive crowd possibly, even occurs allergic symptom; On the other hand, these medicines have certain excitant, and these likely can cause after there is irritating material and direct skin contact pruitus, rubescent, play the malaise symptoms such as goose pimples.Therefore, these antibacterials should be avoided directly to contact with positions such as skins when preparing anti-bacterial fibre.
The cyclic oligomer sugar compounds that cyclodextrin (being called for short CD) is connected with α-Isosorbide-5-Nitrae type glycosidic bond by more than 6 glucopyranose units, can be divided into α-CD, β-CD, γ-CD etc. according to glucose unit number (6,7,8).It has the cavity structure that outside is hydrophilic, inner side is hydrophobic, and can carry out inclusion with multiple small-molecule substance, have the functions such as shielding, Co ntrolled release, active protection, it has the features such as nontoxic, non-stimulated, biodegradable in addition.Therefore, cyclodextrin and the good envelope of derivative thereof and fiber are organically combined, different functional fibers can be formed, to meet the various demands of people.CN 1940171A discloses a kind of preparation method of functional antibacterial fibre, be that cyclodextrin is received on cellulose fibre by crosslinking agent with epoxychloropropane, form the polymer of cyclodextrin and cellulose fibre, this polymer inclusion chloramphenicol, obtains functional antibacterial fibre.Wan Jun-hua etc. (Carbohydrate Polymers, 2008,72:695-710) with a chloro-s-triazine for crosslinking agent by immobilized for cyclodextrin on cellulose, then utilize the hydrophobic cavity inclusion antiseptic miconazole nitrate of cyclodextrin to obtain anti-bacterial fibre.Although these methods can obtain the good fiber of antibacterial effect, but there is the limitation of following aspect: epoxychloropropane method technique is simple, but the utilization rate of itself is low, also can there is hydrolysis in epoxychloropropane in the basic conditions in addition, have a large amount of oncogene products to produce, must be undertaken being separated and removing by certain technology; In one chloro-s-triazine method, a chloro-s-triazine easily moisture absorption itself, thus makes its active reduction, and on the high side.
Polycarboxylic acids method is a kind of Novel ring dextrin solid support method that at present research is more, and it is also fewer cyclodextrin to be grafted to by polycarboxylic acids method report anti-bacterial fibre preparing by cellulose fibre.Qian Liangliang etc. (food and fermentation industries, 2008,34 (2): 16-20) are crosslinking agent with polyacrylic acid, by immobilized for beta-schardinger dextrin-on cellulose, then utilize this cellulose to embed volatilization food antiseptic cinnamic acid, obtain antibacterial cellulose, but immobilized efficiency is on the low side.Therefore, how by cyclodextrin and derivative thereof and efficient, the lasting and combination of environmental protection of cellulose fibre, the hot issue of anti-bacterial fibre investigation and application has been become.
Summary of the invention
In order to overcome the above-mentioned shortcoming and defect of prior art, the object of the present invention is to provide the preparation method of the functional antibacterial fibre cellulose fiber that a kind of immobilized efficiency is high, preparation time is short, and efficiency is high.
Object of the present invention is achieved through the following technical solutions:
A preparation method for functional antibacterial fibre cellulose fiber, comprises the following steps:
(1) cellulose fibre is joined in the sodium hydroxide solution of 1.5 ~ 3mol/L, the weight ratio of cellulose fibre and sodium hydroxide solution is 1:10 ~ 1:40, at 40 ~ 70 DEG C, swelling 1 ~ 4h, is washed with distilled water to neutrality, obtains swelling good cellulose fibre;
(2) add cyclodextrin, the crosslinking agent of 50 ~ 100g, the catalyst of 5 ~ 25g of 50 ~ 150g in often liter of deionized water, at 50 ~ 70 DEG C, heat 15 ~ 30min, after dissolving completely, obtain reaction solution; In reaction solution, add swelling good cellulose fibre, after swelling 15 ~ 30min, then put into ultrasonic 15 ~ 60min in ultrasonic cleaner, supersonic frequency is 20 ~ 80KHz; Finally put in 140 ~ 180 DEG C of air dry ovens after curing reaction 15 ~ 60min, with the cellulose fibre obtaining grafted cyclodextrin after 50 ~ 70 DEG C of hot washes; Wherein, the mass ratio of swelling good cellulose fibre and reaction solution is 1:20 ~ 1:40;
(3) it is in the antibacterials solution of 2 ~ 6g/L that the cellulose fibre of grafted cyclodextrin step (2) obtained adds concentration, to vibrate in shaking table 2 ~ 8h with the hunting speed of 100 ~ 200rpm under room temperature, after deionized water or organic solvent washing, after vacuum drying chamber drying, obtain that there is functional antibacterial fibre cellulose fiber; Wherein, the cellulose fibre of described grafted cyclodextrin and the weight ratio of antibacterials solution are 1:20 ~ 1:50.
Described cyclodextrin is beta-schardinger dextrin-.
Described crosslinking agent is citric acid or butanetetra-carboxylic acid.
Described catalyst is the one in inferior sodium phosphate, sodium dihydrogen phosphate or sodium hydrogen phosphate.
Described antibacterials are the one in Ciprofloxacin Hydrochloride, trichlorine hydroxyl methyl ether or butyl p-hydroxybenzoate.
Described organic solvent is the one in methyl alcohol, ethanol or acetone.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the present invention by comprise cyclodextrin, crosslinking agent, catalyst, cellulose fibre reaction system carry out ultrasonic preliminary treatment, the crystalline texture in cellulose is destroyed by hyperacoustic resonance, make structure relative loose, thus solution more easily enters into cellulosic molecule, improve the reactivity of cellulose fibre, thus improve the immobilized efficiency of cyclodextrin.
(2) the present invention is by being grafted on cellulose fibre by cyclodextrin, form cyclodextrin modified fiber, recycle the cyclodextrin encapsulated antibacterials received on fiber, realize the shielding action of cellulose fibre to medicine of cyclodextrin grafting, control the release of medicine, its drug effect of further performance, reduce side effect, the high availability to medicine.
(3) the functional antibacterial fibre cellulose fiber prepared of the present invention is after arranging, insoluble drug release completely after can also carry out simple inclusion again, finally realize the activity of long duration, greatly strengthen expectation function or the function of commodity.
(4) the functional antibacterial fibre cellulose fiber prepared of the present invention, on cellulose fibre, the percent grafting of cyclodextrin is 3 ~ 15%; The load capacity of antibacterials is 10 ~ 30mg/g bone dry fiber; Antibacterial effect is 10 ~ 100%.
(5) preparation method of the present invention is simple to operate, with low cost.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram before and after the fibre grafting cyclodextrin of embodiments of the invention 1.
Fig. 2 be embodiments of the invention 1 prepare carry cumulative release figure in time under the fiber room temperature of Ciprofloxacin Hydrochloride.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
Cellulose fibre is put into swelling 1h in the sodium hydroxide solution of 1.5mol/L, the weight ratio of cellulose fibre and sodium hydroxide solution is 1:20; Be washed with distilled water to neutrality, for subsequent use; Take 5g beta-schardinger dextrin-, 5g citric acid, 0.5g inferior sodium phosphate join in 50ml deionized water respectively, at 50 DEG C, stir 15min make it to dissolve completely, obtain reaction solution.Swelling for 2g good cellulose fibre is dipped in reaction solution, after swollen 15min, and then ultrasonic 55min in ultrasonic cleaner is put into, frequency is 80KHz, then curing reaction 15min in 150 DEG C of air dry ovens is put into, use 50 DEG C of hot wash fibers 3 times afterwards, obtain the fiber of graft beta-cyclodextrin.It is in the Ciloxan of 2g/l that above-mentioned for 1g fiber is joined 50ml concentration, under room temperature, in the constant-temperature table of 200rpm, 4h is adsorbed in vibration, deionized water is spent 3 times after filtration, then dry 24h in 60 DEG C of vacuum drying chambers, obtains the fiber (sample 1) of load Ciprofloxacin Hydrochloride.
As can be seen from Figure 1: compared with non-graft fibres, the fiber of grafted cyclodextrin is at 1708cm
-1near have new absorption vibration peak, this is the characteristic peak of ester group.As can be seen from Figure 2: Ciprofloxacin Hydrochloride has the feature of the burst release at initial stage and the slow releasing in later stage from the release grafted cyclodextrin fiber, discharge and substantially reach balance after initial 30min release reaches 36%, 240min.
The antibacterial effect of functional antibacterial fibre cellulose fiber prepared by the present embodiment is in table 1.
For contrasting, the present embodiment has also prepared comparative sample 1, preparation process except without except ultrasonic process, all the other and sample 1 with, comparing result is in table 1.
Embodiment 2
Cellulose fibre is put into swelling 2h in the sodium hydroxide solution of 2mol/L, the weight ratio of cellulose fibre and sodium hydroxide solution is 1:30; Be washed with distilled water to neutrality, for subsequent use; Take 5g beta-schardinger dextrin-, 6g citric acid, 0.75g sodium dihydrogen phosphate join in 50ml deionized water, at 60 DEG C, stir 20min make it to dissolve completely, obtain reaction solution.Swelling for 3g good cellulose fibre is dipped in reaction solution, after swollen 20min, and then ultrasonic 30min in ultrasonic cleaner is put into, frequency is 20KHz, then curing reaction 20min in 160 DEG C of air dry ovens is put into, use 60 DEG C of hot wash fibers 3 times afterwards, obtain the fiber of graft beta-cyclodextrin; It is in the Ciloxan of 4g/l that above-mentioned for 2g fiber is put into 50ml concentration, under room temperature, in the constant-temperature table of 200rpm, 6h is adsorbed in vibration, deionized water is spent 3 times after filtration, then dry 24h in 60 DEG C of vacuum drying chambers, obtains the fiber (sample 2) of load Ciprofloxacin Hydrochloride.
The antibacterial effect of functional antibacterial fibre cellulose fiber prepared by the present embodiment is in table 1.
For contrasting, the present embodiment has also prepared comparative sample 2, preparation process except without except ultrasonic process, all the other and sample 2 with, comparing result is in table 1.
Embodiment 3
Cellulose fibre is put into swelling 3h in the sodium hydroxide solution of 3mol/L, the weight ratio of cellulose fibre and sodium hydroxide solution is 1:40; Be washed with distilled water to neutrality, for subsequent use; Take 5g beta-schardinger dextrin-, 5g citric acid, 1g sodium hydrogen phosphate join in 50ml deionized water, at 70 DEG C, stir 30min make it to dissolve completely, obtain reaction solution.Swelling for 4g good cellulose fibre is dipped in reaction solution, after swollen 30min, and then ultrasonic 50min in ultrasonic cleaner is put into, frequency is 45KHz, then curing reaction 30min in 170 DEG C of air dry ovens is put into, use 70 DEG C of hot wash fibers 3 times afterwards, obtain the fiber of graft beta-cyclodextrin; Above-mentioned for 1g fiber being put into 50ml concentration is in the trichlorine hydroxyl methyl ether solution of 6g/l, under room temperature, in the constant-temperature table of 200rpm, 8h is adsorbed in vibration, wash 3 times with ethanol after filtration, then dry 24h in 60 DEG C of vacuum drying chambers, obtain the fiber (sample 3) of load trichlorine hydroxyl methyl ether.
The antibacterial effect of functional antibacterial fibre cellulose fiber prepared by the present embodiment is in table 1.
For contrasting, the present embodiment has also prepared comparative sample 3, preparation process except without except ultrasonic process, all the other and sample 3 with, comparing result is in table 1.
Embodiment 4
Cellulose fibre is put into swelling 2h in the sodium hydroxide solution of 2mol/L, the weight ratio of cellulose fibre and sodium hydroxide solution is 1:30; Be washed with distilled water to neutrality, for subsequent use; Take 5g beta-schardinger dextrin-, 7g citric acid, 0.75g sodium dihydrogen phosphate join in 50ml deionized water, at 60 DEG C, stir 20min make it to dissolve completely, obtain reaction solution.Swelling for 3g good cellulose fibre is dipped in reaction solution, after swollen 20min, and then ultrasonic 25min in ultrasonic cleaner is put into, frequency is 70KHz, then curing reaction 20min in 160 DEG C of air dry ovens is put into, use 60 DEG C of hot wash fibers 3 times afterwards, obtain the fiber of graft beta-cyclodextrin; Above-mentioned for 2g fiber being put into 50ml concentration is in the butyl p-hydroxybenzoate solution of 4g/l, under room temperature, in the constant-temperature table of 200rpm, 6h is adsorbed in vibration, 3 times are washed with ethanol after filtration, then dry 24h in 60 DEG C of vacuum drying chambers, obtains the fiber (sample 4) of load butyl p-hydroxybenzoate.
The antibacterial effect of functional antibacterial fibre cellulose fiber prepared by the present embodiment is in table 1.
For contrasting, the present embodiment has also prepared comparative sample 4, preparation process except without except ultrasonic process, all the other and sample 4 with, comparing result is in table 1.
Embodiment 5
Cellulose fibre is put into swelling 1h in the sodium hydroxide solution of 1.5mol/L, the weight ratio of cellulose fibre and sodium hydroxide solution is 1:20; Be washed with distilled water to neutrality, for subsequent use; Take 5g beta-schardinger dextrin-, 5g butanetetra-carboxylic acid, 0.5g inferior sodium phosphate join in 50ml deionized water, at 50 DEG C, stir 15min make it to dissolve completely, obtain reaction solution.Swelling for 2g good cellulose fibre is dipped in reaction solution, after swollen 15min, and then ultrasonic 45min in ultrasonic cleaner is put into, frequency is 30KHz, then curing reaction 15min in 150 DEG C of air dry ovens is put into, use 50 DEG C of hot wash fibers 3 times afterwards, obtain the fiber of graft beta-cyclodextrin; It is in the Ciloxan of 2g/l that above-mentioned for 1g fiber is put into 50mL concentration, under room temperature, in the constant-temperature table of 200rpm, 4h is adsorbed in vibration, deionized water is spent 3 times after filtration, then dry 24h in 60 DEG C of vacuum drying chambers, obtains the fiber (sample 5) of load Ciprofloxacin Hydrochloride.
The antibacterial effect of functional antibacterial fibre cellulose fiber prepared by the present embodiment is in table 1.
For contrasting, the present embodiment has also prepared comparative sample 5, preparation process except without except ultrasonic process, all the other and sample 5 with, comparing result is in table 1.
Embodiment 6
Cellulose fibre is put into swelling 2h in the sodium hydroxide solution of 2mol/L, the weight ratio of cellulose fibre and sodium hydroxide solution is 1:30; Be washed with distilled water to neutrality, for subsequent use; Take 5g beta-schardinger dextrin-, 7g butanetetra-carboxylic acid, 0.75g sodium hydrogen phosphate join in 50ml deionized water, at 60 DEG C, stir 20min make it to dissolve completely, obtain reaction solution.Swelling for 3g good fiber is dipped in reaction solution, after swollen 20min, and then ultrasonic 30min in ultrasonic cleaner is put into, frequency is 60KHz, then curing reaction 20min in 160 DEG C of air dry ovens is put into, use 60 DEG C of hot wash fibers 3 times afterwards, obtain the fiber of graft beta-cyclodextrin; It is in the Ciloxan of 4g/l that above-mentioned for 1g fiber is put into 50mL concentration, under room temperature, in the constant-temperature table of 200rpm, 6h is adsorbed in vibration, wash 3 times with acetone after filtration, then dry 24h in 60 DEG C of vacuum drying chambers, obtain the fiber (sample 6) of load Ciprofloxacin Hydrochloride.
The antibacterial effect of functional antibacterial fibre cellulose fiber prepared by the present embodiment is in table 1.
For contrasting, the present embodiment has also prepared comparative sample 6, preparation process except without except ultrasonic process, all the other and sample 6 with, comparing result is in table 1.
Embodiment 7
Put into by cellulose fibre in the sodium hydroxide solution of 3mol/L, wherein the weight ratio of cellulose fibre and sodium hydroxide solution is 1:40, and at 70 DEG C, swelling 4h, is washed with distilled water to neutrality, for subsequent use; Take 7.5g beta-schardinger dextrin-, 5g butanetetra-carboxylic acid, 1.25g inferior sodium phosphate join in 50ml deionized water, at 70 DEG C, stir 30min make it to dissolve completely, obtain reaction solution.Swelling for 1.6g good cellulose fibre is dipped in reaction solution, after swollen 30min, and then ultrasonic 60min in ultrasonic cleaner is put into, frequency is 80KHz, then curing reaction 30min in 180 DEG C of air dry ovens is put into, use 70 DEG C of hot wash fibers 3 times afterwards, obtain the fiber of graft beta-cyclodextrin; The fiber of graft beta-cyclodextrin being put into concentration is in the trichlorine hydroxyl methyl ether solution of 6g/l, and the cellulose fibre of grafted cyclodextrin and the weight ratio of trichlorine hydroxyl methyl ether solution are 1:50; Under room temperature, in the constant-temperature table of 200rpm, 8h is adsorbed in vibration, and use methanol wash 3 times after filtering, then dry 24h in 60 DEG C of vacuum drying chambers, obtains the fiber (sample 7) of load trichlorine hydroxyl methyl ether.
The antibacterial effect of functional antibacterial fibre cellulose fiber prepared by the present embodiment is in table 1.
For contrasting, the present embodiment has also prepared comparative sample 7, preparation process except without except ultrasonic process, all the other and sample 7 with, comparing result is in table 1.
Embodiment 8
Put into by cellulose fibre in the sodium hydroxide solution of 1.5mol/L, wherein the weight ratio of cellulose fibre and sodium hydroxide solution is 1:10, and at 40 DEG C, swelling 1h, is washed with distilled water to neutrality, for subsequent use; Take 0.25g beta-schardinger dextrin-, 0.25g butanetetra-carboxylic acid, 0.25g sodium hydrogen phosphate join and add in 50ml deionized water, at 50 DEG C, stir 15min make it to dissolve completely, obtain reaction dissolvent.Swelling for 2.5g good cellulose fibre is dipped in reaction dissolvent, after swelling 15min, then curing reaction 15min in the air dry oven of 140 DEG C is put into, then ultrasonic 15min in ultrasonic cleaner is put into, frequency is 20KHz, use 50 DEG C of hot wash fibers 3 times afterwards, obtain the fiber of graft beta-cyclodextrin.Put into by the fiber of graft beta-cyclodextrin in the butyl p-hydroxybenzoate solution of 2g/l, the cellulose fibre of grafted cyclodextrin and the weight ratio of butyl p-hydroxybenzoate solution are 1:20; Under room temperature, in the constant-temperature table of 100rpm, 2h is adsorbed in vibration, washs 3 times, then dry 24h in 60 DEG C of vacuum drying chambers, obtain the fiber (sample 8) of load butyl p-hydroxybenzoate after filtration with ethanol.
The antibacterial effect of functional antibacterial fibre cellulose fiber prepared by the present embodiment is in table 1.
For contrasting, the present embodiment has also prepared comparative sample 8, preparation process except without except ultrasonic process, all the other and sample 8 with, comparing result is in table 1.
The antibacterial effect of sample prepared by table 1 embodiment 1 ~ 8
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not limited by the examples; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. a preparation method for functional antibacterial fibre cellulose fiber, is characterized in that, comprises the following steps:
(1) cellulose fibre is joined in the sodium hydroxide solution of 1.5 ~ 3mol/L, the weight ratio of cellulose fibre and sodium hydroxide solution is 1:10 ~ 1:40, at 40 ~ 70 DEG C, swelling 1 ~ 4h, is washed with distilled water to neutrality, obtains swelling good cellulose fibre;
(2) add cyclodextrin, the crosslinking agent of 50 ~ 100g, the catalyst of 5 ~ 25g of 50 ~ 150g in often liter of deionized water, at 50 ~ 70 DEG C, heat 15 ~ 30min, after dissolving completely, obtain reaction solution; In reaction solution, add swelling good cellulose fibre, after swelling 15 ~ 30min, then put into ultrasonic 15 ~ 60min in ultrasonic cleaner, supersonic frequency is 20 ~ 80KHz; Finally put in 140 ~ 180 DEG C of air dry ovens after curing reaction 15 ~ 60min, with the cellulose fibre obtaining grafted cyclodextrin after 50 ~ 70 DEG C of hot washes; Wherein, the mass ratio of swelling good cellulose fibre and reaction solution is 1:20 ~ 1:40;
(3) it is in the antibacterials solution of 2 ~ 6g/L that the cellulose fibre of grafted cyclodextrin step (2) obtained adds concentration, to vibrate in shaking table 2 ~ 8h with the hunting speed of 100 ~ 200rpm under room temperature, after deionized water or organic solvent washing, after vacuum drying chamber drying, obtain that there is functional antibacterial fibre cellulose fiber; Wherein, the cellulose fibre of described grafted cyclodextrin and the weight ratio of antibacterials solution are 1:20 ~ 1:50.
2. the preparation method of functional antibacterial fibre cellulose fiber according to claim 1, is characterized in that, described cyclodextrin is beta-schardinger dextrin-.
3. the preparation method of functional antibacterial fibre cellulose fiber according to claim 1, is characterized in that, described crosslinking agent is citric acid or butanetetra-carboxylic acid.
4. the preparation method of functional antibacterial fibre cellulose fiber according to claim 1, is characterized in that, described catalyst is the one in inferior sodium phosphate, sodium dihydrogen phosphate or sodium hydrogen phosphate.
5. the preparation method of functional antibacterial fibre cellulose fiber according to claim 1, is characterized in that, described antibacterials are the one in Ciprofloxacin Hydrochloride, trichlorine hydroxyl methyl ether or butyl p-hydroxybenzoate.
6. the preparation method of functional antibacterial fibre cellulose fiber according to claim 1, is characterized in that, described organic solvent is the one in methyl alcohol, ethanol or acetone.
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| CN105461814B (en) * | 2015-12-14 | 2018-03-27 | 上海交通大学医学院附属仁济医院 | A kind of cellulose acetate derivative and its production and use |
| CN105622962B (en) * | 2016-03-16 | 2017-11-17 | 江南大学 | A kind of preparation method of composite cyclodextrin hydrogel |
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| CN107675503A (en) * | 2017-11-10 | 2018-02-09 | 安徽翰联纺织有限公司 | The preparation method of long acting antibiotic weaving Vegetrable fibre material |
| CN107761183B (en) * | 2017-11-21 | 2018-12-14 | 山西纪兰潞秀家纺有限公司 | It is a kind of with antibacterial, health care, the vegetative fiber cellulose fiber of skin-protecting function and preparation method thereof |
| CN107938164A (en) * | 2017-12-25 | 2018-04-20 | 合肥洁诺无纺布制品有限公司 | A kind of preparation method of the antibacterial plant fiber non-woven fabric of fragrance |
| CN113512886A (en) * | 2020-04-09 | 2021-10-19 | 天津工业大学 | Essential oil-loaded cellulose fiber and preparation method thereof |
| CN112176728B (en) * | 2020-07-09 | 2021-07-09 | 青岛尼希米生物科技有限公司 | Antibacterial, antiviral and deodorant cotton fiber and preparation method and application thereof |
| CN115652630A (en) * | 2022-07-05 | 2023-01-31 | 中国制浆造纸研究院有限公司 | Antibacterial and deodorizing functional fiber and preparation method thereof |
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