CN103276596A - Preparation method of quaternized halamine antibacterial cotton fiber - Google Patents
Preparation method of quaternized halamine antibacterial cotton fiber Download PDFInfo
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Abstract
The invention discloses a preparation method of a quaternized halamine antibacterial cotton fiber. The preparation method disclosed by the invention comprises the following steps of: taking common cotton cloth as a carrier, grafting hydrolyzed alkylsilane on cotton cloth, then carrying out quaternization between a tertiary amine functional group and an alkylhalide group on the cotton cloth to graft a halamine precursor containing the tertiary amine functional group to the cotton cloth to form the cotton cloth carrying a quaternized halamine precursor; and finally, carrying out halogenation reaction to obtain quaternized halamine antibacterial cotton cloth. The process disclosed by the invention avoids synthesizing quaternized halamine precursor silane before grafting, and the synthesis consumes time and energy and needs to use an organic solvent.
Description
Technical field
The present invention relates to technical field of material, be specifically related to a kind of preparation method of quaternized halogen amine antibiotic cotton fiber.
Background technology
Along with the fast development of science and technology and improving constantly of living standards of the people, people have higher requirement to the hygienic function of textiles.Consider that all kinds of textiless are in the process of people's dress, because people's body is interior as sweat, various secretion such as sebum can depend on the textiles, and under adapt circumstance, provide good living environment for all kinds of harmful microorganisms, for its growth and breeding, thus harm people's living environment and healthy.Therefore the textiles of research and development with anti-microbial property has great significance to people's life health.
Wherein, halogen amine (N-halamine) class antiseptic is the organic compound that a class contains halogen nitrogen (N-X) functional group in numerous antiseptics.It kills various bacteriums, virus and other microorganism with the oxidation state halogen atom by the mode of contact.Simultaneously, the anti-bacterial fibre that contains halogen amine antiseptic has the performance of high-efficiency broad spectrum kill bacteria and virus as the novel anti-biotic material of a class, and performance that can simple regeneration, has obtained people's extensive attention.
US Patent No. 20060265815 discloses a kind of quaternary ammonium salt and the covalency condensation reaction of the surface material that contains hydroxy functional group such as cotton fiber etc. method of preparing products such as antibiotic cotton fiber by containing binding groups such as silane.US Patent No. 6969769 adopts 5, the 5-DMH makes raw material and 3-chloropropyl-triethoxysilane adds the synthetic 3-(3-triethoxysilylpropyltetrasulfide)-5 of thermal response in solvent dimethylformamide, the 5-DMH, by the method for chemical bonding it is grafted to the surface of materials such as cotton fiber then, handles producing halogen amine anti-biotic material at last by hypochlorite.
Though more than the prepared antibiotic cotton fiber material of these patented methods have the ability of more intense kill harmful microorganism, but in their preparation process, need at first to synthesize quaternary ammonium salt silane or halogen amine forebody silane, the synthetic of these silane need carry out under organic solvent such as dimethyl formamide and higher temperature, and the reaction time is longer, and reaction will be by mode desolventizings such as decompression distillation after finishing.Take all factors into consideration up till now that existing various antibiotic cotton fiber material prepares more existing shortcomings, we think that exploitation can effectively avoid new antibiotic cotton fiber material and the technology of preparing thereof of these shortcomings necessary.
Summary of the invention
The objective of the invention is to overcome some shortcomings that existing antibiotic cotton fiber material and technology thereof exist, provide that a class chemical constitution novelty, sterilizing high-efficiency broad spectrum, disinfection function are renewable, the preparation simple antibiotic cotton fiber material of route and technology thereof.
Design of the present invention is such: quaternary ammonium salt is the non-oxidative bactericide that a class has positive charge, and its biocidal efficacies is gentle permanent; Halogen amine is a class sterilization high-efficiency broad spectrum, the reproducible novel oxidative bactericide of sterilizing function.If design by distinctive molecular structure, make and contain quaternary ammonium salt functional group and halogen amine functional group body simultaneously on the antibiotic cotton fiber material, take full advantage of their unique physicochemical property and antibacterial characteristics and possible antibiotic cooperative effects between the two separately, just might prepare the antibiotic cotton fiber material of new generation that biocidal efficacies is more powerful, performance is more good.In addition, by earlier the haloalkyl silane after the hydrolysis being grafted on the cotton, the halogen amine forebody that will contain tertiary amine functional group by the quaterisation between the alkylhalide group on tertiary amine functional group and the cotton is grafted on the cotton then, thereby has avoided the synthetic of quaternized halogen amine forebody silane.
For this reason, it is carrier that the present invention adopts common cotton, at first the haloalkyl silane after the hydrolysis is grafted on the cotton, the halogen amine forebody that will contain tertiary amine functional group by the quaterisation between the alkylhalide group on tertiary amine functional group and the cotton is grafted on the cotton then, formation is loaded with the cotton of quaternized halogen amine forebody, obtain quaternized halogen amine antibacterial cotton cloth by halogenation at last, detailed process comprises the steps:
(1) haloalkyl silane grafts on the cotton
With the alkylhalide group siloxanes be added to the water the preparation mass fraction be the haloalkyl silane aqueous solution of 0.1-10%, stir 5-120min at ambient temperature, make the haloalkyl silane hydrolysis, again the cotton fiber is immersed in 5-60min in the above-mentioned solution, then this cotton is placed on 0.5-4h under 90 ℃ of constant temperature, it is standby that the taking-up water cleans the back.The processed mass fraction of haloalkyl silane in water is preferably 2-8%; Mixing time is preferably 15-60min; Cotton fiber soak time is preferably 10-30min; Cotton is preferably 1-2h following standing time at 90 ℃ constant temperature.
(2) contain the preparation of the cotton of quaternized halogen amine forebody
The halogen amine forebody that will contain tertiary amine functional group is added to the water and prepares mass fraction is the aqueous solution of 0.1-10%, the cotton fiber that is loaded with the alkylhalide group siloxanes that step (1) is obtained is immersed in 5-60min in the above-mentioned solution, then this cotton is placed under 90 ℃ of constant temperature and dries 1h, solidify 1-15min again under 120-190 ℃ constant temperature, it is standby that the taking-up water cleans the back.The be added to the water mass fraction of preparation of the halogen amine forebody that contains tertiary amine functional group is preferably 2-8%; The soak time that is loaded with the cotton fiber of alkylhalide group siloxanes is preferably 10-30min; The solidification temperature of cotton under constant temperature is preferably 160-180 ℃; Be preferably 2-5min hardening time.
(3) contain the preparation of the cotton of quaternized halogen amine
The cotton that is loaded with quaternized halogen amine forebody that step (2) is obtained joins in the oxidation state halogen solution, and regulating pH is 4～9 ,-15～50 ℃ of immersion 1～120min down, after the taking-up water cleans, 45 ℃ of following dry for standby.The pH of oxidation state halogen solution is preferably 6～8; The halogenation temperature is preferably 5～25 ℃; The halogenation time is preferably 20～60min.
Described haloalkyl silane has the structure of formula (I):
R wherein
1, R
2And R
3Be C
1～C
8Alkoxyl, hydroxyl, C
1～C
8Alkyl or olefin group, C
1～C
8Haloalkyl or alkenyl halide group or C
1～C
8Hydroxy alkyl, wherein R
1, R
2And R
3In at least one is C
1～C
8Alkoxyl or hydroxyl; R
1, R
2And R
3Be preferably C
1～C
3Alkoxyl; X=Cl, Br, I; N is 1～10 integer; N is preferably 2～4 integer.
The described halogen amine forebody that contains tertiary amine functional group has the structure of formula (II):
R wherein
1And R
2Be C
1-C
20Alkyl or olefin group, C
1-C
8Haloalkyl or alkenyl halide group or C
1-C
8Hydroxy alkyl; R
1And R
2Be preferably C
1-C
3Alkyl; N is 0～8 integer; N is preferably 0～3 integer
R is selected from hydantoins group, 2-imidazolidine ketone group, 4-imidazolidine ketone group, isocyanuric acid lipid group, 1,3,8-thriazaspiro [4.5] decane-2,4-two ketone groups, piperidines group.
Described halogen amine forebody radicals R can be (III)～formula (VIII) shown in each,
R wherein
1', R
2', R
3', R
4', R
5' and R
6' be C
1-C
8Alkyl or olefin group, C
1-C
8Haloalkyl or alkenyl halide group, C
1-C
8Hydroxy alkyl or aminoalkyl, phenyl, aryl, hydrogen, hydroxyl, halogen; Perhaps R
1' and R
2' unite and constitute C
3-C
7Cycloalkyl or cycloolefin group; R
1', R
2', R
3', R
4', R
5' and R
6' be preferably C
1-C
3Alkyl.
Described oxidation state halogen solution is Cl
2, Br
2, NaClO, NaBrO, KClO or KBrO solution, mass concentration is 0.001～15%.Oxidation state halogen solution is preferably NaClO and NaBrO solution, and mass concentration is preferably 0.05～0.5%.
Described halogen amine forebody group includes, but are not limited to above-mentioned group.
Quaternized halogen amine antibiotic cotton fiber by method for preparing has good antibacterial effect.
The present invention's beneficial effect compared with prior art is that quaternized halogen amine antibiotic cotton fiber has good antibacterial effect, its preparation technology's environmental protection, and raw material is cheap and easy to get.By earlier the haloalkyl silane after the hydrolysis being grafted on the cotton, the halogen amine forebody that will contain tertiary amine functional group by the quaterisation between the alkylhalide group on tertiary amine functional group and the cotton is grafted on the cotton then, thereby has avoided the synthetic of quaternized halogen amine forebody silane.
The specific embodiment
The invention will be further described below by embodiment, but embodiment does not limit protection scope of the present invention.
Embodiment 1
N, N-dimethyl chloride ethylamine hydrochloride synthetic
Thionyl chloride (SOCl with 12.83g (0.106mol) 99%
2) join in the 250mL round-bottomed flask, and constantly stir, take by weighing 8.91g (0.10mol) N then, the N-dimethylethanolamine, and under condition of ice bath with N, N-dimethylethanolamine joining dropwise be above-mentioned is equipped with in the 250mL round-bottomed flask of thionyl chloride.After dropwising, the 250mL round-bottomed flask gone in 35-50 ℃ the water-bath and add the 100mL ethanolic solution behind the reaction 1h, be warming up to the solution boiling.Reaction with the solution crystallisation by cooling, discards solution, then with gained crystal vacuumize 2h in 45 ℃ of vacuum drying chambers after finishing.The calculating of weighing, productive rate is 83%.
Embodiment 2
3-dimethyl amido ethyl-5,5-DMH (DEADH) synthetic
With 6.4g (0.05mol) 5,5-DMH and 8.64g (0.06mol) N, N-dimethyl chloride ethylamine hydrochloride is poured into respectively in the 500mL round-bottomed flask that the 100mL99.5% ethanolic solution is housed, add equimolar caustic alcohol more respectively, again above-mentioned two flasks are reacted 30min under condition of ice bath, then they are mixed, under 60 ℃, magnetic agitation 12h.Reaction equation is as follows.After reaction stops, removing by filter accessory substance NaCl, decompression distillation desolventizing ethanol.Then the gained faint yellow solid is put into vacuum drying chamber vacuumize 4h.According to document, be indicator with TBPE, TPB is titrating solution, is titration end-point when titrate becomes yellow green by redness.Measuring its productive rate is 83.24%.The thick product of DEADH is used for elementary analysis, nuclear magnetic resonance test and infrared spectrum (IR) after the chromatographic column separation and purification analyzes, and the result is as follows: elementary analysis test value (calculated value): C
9H
17O
2N
3: N%21.04 (21.09); C%54.49 (54.27); H%8.56 (8.60).Nuclear magnetic resonance
1H composes (D
2O-d2): δ: 1.41 (6H ,-CH
3), 2.24 (6H, N-CH
3), 2.56 (2H, CH
2-N (CH
3)
2), 3.60 (2H, N-CH
2-C).IR:3259,1779,1704,1451,712cm
-1。
Embodiment 3
The 3-r-chloropropyl trimethoxyl silane grafts on the cotton fiber
The configuration quality mark is the aqueous solution of 6% 3-r-chloropropyl trimethoxyl silane, and stirs 30min at ambient temperature, makes 3-r-chloropropyl trimethoxyl silane and deionized water complete miscibility.Again 10 gram cotton fibers are immersed in 15min in the above-mentioned solution, then this cotton are placed on 90 ℃ the interior oven dry of electric heating constant temperature air dry oven 1h.Taking-up is cleaned the back dry for standby with running water.It is that chlorine among the C-Cl is determined that the content that wherein is bonded to the 3-r-chloropropyl trimethoxyl silane on the cotton fiber is measured organochlorine by oxygen flask combustion method.Content of organic chloride: 1.24%.
Embodiment 4
Contain the preparation of the cotton fiber of quaternized halogen amine forebody
The configuration quality mark is 6% 3-dimethyl amido ethyl-5, the aqueous solution of 5-DMH (DEADH), the cotton fiber that 10 grams is loaded with the alkylhalide group siloxanes is immersed in wherein 1h, then behind 95 ℃ electric heating constant temperature air dry oven inner drying 1h, in 180 ℃ electric heating constant temperature air dry oven, solidify 3min again, take out with running water and clean the back dry for standby.
Embodiment 5
Contain the preparation of the cotton fiber of quaternized halogen amine
The configuration quality mark is 0.1% aqueous sodium hypochlorite solution, regulates its pH to 7.0-7.5 with the hydrochloric acid solution of 0.5mol/L simultaneously.The cotton fiber that contains quaternized halogen amine forebody of embodiment 4 preparations is immersed in wherein 45min, respectively washes 3 times with running water and deionized water then, to remove free oxidation state chlorion, again in 45 ℃ air dry oven inner drying 2h.Be 0.28% by its oxidation state chlorinity of iodometric determination.
Embodiment 6
The anti-microbial property test of antibacterial cotton cloth fiber
Be 10 with concentration
7-10
8The Escherichia coli of CFU/mL and staphylococcus aureus poise in the pH=7 phosphate buffer, adopt " absorption process " to measure the antibiotic property of quaternary ammonium bittern amine antibiotic cotton fiber material.Be 1 and 5 minute contact time, the antibiotic cotton fiber material that will be loaded with bacterium liquid then joins the aseptic test tube mesoscale eddies wash-out that contains the pH=7 phosphate buffer also enters eluent with the 0.05N hypo solution reduction of 0.5mL oxidation state chlorine, the solution of contact cotton fiber sample in the test tube is carried out a series of dilutions and places the nutrient agar plate, under 37 ℃ of conditions, cultivated 20-24 hour, carry out plate count to determine existing of survival bacterium.Anti-bacteria test result is as shown in table 1:
Table 1: the antibiotic effect of cotton fiber under different contacts time that contains quaternized halogen amine
aThe concentration of staphylococcus aureus is: 2.61 * 10
7CFU/mL,
bColibacillary concentration is: 1.41 * 10
7CFU/mL.
Above-described embodiment is interpreted as only being used for explanation the present invention and is not used in restriction protection scope of the present invention.After the content of having read the present invention's record, those skilled in the art can make various changes or modifications the present invention, and these equivalences change and modify and fall into claim of the present invention institute restricted portion equally.
Claims (5)
1. the preparation method of a quaternized halogen amine antibiotic cotton fiber is characterized in that, comprises following steps:
(1) haloalkyl silane grafts on the cotton:
With the alkylhalide group siloxanes be added to the water the preparation mass fraction be the haloalkyl silane aqueous solution of 0.1-10%, stir 5-120min at ambient temperature, make the haloalkyl silane hydrolysis, again the cotton fiber is immersed in 5-60min in the above-mentioned solution, then this cotton is placed on 0.5-4h under 90 ℃ of constant temperature, it is standby that the taking-up water cleans the back;
(2) contain the preparation of the cotton of quaternized halogen amine forebody:
The halogen amine forebody that will contain tertiary amine functional group is added to the water and prepares mass fraction is the aqueous solution of 0.1-10%, the cotton fiber that is loaded with the alkylhalide group siloxanes that step (1) is obtained is immersed in 5-60min in the above-mentioned solution, then this cotton is placed under 90 ℃ of constant temperature and dries 1h, solidify 1-15min again under 120-190 ℃ of constant temperature, it is standby that the taking-up water cleans the back;
(3) contain the preparation of the cotton of quaternized halogen amine:
The cotton that is loaded with quaternized halogen amine forebody that step (2) is obtained joins in the oxidation state halogen solution, and regulating pH is 4～9 ,-15 ℃～50 ℃ immersion 1～120min down, after the taking-up water cleans, 45 ℃ of oven dry down.
2. according to the preparation method of the described quaternized halogen amine antibiotic cotton fiber of claim 1, it is characterized in that the described haloalkyl silane of step (1) has the structure of formula (I):
R wherein
1, R
2And R
3Be C
1～C
8Alkoxyl, hydroxyl, C
1～C
8Alkyl or olefin group, C
1～C
8Haloalkyl or alkenyl halide group or C
1～C
8Hydroxy alkyl, wherein R
1, R
2And R
3In at least one is C
1～C
8Alkoxyl or hydroxyl; X=Cl, Br, I; N is 1～10 integer.
3. according to the preparation method of the described quaternized halogen amine antibiotic cotton fiber of claim 1, it is characterized in that the described halogen amine forebody that contains tertiary amine functional group of step (2) has the structure of formula (II):
R wherein
1And R
2Be C
1-C
20Alkyl or olefin group, C
1-C
8Haloalkyl or alkenyl halide group or C
1-C
8Hydroxy alkyl; N is 0～8 integer;
R is selected from hydantoins group, 2-imidazolidine ketone group, 4-imidazolidine ketone group, isocyanuric acid lipid group, 1,3,8-thriazaspiro [4.5] decane-2,4-two ketone groups, piperidines group.
4. according to the preparation method of the described quaternized halogen amine antibiotic cotton fiber of claim 3, it is characterized in that, in the described halogen amine forebody that contains tertiary amine functional group the substituent chemical constitution of R suc as formula (III)～formula (VIII) shown in each,
R wherein
1', R
2', R
3', R
4', R
5' and R
6' be C
1-C
8Alkyl or olefin group, C
1-C
8Haloalkyl or alkenyl halide group, C
1-C
8Hydroxy alkyl or aminoalkyl, phenyl, aryl, hydrogen, hydroxyl, halogen; Perhaps R
1' and R
2' unite and constitute C
3-C
7Cycloalkyl or cycloolefin group.
5. according to the preparation method of the described quaternized halogen amine antibiotic cotton fiber of claim 1, it is characterized in that the described oxidation state halogen of step (3) solution is Cl
2, Br
2, NaClO, NaBrO, KClO or KBrO solution, mass concentration is 0.001%～15%.
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| CN104088134A (en) * | 2014-07-18 | 2014-10-08 | 江南大学 | Preparation method of ultraviolet ray resistant antibacterial fabric |
| CN104264464A (en) * | 2014-09-22 | 2015-01-07 | 上海师范大学 | Preparation method and application of organic cation modified textile fibers |
| CN104628888A (en) * | 2015-02-04 | 2015-05-20 | 江南大学 | Quaternization hadegen amide modified chitosan and method for preparing antibacterial cotton fabric |
| CN105463840A (en) * | 2015-11-18 | 2016-04-06 | 崔志锋 | A novel polymer antibacterial agent |
| CN105601778A (en) * | 2016-01-19 | 2016-05-25 | 江南大学 | Annular halamine type polymeric antibacterial agent containing quaternary ammonium group and preparation method and application of polymeric antibacterial agent |
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| CN104628888A (en) * | 2015-02-04 | 2015-05-20 | 江南大学 | Quaternization hadegen amide modified chitosan and method for preparing antibacterial cotton fabric |
| CN104628888B (en) * | 2015-02-04 | 2017-03-15 | 江南大学 | Quaternized halogen amine modification of chitosan and the method for preparing antibacterial cotton fabric |
| CN105463840A (en) * | 2015-11-18 | 2016-04-06 | 崔志锋 | A novel polymer antibacterial agent |
| CN105601778A (en) * | 2016-01-19 | 2016-05-25 | 江南大学 | Annular halamine type polymeric antibacterial agent containing quaternary ammonium group and preparation method and application of polymeric antibacterial agent |
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| CN108411626B (en) * | 2018-03-06 | 2020-08-25 | 玉林师范学院 | Preparation method and application of quaternary ammonium salt-N-halamine type nano antibacterial fiber |
| CN113336783A (en) * | 2021-06-22 | 2021-09-03 | 山东科技大学 | Multifunctional silane bactericide with surface migration characteristic and preparation and application thereof |
| CN113336783B (en) * | 2021-06-22 | 2022-07-15 | 山东科技大学 | Multifunctional silane bactericide with surface migration characteristic and preparation and application thereof |
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