CN103276596B - Preparation method of quaternized halamine antibacterial cotton fiber - Google Patents
Preparation method of quaternized halamine antibacterial cotton fiber Download PDFInfo
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- CN103276596B CN103276596B CN201310206616.XA CN201310206616A CN103276596B CN 103276596 B CN103276596 B CN 103276596B CN 201310206616 A CN201310206616 A CN 201310206616A CN 103276596 B CN103276596 B CN 103276596B
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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, the hygienic function of people to textiles is had higher requirement.Consider in the process that all kinds of textiles is worn people, due in people's body as sweat, the various secretion such as sebum can depend on textiles, and for all kinds of harmful microorganism provides good living environment under adapt circumstance, for its growth and reproduction, thus the living environment of harm people and healthy.Therefore research and develop the life health of textiles to people with anti-microbial property to have great significance.
Wherein, in numerous antiseptic, halogen amine (N-halamine) class antiseptic is the organic compound that a class contains halogen nitrogen (N-X) functional group.It kills various bacterium, virus and other microorganism with oxidation state halogen atom by the mode of contact.Meanwhile, the anti-bacterial fibre containing halogen amine antiseptic has the performance of high-efficiency broad spectrum kill bacteria and virus as the anti-biotic material that a class is novel, and can the performance of simple regeneration, obtains the extensive attention of people.
US Patent No. 20060265815 discloses a kind of method that the products such as antibiotic cotton fiber are prepared in the covalency condensation reaction of material as cotton fiber etc. containing hydroxy functional group by the quaternary ammonium salt containing binding groups such as silane and surface.US Patent No. 6969769 adopts 5,5-DMH makes raw material and 3-chloropropyl-triethoxysilane heats Reactive Synthesis 3-(3-triethoxysilylpropyltetrasulfide)-5 in solvent dimethylformamide, 5-DMH, then by the method for chemical bonding, it is grafted to the surface of the materials such as cotton fiber, produces halogen amine anti-biotic material finally by hypochlorite process.
Although the antibiotic cotton fiber material above prepared by these patented methods has the ability of stronger kill harmful microorganism, but need first to synthesize quaternary ammonium salt silane or halogen amine forebody silane in their preparation process, the synthesis of these silane needs to carry out under organic solvent is as dimethyl formamide and higher temperature, and the reaction time is longer, will by modes such as decompression distillation except desolventizing after reaction terminates.Consider some shortcomings up till now existing for existing various antibiotic cotton fiber material preparation, we think exploitation can effectively avoid the new antibiotic cotton fiber material of these shortcomings and technology of preparing necessary.
Summary of the invention
The object 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 simple antibiotic cotton fiber material of syntheti c route and technology thereof.
Design of the present invention is such: quaternary ammonium salt is the non-oxidative bactericide of a class with positive charge, and its biocidal efficacies is gentle permanent; Halogen amine is a class sterilization high-efficiency broad spectrum, the reproducible novel oxidized type bactericide of sterilizing function.If by unique Molecular Design, make on antibiotic cotton fiber material simultaneously containing quaternary ammonium salt functional group and halogen amine functional group body, make full use of their respective unique physicochemical properties and antibacterial characteristics and possible antibacterial cooperative effect between the two, just likely prepare the antibiotic cotton fiber material of new generation that biocidal efficacies is more powerful, performance is more excellent.In addition, by first the haloalkyl silane after hydrolysis being grafted on cotton, then by the quaterisation between the alkylhalide group in tertiary amine functional group and cotton, the halogen amine forebody containing tertiary amine functional group is grafted on cotton, thus avoids the synthesis of quaternized halogen amine forebody silane.
For this reason, the present invention adopts common cotton to be carrier, first the haloalkyl silane after hydrolysis is grafted on cotton, then by the quaterisation between the alkylhalide group in tertiary amine functional group and cotton, the halogen amine forebody containing tertiary amine functional group is grafted on cotton, form the cotton being loaded with quaternized halogen amine forebody, obtain quaternized halogen amine antibacterial cotton cloth finally by halogenation, detailed process comprises the steps:
(1) haloalkyl silane grafts on cotton
The preparation mass fraction that is added to the water by alkylhalide group siloxanes is the haloalkyl silane aqueous solution of 0.1-10%, stir 5-120min at ambient temperature, haloalkyl silane is hydrolyzed, again cotton fiber is immersed in 5-60min in above-mentioned solution, then this cotton is placed on 0.5-4h under 90 DEG C of constant temperature, for subsequent use after the cleaning of taking-up water.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 standing time under the constant temperature of 90 DEG C.
(2) preparation of the cotton containing quaternized halogen amine forebody
The preparation mass fraction that halogen amine forebody containing tertiary amine functional group is added to the water is the aqueous solution of 0.1-10%, the cotton fiber being loaded with alkylhalide group siloxanes step (1) obtained is immersed in 5-60min in above-mentioned solution, then 1h is dried under this cotton being placed on 90 DEG C of constant temperature, 1-15min is solidified again under the constant temperature of 120-190 DEG C, for subsequent use after the cleaning of taking-up water.Halogen amine forebody containing tertiary amine functional group be added to the water preparation mass fraction be preferably 2-8%; The soak time being loaded with the cotton fiber of alkylhalide group siloxanes is preferably 10-30min; Cotton solidification temperature is at a constant temperature preferably 160-180 DEG C; Hardening time is preferably 2-5min.
(3) preparation of the cotton containing quaternized halogen amine
The cotton being loaded with quaternized halogen amine forebody step (2) obtained joins in oxidation state halogen solutions, regulates pH to soak 1 ~ 120min at 4 ~ 9 ,-15 ~ 50 DEG C, after taking out the cleaning of use water, and dry for standby at 45 DEG C.The pH of oxidation state halogen solutions is preferably 6 ~ 8; Halogenation temperature is preferably 5 ~ 25 DEG C; The halogenation time is preferably 20 ~ 60min.
Described haloalkyl silane has the structure of formula (I):
Wherein R
1, R
2and R
3for 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 the integer of 1 ~ 10; N is preferably the integer of 2 ~ 4.
The described halogen amine forebody containing tertiary amine functional group has the structure of formula (II):
Wherein R
1and R
2for 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 the integer of 0 ~ 8; N is preferably the integer of 0 ~ 3
R is selected from hydantoins group, 2-imidazolidine keto group, 4-imidazolidine keto group, isocyanuric acid lipid group, 1,3,8-thriazaspiro [4.5] decane-2,4-diones class group, piperidines group.
Described halogen amine forebody radicals R can for shown in any one of (III) ~ formula (VIII),
Wherein R
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; Or R
1' and R
2' combine formation 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 solutions is Cl
2, Br
2, NaClO, NaBrO, KClO or KBrO solution, mass concentration is 0.001 ~ 15%.Oxidation state halogen solutions 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.
The quaternized halogen amine antibiotic cotton fiber prepared by said method has good antibacterial effect.
The present invention's beneficial effect is compared with prior art, quaternized halogen amine antibiotic cotton fiber has good antibacterial effect, and its preparation technology's environmental protection, raw material is cheap and easy to get.By first the haloalkyl silane after hydrolysis being grafted on cotton, then by the quaterisation between the alkylhalide group in tertiary amine functional group and cotton, the halogen amine forebody containing tertiary amine functional group is grafted on cotton, thus avoids the synthesis of quaternized halogen amine forebody silane.
Detailed description of the invention
Below by embodiment, the invention will be further described, but embodiment does not limit the scope of the invention.
Embodiment 1
The synthesis of N, N-dimethyl chloride ethylamine hydrochloride
By the thionyl chloride (SOCl of 12.83g (0.106mol) 99%
2) join in 250mL round-bottomed flask, and constantly stir, then take 8.91g (0.10mol) N, N-dimethylethanolamine, and under condition of ice bath by N, N-dimethylethanolamine dropwise join above-mentioned being equipped with in the 250mL round-bottomed flask of thionyl chloride.After dropwising, 250mL round-bottomed flask is gone to after reacting 1h in the water-bath of 35-50 DEG C and add 100mL ethanolic solution, be warming up to solution boiling.After reaction terminates, by solution crystallisation by cooling, then discard solution, by gained crystal vacuumize 2h in 45 DEG C of vacuum drying chambers.Weigh calculating, productive rate is 83%.
Embodiment 2
The synthesis of 3-dimethyl amido ethyl-5,5-DMH (DEADH)
By 6.4g (0.05mol) 5,5-DMH and 8.64g (0.06mol) N, N-dimethyl chloride ethylamine hydrochloride is poured into respectively and is equipped with in the 500mL round-bottomed flask of 100mL99.5% ethanolic solution, add equimolar caustic alcohol respectively again, again above-mentioned two flasks are reacted 30min under condition of ice bath, then they are mixed, at 60 DEG C, magnetic agitation 12h.Reaction equation is as follows.After reaction stops, crossing and filter accessory substance NaCl, decompression distillation removing etoh solvent.Then gained faint yellow solid is put into vacuum drying chamber vacuumize 4h.According to document, take TBPE as indicator, TPB is titrating solution, and titrate is titration end-point when redness becomes yellow green.Measuring its productive rate is 83.24%.The thick product of DEADH is analyzed for elementary analysis, nuclear magnetic resonance test and infrared spectrum (IR) after chromatographic column separation and purification, and 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
3-r-chloropropyl trimethoxyl silane grafts on cotton fiber
Configuration quality mark is the aqueous solution of the 3-r-chloropropyl trimethoxyl silane of 6%, and stirs 30min at ambient temperature, makes 3-r-chloropropyl trimethoxyl silane and deionized water complete miscibility.Again 10 grams of cotton fibers are immersed in 15min in above-mentioned solution, in the electric heating constant-temperature blowing drying box then this cotton being placed on 90 DEG C, dry 1h.Taking-up running water cleaning post-drying is for subsequent use.The chlorine that the content being wherein bonded to the 3-r-chloropropyl trimethoxyl silane on cotton fiber is measured in organochlorine and C-Cl by oxygen flask combustion method is determined.Content of organic chloride: 1.24%.
Embodiment 4
The preparation of the cotton fiber containing quaternized halogen amine forebody
Configuration quality mark is the 3-dimethyl amido ethyl-5 of 6%, the aqueous solution of 5-DMH (DEADH), the cotton fiber 10 grams being loaded with alkylhalide group siloxanes is immersed in wherein 1h, then after the electric heating constant-temperature blowing drying box inner drying 1h of 95 DEG C, in the electric heating constant-temperature blowing drying box of 180 DEG C, solidify 3min again, taking-up running water cleaning post-drying is for subsequent use.
Embodiment 5
The preparation of the cotton fiber containing quaternized halogen amine
Configuration quality mark is the aqueous sodium hypochlorite solution of 0.1%, regulates its pH to 7.0-7.5 with the hydrochloric acid solution of 0.5mol/L simultaneously.The cotton fiber containing quaternized halogen amine forebody embodiment 4 prepared is immersed in wherein 45min, then respectively washes 3 times with running water and deionized water, to remove free oxidation state chlorion, then in the air dry oven inner drying 2h of 45 DEG C.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 by concentration
7-10
8the Escherichia coli of CFU/mL and staphylococcus aureus poise in pH=7 phosphate buffer, adopt " absorption process " to measure the antibiotic property of quaternary ammonium bittern amine antibiotic cotton fiber material.Contact time is 1 and 5 minute, then the antibiotic cotton fiber material being loaded with bacterium liquid is joined the aseptic test tube mesoscale eddies wash-out containing pH=7 phosphate buffer also enters eluent oxidation state chlorine with the 0.05N hypo solution reduction of 0.5mL, the solution contacting cotton fiber sample in test tube is carried out a series of dilution and is placed in nutrient agar plate, under 37 DEG C of conditions, cultivate 20-24 hour, carry out plate count to determine the existence of surviving bacteria.Anti-bacteria test result is as shown in table 1:
Table 1: the antibiotic effect of the cotton fiber containing quaternized halogen amine under different contact time
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 not used in for illustration of the present invention limiting the scope of the 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 equivalence changes and modification fall into the scope of the claims in the present invention equally.
Claims (5)
1. a preparation method for quaternized halogen amine antibiotic cotton fiber, is characterized in that, comprise following steps:
(1) haloalkyl silane grafts on cotton:
The preparation mass fraction that is added to the water by haloalkyl silane is the haloalkyl silane aqueous solution of 0.1-10%, stir 5-120min at ambient temperature, haloalkyl silane is hydrolyzed, again cotton fiber is immersed in 5-60min in above-mentioned solution, then this cotton is placed on 0.5-4h under 90 DEG C of constant temperature, for subsequent use after the cleaning of taking-up water;
(2) preparation of the cotton containing quaternized halogen amine forebody:
The preparation mass fraction that halogen amine forebody containing tertiary amine functional group is added to the water is the aqueous solution of 0.1-10%, the cotton fiber being loaded with haloalkyl silane step (1) obtained is immersed in 5-60min in above-mentioned solution, then 1h is dried under this cotton being placed on 90 DEG C of constant temperature, 1-15min is solidified again under 120-190 DEG C of constant temperature, for subsequent use after the cleaning of taking-up water;
(3) preparation of the cotton containing quaternized halogen amine:
The cotton being loaded with quaternized halogen amine forebody step (2) obtained joins in oxidation state halogen solutions, regulates pH to be 4 ~ 9, soaks 1 ~ 120min at-15 DEG C ~ 50 DEG C, after taking out the cleaning of use water, dries at 45 DEG C.
2., according to the preparation method of quaternized halogen amine antibiotic cotton fiber according to claim 1, it is characterized in that, the haloalkyl silane described in step (1) has the structure of formula (I):
Wherein R
1, R
2and R
3for 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 the integer of 1 ~ 10.
3. according to the preparation method of quaternized halogen amine antibiotic cotton fiber according to claim 1, it is characterized in that, the halogen amine forebody containing tertiary amine functional group described in step (2) has the structure of formula (II):
Wherein R
1and R
2for C
1-C
20alkyl or olefin group, C
1-C
8haloalkyl or alkenyl halide group or C
1-C
8hydroxy alkyl; N is the integer of 0 ~ 8;
R is selected from hydantoins group, 2-imidazolidine keto group, 4-imidazolidine keto group, isocyanuric acid ester groups, 1,3,8-thriazaspiro [4.5] decane-2,4-diones class group, piperidines group.
4. according to the preparation method of quaternized halogen amine antibiotic cotton fiber according to claim 3, it is characterized in that, the described chemical constitution containing R substituent in the halogen amine forebody of tertiary amine functional group is such as formula shown in any one of (III) ~ formula (VIII)
Wherein R
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; Or R
1' and R
2' combine formation C
3-C
7cycloalkyl or cycloolefin group.
5., according to the preparation method of halogen amine antibiotic cotton fiber quaternized described in claim 1, it is characterized in that, the oxidation state halogen solutions described in step (3) is Cl
2, Br
2, NaClO, NaBrO, KClO or KBrO solution, mass concentration is 0.001% ~ 15%.
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| CN104088134B (en) * | 2014-07-18 | 2016-02-03 | 江南大学 | A kind of preparation method of UV resistant antibiotic fabric |
| CN104264464B (en) * | 2014-09-22 | 2016-05-25 | 上海师范大学 | Preparation method and the application of organic cation modification textile 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 |
| CN105601778B (en) * | 2016-01-19 | 2017-07-11 | 江南大学 | A kind of ring-type halogen amine polymer antibacterial agent containing quaternary ammonium group and its preparation method and application |
| CN105860121A (en) * | 2016-04-06 | 2016-08-17 | 东华大学 | Preparation method of antimicrobial bacterial cellulose material |
| CN106906658B (en) * | 2017-01-10 | 2020-08-07 | 上海师范大学 | Haloamine grafted natural fiber textile and preparation method and application thereof |
| 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 |
| 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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| CN101798324A (en) * | 2010-03-11 | 2010-08-11 | 杭州奥坦斯布艺有限公司 | Method for preparing antibacterial agent achieving antibacterial effect on decorative textile fabric |
| CN102634987A (en) * | 2012-04-27 | 2012-08-15 | 陕西科技大学 | Fluoroalkyl carboxy polysiloxane/nano particle super-hydrophobic composite membrane and preparation method thereof |
| CN102677453A (en) * | 2012-05-25 | 2012-09-19 | 浙江理工大学 | Method for preparing cotton fabric loaded with organosilicon quaternary ammonium and nano titanium dioxide composite antibacterial agent |
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| JPH02234977A (en) * | 1989-03-03 | 1990-09-18 | Toray Ind Inc | Cloth having water-repellency |
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| CN101798324A (en) * | 2010-03-11 | 2010-08-11 | 杭州奥坦斯布艺有限公司 | Method for preparing antibacterial agent achieving antibacterial effect on decorative textile fabric |
| CN102634987A (en) * | 2012-04-27 | 2012-08-15 | 陕西科技大学 | Fluoroalkyl carboxy polysiloxane/nano particle super-hydrophobic composite membrane and preparation method thereof |
| CN102677453A (en) * | 2012-05-25 | 2012-09-19 | 浙江理工大学 | Method for preparing cotton fabric loaded with organosilicon quaternary ammonium and nano titanium dioxide composite antibacterial agent |
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