CN103059305B - Preparation method of antibacterial hydrophobic complexing agent for polyester fibers - Google Patents
Preparation method of antibacterial hydrophobic complexing agent for polyester fibers Download PDFInfo
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- CN103059305B CN103059305B CN201310027956.6A CN201310027956A CN103059305B CN 103059305 B CN103059305 B CN 103059305B CN 201310027956 A CN201310027956 A CN 201310027956A CN 103059305 B CN103059305 B CN 103059305B
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- carboxyl
- guanidine compound
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- antibacterial
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 29
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000835 fiber Substances 0.000 title abstract description 6
- 239000008139 complexing agent Substances 0.000 title abstract 4
- 229920000728 polyester Polymers 0.000 title abstract 3
- -1 polysiloxane Polymers 0.000 claims abstract description 66
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 10
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006482 condensation reaction Methods 0.000 claims abstract description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 50
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 28
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 28
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 22
- 229920004935 Trevira® Polymers 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 239000012362 glacial acetic acid Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 229910000077 silane Inorganic materials 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000006210 lotion Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000003252 repetitive effect Effects 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 238000005201 scrubbing Methods 0.000 claims description 5
- 238000010025 steaming Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- XUQBZZQPEHDPFH-UHFFFAOYSA-N 4-chloro-1-hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1Cl XUQBZZQPEHDPFH-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 3
- 230000000740 bleeding effect Effects 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000003242 anti bacterial agent Substances 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 9
- 238000002329 infrared spectrum Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 4
- 238000009998 heat setting Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 238000002479 acid--base titration Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000004304 visual acuity Effects 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- QBKSWRVVCFFDOT-UHFFFAOYSA-N gossypol Chemical compound CC(C)C1=C(O)C(O)=C(C=O)C2=C(O)C(C=3C(O)=C4C(C=O)=C(O)C(O)=C(C4=CC=3C)C(C)C)=C(C)C=C21 QBKSWRVVCFFDOT-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- FPIRBHDGWMWJEP-UHFFFAOYSA-N 1-hydroxy-7-azabenzotriazole Chemical compound C1=CN=C2N(O)N=NC2=C1 FPIRBHDGWMWJEP-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- QHOPXUFELLHKAS-UHFFFAOYSA-N Thespesin Natural products CC(C)c1c(O)c(O)c2C(O)Oc3c(c(C)cc1c23)-c1c2OC(O)c3c(O)c(O)c(C(C)C)c(cc1C)c23 QHOPXUFELLHKAS-UHFFFAOYSA-N 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229930000755 gossypol Natural products 0.000 description 1
- 229950005277 gossypol Drugs 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- OKDQKPLMQBXTNH-UHFFFAOYSA-N n,n-dimethyl-2h-pyridin-1-amine Chemical compound CN(C)N1CC=CC=C1 OKDQKPLMQBXTNH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a preparation method of an antibacterial hydrophobic complexing agent for polyester fibers, belonging to the field of an antibacterial agent synthetic technology. The preparation method comprises the following steps of: synthesizing carboxylpolysiloxane, wherein the carboxylpolysiloxane is generated from a hydrogen-containing saline and an acrylic acid; preparing a monoguanidyl compound, wherein the monoguanidyl compound is obtained from cyanamide and alkylamine; and carrying out condensation reaction of carboxylpolysiloxane and the monoguanidyl compound so as to obtain the antibacterial hydrophobic complexing agent. According to the invention, polysiloxane with functions of dewatering, decontaminating and the like and groups with antibacterial functions are introduced to a high polymer long chain through a way of copolymerization, so that the preparation method of the antibacterial hydrophobic complexing agent for the polyester fibers has the advantages of high efficiency, broad spectrum, good dispersibility, cheap price and the like, is free from volatility, can be easily processed at high temperature, is easy to store.
Description
Technical field
The invention belongs to antiseptic-germicide synthesis technical field, be specifically related to a kind of preparation method of trevira antibacterial hydrophobic recombiner.
Background technology
Siloxanes softening agent, the flexibility of fibre substrate, elasticity and smooth feeling can be improved for textile finishing, the good hydrophobicity of fabric and soil release performance can be given again, and through its arrange light color or white fabrics whiteness good, also have imitative numb feel, therefore have one's own knack in the stylization arrangement of fabric.
Current of a great variety of antiseptic-germicide, mainly contains five large classes, inorganic antiseptic, organic antibacterial agent, inorganic with organic composite antibiotic agent, natural antibacterial agent, polymer antibacterial agent.Silver-series antibacterial agent is oxidizable, light stability is poor, long-time uses because oxidation goods can turn black, and being on the increase, easily to environment of the heavy metal metal ion discharged in use procedure.Natural organic antibacterial agent poor heat resistance, antibacterial effect is not lasting.Polymer antiseptic-germicide to have the function monomer of anti-microbial property, and by grafting, antibacterial group is incorporated in high polymer long chain by the means such as copolymerization, and having efficient, long-acting, safe, stable etc. has good characteristic.
Summary of the invention
For prior art Problems existing, the object of the invention is to design the technical scheme of the preparation method that a kind of trevira antibacterial hydrophobic recombiner is provided.
The preparation method of described a kind of trevira antibacterial hydrophobic recombiner, is characterized in that comprising following processing step:
1) synthesis of carboxyl polysiloxane: described carboxyl polysiloxane is generated by silane containing hydrogen and vinylformic acid;
2) preparation of single guanidine compound: described single guanidine compound is generated by cyanamide and alkylamine;
3) carboxyl polysiloxane and single guanidine compound condensation reaction:
Carboxyl polysiloxane, single guanidine compound, promotor adding are equipped with in the there-necked flask of agitator, add solvent a and dissolve, be cooled to 0 ~ 5 DEG C; Slow dropping contains the solvent a of straight chain bonding reagent, is naturally warming up to room temperature, stirring reaction 2 ~ 24h, filters with solvent a washing and pressure reducing and steaming solvent a, obtains trevira antibacterial hydrophobic recombiner;
Described carboxyl polysiloxane and the molar ratio of single guanidine compound are determined according to the hydroxy radical content of carboxyl polysiloxane: n(COOH): n (single guanidine compound) is 1:1.2 ~ 1:1.5; Described straight chain bonding reagent and the molar ratio of single guanidine compound are 1.2:1 ~ 1.5:1; The molar ratio of described promotor and single guanidine compound is 1.2:1 ~ 1.5:1;
Above-mentioned straight chain bonding reagent is the one in N, N-dicyclohexylcarbodiimide, triethylamine, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, N, N-DIC, phosphinylidyne diimidazole;
Above-mentioned promotor is the one in I-hydroxybenzotriazole, the chloro-I-hydroxybenzotriazole of 6-, 1-hydroxyl-7-azepine benzotriazole, 4-N, N-Dimethylamino pyridine;
Above-mentioned solvent a is the one in tetrahydrofuran (THF), ethyl acetate, methylene dichloride, DMF.
The preparation method of described a kind of trevira antibacterial hydrophobic recombiner, is characterized in that the described concentration containing straight chain bonding reagent in the solvent a of straight chain bonding reagent is 1.5 ~ 5mmol/10ml.
The preparation method of described a kind of trevira antibacterial hydrophobic recombiner, is characterized in that described carboxyl polysiloxane obtains especially by following steps:
Add in the there-necked flask with agitator by silane containing hydrogen, vinylformic acid, platinum based catalyst, after stirred at ambient temperature is even, be warming up to 70 ~ 90 DEG C, reaction 20 ~ 25h terminates; Suction filtration, underpressure distillation at 50 ~ 65 DEG C of vacuum-drying 24h, obtains carboxyl silicone intermediate after removing impurity and low-boiling-point substance; Getting this intermediate appropriate is slowly added drop-wise in excessive solution b, controls rate of addition, after dropwising, reacts 1 ~ 3h and terminate at 20 ~ 40 DEG C; Be 7 by distilled water repetitive scrubbing to the pH value of washing lotion, suction filtration, at 50 ~ 65 DEG C of vacuum-drying 24h, obtains carboxyl polysiloxane;
Described silane containing hydrogen has following structure:
Wherein R
1, R
2for methyl or ethyl; R
3for H, alkyl or phenyl;
Described platinum based catalyst is the one of Platinic chloride or platinum dioxide or two kinds;
The sulphuric acid soln of described solution b to be volume fraction be 15-60%;
Described silane containing hydrogen and acrylic acid molar ratio are 1.2:1 ~ 2:1; The quality that feeds intake of platinum based catalyst is 0.01% ~ 0.05% of reactant total mass.
The preparation method of described a kind of trevira antibacterial hydrophobic recombiner, is characterized in that described single guanidine compound obtains especially by following steps:
In the there-necked flask having agitator, add alkylamine and Glacial acetic acid respectively, be warming up to 100 ~ 130 DEG C after mixing, stir and lower dropping cyanamide of bleeding, maintaining temperature of reaction is 110 ~ 130 DEG C; After dropwising, continue reaction 20 ~ 40 min, stop heating, cooling; Add the water of 2 times of volumes, heating for dissolving, with sodium hydroxide adjust ph to 10 ~ 13, leave standstill, after separating upper strata material, use the water dissolution of 2 times of volumes again, heating in water bath, carry out regulation system pH value to 7 with the acetum that Glacial acetic acid preparation quality mark is 36%, leave standstill and separate product, rotary evaporation final vacuum is dry, with solvent c recrystallization, obtain single guanidine compound.
Described cyanamide and the molar ratio of alkylamine are 1.5:1 ~ 2:1; Described Glacial acetic acid and the molar ratio of alkylamine are 1.2:1 ~ 1.5:1, and described solvent c is ethanol, chloroform or acetone.
The using method of the trevira antibacterial hydrophobic recombiner that the present invention obtains is as follows: this recombiner adds in silicone oil with the addition of 3% ~ 30%, and two roads for trevira oil operation.Within making the better infiltrated fiber top layer of described antibacterial hydrophobic recombiner, and silicone oil can covered composite yarn agent preferably, and the temperature of relaxation heat setting controls at 100 DEG C ~ 180 DEG C, and the time of relaxation heat setting is 20 ~ 40min.
Compared with prior art, positively effect of the present invention is:
Trevira antibacterial hydrophobic recombiner of the present invention will have the polysiloxane of the functions such as hydrophobic, decontamination and have antibacterial group and be incorporated in high polymer long chain by the means of copolymerization, thus have efficient, wide spectrum, non-volatile, be easy to high temperature process, favorable dispersity, be easy to plurality of advantages such as storing, cheap.
Accompanying drawing explanation
The infrared spectrum of Fig. 1 methyldiethoxysilane, vinylformic acid, carboxyl silicone intermediate and carboxyl polysiloxane;
The infrared spectrum of the mono-guanidine compound of Fig. 2;
The infrared spectrum of Fig. 3 antibacterial hydrophobic recombiner.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1: the synthesis of carboxyl polysiloxane
Get 604.125g (4.5mol) methyldiethoxysilane, 216.18g(3mol) vinylformic acid, 0.082g platinum dioxide add in the there-necked flask with agitator, stirred at ambient temperature evenly after, be warming up to 85 DEG C, reaction 23h terminates; Suction filtration, after underpressure distillation goes out decon and low-boiling-point substance, at 55 DEG C of vacuum-drying 24h, obtains carboxyl silicone intermediate; It is in the sulphuric acid soln of 40% that this intermediate getting half quality is slowly added drop-wise to excessive volume fraction, strictly controls rate of addition, after dropwising, reacts 2h and terminate at 23 DEG C; Be 7 by distilled water repetitive scrubbing to the pH value of washing lotion, suction filtration, at 55 DEG C of vacuum-drying 24h, namely obtains carboxyl polysiloxane;
Characterizing method:
Fourier transform infrared spectroscopy: liquid sample directly drips on printing opacity salt sheet, solid sample adopts pellet technique analysis, and sweep limit is 4000-400cm
-1, wherein scanning times is 32, and resolving power is 4 cm
-1.
As shown in Figure 1, the spectrogram of methyldiethoxysilane, vinylformic acid, carboxyl silicone intermediate is contrasted: 2164 cm in methyldiethoxysilane spectrogram
-1646 cm in shown Si-H stretching vibration absorption peak and vinylformic acid spectrogram
-1shown C=C unsaturated double-bond stretching vibration charateristic avsorption band, all disappears, illustrates that addition reaction of silicon with hydrogen carries out completely in the spectrogram of carboxyl silicone intermediate.
The spectrogram of contrast carboxyl polysiloxane and carboxyl silicone intermediate: 1166 cm in carboxyl silicone intermediate spectrogram
-1, 954 cm
-1the absorption peak at place disappears in the spectrogram of carboxyl polysiloxane, proves-OC
2h
5there is hydrolysis-condensation reaction.
Can be drawn by the spectrogram of carboxyl polysiloxane: 2980cm
-1there is the stretching vibration absorption peak of-OH, 1722 cm
-1occurred the stretching vibration peak of C=O double bond, these 2 demonstrate carboxyl polysiloxane and contain carboxyl; 2960 cm
-1with 2979 cm
-1for Si-CH
3middle CH
3c-H stretching vibration absorption peak, 1266 cm
-1for Si-CH
3middle CH
3symmetric vibration absorption peak, 1086-1119 cm
-1for the stretching vibration absorption peak of Si-O-Si.
In sum, the disappearance of Si-H and C=C proves that addition reaction of silicon with hydrogen carries out completely ,-OC
2h
5the disappearance of group and the appearance of Si-O-Si structure prove intermediate generation hydrolysis-condensation reaction, and the appearance of C=O and-OH illustrates that carboxyl exists, and proves that product is target product thus.
In the present invention, carboxyl polysiloxane also can be synthesized by following steps:
Get 6mol silane containing hydrogen, 3mol vinylformic acid, the Platinic chloride that accounts for reactant total mass 0.03% add in the there-necked flask with agitator, stirred at ambient temperature evenly after, be warming up to 70 DEG C, reaction 25h terminates; Suction filtration, after underpressure distillation goes out decon and low-boiling-point substance, at 50 DEG C of vacuum-drying 24h, obtains carboxyl silicone intermediate; It is in the sulphuric acid soln of 15% that this intermediate getting half quality is slowly added drop-wise to excessive volume fraction, strictly controls rate of addition, after dropwising, reacts 3h and terminate at 20 DEG C; Be 7 by distilled water repetitive scrubbing to the pH value of washing lotion, suction filtration, at 50 DEG C of vacuum-drying 24h, namely obtains carboxyl polysiloxane; Silane containing hydrogen structural formula is
Wherein R
1, R
2for methyl or ethyl; R
3for H, alkyl or phenyl.
Getting 3.6mol silane containing hydrogen, 3mol vinylformic acid, the Platinic chloride accounting for reactant total mass 0.05% and platinum dioxide adds in the there-necked flask with agitator, after stirred at ambient temperature is even, is warming up to 90 DEG C, and reaction 20h terminates; Suction filtration, after underpressure distillation goes out decon and low-boiling-point substance, at 65 DEG C of vacuum-drying 24h, obtains carboxyl silicone intermediate; It is in the sulphuric acid soln of 60% that this intermediate getting half quality is slowly added drop-wise to excessive volume fraction, strictly controls rate of addition, after dropwising, reacts 1h and terminate at 40 DEG C; Be 7 by distilled water repetitive scrubbing to the pH value of washing lotion, suction filtration, at 65 DEG C of vacuum-drying 24h, namely obtains carboxyl polysiloxane; Silane containing hydrogen structural formula is
Wherein R
1, R
2for methyl or ethyl; R
3for H, alkyl or phenyl.
Embodiment 2: the synthesis of single guanidine compound
Get 404.265g(1.5mol) stearylamine, 108.09g (1.8mol) Glacial acetic acid is in in the there-necked flask of agitator, 110 DEG C are warming up to after mixing, to stir and bleed down (water pump) drips 94.5g(2.25mol) cyanamide, maintaining temperature of reaction is 110 DEG C; After dropwising, continue reaction 30 min, stop heating, cooling; Add the water of 2 times of volumes, heating for dissolving, by sodium hydroxide adjust ph about 10, leave standstill, use the water dissolution of 2 times of volumes after separating upper strata material again, heating in water bath, carry out regulation system pH value to 7 with the acetum that Glacial acetic acid preparation quality mark is 36%, leave standstill and separate product, rotary evaporation final vacuum is dry; Single guanidine compound is obtained with ethyl alcohol recrystallization;
Characterizing method:
Fourier transform infrared spectroscopy: liquid sample directly drips on printing opacity salt sheet, solid sample adopts pellet technique analysis, and sweep limit is 4000-400 cm
-1, wherein scanning times is 32, and resolving power is 4 cm
-1.
As seen from Figure 2,1662.64 cm
-1for NH
2scissors flexural vibration absorption peak, 1620 cm
-1for the stretching vibration absorption peak of C=N, 1471cm
-1, 997 cm
-1, 770 cm
-1be respectively angle absorption peak outside the asymmetrical stretching vibration absorption peak of NCN key, symmetric vibration absorption peak and face, prove that product is target product thus.
In the present invention, single guanidine compound also can be synthesized by following steps:
Get 1mol hexadecylamine or other alkyl amine, 1.5mol Glacial acetic acid in in the there-necked flask of agitator, be warming up to 100 DEG C after mixing, to stir and bleed down (water pump) drips 2mol cyanamide, maintaining temperature of reaction is 100 DEG C; After dropwising, continue reaction 40 min, stop heating, cooling; Add the water of 2 times of volumes, heating for dissolving, by sodium hydroxide adjust ph to 13, leave standstill, use the water dissolution of 2 times of volumes after separating upper strata material again, heating in water bath, carry out regulation system pH value to 7 with the acetum that Glacial acetic acid preparation quality mark is 36%, leave standstill and separate product, rotary evaporation final vacuum is dry; With Gossypol recrystallized from chloroform, obtain single guanidine compound.
Get 1mol alkylamine, 1.3mol Glacial acetic acid in in the there-necked flask of agitator, be warming up to 130 DEG C after mixing, to stir and bleed down (water pump) drips 1.8mol cyanamide, maintaining temperature of reaction is 130 DEG C; After dropwising, continue reaction 20min, stop heating, cooling; Add the water of 2 times of volumes, heating for dissolving, by sodium hydroxide adjust ph to 12, leave standstill, use the water dissolution of 2 times of volumes after separating upper strata material again, heating in water bath, carry out regulation system pH value to 7 with the acetum that Glacial acetic acid preparation quality mark is 36%, leave standstill and separate product, rotary evaporation final vacuum is dry; With acetone recrystallization, obtain single guanidine compound.
Embodiment 3: carboxyl polysiloxane and single guanidine compound condensation reaction
The carboxyl-content being recorded carboxyl polysiloxane by acid base titration is 7.60 mmol/g;
Getting 131.58g carboxyl polysiloxane, 404.3g(1.3mol) single guanidine compound, the chloro-I-hydroxybenzotriazole of 286.57g (1.69mol) 6-(6-Cl-HOBt) add and be equipped with in the there-necked flask of agitator, add a certain amount of acetic acid ethyl dissolution, be cooled to 1 DEG C; Slow dropping contains the ethyl acetate solution (concentration of triethylamine is 2.5mmol/10ml) of 157.86g (1.56mol) triethylamine, naturally room temperature is warming up to, stirring reaction 12h, filter, by ethyl acetate washing also pressure reducing and steaming ethyl acetate, obtain trevira antibacterial hydrophobic recombiner.
Characterizing method:
Fourier transform infrared spectroscopy: liquid sample directly drips on printing opacity salt sheet, solid sample adopts pellet technique analysis, and sweep limit is 4000-400 cm
-1, wherein scanning times is 32, and resolving power is 4 cm
-1.
Can be drawn by comparison diagram 1, Fig. 2, Fig. 3: carboxyl polysiloxane infrared spectrum 2980cm in Fig. 1
-1shown in-OH stretching vibration absorption peak disappear in figure 3, single guanidine compound infrared spectrum 1662.64 cm in Fig. 2
-1shown NH
2vibration absorption peak disappear in figure 3, prove that carboxyl and guanidine radicals react thus; Carboxyl polysiloxane infrared spectrum 1086-1119 cm in Fig. 1
-1the characteristic peaks such as shown Si-O-Si stretching vibration absorption peak still exist in figure 3, single guanidine compound infrared spectrum 1620 cm in Fig. 2
-1the characteristic peaks such as shown C=N stretching vibration absorption peak still exist in figure 3, prove that product is target product.
By this recombiner with 3.5% addition add in silicone oil, two roads for trevira oil in operation.The temperature of relaxation heat setting 170 DEG C, the time of relaxation heat setting is 30min.
Succusion is adopted to measure its anti-microbial property; Utilize and adopt German Data physics company OCA40Micro model video contact angle measuring instrument to carry out contact angle test sign hydrophobic function: test under the condition of 20 DEG C, the water yield 2 μ l dripped, rate of addition 1 μ l/s, the test of static contact angle is completed in 10 s after contact, repeat 10 times, average.
Test result is shown in Table 1.
Table 1 antibacterial fiber test result
In the present invention, trevira antibacterial hydrophobic recombiner also can be obtained by following steps:
The carboxyl-content being recorded carboxyl polysiloxane by acid base titration is 7.60 mmol/g;
Get 131.58g carboxyl polysiloxane, the mono-guanidine compound of 1.2mol, 1.44 mol I-hydroxybenzotriazole (HOBt) (promotor) add and be equipped with in the there-necked flask of agitator, (solvent a) dissolves, and is cooled to 0 DEG C to add a certain amount of tetrahydrofuran (THF); Slow dropping contains 1.8mol N, (solvent is solution (N a) for the tetrahydrofuran (THF) of N-dicyclohexylcarbodiimide (DCC) (straight chain bonding reagent), the concentration of N-dicyclohexylcarbodiimide is 1.5mmol/10ml), naturally room temperature is warming up to, stirring reaction 2h, filter, with ethyl acetate washing also pressure reducing and steaming tetrahydrofuran (THF), obtain trevira antibacterial hydrophobic recombiner.
The carboxyl-content being recorded carboxyl polysiloxane by acid base titration is 7.60 mmol/g;
Get 131.58g carboxyl polysiloxane, the mono-guanidine compound of 1.5mol, 2.25mol1-hydroxyl-7-azepine benzotriazole (HOAt) or 4-N, N-Dimethylamino pyridine (DMAP) adds and is equipped with in the there-necked flask of agitator, add a certain amount of methylene dichloride to dissolve, be cooled to 5 DEG C; Slow dropping contains the dichloromethane solution (concentration of 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride is 5mmol/10ml) of 1.95mol 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDCI), naturally room temperature is warming up to, stirring reaction 2h, filter, by washed with dichloromethane and pressure reducing and steaming methylene dichloride, obtain trevira antibacterial hydrophobic recombiner.
In above-described embodiment, straight chain bonding reagent can adopt N, the one in N-dicyclohexylcarbodiimide, triethylamine, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, N, N-DIC, phosphinylidyne diimidazole; Promotor can adopt the one in the chloro-I-hydroxybenzotriazole of I-hydroxybenzotriazole, 6-, 1-hydroxyl-7-azepine benzotriazole, 4-N, N-Dimethylamino pyridine; Solvent a can adopt the one in tetrahydrofuran (THF), ethyl acetate, methylene dichloride, DMF.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (3)
1. a trevira preparation method for antibacterial hydrophobic recombiner, is characterized in that comprising following processing step:
1) synthesis of carboxyl polysiloxane: described carboxyl polysiloxane is generated by silane containing hydrogen and vinylformic acid;
2) preparation of single guanidine compound: add alkylamine and Glacial acetic acid respectively in the there-necked flask having agitator, is warming up to 100 ~ 130 DEG C after mixing, stir and lower dropping cyanamide of bleeding, and maintaining temperature of reaction is 110 ~ 130 DEG C; After dropwising, continue reaction 20 ~ 40 min, stop heating, cooling; Add the water of 2 times of volumes, heating for dissolving, with sodium hydroxide adjust ph to 10 ~ 13, leave standstill, after separating upper strata material, use the water dissolution of 2 times of volumes again, heating in water bath, carry out regulation system pH value to 7 with the acetum that Glacial acetic acid preparation quality mark is 36%, leave standstill and separate product, rotary evaporation final vacuum is dry, with solvent c recrystallization, obtain single guanidine compound; Described cyanamide and the molar ratio of alkylamine are 1.5:1 ~ 2:1; Described Glacial acetic acid and the molar ratio of alkylamine are 1.2:1 ~ 1.5:1, and described solvent c is ethanol, chloroform or acetone;
3) carboxyl polysiloxane and single guanidine compound condensation reaction:
Carboxyl polysiloxane, single guanidine compound, promotor adding are equipped with in the there-necked flask of agitator, add solvent a and dissolve, be cooled to 0 ~ 5 DEG C; Slow dropping contains the solvent a of straight chain bonding reagent, is naturally warming up to room temperature, stirring reaction 2 ~ 24h, filters with solvent a washing and pressure reducing and steaming solvent a, obtains trevira antibacterial hydrophobic recombiner;
Described carboxyl polysiloxane and the molar ratio of single guanidine compound are determined according to the hydroxy radical content of carboxyl polysiloxane: n(COOH): n (single guanidine compound) is 1:1.2 ~ 1:1.5; Described straight chain bonding reagent and the molar ratio of single guanidine compound are 1.2:1 ~ 1.5:1; The molar ratio of described promotor and single guanidine compound is 1.2:1 ~ 1.5:1;
Above-mentioned straight chain bonding reagent is the one in N, N-dicyclohexylcarbodiimide, triethylamine, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, N, N-DIC, phosphinylidyne diimidazole;
Above-mentioned promotor is the one in I-hydroxybenzotriazole, the chloro-I-hydroxybenzotriazole of 6-, 1-hydroxyl-7-azepine benzotriazole, 4-N, N-Dimethylamino pyridine;
Above-mentioned solvent a is the one in tetrahydrofuran (THF), ethyl acetate, methylene dichloride, DMF.
2. the preparation method of a kind of trevira antibacterial hydrophobic recombiner as claimed in claim 1, is characterized in that the described concentration containing straight chain bonding reagent in the solvent a of straight chain bonding reagent is 1.5 ~ 5mmol/10ml.
3. the preparation method of a kind of trevira antibacterial hydrophobic recombiner as claimed in claim 1, is characterized in that described carboxyl polysiloxane obtains especially by following steps:
Add in the there-necked flask with agitator by silane containing hydrogen, vinylformic acid, platinum based catalyst, after stirred at ambient temperature is even, be warming up to 70 ~ 90 DEG C, reaction 20 ~ 25h terminates; Suction filtration, underpressure distillation at 50 ~ 65 DEG C of vacuum-drying 24h, obtains carboxyl silicone intermediate after removing impurity and low-boiling-point substance; Getting this intermediate appropriate is slowly added drop-wise in excessive solution b, controls rate of addition, after dropwising, reacts 1 ~ 3h and terminate at 20 ~ 40 DEG C; Be 7 by distilled water repetitive scrubbing to the pH value of washing lotion, suction filtration, at 50 ~ 65 DEG C of vacuum-drying 24h, obtains carboxyl polysiloxane;
Described silane containing hydrogen has following structure:
Wherein R
1, R
2for methyl or ethyl; R
3for H, alkyl or phenyl;
Described platinum based catalyst is the one of Platinic chloride or platinum dioxide or two kinds;
The sulphuric acid soln of described solution b to be volume fraction be 15-60%;
Described silane containing hydrogen and acrylic acid molar ratio are 1.2:1 ~ 2:1; The quality that feeds intake of platinum based catalyst is 0.01% ~ 0.05% of reactant total mass.
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| CN104131468A (en) * | 2014-08-08 | 2014-11-05 | 南雄鼎成化工有限公司 | Preparation method and application of super-hydrophobic antibacterial finishing agent for cotton fabrics |
| US20170175324A1 (en) * | 2015-12-16 | 2017-06-22 | Chefdry, LLC. | Heat resistant, stain resistant, and anti-bacterial fabric and method of making same |
| CN105755822B (en) * | 2016-02-29 | 2017-11-28 | 苏州印丝特纺织数码科技有限公司 | A kind of preparation method and application of antibacterial soil-releasing finishing agent |
| CN111748098A (en) * | 2020-08-06 | 2020-10-09 | 广州市斯洛柯高分子聚合物有限公司 | A kind of amino silicone oil and preparation method thereof |
| CN114736359B (en) * | 2022-05-27 | 2023-11-14 | 广东腾业科技有限公司 | Copolyester material for itaconic acid monomer modified shampoo bottle and preparation method thereof |
| CN115961470B (en) * | 2022-12-27 | 2026-01-02 | 苍南县一创纺织有限公司 | A mildew-resistant cotton yarn and its manufacturing process |
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