CN105037665A - Titanium dioxide nanoparticle with surface grafted with polyvinyl caprolactam and preparation method of titanium dioxide nanoparticle - Google Patents

Titanium dioxide nanoparticle with surface grafted with polyvinyl caprolactam and preparation method of titanium dioxide nanoparticle Download PDF

Info

Publication number
CN105037665A
CN105037665A CN201510505267.0A CN201510505267A CN105037665A CN 105037665 A CN105037665 A CN 105037665A CN 201510505267 A CN201510505267 A CN 201510505267A CN 105037665 A CN105037665 A CN 105037665A
Authority
CN
China
Prior art keywords
particle
titanium dioxide
tio
dioxide nano
surface grafting
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510505267.0A
Other languages
Chinese (zh)
Other versions
CN105037665B (en
Inventor
唐冬雁
于在乾
冯茜
吕海涛
王旗栋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN201510505267.0A priority Critical patent/CN105037665B/en
Publication of CN105037665A publication Critical patent/CN105037665A/en
Application granted granted Critical
Publication of CN105037665B publication Critical patent/CN105037665B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention relates to a titanium dioxide nanoparticle with the surface grafted with polyvinyl caprolactam and a preparation method of the titanium dioxide nanoparticles. According to the titanium dioxide nanoparticle, the problem that existing nano-TiO2 is difficult to remove after use is solved. The titanium dioxide nanoparticle with the surface grafted with polyvinyl caprolactam is prepared from double-bond TiO2 particles, an in-situ polymerization solvent, an initiator, polyvinyl caprolactam monomers and a molecular weight control agent. The preparation method comprises the following steps: (1) carrying out surface modification on the TiO2 particles by virtue of a coupling agent to form the double-bond TiO2 particles, and dispersing the double-bond TiO2 particles into a proper solvent; and (2) adding the initiator, the monomers and the molecular weight control agent, and carrying out in-situ polymerization. The hydrophilic-hydrophobic transformation temperature of the prepared nanoparticle can be adjusted, thereby being beneficial to the extraction of the titanium dioxide nanoparticle. The titanium dioxide nanoparticle is applied to the fields of cycle use of catalysts, ionic adsorption of heavy metals, recycling of a water treatment agent as well as biomedical materials.

Description

Titanium dioxide nano-particle of a kind of surface grafting Vinylcaprolactam homopolymer and preparation method thereof
Technical field
The present invention relates to a kind of titanium dioxide nano-particle and preparation method thereof.
Background technology
Titanium dioxide (TiO 2) be the semiconductor material that a kind of chemical stability is good, nontoxic, inexpensive.Titanium dioxide nano-particle is easy to preparation, excellent adsorption.Nano-TiO 2there is most valuable optical property, all demonstrate fine development prospect in automotive industry and numerous areas.Nano-TiO 2also there is very high chemical stability, thermostability, nontoxicity, Superhydrophilic, non-migratory, and completely can with Food Contact, so be widely used in anti-ultraviolet material, weaving, photochemical catalysis catalyst, glass with clean, sunscreen, coating, ink, packaging material for food, paper industry, space industry, in lithium cell.
TiO 2permanent sterilization under the effect of light middle-ultraviolet lamp.Experiment proves, with 0.1mg/cm 3the dichloride in anatase type TiO of concentration 2pernicious HeLa cell can be killed up hill and dale, and increasing along with superoxide-dismutase (SOD) addition, TiO 2the efficiency that cancer cells is killed in photochemical catalysis also improves.All more than 98% is reached to the killing rate of bacillus subtilis black variety gemma, Pseudomonas aeruginosa, intestinal bacteria, gold-coloured staphylococci, Salmonellas, tooth branch bacterium and aspergillus; Use TiO 2photochemical catalytic oxidation advanced treatment tap water, can greatly reduce the bacterial count in water, drinks rear without mutagenesis, reaches the standard of safe drinking water; Nano-TiO is added in coating 2sterilization, antifouling, deodorizing, self-cleaning antibacterial antifouling paint can be produced, the place of intensive, the easy breeding of bacterium such as to be applied between hospital ward, Operation theatre and domestic hygiene, capable of purifying air, protect from infection, deodorizing taste removal.Effectively can to kill etc. unwanted bacteria.Nano-TiO 2can ultraviolet be absorbed, can reflect again, scatters ultraviolet, can also, through visible ray, be the ultraviolet protecting agent of superior performance, extremely rising physical shielding type.
Nano titanium oxide is little, active large due to particle diameter, can reflect, scatters ultraviolet, can absorb ultraviolet again, thus have stronger obstructing capacity to ultraviolet.Utilize nano-TiO 2the transparency and ultraviolet absorption ability also can be used as food packaging film, ink, coating, textile fabrics and filler for plastic, can organic uv absorbers be substituted, for the ageing-resistant ability of coating can be improved in coating.Result of study finds, under the effect of daylight or light middle-ultraviolet lamp, make TiO 2activate and generate the radical with high catalytic activity, can very strong photoxidation and reducing power be produced, catalysis, photodissociation can be attached to organism and the part inorganicss such as the various formaldehyde of body surface.The function purified the air of a room can be played.
As can be seen here, TiO 2in photochemical catalysis, heavy metal adsorption and ion reduction, have larger advantage, but nano level titanium dioxide is difficult to separate from water, the more little more difficult separation of particle diameter, therefore after process, in system, removing of nano titania is a stubborn problem.
Summary of the invention
The object of the invention is to solve existing nano-TiO 2the problem using rear difficulty to remove, provides titanium dioxide nano-particle of a kind of surface grafting Vinylcaprolactam homopolymer and preparation method thereof.
The titanium dioxide nano-particle of a kind of surface grafting Vinylcaprolactam homopolymer of the present invention is by the TiO with double bond 2particle, in-situ polymerization solvent, initiator, caprolactam monomer and molecular weight regulator are made; Wherein in-situ polymerization solvent be methyl-sulphoxide, one or more mixtures be mixed by any ratio in tetrahydrofuran (THF), dioxane, methyl alcohol, ethanol and ring propyl alcohol; The mass volume ratio of caprolactam monomer and in-situ polymerization solvent is 1g:5mL; Caprolactam monomer, there is the TiO of double bond 2the mass ratio of particle and initiator is 1:(0.01 ~ 1): (0.001 ~ 0.04), the add-on of molecular weight regulator is 0 ~ 0.01% of the quality of caprolactam monomer.
The preparation method of the titanium dioxide nano-particle of a kind of surface grafting Vinylcaprolactam homopolymer of the present invention, carries out in the steps below:
One, by TiO 2particle dispersion, in dehydrated alcohol, then adds trolamine, and ultrasonic disperse obtains TiO 2particle dispersion; Stir 5min by after coupling agent and deionized water mixing, then add TiO 2in particle dispersion, then adjust ph is 10, then under 65 DEG C of conditions, reacts 12h, then is separated with 6000r/min centrifugation 15 ~ 20min, gets solid formation, and 50 DEG C of oven dry, obtain the TiO with double bond 2particle; Wherein TiO 2the mass volume ratio of particle and dehydrated alcohol, trolamine is 1g:0.1mL:50mL, TiO 2the quality mol ratio of particle and coupling agent is 1g:(0.1 ~ 4mmol), the volume ratio of coupling agent and water is 1:(1.5 ~ 1.6);
Two, the TiO that step one gained has double bond is got 2particle, be scattered in in-situ polymerization solvent, then initiator, caprolactam monomer, molecular weight regulator is added, at the Water Under bath reaction 3 ~ 16h of 70 ~ 80 DEG C, then reaction product is scattered in dehydrated alcohol, leave standstill 10h, remove precipitation, then with 7000r/min centrifugation 15 ~ 20min, remove supernatant, namely complete, wherein in-situ polymerization solvent be methyl-sulphoxide, one or more mixtures be mixed by any ratio in tetrahydrofuran (THF), dioxane, methyl alcohol, ethanol, chloroform and Virahol; The mass volume ratio of caprolactam monomer and in-situ polymerization solvent is 1g:(4 ~ 6) mL; Caprolactam monomer, there is the TiO of double bond 2the mass ratio of particle and initiator is 1:(0.01 ~ 1): (0.001 ~ 0.04), the add-on of molecular weight regulator is 0 ~ 0.01% of the quality of caprolactam monomer.
Polyvinylcaprolactame (PVCL) is a kind of polymkeric substance of responsive to temperature type, there is low consolute temperature (LCST in itself and water, lowercriticalsolutiontemperature), when temperature is dissolved in water lower than PVCL during LCST, when temperature is higher than LCST, PVCL separates out in water.Carrying out coated or grafting by temperature sensing material to there being the functional particles of catalytic performance, can realize " on-off " of particle function, the transfer of particle in water-oily two-phase can be realized under temperature controls.
The double bond of caprolactam monomer used in the present invention is connected directly between in the atom N of amide group, makes the reactive behavior of monomer very low.The response temperature (VPTT) of this monomer polymerization resulting polymers, relevant with the polymerization degree in certain limit, the polymerization degree is higher, and VPTT point is lower.In the in-situ polymerization solvent selected by present embodiment, caprolactam can reach higher degrees of polymerization, and the ratio of the polymerization degree and reaction times, initiator and monomer exists certain corresponding relation.
Parent-hydrophobic the transition temperature of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer prepared by the present invention can regulate; The method of regulating rotary temperature is simple; The value of transition temperature can at the arbitrary value of 25 DEG C ~ 80 DEG C of scopes; When particle changes hydrophobic into, can Spontaneous adsorption in non-polar material surface; When particle changes into hydrophilic, again can be dissolved in water from apolar surfaces, so just be conducive to the extraction of titanium dioxide nano-particle.There is potential using value in the fields such as this particle uses in catalyst recirculation, heavy metal ion adsorbed, water conditioner recovery, bio-medical material.
Accompanying drawing explanation
Fig. 1 is the variation diagram of titanium dioxide FT-IR spectrogram before and after embodiment one surface modification; Wherein a is TiO 2particle, b is the TiO with double bond 2particle;
Fig. 2 is the variation diagram of titanium dioxide FT-IR spectrogram before and after embodiment one step 2 in-situ polymerization;
Fig. 3 is TiO in embodiment one 2the SEM photo of particle;
Fig. 4 is the TiO in embodiment one with double bond 2the SEM photo of particle;
Fig. 5 is the SEM photo of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer in embodiment one;
Fig. 6 is the phase in version of the titanium dioxide nano-particle of the surface grafting Vinylcaprolactam homopolymer that under temperature action prepared by embodiment one;
Fig. 7 is the titanium dioxide nano-particle recycling use schematic diagram of temperature action lower surface grafted polyethylene base hexanolactam.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the titanium dioxide nano-particle of a kind of surface grafting Vinylcaprolactam homopolymer of present embodiment is by the TiO with double bond 2particle, in-situ polymerization solvent, initiator, caprolactam monomer and molecular weight regulator are made; Wherein in-situ polymerization solvent be methyl-sulphoxide, one or more mixtures be mixed by any ratio in tetrahydrofuran (THF), dioxane, methyl alcohol, ethanol and ring propyl alcohol; The mass volume ratio of caprolactam monomer and in-situ polymerization solvent is 1g:5mL; Caprolactam monomer, there is the TiO of double bond 2the mass ratio of particle and initiator is 1:(0.01 ~ 1): (0.001 ~ 0.04), the add-on of molecular weight regulator is 0 ~ 0.01% of the quality of caprolactam monomer.
Polyvinylcaprolactame (PVCL) is a kind of polymkeric substance of responsive to temperature type, there is low consolute temperature (LCST in itself and water, lowercriticalsolutiontemperature), when temperature is dissolved in water lower than PVCL during LCST, when temperature is higher than LCST, PVCL separates out in water.Carrying out coated or grafting by temperature sensing material to there being the functional particles of catalytic performance, can realize " on-off " of particle function, the transfer of particle in water-oily two-phase can be realized under temperature controls.
Parent-hydrophobic the transition temperature of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer prepared by present embodiment can regulate; The method of regulating rotary temperature is simple; The value of transition temperature can at the arbitrary value of 25 DEG C ~ 80 DEG C of scopes; When particle changes hydrophobic into, can Spontaneous adsorption in non-polar material surface; When particle changes into hydrophilic, again can be dissolved in water from apolar surfaces.There is potential using value in the fields such as this particle uses in catalyst recirculation, heavy metal ion adsorbed, water conditioner recovery, bio-medical material.
Embodiment two: present embodiment and embodiment one unlike: described initiator be one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo isobutyl cyano group methane amide, azo dicyclohexyl formonitrile HCN, azo-bis-iso-dimethyl, azo diisobutyl amidine hydrochloride and azo dicyano valeric acid by arbitrarily than the mixture formed.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: described molecular weight regulator is acetylacetone cobalt or potassium ethyl xanthonate.Other is identical with embodiment one or two.
Embodiment four: the preparation method of the titanium dioxide nano-particle of a kind of surface grafting Vinylcaprolactam homopolymer of present embodiment, carries out: in the steps below one, by TiO 2particle dispersion, in dehydrated alcohol, then adds trolamine, and ultrasonic disperse obtains TiO 2particle dispersion; Stir 5min by after coupling agent and deionized water mixing, then add TiO 2in particle dispersion, then adjust ph is 10, then under 65 DEG C of conditions, reacts 12h, then is separated with 6000r/min centrifugation 15 ~ 20min, gets solid formation, and 50 DEG C of oven dry, obtain the TiO with double bond 2particle; Wherein TiO 2the mass volume ratio of particle and dehydrated alcohol, trolamine is 1g:0.1mL:50mL, TiO 2the quality mol ratio of particle and coupling agent is 1g:(0.1 ~ 4mmol), the volume ratio of coupling agent and water is 1:(1.5 ~ 1.6);
Two, the TiO that step one gained has double bond is got 2particle, be scattered in in-situ polymerization solvent, then initiator, caprolactam monomer, molecular weight regulator is added, at the Water Under bath reaction 3 ~ 16h of 70 ~ 80 DEG C, then reaction product is scattered in dehydrated alcohol, leave standstill 10h, remove precipitation, then with 7000r/min centrifugation 15 ~ 20min, remove supernatant, namely complete, wherein in-situ polymerization solvent be methyl-sulphoxide, one or more mixtures be mixed by any ratio in tetrahydrofuran (THF), dioxane, methyl alcohol, ethanol, chloroform and Virahol; The mass volume ratio of caprolactam monomer and in-situ polymerization solvent is 1g:(4 ~ 6) mL; Caprolactam monomer, there is the TiO of double bond 2the mass ratio of particle and initiator is 1:(0.01 ~ 1): (0.001 ~ 0.04), the add-on of molecular weight regulator is 0 ~ 0.01% of the quality of caprolactam monomer.
The double bond of the caprolactam monomer that present embodiment uses is connected directly between in the atom N of amide group, makes the reactive behavior of monomer very low.The response temperature (VPTT) of this monomer polymerization resulting polymers, relevant with the polymerization degree in certain limit, the polymerization degree is higher, and VPTT point is lower.In the in-situ polymerization solvent selected by present embodiment, caprolactam can reach higher degrees of polymerization, and the ratio of the polymerization degree and reaction times, initiator and monomer exists certain corresponding relation.
Embodiment five: present embodiment and embodiment four unlike: the coupling agent described in step one be one or more in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl trichloro silane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyl three tert-butoxy silane, vinyl silane tri-butyl peroxy and vinyltriacetoxy silane by arbitrarily than the mixture formed.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment and embodiment four or five unlike: step one adopts ammoniacal liquor adjust ph.Other is identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six are that one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo isobutyl cyano group methane amide, azo dicyclohexyl formonitrile HCN, azo-bis-iso-dimethyl, azo diisobutyl amidine hydrochloride and azo dicyano valeric acid are by arbitrarily than the mixture formed unlike: the initiator described in step 2.Other is identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: the molecular weight regulator described in step 2 is acetylacetone cobalt or potassium ethyl xanthonate.Other is identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: described in step 2 at the Water Under bath reaction 3 ~ 16h of 75 DEG C.Other is identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine unlike: the caprolactam monomer described in step 2 and the mass volume ratio of in-situ polymerization solvent are 1g:5mL.Other is identical with one of embodiment one to nine.
Embodiment 11: one of present embodiment and embodiment one to ten are unlike: the caprolactam monomer described in step 2, the TiO with double bond 2the mass ratio of particle and initiator is 1:0.1:0.01, and the add-on of molecular weight regulator is 0% of the quality of caprolactam monomer.Other is identical with one of embodiment one to ten.
Embodiment 12: one of present embodiment and embodiment one to ten one are unlike: the caprolactam monomer described in step 2, the TiO with double bond 2the mass ratio of particle and initiator is 1:0.05:0.01, and the add-on of molecular weight regulator is 0.01% of the quality of caprolactam monomer.Other is identical with one of embodiment one to ten one.
Embodiment 13: one of present embodiment and embodiment one to ten two are unlike: the caprolactam monomer described in step 2, the TiO with double bond 2the mass ratio of particle and initiator is 1:0.05:0.004, and the add-on of molecular weight regulator is 0.01% of the quality of caprolactam monomer.Other is identical with one of embodiment one to ten two.
Embodiment 14: one of present embodiment and embodiment one to ten three are unlike: the caprolactam monomer described in step 2, the TiO with double bond 2the mass ratio of particle and initiator is 1:0.05:0.002, and the add-on of molecular weight regulator is 0.01% of the quality of caprolactam monomer.Other is identical with one of embodiment one to ten three.
Embodiment 15: one of present embodiment and embodiment one to ten four unlike: bathing at the Water Under of 75 DEG C described in step 2 reacts 12h.Other is identical with one of embodiment one to ten four.
Beneficial effect of the present invention is verified by following examples:
Embodiment one:
The preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, is characterized in that it carries out in the steps below:
One, by 1gTiO 2particle dispersion, in 50mL dehydrated alcohol, then adds 0.1mL trolamine, ultrasonic disperse, obtains TiO 2particle dispersion; Stir 5min by after 0.94mL vinyltriethoxysilane and the mixing of 1.5mL deionized water, then add TiO 2in particle dispersion, then be 10 by ammoniacal liquor adjust ph, then under 65 DEG C of conditions, react 12h, then be separated with 6000r/min centrifugation 15 ~ 20min, get solid formation, 50 DEG C of oven dry, obtain the TiO with double bond 2particle;
Two, the TiO that 0.1g step one gained has double bond is got 2particle, be scattered in 5mL tetrahydrofuran (THF), then 0.01g 2,2'-Azobis(2,4-dimethylvaleronitrile) and 1g caprolactam monomer is added, at the Water Under bath reaction 12h of 75 DEG C, then reaction product is scattered in dehydrated alcohol, leaves standstill 10h, remove precipitation, then with 7000r/min centrifugation 20min, remove supernatant, namely complete.
Before and after the present embodiment step one surface modification, the change of titanium dioxide FT-IR spectrogram as shown in Figure 1; Wherein a is TiO 2particle, b is the TiO with double bond 2particle; Can see in the drawings after coupling agent is modified, 1000-1250cm -1the absorption peak at place can belong to Si-O-Ti and Si-O, 1578cm -1charateristic avsorption band can belong to double bond, through repeatedly still existing with after washing with alcohol.Show coupling agent and TiO 2particle combines firmly.
Before and after the present embodiment step 2 in-situ polymerization, the change of titanium dioxide FT-IR spectrogram as shown in Figure 2, and a is the TiO with double bond 2particle, b is the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer; As seen from Figure 2,1081cm in figure -1and 1199cm -1the absorption peak at place can belong to the vibration of C-N bond bending, 1479cm -1the absorption peak at place can be attributed to the stretching vibration of c h bond.2923cm -1and 2858cm -1the absorption peak at place can be attributed to the stretching vibration of methyl c h bond.1633cm -1the absorption peak at place corresponds to C=O stretching vibration.TiO after being separated 2particle surface still can detect the charateristic avsorption band of Polyvinylcaprolactame, shows that PVCL grafts on TiO 2particle surface.Fig. 3 is TiO in the present embodiment 2the SEM photo of particle; Fig. 4 is the TiO in the present embodiment with double bond 2the SEM photo of particle; Fig. 5 is the SEM photo of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer in the present embodiment; Comparison diagram 3,4 and 5 can find, TiO 2particle surface covers layer of polyethylene base hexanamide.
Under temperature action, the phase diagram of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer prepared by the present embodiment as shown in Figure 6; Sample bottle photo shows, and when temperature is lower than (LCST of PVCL) during Volume-phase transition temperature, particle is dispersed in water well; When being heated to temperature and being elevated to more than Volume-phase transition temperature, particle is separated out from water.Schematic diagram depicts the change that particle microtexture before and after Volume-phase transition occurs.The titanium dioxide nano-particle recycling use schematic diagram of temperature action lower surface grafted polyethylene base hexanolactam as shown in Figure 7, time more than raised temperature to Volume-phase transition temperature, particle Spontaneous adsorption, in apolar surfaces, can be separated easily from system; When temperature is reduced to below Volume-phase transition temperature, particle is scattered in water again from apolar surfaces.The recycle of particle can be realized.
Embodiment two:
The preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, is characterized in that it carries out in the steps below:
One, by 1gTiO 2particle dispersion, in 50mL dehydrated alcohol, then adds 0.1mL trolamine, ultrasonic disperse, obtains TiO 2particle dispersion; Stir 5min by after 0.94mL vinyltriethoxysilane and the mixing of 1.5mL deionized water, then add TiO 2in particle dispersion, then be 10 by ammoniacal liquor adjust ph, then under 65 DEG C of conditions, react 12h, then be separated with 6000r/min centrifugation 15 ~ 20min, get solid formation, 50 DEG C of oven dry, obtain the TiO with double bond 2particle;
Two, the TiO that 0.1g step one gained has double bond is got 2particle, be scattered in 5mL ethanol, then 0.01g 2,2'-Azobis(2,4-dimethylvaleronitrile) and 1g caprolactam monomer is added, at the Water Under bath reaction 12h of 75 DEG C, then reaction product is scattered in dehydrated alcohol, leaves standstill 10h, remove precipitation, then with 7000r/min centrifugation 20min, remove supernatant, namely complete.
Embodiment three:
The preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, is characterized in that it carries out in the steps below:
One, by 1gTiO 2particle dispersion, in 50mL dehydrated alcohol, then adds 0.1mL trolamine, ultrasonic disperse, obtains TiO 2particle dispersion; Stir 5min by after 0.94mL vinyltriethoxysilane and the mixing of 1.5mL deionized water, then add TiO 2in particle dispersion, then be 10 by ammoniacal liquor adjust ph, then under 65 DEG C of conditions, react 12h, then be separated with 6000r/min centrifugation 15 ~ 20min, get solid formation, 50 DEG C of oven dry, obtain the TiO with double bond 2particle;
Two, the TiO that 0.1g step one gained has double bond is got 2particle, be scattered in 5mL methyl alcohol, then 0.01g 2,2'-Azobis(2,4-dimethylvaleronitrile) and 1g caprolactam monomer is added, at the Water Under bath reaction 12h of 75 DEG C, then reaction product is scattered in dehydrated alcohol, leaves standstill 10h, remove precipitation, then with 7000r/min centrifugation 20min, remove supernatant, namely complete.
Embodiment four:
The preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, is characterized in that it carries out in the steps below:
One, by 1gTiO 2particle dispersion, in 50mL dehydrated alcohol, then adds 0.1mL trolamine, ultrasonic disperse, obtains TiO 2particle dispersion; Stir 5min by after 0.94mL vinyltriethoxysilane and the mixing of 1.5mL deionized water, then add TiO 2in particle dispersion, then be 10 by ammoniacal liquor adjust ph, then under 65 DEG C of conditions, react 12h, then be separated with 6000r/min centrifugation 15 ~ 20min, get solid formation, 50 DEG C of oven dry, obtain the TiO with double bond 2particle;
Two, the TiO that 0.1g step one gained has double bond is got 2particle, be scattered in 5mL dioxane, then 0.01g 2,2'-Azobis(2,4-dimethylvaleronitrile) and 1g caprolactam monomer is added, at the Water Under bath reaction 12h of 75 DEG C, then reaction product is scattered in dehydrated alcohol, leaves standstill 10h, remove precipitation, then with 7000r/min centrifugation 20min, remove supernatant, namely complete.
Embodiment five:
The preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, is characterized in that it carries out in the steps below:
One, by 1gTiO 2particle dispersion, in 50mL dehydrated alcohol, then adds 0.1mL trolamine, ultrasonic disperse, obtains TiO 2particle dispersion; Stir 5min by after 0.94mL vinyltriethoxysilane and the mixing of 1.5mL deionized water, then add TiO 2in particle dispersion, then be 10 by ammoniacal liquor adjust ph, then under 65 DEG C of conditions, react 12h, then be separated with 6000r/min centrifugation 15 ~ 20min, get solid formation, 50 DEG C of oven dry, obtain the TiO with double bond 2particle;
Two, the TiO that 0.1g step one gained has double bond is got 2particle, be scattered in 5mL Virahol, then 0.01g 2,2'-Azobis(2,4-dimethylvaleronitrile) and 1g caprolactam monomer is added, at the Water Under bath reaction 12h of 75 DEG C, then reaction product is scattered in dehydrated alcohol, leaves standstill 10h, remove precipitation, then with 7000r/min centrifugation 20min, remove supernatant, namely complete.
Embodiment six:
The preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, is characterized in that it carries out in the steps below:
One, by 1gTiO 2particle dispersion, in 50mL dehydrated alcohol, then adds 0.1mL trolamine, ultrasonic disperse, obtains TiO 2particle dispersion; Stir 5min by after 0.94mL vinyltriethoxysilane and the mixing of 1.5mL deionized water, then add TiO 2in particle dispersion, then be 10 by ammoniacal liquor adjust ph, then under 65 DEG C of conditions, react 12h, then be separated with 6000r/min centrifugation 15 ~ 20min, get solid formation, 50 DEG C of oven dry, obtain the TiO with double bond 2particle;
Two, the TiO that 0.1g step one gained has double bond is got 2particle, be scattered in 5mL chloroform, then 0.01g 2,2'-Azobis(2,4-dimethylvaleronitrile) and 1g caprolactam monomer is added, at the Water Under bath reaction 12h of 75 DEG C, then reaction product is scattered in dehydrated alcohol, leaves standstill 10h, remove precipitation, then with 7000r/min centrifugation 20min, remove supernatant, namely complete.
Table 1
The phase transition temperature of the titanium dioxide nano-particle of the surface grafting Vinylcaprolactam homopolymer prepared by embodiment one ~ six as shown in Table 1, as shown in Table 1, when other conditions are identical, the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer prepared by different in-situ polymerization solvent possesses different phase transition temperatures, and this is the impact due to in-situ polymerization solvent polarity.
Embodiment seven: the preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, is characterized in that it carries out in the steps below:
One, by 1gTiO 2particle dispersion, in 50mL dehydrated alcohol, then adds 0.1mL trolamine, ultrasonic disperse, obtains TiO 2particle dispersion; Stir 5min by after 0.94mL vinyltriethoxysilane and the mixing of 1.5mL deionized water, then add TiO 2in particle dispersion, then be 10 by ammoniacal liquor adjust ph, then under 65 DEG C of conditions, react 12h, then be separated with 6000r/min centrifugation 15 ~ 20min, get solid formation, 50 DEG C of oven dry, obtain the TiO with double bond 2particle;
Two, the TiO that 0.05g step one gained has double bond is got 2particle, be scattered in 5mL chloroform, then 0.01g Diisopropyl azodicarboxylate, 0.0001g acetylacetone cobalt and 1g caprolactam monomer is added, at the Water Under bath reaction 12h of 75 DEG C, then reaction product is scattered in dehydrated alcohol, leaves standstill 10h, remove precipitation, then with 7000r/min centrifugation 20min, remove supernatant, namely complete.
Embodiment eight: the preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, is characterized in that it carries out in the steps below:
One, by 1gTiO 2particle dispersion, in 50mL dehydrated alcohol, then adds 0.1mL trolamine, ultrasonic disperse, obtains TiO 2particle dispersion; Stir 5min by after 0.94mL vinyltriethoxysilane and the mixing of 1.5mL deionized water, then add TiO 2in particle dispersion, then be 10 by ammoniacal liquor adjust ph, then under 65 DEG C of conditions, react 12h, then be separated with 6000r/min centrifugation 15 ~ 20min, get solid formation, 50 DEG C of oven dry, obtain the TiO with double bond 2particle;
Two, the TiO that 0.05g step one gained has double bond is got 2particle, be scattered in 5mL chloroform, then 0.004g Diisopropyl azodicarboxylate, 0.0001g acetylacetone cobalt and 1g caprolactam monomer is added, at the Water Under bath reaction 12h of 75 DEG C, then reaction product is scattered in dehydrated alcohol, leaves standstill 10h, remove precipitation, then with 7000r/min centrifugation 20min, remove supernatant, namely complete.
Embodiment nine: the preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, is characterized in that it carries out in the steps below:
One, by 1gTiO 2particle dispersion, in 50mL dehydrated alcohol, then adds 0.1mL trolamine, ultrasonic disperse, obtains TiO 2particle dispersion; Stir 5min by after 0.94mL vinyltriethoxysilane and the mixing of 1.5mL deionized water, then add TiO 2in particle dispersion, then be 10 by ammoniacal liquor adjust ph, then under 65 DEG C of conditions, react 12h, then be separated with 6000r/min centrifugation 15 ~ 20min, get solid formation, 50 DEG C of oven dry, obtain the TiO with double bond 2particle;
Two, the TiO that 0.05g step one gained has double bond is got 2particle, be scattered in 5mL chloroform, then 0.002g Diisopropyl azodicarboxylate, 0.0001g acetylacetone cobalt and 1g caprolactam monomer is added, at the Water Under bath reaction 12h of 75 DEG C, then reaction product is scattered in dehydrated alcohol, leaves standstill 10h, remove precipitation, then with 7000r/min centrifugation 20min, remove supernatant, namely complete.
The phase transition temperature of the titanium dioxide nano-particle of the prepared surface grafting Vinylcaprolactam homopolymer of embodiment seven ~ nine as shown in Table 2, as shown in Table 2, when other conditions are identical, initiator possesses different phase transition temperatures from the different mass of monomer than the titanium dioxide nano-particle of the surface grafting Vinylcaprolactam homopolymer prepared, this is owing to being polyreaction termination mode, this radical life is that coupling stops, more polymolecular amount is higher for free radical, and the higher phase transition temperature of molecular weight is higher.
Table 2
Initiator monomer weight ratio 0.01 0.004 0.002
Phase transition temperature DEG C 32.6 35.2 36.0
Embodiment ten: the preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, is characterized in that it carries out in the steps below:
Three, by 1gTiO 2particle dispersion, in 50mL dehydrated alcohol, then adds 0.1mL trolamine, ultrasonic disperse, obtains TiO 2particle dispersion; Stir 5min by after 0.94mL vinyltriethoxysilane and the mixing of 1.5mL deionized water, then add TiO 2in particle dispersion, then be 10 by ammoniacal liquor adjust ph, then under 65 DEG C of conditions, react 12h, then be separated with 6000r/min centrifugation 15 ~ 20min, get solid formation, 50 DEG C of oven dry, obtain the TiO with double bond 2particle;
Four, the TiO that 0.05g step one gained has double bond is got 2particle, be scattered in 5mL chloroform, then 0.01g Diisopropyl azodicarboxylate and 1g caprolactam monomer is added, at the Water Under bath reaction 12h of 75 DEG C, then reaction product is scattered in dehydrated alcohol, leaves standstill 10h, remove precipitation, then with 7000r/min centrifugation 20min, remove supernatant, namely complete.
Embodiment 11: the preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, is characterized in that it carries out in the steps below:
Three, by 1gTiO 2particle dispersion, in 50mL dehydrated alcohol, then adds 0.1mL trolamine, ultrasonic disperse, obtains TiO 2particle dispersion; Stir 5min by after 0.94mL vinyltriethoxysilane and the mixing of 1.5mL deionized water, then add TiO 2in particle dispersion, then be 10 by ammoniacal liquor adjust ph, then under 65 DEG C of conditions, react 12h, then be separated with 6000r/min centrifugation 15 ~ 20min, get solid formation, 50 DEG C of oven dry, obtain the TiO with double bond 2particle;
Four, the TiO that 0.05g step one gained has double bond is got 2particle, be scattered in 5mL chloroform, then 0.004g Diisopropyl azodicarboxylate and 1g caprolactam monomer is added, at the Water Under bath reaction 12h of 75 DEG C, then reaction product is scattered in dehydrated alcohol, leaves standstill 10h, remove precipitation, then with 7000r/min centrifugation 20min, remove supernatant, namely complete.
Embodiment 12: the preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, is characterized in that it carries out in the steps below:
Three, by 1gTiO 2particle dispersion, in 50mL dehydrated alcohol, then adds 0.1mL trolamine, ultrasonic disperse, obtains TiO 2particle dispersion; Stir 5min by after 0.94mL vinyltriethoxysilane and the mixing of 1.5mL deionized water, then add TiO 2in particle dispersion, then be 10 by ammoniacal liquor adjust ph, then under 65 DEG C of conditions, react 12h, then be separated with 6000r/min centrifugation 15 ~ 20min, get solid formation, 50 DEG C of oven dry, obtain the TiO with double bond 2particle;
Four, the TiO that 0.05g step one gained has double bond is got 2particle, be scattered in 5mL chloroform, then 0.002g Diisopropyl azodicarboxylate and 1g caprolactam monomer is added, at the Water Under bath reaction 12h of 75 DEG C, then reaction product is scattered in dehydrated alcohol, leaves standstill 10h, remove precipitation, then with 7000r/min centrifugation 20min, remove supernatant, namely complete.
The phase transition temperature of the titanium dioxide nano-particle of the surface grafting Vinylcaprolactam homopolymer prepared by embodiment ten ~ 12 as shown in Table 3, as shown in Table 3, when other conditions are identical, the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer prepared by the differential responses time possesses different phase transition temperatures, this is that molecular weight is more and more higher owing to passing in time.

Claims (10)

1. a titanium dioxide nano-particle for surface grafting Vinylcaprolactam homopolymer, is characterized in that it is by the TiO with double bond 2particle, in-situ polymerization solvent, initiator, caprolactam monomer and molecular weight regulator are made; Wherein in-situ polymerization solvent be methyl-sulphoxide, one or more mixtures be mixed by any ratio in tetrahydrofuran (THF), dioxane, methyl alcohol, ethanol and ring propyl alcohol; The mass volume ratio of caprolactam monomer and in-situ polymerization solvent is 1g:5mL; Caprolactam monomer, there is the TiO of double bond 2the mass ratio of particle and initiator is 1:(0.01 ~ 1): (0.001 ~ 0.04), the add-on of molecular weight regulator is 0 ~ 0.01% of the quality of caprolactam monomer.
2. the titanium dioxide nano-particle of a kind of surface grafting Vinylcaprolactam homopolymer according to claim 1, is characterized in that described initiator is that one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo isobutyl cyano group methane amide, azo dicyclohexyl formonitrile HCN, azo-bis-iso-dimethyl, azo diisobutyl amidine hydrochloride and azo dicyano valeric acid are by arbitrarily than the mixture formed.
3. the titanium dioxide nano-particle of a kind of surface grafting Vinylcaprolactam homopolymer according to claim 1, is characterized in that described molecular weight regulator is acetylacetone cobalt or potassium ethyl xanthonate.
4. prepare the method for the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer according to claim 1, it is characterized in that it carries out in the steps below:
One, by TiO 2particle dispersion, in dehydrated alcohol, then adds trolamine, and ultrasonic disperse obtains TiO 2particle dispersion; Stir 5min by after coupling agent and deionized water mixing, then add TiO 2in particle dispersion, then adjust ph is 10, then under 65 DEG C of conditions, reacts 12h, then is separated with 6000r/min centrifugation 15 ~ 20min, gets solid formation, and 50 DEG C of oven dry, obtain the TiO with double bond 2particle; Wherein TiO 2the mass volume ratio of particle and dehydrated alcohol, trolamine is 1g:0.1mL:50mL, TiO 2the quality mol ratio of particle and coupling agent is 1g:(0.1 ~ 4mmol), the volume ratio of coupling agent and water is 1:(1.5 ~ 1.6);
Two, the TiO that step one gained has double bond is got 2particle, be scattered in in-situ polymerization solvent, then initiator, caprolactam monomer, molecular weight regulator is added, at the Water Under bath reaction 3 ~ 16h of 70 ~ 80 DEG C, then reaction product is scattered in dehydrated alcohol, leave standstill 10h, remove precipitation, then with 7000r/min centrifugation 15 ~ 20min, remove supernatant, namely complete, wherein in-situ polymerization solvent be methyl-sulphoxide, one or more mixtures be mixed by any ratio in tetrahydrofuran (THF), dioxane, methyl alcohol, ethanol, chloroform and Virahol; The mass volume ratio of caprolactam monomer and in-situ polymerization solvent is 1g:(4 ~ 6) mL; Caprolactam monomer, there is the TiO of double bond 2the mass ratio of particle and initiator is 1:(0.01 ~ 1): (0.001 ~ 0.04), the add-on of molecular weight regulator is 0 ~ 0.01% of the quality of caprolactam monomer.
5. the preparation method of the titanium dioxide nano-particle of a kind of surface grafting Vinylcaprolactam homopolymer according to claim 4, the coupling agent that it is characterized in that described in step one is that one or more in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl trichloro silane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyl three tert-butoxy silane, vinyl silane tri-butyl peroxy and vinyltriacetoxy silane are by arbitrarily than the mixture formed.
6. the preparation method of the titanium dioxide nano-particle of a kind of surface grafting Vinylcaprolactam homopolymer according to claim 4, is characterized in that described step one adopts ammoniacal liquor adjust ph.
7. the preparation method of the titanium dioxide nano-particle of a kind of surface grafting Vinylcaprolactam homopolymer according to claim 4, the initiator that it is characterized in that described in step 2 is that one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo isobutyl cyano group methane amide, azo dicyclohexyl formonitrile HCN, azo-bis-iso-dimethyl, azo diisobutyl amidine hydrochloride and azo dicyano valeric acid are by arbitrarily than the mixture formed.
8. the preparation method of the titanium dioxide nano-particle of a kind of surface grafting Vinylcaprolactam homopolymer according to claim 4, is characterized in that the molecular weight regulator described in step 2 is acetylacetone cobalt or potassium ethyl xanthonate.
9. the preparation method of the titanium dioxide nano-particle of a kind of surface grafting Vinylcaprolactam homopolymer according to claim 4, it is characterized in that described in step 2 at the Water Under bath reaction 3 ~ 16h of 75 DEG C.
10. the preparation method of the titanium dioxide nano-particle of a kind of surface grafting Vinylcaprolactam homopolymer according to claim 4, is characterized in that the mass volume ratio of caprolactam monomer described in step 2 and in-situ polymerization solvent is 1g:5mL.
CN201510505267.0A 2015-08-17 2015-08-17 A kind of titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer and preparation method thereof Active CN105037665B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510505267.0A CN105037665B (en) 2015-08-17 2015-08-17 A kind of titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510505267.0A CN105037665B (en) 2015-08-17 2015-08-17 A kind of titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer and preparation method thereof

Publications (2)

Publication Number Publication Date
CN105037665A true CN105037665A (en) 2015-11-11
CN105037665B CN105037665B (en) 2017-07-28

Family

ID=54444666

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510505267.0A Active CN105037665B (en) 2015-08-17 2015-08-17 A kind of titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105037665B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106084364A (en) * 2016-07-07 2016-11-09 宁国九鼎橡塑制品有限公司 A kind of ball stud dust cover and preparation method thereof
CN110894268A (en) * 2019-12-04 2020-03-20 杭州传化精细化工有限公司 Nanoparticle type in-situ initiator and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101157745A (en) * 2007-09-11 2008-04-09 浙江大学 Method for grafting polymer on inorganic material surface
CN102320654A (en) * 2011-06-22 2012-01-18 哈尔滨工业大学 Surface grafting gathers the TiO of (N-NSC 11448) 2Nanoparticle and preparation method thereof
WO2014005753A1 (en) * 2012-07-06 2014-01-09 Akzo Nobel Coatings International B.V. Method for producing a nanocomposite dispersion comprising composite particles|of inorganic nanoparticles and organic polymers
CN103709340A (en) * 2013-12-29 2014-04-09 哈尔滨工业大学 Method for grafting poly(N-isopropylacrylamide) on surface of powdered activated carbon
CN104017145A (en) * 2014-06-16 2014-09-03 哈尔滨工业大学 Preparation method and application of temperature response material SiO2-poly(N-isopropyl acrylamide)
CN104475166A (en) * 2014-12-16 2015-04-01 天津工业大学 Self-cleaning titanium dioxide composite type photocatalyst

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101157745A (en) * 2007-09-11 2008-04-09 浙江大学 Method for grafting polymer on inorganic material surface
CN102320654A (en) * 2011-06-22 2012-01-18 哈尔滨工业大学 Surface grafting gathers the TiO of (N-NSC 11448) 2Nanoparticle and preparation method thereof
WO2014005753A1 (en) * 2012-07-06 2014-01-09 Akzo Nobel Coatings International B.V. Method for producing a nanocomposite dispersion comprising composite particles|of inorganic nanoparticles and organic polymers
CN103709340A (en) * 2013-12-29 2014-04-09 哈尔滨工业大学 Method for grafting poly(N-isopropylacrylamide) on surface of powdered activated carbon
CN104017145A (en) * 2014-06-16 2014-09-03 哈尔滨工业大学 Preparation method and application of temperature response material SiO2-poly(N-isopropyl acrylamide)
CN104475166A (en) * 2014-12-16 2015-04-01 天津工业大学 Self-cleaning titanium dioxide composite type photocatalyst

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
MIKKO KARESOJA等: "Mesoporous Silica Particles Grafted with Poly(ethyleneoxide-block-N-vinylcaprolactam)", 《JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY》 *
QIAN FENG等: "Temperature-responsive zinc oxide nanorods arrays grafted with poly(N-isopropylacrylamide) via SI-ATRP", 《RSC ADV.》 *
RAJKUMAR PATEL等: "Poly(vinyl chloride)-graft-poly(N-vinyl caprolactam) graft copolymer: synthesis and use as template for porous TiO2 thin films in dye-sensitized solar cells", 《IONICS》 *
ZAI-LIN GONG等: "The fabrication and self-flocculation effect of hybrid TiO2 nanoparticles grafted with poly(N-isopropylacrylamide) at ambient temperature via surface-initiated atom transfer radical polymerization", 《JOURNAL OF MATERIALS CHEMISTRY》 *
姜宇等: "纳米TiO2/聚N-异丙基丙烯酰胺复合水凝胶的合成及其表征", 《化学学报》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106084364A (en) * 2016-07-07 2016-11-09 宁国九鼎橡塑制品有限公司 A kind of ball stud dust cover and preparation method thereof
CN110894268A (en) * 2019-12-04 2020-03-20 杭州传化精细化工有限公司 Nanoparticle type in-situ initiator and preparation method and application thereof
CN110894268B (en) * 2019-12-04 2022-04-19 杭州传化精细化工有限公司 Nanoparticle type in-situ initiator and preparation method and application thereof

Also Published As

Publication number Publication date
CN105037665B (en) 2017-07-28

Similar Documents

Publication Publication Date Title
Thakur et al. Synthesis, characterization and adsorption studies of an acrylic acid-grafted sodium alginate-based TiO2 hydrogel nanocomposite
Pathania et al. Novel guar gum/Al2O3 nanocomposite as an effective photocatalyst for the degradation of malachite green dye
Shaheen et al. A new facile strategy for multifunctional textiles development through in situ deposition of SiO2/TiO2 nanosols hybrid
Ping et al. Surface modification of poly (ethylene terephthalate)(PET) film by gamma-ray induced grafting of poly (acrylic acid) and its application in antibacterial hybrid film
Jašková et al. TiO 2 and ZnO nanoparticles in photocatalytic and hygienic coatings
CN105037665A (en) Titanium dioxide nanoparticle with surface grafted with polyvinyl caprolactam and preparation method of titanium dioxide nanoparticle
CN105413660A (en) Nanosilicon dioxide structure-based high-heavy metal ion adsorption chelating agent and preparation method thereof
Park et al. A facile graft polymerization approach to N-doped TiO2 heterostructures with enhanced visible-light photocatalytic activity
CN106423224A (en) BiVO4/BiOI heterojunction compound photocatalyst and preparation method and application thereof
CN106468021A (en) A kind of preparation method of textile fabric antibacterial finishing agent
Guo et al. Cr (VI)-imprinted polymer wrapped on urchin-like Bi2S3 for reduced photocorrosion and improved photoreduction of aqueous Cr (VI)
Sahiner et al. The synthesis of desired functional groups on PEI microgel particles for biomedical and environmental applications
CN106811968A (en) A kind of shitosan photo-catalytic antibacterial towel
CN108057348A (en) A kind of hydrophily sterilizing dye reverse osmosis membrane and its preparation method
CN105435847A (en) Bi2WO6/BiOI@quaternary ammonium salt inorganic/organic compound photocatalysis bactericide and preparation method thereof
CN113679124B (en) Recyclable antiviral mask and preparation method thereof
CN109453752A (en) A kind of cationic magnetic nanoparticle and its preparation method and application
Peng et al. Target recognition and preferential degradation of toxic chemical groups by innovative group-imprinted photocatalyst with footprint cavity
Sarvalkar et al. A review on multifunctional nanotechnological aspects in modern textile
Ren et al. Chitosan and TiO2 functionalized polypropylene nonwoven fabrics with visible light induced photocatalytic antibacterial performances
CN106362805A (en) Titanium dioxide/graphene/molecularly imprinted composite material and preparation method and application thereof
Hussein et al. Chitosan/TiO2 nanocomposites: Effect of microwave heating and solution mixing techniques on physical properties
Li et al. Efficient iodine capture by a sesbania gum-based polymeric adsorbent for reutilization in bacterial decontamination
CN108752705A (en) A kind of automotive trim panel and preparation method thereof of antibacterial taste removal
CN107082826B (en) A kind of graft modification chitosan microball and its preparation method and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant