CN105037665B - A kind of titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer and preparation method thereof - Google Patents
A kind of titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer and preparation method thereof Download PDFInfo
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Abstract
A kind of titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer and preparation method thereof, the present invention relates to a kind of titanium dioxide nano-particle and preparation method thereof.The invention aims to solve existing nano-TiO2After use the problem of difficult removal.A kind of titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer of the present invention is by the TiO with double bond2Particle, in-situ polymerization solvent, initiator, caprolactam monomer and molecular weight regulator are made；Method：First, using coupling agent to TiO2Particle carries out surface modification, it is possessed double bond, is then dispersed in appropriate solvent；2nd, initiator, monomer, molecular weight regulator are added, is completed in the way of in-situ polymerization.The close hydrophobic transition temperature of particle prepared by the present invention can be adjusted, and be conducive to the extraction of titanium dioxide nano-particle.The present invention is applied to catalyst recycling, heavy metal ion adsorbed, water treatment agent and reclaimed and biomedical materials field.
Description
Technical field
The present invention relates to a kind of titanium dioxide nano-particle and preparation method thereof.
Background technology
Titanium dioxide (TiO2) it is a kind of good, nontoxic, the inexpensive semi-conducting material of chemical stability.Titanium dioxide nano granule
Sub easily prepared, excellent adsorption.Nano-TiO2With most valuable optical property, all shown in auto industry and numerous areas
Go out fine development prospect.Nano-TiO2Also have very high chemical stability, heat endurance, nontoxicity, Superhydrophilic, non-move
Shifting property, and can be contacted completely with food, so being widely used in anti-ultraviolet material, weaving, photocatalysis catalyst, self-cleaning glass
In glass, suncream, coating, ink, packaging material for food, paper industry, aerospace industry, in lithium battery.
TiO2Sterilized for a long time in the presence of light middle-ultraviolet lamp.It is demonstrated experimentally that with 0.1mg/cm3The anatase titanium dioxide of concentration is received
Rice TiO2Pernicious HeLa cell, and increasing with superoxide dismutase (SOD) addition, TiO can thoroughly be killed2Light
The efficiency that cancer cell is killed in catalysis is also improved.To bacillus subtilis black variety gemma, Pseudomonas aeruginosa, Escherichia coli, golden grape
The killing rate of coccus, salmonella, tooth a bacterium and aspergillus reaches more than 98%；Use TiO2Photochemical catalytic oxidation advanced treating is originally
Water, can greatly reduce the bacterial population in water, without mutagenesis after drinking, and reach the standard of safe drinking water；Add in coating
Plus nano TiO2Sterilization, antifouling, deodorization, self-cleaning antibacterial antifouling paint can be produced, applied to hospital ward, operating room and
The place that the bacteriums such as family bathroom space are intensive, easily breed, it is capable of purifying air, prevent infection, deodorization taste removal.Can effectively it kill
Deng harmful bacteria.Nano-TiO2Can absorb ultraviolet, but can reflect, scatters ultraviolet, moreover it is possible to pass through visible ray, be that performance is excellent
More, the extremely ultra-violet protecting agent of promising physical shielding type.
Nano titanium oxide is small due to particle diameter, and activity is big, can reflect, scatters ultraviolet, and ultraviolet can be absorbed again, so that
There is stronger obstructing capacity to ultraviolet.Utilize nano-TiO2The transparency and ultraviolet absorption ability also act as packaging for foodstuff
Film, ink, coating, textile fabrics and filler for plastic, can substitute organic uv absorbers, for that can improve painting in coating
Expect ageing-resistant ability.Result of study is found, makes TiO in the presence of daylight or light middle-ultraviolet lamp2Activate and generate with height
The free radical of catalytic activity, can produce very strong photooxidation and reducing power, can be catalyzed, photodissociation is attached to the various of body surface
The organic matters such as formaldehyde and part inorganic matter.The function of purifying the air of a room can be played.
As can be seen here, TiO2There is larger advantage, but nanoscale in terms of photocatalysis, heavy metal adsorption and ion reduction
Titanium dioxide be difficult to be separated from the water out, particle diameter is smaller to be more difficult to after separation, therefore processing nano titania in system
Removal is a stubborn problem.
The content of the invention
The invention aims to solve existing nano-TiO2There is provided a kind of surface grafting the problem of difficult removal after use
Titanium dioxide nano-particle of Vinylcaprolactam homopolymer and preparation method thereof.
A kind of titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer of the present invention is by with double bond
TiO2Particle, in-situ polymerization solvent, initiator, caprolactam monomer and molecular weight regulator are made；Its situ gathers
Bonding solvent is that the one or more in dimethyl sulfoxide, tetrahydrofuran, dioxane, methanol, ethanol and ring propyl alcohol are mixed by any ratio
The mixture of conjunction；The mass volume ratio of caprolactam monomer and in-situ polymerization solvent is 1g：5mL；Vinyl acyl in oneself
Amine monomers, the TiO with double bond2The mass ratio of particle and initiator is 1：(0.01~1)：(0.001~0.04), molecular weight control
The addition of preparation is the 0~0.01% of the quality of caprolactam monomer.
A kind of preparation method of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer of the present invention, is to press
State step progress：
First, by TiO2Particle is scattered in absolute ethyl alcohol, then adds triethanolamine, and ultrasonic disperse obtains TiO2Particle point
Dispersion liquid；5min is stirred after coupling agent and deionized water are mixed, TiO is then added2In particle dispersion, then adjust pH value and be
10,12h is then reacted under the conditions of 65 DEG C, then separated with 15~20min of 6000r/min centrifugations, take solid formation, 50 DEG C of bakings
It is dry, obtain the TiO with double bond2Particle；Wherein TiO2The mass volume ratio of particle and absolute ethyl alcohol, triethanolamine is 1g：
0.1mL：50mL, TiO2The quality mol ratio of particle and coupling agent is 1g：The volume ratio of (0.1~4mmol), coupling agent and water is
1：(1.5~1.6)；
2nd, the TiO obtained by step one with double bond is taken2Particle, is scattered in in-situ polymerization solvent, then adds and triggers
Agent, caprolactam monomer, molecular weight regulator, 3~16h of water-bath under conditions of 70~80 DEG C then will be anti-
Answer product to be scattered in absolute ethyl alcohol, stand 10h, remove precipitation, then with 7000r/min 15~20min of centrifugation, go
Clearly, that is, complete, wherein in-situ polymerization solvent is dimethyl sulfoxide, tetrahydrofuran, dioxane, methanol, ethanol, chloroform and isopropanol
In the mixture that is mixed by any ratio of one or more；The quality volume of caprolactam monomer and in-situ polymerization solvent
Than for 1g：(4~6) mL；Caprolactam monomer, the TiO with double bond2The mass ratio of particle and initiator is 1：
(0.01~1)：(0.001~0.04), the addition of molecular weight regulator for the quality of caprolactam monomer 0~
0.01%.
Polyvinylcaprolactame (PVCL) is a kind of polymer of responsive to temperature type, and it has low consolute temperature with water
(LCST, lower critical solution temperature), when temperature is less than LCST, PVCL is dissolved in water, works as temperature
When degree is higher than LCST, PVCL is separated out from water.The functional particles for having catalytic performance are coated or are grafted by temperature sensing material, can
To realize " on-off " of particle function, transfer of the particle in water-oil two-phase can be realized under temperature control.
The double bond of caprolactam monomer used in the present invention is connected directly between on the N atoms of amide groups so that
The reactivity of monomer is very low.This monomer polymerize in the response temperature (VPTT) of resulting polymers, certain limit to be had with the degree of polymerization
Close, the degree of polymerization is higher, and VPTT points are lower.In the in-situ polymerization solvent selected by present embodiment, caprolactam can be with
Higher degrees of polymerization is reached, the degree of polymerization and the ratio in reaction time, initiator and monomer have certain corresponding relation.
The parent of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer prepared by the present invention-hydrophobic transformation temperature
Degree can be adjusted；The method for adjusting transition temperature is simple；The value of transition temperature can 25 DEG C~80 DEG C scopes arbitrary value；Grain
, can be with Spontaneous adsorption in non-polar material surface when son is changed into hydrophobic；, can be from apolar surfaces when particle is changed into hydrophilic
Water is redissolved in, the extraction of titanium dioxide nano-particle is so advantageous for.The particle is in catalyst recycling, heavy metal
There is potential application value in the fields such as ionic adsorption, water treatment agent recovery, bio-medical material.
Brief description of the drawings
Fig. 1 be the surface of embodiment one before modified after titanium dioxide FT-IR spectrograms variation diagram；Wherein a is TiO2Particle, b
For the TiO with double bond2Particle；
Fig. 2 is the variation diagram of titanium dioxide FT-IR spectrograms before and after the step 2 in-situ polymerization of embodiment one；
Fig. 3 is TiO in embodiment one2The SEM photograph of particle；
Fig. 4 is the TiO with double bond in embodiment one2The SEM photograph of particle；
Fig. 5 is the SEM photograph of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer in embodiment one；
Fig. 6 is the titanium dioxide nano granule of surface grafting Vinylcaprolactam homopolymer prepared by embodiment one under temperature action
The phase in version of son；
Fig. 7 is the titanium dioxide nano-particle recycling use of temperature action lower surface grafted polyethylene base caprolactam
Schematic diagram.
Embodiment
Technical solution of the present invention is not limited to act embodiment set forth below, in addition between each embodiment
Any combination.
Embodiment one：A kind of titanium dioxide nano granule of surface grafting Vinylcaprolactam homopolymer of present embodiment
Son is by the TiO with double bond2Particle, in-situ polymerization solvent, initiator, caprolactam monomer and molecular weight regulator
It is made；Wherein in-situ polymerization solvent be dimethyl sulfoxide, tetrahydrofuran, dioxane, methanol, ethanol and one kind in ring propyl alcohol or
Several mixtures being mixed by any ratio；The mass volume ratio of caprolactam monomer and in-situ polymerization solvent is 1g：
5mL；Caprolactam monomer, the TiO with double bond2The mass ratio of particle and initiator is 1：(0.01~1)：(0.001
~0.04), the addition of molecular weight regulator is the 0~0.01% of the quality of caprolactam monomer.
Polyvinylcaprolactame (PVCL) is a kind of polymer of responsive to temperature type, and it has low consolute temperature with water
(LCST, lower critical solution temperature), when temperature is less than LCST, PVCL is dissolved in water, works as temperature
When degree is higher than LCST, PVCL is separated out from water.The functional particles for having catalytic performance are coated or are grafted by temperature sensing material, can
To realize " on-off " of particle function, transfer of the particle in water-oil two-phase can be realized under temperature control.
Parent-hydrophobic of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer prepared by present embodiment turns
Temperature can be adjusted；The method for adjusting transition temperature is simple；The value of transition temperature can be in any of 25 DEG C~80 DEG C scopes
Value；, can be with Spontaneous adsorption in non-polar material surface when particle is changed into hydrophobic；, can be from non-pole when particle is changed into hydrophilic
Property surface is redissolved in water.The particle is in catalyst recycling, heavy metal ion adsorbed, water treatment agent recovery, biological doctor
There is potential application value with fields such as materials.
Embodiment two：Present embodiment from unlike embodiment one：Described initiator is azo
Bis-isobutyronitrile, AMBN, ABVN, azo isobutyl cyano group formamide, azo diisopropyl imidazoline hydrochloride, azo two
One or more in isobutyl dimethyl phthalate, azo diisobutyl amidine hydrochloride and azo dicyano valeric acid are by any ratio composition
Mixture.It is other identical with embodiment one.
Embodiment three：Present embodiment from unlike embodiment one or two：Described molecular weight control
Preparation is acetylacetone cobalt or ehtyl potassium xanthate.It is other identical with embodiment one or two.
Embodiment four：A kind of titanium dioxide nano granule of surface grafting Vinylcaprolactam homopolymer of present embodiment
The preparation method of son, is carried out in the steps below：First, by TiO2Particle is scattered in absolute ethyl alcohol, then adds three ethanol
Amine, ultrasonic disperse obtains TiO2Particle dispersion；5min is stirred after coupling agent and deionized water are mixed, TiO is then added2Grain
In sub- dispersion liquid, then adjust pH value for 10, then react 12h under the conditions of 65 DEG C, then with 6000r/min centrifugations 15~
20min is separated, and takes solid formation, and 50 DEG C of drying obtain the TiO with double bond2Particle；Wherein TiO2Particle and absolute ethyl alcohol, three second
The mass volume ratio of hydramine is 1g：0.1mL：50mL, TiO2The 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)；
2nd, the TiO obtained by step one with double bond is taken2Particle, is scattered in in-situ polymerization solvent, then adds and triggers
Agent, caprolactam monomer, molecular weight regulator, 3~16h of water-bath under conditions of 70~80 DEG C then will be anti-
Answer product to be scattered in absolute ethyl alcohol, stand 10h, remove precipitation, then with 7000r/min 15~20min of centrifugation, go
Clearly, that is, complete, wherein in-situ polymerization solvent is dimethyl sulfoxide, tetrahydrofuran, dioxane, methanol, ethanol, chloroform and isopropanol
In the mixture that is mixed by any ratio of one or more；The quality volume of caprolactam monomer and in-situ polymerization solvent
Than for 1g：(4~6) mL；Caprolactam monomer, the TiO with double bond2The mass ratio of particle and initiator is 1：
(0.01~1)：(0.001~0.04), the addition of molecular weight regulator for the quality of caprolactam monomer 0~
0.01%.
The double bond of caprolactam monomer is connected directly between on the N atoms of amide groups used in present embodiment,
So that the reactivity of monomer is very low.This monomer polymerize in the response temperature (VPTT) of resulting polymers, certain limit with polymerizeing
Degree is relevant, and the degree of polymerization is higher, and VPTT points are lower.In the in-situ polymerization solvent selected by present embodiment, caprolactam
Higher degrees of polymerization can be reached, the degree of polymerization and the ratio in reaction time, initiator and monomer have certain corresponding relation.
Embodiment five：Present embodiment from unlike embodiment four：Coupling agent described in step one
For vinyltrimethoxy silane, VTES, vinyl trichlorosilane, (the 'beta '-methoxy ethoxy of vinyl three
Base) in silane, the tert-butoxy silane of vinyl three, vinyl silane tri-butyl peroxy and vinyltriacetoxy silane
One or more are by any mixture than composition.It is other identical with one of embodiment one to four.
Embodiment six：Present embodiment from unlike embodiment four or five：Step one uses ammoniacal liquor
Adjust pH value.It is other identical with one of embodiment one to five.
Embodiment seven：Unlike one of present embodiment and embodiment one to six：Described in step 2
Initiator be azodiisobutyronitrile, AMBN, ABVN, azo isobutyl cyano group formamide, the ring of azo two
One kind or several in hexyl formonitrile HCN, azo-bis-iso-dimethyl, azo diisobutyl amidine hydrochloride and azo dicyano valeric acid
Plant by any mixture than composition.It is other identical with one of embodiment one to six.
Embodiment eight：Unlike one of present embodiment and embodiment one to seven：Described in step 2
Molecular weight regulator be acetylacetone cobalt or ehtyl potassium xanthate.It is other identical with one of embodiment one to seven.
Embodiment nine：Unlike one of present embodiment and embodiment one to eight：Described in step 2
3~16h of water-bath under conditions of 75 DEG C.It is other identical with one of embodiment one to eight.
Embodiment ten：Unlike one of present embodiment and embodiment one to nine：Described in step 2
The mass volume ratio of caprolactam monomer and in-situ polymerization solvent be 1g：5mL.It is other with embodiment one to
One of nine is identical.
Embodiment 11：Unlike one of present embodiment and embodiment one to ten：Step 2 institute
Caprolactam monomer, the TiO with double bond stated2The mass ratio of particle and initiator is 1：0.1：0.01, molecular weight
The addition of controlling agent is the 0% of the quality of caprolactam monomer.Other phases one of with embodiment one to ten
Together.
Embodiment 12：Present embodiment from unlike embodiment one to one of 11：Step 2
Described caprolactam monomer, the TiO with double bond2The mass ratio of particle and initiator is 1：0.05：0.01, molecule
It is the 0.01% of the quality of caprolactam monomer to measure the addition of controlling agent.Other and embodiment one to 11
One of it is identical.
Embodiment 13：Present embodiment from unlike embodiment one to one of 12：Step 2
Described caprolactam monomer, the TiO with double bond2The mass ratio of particle and initiator is 1：0.05：0.004, point
The addition of son amount controlling agent is the 0.01% of the quality of caprolactam monomer.Other and embodiment one to ten
One of two is identical.
Embodiment 14：Present embodiment from unlike embodiment one to one of 13：Step 2
Described caprolactam monomer, the TiO with double bond2The mass ratio of particle and initiator is 1：0.05：0.002, point
The addition of son amount controlling agent is the 0.01% of the quality of caprolactam monomer.Other and embodiment one to ten
One of three is identical.
Embodiment 15：Present embodiment from unlike embodiment one to one of 14：Step 2
The described water-bath 12h under conditions of 75 DEG C.It is other identical with embodiment one to one of 14.
Beneficial effects of the present invention are verified by following examples：
Embodiment one：
The preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, its feature exists
Carried out in the steps below in it：
First, by 1gTiO2Particle is scattered in 50mL absolute ethyl alcohols, then adds 0.1mL triethanolamines, and ultrasonic disperse is obtained
To TiO2Particle dispersion；5min is stirred after 0.94mL VTESs and 1.5mL deionized waters are mixed, then
Add TiO2In particle dispersion, then it is 10 to adjust pH value with ammoniacal liquor, and 12h is then reacted under the conditions of 65 DEG C, then with 6000r/
15~20min of min centrifugations is separated, and takes solid formation, and 50 DEG C of drying obtain the TiO with double bond2Particle；
2nd, the TiO obtained by 0.1g steps one with double bond is taken2Particle, is scattered in 5mL tetrahydrofurans, then adds
0.01g ABVNs and 1g caprolactam monomers, the water-bath 12h under conditions of 75 DEG C then will reaction
Product is scattered in absolute ethyl alcohol, stands 10h, removes precipitation, then with 7000r/min centrifugation 20min, removes supernatant, i.e., complete
Into.
The change of titanium dioxide FT-IR spectrograms is as shown in Figure 1 afterwards before modified on the present embodiment step one surface；Wherein a is
TiO2Particle, b is the TiO with double bond2Particle；It can see in figure after being modified through coupling agent, 1000-1250cm-1Place
Absworption peak can belong to Si-O-Ti and Si-O, 1578cm-1Characteristic absorption peak can belong to double bond, through being washed repeatedly with ethanol
Still had after washing.Show coupling agent and TiO2Particle is firmly combined with.
The change of titanium dioxide FT-IR spectrograms is as shown in Fig. 2 a is with double before and after the present embodiment step 2 in-situ polymerization
The TiO of key2Particle, b is the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer；As seen from Figure 2, in figure
1081cm-1And 1199cm-1The absworption peak at place can belong to the vibration of C-N bond bendings, 1479cm-1The absworption peak at place can belong to
For the stretching vibration of c h bond.2923cm-1And 2858cm-1The absworption peak at place can be attributed to the stretching vibration of methyl c h bond.
1633cm-1The absworption peak at place corresponds to C=O stretching vibrations.The TiO after separation2Particle surface still can detect polyethylene oneself
The characteristic absorption peak of lactams, shows that PVCL grafts on TiO2Particle surface.Fig. 3 is TiO in the present embodiment2The SEM of particle shines
Piece；Fig. 4 is the TiO with double bond in the present embodiment2The SEM photograph of particle；Fig. 5 is surface grafting polyvinyl in the present embodiment
The SEM photograph of the titanium dioxide nano-particle of caprolactam；Comparison diagram 3,4 and 5 is it can be found that TiO2Particle surface covers one
Strata vinyl caproamide.
The titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer manufactured in the present embodiment under temperature action
Phase diagram is as shown in Figure 6；Sample bottle photo shows, (PVCL LCST), particle when temperature is less than Volume-phase transition temperature
It is well dispersed into water；When being heated to temperature and being increased to more than Volume-phase transition temperature, particle is separated out from water.Schematic diagram
Depict occur Volume-phase transition before and after particle microstructure change.Temperature action lower surface grafted polyethylene base caprolactam
Titanium dioxide nano-particle recycling use schematic diagram as shown in fig. 7, when rise temperature to Volume-phase transition temperature more than
When, particle Spontaneous adsorption can be separated easily in apolar surfaces from system；When temperature is reduced to Volume-phase transition temperature
When following, particle is dispersed in water again from apolar surfaces.Recycling for particle can be realized.
Embodiment two：
The preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, its feature exists
Carried out in the steps below in it：
First, by 1gTiO2Particle is scattered in 50mL absolute ethyl alcohols, then adds 0.1mL triethanolamines, and ultrasonic disperse is obtained
To TiO2Particle dispersion；5min is stirred after 0.94mL VTESs and 1.5mL deionized waters are mixed, then
Add TiO2In particle dispersion, then it is 10 to adjust pH value with ammoniacal liquor, and 12h is then reacted under the conditions of 65 DEG C, then with 6000r/
15~20min of min centrifugations is separated, and takes solid formation, and 50 DEG C of drying obtain the TiO with double bond2Particle；
2nd, the TiO obtained by 0.1g steps one with double bond is taken2Particle, is scattered in 5mL ethanol, then adds 0.01g even
The different heptonitrile of nitrogen two and 1g caprolactam monomers, water-bath 12h, then disperses reaction product under conditions of 75 DEG C
In absolute ethyl alcohol, 10h is stood, precipitation is removed, then with 7000r/min centrifugation 20min, removes supernatant, that is, complete.
Embodiment three：
The preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, its feature exists
Carried out in the steps below in it：
First, by 1gTiO2Particle is scattered in 50mL absolute ethyl alcohols, then adds 0.1mL triethanolamines, and ultrasonic disperse is obtained
To TiO2Particle dispersion；5min is stirred after 0.94mL VTESs and 1.5mL deionized waters are mixed, then
Add TiO2In particle dispersion, then it is 10 to adjust pH value with ammoniacal liquor, and 12h is then reacted under the conditions of 65 DEG C, then with 6000r/
15~20min of min centrifugations is separated, and takes solid formation, and 50 DEG C of drying obtain the TiO with double bond2Particle；
2nd, the TiO obtained by 0.1g steps one with double bond is taken2Particle, is scattered in 5mL methanol, then adds 0.01g even
The different heptonitrile of nitrogen two and 1g caprolactam monomers, water-bath 12h, then disperses reaction product under conditions of 75 DEG C
In absolute ethyl alcohol, 10h is stood, precipitation is removed, then with 7000r/min centrifugation 20min, removes supernatant, that is, complete.
Example IV：
The preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, its feature exists
Carried out in the steps below in it：
First, by 1gTiO2Particle is scattered in 50mL absolute ethyl alcohols, then adds 0.1mL triethanolamines, and ultrasonic disperse is obtained
To TiO2Particle dispersion；5min is stirred after 0.94mL VTESs and 1.5mL deionized waters are mixed, then
Add TiO2In particle dispersion, then it is 10 to adjust pH value with ammoniacal liquor, and 12h is then reacted under the conditions of 65 DEG C, then with 6000r/
15~20min of min centrifugations is separated, and takes solid formation, and 50 DEG C of drying obtain the TiO with double bond2Particle；
2nd, the TiO obtained by 0.1g steps one with double bond is taken2Particle, is scattered in 5mL dioxane, then adds
0.01g ABVNs and 1g caprolactam monomers, the water-bath 12h under conditions of 75 DEG C then will reaction
Product is scattered in absolute ethyl alcohol, stands 10h, removes precipitation, then with 7000r/min centrifugation 20min, removes supernatant, i.e., complete
Into.
Embodiment five：
The preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, its feature exists
Carried out in the steps below in it：
First, by 1gTiO2Particle is scattered in 50mL absolute ethyl alcohols, then adds 0.1mL triethanolamines, and ultrasonic disperse is obtained
To TiO2Particle dispersion；5min is stirred after 0.94mL VTESs and 1.5mL deionized waters are mixed, then
Add TiO2In particle dispersion, then it is 10 to adjust pH value with ammoniacal liquor, and 12h is then reacted under the conditions of 65 DEG C, then with 6000r/
15~20min of min centrifugations is separated, and takes solid formation, and 50 DEG C of drying obtain the TiO with double bond2Particle；
2nd, the TiO obtained by 0.1g steps one with double bond is taken2Particle, is scattered in 5mL isopropanols, then adds 0.01g
ABVN and 1g caprolactam monomers, the water-bath 12h under conditions of 75 DEG C, then by reaction product point
Dissipate in absolute ethyl alcohol, stand 10h, remove precipitation, then with 7000r/min centrifugation 20min, remove supernatant, that is, complete.
Embodiment six：
The preparation method of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer, its feature exists
Carried out in the steps below in it：
First, by 1gTiO2Particle is scattered in 50mL absolute ethyl alcohols, then adds 0.1mL triethanolamines, and ultrasonic disperse is obtained
To TiO2Particle dispersion；5min is stirred after 0.94mL VTESs and 1.5mL deionized waters are mixed, then
Add TiO2In particle dispersion, then it is 10 to adjust pH value with ammoniacal liquor, and 12h is then reacted under the conditions of 65 DEG C, then with 6000r/
15~20min of min centrifugations is separated, and takes solid formation, and 50 DEG C of drying obtain the TiO with double bond2Particle；
2nd, the TiO obtained by 0.1g steps one with double bond is taken2Particle, is scattered in 5mL chloroforms, then adds 0.01g even
The different heptonitrile of nitrogen two and 1g caprolactam monomers, water-bath 12h, then disperses reaction product under conditions of 75 DEG C
In absolute ethyl alcohol, 10h is stood, precipitation is removed, then with 7000r/min centrifugation 20min, removes supernatant, that is, complete.
Table 1
The phase of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer prepared by embodiment one~six turns
As shown in Table 1, as shown in Table 1, in the case of other conditions identical, surface prepared by different in-situ polymerization solvents connects temperature
The titanium dioxide nano-particle of branch Vinylcaprolactam homopolymer possesses different phase transition temperatures, and this is due to in-situ polymerization solvent
The influence of polarity.
Embodiment seven：The preparation side of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer
Method, it is characterised in that it is carried out in the steps below：
First, by 1gTiO2Particle is scattered in 50mL absolute ethyl alcohols, then adds 0.1mL triethanolamines, and ultrasonic disperse is obtained
To TiO2Particle dispersion；5min is stirred after 0.94mL VTESs and 1.5mL deionized waters are mixed, then
Add TiO2In particle dispersion, then it is 10 to adjust pH value with ammoniacal liquor, and 12h is then reacted under the conditions of 65 DEG C, then with 6000r/
15~20min of min centrifugations is separated, and takes solid formation, and 50 DEG C of drying obtain the TiO with double bond2Particle；
2nd, the TiO obtained by 0.05g steps one with double bond is taken2Particle, is scattered in 5mL chloroforms, then adds 0.01g
Azodiisobutyronitrile, 0.0001g acetylacetone cobalts and 1g caprolactam monomers, the water-bath under conditions of 75 DEG C
12h, is then scattered in absolute ethyl alcohol by reaction product, stands 10h, precipitation is removed, then with 7000r/min centrifugations
20min, removes supernatant, that is, completes.
Embodiment eight：The preparation side of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer
Method, it is characterised in that it is carried out in the steps below：
First, by 1gTiO2Particle is scattered in 50mL absolute ethyl alcohols, then adds 0.1mL triethanolamines, and ultrasonic disperse is obtained
To TiO2Particle dispersion；5min is stirred after 0.94mL VTESs and 1.5mL deionized waters are mixed, then
Add TiO2In particle dispersion, then it is 10 to adjust pH value with ammoniacal liquor, and 12h is then reacted under the conditions of 65 DEG C, then with 6000r/
15~20min of min centrifugations is separated, and takes solid formation, and 50 DEG C of drying obtain the TiO with double bond2Particle；
2nd, the TiO obtained by 0.05g steps one with double bond is taken2Particle, is scattered in 5mL chloroforms, then adds 0.004g
Azodiisobutyronitrile, 0.0001g acetylacetone cobalts and 1g caprolactam monomers, the water-bath under conditions of 75 DEG C
12h, is then scattered in absolute ethyl alcohol by reaction product, stands 10h, precipitation is removed, then with 7000r/min centrifugations
20min, removes supernatant, that is, completes.
Embodiment nine：The preparation side of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer
Method, it is characterised in that it is carried out in the steps below：
First, by 1gTiO2Particle is scattered in 50mL absolute ethyl alcohols, then adds 0.1mL triethanolamines, and ultrasonic disperse is obtained
To TiO2Particle dispersion；5min is stirred after 0.94mL VTESs and 1.5mL deionized waters are mixed, then
Add TiO2In particle dispersion, then it is 10 to adjust pH value with ammoniacal liquor, and 12h is then reacted under the conditions of 65 DEG C, then with 6000r/
15~20min of min centrifugations is separated, and takes solid formation, and 50 DEG C of drying obtain the TiO with double bond2Particle；
2nd, the TiO obtained by 0.05g steps one with double bond is taken2Particle, is scattered in 5mL chloroforms, then adds 0.002g
Azodiisobutyronitrile, 0.0001g acetylacetone cobalts and 1g caprolactam monomers, the water-bath under conditions of 75 DEG C
12h, is then scattered in absolute ethyl alcohol by reaction product, stands 10h, precipitation is removed, then with 7000r/min centrifugations
20min, removes supernatant, that is, completes.
The phase 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, in the case of other conditions identical, the different quality of initiator and monomer is than system for transition temperature
The titanium dioxide nano-particle of standby surface grafting Vinylcaprolactam homopolymer possesses different phase transition temperatures, and this is due to
Polymerisation terminates mode, and this radical life is that coupling is terminated, and free radical more polymolecular amount is higher, and molecular weight gets over Gao Xiangzhuan
Temperature 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 side of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer
Method, it is characterised in that it is carried out in the steps below：
3rd, by 1gTiO2Particle is scattered in 50mL absolute ethyl alcohols, then adds 0.1mL triethanolamines, and ultrasonic disperse is obtained
To TiO2Particle dispersion；5min is stirred after 0.94mL VTESs and 1.5mL deionized waters are mixed, then
Add TiO2In particle dispersion, then it is 10 to adjust pH value with ammoniacal liquor, and 12h is then reacted under the conditions of 65 DEG C, then with 6000r/
15~20min of min centrifugations is separated, and takes solid formation, and 50 DEG C of drying obtain the TiO with double bond2Particle；
4th, the TiO obtained by 0.05g steps one with double bond is taken2Particle, is scattered in 5mL chloroforms, then adds 0.01g
Azodiisobutyronitrile and 1g caprolactam monomers, the water-bath 12h under conditions of 75 DEG C, then by reaction product point
Dissipate in absolute ethyl alcohol, stand 10h, remove precipitation, then with 7000r/min centrifugation 20min, remove supernatant, that is, complete.
Embodiment 11：The preparation side of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer
Method, it is characterised in that it is carried out in the steps below：
3rd, by 1gTiO2Particle is scattered in 50mL absolute ethyl alcohols, then adds 0.1mL triethanolamines, and ultrasonic disperse is obtained
To TiO2Particle dispersion；5min is stirred after 0.94mL VTESs and 1.5mL deionized waters are mixed, then
Add TiO2In particle dispersion, then it is 10 to adjust pH value with ammoniacal liquor, and 12h is then reacted under the conditions of 65 DEG C, then with 6000r/
15~20min of min centrifugations is separated, and takes solid formation, and 50 DEG C of drying obtain the TiO with double bond2Particle；
4th, the TiO obtained by 0.05g steps one with double bond is taken2Particle, is scattered in 5mL chloroforms, then adds 0.004g
Azodiisobutyronitrile and 1g caprolactam monomers, the water-bath 12h under conditions of 75 DEG C, then by reaction product point
Dissipate in absolute ethyl alcohol, stand 10h, remove precipitation, then with 7000r/min centrifugation 20min, remove supernatant, that is, complete.
Embodiment 12：The preparation side of the titanium dioxide nano-particle of the present embodiment surface grafting Vinylcaprolactam homopolymer
Method, it is characterised in that it is carried out in the steps below：
3rd, by 1gTiO2Particle is scattered in 50mL absolute ethyl alcohols, then adds 0.1mL triethanolamines, and ultrasonic disperse is obtained
To TiO2Particle dispersion；5min is stirred after 0.94mL VTESs and 1.5mL deionized waters are mixed, then
Add TiO2In particle dispersion, then it is 10 to adjust pH value with ammoniacal liquor, and 12h is then reacted under the conditions of 65 DEG C, then with 6000r/
15~20min of min centrifugations is separated, and takes solid formation, and 50 DEG C of drying obtain the TiO with double bond2Particle；
4th, the TiO obtained by 0.05g steps one with double bond is taken2Particle, is scattered in 5mL chloroforms, then adds 0.002g
Azodiisobutyronitrile and 1g caprolactam monomers, the water-bath 12h under conditions of 75 DEG C, then by reaction product point
Dissipate in absolute ethyl alcohol, stand 10h, remove precipitation, then with 7000r/min centrifugation 20min, remove supernatant, that is, complete.
The phase of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer prepared by embodiment ten~12
Transition temperature as shown in Table 3, as shown in Table 3, in the case of other conditions identical, the differential responses time prepare surface grafting
The titanium dioxide nano-particle of Vinylcaprolactam homopolymer possesses different phase transition temperatures, and this is due to over time, to divide
Son amount more and more higher.
Claims (10)
1. a kind of titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer, it is characterised in that it is by with double bond
TiO2Particle, in-situ polymerization solvent, initiator, caprolactam monomer and molecular weight regulator are made；Its situ
Polymer solvent is one or more of by appointing in dimethyl sulfoxide, tetrahydrofuran, dioxane, methanol, ethanol, chloroform and isopropanol
Anticipate than the mixture of mixing；The mass volume ratio of caprolactam monomer and in-situ polymerization solvent is 1g：5mL；Vinyl
Caprolactam monomer, the TiO with double bond2The mass ratio of particle and initiator is 1：(0.01~1)：(0.001~0.04), point
The addition of son amount controlling agent is the 0~0.01% of the quality of caprolactam monomer.
2. a kind of titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer according to claim 1, it is special
Levy and be that described initiator is azodiisobutyronitrile, AMBN, ABVN, azo isobutyl cyano group formyl
In amine, azo diisopropyl imidazoline hydrochloride, azo-bis-iso-dimethyl, azo diisobutyl amidine hydrochloride and azo dicyano valeric acid
One or more by it is any than composition mixture.
3. a kind of titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer according to claim 1, it is special
Levy and be that described molecular weight regulator is acetylacetone cobalt or ehtyl potassium xanthate.
4. the method for the titanium dioxide nano-particle of the surface grafting Vinylcaprolactam homopolymer described in claim 1 is prepared, its
It is characterised by that it is carried out in the steps below：
First, by TiO2Particle is scattered in absolute ethyl alcohol, then adds triethanolamine, and ultrasonic disperse obtains TiO2Particle disperses
Liquid；5min is stirred after coupling agent and deionized water are mixed, TiO is then added2In particle dispersion, then it is 10 to adjust pH value,
Then 12h is reacted under the conditions of 65 DEG C, then is separated with 15~20min of 6000r/min centrifugations, solid formation is taken, 50 DEG C dry,
Obtain the TiO with double bond2Particle；Wherein TiO2The mass volume ratio of particle and absolute ethyl alcohol, triethanolamine is 1g：0.1mL：
50mL, TiO2The quality mol ratio of particle and coupling agent is 1g：The volume ratio of (0.1~4mmol), coupling agent and water is 1：(1.5
~1.6)；
2nd, the TiO obtained by step one with double bond is taken2Particle, is scattered in in-situ polymerization solvent, then adds initiator, ethene
Base caprolactam monomer, molecular weight regulator, 3~16h of water-bath under conditions of 70~80 DEG C, then by reaction product point
Dissipate in absolute ethyl alcohol, stand 10h, remove precipitation, then with 7000r/min 15~20min of centrifugation, remove supernatant, that is, complete,
Wherein in-situ polymerization solvent be one kind in dimethyl sulfoxide, tetrahydrofuran, dioxane, methanol, ethanol, chloroform and isopropanol or
Several mixtures being mixed by any ratio；The mass volume ratio of caprolactam monomer and in-situ polymerization solvent is 1g：(4
~6) mL；Caprolactam monomer, the TiO with double bond2The mass ratio of particle and initiator is 1：(0.01~1)：
(0.001~0.04), the addition of molecular weight regulator is the 0~0.01% of the quality of caprolactam monomer.
5. a kind of preparation of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer according to claim 4
Method, it is characterised in that the coupling agent described in step one is vinyltrimethoxy silane, VTES, ethene
Base trichlorosilane, vinyl three ('beta '-methoxy ethyoxyl) silane, the tert-butoxy silane of vinyl three, vinyl tri-tert mistake
One or more in oxosilane and vinyltriacetoxy silane are by any mixture than composition.
6. a kind of preparation of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer according to claim 4
Method, it is characterised in that described step one adjusts pH value using ammoniacal liquor.
7. a kind of preparation of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer according to claim 4
Method, it is characterised in that the initiator described in step 2 is azodiisobutyronitrile, AMBN, ABVN, idol
Nitrogen isobutyl cyano group formamide, azo diisopropyl imidazoline hydrochloride, azo-bis-iso-dimethyl, azo diisobutyl amidine hydrochloride and idol
One or more in nitrogen dicyano valeric acid are by any mixture than composition.
8. a kind of preparation of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer according to claim 4
Method, it is characterised in that the molecular weight regulator described in step 2 is acetylacetone cobalt or ehtyl potassium xanthate.
9. a kind of preparation of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer according to claim 4
Method, it is characterised in that step 2 3~16h of water-bath under conditions of 75 DEG C.
10. a kind of system of the titanium dioxide nano-particle of surface grafting Vinylcaprolactam homopolymer according to claim 4
Preparation Method, it is characterised in that the mass volume ratio of caprolactam monomer and in-situ polymerization solvent described in step 2 is
1g：5mL.
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