CN108239878A - Hold the preparation method of the TiO2 intercalation graphene oxide coating polyester fabrics of fluorine-based dissaving polymer modification - Google Patents
Hold the preparation method of the TiO2 intercalation graphene oxide coating polyester fabrics of fluorine-based dissaving polymer modification Download PDFInfo
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- CN108239878A CN108239878A CN201810088688.1A CN201810088688A CN108239878A CN 108239878 A CN108239878 A CN 108239878A CN 201810088688 A CN201810088688 A CN 201810088688A CN 108239878 A CN108239878 A CN 108239878A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic System; Titanates; Zirconates; Stannates; Plumbates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/35—Abrasion, pilling or fibrillation resistance
Abstract
The present invention provides a kind of TiO of the fluorine-based dissaving polymer modification in end2The preparation method of intercalation graphene oxide coating polyester fabric.Including：TiO is prepared according to graphene oxide2Intercalation graphene oxide；According to TiO2Intercalation graphene oxide prepares EDA and is modified TiO2Intercalation graphene oxide；TiO is modified according to EDA2Intercalation graphene oxide prepares the TiO of dissaving polymer modification2Intercalation graphene oxide；The TiO modified according to dissaving polymer2Intercalation graphene oxide prepares the TiO of the fluorine-based dissaving polymer modification in end2Intercalation graphene oxide；According to the TiO that fluorine-based dissaving polymer is held to modify2Intercalation graphene oxide prepares the TiO of the fluorine-based dissaving polymer modification in end2Intercalation graphene oxide coating polyester fabric.Prepared Novel polyester fabric has super hydrophobic effect, and integrates the functions such as catalysis, super-hydrophobic, antibacterial, and the TiO of the fluorine-based dissaving polymer modification in end can be effectively promoted by the connection of chemical bond2Fastness between intercalation graphene oxide and dacron improves wearability.
Description
Technical field
The present invention relates to functional fabric fields, and in particular to a kind of TiO of the fluorine-based dissaving polymer modification in end2Intercalation oxygen
The preparation method of graphite ene coatings dacron.
Background technology
Polyester fiber is the first big kind in current synthetic fibers, abbreviation PET fiber.It is with p-phthalic acid or
Dimethyl terephthalate (DMT) and ethylene glycol are raw material through fiber-forming polymer prepared by esterification or transesterification and polycondensation reaction -- it is poly-
Ethylene glycol terephthalate, through fiber made of spinning and post processing.Polyester fiber is that technique is most simple in three big synthetic fibers
Single one kind.Dacron is very more a kind of chemical ＆ blended fabrics in daily life, and price is also relatively cheap, along with it
Have durable, the good, wash and wear of elasticity, corrosion-resistant, insulation, it is fast light and heat-resist the features such as, liked by people.
At present, with the development of science and technology and the demand of Modern Live, new want is also proposed to the performance of dacron
It asks, such as the additional properties such as super-hydrophobic, catalysis, antibacterial.
The existing related patents about functional polyester fabric have very much, and such as Chinese invention patent, " a kind of antibacterial dacron is knitted
The preparation method of object "（CN 104499271A）In, a kind of preparation method of antibacterial dacron fabric is disclosed, this method will be by clothing
The dacrons such as object, the tablecloth, curtain are as former state successively through Na2CO3The mixed solution of solution, alizarin red and honey element, aniline, hydrochloric acid
With the mixed solution of ammonium persulfate, dimercaptosuccinic acid is handled with Beracilline mixed solution and Nano silver solution continuous modification
Afterwards, silver tetrafluoroborate aqueous solution is placed it in, reacts 30min at room temperature, product is washed through massive laundering, after being dried at 40 DEG C,
Antibacterial dacron fabric is made；Such as Chinese invention patent " a kind of preparation method of bionic super-hydrophobic antifouling dacron textile "（CN
102587129A）In, disclose a kind of preparation method of bionic super-hydrophobic antifouling dacron textile, this method
PET fiber surface is roughened using aminolysis and/or alkaline hydrolysis treatment process, it is then that nano-powder and water and oil repellant is whole
Reason agent is applied to by the method for final finishing on fabric, fiber surface coarse structure is made to reach nano-scale, endowing terylene is knitted
Object water repellent, oil-stain-preventing performance.Its common deficiency is that modified dacron additional properties are single, is not carried out multi-functional
Change.
Invention content
In view of the above problems, the TiO the present invention provides a kind of fluorine-based dissaving polymer modification in end2Intercalation graphite oxide
Ene coatings dacron and preparation method thereof, simple for process, easily operated, the dacron of preparation has super-hydrophobic, catalysis, resists
The multiple functions such as bacterium can be applied to the fields such as various bedding, hygienic material, ornament materials.
To achieve these goals, the technical solution adopted by the present invention is as follows：A kind of fluorine-based dissaving polymer modification in end
TiO2The preparation method of intercalation graphene oxide coating polyester fabric, comprises the steps of：
A kind of TiO of the fluorine-based dissaving polymer modification in end2The preparation method of intercalation graphene oxide coating polyester fabric holds fluorine
The TiO of base dissaving polymer modification2It is added in silane coupler solution and fills after the concussion dispersion of intercalation graphene oxide solution
Divide and stir to get mixed solution, rolling process by two leachings two pads mixed solution on dacron, and it is fluorine-based to dry obtained end
The TiO of dissaving polymer modification2Intercalation graphene oxide coating polyester fabric, which is characterized in that the fluorine-based over-expense in the end
The TiO of fluidized polymer modification2Intercalation graphene oxide functional particulate preparation process comprises the steps of：
（1）TiO is prepared according to graphene oxide2Intercalation graphene oxide；
（2）According to the TiO2Intercalation graphene oxide prepares EDA and is modified TiO2Intercalation graphene oxide；
（3）TiO is modified according to the EDA2Intercalation graphene oxide prepares the TiO of dissaving polymer modification2Intercalation aoxidizes stone
Black alkene；
（4）The TiO modified according to the dissaving polymer2Intercalation graphene oxide prepares the fluorine-based dissaving polymer modification in end
TiO2Intercalation graphene oxide.
Preferably, in above-mentioned preparation method, the step（1）It specifically includes：
Graphene oxide is put into hydrothermal reaction kettle, the first preset time is reacted under the first preset temperature, ultrasound second is pre-
If after the time, anhydrous state is dried under the second preset temperature and obtains dewatered graphene oxide；
By the hydrochloric acid, butyl titanate, sodium hydroxide solution of the dewatered graphene oxide and the first preset ratio close
It closes in container after ultrasonic third preset time, acquisition TiO2Intercalation graphene oxide solution；
According to the TiO2Intercalation graphene oxide solution obtains TiO2Intercalation graphene oxide.
Preferably, in above-mentioned preparation method, first preset temperature be 110-130 DEG C, it is described first it is default when
Between for 3-4 hour, second preset time is 30-50 minutes, and second preset temperature is 40-50 DEG C, the oxidation stone
Black alkene and hydrochloric acid, butyl titanate, sodium hydroxide the first preset ratio of quality be 1:3:50:3, the third preset time
It is 3-4 hours.
Preferably, in above-mentioned preparation method, the step（2）It specifically includes：
By the TiO2Intercalation graphene oxide is dispersed in sub- containing ethylene modulators, dicyclohexyl carbon two by the second preset ratio
In the DMF solution of amine and 4- dimethyl-nitrine pyridine, after supersound process, third preset temperature is heated to, reaction the 4th is pre-
If after the time, DMF is washed by deionized water and centrifuges the acquisition EDA modifications TiO2Intercalation graphene oxide.
Preferably, in above-mentioned preparation method, the TiO2Intercalation graphene oxide and the quality of the DMF solution
Second preset ratio is 1:500, DMF with ethylene modulators, dicyclohexylcarbodiimide, 4- dimethyl-nitrine pyridine quality
Than being 1:0.2：0.02:0.004, the third preset temperature is 50-70 DEG C, and the 4th preset time is 9-12 hours.
Preferably, in above-mentioned preparation method, the step（3）It specifically includes：
The EDA is modified TiO2Intercalation graphene oxide be dispersed in by third preset ratio containing dicyclohexylcarbodiimide and
Dispersion is obtained in the nmp solution of 4- dimethyl-nitrine pyridine, pyridine and triphenyl phosphite；
The LiCl powder of 4th preset ratio and dissaving polymer are added in the dispersion simultaneously stirring and dissolving, mixed
Close object；
After the mixture is heated to the 4th preset temperature under magnetic stirring, it is added into the play of 10 times of mixture quality
In the methanol of strong stirring；
The 5th preset time of ultrasonic disperse, steams methanol under the 5th preset temperature, is washed and centrifuged with DMF and is overspend
The TiO of fluidized polymer modification2Intercalation graphene oxide.
Preferably, in above-mentioned preparation method, the TiO of EDA modifications2The quality of intercalation graphene oxide and nmp solution
The third preset ratio be 1:160, NMP with DMAP, pyridine, triphenyl phosphite mass ratio be 1:0.006:0.06:
0.1, the TiO that the EDA is modified2Intercalation graphene oxide and LiCl powder, dissaving polymer quality it is the described 4th pre-
If ratio is 1:0.6:6, the 4th preset temperature be 80-90 DEG C, the 5th preset temperature be 70-80 DEG C, the described 5th
Preset time is 9-10 hours, and the dissaving polymer is Hyperbranched Polymer with Terminal Amido, Hyperbranched Polymer with Terminal Hydroxyl
And any one or more in end carboxyl super branched polymer.
Preferably, in above-mentioned preparation method, the step（4）It specifically includes：
The TiO that the dissaving polymer is modified2Intercalation graphene oxide is dispersed in the mixing of absolute ethyl alcohol and deionized water
In solution, the 6th preset time is ultrasonically treated under the 6th preset temperature and obtains the TiO that dissaving polymer is modified2Intercalation aoxidizes
Graphene dispersion body；
The TiO of dissaving polymer modification is adjusted using acetic acid2Then the pH value of intercalation graphene oxide under mechanical stirring will
The 1H of 5th preset ratio, 1H, 2H, 2H- perfluoro capryl triethoxysilanes are slowly added into dissaving polymer modification
TiO2In intercalation graphene oxide dispersion；
Mixture is stirred at reflux the 7th preset time under the 7th preset temperature, after reaction, it is fluorine-based hyperbranched to obtain the end
Polymer-modified TiO2Intercalation graphene oxide.
Preferably, in above-mentioned preparation method, the 6th preset temperature is room temperature, and the 6th preset time is 3-
4 hours, the TiO of the dissaving polymer modification2Intercalation graphene oxide and absolute ethyl alcohol and the mixed solution of deionized water
（The ratio of ethyl alcohol and water is 8:1）The 5th preset ratio be 1:1.5, acetic acid adjusts the TiO of dissaving polymer modification2
The pH value of intercalation graphene oxide dispersion is 2.5-3, the TiO of dissaving polymer modification2Intercalation graphene oxide and 1H,
The mass ratio of 1H, 2H, 2H- perfluoro capryl triethoxysilane is 1:5, the 7th preset temperature be 80-90 DEG C, the described 7th
Preset time is 6-8 hours.
Preferably, in above-mentioned preparation method, which is characterized in that the weight percent of each raw material in the mixed solution
For：Hold the TiO of fluorine-based dissaving polymer modification2Intercalation graphene oxide 25%-45%, silane coupling agent 75%-55%.
Preferably, in above-mentioned preparation method, which is characterized in that the TiO of the fluorine-based dissaving polymer modification in end2
Two leachings two roll the concrete technology dried again and are after intercalation graphene oxide solution is mixed with silane coupler solution：Dipping temperature is
25-35 DEG C, dip time 10-20min, the pick-up of dacron is 40%-50%, and drying temperature is 50-70 DEG C, dry
Time is 30-60min.
Preferably, in above-mentioned preparation method, the graphene oxide is prepared by following steps：
1）Under the conditions of ice-water bath, a certain amount of natural flake graphite is slowly added into a certain amount of concentrated sulfuric acid, machinery stirs
It mixes until being uniformly mixed；
2）Under the action of mechanical agitation, it is slowly added to a certain amount of K2MnO4Until reaction completely；
3）A certain amount of distilled water mechanical agitation is added in, adds in a certain amount of H after mixing2O2, solution becomes by dark-brown
Glassy yellow；
4）With cleaning solution under the conditions of hydrochloric acid and distilled water Centrifugal dispersion to neutrality, stable graphene oxide solution is obtained.
Preferably, in above-mentioned preparation method, which is characterized in that the natural flake graphite and the quality of the concentrated sulfuric acid
Than being 1:30-1:40, the natural flake graphite and K2MnO4Mass ratio be 1:1-1:6, the natural flake graphite with
H2O2Mass ratio be 1:3-1:10, the volume ratio of the hydrochloric acid and distilled water is 1:5-1:10, the dosage of the distilled water
For 50-3000ml.
In the TiO of the fluorine-based dissaving polymer modification in end provided by the invention2Intercalation graphene oxide coating polyester fabric
Preparation method in, have the advantages that：First, preparation process is simple, raw materials used cheap and easily-available；Secondly, it is obtained
Hold the TiO of fluorine-based dissaving polymer modification2Intercalation graphene oxide good water solubility has super hydrophobic effect, and collects and urge
The functions such as change, super-hydrophobic, antibacterial are in one；Hold the TiO of fluorine-based dissaving polymer modification2Intercalation graphene oxide passes through chemistry
The connection of key can effectively promote its fastness between dacron, improve wearability.Hold fluorine-based dissaving polymer modification
TiO2Intercalation graphene oxide coating polyester fabric has both the functions such as super-hydrophobic, catalysis, antibacterial, uvioresistant, antistatic in one.
It has extremely significant application prospect in fields such as various bedding, hygienic material, ornament materials.
Description of the drawings
In order to illustrate more clearly of this specification embodiment or technical solution of the prior art, below will to embodiment or
Attached drawing needed to be used in the description of the prior art is briefly described, it should be apparent that, the accompanying drawings in the following description is only
Some embodiments described in this specification, for those of ordinary skill in the art, in not making the creative labor property
Under the premise of, it can also be obtained according to these attached drawings other attached drawings.
Fig. 1 is the TiO of the fluorine-based dissaving polymer modification of one embodiment of the invention middle-end2Intercalation graphite oxide ene coatings are washed
The flow chart of the preparation method of synthetic fibre fabric.
Specific embodiment
Purpose, technical scheme and advantage to make the application are clearer, below in conjunction with the application specific embodiment and
Technical scheme is clearly and completely described in corresponding attached drawing.Obviously, described embodiment is only the application one
Section Example, instead of all the embodiments.Based on the embodiment in the application, those of ordinary skill in the art are not doing
Go out all other embodiments obtained under the premise of creative work, shall fall in the protection scope of this application.
Below in conjunction with attached drawing, the technical solution that each embodiment of this specification provides is described in detail.
One embodiment of the invention provides a kind of TiO of the fluorine-based dissaving polymer modification in end2Intercalation graphene oxide
Preparation method, as shown in FIG. 1, FIG. 1 is the TiO of the fluorine-based dissaving polymer modification of one embodiment of the invention middle-end2Intercalation aoxidizes
The flow chart of the preparation method of graphene.The preparation method includes：TiO is prepared according to graphene oxide2Intercalation graphite oxide
Alkene, such as the step S101 in Fig. 1；According to the TiO2Intercalation graphene oxide prepares EDA and is modified TiO2Intercalation graphene oxide,
Such as the step S103 in Fig. 1；TiO is modified according to the EDA2Intercalation graphene oxide prepares the TiO of dissaving polymer modification2
Intercalation graphene oxide, such as the step S105 in Fig. 1；And the TiO modified according to the dissaving polymer2Intercalation aoxidizes
Graphene prepares the TiO of the fluorine-based dissaving polymer modification in end2Intercalation graphene oxide, such as the step S107 in Fig. 1；And
According to the TiO that fluorine-based dissaving polymer is held to modify2Intercalation graphene oxide prepares the TiO of the fluorine-based dissaving polymer modification in end2
Intercalation graphene oxide coating polyester fabric, such as the step S109 in Fig. 1.
Such as the step S101 in Fig. 1, TiO is prepared according to graphene oxide2Intercalation graphene oxide.
The graphene oxide is prepared by following steps：
1）Under the conditions of ice-water bath, 1g natural flake graphites are slowly added into the concentrated sulfuric acid of 23ml, mechanical agitation is until mixed
It closes uniform；
2）Under the action of mechanical agitation, it is slowly added to 3gK2MnO4Until reaction completely；
3）150ml distilled water and 5ml H are added in after completion of the reaction2O2, solution becomes glassy yellow by dark-brown；
4）25ml dilute hydrochloric acid and 125ml distilled water are added in, cleaning solution obtains stable oxidation stone to neutrality under the conditions of Centrifugal dispersion
Black alkene solution.
Next, the graphene oxide prepared is put into hydrothermal reaction kettle, first is reacted under the first preset temperature
Preset time after ultrasonic second preset time, anhydrous state is dried under the second preset temperature and obtains dewatered oxidation stone
Black alkene；By the hydrochloric acid, butyl titanate, sodium hydroxide solution of the dewatered graphene oxide and the first preset ratio close
It closes in container after ultrasonic third preset time, acquisition TiO2Intercalation graphene oxide solution；According to the TiO2Intercalation graphite oxide
Alkene solution obtains TiO2Intercalation graphene oxide.
Wherein, first preset temperature is 110-130 DEG C, and first preset time is 3-4 hours, and described second is pre-
If the time is 30-50 minute, second preset temperature is 40-50 DEG C, the graphene oxide and hydrochloric acid, butyl titanate,
First preset ratio of the quality of sodium hydroxide is 1:3:50:3, the third preset time is 3-4 hours.
Step S103, according to the TiO2Intercalation graphene oxide prepares EDA and is modified TiO2Intercalation graphene oxide.
Specifically, by the TiO2Intercalation graphene oxide is dispersed in by the second preset ratio containing ethylene modulators, two
In the DMF solution of carbodicyclo hexylimide and 4- dimethyl-nitrine pyridine, after supersound process, it is heated to third and presets temperature
Degree after reacting the 4th preset time, washs DMF by deionized water and centrifugation obtains the EDA and is modified TiO2Intercalation oxygen
Graphite alkene.
Wherein, the TiO2Second preset ratio of intercalation graphene oxide and the quality of the DMF solution is 1:500,
The mass ratio of DMF and ethylene modulators, dicyclohexylcarbodiimide, 4- dimethyl-nitrine pyridine are 1:0.2：0.02:0.004,
The third preset temperature is 50-70 DEG C, and the 4th preset time is 9-12 hours.
Step S105 is modified TiO according to EDA2Intercalation graphene oxide prepares the TiO of dissaving polymer modification2Intercalation oxygen
Graphite alkene.
Specifically, the EDA is modified TiO2Intercalation graphene oxide is dispersed in by third preset ratio containing two hexamethylenes
Dispersion is obtained in the nmp solution of base carbodiimide and 4- dimethyl-nitrine pyridine, pyridine and triphenyl phosphite；By the 4th
The LiCl powder and dissaving polymer of preset ratio are added in the dispersion and stirring and dissolving, obtains mixture；By institute
It states after mixture is heated to the 4th preset temperature under magnetic stirring, is added into being vigorously stirred to 10 times of mixture quality
In methanol；The 5th preset time of ultrasonic disperse, steams methanol under the 5th preset temperature, and acquisition is washed and centrifuged with DMF
The TiO of dissaving polymer modification2Intercalation graphene oxide.
Wherein, the TiO that EDA is modified2The third preset ratio of the quality of intercalation graphene oxide and nmp solution is 1:
160, NMP with DMAP, pyridine, triphenyl phosphite mass ratio be 1:0.006:0.06:0.1, the TiO that the EDA is modified2It inserts
The 4th preset ratio of layer graphene oxide and LiCl powder, the quality of dissaving polymer is 1:0.6:6, the described 4th
Preset temperature is 80-90 DEG C, and the 5th preset temperature is 70-80 DEG C, and the 5th preset time is 9-10 hours, described
Dissaving polymer is in Hyperbranched Polymer with Terminal Amido, Hyperbranched Polymer with Terminal Hydroxyl and end carboxyl super branched polymer
Any one or more.
Step S107, the TiO modified according to the dissaving polymer2It is fluorine-based hyperbranched that intercalation graphene oxide prepares end
Polymer-modified TiO2Intercalation graphene oxide.
Specifically, the TiO that the dissaving polymer is modified2Intercalation graphene oxide be dispersed in absolute ethyl alcohol and go from
In the mixed solution of sub- water, the 6th preset time is ultrasonically treated under the 6th preset temperature, obtains dissaving polymer modification
TiO2Intercalation graphene oxide dispersion；The TiO of dissaving polymer modification is adjusted using acetic acid2Intercalation graphene oxide disperses
The pH value of body, then under mechanical stirring by the 1H of the 5th preset ratio, 1H, 2H, 2H- perfluoro capryl triethoxysilanes are slow
It is added to the TiO of dissaving polymer modification2In intercalation graphene oxide dispersion；Mixture is stirred under the 7th preset temperature
The 7th preset time of reflux is mixed, after reaction, obtains the TiO of the fluorine-based dissaving polymer modification in the end2Intercalation graphene oxide.
Wherein, the 6th preset temperature is room temperature, and the 6th preset time is 3-4 hours, the hyperbranched polymerization
The TiO of object modification2Intercalation graphene oxide and absolute ethyl alcohol and the mixed solution of deionized water（The ratio of ethyl alcohol and water is 8:1）
The 5th preset ratio be 1:1.5, acetic acid adjusts the TiO of dissaving polymer modification2Intercalated graphite olefinic oxide disperses
The pH value of body is 2.5-3, the TiO of dissaving polymer modification2Intercalation graphene oxide and 1H, 1H, 2H, 2H- perfluoro capryl three
The mass ratio of Ethoxysilane is 1:5, the 7th preset temperature is 80-90 DEG C, and the 7th preset time is 6-8 hours.
Step S109, the TiO modified according to the fluorine-based dissaving polymer in the end2It is fluorine-based that intercalation graphene oxide prepares end
The TiO of dissaving polymer modification2Intercalation graphene oxide coating polyester fabric.
Specifically, the TiO that fluorine-based dissaving polymer modification will be held2It is added in after the concussion dispersion of intercalation graphene oxide solution
It into silane coupler solution, is sufficiently stirred to obtain mixed solution and is placed in padder immersion liquid slot, roll process by two leachings two
Mixed solution is padded on dacron, then the dacron after padding is placed in baking oven and is dried, end fluorine is made
The TiO of base dissaving polymer modification2Intercalation graphene oxide coating polyester fabric.
Wherein, the weight percent of each raw material is in the mixed solution：Hold the TiO of fluorine-based dissaving polymer modification2
Intercalation graphene oxide 25%-45%, silane coupling agent 75%-55%.Dipping temperature is 25-35 DEG C, dip time 10-
20min, the pick-up of dacron is 40%-50%, and oven temperature is 50-70 DEG C, drying time 30-60min.
Next, illustrate the TiO that fluorine-based dissaving polymer is held to modify with two specific embodiments again2Intercalation aoxidizes
The preparation method of graphene.
Embodiment 1
It puts 1g graphene oxides into hydrothermal reaction kettle, 3h, ultrasonic 30min is reacted at 110 DEG C, filter, nothing is dried at 40 DEG C
Water state obtains dewatered graphene oxide；The above-mentioned graphene oxides of 0.1g are weighed, is placed in closed container, adds in 0.3g's
Hydrochloric acid adds 5g butyl titanates, then adds in the sodium hydroxide solution of 0.3g, and ultrasonic 4h obtains TiO2Intercalation graphene oxide
Solution；Above-mentioned solution is placed in hydrothermal reaction kettle, crystalline forming under hot conditions.It is fully dry in 60 DEG C of drying box again
Into TiO2Intercalation graphene oxide.
Above-mentioned reactant takes 0.1g to be dispersed in first containing 10g ethylene modulators（EDA）, 1g dicyclohexylcarbodiimides and
0.2g4- dimethyl-nitrine pyridine（DMAP）50gDMF solution in, by ultrasonication, by mixture under magnetic stirring
It is heated to 60 DEG C.After reaction 9 hours, the EDA for washing DMF by deionized water and centrifuging needed for acquisition is modified TiO2Intercalation
Graphene oxide.
The TiO that the EDA of synthesis is modified2Intercalation graphene oxide weighs 0.1g and is dispersed in containing 96mgDMAP, 0.96g pyrroles
In the 16gNMP solution of pyridine and 1.6g triphenyl phosphites；The LiCl powder of 60mg and 0.6g dissaving polymers are added to again
In dispersion and stirring and dissolving, mixture is heated to 90 DEG C under magnetic stirring.After the completion, mixture is added drop-wise to 6.6g plays
In the methanol of strong stirring.Then ultrasonic disperse 9 hours under the conditions of 70 DEG C after steaming methanol, are washed with DMF and centrifugation obtain
Obtain the TiO of dissaving polymer modification2Intercalation graphene oxide.
Weigh the TiO of the dissaving polymer modification of 0.1g2Intercalation graphene oxide is dispersed in 0.15g absolute ethyl alcohols and goes
The TiO of dissaving polymer modification is obtained in the mixed solution of ionized water2Intercalation graphene oxide dispersion, and surpass at room temperature
Sonication 3h.The TiO of dissaving polymer modification is adjusted using acetic acid2The pH value of intercalation graphene oxide dispersion is to 2.5, so
Afterwards under mechanical stirring by the 1H of 0.5g, 1H, 2H, 2H- perfluoro capryl triethoxysilanes are slowly added into dissaving polymer
The TiO of modification2In intercalation graphene oxide dispersion.Mixture is stirred at reflux 6h at 80 DEG C.After reaction, centrifugation, washing,
Then it is freeze-dried, obtains the TiO of the fluorine-based dissaving polymer modification in required end2Intercalation graphene oxide.
By the TiO that will hold fluorine-based dissaving polymer modification of above-mentioned preparation2Intercalation graphene oxide is dispersed in water, shake
It is added in silane coupler solution after swinging, is sufficiently stirred to obtain mixed solution and is placed in padder immersion liquid slot, pass through two leachings
Two, which roll process, pads mixed solution on dacron, and then the dacron after padding is placed in baking oven and is dried,
The TiO of the fluorine-based dissaving polymer modification in end is made2Intercalation graphene oxide coating polyester fabric.
Wherein, the TiO of the fluorine-based dissaving polymer modification of the mixed solution middle-end2The weight hundred of intercalation graphene oxide
Divide than being 25%, the weight percent of silane coupling agent is 75%.Dipping temperature is 25 DEG C, and dip time 10min, terylene is knitted
The pick-up of object is 40%, and oven temperature is 50 DEG C, drying time 40min.
Embodiment 2
It puts 1g graphene oxides into hydrothermal reaction kettle, 4h, ultrasonic 30min is reacted at 120 DEG C, filter, nothing is dried at 50 DEG C
Water state obtains dewatered graphene oxide；The above-mentioned graphene oxides of 0.15g are weighed, are placed in closed container, add in 0.45g
Hydrochloric acid, add 7.5g butyl titanates, then add in the sodium hydroxide solution of 0.45g, ultrasonic 3h obtains TiO2Intercalation aoxidizes
Graphene solution；Above-mentioned solution is placed in hydrothermal reaction kettle, crystalline forming under hot conditions.It is filled in 60 DEG C of drying box again
Divide and be dried to TiO2Intercalation graphene oxide.
Above-mentioned reactant takes 0.15mg to be dispersed in first containing 15g ethylene modulators（EDA）, two Asia of 1.5g dicyclohexyls carbon
Amine and 0.3g4- dimethyl-nitrine pyridine（DMAP）75gDMF solution in, by ultrasonication, mixture is stirred in magnetic force
It mixes down and is heated to 60 DEG C.After reaction 11 hours, the EDA for washing DMF by deionized water and centrifuging needed for acquisition is modified
TiO2Intercalation graphene oxide.
The TiO that the EDA of synthesis is modified2Intercalation graphene oxide weighs 0.15g and is dispersed in containing 0.144gDMAP,
In the 24gNMP solution of 1.44g pyridines and 2.4g triphenyl phosphites；Again by the hyperbranched polymerization of LiCl powder and 0.9g of 90mg
Object is added in dispersion and stirring and dissolving, and mixture is heated to 90 DEG C under magnetic stirring.After the completion, mixture is added dropwise
In the methanol being vigorously stirred to 9.9g.Then ultrasonic disperse 10 hours under the conditions of 80 DEG C, after steaming methanol, washed with DMF and
Centrifuge the TiO for obtaining dissaving polymer modification2Intercalation graphene oxide.
Weigh the TiO of the dissaving polymer modification of 0.15g2Intercalation graphene oxide be dispersed in 0.225g absolute ethyl alcohols and
The TiO of dissaving polymer modification is obtained in the mixed solution of deionized water2Intercalation graphene oxide dispersion, and at room temperature
It is ultrasonically treated 3h.It adjusts to obtain the TiO of dissaving polymer modification using acetic acid2The pH value of intercalation graphene oxide dispersion arrives
3, then under mechanical stirring by the 1H of 0.75g, 1H, 2H, 2H- perfluoro capryl triethoxysilanes, which are slowly added into, to be overspend
The TiO of fluidized polymer modification2In intercalation graphene oxide dispersion.Mixture is stirred at reflux 8h at 90 DEG C.After reaction, from
The heart, washing, are then freeze-dried, and obtain the TiO of the fluorine-based dissaving polymer modification in required end2Intercalation graphene oxide.
By the TiO of the fluorine-based dissaving polymer modification in the end of above-mentioned preparation2Intercalation graphene oxide is dispersed in water, concussion
After be added in silane coupler solution, be sufficiently stirred to obtain mixed solution and be placed in padder immersion liquid slot, pass through two leachings two
It rolls process to pad mixed solution on dacron, then the dacron after padding is placed in baking oven and is dried, make
The TiO of fluorine-based dissaving polymer modification must be held2Intercalation graphene oxide coating polyester fabric.
Wherein, the TiO of the fluorine-based dissaving polymer modification of the mixed solution middle-end2The weight hundred of intercalation graphene oxide
Divide than being 45%, the weight percent of silane coupling agent is 55%.Dipping temperature is 35 DEG C, and dip time 20min, terylene is knitted
The pick-up of object is 50%, and oven temperature is 70 DEG C, drying time 60min.
In the TiO of the fluorine-based dissaving polymer modification in end provided by the invention2Intercalation graphene oxide coating polyester fabric
Preparation method in, have the advantages that：First, preparation process is simple, raw materials used cheap and easily-available；Secondly, it is obtained
Hold the TiO of fluorine-based dissaving polymer modification2Intercalation graphene oxide good water solubility has super hydrophobic effect, and collects and urge
The functions such as change, super-hydrophobic, antibacterial are in one；Hold the TiO of fluorine-based dissaving polymer modification2Intercalation graphene oxide passes through chemistry
The connection of key can effectively promote its fastness between dacron, improve wearability.Hold fluorine-based dissaving polymer modification
TiO2Intercalation graphene oxide coating polyester fabric has both the functions such as super-hydrophobic, catalysis, antibacterial, uvioresistant, antistatic in one.
It has extremely significant application prospect in fields such as various bedding, hygienic material, ornament materials.
The foregoing is merely embodiments herein, are not limited to the application.For those skilled in the art
For, the application can have various modifications and variations.All any modifications made within spirit herein and principle are equal
Replace, improve etc., it should be included within the scope of claims hereof.
Claims (11)
1. a kind of TiO of the fluorine-based dissaving polymer modification in end2The preparation method of intercalation graphene oxide coating polyester fabric,
It is characterized by the TiO by the way that fluorine-based dissaving polymer is held to modify2It is added to after the concussion dispersion of intercalation graphene oxide solution
It is sufficiently stirred to obtain mixed solution in silane coupler solution, roll process by two leachings two pads dacron by mixed solution
On, then dry and be prepared, the TiO of the fluorine-based dissaving polymer modification in the end2Intercalation graphene oxide preparation process packet
Containing following steps：
（1）TiO is prepared according to graphene oxide2Intercalation graphene oxide；
（2）According to the TiO2Intercalation graphene oxide prepares EDA and is modified TiO2Intercalation graphene oxide；
（3）TiO is modified according to the EDA2Intercalation graphene oxide prepares the TiO of dissaving polymer modification2Intercalation graphite oxide
Alkene；
（4）The TiO modified according to the dissaving polymer2Intercalation graphene oxide prepares the fluorine-based dissaving polymer modification in end
TiO2Intercalation graphene oxide.
2. preparation method according to claim 1, which is characterized in that the step（1）It specifically includes：
Graphene oxide is put into hydrothermal reaction kettle, the first preset time is reacted under the first preset temperature, ultrasound second is pre-
If after the time, anhydrous state is dried under the second preset temperature and obtains dewatered graphene oxide；
By the hydrochloric acid, butyl titanate, sodium hydroxide solution of the dewatered graphene oxide and the first preset ratio close
It closes in container after ultrasonic third preset time, acquisition TiO2Intercalation graphene oxide solution；
According to the TiO2Intercalation graphene oxide solution obtains TiO2Intercalation graphene oxide.
3. preparation method according to claim 2, which is characterized in that first preset temperature is 110-130 DEG C, described
First preset time is 3-4 hours, and second preset time is 30-50 minutes, and second preset temperature is 40-50 DEG C,
The graphene oxide and hydrochloric acid, butyl titanate, sodium hydroxide the first preset ratio of quality be 1:3:50:3, described
Three preset times are 3-4 hours.
4. preparation method according to claim 1, which is characterized in that the step（2）It specifically includes：
By the TiO2Intercalation graphene oxide is dispersed in sub- containing ethylene modulators, dicyclohexyl carbon two by the second preset ratio
In the DMF solution of amine and 4- dimethyl-nitrine pyridine, after supersound process, third preset temperature is heated to, reaction the 4th is pre-
If after the time, DMF is washed by deionized water and centrifuges the acquisition EDA modifications TiO2Intercalation graphene oxide.
5. preparation method according to claim 4, which is characterized in that the TiO2Intercalation graphene oxide and the DMF are molten
Second preset ratio of the quality of liquid is 1:500, DMF with ethylene modulators, dicyclohexylcarbodiimide, 4- dimethyl-nitrine
The mass ratio of pyridine is 1:0.2：0.02:0.004, the third preset temperature is 50-70 DEG C, and the 4th preset time is 9-
12 hours.
6. preparation method according to claim 1, which is characterized in that the step（3）It specifically includes：
The EDA is modified TiO2Intercalation graphene oxide be dispersed in by third preset ratio containing dicyclohexylcarbodiimide and
Dispersion is obtained in the nmp solution of 4- dimethyl-nitrine pyridine, pyridine and triphenyl phosphite；
The LiCl powder of 4th preset ratio and dissaving polymer are added in the dispersion simultaneously stirring and dissolving, mixed
Close object；
After the mixture is heated to the 4th preset temperature under magnetic stirring, it is added into the play of 10 times of mixture quality
In the methanol of strong stirring；
The 5th preset time of ultrasonic disperse, steams methanol under the 5th preset temperature, is washed and centrifuged with DMF and is overspend
The TiO of fluidized polymer modification2Intercalation graphene oxide.
7. preparation method according to claim 6, which is characterized in that the TiO that EDA is modified2Intercalation graphene oxide and NMP
The third preset ratio of the quality of solution is 1:160, NMP with DMAP, pyridine, triphenyl phosphite mass ratio be 1:
0.006:0.06:0.1, the TiO that the EDA is modified2The quality of intercalation graphene oxide and LiCl powder, dissaving polymer
4th preset ratio is 1:0.6:6, the 4th preset temperature is 80-90 DEG C, and the 5th preset temperature is 70-80
DEG C, the 5th preset time is 9-10 hours, and the dissaving polymer is Hyperbranched Polymer with Terminal Amido, terminal hydroxy group surpasses
Any one or more in branched polymer and end carboxyl super branched polymer.
8. preparation method according to claim 1, which is characterized in that the step（4）It specifically includes：
The TiO that the dissaving polymer is modified2Intercalation graphene oxide is dispersed in absolute ethyl alcohol and the mixing of deionized water is molten
In liquid, the 6th preset time is ultrasonically treated under the 6th preset temperature, obtains the TiO of dissaving polymer modification2Intercalation aoxidizes
Graphene dispersion body；
The TiO of dissaving polymer modification is adjusted using acetic acid2The pH value of intercalation graphene oxide dispersion, is then stirred in machinery
The lower 1H by the 5th preset ratio, 1H, 2H are mixed, 2H- perfluoro capryl triethoxysilanes are slowly added into dissaving polymer and repair
The TiO of decorations2In intercalation graphene oxide dispersion；
Mixture is stirred at reflux the 7th preset time under the 7th preset temperature, after reaction, it is fluorine-based hyperbranched to obtain the end
Polymer-modified TiO2Intercalation graphene oxide.
9. preparation method according to claim 8, which is characterized in that the 6th preset temperature be room temperature, the described 6th
Preset time is 3-4 hours, the TiO of the dissaving polymer modification2Intercalation graphene oxide and absolute ethyl alcohol and deionization
The mixed solution of water（The ratio of ethyl alcohol and water is 8:1）The 5th preset ratio be 1:1.5, acetic acid adjusts hyperbranched polymerization
The TiO of object modification2The pH value of intercalation graphene oxide dispersion is 2.5-3, the TiO of dissaving polymer modification2Intercalation aoxidizes stone
The mass ratio of black alkene and 1H, 1H, 2H, 2H- perfluoro capryl triethoxysilane is 1:5, the 7th preset temperature is 80-90
DEG C, the 7th preset time is 6-8 hours.
10. preparation method according to claim 1, which is characterized in that the weight percent of each raw material in the mixed solution
Than for：Hold the TiO of fluorine-based dissaving polymer modification2Intercalation graphene oxide 25%-45%, silane coupling agent 75%-55%.
11. preparation method according to claim 1, which is characterized in that the TiO of the fluorine-based dissaving polymer modification in end2
Two leachings two roll the concrete technology dried again and are after intercalation graphene oxide solution is mixed with silane coupler solution：Dipping temperature is
25-35 DEG C, dip time 10-20min, the pick-up of dacron is 40%-50%, and drying temperature is 50-70 DEG C, dry
Time is 30-60min.
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| CN111379163A (en) * | 2018-12-29 | 2020-07-07 | 江苏唐工纺实业有限公司 | Based on radial nano TiO2Preparation method of lyophobic polyester fabric |
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