CN112795264B - Hollow nano titanium dioxide @ lauryl sodium sulfate modified graphene/fluorinated copolymer composite leather finishing agent and preparation method thereof - Google Patents

Hollow nano titanium dioxide @ lauryl sodium sulfate modified graphene/fluorinated copolymer composite leather finishing agent and preparation method thereof Download PDF

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CN112795264B
CN112795264B CN202110115022.2A CN202110115022A CN112795264B CN 112795264 B CN112795264 B CN 112795264B CN 202110115022 A CN202110115022 A CN 202110115022A CN 112795264 B CN112795264 B CN 112795264B
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modified graphene
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dodecyl sulfate
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CN112795264A (en
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潘卉
王晓冬
刘国兴
丁涛
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Henan University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses a hollow nano titanium dioxide @ sodium dodecyl sulfate modified graphene/fluorinated copolymer compositeSynthetic leather finishing agent (marked as H-TiO)2The introduction of fluorine elements can effectively improve the water resistance and acid and alkali resistance of a polymer matrix, and the coating effect on the sheep skin shows that the synergistic coating effect of the nano titanium dioxide microspheres with the hollow structure and the reduced modified graphene nanosheets obviously improves the weather resistance and mechanical strength of the leather and endows the sheep leather with certain heat preservation and sanitary properties.

Description

Hollow nano titanium dioxide @ lauryl sodium sulfate modified graphene/fluorinated copolymer composite leather finishing agent and preparation method thereof
Technical Field
The invention belongs to the field of polymer-based composite materials, and particularly relates to a hollow nano titanium dioxide @ sodium dodecyl sulfate modified graphene/fluorinated copolymer composite leather finishing agent and a preparation method thereof.
Background
Finishing is an important operation for improving the added value of leather and beautifying the appearance quality of the leather, and is considered as the 'gold spot technique' of the leather quality by people in the industry, wherein the quality and variety of a finishing agent play a critical role. The leather finishing is to coat a layer of colored or colorless natural or synthetic polymer film on the surface of the dried and finished leather, and the traditional polymer leather finishing material has large solvent usage amount, is not aging-resistant and has serious environmental pollution. The new nano-material and the nano-technology play more and more important roles in improving the traditional coating material and the process thereof so as to improve the quality of leather and increase enterprise benefits. The hollow-structure nano titanium dioxide microspheres and the sodium dodecyl sulfate modified graphene oxide nanosheets prepared in the work are effectively compounded with the fluorinated copolymer matrix through a simple method, the novel hollow nano titanium dioxide @ sodium dodecyl sulfate modified graphene/fluorinated copolymer composite leather finishing agent is prepared, and a good finishing effect is obtained on the sheepskin.
Disclosure of Invention
The invention aims to provide a hollow nano titanium dioxide @ lauryl sodium sulfate modified graphene/fluorinated copolymer composite leather finishing agent and a preparation method thereofEffectively compounded hollow structure nano TiO2The microsphere and the reduced modified graphene nanosheet simultaneously play a synergistic nano-coating effect, so that the weather resistance and the ageing resistance of the sheep leather are obviously improved, the physical and mechanical properties of the sheep leather are improved without influencing the light transmittance and transparency of the coated leather due to the introduction of the reduced modified graphene nanosheet, and the composite coating agent also endows the sheep leather with better heat preservation and sanitation properties.
In order to achieve the purpose, the invention adopts the following technical scheme:
hollow nano TiO2The preparation method of the @ lauryl sodium sulfate modified graphene/fluorinated copolymer composite leather finishing agent comprises the following steps:
(1) adding Butyl Acrylate (BA), Methyl Methacrylate (MMA) and Acrylic Acid (AA) monomers into an emulsifier for pre-emulsification to obtain a pre-emulsified monomer I;
(2) adding Dodecafluoroheptyl methacrylate (DFMA), butyl acrylate, methyl methacrylate and acrylic acid into an emulsifier for pre-emulsification to obtain a pre-emulsified monomer II;
(3) adding an appropriate amount of initiator into the pre-emulsified monomer I, heating to 70-90 ℃ under mechanical stirring, carrying out heat preservation reaction for 0.5-2 hours, then slowly dropwise adding the pre-emulsified monomer II and an appropriate amount of initiator into a reaction system, keeping the temperature of the system at 80-90 ℃ after dropwise adding, and continuing the reaction for 1-3 hours to obtain a product, namely F-PBMA;
(4) respectively taking hollow nano TiO2(as H-TiO)2) Sodium Dodecyl Sulfate (SDS) -modified graphene (recorded as SDS-rGO) or hollow nano TiO2@ dodecyl sodium sulfate modified graphene (marked as H-TiO)2@ SDS-rGO) is firstly ultrasonically dispersed in distilled water to form uniform solution, and then the uniform solution and fluorine modified copolymer emulsion are respectively prepared into hollow nano titanium dioxide/fluorinated copolymer (marked as H-TiO) by a blending method at a certain temperature2F-PBMA, comparative sample)), sodium dodecyl sulfate modified graphene/fluorinated copolymer (noted SDS-rGO/F-PBMA, comparative sample), andhollow nano TiO of target product2@ dodecyl sodium sulfate modified graphene/fluorinated copolymer (noted as H-TiO)2@ SDS-rGO/F-PBMA) composite leather finishing agent and hollow nano TiO2The adding amount of the @ sodium dodecyl sulfate modified graphene is 0.25% -10% of the effective mass of the fluorine modified copolymer emulsion.
Further, the hollow nano TiO in the step (4)2@ dodecyl sodium sulfate modified graphene (marked as H-TiO)2@ SDS-rGO) was prepared as follows: dissolving sodium dodecyl sulfate modified graphene in distilled water, and adding hollow nano TiO into the solution2Uniformly dispersing by ultrasonic, carrying out heat preservation reaction for 20-30 h at 55-65 ℃ under stirring, carrying out centrifugal separation, and drying a product to obtain hollow nano titanium dioxide @ sodium dodecyl sulfate modified graphene, wherein the sodium dodecyl sulfate modified graphene and the hollow nano TiO are2The mass ratio is 1: 1.
Further, hollow nano TiO2The preparation process is as follows:
(1) adding ammonia water into a part of absolute ethyl alcohol according to the volume ratio of 1:10, heating to 45-55 ℃, dissolving ethyl orthosilicate into b part of absolute ethyl alcohol to prepare an ethyl orthosilicate ethanol solution, dropwise adding the ethyl orthosilicate ethanol solution, reacting at 45-55 ℃ for 1-3 h, performing centrifugal separation, washing and drying the obtained precipitate to obtain silicon dioxide nano microspheres (marked as nano-SiO)2) Standby; the volume ratio of the ammonia water to the ethyl orthosilicate is 2:1, and a: b =3: 1;
(2) ultrasonically treating silicon dioxide nano-microspheres, absolute ethyl alcohol and tetrabutyl titanate to form uniform dispersion liquid, dropwise adding a mixed solution of ammonia water, ethyl alcohol and distilled water into the dispersion liquid under stirring (the mixed solution is ultrasonically treated for 5min before dropwise adding to form the uniform solution), continuously reacting for 1-3 h at room temperature after dropwise adding is finished, then carrying out hydrothermal reaction for 20-30 h at 150-200 ℃ on the reaction liquid, centrifugally separating, washing and drying a solid product to obtain titanium dioxide coated silicon dioxide composite nano-particles (marked as SiO)2@TiO2) For standby, the dosage ratio of the silicon dioxide nano-microspheres to the tetrabutyl titanate to the ammonia water is 0.1g: 0.45mL: 0.12mL, and the mixture is reacted in a reaction systemThe volume ratio of the ethanol to the distilled water is 5: 1;
(3) taking dried SiO2@TiO2Dissolving the composite nano particles in 1-5M sodium hydroxide solution to obtain SiO2@TiO2The proportion of the composite nanometer particles to the sodium hydroxide is 1g to 1mol, the mixture reacts for 1 to 3 hours at the temperature of 75 to 85 ℃ under stirring, the centrifugal separation is carried out, the solid product is washed and dried, and the final product, namely the hollow nanometer titanium dioxide (marked as H-TiO)2）。
Further, the preparation process of the sodium dodecyl sulfate modified graphene (SDS-rGO) is as follows: and (2) taking GO, SDS, hydrazine hydrate and distilled water, carrying out ultrasonic mixing uniformly, heating to 95-100 ℃ under stirring, reacting for 1-2 h, carrying out centrifugal separation, washing and drying a solid product to obtain a product of sodium dodecyl sulfate modified graphene, wherein the dosage ratio of GO to SDS to hydrazine hydrate is 0.5g:1g:0.5 mL.
Further, the mass percentage of the butyl acrylate, the methyl methacrylate and the acrylic acid monomer in the step (1) is 48:31: 21; in the step (2), the mass percentage of the butyl acrylate, the methyl methacrylate and the acrylic acid monomer is 48:31:22, and the dosage of the dodecafluoroheptyl methacrylate accounts for 14.85 percent of the total mass of the butyl acrylate, the methyl methacrylate and the acrylic acid monomer.
Further, the emulsifier in the step (1) and the step (2) is Sodium Dodecyl Sulfate (SDS), the adding amount of the emulsifier in the step (1) is 1.8 percent of the total mass of the butyl acrylate, the methyl methacrylate and the acrylic acid monomer, the adding amount of the emulsifier in the step (2) is 2.38 percent of the total mass of the butyl acrylate, the methyl methacrylate and the acrylic acid monomer, and the concentration of the SDS in the emulsifier solution is 12 g/L.
Further, the initiator in the step (3) is Ammonium Persulfate (APS), the addition amount of the initiator in the pre-emulsified monomer I is 1.8% of the total mass of butyl acrylate, methyl methacrylate and acrylic acid monomers in the pre-emulsified monomer I, the addition amount of the initiator when the pre-emulsified monomer II is added is 2.38% of the total mass of butyl acrylate, methyl methacrylate and acrylic acid monomers in the pre-emulsified monomer II, and the concentration of ammonium persulfate in the initiator solution is 30 g/L.
Further, in the step (4), H-TiO2(comparative samples)/F-PBMA (comparative samples), SDS-rGO/F-PBMA (comparative samples) and the target product H-TiO2The preparation process of the @ SDS-rGO/F-PBMA nano composite emulsion comprises the following steps: 0.045g of H-TiO each2SDS-rGO and H-TiO2Respectively dispersing the @ SDS-rGO in 15mL of distilled water, carrying out ultrasonic treatment for 30min, respectively adding 15g of fluorinated copolymer with the solid content of about 30% into the three dispersions, respectively transferring the three dispersions into 50mL of three-neck flask provided with a condenser tube and a thermometer, mechanically stirring the three dispersions for 30min at normal temperature, then heating the dispersions to 80 ℃, and continuously reacting the dispersions for 4H under strong stirring to obtain the hollow nano titanium dioxide/fluorinated copolymer (marked as H-TiO)2F-PBMA, comparative sample)), sodium dodecyl sulfate modified graphene/fluorinated copolymer (noted as SDS-rGO/F-PBMA, comparative sample) and target product hollow nano TiO2@ dodecyl sodium sulfate modified graphene/fluorinated copolymer (noted as H-TiO)2@ SDS-rGO/F-PBMA) composite leather finishing agent.
The application adopts a simple and easy method to prepare a novel fluorinated copolymer-based nano composite leather finishing agent (H-TiO)2The introduction of @ SDS-rGO/F-PBMA), the water resistance and acid and alkali resistance of the polymer matrix can be effectively improved, and the coating effect on the sheep leather shows that the synergistic coating effect of the nano titanium dioxide microspheres with the hollow structure and the reduced modified graphene nanosheets obviously improves the weather resistance and mechanical strength of the leather and endows the sheep leather with certain heat preservation and sanitary properties.
Drawings
FIG. 1 shows hollow nano titanium dioxide particles (H-TiO)2) Reduced graphene nanoplatelets (rGO), sodium dodecyl sulfate modified graphene nanoplatelets (SDS-rGO) and hollow nano titanium dioxide particles/sodium dodecyl sulfate modified graphene composites (H-TiO)2@ SDS-rGO) in the Fourier infrared spectrogram;
FIG. 2 shows the observation of nano SiO under a Scanning Electron Microscope (SEM)2(FIG. 2a), titanium oxide-coated silicon oxide composite nanoparticles (SiO)2@TiO2FIG. 2 b), hollow nano titanium dioxide particles (H-TiO)2FIG. 2 c) and hollow nano-titanium dioxide particles/sodium dodecyl sulfate modified graphene composite (H-TiO)2The morphology of @ SDS-rGO, FIG. 2 d); scale in the figure: 100 nm;
FIG. 3 is for SiO2@TiO2EDS analysis of composite nanoparticles;
FIG. 4 shows reduced graphene nanoplatelets (rGO), sodium dodecyl sulfate-modified graphene nanoplatelets (SDS-rGO) and hollow nano titanium dioxide particles/sodium dodecyl sulfate-modified graphene composites (H-TiO)2@ SDS-rGO);
FIG. 5 is a reduced graphene nanoplate (rGO), sodium dodecyl sulfate modified graphene nanoplate (SDS-rGO) and hollow nano titanium dioxide particles/sodium dodecyl sulfate modified graphene composite (H-TiO)2@ SDS-rGO) in water (mass percentage concentration is 1%);
FIG. 6 shows the fluorine modified copolymer emulsion (F-PBMA) and the composite emulsion (H-TiO) added with different nano materials2the/F-PBMA, SDS-rGO/F-PBMA and H-TiO prepared in example 32@ SDS-rGO/F-PBMA) for 1 month, it can be seen that the emulsion has better stability;
FIG. 7 shows the UV-VISIBLE absorption spectrum (a) and UV-VISIBLE transmission spectrum (b) of the fluorine-modified copolymer emulsion (F-PBMA) and the composite emulsion coating film with different nano-materials added, H-TiO2@ SDS-rGO/F-PBMA was prepared from example 3;
FIG. 8 shows the fluorine modified copolymer (F-PBMA) and the composite emulsion coating film (H-TiO) added with different nano materials2(iv) a combination of/F-PBMA, SDS-rGO/F-PBMA and H-TiO2@ SDS-rGO/F-PBMA) is soaked in water for 24 hours, and then the contact angle of the fluorine modified copolymer coating film to water in air is respectively tested, and the comparison result shows that the fluorine modified copolymer coating film presents hydrophobic property, and H-TiO2The @ SDS-rGO/F-PBMA nano composite coating film (prepared in example 3) has better hydrophobicity and water resistance (the contact angle is more than 100)o）；
FIG. 9 shows fluorine modified copolymer (F-PBMA) and composite emulsion coating (H-TiO) with different nano-materials added2(iv) a combination of/F-PBMA, SDS-rGO/F-PBMA and H-TiO2@ SDS-rGO/F-PBMA) is soaked in a hydrochloric acid and sodium hydroxide solution with the mass percentage concentration of 5 percent for 24 hours, the contact angle of the coating film to water in the air is tested, and the comparison result shows that H-TiO2The @ SDS-rGO/F-PBMA nano composite coating film (prepared in example 3) has better hydrophobicity and acid and alkali stability (the contact angle is more than 100)o），H-TiO2@ SDS-rGO/F-PBMA was prepared from example 3;
FIG. 10 shows fluorine modified copolymer (F-PBMA) and composite emulsion coating (H-TiO) with different nano-materials added2(iv) a combination of/F-PBMA, SDS-rGO/F-PBMA and H-TiO2Stress-strain curve of @ SDS-rGO/F-PBMA), and analysis of the results for H-TiO2The coated film of @ SDS-rGO/F-PBMA has high mechanical strength, H-TiO2@ SDS-rGO/F-PBMA was prepared from example 3;
FIG. 11 shows the uncoated sheep skin (a) and H-TiO, respectively, observed under SEM2The shape of the surface (b) of the coated sheep skin is compared with that of the coated sheep skin with the @ SDS-rGO/F-PBMA, the coated sheep skin is flat and smooth in surface and basically free of defects, and H-TiO2@ SDS-rGO/F-PBMA was prepared from example 3, scale: 100 μm.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited thereto. The aqueous initiator solutions in the following examples were prepared by dissolving 1.2g of ammonium persulfate in 40mL of distilled water. The specific preparation process of the emulsifier comprises the following steps: the SDS was dissolved in 100mL of water (1.2 g).
1. Hollow nano TiO2Fine particles (H-TiO)2) Preparation of
12mL of concentrated aqueous ammonia commercially available in a concentrated amount and 120mL of ethanol are introduced into a 250mL three-necked flask equipped with a condenser tube, a mechanical stirring rod and a thermometer, and the temperature is raised to 50 ℃ with stirring, to which an ethanol solution of tetraethoxysilane (6 mL of tetraethoxysilane dissolved in 40mL of ethanol solvent) is slowly added dropwise, and the mixture is sonicated with a KH2200 type ultrasonic cleaner at a power of 100W5min to form a uniform solution), dripping for 1 h-1.5 h, then continuously stirring at 50 ℃ for reaction for 2h, centrifugally separating, washing with water and absolute ethyl alcohol for three times respectively, and drying in an oven at 60 ℃ for 24h to obtain nano-silica particles (nano-SiO)2) And (5) standby.
Taking dried 0.1g of nano SiO2Firstly putting particles, 15mL of ethanol and 0.45mL of TBOT (tetrabutyl titanate) into a 50mL beaker, carrying out ultrasonic treatment for 30min by 100W to uniformly disperse the particles, slowly dropwise adding a mixed solution of 0.12mL of commercial concentrated ammonia water, 15mL of ethanol and 6mL of distilled water into the beaker under magnetic stirring (the mixed solution is subjected to ultrasonic treatment for 5min before dropwise adding to form a uniform solution), wherein the dropwise adding time is about 1 h-1.5 h, continuously reacting for 2h under stirring after the dropwise adding is finished, then transferring the dispersed solution into a 50mL hydrothermal high-pressure reaction kettle, carrying out hydrothermal reaction for 24h at 180 ℃, carrying out centrifugal separation (8000 revolutions per minute), centrifuging and washing obtained solid products for three times by water and ethanol respectively, then putting the solid products into an oven, and drying the solid products for 24h at 60 ℃ to obtain titanium oxide coated silicon oxide composite nanoparticles, which are marked as SiO2@TiO2And then standby.
0.1gSiO of2@TiO2Adding the composite nano particles into 50mL of 2mol/L sodium hydroxide solution, reacting for 2H under magnetic stirring at 80 ℃, performing centrifugal separation, washing the obtained solid product with distilled water for three times, and drying in a 60 ℃ oven for 24H to obtain hollow nano titanium dioxide particles for later use, wherein the hollow nano titanium dioxide particles are marked as H-TiO2。
2. Preparation of sodium dodecyl sulfate modified graphene (SDS-rGO)
Firstly preparing a graphene oxide aqueous solution by adopting an improved Hummers method, freeze-drying at-30 ℃ (LGJ 12 vacuum freeze dryer) to obtain solid graphene oxide nanosheets (marked as GO), then adding 0.5g of GO, 1g of SDS, 0.5mL of hydrazine hydrate and 50mL of distilled water into a beaker, carrying out 100W ultrasonic treatment for 30min, transferring into a 100mL three-mouth flask provided with a condenser tube and a thermometer, heating to 98 ℃ under magnetic stirring, reacting for 90min at the temperature, carrying out centrifugal separation, washing with distilled water for three times, drying in an oven at 60 ℃ for 24h to obtain a product of sodium dodecyl sulfate modified graphene, marked as SDS-rGO (correspondingly, rGO obtained without adding SDS), and reserving for later use.
3. Hollow nano titanium dioxide @ sodium dodecyl sulfate modified graphene (H-TiO)2@ SDS-rGO) nanocomposite particle preparation
0.1g of SDS-rGO was dissolved in 100mL of distilled water and placed in a 250mL beaker, to which 0.1g of H-TiO was added2And carrying out ultrasonic treatment at 100W for 30min, transferring the dispersion into a 250mL three-neck flask provided with a condenser and a thermometer, heating to 60 ℃, reacting for 24H under magnetic stirring, carrying out centrifugal separation (8000 rpm), placing the solid precipitate in an oven, and drying for 24H at 60 ℃ to obtain hollow nano titanium dioxide/sodium dodecyl sulfate modified graphene nano composite particles, which are marked as H-TiO2@SDS-rGO。
Hollow nano titanium dioxide particle (H-TiO)2) Reduced graphene nanoplatelets (rGO), sodium dodecyl sulfate modified graphene nanoplatelets (SDS-rGO) and hollow nano titanium dioxide particles/sodium dodecyl sulfate modified graphene composites (H-TiO)2@ SDS-rGO) is shown in FIG. 1; the successful preparation of the target product can be seen by comparing the infrared spectra of different nanomaterials in fig. 1.
Nano SiO2Titanium oxide-coated silicon oxide composite nanoparticles (SiO)2@TiO2) Hollow nano titanium dioxide particles (H-TiO)2) And hollow nano titanium dioxide particles/sodium dodecyl sulfate modified graphene composite (H-TiO)2@ SDS-rGO) is detailed in FIG. 2; as can be seen from FIG. 2, the first prepared nano SiO2The grain size is about 290nm, SiO2@TiO2The particle diameter of the composite nanometer particles is increased to about 350nm and is in a flower shape, and the nanometer SiO is removed by alkali etching2H-TiO obtained after nucleation2The particle size of the nano particles is slightly reduced to about 340nm, and the effective composition with SDS-rGO is realized.
SiO2@TiO2EDS analysis of composite nanoparticles is detailed in FIG. 3, and the results in FIG. 3 further illustrate the successful coating of nano-titania on the surface of nano-silica.
Reduced graphene nanoplatelets (rGO), sodium dodecyl sulfate-modified graphene nanoplatelets (SDS-rGO), and voidsNano titanium dioxide particle/sodium dodecyl sulfate modified graphene composite (H-TiO)2The Raman spectrogram of @ SDS-rGO) is shown in figure 4, and the disorder degree of the modified graphene nanosheet is obviously increased after modification and compounding as can be seen from figure 4.
4. Preparation of fluorine-modified copolymer (F-PBMA)
19.2g BA, 12.4g MMA and 8.4g AA were added to 60mL of an emulsifier solution (prepared by dissolving 1.2g SDS in 100mL of distilled water), and the mixture was sheared and emulsified at 3000rmp for 2min to form a pre-emulsified monomer I; 9.6g BA, 6.2g MMA, 4.4g AA and 3g DFMA were added to 40mL of an emulsifier solution (prepared by dissolving 1.2g SDS in 100mL of distilled water), and the mixture was sheared and emulsified at 3000rmp for 2min to form a pre-emulsified monomer II; adding a pre-emulsified monomer I into a 250mL three-neck flask provided with a mechanical stirrer, a condenser pipe and a thermometer, simultaneously adding 24mL of initiator solution (1.2 g of ammonium persulfate is dissolved in 40mL of distilled water), heating to 75 ℃, stirring, reacting for 0.5h, then simultaneously and slowly dropwise adding the pre-emulsified monomer II and the rest 16mL of initiator aqueous solution (1.2 g of ammonium persulfate is dissolved in 40mL of distilled water) into the reaction solution, completing dropping for about 2-2.5 h, heating to 85 ℃ after dropping, stirring, continuing to react for 2h, stopping the reaction, obtaining a fluorine modified copolymer matrix, marking as F-PBMA, measuring the content of active substances to be 30% for later use.
5. H-TiO2Preparation of/F-PBMA nanocomposite
0.045g of H-TiO are weighed2Adding 15mL of distilled water, performing 100W ultrasonic treatment for 30min, adding 15g of fluorine modified copolymer (F-PBMA, effective component content of 30%), stirring at room temperature for 30min, heating to 80 deg.C, stirring, and reacting for 4 hr to obtain H-TiO2(H-TiO) for standby use of/F-PBMA nano composite emulsion 21 percent of the effective substance content of the emulsion by mass percent).
Preparation of SDS-rGO/F-PBMA nanocomposite
Weighing 0.045g of SDS-rGO, adding the SDS-rGO into 15mL of distilled water, carrying out ultrasonic treatment for 30min by 100W, adding 15g of fluorine modified copolymer (the content of effective substances is 30%), stirring the mixed solution for 30min at normal temperature, heating to 80 ℃, stirring, and continuing to react for 4h to obtain the SDS-rGO/F-PBMA nano composite emulsion for later use (the mass percentage of the SDS-rGO in the content of the effective substances of the emulsion is 1%).
Example 1 0.0113g of H-TiO are taken2Dispersing the @ SDS-rGO in 15mL of distilled water, carrying out 100W ultrasonic treatment for 10min to form uniform dispersion liquid, adding 15g of fluorinated copolymer emulsion (F-PBMA, the content of active substances is 30%), stirring at high speed for 5min by adopting 10000rmp of an FJ200 high-speed dispersion homogenizer, transferring into a 50mL three-neck flask provided with a condenser, a mechanical stirrer and a thermometer, stirring at normal temperature for 15min, heating to 80 ℃, continuing stirring at high speed for 1H, finishing the reaction, and obtaining H-TiO2@ SDS-rGO/F-PBMA nano composite leather finishing emulsion (H-TiO)2The mass percentage of the @ SDS-rGO in the effective substance of the emulsion is 0.25 percent).
Example 2 0.0225g of H-TiO was taken2Dispersing the @ SDS-rGO in 15mL of distilled water, carrying out 100W ultrasonic treatment for 15min to form uniform dispersion liquid, adding 15g of fluorinated copolymer (F-PBMA, the content of active substances is 30%), stirring at high speed for 5min by using an FJ200 high-speed dispersion homogenizer, transferring into a 50mL three-neck flask provided with a condenser, a mechanical stirrer and a thermometer, stirring at normal temperature for 15min, heating to 80 ℃, continuing to stir strongly for 1.5H, finishing the reaction, and obtaining the H-TiO2@ SDS-rGO/F-PBMA nano composite leather finishing emulsion (H-TiO)2The mass percentage of the @ SDS-rGO in the effective substance of the emulsion is 0.5 percent).
Example 3 0.0450g of H-TiO was taken2Dispersing the @ SDS-rGO in 15mL of distilled water, carrying out 100W ultrasonic treatment for 20min to form uniform dispersion liquid, adding 15g of fluorinated copolymer emulsion (F-PBMA, the content of active substances is 30%), stirring at high speed for 8min by using an FJ200 high-speed dispersion homogenizer, transferring into a 50mL three-neck flask provided with a condenser tube, a mechanical stirrer and a thermometer, stirring at normal temperature for 20min, heating to 80 ℃, continuing to stir strongly for 2H, finishing the reaction, and obtaining the H-TiO2@ SDS-rGO/F-PBMA nano composite leather finishing emulsion (H-TiO)2The mass percentage of the @ SDS-rGO in the effective substance of the emulsion is 1 percent).
Example 4 0.0900g of H-TiO was taken2@ SDS-rGO was dispersed in 15mL of distilled water, sonicated at 100W for 20min to form a uniform dispersion, and then introduced thereintoAdding 15g of fluorinated copolymer emulsion (F-PBMA, the content of active substances is 30%), stirring at high speed for 8min by using an FJ200 high-speed dispersion homogenizer, transferring into a 50mL three-neck flask provided with a condenser tube, a mechanical stirrer and a thermometer, stirring at normal temperature for 20min, heating to 80 ℃, continuing to stir strongly for 2H, and finishing the reaction to obtain H-TiO2@ SDS-rGO/F-PBMA nano composite leather finishing emulsion (H-TiO)2The mass percentage of the @ SDS-rGO in the effective substance of the emulsion is 2 percent).
Example 5 0.1800g of H-TiO was taken2Dispersing the @ SDS-rGO in 15mL of distilled water, carrying out 100W ultrasonic treatment for 20min to form uniform dispersion liquid, adding 15g of fluorinated copolymer emulsion (F-PBMA, the content of active substances is 30%), stirring at high speed for 10min by using an FJ200 high-speed dispersion homogenizer, transferring into a 50mL three-neck flask provided with a condenser tube, a mechanical stirrer and a thermometer, stirring at normal temperature for 30min, heating to 80 ℃, continuing to stir strongly for 2.5H, finishing the reaction, and obtaining the H-TiO2@ SDS-rGO/F-PBMA nano composite leather finishing emulsion (H-TiO)2The mass percentage of the @ SDS-rGO in the effective substance of the emulsion is 4 percent).
Example 6 0.3600g of H-TiO2Dispersing the @ SDS-rGO in 15mL of distilled water, carrying out 100W ultrasonic treatment for 20min to form uniform dispersion liquid, adding 15g of fluorinated copolymer emulsion (F-PBMA, the content of active substances is 30%), stirring at high speed for 10min by using an FJ200 high-speed dispersion homogenizer, transferring into a 50mL three-neck flask provided with a condenser tube, a mechanical stirrer and a thermometer, stirring at normal temperature for 30min, heating to 80 ℃, continuing to stir strongly for 2.5H, finishing the reaction, and obtaining the H-TiO2@ SDS-rGO/F-PBMA nano composite leather finishing emulsion (H-TiO)2The mass percentage of the @ SDS-rGO in the effective substance of the emulsion is 8 percent).
EXAMPLE 7 0.4500g of H-TiO were taken2Dispersing the @ SDS-rGO in 15mL of distilled water, carrying out 100W ultrasonic treatment for 20min to form uniform dispersion liquid, adding 15g of fluorinated copolymer emulsion (F-PBMA, the content of active substances is 30%), stirring at high speed for 10min by using an FJ200 high-speed dispersion homogenizer, transferring into a 50mL three-neck flask provided with a condenser tube, a mechanical stirrer and a thermometer, stirring at normal temperature for 30min, heating to 80 ℃, continuing to stir strongly for 3h, and finishing the reactionTo obtain H-TiO2@ SDS-rGO/F-PBMA nano composite leather finishing emulsion (H-TiO)2The mass percentage of the @ SDS-rGO in the effective substance of the emulsion is 10 percent).
Respectively taking 0.15g of rGO, SDS-rGO and H-TiO2And H-TiO2The specific result is shown in figure 5, wherein @ SDS-rGO is dispersed in 15mL of distilled water by ultrasonic treatment (KH 2200 type ultrasonic cleaner, power 100W) for 10min, and the dispersion is carried out in water after standing for 24 hours; taking F-PBMA and H-TiO2the/F-PBMA, SDS-rGO/F-PBMA emulsions and the H-TiO prepared in example 32The stability of the @ SDS-rGO/F-PBMA composite coating emulsion sample is observed after 15mL of each sample is stood at normal temperature for 1 month, the specific result is shown in figure 6, and the reduced graphene nanosheets are not dispersed in water and H-TiO can be seen from figure 52SDS-rGO and H-TiO2@ SDS-rGO is stable in dispersion in water. It can be seen from FIG. 6 that both the fluorinated copolymer emulsion and the nanocomposite emulsion exhibited better stability after standing for several months.
F-PBMA、H-TiO2Coating films of/F-PBMA and SDS-rGO/F-PBMA and H-TiO prepared in example 32The ultraviolet-visible absorption and transmission spectrum analysis result of the @ SDS-rGO/F-PBMA nano composite coating film is shown in figure 7, and H-TiO can be seen from figure 7a2The ultraviolet absorption performance of the compound finishing agent is obviously improved by introducing SDS-rGO, and the weather resistance of the finished leather can be effectively improved; the comparison of the ultraviolet-visible transmission spectrum of the film is shown in FIG. 7b, and it can be seen from FIG. 7b that the transmittance of the composite coated film in the visible region is 80% or more, and the coated film can provide better transparency to leather.
Mixing F-PBMA and H-TiO2Coating films of/F-PBMA and SDS-rGO/F-PBMA and H-TiO prepared in example 32The @ SDS-rGO/F-PBMA nano composite coating film is soaked in water for 24 hours and then naturally dried, the change of the contact angle before and after soaking is contrasted, the result is shown in figure 8, and figure 8 shows that H-TiO is introduced simultaneously2The contact angle of the composite coating film after the coating film is coated with SDS-rGO to water in the air is obviously improved; similarly, the coating film was immersed in 5wt% sulfuric acid and 5wt% sodium hydroxide solution for 24 hours and then naturally dried, and the results are shown in FIG. 9, in which the contact angle before and after immersion in the acid-base solution was compared with the contact angle change before and after immersion in the acid-base solution, and it can be seen from FIG. 9 that the contact angle before and after immersion in water and immersion in acid-base was not observedThe obvious change shows that the composite coating film has better water resistance and acid-base resistance.
Respectively taking 10mL of F-PBMA and 1% of H-TiO2Coating emulsion of/F-PBMA and 1% SDS-rGO/F-PBMA and H-TiO prepared in example 32And (2) pouring the @ SDS-rGO/F-PBMA into a polytetrafluoroethylene mold, naturally airing for 48 hours at room temperature, then putting the mold into a vacuum drying oven for drying for 24 hours, and taking the mold out for later use (the thickness of the dried film is 1 mm). The tensile strength, the maximum strength and the elongation at break data (tested on a TCS-2000 microcomputer control electronic universal tester according to GB/T528-2006, the tensile speed is 500 mm/min) and the stress-strain performance of the coating film are tested. The results are detailed in FIG. 10 and Table 1.
TABLE 1F-PBMA, H-TiO2(iv) a combination of/F-PBMA, SDS-rGO/F-PBMA and H-TiO2Physical and mechanical properties of @ SDS-rGO/F-PBMA composite emulsion coating film
Figure DEST_PATH_IMAGE001
Table 1 and FIG. 10 show H-TiO2The @ SDS-rGO/F-PBMA coated film has higher tensile strength and maximum strength.
12g of F-PBMA and 1 percent of H-TiO are respectively taken2(ii)/F-PBMA, 1% SDS-rGO/F-PBMA and H-TiO prepared in example 32The @ SDS-rGO/F-PBMA coating emulsion was sprayed onto about 400 square centimeters of sheep skin using a Wood F-75 type pneumatic spray gun. The thickness of the coating layer measured by a micrometer (0-150mm, combined precision machinery, Shenzhen, China) is 30 micrometers. The thermal conductivity of the uncoated sheepskin and the coated skin surfaces were tested and the results are detailed in table 2.
TABLE 2F-PBMA, H-TiO2(iv) a combination of/F-PBMA, SDS-rGO/F-PBMA and H-TiO2Heat conductivity coefficient of @ SDS-rGO/F-PBMA coated sheep skin
Figure DEST_PATH_IMAGE002
Table 2 lists the fluorine modified copolymer (F-PBMA) and the composite emulsion (H-TiO) with different added nano-materials2/F-PBMASDS-rGO/F-PBMA and H-TiO2The heat conductivity coefficient of the coated sheep skin (tested by adopting a TC3000 heat conductivity coefficient instrument of Xian Xixia electronic technology Co., Ltd., voltage of 1.5V and time interval of 1 s) is smaller, the heat conductivity is reduced, and therefore the leather has certain heat preservation characteristics. It can be seen from the table that H-TiO2The coating of @ SDS-rGO/F-PBMA endows the sheep skin with better heat preservation performance.
12g of each of the H-TiO compounds obtained in examples 1 to 7 were taken2The @ SDS-rGO/F-PBMA nano composite leather finishing emulsion is sprayed on a sheep skin with the thickness of about 400 square centimeters by using a Wujie F-75 type pneumatic spray gun. The thickness of the coating layer measured by a micrometer (0-150mm, combined precision machinery, Shenzhen, China) is 30 micrometers. The thermal conductivity of the uncoated sheepskin and the coated skin surfaces were tested and the results are detailed in table 3.
TABLE 3H-TiO2Heat conductivity coefficient of coated sheep skin of composite coating agent under different percentages of @ SDS-rGO (in percentage by mass of fluorinated copolymer matrix)
Figure DEST_PATH_IMAGE003
Table 3 shows H-TiO2In the heat conductivity test of the coated sheep skin with the composite coating agent prepared when the percentages of the @ SDS-rGO composite nanoparticles to the fluorine-modified copolymer (F-PBMA) matrix (by mass%) were 0.25% (prepared in example 1), 0.5% (prepared in example 2), 1% (prepared in example 3), 2% (prepared in example 4), 4% (prepared in example 5), 8% (prepared in example 6) and 10% (prepared in example 7), respectively, it was found that H-TiO2The heat conductivity value is the smallest when the proportion of @ SDS-rGO is 1%, and the heat conductivity value of the coated leather is improved inversely with the increase of the content, and the possibility that the composite particles with larger concentration are unevenly distributed in the polymer matrix is considered.

Claims (8)

1. Hollow nano TiO2The preparation method of the @ lauryl sodium sulfate modified graphene/fluorinated copolymer composite leather finishing agent is characterized by comprising the following steps ofThe method comprises the following steps:
(1) adding butyl acrylate, methyl methacrylate and acrylic acid monomers into an emulsifier solution for pre-emulsification to obtain a pre-emulsified monomer I;
(2) adding dodecafluoroheptyl methacrylate, butyl acrylate, methyl methacrylate and acrylic acid monomers into an emulsifier solution for pre-emulsification to obtain a pre-emulsified monomer II;
(3) adding a pre-emulsified monomer I into an initiator solution, heating to 70-90 ℃ under mechanical stirring, carrying out heat preservation reaction for 0.5-2 hours, then simultaneously dropwise adding a pre-emulsified monomer II and the initiator solution into a reaction system, and keeping the system temperature at 80-90 ℃ after dropwise adding, and continuing the reaction for 1-3 hours to obtain a product, namely a fluorine modified copolymer emulsion;
(4) taking hollow nano TiO2Ultrasonically dispersing the @ sodium dodecyl sulfate modified graphene in distilled water to form uniform dispersion liquid, adding the fluorine modified copolymer emulsion, and stirring at 70-90 ℃ for 1-3 hours to obtain a target product, namely the hollow nano TiO2@ lauryl sodium sulfate modified graphene/fluorinated copolymer composite leather finishing agent and hollow nano TiO2The adding amount of the @ sodium dodecyl sulfate modified graphene is 0.25% -10% of the effective mass of the fluorine modified copolymer emulsion.
2. The hollow nano TiO of claim 12The preparation method of the @ sodium dodecyl sulfate modified graphene/fluorinated copolymer composite leather finishing agent is characterized in that the hollow nano TiO in the step (4) is adopted2The preparation process of the @ sodium dodecyl sulfate modified graphene is as follows: dissolving sodium dodecyl sulfate modified graphene in distilled water, and adding hollow nano TiO into the solution2Uniformly dispersing by ultrasonic, carrying out heat preservation reaction for 20-30 h at 55-65 ℃ under stirring, carrying out centrifugal separation, and drying a product to obtain hollow nano titanium dioxide @ sodium dodecyl sulfate modified graphene, wherein the sodium dodecyl sulfate modified graphene and the hollow nano TiO are2The mass ratio is 1: 1.
3. The hollow nano TiO of claim 22The preparation method of the @ sodium dodecyl sulfate modified graphene/fluorinated copolymer composite leather finishing agent is characterized in that the preparation method comprises the step of preparing a hollow nano TiO coating agent2The preparation process is as follows:
(1) adding ammonia water into a part of absolute ethyl alcohol according to the volume ratio of 1:10, heating to 45-55 ℃, dissolving ethyl orthosilicate into b part of absolute ethyl alcohol to prepare an ethyl orthosilicate ethanol solution, dropwise adding the ethyl orthosilicate ethanol solution, reacting at 45-55 ℃ for 1-3 h under heat preservation after dripping, performing centrifugal separation, washing and drying the obtained precipitate to obtain silicon dioxide nano microspheres for later use; the volume ratio of the ammonia water to the ethyl orthosilicate is 2:1, and a: b =3: 1;
(2) ultrasonically treating silicon dioxide nano-microspheres, absolute ethyl alcohol and tetrabutyl titanate to form uniform dispersion liquid, dropwise adding a mixed solution of ammonia water, ethyl alcohol and distilled water into the dispersion liquid under stirring, continuously reacting at room temperature for 1-3 h after dropwise adding, then carrying out hydrothermal reaction on the reaction liquid for 20-30 h at 150-200 ℃, carrying out centrifugal separation, washing and drying a solid product to obtain SiO2@TiO2Compounding nanometer particle in the amount of 0.1g to 0.45mL to 0.12 mL;
(3) taking dried SiO2@TiO2Dissolving the composite nano particles in 1-5M sodium hydroxide solution to obtain SiO2@TiO2The proportion of the composite nanometer particles to the sodium hydroxide is 1g to 1mol, the composite nanometer particles and the sodium hydroxide react for 1 to 3 hours at the temperature of 75 to 85 ℃ under stirring, centrifugal separation is carried out, and the solid product is washed and dried to obtain the final product, namely the hollow nanometer titanium dioxide.
4. The hollow nano TiO of claim 22The preparation method of the @ sodium dodecyl sulfate modified graphene/fluorinated copolymer composite leather finishing agent is characterized in that the preparation process of the sodium dodecyl sulfate modified graphene is as follows: and (2) taking GO, SDS, hydrazine hydrate and distilled water, carrying out ultrasonic mixing uniformly, heating to 95-100 ℃ under stirring, reacting for 1-2 h, carrying out centrifugal separation, washing and drying a solid product to obtain a product of sodium dodecyl sulfate modified graphene, wherein the dosage ratio of GO to SDS to hydrazine hydrate is 0.5g:1g:0.5 mL.
5. The hollow nano TiO of claim 12The preparation method of the @ sodium dodecyl sulfate modified graphene/fluorinated copolymer composite leather finishing agent is characterized in that the mass ratio of butyl acrylate, methyl methacrylate and acrylic acid monomer in the step (1) is 48:31: 21; in the step (2), the mass ratio of the butyl acrylate to the methyl methacrylate to the acrylic acid monomer is 48:31:22, and the dosage of the dodecafluoroheptyl methacrylate accounts for 14.85 percent of the total mass of the butyl acrylate, the methyl methacrylate and the acrylic acid monomer.
6. The hollow nano TiO of claim 12The preparation method of the @ sodium dodecyl sulfate modified graphene/fluorinated copolymer composite leather finishing agent is characterized in that the emulsifier in the step (1) and the step (2) is SDS, the adding amount of the emulsifier in the step (1) is 1.8% of the total mass of butyl acrylate, methyl methacrylate and acrylic monomers, the adding amount of the emulsifier in the step (2) is 2.38% of the total mass of butyl acrylate, methyl methacrylate and acrylic monomers, and the concentration of SDS in an emulsifier solution is 12 g/L.
7. The hollow nano TiO of claim 12The preparation method of the @ sodium dodecyl sulfate modified graphene/fluorinated copolymer composite leather finishing agent is characterized in that the initiator in the step (3) is ammonium persulfate, the addition amount of the initiator in the pre-emulsified monomer I is 1.8% of the total mass of butyl acrylate, methyl methacrylate and acrylic acid monomers in the pre-emulsified monomer I, the addition amount of the initiator when the pre-emulsified monomer II is added is 2.38% of the total mass of butyl acrylate, methyl methacrylate and acrylic acid monomers in the pre-emulsified monomer II, and the concentration of ammonium persulfate in the initiator solution is 30 g/L.
8. Hollow nano TiO produced by the production method according to any one of claims 1 to 72@ lauryl sodium sulfate modified graphene/fluorinated copolymer composite leather finishing agent.
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