CN107541572B - Surface-functionalized spherical nano-silicon dioxide-graphene oxide/polymer matrix composite tanning agent and preparation method thereof - Google Patents
Surface-functionalized spherical nano-silicon dioxide-graphene oxide/polymer matrix composite tanning agent and preparation method thereof Download PDFInfo
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Abstract
A kind of surface-functionalized spherical Nano-meter SiO_22Graphene oxide/polymer matrix composite tanning agent and preparation method thereof, prepared novel nano composite tanning agent dissolubility in water phase is good, it is very beneficial for the infiltration and absorption of tanning agent molecule, spherical nano-composite tanning agent is small due to frictional resistance, it is easier to permeate and be filled in leather collagen fabric gap under the mechanical force of rotary drum, it is used for tanning sheep wet-white leather, and thickening rate and capable of reaching 189% for skin substantially increases the utilization rate of skin.Skin shrinkage temperature can reach 80 DEG C or more after tan, and after compounding 0.5% chrome tanning, shrinkage temperature can reach 95 DEG C or more, significantly improve the hydrothermal stability of leather, meet the service performance requirement of resultant Leather.And skin has been also equipped with certain antistatic property and anti-flammability after tan.A kind of novel nano composite tanning agent that can partially replace chrome tanning of this working invention, the chrome-free tanning research to clean provide a kind of new approaches and new method.
Description
Technical field
The invention belongs to field of nanocomposite materials, and in particular to a kind of surface-functionalized ball shaped nano SiO2Aoxidize stone
Black alkene/polymer matrix composite tanning agent and preparation method thereof.
Background technique
Leather industry bring problem of environmental pollution seriously affects the development of curriery all the time, and traditional is tanned
Journey be unable to do without chrome tanning, chromium resource shortage and is more toxic, and thoroughly abandoning chrome tanning is the basic method for solving pollution of chromium, Chrome-free or
Less chrome tannage is one of the hot spot of current global leather circle research, and research is still conceived to the exploitation of conventional tanning agents mostly both at home and abroad
With the improvement of technique for applying, it is difficult to meet the requirement of the good service performance of finished leather with the chrome-free tanning agent that conventional method is developed.
Realize that the key of chrome-free tanning is to improve the stability of tanning agent and collagen cross-linked structure and assign the certain filling of finished leather to imitate
Fruit, this is also exactly what existing syntans cannot have both.By surface-functionalized ball shaped nano SiO2With the effect of chemical bonding
Form is supported on stannic oxide/graphene nano lamella, and with a kind of novel nano composite tanning agent of the effectively compound preparation of polymer, ball
The Nano-meter SiO_2 of shape2Collaboration tanning effect can be played simultaneously during leather tanning with the nano-graphene of two-dimensional slice, in glue
Former azelon and the intermolecular generation high density crosslinking points of tanning agent promote macromolecular chain and skin by the inorganic matter of nano-dispersion
The cross-linked network of leather glue fibrinogen acts on, to form the inorganic-organic network structure of high compaction inside leather, significantly mentions
The hydrothermal stability and mechanical performance of high collagen will also assign leather a series of new excellent properties such as antistatic property and resistance
Combustion property etc..It will be expected to develop a kind of novel nano composite tanning agent that can partially replace even complete substitution chromium, to realize thorough
The clean leather-making at bottom.
Summary of the invention
The present invention improves traditional tanning technology using nanometer new technology and nanometer new material, it is therefore intended for preparing a kind of surface
The spherical Nano-meter SiO_2 of functionalization2Graphene oxide/polymer matrix composite tanning agent and preparation method thereof, spherical SiO2Nanometer is micro-
Grain plays simultaneously with two-dimensional graphene nano lamella cooperates with tanning effect, not only significantly improves the heat stability of tanning
And mechanical performance, the also fabulous filling capacity of imparting leather (thickening obvious), while tanbark softness are plentiful and elastic
It is good.The leather of such tanning agent tanning also has antistatic property (conductivity raising) and certain flame-retarding characteristic.
In order to achieve the above objectives, the invention adopts the following technical scheme:
A kind of surface-functionalized spherical nano-silicon dioxide (SiO2)-graphene oxide/polymer matrix composite tanning agent system
Preparation Method includes the following steps:
(1) by PVA-SiO2Aqueous solution or PEG-SiO2Aqueous solution and GO aqueous solution mixing after under stiring 40~
60 DEG C are reacted 6~8 hours, centrifuge separation, are taken solid dry, are obtained PVA-SiO2- GO or PEG-SiO2- GO, PVA-SiO2Or
PEG-SiO2Mass percent with GO is respectively (2 ~ 50): 1, wherein GO represents graphene oxide, PVA-SiO2Represent surface
The SiO modified by PVA (polyvinyl alcohol)2, PEG-SiO2Represent the SiO that surface is modified by PEG (polyethylene glycol)2；
(2) PVA-SiO is weighed2- GO or PEG-SiO2- GO, situ aggregation method or solution blended process are added to vinyl
In polymeric matrix, surface-functionalized ball shaped nano SiO is prepared2Graphene oxide/polymer-based nano composite tanning agent, wherein
PVA-SiO2- GO or PEG-SiO2- GO accounts for 0.25 wt of wt %~6 % of polyvinyl matrix substance content.
Further, PVA-SiO in the step (1)2Or PEG-SiO2Preparation process it is as follows: ethyl orthosilicate is molten
In ethyl alcohol, after dropwise addition ammonium hydroxide to pH is 9,45~50 DEG C of 1~2h of reaction, the aqueous solution or polyethylene glycol of polyvinyl alcohol is added
Aqueous solution, 50 DEG C of reactions for 24 hours, centrifuge separation, solid ethanol washing, it is dry to get.
Further, the degree of polymerization 1700 of polyvinyl alcohol, (analysis is pure, is purchased from the brilliant pure biochemical technology in Shanghai for alcoholysis degree 88%
Limited liability company, product number: P105124)；The molecular weight of polyethylene glycol be 200 ~ 6000 (analysis it is pure, be purchased from Tianjin
Ke Miou chemical reagent Co., Ltd).
Further, the mass ratio of polyvinyl alcohol or polyethylene glycol and ethyl orthosilicate is (1 ~ 2) ︰ (1 ~ 2).
Preferably, the polyvinyl matrix is one of following: (1) maleic anhydride and acrylic acid are total to
Polymers；(2) acrylic resin；(3) maleic anhydride acrylic copolymer.
Preferably, when polyvinyl matrix is the copolymer of maleic anhydride and acrylic acid, using in situ poly-
It is legal, maleic anhydride is first dissolved in in deionized water obtaining reaction solution I at 75~85 DEG C, then by PVA-SiO2- GO or PEG-
SiO2- GO, which is dissolved in deionized water, obtains reaction solution II, and reaction solution I and reaction solution II are mixed to obtain reaction solution at 75~85 DEG C
The deionized water solution and acrylic acid of ammonium persulfate are added dropwise into reaction solution III simultaneously by III, and temperature control is added dropwise 85
~90 DEG C the reaction was continued 3 ~ 6 hours, after reaction with the sodium hydroxide solution of 30wt % adjust product solution pH value to 5~
6, discharging to get.
Preferably, the mass ratio of the maleic anhydride, acrylic acid and ammonium persulfate be 23 ︰ (37 ~ 38) ︰ (1 ~ 1.5),
PVA-SiO2- GO or PEG-SiO2- GO accounts for the % of 0.25 %~6 of maleic anhydride and acrylic acid gross mass.
Preferably, when polyvinyl matrix is acrylic resin or maleic anhydride acrylic copolymer, use is molten
Liquid blending method, by PVA-SiO2- GO or PEG-SiO2- GO is dissolved in deionized water, adds acrylic resin or maleic anhydride third
Olefin(e) acid copolymer, react at room temperature 3 ~ 4h, discharging to get.
Utilize surface-functionalized ball shaped nano SiO made from above-mentioned preparation method2Graphene oxide/polymer matrix is multiple
Close tanning agent.
Such nano-composite tanning agent is used for tanning sheep wet-white leather, and skin, which thickens rate, can reach 189 %, substantially increase skin
Utilization rate.Remove from office shrinkage temperature after tan and reach 80 DEG C or more, compound 0.5wt%(to account in terms of tare weight) chrome tanning after, shrinkage temperature energy
Reach 95 DEG C or more, significantly improve the hydrothermal stability of leather, meets the service performance requirement of resultant Leather.Especially tan
Leather has been also equipped with certain antistatic property and anti-flammability afterwards.Wherein, the PVA-SiO as made from embodiment 22-GO/PMAAA
Nano-composite tanning agent tanning sheep wet-white leather 4 wt% of tare weight (dosage be), then compound 0.5 wt%(to account in terms of tare weight) chromium
Powder, skin shrinkage temperature can reach 98.2 DEG C after tan.
Detailed description of the invention
Fig. 1 is graphene oxide (GO), the non-functionalized nano SiO in surface2, surface-functionalized ball shaped nano SiO2(i.e.
PVA-SiO2And PEG-SiO2, the degree of polymerization that the molecular weight of PEG is 1500, PVA is 1700, PVA or PEG and ethyl orthosilicate
Mass ratio be 1:1) and surface-functionalized ball shaped nano SiO2Stannic oxide/graphene nano composite (i.e. PVA-SiO2- GO and
PEG-SiO2- GO is made by embodiment 6) FTIR spectrum figure (molecular structure of prepared sample is provided, it was demonstrated that at
Function prepares target product)；
Fig. 2 is the graphene oxide (GO) and surface-functionalized ball shaped nano SiO observed under scanning electron microscope2
(i.e. PVA-SiO2And PEG-SiO2, the degree of polymerization that the molecular weight of PEG is 1500, PVA is 1700, PVA or PEG and positive silicic acid second
The mass ratio of ester is 1:1) pattern；As seen from Figure 2: stannic oxide/graphene nano piece is in silk shape pleated structure, surface
Functionalized nano SiO2It is graininess spheroidal structure, good dispersion, about 50~200 nm of partial size；
Fig. 3 is the surface-functionalized ball shaped nano SiO observed under scanning electron microscope2Stannic oxide/graphene nano is multiple
Close pattern (the i.e. PVA-SiO of object2- GO and PEG-SiO2- GO is made by embodiment 6), it will thus be seen that surface-functionalized spherical shape is received
Rice SiO2It is uniformly distributed and is supported on stannic oxide/graphene nano on piece；
Fig. 4 is different sample (PVA-SiO2 、PEG-SiO2, GO, the PVA-SiO as made from embodiment 62- GO and PEG-
SiO2The degree of polymerization that the molecular weight of-GO, PEG are 1500, PVA is 1700, PVA or PEG and the mass ratio of ethyl orthosilicate is
1:1) dispersibility in water, as shown in Figure 4, surface-functionalized ball shaped nano SiO2(PVA-SiO2Or PEG-SiO2), oxidation
Graphene nanometer sheet and surface-functionalized ball shaped nano SiO2Stannic oxide/graphene nano composite (PVA-SiO2- GO and PEG-
SiO2- GO) stable solution can be formed in water, the several months is placed without precipitating generation；
Fig. 5 is the uv absorption spectra of nano-composite tanning agent (compound made from embodiment 2, embodiment 7 to 9), from
As can be seen that PVA-SiO in figure2- GO or PEG-SiO2- GO significantly improves the uv absorption property of PMAAA, can effectively change
The weatherability of kind leather；
Fig. 6 is the shrinkage temperature pair of leather after commercially available acrylic resin, embodiment 2, tanning agent tan made from embodiment 7 to 9
Than figure (4 wt% that dosage is tare weight), surface-functionalized ball shaped nano SiO2Graphene oxide/polymer-based nano is compound
Tanning agent substantially increases the heat stability of sheep wet-white leather, wherein the PVA-SiO as made from embodiment 22-GO/PMAAA
The shrinkage temperature of tanning skin can achieve 80.4 DEG C, meet the requirement of leather service performance；
Fig. 7 is commercially available acrylic resin, leather thickens rate comparison after tanning agent tan made from embodiment 2, embodiment 7 to 9
Scheme (4 wt% that dosage is tare weight), as shown in Figure 7 surface-functionalized ball shaped nano SiO2Graphene oxide/polymer matrix is received
Rice composite tanning agent thickens obviously leather, wherein the PVA-SiO as made from embodiment 22- GO/PMAAA tanning skin thickens rate
It can achieve 189 %, substantially increase the utilization rate of leather；
Fig. 8 is commercially available acrylic resin, (dosage is skin to leather after tanning agent tan made from embodiment 2, embodiment 7 to 9
4 wt% of weight) electrochemical impedance spectroscopy comparison diagram, impedance experiment be in KCl (0.1 mol/L), K3[Fe(CN)6] (5
) and K mmol/L4[Fe(CN)6] carry out in (5 mmol/L) mixed solution, 5V is superimposed on the DC voltage that voltage is 0.21V
Alternating voltage, nyquist diagram is recorded in the mKHz of 100 KHz ~ 100 frequency range, test equipment is global point of Germany
The Zahner electrochemical workstation that test equipment Co., Ltd provides is analysed, model is IM6ex, all nyquist plots in figure
Spectrogram all includes two parts: the high frequency region of corresponding electronics transfer resistance sizes and the linear low frequency range of corresponding region diffusion process,
Semicircle radius is bigger, and resistance is higher.Surface-functionalized ball shaped nano SiO as shown in Figure 82Graphene oxide/polymer matrix is received
Rice composite tanning agent (i.e. PVA-SiO2- GO/PMAAA and PEG-SiO2- GO/PMAAA) significantly reduce skin compared to straight polymer tanning agent
The resistance of leather enhances the antistatic property of skin.Antistatic property is related with material surface resistance and volume resistance, in general
Surface resistivity is higher, and volume resistivity is higher, and resistance is smaller, and the antistatic property of substance is better.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment, but protection model of the invention
It encloses and is not limited thereto.
1. surface-functionalized ball shaped nano SiO2Preparation
3 mL ethyl orthosilicates are dissolved in 60 mL ethyl alcohol, and it is 9 that ammonium hydroxide (25 wt% ~ 28wt%), which are added dropwise, to pH, and reaction is warm
Degree control is reacted 2 hours at 50 DEG C, obtains reaction solution 1..Weighing 1~6 g polyvinyl alcohol, (referred to as PVA, polyvinyl alcohol gather
Right is 1700, alcoholysis degree 88%) or polyethylene glycol (referred to as PEG, molecular weight 200,400,1500,4000 or
6000) it is sufficiently dissolved into 25 mL deionized waters under ultrasonic (400 W of power) processing, obtains reaction solution 2., polyvinyl alcohol or poly-
The mass ratio of ethylene glycol and ethyl orthosilicate can be 1:1,1:2 and 2:1,2. reaction solution is added to reaction solution 1. in, 50
DEG C stirring under be further continued for reaction 24 hours.Reaction terminates, and is centrifugated (8000 revs/min), solid product dehydrated alcohol is abundant
Washing, 60 DEG C be dried in vacuo polyvinyl alcohol or polyethylene glycol surface modification ball shaped nano SiO2(it is denoted as PVA-SiO2With
PEG-SiO2), spare, this nanoparticle favorable dispersibility in water.
2. the preparation of stannic oxide/graphene nano piece
1 g natural flake graphite powder (Sinopharm Chemical Reagent Co., Ltd., spectroscopic pure) is in ice-water bath and stirs at low speed
Under, it is slowly added into the 25 mL concentrated sulfuric acids, is sufficiently mixed uniformly, obtains reaction solution 1..5 g potassium permanganate are weighed in ice-water bath
With stir at low speed down be added to component in batches reaction solution 1. in, added in 1 hour.2 hours are reacted after adding at room temperature directly
Become blackish green to reaction solution, obtains reaction solution 2..To reaction solution 2. in continuously slowly inject deionized water, control reaction system
Temperature is at 100 DEG C hereinafter, the hydrogen peroxide of 5~10 mL 5v % is added 2. reaction solution to be diluted to 80~100 mL after, until molten
Liquid becomes glassy yellow, detects upper liquid pH=7, filters while hot.With 5 wt% dilute hydrochloric acid solutions and the abundant cleaning product of deionized water
To close to neutrality, it is centrifuged, filtering, 60 DEG C are dried in vacuo to obtain graphite oxide.By graphite oxide in ratio (the quality percentage of 1:100
Than) be scattered in distilled water, being put into cell disruptor Ultrasound Instrument, (JY99-ZD, 400W, the new sesame biotechnology share in Ningbo are limited
Company) in, 2 hours are ultrasonically treated to get graphene oxide water solution, and then Rotary Evaporators revolving is handled, and obtains graphite oxide
Alkene nanometer sheet (graphene oxide, GO), it is spare.
3. surface-functionalized ball shaped nano SiO2The preparation of stannic oxide/graphene nano composite
Ultrasonication is by PVA-SiO2Or PEG-SiO220~100 mL deionized waters are dissolved in, are obtained uniform and stable molten
Liquid is 1.；GO is dissolved in 20~50 mL deionized waters and obtains uniform and stable solution 2. by ultrasonication.Solution 1. with solution 2.
It is reacted 6~8 hours under 60 DEG C, stirring, obtains surface-functionalized ball shaped nano SiO2Stannic oxide/graphene nano composite (is denoted as
PVA-SiO2- GO and PEG-SiO2- GO) solution, it is centrifugated, it is dry, it is spare.PVA-SiO2Or PEG-SiO2With the quality of GO
Percentage is 2:1,5:1,10:1,20:1,25:1 or 50:1.
4. surface-functionalized ball shaped nano SiO2The preparation of graphene oxide/polymer-based nano composite tanning agent
Weigh suitable surface-functionalized ball shaped nano SiO2Stannic oxide/graphene nano composite (PVA-SiO2-GO,
PEG-SiO2- GO), polyvinyl matrix is added to situ aggregation method or nano particle filling (solution blending) method
In, surface-functionalized ball shaped nano SiO is prepared at room temperature2Graphene oxide/polymer-based nano composite tanning agent, wherein PVA-
SiO2- GO or PEG-SiO2- GO accounts for the 0.25 of polymeric matrix effective substance (i.e. the quality of straight polymer in polymeric matrix) content
The % of %~6.
1 23 g maleic anhydride of embodiment is completely dissolved in 100 mL deionized waters at 75~85 DEG C, is obtained instead
Answer liquid 1.；0.30 g PVA-SiO2(degree of polymerization of PVA is 1700 to-GO；The mass ratio of PVA and ethyl orthosilicate is 1:2；PVA-
SiO2It is dissolved in 20 mL deionized waters and being ultrasonically treated 30 minutes for 10:1) with the mass ratio of GO, obtain the reaction solution of stable homogeneous
②；Reaction solution is uniformly mixed under stirring 1. with reaction solution 2. at 75~85 DEG C, obtains reaction solution 3.；1.2 g ammonium persulfates are dissolved in
After 10 mL deionized waters and 36 mL acrylic acid (AA) simultaneously to reaction solution 3. in slowly drop evenly, temperature control is added dropwise
The reaction was continued 4 hours at 85~90 DEG C for system, and reaction terminates to adjust product solution pH value to 5 with the sodium hydroxide solution of 30 wt%
~6, discharging obtains surface-functionalized ball shaped nano SiO2Graphene oxide/maleic anhydride-acrylic copolymer nanometer is multiple
It closes tanning agent and (is denoted as PVA-SiO2-GO/PMAAA)。
2 23 g maleic anhydride (MA) of embodiment is completely dissolved in 100 mL deionized waters at 75~85 DEG C
In, obtain reaction solution 1.； 1.22 g PVA-SiO2- GO or PEG-SiO2The degree of polymerization of-GO(PVA is 1700；The molecular weight of PEG
It is 1500;The mass ratio of PVA, PEG and ethyl orthosilicate is 1:1；PVA-SiO2Or PEG-SiO2Mass ratio with GO is
It 5:1) is dissolved in 50 mL deionized waters and being ultrasonically treated 30 minutes, obtain the reaction solution of stable homogeneous 2.；1. and reaction solution reaction solution
2. being uniformly mixed under strength mechanical stirring at 75~85 DEG C, obtaining reaction solution 3.；1.2 g ammonium persulfates are dissolved in 10 mL deionizations
Water and 36 mL acrylic acid (AA) simultaneously to reaction solution 3. in slowly drop evenly, temperature control is added dropwise at 85~90 DEG C
The reaction was continued 4 hours, and reaction terminates to be adjusted product solution pH value with the sodium hydroxide solution of 30 wt% to 5~6, and discharging obtains table
Face functionalization ball shaped nano SiO2Graphene oxide/maleic anhydride-acrylic copolymer nano-composite tanning agent (is denoted as
PVA-SiO2-GO/PMAAA)。
3 23 g maleic anhydride (MA) of embodiment is completely dissolved in 100 mL deionized waters at 75~85 DEG C
In, obtain reaction solution 1.；2.44 g PVA-SiO2(degree of polymerization of PVA is 1700 to-GO；The mass ratio of PVA and ethyl orthosilicate is
2:1；PVA-SiO2It is dissolved in 80 mL deionized waters and being ultrasonically treated 30 minutes for 20:1) with the mass ratio of GO, obtain stable homogeneous
Reaction solution is 2.；1. 2. reaction solution is uniformly mixed with reaction solution under 75~85 DEG C, strength mechanical stirring, obtain reaction solution 3.；1.2
G ammonium persulfate be dissolved in 10 mL deionized waters and 36 mL acrylic acid (AA) simultaneously to reaction solution 3. in slowly drop evenly, drip
Adding Bi Wendu control, the reaction was continued 4 hours at 85~90 DEG C, and reaction terminates to adjust product with the sodium hydroxide solution of 30wt %
For solution ph to 5~6, discharging obtains surface-functionalized ball shaped nano SiO2Graphene oxide/maleic anhydride-acrylic acid is total
Polymers nano-composite tanning agent (is denoted as PVA-SiO2-GO/PMAAA)。
4 1.20 g PVA-SiO of embodiment2(degree of polymerization of PVA is 1700 to-GO；The mass ratio of PVA and ethyl orthosilicate
For 1:1；PVA-SiO2It is dissolved in 15 mL deionized waters and being ultrasonically treated 30 minutes for 25:1) with the mass ratio of GO, obtain stable homogeneous
Reaction solution 1.；1. reaction solution is added to 80 g acrylic resins (CHINATAN OM, Foshan Shi Telang chemical industry are limited
Company, substance content or solid content: 30 % ± 5) in, it stirs 4 hours at room temperature, discharging obtains surface-functionalized ball shaped nano
SiO2Graphene oxide/acrylic resin nano-composite tanning agent (is denoted as PVA-SiO2-GO/CHINATAN OM)。
5 1.80 g PEG-SiO of embodiment2(molecular weight of PEG is 1500 to-GO；The mass ratio of PEG and ethyl orthosilicate
For 1:2；PEG-SiO2It is dissolved in 15 mL deionized waters and being ultrasonically treated 30 minutes for 50:1) with the mass ratio of GO, obtain stable homogeneous
Reaction solution 1.；1. reaction solution is added to 100 g maleic anhydride acrylic copolymer (CHINATAN TM, Foshan Shi Te
Bright Chemical Co., Ltd., substance content or solid content: 30 % ± 5) in, it stirs 3 hours at room temperature, discharging obtains function of surface
Change ball shaped nano SiO2Graphene oxide/maleic anhydride acrylic copolymer (is denoted as PEG-SiO2- GO/CHINATAN TM) it receives
Rice composite tanning agent.
6 0.5 g PVA-SiO of embodiment2Or PEG-SiO2(molecular weight of PEG is that the degree of polymerization of 1500, PVA is
The mass ratio of 1700, PVA or PEG and ethyl orthosilicate is 1:1) it is dissolved in 50 mL deionized waters, ultrasonic treatment 30
1. min obtains reaction solution；0.1 g GO is dissolved in 20 mL deionized waters, 30 min of ultrasound, obtain reaction solution 2. by reaction solution
1. 2. after mixing with reaction solution, reacting 6 hours for lower 60 DEG C of strength mechanical stirring, it is centrifugated, it is dry, obtain function of surface
Change ball shaped nano SiO2Stannic oxide/graphene nano composite (is denoted as PVA-SiO2- GO or PEG-SiO2- GO).
7 23 g maleic anhydride (MA) of embodiment under stiring, is completely dissolved in 100 mL and goes at 75~85 DEG C
In ionized water, reaction solution is obtained 1.；1.2 g ammonium persulfates are dissolved in 10 mL deionized waters and 36 mL acrylic acid (AA) monomers are same
When to reaction solution 1. in slowly drop evenly, be added dropwise control reaction temperature at 85~90 DEG C the reaction was continued 4 hours, reaction
Terminate, adjusts product solution pH value to 5~6 with the sodium hydroxide solution of 30 wt%, discharging obtains maleic anhydride-acrylic acid
Copolymer tanning agent (is denoted as PMAAA).
8 23 g maleic anhydride of embodiment (MA) under stiring, 100 mL are completely dissolved at 75~85 DEG C
In deionized water, reaction solution is obtained 1.；0.15 g GO, which is dissolved in 20 mL deionized waters, to be ultrasonically treated 30 minutes, obtains reaction solution 2.；
Reaction solution is uniformly mixed under stirring 1. with reaction solution 2. at 75~85 DEG C, obtains reaction solution 3.；1.2 g ammonium persulfates are dissolved in 10
ML deionized water and 36 mL acrylic monomers (AA) simultaneously to reaction solution 3. in slowly drop evenly, be added dropwise, temperature control
The reaction was continued 4 hours at 85~90 DEG C for system, and reaction terminates, and adjusts product solution pH value to 5 with the sodium hydroxide solution of 30wt %
~6, discharging obtains graphene oxide/maleic anhydride-acrylic copolymer nano-composite tanning agent (being denoted as GO/PMAAA).
9 23 g maleic anhydride (MA) of embodiment under stiring, is completely dissolved in 100 mL and goes at 75~85 DEG C
In ionized water, reaction solution is obtained 1.；2.40 g PVA-SiO2 Or PEG-SiO2(degree of polymerization of PVA is 1700；The molecular weight of PEG is
1500, PVA, the mass ratio of PEG and ethyl orthosilicate is 1:1), it is dissolved in 50 mL deionized waters and being ultrasonically treated 30 minutes,
Obtain the reaction solution of stable homogeneous 2.；Reaction solution is uniformly mixed under stirring 1. with reaction solution 2. at 75~85 DEG C, obtains reaction solution 3.；
1.2 g ammonium persulfates be dissolved in 10 mL deionized waters and 36 mL acrylic monomers (AA) simultaneously to reaction solution 3. in slow uniform drop
Add, reaction temperature control is added dropwise, and at 85~90 DEG C, the reaction was continued 4 hours, and reaction terminates, and the sodium hydroxide with 30 wt% is molten
Liquid adjusts product solution pH value to 5~6, and discharging obtains surface-functionalized ball shaped nano SiO2/ maleic anhydride-acrylic acid is total
Polymers nano-composite tanning agent (as PVA-SiO2/ PMAAA or PEG-SiO2/PMAAA)。
(tanning agent dosage is 4 wt% of tare weight, referring in clothing leather for the physical mechanical property comparison of 1 tanbark of table
National standard and iso standard requirement, QB/T 2710-2005, ISO/FDIS 14931:2003)
As shown in Table 1, as can be seen from the table, surface-functionalized ball shaped nano SiO2Graphene oxide/polymer matrix is received
Rice composite tanning agent significantly improves the mechanical property of leather, wherein PVA-SiO made from embodiment 22- GO/PMAAA and
PEG- SiO2The tanning effect of-GO/PMAAA compound is best, this is because in composite tanning agent preparation process, such as embodiment
1, embodiment 2 and embodiment 3, surface-functionalized ball shaped nano SiO2Graphene oxide composite nano particle is dissolved in first along fourth
In enedioic acid anhydride monomer solution, then acrylic monomers is added thereto and carries out copolymerization, such feeding sequence can make
The active group (- OH) on composite nano particle surface is obtained in the course of the polymerization process with the reactive group on comonomer, such as-COOH to change
It learns key effect sufficiently and is securely joined with, so as to reach good tanning effect.
(tanning agent dosage is 4 wt% of tare weight, " is spun referring to GB/T 5454-1997 for the oxygen index (OI) comparison of 2 tanbark of table
Fabric combustibility test oxygen index method ", test equipment is that the JF-3 oxygen index (OI) that analysis instrument factory in Jiangning county's provides is surveyed
Determine instrument)
Oxygen index (OI) is bigger, and oxygen concentration needed for maintaining burning is higher, and more difficult to burn, i.e. flame retardant property are better.It can by table 2
Know, as can be seen from the table, compares other tanning agents, surface-functionalized ball shaped nano SiO2Graphene oxide/polymer matrix is received
Rice composite tanning agent improves the flame retardant property of leather, wherein the PVA-SiO as made from embodiment 22- GO/PMAAA and PEG-
SiO2The flame retardant effect of-GO/PMAAA compound is best.
Claims (8)
1. a kind of surface-functionalized ball shaped nano SiO2Graphene oxide/polymer matrix composite tanning agent preparation method, feature
It is, includes the following steps:
(1) by PVA-SiO2Aqueous solution or PEG-SiO2Aqueous solution and GO aqueous solution mixing after 40~60 DEG C under stiring
Reaction 6~8 hours, centrifuge separation take solid dry, obtain PVA-SiO2- GO or PEG-SiO2- GO, PVA-SiO2Or PEG-
SiO2Mass percent with GO is respectively (2 ~ 50): 1, wherein GO represents graphene oxide, PVA-SiO2Represent surface quilt
The SiO of PVA modification2, PEG-SiO2Represent the SiO that surface is modified by PEG2, PVA is polyvinyl alcohol, and PEG is polyethylene glycol；It is described
PVA-SiO2Or PEG-SiO2Preparation process it is as follows: ethyl orthosilicate is dissolved in ethyl alcohol, be added dropwise ammonium hydroxide to pH be 9,45~50
After DEG C 1~2h of reaction, be added the aqueous solution of polyvinyl alcohol or the aqueous solution of polyethylene glycol, 50 DEG C of reactions for 24 hours, centrifuge separation,
Solid ethanol washing, it is dry to get；
(2) PVA-SiO is weighed2- GO or PEG-SiO2It is poly- to be added to vinyl with situ aggregation method or solution blended process by-GO
It closes in object matrix, prepares surface-functionalized ball shaped nano SiO2Graphene oxide/polymer-based nano composite tanning agent, wherein
PVA-SiO2- GO or PEG-SiO2- GO accounts for 0.25wt %~6wt % of polyvinyl matrix substance content.
2. surface-functionalized ball shaped nano SiO according to claim 12Graphene oxide/polymer matrix composite tanning agent system
Preparation Method, which is characterized in that the degree of polymerization 1700 of polyvinyl alcohol, alcoholysis degree 88%；The molecular weight of polyethylene glycol is 200 ~ 6000.
3. surface-functionalized ball shaped nano SiO according to claim 22Graphene oxide/polymer matrix composite tanning agent system
Preparation Method, which is characterized in that the mass ratio of polyvinyl alcohol or polyethylene glycol and ethyl orthosilicate is (1 ~ 2) ︰ (1 ~ 2).
4. surface-functionalized ball shaped nano SiO according to claim 12Graphene oxide/polymer matrix composite tanning agent system
Preparation Method, which is characterized in that the polyvinyl matrix is one of following: (1) maleic anhydride and acrylic acid
Copolymer；(2) acrylic resin；(3) maleic anhydride acrylic copolymer.
5. surface-functionalized ball shaped nano SiO according to claim 42Graphene oxide/polymer matrix composite tanning agent system
Preparation Method, which is characterized in that when polyvinyl matrix is the copolymer of maleic anhydride and acrylic acid, using original position
Maleic anhydride, is first dissolved in deionized water obtaining reaction solution I by polymerization at 75~85 DEG C, then by PVA-SiO2- GO or
PEG-SiO2- GO, which is dissolved in deionized water, obtains reaction solution II, and reaction solution I and reaction solution II is mixed to obtain reaction at 75~85 DEG C
The deionized water solution and acrylic acid of ammonium persulfate are added dropwise into reaction solution III simultaneously by liquid III, and temperature control is added dropwise and exists
85~90 DEG C the reaction was continued 3 ~ 6 hours, adjusts product solution pH value to 5 with the sodium hydroxide solution of 30wt % after reaction
~6, discharging to get.
6. surface-functionalized ball shaped nano SiO according to claim 52Graphene oxide/polymer matrix composite tanning agent system
Preparation Method, which is characterized in that the mass ratio of the maleic anhydride, acrylic acid and ammonium persulfate be 23 ︰ (37 ~ 38) ︰ (1 ~
1.5), PVA-SiO2- GO or PEG-SiO2- GO accounts for the % of 0.25 %~6 of maleic anhydride and acrylic acid gross mass.
7. surface-functionalized ball shaped nano SiO according to claim 42Graphene oxide/polymer matrix composite tanning agent system
Preparation Method, which is characterized in that when polyvinyl matrix is acrylic resin or maleic anhydride acrylic copolymer, use
Solution blended process, by PVA-SiO2- GO or PEG-SiO2- GO is dissolved in deionized water, adds acrylic resin or maleic anhydride
Acrylic copolymer, react at room temperature 3 ~ 4h, discharging to get.
8. utilizing surface-functionalized ball shaped nano SiO made from any preparation method of claim 1 to 72Graphite oxide
Alkene/polymer matrix composite tanning agent.
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| CN102586507A (en) * | 2012-03-21 | 2012-07-18 | 陕西科技大学 | Method for preparing acrylic resin modified graphene oxide leather tanning agent |
| CN102634613A (en) * | 2012-04-10 | 2012-08-15 | 陕西科技大学 | Preparation method of chitosan modified graphite oxide functional leather tanning agent |
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| CN102634613A (en) * | 2012-04-10 | 2012-08-15 | 陕西科技大学 | Preparation method of chitosan modified graphite oxide functional leather tanning agent |
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