CN102628089B - Preparation method for graphene oxide-modified sulfited fatliquor - Google Patents
Preparation method for graphene oxide-modified sulfited fatliquor Download PDFInfo
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Abstract
The invention relates to a preparation method for a graphene oxide-modified sulfited fatliquor. At present, besides the general performances of softness, plumpness and the like, a functional fatliquor also has the special functions of reinforcement, toughening property, fire resistance, filling property, dyeing aiding property, water-proofness and the like. But the fire resistance of the current lather product needs to be improved. Graphene oxide is prepared by taking natural crystalline flake graphite, sodium nitrate, concentrated sulfuric acid, potassium permanganate and the like as raw materials and is modified and dispersed by ethanolamine and diethanolamine, and the modified and dispersed graphene oxide reacts with maleic anhydride and sodium bisulfite to perform sulfitation to prepare a novel graphene oxide-modified sulfited grease leather fatliquor. A leather adopting the fatliquor is soft and plump in hand feeling, and the physical and mechanical properties, the toughness and the retardant effectiveness of the leather are obviously improved at the same time, and the fatliquor is a novel functional leather fatliquor.
Description
Technical field
The technology of the present invention field belongs to a kind of preparation method of leather fat, particularly a kind of preparation method of graphene oxide modification sulphiting fatting agent.
Technical background
Fatting agent is a kind of leather chemicals of consumption maximum in the leather processing procedure, and the quality of leather fat and function are to the performance important influence of leather products.At present, the fatting agent with certain function is a focus of research and development.It is the flexibility, the surperficial feel that improves leather that increase leather that traditional leather fat mainly acts on, make the plentiful and high resilience of leather, thereby the extensibility that increases finished leather improves yield of leather.And the functional type fatting agent is except having general softness, performance such as plentiful, also have strengthen toughness reinforcing, fire-retardant, fill, help dye, specific function such as waterproof.On the other hand, raising along with living standards of the people, leatherware has got more and more and has used under special occasions, as the vehicles (automobile, high ferro, aircraft), upholster, furniture and fire-fighting protective clothing etc., and bring very big disaster can for people's life, property safety by the fire that the leather burning causes, therefore, the flame retardant properties to leatherware has proposed more and more higher requirement.
Summary of the invention
The present invention aims to provide a kind of preparation method of graphene oxide modification sulphiting fatting agent, and this fatting agent makes it have good snappiness simultaneously at lubricated leather fiber, also has to strengthen effect toughness reinforcing and raising leather flame retardant properties.
For achieving the above object, the present invention has adopted following technical scheme to be:
A kind of preparation method of graphene oxide modification sulphiting fatting agent, its special character is:
(1) preparation of graphene oxide: under condition of ice bath, be that 98% sulfuric acid evenly mixes with SODIUMNITRATE and the massfraction of 200 weight parts of the natural flake graphite of 10 weight parts, 6 weight parts, stir the KMnO that slowly adds 25 weight parts down
4Temperature is raised to 45 ℃ of reactions 30 minutes, again temperature is raised to 85 ℃ of reactions 2 hours. slowly add 300 mL deionized waters continuously, make temperature rise to 95 ℃, under this temperature, kept 30 minutes, be that 30% hydrogen peroxide is handled with the massfraction of 30 weight parts again, make suspension become glassy yellow by brown, regulate pH=6 with sodium hydroxide after washing 3 times, under the ultrasonic power of 600 W, peeled off 3 hours, centrifuging again, under 4000 rev/mins condition centrifugal 5 minutes, filter cake was oxidizing aqueous Graphene;
(2) modification of graphene oxide: the diethanolamine of the thanomin of the trolamine of the graphene oxide of above-mentioned 5 ~ 10 weight parts and 5 ~ 10 weight parts, 50 ~ 100 weight parts, 60 ~ 120 weight parts and 1 weight part tosic acid joined be equipped with in water trap and the decompress filter reactor, being 300 rev/mins, pressure at rotating speed is heated to 100 ℃ under-0.1MPa the decompress filter, insulation reaction 3 hours has obtained modified oxidized Graphene;
(3) preparation of sulphiting grease: the grease of 100～150 weight parts and the modified oxidized Graphene of 20 ~ 30 weight parts are added in the reactor, reaction is 2 ~ 2.5 hours when being warmed up to 100 ~ 120 ℃, add the maleic anhydride of 20 ~ 30 weight parts again 90 ~ 100 ℃ of reactions 1 ~ 1.5 hour, the saturated aqueous solution that adds the sodium bisulfite preparation of 20 ~ 25 weight parts when cooling to 60 ~ 70 ℃ again, insulated and stirred reaction 2～3 hours, cooling to after the room temperature and being neutralized to pH with 20% sodium hydroxide is 6.5～8, obtains brown oily liquid oxidation Graphene modification sulphiting fatting agent.
The grease that is suitable for the method that the present invention relates to has fish oil, lanolin, silkworm chrysalis oil, tallow, lard, Viscotrol C, rapeseed oil, plam oil, Oleum Gossypii semen, Rice pollard oil, soya-bean oil, peanut oil, sweet oil, Fructus Zanthoxyli oil.
Embodiment
The present invention is raw material with the natural flake graphite earlier, be equipped with graphene oxide by the Hummers legal system, being connected with officials such as carbonyl, hydroxyl, carboxyl, epoxy group(ing) at Graphene hexagonal annular plates carbon atom can, both kept the original six-membered ring structure of Graphene, introduced a large amount of hydrophilic radicals again, therefore graphene oxide has certain wettability and surfactivity, it can disperse in water preferably, also better with the compatible performance of polymkeric substance, these character just in time are applicable to the stuffing operation that leather is produced.
The present invention carries out surface modification and dispersion with excess ethanol amine, diethanolamine and trolamine to graphene oxide earlier, utilize the good amino of thanomin, diethanolamine and trolamine to be combined with its surperficial carboxyl, epoxy group(ing) on the one hand, improve dispersed stability.With modified oxidized Graphene, maleic anhydride and sodium bisulfite grease is carried out modification again, introduce two keys by maleic anhydride, introduce sulfonic group with sodium bisulfite, prepare stable fatting agent dispersion system, dexterously graphene oxide is introduced leather fiber, it not only can fill, be deposited on the leather fiber space, and in its molecular structure a plurality of active groups (hydroxyl, carboxyl, epoxy group(ing) etc.) can also with leather peptide molecule chain generation Chemical bond, to give the good snappiness of finished leather and strength property; In addition, the graphene oxide material can form the coking layer of certain thickness densification for finished leather provides abundant charcoal source when leather burns, stop the diffusion of heat and air, the performance flame retardant effect;
The fatting agent that the present invention uses is the product of grease sulphiting, has also opened up new way for recycling and its added value of raising of grease.
Embodiment 1
(1) preparation of graphene oxide: under condition of ice bath, be that 98% sulfuric acid evenly mixes with 10 weight part natural flake graphites, 6 weight part SODIUMNITRATE and the massfraction of 200 weight parts, stir the KMnO that slowly adds 25 weight parts down
4Temperature is raised to 45 ℃ of reactions 30 minutes, again temperature is raised to 85 ℃ of reactions 2 hours. slowly add 300 mL deionized waters continuously, make temperature rise to 95 ℃, under this temperature, kept 30 minutes, handle with the hydrogen peroxide of 30 weight part massfractions 30% again, make suspension become glassy yellow by brown, regulate pH=6 with sodium hydroxide after washing 3 times, under the ultrasonic power of 600 W, peeled off 3 hours, centrifuging again, under 4000 rev/mins condition centrifugal 5 minutes, filter cake was oxidizing aqueous Graphene;
(2) preparation of modified oxidized Graphene: the diethanolamine of the thanomin of the trolamine of the graphene oxide of above-mentioned 5 weight parts and 5 weight parts, 50 weight parts, 60 weight parts and 1 weight part tosic acid joined be equipped with in water trap and the decompress filter reactor, being 300 rev/mins, pressure at rotating speed is heated to 100 ℃ under-0.1MPa the decompress filter, insulation reaction 3 hours has obtained modified oxidized Graphene;
(3) preparation of sulphiting grease: the grease of 100 weight parts and the modified oxidized Graphene of 20 weight parts are added in the reactor, reaction is 2 hours when being warmed up to 100 ℃, add the maleic anhydride of 20 weight parts again 90 ℃ of reactions 1 hour, the saturated aqueous solution that adds the sodium bisulfite preparation of 20 weight parts when cooling to 60 ℃ again, insulated and stirred reaction 2 hours, cooling to after the room temperature and being neutralized to pH with 20% sodium hydroxide is 6.5, can obtain brown oily liquid oxidation Graphene modification sulphiting fatting agent.
Embodiment 2
(1) preparation of graphene oxide: under condition of ice bath, be that 98% sulfuric acid evenly mixes with 10 weight part natural flake graphites, 6 weight part SODIUMNITRATE and the massfraction of 200 weight parts, stir the KMnO that slowly adds 25 weight parts down
4Temperature is raised to 45 ℃ of reactions 30 minutes, again temperature is raised to 85 ℃ of reactions 2 hours. slowly add 300 mL deionized waters continuously, make temperature rise to 95 ℃, under this temperature, kept 30 minutes, handle with the hydrogen peroxide of 30 weight part massfractions 30% again, make suspension become glassy yellow by brown, regulate pH=6 with sodium hydroxide after washing 3 times, under the ultrasonic power of 600 W, peeled off 3 hours, centrifuging again, under 4000 rev/mins condition centrifugal 5 minutes, filter cake was oxidizing aqueous Graphene.
(2) preparation of modified oxidized Graphene: the diethanolamine of the thanomin of the trolamine of the graphene oxide of above-mentioned 6 weight parts and 6 weight parts, 60 weight parts, 72 weight parts and 1.2 weight part tosic acid are joined be equipped with in water trap and the decompress filter reactor, being 300 rev/mins, pressure at rotating speed is heated to 100 ℃ under-0.1MPa the decompress filter, insulation reaction 3 hours has obtained modified oxidized Graphene;
(3) preparation of sulphiting grease: the grease of 110 weight parts and the modified oxidized Graphene of 22 weight parts are added in the reactor, reaction is 2.1 hours when being warmed up to 104 ℃, add the maleic anhydride of 22 weight parts again 92 ℃ of reactions 1.1 hours, the saturated aqueous solution that adds the sodium bisulfite preparation of 21 weight parts when cooling to 62 ℃ again, insulated and stirred reaction 2.2 hours, cooling to after the room temperature and being neutralized to pH with 20% sodium hydroxide is 6.9, can obtain brown oily liquid oxidation Graphene modification sulphiting fatting agent.
Embodiment 3
(1) preparation of graphene oxide: under condition of ice bath, be that 98% sulfuric acid evenly mixes with 10 weight part natural flake graphites, 6 weight part SODIUMNITRATE and the massfraction of 200 weight parts, stir the KMnO that slowly adds 25 weight parts down
4Temperature is raised to 45 ℃ of reactions 30 minutes, again temperature is raised to 85 ℃ of reactions 2 hours. slowly add 300 mL deionized waters continuously, make temperature rise to 95 ℃, under this temperature, kept 30 minutes, handle with the hydrogen peroxide of 30 weight part massfractions 30% again, make suspension become glassy yellow by brown, regulate pH=6 with sodium hydroxide after washing 3 times, under the ultrasonic power of 600 W, peeled off 3 hours, centrifuging again, under 4000 rev/mins condition centrifugal 5 minutes, filter cake was oxidizing aqueous Graphene.
(2) preparation of modified oxidized Graphene: the diethanolamine of the thanomin of the trolamine of the graphene oxide of above-mentioned 7 weight parts and 7 weight parts, 70 weight parts, 84 weight parts and 1.4 weight part tosic acid are joined be equipped with in water trap and the decompress filter reactor, being 300 rev/mins, pressure at rotating speed is heated to 100 ℃ under-0.1MPa the decompress filter, insulation reaction 3 hours has obtained modified oxidized Graphene;
(3) preparation of sulphiting grease: the grease of 120 weight parts and the modified oxidized Graphene of 24 weight parts are added in the reactor, reaction is 2.2 hours when being warmed up to 108 ℃, add the maleic anhydride of 24 weight parts again 94 ℃ of reactions 1.2 hours, the saturated aqueous solution that adds the sodium bisulfite preparation of 22 weight parts when cooling to 64 ℃ again, insulated and stirred reaction 2.4 hours, cooling to after the room temperature and being neutralized to pH with 20% sodium hydroxide is 7.2, can obtain brown oily liquid oxidation Graphene modification sulphiting fatting agent.
Embodiment 4
(1) preparation of graphene oxide: under condition of ice bath, be that 98% sulfuric acid evenly mixes with 10 weight part natural flake graphites, 6 weight part SODIUMNITRATE and the massfraction of 200 weight parts, stir the KMnO that slowly adds 25 weight parts down
4Temperature is raised to 45 ℃ of reactions 30 minutes, again temperature is raised to 85 ℃ of reactions 2 hours. slowly add 300 mL deionized waters continuously, make temperature rise to 95 ℃, under this temperature, kept 30 minutes, handle with the hydrogen peroxide of 30 weight part massfractions 30% again, make suspension become glassy yellow by brown, regulate pH=6 with sodium hydroxide after washing 3 times, under the ultrasonic power of 600 W, peeled off 3 hours, centrifuging again, under 4000 rev/mins condition centrifugal 5 minutes, filter cake was oxidizing aqueous Graphene.
(2) preparation of modified oxidized Graphene: the diethanolamine of the thanomin of the trolamine of the graphene oxide of above-mentioned 8 weight parts and 8 weight parts, 80 weight parts, 96 weight parts and 1.6 weight part tosic acid are joined be equipped with in water trap and the decompress filter reactor, being 300 rev/mins, pressure at rotating speed is heated to 100 ℃ under-0.1MPa the decompress filter, insulation reaction 3 hours has obtained modified oxidized Graphene;
(3) preparation of sulphiting grease: the grease of 130 weight parts and the modified oxidized Graphene of 26 weight parts are added in the reactor, reaction is 2.3 hours when being warmed up to 112 ℃, add the maleic anhydride of 26 weight parts again 96 ℃ of reactions 1.3 hours, the saturated aqueous solution that adds the sodium bisulfite preparation of 23 weight parts when cooling to 66 ℃ again, insulated and stirred reaction 2.6 hours, cooling to after the room temperature and being neutralized to pH with 20% sodium hydroxide is 7.6, can obtain brown oily liquid oxidation Graphene modification sulphiting fatting agent.
Embodiment 5
(1) preparation of graphene oxide: under condition of ice bath, be that 98% sulfuric acid evenly mixes with 10 weight part natural flake graphites, 6 weight part SODIUMNITRATE and the massfraction of 200 weight parts, stir the KMnO that slowly adds 25 weight parts down
4Temperature is raised to 45 ℃ of reactions 30 minutes, again temperature is raised to 85 ℃ of reactions 2 hours. slowly add 300 mL deionized waters continuously, make temperature rise to 95 ℃, under this temperature, kept 30 minutes, handle with the hydrogen peroxide of 30 weight part massfractions 30% again, make suspension become glassy yellow by brown, regulate pH=6 with sodium hydroxide after washing 3 times, under the ultrasonic power of 600 W, peeled off 3 hours, centrifuging again, under 4000 rev/mins condition centrifugal 5 minutes, filter cake was oxidizing aqueous Graphene.
(2) preparation of modified oxidized Graphene: the diethanolamine of the thanomin of the trolamine of the graphene oxide of above-mentioned 9 weight parts and 9 weight parts, 90 weight parts, 108 weight parts and 1.8 weight part tosic acid are joined be equipped with in water trap and the decompress filter reactor, being 300 rev/mins, pressure at rotating speed is heated to 100 ℃ under-0.1MPa the decompress filter, insulation reaction 3 hours has obtained modified oxidized Graphene;
(3) preparation of sulphiting grease: the grease of 140 weight parts and the modified oxidized Graphene of 28 weight parts are added in the reactor, reaction is 2.4 hours when being warmed up to 116 ℃, add the maleic anhydride of 28 weight parts again 98 ℃ of reactions 1.4 hours, the saturated aqueous solution that adds the sodium bisulfite preparation of 24 weight parts when cooling to 68 ℃ again, insulated and stirred was reacted 2.8 o'clock, cooling to after the room temperature and being neutralized to pH with 20% sodium hydroxide is 7.8, can obtain brown oily liquid oxidation Graphene modification sulphiting fatting agent.
Embodiment 6
(1) preparation of graphene oxide: under condition of ice bath, be that 98% sulfuric acid evenly mixes with 10 weight part natural flake graphites, 6 weight part SODIUMNITRATE and the massfraction of 200 weight parts, stir the KMnO that slowly adds 25 weight parts down
4Temperature is raised to 45 ℃ of reactions 30 minutes, again temperature is raised to 85 ℃ of reactions 2 hours. slowly add 300 mL deionized waters continuously, make temperature rise to 95 ℃, under this temperature, kept 30 minutes, handle with the hydrogen peroxide of 30 weight part massfractions 30% again, make suspension become glassy yellow by brown, regulate pH=6 with sodium hydroxide after washing 3 times, under the ultrasonic power of 600 W, peeled off 3 hours, centrifuging again, under 4000 rev/mins condition centrifugal 5 minutes, filter cake was oxidizing aqueous Graphene.
(2) preparation of modified oxidized Graphene: the diethanolamine of the thanomin of the trolamine of the graphene oxide of above-mentioned 10 weight parts and 10 weight parts, 100 weight parts, 120 weight parts and 2.0 weight part tosic acid are joined be equipped with in water trap and the decompress filter reactor, being 300 rev/mins, pressure at rotating speed is heated to 100 ℃ under-0.1MPa the decompress filter, insulation reaction 3 hours has obtained modified oxidized Graphene;
(3) preparation of sulphiting grease: the grease of 150 weight parts and the modified oxidized Graphene of 30 weight parts are added in the reactor, reaction is 2.5 hours when being warmed up to 120 ℃, add the maleic anhydride of 30 weight parts again 100 ℃ of reactions 1.5 hours, the saturated aqueous solution that adds the sodium bisulfite preparation of 25 weight parts when cooling to 70 ℃ again, insulated and stirred reaction 3 hours, cooling to after the room temperature and being neutralized to pH with 20% sodium hydroxide is 8, can obtain brown oily liquid oxidation Graphene modification sulphiting fatting agent.
Embodiment 7 application experiments
Fatting agent and performance index: prepared graphene oxide modification sulphiting rapeseed oil and graphene oxide modification sulphiting lard fatting agent respectively with the inventive method, using to have prepared with quadrat method does not have the sulphiting of graphene oxide modification rapeseed oil and sulphiting lard sample in contrast.Performance index are as follows:
Outward appearance: the light brown soup compound that can flow, free from extraneous odour;
PH value: (10% sample emulsion is measured with the pH test paper) about 8.0;
Solid content: 40%;
Graphene oxide content: 0.50%
Stability of emulsion: easily emulsification in the hot water, emulsion is solution-stabilized to acid, alkali, salt, tannin extract;
Shelf-stability: placement is not stratified half a year.
Leather base sample: goat chrome tanning wet blue (for the preparation of clothing leather).
Stuffing technology:
Application art carries out the stuffing test at the goat leather for garment wet blue routinely.Dyeing and fat-liquoring technology:
Dyeing and stuffing: 200%, 50 ℃ in water;
Dye dosage: Acid Black 1 .0%+ is black 1.0%, 1:10 warm water dilution back adding directly, changes 60 minutes;
The fatting agent consumption: fatting agent 10%, 1:10 hot water dilution back adds 60 minutes;
Fatting agent fixing: formic acid 1.2%, the dilution of 1:10 tap water, gradation adds, require pH 3.8 ±;
Going out drum takes horse, puts in order, estimates after drying.
Use the evaluation of leather: the method with sensory evaluation (hand is touched soon) is estimated item by item to its flexibility, fullness, tint permanence etc.
Detection method:
(1) flame retardant properties detects: weigh flame retardant properties according to rigid plastics combustibility test method GB/T 8333-2008 with vertical combustion method (flaming combustion time, flameless combustion time), oxygen index method and smoke density method;
(2) stuffing Characterization result: press leather tensile strength detection method GB 4689.5-1984 and characterize tensile strength and elongation; Detection side GB4689.7-1984 sign by grain side of leather intensity and stretching, extension height collapses brokenly intensity and collapses brokenly height; The detection method GB 4689.6-1984 that presses the leather tear strength characterizes tear strength.
Table 1. graphene oxide modification sulphiting fatting agent flame retardant effect (the fatting agent consumption is 10 % of tare weight)
Table 2. graphene oxide modification sulphiting fatting agent stuffing effect (the fatting agent consumption is 10 % of tare weight)
From table the result as can be seen, graphene oxide modification sulphiting grease fatting agent not only has flame retardant effect preferably, can also play to strengthen toughness reinforcing effect, significantly improves the effect of using the soft and full feel of leather.
Claims (7)
1. the preparation method of a graphene oxide modification sulphiting fatting agent is characterized in that:
(1) preparation of graphene oxide: under condition of ice bath, be that 98% sulfuric acid evenly mixes with SODIUMNITRATE and the massfraction of 200 weight parts of the natural flake graphite of 10 weight parts, 6 weight parts, stir the KMnO that slowly adds 25 weight parts down
4Temperature is raised to 45 ℃ of reactions 30 minutes, again temperature is raised to 85 ℃ of reactions 2 hours. slowly add 300 mL deionized waters continuously, make temperature rise to 95 ℃, under this temperature, kept 30 minutes, be that 30% hydrogen peroxide is handled with the massfraction of 30 weight parts again, make suspension become glassy yellow by brown, regulate pH=6 with sodium hydroxide after washing 3 times, under the ultrasonic power of 600 W, peeled off 3 hours, centrifuging again, under 4000 rev/mins condition centrifugal 5 minutes, filter cake was oxidizing aqueous Graphene;
(2) modification of graphene oxide: the diethanolamine of the thanomin of the trolamine of the graphene oxide of above-mentioned 5 ~ 10 weight parts and 5 ~ 10 weight parts, 50 ~ 100 weight parts, 60 ~ 120 weight parts and 1 weight part tosic acid joined be equipped with in water trap and the decompress filter reactor, being 300 rev/mins, pressure at rotating speed is heated to 100 ℃ under-0.1MPa the decompress filter, insulation reaction 3 hours has obtained modified oxidized Graphene;
(3) preparation of sulphiting grease: the grease of 100～150 weight parts and the modified oxidized Graphene of 20 ~ 30 weight parts are added in the reactor, reaction is 2 ~ 2.5 hours when being warmed up to 100 ~ 120 ℃, add the maleic anhydride of 20 ~ 30 weight parts again 90 ~ 100 ℃ of reactions 1 ~ 1.5 hour, the saturated aqueous solution that adds the sodium bisulfite preparation of 20 ~ 25 weight parts when cooling to 60 ~ 70 ℃ again, insulated and stirred reaction 2～3 hours, cooling to after the room temperature and being neutralized to pH with 20% sodium hydroxide is 6.5～8, can obtain brown oily liquid oxidation Graphene modification sulphiting fatting agent.
2. the preparation method of graphene oxide modification sulphiting fatting agent according to claim 1 is characterized in that:
(1) preparation of graphene oxide: under condition of ice bath, be that 98% sulfuric acid evenly mixes with 10 weight part natural flake graphites, 6 weight part SODIUMNITRATE and the massfraction of 200 weight parts, stir the KMnO that slowly adds 25 weight parts down
4Temperature is raised to 45 ℃ of reactions 30 minutes, again temperature is raised to 85 ℃ of reactions 2 hours. slowly add 300 mL deionized waters continuously, make temperature rise to 95 ℃, under this temperature, kept 30 minutes, handle with the hydrogen peroxide of 30 weight part massfractions 30% again, make suspension become glassy yellow by brown, regulate pH=6 with sodium hydroxide after washing 3 times, under the ultrasonic power of 600 W, peeled off 3 hours, centrifuging again, under 4000 rev/mins condition centrifugal 5 minutes, filter cake was oxidizing aqueous Graphene;
(2) preparation of modified oxidized Graphene: the diethanolamine of the thanomin of the trolamine of the graphene oxide of above-mentioned 5 weight parts and 5 weight parts, 50 weight parts, 60 weight parts and 1 weight part tosic acid joined be equipped with in water trap and the decompress filter reactor, being 300 rev/mins, pressure at rotating speed is heated to 100 ℃ under-0.1MPa the decompress filter, insulation reaction 3 hours has obtained modified oxidized Graphene;
(3) preparation of sulphiting grease: the grease of 100 weight parts and the modified oxidized Graphene of 20 weight parts are added in the reactor, reaction is 2 hours when being warmed up to 100 ℃, add the maleic anhydride of 20 weight parts again 90 ℃ of reactions 1 hour, the saturated aqueous solution that adds the sodium bisulfite preparation of 20 weight parts when cooling to 60 ℃ again, insulated and stirred reaction 2 hours, cooling to after the room temperature and being neutralized to pH with 20% sodium hydroxide is 6.5, can obtain brown oily liquid oxidation Graphene modification sulphiting fatting agent.
3. the preparation method of graphene oxide modification sulphiting fatting agent according to claim 1 is characterized in that:
(1) preparation of graphene oxide: under condition of ice bath, be that 98% sulfuric acid evenly mixes with 10 weight part natural flake graphites, 6 weight part SODIUMNITRATE and the massfraction of 200 weight parts, stir the KMnO that slowly adds 25 weight parts down
4Temperature is raised to 45 ℃ of reactions 30 minutes, again temperature is raised to 85 ℃ of reactions 2 hours. slowly add 300 mL deionized waters continuously, make temperature rise to 95 ℃, under this temperature, kept 30 minutes, handle with the hydrogen peroxide of 30 weight part massfractions 30% again, make suspension become glassy yellow by brown, regulate pH=6 with sodium hydroxide after washing 3 times, under the ultrasonic power of 600 W, peeled off 3 hours, centrifuging again, under 4000 rev/mins condition centrifugal 5 minutes, filter cake was oxidizing aqueous Graphene;
(2) preparation of modified oxidized Graphene: the diethanolamine of the thanomin of the trolamine of the graphene oxide of above-mentioned 6 weight parts and 6 weight parts, 60 weight parts, 72 weight parts and 1.2 weight part tosic acid are joined be equipped with in water trap and the decompress filter reactor, being 300 rev/mins, pressure at rotating speed is heated to 100 ℃ under-0.1MPa the decompress filter, insulation reaction 3 hours has obtained modified oxidized Graphene;
(3) preparation of sulphiting grease: the grease of 110 weight parts and the modified oxidized Graphene of 22 weight parts are added in the reactor, reaction is 2.1 hours when being warmed up to 104 ℃, add the maleic anhydride of 22 weight parts again 92 ℃ of reactions 1.1 hours, the saturated aqueous solution that adds the sodium bisulfite preparation of 21 weight parts when cooling to 62 ℃ again, insulated and stirred reaction 2.2 hours, cooling to after the room temperature and being neutralized to pH with 20% sodium hydroxide is 6.9, can obtain brown oily liquid oxidation Graphene modification sulphiting fatting agent.
4. the preparation method of graphene oxide modification sulphiting fatting agent according to claim 1 is characterized in that:
(1) preparation of graphene oxide: under condition of ice bath, be that 98% sulfuric acid evenly mixes with 10 weight part natural flake graphites, 6 weight part SODIUMNITRATE and the massfraction of 200 weight parts, stir the KMnO that slowly adds 25 weight parts down
4Temperature is raised to 45 ℃ of reactions 30 minutes, again temperature is raised to 85 ℃ of reactions 2 hours. slowly add 300 mL deionized waters continuously, make temperature rise to 95 ℃, under this temperature, kept 30 minutes, handle with the hydrogen peroxide of 30 weight part massfractions 30% again, make suspension become glassy yellow by brown, regulate pH=6 with sodium hydroxide after washing 3 times, under the ultrasonic power of 600 W, peeled off 3 hours, centrifuging again, under 4000 rev/mins condition centrifugal 5 minutes, filter cake was oxidizing aqueous Graphene;
(2) preparation of modified oxidized Graphene: the diethanolamine of the thanomin of the trolamine of the graphene oxide of above-mentioned 7 weight parts and 7 weight parts, 70 weight parts, 84 weight parts and 1.4 weight part tosic acid are joined be equipped with in water trap and the decompress filter reactor, being 300 rev/mins, pressure at rotating speed is heated to 100 ℃ under-0.1MPa the decompress filter, insulation reaction 3 hours has obtained modified oxidized Graphene;
(3) preparation of sulphiting grease: the grease of 120 weight parts and the modified oxidized Graphene of 24 weight parts are added in the reactor, reaction is 2.2 hours when being warmed up to 108 ℃, add the maleic anhydride of 24 weight parts again 94 ℃ of reactions 1.2 hours, the saturated aqueous solution that adds the sodium bisulfite preparation of 22 weight parts when cooling to 64 ℃ again, insulated and stirred reaction 2.4 hours, cooling to after the room temperature and being neutralized to pH with 20% sodium hydroxide is 7.2, can obtain brown oily liquid oxidation Graphene modification sulphiting fatting agent.
5. the preparation method of graphene oxide modification sulphiting fatting agent according to claim 1 is characterized in that:
(1) preparation of graphene oxide: under condition of ice bath, be that 98% sulfuric acid evenly mixes with 10 weight part natural flake graphites, 6 weight part SODIUMNITRATE and the massfraction of 200 weight parts, stir the KMnO that slowly adds 25 weight parts down
4Temperature is raised to 45 ℃ of reactions 30 minutes, again temperature is raised to 85 ℃ of reactions 2 hours. slowly add 300 mL deionized waters continuously, make temperature rise to 95 ℃, under this temperature, kept 30 minutes, handle with the hydrogen peroxide of 30 weight part massfractions 30% again, make suspension become glassy yellow by brown, regulate pH=6 with sodium hydroxide after washing 3 times, under the ultrasonic power of 600 W, peeled off 3 hours, centrifuging again, under 4000 rev/mins condition centrifugal 5 minutes, filter cake was oxidizing aqueous Graphene;
(2) preparation of modified oxidized Graphene: the diethanolamine of the thanomin of the trolamine of the graphene oxide of above-mentioned 8 weight parts and 8 weight parts, 80 weight parts, 96 weight parts and 1.6 weight part tosic acid are joined be equipped with in water trap and the decompress filter reactor, being 300 rev/mins, pressure at rotating speed is heated to 100 ℃ under-0.1MPa the decompress filter, insulation reaction 3 hours has obtained modified oxidized Graphene;
(3) preparation of sulphiting grease: the grease of 130 weight parts and the modified oxidized Graphene of 26 weight parts are added in the reactor, reaction is 2.3 hours when being warmed up to 112 ℃, add the maleic anhydride of 26 weight parts again 96 ℃ of reactions 1.3 hours, the saturated aqueous solution that adds the sodium bisulfite preparation of 23 weight parts when cooling to 66 ℃ again, insulated and stirred reaction 2.6 hours, cooling to after the room temperature and being neutralized to pH with 20% sodium hydroxide is 7.6, can obtain brown oily liquid oxidation Graphene modification sulphiting fatting agent.
6. the preparation method of graphene oxide modification sulphiting fatting agent according to claim 1 is characterized in that:
(1) preparation of graphene oxide: under condition of ice bath, be that 98% sulfuric acid evenly mixes with 10 weight part natural flake graphites, 6 weight part SODIUMNITRATE and the massfraction of 200 weight parts, stir the KMnO that slowly adds 25 weight parts down
4Temperature is raised to 45 ℃ of reactions 30 minutes, again temperature is raised to 85 ℃ of reactions 2 hours. slowly add 300 mL deionized waters continuously, make temperature rise to 95 ℃, under this temperature, kept 30 minutes, handle with the hydrogen peroxide of 30 weight part massfractions 30% again, make suspension become glassy yellow by brown, regulate pH=6 with sodium hydroxide after washing 3 times, under the ultrasonic power of 600 W, peeled off 3 hours, centrifuging again, under 4000 rev/mins condition centrifugal 5 minutes, filter cake was oxidizing aqueous Graphene;
(2) preparation of modified oxidized Graphene: the diethanolamine of the thanomin of the trolamine of the graphene oxide of above-mentioned 9 weight parts and 9 weight parts, 90 weight parts, 108 weight parts and 1.8 weight part tosic acid are joined be equipped with in water trap and the decompress filter reactor, being 300 rev/mins, pressure at rotating speed is heated to 100 ℃ under-0.1MPa the decompress filter, insulation reaction 3 hours has obtained modified oxidized Graphene;
(3) preparation of sulphiting grease: the grease of 140 weight parts and the modified oxidized Graphene of 28 weight parts are added in the reactor, reaction is 2.4 hours when being warmed up to 116 ℃, add the maleic anhydride of 28 weight parts again 98 ℃ of reactions 1.4 hours, the saturated aqueous solution that adds the sodium bisulfite preparation of 24 weight parts when cooling to 68 ℃ again, insulated and stirred reaction 2.8 hours, cooling to after the room temperature and being neutralized to pH with 20% sodium hydroxide is 7.8, can obtain brown oily liquid oxidation Graphene modification sulphiting fatting agent.
7. the preparation method of graphene oxide modification sulphiting fatting agent according to claim 1 is characterized in that:
(1) preparation of graphene oxide: under condition of ice bath, be that 98% sulfuric acid evenly mixes with 10 weight part natural flake graphites, 6 weight part SODIUMNITRATE and the massfraction of 200 weight parts, stir the KMnO that slowly adds 25 weight parts down
4Temperature is raised to 45 ℃ of reactions 30 minutes, again temperature is raised to 85 ℃ of reactions 2 hours. slowly add 300 mL deionized waters continuously, make temperature rise to 95 ℃, under this temperature, kept 30 minutes, handle with the hydrogen peroxide of 30 weight part massfractions 30% again, make suspension become glassy yellow by brown, regulate pH=6 with sodium hydroxide after washing 3 times, under the ultrasonic power of 600 W, peeled off 3 hours, centrifuging again, under 4000 rev/mins condition centrifugal 5 minutes, filter cake was oxidizing aqueous Graphene;
(2) preparation of modified oxidized Graphene: the diethanolamine of the thanomin of the trolamine of the graphene oxide of above-mentioned 10 weight parts and 10 weight parts, 100 weight parts, 120 weight parts and 2.0 weight part tosic acid are joined be equipped with in water trap and the decompress filter reactor, being 300 rev/mins, pressure at rotating speed is heated to 100 ℃ under-0.1MPa the decompress filter, insulation reaction 3 hours has obtained modified oxidized Graphene;
(3) preparation of sulphiting grease: the grease of 150 weight parts and the modified oxidized Graphene of 30 weight parts are added in the reactor, reaction is 2.5 hours when being warmed up to 120 ℃, add the maleic anhydride of 30 weight parts again 100 ℃ of reactions 1.5 hours, the saturated aqueous solution that adds the sodium bisulfite preparation of 25 weight parts when cooling to 70 ℃ again, insulated and stirred reaction 3 hours, cooling to after the room temperature and being neutralized to pH with 20% sodium hydroxide is 8, can obtain brown oily liquid oxidation Graphene modification sulphiting fatting agent.
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