CN110330652A - A kind of preparation method of the graphene-based polysiloxanes of low-viscosity and the method for reducing graphene-based silicone cross degree - Google Patents
A kind of preparation method of the graphene-based polysiloxanes of low-viscosity and the method for reducing graphene-based silicone cross degree Download PDFInfo
- Publication number
- CN110330652A CN110330652A CN201910559645.1A CN201910559645A CN110330652A CN 110330652 A CN110330652 A CN 110330652A CN 201910559645 A CN201910559645 A CN 201910559645A CN 110330652 A CN110330652 A CN 110330652A
- Authority
- CN
- China
- Prior art keywords
- graphene
- polysiloxanes
- viscosity
- acid
- low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- 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
Abstract
The present invention relates to graphene-based polysiloxanes field, the method that provides a kind of preparation method of low-viscosity graphene polysiloxanes and reduce graphene-based silicone cross degree.Polysiloxanes matrix is prepared under cationic catalysts system, using lipophilic graphene as filler and chemical graft polysiloxanes, it is compound to obtain the graphene-based polysiloxanes of low-viscosity, introduce the polynary depolymerization system of graphene, stablize polysiloxane molecule amount, reduce silicone cross degree, provide a kind of viscosity of effectively control composite material, the method for promoting dispersion stabilization of the graphene in polysiloxanes, simple possible, convieniently synthesized, purification are easy, and greatly prolong the pot life of graphene-based polysiloxanes simultaneously.
Description
Technical field
The present invention relates to graphene-based polysiloxanes fields, provide a kind of preparation side of low-viscosity graphene polysiloxanes
Method and the method for reducing graphene-based silicone cross degree.
Background technique
Graphene is the single layer being made of carbon atom or the two dimensional crystal of layer is claimed due to its excellent various property less
For " dark fund ".Graphene oxide is to handle graphene under the conditions of strong acid strong oxidizing property, then remove one kind obtained through ultrasound
The Graphene derivative of rich oxygen-containing functional group functionalization, and prepare the presoma of redox graphene.Graphene oxide sheet
Oxide regions are rich on layer, lamella edge contains the functional groups such as carboxyl, hydroxyl, contains the officials such as hydroxyl and epoxy group in slice plane
It can group.The presence of oxygen-containing functional group expands the application range of graphene, and functionalization improves graphene oxide and polymer collection
To assign polymer composites more excellent properties, thus physical blending process can be used or chemistry connects in the compatibility of body
Branch method mixes graphene oxide with polysiloxanes.
Wherein compound using chemical graft process progress, since active site is more on graphene oxide, crosslinking degree is big, sticks
Degree steeply rises.Tradition uses alkali as the anionic catalytic system of catalyst since the distribution of polysiloxane molecule amount is wide, product
After vacuum distillation, there is only the polysiloxanes of higher molecular weight in system, it is difficult to polysiloxane molecule amount is reduced, and it is higher
After the polysiloxane-grafted graphene oxide of viscosity, easily lead to generate insoluble insoluble silicon rubber because viscosity is excessive, greatly
Large-scale production difficulty is larger.
Summary of the invention
The purpose of the present invention is to provide polysiloxanes matrix is prepared under cationic catalysts system, with lipophilic graphene
It is compound to obtain the graphene-based polysiloxanes of low-viscosity for filler and chemical graft polysiloxanes, it is multiple to provide a kind of effectively control
The viscosity of condensation material, the method for promoting dispersion stabilization of the graphene in polysiloxanes.
To achieve the above object, the preparation method of the graphene-based polysiloxanes of a kind of low-viscosity of the present invention, it is described
Preparation method includes the following steps:
S1: adding graphene oxide into deionized water, and ultrasonic disperse 30-90min obtains dispersion liquid；
S2: silane coupling agent is added in S1 dispersion liquid, reacts 12-72h at 50-100 DEG C；
S3: products therefrom in S2 is first washed 2-6 times with dehydrated alcohol, then is washed with deionized 1-7 times；
S4: dispersing product obtained in S3 in deionized water, is ultrasonically treated 1h, and 5% hydrazine hydrate reduction 3- is added
12h；
Product obtained in S5:S4 repeats the washing operation of S3, obtains lipophilic graphene after vacuum drying；
S6: siloxanyl monomers, end-capping reagent, catalyst are reacted into 4h at 70-140 DEG C, products therefrom is added silane coupled
Agent is cooled to 50-70 DEG C of reaction 1-3h and obtains low-viscosity polysiloxanes；
S7: it disperses lipophilic graphene obtained in S5 in the resulting low-viscosity polysiloxanes of S6, is stirred well to
Uniformly, 1-5 times of deionized water is then added, 1-3h is dispersed in ultrasonic wave and obtains graphene-based polysiloxanes dispersion liquid；
S8: organic metal salt is added in graphene-based polysiloxanes dispersion liquid obtained in S7, in 10-50 DEG C of reaction 3-
After vacuum drying, the graphene-based polysiloxanes of low-viscosity is made in 8h.
Wherein, the silane coupling agent is at least 3- chloropropyl triethoxysilane, 3- aminopropyl triethoxysilane, 3-
One of (2,3 the third oxygen of epoxy) propyl-triethoxysilicane, triethoxysilane, the graphene oxide is in deionized water
Concentration be 1-10g/L, the concentration of the silane coupling agent in deionized water be 1-15g/L.
Wherein, the siloxanyl monomers are at least hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethyl ring five
One of siloxanes, ten diformazan basic rings, six siloxanes；The silane coupling agent is at least 3- chloropropyl triethoxysilane, 3-
One of aminopropyl triethoxysilane, 3- (2,3 the third oxygen of epoxy) propyl-triethoxysilicane, triethoxysilane；It is described
Catalyst is at least one of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boric acid, chlorosulfonic acid.
Wherein, the concentration of the silane coupling agent is 0.1-5%, and the end-capping reagent concentration is 0.1-1%, the catalysis
Agent concentration is 0.5-2.5%.
Wherein, the organic metal salt is at least one of zinc octoate, iron octoate, iron naphthenate, aphthenic acids tin.
Wherein, concentration of the lipophilic graphene in polysiloxanes is 1-100g/L, and the organic metal salt is in stone
Concentration in mertenyl polysiloxanes dispersion liquid is 0.005-0.025g/L.
A method of reducing graphene-based silicone cross degree, which is characterized in that successively the following steps are included:
S1: graphene oxide is dissolved in alcohol, then ultrasonic wave dispersion is adjusted with acid pH to 2-4, obtains graphene oxide
Depolymerization liquid；
S2: covalent halide is dissolved in deionized water, then ultrasonic wave dispersion is adjusted with acid pH to 1.5-3.5, obtains
Covalent halide depolymerization liquid；
S3: by weight, 10-15 parts of graphene oxide depolymerization liquid, 20-30 parts of covalent halide depolymerization liquid are dissolved in water
In, it is uniformly mixed obtained depolymerization liquid, the graphene-based poly- silicon of the diluted low-viscosity of 5-10 times of deionized water then is added in depolymerization liquid
In oxygen alkane, ultrasonic wave dispersion is adjusted with acid pH to 1-4.
Wherein, the concentration of the graphene oxide in ethanol is 1-10g/L, and the covalent halide is in deionized water
Concentration be 1-25g/L.
Wherein, the alcohol is at least one of ethyl alcohol, propyl alcohol, isopropanol, butanol, amylalcohol；The acid is at least
One of hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, oxalic acid；The covalent halide is at least alchlor, ferric trichloride, tetrachloro
Change one of titanium, thionyl chloride, phosphorus trichloride, phosphorus tribromide.
Beneficial effects of the present invention: preparing polysiloxanes matrix under cationic catalysts system, is with lipophilic graphene
Filler and chemical graft polysiloxanes, it is compound to obtain the graphene-based polysiloxanes of low-viscosity, the polynary depolymerization system of graphene is introduced,
Stablize polysiloxane molecule amount, reduce silicone cross degree, provides a kind of viscosity of effectively control composite material, promote stone
The method of dispersion stabilization of the black alkene in polysiloxanes, while simple possible, convieniently synthesized, purification are easy, and greatly prolong
After the present invention is applied to leather finish, it is wear-resisting, resistance to dry/wet can be obviously improved leather for the pot life of graphene-based polysiloxanes
Wiping and waterproof performance.
Specific embodiment
Now in conjunction with specific embodiment, the present invention is further described.
Embodiment 1:
A kind of preparation method of the graphene-based polysiloxanes of low-viscosity of the present invention, the preparation method include as follows
Step:
S1: adding graphene oxide into deionized water, ultrasonic disperse: 30min obtains dispersion liquid；
S2: silane coupling agent is added in S1 dispersion liquid, reacts 12h at 50 DEG C；
S3: products therefrom in S2 is first washed 2 times with dehydrated alcohol, then is washed with deionized 1 time；
S4: dispersing product obtained in S3 in deionized water, is ultrasonically treated 1h, and 5% hydrazine hydrate reduction 3h is added；
Product obtained in S5:S4 repeats the washing operation of S3, obtains lipophilic graphene after vacuum drying；
S6: reacting 3h for siloxanyl monomers, end-capping reagent, catalyst at 70 DEG C, and products therefrom adds silane coupling agent, drop
Temperature obtains low-viscosity polysiloxanes to 50 DEG C of reaction 1h；
S7: it disperses lipophilic graphene obtained in S5 in the resulting low-viscosity polysiloxanes of S6, is stirred well to
Uniformly, 1 times of deionized water is then added, 1 is dispersed in ultrasonic wave and obtains graphene-based polysiloxanes dispersion liquid；
S8: organic metal salt is added in graphene-based polysiloxanes dispersion liquid obtained in S7, in 10 DEG C of reaction 3h, very
After sky is dry, the graphene-based polysiloxanes of low-viscosity is made.
Wherein, the silane coupling agent is 3- aminopropyl triethoxysilane, and the graphene oxide is in deionized water
Concentration be 2g/L, the concentration of the silane coupling agent in deionized water be 4g/L.
Wherein, the siloxanyl monomers are octamethylcy-clotetrasiloxane；The silane coupling agent is at least 3- aminopropyl three
Ethoxysilane；The catalyst is phosphoric acid.
Wherein, the concentration of the silane coupling agent is 0.1%, and the end-capping reagent concentration is 0.1%, and the catalyst is dense
Degree is 0.5%.
Wherein, the organic metal salt is iron naphthenate.
Wherein, concentration of the lipophilic graphene in polysiloxanes is 1g/L, and the organic metal salt is in graphene
Concentration in based polysiloxane dispersion liquid is 0.005g/L.
Wherein, a kind of method reducing graphene-based silicone cross degree, which is characterized in that successively include with
Lower step:
S1: graphene oxide is dissolved in ethyl alcohol, then ultrasonic wave dispersion obtains graphite oxide to 2 with salt acid for adjusting pH
Alkene depolymerization liquid；
S2: alchlor is dissolved in deionized water, then ultrasonic wave dispersion obtains tri-chlorination to 1 with salt acid for adjusting pH
Aluminium depolymerization liquid；
S3: it is by weight, 10 parts of graphene depolymerization liquid, 20 parts of alchlor depolymerization liquid are soluble in water, it is uniformly mixed
Depolymerization liquid is made, then depolymerization liquid is added in 5 times of graphene-based polysiloxanes of the diluted low-viscosity of deionized water, ultrasonic wavelength-division
It dissipates, with salt acid for adjusting pH to 1.
Wherein, the concentration of the graphene oxide in ethanol is 1g/L, the alchlor in deionized water dense
Degree is 1g/L.
Embodiment 2:
A kind of preparation method of the graphene-based polysiloxanes of low-viscosity of the present invention, the preparation method include as follows
Step:
S1: adding graphene oxide into deionized water, and ultrasonic disperse 90min obtains dispersion liquid；
S2: silane coupling agent is added in S1 dispersion liquid, reacts 72h at 100 DEG C；
S3: products therefrom in S2 is first washed 6 times with dehydrated alcohol, then is washed with deionized 7 times；
S4: dispersing product obtained in S3 in deionized water, is ultrasonically treated 1h, and 5% hydrazine hydrate reduction 12h is added；
Product obtained in S5:S4 repeats the washing operation of S3, obtains lipophilic graphene after vacuum drying；
S6: reacting 8h for siloxanyl monomers, end-capping reagent, catalyst at 140 DEG C, and products therefrom adds silane coupling agent,
It is cooled to 70 DEG C of reaction 3h and obtains low-viscosity polysiloxanes；
S7: it disperses lipophilic graphene obtained in S5 in the resulting low-viscosity polysiloxanes of S6, is stirred well to
Uniformly, 5 times of deionized waters are then added, 3h is dispersed in ultrasonic wave and obtains graphene-based polysiloxanes dispersion liquid；
S8: organic metal salt is added in graphene-based polysiloxanes dispersion liquid obtained in S7, in 50 DEG C of reaction 8h, very
After sky is dry, the graphene-based polysiloxanes of low-viscosity is made.
Wherein, the silane coupling agent is 3- aminopropyl triethoxysilane, and the graphene oxide is in deionized water
Concentration be 2g/L, the concentration of the silane coupling agent in deionized water be 4g/L.
Wherein, the siloxanyl monomers are octamethylcy-clotetrasiloxane；The silane coupling agent is at least 3- aminopropyl three
Ethoxysilane；The catalyst is phosphoric acid.
Wherein, the concentration of the silane coupling agent is 5%, and the end-capping reagent concentration is 1%, and the catalyst concn is
2.5%.
Wherein, the organic metal salt is iron naphthenate.
Wherein, concentration of the lipophilic graphene in polysiloxanes is 100g/L, and the organic metal salt is in graphite
Concentration in alkenyl polysiloxanes dispersion liquid is 0.025g/L.
Wherein, a kind of method reducing graphene-based silicone cross degree, which is characterized in that successively include with
Lower step:
S1: graphene oxide is dissolved in ethyl alcohol, then ultrasonic wave dispersion obtains graphite oxide to 4 with salt acid for adjusting pH
Alkene depolymerization liquid；
S2: alchlor is dissolved in deionized water, then ultrasonic wave dispersion obtains trichlorine to 3.5 with salt acid for adjusting pH
Change aluminium depolymerization liquid；
S3: it is by weight, 15 parts of graphene depolymerization liquid, 30 parts of alchlor depolymerization liquid are soluble in water, it is uniformly mixed
Depolymerization liquid is made, then depolymerization liquid is added in 10 times of graphene-based polysiloxanes of the diluted low-viscosity of deionized water, ultrasonic wave
Dispersion, with salt acid for adjusting pH to 4.
Wherein, the concentration of the graphene oxide in ethanol is 10g/L, the alchlor in deionized water dense
Degree is 25g/L.
Embodiment 3:
A kind of preparation method of the graphene-based polysiloxanes of low-viscosity of the present invention, the preparation method include as follows
Step:
S1: adding graphene oxide into deionized water, and ultrasonic disperse 60min obtains dispersion liquid；
S2: silane coupling agent is added in S1 dispersion liquid, is reacted for 24 hours at 60 DEG C；
S3: products therefrom in S2 is first washed 5 times with dehydrated alcohol, then is washed with deionized 3 times；
S4: dispersing product obtained in S3 in deionized water, is ultrasonically treated 1h, and 5% hydrazine hydrate reduction 3h is added；
Product obtained in S5:S4 repeats the washing operation of S3, obtains lipophilic graphene after vacuum drying；
S6: reacting 4h for siloxanyl monomers, end-capping reagent, catalyst at 110 DEG C, and products therefrom adds silane coupling agent,
It is cooled to 60 DEG C of reaction 1h and obtains low-viscosity polysiloxanes；
S7: it disperses lipophilic graphene obtained in S5 in the resulting low-viscosity polysiloxanes of S6, is stirred well to
Uniformly, 2 times of deionized waters are then added, 1.5h is dispersed in ultrasonic wave and obtains graphene-based polysiloxanes dispersion liquid；
S8: organic metal salt is added in graphene-based polysiloxanes dispersion liquid obtained in S7, in 30 DEG C of reaction 5h, very
After sky is dry, the graphene-based polysiloxanes of low-viscosity is made.
Wherein, the silane coupling agent is 3- aminopropyl triethoxysilane, and the graphene oxide is in deionized water
Concentration be 2g/L, the concentration of the silane coupling agent in deionized water be 4g/L.
Wherein, the siloxanyl monomers are octamethylcy-clotetrasiloxane；The silane coupling agent is at least 3- aminopropyl three
Ethoxysilane；The catalyst is phosphoric acid.
Wherein, the concentration of the silane coupling agent is 1%, and the end-capping reagent concentration is 0.2%, the catalyst concn
It is 0.5%.
Wherein, the organic metal salt is iron naphthenate.
Wherein, concentration of the lipophilic graphene in polysiloxanes is 15g/L, and the organic metal salt is in graphene
Concentration in based polysiloxane dispersion liquid is 0.005g/L.
Wherein, a kind of method reducing graphene-based silicone cross degree, which is characterized in that successively include with
Lower step:
S1: graphene oxide is dissolved in ethyl alcohol, ultrasonic wave dispersion, then with salt acid for adjusting pH to 3.5, obtains oxidation stone
Black alkene depolymerization liquid；
S2: alchlor is dissolved in deionized water, then ultrasonic wave dispersion obtains tri-chlorination to 3 with salt acid for adjusting pH
Aluminium depolymerization liquid；
S3: it is by weight, 12 parts of graphene depolymerization liquid, 25 parts of alchlor depolymerization liquid are soluble in water, it is uniformly mixed
Depolymerization liquid is made, then depolymerization liquid is added in 5 times of graphene-based polysiloxanes of the diluted low-viscosity of deionized water, ultrasonic wavelength-division
It dissipates, with salt acid for adjusting pH to 2.5.
Wherein, the concentration of the graphene oxide in ethanol is 2.5g/L, and the alchlor is in deionized water
Concentration is 10g/L.
It is the optimal embodiment of the present invention with embodiment 3.
Application examples
For the preparation method of low-viscosity graphene polysiloxanes described in further instruction and reduce polysiloxanes friendship
The technical effect of the method for connection degree carries out preparation example 1 and prepares the Experimental comparison of comparative example 1, wherein preparation example 1 and preparation pair
1 preparation method of ratio is consistent, and difference is only that, preparation example 1 uses cationic catalysts system and organometallic salt catalysts, right
Ratio 1 uses anionic catalytic system and organic amine catalyst, investigates the two viscosity situation, and comparing result is as shown in table 1 below:
Polysiloxanes viscosity under 1 different catalysts system of table
According to table 1, present invention gained polysiloxanes viscosity is low, synthetic route simple possible, low-viscosity polysiloxanes
It is avoided that the generation of macromolecular silicon rubber in synthesizing graphite alkene based polysiloxane, while reducing the difficulty of subsequent emulsifying process
Degree.
For the progressive of the graphene-based polysiloxanes of further instruction present invention gained, preparation example 1 is reduced
The processing of silicone cross degree, while the two viscosity situation is investigated with the comparison of preparation example 1 being not handled by, comparing result is as follows
Shown in table 2:
Polysiloxanes viscosity during being stored under 2 different disposal of table
| Preparation example 1 | Prepare comparative example 1 | |
| Viscosity | 135mPa·s | 135mPa·s |
| Viscosity after three days | 135mPa·s | 2800mPa·s |
| Viscosity after seven days | 130mPa·s | 9350mPa·s |
| Viscosity after two weeks | 130mPa·s | Solidification |
| Viscosity after three months | 160mPa·s | Solidification |
According to table 2, method provided by the present invention has delayed the Storage period of graphene-based polysiloxanes significantly, suitable
Storage period in, the variation of polysiloxanes viscosity is smaller, or even have slight decrease, and Comparison study example viscosity steeply rises, until
Solidification, it is simple for process, and greatly prolong the pot life of graphene-based polysiloxanes.
The foregoing descriptions are merely the embodiment using this origination techniques content, any those skilled in the art use this wound
Make done modifications and changes, all belong to the scope of the patents of this creation opinion, and is not limited to those disclosed embodiments.
Claims (9)
1. a kind of preparation method of the graphene-based polysiloxanes of low-viscosity, it is characterised in that: the preparation method includes following step
It is rapid:
S1: adding graphene oxide into deionized water, and ultrasonic disperse 30-90min obtains dispersion liquid；
S2: silane coupling agent is added in S1 dispersion liquid, reacts 12-72h at 50-100 DEG C；
S3: products therefrom in S2 is first washed 2-6 times with dehydrated alcohol, then is washed with deionized 1-7 times；
S4: dispersing product obtained in S3 in deionized water, is ultrasonically treated 1h, and 5% hydrazine hydrate reduction 3-12h is added；
Product obtained in S5:S4 repeats the washing operation of S3, obtains lipophilic graphene after vacuum drying；
S6: reacting 3-8h for siloxanyl monomers, end-capping reagent, catalyst at 70-140 DEG C, and products therefrom adds silane coupling agent,
It is cooled to 50-70 DEG C of reaction 1-3h and obtains low-viscosity polysiloxanes；
S7: dispersing lipophilic graphene obtained in S5 in the resulting low-viscosity polysiloxanes of S6, is stirred well to uniformly,
1-5 times of deionized water is then added, 1-3h is dispersed in ultrasonic wave and obtains graphene-based polysiloxanes dispersion liquid；
S8: organic metal salt is added obtained in S7 in graphene-based polysiloxanes dispersion liquid, in 10-50 DEG C of reaction 3-8h,
After vacuum drying, the graphene-based polysiloxanes of low-viscosity is made.
2. the preparation method of the graphene-based polysiloxanes of low viscosity according to claim 1, it is characterised in that: the silane
Coupling agent is at least 3- chloropropyl triethoxysilane, 3- aminopropyl triethoxysilane, three second of 3- (2,3 the third oxygen of epoxy) propyl
One of oxysilane, triethoxysilane, the concentration of the graphene oxide in deionized water is 1-10g/L, described
The concentration of silane coupling agent in deionized water is 1-15g/L.
3. the preparation method of the graphene-based polysiloxanes of low viscosity according to claim 1, it is characterised in that: the silicon oxygen
Alkane monomer is at least hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic rings, six silicon
One of oxygen alkane；The silane coupling agent is at least 3- chloropropyl triethoxysilane, 3- aminopropyl triethoxysilane, 3-
One of (2,3 the third oxygen of epoxy) propyl-triethoxysilicane, triethoxysilane；The catalyst be at least sulfuric acid, hydrochloric acid,
One of nitric acid, phosphoric acid, boric acid, chlorosulfonic acid.
4. the preparation method of the graphene-based polysiloxanes of low viscosity according to claim 1, it is characterised in that: the silane
The concentration of coupling agent is 0.1-5%, and the end-capping reagent concentration is 0.1-1%, and the catalyst concn is 0.5-2.5%.
5. the preparation method of the graphene-based polysiloxanes of low viscosity according to claim 1, it is characterised in that: described organic
Metal salt is at least one of zinc octoate, iron octoate, iron naphthenate, aphthenic acids tin.
6. the preparation method of the graphene-based polysiloxanes of low viscosity according to claim 1, it is characterised in that: the oleophylic
Property concentration of the graphene in polysiloxanes be 1-100g/L, the organic metal salt is in graphene-based polysiloxanes dispersion liquid
Concentration be 0.005-0.025g/L.
7. a kind of method for reducing graphene-based silicone cross degree, which is characterized in that successively the following steps are included:
S1: graphene oxide is dissolved in alcohol, then ultrasonic wave dispersion is adjusted with acid pH to 2-4, obtains graphene oxide depolymerization
Liquid；
S2: covalent halide is dissolved in deionized water, then ultrasonic wave dispersion is adjusted with acid pH to 1.5-3.5, obtains covalently
Halide depolymerization liquid；
S3: it is by weight, 10-15 parts of graphene oxide depolymerization liquid, 20-30 parts of covalent halide depolymerization liquid are soluble in water,
It is uniformly mixed obtained depolymerization liquid, the graphene-based polysiloxanes of the diluted low-viscosity of 5-10 times of deionized water then is added in depolymerization liquid
In, ultrasonic wave dispersion is adjusted with acid pH to 1-4.
8. the method according to claim 7 for reducing graphene-based silicone cross degree, it is characterised in that: the oxidation
Concentration of the graphene in alcohol is 1-10g/L, and the concentration of the covalent halide in deionized water is 1-25g/L.
9. the method according to claim 8 for reducing graphene-based silicone cross degree, it is characterised in that: the alcohol
At least one of ethyl alcohol, propyl alcohol, isopropanol, butanol, amylalcohol；The acid is at least hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, grass
One of acid；The covalent halide is at least alchlor, ferric trichloride, titanium tetrachloride, thionyl chloride, tri-chlorination
One of phosphorus, phosphorus tribromide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910559645.1A CN110330652A (en) | 2019-06-26 | 2019-06-26 | A kind of preparation method of the graphene-based polysiloxanes of low-viscosity and the method for reducing graphene-based silicone cross degree |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910559645.1A CN110330652A (en) | 2019-06-26 | 2019-06-26 | A kind of preparation method of the graphene-based polysiloxanes of low-viscosity and the method for reducing graphene-based silicone cross degree |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110330652A true CN110330652A (en) | 2019-10-15 |
Family
ID=68142732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910559645.1A Pending CN110330652A (en) | 2019-06-26 | 2019-06-26 | A kind of preparation method of the graphene-based polysiloxanes of low-viscosity and the method for reducing graphene-based silicone cross degree |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110330652A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112794314A (en) * | 2021-04-07 | 2021-05-14 | 山东海科创新研究院有限公司 | Preparation method of high-density graphene heat-conducting film regulated and controlled by groups and obtained product |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160340495A1 (en) * | 2009-11-12 | 2016-11-24 | The Trustees Of Princeton University | Multifunctional graphene-silicone elastomer nanocomposite, method of making the same, and uses thereof |
| CN107201071A (en) * | 2016-05-20 | 2017-09-26 | 南京长江涂料有限公司 | A kind of graphene sheet Conductive mica oil tank static electricity conductive anticorrosive paint and preparation method thereof |
| CN108484933A (en) * | 2018-05-10 | 2018-09-04 | 浙江科峰新材料有限公司 | A kind of organic silicon emulsion and its production technology |
| CN109651816A (en) * | 2018-11-20 | 2019-04-19 | 兴业皮革科技股份有限公司 | A kind of compound emulsion method of graphene-based polysiloxanes |
| CN109666149A (en) * | 2018-11-20 | 2019-04-23 | 兴业皮革科技股份有限公司 | A kind of preparation method of the graphene-based polysiloxanes of silicon oxygen six-membered ring structure |
-
2019
- 2019-06-26 CN CN201910559645.1A patent/CN110330652A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160340495A1 (en) * | 2009-11-12 | 2016-11-24 | The Trustees Of Princeton University | Multifunctional graphene-silicone elastomer nanocomposite, method of making the same, and uses thereof |
| CN107201071A (en) * | 2016-05-20 | 2017-09-26 | 南京长江涂料有限公司 | A kind of graphene sheet Conductive mica oil tank static electricity conductive anticorrosive paint and preparation method thereof |
| CN108484933A (en) * | 2018-05-10 | 2018-09-04 | 浙江科峰新材料有限公司 | A kind of organic silicon emulsion and its production technology |
| CN109651816A (en) * | 2018-11-20 | 2019-04-19 | 兴业皮革科技股份有限公司 | A kind of compound emulsion method of graphene-based polysiloxanes |
| CN109666149A (en) * | 2018-11-20 | 2019-04-23 | 兴业皮革科技股份有限公司 | A kind of preparation method of the graphene-based polysiloxanes of silicon oxygen six-membered ring structure |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112794314A (en) * | 2021-04-07 | 2021-05-14 | 山东海科创新研究院有限公司 | Preparation method of high-density graphene heat-conducting film regulated and controlled by groups and obtained product |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7605284B2 (en) | Process for preparing organically modified polyorganosiloxanes | |
| Chen et al. | Synthesis and characterization of novel room temperature vulcanized (RTV) silicone rubbers using octa [(trimethoxysilyl) ethyl]-POSS as cross-linker | |
| EP2782953B1 (en) | Composition of olefinically functionalsied siloxane oligomers based on alkoxy silanes | |
| CN102977377B (en) | Solvent-free method for preparing polyether modified polysiloxane antifoaming agent | |
| CN1248224A (en) | Method for making hydrophobic silica gels under neutral conditions | |
| CN111100281B (en) | Preparation method of modified graphene oxide catalyst | |
| CN105297427B (en) | A kind of compound for improving amino-modified silicone oil based carbon fiber finish heat resistance and its preparation and application | |
| JP7420474B2 (en) | Modified polymethylhydrosiloxane, modified high-cis conjugated diene polymer, method for producing the same, and rubber composition and tire using the same | |
| EP2877527B1 (en) | Addition-crosslinking silicone composition with low compression set | |
| CN110330652A (en) | A kind of preparation method of the graphene-based polysiloxanes of low-viscosity and the method for reducing graphene-based silicone cross degree | |
| CN103608362B (en) | For the preparation of 1,3-butadiene and the method for cinnamic multipolymer and the purposes in vulcanizable elastic composition thereof | |
| CN107189068A (en) | A kind of preparation method of dimethyl end hydroxyl silicone oil | |
| CN104307570B (en) | A kind of platinum allyl polyether composition catalyst and its preparation method and application | |
| CN104892946B (en) | A kind of polysiloxane-modified daiamid and its preparation method and application | |
| Uragami et al. | Membrane reactor for acceleration of esterification using a special ionic liquid with reaction and separation and microwave heating | |
| CN109384926A (en) | A kind of unsaturated ring oxidation polysiloxanes and its preparation method and application | |
| CN1834133A (en) | Branched benzene siliconic oil | |
| CN100575255C (en) | A kind of method of preparing super-hydrophobic silica by one-step process | |
| CN105017536A (en) | Acyloxy containing hydroxyalkyl polysiloxane and preparation method | |
| CN106750321B (en) | Preparation method of siloxane quaternary ammonium salt | |
| CN112480684B (en) | Silanized graphene/silicone rubber composite material and preparation method and application thereof | |
| CN114874443A (en) | Silicon rubber with low curing shrinkage rate and preparation method thereof | |
| CN113317315A (en) | Low-foam organic silicon surfactant and preparation method and application thereof | |
| CN107778325B (en) | Preparation method of N- [3- (trimethoxysilyl) propyl ] N-butylamine | |
| CN110698675A (en) | Hydroxyl fluorosilicone oil and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191015 |
|
| RJ01 | Rejection of invention patent application after publication |