CN110734593A - Method for preparing emulsion polymerized styrene butadiene rubber from modified graphene - Google Patents
Method for preparing emulsion polymerized styrene butadiene rubber from modified graphene Download PDFInfo
- Publication number
- CN110734593A CN110734593A CN201810794752.8A CN201810794752A CN110734593A CN 110734593 A CN110734593 A CN 110734593A CN 201810794752 A CN201810794752 A CN 201810794752A CN 110734593 A CN110734593 A CN 110734593A
- Authority
- CN
- China
- Prior art keywords
- parts
- mass
- ionic liquid
- graphene
- modified graphene
- 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.)
- Granted
Links
Images
Classifications
-
- 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
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Abstract
The invention provides a method for preparing emulsion polymerized styrene-butadiene rubber from modified graphene, which comprises the steps of (1) preparing an ionic liquid modified graphene viscoelastic fluid, namely adding ionic liquid imidazolium salt and graphene into a mortar, grinding for 2-5 h at room temperature, adding methyl cellulose, continuously grinding for 2-4 h to obtain the ionic liquid modified graphene viscoelastic fluid, (2) coagulating latex, namely adding styrene-butadiene latex into a coagulation kettle, adding the ionic liquid modified graphene viscoelastic fluid (1), stirring and mixing for 30min, adding a demulsifier and soft water at the coagulation temperature of 30-50 ℃, stirring and mixing for 30min, adding a coagulant for coagulation, stirring for 2-5 h at 80-100 ℃ for curing, washing, dehydrating and drying to obtain a polymer.
Description
Technical Field
The invention relates to a method for preparing emulsion polymerized styrene-butadiene rubber from modified graphene, in particular to a method for preparing emulsion polymerized styrene-butadiene rubber from ionic liquid and methyl cellulose modified graphene, and specifically to methods for preparing modified emulsion polymerized styrene-butadiene rubber by using an emulsion method.
Background
The graphene has excellent electrical, optical, thermal, mechanical and high specific surface area properties, and is which is a research hotspot in the fields of physics, chemistry, biology and the like in recent years, but the graphene has poor dispersibility in solvents and matrixes, easy stacking and agglomeration among laminas, and great inconvenience in industrial production and application of the graphene.
CN104893042A discloses vulcanized rubber containing ionic liquid modified graphene oxide and a preparation method thereof, wherein the vulcanized rubber comprises, by mass, 100 parts of rubber, 2-6 parts of ionic liquid modified graphene oxide, 2-10 parts of zinc oxide, 1-5 parts of stearic acid, 1-3 parts of a vulcanization accelerator, 2-5 parts of an anti-aging agent and 1-4 parts of a vulcanizing agent.
CN102712779A discloses a method for preparing graphene dispersion, and a graphene-ionic liquid polymer composite material prepared by the method and a method for preparing the same, which can prepare a graphene-ionic liquid polymer composite material using a graphene dispersion prepared by dispersing graphite into an ionic liquid, CN102142294A discloses graphene-ionic liquid composite materials and a method for preparing the same, wherein the composite material comprises 0.01-99.99% of graphene and 0.01-99.99% of ionic liquid by mass fraction, the ionic liquid has a polar electron cloud structure, the graphene is a graphene sheet structure, and the ionic liquid is doped between graphene sheets through the polar electron cloud structure to form a graphene-ionic liquid composite structure.
CN106009424A discloses fluorine-containing ionic liquid covalent bond modified graphene/fluoroether rubber and a preparation method thereof, wherein the ionic liquid is grafted on the surface of graphite oxide by utilizing chemical reaction among organic functional groups, functional filler is obtained by thermal reduction, the filler, fluoroether raw rubber and a compounding agent are mixed and vulcanized and molded to obtain a final product, the graphene/fluoroether rubber effectively overcomes the defects that graphene is easy to self-aggregate and poor in compatibility with rubber molecules, and the fluoroether rubber filled by utilizing the functional graphene as the filler has good mechanical property, frictional wear resistance and high temperature resistance, and the preparation method is simple and easy to implement and has good application prospects.
CN103102514A discloses ionic liquid modified natural rubber vulcanized rubber containing graphene oxide, graphene oxide is obtained by modifying ionic liquid through a solid grinding method, the modified graphene oxide and natural rubber are mechanically mixed on an open mill or an internal mixer, meanwhile, zinc oxide, stearic acid, an anti-aging agent, an accelerator, a vulcanizing agent, carbon black and other formulas are added to obtain natural rubber mixed rubber containing ionic liquid modified graphene oxide, and then vulcanization processing is carried out to obtain the ionic liquid modified graphene oxide/natural rubber vulcanized rubber.
CN103102514B discloses ionic liquid modified natural rubber vulcanized rubber containing graphene oxide, graphene oxide is obtained by modifying ionic liquid through a solid grinding method, the modified graphene oxide and natural rubber are mechanically mixed on an open mill or an internal mixer, meanwhile, zinc oxide, stearic acid, an anti-aging agent, an accelerator, a vulcanizing agent, carbon black and other formulas are added to obtain natural rubber mixed rubber containing ionic liquid modified graphene oxide, and then vulcanization processing is carried out to obtain the ionic liquid modified graphene oxide/natural rubber vulcanized rubber.
US2014316028(a1), WO2013097605(a1) disclose methods for preparing completely exfoliated graphene/rubber nanocomposites, which process comprises subjecting the emulsion to a flocculation process or spray drying of the composite emulsion, maintaining the form of the graphene oxide/rubber composite emulsion in a liquid state, achieving high dispersion and high dispersion of a layered form in a nano scale, and at the same time, substances capable of generating ionic bonds or surface functional group bonds of chemical graphene oxide are added to the graphene oxide/hydrosol as a surfactant, thereby increasing interfacial bonding between the graphene oxide and the rubber.
Disclosure of Invention
The invention aims to provide a method for preparing emulsion polymerized styrene-butadiene rubber from ionic liquids and methylcellulose modified graphene, and the prepared rubber has excellent wear resistance and mechanical properties.
Therefore, the invention provides a method for preparing emulsion polymerized styrene-butadiene rubber from ionic liquids and methylcellulose modified graphene, which comprises the following steps:
(1) preparing an ionic liquid modified graphene viscoelastic fluid: adding 1200-1500 parts by mass of ionic liquid imidazolium salt into a mortar, adding 100 parts by mass of graphene, grinding for 2-5 hours at room temperature, adding 0.5-2 parts by mass of methyl cellulose, and continuously grinding for 2-4 hours to obtain the ionic liquid modified graphene viscoelastic fluid.
(2) Latex agglomeration: adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, stirring and mixing, adding 5-20 parts by mass of ionic liquid modified graphene viscoelastic fluid (prepared in the step (1)), stirring and mixing for 30min, adding 3-15 parts by mass of demulsifier and 20-100 parts by mass of soft water at a coagulation temperature of 30-50 ℃, stirring and mixing for 30min, adding 5-15 parts by mass of coagulant for coagulation, stirring at 80-100 ℃ for 2-5 h for curing, and then washing, dehydrating and drying to obtain the polymer.
In the preparation of the ionic liquid modified graphene viscoelastic fluid, the ionic liquid is imidazole salt, such as or more selected from 1-butyl-3-methylimidazole hexafluorophosphate, 1-octyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt) and 1-hexyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt.
In the preparation of the ionic liquid modified graphene viscoelastic fluid, the number of graphene layers is less than 20, and the mass ratio of graphene to ionic liquid is 1: 12-1: 15.
The methyl cellulose in the latex coagulation is white or off-white fibrous or granular powder, has no odor, has an average molecular weight of 186.86n (n is the polymerization degree), is about 18000-200000, and is used in an amount of 0.5-2 parts.
The demulsifier in the latex coagulation is a saturated NaCl aqueous solution, and the using amount of the demulsifier is 3-15 parts.
The coagulant used in the latex coagulation is sulfuric acid, and the using amount is 5-15 parts.
The polymer obtained by the invention has the performance of Ny viscosity ML(1+4) 100℃55-70, the 300% stress at definite elongation is 19.5-27 MPa, the tensile strength is more than or equal to 28.0MPa, the elongation at break is more than or equal to 570%, and the abrasion coefficient is less than or equal to 0.09.
The method for preparing emulsion polymerized styrene-butadiene rubber from the ionic liquid and the methyl cellulose modified graphene, provided by the invention, is characterized in that the imidazole salt ionic liquid modified graphene modifies the surface of the graphene without damaging the surface structure by utilizing the interaction between the imidazole salt ionic liquid and pi-pi bonds between the graphene; the dispersion of the ionic liquid in the rubber matrix is improved by the hydrogen bond action of the ionic liquid and the graphene, and the interface interaction between the ionic liquid and the rubber matrix is enhanced, so that the mechanical property of the rubber is improved; the mixed solution of ionic liquid modified graphene is added in the emulsion polymerized styrene butadiene rubber coagulation, and the modification method is simple and easy to operate.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention;
FIG. 2 is a schematic flow diagram of example 1 of the process of the present invention;
FIG. 3 is a schematic flow diagram of example 2 of the process of the present invention;
FIG. 4 is a schematic flow diagram of example 3 of the method of the present invention;
FIG. 5 is a schematic flow diagram of example 4 of the method of the present invention.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The required medicines are all commercial industrial products;
the styrene-butadiene latex is stable emulsion formed by polymerizing and copolymerizing butadiene and styrene through low-temperature emulsion, wherein the pH value is 3-7, and the solid content is 15-25 w%.
Soft water refers to water containing no or less soluble calcium and magnesium compounds, and the content of calcium and magnesium ions in water is usually expressed by the index "hardness". Hardness 1 degree corresponds to 10 mg of calcium oxide per liter of water, and water below 8 degrees is called soft water.
Test methods and their standards:
Ny viscosity GB/T1232.1-2000;
300% stress at definite elongation, tensile strength, elongation at break: GB/T528-2009;
wear coefficient: the measurement was carried out using an Akron abrasion machine according to GB/T1689-1998 standard.
Example 1
(1) Preparing an ionic liquid modified graphene viscoelastic fluid: adding 1200 parts by mass of 1-butyl-3-methylimidazole hexafluorophosphate into a mortar, adding 100 parts by mass of graphene, grinding for 3 hours at room temperature, adding 0.5 part by mass of methylcellulose, and continuously grinding for 4 hours to obtain the 1-butyl-3-methylimidazole hexafluorophosphate modified graphene viscoelastic fluid.
(2) And (2) latex coagulation, namely adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, stirring and mixing, adding 10 parts by mass of 1-butyl-3-methylimidazole hexafluorophosphate modified graphene viscoelastic fluid, stirring and mixing for 30min, adding 5 parts by mass of saturated NaCl aqueous solution while and 100 parts by mass of soft water while are added at the coagulation temperature of 30 ℃, stirring and mixing for 30min, adding 15 parts by mass of sulfuric acid for coagulation, stirring for 3h at 80 ℃ for curing, and then washing, dehydrating and drying to obtain the polymer.
Ny viscosity ML according to the detection standard(1+4) 100℃58, 300 percent stress at definite elongation of 22.4MPa, tensile strength of 29.1MPa, elongation at break of 579 percent and abrasion coefficient of 0.085.
Comparative example 1
The experimental conditions are the same as example 1, except that the graphene is not modified by 1-butyl-3-methylimidazolium hexafluorophosphate and is directly added into the solution (2), and the viscosity ML is measured according to the detection standard, wherein the viscosity ML is Ny(1+4) 100℃51, 300% stress at definite elongation of 17.8MPa, tensile strength of 19.2MPa, elongation at break of 501%, and abrasion coefficient of 0.105.
Example 2
(1) Preparing an ionic liquid modified graphene viscoelastic fluid: adding 1500 parts by mass of 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt into a mortar, adding 100 parts by mass of graphene, grinding at room temperature for 3 hours, adding 1 part by mass of methylcellulose, and continuously grinding for 3 hours to obtain the 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt modified graphene viscoelastic fluid.
(2) And (2) latex coagulation, namely adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, stirring and mixing, adding 5 parts by mass of 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide modified graphene viscoelastic fluid, stirring and mixing for 30min, adding 3 parts by mass of saturated NaCl aqueous solution while and 100 parts by mass of soft water while are added at a coagulation temperature of 50 ℃, stirring and mixing for 30min, adding 5 parts by mass of sulfuric acid for coagulation, stirring for 4h at 80 ℃ for curing, and then washing, dehydrating and drying to obtain the polymer.
Ny viscosity ML according to the detection standard(1+4) 100℃61, 300% stress at definite elongation 25.6MPa, tensile strength 29.0MPa, elongation at break 576%, and abrasion coefficient 0.082.
Comparative example 2
The experimental conditions are the same as example 2, except that the graphene is not modified by 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, and is directly added into the graphene in the step (2), the viscosity ML is measured according to the detection standard, wherein Niy is(1+4) 100℃48, 300% stress at definite elongation of 18.2MPa, tensile strength of 20.3MPa, elongation at break of 511% and abrasion coefficient of 0.112.
Example 3
(1) Preparing an ionic liquid modified graphene viscoelastic fluid: adding 1300 parts by mass of 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt into a mortar, adding 100 parts by mass of graphene, grinding at room temperature for 3 hours, adding 2 parts by mass of methylcellulose, and continuously grinding for 3 hours to obtain the 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt modified graphene viscoelastic fluid.
(2) And (2) latex coagulation, namely adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, stirring and mixing, adding 15 parts by mass of 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide modified graphene viscoelastic fluid, stirring and mixing for 30min, adding 5 parts by mass of saturated NaCl aqueous solution while and 60 parts by mass of soft water while are added at the coagulation temperature of 35 ℃, stirring and mixing for 30min, adding 10 parts by mass of sulfuric acid for coagulation, stirring for 5h at 100 ℃ for curing, and then washing, dehydrating and drying to obtain the polymer.
Ny viscosity ML according to the detection standard(1+4) 100℃65, 300 percent stress at definite elongation of 19.7MPa, tensile strength of 29.8MPa, elongation at break of 570 percent and abrasion coefficient of 0.086.
Comparative example 3
The experimental conditions are the same as example 3, except that graphene is not added, 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt is directly added into the solution (2), and the viscosity ML is measured according to the detection standard of Nib(1+4) 100℃45, 300% stress at definite elongation of 16.3MPa, tensile strength of 21.8MPa, elongation at break of 495%, and abrasion coefficient of 0.118.
Example 4
(1) Preparing an ionic liquid modified graphene viscoelastic fluid: 1400 parts by mass of 1-butyl-3-methylimidazole hexafluorophosphate is added into a mortar, 100 parts by mass of graphene is added, grinding is carried out for 2 hours at room temperature, 1.5 parts of methylcellulose is added, and grinding is continued for 4 hours to obtain the 1-butyl-3-methylimidazole hexafluorophosphate modified graphene viscoelastic fluid.
(2) And (2) latex coagulation, namely adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, stirring and mixing, adding 20 parts by mass of 1-butyl-3-methylimidazole hexafluorophosphate modified graphene viscoelastic fluid, stirring and mixing for 30min, adding 15 parts by mass of saturated NaCl aqueous solution while and 80 parts by mass of soft water while are added at a coagulation temperature of 45 ℃, stirring and mixing for 30min, adding 15 parts by mass of sulfuric acid for coagulation, stirring for 5h at 85 ℃ for curing, and then washing, dehydrating and drying to obtain the polymer.
Ny viscosity ML according to the detection standard(1+4) 100℃61, 300% stress at definite elongation of 20.7MPa, tensile strength of 28.5MPa, elongation at break of 583%, and abrasion coefficient of 0.087.
Comparative example 4
The experimental conditions are the same as example 4, except that graphene is not added, 1-butyl-3-methylimidazolium hexafluorophosphate is directly added into the mixture in the step (2), and the viscosity ML is measured according to the detection standard of Nib(1+4) 100℃52, 300% stress at definite elongation of 16.9MPa, tensile strength of 20.4MPa, elongation at break of 501% and abrasion coefficient of 0.109.
Example 5
(1) Preparing an ionic liquid modified graphene viscoelastic fluid: 1250 parts by mass of 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt) is added into a mortar, 100 parts by mass of graphene is added, grinding is carried out for 5 hours at room temperature, then 0.8 part by mass of methylcellulose is added, and grinding is continued for 3 hours, so that the 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt) modified graphene viscoelastic fluid is obtained.
(2) And (2) latex coagulation, namely adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, stirring and mixing, adding 12 parts by mass of 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide) modified graphene viscoelastic fluid, stirring and mixing for 30min, adding 6 parts by mass of saturated NaCl aqueous solution while and 60 parts by mass of soft water while are added at the coagulation temperature of 35 ℃, stirring and mixing for 30min, adding 7 parts by mass of sulfuric acid for coagulation, stirring for 5h at 100 ℃ for curing, and then washing, dehydrating and drying to obtain the polymer.
Ny viscosity ML according to the detection standard(1+4) 100℃57, 300% stress at definite elongation of 26.8MPa, tensile strength of 29.4MPa, elongation at break of 595%, and abrasion coefficient of 0.088.
Comparative example 5
The experimental conditions are the same as example 5 except that 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt modified graphene and methyl cellulose are not added, and the viscosity ML is measured according to the detection standard of Niy(1+4) 100℃45, 300% stress at definite elongation of 18.1MPa, tensile strength of 19.8MPa, elongation at break of 513% and abrasion coefficient of 0.135.
Example 6
(1) Preparing an ionic liquid modified graphene viscoelastic fluid: 1450 parts by mass of 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt is added into a mortar, 100 parts by mass of graphene is added, grinding is carried out for 3 hours at room temperature, 1.5 parts by mass of methylcellulose is added, and grinding is continued for 2 hours, so that the 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt modified graphene viscoelastic fluid is obtained.
(2) And (2) latex coagulation, namely adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, stirring and mixing, adding 10 parts by mass of 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide modified graphene viscoelastic fluid, stirring and mixing for 30min, adding 5 parts by mass of saturated NaCl aqueous solution while and 100 parts by mass of soft water while are added at the coagulation temperature of 35 ℃, stirring and mixing for 30min, adding 15 parts by mass of sulfuric acid for coagulation, stirring for 5h at 100 ℃ for curing, and then washing, dehydrating and drying to obtain the polymer.
Ny viscosity ML according to the detection standard(1+4) 100℃59, 300% stress at definite elongation of 24.8MPa, tensile strength of 28.6MPa, elongation at break of 581%, and abrasion coefficient of 0.089.
Comparative example 6
The experimental conditions were the same as in example 6 except that no methylcellulose was added, and the viscosity ML was determined according to the test standard to be Ny(1+4) 100℃50, 300% stress at definite elongation of 18.1MPa, tensile strengthThe degree is 20.4MPa, the elongation at break is 515 percent, and the abrasion coefficient is 0.126.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
- The method for preparing emulsion polymerized styrene-butadiene rubber from modified graphene is characterized by comprising the following steps:(1) preparing an ionic liquid modified graphene viscoelastic fluid: adding 1200-1500 parts by mass of ionic liquid into a mortar, adding 100 parts by mass of graphene, grinding for 2-5 hours at room temperature, adding 0.5-2 parts by mass of methyl cellulose, and continuously grinding for 2-4 hours to obtain an ionic liquid modified graphene viscoelastic fluid;(2) latex agglomeration: adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, stirring and mixing, adding 5-20 parts by mass of the ionic liquid modified graphene viscoelastic fluid, stirring and mixing for 30min, adding 3-15 parts by mass of a demulsifier and 20-100 parts by mass of soft water at a coagulation temperature of 30-50 ℃, stirring and mixing for 30min, adding 5-15 parts by mass of a coagulant for coagulation, stirring for 2-5 h at 80-100 ℃, curing, washing, dehydrating and drying to obtain the polymer.
- 2. The method of claim 1, wherein the number of graphene layers is less than 20.
- 3. The method of claim 1, wherein the ionic liquid is an imidazolium salt.
- 4. A process according to claim 3, wherein the imidazolium salt is selected from or more of 1-butyl-3-methylimidazolium hexafluorophosphate, 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, and 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt.
- 5. The method according to claim 1, wherein the methylcellulose is a white or off-white fibrous or granular powder, odorless, and has an average molecular weight of 18000 to 200000.
- 6. The method of claim 1, wherein the emulsion breaker is a saturated aqueous NaCl solution.
- 7. The method of claim 1, wherein said coagulant is sulfuric acid.
- 8. The method of any one of claims 1-7, , wherein the styrene-butadiene latex is a stable emulsion obtained by low temperature emulsion polymerization copolymerization of butadiene and styrene.
- 9. The method according to claim 8, wherein the pH of the styrene-butadiene latex is 3 to 7 and the solid content is 15 to 25 w%.
- 10. The method according to claim 8, wherein the reaction temperature of the low-temperature emulsion polymerization is 3 to 15 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810794752.8A CN110734593B (en) | 2018-07-19 | 2018-07-19 | Method for preparing emulsion polymerized styrene butadiene rubber from modified graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810794752.8A CN110734593B (en) | 2018-07-19 | 2018-07-19 | Method for preparing emulsion polymerized styrene butadiene rubber from modified graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110734593A true CN110734593A (en) | 2020-01-31 |
| CN110734593B CN110734593B (en) | 2021-11-30 |
Family
ID=69235285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810794752.8A Active CN110734593B (en) | 2018-07-19 | 2018-07-19 | Method for preparing emulsion polymerized styrene butadiene rubber from modified graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110734593B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116675888A (en) * | 2023-07-13 | 2023-09-01 | 广东工业大学 | Preparation method of imidazole ionic liquid modified graphene/polyimide composite film and polyimide graphite film |
| CN116790171A (en) * | 2023-06-27 | 2023-09-22 | 福建省三棵树新材料有限公司 | One-pass coating and penetrating film-forming dual-primer-topcoat stone-like paint universal background paint and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102514A (en) * | 2013-01-30 | 2013-05-15 | 南京理工大学 | Ionic liquid modified graphene oxide/natural rubber vulcanized rubber and preparation method thereof |
| CN104893042A (en) * | 2015-05-26 | 2015-09-09 | 南京理工大学 | Rubber vulcanized rubber containing ionic liquid modified graphene oxide and preparation method of vulcanized rubber |
| CN105688809A (en) * | 2016-01-26 | 2016-06-22 | 西南科技大学 | Preparing method for graphene oxide/titanium dioxide nanometer tube composite material |
| JP2017206604A (en) * | 2016-05-17 | 2017-11-24 | Ｊｘｔｇエネルギー株式会社 | Thermoplastic elastomer composition and method for producing the same |
-
2018
- 2018-07-19 CN CN201810794752.8A patent/CN110734593B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102514A (en) * | 2013-01-30 | 2013-05-15 | 南京理工大学 | Ionic liquid modified graphene oxide/natural rubber vulcanized rubber and preparation method thereof |
| CN104893042A (en) * | 2015-05-26 | 2015-09-09 | 南京理工大学 | Rubber vulcanized rubber containing ionic liquid modified graphene oxide and preparation method of vulcanized rubber |
| CN105688809A (en) * | 2016-01-26 | 2016-06-22 | 西南科技大学 | Preparing method for graphene oxide/titanium dioxide nanometer tube composite material |
| JP2017206604A (en) * | 2016-05-17 | 2017-11-24 | Ｊｘｔｇエネルギー株式会社 | Thermoplastic elastomer composition and method for producing the same |
Non-Patent Citations (1)
| Title |
|---|
| 陈杨等: "离子液体改性氧化石墨烯/丁苯橡胶", 《合成橡胶工业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116790171A (en) * | 2023-06-27 | 2023-09-22 | 福建省三棵树新材料有限公司 | One-pass coating and penetrating film-forming dual-primer-topcoat stone-like paint universal background paint and preparation method thereof |
| CN116790171B (en) * | 2023-06-27 | 2024-04-09 | 福建省三棵树新材料有限公司 | One-pass coating and penetrating film-forming dual-primer-topcoat stone-like paint universal background paint and preparation method thereof |
| CN116675888A (en) * | 2023-07-13 | 2023-09-01 | 广东工业大学 | Preparation method of imidazole ionic liquid modified graphene/polyimide composite film and polyimide graphite film |
| CN116675888B (en) * | 2023-07-13 | 2023-12-22 | 广东工业大学 | Preparation method of imidazole ionic liquid modified graphene/polyimide composite film and polyimide graphite film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110734593B (en) | 2021-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104945817B (en) | A kind of itaconate/butadiene copolymer type biological engineering rubber and preparation method thereof | |
| CN104558708A (en) | Multifunctional vulcanized rubber containing polyvinylpyrrolidone-modified graphene oxide and preparation method of multifunctional vulcanized rubber | |
| CN110734587B (en) | Method for preparing nitrile rubber from modified carbon black | |
| CN103554558A (en) | Preparation method of hydroxyethyl methylacrylate rubber grafted and modified clay-enhanced natural rubber composite material | |
| CN113429640A (en) | Rubber composite material containing modified basalt fibers and preparation method thereof | |
| CN110734593A (en) | Method for preparing emulsion polymerized styrene butadiene rubber from modified graphene | |
| CN110734594A (en) | Method for preparing emulsion polymerized styrene butadiene rubber from modified carbon blacks | |
| CN104292391A (en) | Melting production method for unsaturated anhydride grafted chlorinated polyethylene | |
| CN113388245B (en) | Waterproof leaking stoppage grouting material and preparation method and application thereof | |
| CN110734590B (en) | Method for preparing emulsion polymerized styrene-butadiene rubber from ionic liquid and chitosan modified carbon black | |
| CN103289417A (en) | Multi-modified soy protein biodegradable plastic and preparation method thereof | |
| CN110734589A (en) | Method for preparing emulsion polymerized styrene butadiene rubber from modified graphene | |
| CN108948468B (en) | Preparation method of graphene oxide-glass fiber-alumina filling modified oil-resistant corrosion-resistant vulcanized rubber compound | |
| CN110734586B (en) | Method for preparing fluorine-containing nitrile rubber from modified fluorinated graphene | |
| CN107011560A (en) | A kind of functional agglomerate for improving polyethylene heat resistance | |
| CN107337861B (en) | Graphene-butyl rubber material with solvent resistance, preparation method and application thereof | |
| CN114907590A (en) | Synthetic rubber wet masterbatch and preparation method and application thereof | |
| CN110734521B (en) | Method for in-situ reinforcement of emulsion polymerized styrene butadiene rubber by modified carbon nano tube | |
| CN110734591B (en) | Method for preparing fluorine-containing emulsion polymerized styrene-butadiene rubber by modified fluorinated graphene | |
| CN107151335B (en) | Method for preparing clay/rubber nano composite material by slurry blending | |
| CN105622817B (en) | The method that body in-situ polymerization prepares EVA/ graphene composite materials | |
| CN110734592B (en) | Method for preparing oil-extended emulsion polymerized styrene-butadiene rubber by modified carbon nano tube | |
| CN111253643A (en) | Preparation method of graphene oxide reinforced styrene butadiene rubber material | |
| CN106479006A (en) | Elastic composites | |
| CN116731428B (en) | Waste plastic micro-modified nano composite material and preparation method 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |