阅读说明：本技术 一种改性氟化石墨烯制备含氟丁腈橡胶的方法 (Method for preparing fluorine-containing nitrile rubber from modified fluorinated graphene ) 是由 魏绪玲 朱晶 牛承祥 龚光碧 梁滔 李晶 赵玉中 丛日新 于 2018-07-19 设计创作，主要内容包括：本发明提供一种改性氟化石墨烯制备含氟丁腈橡胶的方法,包含：(1)离子液体改性氟化石墨烯乳液的制备：将烧杯中加入乙醇、氟化石墨烯,冰水混合物中超声8～12h,在氟化石墨烯分散液中滴加离子液体,冰水混合物中下搅拌6～10h,得到离子液体改性氟化石墨烯乳液。(2)胶乳凝聚：在烧杯中加入丁腈胶乳、离子液体改性氟化石墨烯乳液(1),超声分散30min～1h,将丁腈胶乳与离子液体改性氟化石墨烯混合液加入凝聚釜搅拌混合30min,在0～15℃温度下,边加入凝聚剂边加入软水,在50～70℃搅拌2～5h进行熟化、然后经洗涤、脱水、干燥得到聚合物。(The invention provides a method for preparing fluorine-containing nitrile butadiene rubber from modified fluorinated graphene, which comprises the steps of (1) preparing an ionic liquid modified fluorinated graphene emulsion, namely adding ethanol and fluorinated graphene into a beaker, performing ultrasonic treatment for 8-12 h in an ice water mixture, dropwise adding an ionic liquid into the fluorinated graphene dispersion liquid, stirring for 6-10 h in the ice water mixture to obtain an ionic liquid modified fluorinated graphene emulsion, (2) performing latex coagulation, namely adding nitrile butadiene latex and the ionic liquid modified fluorinated graphene emulsion (1) into the beaker, performing ultrasonic dispersion for 30 min-1 h, adding the nitrile butadiene latex and the ionic liquid modified fluorinated graphene mixed liquid into a coagulation kettle, stirring and mixing for 30min, adding a coagulant and adding soft water at the temperature of 0-15 ℃, stirring for 2-5 h at the temperature of 50-70 ℃, performing curing, washing, dehydrating and drying to obtain a polymer.)

The method for preparing the fluorine-containing nitrile rubber from modified fluorinated graphene is characterized by comprising the following steps of:

(1) preparing an ionic liquid modified fluorinated graphene emulsion: adding 100 parts by mass of fluorinated graphene into 600-1000 parts by mass of ethanol, performing ultrasonic treatment in an ice water mixture for 8-12 hours to fully disperse the fluorinated graphene, dropwise adding 1200-1500 parts by mass of ionic liquid into a fluorinated graphene dispersion liquid, and stirring in the ice water mixture to obtain an ionic liquid modified fluorinated graphene emulsion;

(2) and (2) latex coagulation, namely adding 5-20 parts by mass of ionic liquid modified fluorinated graphene emulsion into 100 parts by mass of butyronitrile latex, ultrasonically dispersing for 30 min-1 h, adding a mixed solution of the butyronitrile latex and the ionic liquid modified fluorinated graphene into a coagulation kettle, stirring and mixing for 30min, adding 3-15 parts by mass of coagulant into at a coagulation temperature of 0-15 ℃, adding 20-100 parts by mass of soft water into at a coagulation temperature of 50-70 ℃, stirring for 2-5 h, curing, washing, dehydrating and drying to obtain the polymer.

2. The method of claim 1, wherein the number of fluorinated graphene layers is less than 20.

3. The method of claim 1, wherein the ionic liquid is an imidazolium salt.

4. The method according to claim 3, wherein said imidazolium salt is selected from or more of 1-butyl-3-methylimidazolium hexafluorophosphate, 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, and 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide.

5. The method of claim 1, wherein said coagulant is a saturated aqueous NaCl solution.

6. A process as claimed in , wherein the nitrile latex is obtained by emulsion polymerization of butadiene with acrylonitrile, the acrylonitrile content being 25-33% by weight.

7. The method according to claim 6, wherein the acrylonitrile-butadiene latex has an acrylonitrile content of 25-33% by mass.

8. The method according to claim 1, wherein the mass ratio of the fluorinated graphene to the ionic liquid is 1:12 to 1: 15.

9. The method according to claim 1, wherein in the step (1), the stirring time is 6-10 h.

10. The method of claim 1, wherein the ethanol is absolute ethanol having a purity of 99.5%.

Technical Field

The invention relates to a method for preparing fluorine-containing emulsion polymerized styrene-butadiene rubber by ionic liquid modified fluorinated graphene, in particular to a method for preparing fluorine-containing emulsion polymerized styrene-butadiene rubber by emulsion methods.

Background

Fluorinated graphene is the result of partial or total fluorination of graphene, which preserves Sp of some graphene²Structure and Sp of itself³The ionic liquid is salt with a melting point lower than 100 ℃ consisting of organic cations and organic or inorganic anions, has a vapor pressure almost equal to zero, good thermal stability, a very large electrochemical window and structural designability, and has attracted attention in various fields.

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 preparation method of graphene dispersions, and graphene-ionic liquid polymer composites prepared by the method and a preparation method thereof, which are capable of preparing graphene-ionic liquid polymer composites using graphene dispersions prepared by dispersing graphite into an ionic liquid.

CN102142294A discloses graphene-ionic liquid composite materials and a preparation method thereof, wherein the composite materials comprise 0.01-99.99% of graphene and 0.01-99.99% of ionic liquid in parts by mass, the ionic liquid has a polar electronic cloud structure, the graphene is a graphene sheet structure, and the ionic liquid is doped between graphene sheets through the polar electronic 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 nanocomposite, which comprises subjecting an 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, and realizing high dispersion and high dispersion of a layered form in a nano scale, simultaneously, substances can generate ionic bonds or surface functional group bonds of chemical graphene oxide to be added to the graphene oxide/hydrosol as a surfactant, thereby increasing the interfacial bonding between the graphene oxide and the rubber, and the subsequent formulation and vulcanization of the composite material are performed to prepare a vulcanized rubber and dynamic properties, such as high tensile strength, elongation at a stress of , tear strength and the like, and can significantly improve the wear resistance and air barrier property of the vulcanized rubber, and the preparation is simple, low in cost, energy-saving, easy to industrialize, has applicability of , and good economic and social benefits.

WO2015065539(A3), WO2015065539(a2) disclose graphene oxide (S-Go) modified with ionic liquid cetyltrimethylammonium bromide and elastomeric styrene-butadiene rubber (SBR) nanocomposite/carboxymethyl cellulose binder for battery additives.

Disclosure of Invention

The invention aims to provide a method for preparing fluorine-containing nitrile rubber from ionic liquid modified fluorinated graphene, and the prepared nitrile rubber has excellent oil resistance and mechanical properties.

Therefore, the invention provides a method for preparing fluorine-containing nitrile butadiene rubber from ionic liquid modified fluorinated graphene, which comprises the following steps:

(1) preparing an ionic liquid modified fluorinated graphene emulsion: adding 600-1000 parts by mass of ethanol into a beaker, adding 100 parts by mass of fluorinated graphene, performing ultrasonic treatment in an ice-water mixture for 8-12 hours to fully disperse the fluorinated graphene, dropwise adding 1200-1500 parts by mass of ionic liquid into the fluorinated graphene dispersion liquid, and stirring in the ice-water mixture for 6-10 hours to obtain the ionic liquid modified fluorinated graphene emulsion.

(2) Latex agglomeration: adding 100 parts by mass of butyronitrile latex into a beaker, adding 5-20 parts by mass of ionic liquid modified fluorinated graphene emulsion (prepared in the step (1)), ultrasonically dispersing for 30 min-1 h, adding a mixed solution of butyronitrile latex and ionic liquid modified fluorinated graphene into a coagulation kettle, stirring and mixing for 30min, adding 3-15 parts by mass of coagulant and 20-100 parts by mass of soft water at a coagulation temperature of 0-15 ℃, stirring for 2-5 h at a temperature of 50-70 ℃, curing, washing, dehydrating and drying to obtain the polymer.

In the preparation of the ionic liquid modified fluorinated graphene emulsion, 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.

The ethanol is absolute ethanol, and the purity of the ethanol is 99.5%.

In the preparation of the ionic liquid modified fluorinated graphene emulsion, the fluorinated graphene is fluorinated graphene with less than 20 layers, and the mass ratio of the fluorinated graphene to the ionic liquid is 1: 12-1: 15.

The coagulant used in the latex coagulation is a saturated NaCl aqueous solution, and the using amount of the coagulant is 3-15 parts by mass.

The method comprises the step of preparing the acrylonitrile-butadiene latex, wherein the acrylonitrile mass percentage content in the acrylonitrile-butadiene latex is 25-33%.

The method comprises the step of enabling the mass ratio of the fluorinated graphene to the ionic liquid to be 1: 12-1: 15.

According to the method, in the step (1), the stirring time is 6-10 hours.

The method of the invention, wherein the ethanol is absolute ethanol, and the purity of the ethanol is 99.5%.

The polymer obtained by the invention has the following properties:

the content (mass) of the bound acrylonitrile is 28 to 35 percent, and the crude rubber is Niy viscosity ML₍₁₊₄₎ ^100℃40-80, tensile strength more than or equal to 11.0MPa, elongation at break more than or equal to 220, 300% stress at definite elongation more than or equal to 15.0MPa, and oil resistance (ASTM1# oil, GB/T1690, 100 ℃ x 70 h): the volume change rate is more than or equal to 7.5 percent, and the compression permanent deformation is more than or equal to 20 percent.

According to the method for preparing the fluorine-containing nitrile rubber by using the ionic liquid modified fluorinated graphene, the imidazolium ionic liquid modified fluorinated graphene is used for modifying the surface of the fluorinated graphene without damaging the surface structure by utilizing the interaction between pi-pi bonds between the imidazolium ionic liquid and the fluorinated graphene; due to the introduction of fluorine atoms, C-F bonds formed by the fluorine atoms and carbon atoms have high energy and are not easily corroded by chemicals, and the fluorine atoms are added into the nitrile rubber to endow the nitrile rubber with better oil resistance; the existence of fluorine atoms shortens the bond length of the C-C bond and increases the bond energy under the strong electron effect and the shielding protection effect on the C-C bond, thereby improving the corrosion resistance and the rigidity of the rubber.

Drawings

FIG. 1 is a schematic flow diagram of the process 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 acrylonitrile-butadiene latex is latex prepared by polymerizing butadiene and acrylonitrile emulsion, and the mass percentage of acrylonitrile is 25-33%.

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;

oil resistance (ASTM # 1 oil, GB/T1690, 100 ℃ C.. times.70 h).