CN110734594A - Method for preparing emulsion polymerized styrene butadiene rubber from modified carbon blacks - Google Patents
Method for preparing emulsion polymerized styrene butadiene rubber from modified carbon blacks Download PDFInfo
- Publication number
- CN110734594A CN110734594A CN201810794754.7A CN201810794754A CN110734594A CN 110734594 A CN110734594 A CN 110734594A CN 201810794754 A CN201810794754 A CN 201810794754A CN 110734594 A CN110734594 A CN 110734594A
- Authority
- CN
- China
- Prior art keywords
- carbon black
- mass
- parts
- ionic liquid
- stirring
- 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
-
- 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 carbon blacks, which comprises the steps of (1) adding polyvinyl alcohol, formaldehyde and carbon black into a beaker, performing ultrasonic treatment for 1-3 hours at normal temperature to fully disperse the carbon black, dropwise adding an ionic liquid into a carbon black dispersion liquid, stirring for 3-5 hours at normal temperature to obtain ionic liquid modified carbon black, (2) performing latex coagulation, namely adding styrene-butadiene latex into a coagulation kettle, adding an ionic liquid modified carbon black mixed solution (1), stirring and mixing for 30min, adding a demulsifier and soft water at the coagulation temperature of 30-50 ℃, adding a coagulant and coagulating, stirring for 2-5 hours 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 styrene-butadiene rubber from ionic liquids and polyvinyl alcohol modified carbon black, in particular to a method for preparing ionic liquid modified carbon black modified emulsion styrene-butadiene rubber by using an emulsion method.
Background
Carbon black is used as a reinforcing filler in the rubber industry, carbon black is neither typically crystalline nor typically amorphous, and its microstructure is between that of a stone crystal structure and that of an amorphous body, and modification of carbon black is almost all developed around a small number of functional groups on the surface of carbon black at present.
Zhang wave, et al (Zhang wave, Chensming, high school, influence of ionic liquid on electrochemical properties of sulfur-superconducting carbon black composite. electrochemistry 2010,16(1):35-38) prepare a sulfur-superconducting carbon black composite material with 59% of sulfur content from elemental sulfur and superconducting carbon black by a heat treatment method, and x-ray diffraction and scanning electron microscope tests show that the elemental sulfur is uniformly dispersed in the superconducting carbon black with high specific surface area. If room-temperature ionic liquid is added into the electrolyte, the shuttle effect of polysulfide in the composite material in the electrolyte can be effectively weakened, the electrochemical performance of the sulfur composite material is improved, and the charge-discharge test shows that the capacity of the sulfur-superconducting carbon black composite material is still maintained at 483.6mAh/g after the sulfur-superconducting carbon black composite material is circulated in the electrolyte containing the ionic liquid for 50 weeks.
Zhang Xuanmin et al (Zhang Xuanmin, Liupeng, Wang Jingyi, Xiaxing, Jiahong soldier. preparation and performance of ionic liquid modified carbon black-white carbon black double-phase particle reinforced natural rubber vulcanized rubber. rubber and plastic technology and equipment. 2015,41(15): 23-25). An ionic liquid 1-butyl-3 methylimidazolium hexafluorophosphate (BMI) modified carbon black-white carbon black dual-phase particle (CSDPF) is adopted to prepare BMI modified CSDPF (BMI-CSDPF)/Natural Rubber (NR) vulcanized rubber, and the influence of the content of the BMI-CSDPF on the vulcanization performance and the mechanical property of the rubber compound and the dispersion performance of the BMI-CSDPF in the vulcanized rubber is researched. The result shows that with the increase of the consumption of the BMI-CSDPF, the vulcanization speed of the NR mixed rubber is increased and then reduced, and the vulcanization torque is increased continuously; when the amount of BM1-CSDPF is 30 parts, the prepared NR vulcanized rubber has the best tensile property; when the amount is more than 30 parts, the filler begins to form agglomeration in vulcanized rubber; the tearing performance of the vulcanized rubber is continuously improved along with the increase of the amount of the filler.
The preparation method comprises the following steps of treating carbon black by using ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate BMIM.PF6, IL) firstly, carrying out microwave treatment to obtain modified carbon black (m-CB), and using the m-CB for reinforcing the nitrile rubber (NBR), wherein the ionic liquid is modified by the ionic liquid. The structure of m-CB, the vulcanization characteristics and the reinforcing effect of the rubber compound were investigated. The results show that the IL can be adsorbed on the surface of the carbon black and partially and strongly adsorbed on the surface of the carbon black, and the IL can be partially decomposed after micro-transition treatment; m-CB delays vulcanization of the compound; the elongation at break, tensile strength and tearing strength of the NBR/m-CB vulcanized rubber are greatly improved relative to the unmodified carbon black, and the modulus and the hardness are slightly reduced. The mechanism of the modified carbon black reinforced rubber is discussed through researches on the crosslinking density, Dynamic Mechanical Analysis (DMA), morphology and the like of vulcanized rubber.
Zhang Xuanmin et al (Zhang Xuanmin, Liu Peng, Ma Liang, do not dream Yao, Liang Wei, Wang Qi, Jia hong Dynasty, Xuzhao Dong. interaction of ionic liquid and white carbon black and influence on natural rubber performance. synthetic rubber industry, 2016,39(5):404 jia 409) adopts ionic liquid chlorinated 1-allyl-3-methylimidazole (AMI) modified white carbon black, researches interaction of AMI and white carbon black by Fourier transform infrared spectroscopy and solid nuclear magnetic resonance, and researches influence of ionic liquid dosage on vulcanization characteristic, mechanical property and dynamic mechanical property of modified white carbon black filled Natural Rubber (NR). The result shows that hydrogen bond action exists between AMI and the surface of the white carbon black, and the dispersibility of the white carbon black in NR can be obviously improved. AMI can change the vulcanization rate of the white carbon black filled rubber material, and the larger the AMl dosage is, the larger the vulcanization rate of the NR rubber material is. With the increase of the AMI dosage, the tensile property and the tearing property of the modified white carbon black filled NR vulcanized rubber are improved, and when the AMI dosage is 1.0 part, the tensile strength of the vulcanized rubber reaches the maximum value of 23.95 MPa; when the amount of the AM1 is 2.0 parts, the tearing strength of the NR vulcanized rubber reaches the maximum value of 71.47kN/m, and is respectively improved by 102.28% and 41.83% compared with the NR vulcanized rubber filled with unmodified white carbon black. The glass transition temperature of the NR vulcanizate decreases with increasing amounts of AMI.
The preparation method comprises the following steps of modifying the white carbon black by using 1-butyl 3-methylimidazolium hexafluorophosphate (Bmim. PFs) ionic liquid, preparing the modified white carbon black/SBR composite material by using an emulsion coprecipitation method, and researching the vulcanization characteristic, the physical property and the microstructure of the modified white carbon black/SBR composite material by using the emulsion coprecipitation method. The results show that: the interaction between PFe and white carbon black is hydrogen bond; compared with the unmodified white carbon black/SBR composite material, the modified white carbon black/SBR composite material has the advantages that the crosslinking density is increased, the dispersibility of the white carbon black in a rubber matrix is improved, and the tensile strength, the tearing strength and the wear resistance are obviously improved.
The method comprises the steps of preparing novel double-ionic functional ionic liquid bis (methyl p-imidazole) mercaptosuccinate (BMimMS) by utilizing a neutralization reaction of N-methylimidazole and mercaptosuccinic acid, representing the structure of the BMimMS, modifying a white carbon black/Styrene Butadiene Rubber (SBR) composite material by using the BMimMS as an interface modifier, and researching a filler network, a vulcanization characteristic, physical properties and a microscopic form of the BMimMS, wherein the BMimMS is used as an interface modifier, and the dispersion of the white carbon black does not obviously improve the interaction between the BMimMS and the BMimMS, so that the physical properties of the white carbon black/SBR composite material and the low-slip factor (20-0 ℃) of the BMimMS are improved.
CN102504337A discloses ionic liquid modified high-dispersion high-thermal-conductivity white carbon black and a preparation method thereof, wherein the ionic liquid is composed of ionic liquid and white carbon black, the ionic liquid is dialkyl imidazole halide salt, the cation is alkyl with substituent groups of C1, C4, C6 and C8, or the ionic liquid is alkyl pyridine halide salt, the cation is alkyl with substituent groups of C4 and C6, the anion is Cl < - >, and Br < - >, so that the white carbon black has high-dispersion and high-thermal-conductivity performance, the ionic liquid, deionized water and the white carbon black are added into a beaker according to the mass ratio of 1-5: 100: 500, stirred for 30min at 50 ℃, stirred for 3h at 80 ℃ after being uniformly mixed, naturally dried for 12h at room temperature, and finally placed in a vacuum drying box at 80 ℃ for 12h and dried, and the ionic liquid modified white carbon black is obtained.
CN105924981A discloses double-bond-containing imidazolyl ionic liquid modified carbon black/silicone rubber composite force-sensitive conductive material and a preparation method thereof, wherein carbon black is modified on the surface of double-bond-containing imidazolyl ionic liquid, the mass ratio of ionic liquid to carbon black is 1: 4-9, then 15-25 parts of ionic liquid modified carbon black, 100 parts of silicone rubber crude rubber and 1-2 parts of vulcanizing agent are mixed and vulcanized to prepare the composite material.
CN102504337B discloses ionic liquid modified high-dispersion high-thermal-conductivity white carbon black and a preparation method thereof, wherein the ionic liquid is composed of ionic liquid and white carbon black, the ionic liquid is dialkyl imidazole halide salt, the cation is alkyl with substituent groups of C1, C4, C6 and C8, or the ionic liquid is alkyl pyridine halide salt, the cation is alkyl with substituent groups of C4 and C6, and the anion is Cl-Br-, so that the white carbon black has high-dispersion and high-thermal-conductivity performance, the ionic liquid, deionized water and the white carbon black are added into a beaker according to the mass ratio of 1-5: 100: 500, stirred for 30min at 50 ℃ until the ionic liquid, the deionized water and the white carbon black are uniformly mixed, stirred for 3h at 80 ℃, naturally dried for 12h at room temperature, and finally placed in a vacuum drying box at 80 ℃ for 12h and dried, and the ionic liquid modified white carbon black is obtained.
CN102585558B discloses methods for preparing high-dispersion high-thermal-conductivity white carbon black by modifying with ionic liquid under supercritical carbon dioxide, wherein the modified white carbon black is used as a high-dispersion high-thermal-conductivity rubber filling reinforcing agent, the ionic liquid is used for modifying the white carbon black in the supercritical carbon dioxide to ensure that the white carbon black has high-dispersion and high-thermal-conductivity properties, the mass ratio of the ionic liquid to the white carbon black is 2.0: 100.0, the ionic liquid and the white carbon black are respectively added into different high-pressure kettles, and the supercritical carbon dioxide is firstly added into the high-pressure kettles of the ionic liquid to form supercritical carbon dioxide-ionic liquid (sc-CO-ionic liquid2IL), adding supercritical carbon dioxide-ionic liquid fluid into the white carbon black autoclave, and preparing the high-dispersion and high-thermal conductivity white carbon black through supercritical carbon dioxide-ionic liquid modification.
CN103102514A discloses ionic liquid modified natural rubber vulcanized rubber containing graphene oxide, which is characterized in that ionic liquid is modified by a solid grinding method to obtain graphene oxide, 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 the ionic liquid modified graphene oxide, and the natural rubber mixed rubber containing the ionic liquid modified graphene oxide/natural rubber vulcanized rubber is obtained through vulcanization processing.
CN101235252A discloses multifunctional liquid rubber spray paint, which comprises A, B two components, wherein the A component is liquid rubber asphalt emulsion with the solid content of 50-75%, the rubber emulsion contains 2-65%, the asphalt emulsion contains 30-97%, the carbon black contains 0.0-5.0%, the superfine powder contains 0.0-6.0%, the anionic dispersant contains 0.025-2.50%, the anionic surfactant contains 0.025-3.00%, and the B component is an aqueous solution of 3.0-18.0% calcium chloride (89.0-99.2%), sodium chloride (0.50-4.0%) and a composite aluminum-iron polymer (0.3-7.0%), and the two components are sprayed on the same base surface by a two-component airless spraying device for 3-5 seconds to solidify into a 0.5-4 mm adhesive film.
JP2013067706(A) discloses rubber compositions for tires which can improve fuel efficiency and wear resistance in a well-balanced manner and can prevent generation of pores during tire production, and pneumatic tires using the same.A solution is that a rubber composition for tires comprises at least kinds of compounds selected from natural rubber and diene-based synthetic rubber, carbon black, and amphoteric compounds, acidic and basic functional groups, of which is an amphoteric compound in which the amphoteric compound is dissolved in an ionic liquid solution.
GB1365983(a) discloses latex blends comprising a liquid, a preparation of a particulate filler, latex and ferromagnetic particles comprising a pre-blended kaolin clay, optionally calcium chloride, water and ferromagnetic particle coated polyvinyl chloride or (b) carbon black or white carbon.
DE102011001658(A1) discloses that rubber mixtures comprise at least polar or non-polar rubbers and 0.1 to 150 parts of rubber of at least carbon blacks and 0.01 to 50 parts of rubber of at least ionic liquids and/or 0.1 to 150 parts of rubber of at least carbon blacks modified with at least ionic liquids, and further additives, comprising (1) preparing a rubber composition comprising carbon black modification of at least ionic liquids by means of at least solvents, and (2) carbon blacks modified with at least ionic liquids.
WO2009112220(A1) discloses rubber compositions useful for winter tire treads, high grip ice, comprising at least diene rubbers such as natural rubber and/or polybutadiene, 50-150 parts of a reinforcing filler of phenylalanine such as silica and/or carbon black, more than 40 parts of a phenylalanine liquid plasticizer of 1-30, a nonionic surfactant of phenylalanine and 5-40 parts of phenylalanine microparticles.
Disclosure of Invention
The invention aims to provide a method for preparing emulsion polymerized styrene-butadiene rubber from ionic liquids and polyvinyl alcohol modified carbon black, which increases the interaction between the carbon black and the emulsion polymerized styrene-butadiene rubber, and the prepared emulsion polymerized styrene-butadiene rubber has better mechanical property and aging resistance.
Therefore, the invention provides a method for preparing emulsion styrene-butadiene rubber by ionic liquids and polyvinyl alcohol modified carbon black, which comprises the following steps:
(1) ionic liquid modified carbon black: adding 100-200 parts by mass of polyvinyl alcohol, 100-200 parts by mass of formaldehyde and 100 parts by mass of carbon black into a beaker, performing ultrasonic treatment for 1-3 hours at normal temperature to fully disperse the carbon black, dropwise adding 10-20 parts by mass of ionic liquid into a carbon black dispersion liquid, and stirring for 3-5 hours at normal temperature to obtain the ionic liquid modified carbon black.
(2) Latex agglomeration: adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, adding 5-20 parts by mass of ionic liquid modified carbon black mixed solution, 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 ℃, adding 5-15 parts by mass of coagulant for coagulation, stirring for 2-5 h at 80-100 ℃ for curing, and then washing, dehydrating and drying to obtain the polymer.
The carbon black of the invention is the common standard carbon black for rubber.
The ionic liquid is hydrophobic imidazole salt, such as or a mixture of more than one of 1-butyl-3-methylimidazole hexafluorophosphate, 1-octyl-3-methylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1-octyl-2, 3-dimethylimidazole bis (trifluoromethanesulfonyl) imide salt and the like, and the mass ratio of the ionic liquid to carbon black is 1: 5-1: 10.
The demulsifier is a saturated NaCl aqueous solution, and the using amount of the demulsifier is 3-15 parts by mass.
The coagulant is sulfuric acid, and the using amount is 5-15 parts by mass.
The method comprises the step of mixing the ionic liquid and the carbon black in a mass ratio of 1: 5-1: 10.
The method of the invention, wherein the stirring time in the step (2) is 2-5 hours.
The polymer obtained by the invention has the performance of Ny viscosity ML(1+4) 100℃50-65, the 300% stress at definite elongation is 18.0-25.0 MPa, the tensile strength is more than or equal to 28.0MPa, the elongation at break is more than or equal to 560%, and the aging resistance is more than or equal to 0.60.
The method for preparing the emulsion styrene-butadiene rubber by the ionic liquid and the polyvinyl alcohol modified carbon black comprises the steps of introducing ultrasonic waves when the carbon black is dispersed, fully dispersing the carbon black by utilizing the action of an ultrasonic field, then pretreating by using polyvinyl alcohol and formaldehyde, generating polyvinyl formal through the reaction of the formaldehyde and the polyvinyl alcohol on the surface of the carbon black, converting the carbon black into lipophilic carbon black, increasing the combination of the carbon black and lipophilic groups in styrene-butadiene latex, modifying the carbon black by utilizing steps of imidazole salt ionic liquid, modifying the surface of the carbon black without damaging the surface structure by utilizing the physical adsorption action between the imidazole salt ionic liquid and the carbon black, improving the dispersion of the ionic liquid and the carbon black in a rubber matrix by utilizing the hydrogen bonding action of the ionic liquid and the carbon black, and enhancing the interfacial interaction between the ionic liquid and the rubber matrix, so that the mechanical property and the aging resistance of the rubber are improved, and adding the mixed solution of the ionic liquid modified carbon black in the coagulation of the emulsion styrene-butadiene rubber.
Drawings
FIG. 1 is a flow chart 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;
aging coefficient: measured according to GB/T3512-2001.
Example 1
(1) Ionic liquid modified carbon black: adding 100 parts by mass of polyvinyl alcohol, 100 parts by mass of formaldehyde and 100 parts by mass of carbon black into a beaker, performing ultrasonic treatment for 3 hours at normal temperature to fully disperse the carbon black, dropwise adding 20 parts by mass of 1-butyl-3-methylimidazolium hexafluorophosphate into the carbon black dispersion, and stirring for 3 hours at normal temperature to obtain the 1-butyl-3-methylimidazolium hexafluorophosphate modified carbon black.
(2) Latex agglomeration: adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, adding 15 parts by mass of 1-butyl-3-methylimidazolium hexafluorophosphate modified carbon black mixed solution (1), stirring and mixing for 30min, adding 5 parts by mass of saturated NaCl aqueous solution at 35 ℃ while adding 40 parts by mass of soft water, adding 5 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.
The viscosity ML of the polymer is determined according to the detection standard, Ny(1+4) 100℃56, 300 percent stress at definite elongation of 23.1MPa, tensile strength of 29.1MPa, elongation at break of 573 percent and aging resistance of 0.70.
Comparative example 1
The experimental conditions are the same as example 1, except that no ionic liquid is added in the carbon black modification, and the viscosity ML of Ny is measured according to the detection standard(1+4) 100℃50, 300 percent stress at definite elongation of 20.7MPa, tensile strength of 24.5MPa, elongation at break of 556 percent and aging resistance of 0.50.
Example 2
(1) Ionic liquid modified carbon black: adding 200 parts by mass of polyvinyl alcohol, 100 parts by mass of formaldehyde and 100 parts by mass of carbon black into a beaker, performing ultrasonic treatment for 3 hours at normal temperature to fully disperse the carbon black, dropwise adding 15 parts by mass of 1-octyl-3-methylimidazole hexafluorophosphate into the carbon black dispersion liquid, and stirring for 5 hours at normal temperature to obtain the 1-octyl-3-methylimidazole hexafluorophosphate modified carbon black.
(2) Latex agglomeration: adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, adding 10 parts by mass of 1-octyl-3-methylimidazolium hexafluorophosphate modified carbon black mixed solution (1), stirring and mixing for 30min, adding 10 parts by mass of saturated NaCl aqueous solution and 50 parts by mass of soft water at 30 ℃ for coagulation, adding 10 parts by mass of sulfuric acid for coagulation, stirring at 90 ℃ for 4h for curing, and then washing, dehydrating and drying to obtain the polymer.
The viscosity ML of the polymer is determined according to the detection standard, Ny(1+4) 100℃59, 300 percent stress at definite elongation of 22.6MPa, tensile strength of 29.4MPa, elongation at break of 578 percent and aging resistance of 0.74.
Comparative example 2
The experimental conditions were the same as in example 2 except that no ionic liquid was added to the carbon black modification. According to the detection standardMeasuring the viscosity ML of Ni(1+4) 100℃51, 300 percent stress at definite elongation of 18.4MPa, tensile strength of 23.5MPa, elongation at break of 551 percent and aging resistance of 0.56.
Example 3
(1) Ionic liquid modified carbon black: adding 150 parts by mass of polyvinyl alcohol, 100 parts by mass of formaldehyde and 100 parts by mass of carbon black into a beaker, performing ultrasonic treatment for 2 hours at normal temperature to fully disperse the carbon black, dropwise adding 20 parts by mass of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt into a carbon black dispersion liquid, and stirring for 4 hours at normal temperature to obtain the 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt modified carbon black.
(2) Latex agglomeration: adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, adding 10 parts by mass of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide modified carbon black mixed solution (1), stirring and mixing for 30min, adding 80 parts by mass of soft water while adding 6 parts by mass of saturated NaCl aqueous solution at a coagulation temperature of 30 ℃, adding 15 parts by mass of sulfuric acid for coagulation, stirring for 4h at 100 ℃ for curing, and then washing, dehydrating and drying to obtain the polymer.
The viscosity ML of the polymer is determined according to the detection standard, Ny(1+4) 100℃61, 300 percent stress at definite elongation of 19.4MPa, tensile strength of 30.1MPa, elongation at break of 583 percent and aging resistance of 0.68.
Comparative example 3
The experimental conditions were the same as in example 3 except that no polyvinyl alcohol was added to the carbon black modification, and the viscosity ML was determined according to the test standard of Ny(1+4) 100℃52, 300 percent stress at definite elongation of 17.0MPa, tensile strength of 26.4MPa, elongation at break of 561 percent and aging resistance of 0.55.
Example 4
(1) Ionic liquid modified carbon black: adding 120 parts by mass of polyvinyl alcohol, 200 parts by mass of formaldehyde and 100 parts by mass of carbon black into a beaker, performing ultrasonic treatment for 2 hours at normal temperature to fully disperse the carbon black, dropwise adding 10 parts by mass of 1-octyl-2, 3-dimethylimidazole bis (trifluoromethanesulfonyl) imide salt into a carbon black dispersion liquid, and stirring for 5 hours at normal temperature to obtain the 1-octyl-2, 3-dimethylimidazole bis (trifluoromethanesulfonyl) imide salt modified carbon black.
(2) Latex agglomeration: adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, adding 10 parts by mass of 1-octyl-2, 3-dimethyl imidazole bis (trifluoromethanesulfonyl) imide salt modified carbon black mixed solution (1), stirring and mixing for 30min, adding 9 parts by mass of saturated NaCl aqueous solution and 100 parts by mass of soft water at 45 ℃ coagulation temperature, adding 7 parts by mass of sulfuric acid for coagulation, stirring at 90 ℃ for 4h for curing, and then washing, dehydrating and drying to obtain the polymer.
The viscosity ML of the polymer is determined according to the detection standard, Ny(1+4) 100℃65, 300 percent stress at definite elongation of 18.2MPa, tensile strength of 29.1MPa, elongation at break of 567 percent and aging resistance of 0.76.
Comparative example 4
The experimental conditions were the same as in example 4 except that no polyvinyl alcohol was added to the carbon black modification, and the viscosity ML was determined according to the test standard of Ny(1+4) 100℃53, 300 percent stress at definite elongation of 16.0MPa, tensile strength of 25.4MPa, elongation at break of 545 percent and aging resistance of 0.61.
Example 5
(1) Ionic liquid modified carbon black: adding 180 parts by mass of polyvinyl alcohol, 120 parts by mass of formaldehyde and 100 parts by mass of carbon black into a beaker, performing ultrasonic treatment for 2 hours at normal temperature to fully disperse the carbon black, dropwise adding 16 parts by mass of 1-butyl-3-methylimidazolium hexafluorophosphate into the carbon black dispersion liquid, and stirring for 4 hours at normal temperature to obtain the 1-butyl-3-methylimidazolium hexafluorophosphate modified carbon black.
(2) Latex agglomeration: adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, adding 14 parts by mass of 1-butyl-3-methylimidazolium hexafluorophosphate modified carbon black mixed solution (1), stirring and mixing for 30min, adding 12 parts by mass of saturated NaCl aqueous solution at 35 ℃ while adding 55 parts by mass of soft water, adding 10 parts by mass of sulfuric acid for coagulation, stirring at 85 ℃ for 4h for curing, and then washing, dehydrating and drying to obtain the polymer.
Ny viscosity ML according to the detection standard(1+4) 100℃53, 300 percent stress at definite elongation of 24.5MPa, tensile strength of 28.7MPa, elongation at break of 587 percent and aging resistance of 0.79.
Comparative example 5
The experimental conditions are the same as example 5, except that the ionic liquid and the polyvinyl alcohol are not added in the carbon black modification, the carbon black is directly dispersed in the formaldehyde, and the viscosity ML of Ny is measured according to the detection standard(1+4) 100℃50, 300 percent stress at definite elongation of 21.2MPa, tensile strength of 24.3MPa, elongation at break of 551 percent and aging resistance of 0.55.
Example 6
(1) Ionic liquid modified carbon black: adding 140 parts by mass of polyvinyl alcohol, 160 parts by mass of formaldehyde and 100 parts by mass of carbon black into a beaker, performing ultrasonic treatment for 3 hours at normal temperature to fully disperse the carbon black, dropwise adding 12 parts by mass of 1-octyl-3-methylimidazole hexafluorophosphate into the carbon black dispersion liquid, and stirring for 5 hours at normal temperature to obtain the 1-octyl-3-methylimidazole hexafluorophosphate modified carbon black.
(2) Latex agglomeration: adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, adding 10 parts by mass of 1-octyl-3-methylimidazolium hexafluorophosphate modified carbon black mixed solution (1), stirring and mixing for 30min, adding 5 parts by mass of saturated NaCl aqueous solution and 20 parts by mass of soft water at a coagulation temperature of 50 ℃, adding 8 parts by mass of sulfuric acid for coagulation, stirring at 85 ℃ for 4h for curing, and then washing, dehydrating and drying to obtain the polymer.
Ny viscosity ML according to the detection standard(1+4) 100℃55, 300 percent stress at definite elongation of 23.7MPa, tensile strength of 28.9MPa, elongation at break of 578 percent and aging resistance of 0.65.
Comparative example 6
The experimental conditions are the same as example 6, except that the ionic liquid and the polyvinyl alcohol are not added in the carbon black modification, the carbon black is directly dispersed in the formaldehyde, and the viscosity ML of Ny is measured according to the detection standard(1+4) 100℃48, 300 percent stress at definite elongation of 18.9MPa, tensile strength of 24.2MPa, elongation at break of 560 percent and aging resistance of 0.51.
Example 7
(1) Ionic liquid modified carbon black: adding 150 parts by mass of polyvinyl alcohol, 100 parts by mass of formaldehyde and 100 parts by mass of carbon black into a beaker, performing ultrasonic treatment for 2 hours at normal temperature to fully disperse the carbon black, dropwise adding 18 parts by mass of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt into a carbon black dispersion liquid, and stirring for 4 hours at normal temperature to obtain the 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt modified carbon black.
(2) Latex agglomeration: adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, adding 10 parts by mass of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide modified carbon black mixed solution, stirring and mixing for 30min, adding 5 parts by mass of saturated NaCl aqueous solution and 100 parts by mass of soft water at 40 ℃ for coagulation, adding 5 parts by mass of sulfuric acid for coagulation, stirring at 80 ℃ for 4h 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 19.8MPa, tensile strength of 29.0MPa, elongation at break of 591% and aging resistance of 0.80.
Comparative example 7
The experimental conditions were the same as in example 7, except that the carbon black was not modified, and the carbon black was added directly to (2) and the viscosity ML was determined according to the test standard of Ny(1+4) 100℃52, 300 percent stress at definite elongation of 17.0MPa, tensile strength of 23.6MPa, elongation at break of 573 percent and aging resistance of 0.52.
Example 8
(1) Ionic liquid modified carbon black: adding 150 parts by mass of polyvinyl alcohol, 200 parts by mass of formaldehyde and 100 parts by mass of carbon black into a beaker, performing ultrasonic treatment for 3 hours at normal temperature to fully disperse the carbon black, dropwise adding 20 parts by mass of 1-octyl-2, 3-dimethylimidazole bis (trifluoromethanesulfonyl) imide salt into a carbon black dispersion liquid, and stirring for 3 hours at normal temperature to obtain the 1-octyl-2, 3-dimethylimidazole bis (trifluoromethanesulfonyl) imide salt modified carbon black.
(2) Latex agglomeration: adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, adding 16 parts by mass of 1-octyl-2, 3-dimethyl imidazole bis (trifluoromethanesulfonyl) imide salt modified carbon black mixed solution, stirring and mixing for 30min, adding 60 parts by mass of soft water while adding 5 parts by mass of saturated NaCl aqueous solution at a coagulation temperature of 40 ℃, adding 7 parts by mass of sulfuric acid for coagulation, stirring for 3h at a temperature of 90 ℃ for curing, and then washing, dehydrating and drying to obtain the polymer.
Ny viscosity ML according to the detection standard(1+4) 100℃56, 300 percent stress at definite elongation of 22.8MPa, tensile strength of 29.5MPa, elongation at break of 590 percent and aging resistance of 0.76.
Comparative example 8
The experimental conditions were the same as those of example 8, except that the carbon black was not modified, and the carbon black was added directly to (2) and the viscosity ML was determined according to the test standard of Ny(1+4) 100℃53, 300 percent stress at definite elongation of 16.7MPa, tensile strength of 20.5MPa, elongation at break of 541 percent and aging resistance of 0.56.
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 the emulsion styrene-butadiene rubber from modified carbon blacks is characterized by comprising the following steps of:(1) ionic liquid modified carbon black: carrying out ultrasonic treatment on 100-200 parts by mass of polyvinyl alcohol, 100-200 parts by mass of formaldehyde and 100 parts by mass of carbon black for 1-3 hours at normal temperature to fully disperse the carbon black, dropwise adding 10-20 parts by mass of ionic liquid into a carbon black dispersion liquid, and stirring for 3-5 hours at normal temperature to obtain ionic liquid modified carbon black;(2) and (2) latex coagulation, namely adding 100 parts by mass of styrene-butadiene latex into a coagulation kettle, adding 5-20 parts by mass of the ionic liquid modified carbon black, stirring and mixing for 30min, adding 3-15 parts by mass of a demulsifier into at a coagulation temperature of 30-50 ℃, adding 20-100 parts by mass of soft water and 5-15 parts by mass of a coagulant into for coagulation, stirring at 80-100 ℃, curing, washing, dehydrating and drying to obtain the polymer.
- 2. The method of claim 1, wherein the ionic liquid is a hydrophobic imidazolium salt.
- 3. The method according to claim 2, wherein the hydrophobic imidazole salt is or more selected from the group consisting of 1-butyl-3-methylimidazolium hexafluorophosphate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, and 1-octyl-2, 3-dimethylimidazolium bis (trifluoromethanesulfonyl) imide salt.
- 4. The method of claim 1, wherein the emulsion breaker is a saturated aqueous NaCl solution.
- 5. The method of claim 1, wherein said coagulant is sulfuric acid.
- 6. The method of , wherein the styrene-butadiene latex is a stable emulsion obtained by low temperature emulsion polymerization of butadiene and styrene.
- 7. The method according to claim 6, wherein the pH of the styrene-butadiene latex is 3 to 7 and the solid content is 15 to 25 w%.
- 8. The method according to claim 6, wherein the reaction temperature of the low-temperature emulsion polymerization is 3 to 15 ℃.
- 9. The method according to claim 1, wherein the mass ratio of the ionic liquid to the carbon black is 1:5 to 1: 10.
- 10. The method according to claim 1, wherein the stirring time in the step (2) is 2 to 5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810794754.7A CN110734594B (en) | 2018-07-19 | 2018-07-19 | Method for preparing emulsion polymerized styrene butadiene rubber from modified carbon black |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810794754.7A CN110734594B (en) | 2018-07-19 | 2018-07-19 | Method for preparing emulsion polymerized styrene butadiene rubber from modified carbon black |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110734594A true CN110734594A (en) | 2020-01-31 |
| CN110734594B CN110734594B (en) | 2022-03-01 |
Family
ID=69235588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810794754.7A Active CN110734594B (en) | 2018-07-19 | 2018-07-19 | Method for preparing emulsion polymerized styrene butadiene rubber from modified carbon black |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110734594B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591584A (en) * | 2022-03-30 | 2022-06-07 | 山东海益橡胶科技有限公司 | Carbon-filled modified acrylate rubber and composition and preparation method thereof |
| CN114957821A (en) * | 2021-02-24 | 2022-08-30 | 中国石油化工股份有限公司 | White carbon black/emulsion-polymerized styrene-butadiene latex composite rubber, preparation method and application thereof, rubber composition and application thereof |
| CN116396626A (en) * | 2023-03-27 | 2023-07-07 | 江门市胜鹏化工实业有限公司 | Modified white carbon black and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0345607A (en) * | 1989-07-12 | 1991-02-27 | Kurashiki Kako Co Ltd | Rubber composition resistant to crack propagation in aged oil |
| CN104403323A (en) * | 2014-11-18 | 2015-03-11 | 滁州君越高分子新材料有限公司 | Conductive silicone rubber with high rebound resilience |
| CN107266750A (en) * | 2016-04-08 | 2017-10-20 | 中国石油天然气股份有限公司 | It is a kind of for rubber composition of tire tread and preparation method thereof |
-
2018
- 2018-07-19 CN CN201810794754.7A patent/CN110734594B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0345607A (en) * | 1989-07-12 | 1991-02-27 | Kurashiki Kako Co Ltd | Rubber composition resistant to crack propagation in aged oil |
| CN104403323A (en) * | 2014-11-18 | 2015-03-11 | 滁州君越高分子新材料有限公司 | Conductive silicone rubber with high rebound resilience |
| CN107266750A (en) * | 2016-04-08 | 2017-10-20 | 中国石油天然气股份有限公司 | It is a kind of for rubber composition of tire tread and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114957821A (en) * | 2021-02-24 | 2022-08-30 | 中国石油化工股份有限公司 | White carbon black/emulsion-polymerized styrene-butadiene latex composite rubber, preparation method and application thereof, rubber composition and application thereof |
| CN114591584A (en) * | 2022-03-30 | 2022-06-07 | 山东海益橡胶科技有限公司 | Carbon-filled modified acrylate rubber and composition and preparation method thereof |
| CN116396626A (en) * | 2023-03-27 | 2023-07-07 | 江门市胜鹏化工实业有限公司 | Modified white carbon black and preparation method thereof |
| CN116396626B (en) * | 2023-03-27 | 2024-03-01 | 江门市胜鹏化工实业有限公司 | Modified white carbon black and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110734594B (en) | 2022-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110734587B (en) | Method for preparing nitrile rubber from modified carbon black | |
| US9695318B2 (en) | Inorganic/lignin type polymer composite nanoparticles, preparation method therefor and application thereof | |
| CN110734594B (en) | Method for preparing emulsion polymerized styrene butadiene rubber from modified carbon black | |
| CN104558708A (en) | Multifunctional vulcanized rubber containing polyvinylpyrrolidone-modified graphene oxide and preparation method of multifunctional vulcanized rubber | |
| CN101704967A (en) | Preparation method of white carbon black/clay/rubber nanocomposite | |
| JP2023511672A (en) | Modified lignin-reinforced rubber and method for producing the same | |
| CN110734590B (en) | Method for preparing emulsion polymerized styrene-butadiene rubber from ionic liquid and chitosan modified carbon black | |
| CN111423622B (en) | Silicon dioxide nano composite reinforcing agent for hydrogenated nitrile rubber and preparation method thereof | |
| CN107722392B (en) | Carbon quantum dot filler reinforced rubber material and preparation method thereof | |
| CN101942123A (en) | Preparation and application of modified kaolinic | |
| CN104277255A (en) | Application of rubber master batch prepared continuously in hard bead filler of truck tyre | |
| Li et al. | Recent progress of elastomer–silica nanocomposites toward green tires: simulation and experiment | |
| CN110734593A (en) | Method for preparing emulsion polymerized styrene butadiene rubber from modified graphene | |
| Petrova et al. | Specific features of chitosan-montmorillonite interaction in an aqueous acid solution and properties of related composite films | |
| Xiao et al. | Mechanism on surface hydrophobically modification of fibrous wollastonite and its reinforcement of natural rubber | |
| CN110734586B (en) | Method for preparing fluorine-containing nitrile rubber from modified fluorinated graphene | |
| CN110734589A (en) | Method for preparing emulsion polymerized styrene butadiene rubber from modified graphene | |
| CN104327315A (en) | Application of continuously-prepared rubber masterbatch in car tire base rubber | |
| CN115160657A (en) | Rubber masterbatch and preparation method thereof | |
| CN104387628A (en) | Application of continuously prepared rubber master batch in sidewall rubber of truck tires | |
| CN107151335B (en) | Method for preparing clay/rubber nano composite material by slurry blending | |
| CN110734521B (en) | Method for in-situ reinforcement of emulsion polymerized styrene butadiene rubber by modified carbon nano tube | |
| CN103539977B (en) | The preparation method that the strong prestige powder of a kind of modified natural rubber graft modification strengthens native rubber composite material | |
| CN110283478B (en) | Composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber and preparation method thereof | |
| CN110734591B (en) | Method for preparing fluorine-containing emulsion polymerized styrene-butadiene rubber by modified fluorinated graphene |
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 |