阅读说明：本技术 一种改性炭黑制备丁腈橡胶的方法 (Method for preparing nitrile rubber from modified carbon blacks ) 是由 魏绪玲 张华强 付含琦 朱晶 牛承祥 魏玉丽 燕鹏华 胡育林 梁滔 于 2018-07-19 设计创作，主要内容包括：本发明提供一种改性炭黑制备丁腈橡胶的方法,包含：(1)离子液体改性炭黑：将烧杯中加入乙醇、炭黑,常温下超声1～3h,使炭黑充分分散,加入壳聚糖,继续超声1～2h,在炭黑分散液中滴加离子液体,常温下搅拌3～5h,将混合物放入烘箱中,80～110℃下烘干乙醇,得到壳聚糖和离子液体改性的炭黑。(2)胶乳凝聚：将丁腈胶乳烧杯中,加入离子液体改性炭黑(1),超声分散30min～1h,将丁腈胶乳与离子液体改性炭黑混合液加入凝聚釜搅拌混合30min,在0～15℃凝聚温度下,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 nitrile rubber from modified carbon blacks, which comprises the steps of (1) adding ethanol and carbon black into a beaker, performing ultrasonic treatment for 1-3 hours at normal temperature to fully disperse the carbon black, adding chitosan, continuing the ultrasonic treatment for 1-2 hours, dropwise adding ionic liquid into carbon black dispersion liquid, stirring for 3-5 hours at normal temperature, putting the mixture into an oven, drying the ethanol at 80-110 ℃ to obtain the chitosan and ionic liquid modified carbon black, (2) performing latex coagulation, namely adding the ionic liquid modified carbon black (1) into the beaker of nitrile latex, performing ultrasonic dispersion for 30 min-1 hour, adding a mixed solution of the nitrile latex and the ionic liquid modified carbon black into a coagulation kettle, stirring and mixing for 30min, adding coagulant and soft water at 0-15 ℃ at coagulation temperature, stirring for 2-5 hours at 50-70 ℃ to perform curing, and then washing, dehydrating and drying to obtain a polymer.)

The method for preparing the nitrile rubber from modified carbon blacks is characterized by comprising the following steps of:

(1) ionic liquid modified carbon black: adding 600-1000 parts by mass of ethanol, adding 100 parts by mass of carbon black, performing ultrasonic treatment for 1-3 hours at normal temperature to fully disperse the carbon black, adding 5-10 parts by mass of chitosan, continuing ultrasonic treatment for 1-2 hours, dropwise adding 10-20 parts by mass of ionic liquid into the carbon black dispersion liquid, stirring for 3-5 hours at normal temperature, putting the mixture into an oven, and drying ethanol at 80-110 ℃ to obtain ionic liquid modified carbon black;

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

2. The method of claim 1, wherein the ionic liquid is a pyridinium salt.

3. The method according to claim 2, wherein the pyridinium salt is selected from or more of N-hexylpyridinium tetrafluoroborate, N-butylpyridinium nitrate, N-butylpyridinium dinitrile amine salt, and N-butylpyridinium p-methylbenzenesulfonate.

4. The method according to claim 1, wherein the chitosan is polyglucosamine (1-4) -2-amino-B-D-glucose having a viscosity of 0.25 to 0.65 Pa-s.

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

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 reaction temperature of the low-temperature emulsion polymerization is 3 to 15 ℃.

8. 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%.

9. The method of claim 1, wherein in step (1), the carbon black is a standard carbon black for rubber.

10. The method according to claim 1, wherein in the step (2), the stirring time is 2-5 h.

Technical Field

The invention relates to a method for preparing nitrile rubber from pyridinium ionic liquid and chitosan modified carbon black, in particular to a method for preparing nitrile rubber from ionic liquid modified carbon black 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 abrasion resistance in a well-balanced manner and can prevent generation of porosities during tire production, and pneumatic tires using the same.GB 1365983(A) discloses 0 latex mixtures including liquids, preparation of particulate fillers, latex and ferromagnetic particles, at least carbon black including premixed kaolin, optionally calcium chloride, water and ferromagnetic particles coating polyvinyl chloride or (b) carbon black or white carbon.DE 102011001001001 (A1) discloses 1 rubber mixtures including at least carbon black and 0.01- ionic liquid of at least carbon black and 0.01-50 parts of rubber and at least 6851-6851 ionic liquid of at least 6 or styrene acrylic rubber modified with at least 6326-150 parts of styrene acrylic rubber and at least one other ionic liquid including at least one of styrene acrylic acid, styrene acid.

Disclosure of Invention

The invention aims to provide a method for preparing nitrile rubber from pyridinium ionic liquid and chitosan modified carbon black, which increases the interaction between the carbon black and the nitrile rubber, and the prepared nitrile rubber has better low-temperature resistance.

Therefore, the invention provides methods for preparing nitrile rubber by using modified carbon black obtained by pyridinium ionic liquid and chitosan, which comprises the following steps:

(1) ionic liquid modified carbon black: adding 600-1000 parts by mass of ethanol into a beaker, adding 100 parts by mass of carbon black, performing ultrasonic treatment for 1-3 hours at normal temperature to fully disperse the carbon black, adding 5-10 parts by mass of chitosan, continuing ultrasonic treatment for 1-2 hours, dropwise adding 10-20 parts by mass of ionic liquid into the carbon black dispersion liquid, stirring for 3-5 hours at normal temperature, putting the mixture into an oven, and drying the ethanol at 80-110 ℃ to obtain the carbon black modified by the chitosan and the ionic liquid.

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

The carbon black in the ionic liquid modified carbon black is common standard carbon black for rubber, and the mass ratio of the carbon black to ethanol is 1: 6-1: 10.

The chitosan is polyglucosamine (1-4) -2-amino-B-D glucose, and the viscosity is 0.25-0.65 Pa.s.

The ionic liquid in the ionic liquid modified carbon black is pyridine salt, such as or a mixture of several of N-hexylpyridine tetrafluoroborate, N-butylpyridine nitrate, N-butylpyridine dinitrile amine salt, N-butylpyridine p-methylbenzene sulfonate and the like, and the mass ratio of the ionic liquid to the carbon black is 1: 10-1: 5.

In the latex coagulation, is added with 3-15 parts of coagulant and 20-100 parts of soft water, and the coagulant is a saturated NaCl aqueous solution and is used in an amount of 3-15 parts.

In the method of the present invention, in the step (1), the carbon black is standard carbon black for rubber; in the step (2), the stirring time is 2-5 h.

The polymer obtained by the invention has the properties that the bound acrylonitrile amount (mass) is 28-34 percent, and the -nylon viscosity ML₍₁₊₄₎ ^100℃70-80, the 300% stress at definite elongation is 6.0-10.5 MPa, the tensile strength is not less than 19.0MPa, and the elongation at break is not less than 670%.

According to the method for preparing the nitrile rubber by using the pyridinium ionic liquid and the chitosan modified carbon black, chitosan is added, a large amount of hydroxyl and amino are introduced, and the carbon black is subjected to preliminary pretreatment; meanwhile, pyridine salt ionic liquid is added to modify the carbon black, the surface of the carbon black is modified by utilizing the physical adsorption effect between the pyridine salt ionic liquid and the carbon black without damaging the surface structure, and the ethanol solvent can be directly removed by drying; because the condensation temperature is lower, the carbon black structure modified by the ionic liquid is not damaged, the dispersion of the ionic liquid and the carbon black in the rubber matrix is improved by the hydrogen bond action of the ionic liquid and the carbon black, and the interface interaction between the ionic liquid and the rubber matrix is enhanced, so that the mechanical property and the low-temperature resistance of the rubber are improved; the ionic liquid modified carbon black is added in the condensation of the nitrile latex, and the modification method is simple and easy to operate.

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.