Search

CN-122010993-A - Ether-ester double complex and application thereof in preparation of high-activity polyisobutene

CN122010993ACN 122010993 ACN122010993 ACN 122010993ACN-122010993-A

Abstract

The invention discloses an ether-ester double complex and application thereof in preparing high-activity polyisobutene. The ether-ester double-coordination complex comprises a main dosing electron body, a secondary dosing electron body and an initiator. The polyisobutene is prepared under high monomer concentration by precisely regulating and controlling the molar ratio (such as 5-20) of ether/ester in the compound electron donor system, controlling the stability of a complex compound by halogen species in a main distribution electron body, realizing layered regulation and control of electron density through space configuration design and cooperatively inhibiting chain transfer and termination, and has high monomer conversion rate, high activity (high exo-olefin content) and narrow molecular weight distribution (1.2-1.8), wherein the exo-olefin content is more than or equal to 90%, the monomer conversion rate is more than or equal to 95%.

Inventors

  • WU YIBO
  • WANG JIN
  • LUO ZHI
  • LIU RUOFAN
  • DING WEI
  • JIN YUSHUN

Assignees

  • 北京石油化工学院

Dates

Publication Date
20260512
Application Date
20251218

Claims (10)

  1. 1. The ether-ester double-coordination complex is characterized by comprising a main dosing electron body, an auxiliary dosing electron body and an initiator, The main distribution electron body is selected from ether compounds, and the ether compounds have a structural general formula shown in the following formula I: I is a kind of In the formula I, X is F, cl or Br, p is an integer of 0-15, R 1 is one of C 1 –C 5 alkyl, C 2 –C 5 alkenyl and C 6 –C 10 aryl (such as phenyl) which are unsubstituted or substituted by one, two or more groups selected from R c , and R c is F, cl, br or C 1 –C 3 alkyl; The auxiliary distribution electron body is selected from a monoester compound, the general formula of the monoester compound is R a –C(=O)–O–R b , wherein R a is selected from C 1 –C 5 linear alkyl, R b is selected from C 1 –C 5 linear alkyl, C 1 –C 5 branched alkyl or C 1 –C 5 cycloalkyl, and the C 1 –C 5 branched alkyl does not contain tertiary carbon atoms; The initiator is at least one selected from boron initiator, aluminum initiator, titanium initiator and iron initiator; The molar ratio of the main distribution electron body to the auxiliary distribution electron body is 5-20:1; The molar ratio of the main distribution electron body to the initiator is 0.1-1:1.
  2. 2. The ether-ester double complex according to claim 1, wherein the initiator is one, two or more selected from boron trifluoride, boron trichloride, aluminum ethyl dichloride, titanium tetrachloride and iron trichloride.
  3. 3. The ether-ester two-part complex according to claim 1, wherein the ether-ester two-part complex further comprises a solvent; the solvent is selected from one, two or more of n-hexane, cyclohexane, methylcyclohexane and n-heptane.
  4. 4. An ether-ester bis-complex according to claim 3, wherein in formula I, R 1 is selected from F, cl or Br substituted C 1 –C 3 alkyl or halogen substituted C 2 –C 3 alkenyl; In the general formula of the monoester compound, R b is selected from C 1 –C 12 straight-chain alkyl or branched-chain alkyl.
  5. 5. The method for preparing the ether-ester double complex according to any one of claims 1 to 4, wherein the preparation method comprises the steps of mixing a main distribution electron body and an auxiliary distribution electron body in an inert atmosphere under a solvent condition to obtain a mixed solution, cooling to a temperature not higher than 0 ℃, adding an initiator, and stirring to react to obtain the ether-ester double complex.
  6. 6. Use of the ether-ester dual-coordination complexes according to any of claims 1 to 4 for preparing polyisobutenes.
  7. 7. A process for polymerizing polyisobutene, which comprises adding an isobutylene monomer in the presence of a solvent and adding the ether-ester double complex according to any one of claims 1 to 4 to carry out polymerization to obtain the polyisobutene.
  8. 8. The polymerization process of claim 7, wherein the polyisobutylene has a high activity and the terminal olefin content of the polyisobutylene is greater than 90%; The polyisobutene has a number average molecular weight greater than 10000; the polyisobutene has a molecular weight distribution coefficient of not more than 1.8.
  9. 9. The polymerization process of claim 7 wherein the solvent is cooled to polymerization temperature prior to the addition of isobutylene monomer; the polymerization temperature is-50 ℃ to-20 ℃; The ether-ester double complex is added into the reaction system at one time.
  10. 10. The polymerization process of claim 6, wherein the isobutylene monomer concentration in the reaction system is 30wt% to 60wt%; In the reaction system, the concentration of the initiator is 0.0001-0.1 mol/L; The polymerization reaction time is 1-120 minutes; After the polymerization reaction is finished, the conversion rate of the isobutene monomer is more than 95 percent.

Description

Ether-ester double complex and application thereof in preparation of high-activity polyisobutene Technical Field The invention belongs to the field of polymer synthesis, and particularly relates to an ether-ester double-complex compound electron donor technology and application thereof in preparing high-activity polyisobutene. Background The high-activity polyisobutene (HRPIB) is used as a special polymer with the tail end rich in exo-olefin functional groups (the content is more than 60 percent and the industrial preferred level is more than or equal to 75 percent), and the high-activity double bond structure of the molecular chain tail end provides a unique chemical platform for preparing high-performance polymer additives. Through cycloaddition reaction with Maleic Anhydride (MA), HRPIB can directionally synthesize polyisobutene succinimide ashless dispersant, the anti-deposition efficiency of the product in a lubricating oil system is improved by more than 40 percent compared with that of traditional sulfonates, when a third monomer such as 1-decene, acrylic acid and the like is introduced for ternary polymerization, the low-temperature embrittlement temperature of the obtained elastomer thickener can be reduced to below 50 ℃ below zero, and meanwhile, the compatibility index of the elastomer thickener with fluororubber sealing elements is improved to 0.92 (ASTM D2000 standard). In particular, the polyisobutyl monoamine gasoline detergent prepared by the carbonylation-ammonolysis route can lead the sediment reduction rate of the air inlet valve to reach 92% in bench test, which is obviously superior to polyether amine competitive products. Currently, the industrial production mainly depends on boron (BF 3), aluminum (AlCl 3/EtAlCl2) and titanium/iron catalytic systems, wherein secondary alcohol/ether electron donor control technology developed by BASF is representative. Studies have shown that there is a synergistic effect of the pKa value of the oxygen atom in the electron donor with the alkyl steric hindrance index (SSI) in that when isopropanol with pKa=16.5 is used, the monomer conversion can reach 89%, but the molecular weight distribution width (PDI) of the resulting product reaches 2.8, whereas when tert-butanol ether with pKa=18.2 is used, the PDI narrows to 2.3, but the reaction rate decreases by 35%. The trade-off relation of activity and selectivity can be balanced by adjusting the catalyst proportion when the concentration of isobutene monomers is lower than 50wt%, however, when the concentration of the monomers is increased to an industrial level (more than or equal to 50wt%, the beta-hydrogen transfer reaction rate is exponentially increased, so that the chain termination reaction rate is increased from 12% to 38%, three technical defects are finally caused, namely, firstly, the molecular weight distribution is widened to be more than 3.2, the stability of a downstream derivative batch is reduced, secondly, the retention rate of the tail end exo-double bond is reduced by 60% by a threshold value, the capturing capacity of PIBA detergents on nano carbon deposit is directly weakened, thirdly, the monomer conversion rate is limited to be less than 82%, 3-5 times of solvent circulation amount is forced to be adopted by a production enterprise to maintain the reaction, and the energy consumption cost is increased by 28% -35%. Although the high concentration polymerization process has the significant advantage from the industrial economical point of view of analysis that the space-time yield can be improved from 12 kg/(m 3.h) to 18 kg/(m 3.h) in the prior art, the energy consumption of the solvent recovery unit is reduced by 42%, and the carbon emission of unit product is reduced by 0.8tCO 2 e/t, the activity attenuation mechanism of the existing catalytic system under the high concentration condition is not clear, and the competitive adsorption kinetics of the electron donor and the isobutene monomer lack quantitative models, so that the industrial device still needs to operate below 45 weight percent of monomer concentration. Therefore, how to develop a high-efficiency catalytic system suitable for high monomer concentration so as to realize narrow HRPIB molecular weight distribution (PDI is less than or equal to 2.0) and terminal group activity maintenance (exo-double bond is more than or equal to 75%) has become a core task for improving international competitiveness of the domestic polyisobutene industry. Disclosure of Invention In order to solve the technical problems, the invention provides the following technical scheme: An ether-ester double-coordination complex comprises a main dosing electron body, an auxiliary dosing electron body and an initiator, The main electron donor is selected from ether compounds, preferably ether compounds capable of forming stable bi-or multi-dentate coordination structures with Lewis acid (such as AlCl 3、EtAlCl2、BF3 and the like) to construct clusters, and