Coal Tar Derived Metallocene Catalyst for Polymerization of 1-Decene into Low-viscosity Poly-α-Olefin Lubricating Base Oil

The production of poly-α-olefins(PAOs)has attracted attention due to their excellent viscosity-temperature dependence,wear characteristics,oxidative properties,and high thermal stability.In this study,indene extracted during coal tar refining was used as a raw material to synthesize a bis(indenyl)zirconium dichloride metallocene catalyst.A PAO with low viscosity and a high viscosity index was produced via the oligomerization of 1-decene in the presence of both the prepared metallocene and a methylaluminoxane(MAO)co-catalyst.Notably,the effects of different synthesis reaction parameters,such as Al:Zr ratio,amount of catalyst,and reaction temperature,on the conversion ratio and product selectivity were investigated in detail.The produced PAO was thoroughly characterized using Fourier-transform infrared,^(13)C,and^(1)H nuclear magnetic resonance spectroscopies;gas chromatography;and viscosity measurements.At 70℃,the metallocene catalyst created more stable active sites.In addition,the alkylation effect of MAO was noticeable.Interestingly,the obtained catalysis results demonstrated that a high conversion ratio of~93%was achieved at a low reaction temperature of 70℃,with a catalyst dosage of 0.0848 mmol and Al:Zr ratio of 8.48mmol:0.0848mmol.Moreover,under these optimal conditions,the kinematic viscosity of PAO was 4.25 mm2/s at 100℃,and the viscosity index was 139,indicating good viscosity-temperature properties.

Preparation of Poly-α-Olefin Microcapsule Particles Coated with Polyurethane as a Drag Reducer Based on Interface Polymerization

The molecular behavior of polyurethane(PU)coating materials during the surface adsorption of poly-α-olefin as a drag reducing polymer was explored by a molecular dynamics simulation.Three different PU capsule wall materials were synthesized using two reaction monomers,and a poly-α-olefin/PU drag reducer microcapsule was prepared based on interface polymerization.The structure,morphology,thermal stability,compressive strength,and drag reduction performance of the microcapsules were characterized and compared.The results showed that a non-bonding interaction induced the adsorption of the PU coating material,poly-α-olefin and PU then fused at the interface,and the PU coating material was embedded into the inner grooves of poly-α-olefin in the form of a local mosaic,thereby forming a stable core–shell structure.The morphological characterization indicated that PU and poly-α-olefin could form microcapsule structures.The thermal decomposition temperature of the microcapsule was dependent on the type of capsule wall material.The microcapsule structure had a slight effect on poly-α-olefin drag reduction.The system enabled poly-α-olefin to exist in powdered particles through microcapsulation,and had a good dispersion effect that facilitated storage and transport processes.The method effectively inhibited the accumulation and bonding of poly-α-olefin at room temperature.

HOMO- AND COPOLYMERIZATION OF ETHYLENE CATALYZED BY ANSA-METALLOCENES WITH DOUBLY HETERO-BRIDGES

Three ansa-metallocenes(Me_2C)(Me_2Si)Cp_2TiCl_2(1),[(CH_2)_5C](Me_2Si)Cp_2TiCl_2 (2)and (Me_2C)(Me_2Si)Cp_2ZrCl_2 (3)with larger dihedral angles and longer distance from metal to the center of Cp planes were synthesized and used as catalysts for ethylene polymerization in the presence of methylaluminoxane (MAO).In the case of ethylene polymerization,compared the feature structures of unbridged metallocenes, singly bridged metallocenes and doubly bridged metallocenes 1,2,3,there exhibit the relationship bet...

Apparent Kinetics of 1-Decene Polymerization Catalyzed Using the Ionic Liquid[Bmim]_(x)[C_(2)H_(5)NH_(3)]_(1-x)[Al_(2)Cl_(7)]

Poly-α-olefin(PAO)synthetic oil,a regular long-chain alkane produced from the catalytic polymerization ofα-olefin,is a high-quality lubricating base oil with huge market potential.In this study,PAO synthesis based on the catalytic polymerization of 1-decene using the ionic liquid(IL)[Bmim]_(x)[C_(2)H_(5)NH_(3)]_(1-x)[Al_(2)Cl_(7)]as the catalyst was studied.Compared with the conventional catalyst[Bmim][Al_(2)Cl_(7)],the obtained PAO product incorporates more trimers and tetramers of 1-decene and contains few double-bond end groups,demonstrating a better catalytic system for PAO-10 production.The apparent polymerization kinetics of 1-decene in this catalytic system were studied based on the 1-decene concentration,catalyst concentration,and reaction temperature.An apparent kinetic equation for PAO formation was determined,providing a promising strategy for PAO production using 1-decene polymerization.

Mechanism Study of BF_(3)/n-Butanol-catalyzed 1-Decene Oligomerization Reaction

The active catalysts of the BF_(3)/n-C_(4)H_(9)OH-catalyzed 1-decene oligomerization reaction,as well as the distribution of the reaction products,was investigated by molecular simulation.The calculation results show that(BF_(3))_(2)·n-C_(4)H_(9)OH catalyzes the 1-decene oligomerization reaction with higher activity compared to BF_(3)·n-C_(4)H_(9)OH,which is the most catalytically active substance in the BF_(3)/n-C_(4)H_(9)OH catalyst system.The reaction energy barriers and heats of reaction of chain initiation,chain growth,and chain termination in BF_(3)/n-C_(4)H_(9)OH-catalyzed 1-decene oligomerization are calculated to reveal the product distribution.The calculation results show that the contents of the oligomerization reaction products in descending order are trimer,tetramer,pentamer,and dimer.The calculated results were consistent with the experimentally obtained product distribution.

Characterization and Apparent Kinetics of Polymerization of 1-Decene Catalyzed by Boron Trifluoride/Alcohol System

Poly-α-olefin(PAO) synthetic oil is the base oil of high-quality lubricants, and has a huge market potential.We illustrate PAO synthesis by catalytic polymerization of 1-decene with a boron trifluoride(BF_3)/alcohol system. Gas chromatography–mass spectrometry, proton nuclear magnetic resonance and ^(13) C nuclear magnetic resonance analysis confirmed dimer, trimer and tetramer structures of PAO. Each component contained branched chains with a 1,2 insertion of a head-to-tail link; a 2,1 insertion of a tail-to-tail link and a methyl-containing linked structure. At a low conversion rate, the reaction rate was related directly with the reaction temperature and the catalyst/1-decene concentration. An apparent kinetic equation for PAO formation was determined during 1-decene polymerization.

LLDPE prepared by in situ polymerization using a dual-functional catalytic system of Ti(On-Bu)_4 /AlEt_3-Et(Ind)_2-ZrCl_2/MAO

Linear low-density polyethylene (LLDPE) was prepared by in situ polymerization using a dual-functional catalytic system containing Et(Ind)2ZrCl2/MAO and Ti(On-Bu)4 /AlEt3 used as co-polymerization catalyst and dimeriza-tion catalyst, respectively. The catalytic system showed high activity and the polymer with low melting point, narrow molecular weight distribution (MWD) and low crystallinity was produced.