N-valeronitrile-N'-methylimidazolium hexafluorophosphate ([C 4 CNmim]+ PF 6),as a novel ionic liquid with polar nitrile functional group,was prepared.The structure of the ionic liquid was characterized by using IR and 1 H NMR.As a medium,the ionic liquid plays an important role in copolymerization of carbon monoxide (CO) with styrene (St).Some synthetic conditions were determined,including the usage of ionic liquid,palladium composite catalyst and methanol,CO pressure,reaction time and reaction temperature.The influence of these factors on catalytic activity was analyzed.The results show that the catalytic activity has reached 1 724.1 gStCO/(gPd·h) and the catalyst could be reused 5 times under the optimal condition:composite catalyst 0.015 mmol,ionic liquid 3 mL,methanol 0.75 mL,CO pressure 2MPa,reaction time 2 h and reaction temperature 70℃.This CO/St copolymerization within [C 4 CNmim]+ PF 6 system could facilitate ionic liquids with efficient and economical applications to polymeric materials.
Room temperature ionic liquids as solvents for palladium-catalyzed copolymerization of carbon monoxide and styrene were prepared by reaction of aqueous lead tetrafluoroborate with correspond-ing chloride or bromide salts. The recyclability of palladium composite catalyst in various ionic liquids was investigated. [Pd(bipy)2][BF4]2 showed a lower catalytic activity than [Pd(bipy)2][PF6]2 in similar conditions, although the catalytic activity of each composite catalyst in ionic liquids still existed after 4 successive recycles. It was shown the catalytic activity of palladium composite catalyst was higher than that of the catalyst formed in situ from palladium acetate, 2,2′-bipyridyl, and HA (A=PF6-, BF4-) in ionic liquids. The effects of volume of ionic liquids, reaction time, and the dosage of benzoquinone on the copolymerization were also studied.
A series of electron donors,including 1,1-cyclopentanecarboxylic acid diethyl ester (CPCADEE),1,1cyclopentanedimethanol acetic diester (CPDMAD),1,1-biethoxymethyl pentane (BEMP),2,2-diethyl diethylmalonate (DEDEM)and 2,2-diethyl-1,3-propanediol acetic diester (DEPDADE),were synthesized by diethyl malonate (DEM).The purities and structures of the above products were characterized by gas chromatography (GC) and gas chromatography-mass spectrometer (GC-MS),respectively.Furthermore,the possible optimal three-dimensional structures of these donors were simulated by means of Gaussian 03 and Chem 3D.Then these electron donors were coordinated with tetrachloro titanium (TiCl 4) and chloride magnesium (MgCl 2)to obtain the catalysts for the polymerization of propylene.The catalytic activities and properties of polypropylene are greatly improved by adding external donor(ED) when CPCADEE or DEPDADE is used as internal donor(ID).However,when BEMP was used as ID,the highest catalytic activity is obtained without adding ED,which can reduce production costs and simplify catalytic synthesis.The experiments indicate that BEMP has the shortest distance of oxygen atoms and the highest electronegativity.
The copolymerization of CO and styrene catalyzed by Pd/C toward the formation of polyketones(PK)was studied in the N-valeronitrile-N'-methylimidazolium hexafluorophosphate([C4CNmim]+PF-6) medium. The synthesized PK was characterized by Fourier transform infrared(FTIR), elemental analysis, 13C-nuclear magnetic resonance(13C-NMR), differential scanning calorimetry(DSC), thermogravimetric analysis(TGA) and gel permeation chromatography(GPC). The supported ionic liquid film on the surface of Pd/C catalyst can prevent the products from covering the hole of active carbon due to its chemical stability and weak coordination ability with metal ions, and thus efficiently improve the catalytic activity. The effects of different amounts of ionic liquid on the catalytic activity and reusability of the catalyst and the molecular weight of PK were discussed. When the usage of ionic liquid is 10wt%(0.1 g ionic liquid / 1 g active carbon carrier) and the theoretical content of Pd2+ is 5wt%(0.05 g Pd2+/ 1 g active carbon carrier), the highest catalytic activity 2 963.64 gSTCO/(gPd·h) is achieved with the molecular weight and polydispersity index of PK as Mn=9 684, Mw=13 452 and Mw /Mn=1.389.
The dipping method was devised to deposit Pd onto carbon nanotube as supported catalyst(Pd/CNT) for the copolymerization of carbon monoxide(CO) and styrene(ST) towards the formation of polyketone(PK).The Pd/CNT was characterized by X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD) and high-resolution transmission electron microscopy(HRTEM).The construction and crystallization property of PK were evaluated by Fourier transform infrared spectroscopy(FTIR),13C-nuclear magnetic resonance(NMR) and XRD,respectively.The catalyst showed excellent activity and reusability in promoting the fabrication of PK.It can be recycled 14 times with the highest total catalytic activity of 4 239.64 gPK/(gPd·h) at Pd content of 8.63wt%.The results indicate that the prepared catalyst is effective to catalyze the copolymerization of CO and styrene.
A series of 4,4'-disubstituted-[2,2']-bipyridines, featuring electron withdrawing/donating functional groups such as amino, chloro, nitro, ethoxycarbonyl, carboxy, methyl, methoxy and hydroxymethyl, have been synthesized and employed in the copolymerization of carbon monoxide(CO)and styrene. The available bipyridine and its derivatives were coordinated with palladium(Ⅱ)acetate for catalyzing the copolymerization of CO and styrene, and the concomitant polyketone was characterized by means of 13 C NMR, FTIR, differential scanning calorimetry(DSC)and element analysis techniques concerning its structure and thermal performance. The effect of different electron-donating and electron-withdrawing groups on catalyst performance and molecular weight of copolymer was studied under certain experimental condition. It has been proved that the enhancement of electron donating and conjugative effects on bipyridine ligand will not only improve the catalytic activity of the composition, but also increase the molecular weight of the as-prepared polyketone. The catalytic activity is the highest in hydroxymethyl substituted 2,2'-bipyridine ligand(1 356 g STCO/(g Pd · h)), when the molecular weight and polydispersity index of the polyketone are M n=8 502,M w=1 3440 and M w/M n=1.581, respectively.
