Vanadium(V) Complexes Containing Unsymmetrical N-Heterocyclic Carbene Ligands: Highly Efficient Synthesis and Catalytic Behavior towards Ethylene/Propylene Copolymerization

The highly efficient method has been developed for the synthesis of NHC·VOCl_(3) containing symmetrical or unsymmetrical Nheterocyclic carbene(NHC) ligands by the transmetallation reaction of NHC·AgCl with VOCl_(3).The total isolated yield of VOCl_(3)[1,3-(2,4,6-Me_(3)C_(6)H_(2))_(2)(NCH=)_(2)C:](V4') reached 86% by transmetallation reaction,which is much higher than that(48%) by direct coordination method.This methodology has also been used to synthesize the novel vanadium complexes containing unsymmetrical NHC ligands of VOCl_(3)[PhCH_(2)NCH=CHNR)C:](V5',R=2,4,6-Me_(3)C_(6)H_(2);V6',R=2,4-Me_(2)-6-Ph-C_(6)H_(2);V7',R=2,6-^(i)Pr_(2)-C_(6)H_(3)) with high yield,which could not be obtained by direct coordination method.The catalytic activity and copolymerization ability would be improved by introducing unsymmetrical NHC ligands due to their less steric bulky effect.The vanadium complex V5' containing unsymmetrical NHC ligand exhibits higher catalytic activity(3.7×10^(5)g_(copolymer)·mol^(-1) of V·h^(-1)) than that of V4' containing symmetrical NHC ligand.Moreover,the higher propylene incorporation ratio(45.6 mol%) in the copolymers of ethylene with propylene could be obtained by using V5' than that(39.9%) by using V4'.The results would provide a highly efficient strategy for the synthesis of early transition metal complexes containing versitile NHC ligands,affording the catalyst with both high catalytic activity and copolymerization ability for the synthesis of high performance polyolefin elastomers.

Rapid Self-healing and Strong Adhesive Elastomer via Supramolecular Aggregates from Core-shell Micelles of Silicon Hydroxyl-functionalized cis-Polybutadiene

Liquid trimethoxy silane-functionalized cis-polybutadiene(cis-PB-Si(OMe)3),possessing number-average molecular weights of cis-PB segments(Mn,PB)ranging from 1800 g/mol to 5400 g/mol,with cis-1,4 content of ca.80%and high functionality(>96%)could be synthesized by coordination copolymerization of living cis-PB chain ends with ethenyltrimethoxy-silane with neodymium-based catalytic system.The silicon hydroxyl-functionalized cis-polybutadiene(cis-PB-Si(OH)_(3))-based micelles in water have been achieved by in situ hydrolysis of cis-PB-Si(OMe)_(3)in hexane/water mixture(pH=6.8)at 70℃and by sequential removal of residue hexane.The size of the above micelles with soft elastic cis-PB cores could be remarkably enlarged by loading SiO_(2)nanoparticles on their surfaces via hydrogen bonding interaction.Giant supramolecular long chain aggregates or networks formed by hydrogen bonding interaction and possible O—Si—O chemical bonds between cis-PB-Si(OH)3-based micellar surfaces had relatively large size and thus precipitated from water after several months of storage,leading to production of cis-PB-Si(OH)_(3)solid elastomer with extremely low T_(g)at−107.0℃.The left cis-PB-Si(OH)_(3)-based micelles in water with relatively small size gradually formed the water-insoluble cis-PB-Si(OH)_(3)-based supramolecular aggregates or networks.The cis-PB-Si(OH)_(3)-based supramolecular elastomer exhibited excellent self-healing property within 60 s at 25℃.The elastomer(20 mg)in a joint of 25 mm×30 mm(2.7 mg/cm^(2))provided very strong adhesion for two pieces of glass and the bound glass keep unchanged at room temperature for 98 h even hung with 100 g of steel column below.The cis-PB-Si(OH)3-based supramolecular elastomer would have potential applications in adhesives,self-healing materials,damping materials and elastic materials.

Antibacterial and pH-responsive Quaternized Hydroxypropyl Cellulose-g-Poly(THF-co-epichlorohydrin)Graft Copolymer:Synthesis,Characterization and Properties

The novel quaternized hydroxypropyl cellulose-g-poly(THF-co-epichlorohydrin)graft copolymers,HPC-g-QCP(THF-co-ECH),have been successfully synthesized to combine the properties from hydrophilic hard HPC biomacromolecular backbone and hydrophobic flexible polyether branches.Firstly,the P(THF-co-ECH)living chains were synthesized by cationic ring-opening copolymerization of THF with ECH.Secondly,P(THF-co-ECH)living chains were grafted onto HPC backbone by reaction with-OH groups along HPC to produce HPC-g-P(THF-co-ECH)graft copolymers.Thirdly,the mentioned graft copolymers were quaternized by reaction with ternanyamine to generate functionalized HPC-g-QCP(THF-co-ECH).The HPC-g-QCP(THF-co-ECH)graft copolymers exhibited good antibacterial ability against S.aureus or E.coli bacteria.The ibuprofen(IBU)-loaded microparticles of HPC-g-(QC)P(THF-co-ECH)graft copolymers were prepared by electrospraying.The in vitro pH-responsive drug-release behavior of IBU reached up to 75%of drug-loaded at pH=7A.This quaternized graft copolymer was beneficial to solving the problems of a burst effect and fast release of HPC as drug carriers.

Highly Cis-1,4 Selective Polymerization of Conjugated Dienes Catalyzed by ^-heterocyclic Carbene-ligated Neodymium Complexes

Neodymium complexes containing N heterocyclic carbene(NHC)ligands,NdCl5[1,3,R(NCH=)2C]-THF,(Nd1:R=2,6-Pr2C6H3,x=0;Nd2:R=2,6-Et2C6H3,x=1;Nd3:R=2.4,6-Me3C6H2,x=1)were synthesized and employed as precatalysts for the coordination polymerization of conjugated dienes(butadiene and isoprene).In combination with trisobutylaluminium(TIBA),Nd1 promoted butadiene polymerization to produce extremely high cis-1,4(up to 99.0%)polybutadienes with high molecular weight(Mw=250-780 kg·mol 1).The Nd1/TIBA catalytic system also exhibited both high catalytic activity and cis-1,4 selectivity(up to 97.8%)for isoprene polymerization.The catalytic activity,molecular weight and molecular weight distribution of resulting polydienes were directly influenced by Al/Nd molar ratio,aging method,and polymerization temperature.Very interestingly,the high cis-1,4 selectivity of the catalyst towards butadiene and isoprene kept almost unchanged under different reaction conditions.The cis-1,4 polyisoprenes with high molecular weight(Mw=210-530 kg·mol 1)and narrow molecular weight distribution (Mw/Mn=1.9-2.7)as well as high cis-1.4 selectivity(-~97%)could be synthesized by using the aged Nd1/TIBA catalytic system in the presence of isoprene(100 equivalent to Nd)at low AlNd molar ratios of 6-10.Polyisoprenes with low molecular weights(Mw=12-76 kg·mol-7)and narrow molecular weight distributions (Mw/Mn=1.7-2.6)were obtained by using Nd2 and Nd3 as precatalysts,indicating that the molecular weight of resulting polyisoprenes can be adjusted by changing the substitutes of ligand in Nd complex.

Functionalized Copolymers of Isobutylene with Vinyl Phenol: Synthesis,Characterization, and Property

The random copolymers of isobutylene (IB) with polar comonomers of 4-acetoxystyrene (ACS) or 4-tert-butoxystyrene (TBO), P(IB-co-ACS) and P(IB-co-TBO), could be successfully synthesized via cationic copolymerization with FeCh-based initiating system. The kinetics of the cationic copolymerization process was in situ investigated by inserting a diamond probe into the reaction system by ATR-FTIR spectroscopy. The chemical structure and incorporation content of polar comonomers in the copolymers were characterized by GPC with RI/UV dual detectors and 1H-NMR spectroscopy. The corresponding functionalized random copolymers of IB with vinyl phenol P(IB-co-POH) carrying phenolic hydroxyl side groups could be further prepared via the complete hydrolysis of acetoxyl side groups in P(IB-co-ACS) or tert-butoxyl side groups in P(IB-co-TBO) copolymers. The functionalized P(IB-co-POH) copolymers became hydrophilic with water contact angle (WCA) of ca. 80° for the self-assembly in hot water, compared to the hydrophobic polyisobutylene with WCA of ca. 110°. The functionalized P(IB-co-POH) copolymers also displayed an excellent self-healing property due to the interaction of intermolecular hydrogen bonding and formation of three dimentional supramolecular networks from phenolic hydroxyl side groups. Furthermore, P(IB-co-POH) copolymers also provided a good matrix for the homogeneous dispersion for silica nanoparticles due to the formation of hydrogen bonding between copolymer chains and silica nanoparticles.

SYNTHESIS OF pH-RESPONSIVE AMPHIPHILIC DIBLOCK COPOLYMERS CONTAINING POLYISOBUTYLENE via OXYANION-INITIATED POLYMERIZATION AND THEIR MULTIPLE SELF-ASSEMBLY MORPHOLOGIES

Two pH-responsive amphiphilic diblock copolymers, namely polyisobutylene-block-poly[2-（N,N- dimethylamino）ethyl methaerylate] （PIB-b-PDMAEMA） and polyisobutylene-block-poly（metharylic acid） （PIB-b-PMAA）, were synthesized via oxyanion-initiated polymerization, and their multiple self-assembly behaviors have been studied. An exo-01efin-terminated highly reactive polyisobutylene （HRPIB） was first changed to hydroxyl-terminated PIB （PIB-OH） via hydroboration-oxidation of C =C double bond in the chain end, and then reacted with KH to yield a potassium alcoholate of PIB （PIB-O-K＋）. PIB-O-K＋ was immediately used as a macroinitiator to polymerize DMAEMA monomer, resulting in a cationic diblock copolymer PIB-b-PDMAEMA. With the similar synthesis procedure, the anionic diblock copolymer PIB-b- PMAA could be prepared via a combination of oxyanion-initiated polymerization of tert-butyl methacrylate （tBMA） and subsequent hydrolysis of tert-butyl ester groups in PtBMA block. The functional PIB and block copolymers have been fully characterized by 1H-NMR, FT-IR spectroscopy, and gel permeation chromatography （GPC）. These samples allowed us to systematically investigate the effects of block composition on the pH responsivity and various self-assembled morphologies of the copolymers in THF/water mixed solvent. Transmission electron microscopy （TEM） images revealed that these diblock copolymers containing small amount of original PIB without exo-olefin-terminated group are able to self-assemble into micelles, vesicles with different particle sizes and cylindrical aggregates, depending on various factors including block copolymer composition, solvent polarity and pH value.

Syndiospecific Polymerization of Styrene Catalyzed by Half-titanocenes Containing Monodentate Anionic Nitrogen Ligands

Main observation and conclusion Styrene polymerization catalyzed by the half-titanocenes CpTiCl_(2)[1,3-R_(2)(CH_(2)N)_(2)C=N](6b:R=_(2),6-Me_(2)C_(6)H_(3),T_(4):R=_(2),4,6-Me_(3)C_(6)H_(2);T5:R=_(2),6-iPr_(2)C_(6)H_(3))was carried out in the presence of methylaluminoxane(MAO).Compared to the styrene conversion(31%)and syndiospecific index(45%)using reported 6b as precatalyst,T5 bearing ligand with isopropyl substitutes on the N-aryl-rings exhibits much higher styrene conversion(61%)and syndiospecific index(99%),indicating that the catalytic behavior could be improved obviously by the introduction of electronic donating and steric bulky substituents.One N atom in imidazolin-_(2)-iminato ligand was replaced by O atom,affording half-titanocenes CpTiCl_(_(2))[3-C6H5(CH_(2)N)(CH_(2)O)C=N(T1)and CpTiCl_(_(2))[_(2),6-Me_(2)(C6H3O)(NiPr_(2))C=N](T_(2)).Compared to 6b,both higher styrene conversion and syndiospecific index are afforded by using half-titanocene T1 containing_(2)-imino-3-phenyloxazolidine ligand.All the results illustrate that both the chemical structure and the nature of substituents of the ligand have obvious influence on the styrene conversion and syndiospecific index in the polymerization of styrene.All the resulting syndiotactic polystyrenes(sPSs)are highly syndiospecific(rrr>99%).Correspondingly,the sPS prepared using T5/MAO catalytic system exhibits high melting point and narrow molecular weight distribution.The results might show new light on designing more efficient half-titanocenes for styrene polymerization with both high styrene conversion and high syndiospecific selectivity.

Biocompatible,Hemocompatible and Antibacterial Acylated Dextran-g-polyisobutylene Graft Copolymers with Silver Nanoparticles

The novel amphiphilic acylated dextran-g-polyisobutylene(AcyDex-g-PIB)graft copolymers with different branch lengths(A4nPtB,2600-5800 g/mol)and grafti ng numbers(GN,5-28 per 1000 Dex mono saccharide)were successfully synthesized via the nu cleophilic substitution of the hydroxyl(-OH)side groups along AcyDex backb one by the living PIB-THF4+chai ns prepared through cati onic polymerizatio n.The crystallizati on of AcyDex backb one in AcyDex-g-PIB graft copolymers was con fined due to the prese nee of PIB branches and the morphology changed from short rod-like crystals to fragment-like crystals with increasing Mn P|B and GN.The obvious microphase separation occurred due to the incompatibility between hard AcyDex backbone and soft PIB branches.AcyDex-g-PIB graft copolymers exhibit excellent biocompatibility towards HeLa cells and good hemocompatibility with red blood cells(RBCs),both of which increase with increasing GN.The in creases of water con tact angle and roughness on the surface of the graft copolymers with in creasi ng A4nP|B and GN manifest the anti-protein adsorption performance.The amphiphilic AcyDex-g-PIB graft copolymers could self-assemble in aqueous solution into nanospheres,which can be used as pH-sensitive drug carriers and can release 100%of the loaded drug within 72 h at pH=7.4.AcyDex-g-PIB graft copolymers bearing silver nanoparticles(Ag-NPs,0.8 wt%-3.9 wt%,4.5-9.5 nm)show good antibacterial properties.This kind of amphiphilic graft copolymer would have a promising prospect in biological and medical fields.

Amphiphilic Graft Copolymers of Hydroxypropyl Cellulose Backbone with Nonpolar Polyisobutylene Branches

The novel amphiphilic graft copolymers with hydrophilic hard polar hydroxypropyl cellulose(HPC)backbone and hydrophobic soft nonpolar polyisobutylene(PIB)branches have been successfully synthesized through nucleophilic substitution reaction of living PIB chains carrying oxonium ions with the-OH groups along HPC backbone.The PIB branch length in the graft copolymers could be designed by living cationic polymerization and the grafting density could be adjusted by PIB+/-OH molar ratio.The living PIB chains carrying oxonium ion were prepared by transformation of allyl bromide end groups in the presence of AgCI0_(4) and silver nanoparticles(3.2±0.3 nm,0.7 wt%-1.8 wt%)generated in situ from AgBr.The phase-separation morphology was formed in the graft copolymers due to their incompatibility between backbone and branches.The hydrophilicity on the surface of graft copolymer films could be turned to hydrophobicity by increasing grafting density or/and length of PIB branches.The soft PIB segments in graft copolymers provided an unique surface wa self-assembly for ant卜protein adsorption against bovine serum albumin.A small amount of Ag nanoparticles in the copolymers contributed to good antibacterial activities against Staphylococcus aureus or Escherichia coli.

Nanocrystallization-locked Network of Poly(styrene-6-isobutylene-6-styrene)-g-Polytetrahydrofuran Block Graft Copolymer

Poly(styrene-6-isobutylene-6-styrene)triblock copolymer(SIBS),a kind of thermoplastic elastomer with biocompatibility and biostability containing fully saturated soft segments,could be synthesized via living cationic copolymerization.A novel poly[(styrene-co-methylstyrene)-b-isobutylene-b-(styrene-co-methylstyrene)]-g-polytetrahydrofuran(M-SIBS-g-PTHF)block graft copolymer was prepared to increase the polarity and service temperature of SIBS by grafting polar PTHF segments onto SIBS.A series of the above block graft copolymers with average grafting numbers from 2 to 6 and molecular weights of PTHF branches ranging from 200 g·mol^(-1)to 4200 g·mol^(-1)were successfully synthesized via living cationic ring-opening polymerization of tetrahydrofuran(THF)coinitiated by AgCI04.The introduction of PTHF branches led to an obvious microphase separation due to thermodynamic incompatibility among the three kinds of segments of polyisobutylene(PIB),polystyrene(PS)and PTHF.Moreover,the microphase separation promotes the rearrangement of PTHF branches to form the nanocrystallization-locked physically cross-linked network after storage at room temperature for 2 months,leading to insolubility of the copolymers even in good solvents.The melting temperature and enthalpy of PTHF nanocrystallization locked in hard domains of M-SIBS-g5-PTHF-1.1k block graft copolymer increased remarkably up to 153℃and 117.0 J·g^(-1)by 23℃and 11.6 J·g^-1(respectively after storage for long time.Storage modulus(G′)is higher than loss modulus(G″)of M-SIBS-g-PTHF block graft copolymer at temperatures ranging from 100℃to 180℃,which is much higher than those of the SIBS triblock copolymer.To the best of our knowledge,this is the first example of high performance M-SIBS-g-PTHF block graft copolymers containing segments of PIB,PS and PTHF with nanocrystallization-locked architecture.

Correction to"Nanocrystallization-locked Network of Poly(styrene_b-isobutylene-6-styrene)-g-Polytetrahydrofuran Block Graft Copolymer"

The data points of storage modulus(G′)and loss modulus(G″)above 130℃in Figs.14(a)and 14(b)were imprecise because the sample of M-SIBS flowed in rheological test when the test temperature is above 130℃.Therefore,the data points above 130℃in Figs.14(a)and 14(b)need to be deleted.The corrected version of Figs.14(a)and 14(b)is provided below.The descriptions in Figs.14(a)and 14(b)are not changed,and thus additional text corrections are not needed.The authors apologize for any inconvenience caused.