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高分子科学（英文版）
高分子科学（英文版）

王佛松

月刊

0256-7679

wangj@iccas.ac.cn

010-62588927

100190

北京市中关村一街2号化学所院内

高分子科学（英文版）/Journal Chinese Journal of Polymer ScienceCSCDCSTPCD北大核心SCI
正式出版
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    Topological Confinement in Reversibly Interlocked Polymer Networks

    Wan-Ting DaiZhen-Hua XieYu-Bin KeYang You...
    133-140页
    查看更多>>摘要：Recently,we reported a series of reversibly interlocked polymer networks(RILNs),whose mechanical robustness and functionalities improvement was believed to be derived from topological interlocking of two sub-networks,although the direct evidence for the deduction is still lacking.Herein,a specially-designed RILNs system,in which the inter-component hydrogen bonds can be shielded as needed,was prepared and used to study the micro-structures of RILNs,aiming to verify the existence of mechanical interlocking in RILNs.By changing the pH of the swelling solvent,the effect exerted by the inter-component non-covalent bonds was eliminated,so detailed information of the networks struc-ture was exposed.The small angle X-ray scattering(SAXS)and small-angle neutron scattering(SANS)results indicated that swelling-induced structural evolution of the two sub-networks mutually affected each other,even when the inter-component hydrogen bonds were absent,prov-ing the presence of topological interlocking.The findings may help to draw a more accurate physical image and reveal the detailed structure-property relationship of RILNs.
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    Research Progress in the Fabrication of Covalent Organic Framework Membranes for Chemical Separations

    Cui-Ting DingJin-Qiu YuanMeng-Ying XieQing-Yuan Liu...
    141-158页
    查看更多>>摘要：Membrane technology has become one of the most promising separation technologies for its energy saving,high separation efficien-cy,environmental friendliness,and economic feasibility.Covalent organic frameworks(COFs)with intrinsically high porosity,controllable pore size,uniform pore size distribution and long-range ordered channel structure,have emerged as next-generation materials to fabricate advanced separation membranes.This feature article summarizes some latest studies in the development of pure COF membranes in our lab,including their fabrication and applications in chemical separations.Finally,current challenges facing high-performance COF separation membranes are discussed.
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    Chemoselective and Living/Controlled Polymerization of Alkenyl Methacrylates by the Phosphonium Ylide/Organoaluminum Lewis Pairs

    Zhi-Kang ChenWu-Chao ZhaoYi-Ling ZhaoCong-Lei Liu...
    159-167页
    查看更多>>摘要：Chemoselective,living/controlled polymerizations of allyl methacrylate(AMA)and vinyl methacrylate(VMA)with/without methyl methacrylate(MMA)by using the phosphonium ylide/organoaluminum based Lewis pairs(LPs)have been realized.The P-ylide-2/AlMe(BHT)2(P-ylide-2=Ph3P=CHMe and BHT=2,6-iBu2-4-MeC6H2O)was demonstrated to be superior by which homopolymers PAMAs(Mn=27.6-111.5 kg/mol and Ð=1.14-1.25)and PVMAs(Mn=28.4-78.4 kg/mol and Ð=1.12-1.18)and block copolymers PMMA-b-PAMA,PAMA-b-PVMA,PAMA-b-PMMA,PMMA-b-PAMA-b-PMMA,PAMA-b-PMMA-b-PAMA,and PAMA-b-PVMA-b-PAMA were synthesized.In the polymerizations,all of the monomers were reacted by the conjugated ester vinyl groups leaving intactly the nonconjugated acryloxy groups.The pendant acryloxy groups attached to the main chain enable further to post-functionalization by the AIBN-induced radical"thiol-ene"reaction using PhCH2SH.The thiolether side group-containing polymers PAMA-SCH2Ph and PAMA-SCH2Ph-b-PMMA-b-PAMA-SCH2Ph were thus prepared.
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    Preparation of Chemically Recyclable Poly(ether-alt-ester)by the Ring Opening Polymerization of Cyclic Monomers Synthesized by Coupling Glycolide and Epoxides

    Feng RenZhuang-Zhuang LiangMing-Xin NiuChen-Yang Hu...
    168-175页
    查看更多>>摘要：Polyester and polyether are two key oxygenated polymers,and completely alternative sequence of poly(ester-alt-ether)could efficiently combine the advantages(including flexibility,degradability,etc.)of both segments.Currently,despite their copolymers could be synthesized from one-pot mixture of cyclic esters and epoxides,perfectly alternative microstructure is very challenging to realize and typically restricted to certain monomer pairs.Moving forward,synthesizing poly(ester-alt-ether)from commercially available and largescale monomers would be a significant advance.For example,successfully commercialized poly(glycolic acid)(PGA),which is not easily soluble in polymers due to its high crystallinity and is brittle and difficult to control the degradation cycle,would encounter a new paradigm if engineered into poly(ester-alt-ether).In this work,starting from the design of monomer with hybrid structures,we successfully synthesized a series of 1,4-dioxan-2-one containing different substituents based on glycolide(GA)and epoxides using commercially available Salen-Cr(Ⅲ)and PPNCl catalytic systems.The new monomers underwent ring-opening polymerization(ROP)to form a series of poly(ester-alt-ether)with perfectly alternating glycolic acid and propylene glycol repeat units under catalytic system of thiourea/base.The poly(ester-alt-ether)have significantly lower glass-transition temperature than PGA.Additionally,the poly(ester-alt-ether)can be chemically recovered to monomer using Sn(Oct)2 or 1,8-diazabicyclo[5.4.0]undecane-7-ene(DBU)as a catalyst in solution,thus establishing a closed-loop life cycle.From monomers derived from GA and epoxides,this work furnishes a novel strategy for the synthesis of poly(ester-alt-ether)with chemical recyclability.
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    Manipulating the Phase Transition Behavior of Dual Temperature-Responsive Block Copolymers by Adjusting Composition and Sequence

    Zhi ZouXiang XuHai-Tao ZhaoJian-Nan Cheng...
    176-187页
    查看更多>>摘要：Temperature-responsive polymers have garnered significant attention due to their ability to respond to external stimuli.In this work,dual temperature-responsive block copolymers are synthesized via reversible addition-fragmentation chain transfer polymerization(RAFT)polymerization utilizing zwitterionic monomer methacryloyl ethyl sulfobetaine(SBMA)and N-isopropyl acrylamide(NIPAAm)as monomers.The thermal responsive behaviors can be easily modulated by incorporating additional hydrophobic monomer benzyl acrylate(BN)or hydrophilic monomer acrylic acid(AA),adjusting concentration or pH,or varying the degree of polymerization of the block chain segments.The cloud points of the copolymers are determined by UV-Vis spectrophotometry,and these copolymers exhibit both controlled upper and lower critical solubility temperatures(LCST and UCST)in aqueous solution.This study analyzes and summarizes the influencing factors of dual temperature responsive block copolymers by exploring the effects of various conditions on the phase transition temperature of temperature-sensitive polymers to explore the relationship between their properties and environment and structure to make them more selective in terms of temperature application range and regulation laws.It is very interesting that the introduction of poly-acrylic acid(PAA)segments in the middle of di-block copolymer PSBMA55-b-PNIPAAm80 to form PSBMA55-b-PAAx-b-PNIPAAm80 results in a reversal of temperature-responsive behaviors from'U'(LCST＜UCST)to'n'(LCST＞UCST)type,while the copolymer PSBMA55-b-P(NIPAAm80-co-AAx)not.This work provides a clue for tuning the phase transition behavior of polymers for manufacture of extreme smart materials.
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    High Temperature Iron Ethylene Polymerization Catalysts Bearing N,N,N'-2-(1-(2,4-Dibenzhydryl-6-fluorophenylimino)ethyl)-6-(1-(arylphenylimino)ethyl)pyridines

    Chantsalnyam BariashirQiu-Yue ZhangBayasgalan UlambayarGregory A.Solan...
    188-201页
    查看更多>>摘要：The N,N,N'-ferrous chloride complexes,[2-{CMeN(2,4-(CHPh)2-6-FC6H2))-6-(CMeNAr)C5H3N]FeCl2(Ar=2,6-Me2C6H3 Fe1,2,6-Et2C6H3 Fe2,2,6-iPr2C6H3 Fe3,2,4,6-Me3C6H2 Fe4 and 2,6-Et2-4-MeC6H2 Fe5),each possessing one N-2,4-dibenzhydryl-6-fluorophenyl group,were readily synthesized from their respective unsymmetrical bis(imino)pyridines,L1-L5.Structural identification of Fe2 highlighted the variation in the steric properties provided by the dissimilar N-aryl groups.Following pre-treatment with either MAO or MMAO,complexes Fe1-Fe5 all displayed,at an operating temperature of 80 ℃,high activities for ethylene polymerization with levels falling in the order:Fe4＞Fe1＞Fe5＞Fe2＞Fe3.Notably,Fe4/MAO displayed the highest activity of 1.94×107 gPE·molFe-1-h-1 of the study with only a modest loss in performance at 90 ℃.Generally,the resulting polyethylenes were highly linear(Tm range:122-132 ℃),narrowly disperse and of low molecular weight(MW range:6.73-46.04 kg·mol-1),with the most sterically hindered Fe3 forming the highest molecular weight polymer of the series.End-group analysis by1H-and 13C-NMR spectroscopy revealed saturated alkyl(n-propyl and i-propyl)and unsaturated vinyl chain ends indicative of the role of both β-H elimination and chain transfer to aluminum as termination pathways.By comparison with previously reported iron precatalysts with similar tridentate ligand skeletons,it is evident that the introduction of a large benzhydryl group in combination with a fluorine as the ortho-substituents of one N-aryl group has the effect of enhancing thermal stability of the iron polymerization catalyst whilst maintaining appreciable polymer molecular weight.
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    Phosphine/Benzocyclone-based Neutral Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers

    Fei WangLi PanVladislav A.TuskaevSvetlana Ch.Gagieva...
    202-212页
    查看更多>>摘要：The efficient copolymerization of olefin with polar monomers using nickel-based catalysts presents a longstanding challenge.In this contribution,three phosphine-benzocyclone ligands and corresponding neutral nickel catalysts(Ni1:Ar=Ph;Ni2:Ar=2-(C6H5)C6H4;Ni3:Ar=2-[2',6'-(MeO)2-C6H3]C6H4)were prepared and applied for the ethylene polymerization and copolymerization with polar monomers without any cocatalyst.The bulky substituent groups in complexes Ni2 and Ni3 contributed to high catalytic activities(up to 7.24×106 and 9.04×106 g·molNi-1·h-1,respectively),and produced high-molecular-weight polyethylene(MW up to 545.7 kDa).Complex Ni3 exhibited high activities for ethylene polymerization at the level of 106 g·molNi-1·h-1 across a wide range from 30 ℃ to 120 ℃,exhibiting excellent high temperature tolerance.These nickel complexes were also effectively employed in the copolymerization of ethylene with methyl acrylate,ethyl acrylate,butyl acrylate and lauryl acrylate,producing copolymers with high molecular weights(MW up to 80.5 kDa)and high polar monomer incorporation(up to 8.2 mol％).Microstructure analyses revealed that the introduction of large sterically hindered substituents facilitated the incorporation of polar functional units into the polymer backbone.This study demonstrates the potential of these nickel-based catalysts for efficient copolymerization of olefin with polar monomers.
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    Significantly Enhanced Melt Memory Effect of Metallocene-made Isotactic Polypropylene Containing Talc

    Hong-Wen SunFu-Shan WangYan GaoFu-Qing Wei...
    213-222页
    查看更多>>摘要：The melt memory effect is a widely observed phenomenon in semi-crystalline polymers.In practical applications,various additives are usually introduced into polymers,which may affect their melt memory behavior.In this work,the effect of talc on the melt memory effect of met-allocene-made isotactic polypropylene(M-PP)was investigated in detail by using the differential scanning calorimetry.The results indicated that the introduction of talc significantly strengthened the melt memory effect of M-PP.Specifically,the upper limit temperature of Domain Ⅱ in-creased from 161 ℃ to 174 ℃,resulting in a substantial widening of the temperature range of Domain Ⅱa from 1 ℃ to 14 ℃.Analysis of the crystal orientation of the M-PP containing talc cooled from various Ts suggested that the remarkably enhanced melt memory effect could be ascribed to the stabilization of oriented nuclei facilitated by talc.This stabilizing effect was likely attributable to the prefreezing effect or the sorption interac-tion between talc and the M-PP chains.
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    Regio-and Stereoselective Polymerization of Bio-based Ocimene by Rare-Earth Metal Catalysts

    Qi-Yuan WangLi-Peng SangZhen ZhangYang Jiang...
    223-229页
    查看更多>>摘要：Coordination polymerization of renewable β-ocimene has been investigated using asymmetric diiminophosphinate lutetium complex 1,β-diketiminate yttrium complex 2,bis(phosphino)carbazolide yttrium complex 3,half-sandwich benzyl fluorenyl scandium complex 4 and pyridyl-methylene-fluorenyl rare-metal complexes 5a-5c.Complexes 1,4 and 5a-5c show trans-1,2-regioselectivities and high activities,of which 5c exhibits excellent isoselectivity(mmmm＞99％).Conversely,complexes 2 and 3 promote β-ocimene polymerization to produce isotactic cis-1,4-polyocimenes(cis-1,4＞99％,mm＞95％).Diblock copolymers cis-1,4-PIP-block-cis-1,4-POc and cis-1,4-PBD-block-cis-1,4-POc are obtained in one-pot reactions of β-ocimene with isoprene and butadiene using complex 3.Epoxidation and hydroxylation of polyocimene afford functionalized polyolefins with enhanced Tg(from-20 ℃ to 79 ℃ and 74 ℃)and hydrophilicity.
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    Impact of Annealing on the Melt Recrystallization of a-PDLA/α-PLLA Double-layered Films

    Yun-Peng LiHao-Ran ShenShao-Juan WangHao Zhang...
    230-238页
    查看更多>>摘要：Poly(lactic acid)(PLA)as a bio-based polymer with biodegradability and biocompatibility has attracted much attention.To manipulate its properties for different applications,regulation of crystal structure and crystalline morphology becomes an attractive research topic.In this work,the structure evolution of layered samples containing an amorphous poly(D-lactide)(PDLA)layer and a crystalline poly(L-lactide)(PLLA)layer with highly oriented edge-on α lamellar crystals after annealing at 150 ℃ or/and after melt-recrystallization has been studied by AFM,FTIR,and TEM combined with electron diffraction.The results demonstrate that melt recrystallization of the as-prepared sample leads to the formation of abundant randomly oriented PLA stereo-complex(PLA SC)crystals.Annealing at 150 ℃ results in the formation of a small amount of oriented PLA SC crystals at the interface.These PLA SC crystals show great impact on the recrystallization behavior of sample after melting at 190 ℃ and then crystallizing at 90 ℃.First,they impede the mutual diffusion of the overlying PDLA and underlying PLLA,and thus reduce their stereo-complexation ability as manifested by the decreased amount of PLA SC crystals.Second,they act as substrate to initiate the epitaxial crystallization of the overlying PDLA and underlying PLLA,which ensures the production of a highly oriented structure of PDLA and PLLA after melt recrystallization again.
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