This feature article summarizes the synthesis of novel olefin block copolymers using fast syndiospecific living homo- and copolymerization of propylene, higher 1-alkene, and norbornene with ansa-fluorenylamidodimethyl...This feature article summarizes the synthesis of novel olefin block copolymers using fast syndiospecific living homo- and copolymerization of propylene, higher 1-alkene, and norbornene with ansa-fluorenylamidodimethyltitanium- based catalyst according to the authors＇ recent results. The catalytic synthesis of monodisperse polyolefin and olefin block copolymer was also described using this living system.展开更多
We report the polymerization of phenyl isocyanides with the chiral palladium（II） initiating system. The resulting polymers with optically active properties were obtained by polymerization of the racemic isocyanide m...We report the polymerization of phenyl isocyanides with the chiral palladium（II） initiating system. The resulting polymers with optically active properties were obtained by polymerization of the racemic isocyanide monomer （rac-1）, and enantiomerically unbalanced polymerization of the monomer was found, providing substantial evidence for the enantiomer-selective polymerization of rac- 1 mediated through chiral catalyst. A comparison between the enantiomerically pure monomers, 4-isocyanobenzoyl-L-alanine decyl ester （1 s） and 4-isocyanobenzoyl-D-alanine decyl ester （1 r）, revealed a drastic discrepancy in the reactivity ratio of their homopolymerizations. It turned out that the monomer reactivity ratio of ls was higher than that of lr with chiral ligands. The results clearly demonstrated the inclination for incorporation of the ls enantiomer during the polymerization process and thus resulted in the enantiomer-selective polymerization in this system. The effects of the catalyst chirality on the optically active properties of polymerization were investigated, and it was concluded that the formation of higher-ordered conformation with a handed helicity might be attributed to the chiral induction of chiral palladium（II） catalyst. Moreover, the polymers obtained through the enantiomer-selective polymerization of the enantiomerically pure monomer were with a significant improvement of the optical activity if the chirality of the monomer and the catalyst matched with each other.展开更多
Half-titanocene complexes bearing dibenzhydryl-substituted aryloxide ligands （2a-2d） were prepared. Among them, 2e adopted a three-legged distorted tetrahedral geometry evidenced by X-ray crystallography. The poly-1...Half-titanocene complexes bearing dibenzhydryl-substituted aryloxide ligands （2a-2d） were prepared. Among them, 2e adopted a three-legged distorted tetrahedral geometry evidenced by X-ray crystallography. The poly-1,3-butadiene with high molecular weight and narrow molecular weight distribution was obtained by using these complexes as the catalysts activated with methylaluminoxane （MAO）. The catalytic activities of the complexes depended on their structures. The Ti-- O--C bond in the complexes with large angle afforded them with higher activity, while Cp＊-based complexes exhibited lower activities than the Cp-based analogues. The activity of complex increased with increasing the polymerization temperature while the selectivity remained no change, indicating the high thermal stability. Furthermore, the polymerization of 1,3-butadiene catalyzed by 2a/MAO at 0 ℃ has been found in a living fashion.展开更多
Living cationic polymerization of 4-acetoxystyrene(STO)was conducted in CH_(2)Cl_(2) at-15℃ using a dicumyl chloride(DCC)/SnCl_(4)/nBu_(4)NBr initiating system.Impurity moisture initiation was inhibited by adding pro...Living cationic polymerization of 4-acetoxystyrene(STO)was conducted in CH_(2)Cl_(2) at-15℃ using a dicumyl chloride(DCC)/SnCl_(4)/nBu_(4)NBr initiating system.Impurity moisture initiation was inhibited by adding proton trap 2,6-di-tert-butylpyridine(DTBP),and the controlled initiation of DCC was confirmed by ^(1)H nuclear magnetic resonance(^(1)H-NMR)spectroscopy and matrix-assisted laser desorption ionization time-offlight mass(MALDI-TOF-MS)spectrometry.The polymerization kinetics were analyzed to for optimizing the polymerization rate.Allyl-telechelic PSTOs(allyl-PSTO-allyl)with molecular weight(Mn)range of 3540–7800 g/mol and narrow molecular weight dispersity(Mw/Mn)about 1.25 were prepared through nucleophilic substitution with allyltrimethylsilane(ATMS)at approximately 40%monomer conversion.The experimental results indicate that the substitution efficiency of ATMS increased with higher ATMS concentration,temperature,and extended reaction time.Nearly unity ally-functionality for allyl-PSTO-allyl was achieved by adding sufficient SnCl_(4) prior to the substitution.展开更多
A convenient real-time monitoring of monomer concentration during living cationic ring-opening polymerizations of tetrahydrofuran（THF） initiated with methyl triflate（Me OTf） has been developed for kinetic investig...A convenient real-time monitoring of monomer concentration during living cationic ring-opening polymerizations of tetrahydrofuran（THF） initiated with methyl triflate（Me OTf） has been developed for kinetic investigation and determination of equilibrium monomer concentration（[M]e） via in situ FTIR spectroscopy in combination with a diamond tipped attenuated total reflectance（ATR） immersion probe. The polymerization rate was first order with respect to monomer concentration and initiator concentration from the linear slope of ln（[M]0-[M]e）/（[M]-[M]e） versus polymerization time at different temperatures in various solvents. [M]e decreased linearly with initial monomer concentration while increased exponentially with increasing polymerization temperature. The equilibrium also strongly depends on solvent polarity and its interaction with monomer. The equilibrium polymerization time（te） decreased with increasing solvent polarity and decreased linearly with increasing [M]0 in three solvents with different slopes to the same point of bulk polymerization in the absence of solvent. Equation of Mn,e = 72.1/（0.14–0.04[M]e） has been established to provide a simple and effective approach for the prediction for the number-average molecular weight of poly THFs at equilibrium state（Mn,e） in the equilibrium living cationic ring-opening polymerization of THF at 0 °C.展开更多
A general protocol was described for fabricating uniform molecularly imprinted polymer （MIP） particles via controlled living radical precipitation polymerization at ambient temperature. By adopting glutathione as mo...A general protocol was described for fabricating uniform molecularly imprinted polymer （MIP） particles via controlled living radical precipitation polymerization at ambient temperature. By adopting glutathione as model template, benzyl dithiocarbamate as iniferter agent, 4-vinylpyridine as monomer, and ethylene glycol dimethacrylate as cross-linker, it is demonstrated that the polymerization parameters including the iniferter concentration, monomer loading and molar ratio of cross-linker to functional monomer have profound effect on the final particle size and recognition property of the MIP particles. The batch static binding experiments were carried out to estimate the adsorption kinetics, adsorption isotherms and selective recognition of the MIP particles. The adsorption behavior followed the pseudo-second order kinetic model, revealing that the process was chemically carried out. Two adsorption isotherm models were applied to analyze equilibrium data, obtaining the best description by Langmuir isotherm model. In addition, the MIP particles also could selectively recognize glutathione over similar analogs, indicating the possibility for the separation and enrichment of the template from complicated matrices.展开更多
Three-arm and four-arm star-like polybutadienes （PBds） were synthesized via the combination of living anionic polymerization and the click coupling method. Kinetic study showed that the click reaction between the az...Three-arm and four-arm star-like polybutadienes （PBds） were synthesized via the combination of living anionic polymerization and the click coupling method. Kinetic study showed that the click reaction between the azido group terminated PBd-t-N3 and the alkyne-containing multifunctional linking reagent was fast and highly efficient. All coupling reactions were fully accomplished within 40 min at 50 ℃ in toluene in the presence of the reducing agent Cu（0）, proven by 1H-NMR, FTIR and GPC measurements. For the coupling reactions between the PBd-t-N3 polymer and dialkyne-containing compound, the final conversion of the coupled PBd-PBd polymer was ca. 97.0%. When a PBd-t-N3 polymer was reacted with trialkyne-containing or tetraalkyne-containing compound, the conversion of three-arm or four-arm PBd was around 95.5% or 87.0%, respectively. Several factors influencing the coupling efficiency were studied, including the molecular weight of the initial PBd-t-N3, arm numbers and the molar ratio of the azido group to the alkynyl group. The results indicated that the conversion of the target products would be promoted when the molecular weight of the PBd-t-N3 was low and the molar ratio of the azido to alkynyl groups was close to 1.展开更多
Random and block copolymers of 2-methoxyethyl vinyl ether(MOVE)and 2-ethoxyethyl vinyl ether(EOVE)were synthesized within 180 s via IBVE-HCl/SnCl_(4) initiating system in the presence of THF in a microflow system.The ...Random and block copolymers of 2-methoxyethyl vinyl ether(MOVE)and 2-ethoxyethyl vinyl ether(EOVE)were synthesized within 180 s via IBVE-HCl/SnCl_(4) initiating system in the presence of THF in a microflow system.The polymers can be produced continuously and efficiently with extremely narrow molecular weight distributions(M_(w)/M_(n)=1.09-1.18)even at the existence of pendant oxyethylene units Polymerization rate can be accelerated by reducing THF to very low concentration([THF]=50 mmol/L),reaching conversions over 60%and 70%in 60 s for EOVE and MOVE,respectively.Random copolymers poly(MOVE_(100x)-r-EOVE(_(100)(1-x)))(x=0.25,0.5,0.75)experienced very sensitive phase separation process,of which phase separation temperature(T_(ps))can be adjusted between 20 and 70℃by controlling monomer composition.On the other hand,thermally induced phase separation of diblock copolymers poly(MOVE_(100)-b-EOVE_(100))was not so sensitive as its random copolymer counterpart.Relatively bigger difference between phase separation temperatures of heating and cooling process(ΔT_(ps))was found for diblock copolymer.展开更多
In this work, a fluorescent monomer 2-（9-carbazolyl） ethyl vinyl ether（CEVE） was synthesized in our lab, and its photo-induced living cationic copolymerization behavior with isobutyl vinyl ether（IBVE） was invest...In this work, a fluorescent monomer 2-（9-carbazolyl） ethyl vinyl ether（CEVE） was synthesized in our lab, and its photo-induced living cationic copolymerization behavior with isobutyl vinyl ether（IBVE） was investigated in detail using diphenyliodonium chloride（DPICl）/2,2-dimethoxy-2-phenylacetophenone（DMPA） and zinc bromide（Zn Br2） initiating system in dichloromethane solution at 5 °C, -5 °C, and -15 °C, respectively. The living nature of this copolymerization system was confirmed by adding fresh comonomer method after the copolymerization almost finished. In addition, the obtained fluorescent copolymer poly（IBVE-co-CEVE） has a low glass transition temperature（Tg）, below -10 °C.展开更多
For living anionic polymerization(LAP),solvent has a great influence on both reaction mechanism and kinetics.In this work,by using the classical butyl lithium-styrene polymerization as a model system,the effect of sol...For living anionic polymerization(LAP),solvent has a great influence on both reaction mechanism and kinetics.In this work,by using the classical butyl lithium-styrene polymerization as a model system,the effect of solvent on the mechanism and kinetics of LAP was revealed through a strategy combining density functional theory(DFT)calculations and kinetic modeling.In terms of mechanism,it is found that the stronger the solvent polarity,the more electrons transfer from initiator to solvent through detailed energy decomposition analysis of electrostatic interactions between initiator and solvent molecules.Furthermore,we also found that the stronger the solvent polarity,the higher the monomer initiation energy barrier and the smaller the initiation rate coefficient.Counterintuitively,initiation is more favorable at lower temperatures based on the calculated results ofΔG_(TS).Finally,the kinetic characteristics in different solvents were further examined by kinetic modeling.It is found that in benzene and n-pentane,the polymerization rate exhibits first-order kinetics.While,slow initiation and fast propagation were observed in tetrahydrofuran(THF)due to the slow free ion formation rate,leading to a deviation from first-order kinetics.展开更多
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 b...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/AIMe(BHT)_(2)(Pylide-2=Ph_(3)P=CHMe and BHT=2,6-iBu_(2)-4-MeC_(6)H_(2)O) was demonstrated to be superior by which homopolymers PAMAs(M_(n)=27.6-111.5kg/mol and ■=1.14-1.25) and PVMAs(M_(n)=28.4-78.4 kg/mol and ■=1.12-1.18) and block copolymers PMMA-b-PAMA,PAMA-b-PVMA,PAMA-bPMMA,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 PhCH_(2)SH.The thiolether side group-containing polymers PAMA-SCH_(2)Ph and PAMA-SCH_(2)Ph-b-PMMA-b-PAMA-SCH_(2)Ph were thus prepared.展开更多
A novel acrylate inimer, 2-（2-chloroacetyloxy） ethyl acrylate, was prepared by the reaction of 2-hydroxyethyl acrylate with chloroacetyl chloride in the presence of triethylamine. The self-condensing vinyl living ra...A novel acrylate inimer, 2-（2-chloroacetyloxy） ethyl acrylate, was prepared by the reaction of 2-hydroxyethyl acrylate with chloroacetyl chloride in the presence of triethylamine. The self-condensing vinyl living radical polymerization of the inimer was studied and the hyperbranched macromolecules containing ester linkages on their backbone were prepared. All the polymerization products were characterized by 1H NMR. The polymerization degree and the branching parameter were calculated based on the 1H NMR spectra. It has been shown that this inimer exhibits a very distinctive polymerization behavior. Similar to step-growth polymerization, the polymerization degree of the products formed increased exponentially during the early stage of the polymerization, and then the increasing rate slowed down. However, the inimer remained present throughout the polymerization consistent with conventional free radical polymerization. Also, if much longer polymerization time was used, the polymerization system would become gel due to the crosslinking reaction derived from radical-radical recombination. As a result of the unequal reactivity of -CH2Cl and >CHCl, an almost linear product was obtained at a molar ratio of bipy to inimer=0.05, while a relatively high ratio of bipy to inimer 1 favored the formation of the branched structure. The macromolecules formed at a high ratio of bipy to inimer 1 exhibited an excellent solubility in organic solvents such as acetone.展开更多
Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene) oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as in...Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene) oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as initiator. Then the PS-CH2CH2OCOCCl3 (PS-Cl-3) or P(S-b-B)-CH2CH2O-COCCl3 (PSB-Cl-3) was used as the macroinitiator in the polymerization of(meth)acrylates in the presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepared by the integrated living anionic polymerization (LAP)-atom transfer radical polymerization (ATRP). The structures of the PSB-Cl-3 and the P(S-b-MMA) were identified by FTIR and H-1-NMR spectrum, respectively. A new way to design block copolymers (the combination of LAP and ATRP) was developed.展开更多
Supramolecular polymerization properties have been studied for a series of perylene bisimide(PBI)dyes containing identical hydrogen-bonding amide groups in imide positions but variable number or size of alkoxy substit...Supramolecular polymerization properties have been studied for a series of perylene bisimide(PBI)dyes containing identical hydrogen-bonding amide groups in imide positions but variable number or size of alkoxy substituents in bay-positions.展开更多
A series of amine-bridged bis(phenolate)rare-earth(Sc,Y)aryloxides was synthesized and characterized.These complexes were successfully used for the controlled Lewis pair polymerization(LPP)of functional acrylamides in...A series of amine-bridged bis(phenolate)rare-earth(Sc,Y)aryloxides was synthesized and characterized.These complexes were successfully used for the controlled Lewis pair polymerization(LPP)of functional acrylamides in combination with phosphines,affording a new type of polyacrylamides with predictable molecular weight and low molecular weight distribution.The living nature of this LPP was verified by near-quantitative initiation efficiencies,a linear increase of molecular weight vs monomer-to-initiator ratio and monomer conversion,chain extensions,and the synthesis of well-defined block copolymers.The mechanistic studies were performed through the isolation of a zwitterionic intermediate as well as the end-chain analysis of oligomers,showcasing a rare-earth/phosphine cooperation.Furthermore,the resultant polyacrylamides exhibit outstanding thermal stability and great potential for application in photovoltaic devices.展开更多
A series of cis-5-norbornene-endo-2,3-dicarboxylic anhydride （NDCA, M1） derivatives （M2-M4） with different types of nonpolar substituted groups were synthesized and characterized by 1H/13C-NMR and mass spectromet...A series of cis-5-norbornene-endo-2,3-dicarboxylic anhydride （NDCA, M1） derivatives （M2-M4） with different types of nonpolar substituted groups were synthesized and characterized by 1H/13C-NMR and mass spectrometry （MS）. Ring- opening metathesis polymerization （ROMP） of these monomers using the Grubbs third generation catalyst （G3） generated high molecular weight polymers with much improved solubility compared with the NDCA＇s homopolymer. It was found that the solubility of these polymers increased with increased substituent＇s steric hindrance. The living polymerization of NDCA derivative containing the bulkiest substituent （M4） catalyzed by G3 in tetrahydrofuran was confirmed by the kinetic studies with low polydispersity indices （PDI） （〈 1.30）. By using sequential ROMP, well-defined diblock copolymers containing anhydride groups were synthesized.展开更多
Mechanistic transformation approach has been widely applied in polymer synthesis due to its unique feature combining structurally different polymers prepared by different polymerization mechanisms.Reported methods for...Mechanistic transformation approach has been widely applied in polymer synthesis due to its unique feature combining structurally different polymers prepared by different polymerization mechanisms.Reported methods for the formation of block and graft copolymers through mechanistic transformation involve almost all polymerizations modes.However,certain polymerization processes require extensive purification processes,which can be time-consuming and problematic.Recent developments on controlled/living polymerizations involving radical and cationic mechanisms with the ability to control molecular weight and functionality led to new pathways for mechanistic transformations.In this mini-review,we systematically discussed relevant advances in the field through three main titles namely(i)from radical to cationic mechanism,(ii)from cationic to radical mechanism,and(iii)application of specific catalyst systems for both radical and cationic polymerizations.展开更多
The precise synthesis of polymer with narrow molecular weight distribution(?)and well-defined architectures is very essential to exploring the functions and properties of polymer materials.Here,a universal polymerizat...The precise synthesis of polymer with narrow molecular weight distribution(?)and well-defined architectures is very essential to exploring the functions and properties of polymer materials.Here,a universal polymerization method capable of low?and reactive hydrogen compatibility is reported by introducing super-Grignard reagents(R_(2)Mg?Li Cl)into polymer chemistry.Under mild conditions,various monomers,including nonpolar polystyrene and 4-methoxystyrene that cannot be initiated by Grignard reagents,and polar methacrylate,are successfully polymerized with full monomer conversion and low?.This approach is amenable to wide varieties of initiators,polymerization temperature,and feed ratio,which makes it attractive for applications in polymer synthesis.By adding methanol and water during the polymerization process,the reactive hydrogen compatibility of this method is confirmed,which makes this method avoid the rigorous restriction on polymerization conditions of anionic polymerization.Moreover,chain extension polymerization and block copolymerization are achieved and demonstrate the livingness of chain propagation,enabling the facile synthesis of well-defined macromolecular architectures.This work therefore expands the methodology libraries of living polymerization,which may cause inspirations to polymer science.展开更多
This paper reports the kinetics of group transfer polymerization (GTP)of ethyl acrylate (EA)with zinc iodide catalyst in 1,2-dichloroethane using dimethyl ketene methyl trimethylsilyl acetal (MTS) as initiator at 0℃ ...This paper reports the kinetics of group transfer polymerization (GTP)of ethyl acrylate (EA)with zinc iodide catalyst in 1,2-dichloroethane using dimethyl ketene methyl trimethylsilyl acetal (MTS) as initiator at 0℃ and above 0℃. The amount of catalyst used was studied. When zinc iodide catalyst used is more than 10mol% relative to monomer, the rate of polymerization is proportional to the concentration of monomer, whereas zinc iodide catalyst used is less than 10 mol% of the monomer, the rate of polymerization is independent of the monomer concentration.In the GTP of EA an induction period was observed when the zinc iodide contents are less than l0mol%. If the reaction temperature is over 0℃, living species become unstable and diminish, leading to incomplete monomer conversion. The reaction curves equations are obtained. The polymers have narrow molecular weight distributions which are not changed as decreasing zinc iodide contents. The polydispersity is about 1.2.展开更多
Bulk polymerizations of styrene (St) were carried out in the presence of three reversible addition fragmentation chain transfer (RAFT) agents benzyl dithiobenzoate (BDB), cumyl dithiobenzoate(CDB), and 1-phenylethyl d...Bulk polymerizations of styrene (St) were carried out in the presence of three reversible addition fragmentation chain transfer (RAFT) agents benzyl dithiobenzoate (BDB), cumyl dithiobenzoate(CDB), and 1-phenylethyl dithiobenzoate (PEDB) under low ratio of RAFT agent to initiator. The kinetic model was developed to predict polymerization rate, which indicates that the RAFT polymerization of St is a first-order reaction. In the range of experimental conversions, the plots of -ln(1-x) against time t are approximately linear (x is monomer conversion). The kinetic study reveals the existence of strong rate retardation in RAFT polymerization of styrene. A coefficient K_r is defined to estimate the rate retardation in the RAFT system considering the assumption that the retardation in polymerization rate is mainly attributed to slow fragmentation of the intermediate radicals. K_r relates to the structure of RAFT agents as well as the concentrations of RAFT agent and azobis isobutyronitrile (AIBN). For a certain RAFT agent, the value of K_r is enhanced by the increase in the initial concentration of RAFT agent and the higher ratio of RAFT to AIBN. With the same recipe for different RAFT agents, the increasing trend for the values of K_r is BDB<PEDB<CDB.展开更多
文摘This feature article summarizes the synthesis of novel olefin block copolymers using fast syndiospecific living homo- and copolymerization of propylene, higher 1-alkene, and norbornene with ansa-fluorenylamidodimethyltitanium- based catalyst according to the authors＇ recent results. The catalytic synthesis of monodisperse polyolefin and olefin block copolymer was also described using this living system.
基金financially supported by the National Natural Science Foundation of China (Nos. 51673057, 21622402, and 21574036)N. Liu thanks Anhui Provincial Natural Science Foundation (No. 1608085MB41)
文摘We report the polymerization of phenyl isocyanides with the chiral palladium（II） initiating system. The resulting polymers with optically active properties were obtained by polymerization of the racemic isocyanide monomer （rac-1）, and enantiomerically unbalanced polymerization of the monomer was found, providing substantial evidence for the enantiomer-selective polymerization of rac- 1 mediated through chiral catalyst. A comparison between the enantiomerically pure monomers, 4-isocyanobenzoyl-L-alanine decyl ester （1 s） and 4-isocyanobenzoyl-D-alanine decyl ester （1 r）, revealed a drastic discrepancy in the reactivity ratio of their homopolymerizations. It turned out that the monomer reactivity ratio of ls was higher than that of lr with chiral ligands. The results clearly demonstrated the inclination for incorporation of the ls enantiomer during the polymerization process and thus resulted in the enantiomer-selective polymerization in this system. The effects of the catalyst chirality on the optically active properties of polymerization were investigated, and it was concluded that the formation of higher-ordered conformation with a handed helicity might be attributed to the chiral induction of chiral palladium（II） catalyst. Moreover, the polymers obtained through the enantiomer-selective polymerization of the enantiomerically pure monomer were with a significant improvement of the optical activity if the chirality of the monomer and the catalyst matched with each other.
基金financially supported by the National Basic Research Program of China(No.2015CB654700)the National Natural Science Foundation of China(No.U1462124)the National Key Technology R&D Program(No.2014BAE14B00)
文摘Half-titanocene complexes bearing dibenzhydryl-substituted aryloxide ligands （2a-2d） were prepared. Among them, 2e adopted a three-legged distorted tetrahedral geometry evidenced by X-ray crystallography. The poly-1,3-butadiene with high molecular weight and narrow molecular weight distribution was obtained by using these complexes as the catalysts activated with methylaluminoxane （MAO）. The catalytic activities of the complexes depended on their structures. The Ti-- O--C bond in the complexes with large angle afforded them with higher activity, while Cp＊-based complexes exhibited lower activities than the Cp-based analogues. The activity of complex increased with increasing the polymerization temperature while the selectivity remained no change, indicating the high thermal stability. Furthermore, the polymerization of 1,3-butadiene catalyzed by 2a/MAO at 0 ℃ has been found in a living fashion.
基金financially supported by the National Natural Science Foundation of China(No.52373011)。
文摘Living cationic polymerization of 4-acetoxystyrene(STO)was conducted in CH_(2)Cl_(2) at-15℃ using a dicumyl chloride(DCC)/SnCl_(4)/nBu_(4)NBr initiating system.Impurity moisture initiation was inhibited by adding proton trap 2,6-di-tert-butylpyridine(DTBP),and the controlled initiation of DCC was confirmed by ^(1)H nuclear magnetic resonance(^(1)H-NMR)spectroscopy and matrix-assisted laser desorption ionization time-offlight mass(MALDI-TOF-MS)spectrometry.The polymerization kinetics were analyzed to for optimizing the polymerization rate.Allyl-telechelic PSTOs(allyl-PSTO-allyl)with molecular weight(Mn)range of 3540–7800 g/mol and narrow molecular weight dispersity(Mw/Mn)about 1.25 were prepared through nucleophilic substitution with allyltrimethylsilane(ATMS)at approximately 40%monomer conversion.The experimental results indicate that the substitution efficiency of ATMS increased with higher ATMS concentration,temperature,and extended reaction time.Nearly unity ally-functionality for allyl-PSTO-allyl was achieved by adding sufficient SnCl_(4) prior to the substitution.
基金financially supported by the National Natural Science Foundation of China(Nos.51173008 and 51221002)
文摘A convenient real-time monitoring of monomer concentration during living cationic ring-opening polymerizations of tetrahydrofuran（THF） initiated with methyl triflate（Me OTf） has been developed for kinetic investigation and determination of equilibrium monomer concentration（[M]e） via in situ FTIR spectroscopy in combination with a diamond tipped attenuated total reflectance（ATR） immersion probe. The polymerization rate was first order with respect to monomer concentration and initiator concentration from the linear slope of ln（[M]0-[M]e）/（[M]-[M]e） versus polymerization time at different temperatures in various solvents. [M]e decreased linearly with initial monomer concentration while increased exponentially with increasing polymerization temperature. The equilibrium also strongly depends on solvent polarity and its interaction with monomer. The equilibrium polymerization time（te） decreased with increasing solvent polarity and decreased linearly with increasing [M]0 in three solvents with different slopes to the same point of bulk polymerization in the absence of solvent. Equation of Mn,e = 72.1/（0.14–0.04[M]e） has been established to provide a simple and effective approach for the prediction for the number-average molecular weight of poly THFs at equilibrium state（Mn,e） in the equilibrium living cationic ring-opening polymerization of THF at 0 °C.
基金financially supported by the National Natural Science Foundation of China(No.21174111)Graduate Starting Seed Fund of Northwestern Polytechnical University(No.Z2013145)
文摘A general protocol was described for fabricating uniform molecularly imprinted polymer （MIP） particles via controlled living radical precipitation polymerization at ambient temperature. By adopting glutathione as model template, benzyl dithiocarbamate as iniferter agent, 4-vinylpyridine as monomer, and ethylene glycol dimethacrylate as cross-linker, it is demonstrated that the polymerization parameters including the iniferter concentration, monomer loading and molar ratio of cross-linker to functional monomer have profound effect on the final particle size and recognition property of the MIP particles. The batch static binding experiments were carried out to estimate the adsorption kinetics, adsorption isotherms and selective recognition of the MIP particles. The adsorption behavior followed the pseudo-second order kinetic model, revealing that the process was chemically carried out. Two adsorption isotherm models were applied to analyze equilibrium data, obtaining the best description by Langmuir isotherm model. In addition, the MIP particles also could selectively recognize glutathione over similar analogs, indicating the possibility for the separation and enrichment of the template from complicated matrices.
基金financially supported by the National Natural Science Foundation of China(Nos.51233005,21004060 and 51073149)
文摘Three-arm and four-arm star-like polybutadienes （PBds） were synthesized via the combination of living anionic polymerization and the click coupling method. Kinetic study showed that the click reaction between the azido group terminated PBd-t-N3 and the alkyne-containing multifunctional linking reagent was fast and highly efficient. All coupling reactions were fully accomplished within 40 min at 50 ℃ in toluene in the presence of the reducing agent Cu（0）, proven by 1H-NMR, FTIR and GPC measurements. For the coupling reactions between the PBd-t-N3 polymer and dialkyne-containing compound, the final conversion of the coupled PBd-PBd polymer was ca. 97.0%. When a PBd-t-N3 polymer was reacted with trialkyne-containing or tetraalkyne-containing compound, the conversion of three-arm or four-arm PBd was around 95.5% or 87.0%, respectively. Several factors influencing the coupling efficiency were studied, including the molecular weight of the initial PBd-t-N3, arm numbers and the molar ratio of the azido group to the alkynyl group. The results indicated that the conversion of the target products would be promoted when the molecular weight of the PBd-t-N3 was low and the molar ratio of the azido to alkynyl groups was close to 1.
基金financially supported by the National Natural Science Foundation of China(Nos.21422603,U1662120 and 21978152)。
文摘Random and block copolymers of 2-methoxyethyl vinyl ether(MOVE)and 2-ethoxyethyl vinyl ether(EOVE)were synthesized within 180 s via IBVE-HCl/SnCl_(4) initiating system in the presence of THF in a microflow system.The polymers can be produced continuously and efficiently with extremely narrow molecular weight distributions(M_(w)/M_(n)=1.09-1.18)even at the existence of pendant oxyethylene units Polymerization rate can be accelerated by reducing THF to very low concentration([THF]=50 mmol/L),reaching conversions over 60%and 70%in 60 s for EOVE and MOVE,respectively.Random copolymers poly(MOVE_(100x)-r-EOVE(_(100)(1-x)))(x=0.25,0.5,0.75)experienced very sensitive phase separation process,of which phase separation temperature(T_(ps))can be adjusted between 20 and 70℃by controlling monomer composition.On the other hand,thermally induced phase separation of diblock copolymers poly(MOVE_(100)-b-EOVE_(100))was not so sensitive as its random copolymer counterpart.Relatively bigger difference between phase separation temperatures of heating and cooling process(ΔT_(ps))was found for diblock copolymer.
基金supported by the National Natural Science Foundation of China(Nos.21174096,21274100 and 21234005)the Project of International Cooperation of the Ministry of Science and Technology of China(No.2011DFA50530)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘In this work, a fluorescent monomer 2-（9-carbazolyl） ethyl vinyl ether（CEVE） was synthesized in our lab, and its photo-induced living cationic copolymerization behavior with isobutyl vinyl ether（IBVE） was investigated in detail using diphenyliodonium chloride（DPICl）/2,2-dimethoxy-2-phenylacetophenone（DMPA） and zinc bromide（Zn Br2） initiating system in dichloromethane solution at 5 °C, -5 °C, and -15 °C, respectively. The living nature of this copolymerization system was confirmed by adding fresh comonomer method after the copolymerization almost finished. In addition, the obtained fluorescent copolymer poly（IBVE-co-CEVE） has a low glass transition temperature（Tg）, below -10 °C.
基金financially supported by the National Natural Science Foundation of China(U21A20313,22222807)。
文摘For living anionic polymerization(LAP),solvent has a great influence on both reaction mechanism and kinetics.In this work,by using the classical butyl lithium-styrene polymerization as a model system,the effect of solvent on the mechanism and kinetics of LAP was revealed through a strategy combining density functional theory(DFT)calculations and kinetic modeling.In terms of mechanism,it is found that the stronger the solvent polarity,the more electrons transfer from initiator to solvent through detailed energy decomposition analysis of electrostatic interactions between initiator and solvent molecules.Furthermore,we also found that the stronger the solvent polarity,the higher the monomer initiation energy barrier and the smaller the initiation rate coefficient.Counterintuitively,initiation is more favorable at lower temperatures based on the calculated results ofΔG_(TS).Finally,the kinetic characteristics in different solvents were further examined by kinetic modeling.It is found that in benzene and n-pentane,the polymerization rate exhibits first-order kinetics.While,slow initiation and fast propagation were observed in tetrahydrofuran(THF)due to the slow free ion formation rate,leading to a deviation from first-order kinetics.
基金financially supported by the National Natural Science Foundation of China (Nos. 21972112 and 22225104)China Postdoctoral Science Foundation (Nos. 2022TQ0115 and 2022M711297)。
文摘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/AIMe(BHT)_(2)(Pylide-2=Ph_(3)P=CHMe and BHT=2,6-iBu_(2)-4-MeC_(6)H_(2)O) was demonstrated to be superior by which homopolymers PAMAs(M_(n)=27.6-111.5kg/mol and ■=1.14-1.25) and PVMAs(M_(n)=28.4-78.4 kg/mol and ■=1.12-1.18) and block copolymers PMMA-b-PAMA,PAMA-b-PVMA,PAMA-bPMMA,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 PhCH_(2)SH.The thiolether side group-containing polymers PAMA-SCH_(2)Ph and PAMA-SCH_(2)Ph-b-PMMA-b-PAMA-SCH_(2)Ph were thus prepared.
基金Supported by the National Natural Science Foundation of China(No. 2 980 40 0 6 ) and the Youth Foundation of Jiangsuprovince(No.BQ980 2 4)
文摘A novel acrylate inimer, 2-（2-chloroacetyloxy） ethyl acrylate, was prepared by the reaction of 2-hydroxyethyl acrylate with chloroacetyl chloride in the presence of triethylamine. The self-condensing vinyl living radical polymerization of the inimer was studied and the hyperbranched macromolecules containing ester linkages on their backbone were prepared. All the polymerization products were characterized by 1H NMR. The polymerization degree and the branching parameter were calculated based on the 1H NMR spectra. It has been shown that this inimer exhibits a very distinctive polymerization behavior. Similar to step-growth polymerization, the polymerization degree of the products formed increased exponentially during the early stage of the polymerization, and then the increasing rate slowed down. However, the inimer remained present throughout the polymerization consistent with conventional free radical polymerization. Also, if much longer polymerization time was used, the polymerization system would become gel due to the crosslinking reaction derived from radical-radical recombination. As a result of the unequal reactivity of -CH2Cl and >CHCl, an almost linear product was obtained at a molar ratio of bipy to inimer=0.05, while a relatively high ratio of bipy to inimer 1 favored the formation of the branched structure. The macromolecules formed at a high ratio of bipy to inimer 1 exhibited an excellent solubility in organic solvents such as acetone.
基金The Project is supported by the National Natural Science Foundation of China (Grant No. 29634010-2), Shanghai Education Development Foundation Shuguang Program (Project SG97008) and Research Institute of Beijing Yanshan Petrochemical Corporation.
文摘Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene) oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as initiator. Then the PS-CH2CH2OCOCCl3 (PS-Cl-3) or P(S-b-B)-CH2CH2O-COCCl3 (PSB-Cl-3) was used as the macroinitiator in the polymerization of(meth)acrylates in the presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepared by the integrated living anionic polymerization (LAP)-atom transfer radical polymerization (ATRP). The structures of the PSB-Cl-3 and the P(S-b-MMA) were identified by FTIR and H-1-NMR spectrum, respectively. A new way to design block copolymers (the combination of LAP and ATRP) was developed.
文摘Supramolecular polymerization properties have been studied for a series of perylene bisimide(PBI)dyes containing identical hydrogen-bonding amide groups in imide positions but variable number or size of alkoxy substituents in bay-positions.
基金supported by National Natural Science Foundation of China(21871204,22371198)Postgraduate Research&Practice Innovation Program of Jiangsu Province。
文摘A series of amine-bridged bis(phenolate)rare-earth(Sc,Y)aryloxides was synthesized and characterized.These complexes were successfully used for the controlled Lewis pair polymerization(LPP)of functional acrylamides in combination with phosphines,affording a new type of polyacrylamides with predictable molecular weight and low molecular weight distribution.The living nature of this LPP was verified by near-quantitative initiation efficiencies,a linear increase of molecular weight vs monomer-to-initiator ratio and monomer conversion,chain extensions,and the synthesis of well-defined block copolymers.The mechanistic studies were performed through the isolation of a zwitterionic intermediate as well as the end-chain analysis of oligomers,showcasing a rare-earth/phosphine cooperation.Furthermore,the resultant polyacrylamides exhibit outstanding thermal stability and great potential for application in photovoltaic devices.
基金financially supported by the National Natural Science Foundation of China(Nos.21234006 and 21574098)
文摘A series of cis-5-norbornene-endo-2,3-dicarboxylic anhydride （NDCA, M1） derivatives （M2-M4） with different types of nonpolar substituted groups were synthesized and characterized by 1H/13C-NMR and mass spectrometry （MS）. Ring- opening metathesis polymerization （ROMP） of these monomers using the Grubbs third generation catalyst （G3） generated high molecular weight polymers with much improved solubility compared with the NDCA＇s homopolymer. It was found that the solubility of these polymers increased with increased substituent＇s steric hindrance. The living polymerization of NDCA derivative containing the bulkiest substituent （M4） catalyzed by G3 in tetrahydrofuran was confirmed by the kinetic studies with low polydispersity indices （PDI） （〈 1.30）. By using sequential ROMP, well-defined diblock copolymers containing anhydride groups were synthesized.
文摘Mechanistic transformation approach has been widely applied in polymer synthesis due to its unique feature combining structurally different polymers prepared by different polymerization mechanisms.Reported methods for the formation of block and graft copolymers through mechanistic transformation involve almost all polymerizations modes.However,certain polymerization processes require extensive purification processes,which can be time-consuming and problematic.Recent developments on controlled/living polymerizations involving radical and cationic mechanisms with the ability to control molecular weight and functionality led to new pathways for mechanistic transformations.In this mini-review,we systematically discussed relevant advances in the field through three main titles namely(i)from radical to cationic mechanism,(ii)from cationic to radical mechanism,and(iii)application of specific catalyst systems for both radical and cationic polymerizations.
基金funding support from National Natural Science Foundation of China(NSFC,Nos.22271286 and 21971236)the Haixi Institute of CAS(No.CXZX-2017-P01)。
文摘The precise synthesis of polymer with narrow molecular weight distribution(?)and well-defined architectures is very essential to exploring the functions and properties of polymer materials.Here,a universal polymerization method capable of low?and reactive hydrogen compatibility is reported by introducing super-Grignard reagents(R_(2)Mg?Li Cl)into polymer chemistry.Under mild conditions,various monomers,including nonpolar polystyrene and 4-methoxystyrene that cannot be initiated by Grignard reagents,and polar methacrylate,are successfully polymerized with full monomer conversion and low?.This approach is amenable to wide varieties of initiators,polymerization temperature,and feed ratio,which makes it attractive for applications in polymer synthesis.By adding methanol and water during the polymerization process,the reactive hydrogen compatibility of this method is confirmed,which makes this method avoid the rigorous restriction on polymerization conditions of anionic polymerization.Moreover,chain extension polymerization and block copolymerization are achieved and demonstrate the livingness of chain propagation,enabling the facile synthesis of well-defined macromolecular architectures.This work therefore expands the methodology libraries of living polymerization,which may cause inspirations to polymer science.
文摘This paper reports the kinetics of group transfer polymerization (GTP)of ethyl acrylate (EA)with zinc iodide catalyst in 1,2-dichloroethane using dimethyl ketene methyl trimethylsilyl acetal (MTS) as initiator at 0℃ and above 0℃. The amount of catalyst used was studied. When zinc iodide catalyst used is more than 10mol% relative to monomer, the rate of polymerization is proportional to the concentration of monomer, whereas zinc iodide catalyst used is less than 10 mol% of the monomer, the rate of polymerization is independent of the monomer concentration.In the GTP of EA an induction period was observed when the zinc iodide contents are less than l0mol%. If the reaction temperature is over 0℃, living species become unstable and diminish, leading to incomplete monomer conversion. The reaction curves equations are obtained. The polymers have narrow molecular weight distributions which are not changed as decreasing zinc iodide contents. The polydispersity is about 1.2.
文摘Bulk polymerizations of styrene (St) were carried out in the presence of three reversible addition fragmentation chain transfer (RAFT) agents benzyl dithiobenzoate (BDB), cumyl dithiobenzoate(CDB), and 1-phenylethyl dithiobenzoate (PEDB) under low ratio of RAFT agent to initiator. The kinetic model was developed to predict polymerization rate, which indicates that the RAFT polymerization of St is a first-order reaction. In the range of experimental conversions, the plots of -ln(1-x) against time t are approximately linear (x is monomer conversion). The kinetic study reveals the existence of strong rate retardation in RAFT polymerization of styrene. A coefficient K_r is defined to estimate the rate retardation in the RAFT system considering the assumption that the retardation in polymerization rate is mainly attributed to slow fragmentation of the intermediate radicals. K_r relates to the structure of RAFT agents as well as the concentrations of RAFT agent and azobis isobutyronitrile (AIBN). For a certain RAFT agent, the value of K_r is enhanced by the increase in the initial concentration of RAFT agent and the higher ratio of RAFT to AIBN. With the same recipe for different RAFT agents, the increasing trend for the values of K_r is BDB<PEDB<CDB.
