The hydroxyl-terminated polybutadiene （HTPB） possessing high content of 1,4-units was synthesized by anionic polymerization of butadiene, using alkyllithium containing silicon-protected hydroxyl group as initiator a...The hydroxyl-terminated polybutadiene （HTPB） possessing high content of 1,4-units was synthesized by anionic polymerization of butadiene, using alkyllithium containing silicon-protected hydroxyl group as initiator and cyclohexane as solvent. The polymers were characterized by GPC, IR and 1H-NMR. The mechanical properties of cured films were also evaluated. The results show that the content of 1,4-units for HTPBs made by anionic polymerization reaches up to 90%. The molecular weight distribution is very narrow （〈 1.05）. The functionality of hydroxyl groups approaches 2. Compared with free radical HTPB, the elongation at break of anionic HTPB films increased by 70%, while the tensile strength remained nearly unchanged. This new HTPB can be very useful in solid propellant.展开更多
A series of 3-arm ABC and AA＇B and 4-arm ABCD, AA＇BC and AA＇A＂B heteroarm star polymers comprising one poly（4-methylphenyl vinyl sulfoxide） segment and other segments such as polystyrene, poly（a-methylstyrene）...A series of 3-arm ABC and AA＇B and 4-arm ABCD, AA＇BC and AA＇A＂B heteroarm star polymers comprising one poly（4-methylphenyl vinyl sulfoxide） segment and other segments such as polystyrene, poly（a-methylstyrene）, poly（4-methoxystyrene） and poly（4-trimethylsilylstyrene） were synthesized by living anionic polymerization based on diphenylethylene （DPE） chemistry. The DPE-functionalized polymers were synthesized by iterative methodology, and the objective star polymers were prepared by two distinct methodologies based on anionic polymerization using DPE-functionalized polymers. The first methodology involves an addition reaction of living anionic polymer with excess DPE-functionalized polymer and a subsequent living anionic polymerization of 4-methylphenyl vinyl sulfoxide （MePVSO） initiated from the in situ formed polymer anion with two or three polymer segments. The second methodology comprises an addition reaction of DPE-functionalized polymer with excess sec-BuLi and a following anionic polymerization of MePVSO initiated from the in situ formed polymer anion and 3-methyl-1,1-diphenylpentyl anion as well. Both approaches could afford the target heteroarm star polymers with predetermined molecular weight, narrow molecular weight distribution （Mw/Mn 〈 1.03） and desired composition, evidenced by SEC, 1H-NMR and SLS analyses. These polymers can be used as model polymers to investigate structure-property relationships in heteroarm star polymers.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
Copolymers of 1,3-butadiene and p-methylstyrene （p-MS） were synthesized via anionic polymerization. A benzophenone-potassium complex was added to tune the reactivity ratio of the two monomers, leading to random and ...Copolymers of 1,3-butadiene and p-methylstyrene （p-MS） were synthesized via anionic polymerization. A benzophenone-potassium complex was added to tune the reactivity ratio of the two monomers, leading to random and gradient composition alonglthe copolymer chain. The overall composition and microstructure could be controlled and well characterized by GPC and H-NMR. The p-MS was distributed from gradient to random with increasing the content of the benzophenone-potassium complex, and the 1,2-microstrucmre in the polybutadiene sequence increased at the same time. The hydrogenation of the copolymer of 1,3-butadiene and p-MS resulted in the corresponding saturated copolymer with well- defined structure and narrow molecular weight distribution.展开更多
Thermal,mechanical,and viscoelastic properties of polybutadiene-based rubber materials are highly dependent on polybutadiene microstructure.The use of polar modifier in association with alkyllithium is a well-known me...Thermal,mechanical,and viscoelastic properties of polybutadiene-based rubber materials are highly dependent on polybutadiene microstructure.The use of polar modifier in association with alkyllithium is a well-known method to obtain polybutadiene with a high vinyl con tent.Another approach is to use bimetallic initiating species such as alkyllithium combined to heavier alkali metal alkoxide(RONa,ROK...).The polymerization control is n evertheless not achieved and several parameters were found to influe nee it.Using bimetallic in itiating systems based on alkyllithium and a potassium alkoxide,alkyllithium structure,initiator preformation time,and initiator composition were identified as parameters influencing the anionic polymerization process of butadiene and/or polybutadiene microstructure.In addition,the use of trimetallic systems based on alkyllithium,potassium alkoxide,and alkylaluminum was investigated in order to prevent side reactions regardless of the[K]/[Li]ratio and of the initiator preformation time.展开更多
Lithium amides have been proved to be effective anionic initiators for the anionic polymerization of acrylonitrile to get high molecular weight polyacrylonitrile in this study. Polyacrylonitrile with weightaverage mol...Lithium amides have been proved to be effective anionic initiators for the anionic polymerization of acrylonitrile to get high molecular weight polyacrylonitrile in this study. Polyacrylonitrile with weightaverage molecular weight ranging from 1.02 × 10~6 g/mol to 1.23 ×10~6 g/mol (M_w/M_n= 1.9-2.2) could be prepared utilizing lithium amides derived from diisopropylamine, diethylamine, hexamethyldisilazane,dicyclohexylamine, and 2,2,6,6-tetramethylpiperidine as initiators. The polymerization of acrylonitrile proceeded in a homogeneous manner in N,N-di methyl for mamide and insignificant contribution of side reactions was confirmed.展开更多
Anionic polyacrylamide dispersions were prepared by dispersion polymerization in an aqueous salt medium, using acrylamide（AM） and acrylic acid（AA） as monomers and anionic polyelectrolytes as stabilizer. Effects of...Anionic polyacrylamide dispersions were prepared by dispersion polymerization in an aqueous salt medium, using acrylamide（AM） and acrylic acid（AA） as monomers and anionic polyelectrolytes as stabilizer. Effects of salt concentration, and molecular weight and concentration of stabilizers on the stability of the dispersions were investigated using a HAAKE rheometer and optical microscopy. The results showed that stable anionic polyacrylamide dispersions, consisting of smooth, spherical, polydisperse particles, could be obtained under the conditions of salt concentration ranging from 26 wt% to 30 wt%, concentration of stabilizers from 1.2 wt% to 1.8 wt%, and intrinsic viscosity of stabilizers from 2.98 dL·g^-1 to 3.74 dL·g^-1. The apparent viscosity of the stable dispersions changed very little with the shear rate, showing Newton fluid behavior.展开更多
Janus polymerization is featured as a combination of cationic and anionic growing ends in one living polymer chain. In the copolymerization of THF and CL catalyzed by lutetium triflates and initiated by propylene oxid...Janus polymerization is featured as a combination of cationic and anionic growing ends in one living polymer chain. In the copolymerization of THF and CL catalyzed by lutetium triflates and initiated by propylene oxide, three stages are identified by kinetic study including(1) fast cationic polymerization with slow anionic one,(2) fast anionic polymerization with dormant cationic one, and(3)reactivation of cationic polymerization with coupling of anionic and cationic chain ends. In this work, density functional theory(DFT)calculation is employed to investigate the reaction details of ionic polymerization and dormancy. A “tripedal crow” configuration is proposed to illustrate the unique high-coordinated ligand exchange configuration in anionic polymerization in different stages. The trigger of dormancy is determined as chain structures rather than concentration of triflate anion according to both calculation and experimental results.展开更多
The anionic polymerization of N-vinylcarbazole（NVC） by using optically active anionic initiators such as the lithium salts of（S）-1-（9H-fluoren-2-yl）-4-isopropyl-4,5-dihydrooxazole（（S）-1-FIDH） and（S）-2-（9H...The anionic polymerization of N-vinylcarbazole（NVC） by using optically active anionic initiators such as the lithium salts of（S）-1-（9H-fluoren-2-yl）-4-isopropyl-4,5-dihydrooxazole（（S）-1-FIDH） and（S）-2-（9H-fluoren-2-yl）-4-isopropyl-4,5-dihydrooxazole（（S）-2-FIDH） and complexes of（-）-Sparteine with n-butylithium（n-Bu Li-（-）-Sp） or fluorenyl lithium（FILi-（-）-Sp） was achieved. The yield and specific rotation of poly（N-vinylcarbazole）s（poly（NVC）s） were considerably affected by the molar ratio of（S）-FIDH to NVC. The highest yield and specific rotation were obtained with Li-（S）-1-FIDH as an initiator, with a molar ratio of monomer and initiator [M]/[I] = 10/1. The effects of the chiral initiators, type of solvent and the polymerization temperature were investigated. The obtained optical activity of polymers was attributed to asymmetric induction of the chiral initiators.展开更多
Star-branched polyamide 6 was prepared via anionic ring-opening polymerization of ε-caprolactam in the presence of a simple benzene-centered trifunctional activator of N,N＇,N＂-trimesoyltricaprolactam. A high polyme...Star-branched polyamide 6 was prepared via anionic ring-opening polymerization of ε-caprolactam in the presence of a simple benzene-centered trifunctional activator of N,N＇,N＂-trimesoyltricaprolactam. A high polymer yields of above 95% were achieved at 160 ℃ for 15 min utilizing ε-caprolactam magnesium bromide as a catalyst. Compared with its linear counterpart, the resultant star-branched polyamide 6 showed smaller relative viscosity （1.51 ）, decreased melting temperature （218 ℃） and lower crystallinity （24.2%）. The specific properties demonstrated the existence of a star-branched structure and provided potential advantages in engineering applications.展开更多
In this paper, (-)menthyl methacrylate((-)MnMA) was polymerized at 78C in toluene with three types of anionic catalysts, which were complexes of fluorenyllithium with (-)sparteine - ((-)-Sp) , (S, S)-(+)-2, 3-dimethox...In this paper, (-)menthyl methacrylate((-)MnMA) was polymerized at 78C in toluene with three types of anionic catalysts, which were complexes of fluorenyllithium with (-)sparteine - ((-)-Sp) , (S, S)-(+)-2, 3-dimethoxy-1, 4-bis(dimethylamino)butane((+)DDB) and N,N,N,N-tetra- methylethylenediamine(TMEDA), and the chiral optical property of the obtained polymer was studied. The circular dichroism (CD) spectrum of the polymer showed negative Cotton effect.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
The kinetic study of the anionic polymerization of isoprene is carried out in tetrahy-drofuran(THF), using n-BuLi as initiator. Kinetic parameters are obtained, which comprise chain propagation rate constant, kp, and ...The kinetic study of the anionic polymerization of isoprene is carried out in tetrahy-drofuran(THF), using n-BuLi as initiator. Kinetic parameters are obtained, which comprise chain propagation rate constant, kp, and partial rate constants, k3 and k4 + k5, propagation orders with respect to monomer and active species concentrations, α and β, real activation energy, E, as well as partial activation energies, E3 and E4+5 and so on. The relationship between the microstruc-ture of polyisoprene and the ratio of [THF]/[n-BuLi] has been investigated. On the basis of the studies mentioned above, a reasonable mechanism of the anionic polymerization of isoprene in THF is proposed.展开更多
20 wt% polyamide 12 （PA1212） pellets were dissolved in molten caprolactam. The caprolactam was then catalyzed at 180℃ and polymerized by means of anionic ring-opening polymerization to produce in situ blends of the...20 wt% polyamide 12 （PA1212） pellets were dissolved in molten caprolactam. The caprolactam was then catalyzed at 180℃ and polymerized by means of anionic ring-opening polymerization to produce in situ blends of the resultant polyamide 6 （PA6） and PA 1212. Mechanical blends with same ingredient were prepared through melt blending on a twin-screw extruder. Scanning electron microscopy （SEM） observation revealed that contrary to the mechanical blends with small spherulites embedded in the matrix, no phase-separation existed in the in situ blends. The results of thermal analysis by differential scanning calorimetry （DSC） showed that single melting peak and crystallization peak existed for the in situ blends, while two melting and crystallization peaks appeared for the mechanical blends. The in situ blend film and the mixed blend film, both cast from a dilute formic acid solution with a concentration of 0.5 g/L, remained similar crystallization and melting behavior as above. It is proved by solution 13C-NMR analysis that transamidation took place during the in situ blending, and it is suggested that the combination of temperature increasing and the basic surrounding derived from NaOH during polymerization resulted in the occurrence of transamidation. Furthermore, it is proposed that the interchange reaction between PA 1212 and PA6 also resulted from the degradative reaction during the anionic polymerization.展开更多
A star-shaped multifunctional styrene-isoprene copolymer was synthesized with n-BuLi as initiator, divinyl benzene as coupling agent, cyclobexane as solvent by living anionic polymerization. Using this polymer as graf...A star-shaped multifunctional styrene-isoprene copolymer was synthesized with n-BuLi as initiator, divinyl benzene as coupling agent, cyclobexane as solvent by living anionic polymerization. Using this polymer as grafting agent, a novel star-shaped branched polymer, containing several polyisobutylene, was prepared via cationic ~aolymerization. The star PS-b-PI and star-branched polyisobutylene were characterized by GPC, ＇HNMR and FT-IR, and the effects of different adding order and the amount of grafting agent were investigated.展开更多
A simple new method for the syntheses of a highly soluble noncross linked C 60 styrene copolymers by means of lithium camphor initiated anionic polymerization reaction is demonstrated.
Anionic polymerization of methyl methacrylate (MMA), n-butyl methacrylate (nBMA) and glycidyl methacrylate (GMA) initiated by nBuCu(NCy2)Li (1) in tetrahydrofuran (THF) at -50 degrees C to -10 degrees C was investigat...Anionic polymerization of methyl methacrylate (MMA), n-butyl methacrylate (nBMA) and glycidyl methacrylate (GMA) initiated by nBuCu(NCy2)Li (1) in tetrahydrofuran (THF) at -50 degrees C to -10 degrees C was investigated. It was found that the polymerization of MMA and nBMA initiated by 1 proceeded quantitatively in THF to afford PMMA and PBMA with polydispersity index 1.15-1.30 and nearly 100% initiator efficiencies at -10 degrees C. The molecular weights increased linearly with the ratio of [monomer]/[1]. However, a post-polymerization experiment carried out on this system revealed a double polymer peak by GPC when fresh monomer was added after an interval of 10 min. Polymerization of styrene could be initiated by 1, but the initiator efficiency was low.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
A new cyclic monomer, 2-methyl-2-methocycarbonyl-5-methylene 1,3-dioxlan-4-one,wassynthesized successfully. The monomer and intermediate were characterized by ~1H NMR,^(13)C NMR, INEPT (Intensive Nuclei Enhanced by Po...A new cyclic monomer, 2-methyl-2-methocycarbonyl-5-methylene 1,3-dioxlan-4-one,wassynthesized successfully. The monomer and intermediate were characterized by ~1H NMR,^(13)C NMR, INEPT (Intensive Nuclei Enhanced by Polarization Transfer) technique, IR andelemental analysis. Anionic polymerization of the monomer was carried out in anhydrous THF at.70℃, and 9-fluorenyllithium was used as initiator. The polymer strucure was determined byIR, NMR and elemental analysis. Molecular weight of the polymer was estimated by viscositymeasurement in DMSO at 30℃.展开更多
Some chiral binaphthyl crown ethers were synthesized. The anionic polymerization of methyl methacrylate (MMA) was carried out in the presence of t-BuOK, Ph2CHK or Ph2CHNa (RM), and RM coordination initiator by using c...Some chiral binaphthyl crown ethers were synthesized. The anionic polymerization of methyl methacrylate (MMA) was carried out in the presence of t-BuOK, Ph2CHK or Ph2CHNa (RM), and RM coordination initiator by using chiral binaphthyl crown ethers as ligands, respectively. The results showed that in the former case the PMMA obtained has mainly isotactic structure but without optical activity, while in the later case the PMMA produced predominately has syndiotactic structure also without optical activity.展开更多
文摘The hydroxyl-terminated polybutadiene （HTPB） possessing high content of 1,4-units was synthesized by anionic polymerization of butadiene, using alkyllithium containing silicon-protected hydroxyl group as initiator and cyclohexane as solvent. The polymers were characterized by GPC, IR and 1H-NMR. The mechanical properties of cured films were also evaluated. The results show that the content of 1,4-units for HTPBs made by anionic polymerization reaches up to 90%. The molecular weight distribution is very narrow （〈 1.05）. The functionality of hydroxyl groups approaches 2. Compared with free radical HTPB, the elongation at break of anionic HTPB films increased by 70%, while the tensile strength remained nearly unchanged. This new HTPB can be very useful in solid propellant.
基金supported by the National Natural Science Foundation of China(Nos.20844001 and 20874067)the Key Project of Chinese Ministry of Education(No.209049)Natural Science Fund for Colleges and Universities of Jiangsu Province(No.08KJB150015).
文摘A series of 3-arm ABC and AA＇B and 4-arm ABCD, AA＇BC and AA＇A＂B heteroarm star polymers comprising one poly（4-methylphenyl vinyl sulfoxide） segment and other segments such as polystyrene, poly（a-methylstyrene）, poly（4-methoxystyrene） and poly（4-trimethylsilylstyrene） were synthesized by living anionic polymerization based on diphenylethylene （DPE） chemistry. The DPE-functionalized polymers were synthesized by iterative methodology, and the objective star polymers were prepared by two distinct methodologies based on anionic polymerization using DPE-functionalized polymers. The first methodology involves an addition reaction of living anionic polymer with excess DPE-functionalized polymer and a subsequent living anionic polymerization of 4-methylphenyl vinyl sulfoxide （MePVSO） initiated from the in situ formed polymer anion with two or three polymer segments. The second methodology comprises an addition reaction of DPE-functionalized polymer with excess sec-BuLi and a following anionic polymerization of MePVSO initiated from the in situ formed polymer anion and 3-methyl-1,1-diphenylpentyl anion as well. Both approaches could afford the target heteroarm star polymers with predetermined molecular weight, narrow molecular weight distribution （Mw/Mn 〈 1.03） and desired composition, evidenced by SEC, 1H-NMR and SLS analyses. These polymers can be used as model polymers to investigate structure-property relationships in heteroarm star polymers.
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the National Natural Science Foundation of China(Nos.51073149 and 51233005)
文摘Copolymers of 1,3-butadiene and p-methylstyrene （p-MS） were synthesized via anionic polymerization. A benzophenone-potassium complex was added to tune the reactivity ratio of the two monomers, leading to random and gradient composition alonglthe copolymer chain. The overall composition and microstructure could be controlled and well characterized by GPC and H-NMR. The p-MS was distributed from gradient to random with increasing the content of the benzophenone-potassium complex, and the 1,2-microstrucmre in the polybutadiene sequence increased at the same time. The hydrogenation of the copolymer of 1,3-butadiene and p-MS resulted in the corresponding saturated copolymer with well- defined structure and narrow molecular weight distribution.
文摘Thermal,mechanical,and viscoelastic properties of polybutadiene-based rubber materials are highly dependent on polybutadiene microstructure.The use of polar modifier in association with alkyllithium is a well-known method to obtain polybutadiene with a high vinyl con tent.Another approach is to use bimetallic initiating species such as alkyllithium combined to heavier alkali metal alkoxide(RONa,ROK...).The polymerization control is n evertheless not achieved and several parameters were found to influe nee it.Using bimetallic in itiating systems based on alkyllithium and a potassium alkoxide,alkyllithium structure,initiator preformation time,and initiator composition were identified as parameters influencing the anionic polymerization process of butadiene and/or polybutadiene microstructure.In addition,the use of trimetallic systems based on alkyllithium,potassium alkoxide,and alkylaluminum was investigated in order to prevent side reactions regardless of the[K]/[Li]ratio and of the initiator preformation time.
文摘Lithium amides have been proved to be effective anionic initiators for the anionic polymerization of acrylonitrile to get high molecular weight polyacrylonitrile in this study. Polyacrylonitrile with weightaverage molecular weight ranging from 1.02 × 10~6 g/mol to 1.23 ×10~6 g/mol (M_w/M_n= 1.9-2.2) could be prepared utilizing lithium amides derived from diisopropylamine, diethylamine, hexamethyldisilazane,dicyclohexylamine, and 2,2,6,6-tetramethylpiperidine as initiators. The polymerization of acrylonitrile proceeded in a homogeneous manner in N,N-di methyl for mamide and insignificant contribution of side reactions was confirmed.
文摘Anionic polyacrylamide dispersions were prepared by dispersion polymerization in an aqueous salt medium, using acrylamide（AM） and acrylic acid（AA） as monomers and anionic polyelectrolytes as stabilizer. Effects of salt concentration, and molecular weight and concentration of stabilizers on the stability of the dispersions were investigated using a HAAKE rheometer and optical microscopy. The results showed that stable anionic polyacrylamide dispersions, consisting of smooth, spherical, polydisperse particles, could be obtained under the conditions of salt concentration ranging from 26 wt% to 30 wt%, concentration of stabilizers from 1.2 wt% to 1.8 wt%, and intrinsic viscosity of stabilizers from 2.98 dL·g^-1 to 3.74 dL·g^-1. The apparent viscosity of the stable dispersions changed very little with the shear rate, showing Newton fluid behavior.
基金financially supported by the National Natural Science Foundation of China (No. 21871232)the Zhejiang Provincial Natural Science Foundation of China (No. LR15B040001)
文摘Janus polymerization is featured as a combination of cationic and anionic growing ends in one living polymer chain. In the copolymerization of THF and CL catalyzed by lutetium triflates and initiated by propylene oxide, three stages are identified by kinetic study including(1) fast cationic polymerization with slow anionic one,(2) fast anionic polymerization with dormant cationic one, and(3)reactivation of cationic polymerization with coupling of anionic and cationic chain ends. In this work, density functional theory(DFT)calculation is employed to investigate the reaction details of ionic polymerization and dormancy. A “tripedal crow” configuration is proposed to illustrate the unique high-coordinated ligand exchange configuration in anionic polymerization in different stages. The trigger of dormancy is determined as chain structures rather than concentration of triflate anion according to both calculation and experimental results.
基金financially supported by the open project program of Key Laboratory of Environmentally Friendly ChemistryApplications of the Ministry of Education,China(No.09HJYH04)Xiangtan University Doctoral Scientific Research Fund
文摘The anionic polymerization of N-vinylcarbazole（NVC） by using optically active anionic initiators such as the lithium salts of（S）-1-（9H-fluoren-2-yl）-4-isopropyl-4,5-dihydrooxazole（（S）-1-FIDH） and（S）-2-（9H-fluoren-2-yl）-4-isopropyl-4,5-dihydrooxazole（（S）-2-FIDH） and complexes of（-）-Sparteine with n-butylithium（n-Bu Li-（-）-Sp） or fluorenyl lithium（FILi-（-）-Sp） was achieved. The yield and specific rotation of poly（N-vinylcarbazole）s（poly（NVC）s） were considerably affected by the molar ratio of（S）-FIDH to NVC. The highest yield and specific rotation were obtained with Li-（S）-1-FIDH as an initiator, with a molar ratio of monomer and initiator [M]/[I] = 10/1. The effects of the chiral initiators, type of solvent and the polymerization temperature were investigated. The obtained optical activity of polymers was attributed to asymmetric induction of the chiral initiators.
基金supported by a grant from the National High Technology Research and Development Program of China(No.2014AA021201)the National Basic Research Program of China(No.2012CB721104)+1 种基金China Postdoctoral Science Foundation(No.2014M551574)the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Star-branched polyamide 6 was prepared via anionic ring-opening polymerization of ε-caprolactam in the presence of a simple benzene-centered trifunctional activator of N,N＇,N＂-trimesoyltricaprolactam. A high polymer yields of above 95% were achieved at 160 ℃ for 15 min utilizing ε-caprolactam magnesium bromide as a catalyst. Compared with its linear counterpart, the resultant star-branched polyamide 6 showed smaller relative viscosity （1.51 ）, decreased melting temperature （218 ℃） and lower crystallinity （24.2%）. The specific properties demonstrated the existence of a star-branched structure and provided potential advantages in engineering applications.
基金the National Natural Science Foundation of China for financial support
文摘In this paper, (-)menthyl methacrylate((-)MnMA) was polymerized at 78C in toluene with three types of anionic catalysts, which were complexes of fluorenyllithium with (-)sparteine - ((-)-Sp) , (S, S)-(+)-2, 3-dimethoxy-1, 4-bis(dimethylamino)butane((+)DDB) and N,N,N,N-tetra- methylethylenediamine(TMEDA), and the chiral optical property of the obtained polymer was studied. The circular dichroism (CD) spectrum of the polymer showed negative Cotton effect.
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.
文摘The kinetic study of the anionic polymerization of isoprene is carried out in tetrahy-drofuran(THF), using n-BuLi as initiator. Kinetic parameters are obtained, which comprise chain propagation rate constant, kp, and partial rate constants, k3 and k4 + k5, propagation orders with respect to monomer and active species concentrations, α and β, real activation energy, E, as well as partial activation energies, E3 and E4+5 and so on. The relationship between the microstruc-ture of polyisoprene and the ratio of [THF]/[n-BuLi] has been investigated. On the basis of the studies mentioned above, a reasonable mechanism of the anionic polymerization of isoprene in THF is proposed.
基金This work was financially supported by the National Natural Science Foundation of China(No.50373037).
文摘20 wt% polyamide 12 （PA1212） pellets were dissolved in molten caprolactam. The caprolactam was then catalyzed at 180℃ and polymerized by means of anionic ring-opening polymerization to produce in situ blends of the resultant polyamide 6 （PA6） and PA 1212. Mechanical blends with same ingredient were prepared through melt blending on a twin-screw extruder. Scanning electron microscopy （SEM） observation revealed that contrary to the mechanical blends with small spherulites embedded in the matrix, no phase-separation existed in the in situ blends. The results of thermal analysis by differential scanning calorimetry （DSC） showed that single melting peak and crystallization peak existed for the in situ blends, while two melting and crystallization peaks appeared for the mechanical blends. The in situ blend film and the mixed blend film, both cast from a dilute formic acid solution with a concentration of 0.5 g/L, remained similar crystallization and melting behavior as above. It is proved by solution 13C-NMR analysis that transamidation took place during the in situ blending, and it is suggested that the combination of temperature increasing and the basic surrounding derived from NaOH during polymerization resulted in the occurrence of transamidation. Furthermore, it is proposed that the interchange reaction between PA 1212 and PA6 also resulted from the degradative reaction during the anionic polymerization.
文摘A star-shaped multifunctional styrene-isoprene copolymer was synthesized with n-BuLi as initiator, divinyl benzene as coupling agent, cyclobexane as solvent by living anionic polymerization. Using this polymer as grafting agent, a novel star-shaped branched polymer, containing several polyisobutylene, was prepared via cationic ~aolymerization. The star PS-b-PI and star-branched polyisobutylene were characterized by GPC, ＇HNMR and FT-IR, and the effects of different adding order and the amount of grafting agent were investigated.
文摘A simple new method for the syntheses of a highly soluble noncross linked C 60 styrene copolymers by means of lithium camphor initiated anionic polymerization reaction is demonstrated.
基金supported by the National Natural Science Foundation of China(No.20374005)China Petroleum &Chemical Corporation.
文摘Anionic polymerization of methyl methacrylate (MMA), n-butyl methacrylate (nBMA) and glycidyl methacrylate (GMA) initiated by nBuCu(NCy2)Li (1) in tetrahydrofuran (THF) at -50 degrees C to -10 degrees C was investigated. It was found that the polymerization of MMA and nBMA initiated by 1 proceeded quantitatively in THF to afford PMMA and PBMA with polydispersity index 1.15-1.30 and nearly 100% initiator efficiencies at -10 degrees C. The molecular weights increased linearly with the ratio of [monomer]/[1]. However, a post-polymerization experiment carried out on this system revealed a double polymer peak by GPC when fresh monomer was added after an interval of 10 min. Polymerization of styrene could be initiated by 1, but the initiator efficiency was low.
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A new cyclic monomer, 2-methyl-2-methocycarbonyl-5-methylene 1,3-dioxlan-4-one,wassynthesized successfully. The monomer and intermediate were characterized by ~1H NMR,^(13)C NMR, INEPT (Intensive Nuclei Enhanced by Polarization Transfer) technique, IR andelemental analysis. Anionic polymerization of the monomer was carried out in anhydrous THF at.70℃, and 9-fluorenyllithium was used as initiator. The polymer strucure was determined byIR, NMR and elemental analysis. Molecular weight of the polymer was estimated by viscositymeasurement in DMSO at 30℃.
基金This work was supported by the National Natural Science Foundation of China (No. 29974034).
文摘Some chiral binaphthyl crown ethers were synthesized. The anionic polymerization of methyl methacrylate (MMA) was carried out in the presence of t-BuOK, Ph2CHK or Ph2CHNa (RM), and RM coordination initiator by using chiral binaphthyl crown ethers as ligands, respectively. The results showed that in the former case the PMMA obtained has mainly isotactic structure but without optical activity, while in the later case the PMMA produced predominately has syndiotactic structure also without optical activity.
