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
End-functionalization of polydiene rubbers can not only improve its compatibility with inorganic fillers,but also enhance the overall mechanical properties.Nevertheless,for traditional neodymium(Nd)diene polymerizatio...End-functionalization of polydiene rubbers can not only improve its compatibility with inorganic fillers,but also enhance the overall mechanical properties.Nevertheless,for traditional neodymium(Nd)diene polymerization systems,it is highly challenging to achieve such end-functionalizations,because most of polydienyl chains are capped withη3-allyl-Nd moiety during the end of polymerization,which shows very poor reactivity with nucleophile compounds.We launched a new diene polymerization strategy calling coordinative chain transfer polymerization(CCTP)[1].In such a system,all the polydienyl chains are capped withη1-allyl-Al moieties,which reveal greater reactivity with cyclic esters and epoxide compounds,providing an effective manner to prepare polydiene-polyester amphiphilic block copolymers.Inspired by such findings,we now show herein how such types of chain-ends react with isot-hiocyanate to demonstrate an efficient in-situ manner to access end-functionalized polydienes by using CCTP.展开更多
We present a novel generating function(GF)method for the self-condensing vinyl polymerization(SCVP)system with any initial distribution of preexisted polymers.Such a method was proven to be especially useful to invest...We present a novel generating function(GF)method for the self-condensing vinyl polymerization(SCVP)system with any initial distribution of preexisted polymers.Such a method was proven to be especially useful to investigate the semi-batch SCVP system allowing a sequence of feeding operations during the polymerization.Consequently,the number-,weight-,and z-average molecular weights as well as dispersity index of hyperbranched polymers can be explicitly given,which are determined by predetermined feeding details and conversions in each polymerization step.These analytical results are further confirmed by the corresponding Monte Carlo simulations.Therefore,the present GF method has provided a unified treatment to the semi-batch SCVP system.Accordingly,hyperbranched polymers with desired properties can be prepared by designing feeding details and presetting conversions at each step based on the present GF method.展开更多
In recent years,cellulose-based fluorescent polymers have received considerable attention.However,conventional modification methods face challenges such as insolubility in most solvents,fluorescence instability,and en...In recent years,cellulose-based fluorescent polymers have received considerable attention.However,conventional modification methods face challenges such as insolubility in most solvents,fluorescence instability,and environmental risks.In this study,a novel biosynthesis strategy was developed to fabricate fluorescent cellulose by adding fluorescent glucose derivatives to a bacterial fermentation broth.The metabolic activity of bacteria is utilized to achieve in situ polymerization of glucose and its derivatives during the synthesis of bacterial cellulose.Owing to the structural similarity between triphenylamine-modified glucose(TPA-Glc N)and glucose monomers,the TPA-Glc N were efficiently assimilated by the bacterial cells and incorporated into the cellulose matrix,resulting in a uniform distribution of fluorescence.The fluorescence color and intensity of the obtained cellulose could be adjusted by varying the amount of the fluorescent glucose derivatives.Compared to the fluorescent cellulose synthesized through physical dyeing,the fluorescence of the products obtained by in situ polymerization showed higher intensity and stability.Furthermore,fluorescent bacterial cellulose can be hydrolyzed into nanocellulose-based ink,which demonstrates exceptional anti-counterfeiting capabilities under UV light.This biosynthesis method not only overcomes the limitations of traditional modification techniques but also highlights the potential of microbial systems as platforms for synthesizing functional polymers.展开更多
High catalytic efficiencies in ring opening polymerization(ROP)of a large ring-sized macrolactone,ω-pentadecalactone(PDL),by using transition metal Fe(II)-based catalysts were achieved for the first time in this stud...High catalytic efficiencies in ring opening polymerization(ROP)of a large ring-sized macrolactone,ω-pentadecalactone(PDL),by using transition metal Fe(II)-based catalysts were achieved for the first time in this study.Benefited from the bulky nature of the ligatedα-diimine ligands,as evidenced from single-crystal structures,as well as the weakly oxophilic nature of the metal centers,chain transesterification reactions could be partially suppressed,allowing the polymerization proceed in a living-like and semi-controllable manner,i.e.good linear dependence of propagation rates on catalyst concentration and PDL concentration as observed in the detailed kinetics studies.The whole polymerization proceeds via a“coordination-insertion”mechanism,and with the aid of density functional theory(DFT)calculation studies,a“slow insertion→fast elimination”manner was demonstrated for the monomer propagation step,suggesting the insertion of Fe-OR into the carbonyl group C=O as the rate-determining step.The present catalytic system also showed fast chain transfer reactions to alcohol compounds,affording quasi-immortal characteristics.DFT calculations showed that such a transfer reaction only required an energy barrier of 6.4 kcal/mol,performing a good consistency with the fast chain transfer rates.展开更多
Epoxy-terminated hyperbranched polymers （EHBPs） were prepared by proton transfer polymerization and characterized by FT-IR, 1H-NMR and GPC. The solution and thermal properties of the uncured samples and mechanical p...Epoxy-terminated hyperbranched polymers （EHBPs） were prepared by proton transfer polymerization and characterized by FT-IR, 1H-NMR and GPC. The solution and thermal properties of the uncured samples and mechanical properties of cured samples were examined. The thermo-stable products had good solubility in polar solvents, low solution viscosity and Tgs ranging from 15℃ to 33℃ depending on their molecular weights. The mechanical properties of cured films were studied and compared with those of a bisphenol-A type epoxy resin. The films of EHBPs had good impact resistance and high gloss values without sacrificing hardness and adhesion.展开更多
Effects of N-alkyi substituted ethylenediamine derivatives on vinyl polymerization using persulfate as initiator were studied. The apparent kinetic equations and overall activation energies of acrylamide polymerizatio...Effects of N-alkyi substituted ethylenediamine derivatives on vinyl polymerization using persulfate as initiator were studied. The apparent kinetic equations and overall activation energies of acrylamide polymerization were determined using the above mentioned system as initiator. The promoting activities of different diamine derivatives on vinyl polymerization are in the order of tertiary diamine>secondary diamine>primary diamine. Diamines having methyl groups as the substituent on their nitrogen atom possess higher promoting activity than that of having larger alkyl groups. The initial free radicals produced through the redox reaction of persuifate and diamines were studied by spin strapping technique and ESR spectroscopy. The results obtained confirm the fact that the initial free radicals of the diamine species can initiate vinyl polymerization and become the amino end group of the resulting polymers.展开更多
Polynorbornenes were synthesized in the presence of an iron based catalyst, 2,6-bis[1-(2,6-diisopropyl-phenylimino)ethyl]pyridine iron(Ⅱ) dichloride. The FTIR, 1H NMR and 13C NMR analysis results revealed t...Polynorbornenes were synthesized in the presence of an iron based catalyst, 2,6-bis[1-(2,6-diisopropyl-phenylimino)ethyl]pyridine iron(Ⅱ) dichloride. The FTIR, 1H NMR and 13C NMR analysis results revealed that the structure of the obtained polynorbornenes consisted of vinyl addition polymer substructures without any ring-opening structures. The polymers were amorphous with a short-range order, displayed in the WAXD(wide angle X-ray diffraction) diagrams. The glass transition temperatures ranged from 200 to 400 ℃. The effects of the polymerization reaction conditions, such as Al/Fe molar ratio and toluene/CH_2Cl_2 volume ratio, on the activity, intrinsic viscosity and T_g were also studied.展开更多
Investigations show that in monomer water heterogeneous systems polymerization, located in the interface, can disperse the system. Following polymerization in the density gradient field it is shown that in such system...Investigations show that in monomer water heterogeneous systems polymerization, located in the interface, can disperse the system. Following polymerization in the density gradient field it is shown that in such systems latex particles are nucleated from monomer microdroplets, containing a certain amount of polymer molecules. It could be considered that, independently of the nature of the monomer itself, polymerization in monomer water statistic heterogeneous systems modulate emulsion polymerization process.展开更多
Methyl methacrylate (MMA) was polymerized with the rare earth coordination catalyst system of Nd(O? Pr) 3 in toluene. The influences of various ligands in neodymium complexes, molar ratio of Al/Nd, catalyst concent...Methyl methacrylate (MMA) was polymerized with the rare earth coordination catalyst system of Nd(O? Pr) 3 in toluene. The influences of various ligands in neodymium complexes, molar ratio of Al/Nd, catalyst concentration, catalyst aging time, solvents, the third component CCl 4, temperature and time on the polymerization of MMA were studied. The results showed that the polymerization conversion reached more than 80% at a catalyst concentration of 9 2×10 -3 mol/L. The appropriate molar ratio of CCl 4/Nd was 4. Hydrocarbon was preferred for the polymerzation to obtain a high conversion and a high M W of PMMA. The 1H NMR spectra of PMMA indicated that the lower the temperature, the higher the syndiotactic content of PMMA was obtained.展开更多
We report herein the cationic polymerization of isobutylene(IB)under mild conditions is realized with a new binary initiation system generated by simply mixing a Lewis super acid Al(C_(6)F_(5))_(3) and a substituted p...We report herein the cationic polymerization of isobutylene(IB)under mild conditions is realized with a new binary initiation system generated by simply mixing a Lewis super acid Al(C_(6)F_(5))_(3) and a substituted phenol(RPhOH).Polymers with medium and/or high molecular weights(M_(W)=4.9×10^(4)-27.7×10^(4) g·mol^(-1))can be obtained in toluene and temperatures from-20℃to 0℃.NMR spectrum analysis and DFT sim ulation reveals the in situ generated acidic coordinating complex Ak(C_(6)F_(5))_(3)·RPhOH is the initiating active species,which fu rther tran sformed into the ion-pair[Al(C_(6)F_(5))_(3)ORPh]^(-)[PIB]^(+)of the active intermediates upon growing IB monomers where the counter anion[Al(C_(6)F_(5))_(3)R^(O)Ph]-coordinates to the macrocation via the phenoxy oxygen.The catalyst performances are the concert effects of the steric bulkiness and electronics of the counter anion on the coordinating strength to the macrocation,which is significant to the stability of the active species.展开更多
On the basis of population balance a mathematical model is developed to describe the formation of polymer particle in styrene suspension polymerization. The characteristics of coalescence and breakage of droplets and ...On the basis of population balance a mathematical model is developed to describe the formation of polymer particle in styrene suspension polymerization. The characteristics of coalescence and breakage of droplets and the gel effect are analyzed in particular. Parameters of the models are estimated by experimental data on reaction conversion and particle size distribution. The results show that the model is suitable for predicting polymerization processes.展开更多
The polymerization kinetics of 4, 4′-biphenyldicarbonitrile using cuprous chloride-zinc system as catatyst was investigated. the concentration of unreacted cyano group was measured by infrared spectroscopic analysis ...The polymerization kinetics of 4, 4′-biphenyldicarbonitrile using cuprous chloride-zinc system as catatyst was investigated. the concentration of unreacted cyano group was measured by infrared spectroscopic analysis using potassium ferricyanide as the internal reference. It was found that the polymerization rate is directly proportional to the concentrations ofcyano group, cuprous chloride and zinc, and the activation energy of the polymerization is as Tow as 18.4 KJ/mol. In addition, the other kinetics parameters were obtained and discussed.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
Polymerization of styrene and 1,3-butadiene were performed by calix[4]arene-neodymium complexes using di-n-butylmagnesium and tri-iso-butylaluminum as cocatalyst respectively. The effect of the substituent groups in c...Polymerization of styrene and 1,3-butadiene were performed by calix[4]arene-neodymium complexes using di-n-butylmagnesium and tri-iso-butylaluminum as cocatalyst respectively. The effect of the substituent groups in calix[4]arene on the catalytic activity was first investigated.展开更多
Ligand effect of the catalytic system WCl6-Et2AlCl for ring opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD) was investigated. The experimental results show that adding sterically hindered phenol-2...Ligand effect of the catalytic system WCl6-Et2AlCl for ring opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD) was investigated. The experimental results show that adding sterically hindered phenol-2. 6-di-tert-butylcresylol(DTBC) in the catalytic system not only can obviously increase the monomer conversion of polymerization but also improve the mechanical properties, such as notched impact strength (NIS), tensile strength (TS) ect. 5 of the synthesized polyicycolpentadiene (PDCPD). A similar effect can be observed by using a sterically hindered polymeric phenol - linear phenol formaldehyde resin (LPF) as a ligand.展开更多
The macroprocess of particle formation from suspension droplets of styrene in a pdymerizationsystem was investigated.Inorganic hydroxyapatite or its mixture with polyvinyl alcohol as thepolymerization system was used....The macroprocess of particle formation from suspension droplets of styrene in a pdymerizationsystem was investigated.Inorganic hydroxyapatite or its mixture with polyvinyl alcohol as thepolymerization system was used.Those items such as the effects of the Weight fraction of dispersed-phase,the amount of the inorganic stabilizer and the agitation speed on the breakup and coalescence of thetransient dispersed drops etc.Were examined.Results showd that the dynamic behavior of the transi-ent polymer droplets changed in the presence of the suspension stabilizer during the reaction.展开更多
The polymerization of methyl acrylate (MA) with Nd(naph) 3 Al( i Bu) 3 α,α′ dipyridyl catalyst was studied. The molecular weight and its distribution were determined by gel penetration chromatography. Kine...The polymerization of methyl acrylate (MA) with Nd(naph) 3 Al( i Bu) 3 α,α′ dipyridyl catalyst was studied. The molecular weight and its distribution were determined by gel penetration chromatography. Kinetic studies show that the MA polymerization rate is the first order with respect to monomer concentration. The apparent activation energy of MA polymerization is 49 34 kJ·mol -1 .展开更多
The recent advances in accelerated polymerization of N-carboxyanhydrides (NCAs) offer an effective strategy to simplify the preparation of polypeptide materials. However, the fine-tuning of polymerization kinetics, wh...The recent advances in accelerated polymerization of N-carboxyanhydrides (NCAs) offer an effective strategy to simplify the preparation of polypeptide materials. However, the fine-tuning of polymerization kinetics, which is critical to differentiate the main polymerization and the side reactions, remains largely unexplored. Herein we report the modulation of polymerization rate of NCA in a water/oil biphasic system. By altering the aqueous pH, the initial location of the initiators, and the pK_(a) of initiating amines, we observed the change in polymerization time from several minutes to a few hours. Due to the high interfacial activity and low pKa value, controlled polymerization was observed from multi-amine initiators even if they were initially located in the aqueous phase. This work not only improves our understanding on the biphasic polymerization mechanism, but also facilitates preparation of versatile polypeptide materials.展开更多
The present paper deals with the kinetics of polymerization of acrylonitrile (AN) initialed by the redox system of polypropylene-based vanadyi polyimidodiacetate (PV)-thiourea (TU)in aqueous sulfuric acid in the tempe...The present paper deals with the kinetics of polymerization of acrylonitrile (AN) initialed by the redox system of polypropylene-based vanadyi polyimidodiacetate (PV)-thiourea (TU)in aqueous sulfuric acid in the temperature range from 25 to 40℃. The polymerization rate was measured by varying the concentrations of monomer, vanadyl polyimidodiacetate, thiourea and sulfuric acid. The overall rate of polymerization was summarized asRp=2.2×10~5e^(-6.560/RT) [AN]^(1.0)[PV]^(0.50)[TU]^(1.5)[H_2SO_4]^(2.0)The molecular weight of polyacrylonitrile based on the experimental data was:(?)=k 1/T [pv]^(0.50)[TU]^(1.5)[H_2SO_4]^(2.0)These results indicated that the chain radicals are terminated by combination and/or disproportionation rather than chain transfer. The cooperation effect of carboxylic groups and the macromolecular field effect of polymer supporter are the characters of vanadyl polyimidodiacetate such as the case reported in early paper.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Supported by PetroChina Company Limited(2020 B-2711)。
文摘End-functionalization of polydiene rubbers can not only improve its compatibility with inorganic fillers,but also enhance the overall mechanical properties.Nevertheless,for traditional neodymium(Nd)diene polymerization systems,it is highly challenging to achieve such end-functionalizations,because most of polydienyl chains are capped withη3-allyl-Nd moiety during the end of polymerization,which shows very poor reactivity with nucleophile compounds.We launched a new diene polymerization strategy calling coordinative chain transfer polymerization(CCTP)[1].In such a system,all the polydienyl chains are capped withη1-allyl-Al moieties,which reveal greater reactivity with cyclic esters and epoxide compounds,providing an effective manner to prepare polydiene-polyester amphiphilic block copolymers.Inspired by such findings,we now show herein how such types of chain-ends react with isot-hiocyanate to demonstrate an efficient in-situ manner to access end-functionalized polydienes by using CCTP.
基金financially supported by the Project for Talent Engineering of Hebei Province(No.A2016015001)the Project for Top Young Talent of Hebei Province and that for general colleges of Hebei Province(No.BJ2017017)。
文摘We present a novel generating function(GF)method for the self-condensing vinyl polymerization(SCVP)system with any initial distribution of preexisted polymers.Such a method was proven to be especially useful to investigate the semi-batch SCVP system allowing a sequence of feeding operations during the polymerization.Consequently,the number-,weight-,and z-average molecular weights as well as dispersity index of hyperbranched polymers can be explicitly given,which are determined by predetermined feeding details and conversions in each polymerization step.These analytical results are further confirmed by the corresponding Monte Carlo simulations.Therefore,the present GF method has provided a unified treatment to the semi-batch SCVP system.Accordingly,hyperbranched polymers with desired properties can be prepared by designing feeding details and presetting conversions at each step based on the present GF method.
基金supported by the National Natural Science Foundation of China(No.22376111)Shandong Provincial Natural Science Foundation(No.ZR2024YQ026)+2 种基金for Excellent Young Scholars,Taishan Scholar Foundation of Shandong Province(No.tsqn202408237)Youth Innovation Team Project for Talent Introduction and Cultivation in Universities of Shandong Province(No.096-1622002)the Research Foundation for Distinguished Scholars of Qingdao Agricultural University(No.663-1117015)。
文摘In recent years,cellulose-based fluorescent polymers have received considerable attention.However,conventional modification methods face challenges such as insolubility in most solvents,fluorescence instability,and environmental risks.In this study,a novel biosynthesis strategy was developed to fabricate fluorescent cellulose by adding fluorescent glucose derivatives to a bacterial fermentation broth.The metabolic activity of bacteria is utilized to achieve in situ polymerization of glucose and its derivatives during the synthesis of bacterial cellulose.Owing to the structural similarity between triphenylamine-modified glucose(TPA-Glc N)and glucose monomers,the TPA-Glc N were efficiently assimilated by the bacterial cells and incorporated into the cellulose matrix,resulting in a uniform distribution of fluorescence.The fluorescence color and intensity of the obtained cellulose could be adjusted by varying the amount of the fluorescent glucose derivatives.Compared to the fluorescent cellulose synthesized through physical dyeing,the fluorescence of the products obtained by in situ polymerization showed higher intensity and stability.Furthermore,fluorescent bacterial cellulose can be hydrolyzed into nanocellulose-based ink,which demonstrates exceptional anti-counterfeiting capabilities under UV light.This biosynthesis method not only overcomes the limitations of traditional modification techniques but also highlights the potential of microbial systems as platforms for synthesizing functional polymers.
基金financially supported by the National Natural Science Foundation of China(Nos.21901020 and 22003076)China Postdoctoral Science Foundation(No.2021M701818)+1 种基金Shandong Provincial Natural Science Foundation(No.ZR2022QE237)the Qingdao Postdoctoral Applied Research Project.H.Liu sincerely acknowledges financial support from the Taishan Scholars Program(No.tsqn202211165)。
文摘High catalytic efficiencies in ring opening polymerization(ROP)of a large ring-sized macrolactone,ω-pentadecalactone(PDL),by using transition metal Fe(II)-based catalysts were achieved for the first time in this study.Benefited from the bulky nature of the ligatedα-diimine ligands,as evidenced from single-crystal structures,as well as the weakly oxophilic nature of the metal centers,chain transesterification reactions could be partially suppressed,allowing the polymerization proceed in a living-like and semi-controllable manner,i.e.good linear dependence of propagation rates on catalyst concentration and PDL concentration as observed in the detailed kinetics studies.The whole polymerization proceeds via a“coordination-insertion”mechanism,and with the aid of density functional theory(DFT)calculation studies,a“slow insertion→fast elimination”manner was demonstrated for the monomer propagation step,suggesting the insertion of Fe-OR into the carbonyl group C=O as the rate-determining step.The present catalytic system also showed fast chain transfer reactions to alcohol compounds,affording quasi-immortal characteristics.DFT calculations showed that such a transfer reaction only required an energy barrier of 6.4 kcal/mol,performing a good consistency with the fast chain transfer rates.
基金supported by the Natural Science Foundation of Beijing(No.2092023)the Program of Introducing Talents Discipline to Universities(No.B08003)
文摘Epoxy-terminated hyperbranched polymers （EHBPs） were prepared by proton transfer polymerization and characterized by FT-IR, 1H-NMR and GPC. The solution and thermal properties of the uncured samples and mechanical properties of cured samples were examined. The thermo-stable products had good solubility in polar solvents, low solution viscosity and Tgs ranging from 15℃ to 33℃ depending on their molecular weights. The mechanical properties of cured films were studied and compared with those of a bisphenol-A type epoxy resin. The films of EHBPs had good impact resistance and high gloss values without sacrificing hardness and adhesion.
基金The project is financially supported by the National Natural Science Foundation of China
文摘Effects of N-alkyi substituted ethylenediamine derivatives on vinyl polymerization using persulfate as initiator were studied. The apparent kinetic equations and overall activation energies of acrylamide polymerization were determined using the above mentioned system as initiator. The promoting activities of different diamine derivatives on vinyl polymerization are in the order of tertiary diamine>secondary diamine>primary diamine. Diamines having methyl groups as the substituent on their nitrogen atom possess higher promoting activity than that of having larger alkyl groups. The initial free radicals produced through the redox reaction of persuifate and diamines were studied by spin strapping technique and ESR spectroscopy. The results obtained confirm the fact that the initial free radicals of the diamine species can initiate vinyl polymerization and become the amino end group of the resulting polymers.
基金Supported by the Special Funds for Major State Basic Research Projects( No.G19990 64 80 0 ),the National NaturalScience Foundation of China( No.2 973 4141) ,and SKL EP ( 0 0 62 ) ,SINOPEC and CNPC.
文摘Polynorbornenes were synthesized in the presence of an iron based catalyst, 2,6-bis[1-(2,6-diisopropyl-phenylimino)ethyl]pyridine iron(Ⅱ) dichloride. The FTIR, 1H NMR and 13C NMR analysis results revealed that the structure of the obtained polynorbornenes consisted of vinyl addition polymer substructures without any ring-opening structures. The polymers were amorphous with a short-range order, displayed in the WAXD(wide angle X-ray diffraction) diagrams. The glass transition temperatures ranged from 200 to 400 ℃. The effects of the polymerization reaction conditions, such as Al/Fe molar ratio and toluene/CH_2Cl_2 volume ratio, on the activity, intrinsic viscosity and T_g were also studied.
文摘Investigations show that in monomer water heterogeneous systems polymerization, located in the interface, can disperse the system. Following polymerization in the density gradient field it is shown that in such systems latex particles are nucleated from monomer microdroplets, containing a certain amount of polymer molecules. It could be considered that, independently of the nature of the monomer itself, polymerization in monomer water statistic heterogeneous systems modulate emulsion polymerization process.
文摘Methyl methacrylate (MMA) was polymerized with the rare earth coordination catalyst system of Nd(O? Pr) 3 in toluene. The influences of various ligands in neodymium complexes, molar ratio of Al/Nd, catalyst concentration, catalyst aging time, solvents, the third component CCl 4, temperature and time on the polymerization of MMA were studied. The results showed that the polymerization conversion reached more than 80% at a catalyst concentration of 9 2×10 -3 mol/L. The appropriate molar ratio of CCl 4/Nd was 4. Hydrocarbon was preferred for the polymerzation to obtain a high conversion and a high M W of PMMA. The 1H NMR spectra of PMMA indicated that the lower the temperature, the higher the syndiotactic content of PMMA was obtained.
基金financially supported by the National Natural Science Foundation of China(Nos.U21A20279 and 21774119)。
文摘We report herein the cationic polymerization of isobutylene(IB)under mild conditions is realized with a new binary initiation system generated by simply mixing a Lewis super acid Al(C_(6)F_(5))_(3) and a substituted phenol(RPhOH).Polymers with medium and/or high molecular weights(M_(W)=4.9×10^(4)-27.7×10^(4) g·mol^(-1))can be obtained in toluene and temperatures from-20℃to 0℃.NMR spectrum analysis and DFT sim ulation reveals the in situ generated acidic coordinating complex Ak(C_(6)F_(5))_(3)·RPhOH is the initiating active species,which fu rther tran sformed into the ion-pair[Al(C_(6)F_(5))_(3)ORPh]^(-)[PIB]^(+)of the active intermediates upon growing IB monomers where the counter anion[Al(C_(6)F_(5))_(3)R^(O)Ph]-coordinates to the macrocation via the phenoxy oxygen.The catalyst performances are the concert effects of the steric bulkiness and electronics of the counter anion on the coordinating strength to the macrocation,which is significant to the stability of the active species.
文摘On the basis of population balance a mathematical model is developed to describe the formation of polymer particle in styrene suspension polymerization. The characteristics of coalescence and breakage of droplets and the gel effect are analyzed in particular. Parameters of the models are estimated by experimental data on reaction conversion and particle size distribution. The results show that the model is suitable for predicting polymerization processes.
文摘The polymerization kinetics of 4, 4′-biphenyldicarbonitrile using cuprous chloride-zinc system as catatyst was investigated. the concentration of unreacted cyano group was measured by infrared spectroscopic analysis using potassium ferricyanide as the internal reference. It was found that the polymerization rate is directly proportional to the concentrations ofcyano group, cuprous chloride and zinc, and the activation energy of the polymerization is as Tow as 18.4 KJ/mol. In addition, the other kinetics parameters were obtained and discussed.
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Polymerization of styrene and 1,3-butadiene were performed by calix[4]arene-neodymium complexes using di-n-butylmagnesium and tri-iso-butylaluminum as cocatalyst respectively. The effect of the substituent groups in calix[4]arene on the catalytic activity was first investigated.
文摘Ligand effect of the catalytic system WCl6-Et2AlCl for ring opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD) was investigated. The experimental results show that adding sterically hindered phenol-2. 6-di-tert-butylcresylol(DTBC) in the catalytic system not only can obviously increase the monomer conversion of polymerization but also improve the mechanical properties, such as notched impact strength (NIS), tensile strength (TS) ect. 5 of the synthesized polyicycolpentadiene (PDCPD). A similar effect can be observed by using a sterically hindered polymeric phenol - linear phenol formaldehyde resin (LPF) as a ligand.
文摘The macroprocess of particle formation from suspension droplets of styrene in a pdymerizationsystem was investigated.Inorganic hydroxyapatite or its mixture with polyvinyl alcohol as thepolymerization system was used.Those items such as the effects of the Weight fraction of dispersed-phase,the amount of the inorganic stabilizer and the agitation speed on the breakup and coalescence of thetransient dispersed drops etc.Were examined.Results showd that the dynamic behavior of the transi-ent polymer droplets changed in the presence of the suspension stabilizer during the reaction.
文摘The polymerization of methyl acrylate (MA) with Nd(naph) 3 Al( i Bu) 3 α,α′ dipyridyl catalyst was studied. The molecular weight and its distribution were determined by gel penetration chromatography. Kinetic studies show that the MA polymerization rate is the first order with respect to monomer concentration. The apparent activation energy of MA polymerization is 49 34 kJ·mol -1 .
基金the National Natural Science Foundation of China(No.22101194 for Z.Song and No.52233015 for J.Cheng)Natural Science Foundation of Jiangsu Province(No.BK20210733 for Z.Song)+1 种基金Suzhou Municipal Science and Technology Bureau(No.ZXL2021447 for Z.Song)Collaborative Innovation Center of Suzhou Nano Science&Technology,the 111 Project.,Joint International Research Laboratory of Carbon-Based Functional Materials and Devices,and Suzhou Key Laboratory of Nanotechnology and Biomedicine.
文摘The recent advances in accelerated polymerization of N-carboxyanhydrides (NCAs) offer an effective strategy to simplify the preparation of polypeptide materials. However, the fine-tuning of polymerization kinetics, which is critical to differentiate the main polymerization and the side reactions, remains largely unexplored. Herein we report the modulation of polymerization rate of NCA in a water/oil biphasic system. By altering the aqueous pH, the initial location of the initiators, and the pK_(a) of initiating amines, we observed the change in polymerization time from several minutes to a few hours. Due to the high interfacial activity and low pKa value, controlled polymerization was observed from multi-amine initiators even if they were initially located in the aqueous phase. This work not only improves our understanding on the biphasic polymerization mechanism, but also facilitates preparation of versatile polypeptide materials.
文摘The present paper deals with the kinetics of polymerization of acrylonitrile (AN) initialed by the redox system of polypropylene-based vanadyi polyimidodiacetate (PV)-thiourea (TU)in aqueous sulfuric acid in the temperature range from 25 to 40℃. The polymerization rate was measured by varying the concentrations of monomer, vanadyl polyimidodiacetate, thiourea and sulfuric acid. The overall rate of polymerization was summarized asRp=2.2×10~5e^(-6.560/RT) [AN]^(1.0)[PV]^(0.50)[TU]^(1.5)[H_2SO_4]^(2.0)The molecular weight of polyacrylonitrile based on the experimental data was:(?)=k 1/T [pv]^(0.50)[TU]^(1.5)[H_2SO_4]^(2.0)These results indicated that the chain radicals are terminated by combination and/or disproportionation rather than chain transfer. The cooperation effect of carboxylic groups and the macromolecular field effect of polymer supporter are the characters of vanadyl polyimidodiacetate such as the case reported in early paper.
