Optimization of an α‐(Amino acid)‐N‐carboxyanhydride polymerization using the high vacuum technique: Examining the effects of monomer concentration,polymerization kinetics,polymer molecular weight,and monomer purity

l ‐Ornithine‐based poly(peptides) have been widely utilized in the field of drug delivery, however few studies have been conducted examining the details of polymerization. In this article, the effects of monomer concentration, polymerization kinetics, polymer molecular weight and monomer purity were investigated using l ‐carboxybenzyl (Cbz)‐ornithine as a model monomer. The mechanism of polymerization herein follows the normal amine mechanism to produce poly(peptides) having controlled molecular weights, known chain ends and a narrow polydispersity index (PDI). A preferred monomer concentration range was determined, which required minimal polymerization times and allowed for predictable and reproducible molecular weights with narrow PDIs. The impact of monomer purity on the polymerization was established and monomer purification conditions are reported, which produce high‐purity monomer after a single recrystallization. Additionally, the optimized polymerization conditions and monomer purification protocol were combined with a sequential monomer addition technique to produce high molecular weight poly(ornithine) with a narrow PDI and known chain ends. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1385–1391     

Ring‐opening metathesis polymerization of functionalized cyclooctene by a ruthenium‐based catalyst in ionic liquid

This paper describes the synthesis of a novel monomer of 5‐substituted cyclooctene with the pendant of imidazolium salt (7) and the ring‐opening metathesis polymerization of the functionalized cyclooctenes ( 4 and 7 ) in CH₂Cl₂ and ionic liquid [bmim][PF₆] by a ruthenium‐based catalyst RuCl₂(PCy₃)(SIMes)(CHPh) (2). The polymerization, which was carried out in ionic liquid, afforded improved control over the molecular weight (M_n) and polydispersity of the resultant products (PDI <1.4). Furthermore, to facilitate the GPC measurement for molecular weight of polymers, the charged polymers (poly‐ 7 ) were hydrolyzed to give uncharged polymers (poly‐ 4 *) by removing the imidazolium pendant from the polymer chains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3986–3993, 2007     

Manipulation of the molecular weight and branching structure of hyperbranched poly(arylene ether phosphine oxide)s prepared via an A2 + B3 approach

A series of hyperbranched poly(arylene ether phosphine oxide)s (HB PAEPOs) were prepared via an A₂ + B₃ polymerization scheme with tris(4‐fluorophenyl)phosphine oxide as B₃, and a variety of bisphenols as A₂. The effects of the reactivity of the A₂ monomer, the A:B ratio, the addition mode, the solvent, and the concentration on the final molecular weight, polydispersity index (PDI), and degree of branching (DB) were studied. Soluble HB PAEPOs with weight‐average molecular weights of up to 299,000 Da were achieved. Reactions in which the A₂ component was added slowly resulted in lower DBs (0.2–0.5), whereas the slow addition of the B₃ component provided samples with DBs of approximately 0.75. Reactions performed under high‐dilution conditions afforded completely soluble materials with weight‐average molecular weights of 9000–12,100 Da and PDI values as low as 2.20. The molecular weights achieved under high‐dilution conditions were independent of the mode of monomer addition. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3871–3881, 2003     

Cationic polymerization of formaldehyde in liquid carbon dioxide. Part I

A cationic polymerization of formaldehyde which gave a high molecular weight polymer was studied in liquid carbon dioxide at 20–50°C. In the polymerization without any catalyst both the rate of polymerization and the molecular weight of the resulting polymer increased rapidly with a decrease in the loading density of the monomer solution to the reaction vessel, and also increased with an increase in the initial monomer concentration. From these results it was concluded that the initiating species could be ascribed to an impurity contained in the monomer solution. Both the rate of polymerization and the degree of polymerization of the polymer also increased with rising temperature. The carboxylic acid added acted as a catalyst in the polymerization because of increase in the polymer yield, the molecular weight of polymer formed, and the number of moles of polymer chain with increasing dissociation constant of acid used. It was concluded that the polymerization in liquid carbon dioxide proceeded by a cationic mechanism. Methyl formate had no influence on the polymerization, but methanol and water acted as a chain-transfer agent.     

Effect of lithium perchlorate on the spontaneous copolymerization of 4‐vinylpyridine with various electron‐rich vinyl monomers

The spontaneous copolymerization of 4‐vinylpyridine (4‐VP) activated with lithium perchlorate (LiClO₄) with various electron rich monomers (p‐methoxystyrene, MeOSt; p‐methylstyrene, MeSt; styrene, St) was investigated in various solvent systems at 75°C. Increasing the LiClO₄ concentration and the nucleophilicity of the electron rich monomer increased the copolymer yields. Both ¹H‐NMR and elemental analysis confirmed the almost 1:1 copolymer structure for VP/MeOSt system which possessed high molecular weight and narrow polydispersity (PDI). Compared to 4‐VP activated with zinc chloride, LiClO₄ systems showed slightly lower yields and much narrower PDI. We also investigated the spontaneous copolymerization of 4‐VP activated with various protic acids in the reaction with various electron rich comonomers. However, generally protic salt forms showed less solubility in organic solvents and showed low molecular weight polymer products with low yields. The proposed initiation mechanism exhibits the formation of a σ‐bond between the β‐carbons of the two donor‐acceptor monomers, creating the 1,4‐tetramethylene biradical intermediate initiating the copolymerization. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1709–1716, 1999     

Controlled polymerization of 2‐(diethylamino)ethyl methacrylate and its block copolymer with N‐isopropylacrylamide by RAFT polymerization

Poly(2‐(diethylamino)ethyl methacrylate) (PDEAEMA) homopolymers with low polydispersities were synthesized by reversible addition fragmentation chain transfer (RAFT) radical polymerization. The performances of two chain transfer agents, 2‐cyanoprop‐2‐yl dithiobenzoate and 4‐cyanopentanic acid dithiobenzoate (CPADB), were compared. It was found that the polymerization of 2‐(diethylamino) ethyl methylacrylate was under good control in the presence of CPADB with 4,4′‐azobis(4‐cyanopentanoic acid) (ACPA) as initiator in 1,4‐dioxane at 70 °C. The kinetic behaviors were investigated under different CPADB/ACPA molar ratios. A long polymerization inhibition period was observed at high [CPADB]/[ACPA] ratio. The influences of [CPADB]/[ACPA] ratio, monomer/[CPADB] ratio, and temperature were studied with respect to monomer conversion, molecular weight control, and polydispersity index (PDI). The PDI decreased from 1.21 to 1.12, as the CPADB/ACPA molar ratio changed from 2 to 10. The molecular weight of PDEAEMA could be controlled by monomer/CPADB molar ratio. The control over MW and PDI was improved as the temperature increased from 60 to 70 °C; however, an additional increase to 80 °C led to a loss of control. Using PDEAEMA macroRAFT agent, pH/thermo double‐responsive block copolymers of PDEAEMA and poly(N‐isopropylacrylamide) (PDEAEMA‐b‐PNIPAM) with narrow polydispersity (PDI, 1.24) were synthesized. The lower critical solution temperature of PDEAEMA‐b‐PNIPAM block copolymer depended on the environmental pH. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3294–3305, 2008     

分散聚合法制备液相芯片聚苯乙烯磁性复合微球的研究

本文将丙烯酸基磁流体均匀分散到苯乙烯单体中,采用分散聚合法制备出了适于构建液相芯片微球载体的单分散性微米级磁性微球.考察了丙烯酸基磁流体预处理时间、加料顺序和单体量对微球形貌和粒径分布的影响及其条件优化.扫描电镜(SEM)显示磁性微球平均粒径为7.77 μm,具有良好的单分散性(多分散指数PDI为1.03),并且表面光滑致密;用超导量子干涉磁强计测量了Fe3O4纳米粒子的磁化曲线;用红外光谱(FT-IR)和热失重(TG)方法表征了磁性微球的化学结构及Fe3O4含量.     

Reversible addition‐fragmentation chain transfer polymerization of methacrylates containing hole‐ or electron‐transporting groups

The controlled/living radical polymerization of 2‐(N‐carbazolyl)ethyl methacrylate (CzEMA) and 4‐(5‐(4‐tert‐butylphenyl‐1,3,4‐oxadiazol‐2‐yl)phenyl) methacrylate (t‐Bu‐OxaMA) via reversible addition‐fragmentation chain transfer polymerization has been studied. Functional polymers with hole‐ or electron‐transfer ability were synthesized with cumyl dithiobenzoate as a chain transfer agent (CTA) and AIBN as an initiator in a benzene solution. Good control of the polymerization was confirmed by the linear increase in the molecular weight (MW) with the conversion. The dependence of MW and polydispersity index (PDI) of the resulting polymers on the molar ratio of monomer to CTA, monomer concentration, and molar ratio of CTA to initiator has also been investigated. The MW and PDI of the resulting polymers were well controlled as being revealed by GPC measurements. The resulting polymers were further characterized by NMR, UV‐vis spectroscopy, and cyclic voltammetry. The polymers functionalized with carbazole group or 1,3,4‐oxadiazole group exhibited good thermal stability, with an onset decomposition temperature of about 305 and 323 °C, respectively, as determined by thermogravimetric analysis. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 242–252, 2007     

Polymerization initiated by an electron donor–acceptor complex. Part IV. Kinetic study of polymerization of methyl methacrylate initiated by the charge-transfer complex consisting of poly-2-vinylpyridine and liquid sulfur dioxide

A kinetic study has been made of the polymerization of methyl methacrylate (MMA) initiated by a charge-transfer complex of poly-2-vinylpyridine (electron donor) and liquid sulfur dioxide (acceptor) in the presence of carbon tetrachloride. It is concluded that the polymerization proceeds through free-radical intermediates, as with the pyridine-liquid sulfur dioxide complex system. The association constants K of acceptor and polymer electron donors which range widely in their molecular weight were determined spectrophotometrically, and it has been found that both K and overall rate of polymerization R_p of MMA decrease with increasing molecular weight of polymer donor; contrary to this, molecular weight of PMMA formed increases with increasing molecular weight of the polymer donor. Other kinetic behaviors was essentially the same as in the pyridine–liquid sulfur dioxide system, i.e., R_p is proportional to the square root of the concentration of the complex and to the 3/2-order of the monomer concentration; R_p is clearly sensitive to the carbon tetrachloride concentration at low concentration of carbon tetrachloride, but for a higher concentration it is practically independent of the carbon tetrachloride concentration. It has been deduced from a kinetic mechanism for the initiation that a primary radical may be produced from the reduction of carbon tetrachloride by an associated complex consisting of liquid sulfur dioxide–polymer donor and the monomer.     

SYNTHESIS, CHARACTERIZATION AND ANTIMICROBIAL PROPERTIES OF 4-[（4-HYDROXYBENZYLIDENE） AMINO] PHENOL AND ITS POLYMER

The oxidative polycondensation reaction conditions of 4-[(4-hydroxybenzylidene)amino]phenol(4-HBAP)were studied with H_2O_2,air oxygen and NaOCl in an aqueous alkaline medium between 50 and 90℃.The structures of the obtained monomer and polymer were confirmed by FT-IR,UV-Vis,~1H-and ~(13)C-NMR and elemental analysis.The characterization was made by TG-DTA,size exclusion chromatography(SEC)and solubility tests.At the optimum reaction conditions,the yield of poly[4-(4-hydroxybenzylidene amino)phenol](P-4-HBAP)was found to be 48.3%(for H_2O_2 oxidant),80.5%(for air O_2 oxidant)and 86.4%(for NaOCl oxidant).According to the SEC analysis,the number-average molecular weight(M_n),weight-average molecular weight(M_w)and polydispersity index(PDI)values of P-4-HBAP was found to be 8950,10970 g mol~(-1) and 1.225,respectively,using H_2O_2;and 11610,15190 g mol~(-1) and 1.308 respectively, using air O_2 and 7900,9610 g mol~(-1) and 1.216,respectively,using NaOCl.According to TG-DTA analyses,P-4-HBAP was more stable than 4-HBAP against thermal decomposition.The weight loss of P-4-HBAP was found to be 49.27% at 1000℃. The highest occupied molecular orbital(HOMO)and the lowest unoccupied molecular orbital(LUMO)values calculated from electrochemical measurement.Electrochemical energy gaps(E′_g)of 4-HBAP and P-4-HBAP were found to be-5.46, -5.28;-2.26,-2.67;3.20 and 2.61 eV,respectively.According to UV-Vis measurements,optical band gap(E_g)of 4-HBAP and P-4-HBAP were found to be 3.34 and 3.01 eV,respectively.Also,antimicrobial activities of 4-HBAP and P-4-HBAP were examined against selected some bacteria.The electrical conductivity of the polymer was measured after doping with iodine.     

Synthesis of well‐defined cyclodextrin‐core star polymers

The synthesis of 21‐arm methyl methacrylate (MMA) and styrene star polymers is reported. The copper (I)‐mediated living radical polymerization of MMA was carried out with a cyclodextrin‐core‐based initiator with 21 independent discrete initiation sites: heptakis[2,3,6‐tri‐O‐(2‐bromo‐2‐methylpropionyl]‐β‐cyclodextrin. Living polymerization occurred, providing well‐defined 21‐arm star polymers with predicted molecular weights calculated from the initiator concentration and the consumed monomer as well as low polydispersities [e.g., poly(methyl methacrylate) (PMMA), number‐average molecular weight (M_n) = 55,700, polydispersity index (PDI) = 1.07; M_n = 118,000, PDI = 1.06; polystyrene, M_n = 37,100, PDI = 1.15]. Functional methacrylate monomers containing poly(ethylene glycol), a glucose residue, and a tert‐amine group in the side chain were also polymerized in a similar fashion, leading to hydrophilic star polymers, again with good control over the molecular weight and polydispersity (M_n = 15,000, PDI = 1.03; M_n = 36,500, PDI = 1.14; and M_n = 139,000, PDI = 1.09, respectively). When styrene was used as the monomer, it was difficult to obtain well‐defined polystyrene stars at high molecular weights. This was due to the increased occurrence of side reactions such as star–star coupling and thermal (spontaneous) polymerization; however, low‐polydispersity polymers were achieved at relatively low conversions. Furthermore, a star block copolymer consisting of PMMA and poly(butyl methacrylate) was successfully synthesized with a star PMMA as a macroinitiator (M_n = 104,000, PDI = 1.05). © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2206–2214, 2001     

Atom transfer radical polymerization of N‐vinyl carbazole: Optimization to characterization

The homopolymerization of N‐vinylcarbazole was performed with atom transfer radical polymerization (ATRP) with Cu(I)/Cu(II)/2,2′‐bipyridine (bpy) as the catalyst system at 90 °C in toluene. N‐2‐Bromoethyl carbazole was used as the initiator, and the optimized ratio of Cu(I) to Cu(II) was found to be 1/0.3. The resulting homopolymer, poly(N‐vinylcarbazole) (PVK), was formed after a monomer conversion of 76% in 20 h. The molecular weight as well as the polydispersity index (PDI) showed a linear relation with the conversion, which showed control over the polymerization. A semilogarithmic plot of the monomer conversion with time was linear, indicating the presence of constant active species throughout the polymerization. The initiator efficiency and the effect of the variation of the initiator concentration on the polymerization were studied. The effects of the addition of CuBr₂, the variation of the catalyst concentration with respect to the initiator, and CuX (X = Br or Cl) on the kinetics of homopolymerization were determined. With Cu(0)/CuBr₂/bpy as the catalyst, faster polymerization was observed. For a chain‐extension experiments, PVK (number‐average molecular weight = 1900; PDI = 1.24) was used as a macroinitiator for the ATRP of methyl methacrylate, and this resulted in the formation of a block copolymer that gave a monomodal curve in gel permeation chromatography. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1745–1757, 2006     

Self-assembly of amphiphilic liquid crystal polymers obtained from a cyclopropane-1,1-dicarboxylate bearing a cholesteryl mesogen

We study the self-assembly of a new family of amphiphilic liquid crystal (LC) copolymers synthesized by the anionic ring-opening polymerization of a new cholesterol-based LC monomer, 4-(cholesteryl)butyl ethyl cyclopropane-1,1-dicarboxylate. Using the t-BuP(4) phosphazene base and thiophenol or a poly(ethylene glycol) (PEG) functionalized with thiol group to generate in situ the initiator during the polymerization, LC homopolymer and amphiphilic copolymers with narrow molecular weight distributions were obtained. The self-assemblies of the LC monomer, homopolymer, and block copolymers in bulk and in solution were studied by small-angle X-ray scattering (SAXS), differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and transmission electron microscopy (TEM). All polymers exhibit in bulk an interdigitated smectic A (SmA(d)) phase with a lamellar period of 4.6 nm. The amphiphilic copolymers self-organize in solution into vesicles with wavy membrane and nanoribbons with twisted and folded structures, depending on concentration and size of LC hydrophobic block. These new morphologies will help the comprehension of the fascinating organization of thermotropic mesophase in lyotropic structures.     

甲基丙烯酸正丁酯正相微乳液可控/“活性”光聚合动力学研究

以末端含溴原子的光引发剂2-溴异丁酰氧基-2-甲基-1-苯基甲酮(HMPP-Br)为引发剂,2,2,6,6-四甲基哌啶-1-氧自由基(TEMPO)和2,2,6,6-四甲基哌啶醇(TMP)为调控剂,采用光聚合方法研究了甲基丙烯酸正丁酯(n-BMA)/十二烷基硫酸钠(SDS)/水/正丁醇 O/W型正相微乳液体系的光聚合反应动力学.结果表明,改性后的引发剂具有一定的引发活性,且聚合微乳液体系较稳定,聚合反应获得了良好的ln[M]₀/[M]与时间、数均分子量与转化率之间的线性动力学关系,制备了分子量分布较窄的Poly(n-BMA)均聚物.     

γ-Ray-induced copolymerization of ethylene and vinyl chloride in liquid carbon dioxide

The γ-ray-induced copolymerization of ethylene and vinyl chloride with the use of liquid carbon dioxide as a solvent was studied under a total pressure of 400 kg/cm², with a dose rate of 2.5 × 10⁴ rad/hr at 30°C. A rubberlike, sticky polymer is obtained when the molar concentration of vinyl chloride is less than 30% in the monomer mixture, and the polymer is a white powder at higher concentrations of vinyl chloride. Infrared, x-ray, and differential thermal analyses confirm that the polymerization products are noncrystalline, true random copolymers. The rate of copolymerization decreases markedly when a small amount of vinyl chloride is added to ethylene monomer. In the range of vinyl chloride concentration higher than 5%, however, the rate and the molecular weight of copolymer increase with increasing concentration of vinyl chloride. It has been concluded from kinetic considerations based on these results that the rate of initiation increases proportionally with the concentration of vinyl chloride. Further, the growing chain radicals are shown to be deactivated by the cross-termination reaction between the radicals with terminal unit of ethylene and vinyl chloride, and no transfer reaction occurs.     

Preparation of polyvinylpyrrodione microspheres by dispersion polymerization

The preparation of polyvinylpyrrolidone (PVP) microspheres in ethyl acetate by dispersion polymerization with N-vinylpyrrolidone (NVP) as initial monomer, poly(N-vinylpyrrolidone-co-vinyl acetate) (P (NVP-co-VAc)) as dispersant, and 2, 2′-azobisisobutyronitrile(AIBN) as initiator is reported. The influences of monomer concentration, dispersant concentration and initiator concentration on the size of PVP microspheres as well as the monomer conversion were studied. The structure and properties of PVP microspheres were analyzed. The results show that the prepared PVP microspheres have a mean diameter of 3-4 μm. With an increase in NVP concentration, the size and the molecular weight of the PVP microspheres as well as the monomer conversion all increase. With increasing P(NVP-co-VAc) concentrations, the PVP molecular weight and monomer conversion both increase while the size of the microspheres becomes smaller. As the concentration of AIBN increases, the microsphere size and monomer conversion increase whereas the PVP molecular weight decreases. The PVP prepared by dispersion polymerization has a crystal structure, and its molecular weight is lower compared to that prepared by solution polymerization. __________ Translated from Acta Polymerica Sinica, 2007, 11 (in Chinese)     

Atom transfer radical polymerization of ionic liquid 2‐(1‐butylimidazolium‐3‐yl)ethyl methacrylate tetrafluoroborate

Polymeric forms of ionic liquids may have many potential applications because of their high thermal stability and ionic nature. They are generally synthesized by conventional free‐radical polymerization. Here we report a living/controlled free‐radical polymerization of an ionic liquid monomer, 2‐(1‐butylimidazolium‐3‐yl)ethyl methacrylate tetrafluoroborate (BIMT), via atom transfer radical polymerization. Copper bromide/bromide based initiator systems polymerized BIMT very quickly with little control because of fast activation but slow deactivation. With copper chloride as the catalyst and trichloroacetate, CCl₄, or ethyl α‐chlorophenylacetate as the initiator, BIMT was polymerized at 60 °C in acetonitrile with first‐order kinetics with respect to the monomer concentration. The molecular weight was linearly dependent on the conversion. The monomer concentration strongly affected the polymerization: a low monomer concentration caused the polymerization to be incomplete, probably because of catalyst disproportionation in polar solvents. The addition of a small amount of pyridine suppressed such disproportionation, but a further increase in the amount of pyridine greatly slowed the polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5794–5801, 2004     

分散聚合法制备PVP微球的研究

以N-乙烯基吡咯烷酮(NVP)为初始单体,乙酸乙酯为分散介质,采用分散聚合法制备了分散性能良好、粒径为3～4μm的聚乙烯基吡咯烷酮(PVP)微球.考察了单体、分散剂及引发剂浓度对PVP微球的粒径、单体转化率及分子量的影响,并对PVP的结构和性能进行研究.结果表明,单体浓度增加,PVP微球粒径和分子量增大,单体转化率升高;分散剂浓度增加,PVP微球粒径变小,分子量增大,单体转化率升高;引发剂浓度增加,PVP微球粒径变大,分子量减小,单体转化率升高.与溶液聚合法相比,分散聚合法制备的PVP分子量较小且具有一定的结晶性.     

含咪唑离子盐的环辛烯在离子液体中开环易位聚合微观研究

用核磁共振方法研究了带电荷的环辛烯单体在离子液体和CDCl3中开环易位聚合反应的微观特征,根据单体在化学位移δ=5.66~5.58处双键氢积分峰面积的减少和聚合物主链上不饱和双键氢移至高场δ=5.38~5.39处峰面积积分的增加来表征聚合反应的情况.检测和记录了单体在有离子液体参与的条件下均相聚合反应和在CDCl3中的异相聚合反应过程,根据在不同反应体系中Grubbs第二代崔化剂中与Ru相连的苯亚甲基上氢在核磁图谱上δ=19.2处的峰型变化,探讨在两种介质中的不同聚合行为.研究表明,该单体在离子液体介质中的均相聚合有可控聚合的微观特点,并通过ln[M]0/[M]与反应时间的关系曲线,证实了反应的活性特征.     

H_2O/TiCl_4/Py体系引发苯乙烯正离子聚合

研究了在少量吡啶(Py)存在下由水(H2O)四氯化钛(TiCl4)体系引发苯乙烯于二氯甲烷正己烷中进行碳正离子聚合,分别考察[Py]、[H2O]和[TiCl4]对聚合速率、产物分子量与分子量分布的影响.实验结果表明,少量亲核试剂吡啶(Py)对聚合反应起着重要作用,可有效地降低聚合速率和使分子量分布变窄;随着[H2O]和[Py]降低或[TiCl4]增加,聚合产物的分子量增加,而分子量分布指数(Mw Mn)基本维持在1.8左右;随着[Py]增加,聚合速率降低;随着[H2O]和[TiCl4]增加,聚合速率提高.聚合速率对单体浓度呈一级动力学关系,对Py、H2O和TiCl4的反应级数分别为-0.72、0.72和1.86.聚合速率对TiCl4浓度呈接近二级动力学关系,这可能与体系中TiCl4主要以二聚体形式存在有关.聚合转化率和产物分子量均随着反应时间延长而逐渐增大,PS的数均分子量与转化率呈线性增加关系.