聚乙二醇-聚二氧六环酮嵌段共聚物的合成及表征

用辛酸亚锡［Ｓｎ（Ｏｃｔ）２］作催化剂，进行了端羟基聚乙二醇（ＰＥＧ）和１，４ 二氧六环酮（ＤＯＮ）的共聚反应，得到嵌段共聚物ＰＤＯＮ ｂ ＰＥＧ ｂ ＰＤＯＮ．根据１Ｈ ＮＭＲ谱图计算结果表明共聚物组成随两组分投料比而改变．共聚物的ＤＳＣ结果表明嵌段共聚物中ＰＤＯＮ的熔点和结晶度的变化相对较小，而ＰＥＧ的熔点及结晶度均有较大降低．将ＰＥＧ引入可大大提高材料的吸水率．     

异戊二烯/甲基丙烯酸甲酯嵌段共聚物的合成与微结构研究

用稀土催化剂ＲＥ（Ｐ２０４）３ （ｉ Ｂｕ）３Ａｌ ＢｒＣＨ２ＣＨ２Ｂｒ（ＲＥ＝Ｎｄ,Ｐｒ,Ｙ等）合成嵌段共聚物Ｐ（ＩＰ ｂ ＭＭＡ）．系统考察了共聚合反应特征,以ＤＳＣ,１Ｈ ＮＭＲ,１３Ｃ ＮＭＲ技术研究了该嵌段共聚物的微结构．发现以二溴乙烷为添加剂的稀土催化体系是制备Ｐ（ＩＰ ｂ ＭＭＡ）的良好催化剂,共聚物含２个玻璃化转变温度,分别为－７５６℃和１２９℃,嵌段共聚物的结构规整,（ＩＰ）ｍ段以ｃｉｓ １,４结构为主,其含量为９７％左右,３,４ 结构为３％左右,链节间以头 尾方式连接．（ＭＭＡ）ｎ段以间同立构为主,其含量达７４％．     

苯乙烯—甲基丙烯酸甲酯嵌段共聚物的合成与表征

采用阴离子聚合技术合成了一系列苯乙烯－甲基丙烯酸甲酯的两嵌段共聚物。采用ＧＰＣ、ＦＴＩＲ、ＮＭＲ（＾１Ｈ ＮＭＲ，＾１３Ｃ ＮＭＲ和固体ＮＭＲ）和ＤＭＡ等手段进行了表征。结果表明，所得产物为高分子量，窄分布，具有微相分离结构的两嵌段共聚物。     

单茂钛催化剂用于苯乙烯-乙烯嵌段共聚物的合成与表征

乙烯（Ｅ）与苯乙烯（Ｓ）的嵌段共聚合用自制的两种催化剂———茂基三呋喃甲氧基钛［ＣｐＴｉ（ＯＣＨ２Ｏ）３］和茂基三苄氧基钛［ＣｐＴｉ（ＯＣＨ２Ｐｈ）３］进行了研究．考察了促进剂三甲基铝（ＴＭＡ）及乙烯的预聚合时间对聚合结果的影响，发现不同的催化体系有不同的［ＴＭＡ］最佳值以及随着乙烯预聚合时间的延长总的催化效率降低．对嵌段共聚合产物用丁酮、四氢呋喃和氯仿连续萃取分离，得到四氢呋喃中的可溶级分即嵌段共聚物ＰＥ ｂ ｓＰＳ，它占总嵌段共聚合产物的４０ｗｔ％～６０ｗｔ％．对嵌段共聚物用ＤＳＣ、ＷＡＸＤ、ＦＴＩＲ和１３Ｃ ＮＭＲ等方法进行了表征．     

含有机硅多嵌段共聚物的研究：IV.含有机硅多嵌段共聚物的富氧功能

研究了几种新型含有机硅二元和三元多嵌段共聚物的氧，氮选择透过性能。其中双酚Ａ聚羟基醚－聚二甲基硅氧烷二元多嵌段共聚物－（ＰＨＥ－ＰＤＭＳ）的透氧系数Ｐ０２＝５１０Ｂａｒｒｅｒ，氧氮分离系数ａ０２／Ｎ２＝２．２；聚苯醚－聚二甲基硅氧烷－聚对羟基苯乙烯三元多嵌段共聚物－（ＰＰＯ－ＰＤＭＳ－ＰＨＳ）的Ｐ０２＝１５６Ｂａｒｒｅｒ，ｄｏ２／Ｎ２＝２．４，两者都具有良好的力学性能，此外，含有机硅三元多嵌段共聚     

用含偶氮基的聚苯乙烯大分子引发剂合成两亲性嵌段共聚物

采用含偶氮基的聚苯乙烯预聚物（ＰＳ ＡＣＰＣ）作为引发剂，合成了苯乙烯（Ｓｔ）分别与甲基丙烯酸（ＭＡＡ）、甲基丙烯酸（β 羟丙酯）（ＨＰＭＡ）的嵌段共聚物，考察了ＰＳ ＡＣＰＣ引发第二单体的聚合反应行为，以及影响第二单体转化率和均聚物含量、共聚物组成的因素．用溶解性、凝胶渗透色谱（ＧＰＣ）、红外光谱（ＩＲ）、核磁共振（ＮＭＲ）、动态接触角（ＤＣＡ）等表征了嵌段共聚物．     

长软链段对苯二甲酸乙二酯—环氧乙烷多嵌段共聚物的组成…

合成了不同软锻段长度和不同链段含量的系列对苯二甲酸乙二酯－环氧乙烷（ＰＥＴ－ＰＥＯ）多嵌段共聚物，用ＮＭＲ质子谱测定了硬链段一，对部分溶于氯仿的ＰＥＴ－ＰＥＯ多嵌段共聚物进行了分离，并分别测定基氯仿可溶物和不溶物的硬边段一、熔融热谱和热结晶谱，揭示了ＰＥＴ－ＰＥＯ多嵌段共聚物的组成不均一性及其对软段长度和硬链段一的信赖性，进而用ＤＳＣ热谱证明了软链段和硬链段的结晶能力与ＰＥＴ－ＰＥＯ多嵌段共聚物组     

苯乙烯—环氧乙烷嵌段共聚物的阴离子聚合与表征

用二苯甲烷钾为引发剂,阴离子聚合法合成了苯乙烯（Ｓｔ）－环氧乙烷（ＥＯ）嵌段共聚物,并用ＦＴＩＲ,＾１Ｈ－ＮＭＲ,ＳＥＣ,ＷＡＸＤ和动态粘弹谱对共聚物进行了表征。结果表明所得聚合物为分子量可控,窄分布的两嵌段共聚物。     

用SN型催化剂合成苯乙烯－丙烯嵌段共聚物的研究II．共聚物的结构表征与性能

报道用稀土化合物改性的钛系截体催化剂（ＳＮ催化剂）进行苯乙烯和丙烯顺序嵌段共聚合（Ｓｅｑｕｅｎｔｉａｌｂｌｏｃｋｃｏｐｏｌｙｍｅｒｉｚａｔｉｏｎ）的研究，通过对初生嵌段共聚产物进行溶剂萃取与分级，并用１３Ｃ－ＮＭＲ、ＷＡＸＤ．ＤＳＣ，ＤＭＡ和电子显微镜进行表征，推断共聚物为具有等规聚苯乙烯链和等规聚丙烯链段的Ａ－Ｂ型二嵌段共聚物，且各段均能结晶。发现嵌段共聚物比相应的均聚物具有较好的综合力学性能和热性能，而且对ｉＰＳ／ｉＰＰ共混具有良好的增容作用。     

马来酸酐─环氧丙烷共聚物的合成及结构表征

本文将稀土络合物Ｎｄ（Ｐ２０４）３，Ｎｄ（Ｐ５０７），Ｎｄ（ｎａｐｈ）３，Ｎｄ（ａｃａｃ）３．３Ｈ２Ｏ与烷基铝组成的二元体系催化剂用于共聚马来酸酐（ＭＡｎ）与环氧丙烷（ＰＯ）获得成功，并采用１Ｈ－ＮＭＲ研究了共聚的优良催化剂，可得到高转化率，高交替度共聚物，共聚物数均分子量Ｍｎ和分子量分布分别为２０００－３０００，１．３－１．７，共聚物中ＭＡｎ的摩尔含量４０％以上。共聚物组成及序列分布与投料比，催     

甲基丙烯酸丁酯和苯乙烯的原子转移自由基共聚

研究了甲基丙烯酸丁酯（ＢＭＡ）和苯乙烯（Ｓ）这两种不同极性单体的原子转移自由基嵌段共聚和无规共聚,得到了实测分子量与理论分子量相近,分子量分布较窄的嵌段共聚物和无规共聚物．聚合过程中分子量和单体转化率成比例增加,多分散性指数变化不大．用１Ｈ ＮＭＲ法测定共聚组成,Ｋｅｌｅｎ Ｔｕｄｏｓ法计算竞聚率．得到ｒＳｔ＝０９１,ｒＢＭＡ＝０３２．     

聚环氧乙烷大单体与丙烯酸乙酯的共聚及其规整接枝共聚物的表征

 本工作研完了末端为甲基丙烯酸酯型的聚环氧乙烷大单体与丙烯酸乙酯的溶液自由基共聚。结果表明,大单体接枝效率和共聚物分子量受单体总浓度、投料比、大单体分子量及引发剂等的影响,接枝效率最高可达90％以上,分子量可在5-15×10⁴范围内变化。丙烯酸乙酯与大单体共聚的竞聚率为0.83。共聚物用萃取法精制后,用IR、¹H-NMR、裂解色谱、GPC和膜渗透压计等进行了表征。证实产物有预期的规整接枝共聚物结构。平均接枝数为2—11。     

Diffusion in microstructured block copolymer solutions

This work explores the effect of heterogeneity of chemical composition on tracer diffusion, when the characteristic size of the heterogeneities approaches that of the diffusing molecule. A heterogeneous environment is created by the self-assembly of diblock copolymers in solution. The system chosen for this study is polystyrene-polyisoprene diblock copolymers in toluene, which is a common solvent for the two blocks. Above a certain critical concentration, these systems are known to microphase separate into swollen domains of polystyrene and polyisoprene. Diffusion of homopolystyrene through the microstructure is measured in this work. The characteristics of the microstructure are varied by studying block copolymers of different molecular weights and compositions. The tracer diffusion coefficients of the labelled polystyrenes are measured by forced Rayleigh scattering, while the microstructure of the matrix is inferred from small angle X-ray scattering measurements. In this paper, we report results for the diffusion of polystyrenes (molecular weights 3.2 × 10⁴ and 9.0 × 10⁴) in microstructured solutions of three copolymers. Two copolymer samples forming lamellae of alternating polystyrene and polyisoprene microphases and one sample forming polystyrene cylinders embedded in a polyisoprene matrix have been examined. The data indicate that the tracer diffusion coefficient of 3.2 × 10⁴ molecular weight polystyrene in lamellar and cylindrical solutions is comparable to that of the homopolymer in a homogeneous solution of the same concentration. In contrast, the diffusion of 9.0 × 10⁴ molecular weight polystyrene is substantially slower in the structured solutions than in unstructured solutions of the same concentration. For example, the diffusion coefficient of 9.0 × 10⁴ molecular weight polystyrene in a 47% block copolymer solution with cylindrical microstructure is lower than its value in a homogeneous solution of the same concentration by a factor of 30.     

Synthesis and Characterization of Styrene-Isoprene Diblock Copolymers

A simple reusable apparatus for the synthesis of up to 40 g quantities of poly(styrene-b-isoprene) diblock copolymers of reasonably low (1.2 to 1.5) polydispersity has been described. The diblock copolymers synthesized were characterized by gel permeation chromatography (GPC), membrane osmometry, viscosimetry, and nuclear magnetic resonance (NMR) spectroscopy. Number-average molecular weights (M _n) calculated from the raw GPC chromatographs of the diblock copolymers using the summation method and M versus elution volume plots for polystyrene and polyisoprene standards agree well with those measured experimentally with osmometry. It is suggested that for polydisperse block copolymers this method is simpler than the use of a universal calibration curve. Mark-Houwink constants K ans a for polyisoprene having 18% (1,2-), 66% (3,4-), and 16% (1,4-) microstructure were found to be 3.2 × 10^?4 dL/g and 0.67, respectively, in THF at 25°C. In toluene at 30°C, K = 2.0 × 10^?4 dL/g and α = 0.7 were obtained. The diblock copolymers had 26% (1,2-), 60% (3,4-), and 14% (1,4-) microstructure in the isoprene segments, and the values of K and a for these copolymers (PS > 50%, M 20.0 × 10³) in THF at 25°C were 9.0 × 10^?5 dL/g and 0.75. For M < 20.0 × 10³ the value of α was 0.5. The experimental values of [η] were found to be lower than those calculated theoretically, presumably due to the polydisperse nature and the biellipsoidal configuration of the diblock copolymers.     

杯芳烃钕/二正丁基镁/六甲基磷酰胺催化4-乙烯基吡啶的均聚及其与苯乙烯的共聚

聚4-乙烯基吡啶[P（4-VP）]是一种功能高分子,由于在吡啶环上有一个碱性的氮原子,它能进一步与酸反应生成各种盐,与卤代烃生成季铵盐以及与金属离子生成配合物,可用作高分子电解质,高分子试剂,高分子功能材料等,因此有不少文献对它的合成进行了报道,合成聚4-乙烯基吡啶及其与苯乙烯（St）的共聚物,除了用丁基锂作引发剂外,过渡金属的Ziegler-Natta催化剂,以及烷基铝和烷基锌等也常被用作催化剂,但用这些催化剂催化所得的聚4-乙烯基吡啶及其与苯乙烯的共聚物产率低,分子量小。     

Synthesis and characterization of poly[styrene‐b‐methyl(3,3,3‐trifluoropropyl)siloxane] diblock copolymers via anionic polymerization

A series of narrow molecular weight distribution (MWD) polystyrene‐b‐poly[methyl(3,3,3‐trifluoropropyl)siloxane] (PS‐b‐PMTFPS) diblock copolymers were synthesized by the sequential anionic polymerization of styrene and trans‐1,3,5‐trimethyl‐1,3,5‐tris(3′,3′,3′‐trifluoropropyl)cyclotrisiloxane in tetrahydrofuran (THF) with n‐butyllithium as the initiator. The diblock copolymers had narrow MWDs ranging from 1.06 to 1.20 and number‐average molecular weights ranging from 8.2 × 10³ to 37.1 × 10³. To investigate the properties of the copolymers, diblock copolymers with different weight fractions of poly[methyl(3,3,3‐trifluoropropyl)siloxane] (15.4–78.8 wt %) were prepared. The compositions of the diblock copolymers were calculated from the characteristic proton integrals of ¹H NMR spectra. For the anionic ring‐opening polymerization (ROP) of 1,3,5‐trimethyl‐1,3,5‐tris(3′,3′,3′‐trifluoropropyl)cyclotrisiloxane (F₃) initiated by polystyryllithium, high monomer concentrations could give high polymer yields and good control of MWDs when THF was used as the polymerization solvent. It was speculated that good control of the block copolymerization under the condition of high monomer concentrations was due to the slowdown of the anionic ROP rate of F₃ and the steric hindrance of the polystyrene precursors. There was enough time to terminate the ROP of F₃ when the polymer yield was high, and good control of block copolymerization could be achieved thereafter. The thermal properties (differential scanning calorimetry and thermogravimetric analysis) were also investigated for the PS‐b‐PMTFPS diblock copolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4431–4438, 2005     

Polymethylene‐b‐polystyrene diblock copolymer: Synthesis,property, and application

The design and synthesis of well‐defined polymethylene‐b‐polystyrene (PM‐b‐PS, M_n = 1.3 × 10⁴–3.0 × 10⁴ g/mol; M_w/M_n (GPC) = 1.08–1.18) diblock copolymers by the combination of living polymerization of ylides and atom transfer radical polymerization (ATRP) was successfully achieved. The ¹H NMR spectrum and GPC traces of PM‐b‐PS indicated the successful extension of PS segment on the PM macroinitiator. The micellization behavior of such diblock copolymers in tetrahydrofuran were characterized by dynamic light scattering (DLS) and atomic force microscopy (AFM) techniques. The average aggregate sizes of PM‐b‐PS diblock copolymers with the same length of PM segment in tetrahydrofuran solution (1.0 mg mL^?1) increases from 104.2 nm to 167.7 nm when the molecular weight of PS segment increases. The spherical precipitated aggregates of PM‐b‐PS diblock copolymers with an average diameter of 600 nm were observed by AFM. Honeycomb porous films with the average diameter of 3.0 μm and 6.0 μm, respectively, were successfully fabricated using the solution of PM‐b‐PS diblock copolymers in carbon disulfide via the breath‐figure (BF) method under a static humid condition. The cross‐sections of low density polyethylene (LDPE)/polystyrene (PS)/PM‐b‐PS and LDPE/polycarbonate (PC)/PM‐b‐PS blends were observed by scanning electron microscope and reveal that the PM‐b‐PS diblock copolymers are effective compatilizers for LDPE/PS and LDPE/PC blends. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1894–1900, 2010     

Solution properties of styrene-p-chlorostyrene diblock copolymers—II. Light scattering studies in a selective solvent

Conformational behaviour of styrene-p-chlorostyrene diblock copolymers in cumene (a good solvent for polystyrene but a θ solvent for poly-p-chlorostyrene) was studied over the temperature range 15–60° by light scattering, osmotic pressure and intrinsic viscosity measurements. Two samples of copolymer (AB-4 and AB-2) were used. The composition of the samples was c. 50 mol% of styrene and the number-average molecular weights were 27.7 × 10⁴ for the AB-4 and 19.5 × 10⁴ for the AB-2. It was found that below 40° the number-average molecular weight of the AB-4 sample seemed to increase gradually with decreasing temperature and around 40°, marked decreases in the osmotic second virial coefficient and intrinsic viscosity were observed. The Zimm plot for the AB-2 sample was fairly normal at 40°. It seems that the temperature where an anomaly becomes evident in Zimm plots is dependent on the molecular weight of the sample. The experimental results for the diblock copolymers could be understood from the view that intermolecular association took place to some extent in the solutions on lowering the temperature giving rise to multi-molecular micelles.     

Synthesis and characterization of well‐defined diblock and triblock copolymers of poly(N‐isopropylacrylamide) and poly(ethylene oxide)

Well‐defined diblock and triblock copolymers composed of poly(N‐isopropylacrylamide) (PNIPAM) and poly(ethylene oxide) (PEO) were successfully synthesized through the reversible addition–fragmentation chain transfer polymerization of N‐isopropylacrylamide (NIPAM) with PEO capped with one or two dithiobenzoyl groups as a macrotransfer agent. ¹H NMR, Fourier transform infrared, and gel permeation chromatography instruments were used to characterize the block copolymers obtained. The results showed that the diblock and triblock copolymers had well‐defined structures and narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight < 1.2), and the molecular weight of the PNIPAM block in the diblock and triblock copolymers could be controlled by the initial molar ratio of NIPAM to dithiobenzoate‐terminated PEO and the NIPAM conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4873–4881, 2004     

丙烯酸全氟烷基乙基酯嵌段共聚物的组成结构表征

含氟聚合物具有独特的性质 ,使其成为高分子材料领域中的特殊功能材料 .这类聚合物具有高表面活性、高热稳定性、高化学稳定性 ,及既憎水又憎油的“三高”、“两憎”特性[1] ,可用作织物拒水拒油整理剂、防污涂料、流平剂等 .然而含氟单体价格高昂 ,人们希望在满足性能要求的同时 ,尽量减少氟单体的用量 .利用分子设计方法 ,制备结构规整的嵌段共聚物无疑是一种有效的方法 .目前 ,文献中关于含氟嵌段共聚物的制备的方法有负离子聚合法[2 ] 、基团转移聚合法 (GTP) [3 ] 、正离子聚合法[4] 、引发 转移 终止法 (Iniferter) [5] ,以及近年…