Synthesis of well-defined block copolymers and star-branched polymers by using terminal 1,3-butadiene functionalized polymers as reactive building blocks

Terminal 1,3-buadiene (Bd) functional polymers are stoichiometrically reacted with living anionic polymers in a monoaddition manner in THF at ?78 °C, but neither polymerization nor oligomerization occurs under the conditions. By utilizing this reactive but non-polymerizable character of the Bd function toward living anionic polymers, a variety of block copolymers and regular and asymmetric star-branched polymers were successfully synthesized. In these syntheses, the terminal Bd functionalized polymers work effectively as reactive building blocks, namely polymeric efficient linking agents, to construct such architectural polymers. Since all the polymer segments used for the syntheses were derived from living anionic polymers and the linking reactions quantitatively proceeded, the architectural polymers herein synthesized were well-defined in structure and were precisely controlled in chain length. A new protocol based on iterative approach by repeating a two reaction sequence involving linking reaction and re-introduction of Bd group was proposed and developed to successively synthesize asymmetric star-branched polymers up to a 6-arm ABCDEF type. The terminal Bd functionalized polymers were readily and quantitatively converted to anhydride or diepoxide functionalized polymers by Diels–Alder or oxidation reactions. Because of their high reactive termini, the resulting polymers are also usable as reactive building blocks to synthesize the core-functionalized star-branched polymers with carboxylic acids or hydroxyl groups. The reactions between terminal anhydride and amine functionalized polymers were carried out in bulk at 180 °C to examine the synthetic possibility of star-branched polymers under such conditions.     

原子转移自由基偶联法合成星形聚合物

以卤端基聚合物为大分子引发剂,卤化亚铜／２,２‘＝二联二吡啶为催化剂,工业二乙烯基苯、纯间－二乙烯基苯、纯对－二乙烯基苯为偶联剂合成了一系列星形聚合物。研究了偶联反应的影响因素。结果表明,反应体系产生凝胶的趋势随着二乙烯基苯与预聚物配比的增加而增加;偶联反应速度随着反应物总浓度的增加而加大;提高反应温度有利于提高偶联效率;以低单体转化率下合成的预聚物为大分子引发剂时的偶联效率高于高单体转化率下合成     

Benzocyclobutenyl functionalized polymers of cyclotrimerized terminal diynes: synthesis and crosslinking

The monomers 1,13-tetradecadiyne, 1,11-dodecadiyne, 1,9-decadiyne and 1,7-octadiyne were cyclotrimerized, using niobium pentachloride as the catalyst, in the presence of 1,5-hexadiyne, which co-cyclotrimerizes to give a benzocyclobutene (BCB) capping group. Molecular weights of the BCB-capped oligomers were in the 3100–8000 range, with fairly narrow polydispersities. The oligomers were characterized by ¹H NMR and IR spectoscopy, along with GPC and DSC studies. DSC studies on the end-capped oligomers show that each exhibits an exotherm around 260°C, indicative of the formation of carbon–carbon bonds in a crosslinking reaction. The final, crosslinked materials may be regarded as thermosetting thermoplastics, since they are hard at room temperature and soft at 250°C.     

Synthesis and application of polyethylene-based functionalized hyperbranched polymers

Polyethylene is one of the largest volume commodity polymers, with excellent physical and chemical properties. Polyethylene-based functionalized hyperbranched polymers are newly developed materials with unique structures and properties. Their architecturally complex structure – topology, composition and functionality – may be designed for different applications, with reduction of complexity and cost in preparation. This review focuses on the synthesis strategies and applications of polyethylene-based functionalized hyperbranched polymers.     

Azoxyarylene compounds and polymers by a copper-pyridine catalyzed oxidative coupling reaction

Summary Azoxyarylene compounds can be quantitatively formed by oxidative coupling of N-arylhydroxylamines in the presence of a copper-pyridine catalyst and dioxygen. This new method was utilized to synthesize a poly(azoxy arylene). Polymer 5 obtained has a weight average molecular weight of 6,500 and a number average molecular weight of 4,400. Received: 1 February 1999/Revised version: 23 April 1999/Accepted: 23 April 1999     

Synthesis of aromatic carboxyl functionalized polymers by atom transfer radical polymerization

The synthesis of aromatic carboxyl functionalized polymers by atom transfer radical polymerization is described. The α‐bromo‐p‐toluic acid ( 1 ) initiated polymerization of styrene in the presence of copper(I) bromide and 2,2′‐bipyridyl affords quantitative yields of the corresponding aromatic carboxyl functionalized polystyrene ( 2 ). Polymerization proceeded via a controlled free radical process to afford quantitative yields of the corresponding aromatic carboxyl functionalized polymers with predictable molecular weights (M_n = 1600–25 900 g mol⁻¹), narrow molecular weight distribution (M_w /M_n = 1.1–1.40) and an initiator efficiency above 0.87. The polymerization process was monitored by gas chromatographic analysis. The functionalized polymers were characterized by thin layer chromatography, size exclusion chromatography, spectroscopy, potentiometry and elemental analysis. © 2000 Society of Chemical Industry     

偶联法高苯乙烯橡胶的合成

以环己烷为溶剂、苯乙烯和丁二烯为单体、正丁基锂(n-BuLi)为引发剂、四氢呋喃(THF)为结构调节剂,通过活性负离子溶液聚合及偶联合成了高苯乙烯橡胶。研究了聚合温度、苯乙烯/丁二烯(质量比)、相对分子质量、n(THF)/n(n-BuLi)、丁二烯封端对高苯乙烯橡胶力学性能的影响及n(THF)/n(n-BuLi)对偶合效率的影响。结果表明,当苯乙烯/丁二烯质量比为60/40、THF/n-BuLi物质的量比相对为1.0~1.5时,在(63±3)℃下聚合,(75±5)℃下偶合可得到力学性能较好的高苯乙烯橡胶,其数均相对分子质量为(15~20)×104,相对分子质量分布为2.0~2.3。     

Synthesis and evaluation of hexafluorodimethylcarbinol functionalized polymers as microsensor coatings

Polystyrenes, polyacrylates, and poly(3,4-isoprenes) incorporating the hexafluorodimethylcarbinol functionality have been synthesized, characterized, and tested as microsensor coatings on a surface acoustic wave (SAW) device for dimethyl methylphosphonate (DMMP) vapor absorption sensitivity. The syntheses involved monomer functionalization and polymerization or hexafluoroacetone reaction with preformed polymer. All fluoroalcohol functionalized polymer coatings displayed sub parts per million level sensitivity with the slope of the absorption isotherm steepest at low DMMP concentrations. The order of sensitivity for the isomeric polystyrene fluoroalcohols (meta > para ? ortho) paralleled that of the relative free hydroxyl to hydrogen-bonded hydroxyl content. Strong hydrogen bonding between the fluoroalcohol polymers and DMMP vapor was observed by IR spectroscopy. Acylation of the fluoroalcohol group markedly reduced the DMMP sensitivity.     

Synthesis of star-shaped poly(vinyl ether)s by living cationic polymerization: Pathway for formation of star-shaped polymers via polymer linking reactions

Summary: Star-shaped polymers of isobutyl vinyl ether (IBVE) with a microgel core of an aliphatic divinyl ether (2) were synthesized in high yield on the basis of the living cationic polymerization with the HCl/ZnCl₂ initiating system. GPC analysis demonstrated that linear coupling products ("two-armed" polymers) and three-armed star polymers formed during the early stages of the linking reaction, and that subsequent coupling reactions between such low molecular weight star polymers gave star-shaped polymers with more arms. The number of arms ranged from 5 to 22, which increased with increasing [2]₀/[P^*] ratio and/or shortening the arm chain. Received: 11 April 2000/Accepted: 24 April 2000     

合成反应与精馏过程耦合制备四乙酰乙二胺

采用精馏过程与合成反应耦合技术生产四乙酰乙二胺 ,并研究了物料比、反应温度和时间对产率的影响。结果显示最佳工艺条件为 :n(乙二胺 )∶n(乙酸 )∶n(乙酐 ) =1∶2 .5∶6 ,第一步在 1 2 0℃下反应 3h ,第二步在 1 4 0℃下反应 6h。控制合适的精馏回流比 ,总收率可达 79%。     

Synthesis and application of fluorescently labeled phthalic anhydride (PA) functionalized polymers by ATRP

Fluorescent PMMAs containing a phthalic anhydride (PA) group at the chain ends were prepared using the newly developed initiator 7 by atom transfer radical polymerization and subsequent pyrolysis. These polymers allowed for the detection of inter-macromolecular reaction in reactive polymer blends at a low concentration by the use of fluorescence-gel permeation chromatography. The PA-amine coupling reaction proved to be efficient in reactive blending studies for the compatibilization of PS-PMMA blends at low concentration (≤8%) giving a morphology where the average PMMA drop size is 0.6 μm. With 7-nitrobenz-2-oxa-1,3-diazole (NBD) groups as the fluorescent label, the blend morphologies could be visualized in three dimensions by laser confocal microscopy.     

熔融缩聚法制备星形支化聚乳酸

以L-乳酸为原料,季戊四醇为支化剂,使用氯化亚锡和对甲苯磺酸复合催化剂,采用熔融缩聚法合成了星形支化聚乳酸.探讨了支化剂用量、催化剂用量、反应温度和时间等条件对星形支化聚乳酸特性黏数的影响.结果 表明,n(LLA)/n(PET)=1500,催化剂snCl2和对甲苯磺酸用量为单体L-乳酸质量的0.5%,聚合温度为180℃,体系压力为1.5kPa时熔融缩聚12 h,可得到特性黏数为0.634 dL/g的星形聚乳酸.采用凝胶渗透色潜-十八角激光散射仪、黏度计测定了聚合物的摩尔质量、均方旋转半径和特性黏数[η],并证明了支化结构的存在.最后,采用DSC、TG研究了星形聚乳酸的热性能.     

Effects of hetero-armed star-shaped PCL-PLA polymers with POSS core on thermal,mechanical, and morphological properties of PLA

In this study, AB type-heteroarm star-shaped poly(ε-caprolactone)-poly(lactic acid) (PCL-PLA) polymers with polyhedral oligomeric silsesquioxane (POSS) core ((PCL)₄-POSS-(PLA)₄, coded as SPLA) were synthesized successfully by using ring opening polymerization and click chemistry techniques together. The synthesized polymers were compounded with commercial PLA at different blending ratios (PLA/SPLA = 100/0, 95/5, 90/10, and 80/20% wt). The effects of heteroarm SPLA polymers having different arm lengths (n = 10, 20, 30, and 50) on morphological, mechanical, and thermal behaviors of PLA were investigated. It is determined that SPLA polymers with four PLA and four PCL arms on its structure enhanced mechanical properties of PLA. The tensile modulus decreased, and lowest modulus values were observed with blends prepared at 80/20 ratio. Elongation at break values increased in all blends, maximum increment was observed with 1,4-phenylene diisocyanate (PDI) containing SPLA20 blends prepared at 90/10 ratio. This result showed that SPLA20 had optimum chain length for chain extension reactions of between PLA chains. Besides, a trade compatibilizer PDI was utilized to enhance the intercompatibility of binary polymer blends.     

Synthesis and characterization of fluorine–thiophene-based π-conjugated polymers using coupling reaction

A solution processible fluorine–thiophene-based copolymers, namely poly[2,7-bis(4-octyl-2-thienyl)-9,9-dioctylfluorene-co-alt-5,5′-(2,2′-bithiophene)] (P1), poly[2,7-bis(3-octyl-2-thienyl)-9,9-dioctylfluorene-co-alt-5,5′-(2,2′-bithiophene)] (P2), poly[2,7-bis(3,3′-dioctyl-5,5′-bithien-2yl)-9,9′-dioctylfluorene-co-alt-5,5′-(2,2′-bithiophene)] (P3) were synthesized using Suzuki and Stille coupling reaction. The polymers showed weight loss starting around 400 °C indicative of good thermal stability. UV–vis properties and photoluminescence (PL) properties were investigated in toluene. P1, P2 and P3 exhibited the absorption maximum at 450, 428 and 435 nm and their PL spectrum peaked at 587, 559 and 560 nm, respectively. And all polymers, P1, P2 and P3, showed electroluminescence (EL) spectrum peaked at 592, 595 and 607 nm in the range of orange red. The polymers were electrochemically active in oxidation regions. P3 especially showed high oxidation stabilities in 1.17 V vs. Ag/Ag⁺. And P1 and P3 showed higher crystallinity than P2, because they have a repeated unit of 3,3-dialkyl-quaterthiophene.     

A theory of topological separation of linear and star-shaped polymers by two-dimensional chromatography

Topology influences the size of macromolecules, but polymers are usually distributed with respect to molar mass, which also results in the size distribution within a polymeric sample. Due to this fact size-exclusion chromatography (SEC) is not able to separate even moderately polydisperse polymers by topology; the same is also true for the adsorption chromatography (AC). The full separation by molar mass and topology is not possible by any single mode of chromatography. These problems can be solved by means of two-dimensional chromatography which combines SEC and AC mechanisms. A theory of interactive chromatography of linear and star-shaped ideal-chain polymers is used to analyze two-dimensional chromatographic separation of polydisperse linear and star polymers. Basing on this theory, we simulate 2D-chromatograms for model mixtures of polydisperse linear and star-shaped polymers of equal average molar mass, and demonstrate that 2D-separation of such polymers by topology is possible. A possibility to separate symmetric and very asymmetric stars by 2D-chromatography is predicted. The influence of the molar-mass heterogeneity, pore size and adsorption interaction parameter on the 2D chromatographic pattern is analysed, and the conditions for a good separation of linear and star polymers are formulated. The theoretical results are in a qualitative agreement with the experimental data, which have been reported previously by Gerber and Radke.     

星状支化PS的合成与表征

利用原子转移自由基聚合方法,以α-溴代苯乙烷为引发剂,CuBr／2,2'-联二吡啶作为催化体系,合成星状支化聚苯乙烯(PS)。引发二苯甲烷双马来酰亚胺／苯乙烯电荷转移络合物体系就地优先生成多官能团引发剂,再引发苯乙烯聚合。采用核磁共振、凝胶渗透色谱、多角度激光散射和特性黏数等分析方法对聚合过程、聚合物结构、聚合物相对分子质量及其分布进行分析与表征。由多角度激光散射法测定的绝对重均分子量是由凝胶渗透色谱测定的4倍左右,相同相对分子质量的线型PS的特性黏数是星状PS的20倍,证实聚合产物确实具有支化结构。     

Polymer hybrids of functionalized silsesquioxanes and organic polymers utilizing the sol-gel reaction of tetramethoxysilane

The ternary polymer hybrids were prepared by organic polymers such as poly(2-methyl-2-oxazoline) (POZO) or poly(N-vinylpyrrolidone) (PVP) and aminopropylsilsesquioxane (Cube-aminopropyl) utilizing the sol-gel reaction of tetramethoxysilane (TMOS). The prepared polymer hybrids were characterized by IR, thermogravimetric analysis (TGA), X-ray diffraction (XRD), ¹H NMR, scanning electron microscopy (SEM), etc. In this hybrid system, hydrogen-bonding interactions played a critical role in the formation of the transparent polymer hybrids. Polymer hybrids using POZO showed high transparency and homogeneity in a wide range of the feed ratios of POZO to Cube-aminopropyl. On the other hand, in case of polymer hybrids using PVP, higher Cube-aminopropyl ratio brought about the phase separation, indicating the aggregation of the Cube-aminopropyl itself. The homogeneity of ternary polymer hybrids was found to be closely dependent on the difference between strength of hydrogen bonding interaction of polymer and residual silanol groups of silica gel and strength of that of polymer and Cube-aminopropyl. It is also observed that initial decomposition temperature of polymer hybrids was increased with increasing the Cube-aminopropyl ratio.     

Suzuki-Miyaura偶联反应在沙丁胺醇合成中的应用

以5-溴水杨醛为起始原料,经还原、苄基保护、Suzuki-Miyaura偶联、双键加成、亲核取代、钯碳还原等反应合成了沙丁胺醇,反应总收率为56.0%（以5-溴水杨醛计）。并对关键的Suzuki-Miyaura偶联反应条件进行了优化,获得最优的反应条件为：n(中间体II)：n(乙烯基三氟硼酸钾)：n(氯化钯)：n(三苯基膦)：n(碳酸铯)=1:1.2:0.02:0.06:2,在四氢呋喃/水（体积比 9:1,0.5 mol/L,以中间体II物质的量计）混合溶剂中回流反应12h。中间体产物的结构经高分辨质谱（HRMS）、1HNMR以及13CNMR进行了确证。该法反应条件温和、操作简单、可控性强、无需柱层析分离,适合沙丁胺醇的放大制备,具有工业化应用价值。     

Synthesis and self-assembly study of two-armed polymers containing crown ether core

Two functional crown ether initiator, bis[4′-(2-bromobutyryl)]dibenzo-18-crown-6 (BBDC) was synthesized through the condensation of dibenzo-18-crown-6 with 2-bromobutyric acid in the presence of polyphosphoric acid. Atom transfer radical polymerizations of styrene (St), methyl acrylate, methyl methacrylate and butyl acrylate were carried out in bulk to produce the polymers with well-controlled molecular weights and narrow molecular weight distributions (1.12-1.32). Based on ¹H NMR results, both the two bromides of BBDC initiated the polymerizations. The well-defined two-armed polymers were self-assemblized in the presence of potassium cations. Their morphologies of the film obtained were studied by atomic force microscopy with tapping mode.     

Synthesis and characterization of star-shaped block copolymers with polyhedral oligomeric silsesquioxane (POSS)core via ATRP

Star-shaped PMMA-b-PS block copolymers with POSS core were prepared by atom transfer radical polymerization of St using star-shaped POSS/PMMA-Cl as a macroinitiator in presence of CuCl, 2,2,-bipyridine, toluene at 110 °C. The core-first method, which used an active multifunctional core to initiate the growth of polymer chains, was applicable to making star-shaped block copolymers with POSS core. The structure of hybrid star-shaped PMMA-b-PS block copolymers was characterized by GPC and ¹H NMR, respectively.