Prediction and Experimental Characterization of the Molecular Architecture of FRP and ATRP Synthesized Polyacrylate Networks

Summary: This work reports experimental and modeling studies concerning the conventional (FRP) and atom transfer radical polymerization (ATRP) of acrylate/diacrylate monomers. In the framework of a recently developed general approach, kinetic models including crosslinking reactions and branching by chain transfer to polymer are discussed for FRP and ATRP polymerization systems. Besides molecular weight distribution (MWD), fairly good predictions of the z-average radius of gyration could be obtained for these non-linear polymers. A set of experiments was performed at 1 L scale in a batch reactor using n-butyl acrylate (BA) or methyl acrylate (MA) as monovinyl monomers and 1,6-Hexanediol diacrylate (HDDA) or bisphenol A ethoxylate diacrylate (BEDA) as crosslinkers. In FRP experiments, AIBN was used as initiator and ATRP polymerizations were initiated by ethyl 2-bromopropionate (EBrP) and mediated by CuBr using PMDETA (N,N,N′,N″,N″-pentamethyldiethylenetriamine) as ligant. Polymerizations were carried out in solution at 60 °C with different dilutions using toluene and DMF as solvents. Products formed at different polymerization times were analyzed by SEC/RI/MALLS yielding average MW, MWD, z-average radius of gyration and monomer conversion. Important differences in the molecular architecture of the synthesized FRP and ATRP highly branched polyacrylates have been identified. Comparisons of experimental results with predictions have put into evidence the important effect of intramolecular cyclizations at all dilutions, even with ATRP polymerizations.     

Hyperbranched Poly（amide-ester） Mildly Synthesized and Its Characterization

AB2-type-prepolymerized monomer was rapidly （2 h） prepared at room temperature （25 ℃） using commercially available maleic anhydride （MA） and diethanolamine （DEA） as raw materials. By employing toluene-p-sulfonic acid as a catalyzer, a series of hyperbranched poly（amide-ester） （HBPAE） were successfully synthesized from prepared AB2 monomer by solution condensation polymerization through ＂one-step process＂ or ＂pseudo one-step process＂ （using pentaerythritol as a center core）. The processes were carried out at high temperature of 120 ℃ for 6 h in air atmosphere （inert protection free） with reduced pressure distillation （0.08--0.096 MPa）. The results of FT-IR, UV-Vis, TGA, and intrinsic viscosity testing by Ubbelodhe viscometer showed that the prepared HBPAEs possess three-dimensional configuration with unsaturated conjugate structure, large numbers of branches and numerous terminal hydroxyl groups. These result in their low viscosity, high solubility and thermal stability.     

Chain Walking Ethylene Copolymerization with an ATRP Inimer for One‐Pot Synthesis of Hyperbranched Polyethylenes Tethered with ATRP Initiating Sites

A one‐pot procedure for the synthesis of hyperbranched polyethylenes tethered with ATRP initiating sites by chain walking ethylene copolymerization with an acrylate‐type ATRP inimer, 2‐(2‐bromoisobutyryloxy) ethyl acrylate (BIEA) is reported. Because of its ability to incorporate acrylate‐type comonomers and tolerance toward the α‐bromoester group, the chain walking Pd‐diimine catalyst, [(ArNC(Me) (Me)CNAr)Pd(CH₃)(NCMe)]SbF₆ (Ar = 2,6‐(iPr)₂C₆H₃), allowed the successful synthesis of a series of hyperbranched copolymers tethered with 2‐bromoisobutyryl groups at different densities. These copolymers may serve as polyfunctional macroinitiators for the ATRP of functional monomers to further synthesize core‐shell structured functionalized copolymers with a hyperbranched polyethylene core grafted with side chains of the functional monomers.

     

ABg型缩聚形成的超支化聚合物的支化度与分子形态

用聚合反应动力学模型, 详细分析了AB_g型缩聚体系中各种结构单元的演变, 对超支化聚合物支化度的各种定义作了比较, 并对AB_g型反应体系的支化度提出了一个改进的定义, 使得支化度随g的增加而增加, 当g从2增加到无穷大, 最大支化度相应地从0.5增加到1－e^－1. 对均方回转半径的数值计算表明, 在确定的A基团转化率(x), z-均均方回转半径几乎与g无关, 当x＝0.999时, 随着g从2增加到无穷大, z-均回转半径只增加0.1%. 但是, 同样的条件下, z-均聚合度增加到2倍. 这一现象表明在任何指定的A转化率, AB_g型缩聚中形成的超支化聚合物的分子轮廓与g无关, 随着g 增大而在超支化聚合物中增加的结构单元(或聚合度)必定分布在分子内部.     

预聚-酶催化缩聚法合成超支化聚酯及其结构表征

以丙三醇、1,6-己二醇和己二酸为共聚单体,以固定化脂肪酶Novozym435为催化剂,尝试先进行共聚单体的预聚后在有机介质中进行酶催化直接缩聚反应合成脂肪族超支化聚酯的新途径,考察了反应介质和反应温度对酶催化缩聚反应的影响,并采用凝胶渗透色谱和核磁共振确定产物的分子量和结构.结果表明,将单体的预聚与酶催化缩聚反应相结...     

Thermal and Photochemical Crosslinking of Hyperbranched Polyphenylene With Organic Azides

Here, we report on the first example of crosslinking (CL) hyperbranched polyphenylene ( hb–PPh ) with a small molecule crosslinker 1,3,5‐tris(azidomethyl)benzene ( TAMB ). It was successfully shown that CL of the hb–PPh / TAMB (9:1) film is possible either thermally or photochemically making use of fundamentally different reaction mechanisms. Starting from a model reaction to prove the feasibility of the thermal CL reaction, we went on to check both the thermal and the photochemical crosslinkability of micrometer thick films. IR spectroscopy was furthermore used to confirm the CL process. Finally, the thin film morphology of the films before and after CL was investigated by AFM, revealing that the surface morphology was unaffected by the CL processes.     

超支化聚酰胺的合成与表征

N-(二氨基苯甲酰)氨基乙酸;自缩聚;封端反应;超支化聚酰胺的合成与表征     

Synthesis and Characterization of Crosslinked Hyperbranched Polyglycidol Hydrogel Films

Hyperbranched polyglycidol (PGLD) was synthesized via anionic ring‐opening polymerization of glycidol using a special anionic initiator with multiple initiation sites. The resultant polymers were characterized by ¹H and ¹³C‐NMR spectra for confirming their structures, which consisted of linear, hyperbranched and dendritic structures. Molecular weight characteristics were determined by means of the gel permeation chromatography (GPC). With the intention of investigating the possibility of broad applications, PGLD hydrogel films were prepared using various crosslinking agents, i.e., glutaraldehyde and some dicarboxylic acids, and their physical properties such as swelling behavior and tensile (or Young's) modulus were measured and compared.     

高支化聚合物的合成与表征

介绍了近年来在高分子化学领域内十分活跃的高支化聚合物研究的状况。指出了通过ＡＢｘ型单体的缩聚反应和Ａ＝Ｂ－Ｃ＾８型单体的自缩合乙烯都可获得高支化聚合物。目前用以表征高支化聚合物支化度和分子量的方法主要为核心共振法和凝胶渗透色谱法,在实际应用中都存在局限性。     

十八烷基超支化分子的结构表征与破乳性能

以甲醇为溶剂,用十八胺、丙烯酸甲酯和乙二胺为原料,通过迈克尔加成反应和酰胺化缩合反应,制备了1.0 G超支化分子;通过红外光谱、核磁共振手段对合成产品的结构进行了表征,且考察了十八烷基超支化分子对O/W型原油模拟乳液的破乳性能,并与传统的线性破乳剂SP-169进行了对比.结果表明:在温度为50℃、添加量为20 mg/L、破乳时间为120 min的条件下,其脱水率达到了76.2%,脱出水中的含油量为41.9 mg/L;而破乳剂SP-169在相同的条件下的脱水率为61.5%,脱出水中的含油量为52.4 mg/L.     

Computer‐Aided Optimization of Conditions for Fast and Controlled ICAR ATRP of n‐Butyl Acrylate

The potential of initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) for the synthesis of well‐defined poly(n‐butyl acrylate) is analyzed by means of simulations. The kinetic model accounts for reactivity differences between secondary and tertiary macrospecies and considers the possible influence of diffusional limitations. CuBr₂ is used as transition metal salt and the commercially available N,N,N′,N″,N″‐pentamethyldiethylenetriamine as ligand. For targeted chain lengths (TCLs) up to 1000, the ICAR ATRP can be performed relatively quickly, and with ppm levels of ATRP catalyst. For moderate TCLs, slightly higher ppm levels are required if excellent control over chain length is also desired. In all cases, limited loss of end‐group functionality (EGF) results.

     

Synthesis and Characterization of Ag2S Nanocrystals in Hyperbranched Polyurethane at Room Temperature

Ag₂S nanoparticles in hyperbranched polyurethane matrix were prepared through the in situ reaction with thioacetamide as the sulfur source at room temperature. Transmission electron microscopic analysis revealed a uniform spherical shape for Ag₂S nanoparticles, with an average size of about 4-10 nm and a narrow size distribution. X-ray powder diffraction and UV-vis spectroscopy were also used to characterize the obtained nanoparticles     

Modeling of Mechanical Properties of Polymeric Systems with Branching/Crosslinking,Particularly Their Mechanical Resistence and Stability

A theoretical method for the estimation of mechanical characteristics of polymeric structures is proposed. This method uses the statistical polymer method for modeling branched/crosslinked structures. The proposed method is utilized for the estimation of mechanical resistance and stability of microporous polymeric materials. An engineering method for the evaluation of mechanical stability and resistance of polymeric materials is derived.     

含三苯胺单元的超支化共轭聚合物的合成、表征及应用

本实验采用Wittig方法制得了未封端和封端的超支化聚三苯胺-对苯乙烯撑型聚合物,对两种共轭聚合物进行了表征和性能测试.聚合物溶液和固体膜在紫外光照射下均发出较强的绿光.首次对这类聚合物在硝基芳烃化合物荧光猝灭能力进行了初步研究,结果表明:与未封端产物相比,封端后的超支化共轭聚合物在邻硝基甲苯(o-NT)的荧光猝灭效率上有明显提高,当o-NT浓度为21.5×10^-3mol/L时,荧光猝灭效率达到97%.这类共轭聚合物不仅合成操作较为简便,猝灭效率也较高,是一种很有潜力的硝基芳烃化合物荧光检测材料.     

超支化聚酯的合成与应用——纳米银粒子的制备与表征

超支化聚酯的合成与应用——纳米银粒子的制备与表征;超支化聚酯;纳米银;稳定剂;光还原     

Synthesis and properties of hyperbranched poly(ether sulfone)s prepared by self‐polycondensation of novel AB2 monomer

Hyperbranched poly(ether sulfone)s were prepared by the self‐polycondensation of the novel AB₂ monomer, 4‐(3,5‐hydroxyphenoxy)‐4′‐fluorodiphenylsulfone. The high‐molecular‐weight polymers were isolated in good yields. The degree of branching (DB) of the resulting polymers was investigated by the preparation of dendritic and linear model compounds. The DB determined by gated decoupling ¹³C NMR measurements was in the range 0.17–0.41 and was dependent on the base used for the self‐polycondensation. It was found that cesium fluoride was an effective base to form the polymer having the DB of 0.41. The resulting hyperbranched poly(ether sulfone)s showed good solubility in organic solvents. The solubility and the glass transition temperature of the polymers were influenced by the terminal functional groups. The unique thermal crosslinking phenomenon was observed during the DSC measurements of the hydroxyl‐terminated hyperbranched poly(ether sulfone) under air condition. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

双键可控紫外光固化超支化聚氨酯丙烯酸酯的制备与表征

以甘油为核,二乙醇胺(DEOA)和异佛尔酮二异氰酸酯(IPDI)为原料,合成了含6个端羟基的加核型超支化聚氨酯(HBPU-OH),再通过加入IPDI和丙烯酸羟乙酯(HEA)等原料引入聚氨酯基团和丙烯酸双键,制备出加核型双键数目可调的紫外光(UV)固化超支化聚氨酯丙烯酸树脂(HBPUA).用傅里叶交换红外光谱和核磁共振波谱表征了HBPUA的结构,用示差扫描量热仪和热重分析仪研究了HBPUA的热性能.结果表明,合成了超支化结构的HBPUA;HBPUA玻璃化转变温度(T_g)为67.8℃,低于HBPU-OH的T_g(110.0℃),这是由于HEA的引入增加了分子的柔性;HBPU-OH和HBPUA的热分解均出现3个阶段.     

以季戊四醇为"核分子"超支化聚酯-酰胺的合成及表征

以二异丙醇胺(DIPA)与六氢苯酐(HHPA)为原料合成了一种端基带有一个羧基、两个羟基的AB2型单体。用季戊四醇(PETL)作为“核分子”,按一定的摩尔配比与AB2型单体反应,分别得到两种不同的超支化聚酯-酰胺(1GHP、2G—HP)。并采用红外光谱(IR)、凝胶渗透色谱法(GPC)、粘度法等方法对其结构进行了表征。结果表明：1GHP、2G—HP的多分散性指数分别为1．47和2．17,呈现很窄的分子量分布。两种分子的粘度与浓度的关系服从Einstein粘度方程,具有紧凑的球形分子结构。     

Synthesis,characterization, and rheological properties of multiarm stars with poly(glycidol) core and poly(methyl methacrylate) arms by AGET ATRP

Well‐defined multiarm star block copolymers poly(glycidol)‐b‐poly(methyl methacrylate) (PGOHBr‐b‐PMMA_x) with an average number of PMMA arms of 85, 55, and 45 have been prepared. The core‐first approach has been selected as the methodology using atom transfer radical polymerization (ATRP) of MMA from an activated hyperbranched poly(glycidol) as the core. These activated hyperbranched macroinitiators were prepared by esterification of hyperbranched poly(glycidol) (PGOH) with 2‐bromoisobutyryl bromide. The effect of monomer/initiator ratio, catalyst concentration, time, temperature, and solvent on the growing of the arms has been studied in detail in order to optimize the process and to diminish the radical‐radical coupling. The final products and intermediates were characterized by means of size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) and Fourier transform‐infrared (FTIR) spectroscopy. The length of PMMA arms was determined by SEC after cleavage of ester bond linked to PGOH core. Glass transition temperature (T_g), thermal stability and rheological properties of the multiarm star copolymers were also studied. Finally, tapping mode atomic force microscopy (TMAFM) allowed the clear visualization of nano‐sized particles (80–200 nm) corresponding to individual star molecules. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011