环氧化物开环聚合催化体系的研究进展

制备高质量的环氧化聚合物的关键是采用合适的催化剂。在我国 ,对环氧化物聚合催化剂的研究还处于研制开发阶段 ,本文提到的聚合方法各有其局限性 ,阳离子聚合能制造出许多有商业价值的高分子材料 ,但副反应多 ,分子量不易控制 ,一直未能实现工业化。阴离子聚合过程中往往存在转移反应 ,会生成低分子量齐聚物。配位聚合虽然在一定程度上可以实现聚合产物的立体结构调控 ,但反应机理复杂、反应过程难以控制、催化剂价格昂贵 ,目前还不能实现工业化。因此 ,尽快研究开发出一系列合适催化剂用来合成高质量的环氧化聚合物 ,必将带来巨大的经济效益和社会效益。     

双金属氰化物催化环氧化物开环聚合的研究进展

综述了近年来双金属氰化物催化剂制备聚醚多元醇的研究进展,详细介绍了双金属氰化物催化剂的制备及其催化环氧化物的聚合机理、聚合工艺方面的研究现状,并展望了催化剂制备及其催化环氧化物合成聚醚今后的研究方向。     

环硅氧烷开环聚合阴离子催化剂的研究进展

介绍了传统的阴离子催化剂(碱金属催化剂、暂时性催化剂及硅醇盐催化剂)和部分新型催化剂,对阴离子开环聚合催化剂的应用和研究现状进行了综述.     

环氧生物质油开环催化剂的研究进展

环氧生物质油经醇、酸酐和有机酸等亲核试剂攻击,发生开环反应,制备高性能的生物润滑油。近年来,生物质油环氧化-开环的研究主要集中于分子结构对润滑油性能影响和环氧化催化剂的研发,目前,关于环氧生物质油开环催化剂的综述较少。本文总结了环氧生物质油开环催化剂的研究进展,重点论述了液体酸催化剂、固体酸催化剂、离子液体催化剂等。对现有催化体系进行简要分析,并指出各类催化剂的优点、存在的问题及今后的发展方向。     

开环聚合酚醛树脂研究进展

介绍了苯并恶嗪中间体的国内外研究概况。着重介绍了国内近年来在苯并恶嗪中间体合成、树脂固化反应研究和产品应用开发等方面取得的进展。     

希夫碱催化剂催化丙交酯本体开环聚合

合成了希夫碱催化剂,并成功地催化丙交酯本体开环聚合。结果表明,希夫碱催化剂催化合成聚乳酸可达到较高的转化率（高于95％）。研究了单体与催化剂物质的量比、聚合时间及聚合温度对该催化剂催化丙交酯本体开环聚合反应的转化率及所得聚乳酸相对分子质量的影响。当单体与催化剂物质的量比为400,聚合时间24h,聚合温度140℃时,可得到黏均相对分子质量Mq=8．439×10^4的聚乳酸。     

丙交酯开环聚合催化体系的研究进展

介绍了丙交酯开环聚合的三种反应机理:阴离子型开环聚合、阳离子型开环聚合和配位-插入开环聚合。根据其反应机理,催化剂可分为:质子酸型催化体系、路易斯酸型催化体系、碱金属催化体系、金属有机化合物催化体系、氧化物催化体系、稀土化合物催化体系及其他催化体系。此文阐述了这7种催化体系的不同特点,对其催化性能进行了比较。     

环氧化物阳离子开环聚合机理

介绍了环氧化物阳离子开环聚合的机理,主要包括活性链端机理和活性单体机理等。活性链端机理认为聚合的活性中心位于聚合增长链的链端,聚合单体与活性链端接触发生聚合反应实现链增长;活性单体机理认为聚合的活性中心位于单体分子,在活性单体向聚合链端羟基增加的过程中实现链增长。两者相结合可较成功地解释环氧化物开环聚合的实验现象。     

二氧化碳/环氧化合物开环共聚催化剂进展

“双碳”背景下,利用CO₂与环氧化合物为原料制备聚醚碳酸酯多元醇是CO₂化工利用的有效途径。高效的催化剂能够促进CO₂与环氧化物反应,制备更高性能的聚合物产品。本文详细介绍了近3年CO₂与环氧化合物开环共聚催化剂研究的主要进展。文中从非均相催化剂和均相催化剂两个方面,分别对金属羧酸盐、双金属氰化物、金属Salen、金属卟啉以及新型有机催化剂进行归类和综述。低廉的非均相催化剂仍是工业化实验的首选,但如何通过催化剂制备工艺控制活性位点分布,从而控制聚合物产品质量,是未来需要研究的重点。金属Salen催化剂是目前最热门的研究方向,其有机配体结构的多样性赋予多种金属组合配位的可能,期待开发更高效低廉的催化剂。     

二氧化碳与环氧烷开环共聚催化剂研究进展

综述了二氧化碳与环氧烷开环共聚制备聚碳酸酯的各类催化剂的研究进展,指出了研制高效、制备工艺简单、廉价易回收的环境友好催化剂仍是合成聚碳酸酯这一利用方式的研究重点,为二氧化碳的减排和资源化利用提供参考。     

微波辅助开环聚合反应

综述了微波辐照下ε-己内酯、丙交酯、ε-己内酰胺以及其它一些单体的开环聚合研究进展,比较了微波辐照与传统加热方法下的开环聚合。     

Chemospecific ring-opening polymerization of α-methylenemacrolides

α-Methylenemacrolides having various groups, such as aromatic, ether, and amine, were enzymatically, anionically, and radically polymerized. The polymerization with the lipase catalyst successfully afforded polymers only through the ring-opening process, whereas the vinyl polymerizations selectively proceeded by using anionic and radical initiators. The polyesters obtained by the enzymatic polymerization have a polymerizable methacrylic methylene group in the main-chain, in addition to the aromatic and polar groups, and were further radically polymerized to quantitatively produce a cross-linked polymer gel.     

Kinetically controlled siloxane ring-opening polymerization

Some basic aspects of the kinetics and mechanisms of anionic and cationic ring-opening polymerization of cyclic siloxanes are discussed in connection with their use in polymer synthesis. The emphasis is put on the polymerization of strained ring monomers, such as cyclic trisiloxanes, since these provide the possibility of tailoring the polymer structure. Much attention is devoted to association phenomena and to oligomer formation processes.This review is from the Second International Topical Workshop, Advances in Silicon-Based Polymer Science.     

Synthesis of latex particles by ring-opening metathesis polymerization

This paper reviews the recent discoveries that were achieved by our group in the field of particle synthesis via ring-opening metathesis polymerization (ROMP). Both polynorbornene and polybutadiene-based particles were prepared by the respective ROMP of norbornene and cyclooctadiene initiated by (PCy₃)₂Cl₂RuCHPh using several methods of polymerization in dispersed media, such as dispersion, suspension and miniemulsion. Depending upon the process implemented, particles size was found to range from 300 nm to 20 μm.     

Acyclic metathesis during ring-opening metathesis polymerization of cyclopentene

‘Living’ ring-opening metathesis polymerization (ROMP) permits the synthesis of narrow-distribution homopolymers and well-defined block copolymers - provided no side reactions occur. However, acyclic metathesis between the chain end and double bonds in the polymer backbone competes with propagation during ROMP of cyclopentene, even with a mild Mo catalyst, though the rate constant is some 1600-fold smaller. ‘Dead’ chains in the reaction mixture can also be attacked; the products of acyclic metathesis are tagged by quenching the ROMP reaction with pyrenecarboxaldehyde. The extent of acyclic metathesis can be minimized through proper choice of reaction conditions, permitting the synthesis of narrow-distribution polycyclopentene with 100 kg/mol molecular weight.     

Synthesis of comb-shaped copolymers by combination of reversible addition-fragmentation chain transfer polymerization and cationic ring-opening polymerization

Comb-shaped graft copolymers with poly(methyl acrylate) as a handle were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization and ring-opening polymerization (ROP) techniques in three steps. First, copolymers of poly(styrene-co-chloromethyl styrene), poly(St-co-CMS), were prepared by RAFT copolymerization of St and CMS using 1-(ethoxycarbonyl)prop-1-yl dithiobenzoate (EPDTB) as RAFT agent. Second, the polymerization of MA using poly(St-co-CMS)-SC(S)Ph as macromolecular chain transfer agent produced block copolymer poly(St-co-CMS)-b-PMA. Third, cationic ring-opening polymerization of THF was performed using poly(St-co-CMS)-b-PMA/AgClO₄ as initiating system to produce comb-shaped copolymers. The structures of the poly(St-co-CMS), poly(St-co-CMS)-b-PMA and final comb-shaped copolymers were characterized by ¹H NMR spectroscopy and gel permeation chromatography (GPC).     

Branched aliphatic polyesters by ring-opening (co)polymerization

The rapid development of biodegradable and biocompatible materials for biomedical applications is reflected in the search for new methods for aliphatic polyester modification applicable in this field. One possible approach is modification by changes to the polymer topology.This review covers the main methods of synthesis of branched aliphatic biodegradable and biocompatible (co)polyesters, where the ring-opening polymerization (ROP) of cyclic esters or cyclic carbonates is the leading process. First, literature examples of ring-opening multibranching polymerization (ROMBP) of AB₂-type hydroxyl-substituted cyclic lactones, lactides and carbonates are cited followed by the presentation of the application of AB-type cyclic esters and additionally AB₂ cyclic ethers or esters as “branching monomers” for the synthesis of branched polyesters based on polycaprolactone (PCL), polylactide (PLA) and polyglycolide (PGA). In the following part, methods involving the combination of the ROP of AB-type cyclic esters and condensation processes leading to branched structures are summarized. Other related strategies leading to “dendri-star” or “core–shell” copolyesters are also discussed. Several examples of approaches to PCL and PLA graft copolymer syntheses are also shown. The advantages and disadvantages of the presented methodologies of branched polyester synthesis are highlighted. Finally, the influence of the branched structure on the properties of the presented class of polyesters, important from the application point of view, is considered.     

Mechanism and kinetics of the free radical ring-opening polymerization of cyclic allylic sulfide lactones

The polymerization of 7-, 8- and 11-membered lactones, 6-methylene-1,4-oxathiepan-7-one, 3-methylene-1,5-oxathiocan-2-one and 3-methylene-1-oxa-5-thiacycloundecan-2-one in benzene at 70, 40–70 and 40–65 °C, respectively, is presented. All polymerizations proceeded with complete ring-opening up to approximately 25% conversion, where insoluble polymer was formed. Evidence is given attributing polymer double bond loss to crosslinking, although redistribution of the molecular weights via addition to polymer double bonds followed by β-fragmentation also appears to occur for polymerizations of the 8- and 11-membered lactones. Michael adducts of lactones with 2-methyl-2-propanethiol were prepared as models for chain-transfer products of hydrogen abstraction by carbon-centred radicals. Polymerization rates were found to increase marginally with ring size. Arrhenius parameters obtained for the polymerizations of the 8- and 11-membered lactones indicated that the addition step was more important than fragmentation in determining the rate of propagation.     

Kinetic study on the ring-opening polymerization of octamethylcyclotetrasiloxane (D4) in miniemulsion

A kinetic study on the ring-opening polymerization (ROP) of octamethylcyclotetrasiloxane (D4) in miniemulsion is presented in this work. The polymerization is initiated by dodecylbenzenesulfonic acid (DBSA) which also serves as the surfactant (inisurf). The influence of the size of monomer droplet and the concentration of DBSA on the polymerization rate were studied. Since the main place for the ROP of D4 was confirmed to be at the oil/water interface, a three-layer interface model was proposed to analyze the distribution of molecules at the interface and the effects of DBSA. A kinetic equation is then developed based on this model. In the equation, the polymerization rate (R_p) is related to the initial monomer concentration ([D4]₀), the droplet radius (r), the coverage of DBSA on monomer droplets surface (x). The polymerization rate can be predicted from the kinetic equation feeding all parameters with their experimental values. Finally, the equation gave a good accordance between the predicted polymerization rate data and the experimental results under different polymerization conditions.