Rheological and chemorheological studies of cyclic aryl ether ketone and aryl ether thioether ketone oligomers containing the 1,2-dibenzoylbenzene moiety

The melt stability, shear rate, and temperature dependence of steady-state shear viscosity of molten cyclic aryl ether ketone and thioether ketone oligomers containing the 1,2-dibenzoylbenzene moiety have been investigated. The isothermal chemorheology of the ring-opening polymerization of cyclic oligomers 4 and 9 in the presence of a nucleophilic initiator was also conducted. The cyclic aryl ether ketone oligomers are thermally stable in the melt, and their melt viscosity is several orders of magnitude lower than their high molecular weight linear counterparts. At a given temperature, the steady-state shear viscosity of the molten cyclics initially undergoes shear thinning as the shear rate increases, and once the shear rate is above 10 s⁻¹, the molten cyclic oligomers behave like Newtonian fluids. For the amorphous cyclic oligomers studied, the steady-state shear viscosity at 100 s⁻¹ at a given temperature only depends on their glass transition temperature. The cyclic aryl thioether ketone oligomers are thermally unstable in the melt and undergo ring-opening polymerization in the absence of an initiator to form high molecular weight linear polymers with a concomitant rapid increase in viscosity. The rate of change in viscosity increases with temperature and is promoted by the addition of a catalytic amount of elemental sulfur or a disulfide such as 2,2-dithiobis(benzothiazole). It is hypothesized that the ring-opening polymerization is initiated by the in situ generated thiyl radical(s) and proceeds via a free radical route. © 1996 John Wiley & Sons, Inc.     

Aromatic disulfide polymers back to macrocyclic disulfide oligomers via cyclo-depolymerization reaction

A brand new and highly efficient method has been developed for the synthesis of aromatic macrocyclic disulfide oligomers. Cyclization was achieved by cyclo-depolymerization (CDP) of aromatic disulfide polymer in the presence of catalytic amount of thiols and weak base. The cyclic oligomers undergo a facile free-radical ring-opening polymerization to form high molecular weight polymer. Comparing with the conventional method for the preparation of macrocyclic aromatic oligomers by catalytic oxidation of dithiols, highly dilute condition was not necessary using the new method. The macrocyclics in high yield and with narrow molecular weight distribution were obtained. This method also provides a convenient technology for the recycle of aromatic disulfide polymers.     

Exfoliation of layered silicate facilitated by ring-opening reaction of cyclic oligomers in PET-clay nanocomposites

Ethylene terephthalate cyclic oligomers (ETCs) have been successfully polymerized to a high molecular weight poly(ethylene terephthalate) (PET) employing the advantages of the low viscosity of cyclic oligomers and lack of chemical emissions during polymerization. Using ring-opening polymerization of ETCs with organically modified montmorillonite (OMMT), we intend to ascertain the possibility of preparing high performance PET/clay nanocomposites. Due to the low molecular weight and viscosity, ETCs are successfully intercalated to the clay gallerys, what is evidenced by XRD showing a down-shift of basal plane peak of layered silicate along with TEM investigation. Subsequent ring-opening polymerization of ETCs in-between silicate layers yielded a PET matrix of high molecular weight along with high disruption of layered silicate structure and homogeneous dispersion of the latter in the matrix. Although co-existence of exfoliation and intercalation states of silicate layers after polymerization of ETCs rather than perfect exfoliation was observed, a dramatic increase in d-spacing along with fast polymerization presents us a great potential of cyclic oligomer process in producing a thermoplastic polymer-clay nanocomposites of extremely well-dispersed silicate nanoplatelets and the corresponding high performances.     

丙交酯开环法合成聚乳酸工艺探讨

研究了丙交酯开环法合成聚乳酸的工艺路线,考察了反应温度、反应时间、催化剂用量等工艺条件对聚乳酸分子质量的影响,在优化工艺条件下可以得到高分子质量和高结晶度的聚乳酸。     

Synthesis and characterization of a novel amphiphilic poly (ethylene glycol)–poly (ε-caprolactone) graft copolymers

A series of amphiphilic graft copolymers PEO-g-PCL with different poly (ε-caprolactone) (PCL) molecular weight were successfully synthesized by a combination of anionic ring-opening polymerization (AROP) and coordination-insertion ring-opening polymerization. The linear PEO was produced by AROP of ethylene oxide (EO) and ethoxyethyl glycidyl ether initiated by 2-(2-methoxyethoxy) ethoxide potassium, and the hydroxyl groups on the backbone were deprotected after hydrolysis. The ring-opening polymerization of CL was initiated using the linear poly (ethylene oxide) (PEO) with hydroxyl group on repeated monomer as macroinitiator and Sn(Oct)₂ as catalyst, then amphiphilic graft copolymers PEO-g-PCL were obtained. By changing the ratio of monomer and macroinitiator, a series of PEO-g-PCL with well-defined structure, molecular weight control, and narrow molecular weight distribution were prepared. The expected intermediates and final products were confirmed by ¹H NMR and GPC analyzes. In addition, these amphiphilic graft copolymers could form spherical aggregates in aqueous solution by self-assemble, which were characterized by transmission electron microscopy, and the critical micelle concentration values of graft copolymers PEO-g-PCL were also examined in this article.     

Challenging activated monomer ring-opening polymerization for direct synthesis of thiol end-functionalized polyesters

A direct, non-enzymatic procedure for the synthesis of thiol-functionalized polylactones was developed and optimized by using 2-mercaptoethanol, the simplest unprotected thiol-containing initiator for cationic ring-opening polymerization, catalyzed by HCl and methanesulfonic acid in dichloromethane solutions. Thiol-functionalized polylactones with a molecular weight of up to approximately 5000 Da were obtained in a controlled manner. It was observed that acid can play the dual role of activator and initiator, and for the first time, it was shown that abundant HCl and/or ambient temperature lead to the formation of undesired α-carboxy-ω-chloro-functionalized polylactones that form in parallel with the targeted thiol-functionalized ones. A plausible pathway towards the formation of chlorinated products is proposed based on an active-chain-end mechanism, and the procedure was optimized to eliminate its contribution to the polymerization process, thus allowing for the activated-monomer mechanism to prevail. Molecular weight characterization was performed using ¹H NMR and size-exclusion chromatography. The results indicate that the polymers obtained under optimized conditions possess high SH functionality and moderate polydispersity, and that ring-opening polymerization proceeded in a controlled fashion. The proposed method allows for the preparation of metal free materials readily suitable for biomedical and/or electronic applications.     

聚芳双硫醚/膨胀石墨/碳纤维纳米复合材料双极板的研制

以环状芳香双硫醚低聚物(COBDS)、膨胀石墨(EG)及碳纤维(CF)为原料,通过原位开环聚合制备出纳米复合材料双极板,并研究了这种复合材料的密度、电导率、弯曲强度、微观形态等特性.结果表明,这种纳米复合材料双极板具有密度小、导电性良好、弯曲强度较高以及气密性良好等优点.     

Microwave‐assisted synthesis of polyglycerol from glycerol carbonate

Microwave irradiation of glycerol carbonate allows formation of glycidol, which readily polymerizes to form polyglycerol under mild conditions comparatively to the classical polyetherification reaction involving high temperature and basic conditions. Analysis of the crude reactional mixture indicated the presence of low‐molecular weight oligomers constituted mainly of di, tri, and tetraglycerols with small quantities of higher molecular weights oligomers. Molecular size distribution was relatively similar to that of polyglycerols obtained under basic condition, even if these latter contained slightly higher amounts of high‐molecular weight oligomers. Structure of oligomers differs slightly according to the conditions of polymerization, and polyglycerols are obtained under microwave activation containing higher contents of cyclic isomers, whereas polyglycerols obtained under basic conditions contain more ramified isomers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Highly efficient ring-opening polymerization of tetrahydrofuran by anhydrous ferric chloride

Poly(tetramethylene ether glycol) (PTMG), widely used as a precursor in the fabrication of commodity polymers, is typically produced byacid-catalyzed polymerization of tetrahydrofuran (THF). Herein, we report a detailed investigation of the cationic ring-opening polymerization of THF catalyzed by ferric chloride (FeCl₃), which can be considered as a strong Lewisacid. The polymerization reactions were performed in the presence of acetic anhydride at 20°C with FeCl₃, which readily produced poly(tetramethylene ether glycol diester) (PTMG_DE). A maximum yield of 79.2% was obtained within 30 min using a FeCl₃ to acetic anhydride molar ratio of 5:4. The resulting polymers generally exhibited low molecular weights and a narrow polydispersity index and could be easily converted into PTMG using aqueous NaOH. In contrast with the FeCl₃-acetic anhydride system, other iron-based catalysts such as FeCl₂ and FeCl₃·6H₂O did not show any noticeable activity in the polymerization of THF. The proposed mechanism involves initiation of the acetyl cation generated by FeCl₃, propagation by nucleophilic addition of THF, and termination by the acetate anion, accounting for the high activity of the FeCl₃ catalyst for THF polymerization. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47999.     

Synthesis of amphiphilic macrocyclic graft copolymer consisting of a poly(ethylene oxide) ring and multi-poly(?-caprolactone) lateral chains

A series of amphiphilic macrocyclic graft copolymers composed of a hydrophilic poly(ethylene oxide) as ring and hydrophobic poly(?-caprolactone) as lateral chains with different grafting lengths and densities of side chains were prepared by a combination of anionic ring-opening polymerization and coordination-insertion ring-opening polymerization. The anionic ring-opening copolymerization of ethylene oxide (EO) and ethoxyethyl glycidyl ether (EEGE) was carried out first using triethylene glycol and diphenylmethyl potassium (DPMK) as co-initiators, and a linear α,ω-dihydroxyl poly(ethylene oxide) with pendant protected hydroxymethyls (l-poly(EO-co-EEGE)) was obtained. The monomer reactivity ratios of these compounds are r_1(EO) = 1.20 ± 0.01 and r_2(EEGE) = 0.76 ± 0.02, respectively. Then the ring closure of l-poly(EO-co-EEGE) was achieved via an ether linkage by reaction with tosyl chloride (TsCl) in the presence of solid KOH. The crude cyclized product containing the linear chain-extended polymer was hydrolyzed in acidic conditions first and then purified by treating with α-CD. The pure cyclic copolymer of EO and glycidol (Gly) with multipendant hydroxymethyls [c-poly(EO-co-Gly)] as the macroinitiator was used further to initiate the ring-opening polymerization of ?-caprolactone (CL), and a series of amphiphilic macrocyclic graft copolymers c-PEO-g-PCL were obtained. The final products and intermediates were characterized by GPC, NMR and MALDI-TOF in detail.     

聚丁二酸丁二醇酯环状二聚物的纯化、表征及其开环聚合的研究

从聚丁二酸丁二醇酯(PBS)的环状低聚物中分离提纯出了PBS的环状二聚物〔cyclic dimer of poly(butylenesuccinate),CDBS〕,采用核磁、质谱对该环状二聚物进行了表征,研究表明,通过分离纯化得到了纯度高的PBS的环状二聚物。以纯化的CDBS为原料、十二醇为初始剂、辛酸锡作催化剂,采用开环聚合的方法合成了PBS,采用核磁、红外光谱对合成的PBS的结构进行了表征,并研究了开环聚合温度、聚合时间以及催化剂用量对PBS的分子量、单体转化率的影响,结果表明,开环反应温度220℃左右,反应3 h,PBS的相对分子质量(简称分子量,下同)可达到63 300,与直接酯化-缩聚法相比,采用开环聚合法能提高PBS的制备效率。     

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.     

磷腈类催化剂研究进展

介绍了几种磷腈类的开环聚合催化剂,详细描述了无机磷腈盐、有机磷腈盐及氧化磷腈的制备路线,并介绍了这几种催化剂各自的特点。用其合成出的聚合物可克服目前KOH催化聚合物相对分子质量较小、分布宽、不饱和度高等缺点。与双金属氰(DMC)催化剂相比,它具有能使用小分子做起始剂、可直接用环氧乙烷封端以获得伯羟基、聚醚分子的头-尾(H-T)选择率高等优点。     

Synthesis of low molecular weight-hydroxy polycaprolactone macromonomers by coordinated anionic polymerization in protic conditions

This article reports the development of a new catalytic process that takes advantage of the exchange reaction between aluminium alkoxides and alcohols to obtain functionalized low molecular weight oligomers by anionic ring-opening polymerization. The aluminium alkoxides can be used in homogeneous medium or grafted on a porous support to make possible a heterogeneous process. ω-Hydroxy oligo polycaprolactones macromonomers with 2-hydroxyethylmethacrylate or hydroxymethylstyrene as polymerizable end groups have been synthesized and characterized by NMR and SEC. Mass spectrometry (LSIMS) has been used in an attempt to determine the MWD. These macromonomers have been engaged in copolymerization with styrene and the reactivity ratios have been approached. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2357–2372, 1997     

PET环状低聚物的表征及其开环聚合研究

以对苯二甲酸双(2-羟乙基)酯(BHET)为原料,通过悬浮法合成了聚对苯二甲酸乙二醇酯(PET)的环状低聚物(COET),对COET的结构和性能进行了表征;研究了COET的开环聚合及其在PET熔体中的开环聚合,探究了开环聚合工艺条件对其聚合产物的影响.结果表明:由核磁共振氢谱和碳谱表征悬浮法合成产物为COET,其主要以...     

Two-Component initiator systems for the ring-opening polymerization of oligomeric cyclic bisphenol-A carbonates. Studies with in situ generated wittig salts

A two-component initiator system based on the in situ generation of Wittig salts (alkytriarylphosphonium bromides) has been developed for the ring-opening polymerization of cyclic bisphenol-A (BPA) carbonate oligomers for potential use in composite applications so that the prepolymer can suitably wet the composite material before being converted to high molecular weight polymer. The Wittig salt precursors (an alkyl bromide, such as hexadecyl bromide, and a triarylphosphine, such as triphenylphosphine) did not independently initiate significant ring-opening polymerization of the oligomeric cyclic BPA carbonate mixture. However, when the two mixtures of cyclic BPA carbonate oligomers and initiator component were combined, a high molecular weight polymer (M_w = ∼ 65,000) was produced. The polymerization initiating species is thought to be hexadecyltriphenyl-phosphonium bromide. Consistent with this hypothesis is the observation that authentic Wittig salts did initiate ring-opening polymerization to provide high molecular weight polycarbonate. The effects of structure and concentration of the initiator components, reaction temperature, time, etc. on polymerization were studied; in general, the degree of polymerization ranged from 65 to 85%. © 1996 John Wiley & Sons, Inc.     

Synthesis and curing behavior of macrocycle‐terminated poly(aryl ether ketone)s

BACKGROUND: The introduction of poly(ether ether ketone)‐based carbon‐fiber composites accelerated the application of poly(ether ether ketone)s in advanced composite materials. In order to improve the compatibility and processability with reinforced components, polymers with low melt viscosity are preferable. RESULTS: Novel fully aromatic macrocycle‐terminated poly(aryl ether ketone)s (MCPAEKs) were prepared by condensation of macrocyclic aryl ether ketone dimers containing hydroxyphenyl groups and fluorine end‐capped poly(aryl ether ketone) oligomers. Compared with liner poly(aryl ether ketone)s, MCPAEKs showed much lower melt viscosities at low temperature. In the presence of caesium fluoride, the crosslinking reaction of MCPAEKs afforded fully aromatic thermoset poly(aryl ether ketone)s by ring‐opening reaction. CONCLUSION: The MCPAEKs exhibited high thermal stability due to their wholly aromatic structures. After crosslinking, the glass transition temperatures and complex melt viscosities of the polymers were increased greatly. Although there was some residual cesium fluoride or phenoxides produced by ring‐opening reaction, the thermoset poly(aryl ether ketone)s obtained had good thermal stability with temperatures at 5% weight loss above 475 °C. Copyright © 2009 Society of Chemical Industry     

Two-component initiator systems for the ring-opening polymerization of oligomeric cyclic bisphenol-A carbonates: The in situ cleavage of disulfides by triarlyphosphines

A two-component initiator system based on the in situ cleavage of phenyl disulfide by a triarylphosphine has been developed for the ring-opening polymerization of cyclic bisphenol-A (BPA) carbonate oligomers. This development has potential use in composite applications such that the prepolymer can suitably wet the composite material before being converted to high-molecular-weight polymer. The initiator precursors (phenyl disulfide and triphenylphosphine) do not independently initiate significant ring-opening polymerization of the oligomeric cyclic BPA carbonate mixture. A mixture of cyclic BPA carbonate oligomers and one of the initiator components (phenyl disulfide), combined and heated at 300°C with a mixture of the cyclics and the other initiator component (triphenylphosphine), does produce a high-molecular-weight polymer (M_w = ∼ 70,000). The polymerization-initiating species is thought to be thiophenyltriphenylphosphonium thiophenoxide. The effects of concentration of the initiator components, reaction temperature, time, and so forth on polymerization were studied; in general, the degree of polymerization ranged from about 65 to 75%. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2251–2255, 1997     

双酚A聚碳酸酯合成新方法的研究进展

介绍了双酚A聚碳酸酯不同于工业生产中常用的光气法和熔融酯交换法的3种新的合成方法,即固相缩聚法、开环聚合法、完全非光气法的实施方法、主要特点及其新进展,探讨了各种方法存在的主要问题以及对生成的聚合物结构和性能的影响。固相缩聚是由预聚物结晶后在固相缩聚,可以获得结晶型双酚A聚碳酸酯并提高聚合物质量;开环聚合法首先合成环状碳酸酯低聚物再开环聚合得到聚合物,可以获得很高分子质量聚合物;完全非光气法在合成过程中完全避免了光气的使用,环境友好,聚合物质量高,很有发展前景。     

Synthesis of hyperbranched polymers via a facile self-condensing vinyl polymerization system - Glycidyl methacrylate/Cp2TiCl2/Zn

A facile self-condensing vinyl polymerization (SCVP) system, the combination of glycidyl methacrylate, Cp₂TiCl₂ and Zn, has been firstly used to prepare novel hyperbranched polymers, consisting of vinyl polymers as the backbone, and cyclic ester polymers (poly(?-caprolactone) or poly(l-lactide)) as the side chains. The polymerizations are initiated by the epoxide radical ring-opening catalyzed by Cp₂Ti(III)Cl which is generated in situ via the reaction of Cp₂TiCl₂ with Zn. The key to success is that the polymerizations can proceed concurrently via two dissimilar chemistries possessing the opposite active initiating species, including ring-opening polymerization (ROP) and controlled/living radical polymerization (CRP). We have demonstrated that this facile one-step polymerization technique can be applied successfully to prepare highly branched polymers with a multiplicity of end reactive functionalities including Ti alkoxide, hydroxyl and vinyl functional groups.