Synthesis and Hydrogenation of 1,2-1,4-1,2-Stereotriblock Polybutadienes and the Study of Their Properties

The effects of various polar modifiers, their concentration, and the polymerization temperature on the microstructure of poly-butadiene obtained during anionic polymerization using lithium α-methyl naphthalene as the bifunctional initiator were studied. 1,2-1,4-1,2-Stereotriblock polybutadiene was synthesized by polymerization in cyclohexane to a certain conversion and polymerization was completed in the presence of diethylene glycol dimethyl ether. The microstructure of the stereotriblock copolymer was characterized by IR and ¹H-NMR. GPC showed that the stereo-block polybutadiene has a narrow MWD. Two T_g's of the copolymer with higher molecular weight exist, as shown by dynamic mechanical test. The stereotriblock copolymer was hydrogenated using cobalt 2-ethyl hexanoate and triisobutyl aluminum as the catalyst. The hydrogenated product was shown to be a (butene-1-ethylene-butene-1) triblock copolymer which consists of more than 30% crystallinity and exhibits the behavior of a thermoplastic elastomer. The relationship between stress-strain properties arid the contents of the blocks was also studied.     

原位制备淀粉接枝聚乳酸

研究了淀粉与乳酸的原位接枝反应.结果表明,利用乳酸中所含的水先将淀粉糊化,然后在95℃下减压反应,可直接得到淀粉-聚乳酸接枝共聚物.研究发现,上述反应体系中可原位生成丙交酯.该丙交酯的开环聚合是淀粉发生接枝反应的主要原因.利用定量核磁共振等方法对接枝产物的微结构进行了详细的解析.     

Effect of cobalt(III) 1-nitroso-2-naphtholate on free-radical polymerization to vinyl monomers

It has been shown that, at 70°C, cobalt(III) 1-nitroso-2-naphtholate inhibits the free-radical polymerization of styrene, methyl methacrylate, butyl methacrylate, and butyl acrylate. The induction period linearly increases with complex concentration. The polymerization of styrene (120°C) carried out in the presence of cobalt(III) 1-nitroso-2-naphtholate shows typical features of pseudoliving polymerization, namely, linear ln[M]₀/[M]-time and molecular mass-conversion plots. When the monomers are allowed to stand with a complex (7 × 10^?3 mol/l) and an initiator (5 × 10^?3 mol/l) for 1 day at 20°C, the ESR signal corresponding to the nitroxide radical appears. In the course of polymerization, the signal disappears, indicating the consecutive transformation of the cobalt(III) 1-nitroso-2-naphtholate radical into the macronitroxide adduct. Polystyrene samples isolated at various conversions initiate the secondary polymerization of styrene and its block copolymerization with methyl methacrylate.     

铁、钴催化剂乙烯聚合原位紫外-可见光谱研究

利用乙烯常压聚合原位紫外 可见 (UV Vis)光谱技术 ,对 3个铁、钴络合物作为催化剂前体的催化剂体系进行了研究 .3个铁、钴络合物分别为 2 ,6 双 [1 (2 ,6 二甲基苯基亚胺 )乙基 ]吡啶二氯化铁 (a)、2 ,6 双 [1 (2 ,4,6 三甲基苯基亚胺 )乙基 ]吡啶二氯化铁 (b)和 2 ,6 双 [1 (2 ,6 二异丙基苯基亚胺 )乙基 ]吡啶二氯化钴(c) .实验结果表明 ,MAO对络合物催化剂前体的活化作用是一个快速过程 ;在聚合条件下分别观察到 5 6 0、6 30和 5 80nm的活性峰 ,考察了它们在聚合过程中的生长和在加入无水乙醇逐步使催化剂中毒时活性峰的消失规律 .对催化剂活性物种的结构和聚合机理进行了探讨     

Sequence-regulated copolymers via tandem catalysis of living radical polymerization and in situ transesterification

Sequence regulation of monomers is undoubtedly a challenging issue as an ultimate goal in polymer science. To efficiently produce sequence-controlled copolymers, we herein developed the versatile tandem catalysis, which concurrently and/or sequentially involved ruthenium-catalyzed living radical polymerization and in situ transesterification of methacrylates (monomers: RMA) with metal alkoxides (catalysts) and alcohols (ROH). Typically, gradient copolymers were directly obtained from the synchronization of the two reactions: the instantaneous monomer composition in feed gradually changed via the transesterification of R(1)MA into R(2)MA in the presence of R(2)OH during living polymerization to give R(1)MA/R(2)MA gradient copolymers. The gradient sequence of monomers along a chain was catalytically controlled by the reaction conditions such as temperature, concentration and/or species of catalysts, alcohols, and monomers. The sequence regulation of multimonomer units was also successfully achieved in one-pot by monomer-selective transesterification in concurrent tandem catalysis and iterative tandem catalysis, providing random-gradient copolymers and gradient-block counterparts, respectively. In contrast, sequential tandem catalysis via the variable initiation of either polymerization or in situ transesterification led to random or block copolymers. Due to the versatile adaptability of common and commercially available reagents (monomers, alcohols, catalysts), this tandem catalysis is one of the most efficient, convenient, and powerful tools to design tailor-made sequence-regulated copolymers.     

Nanometer particles synthesis in reverse micelles: Influence of the size and the surface on the reactivity

In this paprr we are presenting the synthesss “in situ” of nanoparticles in reverse micelles. In the case of aggregates containing copper ions, it is possible to form metallic particles surrounded or not by an oxide layer. By mixing aggregates containing cadmium and sulphide ions, CdS particles are formed. The size and polydispersity of the particles are controlled. The photoelectron transfer reaction depends mainly on the surface composition. In the range of 1 to 5 nm, the efficiency in the electron transfer does not depend on the size of the particle. The reverse micelles are formed by using either sodium di(2-ethyl hexyl)sulfosuccinate, usually called {AOT} or mixed bivalent and sodium di(2-ethyl hexyl)sulfosuccinate {AOl/M(AOT)₂}.     

电化学聚合漆酚钴膜引发甲基丙烯酸甲酯（MMA）聚合的研究

利用电化学技术合成的聚合漆酚（EPU）与氯化钴的异丙醇溶液反应,得到电化学聚合漆酚钴配合物膜,经XPS光电子能谱、红外光谱、TG－DTA、动态机械热分析（DMTA）以及原子发射光谱（AES）等手段进行表征并确定其结构。由于每个钴离子与EPU分子中两个链节单元的羟基发生配位引进进一步交联。因此玻璃化转变温度和耐热性能均得到提高。实验表明,在常温下的Na2SO3水体系（pH值为7）中配合物膜能引发甲基丙烯酸甲酯（MMA）聚合。     

电化学聚合漆酚钴膜配位结构与催化性能研究

电化学方法合成的聚合漆酚 (EPU)通过与氯化钴的异丙醇溶液作用 ,生成聚合漆酚钴配合物膜(EPU Co3+ ) .采用红外光谱、XPS光电子能谱、DTA TG、动态机械热分析 (DMTA)以及原子发射光谱 (AES)等手段进行表征 ,确定其配位结构 ,即每个钴离子与EPU中两个链节单元的羟基发生配位而交联 ,因此玻璃化转变温度和耐热性能均得到提高 .实验表明 ,此配合物膜在室温下的Na2 SO3水体系 (pH =7)中能催化引发VAc的聚合     

不对称二亚胺异双核钴镍催化剂的合成及乙烯聚合研究

合成了不对称异双核钴镍催化剂MN5CoNi.该催化剂经AlEt3,MMAO,AlEt3/[PhMe2NH][B(C6F5)4](B)或MMAO/B活化后用于乙烯聚合.异双核催化剂与相应的等摩尔双组分混合单核催化剂相比,以TEA作助催化剂时,异双核催化剂的Co和Ni中心的活性都远低于双组分混合体系,且Ni中心生成的聚乙烯含量低于双组分混合体系,异双核催化剂中的Co和Ni中心同时被抑制.以MMAO作助催化剂时,异双核催化剂的活性虽低于双组分混合体系,但是异双核催化剂中的两种金属中心的活性都有了较大的提高,且Ni中心生成的聚乙烯含量高于后者.同时考察了活性随时间变化,发现异双核催化剂中活性衰减比双组分混合体系慢,说明异双核体系中Co和Ni中心在MMAO活化下比双组分混合体系的金属中心更稳定.当以TEA/B作助催化剂时,异双核催化剂中Co和Ni中心的活性有所提高,但仍远低于双组分混合体系,且Ni中心生成的聚乙烯含量低于后者,说明Ni被选择性抑制.当使用MMAO/B作助催化剂时,结果与MMAO类似.     

The Influence of Activating Agents on the Controlled Synthesis of Poly(methyl methacrylate) in the Presence of Ruthenacarboranes

The radical polymerization of methyl methacrylate catalyzed by systems based on the carborane complexes of ruthenium(III) is studied in the presence of a number of activating agents: tin 2-ethyl hexanoate, aluminum isopropoxide, isopropylamine, and AIBN. It is shown that in the presence of the systems under consideration, polymerization proceeds in a controlled mode via the ATRP mechanism (AGET or ICAR ATRP) at catalyst concentrations with ppm level relative to that of the monomer. As the degree of monomer conversion grows, the molecular weight of the polymer increases linearly while its polydispersity coefficients decrease linearly. The role of the mentioned agents is to transfer the catalyst to the active form containing a metal atom in the oxidation number +2 and able to interact with halogen-terminated dormant polymer chains. It is first shown that the carborane complexes of ruthenium(II) are applicable for the catalysis of controlled radical polymerization.     

Cobalt(II) phenoxy-imine complexes in radical polymerization of vinyl acetate: The interplay of catalytic chain transfer and controlled/living radical polymerization

A series of cobalt(II) phenoxy-imine complexes (Co^II(FI)₂) have been synthesized to mediate the radical polymerization of vinyl acetate (VAc) and methyl acrylate (MA) to evaluate the influence of chelating atoms and configuration to the control of polymerization. The VAc polymerizations showed the properties of controlled/living radical polymerization (C/LRP) with complexes 1a and 3a , but the catalytic chain transfer (CCT) behaviors with complexes 2a , 1b , 2b , and 3b . The control of VAc polymerization mediated by complex 1a could be improved by decreasing the reaction temperature to approach the molecular weights that not only linearly increased with conversions but also matched the theoretical values and relatively narrow molecular weight distributions. The catalytic chain transfer polymerizations (CCTP) mediated by complexes 2a , 1b , 2b , and 3b were characterized by Mayo plots and the polymer chain end double bonds were observed by ¹H NMR spectra. The tendency toward C/LRP or CCTP in VAc polymerization mediated by Co^II(FI)₂ could be determined by the ligand structure. Cobalt complex coordinated by the ligand with more steric hindered and less electron-donating substituents favored the controlled/living radical polymerization. In contrast, the efficiency of CCT process could be enhanced by less steric hindered, more electron-donating ligands. The controlled/living radical polymerization of MA, however, could not be achieved by the mediation of these cobalt(II) phenoxy-imine complexes. Associated with the results of polymerization mediated by other cobalt complexes, this study implied that the configuration and spin state of cobalt complexes were more critical than the chelating atoms to the control behavior of radical polymerization. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 101–113     

Effects of coordinately unsaturated cobalt complexes on radical polymerization of vinyl monomers

The tetrahedral cobalt(II) complexes A-D are found to possess an unusual coordinately unsaturated nature. These additives significantly inhibit the thermal polymerization of acrylamide and further, they impart significant induction period during AIBN initiated polymerization of MMA and acrylamide. Some evidence has been obtained to show that the additives' effect plausibly results because of the reaction of the coordinately unsaturated cobalt complexes with radicals present in the system.     

Novel biodegradable adaptive hydrogels: controlled synthesis and full characterization of the amphiphilic co-networks

Adaptive and amphiphilic poly(N,N-dimethylamino-2-ethyl methacrylate-graft-poly[epsilon-caprolactone]) co-networks (netP(DMAEMA-g-PCL)) were synthesized from a combination of controlled polymerization techniques. Firstly, PCL cross-linkers were produced by ring-opening polymerization (ROP) of epsilon-CL initiated by 1,4-butane-diol and catalyzed by tin(II) 2-ethylhexanoate ([Sn(Oct)2]), followed by the quantitative esterification reaction of terminal hydroxyl end-groups with methacrylic anhydride. Then, PCL cross-linkers were copolymerized to DMAEMA monomers by atom-transfer radical polymerization (ATRP) in THF at 60 degrees C using CuBr complexed by 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) and 2-ethyl isobutyrylbromide (EiBBr) as catalytic complex and initiator, respectively. A comprehensive study of gel formation was carried out by employing dynamic light scattering (DLS) to determine the gel point as a function of several parameters and to characterize the viscous solutions obtained before the gel point was reached. The evolution of the mean diameters was compared to a model previously developed by Fukuda and these attest to the living formation of the polymer co-network. Furthermore, we also demonstrated the reliability of ATRP for producing well-defined and homogeneous polymer co-networks by the smaller deviation from Flory's theory in terms of cross-linking density. For sake of clarity, the impact of polymerization techniques over the final structure and, therefore, properties was highlighted by comparing two samples of similar composition, but that were produced by either ATRP or thermal-initiated free-radical polymerization (FRP).     

Versatile cobalt complexes for initiating immortal ring‐opening polymerization (ROP) of lactide (LA), mediating living radical polymerization of t‐butyl acrylate (tBA) and catalyzing copolymerization of LA and tBA by combination of ROP and organometallic‐mediated radical polymerization

Low‐cost, highly active and versatile amino‐bis(phenolate) cobalt complexes are developed. The cobalt complexes can control living polymerization of different categories of monomers including lactide (LA) by immortal ring‐opening polymerization in argon and even in air and acrylate via living radical polymerization (LRP). The cobalt‐based catalysts were used for copolymerization of LA and acrylate. The immortal polymerization of LA using the cobalt complexes as initiators proceeds in argon and even in air and without the requirement for extensive drying techniques or inert atmosphere whilst retaining end‐group fidelity. The cobalt complexes are used to mediate LRP of t‐butyl acrylate (tBA) in methanol. The block copolymerization of LA and tBA catalyzed by single‐site cobalt organometallic catalyst is also reported for the first time. This cobalt system offers a versatile and green way to produce homopolymers and block copolymers.     

Synthesis of bifluorenes via cobalt halide radical coupling

Reaction of in situ generated lithium fluorenide salts with cobalt chloride results in formation of the corresponding bifluorenes. The scope of fluorenes that can be coupled include those containing substituents amenable to polymerization for application to poly(bifluorene) synthesis and alkyl substituted fluorenes for use in the preparation of bimetallic transition metal complexes. Based on experiments using a radical trap, the reaction mechanism involves reduction of cobalt and subsequent fluorenyl radical coupling. Overall, this study demonstrates a simple and effective method for preparation of hindered tertiary and quaternary C-C bonds using a readily available and inexpensive coupling agent.     

Thermal polymerization of cobalt(II) and nickel(II) acrylates: Use of in situ dielectric measurements

In situ dielectric spectroscopy at frequencies ranging from 1 to 10⁵ Hz was used to study chemical transformations during the heating of cobalt(II) and nickel(II) acrylates from ?160 to +400°C. On the basis of analysis of the evolution of dielectric relaxation time spectra, processes that correspond to three macroscopic stages in different temperature intervals were distinguished: dehydration, solid-state thermal polymerization, and decarboxylation of metallopolymers. These processes lead to the formation of a polymer matrix that stabilizes nanosized metal or metal oxide phases. In the case of cobalt acrylate, the crosslinking step occurs in a temperature interval other than that of polymerization. It was found that electric conductivity varies over six orders of magnitude upon the formation of the nanosized metal phase.     

In situ Polymerization Technique for Obtaining Composite Materials Based on Polyethylene,Multi-walled Carbon Nanotubes and Cobalt Nanoparticles

Specific features of formation of composite materials based on polyethylene, multi-walled carbon nanotubes, and cobalt nanoparticles (MWCNT–PE and Co/MWCNT–PE) by in situ polymerization were revealed. The in situ polymerization technique is based on ethylene polymerization on a highly dispersed Ti-containing catalyst supported on the surface of MWCNT and Со/MWCNT. This method ensures uniform distribution of MWCNT and Co/MWCNT in the polyethylene matrix. The effect of MWCNT and Со/MWCNT on the final properties of the composite materials was determined. Introduction of MWCNT into the polyethylene matrix increases the specific electrical conductivity of the material. Such composite materials can be used for preparing concentrates with preset composition for the subsequent preparation of antistatic coatings. Introduction of the Со/MWCNT filler into the polyethylene matrix makes the material paramagnetic owing to Co nanoparticles and allows its use for preparing coatings that efficiently protect from electromagnetic radiation.     

Nanostructured block-random copolymers with tunable magnetic properties

It was recently shown that block copolymers (BCPs) produced room-temperature ferromagnetic materials (RTFMs) due to their nanoscopic ordering and the cylindrical phase yielded the highest coercivity. Here, a series of metal-containing block-random copolymers composed of an alkyl-functionalized homo block (C(16)) and a random block of cobalt complex- (Co) and ferrocene-functionalized (Fe) units was synthesized via ring-opening metathesis polymerization. Taking advantage of the block-random architecture, the influence of dipolar interactions on the magnetic properties of these nanostructured BCP materials was studied by varying the molar ratio of the Co units to the Fe units, while maintaining the cylindrical phase-separated morphology. DC magnetic measurements, including magnetization versus field, zero-field-cooled, and field-cooled, as well as AC susceptibility measurements showed that the magnetic properties of the nanostructured BCP materials could be easily tuned by diluting the cobalt density with Fe units in the cylindrical domains. Decreasing the cobalt density weakened the dipolar interactions of the cobalt nanoparticles, leading to the transition from a room temperature ferromagnetic (RTF) to a superparamagnetic material. These results confirmed that dipolar interactions of the cobalt nanoparticles within the phase-separated domains were responsible for the RTF properties of the nanostructured BCP materials.     

Synthesis and supramolecular organization of amphiphilic diblock copolymers combining poly(N,N-dimethylamino-2-ethyl methacrylate) and poly(epsilon-caprolactone)

Well-defined poly(epsilon-caprolactone) (PCL)/poly(N,N-dimethylamino-2-ethyl methacrylate (PDMAEMA) diblock copolymers were synthesized, and their self-assembly was investigated as micelles both in aqueous solutions and in thin solid deposits. The synthetic approach combines controlled ring opening polymerization (ROP) of epsilon-caprolactone (CL) and atom transfer radical polymerization (ATRP) of N,N-dimethylamino-2-ethyl methacrylate (DMAEMA). Diblock copolymers were prepared by ROP of CL initiated by (Al(OiPr)3), followed by quantitative reaction of the PCL hydroxy end-groups with bromoisobutyryl bromide. The alpha-isopropyloxy omega-2-bromoisobutyrate poly(epsilon-caprolactone) (PCL-Br) obtained was used as a macroinitiator for the ATRP of DMAEMA. The molecular characterization of those diblock copolymers was performed by 1H NMR spectroscopy and gel permeation chromatography (GPC) analysis. The self-assembly of the copolymers into micellar aggregates in aqueous media was followed with dynamic light scattering (DLS), as a function of concentration and the pH. In parallel, the morphology of the solid deposits of those micelles was examined with atomic force microscopy (AFM).     

由A2和CB2型单体合成端羟基超支化聚(脲-氨酯)

超支化聚合物是一类高度支化的具有三维椭球状立体构造的大分子[1]. 由于具有传统线型聚合物所没有的低熔体粘度、高流变性、良好的溶解性及大量末端官能团等一系列独特的物理化学特性, 超支化聚合物自 20世纪 80年代末在杜邦公司诞生以来[2]便很快成为高分子科学界研究的一个热点[3～7], 预计其将在医药载体、大分子建筑"砌块"、催化剂和流变添加剂等诸多领域得到广泛应用[8].