Homopolymerization of ω‐Styryl‐Polystyrene Macromonomers in the Presence of CpTiF3/MAO

Summary: ω‐Styryl‐polystyrene macromonomers were synthesized by anionic induced deactivation reactions. Their homopolymerization in the presence of a fluorinated half‐sandwich metallocene catalyst (CpTiF₃/MAO) was investigated. In spite of the intrinsic lower reactivity of these macromonomers with respect to the micromolecular monomer, coordination homopolymerization was possible. The influence of several experimental parameters on the polymerization yield and degree could be demonstrated. In most cases, under identical experimental conditions, higher polymerization yields and degrees were observed with respect to the CpTiCl₃/MAO catalyst.

The synthesis of p‐polystyryl‐substituted styrene derivatives by the homopolymerization of ω‐styryl‐polystyrene macromonomers in the presence of CpTiF₃.     

Synthesis and Characterization of α,ω‐Heterofunctional Poly(ethylene oxide) Macromonomers

A novel α,ω‐heterofunctional poly(ethylene oxide) (PEO) macromonomer possessing methacryloyl and thienyl end groups was prepared by ring‐opening polymerization of ethylene oxide initiated by potassium thienylethoxide and termination of the living PEO ends with methacryloyl chloride. Incorporation of methacryloyl and thienyl groups was confirmed by free‐radical and oxidative polymerization processes, respectively, and by means of ¹H NMR analysis.

     

An Easy Way Toward ε‐Caprolactone Macromonomers by Microwave Irradiation Using Early Lanthanide Halides as Catalysts

Poly(ε‐caprolactone) macromonomers were synthesized under microwave irradiation from commercial caprolactone, using commercial hydrated lanthanide halides as catalysts. The molecular weight of the polymers was in the range 3 000–5 000. Higher molecular weights (5 000–20 000) and lower polydispersity indices were obtained with THF adducts of the lanthanide halides as catalysts and also by applying longer reaction times or using diethylene glycol as a coupling reagent.     

Reactive surfactants in heterophase polymerization. Part XXII—incorporation of macromonomers used as stabilizers in styrene dispersion polymerization

The effect of several parameters on the incorporation yield of poly(ethylene oxide) macromonomers at the surface of the particles, for the dispersion polymerization of styrene in ethanol–water mixtures, has been studied. The reactivity of the macromonomer is a key parameter in the mechanism of stabilization of the micrometer-size polymer particles, because it partly determines the amount and the composition of the copolymer stabilizer available at any moment during the process. The polarity of the reaction medium also strongly influences the polymerization process: higher incorporation yield and grafting density were obtained in medium of lower polarity. Besides, a chain length of around 50 ethylene oxide units for the macromonomer were needed to produce stable monodisperse particles with a significant incorporation yield. Thus, an incorporation yield as high as 53% and a grafting density corresponding to a surface area of 232 Ų/molecule have been obtained in a one-step process by using a methacrylate macromonomer. In an optimized two-step process resulting in monodisperse polymer particles, 80% incorporation yield with a very high grafting density (175 Ų/molecule) were reached. The particles with high grafting density (surface area lower than 600 Ų/molecule) could be transferred in water and exposed to a freeze–thaw cycle without massive flocculation, illustrating the efficiency of the steric stabilization. © 1997 John Wiley & Sons, Ltd.     

Thiol-ene UV-curable coatings using vegetable oil macromonomers

Allyl, acrylate, and vinyl ether derivatives of castor oil were synthesized and blended with multifunctional thiols for evaluation as thiol-ene ultraviolet (UV) curable systems. The UV cured films were characterized and evaluated via ASTM tests, gel content, and dynamic mechanical analysis (DMA) as a function of time. Fourier transform infrared spectroscopy and DMA studies established that property advancement resulted from auto-oxidation, continued thiol-ene polymerization, or a combination of both mechanisms.     

Thermo-Associative and Salt-Associative Graft Copolymers of Surfactant Macromonomers and Acrylamide: Synthesis and Solution Properties in Dilute Aqueous Solutions

Three new surfactant macromonomers (SMM) with different ethylene oxide (EO)/propylene oxide (PO) ratios (for SMM1, SMM2, and SMM3, the EO/PO ratios were 1:0.5, 1:0.9, and 1:1.25, respectively) were synthesized by the reaction between PEO-PPO di-block polymers having terminal tertiary amine groups and chloropropene. Graft copolymers of acrylamide and SMM (PAM-g-SMM) were prepared with different SMMs and grafting densities in water, and the products were confirmed by FTIR and elemental analysis. Owing to the strong hydrophobicity of the graft, the PAM-g-SMM3 was not water soluble. However, PAM-g-SMM1 and PAM-g-SMM2 aqueous solutions had good surface activity and their surface tensions were 44.26 and 37.63 mN/m at a concentration of 1000 mg/L, respectively. In general, in diluted graft PAM solutions, the copolymer predominantly formed intrapolymeric associates. The PAM-g-SMM2 was both thermo-associative and salt-associative in dilute solution. For PAM-g-SMM2, when the temperature and salt concentration increased, interpolymeric aggregations were formed.     

梳型接枝共聚物的合成（IV）-氯乙酸降冰片烯甲酯引发苯乙烯、甲基丙烯酸甲酯原子转移自由基聚合的研究

首次报道以自制氯乙酸降冰片烯甲酯（NMCA）为引发剂的苯乙烯、甲基丙烯酸 甲酯的原子转移自由基（ATRP）本体聚合。详细考察了单体转化与反应时间、产物 分子量及分子量分布间的关系。研究发现,此引发引发甲基丙烯酸甲酯ATRP反应所 得聚合物的分子量分布较宽（PDI = 1.80～2.45),且实测值（GPC）与理论值偏差 较大。而NMCA引发的苯乙烯的ATRP反应可得分子量分布较窄（PDI = 1.54)、实验 值（GPC）与理论值基本吻合的产物。单体转化率随反应时间的变化及产物分子量 随单体转化率变化研究证明这一聚合反应具有活性聚合反应特征。产物的NMR分析 证明所合成产物分子中降冰片烯环上双键未参与聚合反应。     

Pulsed‐laser polymerization‐gel permeation chromatographic determination of the propagation‐rate coefficient for the methyl acrylate dimer: A sterically hindered monomer

The methyl acrylate dimer (MAD) is a sterically hindered macromonomer, and the propagating radical can fragment to an unsaturated end group. The propagation‐rate coefficient (k_p) for MAD was obtained by pulsed‐laser polymerization (PLP). The Mark–Houwink–Sakaruda parameters required for the analysis of the molecular weight distributions (MWDs) were obtained by multiple‐detector gel permeation chromatography (GPC) with on‐line viscometry. The small radical created by the fragmentation results in a short‐chain polymer that means the MWD may no longer be given by that expected for “ideal” PLP conditions; simulations suggest that the degree of polymerization required for “ideal” PLP conditions can be obtained from the primary point of inflection provided the GPC traces also show a clear secondary inflection point (radicals terminated by the second, rather than the first, pulse subsequent to initiation). Over the temperature range of 40–75 °C, the data can be best fitted by k_p/dm³ mol^?1 s^?1 = 10^6.1 exp(?29.5 kJ mol^?1), with a moderately large joint confidence interval for the Arrhenius parameters. The data are consistent with an increased activation energy and reduced frequency factor as compared with acrylate or methacrylate; both of these changes can be ascribed to hindrance. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3902–3915, 2001     

A Helical Poly(macromonomer) Consisting of a Polyacetylene Main Chain and Polystyrene Side Chains

A novel helical poly(macromonomer) [poly(M‐PS): absolute = 82 800–252 000, determined by GPC/RALLS] with a polyacetylene main chain and polystyrene (PS) side chains was synthesized by the polymerization of acetylene‐terminated M‐PS [ = 2 000, / = 1.20, = 18] with an Rh catalyst. M‐PS was prepared by ATRP of styrene using the acetylene‐containing initiator 2‐bromo‐2‐methylpropionic acid (S)‐1‐methylpropargyl ester ( l ). In solutions, poly(M‐PS) exhibited an intense CD signal at 345–355 nm, indicating that it possessed a predominantly one‐handed helical conformation. Poly(M‐PS) had a stable helical conformation irrespective of solvents and temperature.

     

A Facile Two‐Step Route to Branched Polyisoprenes via ABn‐Macromonomers

A facile two‐step synthesis for branched poly(isoprene)s (PI) based on polyaddition of AB_n‐type macromonomers is described. The synthesis of the macromonomers was achieved by anionic polymerization of isoprene and subsequent end‐capping of the polymers by addition of chlorodimethylsilane to the living carbanions. This led to PI‐based macromonomers with narrow polydispersity ( / < 1.15) and molecular weights in the range of 1 700 – 22 100 g · mol⁻¹. Synthesis of the branched polymers was carried out by a hydrosilylation‐based polymerization of the macromonomers. Characterization via SEC, SEC‐MALLS, coupled SEC‐viscosimetry and ¹H‐NMR‐spectroscopy supported the formation of branched structures. Interestingly, these branched polymers exhibited α‐values that were similar to those reported for hyperbranched polymers based on AB₂‐monomers.