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1.
Stacy J. Taylor Robson F. Storey 《Journal of polymer science. Part A, Polymer chemistry》2004,42(23):5942-5953
3,3′,5,5′‐Tetrakis(2‐chloro‐2‐propyl)biphenyl (biphenyl tetracumyl chloride, BPTCC) and 1,3‐bis[3,5‐bis(2‐chloro‐2‐propyl)phenoxy]propane (diphenoxypropane tetracumyl chloride, DPPTCC) were synthesized as initiators for quasiliving cationic polymerization of isobutylene (IB). In the synthesis of BPTCC, tetrafunctionality was achieved via the coupling of dimethyl 5‐bromoisophthalate (DMBI) using nickel dibromide bis(triphenylphosphine) and zinc in the presence of a base; in the synthesis of DPPTCC, two equivalents of dimethyl 5‐hydroxyisophthalate were linked via reaction with 1,3‐dibromopropane in the presence of potassium carbonate. Both initiators were used to initiate the polymerization of IB under quasiliving cationic polymerization conditions. PIB initiated from BPTCC revealed a chain end/molecule value (as determined by 1H‐NMR) of 3.85, verifying the nearly exclusive production of 4‐arm polyisobutylene (PIB). GPC analysis revealed a narrow peak representing the target four‐arm PIB, with a slight shoulder at high elution volumes (low molecular weights). GPC analysis of the PIB initiated by DPPTCC revealed multimodal distributions, suggesting the formation of two‐, three‐, and four‐arm star polymers during the polymerization. This behavior was attributed to Friedel–Crafts alkylation of the initiator core after the addition of one IB unit, which was activated by the electron‐donating oxytrimethyleneoxy linking moiety. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5942–5953, 2004 相似文献
2.
O. D. Greenwood S. Tasker J. P. S. Badyal 《Journal of polymer science. Part A, Polymer chemistry》1994,32(13):2479-2486
Dielectric barrier air discharge treatment of polyethylene, polypropylene, polyisobutylene, polystyrene, and polyisoprene substrates has been characterized by x-ray photoelectron spectroscopy (XPS). The relative reactivities of these polymers towards silent discharge oxidation are rationalized in terms of ozone molecules interacting with an excited surface. © 1994 John Wiley & Sons, Inc. 相似文献
3.
4.
A. V. Orlinkov T. V. Chulochnikova A. I. Nesmelov V. B. Murachev E. A. Ezhova A. M. Evtushenko 《Russian Chemical Bulletin》1996,45(5):1124-1127
The effects of the nature of halogens in the initiatingtert-butyl halide-aluminum-containing Lewis acid system on the number average molecular weightM
n
and the structure of end groups of polyisobutylene macromolecules obtained in the cationic polymerization of isobutylene in hexane at -78 °C were studied. An increase inM
n
is observed in the transition from chlorine to bromine and iodine, accompanied by a decrease in the fraction of end C=C groups and an increase in the relative content of C-Hal groups (Hal = Cl, Br, and I). When atoms of different halogens are present in the counterion, more bulky atoms preferentially participate in the formation of the end groups. The results are interpreted within the framework of the principle of hard and soft acids and bases.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1184–1187, May, 1996. 相似文献
5.
V. B. Murachev A. L. Nesmelov V. S. Byrikhin E. A. Ezhova A. V. Orlinkov L. S. Akhrem M. E. Vol'pin 《Russian Chemical Bulletin》1996,45(5):1115-1119
Polymerization of isobutylene inn-hexane at -78 °C in the presence of the complex of benzoyl chloride with AIBr3 (1 : 2) was investigated. The results were compared to those obtained previously for the polymerization of this monomer induced by the complex of acetyl bromide with AlBr3. Both complexes initiate the polymerization only by acyl cations. The number average molecular weight (M
n
) of the polymer linearly increases as the degree of isobutylene conversion increases. The polymerization restarts after repeated addition of the monomer, andM
n
continues to increase linearly. The efficiency of the initiaton by the benzoyl chloride complex does not exceed 6.2 %; the reaction has the second order with respect to the initiator in the case of PhCOCI · A12Br6; and the chain-propagation rate constant is 13.9 L mol–1 s t. The use of PhCOCI Al2Br6 as the initator of the polymerization of isobutylene allows one to prepare macromolecules with very low contents of the terminal C=C double bonds and with narrow molecular weight distributions. Unlike the MeCOBr·AlBr3 complex, PhCOCl · AlBr3 does not initiate polymerization of isobutylene.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1175–1179, May, 1996. 相似文献
6.
高水相W/O型乳化膏体油膜稳定性的研究 总被引:3,自引:0,他引:3
高水相W/O型乳液是指水相体积占74%以上,属于高度不稳定的分散体系[1,2].乳化炸药的问世,使这种高水相W/O型乳液有了新的实际应用.这种炸药是90%~95%重的硝酸铵盐(占水相80%~90%重)水溶液高度分散在5%~10%的油相中构成W/O型乳... 相似文献
7.
The effect of the chemical structure of styrene-based epoxides, namely, styrene epoxide (SE), α-methylstyrene epoxide (MSE), p-methylstyrene epoxide (pM-SE) and α-methyl-p-methylstyrene epoxide (pM-MSE), in conjunction with TiCl4, on the initiation efficiency (Ieff) in the carbocationic polymerization of isobutylene (IB) was investigated. SE yielded living polymerization, but the initiation efficiency was low when compared to MSE (Ieff=8% and 35%, respectively). pM-SE led to non-living IB polymerization, while pM-MSE revealed linear Mn-conversion plot and narrow MWD with a non-linear first order rate plot. Among the epoxides investigated, MSE was the best initiator to scale up the one-step synthesis of polyisobutylenes (PIBs) carrying one primary hydroxyl head group and one tertiary chloride end group. The hydroxyl functionality of these PIBs determined by 1H-NMR was Fn=1.09±0.16 from 24 experiments. 相似文献
8.
This series of papers concern new materials for possible biological applications created by combining the chemistry of highly reactive cyanoacrylates (CAs) with polyisobutylene (PIB) rubbers. First, a new strategy for the synthesis of CA–telechelic PIBs is described. Subsequently, the strategy is employed for the synthesis of low viscosity (syringible) CA–telechelic three‐arm star PIB [Ø(PIB–CA)3]. The intermediates of the synthesis route are characterized by 1H NMR spectroscopy. Injecting liquid Ø(PIB–CA)3 into living tissue (fresh chicken egg) produces a bolus of crosslinked PIB rubber. The spectacular oxidative resistance of this rubber is documented by its resistance to concentrated HNO3. A structural model of the crosslinked rubber obtained upon contacting Ø(PIB–CA)3 with proteinaceous tissue is proposed. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
9.
Low cost bifunctional initiators for bidirectional living cationic polymerization of olefins. I. isobutylene
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Turgut Nugay Balazs L. Keszler Tejal Deodhar Nihan Nugay Joseph P. Kennedy 《Journal of polymer science. Part A, Polymer chemistry》2017,55(22):3716-3724
We describe the discovery of novel low cost bifunctional initiators 2,4,7,9‐tetramethyl‐tricyclo[6.2.0.036]deca‐1(8),2,6‐triene‐4,9‐diol (bBCB‐diOH) and 4,9‐dichloro,2,4,7,9‐tetramethyl‐tricyclo[6.2.0.036]deca‐1(8),2,6‐triene (bBCB‐diCl), for living cationic bidirectional polymerization of olefins, for example, isobutylene. bBCB‐diOH was quantitatively synthesized in one step by UV radiation of commercially available diacetyl durene (DAD) and bBCB‐diCl by hydrochlorination of bBCB‐diOH. These molecules, in conjunction with TiCl4 coinitiator, initiate the living polymerization of isobutylene. Livingness was demonstrated by linear conversion versus molecular weight (MW) plots and narrow MW distributions. Polymerizations are slower than those initiated by the universally used “hindered” bifunctional initiator 5‐tert‐butyl‐1,3‐bis(1‐chloro‐1‐methyl)benzene and are suitable for rate studies. Herein, we report the synthesis, by the use of bBCB‐diCl, of relatively low MW (M n < 3000 g mol?1) allyl‐telechelic polyisobutylene (PIB) used for the synthesis of PIB‐based polyurethanes and that of relatively high MW (M n > 30,000) living PIB telechelics for the synthesis of thermoplastic elastomers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3716–3724 相似文献
10.
Sergei V. Kostjuk Hui Yee Yeong Brigitte Voit 《Journal of polymer science. Part A, Polymer chemistry》2013,51(3):471-486
This review highlights recent approaches toward polyisobutylene (PIB) by an energy efficient room temperature cationic polymerization. Special focus is laid on our own work using modified Lewis acids and nitrile‐ligated metal complexes associated with weakly coordinating anions. In both cases, suitable conditions have been found for efficient production of PIB characterized by medium to low molar masses and a high content of exo double bonds as end groups—the typical features of highly reactive PIB, an important commercial intermediate toward oil and gasoline additives. These and other approaches demonstrate that the cationic polymerization of isobutylene is still not fully explored, and new innovative catalyst systems can lead to surprising results of high commercial interest. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 相似文献