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91.
92.
端羟基P(GA-b-AMMO)的合成与表征 总被引:1,自引:1,他引:0
以1,3,5-三羟乙基异氰脲酸酯(THEIC)为起始剂,经环氧氯丙烷开环聚合和叠氮化取代等反应首先制成带有氮杂环结构的数均相对分子质量(Mn)为2500~3000的三官能度叠氮缩水甘油醚(TGAP),然后以TGAP为大分子起始剂,引发3-叠氮甲基-3-甲基氧杂环丁烷(AMMO)进行开环聚合制备出一种新型叠氮粘合剂P(GA-b-AMMO)。采用红外、核磁共振(1H NMR和13C NMR)和凝胶渗透色谱(GPC)对P(GA-b-AMMO)的分子结构、组成和Mn进行了表征。考察了聚合温度及投料比等因素对聚合反应的影响,确定了该体系下聚合的优化条件为:n(BF3·OEt2)/n(TGAP)/n(AMMO)=1.35/1/12~16,聚合温度为0~3 ℃。P(GA-b-AMMO)的Mn、羟值(OH)测试结果均表明在该优化条件下聚合较为可控,产品总收率≥80.0%,官能度≥2.70,Mn达到4000~4400且与相应理论值均较为接近。力学性能测试表明与均聚醚TGAP相比,P(GA-b-AMMO)表现出较好的力学性能,以异氟尔酮二异氰酸酯(IPDI)为固化剂,其纯胶片常温力学强度为2.04 MPa,而常温延伸率可达261%,较低分子量的TGAP提高约2倍。 相似文献
93.
This paper describes the preparations and lithium-ion conductivities of various solid polymer electrolytes for potential use in high-energy density lithium-ion batteries. The ring opening polymerization of epoxides (M1–M6), catalyzed by Zn(II), Cu(II) and Cd(II) complexes in the presence of tetrabutylammonium bromide (TBAB), yielded polyethers (P1–P6) in which phosphates were attached as pendant groups. A reaction condition where Zn(II) catalyst used slightly excess to TBAB increased the polymerization rate remarkably and yielded the polyethers with higher molar masses in a short time. These polymerizations proceeded following a “monomer activated anionic ring opening polymerization” mechanism. These living like polymerizations also progressed according to “formation of polymer chain per initiator” model. The solid-state lithium-ion conductivities of these polymers were examined using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The conductivity of one of the solid polymer electrolytes with 40 wt% of LiTFSI was 5.2 × 10−5 S cm−1 at room temperature and 2.9 × 10−4 S cm−1 at 80 °C. 相似文献
94.
Most studies on surface-initiated controlled polymerizations for the synthesis of polymeric covalent organic-inorganic hybrid materials focus on chemical methods requiring specific modifications of the inorganic substrate. Few mechanistically-aware approaches have been undertaken towards exploiting the reactivity of defects induced by physical techniques such as ionizing radiations or UV–Vis light. Within this framework, we take grafted polymerization of styrene from γ-irradiated silica as a mechanistic testing ground where para- and diamagnetic silica defects are present, and polymerization proceeds through both radical and cationic mechanisms, resulting in a bimodal molecular weight distribution. We show that these mechanistic intricacies can be sorted out by resorting to the chemical arsenal developed in the last decades for controlled polymerizations. Specifically, we obtained a silica-polystyrene grafted material by cationic grafting from at 30 °C, a unimodal molecular weight distribution, and a relatively high molecular weight (Mn = 7.4 kDa) with a PDI of 1.68. 相似文献
95.
Polymer/reduced graphite oxide (rGO) composite nanoparticles with a high electrical conductivity were synthesized using the miniemulsion polymerization technique. The rGO was modified with a reactive surfactant, 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), to facilitate monomer intercalation into the rGO nanogalleries. The AMPS-modified rGO was emulsified in the presence of styrene (St) and butyl acrylate (BA) monomers, and the stable miniemulsion was polymerized to form poly(St-co-BA)/rGO composite latex nanoparticles. The transition in the composite nanoparticles from an electrical insulator to an electrical conductor occurred at an rGO content of 10 wt% (relative to the monolayer content), yielding an electrical conductivity of 0.49 S/cm. The electrical conductivity of the composite nanoparticles reached 2.22 S/cm at 20 wt% rGO, yielding a much better conductivity than other polymer composites prepared using a GO filler. Importantly, the miniemulsion polymerization method for fabricating poly(St-co-BA)/rGO composite nanoparticles is easy, green, low-cost, and scalable, providing a universal route to the rational design and engineering of highly conductive polymer composites. 相似文献
96.
Rakhi Sood Mona Marie Obadia Bhanu Prakash Mudraboyina Biao Zhang Anatoli Serghei Julien Bernard Eric Drockenmuller 《Polymer》2014
Nitroxide-mediated radical polymerization of a tailor-made acrylate carrying a 1,2,3-triazole group with an undecanoyl spacer affords a well-defined (Mn = 7860 g mol−1 and D = 1.39) neutral polyacrylate precursor. A series of 1,2,3-triazolium-based poly(ionic liquid)s (TPILs) is then obtained by straightforward quaternization of the 1,2,3-triazole groups with methyl iodide and subsequent anion metathesis reactions. Among the prepared materials, TPIL with bis(trifluoromethane)sulfonimide anion exhibits low glass transition temperature (Tg = −40 °C), high thermal stability (Td10 = 325 °C) and anhydrous ionic conductivity of 4 × 10−6 S cm−1 at 30 °C, as measured by differential scanning calorimetry, thermogravimetric analysis and broadband dielectric spectroscopy, respectively. 相似文献
97.
An electronically conductive polyelectrolyte is prepared by the sequential polymerization of a bifunctional imidazolium-based ionic liquid (IL) monomer, composed of a thienyl and vinyl containing cation paired with a tetrafluoroborate anion. In the first step, potentiodynamic electropolymerization of the thienyl moiety forms a cationic polyalkylthiophene that is soluble in select organic solvents. Cyclic voltammetry (CV) was used to determine the polymer p-doping potential (0.31 V) and the bipolaronic state (1.49 V). The polymer exhibits electrochromism, converting from red in the neutral state (λmax = 443 nm) to dark blue in the polaronic state (λmax = 819 nm). The solution-processable polymer can be cast into a film, masked and patterned by UV-initiated free radical polymerization of the vinyl moiety. Small-angle X-ray scattering (SAXS) revealed that the insoluble crosslinked polyalkylthiophene–polyvinylimidazolium adopts a lamellar structure with a lattice spacing of 3.3 nm. Four-probe d.c. conductivity measurements determined the de-doped electrical conductivity was 1.0 × 10−2 S/cm. The results underscore the importance of the anion in controlling the polymerization of IL monomers. 相似文献
98.
Sellamuthu N. Jaisankar Neelamegan Haridharan Adhigan Murali Ponyrko Sergii Milena Špírková Asit Baran Mandal Libor Matějka 《Polymer》2014
The sidewall functionalization of single-walled carbon nanotubes (SWCNTs) was established by poly (methyl methacrylate) (PMMA) using controlled radical polymerization (CRP) method. A bromide functionalized SWCNT (SWCNT-Br) has been used as an initiator for the synthesis of SWCNT-graft-PMMA (SWCNT-g-PMMA). The efficiency of the sacrificial initiator (S) was monitored during the polymerization process. The obtained polymers possess a uniform distribution of molecular weight with a lower polydispersity index of 1.36. The SWCNTs-based initiator acts as an efficient medium for the controlled growth of polymer on the SWCNTs surfaces. The presence of bimodal gel permeation chromatographic (GPC) curve for the SWCNT-g-PMMA(S) obtained through sacrificial initiator (S) confirms uncontrolled behavior. However, the clear sharp peak for SWCNT-g-PMMA obtained without sacrificial initiator shows its well-controlled process of polymerization, which acts as a mimic to bone cement. The efficiency of the functionalization of SWCNT and the controlled formation of SWCNT-g-PMMA composites were characterized by TGA, Raman, TEM, NMR, XPS and dispersion measurements. 相似文献
99.
Linear amphiphilic diblock copolymers of polylactide (PLA) and poly(2-dimethylaminoethyl methacrylate) (PDMAEMA) were synthesized by atom transfer radical polymerization (ATRP) of DMAEMA followed by ring-opening polymerization (ROP) of LLA using the bifunctional initiator, 2′-hydroxyethyl 2-bromoisobutyrate. NMR showed that the resulting PLA block was racemic and a quaternization/precipitation technique showed that there were significant amounts of racemic PLA homopolymer. In addition, simultaneous ATRP of DMAEMA and ROP of l-lactide by tin octoate were conducted at varied temperatures, indicating 90 °C as a suitable compromise temperature; this one-pot process also led to racemization and P(L)LA homopolymer. The racemization was attributed to reversible deprotonation of LLA by the N(CH3)2 moiety of (P)DMAEMA and the PLA homopolymer impurity was related to in situ formation of lactoyl lactate (LA–LA) due to nucleophilic ring opening of lactide by the amino moieties of (P)DMAEMA. The methods presented can be useful for the preparation of PDMAEMA–b–PLA/PLA composites in a two-step process or in a single step, one-pot process. 相似文献
100.
Highly monodisperse polystyrene nanoparticles with mean diameters of less than 100 nm are synthesized via aqueous emulsion polymerization using an amphoteric initiator (VA-057) in the presence of sub-millimolar concentrations of anionic surfactant. Since the net charge on the initiator is almost zero at neutral pH, the resultant latex particle size is mainly determined by surfactant adsorption. Polymerizations were performed in the presence of a range of anionic surfactants with differing critical micelle concentrations (CMC) by varying the concentrations of surfactant, initiator and monomer, and also the ionic strength. Sodium dodecyl benzene sulfonate (SDBS), sodium hexadecyl sulfate (SHS), and sodium octadecyl sulfate (SOS) have relatively low CMCs and so enable formation of highly monodisperse nanoparticles at relatively low (sub-millimolar) surfactant concentrations, CS (i.e. below the CMC in each case). Empirically, it was found that the particle number, Np, and coefficient of variation of the particle size, CV, were strongly dependent on the CS/CMC ratio: Np increased almost in proportion with the square of this ratio, while the CV exhibited a minimum at approximately CS/CMC = 0.20. Higher ionic strength reduced the particle size, which is consistent with the above relationship because the addition of salt lowers the CMCs of ionic surfactants. Polymer latex particles produced using such formulations form highly regular, close-packed colloidal arrays. 相似文献