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1.
A novel reversible addition–fragmentation chain transfer polymerization (RAFT) of methyl methacrylate (MMA) in the presence of oxygen was carried out for the first time without added chemical initiators. The polymerization was mediated by 2‐cyanoprop‐2‐yl 1‐dithionaphthalate (CPDN) or cumyl dithionaphthalenoate (CDN) as RAFT agent. The polymerization demonstrated the features of a living/controlled radical polymerization. The polymerization rate increased with oxygen concentration. Polymers with molecular weight Mn up to 520,000 g/mol, polydispersity Mw/Mn ~1.46 and RAFT efficiency Mn,th/Mn,GPC ~1.026 in the case of CPDN and Mn ~331,500 g/mol, Mw/Mn ~1.35, and Mn,th/Mn,GPC ~1.137 in the case of CDN were obtained. The possible mechanism of the thermal‐initiated RAFT polymerization of MMA in the presence of oxygen was discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3343–3354, 2006  相似文献   

2.
This article is a critical analysis of kinetic dataavailable on carbocationic polymerizations. A survey of published propagation rate constant (kp) data revealed several orders of magnitude differences. In this article, an explanation of this apparent discrepancy is offered with a case study involving the carbocationic polymerization of 2,4,6‐trimethylstyrene (TMS). With the polymerization mechanism originally proposed for this system, kp = 1.35 × 104 L mol?1 s?1 was extracted from experimental data with the Predici polyreaction package. The alternative mechanism yielded kp = 1.01 × 107 L mol?1 s?1, close to that predicted by Mayr's Linear Free Energy Relationship (LFER). We propose that true rate constants can only be obtained from direct competition experiments or from kinetic interpretation based on independently proven mechanisms. The second part of this review discusses critical analysis of the temperature and concentration dependence of various living IB systems. Comparison of the temperature dependence in systems initiated with 2‐ chloro‐2,4, 4‐ trimethylpentane (TMPCl)/TiCl4 from various laboratories yielded of ΔH ~?25 and ?34.5 kJ/mol for high and low TMPCl/TiCl4 ratios, respectively. Aromatic (cumyl‐type) initiators show ΔH ~ ?40 kJ/mol, whereas H2O/TiCl4 in the presence of the strong electron‐ pair donor dimethylacetamide gave ΔH = ?12 kJ/mol. The significant differences indicate different underlying mechanisms with complex elementary reactions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5394–5413, 2005  相似文献   

3.
The radical ring‐opening copolymerization of 2‐isopropenyl‐3‐phenyloxirane (1) with styrene (St) was examined to obtain the copolymer [copoly(1‐St)] with a vinyl ether moiety in the main chain. The copolymers were obtained in moderate yields by copolymerization in various feed ratios of 1 and St over 120 °C; the number‐average molecular weights (Mn) were estimated to be 1800–4200 by gel permeation chromatography analysis. The ratio of the vinyl ether and St units of copoly(1‐St) was estimated with the 1H NMR spectra and varied from 1/7 to 1/14 according to the initial feed ratio of 1 and St. The haloalkoxylation of copoly(1‐St) with ethylene glycol in the presence of N‐chlorosuccinimide produced a new copolymer with alcohol groups and chlorine atoms in the side group in a high yield. The Mn value of the haloalkoxylated polymer was almost the same as that of the starting copoly(1‐St). The incorporated halogen was determined by elemental analysis. The analytical result indicated that over 88% of the vinyl ether groups participated in the haloalkoxylation. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3729–3735, 2000  相似文献   

4.
The overall objective of this research is the creation of novel star polymers consisting of well‐defined stable cores out of which radiate multiple poly(isobutylene‐co‐styrene) [P(IB‐co‐St)] arms whose glass‐transition temperature (Tg) can be controlled over a wide range (?73 to +100 °C) and whose arm termini are fitted with multipurpose (e.g., crosslinkable) functionalities. The first article of this series relates the synthesis and characterization of azeotropic IB/St copolymers [P(IB‐aze‐St)], which are to be subsequently used as end‐functional arms of the target stars. The P(IB‐aze‐St)s are models for statistical IB/St copolymers. The azeotropic composition is 21/79 (mol/mol) IB/St, and NMR, Fourier transform infrared, and gel permeation chromatography techniques demonstrate copolymer compositional homogeneity over the 12–96% conversion range. Conditions were developed for living azeotropic IB/St copolymerization. The livingness of the azeotropic copolymerization was proven by kinetic investigations. P(IB‐aze‐St)s with number‐average molecular weights of up to 24,000 g/mol and polydispersity indices (weight‐average molecular weight/number‐average molecular weight) less than 1.5 were prepared. The copolymerization reactivity ratios were determined: rIB = 3.41 ± 0.23 and rSt = 1.40 ± 0.26. The effect of the P(IB‐aze‐St) molecular weight on Tg was studied by DSC. Tg increases linearly with the number‐average molecular weight and reaches a plateau at 62 °C at 24,000 g/mol. The heat stability of P(IB‐aze‐St) was investigated by thermogravimetric analysis, and a 5% weight loss was found at 250 °C in air. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1515–1524, 2001  相似文献   

5.
A series of easily accessible and stable Schiff‐base nickel complexes (complex 1 – 4 ) in conjunction with methylaluminoxane (MAO) were employed for the synthesis of relatively high molecular weight β‐pinene polymers at high temperature with high productivity. The ligand structure of the complex had a substantial effect on the polymerization in terms of the productivity and the molecular weight. With complex 4 in the presence of MAO, high molecular weight polymers of β‐pinene (Mn ~ 10,900) were obtained at 40 °C with an extremely high productivity up to 1.25 × 107 g polyβ‐pinene/mol of Ni. 1H NMR analyses showed that the obtained β‐pinene polymer was structurally identical to that formed by conventional cationic Lewis acid initiators. The polymerization was presumably initiated by the nickel cation formed by the reaction of the schiff‐base nickel complex and MAO, while the propagation proceeded in a manner typical for a conventional carbocationic polymerization process. Direct evidence for the carbocationic polymerization was offered by the fact that quenching of the polymerization with methanol at a low monomer conversion resulted in incorporation of a methoxyl end group into the polymer chain. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3739–3746, 2007  相似文献   

6.
The carbocationic copolymerization of isobutylene (IB) and styrene (St) was investigated using real time FTIR monitoring. Depending on the concentration of the individual monomers, and their ratio in the feed, initial rapid monomer consumption was observed. Instantaneous reactivity ratios (rIB(inst) and rSt(inst)) obtained from apparent rate constants of monomer consumption strongly depended on concentration.  相似文献   

7.
Boron‐ and silicon‐containing conjugated homo‐ and copolymers could be synthesized using acyclic diene metathesis (ADMET) condensation of bis‐styryl monomers. Both, tri‐and tetra‐coordinated boron monomers were successfully polymerized forming homopolymers, or random copolymers (if polymerized together with a silicon containing co‐monomer). Polymer molecular weights Mn were measured at ~6000 to 15,000 g/mol (NMR end group analysis) with molecular weight distributions Mw/Mn ~1.8 to 2.2. The polymers absorbed at λmax ~317 to 406 nm and emitted at λmax ~370 to 494 nm with fluorescent quantum efficiencies ~24 to 48%. The copolymer with tri‐coordinate boron showed highly efficient fluorescence quenching in the presence of fluoride ions at ratios boron/fluoride ~5/1, demonstrating its potential as anion sensor. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1707–1718  相似文献   

8.
A series of well‐defined amphiphilic diblock copolymers consisting of hydrophobic polyisobutylene (PIB) and hydrophilic poly(2‐(diethylamino)ethyl methacrylate) (PDEAEMA) segments was synthesized via the combination of living carbocationic polymerization and reversible addition fragmentation chain transfer (RAFT) polymerization. Living carbocationic polymerization of isobutylene followed by end‐capping with 1,3‐butadiene was first performed at ?70 °C to give a well‐defined allyl‐Cl‐terminated PIB with a low polydispersity (Mw/Mn =1.29). This end‐functionalized PIB was further converted to a macromolecular chain transfer agent for mediating RAFT block copolymerization of 2‐(diethylamino)ethyl methacrylate at 60 °C in tetrahydrofuran to afford the target well‐defined PIB‐b‐PDEAEMA diblock copolymers with narrow molecular weight distributions (Mw/Mn ≤1.22). The self‐assembly behavior of these amphiphilic diblock copolymers in aqueous media was investigated by fluorescence spectroscopy and transmission electron microscope, and furthermore, their pH‐responsive behavior was studied by UV‐vis and dynamic light scattering. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1478–1486  相似文献   

9.
Multiarm star‐branched polymers based on poly(styrene‐b‐isobutylene) (PS‐PIB) block copolymer arms were synthesized under controlled/living cationic polymerization conditions using the 2‐chloro‐2‐propylbenzene (CCl)/TiCl4/pyridine (Py) initiating system and divinylbenzene (DVB) as gel‐core‐forming comonomer. To optimize the timing of isobutylene (IB) addition to living PS⊕, the kinetics of styrene (St) polymerization at −80°C were measured in both 60 : 40 (v : v) methyl cyclohexane (MCHx) : MeCl and 60 : 40 hexane : MeCl cosolvents. For either cosolvent system, it was found that the polymerizations followed first‐order kinetics with respect to the monomer and the number of actively growing chains remained invariant. The rate of polymerization was slower in MCHx : MeCl (kapp = 2.5 × 10−3 s−1) compared with hexane : MeCl (kapp = 5.6 × 10−3 s−1) ([CCl]o = [TiCl4]/15 = 3.64 × 10−3M; [Py] = 4 × 10−3M; [St]o = 0.35M). Intermolecular alkylation reactions were observed at [St]o = 0.93M but could be suppressed by avoiding very high St conversion and by setting [St]o ≤ 0.35M. For St polymerization, kapp = 1.1 × 10−3 s−1 ([CCl]o = [TiCl4]/15 = 1.82 × 10−3M; [Py] = 4 × 10−3M; [St]o = 0.35M); this was significantly higher than that observed for IB polymerization (kapp = 3.0 × 10−4 s−1; [CCl]o = [Py] = [TiCl4]/15 = 1.86 × 10−3M; [IB]o = 1.0M). Blocking efficiencies were higher in hexane : MeCl compared with MCHx : MeCl cosolvent system. Star formation was faster with PS‐PIB arms compared with PIB homopolymer arms under similar conditions. Using [DVB] = 5.6 × 10−2M = 10 times chain end concentration, 92% of PS‐PIB arms (Mn,PS = 2600 and Mn,PIB = 13,400 g/mol) were linked within 1 h at −80°C with negligible star–star coupling. It was difficult to achieve complete linking of all the arms prior to the onset of star–star coupling. Apparently, the presence of the St block allows the PS‐PIB block copolymer arms to be incorporated into growing star polymers by an additional mechanism, namely, electrophilic aromatic substitution (EAS), which leads to increased rates of star formation and greater tendency toward star–star coupling. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1629–1641, 1999  相似文献   

10.
Cationic cyclopolymerization of 2‐methyl‐5,5‐bis(vinyloxymethyl)‐1,3‐dioxane ( 1 ), a divinyl ether with a cyclic acetal group, was investigated with the HCl/ZnCl2 initiating system in toluene and methylene chloride at ?30 °C. The reaction proceeded quantitatively to give gel‐free, soluble polymers in organic solvents. The number‐average molecular weight (Mn) of the polymers increased in direct proportion to monomer conversion, and further increased on addition of a fresh monomer feed to the almost completely polymerized reaction mixture, indicating that the polymerization proceeded in living/controlled manner. The contents of the unreacted vinyl groups in the produced soluble polymers were less than ~3 mol %, and therefore, the degree of cyclization was determined to be ~97%. In contrast, the pendant cyclic acetal groups remained intact in the polymers under the present cationic polymerization conditions. These facts show that cyclopolymerization of 1 almost exclusively occurred and the poly(vinyl ether)s with the cyclized repeating units and cyclic pendant acetal rings were obtained. Glass transition temperature (Tg) and thermal decomposition temperature (Td) of poly( 1 ) (Mn = 7870, Mw/Mn = 1.57) were found to be 166 and 338 °C, respectively, indicating that poly( 1 ) had high Tg and high thermal stability. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 952–958, 2010  相似文献   

11.
Free radical copolymerization of sulfur dioxide with phenylacetylene (PA) in o-dichlorobenzene was studied in a range of temperatures from 30 to 80oC as a function of total monomer concentration ([SO2] + [PA]). PA content in the copolymers increases with decreasing total monomer concentration and increasing temperature. M w/M n becomes sharper with decreasing the total monomer concentration, but does not depend upon feed compositions which are changed keeping total monomer concentration constant at 2, 4, and 6 mol/L, respectively. These results strongly indicate the existence of depropagation. Thermal decomposition of the copolymers happens more easily than PA homopolymer and the carbon-centered free radicals are detected during the decomposition. Reactivity of ~ CH??(Ph) free radical (~ PA · ) is also discussed.  相似文献   

12.
A combination of living polymerization of ylides and atom transfer radical polymerization (ATRP) was used successfully in the design and synthesis of well‐defined polymethylene‐b‐poly(methyl methacrylate) (PM‐b‐PMMA) and polymethylene‐b‐poly(n‐butyl acrylate) (PM‐b‐Pn‐BuA). Tripolymethylene borane were firstly synthesized by living polymerization of dimethylsulfoxonium methylides and then oxidated quantitatively through trimethylamine‐N‐oxide dihydrate to provide a series of low‐polydispersity hydroxyl‐terminated polymethylenes (PM‐OHs) with different molecular weight. Subsequently, such polymers were converted into polymethylene‐based macroinitiators (PM‐MIs, Mn(GPC) = 1900–10,400 g/mol; Mw/Mn = 1.12–1.23) in ~100% conversion. ATRPs of methyl methacrylate and n‐butyl acrylate were successfully conducted using PM‐MI to produce well‐defined diblock copolymers of PM‐b‐PMMA and PM‐b‐Pn‐BuA, respectively. The GPC traces indicated the successful extension of PMMA and Pn‐BuA segment (Mn(GPC) of PM‐b‐PMMA = 3980–10,100 g/mol; Mw/Mn = 1.16–1.22; Mn of PM‐b‐Pn‐BuA = 7400–9200 g/mol; Mw/Mn = 1.14–1.18). Atomic force microscopy (AFM) was used to characterize the structures of the precipitated PM‐b‐PMMA micelles, which were formed in toluene. The blend of LDPE/PMMA was prepared with PM‐b‐PMMA as compatibilizer. The scanning electron microscopy (SEM) results showed that the compatibilization of the LDPE/PMMA was improved greatly by the incorporation of PM‐b‐PMMA. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5671–5681, 2009  相似文献   

13.
Olefin group‐carrying styrene, 1‐but‐3‐enyl‐4‐vinylbenznene (BVB), was polymerized via atom transfer radical polymerization (ATRP) initiated from C‐methylcalix [4]resorcinarene‐based multifunctional initiator (CRA‐bib) at low conversion to produce star polymer [poly(BVB)] with narrow molecular weight distribution (Mw/Mn < 1.35). The copolymerization of styrene (St) with poly(BVB) (Mn = 11,000, Mw/Mn = 1.23) as a macroinitiator afforded star block copolymer [poly(BVB‐b‐St)] with Mn = 35,000 and Mw/Mn = 1.44. The BVB layer of poly(BVB‐b‐St), located between the St shell and the CRA core, was crosslinked by olefin metathesis reaction of olefin groups o the BVB moieties. The removal of the CRA core of the crosslinked poly(BVB‐b‐St) by hydrolysis using KOH as a base gave polymeric hollow sphere [poly(cored crossBVB‐b‐St)] with good solubility in organic solvents. The morphological structure of the poly(cored crossBVB‐b‐St) showed spherical aggregates in THF by scanning electron microscopy (SEM). Furthermore, the nanocapsule structure of poly(cored crossBVB‐b‐St) with hollow spheres was found to be observed by transmission electron microscopy (TEM). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4879–4888, 2008  相似文献   

14.
Our objective was the precision synthesis of novel stars consisting of a well‐defined calix[8]arene core out of which radiate eight poly(isobutylene‐aze‐styrene) [P(IB‐aze‐St)] arms fitted with crosslinkable end groups. We reached our objective by preparing the octafunctional calixarene derivative C[8]OCH3, inducing the living azeotropic copolymerization of IB/St charges with the C[8]OCH3/BCl3·TiCl4 initiating system, and end‐quenching living IB/St copolymerizations with allyltrimethylsilane. With this strategy, we obtained stars C[8]? [P(IB‐aze‐St)? CH2CH?CH2]8 of various molecular weights. The number of ? CH2CH?CH2 termini of the arms was 8.0 ± 0.2 by quantitative 1H NMR analysis. The eight allyl termini were quantitatively converted to ? CH2CH2CH2OH termini by hydroboration/oxidation. To confirm that the latter second‐generation stars possessed eight primary alcohol end groups, we quantitatively converted the ? CH2OH termini to ? OSi(CH3)3 termini, the concentration of which was quantitated by 1H NMR spectroscopy. According to this analysis, the stars contained 8.0 ± 0.3 hydroxyl termini. The glass‐transition temperatures of the P(IB‐aze‐St) arms increased from 59 to 65 °C as the weight‐average molecular weights of the arms increased from about 2500 to about 4300 g/mol, respectively. The α and K constants of the Mark–Houwink–Sakurada relationship and the intrinsic viscosity of a representative allyl‐telechelic star were determined and compared with a linear azeotropic IB/St copolymer of similar molecular weight. The crosslinking of C[8]? [P(IB‐aze‐St)CH2CH2CH2OH]8 stars with 4,4′‐methylene bis(phenyl) diisocyanate and 2,4‐tolylene diisocyanate in various solvents afforded tightly crosslinked films of potential interest for scratch‐resistant coatings, mar‐resistant coatings, or both. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1525–1532, 2001  相似文献   

15.
Cationic polymerizations of isobutylene (IB) with H2O/FeCl3/isopropanol (iPrOH) initiating system were conducted in nonpolar hydrocarbon media, such as n‐hexane or mixed C4 fractions at ?40 to 20 °C. This cationic polymerization is a chain‐transfer dominated process via highly selective β‐proton elimination from ? CH3 in the growing chain ends, leading to formation of highly reactive polyisobutylenes (HRPIBs) with large contents (> 90 mol %) of exo‐olefin end groups (structure A ). The content of structure A remained nearly constant at about 97 mol % during polymerization and isomerization via carbenium ion rearrangement could be suppressed in nonpolar media. First‐order kinetics with respect to monomer concentration was measured for selective cationic polymerization of IB in the mixed C4 fraction feed at ?30 °C and the apparent rate constant for propagation was 0.028 min?1. High polymerization temperature (Tp) or [FeCl3] accelerate β‐proton elimination or isomerizations and simultaneously decrease selectivity of β‐proton abstraction from ? CH3. Molecular weight decreased and molecular weight distribution (MWD) became narrow with increasing Tp or [FeCl3]. To the best of our knowledge, this is the first example to achieve high quality HRPIBs with near 100% of exo‐olefin terminals and relatively narrow MWD (Mw/Mn = 1.8) by a single‐step process in nonpolar hydrocarbon media. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4200–4212  相似文献   

16.
Differential scanning calorimetry has been used to examine blends of a poly(ethylene oxide) (PEO), Mn = 300 g/mol, and a poly(methylmethacrylate) (PMMA), Mn = 10,000 g/mol, across the complete composition range. The relatively low molar mass of the PEO minimizes interference from crystallization. In the midrange of composition, ~25–70% PEO, two broad, but distinct, glass transitions are resolved. These are interpreted as distinct glass transitions of the two components, as anticipated by the self‐concentration model of Lodge and McLeish. The composition dependence of the observed transitions is well described by the self‐concentration approach, using lengthscales of approximately two‐thirds of the Kuhn length. The results are compared with previous measurements on PEO/PMMA blends and other miscible systems. The principal, general conclusion is that one should actually expect two glass transitions in a miscible polymer blend or polymer solution; the rule of thumb that two transitions indicate immiscibility is incorrect. Furthermore, attempts to rationalize two transitions on the basis of incomplete segmental mixing, or other unspecified “nanoheterogeneity,” may not be justified in many cases. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 756–763, 2006  相似文献   

17.
The aliphatic polyurethane with pendant anthracene moieties (PU‐anthracene) was prepared from polycondensation of anthracen‐9‐yl methyl 3‐hydroxy‐2‐(hydroxymethyl)‐2‐methylpropanoate (anthracene diol), 1 with hexamethylenediisocyanate in the presence of dibutyltindilaurate in CH2Cl2 at room temperature for 10 days. Thereafter, the PU‐anthracene (Mn,GPC = 12,900 g/mol, Mw/Mn = 1.87, relative to PS standards) was clicked with a linear α‐furan protected‐maleimide terminated‐poly(methyl methacrylate) (PMMA‐MI) (Mn,GPC = 2500 g/mol, Mw/Mn = 1.33), or ‐poly(ethylene glycol) (PEG‐MI) (Mn,GPC = 550 g/mol, Mw/Mn = 1.09), to result in well‐defined PU‐graft copolymers, PU‐g‐PMMA (Mn,GPC = 23800 g/mol, Mw/Mn = 1.65, relative to PS standards) or PU‐g‐PEG (Mn,GPC = 11,600 g/mol, Mw/Mn = 1.45, relative to PS standards) using Diels–Alder reaction in dioxane/toluene at 105 °C. The Diels–Alder grafting efficiencies were found to be over 93–99% using UV spectroscopy. Moreover, the structural analyses and the thermal transitions of all copolymers were determined via 1H NMR and DSC, respectively. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 521–527  相似文献   

18.
Monodisperse polystyrene (PS) particles were prepared by a living radical dispersion polymerization with a reversible addition‐fragmentation chain transfer (RAFT) agent in an ethanol medium. In the presence of RAFT agent, the effects of various reaction parameters on the characteristics of PS particles were systematically investigated. When no RAFT agent was involved, the number‐average molecular weight (Mn) of the PS particles increased from 17,800 to 30,000 g/mol, but the weight‐average diameter (Dw) decreased from 2.54 to 2.06 μm with the increase of poly(N‐vinylpyrrolidone) content from 4.0 to 16.0 wt %. No correlation between the Mn and the coefficient of variation (CV) was observed. However, when the RAFT concentration varied from 0 to 2.0 wt %, all of the conversion, Mn, Dw, CV, and polydispersity index (Mw/Mn) decreased. This indicates that the RAFT agent alters the inverse behavior between the molecular weight (MW) and particle size shown in the conventional dispersion polymerization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 872–885, 2008  相似文献   

19.
Polyisobutylene‐b‐poly(N,N‐diethylacrylamide) (PIB‐b‐PDEAAm) well‐defined amphiphilic diblock copolymers were synthesized by sequential living carbocationic polymerization and reversible addition‐fragmentation chain transfer (RAFT) polymerization. The hydrophobic polyisobutylene segment was first built by living carbocationic polymerization of isobutylene at ?70 ° C followed by multistep transformations to give a well‐defined (Mw/Mn = 1.22) macromolecular chain transfer agent, PIB‐CTA. The hydrophilic poly(N,N‐diethylacrylamide) block was constructed by PIB‐CTA mediated RAFT polymerization of N,N‐diethylacrylamide at 60 ° C to afford the desired well‐defined PIB‐b‐PDEAAm diblock copolymers with narrow molecular weight distributions (Mw/Mn ≤1.26). Fluorescence spectroscopy, transmission electron microscope, and dynamic light scattering (DLS) were employed to investigate the self‐assembly behavior of PIB‐b‐PDEAAm amphiphilic diblock copolymers in aqueous media. These diblock copolymers also exhibited thermo‐responsive phase behavior, which was confirmed by UV‐Vis and DLS measurements. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1143–1150  相似文献   

20.
Two novel monomers, ambrettolide epoxide and isopropyl aleuriteate, encompassing functional groups, were obtained in a single step from commercially available materials. Novozym 435 catalyzed ring opening polymerization of ambrettolide epoxide furnished a polymer of Mn = 9.7 kg/mol and PDI = 1.9 while the epoxide groups remained unaffected during the polymerization. Selective polymerization of the primary hydroxyl groups of isopropyl aleuriteate using Novozym 435 was feasible and a polymer with moderate molecular weight (Mn = 5.6 kg/mol, PDI = 3.2) was isolated in moderate yield (43%). Subsequently, copolymerization of isopropyl aleuriteate with ε‐CL in different ratios was performed, resulting in soluble, hydroxy functional polymers with good molecular weights (Mn = 10.4–27.2 kg/mol) in good yield (71–78%). The secondary hydroxy groups in the polymer reacted easily with hexyl isocyanate, showing the potential of isopropyl aleuriteate as a comonomer for the synthesis of functional polyesters. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5968–5978, 2007  相似文献   

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