共查询到20条相似文献,搜索用时 0 毫秒
1.
Huadong Tang Jianbin Tang Shijie Ding Maciej Radosz Youqing Shen 《Journal of polymer science. Part A, Polymer chemistry》2005,43(7):1432-1443
Polymeric forms of ionic liquids have many potential applications because of their high thermal stability and ionic nature. Two ionic liquid monomers, 1‐(4‐vinylbenzyl)‐3‐butyl imidazolium tetrafluoroborate (VBIT) and 1‐(4‐vinylbenzyl)‐3‐ butyl imidazolium hexafluorophosphate (VBIH), were synthesized through the quaternization of N‐butylimidazole with 4‐vinylbenzylchloride and a subsequent anion‐ exchange reaction with sodium tetrafluoroborate or potassium hexafluorophosphate. Copper‐mediated atom transfer radical polymerization was used to polymerize VBIT and VBIH. The effects of various initiator/catalyst systems, monomer concentrations, solvent polarities, and reaction temperatures on the polymerization were examined. The polymerization was well controlled and exhibited living characteristics when CuBr/1,1,4,7,10,10‐hexamethyltriethylenetetramine or CuBr/2,2′‐bipyridine was used as the catalyst and ethyl 2‐bromoisobutyrate was used as the initiator. Characterizations by thermogravimetric analysis, differential scanning calorimetry, and X‐ray diffraction showed that the resulting VBIT polymer, poly[1‐(4‐vinylbenzyl)‐3‐butyl imidazolium tetrafluoroborate] (PVBIT), was amorphous and had excellent thermal stability, with a glass‐transition temperature of 84 °C. The polymerized ionic liquids could absorb CO2 as ionic liquids: PVBIT absorbed 0.30% (w/w) CO2 at room temperature and 0.78 atm. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1432–1443, 2005 相似文献
2.
3.
4.
Yan Shi Zhifeng Fu Bingyi Li Wantai Yang 《Journal of polymer science. Part A, Polymer chemistry》2006,44(8):2468-2475
A stable nitroxyl radical functionalized with an initiating group for atom transfer radical polymerization (ATRP), 4‐(2‐bromo‐2‐methylpropionyloxy)‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy (Br‐TEMPO), was synthesized by the reaction of 4‐hydroxyl‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy with 2‐bromo‐2‐methylpropionyl bromide. Stable free radical polymerization of styrene was then carried out using a conventional thermal initiator, dibenzoyl peroxide, along with Br‐TEMPO. The obtained polystyrene had an active bromine atom for ATRP at the ω‐end of the chain and was used as the macroinitiator for ATRP of methyl acrylate and ethyl acrylate to prepare block copolymers. The molecular weights of the resulting block copolymers at different monomer conversions shifted to higher molecular weights and increased with monomer conversion. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2468–2475, 2006 相似文献
5.
Synthesis and radical polymerization of methacrylate endowed with bicyclobis(γ‐butyrolactone) moiety through methylene linker
下载免费PDF全文
![点击此处可从《Journal of polymer science. Part A, Polymer chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Ryu Yamasaki Atsushi Sudo Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2015,53(21):2462-2468
A series of methacrylates bearing bicyclobis(γ‐butyrolactone) (BBL) moiety were synthesized and radically polymerized to afford the corresponding poly(methacrylate)s bearing BBL moiety in the side chain, with expecting that the high polarity and rigidity of BBL would be inherited by the polymers. The resulting polymers were soluble in polar aprotic solvents such as dimethyl sulfoxide and N,N‐dimethylformamide because of the high polarity of the BBL moiety. The glass transition temperatures (Tg) of the polymers depended on the length of methylene linker that tethered the methacrylate and BBL moieties, making the use of shorter linkers lead to higher Tgs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2462–2468 相似文献
6.
7.
Tadeusz Biedro Przemysaw Kubisa 《Journal of polymer science. Part A, Polymer chemistry》2002,40(16):2799-2809
Atom transfer radical polymerization (ATRP) of acrylates in ionic liquid, 1‐butyl‐3‐methylimidazolium hexaflurophospate, with the CuBr/CuBr2/amine catalytic system was investigated. Sequential polymerization was performed by synthesizing AB block copolymers. Polymerization of butyl acrylate (monomer that is only partly soluble in an ionic liquid forming a two‐phase system) proceeded to practically quantitative conversion. If the second monomer (methyl acrylate) is added at this stage, polymerization proceeds, and block copolymer formed is essentially free of homopolymer according to size exclusion chromatographic analysis. The number‐average molecular weight of the copolymer is slightly higher than calculated, but the molecular weight distribution is low (Mw/Mn = 1.12). If, however, methyl acrylate (monomer that is soluble in an ionic liquid) is polymerized at the first stage, then butyl acrylate in the second‐stage situation is different. Block copolymer free of homopolymer of the first block (with Mw/Mn = 1.13) may be obtained only if the conversion of methyl acrylate at the stage when second monomer is added is not higher than 70%. Matrix‐assisted laser desorption/ionization time‐of‐flight analysis confirmed that irreversible deactivation of growing macromolecules is significant for methyl acrylate polymerization at a monomer conversion above 70%, whereas it is still not significant for butyl acrylate even at practically quantitative conversion. These results show that ATRP of butyl acrylate in ionic liquid followed by addition of a second acrylate monomer allows the clean synthesis of block copolymers by one‐pot sequential polymerization even if the first stage is carried out to complete conversion of butyl acrylate. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2799–2809, 2002 相似文献
8.
9.
Alexandra Muoz‐Bonilla María L. Cerrada Marta Fernndez‐García 《Journal of polymer science. Part A, Polymer chemistry》2005,43(20):4828-4837
The syntheses of triblock copolymers by the atom transfer radical polymerization of tert‐butyl and iso‐butyl acrylates as inner blocks with cyclohexyl methacrylate as outer blocks are reported. The living behavior and blocking efficiency of these polymerizations were investigated in each case. The use of difunctional macroinitiators led to ABA triblock copolymers with narrow polydispersities and controlled number‐average molecular weights. These copolymers were prepared from bromo‐terminated macroinitiators of poly(tert‐butyl acrylate) and poly(iso‐butyl acrylate), with copper chloride/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as the catalytic system, at 40 °C in 50% (v/v) toluene solutions. The block copolymers were characterized with size exclusion chromatography and 1H NMR spectroscopy. Differential scanning calorimetry measurements were performed to reveal the phase segregation. The glass transition of the inner block was not clearly detected, with the exception of the copolymer synthesized with the longest poly(iso‐butyl acrylate) macroinitiator length. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4828–4837, 2005 相似文献
10.
Natalia Davidenko Dionisio Zaldívar Carlos Peniche Roberto Sastre Julio San Romn 《Journal of polymer science. Part A, Polymer chemistry》1996,34(13):2759-2766
The effect and the participation of the furfuryl ring, in particular the hydrogen at position C-5 in the free radical polymerization are analyzed following the polymerization of furfuryl acrylate (FA) and furfuryl methacrylate (FM) initiated by AIBN under photochemical activation. The results obtained indicate that the polymerization of FA deviates from the classical free radical kinetic scheme, giving rise to crosslinked polymers even at a degree of conversion lower than 7%. This behavior is well explained taking into consideration the participation of the furfuryl ring which acts as a degradative transfer agent. This was demonstrated by the kinetic analysis of the free radical polymerization of MMA initiated by the thermal decomposition of AIBN in the presence of different concentrations of furfuryl acetate. © 1996 John Wiley & Sons, Inc. 相似文献
11.
A stable nitroxyl radical functionalized with two initiating groups for atom transfer radical polymerization (ATRP), 4-(2,2-bis-(methyl 2-bromo isobutyrate)-propionyloxy)-2,2,6,6-tetramethyl-1-piperidinyloxy (Br2-TEMPO), was synthesized by reacting 4-hydroxyl-2,2,6,6-tetramethyl-1-piperidinyloxy with 2,2-bis-(methyl 2-bromo isobutyrate) propanoic acid. Stable free radical polymerization of styrene was then carried out using a conventional thermal initiator, dibenzoyl peroxide, along with Br2-TEMPO. The obtained polystyrene had two active bromine atoms for ATRP at the ω-end of the chain and was further used as the macroinitiator for ATRP of methyl acrylate and ethyl acrylate to prepare AB2-type miktoarm star-shaped copolymers. The molecular weights of the resulting miktoarm star-shaped copolymers at different monomer conversions shifted to higher molecular weights without any trace of the macroinitiator, and increased with monomer conversion. 相似文献
12.
Improving the knowledge and design of end groups in polymers produced by free radical polymerization
W. Ken Busfield Ian D. Jenkins Tomoyuki Nakamura Michael J. Monteiro Ezio Rizzardo Shuji Sayama San H. Thang Phuc Van Le Clovia I. Zayas-Holdsworth 《先进技术聚合物》1998,9(1):94-100
Several techniques have been used to probe polymer end groups. The nitroxide radical trapping technique has been used (i) to show that initiator-derived unsaturated end groups in polymethyl methacrylate can be minimized by using t-hexyl peroxypivalate as the initiator (ii) to predict the end and penultimate groups in acrylonitrile/ethyl vinyl ether copolymer produced by t-butoxyl initiation by analogy with the initiation mechanism (iii) to predict probable end groups in polyacrylonitrile and polystyrene produced by cyanoisopropyl initiation in the presence of adventitious oxygen. NMR techniques have been used to show that the end groups of functionalized oligomers, made from styrene and methacrylonitrile by the addition-fragmentation chain transfer technique with allylic sulphides, conform to the expected structures. © 1998 John Wiley & Sons, Ltd. 相似文献
13.
Shijing Cheng Mingqiang Zhang Tianyu Wu Sean T. Hemp Brian D. Mather Robert B. Moore Timothy E. Long 《Journal of polymer science. Part A, Polymer chemistry》2012,50(1):166-173
Copolymers of n‐butyl acrylate and phosphonium ionic liquid monomers possessing various alkyl substituents and counterions were synthesized through a combination of conventional free radical copolymerization and anion exchange. Differential scanning calorimetry and dynamic mechanical analysis provided the thermal and mechanical properties of these phosphonium cation‐containing random copolymers. Factors including alkyl chain length of phosphonium substituents, counterion type, as well as ionic concentration significantly influenced the association of phosphonium cations. Phosphonium ionomers with trialkyl substituents on phosphonium cations did not display the characteristic small‐angle X‐ray scattering peak, suggesting the absence of ionic clusters. However, low q peaks in wide‐angle X‐ray diffraction was indicative of significant concentration fluctuations wherein the ionic monomeric units associated. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
14.
Yasemin Yuksel Durmaz Manolya Kukut Norbert Moszner Yusuf Yagci 《Journal of polymer science. Part A, Polymer chemistry》2009,47(18):4793-4799
A block copolymer of cyclohexene oxide (CHO) and styrene (St) was prepared by using bifunctional visible light photoinitiator dibenzoyldiethylgermane (DBDEG) via a two‐step procedure. The bifunctionality of the photoinitiator pertains to the sequential photodecomposition of DBDEG through acyl germane bonds. In the first step, photoinitiated free radical promoted cationic polymerization of CHO using DBDEG in the presence of diphenyliodonium hexafluorophosphate (Ph2I+PF) was carried out to yield polymers with photoactive monobenzoyl germane end groups. These poly(cyclohexene oxide) (PCHO) prepolymers were used to induce photoinitiated free radical polymerization of styrene (St) resulting in the formation of poly(cyclohexene oxide‐block‐styrene) (P(CHO‐b‐St)). Successful blocking has been confirmed by a strong change in the molecular weight of the prepolymer and the block copolymer as well as NMR, IR, and DSC spectral measurements. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4793–4799, 2009 相似文献
15.
Synthesis of traditional and ionic polymethacrylates by anion catalyzed group transfer polymerization
下载免费PDF全文
![点击此处可从《Journal of polymer science. Part A, Polymer chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Veronika Strehmel Volker Senkowski 《Journal of polymer science. Part A, Polymer chemistry》2015,53(24):2849-2859
The hydrophobic ionic liquid 1‐butyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imide was successfully used as solvent in group transfer polymerization of traditional methacrylates (methyl methacrylate, n‐butyl methacrylate, and benzyl methacrylate) and of ionic liquid methacrylates (ILMAs). This demonstrates that this ionic liquid makes reaction conditions, which do not require the use of ultra‐dried solvents. The ILMAs were N‐[2‐(methacryloyloxy)ethyl]‐N,N‐dimethyl‐N‐alkylammonium bis(trifluoromethylsulfonyl)imides bearing methyl, ethyl, propyl, butyl, or hexyl substituents. Increasing size of the alkyl substituent at the cation results in decreasing glass transition temperature in case of both ionic liquid methacrylates and polymers derived of them. Furthermore, the glass transition temperature is significantly higher for these polymers compared with the ionic liquid methacrylates, and the effect of glass transition temperature reduction with increasing size of the alkyl substituent is stronger for the polymers. A mechanism was proposed explaining the catalytic function of the ionic liquid used as solvent for polymerization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2849–2859 相似文献
16.
Yakov S. Vygodskii Olga A. Mel'nik Elena I. Lozinskaya Alexander S. Shaplov Inna A. Malyshkina Nadejda D. Gavrilova Konstantin A. Lyssenko Mikhail Yu. Antipin Denis G. Golovanov Alexander A. Korlyukov Nikolai Ignat'ev Urs Welz‐Biermann 《先进技术聚合物》2007,18(1):50-63
Various 1,3‐dialkylimidazolium and tetraalkylphosphonium ionic liquids (ILs), including novel ones, have been studied as reaction media for free radical polymerization of methyl methacrylate (MMA), acrylonitrile (AN) and 1‐vinyl‐3‐ethylimidazolium salts (ViEtIm+)Y?. The influence of IL's nature upon the polymer formulation was investigated. The use of different ionic liquids allows not only to obtain the polymers with high molecular weight (PMMA, up to 5,770,000 g/mol; PAN, up to 735,000 g/mol and poly[(ViEtIm+)Y?], up to 1,130,000 g/mol) in high yields, but also to control the polymerization rate and molecular mass. The physicochemical characteristics, including mechanical properties, thermal stability and heat‐resistance of the obtained polymers were studied in order to compare with those of polymers prepared in a traditional media. It was found that elongation, tensile modulus and strength of PAN, which was synthesized in ionic liquid, are reliatively higher. The influence of IL's nature upon their ionic conductivity and the formation of conductive polymers from molten‐salt‐type vinyl monomers was investigated. Molecular design of the polymers simultaneously with the influence of IL's nature in order to achieve higher ionic conductivity is discussed. Flexible, transparent polymer films, obtained in different ways, show relatively high ionic conductivity (of about 10?5 S cm?1 at 20°C). Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
17.
Zulma Jiménez Christopher Bounds Charles E. Hoyle Andrew B. Lowe Hui Zhou John A. Pojman 《Journal of polymer science. Part A, Polymer chemistry》2007,45(14):3009-3021
Polymerizable ionic liquids were synthesized from the neutralization reaction between trialkylamines (tributylamine, trihexylamine, trioctylamine, 2‐(dimethyl‐amino)ethyl acrylate, and 2‐(dimethylamino)ethyl methacrylate) and acid‐containing (meth)acrylates to study the kinetics of their photopolymerization. The ionic liquids formed from acrylic acid and methacrylic acid with trialkylamines showed low or moderate increases in rate compared to their monofunctional analogues. The ionic liquids formed from (meth)acrylic acid and a tertiary amine with a pendant acrylate exhibited rates typical of traditional di(meth)acrylates, although the (meth)acrylates were not covalently attached to the same molecule. All of the phosphate‐based ionic liquids exhibited very rapid polymerization rates and strong dependence on the initial viscosity. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3009–3021, 2007 相似文献
18.
Tobias Janoschka Anke Teichler Andreas Krieg Martin D. Hager Ulrich S. Schubert 《Journal of polymer science. Part A, Polymer chemistry》2012,50(7):1394-1407
This work describes the polymerization of the free secondary amine bearing monomer 2,2,6,6‐tetramethylpiperidin‐4‐yl methacrylate (TMPMA) by means of different controlled radical polymerization techniques (ATRP, RAFT, NMP). In particular, reversible addition‐fragmentation chain transfer (RAFT) polymerization enabled a good control at high conversions and a polydispersity index below 1.3, thereby enabling the preparation of well‐defined polymers. Remarkably, the polymerization of the secondary amine bearing methacrylate monomer was not hindered by the presence of the free amine that commonly induces degradation of the RAFT reagent. Subsequent oxidation of the polymer yielded the polyradical poly(2,2,6,6‐tetramethylpiperidinyloxy‐4‐yl methacrylate), which represents a valuable material used in catalysis as well as for modern batteries. The obtained polymers having a molar mass (Mn) of 10,000–20,000 g/mol were used to fabricate well‐defined, radical‐bearing polymer films by inkjet‐ printing. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
19.
Berran Sanay Bernd Strehmel Veronika Strehmel 《Journal of polymer science. Part A, Polymer chemistry》2020,58(22):3196-3208
Investigation of photopolymerization kinetics of 4-(4-methacryloyloxyphenyl)-butan-2-one (1) in comparison with 2-phenoxyethyl methacrylate (2) and phenyl methacrylate (3) using a UV-LED emitting at 395 nm shows significantly faster polymerization of 1 compared to both 2 and 3 at 40°C. Vitrification affects photopolymerization kinetics of all methacrylates under investigation. Interestingly, quantitative final conversion is observed during photoinitiated polymerization of 1 and 2 whereas 3 shows limited conversion at about 80%. Furthermore, higher degree of polymerization is obtained by photoinitiated polymerization of 1 compared to 2 and 3. This shows that the 3-oxobutyl substituent at the phenyl ring of 1 significantly affects both polymerization kinetics and final conversion of the photoinitiated polymerization. Moreover, an additional higher molecular weight fraction is observed in case of polymerization of 1 at 85°C that is above the glass transition temperature of the polymer formed during photoinitiated polymerization. As a thermal polymerization at 85°C in the absence of light results in a high molecular weight polymer as well, an additional thermal process may be discussed as reason for the higher molecular weight polymer fraction in case of the photopolymer made at 85°C. 相似文献
20.
Polymeric 1-vinyl-3-octylimidazolium hexafluorophosphate was synthesized in situ on stainless steel wire by surface radical chain-transfer polymerization and used as sensitive coatings in solid-phase microextraction. The outer surface of the stainless steel wire was firstly coated with microstructured silver layer via silver mirror reaction and then functionalized with self-assembled monolayers of 1,8-octanedithiol, which acted as chain transfer agent in the polymerization. Coupled to gas chromatography, extraction performance of the fiber was studied with both headspace and direct-immersion modes using benzene, toluene, ethylbenzene and xylenes (BTEX), phenols and polycyclic aromatic hydrocarbon (PAHs) as model analytes. In combination with the microstructured silver layer, the PIL-coated fiber exhibited high extraction efficiency. Linear ranges for BTEX with headspace mode were in the range of 0.2-1000 μg L(-1) for benzene, and 0.1-1000 μg L(-1) for toluene, ethylbenzene and xylenes. Limits of detection (LODs) were from 0.02 to 0.05 μg L(-1). Wide linear ranges of direct-immersion mode for the extraction of several phenols and PAHs were also obtained with correlation coefficients (R) from 0.9943 to 0.9997. The proposed fiber showed good durability with long lifetime. RSDs of 56 times extraction were still in an acceptable range, from 8.85 to 22.8%. 相似文献