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1.
The water-soluble monomers, 1-methyl-4-vinylimidazole, 1-methyl-5-vinylimidazole, 1-ethyl-5-vinylimidazole, and 1-propyl-5-vinylimidazole have been synthesized, polymerized, and copolymerized with 4(5)-vinylimidazole. The copolymers were characterized by 14C-labeling, NMR, pKa determination and viscosity measurements. The monomer reactivity ratios determined by 14C counting are r1 = 1.04; r2 = 0.94 [M1 = 4(5)-vinylimidazole, M2 = 1-methyl-4-vinylimidazole] and r1 = 1.01; r2 = 0.86 [M1 = 4(5)-vinylimidazole, M2 = 1-methyl-5-vinylimidazole]. The esterolytic activity of the copolymers for the hydrolysis of p-nitrophenyl acetate (PNPA) at pH 7–8 in 28.5% ethanol–water was higher than that of the mixtures of homopolymers. At pH 5–6 the esterolytic activities of the copolymers and the mixtures were similar. The most efficient esterolytic activity for PNPA hydrolysis at pH 7.11 in 28.5% ethanol–water occurred for copolymers containing 75 mole % 4(5)-vinylimidazole and for copolymers containing 1-methyl-4-vinylimidazole rather than 1-methyl-5-vinylimidazole.  相似文献   

2.
Two diastereomeric derivatives of norbornene, dimethyl (1R,2R,3S,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate and dimethyl (1R,2S,3S,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate, were synthesized and polymerized using ring-opening metathesis polymerization (ROMP). For comparative purposes, diastereomeric derivatives of Dewar benzene, dimethyl (1R,2S,3R,4S)-bicyclo[2.2.0]hex-5-ene-2,3-dicarboxylate and dimethyl (1R,2S,3S,4S)-bicyclo[2.2.0]hex-5-ene-2,3-dicarboxylate, were also synthesized and polymerized using ROMP. The polymerization reactions proceeded in a controlled manner as evidenced in part by linear relationships between the monomer-to-catalyst feed ratios and the molecular weights of the polymer products. Chain extension experiments were also conducted which facilitated the formation of block copolymers. Although the poly(norbornene) derivatives exhibited glass transition temperatures that were dependent on their monomer stereochemistry (cis: 115°C vs. trans: 125°C), more pronounced differences were observed upon analysis of the polymers derived from Dewar benzene (cis: 70°C vs. trans: 95°C). Likewise, microphase separation was observed in block copolymers that were prepared using the diastereomeric monomers derived from Dewar benzene but not in block copolymers of the norbornene-based diastereomers. The differential thermal properties were attributed to the relative monomer sizes as reducing the distances between the polymer backbones and the pendant stereocenters appeared to enhance the thermal effects.  相似文献   

3.
In an effort to exploit the enhancement in catalytic activity which might be derived through hydrophobic interactions between polymeric catalyst and substrate, 1-methyl-5-vinylimidazole (1-Me-5-VIm), 1-methyl-4-vinylimidazole (1-Me-4-VIm), 1-butyl-5-vinylimidazole (1-Bu-5-VIm), and 1-butyl-4-vinylimidazole (1-Bu-4-VIm) have been synthesized and polymerized. In 28.5% ethanol-water, poly(1-alkyl-5-vinylimidazoles)proved to be efficient catalysts for the hydrolysis of various 3-nitro-4-acyloxybenzoic acids (Sn-, where n denotes the acyl chain length). Order of magnitude rate enhancements, as compared to the model compound, 1,5-dimethylimidazole (1,5-DMIm) were observed in the poly(1-alkyl-5-vinylimidazole)-catalyzed solvolysis of S12- and S18-. Poly(1-Me-5-VIm) catalyzes the hydrolysis of S18-88 times faster than does 1,5-DMIm. The poly(1-Me-5-VIm)-catalyzed hydrolysis of S18- in ethanol-water was analyzed in terms of a simple Michaelis-Menten type mechanism. Vmax and Km were determined to be 40.2 X 10(-7) M min-1 and 2.20 X 10(-5) M, respectively.  相似文献   

4.
The effect of monomer micellization on the polymerization was studied from the standpoint of stereochemistry in the polymerization. Quaternary salts (CnBr) of dimethylaminoethyl methacrylate with n-alkyl bromide having N (=4, 8 and 12) carbon atoms were polymerized with radical initiators in isotropic and anisotropic media and the resulting polymers were converted to poly (methyl methacrylate) (PMMA) to determine their tacticity. Tacticities of poly (C12Br)s were little affected by initiators and solvents used for their preparations. There was little dependence of the tacticities on alkyl chain length (N) for poly (CnBr)s prepared in water and dimethylformamide (DMF). Most of polymers produced here conformed to Bernoullian propagation statistics and a definite difference was not found in the tacticities between the polymers prepared in isotropic and anisotropic media. From the results obtained here it was deduced that the micellar aggregation has little influence upon the stereochemistry in the polymerization of the quaternary monomers. © 1994 John Wiley & Sons, Inc.  相似文献   

5.
Polyacrylamides possessing an amino group at the terminus of the branch chain as the potential site for amino acid and/or nucleic acid base grafting have been prepared. This type of polyacrylamide would provide a substantial spacing distance between the polymer main chain and pendant groups. Poly(2-amino-2-methylpropyl)acrylamide (PDMPA) and optically active poly(2-amino-2-methylbutyl)acrylamide (PDMBA) were characterized using vapor phase osmometry (VPO), gel permeation chromatography (GPC), and dilute solution viscometry. In addition, copolymers of poly(2-amino-2-methylpropyl)acrylamide with N-vinylpyrrolidinone, N-vinylimidazole, and H(5)-vinylimidazole, were prepared.  相似文献   

6.
Unsaturated macromolecular carboxybetaines were obtained by reaction of poly(4-vinylpyridine) and poly(N-vinylimidazole) with propiolic acid. A kinetic model was presented for 4-methylpyridine. It consists of three coupled reactions: neutralization, addition which involves two molecules of acid and leads to a cation–anion pair structure, where the cation results from the addition of the amine nitrogen to the triple bond of acid, and an equilibrium reaction between the ion-pair structure and the betaine structure. The addition rate was found to be higher for poly(4-vinylpyridine) than for poly(N-vinylimidazole); it was also higher in water than in a water–methanol mixture. The reaction with acetylenedicarboxylic acid was carried out on poly(N-vinylimidazole), but the transformed units showed the structure that results from propiolic acid. The betaine products from 4-methylpyridine did not polymerize by radical initiation. The polymeric products show characteristics of photocrosslinking polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1615–1623, 1998  相似文献   

7.
The stereoregularity of poly(methyl acrylate) and poly(methyl acrylate-αd) was determined from the NMR spectra. A method of quantitative determination of stereoregularity of poly(methyl acrylate) proposed in this paper is based on the fact that in the 100 Mc./sec. NMR spectrum the absorption peaks due to methylene protons in syndiotactic configurations overlap absorptions due to only one of two methylene protons in isotactic configurations. The stereostructure of poly(methy1 acrylates) polymerized with anionic catalysts such as Grignard reagents, n-butyllithium, and LiAlH4 is generally richer in isotactic diads than in syndiotactic diads. For example, poly(methyl acrylate) polymerized with phenylmagnesium bromide as catalyst at ?20°C. consists of 99% isotactic and 1% syndiotactic diads. In radical polymerization, the isotacticity of poly(methyl acrylate) is independent of polymerization temperature. Poly(methyl acrylates) polymerized with a Ziegler-Natta catalyst consisting of Al(C2H5)2Cl and VCl4 have configurations similar to those polymerized by radical initiators. The stereoregularity of poly(methyl acrylate-α-d) resembled that of poly(methyl acrylate) polymerized under the same conditions.  相似文献   

8.
The 3‐ and 4‐aminophenylacetylenes protected by t‐butoxycarbonyl (t‐Boc) and 9‐fluorenylmethoxycarbonyl (Fmoc) groups ( 3a – 6a ) were synthesized and polymerized using [(nbd)RhCl]2 ( 1 ) and [(nbd)Rh+‐η6‐PhB?Ph3] ( 2 ) catalysts. The t‐Boc‐containing polymers [poly( 3a ) and poly( 4a )] were obtained in high yield (82–91%). Among the Fmoc‐protected monomers, the para‐derivative polymerized well [poly( 6a ); yield = 85–94%], whereas its meta‐substituted analogue did not afford high molecular weight polymer in good yield [poly( 5a ); yield = 10–15%]. The use of KN(SiMe3)2 as a cocatalyst in conjunction with 1 led to a dramatic increase in the molecular weight of the polymers. The acid‐ and base‐catalyzed removal of the t‐Boc and the Fmoc groups, respectively, generated primary amine‐containing polymers [poly( 3b )–poly( 6b )] which cannot be obtained directly by the polymerization of the corresponding monomers. The solubility characteristics of the polymers bearing protected amino groups were quite different from those of the unprotected ones, the former being soluble in polar solvents, whereas the latter displayed poor solubility even in polar protic or highly polar aprotic solvents. The attempts to accomplish the free‐standing membrane fabrication by solution casting were successful only for poly( 3a ), and an augmentation in the gas permeability and CO2/N2 permselectivity was discerned in comparison with the unsubstituted poly(phenylacetylene) and poly(mt‐butyldimethylsiloxyphenylacetylene). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1853–1863, 2009  相似文献   

9.
Functional poly(ethylene oxide) stars were prepared by free‐radical copolymerization of poly(ethylene oxide) macromonomers with divinylbenzene in water. The poly(ethylene oxide) arm was prepared by anionic polymerization using 2‐[2‐(N,N‐dimethylamino)ethoxy]ethanol potassium alkoxide as the initiator. These functional stars were converted into peripherally charged stars by quaternization of the peripheral tertiary amino groups with methyl iodide.  相似文献   

10.
Water-soluble copolymers containing imidazole and N-alkylated imidazole pendant groups have been synthesized in order to investigate the hydrophobic interactions between polymeric catalysts and long alkyl chain ester substrates. Copoly[1-methyl-4-vinyl-imidazole/4(5)-vinylimidazole],copoly[1-methyl-5-vinylimidazole/4(5)-vinylimidazole], copoly[1-ethyl-5-vinylimidazole/4-(5)-vinyl-imidazole] and copoly[1-propyl-5-vinylimidazole/4(5)-vinylimidazole] were synthesized and their catalytic activity toward 3-nitro-4-acyloxybenzoic acid substrates (Sn?) was determined in 28.5% ethanol–water and in water and compared with that of the mixtures of homopolymers. Hydrophobic interactions were important for rate enhancement of the hydrolysis of long-chain ester substrates compared to that of short-chain ester substrates. The copolymers catalyzed the hydrolysis of 3-nitro-4-dodecanoyloxy-benzoic acid (S12?) about two times faster than the mixtures at pH 7.11 in 28.5% ethanol–water. The hydrolysis of S12? by the copolymers was about five times faster in water than 28.5% ethanol–water.  相似文献   

11.
2-Hydroxy-4-methacryloyloxybenzaldehyde (2H4MBA), prepared from methacryloyl chloride and 2,4-dihydroxybenzaldehyde, was polymerized in methyl ethyl ketone at 70°C using benzoyl peroxide as a free radical initiator. Polychelates were obtained from N,N-dimethylformamide solutions of poly(2H4MBA) on addition of aqueous solutions of Cu(II)/Ni(II) ions. The polymers and polychelates were characterized by elemental analyses and spectral studies. The IR spectra of these polychelates suggest that metals are coordinated through the oxygen of the aldehyde group and oxygen of the phenolic—OH group. The electronic spectra, EPR, and magnetic moments of polychelates showed an octahedral and square planar structure for poly(2H4MBA)-Ni(II) and poly(2H4MBA)-Cu(II) complexes, respectively. X-ray diffraction studies reveal that the polychelates are highly crystalline. The thermal properties of polymer-metal complexes and their catalytic activity are discussed. © 1996 John Wiley & Sons, Inc.  相似文献   

12.
甲壳型液晶高分子是我国科学家最早设计和合成、受到国际学术界广泛关注的一类新型液晶高分子[1~ 6 ] .迄今已合成出 1 0个系列 1 0 0多种甲壳型液晶高分子 ,其中多数以乙烯基氢醌 [7] 、乙烯基对苯二胺 [8] 、乙烯基对苯二甲酸 [9] 和 2 -羟基 - 5-氨基苯乙烯 [10 ] 为关键中间体 .液晶核由 3个苯环以— COO—或— CONH—连接而成 .由于— COO—和— CONH—易与阳离子和阴离子相互作用 ,故已报道的甲壳型液晶高分子都是由自由基聚合反应制得 ,而很难用离子型聚合反应合成 .本文设计合成了一类未见文献报道的小分子液晶化合物 ,由此…  相似文献   

13.
以1-乙烯咪唑和1,4-对二氯苄为原料, 通过自由基聚合和季铵化交联反应, 制得了一种新型聚合离子液体吸附剂——聚乙烯基苄基咪唑氯(P[VBnim]Cl), 并用元素分析、 凝胶渗透色谱、 红外光谱、 扫描电子显微镜、 物理吸附分析仪及热重分析等方法对其组成、 结构、 颗粒形貌、 比表面积、 孔结构及热稳定性进行了表征. 结果表明, P[VBnim]Cl 结构中对二氯苄与乙烯咪唑的摩尔比约为1∶3; 产物为米黄色蓬松粉末, 易吸水, 其初始颗粒直径为50~80 nm, 比表面积为13.86 m2/g, 平均孔径9.94 nm, 属于介孔结构材料, 初始热分解温度为274 ℃, 具有较好的热稳定性. 同时, P[VBnim]Cl对中低温煤焦油模型油中的苯酚具有优异的吸附性能, 其吸附能力是活性炭的2~10倍, 该吸附剂用乙酸乙酯再生后, 吸附效果仍然较好, 可以循环使用.  相似文献   

14.
A novel optically active phenylacetylene derivative, N‐(tert‐butoxycarbonyl)‐4‐ethynyl‐L ‐phenylalanine methyl ester ( 1 ), was synthesized from L ‐tyrosine and polymerized with a rhodium catalyst. The corresponding polymer [poly( 1 )] with a moderate molecular weight was obtained in a high yield. The alkaline hydrolysis of poly( 1 ) gave poly[N‐(tert‐butoxycarbonyl)‐4‐ethynyl‐L ‐phenylalanine] [poly( 2 )] carrying free carboxy groups. Polarimetric, CD, and UV–vis spectroscopy analyses revealed that poly( 1 ) took a predominantly one‐handed helical structure in MeOH and toluene, and poly( 2 ) took a helical structure in MeOH. The secondary structures of poly( 1 ) and poly( 2 ) could be tuned with heat and solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1691–1698, 2007  相似文献   

15.
In the previous paper, some ω-(1-imidazolyl) and ω-[4(5)-imidazolyl]alkanoic acids were synthesized and grafted onto poly(vinylamine). These water soluble catalysts of varying apolarity contain both hydrophobic and electrostatic binding sites for neutral and charged substrates. The influence of side chain length, percent graft, and the substitution in the imidazole ring are described. The grafts possessing the longer side chains and lesser apolar weight were more efficient catalysts than the grafts containing numerous short side chains and greater apolar weight. These grafts exhibited slower rates than poly[4(5)-vinylimidazole].  相似文献   

16.
Phenylacetylene (PA) derivatives having two polar groups (ester, 2a – d ; amide, 4) or one cyclic polar group (imide, 5a – c ) were polymerized using (nbd)Rh+[(η6‐C6H5)B?(C6H5)3] catalyst to afford high molecular weight polymers (~1 × 106 – 4 × 106). The hydrolysis of ester‐containing poly(PA), poly( 2a) , provided poly(3,4‐dicarboxyPA) [poly ( 3 )], which could not be obtained directly by the polymerization of the corresponding monomer. The solubility properties of the present polymers were different from those of poly(PA) having no polar group; that is, poly( 2a )–poly( 2d ) dissolved in ethyl acetate and poly( 4 ) dissolved in N,N‐dimethylformamide, while poly(PA) was insoluble in such solvents. Ester‐group‐containing polymers [poly( 2a )–poly( 2d )] afforded free‐standing membranes by casting from THF solutions. The membrane of poly( 2a ) showed high carbon dioxide permselectivity against nitrogen (PCO2/PN2 = 62). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5943–5953, 2006  相似文献   

17.
The Cu(II) complexes of copolymers having pendant sulfide and imidazolyl groups were prepared by a free radical copolymerization of ethylvinylsulfide with vinylimidazole, and their properties and function were studied spectrophotometrically in comparison with those of poly[4(5)-vinylimidazole]. The complexes were found to be effective as catalysts for the oxidation of hydroquinone. Visible and ESR spectra of the Cu(II)-copolymer complexes were similar to those of the Cu(II)-homopolymer complexes, while the catalytic activity for the oxidation was different between these complex systems. A rapid reaction followed by a slow reaction, particularly at high ethylvinylsulfide content in the copolymers, was observed in the Cu(II)-copolymer complex systems, but a continuous reaction proportional to the reaction time was observed in the Cu(II)-homopolymer complex systems. The reoxidation rate of Cu(I) to Cu(II) complex, which was little affected by the concentration of imidazolyl group, decreased with a rise of the ethylvinylsulfide content in the copolymer. It was suggested that the sulfur atom of the sulfide group was weakly coordinated to Cu(II) but strongly to Cu(I), and an electron transfer reaction from substrate to the Cu(II) complex was increased, while reoxidation reaction of the Cu(I) complex was decreased in the copolymer complex systems.  相似文献   

18.
Preparations of poly[(3-hydroxypropyl)oxirane] and poly[(4-hydroxybutyl)oxirane] are described. Three routes to poly[(3-hydroxypropyl)oxirane] are discussed, each of which involves the methanolysis of a polymeric ester. (3-Acetoxypropyl)oxirane, [3-(m-chlorobenzoyloxy)propyl]oxirane, and (3-chloropropyl)oxirane were polymerized using the AIEt3/H2O/AcAc initiator system. Poly[(3-acetoxypropyl)oxirane] and poly{[3-(m-chlorobenzoyloxy)propyl]oxirane} were converted directly to poly[(3-hydroxypropyl)oxirane] by methanolysis, the former under either acidic or basic conditions only. Poly[(3-chloropropyl)oxirane] was first converted to poly[(3-benzoyloxypropyl)oxirane] by treatment with tetrabutylammonium benzoate; subsequent basic methanolysis then afforded poly[(3-hydroxypropyl)oxirane]. Poly[(3-hydroxypropyl)oxirane] is a colorless elastomer which can be cast into tough, clear films from water or methanol. Poly[(4-hydroxybutyl)oxirane] was prepared from poly[(4-chlorobutyl)oxirane] by benzoyloxylation and subsequent methanolysis. Poly[(4-hydroxybutyl)oxirane] is insoluble in water, but is hydrophilic and can be cast into tough films from methanol or dimethylsulfoxide.  相似文献   

19.
Polymers containing silatrane units were prepared by the free radical polymerization of methacryloylsilatrane (MPS), and their conductivities were evaluated. We confirmed that MPS can be polymerized without excessive decomposition of the silatrane units by the radical polymerization initiated by azobisisobutyronitrile. The chemical structure of the polymerized MPS (pMPS) was characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectroscopy. The pMPS formed a homogeneous complex with lithium trifluoromethyl sulfonate (LiOTf), although the obtained pMPS/LiOTf complex did not show conductivity. The negligible conductivity was caused by the high glass transition temperature (Tg) of the pMPS matrix, which exceeded 70°C. The pMPS was subsequently utilized as a salt‐dissociation enhancer for the poly(ethylene oxide)‐based polymer electrolyte. MPS was copolymerized with poly[methacryloyl oligo(ethylene oxide)] (pMEO) by free radical polymerization. When the pMEO incorporated a small amount of MPS units (i.e. lower than 15 mol%), the elevation in Tg was not observed, and the conductivity markedly improved. Among the series of copolymers and when compared with pristine pMEO, the copolymer containing 6.3% of MPS units had the maximum conductivity (3.1 × 10?4 S cm?1 at 80°C). The Vogel–Fulcher–Tammann fitting parameters showed that the conductivity was improved by the increase in the number of carrier ions. The enhancement in salt dissociation was presumably due to the homogeneous incorporation of polar MPS units. However, when the MPS unit content exceeded 15 mol%, the conductivity was lowered because of the increase in Tg. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

20.
A polystyrene with pendant calix[4]pyrroles was prepared via ‘click reaction’ strategy. First, a poly(styrene-co-chloromethylstyrene) with approximately 12% of chloro groups was prepared by conventional free radical polymerisation. The chloro groups were then converted to azido groups using NaN3 in N,N-dimethylformamide. An alkyne-functionalised calix[4]pyrrole was then coupled to the azido-functionalised polystyrene by click chemistry with high efficiency. The resulting polystyrene with pendant calix[4]pyrroles was used to extract fluoride and chloride anions (as their tetrabutylammonium salts) from their aqueous solutions to organic media.  相似文献   

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