Alkali cation binding of polymers with different sized crown ethers and photodimerizable units

The polymers which have different sized crown ethers as alkali cation binding sites and photodimerizable cinnamoyl units were prepared by the cationic copolymerization of corresponding monomers. The crown–cation complexation ratio (1:1 or 2:1) was investigated by measuring quantum yields ? of the photodimerization of the crown-connected cinnamoyl units in the presence of alkali metal chlorides and also by measuring the shift of λ_max of alkali metal picrates in THF on addition of the crown polymers. A significant 1:2 complex formation of alkali cations with two different sized crown ether units in the side chain of the polymers was confirmed. The alkali metal cation binding ability and selectivity of the polymers, which were studied by a method of picrate salts extraction, were markedly different from those expected from the combination of polymers of same ring-size crown ether units. When irradiated with ultraviolet (UV) light, the cinnamic acid ester groups of the polymers caused dimerization even in dilute solutions. The cation binding ability of the polymers was largely enhanced by the photodimerization of the cinnamoyl moieties with suitable template cations.     

Study of photopolymer. XVII. Synthesis of novel photosensitive polymers with pendant photosensitive group and photosensitizer groups

Novel photosensitive polymers with pendant photosensitive group, such as cinnamic ester, and photosensitizer groups, such as N-carbamoyl-p-nitroaniline and N-carbamoly-4-nitro-1-naphthylamine, were synthesized from radical copolymerizations of (2-cinnamoyloxy)ethylmethacrylate with photosensitizer monomers, such as p-nitrophenylmethacrylamide and 4-nitro-1-na-phthylmethacrylamide, by using asobisisobutyronitrile (AIBN) in benzene and from the copolymerizations of (2-hydroxy)ethylmethacrylate or (2-hydroxy)ethylacrylate with photosensitizer monomers by using AIBN in DMF. This procedure was followed by condensation reactions of the copolymers with cinnamoyl chloride with pyridine as HCL acceptor in the same reaction flask. The photoreactivities of the polymers obtained were influenced by the concentration of photosensitive group and photosensitizer groups and their ratio in the polymer matrix. In addition, the photosensitivity of cinnamic ester groups attached to a soft polymer segment was higher than that of cinnamic ester group attached to a hard polymer segment when these polymers had the same pendant N-carbamoyl-p-nitroaniline group as photosensitizer. Furthermore, the spacer length between the polymer chain and photosensitizer group was important for increasing the photoreactivity of the photosensitive group in the polymers with pendant cinnamic ester and N-carbamoyl-p-nitroaniline groups.     

Cation binding properties of photodimerizable polymers bearing benzodiglyme units

The polymers which have glyme units as alkali cation binding sites and photodimerizable cinnamoyl units were prepared by the radical polymerization of corresponding monomers. The alkali cation binding ability and selectivity of the polymers, which were studied by a method of picrate salts extraction, were strongly dependent on the length of glyme chains. When irradiated with ultraviolet light, the cinnamoyl groups caused dimerization in dilute solutions. Although the photodimerization of the polymers with relatively short glyme chains enhanced their cation binding ability, the photodimerization of the polymers bearing long glyme chains reduced their cation binding ability. The use of alkali metal cations as templates emphasized the effect of photodimerization on the cation binding properties. The effect of alkali metal cations on the quantum yields of the photodimerization of the polymers showed that two or more benzodiglyme units took part in the binding of one cation. The polymers bearing benzodiglymes, crown ethers, and cinnamoyl moieties were also prepared by the radical copolymerization of the corresponding monomers. It was found that the crown ether units of the copolymers predominantly participated in the cation binding. The photodimerization of the copolymers with suitable alkali metal cations as templates strongly enhanced their cation binding ability.     

Amphiphilic copolymers with increased affinity for substrates

The copolymers of methyl quaternized 2-dimethylaminoethyl acrylate and styrene, 2-vinyl naphthalene, acrylic acid iso-octyl ester, or acrylic acid n-butyl ester have been prepared. Studies were made of the binding of a “binding probe,” methyl orange, by the copolymers in aqueous solution. The first binding constants and the thermodynamic parameters in the course of the binding were evaluated. Furthermore, the intensity of fluorescence of a hydrophobic fluorescent probe, 2-p-toluidinylnaphthalene-6-sulfonate, in the presence of these polymers was investigated. In addition, the fluorescence spectra of monomer and excimer emissions of the polymers with aromatic residues were measured. The excimer/monomer fluorescence intensity ratio was studied in the presence of various additives such as methyl orange, urea, methanol, and NaCl to gain an insight into the nature of microdomains in the polymer. The nature and phenomena of dye binding and hydrophobic fluorescent probe binding with the polymers are discussed. © 1993 John Wiley & Sons, Inc.     

Polycondensation of pyridine-2,6-dicarboxylic acid with some di- and tetraamino compounds

Pyridine-2,6-dicarboxylic acid phenyl ester was condensed with 3,3′-diaminobenzidine and 3,3′,4,4′-tetraaminodiphenyl ether. Polyamides were also synthesized by condensation of the above ester with p-phenylenediamine, benzidine, 4,4′-diaminodiphenyl sulfide and 4,4′-diaminodiphenyl sulfone. These amides had higher inherent viscosities and greater thermal stability than was reported before. Model compounds of imidazoles were prepared by condensation of the same ester with o-phenylenediamine and 2,3-diaminopyridine and of polyamides by condensation with aniline and 2-aminopyridine. In the case of the polyimidazole, the completely closed ring of imidazole did not form. The ultraviolet spectra of model compounds were compared with those of the polymers. The thermogravimetric curves show that the polymers are stable up to more than 400°C under argon atmosphere. All polymers were insoluble in most organic and inorganic solvents. They dissolved only partially in DMSO and DMF. Inherent viscosity was measured for the soluble polymer fraction.     

含1,3-亚丙基冠醚的合成

为了进一步研究亚丙基冠醚的络合行为,合成了三种含1,3-亚丙基冠醚,即2,3-苯并-1,4,7,11-四氧-环十三-2-烯(苯并-13-冠-4)(1)、2,3-苯并-1,4,8,11,14-五氧-环十七-2-烯(苯并-17-冠-5)(2)、2,3-苯并-1,4,7,10,14,17-六氧-环十九-2-烯(苯并-19-冠-6)(3)。通过元素分析、红外光谱、质谱、核磁共振谱和 X-衍射晶体结构分析,确证了它们的结构。     

A tracer study of the hydrolysis of methyl methacrylate and methyl acrylate units in homopolymers and copolymers

Homopolymers and copolymers were prepared from methyl methacrylate, methyl acrylate, and styrene by radical reactions at 60°C. Monomers suitably labeled with carbon-14 were used so that it was possible to monitor the hydrolysis of ester groups in the polymers during treatment under alkaline conditions. It was found that methyl acrylate units were hydrolyzed completely whatever their environment in a polymer chain. Under the same conditions only about 9% of the ester groups in a homopolymer of methyl methacrylate reacted; the proportion was increased by the introduction of comonomer units into the polymer chain. For copolymers of methyl methacrylate with methyl acrylate the extent of reaction may be correlated with the lengths of the sequences of methyl methacrylate units.     

Interaction of inorganic salts with polar polymers. II. Infrared studies of polymer–inorganic nitrate systems

Certain inorganic nitrate salts are quite soluble in the polymers studied, namely, cellulose acetate, poly(vinyl acetate), poly(vinyl alcohol), poly(methyl methacrylate), and poly(methyl acrylate). Large effects upon the glass-transition temperature were observed in those systems where the transition could be readily measured. Large shifts in the infrared spectra of both the inorganic nitrate salts and in the polymer carbonyl and ester ether frequencies have been observed. These observations have been interpreted in terms of complex formation between these polymers and salts in the solid state. The proposed structure of the complex explains the nature of the infrared shifts both for the nitrate salts and the polymers as well as explaining the concentration effects observed. Effects of the solvating environment upon the salt and polymer spectra remain unexplained. The large glass-transition effects are a result of the degree of solubility of the salts in the polymers and the interactions between them. However, the reason why, in some cases, the change in the transition temperature as a function of concentration goes through a maximum is unclear.     

Four-center type photopolymerization in the solid state. III. Polymerization of phenylene diacrylic acid and its derivatives

The solid-state photopolymerization of phenylene diacrylic acid (PDA) and its derivatives was studied as an application of solid-state photodimerization of cinnamic acid to photopolymerization of corresponding bifunctional molecule which has two cinnamic units in a single molecule. p- and m-PDA, and their esters and amides were prepared and investigated with respect to their photopolymerizability. Many of them have been found to polymerize into linear high polymers with the cyclobutane rings in the main chain on irradiation by ultraviolet or visible light. The polymerization process, the structure of the polymers, and their general properties were investigated in several ways. All the polymers are very similar to poly-2,5-distyrylpyrazine and poly-1,4-bis(β-pyridyl-2-vinyl) benzene with respect to their polymerization behavior, polymer structure, and some polymer properties: these polymers are soluble in a limited number of solvents, they have a high melting point and an extremely high crystallinity. On the basis of chemical behavior of poly-PDA and its phenyl ester the possible steric configurations of these polymers are discussed. It is demonstrated for the PDA series that solid-state dimerization can be generally extended to solid-state photopolymerization of the compound having two dimerizable units in a single molecule, although the crystal structure renders polymerization impossible in certain cases.     

Molecular design of crown ethers .18.~1 Cationextractability and selectivities of selena-13- to 14-crown-4

Three selena-crown-4 derivatives have been prepared and their cation binding abilities and selectivities with alkali and heavy metal ions have been evaluated by solvent extraction of aqueous metal picrates to show the highest Ag extractability for novel benzo-selena-14-crown-4 (2,3-benzo-7,12-diselena-1, 4-dioxacyclotetradecane-2-ene) over any other crown ethers.     

Novel synthesis of photocrosslinkable polymers

A new preparative route to photocrosslinkable polymers in which the polymers are produced directly from the polymerization of vinyl monomers having photocrosslinkable groups has been investigated. The photosensitive resins thus produced have higher sensitivity and resolution than conventional photosensitive resins. The monomers were synthesized from the esterification of vinylphenols or vinyl β-chloroethyl ether with cinnamic acid, β-styrylacrylic acid, and their homologs, and from the etherification of vinyl β-chloroethyl ether with hydroxychalcones. Homopolymerizations of these monomers and their copolymerizations with other comonomers were investigated with the use of both radical and ionic initiators. It is shown that radical polymerization of the monomers gave soluble polymers only at low conversion. Anionic initiators did not initiate polymerization. Cationic polymerization imparted soluble polymers in high yield, except for the monomers bearing cyano groups, which generally gave insoluble polymers. Infrared and NMR spectroscopic investigation of the cationically obtained soluble polymers and comparative investigation by cationic polymerization of model compounds indicated that polymerization of the monomers proceeds through the vinyl double bond without affecting the photosensitive unsaturated bond. Thus, linear photocrosslinkable polymers with an intact photoreactive group may be produced by cationic polymerization. In general, these polymers have uniform structure and modifiable physical properties depending on the monomer used. The polymer thus obtained from β-vinyloxyethyl cinnamate has been shown to have excellent properties for use as a photo-resist.     

Solvent-free MALDI investigation of the cationization of linear polyethers with alkali metals

The MALDI technique with solvent-free sample preparation has been applied to evaluate relative gas-phase affinities of polyether chain polymers with alkali metal cations. The study is performed on poly(ethylene glycol) and poly(propylene glycol) polymers of different lengths (PEG600, PEG1000, PPG425, PPG750) and the alkali metal cations Li(+), Na(+), K(+), and Cs(+). The experiments show that the lattice energy of the alkali metal salts employed as cation precursors can have a strong influence on the outcome of conventional MALDI measurements. With the solvent-free method, these crystal binding effects can be made negligible by combining in the same sample alkali metal salts with different counterions. The recorded MALDI spectra show that the polyether-cation aggregation efficiencies decrease systematically with growing cation size. This cation size selectivity is considerably enhanced for the polymers with the shorter chains, which can be attributed to the reduced ability of the polymer to build a coordination shell around the larger cations. The steric effects introduced by the side CH3 group of propylene glycol with respect to ethylene glycol also enhance the preference for cationization of the polymer by the smaller cations. These observations correct some qualitative trends derived from previous studies, which did not account for lattice energy effects of the cation precursors.     

Synthesis of hyperbranched degradable polymers by atom transfer radical (Co)polymerization of inimers with ester or disulfide groups

Degradable hyperbranched polymers with multiple alkyl halide chain ends were synthesized by the atom transfer radical polymerization of inimers containing ester (2‐(2′‐bromopropionyloxy)ethyl acrylate) or disulfide (2‐(2′‐bromoisobutyryloxy)ethyl 2′′‐methacryloyloxyethyl disulfide) groups. Both the homo‐ and copolymerizations (with styrene in the former case and methyl methacrylate in the latter) were studied. The hyperbranched polymers derived from the ester‐type inimer were hydrolytically degradable under basic conditions, whereas those derived from the disulfide‐containing inimer could be efficiently degraded in the presence of reducing agents such as tributylphosphine. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

Synthesis of self‐photosensitizing polyesters containing donor–acceptor norbornadiene moieties and benzophenone groups and their photochemical reactions

The ring‐opening copolymerization of a glycidyl ester derivative having a benzophenone group and the donor–acceptor norbornadiene (D‐A NBD) dicarboxylic acid, 5‐(4‐methoxyphenyl)‐1,4,6,7,7‐pentamethyl‐2,5‐norbornadiene‐2,3‐dicarboxylic acid, monoglycidyl ester derivatives with D‐A NBD dicarboxylic anhydride using tetraphenylphosphonium bromide as a catalyst proceeded smoothly to give novel self‐photosensitizing NBD polymers in good yields. The molecular weight of these polyesters was about 4,000, and lower than that of analogous NBD polymers having no benzophenone group. All the synthesized NBD polymers isomerized smoothly to the corresponding quadricyclane (QC) polymers upon UV irradiation in tetrahydrofuran (THF) solution and in the film state. The rate of the photoisomerization of the D‐A NBD moieties in these polymers was higher than that of the D‐A NBD moieties in the polymer having no photosensitizing group. Furthermore, the rate of the photoisomerization of the D‐A NBD moieties in these polymers was also higher than that of the NBD polymer with low molecular weight photosensitizer in dilute solution. The photo‐irradiated polymers having QC moieties released thermal energies of 146–180 J/g. The D‐A NBD moieties contained in these NBD polymers possessed fair to good fatigue resistance. The degradation of the NBD moieties in these polymers was 15–30% after 50 repeated cycles of interconversion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2978–2988, 2007     

A2和B3单体重氮偶合反应制备超支化偶氮聚合物

利用A2/B3单体通过重氮偶合反应制备了超支化偶氮聚合物.利用核磁共振、红外光谱、紫外光谱和DSC热分析手段表征了聚合物的结构、光谱性能和玻璃化转变温度.合成的超支化偶氮聚合物具有很好的光响应性能,用488nm Ar+激光对超支化偶氮聚合物薄膜进行光加工,得到了规则的表面起伏光栅.     

Directed deposition of functional polymers onto porous substrates using metal salt inhibitors

This paper demonstrates the ability to control the location of polymer deposition onto porous substrates using vapor phase polymerization in combination with metal salt inhibitors. Functional polymers such as hydrophobic poly(1H,1H,2H,2H-perfluorodecyl acrylate), click-active poly(pentafluorophenyl methacrylate), and light-responsive poly(ortho-nitrobenzyl methacrylate) were patterned onto porous hydrophilic substrates using metal salts. A combinatorial screening approach was used to determine the effects of different transition metal salts and reaction parameters on the patterning process. It was found that CuCl(2) and Cu(NO(3))(2) were effective at uniformly inhibiting the deposition of all three polymers through the depth of the porous substrate and along the entire cross section. This study offers a new and convenient method to selectively deposit a wide variety of functional polymers onto porous materials and will enable the production of next-generation multifunctional paper-based microfluidic devices, polymeric photonic crystals, and filtration membranes.     

Cross‐linking photopolymerization of monoacrylate initiated by benzophenone

The chain‐end structure of the photopolymerized acrylate using benzophenone as an initiator was investigated as well as polymerization behavior. Dodecyl acrylate was used as a monomer in this study. Gelation occurred during ultraviolet (UV) irradiation, whereas a cross‐linker was not employed. Conversion‐time profile below gel point gave a linear first‐order plot suggesting that the steady‐state was held throughout polymerization. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectra of the resultant polymer indicated that most polymers had an acryloyl group at one of the chain‐ends, while some polymers had an acryloyl group at each chain‐end. The cross‐linking reaction leading to gelation would have been caused by the subsequent copolymerization of the residual monomer with the latter polymer having two acryloyl groups. Dissolved oxygen in the monomer solution influenced the polymer structure giving hydroxyl group at chain‐end. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1545–1553     

Study of photopolymer. XIX. Novel syntheses of the polymers with pendant ester and chloromethyl groups by addition reactions of the copolymer of glycidyl methacrylate with acid chlorides

Polymer with pendant cinnamic ester and chloromethyl groups was synthesized by the addition reaction of poly(glycidyl methacrylate–co–methyl methacrylate) (PGMA) with cinnamoyl chloride. Also, polymers with pendant benzoic esters and chloromethyl groups were synthesized by reaction of PGMA with the corresponding benzoyl chlorides. Furthermore, polymers with cinnamic or benzoic esters and alkylazide groups were prepared by the substitution reaction of the obtained polymers with sodium azide.     

冠醚配合物热力学性质的研究 X: 用NMR研究15-冠-5-衍生物与钠离子的配位反应

用^2^3Na NMR研究了15-冠-5(15C5), 2,3-苯并-15-冠-5(B-15C5), 2,3-苯并-6-甲基-15-冠-5(BCl-15C5), 2,3-苯并-8,12-二甲基-15-冠-5(BC2-15C5)在丙酮中与Na^+的配位反应, 由此探索甲基的影响, 实验结果表明, 当在金属盐溶液中加入冠醚, 配体为15C5时, 体系表观化学位移移至低场, 配体为B-15C5, BC1-15C5, BC2-15C5时, 体系在表观化学位移移至高场, 后者与苯并-18-冠-6及其甲基衍生物不同, 这是由于苯环在空间排布不同所致, 用Newton-Raphson法和描坑法(Pit-mapping)拟合实验数据, 发现BC1-15C5和BC2-15C5除形成NaL^+和NaL2^+外还有不稳定的Na3L2^3^+形成。本文对形成过程和生成NaL^+反应的平衡常数lgK11与甲基数的关系亦作了讨论, lgK11与甲基数目n近似成直线关系, 可用下式表示: lgK11=3.50-0.80n, n=0,1,2。     

SYNTHESIS OF POLYMERS WITH PHOSPHONIUM END GROUPS BY ATOM TRANSFER RADICAL POLYMERIZATION

The end groups of polymers prepared by atom transfer radical polymerization (ATRP), are well-defined and determined by the initiator used, at least one of them is a halogen end group. The halogen end groups can be transformed to other functionalities such as phosphonium salts as demonstrated in this paper. Kinetic studies with the compounds 1-phenylethyl bromide and methyl 2-bromopropionate, models for the polystyrene and polyacrylate chain ends respectively, indicated that bromine end groups were readily transformed to phosphonium end groups upon the addition of phosphines. Stability tests with the obtained phosphonium salts showed that 1-phenylethyl trialkylphosphonium bromide was stable, even at higher temperatures and in the presence of free phosphines. The stability of the propionate analogue was limited due to the presence of the ester group in the molecule. Polystyrene and poly(methyl acrylate) phosphonium salts were synthesized and the presence of the end groups was demonstrated by ¹H NMR and ESI-MS or MALDI-TOFMS.