用双官能团引发剂进行的原子转移自由基嵌段和无规共聚

原子转移自由基聚合［１］,可同时适用于非极性单体和极性单体,如苯乙烯、二烯烃类和（甲基）丙烯酸酯、丙烯腈类单体［１～３］,这是传统的活性聚合如阴离子聚合和基团转移聚合所不及的;可以用于制备包括无规、嵌段、星形与高支化物在内的诸多结构清晰的高分子化合物...     

含五苯基吡咯侧基聚丙烯酸酯的制备及其聚集诱导发光增强性能

设计合成了具有聚集诱导发光增强活性(AEE)的含五苯基吡咯的甲基丙烯酸酯单体M-PPP,并通过自由基聚合制备了系列均聚物及不同五苯基吡咯侧基含量的聚甲基丙烯酸酯共聚物.所制备的均聚物P与共聚物CP在THF/H_2O体系中均具有AEE特性,在水含量大于20%时荧光开始增加,大于80%时荧光快速增加,95%时相对荧光强度达到最大;单体M-PPP则在水含量低于70%时荧光强度略有降低,随后迅速增加,95%后荧光强度下降.五苯基吡咯侧基含量较高的共聚物表现出更好的AEE特性.进一步的研究发现,共聚物CP在THF/H_2O混合溶液中能够对赖氨酸产生荧光点亮型响应.     

Controlled synthesis and association behavior of graft Pluronic in aqueous solutions

Poly(vinyl pyrrolidone) (PVP) was grafted onto Pluronic F127 (PEO-PPO-PEO) to produce novel amphiphilic PVP-g-F127 graft copolymers. A controlled synthesis method was used to graft PVP onto different parts of F127. Two types of graft polymers were obtained: one has PVP grafted onto the PEO part of F127 and the other has PVP grafted onto the PPO part of F127. The association behavior of the two modified polymers was examined using differential scanning calorimetry, surface tension measurements, and dynamic light scattering.     

Grafting and Degradation Reactions at the Synthesis of Interpenetrating Polymer Networks in Situ from Polyethylene and Butyl Methacrylate

Abstract

The grafting and degradation reactions accompanying the synthesis of interpenetrating polymer networks (IPN) in situ consisting of polyethylene (PE) and poly(butyl methacrylate) (PBMA) were investigated under model conditions. After polymerization at 110°C it was found that the 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane (Luperox-101) had a destructive effect on the PBMA network formed provided the temperature was raised to 160°C. Simultaneously in this reaction stage, further linkage of the PBMA chains with PE originates from a recombination of macroradicals from both polymers. In the thermally initiated polymerization of BMA (in the absence of peroxide), PE is grafted with BMA but no crosslinking of PE takes place. If a mixture of initiators (2,2′ - azo-bis-isobutyronitrile and Luperox-101) was used, a retardation of PE grafting with BMA was observed. A considerable degree of PE crosslinking and grafting of PBMA onto a PE network was achieved if both polymers were mixed with 3 mass % of Luperox-101.     

Positive working resists sensitive to visible light,I: poly(tert-butyl and 2-phenylpropyl-2 methacrylates) sensitized with diphenyliodonium salt — p-aminobenzylidene dye system

Visible-light-sensitive positive type resists have been developed. The chemistry to form images is based on the cleavage of side chain ester bonds of poly(methacrylates) catalyzed by an acid which is generated on sensitized photodecomposition of a diphenyliodonium (DPI) salt. Homopolymers and copolymers of tert-butyl methacrylate (BMA) and 2-phenylpropyl-2 methacrylate (PPMA) were used as acid labile polymers. Exposure of thin films of the poly(methacrylates) containing DPI salt and p-dimethylaminobenzylidene derivatives to an Ar laser beam emitting 488 nm light and subsequent heat treatment resulted in solubility alteration of the polymers, which became soluble in a protic solvent system. Considerable reduction of film thickness was observed after heating an image-wise exposed thin film of PPMA polymers. The minimum exposure energies of 488 nm light for the positive image formation were 60 mJ/cm² and 40 mJ/cm² for BMA and PPMA homopolymers, respectively.     

含碘聚甲基丙烯酸酯类X光显影材料的制备

由甲基丙烯酸正丁酯（BMA）与2-(2'-碘苯甲酰)-O-甲基丙烯酸乙酯(2-IEMA)自由基共聚制备了一种X光显影材料。1H NMR分析表明,该共聚物中2种结构单元之比与投料比吻合。GPC测得该共聚物的分子量随2-IEMA含量增加而降低。DSC分析表明,共聚物的玻璃化转变温度在22.3~28.0 ℃之间,与Fox方程计算值比较接近,而且随2-IEMA含量的增加而升高。TGA测得共聚物的分解温度为250 ℃,具有很好的热稳定性。力学性能测试结果表明,共聚物的拉伸强度随BMA含量的增加而增加,最大拉伸强度可达到7.46 MPa。X光显影性测试表明,该共聚物具有良好的显影性,显影效果随2-IEMA含量增加而增强。     

Modification and Application of Poly(Ethylene Terephethalate) Nonwoven Fiber Using Octadecyl Acrylate and Acrylic Acid as Oil Sorbers

Three series of crosslinked octadecyl acrylate and acrylic acid copolymers were prepared through suspension copolymerization based on acrylic acid content (10, 30, 50%wt. ratio). Divinyl benzene (DVB) was used as a crosslinker with different weight ratios (1, 4 and 10%). Isopropyl alcohol or dioctyl phthalate and methyl benzoate were used as two different reaction solvents in the presence of ABIN as initiator. The prepared crosslinked copolymers were characterized by SEM, TGA and FTIR spectroscopic analyses. The prepared polymers were coated onto poly(ethylene terephethalate) nonwoven fiber (NWPET). The effect of copolymerization feed composition, crosslinker wt% and reaction media or solvent on swelling properties of crosslinked polymers were studied through the oil absorption tests in toluene and 10% of diluted crude oil with toluene. It was noticed that the maximum swelling of crosslinked copolymers was increased from 30 to 100 g/g after grafting of copolymers onto NWPET.     

Copolymers of 2-hydroxyethyl methacrylate and alkyl methacrylates. I. Synthesis and characterization

Copolymerization of 2-hydroxyethyl methacrylate (HEMA) with ethyl methacrylate (EMA) and n-butyl methacrylate (BMA) was carried out in bulk at 70°C ± 1°C using 0.2% benzoyl peroxide as initiator in nitrogen atmosphere. Number average molecular weight (M _n) of the copolymers was determined by dynamic osmometry. Intrinsic viscosity [η] of HEMA-BMA copolymers was evaluated at 35°C in dimethyl formamide. These copolymers were also characterized by infrared spectroscopy and density measurements. Cohesive energy densities (CED) of these polymers were determined by observing their swelling behavior in different solvents. It was found that a decrease in alkyl methacrylate content resulted in an increase in the CED values of the copolymers.     

An enzyme-immobilization method for integration of biofunctions on a microchip using a water-soluble amphiphilic phospholipid polymer having a reacting group

A water-soluble phospholipid polymer having an active ester group in the side chain, poly[2-methacryloyloxyethyl phosphorylcholine (MPC)-co-n-butyl methacrylate (BMA)-co-p-nitrophenyloxycarbonyl polyethyleneglycol methacrylate (MEONP)(PMBN), was used for the immobilization of an enzyme on a plastic microchip. The MPC polymers with BMA units were adsorbed onto the poly(methyl methacrylate)(PMMA) microchip, and the active ester group in the MEONP unit reacted with the amino groups of the proteolytic enzyme, trypsin. Trypsin was immobilized on the sample reservoir, and catalyzed the hydrolysis of the fluorescently labeled ArgOEt to Arg. The consequent separation of product from the substrate, and their detection, were integrated on the microchip and this meant that all procedures from the enzymatic activity to product detection were completed in less than three minutes.     

仿细胞膜结构共聚物的合成及涂层性能

采用饥饿法将2-甲基丙烯酰氧乙基磷酰胆碱(MPC)分别与甲基丙烯酸十八烷基酯(SMA)、 甲基丙烯酸十二烷基酯(LMA)及甲基丙烯酸正丁酯(BMA)聚合, 通过改变投料比例和沉淀剂种类, 合成了一系列含磷酰胆碱基团的仿细胞膜结构的两亲性二元随机共聚物. ¹H NMR和元素分析结果表明, 合成的两亲性二元随机共聚物的组成与投料比相近. DSC结果表明, 聚合物具有较低的玻璃化转变温度. 表面张力及水的动态接触角(DCA)研究发现, 聚合物涂层表面具有明显的两亲性及表面结构易变性, 在空气中憎水基团在表面取向, 在水环境中亲水的磷酰胆碱基团则迁移取向到涂层表面形成仿细胞外层膜结构界面, 最终形成不溶于水的仿细胞膜结构涂层.     

Amphiphilic diblock,triblock, and star block copolymers by living radical polymerization: Synthesis and aggregation behavior

Copper(I)‐mediated living radical polymerization was used to synthesize amphiphilic block copolymers of poly(n‐butyl methacrylate) [P(n‐BMA)] and poly[(2‐dimethylamino)ethyl methacrylate] (PDMAEMA). Functionalized bromo P(n‐BMA) macroinitiators were prepared from monofunctional, difunctional, and trifunctional initiators: 2‐bromo‐2‐methylpropionic acid 4‐methoxyphenyl ester, 1,4‐(2′‐bromo‐2′‐methyl‐propionate)benzene, and 1,3,5‐(2′‐bromo‐2′‐methylpropionato)benzene. The living nature of the polymerizations involved was investigated in each case, leading to narrow‐polydispersity polymers for which the number‐average molecular weight increased fairly linearly with time with good first‐order kinetics in the monomer. These macroinitiators were subsequently used for the polymerization of (2‐dimethylamino)ethyl methacrylate to obtain well‐defined [P(n‐BMA)_x‐b‐PDMAEMA_y]_z diblock (15,900; polydispersity index = 1.60), triblock (23,200; polydispersity index = 1.24), and star block copolymers (50,700; polydispersity index = 1.46). Amphiphilic block copolymers contained between 60 and 80 mol % hydrophilic PDMAEMA blocks to solubilize them in water. The polymers were quaternized with methyl iodide to render them even more hydrophilic. The aggregation behavior of these copolymers was investigated with fluorescence spectroscopy and dynamic light scattering. For blocks of similar comonomer compositions, the apparent critical aggregation concentration (cac = 3.22–7.13 × 10^?3 g L^?1) and the aggregate size (ca. 65 nm) were both dependent on the copolymer architecture. However, for the same copolymer structure, increasing the hydrophilic PDMAEMA block length had little effect on the cac but resulted in a change in the aggregate size. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 439–450, 2002; DOI 10.1002/pola.10122     

Photolysis of copolymers of p-methoxyacrylophenone with p-biphenyl methacrylate and 2-naphthyl methacrylate

Copolymers of p-methoxyacrylophenone (PMeOAP) with 2-naphthyl methacrylate (2NMA) and p-biphenyl methacrylate (BMA) containing 0–4·2 wt % of 2NMA and 0–4·9 wt % of BMA were prepared. The photolysis of these copolymers under 366 nm irradiation in dilute ethyl benzoate solution at ambient temperature was studied viscometrically. Increasing content of triplet energy acceptors (2NMA and BMA) in copolymers caused decrease of quantum yields for main chain scissions. The same efficiency was observed for bound 2NMA and BMA, though naphthalene was about twice more efficient than biphenyl in intermolecular triplet energy transfer. The 25-times longer life-time of the excited triplet state of poly-p-methoxyacrylophenone (PPMeOAP) compared to polyacrylophenone does not lead to increase of intramolecular triplet energy transfer. According to Perrin's model of static quenching. the calculated radius of the quenching sphere in both copolymers of PMeOAP was about 16 A and in copolymers 1- and 2-vinylnaphthalene-acrylophenone about 13 A. The value obtained for low-molecular model compounds was about 10 A. Results indicate that there is probably no isothermic triplet energy transfer between identical p-methoxyacrylophenone chromophores.     

对氯甲基苯乙烯与丙烯腈、甲基丙烯酸酯类的自由基共聚研究

<正> 对氯甲基苯乙烯(p-CMS)是合成功能高分子的一个非常有用的起始单体,利用它的均聚以及与其它烯类单体的共聚反应,可制得含活性基团的高分子材料。但以往对该单体的聚合及共聚研究,较多的是以邻、间、对位氯甲基取代苯乙烯的混合物作为研究对象。本文采用纯对氯甲基苯乙烯,在开展对其基本性质、均聚反应机理研究的同     

Controlled copolymerization of 1‐octene and butyl methacrylate via RAFT and their nonisothermal model‐free thermokinetic decomposition study

Reversible addition fragmentation chain transfer (RAFT) copolymerization of 1‐octene and butyl methacrylate (BMA) was carried out for the first time using 4‐cyano‐4‐(phenylcarbonothioylthio)pentanoic acid as RAFT agent in N,N′‐dimethyl formamide. Poly(1‐octene‐co‐BMA) copolymers with well‐controlled molecular weights and narrow molecular weight distribution were obtained throughout the polymerization. The copolymers have been well characterized by different analytical techniques such as SEC, FT‐IR, NMR, SEM, AFM, XRD, and TG analyses. FT‐IR and NMR analyses confirmed the synthesis of poly(1‐octene‐co‐BMA) copolymers. SEM and AFM analyses demonstrated the wavy‐lamellar morphological structure of the copolymers. Thermogravimetric analysis revealed good thermal stability of poly(1‐octene‐co‐BMA) copolymers synthesized via RAFT mediated polymerization. The thermokinetic parameters were evaluated by adopting model‐free methods of Friedman and Flynn–Wall–Ozawa using the nonisothermal thermogravimetric data. The multivariate nonlinear regression analysis established the most appropriate kinetic model and the corresponding kinetic parameters of thermal decomposition of poly(1‐octene‐co‐BMA) copolymers were also calculated. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2093–2103     

Thermally Regenerable Ion-Exchange Resins by Photografting

Crosslinked polymer beads containing regions of acidic and basic groups are the preferred structures for the efficient operation of a thermally regenerable ion-exchange process. Such systems can be prepared by various methods. Here the approach of using polymers and copolymers containing photo-labile groups as grafting sites is described. The polymers studied were polytriallylamine hydrochloride (polyTAA) and copolymers of propyldiallylamine hydrochloride (PDAA) and allyl benzoin methyl ether (ABME), of ABME and acrylic acid (AA), and of ABME and methyl acrylate (MA). The maximum amount of photografting of MA onto polyTAA was 12%. Very little photografting of MA onto PDAA:ABME copolymers was obtained. Photografting of TAA to AA:ABME and to MA:ABME copolymers occurred readily by using radiation of 360 nm wavelength, with the best yields of photografted polymer being about 60% when a MA:ABME copolymer was irradiated in a suspension. The effect of suspending medium, stirring rate, irradiation time, irradiation intensity, solvent, solids concentration, percentage of ABME in the MA:ABME copolymer, additional crosslinkers, surfactants, and the acid:base ratio in the hy-drolyzed resin prepared by photografting TAA onto MA:ABME copolymers on the yield, physical strength, shape, and ion-exchange properties of the resins is reported.     

The adsorption of cationic and amphoteric copolymers on glass surfaces: zeta potential measurements,adsorption isotherm determination,and FT Raman characterization

The adsorption of cationic and amphoteric copolymers onto controlled pore glass (CPG) powders has been studied by measurement of the powder particle zeta (zeta) potential, by determination of the adsorption isotherm, and by FT Raman measurements of the polymer-coated powder. The cationic polymers consisted chiefly of homopolymers of dimethyldiallylammonium chloride (DMDAAC) or copolymers of DMDAAC and acrylamide. The amphoteric polymers studied included copolymers of DMDAAC and acrylic acid. The comonomer ratio was varied to explore the dependence of cationic charge density on the extent and effect of adsorption. Both types of polymers adsorb onto the anionic glass surface via an ion-exchange mechanism. Consequently, a correspondingly higher mass of a low-charge-density copolymer adsorbs than of a cationic homopolymer. The presence of the anionic portion in the amphoteric polymers does not significantly alter this picture. The zeta potential, however, reflects the overall nature of the polymer. Cationic polymers effectively neutralize the glass surface, while amphoteric polymers leave the zeta potential net negative. Adsorption isotherms, determined via the depletion technique using colloidal titration, were used to "calibrate" a FT Raman method. The latter was used to determined the amount of adsorbed polymer under solution conditions in which colloidal titration could not be performed.     

用双硫酯链转移法合成嵌段聚合物

研究了以双硫酯为链转移剂进行的均聚和嵌段共聚物的合成 .首先合成大分子链转移剂 ,得到分子量可控、多分散性系数较小的均聚物PMMA、PBMA、PEMA、PEA、PBA、PMA、PSt,多分散性系数一般小于 1 30 .在相同的条件下 ,甲基丙烯酸酯类的聚合速度最快 ,苯乙烯其次 ,丙烯酸酯类最慢 .用末端带有双硫酯基团的PSt、PBMA、PBA为链转移剂 ,加入多种第二单体聚合得到实测分子量与理论分子量接近 ,且多分散性系数较小的两嵌段聚合物 .在链转移剂和引发剂的比例为 3∶1～ 6∶1的范围内 ,聚苯乙烯同样可以作为第一嵌段得到和其它酯类单体的两嵌段聚合物 .1 H NMR方法证明了聚合物的末端带有双硫酯基团 .嵌段聚合时必须加入微量的自由基引发剂以形成大分子自由基 ,达到较好的控制聚合效果     

Correlation between the structure of water in the vicinity of carboxybetaine polymers and their blood-compatibility

The structure and hydrogen bonding of water in the vicinity of carboxybetaine homopolymer (poly[1-carboxy-N,N-dimethyl-N-(2'-methacryloyloxyethyl)methanaminium inner salt] (PolyCMB), and a random copolymer of CMB and n-butyl methacrylate, Poly(CMB-r-BMA), with various molecular weights were analyzed in their aqueous solutions and thin film with contours of O-H stretching of Raman and attenuated total reflection infrared (ATR-IR) spectra, respectively. The relative intensity of the collective band (C value) corresponding to a long-range coupling of O-H stretchings of the Raman spectra for aqueous solution of Poly(CMB-r-BMA) was very close to that for pure water, which is in contrast with the smaller C value in aqueous solution of ordinary polyelectrolytes. The number of hydrogen bonds collapsed by the presence of one monomer residue (N(corr) value) of PolyCMB and Poly(CMB-r-BMA) (CMB, 45 mol %) (M(w), 1.14 x 10(4) and 1.78 x 10(4), respectively) could be calculated from the C value. The N(corr) values were much smaller than those for ordinary polyelectrolytes and close to those for nonionic water-soluble polymers such as poly(ethylene glycol) and poly(N-vinylpyrrolidone). Furthermore, a water-insoluble Poly(CMB-r-BMA) with a large BMA content (M(w) = 347 kD, CMB 27 mol %) could be cast as a thin film (thickness, ca. 10 microm) on a ZnSe crystal for the ATR-IR analyses. At an early stage of sorption of water into the Poly(CMB-r-BMA) film, the O-H stretching band of IR spectra for the water incorporated in the film was similar to that for free water, which is in contrast with the drastic change in the O-H stretching band of water incorporated in polymer films such as poly(methyl methacrylate) (PMMA) and poly(n-butyl methacrylate) (PBMA). The theoretical vibrational frequency for water molecules hydrating a betaine molecule calculated by using a density functional method supported the experimental results. The adhesion of human platelets to Poly(CMB-r-BMA) films was much less than that to PMMA and PBMA. With an increase in the content of CMB residue, the number of platelets adhered to the Poly(CMB-r-BMA) film drastically decreased and then gradually increased, probably due to the increase in the roughness of the film surface. These results suggest that the carboxybetaine monomer residues with a zwitterionic structure do not significantly disturb the hydrogen bonding between water molecules in both aqueous solution and thin film systems, resulting in the excellent blood-compatibility of the carboxybetaine polymers.     

Block copolymerization of tert‐butyl methacrylate with α,ω‐difunctionalized polystyrene macroiniferter and hydrolysis to amphiphilic block copolymer

The block copolymerization of tert‐butyl methacrylate (tBMA) with a difunctionalized polystyrene (PS) macroinitiator was investigated. The polymerizations were performed under UV light irradiation using PS bearing α‐ and ω‐functionalized end groups containing diethyldithiocarbamyl groups as a macroiniferter. Kinetic studies indicate the molecular weights of triblock copolymers increased linearly with the conversion. Block copolymers with different lengths of PtBMA segments were easily prepared by varying the ratio of tBMA and PS macroiniferter or by controlling the monomer conversion. The formations of block copolymers were characterized by gel permeation chromatographic, ¹H NMR, and DSC analyses. PtBMA segments of the triblock copolymer were subsequently hydrolyzed quantitatively to poly(methacrylic acid) segments using concentrated HCl as a catalyst in a refluxing solution of dioxane, and then an amphiphilic ABA triblock copolymer was produced. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1450–1455, 2001     

Photo-oxidation-reduction sensitized by copolymers of [2-(9,10-anthraquinonyl)]methyl methacrylate

Copolymers of [2-(9,10-anthraquinonyl)]methyl methacrylate (AQMMA) with (2-naphthyl)-methyl methacrylate (NMMA) and benzyl methacrylate (BMA) were prepared. The photo-sensitizing efficiencies of these polymers for the oxidation-reduction of l-ascorbic acid and Fast Red A were examined in dimethylformamide. AQMMA-BMA copolymers with 6 and 14 mole% of AQMMA afforded nearly equal quantum yields, 1.6 times as large as that of a low molecular model compound, [2-(9,10-anthraquinonyl)]methyl acetate (AQMAc). The observed increase in the quantum yield is discussed in terms of energy delocalization, decreased rate of diffusion and cage effect by polymer segments. AQMMA-BMA-NMMA copolymers gave decreased quantum yields owing to intramolecular quenching of the anthraquinone triplet by the naphthalene unit. The intramolecular quenching was interpreted according to Perrin's model of static quenching. With the radius of quenching sphere assumed to be 13 A, the local naphthalene concentration around the anthraquinone unit was suggested to be approximately 20 times as small as that in solid films.