以两性高分子作反相悬浮稳定剂合成吸水剂

以聚（甲基丙烯酸十二酯－丙烯酸）两性共聚物为稳定剂，用反相悬浮聚合法合成了丙烯酸／丙烯酰胺／甲基丙烯酸羟乙酯三元共聚型超强吸水剂：吸蒸馏水1150mL.g^-1，吸0．9％NaCl溶液91mL.g^-1，研究了稳定剂结构及用量，单体组成，交联剂，链转移剂，中和程度等聚合条件及吸水剂性能的影响，实验表明甲基丙烯酸十二酯－丙烯酸共聚物是一种很好的反相悬浮稳定剂。     

聚(丙烯酰胺-丙烯酸高级酯)的溶液性质研究

采用沉淀聚合法分别合成了丙烯酰胺与丙烯酸十四酯、丙烯酸十六酯、丙烯酸十八酯一系列疏水缔合型共聚物。对共聚物溶液性质及疏水基团浓度、电解质浓度、温度等因素对共聚物溶液性能的影响进行了研究,结果表明这类疏水缔合型聚合物表观出较好的耐温、耐盐等性能。     

水溶性疏水缔合型聚(丙烯酰胺-丙烯酸十六酯)溶液性质的研究

采用沉淀聚合法制备水溶性的丙烯酰胺－丙烯酸十六疏水缔合型共聚物,研究了共聚物水溶液的性质及其影响因素。随着疏水基团含量增加,共聚物在纯水中及NaCl溶液中的特性粘数[η]均减小,疏水基团临界缔合浓度降低。共聚物溶液浓度高于监界缔合浓度时,溶液表现粘度急剧增加,表明溶液中分子间缔合大量形成。     

丙烯酰胺和表面活性大单体共聚物的合成及其性能研究

首先合成表面活性大分子单体丙烯酸聚氧乙烯（２３）－十二烷基酯（ＡＡ－ＰＯＥＬＥ）,再通过与丙烯酰胺共聚合的方法得到在水溶性聚合物聚丙烯酰胺分子结构中引入疏水基团的共聚物改性ＰＡＭ。因ＡＡ－ＯＰＥＬＥ单体具有表面活性,所以共聚合时无需添加乳化剂。当改性ＰＡＭ中疏水基团含量为１．１０ｍｏｌ％时,其水溶液表现出独特的流变性和增稠性,着重讨论了改性ＰＡＭ作为乳胶增稠剂的性能。     

光交联法合成新型温敏性水凝胶的研究

合成了丙烯酸β－羟基丙酯（β－HPAT）－N－肉桂酰氧甲基丙烯酰胺（CMMAM）共聚物，采用光交联法制备了温敏性共聚水凝胶，实验结果表明：共聚物交联程序随光照时间延长而增大，在一定温度范围内，水凝胶的溶胀率（SR）随温度升高而减小，表现出显著的温敏行为。     

(丙烯酰胺-丙烯酸十六酯)共聚物的合成及其增稠性能研究

采用沉淀聚合法合成丙烯酰胺 -丙烯酸十六酯共聚物。重点讨论了合成条件如单体配比、引发剂用量、温度等对共聚反应的影响以及共聚物对苯丙乳胶的增稠性能的影响。并用DMTA和凯达尔定氮法表征了共聚物组成 ,结果表明 :所合成的共聚物可以作为疏水缔合型增稠剂使用     

丙烯酰胺与丙烯酸十四酯共聚物的合成及性能研究

利用过氧化苯甲酰为引发剂探讨了丙烯酰胺（ＡＭ）和丙烯酸十四酯（ＴＡ）的自由基共聚合。重点讨论了合成条件如引发剂用量，单体配比、溶剂、温度等对共聚反应及共聚物对苯丙乳胶增稠性能的影响。并用ＩＲ和凯达定氮法表征了共聚物的组成，实验结果表明，ＡＭｔ ＴＡ进行沉淀聚合所得到的共物分子量足够大，可以作为疏水缔合型稠剂使用。     

N-异丙基丙烯酰胺/丙烯酸胆甾醇酯共聚物研究

合成和表征了N 异丙基丙烯酰胺 (NIPAM)与丙烯酸胆甾醇酯 (CHA)的共聚物 .利用表面张力和荧光探针法研究了共聚物水溶液的表面活性性能 ,确定了其临界胶束浓度 (CMC) .利用浊度法和荧光探针法测定了共聚物的最低临界溶液温度 (LCST) .研究发现 ,在聚N 异丙基丙烯酰胺 (PNIPAM)分子链中引入疏水结构单元CHA会使其LCST下降 ;且随着共聚物中CHA含量的增加 ,LCST下降幅度增加 .在PNIPAM链段中引入少量的CHA就会使其表现出明显的两亲性 ,共聚物在水中能形成有壳核结构的稳定胶束 .通过将疏水化合物胆甾醇作为模拟药物包埋在胶束的疏水核中的研究 ,证实所得的胶束能包埋疏水药物 ,且随着包埋胆甾醇含量的增加 ,胶束平均粒径增大 .     

水溶性聚合物和两亲聚合物：聚（丙烯酰胺－co－丙烯酸钠）－g－聚（β－胺基丙酸）接枝共聚物

合成了端丙烯酰胺基聚（β－胺基丙酸）大分子单体，用端基滴定法和１Ｈ－ＮＭＲ法测定了大分子单体的分子量，用＾１＾３Ｃ－ＭＮＲ和氢氧化钠水解法测定了支化度，在水溶液中用硫酸亚铁／异丙苯过氧化氢氧化还原引发体系引发丙烯酰胺，丙烯酸钠与聚（β－胺基丙酸）大分子单体的共聚反应，合成了聚（丙烯酰胺－ｃｏ－丙烯酸钠）－ｇ－聚（β－胺基丙酸）用１Ｈ－ＮＭＲ和滴定法测定了接枝共聚物的组成。溶液性质的数据表明，与部分     

丙烯酰胺—丙烯酸十四酯共聚物镍配合物的结构及催化性能

合成了一系列丙烯酰胺－丙烯酸＋四酯共聚物镍配合物;采用ESR、XPS、 IR、DTA－TG和电导率法,研制了其中存在的配位结构。通过镍配合物催化甲基丙烯酸甲酯的聚合反应,考察了它们的催化性能,并证明了该催化剂具有高活性和低污染性。     

Copolymers of 2-hydroxyethyl methacrylate and alkyl acrylates: Studies of molecular weight distribution and thermal behavior

Several copolymers of 2-hydroxyethyl methacrylate (HEMA) with methyl acrylate (MA), ethyl acrylate (EA), n-butyl acrylate (BA), and methyl methacrylate (MMA) were prepared at 70°C in nitrogen atmosphere using 0.2% (w/v) benzoyl peroxide as initiator. The copolymer composition was evaluated by estimation of hydroxyl group in the copolymers. Intrinsic viscosity of HEMA–EA, HEMA–BA, and HEMA–MMA copolymers was determined at 35°C in dimethyl formamide. Molecular weight distribution of copolymer samples was evaluated by gel permeation chromatography. Thermal behavior of the copolymers was investigated by dynamic thermogravimetry. Thermal stability decreased on increasing HEMA content in MA, EA, and BA copolymers. However, a reverse trend was observed in HEMA–MMA copolymers.     

Thermosensitive superabsorbents based on poly(N,N-diethylacrylamide-co-sodium acrylate)

A series of poly(N,N-diethylacrylamide-co-sodium acrylate) with a degree of crosslinking of 1 mol%have been prepared as thermosensitive superabsorbents for water.The critical swelling temperatures or the volume phase transition temperature(VPTT) and the water absorption capacity of the polymers can be modulated by varying the amount of sodium acrylate(0-60 mol%) in the copolymers.The water absorption and swelling properties of the different hydrogels have been studied as function of temperature.The crosslinked copolymers can absorb large amounts of water at ambient temperatures and dehydrate at higher temperatures with relative ease,making the absorbent materials thermally responsive and thus reusable.The water absorption capacity of the copolymers depends on the pH of the media as the acrylate monomer has a higher water absorption in its deprotonated state.Added urea in the media raises and sharpens the VPTT values of the copolymers containing sodium acrylate.     

含氟丙烯酸酯共聚物结晶性与涂膜表面润湿性能研究

以甲基丙烯酸2-全氟辛基乙酯( FOEMA)分别和不同烷烃链长丙烯酸酯(RA,CH2=CHCOOCnH2n+1,n=4,8,12,16,18)为单体,用自由基聚合法合成了一系列的含氟丙烯酸酯共聚物,通过X射线衍射(XRD)和示差扫描量热法(DSC)对共聚物进行了表征,发现结晶性与丙烯酸酯的烷烃链长度密切相关,当n=4,...     

BARRIER PROPERTIES OF VINYLIDENE CHLORIDE COPOLYMERS

The permeability coefficients of a series of copolymers of vinylidene chloride (VDC)with methyl acrylate (MA), butyl acrylate (BA) or vinyl chloride (VC) (as comonomer)to oxygen and carbon dioxide have been measured at 1.0 MPa and 30℃, while those towater vapor have been measured at 30℃ and 100% relative humidity All the copolymersare semicrystalline. VDC/MA copolymers have lower melting temperature compared withVDC/BA copolymers, while that melting temperature of VDC/VC copolymer is higherthan that of VDC/acrylate copolymers with the same VDC content. The barrier propertyof the copolymers is predominantly controlled by crystallite, free volume fraction, andcohesive energy The permeability coefficients of VDC/MA copolymers to oxygen, carbondioxide, and water vapor were successfully correlated with the ratio of free volume tocohesive energy.     

BARRIER PROPERTY AND STRUCTURE OF ACRYLONITRILE/ACRYLIC COPOLYMERS

A series of acrylonitrile (AN) copolymers with methyl acrylate (MA) or ethyl acrylate(EA) as comonomer (5--23 wt%) was prepared by free-radical copolymerization. The per-meability coefficients of the copolymers to oxygen and carbon dioxide were measured at1.0 MPa and at 30℃, and those to water vapor also measured at 100% relative humidityand at 30℃. All the AN/acrylic copolymers are semicrystalline. As the acrylate contentincrease, the permeability coefficients of the copolymers to oxygen and carbon dioxide areincreased progressively but those to water vapor are decreased progressively The gas per-meability coefficients of the polymers were correlated with free-volume fractions or the ratioof free volume to cohesive energy.     

含疏水链节的聚N-异丙基丙烯酰胺共聚物的温敏性

采用溶液聚合法合成了一系列N-异丙基丙烯酰胺(NIPAM)与甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯或甲基丙烯酸丁酯的无规共聚物,用浊度观测法和光散射法测定了不同共聚物水溶液的温敏相转变行为.结果表明:所得共聚物的低临界溶解温度(LCST)均低于均聚物PNIPAM的,酯类单体的结构和含量对共聚物的LCST有显著影响,其中酯基上的烷基对共聚物LCST的影响能力大于丙烯酸酯α位上的烷基,前者对增大共聚物的疏水性有更大贡献.通过NIPAM与特定丙烯酸酯单体进行无规共聚可以合成转变温度低于PNIPAM均聚物且具有预设LCST数值的水溶性温敏聚合物.     

Photooxidative and pyrolytic degradation of methyl methacrylate-alkyl acrylate copolymers

Different compositions of poly(methyl methacrylate-co-methyl acrylate) (PMMAMA), poly(methyl methacrylate-co-ethyl acrylate) (PMMAEA) and poly(methyl methacrylate-co-butyl acrylate) (PMMABA) copolymers were synthesized and characterized. The photocatalytic oxidative degradation of all these copolymers were studied in presence of two different catalysts namely Degussa P-25 and combustion synthesized titania using azobis-iso-butyronitrile and benzoyl peroxide as oxidizers. Gel permeation chromatography (GPC) was used to determine the molecular weight distribution of the samples as a function of time. The GPC chromatogram indicated that the photocatalytic oxidative degradation of all these copolymers proceeds by both random and chain end scission. Continuous distribution kinetics was used to develop a model for photocatalytic oxidative degradation considering both random and specific end scission. The degradation rate coefficients were determined by fitting the experimental data with the model. The degradation rate coefficients of the copolymers decreased with increase in the percentage of alkyl acrylate in the copolymer. This indicates that the photocatalytic oxidative stability of the copolymers increased with increasing percentage of alkyl acrylate. From the degradation rate coefficients, it was observed that the photocatalytic oxidative stability follows the order PMMABA > PMMAEA > PMMAMA. The thermal degradation of the copolymers was studied by using thermogravimetric analysis (TGA). The normalized weight loss and differential fractional weight loss profiles indicated that the thermal stability of the copolymer increases with an increase in the percentage of alkyl acrylate and the thermal stability of poly(methyl methacrylate-co-alkyl acrylate)s follows the order PMMAMA > PMMAEA > PMMABA. The observed contrast in the order of photostability and thermal stability of the copolymers was attributed to different mechanisms involved for the scission of polymer chain and formation of different products in both the processes.     

Binary and ternary copolymers of norbornene and its derivatives with acrylates as novel materials for optoelectronics

The free-radical copolymerization of norbornene with methacrylate, tert-butyl acrylate, acrylic acid, and decyl acrylate and the benzoyl peroxide-initiated copolymerization of tert-butyl norbornenecar-boxylate and tert-butyl acrylate are studied for the first time. Novel binary and ternary copolymers are obtained, and experimental conditions (the temperature and time of reaction, initiator concentration, and comonomer ratio) affecting the compositions, molecular masses, glass-transition temperatures, and yields of the copolymers are determined. It is ascertained that the copolymers of norbornene with methyl acrylate and tert-butyl acrylate have high transparency (93?C94%) in the range 300?C800 nm. Because of this fact, the copolymers show promise as matrices for creation of nanocomposite materials suitable for optoelectronic applications.     

自交联型含氟丙烯酸酯共聚物的合成与表征

含氟丙烯酸酯;自交联;无皂乳液;接触角滞后     

Liquid Chromatographic Analysis of Styrene-Methacrylate and Styrene-Acrylate Copolymers

Abstract

Copolymers of styrene-methacrylate (methyl-, ethyl-, and n-butyl-) and styrene-acrylate (methyl-, ethyl-, and n-butyl-) were prepared by solution polymerization at a low degree of conversion. These copolymers were separated according to composition by liquid adsorption chromatography. Silica gel was the stationary phase and a mixture of chloroform and ethanol was the mobile phase. Ethanol content in the mobile phase affected the elution of the copolymers and methacrylate or acrylate rich copolymers required much ethanol to elute from a column. The retention of the copolymers was controlled by column temperature and the copolymers tended to retain in a column at higher column temperature. A linear gradient elution method way to increase ethanol in the mobile chase was effective to separate the copolymers in the order of increasing the methacrylate or acrylate content. Styrene rich copolymers eluted first from a column. Resolution between two adjacent peaks was improved with the increase in column temperature. In a mixture of copolymers of styrene-methacrylate or styrene-acrylate (methyl, ethyl, and n-butyl) having the same styrene content, the elution was in the order of n-butyl, ethyl, and methyl methacrylate or acrylate copolymers with styrene. In copolymrs having the same styrene content, a mixture of copolymrs having diffrent ester groups was separated and a mixtue of copolymrs having the same estr group (e.g., styrene-methyl mth-acrylate and styrene-methyl acrylate copolymers) was not separated.