Solution properties and chain flexibility of poly(p-tert-butylstyrene)

The dilute solution properties of anionically synthesized poly(p-tert-butylstyrene) (PtBS) were studied in tetrahydrofuran, cyclohexane 1,4-dioxane, 1-nitropropane and 2-octanol. Cyclohexane and tetrahydrofuran are good solvents for PtBS, 1,4-dioxane is of intermediate solvent power, and 1-nitropropane and 2-octanol are theta solvents. The unperturbed dimension results show PtBS to be a more extended chain than polystyrene. These observations are interpreted in light of rotational isomeric state (RIS) models for polystyrene and poly(p-chlorostyrene) and experimental data available for polystyrene and its substituted derivatives.     

聚甲基丙烯酸2,2,3,3-四氟丙醇酯的合成

合成了单体甲基丙烯酸2,2,3,3-四氟丙醇酯,并用明胶和十二烷基苯磺酸钠作为分散剂,通过悬浮聚合法合成了此单体的均聚物。采用激光粒径分布仪、光学显微镜、差示扫描量热仪、广角X射线衍射仪等表征了聚合物性能。结果表明,所得聚合物颗粒圆滑,粒径分布在1．2～187．3μm,且呈现双分布;聚合物玻璃化转变温度为74．2℃,熔体流动性较差;聚合物具有好的憎水、憎油性能和耐酸碱性能。     

Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(methyl methacrylate)

Summary Poly(n-propyl methacrylate) is known to be immiscible with poly(methyl methacrylate) (PMMA). However, we have found that poly(methoxymethyl methacrylate) is miscible with PMMA, indicating the importance of ether oxygen atoms in achieving miscibility. On the other hand, poly(methylthiomethyl methacrylate) is immiscible with PMMA.     

Synthesis and characterization of polypropylene-based polymer hybrids linking poly(methyl methacrylate) and poly(2-hydroxyethyl methacrylate)

Isotactic polypropylene-based polymer hybrids linking poly(methyl methacrylate) (PMMA) and poly(2-hydroxyethyl methacrylate) (PHEMA) were successfully synthesized by a graft copolymerization from maleic anhydride-modified polypropylene (PP-MAH). PP-MAH reacted with ethanolamine to produce a hydroxyl group containing polypropylene (PP-OH) and the thus obtained PP-OH was treated with 2-bromoisobutyryl bromide and converted to a 2-bromoisobutyryl group containing polypropylene (PP-Br). The metal-catalyzed radical polymerization of MMA with PP-Br was performed using a copper catalyst system in o-xylene solution at 100 °C to give the PP-based polymer hybrids linking PMMA segments (PP-PMMA hybrids). Thus obtained PP-PMMA hybrids demonstrated higher melting temperature than PP-Br and microphase-separation morphology at the nanometer level owing to the chemical linkage between both segments. On the other hand, the polymer hybrids linking PHEMA segment (PP-PHEMA hybrids) were also obtained by the radical polymerization of HEMA with PP-Br in o-xylene slurry at 25 °C. TEM observation suggested that the polymerization mainly initiated on the surface of the PP-Br powder, led to the peculiar core-shell-like morphology. These PP-PHEMA hybrid powders showed a good affinity with water due to the hydrophilicity of the PHEMA segments.     

聚甲基丙烯酸氨基乙酯的合成及染色性能

以白油为分散介质,偶氮二异丁腈为引发剂,甲基丙烯酸氨基乙酯为单体,采用反相悬浮聚合法合成聚甲基丙烯酸氨基乙酯(PTAM),研究了引发剂用量、反应温度、反应时间、单体浓度对PTAM特性粘数的影响。将PTAM与聚丙烯腈(PAN)共混纺丝制得共混纤维,用酸性染料染色,考察其上染率。结果表明:合成PTAM的最佳工艺条件为引发剂质量分数0.05%,单体质量分数60%,反应温度65℃,反应时间2h,所得PTAM的特性粘数为690mL/g。染色实验结果表明,PTAM质量分数为7%时,PAN共混纤维的上染率达88%。     

Synthesis of poly(chloroprene-co-isobutyl methacrylate) and its compatibilizing effect in polychloroprene/poly(isobutyl methacrylate) blends

A copolymer of chloroprene (CP) and isobutyl methacrylate (iBMA) [poly(CP-co-iBMA)] was prepared in benzene by radical copolymerization. For comparison, the graft copolymer of iBMA onto polychloroprene (CR) [poly(CR-g-iBMA)] was also prepared. The glass transition temperature of the poly(CP-co-iBMA) was about ?32.4°C. The monomer reactivity ratios determined by the Finneman-Ross method were given as r₁ (CP) = 1.80 and r₂ (iBMA) = 0.74 in the copolymerization of CP and iBMA, respectively. Miscibility of blends of CR and poly(isobutyl methacrylate) (PiBMA), prepared by casting from tetrahydrofuran (THF) solution, was investigated by their glass transition temperature behaviors and morphologies. Although the blends of CR and PiBMA were incompatible, the addition of poly(CP-co-iBMA) or poly(CR-g-iBMA) enhanced miscibility between the two base polymers. It was found that the extent of partial miscibility becomes larger when adding poly(CP-co-iBMA) than poly(CR-g-iBMA) as a third component to the CR/PiBMA blend of 50/50 wt % composition. © 1993 John Wiley & Sons, Inc.     

Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(styrene-co-acrylonitrile) and poly(p-methylstyrene-co-acrylonitrile)

The miscibility of poly(methoxymethyl methacrylate) (PMOMA) and poly(methylthiomethyl methacrylate) (PMTMA) with poly(styrene-co-acrylonitrile) (SAN) and poly(p-methylstyrene-co-acrylonitrile) (pMSAN) was studied by differential scanning calorimetry. PMOMA is miscible with SAN having an acrylonitrile (AN) content around 30 wt %. However, PMOMA is immiscible with any of the pMSAN having AN contents between 9 and 36 wt % and with pMSAN having AN contents between 19 and 34 wt %. The miscibility of the blends enables the evaluation of various segmental interaction parameters.     

Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(vinylidene fluoride)

Summary The miscibility behaviour of poly(methoxymethyl methacrylate) (PMOMA) and poly(methylthiomethyl methacrylate) (PMTMA) with poly(vinylidene fluoride) (PVDF) was examined by differential scanning calorimetry. PMOMA/PVDF blend system was judged to be miscible on the bases of the presence of a single, composition-dependent glass transition for the blend and a pronounced melting point depression of the PVDF component. Furthermore, lower critical solution temperature (LCST) behaviour was observed for all PMOMA/PVDF blends. PMTMA/PVDF blends were found to be immiscible. Based on the melting point depression of PVDF in PMOMA/PVDF blends, the interaction parameter B was found to be -14.5 J/cm³.     

甲基丙烯酸正丁酯-含氢硅油的合成与表征

采用钯作催化剂,合成了甲基丙烯酸正丁酯-含氢硅油接枝聚合物,并用FTIR、NMR、GPC对产物进行表征。结果表明。Si-H键可与C=C键发生加成反应,甲基丙烯酸正丁酯可以接枝到含氢硅油上。     

Thermal analyses of graft copolymers of poly (methyl methacrylate) main chain with poly (propylene oxide-b-ethylene oxide) graft chain

Poly(methyl methacrylate-g-(propylene oxide-b-ethylene oxide)) and poly (methyl methacrylate-g-(ethylene oxide-b-propylene oxide)), comprising chemically dissimilar sequences, exhibit intramolecular phase separation. These compositions have applications in coatings and as surface-tension modifiers. This paper presents the thermal behavior of these graft copolymers: separate samples of the homopolymer and of the grafts were also analyzed to provide comparisons. The phase behavior has been analyzed by differential scanning calorimetry and by dynamic-mechanical thermal measurements. Two glass transitions (T_g) are observed, caused by the partial incompatibility within the copolymers. The activation energy of the T_g relaxation process of the main chain is decreased by the graft chain. The influence of poly(propylene oxide-b-ethylene oxide) grafts on the thermal degradation of the poly(methyl methacrylate) (PMMA) main chain was studied by using thermogravimetric analysis. Prolysis of the graft copolymers occurs in three stages and begins on the graft chain and at a lower temperature than the pyrolysis of pure PMMA. Both the phase behavior and the thermal stability are found to depend sensitively on the composition of the copolymer. © 1993 John Wiley & Sons, Inc.     

Synthesis and structure of the poly(methyl methacrylate) microlatex

Microemulsion polymerization is a new approach for preparing nanosize polymer materials. In this article, a nanosize poly(methyl methacrylate) (PMMA) was prepared by a novel microemulsion polymerization. The kinetics of the polymerization and the effects of the temperature, the monomer, and emulsifier/water ratio on the polymerization were investigated by means of the conversion, the transmittance, and the refractive index measurements. The structure of the obtained PMMA microlatex was studied through transmission electron microscopy (TEM), nuclear magnetic resonance (¹H‐NMR), and differential scanning calorimetry (DSC). The results show that the polymerization exhibits typical kinetic characteristics of a microemulsion polymerization, i.e., there only exists two rate stages: a stage of increasing rate, and a stage of decreasing rate, and no constant rate stage is observed during the polymerization. The obtained PMMA microparticles are very uniform, regular, and small, being about 17–33 nm in the number‐average diameter. The polymer has higher molecular weight (1.71 × 10⁶ viscosity average molecular weight), higher tacticity (51% syndiotacticity), and higher glass transition temperature (127°C), much different from the commercial PMMA. Experimentally, a stable and transparent PMMA microlatex with higher polymer content (30–40 wt %), lower weight ratio of emulsifier to water (E/W ≤ 0.03) and emulsifier to monomer (E/M ≤ 0.05) as well as smaller particle size (d_p < 40 nm), has been prepared, which is very important for the industrialization of the microemulsion polymerization technique. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2839–2844, 2002     

Synthesis and characterization of poly(methyl methacrylate) star polymers

Star-branched poly(methyl methacrylate)s (PMMA) were synthesized by linking ‘living’ arms (produced by anionic polymerzation) with ethylene glycol dimethacrylate. Stars having arm molecular weights of 10000 and 40000 and between 4.9 and 18.7 branches were produced. The polymers were characterized using light scattering, size exclusion chromatography, and viscometry. It was found that well-defined PMMA stars were obtained only at the higher (40000) arm molecular weight. The stars prepared using the lower molecular weight (c. 10000) arms contained very high molecular weight gel components.     

Miscible blends of poly(n-vinyl-2-pyrrolidone) with poly(3-chloropropyl methacrylate), poly(2-bromoethyl methacrylate) and poly(2-iodoethyl methacrylate)

Summary Poly(N-vinyl-2-pyrrolidone) is miscible with poly(3-chloropropyl methacrylate), poly(2-bromoethyl methacrylate) and poly(2-iodoethyl methacrylate) as shown by the optical clarity and the glass transition behaviour of the blends. The miscible blends degrade before phase separation could be induced by heating. The three T_g-composition curves can be fitted by the Gordon-Taylor equation. The implication of the Gordon-Taylor k parameters of the blends is discussed.     

Thermal stability of poly(styrene-b-methyl methacrylate) and poly(styrene-b-ethylene-co-1-butene-b-methyl methacrylate)

Summary The thermal stability of poly(styrene-b-methyl methacrylate) diblock copolymers (= P(S-b-MMA)) and poly(styrene-b-ethylene-co-1-butene-b-methyl methacrylate) triblock copolymers (=P(S-b-EB-b-MMA)) was investigated. Well-defined high molecular weight block copolymers with narrow molecular weight distribution (MWD) were molded at different temperatures in vacuum and the alteration of the MWD was sensitively monitored by gel permeation chromatography (GPC). Up to 240°C P(S-b-MMA) shows almost no broadening of the MWD. At higher temperatures low molecular weight polystyrene-rich portions are formed. The number average molecular weight (M_n) is strongly reduced. P(S-b-EB-b-MMA) triblock copolymers show broadening of the MWD to higher and lower molecular weights at elevated temperatures, probably caused by chain scission and linking reactions of the EB block. M_n remains approximately constant. Up to 240°C the broadening of the MWD is not very pronounced. In comparison to unhydrogenated P(S-b-B-b-MMA) triblock copolymers, the thermal stability of P(S-b-EB-b-MMA) is greatly enhanced.     

Synthesis and characterization of poly(dimethylamino ethyl methacrylate)–poly(ethylene oxide)–poly(dimethylamino ethyl methacrylate) triblock copolymers

Novel, monodispersed, and well‐defined ABA triblock copolymers [poly(dimethylamino ethyl methacrylate)–poly(ethylene oxide)–poly(dimethylamino ethyl methacrylate)] were synthesized by oxyanionic polymerization with potassium tert‐butanoxide as the initiator. Gel permeation chromatography and ¹H‐NMR analysis showed that the obtained products were the desired copolymers with molecular weights close to calculated values. Because the poly(dimethylamino ethyl methacrylate) block was pH‐ and temperature‐sensitive, the aqueous solution behavior of the polymers was investigated with ¹H‐NMR and dynamic light scattering techniques at different pH values and at different temperatures. The micelle morphology was determined with transmission electron microscopy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of fluorescent poly(methyl methacrylate) via AGET ATRP

Polymerization of methyl methacrylate (MMA) was successfully carried out via activator generated by electron transfer for atom transfer radical polymerization technique with naphthalene-1,5-diyl-bis (2-bromo-2-methylpropanoate) as an initiator, CuCl₂/bpy complex as a catalyst and tin(II) 2-ethylhexanoate (Sn(EH)₂) as a reducing agent in anisole. The polymerization showed typical features of “living”/controlled radical polymerization such as a linear increase of the molecular weights of the polymers with monomer conversion and relatively narrow polydispersities throughout the polymerization process. The resultant fluorescent poly(methyl methacrylate) was characterized by nuclear magnetic resonance spectroscopy, infrared absorption spectroscopy, ultraviolet absorption spectrophotometry and fluorescence spectrophotometry.     

Synthesis of poly(butyl methacrylate) in three-component cationic microemulsions

The polymerization of butyl methacrylate in three-component microemulsions prepared with the cationic surfactant dodecyltrimethlammonium bromide is reported here as a function of monomer and surfactant content in parent microemulsions, type and concentration of initiator, and temperature. Fast reaction rates and high conversions are achieved in all cases. Final latexes are bluish-opaque and stable, and contain spherical particles with diameters in the range of 20 to 30 nm, depending on composition of the parent microemulsions and reaction conditions. Each of these particles is composed of a few macromolecules of high molecular weight (2 to 4 × 10⁶ Dalton). Both particle size and average molecular weight remain constant throughout the reaction, suggesting a continuous nucleation mechanism. Analysis of the molecular weight distribution indicates that the controlling termination mechanism is chain-transfer to monomer. © 1996 John Wiley & Sons, Inc.     

The limits of linear viscoelasticity in poly(methyl methacrylate) and poly(ethyl methacrylate)

The limit of linear viscoelasticity is determined for poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA) in uniaxial tension creep over the temperature range of 20° to T_g ?10°C. The time span covered is from 10 to 1000 sec. The linear limit is defined as the point at which the creep compliance deviates by more than 1% from its mean value in the linear viscoelastic range. For both materials, the stress limit of linear viscoelasticity falls to a minimum or plateau level at a temperature below T_g. It is suggested that the β-mechanism plays an important role in the existence of this minimum.     

含规整 PMMA支链的 PBA合成及其力学性能

研究了聚甲基丙烯酸甲酯大单体与丙烯酸丁酯在苯中的共聚，该大单体由甲基丙烯酸甲酯在巯基乙酸链转移剂存在下聚合，用甲基烯酸缩不甘油酯封端，研究了共聚速率、大单体相对分子质量、大单体与小单体投料比、引发剂用量、单体浓度及共聚温度对接枝效率及共聚物相对分子质量的影响。用分级沉淀法精制共聚物。用凝胶渗透色谱法、红外光谱法及差示扫描量热法对共聚物进行表征，用蒸汽压式渗透压力计及膜渗透压测定了结构参数，结果表明，平均接枝数随转化率增加而降低，在一定的组成范围内，共聚物呈热塑性弹性体行为。