DL—丙交酯与甲基含氢硅油共聚反应研究（Ⅰ）

研究了丙交酯与含氢硅油在辛酸亚锡催化下的共聚反应,对催化剂用量、反应温度对共聚物得率的影响进行了考察。     

Synthesis, characterization and properties of chitosan modified with poly(ethylene glycol)-polydimethylsiloxane amphiphilic block copolymers

Synthesis of poly(ethylene glycol)-polydimethylsiloxane amphiphilic block copolymers is discussed herein. Siloxane prepolymer was first prepared via acid-catalyzed ring-opening polymerization of octamethylcyclotetrasiloxane (D₄) to form polydimethylsiloxane (PDMS) prepolymers. It was subsequently functionalized with hydroxy functional groups at both terminals. The hydroxy-terminated PDMS can readily react with acid-terminated poly(ethylene glycol) (PEG diacid) to give PEG-PDMS block copolymers without using any solvent. The PEG diacid was prepared from hydroxy-terminated PEG through the ring-opening reaction of succinic anhydride. Their chemical structures and molecular weights were characterized using ¹H NMR, FTIR and GPC, and thermal properties were determined by DSC. The PEG-PDMS copolymer was incorporated into chitosan in order that PDMS provided surface modification and PEG provided good water swelling properties to chitosan. Critical surface energy and swelling behavior of the modified chitosan as a function of the copolymer compositions and contents were investigated.     

Synthesis and properties of polyethylene and polypropylene containing hydroxylated cyclic units in the main chain

Polyethylene and isotactic polypropylene containing hydroxylated cyclic units were synthesized by copolymerization of ethylene or propylene and cyclodiolefins, dicyclopentadiene (DCPD), 5-vinyl-2-norbornene (VNB), 5-ethylidene-2-norbornene (ENB), with zirconocene catalysts and subsequent hydroboration reaction of residual unsaturated group. The resulting hydroxylated copolymers showed higher glass transition temperature (T_g) than the original and hydrogenated copolymers. Relationship between the cyclodiolefin content and ΔT_g (ΔT_g=difference of T_g between hydroxylated copolymer and hydrogenated copolymer) was given by a straight line independent of the structure of the comonomers. Improvement in shape memory effect was observed in the hydroxylated ethylene-VNB copolymer.     

Silicone elastomers with high dielectric permittivity and high dielectric breakdown strength based on dipolar copolymers

Dielectric elastomers (DEs) are a promising new transducer technology, but high driving voltages limit their current commercial potential. One method used to lower driving voltage is to increase dielectric permittivity of the elastomer. A novel silicone elastomer system with high dielectric permittivity was prepared through the synthesis of siloxane copolymers, thereby allowing for the attachment of high dielectric permittivity molecules through copper-catalysed azide-alkyne 1,3-dipolar cycloaddition (CuAAC). The copolymers have a high degree of chemical freedom, as the dimethylsiloxane spacer units between the functional groups, as well as the degree of functionalisation, can be varied. Thus, the best overall properties were obtained for an elastomer prepared with a copolymer with a 1200 g mol⁻¹ dimethylsiloxane spacer unit and 5.6 wt% of the high dielectric permittivity molecule 1-ethynyl-4-nitrobenzene. Here, a high increase in dielectric permittivity (∼70%) was obtained without compromising other favourable DE properties such as elastic modulus, gel fraction, dielectric loss and electrical breakdown strength.     

Conjugated rod-coil block copolymers: Synthesis, morphology, photophysical properties, and stimuli-responsive applications

Conjugated rod-coil block copolymers have been accorded great importance since they provide a powerful route towards supramolecular objects with novel architectures, functions and physical properties. This review summarizes recent progress on the synthesis, morphology, optoelectronic properties and applications of such block copolymers. The combination of the precise condensation and living polymerization through the grafting-from or grafting-onto methodology produce various architectures of conjugated rod-coil block copolymers, including rod-coil, coil-rod-coil, rod-coil-coil, and rod-coil-rod. In the following, the relationships between polymer morphologies and photophysical properties in different phases are reviewed, as classified by solution micelles, thin films or bulk samples, polymer brushes and electrospun nanofibers. The effects of the rod/coil ratio and polymer architecture on the morphology and optoelectronic properties are discussed. The control of nanosize domain and the aligned direction of conjugated rods are the key issues for enhancing the optoelectronic device performance. Moreover, novel multifunctional sensory materials based on combining the tunable photophysical properties of the π-conjugated rod and the stimuli-responsive coil are also highlighted. It is believed that conjugated rod-coil block copolymers could spark the future evolution of nanostructured polymers for multifunctional device applications.     

Morphology and thermomechanical properties of main-chain polybenzoxazine-block-polydimethylsiloxane multiblock copolymers

The main-chain polybenzoxazine-block-polydimethylsiloxane multiblock copolymers were synthesized via the Mannich polycondensation among 4,4′-dihydroxyldiphenylisopropane, 4,4′-diaminodiphenylmethane, aminopropyl-terminated polydimethylsiloxane and paraformaldehyde. The multiblock copolymers were characterized by means of Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR) and size exclusion chromatography (SEC). Atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS) showed that the multiblock copolymers displayed microphase-separated morphology. Owing to the presence of the main-chain polybenzoxazine blocks, the multiblock copolymers are thermally-crosslinkable. The curing behavior of the multiblock copolymers was investigated according to the analysis of non-isothermal curing kinetics. The measurement of static contact angles showed that with the inclusion of polydimethylsiloxane blocks, the polybenzoxazine thermosets resulting from the multiblock copolymers displayed the improved surface hydrophobicity.     

Surface properties of polyamides modified with reactive polydimethylsiloxane oligomers and copolymers

Surface modification of polyamide-6 (PA-6) was investigated by melt blending with silicone-urea copolymers or organofunctionally terminated polydimethylsiloxane oligomers. Blends were prepared in a laboratory scale high-shear melt mixer. Surface characteristics of the blends were determined by static water contact angle measurements and X-ray photoelectron spectroscopy. Effect of the type, composition, average molecular weight and amount of the silicone additive in the blends, on the surface properties were determined. Influence of the thermal history of the samples on the surface properties was also investigated. All of the blends showed formation of silicone rich surfaces. Surface modification was permanent due to either the formation of chemical bonds between additive and polyamide and/or very strong hydrogen bonding between urea and amide groups.     

Synthesis and properties of new copolymers containing hindered amine

Eight new copolymers containing hindered amine (HA) were synthesized by copolymerization of vinyl monomers [styrene (St), methyl methacrylate (MMA)] with new functional monomers produced by reaction of 4-amino-2,2,6,6-tetramethylpiperidine (ATMP) and epoxy compounds containing double bond, and mixture copolymerization of vinyl monomers (St and MMA) with a mixture of ATMP and above epoxy compounds. The structure of these new copolymers were characterized by IR, NMR, and elemental analysis. The properties of these new copolymers were described and their photoprotecting effectiveness examined. Experimental results indicate that they possess high photoprotecting effectiveness comparable to or higher than that of a commercial polymeric HALS “PDS.” © 1996 John Wiley & Sons, Inc.     

Polydimethylsiloxane-modified chitosan I. Synthesis and structural characterisation of graft and crosslinked copolymers

Graft and crosslinked polydimethylsiloxane (PDMS)-chitosan copolymers were prepared through the reaction between mono and difunctional glycidoxypropyl-terminated PDMSs and chitosan. The transformation of amino groups of chitosan through the reaction with epoxy groups was confirmed by FT-IR and ¹³C cross-polarization (CP) magic-angle spinning (MAS)-NMR analysis. Chitosan-based materials modified with about 40% and 60% hydrophobic polydimethylsiloxane were obtained, respectively. As proved by wide angle X-ray analysis, the crystallinity of chitosan was strongly decreased through the incorporation of PDMS sequences. However, both graft and crosslinked copolymers still present a partial crystalline structure. Their X-ray patterns are not only different as compared to chitosan but also as compared to each other. For the graft copolymer, three diffraction peaks were observed at 2θ = 8.4°, 11.2° and 21.2°, indicating the formation of a new partially crystalline phase and the modification of the interplanar distances for the phases similar to chitosan. The crosslinked copolymer is even less crystalline, the peak around 2θ = 20° being strongly decreased. Different thermal behaviour of siloxane modified chitosan was registered for graft and crosslinked copolymers; the graft sample is less stable than chitosan, while the crosslinked copolymer showed an intermediate stability between chitosan and polydimethylsiloxane precursors.     

Synthesis of siloxanes containing reactive side chains

The synthesis and characterization of siloxanes containing methacrylate, epoxy, and amino side chains are described. Direct hydrosilylation of unsaturated methacrylate or epoxy compounds with methyl hydrogen siloxanes resulted in the attachment of methacrylate or epoxy groups as side chains on the siloxane in good yields. Amino side chains on siloxanes were formed by acidic hydrolysis of the ketenimine side chains, obtained by hydrosilylation of unsaturated ketenimines with methyl hydrogen siloxanes. Details of the preparation and characterization of such unsaturated ketenimines are reported.This paper is from the Second International Topical Workshop, Advances in Silicon-Based Polymer Science.     

甲基MQ及MTQ型硅酮树脂的合成及其特性

研究了以偏硅酸钠、六甲基二硅氧烷为基本原料合成甲基ＭＱ及ＭＴＱ型硅酮树脂的方法,内容包括水解反应温度的影响,投料比例的影响,反应时间的影响,交链剂对ＭＴＱ型树脂性能的影响以及ＭＱ及ＭＴＱ树脂与液体硅橡胶配伍作为胶粘剂的粘接性能的研究等。     

喹喔啉类衍生物与甲基噻吩共聚物的合成及性质

在二价镍配合物催化下,2,5-二溴-3-甲基噻吩格氏试剂与5,8-二溴-萘基喹喔啉和5,8-二溴-菲基喹喔啉共聚,得到相应的喹喔啉类共轭共聚物,收率分别为65%和68%。通过FT IR、1H-NM R对聚合物及中间体的结构进行了表征。聚合物的循环伏安图中,分别在0.66 V(Epa)/0.37 V(Epc)(Copo ly-m er I),0.78 V(Epa)/-0.06V(Epc)和1.26(Epa)/0.46(Epc)(Copo lym erⅡ)处观察到氧化还原峰,表明该类聚合物有电化学活性。在紫外-可见光谱中,分别在263 nm,323 nm处(Copo lym erⅠ)和299 nm,402 nm处(Copo lym erⅡ)出现吸收峰。所得聚合物分别在504 nm和513 nm处出现荧光最大发射峰。     

Fumed silica filled poly(dimethylsiloxane-urea) segmented copolymers: Preparation and properties

Novel fumed silica filled thermoplastic poly(dimethylsiloxane-urea) (TPSU) segmented copolymers were synthesized and characterized. TPSU copolymers were prepared from a cycloaliphatic diisocyanate, aminopropyl terminated PDMS oligomers with number average molecular weights of 3,200, 10,800 and 31,500 g/mol and 2-methyl-1,5-diaminopentane chain extender. Two different types of fumed silica HDK H2000 (hydrophobic) and HDK N20 (hydrophilic) were utilized and incorporated into silicone-urea copolymers in amounts of 1-60% by weight. Influence of the silica type (hydrophilic versus hydrophobic), amount of silica loading and the PDMS soft segment molecular weight on the morphology, tensile properties and modulus-temperature behavior of the nanocomposites were determined. Major observations of this study were: (i) under the blending conditions used, incorporation of silica does not seem to interfere significantly with the hydrogen bonding between urea groups, (ii) incorporation of silica does not affect the glass transition temperature of PDMS, (iii) incorporation of silica influences the tensile and thermomechanical properties of silicone-urea segmented copolymers significantly, (iv) average molecular weight of the PDMS soft segment in the silicone-urea copolymer plays a critical role on the improvement of the tensile properties of the fumed silica/TPSU composites.     

含氢硅油在聚合物制备中的应用进展

综述了含氢硅油在制备接枝、嵌段、网络共聚物等方面的应用,概述了含氢硅油在制备乳化剂、消泡剂、柔软剂、农用助剂、日化助剂、涂料添加剂、仿生超疏水界面及硅橡胶等应用领域的最新进展。     

有机硅改性环氧树脂的制备及其性能研究

以3种有机氯硅烷单体水解制备有机硅单体,有机硅单体改性了环氧树脂,水解条件为温度35～40℃,时间1～1.5 h,用水量n(H2O)∶n(Cl)=(6～7)∶1。通过红外光谱分析表明,有机硅主要是与环氧树脂中羟基发生化学反应。对环氧树脂改性前后的力学性能、耐热性和防潮性进行测试,结果表明,当n(R)/n(Si)为1.5时,拉伸强度可达23.91 MPa,弯曲强度达到29.24 MPa,冲击强度达到10.02 kJ/m2,50%的质量热损失温度431℃,分别比改性前提高了3.86 MPa,9.49 MPa,6.18 kJ/m2,30℃;同时,改性后树脂防潮性能也得到了提高。     

Synthesis and characterization of trifluoromethyl substituted styrene polymers and copolymers with methacrylates: Effects of trifluoromethyl substituent on styrene

2-Trifluoromethyl styrene (2TFMS), 2,5-bis(trifluoromethyl) styrene (25BTFMS), and 3,5-bis(trifluoromethyl) styrene (35BTFMS) were synthesized. These styrenes were readily polymerized in bulk and also in solution using AIBN as a free radical initiator. The polymerization rate of these trifluoromethyl substituted styrenes and other monomers such as styrene (St), pentafluorostyrene (PFS) and 4-trifluoromethyl-tetrafluorostyrene (TFMTFS) were measured in benzene and dioxane by monitoring the ¹H NMR spectra of the double bond hydrogen. The order of polymerization rates was TFMTFS > 35BTFMS > 25BTFMS > PFS > 2TFMS > St. T_gs of styrene polymers with CF₃ substituted on the ortho position of the phenyl ring were much higher than those of the meta and para substituted styrenes due to the steric hindrance of the bulky CF₃ group close to the polymer main chain, which resulted in a decrease in the segment mobility of the polymer chains and an increasing T_g of the polymers. The copolymers of 2TFMS with methyl methacrylate (MMA) and also 25BTFMS with trifluoroethyl methacrylate (TFEMA) were prepared. T_gs of the copolymers were in the range of 120-145 °C and the copolymers were transparent and thermally stable. The copolymer films were flexible and exhibited high transmittance as the homopolymers of MMA and TFEMA. Thus, these copolymers may be utilized as novel optical materials.     

Synthesis and properties of triblock copolymers containing PDMS via AGET ATRP

The bromo-terminated macroinitiator was prepared by direct addition reaction of difunctional poly(dimethylsiloxane) (PDMS) containing methyl methacrylate end groups with hydrobromic acid in acetic acid under mild conditions, and well-defined triblock copolymers of poly(methyl methacrylate-b-dimethylsiloxane-b-methyl methacrylate) (MMA-b-DMS-b-MMA) were synthesized via activators generated by election transfer atom transfer radical polymerization (AGET ATRP). The gel permeation chromatography data obtained verified the polymerization and showed the well controlling of the reaction. FTIR and ¹H NMR measured the structure of the macroinitiator and copolymers. The contact angle measurement indicated that the water contact angles decreased gradually with the increasing of PMMA block content. The self-assembly behaviors of the triblock polymer were studied by transmission electron micrograph, scanning electron microscopy, and dynamic light scattering measurement. The results indicated that the polymers could self-assemble into various complex morphologies in different solvents and the morphologies depended on the properties of solvents. The possible molecular packing models for self-assembly behaviors of the ABA triblock polymers were proposed.     

Synthesis and chiroptical properties of liquid crystalline copolymers containing azobenzene chromophores

A series of new liquid crystalline copolymers, poly[((S)‐2‐methyl‐1‐butyl methacrylate)‐co‐(6‐(4‐(4‐cyanophenylazo)phenoxy)hexyl methacrylate)], with different contents of chiral units of 17, 36, 54 and 78 mol% were synthesized. The structures and properties of the copolymers were characterized and evaluated using infrared, ¹H NMR and UV spectroscopy, differential scanning calorimetry, gel permeation chromatography and circular dichroism (CD). The CD results suggested that absorptions of azobenzene chromophores were observed in films of copolymer containing 17, 36 or 54 mol% chiral units, but not in the film of copolymer containing 78 mol% chiral units. Also, CD values of the copolymeric films decreased with increasing chiral content. After irradiation with linear polarized light at 442 nm, CD values were changed in all the copolymeric films, and the CD values increased with decreasing chiral content in a nonlinear way, while the photoinduced change of chirality of the copolymers increased in a linear way with decreasing chiral content. The results are discussed in terms of interactions between structures and chiroptical properties. Copyright © 2007 Society of Chemical Industry     

Preparative fractionation and characterization of polycarbonate/eugenol-siloxane copolymers

Bisphenol-A polycarbonate/eugenol-siloxane copolymers were fractionated at the preparative scale by the continuous polymer fractionation (CPF) technique. It is the first example of copolymer fractionation by CPF. The distribution of siloxane species across the fractions was assessed for copolymers differing in initial siloxane concentration and block length. On- and off-line combinations of size exclusion chromatography and infrared spectroscopy were used to analyze chemical composition (CC) of the unfractionated samples across the molecular weight distribution enabling comparison with the fractions. A polycarbonate-siloxane copolymer containing 10 wt% of very short siloxane blocks (dp=2) was fractionated solely according to molecular weight (MW). By contrast, a copolymer containing 5 wt% siloxane blocks with a larger degree of polymerization (dp=23) was fractionated according to MW, as well as to CC. This ‘chemical drift’ effect for the larger siloxane block length can be ascribed to large solubility differences of low MW chains, which drastically vary in composition according to the (small) number of siloxane blocks they contain.     

Poly(arylene ether nitrile) copolymers containing pendant phenyl: Synthesis and properties

A series of poly(arylene ether nitrile) copolymers (PENAPs) were synthesized with bisphenol A (BP-A), bisphenol AP (BP-AP) and 2,6-Dichlorobenzonitrile (DCBN) via a nucleophilic substitution polycondensation reaction. FTIR and ¹H-NMR were used to confirm the structure of PENAPs. Glass transition temperature (T_g) of PENAPs determined by differential scanning calorimetry (DSC) ranged from 154.2 to 200.8°C. The 5% weight lost temperature (T_5%) of PENAPs were 418.9–447.7°C. The tensile and DMA test indicated that PENAPs possessed excellent mechanical properties with tensile strength more than 92.8 MPa and storage modulus more than 1.0 GPa at about 150°C. The melt flowability was measured by rheology properties testing ranging from 80 to 1639 GPa at 290°C and under shear frequency 100 Hz, which indicated the copolymers had good flowability and thermal stability. Additionally, PENAPs could be dissolved in many solutions, which meant PENAPs had good solubility and can be processed by solution method.