有机硅聚合物共混改性环氧树脂水分散液的制备、表征及成膜后的性能

用氨基硅油微乳液与水的原位分散方法,制备了有机硅聚合物共混改性接枝环氧树脂水分散液,采用FT—IR、ATR、TEM以及TGA等对该水分散液的粒子形态、粒径以及成膜后的物理性能进行了表征。实验结果表明：与未改性的水分散液相比,改性水分散液的粒径减小,粒径分布变宽,粘度增大。TEM照片表明：有机硅聚合物在分散过程中被包裹在环氧树脂内部,形成“核-壳”结构的复合颗粒。改性水分散液成膜后的疏水、疏油性能和热性能显著提高,表面能降低。膜的超薄切片TEM照片显示：有机硅聚合物在成膜过程中向表面取向与迁移,FT—IR与ATR的测试结果进一步证实它们在膜的表面富集。     

侧链含有蓝相液晶基元的聚硅氧烷液晶的合成及表征

采用蓝相小板块液晶单体反式4-乙烯基反式-4′-丙基双环己烷（3HHV）和反式-4-丙烯基反式-4′-丙基双环己烷(4HHV)同时接枝到聚甲基含氢硅氧烷上,制备了聚硅氧烷侧链液晶聚合物。采用红外光谱和核磁共振氢谱对液晶单体及相应的聚合物进行结构表征,采用热台偏光显微镜,X-射线衍射和热分析对单体和聚合物的液晶行为及热性能进行研究。结果表明：液晶单体3HHV显示蓝相镶嵌织构,液晶单体4HHV显示胆甾相油纹状织构,它们的介晶区间温度分别为30.6 °C和49.7 °C,且均在低于室温就显示出液晶性。相应的液晶聚合物显示向列相纹影织构,介晶区间温度为192.6 °C,在低于室温时也显示出液晶性,且热分解温度达到310 °C以上,比其他环芳烃类介晶基元接枝聚硅氧烷主链的液晶聚合物具有更优越的热稳定性。     

Surface Properties of Mesophase‐Forming Fluorinated Bicycloacrylate/Polysiloxane Methacrylate Copolymers

Novel random copolymers were synthesized by free‐radical polymerization of a bicycloacrylate monomer carrying a fluorocarbon chain side group (BAF10) with a methacrylate monomer having a polysiloxane side graft (SiMA). The copolymers with higher contents of BAF10 gave rise to a well‐ordered smectic bilayer mesophase. The surface structure of the derived polymer films was investigated by measurements of the contact angle with several interrogating liquids and X‐ray photoelectron spectroscopy (XPS) at different photoemission angles. The values of the contact angles were used to evaluate the film surface tension, following different additive‐component and equation‐of‐state methods. The low surface energies found were attributed to the pronounced hydrophobicity and oleophobicity of the outermost surface caused by the preferential segregation of the fluorocarbon chains to the polymer–air interface.

     

排龈硅橡胶在高强度纤维桩核修复应用中的护理探讨

目的 探讨排龈硅橡胶在高强度纤维桩核修复中的应用及护理体会.方法 使用Magic FoamCord排龈硅橡胶为32例备牙患者排龈,用Rapid硅橡胶印模材制取印模.结果 32副工作模均一次操作完成,印模印迹清晰准确,预备体肩台及边缘暴露清晰,符合临床要求.结论 Magic FoamCord排龈硅橡胶在口腔固定修复中应用效果好,可以明显提高修复疗效.     

聚硅氧烷酯类液晶(PMMS)气相色谱固定液的研究——Ⅱ.侧链为对苯二酚二苯甲酸酯型的PMMS

设计并合成了文题的PMMS:Ⅱ、Ⅲ两类各8个。Ⅱ类的侧链为对-正烷氧基(Ⅲ类为对-正烷基)苯甲酸、苯甲酸对苯二酚酯型。对硅氢加成反应物的含氢硅油和最终产物用NMR和VPO方法进行测定,表明硅氢加成反应的完全和产物PMMS的高分子量。这些PMMS大多数具有较宽的液晶相温度范围(100℃左右)。从热失重分析说明PMMS具有比相应小分子液晶更高的化学热稳定性,高温下流失小。对于Ⅱ类的毛细管气相色谱考察研究表明,作为固定液,PMMS兼有高分子硅油固定液和小分子液晶固定液的优良性能,并对复杂的多环芳烃混合物有令人满意的分离效果。     

紫外光固化聚二甲基硅氧烷脲撑氨基甲酸甲基丙烯酸酯的研究——Ⅱ亲水疏水共聚网络体系

本文以α、ω-二氨丙基封端的聚二甲基硅氧烷、甲苯二异氰酸酯、甲基两烯酸羟乙酯为原料,合成了甲基丙烯酸酯封端的聚二甲基硅氧烷聚氨酯。并以此作为反应性低聚物,以甲基丙烯酸羟乙酯为亲水性反应稀释剂,通过紫外光固化,合成了一系列聚硅氧烷含量不同的共聚网络。应用红外光谱、凝胶含量测定、热分析、动态力学性能、吸水性实验等方法,对它们的固化程度、亲水疏水性能进行了研究。结果表明:体系中存在着两相结构,增加稀释剂的含量,材料的吸水性增加。通过调节疏水性的聚二甲基硅氧烷和亲水性的甲基丙烯酸羟乙酯的含量可改变体系的亲水疏水平衡。     

Factors influencing optical 3D scanning of vinyl polysiloxane impression materials

PURPOSE: Future growth in dental practice lies in digital imaging enhancing many chairside procedures and functions. This revolution requires the fast, accurate, and 3D digitizing of clinical records. One such clinical record is the chairside impression. This study investigated how surface angle and surface roughness affect the digitizing of vinyl polysiloxane impression materials. MATERIALS AND METHODS: Seventeen vinyl polysiloxane impression materials were digitized with a white light optical digitizing system. Each sample was digitized at 3 different angles: 0 degrees, 22.5 degrees, and 45 degrees, and 2 digitizer camera f-stops. The digitized images were rendered on a computer monitor using custom software developed under NIH/NIDCR grant DE12225. All the 3D images were rotated to the 0 degrees position, cropped using Corel Photo-Paint 8 (Corel Corp, Ottawa, Ontario, Canada), then saved in the TIFF file format. The impression material area that was successfully digitized was calculated as a percentage of the total sample area, using Optimas 5.22 image processing software (Media Cybernetics, LP, Silver Spring, MD). The dependent variable was a Performance Value calculated for each material by averaging the percentage of area that digitized over the 3 angles. New samples with smooth and rough surfaces were made using the 7 impression materials with the largest Performance Values. These samples were tested as before, but with the additional angle of 60 degrees. Silky-Rock die stone (Whip Mix Corp, Louisville, KY) was used as a control. RESULTS: The Performance Values for the 17 impression materials ranged from 0% to 100%. The Performance Values for the 7 best materials were equivalent to the control at f/11 out to a surface angle of 45 degrees; however, only Examix impression material (GC America Inc, Alsip, IL) was equivalent to the control at f/11/\16. At the 60 degrees surface angle with f/11/\16, the Performance Values were 0% for all the impression materials, whereas that for the control was 90%. The difference in the Performance Values for the smooth and rough surface textures was 7%, which was not significant. CONCLUSIONS: The digitizing performance of vinyl polysiloxane impression materials is highly material and surface angle-dependent and is significantly lower than the die stone control when angles to 60 degrees are included. It is affected to a lesser extent by surface texture.     

Microstructure Induced Rigidity of Polysiloxane Yielding Hierarchical Self‐Assembly of Alkyl Side Chains

The influence of a backbone microstructure on the side chain crystallization of a comb‐like polymer is analyzed systematically using a tailor‐made random versus block siloxane copolymer system. While the side alkyl chains of the random siloxane undergo a stepwise order–disorder (OD) transition to form well‐ordered orthorhombic structure at low temperature, the packing structure of the alkyl chains pertaining to the block siloxane maintains their original hexagonal lattice up to a temperature of as low as 173 K. The unit lattice ordering of side alkyl chains in the random siloxane polymer is also accompanied by a major restructuring of the backbone conformation ultimately losing out long range ordered structure in the solid state. The OD transitions of side alkyl chains and their dynamic relationship with the backbone conformation are established unambiguously by a combination of temperature dependent small‐angle X‐ray and wide‐angle X‐ray scattering techniques. The observed conformational variations in random versus block polymers are explicitly discussed in terms of molecular chain mobility and theory of macromolecular chain conformation.     

Synthesis of Dendritic Polyethylene Brushes with Polysiloxane as the Main Chain

A new synthetic procedure is described for the preparation of dendritic polyethylene brushes with polysiloxane as the main chain, describing for the first time that it is possible to simply and efficiently prepare highly branched architectures for this type of polymer. Furthermore, as a result of the polymer brush architecture, polyethylene acts as the side chains and Si O Si as the backbone. The number average molecular weight (M _n) of the polyethylene brushes, which is determined using a multiple angle laser light scattering detector, increases from 5946 to 27 684 g mol⁻¹ while retaining relatively narrow polydispersities (1.5–2.4). The polymer brushes are characterized by solid ²⁹Si NMR and high‐temperature ¹H NMR spectra. In addition, X‐ray photoelectron spectroscopy and gel permeation chromatography were used to confirm the structure.

     

Dynamic viscoelastic properties of vinyl polysiloxane denture soft lining materials

Summary The aim of this study was to investigate the dynamic viscoelastic properties of seven commercially available vinyl polysiloxane denture soft lining materials. Five rectangular specimens (2 × 10 × 30 mm) were prepared from each material. The complex modulus E* (MPa) and loss tangent (tan δ) of each specimen were determined with a non‐resonance forced vibration method using an automatic dynamic viscoelastometer at 1 Hz after 1 day of dry storage, and after 1, 30, 60, 90 and 180 days of wet storage at 37 °C. All data were analysed using one‐way anova and Bonferroni/Dunn’s test for multiple comparisons with a significance level of P < 0·01. All materials varied widely in terms of viscoelasticities and showed both an increase in E* and a decrease in tan δ at 1 Hz after the 1‐day wet storage. After 60 days of wet storage, both E* and tan δ did not change significantly. The stiffer materials (>30% filler content) with high E* values (>2·00 MPa) showed elastic behaviour with tan δ values of around 0·03. The softer materials (6% filler content) with high tan δ values (initial value > 0·10) showed viscous behaviour and were easily affected by water absorption after the 1‐day wet storage. It can be concluded that for the proper selection of vinyl polysiloxane denture soft lining materials, it is very important to evaluate the viscoelastic properties after 60 days of wet storage.