端烷氧基有机硅改性聚醚的初步研究

将双烯丙基聚醚和端含氢硅氧烷共聚后,再用乙烯基三乙氧基硅烷封端的方法制备了有机硅改性聚醚共聚物：采用核磁共振谱和DSC进行表征,表明合成了目标产物,对合成共聚物的分子质量测试及制备硫化胶的性能研究表明,还需进一步提高共聚物的分子质量。     

加工方式对沉淀法白炭黑补强硅弹性体的影响

本文探索了沉淀法白炭黑填充有机硅弹性体的加工方式。结果发现,沉淀法T36白炭黑加工时存在轻微结构化现象;在分次加入润湿剂、二次热处理后,硅弹性体强度可达8MPa,比常规加工方式提高约2MPa。     

Effect of filler type on the response of polysiloxane elastomers to cyclic stress at elevated temperatures

A variety of inorganic fillers are investigated to determine their impact on the response of filled polysiloxane elastomers to cyclic stress in hot air and in hot poly(dimethylsiloxane) PDMS fluid environments. Three fillers stabilize the polysiloxane networks to cyclic stress: zinc oxide, tin oxide, and copper oxide. Four fillers enhance network degradation: aluminum oxide, calcium oxide, titanium oxide, and tungsten oxide. The roles of testing environment, of diphenylsiloxane content of the polysiloxane network, of filler loading, of the stoichiometric balance of network precursors, and of molecular weight between cross-links are investigated. Although each influences the response of the elastomer to cyclic stress at elevated temperature, filler type exerts the primary influence. Silane-treated fillers are used to demonstrate that differences based on filler type do not arise because of changes in the strength of polymer-filler interactions. No correlation between stability of the filled elastomer to cyclic stress in hot air and filler particle size distribution, filler surface acid/base character, or the presence of specific inorganic contaminants in the filler is observed. It is proposed that the intrinsic ability of certain inorganic oxides to catalyze and/or inhibit polysiloxane degradation reactions determines the response of the filled elastomers to cyclic stress at elevated temperature. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1805–1820, 1997     

Controlled destruction of residual crosslinker in a silicone elastomer for drug delivery

In drug delivery systems that use silicone elastomers as a diffusion matrix for the active drug, it is common to crosslink the material by the hydrosilylation reaction. In this platinum‐catalyzed reaction, vinyl groups on a polymer add to the methyl siloxane hydride (MHS) groups on a low molecular mass crosslinker. With an excess of crosslinker, a fast curing is achieved and a fully crosslinked material is formed. Unreacted MHS groups were shown to remain in the elastomer after curing because of the excess crosslinker. In this work, a simple procedure was developed to eliminate the unreacted MHS groups from the final product. We found that storage of the product at +40°C and 75% relative humidity for a few weeks will effectively destroy the residual MHS groups in the elastomer. The effects of varying levels of humidity, oxygen, and temperature on this postcuring procedure were studied. The amount of MHS groups was measured with NMR and IR spectroscopy. We also found that the hardness of the material increased by approximately 25% as a consequence of this postcuring treatment. This increase is probably due to a secondary crosslinking reaction between MHS and silanol groups. Heat treatment at higher temperatures led to an even further increase in the hardness and compression modulus. Because no MHS groups remained in the elastomer when this heat treatment was started, it is apparent that another secondary crosslinking reaction is occurring, probably silanol condensation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2254–2264, 2002     

硅橡胶/聚氨酯热塑性弹性体的制备

采用过氧化物硫化体系制备了硅橡胶(VSR)与聚氨酯(TPU)质量比为50/50的VSR/TPU热塑性弹性体。考察了VSR的硫化条件,研究了抑制剂4-羟基2,2,6,6-四甲基哌啶氧(TEMPO)用量对VSR/TPU体系动态硫化过程及性能的影响。结果表明,当Hakke流变仪转速为110 r/min、硫化温度为180℃、硫化剂2,5-二甲基-2,5双(过氧化叔丁基)己烷用量为1.0份(质量,下同)、抑制剂TEMPO用量为0.3份时,制备的VSR/TPU热塑性弹性体具有较精细的相态,分散相VSR在TPU连续相中分散较均匀,热塑性弹性体的拉伸强度及扯断伸长率分别达到4.4 MPa及291%,流变性能较好,压缩永久变形最小。     

Studies of cyclic and linear poly(dimethylsiloxanes): 19. Glass transition temperatures and crystallization behaviour

Differential scanning calorimetry (d.s.c.) was used to investigate the thermal behaviour of cyclic and linear poly(dimethylsiloxanes) over the temperature range 103–298 K. Fractions of the polymers studied had number-average molar masses in the range 160 < M_n < 25 500 g mol^?1 and heterogeneity indices $\text{M}{}_{\mathrm{<mtext>w</mtext>}}\text{M}{}_{\mathrm{<mtext>n</mtext>}}\text{< 1.1}$ in most cases. D.s.c. was applied to measure the glass transition temperatures T_g cold crystallization temperatures T_c and polymer crystalline melting temperatures T_m of the oligomer and polymer fractions. Cyclic siloxanes [(CH₃)₂SiO]_x with number-average numbers of skeletal bonds n_n in the range 24 ≦ n_n ≦ 79 and linear siloxanes (CH₃)SiO[(CH₃)₂SiO]_ySi(CH₃)₃ with n_n in the range 10 ≦ n_n ≦ 40 were found not to crystallize. The T_g values of the linear siloxanes were found to be in agreement with values in the literature and they increased with increasing M_n. By contrast, the T_g values of the cyclics were found to decrease with increasing M_n.     

Adhesion between addition‐curable silicone elastomer and nylon using diallylbisphenol A as adhesion promoter

It was found that the incorporation of a small amount of 2,2′‐diallylbisphenol A in a two‐component room‐temperature vulcanizing (RTV) silicone produced excellent adhesion on nylon substrates, whereas no adhesion was observed when this additive was excluded from the formulation. The effect of the chemical structure and the functionalities of this adhesion promoter were investigated by evaluation of several other molecules bearing both allylic and phenolic groups. No adhesion improvement was observed when 2‐allyl 4‐cumylphenol or 2‐allylphenol was used as the adhesion promoter, whereas with 2‐allylbisphenol A there was good adhesion between the two surfaces. Although it is quite clear that allyl groups react with the adhesive through the hydrosilylation reaction during the cure process of the RTV material, the interaction of the phenolic group with polymer surfaces seems to be largely dependent on the steric effect, that is, the ability of the OH group to be close enough to the plastic surface to develop a strong hydrogen bond. The minimum temperature required for adhesion to occur between nylon and RTV was determined to be in the range of 50°C–60°C. This temperature corresponds to the glass‐transition temperature of the amorphous part of the nylon. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3496–3499, 2003     

Studies of cyclic and linear poly(dimethylsiloxanes): 18. Surface pressures of the monolayers in the plateau region

Measurements of the two-dimensional surface pressure π have been made as a function of average area per monomer A at areas too small to support a single monolayer, for films of cyclic and linear poly(dimethylsiloxane) (PDMS) spread on the surface of water at temperatures between 6°C and 31°C. The number-average numbers of monomer units were 10 to 196 for the rings and 10 to 1.2 × 10⁵ for the linear chains. The surface pressures were stable with time for films formed from molecules with more than 20 monomer units. For these films, two plateaux of surface pressure linked by a rounded step were observed for both rings and chains, and the step occurred at the same average area per monomer. However, although the levels of the plateaux were the same for films formed from all linear species, increases in levels of the plateaux with decreasing number of monomer units were observed for cyclic species. The temperature coefficient of the surface pressure was negative in all instances, suggesting that surface entropy is gained upon compression. The unstable films formed from the linear and cyclic decamers were also studied. The former displayed a step in the plateau region, the latter did not appear to. The present findings suggest that cyclic and linear PDMS with more than 20 monomer units collapse by a common mechanism. If the long-standing hypothesis that PDMS collapses by adopting a helical configuration is correct, this implies that rings with as few as 20 repeat units on the average coil into helices.     

大二醇软链段混合比对聚氨酯弹性体的性能影响

以α,ω-双(γ-羟丙基)聚二甲基硅氧烷(BHPDMS)和聚氧四甲基二醇(PHMO)混合大二醇作为软链段,以1,4-丁二醇(BDO)为扩链剂,采用两步溶液聚合法合成了大二醇基芳香聚氨酯(PU)弹性体,其中w(硬链段)=40%。使用傅里叶红外光谱(FT-IR)法和差示扫描量热法(DSC),研究了混合大二醇中BHPDMS与PHMO的质量比对该PU弹性体的结构形态和性能的影响。结果表明,当混合大二醇中w(PHMO)=40%-60%时,所得PU弹性体具有优异的综合力学性能和表面疏水性。     

Calculations of diffusion coefficients of cyclic poly(dimethylsiloxanes)

The Kirkwood equation and a Monte-Carlo technique which employs Metropolis sampling have been used to calculate diffusion coefficients (D) for low molar mass cyclic poly(dimethylsiloxanes). Correlations between calculated and experimental values of D show that the effective segment size is larger for cyclic than for linear PDMS. Thus, free-draining flow is reduced for the cyclic species consistent with its greater segment density. The cyclic molecules also show enhanced diffusion coefficients at very low molar masses which may be associated with the rigid toroidal shapes of these molecules.     

有机硅/丁二醇扩链剂混合比对混合大二醇基聚氨酯弹性体的性能影响

以α,ω-双(γ-羟丙基)聚二甲基硅氧烷(BHPDMS)和聚氧四甲基二醇(PHMO)混合大二醇为软链段;以1,4-丁二醇(BDO)为主要扩链剂,1,3-双(4-羟丁基)-1,1,3,3-四甲基二硅氧烷(BHTD)为次级扩链剂,所有试样中硬链段均由4,4'-二苯基甲烷二异氰酸酯(MDI)和混合扩链剂所构成,且w(硬链段)=40%;采用两步溶液聚合法制备混合大二醇基芳香聚氨酯(PU)弹性体。通过力学性能测试、差示扫描量热法(DSC)和动力学热分析法(DMTA),研究了混合扩链剂中n(BDO)/n(BHTD)比值对该PU弹性体性能的影响。结果表明,当n(BDO):n(BHTD)=3:2时,所得PU弹性体具有优异的综合性能;引入BHTD扩链剂后,破坏了硬链段的有序性。     

Recent advances in the rheooptical characterization of silicon-containing networks

Recent advances in the various theories of strain-birefringenece of polymer networks are presented. The classical theories as well as the more advanced models are outlined together with some recent theoretical results on poly (dimethylsiloxane). Reference to work on other Si-containing polymers is made. The problems of intermolecular correlations occurring in polymer networks and their effect on the observed optical properties are discussed with reference to the optical-configuration parameter. Conclusions report areas of current research.This review was presented at the Second International Topical Workshop, Advances in Silicon-Based Polymer Science.     

聚1-丁烯热塑性弹性体的老化与防护

以拉伸性能为主要检测指标，考察了聚1-丁烯[P(1-Bt)]热塑性弹性体的热氧老化、紫外光老化和耐酸碱老化性能，制备了P(1-Bt)和三元乙丙胶(EPDM)防水卷材试样并进行对比：结果表明：单独使用抗氧剂1010，其用量在0．1～0．2质量份时具有较好的防热氧效果；1010与DLTP配合使用效果更佳，最佳配比为m(1010)：n(DLTP)=1：3(1010为0．2份)。热氧防老剂与紫外光吸收剂并用明显优于热氧防老剂或紫外光吸收剂单用时的防紫外光效果；ZnO对热氧老化和紫外光老化也具有很好的防护作用。P(1-Bt)制备的防水卷材的耐紫外光老化性能接近EPDM防水卷材，耐酸碱性能优于后者。     

A novel electric elastomer based on starch/transformer oil drop/silicone rubber hybrid

The electrorheological fluid composed of starch particles and silicone oil/transformer oil was dispersed into 107 silicone rubber, and then two types of electric elastomers were prepared in the absence and presence of a curing electric field, respectively. The storage modules were measured using dynamic mechanical analysis with the round disk compression clamp. The results indicate that the storage modulus sensitivity of electric elastomers composed of pure transformer oil is the highest, that of electric elastomers composed of pure silicone oil takes second place, and that of electric elastomers composed of mixture oil is the smallest. For the given starch concentration, the storage modulus sensitivity attains a maximum value of 3.88 when the mass ratio between the transformer oil and 107 silicone rubber is 1. For the given mass ratio of 1, the effects of starch concentration and the presence or absence of the curing electric field on the storage modulus of electric elastomers were studied. When the starch concentration is 5 wt %, the storage modulus of the elastomer without the electric field (denoted as A‐elastomer) is 20.1 kPa, whereas that of the elastomer with the electric field (denoted as B‐elastomer) is 101.8 kPa. The storage modulus sensitivity attains a maximum value of 4.07. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structural silicone sealants after exposure to laboratory test for durability assessment

During the service life of structural sealant glazing (SSG) facades, the load-bearing capacity of the silicone bonds needs to be guaranteed. Laboratory tests can assess the durability of SSG-systems based on mechanical characteristics of the bond after simultaneous exposure to both climatic and mechanical loads. This article studies how the material characteristics of two common structural sealants are affected by laboratory and field exposure. Dynamic mechanical analysis (DMA) confirms a reduction in the dynamic modulus of exposed silicone samples. Results from thermogravimetric analysis, Fourier-transform infrared spectroscopy, differential scanning calorimetry, and small-angle X-ray scattering/wide-angle X-ray scattering show differences between the two sealants and indicate no/minor changes in the composition and morphology of the laboratory and field exposed sealants. Mechanical characterization methods, such as DMA, and tensile and shear testing of the structural bond, are shown to be sensitive toward the combined climatic and mechanical loadings, and are hence suitable for studying degradation mechanisms of structural sealants.     

Impact modification of waste PET by polyolefinic elastomer

Waste poly(ethylene terephthalate) [PET] and a polyolefinic elastomer (POE), Engage? 8150, were melt blended in a co‐rotating twin screw extruder having initial distributive mixing followed by high shearing/stretching. Compositions having POE up to 10% with and without poly(ethylene‐co‐acrylic acid), as a compatibilizer were studied. The blends were characterized for mechanical, thermal and rheological properties as well as for morphological characteristics. Incorporation of POE improved the impact properties of PET very significantly. © 2003 Society of Chemical Industry     

有机聚硅氧烷接枝聚醋酸乙烯酯的研究

本工作合成了聚二甲基硅氧烷—8—聚醋酸乙烯酯,通过红外光谱、核磁共振光潜、电子显微镜照相等技术表征了接枝共聚物结构。研究了接枝率与反应时间、分子量大小、引发剂用量的关系。     

有机硅树脂合成及其共混改性研究

通过实验筛选出合成有机硅树脂的配方，讨论了原料配比、水解温度，介质酸度和溶剂组成对有机硅树脂的影响。采用傅里叶变换红外光谱表征了聚甲基丙烯酸丁酯(PBMA)共混改性有机硅树脂前后的结构特征；采用扫描电子显微镜分析了有机硅树脂、PBMA和PBMA共混改性有机硅树脂的微观结构，进而探讨，改性有机硅树脂室温同化机理，即有机硅树脂分子和PBMA分子之间的互相介入、互相贯穿使之形成网络，具有了自由基协同效应。     

Rapid formation of soft hydrophilic silicone elastomer surfaces

We report on the rapid formation of hydrophilic silicone elastomer surfaces by ultraviolet/ozone (UVO) irradiation of poly(vinylmethyl siloxane) (PVMS) network films. Our results reveal that the PVMS network surfaces render hydrophilic upon only a short UVO exposure time (seconds to a few minutes). We also provide evidence that the brief UVO irradiation treatment does not cause dramatic changes in the surface modulus of the PVMS network. We compare the rate of formation of hydrophilic silicone elastomer surfaces made of PVMS to those of model poly(dimethyl siloxane) (PDMS) and commercial-grade PDMS (Sylgard-184). We find that relative to PVMS, 20 times longer UVO treatment times are needed to oxidize the PDMS network surfaces in order to achieve a comparable density of surface-bound hydrophilic moieties. The longer UVO treatment times for PDMS are in turn responsible for the dramatic increase in surface modulus of UVO treated PDMS, relative to PVMS. We also study the formation of self-assembled monolayers (SAMs) made of semifluorinated organosilane precursors on the PVMS-UVO and PDMS-UVO network surfaces. By tuning the UVO treatment times and by utilizing mono- and tri-functional organosilanes we find that while mono-functionalized organosilanes attach directly to the substrate, SAMs of tri-functionalized organosilanes form in-plane networks on the underlying UVO-modified silicone elastomer surface, even with only short UVO exposure times.     

一元羧酸结构参数对两种硅橡胶膜渗透萃取的影响研究

论文研究了甲基硅橡胶膜（PDMS）和乙烯基硅橡胶膜(PVMS)对一元羧酸的渗透萃取效果,建立了有机物结构参数与膜渗透萃取效果的关系。研究发现,PVMS膜比PDMS膜对一元羧酸有较好的萃取效果。结合一元羧酸结构参数与硅橡胶膜结构,对渗透萃取效果进行分析。结果表明：对于硅橡胶膜,随着有机物辛醇-水分配系数(Kow或P)、分子摩尔体积（Vm）、分子极化率（a）的增大,固有溶解度（S）的减小,一元羧酸的萃取率依次升高;经线性回归拟合分析,辛醇-水分配系数(Kow或P)与硅橡胶膜萃取率有良好的相关性（R2均在0.96以上）;分子摩尔体积（Vm）对硅橡胶膜萃取率表现出一定的相关性（R2均在0.81以上）;偶极矩（u）并未有表现出明显的规律性。