Synthesis and characterization ofα-{3-[(2,3-dihydroxy) propoxy]propyl}-ω-butylpolydimethylsiloxanes

Hydrosilylation has been carried out between Si-H terminated polydimethylsiloxanes with narrow molecular weight distribution and protected 3-allyloxy-l,2-propanediol, and after subsequently alcoholyzed, α-{3-[（2,3-dihydroxy）propoxy]propyl}-ω- butyl-polydimethylsiloxanes with varying number of （（Si（CH3）2-O） unit were obtained. At each step, the produced compounds were carefully characterized. The results showed that each step was successfully carried out and target products were achieved.

Ultrahydrophobic melamine sponge via interfacial modification with reduced graphene oxide/titanium dioxide nanocomposite and polydimethylsiloxane for oily wastewater treatment

Three-dimensional(3D)porous absorbents have attracted significant attention in the oily wastewater treatment technology due to their high porosity and elasticity.Given their amphiphilic surface,they have a propensity to simultaneously absorb water and oil,which restricts their range of applications.In this study,a reduced graphene oxide and titanium dioxide nanocomposite(rGO/TiO_(2))was used to fabricate an ultra-hydrophobic melamine sponge(MS)through interfacial modification using a solution immersion technique.To further modify it,poly-dimethylsiloxane(PDMS)was grafted onto its surface to establish stronger covalent bonds with the composite.The water contact angle of the sponge(rGO/TiO_(2)/PDMS/MS)was 164.2°,which satisfies the condition for ultrahydrophobicity.The evidence of its water repellency was demonstrated by the Cassie-Baxter theory and the lotus leaf effect.As a result of the increased density of rGO/TiO_(2)/PDMS/MS,it recorded an initial capacity that was 2 g/g lower than the raw MS for crude oil absorption.The raw MS retained 53% of its initial absorption capacity after 20 cycles of absorption,while rGO/TiO_(2)/PDMS/MS retained 97%,suggesting good recyclability.Excellent oil and organic solvent recovery(90%-96%)was demonstrated by rGO/TiO_(2)/PDMS/MS in oil-water combinations.In a continuous separation system,it achieved a remarkable separation efficiency of 2.4×10^(6)L/(m^(3)·h),and in turbulent emulsion separation,it achieved a demulsification efficiency of 90%-91%.This study provides a practical substitute for massive oil spill cleaning.

Influence of water vapor on the separation of volatile organic compound/nitrogen mixture by polydimethylsiloxane membrane

In the industrial treatment of waste volatile organic compound(VOC)streams by membrane technology,a third impurity,generally,water vapor,coexists in the mixture of VOC and nitrogen or air,and can affect membrane performance and the design of the industrial process.This study focused on the investigation of the effect of water vapor on the separation performance of the separation of VOC/water/nitrogen mixtures by a polydimethylsiloxane(PDMS)membrane.Three types of VOCs:water-miscible ethanol,water-semi-miscible butanol,and water-immiscible cyclohexane,were selected for the study.Different operating parameters including,concentration of the feed VOC,feed temperature,and concentration of the feed water were compared for the separation of binary and ternary VOC/nitrogen mixtures.The interaction between the VOC and water was analyzed to explain the transportation mechanism after analyzing the difference in the membrane performance for the separation of binary and ternary mixtures.The results indicated that the interaction between the VOC(or nitrogen)and water is the key factor affecting membrane performance.Water can promote the permeation of hydrophilic VOC but prevent hydrophobic VOC through the membrane for the separation of ternary VOC/water/nitrogen mixtures.These results will provide fundamental insights for the design of the recovery application process for industrial membrane-based VOCs,and also guidance for the investigation of the separation mechanism in vapor permeation.

α,ω-羟基聚二甲基硅氧烷和聚苯乙烯共混物的制备、硫化及力学性能研究

以α,ω-羟基聚二甲基硅氧烷(PDMSO)和苯乙烯(St)为原料,在过氧化苯甲酰(BPO)存在下,St在PDMSO中进行自由基聚合,获得了在室温下稳定的、可流动的α,ω-羟基聚二甲基硅氧烷(PDMSO)和聚苯乙烯(PS)的共混物(PDMSO/PS),对共混物做了透射电镜测试(TEM),照片显示,PS作为分散相分散在PDMSO的连续相中。用二丁基二月桂酸锡作催化剂,甲基三乙氧基硅烷作硫化剂,在室温下对该共混物进行了硫化成型;对所得硫化胶片进行了力学性能测试。结果表明,胶片具有较好的拉伸强度和弹性。

α,ω-羟基聚二甲基硅氧烷和交联聚苯乙烯共混物的制备、硫化及力学性能

以二乙烯苯(DVB)为交联剂,在过氧化苯甲酰(BPO)的引发下,苯乙烯(St)可在α,ω-羟基聚二甲基硅氧烷(PDMS)中就地进行自由基聚合,当体系中DVB的量控制在DVB/St≤2.0%(质量)范围内即可获得稳定的、具有流动性的α,ω-羟基聚二甲基硅氧烷(PDMS)/交联聚苯乙烯(CLPS)共混物。向共混物中加入过量的甲基三乙氧基硅烷(MTES)可使其在室温下硫化成弹性体材料。其力学性能明显优于PDMS/PS共混物的硫化材料。并且随着MTES量的增加,材料的拉伸强度增强而断裂伸长率逐渐降低。此外,在PDMS/CLPS共混物的TEM研究中发现了特殊的微观相分离结构。

高分子化学探索性实验:α,ω-羧基聚二甲基硅氧烷的可控合成

以高分子化学实验课程为载体,将学生课外科研活动与高分子化学实验以及任课教师所在科研团队的科研成果有机结合起来,把功能高分子的设计与结构表征提前引入到高分子化学实验中,形成了一整套较为完整、具有探索性和综合性的高分子化学实验实施方案。以α,ω-羧基聚二甲基硅氧烷（α,ω-羧基硅油）的可控合成为例,通过引导本科生独立地进行文献检索、实验方案设计、材料合成和结构表征及实验报告撰写,既提高了他们利用已学的有机化学和高分子化学知识进行综合分析的能力,又培养了其查阅文献、分析文献和形成创新性思维的能力。

Blood Compatibility of Amphiphilic Poly(N-α-acrylamide-L-lysine-<i>b</i>-dimethylsiloxane) Block Copolymers

Amphiphilic block copolymers poly(LysAA-b-DMS) consisting of a hydrophilic poly(N-α-acrylamide-L-lysine) [poly(LysAA)] segment with different molecular weights and a hydrophobic polydimethylsiloxane (PDMS) segment were prepared as follows. The precursor copolymer poly(Boc-LysAA-OtBu-b-PDMS) was obtained from radical polymerization of N-α-acrylamide-N-ε-tert-butoxycarbonyl-L-lysine-tert-butylester (Boc-LysAA-OtBu) initiated with 4,4’-azobis(polydimethylsiloxane 4-cyanopentanoate) (azo-PDMS) with the molecular weight of PDMS Mw = 4.3 × 103 in the presence of 2-mercaptoethanol (2-ME) as a chain-transfer agent. Removal of the protecting groups of the precursor copolymer was carried out in 80% trifluoroacetic acid aqueous solution to give poly(LysAA-b-DMS)-1-3. The weight average molecular weight of poly(LysAA-b-DMS)-1-3 was Mw = 1.02 × 104 – 2.52 × 104. From the 1H-NMR and fluorescence spectra measurements, poly(LysAA-b-DMS)-1-3 was determined to self-organize and form core-shell micelles in water. The critical micelle concentration (CMC) increased to 1000 - 4000 mg·L–1 with increasing molar ratio of the poly(LysAA) segment from 0.42 to 0.65. From morphological analysis with a scanning probe microscope (SPM), poly(LysAA-b-DMS) has microphase-separated structures made up of hydrophilic and hydrophobic regions with the domain size ranging from several tens to several hundreds of nanometers. Inhibition of thrombin activity of poly(LysAA-b-DMS) was evaluated from the Michaelis constant (KM) and catalytic activity (kcat) for the enzymatic reaction of thrombin and synthetic substrate S-2238 in the presence of poly(LysAA-b-DMS). The KM and kcat were 0.10 - 0.11 mM and 4.04 × 105 – 4.26 × 105 min–1, respectively. Fibrinolytic activity was also verified from the transformation of plasminogen to plasmin by tissue plasminogen activator (t-PA) using synthetic substrate S-2251 in the presence of poly(LysAA-b-DMS). The KM and kcat were 0.07 mM and 5.73 × 106 –5.95 × 106 min–1, respectively.

Impact of polydimethylsiloxanes on physicochemical and tribological properties of naphthenic mineral oil(KN 4010)-based titanium complex grease

Titanium complex greases were prepared by using naphthenic mineral oil and polydimethylsiloxane as the mixed base oil. The effect of polydimethylsiloxane molecular weight and polydimethylsiloxane content in mixed base oil on the physicochemical and tribological properties of titanium complex greases was investigated.As compared to the sole mineral oil-based titanium complex grease, the use of polydimethylsiloxane(H201-350)as a co-base oil increased the dropping point from 310 to 329℃, decreased the oil separation from 3.7% to 2.3%,reduced the corrosion extent, and obviously improved the tribological properties. When the mixed oil-based titanium complex grease was used as a lubricant, lubricating films of polydimethylsiloxane were probably formed on the surfaces of friction pairs, giving good lubricating property.

Recent advances in lithographic fabrication of micro-/nanostructured polydimethylsiloxanes and their soft electronic applications

The intensive development of micro-/nanotechnologies offers a new route to construct sophisticated architectures of emerging soft electronics.Among the many classes of stretchable materials,micro-/nanostructured poly(dimethylsiloxane)(PDMS)has emerged as a vital building block based on its merits of flexibility,stretchability,simple processing,and,more importantly,high degrees of freedom of incorporation with other functional materials,including metals and semiconductors.The artificially designed geometries play important roles in achieving the desired mechanical and electrical performances of devices and thus show great potential for applications in the fields of stretchable displays,sensors and actuators as well as in health-monitoring device platforms.Meanwhile,novel lithographic methods to produce stretchable platforms with superb reliability have recently attracted research interest.The aim of this review is to comprehensively summarize the progress regarding micro-/nanostructured PDMS and their promising soft electronic applications.This review is concluded with a brief outlook and further research directions.

Moth-eye Structured Polydimethylsiloxane Films for High-Efficiency Perovskite Solar Cells

Large-area polydimethylsiloxane(PDMS)films with variably sized moth-eye structures were fabricated to improve the efficiency of perovskite solar cells.An approach that incorporated photolithography,bilayer PDMS deposition and replication was used in the fabrication process.By simply attaching the moth-eye PDMS films to the transparent substrates of perovskite solar cells,the optical properties of the devices could be tuned by changing the size of the moth-eye structures.The device with 300-nm moth-eye PDMS films greatly enhanced power conversion efficiency of ~21 % due to the antireflective effect of the moth-eye structure.Furthermore,beautiful coloration was observed on the 1000-nm moth-eye PDMS films through optical interference caused by the diffraction grating effect.Our results imply that moth-eye PDMS films can greatly enhance the efficiency of perovskite solar cells and building-integrated photovoltaics.

A STUDY ON RADIATION CROSSLINKING OF POLYDIMETHYLSILOXANE (PDMS) RUBBER LATEX

Polydimethylsiloxane (PDMS) rubber latex with two sorts of sensitizers, trimethylol propane tri-methacrylate (TMPTMA) and diethylene glycol di-acrylate (DEGDA), was irradiated with γ-rays and electron beams in various conditions. The radiation crosslinking reaction of PDMS occurs in the inner phase of the latex and is relatively isolated from the water phase. Therefore the oxygen and the radicals produced by the radiolysis reaction of water almost have no effect on the crosslinking reaction of polymer. The experimental data correspond with the Charlesby-Pinner relationship in the main. The gelation doses, degree of crosslinking and degradation as well as G values of crosslinking were calculated. From them, the sensitization coefficients were derived to offer a quantitative measurement of the enhancing effect of sensitizer on the radiation crosslinking.

Synthesis and characterization of a novel hydroxypolyether blocked polydimethylsiloxane PEO-b-PDMS-b-PEO

A novel hydroxypolyether blocked polydimethylsiloxane, poly（ethylene oxide） propyl-b-polydimethylsiloxane-b-propyl poly（ethylene oxide） （PEO-b-PDMS-b-PEO） was synthesized by simple hydrosilation reaction of poly（ethylene glycol） monoallyl ether with α,ω-dihydrogen terminated PDMS （HPDMS）. Fourier transform infrared spectroscopy （FTIR） and IH NMR were used to identify the structure of PEO-b-PDMS-b-PEO and intermediate product HPDMS. Based on the effect investigations of temperature, reactant molar ratio, catalyst and time on the hydrosilation, it was found that the conversion of Si-H bond to SiC bond increased with the increase of catalyst and time, and the reaction completed when the content of catalyst was 22μg/g and the time was 5 h, respectively. Urethane reaction of OH and NCO group confirms that PEO-b-PDMS-b-PEO is more reactive toward to diisocyanate than α,ω-dihydroxylbutyl terminated PDMS.

Properties of polydimethylsiloxane hydrophobic modified duplex microarc oxidation/diamond-like carbon coatings on AZ31B Mg alloy

A reliable,high-performance coating procedure was developed using PDMS to modify a duplex MAO/DLC coating on an AZ31B Mg alloy.First,the duplex MAO/DLC coating was fabricated via a combined MAO and unbalanced magnetron sputter process.Subsequently,a PDMS solution was used to modify the MAO/DLC coating via a conventional dip-coating method.The surface characteristics,bond strength,hardness,tribological behaviour,and corrosion resistance of the coated samples were evaluated via SEM,CA,Raman spectroscopy,friction and wear behaviour,polarisation curve,and NSS tests.The PDMS modification reduced the HIT of MAO/DLC coating from 15.96 to 8.34GPa;this is ascribed to the penetration of PDMS,which has good rheological properties to form a viscoelastic Si-based organic polymer layer on the MAO/DLC coating.However,the PDMS-modified MAO/DLC coating was denser,hydrophobic,and had higher bond strength compared with MAO-and MAO/DLC-coated samples.Moreover,the PDMS modification reduced the COF and wear rate of the duplex MAO/DLC coating.This indicates that the PDMS improved the tribological behaviour owing to the transferred Si oxide that originated from the Si-O network of the PDMS,as well as the low graphitisation of the DLC layer during sliding.Furthermore,the corrosion current density of the MAO/DLC-coated sample modified by PDMS for 10min decreased by two order of magnitude compared with that of the MAO/DLC-coated sample but by five orders of magnitude compared with that of the bare substrate.The NSS tests proved that the PDMS layer slowed the corrosion of the Mg alloy under long-term service,enhancing the corrosion protection efficiency.The results are attributed to the high bond strength and lubricant MAO/DLC layer,and the dual role of sealing and hydrophobicity of PDMS.Therefore,PDMS modification is promising for the fabrication of protective materials for Mg alloys that require corrosion and wear resistance.

INFLUENCE OF SURFACE-MODIFICATION FOR CALCIUM CARBONATE ON THE INTERACTION BETWEEN THE FILLERS AND POLYDIMETHYLSILOXANE

The surface of calcium carbonate(CaCO_3)particles was modified with stearic acid(SA)and the chemical structures of the product were characterized by FT-IR analysis.The interaction between polydimethylsiloxane(PDMS)and CaCO_3 fillers with different surface character was investigated by means of dynamic rheological and bound rubber tests for uncured compounds and mechanical properties measurements for the corresponding vulcanites.The results of dynamic tests indicate that with the increase of SA mass fraction...

Synthesis and characterization of poly(phthalazinone ether nitrile) (PPEN)-polydimethylsiloxane (PDMS) block copolymers

Block copolymers with different backbone compositions have been prepared by the condensation of dimethylamino terminated poly（dimethylsiloxane） （PDMS） and hydroquinone terminated poly（phthalazinone ether nitrile） （PPEN） in the presence of chlorobenzcne/N-methyl pyrrolidone （NMP） as solvents. The products were characterized by FTIR, ^1H NMR and gel permeation chromatography. Differential scanning calorimetry analysis indicated that the block copolymers showed separated microphase.

Ethanol Recovery from Fermentation Broth by Pervaporation Using a Composite polydimethylsiloxane Membrane

The pervaporation behavior of fermentation broth was investigated experimentally and compared with those started with ethanol mixtures. Ethanol was produced by Saccharomyces cerevisiae utilizing technical grade glucose and recovered by pervaporation using a composite polydimethylsiloxane (PDMS) membrane prepared in our laboratory. Ethanol concentration in fermentation broth decreased to a relatively low level when pervaporation was coupled with fermentation. The more active cells appeared in the fermentation broth, the better the membrane performance was.

Separation of Sulfur/Gasoline Mixture with Polydimethylsiloxane/ Polyetherimide Composite Membranes by Pervaporatlon

Worldwide environment has resulted in a limit on the sulfur content of gasoline.It is urgent to investigate the desulfurization of gasoline.The polydimethylsiloxane(PDMS)/polyetherimide(PEI)composite membranes were prepared by casting a PDMS solution onto porous PEI substrates and characterized by scanning electron microscope(SEM).The membranes were used for sulfur removal from gasoline by pervaporation.The effects of feed temperature,sulfur content in the feed and PDMS layer thickness on membrane performance were investigated,and an activation energy of permeation was obtained.Experimental results indicated that higher feed temperature yielded higher total flux and lower sulfur enrichment factor.The total flux varied little with the increase of sulfur content in the feed,but the sulfur enrichment factor first increased with the amount of thiophene added into the gasoline,and then the variation was little.The increase of PDMS layer thickness resulted in a smaller flux but a larger sulfur enrichment factor.The result indicates that the PDMS/PEI composite membranes are promising for desulfurization by pervaporation.

Polydimethylsiloxane (PDMS) Composite Membrane Fabricated on the Inner Surface of a Ceramic Hollow Fiber: From Single-Channel to Multi-Channel

The fabrication of a separation layer on the inner surface of a hollow fiber (HF) substrate to form an HF composite membrane offers exciting opportunities for industrial applications, although challenges remain. This work reports on the fabrication of a polydimethylsiloxane (PDMS) composite membrane on the inner surface of a single-channel or multi-channel ceramic HF via a proposed coating/crossflow approach. The nanostructures and transport properties of the PDMS HF composite membranes were optimized by controlling the polymer concentration and coating time. The morphology, surface chemistry, interfacial adhesion, and separation performance of the membranes were characterized by fieldemission scanning electron microscope (FE-SEM), attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy, the nano-indentation/scratch technique, and pervaporation (PV) recovery of bio-butanol, respectively. The formation mechanism for the deposition of the PDMS layer onto the inner surface of the ceramic HF was studied in detail. The optimized inner surface of the PDMS/ceramic HF composite membranes with a thin and defect-free separation layer exhibited a high flux of ~1800 gm-2h-1 and an excellent separation factor of 35–38 for 1 wt% n-butanol/water mixtures at 60
C. The facile coating/cross-flow methodology proposed here shows great potential for fabricating inner-surface polymer-coated HFs that have broad applications including membranes, adsorbents, composite materials, and more.

Comparison of Apical Leakage in Root Canal Obturation Using Bioceramic and Polydimethylsiloxane Sealer (<i>In Vitro</i>)

Background: One of the ideal properties of a root canal sealer is to have a good sealing ability, especially at the apical third of the root. Objective: To evaluate the comparison of the apical leakage between obturation using bioceramic sealer (BS) and polydimethylsiloxane sealer (PS). Materials and Methods: Thirty-six mandibular premolars were equally divided into two groups and were obturated with single cone technique. The sealers used for Group I and Group II were BS and PS respectively. After obturation, the samples were incubated (37&deg;C, 24 h), sealed with two coats of nail polish except for 2 mm from the apex, submerged in the Indian ink for 7 days, decalcified, dehydrated, and made transparent according to Robertson technique. Dye penetration was evaluated under stereomicroscope. Samples without dye penetration were given score 0, dye penetration ≤ 0.5 mm were given score 1, 0.51 - 1 mm were given score 2, and >1 mm were given score 3. Result: The largest proportion distribution in BS group was at the score 1 (55.6%), whereas in PS group was at the score 2 (44.4%). Conclusion: Bioceramic sealer showed similar apical leakage to polydimethylsiloxane sealer. Clinical Relevance: Based on this study, bioceramic sealer can be recommended to be used as sealer with low level of apical leakage as well as polydimethylsiloxane sealer.

Modeling of Pervaporation Separation Benzene from Dilute Aqueous Solutions Through Polydimethylsiloxane Membranes

A modified solution-diffusion model was established based on Flory-Huggins thermodynamic theory and Fujita's free volume theory. This model was used for description of the mass transfer of removal benzene from dilute aqueous solutions through polydimethylsiloxane (PDMS) membranes. The effect of component concentration on the interaction parameter between components, that of the polymer membrane on the selectivity to benzene, and that of feed concentration and temperature on the permeation flux and separation factor of benzene/water through PDMS membranes were investigated. Calculated pervaporation fluxes of benzene and water were compared with the experimental results and were in good agreement with the experimental data.