Thermal evolution and crystallisation of polydimethylsiloxane–zirconia nanocomposites prepared by the sol–gel method

Polydimethylsiloxane–zirconia nanocomposites have been prepared by hydrolysis of diethoxydimethylsilane and zirconium n-propoxide in different molar ratios. Transparent, homogeneous and non-porous xerogels have been obtained up to 70 mol% ZrO₂ content. The starting xerogels have been pyrolyzed under argon atmosphere up to 1400°C and the structural evolution of samples treated at different temperatures has been followed by X-ray diffraction, transmission electron microscopy, infrared and ²⁹Si solid state nuclear magnetic resonance spectroscopies, thermal analyses and N₂ sorption measurements. The polymer-to-ceramic conversion leads to the structural rearrangement of the siloxane component with the production at 600°C of high surface area materials with pore sizes below 3 nm. Samples are amorphous up to 800°C. At 1000°C, the structural evolution of the silicon moiety produces an amorphous oxycarbide phase whereas the primary crystallisation of tetragonal zirconia takes place, with crystallinity and crystallite sizes depending on the ZrO₂ content. At 1400°C, the silicon oxycarbide phase generates a mixture of amorphous silica and crystalline silicon carbide polymorphs. In this matrix, tetragonal and monoclinic ZrO₂ phases are present with ZrO₂ average crystallite dimensions never exceeding 20 nm, for ZrO₂ content ≤50 mol%. The tetragonal/monoclinic ratio as well as the crystallite sizes appear strictly related to the chemical composition. ©     

有机硅烷偶联剂改性紫外光固化超支化聚醚基水性聚氨酯的性能

采用超支化聚酯Boltorn H 20与丁二酸酐反应,制备了亲水性超支化聚酯,然后与甲基丙烯酸酯基改性的聚醚基聚氨酯预聚体和3-异氰酸酯基丙基三乙氧基硅烷(IPTS)反应,合成了有机硅烷偶联剂改性紫外光固化聚醚基超支化水性聚氨酯(WHPU)。考察了有机硅烷偶联剂用量对WHPU的耐酸性、固化时间、凝胶质量分数、附着力、水接触角、水吸附率、乳液粒径分布及热稳定性的影响。结果表明,当IPTS与Boltorn H 20中羟基的摩尔比为6/16时,固化后的WHPU膜的凝胶质量分数为92%,在玻璃表面的附着力达到0级;与不含有机硅烷偶联剂的WHPU相比,该涂膜的水接触角和热稳定性分别提高了34°和22℃,其吸水率从13.8%降低到4.3%。     

Synthesis and properties of ultraviolet/moisture dual‐curable polysiloxane acrylates

Ultraviolet (UV)/moisture dual‐curable polysiloxane acrylates (PSAs) were prepared from N,N‐bis[3‐(triethoxysilyl)propyl]amine (G402) and ethoxylated trimethylolpropane triacrylate (EB160) through Michael addition. The obtained prepolymers were characterized by ¹H‐NMR and FTIR. The rheological behavior of the prepolymers exhibited the properties of a Bingham fluid and the apparent viscosity was directly correlated with molecular weight. The photocuring kinetics of PSA were studied using photo‐DSC and all the polymerization conversions were high. With increasing content of tertiary amine in the prepolymer, the photocuring rate in air increased as well. The moisture‐curing kinetics of the prepolymers was studied using FTIR. It was found that the curing mechanism may be described as the transforming of Si O C into Si O Si structure, which was consistent with the theoretical expectation. DSC and TGA were used to characterize the glass‐transition temperatures and the thermomechanical stability of the prepolymers. Measurements of physical properties showed excellent gloss, impact strength, and high electric resistance for both UV‐ and moisture‐cured films, but poor adhesion for UV‐cured films and lower hardness for moisture‐cured films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 846–853, 2005     

Block polymers from isocyanate-terminated intermediates. III. Preparation and properties of cured diene–urea block polymers

Isoprene–urea and butadiene–urea block polymers have been prepared by reaction of isocyanate-terminated prepolymers with diamines and diisocyanates. It was found that the per cent of blocked urea in these copolymers is dependent on the isocyanate–diamine stoichiometry. Stress–strain data were obtained on sulfur-cured copolymers. Stress levels at any given extension were directly dependent on the urea content, however, ultimate strength was maximized at about 35 wt-% urea. Slight variations in urea structure produced rather dramatic changes in the modulus of these cured elastomers. Diamine–diisocyanate stoichiometry did not affect the physical properties of these cured copolymers at equal or excessive diamine concentrations. However, at excess diisocyanate levels, elastomeric properties deteriorated rapidly. Finally, stress–strain properties were affected by polymerization solvent. Copolymers prepared in hexane gave higher values of stress at low strains than corresponding elastomers prepared in toluene. These latter results are explained in terms of the nonaqueous emulsion in which the urea blocks form.     

超支化聚氨酯丙烯酸酯的合成及其固化膜性能

以合成的甲苯-2,4-二异氰酸酯.丙烯酸羟丙酯(TDI.HPA)单体对超支化聚酯(HBPE)进行端羟基改性,得到超支化聚氨酯丙烯酸酯(HBPUA)。研究了反应温度、时间对产物游离—NCO含量的影响,通过摆杆硬度、附着力、柔韧性、冲击强度等测试研究了活性单体的种类及用量对固化膜性能的影响,并采用FT-IR及TG对HBPE,HBPUA及其固化膜进行了表征和分析。结果表明,合成HBPUA的最佳条件为:n(2,4-TDI):n(HPA):n(HBPE)=6:6:1,反应温度70℃,反应时间3 h,催化剂二月桂酸丁基锡(DBTDL)用量为总质量的0.6%;TDI.HPA的合成反应温度35℃,反应时间2.5 h,DBTDL用量为总质量的0.4%。采用己二醇二丙烯酸酯为活性单体并控制其质量分数为20%时,超支化聚氨酯丙烯酸酯涂膜的力学性能、热稳定性较好。     

Structure–properties relations of thermally cured epoxy–lignin polyblends

A bisphenol A based epoxy adhesive (EP) was modified by polyblending with Kraft Lignin (L). A systematic investigation of the thermally cured EP-L polyblends with up to 40% by weight L was undertaken. Adhesive shear tests, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and solid-state CP-MAS NMR spectroscopy were performed to establish the effect of L on the mechanical properties of the polyblends and on the morphology of these crosslinked structures. The possibility of an enhanced degree of bonding between L and the EP network is discussed. This bonding can arise from a chemical reaction between L and some unreacted amine groups present in the hardener.     

Hydrolytic degradation of cured urea–formaldehyde resin

The degradation of cured urea–formaldehyde (UF) resin in aqueous suspension was investigated by gravimetric analysis of the changes in the content of nonextractable low-molecular components. In acid conditions (pH 4.0) at 47°C the consecutive processes of post-curing and of polymer break-down (activation energy 90 kJ/mol) are detectable whereas at 80°C and 97°C only the formation of the extractable hydrolysates is observed. The degraded polymer contains less carbonyl groups than does the original resin substrate as shown by means of infrared (IR) analysis. In contrast to the results of the tests carried out in acid conditions, in neutral and basic aqueous media the hydrolytic decomposition of UF macromolecular network is less significant. During the hydrolysis of UF polymer at 30°C–45°C the concentration of formaldehyde released from the resin to the aqueous phase increases initially (2 days) at a relatively high rate both at acid and alkaline pH. Then its growth slows down but is still detectable in acid conditions, whereas in basic medium no further liberation of HCHO is observed.     

Acrylated lesquerella oil in ultraviolet cured coatings

A triglyceride of hydroxy fatty acids, lesquerella oil (LO), was structurally modified and used for the first time in the design, synthesis and evaluation of UV cured coatings. The results demonstrate that LO derivatives improved adhesion to metal substrates. For instance, methacrylated LO significantly improved adhesion to steel, and hydroxyethylmethacrylated LO improved adhesion to steel and aluminum substrates. The use of LO derivatives slightly lowered crosslink density and solvent resistance, and increased flexibility at the expense of T_g.     

SBS/丙烯酸酯紫外光固化压敏胶的结构与固化过程

对由SBS(苯乙烯-丁二烯-苯乙烯嵌段聚合物)和丙烯酸酯类单体组成的胶液进行紫外光(UV)辐照固化,制备压敏胶(PSA)。采用UV-DSC(差示扫描量热法)、FT-IR(红外光谱)等检测手段对UV固化胶液的聚合反应过程、PSA的结构进行了表征和分析,并提出了简单的结构模型。结果表明:胶液中的丙烯酸酯类单体发生自由基聚合反应,并与SBS发生接枝和交联反应,形成半互穿聚合物网络(semi-IPN)结构;固化后PSA的交联程度随SBS用量的增加而增大;当w(SBS)=5%时,PSA的凝胶含量可达到46%;在UV辐照下,SBS/丙烯酸酯胶液的反应速率随UV辐照强度或光引发剂用量的增加而增大,固化反应在80s内已基本完成。     

Preparation and pervaporation performances of fumed‐silica‐filled polydimethylsiloxane–polyamide (PA) composite membranes

Fumed‐silica‐filled polydimethylsiloxane (PDMS)–polyamide (PA) composite membranes were prepared by the introduction of hydrophobic fumed silica into a PDMS skin layer. The cross‐sectional morphology of these filled composite membranes was observed with scanning electron microscopy. Their pervaporation performances were tested with aqueous ethanol solutions at 30, 35, and 40°C. Increasing the amount of the fumed silica resulted in significantly enhanced ethanol permeability of the membranes. When the content of the fumed silica in the PDMS skin layer was 20 wt %, the ethanol permeability increased to nearly twice that of the unfilled PDMS–PA composite membrane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Polyurethane–urea anionomer dispersions. I

Polyurethane–urea anionomer dispersions with different stoichiometric DMPA/polyol and NCO/OH ratios were preapred from poly(oxypropylene)glycol, toluene diisocyanate (TDI), dimethylolpropionic acid (DMPA), and ethylenediamine (EDA). The dispersion-cast films were prepared and characterized by mechanical properties, dynamic mechanical analysis (DMA), and differential scanning calorimetry (DSC). Increasing the hard-segment content by either increasing the DMPA/polyol or the NCO/OH ratios affects the glass transition temperature (T_g) of the soft segments. © 1994 John Wiley & Sons, Inc.     

Recovery of alcohols from water using polydimethylsiloxane–silica nanocomposite membranes: Characterization and pervaporation performance

Different polydimethylsiloxane (PDMS) nanocomposite membranes were synthesized by incorporating various contents of nanosized silica particles to improve the PDMS pervaporation (PV) performance. A uniform dispersion of silica nanoparticles in the PDMS membranes was obtained. The nanocomposite membranes were characterized morphologically by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results showed that surface roughness increases by incorporating silica, and this decreases absorption of penetrants on the membrane. Swelling studies showed that the presence of silica nanoparticles into the PDMS membranes decreases degree of swelling, which can be attributed to rigidification of the PDMS matrix. Additionally, the results revealed that helium permeability decreases through the nanocomposite membranes, due to the more polymer chains packing. Effects of silica on recovery of isopropanol (IPA) from water mixtures were also investigated. Based on the results, incorporating silica nanoparticles promotes significantly the PDMS membrane selectivity because the polymer chains are rigidified and also the polymer free volume decreases. However, permeation flux decreases as diffusion of the penetrants reduces in the presence of silica nanoparticles within the PDMS membranes. As PV performance depends on operating conditions, effects of feed composition, and temperature were also studied. Moreover, recoveries of IPA, ethanol, and methanol from water mixtures were compared using the PDMS‐silica nanocomposite membranes. The results demonstrated that polarity and solubility of alcohols affect permeation flux and selectivity resulting in the higher permeation flux and selectivity for IPA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Water‐borne melamine–formaldehyde‐cured epoxy–acrylate corrosion resistant coatings

Organic protective coatings are widely used in corrosion control. However, environmental standards establish that the volatile organic compounds either must be removed or controlled at the lowest possible levels. The carcinogenic environmental impact of volatile organic compounds has led to the substitution of solvent‐borne coatings by water‐borne coating systems. Among recently developed water‐borne coatings, epoxy‐ and acrylic‐based coatings have a special significance over other reported water‐borne systems. Keeping in mind, the importance of water‐borne coatings in the present work, we report the synthesis of water‐borne epoxy–acrylate (EpAc) and melamine–formaldehyde (MF) as well as formulation of their anticorrosive coatings. The structural elucidation of MF‐cured EpAc was carried out by FTIR, ¹H NMR, and ¹³C NMR spectroscopic techniques. The coatings of EpAc‐MF were applied on mild steel strips and were evaluated for physicochemical, physicomechanical characterization, and the anticorrosive performance under different environmental conditions. The present coating system EpAc coatings exhibited superior performance as compared to the reported water‐borne epoxy–acrylatecoatings. The presence of melamine–formaldehyde in the resin increases the scratch hardness, impact resistance, alkali resistance, and thermal stability of these coatings. EpAc‐MF‐1 was found to cure at ambient temperature and exhibit good physicomechanical properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Cross-linking decrystallized and partially acetylated cotton yarn with dimethylol–dihydroxy–ethylene–urea

Easy-care finishing of cotton fabrics invariably results in the loss of mechanical properties of the fabrics. There have been many attempts from time to time by different workers to reduce the above loss in the mechanical properties. But the problem is yet to be resolved satisfactory. As the uniform distribution of cross-links in the resin-finished structure of cellulose is the key for achieving a better balance of mechanical properties, the present work aims at a suitable modification of the cellulose matrix to achieve the goal. The paper reports the mechanical properties of the modified and cross-linked cotton yarn. The cross-linked samples of the modification treatment involving swelling the yarn at normal stretch with 20% NaOH and partially acetylating without washing off the alkali have displayed higher tenacity, elongation, and toughness, with better easy-care properties as compared to the control.     

Mechanical and thermal properties of UV cured mixtures of linear and hyperbranched urethane acrylates

The properties of urethane acrylate resin mixtures based on the linear and hyperbranched aliphatic polyesters were examined. Linear polyester was synthesized from neopentil glycol and adipic acid. Hyperbranched polyester of the third generation was synthesized from 2,2-bis(hydroxymethyl)propionic acid and di-trimethylol propane. The modification of 60% of hyperbranched aliphatic polyester OH end groups was carried out with isononanoic acid or with soybean fatty acids. Two hyperbranched urethane acrylates, with the same degree of acrylation, and one linear urethane acrylate were obtained by reaction of appropriate polyester and isophorone diisocyanate and 2-hydroxyethyl acrylate. The influence of added amount of HUA and nature of non-acrylic end groups on the rheological, mechanical and thermal properties of the uncured and UV cured mixtures diluted with 20 wt.% hexanediol diacrylate was examined. The nature of non-acrylic end groups have great effect on the interaction between linear and hyperbranched urethane acrylates, which further has a crucial influence on the examined properties of uncured and UV cured mixture samples.     

三官能度含磷聚氨酯丙烯酸酯的合成及性能研究

采用异佛尔酮二异氰酸酯、羟基封端的聚丙二醇或聚己二酸丁二醇酯、丙烯酸羟乙酯合成含异氰酸基的聚氨酯丙烯酸酯与三氯氧磷和乙二醇合成的磷酸三乙二醇酯反应,制备了三官能度的含磷聚氨酯丙烯酸酯聚合物,并用红外光谱对其进行了表征。以该类聚合物和三缩丙二醇双丙烯酸酯为基料配制光固化涂料,并对其固化膜性能进行了研究。结果表明:不同聚合物所配制的涂料性能有一定差异,但都具有较好的光固化性能,固化涂膜各种物理性能优良,热稳定性能好,480℃下残重7.8%以上。     

Preparation and properties of polydimethylsiloxane‐mica composites

This is a comparison study of the effects of various colloids on polydimethylsiloxane (PDMS) nanocomposites. Mica of layered structure and silica of nanospherical shape were both used with different content. Silane coupling agent was used for surface modification of mica to improve its dispersion. Wide X‐ray diffraction patterns showed no intercalation during the incorporation of mica into PDMS matrix. Rheological characterization of the PDMS composites before curing showed that viscosities of PDMS‐mica composites were much lower than that of PDMS composites with silica, particularly at low shear rates. Scanning electron microscope (SEM) suggested the existence of mica lamellar structure with high aspect ratio within the PDMS matrix. After vulcanization at room temperature, PDMS‐mica composites could obtain mechanical properties close to that of PDMS composites with silica at same filler content. The cooperative effects of mica with silica showed that same mechanical properties of PDMS composites could be obtained at much lower viscosity, cost, and processing insecurity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Studies on mechanical,thermal, and morphology of diglycidylether‐terminated polydimethylsiloxane‐modified epoxy–bismaleimide matrices

An epoxy matrix system modified by diglycidylether‐terminated polydimethylsiloxane (DGETPDMS) and bismaleimide (BMI) was developed. Epoxy systems modified with 4, 8, and 12% (by wt) of DGETPDMS were made using epoxy resin and DGETPDMS, with diaminodiphenylmethane as the curing agent. The DGETPDMS‐toughened epoxy systems were further modified with 4, 8, and 12% (by wt) of BMI, namely (N,N′‐bismaleimido‐4,4′‐diphenylmethane). DGETPDMS/BMI/epoxy matrices were characterized using differential scanning calorimetry, thermogravimetric analysis, and heat deflection temperature analysis. The matrices, in the form of castings, were characterized for their mechanical properties, viz. tensile strength, flexural strength, and impact test, as per ASTM methods. Mechanical studies indicate that the introduction of DGETPDMS into epoxy resin improves the impact strength, with reduction in tensile strength, flexural strength, and glass transition temperature, whereas the incorporation of BMI into epoxy resin enhances the mechanical and thermal properties according to its percentage content. However, the introduction of both DGETPDMS and BMI enhances the values of thermomechanical properties according to their percentage content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 668–674, 2006     

Block polymers from isocyanate-terminated intermediates. IV. Properties of cured butadiene–ε-caprolactam block polymers

Butadiene–ε-caprolactam block polymers containing a high proporation of 1,2 units in the butadiene-segments were synthesized and physical properties were measured on the cured copolymers. Flexural strength and impact resistance both increase regularly with increasing ε-caprolactam content in peroxide cured copolymers. This behavior is explained by the higher values of flexural modulus and impact resistance for poly(ε-caprolactam) compared with peroxide-cured polybutadiene resins. Copolymers reinforced with silica showed higher heat distortion temperatures but lower impact resistance than corresponding unfilled samples. Arrhenius plots of flexural properties at various test temperatures were linear. Both flexural modulus and strength decreased regularly with increasing test temperature. Flexural properties of filled copolymers were relatively unaffected by heat aging up to 204°C for several weeks, however, dramatic decreases in these properties were noted in a matter of days when heat aging was done at 260–316°C. These results are explained by the rapid degradation of poly(ε-caprolactam) above its melting point. Block polymers whose butadiene segments contained a high proportion of 1,4 units were also synthesized. These copolymers were elastomeric when cured with either sulfur or peroxide.     

Water absorption and hygrothermal ageing of ultraviolet cured glass‐fiber reinforced acrylate composites

In this article, an ultraviolet curable glass fiber reinforced polymer (UV‐GFRP) composite developed for fast repair or strengthening of concrete structures, was investigated on its water absorption and hygrothermal ageing behaviors. Cured UV‐GFRP coupons were subjected to immersion in distilled water or concrete pore solution (pH value around 13) for 4–8 months at room temperature and elevated temperatures (40 and 60°C), respectively. Water absorption and thermomechanical properties of the samples were tested as a function of immersion time. Water uptake curves of UV‐GFRP exposed to elevated temperatures and/or alkaline solutions show serious mass loss. Debonding of fibers from resin matrix brought in increased coefficient of diffusion along fiber directions, due to the capillary effect. After 4 months of immersion in both media, the tensile strength of UV‐GFRP was deteriorated remarkably, while the tensile modulus was less affected. According to Arrhenius equation, the tensile strength of UV‐GFRP is predicted to remain 77.6% of its original value after50 years when immersed in water at 20°C, but only 24.5% left in the case of alkaline solution. This suggests that the present UV‐GFRP system does not suit for the application in strong alkaline environments. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers