四苯乙炔基硅烷的合成及热性能研究

为得到耐热的含有苯乙炔官能团的有机硅单体,通过苯乙炔锂(由苯乙炔与丁基锂制得)与四氯硅烷的反应,合成了四苯乙炔基硅烷(TPES),通过多次重结晶获得了纯度为99.5%的TPES,并用FTIR、1HNMR、13C NMR、29Si NMR及元素分析对其结构进行了表征。对TPES及其400℃固化物的DSC、FTIR和TGA的分析表明:TPES的熔融温度范围宽达113℃(199℃~312℃);在氮气中失重5%时的温度Td5为710.8℃,800℃残炭率高达93.3%,空气中的Td5为595℃,800℃残炭率也达58.3%,耐热性能十分优异,具备作为一种耐高温聚合物材料的优秀潜质。     

Novel heat resistant methyl‐tri(phenylethynyl)silane resin: Synthesis,characterization and thermal properties

Methyl‐tri(phenylethynyl)silane (MTPES) was successfully synthesized by the reaction of lithium phenylacetylide with methyltrichlorosilane. The structure was characterized by HRMS, FTIR, ¹H‐NMR, ¹³C‐NMR, ²⁹Si‐NMR, and elementary analysis. Thermal cure process was monitored by DSC, DMA, and FTIR. MTPES was heated to free flowing liquid around 130°C and thermally polymerized at 327–377°C to form thermoset. Thermal and oxidative properties were evaluated by TGA analysis. Thermoset exhibits extremely high heat‐resistance and TGA curve in nitrogen shows the temperature of 5% weight loss (Td₅) of 695°C and total weight loss at 800°C of 7.1%. TGA shows a high Td₅ of 565°C even in air, although the total weight loss at 800°C was 56.1% of the initial weight, much higher than that in nitrogen. The high heat resistance of MTPES was ascribed to crosslinking reaction concerning ethynyl groups. Aging studies performed at elevated temperatures in air on a thermoset showed that MTPES is oxidatively stable to 300°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2488–2492, 2006     

两种甲基苯乙炔硅烷的共聚物酰亚胺改性研究

以苯乙炔与甲基二氯硅烷、甲基三氯硅烷在有机锂试剂中反应,合成了甲基二苯乙炔基硅烷(MD-PES)和甲基三苯乙炔基硅烷(MTPES)2种新型耐高温有机硅树脂。TGA和500℃烧蚀测试经酰亚胺(Imide)改性的二者共聚物的复合材料表明:其耐热保持性优异,5%热失量温度最高可达643℃,800℃质量保留率可达94.7%;材料具有较好的力学性能,弯曲强度、硬度及冲击强度可分别达到235 MPa、61和104.5 kJ/m2;复合材料介电常数与介电损耗正切值变化较小,介电性能优异;饱和吸水率在1.15%~4.79%,耐湿性能优异。     

Thermal cure behavior and pyrolysis of methyl‐tri(phenylethynyl)silane resin

A polyfunctional organic–inorganic hybrid monomer, methyl‐tri(phenylethynyl)silane (MTPES) could be thermally polymerized by a free radical mechanism to a highly crosslinked structure of interest as a high temperature composite matrix resin. The structural changes during thermal cure process were characterized by fourier transform infrared spectrum and ¹³C‐CP‐MAS‐NMR spectrum. The disappearance of secondary acetylene stretching band at 2166 cm^?1 was used successfully to monitor cure reaction accompanied with the formation of cis‐polyene structure at 1600 and 754 cm^?1. The possible cure mechanism of MTPES was also proposed. The pyrolysis of cured MTPES under a stream of argon to 1450°C gave a ceramic in high yield (81%). Thermal conversion of polymer to ceramic was studied by means of X‐ray diffraction, Raman spectrum, and energy dispersive spectrometer analysis. The results showed that pyrolytic products were made up of β‐SiC, graphite, and glassy carbon. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal characteristics and pyrolysis of methyl‐di(phenylethynyl)silane resin

Thermal stability of a recently synthesized polymeric methyl‐di(phenylethynyl)silane (MDPES) resin was studied using a number of thermal and spectrometric analytical techniques. The polymer exhibits extremely high thermal stability. Thermogravimetric analysis (TGA) shows that the temperature of 5% weight loss (T_d5) was 615°C and total weight loss at 800°C was 8.9%, in nitrogen atmosphere, while in air, T_d5 was found to be 562°C, and total weight loss at 800°C was found to be 55.8% of the initial weight. Differential thermal degradation (DTG) studies show that the thermal degradation of MDPES resin was single‐stage in air and two‐stage in nitrogen. The thermal degradation kinetics was studied using dynamic TGA, and the apparent activation energies were estimated to be 120.5 and 114.8 kJ/mol in air, respectively, by Kissinger and Coats–Redfern method. The white flaky pyrolysis residue was identified to be silicon dioxide by FTIR and EDS, indicating that the thermal stability of polymer may be enhanced by the formation of a thin silicon dioxide film on the material surface. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 103: 605–610, 2007     

Crosslinkable poly(aryl ether ketone)s containing pendant phenylethynyl moieties: Synthesis, characterization and properties

A novel phenylethynyl-contained bisphenol monomer, (2,5-dihydroxyphenyl)(4-(2-phenylethynyl)phenyl)methanone (PEBP), has been synthesized and characterized. The resultant monomer was copolymerized with hydroquinone and 4,4′-difluorobenzophenone by means of an aromatic nucleophilic substitution reaction to provide a series of crosslinkable poly(aryl ether ketone)s containing pendant phenylethynyl moieties (PE-PAEKs). The solubility of PE-PAEKs tended to be improved with the increase in PEBP content. Wide-angle X-ray diffraction (WAXD) results showed that introduction of bulky pendant groups into molecular chains led to decrease in crystallinity. PE-PAEKs were successfully cured upon heating. Dynamic mechanical analysis (DMA) results indicated that the glass-transition temperature (T_g) of the cured PE-PAEKs was increased. Thermogravimetric analysis (TGA) results implied that the thermal stability of the cured PE-PAEKs was excellent.     

Radical polymerization of (phenylethynyl)styrenes and characterization of poly(phenylethynyl)styrenes as a thermally curable material

Summary The radical polymerizations of 2-, 3-, and 4-(phenylethynyl)styrenes (1a–c) and the copolymerizations of 1a–c (M₁) with styrene (M₂) were carried out using AIBN as the initiator in toluene at 60°C. The number-average molecular weights (M _ns) were extremely low for poly(2-phenylethynylstyrene) (2a) and poly[(phenylethynyl)styrene-co-styrene] (3a), and increased in the order of 2a, 3a << 2b, 3b < 2c, 3c. Monomer reactivity ratios were determined as r ₁= 1.80 and r ₂= 0.51 for 1a, r ₁= 1.72 and r ₂= 0.53 for 1b, and r ₁= 3.17 and r ₂= 0.24 for 1c. Polymers 2a–c and 3a–c underwent an exothermic reaction at elevated temperature to form organic solvent-insoluble polymers. Although the decomposition of 2a was observed from 200°C, 2b and 2c exhibited a high heat-resistance property in both nitrogen and air atmospheres, in particular, 2b showed no significant weight loss below 450°C. Received: 28 January 1998/Accepted: 5 March 1998     

5,12-(二苯乙炔基)丁省的合成及其化学发光

由邻苯二甲酸酐与萘作用生成2-α-萘羰基苯甲酸,产率63%。2-α-萘羰基苯甲酸在无水A lC l3、NaC l催化下脱水重排,得到5,12-丁省醌,产率68%。5,12-丁省醌与苯乙炔基锂在二氧六环,DMF中反应4 h,水解后的混合物不经分离直接与氯化亚锡的盐酸溶液避光反应10 h,一步法合成目标物,收率53%。     

Synthesis,characterization and curing of m-diethylaminophenol-formaldehyde resin

Polycondensation of m-diethylaminophenol with formaldehyde has been studied under various reaction conditions. The resins formed are fusible and soluble in common organic solvents. All the resin samples have been characterized by spectral studies, measurement of solution viscosity, estimation of M?ⁿ and by t.g.a. The curing of selected resin samples by hexamine has been studied both by measuring percentage of cured material as a function of time at different temperatures and by differential scanning calorimetry. The d.s.c. data have been analyzed by various methods to evaluate the gross kinetic parameters of the curing reactions.     

硅烷芳炔-硅氧烷芳炔嵌段共聚物的合成与表征

合成了不同链段长度的卤代硅氧烷,并用其与间二乙炔基苯格氏试剂反应,合成了两种硅烷芳炔-硅氧烷芳炔嵌段共聚物（SiO-b-PSA）,并制成碳纤维增强树脂复合材料。利用红外光谱（FT-IR）、核磁共振氢谱（¹H NMR）、凝胶渗透色谱（GPC）、旋转流变、差示扫描量热分析（DSC）、热失重分析（TGA）和悬梁臂冲击实验对共聚物及其复合材料的结构和性能进行表征。研究结果表明所合成的共聚物具有优良的耐热性和韧性,硅烷芳炔-硅氧烷芳炔嵌段共聚物在氮气气氛下的T_d5高于513℃,1000℃残留率高于78.9%,硅烷芳炔-硅氧烷芳炔嵌段共聚物/碳纤维复合材料的冲击强度高达（30.92±0.44） kJ·m^-2。     

Synthesis,characterization, and thermal curing of a novel polyhedral oligomeric octa(propargylaminophenyl)silsesquioxane

A novel polyhedral oligomeric octa(propargylaminophenyl)silsesquioxane (OPAPS, (SiO_1.5C₆H₄NHCH₂C?CH)₈) was prepared from octa(aminophenyl)silsesquioxane and propargyl bromide. The chemical structure of OPAPS was characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance, X‐ray diffraction (XRD), high‐performance liquid chromatography, gel permeation chromatography, differential scanning calorimetry, and thermal gravimetric analysis (TGA). The structure of the thermally cured polymer of OPAPS was characterized by FTIR, XRD, and TGA. It had good thermal stability. TGA demonstrated that the thermal decomposition temperatures (T_d5) of the cured OPAPS polymer in nitrogen and air were 455.6 and 458.8°C, respectively. The thermal curing reaction kinetics of OPAPS were studied and some kinetic parameters were obtained. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis,characterization, and curing of o-and p-chlorophenol-furfural resins

Polycondensation of furfural, respectively, with o- and p-chlorophenols has been carried out under various reaction conditions. All the resin samples have been characterized by spectral studies, viscometric measurement and by the estimation of the number-average molecular weight. Thermogravimetric analysis (TGA) of selected resin samples has been carried out. The kinetics of curing reaction of selected resin samples has been investigated by differential scanning calorimetry (DSC). The properties of the glass laminates prepared using each of the two types of resins showed that the latter are much less suitable than phenol-furfural resin as matrices for the fabrication of laminates.     

1-甲氧基-9,10-双(苯乙炔基)蒽的合成

由１－硝基蒽醌与甲酸钠作用生成１－甲氧基蒽醌,收率７５％。１．甲氧基蒽醌与苯乙炔基溴化镁在ＴＨＦ中回流２４ｈ,水解后的混合物不经分离直接与氯化亚锡的乙酸溶液反应３０ｍｉｎ,一步法合成了题示化合物,收率４６％。     

Novel phenyl acetylene terminated poly(carborane‐silane): Synthesis,characterization, and thermal property

Phenyl acetylene terminated poly(carborane‐silanec) (PACS) was synthesized by the couple reaction of methyldichlorosilane with 1,7‐dilithio‐m‐carborane and lithium phenylacetylide. The structure was characterized using FTIR, ¹H‐NMR, ¹³C‐NMR, ²⁹Si‐NMR, and gel permeation chromatography. PACS exhibits solubility in common organic solvents. Thermal and oxidative properties were evaluated by thermogravimetric analysis (TGA). Thermoset exhibits extremely thermal and oxidative property and TGA curves show that the temperature of 5% weight loss (Td₅) is 762°C and char yield at 800°C is 94.2% in nitrogen. In air, surprisingly, both Td₅ and char yield at 800°C show slight increase, which is greater than 800°C and 95.6%, respectively. After pyrolysis, the char has no additional weight loss up to 800°C in air. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2498–2503, 2007     

Synthesis,characterization, and UV curing kinetics of hyperbranched polycarbosilane

Hyperbranched polycarbosilane with allyl end groups was synthesized via hydrosilylation of methyldiallyldilane, and characterized by Fourier transform infrared spectroscopy, ¹H, ¹³C, ²⁹Si nuclear magnetic resonance, and size exclusion chromatography/multiangle laser light scattering. The degree of branching and average number of branches of the resulted polymer determined by ²⁹Si NMR spectroscopy is 0.58 and 0.42, and the exponent α in Mark–Houwink equation is 0.33 based on the relationship between viscosity and molecular weight. UV curing behaviors of the hyperbranched polycarbosilane were investigated using differential scanning photocalorimeter, and the effects of diluent's concentration, light intensity, reaction atmosphere, and temperature on the curing behaviors and kinetics were studied in detail. It was found that curing reaction can be accomplished rapidly under UV irradiation within 40 s both in air and in nitrogen atmosphere if acrylic reactive diluent was employed. The result suggests that it is an effective way to increase the curing reactivity by incorporating acrylic reactive diluents with high UV sensitivity into the polycarbosilane system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis,characterization, and swelling behavior of poly(N-hydroxymethylacrylamide) grafted poly(vinyl alcohol)

In this study, the graft copolymerization of N-hydroxymethylacrylamide (NHMAAm) with poly(vinyl alcohol) (PVA) was carried out by using potassium persulfate/N,N,N,N-tetramethylethylenediamine (K₂S₂O₈) to improve physicochemical properties and functionality of PVA. The structures of PVA-g-poly-NHMAAm (PNHMAAm) copolymers were characterized by Fourier transform infrared, elemental analysis, nuclear magnetic resonance (¹H-NMR), ¹³C-NMR, and size exclusion chromatography. Their thermal behaviors were investigated by differential scanning calorimetry and thermogravimetric analysis (TGA). The TGA results indicated that the graft copolymers show better thermal stability then PVA. The effects of reaction time, temperature, NHMAAm, and K₂S₂O₈ concentrations on grafting parameters were examined. The maximum grafting yield (34.01%) was provided when reaction was carried out under optimum conditions (time = 2 hr, T = 40°C, [NHMAAm] = 0.25 M, [K₂S₂O₈] = 4.56 × 10⁻³ M). Moreover, PVA-g-PNHMAAm membranes were prepared and their swelling behaviors were studied. The results demonstrated that swelling degree of graft membranes increased almost 3.5-fold compared to PVA membrane.     

三炔丙基异氰尿酸酯的合成、表征及其非等温固化动力学

以3-溴丙炔、异氰尿酸为原料,利用相转移催化剂合成了三炔丙基异氰尿酸酯(TPIC),并用FT-IR、¹H NMR对其结构进行了表征。用TGA表征了热固化后的TPIC的热性能。结果表明：热固化后的树脂在375℃开始分解,800℃的残炭率达75%。根据DSC曲线,TPIC的熔点为167℃左右,并用Kissinger、Flynn-Wall-Ozawa和Friedman-Reich-Levi法分别计算了热固化反应活化能,它们分别为46.81、48.70和40.92 kJ·mol^-1,热固化反应级数都接近1,并探讨了固化反应过程与机理。通过对比分析表明,这3种方法均适用于TPIC体系。     

Synthesis, characterization and non-isothermal curing kinetics of tri-propargyl isocyanurate

以3-溴丙炔、异氰尿酸为原料,利用相转移催化剂合成了三炔丙基异氰尿酸酯(TPIC),并用FT-IR、¹H NMR对其结构进行了表征。用TGA表征了热固化后的TPIC的热性能。结果表明：热固化后的树脂在375℃开始分解,800℃的残炭率达75%。根据DSC曲线,TPIC的熔点为167℃左右,并用Kissinger、Flynn-Wall-Ozawa和Friedman-Reich-Levi法分别计算了热固化反应活化能,它们分别为46.81、48.70和40.92 kJ·mol^-1,热固化反应级数都接近1,并探讨了固化反应过程与机理。通过对比分析表明,这3种方法均适用于TPIC体系。     

Synthesis,characterization, and flocculation properties of poly(acrylamide‐methacryloxyethyltrimethyl ammonium chloride‐methacryloxypropyltrimethoxy silane)

A novel hydrophobically modified and cationic flocculant poly(acrylamide‐methacryloxyethyltrimethyl ammonium chloride‐methacryloxypropyltrimethoxy silane) (P(AM‐DMC‐MAPMS)) was synthesized by inverse emulsion polymerization. The molecular structure of hydrophobically cationic polyacrylamide (HCPAM) was characterized by FTIR and ¹H‐NMR. The effects of DMC and MAPMS feed ratio on intrinsic viscosity and solubility were measured. The effects of hydrophobically cationic flocculants on reactive brilliant red X‐3B solution and kaolin suspension were studied. It was found that the introduction of MAPMS could increase the intrinsic viscosities of P(AM‐DMC‐MAPMS) and enhance the flocculation properties to anionic dye solution and kaolin suspension, but reduced their water‐solubility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

枝状聚(苯基-二甲基)硅烷的合成及其性质研究

以苯基三氯硅烷、二甲基二氯硅烷为原料，利用伍兹反应使其共聚生成聚（苯基二甲基）硅烷。在不同投料比下，发现枝化度越高，聚合物分子量越小，分子量分布越宽，产率越高；并用红外光谱厦29Si—NMR谱对其结构进行表征，用紫外光谱和热失重表征其光学性质和热稳定性，发现聚合物在211nm处有尖锐吸收峰，并拖尾至380nm处，热分解温度约在500℃左右，高于一般的线形聚硅烷。