高温煤焦油增韧酚醛泡沫的制备及性能表征

以高温煤焦油为原料,部分替代石油基苯酚合成可发泡性酚醛树脂,通过发泡工艺制备煤焦油酚醛泡沫。利用气相色谱质谱仪和红外光谱仪分别对高温煤焦油和酚醛泡沫进行分析表征;采用光学显微镜、热重分析仪、极限氧指数仪、导热系数仪等对酚醛泡沫的表观形貌、压缩强度、粉化率、热稳定性、阻燃性能和隔热性能进行表征。结果表明,煤焦油酚醛泡沫的压缩强度有所降低,但是泡沫的韧性提高,其粉化率下降。同时煤焦油酚醛泡沫具有良好的热稳定性,当替代率为10%-15%时,极限氧指数最高为36.1%,导热系数最低为0.034 W/（m·K）。这说明,高温煤焦油能够部分替代苯酚制备出性能优良的酚醛泡沫,为高温煤焦油的高值化利用提供了新的思路。     

热塑性聚氨酯微孔发泡材料的表观密度与其力学性能的关系

用高压CO2流体通过升温发泡法制备了一系列不同表观密度的热塑性聚氨酯(TPU)微孔发泡材料,探究了TPU发泡材料的表观密度与其力学性能的关系.微孔发泡材料的泡孔结构和表皮结构由扫描电子显微镜表征;不同表观密度材料的力学性能利用万能材料试验机和旋转流变仪表征.研究发现:TPU微孔发泡材料的表观密度主要是由材料皮层厚度占比和泡孔层密度决定的,皮层厚度占比越小和泡孔面积占有率越高,泡沫的表观密度越小;微孔发泡材料在线性应变区的压缩模量E与材料表观密度ρ的关系为:E∝ρ1.7,符合泡沫材料压缩模量与表观密度呈指数关系的基本结论;循环压缩实验中,随微孔发泡材料表观密度减小,损耗百分比增大,残余应变减小;流变实验中,微孔发泡材料的模量随表观密度变化没有明显的变化,阻尼因子tanδ随泡沫表观密度变化不呈单一的规律性.同时,阐明了微孔发泡材料的压缩模量E和损耗百分比随表观密度变化的机理.     

空心玻璃微珠复合聚酰亚胺泡沫的泡孔结构与性能

通过填充空心玻璃微珠,采用预聚法制备了空心玻璃微珠复合聚酰亚胺泡沫,研究了空心玻璃微珠填充量对复合聚酰亚胺泡沫的泡孔结构、热性能和压缩性能的影响规律。结果表明,随着空心玻璃微珠填充量的增加,聚酰亚胺泡沫泡孔结构变得精细,并且热稳定性、玻璃化转变温度和压缩性能都随之提高。当填充量(空心玻璃微珠与均苯四甲酸酐的质量比)达到20%时,泡沫5%热失重温度提高了13.9℃,玻璃化转变温度提高了8.1℃,压缩强度提高了约21%,压缩模量提高了约12%。     

低温煤焦油增韧酚醛泡沫的制备及性能表征（英文）

本研究以低温煤焦油为原料，部分替代石油基苯酚制备煤焦油基酚醛泡沫（CPF），对CPFs的化学结构、表观形貌、压缩强度、粉化率、热稳定性、阻燃性能和隔热性能进行了表征。结果表明，CPFs与常规酚醛泡沫的化学结构相似。与常规酚醛泡沫相比，30%CPF和40%CPF的压缩强度分别增加了18.3%和55.9%；且由于脂肪结构如烷基酚的引入，使得泡沫的韧性显著提高，其粉化率分别下降了22.9%和50.8%。此外，CPFs在低温下的热稳定性增加。尽管CPFs的极限氧指数下降，导热系数增加，但依然保持较好的阻燃和隔热性能。这说明低温煤焦油能够高比例地替代苯酚制备出性能优良的酚醛泡沫，为低温煤焦油的高值化利用提供了新的思路。     

THIEC改性三聚氰胺甲醛树脂泡沫的制备及其性能表征

首先,采用三-(2-羟乙基)异氰酸脲酯(THIEC)作为增韧剂对三聚氰胺甲醛树脂(蜜胺树脂)进行化学改性,以提高树脂的韧性。然后,将改性蜜胺树脂与表面活性剂、发泡剂、固化剂、成核剂等充分混合搅拌,采用普通热发泡法制得三聚氰胺甲醛树脂泡沫(蜜胺泡沫)。用扫描电子显微镜(SEM)、氧指数仪、万能电子试验机、导热系数仪对蜜胺泡沫的形态结构、阻燃性能、力学性能及热绝缘性能进行了测试和分析。探究了发泡剂、固化剂用量对蜜胺泡沫表观密度及形态的影响。结果表明:当THIEC、发泡剂、固化剂、成核剂的用量依次为蜜胺树脂质量的15%、10%、6%、2%,发泡温度为80℃时,蜜胺泡沫的压缩强度达到150kPa、极限氧指数为34、导热系数为0.027W/(m·K),综合性能良好。     

可膨胀石墨阻燃高回弹聚氨酯泡沫塑料的性能

在原料中添加可膨胀石墨(EG),采用一步法合成了阻燃型高回弹聚氨酯软泡,研究了EG对泡沫性能的影响.用扫描电镜和光学显微镜观察了EG粒子在泡沫内的固着状态及其对泡孔形貌和泡沫燃烧后的炭层形貌的影响.垂直-水平燃烧实验和极限氧指数实验检测了EG的添加量对于泡沫燃烧的抑制情况.考察了EG粒子的含量对泡沫密度、拉伸及压缩力学...     

含磷有机硅杂化环氧树脂固化体系性能研究

通过磷酸与γ-环氧丙氧基三甲氧基硅烷反应得到含磷有机硅氧烷,并加入到环氧树脂/4,4'-二氨基二苯基甲烷体系中混合,通过溶胶-凝胶的方法制备了含磷有机硅杂化环氧树脂固化物.对固化体系进行了玻璃化转变温度、热失重、阻燃、拉伸强度、冲击强度测试分析.结果表明,该固化体系的阻燃性得到提高,极限氧指数在25.8～29.3,玻璃化转变温度得到提高,在161～179℃;虽然初始分解温度比纯环氧树脂固化物低,但800℃残炭率可以达到26.5%,提高了36%;拉伸强度得到提高,在71～94 MPa,冲击强度可以达到14.36 kJ/m2,提高了14%.该固化体系具有较好的阻燃性能和热性能,同时具有较好的力学性能.     

偶氮复合发泡剂对交联聚氯乙烯泡沫结构和性能的影响

采用异氰酸酯和环氧树脂作为交联剂,偶氮二异丁腈（AIBN）和偶氮二甲酰胺（AC）作为发泡剂制备了交联聚氯乙烯泡沫材料。 通过扫描电子显微镜分析了两种发泡剂的粒径、比例以及用量对泡孔结构的影响。 结果表明,AIBN的粒径对泡沫的泡孔结构影响不大,但其用量增加导致泡沫密度减小;AC的粒径对泡孔结构产生一定的影响,最优的粒径范围为8～20 μm,并且随着用量增加,泡孔尺寸变小,但对密度影响不大。 采用DSC研究了AIBN和AC在预混料中的分解情况,提出了两种发泡剂影响泡沫的泡孔结构的机理。 对泡沫材料力学性能的分析表明,泡沫的强度随密度的增加而增加,剪切变形则在60～80 kg/m3密度范围内出现最大值。     

带环氧基团纳米二氧化硅改性酚醛树脂的合成及热性能

以苯酚、甲醛、带环氧基团纳米二氧化硅(RNS-E)为原料,采用原位聚合法合成了RNS-E改性酚醛树脂.利用红外光谱(FT-IR)对其结构进行了分析,并利用热重分析(TGA)对其热性能进行了研究.结果表明,改性后的酚醛树脂热稳定性得到提高,当RNS-E的加入量为4%时(质量分数),失重10%时的热分解温度(t10%)较酚醛树脂的提高了15℃,1 000℃下残炭率较酚醛树脂提高了7%.     

聚酰亚胺泡沫材料的制备与性能表征

采用3,3′,4,4′-二苯甲酮四甲酸二酐(酮酐,BTDA)和4,4′-二氨基二苯甲烷(MDA)为主要原料制备了一种聚酰亚胺泡沫材料.采用傅里叶变换红外光谱(FTIR)、核磁共振氢谱(1H-NMR)、扫描电镜(SEM)、导热系数测定仪、热失重分析(TGA)、差式扫描量热分析(DSC)及驻波管分别对前聚体粉末化学结构、泡沫泡孔结构、热性能及声学性能进行了表征.研究结果表明前聚体粉末以聚酰胺酯和铵盐两种形式存在,所得泡沫泡孔均匀,并且随前聚体干燥温度升高,泡孔尺寸变小.泡沫的导热系数λ为7.62×10-3W/(m.K),失重5wt%的分解温度Td5为540℃,玻璃化转变温度Tg为306℃,表明其具有优良的隔热耐热性.并且由声学测试可知在0～2000Hz频率范围内,吸声系数可达0.79,传声损失可达19.4dB,具有低频吸声、隔声性.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.