富芳烃原料合成沥青树脂的研究

以菲，催化裂化油浆的富芳烃馏分和蒽油为原料，以苯甲醛为交联剂，合成沥青树脂，并考察了不同原料合成沥青树脂的反应性，应用元素分析，FT-IR，NMR等手段，初步分析了原料及沥青树脂的结构和性能，并以此为基础推测可能的反应机理，探讨了不同原料对沥青树脂的结构和性能的影响，结果表明，树脂合成反应中的反应性因原料的不同而表现各异；沥青树脂的反应机理为质子引发下的阳离子型缩聚反应。     

萘-萘酚-苯甲醛沥青树脂的合成研究

在浓硫酸的催化作用下,采用阳离子聚合法在萘-苯甲醛二元组分沥青树脂分子链上引入了萘酚分子,合成了萘-萘酚-苯甲醛三元组分沥青树脂。用FT-IR光谱仪表征了合成树脂的结构。通过单因素实验,考察了合成条件对沥青树脂软化点、结焦值和黏结强度等黏结性能的影响规律。实验结果表明,合成萘-萘酚-苯甲醛沥青树脂适宜的工艺条件:萘、萘酚和苯甲醛的物质的量比为0.67∶0.33∶1,反应温度为160℃,反应时间为300 min,催化剂用量为10%。在此条件下,合成沥青树脂的软化点为87.5℃,结焦值为32.1%,黏结强度为41.1。改变反应体系中萘酚的物质的量,能获得具有不同黏结性能的萘-萘酚-苯甲醛三元组分沥青树脂。     

由蒽油制备COPNA树脂

以煤焦油中提取的蒽油为单体,苯甲醛为交联剂,在对甲苯磺酸的催化作用下合成缩合多核芳烃(COPNA)树脂。采用FT-IR研究其反应机理;热重分析仪研究该COPNA树脂的热行为;环球法测定了该树脂的软化点;以及元素分析仪分析其元素组成。结果表明,蒽油能够与苯甲醛合成COPNA树脂,其反应机理为酸催化下的阳离子型缩聚反应;COPNA树脂具有较好的耐热性和炭收率。     

萘-水杨醛沥青树脂的合成研究

以萘为单体,水杨醛为交联剂,在对甲基苯磺酸催化作用下合成了一种新型的萘-水杨醛沥青树脂。采用FT-IR研究了反应机理;采用TGA分析了合成树脂的热失重行为;通过单因素实验,考察了合成条件对沥青树脂收率、软化点和结焦值的影响规律。结果表明,萘与水杨醛在酸催化下发生了阳离子型缩聚反应;萘-水杨醛沥青树脂适宜的合成工艺条件为:萘和水杨醛的物质量比为1∶1,反应温度为150℃,反应时间为300 min,催化剂用量为10%。在此条件下,合成沥青树脂的收率为81.4%,软化点为79.6℃,结焦值为29.3%。水杨醛中羟基的位阻作用,有利于合成低软化点的沥青树脂黏结剂。     

苯甲醛对煤焦油软沥青的聚合改性研究

以低喹啉不溶物含量(w(QI)0.1%)的煤焦油软沥青为原料,在浓硫酸催化作用下用苯甲醛对其进行聚合改性,制备性能优良的浸渍剂沥青。采用FT-IR研究了苯甲醛的改性机理,并用TGA分析了改性沥青的热失重行为,通过单因素实验考察了改性条件对改性沥青的软化点、结焦值和族组成等性能的影响规律。结果表明,苯甲醛改性煤焦油软沥青制备炭材料用浸渍剂沥青较适宜的工艺条件为:煤焦油软沥青与苯甲醛的摩尔比为1∶1,反应温度为160℃,反应时间为150 min,催化剂用量为8%。在此条件下,改性沥青的软化点为95.1℃,结焦值为47.8%,QI含量为0.36%,达到了高性能浸渍剂沥青的指标要求。     

催化油浆重质芳烃制备沥青树脂

以催化油浆重质芳烃为原料,苯甲醛为交联剂,在浓硫酸作催化剂条件下,合成沥青树脂。采用FTIR探究了反应机理,采用TGA考察了合成树脂的热重反应性能。通过单因素实验,考察了合成条件对沥青树脂软化点、残炭量、收率的影响。结果表明,反应机理为质子催化下的缩聚反应;合成树脂的工艺条件为:交联剂用量70%,反应时间为5 h,反应温度为130℃,催化剂用量为6%。合成树脂的收率为83.2%,残炭量为27.6%,软化点为76.5℃。     

阳离子交换树脂催化合成苯甲醛1,2-丙二醇缩醛的研究

在强酸性阳离子交换树脂存在下,以苯甲醛和1,2-丙二醇为原料合成苯甲醛1,2-丙二醇缩醛。考察了反应时间、原料配比和催化剂用量等因素对合成反应的影响,确定了较佳的工艺条件:n(苯甲醛)∶n(1,2-丙二醇)=1∶1.3,带水剂环己烷为40 mL(苯甲醛为0.1 mol的情况下),强酸性阳离子交换树脂用量为2.0 g,84℃~87℃回流反应2 h。苯甲醛1,2-丙二醇缩醛的平均收率可达到91.5%,产品纯度达99.2%。     

强酸性离子交换树脂催化合成5-乙氧羰基-4-苯基-6-甲基-3,4-二氢嘧啶-2(H)-酮

在732型强酸性离子交换树脂催化下,以苯甲醛、乙酰乙酸乙酯与尿素为原料,一步合成了5-乙氧羰基-4-苯基-6-甲基-3,4-二氢嘧啶-2(H)-酮.优化的反应条件如下:苯甲醛、乙酰乙酸乙酯与尿素的摩尔比为1:3:2,732树脂用量为0.6 g,乙醇为溶剂,反应温度为80～84℃,反应时间为2 h.此时目标产物的收率为97.96%.     

石油沥青合成低软化点、高残炭沥青树脂

两种石油沥青在低温下合成沥青树脂，考察了工艺参数和原料组成对沥青树脂性能的影响。结果表明，大庆石油沥青反应活性适中、含胶质—沥青质较少，可以合成具有软化点(SP)为80～112C、残炭(CY)为59．13％、β树脂(TI～PS)含量为21．19％、喹啉不溶物(QI)值为1．32％、灰分为0．02％的优质沥青树脂，该沥青树脂已能够满足作为浸渍剂的要求。     

煤沥青的热分析

采用溶剂分离的方法对煤沥青进行组分分离,并通过TG,DTG以及DSC对煤沥青及α树脂、β树脂和γ树脂进行了分析.结果表明,煤沥青中重组分的热失重开始温度及最大失重速率温度较高,煤沥青与β树脂和γ树脂在400℃～500℃范围内均出现两个放热峰,α树脂在400℃～500℃范围内只有一个放热峰.     

热聚合-氧化法制备高β树脂改性沥青

以中温沥青为原料,通过溶剂萃取沉降分离获得低喹啉不溶物含量(QI<0.1%)的精制沥青。对精制沥青进行热聚合-空气氧化改性处理,得到高β树脂含量的改性沥青。经特定热聚合条件处理后,研究了空气氧化阶段的反应温度、氧化时间和空气流量对沥青改性的影响。实验结果表明,在空气氧化阶段,当氧化温度为280℃,氧化时间为2h,空气流量为0.04m³/h时,可以获得软化点为220℃、甲苯不溶物为61.59% 、喹啉不溶物为4.35%、结焦值为78.44%,β树脂含量为57.24%的优质改性沥青。     

Heat treatment of anthracene oil under pressure

The heat treatment of the anthracene fraction of coal tar under pressure is investigated. In the production of synthetic pitch, the temperature is varied in the range 400–480°C. The duration of the process is 5 h, and the pressure is 3–5 MPa. After treatment at temperatures below 480°C, the pitch produced lacks the quinoline-insoluble fraction. Chemical analysis shows that increasing the treatment temperature results in consumption of cata-condensed aromatic hydrocarbons, with simultaneous accumulation of peri-condensed aromatic hydrocarbons. NMR and IR spectroscopy indicates simultaneous increase in the aromatic index and the degree of condensation of samples with increase in the treatment temperature, as the result of dealkylation and condensation. Optical analysis shows clearly expressed mesogenic properties of the synthetic pitch. Pitch produced by low-temperature synthesis forms needle coke, with a greater anisotropy and greater real density than coke obtained from pitch produced by high-temperature synthesis. With increase in pressure in the course of coking, the anisotropy and the real density decline for low-temperature pitch, but increase for high-temperature pitch.     

The role of impregnants in determining the behaviour of graphite anodes

The lifetime of graphite anodes in sulphuric acid media can be increased by a factor of 3.2 by multiple impregnation with coal tar pitch. For single impregnation, linseed oil yielded the largest improvement. The results were interpreted on the premise that properties such as viscosity, melting point and coking value determine the effectiveness of the impregnant. The proper selection of the impregnant and procedure of impregnation is dependent on the electrolysis temperature.     

环氧树脂蓖麻油双重改性水性聚氨酯皮革涂饰剂的合成与性能

以聚氧化丙烯二醇(PPG)和异佛尔酮二异氰酸酯(IPDI)为原料,蓖麻油(CO)和环氧树脂(E-44)为交联剂,采用预聚体分散法合成了一系列用于皮革涂饰的环氧树脂蓖麻油双重改性水性聚氨酯(ECOWPU)。采用FTIR、TEM、DSC、TGA对聚合物结构及膜的性能进行了分析。FTIR表明聚合物中引入了蓖麻油和环氧树脂,羟基和环氧基均参与反应。通过TEM可观察乳液颗粒呈球形,粒径较为均匀。DSC表明,改性后胶膜的微相分离程度增大。TGA表明,环氧树脂和蓖麻油的加入提高了聚氨酯的热稳定性。蓖麻油、E-44含量的增加,均使胶膜拉伸强度逐渐增大,断裂伸长率、吸水率降低。当蓖麻油添加量为4.9%,E-44添加量为7%时,胶膜的综合性能最佳。     

Study of the modification of coal-tar pitch with p-methyl benzaldehyde

Coal-tar pitch is modified with p-methyl benzaldehyde (PMB) in the presence of p-toluene sulfonic acid (PTS). The main characteristics of the modified pitches such as coking value, softening point and solubility are studied in this paper. The molecular structures of the modified pitches are studied using FT-IR and ¹H-NMR spectroscopy techniques. In addition, the morphologies of the modified pitches are inspected with SEM, and the optical textures of resultant semi-cokes are characterized by polarized-light microscopy. Results show that the modified pitches have much higher coking value and β-resins content than the parent pitch. There exist many microfibers with a uniform distribution in the modified pitches. Moreover, the modification results in an improvement in the optical textures of resultant semi-cokes.     

Production of coal pitch by the oxidation of coal extracts in anthracene oil

If anthracene oil is used to produce extracts from 2B, D, 2G, GZh coal, coal pitch may be produced by oxidation of the extracts using atmospheric oxygen. The resulting pitch is characterized by higher yield and by a greater coke residue than is observed in pitch produced from anthracene oil without added coal in analogous conditions. Ultrasound treatment for 3 h on an IL10-0.63 unit ensures complete solution of the coal (4–9%) in the anthracene oil. The mineral component of the coal also enters the solution and is then concentrated in the pitch formed. To reduce the ash content of the pitch, ash must preliminarily be removed from the initial coal. For the example of 2B and D coal, it is found that reducing the ash content of the coal to ~1% and subsequent solution in the anthracene oil to a coal concentration of 5–8% yields a coal extract such that pitch with no more than 0.4% ash and up to 41% coke residue is formed on oxidation by atmospheric oxygen.     

The effect of composition of tar bond on the properties of tarred magnesite refractories

Conclusions The most effective agents for the production of tarred magnesite articles are the bonds prepared from 70% medium-temperature coal-tar pitch and 30% anthracene oil (permissible limits, 20–40%).The anthracene fraction as a solvent pitch in the preparation of the bond can replace anthracene oil.The pitch distillates as a component of the bond give inferior results compared with anthracene oil and fraction. However, considering the high cost and scarcity of the latter, in some cases, pitch distillates can be recommended for preparing bonds for the production of tarred magnesite goods.With the use of carbon oil pitch (20% coal and 80% pitch distillates) as the bond we obtain tarred magnesite specimens of satisfactory quality. From tests of petroleum bitumen we obtained unsatisfactory results. Introduction into the refractory batch of finely milled coal and coke can be of interest in the production of slag-resistant tarred magnesite articles for lining slag zones of converters.To solve the problem of the use of bonds of the recommended composition in the production of tarred magnesite refractories for lining oxygen converters, it will be necessary to carry out industrial tests.The rules obtained in this paper for the effect of composition of bonds on the properties of tarred magnesite refractories can be used for developing the technology for tarred magnesite-dolomite and tarred dolomite refractories.Translated from Ogneupory, No. 1, pp. 39–44, January, 1966.     

Carbonization and liquid-crystal (mesophase) development. 18. carbonization of coal-extract solutions (non-hydrogenated): influence of digestion conditions upon optical texture of cokes

Coal-extract solutions have been produced by the dissolution of a prime coking coal in anthracene oil followed by the removal of the undissolved solids. A range of coal-extract solutions prepared under different conditions was carbonized and the optical texture of the polished surfaces of the resultant cokes were assessed. The coal-extract solution prepared with the longest digestion time and at the highest temperature produced a coke with the largest anisotropic domains with some flow structure. Removal of the anthracene oil component of the coal-extract solution by extraction with selected solvents modified the carbonization behaviour such that although the coke yield increased substantially there was a significant decrease in the size of the anisotropic domains of the resultant cokes.