中低温煤焦油基炭微球的制备

通过馏分切割、温和加氢相结合对中低温煤焦油进行精制处理，精制后的原料采用分级热聚制备中间相炭微球。考察了精制处理条件对原料性质、中间相炭微球宏观外貌及微晶结构的影响。采用FTIR、GC-MS、族组成、元素分析对原料进行表征，采用SEM、XRD对中间相炭微球进行表征。结果表明：中低温煤焦油中300～430℃馏分油是制备中间相炭微球的较佳馏分。300～430℃馏分油中正庚烷可溶物（HS）质量分数高达84.76%，吡啶不溶物（PI）质量分数低至0.23%，杂原子含量低，芳烃化合物的环数为2～4环。300～430℃馏分油在T_H=350℃、p=8MPa、t=1.5h、剂油比1∶40（质量比）的条件下温和加氢得到的精制原料，经420℃热聚6h得制备的中间相炭微球宏观外貌、微晶结构较好。中低温煤焦油基炭微球的粒径范围为5～15μm，小球表面光滑，微观结构为地球仪型，经1450℃高温煅烧后，石墨化度达到12.33%。     

剂油比对煤焦油沥青质加氢过程的影响

以中低温煤焦油沥青质为原料,采用NiMoW/γ-Al_2O_3商业催化剂,在反应温度380℃、反应压力8 MPa和反应时间1.5 h条件下,分别在不同剂油质量比(1∶25、1∶20、1∶15、1∶10)条件下进行加氢实验,通过采用元素分析、FT-IR、XRD、~1H-NMR和XPS等分析表征手段,考察不同剂油质量比对中低温煤焦油沥青质加氢转化过程的影响。结果表明,随着剂油质量比的增加,沥青质转化率提高,加氢产物分布也发生大幅变化,沥青质和芳香分轻质化转化为饱和分。但随着剂油质量比的进一步提高,同时也发生了更多的裂化反应和缩合反应,剂油质量比在合适范围能够很好地起到加氢轻质化且抑制结焦的效果。     

Amine-containing olefin copolymer with CO2-switchable oil absorption and desorption

Global decrease in crude oil resources and frequent crude oil leaks cause the energy crisis and ecological pollution. The absorption and release of leaked crude oil through absorption materials are a necessary process for environmental protection and recycling. In this article, a CO₂-responsive olefin copolymer was obtained by copolymerization of styrene and an amine-containing olefin monomer. The structure of resultant copolymer was characterized by FTIR; thermal properties and CO₂-responsive morphology changes were determined by DSC/TGA and SEM, respectively. Copolymers had certain absorption capacity for toluene with absorption rate up to 180.0%. The absorbed toluene could be released upon CO₂ stimulation with desorption rate up to 84.6%. The CO₂-responsive copolymer could be regenerated through a simple heating process and showed stable absorption–desorption performance even after being recycled for 4 times. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47439.     

A highly transparent and thermally stable copolymer of 1‐adamantyl methacrylate and styrene

Thermal and optical properties of copolymers of 1‐adamantyl methacrylate (AdMA) and styrene (St) prepared by free radical polymerization in the bulk are investigated. The copolymer forms an azeotrope when the composition is AdMA/St = 55/45 mol%. The glass transition temperature and decomposition temperature of the azeotropic copolymer are 170 and ca 340 °C, respectively. The refractive index increases nonlinearly with St content from 1.522 to 1.591. The light scattering loss at 633 nm is 28.1 dB km^?1, which is less than half of that of polystyrene. The total optical loss including molecular vibrational absorption, which is evaluated using a copolymer‐based optical fiber, is 292–645 dB km^?1 at 500–700 nm. These values correspond to transmittances of 86–93% for a 1 m optical path length. © 2014 Society of Chemical Industry     

High‐performance thermosets with tailored properties derived from methacrylated eugenol and epoxy‐based vinyl ester

A renewable chemical, eugenol, is methacrylated to produce methacrylated eugenol (ME) employing the Steglich esterification reaction without any solvent. The resulting ME is used as a low‐viscosity co‐monomer to replace styrene in a commercial epoxy‐based vinyl ester resin (VE). The volatility and viscosity of ME and styrene are compared. The effect of ME loading and temperature on the viscosity of the VE–ME resin is investigated. Moreover, the thermomechanical properties, curing extent and thermal stability of the fully cured VE–ME thermosets are systematically examined. The results indicate that ME is a monomer with low volatility and low viscosity, and therefore the incorporation of ME monomer in VE resins allows significant reduction of viscosity. Moreover, the viscosity of the VE–ME resin can be tailored by adjusting the ME loadings and processing temperature to meet commercial liquid molding technology requirements. The glass transition temperatures of VE–ME thermosets range from 139 to 199 °C. In addition, more than 95% of the monomer is incorporated and fixed in the crosslinked network structure of VE–ME thermosets. Overall, the developed ME monomer exhibits promising potential for replacing styrene as an effective low‐viscosity co‐monomer. The VE–ME resins show great advantages for use in polymer matrices for high‐performance fiber‐reinforced composites. This work is of great significance to the vinyl ester industry by providing detailed experimental support. © 2018 Society of Chemical Industry     

PREDICTING THE TIMING AND CHARACTERISTICS OF PETROLEUM FORMATION USING TAR MATS AND PETROLEUM ASPHALTENES: A CASE STUDY FROM THE NORTHERN NORTH SEA

The Northern Viking Graben area in the Norwegian North Sea was studied in order to investigate the petroleum formation characteristics of the Upper Jurassic Draupne Formation. In this area, the organofacies of the Draupne Formation, and consequently its petroleum generation characteristics, show significant variations. These variations represent a major risk, particularly in the context of basin modelling studies. Therefore, tar‐mat asphaltenes, oil asphaltenes and source‐rock samples from this area were studied in order to evaluate the use of migrated asphaltenes from petroleum reservoirs and tar mats in basin modelling. The samples were studied using bulk kinetic analysis, open‐system pyrolysis‐gas chromatography and elemental analyses, and the results were integrated into a basin modelling study. The results from these different sample materials were compared both to each other and to natural petroleum, in order to assess their significance for future petroleum exploration activities. We show that in cumulative petroleum systems, the transformation characteristics of the asphaltenes incorporate those of the individual source rock intervals which have contributed to the relevant reservoir system. Thus, the petroleum formation window predicted by the use of asphaltene kinetics is broad, and covers the majority of the formation windows predicted from the individual source rock samples. In addition, the molecular characteristics of asphaltene‐derived hydrocarbons show that compositional characteristics, such as aromaticity, correspond more closely to natural oils than to the respective source‐rock products. Our results confirm that the heterogeneous nature of the Draupne Formation results in a significantly broader petroleum formation window than is conventionally assumed. We propose that oil and tar‐mat asphaltenes from related reservoirs represent macromolecules which account for this heterogeneity in the source rock, since they represent mixtures of charges from the different organofacies. One conclusion is that the use of oil and tar‐mat asphaltenes in kinetic studies and compositional predictions may significantly improve definitions of petroleum formation characteristics in basin modelling.     

双膦胺镍-甲基铝氧烷体系催化苯乙烯聚合

研究了具有新型结构的双膦胺镍配合物N,N-双(二苯膦基)-对甲氧基苯胺二氯化镍-甲基铝氧烷(PNP-N i-MAO)催化体系对苯乙烯聚合的催化性能,考察了聚合温度、n(A l)∶n(PNP-N i)、PNP-N i的浓度和苯乙烯的浓度对催化活性、苯乙烯转化率、聚苯乙烯相对分子质量及其分布的影响,并用核磁共振和凝胶色谱对聚苯乙烯的结构进行了表征。实验结果表明,在聚合温度25℃、聚合时间1h、n(A l)∶n(PNP-N i)=300、c(苯乙烯)=2.3m ol/L、c(PNP-N i)=0.4mm ol/L、甲苯为溶剂的适宜条件下,苯乙烯的转化率可达95%以上,催化活性达到5×105g/(m ol.h)左右。核磁共振和凝胶色谱表征结果显示,所得聚苯乙烯为无规结构,重均相对分子质量约为1×104,相对分子质量分布Mw/Mn约为2。     

乙烯基硅氧烷改性苯丙乳液的研究

在苯乙烯 -丙烯酸酯乳液共聚反应后期 ,加入少量乙烯基硅氧烷 ,制得改性苯丙乳液 ,通过红外光谱初步确定了聚合物结构。研究了反应温度、反应时间、有机硅加入方式、乳化剂用量等因素对反应进程、乳液稳定性及涂膜性能的影响。     

高分子表面活性剂对超声辐照下苯乙烯乳液聚合的影响

在超声辐照引发苯乙烯乳液聚合中加入一种新型的以羧甲基纤维素为基础的高分子表面活性剂(CMC—A9)，讨论了高分子表面活性剂对反应动力学的影响。实验表明，超声辐照下初级自由基并非由通常认为的高分子表面活性剂产生，而是十二烷基硫酸钠在超声辐照下断裂，产生自由基。通过对反应动力学的研究，发现超声辐照下乳液聚合机理不同于常规乳液聚合，聚合反应过程只有两个阶段，即加速期和减速期，不存在恒速期。加入CMC—A9高分子表面活性剂，可以在较短的时间内和较低的超声功率下达到较高的单体转化率。     

碳黑对苯乙烯自由基聚合反应影响的研究

研究了碳黑对苯乙烯单体聚合物反应的影响，结果表明，用过氧化苯甲酰作引发剂，普通碳黑子对苯乙烯的聚合有强烈的阻聚作用，而用偶氮二异丁腈引发聚合物时，普通碳黑的阻聚性很小，当时碳黑进行接枝处理后，接枝碳黑对苯乙烯自由基聚合的影响程度与接枝方法有关，其中过氧化苯甲酰 自由基枝枝碳黑的聚性变化较大。