聚醚酮合成产物中二苯砜回收工艺的研究

聚醚酮是一种性能优异的特种工程塑料,广泛应用于航空航天、汽车制造、医疗器械、计算机及精密仪器等领域。该塑料有几种生产工艺,其中一种是以二苯砜为溶剂。二苯砜在聚醚酮生产过程中作为反应物系的溶剂,反应结束后采用丙酮浸取回收。根据设计的几种工艺,通过实验比较,得到了效果较好的改进脂肪提取式工艺,为聚醚酮精制工艺设计提供了充分的依据;同时,实验中获得的最佳操作条件,为实际生产提供了参考数据。     

Exposure and effects assessment of persistent organohalogen contaminants in arctic wildlife and fish

Persistent organic pollutants (POPs) encompass an array of anthropogenic organic and elemental substances and their degradation and metabolic byproducts that have been found in the tissues of exposed animals, especially POPs categorized as organohalogen contaminants (OHCs). OHCs have been of concern in the circumpolar arctic for decades. For example, as a consequence of bioaccumulation and in some cases biomagnification of legacy (e.g., chlorinated PCBs, DDTs and CHLs) and emerging (e.g., brominated flame retardants (BFRs) and in particular polybrominated diphenyl ethers (PBDEs) and perfluorinated compounds (PFCs) including perfluorooctane sulfonate (PFOS) and perfluorooctanic acid (PFOA) found in Arctic biota and humans. Of high concern are the potential biological effects of these contaminants in exposed Arctic wildlife and fish. As concluded in the last review in 2004 for the Arctic Monitoring and Assessment Program (AMAP) on the effects of POPs in Arctic wildlife, prior to 1997, biological effects data were minimal and insufficient at any level of biological organization. The present review summarizes recent studies on biological effects in relation to OHC exposure, and attempts to assess known tissue/body compartment concentration data in the context of possible threshold levels of effects to evaluate the risks. This review concentrates mainly on post-2002, new OHC effects data in Arctic wildlife and fish, and is largely based on recently available effects data for populations of several top trophic level species, including seabirds (e.g., glaucous gull (Larus hyperboreus)), polar bears (Ursus maritimus), polar (Arctic) fox (Vulpes lagopus), and Arctic charr (Salvelinus alpinus), as well as semi-captive studies on sled dogs (Canis familiaris). Regardless, there remains a dearth of data on true contaminant exposure, cause-effect relationships with respect to these contaminant exposures in Arctic wildlife and fish. Indications of exposure effects are largely based on correlations between biomarker endpoints (e.g., biochemical processes related to the immune and endocrine system, pathological changes in tissues and reproduction and development) and tissue residue levels of OHCs (e.g., PCBs, DDTs, CHLs, PBDEs and in a few cases perfluorinated carboxylic acids (PFCAs) and perfluorinated sulfonates (PFSAs)). Some exceptions include semi-field studies on comparative contaminant effects of control and exposed cohorts of captive Greenland sled dogs, and performance studies mimicking environmentally relevant PCB concentrations in Arctic charr. Recent tissue concentrations in several arctic marine mammal species and populations exceed a general threshold level of concern of 1 part-per-million (ppm), but a clear evidence of a POP/OHC-related stress in these populations remains to be confirmed. There remains minimal evidence that OHCs are having widespread effects on the health of Arctic organisms, with the possible exception of East Greenland and Svalbard polar bears and Svalbard glaucous gulls. However, the true (if any real) effects of POPs in Arctic wildlife have to be put into the context of other environmental, ecological and physiological stressors (both anthropogenic and natural) that render an overall complex picture. For instance, seasonal changes in food intake and corresponding cycles of fattening and emaciation seen in Arctic animals can modify contaminant tissue distribution and toxicokinetics (contaminant deposition, metabolism and depuration). Also, other factors, including impact of climate change (seasonal ice and temperature changes, and connection to food web changes, nutrition, etc. in exposed biota), disease, species invasion and the connection to disease resistance will impact toxicant exposure. Overall, further research and better understanding of POP/OHC impact on animal performance in Arctic biota are recommended. Regardless, it could be argued that Arctic wildlife and fish at the highest potential risk of POP/OHC exposure and mediated effects are East Greenland, Svalbard and (West and South) Hudson Bay polar bears, Alaskan and Northern Norway killer whales, several species of gulls and other seabirds from the Svalbard area, Northern Norway, East Greenland, the Kara Sea and/or the Canadian central high Arctic, East Greenland ringed seal and a few populations of Arctic charr and Greenland shark.     

Contaminant blubber burdens in Atlantic bottlenose dolphins (Tursiops truncatus) from two southeastern US estuarine areas: Concentrations and patterns of PCBs, pesticides, PBDEs, PFCs, and PAHs

Polychlorinated biphenyls (PCBs), chlorinated pesticides (i.e., dichlorodiphenyltrichloroethane (DDT) and its metabolites, chlordanes (CHLs), dieldrin, hexachlorobenzene (HCB), and mirex), polybrominated diphenyl ethers (PBDEs), perfluorinated chemicals (PFCs), and polyaromatic hydrocarbons (PAHs) were measured in blubber biopsy samples collected from 139 wild bottlenose dolphins (Tursiops truncatus) during 2003-2005 in Charleston (CHS), SC and the Indian River Lagoon (IRL), FL. Dolphins accumulated a similar suite of contaminants with ∑ PCB dominating (CHS 64%, IRL 72%), followed by ∑ DDT (CHS 20%, IRL 17%), ∑ CHLs (CHS 7%; IRL 7%), ∑ PBDE (CHS 4%, IRL 2%), PAH at 2%, and dieldrin, PFCs and mirex each 1% or less. Together ∑ PCB and ∑ DDT concentrations contributed ∼ 87% of the total POCs measured in blubber of adult males. ∑ PCBs in adult male dolphins exceed the established PCB threshold of 17 mg/kg by a 5-fold order of magnitude with a 15-fold increase for many animals; 88% of the dolphins exceed this threshold. For male dolphins, CHS (93,980 ng/g lipid) had a higher ∑ PCBs geomean compared to the IRL (79,752 ng/g lipid) although not statistically different. In adult males, the PBDE geometric mean concentration was significantly higher in CHS (5920 ng/g lipid) than the IRL (1487 ng/g). Blubber ∑ PFCs concentrations were significantly higher in CHS dolphins. In addition to differences in concentration of PCB congeners, ∑ PBDE, TEQ, ∑ CHLs, mirex, dieldrin, and the ratios ∑ DDE/∑DDT and trans-nonachlor/cis-nonachlor were the most informative for discriminating contaminant loads in these two dolphin populations. Collectively, the current ∑ PCB, ∑ DDT, and ∑ PBDEs blubber concentrations found in CHS dolphins are among the highest reported values in marine mammals. Both dolphin populations, particularly those in CHS, carry a suite of organic chemicals at or above the level where adverse effects have been reported in wildlife, humans, and laboratory animals warranting further examination of the potential adverse effects of these exposures.     

超重力法制备La_(0.5)Pb_(0.5)MnO_3及其在碳酸二苯酯合成中的应用

采用液液相共沉淀法在旋转填充床中合成钙钛矿型复合氧化物La0.5Pb0.5MnO3的前驱体,再经高温焙烧后制备出碳酸二苯酯合成催化剂的载体材料。考察了旋转填充床转速、反应物流量和添加分散剂PEG对La0.5Pb0.5MnO3物性的影响,通过XRD、BET、SEM、粒度分析手段对载体进行表征。结果表明,旋转填充床转速为1200r.min-1,反应物流量为80L.h-1,加入PEG10000时可制备出纯晶相的钙钛矿载体,相应的载钯(Pd占载体质量的0.5%)催化剂在氧化羰基化合成碳酸二苯酯反应中的活性最好。当反应总压为5MPa、CO/O2分压比为96:6、反应时间3h、反应温度65℃时,碳酸二苯酯收率可达13.30%。     

聚乙二醇对旋转填充床制备La_(0.5)Pb_(0.5)MnO_3载体的影响

采用旋转填充床液液相共沉淀法制备了钙钛矿复合氧化物La0.5Pb0.5MnO3,以其作为载体制备了0.5%Pd(质量分数)/La0.5Pb0.5MnO3催化剂合成碳酸二苯酯。为了提高催化剂的活性,采用聚乙二醇(PEG)为分散剂对载体表面改性,通过XRD,SEM,BET手段对其物性进行表征,并对催化剂进行了活性评价。结果表明:PEG良好的空间位阻效应可以增加载体的分散度和比表面积,提高催化剂的活性。PEG10 000浓度为0.001 5 mol/L时效果最佳,载体比表面积达53.73 m2/g。反应温度65℃,总压5 MPa,p(CO)∶p(O2)=94∶6,反应3 h,DPC收率达13.30%。反应9 h,该条件下DPC收率可达21.90%。     

碳酸乙烯酯酯交换合成碳酸二苯酯

为利用碳酸乙烯酯固定的CO2,拓展碳酸二苯酯的合成方法,对碳酸乙烯酯酯交换合成碳酸二苯酯的反应进行了热力学分析,并考察了催化剂、反应温度、催化剂质量分数和反应时间对合成碳酸二苯酯的影响。结果表明:碳酸乙烯酯与苯酚的酯交换反应在热力学上是不可行的,而将苯酚乙酰化后可以实现由碳酸乙烯酯经酯交换合成碳酸二苯酯;不同催化剂催化酯交换反应时,n-Bu2SnO显示了最高的酯交换选择性。当反应温度为190℃,碳酸乙烯酯与乙酸苯酯的摩尔比为1∶2,n-Bu2SnO质量分数8%,反应时间10 h时,碳酸乙烯酯的转化率为15.1%,酯交换选择性64.2%,碳酸二苯酯的收率7.5%。     

四苯基联苯二酚双磷酸酯的合成研究

用三氯氧磷、4,4’-二羟基联苯、苯酚为原料合成阻燃剂四苯基对联苯二酚双磷酸酯（DBBDP）,采用单因素实验法分别对物质的量之比、反应时间、反应温度进行讨论,确定了最佳的反应条件：三氯氧磷、4,4’-二羟基联苯和苯酚的物质的量之比为6︰1︰4.1;第1步反应温度为105～120℃,反应时间为4 h;第2步反应温度为120～150℃,反应时间为5 h;无水三氯化铝为催化剂,用量为4,4’-二羟基联苯的2%,产品收率为82.1%。产品经红外光谱和元素分析确定其结构和组成,通过热重分析表明产品的耐热性能良好。     

聚醚酮合成产物中二苯砜的浸取工艺

以二苯砜为溶剂合成聚醚酮时,反应结束后,产物、溶剂、副产物、原料等掺杂在一起,常温下形成固体混合物。为了将产物与其它物料分离,通常将混合固体粉碎,首先用溶剂将二苯砜浸出,然后再经蒸馏、干燥,回收二苯砜。本研究从脂肪提取工艺、抽提工艺、蒸煮工艺及循环等工艺出发,探索了聚醚酮合成产物中二苯砜的浸出过程。试验结果表明改进脂肪提取工艺是浸出二苯砜的最适宜工艺,其过程简单,控制容易,整批物料处理周期为2.16 h,丙酮消耗量为0.03 L,物料粉化率为零。同时,明确了浸取过程的机理,为二苯砜浸出的工业生产过程的工艺设计奠定了基础。     

三光气法碳酸二苯酯的合成工艺

利用三光气代替光气合成碳酸二苯酯,考查了催化剂的加入时间、混料方式、反应温度以及提纯方式对产品质量以及收率的影响。产品纯度≥99.5%,以三光气计,产品收率≥98%;以苯酚计,产品收率≥98.5%。     

零价铁降解多溴联苯醚影响条件的研究

通过离子色谱的方法,利用零价铁对水中的多溴联苯醚进行还原性脱溴,对影响因素进行了研究和探讨。试验结果表明：酸性条件有利于脱溴反应的进行;较高的十溴联苯醚初始浓度有利于脱溴反应的进行;零价铁的粒径越小,其对多溴联苯醚的脱溴效果也越好;温度越高时,多溴联苯醚的脱溴率也越高。研究结果将为利用零价铁渗透式反应墙去除水中的多溴联苯醚污染物提供理论依据。