水溶性共聚酯的合成研究

以聚对苯二甲酸乙二醇酯(PET)为基体,引入第三单体间苯二甲酸乙二醇酯-5-磺酸钠(SIPE)和第四单体间苯二甲酸(IPA),通过直接酯化-缩聚工艺路线合成水溶性共聚酯,系统研究了二元酸配比、SIPE添加量对共聚酯的合成和常规性能的影响,利用核磁共振定性分析了共聚酯的大分子链序列结构。结果表明SIPE主要影响共聚酯的流动性能和常规性能,IPA主要影响共聚酯的耐热性能。核磁表明SIPE和IPA均成功引入共聚酯大分子链结构中,且符合多单体改性和高比例IPA改性的分子序列结构特点。     

阳离子染料易染聚酯ECDP小试研制报告

本研究介绍在普通聚酯的基础上,加入第三单体5—间苯二甲酸二甲酯磺酸钠(SIPM)和第四单体聚乙二醇(PEG),克服了阳离子染料易染聚酯 ECDP,由于加入第三,第四单体,大部分产品发黄的倾向。采用本研究的工艺所得 ECDP 切片色相好于国内同类产品。     

低熔点PET的制备

在常规PET生产中加入适当的第三单体和第四单体可制备低熔点聚酯。以精对苯二甲酸(PTA)和乙二醇(EG)为原料,加入适当的间苯二甲酸(或己二酸)、1,4-丁二醇(或6-己二醇),聚乙二醇的质量分数(相对二元羧酸)为5％～8％,采用质量分数为0.005％～0.008％钛系催化剂,生产的低熔点聚酯熔点为110～120℃,且热稳定性好。     

化学法循环再生阳离子染料可染聚酯的性能研究

以废旧纺织品、 乙二醇及甲醇为主要原料,添加共聚单体间苯二甲酸-5-磺酸钠,采用化学法循环再生的方法合成阳离子染料可染聚酯(RCD).分析了该共聚酯的化学结构与组成、结晶性能、热性能和相应的预取向纤维的牵伸性能,并将该共聚酯与精对苯二甲酸及乙二醇为主要原料的直接酯化法工艺生产的阳离子染料可染聚酯(CD)进行对比分析.结...     

阳离子染料可染聚酯的流变性研究

对阳离子染料可染聚酯(CDP)系列切片进行了流变学研究,论述了分子量、第三单体含量、温度等因素对阳离子染料可染聚酯的流变性的影响,为聚合工艺及纺丝工艺的参数确定提供了理论依据.     

聚酯工业发展新动向

介绍了 PET、PEN、PTT、PBT等聚酯的性能、开发、应用、原料、市场需求及预测 ,着重讨论了 PEN和 PTT两种新型聚酯单体奈二甲酸二甲酯 (NDC)和 1,3- PDO(1,3-丙二醇 )合成工艺路线和应用前景 ,并提出了我国加快新聚酯开发的建议。     

水性聚酯漆的制备与表征

以间苯二甲酸-5-磺酸钠(5-SSIPA)为水性单体,与多元醇、羧酸熔融缩聚得到水性聚酯,以六甲氧基甲基三聚氰胺(CYMEL303)为固化剂制备了漆膜。探讨了聚合工艺及水性单体用量对聚酯性能的影响,考察了固化剂用量对漆膜性能的影响。结果表明:不同聚合方法制备的聚酯水溶性存在差异;随着5-SSIPA用量提高,聚酯水溶性先增高后降低;随固化剂用量提高,漆膜的铅笔硬度、附着力增加,耐冲击性能先提高后下降。     

有机氧化磷类阻燃剂在聚酯合成中的应用工艺探讨

通过对磷系阻燃剂的筛选和工艺试验,认为2-羟乙基苯基次磷酸(CEPPA)、[(6-氧(6H)-二苯并-(c,e)(1,2)-氧磷杂己环-6-酮)甲基]-丁二酸(DDP)是工业化生产共聚阻燃聚酯较为合适的阻燃剂。可控制低温反应和柔性化程度高的装置是共聚阻燃聚酯生产应具备的条件,在上海石化年产1万t聚酯生产线上成功实现了共聚阻燃聚酯的工业化连续生产。结合连续式共聚阻燃聚酯合成技术和产品的开发,对生产试验中使用的两种磷系阻燃剂进行了应用研究及对比分析。     

磺酸盐型水性聚酯的合成与性能研究

本研究以二乙二醇(DEG)、间苯二甲酸(IPA)及间苯二甲酸-5-磺酸钠(5-SSIPA)为单体进行熔融聚合得到含有磺酸基团的水性聚酯。实验通过调控水性聚酯中亲水单体间苯二甲酸-5-磺酸钠的摩尔比来研究其性能变化。运用核磁共振氢谱(1H-NMR)、原子力显微镜(AFM)、电泳光散射(ELS)等多种方法对水性聚酯的物理、化学性能进行表征。结果表明:该聚酯具有良好的水分散性、稳定性,且在亲水性单体5-SSIPA与IPA的摩尔比由0增至0.20的过程中,在水分散性提高的同时其他性能也发生相应变化。     

羟基型水性聚酯-丙烯酸树脂杂化体的合成研究

以2-丁基-2-乙基-1,3-丙二醇(BEPD)等多元醇、苯酐(PA)等多元酸聚合得到不饱和聚酯,与甲基丙烯酸-2-羟基乙酯(2-HEMA)、丙烯酸(AA)等丙烯酸类单体自由基聚合,制得羟基型水性聚酯–丙烯酸树脂杂化体。以六甲氧基甲基三聚氰胺(CYMEL 303)为固化剂,制成了水性聚酯丙烯酸树脂–氨基烤漆。通过样品分析与性能测试确定了最佳工艺及配方。结果表明,选用本体聚合制备分子量在1 500左右的不饱和聚酯,2-丁基-2-乙基-1,3-丙二醇的用量为聚酯总物质的12%,引发剂过氧化二苯甲酰(BPO)的用量为5%,丙烯酸的用量为丙烯酸单体总量的12%,丙烯酸树脂的玻璃化温度为19.8℃,水性树脂/氨基固化剂配比为3∶1,其制得的涂膜具有优良的综合性能。制得的涂料耐水性(25℃、360 h)、贮存稳定性(50℃、20 d)和耐溶剂性良好。     

超柔软易染新型聚酯的热性能研究

超柔软易染聚酯是一种新型功能性聚酯产品。通过差示扫描量热测试,就其构成成分对玻璃化转变温度、冷结晶温度、熔点、熔融结晶温度的影响进行了研究,为后道加工工艺的选择提供参考依据。     

Production of micron-size monodisperse polymer particles by seeded polymerization utilizing dynamic swelling method with cooling process

Monodisperse polystyrene particles (6.6 μm diameter) were produced by seeded polymerization utilizing the dynamic swelling method with cooling process as follows. Monodisperse polystyrene seed particles (1.8 μm diameter) were dispersed in ethanol/water (3/4 w/w) medium containing styrene monomer, benzoyl peroxide as initiator and poly(vinyl alcohol) as stabilizer at 65d?C. By lowering the temperature to ?5d?C at a speed of ?1d?C/min the polystyrene seed particles were swollen from 1.8 to 7.7 μm by the absorption of styrene monomer, keeping the high monodispersity. An appropriate amount of water was then added to the dispersion at ?5d?C to depress the redissolution of styrene from the swollen particles into the medium. By elevating the temperature the seeded polymerization was carried out at 70d?C. The production of submicron-size polystyrene new particles as a by-product was depressed by the addition of NaNO₂ to the medium.     

回收四氟乙烯生产六氟丙烯的技术研究

四氟乙烯(TFE)是最重要的含氟单体之一,利用回收的TFE生产六氟丙烯(HFP)是一种新的技术探索。综合分析了铜洗脱CO工艺、TFE回收处理工艺、氟化工精馏工艺以及TFE生产HFP反应工艺的应用,进行了回收TFE生产HFP的设计研究。     

尼龙6生产中注带处单体烟的回收

分析比较了尼龙 6生产中注带处单体烟的几种回收方法。利用萃取水与注带的单体烟在吸收塔内逆向传质吸收而将单体予以截留的工艺 ,对单体的吸收效果最好。单体的实际回收率可达 98%以上。讨论了影响吸收效率的主要因素及在吸收塔顶加装除沫器的设计     

丙烯腈共聚物中丙烯腈单体残留量的控制方法

采用顶空气相色谱法,系统研究了丙烯腈共聚制品生产过程中工艺参数的调整对丙烯腈单体残留量的影响。分别对原料预热温度、机筒温度、注射压力进行了优化和选择。结果表明:对于ABS和AS原料,都选择80℃的预热温度,并分别选择(260、260、250、230)℃、(230、230、220、200)℃的机筒温度组合以及低压、高压的注射压力为最优工艺参数,丙烯腈共聚制品中的丙烯腈单体残留量与对应的生产原料相比,分别下降了5.31%~15.1%,而在其他工艺条件下生产的丙烯腈共聚制品,其丙烯腈单体残留量下降不明显,甚至大部分呈上升趋势。     

Mechanism of nickel catalysed dehalogenative step polymerization of aryl dibromides

Dehalogenative polycondensation of 3,6-dibromo-N-alkylcarbazoles was catalysed by a Ni(O)-based complex generated in N,N-dimethylacetamide by electroreduction of NiBr₂/2,2′-bipyridine. The process involves three different reaction steps, which are successively: electrolysis of Ni(II) to Ni(O); insertion of the latter into a C? Br bond of monomer leading to C? Ni? Br* active species; dehalogenative coupling between active species and monomer yielding oligomers. From the kinetics of electrogeneration of the catalytic system in absence of monomer, a first-order reaction was determined. Insertion and coupling reactions were found to be second-order and comparison of the values of the corresponding rate constants clearly showed that coupling is the rate-determining step of the process. Simultaneous size exclusion chromatography and cyclic voltammetry measurements were carried out in the course of the electrosynthesis of poly(N-alkylcarbazole)s. The change in the molar mass population distribution as a function of electrolysis time revealed a step polymerization process, while showing a termination of the chain growth due to the occurrence of monobrominated species. The study of the effect of the [monomer]/[catalyst] ratio on the molar mass population change indicated that the coupling of active species (Ni(O)-activated monomer) is responsible for the chain growth.     

Free radical solution oligomerization of styrene in a continuous-stirred tank reactor train

For free radical oligomerization of styrene, a scheme for calculating the molecular weight distribution and conversion in a continuous-stirred tank reactor (CSTR) train is developed, which also allows the calculation of molecular weight distribution (MWD) for batch reaction. Calculations show that under conventional or near dead-end condition: (1) increasing initial initiator concentration, reaction time and reaction temperature, and decreasing initial monomer concentration cause P?_n and P?_w to decrease and MWD to narrow; (2) increasing initial initiator concentration, reaction time and reaction temperature, and increasing monomer concentration cause monomer conversion to increase; (3) a single CSTR gives a lower rate of oligomer production, but a narrower MWD than does a batch reactor.     

Preparation and water absorbency of a novel poly(acrylate‐co‐acrylamide)/vermiculite superabsorbent composite

A novel poly(acrylate‐co‐acrylamide)/expanded vermiculite (EVMT) superabsorbent composite was synthesized by aqueous solution polymerization method. The water absorbency of the superabsorbent composite still reaches 850 g/g when 50 wt % EVMT is added, which is significant in decreasing the production cost of the superabsorbent composites. By controlling the molar ratio of acrylic acid monomer and acrylamide monomer, and neutralization degree of acrylic acid, the hydrophilic groups on the composite can be adjusted, and it is found that the collaborative absorbent effect of ? CONH₂, ? COOK, and ? COOH groups is superior to that of single ? CONH₂, ? COOK, or ? COOH group. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 735–739, 2007     

A case study for reactor network synthesis: the vinyl chloride process

A key objective of the integrated reactor network synthesis approach is the development of waste minimizing process flowsheets (Lakshmanan & Biegler, 1995). With increasing environmental concerns in process design, there is a particularly strong need to maximize conversion to product and avoid generation of wasteful byproducts within the reactor network. This also avoids expensive treatment and separation costs downstream in the process. In this study, we present an application of the mixed integer nonlinear programming (MINLP)-based reactor network synthesis strategy developed by Lakshmanan and Biegler (1996a). Here we focus on applying these reactor network synthesis concepts to the vinyl chloride monomer production process. Vinyl chloride is currently produced by a balanced production process from ethylene, chlorine and oxygen with three separate reaction sections: oxychlorination of ethylene; direct chlorination of ethylene; and pyrolysis of ethylene dichloride. The hydrogen chloride produced in the pyrolysis reactor is used completely in the oxychlorination reactor. Byproducts such as chlorinated hydrocarbons and carbon oxides are generated by these reaction sections. These are studied using reaction kinetic models for the three reaction sections. The case study results in optimal reactor networks that improve the conversion of ethylene to vinyl chloride and minimize the formation of byproducts. These results are used to generate an improved flowsheet for the production of vinyl chloride monomer. Moreover, an overall profit maximization, that includes the effect of heat integration, is presented and a set of recommendations that improve the selectivity of vinyl chloride production are outlined. Finally, the optimal reactor structures, overall conversion and annual profit are shown to be only mildly sensitive with respect to small changes in the kinetic parameters.     

对发展我国有机硅甲基单体生产的思考

对我国有机硅甲基单体的生产与国际先进水平进行比较，从原料制备及质量、铜催化剂与触体配方、工艺过程与工艺条件优化、流化反应床的工程放大、单体精馏与富余单体利用、生产过程中的三废治理、甲基乙烯基单体生产等８个方面提出一些想法和见解