α-烯烃减阻剂特性粘度的研究

第31卷第2期新疆大学学报(自然科学版)Vol 31. No. 2014年5月Journal of Xinjiang University(Natural Science Edition)Study on Intrinsic Viscosity of a-olefin DragReducing Agent(DRAZHU Gui-dan', LU Jiang-yin't, WANG Chun-xiao2, QI Yan-jiehemistry Gr Chemical Erals of Ministry of Education,Xinjiang University, Urumqi, Xinjiang 830046, China,2. Nantong economic-technological development area administration of work safety, Nantong, Jiangsu 226009, China)Abstract: Catalyst a-olefin DRA(Drag Reducing Agent) synthesized by bulk polymerization TiCl4/Al(Et)3 use IR andXRD to study the structure of the polymer. This study is about the polymer operation condition effect of the drag reducingpolymer intrinsic viscosity. The result indicate viscosity could reach 8.8 dl/g drag reducing efficiency can reach 43. 12%which means in certain range drag reducing efficiency is proportional to viscosity. The optimal operation conditions are at3C, the dosages of the main catalyst(TiCl4/MgCl2), co-catalyst(Al(Et)3), and diphenyldimethoxysilane(DDS)are 0.085g, 0. 14 ml and 0.04 mL, respectivelyKey words: drag reducing, bulk polymerization, intrinsic viscosity, catalyst, efficiencyCLC number: TQ325 1 Document Code:A Article ID: 1000-2839(2014)02-0199-06α-烯烃减阻剂特性粘度的研究朱桂丹1,陆江银,王春晓2,齐艳杰1(1.新疆大学化学化工学院,石油天然气精细化工教育部重点实验室,新疆乌鲁木齐8300462.南通市经济技术开发区化工安全生产监督管理局,江苏南通226009)摘要:通过本体聚合在催化剂TCl4A(Et)3作用下合成a烯烃减阻剂,通过红外光谱(IR)和X射线衍射(XRD)对聚合物进行结构分析,研究了合成聚合物影响因素对减阻聚合物特性粘度的影响.结果表明当粘度达到8.8dg时减阻率可达到43.1%,即在一定范围内减阻率与粘度成正比.此时合成减阻剂的最优条件为3C,主催化剂(TiCl4MgCl2)助催化剂(Al(Et)3)和二苯基二甲氧基硅烷(ODS)用量分别是0.085克,0.14毫升和0.04毫升关键词:减阻,本体聚合,特性粘度,催化剂,效率0 IntroductionOil-soluble Drag Reducing Agent is a kind of olefin polymer with super-high molecular weight, a small amount ofwhich to crude oil or product oil can increase transmission capacity and improve transportation safety effectively.Atpresent, every year more than10x10 t drag reducing agent is consumed worldwide, and drag reducing agent is widelyused in pipelines all over the world to reduce the cost dramatically, plus lessen environmental pollution 2-6. but theproblem of shear degradation is inevitable, and the shear resistance has significant impact on drag reducing propertiesViscosity change is related with shear degradation, so the shear resistance of the polymer could be represented by theviscosity changUnder the same test conditions, molecular weight is an evaluation standard for resistance. because the value ofviscosity can suggest molecular weight qualitatively, so the value of resistance can be indicated indirectly. The breakingof polymer molecular chains caused by the ultrasonic shear has the same results in evaluation of the shear stability aswhich caused by the mechanical rupture, during the ultrasonic shear, the intrinsic viscosity of polymer decreased, so theReceived Date: 2014-01-18中国煤化工Foundation Item: supported by the National Natural Science Foundation of China(20963010CNMHGBiography ZHU Gui-dan(1988), female, a master student, the research direction is oil drag rearCorresponding author: LU Jiang-yin(1964-), male, Docter, Professor, Master Tutor, Engaged in the study of industrial catayst.新疆大学学报(自然科学版)2014年measurement of intrinsic viscosity after ultrasonic shear shows the shear stability of polymer indirectly s. In additionmolecular weight is another evaluation standard for the polymer shear stability, Nurulla consider that the higher thepolymer molecular is, the better the shear stability is. Because the value of intrinsic viscosity can manifest the polymermolecular weight qualitatively, the larger the intrinsic viscosity is, the higher the polymer molecular weight is, thevalue of the intrinsic viscosity can indicate the polymer shear stability indirectlyIn this paper, a-hexylene/a-dodepolymers were synthesized with TiCl/Al(Et)3 as catalysts and a-olefimonomers by bulk polymerization, the effects of the reaction temperature, catalyst dosage, DDS dosage and solutionon the intrinsic viscosity of the dRa were investigated. Also, the intrinsic viscosity of the polymer afterItrasonic shear was researched1 Experimental1.1 Materials and facilituesa-dodecene(Fluka product), moisture content is not higher than 25 mg/L; a-hexene, J&Ks U.s. import; TiCl4/MgCl2, brown powder, Beijing Chemical Industry Research Institute; Al(Et)3, industrial grade, made in Japan; hexaneand ethanol (AR)ZKX-2 vacuum glove box, Nanjing University Instrument Factory; DZF-6030A vacuum drying oven and dHG9070A-type air blowing thermostatic oven, Shanghai Scientific Instrument Co, Ltd ; AR224CN millionth electronicbalance, Ohaus Instruments(Shanghai)Co., Ltd1. 2 Preparation for polymersThe monomer was dehydrated with 5A zeolite. High purity nitrogen was dehydrated using H2SO4 and CaCl2respectively; and the Glass Instruments and Stirring Bar with magnetic core were dried in air blowing thermostatic oven20C from 4 to 6 hours. The metage of main catalyst was completed in a vacuum glove box, using the co-catalystunder the protection of high-purity nitrogen. Polymerization process was carried out in self-prepared polymerizationbottle, and high purity nitrogen was used repeatedly to eliminate oxygen in the bottle before polymerization beginsThe monomer ar-dodecene and a-hexene, the co-catalyst Al(Et)3 and the main catalyst TiCl4 /MgCl2 were added inthe polymerization bottle, respectively. At the same time, the reaction temperature was controlled with ice-salt bathWhen the main catalyst no longer sinked and Stirring Bar with magnetic core no longer rotated, the polymeric bottlewas sealed up and moved to react in refrigerator. After reaction, the product was washed with ethanol and thenmoved inside vacuum drying oven(60"C)to dry until constant weight. Dried products were dissolved with hexane todetermine1.3 Determination of viscosity (n)The polymer was dissolved with hexane at the temperature of 25"C and then the viscosity was determined byUbbelohde viscometer1.4 Evaluation of shear strength resistanceThe breaking of polymer molecular chains caused by the ultrasonic shear) could achieve the same effect of shearrength compared to mechanical rupture, also the viscosity of polymer would change, so the measurement of viscosityfter ultrasonic processing indirectly showed the shear properties of polymer. The polymer solution was put into theultrasonic cone bottle and laid under ultrasonic signals of output voltage of 220V, frequency 40KHZ, power 200wconditions2 Results and discussion2.1 Analysis of Infrared (Ir) spectroscopyFT-IR spectra of polymeric product are shown in fig. 1. The characteristic bands appeared in the spectrum ofproduct are C-C stretching vibration appeared near 1 461.5 cm", -CH3 bendingThe stretching vibration and bending vibration of saturated hydrocarbon wer中国煤化工852.7cmrespectively, such vibrations were the strong bands. The bending vibrationCNMHG4615cmwhere, n<4. The FT-iR spectra showed a great consistency with structure of the product第2期ZHU Gui-dan, et al. Study on Intrinsic Viscosity of ar-olefin Drag Reducing Agent(DRA)2.2 Analysis of XRDThe XrD of polymer was dissolved by dimethyl benzene and then deposited by alcohol were shown in fig. 2Disperse diffractive peak appeared at 20=20, and it belongs to long-chain olefin because seams ranges are near0.35-0.39 nm. To sum up, fig. 2 was the curve of disperse diffractive peak, which showed a low degree of crystallineRigid group was not involved in the reaction, suggesting the polymer was the flexible one3000350040004500Fig 1 Ir pattern of the polymerFig 2 XRD Pattern of the polymerIn this paper, we investigated a great number of references to adopt orthogonal experiment factor level table(L164), and the orthogonal test factors were listed in table 1. Using Mark-Houwink equation, according to the formulan=KM, in which, K=1.544x10 and a=0.708, and viscosity results and the measurements of viscosity averagemolecular weight were listed in table 2Table 1 Orthogonal experiment factor level table(L164)0.050.240.041:210A: main catalyst dosage; B: co-catalyst dosage; C: Volume ratio of olefins (a-hexene: ar-dodecene); D: reactiontime; E: reaction temperatureTable 2 Measurements of viscosityNo.n(d/g)M(×106)No.m(d/g)M2(×106)6.046.163.159.22108.455.87127.668.124.66The range of polymers viscosity analysis was listed in the following tabl中国煤化工As can be seen in table 3. the best reaction conditions were alB4c2DO-catalyst dosage, volume ratio of olefins(ar-hexene: ar-dodecene), reactionCNMHGcre are 0. 08g,0.1g,2:1,24hand-5°C02新疆大学学报(自然科学版)2014年Table 3 Range analysis of polymerFactor ParameterABCE33.2825.3830.512873272830.1032.22314530.8529.6531.1328.55296l34.429.7431.2330.647.181.292.260.92the same time, the range analysis results showed that the influencing sequence of the viscosity from high tore the co-catalyst dosage, the main catalyst dosage, polymerization temperature, the ratio of monomers andpolymerization time, respectivelyler the optimum conditions of polymerization( the main catalyst dosage.08 g, the co-catalyst dosage. 10 mL,polymerization temperature 5C, the ratio of monomers 2: 1, and polymerization time 24 h ), the intrinsic viscosity ofthe polymers reached 9.84 dl/ g2.3 Effect of main catalyst dosage on viscosityFig 3 shows effect of main catalyst dosage on viscosity. As can be seen in the chart, under experimental conditionmentioned in this paper, with more main catalyst used, the viscosity increased slowly, but after the dosage reached 0.06g, the viscosity started to decrease. When the main catalyst dosage was 0.085 g, the viscosity could receive a maximumvalue of 10.30 dl/ g. When the main catalyst dosage was low, excess alkyl aluminum not only interacted with TICl4to form active center, but also TiCl4 could be deoxidized to inactive TiCl2. Overall, in a certain range with the maincatalyst increased, the viscosity increased2.4 Effect of co-catalyst dosage on viscosityFig 4 shows the effect of co-catalyst dosage on viscosity. The results illustrated that the effect of co-catalystdosage on intrinsic viscosity was different from the main catalyst. When the co-catalyst dosage was between 0.06mL-0 14 mL, viscosity increased, but then with the co-catalyst dosage increased, the viscosity decreased graduallyThe maximum value of viscosity up is 10.80 dI/g, and the optimal co-catalyst dosage was 0. 14 mL. When the co-catalystdosage was high, excess alkyl aluminum was adsorbed on active center; interfered with the monomer coordination tothe active sites to reduce the catalytic activity1.510.00.050.060.070.080.090.10V(AI(Et)3)/mlFig 3 Effect of main catalyst dosage on viscosityFig 4 Effect of co-catalyst dosage on viscosity2.5 Effect of polymerization temperature on viscosity中国煤化工In terms of heterogeneous olefin coordination polymerization withCNMHGrelease in the reaction process, and further gel would appear soon in the reaction system lol. Thus, controlling reaction第2期ZHU Gui-dan, et al. Study on Intrinsic Viscosity of ar-olefin Drag Reducing Agent(DRA)temperature is significant. Fig. 5 shows the changes of viscosity with reaction temperature. The results illustratedthat at a range of-10C to-3C, with temperature increased, the viscosity increased, but then decreased. When thetemperature was -3C, the viscosity could receive a maximum value. This relationship could be explained by theArrhenius equationk=ko exp(kr), Where, Ea is the activation energy, ko is the pre-exponential factorition of this equation leads toIn=-RG-7)From the formula, it could be seen with the temperature increased, the rate of reaction increased. As shownin the preceding part of the text, when the reaction rate was rapid, it accelerated the system viscosity which madethe monomer diffusion and mass transfer blocked, and then easily led to gelatin phenomena, ultimately it was notonducive to the increasing of viscosityWhen the temperature was too low, monomer could not completely polymerize within the reaction time, and theviscosity of final product could not be very high. Therefore, only the temperature must be controlled well can we get ahigher viscosity value of polymer2.6 Effect of electron donor on viscosityIn the new-style and efficient Ziegler-Natta catalyst system, the addition of electron donor could significantlychange the performance of catalyst to control molecular weight and molecular weight distribution(MWD), also affecthe viscosity of the polymer, Huang Baotongl2 pointed out that diphenyldimethoxysilane(DDS)not only enabledhigher activity of catalytic system and stereo-selective, but also had an impact on the polymer microstructure andmolecular weight. Therefore, different dosage of Dds as an outer electron donor had been used to study its effectity, which corresponds to the result of fig. 6. From the figure we can see that only at a suitable range ofconcentration can the reaction reacted toward the direction of an increase in viscosity. The dosage of DDs had anobvious effect on viscosity, and with the increase of DDS, viscosity increased first, but then decreased. When thedosage of DDS was 0.04 mL, viscosity could reach a maximum value of 10.77 dl/g. When the amount of dds waslow, the addition of Dds could contribute to the conversion of random from catalyst active sites to isotactic active siteand such regulations increased the number of isotactic active sites, thereby improved viscosity. Oppositely, an overdosage of DDS would combine with Al(Et)3 to reduce the number of Al(Et)3, and thus led to a decrease of viscosity10.00.000.02VOdDSWmlFig 5 Effect of polymerization temperature onintrinsic viscosityFig 6 The influence between viscosity and dosage of DDs2.7 Effect of solution blending on viscositPolymer blend is an important means of polymer modification! 4. Due to less material and simple operationsolution blending has been widely used in laboratory for basic research. The performance of blend system would bedifferent from the one of single component, especially the rheology. The中国煤化工of 7# and15# were investigated after being mixed, the results are shown in Fig. 7. Thefirst but thenincreased with the addition of the content of component 7#, and could reachCNMHGcertain ratiowhich, was even higher than the one of a single component. The explanation may be that, when after being blended新疆大学学报(自然科学版)2014年the system turned out to be an interlocking structure, such structures increased the flow resistance and led to an increasein blend viscosity2. 8 Effect of ultrasonic degradation on viscositywith the assistance of ultrasonic, polymer solution showed obvious characteristics of ultrasonic degradation owingto large shear stress, and viscosity would decrease. So shear stability of polymer solution with different viscosity valueswere researched by the means of ultrasonic degradation, and results were shown in Fig 8we can see. vIscosityshowed downward trend with the increasing of shear time. At the same time, with increasing of the polymer initiaviscosity, viscosity of polymer solution decreased more slowly. It suggested that the higher of the polymer initialviscosity (i. e, the larger the initial viscosity-average molecular weight) was, the better the anti-shearing stability wasThus, the distribution of polymer molecular weight could be controlled by changing the reactants dasage and reactionconditions, so as to achieve an optimization of shear stress of polymer, which had important applicationsinitial viscosity=7.35tv=8.26initial viscosity=9.06nitial viscosity=10.77司807.57/(wt)ig 8 The influence between intrinsic viscosityFig 7 Variation of system viscosity with blended solution2.9 The relationship between viscosity and drag reductionDifferent polymerization conditions of drag reducing efficiency were shown in Tab. 4. It can be seen that, dragreducing efficiency is proportional to viscosity in a certain range. Under the polymerization D, the viscosity and dragreducing efficiency are 10.80 dl/g and 43. 12% respectively. That's probably because the molecular weight of polymeris so high that its viscosity is very high which means it has a long chain, offers a great opportunity for moleculeentanglement and interaction thus further increased drag-reduction performanceTable 4 The drag reducing efficiency in the different polymerizationConditonsABViscosity /dl/ g8.269069.41080Drag Reduction /4.1636.238.5043.123 ConclusionsStudy on the relationship between the operation condition of polymerization and the intrinsic viscosity of dragreducing polymer revealed that in a certain range with the increase of the dosage of main catalyst the viscosity increasesand when the dosage of main catalyst reaches a certain value, the viscosity would decrease. Meanwhile, the co-catalysdosage, the polymerization temperature and the dosage of Dds are also presented the same change rule. On thecontrary, viscosity showed downward trend with the increasing of ultrasonic degradation time, And the viscosity ofblends declined first but then increased with the addition of the content of component 7#, and could reach a maximumvalue within a certain ratio, which, was even higher than the one of a single component. In one word, drag reducingefficiency is proportional to viscosity in a certain range and as to the differentchanging the values of influencing factors, their drag reducing properties coul中国煤化工" thesized byheir intrinsicCNMHGvIscOSitIes(下转第211页)第2期米尔阿迪力江·麦麦提,等:基于智能设备的汉语学习软件的研究与开发2]张海藩软件工程导论[M]北京:清华大学出版社,2006112-11.③]韩万江软件工程案例教程M北京机械工业出版社,2007,45-48.韩超梁泉 Android系统原理及开发要点详解M北京:电子工业出版社,2010,340-3435 Katysovas T A first look at Google Android. [s 1. Free University of Bolz6 DIMARZIO J F. Android: a programmer's guide[M]. New York: McGraw-Hill, 20087] RICK Rogers, BLAKE Meike, ZIGUARD Medniek, et al. Android应用开发M李耀亮,译北京:人民邮电出版社,20108]田俊静张波,黄湘情 Android基础教程[M北京:人民邮电出版社,2011,53-57⑨]吴亚峰索依娜. Android核心技术与实例详解.北京:电子工业出版社,2010,248-25010林城 Android2.3应用开发实战北京:机械工业出版社,201160180.李金霖,赖超,龙曦等基于 Android平台的手机日程管理系统J计算机与数字工程:20113(39):67-68.12]汪永松 Android平台开发之旅M]北京:机械工业出版社,2011,18618913]巢文涵 Android多媒体开发高级编程[M].北京:清华大学出版社,2012,125-12914宋小倩,周东升基于 Android平台的应用开发研究[软件导刊,2011,10(2):104-10615]赵亮,张维基于 Android技术的界面设计与研究[电脑知识与技术,2009,29(5):184-18516蓝坤,张跃. Android在远程医疔信息系统中的应用J计算机应用,2013.336):1791-1792.责任编辑:闫新(上接第204页The authors thank the Physics and Chemistry Detect Center of the Xinjiang University for the XRDanalyses and the IR experiments参考文献1 Hellsten M. Drag-reducing surfactants JJ Surfactants Deterg, 2001, 4(1 ): 652 Li G P, Yang R, Wang K H. The new progress of drag reducer in research and production at home and abroad[ J]. Oil &eGas Storageand Transportation, 2000, 19(1):33 Hu T N. Optimization strategy on batch transportation of oil product J]. Oil Gas Storageand Transportation, 1997,[4 Boschat J, Sabathier J. Ecuador plans expanded crude-oil lineJ. Oil& Gas Journal, 1995, 1: 37.5 Sellin R H J, Hoyt J W, Scrivener O. The effect of drag-reducing additives on fluid flows and their industrial applicatiopart 1: basic aspects[J]. J Hydraulic Res, 1982, 20(1):296 Brostow W. Drag reduction in flow: Review of applications, mechanism and prediction[J]. J Ind Eng Chem, 2008, 14(4)7 Moussa T, Tiu C, Sridhar T. Effect of solvent on polymer degradation in turbulent HowJ. J Non-Newton Fluid, 199348(3):2618 Kanwal F, Liggat J J, Pethrick R A. Ultrasonics degradation of polystyrene solutions[J]. Polym Degrad Stabil, 2000, 689 Nurulla I, Tanimoto A, Shiraishi K, et al. Preparation of [pil-conjugated polymers consisting of 2-decylbenzimidazole andthiophene units and chemical properties of the polymers[J]. Polymer, 2002, 43: 1287.[10 Mi H Y, Wang J D, Li H P, et al. Study on oil-soluble drag reducing agent with ultra high molecular weight made by bulkpolymerization[J] Journal of Functional Polymers, 2005, 18(3 ):499-50311 Boor J Jr Ziegler-Natta Catalysts and Polymerization[M. New York: Academic Press Inc, 197912 Huang B T, Wang Z Q. The Progress of Olefins Diolefins Coordination Polymerization(M]. Beijing: Science Press, 1998[13 Zhao H K, Li H P, Zhou Q X Effect of dimethoxydiphenylsilane on active centers ofa-olefin polymerization J. Petro& ChemicalTechnology,2005,34(8):744-748[14 Paul D R, Barlow J W. A binary interaction model for miscibility of copolyTYHCNMHG责任编辑:周蓉