α-烯烃减阻剂特性粘度的研究 α-烯烃减阻剂特性粘度的研究

α-烯烃减阻剂特性粘度的研究

  • 期刊名字:新疆大学学报(自然科学版)
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  • 论文作者:朱桂丹,陆江银,王春晓,齐艳杰
  • 作者单位:新疆大学化学化工学院,南通市经济技术开发区化工安全生产监督管理局
  • 更新时间:2020-03-23
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第31卷第2期.新疆大学学报(自然科学版)Vol.31, No.2 .2014年5月Jourmal of Xinjiang University(Natural Science Edition)May, 2014Study on Intrinsic Viscosity of a-olefin DragReducing Agent(DRA 1)*ZHU Gui-dan' , LU Jiang-yinl+, WANG Chun-xiao2, QI Yan-jie'(1.College of Chemistry & Chemical Engineering, Key Laboratory of Oil and Gas Fine Chemicals of Ministry of Education,Xinjiang University, Urumqi, Xinjiang 830046, China;2. Nantong economic-technological development area administration of work safery, 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 efect of the drag reducingpolymer intrinsic viscosity. The result indicate viscosity could reach 8.8 dl/g drag reducing ficiency can reach 43.12%which means in certain range drag reducing eficiency is proportional to viscosity. The optimal operation conditions are at-3"C, the dosages of the main catalyt(TiClL/MgCl), co-catalyst(Al(Et)3), and diphenyldimethoxysilane(DDS) are 0.085g, 0.14 ml and 0.04 mL, respectively.Key words : drag reducing, bulk polymerization, intrinsic viscosity, catalyst, eficiencyCLC number: TQ325.1 Document Code: A Article ID : 1000-2839(2014)02-0199-06a-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.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830046;2.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2600摘要:通过本体聚合在催化剂TiCl4/Al(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8.8 dl/g时减阻率可达到43.1%,即在- -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3°C,主催化剂(TiCl/MgCl2)、助催化剂(AI(Et)3)和二苯基二甲氧基硅烷(DDS)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 efectively'". 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 pollutionl2-61. But theproblem of shear degradation is inevitable, and the shear resistance has significant impact on drag reducing properties7.Viscosity change is related with shear degradation, so the shear resistance of the polymer could be represented by theviscosity change.Under 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 the* Received Date: 2014-01-18Foundation Item: supported by the National Natural Science Foundation of China (20963010).Biography: ZHU Gui-dan( 1988-), female, a master student, the research direction is oil drag reducing agent.i Corresponding 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 indirectlys8. In addition,molecular weight is another evaluation standard for the polymer shear stability, Nurullal9 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 indirectly.In this paper, a-hexylene/a-dodecene copolymers were synthesized with TiCl/Al(Et)3 as catalysts and a-olefin asmonomers by bulk polymerization, the efects of the reaction temperature, catalyst dosage, DDS dosage and solutionblending on the intrinsic viscosity of the DRA were investigated. Also, the intrinsic viscosity of the polymer afterultrasonic shear was researched.1 Experimental1.1 Materials and facilituesa-dodecene (Fluka product), moisture content is not higher than 25 mg/L; a-hexene, J&K's 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 vacum glove box, Nanjing University Instrument Factory; DZF-6030A vacum drying oven and DHG-9070A-type air blowing thermostatic oven, Shanghai Scientific Instrument Co.,Ltd; AR224CN millionth electronicbalance, Ohaus Instruments (Shanghai) Co., Ltd.1.2 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 ovenat 120°C 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 begins.The monomer a 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 bath.When 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 vacum drying oven (60°C) to dry until constant weight. Dried products were dissolved with hexane todetermine.The polymer was dissolved with hexane at the temperature of 25°C and then the viscosity was determined byUbbelohde viscometer.1.4 Evaluation of shear strength resistanceThe breaking of polymer molecular chains caused by the ultrasonic shearl8l could achieve the same effect of shearstrength compared to mechanical rupture, also the viscosity of polymer would change, so the measurement of viscosityafter 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 200Wconditions.2 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 bending vibration on the line near 1 376.7 cm !.The stretching vibration and bending vibration of saturated hydrocarbon were about 2 920.6 cm-1 and 2 852.7 cm 1respectively, such vibrations were the strong bands. The bending vibration strengths of -(CH2)n- near 1 461.5 cm-',where, 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 a-olefin Drag Reducing Agent(DRA )2012.2 Analysis of XRDThe XRD of polymer was dissolved by dimethyl benzene and then deposited by alcohol were shown in fig.2.Disperse diffractive peak appeared at 20= 20*, and it belongs to long-chain olefin because seams ranges!9l are near0.35~0.39 nm. To sum up, fig.2 was the curve of disperse difractive peak, which showed a low degree of crstalline.Rigid group was not involved in the reaction, suggesting the polymer was the flexible one.1500 1000 1500 2000 2500 3000 3500 4000 450010304060Wave number/cm-120 /(degreeFig 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(L1645), and the orthogonal test factors were listed in table 1. Using Mark-Houwink equation, according to the formulaη= KM", in which, K= 1.544x 104 and a=0.708, and viscosity results and the measurements of viscosity averagemolecular weight were listed in table 2.Table 1 Orthogonal experiment factor level table (L164 )Factor Level A(g)B(ml) C(ratio) D(h)E(°)0.080.53:20.06.42:240.05).21:360.040.118A: main catalyst dosage; B: co-catalyst dosage; C: Volume ratio of olefins (ar-hexene:a-dodecene); D: reactiontime; E:reaction temperature.Table 2 Measurements of viscosityNo.n(dl/g)M,(x10-6)No. n(dl/g)6.043.076.163.159.225.5706.343.288.454.92118.094.639.575.879.065.436.703.55136.483.398.264.7746.283.247.354.84157.243.967.664.29168.124.66The range of polymers viscosity analysis was listed in the following table:As can be seen in table 3, the best reaction conditions were A1B4C2D2E3, what's more, main catalyst dosage,co-catalyst dosage, volume ratio of olefins (ar-hexene:a-dodecene), reaction time and reaction temperature are 0.08g,0.1g, 2:1, 24 h and -5°C.新疆大学学报(自然科学版)2014年Table 3 Range analysis of polymerFactor Parameters .AK133.2825.3830.5128.7327.28K229.9730.10 .32.2231.4530.85K329.6531.13 .28.5529.6132.25K428.1234.4129.7431.2330.64<18.326.34 .7.637.186.82k27.497.528.067.86.717.417.787.147.4006k47.038.607.437.817.661.292.260.92 .0.611.24At the same time, the range analysis results showed that the influencing sequence of the viscosity from high tolow were the co-catalyst dosage, the main catalyst dosage, polymerization temperature, the ratio of monomers andpolymerization time, respectively.Under the optimum conditions of polymerization ( the main catalyst dosage0.08 g, the co catalyst dosage0.10 mL,polymerization temperature -5 C, the ratio of monomers 2:1, and polymerization time 24 h) , the intrinsic viscosity ofthe polymers reached 9.84 dl/g.2.3 Efect 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 increased.2.4 Efect of co-catalyst dosage on viscosityFig.4 shows the effect of co- catalyst dosage on viscosity. The results ilustrated 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 gradually.The maximum value of viscosity up is 10.80 dl/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 activity.10.5-1110.0-109.9.0电8.5-8.7.57.00.04 0.05 0.06 0.07 0.00.09 0.100.00.0.2 030.205m(TO4VgVAI(E0)3/mlFig 3 Effect of main catalyst dosage on viscosityFig 4 Effect of co-catalyst dosage on viscosity2.5 Eftect of polymerization temperature on viscosityIn terms of heterogeneous olefin coordination polymerization with Ziegler-Natta catalyst, a lot of heat wouldrelease in the reaction process, and further gel would appear soon in the reaction systeml0 . Thus, controlling reaction第2期ZHU Gui-dan, et al: Study on Intrinsic Viscosity of ar olefn Drag Reducing Agent(DRA)203temperature is significant. Fig.5 shows the changes of viscosity with reaction temperature. The results ilustratedthat at a range of -10°C to -3°C, with temperature increased, the viscosity increased, but then decreased. When thetemperature was -3°C, the viscosity could receive a maximum value. This relationship could be explained by theArrhenius equation.k= ko exp(-品),Where, E。is the activation energy, ko is the pre-exponential factor.Integration of this equation leads toln务=--号(方-+).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 acelerated the system viscosity which madethe monomer diffusion and mass transfer blocked, and then easily led to gelatin phenomena, ultimately it was notconducive to the increasing of viscosity.When 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 polymer.2.6 Eftect 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 afectthe viscosity of the polymrl"l. Huang Baotong121 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 effecton viscosity, 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 efect 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 site,and 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 viscosityl131.0.5T11.0-10.0-10.5-9.5-9.0-.5-8.5-司9.0-7.7.07.5--12-1086422售460.00 0.02 0.04 0.06 0.08 0.10polymerization temperature('C)V(DDS)/mlFig 5 Efect of polymerization temperature onintrinsic viscosityFig 6 The inftuence between viscosity and dosage of DDS2.7 Eftect of solution blending on viscosityPolymer blend is an important means of polymer modification4I. Due to less material and simple operation,solution blending has been widely used in laboratory for basic research. The performance of blend system would bediferent from the one of single component, especially the rheology. Therefore, the changes of viscosity of 7# and15# were investigated after being mixed, the results are shown in Fig.7. The viscosity of blends declined first but thenincreased with the addition of the content of component 7#, and could reach a maximum value within a certain ratio,which, 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 viscosity.2.8 Efect 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 diferent viscosity valueswere researched by the means of ultrasonic degradation, and results were shown in Fig.8. As we can see, viscosityshowed downward trend with the increasing of shear time. At the same time, with increasing of the polymer initialviscosity, 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 was.Thus, 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 applications.119.10一- initial viscosity=7.35. initial viscosity= -8.268.5-一initial viscosity-9.06→- initial viscosity=10.77号6F5.7.7.00 2040 60 80100-2 024681012141618207* (w% )shear time(min)Fig 8 The influence between intrinsic viscosityand ultrasonic degradationFig 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 efliciency 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 performance.Table 4 The drag reducing fficiency in the different polymerizationConditonsAViscosity /dl/8.269.810.8(Drag Reduction /%34.16 .36.2338.5043.123 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-catalystdosage, 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 different drag reducing polymers synthesized bychanging the values of infuencing factors, their drag reducing properties could be known by measuring their intrinsicviscosities.(下转第211页)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211[2] 张海藩.软件工程导论[M].北京:清华大学出版社, 206112-114.3] 韩万江软件工程案例教程[M]北京:机械工业出版社, 2007,45-48.[4] 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, 2010,340-343.5] Katysovas T .A first look at Google Android.[s1]:Free University of Bolzano, 2008,12-26[6] DIMARZIO J F. Android: a programmer's guide[M].New York: McGraw-Hill, 2008.7] 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, 2010.8] 田俊静,张波,黄湘情Android基础教程[M].北京:人民邮电出版社, 2011,53-57.[9]吴亚峰,索依娜.Android 核心技术与实例详解[M].北京:电子工业出版社, 2010,248-250.[10]林城.Android 2.3应用开发实战[M]北京:机械工业出版社, 2011,160-180.[1] 李金霖,赖超,龙曦等基于Android 平台的手机日程管理系统[].计算机与数字工程: 2011,3 (39) :67-68.[12]汪永松.Android平台 开发之旅[M]北京:机械工业出版社, 2011,186 189.3] 巢文涵.Android多媒体开发高级编程[M].北京:清华大学出版社, 2012,125-129.[14] 宋小倩,周东升基于Android平台的应用开发研究[D.软件导刊,2011,10(2):104- 106.[15]赵亮, 张维基于Android技术的界面设计与研究[D.电脑知识与技术,2009,29(5): 184-185.[16]蓝坤, 张跃. Android在远程医疗信息系统中的应用[].计算机应用,2013,33(6): 1791-1792.责任编辑:闫新云(上接第204页)AcknowledgementsThe 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 [J]J Surfactants Deterg, 2001, 4(1):65.[2] LiG P, Yang R, Wang K H. The new progress of drag reducer in research and production at home and abroad[J]. Oil &Gas Storageand Transportation, 2000, 19(1): 3.[3] Hu T N. Optimization strategy on batch transportation of oil product[J]. Oil & Gas Storageand Transportation, 1997,16(6): 11-14.[4] Boschat J, Sabathier J. Ecuador plans expanded crude-oil line[J]. Oil&Gas Journal, 1995, 1: 37.[5] Sellin R H J, Hoyt J W, Scrivener O. The efect of drag- reducing additives on fuid flows and their industrial applicationspart 1: basic aspects[J]. J Hydraulic Res, 1982, 20(1): 29.[6] Brostow W. Drag reduction in flow: Review of applications, mechanism and prediction[J]. J Ind Eng Chem, 2008, 14(4):409-416.7] Moussa T, Tiu C, Sridhar T. Effect of solvent on polymer degradation in turbulent flow[J]. J Non-Newton Fluid, 1993,48(3): 261.[8] Kanwal F, Liggat J J, Pethrick R A. UItrasonics degradation of polystyrene solutions[J]. Polym Degrad Stabil, 2000, 68:44] Nurulla I, Tanimoto A, Shiraishi K, et al. Preparation of [pi-conjugated polymers consisting of 2-decylbenzimidazole andthiophene units and chemical properties of the polymers[J]. Polymer, 2002, 43:1287.[10] MiH Y, WangJ 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 ): 499-503.[11]Boor J Jr. Ziegler-Natta Catalysts and Polymerization[M]. New York: Academic Press Inc, 1979.[12] Huang B T, Wang Z Q. The Progress of Olefins & Diolefins Coordination Polymerization[M]. Bejing: Science Press, 1998.[13] Zhao H K, Li H P, Zhou Q X. Effect of dimethoxydiphenylsilane on active centers ofa-olefin polymerization[J]. Petro&zChemicalTechnology, 2005, 34(8): 744-748.[14] Paul D R, Barlow J W. A binary interaction model for miscibility of copolymers in blends[J]. Polym Rev, 1984, 25(4):487-497.责任编辑:周蓉

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