摘要
溶解度参数是研究聚合物溶解的重要参数,在聚合物行业受到广泛的重视,目前研究表明其只是针对纯物质而言。而在工业生产或实验研究中的原料或者产品常常并不是纯物质,或多或少含有一些杂质或添加剂,这就限制了溶解度参数的使用。研究过程中常常或者需要先提纯研究对象,或者干脆就忽略了杂质的影响,但是到底杂质的存在对聚合物的溶解度参数有没有影响或者有多大的影响没有见到相关报道。为了使得溶解度参数在这些体系也能够使用,本文以杂质对聚合物溶解度参数的影响为研究对象,并且选择聚丙烯专用涂料中常用的一种附着力促进剂氯化聚丙烯为例展开研究。
本文首先采用薄层色谱法验证了CPP-4中共混物的存在,然后选择了对CPP进行分离提纯的最佳条件。
接着对四种氯化聚丙烯提纯后和提纯前的氯含量进行了分析,并对其结果进行了讨论。结论是,对于油墨用的氯含量30%的氯化聚丙烯CPP-2来说,杂质是其高氯化物,是合成中的副产品。而对于涂料用的氯含量为25%附近的氯化聚丙烯CPP-4来说,杂质是为了改进其性能而人为加入的,其氯含量要比原纯样品低。
测定了不同氯含量的氯化聚丙烯提纯前后在各种溶剂中的溶解情况,结果表明对于选择的38种溶剂,提纯前后样品的溶解性能没有变化。进而用Hansen的方法,优化求出了用于油墨和用于涂料的两种氯化聚丙烯的三维溶度参数,并讨论了Hansen法求三维溶度参数的精度。
浊度滴定法是测定聚合物溶解度参数的一种最为经典的方法。引起实验误差的主要原因是浊点的判断,本文采用激光浊度滴定的方法,首先确定了实验中判断滴定终点的统一方法,提高了结果的精度。研究了溶剂和沉淀剂对浊度法测定溶度参数的影响。测定了不同氯含量氯化聚丙烯提纯前后的的溶解度参数,随着氯含量的增加,溶解度参数变大。并且实验结果也说明杂质的存在对氯化聚丙烯的溶解度参数存在一定的影响,但是不大。
采用特性黏度法测定了CPP-4中杂质的溶解度参数,发现其溶度参数值比Hansen法或是浊度滴定法得到的提纯后CPP-4的溶度参数要高,说明其中的杂质极性较高。
Solubility parameter has caught a wide attention in polymer industry ,since it is a powerful weapon in the study of polymer dissolved ,but the study showed that it only could be used in pure substances. Raw materials or products in industrial production or experimental study always are not pure, which contain more or less impurities or additives, all of these limit the use of solubility parameter,and we should purify the products in the course of study and research, or simply to ignore the impact of the impurities. There has been not relevant reports whether or not the existence of impurities in the polymer put influence on its solubility parameter. In this paper,we choose chlorinated polypropylene a adhesion promotion in coatings an example of studing to show the impact of impurities to solubility parameters of polymer in order to using solubility parameters in these systems.
TLC is used to verify the existence of impurities in CPP-4 firstly. The best experiment condition was selected to purify CPP. Then the chlorine content of four kinds of CPP both before and after the purification was analyzed and the results were discussed. The impurities in CPP-2 which contains about 30 percent of chlorine used in ink are by-products with high chloride content. As for the impurities in CPP-4 which contains about 25 percent of chlorine used in coatings,it is added to improve its performance by adding artificial, and its chlorine content is lower than the original pure samples'.
The solution of four kinds of CPP both before and after the purification was tested in various solvents. The results show that the dissolution performance of samples before and after the purification has not changed in the 38 kinds of solvents we choosed. The three-dimensional solubility parameter of CPP-2 and CPP-4 was obtained by Hansen method. The accuracy of three-dimensional solubility parameter determined by Hansen method was discussed.
Turbidimetric titration is the most classic way to test the polymer's solubility paramete. A unified method to determine the cloud point was indentified firstly in this paper which could improve the accuracy of the results,because the judgement of the cloud point is the kay reason in experimental error. The impacts of solvents and non-solvents to solubility parameters determined by turbidimetric titration were studied. The solubility parameters of CPP was experimented ,the result showes that the solubility parameter is on the rise while the chlorine content increasing.
The solubility parameter of impurities in CPP-4 was determined by inherent viscosity .Its solubility parameter is higher than the solubility parameter of CPP-4 after purification determined by Hansen method and turbidimetric titration ,indicated that the polar of impurities is higher than purity CPP-4.
引文
[1]范忠雷.氯化聚丙烯及其马来酸酐接枝物基础性质的研究[D].郑州大学博士学位论文.2003.
[2]马向东,刘大壮,孙培勤.氯化聚丙烯接枝马来酸酐的合成研究[J].涂料工业,2007,37(7),29-31.
[3]马向东.氯化聚丙烯及其马来酸酐接枝物基础性质的研究[D].郑州大学博士论文,2003.
[4]董雪茹.氯化聚丙烯的接枝改性及其乳液性质的研究[D].郑州大学博士论文,2003.
[5]刘敏,刘大壮.甲苯改性氯化聚丙据接枝物的合成及应用[J].上海涂料,2006,44(5):4-6.
[6]刘敏,刘大壮,孙培勤,孙绍晖.离子液体催化氯化聚丙烯与甲苯烷基化反应的研究[J].胶体与聚合物,2005,23(4):18-20.
[7]涂料工艺编委会.涂料工艺(第三版)[M].化学工业出版社,1997,61-77.
[8]逯云峰,孙国文,蒋荣.聚丙烯原料杂质对聚合的影响及净化技术的发展[J].四川化工,2005,6(8):24-27.
[9]张跃.几种杂质对DMDAAC单体聚合反应性影响的研究[D].南京理工大学硕士论文,2006.
[10]夏志林,范正休,邵建达.薄膜内杂质分布的分形特征[J].中国激光,2006,33(1):111-115.
[11]艾秀娟.环氧树脂中杂质的分析报告[J].江西化工,2003,3(1):76-77.
[12]Hildebrand J H.J.Am.Chem.Soc,1929,51:66.
[13]Hildebrand J H,Scott R L.The Solubility of non-elctrolyters(3rd ed)[M].New York:Reinhold,1949.
[14]Burrel H.Offical Digest,1955,27(369):726-758.
[15]Hansen C M.The Three Dimensional Solubility Parameter-Key to Paint Component Affinities:Ⅰ.Solvents,Plasticizers,Polymers,and Resins[J].Journal of Paint Technology,1967,39(505):104-117.
[16]Hansen C M.The Three Dimensional Solubility Parameter-Key to Paint Component Affinities:Ⅱ.Dyes,Emulsifiers,Mutual Solubility and Compatibility,and Pigments[J].Journal of Paint Technology,1967,39(511):505-510.
[17]Hansen C M.The Three Dimensional Solubility Parameter-Key to Paint Component Affinities:Ⅲ.Independent calculation of the parameter components[J].Journal of Paint Technology,1967,39(511),511-514.
[18]Karger B L,Snyder LR,Eon C.Analyt.Chem,1978,50(2126).
[19]刘国杰,黑恩成.一个新的溶解度参数[J].化工学报,1994,45(6):665-672.
[20]俞春芳,黑恩成,刘国杰.聚合物的溶剂选择与新的两维溶解度参数[J].化工学报,2001,52(4):288-294.
[21]夏正斌,涂伟萍,杨卓如,陈焕欣.溶解度参数在研制高薪能丙烯酸聚氨酯涂料中的应用[J].高校化学工程学报,2001,15(1):88-92.
[22]游长江,石小华.溶解度参数分析PVC共混物相容性[J].化学建材,1999,4:9-12.
[23]李跟宝,周龙保,刘圣华,潘克煜.运用溶解度参数理论研究二甲醚与其它燃料、润滑添加剂、聚合物的相容性[J].内燃机学报,2005,23(4):352-356.
[24]Hansen C M.Broendby Den.Polymer additives and solubility parameters.Progress in Organic Coatings[J].Elsevier B V,2004,51(2):109-112.
[25]Hansen C M.Aspects of solubility,surfaces and diffusion in polymers[J].Progress in Organic Coatings,2004,51(1),55-66.
[26]周瑞明.粘接机理的扩散理论与溶解度参数[J].温州师范学院学报(自然科学版),1994,3:60-64.
[27]常静.环氧/丙烯酸树脂相容性及自分层行为研究[D].郑州大学,2006.
[28]Hansen C M.Broendby Den.Polymer additives and solubility parameters.Progress in Organic Coatings[J].Elsevier B V,2004,51(2):109-112.
[29]Frisch P D.Application of solubility-parameters to agricultural chemical problems[J].ASTM Special Publication,1996,1312:21-35.
[30]Kim Youngeun,Hwang JiHwan,Baek Namln.Kim WooSik.A novel application of solubility parameter in extraction of bioactive substances from natural products[J].AIChE Annual Meeting and Fall Showcase,Conference Proceedings[C].American Institute of Chemical Engineers,2005,4489-4501.
[31]Marcus Yizhak.Are solubility parameters relevant to supercritical fluids?[J].Journal of Supercritical Fluids,2006,38(1):7-12.
[32]黄雪红,许国强.SBS和MMA-丙烯酸丁酯接枝聚合物的溶解性和溶度参数的订定[J].合成橡胶工业,1998,21(2):99-101.
[33]北京大学化学高分子教研室.高分子实验与专论[M].北京大学出版社,1990.
[34]Imaizumi Mitsuhiro,Nagata Takefumi,Goto Yasutomo,Okino Yoshiro,Takahashi Tatsuhiro,Koyama Kiyohito.Solubility parameters of biodegradable polymers from turbidimetric titrations[J].Kobunshi Ronbunshu,2005,62(9):438-440.
[35]Jayasri A,Yaseen M.Solubility parameters of polymeric materials by turbidimetric titration[J].Proc.- Semin.Polym.Surf.Coat,1982.
[36]S C NG,K K CHEE.Solubility parameters of copolymers as determined by turbidimetry[J].Eur.Polym.t,1997,33(5):749-752.
[37]范忠雷,刘扬等.氯化聚丙烯相关物性参数的测定[J].塑料工业,2003,31(4):44-47.
[38]肖聪明,颜文礼.反相气相色谱测定距本息的溶解度参数[J].色谱.1998,16(4):354-355.
[39]宋栩兵,许承威.薄层色谱法测定聚苯烯的溶解度参数[J].高等学校化学学报,1982,3(2):271-273.
[40]刘德新,李桂贞.薄层色谱法测定聚合物溶解度参数的研究[J].塑料工业, 1991,(4):46-49.
[41]复旦大学高分子科学系等.高分子实验技术[M].上海:复旦大学出版社,1996.
[42]左榘,张越等.溶胀动力学法测定高聚物溶度参数[J].高等学校化学学报,1994年4月,15(4):620-623.
[43]Small P.S..Some factors affecting the solubility of polymers[J].J Appl Chem,1953,3:71.
[44]Fedors R.F.A method for estimation both the solubility parameters and molar volumes of liquids[J].Polymer Eng and Sci,1974,14(2):147.
[45]D.W.范克雷维伦.聚合物的性质-性质的估算及其与化学结构的关系.许元泽等.北京:科学技术出版社,1981.
[46]李俊山,姜本法等.橡胶助剂溶解度参数的理论估算[J].橡胶工业,1992,39(11):685.
[47]高素莲,周宁国.现代分离纯化与分析技术在高分子材料研究中的应用[M].中国科学技术出版社,2004.
[48]董炎明.高分子分析手册[M].北京:中国石化出版社,2004,60.
[49]杨建军,吴明元等.CR/VAC/MMA/AA四元接枝共聚物合成及接枝率的研究[J].安徽大学学报(自然科学版),2005年1月,29(1):68.
[50]杨建军,吴明元等.氯丁橡胶/苯乙烯/甲基丙烯酸甲酯/丙烯酸接枝共聚物的合成[J].合成橡胶工业,2005,28(2):95.
[51]冯惠荣,王平等.接枝氯丁胶粘剂接枝率的测定[J].中国胶粘剂.3(6):41.
[52]林水东.聚丙烯固相接枝甲基丙烯酸乙酯改性研究[J].龙岩学院学报,2005,23(3):100.
[53]马向东,刘大壮等.氯化聚丙烯接枝马来酸酐接枝率的测定[J].粘接,2002,23(5),12.
[54]黄雪红,许国强。MMA、BA与SBS接枝共聚的研究[J]。石油化工,1998,27(9):648-652.
[55]崔小明.氯化聚丙烯的应用与开发[J].陕西化工,1996,4:5-7
[56]金栋.氯化聚丙烯的生产应用与市场前景[J].四川化工与腐蚀控制,2002,5(4):48-52
[57]范忠雷,唐四叶,刘大壮,朱冬生.氯化聚丙烯研究进展[J].现代化工,2004,24(12):16-19.
[58]傅和青,黄洪,张心亚,陈焕钦.氯化聚丙烯接枝改性研究[J].化学与粘合.2004,1:23-25
[59]Siye Tang,Dazhuang Liu.Determination of three-dimension solubility parameters of chlorinated polypropylene by ultrasonic degradation[J].Physics Chemistry of Liquids,2006,44(5):490-498.
[60]范忠雷,刘大壮.氯化聚丙烯溶度参数的研究[J].中国胶粘剂,2002,12(3):10-13.
[61]崔慧,陶绪泉.薄层色谱在高分子研究中的应用[J].分析化学,1995,23(5):586-593.
[62]欧玉静,赵霞,冯辉霞等.氯化聚丙烯及其马来酸酐接枝物的氯含量研究[J].粘接,2007,28(6):24-25.
[63]刘敏,唐四叶等.氧瓶燃烧-点位滴定法测定有机氯化物的氯含量[J].上海涂料,2005,43(9):35-37.
[64]高振,丁利,刘大壮等.改良氧瓶燃烧-离子色谱法测定氯化聚丙烯中的氯含量[J].化工时刊,2007,21(8):42-44.
[65]E P Lieberman.Quantification of the Hydrogen Bonding Parameter[J].Official Digest,1962,(1):30-51.
[66]刘大壮,常静,孙培勤.温度对马来酸酐改性的丙烯-丁烯共聚物的Hansen 三维溶度参数的影响[J].郑州大学学报(工学版),2005,26(2):1-5.
[67]Tadanori Funasaka et al.Adhesive ability and solvent solubility of propylene-butane copolymers modified with maleic anhydride[J].International Journal of Adhesion and Adhesives,1962,(19):367-371.
[68]Irwin A Wiehe.Polygon mapping with two-dimensional solubility parameters[J].Industry Engineering Chemistry Research,1995,34:661-673.
[69]Dazhuang Liu,Zhonglei Fan,Peiqin Sun and Xueru Dong.Solution properties of chlorinated polypropylene and maleic anhydride grafted chlorinated polypropylene[J].Physics and Chemirstry of Liquids,2004,42(6):551-560.
[70]唐四叶.氯化聚丙烯溶液性质和超声降解动力学的研究[D].郑州大学博士论文,2006.
[71]Hansen C M.The Universality of The Solubility Parameter[J].I&EC Product Research and Development,1969,8(1):2-11.
[72]Hansen C M,Broendby Den.50 Years with solubility parameters -past and future[J]..Progress in Organic Coatings.Elsevier B V,2004,51(1):77-84.
[73]Farhad Gharagheizi,Mehdi Sattari,Mahmood Torabi Angaji.Effect of Calculation Method on Values of Hansen Solubility Parameters of Polymers[J].Polymer Bulletin,2006,57:377-384.
[74]K.W.SUH,J.M.CORBETT.Solubility Parameters of Polymers from Turbidimetric Titrations[J].Journal of Applied Polymer Science,1968,12:2359-2370.
[75]K.W.SUH,J.M.CORBETT.Solubility Parameters of Polymers from Turbidimetric Titrations[J].Journal of Applied Polymer Science,1968,12:2359-2370.
[76]何曼君.高分子物理[M].复旦大学出版社,2003,7.