Error analysis of determination for grafting ratio of compatibilizer maleic anhydride⁃grafted polypropylene through acid⁃base back titration

doi:10.19491/j.issn.1001-9278.2023.10.011

Abstract

Abstract:

Based on the error propagation formula， an error model was established for the determination of grafting ratio of PP⁃g⁃MAH through acid⁃base back titration. The effects of sampling amount， concentration of HCl⁃isopropanol solution， and content of grafted maleic anhydride on the determination error of grafting ratio were investigated. PP⁃g⁃MAH was prepared in the laboratory and analyzed by using infrared spectroscopy. The grafting ratio of samples was determined through acid⁃base back titration at different sample amounts and HCl⁃isopropanol solution concentrations. The determination errors of two different maleic anhydride contents of PP⁃g⁃MAH were compared. The results indicated that maleic anhydride was grafted onto the PP molecular chain. The precipitation of PP⁃g⁃MAH and the entrapment effect on KOH were considered as the main reasons for a large determination error and poor reproducibility of grafting ratio. The reduction of the concentrations of acid and base titration solutions and the increase of the sampling amount could reduce the determination error. The minimum determination error was achieved when the concentrations of acid and base titration solutions were 0.01 mol/L. The relative standard deviation of grafting ratio of the prepared PP⁃g⁃MAH was 32 % when the sampling amount was 0.2 g and the concentrations of acid and base titration solutions were 0.01 mol/L. The established error model can be used to optimize the test conditions for the grafting ratio PP⁃g⁃MAH and reduce the determination errors.

Key words: polypropylene, maleic anhydride, grafting ratio, compatibilizer, error propagation formula

CLC Number:

TQ317.2

LI Zhao, JIA Yuanshan. Error analysis of determination for grafting ratio of compatibilizer maleic anhydride⁃grafted polypropylene through acid⁃base back titration[J]. China Plastics, 2023, 37(10): 77-84.

Figures/Tables 10

Fig.1. Relationship between sampling amount and relative standard deviation of grafting ratio

Fig.2. Relationship between concentration of HCl⁃isopropanol solution and relative standard deviation of grafting ratio

Fig.3. Relationship between content of grafted maleic anhydride and the relative standard deviation of grafting ratio and local enlarged view

Fig.4. FTIR of pure PP and PP⁃g⁃MAH

Fig.5. Possible structure of PP⁃g⁃MAH by free radical grafting reaction

Fig.6. Relative standard deviation of grafting ratio under different sampling amounts

Fig.7. Dissolution and precipitation of PP⁃g⁃MAH in xylene and schematic diagram of encapsulation for KOH by PP⁃g⁃MAH

Fig.8. Relative standard deviation of grafting ratio under different concentrations of HCl⁃isopropanol solution

Fig.9. Schematic diagram of entrapment of KOH by PP⁃g⁃MAH precipitation after titration

Fig.10. Determination results of PP⁃g⁃MAH grafting ratio with different maleic anhydride content

References 35

1	徐润君. 国内聚丙烯市场供需分析［J］. 齐鲁石油化工， 2019， 47（2）： 159⁃164.
	XU R J. Analysis of supply and demand in the domestic polypropylene market［J］ Qilupetrochemical Technology， 2019， 47 （2）： 159⁃164.
2	常敏. 全球聚丙烯供需分析及预测［J］. 世界石油工业， 2021， 28（4）： 44⁃50，65.
	CHANG M. Analysis and forecast of global polypropylene supply and demand［J］. World Petroleum Industry， 2021， 28（4）： 44⁃50， 65.
3	闫海生，杨卫兰，高利平. 中国聚丙烯生产工艺技术及品种牌号分析［J］. 现代化工， 2021， 41（5）： 13⁃5，9.
	YAN H S， YANG W L， GAO L P. Analysis on China's polypropylene production technologies and varieties［J］. Modern Chemical Industry， 2021， 41（4）： 13⁃15， 19.
4	CICOGNA F， COIAI S， MOLITERNI D， et al. Co⁃agent mediated functionalization of LDPE/iPP mixtures for compatibilization of WEEE⁃recovered polyvinylchloride［J］. Polymer International， 2016， 65（6）： 621⁃630.
5	ASGARI M， MASOOMI M. Thermal and impact study of PP/PET fibre composites compatibilized with glycidyl methacrylate and maleic anhydride［J］. Composites Part B： Engineering， 2012， 43（3）： 1 164⁃1 170.
6	KHALEDI B， EBRAHIMI N G. Structural analysis of poly（ethylene terephthalate） modified by polypropylene⁃graft⁃maleic anhydride from rheological data［J］. Journal of Applied Polymer Science， 2019， 136（1）： 46896.
7	KUČERA F， PETRUŠ J， POLáČEK P， et al. Controlled reactive modification of polypropylene with maleic anhydride via solvent⁃free technique［J］. Polymer Degradation and Stability， 2019， 168： 108934.
8	王盼盼，韩龙，王莉，等. 高接枝率聚丙烯接枝马来酸酐的制备［J］. 塑料工业， 2018， 46（9）： 35⁃38.
	WANG P P， HAN L， WANG L， et al. Preparation of high grafting ratio polypropylene graft maleic anhydride［J］. China Plastic Inductry， 46（9）： 35⁃38.
9	罗志，李化毅，张辽云. 超细聚丙烯固相接枝马来酸酐用作相容剂的研究［J］. 石油化工， 2017， 46（6）： 731⁃8.
	LUO Z， LI H Y， ZHANG L Y. Preparation and application of PP⁃g⁃MAH via ultrafine PP particles［J］. Petrochemical Technology， 2017， 46（6）： 731⁃738.
10	LOU J， LUO Z， LI Y. The effect of epoxy and tetramethyl thiuram disulfide on melt⁃grafting of maleic anhydride onto polypropylene by reactive extrusion［J］. Journal of Applied Polymer Science， 2016， 133（22）： 43422.
11	周毅，周亚洲. 三元乙丙橡胶接枝顺酐接枝率测定的影响因素［J］. 武汉工程大学学报， 2011， 33（8）： 37⁃39，44.
	ZHOU Y， ZHOU Y Z. Factors influening determination of graft yield in grafting of MAH onto EPDM［J］. J Wuhan Inst Tech， 2011， 33（8）： 37⁃39， 44.
12	雷彩红，李善良，黄伟良，等. 1⁃十六烯对马来酸酐熔融接枝聚丙烯接枝行为的影响［J］. 高分子材料科学与工程， 2011， 27（4）： 95⁃98.
	LEI C H， LI S L， HUANG W L， et al. Melt grafting behavior of maleic anhydride onto polypropylene using 1⁃hexadecene as second monomer［J］. Polymer Materials science and engineering， 2011， 27（4）： 95⁃98.
13	陈晓东，柴振中，杨涛，等. 无气味高接枝率马来酸酐接枝聚丙烯的制备与应用［J］. 塑料工业， 2009， 37（2）： 62⁃66.
	CHEN X D， CHAI Z Z， YANG T， et al. Preparation and application of odorless and high grafting ration PP⁃g⁃MAH［J］. China Plastics and Industry， 2009， 37（2）： 62⁃66.
14	陈晓丽，段良福，刘文鹏，等. 聚丙烯接枝马来酸酐的研究［J］. 塑料助剂， 2006（1）： 18⁃22.
	CHEN X L， DUAN L F， LIU W P， et al. Study on the grafting of PP with maleic anhydr ide by reactive extrusion［J］. Plastics Additives， 2006（1）： 18⁃22.
15	SCLAVONS M， FRANQUINET P， CARLIER V， et al. Quantification of the maleic anhydride grafted onto polypropylene by chemical and viscosimetric titrations， and FTIR spectroscopy［J］. Polymer， 2000， 41（6）： 1 989⁃1 999.
16	DE ROOVER B， SCLAVONS M， CARLIER V， et al. Molecular characterization of maleic anhydride⁃functionalized polypropylene［J］. Journal of Polymer Science Part A： Polymer Chemistry， 1995， 33（5）： 829⁃842.
17	袁锦瑶，高峰，周正亚，等. 聚丙烯接枝马来酸酐接枝率的测定［J］. 中国塑料， 1995， 9（3）： 56⁃60.
	YUAN J Y， GAO F， ZHOU Z Y，et al. Determination of grafting grade of PP grafted maleic anhydride［J］. China Plastics， 1995， 9（3）： 56⁃60.
18	张立峰，郭宝华，张增民. 马来酸酐接枝聚丙烯的固相合成以及酸酐含量的测定［J］. 清华大学学报（自然科学版）， 2001， 41（10）： 5⁃8.
	ZHANG L F， GUO B H， ZHANG Z M. Synthesis of PP⁃g⁃MAH via solid grafting with a quantitative express method for analyzing MAH content［J］. J Tsinghua Univ（Sci&Tech）， 2001， 41（10）： 5⁃8.
19	张志坚，崔丽荣，章建忠，等. 红外光谱法测定玻纤用PP蜡乳液马来酸酐的接枝率［J］. 玻璃纤维， 2019（5）： 13⁃17.
	ZHANG J R， CUI L R， ZHANG J Z， et al. Determination of maleic anhydride grafting ratio of PP wax emulsion used for glass fiber by infrared spectroscopy［J］. Fiber Glass， 2019（5）： 13⁃17.
20	SCLAVONS M， CARLIER V， DE ROOVER B， et al. The anhydride content of some commercial PP⁃g⁃MA： FTIR and titration［J］. Journal of Applied Polymer Science， 1996， 62（8）： 1 205⁃1 210.
21	何丽霞，陈冬梅. 马来酸酐接枝液体异戊橡胶接枝率的测试方法［J］. 功能高分子学报， 2015， 28（4）： 398⁃402.
	HE L X， CHEN D M. Test method of grafting ratio of maleic anhydride grafted liquid isoprene rubber［J］. Journal of Functional Polmers， 2015， 28（4）： 398⁃402.
22	王学敏，刘大壮. 酸碱滴定法测定马来酸酐接枝氯化聚丙烯的接枝率［J］. 工程塑料应用， 2009， 37（1）： 52⁃55.
	WANG X M， LIU D Z. Study on the graftng yeld of malec anhydrde grafted chlorinated polypropylene by neutralization titration［J］. Engineering Plastics Application， 2009， 37（1）： 52⁃55.
23	高永芝，张建斌，刘建伟. 酸碱滴定法测定马来酸酐接枝聚丙烯中的酸酐含量［J］. 工程塑料应用， 2005， 33（5）： 46⁃48.
	GAO Y Z， ZHANG J B， LIU J W. Study on the acid anhydride content in maleic anhydride graft polypropylene by neutralization titration［J］. Engineering Plastics Application， 2005， 33（5）： 46⁃48.
24	西安工业大学. 一种聚合物混合加工的方法： 201510262129.4［P/OL］. 2015⁃05⁃21.
25	BETTINI S H P， DE MELLO L C， MUñOZ P A R， et al. Grafting of maleic anhydride onto polypropylene， in the presence and absence of styrene， for compatibilization of poly（ethylene terephthalate）/（ethylene–propylene） blends［J］. Journal of Applied Polymer Science， 2013， 127（2）： 1 001⁃1 009.
26	MUÑOZ P A R， BETTINI S H P. Montmorillonite as support for peroxide in the melt grafting of maleic anhydride onto polypropylene［J］. Journal of Applied Polymer Science， 2016， 133（42）： 44134
27	庞彦斌. 密度法测量原油含水率的误差分析［J］. 石油大学学报（自然科学版）， 1994，18（6）： 116⁃121.
	PANG Y B. Analysis on errors in measuring water content with density method［J］. Journal of University of Petroleum（Edition of Natural Science）， 1994， 18（6）：116⁃121.
28	李荣才. 误差传递在改进化学分析规程中的一例［J］. 湖南化工， 1986 （1）： 9⁃15.
	LI R C. An example of error propagation in improving chemical analysis procedures［J］. Hunan Chemical Industry， 1986 （1）： 9⁃15
29	郑用熙. 分析化学中的数理统计方法［M］. 北京：科学出版社， 1986：88⁃92.
30	殷敬华，郑安呐，盛京. 高分子材料的反应加工［M］. 北京：科学出版社， 2008：213⁃256.
31	GAYLORD N G， MISHRA M K. Nondegradative reaction of maleic anhydride and molten polypropylene in the presence of peroxides［J］. Journal of Polymer Science： Polymer Letters Edition， 1983， 21（1）： 23⁃30.
32	QIU W， ENDO T， HIROTSU T. Interfacial interaction， morphology， and tensile properties of a composite of highly crystalline cellulose and maleated polypropylene［J］. Journal of Applied Polymer Science， 2006， 102（4）： 3 830⁃3 841.
33	肖祥雄，张兴华. 返滴定法测定PP⁃g⁃MAH的接枝率［J］. 化工之友， 2007（9）： 44⁃45.
	XIAO X X， ZHANG X H. Determination of grafting ratio of PP⁃g⁃MAH by back titration method［J］. Friend of Chemical Industry， 2007（9）： 44⁃45.
34	王爱平，宋永明，王清文，等. 利用挤出技术制备马来酸酐接枝聚丙烯［J］. 东北林业大学学报， 2006， 34（6）： 87⁃89.
	WANG A P， SONG Y M， WANG Q W， et al. Preparation of maleic anhydride grafted polypropylene by reactive extrusion［J］. Journal of Northeast Forestry University， 2006， 34（6）： 87⁃89.
35	HENRY G R P， DROOGHAAG X， ROUSSEAUX D D J， et al. A practical way of grafting maleic anhydride onto polypropylene providing high anhydride contents without sacrificing excessive molar mass［J］. Journal of Polymer Science Part A： Polymer Chemistry， 2008， 46（9）： 2 936⁃2 947.

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