聚羧酸系高性能减水剂分子在稀溶液中尺寸及其在体积排除色谱表征中表观分子量的模型研究

王衍伟; 赵红霞; 舒鑫; 杨勇; 冉千平

doi:10.11777/j.issn1000-3304.2017.16297

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聚羧酸系高性能减水剂分子在稀溶液中尺寸及其在体积排除色谱表征中表观分子量的模型研究

研究论文 | 更新时间：2021-03-19

- 聚羧酸系高性能减水剂分子在稀溶液中尺寸及其在体积排除色谱表征中表观分子量的模型研究
- Modelling the Equilibrium Sizes of Comb-shaped MPEG-type Polycarboxylate-type Superplasticizers in Dilute Solution and Their Apparent Molecular Weight in Conventional Size Exclusion Chromatography
- 高分子学报 2017年第6期页码：1008-1018
- 作者机构：
  
  1.江苏苏博特新材料股份有限公司高性能土木工程材料国家重点实验室南京 211103
  2.苏州大学材料与化学化工学部新型功能高分子材料国家地方联合工程实验室苏州 215123
- 作者简介：
  
  冉千平, E-mail:qpran@cnjsjk.cn Qian-ping Ran, E-mail:qpran@cnjsjk.cn
- 基金信息：
  
  国家自然科学基金(51408273);高性能土木工程材料国家重点实验室开放基金(2014CEM001);国家自然科学基金(21204061)
- DOI：10.11777/j.issn1000-3304.2017.16297
  中图分类号：
- 纸质出版日期：2017-6-20，
  
  收稿日期：2016-9-23，
  
  修回日期：2016-10-10，
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王衍伟, 赵红霞, 舒鑫, 杨勇, 冉千平. 聚羧酸系高性能减水剂分子在稀溶液中尺寸及其在体积排除色谱表征中表观分子量的模型研究[J]. 高分子学报, 2017,(6):1008-1018.

Yan-wei Wang, Hong-xia Zhao, Xin Shu, Yong Yang, Qian-ping Ran. Modelling the Equilibrium Sizes of Comb-shaped MPEG-type Polycarboxylate-type Superplasticizers in Dilute Solution and Their Apparent Molecular Weight in Conventional Size Exclusion Chromatography[J]. Acta Polymerica Sinica, 2017,(6):1008-1018.
王衍伟, 赵红霞, 舒鑫, 杨勇, 冉千平. 聚羧酸系高性能减水剂分子在稀溶液中尺寸及其在体积排除色谱表征中表观分子量的模型研究[J]. 高分子学报, 2017,(6):1008-1018. DOI： 10.11777/j.issn1000-3304.2017.16297.

Yan-wei Wang, Hong-xia Zhao, Xin Shu, Yong Yang, Qian-ping Ran. Modelling the Equilibrium Sizes of Comb-shaped MPEG-type Polycarboxylate-type Superplasticizers in Dilute Solution and Their Apparent Molecular Weight in Conventional Size Exclusion Chromatography[J]. Acta Polymerica Sinica, 2017,(6):1008-1018. DOI： 10.11777/j.issn1000-3304.2017.16297.

摘要

针对被称为“第一代聚羧酸高性能减水剂”（以下简称为MPEG-type PCE）的甲基丙烯酸（MAA）/烯酸甲酯（MAA-MPEG）梳状共聚物分子，从高分子物理基础理论出发，构建等效自由连接链模型，结合前人的理论结果和实验数据，得到了MPEG-type PCE分子的回转半径、流体力学半径及其相应的支化参数的数学表达式.在此基础上，报道了以下三方面的工作：首先，将计算结果与文献中的实验结果进行比较，检验模型的合理性；其次，利用所建立的数学模型考察主链分子量、侧链分子量和侧链接枝密度对PCE分子的回转半径和流体力学半径的影响；最后，结合近年来发展的体积排除色谱分离理论，对PCE分子的真实分子量与其常规体积排除色谱“表观分子量”（又被称为GPC分子量）两者之间的差异进行了分析.本文所提出的计算模型和数学表达式没有不确定的指前因子，可用来估算MPEG-type PCE分子在稀水溶液中的尺寸以及根据其GPC分子量估算真实分子量.

Abstract

A simple "equivalent freely-jointed chain" model

parameterized with literature data on the persistence length of linear poly(methacrylic acid) (PMA) and poly(ethylene oxide) (PEO)

and the molecular weight dependence of the radius of gyration of linear PEO in aqueous solution

is developed for the so-called MPEG-type comb-shaped polycarboxylate ester-or ether-based superplasticizers (PCEs). The model yields analytical expressions of the radius of gyration

the hydrodynamic radius

as well as their respective branching parameters and the characteristic size ratio of the radius of gyration to the hydrodynamic radius as a function of backbone molecular weight

side chain molecular weight

and the number of side chains

assumed to be evenly distributed along the polymer backbone

in the continuum limit. Our calculations andexperimental results in the literature showed a fairly good agreement

especially when a correction factor of magnitude 1.1 for the radius of gyration and of 1.4 for the hydrodynamic radius weretaken into account. After model validation

more predictions were made based on this simple model. Results of the radius of gyration and the hydrodynamic radius were presented as a function of the molecular weight of the PMA backbone

the molecular weight of the PEO side chains

and the molar ratio of methacrylic acid to polyalkyleneglycol methacrylate (known as the C/E ratio). It was found that the ratio of the radius of gyration to the hydrodynamic radius of PCEs fell mostly in the range of 0.85 to 1.0

notably less than those commonly found for linear polymers. To further facilitate applications of our theoretical model in practice

predictions were made to the ratio of the apparent molecular weight measured in aqueous size exclusion chromatography by conventional column calibration using linear poly(ethylene oxide) polymer standards to the true molecular weight measured by

e.g

light scattering

by assuming that polymers having the same retention volume had approximately the same hydrodynamic radius. While it was common for branched polymers that the apparent GPC molecular weight using a linear polymer standard was less than their true molecular weight

the reverse could also be found for PCEs due to its copolymer feature. The mathematical model developed in this work

besides its simplicity

does not contain undetermined numerical prefactors

which avoids ambiguity in its practice.

关键词

梳形共聚物等效自由连接链回转半径流体力学半径体积排除色谱

Keywords

Comb-shaped polycarboxylate-type superplasticizersFreely jointed chainRadius of gyrationHydrodynamic radiusSize exclusion chromatography

references

Qianping Ran , Shishan Wu , Yuncan Zhang , Fen Wu . . Polymer Bulletin , 2014 . ( 2 ): 68 - 77.

冉千平 , 吴石山 , 张云灿 , 吴汾 . . 高分子通报 , 2014 . ( 2 ): 68 - 77.

Changwen Miao , Qianping Ran , Jinxiang Hong , Jing Xu , Dongliang Zhou . . Materials China , 2009 . 28 ( 11 ): 36 - 45.

缪昌文 , 冉千平 , 洪锦祥 , 徐静 , 周栋梁 . . 中国材料进展 , 2009 . 28 ( 11 ): 36 - 45.

Xiangming Kong , Enxiang Cao , Shanshan Hou . . China Concrete , 2010 . ( 5 ): 28 - 37.

孔祥明 , 曹恩祥 , 侯珊珊 . . 混凝土世界 , 2010 . ( 5 ): 28 - 37.

Ziming Wang . Synthesis, Performance and Application of Polycarboxylate-type High Performance Superplasticizers , : Beijing China Architecture & Building Press , 2009 . 90 - 96.

王子明 . 聚羧酸系高性能减水剂—制备、性能与应用 , : 北京中国建筑工业出版社 , 2009 . 90 - 96.

Jie Xiong , Jianzu Wang , Qianping Ran , Yingli An , Zhenkun Zhang , Linqi Shi . . Acta Polymerica Sinica , 2013 . ( 6 ): 750 - 754 . http://www.gfzxb.org/CN/abstract/abstract13906.shtml.

熊洁 , 王建祖 , 冉千平 , 安英丽 , 张珍坤 , 史林启 . . 高分子学报 , 2013 . ( 6 ): 750 - 754 . http://www.gfzxb.org/CN/abstract/abstract13906.shtml.

E F Casassa , G C Berry . . J PolymSci, Part A-2: PolymPhys , 1966 . 4 ( 6 ): 881 - 897.

J E G Lipson . . Macromolecules , 1991 . 24 1327 - 1333 . DOI:10.1021/ma00006a018http://doi.org/10.1021/ma00006a018.

Y Nakamura , Y N Wan , J W Mays , H Iatrou , N Hadjichristidis . . Macromolecules , 2000 . 33 8323 - 8328 . DOI:10.1021/ma0007076http://doi.org/10.1021/ma0007076.

I Teraoka . . Macromolecules , 2004 . 37 6632 - 6639 . DOI:10.1021/ma0494939http://doi.org/10.1021/ma0494939.

Y W Wang , I Teraoka , F Y Hansen , G H Peters , O Hassager . . Macromolecules , 2011 . 44 403 - 412 . DOI:10.1021/ma102308qhttp://doi.org/10.1021/ma102308q.

C Gay , E Raphaël . . Adv Colloid Interface Sci , 2001 . 94 229 - 236 . DOI:10.1016/S0001-8686(01)00062-8http://doi.org/10.1016/S0001-8686(01)00062-8.

R J Flatt , I Schober , E Raphaël , C Plassard , E Lesniewska . . Langmuir , 2009 . 25 845 - 855 . DOI:10.1021/la801410ehttp://doi.org/10.1021/la801410e.

C Giraudeau , J-B d'Espinose de Lacaillerie , Z Souguir , A Nonat , R J Flatt . . J Am Ceram Soc , 2009 . 92 ( 11 ): 2471 - 2488 . DOI:10.1111/jace.2009.92.issue-11http://doi.org/10.1111/jace.2009.92.issue-11.

D Marchon , U Sulser , A Eberhardt , R J Flatt . . Soft Matter , 2013 . 9 10719 - 10728 . DOI:10.1039/c3sm51030ahttp://doi.org/10.1039/c3sm51030a.

Ran Qianping(冉千平), Somasundaran P, Miao Changwen(缪昌文), Liu Jiaping(刘加平), Wu Shishan(吴石山), Shen Jian(沈健). J Colloid InterfSci, 2009, 336: 624-633

Qianping Ran ,Min Qiao , Jiaping Liu , Changwen Miao . . Colloid PolymSci , 2012 . 290 ( 5 ): 435 - 443.

冉千平 , 乔敏 , 刘加平 , 缪昌文 . . Colloid PolymSci , 2012 . 290 ( 5 ): 435 - 443.

P G de Gennes . Scaling Concepts in Polymer Physics , : Ithaca Cornell University Press , 1979 . 29 - 51.

Manjun He , Hongdong Zhang , Weixiao Chen , Xixia Dong . Polymer Physics , : Shanghai Fudan University Press , 2007 . 26 - 50.

何曼君 , 张红东 , 陈维孝 , 董西侠 . 高分子物理 , : 上海复旦大学出版社 , 2007 . 26 - 50.

M Rubinstein , R H Colby . Polymer Physics , : New York Oxford University Press , 2003 . 49 - 70.

Teraoka I. Polymer Solutions: An Introduction to Physical Properties.New York: John Wiley & Sons, 2002. 184-188

M Doi , S F Edwards . The Theory of Polymer Dynamics , : Oxford Clarendon Press , 1986 . 97 - 106.

J F Douglas , J Roovers , K F Freed . . Macromolecules , 1990 . 23 4168 - 4180 . DOI:10.1021/ma00220a022http://doi.org/10.1021/ma00220a022.

H Lee , R M Venable , A D MacKerell , R W Pastor . . Biophys J , 2008 . 95 ( 4 ): 1590 - 1599 . DOI:10.1529/biophysj.108.133025http://doi.org/10.1529/biophysj.108.133025.

H Lee , A H de Vries , S J Marrink , R W Pastor . . J PhysChem B , 2009 . 113 ( 40 ): 13186 - 13194.

A V Dobrynin . . Macromolecules , 2005 . 38 ( 22 ): 9304 - 9314 . DOI:10.1021/ma051353rhttp://doi.org/10.1021/ma051353r.

Y Rouault , O V Borisov . . Macromolecules , 1996 . 29 ( 7 ): 2605 - 2611 . DOI:10.1021/ma951126xhttp://doi.org/10.1021/ma951126x.

M S Sulatha , U Natarajan . . IndEngChem Res , 2012 . 51 ( 33 ): 10833 - 10839.

M Doi . Introduction to Polymer Physics , : Oxford Clarendon Press , 1996 . 16 - 18.

K Devanand , J C Selser . . Macromolecules , 1991 . 24 ( 22 ): 5943 - 5947 . DOI:10.1021/ma00022a008http://doi.org/10.1021/ma00022a008.

S Kawaguchi , G Imai , J Suzuki , A Miyahara , T Kitano , K Ito . . Polymer , 1997 . 38 ( 12 ): 2885 - 2891 . DOI:10.1016/S0032-3861(96)00859-2http://doi.org/10.1016/S0032-3861(96)00859-2.

J Fischer , D Paschek , A Geiger , G Sadowski . . J PhysChem B , 2008 . 112 ( 43 ): 13561 - 13571.

K Prasitnok , M R Wilson . . PhysChemChemPhys , 2013 . 15 ( 40 ): 17093 - 17104.

Lianghe Shi . Gel Chromatography , : Beijing Science Press , 1980 .

施良和 . 凝胶色谱法 , : 北京科学出版社 , 1980 .

C Jackson , Y J Chen , J W Mays . . J ApplPolymSci , 1996 . 61 ( 5 ): 865 - 874.

Z Grubisic , P Rempp , H Benoit . . J PolymSci Part B: PolymLett , 1967 . 5 ( 9 ): 753 - 759.

Y W Wang , I Teraoka , F Y Hansen , G H Peters , O Hassager . . Macromolecules , 2010 . 43 ( 3 ): 1651 - 1659 . DOI:10.1021/ma902377ghttp://doi.org/10.1021/ma902377g.

L J Zhu , X Y Wang , J F Li , Y W Wang . . Macromol Theory Simul , 2016 . 25 ( 5 ): 482 - 496 . DOI:10.1002/mats.201600033http://doi.org/10.1002/mats.201600033.

Lu YY, An L J, Wang Z G. Macromolecules, 46(14):5731-5740

Yuyuan Lu , Tongfei Shi , Lijia An . . Acta Polymerica Sinica , 2011 . ( 9 ): 1060 - 1067 . http://www.gfzxb.org/CN/abstract/abstract13427.shtml.

卢宇源 , 石彤非 , 安立佳 . . 高分子学报 , 2011 . ( 9 ): 1060 - 1067 . http://www.gfzxb.org/CN/abstract/abstract13427.shtml.

Y F Houst , P Bowen , F Perche , A Kauppi , P Borget , L Galmiche , J F Le Meins , F Lafuma , R J Flatt , I Schober , P F G Banfill , D S Swift , B O Myrvold , B G Petersen , K Reknes . . CemConcr Res , 2008 . 38 ( 10 ): 1197 - 1209 . DOI:10.1016/j.cemconres.2008.04.007http://doi.org/10.1016/j.cemconres.2008.04.007.

G C Berry . . J PolymSci, Part B: PolymPhys , 1988 . 26 ( 5 ): 1137 - 1142 . DOI:10.1002/polb.1988.090260517http://doi.org/10.1002/polb.1988.090260517.

T Konishi , T Yoshizaki , H Yamakawa . . Macromolecules , 1991 . 24 ( 20 ): 5614 - 5622 . DOI:10.1021/ma00020a021http://doi.org/10.1021/ma00020a021.

Q Zhang , Q P Ran , H X Zhao , X Shu , Y Yang . . J Dispersion SciTechnol , 2017 . 38 ( 5 ): 721 - 728 . DOI:10.1080/01932691.2016.1192043http://doi.org/10.1080/01932691.2016.1192043.

G Gelardi , N Sanson , G Nagy , R J Flatt . . Polymers , 2017 . 9 ( 2 ): 61 DOI:10.3390/polym9020061http://doi.org/10.3390/polym9020061.

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