异戊烯基聚氧乙烯醚分子量对聚羧酸超塑化剂单体序列结构的影响
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摘要
采用不同分子量(500、1 200、2 400 g/mol)的异戊烯基聚氧乙烯醚(IPEG)大单体与丙烯酸在水溶液中经自由基聚合,得到不同分子结构的聚羧酸超塑化剂样品。测定了聚羧酸样品的分子量及分子量分布和聚羧酸超塑化剂分子的单体序列结构(AAA、AAE、EAE,其中A为丙烯酸,E为IPEG大单体),计算得到了不同样品中3种单体序列结构的比例组成,并测定了不同单体序列结构的聚羧酸分子在水泥颗粒上的吸附量和分散性能。结果表明,分子量为2 400 g/mol的IPEG制备的聚羧酸超塑化剂样品含有更多的AAA序列结构,分子量分布窄、在水泥颗粒上的吸附速率慢、吸附量低,对水泥颗粒有较佳的分散和分散保持能力。
A series of carboxylate superplasticizers(PCEs) with various chemical structures were synthesized via free radical copolymerization from acrylic acid(AA) and isoprenyloxy polyethylene glycol(IPEG, E) with different molecule mass(i.e., 500,1 200, and 2 400 g/mol). The molecular weight characters and monomer sequences(AAA, AAE, EAE) of PCE polymers were detected, and the content ratios of monomer sequences were calculated. The adsorption amount and dispersive ability of PCE with different monomers sequences were also measured. The results indicate that PCE prepared by IPEG with the molecular weight of2 400 g/mol containing a higher AAA monomer sequence presents a lower molecular mass distribution, a lower adsorption rate/amount, and excellent water reducing/retention ability to cement particles.
A series of carboxylate superplasticizers(PCEs) with various chemical structures were synthesized via free radical copolymerization from acrylic acid(AA) and isoprenyloxy polyethylene glycol(IPEG, E) with different molecule mass(i.e., 500,1 200, and 2 400 g/mol). The molecular weight characters and monomer sequences(AAA, AAE, EAE) of PCE polymers were detected, and the content ratios of monomer sequences were calculated. The adsorption amount and dispersive ability of PCE with different monomers sequences were also measured. The results indicate that PCE prepared by IPEG with the molecular weight of2 400 g/mol containing a higher AAA monomer sequence presents a lower molecular mass distribution, a lower adsorption rate/amount, and excellent water reducing/retention ability to cement particles.
引文
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[22]WINNEFELD F,BECKER S,PAKUSCH J,et al.Effects of the molecular architecture of comb-shaped superplasticizers on their performance in cementitious systems[J].Cem Concr Comp,2007,29(4):251-262.
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[24]WANG Guoyong,BAI Yanyun,MA Xiaoyuan,et al.Effects of the PEG length of polycarboxylate-based terpolymers on their dispersion properties[J].J Mol Liq,2017,225(1)225:333-338.
[25]QIU Xueqing,PENG Xiongyi,YI Conghua,et al.Effect of Side Chains and Sulfonic Groups on the Performance of Polycarboxylate-Type Superplasticizers in Concentrated Cement Suspensions[J].J Disper Sci Technol,2011,32(2):203-212.
[2]NGUYEN G,NICOLE D,SWISTEK M.Sequence distribution of the methyl methacrylate-ethyl acrylate copolymer by 13C n.m.r.spectroscopy[J].Polymer,1997,38:3455-3461.
[3]KIN Y,JAMES HARWOOD H.Analysis of sequence distribution in methyl methacrylate-methyl acrylate copolymers by 13C NMRspectroscopy[J].Polymer,2002,43:3229-3237.
[4]BORGET P,GAOMICHE L,LEMEINS J F,LAFUMA F.Microstructural characterization and behavior in different salt solutions of sodium polymethacrylate-g-PEO comb copolymers[J].Colloids Surf,A:Eng.Aspects,2005,260(6):173-182.
[5]ROZZONI A,BELLOTTO M,Configurational NMR study of sodium polymethacrilate-g-PEO comb polymers[C]//13th International Congress on the Chemistry of Cement,Madrid,Spain,2011.
[6]PIKELMANN J,LI H Q,BAUMANN R,PLANK J.A 13C NMRspectroscopic study on the repartition of acid and ester groups in MPEG type PCEs prepared via radical copolymerization and grafting techniques[C]//11th CANMET/ACI International Conference on Superplasticizers and Other Chemical Admixtures in Concrete,Ottawa,Canada,2015,SP-302-02:25-37.
[7]Plank J,LI H Q,IIG M,et al.A microstructural analysis of isoprenol ether-based polycarboxylates and the impact of structural motifs on the dispersing effectiveness[J].Cem Concr Res,2016,84(7):20-29.
[8]PLANK J,HIRSCH C.Impact of zeta potential of early cement hydration phases on superplasticizer adsorption[J].Cem Concr Res,2007,37(4):537-542.
[9]ALONSO M M,PUERTAS F.Adsorption of PCE and PNSsuperplasticisers on cubic and orthorhombic C3A effect of sulfate[J].Constr Build Mater,2015,78(3):324-332.
[10]YAMADA K,TAKAHASHI T,HANEHARA S,et al.Effects of the chemical structure on the properties of polycarboxylate-type superplasticizer[J].Cem Concr Res,2000,30(5):197-207.
[11]ZOU Fubing,TAN Hongbo,GUO Yulin,et al.Effect of sodium gluconate on dispersion of polycarboxylate superplasticizer with different grafting density in side chain[J].J Ind Eng Chem,2017,55(11):91-100.
[12]DALAS F,POURCHET S,NONAT A,et al,Fluidizing efficiency of comb-like superplasticizers:The effect of the anionic function,the side chain length and the grafting degree[J].Cem Concr Res,2015,71(5):115-123.
[13]DALAS F,POURCHET S,NONAT A,et al.Tailoring the anionic function and the side chains of comb-like superplasticizers to improve their adsorption[J].Cem Concr Res,2015,67(1):21-30
[14]POURCHET S,LIAUTAUD S,RINALDI D,Effect of the repartition of the PEG side chains on the adsorption and dispersion behaviors of PCP in presence of sulfate[J].Cem Concr Res,2012,42(2):431-439.
[15]ZHANG Yanrong,KONG Xiangming,LU Zhenbao.Effects of the charge characteristics of polycarboxylate superplasticizers on the adsorption and the retardation in cement pastes[J].Cem Concr Res,2015,67(1):184-196.
[16]YAMADA K,OGAWA S,HANEHARA S.Controlling of the adsorption and dispersing force of polycarboxylate-type superplasticizer by sulfate ion concentration in aqueous phase[J].Cem Concr Res,2001,31(3):375-383.
[17]FERRARI L,KAUFMANN J,WINNEFELD F,et al.Interaction of cement model systems with superplasticizers investigated by atomic force microscopy,zeta potential and adsorption measurements[J].JColloid Interf Sci,2010,347(7):15-24
[18]李顺,余其俊,韦江雄.聚羧酸减水剂的分子结构对水泥水化过程的影响[J].硅酸盐学报,2012,40(2):613-619.LI Shun,YU Qijun,WEI Jiangxiong.J Chin Ceram Soc,2012,40(2):613-619.
[19]田亚坡.聚羧酸高性能减水剂在水泥和辅助性凝胶材料表面的吸附特性研究[M].广州:华南理工大学,2013.TIAN Yapo.The adsorption behavior of polycarboxylate superplasticiazer on the surface of cement and supplementary cementitious particles(in Chinese,dissertation).Guangzhou:South China University of Techchology,2013.
[20]PLANK J,SACHSENHAUSER B.Experimental determination of the effective anionic charge density of polycarboxylate superplasticizers in cement pore solution[J].Cem Concr Res,2009,39:1-5.
[21]刘明,聚羧酸减水剂对水泥水化的影响及相关机理研究[D].武汉:武汉理工大学,2015.LIU Ming.Effects and Related Mechanisms of Polycarboxylate Superplasticizers on Cement Hydration(in Chinese,dissertation),Wuhan,Wuhan University of Technology,2015.
[22]WINNEFELD F,BECKER S,PAKUSCH J,et al.Effects of the molecular architecture of comb-shaped superplasticizers on their performance in cementitious systems[J].Cem Concr Comp,2007,29(4):251-262.
[23]向顺成,史才军,吴林妹,等.不同长度侧链的梳状结构聚羧酸盐的合成及其对新拌水泥浆体性能的影响[J].硅酸盐学报,2015,43(5):570-578.XIANG Shuncheng,SHI Caijun,WU Linmei.J Chin Ceram Soc,2015,43(5):570-578.
[24]WANG Guoyong,BAI Yanyun,MA Xiaoyuan,et al.Effects of the PEG length of polycarboxylate-based terpolymers on their dispersion properties[J].J Mol Liq,2017,225(1)225:333-338.
[25]QIU Xueqing,PENG Xiongyi,YI Conghua,et al.Effect of Side Chains and Sulfonic Groups on the Performance of Polycarboxylate-Type Superplasticizers in Concentrated Cement Suspensions[J].J Disper Sci Technol,2011,32(2):203-212.
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