一种聚羧酸系减水剂的合成与性能

设计采用两步聚合法,即先通过一定分子质量的聚乙二醇(PEG)与丙烯酸(AA)在一定条件下发生酯化反应形成高分子大单体—聚乙二醇丙烯酸酯(PEGA),然后在水溶液中通过引发剂、PEGA和丙烯酸、甲基丙烯磺酸钠(MAS)发生共聚反应合成聚羧酸系减水剂.采用单因素变量试验法,分别研究了单体比例、引发剂用量、聚合温度、聚合时间及加料方式对聚合物性能的影响,从而得出合成聚羧酸系高性能减水剂的一种最佳工艺,并对试制产品进行了性能测试.结果表明:聚羧酸系减水剂具有优良的分散性能,能较长时间地保持水泥浆的流动性.     

含有聚环氧乙烷支链的聚羧酸型高效减水剂的合成及表征

以丙烯酸类单体及其衍生物和聚乙二醇大分子单体为原料,通过自由基共聚和酯化接枝反应合成了两种带环氧乙烷支链的聚羧酸型高效减水剂,通过对合成配方与反应条件的正交设计,确定了最佳合成工艺参数;对合成产物的减水率及保塑性能进行了探讨,并对其分子量及分子结构进行了表征．结果表明,2种合成产物的掺量为0．4％时,混凝土减水率均超过30％,且具有较好的保塑性能,减水保塑性能优于萘系高效减水剂．     

含有聚环氧乙烷支链的聚羧酸型高效减水剂的合成及表征

以丙烯酸类单体及其衍生物和聚乙二醇大分子单体为原料,通过自由基共聚和酯化接枝反应合成了两种带环氧乙烷支链的聚羧酸型高效减水剂,通过对合成配方与反应条件的正交设计,确定了最佳合成工艺参数;对合成产物的减水率及保塑性能进行了探讨,并对其分子量及分子结构进行了表征.结果表明,2种合成产物的掺量为0.4%时,混凝土减水率均超过30%,且具有较好的保塑性能,减水保塑性能优于萘系高效减水剂.     

聚羧酸系高效减水剂的合成及机理研究

概述了聚羧酸系高效减水剂的研究进展和发展现状,讨论了聚羧酸系减水剂的合成方法、分子结构、分子结构与性能的关系以及其作用机理,并提出了聚羧酸系减水剂有待解决的问题及其研究发展趋势.     

聚羧酸高效减水剂结构与性能关系的研究

将丙烯酸、甲基丙烯磺酸钠和马来酸酐聚乙二醇单甲醚单酯通过自由基聚合，合成了聚羧酸高效减水剂，研究了减水剂结构与性能之间的关系，提出了聚羧酸高效减水剂的作用机理。     

聚羧酸高效减水剂结构与性能关系的研究

将丙烯酸、甲基丙烯磺酸钠和马来酸酐聚乙二醇单甲醚单酯通过自由基聚合,合成了聚羧酸高效减水剂,研究了减水剂结构与性能之间的关系,提出了聚羧酸高效减水剂的作用机理.     

酯化-共聚合成高效减水剂WD-1

以甲基丙烯酸与聚乙二醇为主要原料,经酯化制得聚乙二醇丙烯酸酯,将酯化物与烯丙基磺酸钠、甲基丙烯酸共聚制备出聚羧酸系高效减水剂WD-1.对产品进行了红外光谱分析,探讨了聚乙二醇的聚合度(n)、聚乙二醇封端与否以及酯化温度对聚羧酸系减水剂主要性能的影响.结果表明:采用n=9的聚乙二醇单甲醚进行酯化,温度为80℃时,产品具较好的综合性能;产品红外谱图与设计分子结构相符;聚羧酸系高效能减水剂WD-1可以使水泥具有较好的净浆流动度,混凝土减水率可达26.9%.     

木质素磺酸钠聚羧酸减水剂的制备研究

以木质素磺酸钠作为聚羧酸减水剂的合成原料,在水溶液中与聚羧酸减水剂单体进行接枝共聚反应,制得木质素磺酸钠聚羧酸减水剂,并对其制备工艺进行优化,得到最优实验方案为:木质素磺酸钠质量分数为16%,PEG-1000和MA的物质的量比为0.9∶1.0,丙烯酸与马来酸酐物质的量比为2.8∶1.0,聚合时间为3h,酯化时间为4h,最优条件下制得的产品的水泥净浆流动度(掺量为0.2%,水灰质量比为0.29)为241mm。红外测试表明木质素磺酸钠分子结构上成功接上了聚氧乙烯基、酯基、羧酸基及酰胺基等官能团。     

新型聚羧酸系外加剂合成工艺研究

通过确定不同的引发剂用量、聚乙二醇投入量、聚氧化乙烯侧链长度以及酯化反应的温度和时间，对所合成的新型聚羧酸系外加剂的性能进行比较。试验结果表明，在新型聚羧酸系外加剂的合成过程中，存在着最佳范围的引发剂用量、聚乙二醇投入量、聚氧化乙烯侧链长度和最佳的酯化反应温度和时间，优化了新型聚羧酸外加剂的合成工艺。     

磷酸盐型聚羧酸减水剂的合成及性能研究

采用丙烯酸与聚乙二醇磷酸酯进行酯化后得到含有磷酸基团的酯化产物，再与乙二醇单乙烯基聚乙二醇醚在氧化还原体系下共聚制备磷酸盐型聚羧酸减水剂(PCE-P).采用红外光谱(FTIR)、凝胶色谱(GPC)对减水剂进行结构表征，并进行表面张力测试、总有机碳(TOC)测试以及混凝土实验，结果表明：合成的磷酸盐型聚羧酸减水剂对黏土具有较好的耐受性，能降低混凝土的黏度.     

Effect of Molecular Structure on the Performance of Polyacrylic Acid Superplasticizer

The effects of structure parameters, such as molecular structure, segment kinds, molecular weight, and organic functional groups, on the performance of polyacrylic acid superplasticizer were discussed. According to the differences of chain sections, functional groups, eic, polyacrylic acid superplasticizer could be divided into A, B, C three parts. Among them, A chain section included sulfonic acid groups, B chain section carboxyl groups, C chain section polyester. Polyacrylic acid superplasticizers with different matching of A, B, C chain sections, different length of C chain section and different molecular weights were synthesized by acrylic acid, polyethylene glycol, sodium methyl allylsulfonate; the relation between the molecular structure and perfolxnance was also studied. The expetimental results indicate that the water-reduction ratio increases obviously with the increment of the proportion of sodium methyl allylsulfonate chain section in the molecular; the slump retention increases greatly with the increment of the proportion of acrylic acid chain section; the dispersion of cement particles increases with the increment of the chain length of polyethylene glycol; when the molecular weight is in the range of 5000, the dispersion and slump retentibity increase with the increment of the average molecular weight of polymers.     

Synthesis of new polyether polycarboxylate superplasticizer

The effects of various factors on the synthesis process and the performances of product, including batch feeding way and the dosage of the radical initiator, the system concentration, the reaction temperature and the reaction time were discussed. A kind of polycarboxylate superplasticizer with allyl alcohol polyethylene glycol, maleic anhydride and methacrylic acid sulfonic sodium as main raw materials has been synthesized. Their relative effectiveness as dispersants was evaluated in cement paste by measuring paste fluidity. The optimum parameters of technology and the appropriate proportion of raw materials were obtained. As a result, the new high performance superplasticizer suitable for high-performance concrete has been synthesized. The structure of copolymer was characterized and analyzed by FT-IR spectra. Results indicated that product copolymer structure was consistent with the ideal molecular structure designed.     

聚羧酸减水剂对不同晶型C3S早期水化放热的影响

采用水化微量热仪研究了不同类型聚羧酸减水剂对不同晶型C3S水化放热特性的影响。结果表明:单斜晶系(M)C3S、三方晶系(R)C3S的水化放热速率峰值相比三斜晶系(T)C3S显著降低,且水化放热峰出现延迟,MC3S的水化放热峰延迟最明显。三种晶型C3S的3d水化放热总量由大到小为:TC3S、MC3S、RC3S。不同分子结构的甲氧基聚乙二醇甲基丙烯酸酯系聚羧酸减水剂,主链越短,支链越长,对TC3S的水化延迟作用越大。乙烯基聚乙二醇醚系聚羧酸减水剂对三种晶型C3S的水化放热过程延迟作用由大到小为:RC3S、MC3S、TC3S。对水化放热曲线进行的Krstulovic-Dabic模型研究表明,C3S的水化过程为NG-D类型水化历程。     

高酯化率MPEGAA大单体的合成

采用丙烯酸（从）和聚乙二醇单甲醚（MPEG）为主要反应原料,通过逐步滴加带水剂甲苯的方法,研究其主要反应条件对酯化率的影响。在温度为90℃的条件下,制备的聚羧酸减水剂的活性大单体聚乙二醇单甲醚丙烯酸酯（MPEGAA）酯化率高达99．6％,双键保留率高达91．5％。测试了应用该大单体所合成的聚羧酸减水剂与几种水泥的适应性和分散保持性。     

Effect of PCEs with Different Functional Groups on the Performance of Cement Paste

The adsorption behaviors and dispersing properties of polycarboxylate superplasticizer(PCE) with different functional groups were systematically analyzed to reveal the theory and methods of modifying PCE molecular structures and regulating PCE performances. By substituting carboxylic groups with sulfonic groups, ester groups or acylamino groups, respectively, modified PCEs with different functional groups were synthesized. Results show that introducing low amount of ester groups or sulfonic groups into the PCE molecules has no negative effects on the fluidity of cement paste, while introducing acylamino groups into PCE molecules significantly weakens the fluidity of cement paste. At low amount(when the molar ratio of sodium methallyl sulfonate to TPEG is lower than 0.4), the rapid adsorption of sulfonic groups onto the cement particles contributes to the high dispersing performance of the sulfonic group modified PCEs. When the substitution ratio of acrylic acid by sulfonic acid is higher than 0.4, the viscosity and the yield stress of cement paste increases sharply. Redundant sulfonic groups lead to the excessive charge density of the PCE, which contributes to the inhomogeneous adsorption on the cement grains and hence results in the decline of the dispersing performance. Substitution of carboxylic group by acylamino group or ester group slightly changes the viscosity as well as the yield stress of cement paste. Introducing sulfonic group into PCE molecule improves the adsorption behavior of PCEs, while introducing ester group or acylamino group into PCE depresses the adsorption properties.     

Synthesis and properties of an AMPS-modified polyacrylic acid superplasticizer

A 2-acrylamide-2-methyl propylene sodium sulfonic (AMPS)-modified polyacrylic acid superplasticizer was synthesized using aqueous solution polymerization with the major monomers including the self-made active macromers polyethylene glycol mono-methyl ether acrylate acrylic (MPEGAA), acrylic acid (AA), AMPS, and sodium methyl allyl sulfonate (SMAS). The ratios of the monomers were determined using an orthogonal experiment. This research focused on the effects of the dosages of different macromers, the polymerization conditions, and the length of MPEGAA side chains on the properties of the AMPS-modified polyacrylic acid superplasticizer. The best polymerization conditions of the AMPS-modified polyacrylic acid superplasticizer are when (n(MPEGAA):n(SMAS):n(AMPS):n(AA) equals 0.1:0.1:0.2:0.65, the molecular weight of monomethoxypolyethylene glycol is 1 200, the initiator ammonium persulfate accounts for 5% of the total mass of the polymerized monomers, the polymerization temperature is 80 °C, and the reaction time is 4 h. The AMPS-modified polyacrylic acid superplasticizer synthesized in the best conditions exhibited excellent dispersivity and dispersion retainability. When the dosage ratio was 0.24%, the initial fluidity was 400 mm and the fluidity had nearly no loss after 1 h.     

Microstructural Characteristics Analysis of PCE Copolymer from Methyl Allyl Polyethylene Glycol and Methacrylic Acid based on Determination of Monomer Reactivity Ratios

The reactivity ratio of monomer and the microstructure of copolymer as polycarboxylate ether (PCE) superplasticizer were investigated.Polycarboxylate ethers (PCEs) were synthesized from methyl allyl polyethylene glycol (MAPEG,M_w=2 400 g/mol) and methacrylic acid (MAA) via aqueous free radical copolymerization in low conversion (P20%).Gel permeation chromatography (GPC) and high performance liquid chromatography (HPLC) were used to track the residual concentration of the reactants and the amount of copolymer formed during the copolymerization.The reactivity ratios of monomers,MAPEG and MAA,were determined as r_(1(MAPEG))=0.0489 and r_(2(MAA))=1.6173,respectively,by employing the K-T and YBR methods.According to the obtained monomer reactivity results,the sequence distribution of the copolymer,the number average length of MAA in the polymerisate were found to decline with the decrease of the mole fraction of MAA in the polymerization system.As a result,the distribution of chain segments becomes narrower and the copolymer structure becomes more uniform.Therefore,uniform polymers could be obtained by slowly adding MAA monomer during copolymerization process.     

Effects of molecular structure of polycarboxylate-type superplasticizer on the hydration properties of C3S

Effects of polycarboxylate-type superplasticizer(PC) molecular structure on the hydration heat of tricalcium silicate(C3S) paste and polymerization degree of hydration products(C-S-H gel) were researched by using TAM AIR isothermal microcalorimetry(TA) and 29Si nuclear magnetic resonance(NMR).Methoxy polyethylene glycol-methacrylates-based polycarboxylate superplasticizers with different side chain lengths and main chain lengths were employed.PC molecules with shorter main chain or longer side chains caused stronger retardation of C3S early hydration and lesser increase of C3S 3 d hydration degree.NMR measurement indicated that the incorporation of PC increased the hydration degree of C3S paste and the polymerization degree of silicon-oxygen tetrahedron of C-S-H gel.The tendency for C3S 7 d hydration degree to improve was more pronounced while PC molecules with longer main chain or shorter side chain were added.Whereas,PC molecules with longer main chains or longer side chains increased the 7 d polymerization degree of C-S-H gel.     

磺化淀粉-聚羧酸复合减水剂的制备与表征

由于保护环境的原因,以天然高分子为原料来合成高效减水剂已经成为混凝土外加剂研究领域的新热点.本文研究了采用磺化糊精取代部分功能大单体来合成复合聚羧酸减水剂的方法.结果显示:当磺化糊精取代功能单体40%、复合聚羧酸减水剂掺量为0.5%时,水泥净浆的初始流动度达255,mm,1,h 后其流动度仍为250,mm.淀粉酸解后,增加亲水的羟基基团导致初期水化缓慢,而增加 Zeta 电位使水泥颗粒更易于分散.在复合减水剂中,长链 Starch 与短链的聚羧酸减水剂主链将被吸附于水泥颗粒表面上,交替发生静电与空间位阻作用,起到了增加减水率和降低缓凝的效果.