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.     

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。     

The synthesis technique of polyacrylic acid superplasticizer

Using water separation technique,acrylic acid （AA） and polyethylene glycol （PEG） 1000,of which the ratio was 1.5,were esterified and the optimum esterification ratio of 90% could be reached under the condition of 110 ℃×3 h.Using polyoxyethylene acrylate macromonomer （PA） prepared in the esterification,AA and sodium methylacryl sulfonate （MAS） as monomers,a copolymer which could be used as superplasticizer was prepared by free radical coolymerization in n（PA）：n（AA）：n（MAS） of 1：7：3.When the synthesis condition was 80 ℃× 5 h,the optimal dosage of initiator was 3.0%-4.0%,the fluidity of cement paste with the samples could reach 270 mm.By analyzing the effect of the content of residual small molecule sulfonic monomer on the properties of sample,n（MAS）/n（PA） was controlled in a range of 2.5-3.8.     

反相乳液聚合法制备两性聚羧酸高聚物 MPEGAA/AA/DAC及其性能研究

以自制大分子单体聚乙二醇单甲醚丙烯酸酯(MPEGAA)、丙烯酸(AA)和自制丙烯酰氧乙基三甲基氯化铵(DAC)为原料,通过反相乳液聚合技术,制备了两性聚羧酸高聚物MPEGAA/AA/DAC.采用傅里叶红外光谱法(FTIR)、核磁共振碳谱(¹³C NMR)方法对两性聚羧酸高聚物的结构和组成进行了表征,考察了反相乳液聚合条件对单体转化率及90 min内水泥净浆流动度保持率的影响,并对添加了质量分数为0.20%两性聚羧酸高聚物MPEGAA/AA/DAC混凝土的性能进行了探讨.结果显示,当选用单体质量分数为40%,n(AA)/n(MPEGAA)=3,n(DAC)/n(MPEGAA)=0.5,占油相质量3.5%的Span-80/Tween-80为乳化剂,油水体积比V_o/V_w=0.45,占单体总质量1.5%的2,2’-偶氮二异丁腈(AIBN)为引发剂,引发温度为50 ℃,反应时间为6 h时,制得的两性聚羧酸高聚物具有优越的保塑性能和较高的早期抗压强度性能.     

两性聚羧酸类高聚物阳离子丙烯酸酯单体DAC的制备及其性能

以丙烯酸甲酯(MA)与2-氯乙醇(CE)为反应原料,通过酯交换反应制备了丙烯酸氯乙醇酯(CA)中间体,再将CA与三甲胺(TMA)水溶液反应,合成了一种用于制备两性聚羧酸类高聚物的阳离子丙烯酸酯单体(丙烯酰氧乙基三甲基氯化铵,DAC).采用FTIR和¹HNMR对DAC结构进行了表征,并考察了n(TMA)/n(CA)、催化剂用量、阻聚剂用量、反应温度和反应时间对CA转化率和DAC质量分数的影响.结果显示:最佳制备工艺条件为n(TMA)/n<     

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.     

聚羧酸助磨剂合成及其性能

利用水泥粉磨过程中的机械力促使水解聚马来酸酐（HPMA）与聚乙二醇单甲醚（MPEG）进行酯化反应形成聚羧酸助磨剂。试验研究了HPMA、MPEG、HPMA与MPEG的混合物、HPMA与MPEG的反应合成物对水泥助磨效果以及对砂浆性能的影响。结果表明,HPMA与MPEG都有一定的助磨性,HPMA与MPEG的混合物和反应合成物具有更佳的助磨性能,且可以改善水泥砂浆的流动性能和显著提高水泥砂浆的早期强度。激光拉曼光谱测试表明HPMA与MPEG的混合物和反应合成物与水泥共同粉磨后吸附在水泥颗粒表面,具有相似的拉曼位移图谱。     

Preparation and microstructure characterization of poly-sialate-disiloxo type of geopolymeric cement

In order to investigate the influence of three key molar ratios (n(SiO₂)/n(Al₂O₃), n(K₂O)/n(Al₂O₃) and n(H₂O)/n(K₂O)), a total of nine potassium poly-sialate-disiloxo (K-PSDS) geopolymeric cement matrices were designed according to orthogonal design principle. Subsequently, XRD, ESEM-EDXA and MAS-NMR techniques were employed to further characterize the microstructure of the most fully reacted geopolymeric cement matrix. The experimental results show that n(K₂O)/n(Al₂O₃) has the most significant effect on compressive strength amongst the three ratios. The highest compressive strength (20.1 MPa) can be achieved when n(SiO₂)/n(Al₂O₃)=6.5, n(K₂O)/n(Al₂O₃)=0.8 and n(H₂O)/n(K₂O)=10.0. The FTIR spectra of nine PSDS geopolymeric cement matrices also indicate that geopolymeric cement matrix with the highest strength is the most fully reacted one and possesses the largest amount of geopolymeric cement products. The microscopic analysis reveals that PSDS geopolymeric cement matrix possesses structural characteristics similar to gel substances in having a wide range of Si endowments, but predominantly the framework molecular chains of Si partially replaced by 4-coordinated Al tetrahedral.     

酸性离子液体催化合成乙二醇硬脂酸酯

以硬脂酸和乙二醇为原料,酸性离子液体为催化剂,制备了乙二醇硬脂酸酯。结果表明,离子液体催化活性很高,在醇酸摩尔比1 1,反应温度120℃,反应时间3h的条件下,酯化转化率可达91.65%,且离子液体稳定,可循环使用。     

Preparation and adsorption property of phenyltriethoxysilane modified SiO2 aerogel

The hydrophobic silica aerogel (SiO₂ aerogel) was prepared by in situ polymerization sol-gel method and ethanol supercritical drying, with tetraethoxysilane (TEOS) as silica source, phenyltriethoxysilane (PTES) as modifier, ethanol as solvent and ammonia as catalyst. The effects of n(PTES)/n(TOES) were investigated on gel time, structure, and hydrophobicity. The SiO₂ aerogel was measured by Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The effects of n(PTES)/n(TOES) were also studied on adsorption property of pentane, hexane, heptane, octane, benzene, toluene, o-xylene, nitromethane, nitroethane, and nitrobenzene. The adsorption intensity of SiO₂ aerogel was compared with that of activated carbon. The results show, with the increasing of n(PTES)/n(TOES), the surface area, pore volume, and pore size of SiO₂ aerogel decreased, gel time and hydrophobicity increased, and the contact angle could be 154° with n(PTES)/n(TOES)=0.7. The adsorption intensity of SiO2 aerogel with n(PTES)/n(TOES)=0.5 was bigger than that of activated carbon with an average 5.84 times of 10 organic liquid. The adsorption intensity of aerogel with n(PTES)/n(TOES) =0.1 was the best one in all samples with the average 8.33 times compared with that of activated carbon.     

聚乙二醇单甲醚固-固相变材料的合成与性能测试

为得到相变温度较低,相变焓较高的相变材料,以聚乙二醇单甲醚(MPEG)为软段,4,4′-二苯基甲烷二异氰酸酯(MDI)、新戊二醇(NPG)为硬段,合成聚氨酯固-固相变储能材料.利用差示扫描量热仪(DSC)、热重分析仪(TGA)、红外光谱(IR)、偏光显微镜(POM)分析了材料的形态结构和相变行为.结果表明:所制备的相变材料具有良好的固-固相变储热性能,相变焓达到146.6 J/g,相变温度为43.92℃,且具有很好的热稳定性.相过程的变实质是相变材料中的软段MPEG在结晶态与为非晶态之间相互转化的过程.     

Probing development of microstructure of early cement paste using 1H low-field NMR

Development of microstructure of early cement paste (0–6 h) was investigated with ¹H low-field NMR. It was found that T ₂ (transverse relaxation time) distributions of fresh cement paste were bimodal and two peaks were ‘long component’ and ‘short component’. Separation degree of two peaks was a sign of exchange of water within flocculation and outside flocculation. Factors such as water cement ratio, specific surface area and dosage of superplasticizer had influences on the separation degree: the separation degree increased with the water cement ratio; the separation degree of cement paste prepared with cement with a high specific surface area was zero; dosage of superplasticizer will decrease separation degree. Results also suggested that T ₂ distribution gradually moved to the left and T ₂ of long component and initial fluidity were linearly correlated.     

新型羧酸盐高效减水剂的合成试验

根据混凝土外加剂分子设计理论，试验采用了自制丙烯酸聚乙二醇单酯、丙烯酸钠盐和二乙烯三胺通过Michael加成制得一种新型羧酸盐高效减水剂．对该新型减水剂进行了水泥净浆流动度测试，结果表明该减水剂具有良好的分散能力与流动保持性，其掺量的质量分数为1．5％，水灰质量比为0．29时，水泥净浆流动度达218mm。     

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.     

早强型聚羧酸减水剂的合成及性能研究

以丙烯酸(AA)、异丁烯醇聚氧乙烯醚(HPEG)、甲基丙烯磺酸钠(SMAS)等为单体,分别采用丙烯酰胺(AM)、羟甲基丙烯酰胺(HAM)取代部分丙烯酸,通过水溶液聚合法制备出具有早强功能的聚羧酸系减水剂,并探讨了合成条件对水泥净浆流动度的影响.研究结果表明:在单体摩尔比n(AA)∶n(HPEG)∶n(SMAS)=4∶1∶0.36、反应温度为80℃、过硫酸铵(APS)用量为单体总质量的3%时,制备出的聚羧酸减水剂的分散性能较优.当AM取代为18%时,对提高混凝土的早期强度效果较佳,AM比HAM具有更好的早强效果.     

固体超强酸催化剂S_2O_8~(2-)/Nd_2O_3-ZrO_2-Al_2O_3催化乙酸与低级醇的酯化反应研究

通过稀土固体超强酸作催化剂,对乙酸与低级醇的酯化反应进行研究.结果表明,三元稀土固体超强酸S2O2-8/Nd2O3-Zr O2-Al2O3具有优良的催化性能,其它最佳条件为:酸醇摩尔比为1 2,催化剂用量0.75 g,乙酸用量0.1 mol,反应时间3 h.在此条件下,酯化率可达到96.16%,催化剂重复使用3次以内,酯化率仍可达到92%以上.     

生物油模化物催化酯化的实验研究

采用生物质活性炭固载,用甲苯磺酸作催化剂,对生物质热解油的模化物乙酸和乙醇进行催化酯化反应。考察醇酸摩尔比、催化剂用量和反应时间对酯化反应的影响,确定最佳反应条件：固定乙酸用量为0．2mol,反应液微沸时,当醇酸摩尔比为2．8：1,催化剂用量1．0g,反应时间2h,乙酸酯化率接近87％时,且最佳条件下的实验重复性良好,催化剂可重复使用,也可用于生物油的催化酯化反应。     

聚羧酸系高效减水剂的合成及其作用机理研究

分析了聚羧酸系高效减水荆的结构与性能之间的关系，探讨了减水剂分子的主链结构单元与支链结构单元的功能与作用，并分类介绍了聚羧酸系的分子结构设计及其合成的研究与进展。结果表明，聚羧酸系减水剂的性能与其分子结构的主链和支链的结构单元、官能团的位置及其种类有关。在分子主链上引入大量合适大小分子量的聚乙二醇或聚氧乙烯接枝链和少量它们的嵌段链及一定构成比例的磺酸基团，可使减水剂在发挥低掺量高分散性的同时，产生良好的保塑性，且在合成过程中发现，聚氧烷基中的端羟基易引起凝胶。在此基础上结合原料的来源及其成本，选用聚乙二醇与丙烯酸在对甲苯磺酸作催化剂的条件下进行酯化，然后与甲基丙烯磺酸钠进行共聚，并加入一定量的丙烯酸单体来调节主链的大小及侧链上的羧基与磺酸基的相对构成比例，从而得到一种高性能减水剂。     

Rheological behaviors of fresh cement pastes with polycarboxylate superplasticizer

The rheologicalbehaviors of fresh cement paste with polycarboxylate superplasticizer were systematically investigated.Influentialfactors including superplasticizer to cement ratio(Sp/C),water to cement ratio(w/c),temperature,and time were discussed.Fresh cement pastes with Sp/Cs in the range of 0 to 2.0% and varied W/Cs from 0.25 to 0.5 were prepared and tested at 0,20 and 40 °C,respectively.Flowability and rheologicaltests on cement pastes were conducted to characterize the development of the rheologicalbehavior of fresh cement pastes over time.The exprimentalresults indicate that the initialflowability and flowability retention over shelf time increase with the growth in superplasticizer dosage due to the plasticizing effect and retardation effect of superplasticizer.Higher temperature usually leads to a sharper drop in initialflowability and flowability retention.However,for the cement paste with high Sp/C or w/c,the flowability is slightly affected by temperature.Yield stress and plastic viscosity show similar variation trends to the flowability under the abovementioned influentialfactors at low Sp/C.In the case of high Sp/C,yield stress and plastic viscosity start to decline over shelf time and the decreasing rate descends at elevated temperature.Moreover,two equations to roughly predict yield stress and plastic viscosity of the fresh cement pastes incorporating Sp/C,w/c,temperature and time are developed on the basis of the existing models,in which experimentalconstants can be extracted from a database created by the rheologicaltest results.     

Effect of competitive adsorption between sodium tripolyphosphate and naphthalene superplasticizer on fluidity of cement paste

The adsorption amount, ζ-potential of cement particles and fluidity of cement paste were tested to research the competitive adsorption between naphthalene superplasticizer(FDN) and STPP. The experimental results showed that the presence of STPP could significantly improve the fluidity of cement paste and reduce the fluidity loss with FDN. There existed a competitive adsorption between STPP and FDN. STPP and calcium ions formed complexes; they preferentially adsorbed onto surface of cement particles and preempt adsorption points of FDN; and it reduced adsorption amount of FDN. In the absence of STPP, saturation adsorption amount of FDN was 5.93 mg/g; but when the dosage of STPP was 0.1%, it reduced to 4.3 mg/g(about 72.5%). The adsorption amount of FDN was reduced by STPP, but ζ-potential of cement particles enhanced and fluidity of cement paste increased because of strong negative charge effect of the complexes. Adsorption of the complexes would delay Ca2+ into liquid and inhibit formation of active adsorption points. Then, content of FDN in liquid increased with the addition of STPP and ζ-potential of cement particles became stable. In this way, fluidity loss of cement paste reduced.