水性纯丙乳液的合成及单体配比对乳液附着性能的影响

以甲基丙烯酸甲酯(MMA)、丙烯酸异辛酯(2-EHA)分别为硬单体、软单体,甲基丙烯酸(MAA)为功能单体,过硫酸铵(APS)为引发剂,十二烷基硫酸钠(SDS)、脂肪醇聚氧乙烯醚(AEO-9)为乳化剂,采用半连续种子乳液聚合方法合成单体配比不同的水性聚丙烯酸酯乳液。利用衰减全反射-傅立叶变换红外光谱、核磁共振氢谱、凝胶渗透色谱、热重分析和动态热机械分析层测定水性聚丙烯酸酯的结构及性能。结果表明：随着硬软单体比的减小,聚丙烯酸酯乳液的粒径约为100nm;聚丙烯酸酯共聚物的低分子量部分,数均分子量约为3万,重均分子量约为5万;乳液膜的热分解温度从327.5℃升高到343.5℃,玻璃化转变温度从21℃降至-3.5℃;乳液的表面张力从39.83mN/m降至36.71mN/m、界面张力从19.01mN/m降至4.87mN/m、接触角从62.6°降到27.8°,附着牢度从50%提高到95%,当硬软单体比为7：13时,乳液的润湿性最好,附着牢度最高,满足乳液在BOPP薄膜上的应用要求。说明提高聚合物中软单体含量有利于提高乳液的润湿性,从而提高乳液的附着力。     

涂料用核壳型纯丙乳液的合成研究

采用甲基丙烯酸甲酯和丙烯酸正丁酯为核层单体,丙烯酸异辛酯、丙烯酸和甲基丙烯酸正丁酯为壳层单体,合成具有核壳结构的纯丙乳液。通过对丙烯酸羟丙酯对乳液成膜性能影响的讨论,得出丙烯酸羟丙酯用量不能超过聚合单体总量的1.5%。讨论了核层玻璃化转变温度,以及核层/壳层的质量比对乳液力学性能的影响。核层玻璃化转变温度为45℃,核层/壳层的质量比为40∶60时,所得核壳乳液的力学性能最为理想,符合涂料的使用要求。     

纯丙乳液研究进展

纯丙乳液是甲基丙烯酸酯类、丙烯酸酯类、丙烯酸三元共聚乳液的简称，是一种重要的中间产品或原料。常规的乳液聚合制备的纯丙乳液，性能较差，不能满足纯丙乳液的实际应用要求。综述了纯丙乳液在微量功能单体的引入、乳化体系、引发体系及聚合工艺方面的研究进展，并指出获得性能优良纯丙乳液的途径。     

PE/PP薄膜油墨用低温自交联丙烯酸酯乳液的合成及表征

以甲基丙烯酸甲酯、丙烯酸丁酯、双丙酮丙烯酰胺、丙烯酸为共聚单体,采用半连续种子乳液聚合工艺合成PE/PP薄膜油墨用低温自交联丙烯酸酯乳液,采用FTIR、TEM、DSC对乳液结构及固化性能进行了表征。结果表明,随着w(DAAM)增加,乳液粒径和凝胶率均有不同程度的增大,油墨的耐水时间和附着牢度先增大再减小,当w(DAAM)=2%,m(ADH)/m(DAAM)=0.8时,油墨附着牢度>90%,耐水时间≤150 h,揉搓牢度合格;FTIR结果表明,乳液在固化成膜过程中发生酮肼交联反应;DSC结果表明,发生酮肼交联反应后聚合物的玻璃化转变温度提高5.2℃;TEM结果表明,乳液粒子呈规则球形,有明显的核壳结构。     

纯丙弹性乳液的合成、应用及性能

研究了不同结构及不同配方的纯丙弹性乳液的合成及性能 ,并配制了聚合物乳液建筑防水涂料及聚合物水泥防水涂料。讨论了不同结构、不同Tg和不同引发剂、乳化剂用量对乳液性能及乳液 /水泥混合稳定性产生的影响。     

色粉纸用自交联丙烯酸树脂乳液的合成及性能

根据色粉纸表面固砂的性能要求,以丙烯酸丁酯(BA)、甲基丙烯酸异辛酯(EHMA)为软单体、丙烯酸甲酯(MA)、甲基丙烯酸甲酯(MMA)为硬单体,丙烯酸羟丙酯(HPA)为交联单体,甲基丙烯酸(MAA)、甲基丙烯酸缩水甘油酯(GMA)作为功能单体,采用半连续种子乳液聚合法,制备了具有核壳结构的水性丙烯酸酯树脂乳液(WSAE-G),进一步将其作为色粉纸表面固砂用黏合剂和成膜剂.讨论了GMA用量对乳液粒径、稳定性和黏度等的影响.利用DLS和TEM对乳液乳胶粒子的大小及形貌进行了表征,使用TG、DSC以及万能材料试验机对胶膜的性能进行了测试.对固砂产品表面进行SEM测试.结果表明:GMA用量为1％(以混合单体总质量为基准,下同)时,乳液粒径为142.4 nm,PDI为0.063,乳液分散稳定指数(TSI)为0.162287.TEM显示,乳液具有清晰的核壳结构.胶膜拉伸强度达9.057 MPa.制得的色粉纸层间结合力为244.9 J/m2,所形成的固砂层均匀、磨砂性较好且不易掉砂.     

DAAM对室温自交联纯丙乳液性能的影响

以衣康酸二丁酯(DBI)为第1功能单体、双丙酮丙烯酰胺(DAAM)为第2功能单体,合成了固含量为45%的纯丙乳液,并在室温与己二酰肼(ADH)交联。通过控制DAAM的用量,制备了一系列的室温自交联乳液,研究了DAAM用量对乳液和乳胶膜性能的影响。结果表明,DAAM的加入对乳液和胶膜的各项性能均有一定改善,DAAM的适用量为3%。     

丙烯酸异辛酯在核壳型纯丙乳液中的应用

用甲基丙烯酸甲酯和丙烯酸正丁酯为核,丙烯酸异辛酯、丙烯酸和甲基丙烯酸正丁酯为壳,合成具有核壳结构的丙烯酸乳液;根据凝胶率、膜吸水率和乳液的黏度对乳液的影响确定功能单体的加入量为总单体的1.5%;讨论了核层玻璃化转变温度以及核层单体与壳层单体的质量比对乳液力学性能的影响;核层玻璃化转变温度为45℃,核层单体与壳层单体的比为40:60时所得的核壳乳液的力学性能最为理想。     

核壳型含氟丙烯酸酯乳液的合成及表征

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、甲基丙烯酸六氟丁酯(HFMA)等为主要原料,采用多步乳液聚合法,合成了具有核壳结构的含氟丙烯酸酯乳液。实验结果表明,主要单体质量比m(MMA)∶m(BA)=45∶55,核壳单体质量比为6∶4,含氟单体质量分数为7%,乳化剂质量分数为3%~4%时,制备得到的含氟丙烯酸乳胶粒子具有软核/硬壳结构,粒径为120 nm,乳胶膜吸水率为7%。通过傅里叶红外光谱法(FTIR)对乳液结构进行表征,结果表明,含氟单体参与了有效聚合;差示量热扫描(DSC)和热重分析法(TG)分析结果表明,聚合物存在两个玻璃化温度(-10.2℃和58.4℃),且热分解温度比不含氟的聚合物提高了59℃;接触角测试结果表明,当w(HFMA)≥7%时,乳胶膜正面与水的接触角为98.2,°说明所合成的核壳结构含氟丙烯酸酯乳液中有机氟富集于壳层,涂膜的耐热、疏水性良好。     

核壳纯丙乳液的结构形态对Tg及MFT影响的研究

研究了核壳纯丙乳液聚合中乳液结构对其玻璃化转变温度、最低成膜温度的影响，以及单体种类、核壳比、核壳设计Tg对乳液性能的影响，还通过TEM、AFM研究了乳液颗粒形态及核壳乳液成膜后的表面形态。     

室温自交联水性聚丙烯酸酯乳液的合成、结构与性能

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、丙烯酸(AA)和双丙酮丙烯酰胺(DAAm)为共聚单体,采用半连续种子乳液聚合工艺,合成了具有核–壳结构的室温自交联水性聚丙烯酸酯乳液。以十二烷基硫酸钠(SDS)与辛基酚聚氧乙烯醚(OP-10)为复合乳化剂,研究了其用量对聚合反应稳定性的影响,讨论了不同DAAm用量下乳胶粒的粒径分布、漆膜耐水性和力学性能,确定了较佳的用量:复合乳化剂用量为单体质量的3.0%,w(DAAm)为4%。透射电镜(TEM)分析表明,乳胶粒具有明显的核–壳结构。热分析表明,以己二酰肼(ADH)为交联剂,交联后漆膜的玻璃化转变温度明显提高,红外光谱分析证明了酮肼交联反应的发生。     

交联型聚丙烯酸酯乳液的研究

采用半连续法合成了一种交联型聚丙烯酸酯乳液,讨论了交联单体的用量、外加交联剂的用量、固化温度等因素对胶粘剂性能的影响。研究表明,交联单体用量约为8.8%,制得的胶粘剂性能优良;外加4‰的交联剂,在110℃下烘干固化,可显著提高胶粘剂的耐水性。     

Synthesis and characterization of low-temperature self-crosslinkable acrylic emulsion for PE film ink

A low-temperature self-crosslinkable acrylic emulsion was synthesized by semi-continuous emulsion polymerization technology using methyl methacrylate (MMA), butyl acrylate (BA), acrylic acid (AA) and diacetone acrylamide (DAAM) as monomers and adipic dihydrazide (ADH) as crosslinker. Transmission electron microscope (TEM) micrograph disclosed spherical emulsion particles possess core–shell structure. Fourier transform infrared (FTIR) spectrogram showed that crosslinking reaction between CO groups of DAAM and NHNH₂ groups of ADH can occur during coating film formation at low temperature, even at room temperature. Differential scanning calorimeter (DSC) analysis indicated that glass transition temperature (Tg) of the crosslinked film is increased by 5 °C. Thermogravimetric analysis (TGA) curves demonstrated that self-crosslinking reaction improves thermal stability of film. As DAAM content increased from 0% to 2%, water absorption ratio of film decreased from 26.2% to 7.4%, adhesion ratio on the PE thin film increased from 0% to 97%. While the n(ADH)/n(DAAM) ratio increased from 0:1 to 0.8:1, crosslinking density of films was increased from 0% to 88%, water absorption ratio decreased from 36.5% to 7.4% and adhesion ratio on the PE thin film increased from 0% to 97%. The optimal DAAM content and n(ADH)/n(DAAM) ratio was 2% and 0.8:1 in this experiment. The emulsion has good potential application in water-based ink for PE film.     

RAFT聚合制备水性高颜料分散性油墨乳液

以3-烯丙氧基-2-羟基-1-丙磺酸钠(COPS-1)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为原料,通过可逆加成-断裂链转移(RAFT)聚合制得高分子乳化剂,进而制备水性丙烯酸酯油墨乳液.通过FTIR对高分子乳化剂进行结构分析,并对其进行相对分子质量及分布和临界胶束浓度分析.探讨RAFT试剂〔S,S′-二(α,α′-二甲基-α″-乙酸)三硫代碳酸酯〕用量、高分子乳化剂亲水单体比例和亲水单体用量等对乳液性能的影响.结果表明:RAFT聚合所制备的高分子乳化剂具有良好的乳化性能,且相对分子质量分布较窄.其最佳制备工艺为RAFT试剂最佳用量为乳液单体质量的0.6％,亲水单体的最佳比例为m(COPS-1):m(AMPS):m(丙烯酸)=1:2:3,最佳亲水单体用量为高分子乳化剂单体质量的25％.乳胶粒子分散均匀,制备的乳胶膜具备两个玻璃化转变状态.     

聚氨酯乳液的改性及其应用研究

用丙酮法合成了固含量为35%的聚氨酯成膜乳液。主要考查了复合型软段对聚氨酯成膜乳液及其胶膜性能的影响,并考查了乳液在水性印刷油墨中的应用。结果表明,亲水基团-COOH质量分数达到1.5%,能保证乳液的力学稳定性;随着不同聚多元醇复配比例的变化,乳液的稳定性和黏度、聚氨酯胶膜的力学性能以及吸水性均呈规律性变化,所制备的水性聚氨酯油墨对PET薄膜的附着力好。     

Synthesis and characterization of self-crosslinkable zinc polyacrylate latices at room temperature

The zinc ion self-crosslinkable polyacrylate latexes (PAs) cured at room temperature were synthesized by seeded semi-continuous emulsion polymerization with zinc oxide (ZnO) as crosslinker. The ZnO and methacrylic acid (MAA) mass contents, method of ZnO introduction in relation to the degree of crosslinking, and the properties of self-crosslinkable latices are examined and discussed. The characterization techniques such as Fourier transform infrared spectroscopy (FTIR), differential scanning calorimeter (DSC), transmission electron microscopy (TEM), and thermal gravimetric analysis (TGA) have been used to determine the structure and properties of PAs. The experimental results show that in a certain range, the average particle size decreases with an increase in the content of MAA, while the latex stability is undoubtedly improved. The optimum mass content of MAA is 12?% of the total monomers. The optimum amount of ZnO needed is 25?% (mole fraction) of MAA, and the optimum temperature of ZnO introduction is 60?°C. TEM analyses show that the latex particles are coarse spherical particles with surface enriched with comprising abundant carboxyl groups, and zinc ions are dissociated as zinc ammine complex in the aqueous phase. FTIR analyses confirm that the chelate crosslinking occurs between zinc ions and carboxylic acid during the film-forming process. The DSC results indicate that the glass transition temperature (T _g) of PAs increases as a function of the formation of a coordinate structure, and the obtained film exhibits excellent initial hardness and sandability. TGA analyses demonstrate that the introduction of ZnO evidently enhances the thermal stability of self-crosslinkable PAs.     

自交联封闭性乳液的合成与性能

以双丙酮丙烯酰胺（DAAM）、甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）和甲基丙烯酸（MAA）为共聚单体,采用半连续种子乳液聚合工艺合成自交联封闭性聚丙烯酸酯乳液（PAE）,考察了DAAM和复合乳化剂对乳液聚合稳定性以及涂膜性能的影响。研究发现：随着DAAM含量的增加,乳液聚合稳定性下降,粒径增大,涂膜的耐介质性能和交联度提高,合适的DAAM加入量为总单体质量的3.0%,DAAM和己二酰肼(ADH)的最佳摩尔比为2∶1。采用SDBS+OP-10+OP-40为复合乳化剂体系,选用乳化剂的含量为2.35%,阴/非离子乳化剂质量比为1∶1.25;复合乳化剂在种子、核、壳比例为1.5∶1∶2,制备的乳液具有较好的聚合稳定性（乳液凝胶率低和单体转化率高）,乳液耐电解质（钙离子）稳定性好,涂膜具有优异的封闭性。傅里叶红外光谱（FTIR）表明在涂膜形成过程中DAAM的酮羰基与ADH的酰肼基反应生成腙（C=N）,TEM分析显示乳液的乳胶粒子呈核壳结构,TGA分析发现DAAM改性的PAE降低了涂膜的热稳定性。     

聚苯乙烯丙烯酸丁酯乳液的制备及其性能研究

本文采用预乳化种子乳液聚合工艺,制备聚丙烯酸酯乳液涂料.并在乳液聚合过程中加入了功能性单体和活性酮基交联单体,研究结果表明:功能单体和活性酮基单体的加入提高了乳液的性能.     

交联改性苯丙乳液在水性油墨中的应用

分别以邻苯二甲酸二烯丙酯(DAP)、杂环甲基丙烯酸酯单体(TRM WAM Ⅲ)和乙酰乙酸基甲基丙烯酸乙酯(AAEMA)作为传统苯丙乳液的交联改性剂,采用预乳化半连续乳液聚合法制备交联改性苯丙乳液;然后以此为连接料,制备水性油墨.研究了传统苯丙乳液、交联改性苯丙乳液以及进口同类产品对水性油墨的摩擦牢度、稳定性能和耐水性能...     

Synthesis and characterization of low crystalline waterborne polyurethane for potential application in water-based ink binder

Waterborne polyurethane dispersions (PUDs) with low crystallization and narrow nanoparticles distribution were synthesized from poly(propylene glycol) (PPG), isophorone diisocyanate (IPDI), dimethylolpropionic acid (DMPA) via a environmental and simple process combined prepolymer isocyanate process with acetone process. For used as ink binder, the acid numbers of PUDs were analyzed. It was found that the acid number changed with the solid content and mainly increased with increasing hard-/soft-segment molar ratio. Fourier transform infrared (FTIR) spectroscopy, proton nuclear magnetic resonance spectroscopy (¹H NMR), transmission electron microscope (TEM), differential scanning calorimetry (DSC), thermogravimetric (TG), X-ray diffractometer (XRD) and polarizing optical microscopy (POM) measurements were utilized to characterize the bulk structures and thermal properties of PUDs. The results show that nanoscale waterborne polyurethane dispersions synthesized through the combined process have good thermal stability and weakly crystallinity, which is suitable for the use of water-based ink binder. The performance of PUDs can be optimized for the application as ink binder when the hard-/soft-segment molar ratio is 4 or 5.