摘要
可再分散乳胶粉与传统乳液相比具有突出的优点，如无残留单体等VOC组分、贮存稳定、没有受冻或微生物污染的风险、包装简单、运输方便等，因而得到了较为广泛的应用，特别是在零VOC的干粉涂料相关领域，具有广阔的发展应用前景。但是，目前的可再分散乳胶粉仍然存在耐水性和成膜性能较差的问题，对干粉涂料成膜过程、聚乙烯醇接枝丙烯酸酯类乳液聚合的稳定性等关键问题也缺乏深入的研究，这些都限制了可再分散乳胶粉的产品创新、性能提升和应用领域的拓展。本文通过粒子设计等手段合成了具有软核硬壳结构的丙烯酸聚合物乳液，制得了性能较好的可再分散聚合物乳胶粉及其零VOC干粉涂料，并在此基础上对制约可再分散乳胶粉性能提升的关键性技术进行了深入研究，同时尝试将新兴技术在可再分散乳胶粉制备中进行应用，因而具有重要的理论和现实意义。本文主要研究内容如下：
本文首先对核壳乳液聚合配方和喷雾干燥参数等可再分散乳胶粉制备的基本要素进行了考查，并对不同条件下乳胶粉的出粉率、含水率、表观形态和再分散性等性能进行了评估，得出了可再分散乳胶粉制备的基本配方和喷雾干燥过程的工艺参数设置，即核层Tg=-10℃，壳层Tg=70℃，核壳质量比3:1，MAA用量为壳层单体质量的16wt%，喷雾干燥进口温度为120℃，雾化盘转速为24,000rpm，进料速率为20~40ml/min。然后将可再分散乳胶粉应用于干粉涂料中，改变乳胶粉的加入量并对涂料样品的成膜性能进行了考查，确定乳胶粉用量10.0g、PVC=36.58vol%为配方中可再分散乳胶粉的最优添加量。通过上述研究，不仅制得了性能较佳的丙烯酸聚合物乳胶粉及其干粉涂料产品，也为后续新技术和相关理论的研究奠定了基础。
为了进一步提高可再分散聚合物乳胶粉的性能，本文将聚合物乳液合成中的交联改性技术应用于可再分散乳胶粉的制备中，将交联单体N-羟甲基丙烯酰胺(NMA)加入到原始乳液合成中，考查了NMA用量对乳液聚合、喷雾干燥工序和所得可再分散乳胶在干粉涂料中粘结性能的影响。在乳液聚合方面，由于NMA单体本身的高反应活性和水溶性，发现随着NMA用量的增加，乳液的粒径、单分散指数和乳液黏度随之增大，反应体系稳定性下降，因此确定NMA的最高使用量为3.0wt%。在喷雾干燥和产品性能方面，NMA用量的增加对于干燥所得乳胶粉流动性、堆积密度都起到了明显的改善作用，原始乳液的成膜性能和乳胶粉在干粉涂料中的成膜粘结性能也相应增强。
本文对干粉涂料和乳液涂料的成膜进行了比较，对最终漆膜的结构和性能进行了分析。结果发现由于聚合物粒子沉降行为的不同，两种涂料成膜的均匀程度存在差异。在涂料成膜过程中颜填料粒子都会出现一定程度的沉降，但是对于普通乳液涂料，聚合物粒子可以维持稳定的分散状态，所以液态漆膜的上表面处会出现单纯的聚合物乳液层，并演变为纯聚合物表层；而对于干粉涂料，再分散的聚合物粒子与颜填料粒子一样倾向于沉降，最终形成均匀结构的漆膜。由于喷雾干燥过程中乳液粒子发生不可逆融合，使得再分散乳液的粒径增大，粒子间毛细管直径增大，成膜推动力减小，从而导致干粉涂料成膜的致密程度较低。由此可知，制约可再分散乳胶粉在干粉涂料中应用和性能提升的关键是喷雾干燥过程中乳液粒子的不可逆融合，而该过程又进而影响了再分散乳液的沉降稳定性和粒径恢复。
本文采用PVA作为聚合保护胶体，对PVA-MMA体系和PVA-VAc体系的乳液聚合实验进行了横向对照研究。通过基元反应速率分析、PVA接枝比例测定、乳液聚合物中接枝产物的分离以及分析，发现PVA-MMA乳液聚合体系中PVA接枝的程度要大于PVA-VAc体系。结合乳液聚合体系的动力学行为(转化率-时间、粒径-时间)，发现在PVA-MMA体系中，水相中的单体分子和活性分子链有足够的时间进入乳液粒子并使其尺寸不断长大；在这个过程中，已经接枝固定在粒子原表面的PVA分子会被包埋在乳液粒子内部，使得粒子表面的PVA分子数量减少，乳液胶体稳定性降低。由此得出结论，正是由于PVA分子在聚丙烯酸酯粒子内“层层接枝”的发生，导致了PVA-MMA乳液聚合反应的不稳定。
最后，本文研究了聚合物-SiO2核壳复合粒子乳液的合成及其可再分散乳胶粉制备技术。首先考查了在含有小分子乳化剂胶束的模板乳液中制备聚合物-SiO2核壳复合粒子的可行性。结果发现，利用阳离子乳液体系中负电性的硅烷低聚物与模板粒子间的静电吸引力，可以获得具有规整核壳结构的聚合物-SiO2核壳粒子。接着使用阳离子核壳复合乳液进行可再分散乳胶粉的制备，对核层聚合物玻璃化温度、SiO2壳层厚度对于乳胶粉形态和再分散性的影响进行了考查。发现由于SiO2壳层的存在，聚合物耐受喷雾干燥的最低玻璃化温度由＞40℃降低到了10℃；随着SiO2壳层厚度的增加，所得乳胶粉的流动性和再分散性能有所改善，但是当正硅酸乙酯(TEOS)用量增加到55wt%及以上时，乳液粒子的融合增大，乳胶粉再分散性出现降低的趋势。
Compared with the polymeric products of emulsion state, redispersible polymer powderdoes not contain water as dispersion medium and makes it possible to save the packing,storage and transportation cost of products during the distribution process. Also because of itspowder state, redispersible polymer powder could be blended with cement, filler and pigmentpowders to prepare one-pack dry-mixed concrete or architectural coatings, which areconvenient and healthy for use. However there generally exist two disadvantages for currentpolyacrylate redispersible powder products: comparatively poor water resistance and binderperformance. Meantime the preparation technologies have made little progress from thetraditional―soft-core/hard-shell‖and macromolecular protective colloids technologies since1990s. On the theoretical side, the film formation process of dry-mixed coatings and thereason for unstability of PVA-MMA polymerization system are still indistinct, which limit thetechnical innovation and application performance of polyacrylate redispersible powder.
In this thesis we attempted to apply some new technologies in the manufacture ofpolyacrylate redispersible powder and did research on several key theoretical questions, inorder to get a deeper understanding of the preparation process and find out some innovativemethods to improve product performance, which are of great significance in both academicand industrial aspects. The main research topics and relevant conclusions are as follows:
The preparation process of redispersible powder was studied step by step at first, in orderto find out a basic recipe and relevant spray drying parameters to get redispersible powderwith qualified properties. The research results were shown as below: Tgof "soft core"-10oC,Tgof "hard shell"70oC, mass ratio of core/shell components3:1, MAA amount16wt%, inlettemperature120oC, rotating speed24,000rpm and feed rate20~40ml/min. Then theresultant redispersible powder from above formula was applied in dry-mixed coatings and thecoatings properties were tested, from which the optimal amount of redispersible powder wasdetermined as10.0g with PVC of36.58vol%. Through these studies the whole process ofredispersible powder preparation and application was made clear and the recipe andparameters would act as the groundwork for the following studies on innovative technologiesand fundamental theories.
The corsslinking modification technique was applied in the preparation of polyacrylateredispersible powder by adding crosslinking monomer N-hydroxymethyl acrylamide (NMA)into the polymerization of original emulsions, and the influences of NMA amount onemulsion polymerization, spray drying and properties of resultant powders were studied. Inpolymerization aspect it was found that the particle size, particle distribution index andviscosity of original emulsions increased with the increasing of NMA amount, while thecolloidal stability was lowered. This was determined by the high reactivity and watersolubility of NMA, which easily led to homopolymerization of NMA rather copolymerizationwith other monomers. So the NMA amount was selected as3.0wt%to guarantee the stabilityof original emulsion synthesis. In spray drying and property aspect, the increasing of NMAamount was proved to be beneficial for the improvement of flowing, stacking and bondproperties of the redispersible powders. These results confirmed that the crosslinkingmodification worked in the performance enhancement of redispersible polymer powder.
The film-formation mechanisms of dry-mixed coatings (based on the redispersiblepolymer powder) and latex coatings (based on the original polymer emulsion) were studiedand compared according to the structure and properties of the coatings films. It was found thatthere were two structural differences in the films of both products, which directly influencedtheir mechanical properties. One was homogeneous degree: There existed stratificationphenomenon in the film of latex coatings, which contained an upper polymer layer near thefilm/air interface and a bottom polymer-filler composite layer near the film/substrate interface,while the film of dry-mixed coatings only had uniform polymer-filler composite structure.This was mainly due to their different settlement conditions. In both coatings products fillerparticles tended to subside, but the settlement behaviors of polymer particles were different.In latex coatings the polymer particles were more stable in the coatings dispersions, so theycould remain in the upper part of the dispersion while filler particles subsided towards bottom,and finally dried to form the upper polymer layer of film. In dry-mixed coatings, unstablepolymer particles tended to subside together with filler particles and finally formed film ofuniform structure. The other difference was the compact degree: It was found that the innerstructure of latex coatings film was much more compact than the dry-mixed coatings film,and this was because that the particle size of re-dispersed polymer particles were much larger than the original ones due to the insufficient re-dispersion of redispersible powder, whichweakened the capillary forces of film formation. With the reasons of structural differencesabove, we found that both the instability and insufficient re-dispersion of dry-mixed coatingswere attributed to the irreversible coalescence of polymer particle in spray drying, and thiswas just the key point to improve dry-mixed coatings performance.
Lateral comparison was conducted between PVA-MMA emulsion polymerization andstable PVA-VAc emulsion polymerization, to find out the reason for the instability ofemulsion polymerization of acrylate monomers with PVA as protective colloid. Through theanalysis of the rate of elementary reactions, the proportion of grafted PVA molecules and thegrafting extent of the final copolymers, we could get the conclusion that the grafted amount ofPVA was even larger in the PVA-MMA copolymers than PVA/VAc ones, so the grafted modeof PVA was considered. Based on the reaction kinetics, it was found that the slower initiationand propagation rates of sulfate radical towards MMA was responsible, for they allowed theparticles to grow up all through the reaction process and resulted in―layer-by-layer‖graftingstructure of PVA. As the surface-grafting density of PVA was lowered, the colloidal stabilityof PVA-MMA emulsion was reduced consequently.
As inorganic components have higher melting point and better thermo-tolerance thanpolymer components, polymer-SiO2core/shell composite particles were utilized to prepareredispersible powder instead of―soft-core/hard-shell‖polymer particles. First a one-pot routetowards polymer-SiO2core/shell composite particles was developed through the templatesol–gel processing of alkoxysilane in emulsifier-involved aqueous emulsions, and it wasfound that the core/shell structure could be obtained on the basis of cationic templateemulsions for the electrostatic attraction between template particles and siloxane oligomers.Afterwards the composite emulsions were used to prepare redispersible powder and thefactors such as the Tgof core polymer component, the thickness of SiO2shell were studiedbased in the morphology and re-dispersion ability of redispersible powder. It was found thatwith the help of SiO2shell the Tgof inner polymer core could be reduced to10oC, and thiswas of great significance to further lower the MFFT of redispersible powder. The flowingre-dispersion properties of powder were improved with the increasing of TEOS amount, i.e.the thickness of SiO2shell, then declined when the TEOS amount exceeded55wt%. This was because that more free siloxane oligomers were generated with TEOS amount increasing andaggravated the coalescence of particles in spray drying process.
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