木器用多重交联羟基丙烯酸酯乳液的制备与应用研究

以丙烯酸丁酯(BA)及甲基丙烯酸甲酯(MMA)为主单体,丙烯酸(AA)、甲基丙烯酸羟乙酯(HEMA)以及双丙酮丙烯酰胺(DAAM)/己二酸二酰肼(ADH)自交联体系为功能性单体,采用半连续乳液聚合工艺制备木器用多重交联羟基丙烯酸酯乳液。探究了HEMA、DAAM/ADH、AA用量以及玻璃化转变温度(T_g)对乳液和涂膜性能的影响。结果表明:当羟基含量为4%,DAAM、AA分别占单体总量的2%、1.5%,且乳液T_g设计为20℃时,制备的羟基丙烯酸酯乳液配制成的双组分木器清漆,涂膜硬度可达2H、附着力为0级、耐水性优异且耐化学品性好。     

酰肼交联体系对外交联核壳结构苯丙乳液成膜性能的影响

以双丙酮丙烯酰胺(DAAM)和己二酸二酰肼(ADH)为交联单体,采用核壳乳液聚合法对常规苯丙乳液进行改性,制备了室温外交联型苯丙乳液。着重探讨了DAAM/ADH体系对苯丙乳液粒径、稳定性、干燥时间、涂膜强度以及耐水性等影响。研究结果表明:该苯丙乳液具有较明显的核壳结构,并且涂膜具有共价交联结构;当n(ADH)∶n(DAAM)=0.75∶1时,涂膜具有相对最好的综合性能,其铅笔硬度、拉伸强度和耐水性明显提高,并且室温干燥时间也明显缩短。     

N-羟甲基丙烯酰胺/苯丙乳液的制备与性能

本文合成了N-羟甲基丙烯酰胺(NMA)/苯丙乳液,讨论了NMA和乳化剂用量对乳液各种物理、化学性能的影响。结果表明:当NMA占单体质量分数的2%时,乳液的各项性能最好,明显提高了硬度和交联性能,耐水性也达到最优,该乳液在纸张涂层剂等方面有潜在应用价值。     

一种高光泽聚丙烯酸酯乳液的制备及性能研究

以St(苯乙烯)为硬单体、BMA(甲基丙烯酸丁酯)为软单体、HEMA(甲基丙烯酸羟乙酯)为功能单体、自制A-35(水溶性丙烯酸酯树脂)为乳化剂、DAAM(双丙酮丙烯酰胺)和ADH(己二酸二酰肼)为交联单体,采用种子乳液聚合法制备了一种新型水性上光涂料用聚丙烯酸酯乳液。研究结果表明:当m(St)∶m(BMA)=50∶42~45∶52、w(A-35)=20%~30%(相对于乳液总固含量而言)、w(HEMA)=2%和w(DAAM)=2.5%(均相对于单体总质量而言)时,该乳液的硬度、附着力和储存稳定性相对最佳,并且涂膜可室温固化,而且其光泽度、耐水性、耐溶剂性及耐磨性均满足水性上光涂料的使用要求。     

室温自交联型丙烯酸酯改性聚氨酯乳液的制备

本文以异佛尔酮二异氰酸酯(IPDI)、聚酯二元醇(Mn=1500)、二羟甲基丙酸(DMPA)、甲基丙烯酸羟乙酯(HEMA)、甲基丙烯酸甲酯(MMA)、双丙酮丙烯酰胺(DAAM)等作为主要原料合成聚丙烯酸酯-聚氨酯乳液(PUA)。考察了MMA、DAAM含量及DAAM/ADH不同比例对PUA的乳液粒径、涂膜耐水性和硬度等的影响。通过红外光谱、激光粒度仪等手段,选取了制备PUA较好的工艺配方,为合成性能优异的聚丙烯酸酯-聚氨酯乳液奠定了的基础。     

羟基丙烯酸酯乳液的合成及性能研究

以丙烯酸丁酯,甲基丙烯酸,甲基丙烯酸羟乙酯为单体,采用种子乳液聚合的方法制备羟基丙烯酸酯乳液,用红外光谱分析了共聚乳液的结构。乳液聚合的最佳条件为:反应温度为75-85℃,引发剂用量为单体用量的0.3%。羟基单体用量增加,乳液稳定性降低,凝胶含量增加,涂膜的耐水性下降,涂膜硬度增大,附着力增强。     

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%。     

水性油墨用室温自交联纯丙乳液的合成及应用

以甲基丙烯酸甲酯(MMA)、丙烯酸异辛酯(2-EHA)、甲基丙烯酸(MAA)、双丙酮丙烯酰胺(DAAM)为聚合单体,己二酰肼(ADH)为交联剂,采用半连续种子乳液聚合法合成软核硬壳结构的水性纯丙乳液。利用ATR-FTIR、TEM、GPC、TG、DMA表征水性纯丙乳液的结构和性能。结果表明:乳液成膜过程中DAAM中的—CO—与ADH中的—NHNH_2发生反应,交联度增加,提高了乳液膜的耐水性、热稳定性、玻璃化转变温度和油墨在双向拉伸聚丙烯(BOPP)薄膜上的附着力。当DAAM用量(以MMA和2-EHA的总质量为基准,下同)从0增加到2%,m(ADH)∶m(DAAM)=0.7∶1.0时,乳液膜的吸水率从24.2%降到7.6%,油墨的附着力从87%升至100%;当m(ADH)∶m(DAAM)从0∶1增加到0.7∶1.0,DAAM用量为2%时,乳液膜的吸水率从28.1%降至7.6%,油墨的附着力从0增至100%。当DAAM用量为2%,m(ADH)∶m(DAAM)为0.7∶1.0时,水性纯丙乳液可用作环保型水性油墨的连接料。     

金属防腐漆用双重自交联丙烯酸乳液的制备及其性能研究

以甲基丙烯酸甲酯(MMA)和丙烯酸2-乙基乙酯(2-EHA)为主单体,甲基丙烯酸(MAA)、乙烯基三乙氧基硅烷(A-151)、双丙酮丙烯酰胺(DAAM)和己二酸二酰肼(ADH)的酰肼交联体系以及丙烯酸磷酸酯(PAM-100)为功能单体,采用反应型乳化剂SE-10N,通过预乳化乳液聚合工艺合成了金属防腐漆用双重自交联丙烯酸酯乳液。考察了乳液Tg、MAA、SE-10N、A-151、DAAM/ADH和PAM-100对乳液及其金属防腐漆涂膜的影响。结果表明:当乳液设计Tg为30℃、MAA用量为单体总量的3%、反应型乳化剂SE-10N用量为单体总量的2.5%、A-151用量为单体总量的2%、DAAM用量为单体总量的2%、PAM-100用量为单体总量的3%时,所制备的自交联丙烯酸酯乳液配制成的金属防腐涂料,具有附着力好、耐盐水、耐酸碱、耐盐雾等特点。     

可聚合乳化剂制备高固含量丙烯酸酯乳液

以甲基丙烯酸甲酯(MMA)为硬单体、丙烯酸丁酯(BA)为软单体、丙烯酸(AA)和N-羟甲基丙烯酰胺(NMA)为功能性单体以及过硫酸铵(APS)为引发剂,合成了固含量为41%左右的丙烯酸酯乳液。研究结果表明,可聚合乳化剂(F-6)、NMA和反应温度等对丙烯酸酯乳液性能有影响。当反应温度为85℃左右、F-6用量为0.5%和NMA用量为0.25%时,合成的丙烯酸酯乳液的综合性能较好。     

碱溶性丙烯酸树脂在水性木器漆乳液制备中的应用

以碱溶性丙烯酸树脂作为乳化剂,以丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸正丁酯、丙烯酸2-乙基己酯为共聚单体,双丙酮丙烯酰胺为交联单体,过硫酸钾为引发剂,系统研究了碱溶性丙烯酸树脂的相对分子质量、酸值、用量及配伍,交联单体的用量对乳液聚合稳定性,乳液粒径及分布,涂膜的耐水性、耐醇性、硬度及最低成膜温度的影响。结果表明:当低酸值低相对分子质量碱溶性丙烯酸树脂与高酸值高相对分子质量碱溶性丙烯酸树脂复配且质量比为7:3~9:1,总量为单体的16%~26%时,聚合稳定性均较好且粒径可控制在50~80 nm之间。涂膜室温养护7 d的硬度可达到3H,耐水白可达400 h,经60°白酒浸泡7 d涂膜无变化,表明这种乳液可适合用作木器家具涂料的成膜物质。     

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。     

水性苯丙防腐涂料清漆的研究与改进

采用半连续种子乳液聚合工艺,以苯乙烯为主要硬单体、丙烯酸丁酯为主要软单体,以功能单体为附着力及耐腐蚀性促进单体,以双丙酮丙烯酰胺为交联单体,制备了稳定性良好的苯丙聚合物乳液。所得聚合物乳液的固含量约为40%、乳胶粒子粒径约为130 nm,乳液通过3%氯化钙水溶液测试和2 500 r/min机械搅拌测试。确定了消泡剂种类及用量,所得漆膜无气泡,表面平滑无缩孔。选用合适的水性闪锈抑制剂,喷漆后无闪蚀,漆膜平整均匀。所得清漆漆膜耐水性14 d未起泡、30 d未生锈,耐盐水性15 d未生锈,耐碱性30 d未生锈、未起泡。     

Study on the preparation and properties of styrene–butyl acrylate–silicone copolymer latices

Copolymer latices of styrene–butyl acrylate–silicone were prepared using a semicontinuous addition process and batch and monomer emulsion addition processes. The results showed that a stable latex with narrow particle size dispersion and a high monomer conversion can be obtained only by the semicontinuous addition process. The simultaneous free‐radical and ionic copolymerization mechanisms were discussed. 3‐Methacryloyloxypropyl trimethoxysilane in this work was used as a coupling agent to form a chemical bond between vinyl polymer and polysiloxane. It was found that the copolymerization reaction and the properties of latex and latex film were obviously influenced by silicone content. When the silicone content was less than 25 wt %, copolymerization proceeded readily and a stable latex could be prepared. With increasing silicone content, monomer conversion, latex stability, film hardness, and tensile strength decreased, whereas the water resistance and impact strength increased. Results of Soxhlet extraction, silicon analysis, and dynamic mechanical properties of latex polymer confirmed the occurrence of copolymerization. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3194–3200, 2001     

Nonionic surfactant-stabilized raspberry-like polymer/silica nanoparticles latex with film formability

Raspberry-like P(St-BA)/SiO₂ nanoparticle latexes were prepared via miniemulsion polymerization of styrene (St) and butyl acrylate (BA) in the presence of 20 nm glycerol-modified SiO₂ sol as a Pickering emulsifier and octaphenyl polyoxyethylene (CA-897) as a nonionic surfactant, using 2,2-azobis (isobutyronitrile) (AIBN) as an initiator. 2-(Methacryloyl) ethyltrimethylammonium chloride (MTC) was introduced to act as an auxiliary monomer to enhance the attraction of SiO₂ sol onto latex nanoparticles (NPs) via increasing their electrostatic interaction with negative-charged SiO₂ sol. The average particle sizes of the latex particles can be well controlled from 200 to 360 nm by variation of the SiO₂ sol content as well as soft monomer BA component. The latex NPs displayed a good colloidal stability with excellent resistance to both strong acidic and basic environment. Furthermore, the nanosized latexes exhibited good film formability. The influence of reaction parameters, e.g., the initial silica amount and soft monomer BA content was systematically investigated on the film performances, such as hardness, abrasive resistance, water absorption, gloss. The results indicated that the increase of SiO₂ sol content can contribute to the increase of the film hardness and water absorption ability, while increasing BA component is beneficial to the improvement of the film gloss.     

Synthesis of a latex with bimodal particle size distribution for coating applications using acrylic monomers

Multipart emulsion polymerization of methyl methacrylate (MMA) and butyl acrylate (BA) was carried out in this work. The target was to achieve stability during the polymerization and to determine the proper hydrophilic–lipophilic balance (HLB) value for the stable system, using different types of non-ionic emulsifiers, sodium lauryl sulphate and their combinations. After determination of proper value of HLB (36.2), the best emulsifier combination on the basis of minimization of coagulum level was determined. This combination was 20 wt.% of KENON30 to SLS. The effect of monomer feed composition on the dry latex film properties was investigated to approach a monomer feed composition dealt with a proper T_g. The prepared latex showed a bimodal particle size distribution, due to the proper feeding policy in semibatch emulsion copolymerization process. The monomer feed composition of 45 wt.% MMA and 55 wt.% BA with a proper T_g was selected for the final improvement of coating properties such as UV resistance and adhesion. Adding acrylic acid (AA) and N-methylol acrylamide (NMA) to the reaction mixture improved the UV resistance and adhesion property of dry latex film. The flow and leveling, gloss, adhesion, UV resistance and water resistance of the produced bimodal latex showed good quality in comparison with the similar commercial resins used in coating applications.     

纳米二氧化硅水性塑料涂料的研制

采用核壳乳液聚合工艺和功能单体对乳液进行改性,制备了具有核/壳结构的苯丙乳液,与纳米二氧化硅复合,得到高性能的啦性纳米复合塑料涂料。介绍其涂膜硬度达到3H以上,耐热在100℃沸水中不回粘,耐水性好、丰满度高的特点。     

Effect of acrylic monomer content on the properties of waterborne poly(urethane‐urea)/acrylic hybrid materials

Stable waterborne poly(urethane‐urea) (WBPU; soft segment content: 57%; dimethylol propionic acid: 19 mol %/5.8 wt %)–polyacrylate(methyl methacrylate/n‐butyl acrylate) (weight ratio: 4/1) hybrid latex (emulsions) with different acrylic contents [0, 10, 20, 30, and 40 wt % based on poly(urethane‐urea)] and without external surfactant were successfully prepared by in situ polymerization during a prepolymer mixing process. However, the as‐polymerized hybrid latex containing 50 wt % of acrylic monomer content was found to be unstable, indicating that about 50 wt % of acrylic monomer content was beyond the limit value of self‐emulsifying ability of WBPU anionomer prepared in this study. The breadth of particle size distribution of hybrid latex increased markedly from 20–75 to 55–275 nm with increasing acrylic monomer content from 0 to 40 wt %. The pristine WBPU and hybrid latex samples containing 10, 20, and 30 wt % of acrylic monomer showed unimodal distributions, whereas the hybrid sample having 40 wt % acrylic monomer content displayed a bimodal distribution with the broadest breadth. As acrylic monomer content increased, the yield point of stress–strain curve, hardness, glass transition, and water resistance of hybrid film samples increased, whereas their abrasion resistance, elongation at break, and elasticity decreased. The tensile strength of hybrid film samples (10–30 wt % of acrylic monomer content) was almost the same as that of pristine WBPU film sample, indicating the intimate molecular mixing between poly(urethane‐urea) and polyacrylate molecules in hybrids. However, the hybrid sample having 40 wt % acrylic monomer showed significantly diminished performance, which might be due to the deviation from intimate molecular mixing. From these results, the optimum acrylic monomer content was found to be about 30 wt %, which realized reasonably advantages of both poly(urethane‐urea) and acrylic polymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

水性丙烯酸酯乳液的合成及性能研究

以双丙酮丙烯酰胺（DAAM）为功能性单体,采用预乳化半连续种子乳液聚合法合成水性丙烯酸酯乳液,添加己二酸二酰肼（ADH）为交联剂,构成室温自交联体系。考察了DAAM、ADH用量对乳液及其乳胶膜性能的影响。用傅里叶红外光谱仪（FT-IR）对交联反应进行了表征。通过差示扫描量热法、力学性能和耐溶剂性能的测试等方法研究了乳液和乳胶膜的性能。结果表明,当DAAM用量为2.4%~3.5%,ADH与DAAM的当量比为1~1.2时,乳液和乳胶膜的综合性能较好。