含氟核壳苯丙乳液的合成与涂膜性能研究

以全氟烷基乙基甲基丙烯酸酯(FMA)为含氟单体、可聚合型烯丙氧基壬基酚聚氧乙烯(10)醚硫酸铵(DNS-86)为乳化剂,采用半连续法制备了具有核壳结构的含氟苯丙乳液.采用FT-IR、TEM、TGA分别对共聚物的组成、乳胶粒形态与涂膜热稳定性进行了表征,并对涂膜接触角及耐化学性进行了分析.结果表明,当FMA用量为8.0%时,所得乳液涂膜的水/油接触角分别为111.5°与67.9°,涂膜的耐化学和热稳定性优良.     

含氟水性聚氨酯-丙烯酸酯涂料的制备及其成膜强度和耐水性的研究

采用原位乳液聚合法,合成了含氟自交联型水性聚氨酯-丙烯酸酯(FPUA)乳液.研究了单体物质的量比、环氧基团含量和氟单体含量对乳液制备过程、乳液及涂膜性能的影响.通过红外光谱、热重分析对其结构和膜性能进行表征,并对涂膜表面的水接触角进行了研究.结果表明:n(—NCO)∶n(—OH)=1.4、n(—NHNH2)∶n(—CO—)=1、GMA用量为4％、含氟单体用量为6％时,合成乳液稳定性良好,涂膜的耐水性和热稳定性良好.在成膜时复合乳液中的氟基团向空气/聚合物界面伸展,有效地覆盖涂膜表面,降低涂膜表面能,水在涂膜上的接触角达到117.2°.     

氟改性UV固化超支化水性聚氨酯的制备与性能研究

采用HDI三聚体(HDT)和二乙醇胺(DEOA)自制六羟基多元醇;采用异佛尔酮二异氰酸酯(IPDI)、全氟己基乙基醇(TEOH-6)和三羟甲基丙烷(TMP)自制含氟二元醇;以IPDI、聚碳酸酯二元醇(PCDL)、含氟二元醇、二羟甲基丁酸(DMBA)、季戊四醇三丙烯酸酯(PETA)为主要原料合成—NCO半封端的聚氨酯,将六羟基多元醇加入到聚氨酯中,制备了氟改性UV固化超支化水性聚氨酯(FWPU)。采用光学接触角、纳米粒度仪、电子拉力机、原子力显微镜等对涂膜的结构与性能进行了测试。研究了含氟二元醇添加量对涂膜疏水性、力学性能、硬度、热稳定性等的影响。结果表明:随着含氟二元醇的加入,乳液粒径逐渐增大、分布变宽,涂膜接触角增加、吸水率大幅降低、热稳定性增强、拉伸强度大幅度增大、硬度达到4H。当含氟二元醇含量为8%时,涂膜的综合性能最佳。     

环氧乳液与含氟乳液的拼混研究

运用种子乳液聚合法制备了固含量(固体质量分数)为45%的含氟乳液;运用后乳化法制得了环氧乳液。ATR-FTIR测试表明环氧乳液与含氟乳液进行了有效的拼混。运用KrussK12型动态表面能分析仪测试了含氟涂膜对水和十六烷的接触角,对影响拼混乳液涂膜性能的因素如环氧树脂及其固化剂的比例、氟原子含量、成膜基材材质、成膜温度等进行了探讨研究。结果表明制备的含氟拼混乳液性能良好。     

含氟丙烯酸酯乳液合成及其内墙涂料防涂鸦性的研究

以烯丙氧基羟丙基磺酸钠(COPS-1)、壬基酚聚氧乙烯醚硫酸铵(CO-436)和NP-10为复合乳化剂,过硫酸铵为引发剂进行了含氟丙烯酸酯乳液聚合研究,测定不同含氟单体含量制备的乳液干膜及漆膜与水、油的接触角,比较含氟单体含量、不同交联单体及含量对涂膜耐污性能的影响。研究结果表明:随含氟单体含量增加,乳液干膜及涂膜与水、油接触角增大;由12%甲基丙烯酸十二氟庚酯、5%双丙酮丙烯酰胺所合成的含氟丙烯酸酯乳液,稳定性高,耐沾污性好;当乳液含量为涂料配方总量的36%时,涂膜对水彩污迹的耐污性能明显改善,且遮盖力好。     

含氟丙烯酸酯乳液高疏水性与低氟含量的平衡探索

为了研究含氟丙烯酸酯乳液涂膜的疏水性与氟含量的平衡关系,以甲基丙烯酸十二氟庚酯(DFHM)为含氟单体,双丙酮丙烯酰胺(DAAM)和己二酸二酰肼(ADH)为交联单体,采用半连续核壳乳液聚合的方法合成了一系列自交联含氟丙烯酸酯共聚物乳液。研究表明:含氟单体含量为12%(即氟含量为6.84%,均以聚合单体的总质量计,下同)时,含氟基团在涂膜表面可以达到饱和,乳液固含量可达38.2%;再添加4%交联单体,涂膜的水接触角为116.6°。当含氟单体含量降为4%(氟含量2.28%)时,通过提高成膜温度或添加成膜助剂,也可使涂膜表面的水接触角达到104.2°,具有较好的疏水性能。     

含氟水性聚氨酯的制备及其性能研究

采用八氟戊醇(F8)改性水性聚氨酯,制备了含氟水性聚氨酯(FWPU),并且通过红外光谱对FWPU的结构进行了表征。研究了F8含量对FWPU乳液及其涂膜的影响。研究表明,F8的加入,明显提高了涂膜的耐水性能。当F8含量为8%时,涂膜的吸水率从未改性的12.2%减少到3.1%,接触角从80°提高到108°。乳液粒径先增大后减少,当F8含量为4%时,乳液粒径最大,达到157 nm。TGA测试结果表明,改性后的FWPU涂膜热稳定性有所提高。     

聚合工艺条件对含氟涂膜表面性能的影响

运用种子乳液聚合法制备了较高性价比的含氟乳液。FTIR光谱和DSC测试表明,含氟单体参与了聚合反应。运用KrussK12型动态表面能分析仪,测定聚合工艺中以不同用量的乳化剂、引发剂、含氟单体、N 羟甲基丙烯酰胺(N MA)在不同的单体滴加速度下合成的乳液涂膜对水和十六烷的接触角,结果表明,w(乳化剂)=3 5%、w(引发剂)=0 45%、w(N MA)=4%、聚合物中x(F)=14%时,乳液涂膜对水和十六烷的接触角较佳,对水的接触角达115°,涂膜表现出良好的表面性能。     

核壳型短链含氟丙烯酸酯乳液的合成及表征

该文研究了核壳型短链含氟丙烯酸酯乳液的合成与表征。以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)的共聚体为核,短氟碳链2-(全氟己基)乙基甲基丙烯酸酯(FMA6)和非氟烷基丙烯酸酯的共聚体为壳,采用多步乳液聚合法,合成系列具有核壳结构的含氟丙烯酸酯乳液,研究了壳相中氟单体用量和非氟烷基丙烯酸酯的烷基链长度n(链长n=4、8、12、16、18)对产物疏水疏油性能的影响,并对产物进行表征。结果表明:当采用氟单体用量为总单体质量的8.5%,甲基丙烯酸十六酯(CMA)的共聚体为壳层时,由合成乳液制得的乳胶膜的疏水疏油性最佳,对水接触角为124.67°,对二碘甲烷接触角为112.76°。FTIR、TEM和DSC/TGA表征表明,原料单体均参加了反应;乳液颗粒具有明显的核壳结构;聚合物存在两个玻璃化温度(-18.87℃和32.08℃),热分解温度比不含氟的聚合物提高了近20℃。由此说明,用合成的核壳型短链含氟丙烯酸酯乳液制得的涂膜具有优异的疏水疏油性和耐热性能。     

UV固化含氟低聚物的制备及性能研究

首先由甲基丙烯酸十二氟庚酯（ DFHMA）与乙醇胺通过 Michael加成反应得到含氟醇;其次以含氟醇、马来酸酐和甲基丙烯酸缩水甘油酯（ GMA）合成活性含氟中间体;最后将之与异佛尔酮二异氰酸酯（ IPDI）、季戊四醇三丙烯酸酯（ PETA）反应得到可紫外光（ UV）固化的含氟低聚物。采用红外光谱、核磁共振对产物结构进行表征。以所得低聚物制备 UV固化涂膜,通过测试涂膜接触角、热稳定性、硬度等研究不同含氟醇添加量对涂膜性能的影响。结果表明：当含氟醇质量分数从 0增加到 10%时,涂膜水接触角从 56. 3°上升到 98. 2°,表面自由能由 52. 62 mN/m降至 22. 96 mN/m,且涂膜热稳定性提高,硬度提高。     

高分子附聚法制备超大粒径聚丁二烯胶乳

以自制丙烯酸胶乳为高分子附聚剂,以粒径300nm聚丁二烯胶乳(PBL-0700)为起始胶乳,采用高分子附聚法制备了500～600nm超大粒径聚丁二烯胶乳(目标胶乳),考察了附聚剂加入量、放置时间、后稳定剂的加入、附聚温度等因素对目标胶乳粒径的影响,确定了高分子附聚法超大粒径聚丁二烯胶乳制备工艺。     

核壳型丙烯酸酯乳胶的合成

采用丙烯酸下酯、丙烯酸乙酯和甲基丙烯酸甲酯作为主单体，甲基丙烯酸为功能单体，通过对单体配比和乳化剂用量的选择，得到了一种粘度适当、稳定性良好的乳胶，并进一步考察了涂层的附着力、硬度和抗水性。结果表明，该胶可以满足多种类型乳胶涂料的要求。     

Synthesis and characteristics of poly(methyl methacrylate-methacrylic acid-3,3-(trimethoxysilyl) propyl methacrylate) hollow latex particles and their application to drug carriers

In this study, the hollow latex particle was synthesized by three processes. The first process was to synthesize the poly(methyl methacrylate-co-methacrylic acid) (poly(MMA-MAA)) copolymer latex particles by the method of soapless emulsion polymerization. Following the first process, the second process was to polymerize MMA, MAA, 3,3-(trimethoxysilyl) propyl methacrylate (MPS), and ethylene glycol dimethacrylate in the presence of poly(MMA-MAA) latex particles to form the linear poly(MMA-MAA)/crosslinking poly(MMA-MAA-MPS) core–shell latex particles. In the third process, the core–shell latex particles were heated in the presence of ammonia to form the poly(MMA-MAA-MPS) hollow latex particles. A sufficient heating time and high-heating temperature were necessary for the ammonia to dissolve the linear poly(MMA-MAA) core to form a perfect hollow structure. The crosslinking poly(MMA-MAA-MPS) shell was a barrier for the ammonia to diffuse into the latex particles so that the latex particle with the high-crosslinking shell showed an imperfect hollow structure. Besides, the hollow poly(MMA-MAA-MPS) latex particles reacted with ZnO nanoparticles, which were synthesized by a traditional sol-gel method, to form the polymer/inorganic poly(MMA-MAA-MPS)/ZnO composite hollow latex particles. With the increase of crosslinking degree would increase the amount of ZnO bonding. Moreover, the poly(MMA-MAA-MPS) hollow latex particles were used as carriers to load with the model drug, caffeine. The release of caffeine from poly(MMA-MAA-MPS) hollow latex particles was investigated.     

遮盖性空心乳液的制备及其在水性油墨中的应用

采用核壳乳液聚合法制备聚甲基丙烯酸甲酯(MMA)-甲基丙烯酸(MAA)-丙烯酸丁酯(BA)为亲水核,聚苯乙烯(St)-丙烯腈(AN)-二乙烯苯(DVB)为疏水硬壳的核壳型乳液,然后进行碱溶胀处理,制得具有中空结构的遮盖性空心乳液。考察了MAA用量、核壳比(核单体与壳单体的质量之比,下同)对空心乳液中空度及遮盖性的影响,并利用透射电镜(TEM)、扫描电镜(SEM)对空心乳液的结构形态进行了表征。结果表明,当核单体中MAA用量为核单体总量的30%(质量分数),核壳比为1∶6时,乳胶粒的中空度约为50%,空心乳液遮盖性最强,应用于水性油墨中能够获得良好的综合性能。     

Effect of serum components on styrene/butyl acrylate latex film formation: An in situ examination by ultramicroscopy

Film formation by a surfactant‐stabilized, peroxide‐initiated styrene/butyl acrylate latex was followed in situ by ultramicroscopy. The effects of latex serum components on film formation were observed first by the subjection of the latex to extensive dialysis and then by the separate addition of salt and surfactants. Domains of different particle concentrations were observed in the latex dispersion during liquid evaporation, and their positions were related to those of defects in the dry film. Films obtained with the dialyzed latex showed macroscopic defects, which were not seen in the as‐prepared latex. Partially reconstituted latex (dialyzed, with the later addition of salt but not surfactant) behaved like the as‐prepared latex. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 159–167, 2003     

自交联反应性丙烯酸酯类微凝胶乳液及其涂膜的性能

采用半连续种子乳液聚合法,以三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)为交联剂、甲基丙烯酸缩水甘油酯(GMA)和甲基丙烯酸(MAA)为功能单体,合成了具有球形结构的自交联反应性丙烯酸酯类微凝胶乳液,并对其结构、性能以及涂膜的性能进行了研究.结果表明,合成的产物是带有悬吊双键及环氧基团的球形自交联反应性丙烯酸酯类微凝胶乳液,其粒径在40～50 nm,呈假塑性;当TMPTMA的质量分数为3%～6%、MAA的质量分数为3.00%～5.00%时,热处理后涂膜的耐水性和力学性能最佳.     

Double in-situ synthesis of polyacrylate/nano-TiO2 composite latex

Polyacrylate/nano-TiO₂ composite latex was prepared via double in-situ polymerization using acrylamide (AM), vinyl acetate (VAc), butyl acrylate (BA) and methyl methacrylate (MMA) as monomers, tetrabutyl titanate (Ti(OBu)₄) as precursor of TiO₂. The morphology, structure and distribution of composite latex were characterized by Transmission Electron Microscope (TEM), Fourier Transform Infrared Spectroscopy (FTIR), Dynamic Light Scattering (DLS) and X-Ray Diffraction (XRD). The thermal stability, anti-yellowing and antibacterial properties of composite latex were also investigated. The results showed that nano-TiO₂ consisted in polyacrylate latex and it was located on the surface of latex particles. The average particle size of polyacrylate/nano-TiO₂ composite latex was 156.6 nm, which was bigger than that of pure polyacrylate (125.1 nm). The introduction of nano-TiO₂ improved the thermal stability, anti-yellowing and antibacterial properties of the latex film. At last, the polyacrylate/nano-TiO₂ composite latex was applied in leather finishing. Compared with polyacrylate latex, the properties of the leather finished by polyacrylate/nano-TiO₂ composite latex were enhanced: water vapor permeability increased by 58% and water uptake decreased by 3.52%.     

用于可再分散乳胶粉的阳离子苯丙乳液的合成

采用种子乳液聚合法,以十六烷基三甲基溴化铵(CTAB)为乳化剂,偶氮二异丁眯盐酸盐(AIBA)为引发剂,引入亲水性阳离子单体甲基丙烯酰氧乙基三甲基氯化铵(DMC)及功能性单体丙烯酰胺(AM)〔m(DMC)∶m(AM)=1∶1〕来制备用于可再分散乳胶粉的阳离子苯丙乳液。探讨了聚合反应温度、乳化剂用量、引发剂用量、种子单体用量、阳离子单体用量等对乳液及可再分散乳胶粉性能的影响。确定最佳配方和工艺条件为:聚合反应温度为(80±2)℃、DMC添加量为2%(以主要聚合单体质量计,下同)、CTAB用量为2%(以单体总质量计,下同)、AIBA用量为0.53%(以单体总质量计,下同)、种子单体用量为10.0%(以单体总质量计,下同)。在该工艺条件下,合成的阳离子苯丙乳液粒径大小和分布适中、性能稳定,由其所制得的可再分散乳胶粉含水率低、平均粒径小、再分散性优良。     

Synthesis and characterization of fluorinated polyacrylate latex emulsified with novel surfactants

The fluorinated polyacrylate latex were successfully prepared with semi- continuous seeded emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA) and hexafluorobutyl methacrylate (HFMA) which was initiated with potassium persulfate (KPS) initiator and emulsified with the novel mixed surfactants of sodium lauryl glutamate (SLG) and alkylphenol ethoxylates (OP-10). The structure of the resultant latex was confirmed by Fourier transform infrared spectroscopy (FTIR). The particle size of the latex was measured by Zetatrac dynamic light scattering detector. The film of latex was tested by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and contact angle (CA). The optimum conditions of preparing the novel fluorinated polyacrylate latex are optimized and the results are as follows: the amount of emulsifiers is 4.0%; mass ratio of SLG to OP-10 is 1:1, the amount of the initiator is 0.6%. The mass ratio of MMA to BA is 1:1 and the amount of HFMA is 7.0%. In this case, the conversion is high and the polymerization stability is good. In addition, the water resistance and thermal properties of the latex films were improved significantly in comparison with the film of the latex prepared without the fluorinated monomer.     

导电聚苯胺／丁苯吡胶乳复合聚合物

以丁苯吡胶乳（ＰＳＢＲＬ）为稳定剂，苯胺（Ａｎ）进行氧化聚合，制得的导电ＰＡｎ／ＰＳＢＲＬ复合聚合物可直接浇铸成膜，亦可经破乳后用其沉淀物经热压成膜。氧化聚合条件：［ＨＣｌ］＝１．４ｍｏｌ／Ｌ，［Ａｎ］＝０．５ｍｏｌ／Ｌ，［氧化剂］＝０．２５ｍｏｌ／Ｌ。胶膜性质：当该复合聚合物中ＰＡｎ含量约为５０％时，电导率可达５×１０２Ｓ／ｍ左右，拉伸强度约１３ＭＰａ，扯断伸长率为５３％，在空气气氛中贮存２８ｄ电导率基本不变。