核壳型硅丙复合乳液的合成及其性能研究

用单体预乳化法和半连续种子乳液聚合法合成了核壳型硅丙复合乳液,研究了壬基酚聚氧乙烯醚-2-磺酸基琥珀酸单酯二钠盐(MS-1)与十二烷基硫酸钠(SDS)复配比例、核层聚合乳化剂补加速率及壳层聚合乳化剂补加速率对乳液性能和乳胶粒粒径及其分布的影响。考察了复配乳化剂用量对单体转化率、涂膜耐水性的影响规律。结果表明,所合成的系列乳液中,复配乳化剂所合成乳液的乳胶粒粒径小,粒径最小为72.99nm,乳液黏度大,其最大值为60.0mPa.s;而采用MS-1单一乳化剂所合成乳液的乳胶粒粒径分布最窄,其多分散性指数(PDI)为0.01,乳液黏度最小,其值为37.78mPa.s。当核层和壳层聚合乳化剂持续补加时间分别为120min和210min时,聚合体系乳胶粒数目基本保持不变,后续加入的单体在种子乳胶粒表面进行聚合,形成"核壳"结构。此外,随着乳化剂用量增加,单体的转化率提高但涂膜的耐水性下降。并用红外、透射电镜分别对聚合物分子链结构和乳胶粒形貌结构进行了表征。     

单组分核壳型苯丙乳液制备及其木材粘接性能研究

采用两阶段饥饿态种子乳液聚合法,制备了以PS(聚苯乙烯)基聚合物为核、以PA(聚丙烯酸酯)基聚合物为壳的核壳型苯丙复合乳液,研究了核单体组成对核壳型苯丙乳液乳胶膜热性能、吸水率、胶接性能等的影响。研究结果表明:不同试验条件都可以制得核壳型苯丙乳胶粒;随着核单体中BA(丙烯酸丁酯)含量的增加,苯丙乳胶膜吸水率显著降低;在构建核壳结构化乳胶粒后,苯丙乳液的胶接性能较苯丙无规共聚物乳液显著提高,其胶接强度大幅度增加且耐沸水开裂时间显著延长。     

微波辐射强化制备含氟硅丙烯酸酯共聚物乳液

采用多步种子乳液聚合法,以丙烯酸丁酯、甲基丙烯酸甲酯、g-(甲基丙烯酰氧)丙基三甲氧基硅烷和甲基丙烯酸六氟丁酯为原料在微波辐射下制备了核-壳型含氟硅丙烯酸酯共聚物乳液. 并研究了共聚物的结构、乳胶粒的形态和聚合过程中粒径的变化. 结果表明,所得乳胶粒子呈核-壳结构,与常规加热相比,微波的引用能加快反应速率,形成核-壳结构. 壳层富集含氟硅聚合物的核-壳形态有利于含氟硅结构单元在聚合物膜表面的分布,当氟硅单体为6%(w)时,乳胶膜对水的接触角达91.3o. 加入氟硅组分显著提高了聚合物膜的耐水性,当其含量从0增大到18%时,乳胶膜的吸水率从20.1%降低到3.54%.     

NMA改性PVAc基反向核壳结构乳液的制备及其性能研究

采用粒子设计手段,通过半连续种子乳液聚合法制备了以PVAc(聚醋酸乙烯酯)为核、PS(聚苯乙烯)为壳、MA(马来酸酐)为桥接单体的反向核壳结构乳液。以具有自交联属性的NMA(N-羟甲基丙烯酰胺)为功能单体,在壳层表面通过接枝共聚方法进行功能性修饰。核壳结构化的构建及表面功能性修饰赋予复合乳液室温交联特性,构建的乳胶粒子形貌呈草莓型。w(NMA)=1.0%、2.0%(相对于单体总质量而言)时,粒径均匀约为157 nm。复合乳液胶接试件耐水性增强,可耐沸水煮180 min;且剪切湿强度明显提升,最大湿强度达到2.2 MPa。     

核壳型聚苯乙烯/聚甲基丙烯酸甲酯复合乳液的制备

以过硫酸铵(APS)为引发剂,用种子乳液聚合方法,合成出以聚苯乙烯(PSt)为核, 聚甲基丙烯酸甲酯(PMMA)为壳的复合乳液。透射电子显微镜观察了核壳复合乳胶粒的形态,光散射粒径分布仪(PCS)测量胶乳粒径大小及其分布。最终成功地制得了核壳型PS/PMMA复合乳液,所得复合乳胶粒粒径大小在60～90nm左右,且单分散性较好。     

核壳结构聚硅氧烷/丙烯酸酯复合乳液(Ⅰ)乳化剂对乳液聚合过程及粒径分布和粒子形态的影响

采用种子乳液半连续法合成了具有高有机硅含量的聚硅氧烷/丙烯酸酯核壳结构复合乳液,研究乳化剂的种类、复配比例及质量浓度对有机硅／丙烯酸酯壳核乳液性能与乳胶粒径、分布和结构的影响.结果表明：阴离子乳化剂十二烷基硫酸钠(SDS)、十二烷基磺酸钠(SDS-2)、十二烷基苯磺酸钠(SDBS)所合成的乳胶粒子粒径依次增大,SDS与非离子型乳化剂OP-10复配使用时,随OP-10质量分数的增加,聚合速率和转化率降低,化学稳定性增加,乳胶粒子粒径增大,分布变宽,确定了复合乳化剂的最佳配比.随复合乳化剂浓度的增加,聚合速率加快、转化率增加,乳胶粒子粒径减小而分布加宽.通过改变乳化剂加入方式可减小乳胶粒子的粒径分布.为减少壳层聚合物新粒子的产生,需严格控制乳化剂的浓度,使加入的壳层单体处于“饥饿”状态,在乳胶粒子表面富集、引发聚合,形成表层“过渡层”,最终形成核壳结构复合粒子.     

A-187改性核壳型聚丙烯酸酯乳液的制备及性能表征

以甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸-2-乙基己酯、γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷(A-187)等为原料,过硫酸铵为引发剂,通过种子乳液聚合法制备了具有核-壳结构的A-187改性聚丙烯酸酯(SACR)系列微复合高分子乳液。表征了乳胶粒子的结构形态及粒度分布,测定了聚合物的玻璃化转变温度、拉伸强度和聚合物薄膜的吸水率。所得SACR系列微复合聚合物乳液的乳胶粒子具有核壳结构,粒径分布较窄,聚合物的玻璃化转变温度随A-187加量的增加有所升高,聚合物的力学性能和聚合物的耐水性能有所改善。     

交联剂含量对核壳型聚丙烯酸酯乳液及胶膜性能的影响

以三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)为交联单体,采用半连续种子乳液聚合法,以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)为主要单体合成了核壳型聚丙烯酸酯乳液,研究了核层TMPTMA含量对乳液及胶膜性能的影响。结果表明,在一定范围内,随着核层TMPTMA含量的增加,乳胶粒子的平均粒径减小,凝聚率增大;胶膜的拉伸强度及断裂伸长率均增大,与水的接触角变小;在反应条件、单体种类及配比相同的情况下,核壳型丙烯酸酯乳胶膜比非核壳型乳胶膜的杨氏模量及拉伸强度明显变大。     

原位聚合法制备纳米TiO2/有机硅改性丙烯酸酯复合乳液

用硅烷偶联剂对纳米二氧化钛(TiO2)粒子表面进行预处理，使其表面由亲水性变为疏水性，并在其表面接枝上可反应的有机官能团。通过改性纳米TiO2表面上的原位聚合反应，制备了纳米TiO2／硅丙复合乳液。透射电子显微镜观察结果显示，乳液中存在两种结构的乳胶粒子：一种是以聚丙烯酸酯为核、有机硅聚合物为壳的核壳结构硅丙乳胶粒子；另一种是以纳米TiO2为核、有机聚合物为壳的纳米TiO2／聚合物复合结构乳胶粒子。乳胶粒子的结构形态可由乳化剂的用量控制。该复合乳液具有较好的杀菌效果，在较短时间内对细菌的杀灭率可达90％以上。     

丙烯酸酯弹性乳液的制备及应用研究

采用多步半连续滴加种子乳液聚合方法，合成了具有双层和三层核壳结构的丙烯酸酯弹性乳液。采用FT—IR确认了聚合物的结构，研究了乳胶粒子层数、各层单体的种类及用量对胶膜性能及应用性能的影响。     

种子聚合法制备PS/PAA核壳微球的研究

设计制备了以疏水性聚苯乙烯(PS)为核、以亲水性聚丙烯酸(PAA)为壳的PS/PAA核壳结构复合微球。首先利用无皂乳液聚合法制备了亚微米级的PS微球,再以其为种子,利用种子无皂乳液聚合法制备PS/PAA核壳微球。在种子聚合阶段,选用AIBN当引发剂,经过红外光谱(IR)表征,表明当使用油溶性引发剂偶氮二异丁腈(AIBN),使其最终形成PS/PAA核壳结构微球。这种方法解决了亲水性较强的单体在以水为介质时在PS微球溶于少量的苯乙烯(St),并在引发聚合之前经过充分的吸附溶胀,可使亲水性单体AAc在PS种子微球表面聚合生成壳层,解决表面不容易直接聚合生成壳层的问题。     

热敏乳液薄膜的制备及性能

本文介绍了一种可以通过三步法制得的具有亲油的核和亲水的壳的高分子微胶粒。首先,通过乳液聚合得到甲基丙烯酸正丁酯与甲基丙酸甲酯的共聚物乳液(p-(BMA-MMA));利用(p-(BMA-MMA)乳液作为种子,用一种氧化还原引发体系引发反应,通过控制反应条件,在乳胶粒表面包覆一层均匀的聚甲基丙烯酸缩水甘油酯(p-GMA)外壳,壳层聚合物的含量为5~15wt.%之间;最后,壳层表面的环氧基团与三乙醇胺盐酸盐反应,环氧基团转变为季铵盐,使外壳成为极性的亲水表面。核-壳型固体微胶粒可以在水中较好地分散并形成稳定的乳液。通过旋涂法将固体乳液颗粒和PVA的混合水溶液涂在铝版基上,室温下干燥,可得到乳液薄膜。实验发现,室温下核-壳乳液薄膜与水的接触角在16.1°-27.5°范围内,可经过150℃短时间的烤版处理后,接触角将超过87,°表明乳液薄膜通过加热后完全由亲水性转为亲油性。同时,该乳液薄膜在烤版前很容易用中性水由版基上冲洗掉,但烤版后不再能够被洗掉。当在乳液薄膜中加入一种红外染料(最大吸收波长在830nm)后,该薄膜变得对830nm的LD激光敏感,并通过LD激光曝光和中性水显影后,得到阴图型图像。     

STUDIES ON SYNTHESIS OF SILICA SOL-ORGANIC POLYMER COMPOSITE EMULSION

An emulsion of polystyrene/poly (butylacrylate-methyl methacrylate acrylic acid) core/shell latex particles (PS/P (BA-MMA-AA)) has been prepared by use of three synthetic methods. The effects of synthetic methods on the distribution of carboxyl groups in latex particles were studied. The results show that the seed emulsion polymerization in which the pre-emulsified monomers were added by dropping method to the second stage is the best technique for obtaining the optimum distribution of carboxyl groups on the surface of the latex particles. Furthermore, by using PS/P (BA-MMA-AA), a type of novel composite emulsion of silica sol-PS/P (BA-MMA-AA) was synthesized with the above method. By observation through transmission EM, the morphology of the latex particles obtained shows that a composite structure has been formed between silica sol particles and organic polymer particles.     

Preparation and morphological characterization of two- and three-component natural rubber-based latex particles

Different emulsion polymerization processes allowed variation in the microstructure of composite natural rubber (NR)-based latex particles. A prevulcanized and a not-crosslinked natural rubber latex were coated with a shell of crosslinked poly(methyl methacrylate) (PMMA) or polystyrene (PS). The bipolar redox initiating system tert-butyl hydroperoxide/tetraethylene pentamine promoted a core–shell arrangement. Furthermore, PS subinclusions were introduced into the NR core. The initiators used for the subinclusion synthesis were azobisisobutyronitrile at high temperature and a redox initiation system consisting of tert-butyl hydroperoxide/dimethylaniline at low temperature. The morphology of the resulting latex interpenetrating networks (IPN) was characterized by transmission electron micros-copy (TEM) and scanning electron microscopy (SEM). Different staining methods allowed us to increase the contrast between the NR phase and the secondary polymers in the composite latex particles. A semicontinuous feeding process decreased the PS subinclusions size by a factor of 6 in comparison with a batch reaction. Depending on the NR/styrene swelling ratio, the crosslinking degree, and the polymerization temperature used, distinct differences of the phase arrangement of polymers in the latex particles were revealed. © 1996 John Wiley & Sons, Inc.     

Synthesis and Characterisation of New Structured Latices for Improved Adhesion to Polyester Films

The paper describes the synthesis, in an emulsion polymerisation process, of an acrylic copolymer, poly(methyl methacrylate-co-ethyl acrylate), in the presence of a hydrophilic polyester. This polyester has a structure close to that of poly(ethylene terephthalate) (PET) but is made hydrophilic by sulphonate-bearing moieties. It was specially designed to promote the adhesion of latex films to PET. In water, it forms aggregates with a mean diameter of 20nm. These aggregates act as seed particles and the synthesis proceeds like an inverted core–shell emulsion polymerisation. The hydrophilic polyester forms the main component of the shell of the final latex particles. The acrylic copolymer is located mainly in the core. Despite the strong incompatibility between the two polymers, they mix to a certain extent, as clearly shown by the analysis of the mechanical properties of the latex films. This unexpected mixing is due to the synthesis procedure. The acrylic monomers are added slowly and polymerise as soon as they reach the seed particles, before having time to completely phase-separate from the polyester. Knowledge of the particle and latex film structure is used to interpret adhesive properties of the latex films. © of SCI.     

Preparation and structure control of hollow polymer particles: Influence of seeded emulsion polymerization and alkalization treatment process

Hollow polymer latex particles containing a hydrophilic core were prepared by seeded emulsion polymerization with MAA/BA/MMA/St as comonomers, followed by stepwise alkalization treatment with ammonia. The size and morphology of composite latex particles was determined by TEM. The effects of the seeded emulsion polymerization conditions and alkalization treatment on the size and hollow structure of latex were investigated. The results showed that the optimum content of crosslinking agent in the shell polymers was about 0.5–1.0 wt %, emulsifier was about 0.8–1.1 wt %, and the core/shell weight ratio was 1/7. To obtain uniform hollow latex particles with large size, the starved feeding technique should be adopted in seeded emulsion polymerization, and the neutralization temperature should equal to the T_g of the shell polymer. Then, the obtained polymer particles under this condition had an excellent hollow structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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。     

Morphological prediction and its application to the synthesis of polyacrylate/polysiloxane core/shell latex particles

A theoretical analysis and a morphological prediction of polyacrylate (PA)/polysiloxane (PSi) latex particles with core/shell morphologies were first conducted based on interfacial tensions and relative volumes of the two polymers in the latex system. The results indicated that the normal core/shell morphology particles (PSi/PA), with hydrophobic polysiloxane as the core and with hydrophilic polyacrylate as the shell, can be easily formed. Although the inverted core/shell morphology particles (PA/PSi) with polyacrylate as the core could not be formed in most cases, even if the fraction volume of polysiloxane was larger than 0.872, which is the smallest value of forming a PA/PSi particle, the PSi/PA particles were unavoidably formed simultaneously with PA/PSi particle formation. The synthesis of PA/PSi particles containing equal amounts of polyacrylate and polysiloxane was then carried out using seeded emulsion polymerization. Before the cyclosiloxane cationic polymerization, 3‐methacryloyloxypropyl trimethoxysilane (MATS) was introduced into the polyacrylate seed latex to form an intermediate layer and chemical bonds between the core and the shell polymers. The characterization by transmission electron microscopy (TEM) demonstrated that the perfect PA/PSi core/shell particle is successfully synthesized when both the core and the shell polymers are crosslinked. The experiments showed that both the hardness and water adsorption ratio characteristics of latex films of the PA/PSi particles are in good agreement with those of the polysiloxane film. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2251–2258, 2001     

Synthesis of poly(acrylate-styrene)/poly(acrylate-styrene) core/shell latex and TOPEM-DSC characterization

Poly(acrylate-styrene)/poly(acrylate-styrene) core/shell latex particles were synthesized via seeded semi-continuous emulsion polymerization. Both core polymer (CP) and shell polymer (SP) were copolymerized by using three identical monomers of methyl methacrylate (MMA), butyl acrylate (BA) and styrene (St) with different composition ratios. The synthesized core/shell latex particle presents a phase separated state with the interfacial layer between CP and SP. In this study, the weight fractions and the corresponding thickness of this interfacial layer, CP and SP phase in the core/shell latex particle has be successfully calculated by using multi-frequency temperature-modulated differential scanning calorimetry (TOPEM-DSC). The results indicate that the interfacial layer thickness of the core/shell latex particle is determined by the core/shell structure, such as hard core/soft shell (defined as HC/SS) and soft core/hard shell (defined as SC/HS), the glass transition temperature (T_g) of the “hard” phase (correspondingly core or shell for HC/SS or SC/HS structure, respectively), and the existence of hydrophilic monomer during the copolymerization process such as acrylic acid. Meanwhile, the influence of film-formation-temperature on the microstructure of the latex films was systematically explored in this work.     

Synthesis of ambient temperature self-crosslinking VTES-based core–shell polyacrylate emulsion via modified micro-emulsion polymerization process

Modified micro-emulsion polymerization was successfully used to synthesize a kind of ambient temperature self-crosslinking core–shell emulsion, consisting of polyacrylate core and vinyltriethoxysilane (VTES) modified polyacrylate shell, by varying the ratio of soft monomer (BA) and hard monomer (MMA) which is different in the core and shell. The emulsion and its film formed at ambient temperature were characterized by attenuated total reflectance-fourier transform infrared spectroscopy (ATR-FTIR), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Core–shell structure was clearly shown in TEM micrographs, and two distinct glass transition temperatures (T _g) were confirmed by DSC analysis. Lower T _g of core phase analyzed by DSC and self-crosslinking properties of VTES characterized by crosslinking degree cause latex particles form continuous film at ambient temperature. Thermal and mechanical properties and the surface properties of the latex films were also investigated. Results showed that the core–shell latex films containing 5 and 7.5 % VTES exhibited higher thermal stability, better mechanical properties, higher contact angle, and water resistance compared with pure polyacrylate film.