Structure and property characterization of nanograde core‐shell polyurethane/polyacrylate composite emulsion

Anionic aqueous polyurethane dispersion was synthesized through self‐emulsifing method from cycloaliphatic isophorone diisocyanate (IPDI) and dimethylolpropionic acid (DMPA). The carboxyl acid group in DMPA was used to make the polyurethane dispersible. The polyurethane/polyacrylate (PU/PA) composite particles were also prepared by seeded surfactant‐free emulsion polymerization; the cycloaliphatic polyurethane aqueous dispersion was used as seed particles. The structures and properties of the composite emulsion as well as the physical mixture of polyurethane dispersion and polyacrylate emulsion were characterized by FTIR, DSC, dynamic light scattering, TEM, X‐ray photoelectron spectroscopy (ESCA), and electronic tensile machine. The results showed that the synthesized PU/PA composite emulsion was found to form inverted core‐shell structure with polyacrylate as the core and with polyurethane as the shell, and its diameter of particles is in the range of nanograde, the crosslinking reaction was existed in composite emulsion. The intimate molecular mixing of crosslinking polymers are also claims to result in a superior balance of properties compared to physical blends of polyurethane dispersion and acrylate emulsion. The crosslinking mechanism of PU/PA composite emulsion was also discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

低亲水基丙烯酸酯-聚氨酯复合乳液涂膜的热分析研究

以异佛尔酮二异氰酸酯(IPD I)、聚已二酸-1,4丁-二醇酯(PBA)、二羟甲基丙酸(DMPA)、丙烯酸酯(PA)为主要原料,采用自乳化工艺制备了固体质量分数均为40%,亲水基团(DMPA的羧基)占固体质量百分数为1%的一系列稳定的聚氨酯-丙烯酸酯复合乳液(PUA);用热重分析(TG)、示差扫描量热分析(DSC)、动态机械热分析(DMA)方法研究PBA的相对分子质量、聚氨酯与丙烯酸酯的质量分数比(PU/PA)对PUA膜热性能的影响。热分析研究表明,增加PBA相对分子质量和加入适量的丙烯酸酯能提高PUA分子的有序程度,有利于PUA成膜物耐热性能的改善;随着PBA相对分子质量的增加,PU软段的非晶部分和PA的硬段相容性增强,微观相分离减小,乳液的混合能达到分子水平。     

Aqueous PUA emulsion prepared by dispersing polyurethane prepolymer in polyacrylate emulsion

Waterborne polyurethane/polyacrylate (PUA) emulsions were prepared by dispersing polyurethane (PU) prepolymer in polyacrylate (PA) emulsion; therefore, the PU particles formed in the presence of PA nanoparticles. The particle size and its distribution of the composite PUA emulsion were determined by dynamic light scattering. The result shows that the average particle size increases initially and then decreases with increasing PA content, which is confirmed by transmission electron microscope characterization. The surface properties of PUA films were analyzed by water contact angle and atomic force microscope topography. It indicates that the water contact angle and the average roughness of the composite PUA films are larger than those of the PU film. Meanwhile, mechanical properties test, scanning electron microscopy, and thermogravimetric analyses disclose that the PUA films are characterized by enhanced tensile strength, rough fractured surface, and good thermal stability. The preparation method proposed in this article is an effective and convenient way to manufacture composite PUA emulsion. The composite PUA emulsion can be potentially used in coatings. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43203.     

单体含量对核壳结构聚氨酯-聚丙烯酸酯乳液性能影响

以水性聚氨酯（PU）为种子乳液,以丙烯酸酯（PA）为聚合性单体,采用种子乳液聚合法合成核壳结构聚氨酯-聚丙烯酸酯乳液（PUA）。研究了单体含量对乳液及胶膜性能的影响。实验结果表明：随着乙烯基单体含量的增加,乳液颜色加深,稳定性下降,胶膜的断裂伸长率降低,硬度和耐水性增加。当乙烯基单体和PU百分比（M／P）为25％时,乳液的稳定性大于12个月,胶膜的断裂伸长率为498％,硬度为0．64,吸水性为22．8％。红外光谱分析表明合成了PUA。     

丙烯酸酯改性水性聚氨酯乳液的制备及性能研究

采用物理共混和核-壳聚合法制备了丙烯酸酯改性水性聚氨酯(PU/PA,PUA)乳液,并对不同改性方法制得的乳液进行了研究。通过红外(FTIR)、透射电镜(TEM)、差示扫描量热(DSC)、热重分析(TGA)、耐水性和力学性能测试等研究了丙烯酸酯改性聚氨酯乳液及涂膜的结构与性能。结果表明具有核-壳结构的PUA乳液涂膜耐水性、耐热性和固含量较水性聚氨酯(PU)有明显的提高,力学性能稍有下降;PUA综合性能优于PU/PA。     

Preparation,properties, and applications of acrylic–polyurethane hybrid emulsions in extinction electrophoresis

Aqueous acrylic–polyurethane hybrid emulsions (PUA) were fabricated by semibatch emulsion copolymerization using a mixture of acrylic (AC) monomers in the presence of an isocyanate terminated polyurethane (PU). The effects of PU content on the morphology of the hybrid emulsions and film properties were here investigated in detail using FT‐IR, UV, TEM, and SEM. TEM images clearly showed that hybrid emulsions exhibited a core‐shell structure before neutralization. However, after neutralization with N,N‐dimethylethanolamine, the typical particles exhibited phase inversion, producing particles with irregular hemispheres shapes and diameters about 0.5 μm. SEM images showed that the film surface became rougher as PU content increased, peaking at 10 wt %, the gloss of this film was 23.1 (60°). The UV transmittance spectra of the PUA hybrid emulsion within a wavelength range 700–200 nm decreased as PU content increased. This was consistent with the changes in the surface roughness of the film. Electrophoresis took place on an aluminum alloy surface and the product was dried at 120°C. The film exhibited excellent mechanical performance due to curing reaction between the N?C?O group on PU and hydroxyl group on the AC copolymer. The gloss of the film was found to be as low as 4.0 after electrophoresis testing. These films may be useful in practical extinction electrophoresis. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40078.     

聚氨酯-聚丙烯酸酯复合乳液的合成与表征

将自制的自乳化 PU乳液代替常规乳液聚合的乳化剂 ,用丙烯酸丁酯为单体 ,偶氮二异丁腈为引发剂在 PU乳液中均聚形成 PUA乳液 ,对该体系的聚合动力学及复合乳液的胶膜性质进行了研究。     

水性聚氨酯/苯丙复合乳液的合成及其在表面施胶中的应用

以N-甲基二乙醇胺(MDEA)为扩链剂制备了水性聚氨酯(PU)乳液,并用其与苯乙烯(St)、丙烯酸丁酯(BA)和丙烯酸羟乙酯混合单体制备了PU/苯丙(PUA)复合乳液,用傅里叶变换红外光谱表征了复合乳液的结构,考察了PU及复合乳液性能的影响因素,并研究了复合乳液的表面施胶性能.结果表明,在-NCO/-OH(摩尔比)为1.7～1.9、MDEA质量分数为10%、中和度为100%的条件下,合成了平均粒径为75 nm左右的水性PU;当反应温度为80 ℃时,PUA复合乳液呈乳白色且无凝胶产生;当BA∶ St(质量比)为1.5～2.0∶ 1.0时,PUA复合乳液的抗水性较好;当BA质量分数由30%增加到40%时,PUA复合乳液的粒径增大,粒径分布变宽;在室温下用质量分数为0.2%的PUA复合乳液对原纸进行表面施胶时,纸张的施胶度达到33%;在105 ℃下,仅需很短的熟化时间下机纸张的施胶度可达95%.     

Interfacial‐initiated seeded emulsion polymerization: preparation of polystyrene/poly(methacrylic acid) core/shell particles in the absence of surfactant

Composite polymer particles with hydrophobic polystyrene (PSt) as the core and hydrophilic poly(methacrylic acid) (PMAA) as the shell were prepared through two‐stage emulsion polymerization without any surfactant. In the first step, narrowly distributed PSt seed particles were prepared by surfactant‐free emulsion polymerization with 2,2′‐azobis(2‐methylpropionamide) dihydrochloride (AMPA) as the initiator. In the second step, hydrophilic PMAA shells were fabricated onto PSt seed particles through redox interfacial‐initiated seeded emulsion polymerization with cumyl hydroperoxide (CHPO)/ferrous sulfate/ethylenediaminetetraacetic acid (EDTA)/sodium formaldehydesulfoxylate (SFS), where the initiation took place mainly at the interface between PSt seed particles and the aqueous medium. The composite particles were characterized with transmission electron microscopy, fourier transform infrared spectroscopy and dynamic light scattering, and the results show that a core/shell structure was successfully built. Hydrodynamic radius (R_h) of the composite particles increased with the amount of polymerized monomers in the seeded emulsion polymerization. Copyright © 2006 Society of Chemical Industry     

蓖麻油和环氧树脂改性水性聚氨酯-丙烯酸酯的合成与表征

以甲苯二异氰酸酯(TD I)、聚醚型多元醇(N210)、2,2-二羟甲基丙酸(DMPA)、甲基丙烯酸甲酯(MMA)等为主要原料,蓖麻油(C.O.)和脂肪族环氧树脂(RE)为交联剂,以原位乳液聚合法制备出聚氨酯-丙烯酸酯(PUA)复合乳液。以无皂乳液聚合法合成了聚丙烯酸酯乳液(PA),再与聚氨酯(PU)乳液机械混合得到PU/PA共混乳液。探讨了蓖麻油C.O.、RE对复合乳液及涂膜性能的影响,烯丙氧基羟丙基磺酸钠(COPS-1)用量对共混乳液和涂膜性能的影响。结果表明,C.O.、RE分别占PU干质量的5.0%～7.0%和2.0%～3.0%,COPS-1占单体总质量的2.0%时,乳液和涂膜综合性能较好。PUA比PU/PA柔韧性好、断裂伸长率高及附着力好,硬度低,成本高。红外光谱分析发现,PUA与PU/PA中—NH—全部形成氢键。TEM观察到,PUA形成核-壳结构的粒子,粒径较小。通过AFM扫描发现,PUA存在硬段与软段的微相分离。     

端羟基聚丙烯酸酯分子量对PUA性能的影响

异佛尔酮二异氰酸酯(IPDI)、聚己内酯二醇(PCL)为主要原料合成聚氨酯预聚体,甲基丙烯酸甲酯和丙烯酸丁酯合成端羟基共聚物,两者共聚并在水中分散,得到丙烯酸酯改性水性聚氨酯(PUA)。PUA乳液形貌表征结果表明,当聚丙烯酸酯数均分子量达到9 041时,复合乳液的稳定性变差;复合乳液平均粒径随聚丙烯酸酯(PA)分子量增大而增加,但都小于150 nm,并呈现典型的核壳结构。FTIR测试表明,随着PA链段分子量增大,其氢键相互作用相对减弱。DSC测试显示在PA分子量较低时,PA和PU链段是相容的。TG和拉伸测试结果显示,PUA的热稳定性及力学性能都得到明显改善。     

丙烯酸树脂改性水性聚氨酯的结构与性能研究

采用丙烯酸树脂对水性聚氨酯进行改性，得到了共混改性（PU／PA）、共聚改性（PUA’）、接枝改性（PUA）3种丙烯酸改性水性聚氨酯聚合物。通过对改性聚氨酯乳液的激光粒度分析，乳胶膜的红外光谱、热分析、透明性、耐化学性及扫描电镜进行分析，结果表明：改性后的水性聚氨酯，各项性能均有不同程度的提高。在机械共混聚合物PU／PA体系中，聚氨酯分子链和丙烯酸树脂分子链间具有一定的相容性及共混性；在共聚反应聚合物PUA’、PUA体系中，聚氨酯分子链和丙烯酸树脂分子链形成核壳结构，且在PUA中，聚氨酯分子链和丙烯酸树脂分子链之间形成的化学键，可以有效的提高二者的相容性及共混程度。     

Sol–gel process of alkoxysilane in emulsifier‐involved aqueous emulsions: A one‐pot synthetic route to emulsions of core‐shell composite particles and their applications

In this work, a one‐pot route to prepare emulsions of silica/polymer core‐shell composite particles was developed through the direct sol–gel processing of alkoxysilane on the surface of newly synthesized template polymer particles in emulsifier‐involved aqueous emulsions. It included two continuous steps: first, the polymer emulsions were synthesized through emulsion polymerization, and second, the template particles in the emulsions were directly coated with silica via sol–gel reaction of precursors without adding ethanol or removing emulsifiers. The size and morphology of the composite particles were characterized, and the results showed that the silica/polymer composite particles with core‐shell structure could be prepared only on the basis of cationic template emulsions, and the in situ‐coating reaction of sol–gel precursors carried on easier with the increasing of the positive charge density on the surface of template particles. The films formed from the composite emulsions were found to have superior optical and flame‐retardant properties compared to polymer films, owing to the core‐shell composite microstructure of the particles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and properties of microcapsule with EVA core‐PU shell structure

Microcapsule with poly(ethylene‐co‐vinylacetate) (EVA) core‐polyurethane (PU) shell structure was synthesized by interfacial polymerization in aqueous polyol dispersion with ethylene diamine as the chain extender of toluene diisocyanate in poly(vinyl alcohol) aqueous solution as the stabilizing agent. The effects of polyol constituent on the average particle size and distributions, morphologies, color strength, and friction fastness of core‐shell particles were investigated to design microcapsule. The friction fastness of printed fabrics with EVA core‐PU shell microcapsules became the increase to 4–5 grades. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 893–902, 2007     

聚氨酯-丙烯酸酯复合乳液的合成及力学性能

采用三乙胺水溶液中和乳化法制备了用己二酸二酰肼封端的PU水分散体,并以此为种子,加入甲基丙烯酸甲酯、丙烯酸丁酯和双丙酮丙烯酰胺用双引发剂进行乳液聚合得到复合乳液。动态力学测试结果表明该复合乳液材料为相分离体系,组分有一定的相容性并依赖于组成比。拉伸实验结果表明随硬组分甲基丙烯酸甲酯含量的增加,抗拉强度增加,材料由橡胶向脆性塑性转变;复合乳液比乳液混合物有较高的强度和伸长率。     

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。     

聚氨酯-丙烯酸酯水分散体系稳定性研究

通过PUA水分散液一些物理性质 ,如 ζ电位、临界聚沉值 (C .C .C)、pH值、粒径及密度等的测量 ,用DLVO理论分析了聚氨酯 丙烯酸酯水分散体系的稳定性 ,并与实验测定的水分散液在不同条件下的稳定性相对照。结果表明 :用DLVO理论分析具有不同羧基 (—COOH)含量的PUA水分散液的稳定性时所得结果 ,与实验结果较吻合 ;而用该理论分析不同丙烯酸酯 (PA)含量的PUA水分散液时 ,与实验结果有偏差 ,可能与DLVO理论假设粒子形态为球形有关     

聚氨酯-聚丙烯酸酯复合乳液的原位合成与表征

采用原位合成法制备了聚氨酯-聚丙烯酸酯（PUA）复合乳液,通过FTIR,TEM,激光力度分析仪及耐水性分析讨论了R（n（NCO）：n（OH））,亲水性扩链剂含量、稀释剂用量以及乳化剂含量对PUA复合乳液及涂膜性能的影响。研究结果表明。R太大或太小都会导致乳液外观和稳定性变差,粒径增大,吸水率提高;DMPA含量增加有利于乳液稳定性提高,粒径也会减小。但是对涂膜的吸水性增加;稀释剂的加入可以改善乳液分散性,提高乳液稳定性;而乳化剂用量增加时,复合乳液粒径减小,粒径分布变窄,耐水性变差。     

丙烯酸酯改性水性聚氨酯核壳复合乳液工艺探究

为了探究聚合工艺对丙烯酸酯(PA)改性水性聚氨酯(PU)性能的影响,选用不同的聚合工艺,合成了具有核壳结构的PUA复合乳液.通过高分辨透射电镜(TEM)、傅里叶红外光谱(FT-IR)、拉伸力学测试和热重(TG)等测试手段比较了不同工艺和引发剂类型对共聚物乳液形态和胶膜性能的影响.研究结果显示,使用偶氮二异丁腈( AIBN)作为引发剂,采用PA单体前乳化法可以得到具有明显核壳结构的复合乳液,乳胶膜综合性能最好,PU和PA具有更好的相容性.     

Preparation of toughened PMMA through PEG-modified urethane acrylate/PMMA core–shell composite particles

Poly(urethane acrylate) (PUA)/poly(methylmethacrylate) (PMMA) core–shell composite particles were prepared by two-stage emulsion polymerization. The sizes of composite particles could be varied from 25 to 210 nm by introducing polyoxyethylene (POE) groups to the urethane acrylate molecular backbone. Core–shell morphology was identified by investigating the polarity of the surface of the core and shell polymer particles and by measuring the contact angle of the composite particles. A composite particle prepared with relatively small particles (about 20 nm) did not show the core/shell morphology, because the high polar surface of the core polymer particle and the low-stage ratio of the core to the shell cause the formation of a core/shell two-stage latex to be more thermodynamically unstable. The fracture toughness of rubber-toughened PMMA containing PUA/PMMA composite particles increased as the particle sizes decreased and the shell thickness of the composite particles increased. In particular, when the average size of the composite particle was about 43 nm and the stage ratio was 50/50, the fracture toughness of the rubber-toughened PMMA increased more than three times compared with that of pure PMMA. Furthermore, the transparency of toughened PMMA could be maintained up to 91% in the visible spectra range. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2291–2302, 1998