反应性复合乳液的合成、表征及其交联反应

利用种子半连续乳液聚合方法合成了核层或壳层带有环氧基以及壳层带有羧基的3种不同核/壳结构的乳胶粒子,通过物理共混带环氧基和羧基的乳胶粒子,得到了两种反应性复合乳液.利用透射电镜和激光动态光散射对乳胶粒子进行了表征,其粒径分布较窄,粒径分布的多分散系数为0.062,平均粒径约76 nm,乳胶粒子具有明显的核/壳结构.通过胶膜的凝胶率和膨胀率的测定和红外光谱分析对反应性复合乳液中乳胶粒子的扩散及交联反应进行了研究,并探讨了不同核壳结构复合乳液对涂膜机械性能的影响.研究表明,当反应性复合乳液中的环氧基和羧基分别分布在乳胶粒子的核层和壳层时,有利于聚合物分子链的充分扩散和化学交联反应的进行,从而提高涂膜的物理化学性能,当甲基丙烯酸缩水甘油酯(GMA)含量为10 wt%时,涂膜的拉伸强度达20.3 MPa.     

Nanocomposites based on crosslinked polyacrylic latex/silver nanoparticles for waterborne high‐performance antibacterial coatings

Functional polymer/AgNPs nanocomposites have been prepared. Silver nanoparticles (NPs) were synthesized to which polyacrylamide, PAAm, was covalently bound. PAAm was synthesized via a RAFT reaction and carried thiol and carboxylic acid end groups. Thiol was used to bind the polymer to the metal surface and carboxyl for further reactions. The AgNPs were used in a post‐crosslinking reaction with a separately synthesized poly(butyl acrylate‐co‐methyl methacrylate)/polyglycidyl methacrylate core/shell latex bearing epoxy functional groups. Dynamic mechanical analysis showed that the functional AgNPs effectively crosslinked the latex polymer, and that the final product had excellent mechanical strength. Antibacterial tests revealed that the nanocomposite films had strong antibacterial activity against all types of the bacteria and the immobilization of silver NPs by crosslinking retarded the release of silver in comparison to the uncrosslinked ones. With the presented method, it is possible to obtain ductile antibacterial nanocomposites to be used as waterborne functional coatings. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1435–1447     

Ultra-robust,self-healable and recyclable polyurethane elastomer via a combination of hydrogen bonds,dynamic chemistry,and microphase separation

Flexibility, robustness, transparency, and recyclability are critical to the application of self-healing polymer materials in the field of flexible electronics. However, integrating all the above properties remains a huge challenge to date. In this work, we put forward a facile strategy to prepare polyurethane (PU) elastomer with ultra-high strength and self-healing performance based on hydrogen bonds, disulfide dynamic chemistry, and microphase separation at the same time. Three different self-healing PUs were obtained by introducing disulfide bonds and different types of hydrogen bonds. A robust, transparent, and recyclable PU with amino-terminated chain extender (PUA) with fast and efficient self-healing performance was prepared. The mechanical and self-healing properties of the PUA were effectively balanced by the synergistic effect of reversible interaction of disulfide bonds and the formation of microphase separated structure. The results indicated that the PUA exhibited high transparency up to 90% and excellent mechanical property, e.g. the tensile strength and elongation at break can reach 37.10 MPa and 1080%, respectively. Meanwhile, it can achieve a high self-healing efficiency of 96.8% at 80 °C for 4 h and maintain 84% of the initial mechanical strength even after four times of recycling. Moreover, the colloid graphite/PUA flexible strain sensor was prepared by the combination of colloid graphite and PUA, which can accurately detect both large and tiny scale deformations.     

Preparation and characterization of emulsifier-free core–shell interpenetrating polymer network-fluorinated polyacrylate latex particles

The emulsifier-free core–shell interpenetrating polymer network (IPN) fluorinated polyacrylate latex particles with fluorine rich in shell were prepared by emulsifier-free seeded emulsion polymerization with water as the reaction medium. The fluorinated copolymer could be fixed on the particle surface due to the formation of interpenetrating polymer network. The resultant core–shell particles were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS) analysis, Fourier transform infrared (FTIR) spectrometry, X-ray photoelectron spectroscopy (XPS) analysis and thermogravimetric analysis (TGA). The core–shell particles possessed very narrow monomodal particle size distributions. XPS analysis of the latex film displayed that perfluoroalkyl groups had the tendency to enrich at surface and there was a gradient concentration of fluorine in the structure of the latex film from the film–air interface to the film–glass interface. In addition, compared with the latex film of crosslinked polyacrylate prepared under the same condition, the emulsifier-free core–shell IPN-fluorinated polyacrylate latex film showed better thermal stability, higher contact angle and lower water uptake.     

Crosslinking in Acetoacetoxy Functional Waterborne Crosslinkable Latexes

Chain crosslinking through the different stages of the production of acetoacetoxy ethyl methacrylate (AAEMA) containing acrylic latexes was studied; namely, during the synthesis step, after latex neutralization and after crosslinking with diamines. The gel content of the latex increased with increasing amounts of the functional AAEMA monomer likely due to dimethacrylate impurities contained in the monomer. Moreover, the neutralization of the latex with ammonia had important implications in the microstructure of the polymer. A base catalyzed Michael addition reaction between acetaocetoxy groups and terminal double bonds present in the polymer particles produced chain pre-crosslinking that affected the further crosslinking reaction with diamines. The compatibility of the diamines with the polymer matrix and the ratio diamine/acetoacetoxy used to crosslink the latex during film formation also played an important role in the crosslinking efficiency as evaluated by solvent resistance of crosslinked films.     

Modification of aqueous polyurethanes by forming latex interpenetrating polymer networks with polystyrene

A series of latex particles with interpenetrating polymer network structure have been synthesized from waterborne polyurethane (PU) and polystyrene (PS). The effect of PU/PS composition, cross-linking density in the PS domain as well as in PU have been studied in terms of dispersion size, transmission electron microscopy morphology, mechanical and dynamic mechanical properties in addition to swellability in water and toluene of the dispersion cast film. It was found that inverted core (PS)–shell (PU) morphology was well defined and that the domain size as well as the film properties were well controlled by the latex composition and cross-linking density of both phases. Received: 15 March 2000 Accepted: 21 February 2001     

室温自交联丙烯酸酯乳液的制备与表征

使用3种含不饱和双键硅氧烷,乙烯基三(β-甲氧基乙氧基)硅烷(A172)、乙烯基三乙氧基硅烷(VTES)和γ-甲基丙烯酰氧丙基三甲氧基硅烷(A174)为功能单体,采用半连续乳液聚合法制备了室温自交联丙烯酸酯乳液,探讨了硅氧烷功能单体在不同pH条件下水解情况以及其种类和用量对乳液及乳胶膜性能的影响.结果表明,pH在7～9之间时硅氧烷功能单体水解最慢;A172在pH为8.4时5h内就水解完全;增加VTES和A174的用量均能提高乳胶膜的交联度、力学性能和耐水性.控制聚合过程的pH值以抑制硅氧烷功能单体的水解并调节乳液成膜时的pH值以加速硅氧烷功能单体的水解从而增强胶膜的交联程度,发现酸性或碱性条件下得到乳胶膜比中性条件下胶膜的力学和耐水性能均有不同程度的提高,并且在酸性条件下胶膜的性能提高最多.对比使用A174和VTES制备的胶膜,发现这种方法对含有A174胶膜的效果不明显,而含VTES胶膜的性能提高最为显著.     

Characterization of kaolinite/emulsion-polymerization styrene butadiene rubber (ESBR) nanocomposite prepared by latex blending method: Dynamic mechanic properties and mechanism

The latex blending method was chosen to prepare Kaolinite/emulsion-polymerization styrene butadiene rubber (ESBR) nanocomposite to improve the interaction between filler particles and rubber matrix chains. The influences of kaolinite particles size, filler contents, and flocculants types on dynamic mechanical properties and the relative reinforcement mechanism of the prepared composite were systematic investigated and proposed. The transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that the kaolinite particles were finely dispersed into the rubber matrix and arranged in parallel orientation. The prepared nanocomposites by latex blending exhibited improved crosslinking characteristic and dynamic mechanical parameters. The KAl (SO₄)₂ flocculant presented obvious modification in dynamic properties and crosslinking characteristic. Both the decrease in kaolinite particle size and the increase in kaolinite content can greatly improve the storage modulus and reinforcing effect of kaolinite/ESBR nanocomposites. The dynamic reinforcement mechanism of kaolinite can be explained by filler network including a certain thickness of rubber shell on the surface of kaolinite lamellar structure and the aggregations network between kaolinite particles The optimum way to balance the dynamic properties of rubber nanocomposites at different temperatures is to reduce the surface difference between kaolinite and rubber matrix and the degree of filler-filler networking on the basis of kaolinite with nanoscale (nanometer effect).     

Synthesis and properties of a novel hyperbranched polyphosphate acrylate applied to UV curable flame retardant coatings

A series of hyperbranched polyphosphate acrylates (HPPAs) being used for UV curable flame retardant coatings were prepared by the reaction of tri(acryloyloxyethyl) phosphate (TAEP) with piperazine at given ratios, and characterized using FTIR, ¹H NMR and GPC measurements. HPPA was blended with TAEP in different ratios to obtain a series of UV curable resins. Their maximum photopolymerization rates and final unsaturation conversion (P^f) in the cured films at the presence of a photofragmenting initiator were investigated. The results showed that the P^f increased along with HPPA content and the pure HPPA has the maximum value of 82.1% in the photo-DSC analysis. The data from dynamic mechanical thermal analysis showed that HPPA has good miscibility with TAEP. The crosslinking density and T_g of the cured film decrease along with the content of HPPA in the blend. The mechanical properties of the cured films were also investigated. Less than 20% HPPA addition improved both the tensile strength and elongation at break without damaging the modulus. The HPPA₂₀TAEP₈₀ film with 20% HPPA addition has the highest tensile strength of 31.7 MPa and an elongation at break two times that of cured TAEP. The flame retardancy of the UV cured films was investigated by the limiting oxygen index (LOI). The cured TAEP/HPPA samples greatly expanded when burning, and the degree of expansion increased along with HPPA content. However, the LOI values decreased from 47.0 to 34.0 along with HPPA content, which can be ascribed to that the flame retardancy of TAEP is mainly acting in the gas phase, whereas HPPA mainly acting in condensed phase, and the gas phase mechanism holds the dominant effect while their blends are burning.     

High Solid Acrylic–Melamine Latexes with Tunable Crosslinking Capability

Miniemulsion polymerization is employed to produce high solid content (50%) acrylic/melamine latexes with varied crosslinking capability, for their potential application as waterborne crosslinkable coatings. This synthesis strategy allows the efficient incorporation of a hydrophobic crosslinker, iso‐butylated melamine (iBMF), into polymer particles, and to obtain latexes with different iBMF concentrations and acrylic polymer with varied content of hydroxylic groups (OH–). The involved crosslinking mechanisms and the physical transformations during film thermosetting of acrylic/iBMF nanocomposite are exhaustively investigated by combining thermal, spectroscopic, and thermo‐mechanical analyses. The influence of reactive groups concentration (iBMF and OH– content in the acrylic polymer) on the rate of curing, the crosslinking degree, and consequently onto the sensitive properties of cured films are discussed here.     

Studies on radiation grafting of methyl methacrylate onto natural rubber for improving modulus of latex film

Methyl methacrylate (MMA) can be grafted onto natural rubber (NR) in latex by gamma irradiation for improving the mechanical properties of the dry films. Physical blending of MMA-grafted NR latex with radiation vulcanized natural rubber latex (RVNRL) or simultaneous radiation grafting and crosslinking are found to be useful techniques for improving the properties of latex films. Moduli of the films are improved with increasing MMA content; however, tensile strength is reduced. High modulus without much reduction in tensile strength can be achieved if the MMA content is 50–60 parts per hundred rubber.     

SYNTHESIS AND PROPERTIES OF ACRYLIC-BASED SUPERABSORBENTS WITH ENHANCED CROSSLINKING ON PARTICLE SURFACE

A series of acrylic-based superabsorbent resins were synthesized by inverse suspension polymerization, using potassium persulfate as the initiator, N, N＇-methylene bisacrylamide （BIS） and divinylbenzene （DVB） as the multiple crosslinking agents. The morphology of the resulting superabsorbent resins revealed by SEM demonstrated that a hard shell layer was indeed formed due to surface crosslinking. The swelling and deswelling properties, and the mechanical strength of superabsorbents were investigated. The results indicated that the adding time of DVB and the amount of DVB participated in the crosslinking show a significant influence on the properties of superabsorbents. When DVB was added in polymerization later, the amount of DVB participated in reaction decreases and the surface crosslinked shell becomes thinner. It is suitable for DVB to be introduced in the later stage of the polymerization process, because the absorption rate of resin is efficiently improved in conjunction with higher water absorption. Furthermore, it was found that the mechanical strength of swollen superabsorbent with surface crosslinking was indeed enhanced in comparison with that of the conventional one.     

Self‐healing polyurethane based on disulfide bond and hydrogen bond

Tough and transparent polyurethane networks with self‐healing capability at mild temperature conditions were successfully prepared in a 1‐pot procedure. The self‐healing ability of synthesized polyurethane comes from the covalent disulfide metathesis and non‐covalent H‐bonding. The mechanical testing indicates that disulfide metathesis reforms the covalent bonds on a longer time scale, while H‐bonding gives rise to a healing efficiency of around 46% in the early healing processing. The compromise between mechanical performance and healing capability is reached by tailoring the concentration of disulfide. The tensile strength of the sample with 100% self‐heal efficiency can get to 5.01 MPa, which can be explained by higher mobility of polymer chain under ambient temperature from creep testing.     

New trend of radiation application to polymer modification — irradiation in oxygen free atmosphere and at elevated temperature

Polycarbosilane (PCS) fiber as a precursor for ceramic fiber of silicon carbide was cured by electron beam (EB) irradiation under oxygen free atmosphere. Oxygen content in the cured PCS fiber was scarce and the obtained silicon carbide (SiC) fiber with low oxygen content showed high heat resistance up to 1973 K and tensile strength of 3 GPa. Also, the EB cured PCS fiber with very low oxygen content could be converted to silicon nitride (Si₃N₄) fiber by the pyrolysis in NH₃ gas atmosphere, which was the new processing to produce Si₃N₄ fiber. The process of SiC fiber synthesis was developed to the commercial plant.

The other application was the crosslinking of polytetrafluoroethylene (PTFE). PTFE, which had been recognized to be a typical chain scission polymer, could be induced to crosslinking by irradiation at the molten state in oxygen free atmosphere. The physical properties such as crystallinity, mechanical properties, etc. changed much by crosslinking, and the radiation resistance was much improved.     

具有双交联网络结构的纳米复合材料的制备及介电性能

利用官能团反应活化能的差异, 通过控制反应温度和时间制备了一种具有双交联网络结构的钛酸钡/聚芳醚酮纳米复合膜(BT-BCB/c-DPAEK). 对比研究纯聚合物薄膜及未经交联处理和仅进行单交联处理的复合薄膜发现, BT-BCB/c-DPAEK具有更加优异的力学性能和热性能, 并且其介电性能表现出良好的频率稳定性和温度稳定性. 由于双交联网络对于复合材料两相间界面的改善及高温下对聚合物分子链运动的限制, BT-BCB/c-DPAEK表现出十分优异的储能性能, 特别是在150 ℃, 300 MV/m场强下依然保持1.75 J/cm³的储能密度和80%的放电效率.     

刚性聚合物微球透明增韧聚苯乙烯

通过多步复合乳液聚合方法合成了一种具有核壳结构的刚性聚合物微球.不同粒径、用量及核层交联密度的核壳微粒(C-S)与聚苯乙烯(PS)共混得到PS/C-S复合材料.通过对其冲击强度及透明性的研究表明增韧PS的最佳条件是核壳微粒的粒径大于100nm,复合材料中的微粒含量在2%～5%,核层具有适当的交联度.在未影响材料透明性的前提下,材料的韧性比纯PS提高2倍     

In situ latex synthesis of magnetic polymer nanocomposites for application in magnetorheological materials

A new magnetic polymer nanocomposite based on Fe₃O₄ nanoparticles and nature rubber was prepared by the in situ latex method. This process was fast, versatile, reliable, safe, environmentally friendly, and inexpensive. The magnetorheological effect and mechanical properties of magnetic polymer nanocomposites were investigated in detail. The tensile strength of magnetic polymer nanocomposites without other reinforcing fillers was about 14.6 MPa. At the same time, the relative and absolute magnetorheological effect was about 365.0% and 3.64 MPa, respectively, which were almost 10 times with respect to other magnetic polymer nanocomposites based on nature rubber. Furthermore, the relationships between microstructure and mechanical behavior of magnetic polymer nanocomposites were simulated and discussed by the numerical treatment of a new theoretical model associated with finite element analysis for explaining the micro‐mechanism of magnetic polymer nanocomposites with high performance. The work did not only provide a universal route for the rational design and preparation of magnetic polymer nanocomposites with simultaneously high magnetic sensitivity and mechanical properties for various applications but also propose a new method to improve dispersion of magnetic particles in nature rubber for various applications.     

Studies on the preparation of hydrolyzed starch-g-PAN (HSPAN)/PVA blend films--Effect of the reaction with epichlorohydrin

Absorbent hydrolyzed starch-g-PAN (HSPAN)/polyvinylalcohol (PVA) blend films crosslinked with epichlorohydrin (ECH) were prepared to overcome the phase separation and improve the mechanical properties of blend films. The absorbency of HSPAN/PVA blend films decreased with PVA contents due to the reduction of HSPAN contents which is known to play a major role in absorbing ability of the film. And also the absorbency decreased with the ECH contents due to the crosslinking reaction. As far as the solubility is concerned, it increased with PVA contents which is water soluble. But because of the crosslinking reaction between HSPAN and PVA by ECH, the solubility decreased with ECH contents. In the mechanical properties, the strength as well as the strain at break of the HSPAN/PVA blend films were improved very much if compared with HSPAN film, and those mechanical properties were improved even more by the reaction with ECH. The DSC thermograms of HSPAN films showed two major endothermic peaks at 32 and 128 °C, while those of PVA film showed two major endothermic peaks at 49 and 190 °C. In the non-crosslinked blend films, each four endothermic peak was apparent. But as the ECH content increased, both peaks at 128 and 190 °C disappeared and a new peak appeared at the intermediate temperature. In other words, the compatibility of blend films was increased by the reaction with ECH. Also, from the results of TGA, it was confirmed that the thermal degradation of blend films was decelerated by the crosslinking reaction.     

Microwave promoted rapid curing reaction of phenolic fibers

Curing reaction of the as-spun fiber derived from melt-spinning of a novolac resin in a solution of formaldehyde and hydrochloric acid was carried out under microwave irradiation by controlling the reaction time. IR spectroscopy, scanning electron microscopy, and dynamic mechanical analysis were employed to characterize the change of structure and mechanical performance of these phenolic fibers. At the heating rate of 1.2 °C min⁻¹ or in a period of 86 min the homogeneous highly crosslinked phenolic fiber was obtained with the maximum tensile strength being similar with that of the fiber cured under conventional heating reflux (8 h), suggesting that microwave irradiation promotes not only the diffusion of ⁺CH₂OH from the skin into the inner layer of the fiber but also the reaction of ⁺CH₂OH with the phenolic ring in a suitable extent. During pyrolysis the increase of crosslinking degree in the phenolic fibers diminishes the formation of low molecular weight compounds and promotes the formation of graphite layers.     

Impact modification of thermoplastics by methyl methacrylate and styrene-grafted natural rubber latexes

The preparation and characterization of polymer blends with structured natural rubber (NR)-based latex particles are presented. By a semicontinuous emulsion polymerization process, a natural rubber latex (prevulcanized or not) was coated with a shell of crosslinked polymethylmethacrylate (PMMA) or polystyrene (PS). Furthermore, core–shell latexes based on a natural rubber/crosslinked PS latex semi-interpenetrating network were synthesized in a batch process. These structured particles were incorporated as impact modifiers into a brittle polymer matrix using a Werner & Pfleiderer twin screw extruder. The mechanical properties of PS and PMMA blends with a series of the prepared latexes were investigated. In the case of PMMA blends, relatively simple core (NR)–shell (crosslinked PMMA) particles improved the mechanical properties of PMMA most effectively. An intermediate PS layer between the core and the shell or a natural rubber core with PS subinclusions allowed the E-modulus to be adjusted. The situation was different with the PS blends. Only core–shell particles based on NR-crosslinked PS latex semi-interpenetrating networks could effectively toughen PS. It appears that microdomains in the rubber phase allowed a modification of the crazing behavior. These inclusions were observed inside the NR particles by transmission electron microscopy. Transmission electron photomicrographs of PS and PMMA blends also revealed intact and well-dispersed particles. Scanning electron microscopy of fracture surfaces allowed us to distinguish PS blends reinforced with latex semi-interpenetrating network-based particles from blends with all other types of particles.