用乳液法合成丙烯酸丁酯-甲基丙烯酸共聚胶乳

采用乳液聚合法合成了丙烯酸丁酯和甲基丙烯酸共聚胶乳,用红外光谱对胶乳的结构进行了表征,讨论了加料方式、水油体积比和引发剂与胶乳性能的关系。结果表明,聚合中分3次加料可使反应更平稳地进行;控制水油体积比在1.50左右更易于反应的控制,胶乳性能也较好;引发剂质量分数为0.2%~0.4%时反应体系稳定,胶乳中的单体残留量少,共聚胶乳的性能较好。     

Emulsion copolymerization of styrene and butyl acrylate by reverse atom transfer radical polymerization

Reverse atom transfer radical copolymerization of styrene (St) and butyl acrylate was carried out in emulsion under normal emulsion conditions, using CuBr₂/bpy complex as catalyst. The effects of surfactant type, initiator type and concentration, and CuBr₂ addition on the system livingness, polymer molecular weight control, and latex stability were examined in detail. It was found that the Polysorbate 80 (Tween 80) and azodiisobutyronitrile gave the best exhibition in this system, polymer samples were got with narrow molecular‐weight dispersity (M_w/M_n = 1.1–1.2) and linear relationships of molecular weight versus monomer conversion, as well as a relatively low polydispersity index (<0.1). Through the GPC and SEM analysis, the polymerization processes under these conditions showed good living/control characteristics relative to the processes under normal emulsion polymerization, although the latex stability was susceptible to the CuBr₂ catalyst. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

无皂乳液聚合合成单分散纯丙乳液

研究了甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、丙烯酸羟乙酯的无皂乳液聚合,考察了单体浓度、引发剂用量、温度、单体配比等对无皂乳液聚合的影响,得到了单分散高固含量的纯丙乳液。     

丙烯酰胺共聚物乳液增稠剂的合成及性能研究

以丙烯酰胺(AM)和2-丙烯酰胺基-2-甲基丙磺酸钠(SAMPS)为聚合单体,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,采用反相乳液聚合法,合成了微交联型丙烯酰胺共聚物乳液。当n(AM)∶n(SAMPS)=3∶2,MBA为单体总质量的0.08%,过硫酸铵为单体总质量的0.03%,异丙醇为单体总质量的0.3%,亚硫酸氢钠为单体总质量的0.06%时,合成产物具有优良的增稠性能和耐电解质性能。测试结果表明,质量分数1%的聚合物水溶液黏度大于1.0×105mPa.s,质量分数1.2%的聚合物水溶液在质量分数0.1%氯化镁和氯化钠存在时的黏度保持率分别为32.76%和24.66%。另外该聚合物乳液的残留丙烯酰胺(2 mg/kg,反相时间(15 s。     

Reactive surfactants in heterophase polymerization. VI. Synthesis and screening of polymerizable surfactants (surfmers) with varying reactivity in high solids styrene—butyl acrylate—acrylic acid emulsion polymerization

Several polymerizable surfactants (surfmers) have been used in the semi-continuous emulsion copolymerization of styrene, butyl acrylate, and acrylic acid. Three of the (anionic) surfmers (sodium 11-crotonoyl undecan-1-yl sulfate, sodium 11-methacryloyl undecan-1-sulfate, and sodium sulfopropyl tetradecyl maleate) were prepared in house with purities between 53 and 82%. Physicochemical properties such as the critical micelle concentration, the adsorption isotherm, and the specific adsorption area were determined. The surfmers were then used with constant addition profiles in semicontinuous reactions, and the instantaneous conversions of the main monomers determined. The particle size, amount of coagulum, surface tension, and stability against electrolyte solutions of the latices were evaluated. Films were cast of some of the latices, and the visual appearance and water adsorption were assessed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 183–1820, 1997     

无皂乳液聚合制备AANa-VAc-TFEMA纳米含氟乳液

以丙烯酸钠(AANa)、乙酸乙烯酯(VAc)和甲基丙烯酸三氟乙酯(TFEMA)为单体进行无皂乳液聚合,合成了P(AANa-VAc-TFEMA)纳米含氟乳液,考察了反应温度、引发剂用量、单体配比对聚合的影响,并着重对聚合物乳液的粒径进行了研究。结果表明:该聚合单体的转化率可达到97.00%以上,聚合得到的无皂乳液稳定性好、粒径分布均匀。通过控制单体配比中AANa的含量及VAc与TFEMA的比例,可以得到纳米含氟乳液。     

Immobilization of penicillin acylase on copolymer of butyl acrylate and ethylene glycol dimethacrylate

The effects of glutaraldehyde, enzyme concentrations and reactants volumes, ionic strength, pH value and carrier particle diameter on immobilization of penicillin acylase onto acrylic carriers were studied. The activity of immobilized enzyme preparations was also studied over a range of pH values and temperatures and thermal and pH stabilities were determined. The use of the immobilized preparation for penicillin G hydrolysis in a batch reactor was investigated. The immobilized enzyme gave a significant reduction in hydrolysis time compared to hydrolysis by the native enzyme.     

Effect of the chain‐transfer‐agent content on the emulsion polymerization process and adhesive properties of poly(n‐butyl acrylate‐co‐acrylic acid) latexes

The effect of water on regenerated silkworm silk fibers has been studied and compared with that of water on natural silkworm silk fibers. Regenerated fibers are spun from an N‐methylmorpholine‐N‐oxide (NMMO) fibroin solution through a wet‐spinning process, leading to fibers with two distinct tensile behaviors, labeled as brittle and ductile, respectively. Regenerated fibers show a significant contraction when immersed in water. Contraction increases further after drying. In contrast, natural silkworm silk fibers show a negligible contraction when submerged in water. Regenerated fibers tested in water are considerably more compliant than samples tested in air, though their stiffness and tensile strength are significantly reduced. It has been shown that the tensile properties of brittle regenerated fibers can be modified by a wet‐stretching process, which consists of deforming the fiber while immersed in water. Regenerated wet‐stretched fibers always show a ductile behavior independent from their initial tensile behavior. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of thiol‐terminated poly(ethylene oxide) for chemisorption to gold surface

Thiol‐terminated poly(ethylene oxide) (PEO) was synthesized using two different approaches: esterification of terminal hydroxyl groups with mercaptoacetic acid and amidation using N‐hydroxysuccinimidyl PEO (NHS–PEO) and cysteine. The reaction of hydroxyl‐terminated PEO with mercaptoacetic acid was carried out in boiling toluene. Different thiolated PEOs, including linear PEOs of varying molecular weights and end‐group types, and star‐type PEOs were synthesized. Nuclear magnetic resonance and infrared spectroscopy were used to characterize the products. The reaction kinetics were also briefly investigated. Gel permeation chromatography was used to investigate the relative amounts of the mono‐ and disubstituted products in the α,ω‐dihydroxy PEOs. NHS–PEO was used both to attach terminal thiol groups via reaction with cysteine and to conjugate other amino acids (and potentially any amino‐containing molecule) to PEO. Reactions using NHS–PEO were carried out at room temperature in water. The chemisorption of these thiolated PEOs to gold was expected to yield surfaces resistant to biofouling, in particular to unwanted protein adsorption. Chemisorption of amino acid–, peptide‐, or protein‐terminated PEOs in addition may yield surfaces having specific biological activity. Work on these aspects will be reported elsewhere. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 594–607, 2003     

Compatibilization of polystyrene/poly(butyl methacrylate)/poly[(ethylene glycol) dimethacrylate] blends via concentrated emulsion polymerization

Two concentrated emulsions in water containing styrene and butyl methacrylate (BMA) as dispersed phases were prepared. Each of them contained a small amount of an amphiphilic macromonomer, poly[(ethylene glycol) dimethacrylate] (PEGD), in the continuous phase. The two concentrated emulsions were partially polymerized at 50 °C until conversions of about 22.5 % were reached. They were then mixed mechanically and the mixture was subjected to complete polymerization. During the latter polymerization, homopolymers of styrene and BMA and copolymers of the two were generated. The copolymers, particularly the crosslinked structures, which were formed through copolymerization of PEGD with styrene and BMA at the interface of the latexes, provided compatibilizers for the homopolymers. This blend of homopolymers, copolymers and crosslinked structures possessed excellent toughness and processability. The blends were characterized by their gel content, and by X‐ray photoelectron spectroscopy, rheometric testing, dynamic mechanical thermal analysis, transmission electron microscopy and impact strength measurements. Copyright © 2005 Society of Chemical Industry     

种子乳液聚合制备MCPU-PMMA复合乳液

本文采用改性蓖麻油合成了软段中含不饱和双键的阴离子聚氨酯水分散液（MCPU），将其作为可聚合乳化剂和种子成分同甲基丙烯酸甲酯（MMA）进行共聚，制得了MCPU－PMMA复合乳液。1HNMR谱图显示MCPU中含有双键结构,共聚后双键消失。通过考察单体转化率和复合乳液平均粒径、凝胶量及成膜耐水及甲苯性探讨了影响种子乳液聚合的多种因素：采用过硫酸钾作为引发剂，单体转化率高，乳液粒径小，成膜耐水及甲苯性好；反应的表观活化能Ea为164.86kJ/mol，反应温度控制在70℃较适宜；聚合反应速率Rp∝［I］1.0856，引发剂用量宜控制在聚合有效组份总质量的0.5％。     

Efficient preparation and characterization of paraffin-based microcapsules by emulsion polymerization

Microencapsulated phase-change materials (MEPCMs) with paraffin as the core and poly(methyl methacrylate) (PMMA) and PMMA copolymers as the shell were prepared by emulsion polymerization using redox initiators at low temperatures. Fourier transform infrared spectroscopy was used to characterize the chemical composition of MEPCMs. The thermal properties and thermal stabilities of MEPCMs were tested by differential scanning calorimetry and thermogravimetric analysis. The morphologies and sizes of the microcapsules were investigated by scanning electron microscopy and particle size distribution analysis. The results indicated that the yield of microcapsules is as high as 96.2%, and the encapsulation efficiency of paraffin is nearly 100% when the paraffin content in MEPCM is 70%. The MEPCMs have good stability: the leakage ratios of MEPCMs can be less than 1% after 50 heating–cooling cycles. Therefore, the microencapsulation of paraffin using redox initiators has good production and application prospects. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47552.     

Semi-continuous emulsion copolymerization of butyl methacrylate with polymerizable anionic surfactants

Two polymerizable anionic surfactants sodium 4-(ω-acryloyloxyalkyl)oxy benzene sulfonate (SABS-n, n=8 or 10) have been successfully used in the semi-continuous emulsion copolymerization with butyl methacrylate (BMA). After generating seeding particles in an emulsion consisting SABS-8 or SABS-10 and small amount of BMA using a redox initiator ammonium persulfate (APS)/tetramethylethylenediamine (TMEDA) at room temperature, most of BMA was added drop-wise to the polymerizing emulsion system during a period of 4-8 h. These emulsion copolymerizations produced nanosized latexes with high polymer/surfactant weight ratios up to about 12/1 and nearly monodisperse particles ranging from 18 to 33 nm in diameter. X-ray photoelectron spectroscopy results showed that SABS-n was significantly enriched on the surface of latex particles. The effects of concentrations of SABS-n, BMA, and APS/TMEDA and the latex characteristics during the continuous addition of monomer were studied. A possible polymerization mechanism was proposed.     

无皂乳液聚合制备PUA乳液的稳定性研究

采用无皂乳液聚合法制备丙烯酸酯一聚氨酯复合乳液（PUA）。HEMA作为交联剂引入到聚氨酯主链上,利用核壳交联制得复合乳液。研究了不同的合成工艺、丙烯酸酯单体、DMPA及HEMA含量,引发剂种类等对乳液稳定性的影响。研究发现,将丙烯酸酯单体溶胀于水性聚氨酯乳液中再进行聚合可大大提高乳液的稳定性;采用1．0％～12％的AIBN为引发剂、DMPA质量分数为4．5％、HEMA质量分数为4．0％～4．5％、丙烯酸酯单体质量分数为30％时,可制得外观及稳定性良好的PUA复合乳液。     

丙烯酸酯-富马酸酯共聚乳液的合成及表征

采用半连续乳液聚合方法,以甲基丙烯酸甲酯（MMA）、富马酸二丁酯（DBF）为主单体,丙烯酸（AA）为功能单体,十二烷基硫酸钠（SDS）为乳化剂,过硫酸钾（KPS）为引发剂,合成了固含量为30%的共聚物乳液。探讨了单体配比、SDS用量、KPS用量对乳液及胶膜性能的影响。结果表明,乳胶粒子有核壳结构,当DBF/MMA比例为1/1.5,SDS为单体总质量的3%,KPS为0.4%时,乳液涂料综合性能达到最佳,涂膜光泽度、附着力良好,力学性能及耐化学试剂性能优良。     

Synthesis of poly(butyl acrylate‐co‐methyl methacrylate)/montmorillonite waterborne nanocomposite via semibatch emulsion polymerization

Poly(butyl acrylate‐co‐methyl methacrylate)‐montmorillonite (MMT) waterborne nanocomposites were successfully synthesized by semibatch emulsion polymerization. The syntheses of the nanocomposites were performed in presence of sodium montmorillonite (Na‐MMT) and organically modified montmorillonite (O‐MMT). O‐MMT was used directly after the modification of Na‐MMT with dimethyl dioctadecyl ammonium chloride. Both Na‐MMT and O‐MMT were sonified to obtain nanocomposites with 47 wt % solids and 3 wt % Na‐MMT or O‐MMT content. Average particle sizes of Na‐MMT nanocomposites were measured as 110–150 nm while O‐MMT nanocomposites were measured as 200–350 nm. Both Na‐MMT and O‐MMT increased thermal, mechanical, and barrier properties (water vapor and oxygen permeability) of the pristine copolymer explicitly. X‐ray diffraction and transmission electron microscope studies show that exfoliated morphology was obtained. The gloss values of O‐MMT nanocomposites were found to be higher than that of the pristine copolymer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42373.     

反相乳液聚合合成聚丙烯酰胺

以甲苯为介质,Span80/Span20为乳化剂,叔丁基过氧化氢/亚硫酸氢钠氧化还原体系为引发剂,采用反相乳液聚合制备了分子量高达9.4×106的聚丙烯酰胺乳液。研究了乳化剂种类及用量、引发剂种类及用量、油水比、单体浓度,反应温度对共聚物相对分子量、聚合转化率以及聚合反应速率的影响。其最佳聚合配方及工艺条件为:油水体积比为1.4,单体浓度30%,引发剂用量0.003%,乳化剂用量12%,聚合温度30℃。     

Synthesis,Characterization, and Antimicrobial Properties of p-Chloroacetophenone Oxime-Based Furan Resins

A copolymer resin, p-chloroacetophenone oxime-furfuraldehyde (CAOFU), and a terpolymer resin, p-chloroacetophenone oxime-formaldehyde-benzoic acid (CAOFUBA), were synthesized in the presence of hydrochloric acid as catalyst. The structures of copolymer and terpolymer were established by FT-IR and ¹H NMR techniques. Molecular weight and polydispersity index were determined by gel permeation chromatography. The thermal stability was evaluated by thermogravimetric analyses (TGA). Softening temperatures (T_s) of these polymers were obtained from differential scanning calorimetry (DSC). All the synthesized polymers have shown reasonably good antimicrobial activities.     

Morphology of poly(butyl acrylate)/poly(styrene‐co‐methyl methacrylate) latex prepared by starved emulsion polymerization: II. Development of particle morphology

Heterogeneous latexes were prepared by a two‐stage seeded emulsion polymerization process under monomer starved conditions at 80 °C using potassium persulfate as the initiator and sodium dodecyl sulfate as the emulsifier. Poly(butyl acrylate) latexes were used as seeds. The second‐stage polymer was poly(styrene‐co‐methyl methacrylate). By varying the amount of methyl methacrylate (MMA) in the second‐stage copolymer, the polarity of the copolymer phase could be controlled. It was found that the latex particles displayed different morphologies depending on the monomer ratio. The amount of MMA had a significant effect on the evolution of morphology. The morphologies were observed by transmission electron microscopy. In addition, the evolution of the particle morphology was predicted by the mathmatical model for cluster migration. The model gave the same trends as the experimental results. © 2002 Society of Chemical Industry     

苯乙烯/丙烯酸丁酯反向原子转移自由基乳液聚合的合成与表征

采用Tween 80为乳化剂,FeCl3.6H2O/EDTA/AIBN为催化引发体系,在乳液体系中对苯乙烯、丙烯酸丁酯进行反向原子转移自由基(RATRP)共聚合。考察了原料加入方式、过渡金属催化剂浓度及反应温度对RATRP乳液聚合影响。结果表明,得到聚合物的分子量与单体转化率呈线性增长,分子量分布较窄(PDI为1.40)的无规共聚物。借助于凝胶渗透色谱(GPC)和红外光谱仪(IR)对RATRP共聚乳液进行表征,表明加入催化体系进行RA-TRP乳液聚合是"活性"可控聚合。