Synthesis of cationic flocculants by the inverse microemulsion copolymerization of acrylamide with 60% 2‐acryloxyethyltrimethyl ammonium chloride in the monomer feed. II. Influence of the formulation composition,hydrophilic‐lipophilic balance,starting polymerization temperature,and reaction time

Acrylamide/2‐acryloxyethyltrimethylammonium chloride copolymers in inverse microemulsions, with 60% 2‐acryloxyethyltrimethyl ammonium chloride in the monomer feed and a concentration of active matter of 30% (w/w) as flocculants, were obtained by inverse microemulsion copolymerization. Inverse microemulsion formulations of comonomers, interesting from both technical and economical viewpoints, were polymerized by semicontinuous free‐radical copolymerization with sodium disulfite as the initiator. The influence of the formulation composition, hydrophilic‐lipophilic balance (HLB), starting polymerization temperature, and reaction time on the polymerization and final properties of the products as flocculants was studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:186–197, 2007     

引发剂对纤维素接枝丙烯酰胺反应的影响

分别以硝酸铈铵、过硫酸钾和过硫酸钾/亚硫酸钠为引发剂,以马尾松漂白硫酸盐浆纸浆纤维素为骨架接枝丙烯酰胺,在单体浓度为0.75 mol/L、温度为45℃、反应时间为3 h时,得到硝酸铈铵和过硫酸钾的最佳浓度为3.0 mmol/L和5.0 mmol/L,过硫酸钾/亚硫酸钠在用量为6%时的最佳质量比为1.5,三者相应的接枝率分别为40%、48%和60%。同时比较了不同条件下三种引发剂的接枝效果,结果表明,过硫酸钾/亚硫酸钠的接枝效果最好,但均聚物含量高;硝酸铈铵作为引发剂虽然接枝效果不及前两者,但均聚物含量很低。     

Dispersion copolymerization of acrylamide with acrylic acid in an aqueous solution of ammonium sulfate: Synthesis and characterization

Dispersion copolymerization of acrylamide with acrylic acid in an aqueous solution of ammonium sulfate using poly(2‐acrylamido‐2‐methylpropanesulfonic acid sodium) as the stabilizer and ammonium persulfate (APS) as the initiator was investigated. The influence of initiator concentration, stabilizer concentration, ammonium sulfate concentration, chain‐transfer agent concentration, and polymerization temperature on the copolymerization was discussed. The results showed that varying the ammonium sulfate concentration could affect the particle size and the intrinsic viscosity of the copolymer significantly. With increasing the stabilizer concentration, the particle size of the copolymer decreased first, and then increased, meanwhile the intrinsic viscosity of the copolymer decreased. The increase of initiator concentration, chain‐transfer agent concentration, and polymerization temperature resulted in the increase in the particle size. Polydisperse spherical particles were formed in the system, and the kinetics for the dispersion copolymerization were discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3685–3690, 2006     

Synthesis and properties of copolymer microemulsions of siloxane and acrylate with a high solid content

Copolymer microemulsions of methyl methacrylate, butyl acrylate, and vinyltriisopropoxysilane with high monomer/surfactant ratios were prepared through a seeded semicontinuous polymerization in the presence of a redox initiator, ammonium persulfate/sodium hydrosulfate. The mean diameter of the particles decreased with an increase in the amount of the surfactant, the monomer concentration, and the vinyltriisopropoxysilane/monomer ratio, but it increased with an increase in the concentration of the initiator. When the initiator concentration was 0.23% (ammonium persulfate/sodium hydrosulfate = 1.5 : 1), the concentration of the composite surfactant was 0.9 wt %, and the reaction temperature was 50°C; the solid content of the microemulsion could be up to 43% with a small particle size (mean diameter) of 39.8 nm. The chemical, freeze–thaw, and mechanical stability of the latexes was tested as well as the thermal stability of the films. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 851–857, 2007     

Polymerization of acrylamide in styrene containing inverse microemulsions: polymerization kinetics and polymer product composition studies

The kinetics of free‐radical homopolymerization and copolymerization of acrylamide (AAm) and styrene (S) initiated by water‐soluble ammonium peroxodisulfate, (APS) or by toluene‐soluble dibenzoyl peroxide (DBP) in inverse microemulsion toluene/S/AOT (sodium bis(2‐ethylhexyl)sulfosuccinate)/water/AAm characterized by a low volume fraction of the aqueous phase (Φ_aw ≈ 0.08) as a function of the concentration of S in the oil phase of the inverse microemulsion system have been studied. S strongly decreases the rate of AAm/S (co)polymerization. This is valid for both APS and DBP initiators. Kinetic measurements indicate the important role for cross‐initiation of water soluble AAm growing chains and of oil soluble S analogues activated by the primary free‐radicals generated from APS (or from DBP) in the dispersed water droplets (or in the continuous oil‐phase) of the inverse microemulsion, respectively. With inverse microemulsions containing toluene (70.73 %)/S (2.44 %)/AOT(17.56 %)/water (7.32 %)/AAm (1.95 %), after polymerization (initiator APS, 3.04 × 10⁻² mol dm⁻³ of water) and separation of the polymeric components, the following yields were obtained: AAm/S (co)polymer (89.20 mass%; ie 62.24 mass% of AAm structural units and 26.96 mass% of S structural units), polyacrylamide (9.4 mass%) and polystyrene (1.4 mass%). © 2000 Society of Chemical Industry     

过硫酸盐引发棉纤维接枝的研究

以过硫酸盐与硫代硫酸钠为引发剂,使丙烯酰胺与棉纤维进行接枝共聚,研究了过硫酸盐的加入方式和加入量对接枝反应的影响,发现采用过硫酸铵与过硫酸钾两种氧化剂、两步加入的办法能够克服体系中氧气的阻聚作用,又能得到较高的单体转化率和接枝率。     

Monomer reactivity ratios for acrylonitrile/ammonium itaconate during aqueous‐deposited copolymerization initiated by ammonium persulfate

Monomer reactivity ratios of acrylonitrile/ammonium itaconate during aqueous‐deposited copolymerization initiated by ammonium persulfate were investigated. Kelen–Tudos method was used to examine the reactivity ratios. It was shown that the reactivity ratios were influenced by the conversions and temperatures of copolymerization. The reactivity ratios in aqueous‐deposited copolymerization system were similar to those in the solution polymerization system at polymerization conversions of less than 5% [reactivity ratio of acrylonitrile (r₁) 0.842 ± 0.02, reactivity ratio of ammonium itaconate (r₂) = 3.624 ± 0.02]. The reactivity ratio of AN rises and that of (NH₄)₂IA decreases, when the polymerization conversion increases till 13%. Aqueous‐deposited copolymerization initiated by AIBN was also studied. It was found that some polymers were formed in water phase and the monomers had different reactivity ratios by comparison with those initiated by ammonium persulfate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4645–4648, 2006     

球形纤维素珠体-AN-AM接枝共聚物的制备

以球形纤维素珠体为原料,丙烯腈(AN)和丙烯酰胺(AM)为单体,硝酸铈铵和过硫酸钾(KPS)为引发剂,制备纤维素珠体-AN-AM接枝共聚物,并通过正交单因素实验,研究了反应温度、引发剂用量、单体用量、反应时间等因素对接枝效果的影响。实验结果表明:当反应温度为60℃,引发剂硝酸铈铵用量为20%,KPS用量为15%(引发剂与单体AN的质量百分比),单体AN浓度为0.75 mol/L,AM浓度为0.28 mol/L,硝酸浓度为0.14 mol/L,反应时间为3 h时,接枝效果最好。此条件下,AN、AM与纤维素的接枝率可达259.4%,接枝效率可达49.40%。     

反相乳液共聚淀粉-丙烯酰胺-丙烯酰氧乙基三甲基氯化铵的合成及应用

以无水亚硫酸钠（Na2SO3）和过硫酸铵【（NH4）2S2O8】为51发剂,通过反相乳液聚合制备了淀粉／丙烯酰胺（AM）／丙烯酰氧乙基三甲基氯化铵（DAC）三元共聚物,讨论了乳化剂种类、引发剂用量、反应温度和反应时间对反应产物的影响,确定了最佳反应条件：选用OP-10与Span-80复配乳化剂,51发剂用量为0．15％,反应温度为35℃,反应时间为5h,在此条件下得到的产物特性粘数为465mL／g。用红外光谱对接枝共聚物的结构进行了表征。对生活污水的应用实验表明,该接枝共聚物有很好的絮凝效果。     

N-丁基马来酰亚胺/苯乙烯共聚合机理研究

研究了氘代氯仿中Ｎ－丁基马来酰亚胺（ＮＢＭＩ）和苯乙烯的络合性能。在多组分Ｏ／Ｗ微乳液中,用过硫酸钾引发ＮＢＭＩ和Ｓｔ进行微乳液共聚合,考察了聚合温度,单体配比对共聚合的影响,并对共聚机理进行了研究。结果表明,ＮＢＭＩ／Ｓｔ微乳液共聚合是按照自由－络合机理进行的,在共聚合过程中,既有自由单体参与,又有电荷转移络合物（ＣＴＣ）参与。     

淀粉在CH3OH-H2O溶液中与MA进行接枝共聚的研究

在ＣＨ３ＯＨ－Ｈ２Ｏ溶液中,以过硫酸铵作引发剂进行淀粉与丙烯酸甲酯的接枝共聚反应,测定了共聚物接枝链的粘均相对分子质量、接枝效率、接枝频率,扫描电镜与力学性能。     

Graft copolymerization of methyl methacrylate onto sago starch using ceric ammonium nitrate and potassium persulfate as redox initiator systems

The graft copolymerization of methyl methacrylate (MMA) onto sago starch was carried out in aqueous media by different initiators of ceric ammonium nitrate (CAN) and potassium persulfate (PPS) and under a nitrogen gas atmosphere. Using CAN as an initiator, the maximum percentage of grafting (%G) was ascertained to be 246% at the following optimum conditions: a 70°C reaction temperature, a 2‐h reaction period, 2.0 mmol of CAN, 0.4 mmol of nitric acid, and 141 mmol of MMA. The maximum %G achieved with PPS as the initiator was 90%. The optimum conditions were a 50°C reaction temperature, a 1.5‐h reaction period, 47 mmol of monomer, and 1.82 mmol of PPS. The grafting of MMA onto sago starch was confirmed by the IR spectra of pure sago starch, MMA, and MMA grafted sago starch. This material may have application as a biodegradable plastic. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1375–1381, 2001     

黄原胶与丙烯酰胺接枝共聚反应的研究

以过硫酸铵为引发剂,在氮气保护下,研究了黄原胶与丙烯酰胺的接枝共聚反应。考察了单体浓度、引发剂浓度、反应温度和反应时间等因素对接枝率及接枝效率的影响,探讨了过硫酸铵引发黄原胶接枝丙烯酰胺共聚反应的基本规律。采用红外光谱、X射线粉末衍射对接枝共聚物的结构进行研究,用热重分析法表征了产物的热性能,并初步探讨了接枝机理。结果表明,过硫酸铵能有效地引发黄原胶与丙烯酰胺的接枝共聚反应,并且接枝率和接枝效率随单体浓度、引发剂浓度、反应温度的变化出现极大值,随反应时间的延长不断上升,直至基本不变。     

Stability and copolymerization of concentrated emulsion of styrene and butyl acrylate in the presence of polyurethane macromonomer

A study has been made of the stability and copolymerization of concentrated emulsion of styrene (St) and butyl acrylate (BA) in the presence of polyurethane macromonomer (DPUA), which contains C?C at one end. First, the DPUA macromonomer was synthesized from the appropriate amount of 2,4‐diisocyanate (TDI), polypropylene glycol (PPG), 2‐hydroxyethyl methylacrylate (HEMA), dimethylolpropionic acid (DMPA), and triethylamine (TEA) by four steps. Then, the DPUA was dissolved in St‐BA monomer mixtures. The DPUA/St‐BA concentrated emulsion copolymerization using sodium dodecyl sulfate/cetyl alcohol (SDS/CA) as composite surfactant and polyvinyl alcohol (PVA) as liquid film reinforcer, and ammonium persulfate/sodium hydrogen sulfate (APS/SHS) as redox initiator system was carried out at 30°C. The effect of NCO/OH molar ratio, surfactants' concentration, mass ratio of DPUA/St‐BA, initiators' concentration, volume fraction of the monomer phase (Φ), and temperature on the stability or the copolymerization of the concentrated emulsion of DPUA/St‐BA were investigated. The average size and distribution of the latex particles obtained under different conditions were also analyzed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1992–1999, 2007     

Saline solution absorbency and structure study of poly (AA-AM) water superabsorbent by inverse microemulsion polymerization

A series of novel copolymer superabsorbents based on acrylamide (AM), acrylic acid(AA) were prepared by inverse microemulsion copolymerization using ammonium persulfate (APS) as the initiator and N,N-methylenebisacrylamide (MBA) as the crosslinking agent and OP-10 and SDS as complex surfactants. The synthetic variables (amount of crosslinking agent and initiator, water/oil ratio, monomer/surfactant ratio and AA/ Am ratio) and their effects on the absorbencies of the synthesized superabsorbents were investigated. The experimental results of superabsorbent polymers (SAPs) showed the maximum saline solution absorbency of 130 g/g within 75 min, and the saline solution absorbency of 111 g/g within 30 min. FTIR indicated the structure of the acrylic acid and acrylamide copolymer. SEM indicated that the particles prepared with higher crosslinker content (0.03%) showed smaller pore sizes and less porous structures compared with those with less crosslinker content (0.01%) and the number of the micropores largely decreased with the water/oil ratio increasing from 8% to 14%.     

Preparation of water soluble Am–AA–SSS copolymers by inverse microemulsion polymerization

Inverse microemulsion copolymerization of acrylamide (Am), acrylic acid (AA), and sodium 4-styrenesulfonate (SSS) initiated by redox initiators composed of ammonium peroxodisulphate (APS) and sodium bisulfite, and stabilized by the mixed emulsifier system sorbitan monooleate (Span-80) and polyoxyethylene sorbitan monooleate (Tween 80) were examined as a function of the combination of hydrophilic (Tween 80) and hydrophobic (Span 80) emulsifiers, reaction temperature, AM/AA mass ratio, SSS concentration, and initiator concentration. The physicochemical and thermal properties and the structure of this copolymer were also determined and discussed. The reaction rates for all runs of the experiments exhibited two intervals, which were typical of microemulsion polymerization. The copolymer had only one glass transition temperature of 115.5 °C, indicating a random structure.     

苯乙烯/丙烯酸丁酯交联体系乳液聚合动力学研究

以十二烷基苯磺酸钠(SDBS)为乳化剂,过硫酸钾(KPS)引发苯乙烯/丙烯酸丁酯(St/BA)乳液共聚,加入二甲基丙烯酸乙二醇酯(EGDMA)、聚丁二烯生胶(PB)作为交联剂,研究了聚合温度、引发剂浓度、乳化剂浓度、单体配比对聚合速率的影响。实验结果表明,共聚体系的表观活化能为70.67kJ/mol,聚合初始速率与引发剂浓度的0.43次方、乳化剂浓度的0.56次方和单体BA的0.49次方成正比。     

淀粉/AA/AM/MA反相悬浮法合成高吸水树脂

以含阻聚剂的工业级丙烯酸(AA)、丙烯酸甲酯(MA)及木薯淀粉、丙烯酰胺(AM)为原料,采用反相悬浮法,使用自配分散剂,环己烷为连续相,过硫酸钾和亚硫酸氢钠为引发剂,N,N-亚甲基双丙烯酰胺为交联剂合成了高吸水树脂。结果表明,最佳工艺条件为:m(淀粉)∶m(AA)∶m(AM)=1.0∶4.5∶0.9,MA、交联剂加入量分别为5.0%,0.3%(相对AM和AA总质量),引发剂(两次引发)浓度分别为2.0,13.5 mmol/L,油水比例为1.90∶1.00(体积比)。在上述条件下制得的树脂的吸水率≥600 g/g,吸盐率≥60 g/g,环己烷回收率为97.3%。由于引入适量的MA,产物吸水率和吸盐率提高了20%,产物形态由最初的粘接颗粒变成分散颗粒。     

A comparison of composition and sequence distribution of p(AM-MADQUAT) prepared by solution and inverse microemulsion polymerization

Acrylamide (AM)/2-(methacryloyloxy)ethyltrimethylammonium chloride (MADQUAT) copolymers were prepared by solution and inverse microemulsion polymerization using ammonium persulfate ((NH₄)₂S₂O₈)/sodium hydrosulfite (NaHSO₃) as redox initiator at 30 °C. The comonomer reactivity ratios, determined using the Kelen–Tudos (KT) method, were r _A = 0.30, r _M = 1.31 in solution and r _A = 0.63, r _M = 1.13 in the inverse microemulsion, respectively. The copolymer microstructure was deduced from the run number and the heterogeneity, based on reactivity ratios. It was found that copolymerization in the inverse microemulsion resulted in close to ideal copolymerization, giving almost random copolymers; copolymerization in solution resulted in some alternating copolymers. The copolymer compositions indicated that high-conversion samples obtained from the inverse microemulsion are much more homogeneous in composition compared with those obtained in solution. It was found that the composition distribution of the copolymer prepared by inverse microemulsion polymerization remained at approximately the feed ratio. The sequence distribution of the copolymer was predicted by first-order Markov statistical and Bernoulli statistical models, respectively. The results showed that the sequence distribution of the copolymer prepared by inverse microemulsion polymerization was almost random, which led to a wider cationic charge distribution and a microstructure that was coincident with the feed ratio.     

微波辐射合成多功能腐植酸-马来酸酐共聚物陶瓷添加剂

采用微波辐射技术,以天然有机质钠盐腐植酸钠(NaHA)为原料,以马来酸酐(MA)为改性单体,通过自由基共聚合制备了新型腐植酸钠-马来酸酐共聚物(NaHA-co-MA)陶瓷添加剂。探讨了引发剂种类对陶瓷泥浆流动性的影响,确定硝酸铈铵为最有效引发剂。通过正交试验得到最佳合成条件为引发剂用量0.04%(质量分数)、NaHA与MA质量比1.2∶1.0、微波功率320W、间歇辐射时间15min、聚合后中和程度pH为7.5,此时陶瓷泥浆的相对黏度为1.34,流动性最好。采用红外光谱分析及坯体强度、可塑性测试等手段对NaHA-co-MA结构和性能进行分析:红外光谱显示NaHA结构中的-OH为与MA接枝共聚的活性点;坯体强度和可塑性试验表明,当NaHA-co-MA添加量为基体的0.08%(质量分数)时,坯体的干燥强度达4.16mPa,可塑性指标为5.49kg.cm,经与NaHA比较,综合性能有较大提高。