Aqueous dispersion polymerization of amphoteric polyacrylamide

The terpolymer of acrylamide (AM), dimethylaminoethyl methacrylate methyl chloride (DMC), and acrylic acid (AA) was synthesized with their molar ratio of 70 : 15 : 15 through dispersion polymerization in aqueous solution of ammonium sulfate (AS), using poly(dimethylaminoethyl methacrylate methyl chloride) (PDMC) as stabilizer and 2,2′‐azobis(2‐amidinopropane) dihydrochloride (V‐50) as initiator. The particle size of the terpolymer ranged from 5 to 8 μm and the intrinsic viscosity was from 5.5 to 11.6 dL g^?1. The terpolymer had anti‐ polyelectrolyte effect under low AS concentration, but polyelectrolyte effect with the concentration beyond 10%. Polymerization dispersion with low apparent viscosity, uniform particles, good stability, and high molecular weight terpolymer was obtained in single stage. The effects of varying concentrations of salt, stabilizer, and monomers on particle morphology and intrinsic viscosity were investigated. With increasing concentration of AS and PDMC, the intrinsic viscosity of terpolymer increased, then decreased afterward. However, it increased gradually with increase in monomer concentration. The particle size was enlarged with increasing of AS and monomer concentration and decreasing of PDMC concentration. The optimum condition was the concentrations of salt, stabilizer, and monomers 28%, 3.0%, and 8% to 15%, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Water‐soluble copolymers. III. Two‐step terpolymerization of acrylamide,acrylic acid,and acryloyloxyethyl trimethylammonium chloride

Terpolymerization of acrylamide (AM), acrylic acid (AA), and acryloyloxyethyl trimethylammonium chloride (DAC) was studied in aqueous solution by a two‐step polymerization method, consisting of adiabatic polymerization until reaching a maximum temperature and following retaining temperature for maturation. A redox agent:promotor triad‐initiating system was employed as an initiator. The effects of various parameters on terpolymerization were investigated. The optimum values were obtained at the DAC:AA molar feed ratio and the total monomer concentration, at the oxidant:reductant ratio and total redox agent concentration, and at the promotor concentration and redox agent:promoter ratio. The structure of the terpolymer was identified by Fourier transform infrared (FTIR) and ¹³C NMR spectroscopy. And the terpolymer composition was agreed favorably with feed ratio. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3278–3284, 2007     

均匀设计优化聚丙烯酰胺合成工艺

采用氧化还原引发体系、利用半绝热水溶液聚合的方法,制备甲基丙烯酰氧乙基三甲基氯化铵-二甲基二烯丙基氯化铵-丙烯酰胺(DMC-DMDAAC-AM共聚物)阳离子型絮凝剂,研究了单体配比、阳离子摩尔分数、引发剂用量以及助剂配比对产品性能的影响,详细研究了产品的特性黏度和溶解性能的影响因素.在单体配比不变的条件下,提高了产物的阳离子度,从而提高了产物的絮凝性能.结合均匀设计对实验进行分析表明,最佳的反应物摩尔分数为丙烯酰胺:16.72%,甲基丙烯酰氧乙基三甲基氯化铵:12.84%,二甲基二烯丙基氯化铵:13.56%,去离子水:53.64%,乙二胺四乙酸二钠:0.003 12%,偶氮二异丁脒盐酸盐:0.044 22%,过硫酸钠:0.001 82%,甲醛合次硫酸氢钠二水:0.001 76%.并利用红外光谱和棱磁对合成的共聚物进行了结构表征.     

Water‐soluble copolymers. V. Synthesis of low molecular weight amphoteric polyacrylamide by foamed copolymerization

Amphoteric polyacrylamide of acrylamide, acryloyloxyethyl trimethylammonium chloride, sodium acrylate, and acrylic acid was synthesized by foamed copolymerization. The effects of monomer concentration and composition, initiator concentration and composition, sodium bicarbonate and stabilizer content on the polymer intrinsic viscosity and monomer conversion were examined. The monomer conversion increased with increasing initiator concentration, sodium bicarbonate and stabilizer content. The polymer intrinsic viscosity decreased with increasing initiator concentration. The structure and low molecular weight of the amphoteric polymer were identified by fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC), respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

偏氯乙烯/丙烯腈/苯乙烯悬浮共聚合动力学

本文研究了偏氯乙烯（ＶＤＣ）／丙烯腈（ＡＮ）／苯乙烯（Ｓｔ）三元悬浮共聚合体系的聚合机理、共聚速率、非聚物组成及其特性粘度的影响因素。实验表明随着投料配比的改变,可分成四个不同聚合机理区域。Ｓｔ对ＶＤＣ／ＡＮ／Ｓｔ三元悬浮共聚有缓聚作用。ＶＤＣ三元悬浮共聚速率可用半经验模型,ｄＣ／ｄｔ＝αＣ＾β「Ⅰ」ｏ＾γｅｘｐ（－γｋｄｔ）描述,由实验得到模型参数γ值为２．２４,模型参数α、β是聚合温度与引发剂浓度的函数。ＶＤＣ－ＡＮ－Ｓｔ三元悬浮共聚物存在着较宽的ＶＤＣ组成分布,并受到单体ＡＮ水溶性的影响,经ＡＮ动态相平衡校正后,可预测ＶＤＣ三元共聚物组成。ＶＤＣ－ＡＮ－Ｓｔ共聚物的特性粘度随着转化率的升高而增大。在相同引发剂用量下,高转化率ＶＤＣ－ＡＮ－Ｓｔ共聚物特性粘度的对数与温度的倒数成线性关系。     

新水溶液均相法制备两性聚丙烯酰胺的研究

采用氧化还原引发体系与AIBA为复合分段引发剂,在绝热水溶液体系中进行丙烯酸钠／丙烯酰胺／丙烯酰氧基乙基三甲基氯化铵自由基共聚合。研究了聚合温度、氧化还原引发体系用量、AIBA用量、单体浓度、共聚单体中DAC、AM含量,复合分散剂用量及其HLB值等对聚合反应单体转化率和聚合物特性黏度的影响。聚合物特性黏度随引发剂用量和单体浓度的增大而增大的实验结果证实了该两性聚丙烯酰胺水溶液均相制备过程中凝胶效应的存在。     

P(AM-DADMAC)的反相乳液聚合及其表征

利用反相乳液聚合法制备了阳离子共聚物P(AM-DADMAC),考察了乳化剂、分散介质、引发剂、单体浓度等因素对乳液体系稳定性和共聚物特性粘度的影响。结果表明:以Span80和Tween80为复合乳化剂且浓度为4%、煤油为分散介质、油水体积比为0.5、Va-044为引发剂且浓度为0.08%～0.1%、水相单体浓度为45%时,反相乳液聚合体系稳定,且能得到特性粘度较大的阳离子共聚物。利用红外谱图证实了共聚物P(AM-DADMAC)的结构。电镜照片显示,胶体颗粒为球形,尺寸在1～9μm之间。     

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     

Preparation,characterization, and flocculation performance of P(acrylamide‐co‐diallyldimethylammonium chloride) by UV‐initiated template polymerization

This study prepared TPDA, a high‐intrinsic‐viscosity cationic polyacrylamide, through ultraviolet (UV)‐initiated template polymerization. Acrylamide (AM) and diallyldimethylammonium chloride (DMD) served as monomers, and poly sodium polyacrylate (PAAS) served as the template. The structure of TPDA was characterized by Fourier‐transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and thermogravimetric analysis. The synthetic conditions of TPDA were studied and optimized by single‐factor experiments. An optimized product was obtained at an intrinsic viscosity of 11.3 dL g^?1 and a conversion rate of 97.2% with a total monomer concentration of 20%, DMD concentration of 30%, initiator concentration of 0.045%, pH of 8, EDTA concentration of 0.3%, and UV irradiation of 90 min. Results showed that TPDA was the copolymer of AM and DMD with a micro‐block structure at the molecular chain. Given its high intrinsic viscosity and cationic block structure, TPDA performed better in kaolin flocculation than that prepared without template addition. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41747.     

P（AM-DMC-AANa）共聚物的制备及絮凝性能的研究

采用光辅助引发技术,通过水溶液聚合法研究了丙烯酰胺（AM）、甲基丙烯酰氧乙基三甲基氯化铵（DMC）和丙烯酸钠（AANa）三元共聚物P（AM-DMC-AANa）的制备工艺.考察了引发温度、w（单体）、溶液pH值和w（引发剂）对聚合结果的影响,同时与传统的引发剂引发结果进行了对比,并探究了不同因素对聚合物絮凝性能的影响.结果表明,在引发温度40℃、w（单体）=40％、pH=6、w（引发剂）=0.018 0％时,产物特性粘数9.72 dL/g,溶解时间99 min;在w[P （AM-DMC-AANa）]=0.025 0％,特性粘数9.72 dL/g,聚合物离子度35％的条件下,上清液透光率90.25％,絮凝率80.76％,脱水率88.63％.     

Polymers with pendant isocyanate groups. III. Synthesis and properties of poly(styrene-co-acrylonitrile-co-styrylisocyanate)

The terpolymer poly(styrene-co-acrylonitrile-co-styrylisocyanate) was synthesized by radical initiation directly from styrene, acrylonitrile, and cinnamoyl azide. The monomer feed–terpolymer composition relationship was determined by Slocombe's triangular graph. The solubility, intrinsic viscosity, and melting range of the various terpolymers and the chemical reactions of the pendant isocyanate groups toward alcohol and amines were investigated.     

Preparation of nanometer‐sized poly(methacrylic acid) particles in water‐in‐oil microemulsions

A water‐in‐oil microemulsion, water‐in‐cyclohexane stabilized by poly(ethylene glycol) tert‐octylphenyl, was developed to prepare poly(methacrylic acid) (PMAA) particles. Up to 100% conversion of the amphiphilic monomer, methacrylic acid (MAA), which could not be converted to the polymer efficiently in a dioctylsulfosuccinate sodium salt/toluene microemulsion, was achieved. The viscosity‐average molecular weight of the PMAA prepared was 1.45 × 10⁵ g/mol. The effects of some polymerization parameters, including the reaction temperature and the concentrations of the initiator and the monomer, on the polymerization of MAA were investigated. The results showed that the polymerization rate of MAA was slower than that of acrylamide in the microemulsions reported in the literature. The degree of conversion increased with the initiator concentration, reaction temperature, and monomer concentration. However, the stable microemulsions became turbid during the polymerization when the reaction temperature was at 70°C or at a high monomer concentration (40 wt %) The synthesized PMAA particles were spherical and had diameters in the range of ～50 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2497–2503, 2006     

Melt grafting of n‐butyl methacrylate onto poly(vinyl chloride): Synthesis and characterization*

The graft copolymerization of n‐butyl methacrylate monomer onto compounded poly(vinyl chloride) was carried out by melt‐mixing process in a Brabender plasticorder (BPCR) using a free‐radical initiator. The reaction conditions such as initiator and monomer concentration, shear rate (rpm), residence time, and temperature were optimized in the mixing head of BPCR attached to a torque rheometer. The graft copolymers were Soxhlet extracted with cyclohexane and were characterized by intrinsic viscosity, FTIR, and ¹³C‐NMR spectroscopy. A maximum of 14% grafting was obtained. The graft copolymer showed significant improvement in processibility and both thermal and mechanical properties. Scale‐up studies of the optimized recipe were carried out in a single‐screw extruder for commercial trials/evaluation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2442–2449, 2004     

碳纤维原丝用聚丙烯腈的聚合反应条件

采用水相沉淀聚合法,以过硫酸铵为引发剂,制备了丙烯腈-丙烯酸甲酯-甲叉丁二酸三元共聚物,研究了聚合温度、单体浓度、引发剂浓度对聚丙烯腈共聚物相对分子质量和单体转化率的影响。结果表明:当反应温度为58℃,反应时间为2.5 h,单体质量分数为25%,引发剂质量分数为1.5%时,聚合物的黏均分子质量达3.8×105,单体转化率为79%。     

Study of P(AM‐NVP‐DMDA) hydrophobically associating water‐soluble terpolymer

A new kind of hydrophobically associating water‐soluble terpolymer P(AM‐NVP‐DMDA) was synthesized by free radical terpolymerization. Compared with micellar terpolymerization, this terpolymerization can be conducted in aqueous solution in absence of external surfactant, because the hydrophobic monomer is surface active. Synthesis, structure, and solution properties of P(AM‐NVP‐DMDA) terpolymer were studied, including its electrolyte effect, rheological behavior, temperature dependence of viscosity, dilute solution property, and the polymer–alkali, polymer–surfactant interaction. The terpolymer shows strong hydrophobic effect, and the terpolymer aqueous brine solution exhibits high viscosity at low polymer concentration. Incorporation of N‐vinyl‐pyrrolidone into the terpolymer causes an improvement in thermal stability of the terpolymer. The transmission electron photomicrograph analysis of the terpolymer indicates that the presence of the microphase separation of the terpolymer in aqueous solution plays an important role in the viscosification efficiency of the terpolymer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 211–217, 1999     

聚甲基丙烯酸氨基乙酯的合成及染色性能

以白油为分散介质,偶氮二异丁腈为引发剂,甲基丙烯酸氨基乙酯为单体,采用反相悬浮聚合法合成聚甲基丙烯酸氨基乙酯(PTAM),研究了引发剂用量、反应温度、反应时间、单体浓度对PTAM特性粘数的影响。将PTAM与聚丙烯腈(PAN)共混纺丝制得共混纤维,用酸性染料染色,考察其上染率。结果表明:合成PTAM的最佳工艺条件为引发剂质量分数0.05%,单体质量分数60%,反应温度65℃,反应时间2h,所得PTAM的特性粘数为690mL/g。染色实验结果表明,PTAM质量分数为7%时,PAN共混纤维的上染率达88%。     

新型酸液稠化剂的制备与性能评价

酸化处理是油气井增产增注的重要措施之一,而其中稠化剂是酸液中一种重要的酸性添加剂.文章中以二甲基二烯丙基氯化铵（DMDAAC）和丙烯酰胺（AM）为原料,过硫酸铵-亚硫酸氢钠为引发剂,采用水溶液聚合制备共聚物PDA（（Poly DMDAAC-AM）.实验考察了单体配比、总单体质量分数和引发剂用量等反应条件对共聚物特性粘数和单体转化率的影响.结果表明,经红外检测AM和DMDAAC发生了聚合,单体配比n（AM）∶n（DMDAAC）=8∶2,单体总质量分数为20％,引发剂用量为过硫酸铵和亚硫酸氢钠各占单体总质量的0.04％,最高单体转化率为67.70％,最佳特性粘数为505.59 mL/g.实验采用石油工业标准（SY/T6214-1996）对产品性能进行了评价,结果表明产品性能优良,可用作酸液稠化剂.     

AIBA·2HCl-NaHSO3引发下DMDAAC-AM共聚物的合成与表征

采用偶氮二异丁脒二盐酸盐(AIBA·2HCl)和NaHSO₃(RH)组成的引发体系,研究了引发剂浓度、溶液的pH值、引发剂复配和加料方式等因素对二甲基二烯丙基氯化铵(DMDAAC)-丙烯酰胺(AM)共聚合反应规律的影响.结果表明：在30 ℃、n_AM∶n_DMDAAC=4∶1、ω(monomer) =30％和引发剂AIBA·2HCl-RH的浓度为1.0×10^-4 mol·L^-1的条件下, pH=7.0时, DMDAAC-AM共聚物的特性黏数达11.56 dl·g^-1;pH=10.0时,特性黏数最高达13.60 dl·g^-1.采取连续加料方式,可获得阳离子度38.8％,特性黏数达11.61 dl·g^-1的共聚物.进一步测得该引发体系30 ℃下,聚合反应的表观活化能为33.25 kJ·mol^-1,单体的竞聚率为γ_AM=6.800,γ_DMDAAC=0.174.     

Synthesis,characterization, and rheological studies of methacrylic acid–ethyl acrylate–diallyl phthalate copolymers

Copolymerization of methacrylic acid (MAA) and ethyl acrylate (EA) was performed by the emulsion polymerization technique in the presence of a mixture of ionic and nonionic emulsifiers, at 85°C, using potassium persulfate as initiator (0.16 wt % of monomer). The molar ratio of MAA : EA varied between 44 : 56 and 54 : 46 in the monomer feed. Copolymers of MAA and EA were synthesized by incorporating diallyl phthalate (DAP) with varying concentrations (0–1.7 mol % of total monomer) in the feed. A copolymer latex of MAA, EA, and DAP was also prepared by the variable feed process. The intrinsic viscosity and gel content were determined. Copolymers were characterized by IR and NMR spectroscopic techniques. The composition of copolymers was determined by ¹H‐NMR spectra and sequential distribution from ¹³C{¹H}‐NMR spectra. The pH of the copolymer emulsion varied between 3 and 10 by addition of aqueous ammonia (23% w/w) and its effect on Brookfield viscosity was studied. The effects of copolymer composition, crosslinking agent concentration in the feed, monomer feed process, polymer solid contents, and shear rate on Brookfield viscosity were studied at pH ～ 8. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1430–1441, 2003     

复合引发体系合成两性离子聚合物P(AM-DMAPS)

以氧化还原引发剂和偶氮类引发剂组成复合引发体系,引发两性离子单体（DMAPS）与丙烯酰胺（AM）在盐溶液中进行自由基共聚合反应,获得了甜菜碱型两性离子共聚物P(AM-DMAPS),采用红外光谱对共聚物进行表征。考察了总单体的质量分数、引发剂用量、引发剂各组分物质的量之比、反应温度等因素对聚合物特性黏数的影响;获得最适宜反应条件：总单体的质量分数30%,引发剂用量0.025%,反应温度20 ℃,氧化还原引发剂组分与偶氮引发剂组分的物质的量之比1∶3。在该反应条件下,可获得特性黏数高达20.2 mL/g的目标产物。