氯乙烯/异丁基乙烯基醚乳液共聚物的合成

以(NH4)2S2O8／Na2SO3／CuSO4为氧化-还原引发体系、十二烷基硫酸钠(SDS)为乳化剂，采用间歇乳液聚合合成氯乙烯／异丁基乙烯基醚(VC／IBVE)共聚物。结果表明，当投料单体中IBVE质量分数增加时,相同聚合时间的聚合转化率和共聚物特性粘度明显降低。当转化率小于70％时，共聚物平均组成变化不大；聚合温度增加使聚合速率增加，但共聚物特性粘度减小；SDS浓度对聚合速率和共聚物特性粘度的影响很小；随引发体系浓度增加．聚合速率增加，共聚物特性粘度变化不大。     

N-苯基马来酰亚胺/苯乙烯/丙烯腈/α-甲基苯乙烯乳液共聚动力学

以十二烷基硫酸钠（SDS）为乳化剂,过硫酸钾（KPS）引发剂引发N-苯基马来酰亚胺／苯乙烯／丙烯腈／α-甲基苯乙烯（PMI／St／AN／α-MeSt）进行四元乳液共聚,考察了聚合温度,引发剂浓度,乳化剂浓度,α-MeSt浓度对聚合速率的影响。结果表明,共聚体系的表观活化能为84．14kJ／mol,聚合初始速率同引发剂浓度的0．46次方和乳化剂浓度的0．57次方成正比。乳化剂浓度8．4mmol／L,引发剂浓度1．8mmol／L,聚合温度75℃,聚合1h,85℃熟化2h是较为合理的反应条件。α-MeSt的浓度对聚合速率有很大的影响,应控制在0．35mol／L以下。     

三元共聚物P(IA/MA/AMPS)的合成及阻垢性能评价

以衣康酸(IA)、马来酸(MA)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为单体,以过硫酸铵为引发剂,以水为溶剂,通过自由基聚合合成了一种新型的三元共聚物,探讨了单体配比、聚合温度、引发剂用量、聚合时间等合成条件对阻垢性能的影响,确定了最佳的合成条件为:单体配比n(IA)∶n(MA)∶n(AMPS)=1∶1∶1,聚合温度80℃,引发剂占单体质量分数的5%,聚合时间2h;用红外分光光度仪分析证明得到了预期的产物结构,并测定了产物的特性黏度和固含量。通过静态法对三元共聚物的阻垢性能进行评价,在加剂量为50mg/L时阻碳酸钙率最佳可达93.6%,是一种性能优异的阻垢剂。     

AM/AMPS/DMAM三元共聚物的合成及性能研究

为提高驱油用聚合物的耐温抗盐性,采用N,N-二甲基丙烯酰胺(DMAM)与2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、丙烯酰胺(AM)通过氧化还原引发剂体系聚合方法合成了AM/AMPS/DMAM三元共聚物,用正交实验法确定了最佳合成方案为:温度40℃,pH值为11,引发剂浓度为0.18%,单体浓度为13%,DMAM加量为2%。对共聚物的耐盐性及热稳定性进行测试,在标准盐水中共聚物为2500 mg/L,温度为30℃时,粘度可达到35.3 mPa.s;温度为90℃时,粘度为9.70 mPa.s。结果表明,AM/AMPS/DMAM三元共聚物具有较好的抗盐性能和增粘性能,但抗温效果并不明显,有待进一步改进。     

聚丙烯酸钠高吸水剂的合成和性能评价

以丙烯酸（从）共聚单体,分别以过硫酸钾（KPS）和N,N-亚甲基双丙烯酰胺（NMBA）为引发剂和交联剂,采用水溶液聚合法合成聚丙烯酸钠高吸水性树脂。评价了SAP在蒸馏水的吸水速率及SAP在水中的保水能力。探讨了单体浓度（M）、引发剂浓度（I）、交联剂浓度（C）、聚合温度（℃）对SAP在自来水中吸水倍率的影响。结果表明：在AA浓度为40％：交联剂N,N′-亚甲基双丙烯酰胺质量分数为单体总量的0．035％;引发剂质量分数为0．10％;聚合温度为80℃;合成得到的高吸水性树脂吸蒸馏水率达到1050g／g。     

乙烯基吡咯烷酮/乙烯己内酰胺共聚物的制备及其头发卷曲保持性能研究

以N-乙烯基吡咯烷酮(NVP)、N-乙烯基己内酰胺(NVCL)为单体,以水与乙醇为复合溶剂,以自由基聚合法合成了乙烯基吡咯烷酮/乙烯基己内酰胺(VP/CL)共聚物。采用红外光谱表征了其结构,采用黏度法测试其K值,以浊点法测试其温敏性,并考察了引发剂、反应温度、单体浓度等对共聚物K值的影响,以及单体比例对于温敏性能的影响。结果表明引发剂偶氮二异丁腈(AIBN)用量为质量分数0.3%～0.4%、反应温度65℃、单体质量分数40%、NVCL物质的量分数在40%～50%时,可合成K值与浊点较高、性能稳定的VP/CL共聚物。VP/CL (物质的量比50:50)共聚物浊点为53℃,其在相对湿度90%的高湿条件下对头发的卷曲保持率高达76%,呈现很强的定型能力。     

以己二酸二乙酯为偶联剂的正丁基锂/四氢糠醇乙醚体系合成苯乙烯-丁二烯共聚物

以正丁基锂(n-BuLi)为引发剂,环己烷与己烷混合作为溶剂,四氢糠醇乙醚(ETE)为极性调节剂,己二酸二乙酯(DEAP)为偶联剂,采用负离子聚合法合成了苯乙烯-丁二烯共聚物,考察了ETE用量及反应温度对聚合反应速率、共聚物组成以及共聚物微观结构的影响,也考察了DEAP用量对偶联效率的影响。结果表明,随着ETE用量的增加或聚合温度的升高,聚合反应速率逐渐增大。当反应温度为35~50℃、ETE用量为200~300μg/g时,共聚物中乙烯基结构含量随ETE用量的增加和聚合温度的降低而增大,乙烯基的质量分数最多可达67.2%,苯乙烯单元在共聚物中趋于无规分布。当DEAP与n-BuLi的摩尔比为0.25时,偶联效率最高可达60.90%。     

腐植酸钠-丙烯酰胺接枝共聚物的合成

采用水溶液聚合方法,以过硫酸钾为引发剂,以腐植酸钠、丙烯酰胺为原料进行接枝共聚反应。考察了引发剂用量、物料比、反应温度和反应时间等因素对合成腐植酸钠-丙烯酰胺接枝共聚物的影响。确定最佳聚合工艺条件为：反应温度70℃、反应时间6h、引发剂用量2．5％、丙烯酰胺与腐植酸钠质量比50：1（g：g）。通过红外光谱对共聚物的结构进行了表征,试验结果表明合成了目标产物。     

马来酸酐/丙烯酸/丙烯酸甲酯共聚阻垢剂的合成及应用性能研究

以马来酸酐、丙烯酸、丙烯酸甲酯为原料合成了新型三元共聚物阻垢分散剂,探讨了单体配比、引发剂用量、聚合温度、聚合时间等对共聚物阻垢性能的影响,得出了最佳合成条件:引发剂用量4%;n(马来酸酐):n(丙烯酸):n(丙烯酸甲酯)=2∶2∶1;反应温度70℃;反应时间3 h;得到的产品阻垢率为88.37%。并研究了水质条件及共聚物用量与阻垢性能之间的关系。     

两性共聚物P(AM-co-SPE)的合成及盐溶液性质

以1,3-丙磺酸内酯和甲基丙烯酸N,N-二甲基氨基乙酯(DMAEMA)为原料,合成功能单体N,N-二甲基-N-甲基丙烯酰氧乙基-N-(3-磺丙基)铵甜菜碱(SPE),然后将该单体和丙烯酰胺(AM)进行自由基共聚反应,制备了两性共聚物P(AM-co-SPE),红外光谱表征了合成的功能单体及两性共聚物结构,探讨了聚合反应影响因素及两性共聚物在盐水中的黏度行为。结果表明,以过硫酸钾为引发剂,在聚合温度为60℃、引发剂用量为0.5%、单体SPE比例为10%时,获得两性共聚物特性黏数高达93mL·g~(-1);该两性共聚物在盐水中有明显增黏效果,且共聚物黏度随盐浓度增加而增大,尤其是在Ca~(2+)和Zn~(2+)盐溶液中增黏效果更佳,表现出明显的反聚电解质溶液性质。     

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     

苯乙烯-丙烯腈-马来酸酐三元共聚物的合成及其在PC/ABS中的应用

采用本体聚合的方法,以苯乙烯、丙烯腈、马来酸酐为反应单体,加入引发剂、链转移剂合成了苯乙烯-丙烯腈-马来酸酐(SAM)三元共聚物.研究了引发剂种类、用量及链转移剂用量对三元共聚物摩尔质量的影响,寻求最优的合成条件;并以自制的SAM来增容聚碳酸酯(PC)/丙烯腈-丁二烯-苯乙烯(ABS)共混物,探讨了SAM对共混物性能的影响.通过红外(FTIR)、核磁(1H-NMR)、差示扫描量热仪(DSC)对三元聚合物结构进行了分析.研究表明:引发剂偶氮二异丁腈(AIBN)效果优于过氧化苯甲酰(BPO),苯乙烯、丙烯腈、马来酸酐物质的量之比为60:38:2,链转移剂十二硫醇(TDM)和引发剂偶氮二异丁腈(AIBN)的用量均为单体总质量的0.1%时,可获得摩尔质量为80 000g/mol左右的三元共聚物SAM;SAM对PC/ABS共混物起到了增容作用.     

Ferroelectric polymers with large electrostriction; based on semicrystalline VDF/TrFE/CTFE terpolymers

This paper discusses a new ferroelectric polymer with large electrostrictive response (∼4%) at ambient temperature, which is based on a processable semicrystalline terpolymer comprising vinylidene difluoride (VDF), trifluoroethylene (TrFE), and chlorotrifluoroethylene (CTFE). This VDF/TrFE/CTFE terpolymer was prepared by a combination of bulk polymerization process and a borane/oxygen initiator at ambient temperature. The incorporated bulky CTFE units in the terpolymer seem to reduce the crystalline domain size and move the ferroelectric-paraelectric (F-P) phase transition to near ambient temperature with a very small energy barrier. Some terpolymers exhibited common ferroelectric relaxor behaviors with a broad dielectric peak that shifted toward higher temperatures as the frequency increased, and a slim polarization hysteresis loop at near the dielectric peak (around ambient temperature) that gradually evolved into a normal ferroelectric polarization hysteresis loop with reduced temperature.     

Water‐soluble copolymers. II. Inverse emulsion terpolymerization of acrylamide,sodium acrylate,and acryloyloxyethyl trimethylammonium chloride

Inverse emulsion terpolymerization of acrylamide, sodium acrylate, and acryloyloxyethyl trimethylammonium chloride was investigated. Aqueous monomer solutions were emulsified in diesel oil with a blend of two surfactants (SPAN80 and TWEEN80) using 2,2′‐azobis(2‐amidinopropen)‐dihydrochloride as the initiator. The effects of temperature, initiator concentration, monomer concentration and composition, and emulsifier content on the polymerization conversion and the polymer intrinsic viscosity were examined. Polymer intrinsic viscosity increased with a decreasing concentration of initiator and an increasing concentration of monomer. The sizes of the latex particles of the terpolymer emulsions were observed with a scanning electron microscope, and the structure of the terpolymer was identified by FTIR spectroscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1381–1385, 2006     

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。     

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%。     

Structural and ferroelectric response in vinylidene fluoride/trifluoroethylene/hexafluoropropylene terpolymers

Poly(vinylidene fluoride/trifluoroethylene/hexafluoropropylene) terpolymers were synthesized by bulk polymerization process at ambient temperature based on alkyl borane/oxygen initiator. The ferroelectric and dielectric properties were investigated and compared with those of poly(vinylidene fluoride/trifluoroethylene) copolymer. The DSC, X-ray and FT-IR results suggest that the third comonomer in the polymer chain breaks the large polar domains into smaller domain size and reduces the crystallinity of terpolymer. As a result, both the ferroelectric-paraelectric phase transition and melting process take place at lower temperature. The smaller domain makes the dipoles reversal at lower electric field and reduces the polarization hysteresis as well as polarization level. High electrostrictive strain (2.5%) was obtained at low electric field for terpolymer with small quantity of HFP. The polarization and dielectric behaviors imply that the terpolymer is a typical ferroelectric relaxor. The terpolymer also shows higher room temperature dielectric constant than that of copolymer due to the lower phase-transition temperature.     

Kinetics of atom transfer radical polymerization of crosslinkable terpolymer P(MMA‐BA‐HEMA)

A crosslinkable terpolymer P(MMA‐BA‐HEMA) was prepared by atom transfer radical copolymerization of 2‐hydroxyethyl methacrylate, methyl methacrylate and butyl acrylate. The structure of the terpolymer was characterized by ¹H NMR and gel permeation chromatography. The effects on the polymerization of ligand, initiator, solvent, CuCl₂ added in the initial stage and reaction temperature were investigated. The optimal reaction conditions were ethyl 2‐bromopropionate as initiator, CuCl/PMDETA as catalyst, cyclohexanone as solvent, catalyst/ligand = 1:1.5, [M]₀:[I]₀ = 200:1 and temperature 70 °C. The reaction followed first‐order kinetics with respect to monomer concentration, indicating the best control over the polymerization process, a constant concentration of the propagating radical during the polymerization, efficient control over M_n of the polymer and low polydispersity (M_w/M_n < 1.3). © 2013 Society of Chemical Industry     

高单体进料浓度下丙烯腈连续水相沉淀共聚的研究Ⅱ聚合物颗粒形态

以ＫＰＳ－ＮａＨＳＯ３－Ｆｅ２＋ 为引发体系,在５ 升ＣＳＴＲ 中进行了高单体进料浓度（＞ ２８％ ）的丙烯腈（ＡＮ）－丙烯酸甲酯（ＭＡ）－苯乙烯磺酸钠（ＳＳＳ）三元连续水相沉淀共聚,系统考察了搅拌条件、单体进料浓度、引发剂浓度及配比、ｐＨ 值、平均停留时间和聚合温度等工艺因素对聚合物颗粒形态的影响。结果表明,有利于提高聚合反应速率的因素,包括提高单体进料浓度、引发剂浓度、ｐＨ值和聚合温度等均有利于改善颗粒形态,其中搅拌强度和单体进料浓度影响最明显。适当延长平均停留时间也对颗粒形态稍有改善。