二甲氨基链中多官能化溶聚丁苯橡胶的合成

采用负离子溶液聚合法,以仲丁基锂为引发剂、环己烷为溶剂、四氢呋喃为结构调节剂,以及1,1-双（4-二甲基氨基苯基）乙烯为官能化共聚单体与丁二烯和苯乙烯进行活性负离子共聚合,制备了二甲氨基链中多官能化丁二烯-苯乙烯共聚物,考察了聚合温度和结构调节剂用量对聚合动力学和聚合物微观结构的影响。结果表明,共聚物链中二甲氨基官能团数量可通过调整聚合温度和结构调节剂用量进行准确控制,随聚合温度升高和四氢呋喃用量的增加,单体的总反应速率和转化率都逐渐增大;聚合物中1,2-结构的含量随结构调节剂用量的增加而逐渐增大,随聚合温度升高而逐渐减小。求得聚合温度为50 ℃时丁二烯和苯乙烯单体的平均竞聚率为69.67。     

苯乙烯无规均匀分布的中乙烯基溶聚丁苯橡胶的合成及性能

采用负离子活性聚合法,用四氢呋喃-叔丁基氧钾二元调节体系合成了苯乙烯无规均匀分布的中乙烯基溶聚丁苯橡胶(SSBR),考察了调节体系对苯乙烯无规分布的均匀性、1,2-结构含量、聚合速率以及产物物理机械性能和动态力学性能的影响。结果表明,叔丁基氧钾对苯乙烯无规分布的均匀性起主要调节作用,四氢呋喃对1,2-结构含量起主要调节作用;增加四氢呋喃和叔丁基氧钾的用量则聚合速率加快;与常规SSBR相比,所合成苯乙烯无规均匀分布的中乙烯基SSBR的综合性能更好。     

双硅氧烷端基溶聚丁苯橡胶的合成

采用负离子聚合方法,以环己烷-己烷为溶剂、四氢呋喃为结构调解剂、双锂为引发剂进行丁二烯-苯乙烯共聚,聚合结束后加入r-氯丙基三甲氧基硅烷进行封端,得到双硅氧烷端基的溶聚丁苯橡胶(SSBR),并用核磁共振对其进行了表征.结果表明,所合成的产物为双硅氧烷端基SSBR;并通过核磁共振谱图计算了不同相对分子质量的SSBR的封端效率.     

高结合苯乙烯含量且均匀无规分布的溶聚丁苯橡胶的合成(英文)

采用负离子活性聚合的方法,以正丁基锂为引发剂、环己烷为溶剂、四氢呋喃为极性调节剂、叔戊醇钾为无规化剂,合成了结合苯乙烯质量分数为40%且均匀无规分布、1,2-结构质量分数为35%~40%的溶聚丁苯橡胶;考察了四氢呋喃用量和叔戊醇钾用量对产物的苯乙烯无规分布均匀性、1,2-结构含量等的影响。结果表明,四氢呋喃只能使苯乙烯-丁二烯无规共聚,苯乙烯的均匀无规分布主要受叔戊醇钾加入量的影响;当四氢呋喃和叔戊醇钾与正丁基锂的摩尔比分别为50和15.33×10-3时,在整个大分子链的增长过程中结合苯乙烯含量都保持在设计值附近,表明苯乙烯在大分子链上基本为均匀无规分布;四氢呋喃对于产物1,2-结构含量的调节起主要作用,而叔戊醇钾基本无影响,二者对产物的相对分子质量及其分布和共聚组成基本无影响。     

四氢呋喃-水-萃取剂的等压气液平衡数据的测定

采用新型的双循环沸点仪测定了在101.3 kPa下四氢呋喃-水-乙二醇和四氢呋喃-水-1,4-丁二醇体系的等压气液平衡数据.讨论了不同萃取剂对四氢呋喃的相对挥发度的影响.实验结果表明,乙二醇和1,4-丁二醇都能消除四氢呋喃-水体系的共沸点,并使四氢呋喃对水的相对挥发度明显提高,可作为萃取分离四氢呋喃-水的萃取剂.     

四氢呋喃-甲苯-氟苯-水体系汽液平衡数据的测定和关联!

采用单级循环汽液平衡釜测定了常压下四氢呋喃-甲苯、四氢呋喃-氟苯、四氢呋喃-水、甲苯-氟苯、四氢呋喃-甲苯-水、四氢呋喃-氟苯-水和四氢呋喃-甲苯-氟苯-水体系的汽液平衡数据,采用Herington方法对二元汽液平衡数据进行热力学一致性校验;分别以NRTL和UNIQUAC方程为相平衡模型,通过化工辅助软件分别对二元、三元体系的汽液平衡数据进行关联,确定模型参数和相平衡模型;采用6对二元模型参数关联出四元体系的汽液平衡数据,并与实验值进行比较。结果表明:实验值与计算值的相对偏差均小于5%,说明实验与计算值一致。研究结果为四氢呋喃、甲苯、氟苯和水混合液的分离提供了一定基础数据。     

星形杂臂异戊二烯-丁二烯/苯乙烯橡胶的合成与性能

采用异戊二烯聚合-二乙烯基苯(DVB)偶联-再引发丁二烯/苯乙烯聚合的方法合成了具有星形杂臂结构的异戊二烯-丁二烯/苯乙烯橡胶(s-ISBR).结果表明,DVB偶联效率可达60%,通过调节DVB用量可将臂数控制在2.6～6.1.采用四氢呋喃(THF)、1,1,4,7,7-五甲基二乙烯基三胺(PMDETA)或其复合体系可将3.4-PI,1.2-PB摩尔分数分别控制在8%～29% 和11%～65%.s-ISBR具有较高的撕裂强度和低的滚动阻力.     

有机-无机杂化黏土催化四氢呋喃聚合

采用后合成方法,将γ-巯基丙基三乙氧基硅烷嫁接到黏土表面,获得含磺酸有机功能团的黏土固体酸催化剂。经XRD、N₂ 吸附-脱附、FTIR、吡啶吸附和酸量滴定等物性结构表征及催化四氢呋喃聚合的反应活性评价,结果表明,改性后的黏土保持了原有黏土介孔结构,孔径分布集中在3 ～4.3 nm,酸量增加了35％,在催化四氢呋喃聚合反应中显现出较高的催化活性,在反应温度为35℃、反应时间为8 h的条件下,聚合产物收率达30％,得到数均分子量为2000左右、可用作氨纶生产原料的聚合物。     

杂多酸-乙酐催化四氢呋喃聚合的反应机理

研究了体系中存在乙酐时,四氢呋喃在杂多酸催化下进行阳离子开环聚合的反应机理。结果表明,杂多酸—乙酐络合物有较高的引发活性,该反应在笼型结构（四氢呋喃与杂多酸络合形成）中的杂多酸表面进行,经历了四氢呋喃与杂多酸络合、乙酐与杂多酸络合引发、四氢呋喃开环聚合及链终止反应等阶段,建立了以笼型结构为中心的机理模型。     

耐低温溶聚丁苯橡胶的合成与性能

以2-（乙氧甲基）四氢呋喃为结构调节剂,采用负离子聚合法合成了耐低温溶聚丁苯橡胶（SSBR）,考察了2-（乙氧甲基）四氢呋喃用量和反应温度对SSBR微观结构的影响,研究了SSBR的物理机械性能和动态力学性能,并与市售SSBR产品进行了对比。结果表明,该调节剂具有温度不敏感性,当反应温度为60℃、2-（乙氧甲基）四氢呋喃质量分数为140×10^-6时,所制得SSBR的结合苯乙烯与1,2-结构质量分数分别为15%和50%,苯乙烯在分子链上的无规度达到100%,玻璃化转变温度为-47℃;与市售SSBR产品相比,所制得SSBR的回弹性较好,永久变形小,耐磨性能良好,耐老化性能略优,滚动阻力较低。     

阴离子法丁羟的合成及其微观结构控制研究

以（CH3）3CSi（CH3）2O（CH2）3Li为引发剂，采用阴离子聚合法合成了丁羟胶，通过核磁共振对其进行了表征，并研究了引发剂浓度、单体浓度、极性添加剂四氢呋喃等对聚合物微观结构的影响，并分析了极性添加剂对其微观结构的影响机理。结果表明，引发剂浓度、单体浓度等对丁羟的微观结构影响甚微，而通过调节极性添加剂四氢呋喃的用量可控制丁羟胶的主链微观结构。     

溶剂极性的经验参数E_T在共轭二烯烃阴离子聚合中的应用

首次研究了以正丁基锂引发的共轭二烯烃在不同溶剂中聚合的反应活性与溶剂极性的经验参数E_T的关系,并导出了五个半定量关系式,由这些方程式可方便地预先估计在相应溶剂中的动力学和热力学常数.     

High ionic transfer of a hyperbranched-network gel copolymer electrolyte for potential electric vehicle (EV) application

Hyperbranched network-based gel copolymer electrolytes are synthesized by in situ free radical polymerization. This research is separated into two parts: the first is an investigation of modified bismaleimide oligomer (MBMI) as a free volume additive, and the second investigates the salt concentration effect on high power application. A polymer electrolyte with MBMI additive provided more free volume space, and the ionic conductivity of gel copolymer electrolytes was measured as a function of the salt concentration of lithium hexafluorophosphate (LiPF₆). The highest ionic conductivity and the lowest activation energy of hyperbranched-network gel copolymer electrolytes were determined to be 7.72 × 10⁻³ S/cm at 23 °C and 5.41 kJ/mol, respectively. Furthermore, the MBMI additive and the optimal concentration of lithium salt increased the free space for carrier ions and contributed to increasing capacity and working voltage at a high rate discharge (8C). The reliability and cycling ability of lithium polymer batteries are as good as lithium ion batteries for potential electric vehicle (EV) application.     

用PS-SnCl_4-CH_3COC_2H_5固载引发剂引发异丁基乙烯基醚聚合及其动力学

用PS-SnCl_4-CH_3COC_2H_5固载引发剂引发了异丁基乙烯基醚(IBVE)的聚合反应,研究了诸因素对IBVE聚合反应的影响。结果表明,在大气环境和常温下,IBVE本体聚合的动力学方程为R_p=K[I]~(2/3)。对不同的助剂,R_p的递减顺序为CH_2ClCH_2Cl,CCl_4,CHCl_3。聚合反应初期和中期的反应活化能分别为-26.48kJ/mol和45.63kJ/mol。聚合物的(?)_n随反应时间或单体转化率的增加而增大。在适宜的温度下,当固载引发剂用量较少,助剂用量较大时,该反应为易控制的匀速反应。     

Formation of SBS thermoplastic block copolymer using hexamethyleneimine alkenyl lithium (N‐Li) initiator

Styrene and butadiene block copolymers (SBS) end functionalized with amino group at the initiating chain ends were synthesized using hexamethyleneimine alkenyl lithium (N‐Li) as initiator, tetrahydrofuran (THF) as polar modifier, and cyclohexane as solvent. By attaching a few number of butadiene molecules to N‐lithium hexamethyleneimine, a new N‐Li initiator that can effectively initiate the polymerization of SBS was obtained. ¹H NMR spectrums of the N‐Li initiator terminated by ethanol, end functionalized polystyrene, and SBS block copolymer proved the structure of N‐Li and its ability to initiate the polymerization of styrene and SBS block copolymer. Kinetics studies suggested that the polymerization rate of styrene in the first block reached the maximum when the ratio of THF/Li was increased to 5, while further increase of the ratio of THF/Li could not improve the polymerization rate. The molecular weight distribution (MWD) of SBS initiated by N‐Li varied with the ratio of THF/Li. The vinyl content of polybutadiene block increased by improving the ratio of THF/Li, while the content of cis‐1,4 and trans‐1,4 structures decreased. The vinyl content of end functionalized SBS was somewhat higher than that of SBS initiated by classical n‐butyllithium when other condition was the same. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 81–88, 2006     

Anionic ring‐opening polymerization of adipic anhydride initiated by potassium poly(ethylene glycol)ate

Poly(adipic anhydride) (PAA) was prepared by the ring‐opening polymerization of adipic anhydride (AA) initiated by potassium poly(ethylene glycol)ate. The effects of various factors, such as the amount of initiator, concentration of the monomer, reaction time and temperature, and polarity of the solvent on the polymerization were investigated. The crude polymerized product was a mixture of PAA homopolymer and poly(ethylene glycol)–poly(adipic anhydride) block copolymer, as confirmed by ¹H‐NMR and gel permeation chromatography. Chain‐transfer reactions occurred intensively for the AA polymerization in both the nonpolar solvent toluene and the polar solvents CHCl₃ and tetrahydrofuran, which predominantly determined the molecular weight and the monomer conversion for the polymerized product. The lower monomer conversion in toluene was ascribed to a lower livingness for the initiator in the nonpolar solvent when compared with other two, polar solvents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2194–2201, 2003     

New perfectly difunctional organolithium initiators for block copolymer synthesis: Synthesis of dilithium initiators in the absence of polar additives

New types of difunctional organolithium initiators have been prepared by addition of sec or tert-butyl lithium on two families of non polymerizable precursors having two non-conjugated double bonds. They were made in pure hydrocarbon solvents such as n-hexane, the dilithium adducts being insoluble and easily purified by elimination of monofunctional species. However, they easily initiate the polymerization of monomers such as conjugated dienes, giving soluble and stable difunctional living polymers in the complete absence of any polar additive.     

富勒烯(C_(60))-苯乙烯-丙烯酸三元共聚物的合成及其润滑性能

通过自由基聚合合成了一种新型纳米级富勒烯 苯乙烯 丙烯酸三元共聚物,该聚合物易溶于碱性水、甲醇、四氢呋喃等溶剂。采用FTIR、UV 240等进行结构表征。TEM分析表明其在水溶液中形貌为理想的球形,平均粒径约为36nm。四球机试验测试结果表明,一定浓度的该富勒烯共聚物可有效增强抗磨能力。对其磨斑表面采用电子扫描显微镜分析,结果表明,磨痕变浅,磨斑减小,有效地降低了磨损。     

富勒烯(C60)-苯乙烯-丙烯酸三元共聚物的合成及其润滑性能

通过自由基聚合合成了一种新型纳米级富勒烯-苯乙烯-丙烯酸三元共聚物，该聚合物易溶于碱性水、甲醇、四氢呋喃等溶剂。采用FTIR、UV-240等进行结构表征。TEM分析表明其在水溶液中形貌为理想的球形，平均粒径约为36nm。四球机试验测试结果表明，一定浓度的该富勒烯共聚物可有效增强抗磨能力。对其磨斑表面采用电子扫描显微镜分析,结果表明，磨痕变浅．磨斑减小．有效地降低了磨损。