新型杂化单体4-(1-丙烯基)氧丁基缩水甘油醚的合成及光聚合性能研究

通过3步反应合成了一种新型杂化单体4-(1-丙烯基)氧丁基缩水甘油醚(POBGE)。使用傅立叶红外光谱和核磁共振仪对相应产物结构进行了表征。同时使用傅立叶实时红外(FT-RTIR)对该杂化单体的光聚合性能进行了研究。考察了引发剂种类,不同浓度光引发剂,不同光照强度对杂化单体的光聚合性能的影响。结果表明,光引发剂硫鎓盐的引发性能要优于碘鎓盐,随着光引发剂浓度以及光照强度的增大杂化单体双键及环氧基团的转化率都相应提高。     

新型杂化光聚合体系

光固化方式的复合化是对光固化体系进行改性的重要方法。通过将自由基和阳离子以及阳离子和阳离子配合组成新的光固化体系,可以得到优良的固化体系。本论文以多种丙烯酸酯,乙烯基醚,环氧树脂,以及实验室合成的杂化单体等做为基础材料进行混合杂化光聚合体系,杂化单体光聚合体系的光固化动力学比较,并对羟基化合物对各体系的影响进行分析。实验结果表明,杂化单体在转化率,转化速度,对羟基化合物不敏感性等多方面都比混合杂化体系有明显优势。     

含硫杂蒽酮类光引发剂的聚合体系的光固化研究

首次Ｎ１２１型紫外光固化测试仪研究以硫杂蒽酮为光引发剂的光聚合体系的光固化性能。为测定以硫杂蒽桐为光引发剂的光聚合体系的光聚全速度提供了新的方法，同时讨论了光 发射波长与光引发剂的吸收波长的关系。     

可聚合单组分硫杂蒽酮类光引发剂的合成及性能研究

硫杂蒽酮衍生物紫外吸收强、峰形宽、夺氢能力强,易于调控实现与LED光源的匹配。本文制备了可聚合的含助引发剂叔胺的硫杂蒽酮类光引发剂,室温呈液态,可溶解范围宽。产物在390～405 nm范围有较强吸收,摩尔消光系数达10⁴,相比硫杂蒽酮类市售商品,其最大紫外吸收峰红移15～20 nm,且具有较快的分子内电荷转移,迁移率由17.6%降为6.2%。光解性能研究表明其具有光漂白能力,与光固化单体和树脂相容性好。     

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。     

两性可聚合型丙烯酸酯单体的合成及应用

以甲基丙烯酸二甲氨基乙酯(DM)和氯乙酸钠为原料进行季铵化反应,合成一类新型的两性可聚合型丙烯酸酯单体。考察了季铵化反应时间、温度等因素对单体合成的影响,用混合指示剂两相滴定法测定反应转化率,同时用红外光谱和核磁波谱对产物结构进行了分析。结果表明:以水为溶剂,DM与ClCH2COONa的物质的量比为1∶1.05,在70℃下,反应7h,叔胺转化率可达93.97%。用上述自制单体制备高分子乳化剂,将其用于乳液聚合,制得性能优良的阳离子乳液和阴离子乳液。     

表面活性单体DMBAC光聚合动力学研究

采用偶氮二异丁脒盐酸盐(AIBA)作为光引发剂,光引发聚合并研究了阳离子表面活性单体——甲基丙烯酰氧乙基二甲基苄基氯化铵(DMBAC)的均聚及其与丙烯酰胺(AM)共聚合反应的动力学行为,聚合反应均在高于DMBAC临界胶束浓度(CMC)的条件下进行.研究结果显示DMBAC均聚合反应速率与引发剂浓度的0.29次方以及单体浓度的0.89次方成正比,均聚合反应的表观活化能约为13.74 kJ/mo1;DMBAC与AM共聚合反应速率与引发剂浓度的0.82次方以及单体总浓度的0.83次方成正比,共聚合反应的表观活化能约为10.97 kJ/mo1;同时测得DMBAC与AM共聚合反应的单体竞聚率为r1=0.27(AM)、r2=2.00(DMBAC),说明AM趋向于形成共聚物,而DMBAC更趋向于形成均聚物.     

膨润土杂化改性聚丙烯共混体系性能研究

以乙醇为分散介质,过氧化二苯甲酰为引发剂,硫代硫酸钠为催化剂,合成了与聚丙烯具有良好复配性能的膨润土杂化改性聚苯乙烯材料(PS/H)。研究了PP/PS、PP/(PS/H)共混体系的性能。结果表明:原位悬浮聚合产物粒子中存在PS及有机改性的膨润土H,且膨润土在聚合产物中分散性良好;对于PP/PS和PP/(PS/H)共混体系,PS及PS/H的加入影响了PP的结晶形态,使共混体系结晶速率增加,相同比例的共混体系PP/(PS/H)对于PP/PS而言,其熔融峰位置向低温偏移,体系熔点略低,其结晶峰位置向高温偏移,结晶温度有较明显的提高;动态温度扫描结果显示,共混体系的表观粘度随着温度的升高而降低,同等PS含量下,由于杂化体系中膨润土的引入,PP/(PS/H)体系的表观粘度高于PP/PS体系;XRD测试结果表明,在熔融共混加工过程中聚合物链没有插层到膨润土片层中。     

含甲基丙烯酰氧基的甲基丙烯酰胺单体的合成与性能研究

用甲基丙烯酰氯分别与乙醇胺和二乙醇胺反应合成了两种单体。以实时红外光谱(RT-IR)法分别研究了两种单体和三缩乙二醇双甲基丙烯酸酯(SR209)混合物的光聚合动力学性质,考察了不同引发剂对聚合性能的影响,并采用动态力学分析仪(DMA)测试了光固化后材料的力学性能。结果表明,与二苯甲酮(BP)相比,2-羟基2-甲基-1-苯基丙酮(1173)对两种单体具有较好的引发效果。两种单体加入三缩四乙二醇双甲基丙烯酸酯(SR209)中后,对体系光固化后的产物力学性能有不同影响。     

不同链长脂肪胺助引发剂的合成及光固化性能研究

通过麦克尔加成反应合成了不同链长的脂肪胺助引发剂,采用了实时红外技术对其光聚合性能进行研究,考察了不同胺链长、光引发剂浓度,不同单体对光聚合性能的影响。结果表明,随着链长的增加,光聚合反应速率和转化率没有多大的差别,在所研究的浓度范围内,随着助引发剂用量的增加,光聚合反应速率和转化率都相应的增加,对于二苯甲酮的选择有一个最佳用量,而二苯甲酮的结构对光聚合反应速率也有一定的影响,另外随着单体的官能度的增加,光聚合的反应转化率降低。     

阳离子单体的开发与应用

本文介绍了系列阳离子CHA、QSA、DMC的合成方法。研制的CHA有机杂质含量低,颜色浅;QSA醚化反应率高,产品糊液稳定;DMC工艺已建成300t/a规模的生产装置,产品质量指标达到国外同类产品水平。3种阳离子单体在造纸、油田、水处理、洗涤等方面有广泛的应用,具有良好的社会和经济效益。     

Preparation of Cyclosilalkylenesiloxane Monomers and Their Cationic ROP

A novel series of cyclosilalkylenesiloxane monomers was prepared having larger alkylene units, hexanylene, octanylene, decanylene, and tetradecanylene, than previously reported. The rings also contain at least one tetramethyldisiloxanylene unit and undergo ring-opening polymerization via the siloxane bond. Thus, poly(1,1,8,8-tetramethyl-9-oxa-1,8-disilanonanylene), poly(1,1,10,10-tetramethyl-11-oxa-1,10-disilaundecanylene), poly(1,1,12,12-tetramethyl-13-oxa-1,12-disilatridecanylene), and poly(1,1,16,16-tetramethyl-17-oxa-1,16-disilaheptadecanylene) were prepared using a strongly acidic ion exchange resin. The polymers were obtained in yields of 74–86%, similar to that obtained for cyclosiloxane equilibration polymerization. The monomers were characterized using ¹H, ¹³C, and ²⁹Si NMR, FTIR, GC-MS, and elemental analysis. The polymers were characterized using ¹H, ¹³C, and ²⁹Si NMR, DSC, TGA, FTIR, GPC, and refractive index.     

氟代聚丙烯酸酯改性阳离子型聚氨酯乳液的制备

以丙烯酸十二氟庚酯(FA)、丙烯酸羟丙酯(HpAA)为单体,通过偶氮二异丁腈(AIBN)引发聚丙烯酸酯自由基在交联的聚氨酯预聚体中进行聚合,并用N-甲基二乙醇胺(MDEA)进行亲水基扩链,溶液聚合相转化法制得新型氟代聚丙烯酸酯改性阳离子型聚氨酯复合乳液(FPUA)。对聚合物结构、乳胶粒形态进行表征。结果表明,以丙酮为溶剂,n_(NCO)/n_(OH)=1.3,MDEA质量分数6.5%、FA质量分数为8%时能得到半透明蓝光、稳定性良好的核-壳结构乳液,FPUA胶膜拉伸强度为19 MPa,吸水率为6.9%,接触角为101°,产品的耐水性优良。     

Interaction Between Nonionic and Gemini (Cationic) Surfactants: Effect of Spacer Chain Length

The interaction between mixtures of nonionic surfactant polyethylene glycol p-(1,1,3,3-tetramethyl butyl)-phenyl ether and cationic gemini surfactants alkanediyl-α,ω-bis(dimethyldodecylammonium bromide) (12-s-12, where s = 2, 4 and 6) was studied using surface tension and small-angle neutron scattering measurements. Marked interaction was observed for the investigated surfactants mixtures which depend upon the hydrophobic spacer length of the gemini surfactant and also on the fraction of nonionic surfactant in the mixed systems. The results are discussed in terms of interaction parameters calculated according to the theory of regular solutions which uses the critical micelle concentration determined tensiometrically to calculate the molecular interaction parameter and the mole fractions of the two components in the mixed micelles. A relatively high negative molecular interaction parameter value (up to −3.40) obtained for mixtures of nonionic and cationic gemini surfactant indicates a presence of strong attractive interaction in the mixed system that increases with the spacer length of the gemini surfactant. Micellar parameters deduced from small-angle neutron scattering measurements also compliment the surface tension results.     

Synthesis and Characterization of a Novel Short Fluorocarbon Chain Cationic Surfactant

A novel short fluorocarbon chain cationic surfactant has been synthesized to reduce the bioaccumulation of traditional fluorocarbon surfactants and maintain excellent surface properties simultaneously. The structure, surface activity, and micelle formation of surfactants have been investigated by surface tension, conductivity, dynamic light scattering, steady-state fluorescence, Fourier transform infrared spectroscopy, and Nuclear magnetic resonance. The novel surfactant (yield more than 81%) exhibited good surface activity, the critical micelle concentration and surface tension were below 2.35 mmol L⁻¹ and 20.54 mN m⁻¹ in the range of temperature from 288 to 303 K, respectively. The surface tension decreased to 17.45 mN m⁻¹ with an increase in temperature. The thermodynamic parameters (, and ) of micellization for surfactants were evaluated, which implying the micellization process was contributed primarily by the entropy driving. In addition, the aggregation behavior of surfactants was also studied in detail, which demonstrated a small micelle aggregation number of 9.40 and large size distribution of 164–342 nm.     

不同链长可聚合硼酸酯表面活性剂的合成及性能

以硼酸、N-羟甲基丙烯酰胺、烷基二乙醇胺等为主要原料,合成了链长为八烷基(octyl borate ester,简称为OBE)、十二烷基(lauryl borate ester,简称为LBE)和十六烷基(hexadecyl borate ester,简称为HBE)的可聚合硼酸酯表面活性剂,研究了反应溶剂、阻聚剂、反应温度等因素对收率的影响,由IR和1HNMR对产物进行了结构表征。得到的优选条件为溶剂苯50 mL、阻聚剂吩噻嗪质量分数0.8%、反应温度60℃,LBE收率可达93.3%,OBE和HBE收率分别可达95.7%和89.6%;并考察了3种硼酸酯的表面张力和乳化性能,25℃时,OBE的CMC为5.2 mmol/L,γCMC为31.8 mN/m;LBE的CMC为0.069 mmol/L,γCMC为29.5 mN/m;HBE的CMC为0.087mmol/L,γCMC为28.6 mN/m。     

Synthesis,Characterization and Aqueous Properties of a New Hybrid Fluorocarbon Cationic Surfmer

A novel hybrid fluorocarbon cationic surfmer has been synthesized and its aggregation and surface properties have been studied by surface tension, electrical conductivity, steady‐state fluorescence, Rayleigh light scattering, dynamic light scattering and transmission electron microscopy. Through surface tension, electrical conductivity, steady‐state fluorescence and Rayleigh light scattering measurements, the effectiveness of surface tension reduction, the maximum surface excess concentration, the minimum area occupied per surfactant molecule at the air/water interface, the micropolarity and aggregation number of micelles were investigated. The results shows that the surfmer has superior surface activity and lower micropolarity than other surfmers. The critical micelle concentration at different temperatures and a series of thermodynamic parameters (, , and , , , and ) of micellization were evaluated. The thermodynamic parameters showed that the micelle formation was entropy‐driven in the temperature range of 15–40 °C. The size and morphology of the aggregates were also confirmed by dynamic light scattering and transmission electron microscopy.     

不同碳链长度的离子液体对蛋白核小球藻的毒性影响研究

研究了三种不同碳链长度的咪唑类硝酸盐离子液体1-癸基-3-甲基咪唑硝酸盐([DMIM]NO_3)、1-辛基-3-甲基咪唑硝酸盐([OMIM]NO_3)、1-己基-3-甲基咪唑硝酸盐([HMIM]NO_3)对蛋白核小球藻的急性毒性的影响。结果表明,[DMIM]NO_3、[OMIM]NO_3、[HMIM]NO_3对蛋白核小球藻的半生长抑制浓度(IC_(50)-96h)分别是0.23mg/L、2.52mg/L、3.81mg/L,离子液体碳链中碳原子数越多,其IC_(50)越小,对蛋白核小球藻的毒性作用越大。三种离子液体的毒性大小:[DMIM]NO_3[OMIM]NO_3[HMIM]NO_3。