氯化聚乙烯的热可逆共价交联

采用新型热可逆共价交联剂 ,以溶液反应法使氯化聚乙烯 (CPE)交联制得了凝胶量在 80 %左右的共价交联CPE ,研究了不同牌号CPE、催化剂及其用量、反应温度、反应时间及交联剂用量对CPE交联程度的影响 ,并测定了共价交联CPE的热可逆转化特性     

聚氯乙烯的热可逆共价交联

利用环戊二烯 (CPD)在常温下自动二聚形成双环戊二烯 (DCPD)、在高温下DCPD又可解聚成CDD的热可逆Diels Alder反应 ,合成了DCPD二羧酸衍生物 ,并将其引作聚氯乙烯 (PVC)的共价交联 ,研究了交联剂种类和用量对交联程度、力学性能和流动特性的影响及交联产物的热可逆转化行为 ,制得了力学性能和耐热性均有所提高的热可逆共价交联PVC     

热可逆共价交联氯化聚乙烯的制备和性能

以双环戊二烯二羧酸钾 [DCPD(COOK) 2 ]为交联剂 ,通过共混反应法制得了共价交联的氯化聚乙烯(CPE)热塑性弹性体 (TPE) ,研究了共混反应条件 (温度、时间及交联剂用量等 )对TPE物性的影响 .反应溶解性和IR测定数据证明 ,DCPD(COOK) 2 与CPE分子链上的活性氯反应形成共价酯键而交联 ;物性测定数据表明 ,交联CPE的主要力学性能接近CPE常规硫化胶 ,不同的是该交联聚合物具备可塑性 ,经反复加工三次后 ,其力学性能还略有提高     

活性氯型丙烯酸酯橡胶的热可逆共价交联

利用热可逆季铵化反应特性,将含叔胺功能基团的聚合物用于活性氯型丙烯酸酯橡胶(ACM)的热可逆共价交联。通过乳液聚合方法合成了丙烯酸丁酯(BA)/4-乙烯基吡啶(4-VP)共聚物交联剂,考察了交联剂用量、模压温度和模压时间对ACM交联程度、力学性能的影响,并通过DSC、变温扭矩测定、热塑再加工成型等方法研究了交联ACM胶样的热可逆性。研究表明,BA-4-VP共聚物交联的炭黑填充ACM胶样拉伸强度可达8.5MPa,并可进行热塑模压成型,再次加工成型后胶样断裂强度增大、伸长率下降。     

开环共聚法合成热可逆共价交联聚醚橡胶

以烷基铝为催化剂,双环戊二烯二甲酸双缩水甘油酯为交联单体,与环氧氯丙烷、环氧乙烷、环氧丙烷进行离子型开环共聚,制得了热可逆共价交联的聚醚橡胶．研究了聚合方法、聚合配方和工艺条件对单体转化率、共聚物组成的影响．通过 Ｉ Ｒ 和 Ｄ Ｓ Ｃ 测定及反应溶解性和高温成型实验,证明了共聚物的结构及共价交联的热可逆转化特性．     

热可逆交联环氧树脂的动态结构与性能研究

通过双马来酰亚胺与侧链带有呋喃官能团线性环氧树脂间的Diels-Alder反应,制备了热可逆交联的环氧树脂(DAERs),通过热分析、固体核磁共振技术和力学性能测试详细研究了该热可逆交联聚合物中的热可逆转变过程、动态化学键演化以及交联度对力学性能的影响.示差扫描量热法(DSC)和动态热机械分析(DMA)等热分析结果表明,可逆共价键的化学交联作用提高了材料的玻璃化转变温度,随着交联度的增大,热可逆共价键断裂及玻璃化转变协同作用导致材料软化温度显著提高,进而提高了材料的耐热性.通过变温13C固体NMR实验原位监测DA/retro-DA反应过程,发现DAERs中通过DA反应形成的交联网络结构可以在高温解交联而生成呋喃与马来酰亚胺小分子化合物,而低温时呋喃与马来酰亚胺化合物又再次反应得到DA加成结构,进而从分子水平上为材料的热可逆交联特性提供了关键的实验证据.而原样品和溶液法再加工样品的拉伸实验结果表明,可逆交联DA反应不但使样品具有较高的力学强度,而且使交联聚合物具有了再加工的能力.     

交联羧甲基壳聚糖对铅离子的吸附研究

以壳聚糖为原料,先在氨基上引入羧甲基制备出N-羧甲基壳聚糖,再和环氧氯丙烷发生交联反应,合成出新型交联羧甲基壳聚糖,FTIR表征其结构。研究了交联羧甲基壳聚糖对Pb2+的吸附性能,探讨了交联剂用量、铅离子溶液的pH值、温度、吸附时间等因素对其吸附性能的影响,并考察了交联羧甲基壳聚糖对铅离子吸附动力学和热力学实验。实验结果表明,交联羧甲基壳聚糖对铅离子的吸附量优于壳聚糖,平衡吸附量可达297.6 mg/g。交联羧甲基壳聚糖对铅离子的吸附符合准二级动力学模型和Langmuier等温吸附,吸附主要依靠结构中的羧基和氨基基团。     

磁性交联壳聚糖微球对Cu2+的吸附性能研究

以Fe_3O_4为磁核,环氧氯丙烷为交联剂,制备磁性交联壳聚糖微球(MCB)。采用FTIR、XRD及SEM对MCB进行表征分析,结果表明壳聚糖发生了交联反应,且Fe_3O_4被壳聚糖包埋。通过正交试验L_9(3~4),得到MCB的最优制备工艺条件为:环氧氯丙烷用量为3.0 mL,反应温度为45℃,反应时间为3.0 h,MCB对Cu~(2+)的吸附率可达63.70%。同时在单组分体系中研究了MCB对Cu~(2+)的吸附行为,结果表明:MCB对Cu~(2+)的最佳吸附pH值为5.0,MCB对Cu~(2+)的吸附遵循Langmuir等温吸附模型;动力学研究表明,MCB对Cu~(2+)的吸附过程符合拟二级吸附动力学方程。     

水溶性酚醛树脂的合成及其交联性能研究

考察了部分水解聚丙烯酰胺/水溶性酚醛树脂交联体系的成胶特性,发现在聚合物浓度为1.0％时,随着交联剂浓度的增加,形成的凝胶的粘度增加,交联剂用量为0.5％,凝胶强度在30 min左右达到最高值;考察了温度、物料比等水溶性酚醛树脂的合成条件对最终凝胶体系粘度的影响,最佳反应温度为60℃,甲醛苯酚的最佳摩尔比为3:1;向甲...     

基于单独MBA凝胶纤维的RAFT聚合制备聚合物微米管

研究凝胶形成温度对N,N'-亚甲基双丙烯酰胺(MBA)凝胶纤维尺寸的影响, 发现凝胶纤维平均直径随着凝胶形成温度的降低而降低, 在-25 ℃下可得到平均直径为1.1 μm的小尺寸凝胶纤维. 在不加共聚单体条件下, 以1.1 μm小尺寸MBA纤维为模板和反应单体, 通过可逆加成断裂链转移(RAFT)自由基聚合, 以较高收率得到形貌规整并有一定自支撑能力的聚合物微米管. 研究各种反应条件对聚合反应的影响, 结果表明RAFT试剂用量、引发剂用量及反应温度都会影响产物形貌及收率. 采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)和红外光谱仪表征了聚合物微米管的微观形貌和组成, 热失重分析表明产物具有很高的耐热性能.     

丙烯酸乙酯/烯丙基缩水甘油醚共聚物的热可逆共价交联

研究了双环戊二烯基二羧酸及其铵盐对丙烯酸乙酯 /烯丙基缩水甘油醚共聚物的交联反应 ,对比了二者的交联速度 .用DSC评价了它们的热可逆转化行为 .制得了热可逆部分达 79 7%的共价交联环氧型丙烯酸酯橡胶     

Thermally reversible linking of halide-containing polymers by potassium dicyclopentadienedicarboxylate

A novel crosslinker for thermally reversible covalent (TRC) linking of halide-containing polymers is suggested. Chlorine-containing polymers such as chloromethylstyrene copolymers, chlorinated polypropylene, polyvinylchloride, chlorinated polyisoprene, and polyepichlorohydrin were crosslinked with potassium dicyclopentadienedicarboxylate (KDCPDCA). The crosslinker was prepared by reacting potassium ethoxide with dicyclopentadienedicarboxylic acid. Because of the low solubility of KDCPDCA in organic solvents, a phase transfer catalyst, benzyltrimethyl-ammonium bromide, was employed for the crosslinking reaction. The crosslinking reaction occurred at a higher rate in a polar solvent, such as dimethylformamide, than in a nonpolar one, such as toluene, and was affected by the nature of the chlorine-containing polymer. Some of the polymers crosslinked even at room temperature. The chain-extending reaction between KDCPDCA and a α,ω-dihalide compound such as α,α′-dichloro-p-xylene, 1,4-dichlorobutane, or 1,4-dibromobutane also was carried out to obtain linear oligomers. The IR spectra indicated that the crosslinking and chain-extending reactions were based on the esterification between the halide carbon bonds of the polymer and the COOK groups of KDCPDCA. The flowability at 195 °C and solubility on heating in a dichlorobenzen-maleic compound mixture of the crosslinked polymers indicated that the TRC crosslinking occurred via the reversible Diels–Alder cyclopentadiene/dicyclopentadiene conversion as long as the polymer was thermally stable and did not contain olefinic CC bonds. The TRC linking also was confirmed by the rapid decrease of the specific viscosity of the obtained linear oligomers on heating. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4390–4401, 1999     

Crosslinking of chlorine‐containing polymers by dicyclopentadiene dicarboxylic salts

Alkali‐ and alkali‐earth‐metal salts of dicyclopentadiene dicarboxylic acid (DCPDCA) were prepared and employed as crosslinkers for chlorine‐containing polymers such as polychloromethylstyrene (PCMS), chlorinated polypropylene (CPP), polyepichlorohydrin (PECH), and poly(vinyl chloride) (PVC). Thermally reversible covalent crosslinks (i.e.,  DCPD bridges) between polymer chains were generated through esterification between the chlorine–carbon bonds of the polymer and the carboxylic salt groups of the crosslinker. The crosslinking reactivity decreased in the following sequence: K > Na > LiDCPDCA > alkali‐earth‐metal salts of DCPDCA. In addition, PCMS and CPP had higher gelation rates than PECH and PVC. Good flowability at about 195 °C and solubility in maleimide‐containing dichlorobenzene on heating indicated that the crosslinked PCMS and CPP exhibited thermally reversible crosslinking because of dimer/monomer (cyclopentadiene) conversion of  DCPD moieties via reversible Diels–Alder cycloaddition. Samples of PECH and PVC crosslinked by the alkali salts of DCPDCA were insoluble even when heated in maleimide‐containing dichlorobenzene. However, these crosslinked polymers could be dissolved partially after the same treatment when the crosslinker was an alkali‐earth‐metal salt of DCPDCA. Thermal degradation such as dehydrochlorination of the PECH and PVC might have been responsible for uncontrolled crosslinking because these two polymers are known to be thermally unstable. The unreacted COOK, COONa, or COOLi of the crosslinkers might have initiated base‐induced dehydrochlorination when PECH and PVC were heated at high temperatures. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 818–825, 2000     

Emulsion procedures for thermally reversible covalent crosslinking of polymers

Quaternization and dequaternization of tertiary amine compounds were employed to obtain thermally reversible ionene networks from aqueous colloidal polymer dispersions prepared via emulsion polymerization. Chlorine‐functionalized polymers prepared via the emulsion copolymerization of styrene (St), butylacrylate (BA), or both with chloromethylstyrene, and amino‐functionalized polymers prepared via the emulsion copolymerization of St, BA, or both with 2‐(dimethylamino)ethylacrylate or 4‐vinylpyridine, were reacted without polymer separation, with a ditertiaryamine crosslinker and a dihalide crosslinker, respectively, to obtain crosslinked polymers. Crosslinked polymers were also obtained via the reaction of a chlorine‐functionalized polymer dispersion with an amino‐functionalized polymer dispersion or via the drying of the polymer blend prepared from the two kinds of dispersions. Reactive solubility experiments, flowability investigations (by thermocompression at ca. 215 °C), IR, and ¹H NMR analyses of the obtained crosslinked polymers indicated that the generated ionene bridges dequaternized on heating and requaternized on cooling. In comparison with solution crosslinking, no organic solvent was employed, and simple procedures were required for the preparation of the thermally reversible covalent crosslinked polymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4373–4384, 2000     

热可逆共价交联反应及其研究进展

梗概评述了环戊二烯（ＣＰＤ）与双环戊二烯（ＤＣＰＤ）之间Ｄｉｅｌｓ－Ａｌｄｅｒ反应的特点,以及将其引作大分子间交联键的思路;以此为基础详细讨论了热可逆共价交联聚合物的分析方法。制备路线,以及利用这一反应目前所达到的研究水平和成就 。     

Synthesis of crosslinked poly(butyl methacrylate‐co‐pentaerythritol triacrylate) gel by single electron transfer‐living radical polymerization and its oil‐absorbing properties

A novel high oil‐absorbing crosslinked gel was synthesized by copolymerization of butyl methacrylate (BMA) with a small amount of pentaerythritol triacrylate (PETA) crosslinker using single electron transfer‐living radical polymerization (SET–LRP) initiated with carbon tetrachloride (CCl₄) and catalyzed by Cu(0)/hexamethylenetetramine (HMTA) in N, N‐dimethylformamide (DMF). The polymerization followed first‐order kinetics as indicated by linear increase of monomer concentration with reaction time. Effects of reaction temperature, crosslinker, initiator, and catalyst on the oil‐absorbing properties of the crosslinked gel were investigated in detail. The oil absorptions of the crosslinked gel to chloroform, toluene could reach 51.9, 34.5 g/g, respectively. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Cross-linking of Polymer of Intrinsic Microporosity (PIM-1) via nitrene reaction and its effect on gas transport property

Polymer of Intrinsic Microporosity (i.e. PIM-1) has been crosslinked thermally via nitrene reaction using polyethylene glycol biazide (PEG-biazide) as a crosslinker. The crosslinking temperature was optimized using TGA coupled with FT-IR spectroscopy. The dense membranes containing different ratios of PIM-1 to PEG-biazide were cast from chloroform solution. Crosslinking of PIM-1 renders it insoluble even in excellent solvents for the uncrosslinked polymer. The resulting crosslinked membranes were characterized by FT-IR spectroscopy, TGA and gel content analysis. The influence of crosslinker content on the gas transport properties of PIM-1, its density and fractional free volume (FFV) were investigated. Compared to the pure PIM-1 membrane, the crosslinked PIM-1 membranes showed better gas separation performance especially for CO₂/N₂, CO₂/CH₄ and propylene/propane (C₃H₆/C₃H₈) gas pairs and as well as suppressed penetrant-induced plasticization under high CO₂ pressure.