高分子量线性聚二氯磷腈的合成研究

由六氯环三磷腈(HCCP)熔融开环合成聚二氯磷腈(PDCP),讨论了原料纯化、聚合温度、催化剂、聚合时间等因素对聚合反应的影响。结果表明,合成高分子量线性聚二氯磷腈的合适条件为:经过重结晶、升华处理的HCCP,在260℃无水三氯化铝催化下,聚合12¹7 h,可得到高分子量线性聚二氯磷腈,产率达90%以上,相对分子质量达9.5×10517 h,可得到高分子量线性聚二氯磷腈,产率达90%以上,相对分子质量达9.5×105¹1.6×105。     

高分子量线性聚二氯磷腈的合成研究

由六氯环三磷腈(HCCP)熔融开环合成聚二氯磷腈(PDCP),讨论了原料纯化、聚合温度、催化剂、聚合时间等因素对聚合反应的影响。结果表明,合成高分子量线性聚二氯磷腈的合适条件为:经过重结晶、升华处理的HCCP,在260℃无水三氯化铝催化下,聚合12~17 h,可得到高分子量线性聚二氯磷腈,产率达90%以上,相对分子质量达9.5×105~11.6×105。     

聚二氯磷腈制备工艺的研究

以六氯环三磷腈为原料,直接热开环聚合制备线性聚二氯磷腈。深入探讨了影响聚二氯磷腈合成的因素,找出了最佳的合成工艺,即反应温度250℃,反应时间10h,产品提纯的工艺为:先用苯将其溶解再用正庚烷提取,最高收率为64%,并采用红外(FT-IR)光谱对产物的结构进行表征。     

微生物法生产丙烯酰胺技术

介绍了丙烯酰胺的生产过程。微生物与化学催化法生产丙烯酰胺进行了比较，有很多优点；反应在常温，常压下进行下，能耗低，设备操作简单，安全，丙烯腈轮率达９９．９９％；产品纯度高，适于生产“三次采油”用超高分子量聚丙烯酰胺。     

悬浮聚合法制取不同分子量级别的聚甲基丙烯酸甲酯

采用粉状MgCO3 作为分散剂 ,悬浮聚合制取了分子量从 2 4× 10 4 ～ 2 5 4× 10 4 的聚甲基丙烯酸甲酯。考察了温度、引发剂种类和浓度、分子量调节剂、转化率对聚合物分子量的影响规律 ,用粘度法测量了聚合物聚甲基丙烯酸甲酯 (PMMA)的分子量。结果表明 :温度的升高、引发剂浓度的增大、分子量调节剂的加入都会导致分子量的减小 ,随着转化率的提高 ,聚合物的分子量增大。在同等条件下 ,引发剂过氧化苯甲酰 (BPO)聚合所得的分子量较偶氮二异丁腈 (AIBN)高。通过实验 ,得到了满足作者需求的分子量 (96× 10 4 ～ 10 0× 10 4 )的聚合物的聚合条件为 :分散剂MgCO3 用量 1% ,单体∶水相 =1∶2 5 (质量比 ) ,引发剂BPO浓度 0 5 % ,反应温度 70℃ ,反应时间 3h。     

六氯环三磷腈的合成

由氯化铵和五氯化磷合成了环状和线性磷腈氯化物混合产品。最佳合成工艺条件为PCl5∶NH4Cl=1∶1 3,反应时间 6～ 7h。在最佳合成工艺条件下制备的纯六氯环三磷腈的熔点为 112 6～ 114℃。本实验发现氯化铵的颗粒度对产品收率有影响 ,氯化铵的粒度越小 ,产品收率越高。另外 ,在溶剂四氯乙烷回收使用时产品收率有所下降。     

六氯环三磷腈合成新工艺

提出了五氯化磷气化法合成六氯环三磷腈新工艺。以氮气做载气,五氯化磷气态进料,与氯化铵在惰性有机溶剂中催化反应合成了六氯环三磷腈。在N2流量60mL/min,五氯化磷升华温度170℃,溶剂用量110mL,反应温度131±1℃,ZnCl20.1g,PCl523.1g,NH4Cl5.4g,反应时间185min条件下得粗磷腈12.0g,收率92.31%。经精制,得到六氯环三磷腈7.9g,总产率达40%(以五氯化磷计)。产品六氯环三磷腈熔点112.4～114℃。元素分析结果N11.98%,P26.50%,Cl60.64%;用IR谱、质谱进行了表征。     

利用Heck反应制备立构规整聚(3-己基噻吩)

采用Heck反应法合成了具有较高分子量和立构规整度的聚(3-己基噻吩)。研究了溶剂的种类及配比、相转移催化剂及催化剂的种类以及反应温度、反应时间对所得聚(3-己基噻吩)的分子量和规整度的影响。用凝胶色谱(GPC)和核磁共振谱(1HNMR)对聚(3-己基噻吩)的分子量及立构规整度进行了表征。用紫外-可见分光光度计和荧光分光光度计研究了聚(3-己基噻吩)的吸收光谱和发射光谱。结果表明,当溶剂为二甲基甲酰胺与四氢呋喃(DMF:THF=1:1)的混合溶剂,采用醋酸钯[用量为单体量的5%(摩尔分数)]为催化剂,四丁基溴化铵[用量为单体量的100%(摩尔分数)]为相转移催化剂时,在80℃下反应12h所得聚(3-己基噻吩)的分子量可达6700,立构规整度超过96%。     

氟烷氧基磷腈聚合物的合成硫化及性能

随着对不燃、耐油、耐低温性能硫化胶需求量的增长,美国和苏联都开展了对氟烷氧基磷腈()聚台物的合成、硫化及其性能的研究。1 的合成的主链是由氮原子和带有机侧链的磷交替组成,并有二种方法对高分子聚二氯磷腈()中的氯用氟烷氧基团进行氯的亲核取代而获得含氟磷腈聚合物(1)用碱金属的氟醇化物(氟烷氧基碱     

水溶性氧肟酸型高分子絮凝剂的研制

用聚丙烯酰胺合成氧肟酸型高分子絮凝剂,研究了温度、聚丙烯酰胺分子量、原料物料此、反应时间对反应的影响。实验结果表明：聚丙烯酰胺改性最佳反应温度是30℃,聚丙烯酰胺／盐酸羟胺（摩尔比）为1：1．5,反应时间为8h,聚丙烯酰胺分子量为3×10^6～6×10^6。     

聚合物—表面活性剂复合体系的核磁共振研究

用核磁共振（NMR）研究聚合物-表面活性剂复合体系的具体实例,分别对用于聚合物与表面活性剂相互作用及聚合物-表面活性剂团族结构剖析等领域的^13C-NMR、^13C-及反离子^23Na^ -弛豫、顺磁共振驰豫（PR-NMR）、二维核子Overhauser增强核磁共振（2D-NOESY-NMR）等手段作了详尽的概述,在^13C-NMR研究中发现PVP-C12BE体系台PVP骨架上α-CH、β-CH2和吡咯环上与N相连的亚甲基吸附在C^12BE胶束表面的碳氢链部位,其相互作用驱动力为疏水力。^13CNMR、^23Na^ -NMR研究表明在PEG-SDS团族结构中大部分PEG链节环绕在SDS胶束周围,少部分PEG链节吸附在烃/水界面上;2D-NOESY-NMR研究结果表明,有少部分PEG链节渗入到SDS胶束内部;PR-NMR结果显示少部分PEG链节存在于SDS胶束双电层内,PEG-SDS团族的化学计量组成为PEG/SDS=1.9。^13C-NMR研究表明PVP-AS团族为项链状结构,PVP-AS团族为项链状结构,PVP-SDS团族为膨胀笼状结构。     

Characterization of epoxidized natural rubber by 2D NMR spectroscopy

Assignment of signals in aliphatic region of ¹H NMR spectrum for epoxidized natural rubber was carried out through NMR spectroscopy. The epoxidized natural rubber was prepared by epoxidation of purified natural rubber with peracetic acid in latex stage followed by degradation with propanal and ammonium persulfate. The resulting liquid epoxidized natural rubber was characterized through 1D- and 2D-NMR spectroscopy. The unknown signals in the aliphatic region of the ¹H NMR spectrum were assigned through ¹³C NMR and two-dimensional heteronuclear shift correlation (HETCOR) measurement. The assignments were proved by two-dimensional inverse detected heteronuclear long-range shift correlation (HMBC) and two-dimensional homonuclear shift correlation (COSY) measurements, and they were supported with epoxidized squalene as a model compound through NMR spectroscopy.     

~(15)N标记的苯基五唑的合成、表征及分解反应机理

以15 N标记的亚硝酸钠和叠氮化钠为原料,低温下合成出15 N标记的对甲氧基苯基五唑(p-MOPP)和对叔丁基苯基五唑(p-tBPP)。利用低温1 H NMR、13 C NMR和15 N NMR等一维核磁技术及gHSQC和gHMBC等二维核磁技术进行了p-tBPP的1 H、13 C、15 N NMR谱化学位移全归属。通过变温1 H NMR和15 N NMR研究了五唑化合物的稳定性,推测了其分解反应机理。     

高支化度酯类增塑剂的结构鉴定

利用AV50 0核磁共振波谱仪鉴定了一种从聚氨酯材料中分离出的增塑剂。这是一种新型的性能优良的耐迁移性脂肪族增塑剂。使用的手段有红外光谱 ,1 H NMR ,1 3C NMR ,1 3C 1 HCOSY ,1 H 1 HCOSY以及DEPT等技术。     

Determination of unsaturated fatty acid composition by high-resolution nuclear magnetic resonance spectroscopy

High-resolution nuclear magnetic resonance (NMR) spectroscopy provides useful data for analyzing fatty acid compositions of edible vegetable oils. Quantitation of each fatty acid was carried out by evaluation of particular peaks. According to the ¹H NMR method, terminal methyl protons, divinyl protons, and allyl protons are useful to calculate linolenic acid, linoleic acid, and oleic acid, respectively. The ω-2 carbon, divinyl carbon, and allylic carbons were used for calculation of these acids by the ¹³C NMR method. Compositional results obtained by NMR coincided well with those of the conventional gas chromatography (GC) method. Results from ¹³C NMR were in better agreement with those from GC than were the results obtained by the ¹H NMR method.     

Determination of unsaturated fatty acid composition by high-resolution nuclear magnetic resonance spectroscopy

High-resolution nuclear magnetic resonance (NMR) spectroscopy provides useful data for analyzing fatty acid compositions of edible vegetable oils. Quantitation of each fatty acid was carried out by evaluation of particular peaks. According to the ¹H NMR method, terminal methyl protons, divinyl protons, and allyl protons are useful to calculate linolenic acid, linoleic acid, and oleic acid, respectively. The ω-2 carbon, divinyl carbon, and allylic carbons were used for calculation of these acids by the ¹³C NMR method. Compositional results obtained by NMR coincided well with those of the conventional gas chromatography (GC) method. Results from ¹³C NMR were in better agreement with those from GC than were the results obtained by the ¹H NMR method.     

Synthesis and characterization of the layered sodium silicate ilerite

A sodium ilerite, molar ratios 1Na₂O:8.2SiO₂:10.2H₂O, was obtained with a good crystalline structure and characterized by several NMR techniques in addition to X-ray diffraction (XRD). The X-ray pattern of the as-synthesized ilerite is in very good agreement with the structure proposed by Gies and coworkers. The narrow ²⁹Si MAS NMR signals (FWHM=0.3 ppm) indicate a good short-range order of the framework. The proton dynamics influences several ²⁹Si NMR parameters. The 16 ppm signal in the ¹H MAS NMR spectra is explained by a proton in a bridging position in the short (2.3 Å) O4–O4 bonding. The quadrupole coupling constant C_qcc=100 kHz with η=0.2 for the 16 ppm signal, which was obtained from the ²H MAS NMR spectra, confirms this explanation. ¹⁷O NMR shows also a separate signal for SiOH groups but cannot resolve the three expected lines for SiOSi. PFG NMR detects a small mobile portion of water in the ilerite, which is located probably on the external surface of the crystallites. An intracrystalline diffusion coefficient of the intercalated water molecules of the order of magnitude 10⁻¹⁵ m² s⁻¹ was obtained by NMR tracer exchange experiments.     

一种二齿型离子液体的合成

以乙二醛、甲醛、氨水和叔丁胺为原料,在甲醇溶剂中合成1-叔丁基咪唑。由1-叔丁基咪唑与1,4-二溴丁烷反应合成一种二齿型离子液体——1,4-二(1-叔丁基咪唑)丁烷溴化物,产物经IR,1H NMR和13C NMR予以表征。     

离子液体1,4-二(1-异丙基咪唑)丁烷溴化物的合成研究

以乙二醛、甲醛、氨水和异丙胺为原料,甲醇为溶剂,合成1-异丙基咪唑。由1-异丙基咪唑与1,4-二溴丁烷反应,合成一种二齿型离子液体1,4-二(1-异丙基咪唑)丁烷溴化物,产物经IR、1H NMR和13C NMR予以表征。     

线型聚苯乙烯支载手性咪唑烷酮的制备

以N-叔丁氧羰基-L-酪氨酸乙酯为原料,经系列反应制备(S)-4-[4′-(对乙烯基苄氧基)苄基]-1-苯基-2-咪唑烷酮手性单体,用AIBN作引发剂,与苯乙烯溶液聚合制备线型聚苯乙烯支载的手性咪唑烷酮,用IR、1H-NMR、13C-NMR及元素分析对其结构进行表征,所得数据与其结构相吻合。