3-叠氮甲基-3-乙基氧杂环丁烷及其均聚物的合成与性能

为开发新型含能黏合剂,以三羟甲基丙烷、碳酸二乙酯、对甲苯磺酰氯、叠氮化钠为原料,合成出一种新型叠氮类氧杂环单体3-叠氮甲基-3-乙基氧杂环丁烷（AMEO）。用核磁、红外、元素分析和DSC表征了AMEO的结构与性能。以1,4-丁二醇为起始剂,三氟化硼乙醚络合物为催化剂,二氯甲烷为溶剂,AMMO为单体,借助于阳离子开环聚合,合成出聚3-叠氮甲基-3-乙基氧杂环丁烷（PAMEO）。用红外光谱、核磁共振、元素分析、羟值、数均分子质量表征和测定了聚合物的结构和性能。     

3-溴甲基-3-甲基氧杂环丁烷均聚物的合成及表征

以1,4-丁二醇(BDO)为引发剂,三氟化硼乙醚络合物(BF3·Et2O)为催化剂,3-溴甲基-3-甲基氧杂环丁烷(BrMMO)为单体,CH2Cl2为溶剂,按阳离子开环聚合机理,合成出有机黏合剂3-溴甲基-3-甲基氧杂环丁烷均聚物(PBrMMO).研究了低温条件下单体转化率随时间的变化情况,得出BrMMO转化率-时间曲线,考察了催化剂用量和反应体系温度对可控聚合的影响,确定出BrMMO可控聚合的最佳条件:BF3·Et2O与BDO的摩尔比为0.5∶1.0,0℃下加入单体并熟化3d.用IR、1HNMR、DSC及TGA对最终产物的结构与性能进行了表征.     

1-甲基-3-苯基哌嗪的合成

研究了1 甲基 3 苯基哌嗪的合成工艺。以N 甲基乙醇胺和环氧苯乙烷为起始原料,在80℃下反应4h,得到N (2 羟乙基) N 甲基 α 羟基 β 苯乙基胺,在0～10℃下将其滴加入氯化亚砜,并在45℃下反应2h,生成N (2 氯乙基) N 甲基 α 氯 β 苯乙基胺,通入过量HCl,得其盐酸盐,在40～45℃下再加入氨水反应3h,经减压蒸馏,重结晶得到目标化合物1 甲基 3 苯基哌嗪,总收率43 9%。目标化合物结构经核磁共振分析验证。     

3-硝酸酯甲基-3-甲基氧杂环丁烷的合成及表征

为发展硝酸酯聚醚黏结剂,以3-羟甲基-3-甲基氧杂环丁烷（HMMO）为底物,N2O5为硝化剂,制备了一种含能单体3-硝酸酯甲基-3甲基氧杂环丁烷（NIMMO）。讨论了N2O5与HMMO的摩尔比及反应温度对选择性硝化的影响。确定了最佳反应条件：N2O5与HMMO的摩尔比为（1．0～1.1）：1．0,温度为-15～-10℃,滴加完毕后待温度下降时立即中和终止反应。通过红外、核磁及元素分析对产品进行结构表征,表明是目标化合物,差热分析表明NIMMO的热稳定性较好。     

3-叠氮甲基-3-甲基氧杂环丁烷与四氢呋喃共聚醚的合成与表征

以1,4-丁二醇(BDO)为引发剂,三氟化硼·乙醚(BF3·Et2O)为催化剂,使3-叠氮甲基-3-甲基氧杂环丁烷(AMMO)与四氢呋喃进行本体法阳离子开环聚合,得到3-叠氮甲基-3-甲基氧杂环丁烷与四氢呋喃的共聚醚(PAT).通过红外光谱、核磁共振氢谱、碳谱和凝胶渗透色谱对共聚醚进行表征.结果表明,合成的共聚醚中两种不同结构单元的摩尔比与投料比基本吻合,共聚醚的相对分子质量可控、分布较窄.差热扫描量热法测得PAT的玻璃化转变温度为-59.2℃,分解峰温为264.1℃,表明其具有良好的低温性能和热稳定性.     

胺基取代单茂钛/甲基铝氧烷催化乙烯聚合

采用胺基取代单茂钛{Cp*TiCl2N[Si(CH3)3]2}与甲基铝氧烷组成的催化体系进行乙烯聚合,得到聚乙烯 (PE)。该体系催化活性在40℃下最高,达78．5 kg,(mol·h)。PE的相对分子质量随聚合温度的下降有明显增大,在 0-60℃时重均分子量为(16-60)×104。对PE的差示扫描量热法及核磁共振碳谱表征结果表明,通过控制不同的聚合条件,PE的熔融温度可以在118-130℃变化。聚合温度和n(Al)/n(Ti)对PE的支化度都有显著影响,PE的支化类型主要为丁基支链。     

含能粘合剂合成研究新进展(续一)

<正> (上接第4期)4取代环氧丁烷聚合物合成4.1取代环氧丁烷的可控聚合3,3-双(叠氮甲基)环氧丁烷(BAMO)和3-叠氮甲基-3-甲基环氧丁烷(AMMO)均聚和共聚醚以及与四氢呋喃的共聚醚是目前人们研究最为深入的叠氮甲基取代环氧丁烷聚合物。与取代缩水甘油醚单体比较,尽管环氧丁烷和环氧丙烷母体的环张力大致相同,但在阳离子开环聚合过程中,后者存在严重的链“回咬”副反应,生成环齐聚物,使得最终聚合产物的相对分子质量和官能度难以提高。可利用环氧丁烷     

星形环氧化聚异戊二烯偶联活性聚异戊二烯基锂的研究

以正丁基锂为引发剂、环己烷为溶剂,在异戊二烯负离子聚合体系中加入新型偶联剂星形环氧化聚异戊二烯进行偶联反应,合成了星形多支化聚异戊二烯,考察了偶联剂用量、偶联剂环氧度、偶联反应时间及偶联温度对偶联反应的影响。结果表明,在偶联剂环氧基的摩尔总量与聚异戊二烯基锂的摩尔总量的比值为1.0、环氧化聚异戊二烯环氧度为20%~70%、反应时间为48 h、反应温度为60℃的条件下可合成偶联效率较高的支化聚异戊二烯。     

3-甲基-喹噁啉-2-羧酸的合成

以喹乙醇为原料,经酸性还原,碱性水解、中和后得到3-甲基-喹噁啉-2-羧酸,探讨了反应条件对产率的影响。结果表明,喹乙醇在铁粉的酸性水溶液中活化后,85~90℃还原1 h,有机溶剂萃取得到N-羟乙基-3-甲基-2-喹噁啉酰胺,而后在12%氢氧化钠溶液中80~90℃水解6 h,盐酸酸化,得到纯度大于98%的3-甲基-喹噁啉-2-羧酸,总收率为60.6%。     

3-氯-2-甲基-2-羟基丙基脲的合成

采用2-甲基环氧氯丙烷、尿素为原料．对合成3-氯-2-甲基-2-羟基丙基脲的方法进行了研究。最佳工艺条件为：原料体积比V（2-甲基环氧氯丙烷）／V（50％尿素水溶液）=0．58,反应温度为70～80℃,反应时间为75min,C（Na3PO4）=0．1mol／L10mL．所得产物的环氧值和氯离子生成率都比较小,产物以3-氯-2-甲基-2-羟基丙基脲为主。     

3-叠氮甲基-3-甲基氧丁环的合成

以三羟甲基乙烷与碳酸二乙酯为原料,经环化反应合成了3-羟甲基-3-甲基氧丁环(HMM O)。在低温下,HMM O与对甲苯磺酰氯反应生成3-磺酸酯甲基-3-甲基氧丁环(M TM O)。M TM O和叠氮化钠发生叠氮化反应形成叠氮单体3-叠氮甲基-3-甲基氧丁环(AMM O)。三步反应收率分别为76%,96%,85%。用核磁、红外、元素分析和DSC表征了化合物的结构与性能。结构鉴定表明为目标化合物AMM O。     

Hyperbranched poly(3-ethyl-3-hydroxymethyloxetane) via anionic polymerization

Anionic polymerization of 3-ethyl-3-hydroxymethyl oxetane was achieved using NaH with coinitiators benzyl alcohol (BA) or trimethylol propane (TMP). Pendent hydroxyls facilitate a multibranching polymerization. NMR confirmed the presence of linear, dendritic, and terminal repeat units. For TMP initiated polymerizations there was an acetone soluble portion which was more branched (DB=0.48) than the acetone insoluble portion (DB=0.20). Polymers were not soluble in water, ether or THF, but were partially soluble in acetone and completely soluble in methanol, benzene, chloroform, and DMSO. MALDI-TOF analysis showed relatively low molecular weights (around 500) and confirmed the presence of both cyclic and TMP endgroups.     

Atom transfer radical polymerization of methyl acrylate from a multifunctional initiator at ambient temperature

A multifunctional initiator for ATRP has been synthesized by reacting a hyperbranched polyether, based on 3-ethyl-3-(hydroxymethyl)oxetane, with 2-bromo-isobutyrylbromide. The macroinitiator contained approximately 25 initiating sites per molecule. It was used for the atom transfer radical polymerization of methyl acrylate mediated by Cu(I)Br and tris(2-(dimethylamino)ethyl)amine (Me₆-TREN) in ethyl acetate at room temperature. This yielded a co-polymer with a dendritic-linear architecture. The large number of growing chains from each macromolecule increases the probability of inter-and intramolecular reactions. In order to control these kinds of polymerizing systems and prevent them from forming a gel, the concentration of propagating radicals must be kept low. The polymerizations under these conditions were well controlled. When a ratio of initiating sites-to-catalyst of 1:0.05 was used, the polymers from all of the reactions had a low polydispersity, ranging from 1.1 to 1.4. None of the polymerizations under these conditions gave gelation. Monomer conversions as high as 65% were reached while maintaining control over the polymerization.     

3-溴甲基-3-氰乙氧基甲基氧丁环的合成

3 溴甲基 3 羟甲基氧丁环 (BMHMO)与丙烯腈 (AN)发生加成反应 ,生成 3 溴甲基 3 氰乙氧基甲基氧丁环 (BMCMO)。考察了催化剂、反应时间、BMHMO与AN的量比对反应的影响。确定出最佳的反应条件为 :w(NaOH) =2 0 %的水溶液为催化剂 ,n(BMHMO)∶n(AN) =1.0∶1.3,AN滴加完毕后在室温下搅拌 2～ 3h ,此时减压蒸馏可得到产品 ,产率 86 %。     

Synthesis and properties of cationic photopolymerizable hyperbranched polyesters with terminal oxetane groups by the couple-monomer polymerization of carboxylic anhydride with hydroxyl oxetane

The hyperbranched polyesters with terminal oxetane groups were synthesized via couple-monomer methodology based on carboxylic anhydride and hydroxyl oxetane. Two competitive reactions, ring-opening reaction of carboxylic group with oxetane group and esterification of carboxylic group with hydroxyl group, occurred synchronously during the polymerization. The results showed that the hyperbranched polyesters, poly(SA-EHO) and poly(SA-EHPO), were synthesized successfully when succinic anhydride (SA) was selected to react with 3-Ethyl-3-(hydroxymethyl)oxetane (EHO) and 3-ethyl-3-((4-hydroxymethyl)phenoxymethyl)oxetane (EHPO), respectively. The degree of branching was determined to be about 0.7 for poly(SA-EHO) from the ¹H NMR result, which was higher than those reported in literature, indicating that the esterification was dominant. The glass transition temperatures (T_g)s were measured as −11.5 °C for poly(SA-EHO) and 14.3 °C for poly(SA-EHPO) by DSC. The number average molecular weights were 1914 g/mol and 2108 g/mol with the polydispersity indices of 2.39 and 2.28 for poly(SA-EHO) and poly(SA-EHPO), respectively. Both poly(SA-EHO) and poly(SA-EHPO) were added to bisphenol A epoxy resin, EP828, with different contents and cured under UV exposure. From the DMTA and tensile results, the UV cured poly(SA-EHPO) showed higher T_g and tensile strength compared with poly(SA-EHO) because of the existence of phenyl group in poly(SA-EHPO) chain. Moreover, both the T_gs and mechanical strength decreased, whereas the elongation percents at break increased with poly(SA-EHO) and poly(SA-EHPO) increased. This indicates that the flexibility of cured films was improved by the addition of poly(SA-EHO) and poly(SA-EHPO) in the formulations.     

6-乙酰氧基-4(3氢)-喹唑啉酮的合成

以2-氨基-5-羟基苯甲酸为原料,与甲酰胺环合得到6-羟基-4(3氢)-喹唑啉酮,再用乙酸酐酯化得到6-乙酰氧基-4(3氢)-喹唑啉酮。研究了每步反应的投料比和反应温度对收率、纯度的影响。结果表明,①6-羟基-4(3氢)-喹唑啉酮的最佳工艺条件为:2-氨基-5-羟基苯甲酸与甲酰胺的摩尔比是1∶15,温度160℃,反应时间4 h;②6-乙酰氧基-4(3氢)-喹唑啉酮的最佳工艺条件为:6-羟基-4(3氢)-喹唑啉酮与乙酸酐的摩尔比是1∶1.2,温度80℃,反应时间3 h;两步反应的总产率达96%,产物纯度>99.0%。     

La-Al2O3催化正丁醛自缩合合成辛烯醛反应

辛醇(2-乙基己醇)是一种重要的增塑剂醇。正丁醛自缩合合成辛烯醛是工业生产辛醇的重要步骤之一。为克服工业正丁醛自缩合反应因使用强碱水溶液催化剂所带来的设备腐蚀、污染环境、生产成本高等缺点,采用La改性γ-Al₂O₃催化剂(La-Al₂O₃)催化正丁醛自缩合反应。首先研究了制备方法和制备条件对La-Al₂O₃催化性能的影响,发现采用胶溶法、于700℃下焙烧4 h得到的La-Al₂O₃催化性能较好,具有相互匹配的酸碱中心是催化性能较好的关键。以适宜条件下制备的La-Al₂O₃为催化剂,研究了反应条件对正丁醛自缩合反应的影响,得到适宜的反应条件为:催化剂与正丁醛质量比为0.15、反应温度180℃、反应时间8 h。在此条件下,正丁醛的转化率最高达到90.6%,辛烯醛的选择性为91.7%。该催化剂重复使用4次,催化活性无明显下降。通过对反应液进行GC-MS分析,确定了正丁醛自缩合反应体系中的副产物,进而推测了可能的副反应,建立了La-Al₂O₃催化正丁醛自缩合合成辛烯醛的反应网络。     

3-乙基-2-羟基-2-环戊烯-1-酮的合成研究

以正丁酸乙酯和草酸二乙酯为主要原料,合成了香料化合物3-乙基-2-羟基-2-环戊烯-1-酮。首先由正丁酸乙酯和草酸二乙酯经Claisen缩合生成2-乙基-3-羰基-丁二酸乙酯,其与丙烯酸乙酯发生Michael加成,随后Dieckmann酯缩合得到5-乙基-3,5-二乙酯基-2-羟基-2-环戊烯-1-酮,然后经水解脱羧获得3-乙基-2-羟基-2-环戊烯-1-酮。初步考察并优化了各步反应的工艺条件,产品总收率达44.46%。     

Synthesis and characterization of acrylate–oxetane interpenetrating polymer networks through a thermal-UV dual cure process

In the present work, a thermal-UV dual-cure process was performed on acrylate–oxetane systems. A 1:1 molar mixture of difunctional acrylate–oxetane mixture was prepared starting from 2,2-Bis(4-(3-acryloxy-2-hydroxypropoxy)phenyl)propane (BPADA) and 3-ethyl-3-{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (OXT-221, DOX). Following a difunctional oxetane-acrylic monomer (OXAC) was synthesized.     

Core–shell type multi‐arm azide polymers based on hyperbranched copolyether as potential energetic materials in solid propellants

A series of novel multi‐arm azide copolymers (POGs) with the same hyperbranched poly[3‐ethyl‐3‐(hydroxymethyl)oxetane] core (PEHO‐c) and different content of linear glycidyl azide polymer shell (GAP‐s) have been synthesized by sequential cationic ring‐opening polymerization and azidation. Detailed structural information of these copolyethers was deduced from Fourier transform infrared, ¹H NMR and inverse gated decoupled ¹³C NMR spectroscopies, matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry, gel permeation chromatography and elemental analysis. The molecular weight of POG having GAP‐s and PEHO‐c with a molar ratio 14.95:1 (R_s/c) was around 31 000 g mol^?1, far above that of linear GAP (around 4000 g mol^?1). The apparent viscosity and glass transition temperature (?51 to ?23 °C) decreased first and then slightly increased with increasing molecular weight. Thermal analysis revealed that all the obtained POGs exhibited excellent resistance to thermal decomposition up to 220 °C. Moreover, the energetic properties, investigated using oxygen bomb calorimetric measurements, indicated that the enthalpy of formation of the POGs was higher than that of general linear GAP, but similar to that of branched GAP under reasonable R_s/c. The compatibilities of the POGs with common materials used in solid propellants were studied using differential scanning calorimetry and the results indicated that the POGs had good compatibility with these materials. © 2017 Society of Chemical Industry