优化工艺控制,提高氯醇反应过程丙烯转化率

根据反应原理并结合生产运行情况,探讨氯醇化反应中影响丙烯转化率的因素——原料水中氯离子含量、原料水温度、氯醇化反应温度、氯丙醇浓度、原料水流量及丙烯与氯气进料量的摩尔配比等,提出通过优化工艺控制,降低丙烯消耗的措施,为环氧丙烷生产优化中间控制,降低生产成本提供重要参考。     

影响氯丙醇收率的因素与优化控制

根据反应原理并结合生产实践,定性分析、探讨了氯醇法生产环氧丙烷的关键工序———氯醇化工序中影响氯丙醇收率的因素,提出了提高氯丙醇收率的优化控制措施。     

氯醇化反应影响因素探讨

着重对环氧丙烷生产中的关键步骤－氯醇化反应的影响因素进行了探讨,分析了丙烯纯度,氯醇化反应温度,产物氯丙醇浓度对氯醇化反应的影响,期望能对环氧丙烷的优化生产和提质降耗起到一定作用。     

氯醇化反应影响因素探讨

着重对环氧丙烷生产中的关键步骤———氯醇化反应的影响因素进行了探讨,分析了丙烯纯度、氯醇化反应温度、产物氯丙醇浓度对氯醇化反应的影响,期望能对环氧丙烷的优化生产和提质降耗起到一定作用。     

氯化铋催化合成1-苯胺基-2-丙醇

1-苯胺基-2-丙醇的合成方法主要有两种,一种是以苯胺和环氧丙烷为原料进行合成,另一种是以苯胺和1-氯-2-丙醇为原料进行合成.我们在实验中发现,在BiCl3存在下不加任何溶剂,苯胺和环氧丙烷即可在室温下高收率合成1-苯胺基-2-丙醇.     

联苯取代哌嗪丙醇类α1受体阻滞剂的合成

芳基哌嗪类化合物是一类具有α1受体亚型选择性的α1受体阻滞剂。文章采用苯酚与3-氯-1,2-环氧丙烷反应得到苯氧基取代环氧丙烷,再用联苯取代哌嗪对环氧开环,合成了联苯取代哌嗪-2-丙醇类衍生物,总收率达64%以上。合成的目标化合物均经MS和1H-NMR谱进行了结构确认。     

氯丙醇皂化制环氧丙烷反应过程研究

通过考察氯丙醇与Ca（OH）2皂化反应过程以及环氧丙烷在Ca（OH）2环境下水解反应过程,得到氯丙醇皂化与环氧丙烷水解反应数据,并借助Origin回归得到动力学反应方程,比较不同温度、碱倍率下氢氧化钙与氯丙醇反应过程中皂化与水解反应的差异,为环氧丙烷生产过程的模拟与优化提供数据支持和理论基础。     

氯丙醇减压皂化生产环氧丙烷

氯丙醇减压皂化生产环氧丙烷＊刘家祺孙广智刘禾（天津大学化工系，天津３０００７２）（天津化工设计院，天津３００１９３）氯丙醇减压皂化生产环氧丙烷＊刘家祺孙广智刘禾（天津大学化工系，天津３０００７２）（天津化工设计院，天津３００１９３）关键词氯丙醇环氧丙...     

工业色谱在环氧丙烷装置上的应用

采用氯醇法生产环氧丙烷,首先要将丙烯和氯输入氯化塔中与水进行次氯酸化反应,生成中间产品氯丙醇,然后将氯丙醇与石灰乳输入皂化塔进行皂化反应,再经精馏后得到环氧丙烷。在次氯酸化反应过程中,为了充分利用     

1-取代苯氧基-3-(4-芳基-1-哌嗪)-2-丙醇类α_1-受体拮抗剂的合成及生物活性

为寻找高选择性的α1-受体拮抗剂,该文分别以3-羟基二苯甲酮和4-甲氧基苯酚为原料,在碱性条件下与3-氯-1,2-环氧丙烷(Ⅱ)发生取代反应,得到3-取代苯氧基-1,2-环氧丙烷(Ⅲ),再经芳基哌嗪开环合成了7个3-苯甲酰基苯氧基取代和对甲氧基苯氧基取代的哌嗪-2-丙醇类化合物(Ⅴa~Ⅴg),其结构经1HNMR、MS、IR和元素分析确证。采用大鼠离体肛尾肌张力实验对目标化合物的α1-受体拮抗活性进行了测试,结果显示,这些化合物均具有较好的α1-受体拮抗活性(pA2>6),其中化合物(Ⅴg)活性最强(pA2=8.13±0.25)。     

Synthesis of amphiphilic macrocyclic graft copolymer consisting of a poly(ethylene oxide) ring and multi-poly(?-caprolactone) lateral chains

A series of amphiphilic macrocyclic graft copolymers composed of a hydrophilic poly(ethylene oxide) as ring and hydrophobic poly(?-caprolactone) as lateral chains with different grafting lengths and densities of side chains were prepared by a combination of anionic ring-opening polymerization and coordination-insertion ring-opening polymerization. The anionic ring-opening copolymerization of ethylene oxide (EO) and ethoxyethyl glycidyl ether (EEGE) was carried out first using triethylene glycol and diphenylmethyl potassium (DPMK) as co-initiators, and a linear α,ω-dihydroxyl poly(ethylene oxide) with pendant protected hydroxymethyls (l-poly(EO-co-EEGE)) was obtained. The monomer reactivity ratios of these compounds are r_1(EO) = 1.20 ± 0.01 and r_2(EEGE) = 0.76 ± 0.02, respectively. Then the ring closure of l-poly(EO-co-EEGE) was achieved via an ether linkage by reaction with tosyl chloride (TsCl) in the presence of solid KOH. The crude cyclized product containing the linear chain-extended polymer was hydrolyzed in acidic conditions first and then purified by treating with α-CD. The pure cyclic copolymer of EO and glycidol (Gly) with multipendant hydroxymethyls [c-poly(EO-co-Gly)] as the macroinitiator was used further to initiate the ring-opening polymerization of ?-caprolactone (CL), and a series of amphiphilic macrocyclic graft copolymers c-PEO-g-PCL were obtained. The final products and intermediates were characterized by GPC, NMR and MALDI-TOF in detail.     

Fluorinated ?-caprolactone: Synthesis and ring-opening polymerization of new α-fluoro-?-caprolactone monomer

Fluorinated polyester was synthesized from a novel α-fluoro-?-caprolactone monomer (α-FCL). The monomer was synthesized from commercially available cyclohexene oxide in three steps. Baeyer-Villiger reaction using 3-chloroperoxybenzoic acid of the corresponding 2-fluorocyclohexanone resulted in formation of two isomeric lactones α-and-?-fluoro-?-caprolactones in 1:1.2 molar ratio, respectively. Poly(α-fluoro-?-caprolactone) was synthesized by bulk ring-opening polymerization of α-fluoro-?-caprolactone monomer (α-FCL) catalyzed by stannous octanoate, Sn(Oct)₂ at 120 °C for 6 h. Relationships between reaction time, polymer yield, and molecular weight were established. The ring-opening polymerization of ?-fluoro-?-caprolactone (?-FCL) produce geminal fluorohydrin, which is not stable and it is subsequently dehydrofluorinated to give the corresponding aldehyde. Copolymerization of α-FCL with ?-caprolactone (?-CL) in various feed ratios was also investigated. Detail microstructure analyses of the copolymers were accomplished from ¹H, ¹³C and 2-D NMR data. Presence of fluorine atoms is expected to regulate the chemical and physical properties of the polyester.     

纳米氧化锌催化丙交酯开环聚合的研究

采用纳米氧化锌为催化剂进行L-丙交酯(L-LA)的开环聚合,研究了催化剂用量、反应温度和反应时间对聚合反应的影响.结果表明,纳米氧化锌在催化聚合转化率和聚合产物分子量上,均显示出较好的催化性能.采用了FTIR、DSC、WAXD等方法对聚乳酸的结构进行了表征,结果表明聚乳酸是L-丙交酯开环聚合产物.     

丙交酯与聚乳酸的合成

以D,L-乳酸为单体,氧化锌为催化剂,将乳酸合成D,L丙交酯;再以辛酸亚锡为催化剂,使丙交酯单体开环聚合制备聚乳酸。结果表明,乳酸在130℃、氧化锌质量分数为1.1%时,其粗产品产率大于60%;丙交酯聚合时,辛酸亚锡用量为0.02 mL时,聚合温度为160℃,常压聚合5 h即可得到粘均分子质量为6.0×104的聚乳酸;测试结果表明丙交酯在辛酸亚锡作用下发生了开环反应。     

SG1-based alkoxyamine bearing a N-succinimidyl ester: A versatile tool for advanced polymer synthesis

This paper reports the preparation of a MAMA-SG1 (BlocBuilder™) derived alkoxyamine bearing a N-succinimidyl (NHS) ester group 1, valuable for functional and advanced polymer synthesis. This alkoxyamine was exploited following two strategies: (i) a post-functionalization approach based on the transformation of α-NHS chain ends of polymers previously obtained by nitroxide mediated polymerization (NMP) from 1 (path A) and (ii) a pre-functionalization approach based on the functionalization of alkoxyamine 1 prior to NMP (path B). Path A was demonstrated by derivatization of α-NHS functionalized polystyrenes with ethanolamine, yielding hydroxyl-functionalized polystyrenes. Path B was illustrated by two examples: first, a OH functional alkoxyamine initiator, prepared by reaction of 1 with ethanolamine, was used for the synthesis of polystyrene-b-poly(d,l-lactide) by combining NMP and ring-opening polymerization. Secondly, a poly(propylene oxide)-SG1 macroalkoxyamine, obtained from reaction of 1 with NH₂-functionalized poly(propylene oxide), was used as a macroinitiator for NMP of styrene to obtain a PS-b-PPO block copolymer.     

微量活性引发剂促进惰性引发剂引发环氧乙烷的开环聚合速率研究

研究了利用微量更活泼的阴离子引发剂促进具引发惰性的磺胺嘧啶钠引发环氧乙烷开环聚合的反应速度，作了系列比较，并讨论了其影响速率的机制。     

Synthesis of novel amphiphilic graft copolymers composed of poly(ethylene oxide) as backbone and polylactide as side chains

A well-defined amphiphilic comb-like copolymer of poly(ethylene oxide)(PEO) as main chain and polylactide (PLA) as side chain was successfully prepared via a combination of anionic polymerization and coordination-insertion ring-opening polymerization. The anionic copolymerization of ethylene oxide (EO) and ethoxyethyl glycidyl ether (EEGE) was carried out using potassium 2-(2-methoxyethoxy)ethoxide as initiator, and then ethoxyethyl groups of EEGE units of the copolymers obtained were removed by hydrolysis. Two copolymers of methoxypoly(ethylene oxide-co-glycidol) [mpoly(EO-co-Gly)] were formed with multiple hydroxyl sites (the molar ratio values of Gly to EO in copolymers: 1/10.6 and 1/5.2; Mn: 10,100 and 5,020 respectively), and them were used further to initiate the ring-opening polymerization of lactide in the presence of stannous octoate, and a well-defined comb-like copolymer of PEO as main chain and PLA as side chain was obtained. The intermediate and final products of PEO-g-PLA were characterized by GPC and NMR in detail.     

农药杀螨剂克螨特合成研究

以对叔丁基苯酚和环氧环己烷作为起始原料,经过开环,氯磺化,酯化合成克螨特。探讨了反应机理和优惠工艺条件,总收率>81%,产品含量>92%。     

Synthesis and characterization of a novel amphiphilic poly (ethylene glycol)–poly (ε-caprolactone) graft copolymers

A series of amphiphilic graft copolymers PEO-g-PCL with different poly (ε-caprolactone) (PCL) molecular weight were successfully synthesized by a combination of anionic ring-opening polymerization (AROP) and coordination-insertion ring-opening polymerization. The linear PEO was produced by AROP of ethylene oxide (EO) and ethoxyethyl glycidyl ether initiated by 2-(2-methoxyethoxy) ethoxide potassium, and the hydroxyl groups on the backbone were deprotected after hydrolysis. The ring-opening polymerization of CL was initiated using the linear poly (ethylene oxide) (PEO) with hydroxyl group on repeated monomer as macroinitiator and Sn(Oct)₂ as catalyst, then amphiphilic graft copolymers PEO-g-PCL were obtained. By changing the ratio of monomer and macroinitiator, a series of PEO-g-PCL with well-defined structure, molecular weight control, and narrow molecular weight distribution were prepared. The expected intermediates and final products were confirmed by ¹H NMR and GPC analyzes. In addition, these amphiphilic graft copolymers could form spherical aggregates in aqueous solution by self-assemble, which were characterized by transmission electron microscopy, and the critical micelle concentration values of graft copolymers PEO-g-PCL were also examined in this article.     

Synthesis of α,ω-hydroxyalkyl telechelic polydimethylsiloxane soft segments and preparation of waterborne polyurethane–polydimethylsiloxane block copolymers

In this paper, by optimizing synthesis process of α,ω-hydroxyalkyl telechelic polydimethylsiloxane, α,ω-bis(3-(1-methoxy-2-hydroxypropoxy)propyl)polydimethyl siloxane (PMTS), the yield of hydrosilylation product, 1,3-bis(glycidoxypropyl) tetramethyldisiloxane exceed 86.5%. By tracing the change of methanol (gravimetry) and measuring the change of molecular weights of polydimethylsiloxanes at different reaction time (titration), the optimum reaction time of methoxylation reaction and ring-opening polymerization was determined as 8 and 12 h. Using α,ω-bis(3-(1-methoxy-2-hydroxypropoxy)propyl)polydimethyl siloxane with different molecular weights, waterborne polyurethane–polydimethylsiloxane block copolymer were prepared. The influences of molecular weights and content of α,ω-hydroxyalkyl telechelic polydimethylsiloxane on the waterborne polyurethane–polydimethylsiloxane block copolymers were investigated in detail. The addition of α,ω-hydroxyalkyl telechelic polydimethylsiloxane could improve the water-resistance property obviously and increase the elongation at break. However, the mechanical property was reduced with increase of content and molecular weight of α,ω-hydroxyalkyl telechelic polydimethylsiloxane.