阳离子交换树脂催化合成乳酸异戊酯的研究

以阳离子交换树脂为催化剂，研究了乳酸与异戊醇合成乳酸异戊酯的反应条件，结果表明：用1.0g阳离子交换树脂作催化剂、0.1mol（9g）乳酸，当乳酸与异戊醇的摩尔比为1:2，在回流条件下反应3h后，酯产率可达87.5%，本方法具有催化活性较高，对设备无腐蚀、三废排放少，催化剂可重复使用多次等特点。     

强酸性树脂催化合成丙酸烯丙酯的工艺研究

利用强酸性阳离子交换树脂催化合成了丙酸烯丙酯，实验表明：树脂催化剂用量为1．0g，反应的酸醇量比为3：2时，反应效果较佳，产品收率达68％。同时，对树脂的重复使用性能进行了测试，结果表明：树脂在重复使用6次后，其催化性能保持不变。另外，也与其他催化剂的催化效果进行了比较，说明了强酸性树脂在合成丙酸烯丙酯中的独特优越性。并合成了乙酸烯丙酯、丁酸烯丙酯和戊酸烯丙酯。     

活性炭负载磷钨酸催化合成苹果酯

以活性炭负载磷钨酸为催化合成了苹果酯，确定了反应的最优条件，实验结果表明，催化剂的催化活性高，可重复使用。     

凹凸棒负载KF催化合成乙二醇烯丙基醚

采用浸渍法制备氟化钾/凹凸棒(KF/ATP)固体碱催化剂,催化丙烯醇与环氧乙烷(EO)反应合成乙二醇烯丙基醚。考察了催化剂焙烧温度、KF负载量对催化性能的影响,采用X射线衍射(XRD)、透射电子显微镜(TEM)、Hammett指示剂法等手段对催化剂进行表征。结果表明:焙烧温度为400℃,KF负载量为30%时,生成的活性组分K2MgF4均匀分散在ATP表面,K2MgF4与KF的协同作用使得催化剂对烯丙醇和EO反应的催化活性最高。KF/ATP固体碱催化剂用于催化合成乙二醇丙烯基醚的最佳工艺条件为:反应温度100℃,反应压力为0.20~0.35 MPa,催化剂用量为1.5%,n(丙烯醇):n(EO)为5:1,反应时间为2 h,EO转化率达97.5%。     

负载Fe3+强酸性离子交换树脂催化合成乙酸苄酯

用D072型强酸性阳离子交换树脂负载Fe3+,制备用于合成乙酸苄酯的催化剂。结果表明,树脂负载Fe3+的条件为:Fe3+起始浓度为32.55 mmol/L,负载时间为3.0 min,负载温度为35.0℃,烘干温度为50.0℃。树脂催化合成乙酸苄酯的反应条件为:乙酸与苯甲醇的摩尔比为1∶1,催化剂用量为乙酸质量的15.0%,反应温度100℃,反应时间200 min,乙酸的转化率为67.10%,其催化活性比原树脂的催化活性提高了14.66%。     

负载Fe~（3＋）强酸性离子交换树脂催化合成乙酸苄酯

用D072型强酸性阳离子交换树脂负载Fe3＋,制备用于合成乙酸苄酯的催化剂。结果表明,树脂负载Fe3＋的条件为：Fe3＋起始浓度为32.55 mmol/L,负载时间为3.0 min,负载温度为35.0℃,烘干温度为50.0℃。树脂催化合成乙酸苄酯的反应条件为：乙酸与苯甲醇的摩尔比为1∶1,催化剂用量为乙酸质量的15.0%,反应温度100℃,反应时间200 min,乙酸的转化率为67.10%,其催化活性比原树脂的催化活性提高了14.66%。     

涤纶常压染色促染剂的制备及应用

以有机碱三乙醇胺为催化剂,邻苯二甲酸酐(简称苯酐)与自制阳离子改性剂WLS反应,制备苯酯助剂,并将其作为涤纶分散黑ECT染料常压染色的促染剂。通过系统研究,优化出苯酯合成工艺,并探讨苯酯助剂与N-正丁基邻苯二甲酰亚胺(简称亚胺)复配对分散黑ECT常压染色性能的影响。结果表明:苯酯与亚胺有很好的协同效应,二者质量比按2∶1复配时,可获得最佳染色效果。该复配促染剂应用于涤纶常压染色中,染色后织物先进行195℃焙烘2.5 min,再还原清洗,织物的染色深度K/S值和上染百分率较常压无助剂、同条件染色工艺显著提高,而且基本达到传统高温高压的染色效果。     

强酸性阳离子交换树脂催化合成丁二酸二丁酯

以强酸性阳离子交换树脂为催化剂催化正丁醇和丁二酸反应，合成了丁二酸二丁酯，在0.025 mol丁二酸、0.2 mol正丁醇、1.5 g强酸性阳离子交换树脂和回流分水120 min的条件下，丁二酸二丁酯收率为95.7%，树脂重复使用4次，其活性变化不大。     

五氯硝基苯催化加氢法合成3,5-二氯苯胺

3,5-二氯苯胺是一种重要农药中间体.采用多氯代硝基苯催化加氢脱氯合成3,5-二氯苯胺是一种清洁合成工艺.研究了合成路线中五氯硝基苯催化加氢制备五氯苯胺工艺,主要考察了催化剂、溶剂、反应温度和反应压力对加氢反应的影响.结果表明:与骨架镍相比,Pd/C催化剂具有较好的催化活性和选择性,虽然负载量为10%Pd/C比5%Pd/C催化活性高,但易发生深度脱氯;反应适宜的溶剂为环己烷;在优化的反应条件下,五氯硝基苯转化率可达99%以上,五氯苯胺选择性可达95%以上.     

强酸性树脂催化合成正丁酸烯丙酯的工艺研究

利用强酸性阳离子交换树脂催化合成了正丁酸烯丙酯,由实验可知:反应的酸醇量比为3:2,树脂催化剂用量为1.0g时,反应效果最佳,产品收率可达67%.同时,对树脂的重复使用性能进行了测试,结果表明:树脂在使用7次后,其催化性能保持不变.通过与其他催化剂的催化效果进行比较,说明了强酸性树脂在合成正丁酸烯丙酯的独特优越性。     

Removal of Cationic Dyes from Aqueous Solution by Hydrophobically Modified Poly(acrylic Acid) Hydrogels

Hydrophobically modified poly(acrylic acid) hydrogels were synthesized using acrylic acid (AA), methyl methacrylate (MMA), ethyl methacrylate (EMA) and butyl methacrylate (BMA) as copolymer monomers. These hydrogels were carried out for removal cationic dyes from aqueous solution. It was found that the adsorption of cationic dye depended on the length of the side chain, hydrophobic monomer (MMA, EMA and BMA) content and pH of the solution. Increasing the hydrophobic monomer content led to an increase in the adsorption of cationic dyes on the hydrogels. The adsorption kinetics and isotherms of hydrogels were in good agreement with pseudo–second-order equation and the Langmuir equation, respectively. The cationic dyes adsorption of hydrogels involved a mechanism that combined swelling and electrostatic and hydrophobic interaction.     

Lipase made active in hydrophobic media by coupling with polyethylene glycol

Lipases from various microorganisms were chemically modified with polyethylene glycol derivatives: 2,4-bis[O-methoxypoly(ethylene glycol)]-6-chloro-s-triazine (activated PEG₂, a chain-shaped polymer) and copolymer of polyoxyethylene allyl methyl diether and maleic anhydride (activated PM, a comb-shaped polymer). Because each polymer is amphipathic, the modified lipases become soluble not only in aqueous solution but also in hydrophobic media. They exhibit potent catalytic actions for ester synthesis and ester exchange reactions, the reverse reaction of hydrolysis, in transparent organic solvents and also in oily substrates without organic solvents. With PEG₂-lipases, macrocyclic lactone and gefarnate (geranyl farnesylacetate) were synthesized in high yields from 16-hydroxy-hexadecanoic acid ethyl ester and from farnesylacetic acid and geraniol in organic solvents, respectively. The modified lipase catalyzed the esterification preferentially with the (R)-isomer of secondary alcohols. Because the ester synthesis reactions with modified lipase proceeded in the transparent benzene system, the kinetic parameters (Michaelis constant and maximum velocity) were obtained by reciprocal plotting according to the Michaelis equation. With comb-shaped polymer as modifier, PM-lipase catalyzed effectively the reverse reaction of hydrolysis in organic solvents. The properties of each modified lipase are discussed in relation to those of the nonmodified lipase. Presented at the 84th Annual Meeting of the American Oil Chemists' Society held on April 25–29, 1993, in Anaheim, CA.     

阳离子水性聚氨酯的合成及其在染整中的应用

采用逐步聚合法,选用异佛尔酮二异氰酸酯（IPDI）和聚乙二醇（PEG1000）为预聚单体,自制的端羟基季铵盐为阳离子扩链剂,利用亚硫酸氢钠对异氰酸酯基封端处理后对体系进行去离子水分散乳化,合成了一种反应型阳离子水性聚氨酯（WPU）固色剂,考察了预聚反应温度、nNCO／nOH比值以及扩链剂用量对阳离子WPU性能的影响。结果表明,当预聚反应nNCO／nOH比值为2．0、温度70℃,季铵盐扩链剂质量分数为9％（相对于预聚物）时,合成阳离子WPU性能较好;将其用于活性染料或直接染料染色棉织物的固色处理,耐皂洗牢度及耐摩擦色牢度效果良好,其中湿摩擦牢度能够达到4级。     

吸湿阻燃涤纶短纤维的开发

以对苯二甲酸乙二酯为主体分子结构,添加共聚型磷系阻燃剂和含有吸湿官能团的单体改性聚酯大分子链,以其改性聚酯切片为原料制得吸湿阻燃短纤维,其断裂强度、断裂伸长率等主要指标达到要求;制得阻燃涤纶织物极限氧指数大于30%。     

Synthesis and cationic photopolymerization of a new fluorinated oxetane monomer

A new fluorinated oxetane monomer (FOX) was prepared using a fluorinated alcohol by phase transfer catalysis in a Williamson ether synthesis. The new fluorinated monomer was used in cationic photopolymerization as comonomer of 3,3′-[oxydi(methylene)]bis(3-ethyloxetane). The presence of the FOX monomer induces a decrease of the glass transition temperature, thermal stabilization and an increase of the final oxetane group conversion. Completely hydrophobic surfaces were obtained with a selective enrichment of the fluorinated comonomer, as confirmed by contact angle and XPS analysis.     

新型Gemini阳离子表面活性剂的合成和性能（3）—在烷基链中引入易水解基团促进生物降解

概述了烷基链中含有酰受基和酯基的Gemini阳离子表面活性剂的合成,表面活性和生物降解性,含有酰胺基的Gemini阳离子具有优良的表面活性,但几乎不能生物降解,而含有酯基的Gemini阳离子不仅具有优良的表面活性,而且具有良好的生物降解性。     

疏水改性阳离子高分子絮凝剂P（AM—DMC—CnDMB）的合成与性能研究

以丙烯酰胺（AM）、甲基丙烯酰氧乙基三甲基氯化铵（DMC）、疏水单体CnDMB为原料,通过自由基水溶液共聚合法制备了疏水改性阳离子絮凝剂P（AM—DMC—CnDMB）,考察了不同合成工艺条件下得到的不同结构的聚合产物的絮凝性能。研究结果表明,疏水单体为C4DMB和C8DMB、疏水单体含量为1mol％、絮凝剂加量为20mg／L时,综合絮凝效果较好。用所制备的疏水改性阳离子絮凝剂和普通阳离子型絮凝剂P（AM—DMC）处理城市生活污水,结果发现,疏水改性阳离子型絮凝剂处理效果优于阳离子型絮凝剂。     

Polymerization of fluoroacrylate and guar gum copolymer as a new pretreatment paste for ink‐jet printing of polyester

A novel pretreatment paste containing fluoroacrylate copolymer and modified Guar Gum was carried out on the polyester fabric to provide partial water repellency and printability after inkjet printed with water‐based disperse dye inks. The stable fluorinated pastes were prepared via miniemulsion polymerization of fluoroalkyl acrylates, styrene, 2‐ethylhexyl acrylate, and modified guar gum in the presence of AIBN as initiator, CTAB and polyoxyethylene polyaryl ether as surfactants under suitable reaction conditions. In the analysis of monomer conversion and particle size, the highest polymerization rate with smallest particle size was obtained with increasing concentration of surfactants and initiator but the decreasing degree of substitution of guar gum to imply stronger interactions between fluoroacrylate monomers, hydroxyl groups of modified guar gum and EO units of nonionic surfactants. The 30% of stock fluorinated paste with urea concentration of 6% provided the prints with highest K/S value, satisfactory edge acuity and least color difference between front and back sides of the fabric to show more transparency. The rating 80 of water repellency tested on the best treated polyester fabric demonstrated stain proof properties after sprayed with water and dried. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

抗起球聚酯纤维制造方法(Ⅲ)

介绍通过与第三、第四单体共缩聚及表面处理的方法来制备抗起球聚酯纤维。共缩聚可引入的化合物类型有:碳原子数为14～22的不饱和脂肪酸二聚体;含有两个羟基或羧基的不饱和脂肪族单体;二苯基硅烷二醇,还可添加乙烯类共聚物等。织物表面外理通常采用酚类碱盐溶液、甲醛及强碱溶液与一级胺溶液处理。此外,还可将改性聚酯进行表面处理来制取抗起球聚酯纤维。     

阳离子可染聚酯酯型改性剂的合成研究

以质量分数15%的硫酸为催化剂,将己二酸与乙二醇进行酯化反应,合成了阳离子可染聚酯的改性剂己二酸乙二醇酯,对催化剂用量、反应温度、反应时间、投料比等因素进行了探讨,采用红外光谱法对产物进行了表征。结果表明:当催化剂质量分数为0.05%,乙二醇:己二酸(摩尔比)为3.2:1,反应温度115~120℃,反应时间3.5 h时,其酯化率超过90%,且粘度低于0.05 Pa.s。红外光谱分析表明,产物中含有酯键,说明己二酸与乙二醇发生了酯化反应。