环已酮—甲醛树脂

环己酮-甲醛树脂综合性能良好,是一种新型涂料添加剂.其生产方法有三种甲基环己酮与甲醛共缩合;环己酮与甲醛在有机溶剂和氢氧化钠存在下一步共缩合;环己酮与甲醛在碱性条件下两步合成.工业上采用第三种方法.     

环已酮-甲醛树脂

环己酮-甲醛树脂综合性能良好,是一种新型涂料添加剂.其生产方法有三种:甲基环己酮与甲醛共缩合;环己酮与甲醛在有机溶剂和氢氧化钠存在下一步共缩合;环己酮与甲醛在碱性条件下两步合成.工业上采用第三种方法.     

苯乙酮-环己酮-甲醛共缩聚树脂的合成研究

以苯乙酮、环己酮和甲醛为原料,氢氧化钠为催化剂合成苯乙酮-环己酮-甲醛共缩聚树脂,研究了环己酮/苯乙酮摩尔比、预反应时间、甲醛加料方式等对树脂软化点和羟值的影响,借助FT—IR及^1H-NMR对聚合产物进行了表征。发现在醛酮摩尔比为1．3、环己酮/苯乙酮摩尔比为1．0、氢氧化钠用量为3．0％（质量分数）、预反应时间为1．5h、甲醛一次性加入时,可获得软化点为51．3℃、羟值为119．0mgKOH／g的苯乙酮-环己酮-甲醛树脂。FT—IR和^1H—NMR结果表明通过预反应有利于苯乙酮参与共缩聚反应。     

环己酮-甲醛树脂的合成工艺研究

本文介绍了以环己酮、甲醛为原料合成环己酮 -甲醛树脂的合成工艺过程。重点阐述了反应温度、原料配比及甲苯用量对树脂质量的影响 ,得出了最佳工艺条件。     

环己酮市场火热背后的冷思考

作为一种重要的化工原料,环己酮主要用于生产己内酰胺、己二酸等化工中间体,该领域约占环己酮消费量的70％;其余应用于有机溶剂、环己酮-甲醛树脂,以及油墨、制药、农药、胶粘剂、感光材料等非尼龙领域。我国环己酮产业是伴随着己内酰胺行业的成长而发展起来的。     

固体酸催化环己酮自缩合制备二聚酮的研究

以改性酸性氧化铝为催化剂,进行了环己酮自缩合合成环己酮二聚体的催化反应。考察了反应温度、催化剂用量和反应时间等条件对环己酮自缩合反应的影响。在反应温度150℃、催化剂用量10%（质量分数）、反应时间5 h时的优化反应条件下,环己酮的一次性转化率达到80.2%,二聚酮的选择性为99.9%。与液体催化剂相比,固体酸性氧化铝催化剂具有良好的催化活性和选择性,是一种绿色高效固体酸催化剂。     

环己酮自缩合反应固体催化剂的研制

针对浓硫酸作为环己酮缩合反应催化剂的缺点,合成了三种固体催化剂,在给定实验条件下催化环己酮自缩合反应普遍可以达到超过70%以上的转化率和95%以上的选择性,而且产品便于提纯,具有良好的工业价值和应用前景.选定催化剂和正庚烷作为带水剂通过正交实验考察了反应条件对环己酮转化率的影响.结果发现,影响最大的是催化剂的用量,带水剂用量影响最小,最优化的反应条件为催化剂用量为4 g,带水剂用量60 mL,反应时间8 h.     

2-(1-环己烯基)环己酮的合成

以稀硫酸或碱作催化剂,环己酮自身催化缩合生成2-(1-环己烯基)环己酮.考察了使用稀硫酸、碳酸钠、碳酸钾催化剂在不同条件下的缩合反应,结果表明,用价廉的Na2CO3作催化剂可取,并可使生产成本大大降低.     

合成环己酮乙二缩酮新方法

文章介绍了用无水AlCl3作催化剂,在带水剂环己烷的作用下,用环己酮和乙二醇缩合制环己酮乙二缩酮的新合成方法,并对具体工艺条件进行了分别讨论。     

红外光谱法测定β-萘磺酸盐甲醛缩合物的核体数

研究了用红外光谱法测定β－萘磺酸盐甲醛缩合物核体数的原理和方法,对不同萘与甲醛配比下合成的β－萘磺酸盐甲醛缩合物进行核体数测定,结果显示核体数随着甲醛摩尔数增加而增加。     

Chemical polymerization of pyrrole in the presence of ketone–formaldehyde resins

The chemical polymerizations of pyrrole in the presence of acetophenone and formaldehyde, cyclohexanone, acetaldehyde, and formaldehyde, cyclohexanone and formaldehyde, cyclohexanone, resorcinol, and formaldehyde, cyclohexanone and lignosulfonate formaldehyde, and cyclohexanone, pyrrole, and formaldehyde were accomplished with Ce(IV) salt in acetonitrile solutions. The roles of the resin type, the addition order of the reactants, and the concentrations of the pyrrole and resin on the solubility and conductivity of the resulting products were investigated. The cyclohexanone–acetaldehyde–formaldehyde resin/polypyrrole copolymer had the highest solubility in dimethylformamide. The conductivity and solubility of the copolymers could be controlled by the Ce(IV)/pyrrole/resin molar ratio. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 618–624, 2005     

Block copolymers of cyclohexene oxide and ketonic resins via condensation and promoted cationic polymerization

Block copolymers of cyclohexene oxide (CHO) and ketonic resin were prepared by using ketonic resins as free radical photoinitiators via two‐step procedure. In the first step, cyclohexanone–formaldehyde and acetophenone–formaldehyde resins were modified during their preparation with benzoin and benzoin isobutyl ether. Then, AB or ABA type block copolymers depending on the resin employed were obtained by irradiation of these resins in the presence of pyridinium salt and CHO as a cationically polymerizable monomer. By this way, block copolymers of CHO with ketonic resin were prepared and characterized by GPC, DCS, FTIR, and ¹H NMR spectral measurements. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis of cyclohexanone formaldehyde resin‐methylmethacrylate block‐graft copolymers via ATRP

Well defined block‐graft copolymers of cyclohexanone‐formaldehyde resin (CFR) and methylmethacrylate (MMA) were prepared via atom transfer radical polymerization (ATRP). In the first step, cyclohexanone formaldehyde resin (CFR) containing hydroxyl groups were modified with 2‐bromopropionyl bromide. Resulting multifunctional macroinitiator was used in the ATRP of MMA using copper bromide (CuBr) and N,N,N′,N″,N″‐pentamethyl‐diethylenetriamine (PMDETA) as catalyst system at 90°C. The chemical composition and structure of the copolymers were characterized by nuclear magnetic resonance (¹H‐NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and molecular weight measurement. Molecular weight distributions of the CFR graft copolymers were measured by gel permeation chromatography (GPC). M_n values up to 19,000 associated with narrow molecular weight distributions (polydispersity index (PDI) < 1.6) were obtained with conversions up to 49%. Coating properties of synthesized graft copolymers such as adhesion and gloss values were measured. They exhibited good adhesion properties on Plexiglas substrate. The thermal behaviors of all polymers were conducted using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

In situ modification of cyclohexanone formaldehyde resin with boric acid for high‐performance applications

A boron‐containing cyclohexanone formaldehyde resin (BCFR) was synthesized from cyclohexanone, formaldehyde, and boric acid. The effects of the boric acid concentration, solubility, molecular weight, and thermal properties on the product were investigated. Characterization of the BCFRs was done by NMR spectroscopy, gel permeation chromatography, and Fourier transform infrared–attenuated total reflectance spectroscopy. The thermal properties of the samples were determined with differential scanning calorimetry and thermogravimetric analysis. The study results demonstrate that the resin had higher heat‐resistance properties than the commonly modified cyclohexanone formaldehyde resin. The obtained samples were also characterized morphologically by scanning electron microscopy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

New melamine–formaldehyde–ketone polymers. III. Coatings from melamine and reactive solvents based on cyclohexanone

The conditions and methods of preparing novel melamine–formaldehyde–cyclohexanone coatings are presented. The coatings were prepared by dissolving melamine in reactive solvents based on formaldehyde and cyclohexanone. The latter were prepared at different molar ratios of the components. The water resistance of the resulting coatings was measured. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1083–1092, 2006     

New melamine–formaldehyde–ketone polymers. II. Dissolution of melamine in reactive solvents prepared from cyclohexanone

Reactive solvents of melamine were prepared from cyclohexanone and excess of formaldehyde in the presence of triethylamine catalyst. The solubility of melamine in the solvents was evaluated and the mechanism of dissolution explained on the basis of ¹H‐NMR and IR spectroscopy. Attempts to cure the melamine solutions resulted in melamine–formaldehyde–cyclohexanone polymers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 77–85, 2005     

环己酮精细化发展战略

介绍了环己酮及其衍生物在非己内酰胺用途的主要应用 ,重点讨论了环己酮后续新产品酮醛树脂的开发思路     

ABA-type block copolymers containing poly(dimethylsiloxane) and ketonic resins

Block copolymer containing segments of poly(dimethylsiloxane) (PDMS) and ketonic resins were synthesized. Dihydroxy-terminated PDMS were reacted with the isophorone diisocyanate (IPDI) to obtain the diisocyanate-terminated PDMSs (urethane). These urethanes were reacted with reactive hydroxyl groups in the cyclohexanone–formaldehyde, acetophenone–formaldehyde, and in situ melamine-modified cyclohexanone–formaldehyde resins. Formation of block copolymers was illustrated by several characterization methods, such as chemical and spectroscopic analysis and gel permeation chromatography. The solubilities of the block copolymers were determined, and their surface properties were investigated by contact angle measurements. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 643–648, 1998     

新型糠酮呋喃树脂的研究

以聚乙烯醇、三聚氰胺为改性剂,改性由环己酮、尿素、甲醛和糠醇缩合而成的糠酮呋喃树脂,该树脂是一种新型铸造用的呋喃树脂。反应分三步：酮醛缩合、脲醛缩合、合成树脂。改性呋喃树脂氮含量、游离甲醛含量都明显降低,树脂强度高,粘度小,附着力好,且该工艺具有生产能耗低,工艺简单,产品耐酸耐碱性能好等优点。文章介绍用新型催化剂合成糠...     

新型糠酮树脂的研究

改性糠酮树脂是由环己酮、尿素、甲醛和糠醇缩合而成的新型铸造用的呋喃树脂。其反应分三步,第一步是酮醛树脂的合成,第二步是脲醛树脂的合成,第三步是糠酮树脂的缩聚,制得改性糠酮呋喃树脂,其具有光泽好、硬度高、附着力好、铸造时表面光滑容易脱模,且生产成本低、合成工艺简单、耐酸耐碱性能好等优点。本文介绍了该树脂的合成方法及合成工艺条件的选择与确定,及其最佳固化剂量和固化时间的确定。