1，1＇－二（1，3－二氧代长链烷基）二茂铁的合成与表征

用１，１＇－二乙酰基二茂铁与酯的Ｃｌａｉｓｅｎ缩合反应合成了５个新的１，１＇－二（１，３－二氧代长链烷基）二茂铁，其通式为Ｃ５Ｈ４ＦｅＣ５Ｈ４（ＣＯＣＨ２ＣＯＣｎＨ２ｎ＋１）２，ｎ＝５～９。通过元素分析、紫外－可见光谱、红外光谱、核磁共振氢谱和质谱对这些化合物进行了表征。结果表明，这些β－二酮仅以烯醇式存在。     

资生堂公司关于凝血酸的配方专利（续前）

资生堂公司关于凝血酸的配方专利（续前）北村谦二中山泰一由广州市百星生物工程有限公司提供ＮＨＲ３Ｒ１—ＮＨ—（ＣＨ２）４ＣＨ—ＣＯ—Ｒ２Ｒ３＝Ｈ,ＳＯ２——ＣＨ３Ｒ１—ＮＨ—ＣＨ—（ＣＨ２）３—ＣＨ—ＣＯ—Ｒ２＋ＮＨ２ＮＨＲ３Ｒ３＝Ｈ,ＳＯ２——ＣＨ３...     

一类新型二胺的合成研究

报道了以２种不同的还原体系ＮＨ２ＮＨ２－ＲａｎｅｙＮｉ／Ｃ２Ｈ５ＯＨ和Ａｌ—Ｈｇ／Ｈ２Ｏ,将３－取代－１,５－二（２－硝基苯氧基）－３－氮杂戊烷（Ⅰ～Ⅶ）还原为相应的二胺（Ⅷ～ⅩⅣ）,取代基分别为ＣＨＣＨ２ＣＨ２,ｎ－Ｃ４Ｈ９—,ＣＨ３ＯＣＨ２ＣＨ２—,Ｃ２Ｈ５ＯＣＨ２ＣＨ２—,ｎ－Ｃ４Ｈ９ＯＣＨ２ＣＨ２—,ＣＨ３ＯＣＨ２ＣＨ２ＯＣＨ２ＣＨ２—,ｎ－Ｃ４Ｈ９ＯＣＨ２ＣＨ２ＯＣＨ２ＣＨ２—。产物经元素分析、１ＨＮＭＲ和ＭＳ证实其结构。     

顺、反异构钼硫簇合物〔(C_2H_5)_4N〕_2〔Mo_2S_4(SCH_2CH_2S)_2〕的合成、结构和性质研究

用（ＮＨ４）２ＭｏＳ４，ＣｏＣｌ２，ＮｉＣｌ２，ＨＳＣＨ２ＣＨ２ＳＨ和Ｅｔ４ＮＢｒ在ＣＨ３ＯＨＣＨ３ＯＮａ溶液中反应，得到了顺（Ａ），反（Ｂ）异构体的原子簇化合物［（Ｃ２Ｈ５）４Ｎ］２［Ｍｏ２Ｓ４（ＳＣＨ２ＣＨ２Ｓ）２］的晶体。用Ｘ—射线单晶衍射法测定了顺、反异构体簇合物Ａ和Ｂ晶体结构，其晶胞参数Ａ为ａ＝２．６０４４（２）ｎｍ，ｂ＝１．９８８６（２）ｎｍ，Ｃ＝２．６３０２（Ｉ）ｎｍ，Ｖ＝１３．５８６ｎｍ３，β＝９３．３３°（２）；Ｂ为ａ＝１．０４４（２）ｎｍ，ｂ＝１．４１５８（２）ｎｍ，Ｃ＝１．１４１７（２）ｎｍ，Ｖ＝１．６３８ｎｍ３，β＝１００．４７°，经块距阵最小二乘法修正最终得偏离因子Ｒ＝０．０８８（Ａ），Ｒ＝０．０８９（Ｂ）。同时还对簇合物的红外光谱和紫外可见光谱也进行了研究。     

O,O—二烷基磷酰胍及衍生物的合成

用硫脲，Ｓ－乙基异硫脲和胍与二烷基亚磷酸酯在四氯化碳的碱溶液中反应得到产率满意的磷酰化产物，它们的通式是：（ＲＯ）２ＰＮＨＣＮＲ′Ｒ″ＯＮＨ和（ＲＯ）２ＰＮＨＣＯＳＥｔＮＨ２，其中：Ｒ＝ｎ－Ｃ４Ｈ９—，ｉ－Ｃ４Ｈ９—，ｓｅｃ－Ｃ４Ｈ９—，ｎ－Ｃ６Ｈ１３—；Ｒ′＝Ｒ″＝Ｈ－，ＣＨ３ＣＨ２—。其中７种化合物未见文献报道。以上这些产物对金属离子的萃取作用，本文作了初步探索     

1-羟基乙叉-1,1-二膦酸铜(Ⅱ)固体配合物的研究

本文合成了六种１－羟基乙叉－１１二膦酸ＣＨ３Ｃ（ＯＨ）（ＰＯ３Ｈ２）２（简称ＨＥＤＰ）与Ｃｕ（Ⅱ）的固体配合物。用元素分析和热重分析确定了这些配合物的组成Ｃｕ（Ｈ３Ｌ）２．１２Ｈ２Ｏ、Ｎａ４Ｃｕ（ＨＬ）２８Ｈ２ＯＣｕＨ２Ｌ．２Ｈ２Ｏ、ＮａＣｕＨＬ．６Ｈ２Ｏ、Ｎａ２ＣｕＬ．５Ｈ２Ｏ、Ｃｕ２Ｌ．３Ｈ２Ｏ（其中Ｌ＝ＣＨ３Ｃ（ＯＨ）（ＰＯ３）２）。用红外光谱和热分析对合成产物的结构及热稳定性作了系统的研究。通过电位滴定法讨论了Ｃｕ（Ⅱ）与ＨＥＤＰ之间的配位作用。     

1—羟在乙叉—1,1—二膦酸铜（Ⅱ）固体配合物的研究

本文合成了六种１－羟基乙叉－１，１－二膦酸ＣＨ３Ｃ（ＯＨ）（Ｐ３Ｈ２）２与Ｃｕ的固体配合物。用元素分析和热重分析确定了这些配合物的组成Ｃｕ（Ｈ３Ｌ）２，１２Ｈ２Ｏ，Ｎａ４Ｃｕ（ＨＬ）２８Ｈ２ＯＣｕＨＬ，６Ｈ２Ｏ，Ｎａ２ＣｕＬ，５Ｈ２Ｏ，Ｃｕ２Ｌ．３Ｈ２Ｏ。用红外光变和热分析对产物的结构及热稳定性作了系统的研究。     

用相转移催化剂催化合成4-烷基苯甲酸

以烷基苯乙酮为原料,工业废氯气的回收碱液次氯酸钠溶液为氧化剂,在相转移催化剂聚乙烯醇（ＰＥＧ）作用下,合成了４－烷基苯甲酸ＲＣＯＯＨ（Ｒ＝ＣＨ３,ＣＨ３（ＣＨ２）ｎ,ｎ＝１～４）。优选出最佳工艺条件：ｎ（次氯酸钠）∶ｎ（烷基苯乙酮）为４．０∶１．０,反应混合液ｐＨ≥１３,相对１ｍｏｌ烷基苯乙酮ＰＥＧ－４００用量为２００ｍＬ,烷基苯甲酸收率大于９０％,质量分数大于９５％。     

化学配方与制备

化学配方与制备聚酯阻燃剂（苯基氧膦基）丙酸酯的制备用乙二醇使ＨＯＰ（Ｏ）（Ｃ６Ｈ５）ＣＨ２ＣＨ２ＣＯ２Ｈ酯化，在８２─８８℃和１．３３３─１．９９９ｋＰａ下蒸馏除去水，得到ＨＯＰ（Ｏ）（Ｃ６Ｈ５）ＣＨ２ＣＨ２ＣＯ２ＣＨ２ＣＨ２ＯＨ，该化合物适于聚酯树...     

合成2,6-二甲基苯胺的催化剂及工艺条件研究

通过实验筛选出该反应的催化剂为Ｖ２Ｏ５ － Ｃｒ２Ｏ３ － Ａｌ２Ｏ３ ,确定了浸渍法制备的浸渍液质量分数为１３－２％ ,催化剂中主催化剂Ｖ２Ｏ５ 的最佳质量分数为１０ ％ ,最佳改性金属氧化物为Ｃｒ２Ｏ３及最适宜比例为ｎ（Ｖ２Ｏ５）∶ｎ（Ｃｒ２Ｏ３） ＝１０∶１ 。通过工艺条件考察,筛选出最佳工艺条件为：反应温度３７０ ℃,原料配比ｎ（Ｃ７Ｈ７ＮＨ２）∶ｎ（ＣＨ３ＯＨ）∶ｎ（Ｈ２Ｏ）＝ １∶３∶１,液时空速０－５／ｈ,原料中加入水可明显提高目的产物选择性。反应转化率为７４－２９ ％ ,目的产物选择性为５１－２４ ％ 。     

有机硅改性环氧树脂的制备及其性能研究

以3种有机氯硅烷单体水解制备有机硅单体,有机硅单体改性了环氧树脂,水解条件为温度35～40℃,时间1～1.5 h,用水量n(H2O)∶n(Cl)=(6～7)∶1。通过红外光谱分析表明,有机硅主要是与环氧树脂中羟基发生化学反应。对环氧树脂改性前后的力学性能、耐热性和防潮性进行测试,结果表明,当n(R)/n(Si)为1.5时,拉伸强度可达23.91 MPa,弯曲强度达到29.24 MPa,冲击强度达到10.02 kJ/m2,50%的质量热损失温度431℃,分别比改性前提高了3.86 MPa,9.49 MPa,6.18 kJ/m2,30℃;同时,改性后树脂防潮性能也得到了提高。     

Spectral,thermal, and photoreactivity studies on epoxy resin containing benzylidene units in the main chain

A photosensitive epoxy resin was synthesized from bis(4‐hydroxy ‐3‐methoxy benzylidene) acetone and epichlorohydrin using solution polycondensation method. The prepared epoxy resin was characterized by UV, IR, ¹H NMR, and ¹³C NMR spectroscopy. The thermal stability of the epoxy resin was assessed by thermogravimetric analysis. The glass transition temperature of the polymer was determined by differential scanning calorimetry. The photocrosslinking property and photopolymerizing ability of the epoxy resin were studied in film and solution state using UV spectroscopy. The effect of photo acid generator and sensitizer on photosensitivity of the resin was also investigated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Wavelength‐shift fluorescent probes for monitoring of polymerization

The feasibility of using wavelength‐shift fluorescent probes for cure monitoring of an epoxy resin and an acrylic resin was evaluated. 4‐(N,N‐dihexylaminostyryl)‐4′‐pyridinium propylsulfonate (DHASP‐PS), as well as each of other wavelength‐shift fluorescent probes, was dissolved in the epoxy resin, a stoichiometric mixture of diglycidyl ether of bisphenol A and 4,4′‐methylene‐bis(cyclohexylamine). The fluorescence and the excitation spectra of each of the probes dissolved in the epoxy resin were then measured at various times during the cure of the epoxy resin at 60°C. The fluorescence and the excitation spectra of the probe DHASP‐PS dissolved in methyl methacrylate (MMA) were also measured at various times during the cure of the acrylic resin at 55°C. Since the peak fluorescence wavelength of each of the wavelength‐shift fluorescent probes decreased during the cure of the epoxy resin or MMA, these fluorescent probes can be used for monitoring the polymerization reactions of epoxy resins and vinyl resins. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 747–750, 2006     

Synthesis of Copolymers Containing Double Spiro Orthocarbonate and Used as Anti-shrinkage Additives in Epoxy Resin Composite

A novel copolymer containing a double spiro orthocarbonate structure, poly 3-methylene-9-methyleneoxy-3,9-Bis(hydroxymethyl)-1,5,7,11-tetraoxaspiro[5.5] undecane (SOC), was synthesized. The structure of SOC was confirmed by ¹H, ¹³C NMR and FTIR spectra. Prepolymer (SOCP) reacting from SOC and 2,4-toluene diisocynate (TDI) was prepared and used as anti-shrinkage additives in the cationic polymerization of epoxy resin (EP-51). The volume changes of the cured epoxy resin containing SOCP were investigated by density measurements with an electronic hydrometer. The mechanical properties of the modified epoxy resin were investigated by adhesive strength, impact strength and flexural strength, while thermal properties were investigated by thermal gravimetric analysis (TGA).     

Development of Siloxane Based Tetraglycidyl Epoxy Nanocomposites for High Performance Applications—Study of the Mechanical,Thermal, Water Absorption and Flame Retardant Behaviour

A study was made in the present investigation on siloxane containing tetraglycidyl epoxy nanocomposites in order to determine their suitability for use in high performance applications. The synthesis of the siloxane tetraglycidyl epoxy resin denoted as ‘E’ was done and it was characterized by Fourier Transform Infrared (FT-IR) spectra and ¹H, ¹³C Nuclear Magnetic Resonance (NMR) spectra. Nanoclay and polyhedral oligomeric silsesquioxanes (POSS)-amine nanoreinforcements denoted as N1 and N2 were incorporated into the synthesized epoxy resin. Curing was done with diaminodiphenylmethane (DDM) and bis (3-aminophenyl) phenylphosphine oxide (BAPPO) curing agents denoted as X and Y respectively. The mechanical, thermal, flame retardant and water absorption behaviour of the epoxy nanocomposites were studied and the results are discussed.     

环氧改性水性聚氨酯的合成工艺及性能

采用甲苯二异氰酸酯(TDI-80)、聚醚二醇(N220)、二羟甲基丙酸((DMPA)、环氧树脂和丙烯酸羟丙酯(HPA)为主要原料,合成了环氧改性的水性聚氨酯乳液。研究了反应温度、乳化分散速度、中和度和环氧树脂的用量对乳液及涂膜性能的影响。结果表明:当乳化分散速度为4 000~5 000 r/min,中和度为90%~95%,环氧树脂的添加量为4%~6%时,可得到性能较好的乳液。通过环氧树脂改性的水性聚氨酯涂膜具有硬度高、耐水性和力学性能好的特点。     

Development of dimethylsiloxane based tetraglycidyl epoxy nanocomposites for high performance,aerospace and advanced engineering applications

A study was made in the present investigation on bis(p-aminophenoxy) dimethylsiloxane based tetraglycidyl epoxy nanocomposites in order to determine its suitability for use in high performance applications. The synthesis of the siloxane tetraglycidyl epoxy resin denoted as ‘F’ was done and it was characterized by Fourier transform infrared spectra (FT-IR) and ¹H, ¹³C nuclear magnetic resonance (NMR) spectra. Nanoclay and polyhedral oligomeric silsesquioxanes (POSS)-amine nanoreinforcements denoted as N1 and N2 were incorporated into the synthesized epoxy resin. Curing was done with diaminodiphenylmethane (DDM) and bis(3-aminophenyl) phenylphosphine oxide (BAPPO) curing agents denoted as X and Y respectively. The mechanical, thermal, flame retardant and water absorption behavior of the epoxy nanocomposites were studied and the results are discussed.     

输油管线用熔结环氧粉末涂料的制备

采用线型酚醛环氧树脂(ENR)、环氧树脂E-12、固化剂JECP-02B制备了输油管线用熔结环氧粉末涂料。考察了线型酚醛环氧树脂与环氧树脂E-12质量比对涂料性能的影响,以及固化剂JECP-02B、流平剂GLP588和固化促进剂2-甲基咪唑对固化行为的影响,用红外光谱分析了固化前后树脂的变化,m(ENR)/m(E-12)=(75/25)~(25/75)、m(固化剂)/m(环氧树脂)=1/4、m(流平剂)/m(环氧树脂)=2/100、m(2-甲基咪唑)/m(环氧树脂)=(0.1~0.15)/100时,涂层性能达到输油管线防腐指标(SY/T 0315-97)。长庆化工有限责任公司用该技术扩大生产约10 t环氧粉末涂料,用于长庆油田输油管线的防腐,产品满足了1.5 m in/230℃快速固化的施工要求。     

Synthesis and characterization of emulsion‐type curing agent of water‐borne epoxy resin

Self‐emulsified water‐borne epoxy curing agent of nonionic type was prepared using triethylene tetramine (TETA) and derivative of epoxy resin as a capping agent, which was synthesized by liquid epoxy resin (E51) and polyethylene glycol (PEG), and the curing agent possessed emulsification and curing properties at the same time. The curing agent with good property of emulsifying liquid epoxy resin could be obtained under the condition of the molar ratio of PEG : E51 : TETA as 0.8 : 1 : 3.5 at 80°C for 5 h. The mean particle size of the emulsion liquid was about 220 nm with the prepared curing agent and epoxy resin at the mass ratio of 1 : 3. The structure of the emulsion‐type curing agent was confirmed by FTIR and ¹H NMR spectra, and the mechanism of cured film formation was also analyzed by SEM photographs. The cured film prepared by the emulsion‐type curing agent and epoxy resin under ambient cure conditions showed good properties even at high staving temperature. This study provides useful suggestions for the application of the water‐borne epoxy resins in coating industry. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2652–2659, 2013     

丙氨酸与苯丙氨酸复合改性的水性环氧树脂制备及性能研究

以相对分子质量低的环氧树脂E－51为原料,丙氨酸（Ala）与苯丙氨酸（Pha）为复合改性剂,制备出稳定的水性环氧树脂,采用红外光谱（FT-IR）、化学滴定等方法对产物进行了表征和分析,优选了综合性能优良的固化剂与制备的水性环氧树脂固化成膜,同时对涂膜性能进行测试。结果表明：适宜的反应温度为90℃,反应时间为100min;当复合改性剂n（Alal：n（Pha）=2：3时,此时制备的水性环氧树脂,与汉中H228Z水性环氧固化剂固化所形成的涂膜具有最优的综合性能,涂膜附着力1级,柔韧性1mm,耐冲击性40cm,铅笔硬度5H,耐酸性（5％Hcl）24h,耐碱性（5％NaOH）72h。