UV固化多臂型含氟聚氨酯的制备及性能研究

采用甲基丙烯酸十二氟庚酯（ DFHMA）与 3-氨基 -1,2-丙二醇反应得到自制含氟二元醇;以异佛尔酮二异氰酸酯（ IPDI）、聚碳酸酯二元醇（ PCDL）、季戊四醇三丙烯酸酯（ PETA）、一缩二丙三醇（ DIGLYCEROL）、含氟二元醇为主要原料合成了 UV固化多臂型含氟聚氨酯,采用红外光谱和核磁共振氢谱对自制含氟二元醇和聚合物进行了表征,并对聚合物涂层的水接触角、耐水性、热稳定性、硬度、力学性能等进行了测试。结果表明：含氟二元醇的引入使得涂膜的水接触角上升,耐水性提升,热稳定性提高,硬度增加。在含氟二元醇含量为 8%时,涂层的综合性能最佳。     

含氟（甲基）丙烯酸酯单体的合成及应用

本文阐述了国内外含氟（甲基）丙烯酸酯单体的开发应用情况，详细地介绍了含氟（甲基）丙烯酸酯单体的合成方法，并对我国含氟（甲基）丙烯酸酯单体的开发提出了建议。     

UV固化含氟低聚物的制备及性能研究

首先由甲基丙烯酸十二氟庚酯（ DFHMA）与乙醇胺通过 Michael加成反应得到含氟醇;其次以含氟醇、马来酸酐和甲基丙烯酸缩水甘油酯（ GMA）合成活性含氟中间体;最后将之与异佛尔酮二异氰酸酯（ IPDI）、季戊四醇三丙烯酸酯（ PETA）反应得到可紫外光（ UV）固化的含氟低聚物。采用红外光谱、核磁共振对产物结构进行表征。以所得低聚物制备 UV固化涂膜,通过测试涂膜接触角、热稳定性、硬度等研究不同含氟醇添加量对涂膜性能的影响。结果表明：当含氟醇质量分数从 0增加到 10%时,涂膜水接触角从 56. 3°上升到 98. 2°,表面自由能由 52. 62 mN/m降至 22. 96 mN/m,且涂膜热稳定性提高,硬度提高。     

氟化工专利精选

可固化的含氟弹性体组合物和由其制得的热空气软管 该组合物由过氧化物可固化的含氟弹性体（无定形弹性体的含氟聚合物）、炭黑和增塑剂组成,由其制得的固化（即交联的）热空气软管（例如涡轮增压器软管）具有耐热性和机械性能的出色平衡。     

氟塑料板,片,棒,管,膜加工及应用（一）

氟塑料是各种含氟塑料的总称。有单一氟塑料如聚四氟乙烯（PTFE）,有二元共聚的含氟塑料聚全氟乙丙烯（FEP）及其它等等。这二种氟塑料是含氟塑料中的典型。PTFE由于它的加工方法特殊,性能优异为含氟塑料的典型;FEP的加工方法类同于热塑性塑料。加工比PTFE易而性能类同于PTFE,是含氟热塑性塑料的典型。本文重点介绍上述二种含氟塑料,并尽力涉及其它含氟塑料。在介绍中,本着常规的作一般介绍,新产品、新工艺、新应用作较详介绍,以供参考。五含氟塑料的板、片、膜、瞥、棒的尺寸分类板：厚度（imim）1．5以上片：厚度（Inm…     

含氟调聚醇的制备

以四氟乙烯和甲醇为原料，在溶剂和自由基引发剂存在下调聚反应生成通式为H（CF：CF2）nCH：OH（n为1～6）的含氟醇，通常都生成低聚合度（n为1～3）的含氟多聚醇，要获得高纯度的高聚合度（n为4～5）的含氟多聚醇极不容易。介绍了在合成、分离常规含氟多聚醇的基础上，通过优化反应条件、采用区域精炼等分离方法；获得了反应产物中高聚合度（n为4～5）的含氟多聚醇的含量大幅度上升、分离后纯度高于99％的十六氟壬醇和二十氟十一醇的预期效果。     

自交联含氟乳胶膜耐介质性能的研究

用种子乳液聚合法制备了具有核壳结构的含氟乳液，从FTIR、TEM的表征来看，得到了性能较好的、具有核壳结构的含氯乳液。通过测试含氟乳胶膜的耐介质性，并运用JC2000A静态接触角测量仪测定乳胶膜的接触角，研究了FBA（甲基丙烯酸含氟酯）用量、FBA加入方式、NMA（N-羟甲基丙烯酰胺）用量、乳化剂用量对含氟乳胶膜耐介质性的影响。结果表明，配方中FBA用量为20％（孽尔分数）、NMA用量为4％（质量分数）、乳化剂用量2．8％（质量分数），而且将FBA全部放在壳层聚合，可得到性能较住的含氟乳胶膜。     

含氟表面活性剂的研究进展

介绍了含氟表面活性剂的分类结构、特性、合成方法及应用领域。重点介绍其在传统工业（化工、纺织、造纸及橡胶工业）和在含氟材料合成中的应用现状。针对目前存在的问题,提出了对人类健康和生存环境造成影响的PFOS（Pedluorooctane Sulfonate）和PFOA（Perfluorooctanoic Acid）的研究方向,并概述了含氟表面活性剂近年来的研究进展。     

结构可控含氟共聚物的合成及其应用研究新进展

近年来,含氟聚合物以其优异的耐热性、耐氧化性、耐候性、耐腐蚀性以及低介电常数、低表面能等特点,在疏水材料、抗污材料、表面活性剂、造影剂等领域具有广泛的应用前景,受到研究者的密切关注,各种拓扑结构的含氟共聚物被设计合成出来并在相关领域得到应用。本文首先简要介绍了含氟聚合物的性质和研究现状,然后详细叙述了可逆加成-断裂链转移聚合（RAFT）、原子转移自由基聚合（ATRP）、碘转移自由基聚合（ITP）、单电子转移活性聚合（SET-LRP）、氮氧稳定自由基聚合（NMP）以及活性阴离子聚合（LAP）等聚合方法在结构可控含氟共聚物合成中的研究新进展,并对其聚合机理、优缺点以及所得共聚物的性质和应用进行了总结,最后对结构可控含氟共聚物的设计、合成及实际应用前景进行了展望,提出发展绿色环保功能性含氟聚合物将是未来的主要研究热点。     

TiO2/含氟树脂复合超疏水涂层的制备

采用自由基溶液聚合法与共混法制备Ti O2/含氟树脂（FA）超疏水涂层。分别以甲基丙烯酸丁酯（BA）和苯乙烯（ST）为软硬单体,甲基丙烯酸十二氟庚酯（DFMA）为低表面能单体,丙烯酸（AA）为功能单体,甲苯（MB）为溶剂,通过自由基溶液聚合法制备含氟树脂（FA）。将无机纳米TiO2粒子均匀分散于含氟树脂中,然后以提拉法涂覆于基质表面即得TiO2/含氟树脂复合涂层。用接触角仪、紫外可见光光度计、红外光谱、扫描电镜、综合热分析对涂层进行了测试表征。实验结果表明：当DFMA含量为15%,含氟树脂涂层与水的接触角为105°,涂层在310℃以下可基本保持稳定结构。当TiO2（60nm）粒子的掺杂质量分数为15%时,所制备复合涂层的疏水角为151°,透过率可达65-75%。     

滇韭挥发性成分分析

用同时蒸馏萃取装置提取挥发油并用气相色谱-质谱联用仪对滇韭挥发性成分进行了分离和鉴定,分离并鉴定出95个组分,占峰面积的71 50%,用面积归一化法测定了各种成分的质量分数,其主要挥发性成分为:w(三甲基磷化硫醚) =0 15%,w(丁基丙烯基硫醚) =0 03%,w(1, 2 二乙硫基乙烯) =0 38%,w(烯丙基甲基硫醚) =0 79%,w(二烯丙基硫醚) =0 11%,w(2 甲氧基茴香硫醚) =0 15%,w(甲基乙基二硫醚) =0 02%,w(二甲基二硫醚) =0 08%,w(二烯丙基二硫醚) =0 10%,w(二丙基二硫醚) =1 03%,w〔(甲硫基)二甲基二硫醚〕=0 17%,w(甲基1 丙烯基二硫醚) =0 32%,w(二2 羟基乙基二硫醚) =0 11%,w(二甲基三硫醚) =0 02%,w(甲基2 丙烯基三硫醚) =0 06%,w(二2 丙烯基三硫醚) =0 45%,w(二丙基三硫醚) =1 54%,w(二甲基四硫醚) =0 39%,w(4H 噻唑) =0 02%,w(4, 5 二甲基噻唑) =0 50%,w(4, 5 二甲基异噻唑) =0 06%,w(5 甲氧基噻唑) =0 24%,w(3, 4 二甲基异噻唑) =0 22%,w(3, 4 二甲基噻吩) =0 27%,w(4H 2 乙基噻吩) =0 02%,w(1, 3 二噻烷) =0 03%,w(1, 3, 5 三噻烷) =0 03%,w(1, 2 二硫戊环) =0 09%,w〔2, 4 二硫杂戊烷〕=0 98%,w(3, 5 二乙基1, 2, 4 三硫戊环) =0 55%,w(二甲基亚砜) =0 05%,w(3 甲硫基丁醛) =0 02%,w(2 甲基硫代乙酸) =0 37%,w     

Chiral platinum(II) metallointercalators with potent in vitro cytotoxic activity

Four platinum(II) metallointercalating complexes of 1,10-phenanthroline (phen) with the chiral ancillary ligands trans-R,R- and trans-S,S-1,2-diaminocyclohexane (R,R- and S,S-dach, respectively), and N,N'-dimethyl-R,R- and N,N'-dimethyl-S,S-1,2-diaminocyclohexane (Me(2)-R,R-dach and Me(2)-S,S-dach, respectively) have been synthesised and characterised. The crystal structure of [Pt(Me(2)-S,S-dach)(phen)](ClO(4))(2)1.5 H(2)O (C(20)H(26)Cl(2)N(4)O(9.5)Pt) has been determined; orthorhombic, space group P2(1)2(1)2(1)(No. 19), a=23.194(8), b=25.131(9), c=8.522(3) A. In vitro cytotoxic assays (IC(50)) in the human bladder cancer cell line 5637 and in the murine leukemia L1210 cell line revealed that [Pt(S,S-dach)(phen)](ClO(4))(2) (0.091 and 0.13 microM, respectively) and [Pt(R,R-dach)(phen)](ClO(4))(2) (0.54 and 1.50 microM, respectively) were more cytotoxic than cisplatin (0.31 and 0.50 microM, respectively) and considerably more cytotoxic than their methylated counterparts, [Pt(Me(2)-R,R-dach)(phen)](ClO(4))(2) and [Pt(Me(2)-S,S-dach)(phen)](ClO(4))(2) (both>23 microM). Chiral discrimination for [Pt(S,S-dach)(phen)](ClO(4))(2) over its R,R-enantiomer was observed in all 13 cancer cell lines investigated. Moreover, [Pt(S,S-dach)(phen)](ClO(4))(2) was more active than cisplatin in all cell lines tested and shows only partial cross-resistance to cisplatin in two cisplatin resistant cell lines.     

Structural Diversity and Defensive Properties of Norditerpenoid Alkaloids

We have tested the insect antifeedant and toxic activity of 43 norditerpenoid alkaloids on Spodoptera littoralis and Leptinotarsa decemlineata including eserine (physostigmine), anabasine, and atropine. Antifeedant effects of the test compounds were structure- and species-dependent. The most active antifeedants to L. decemlineata were 1,14-diacetylcardiopetaline (9) and 18-hydroxy- 14-O-methylgadesine (33), followed by 8-O-methylconsolarine (12), 14-O-acetyldelectinine (27), karakoline (7), cardiopetaline (8), 18-O-demethylpubescenine (13), 14-O-acetyldeltatsine (18), takaosamine (21), ajadine (24), and 8-O-methylcolumbianine (6) (EC50 < 1 microg/cm2). This insect showed a moderate response to atropine. S. littoralis had the strongest antifeedant response to 24, 18, 14-O-acetyldelcosine (19), and delphatine (29) (EC50 < 3 microg/cm2). None of the model substances affected the feeding behavior of this insect. The most toxic compound to L. decemlineata was aconitine (1), followed by cardiopetalidine (10) (% mortality > 60), 14-deacetylpubescenine (14), 18-O-benzoyl-18-O-demethyl-14-O-deacetylpubescenine (17), 14-O-acetyldelcosine (19), 14-deacetylajadine (25) and methyllycaconitine (30) (% mortality > 45). Orally injected S. littoralis larvae were negatively affected by 1, cardiopetaline (8), 10, 1,14-O-acetylcardiopetalidina (11), 12, 14, 1,18-O-diacetyl-19-oxo-gigactonine (41), olivimine (43), and eserine in varying degrees. Their antifeedant or insecticidal potencies did not parallel their reported nAChR binding activity, but did correlate with the agonist/antagonist insecticidal/antifeedant model proposed for nicotininc insecticides. A few compounds [14, tuguaconitine (38), 14-demethyldelboxine (40), 19, dehydrodelsoline (36), 18-O-demethylpubescenine (13), 41, 9, and delcosine (23)] had selective cytotoxic effects to ward insect-derived Sf9 cells. None were cytotoxic to mammalian CHO cells and none increased Trypanosoma cruzi mortality. The selective cytotoxic effects of some structures indicate that they can act on biological targets other than neuroreceptors.     

Composition and Antifungal Activity of the Essential Oil of the Brazilian Chenopodium ambrosioides L.

The antifungal activity of essential oil (EO) from the Brazilian epazote (Chenopodium ambrosioides L.) was evaluated by the poison food assay at concentrations of 0.3%, 0.1%, and 0.05% with eight postharvest deteriorating fungi (Aspergillus flavus, Aspergillus glaucus, Aspergillus niger, Aspergillus ochraceous, Colletotrichum gloesporioides, Colletotrichum musae, Fusarium oxysporum, and Fusarium semitectum). EO components were tentatively identified by Kováts retention indices (RIs) using gas chromatography and gas chromatography combined with mass spectrometry (GC-MS). Growth of all fungi was completely inhibited at 0.3% concentration, and by 90% to 100% at 0.1% concentration. The following 13 tentatively identified compounds (relative percent) accounted for 90.4% of the total volatile oil: alpha-terpinene (0.9), p-cymene (2.0), benzyl alcohol (0.3), p-cresol (0.3), p-mentha-1,3,8-triene (0.2), p-cimen-8-ol (0.6), alpha-terpineol (0.5), (Z)-ascaridole (61.4), piperitone (0.9), carvacrol (3.9), (E)-ascaridole (18.6), (E)-piperitol acetate (0.5), and (Z)-carvyl acetate (0.3). Autobiographic thin layer chromatography of the EO to separate the principal fungitoxic fraction yielded only one fraction that completely inhibited the growth of all test fungi at a concentration of 0.1%. This fraction was characterized by RIs and GC-MS presenting a composition (%) of p-cymene (25.4), (Z)-ascaridole (44.4), and (E)-ascaridole (30.2). The results suggest ascaridoles were the principal fungitoxic components of the EO.     

Synthetic potential of molluscan sulfatases for the library synthesis of regioselectively O-sulfonated D-galacto-sugars

The substrate specificities of three molluscan sulfatases (E.C. 3.1.6.1; snail, abalone, and limpet origins) were investigated with assorted p-nitrophenyl (pNP) di-O-sulfonated beta-D-galactopyranosides and beta-lactosides [3,6-SO(3) Gal (1), 3',6'-SO(3) Lac (2), 4, 6SO(3) Gal (3), 2,6-SO(3) Gal (4), 3,4-SO(3) Gal (5), and 3,6-SO(3) GalNAc (6); Ac, acetyl; Gal, galactose; Lac, lactose] together with mono-O-sulfonated beta-D-galactopyranoside [pNP 3SO(3)-Gal (7)] and tri-O-sulfonated alpha-D-galactopyranoside [2,3,6-SO(3)-alpha-Gal (11)]. Some notable differences between the substrate specificity of the three sulfatases were disclosed; snail sulfatase hydrolyzed the 3O- and 2O-sulfo groups of 1 and 4, respectively, to afford 6SO(3) Gal (9) in high yields, while the abalone enzyme did not act on 4. Only the limpet enzyme could cleave the 3O-sulfo groups of 7 to give pNP beta-galactoside. In contrast, every enzyme could utilize 11 as a good substrate to afford a mixture of 6SO(3)-alpha-Gal (13) and 2,6-SO(3) alpha-Gal (12). None of the enzymes could cleave the O-sulfo groups of 5 and 6, which indicates that a primary 6O-sulfo group tends to promote the enzymatic hydrolysis of O-sulfo groups at the secondary positions.     

Hydrogen-bond detection, configuration assignment and rotamer correction of side-chain amides in large proteins by NMR spectroscopy through protium/deuterium isotope effects

The configuration and hydrogen-bonding network of side-chain amides in a 35 kDa protein were determined by measuring differential and trans-hydrogen-bond H/D isotope effects by using the isotopomer-selective (IS)-TROSY technique, which leads to a reliable recognition and correction of erroneous rotamers that are frequently found in protein structures. First, the differential two-bond isotope effects on carbonyl (13)C' shifts, which are defined as Delta(2)Delta(13)C'(ND) = (2)Delta(13)C'(ND(E))-(2)Delta(13)C'(ND(Z)), provide a reliable means for the configuration assignment for side-chain amides, because environmental effects (hydrogen bonds and charges, etc.) are greatly attenuated over the two bonds that separate the carbon and hydrogen atoms, and the isotope effects fall into a narrow range of positive values. Second and more importantly, the significant variations in the differential one-bond isotope effects on (15)N chemical shifts, which are defined as Delta(1)Delta(15)N(D) = (1)Delta(15)N(D(E))-(1)Delta(15)N(D(Z)) can be correlated with hydrogen-bonding interactions, particularly those involving charged acceptors. The differential one-bond isotope effects are additive, with major contributions from intrinsic differential conjugative interactions between the E and Z configurations, H-bonding interactions, and charge effects. Furthermore, the pattern of trans-H-bond H/D isotope effects can be mapped onto more complicated hydrogen-bonding networks that involve bifurcated hydrogen-bonds. Third, the correlations between Delta(1)Delta(15)N(D) and hydrogen-bonding interactions afford an effective means for the correction of erroneous rotamer assignments of side-chain amides. Rotamer correction by differential isotope effects is not only robust, but also simple and can be applied to large proteins.     

Fourth Meeting on Fire-Retardant Polymers

The Fourth Meeting on Fire-Retardant Polymers was held from September 9 to September 11, 1992, at Albert-Ludwige-University, Freiburg im Breisgau, Germany. The meeting was organized by the Freiburg Materials Research Center (FMF) in close collaboration with the University of Torino, Department of Chemistry, IPM (Torino, Italy); University Louis Pasteur and Ecole d' Application des Hauts Polymer (EAHP—Strasbourg, France), and University of Kaiserslautern (Germany), and was supported by EPF (European Polymer Federation) of GPF (Group Fransais des Polymers). The Organizing Committee included R. Mulhaupt (Chairman, Germany), G. Camino (Italy), W. Becker (Germany), J. Brossas (France), and L. Costa (Italy). The Scientific Committee included W. Becker (BASF AG, Germany), G. Camino (University of Torino), P. Flury (Ciba-Geigy AG, Switzerland), I. C. McNeill (University of Glasgow, UK), R. Mulhaupt (University of Freiburg, Germany), J. Otton (Rhone-Poulenc, France), J.-C. Robinet (Norsolor, France), J. Troitzsch (Wiesbaden, Germany), J. Brossas (EAHP, Strasbourg), L. Costa (University of Turin), R. Locatelli (Himont, Ferrara, Italy), C. Moye (Centre Scientifique et Technique du Batiment, Name-la-Valle, France), S. Russo (University of Sassart, Italy), A. Sainrat (Lab. Nat. d'Essais, Paris, France), and D. Woolley (Fire Research Station, Borehamwood, UK).     

HS-SPME/GC-MS法分析香椿芽、叶的挥发性化学成分

采用顶空固相微萃取/气相色谱-质谱(HS-SPME/GC-MS)联用技术分析香椿芽、叶的挥发性化学成分,用峰面积归一化法测定了各挥发性物质的相对质量分数。结果表明:从香椿芽萃取物中鉴定出26个成分,占挥发性组分总质量的74.86%,主要成分是β-石竹烯(质量分数,下同,10.12%),2-氮杂环丙烷乙基胺(10.09%),2-氨氧基丙酸(10.03%),β-香柠檬烯(8.78%),桉-4(14),11-二烯(6.59%),α-荜澄茄油烯(3.02%),α-雪松烯(2.88%),罗勒烯(2.69%),8-异丙烯基-1,5-二甲基-1,5-环癸二烯(2.36%),2-羟基乙基联氨(2.10%),丙基柏木醚(2.07%),羟基乙醛(1.88%),环癸烷醇(1.63%),外-葑醇(1.54%),1,3,8-对?三烯(1.46%),α-姜黄烯(1.18%);从香椿叶萃取物中鉴定出46种成分,占挥发性组分总质量的91.2%,主要成分是β-石竹烯(46.87%),(E)-2-己烯醛(5.29%),α-石竹烯(4.12%),8-异丙烯基-1,5-二甲基-1,5-环癸二烯(3.96%),β-香柠檬烯(3.48%),桉-4(14),11-二烯(3.37%),α-荜澄茄油烯(3.23%),β-波旁烯(2.41%),2-氮杂环丙烷乙基胺(2.23%),α-法呢烯(1.42%),异石竹烯(1.22%),β-萜烯(1.03%)。     

服装用静电植绒胶的合成与应用

以丙烯酸丁酯(BA)为软单体、丙烯酸甲酯(MA)为硬单体、2-乙基己烷丙烯酸酯(2-EHA)为特软单体、丙烯酸(AA)为亲水单体、二甲基丙烯酸乙二醇酯(EGDM)为交联剂、平平加(O-25)和十二烷基硫酸钠(SDS)为复合乳化剂、过硫酸钾(KPS)和偏重亚硫酸钠(SM)为氧化还原型引发剂,采用乳液共聚法合成环保型静电植绒胶。结果表明:当m(BA)∶m(MA)∶m(2-EHA)∶m(AA)∶m(EGDM)∶m(0-25/SDS)∶m(KPS/SM)=100∶40∶4∶8∶3∶(26/7)∶(1/1.0)时,胶粘剂稳定性较好;此时静电植绒织物中无游离甲醛含量和APEO含量,其摩擦牢度2 500次且柔软度为4~5级,符合生态服装面料的使用要求。     

Cofactor-apoprotein hydrogen bonding in oxidized and fully reduced flavodoxin monitored by trans-hydrogen-bond scalar couplings

Hydrogen bonding plays a key role in the tight binding of the FMN cofactor and the regulation of its redox properties in flavodoxins. Hydrogen bonding interactions can be directly observed in solution by multidimensional heteronuclear NMR spectroscopy through the scalar couplings between donor and acceptor nuclei. Here we report on the detection of intermolecular trans-hydrogen-bond couplings ((h)J) between the flavin ring system and the backbone of Desulfovibrio vulgaris flavodoxin in the oxidized and the two-electron reduced states. For this purpose, experiments are adapted from pulse sequences previously applied to determining (h)J coupling constants in nucleic acid-base pairs and proteins. The resulting (h2)J(N,N), (h4)J(N,N), (h3)J(C,N), and (h1)J(H,N) couplings involve the (15)N(1), (13)C(2), and (15)N(3) nuclei of the pyrimidine moiety of FMN, whereas no such interactions are detectable for (13)C(4) and (15)N(5). Several long-range (15)N-(15)N, (13)C-(15)N, and (1)H-(15)N J-coupling constants within the flavin are obtained as "by-products". The magnitudes of both (h)J and regular J couplings are found to be dependent on the redox state. In general, good correlations between (h)J coupling constants and donor-group (1)H chemical shifts and also crystallographic donor-acceptor distances are observed.