新型配位聚合物的合成研究

通过水热法合成新型的三维异金属配位聚合物{Na Nd(C2O4)2[HN(CH3)2](H2O)2·H2O}n。利用X-射线单晶衍射、元素分析、红外光谱和粉末X-射线衍射对其结构进行了表征。由X-射线单晶衍射分析可得:配位聚合物为单斜晶系,结晶在P21/n空间群,配合物晶体学参数:a=9.699(6)nm,b=11.849(8)nm,c=12.369(8)nm,β=99.236(6),Z=4;红外光谱分析表明,配合物在3388cm-1处的强宽峰为水的O-H伸缩振动吸收峰,1608cm-1处为羧基中C=O振动吸收峰,1396cm-1处为二甲基胺的振动吸收峰。通过热重分析结果观察,配位聚合物的二维框架结构的稳定温度达到350℃左右,其热稳定性较好。配位聚合物通过C2O42-以两种不同的配位模式连接成二维层状结构,并通过C2O42-进一步构建出三维空间结构。     

3-碘-4-苯基香豆素的简便合成

用苯酚与苯丙炔酸反应生成苯丙炔酸苯酯,在碱性条件下与碘单质发生反应,合成3-碘-4-苯基香豆素。用无机碱碳酸氢钠在硝基甲烷溶剂中合成3-碘-4-苯基香豆素时间最短,产率最高。     

有机硅氧烷改性苯丙乳液的研究

在苯乙烯—丙烯酸酯乳液共聚反应中,加入少量乙烯基硅氧烷,制得改性苯丙乳液,通过红外光谱初步确定了聚合物结构。研究了乳化剂用量、单体配比、有机硅用量等因素对反应进程、乳液稳定性及涂膜性能的影响。     

聚卟啉的制备及其在光氧化催化反应中的应用

通过Sonogashira Hagihara偶联聚合制备了一系列具有多孔结构的网状交联聚卟啉光催化剂,设计了双溴双炔卟啉和四溴卟啉两种结构的卟啉单体,通过双溴双炔卟啉自聚得到多孔有机聚卟啉(PPOP-1),通过四溴卟啉与含双炔基的单体(1,7-辛二炔、对苯二炔、联苯二炔)共聚得到聚卟啉PPOP-2、PPOP-3和PPOP-4.通过SEM和物理吸附仪观测聚合物的表面形貌和表征孔结构.结果显示,4种聚合物均具有均匀的颗粒形态和微孔结构,孔径约1 nm,比表面积分别为38.484、12.494、10.880和19.858 m2/g.以聚卟啉为异相光催化剂,通过可见光诱导二苄胺、缩硫酮、二苄基硫醚的有氧氧化证实了其对C—N和C—S键的氧化均具有优于单体催化剂的催化活性.PPOP-1(0.01 mmol)在可见光下催化二苄胺(0.1 mmol)的氧化反应,8 h后体系原料转化率和选择性均可达99％.经过4次循环催化后,PPOP-1仍保持较高的催化活性,原料转化率仍能达到99％.     

费托合成铁基催化剂上CO和H2的吸附特性

在25～300℃和0.1～2.5MPa范围内,利用程序升温脱附及原位漫反射红外光谱考察了CO,H2及合成气在费托合成沉淀铁基催化剂上的吸附行为.程序升温脱附表明,CO在铁基催化剂表面上存在线性、孪性及桥式吸附,对H2则有强、弱两类吸附活性中心;CO吸附红外光谱表明,2170和2116cm-1处存在明显的线性吸附双峰,1623～1313cm-1处存在少量表面态吸收峰,且随温度升高,在2360和2319cm-1处出现了CO2的特征吸收峰,催化剂表面对CO的吸附受温度和压力影响;合成气共吸附反应的红外光谱表明,费托合成烃生成机理及含氧化合物生成机理可用吸附态物种的变化解释,升高温度有利于CO加氢反应进行,高温高压有利于C2+含氧化合物生成.     

复合有机硅改性苯丙乳液的性能

以苯乙烯(St)、丙烯酸异辛酯(EA)和丙烯酸丁酯(BA)为主要单体,丙烯酸(AA)为功能单体,十二烷基苯磺酸钠(SDS)和壬基酚聚氧乙烯醚(OP-10)为复合乳化剂,γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)、乙烯基三甲氧基硅烷(A-171)和八甲基环四氧硅烷(D4)为有机硅改性剂,通过乳液聚合合成了不同有机硅改性苯丙乳液。研究了复合乳化剂的用量及配比,软硬单体质量比,以及复合有机硅改性剂的配比与用量对苯丙乳液性能的影响,确定了合成有机硅改性苯丙乳液的较佳用量:有机硅的质量分数为6%,软单体(EA、BA)和硬单体(St)的质量比为1∶2,OP-10与SDS的质量比为3∶2,且复合乳化剂的用量为3%。通过红外光谱和热重分析对苯丙乳液,KH570、A-171或D4单一改性以及复合改性苯丙乳液进行了表征,测试了各种乳液及其涂膜的性能。结果表明,有机硅改性后苯丙乳液的综合性能明显提高,复合有机硅改性苯丙乳液的性能最好。当复合有机硅中KH570、A-171和D4的质量比为1∶2∶1时,合成的复合有机硅改性苯丙乳液的固含量为41.33%,粒径80.09 nm,黏度127 mPa·s,其漆膜硬度为2H,吸水率9.34%,失重温度区间在450~520°C,高于苯丙乳液的350~420°C以及由KH-570、A-171或D4单一改性苯丙乳液的390~430°C。     

研发动态

乙烯基硅氧烷改性苯丙乳液大连轻工业学院的高世萍等以苯乙烯、丙烯酸丁酯为原料 ,在共聚反应后期 ,加入少量乙烯基三乙氧基硅烷 ,制得改性苯丙乳液。通过红外光谱初步确定了聚合物的结构。讨论了反应温度、反应时间、有机硅单体加入方式、乳化剂用量等因素对反应进程、乳液稳定性及涂膜性能的影响。最佳反应条件为 :初期反应温度 78～ 81℃ ,后期升温至 83～ 86℃ ,反应时间 5h ,有机硅用量为 4%～ 1 0 % ,复合乳化剂用量为 1 5 %～ 2 0 %。采用预聚接枝法制得的苯丙乳液产品性能良好。有机硅树脂在耐热型粉末涂料中的应用中国科技大学的…     

聚酰亚胺液晶取向膜的制备及性能研究

以1,3-二硝基苯为原料通过四步合成了3,5-二氨基联苯,将制得的二胺单体分别与环丁烷四甲酸二酐和均苯四甲酸二酐聚合得到二种新型聚酰亚胺。通过核磁氢谱和红外光谱分别对单体和聚合物的结构进行了表征,测试了聚合物的溶解性、热稳定性以及用作液晶取向膜的性能。制得的聚酰亚胺薄膜具有良好的热稳定性和平行取向性能。     

聚乙二醇二酸(2-羟甲基-3,5,6-三甲基吡嗪)酯的合成

以二环己基碳二亚胺(DCCI)为缩合剂,用聚乙二醇-2000-二酸来修饰2 羟甲基 3,5,6 三甲基吡嗪,产率69%。通过熔点、IR和1HNMR对产物进行了表征,熔点为45～48℃;红外特征吸收为1747cm-1(CO),1254cm-1(C—O—C);1HNMR为1 9(—CH3,3H,s),2 2(—CH3,6H,s),4 2(—CH2—,2H,s),3 6(—OCH2—,multi-H,s)。     

淀粉标签胶耐水性的改性研究

木薯淀粉经H2O2氧化后,在糊化过程中以H3PO4为酸催化剂,通过添加甲醛和尿素进行复合改性,由此制备出一种改性氧化淀粉粘合剂;然后将其分别与苯丙乳液(SAE)、脲醛树脂(UF)、改性脲醛树脂(M-UF)和SAE/M-UF进行交联复配制取标签用复合粘合剂,并利用傅里叶红外光谱(FT-IR)技术分析了交联复配过程中基团的变化情况。结果表明:改性氧化淀粉粘合剂的脱标时间为2h;相应的复合粘合剂的脱标时间分别为6、24、48、73h,即均能满足现代标签胶的使用要求;-OH伸缩振动吸收峰在复配过程中有变窄的趋势;反应过程中生成的UF在1550～1650cm-1附近出现了2～3个新的吸收峰,分别对应C-N和-NH-的伸缩振动吸收峰;复配过程中引入的SAE会在1750cm-1附近出现酯基的吸收峰。     

Synthesis of UV‐curable difunctional silane monomer based on 3‐methacryloxy propyl trimethoxysilane (3‐MPTS) and its UV‐curing characteristics and thermal stability

In the present investigation, silicon containing UV‐curable difunctional monomer was synthesized by reacting 3‐methacryloxy propyl trimethoxysilane (3‐MPTS) with acrylic acid using anhydrous ether as a solvent under inert atmosphere. The synthesized acryloxymethacryloxy silane monomer was characterized by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopy. The silane monomer along with 4 wt % photoinitiator (Darocure 1173) was cured under UV‐light for different exposure time. The curing characteristic of the monomer was investigated using FTIR spectroscopy. The conversion of the double bond due to curing has been evaluated from the peak intensity of the C?C double bond (at 1636 cm^?1) in the FTIR spectrum considering the peak intensity at 1720 cm^?1 due to C?O as internal standard. The maximum double bond conversion is observed to be 72%. The optimum cure time for the silane monomer has been estimated to be 7.8 sec. The UV‐cured sample decomposes at 440°C. The char residue is 35% at 700°C. The synthesized UV‐curable silane monomer may be useful for UV‐coating formulations, for fabrication of 3D‐objects by lithographic technique and as a precursor for organic–inorganic hybrid materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of bio-based high-strength elastomer through in-situ generated ionic network based on itaconic acid in natural rubber

采用原位共混法使可再生的生物基材料衣康酸与氧化锌在天然橡胶（NR）中原位生成衣康酸锌,然后通过过氧化二异丙苯引发衣康酸锌接枝到NR分子链上,构筑羧酸锌离子网络。结果表明,该离子网络的可逆性能可有效提高NR的强度,无炭黑填充NR的拉伸强度达到16.7 MPa,扯断伸长率达472%,储能模量和损耗模量均增大。     

一种双官能团环氧单体的合成及其UV固化性能研究

作者用廉价易得的乙二醇和石油化工产品双环戊二烯(DCPD)在H2SO4的催化下得到2 [(三环[5.2.1.02,6]癸 4 烯 8 基)氧]乙醇(TDEE)。通过正交实验得出其最佳合成条件:n(DCPD)∶n(乙二醇)=2∶3,以占二者总质量28 9%的w(H2SO4)=98%的硫酸做催化剂,在120℃反应5h。此条件下,TDEE的产率达76 8%。再经过己二酸酯化和环氧化合成了一种脂环族双官能团环氧单体———己二酸二{2 [(5 氧杂四环[6.2.1.02,7.04,6]十一烷 9 基)氧]}乙基酯(OTUEA),并对反应条件进行了优化。酯化反应的适宜条件是:每1mol己二酸用甲苯6 5mol作为带水剂,n(己二酸)∶n(H2SO4)=9∶1,己二酸二{2 [(三环[5.2.1.02,6]癸 4 烯 8 基)氧]}乙酯(TUEA)的产率可达97 7%;环氧化反应的适宜条件为:n(PhCO3H)∶n(TUEA)=2 2∶1,温度0℃,反应时间24h,环氧化产率为95 4%。用FTIR、1HNMR对其结构进行了表征。利用紫外灯与FTIR并用的方法对其UV固化行为进行了研究,得到其转化率随时间的变化曲线,将它与商业化的产品UVR-6110的UV固化行为比较,发现OTUEA的UV固化活性更高,是一种很好的阳离子型UV固化单体。     

二茂铁甲酸原位接枝环氧化端羟基聚丁二烯的合成研究

选用四丁基溴化铵作相转移催化剂,进行二茂铁甲酸(FcCA)接枝环氧化端羟基聚丁二烯(EHTPB)的合成研究.合成产物的红外光谱和1H-NMR显示,在1714和1276 cm-1处表现出明显的羧酸酯基团特征吸收峰,在1139和823 cm-1处表现出茂环特征吸收峰,在4.2～4.9处显示茂环上9H的核磁共振谱带.化学分析...     

含吡啶环二胺及其可溶性聚酰亚胺的制备与表征

以对羟基苯乙酮和苯甲醛为原料,通过亲核取代反应、改进的Chichibabin反应和水合肼催化还原合成了一种新型含吡啶环的芳香二胺4-苯基-2,6-双[4-(4-胺基苯氧基)苯]吡啶(ρ-PAPP),以N,N-二甲基甲酰胺(DMF)为溶剂,将ρ-PAPP与双酚A型二酐（BPADA）通过2步法合成了含吡啶环的新型聚酰亚胺。用红外光谱、差示扫描量热分析、热重分析、X射线衍射、溶解性测试等对聚合物的结构和性能进行了表征。结果表明,所得聚合物在1780、1723、1376 cm-1左右出现了聚酰亚胺的特征吸收峰;实验所得的聚酰亚胺能很好地溶解在常见有机溶剂中;玻璃化转变温度为191.2 °C;氮气气氛中,热失重10 %时的温度为473.8 °C,800 °C的残炭率为43 %;同时还有较好的力学性能,拉伸强度为98.5 MPa,拉伸模量为1.24 GPa,吸水率为0.67 %。     

红外光谱法测热可逆共价键交联氯醇橡胶的组成

以交联单体双环戊二烯二甲双缩水甘油酯（ＤＧＤＣＡ）的特征峰（１７１２ｃｍ＾－１）和环氧氯丙烷均聚物（ＰＥＣＨ）的特征峰（７５０ｃｍ＾－１）为定量计算的基准峰,测定不同质量比的ＤＧＤＣＡ与ＰＥＣＨ混合物ＩＲ谱图。混合物组成与光密度比值（Ｄ１７１２／Ｄ７５０）关系的回归方程为：（Ｄ１７１２／Ｄ７５０＝０．０２０９＋６．６４ＷＤＧＤＣＷＥＣＨ）,进而建立了通过Ｄ１７１２／Ｄ７５０求取共聚物中ＤＧＤＣＡ结     

Synthesis,characterization, and curing of a new acrylate‐based dental restorative resin

The synthesis of monomer 1,3‐bis [(2‐hydroxy‐3‐acrylate) propyloxy]2‐hydroxy propane (BHAPP) is reported for the possible use in dental restoratives. The monomer was prepared by the reaction of acrylic acid with diglycerol diglycidyl ether (DGE) in the presence of triethyl amine as a catalyst. The progress of the reaction at 60°C followed by measuring the intensity of the epoxide absorption peak at 915 cm^?1 which has reached to its minimum value after 5 h. The structure of the monomer was characterized by FTIR and ¹H‐NMR. The monomer was a moderately viscous light yellow color liquid having a refractive index of 1.544. Thermal curing of the monomer in DSC in the presence of benzoyl peroxide showed exothermic peak with maximum temperature (T_p) varied from 89 to 107°C depending on the heating rate and activation energy of 83 kJ/mol. Photopolymerization of the monomer by visible light in the presence of camphorquinone and N,N‐dimethylaminoethyl methacrylate as the photoinitiating system showed maximum 60% conversion after 40 s exposure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Soybean (<Emphasis Type="Italic">Glycine max</Emphasis>) Root Lignification Induced by Ferulic Acid. The Possible Mode of Action

Ferulic acid, in the form of feruloyl CoA, occupies a central position as an intermediate in the phenylpropanoid pathway. Due to the allelopathic function, its effects were tested on root growth, H(2)O(2) and lignin contents, and activities of cinnamyl alcohol dehydrogenase (CAD, EC 1.1.1.195) and peroxidase (POD, EC 1.11.1.7) from soybean (Glycine max (L.) Merr.) root seedlings. Three-day-old seedlings were cultivated in half-strength Hoagland's solution (pH 6.0), with or without 1.0 mM ferulic acid in a growth chamber (25 degrees C, 12/12 hr light/dark photoperiod, irradiance of 280 mumol m(-2) s(-1)) for 24 or 48 hr. Exogenously supplied ferulic acid induced premature cessation of root growth, with disintegration of the root cap, compression of cells in the quiescent center, increase of the vascular cylinder diameter, and earlier lignification of the metaxylem. Moreover, the allelochemical decreased CAD activity and H(2)O(2) level and increased the anionic isoform PODa5 activity and lignin content. The lignin monomer composition of ferulic acid-exposed roots revealed a significant increase of guaiacyl (G) units. When applied jointly with piperonylic acid (an inhibitor of the cinnamate 4-hydroxylase, C4H), ferulic acid increased lignin content. By contrast, the application of 3,4-(methylenedioxy) cinnamic acid (an inhibitor of the 4-coumarate:CoA ligase, 4CL) with ferulic acid did not. Taken together, these results suggest that ferulic acid may be channeled into the phenylpropanoid pathway (by the 4CL reaction) and, further, may increase the lignin monomer amount solidifying the cell wall and restricting the root growth.     

4-硝基苯乙烯基吡啶类氢键液晶的合成及表征

该文用4-硝基苯甲醛和4-甲基吡啶合成了质子受体4-硝基苯乙烯基吡啶,用无水乙醇重结晶得黄色固体,其熔点126.8～128.9℃,产率27%。用4-羟基苯甲酸和1-溴代正烷合成了质子供体4-烷氧基苯甲酸,用体积分数为95%的乙醇重结晶,所得4种中间体产率都在20%左右。最后,以上述两个中间体为原料,制备了系列4-硝基苯乙烯基吡啶类氢键型液晶。IR和1H NMR证实了各中间体结构。POM、IR、DSC检测了各复合物。POM拍摄的向列相、近晶相液晶织构表明,3种该氢键复合物均呈现明显的液晶态,且n=3时为向列相,n=5、8时为近晶相;IR图谱3500～2500cm-1处峰的变化及羰基向高波数位移,证明了羧基和吡啶间的分子间氢键代替了羧基间的分子间氢键。各复合物的液晶区间范围比各相应单体增大了1倍,表明羧酸吡啶间氢键起到了稳定液晶态的作用。     

Synthese einiger neuer 3,4-Diarylsydnone

Synthesis of Some New 3,4-Diarylsydnones The synthesis of some new sydnones 4 is described. Their characteristic absorption maxima, mass spectroscopic fragmentation and CO-valence vibrations are given. The sydnones 4 are synthezid by nitrosation of C, N-diarylglycines 3 (from strecker synthesis) and subsequent cyclization with Ac₂O. The primarily formed C,N-diaryl-α-aminoacetic acid nitrils ( 1 ) are decomposed with conc. HCl yielding glycines ( 3 ) in good yields.