微波法制备纤维素长链酰基酯及表征

纤维素和高级脂肪酸在均相条件下借助微波辐射合成了纤维素长链脂肪酸酯.当对纤维素/月桂酸/甲苯磺酰氯反应体系进行微波辐照,反应时间从传统加热(80℃)F的24 h下降至90 s,而其产物的取代度最人为2.56,研究了原料配比、微波时间等对产物取代度(DS)、质量收率和摩尔收率的影响以及DS与产物溶解性的关系,并对产物的结构进行了表征.结果表明脂肪酸酯基接枝在了纤维素骨架上,由此制备的纤维素薄膜材料具有一定的机械性能.     

新型可降解聚富马酸硅基酯的合成与表征

以富马酸二叔丁基酯和2,2-双(p-二甲基-氯硅氧基苯)丙烷为单体,通过缩聚合成得到聚[富马酸-2,2-双(p-二甲基硅氧烷-苯基)丙烷硅基酯],采用核磁共振氢谱、差示扫描量热法、热失重分析和凝胶渗透色谱表征了聚合物.结果表明,该聚合物的重均分子量为6 912,聚合度为15.6,玻璃化转变温度为16.7℃,具有良好的热...     

共反应剂法均相合成长链脂肪酸纤维素酯

在纤维素LiCl/N,N-二甲基乙酰胺(DMAc)均相溶液体系中,以对甲苯磺酰氯(TosCl)为共反应剂,原位活化脂肪酸(RCOOH),合成了长链脂肪酸纤维素酯。采用红外光谱、核磁共振谱、X射线衍射、热重等分析手段对产品进行了表征。考察了脂肪酸含碳原子个数、反应物配比、反应温度、反应时间等酯化条件对产品取代度的影响。结果表明:当反应物纤维素葡萄糖苷(AGU)∶RCOOH∶TosCl=1∶3∶3,反应温度为85℃,反应时间为24h时,产品取代度最高,且随着长链脂肪酸碳原子数目的增加,产物酯化度下降。热重分析结果表明,酯化反应削弱了纤维素分子间及分子内的作用力,赋予了长链脂肪酸纤维素酯较低的热加工温度。长链脂肪酸纤维素酯在有机溶剂中的溶解度随取代度的增加而提高。     

Synthesis of oxygenated fatty acid esters from santalbic acid ester

The reaction of methyl octadec-trans-11-en-9-ynoate (1) with mercuric sulfate in the presence or absence of sulfuric acid is described. Treatment of 1 with mercuric sulfate in absolute methanol yielded methyl 9(10)-oxoocta-dec-trans-11-enoates (Product A). This product, upon treatment withm-chloroperbenzoic acid, afforded methyltrans-11,12-epoxy-9-oxooctadecanoate (4) and methyl 10-oxooctadec-trans-11-enoate (2). Sodium borohydride reduction of A furnished the corresponding hydroxy esters. The treatment of 1 with mercuric sulfate in the presence of sulfuric acid gave as major product methyl 9(10)-oxo-11(12)-methoxyoctadecanoates and methyl 9(10)-oxoocta-dec-trans-11-enoates as a minor product. When methyl 11,12-epoxyoctadec-9-ynoate was reacted with acid in methanol, methyl 12-hydroxy-11-methoxyoctadec-9-ynoate was formed, which on treatment with zinc chloride in CCl₄ yielded methyl 9,12-epoxyoctadec-9,11-dienoate exclusively. The preparation of oxo fatty esters from the total methyl esters ofSantalum album was also demonstrated. The structures of the products were established by chemical derivatization and spectral characterization.     

长链烷基酯/环氧基(聚)醚改性硅油的合成及表征

以三甲基环戊二烯基铂为催化剂,将甲基丙烯酸十八酯(SMA)、烯丙基环氧(聚)醚和低含氢硅油(PHMS)通过硅氢加成反应,合成了长链烷基酯/环氧基(聚)醚共改性硅油(PEESO)。根据催化剂用量、原料配比、反应温度以及反应时间对Si—H转化率的影响关系,设计了均匀正交实验。在正交实验结果基础上借助反应条件的单因素分析,确定了最佳反应条件:催化剂用量为反应物质量的0.004%,物料比n(PHMS)∶n(CC)=1∶1.05,反应温度为72℃,反应时间为3 h。采用傅里叶变换红外光谱(FTIR)和核磁共振氢谱(1HNMR)对产物结构进行表征,结果表明,长链烷基酯和环氧基(聚)醚成功接枝到聚硅氧烷主链中。     

氢化葵花油脂肪酸蔗糖酯的合成

以氢化葵花油为原料 ,采用两步法合成了氢化葵花油脂肪酸蔗糖酯。探讨了反应温度、时间、压力、催化剂用量、助熔剂等对蔗糖酯收率的影响规律。结果表明 :当助熔剂和催化剂分别为 30 %和 2 .1%时 ,在 15 0℃下反应 6h ,产物收率达 4 5 %以上。     

10-十一烯酸四氟丙酯的合成及表征

以四氟丙醇和10-十一烯酸为原料,采用直接酯化法合成了10-十一烯酸四氟丙酯(UATE),通过FT-IR和1H NMR对UATE进行了结构表征,考察了反应温度、四氟丙醇用量、催化剂用量、甲苯用量及反应时间5个因素对UATE酯化率的影响。通过响应面实验设计对UATE合成工艺进行优化,确定其最佳合成工艺条件为:n(四氟丙醇)∶n(10-十一烯酸)=3∶1,催化剂浓硫酸用量为0.5%,甲苯用量为7.6 m L,反应时间10 h,反应温度为138℃,在该条件下UATE酯化率最大为78.6%。     

铜铬催化剂催化脂肪酸甲酯加氢制备脂肪醇的研究

采用共沉淀法制备了铜铬催化剂并用于催化脂肪酸甲酯加氢反应制备脂肪醇。考察了催化剂种类和用量、反应温度、反应时间和反应压力等因素对反应结果的影响。确定了最佳实验条件,脂肪酸甲酯2.5g,m(铜铬催化剂)∶m(原料)=3∶200,反应温度230℃,氢气压力6MPa,反应时间6h。在该条件下,产物脂肪醇羟值186mgKOH/g,碘值22I2g/100g。另外,该催化剂回收重复利用5次后,脂肪醇的羟基值没有明显降低,具有较好的重复使用性能。     

长链聚酰亚胺的制备与表征

以长链二胺4,4' 二(4 氨基苯氧基)二苯砜(BAPS)为单体,采用两步法分别与二酐PMDA、ODPA、BPADA合成了3种链长的聚酰亚胺。实验利用GPC监测0 05mol/L聚酰胺酸(PAA)的数均聚合度(Xn)及相对分子质量分布随缩聚时间的变化关系,结果表明该反应为一逐步缩聚反应,缩聚速率随二酐电子亲和性(EA)的递增而增加;与预聚体聚酰胺酸相比,热处理环化得到聚酰亚胺其数均分子质量( Mn)和特性粘度[η]均有所下降,而分布指数(D)增大。此外还利用红外光谱(FTIR)、差分扫描量热法(DSC)、热重分析(TGA)等对聚酰亚胺进行了表征,结果表明聚酰亚胺(PI)的玻璃化温度(tg)和热分解温度(td)随着聚合单元长度的增加而降低。     

Preparation of long-chain fatty acid chlorides

Summary A rapid method has been found for preparing the long-chain fatty acid chlorides, which eliminates purification by distillation. It gave a quantitative yield of product containing less than 1.5% free acid. The method involves treating the free acid with phosphorus pentachloride or trichloride in an inert organic solvent and removing the excess chlorinating agent by washing the solvent phase with water. Phosphorus pentachloride and Skellysolve “F” were preferred for laboratory preparations. For commercial purposes however either chlorinating agent could be used in a variety of inert organic solvents. Infrared analysis was found to give a rapid measure of the free acid content of the prepared acid chlorides. Presented at the fall meeting, American Oil Chemists' Society, Philadelphia, Pa., Oct. 10–12, 1955. Issued as N. R. C. No. 4240.     

脂肪酸淀粉酯的合成与结构表征

脂肪酸淀粉酯是一种新型的非离子型表面活性剂,具有广泛的应用价值.以天然的淀粉和大豆油为原料,通过化学法进行酯化改性,制得混合脂肪酸淀粉酯.研究了基本的合成路线,并用FT-IR和UV对其结构进行表征.产物乳化性能比较优越.     

Synthesis and characterization of poly(ester ether siloxane)s

A series of novel thermoplastic elastomers based on ABA‐type triblock prepolymers, poly[(propylene oxide)–(dimethylsiloxane)–(propylene oxide)] (PPO‐PDMS‐PPO), as the soft segments, and poly(butylene terephthalate) (PBT), as the hard segments, was synthesized by catalyzed two‐step melt transesterification of dimethyl terephthalate (DMT) with 1,4‐butanediol (BD) and α,ω‐dihydroxy‐(PPO‐PDMS‐PPO) (M?_n = 2930 g mol^?1). Several copolymers with a content of hard PBT segments between 40 and 60 mass% and a constant length of the soft PPO‐PDMS‐PPO segments were prepared. The siloxane‐containing triblock prepolymer with hydrophilic terminal PPO blocks was used to improve the compatibility between the polar comonomers, i.e. DMT and BD, and the non‐polar PDMS segments. The structure and composition of the copolymers were examined using ¹H NMR spectroscopy, while the effectiveness of the incorporation of α,ω‐dihydroxy‐(PPO‐PDMS‐PPO) prepolymer into the copolyester chains was controlled by chloroform extraction. The effect of the structure and composition of the copolymers on the transition temperatures (T_m and T_g) and the thermal and thermo‐oxidative degradation stability, as well as on the degree of crystallinity, and some rheological properties, were studied. Copyright © 2006 Society of Chemical Industry     

Synthesis and characterization of hyperbranched poly(silyl ester)s

Hyperbranched poly(silyl ester)s were synthesized via the A₂ + B₄ route by the polycondensation reaction. The solid poly(silyl ester) was obtained by the reaction of di‐tert‐butyl adipate and 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The oligomers with tert‐butyl terminal groups were obtained via the A₂ + B₂ route by the reaction of 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyl‐trisi1oxane with excess amount of di‐tert‐butyl adipate. The viscous fluid and soft solid poly(silyl ester)s were obtained by the reaction of the oligomers as big monomers with 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The polymers were characterized by ¹H NMR, IR, and UV spectroscopies, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The ¹H NMR and IR analysis proved the existence of the branched structures in the polymers. The glass transition temperatures (T_g's) of the viscous fluid and soft solid polymers were below room temperature. The T_g of the solid poly(silyl ester) was not found below room temperature but a temperature for the transition in the liquid crystalline phase was found at 42°C. Thermal decomposition of the soft solid and solid poly(silyl ester)s started at about 130°C and for the others it started at about 200°C. The obtained hyperbranched polymers did not decompose completely at 700°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3430–3436, 2006     

Synthesis and characterization of cellulose ethers/Eu(III)

The coordination complexes of the crystalline structure of cellulose ethers/Eu(III) with fluorescence emission, viz CMC/Eu(III), MC/Eu(III), and HEC/Eu(III), were synthesized and characterized. Results showed the emission spectra of Eu³⁺ ions in these coordination compounds, which originates from electric dipole transition. The main emission peak at 615 nm generated from ⁵D₀→⁷F₂ transition of Eu³⁺ ions. Their absorption and excitation spectra were different, because the effect of the high polarity of water and having both hydrogen bond donor and acceptor properties on the excited molecule is different from the effect on the ground state of the molecule. Our study demonstrated that the Degree of Substitute (DS) of CMC could influence the fluorescence intensity (FI) of CMC/Eu(III). The emission intensity of CMC/Eu(III) varies with the DS of CMC. For example, when the DS of CMC was 0.89, the FS (fluorescent spectra) of solid CMC/Eu(III) displayed three emission peaks Eu(III): the strongest emission peak at 615 nm (⁵D₀→⁷F₂ transition) and other two weaker peaks at 583 nm (⁵D₀→⁷F₁ transition) and at 652 nm (⁵D₀→⁷F₃ transition), respectively. The concentration of Eu(III) could also affect the FI of these coordination complexes. The FI of the coordination complexes peaked at 615 nm all reached maximum when Eu³⁺ concentration was at 5% (wt/wt). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 743–747, 2005     

Gas chromatographic separation of long-chain fatty nitriles and long-chain acid amides

A method is described for the chromatographic separation of long-chain fatty nitriles and long-chain acid amides on a cyanopropyl silicone column. We found that better separations were obtained for these compounds using a cyano column than with any column previously reported. Formerly Armak Company.     

脂肪酸甲酯磺酸盐的制备、性能及应用研究进展

脂肪酸甲酯磺酸盐是一种生物相容性好、去污力优良和抗硬水能力强的高效、低毒表面活性剂。简要介绍了脂肪酸甲酯磺酸盐的制备方法、物理化学性能及其在洗涤剂中的应用。     

Synthesis of substituted fatty oxathiolanes and thioethers from an allylic oxo fatty acid ester

Substituted oxathiolane and thioether derivatives have been synthesized from an allylic oxo fatty acid ester. The reaction of methyl 4-oxo-trans-2-octadecenoate with 3-mercaptopropan-1,2-diol (1-thioglycerol) affords methyl 4-(3′-hydroxymethyl-1′,4′-oxathiolane)-2(3)-(O-mercaptopropan-1″,2″-diol)-octadecanoate (II), methyl 4-oxo-2(3)-(O-mercaptopropan-1′,2′-diol)-octadecanoate (III), methyl 4-(3′-hydroxy-l′,5′-oxathiane)-2 (3)-(S-mercaptopropan-1″,2″-diol)-octadecanoate (IV), methyl 4-oxo-2(3)-(S-mercaptopropan-1′, 2′diol)-octadecanoate (V) and methyl 4-(3′-hydroxymethyl-1′, 4′-oxathiolane)-2(3)-(S-mercaptopropan-1″, 2″-diol)-octadecanoate (VI). Structures of the individual reaction products have been established on the basis of spectral data and microanalyses.     

2-(4-溴甲基苯基)丙酸及其酯的合成

以对甲苯苯乙腈为原料经甲基化、水解和溴代3步反应合成了2-(4-溴甲基苯基)丙酸和以对甲基苯乙酸乙酯为原料经甲基化和溴代两步合成2-(4-溴甲基苯基)丙酸乙酯.重点探讨了甲基化反应的反应时间及不同相转移催化剂聚乙醇(PEG)对反应的影响.实验结果表明,甲基化反应以8 h为宜,对甲基苯乙腈和对甲苯苯乙酸乙酯甲基化反应的最...     

Preparation and characterization of cellulose nitrate-acetate mixed ester fibers

Cellulose nitrate-acetate mixed esters (CNA) were synthesized by nitration of cellulose diacetate, using HNO₃/H₂SO₄ as nitration agent. The CNA structures were confirmed and analyzed by IR and ¹H NMR. A decrease in molecular weight and an increase in nitrate group content were observed with increasing H₂SO₄ ratio and reaction time. The highest degree of nitrate substitution, 9.2%, for CNA was achieved with the reaction time of 6h in concentrated HNO₃. Increasing HNO₃ ratio in nitration media resulted in more thermally stable CNA. CNA fibers were prepared by altering the polymer concentration from 15 to 30% in an 85:15 (w/w) acetone:water solvent. The electrospun CNA fibers were characterized by SEM to investigate the influence of different NO₂% on fiber formation, diameters and architectures.     

(E)-3-甲氧基丙烯酸甲酯的合成

乙烯基甲基醚与光气在溶剂和催化剂存在下进行加成反应,生成酰氯化物3-氯-3-甲氧基丙酰氯,酰氯化物与甲醇在有机碱存在下反应生成3-氯-3-甲氧基丙酸甲酯,氯代烷基酯在无机碱和催化剂存在下进行裂解反应脱HCI得到且标产物(E)-3-甲氧基丙烯酸甲酯(MAME).选择了较合适的催化剂类型,较佳的乙烯基甲基醚:光气:有机碱C...