N—（2—苯基氨基乙基）乙酰胺类化合物的合成

合成了３个Ｎ－（２－苯基氨基乙基）乙酰胺类化合物，对合成工艺上进行了改进，降低了成本，提高了收率。     

Synthesis of POSS-containing fluorosilicone block copolymers via RAFT polymerization for application as non-wetting coating materials

By using a polydimethylsiloxane (PDMS) macro-chain transfer agent with trithiocarbonate groups at both ends, fluorosilicone block copolymers containing polyhedral oligomeric silsesquioxane (POSS) were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. Acryloisobutyl POSS (APOSS) and 2,2,3,4,4,4-hexafluorobutyl acrylate (HFBA) were sequentially introduced into the copolymers. The obtained triblock copolymers PDMS-b-(PAPOSS)₂ exhibited a low polydispersity index (PDI) of less than 1.42 in the first 6 h of polymerization, but the PDI value became broader later because of the steric hindrance of the POSS macromer. The POSS-containing fluorosilicone pentablock copolymers with a PDI of about 2.0, which were prepared by the further RAFT polymerization of HFBA, showed clear microphase separation. The average roughness values of the copolymer films were enhanced by introducing POSS, and a certain POSS content led to a significant decrease of the receding contact angle. Measurements of water contact angles and ice shear strengths demonstrated that the non-wetting properties of the copolymer films were improved by the incorporation of both POSS and fluorine blocks. The block copolymers combine the advantages of POSS, PDMS and fluoropolymers, and can be potentially applied as non-wetting coating materials for anti-icing or anti-frosting.     

N-(2-甲胺基乙基)邻苯二甲酰亚胺盐酸盐的合成

以乙醇胺为原料合成N-甲基乙二胺,采用新方法将其N-邻苯二甲酰化合成N-（2-甲胺基乙基）邻苯二甲酰亚胺,用于胺基保护以提高N-甲基乙二胺在亲核反应中的选择性,总收率32．5％。     

N-(2-氨乙基)吗啉的合成研究

以乙醇胺与吗啉为原料分两步制取N-(2-氨乙基)吗啉,第一步收率为69.6%,第二步收率为65.2%.N-(2-氨乙基)吗啉纯度为99.5%,红外谱图符合文献值.     

2-氯苄基-N-琥珀酰亚胺基碳酸酯的合成研究

以2-氯苄醇和三氯甲基碳酸双酯为起始原料,以二氯乙烷为溶剂,合成了氯甲酸2-氯苄酯,并和N-羟基琥珀酰亚胺反应制备得到肽类保护剂2-氯苄基-N-琥珀酰亚胺基碳酸酯。对反应条件进行了优化,两步反应的总收率接近50%,所得产品经1H NMR确证。     

Reactions of 2-(4-morpholinothio)- and 2-(4-morpholinodithio)benzothiazole in the presence of polyisoprene

2-(4-Morpholinothio)benzothiazole (MOR) and 2-(4-morpholinodithio)-benzothiazole (MDB) were reacted, in combination with sulfur and ZnO, in the presence of polyisoprene (IR). Samples were heated in a DSC at 2.5°C/min and characterized by swelling experiments. The products formed at various temperatures were analyzed by HPLC. Crosslinking only occurred once all the benzothiazole sulfenamide had been consumed, the onset of vulcanization characterized by a considerable increase in 2-mercaptobenzothiazole (MBT) concentration. Crosslinking occurred earlier in all corresponding MDB formulations. Higher crosslink densities were recorded with addition of ZnO. The delayed action experienced in MOR systems was attributed to an exchange reaction between benzothiazole-terminated pendent groups and MOR and not due to the stability of the disulfide, MDB. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1093–1099, 1997     

苯噻氰

苯噻氰是一种性能优良的杀菌剂,有3种常见合成方法,包括2种2-巯基苯并噻唑法和1种氯甲基化法。一种2-巯基苯并噻唑法是用2-巯基苯并噻唑与溴氯甲烷反应生成2-氯甲基硫代苯并噻唑,2-氯甲基硫代苯并噻唑再与硫氰化钠反应得到苯噻氰;另一种2-巯基苯并噻唑法是先将溴氯甲烷与硫氰化钠反应生成硫氰酸氯甲酯,然后硫氰酸氯甲酯与2-巯基苯并噻唑反应得到苯噻氰。氯甲基化法是先用2-巯基苯并噻唑与多聚甲醛和氯化氢反应生成2-氯甲基硫代苯并噻唑,2-氯甲基硫代苯并噻唑再与硫氰化钠反应得到苯噻氰。     

N-(2-呋喃甲酰基)氨基酸的合成

在温和的条件下,以2-呋喃甲酸为起始原料,通过3步合成了标题化合物,产率达89.6%～93.3%,通过~1HNMR、IR对其结构进行了表征.     

Synthesis and pH-dependent micellization of 2-(diisopropylamino)ethyl methacrylate based amphiphilic diblock copolymers via RAFT polymerization

The polymerization of 2-(diisopropylamino)ethyl methacrylate (DPA) by RAFT mechanism in the presence of 4-cyanopentanoic acid dithiobenzoate in 1,4-dioxane was studied. The DPA homopolymer was employed as a macro chain transfer agent to synthesize pH-sensitive amphiphilic block copolymers using poly(ethylene glycol) methyl ether methacrylate (PEGMA) as the hydrophilic block. ¹H NMR and GPC measurements confirmed the successful synthesis of these copolymers. Potentiometric titrations and fluorescence experiments proved that the copolymers underwent a sharp transition from unimers to micelles at a pH of ∼6.7 in phosphate buffered saline solutions. It was found that the hydrophilic/hydrophobic balance of these block copolymers had no apparent effect on their pH-induced micellization behaviors. The DLS investigation revealed that the micelles have a mean hydrodynamic diameter below 60 nm with a narrow size distribution.     

Synthesis of poly(trioctylammonium p-styrenesulfonate) homopolymers and block copolymers by RAFT polymerization

A method to prepare sulfonated polystyrene-containing block copolymers has been investigated by neutralizing styrene sulfonic acid with trioctylamine to produce the hydrophobic monomer trioctylammonium p-styrenesulfonate (SS-TOA). This monomer was polymerized by reversible addition fragmentation chain transfer (RAFT) polymerization to produce PSS-TOA homopolymers. A PSS-TOA homopolymer was then used as a macro-RAFT agent for the polymerization of styrene to prepare poly(trioctylammonium p-styrenesulfonate)-block-poly(styrene) (PSS-TOA-b-PS). These block copolymers could be ion-exchanged to produce either the hydrophilic sodium salt form of PSS or a hydrophobic quaternary ammonium salt. This approach will be useful for preparing PSS-containing block copolymers with a range of hydrophobic blocks for applications such as ion-exchange membranes.     

Synthesis and self-assembly behaviors of three-armed amphiphilic block copolymers via RAFT polymerization

The novel trifunctional reversible addition-fragmentation chain transfer (RAFT) agent, tris(1-phenylethyl) 1,3,5-triazine-2,4,6-triyl trithiocarbonate (TTA), was synthesized and used to prepare the three-armed polystyrene (PS₃) via RAFT polymerization of styrene (St) in bulk with thermal initiation. The polymerization kinetic plot was first order and the molecular weights of polymers increased with the monomer conversions with narrow molecular weight distributions (M_w/M_n ≤ 1.23). The number of arms of the star PS was analyzed by gel permeation chromatography (GPC), ultraviolet visible (UV-vis) and fluorescence spectra. Furthermore, poly(styrene-b-N-isopropylacrylamide)₃ (PS-b-PNIPAAM)₃, the three-armed amphiphilic thermosensitive block copolymer, with controlled molecular weight and well-defined structure was also successfully prepared via RAFT chain extension method using the three-armed PS obtained as the macro-RAFT agent and N-isopropylacrylamide as the second monomer. The copolymers obtained were characterized by GPC and ¹H nuclear magnetic resonance (NMR) spectra. The self-assembly behaviors of the three-armed amphiphilic block copolymers (PS-b-PNIPAAM)₃ in mixed solution (DMF/CH₃OH) were also investigated by high performance particle sizer (HPPS) and transmission electron microscopy (TEM). Interestingly, the lower critical solution temperature (LCST) of aqueous solutions of the three-armed amphiphilic block copolymers (PS-b-PNIPAAM)₃ decreased with the increase of relative length of PS in the block copolymers.     

酰化反应合成N-(2-溴-4-甲氧基苯基)丙烯酰胺的研究

研究了2-溴-4-甲氧基苯胺与丙烯酰氯发生酰化反应合成了N-(2-溴-4-甲氧基苯基)丙烯酰胺的方法。以95.7%的收率得到N-(2-溴-4-甲氧基苯基)丙烯酰胺。探讨了反应物物质的量比、反应时间、反应温度和碱的添加对酰化反应的影响。该方法原料易得,反应条件易于控制,收率高,对环境友好。     

3-N,N-双(β-甲氧基乙基)氨基-4-甲氧基乙酰苯胺合成研究

研究了用2-氯乙基甲醚和3-氨基-4-甲氧基乙酰苯胺合成标题化合物的反应条件。发现反应的主要因素在于反应过程中PH值和温度的控制。在整个反应过程中用缓冲溶液体系控制PH为5.5—6.5的条件下,反应温度为125℃左右分批加入2-氮乙基甲醚可得到收率大于91%、GC含量大于98%的产品。     

微波辐射合成N-(2-羟乙基)-邻苯二甲酰亚胺

在微波辐射下，邻苯二甲酸酐和乙醇胺反应可直接合成N-（2-羟乙基）-邻苯二甲酰亚胺。最佳条件为：辐射功率为259W，辐射时间为6min，邻苯二甲酸酐与乙醇胺的物质的量比为1：1.05，产率可达87.1％。     

N-(1-丁基-2-吡咯甲酰基)氨基酸甲酯的合成

在室温下,氨基酸甲酯和1-丁基-2-三氯乙酰基吡咯经酰基化反应,以81.3%~87.1%的产率,合成了系列N-(1-丁基-2-吡咯甲酰基)氨基酸甲酯,通过1HNMR,IR,MS和元素分析对其结构进行了表征。     

盖布瑞尔合成法制备N-(2-羟乙基)-邻苯二甲酰亚胺

报道了通过盖布瑞尔合成法制备N (2 羟乙基) 邻苯二甲酰亚胺。以DMF为溶剂,邻苯二甲酰亚胺钾盐与氯乙醇在90℃下反应12h,N (2 羟乙基) 邻苯二甲酰亚胺的收率为86%。讨论了反应温度、反应时间、物料比例以及不同溶剂对反应收率的影响。该方法操作简便,实验条件温和,后处理简便,适合N (2 羟乙基) 邻苯二甲酰亚胺的实验室制备。     

N-(2-氰乙基)二乙醇胺改性水性聚氨酯胶黏剂的合成与性能

以N-(2-氰乙基)二乙醇胺(NCD)作为扩链剂合成了不同NCD含量的水性聚氨酯(WPUs)。红外光谱测试分析了水性聚氨酯的结构以及NCD的加入对聚氨酯氢键作用力的影响,结果表明,聚氨酯氢键作用力随着NCD含量的增大先增大后减小。DSC、力学性能和T型剥离强度测试表明:随着NCD含量的增大,聚氨酯的结晶性得到提升,胶膜的拉伸强度及T型剥离强度呈先上升后下降的趋势,当NCD质量分数为6%时,力学强度达到20 MPa,断裂伸长率为394%,T型剥离强度达到29 N/cm。     

Synthesis of poly(vinyl alcohol) combs via MADIX/RAFT polymerization

Poly(vinyl acetate) combs have been prepared via macromolecular design via interchange of xanthate (MADIX)/reversible addition-fragmentation chain-transfer (RAFT) polymerization using xanthate functionalized polymer cores. The comb backbones were prepared using well-defined poly(vinyl alcohol) PVA polymers with a degree of polymerization of 20, 100 and 170, respectively. Functionalization with xanthates via R-group or a Z-group approach resulted in the formation of macromolecular MADIX agents. While Z group designed macromolecular xanthate agents appeared to inhibit the polymerization of vinyl acetate (VAc), R group designed macromolecular xanthate agents achieved to mediate efficiently the bulk polymerization of VAc affording PVAc combs. However, the growth of the combs was accompanied at low conversions by the formation of linear polymer chains as a result of the constant initiation (AIBN) and shoulders, which can be attributed to intermolecular coupling reactions. The proportions of single chains and termination products were observed to increase with the degree of polymerization of the macromolecular MADIX agents broadening the molecular weight distribution. As a result of a stable ester link between the branches and the PVA backbone, the branched PVAc architectures were finally hydrolyzed to afford poly(vinyl alcohol) combs.     

Kinetics of RAFT emulsion polymerization of styrene mediated by oligo(acrylic acid‐b‐styrene) trithiocarbonate

The kinetics of ab initio reversible addition‐fragmentation chain transfer (RAFT) emulsion polymerization of styrene using oligo(acrylic acid‐b‐styrene) trithiocarbonate as both polymerization mediator and surfactant were systematically investigated. The initiator concentration was set much lower than that in the conventional emulsion polymerization to significantly suppress the irreversible termination reaction. It was found that decreased rapidly but the nucleation efficiency of micelles increased with the decrease of the initiator concentrations due to the significant radical exit. The particle number ( ) did not follow the classic Smith–Eward equation but was proportional to [I]^?0.4[S]^0.7. It was suggested that RAFT emulsion polymerization could be fast enough for commercial use even at extremely low initiator concentrations and low macro‐RAFT agent concentrations due to the higher particle nucleation efficiency at lower initiator concentration. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2126–2134, 2016     

N-(3-氨基丙基)糠胺的合成及抑菌性研究

以糠胺及丙烯腈为原料,通过亲核加成、氢化反应合成了标题化合物,并通过多种谱学手段表征确证。在优化条件下,产物的总收率为75%,含量98%(HPLC)。该化合物对受试革兰氏阴性菌、阳性菌皆有明显的抑制作用。