二苯甲酮类高分子水溶性紫外线吸收剂的合成与表征

将2,4二羟基二苯甲酮与丙烯酰氯反应合成了2-羟基-4-丙烯酸酯基-二苯甲酮中间体,而后利用2-羟基-4-丙烯酸酯基-二苯甲酮中的双键与丙烯酰胺共聚产物反应,生成了水溶性紫外线吸收剂共聚产物。采用红外光谱,紫外光谱手段对产物进行了表征。结果表明产物水溶性好,在266nm处有强紫外吸收。     

二苯甲酮-三嗪紫外线吸收剂的合成及结构性能研究

以2,4-二羟基二苯甲酮、三聚氯氰、间苯二酚作为主要原料,通过2种方法合成二苯甲酮-三嗪混合型紫外线吸收剂(简称混合型吸收剂)。方法 A为由2,4-二羟基二苯甲酮、三聚氯氰制得4-(4,6-二氯-1,3,5-三嗪-2-氧基)-2-羟基二苯甲酮(化合物Ⅰ),化合物Ⅰ再与间苯二酚反应制得混合型吸收剂;方法 B为由三聚氯氰、间苯二酚制得2,4-二(2,4-二羟基苯基)-1,3,5-三嗪(化合物Ⅱ),化合物Ⅱ再与2,4-二羟基二苯甲酮反应制得混合型吸收剂,研究了化合物Ⅰ、化合物Ⅱ、混合型吸收剂的结构与性能。结果表明:方法 A合成的混合型吸收剂收率为73.5%,方法 B的收率为70.4%,所合成的产物为目标产物;所合成的中间产物及最终产物不溶于水及部分有机溶剂;混合型吸收剂在波长275,345 nm处有最大吸收峰,在波长为255~280,335~400 nm时,混合型吸收剂的紫外吸收性能优于化合物Ⅰ和化合物Ⅱ,在波长为280~310 nm时,3种紫外线吸收剂的紫外吸收性能由大到小依次为混合型吸收剂、化合物Ⅰ、化合物Ⅱ。     

含二苯甲酮类高分子水溶性紫外线吸收剂的合成与表征

将具有较好紫外线吸收能力的2,4二-羟基二苯甲酮(UV-0)与丙烯酰氯反应合成2羟-基-4丙-烯酸酯基-二苯甲酮(HAB)中间体,而后利用HAB中的双键与二甲基氨基丙基丙烯酰胺(DMAPAA)进行共聚反应,合成了水溶性紫外线吸收剂共聚物。采用红外光谱(FTIR),核磁共振(1H-NMR),紫外光谱(UV)等表征手段对产物进行结构表征。通过紫外光谱表明,产物在351 nm处有强紫外吸收。     

二苯甲酮类聚乙二醇基水溶型紫外线吸收剂的合成与表征

将2,4-二羟基二苯甲酮(UV-0)与氯乙酰氯反应合成2-羟基-4-氯乙酸酯基二苯甲酮(2H4CBP)中间体,然后利用氯乙酸酯基中活泼α-氯与不同分子量的聚乙二醇钠反应,合成了一系列聚乙二醇基水溶型紫外线吸收剂.采用红外光谱(FT-IR)、紫外光谱(UV)、核磁(1H-NMR)等手段对产物进行了结构表征.考察了不同平均分子量的聚乙二醇(PEGC(MW))对产物水溶解性能的影响,通过分光光度计测定计算了产物的紫外吸收效果残存率并考察了产物的光稳定性.结果表明当 PEG 平均分子量(MW)达到 1540 时,产物水溶性最好,溶解度为 6.87;产物在 243 nm、290 nm 和 322 nm处有强紫外吸收,并显示出较好的光稳定性;产物 PEG2000-g-(UV-0)2和PEG1540-g-(UV-0)2 在 290 nm处的摩尔消光系数分别为17899.7 L·mol-1·cm-1和17073.6 L·mol-1·cm-1.     

含二苯甲酮结构水溶性梳状高分子紫外线吸收剂的合成

将2,4-二羟基二苯甲酮(UV-0)、聚乙二醇单甲醚(mPEG)与丙烯酰氯反应合成中间体2-羟基-4-丙烯酸酯基二苯甲酮(2H4ABP)和聚乙二醇单甲醚丙烯酸酯,然后通过自由基溶液共聚合,将聚乙二醇单甲醚丙烯酸酯与2H4ABP、丙烯酸进行共聚合合成了一系列梳状水溶性高分子紫外线吸收剂。采用FT-IR、1H-NMR、UV等手段对产物进行了结构表征。紫外测试结果表明产物在244、291、340 nm处有强紫外吸收,与UV-0相比发生了明显红移。通过分光光度计测定计算了产物的紫外吸收效果残存率并考察了产物的光稳定性,结果表明产物有较好的光稳定性。     

侧基聚醚/二苯甲酮紫外吸收基聚硅氧烷的合成与表征

以H2PtCl6.6H2O为催化剂,甲苯为溶剂,通过硅氢化反应将端烯丙基聚氧乙烯聚氧丙烯醚(F6)和紫外吸收剂4-(3-烯丙氧-2-羟基)丙氧基-2-羟基二苯甲酮(AHDBP)同时引入聚甲基含氢硅氧烷(PHMS),合成了侧基聚醚/二苯甲酮紫外吸收基聚硅氧烷(PE-PUVSi),并用IR、UV和1HNMR对产物结构进行了表征。结果表明,在反应温度为80℃~100℃,甲苯用量为m(甲苯)∶m(PHMS)=1∶1,n(C=C)∶n(Si-H)=1.23∶1,n(F6)∶n(AHDBP)=2∶1的条件下可得到具有良好水溶性和对波长为243.6 nm、289.2 nm、325.0 nm处的紫外光有强吸收作用的产物。     

二苯甲酮类紫外吸收基聚硅氧烷的合成与表征

在铂催化剂作用下,用4-(3-烯丙氧基-2-羟基)丙氧基-2-羟基二苯甲酮(MUV-O)与含氢硅油(PHMS)在甲苯溶剂中的硅氢化加成反应,合成了一种侧链携带有二苯甲酮类紫外吸收基团的聚硅氧烷(PUVS i)。用红外光谱1、HNMR1、3CNMR、紫外光谱等对产物结构进行了表征。研究了合成反应条件,结果表明:当硅氢化反应温度为80~100℃,催化剂氯铂酸用量为原料总质量的(10~50)×10-6,m(MUV-O)∶m(PHMS)=16.4∶30时,产物PUVS i的接枝率可达91%。新合成的二苯甲酮类紫外吸收基聚硅氧烷PUVS i,对波长为243.2(吸光度A=0.797)、288.2(吸光度A=1.013)、325.4 nm(吸光度A=0.847)的紫外光有强吸收作用。     

二苯甲酮类聚乙二醇单甲醚基水溶型紫外线吸收剂的合成与表征

将2,4-二羟基二苯甲酮(UV-0)与氯乙酰氯反应合成2-羟基-4-氯乙酸酯基二苯甲酮(2H4CBP)中间体,然后利用氯乙酸酯基中活泼α-氯与聚乙二醇单甲醚醇钠反应,合成了一种新型聚乙二醇单甲醚基水溶型紫外线吸收剂,并对产物进行了结构表征。产物有较好的光稳定性,其水溶液在243、2903、22 nm处与UV-0有类似的3条特有吸收谱带,对波长200~400 nm的紫外光有良好的吸收作用。     

可聚合型紫外吸收剂及其聚合物的合成、表征和耐老化性能

为了解决涂层耐老化性能差和传统小分子紫外吸收剂迁移、挥发的问题,以对羟基苯乙酮、4-羟基二苯甲酮、2,4-二羟基二苯甲酮3种苯酮类化合物和N-羟甲基丙烯酰胺为原料,经Friedel-Crafts反应合成3种具有可交联特性的聚合型紫外吸收剂(3-丙烯酰胺甲基-4-羟基苯乙酮(A)、3-丙烯酰胺甲基-4-羟基二苯甲酮(B)和3,5-二丙稀酰胺甲基-2,4-二羟基二苯甲酮(C))。通过紫外吸收光谱分析,表明其对紫外线均具有较强的吸收能力。后采用溶液聚合法,将A、B和C分别与丙烯酸树脂聚合,得到3种具有紫外吸收特性的丙烯酸树脂。采用红外光谱和QUV紫外加速老化分析研究了其结构和性能。结果表明,紫外吸收剂成功接枝到丙烯酸树脂中,且接枝后丙烯酸树脂的耐老化性能得到了显著提高,耐老化时间比纯丙烯酸树脂增强300 h以上。     

聚合型紫外线吸收剂的合成研究Ⅰ.含2-羟基-4-丙烯酸酯基二苯甲酮的丙烯酸酯类乳液聚合

通过“粒子设计”利用核壳乳液聚合技术以功能型紫外线吸收剂、苯乙烯、丙烯酸丁酯、甲基丙烯酸甲酯、丙烯酸乙酯为单体制备出核壳结构的聚合物乳胶粒。其中,功能型紫外线吸收剂2-羟基-4-丙烯酸酯基二苯甲酮由2,4-二羟基二苯甲酮和丙烯酰氯制备。通过紫外分光光度法测试,此乳胶粒的吸收度大于同浓度下的功能型单体及2,4-二羟基二苯甲酮。     

Comparative study of the influence of active groups of chitosan derivatives on antifungal activity

In this study, series of chitosan derivatives containing active groups were synthesized and evaluated for their antifungal activity against three crop‐threatening fungi, Fusarium oxysporum. f. sp. Vasinfectum, Alternaria solani, and Valsa mali. Schiff bases of carboxymethyl chitosan (As: 2‐(2‐hydroxy‐5‐nitrobenzylideneamino)‐6‐carboxymethyl chitosan; Bs: 2‐(2‐hydroxyl‐5‐chlorobenzaldimino)‐6‐carboxymethyl chitosan), N‐substituted carboxymethyl chitosan (An: 2‐(2‐hydroxyl‐5‐nitrobenzylamino)‐6‐carboxymethyl chitosan; Bn: 2‐(2‐hydroxyl‐5‐chlorobenzylamino)‐6‐carboxymethyl chitosan) and 2‐urea‐carboxymethyl chitosan (Au: 2‐(2‐nitrophenylurea)‐6‐carboxymethyl chitosan; Bu: 2‐(2‐chlorophenylurea)‐6‐carboxymethyl chitosan) were synthesized, and their antifungal activity was comparatively studied by hypha measurement in vitro, respectively. Results obtained from this study revealed that the active groups combined with Schiff bases functional groups (C?N) could strengthen the antifungal activity most effectively among the compounds studied in this work. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Novel physical hydrogels composed of opened‐ring poly(vinyl pyrrolidone) and chitosan derivatives: Preparation and characterization

A novel, physically stabilized hydrogel system composed of chitosan (Chi) or its derivatives [e.g., carboxymethyl chitosan (CMC), sodium carboxymethyl chitosan, or trimethyl carboxymethyl chitosan (TMCMC)] with poly(vinyl pyrrolidone) (PVP) or opened‐ring poly(vinyl pyrrolidone) (OR–PVP) were prepared and characterized. TMCMC was synthesized by a novel method with dimethylsulfate as the methylation agent. The synthesized materials were characterized by Fourier transform infrared spectroscopy, ¹H‐NMR, ¹³C‐NMR, and size exclusion chromatography. The mechanical properties, gel fraction, swelling behavior, and water state of the prepared hydrogels were investigated. Gelation occurred when the OR–PVP and Chi solutions were blended within a few seconds. However, the gelation of the OR–PVP and CMC solutions needed pH adjustment. No gelation occurred when the solutions of TMCMC and PVP or OR–PVP were blended. The quaternization or protonization of  NH₂ groups may have prevented the gelation of the solutions. The amino groups of Chi derivatives should have been free to take part in hydrophilic bonds between the two polymers. The physical entanglement of polymeric chains and strong hydrogen bonds between the polymers were considered as mechanisms for the formation of the physical hydrogels. The physical hydrogels showed ionic and pH‐sensitive swelling properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

羧甲基壳聚糖席夫碱的制备及抗菌性能研究

在超声波作用下,以自制的低分子量羧甲基壳聚糖与香草醛为原料,制备了低分子量羧甲基壳聚糖香草醛席夫碱。利用FI-IR对其结构进行了表征,研究了香草醛与羧甲基壳聚糖中氨基的反应摩尔比、反应温度、反应时间及超声波功率对产物氨基取代度的影响。结果表明：当香草醛与羧甲基壳聚糖中氨基的摩尔比为1∶0.8、反应时间为3 h、反应温度为70℃、超声波作用功率为70 W时,羧甲基壳聚糖香草醛席夫碱的氨基取代度可达到82.5%;将羧甲基壳聚糖席夫碱与羧甲基壳聚糖的抗菌性能进行了比较,发现羧甲基壳聚糖香草醛席夫碱对金黄葡萄球菌和大肠埃希菌的抑菌圈宽度分别比羧甲基壳聚糖的抑菌圈宽0.7 mm和0.5 mm。     

Adsorption of guanosine,cytidine, and uridine on a β‐cyclodextrin derivative grafted chitosan

A β‐cyclodextrin derivative grafted chitosan (CDD‐C) was synthesized with chitosan and carboxymethyl‐β‐cyclodextrin (β‐CD). Its structure was characterized by elemental, infrared spectra, and X‐ray diffraction analyses. The degree of substitution by the carboxymethyl‐β‐CD moiety achieved 0.27 with the addition of DMF to the reaction solution. The results are in agreement with the expectations. The static adsorption properties for guanosine, cytidine, and uridine were studied. Experimental results demonstrated that CDD‐C had higher adsorption capability for guanosine than cytidine and uridine, and the adsorption capacity for guanosine was 74.20 mg/g. The adsorption capacity was greatly influenced by pH, time, and temperature. The introduction of chitosan enhanced the adsorption ability and adsorption selectivity of β‐CD for guanosine. This novel derivative of chitosan is expected to have wide applications in separation, concentration, and analysis of guanosine, cytidine, and uridine in biological sample. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3050–3055, 2007     

磁性N-羧甲基壳聚糖造影剂的制备及性能

采用简单经济(与传统微乳法、热分解法等比较)的方法制备出一种磁性N-羧甲基壳聚糖造影剂。首先对壳聚糖的氨基进行羧甲基化制备N-羧甲基壳聚糖,然后在其链上采用原位生成Fe3O4纳米粒子的方法制备出磁性N-羧甲基壳聚糖,并对其进行了表征及性能的测试。热重分析结果表明,Fe3O4的生成量与N-羧甲基壳聚糖中羧甲基的含量有关,其生成量随着羧甲基含量的增加而增加,但当羧甲基的含量增加到一定程度时,Fe3O4的生成量达到某一峰值。透射电镜结果表明,生成的Fe3O4纳米粒子的粒径约为5～10 nm。磁共振成像结果显示,该磁性N-羧甲基壳聚糖的横向弛豫率为82.82 mmol/(L.s),高于超顺磁性氧化铁作为磁共振成像造影剂时R2需大于62 mmol/(L.s)的最低标准,可作为潜在的磁共振成像阴性造影剂。     

Preparation of amphoteric N,O‐carboxymethyl hydroxypropyl chitosan by a two‐step reaction

A novel N,O‐carboxymethyl hydroxypropyl chitosan (HPCMS) derivative was prepared by a two‐step reaction. Water‐soluble hydroxypropyl chitosan (HPCS) with a degree of substitution of hydroxypropyl higher than 0.8 was first synthesized by the reaction of chitosan (CS) with propylene oxide (PO) with alkali as a catalyst. Then, amphoteric chitosan derivatives (HPCMS) with a degree of substitution of carboxymethyl ranging from 0.42 to 1.38 were prepared by the reaction of HPCS with chloroacetic acid in an aqueous solution with alkali as a catalyst. The structures of the polymers were characterized by Fourier transform infrared spectroscopy and NMR; this showed that the hydroxypropylation mainly occurred on the ? OH groups at the C‐6 of CS in the reaction of CS with PO. In the reaction of HPCS with chloroacetic acid, both the ? OH and ? NH₂ groups of HPCS were susceptible to the carboxymethylation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40460.     

羧甲基壳聚糖的制备与性能研究

以壳聚糖为原料制备了羧甲基壳聚糖,考察了NaOH用量、一氯乙酸用量、反应时间和反应温度对羧甲基壳聚糖取代度的影响,得出羧甲基化的最佳条件为：壳聚糖／一氯乙酸／氢氧化钠（m／m）=1：3．2：4,反应时间为3h,反应温度为60℃,制得产物的水溶性有较大提高,并利用红外光谱对产物结构进行了表征。     

改性壳聚糖对处理污泥脱水性能影响的研究

研究了聚合氯化铝、壳聚糖和3种羧甲基壳聚糖(N-羧甲基壳聚糖、N,O-羧甲基壳聚糖和O-羧甲基壳聚糖)絮凝剂对污泥的脱水性能作用。实验结果表明,羧甲基壳聚糖作为絮凝剂对污泥进行脱水时,形成的絮体强度大,不易破碎,对污泥脱水的效果明显好于普通絮凝剂。在3种所研究的羧甲基壳聚糖中,N-羧甲基壳聚糖对污泥的脱水效果最好,污泥比阻抗最低,与未加絮凝剂时相比,含水率从99.1%下降到73%,污泥的体积减少为原来的1/30,热值提高为原来的40倍。     

Synthesis and property studies of N‐carboxymethyl chitosan

N‐carboxymethyl chitosans (N‐CMC) were synthesized from chitosan in water with chloroacetic acid instead of comparatively expensive glyoxylic acid. The optimal reaction conditions were 90°C and 4 h with a ratio of chloroacetic acid to chitosan 5 : 1(w/w). The degree of substitution of product exceeded 1.32. The N‐carboxymethyl chitosans were characterized by XRD, FTIR, ¹H‐NMR, and the water solubility and isoelectric point of N‐CMC with different degrees of substitution were determined. FTIR and ¹H‐NMR data has confirmed that the substitution reaction occurred on the amino groups. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

羧甲基壳聚糖对Fe2+的络合及光谱分析

本文研究羧甲基壳聚糖对Fe^2＋的吸附性能,探讨了时间、PH值等对吸附性质的影响.PH=6时羧甲基壳聚糖对Fe^2＋最大吸附量为0.7mmol/g.并通过IR和UV光谱证实了羧甲基壳聚糖对Fe^2＋的络合作用.