均相制备纤维素/丙烯酰胺/甲基丙烯酸丁酯接枝共聚物的研究

以氢氧化钠/硫脲/尿素新型溶液溶解纤维素,在均相条件下以丙烯酰胺(AM)、甲基丙烯酸丁酯(BMA)为接枝单体,过硫酸铵为引发剂,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,通过自由基聚合法制备出了纤维素/AM/BMA接枝共聚物。考察了聚合温度、时间以及(NH4)2S2O8、AM、BMA、MBA的用量对接枝效果的影响。利用红外光谱(FT-IR)、X射线衍射(XRD)和扫描电镜(SEM)对接枝产物进行了结构表征。实验结果表明,纤维素/AM/BMA接枝共聚物的最佳合成条件为:m(纤维素)∶m(AM)∶m(BMA)∶m[(NH4)2S2O8]∶m(MBA)=1∶4∶2∶0.05∶0.006,反应温度为65℃,反应时间为2h,在此条件下接枝率可达87%,接枝效率为36%。制备的纤维素/AM/BMA接枝共聚物的吸水倍率为583g/g。     

BmimCl离子液体中纤维素-聚己内酯的合成与表征

以阔叶浆纤维素为原料,钛酸四正丁酯为催化剂,离子液体1-丁基-3-甲基咪唑氯盐(BmimCl)为溶剂,均相条件下与ε-己内酯单体进行开环聚合制备纤维素-聚己内酯接枝共聚物,探讨了单体与催化剂用量、反应温度与时间等条件对纤维素接枝率的影响,并用热重分析、X-射线衍射、核磁共振氢谱等手段对接枝共聚物进行了表征。结果表明,当ε-己内酯与纤维素摩尔比为21 mol/mol,反应时间为24 h,反应温度为120℃,催化剂与纤维素质量比为12%时,纤维素的接枝率最高达到86.7%;纤维素接枝ε-己内酯后,纤维素结晶结构被破坏,热稳定性下降,核磁共振氢谱分析显示ε-己内酯在与纤维素接枝反应的同时发生了自聚反应,生成聚己内酯。     

丙烯酸单体接枝纳米纤维素晶须的研究

以K2S2O8为引发剂,在纳米纤维素晶须(NCW)上接枝丙烯酸单体(AA),制备出丙烯酸接枝改性的纳米纤维素晶须.通过傅立叶变换红外光谱(FTIR)、透射电镜(TEM)、热重分析(TGA)等测试方法对接枝产物的性能进行了分析,并采用电导滴定的方法计算了接枝率以及表面取代基团含量.研究了反应条件对接枝率和接枝效率的影响.结果表明,在引发剂浓度为4 mmol/L,引发时间为5 min,纳米纤维素晶须与丙烯酸单体摩尔比为1: 1.5,反应时间为6 h的条件下,得到了接枝率为14.09%的丙烯酸接枝纳米纤维素晶须.实验证明,在NCW上可以接枝上丙烯酸,接枝率为14.09%的产物与NCW具有相似的表面形貌和热性能;TEM分析可知,接枝产物的分散性得到了提高;表面取代基团含量测试表明,接枝产物表面上的亲水性分散基团含量比NCW增加了5倍以上.     

丙烯酸单体接枝纳米纤维素晶须

以K2S2O8为引发剂,在纳米纤维素晶须(NCW)上接枝丙烯酸单体(AA),制备出丙烯酸接枝改性的纳米纤维素晶须。通过傅立叶变换红外光谱(FTIR)、透射电镜(TEM)、热重分析(TGA)等测试方法对接枝产物的性能进行了分析,并采用电导滴定的方法计算了接枝率以及表面取代基团含量。研究了反应条件对接枝率和接枝效率的影响。结果表明,在引发剂浓度为4mmol/L,引发时间为5min,纳米纤维素晶须与丙烯酸单体摩尔比为1∶1.5,反应时间为6h的条件下,得到了接枝率为14.09%的丙烯酸接枝纳米纤维素晶须。实验证明,在NCW上可以接枝上丙烯酸,接枝率为14.09%的产物与NCW具有相似的表面形貌和热性能;TEM分析可知,接枝产物的分散性得到了提高;表面取代基团含量测试表明,接枝产物表面上的亲水性分散基团含量比NCW增加了5倍以上。     

纤维素壳聚糖抗菌材料的制备

以制浆造纸中的木浆为原料,以过硫酸钾为引发剂,将木浆中的纤维素与壳聚糖进行接枝共聚,在可控制的条件下,合成具有抗菌性能的纤维素材料,并研究了合成时的接枝条件及其对接枝率、接枝效率的影响。研究结果表明,影响壳聚糖和纤维素的接枝共聚反应的主要因素包括K2S2O8浓度、预处理时间、预处理温度、反应温度、反应时间、壳聚糖浓度、交联剂用量等。用红外光谱技术分析了产物的结构。综合考虑应用效果和成本,确定了壳聚糖和纤维素的接枝共聚反应的最佳条件。     

纤维素接枝甲基丙烯酸乙酯的合成及表征

在过氧化氢和亚铁离子组成的氧化还原体系中加入第三组分二氧化硫脲(TD),将单体甲基丙烯酸乙酯(EMA)接枝于纤维素纤维上。探讨了单体EMA用量、过氧化氢用量、TD用量、反应温度、反应时间、去离子水用量等因素对接枝率、接枝效率的影响。结果显示纤维素接枝EMA的最佳工艺条件为:纤维8 g,EMA 6 g,过氧化氢0.02 g,TD 0.5 g,去离子水150 mL,反应温度50℃,反应时间1 h。红外光谱、扫描电镜分析均表明EMA接枝到了纤维素结构上。     

蔗渣/LiCl/DMAc溶液体系及其纤维素接枝聚丙烯酰胺的制备

为了发展利用植物生物质资源,采用将蔗渣溶于LiCl/DMAc体系并利用溶解于其中的物质与丙烯酰胺进行均相接枝反应以制备蔗渣接枝聚丙烯酰胺。结果表明蔗渣在160℃活化1h,烘干后与100g/L的LiCl/DMAc体系以固液比1∶50混合,然后在160℃加热4h的条件下可以取得81.3%的溶解率。溶液中不但含有纤维素,而且含有半纤维素和木质素。该溶液在30℃、N2环境且丙烯酰胺分两次投料的条件下进行共聚的接枝率达到62.86%。进一步的实验表明蔗渣接枝物的主要成分是纤维素-g-聚丙烯酰胺。这为植物生物质的高值化利用提供了新的途径。     

氧化微晶纤维素–壳聚糖薄膜状敷料制备与表征

采用氧化微晶纤维素–壳聚糖接枝物为材料,在不同壳聚糖接枝率、铸膜液浓度以及成膜温度的条件下制备薄膜状医用敷料。利用扫描电子显微镜对膜的结构进行表征。探讨铸膜液浓度、成膜温度、接枝率对氧化微晶纤维素–壳聚糖生物膜光学性能、溶胀率、溶失率、孔隙率和力学性能的影响。结果表明,当成膜温度为50℃,接枝率为42.4%,铸膜液浓度为40 g/L时,氧化微晶纤维素–壳聚糖薄膜性能比较优异,光透过率为75.7%,溶胀率为169.09%,溶失率为10.91%,孔隙率为95.2%,拉伸强度为80.06 MPa,断裂伸长率为35.5%,其有望成为一种新型医用敷料,促进壳聚糖和氧化微晶纤维素在医用领域的发展。     

一种新型球形纤维素吸附剂的制备Ⅱ.纤维素/AMPS接枝共聚物的合成

以交联球形纤维素珠体为骨架,以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为单体,通过接枝共聚的方法赋予球形纤维素吸附剂强酸型基团——磺酸基,因此首先合成出纤维素/AMPS共聚物,并进行制备条件的优选实验,得出最佳的制备工艺条件为:以Na2SO3/K2S2O8作为引发体系,引发剂的用量为2.5%,单体与纤维素的最佳比值为1.5∶1(W/W),反应温度40℃,反应时间4.0h。在上述工艺条件下,所制备出的纤维素/AMPS接枝共聚物的接枝率为46.9%,而AMPS的均聚物含量仅为5.4%。     

铈离子引发纤维素接枝甲基丙烯酸丁酯制备吸油材料的制备

以棉浆粕为基材,硝酸铈铵/HNO3为引发剂,甲基丙烯酸丁酯(BMA)为接枝单体,N ,N'-亚甲基双丙烯酰胺为交联剂,采用悬浮震荡接枝聚合反应制备了纤维素基吸油材料。采用红外光谱、X射线衍射、扫描电镜、热重分析、差示量热等手段对产物结构进行了表征,考察了棉浆粕的引发及其后的接枝聚合反应,得到最佳工艺条件为：采用含有铈离子的0.15 mol/L的HNO3水溶液在45 ℃下将棉浆粕活化处理2.5 h后,在HNO3水溶液及交联剂存在下,与BMA发生接枝聚合反应;反应配比为纤维素/引发剂/单体/交联剂=1/0.03/1.5/0.03,聚合反应温度为50 ℃,反应时间为24 h。所得纤维素与BMA的接枝共聚物有较高的接枝率及理想的吸油性能。     

Comparative study of homogeneous solvents for the esterification crosslinking of cellulose with 1,2,3,4‐butanetetracarboxylic dianhydride and water absorbency of the reaction products

Superabsorbent hydrogels were prepared via esterification crosslinking of cellulose with 1,2,3,4‐butanetetracarboxylic dianhydride (BTCA) in three solvent systems: lithium chloride (LiCl)/N‐methyl‐2‐pyrrolidinone (NMP), LiCl/N,N‐dimethylacetamide (DMAc), and tetrabutylammonium fluoride/dimethyl sulfoxide (TBAF/DMSO). The absorbency of the hydrogels was strongly dependent on the BTCA feed to cellulose ratio as well as the nature of the solvent system used. The rate of cellulose esterification was enhanced in TBAF/DMSO relative to the other systems, and the highest water absorbency of the hydrogels (987 g g^?1 polymer) was also achieved using this system. The hydrogels obtained in the TBAF/DMSO system had a similar degree of both crosslinking and grafting, indicating that both reactions were promoted to the same extent in this solvent, whereas crosslinking was preferentially enhanced over grafting in the LiCl/NMP and LiCl/DMAc systems. The difference in the composition of the hydrogels was attributed to the difference in the electronegativity of the fluoride and chloride anions in these solvents. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Graft polymerization of some vinyl monomers onto alkali-treated cellulose

Treatment of cellulose by different concentrations of alkali, namely, 5–30% NaOH, changed its fine structure and transferred cellulose I into cellulose II. The decreased crystallinity due to alkali treatment and the transformation of cellulose I into cellulose II lowered the reactivity of cellulose toward the grafting polymerization reactions. Compactness of the structure as a result of the treatment of cellulose with 5% sodium hydroxide concentration decreased the rate of the grafting reaction and the grafting yield. On the other hand, such treatment of cellulose with different concentrations of alkali increased the rate of ceric consumption, i.e., increased the rate of oxidation of cellulose. Thus, the termination reaction of the grafting polymerization process may occur as a result of such oxidation and because of the increase of the active sites onto cellulose, leading to a decrease of the grafting yields and rate of grafting polymerization reaction by using the free-radical grafting process. The use of the ionic-xanthate method of grafting polyvinyl- and polyallyl-on alkali-treated cellulose shows an increase of grafting efficiency and grafting yields. Maximum grafting efficiency and yields were achieved when cellulose was treated with sodium hydroxide concentration below 15%, and maximum crystallinity indices were obtained. Using 15–25% sodium hydroxide lowered the indices of crystallinity, and lower grafting yields and grafting efficiency were achieved. Thus, transformation of cellulose I into cellulose II decreased the reactivity of these treated celluloses toward graft polymerization reactions by the use of the ionic-xanthate method. In our opinion, termination reactions may also occur and affect the results.     

Factors affecting vapor phase photografting of vinyl monomers on cellulose

Effects of water contained in the sample, the type of sensitizer, and the nature of vinyl monomer on vapor phase photografting on cellulose were investigated at 60°C. The grafting was enhanced by the water contained in the cellulose sample, resulting in an increased percent grafting with increasing the quantity of water. The use of sensitizers such as ferric chloride, ferrous sulfate, ceric ammonium nitrate, hydrogen peroxide, benzophenone, and sodium anthraquinone-2,7-disulfonate led to accelerated graftings. However, the maximum grafting was observed at an optimum quantity of sensitizer for each sensitized system, and the formation of grafted polymer was restricted by the use of sensitizer beyond the quantity. Ferric chloride and hydrogen peroxide exhibited higher activities among the sensitizers. With respect to the nature of monomer, methyl methacrylate, acrylic acid, methacrylic acid, and acrylonitrile were observed to be introduced into cellulose substrate by the vapor phase photografting, though no initiation was recorded for styrene and N-vinylpyrrolidone. However, the latter monomers were introduced by using monomer mixtures with acrylonitrile, affording a maximum percent grafting at a certain monomer composition.     

Radiation-induced graft copolymerization of mixtures of styrene and acrylamide onto cellulose acetate. VI. Permeability of sodium chloride and sodium sulfate

Acrylamide, styrene, and mixtures of acrylamide and styrene were grafted onto cellulose acetate film. The permeabilities of sodium chloride and sodium sulfate through the ungrafted and grafted cellulose acetate films were studied. Permeability increases with the increase in the extent of grafting of acrylamide; whereas it decreases with the increase in the extent of grafting of styrene onto cellulose acetate. The same trend in permeability was observed when cellulose acetate was grafted with the binary monomer mixture. Permeability is also found to depend on the nature of the solute dissolved in water. The results were discussed in terms of free volume concept of the water-swollen films.     

Grafting biodegradable polyesters onto cellulose

To increase the compatibility between cellulose fibers and polyester matrix an original method for grafting hydrophobic oligoesters onto cellulose was proposed. Two kinds of cellulose substrates were employed as cellulose films and microcrystalline cellulose powder. Different oligoesters containing reactive end groups based on poly(DL ‐lactic acid) PDL‐LA, poly(ε‐caprolactone) PCL and poly(3‐hydroxyalkanoate)s PHA were first prepared and characterized by size exclusion chromatography (SEC), nuclear magnetic resonance (NMR), and differential scanning calorimetry (DSC). The carboxylic end groups of the polyesters were activated using thionyl chloride (SOCl₂) to increase the esterification reaction with the hydroxyl groups of the cellulose. The esterification was realized in a heterogenous medium without any catalyst by deposition of chloride oligoesters in solution (2–100 g L⁻¹) onto cellulose film at different temperatures (25–105°C) during 1–12 h. The successful grafting on the various substrates was confirmed on the basis of FTIR spectroscopy, contact angle measurement, X‐ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). In particular, it is shown that a small quantity of grafted oligoesters led to a significant increase of the hydrophobic character of the cellulose with a contact angle near 130°. The increase of hydrophobicity of cellulose is independent of the nature and length of grafting oligoesters. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

超细纤维素胶体和丙烯酰胺的接枝共聚

本文用纤维素材料经酸分解制备具有平衡聚合度（LODP）的微晶纤维素，再分散成超细纤维素胶体（准均相纤维素体系）。用扫描电镜（SEM）观察处理前后的纤维素颗粒尺寸，并比较它们和丙烯酰胺接枝共聚的反应速率、聚合转化率、接枝率、接技效率、聚丙烯酰胺支链的分子量及其分布的情况。     

Thermal decomposition of cellulose/synthetic polymer blends containing grafted products. V. Cellulose/polystyrene blends

Homogeneous grafting of styrene onto cellulose was carried out in a dimethylacetamide/lithium chloride solvent system. The grafted products were added to cellulose/polystyrene (PS) blends as compatibilizers. The thermal decomposition behavior of the blends was investigated by thermogravimetry. The thermal stability of the blends decreased with an increase in grafted product content. The crystallinity of the blends decreased with grafted product content. The microphase‐separated structures of the blends became finer with grafted product content. The glass transition temperatures for cellulose and PS in the blends were lowered with grafted product content. Differences in thermal decomposition behavior of the blends were correlated with compatibility. Thermogravimetry was effective for compatibility estimation in cellulose/PS blends containing grafted products. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

纤维素与MBA接枝共聚物在离子液体中的制备

以N,N’-亚甲基双丙烯酰胺(MBA)为单体,过硫酸钾为引发剂,研究了MBA与纤维素在离子液体中的接枝共聚反应。通过正交单因素实验,研究了反应时间、单体用量、反应温度、引发剂用量对接枝效果的影响。实验结果表明:当反应时间为2 h,单体与纤维素质量比为3∶1,反应温度为50℃,引发剂用量为0.05 g时,接枝效果最好。此条件下,MBA与纤维素的接枝率可达38.06%。     

离子液体中疏水改性羟乙基纤维素的合成

采用大分子反应法,将疏水性单体l-溴代十二烷(BD)接枝到羟乙基纤维素(HEC)上,对羟乙基纤维素进行疏水改性,制备了疏水改性羟乙基纤维素(HMHEC)。研究了离子液体种类、反应温度、羟乙基纤维素浓度和BD用量对HMHEC性能的影响。最佳合成条件为:HEC浓度为3%(质量分数),溶解时间1 h,溶解温度100℃,反应时间2 h,反应温度80℃,BD用量为2 mL。在1-烯丙基-2-甲基-咪唑氯盐体系中合成的HMHEC性能好于在1-丁基-2-甲基咪唑氯盐中合成的HMHEC。     

Preparation of Sulfonamide Containing Cellulose Based Sorbent for Removal of Mercury Ions

A new sulfonamide containing cellulose based sorbent was prepared in three steps; poly (acrylonitrile) (PAN) grafting onto cellulose by redox polymerization method, amination of PAN grafted cellulose with ethylenediamine, and sulfamidation with benzene sulfonyl chloride. The resulting polymeric sorbent, which had a sulfonamide content of 3.4 mmol/g, was effective for the removal of mercury ions from aqueous solutions. The mercury sorption capacity of the sorbent is around 1.95 mmol/g under non-buffered conditions. The experiments performed under identical conditions with some metal ions reveal that Cd(II), Mg (II), Zn(II), and Fe(III) ions are also extractable in low quantity (0.02–0.46 mmol/g). The sorbed mercury can be eluted by repeated treatment with hot acetic acid.