Graft polymerization of acrylic acid onto macroporous polyacrylamide gel (cryogel) initiated by potassium diperiodatocuprate

Potassium diperiodatocuprate-initiated graft polymerization was found to be an efficient and convenient method for grafting of acrylic acid (AAc) onto superporous polyacrylamide gels, so called cryogels (pAAm cryogels). It was possible to achieve grafting degrees as high as 70% with about 25% yield of grafted polymer with respect to the initial amount of monomer. The superporous structure of the cryogels promoted grafting by providing an ample surface of the gel for grafting, ensuring good mass transfer inside the gel sample and allowing to wash easily both homopolymer of AAc and insoluble by-products formed during the polymerization reaction. The grafted cryogels could be dried at 60 °C and re-swollen with retaining their properties. The adsorption of water vapours by dried pAAm cryogels was marginally dependent on the degree of grafting. The swelling of AAc-grafted pAAm cryogel increased pronouncedly with increasing pH. The adsorption of low-molecular weight ligand, Cu(II), by AAc-grafted pAAm cryogels increased linearly with the degree of grafting, while binding of high-molecular weight ligand, lysozyme, increased linearly till the degree of grafting of about 40% followed by a sharp, nearly three-fold increase in lysozyme binding when the degree of grafting increased from 60 to 70%. The results indicate that a ‘tentacle’-type binding of lysozyme to grafted polyAAc takes place after a certain degree of grafting has been reached.     

内嵌SiO_2纳米颗粒的超大孔复合晶胶的制备(英文)

Supermacroporous composite cryogels embedded with SiO2 nanoparticles were prepared by radical cryogenic copolymerization of the reactive monomer mixture of acrylamide(AAm) and N,N-methylene-bis-acrylamide(MBAAm) containing SiO2 nanoparticles(mass ratios of nanoparticles to the monomer AAm from 0.01 to 0.08) under the freezing-temperature variation condition in glass columns.The properties of these composite cryogels were measured.The height equivalent to theoretical plate(HETP) of the cryogel beds at different liquid flow rates was determined by residence time distribution(RTD) using tracer pulse-response method.The composite cryogel matrix embedded with the mass fraction of SiO2 nanoparticles of 0.02 presented the best properties and was employed in the following graft polymerization.Chromatographic process of lysozyme in the composite cryogel grafted with 2-acrylamido-2-methyl-1-propanesulfonic acid(AMPSA) was carried out to evaluate the protein breakthrough and elution characteristics.The chromatography can be carried out at relatively high superficial velocity,i.e.,15 cm·min-1,indicating the satisfactory mechanical strength due to the embedded nanoparticles.     

超大孔聚丙烯酰胺晶胶微球的制备及其生物相容性和吸附性能

利用反相悬浮结合溶剂结晶致孔法制备了具有超大孔隙、球形度良好的聚丙烯酰胺晶胶微球,晶胶微球平均粒径为234.1 mm,孔径约为10～50 mm。采用原位接枝法,将2-丙烯酰胺基-2-甲基-1-丙烷磺酸（AMPSA）接枝到晶胶微球孔隙表面上,得到了带有磺酸基团的阳离子交换晶胶微球。考察了晶胶微球的生物相容性和吸附蛋白质及重金属离子Cu²⁺的性能,结果表明：在大肠杆菌培养液中,添加晶胶微球,对大肠杆菌的生长影响不大。接枝了AMPSA的晶胶微球表现出更强的吸附Cu²⁺的能力,吸附容量达到1.14 mmol·g^-1。同时,接枝后的晶胶微球也具有一定吸附蛋白质的能力,溶菌酶的吸附容量达到54.5 mg·g^-1。因此,该大孔晶胶可望在微生物固定化、生物分离和重金属离子吸附中会发挥更大的作用。     

Structural,morphological and thermal characterization of poly (2-hydroxyethyl methacrylate-co-acrylonitrile) (P (HEMA-co-AN)) Cryogels: evaluation of water sorption potential and cytotoxicity

Cryogels are macroporous hydrogels which are synthesized through cryogelation method. In the present study cryogels of poly (2-hydroxyethyl methacrylate-co-acrylonitrile) (P (HEMA-co-AN)) were synthesized by copolymerization of 2-hydroxyethyl methacrylate (HEMA) and acrylonitrile (AN) monomers by redox polymerization using cryogelation technique. The synthesized cryogels were characterized by FTIR, SEM, XRD, DSC and TGA techniques. Different compositions of the cryogels were prepared by varying concentrations of the monomers and redox initiators in the feed mixture. These cryogels were then subjected to swelling studies and porosity determination. The swelling behavior was studied as function of concentration of the monomers, redox initiators, temperature, pH, and simulated biological fluids. The prepared cryogels were also characterized for their network parameters using water sorption data. The biocompatibility of P (HEMA-co-AN) cryogel was evaluated by in vitro cytotoxicity test. The results indicated that the P (HEMA-co-AN) cryogel had macroporous morphology and exhibited good water absorption capacity. Moreover, the cryogel was thermally stable and biocompatible in nature.     

Self‐driven graft polymerization of vinyl monomers on poultry chicken feathers in the absence of initiator/catalyst

An efficient and simple method for graft copolymerization of powdered chicken feather (CF) with vinyl monomers without any free radical initiator is reported. Various vinyl monomers such as glycidyl methacrylate (GMA), styrene (S), and methyl methacrylate (MMA); (20–60 wt % with respect to CF) were successfully grafted to chicken feather (CF) by using sodium dodecyl sulfate (SDS, 0.086–0.5 mmol) in the absence of any catalyst or initiator. Most likely, the hydrophilicity, hydrophobicity, and complex forming properties of chicken feather keratin with surfactant molecules were responsible for efficient grafting of polymers on CF surface. The effect of polymerization conditions, such as monomer concentration, temperature, and time of reaction, on the grafting parameters such as monomer conversion, grafting efficiency, and molar grafting ratio were studied. The described method showed a good potential of using low cost, easily accessible poultry chicken feathers as grafting material and self catalyzing agent for graft copolymerization with vinyl monomers to produce low cost commodity plastic for various end uses. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44645.     

三元乙丙橡胶/丁腈橡胶并用胶增容剂丙烯腈接枝三元乙丙橡胶共聚物的研制

采用溶液聚合法制备三元乙丙橡胶(EPDM)/丁腈橡胶(NBR)并用胶增容剂丙烯腈(AN)接枝EPDM(PANg-EPDM)共聚物,研究AN/EPDM用量比、引发剂BPO用量、溶剂种类、反应温度和反应时间对接枝率的影响。结果表明,在AN/EPDM用量比为5/6、引发剂BPO质量分数为0.005、溶剂为正庚烷、反应温度为70℃、反应时间为2.5 h的最佳溶液聚合反应条件下,PAN-g-EPDM共聚物的接枝率为26%,该接枝率的PAN-g-EPDM共聚物对EPDM/NBR并用胶增容性较好。     

Graft copolymerization of methyl acrylate onto cellulose initiated by potassium ditelluratoargentate(III)

A novel redox system, potassium ditelluratoargentate(III) (DTA)–cellulose, was employed to initiate the graft copolymerization of methyl acrylate onto cellulose in alkali aqueous solution. Grafting parameters, such as total conversion, grafting efficiency and grafting yield, were evaluated comparatively. The dependence of these parameters on temperature, reaction time, initiator concentration and ratio of monomer to cellulose was also investigated. Graft copolymers with high grafting parameters were obtained, which indicated that the DTA–cellulose redox pair is an efficient initiator for cellulose grafting. The proof of grafting was obtained from gravimetric analysis and infrared spectra. A tentative mechanism involving a two‐step single‐electron‐transfer process of DTA is proposed to explain the generation of radicals and initiation. Thermogravimetry, X‐ray diffraction and scanning electron microscopy were also carried out to study the thermal stability, crystallinity and morphology of the grafted copolymers. Copyright © 2004 Society of Chemical Industry     

淀粉与苯乙烯/甲基丙烯酸甲酯乳液共聚合

研究了淀粉与苯乙烯 (St)、甲基丙烯酸甲酯 (MMA)的接枝聚合反应。以焦磷酸锰 [Mn(H2 P2 O7) 3 ]3 -为引发剂 ,以十二烷基苯磺酸钠为乳化剂 ,考察引发剂浓度、反应温度、单体浓度对原位聚合反应中单体的转化率(X % )、接枝率 (G % )、接枝效率 (GE % )的影响。实验结果表明最高接枝率可达到 5 2 .4 % ,接枝效率可达 77.2 %。     

丙烯酸酯接枝NR乳液的稳定性研究

以天然胶乳和丙烯酸酯为主单体进行了种子乳液聚合,设计正交实验,详细考查了天然胶乳/丙烯酸酯比例、丙烯酸酯软/硬单体比例、丙烯酸酯功能单体用量、引发剂用量、乳化剂用量、反应温度及反应时间对丙烯酸酯单体转化率和接枝率的影响,得到了稳定的丙烯酸酯接枝NR乳液的优化工艺和配比。     

Maleic anhydride/styrene melt grafting and crosslinking onto ethylene‐octene copolymer

Melt grafting of the multimonomer system of maleic anhydride (MAH)/styrene (St) onto ethylene‐octene copolymer (POE) was performed by a twin‐screw extruder. The effects of St and initiator contents as well as MAH/St on the grafting reaction were investigated. The structure and properties of the grafted POE were characterized by the Fourier transform infrared spectroscopy, melt flow index, dynamic rheological behaviors, and thermogravimetric analysis. It is shown that the addition of St can significantly enhance MAH grafting degree onto POE. MFI values of grafted POE are affected not only by MAH/St copolymer concentration, but also by initiator concentration. These data indicate that the interaction and reaction between MAH and St monomers plays an important role in the grafting reaction. St improves the grafting reactivity of MAH and reacts with MAH before the two monomers graft onto POE. And high grafting degree can be obtained while the gel content is still low. Compared with neat POE, grafted POE shows different dynamic rheological behaviors and high thermal stability. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Peroxide-initiated grafting of acrylamide on to polyethylene surfaces

Acrylamide has been grafted onto the surface of a polyethlene film with the aid of a peroxide initiator (tert-butyl peroxyneodecanoate). The peroxide was first swollen into the film from cyclohexane solution; the film was then dried under reduced pressure at room temperature. Excess initiator, adsorbed on the surface, was washed off with acetone. The grafting reaction was carried out by placing the film in a boiling solution of the monomer in water. After grafting, the film was extracted with water to remove monomers and homopolymer. The grafted films were characterized by infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), gravimetric measurements, and contact angle measurements. The graft yield was found to increase with reaction time up to about 5–15 min and thereafter level off. The presence of air was found to retard the grafting reaction. Increase in monomer concentration gave an almost continuous increase in graft yield, but high concentrations were not necessary to cover the surface of the film with polyacrylamide. This grafting has been found to function, but the process requires further development to reduce the total grafting time before it can be used commercially.     

黄原胶与丙烯酰胺接枝共聚反应的研究

以过硫酸铵为引发剂,在氮气保护下,研究了黄原胶与丙烯酰胺的接枝共聚反应。考察了单体浓度、引发剂浓度、反应温度和反应时间等因素对接枝率及接枝效率的影响,探讨了过硫酸铵引发黄原胶接枝丙烯酰胺共聚反应的基本规律。采用红外光谱、X射线粉末衍射对接枝共聚物的结构进行研究,用热重分析法表征了产物的热性能,并初步探讨了接枝机理。结果表明,过硫酸铵能有效地引发黄原胶与丙烯酰胺的接枝共聚反应,并且接枝率和接枝效率随单体浓度、引发剂浓度、反应温度的变化出现极大值,随反应时间的延长不断上升,直至基本不变。     

以Fe~(2+)-H_2O_2氧化还原体系引发木薯淀粉与醋酸乙烯酯接枝共聚反应研究

研究了以Fe2+-H2O2为引发剂的木薯淀粉与醋酸乙烯酯的接枝共聚反应,并对重要的反应条件进行了讨论。结果表明:当单体与淀粉的质量配比为1.0~2.0,引发剂浓度为1.0 mmol/L,H2O2与Fe2+的摩尔比为2,反应温度为40°C,反应时间为3 h,采用Fe2+→单体→H2O2的加料顺序时,可以得到较高的转化率、接枝率、接枝效率,分别为86.47%、55.30%及31.98%,并探讨Fe2+-H2O2的引发机理。通过Srectrum One红外光谱及电镜对接枝物的结构进行了分析。     

Grafting acrylonitrile and acrylic acid monomers on cellulosic materials

Graft copolymers of acrylonitrile and of acrylic acid monomers on cellulosic materials were obtained by use of ceric ion initiator in aqueous medium at a 50% (w/w) cellulose-monomer ratio. The variations of poly(acrylonitrile) grafts and of the efficiency of grafting with ceric ion concentration, and of poly(acrylic acid) grafts with temperature are examined. The dependence of water retention capacity of the grafted fibers with the graft level is reported.     

S-DMDAAC-AM阳离子型高分子絮凝剂的合成及性能研究

以淀粉(S)、二甲基二烯丙基氯化铵(DMDAAC)、丙烯酰胺(AM)为原料,采用氧化还原引发体系,合成r接枝共聚物S-DMDAAC-AM.考察了反应温度、反应时间、引发剂浓度、单体配比等因素对接枝共聚体系的接枝率、接枝效率和絮凝效果等因素的影响.试验结果表明,最优条件为淀粉(S):单体总量=3.5 g∶10.5 g,反...     

乙酸乙烯酯接枝改性海藻酸钙凝胶微球

为了降低海藻酸钙凝胶微球的溶胀度,以乙酸乙烯酯（VAc)对海藻酸钠进行自由基接枝共聚,进而制备具有较低溶胀度的聚乙酸乙烯酯改性海藻酸钙(Ca-SA-PVAc)凝胶微球。红外光谱表明,改性之后海藻酸钙的分子上生成新的化学键;热重分析表明,改性微球受热失水行为发生变化,热稳定性提高;扫描电镜表明,改性微球结构孔隙结构发达;接枝反应条件如反应温度、VAc的浓度、引发剂用量、海藻酸钠浓度、钙离子浓度及反应时间等对改性凝胶微球在生理盐水中的抗溶胀性具有不同程度的影响。通过改变反应条件以控制接枝反应参数,可以获得溶胀行为可控的改性海藻酸钙凝胶微球。     

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.     

双氧水引发下淀粉／丙烯腈接枝聚合物的制备与分析

以淀粉为原料,在双氧水的引发下,与丙烯腈进行接枝反应制备淀粉接枝聚合物。考察了温度、时间、引发剂浓度、接枝剂浓度等单因素对接枝率的影响。对影响接枝反应的各种因素,如反应物的用量、反应时间、引发剂浓度等进行了深入细致的分析探讨,由正交试验确定出双氧水为引发剂,进行淀粉接枝反应的最佳工艺条件为：反应温度85℃,反应时间3h,料液比1：100,引发剂浓度17．143mmoL／L,丙烯腈浓度0．114mmol／L。     

衣康酸-丙烯酰胺高吸水树脂的合成

用过硫酸钾做引发剂,通过水溶液聚合法制得了淀粉/膨润土接枝衣康酸(IA)和丙烯酰胺(AM)高吸水树脂.研究了m(AM)/m(IA),IA,交联剂用量及引发剂用量等对吸液性能的影响.在固定反应温度70℃,反应时间为6～10 h的条件下,吸水的最佳条件为:m(AM)/m(IA)为9.3∶0.7,IA中和度为75％,交联剂质量为单体总质量的0.05％,引发剂过硫酸钾(KPS)质量是单体总质量的0.30％.吸生理盐水的最佳条件为:m(AM)/m(IA)为9.1∶0.9,IA中和度为75％,交联剂质量为单体总质量的0.03％,引发剂KPS质量是单体总质量的0.50％.     

Graft copolymerization of vinyl monomers onto silk fibers initiated by a semiconductor‐based photocatalyst

Graft copolymerization onto silk (Bombyx mori) was carried out with vinyl monomers (methyl methacrylate and acrylamide) and initiated by a semiconductor‐based photocatalyst (cadmium sulfide). The utility of a semiconductor as an initiator in free‐radical photografting and the effects of ethylene glycol and triethylamine with cadmium sulfide on graft copolymerization were explored. Depending on the reaction conditions, 10–48% grafting with methyl methacrylate and 4–26% grafting with acrylamide were achieved. The reaction conditions were optimized, and the grafted fibers were characterized with scanning electron microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetry analysis, and tensile strength measurements. The chemical resistance and water absorption of the grafted fibers were compared with those ungrafted fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007