淀粉接枝丙烯酸/醋酸乙烯酯高吸水性树脂的制备

以过硫酸铵为引发剂,N,N-亚甲基双丙烯酰胺为交联剂,淀粉与丙烯酸/醋酸乙烯酯混合单体通过接枝共聚,制备了吸水及耐盐性能均较好的淀粉接枝丙烯酸/醋酸乙烯酯高吸水性树脂(CGAV)。最佳工艺条件为:淀粉10.0 g,m(混合单体)∶m(淀粉)=4∶1,w(引发剂)=0.3%,w(交联剂)=0.05%,于45℃反应2h~3 h。在最佳工艺条件下制得的CGAV吸去离子水率760 g.g-1,吸0.9%NaC l水溶液率68 g.g-1。     

丙烯酸/2-丙烯酰胺基-2-甲基丙磺酸高吸水树脂的反相悬浮聚合及其性能

采用反相悬浮聚合法,通过均匀实验设计,制备了聚(丙烯酸(AA)/2-丙烯酰胺基-2-甲基丙磺酸(AMPS)）(PAAMPS)高吸水树脂,探讨了单体摩尔分数及其中和度、引发剂及交联剂摩尔分数（相对于单体总量）对蒸馏水、质量分数0.9%NaCl水溶液中吸液性能的影响,并经实验数据拟合,得到了二次回归方程,比较了优化配方、单因素实验的模拟值和实验值,结果表明,模拟值与优化值基本接近,其优化工艺参数为：AMPS占单体的摩尔分数8%,中和度为75%,交联剂、引发剂用量与单体的摩尔分数分别为0.035%和0.17%,单体总质量浓度为30%,分散剂用量为单体质量分数的0.5%,反应温度70 ℃,反应时间1.5 h。 此条件下合成的PAAMPS在蒸馏水、0.9%NaCl水溶液中的吸液倍率分别为1.600和130 g/g。     

反相悬浮法制备AA-AM共聚耐盐高吸水性树脂

对反相悬浮法制备丙烯酸 (AA)和丙烯酰胺 (AM)二元共聚高吸水性树脂的工艺进行了研究。实验表明 ,该工艺的最佳条件为 :AA 2 0g( 2 80mmol) ,n(AA)∶n(AM +AA) =0 .6 ,交联剂N ,N 亚甲基双丙烯酰胺的用量为单体总质量的 0 .2‰ ,引发剂过硫酸钾的用量为单体总质量的 0 .6‰ ,聚合温度 6 5℃ ,聚合时间 1.5h。AA -AM的吸水率为 12 5 0g·g-1,吸盐水率为 14 0g·g-1。     

速溶型高吸水性树脂的制备及性能研究

以丙烯酸为单体，Ｋ＿２Ｓ＿２Ｏ＿８为引发剂，Ｎ，Ｎ’－亚甲基双内烯酰胺为交联剂，进行反相乳液聚合，制得内交联高吸水性树脂。研究了聚合物吸水性能与内烯酸浓度，丙烯酸中和度，引发剂用量，交联剂用过的关系。考察了该树脂的吸水速率，保水性，在不同电解质溶液中的吸水速度及水饱和树脂在盐水中的失水率。     

微波法合成淀粉接枝丙烯酸盐类高吸水性树脂的研究

以N,N′-亚甲基双丙烯酰胺为交联剂、过硫酸铵为引发剂、在微波辐照下对淀粉接枝丙烯酸盐共聚进行了系统的研究,确定了最佳的反应条件,合成了粉末状的高吸水性树脂。并用FTIR和固体NMR等方法探讨了淀粉一丙烯酸盐接枝共聚物的结构特征。实验结果表明,利用微波技术合成淀粉一丙烯酸盐接枝共聚物可实现一次合成、干燥,简化合成工艺。淀粉与丙烯酸盐质量比为40／100左右时产物的接枝率最大,且吸水速率明显高于化学法合成的高吸水树脂。     

高吸水性树脂聚丙烯酸钠盐制备工艺研究

研究他聚俩烯酸钠在溶液聚合中，引发剂、交联剂、丙烯酸中和度、单体浓度和反应温度对树脂吸水性的影响，从中获得最佳合成工艺，制得树脂性能为吸去离子水１４００ｇ／ｇ，吸０。９％ＮａＣｌ溶液１５０ｇ／ｇ，吸水速率快，保水性较好。     

钻井液用交联-接枝淀粉的制备及性能

以N,N′-亚甲基双丙烯酰胺为交联剂,过硫酸铵为引发剂,采用“溶剂法”工艺合成了高粘度抗剪切丙烯酸钠接枝淀粉(St),考察了单体、引发剂和交联剂用量、丙烯酸中和度、反应时间及反应温度对合成交联丙烯酸钠接枝淀粉糊液粘度的影响。 结果表明,其优化反应条件为：m(淀粉)∶m(丙烯酸）=1∶1.5,乙醇质量分数为80%,过硫酸铵的用量为单体总质量的1%,交联剂为单体总质量的0.6%,反应时间2.5 h,反应温度为55 ℃,丙烯酸中和度为70%。 该交联接枝淀粉糊液具有良好的触变性,在4%盐水泥浆中的添加量为14.0 g/L时,表观粘度为26.0 mPa·s,滤失量为7.2 mL;在饱和盐水泥浆中添加量为23.5 g/L时,表观粘度为54.5 mPa·s,滤失量为3.1 mL;在80 ℃高温下老化16 h其表观粘度及滤失量等性能基本保持不变,表现出良好的增粘、降失水作用和抗盐、抗老化性能。     

二甲基二烯丙基氯化铵/丙烯酸共聚凝胶的辐射合成与性质研究

采用γ辐射溶液聚合法合成了几种二甲基二烯丙基氯化铵 丙烯酸 (DADMAC AA)共聚凝胶 .实验结果表明单位体积溶液中二组分单体总摩尔数和丙烯酸 (AA)相对含量的增加使共聚凝胶力学强度明显增高 .在两种单体等摩尔比的情况下共聚体的凝胶含量随剂量增加而增加 ,且明显高于聚N ,N′ 二甲基二烯丙基氯化铵 (PolyDADMAC)凝胶 .体系中少量κ 卡拉胶 (KC)的加入可增强共聚凝胶韧性但对凝胶含量和强度影响甚微 .共聚凝胶溶胀性能测定结果表明DADMAC与AA摩尔比为 1∶2时凝胶溶胀比与体系pH值的关系呈现聚两性电解质性质 ,等电点pH值接近 4 5 .这种聚两性电解质性质在对铼Re(Ⅶ )离子浓集中也有所表现     

均相条件下甲壳素基高吸水树脂的制备及性能研究

利用冻融循环处理破坏甲壳素致密的晶体结构和氢键相互作用,使甲壳素溶解在8 wt%NaOH/4wt%urea水溶液中,制备了碱-甲壳素均相溶液.采用静态溶液聚合法,以过硫酸铵(APS)为引发剂、甲叉双丙烯酰胺(MBA)为交联剂,在均相条件下制备了甲壳素接枝聚丙烯酸钠高吸水树脂.研究了丙烯酸、NaOH、MBA和APS用量以及反应温度和时间对产物吸水性能和得率的影响.在最优化条件下制备的树脂的最大吸蒸馏水、自来水、生理盐水和人工尿液倍率分别可达1251,455,84和77 g.g-1.采用FTIR和XRD对合成的树脂进行初步结构表征,证明反应过程中甲壳素与丙烯酸发生了接枝共聚反应,而不是甲壳素与聚丙烯酸钠的简单物理共混.     

CAN引发S—DMDAAC—AM接枝共聚的研究

以硝酸铈铵(CAN)为引发剂,以淀粉(S)、二甲基二烯丙基氯化铵(DMDAAC)和丙烯酰胺(AM)为原料,通过反相乳液聚合,合成接枝共聚物。研究了加料顺序、引发剂浓度、单体与淀粉配比、油水体积比、乳化剂用量等因素对产品性能的影响。并用IR和1H-NMR对接枝产物进行了分析表征。     

Gamma Radiation-Induced Template Polymerization of Acrylic Acid in the Presence of Polyactrylamide

Abstract

Poly(acrylamide-acrylic acid) resin p(AM-AA) was prepared by gamma radiation-induced polymerization of acrylic acid in the presence of polyacrylamide as a template polymer. The polymerization was studied by a free radical mechanism at different experimental conditions such as: absorbed dose, monomer concentration, polymer/monomer molar ratio and the weight-average molecular weight or the swelling degree of added polymer. The resin was obtained at dose > 10 KGy and there is no significant change in the swelling degree of the resin. The results showed that the capacity of the resin increases by increasing the monomer concentration, the weight-average molecular weight of the added polymer and decreases by increasing polymer/monomer molar ratio and the swelling degree of the added polymer. It was also found that the capacity of the resin depends on the radiation dose.     

Photo-grafting Poly(acrylic acid) onto Poly(lactic acid) Chains in Solution

Poly(lactic acid)(PLA)is one of the most important bio-plastics,and chemical modification of the already-polymerized poly(lactic acid)chains may enable optimization of its material properties and expand its application areas.In this study,we demonstrated that poly(lactic acid)can be readily dissolved in acrylic acid at room temperature,and acrylic acid can be graft-polymerized onto poly(lactic acid)chains in solution with the help of photoinitiator benzophenone under 254 nm ultraviolet(UV)irradiation.Similar photo-grafting polymerization of acrylic acid(PAA)has only been studied before in the surface modification of polymer films.The graft ratio could be controlled by various reaction parameters,including irradiation time,benzophenone content,and monomer/polymer ratios.This photo-grafting reaction resulted in high graft ratio(graft ratio PAA/PLA up to 180%)without formation of homopolymers of acrylic acid.When the PAA/PLA graft ratio was higher than 100%,the resulting PLA-g-PAA polymer was found dispersible in water.The pros and cons of the photo-grafting reaction were also discussed.     

Membranes permselectives obtenues par greffage radiochimique des acides acrylique et methacrylique sur des films de poly(chlorure de vinyle)

Membranes were prepared by subjecting to gamma-rays PVC films swollen in a mixture of acrylic acid and methylene chloride. The kinetics of the reaction were investigated as a function of monomer concentration, temperature and dose-rate. The swelling properties of the resulting membranes were studied as well as those of PVC films grafted with methacrylic acid. It was found that PVC films grafted with methacrylic acid only swell slightly in water even for high grafting ratios and the swelling is very slow. At elevated temperatures the films swell more quickly and reach a higher limiting swelling, but the effect is small. PVC films grafted with acrylic acid swell much more quickly and reach much higher swelling ratios. The extent of swelling markedly increases with temperature but this effect is not reversible: once the membranes have reached a high swelling ratio at elevated temperatures, they keep the same ratio when dipped in water at 20°. The Arrhenius plot of the swelling ratio exhibits a break at 50–60° apparently corresponding to a glass transition temperature. In methanol the swelling is significantly higher for PVC films grafted with methacrylic than with acrylic acid. Swelling of the membranes was also investigated in mixtures of water with methanol and methanol with methylene chloride. The results are interpreted by assuming a strong dipole-dipole interaction between the grafted branches and the trunk polymer resulting in a quasimolecular dispersion of the carboxylic chains in the PVC matrix. The latter acts as a barrier against the penetration of water. Heat treatment favours a segregation of the two polymeric species into microphases and this non-reversible transformation is assumed to be responsible for the unexpected behaviour of PVC films grafted with acrylic acid. The significant differences between the properties of PVC films grafted with either acrylic or methacrylic acid are attributed to the much higher hydrophobic character of the methacrylic chains.     

Sur une exaltation de l'“effet de matrice” lors de la polymerisation de l'acide acrylique dans certains melanges ternaires

The polymerization of acrylic acid proceeds with an extremely high degree of auto-acceleration in certain ternary mixtures. The most drastic effects are observed when small amounts of methanol are added to a dilute solution of acrylic acid in n-hexane. In such systems the auto-acceleration index “β” may exceed 10. β Was found to exhibit a maximum over a fairly narrow range of concentrations. Moreover, the values of β are highest at temperatures between ?5 and + 10°, where a maximum of 16 is reached. The swelling of poly(acrylic acid) in the various reacting mixtures was measured and the molecular associations of the monomer with itself and with methanol were investigated. It was concluded that the “exaltation of the matrix effect” in some of the systems is caused by the complex [(Acrylic acid)₂, McOH]. This complex associates very rapidly with the polymer formed in the early stages of the reaction to produce a structure in which ultrafast propagation occurs. The swelling of the polymer favours the accessibility of the monomer to the polymeric chains during polymerization, leading to auto-acceleration which progresses with conversion and gives rise to a reaction with explosive character.     

聚丙烯酸接枝辛基酚聚氧乙烯醚的合成、表征和胶束化

通过自由基聚合, 丙烯酸(AA)与辛基酚聚氧乙烯醚丙烯酸酯活性大单体(C8PhEO10Ac)共聚,合成了以聚丙烯酸为主链、C8PhEO10Ac 为支链的水溶性两亲接枝共聚物(PAA-g-C8PhEO10Ac), 用凝胶渗透色谱(GPC)测定其相对数均分子质量为4.37×10⁴, 用FTIR和1H-NMR表征了共聚物的结构和组成, 共聚物分子中丙烯酸单体与活性大单体的摩尔比为9:1, 每个共聚物分子中平均约有32个C8PhEO10侧链. 用表面张力法、荧光探针法和透射电子显微镜对共聚物在水溶液中的自组装行为进行了初步研究, 结果表明, 共聚物分子在第一临界胶束浓度cmc1)和第二临界胶束浓度(cmc2)时都形成了球型胶束. 与cmc1时相比, cmc2时溶液表面张力进一步降低, 胶束内部极性进一步减小, 而且胶束粒径增大、结构紧密. 氯化钠的加入可使共聚物溶液的表面张力和胶束内部极性降低.     

Radiation Synthesis of Superabsorbent Hydrogels Based on Chitosan and Acrylic Acid for Controlled Drug Release

Superabsorbent hydrogels based on the natural polymer chitosan and acrylic acid (CS/AAc) was prepared using ⁶⁰Co gamma radiation as a source of initiation and crosslinking. The factors, which affect the preparation of CS/AAc hydrogels such as irradiation dose, CS/AAc ratios, and acrylic acid monomer concentrations, to get the best optimum conditions, were investigated. The kinetic studies of the swelling of CS/AAc hydrogel showed that it follows a Fickian type of water diffusion. The Fickian constant value ‘n’ was more than 0.5 with a high swelling capacity of 300 g/g as superabsorbent hydrogel. In addition, the suitability of CS/AAc hydrogel as carrier material for the drug Chlortetracycline-HCl has been investigated by adsorption isotherm studies. The performance of drug release from hydrogel systems, influenced by acrylic acid ratio and the effect of pH of the medium was studied.     

粉煤灰复合聚丙烯酸钠凝胶的制备及其溶胀性能

粉煤灰(CFA)存在的情况下,采用自由基溶液聚合法,以过硫酸钾(KPS)为引发剂,N,N'-亚甲基双丙烯酰胺(NNMBA)为交联剂,制备了粉煤灰复合聚丙烯酸钠凝胶(CFAPAANa)。 以丙烯酸单体质量为基准,当交联剂用量为0.08%,引发剂用量为0.4%,粉煤灰用量为3%,丙烯酸中和度为70%,聚合温度为70 ℃时,所合成的粉煤灰复合聚丙烯酸钠凝胶在蒸馏水和生理盐水中平衡溶胀比最高,分别为1556(g/g)和168(g/g)。 考察了复合凝胶在不同介质溶液中的溶胀动力学,保水性能以及在土壤中的降解行为。 溶胀动力学研究表明,蒸馏水中溶胀初期复合凝胶聚合物链段的扩散运动能够调控凝胶溶胀的快慢及程度,而生理盐水中水分子的平移和对流运动在凝胶的溶胀过程中起着关键性作用。 保水和降解实验结果表明,25 ℃时,50 h凝胶保水率为64%,土壤中50 d时降解率达60%。 相比于聚丙烯酸钠凝胶,粉煤灰复合凝胶保水率提高了8%。     

氧化淀粉基高吸水性树脂的制备及表征

以过硫酸铵为引发剂,N,N’-亚甲基双丙烯酰胺为交联剂,制备氧化淀粉―丙烯酸―丙烯酰胺高吸水性树脂,并采用红外光谱、X射线衍射等手段对产品的结构进行表征。通过单因素实验优化其制备工艺,最佳工艺条件为:氧化淀粉基体用量为50%,丙烯酸/丙烯酰胺质量比为4∶1,丙烯酸中和度为70%,引发剂过硫酸铵用量为0.5%,交联剂N,N’-亚甲基双丙烯酸胺用量为0.15%,反应温度为80℃,反应时间为3 h。此条件下,氧化淀粉基高吸水性树脂的吸水率达到972.4 g/g。     

硫酸铵水溶液中分散聚合法制备两性共聚物P(AM-co-AA-co-DAC-co-DMC)

利用分散聚合技术,在硫酸铵水溶液中以丙烯酰胺(AM)、丙烯酸(AA)、丙烯酰氧乙基三甲基氯化铵(DAC)、甲基丙烯酰氧乙基三甲基氯化铵(DMC)为单体,合成了两性共聚物P(AM-co-AA-co-DAC-co-DMC).用FTIR,13C-NMR,TEM等方法表征了聚合物的结构和组成.考察了不同分散稳定剂、正负离子单体配比和pH对分散聚合的影响,并对P(AM-co-AA-co-DAC-co-DMC)水基分散聚合条件及稳定性进行了一些探讨.实验表明,在硫酸铵水溶液中制得较稳定的P(AM-co-AA-co-DAC-co-DMC)分散体系,应选用非离子型或阳离子型的分散稳定剂,如聚乙烯吡咯烷酮(PVP)、聚甲基丙烯酰氧乙基三甲基氯化铵(PDMC)、聚丙烯酰氧乙基三甲基氯化铵(PDAC),而其pH应在2到4之间.当选用占总质量1.5%的聚乙烯吡咯烷酮(PVP)为分散稳定剂,引发温度为40℃,正负离子单体物质的量比值大于1,pH=3时,可以制得总离子度超过25%的纳米级两性聚合物.     

Crystallinity in Free Radical Polymerized Polyvinyl p-t-butylbenzoate)

The photoinduced graft polymerization of acrylic acid and n-butyl acrylate on polyvinyl chloride or carbon monoxide-vinyl chloride copolymer by using benzophenone as a sensitizer was carried out. In graft polymerization of acrylic acid, the degree of grafting was low. However, graft polymerization of n-butyl acrylate or acrylic acid-n-butyl acrylate were higher than that of acrylic acid. Turbidimetry, DTA, and TGA of the graft polymer were examined. As the graft polymer was a weak polyacid, the pK_a was estimated according to the Henderson equation, and the relationship between pK_a and the acrylic acid unit content in the graft polymer was derived.