聚乙烯辐照接枝体系改变pH对接枝率的影响

采用γ射线辐照引发接枝的方法，在高密度聚乙烯（HDPE）上接枝丙烯酸（AA）和对接枝苯乙烯磺酸钠（SSS），制备了一种含羧酸基团和磺酸基团的阳离子交换膜，详细研究了反应体系在不同pH值下的接枝率变化规律。实验表明，在共辐照接枝方法中，当AA与SSS一步法接枝HDPE或接枝上AA的HDPE膜再共辐照接枝SSS时，总接枝率（Gt）及对苯乙烯磺酸钠的接枝率（Gs）随体系的pH的降低而升高，在预辐照一步法接枝中，Gt与Gs随体系pH的降低先升高后又有所降低，综合分析认为，改变pH值使体系粘度发生变化，从而影响了单体向基体的扩散速率。     

磺酸型阳离子交换膜的性能研究

通过辐照接枝法在高密度聚乙烯(HDPE)上引入磺酸基团,从而制备了一种强酸性阳离子交换膜。就所制备离子交换膜的热稳定及化学稳定性能进行了详细考察。结果表明,接枝膜上引入磺酸基团后抗氧化性能较仅含羧酸基团的离子交换膜有所提高,接枝膜的热稳定性较之接枝前稍差,热重分析表明,接枝后样品的成碳量较接枝前有相当大的提高,原因归结于表面接枝层对成碳过程有促进作用。由于接枝膜中HDPE组份的“结晶破坏”及接枝链对晶区的“稀释作用”综合影响,结晶度随着接枝率的升高而降低。     

γ射线辐照聚偏氟乙烯接枝苯乙烯磺酸乙酯

以聚偏氟乙烯(Polyvinylidene fluoride,PVDF)树脂为基材,采用γ射线预辐射接枝法在PVDF树脂上接枝苯乙烯磺酸乙酯(Ethyl styrenesulfonate,ETSS),探讨吸收剂量、接枝温度、接枝反应时间及单体浓度对接枝率的影响。之后在95℃水解PVDF-g-PETSS聚合物得到PVDF接枝苯乙烯磺酸(PVDF-g-PSSA)离子交换树脂。红外光谱、X射线光电子能谱、热重分析证明PVDF-g-PETSS及PVDF-g-PSSA被成功制备。当接枝率为120%时,PVDF-g-PSSA的离子交换容量达到2.05 mmol/g。这种将带有磺酸基团的单体通过辐照接枝引入PVDF基材然后水解的方法简单、高效、污染小,有望在离子交换树脂及离子交换膜的制备中得到应用。     

SBS粉体预辐射接枝丙烯酸研究

以60Coγ射线为辐射源,对SBS粉体在空气中进行预辐照,然后将一定量粉体置于丙烯酸水溶液体系中进行接枝反应。研究了反应时间、反应温度、单体浓度和吸收剂量对接枝率的影响。傅里叶变换红外光谱(FTIR)分析结果证明了羧酸基团的成功引入,并对接枝后粉体的热重分析,结晶度和表面形貌进行了研究。     

电子束引发双功能基阳离子交换膜的制备研究

在所有的离子交换膜中,最引人注目的当数20世纪70年代已商品化的Nation系列膜。具有磺酸功能基的Nation膜电阻低,但用在氯碱工业时电流效率低。1974年Seko发明了全氟羧酸阳离子交换膜,使电流效率有实质性提高,并推动了复合膜的发展。复合膜具有磺酸膜的低电阻性能和羧酸膜的高电流效率。本工作采用辐射接枝法制备含羧酸基团和磺酸基团的双功能基阳离子交换膜,目的主要是以低成本且简单可行的辐射接枝法代替共聚法,制备稳定性好、低电阻、高电流效率的阳离子交换膜。     

电子束共辐照接枝改性聚醚砜微孔膜

用电子束共辐照技术在聚醚砜微孔膜上接枝了甲基丙烯酸。改变接枝单体的浓度和吸收剂量获得具有不同接枝率的改性聚醚砜膜。系统研究了接枝率与单体浓度和吸收剂量间的关系,得到最佳的单体浓度和吸收剂量。接枝膜用傅里叶红外光谱仪(FT-IR)进行表征,接枝膜表面及断面形态用扫描电子显微镜(SEM)观察,并测试了接枝膜的亲水性接触角。     

聚丙烯胺肟螯合纤维的辐射合成及其对Pb(Ⅱ)离子的吸附性能

采用预辐照接枝法,在空气或氮气气氛下利用电子束对聚丙烯纤维进行辐照。然后,将样品置于4种不同溶剂(水、甲醇、正丁醇、10％甲醇水溶液)的丙烯腈溶液体系中进行接枝反应,并通过与盐酸羟胺溶液反应,引入胺肟基团,获得一种机械性能较好的偕胺肟螯合纤维(PPAO)。最后浸于硝酸铅标准溶液中,测定其对铅的吸附量。结果表明,接枝率与预辐照气氛、反应温度、反应液体积、单体浓度都有密切关系。聚丙烯纤维在水溶液和10％甲醇水溶液中接枝率较高。当纤维在空气中预辐照,丙烯腈单体体积浓度为30％,温度为70℃时,聚丙烯纤维的接枝率最高;对Pb(Ⅱ)的吸附容量为0．362mg／g(纤维)。     

γ辐射接枝甲基丙烯酸改善聚醚砜膜亲水性的研究

利用 γ 射线共辐照技术在聚醚砜(PES)膜上接枝了甲基丙烯酸。通过改变甲基丙烯酸单体浓度,获得了具有不同接枝率的改性 PES 膜。研究结果表明,在单体浓度<10%的范围内,接枝率与单体浓度成线性关系,提高接枝率有助于改善聚醚砜膜的亲水性。     

预辐射接枝法制备FEP-g-PSSA/AA膜

采用γ射线预辐射接枝方法制备了FEP—g—PSSA／AA膜，反应制得的接枝膜是一种含氟磺酸型质子交换膜。系统研究了影响接枝反应的阻聚剂用量、膜的厚度、单体摩尔比及总摩尔浓度变化等因素。结果表明，丙烯酸（Acrylic acid，AA）与苯乙烯磺酸钠（Sodium styrene sulfonate，SSS）对全氟乙丙烯（Polytetranuoroethyleneco-hexanuoropropylene，FEP）的接枝率几乎不受膜厚度变化的影响，而且全氟乙丙烯（FEP）辐照后放置三个月再进行接枝反应，接枝率也几乎没有变化。     

HDPE膜预辐照接枝VBTAC制备阴离子交换膜

在氮气保护下,利用预辐照接枝技术在高密度聚乙烯(HDPE)膜上接枝苯乙烯三甲基氯化铵(VBTAC)单体,以甲基丙烯酸二甲氨基乙酯(DMAEMA)单体作为接枝辅助单体来提高VBTAC的接枝率,制备出阴离子交换膜,解决了在HDPE上难以直接接枝聚合VBTAC的问题.本文研究了接枝条件及接枝液的组分对接枝的影响,并用X射线显微分析方法研究了VBTAC的接枝进程和接枝分布.     

One step graft copolymerization of acrylic acid and sodium styrene sulfonate onto high－density polyethylene film by preirradiation method

High-density polyethylene(HDPE)films were irradiated by ^60Co gamma ray with a dose of 100kGy in air and then immersed in aqueous solution of acrylic acid(AA) and sodium styrene sulfonate(SSS) at different temperature.The effects of grafting conditions such as temperature,reaction time ,Mohr‘s salt concentration,and total concentration of monomer on grafting yield were studied.Both grafting yield of AA and SSS onto HDPE respectively increases with total concentration of monomer on grafting yield were studied.Both grafting yield of AA and SSS onto HDPE respectively increases with total concentration of monomers.The highest grafting yield was observed at 3mol/L monomers where the grafted PE swelled to the largest extent in the monomers mixture.The grafting yield increases with reaction time and then levels off.At higher temperature,the grafting yield decreases with Mohr‘s salt concentration,but increases at low temperature when Mohr‘s salt concentration is 0.083%.Which can be interpreted that in the presence of Fe^2 diperoxides and hydroperoxides may decompose at low temperature to form radical which can initiate the grafting.The physical and chemical properties of grafting films were also investigated.     

Study of radiation-induced grafting of acrylic acid-sodium styrene sulfonate onto poly （tetrafluoroethylene-cohexafluoropropylene） film

Poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) films were immersed in aqueous solution of acrylic acid (AA) and sodium styrene sulfonate (SSS), then irradiated by ^60Co γ-rays at 25℃. The effects o| reaction time, absorbed dose, dose-rate, inhibitor and monomer concentration on the grafting yield were studied. Grafting yields of both AA and SSS onto FEP, respectively, increase with irradiation dose, but some saturation will appear at high dose and monomer concentration. The grafting yield increases with reaction time and then levels off. The grafting of SSS onto FEP is more difficult than the grafting of AA. The analysis of grafted membranes using DSC and FT-IR have been done.     

接枝丙烯酸聚乙烯表面诱导生成硫化镉及其形貌研究

分别以体积比为1∶1的异丙醇/水、甲醇/水混合溶剂作为接枝溶剂,通过调节丙烯酸单体浓度得到不同接枝率和不同表面接枝链分布的接枝膜,用接枝膜诱导形成了不同形貌特征的硫化镉.研究表明,接枝率越大,硫化镉在聚乙烯接枝膜表面的分布越密集;与甲醇/水为混合接枝溶剂相比,在异丙醇/水为混合接枝溶剂的接枝膜上的硫化镉颗粒分布比较均匀.     

PE－AA辐射接枝共聚合的反应历程研究

研究了聚乙烯（ＰＥ）与丙烯酸（ＡＡ）、甲基丙烯酸（ＭＡＡ）的接枝共聚反应，探讨了接枝反应过程及特征：单体首先在ＰＥ表面接枝，然后进入内部进行本体接枝。研究表明：表面接枝为动力学控制，本体接技系扩散控制，单体在膜内的扩散与单体极性及聚合物的结晶度等有关     

Radiation-induced grafting of N-isopropylacrylamide and acrylic acid onto polypropylene films by two step method

Binary graft copolymerization of pH sensitive acrylic acid (AAc) and thermosensitive N-isopropylacrylamide (NIPAAm) monomers onto pre-irradiated polypropylene films (PP) was carried out by two individual steps using a Co⁶⁰ gamma radiation source. The influence of preparation conditions, such as pre-irradiation dose and reaction time on grafting yield was studied. The swelling behavior and FTIR-ATR study for PP films grafted films were investigated.     

新型抗凝血渗析膜的研制──聚乙烯膜上丙烯酸和苯乙烯的辐射接枝

以丙烯酸和苯乙烯为单体，聚乙烯膜为基体，利用过氧化预辐照接枝技术，研制出一种具有亲水－疏水平衡结构的新型抗凝血渗析膜。探讨了单体组成对膜性能的影响。结果表明：当丙烯酸和苯乙烯单体组成为１∶１（体积比）时，接枝膜具有较好的机械性能。与未接枝膜相比，抗凝血性提高了约３０倍，渗析性提高约１０倍。     

Preparation of composite polymer electrolytes by electron beam-induced grafting: Proton- and lithium ion-conducting membranes

Two classes of composite polymer electrolyte membranes, one conducting lithium ions (Li⁺) and the other conducting protons (H⁺) were prepared using simultaneous electron beam-induced grafting. Porous poly(vinylidene fluoride) (PVDF) films were impregnated with styrene and subjected to electron beam (EB) irradiation to obtain polystyrene (PS) filled PVDF precursor films that were subsequently treated with either chlorosulfonic acid/1,1,2,2-tetrachloroethane mixture to obtain H⁺-conducting composite membranes or LiPH₆/EC/DEC liquid electrolyte to obtain Li⁺-conducting composite membranes. The properties of the obtained membranes were evaluated using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and AC impedance measurements. The obtained membranes were found to achieve grafting content up to 46% with superior Li⁺-conductivity of 1.91 × 10⁻³ S/cm and H⁺-conductivity of 5.95 × 10⁻² S/cm. The results of this work show that simultaneous radiation-induced grafting with EB is a promising method to prepare high quality ion-conducting membranes for possible use in fuel cells and lithium batteries.     

Physicochemical study of radiation-grafted LDPE copolymer and its use in metal ions adsorption

Graft copolymerization of (acrylonitrile-co-N-vinylpyrrolidone) AN/NVP binary monomer onto (low density polyethylene) LDPE film was achieved using simultaneous irradiation method. The influence of grafting conditions such as solvent type, comonomer composition and comonomer concentration on the grafting process were investigated. The prepared grafted films were chemically modified into amidoximated form using hydroxyl amine hydrochloride (NH₂OH · HCl). The untreated and amidoximated grafted films were characterized by studying their FT-IR spectroscopy, swelling behavior and mechanical properties. The ability of the amidoximated grafted films to adsorbed metal ions such as Cr³⁺, Ni²⁺, Cd²⁺, Ag⁺ and Pb²⁺ was evaluated. The parameters that might influence the metal ions adsorption capacity of treated grafted LDPE films such as comonomer compositions, the degree of grafting, the feeding metal ions solution concentration and the pH were discussed. The obtained results illustrate that the amidoximated grafted films could be fruitful in the practical field of water treatment.