Grafting of Tetrafluoroethylene onto Polyethylene by Pre-irradiation Technique

Grafting of tetrafluoroethylene onto polyethylene was carried out by a pre-irradiation technique. It was found that grafting proceeds very rapidly at -35°C in the liquid phase of tetrafluoroethylene. Takathene, which was prepared by a radiation process at Takasaki Radiation Chemistry Research Establishment, was found to be most suitable for grafting compared to other polyethylenes. The specific surface is extremely high in the Takathene, and this may be the most important reason for the high grafting speed. On the other hand, IR measurements of the grafted copolymers showed a characteristic absorption band at 1110 cm-1 which may be attributed to the structure of the grafting (branching) position. It was also found that grafted polytetrafluoroethylene can be crystallized during grafting. This is the first case of grafted polymers being in a crystalline state.     

聚乙烯薄膜等离子体接枝甲基丙烯酸及阻燃性能的研究

以聚乙烯为基础,通过等离子体接枝方法接枝甲基丙烯酸.研究了接枝反应条件对接枝率的影响,并对接枝样品的阻燃性能进行了表征.接枝后样品的点燃时间明显延长,极限氧指数明显提高,成炭量明显增加,说明接枝后的侧基(-COOH,-COO^-Na⁺和-COO^-K⁺)在热降解过程中不仅自身参与成炭,而且大大促进了基体聚合物的成炭过程.     

Surface modification of commercial composite polyamide reverse osmosis membranes

Radical grafting of two monomers, methacrylic acid and polyethylene glycolmethacrylate, onto commercial composite polyamide reverse osmosis membranes was performed. A redox system was used for initiation, and grafting was performed in an aqueous medium at room temperature. Surface grafting was characterized by ATR-FTIR, ESCA and streaming potential measurements. It was found that the membranes were surface modified without damage to their transport properties.     

Effect of swelling on radiation-induced grafting of styrene to polyethylene

The radiation-induced grafting of low-density polyethylene in contact with styrene solution was studied. The effect of the degree of swelling of the polymer on the rate of grafting was investigated by diluting the styrene with methanol and with n-octane. For styrene-methanol solution, the rate of grafting was found to increase with degree of swelling, passing through a maximum when the sorbed solvent reaches 6.2 wt-% (70 vol-% methanol in the outside solution) and decreasing therafter. The methanol fraction of the sorbed liquid is far too small to cause precipitation of the grafted chains and inhibition of their termination rate. The dilution of styrene by octane has no effect on the swelling of polyethylene, but it decreases the grafting rate over the entire concentration range. The results are explained in terms of the concentration of sorbed monomer and the viscosity of the amorphous region of the polyethylene swollen by nonpolar liquids. Supporting evidence for the mechanism is presented in the form of grafting kinetic data as a function of dose rate (2.8 × 10²?9.5 × 10⁴ rad/hr), and post-irradiation grafting measurements for polyethylene in methanol-styrene (70/30, v/v). The data indicate that at the maximum grafting rate an optimum is achieved between a high concentration of sorbed monomer and a low viscosity for the poorly swelled polymer matrix.     

Changes in row structure of extruded polyethylene film on grafting with styrene. I. Distribution of polystyrene and crystalline reorientation

Extruded films of linear polyethylene were grafted with styrene in a 1:2 styrene---methanol solution and pure styrene. The reaction was induced by simultaneous γ irradiation. Crystallinity of polyethylene was hardly affected by a polystyrene-to-polyethylene ratio as high as 13.5. From the anisotropy of film growth and small-angle x-ray diffraction it was concluded that polystyrene incorporated both into intercrystalline layers and newly formed domains alongside the stacks of lamellae. The proportion of polystyrene in interlamellar layers depends on the length of grafted chains; that is, on grafting conditions. A higher than expected proportion of occluded homopolystyrene was found in films grafted in methanol solution. The glass transition temperature of polystyrene decreased with grafting yield. Grafting in methanol solution produced changes in the x-ray orientation pattern of polyethylene. This was ascribed to untwisting and straightening crystalline lamellae in the row nucleated cylindrites.     

Surface modification of polymers. I. Vapour phase photografting with acrylic acid

Surfaces of low density polyethylene, high density polyethylene, and polystyrene have been modified by grafting with acrylic acid. Benzophenone and acrylic acid in the vapor phase were UV-irradiated in the presence of a polymer substrate. Grafting with acrylic acid took place in a thin layer on the surface, thus increasing the wettability of the polymer. After 5 min of irradiation, the contact angle against water had decreased to 20° for polystyrene and 50° for the polyethylene samples. ESCA measurements on samples irradiated for 5 min showed a 90% poly(acrylic acid) coverage of the surface for polystyrene, 63% for low density polyethylene, and 56% for high density polyethylene. Acetone or ethanol were used as carriers of monomer and initiator. Acetone was able to initiate grafting and was found to promote and direct grafting to the surface. The stability of the acrylic acid grafted surfaces was studied by contact angle measurements and ESCA. At room temperature, the grafted layer is confined to the surface, but when the material was heated in air the surface was reshaped into a hydrophobic one. The process was reversible. In aqueous surroundings at elevated temperatures the hydrophilic character of the surface was restored.     

LLDPE/SMA共混膜表面接枝PEG的研究

聚乙烯综合性能优良且价格低廉,但由于较低的表面能和惰性化学结构,其着色性、生物相容性及制品表面涂饰性能差,与各种涂饰剂的粘结强度很低,限制了其用途的拓展,须进行表面改性.聚乙烯制品的表面改性方法已有不少研究报道[1~4],相对而言,采用添加表面改性剂的方法在工艺上仍最     

Effect of solvent on radiation grafting and crosslinking of polyethylene

Crosslinking of polyethylene influences its swelling properties. It could be expected that pre-crosslinking of polyethylene influences the rate and yield of grafting as well. This is demonstrated by pre-crosslinking of polyethylene and by its subsequent grafting with styrene after the trapped radicals had been annealed out.In order to obtain more direct information about the influence of swelling agent on polyethylene crosslinking, the elastic modulus of the crosslinked polyethylene was investigated. Stress–strain curves of polyethylene samples irradiated in different environments were recorded in molten state at 165 °C. The results show that irradiation of swollen polyethylene produces fewer effective crosslinks than does irradiation of dry polymer.     

Effect of sovents on radiation-induced ionic graft polymerization

The influence of various solvents on radiation-induced cationic (grafting of vinyl-n-butyl ether onto polyethylene) and anionic (grafting of 2-methyl-5-vinylpyridine onto polyethylene) graft polymerization was studied. This ionic grafting was performed in thoroughly dried systems at room temperature. It was established that electron-acceptor solvents promote cationic grafting but that electron-donor solvents promote the anionic. A clear correlation between the donor number of solvents and grafting value by the anionic mechanism was shown. There was no correlation between dielectric constants and grafting values. The reaction orders, according to monomer concentration by 2-methyl-5-vinylpyridine grafting in various solvents, were equal to approximately 1.5 and 2 for the radical and anionic mechanisms, respectively. The effect of solvents on radiation-induced ionic graft polymerization is discussed. The results of this study indicate the correct choice of solvents for radiation-induced ionic grafting.     

超支化聚乙烯接枝马来酸酐及其过程中交联和降解反应的抑制

采用后过渡金属催化剂二-(2,6-二异丙基苯基)丁二亚胺溴化镍(IBNB),通过均相聚合法合成了高分子量和高支化度的超支化聚乙烯(HBPE).以二特戊基过氧化物(DTAP)为引发剂,研究了HBPE接枝马来酸酐(MAH)反应,并用N,N-二乙基肉桂酰胺(DECA)作为抑制剂,有效地抑制了接枝反应体系中的交联和降解副反应.接枝反应体系中分别加入相同摩尔量的DECA、N,N-二甲基乙酰胺、苯乙烯、3-(2-呋喃)丙烯酸、肉桂酸乙酯,通过比较接枝产物的凝胶含量和分子量,发现DECA抑制交联和降解副反应的效果最好,同时解释了DECA的作用机理.     

聚苯乙烯固载聚乙二醇的合成及表征

聚乙二醇在钠或浓氢氧化钠作用下接枝到氯甲基化聚苯乙烯树脂上，制成聚苯乙烯固载聚乙二醇树脂，讨论了影响接枝反应的条件．接枝反应的结果进行了电镜照片和红外光谱分析．     

Radiation-induced grafting polymerization by the ionic mechanism

A technique of radiation-induced grafting under conditions of extreme drying of monomers has been developed. Under such conditions, radiation-induced grafting polymerization of isobutylene, -methylstyrene, vinyl-n-butyl ether, styrene, acrylonitrile, and 4-vinylpyridine by the ionic mechanism at room temperature has been performed. The grafted copolymers of polyethylene, Teflon and polyvinyl chloride with monomers polymerized only ionically (isobutylene, -methylstyrene, vinyl-n-butyl ether) have been obtained for the first time. The kinetics of the radiation-induced grafting of vinyl-n-butyl ether on to polyethylene have been studied; the ionic mechanism has been confirmed. It has been found that the rates of the radiation-induced ionic grafting of styrene, acrylonitrile, and 4-vinylpyridine are much greater than those for radical grafting. The highest grafting rates are observed for 4-vinylpyridine. The mechanism of radiation-induced ionic grafting polymerization has been discussed; generalized kinetic equations have been derived to account for the contributions from radical and ionic processes.     

Electron Spin Resonance Study on Grafting of Tetrafluoroethylene onto Polyethylene

An ESR study has been made on the course of grafting of tetrafluoroethylene onto polyethylene. Alkyl and allyl radicals trapped in the polymers were measured under various grafting conditions. It was observed that alkyl radicals decay very rapidly when monomers are in contact with the irradiated polymer, while allyl radicals decay very slowly even in the presence of monomers as in the decay of radicals in irradiated polymers without monomers. The effect of pre-irradiation temperature on grafting was also studied, and the rate of grafting was found to be much faster for lower pre-irradiation temperatures. From these experimental results it was concluded that alkyl radicals play an important Tole in the initiation reaction of grafting.     

Grafting of maleic anhydride on polyethylene. II. Mechanism of grafting in a homogeneous medium in the presence of radical initiators

Grafting of maleic anhydride on polyethylene is found to take place also in a homogeneous medium. The course of reaction in nitrogen and in air and the influence of temperature of initiator and polymer concentrations suggest that grafting is due to the chain transfer reaction to polyethylene.     

Preparation of cation-exchange membrane containing bi-functional groups by radiation induced grafting of acrylic acid and sodium styrene sulfonate onto HDPE: Influence of the synthesis conditions

Electron beam radiation induced grafting of acrylic acid (AA) and sodium styrene sulfonate (SSS) onto high-density polyethylene (HDPE) membranes was investigated by the pre-irradiation method, and a cation-exchange membrane containing bifunctional groups was synthesized. The effects of grafting conditions such as monomer concentration, radiation dose and temperature on grafting yield were studied. The dependence of grafting yield on pre-irradiation dose and monomer concentration was found to be 0.54 and 2.21, respectively. The activation energy for the grafting was calculated to be 22.2 kJ/mol. Infrared spectroscopy analysis of the grafted membrane confirmed the existence of sulfonate and carboxylic acid groups.     

Radiolytic Grafting of Styrene on Polymethylpentene Film

Gamma ray initiated grafting of styrene on three polymers gave rates in the order polyethylene > polypropylene > polymethylpentene, with saturation absorption of styrene in the order polymethylpentene > polypropylene > polyethylene, indicating that the plasticizing action of absorbed styrene possibly causes increased termination rate and reduced over-all grafting rate. The rate of styrene grafting on polymethylpentene was unaffected by temperature change in the range from 23 to 85°C. Above a certain critical film thickness, styrene grafting rate is proportional to film surface area rather than film weight.     

氯化原位接枝反应制备羟基官能化CPE——结构表征

以高密度聚乙烯(HDPE)为基体,采用气-固氯化原位接枝反应合成了以氯化聚乙烯(CPE)为骨架聚合物、丙烯酸-2羟基乙酯(HEA)为支链的接枝共聚物.反应中不需要加入任何引发剂,以氯自由基引发接枝及氯代反应,得到羟基官能化CPE接枝聚合物.并用1H-NMR,FT-IR,GPC及X-射线衍射等对接枝共聚物的结构进行了表征.     

The Radiation-Induced Grafting of Vinyl Monomers to Polyethylene Terephthalate Fibers. Part I. Styrene

Some kinetic features of the mutual radiation grafting of styrene to polyethylene terephthalare fibers have been investigated. The effects of type of swelling agent, monomer concentration, and temperature have been determined. In general a maximum in the grafting rate was found to occur both with the concentration of swelling agent and with temperature. Undrawn fibers were found to graft at higher rates and maximum yield than drawn fibers. These and other features are discussed in terms of a simple grafting scheme coupled with diffusion controlled kinetics.     

Kinetics of radiation-induced grafting reactions. I. Polyethylene–styrene systems

By means of bromine labeling and ESR, the grafting reactions of styrene onto preirradiated polyethylene have been investigated. Not all the radicals produced by irradiations participate in grafting reactions all together, but they are rendered active bit by bit by the swelling of crystalline parts of polyethylene. The growing rates for polystyryl graft chains at 20°C decrease from 4 monomer units/active site/sec to one-fourth the initial value after 100 min. On the contrary, the average lifetimes increase from <10³ sec to >2.6 × 10³ sec. The number-average molecular weight of graft chains also increases with reaction times and rises to 3.5 × 10⁵ after 90 min at 20°C.     

The effect of additives on radiation-induced grafting of AA and SSS onto HDPE

A kind of ion-exchange membrane with strong acid and weak acid groups was prepared by radiation-induced grafting of acrylic acid (AA) and sodium styrene sulfonate (SSS) onto high-density polyethylene membrane (HDPE). The effect of additives such as sodium acetate, sodium chloride on grafting yield was studied. It was found that for either pre-irradiation method or simultaneous radiation method, the weak acid salt of strong alkali sodium acetate had a complex effect on the grafting yield by “pH effect” and “ion pair effect”, and the neutral salt sodium chloride was helpful to the increase of grafting yield by “ion pair effect”.