Radiation grafting of N,N-dimethylaminoethylmethacrylate onto poly(ethylene terephthalate)

Summary Radiation-induced graft polymerization of N,N-dimethylaminoethylmethacrylate (DMAEMA) from 50% solution in chloroform onto poly(ethylene terephthalate) (PET) was carried out by means of mutual γ-irradiation of polymer in presence of liquid or vapor phase monomer solutions (direct method), or by grafting of monomer from this liquid solution onto polymer preirradiated in air. It has been shown higher effectiveness of grafting by the direct method from vapor phase of monomer or by the preirradiation method as compared with direct grafting from liquid monomer solution. Grafting did not affect crystallinity, transparency and durability of the starting PET. Received: 18 November 1999/Revised version: 7 February 2000/Accepted: 8 February 2000     

The study on radiation grafting of acrylic acid onto fluorine-containing polymers. III. Kinetic study of preirradiation grafting onto poly(tetrafluoroethylene–hexafluoropropylene)

A kinetic study has been made on the preirradiation grafting of acrylic acid (AAc) onto poly(tetrafluoroethylene–hexafluoropropylene) (FEP) film. The effect of grafting conditions was investigated. The dependencies of the grafting rate on preirradiation dose and monomer concentration were found to be 0.58 and 1.25 order, respectively. The overall activation energy for the graft polymerization was 7.4 kcal/mol. The final degree of grafting increased with preirradiation dose and monomer concentration and slightly decreased as the grafting temperature was elevated. The relationship between the grafting rate and film thickness gave a negative first-order dependency, which is in agreement with that obtained for polytetrafluoroethylene—AAc grafting system. It was reasonably concluded that this grafting proceeds from the surface to the center of film with progressive monomer diffusion through the grafted layer which swells in the monomer solution.     

Radiation-grafting of N,N-dimethylaminoethylmetacrylate onto polyethylene film by preirradiation method

Radiation-induced graft polymerization of N,N-dimethylaminoethyl-metacrylate onto low density polyethylene (LDPE) film by the preirradiation method in presence of air was investigated. The appropriate reaction conditions at which the graft polymerization was carried out are reported. Received: 4 December 1996/Revised: 5 March 1997/Accepted: 10 March 1997     

Gamma preirradiation and grafting of 2N-morpholino ethyl methacrylate onto polypropylene fabric

The radiation-induced grafting of 2N-morpholino ethyl methacrylate (MEMA) in aqueous solution onto polypropylene fabric by a preirradiation technique has been investigated. Among the most important factors affecting the graft yield are monomer concentration, irradiation dose, reaction temperature, and time. It was found that the graft yield increased with increasing monomer concentration, grafting temperature, and preirradiation dose. The kinetic studies showed that the dependence of the grafting rate on monomer concentration is of 1.1 order. Moreover, the calculated overall activation energy was 14.2 kcal/mol. The grafted PP fabric shows an increase in moisture regain with increasing graft yield. Also, the dyeability with acid dye was significantly increased due to grafting with MEMA. © 1995 John Wiley & Sons, Inc.     

Radiation Graft Copolymerization of Acrylic Acid and <Emphasis Type="Italic">N</Emphasis>-Isopropylacrylamide from binary mixtures onto Polytetrafluoroethylene

Summary Acrylic acid and N-isopropylacrylamide were grafted from their binary mixtures in water onto polytetrafluoroethylene films -preirradiated in air. Effects of preirradiation dose as well as temperature of grafting on efficiency of this process were investigated, the optimal values of dose and temperature were 20 kGy and 50 °C, respectively. The calculated monomers reactivity ratios by their graft copolymerization (r₁ and r₂ ) were 0.35 and 0.01, respectively. The grafted copolymers exhibited a temperature-responsive character in the range of 17-30 °C.     

Modification of cellulosic fabrics to impart flame retardancy properties

Graft copolymerization of dimethylaminoethyl methacrylate (DMAEMA) onto cotton‐cellulose in the fabric form was carried out using a cellulose‐thiocarbonate‐ammonium persulphate redox initiation system. Effects of the concentration of the monomer, effect of liquor ratio, grafting time, and temperature were studied. The results point out the following important aspects of flame retardation of cellulose fabrics. (1) The graft polymerization of DMAEMA can improve the flame retardant properties of cellulose fabrics. (2) Tertiary amine grafted to cellulosic fabrics is suitable for nitrogen compounds that can effectively operate as synergists. The flame retardant properties of the poly‐DMAEMA‐ grafted‐phosphorylated cellulosic materials were found to be excellent even after 25 dry clean washings. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Studies on grafting of acrylic acid onto polypropylene melt‐blown nonwovens induced by electron‐beam preirradiation

We report the graft copolymerization of acrylic acid onto the polypropylene (PP) melt‐blown nonwovens induced by electron beam (EB) preirradiation in this article. The occurrence of the graft copolymerization was confirmed by means of XPS, FTIR, and SEM. The effects of preirradiation dose, monomer concentration, bath ratio, reaction time, and temperature on the graft ratio were investigated. The water conservation, water absorption rate, and K⁺ exchange capacity were also determined on the grafted PP melt‐blown nonwovens, which showed that EB preirradiation‐induced grafting was an effective way to improve the hydrophicility of PP melt‐blown nonwovens. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4971–4977, 2006     

Introduction of quaternary amines onto a film surface by graft polymerization

Quaternary amines were introduced onto a poly(ethylene terephthalate) (PET) film surface by two different methods using UV-induced graft polymerization. The first involves a two-step reaction: graft polymerization of N,N′-(dimethylamino)ethyl methacrylate (DMAEMA) onto the PET film, followed by quaternization of the tertiary N,N′-dimethylamino groups of grafted chains using alkyl bromides (R_nBr). The second is direct graft polymerization of DMAEMA having pendant quaternary amines onto the PET film. The alkyl bromides used for quaternization of the monomers and graft chains include: n-propyl, n-butyl, n-octyl, n-lauryl, and n-cetyl bromide. The two-step method could quaternarize 90% of the pendant N,N′-dimethylamino groups of the graft chains when R₃Br was used. The extent of quaternization decreased with the increasing carbon number of alkyl bromide. The direct one-step method gave a graft amine density of 8 nmol/cm² when the monomer quaternized with R₃Br was used for the graft polymerization in the presence of 1 X 10^-3M sodium metaperiodate. The carbon number of alkyl chains in the quaternary amines estimated from XPS spectra was in good agreement with that of R_nBr used for quaternization. © 1996 John Wiley & Sons, Inc.     

Study of electron beam preirradiation-induced graft copolymerization of acrylic acid onto powdered isotactic polypropylene

In order to obtain required polymer materials, acrylic acid was grafted onto powdered isotactic polypropylene by an electron beam preirradiation technique. All processes (including irradiation, storage of the samples, and grafting polymerization) were carried out in air. The effects of irradiation dose, storage time, reaction temperature, morh's salt, acid, and monomer concentration were investigated and discussed in detail. The results show that the grafting can be achieved well without purging oxygen, and morh's salt is indispensable for initiating grafting reaction and decreasing the homopolymerization. Optimal reaction conditions can be generalized for large-scale production of the desired polymer materials. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1357–1362, 1999     

Radiation grafting of acrylic acid onto fluorine-containing polymers. I. Kinetic study of preirradiation grafting onto poly(tetrafluoroethylene)

Preirradiation grafting of acrylic acid onto poly(tetrafluoroethylene) film was studied. The trapped radicals formed upon irradiation are able to induce graft polymerization under appropriate conditions. The influence of the grafting conditions were analyzed kinetically. The grafting reaction begins close to the film surface and proceeds into the center with progressive monomer diffusion through the grafted layer. The dependences of the grafting rate on preirradiation dose and monomer concentration were found to be 0.2 and 1.1 order, respectively. The overall activation energies for this grafting were calculated to be 15.2 and 4.8 kcal/mol below and above 35°C, respectively. The relationship between the grafting rate and film thickness gave a negative first-order dependence.     

利用低温等离子体进行聚砜膜的表面改性

利用低温等离子体引发接枝反应,在表面带负电的聚砜膜上引入带正电的单体聚合物,从而减少膜表面净电荷.通过测定膜的电渗流量来确定其表面电荷以作为膜表面改性效果的定量评价标准.考察了照射时间、照射功率和接枝反应时间对膜改性效果的影响,并对比了原膜与改性膜的膜污染特性.结果表明,改性后的膜表面净电荷减少,抗污染特性提高.     

Proton exchange membranes by grafting of styrene–acrylic acid onto FEP by preirradiation technique. I. Effect of synthesis conditions

Grafting of styrene–acrylic acid (sty–AA) polymer onto fluorinated ethylene propylene copolymer (FEP) was carried out by preirradiation of FEP with γ‐rays. Effect of reaction conditions on the degree of grafting such as total radiation dose, monomer concentration, temperature, and time of grafting has been studied. From the study, it is seen that the degree of grafting is strongly dependent on the reaction conditions. The rate dependence of 0.53 (～0.5) and 1.03 (～1) have been obtained with respect to total dose and monomer concentration, respectively indicating that radiation induced grafting follows free radical polymerization. The activation energy for the grafting in the temperature range of 60–90°C is found to be 33 kJ/mol. The results indicate that the grafting takes place by the front mechanism where the grafting starts at surface and slowly proceeds inwards by diffusion of the monomer through the swollen grafted chains. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2572–2577, 2003     

Alkali‐responsive membrane prepared by grafting dimethylaminoethyl methacrylate onto ethylene vinyl alcohol copolymer membrane

An alkali‐responsive membrane was prepared by grafting dimethylaminoethyl methacrylate (DMAEMA) onto ethylene vinyl alcohol copolymer (EVAL) membrane using ultraviolet (UV) irradiation graft polymerization. A subtranslucent state of EVAL membrane swelling in the DMAEMA solution was observed, and such a state enabled the passage of UV light through all the pores, inducing graft polymerization inside the pores and on the back. Attenuated total reflectance Fourier‐transform infrared spectrometer (ATR‐FTIR), X‐ray photoelectron spectroscopy (XPS), field‐emission scanning electron microscopy (FESEM), and energy‐dispersive X‐ray spectroscope (EDX) confirmed that the poly(DMAEMA)‐grafted chains existed not only on the top surface, but also inside the pores and on the back. Atomic force microscopy (AFM) and nitrogen adsorption analysis confirmed that the grafted chains collapsed in air, and decreased the surface roughness, surface area, and pore size of the grafted membranes. Alkali‐responsive properties of the poly(DMAEMA)‐grafted EVAL membrane (i.e., contact angle, permeability, and selectivity) were observed in the pH range of 9–10. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41775.     

Studies on acrylic acid–grafted polyester fabrics by electron beam preirradiation method. I. Effects of process parameters on graft ratio and characterization of grafting products

Polyester fabrics were preirradiated by electron beam in air and then grafted by acrylic acid (AA) without excluding oxygen. Effects of preirradiation dose, monomer concentration, reaction temperature, storage time, sulfuric acid, and Mohr's salt were investigated in detail and are discussed. The results suggest that it is practicable and effective to graft AA onto polyester fabrics by means of the preirradiation method. FTIR and SEM were used to characterize AA‐grafted polyester fabrics. A new band appearing at 1546 cm^?1 in the FTIR spectrum implies that AA was indeed introduced onto PET macromolecules. Changes of the diameter and the surface structure of fabric fibers presented in SEM micrographs make it clear that a layer of grafted poly(acrylic acid) was formed on the surface of these PET fibers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3931–3938, 2003     

Phase‐transfer‐agent‐aided polymerization and graft copolymerization of acrylamide

The use of phase‐transfer catalysts, with water‐insoluble initiators, for polymerization and graft copolymerization reactions was explored. The polymerization of a water‐soluble vinyl monomer, acrylamide (AAm), and the graft copolymerization of AAm onto a water‐insoluble polymer backbone, isotactic polypropylene (IPP), with a water‐insoluble initiator, benzoyl peroxide (BPO), and a phase‐transfer catalyst, tetrabutyl ammonium bromide (Bu₄N⁺Br^?), were carried out in a water/xylene binary solvent system. The conversion percentage of AAm into polyacrylamide (PAAm) and the percentage of grafting of AAm onto IPP were determined as functions of various reaction parameters, such as the BPO, AAm, and phase‐transfer‐catalyst concentrations, the amounts of water and xylene in the water/xylene mixture, the time, and the temperature. The graft copolymer, IPP‐g‐PAAm, was characterized with IR spectroscopy and thermogravimetric analysis. By a comparison of the results of the phase‐transfer‐catalyzed graft copolymerization of AAm onto IPP and the preirradiation method, it was observed that the optimum reaction conditions were milder for the phase‐transfer‐catalyst‐aided graft copolymerization. Milder reaction conditions, including the temperature, the time of reaction, and a moderate initiator (BPO), in comparison with high‐energy γ‐rays, led to better quality products, and the reaction proceeded smoothly with high productivity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2364–2375, 2004     

Graft copolymers of starch with mineral acid salts of dimethylaminoethyl methacrylate. Preparation and testing as flocculating agents

Mineral acid salts of dimethylaminoethyl methacrylate (DMAEMA) have been graft polymerized onto starch with ferrous ammonium sulfate–hydrogen peroxide initiation. The nitric acid salt was used in most reactions, and graft polymerizations were run in both water and aqueous–organic solvent systems. Increased monomer concentration in water led to an increase in both the percentage of poly(DMAEMA · HNO₃) in the graft copolymer (percent add-on) and the molecular weight of grafted branches. Variations in initiator concentration altered the percent add-on only slightly but affected the molecular weight of grafted polymer significantly. When swollen starch, in contrast with unswollen starch was used in graft polymerization reactions run in water, the product had a higher per cent add-on and a larger number of grafted branches of lower molecular weight. The efficiency of starch–poly(DMAEMA · HNO₃) graft copolymers as flocculants for diatomaceous silica increased with per cent add-on; however, variations in grafting frequency and graft molecular weight had less effect on the behavior of these materials as flocculants.     

Radiation synthesis of a thermo-pH responsive binary graft copolymer (PP-g-DMAEMA)-g-NIPAAm by a two step method

Summary  (PP-g-DMAEMA)-g-NIPAAm was synthesized using gamma radiation from a ⁶⁰Co source. Graft polymerization of N,N’-dimethylaminoethylmethacrylate (DMAEMA) onto polypropylene (PP) was accomplished in about 100 percent yield by the mutual irradiation technique at a dose of 10 kGy. Grafting of N-isopropylacrylamide (NIPAAm) onto PP-g-DMAEMA was carried out by the pre-irradiation method with doses from 20 to 100 kGy. The influence of temperature, reaction time, and monomer concentration on grafting yield was studied. Grafting processes were confirmed by infrared spectroscopy (FTIR-ATR). (PP-g-DMAEMA)-g-NIPAAm films were characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The lower critical solution temperature (LCST) and critical pH point of the films were obtained by water contact angle and percent swelling measurements. The LCST was also determined by DSC. We report here hare a new binary graft copolymer which shows two LCST values, synthesized in two steps.     

Development of membranes by radiation grafting of acrylamide into polyethylene films: Influence of synthesis conditions

SYNOPSIS: The graft copolymerization of acrylamide monomer into polyethylene films was carried out by the preirradiation method. The influence of synthesis conditions, such as monomer concentration, preirradiation dose, reaction temperature, Mohr's salt, and pregrafting storage was investigated. The order of dependence of the rate of grafting on preirradiation dose and monomer concentration was found to be 0.87 and 1.86, respectively. An activation energy of 22.9 kJ/mol for the grafting reaction was obtained. The storage of preirradiated polyethylene film at −4°C prior to the reaction showed a decrease in the degree of grafting up to 10 days, beyond which the degree of grafting remained constant. The addition of FeSO₄ in the grafting medium not only inhibits the homopolymerization of the monomer but also decreases the degree of grafting. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1331–1337, 2000     

Factorial experimental design for graft copolymerization of styrene and methyl methacrylate onto styrene–butadiene rubber

The graft copolymerization of styrene (ST) and methyl methacrylate (MMA) onto styrene–butadiene rubber (SBR) latex prepared by seeded emulsion polymerization has been studied under various reaction conditions using cumene hydroperoxide redox initiator. The mechanism of graft copolymerization has been investigated. The synthesized graft copolymers were purified and then characterized by proton nuclear magnetic resonance (¹H NMR) analysis. A 2 2 fractional factorial experimental design was applied to study the effects of the process variables such as the amount of initiator and emulsifier, the presence or absence of chain‐transfer agent, ST to MMA ratio, monomer to rubber ratio, and reaction temperature on the grafting efficiency. The analysis of the results from the design showed the sequence of the main effect on the observed response of the grafting of ST and MMA onto SBR and that the amount of chain‐transfer agent had a significant effect. Transmission electron microscopy was used to study the morphology of the graft copolymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2867–2874, 2006     

DMAEMA/SAMPS反相乳液聚合动力学

用过硫酸铵为引发剂 ,失水山梨醇酐单油酸酯 (Span-80 )为乳化剂 ,研究了甲基丙烯酸 -N、N-二甲胺基乙酯 (DMAEMA) /2 -丙烯酰胺基 -2 -甲基丙磺酸钠 (SAMPS)反相乳液聚合的聚合反应动力学。得到的动力学方程为 Rp∝ [Span-80 ] -0 .6 8[(NH4) 2 ] S2 O8] 0 .46 [SAMPS] 0 .6 0 [DMAEMA] 1 .1 2。聚合反应起始阶段和自动加速阶段的活化能分别为 5 3.6 8KJ· mol-1 和 32 .2 9KJ· mol-1 。