Synthesis and characterization of dextrin‐grafted polypropylene

We carried out the graft copolymerization of the water‐soluble natural polymer dextrin onto preirradiated polypropylene (PP) in an aqueous medium using benzoyl peroxide (BPO) as the radical initiator. PP was irradiated by γ rays from a Co⁶⁰ source at a constant dose rate of 3.40 kGy/h to introduce hydroperoxide linkages, which served as the sites for grafting. The graft copolymerization was studied as a function of different reaction parameters, and the maximum percentage grafting (P_g; 55%) of dextrin onto PP was obtained at optimum conditions of [BPO] = 5.165 × 10⁻² mol/L, temperature = 60°C in 120 min with 15 mL of water. Different grafting parameters, such as the percentage apparent grafting, percentage grafting, and percentage true grafting have been evaluated. The graft copolymers were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy. Swelling studies were carried out in pure, binary, ternary, and quaternary solvent systems composed of water, ethanol (EtOH), dimethyl sulfoxide (DMSO), and N,N‐dimethylformamide (DMF) at different ratios. The maximum swelling percentage PP‐g‐dextrin (both composite and true graft) was observed in pure DMSO and DMF followed by EtOH and water. Water‐retention studies of PP and PP‐g‐dextrin (both composite and true graft) were investigated at different time periods, temperatures, and pH values. The maximum percentage water retention of PP‐g‐dextrin (composite, 124%) was observed at 8 h and 50°C in a neutral medium (pH 7). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of polyethylene modified through phase‐transfer‐catalyzed graft copolymerization

In an effort to impart biodegradability, polyethylene (PE) was modified through the graft copolymerization of vinyl monomers such as acrylamide (AAm) and acrylic acid (AAc) by a phase‐transfer‐catalyst method. The grafting percentage of AAm and AAc for PE was found to be dependent on the dibenzoyl peroxide concentration, monomer concentration, time, temperature, and concentration of the phase‐transfer catalyst. Some AAm‐ and AAc‐grafted PE samples were prepared by chemical, UV, and γ‐radiation methods. The biodegradation of samples of PE, polyethylene‐g‐polyacrylamide, and polyethylene‐g‐poly(acrylic acid) prepared by all these methods was studied. The weight loss of the samples over a period of time was observed with soil‐burial tests. The grafted samples prepared by the phase‐transfer‐catalyst method showed better biodegradation results than those prepared by other methods of grafting. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Surface modification of polymethyl methacrylate intraocular lenses with the mixture of acrylic acid and acrylamide via plasma‐induced graft copolymerization

An approach is presented for the graft copolymerization of acrylic acid (AAc) and acrylamide (AAm) mixture onto the surfaces of polymethyl methacrylate intraocular lenses (PMMA IOLs) treated with an Argon gas plasma, followed by the exposure to the oxygen atmosphere. In this case, peroxides formed by the plasma treatment are likely to be responsible for initiating the graft copolymerization. The amount of peroxides on the surface of PMMA IOLs was determined using 1,1‐diphenyl‐2‐picrylhydrazyl, and the maximum amount was found with the plasma treatment at 30 W for 20 s under 5 mTorr pressure. The surfaces of the grafted PMMA IOLs were characterized using Fourier transform infrared spectroscopy‐attenuated total reflectance (FTIR‐ATR), electron spectroscopy for chemical analysis, and contact angle meter. The FTIR‐ATR spectrum of PMMA‐g‐AAc‐AAm showed the characteristic band of PAAc at 1580 cm^?1 together with those of PAAm at 1670 and 1630 cm^?1, confirming that the copolymer of AAc and AAm was successfully grafted onto the surfaces of PMMA IOLs. The experimental data of O1s/C1s and N1s/C1s reasonably concurred with the calculated data, a strong indication that the pH value of the reaction medium at 3.77 could produce a graft with an equal molar ratio. Surface tension of the samples increased to 52 dyn/cm due to the graft of the hydrophilic monomers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2361–2366, 2002     

Syntheses and properties of N‐vinylpyrrolidione‐g‐EPDM and its modified polymer

The graft copolymerizations of N‐vinylpyrrolidione(NVP) onto ethylene–propylene–diene terpolymer (EPDM) were carried out with benzoyl peroxide (BPO) as an initiator in toluene. The synthesized EPDM‐g‐NVP (ENVP) was characterized by infrared (IR) spectroscopy and gel permeation chromatography (GPC). The effects of initiator and monomer concentrations, reaction time, and temperature were investigated in the graft copolymerization. The highest graft efficiency was obtained at 0.04 mol of NVP, 2 g of EPDM, 2 wt % of BPO and 80°C for 72 h. Modified ENVP (MENVP) was obtained by the reaction of ENVP and KOH in MeOH. Properties of EPDM, ENVP, and MENVP were investigated by a thermogravimetric analyzer (TGA), an instron tensile tester, a Fade‐O‐Meter, and a UV spectrophotometer. Tensile strength and light resistance of ENVP were better than those of MENVP. The dyeability of polymers was increased in following order: MENVP > ENVP > EPDM. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1177–1184, 1999     

A new polymerization method and kinetics for acrylamide: Aqueous two‐phase polymerization

The concept of aqueous two‐phase polymerization and a new polymerization method for the preparation of water‐soluble polymers are presented. The phase diagram of poly(acrylamide) (PAAm)‐poly (ethylene glycol) (PEG)‐water two‐phase system was measured by the gel permeation chromatography (GPC). The aqueous two‐phase of PAAm‐PEG‐water system can be easily formed. The critical concentration of phase separation was affected by the molecular weight of PEG. The aqueous two‐phase polymerization of acrylamide (AAm) has been successfully carried out in the presence of PEG by using ammonium persulfate (APS) as the initiator. The polymerization behaviors with varying concentration of AAm, initiator and PEG, the polymerization temperature, the molecular weight of PEG, and emulsifier types were investigated. The activation energy of aqueous two‐phase polymerization of AAm was 132.3 kJ/mol. The relationship of initial polymerization rate (R_p0) with APS and AAm concentrations was R_p0 ∝ [APS]^0.72 [AAm]^1.28. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of starch‐graft‐polyacrylonitrile hydrolyzate and its characterization

The graft copolymerization of three vinyl monomer species, acrylonitrile (AN), acrylamide (AAm), and acrylic acid (AA), onto starch was carried out with ceric salt (Ce salt) as an initiator. With 3 mmol/L Ce salt, the monomer activity onto starch decreased in the following order: AN > AAm > AA. Grafting efficiency with AN as the grafting monomer was greater than 90%, but with AA and AAm, it was less than 50%. Starch‐graft‐polyacrylonitrile was hydrolyzed to introduce amide and carboxyl groups into starch. The hydrolyzates were analyzed with infrared spectroscopy. The hydrolysis reaction was accelerated with increasing alkali concentration, reaction temperature, and time. The water absorbancy of the hydrolyzate increased with an increasing carboxyl molar fraction in the polymer, and it dissolved in water above a 0.6 molar fraction. The absorbancy of water was 2 times higher than that of a NaCl aqueous solution. The copper‐ion‐exchange capacity of the sample was greater in graft copolymers with higher carboxyl group contents. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1437–1443, 2001     

High molecular weight hydrophilic functional copolymers by free‐radical copolymerization of acrylamide and of N‐acryloylmorpholine with N‐acryloxysuccinimide: Application to the synthesis of a graft copolymer

Free‐radical solution copolymerization of acrylamide (AAm) and of a disubstituted acrylamide derivative, N‐acryloylmorpholine (NAM), with N‐acryloxysuccinimide (NAS) was investigated with the aim to obtain a copolymer of at least 100,000 g mol^?1. Different polymerization conditions likely to increase the molecular weight were studied such as monomer and initiator concentrations, temperature, and nature of the solvent. The molecular weights were determined by SEC using a light‐scattering detector. The grafting of end‐functionalized polysaccharide chains onto such high molecular weight poly(NAM‐co‐NAS) was performed and a graft copolymer bearing a high number of saccharidic branches was obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1808–1816, 2003     

聚乙烯的化学改性——丙烯酸在聚乙烯上的接枝共聚及其表征

在二甲苯溶液中以过氧化苯甲酰为引发剂研究了丙烯酸在聚乙烯上的接枝共聚。讨论了反应温度、单体浓度和引发剂浓度对接枝率的影响。用红外光谱、ＸＰＳ、薄层色谱和接触角证实了接枝物的存在。又制备了接枝物钠盐。     

Plasma‐induced solid‐state polymerization modified poly(tetrafluoroethylene) membrane for pervaporation separation of aqueous alcohol mixtures

Acrylamide (AAm) solid state polymerization was induced using argon plasma to improve the pervaporation performance of poly(tetrafluoroethylene) (PTFE) membranes (PTFE‐g‐PAAm) in aqueous alcohol mixtures. The surface morphology, chemical composition, and hydrophilicity changes in the PTFE and PTFE‐g‐PAAm membranes were investigated using ATR‐FTIR, SEM, AFM, X‐ray photoelectron spectroscopy, and water contact angle measurements. The surface hydrophilicity rapidly increased with increasing Ar exposure time, but decreased after longer Ar exposure time because of the degradation in the PTFE‐g‐PAAm membrane grafted layer. Compared with the hydrophilicity of the pristine PTFE membrane (water contact angle = 120°), the argon plasma induced acrylamide (AAm) solid‐state polymerization onto the PTFE surface (water contact angle = 43.3°) and effectively improved the hydrophilicity of the PTFE membrane. This value increases slowly with increasing aging time and then reaches a plateau value of about 50° after 10 days of storage under air. The pervaporation separation performances of the PTFE‐g‐PAAm membranes were higher than that of the pristine PTFE membrane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:909–919, 2006     

Characterization of hydrogels prepared by the γ irradiation of aqueous solutions of acrylamide and N‐vinyl‐2‐pyrrolidone comonomers

Copolymer hydrogels were prepared through the γ irradiation of aqueous solutions composed of different ratios of acrylamide (AAm) and vinyl pyrrolidone (VP) monomers. The chemical structure, thermal stability, and structural morphology of the hydrogels were characterized with Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA), and scanning electron microscopy, respectively. The IR spectroscopy analysis showed the formation of copolymerization and the presence of hydrogen bonding. The TGA study showed that the AAm/VP‐based hydrogels possessed higher thermal stability than polyacrylamide (PAAm). However, the thermal stability of the AAm/VP hydrogels increased with an increasing ratio of the VP component. The study of the swelling kinetics in water showed that all the hydrogels reached the equilibrium state after 24 h. However, the AAm/VP‐based hydrogels showed swelling in water that was lower than that of the hydrogel based on pure AAm. Meanwhile, the degree of swelling of the AAm/VP‐based hydrogels decreased with an increasing ratio of VP in the feeding solutions. The results showed that the PAAm and AAm/VP‐based hydrogels prepared at 50 kGy were affected by a change in the temperature around 25°C, whereas the hydrogels prepared at 25 kGy did not show this characteristic. However, the hydrogels prepared at different doses displayed reversible pH character. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Starch‐grafted polypropylene: Synthesis and characterization

Graft copolymerization of starch has been carried out onto preirradiated polypropylene (PP) in an aqueous medium using benzoyl peroxide (BPO) as the radical initiator. The maximum percentage of grafting (115%) of starch onto PP was obtained at optimum conditions of BPO concentration, 1.239 × 10⁻³ moles; temperature, 65°C; in 120 min. using 30 mL of water. Swelling studies were carried out in pure, binary, ternary and quaternary solvent systems comprising of water, ethanol (EtOH), dimethylsulphoxide (DMSO), and N,N‐dimethylformamide (DMF) in different ratios. Maximum swelling is observed in DMSO and DMF, followed by EtOH and least in water for true graft. Water retention studies of pristine PP and PP‐g‐Starch (both composite and true graft) were investigated at different time periods, temperature and pH. The composite contains grafted PP, unreacted starch and unreacted PP whereas true graft is the product from which both unreacted polymers have been removed. Maximum % water retention of PP‐g‐Starch (composite) (110%) was observed in 8 h at 50°C in neutral medium (pH = 7). The graft copolymers were characterized by FTIR, DTG, DTA, TGA, and SEM. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Melt grafting of n‐butyl methacrylate onto poly(vinyl chloride): Synthesis and characterization*

The graft copolymerization of n‐butyl methacrylate monomer onto compounded poly(vinyl chloride) was carried out by melt‐mixing process in a Brabender plasticorder (BPCR) using a free‐radical initiator. The reaction conditions such as initiator and monomer concentration, shear rate (rpm), residence time, and temperature were optimized in the mixing head of BPCR attached to a torque rheometer. The graft copolymers were Soxhlet extracted with cyclohexane and were characterized by intrinsic viscosity, FTIR, and ¹³C‐NMR spectroscopy. A maximum of 14% grafting was obtained. The graft copolymer showed significant improvement in processibility and both thermal and mechanical properties. Scale‐up studies of the optimized recipe were carried out in a single‐screw extruder for commercial trials/evaluation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2442–2449, 2004     

Graft copolymerization of acrylic acid onto methylcellulose by potassium permanganate‐p‐xylene redox pair

Poly(acrylic acid) was grafted onto methylcellulose in aqueous media by a potassium permanganate‐p‐xylene redox pair. Within the concentration range from 0.93 × 10^?3 to 9.33 × 10^?3M, p‐xylene, the graft copolymerization reaction exhibited minimum and maximum graft yields and was associated with two precursor‐initiating species, a p‐xylyl radical and its diradical derivative. The efficiency of the graft was low, not higher than 12.9% at a p‐xylene concentration of 0.93 × 10^?3M and suggested the dominance of a competitive homopolymerization reaction under homogeneous conditions. The effect of permanganate on the graft yield was normal and optimal at 135% graft yield, corresponding to a concentration of the latter of 33.3 × 10^?3M over the range from 8.3 × 10^?3 to 66.7 × 10^?3M. The conversion in graft yield showed a negative dependence on temperature in the range 30–60°C and suggested a preponderance of high activation energy transfer reaction processes. The calculated composite activation energy for the graft copolymerization was 7.6 kcal/mol. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 278–281, 2004     

Graft copolymerization of an itaconic acid/acrylamide monomer mixture onto poly(ethylene terephthalate) fibers with benzoyl peroxide

A mixture of acrylamide (AAm) and itaconic acid (IA) was grafted onto poly(ethylene terephthalate) (PET) fibers with benzoyl peroxide in aqueous media. The effects of polymerization conditions such as the temperature, polymerization time, initiator concentration, and monomer mixture ratio on grafting were investigated. The maximum graft yield was 76.1% with an AAm/IA mixture ratio of 90/10 (mol/mol). The graft yield was as low as 3% in the single grafting of IA, whereas the use of AAm as a comonomer increased the amount of IA that entered the fiber structure to 33.5%. An increase in the temperature from 65 to 85°C increased the grafting rate and saturation graft yield. However, an increase in the temperature above 85°C decreased the saturation graft yield. The graft yield increased up to an initiator concentration of 1.0 × 10^?2 M and decreased afterwards. The grafting rate was 0.65th‐ and 0.74th‐order with respect to the initiator and AAm concentrations, respectively. The densities, diameters, and moisture‐regain values of the AAm/IA‐grafted PET fibers increased with the graft yield. Similarly, there was an increase in the dyeability of the AAm/IA‐grafted fibers with acidic and basic dyes. The grafted fibers were characterized with Fourier transform infrared and thermogravimetric analysis, and their morphologies were examined with scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1795–1803, 2005     

Effect of aging on synthesis of graft copolymer of EPDM and styrene (EPDM‐g‐PS)

The effect of aging on synthesis by the graft copolymerization of styrene onto random ethylene–propylene–diene monomer with benzoyl peroxide (BPO) as the initiator is described. Results showed that yields of graft copolymer are increased in the first 10 min. After 10 min, the total polymer produced has a maximum at about 25 min. However, the portion of the graft copolymer is decreased and the portion of the pure polystyrene is increased. In addition, the influence factors, such as reaction time, temperature, BPO concentrations and styrene concentrations, effect of solvents on the extent of graft copolymerization were discussed. The extent of grafted copolymerization was verified by hexane and acetone Soxhlet (solvent extraction). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4809–4813, 2006     

Synthesis and properties of high oil‐absorbent 4‐tert‐butylstyrene‐EPDM‐divinylbenzene graft terpolymer

The graft crosslinking polymerization of 4‐tert‐butylstyrene (tBS) and divinylbenzene (DVB) onto ethylene–propylene–diene (EPDM) was carried out in toluene by using benzoyl peroxide (BPO) as an initiator. The synthesized graft terpolymer, tBS‐EPDM‐DVB (PBED), was extracted with tetrahydrofuran (THF) into gel (called as PBED I) and sol, and then they were identified by infrared (IR) spectroscopy. The effects of solvent amount, molar ratio of DVB to tBS, EPDM content, initiator concentration, reaction temperature, and reaction time on the graft crosslinking polymerization were examined. Among them, solvent amount and molar ratio of DVB to tBS were the important factors for this reaction system. Maximum oil absorbency of PBED I was 84.0 g/g but its oil‐absorption kinetic rate was very low. Sol PBED can be reused as oil absorbent (named as PBED II) through photocrosslinking by ultraviolet light irradiation. Although the oil absorbencies of PBED II were lower than those of PBED I in most cases, their oil absorption kinetic rates were higher than oil absorbencies of PBED I. The highest value of oil absorbency of PBED II was 56.0 g/g. The thermal stability of PBED I was studied by TGA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2119–2129, 2002     

Mass transfer and radical flux effects in dispersed‐phase polymerization of isooctyl acrylate

The kinetics of dispersed phase polymerization of a highly water‐insoluble monomer (isooctyl acrylate) were explored in emulsion, miniemulsion, and microsuspension polymerization. The effects of monomer water solubility and choice of initiator (oil‐ vs. water‐soluble) strongly impact the final product (particle size and molecular weight distribution). For emulsion polymerization, as the surfactant concentration was increased, there was a transition from homogenous to micellar nucleation near the CMC, then a drop in nucleation rate at high surfactant concentration due to insufficient radical flux to support more nucleation. For miniemulsion polymerization, a slow rate of growth of (droplet) nucleation with surfactant concentration was found, followed (at the CMC) by an increase in the rate of nucleation with added surfactant as the mode of nucleation switched to micellar. The conversion‐time kinetics of microsuspensions could be modeled with a bulk polymerization model. IOA is sufficiently insoluble in the aqueous phase that emulsion polymerization may or may not be reaction limited. The presence of a stabilizer such a PAA, the use of an oil‐soluble initiator such as BPO, and the insolubility of IOA in the aqueous phase all push the polymerization locus toward droplet (microsuspension) nucleation and bulk kinetics.© 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5649–5666, 2006     

聚乙烯固相接枝马来酸酐的研究

研究了以过氧化苯甲酰（ＢＰＯ）为引发剂,二甲苯为界面剂,粉状聚乙烯（ＨＤＰＥ、ＬＬＤＰＥ）固相接枝马来酸酐（ＭＡＨ）的反应。讨论了反应温度、引发剂用量、单体用量和界面剂种类等对接枝反应的影响,并用红外光谱法证实了接枝反应。结果表明,ＰＥ固相接枝ＭＡＨ反应对温度敏感,随温度升高,接枝率提高;在一定范围内,接枝率随引发剂用量、单体用量和搅拌转速、界面剂用量的增加而提高;界面剂用量虽少,但能促进ＢＰＯ、ＭＡＨ在ＰＥ上的反应。通过接枝反应可得到接枝率为９％左右的ＰＥ－ｇ－ＭＡＨ产物和接枝率为１３％以上的ＬＬＤＰＥ－ｇ－ＭＡＨ产物     

Polymerization of acrylamide in styrene containing inverse microemulsions: polymerization kinetics and polymer product composition studies

The kinetics of free‐radical homopolymerization and copolymerization of acrylamide (AAm) and styrene (S) initiated by water‐soluble ammonium peroxodisulfate, (APS) or by toluene‐soluble dibenzoyl peroxide (DBP) in inverse microemulsion toluene/S/AOT (sodium bis(2‐ethylhexyl)sulfosuccinate)/water/AAm characterized by a low volume fraction of the aqueous phase (Φ_aw ≈ 0.08) as a function of the concentration of S in the oil phase of the inverse microemulsion system have been studied. S strongly decreases the rate of AAm/S (co)polymerization. This is valid for both APS and DBP initiators. Kinetic measurements indicate the important role for cross‐initiation of water soluble AAm growing chains and of oil soluble S analogues activated by the primary free‐radicals generated from APS (or from DBP) in the dispersed water droplets (or in the continuous oil‐phase) of the inverse microemulsion, respectively. With inverse microemulsions containing toluene (70.73 %)/S (2.44 %)/AOT(17.56 %)/water (7.32 %)/AAm (1.95 %), after polymerization (initiator APS, 3.04 × 10⁻² mol dm⁻³ of water) and separation of the polymeric components, the following yields were obtained: AAm/S (co)polymer (89.20 mass%; ie 62.24 mass% of AAm structural units and 26.96 mass% of S structural units), polyacrylamide (9.4 mass%) and polystyrene (1.4 mass%). © 2000 Society of Chemical Industry     

Low protein fouling polypropylene membrane prepared by photoinduced reversible addition‐fragmentation chain transfer polymerization

In this study, 2‐hydroxyethyl methacrylate and N‐isopropyl acrylamide was block grafted onto the polypropylene macroporous membrane surface by photo‐induced reversible addition‐fragmentation chain transfer (RAFT) radical polymerization with benzyl dithiobenzoate as the RAFT agent. The degree of grafting of poly(2‐hydroxyethyl methacrylate) on the membrane surface increased with UV irradiation time and decreased with the chain transfer agent concentration increasing. The poly(2‐hydroxyethyl methacrylate)‐ grafted membranes were used as macro chain transfer agent for the further block graft copolymerization of N‐isopropyl acrylamide in the presence of free radical initiator. The degree of grafting of poly(N‐isopropyl acrylamide) increased with reaction time. Furthermore, the poly(2‐hydroxyethyl methacrylate)‐ grafted membrane with a degree of grafting of 0.48% (wt) showed the highest relative pure water flux and the best antifouling characteristics of protein dispersion. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012