Improved synthesis of poly(MAA)–starch graft copolymers

Graft copolymerization of methacrylic acid (MAA) onto starch using a potassium persulfate/sodium thiosulfate redox initiation system was investigated. Emphasis was placed on the promotion of graft formation while minimizing homopolymerization. This could be achieved through a thorough investigation into the major factors affecting the polymerization reaction such as the state of the starch, redox ratio of the initiator, monomer and initiator concentrations, time and temperature of polymerization, and material-to-liquor ratio. The results obtained imply that the magnitude of the polymer yield including total conversion, graft yield, and homopolymer are determined by these factors. The yield is favored under the influence of higher temperature, longer time, short liquor, and increased monomer and initiator concentrations. A poly-(MAA)–starch graft copolymer is the main product of the polymerization reactions only when starch was preswelled (through cooking prior to grafting). Moreover, this grafted product could be precipitated by more dilution with water and easily separated by filtration. Hence, the results of the current work formed the basis of a novel method for the synthesis of poly(MAA)–starch graft copolymers. The mechanisms involved in the synthesis are reported. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1709–1715, 1998     

Synthesis and characterization of lignin–poly(acrylamide)–poly(2‐methacryloyloxyethyl) trimethyl ammonium chloride copolymer

In this work, two monomers, acrylamide (AM) and [2‐(methacryloyloxy)ethyl]trimethylammonium chloride (DMC) were copolymerized from kraft lignin (KL) in an aqueous suspension initiated by free radical copolymerization in the presence of potassium persulfate. The impact of copolymerization conditions on the charge density and molecular weight of the copolymers was investigated. The molecular weight and mass balance analyses confirmed that the homopolymer [polyDMC (PDMC) and polyAM (PAM)] and undesired copolymer (AM–DMC) productions dominated as time, initiator, and DMC dosage increased more than the optimum values. The activation energy of the polymerization of KL and AM (43.02 kJ mol^?1), KL and DMC (21.99 kJ mol^?1), AM (14.54 kJ mol^?1), DMC (10.34 kJ mol^?1), and AM and DMC (18.13 kJ mol^?1) was determined. Proton nuclear magnetic resonance, Fourier transform infrared spectroscopy, thermogravimetric analysis, and elemental analysis confirmed the production of KL–AM–DMC copolymer. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46338.     

Amphiphilic graft copolymer latex membranes. VI. Poly(vinyl alcohol)–acrylonitrile–N-hydroxyethyl acrylamide graft copolymer latex membranes

Poly(vinyl alcohol)(PVA)–acrylonitrile(AN)–N-hydroxyethyl acrylamide (HEAAm) graft copolymer latex membranes were prepared and properties of the membranes were compared with those of PVA–AN graft latex membranes and Cuprophane PT-150. The physical constants of HEAAm were determined and the tautomerization between hydroxyethyl amide group and aminoethyl ester group upon pH changes was ascertained by infrared spectrum of poly(HEAAm) film. An increase in HEAAm content in the membrane enhanced permeabilities of solute in aqueous solutions in comparison with PVA–AN graft latex membranes, maintaining good mechanical properties in wet state. With pH variation, the permeability of the nonionic solute was unchanged, but that of the anionic solute in acidic condition was superior to that in basic condition, and the permeability of the cationic solute exhibited the opposite trend. The behavior of ionic solute were attributable to the effect of the tautomerization of the functional group in the membrane.     

Morphologies of poly(vinylcarbazole)–polyisoprene graft copolymer and blend

The microstructures of a poly(vinylcarbazole-g-isoprene) and blend of poly(vinylcarbazole) (PVCz) and polyisoprene (PIP) were studied by transmission electron microscopy (TEM). In the graft copolymer, the unique microphase separated structure was observed. In the blend, the blend ratio did not correspond to the area ratio on the TEM photograph. It is suggested that the results are caused by rigid and crystalline PVCz and low glass-transition temperature of PIP. © 1995 John Wiley & Sons, Inc.     

Properties and applications of lignin–acrylamide graft copolymer

Free-radical, graft polymerization of acrylamide onto lignin occurs in photolysed, distilled dioxane containing calcium chloride and trace quantities of ceric ion. The yield of the reaction is controlled by the amount of oxygen present during dioxane photolysis, the duration of photolysis, and the amount of calcium chloride in the reaction mixture. Polyacrylamide homopolymer is formed during the reaction and can be removed from the graft copolymer by base dialysis. Side chains of the reaction product can be hydrolyzed to partially hydrolyzed polyacrylamide by solution in aqueous base. Hydrolysis raises the limiting viscosity number of the product by a factor of up to 47. As a drilling mud additive, the ability of the reaction product to lower yield point, lower gel strength, or lower API filtrate volume increases with increasing degree of hydrolysis.     

Preparation of poly (MAA)‐crosslinked pregelled starch graft copolymer and its application in waste water treatments

Propelled starch (PG) was first crosslinked with epichlorohydrin to obtain insoluble crosslinked pregelled starch (CPS). The latter was graft copolymerized with different amounts of Methacrylic acid using potassium persulphate as initiator. This was done to obtain six levels of poly (MAA)‐crosslinked pregelled starch graft copolymers (PMCPS) having different graft yields (expressed as meq COOH/100 g starch) with increasing order and designated as (PMCPS 1 to PMCPS 6). The latter copolymers were dispersed in aqueous solution of heavy metal ions (Cu²⁺, Pb²⁺, Cd²⁺, and Hg²⁺) and filtered to form polymer‐metal ions complex. Different factors affecting the heavy metal ions removal such as pH, extent of grafting, treatment time and starch dose were studied in detail. It was found from the obtained results that; the residual metal ions removal from their aqueous solutions increased with (a) increasing the extent of grafting of PMCPS i.e., from PMCPS 1 to PMCPS 6; (b) Increasing the pH of the metal ions solution complex from 1 to 8; (c) increasing the starch dosage from 0.25 to 2.0% (W/V), then leveled off thereafter, (d) increasing the time of the reaction up to 20 min then leveled off after that. On the other hand, Pb, Cd and Hg ions were also removed from their solutions with different extent. Furthermore, the prepared copolymer could be recovered by washing the metal ions from the complex with weak acid 1N HNO₃ (pH 2) and the metal‐binding activity of the starch was slightly reduced by this process. Finally, the ability of PMCPS to remove three types of basic dyes from their solutions was also reported. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Infrared spectroscopy and electrical properties of ternary poly(acrylic acid)–metal–poly(acrylamide) complexes

Fourier transform infrared spectroscopy (FTIR) and electrical measurements were used for the characterization of the interpolymer complexation between poly(acrylic acid) (PAA) and poly(acrylamide) (PAAm) and also the ternary PAA–metal–PAAm complexes. The interpolymer complexes were prepared by adjusting the pH value of the mixture solutions at different PAA weight fractions (W_PAA). The ternary complexes were prepared by mixing metal chloride solutions (such as ErCl₃ and LaCl₃) with different concentrations to PAA–PAAm mixtures and adjusting the pH value for different W_PAA. It was found that the IR spectra of the interpolymer complexes showed absorption bands at shifted positions and of intensities different from those of the parent polymers. Also, the examination of the spectra of the ternary metal–polymer complexes revealed that they depend on the nature, lency, ionic radius, and concentration of the added metal chlorides. Analysis of the electrical results showed that the electrical conductivity of the interpolymer complexes are always lower than those of PAA and PAAm, which was attributed to the decrease in the mobility of the polymer chains as a result of the complexation. Also, the conductivity of the ternary metal complexes showed a dependence on the properties of the additives and were found to decrease with increasing their concentrations. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2699–2705, 2002     

A new biodegradable plastic made from starch graft poly(methyl acrylate) copolymer

A starch graft poly(methyl acrylate) copolymer was developed having grafted side chains with molecular weight of less than 500,000. This material can be easily extruded into a film which shows excellent initial tensile strength and elongation. Tensile strength, however, falls off rapidly after 70 hr of water immersion at 25°C. Starch graft poly(methyl acrylate) films show excellent susceptibility to fungal growth, some samples losing more than 40% of their weight after 22 days of incubation with Aspergillus niger. Tensile tests and scanning electron micrographs of the incubated samples, after being freed of mycelium, indicate substantial biodegradation of the starch portion of the copolymer. This material may have application as a biodegradable plastic mulch.     

1,2‐propanediol–cellulose–acrylamide graft copolymers

1,2‐Propanediol–cellulose–acrylamide graft copolymers (PCACs) were developed for enhanced oil recovery. They were prepared with acrylamide and 1,2‐propanediol (PDO)–cellulose, which was formed through the addition of glycols to cellulose by the Shotten–Baumann reaction between 3‐chloro‐1,2‐propanediol and cellulose. The graft copolymerization was initiated with a redox system between Ce⁴⁺ and glycols in cellulose. The infrared spectrum of PDO–cellulose had some characteristic absorption bands around 2960 (νC? H) and 1050 cm^?1 (νC? O) that also appeared for the PDO group and pyranose ring of cellulose, respectively. The rate of Ce⁴⁺ consumption by PDO–cellulose was investigated through the calculation of the overall kinetic constant from the slopes of ln(D ? D_R) versus time (where D is the absorbance and D_R is the absorbance of the original polysaccharide solution) The results showed that PDO–cellulose had high reactivity and that there were two mechanisms of oxidation by Ce⁴⁺ with PDO–cellulose. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3022–3029, 2004     

Synthesis and physicochemical properties of graft copolymer of corn starch and acrylamide

Graft copolymerization of corn starch with acrylamide using ceric ammonium sulphate/citric acid initiation system has been studied under nitrogen atmosphere in aqueous medium. The grafting parameters are favored by increasing monomer concentration and reaction time but are affected by higher concentration of initiator and high temperature. The optimum conditions established for grafting were as follows: the concentration of initiator, 0.003 mol/L; the concentration of citric acid, 0.03 mol/L; monomer/starch, 1:1 feed ratio (w/w); reaction time, 3.0 h; and temperature, 35°C. The extent of grafting was examined by Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy. Both swelling power and solubility increased with the increase in temperature. Graft copolymerization increased swelling power and reduced solubility. Rapid visco‐analyzer pasting profile was studied. Graft copolymerization of corn starch results in high pasting temperature, high peak viscosity, and setback as compared with native starch. Breakdown was retarded at low percentage grafting (6.60%) but increased at high percentage grafting (60.27%). POLYM. COMPOS. 28:47–56, 2007. © 2007 Society of Plastics Engineers     

Characterization of the chromium (III)-crosslinked collagen–poly(butyl acrylate) graft copolymer

The redox, free radical-initiated graft polymerization of butyl acrylate onto chromium (III)-crosslinked collagen has been investigated previously. In the experiments reported here we set out to determine whether true grafting had occurred and, if so, the molecular weight of the synthetic polymer that was grafted to the collagen. The butyl acrylate grafted product was successively extracted with acetone and ethyl acetate to remove homopolymers. The solvent-extracted product was then subjected to enzymatic degradation, followed by chloroform fractionation, and finally gel permeation chromatography of the chloroform-soluble fraction. Viscosity studies of the final fractionated product indicated that the molecular weight was about 1 million. Viscosity studies of the two homopolymers extracted with acetone and ethyl acetate show that the molecular weights of these homopolymers were somewhat less than that of the isolated polymer–peptide fragment. The fractionated polymer–peptide unit contained 2.83% amino acids, indicating that there are about 288 amino acids in the peptide attached to the polymer molecule. This polymer is composed of approximately 8100 monomer units. The IR spectra confirmed that this fraction is principally poly(butyl acrylate) with amide, OH, and NH absorption bands contributed by the peptide. The isolation and characterization of the polymer–peptide fragment provided proof of graft polymerization onto the collagen molecule.     

High strength poly(meth)acrylamide copolymer hydrogels

Summary The hydrogels described here are copolymers of acrylamide and methacrylamide highly cross-linked with piperazine diacrylamide or 4, 7, 10-trioxa-1, 13-tridecanediamine diacrylamide by radical polymerisation in highly concentrated aqueous and aqueous gelatin solutions. The hydrogels were characterised by their compressive strength, refractive indices, densities, ‘free’ water contents and degree of swelling. The hydrogels cross-linked with piperazine diacrylamide gave strong glassy hydrogels, which we have termed “hydroglasses”. Cross-linking with 4, 7, 10-trioxa-1, 13-tridecanediamine diacrylamide, which contains a long flexible spacer, did not result in a more elastic gel. Polymerisation in an aqueous gelatin solution improved the mechanical properties of the gel enormously.     

Degradation behavior of poly (caprolactone)–poly(ethylene glycol) block copolymer/low–density polyethylene blends

Blends of poly(carprolactone)-poly(ethylene glycol) block polymer (PCE) with low-density polyethylene (LDPE) were prepared by extrusion followed by compression molding into thin film specimens. The morphology, thermal properties, degradation, and mechanical behavior of the blends were investigated by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), water immersion, static tensile testing, and dynamic mechanical analysis (DMA). The LDPE/PCE blends were immiscible for all chemical compositions. A LDPE/PCE (75/25 wt%) blend exhibited small reductions in weight and tensile strength after immersion in a buffer solution (pH = 5.0) at 50°C for extended periods of time. However, grafting maleic anhydride onto the LDPE/PCE blends improved the compatibility between the LDPE and PCE phases. Consequently, a 75/25 wt% blend of maleated LDPE/PCE exhibited significant losses in weight and tensile strength after immersion in the buffer solution. For comparison, blends of poly(caprolactone) (PCL) with LDPE were fabricated by similar techniques. The effect of compatibilizer on the degradation of LDPE/PCE and LDPE/PCL is discussed.     

Interactions between poly(acrylamide)–poly(itaconic acid) and cerium(IV)–nitrilotriacetic acid redox pair in the synthesis of acrylamide and itaconic acid homo‐ and copolymers

Homopolymers of itaconic acid (PIA) and its copolymers with acrylamide (P(IA‐AAm) were synthesized using ceric ammonium nitrate (NH₄)₂Ce(NO₃)₆ in combination with nitrilotriacetic acid (NTA) as redox initiator, and potassium persulphate at pH 1. The chain structures of the resulting products have been studied by FTIR spectroscopy. It is concluded from a comparison of spectroscopic results with gravimetric and viscometric data that the depressions in the yields and viscosity numbers in the case of Ce(IV)–NTA redox pair result from interactions between the constituents of the redox initiator and IA. Spectra of the insoluble and pale yellow precipitates, which are formed during the first 4 h of the reaction, after addition of Ce(IV) solution to the NTA and NTA–IA homogeneous solutions, also indicate the presence of various oxidation products. Furthermore, it is observed that H‐bonded homopolymer complex obtained from PAAm–PIA blends, prepared from aqueous solutions containing equal unit moles of each polymer, contain both ordered and defective structures. © 2001 Society of Chemical Industry     

Study of dynamic mechanical properties of poly(vinyl chloride)–ethylene vinyl acetate copolymer and poly(vinyl chloride)–chlorinated ethylene vinyl acetate copolymer mixtures

The compatibility of the mixtures poly(vinyl chloride)—ethylene vinyl acetate copolymer and poly(vinyl chloride)—chlorinated ethylene vinyl acetate copolymer was studied by the method of dynamic mechanical testing. The character of G′ and G″ was confronted with the Takayanagi model. In all cases a limited compatibility of the components was observed.     

淀粉接枝丙烯酰胺的合成及其絮凝性能的研究

以玉米淀粉(St)和丙烯酰胺(AM)单体为原料,采用过硫酸钾引发剂合成了淀粉接枝丙烯酰胺共聚物(St-g-AM)。用红外光谱对接枝共聚物进行了结构表征,用粘度法测定了分子量。讨论了聚合反应的各个因素对接枝共聚反应的影响,考察了接枝共聚物的絮凝性能。结果表明,以接枝效率为考察目标,其最佳的合成工艺为:引发剂的浓度为0.07 g/100 mL,淀粉与丙烯酰胺的质量比为1∶2.2,反应温度为65℃,反应时间3 h。淀粉接枝丙烯酰胺共聚物比430万分子量的聚丙烯酰胺(PAM)对高岭土水样的絮凝性能更好,当接枝共聚物的投加量为6 mg/L时,对高岭土水样的浊度去除率达到81.77%。最佳条件所合成出的淀粉接枝丙烯酰胺的分子量为75万。     

Fine structure of cellophane–acrylamide graft copolymer by the ceric ion method

The relationship between the grafting yield and the structure of graft copolymer is studied by measuring the branched chain lengths, the number of branches, the crystallinities, and the diffraction intensities of the (101) and (101 ) + (002) planes determined by x-ray diffraction, and the distribution of branched polymers, observed by interferometry. Over a relatively wide range of grafting yield the number of initiating sites is almost constant and about 1–2 per 2 moles of cellulose chain. Therefore, the increase of grafting yield seems to be due mainly to the propagation of branched polymers. Branched polymers are assumed to be formed in cellulose crystallites both on the normal (101) planes and in the amorphous regions of cellulose. It is found that branched polymers grow from the outer layer into the inner part of the film as the grafting yield increases. At more than 250% of grafting yield, however, branched polymers are uniformly formed throughout the layer of film in which the crystalline regions of cellulose are gradually destroyed. This result agrees with the dimensional change of gel film during the reaction. The temperature dependence of tensile strength and elongation and the wet strength of graft copolymer are also investigated. At higher grafting yields, such as 250%, the crystalline structure of cellulose is disturbed by the formation of branched polymer, and no improvement in waterproofness can be expected from grafting; the secondary bonding between branched polymers may be presumed to be same as those among cellulose. In addition, the fine cracking of the film in the burst state is found to appear more easily as the grafting yield increases, in which the aggregating state of cellulose is recognized to be changed by the formation of branched polymer.     

Synthesis and characterization of cassava starch graft poly(acrylic acid) and poly[(acrylic acid)‐co‐acrylamide] and polymer flocculants for wastewater treatment

Starch‐g‐poly(acrylic acid) and poly[(acrylic acid)‐co‐acrylamide] synthesized via chemically crosslinking polymerization were then each mixed with inorganic coagulants of aluminum sulfate hydrate [Al₂(SO₄)₃·18H₂O], calcium hydroxide [Ca(OH)₂], and ferric sulfate [Fe₂(SO₄)₃] in a proper ratio to form complex polymeric flocculants (CPFs). All CPFs exhibited low water absorbency than those of the uncomplexed superabsorbent copolymers. The color reduction by the CPFs was tested with both synthetic wastewater and selected wastewater samples from textile industries. The synthetic wastewater was prepared from a direct dye in a concentration of 50 mg dm^?3 at pH 7. The CPFs of poly[(acrylic acid)‐co‐acrylamide] with calcium hydroxide at a ratio of 1:2 is the most effective CPF for the wastewater color reduction. The CPF concentration of 500 mg dm^?3 could reduce the color of the synthetic wastewater containing the direct dye solution by 95.4% and that of the industrial wastewater by 76%. Starch‐g‐poly(acrylic acid)/Ca(OH)₂ CPF can reduce the synthetic direct dye and the industrial wastewater by 74% and 18%, respectively. Chemical oxygen demand, residual metal ion concentrations, pHs, turbidity of the wastewater were also investigated and the potential use of the complex polymer flocculants for textile wastewater treatment was indicated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2915–2928, 2006     

Fractionation of a propylene – styrene graft copolymer

A modified Baker-Williams apparatus supplemented with photoelectric control of elution cycles was designed and used for the fractionation of propylene-styrene graft copolymer. The results of the fractionation were evaluated with the aid of the TUNG function. This showed that the major part of the copolymer is homogeneous in composition and molecular weight.     

Antielectrostatic poly(ether ester) block copolymer of poly(ethylene terephthalate‐co‐isophthalate)–poly(ethylene glycol)

Poly(ethylene terephthalate) (PET) fiber has a low moisture regain, which allows it to easily gather static charges, and many investigations have been carried out on this problem. In this study, a series of poly(ethylene terephthalate‐co‐isophthalate) (PEIT)–poly(ethylene glycol) (PEG) block copolymers were prepared by the incorporation of isophthalic acid (IPA) during esterification and PEG during condensation. PEG afforded PET with an increased moisture affinity, which in turn, promoted the leakage of static charges. However, PET also then became easier to crystallize, even at room temperature, which led to decreased antistatic properties and increased manufacturing inconveniences. IPA was, therefore, used to reduce the crystallinity of the copolymers and, at the same time, make their crystal structure looser for increased water absorption. Moreover, PET fibers with incorporated IPA and PEG showed good dyeability. In this article, the structural characterization of the copolymers and antistatic and mechanical properties of the resulting fibers are discussed. At 4 wt % IPA, the fiber containing 1 mol % PEG with a molecular weight of 1000 considerably improved antistatic properties and other properties. In addition, the use of PEIT–PEG as an antistatic agent blended with PET or modified PET fibers also benefitted the antistatic properties. Moreover, PEIT–PEG could be used with another antistatic agent to produce fibers with a low volume resistance. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1696–1701, 2003