Structure and properties of cellulose graft copolymers. I. Radiation-induced rayon–styrene graft copolymer

Rayon–styrene graft copolymers were prepared by the direct radiation method, with the use of the preswelling technique, by irradiation with γ-rays from ⁶⁰Co. The grafting was carried out in bulk styrene and in styrene–solvent mixtures, such as styrene–methanol and styrene–acetone, to study their effect on the graft copolymerization reaction and the structure of the resulting graft copolymer. The effects of carbon tetrachloride, a chain-transfer agent, was also investigated. Three different types of rayon yarn were used; Fortisan, a modifier-type high wet-modulus rayon, and a high-tenacity tire yarn, in order to study the effect of rayon microstructure on the grafting reaction. The molecular structure of the rayon–styrene graft copolymers was studied by hydrolyzing away the cellulose backbone and measuring the molecular weights of the grafted polystyrene branches. For grafting in bulk styrene, the molecular weights of the grafted polystyrene ranged from 400,000 to 1,000,000, while those of the polystyrene homopolymer formed in the outside solution were of the order of 30,000–50,000. The molecular weights of the grafted polystyrene branches tended to increase with per cent grafting in the graft copolymer. For grafting in styrene–methanol and styrene–acetone mixtures, the molecular weights of the polystyrene branches decreased with increasing solvent content. The addition of carbon tetrachloride to bulk styrene resulted in a sharp decrease in the molecular weights of the grafted branches. The grafting frequency or number of polystyrene branches per cellulose chain was calculated from the per cent grafting and the molecular weights of the polystyrene branches. The morphology of the rayon–styrene graft copolymers and some of their physical properties are discussed.     

Gas permeation in miscible homopolymer–copolymer blends. I. Poly(methyl methacrylate) and styrene/acrylonitrile copolymers

Gas transport properties in homogeneous blends of PMMA with each of two SAN random copolymers, containing 13.5 and 28% by weight of acrylonitrile respectively, have been measured at 35°C for He, H₂, O₂, N₂, Ar, CH₄, and CO₂. For all cases, the permeability and diffusion coefficients are higher than that expected from the semilogarthmic additivity rule. On the other hand, the solubility coefficients and the ideal gas separation factors follow this rule well. These results for PMMA/SAN blends differ from those observed recently for other miscible blend systems; however, they agree well with recent theories proposed to describe gas sorption and permeation behavior in polymer mixtures. The composition dependence of gas transport properties observed in PMMA/SAN blends is attributed to the very weak net interactions between PMMA and SAN produced by repulsions between styrene and acrylonitrile units in the SAN random copolymers. Gas transport properties in phase-separated PMMA/SAN blends have also been studied. The phase-separated blends show sorption and permeation properties very similar to the corresponding homogeneous blends which can be explained by an isotropic, interconnected, two-phase model proposed by Kraus and Rollmann. Gas permeabilities for the solution cast PMMA films used here are compared with melt-extruded specimens used previously, and the differences are attributed to molecular orientation.     

Effect of degradative treatments on cotton graft copolymers. Part IV. Hydrolytic susceptibility of poly(acrylonitrile)-cotton graft copolymers

Acrylonitrile (AN) was graft polymerized to different levels onto cotton fabric using ferrous cellulose thiocarbonate-hydrogen peroxide redox system. The hydrolytic susceptibility toward 0.5 N HCl at 40°, 60°, and 80°C for 15–90 minutes of copolymers having 12, 15, and 22.5% graft was studied and compared with those of ungrafted and initiator-treated cottons. Hydrolytic susceptibility was assessed by monitoring carboxylic groups, copper number, nitrogen content (in the case of the copolymers) and tensile strength of the five substrates. Results obtained concluded that poly(AN)-cotton graft copolymers were more susceptible to acid degradation than the ungrafted and initiator-treated cottons when the acid treatment was performed under mild conditions. On the other hand, they were less susceptible when the acid treatment was carried out under relatively severe conditions.     

Behavior of chemically modified cellulose towards dyeing. IV. Dyeability of poly(methyl vinyl pyridine)-cellulose graft copolymers before and after treatment with epichlorohydrin

Grafting of 2-methyl-5-vinyl pyridine (MVP) onto partially carboxymethylated cotton having 6 meq COOH/100 g cellulose (PCMC) was effected by a Fe²⁺-H₂O₂ redox system. Different graft yields were obtained by varying MVP concentration from 10 to 100 wt % PCMC. In a subsequent step these graft copolymers were treated with epichlorohydrin. Dyeing of untreated cotton, PCMC, PCMC grafted with MVP, and epichlorohydrin-treated poly(MVP)-PCMC graft copolymers was carried out at room temperature (27°C) for varying lengths of time (2.5–60 min) in the absence of alkali catalyst or any other additives. Three reactive dyes, Procion Red M-GS, Procion Orange Brown H-2GS, and Remazole Brilliant Blue; a direct dye, Orangé Solophényle 2RL; and an acid dye, Erio Blue Marine 2GR were used at a concentration of 2% by weight of material. It was found that none of the three reactive dyes or the acid dye interacts with untreated cotton or PCMC. In contrast, the direct dye did. PCMC grafted with MVP, on the other hand, showed a substantial extent of dye exhaustion regardless of the dye used. After-treatment of poly(MVP)-PCMC graft copolymers with epichlorohydrin significantly enhanced the extent of dye exhaustion. The latter reacted almost 100% with all the dye examined, irrespective of the graft yield, which varied from 1.6% to 63%. Dyeings for reactive dyes withstood soaping for 1 hr at boil and extraction with 50% dimethylformamide, whereas dyeings for the direct dye and the acid dye failed to do so. It is believed that the presence of pyridine moieties in the graft act as an internal, built-in catalyst for expediting the reaction of reactive dyes with cellulose hydroxyls and behave as a weak base capable of salt-linkage formation in case of the acid and direct dyes.     

丙烯腈-三元乙丙橡胶-苯乙烯接枝共聚物AES的表征

采用苯乙烯和丙烯腈接枝三元乙丙橡胶合成丙烯腈-三元乙丙橡胶-苯乙烯接枝共聚物AES,用其和苯乙烯-丙烯腈（SAN）树脂共混得到AES树脂。对合成的AES树脂样品进行常温相对分子质量及相对分子质量分布的测定,红外光谱、热稳定性与微观结构表征,并与目标样品进行对比。得出三元乙丙橡胶已接枝上SAN支链,即三元乙丙橡胶与苯乙烯及丙烯腈发生了接枝共聚合反应;合成样品相对分子质量及相对分子质量分布数据、热稳定性数据及微观结构与目标样品接近;合成样品AES粉料和SAN树脂基本均匀混合的结论。     

Poly(methyl methacrylate)–cellulose nitrate copolymers. I. Preparation

Poly(methyl methacrylate)–cellulose nitrate copolymers were prepared in the form of rods and sheets by bulk polymerization using benzoyl peroxide as initiator. Suspension polymerization did not succeed in preparing poly(methyl methacrylate)–cellulose nitrate copolymers, especially when cellulose nitrate of 11.4% nitrogen content was used. The parameters such as cellulose nitrate concentration, nitrogen content of cellulose nitrate, the amount of initiator and the reaction time, and the temperature are discussed. The prepared copolymers were irradiated for specified periods of up to 11.83 Mrad. It was found that poly(methyl methacrylate)–cellulose nitrate copolymers did not dissolve in any conventional solvent, but they swelled. Swelling decreases with increasing cellulose nitrate concentrations, nitrogen content of cellulose nitrate, and irradiation dose, indicating the crosslinked structure of the prepared copolymers.     

Biodegradation of gelatin graft copolymers. III

Gelatin-g-poly(methyl acrylate) and gelatin-g-poly(acrylonitrile) copolymers were prepared in an aqueous medium using K₂S₂O₈ initiator. A plausible mechanism has been put forward for the observed grafting behavior of monomers. Gelatin-g-PAN showed a greater resistance to mixed bacterial inolucum compared to gelatin-g-PMA samples. The rate of degradation decreased with the increase in grafting efficiency. A parallel set of experiments carried out by employing the samples as the only source of both carbon and nitrogen showed a marginal but definite increase in the utilization of the polymer. The nitrogen analysis also showed the utilization of the polymer. Scanning electron micographs of the polymer films do show extensive pitting after microbiological testing.     

Anionic graft copolymers. I. Poly(vinyl chloride)-g-polystyrene. Preparation and characterization

Graft copolymers of PVC-g-PS of controlled branching were prepared by carbanionic deactivation. The reaction products were characterized mainly by GPC. It appears that secondary reactions affect the efficiency of the grafting, chiefly at low ratios of polystyrene to poly(vinyl chloride). Techniques of grafting and analyses are discussed.     

Synthesis and applications of reactive carbohydrates. III. Preparation and methylolation of polyacrylamide-carboxymethyl cellulose graft copolymers

Carboxymethyl cellulose (CMC) was treated with HCl at 80°C for different time periods (15 – 60 min). The hydrolyzed CMC samples as well as the original sample were graft copolymerized with acrylamide using K₂S₂O₈ as initiator. It was disclosed that the increasing duration of acid hydrolysis is accompanied by a progressive increment in the copper number of CMC, meanwhile its carboxyl content decreases. Acid hydrolysis enhances significantly the susceptibility of the CMC toward grafting. The latter reduces the copper number of the hydrolyzed CMC samples most probably via conversion of the aldehydic to carboxylic groups under the action of K₂S₂O₈ during grafting. Grafting also reduces the carboxyl content of the original CMC sample while increasing those of the hydrolyzed CMC samples. Methylolation of the polyacrylamide-CMC graft copolymers results in reactive finishes. When the latter were applied to cotton fabric according to the conventional pad-dry-cure method followed by a thorough washing, the fabric retained ca. 86% of the finish derived from the copolymer of CMC and 92% of finishes derived from the copolymers of hydrolyzed CMC.     

ATRP法均相制备纤维素/甲基丙烯酸丁酯接枝聚合物

在纤维素LiCl/DMAc均相溶液中,通过氯乙酰氯（ClC₂OCl）与纤维素的均相酰化反应制得纤维素氯乙酸酯（Cellulose-ClAc）后,将其溶解在DMAc中,在FeCl₂/4-二甲氨基吡啶（DMAP）的催化作用下,引发甲基丙烯酸丁酯（BMA）的均相ATRP 聚合反应,制备了纤维素/BMA接枝共聚物（Cellulose-g-PBMA）,考察了反应时间、反应温度、反应物配比等对酰化及接枝聚合反应的影响,并通过测试Cellulose-g-PBMA薄膜的接触角,对最终产物的疏水性能进行了研究;采用FTIR、NMR、SEM、TEM、AFM等分析手段对Cellulose-ClAc及Cellulose-g-PBMA的结构进行了表征;利用GPC分析了接枝聚合反应的活性特征。     

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.     

Effect of degradative treatments on cotton graft copolymers. Part V. Behavior of poly(acrylamide)-cotton graft copolymers toward acid treatments

Polyacrylamide (Aam)-cotton graft copolymers having 9, 14.5, and 20% graft were synthesized using ferrous cellulose thiocarbonate-hydrogen peroxide redox system. These copolymers as well as ungrafted and initiator-treated cottons were subjected to acid treatments (0.5 N HCl) at 40°, 60°, and 80°C for 15-90 minutes. Hydrolytic susceptibility of the five substrates was assessed by monitoring carboxylic groups, copper, number, nitrogen content (in case of the copolymers), and tensile strength. Results obtained concluded that the copolymers exhibit higher resistance to acid hydrolysis than the ungrafted and initiator-treated cottons. This was explained in terms of involvement of the ? CONH₂ groups of the graft in an interaction with HCl.     

Graft copolymers of starch. III. Copolymerization of gelatinized wheat starch with acrylonitrile. Influence of chain modifiers on copolymer composition

A study was made of the influence of selected chain modifiers on both the molecular weight of grafted polyacrylonitrile and the grafting frequency of the starch–polyacrylo-nitrile graft copolymer. Gelatinized wheat starch was used with ceric ammonium nitrate as the initiator. The organic chain modifiers investigated were ethyl mercaptan, 1-dodecanethiol, methyl ethyl ketone, acetaldehyde, and chloroform. Sodium chromate, cupric bromide, cupric nitrate, cupric acetate, and cupric chloride were also tested as chain modifiers. In the presence of cupric chloride, there was a tenfold reduction in the molecular weight of grafted polyacrylonitrile; however, fewer chains were grafted to the starch backbone than were observed without cupric chloride.     

Poly(methyl methacrylate)–cellulose nitrate copolymers. II. Physical and mechanical properties

Poly(methyl methacrylate)–cellulose nitrate copolymers were prepared by bulk polymerization using benzoyl peroxide as initiator. Cellulose nitrates of two different nitrogen contents (11.4 and 12.2%) were used. The prepared copolymers were γ-irradiated for specified periods of up to 11.83 Mrad. Their physical and mechanical properties were measured before and after irradiation. The title copolymers showed lower modulus, tensile strength, and elongation at break than poly(methyl methacrylate) itself, but they showed better hardness and abrasion. Irradiation to up to 6.57 Mrad improved the modulus of the copolymers. Hardness and abrasion were improved by increasing cellulose nitrate content. The prepared copolymers that contained cellulose nitrate of 11.4% nitrogen showed secondary transition points. The increase of cellulose nitrate concentration shifted both first and second transition points to relatively higher values.     

Cellulose graft copolymers. III. Effects of oxygen on graft copolymerization of ethyl acrylate with γ-irradiated cellulose

The effects of oxygen on graft copolymerization of ethyl acrylate from methanol–water systems with γ-irradiated fibrous cotton cellulose were investigated by electron spin resonance spectroscopy and by the formation of cellulose–poly(ethyl acrylate) copolymer. The concentrations of free radicals in cellulose irradiated dry in an atmosphere of nitrogen at 25°C decreased during postirradiation storage in nitrogen or oxygen. The concentration of free radicals in the irradiated cellulose, moisture regain of the irradiated cellulose, and formation of cellulose–poly(ethyl acrylate) copolymer decreased with increase in temperature and time of postirradiation storage and to a greater extent when stored in oxygen rather than in nitrogen. From the decrease in moisture regain of irradiated cellulose during postirradiation storage, it was concluded that increased intermolecular bonding occurred in irradiated cellulose during storage in both nitrogen and oxygen atmospheres. When irradiated celluloses which had been stored in either oxygen or nitrogen were copolymerized with ethyl acrylate at 60°C, less formation of copolymer was observed than when the copolymerization reactions were conducted at 25°C. It was concluded that there was no evidence for the formation or decomposition of cellulose peroxides during these reactions and that formation of graft copolymer depended primarily on the concentration of free radicals in the irradiated cellulose at the time of copolymerization.     

Synthesis and properties of graft copolymer of cellulose diacetate with poly(caprolactone monoacrylate)

Cellulose diacetate grafting poly(caprolactone monoacrylate) copolymers (CDA‐g‐PCLA) were synthesized by a two‐step reaction of cellulose diacetate (CDA) with poly(caprolactone monoacrylate) (PCLA). The isocyanate‐terminated intermediate (NCOPCLA) was prepared and grafted onto cellulose diacetate chains. The results of the structure analysis indicated that PCLA was connected to CDA by chemical bonding. The flow temperature of graft copolymers was lower than that of the pure CDA and decreased with increasing the grafting percentage. Outdoor soil burial tests and active sludge tests indicated that the graft copolymers have good biodegradability in natural conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 85–90, 2003     

Ultraviolet-radiation-induced graft copolymerization of styrene and acrylonitrile onto cotton cellulose

Photoinitiated graft copolymerization of the vinyl monomers, styrene and acrylonitrile, onto cotton cellulose was studied using uranyl nitrate and ceric ammonium nitrate as photoinitiators. Uranyl nitrate photoinitiation showed a higher level of grafting for styrene, whereas in the case of acrylonitrile ceric ammonium nitrate was found to be the better photoinitiator. Optimized conditions of grafting, when employed to cotton swollen with sodium hydroxide and zinc chloride, enhanced the graft levels for both monomers. Grafted samples were subjected to thermal analysis, as well as estimation of moisture regain and tenacity. Thermal stability increased, whereas, the moisture regain and tenacity decreased, with the increase in graft add-on in the case of both monomers. Acrylonitrile-grafted cotton showed dyeability with cationic dye that improved with the level of graft add-on. Possible explanations have been given.     

Blended graft copolymer of carboxymethyl cellulose and poly(vinyl alcohol) with banana fiber

Conducting hydrogel copolymer was prepared by graft copolymerization of carboxymethyl cellulose (CMC) and boric acid onto poly(vinyl alcohol) (PVA). The dielectric properties of CMC‐g‐PVA/prehydrolyzed banana blend have been investigated as a function of frequency, with special reference to pure prehydrolyzed banana. Also, the static bending for the blend was determined and no abrupt failure was observed. The dielectric properties measured were dielectric constant (ε′), dissipation factor (tan δ), and loss factor (ε″). At high frequencies, a transition in the relaxation behavior was observed, whereby the dielectric constant, loss tangent, and loss factor decreased with frequency. Experimental ε′ values of the blend are greater than those of prehydrolyzed banana. The dielectric behavior depends greatly on the nature of the present group, the crystallinity of the system, and the degree of hydrogen bonding between the different chains. The variation of the dielectric properties was correlated with blend morphology and also to the possibility for interfacial polarization that arises because of the differences in conductivities of the two phases. It was found from the infrared spectra that the incorporation of CMC‐g‐PVA copolymer decreases the crystallinity of the blend and also decreases the degree of hydrogen bonding, which results in a high dielectric constant. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1842–1848, 2006     

Poly(p-phenylene) graft copolymers with polytetrahydrofuran/polystyrene side chains

1,4-Dibromo-2,5-bis(bromomethyl)benzene was used as a bifunctional initiator in cationic ring opening polymerization (CROP) of tetrahydrofuran. The resulting macromonomer, with a central 2,5-dibromobenzene ring, was reacted in combination with 2,5-dihexylbenzene-1,4-diboronic acid by a Suzuki coupling, in the presence of Pd(PPh₃)₄ as catalyst, leading to a poly(p-phenylene) (PPP) with alternating polytetrahydrofuran (PTHF) and hexyl side chains. A polystyrene (PSt) based macromonomer with a central benzene ring bearing cyclic boronic acid propanediol diester groups, synthesized by atom transfer radical polymerization (ATRP), was also used as partner for PTHF in the cross-coupling reaction. A PPP with alternating PSt and PTHF side chains was obtained. PTHF macromonomer was also homopolymerized by a Yamamoto reaction. The resulting PPPs have high solubility in common organic solvents at room temperature. The new polymers were characterized by GPC, ¹H NMR, ¹³C NMR, IR and UV analysis. Thermal behavior of the precursor PTHF macromonomer and the final polyphenylenes were investigated by TGA and DSC analyses and compared.