Preparation,characterization, and properties of cellulose–polyacrylamide graft copolymers

Graft copolymers of acrylamide on cellulose materials (α‐cellulose 55.8%, DP 287.3) obtained from Terminalia superba wood meal and its carboxymethylated derivative (DS 0.438) were prepared using a ceric ion initiator and batch polymerization and modified batch polymerization processes. The extent of graft polymer formation was measured in graft level, grafting efficiency, molecular weight of grafted polymer chains, frequency of grafting as a function of the polymerization medium, and initiator and monomer concentrations. It was found that the modified batch polymerization process yielded greater graft polymer formation and that graft copolymerization in aqueous alcohol medium resulted in enhanced levels of grafting and formation of many short grafted polymer chains. Viscosity measurements in aqueous solutions of carboxymethyl cellulose‐g‐polyacrylamide copolymer samples showed that interpositioning of polyacrylamide chains markedly increased the specific viscosity and resistance to biodegradation of the graft copolymers. The flocculation characteristics of the graft copolymers were determined with kaolin suspension. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 913–923, 2003     

Graft copolymerizations of modified cellulose,grafting of acrylonitrile,and methyl methacrylate on carboxy methyl cellulose

Graft copolymers of acrylonitrile (ACN), methyl methacrylate (MMA), and their mixtures on carboxy methyl cellulose (d.S 0.4–0.5) were prepared by the use of ceric ion initiator in aqueous medium. The graft copolymers were characterized by IR spectroscopy. The extent of graft copolymerization of ACN and MMA was measured in terms of graft level, molecular weight of grafted polymer chains, and the frequency of grafting as functions of ceric ion concentration. It was found that at comparable reaction conditions, the molecular weight of the grafted polymer chains and the frequency of grafting were not of the same order of magnitude. For the monomer mixtures, the copolymer compositions obtained from the total nitrogen contents of the copolymer samples showed that a disproportionately low amount of ACN monomeric units were incorporated into the graft copolymer, even at high ACN content of the feed. © 1996 John Wiley & Sons, Inc.     

Swelling and rheology of saponified starch–g–polyacrylonitrile copolymers. Effect of starch granule pretreatment and grafted chain length

A series of well-characterized starch–g–polyacrylonitrile (PAN) graft copolymers was prepared from corn starch which had been heated in water at temperatures up to 94°C to vary the extent of starch granule swelling and disruption. Graft polymerization onto gelatinized starch gave less frequent grafting of higher molecular weight PAN than comparable graft polymerizations onto ungelatinized starch. A graft copolymer was also prepared from gelatinized starch under high dilution conditions to give lower molecular weight grafted PAN and more frequent grafting. Graft copolymers were then saponified with sodium hydroxide to convert nitrile substituents to a mixture of carboxamide and sodium carboxylate. Saponified graft copolymers were only partially water soluble and consisted largely of highly swollen, insoluble gel, which was separated from solubles for the study of physical properties. Saponification mixtures were also dried to yield highly absorbent polymer films. With the exception of the graft copolymer prepared under high dilution conditions, the physical properties of saponified graft copolymers depended on whether or not the granules of starch were gelatinized before graft polymerization. Compared with saponified graft copolymers derived from ungelatinized starch, those prepared from gelatinized starch gave films that absorbed larger amounts of aqueous fluids. Also, the gel fractions from these saponified gelatinized polymers exhibited higher water swelling, lower shear modulus, and a lower reduced viscosity function (η/cQ). The saponified graft copolymer prepared from gelatinized starch under high dilution conditions more closely resembled those prepared from ungelatinized starch, suggesting that molecular weight of grafted PAN and the grafting frequency rather than starch granule pretreatment might be the most important factor which influences properties.     

Graft polymerization of vinyl acetate onto starch. Saponification to starch–g–poly(vinyl alcohol)

Graft polymerizations of vinyl acetate onto granular corn starch were initiated by cobalt-60 irradiation of starch-monomer-water mixtures, and ungrafted poly(vinylacetate) was separated from the graft copolymer by benzene extraction. Conversions of monomer to polymer were quantitative at a radiation dose of 1.0 Mrad. However, over half of the polymer was present as ungrafted poly-(vinyl acetate) (grafting efficiency less than 50%), and the graft copolymer contained only 34% grafted synthetic polymer (34% add-on). Lower irradiation doses produced lower conversions of monomer to polymer and gave graft copolymers with lower % add-on. Addition of minor amounts of acrylamide, methyl acrylate, and methacrylic acid as comonomers produced only small increases in % add-on and grafting efficiency. However, grafting efficiency was increased to 70% when a monomer mixture containing about 10% methyl methacrylate was used. Grafting efficiency could be increased to over 90% if the graft polymerization of vinyl acetate-methyl methacrylate was carried out near 0°C, although conversion of monomers to polymer was low and grafted polymer contained 40-50% poly(methyl methacrylate). Selected graft copolymers were treated with methanolic sodium hydroxide to convert starch–g–poly(vinyl acetate) to starch–g–poly(vinyl alcohol). The molecular weight of the poly(vinyl alcohol) moiety was about 30,000. The solubility of starch–g–poly(vinyl alcohol) in hot water was less than 50%; however, solubility could be increased by substituting either acid-modified or hypochlorite-oxidized starch for unmodified starch in the graft polymerization reaction. Vinyl acetate was also graft polymerized onto acid-modified starch which had been dispersed and partially solubilized by heating in water. A total irradiation dose of either 1.0 or 0.5 Mrad gave starch–g–poly(vinyl acetate) with about 35% add-on, and a grafting efficiency of about 40% was obtained. A film cast from a starch–g–poly(vinyl alcohol) copolymer in which homopolymer was not removed exhibited a higher ultimate tensile strength than a comparable physical mixture of starch and poly(vinyl alcohol).     

Graft copolymerization of vinyl monomers on cellulosic materials

Graft copolymers of acrylonitrile, ethyl acrylate, methyl acrylate, ethyl methacrylate and methyl methacrylate and of acrylonitrile/ethyl methacrylate and acrylonitrile/methyl methacrylate monomer mixtures on carboxymethylcellulose (degree of substitution 0.4–0.5) were prepared by use of ceric ion initiator in aqueous medium. The extent of graft polymer formation was measured in terms of graft level, molecular weight of grafted polymer chains and frequency of grafting as function of ceric ion concentration. It was found that at comparable reaction conditions, the molecular weight and frequency of grafting were not of the same order of magnitude. For the monomer mixtures, the copolymer compositions obtained from the total nitrogen content of the acrylonitrile/alkyl methacrylate copolymer samples showed that a relativity low amount of the acrylonitrile monomeric units were incorporated into the graft copolymer even at high acrylonitrile content of the feed.     

新型聚乙烯-g-聚乳酸接枝共聚物的合成与表征

报道了一类主链为聚乙烯(PE)共聚物,侧链为生物基聚乳酸(PLA)的新型接枝共聚物及其制备方法,并对接枝共聚物结构与性能进行了深入的表征。采用配位聚合与开环聚合相结合的方法,以羟基功能化的聚乙烯共聚物为主链,通过羟基引发L-丙交酯(L-LA)的开环聚合,从而获得聚乙烯-g-PLA接枝共聚物。通过控制单体比例和反应条件,可同时实现接枝共聚物的主链结构以及侧链结构调控。结果表明,少量PLA接枝链的引入可在不明显降低拉伸强度的情况下,有效地改善接枝共聚物的断裂伸长率。热性能表征发现侧链PLA的引入限制了主链聚乙烯的结晶,造成了接枝共聚物结晶温度以及熔点的下降。该接枝共聚物展现出了可用于PLA等生物基聚酯材料的增韧改性或共混增容剂的应用潜力,也为此类接枝共聚物的合成与性能调控提供了重要的参考。     

Upcycling by grafting onto semi-crystalline polymers using supercritical CO2

The creation of graft copolymers by selectively grafting a second polymer to the amorphous fraction of a semi-crystalline polymer in supercritical CO₂ is demonstrated herein. The graft copolymer is synthesized by free radical polymerization of a vinyl monomer within the semi-crystalline polymer below its melt temperature. Such conditions afford selective grafting on the amorphous regions (block “B”) while leaving the crystalline domains (block “A”) unmodified. Accordingly, unique A-B, A-B-A, A-B-A-B-A, and so forth. block structures are formed. In this work, styrene is polymerized within polyamide 6, polyethylene terephthalate, and isotactic polypropylene. Purification of these material is performed to remove the un-grafted homopolymer, allowing for determination of the graft yield, the portion of polymer which covalently bonds to the semi-crystalline matrix. Grafting yields achieved in polyamide 6, polyethylene terephthalate, and isotactic polypropylene were 98%, 59%, and 15%, respectively. Property enhancements were observed upon further characterization of polystyrene-polyamide 6 copolymers, including high glass transition temperatures, the ability to be remelted, and tunable grafting molecular weight. Additionally, hydrophobicity is controlled by varying polystyrene composition. The remarkable range of accessed properties demonstrates this as a potential route to upcycling plastics.     

Graft copolymerization of N‐vinyl‐2‐pyrrolidone onto sodium carboxymethylcellulose with azobisisobutyronitrile as the initiator

Graft copolymers of sodium carboxymethylcellulose with N‐vinyl‐2‐pyrrolidone were prepared in aqueous solutions with azobisisobutyronitrile as the initiator. The graft copolymers [sodium carboxymethylcellulose‐g‐poly(N‐vinyl‐2‐pyrrolidone)] were characterized with Fourier transform infrared spectroscopy, elemental analysis, nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and scanning electron microscopy. The grafting parameters, including the graft yield of the graft copolymer and the grafting efficiency of the reaction, were evaluated comparatively. The effects of reaction variables such as the time, temperature, and monomer and initiator concentrations on these parameters were studied. The graft yield and grafting efficiency increased and then decreased with increasing concentrations of N‐vinyl‐2‐pyrrolidone and azobisisobutyronitrile and increasing polymerization temperatures. The optimum temperature and polymerization time were 70°C and 4.30 h, respectively. Further changes in the properties of grafted sodium carboxymethylcellulose, such as the intrinsic viscosity, were determined. The overall activation energy for the grafting was also calculated to be 10.5 kcal/mol. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 936–943, 2007     

超临界二氧化碳中丙烯酸乙酯/3-氯丙烯接枝天然橡胶的合成与表征

采用超临界二氧化碳溶胀聚合法,以丙烯酸乙酯（EA）/3-氯丙烯（AC）为单体对天然橡胶进行了接枝改性,合成了接枝共聚物NR-g-(EA/AC)。考察了压力和引发剂用量对接枝聚合反应的影响;对NR-g-( EA/AC)进行了红外光谱、力学性能、耐溶剂性、耐燃性、硬度的测试及接枝效率和接枝率的计算,并与溶液聚合法所得NR-g-( EA/AC)的性能进行了比较。结果发现,在接枝橡胶中成功的引入了—C=O和—Cl基团;接枝橡胶的弹性模量、拉伸强度、硬度、耐燃性和耐溶剂性较天然橡胶的有了显著提高。使用溶液法和超临界二氧化碳溶胀聚合法改性天然胶乳都获得了较高的转化率和接枝率,所得产品的机械力学性能相近,但溶液法所得产品的耐溶剂性能优于后一种方法。由于超临界二氧化碳的绿色溶剂性质,超临界二氧化碳溶胀聚合法有望取代溶液聚合法而发展成一种绿色的接枝改性天然橡胶方法。     

超声-微波共辐射法合成纤维素-MMA接枝共聚物

引言纤维素作为一种天然的可再生高分子材料,存在于丰富的绿色植物中,是自然界取之不尽用之不竭的清洁资源。因此,在煤、石油、天然气的储量日益减少的今天,纤维素可作为一种可持续发展的绿色资源来研究和开发。而且天然植物纤维资源丰富、价格低廉,并且具有较好的生物可降解性,在     

Radiochemical graft copolymerization of methacrylonitrile and binary mixture of methacrylonitrile with 4-vinylpyridine onto isotactic polypropylene fiber

Graft copolymerization of methacrylonitrile (MAN) and its binary mixture with 4-vinylpyridine (4-VP) onto isotactic polypropylene (IPP) fiber has been studied in aqueous medium by the preirradiation method. Optimum conditions for obtaining the maximum percentage of grafting have been evaluated. Rate of grafting (Rg) has been determined as a function of total initial monomer concentration. The graft copolymers are characterized by IR spectroscopy, by thermogravimetric analysis, and by isolating the polymer from the graft copolymer. The effect of MAN, an acceptor monomer, on percentage of grafting of 4-VP, a donor monomer, has been discussed in the light of the mechanism proposed for grafting by the radiochemical method. © 1994 John Wiley & Sons, Inc.     

Synthesis of cassava starch‐g‐poly(methyl methacrylate) copolymers with benzoyl peroxide as an initiator

Graft copolymers of cassava starch and methyl methacrylate (MMA) were synthesized by free‐radical polymerization with benzoyl peroxide (BPO) as an initiator in an aqueous medium at 80°C. The formation of graft copolymers was confirmed by analysis of the obtained products with Fourier transform infrared spectroscopy and scanning electron microscopy. The effects of the amount of cassava starch, the amount of MMA monomer, the amount of BPO, and the reaction time on the grafting characteristics were studied. The optimum condition for grafting were obtained when 5 g of cassava starch, 5 g of MMA, 0.1 g of BPO, and a reaction time of 3 h were used. These condition provided a graft copolymer with 25.00% add‐on, 81.40% monomer conversion, 54.30% homopoly(methyl methacrylate) formed, 45.70% grafting efficiency, 37.20% grafting ratio, and 95.54% yield. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4083–4089, 2006     

Polyallene-based graft copolymer via 6-methyl-1,2-heptadien-4-ol and methyl methacrylate

A series of well-defined graft copolymers with a polyallene-based backbone and poly(methyl methacrylate) side chains were synthesized by the combination of living coordination polymerization of 6-methyl-1,2-heptadien-4-ol and atom transfer radical polymerization of methyl methacrylate. We first prepared poly(alcohol) with polyallene repeating units via 6-methyl-1,2-heptadien-4-ol by living coordination polymerization initiated by [(η³-allyl)NiOCOCF₃]₂, followed by transforming the pendant hydroxyl groups into halogen-containing ATRP initiation groups. Next, grafting-from route was used for the synthesis of the well-defined graft copolymer with excellent solubility: poly(methyl methacrylate) was grafted to the backbone via ATRP of methyl methacrylate. This kind of graft copolymer is the first example of graft copolymer via allene derivative and methacrylic monomer.     

Structural control in radical polymerization with 1,1 diphenylethylene: 2. Behavior of MMA-DPE copolymer in radical polymerization

Copolymers of 1,1-diphenylethylene (DPE) behave in a very special way in radical polymerization. Particularly, the behavior of MMA-DPE copolymers in radical polymerization is investigated. The results reveal that the semiquinoid structure of the precursor polymer identified in a previous contribution is activated by the attack of free radicals and thus, in a second stage polymerization with a second monomer, block copolymers are formed. The block copolymer yield depends strongly on the ratio between the amount of DPE-containing precursor polymer and the initiator and monomer concentration used in the second stage. The mechanism proposed is able to explain at least qualitatively all experimental results including the restriction of this mode of control of radical polymerization to the formation of diblock copolymers only.     

Synthesis and characterization of graft copolymers of syndiotactic polystyrene with polybutadiene and 4‐methylstyrene

The basic method for synthesizing syndiotactic polystyrene‐g‐polybutadiene graft copolymers was investigated. First, the syndiotactic polystyrene copolymer, poly(styrene‐co‐4‐methylstyrene), was prepared by the copolymerization of styrene and 4‐methylstyrene monomer with a trichloro(pentamethyl cyclopentadienyl) titanium(IV)/modified methylaluminoxane system as a metallocene catalyst at 50°C. Then, the polymerization proceeded in an argon atmosphere at the ambient pressure, and after purification by extraction, the copolymer structure was confirmed with ¹H‐NMR. Lastly, the copolymer was grafted with polybutadiene (a ready‐made commercialized unsaturated elastomer) by anionic grafting reactions with a metallation reagent. In this step, poly(styrene‐co‐4‐methylstyrene) was deprotonated at the methyl group of 4‐methylstyrene by butyl lithium and further reacted with polybutadiene to graft polybutadiene onto the deprotonated methyl of the poly(styrene‐co‐4‐methylstyrene) backbone. After purification of the graft copolymer by Soxhlet extraction, the grafting reaction copolymer structure was confirmed with ¹H‐NMR. These graft copolymers showed high melting temperatures (240–250°C) and were different from normal anionic styrene–butadiene copolymers because of the presence of crystalline syndiotactic polystyrene segments. Usually, highly syndiotactic polystyrene has a glass‐transition temperature of 100°C and behaves like a glassy polymer (possessing brittle mechanical properties) at room temperature. Thus, the graft copolymer can be used as a compatibilizer in syndiotactic polystyrene blends to modify the mechanical properties to compensate for the glassy properties of pure syndiotactic polystyrene at room temperature. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of poly(p-phenylene vinylene) and derivatives via a new precursor route, the dithiocarbamate route

A new synthetic route towards poly(para-phenylene vinylene) (PPV) and its derivatives has been investigated. In this route, a bis-dithiocarbamate monomer is polymerized towards a dithiocarbamate precursor polymer by the addition of a strong base (LDA). The corresponding conjugated polymer is obtained via a heat treatment of the precursor polymer. This dithiocarbamate (DTC) precursor route strikes an optimal balance between several straightforward but sometimes troublesome precursor routes and the more complex sulphinyl precursor route yielding superior purity materials. The novelty lies in the fact that the monomer synthesis is not as difficult as compared to the sulphinyl route and this without losing the quality and accessibility of the precursor polymer. In the paper, the mechanism of the polymerization process is discussed and strong indications for radical as well as anionic mechanisms are presented.     

Investigation of radiation grafting of vinyl acetate onto (tetrafluoroethylene–perfluorovinyl ether) copolymer films

A study has been made of radiation-induced grafting of vinyl acetate (VAc) on to (tetrafluoroethylene–perfluorovinyl ether) copolymer (PFA). Effects of grafting conditions such as inhibitor and monomer concentrations and irradiation dose on the grafting yield were investigated. In this grafting system, ammonium ferrous sulphate (Mohr′s salt) was added to the monomer-solvent mixture to minimize the homopolymerization of VAc and the most suitable concentration was found to be 2.0 wt%. It was found that the dependence of the initial grafting rate on monomer concentration is of the order 1.5. The degree of grafting tends to level off at high irradiation doses due to the recombination of formed free radicals without initiating graft polymerization. Some properties of the prepared graft copolymer such as swelling behaviour, electrical conductivity, thermal and mechanical properties were also investigated. The electrical conductivity was improved by hydrolysis of poly(vinyl acetate) in the grafted chains to their respective vinyl alcohols. The tensile properties were improved by grafting; however, the elongation percent decreased. The DTA data showed thermal stability of such graft copolymers for temperatures up to 300°C, but stability decreased at higher temperatures.     

双亲性氯化聚乙烯接枝共聚物的吸水膨胀性能

采用反相悬浮法制备了颗粒状接枝共聚物———氯化聚乙烯接枝丙烯酸(CPE-g-AA)、氯化聚乙烯接枝丙烯酰胺(CPE-g-AM)和氯化聚乙烯接枝混合单体丙烯酸、丙烯酰胺[CPE-g-(AA-AM)],并通过热压法制得接枝共聚物片材。考察了颗粒状接枝共聚物和接枝共聚物片材的吸水膨胀性能。结果表明,接枝共聚物的吸水性能与接枝单体的种类及其接枝率有关,相同接枝率的CPE-g-AA的吸水量比CPE-g-AM的大。当混和单体丙烯酸/丙烯酰胺的质量比为2/2时,所得接枝共聚物的抗盐性能最好。接枝共聚物片材可反复吸水膨胀,接枝率为62%的CPE-g-AA片材的二次吸水达到平衡时的吸水率和膨胀率分别为120%和41%。通过测定接枝共聚物的接触角表明,CPE-g-AA对水的润湿作用比CPE-g-AM明显。     

Synthesis of Graft Copolymers and Their Preliminary Use as a Compatibilizer in Polymer Solar Cells

Poly(p-xylylene)-graft-poly(butylacrylate-g-fullerene) or PPX-g-PBAFu was synthesized by using Wessling route and atom transfer radical addition (ATRA) techniques. The graft copolymers were used as a compatibilizer in the bulk heterojunction (BHJ) polymer solar cells of poly(3-hexylthiophene) (P3HT) and fullerene (C₆₀). The results from AFM micrographs showed that the phase size of P3HT and the aggregated C₆₀ in the blended system was decreased from 300 to 30 nm after adding the copolymer (20 pph). Furthermore, the efficiencies of the BHJ cells from J-V curve were remarkably increased five times after adding the copolymer.     

Block copolymerization by a cation to anion transformation process: 2. Polymerization of styrene by polyTHF possessing terminal secondary nitranions

A route for preparing block copolymers by a cation to anion transformation is examined. PolyTHF possessing a terminal secondary amine group is prepared by reacting living polymer with excess of the primary amine, then metallated with potassium to create a terminal nitranion. This is then used to initiate the anionic polymerization of styrene, but initiation is relatively slow and, although all the styrene is consumed, only about 30% of polyTHF chains form a block copolymer.