Grafting of poly (methyl acrylate) onto sulfite pulp fibers and its effect on water absorbance

To prepare super water absorbent hydrogels of wood cellulose fibers, poly (methyl acrylate) (PMA) was copolymerized onto softwood sulfite pulp fibers using free radical initiator followed by alkaline hydrolysis. Ceric ammonium nitrate (CAN) was used as the free radical initiator. Effects of various parameters such as fiber concentration, monomer/pulp (M/pulp) ratio, CAN concentration, and reaction time on the grafting yield and on other grafting parameters were investigated. The graft conversion was the same from low to medium fiber concentration. The amount of initiator required was found to be independent of fiber concentration to achieve maximum grafting yield. Different fiber fractions (classified based on their length) have no effect on the grafting yield. The evidence of graft copolymerization was determined by using ATR‐IR spectroscopy. The X‐ray diffraction (XRD) analysis shows that grafting takes place both in amorphous and crystalline regions of cellulose fibers and the decrease in crystallinity of the grafted fibers with an increase in grafting yield was confirmed. The surface morphology of the PMA‐g‐cellulose was characterized by scanning electron microscopy (SEM). The water retention value of the hydrolyzed grafted pulp was determined based on a centrifugation technique. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Functional biohybrid materials synthesized via surface-initiated MADIX/RAFT polymerization from renewable natural wood fiber: Grafting of polymer as non leaching preservative

Crude wood fibers represent a wide class of renewable resources. The surface modification of such materials via covalent grafting of polymer offers new surface properties with non-leaching coating. The grafting of the polymer chains was achieved by surface-initiated controlled radical polymerization through a grafted xanthate chain transfer agent. Macromolecular design via interchange of xanthate (MADIX) technique was chosen to graft poly(vinyl acetate), polystyrene, poly(n-butyl acrylate) and poly(4-vinylbenzyl chloride)-polystyrene amphiphilic cationic copolymers. Water contact angle measurements highlighted the hydrophobization of the wood fiber surface with a nanoscaled polymer monolayer indicating the appropriate coverage of the fiber. X-ray photoelectron spectroscopy showed the successful grafting of the polymer after drastic washing procedure. The quaternization of the grafted polystyrene-co-poly(4-vinyl benzyl chloride) copolymers with tertiary amine allows the introduction of biocide quaternary ammonium functions while preserving the hydrophobic character of the modified wood fiber when introducing a long alkyl chain in the statistical copolymer. Finally, the cationic copolymer was subjected to Coniophora Puteana to evaluate its propensity to limit the fungi expansion.     

Paper‐sheet biocomposites based on wood pulp grafted with poly(ε‐caprolactone)

Kraft pulp fibers were used as substrates for the grafting of poly(ε‐caprolactone) (PCL) from available hydroxyl groups through ring‐opening polymerization, targeting three different chain lengths (degree of polymerization): 120, 240, and 480. In a paper‐making process, paper‐sheet biocomposites composed of grafted fibers and neat pulp fibers were prepared. The paper sheets possessed both the appearance and the tactility of ordinary paper sheets. Additionally, the sheets were homogenous, suggesting that PCL‐grafted fibers and neat fibers were compatible, as demonstrated by both Fourier transform infrared spectroscopy microscopy and through dye‐labeling of the PCL‐grafted fibers. Finally, it was shown that the paper‐sheet biocomposites could be hot‐pressed into laminate structures without the addition of any matrix polymer; the adhesive joint produced could even be stronger than the papers themselves. This apparent and sufficient adhesion between the layers was thought to be due to chain entanglements and/or co‐crystallization of adjacent grafted PCL chains within the different paper sheets. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42039.     

Photo-induced polymerization of methyl acrylate vapors on prewetted polyamide and polyester fibers

Photo-induced polymerization of methyl acrylate vapors on polyamide and polyester fibers occurred when these fibers were wetted with the polar solvents methanol, N,N-dimethylformamide, or dimethyl sulfoxide (neat or in aqueous solution). Polymer grafting was accompanied by homopolymer formation, with the amount of grafting and ratio of grafting to homopolymerization being dependent on the fiber type, the solvent used to wet the fiber, and the amount of water present in the wetting solution. Overall deposition of polymer was higher on polyamide than on polyester under all wetting conditions. Water present in the wetting agent had a limited effect on polymerization of poly(methyl acrylate) on polyamide, whereas water caused a rapid decrease in polymerization on polyester. The nature of polymer grafting on the fibers under various wetting conditions was examined by scanning electron microscopy and tensile property measurements, and the mode of polymer deposition was outlined in light of our findings.     

Grafted carbon fibers and their physicochemical properties. I. Grafting of methacrylic acid onto carbon fibers

A simple, reproducible method for grafting different carbon fibers (modified and unmodified, high‐modulus, and high‐tensile) with methacrylic acid is presented. The grafted carbon fibers were characterized by wetting measurements and electrokinetic studies. Scanning electron microscopy micrographs showed grafted polymer chains on all carbon fiber surfaces. The success of the grafting procedure depends on a suitable modification of the fiber surface. The amount and size of the grafted polymer chains on modified carbon fibers depend on the amount of initiator used. Contact angle measurements indicate an increase of the contact angle versus water and a decrease versus diiodomethane. The surface polarity calculated from the surface tensions obtained from contact angle values decreases for all systems under investigation. Zeta (ζ) potential measurements confirmed these results. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1175–1185, 1999     

ESCA spectroscopy of poly(methyl methacrylate) grafted onto wood fibers

The incompatibility of hydrophilic wood fiber and hydrophobic polymers is the main difficulty with wood thermoplastic polymer composites. To overcome this issue, many researchers suggest grafting polymer onto wood fiber for improving the interfacial adhesion during mixing. A systematic ESCA study of chemi-thermo-mechanical pulp (CTMP) grafted fiber has been performed to provide chemical information about surface composition modification. The material analyzed included initial CTMP fiber, the pure polymer i.e., poly(methyl methacrylate) (PMMA) as reference material, and grafted fiber at different polymer loadings. Interest is focused on the carbon and oxygen spectra. Samples at high polymer loading or high grafting level have an O/C, C₁, C₂, C₄, O₁, and O₂ intensities much similar to those of the PMMA but a little different since some wood fiber sites have still not fixed the polymer. ESCA spectra provide information on about 1–5 nm depth. The ESCA technique allows the monitoring of grafting polymer onto wood fiber as a surface phenomenon.     

Preparation of a novel polymer monolith with high loading capacity by grafting block poly(PEGA–mPEGA) for high-efficiency solid phase synthesis

The polymer monolith for solid-phase synthesis with high efficiency was prepared through in situ copolymerization of chloromethylstyrene and ethylene glycol dimethacrylate (PCMS–EDMA). The obtained monolith was grafted by two kinds of poly(ethylene glycol) acrylate oligomer, poly(ethylene glycol) acrylate (PEGA) and poly(ethylene glycol) methyl ether acrylate (mPEGA). The monolith was grafted via activators generated by electron transfer atom transfer radical polymerization (AGET ATRP) with the increased number of functional groups (–OH). About 0.61–0.81 mmol/g hydroxyl group resulted from side groups in each grafting polymer chain. PmPEGA in the grafting block copolymer chains can increase the distance between the adjacent reactive sites of PEGA (–OH) in each polymer chain. Therefore, the grafted monoliths with the block copolymer of PEGA-co-mPEGA can give high yield (85%) and purity (93%) of the crude peptide (a difficult sequence-acyl carrier protein fragment 65–74) under the condition of high loading capacity (0.76 mmol/g). These results were higher than those by the grafted monolith with only polymer of PEGA (72% and 81%, respectively) and commercial Wang resin (43% and 39%, respectively). The synthetic efficiency on the grafted monolith with block copolymer in the continuous flow technique was 5–6 folds higher than Wang resins in the manual operation conditions.     

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.     

Surface modification of ultra-high molecular weight polyethylene fibers by γ-radiation-induced grafting

A technique for grafting acrylic polymers on the surface of ultra-high molecular weight polyethylene (UHMWPE) fibers utilizing ⁶⁰Co gamma radiation at low dose rates and low total dose has been developed. Unlike some of the more prevalent surface modification schemes, this technique achieves surface grafting with complete retention of the exceptional UHMWPE fiber mechanical properties. In particular, poly(butyl acrylate) and poly(cyclohexyl methacrylate) were successfully grafted onto UHMWPE fibers with no loss in tensile properties. The surface and tensile properties of the fibers were evaluated using Fourier transform infrared/photoacoustic spectroscopy (FTIR/PAS), X-ray photoelectron spectroscopy (XPS), and tensile tests. The reinforcement efficiency of untreated, polymer-grafted, and plasma-treated UHMWPE fibers in polystyrene and a poly(styrene-co-butyl acrylate-co-cyclohexyl methacrylate) statistical terpolymer was characterized using mechanical tensile tests. The thermoplastic matrix composites were prepared with 4 wt% discontinuous (10 mm), randomly distributed UHMWPE fibers. An approximate 30% increase in composite strength and modulus was observed for poly(cyclohexyl methacrylate)-grafted fibers in the terpolymer and polystyrene matrices. A comparable improvement was realized with the plasma-treated fibers. On the other hand, poly(butyl acrylate) grafts induced void formation, i.e. energy dissipation through plastic deformation and volume expansion at the fiber/matrix interface in terpolymer composites. The latter resulted in a 75% increase in the elongation to failure. The effect of polymer grafts on fiber/matrix adhesion is discussed in terms of the graft and matrix chain interactions and solubility, graft chain mobility, and fracture surface characteristics as determined by scanning electron microscopy (SEM).     

Enhancement of PVC/ENR blend properties by poly(methyl acrylate) grafted oil palm empty fruit bunch fiber

Effect of oil palm empty fruit bunch (OPEFB) fiber and poly(methyl acrylate) grafted OPEFB on several mechanical properties of poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blends were studied. The composites were prepared by mixing the fiber and the PVC/ENR blends using HAKEE Rheomixer at the rotor speed of 50 rpm, mixing temperature 150°C, and mixing period of 20 min. The fiber loadings were varied from 0 to 30% and the effect of fiber content in the composites on their ultimate tensile strength (UTS), Young's modulus, elongation at break, flexural modulus, hardness, and impact strength were determined. An increasing trend was observed in the Young's modulus, flexural modulus, and hardness with the addition of grafted and ungrafted fiber to the PVC/ENR blends. However the impact strength, UTS, and elongation at break of the composites were found to decrease with the increase in fiber loading. An increase in elongation at break and UTS and decrease in the flexural and Young's modulus was observed with the addition of PMA‐g‐OPEFB fiber compared to ungrafted fiber. This observation indicates that grafting of PMA onto OPEFB impart some flexibility to the blend. The morphology of cryogenically fractured and tensile fracture surfaces of the composites, examined by a scanning electron microscope shows that the adhesion between the fiber and the matrix is improved upon grafting of the OPEFB fiber. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Study on the Graft Reaction of Poly(propylene) Fiber with Acrylic Acid

Summary: In this paper, the graft of poly(propylene) fiber with acrylic acid is investigated. The effects of grafting temperature, monomer concentration, and grafting time on the grafting degree of acrylic acid onto poly(propylene) fiber are discussed. In contrast to the conventional method of determining the grafting degree gravimetrically, the acid‐base titration method used in this paper was more efficient, even at low grafting degree. High‐performance liquid chromatography (HPLC) was used to estimate the averaged length of the grafted poly(acrylic acid) chains on each grafted site of poly(propylene) backbone. And also a mechanism for the grafting polymerization is proposed.

Possible microstructures of two PP‐g‐AA samples at the same grafting degree.     

Studies of mechanical and moisture regain properties of methyl methacrylate grafted silk fibers

The mechanical properties such as the tenacity, breaking extension, initial modulus, elastic and work recovery, and stress relaxation behavior of methyl methacrylate (MMA) grafted silk fibers prepared under different conditions were measured and explained in terms of the relative dominance of the stress concentration, reduction in the interchain cohesion, and fiber matrix stiffening at different grafting percentages. The moisture regain characteristics of fibers grafted in the presence of different solvents were also studied and compared. The grafting of MMA on silk was found to improve the recovery properties significantly without affecting the stress relaxation behavior. The moisture regain studies indicate that moisture regain is reduced with increasing length of the grafted poly(MMA) chains. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 969–974, 2002; DOI 10.1002/app.10202     

IGC Characterization of PMMA Grafted onto CTMP Fiber

Inverse Gas Chromatography (IGC) was used to characterize chemithermomechanical pulp (CTMP) wood fiber surfaces modified by polymer grafting. From the retention times at infinite dilution over a range of temperatures, the differential heat of adsorption, ΔH^oA, the standard free energy, ΔG^oA, and the standard entropy of adsorption, ΔS^oA, have been determined for the n-alkanes vapors C₈-C₁₁ on CTMP wood fibers grafted with poly(methylmethacrylate) (PMMA) at various polymer loadings (PL). The dispersive component of the surface free energy γ^LS (London) has also been calculated by using a method based on the increment of ΔG^oA per CH₂ group. Comparison of results for the original material, CTMP and PMMA, with those of the grafted fibers has allowed the evaluation of surface modification. Grafted samples at high PL show values of ΔH^oA, ΔG^oA, and γ^LS approaching those of the pure PMMA indicating a high density of polymer chains grafts on the CTMP wood fiber.     

High Stiffness Natural Fiber‐Reinforced Hybrid Polypropylene Composites

Abstract

Natural fibers are potentially a high‐performance non‐abrasive reinforcing fiber source. In this study, pulp fibers [including bleached Kraft pulp (BKP) and thermomechanical pulp (TMP)], hemp, flax, and wood flour were used for reinforcing in polypropylene (PP) composite. The results show that pulp fibers, in particular, TMP‐reinforced PP has the highest tensile strength, possibly because pulp fibers were subjected to less severe shortening during compounding, compared to hemp and flax fiber bundles. Maleic‐anhydride grafted PP (MAPP) with high maleic anhydride groups and high molecular weight was more effective in improving strength properties of PP composite as a compatiblizer. Coupled with 10% glass fiber, 40% TMP reinforced PP had a tensile strength of 70 MPa and a specific tensile strength comparable to glass fiber reinforced PP. Thermomechanical pulp was more effective in reinforcing than BKP. X‐ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM) were used to aid in the analysis. Polypropylene with high impact strength was also used in compounding to improve the low‐impact strength prevalent in natural fiber‐reinforced PP from injection molding.     

Grafting of ethyl acrylate onto monofilament polyester fibers using benzoyl peroxide

Ethyl acrylate was grafted onto monofilament poly(ethylene terephthalate) fibers using benzoyl peroxide as a chemical initiator. Breaking tenacity and densities of grafted fibers decreased while breaking elongation increased with the graft yield. Scanning electron micrographs showed that the fiber geometry and its diameter were not affected by grafting. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1701–1705, 1998     

Hydrophobic cellulose fibers via ATRP and their performance in the removal of pyrene from water

In the present work, cellulose fibers were modified by grafting with poly(lauryl acrylate) and poly(octadecyl acrylate). The grafted materials were prepared by polymerization of the corresponding monomers via surface initiated atom transfer radical polymerization, starting from cellulose papers previously modified with 2‐bromoisobutyryl groups. The polymerizations were carried out in the presence of ethyl‐2‐bromoisobutyrate, as a sacrificial initiator, added to control the molecular weight of the anchored segments, and polymerization kinetics. The grafting of both polymers was confirmed by infrared spectroscopy and elemental analysis. The effect of grafting these polymers on the thermal stability, morphology, and surface properties of cellulose fibers was studied using thermogravimetric analysis, scanning electron microscopy, and measuring water contact angle, respectively. The results reveal that grafting poly(lauryl acrylate) and poly(octadecyl acrylate) to cellulose confers the filter paper a hydrophobic character, and increases its affinity with pyrene, allowing the removal of this pollutant from water. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44482.     

接枝改性丙烯酸乳液压敏胶的研制

通过采用接枝聚合工艺将甲基丙烯酸甲酯接枝到丙烯酸乳液的分子中,研制出一种新型的丙烯酸乳液可剥离压敏胶,用透射电镜和示差扫描量热仪对其进行了分析。实验结果表明：接枝聚合物的乳胶粒呈雪人型,而未接枝的、共混的丙烯酸乳液粒子呈圆形。接枝聚合物的玻璃化温度与未接枝、共混的丙烯酸乳液不相同。在主配方基本不变的条件下,通过调节接枝甲基丙烯酸甲酯的用量,可得到性能良好的乳液型可剥离压敏胶。当丙烯酸用量为4％,引发剂用量为0．4％,丙烯酸-2-羟丙酯用量为2％时,压敏胶性能良好。经过优化配方,合成了满足企业产品质量要求的压敏胶。     

Polymer-grafted cellulose fibers. II. Polymer localization and induced alterations in fiber morphology

In methyl acrylate- or acrylonitrile-grafted northern softwood Kraft or southern softwood Kraft pulp fibers, polymer grafts are present almost homogeneously throughout the fiber wall, although some surface enhancement is observed. On unhydrolyzed fiber surfaces, acrylonitrile grafts protrude in clumps of tangled polymer tufts whereas methyl acrylate grafts form a more uniform, sometimes knobby surface coating. Grafting followed by hydrolysis causes extensive lengthwise splits in the S1 layer, which pulls away from the S2 layer. In the hydrolyzed solvent-dried fiber, the internal grafted polymer/cellulose domains create a unique filamentous and lamellar periodic substructure in the S2 wall. Coexisting with this substructure are numerous microvoids and occasional large pores. We believe that the enhanced absorbency of these fibers can be attributed to the S1 layer disruption, the presence of osmotically active polymer (sodium polyacrylate) incorporated extensively within the S2 wall, and the presence of a drastically altered, more accessible S2 wall substructure. Analytical electron microscopy is shown to be a useful technique for investigating polymer grafts in cellulose fibers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1471–1485, 1997     

Grafting of methyl methacrylate onto silk fibers initiated by tri-n-butylborane

Structural characteristics of the methyl methacrylate (MMA)-grafted silk fibers using tri-n-butylborane as an initiator were analyzed by infrared spectroscopy and differential scanning calorimetry (DSC), and their refractive index and tensile properties were measured. Graft polymerization was promoted by FeCl₃ pretreatment of the silk. The graft yield reached a maximum by the immersion in 4% FeCl₃ solution for 1 min at 25°C. The infrared spectrum of poly(MMA)-grafted silk fibers showed overlapped absorption bands of silk fibroin with the β structure and of the grafted MMA polymer. A grafted silk fiber with graft yield of more than 140% exhibited two endothermic peaks at 321°C and 396°C on the DSC curve, attributed to the thermal decomposition of silk fibroin and grafted poly(MMA) chain, respectively. Refractive index measurements suggested that the molecular orientation and the crystallinity of the silk fiber decreased with increasing graft yield. Electron photomicrographs showed that silk was coated by grafted PMMA. The tensile strength of the grafted silk decreased rapidly by the grafting even at a lower level.     

Structure and properties of tussah silk fibers graft-copolymerized with methacrylamide and 2-hydroxyethyl methacrylate

Tussah silk fibers were graft-copolymerized with methacrylamide (MAA) and 2-hydroxyethyl methacrylate (HEMA) in aqueous media, using a chemical redox system as an initiator. High weight gain values were obtained with both grafting agents (up to 175%). The extent of homopolymerization was negligible for the MAA grafting system over the entire range of monomer–silk ratios examined, while polymer deposition on the fiber surface occurred when the HEMA–silk ratio exceeded 0.5% (w/w). The moisture content of poly(MAA)-grafted silk fibers was enhanced by grafting. Breaking load, elongation at break, and energy decreased at low weight gain (0–20%) and then remained rather constant. The DSC curves of poly(MAA)-grafted silk showed a new endotherm at about 280°C, due to the melting of poly(MAA) chains. The loss modulus peak of poly(HEMA)-grafted silk fibers broadened and shifted to a lower temperature, showing a tendency to split into two peaks at high weight gain. On the other hand, grafting with poly(MAA) induced a noticeable upward shift of the loss peak. The TMA curves showed that grafting with poly(MAA) resulted in a higher extent of fiber contraction from room temperature to about 250°C. Moreover, the intensity of the final contraction step at about 350°C decreased with increasing weight gain and shifted to a lower temperature. The Raman spectra of grafted fibers were characterized by overlapping of the characteristic lines of both silk fibroin and polymer, the latter showing an intensity proportional to the amount of weight gain. Among the conformationally sensitive vibrational modes of tussah silk fibroin, the amide III range was significantly modified by grafting with both poly(MAA) and poly(HEMA). © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1393–1403, 1998