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1.
Polybutadiene has widespread use as a commodity as well as a specialty polymer, but currently, it is prepared from non-renewable feedstocks. Herein, we report the synthesis of rubbery unsaturated polycarbonates (RUPCs) as green alternatives for polybutadiene. We prepared two RUPCs (respectively, denoted as RUPC1 and RUPC2) via the copolymerization of carbon dioxide (CO2) and a mixture of saturated and unsaturated long-chain epoxides using a Co(III) catalyst. The RUPCs were reacted with a styrene monomer via free-radical polymerization to prepare RUPC-graft-Polystyrene. All of the prepared polymers were characterized by 1H nuclear magnetic resonance spectroscopy and gel permeation chromatography. For RUPC, the number average molecular weight (Mn) increased by three-fold after the grafting reaction. Differential scanning calorimetry analysis confirmed that the glass transition temperature (Tg) of the RUPCs were low (~ −40°C) and approached those of polybutadienes. After polystyrene chains had been grafted onto the RUPC backbone, the Tg increased to 81°C. These green RUPCs have the potential to replace non-renewable polybutadiene in some applications such as high impact materials. 相似文献
2.
The compatibilizing effect of poly(styrene-graft-ethylene oxide) in polystyrene (PS) blends with poly(n-butyl acrylate) (PBA) and poly(n-butyl acrylate-co-acrylic acid) (PBAAA) was investigated. No significant effects of the graft copolymer on the domain size were found in the PBA blends. By functionalizing PBA with acrylic acid, the average size of the polyacrylate domains was reduced considerably by the graft copolymer. Thermal and dynamic mechanical analysis of the PS/PBAAA blends revealed that the PBAAA glass transition temperature (Tg) decreased with increasing graft copolymer content. The effect of the graft copolymer in the PS/PBAAA blends can be explained by interactions across the interface due to the formation of hydrogen bonds between the poly(ethylene oxide) (PEO) side chains in the graft copolymer and the acrylic acid segments in the PBAAA phase. Hydrogen bonding was confirmed by IR analysis of binary blends of PEO and PBAAA. Partial miscibility in the PEO/PBAAA blends was indicated by a PEO melting point depression and by a Tg reduction of the PBAAA phase. The thermal properties of the PEO/PBA blends indicated only very limited miscibility. © 1996 John Wiley & Sons, Inc. 相似文献
3.
Mohamed Mahmoud Nasef Hamdani Saidi Hussin Mohd Nor Ooi Mun Foo 《Polymer International》2000,49(12):1572-1579
The physical and chemical properties of polystyrene grafted and sulfonated polytetrafluoroethylene (PTFE‐graft‐PSSA) membranes prepared by radiation‐induced grafting of styrene onto commercial PTFE films using simultaneous irradiation technique followed by a sulfonation reaction are evaluated. The investigated properties include water uptake, ion exchange capacity, hydration number and ionic conductivity. All properties are correlated with the amount of grafted polystyrene (degree of grafting). The thermal stability of the membrane evaluated by thermal gravimetric analysis (TGA) is compared with that of original and grafted PTFE films. The membrane surface structural properties are analysed by electron spectroscopy for chemical analysis (ESCA). Membranes having degrees of grafting of 18 % and above show a good combination of physical and chemical properties that allow them to be proposed for use as proton conducting membranes, provided that they have sufficient chemical and mechanical stability. © 2000 Society of Chemical Industry 相似文献
4.
Conjuge bonding oligosalicylaldehyde‐graft‐oligoaniline (OSA‐graft‐OA) was synthesized from the polycondensation reaction of oligosalicylaldehyde (OSA) with oligoaniline (OA). There were various functional groups such as ? OH, ? NH and ? CH?N in the structure of the graft cooligomer. The physical properties of graft‐co‐oligomers such as melting temperature and solubility were studied: number‐average molecular weight, mass‐average molecular weight, and a polydispersity index of OA, OSA, and fractions of the graft cooligomers [(OSA‐graft‐OA)‐I] and [(OSA‐graft‐OA)‐II] were found to be 740, 780 g mol?1,1.05; 3700, 5990 g mol?1, 1.62; 990, 2770 g mol?1, 2.80 and 1300, 4100 g mol?1, 3.15, respectively. The FTIR and UV‐Vis spectra of the graft cooligomer were compared with those of beginning oligomers. The spectral analyses results showed that the OSA‐graft‐OA synthesized from the polycondensation reaction of aromatic amine with aldehyde that have long oligophenol macromolecule bonded each other with an azomethine bridge through oligophenylamine side chains. The thermal stability of the graft cooligomer and oligomers were measured by thermogravimetric analysis (TG) under an air atmosphere. According to TG analyses, the carboneous residues of the [(OSA‐graft‐OA)‐I) (soluble in ethanol) and (OSA‐graft‐OA)‐II) (soluble in toluene)] were 23 and 40%, respectively, at 1000°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 218–226, 2002 相似文献
5.
In this study, the graft copolymerization of N-hydroxymethylacrylamide (NHMAAm) with poly(vinyl alcohol) (PVA) was carried out by using potassium persulfate/N,N,N,N-tetramethylethylenediamine (K2S2O8) to improve physicochemical properties and functionality of PVA. The structures of PVA-g-poly-NHMAAm (PNHMAAm) copolymers were characterized by Fourier transform infrared, elemental analysis, nuclear magnetic resonance (1H-NMR), 13C-NMR, and size exclusion chromatography. Their thermal behaviors were investigated by differential scanning calorimetry and thermogravimetric analysis (TGA). The TGA results indicated that the graft copolymers show better thermal stability then PVA. The effects of reaction time, temperature, NHMAAm, and K2S2O8 concentrations on grafting parameters were examined. The maximum grafting yield (34.01%) was provided when reaction was carried out under optimum conditions (time = 2 hr, T = 40°C, [NHMAAm] = 0.25 M, [K2S2O8] = 4.56 × 10−3 M). Moreover, PVA-g-PNHMAAm membranes were prepared and their swelling behaviors were studied. The results demonstrated that swelling degree of graft membranes increased almost 3.5-fold compared to PVA membrane. 相似文献
6.
Inderjeet Kaur BN Misra Baljit Singh Nirupma Gupta Neelam Sharma 《Polymer International》2004,53(10):1572-1580
The graft copolymerization of styrene (st) and methacrylonitrile (MAN) onto Tefzel film in aqueous media by the preirradiation method has been studied. In order to follow the effect of preswelling of the backbone polymer, grafting was attempted onto preirradiated Tefzel film and monomer preswollen, preirradiated Tefzel film. Optimum conditions pertaining to maximum percentage of grafting of st and MAN have been evaluated. Grafting onto preswollen, preirradiated Tefzel film displayed better results. The effect of different alcohols of increasing chain length on the percentage of grafting of st and MAN was also studied. Graft copolymerization of st showed an increase, while grafting with MAN exhibited a decrease, in the percentage of grafting in the presence of alcohols as compared to that obtained in the aqueous medium. Characterization of the graft copolymers was made by IR and thermogravimetric studies. Tefzel‐graft‐polystyrene showed improved thermal stability while the MAN grafted onto preswollen, preirradiated Tefzel film produced graft copolymer with poor thermal stability. Copyright © 2004 Society of Chemical Industry 相似文献
7.
Chitosan-graft-polyacrylamide (Ch-g-PAM) was synthesized without any radical initiator or catalyst using microwave (MW) irradiation. Under optimal grafting conditions, 169% grafting was observed at 80% MW power in 1.16 min. Conventionally under similar conditions a maximum grafting of 82% could be achieved in 1 h using K2S2O8/ascorbic acid as redox initiator coupled with Ag+ ions as catalyst and atmospheric oxygen as co-catalyst on a thermostatic water bath at 35±0.2 °C. The representative microwave synthesized graft copolymer was characterized by Fourier transform-infrared spectroscopy, thermo gravimetric analysis and X-ray diffraction measurement, taking chitosan as a reference. The effects of reaction variables as monomer/chitosan concentration, MW power and exposure time on the graft co-polymerization were studied. A probable free radical mechanism for grafting under microwaves has been proposed. The solubility pH for the grafted samples with different extent of grafting was monitored. The adsorption capacity of chitosan was much enhanced after grafting. The microwave synthesized Ch-g-PAM in comparison to that prepared conventionally was found to have much more adsorption ability for Ca2+ and Zn2+ ions in aqueous solution. 相似文献
8.
The graft copolymer of polystyrene and polyamide 6 (PS-g-PA6) was investigated by anionic polymerization of ε-caprolactam (CL), using the free radical copolymer of styrene and a kind of allyl monomer containing N-carbamated caprolactam group as macroactivator (PS-CCL). CL monomers were grafted onto PS-CCL backbone via initiating N-carbamated caprolactam (CCL) pendants along its backbone to form the graft copolymer in the presence of catalyst sodium caprolactamate. The macroactivator was characterized by Fourier-transform infrared spectroscopy and nuclear magnetic resonance, and the graft copolymer by the selective solvent extraction technique using methanol and chloroform as solvents. PS-g-PA6 copolymers with different PS content were synthesized to study the effect of PS on morphology, crystallinity, dimensional stability, and thermal properties, using scanning electron microscopy, X-ray diffraction, water absorption measurement, thermogravimetric analysis, and differential scanning calorimetry. The results show the percentage crystallinity of graft copolymer decreases with increasing PS content, but the addition of PS scarcely influences the crystalline structure of PA6. The graft copolymer has improved thermal properties and dimensional stability. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
9.
Series of graft copolymers with [Poly(epichlorohydrin-co-ethylene oxide)] [Poly(ECH-co-EO)] as backbone and polystyrene (PS), poly(isoprene) (PI) or their block copolymers as side chains were successfully synthesized by combination of ring-opening polymerization (ROP) with living anionic polymerization. The Poly(ECH-co-EO) with high molecular weight (Mn = 3.3 × 104 g/mol) and low polydispersity index (PDI = 1.34) was firstly synthesized by ring-ROP using ethylene glycol potassium as initiator and triisobutylaluminium (i-Bu3Al) as activator. Subsequently, by “grafting onto” strategy, the graft copolymers Poly(ECH-co-EO)-g-PI, Poly(ECH-co-EO)-g-PS and Poly(ECH-co-EO)-g-(PI-b-PS) were obtained using the coupling reaction between living PI−Li+, PS−Li+ or PS-b-PI−Li+ species capped with or without 1,1-diphenylethylene (DPE) agent and chloromethyl groups on poly(ECH-co-EO). By model experiment, the addition of DPE agent was confirmed to have an important effect on the grafting efficiency at room temperature. Finally, the target graft copolymers and intermediates were characterized by SEC, 1H NMR, MALLS and FTIR in detail, and thermal behaviours of the graft copolymers were also investigated by DSC measurement. 相似文献
10.
Liaoyun Zhang Guoqiang Fan Cunyue Guo Jin‐Yong Dong Youliang Hu Mingbao Huang 《Polymer International》2006,55(6):675-680
Isotactic polypropylene graft copolymers, isotactic[polypropylene‐graft‐poly(methyl methacrylate)] (i‐PP‐g‐PMMA) and isotactic[polypropylene‐graft‐polystyrene] (i‐PP‐g‐PS), were prepared by atom‐transfer radical polymerization (ATRP) using a 2‐bromopropionic ester macro‐initiator from functional polypropylene‐containing hydroxyl groups. This kind of functionalized propylene can be obtained by copolymerization of propylene and borane monomer using isospecific MgCl2‐supported TiCl4 as catalyst. Both the graft density and the molecular weights of i‐PP‐based graft copolymers were controlled by changing the hydroxyl group contents of functionalized polypropylene and the amount of monomer used in the grafting reaction. The effect of i‐PP‐g‐PS graft copolymer on PP‐PS blends and that of i‐PP‐g‐PMMA graft copolymer on PP‐PMMA blends were studied by scanning electron microscopy. Copyright © 2006 Society of Chemical Industry 相似文献
11.
Polystyrene (PS)‐incorporated polyhedral oligomeric silsesquioxanes (POSS) organic–inorganic hybrid graft copolymer could be achieved by click coupling reaction between alkyne groups in POSS and azido groups in PS via “graft onto” strategy. Alkyne‐functionalized POSS was synthesized via thiol‐ene facile click reaction and subsequent amidation reaction with very high yield. Azido‐multifunctionalized PS could be synthesized by chloromethylation and subsequent azido reaction. The chemical structures of PS‐(CH2Cl)m, PS‐(CH2N3)m, and PS‐g‐POSS were determined by Fourier transform infrared and 1H NMR characterization. PS‐g‐POSS presented a better hydrophobic property with contact angle of 113° than that of PS (85°). And PS‐g‐POSS with ≤5% of grafting degree had lower glass transition temperature (Tg) than that of PS and then it increased up to 112°C with grafting degree. An obvious aggregation of POSS phase with 10–80 nm in size was formed in PS‐g‐POSS matrix. In addition, 5 wt % of PS‐g‐POSS was added to general purpose polystyrene (GPPS) to remarkably improve its tensile strength from 45 to 57 MPa. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013 相似文献
12.
Conductive pyrrole monomer was grafted on vinyl modified sepiolite by surface initiated emulsion graft polymerization. Effect of process variables such as monomer, initiator, and surfactant on degree of grafting (%) were investigated. Maximum 745% degree of grafting was obtained at optimized grafting conditions. Structural changes in sepiolite by grafting of polypyrrole chains was confirmed by Fourier transform infrared spectroscopy and X-ray diffraction techniques. Surface morphology of the grafted nanohybrid was investigated by scanning electron microscopy (SEM). Thermal studies were carried out to acquire information concerning thermal stability of the synthesized materials and it was found increasing with the increase in grafting (%) of polypyrrole in sepiolite grafted polypyrrole (MS-g-PPy). Complex impedance spectroscopic analysis was carried out to study the effects of grafting of PPy on the ac electrical properties of synthesized nanohybrid composite at ambient temperature in the frequency range of 0.5–107 Hz. The value of electrical conductivity was affected by degree of grafting (%) and maximum value of 0.85 × 10−4 S/cm was achieved. Both dielectric loss factor and permittivity increase with the decrease of frequency exhibiting strong interfacial polarization at low frequency. 相似文献
13.
Starch nanocrystals‐g‐polystyrene (StN‐g‐PS) was synthesized by free radical emulsion copolymerization of starch nanocrystals with styrene. The effect of polymerization conditions on grafting efficiency (GE) and grafting ratio (GR) were investigated. It was found that during graft copolymerization procedure both GE and GR increase with increasing monomer concentration and reaction time. As a result the high GE and high GR can be achieved. The good linear fit of the GR with ASt/AOH (the absorption strength ratio of aromatic ring peaks and hydroxyl group peaks) confirmed that during graft copolymerization, FTIR spectra can be used as a simple method for determining GR. X‐ray diffraction showed that the crystallinity of StN‐g‐PS decreased slightly with increasing GR. Grafted polystyrene side chains can improve the interface compatibility of starch nanocrystals with the hydrophobic polymer matrix. The mechanical properties of StN‐g‐PS/rubber nanocomposites can be obviously enhanced. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40571. 相似文献
14.
For increasing the compatibility of polystyrene (PS) and polyolefin elastomer (POE) blends, a Lewis acid catalyst, aluminium chloride (AlCl3), was adopted to initiate the Friedel-Crafts alkylation reaction and induce the formation of PS-graft-POE copolymer. The dynamic mechanical and rheological tests were used to study the effects of catalyst content on the miscibility and rheological behaviors. The results showed that the viscosity increased and the MFI decreased with the increase of the catalyst content. However, when the catalyst content was overmuch, the viscosity decreased and the MFI increased. The variety of miscibility and rheological behaviors of PS/POE blends was the results of the competition between in situ graft reaction and decomposition of blending compounds. 相似文献
15.
The grafting of polystyrene onto dissolved starch in a twin screw extruder has been studied. This copolymerization was initiated using the thermal initiators benzoyl peroxide and K2S2O8. As end product a mixture containing polystyrene‐grafted starch, homopolymer of polystyrene and starch was obtained. Parameters like screw rotation rate, fully filled length of the extruder, wall temperature and throughput have been varied in order to obtain information about their influence on conversion, graft percentages and molecular weight of the materials formed. To increase the amount of graft points, maleic acid anhydride (MAH) was added resulting in an increased grafting of polystyrene onto starch. Graft percentages of 60% could be achieved. The total conversion of styrene could be controlled by adjusting extruder parameters like barrel temperature, fully filled length and initiator type. Conversions of 95% were found. Molecular weights of the polystyrene formed could be controlled by adding a chain transfer agent (dodecylmercaptan) to the styrene phase. In this way the molecular weight (Mn) of the styrenic part could be varied from 20,000 to 140,000. The experiments with the chain transfer agent showed that the grafting of polystyrene onto starch is a process occurring at the interface between the dissolved starch and the styrene phase. 相似文献
16.
Core–shell‐type microspheres with microphase‐separated shells of polystyrene (PS) and poly(ethylene glycol) (PEG) (microsphereblock: molar ratio: PS/PEG 49.1/45.9 mol %; Mw: PS chain: 1.07 × 104, PEG chain 1.0 × 104; the ratio of arm numbers of PEG to PS: 1.0; microspheregraft: molar ratio: PS/PEG 33.8/55.9 mol %; Mw: PS chain: 1.54 × 104, PEG chain 1.0 × 104, the ratio of arm numbers of PEG to PS: 2.55) were synthesized by crosslinking of spherical domains of poly(2‐hydroxyethyl methacrylate) (PHEMA) and poly(4‐vinyl pyridine) (P4VP) of the microphase‐separated films of poly(ethylene glycol)‐block‐poly(2‐hydroxyethyl methacrylate)‐block‐polystyrene triblock terpolymer (Mn: 2.18 × 104; molar ratio: PS 49.1 mol %, PHEMA 5.0 mol %, PEG 45.9 mol %) and polystyrene‐block‐[poly(4‐vinyl pyridine)‐graft‐poly(ethylene glycol)] block–graft copolymer (Mn: 4.56 × 104; molar ratio: PS 33.8 mol %, P4VP 10.3 mol %, PEG 55.9 mol %; branch number of PEG: 2.55), respectively. The structures of microphase‐separated films were investigated by transmission electron microscopy and small‐angle X‐ray scattering. The effects of the arm number ratio of PS to PEG and the total arm number on the stability of the water/benzene emulsion were investigated. The emulsion stability of oil in water was improved by using the microsphere synthesized with the microspheregraft. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 321–331, 2004 相似文献
17.
The graft copolymerization of N,N‐dimethylacrylamide (DMA) and acrylamide (AM) were carried out onto different polysaccharide backbones separately. The graft copolymers were synthesized by ceric ion induced redox polymerization technique. Three polysaccharides were used, namely hydroxyethyl starch (HES), hydroxyethyl cellulose (HEC) and Amylopectin (AP), for the grafting reactions. Among the three polysaccharides, HEC has linear structure, while HES and AP have a branch one. The graft copolymers were characterized by intrinsic viscosity measurements, FTIR spectroscopy, NMR (both 1H and 13C) spectroscopy, and thermal analysis. Flocculation performances of the graft copolymers were evaluated in 1 wt % kaolin and in 0.25 wt % iron ore suspensions. A detailed comparative study of the flocculation properties of the synthetic graft copolymers was also made. It showed that graft copolymers based on DMA were better flocculants than those based on AM. Among the synthetic graft copolymers, HES‐g‐Poly (DMA) performed best when compared with the other synthetic graft copolymers as well as to the commercial flocculants in the same suspensions. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013 相似文献
18.
A new graft copolymers poly(aryl ether sulfone)‐graft‐polystyrene (PSF‐g‐PS) and poly(aryl ether sulfone)‐graft‐[polystyrene‐block‐poly(methyl methacrylate)] (PSF‐g‐(PS‐b‐PMMA)) were successfully prepared via atom transfer radical polymerisation (ATRP) catalyzed by FeCl2/isophthalic acid in N,N‐dimethyl formamide. The products were characterized by GPC, DSC, IR, TGA and NMR. The characterization data indicated that the graft copolymerization was accomplished via conventional ATRP mechanism. The effect of chloride content of the macroinitiator on the graft copolymerization was investigated. Only one glass transition temperature (Tg) was detected by DSC for the graft copolymer PSF‐g‐PS and two glass transition temperatures were observed in the DSC curve of PSF‐g‐(PS‐b‐PMMA). The presence of PSF in PSF‐b‐PS or PSF‐g‐(PS‐b‐PMMA) was found to improve thermal stabilities. © 2002 Society of Chemical Industry 相似文献
19.
Synthesis and self-assembly behaviors of three-armed amphiphilic block copolymers via RAFT polymerization 总被引:1,自引:0,他引:1
Weidong Zhang 《Polymer》2008,49(21):4569-4575
The novel trifunctional reversible addition-fragmentation chain transfer (RAFT) agent, tris(1-phenylethyl) 1,3,5-triazine-2,4,6-triyl trithiocarbonate (TTA), was synthesized and used to prepare the three-armed polystyrene (PS3) via RAFT polymerization of styrene (St) in bulk with thermal initiation. The polymerization kinetic plot was first order and the molecular weights of polymers increased with the monomer conversions with narrow molecular weight distributions (Mw/Mn ≤ 1.23). The number of arms of the star PS was analyzed by gel permeation chromatography (GPC), ultraviolet visible (UV-vis) and fluorescence spectra. Furthermore, poly(styrene-b-N-isopropylacrylamide)3 (PS-b-PNIPAAM)3, the three-armed amphiphilic thermosensitive block copolymer, with controlled molecular weight and well-defined structure was also successfully prepared via RAFT chain extension method using the three-armed PS obtained as the macro-RAFT agent and N-isopropylacrylamide as the second monomer. The copolymers obtained were characterized by GPC and 1H nuclear magnetic resonance (NMR) spectra. The self-assembly behaviors of the three-armed amphiphilic block copolymers (PS-b-PNIPAAM)3 in mixed solution (DMF/CH3OH) were also investigated by high performance particle sizer (HPPS) and transmission electron microscopy (TEM). Interestingly, the lower critical solution temperature (LCST) of aqueous solutions of the three-armed amphiphilic block copolymers (PS-b-PNIPAAM)3 decreased with the increase of relative length of PS in the block copolymers. 相似文献
20.
Synthesis of seaweed polysaccharide‐based polyvinylpyrrolidone copolymer with adhesive properties
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Polyvinylpyrrolidone (PVP) grafted sulfated polysaccharide of the seaweed Cystoseira indica (CIsps) (CIsps‐graft‐PVP) was synthesized in aqueous medium under microwave irradiation in the presence of potassium persulfate (KPS), as a free radical initiator. Varying the reaction parameters, e.g., concentration of PVP and KPS, reaction time and temperature, optimum grafting condition was identified as the one having the highest grafting ratio (Gr 2.30) and grafting efficiency (Ge 0.92). The grafted copolymer was characterized by FT‐IR, 13C‐NMR and thermo gravimetric analysis (TGA). The 5% (w/v) dispersion of the new material CIsps‐graft‐PVP in water exhibited comparable binding properties with papers, polyethylene sheets, and wood pieces as against that of a commercial adhesive. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42383. 相似文献