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1.
S‐allyl‐4‐methyldithiobenzoate was synthesized and used as a chain transfer agent for the RAFT polymerization of butyl acrylate to produce a functionalized acrylic rubber. A solution of 8 wt% of this functionalized rubber was prepared in styrene and polymerized to generate a material called acrylic rubber‐modified polystyrene (AMP) constituted by well‐dispersed particles of poly(butyl acrylate)‐block‐poly(styrene) into a polystyrene matrix. Impact strength of injection‐molded samples of AMP was measured and compared with the general purpose polystyrene (GPPS) and the high impact polystyrene (HIPS). AMP itself showed an impact strength value similar to GPPS; however, when AMP was blended with conventional HIPS, the resulting material exhibited an improvement of 76–91% as compared to HIPS by itself, without affecting negatively tensile properties. Transmission electron microscopy analysis revealed both kinds of dispersed phases, i.e. the typical salami particles of polybutadiene coming from HIPS (size: 0.5–2 µ) and small particles from poly(butyl acrylate)‐block‐poly(styrene) (size: ~50 nm). We clearly showed that such a bimodality of the particle size distribution caused the positive synergistic effect on impact strength. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

2.
The polymers poly[(2,2‐dimethyl‐1,3‐dioxolane‐4yl) methyl acrylate] (PDMDMA) and four‐armed PDMDMA with well‐defined structures were prepared by the polymerization of (2,2‐dimethyl‐1,3‐dioxolane‐4yl) methyl acrylate (DMDMA) in the presence of an atom transfer radical polymerization (ATRP) initiator system. The successive hydrolyses of the polymers obtained produced the corresponding water‐soluble polymers poly(2,3‐dihydroxypropyl acrylate) (PDHPA) and four‐armed PDHPA. The controllable features for the ATRP of DMDMA were studied with kinetic measurements, gel permeation chromatography (GPC), and NMR data. With the macroinitiators PDMDMA–Br and four‐armed PDMDMA–Br in combination with CuBr and 2,2′‐bipyridine, the block polymerizations of methyl acrylate (MA) with PDMDMA were carried out to afford the AB diblock copolymer PDMDMA‐b‐MA and the four‐armed block copolymer S{poly[(2,2‐dimethyl‐1,3‐dioxolane‐4yl) methyl acrylate]‐block‐poly(methyl acrylate)}4, respectively. The block copolymers were hydrolyzed in an acidic aqueous solution, and the amphiphilic diblock and four‐armed block copolymers poly(2,3‐dihydroxypropyl acrylate)‐block‐poly(methyl acrylate) were prepared successfully. The structures of these block copolymers were verified with NMR and GPC measurements. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3062–3072, 2001  相似文献   

3.
ABA block copolymers of methyl methacrylate and methylphenylsilane were synthesized with a methodology based on atom transfer radical polymerization (ATRP). The reaction of samples of α,ω‐dihalopoly(methylphenylsilane) with 2‐hydroxyethyl‐2‐methyl‐2‐bromoproprionate gave suitable macroinitiators for the ATRP of methyl methacrylate. The latter procedure was carried out at 95 °C in a xylene solution with CuBr and 2,2‐bipyridine as the initiating system. The rate of the polymerization was first‐order with respect to monomer conversion. The block copolymers were characterized with 1H NMR and 13C NMR spectroscopy and size exclusion chromatography, and differential scanning calorimetry was used to obtain preliminary evidence of phase separation in the copolymer products. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 30–40, 2003  相似文献   

4.
A novel six‐arm star block copolymer comprising polystyrene (PS) linked to the center and π‐conjugated poly (3‐hexylthiophene) (P3HT) was successfully synthesized using a combination of atom transfer radical polymerization (ATRP) and click reaction. First, star‐shaped PS with six arms was prepared via ATRP of styrene with the discotic six‐functional initiator, 2,3,6,7,10,11‐hexakis(2‐bromoisobutyryloxy)triphenylene. Next, the terminal bromides of the star‐shaped PS were substituted with azide groups. Afterward, the six‐arm star block copolymer PS‐b‐P3HT was prepared using the click coupling reaction of azide‐terminated star‐shaped PS with alkynyl‐terminated P3HT. Various techniques including 1H NMR, Fourier‐transform infrared and size‐exclusion chromatography were applied to characterize the chemical structures of the intermediates and the target block copolymers. Their thermal behaviors and optical properties were investigated using differential scanning calorimetry and UV–vis spectroscopy. Moreover, atomic force microscopy (AFM) was utilized to observe the morphology of the star block copolymer films. In comparison with two linear diblock copolymer counterparts, AFM results reveal the effect of the star block copolymer architecture on the microphase separation‐induced morphology in thin films. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

5.
The synthesis of poly(tert‐butyl acrylate‐block‐vinyl acetate) copolymers using a combination of two living radical polymerization techniques, atom transfer radical polymerization (ATRP) and reversible addition‐fragmentation chain transfer (RAFT) polymerization, is reported. The use of two methods is due to the disparity in reactivity of the two monomers, viz. vinyl acetate is difficult to polymerize via ATRP, and a suitable RAFT agent that can control the polymerization of vinyl acetate is typically unable to control the polymerization of tert‐butyl acrylate. Thus, ATRP was performed to make poly(tert‐butyl acrylate) containing a bromine end group. This end group was subsequently substituted with a xanthate moiety. Various spectroscopic methods were used to confirm the substitution. The poly(tert‐butyl acrylate) macro‐RAFT agent was then used to produce (tert‐butyl acrylate‐block‐vinyl acetate). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7200–7206, 2008  相似文献   

6.
7.
A polystyrene‐b‐poly(2‐vinylpyridine) block copolymer containing a methylhydridosilane linking group was chemically grafted to an 8‐trichlorosilyloctene monolayer via a simple one‐step hydrosilylation reaction. The resulting Y‐shaped thin film exhibited a low grafting density, which was characteristic of the grafting‐to technique. To further reduce the miscibility of the two arms, methyl iodide was reacted with the poly(2‐vinylpyridine) block to produce quaternary ammonium groups. The surfaces before and after quaternization were both solvent‐switchable when subjected to block‐selective solvents. Tensiometry, ellipsometry, attenuated total reflection/Fourier transform infrared, and atomic force microscopy were used to characterize the properties and morphology of both unquaternized and quaternized samples. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5608–5617, 2006  相似文献   

8.
Styrene (St) was polymerized with α,α′‐bis(2′,2′,6′,6′‐tetramethyl‐1′‐piperidinyloxy)‐1,4‐diethylbenzene ( 1 ) as an initiator (bulk, [St]/] 1 ] = 570) at 120 °C for 5.0 h to obtain polystyrene having 2,2,6,6‐tetramethylpiperidiloxy moieties on both sides of the chain ends ( 2 ) with a number‐average molecular weight (Mn) of 14,300 and a polydispersity index [weight‐average molecular weight/number‐average molecular weight (Mw/Mn)] of 1.14. 4‐Vinylbenzyl glucoside peracetate ( 3a ) was polymerized with 2 as a macromolecular initiator and dicumyl peroxide (DCP) as an accelerator in chlorobenzene at 120 °C. The polymerization with the [ 3a ]/[ 2 ]/[DCP] ratio of 30/1/1.2 for 5 h afforded a product in a yield of 73%; it was followed by purification with preparative size exclusion chromatography to provide the ABA triblock copolymer containing the pendant acetyl glucose on both sides of the chain ends ( 4a ; Mn = 21,000, Mw/Mn = 1.16). Similarly, the polymerization of 4‐vinylbenzyl maltohexaoside peracetate produced the ABA triblock copolymer containing the pendant acetyl maltohexaose on both side of the chain end ( 4b ; Mn = 31,800, Mw/Mn = 1.11). Polymers 4a and 4b were modified by deacetylation into amphiphilic ABA triblock copolymers containing the pendant glucose and maltohexaose as hydrophilic segment, 5a and 5b , respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3978–3985, 2006  相似文献   

9.
We have developed a metal free synthetic pathway to homopolypeptide rod‐coil block copolymers. The concept was proven for the synthesis of poly(benzyl‐L ‐glutamate‐b‐styrene). A dual initiator containing a primary amine and a nitroxide group was used in a macroinitiation approach with high initiation efficiency. Good control over the molecular weight in the ring opening polymerization of benzyl‐L ‐glutamate N‐carboxyanhydride was obtained in DMF at 0 °C yielding poly(benzyl‐L ‐glutamates) with low polydispersities around 1.1. The almost quantitative incorporation of the dual initiator was confirmed by MALDI‐ToF analysis. Macroinitiation of styrene by nitroxide‐mediated controlled radical polymerization yielded the block copolymer with high structural control. The diblock structure was confirmed by molecular weight increase upon macroinitiation by size exclusion chromatography and retention time comparison with homopolymers using gradient polymer elution chromatography. Both polymerizations were also successfully conducted in one pot without intermediate isolation owing to the high compatibility of both polymerization techniques. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3068–3077, 2008  相似文献   

10.
Water‐soluble and photoluminescent block copolymers [poly(ethylene oxide)‐block‐poly(p‐phenylene vinylene) (PEO‐b‐PPV)] were synthesized, in two steps, by the addition of α‐halo‐α′‐alkylsulfinyl‐p‐xylene from activated poly(ethylene oxide) (PEO) chains in tetrahydrofuran at 25 °C. This copolymerization, which was derived from the Vanderzande poly(p‐phenylene vinylene) (PPV) synthesis, led to partly converted PEO‐b‐PPV block copolymers mixed with unreacted PEO chains. The yield, length, and composition of these added sequences depended on the experimental conditions, namely, the order of reagent addition, the nature of the monomers, and the addition of an extra base. The addition of lithium tert‐butoxide increased the length of the PPV precursor sequence and reduced spontaneous conversion. The conversion into PPV could be achieved in a second step by a thermal treatment. A spectral analysis of the reactive medium and the composition of the resulting polymers revealed new evidence for an anionic mechanism of the copolymerization process under our experimental conditions. Moreover, the photoluminescence yields were strongly dependant on the conjugation length and on the solvent, with a maximum (70%) in tetrahydrofuran and a minimum (<1%) in water. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4337–4350, 2005  相似文献   

11.
A new hybrid amphiphilic system between a polyacrylic acid (PAA) synthetic segment, and a hydrophobic β‐sheet forming peptide segment, poly(L ‐valine) (PLVAL) was synthesized using a combination of Atom Transfer Radical Polymerization, Click Chemistry, and Nickel catalyzed ring opening of L ‐valine N‐carboxyanhydride. This is the first reported use of Click Chemistry as an intermediary step for the ω‐amino functionalization of polymers to obtain macroinitiators that are free from deactivating or interfering molecules to be used in subsequent Ni‐catalyzed ring opening reaction. The efficiency of the end‐group functionalization in the macroinitiator is about 90%. Three different PAA‐b‐PLVAL hybrid copolymers with molecular weight range of 8000–15,000 and Mw/Mn <1.3 had been prepared by varying the monomer to macroinitiator ratio. In addition, the highest achievable molecular weight in the copolymerization was found to be limited by the solubility of the growing chains. This combined synthetic approach can potentially be extended for the synthesis of a multitude of other peptide hybrid systems, and hence will be of interest in the preparation of peptide hybrid systems. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2646–2656, 2007  相似文献   

12.
Poly(ethylene oxide) (PEO) star polymer with a microgel core was prepared by atom transfer radical poylmerization (ATRP) of divinyl benzene (DVB) with mono‐2‐bromoisobutyryl PEO ester as a macroinitiator. Several factors, such as the feed ratio of DVB to the initiator, type of catalysts, and purity of DVB, play important roles during star formation. The crosslinked poly(divinyl benzene) (PDVB) core was further obtained by the hydrolysis of PEO star to remove PEO arms. Size exclusion chromatography (SEC) traces revealed the bare core has a broad molecular weight distribution. PEO–polystyrene (PS) heteroarm star polymer was synthesized through grafting PS from the core of PEO star by another ATRP of styrene (St) because of the presence of initiating groups in the core inherited from PEO star. Characterizations by SEC, 1H NMR, and DSC revealed the successful preparation of the target star copolymers. Scanning electron microscopy images suggested that PEO–PS heteroarm star can form spherical micelles in water/tetrahydrofuran mixture solvents, which further demonstrated the amphiphilic nature of the star polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2263–2271, 2004  相似文献   

13.
A bromine capped star‐shaped poly(methyl methacrylate) (S‐PMMA‐Br) was synthesized with CuBr/sparteine/PT‐Br as a catalyst and initiator to polymerize methyl methacrylate (MMA) according to atom transfer radical polymerization (ATRP). Then, with S‐PMMA‐Br as a macroinitiator, a series of new liquid crystal rod–coil star block copolymers with different molecular weights and low polydispersity were obtained by this method. The block architecture {coil‐conformation of the MMA segment and rigid‐rod conformation of 2,5‐bis[(4‐methoxyphenyl)oxycarbonyl] styrene segment} of the four‐armed rod–coil star block copolymers were characterized by 1H NMR. The liquid‐crystalline behavior of these copolymers was studied by differential scanning calorimetry and polarized optical microscopy. We found that the liquid‐crystalline behavior depends on the molecular weight of the rigid segment; only the four‐armed rod–coil star block copolymers with each arm's Mn,GPC of the rigid block beyond 0.91 × 104 g/mol could form liquid‐crystalline phases above the glass‐transition temperature of the rigid block. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 733–741, 2005  相似文献   

14.
The amphiphilic organoboron block copolymer poly (styreneboronic acid)‐block‐polystyrene ( PSBA‐b‐PS ) has been prepared through a postpolymerization modification route from the silicon‐functionalized block copolymer poly(4‐trimethylsilylstyrene)‐block‐polystyrene ( PSSi‐b‐PS ). PSBA‐b‐PS is obtained through highly selective reaction of PSSi‐b‐PS with BBr3 at room temperature and subsequent hydrolysis of the BBr2‐functionalized intermediate. Transmission electron microscopy studies demonstrate that PSBA‐b‐PS undergoes pH dependent micellization in aqueous solution. Different morphologies could be realized by using different mixtures of water and organic solvents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2438–2445, 2010  相似文献   

15.
Novel thermo‐responsive poly(N‐isopropylacrylamide)‐block‐poly(l ‐lactide)‐block‐poly(N‐isopropylacylamide) (PNIPAAm‐b‐PLLA‐b‐PNIPAAm) triblock copolymers were successfully prepared by atom transfer radical polymerization of NIPAAm with Br‐PLLA‐Br macroinitiator, using a CuCl/tris(2‐dimethylaminoethyl) amine (Me6TREN) complex as catalyst at 25 °C in a N,N‐dimethylformamide/water mixture. The molecular weight of the copolymers ranges from 18,000 to 38,000 g mol?1, and the dispersity from 1.10 to 1.28. Micelles are formed by self‐assembly of copolymers in aqueous medium at room temperature, as evidenced by 1H NMR, dynamic light scattering (DLS) and transmission electron microscopy (TEM). The critical micelle concentration determined by fluorescence spectroscopy ranges from 0.0077 to 0.016 mg mL?1. 1H NMR analysis in selective solvents confirmed the core‐shell structure of micelles. The copolymers exhibit a lower critical solution temperature (LCST) between 32.1 and 32.8 °C. The micelles are spherical in shape with a mean diameter between 31.4 and 83.3 nm, as determined by TEM and DLS. When the temperature is raised above the LCST, micelle size increases at high copolymer concentrations due to aggregation. In contrast, at low copolymer concentrations, decrease of micelle size is observed due to collapse of PNIPAAm chains. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3274–3283  相似文献   

16.
The block copolymer poly(ethylene oxide)‐b‐poly(4‐vinylpyridine) was synthesized by a combination of living anionic ring‐opening polymerization and a controllable radical mechanism. The poly(ethylene oxide) prepolymer with the 2,2,6,6‐tetramethylpiperidinyl‐1‐oxy end group (PEOT) was first obtained by anionic ring‐opening polymerization of ethylene oxide with sodium 4‐oxy‐2,2,6,6‐tetramethylpiperidinyl‐1‐oxy as the initiator in a homogeneous process. In the polymerization UV and electron spin resonance spectroscopy determined the 2,2,6,6‐tetramethylpiperidinyl‐1‐oxy moiety was left intact. The copolymers were then obtained by radical polymerization of 4‐vinylpyridine in the presence of PEOT. The polymerization showed a controllable radical mechanism. The desired block copolymers were characterized by gel permeation chromatography, Fourier transform infrared, and NMR spectroscopy in detail. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4404–4409, 2002  相似文献   

17.
The syntheses of amphiphilic block copolymers are successfully performed in water by chain extension of hydrophilic macromolecules with styrene at 80 °C. The employed strategy is a one‐pot procedure in which poly(acrylic acid), poly(methacrylic acid) or poly(methacrylic acid‐co‐poly(ethylene oxide) methyl ether methacrylate) macroRAFTs are first formed in water using 4‐cyano‐4‐thiothiopropylsulfanyl pentanoic acid (CTPPA) as a chain transfer agent. The resulting macroRAFTs are then directly used without further purification for the RAFT polymerization of styrene in water in the same reactor. This simple and straightforward strategy leads to a very good control of the resulting amphiphilic block copolymers.

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18.
A poly(p‐phenylene) (PPP)‐poly(4‐diphenylaminostyrene) (PDAS) bipolar block copolymer was synthesized for the first time. A prerequisite prepolymer, poly(1,3‐cyclohexadiene) (PCHD)‐PDAS binary block copolymer, in which the PCHD block consisted solely of 1,4‐cyclohexadiene (1,4‐CHD) units, was synthesized by living anionic block copolymerization of 1,3‐cyclohexadiene and 4‐diphenylaminostyrene. To obtain the PPP‐PDAS bipolar block copolymer, the dehydrogenation of this prepolymer with quinones was examined, and tetrachloro‐1,2‐(o)‐benzoquinone was found to be an appropriate dehydrogenation reagent. This dehydrogenation reaction was remarkably accelerated by ultrasonic irradiation, effectively yielding the target PPP‐PDAS bipolar block copolymer. The hole and electron drift mobilities for PPP‐PDAS bipolar block copolymer were both on the order of 10?3 to 10?4 cm2/V·s, with a negative slope when plotted against the square root of the applied field. Therefore, this bipolar block copolymer was found to act as a bipolar semi‐conducting copolymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

19.
Poly(2‐(diethylamino)ethyl methacrylate) (PDEAEMA) homopolymers with low polydispersities were synthesized by reversible addition fragmentation chain transfer (RAFT) radical polymerization. The performances of two chain transfer agents, 2‐cyanoprop‐2‐yl dithiobenzoate and 4‐cyanopentanic acid dithiobenzoate (CPADB), were compared. It was found that the polymerization of 2‐(diethylamino) ethyl methylacrylate was under good control in the presence of CPADB with 4,4′‐azobis(4‐cyanopentanoic acid) (ACPA) as initiator in 1,4‐dioxane at 70 °C. The kinetic behaviors were investigated under different CPADB/ACPA molar ratios. A long polymerization inhibition period was observed at high [CPADB]/[ACPA] ratio. The influences of [CPADB]/[ACPA] ratio, monomer/[CPADB] ratio, and temperature were studied with respect to monomer conversion, molecular weight control, and polydispersity index (PDI). The PDI decreased from 1.21 to 1.12, as the CPADB/ACPA molar ratio changed from 2 to 10. The molecular weight of PDEAEMA could be controlled by monomer/CPADB molar ratio. The control over MW and PDI was improved as the temperature increased from 60 to 70 °C; however, an additional increase to 80 °C led to a loss of control. Using PDEAEMA macroRAFT agent, pH/thermo double‐responsive block copolymers of PDEAEMA and poly(N‐isopropylacrylamide) (PDEAEMA‐b‐PNIPAM) with narrow polydispersity (PDI, 1.24) were synthesized. The lower critical solution temperature of PDEAEMA‐b‐PNIPAM block copolymer depended on the environmental pH. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3294–3305, 2008  相似文献   

20.
Block copolymers of poly(glycidol)‐b‐poly(4‐vinylpyridine) were obtained by ATRP of 4‐vinylpyridine initiated by ω‐(2‐chloropropionyl) poly(glycidol) macroinitiators. By changing the monomer/macroinitiator ratio in the synthesis polymers with varied P4VP/PGl molar ratio were obtained. The obtained block copolymers showed pH sensitive solubility. It was found that the linkage of a hydrophilic poly(glycidol) block to a P4VP influenced the pKa value of P4VP. DLS measurements showed the formation of fully collapsed aggregates exceeding pH 4.7. Above this pH values the collapsed P4VP core of the aggregates was stabilized by a surrounding hydrophilic poly(glycidol) corona. The size of the aggregates depended significantly upon the composition of the block copolymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1782–1794, 2009  相似文献   

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