共查询到20条相似文献,搜索用时 15 毫秒
1.
Haodi Wang Li Zhang Binyuan Liu Bing Han Zhongyu Duan Cuiyun Qi Dae‐Won Park Il Kim 《Macromolecular rapid communications》2015,36(18):1646-1650
High molecular weight cyclic poly(ε‐caprolactone)s (cPCLs) with variable ring size are synthesized via light‐induced ring closure of α,ω‐anthracene‐terminated PCL (An‐PCL‐An). The ring size of cPCL is tunable simply by adjusting the polymer concentration from 10 to 100 mg mL−1 in THF. The cycloaddition via the bimolecular cyclization of An‐PC‐An is well characterized by a variety of analyses such as 1H NMR and UV–vis spectroscopies, gel‐permeation chromatography, and differential scanning calorimetry. The reversible dimerization of An induced by heating enables the cyclic PCL to have a switchable “on–off” capability. This novel light‐induced ring‐closure technique can be one of the most powerful candidates for producing various well‐defined cyclic polymers in highly concentrated polymer solution.
2.
C. Flesch C. Delaite P. Dumas E. Bourgeat‐Lami E. Duguet 《Journal of polymer science. Part A, Polymer chemistry》2004,42(23):6011-6020
We report the coating of maghemite (γ‐Fe2O3) nanoparticles with poly(ε‐caprolactone) (PCL) through a covalent grafting to technique. ω‐Hydroxy‐PCL was first synthesized by the ring‐opening polymerization of ε‐caprolactone with aluminum isopropoxide and benzyl alcohol as a catalytic system. The hydroxy end groups of PCL were then derivatized with 3‐isocyanatopropyltriethoxysilane in the presence of tetraoctyltin. The triethoxysilane‐functionalized PCL macromolecules were finally allowed to react on the surface of maghemite nanoparticles. The composite nanoparticles were characterized by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). Effects of the polymer molar mass and concentration on the amount of polymer grafted to the surface were investigated. Typical grafting densities up to 3 μmol of polymer chains per m2 of maghemite surface were obtained with this grafting to technique. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6011–6020, 2004 相似文献
3.
Giovanni Maglio Giuseppe Nese Margherita Nuzzo Rosario Palumbo 《Macromolecular rapid communications》2004,25(12):1139-1144
Summary: Star‐shaped hydroxy‐terminated poly(ε‐caprolactone)s (ssPCL), with arms of different lengths, were obtained by ring‐opening polymerization (ROP) of ε‐caprolactone initiated by pentaerythritol, and were condensed with α‐methyl‐ω‐(3‐carboxypropionyloxy)‐poly(ethylene oxide)s ( = 550–5 000) to afford four‐armed PCL‐PEO star diblock copolymers (ssPCL‐PEO). The polymers were characterized by 1H and 13C NMR spectroscopy and size‐exclusion chromatography (SEC). The melting behavior of ssPCLs was studied by differential scanning calorimetry (DSC). X‐ray diffraction and DSC techniques were used to investigate the crystalline phases of ssPCL‐PEOs.
The part of the synthesis of four‐armed star‐shaped diblock poly(ε‐caprolactone)‐poly(ethylene oxide) copolymers as described. 相似文献
4.
Sarah El Habnouni Vincent Darcos Jean Coudane 《Macromolecular rapid communications》2009,30(3):165-169
A new functional lactone, α‐iodo‐ε‐caprolactone (αIεCL), was synthesized from ε‐caprolactone by anionic activation using a non‐nucleophilic strong base (lithium diisopropylamide) followed by an electrophilic substitution with iodine chloride. Ring‐opening (co)polymerizations of the resulting monomer with ε‐caprolactone were carried out using tin 2‐ethylhexanoate as a catalyst in toluene at 100 °C. Homopolymerization of αIεCL was achieved, and poly(αIεCL) was fully characterized by SEC, 1H NMR and elemental analysis. Random copolymerizations of αIεCL with εCL were controlled with experimental molecular weights close to the theoretical values, narrow molecular weight distributions and a good agreement between experimental and theoretical molar compositions of αIεCL.
5.
Mingxiao Deng Xuesi Chen Longhai Piao Xuefei Zhang Zhongli Dai Xiabin Jing 《Journal of polymer science. Part A, Polymer chemistry》2004,42(4):950-959
Biodegradable, amphiphilic, four‐armed poly(?‐caprolactone)‐block‐poly(ethylene oxide) (PCL‐b‐PEO) copolymers were synthesized by ring‐opening polymerization of ethylene oxide in the presence of four‐armed poly(?‐caprolactone) (PCL) with terminal OH groups with diethylzinc (ZnEt2) as a catalyst. The chemical structure of PCL‐b‐PEO copolymer was confirmed by 1H NMR and 13C NMR. The hydroxyl end groups of the four‐armed PCL were successfully substituted by PEO blocks in the copolymer. The monomodal profile of molecular weight distribution by gel permeation chromatography provided further evidence for the four‐armed architecture of the copolymer. Physicochemical properties of the four‐armed block copolymers differed from their starting four‐armed PCL precursor. The melting points were between those of PCL precursor and linear poly(ethylene glycol). The length of the outer PEO blocks exhibited an obvious effect on the crystallizability of the block copolymer. The degree of swelling of the four‐armed block copolymer increased with PEO length and PEO content. The micelle formation of the four‐armed block copolymer was examined by a fluorescent probe technique, and the existence of the critical micelle concentration (cmc) confirmed the amphiphilic nature of the resulting copolymer. The cmc value increased with increasing PEO length. The absolute cmc values were higher than those for linear amphiphilic block copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 950–959, 2004 相似文献
6.
Poly(ethylene‐b‐ε‐caprolactone) (PE‐b‐PCL) diblock copolymers were synthesized by ring‐opening polymerization (ROP) of ε‐caprolactone (CL) with α‐hydroxyl‐ω‐methyl polyethylene (PE‐OH) as a macroinitiator and ammonium decamolybdate (NH4)8[Mo10O34] as a catalyst. Polymerization was conducted in bulk (130–150°C) with high yield (87–97%). Block copolymers with different compositions were obtained and characterized by 1H and 13C NMR, MALDI‐TOF, SAXS, and DSC. End‐group analysis by NMR and MALDI‐TOF indicates the formation of α‐hydroxyl‐ω‐methyl PE‐b‐PCL. The PE‐b‐PCL degradation was studied using thermogravimetric analysis (TGA) and alkaline hydrolysis. The PCL block was hydrolyzed by NaOH (4M), without any effect on the PE segment. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
7.
Ajay S. Kasegaonkar Haitham Barqawi Wolfgang H. Binder 《Journal of polymer science. Part A, Polymer chemistry》2015,53(5):642-649
Here, we report on the synthesis and different crystallization behavior of linear‐ and star‐ PCL's containing a photocleavable linker (5‐hydroxy‐2‐nitro benzaldehyde), modulated by photochemical switching. Basis is the attachment of a photocleavable moiety close to the star‐core of a three‐arm star poly(caprolactone), so that the crystallization behavior can be controlled via a photochemical stimulus. The polymerization of ε‐caprolactone using a trivalent photocleavable initiator and stannous octanoate catalyst resulted in the synthesis of different molecular weights of star‐shaped photocleavable polymers. Various techniques like 1H NMR and ESI‐TOF‐MS confirmed the successful synthesis of the star‐shaped polymers. Complete photocleavage is ensured via GPC, HPLC, and ESI‐TOF‐MS. DSC studies clearly indicated the enhancement in crystallinity after photocleavage of the star‐shaped poly(ε‐caprolactone)s. Hence, for the first time phototriggered crystallization behavior of PCL polymers is reported, where the confinement exerted by the star architecture is removed by photoirradiation. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 642–649 相似文献
8.
Meiran Xie Jiaxin Shi Liang Ding Jinxin Li Huijing Han Yiqun Zhang 《Journal of polymer science. Part A, Polymer chemistry》2009,47(12):3022-3033
This article described the synthesis of cyclic poly(ε‐caprolactone) (PCL) via ring‐closing metathesis (RCM), ring closing enyne metathesis (RCEM), and “click” reaction of different difunctional linear PCL. Linear PCL precursors were prepared by ring‐opening polymerization (ROP) of ε‐caprolactone in bulk using 10‐undecen‐1‐ol or propargyl alcohol as the initiator, followed by reacting with corresponding acyl chloride containing vinyl or azido end group. The subsequent end‐to‐end intramolecular coupling reactions were performed under high dilution conditions. The successful transformation of linear PCL precursor to cyclic PCL was confirmed by Gel permeation chromatography, 1H NMR, and Fourier transform infrared measurements. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3022–3033, 2009 相似文献
9.
Juan Huang Zhongyu Li Xuewei Xu Yong Ren Junlian Huang 《Journal of polymer science. Part A, Polymer chemistry》2006,44(11):3684-3691
A well‐defined comblike copolymer of poly(ethylene oxide‐co‐glycidol) [(poly(EO‐co‐Gly)] as the main chain and poly(ε‐caprolactone) (PCL) as the side chain was successfully prepared by the combination of anionic polymerization and ring‐opening polymerization. The glycidol was protected by ethyl vinyl ether to form 2,3‐epoxypropyl‐1‐ethoxyethyl ether (EPEE) first, and then ethylene oxide was copolymerized with EPEE by an anionic mechanism. The EPEE segments of the copolymer were deprotected by formic acid, and the glycidol segments of the copolymers were recovered after saponification. Poly(EO‐co‐Gly) with multihydroxyls was used further to initiate the ring‐opening polymerization of ε‐caprolactone in the presence of stannous octoate. When the grafted copolymer was mixed with α‐cyclodextrin, crystalline inclusion complexes (ICs) were formed, and the intermediate and final products, poly(ethylene oxide‐co‐glycidol)‐graft‐poly(ε‐caprolactone) and ICs, were characterized with gel permeation chromatography, NMR, differential scanning calorimetry, X‐ray diffraction, and thermogravimetric analysis in detail. The obtained ICs had a channel‐type crystalline structure, and the ratio of ε‐caprolactone units to α‐cyclodextrin for the ICs was higher than 1:1. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3684–3691, 2006 相似文献
10.
Peng‐Fei Gou Wei‐Pu Zhu Zhi‐Quan Shen 《Journal of polymer science. Part A, Polymer chemistry》2008,46(6):2108-2118
Two novel multifunctional precursors with eight alcoholic hydroxyls were synthesized by derivatization of resorcinarene. Well‐defined eight‐arm star‐shaped poly(ε‐caprolactone)s (SPCLs) with reasonably narrow molecular weight distributions have been successfully prepared using the precursors as macro‐initiators and yttrium tris(2,6‐di‐tert‐butyl‐4‐methylphenolate) [Y(DBMP)3] as catalyst at 40 °C. The molecular weight of SPCLs was characterized by end group 1H NMR analyses and size‐exclusion chromatography, which could be well controlled by the molar ratio of the monomer to the precursor. The polymerization is more controllable with the precursor holding longer hydrocarbon chains as R groups. Differential scanning calorimetry analyses suggested that the maximal melting point, the crystallization temperature, and the degree of crystallinities of SPCLs increased with the increasing of the molecular weight, and were significantly lower than that of the counterpart linear poly(ε‐caprolactone) (LPCL). Furthermore, polarized optical microscopy indicated that LPCL showed fast crystallization rate with apparent Maltese cross pattern, whereas SPCL exhibited irregular spherulite and apparently slower crystallization rate. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2108–2118, 2008 相似文献
11.
Xiaomei Fang Ronald Hutcheon Daniel A. Scola 《Journal of polymer science. Part A, Polymer chemistry》2000,38(8):1379-1390
Microwave irradiation was applied to synthesize poly(ε‐caprolactam‐co‐ε‐caprolactone) directly from the anionic catalyzed ring opening of two cyclic monomers, ε‐caprolactam and ε‐caprolactone using a variable frequency microwave furnace, programmed to a set temperature and controlled by a pulsed power on–off system. Dielectric properties of ε‐caprolactam, ε‐caprolactone, and their mixture were measured in the microwave range from 0.4 to 3 GHz, showing that both ε‐caprolactam and ε‐caprolactone exhibited effective absorption of microwave energy to induce a fast chemical reaction. The microwave induced anionic copolymerization of ε‐caprolactam and ε‐caprolactone generated copoly(amide‐ester)s in yields as high as 70%. Conventional thermal and microwave copolymerization studies were also conducted for comparison with the microwave results. These studies demonstrated that an effective and efficient microwave method to copolymerize ε‐caprolactam with ε‐caprolactone in higher yield, higher amide content, and higher Tg 's, relative to the thermal process, has been developed. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1379–1390, 2000 相似文献
12.
Yahia Lemmouchi Michael C. Perry Allan J. Amass Khirud Chakraborty Etienne Schacht 《Journal of polymer science. Part A, Polymer chemistry》2007,45(17):3975-3985
Biodegradable, amphiphilic, diblock poly(ε‐caprolactone)‐block‐poly(ethylene glycol) (PCL‐b‐PEG), triblock poly(ε‐caprolactone)‐block‐poly(ethylene glycol)‐block‐poly(ε‐caprolactone) (PCL‐b‐PEG‐b‐PCL), and star shaped copolymers were synthesized by ring opening polymerization of ε‐caprolactone in the presence of poly(ethylene glycol) methyl ether or poly(ethylene glycol) or star poly(ethylene glycol) and potassium hexamethyldisilazide as a catalyst. Polymerizations were carried out in toluene at room temperature to yield monomodal polymers of controlled molecular weight. The chemical structure of the copolymers was investigated by 1H and 13C NMR. The formation of block copolymers was confirmed by 13C NMR and DSC investigations. The effects of copolymer composition and molecular structure on the physical properties were investigated by GPC and DSC. For the same PCL chain length, the materials obtained in the case of linear copolymers are viscous whereas in the case of star copolymer solid materials are obtained with low Tg and Tm temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3975–3985, 2007 相似文献
13.
Gang‐Yin Shi Li‐Ping Yang Cai‐Yuan Pan 《Journal of polymer science. Part A, Polymer chemistry》2008,46(19):6496-6508
Well‐defined hetero eight‐shaped copolymers composed of polystyrene (PS) and poly(ε‐caprolactone) (PCL) with controlled molecular weight and narrow molecular weight distribution were successfully synthesized by the combination of ring‐opening polymerization, ATRP, and “click” reaction. The synthetic procedure involves three steps: (1) preparation of a tetrafunctional PS and PCL star copolymer with two PS and two PCL arms using the tetrafunctional initiator bearing two hydroxyl groups and two bromo groups; (2) synthesis of tetrafunctional star copolymer, (α‐acetylene‐PCL)2(ω‐azido‐PS)2, by the transition of terminal hydroxyl and bromo groups to acetylene and azido groups through the reaction with 4‐propargyloxybutanedioyl chloride and NaN3 respectively; (3) intramolecular cyclization reaction to produce the hetero eight‐shaped copolymers using “click” chemistry under high dilution. The 1H NMR, FTIR, and gel permeation chromatography techniques were applied to characterize the chemical structures of the resulted intermediates and the target polymers. Their thermal behavior was investigated by DSC, and their crystallization behaviors of PCL were studied by polarized optical microscopy. The decrease in chain mobility of the eight‐shaped copolymers restricts the crystallization of PCL and the crystallization rate of PCL is slower in comparison with their corresponding star precursors. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6496–6508, 2008 相似文献
14.
Jing‐Liang Wang Lu Wang Chang‐Ming Dong 《Journal of polymer science. Part A, Polymer chemistry》2005,43(22):5449-5457
Six‐arm star‐shaped poly(ε‐caprolactone) (sPCL) was successfully synthesized via the ring‐opening polymerization of ε‐caprolactone with a commercial dipentaerythritol as the initiator and stannous octoate (SnOct2) as the catalyst in bulk at 120 °C. The effects of the molar ratios of both the monomer to the initiator and the monomer to the catalyst on the molecular weight of the polymer were investigated in detail. The molecular weight of the polymer linearly increased with the molar ratio of the monomer to the initiator, and the molecular weight distribution was very low (weight‐average molecular weight/number‐average molecular weight = 1.05–1.24). However, the molar ratio of the monomer to the catalyst had no apparent influence on the molecular weight of the polymer. Differential scanning calorimetry analysis indicated that the maximal melting point, cold crystallization temperature, and degree of crystallinity of the sPCL polymers increased with increasing molecular weight, and crystallinities of different sizes and imperfect crystallization possibly did not exist in the sPCL polymers. Furthermore, polarized optical microscopy analysis indicated that the crystallization rate of the polymers was in the order of linear poly(ε‐caprolactone) (LPCL) > sPCL5 > sPCL1 (sPCL5 had a higher molecular weight than both sPCL1 and LPCL, which had similar molecular weights). Both LPCL and sPCL5 exhibited a good spherulitic morphology with apparent Maltese cross patterns, whereas sPCL1 showed a poor spherulitic morphology. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5449–5457, 2005 相似文献
15.
Moon Suk Kim Kwang Su Seo Gilson Khang Hai Bang Lee 《Macromolecular rapid communications》2005,26(8):643-648
Summary: The polymerization of ε‐caprolactone (CL) in the presence of HCl · Et2O by an activated monomer mechanism was performed to synthesize diblock or triblock copolymers composed of poly(ethylene glycol) (PEG) and poly(ε‐caprolactone) (PCL). The obtained PCLs had molecular weights close to the theoretical values calculated from the CL to PEG molar ratios and exibited monomodal GPC curves. We successfully prepared PEG and PCL block copolymers by a metal‐free method.
The non‐metal catalyzed living ring‐opening polymerisation of ε‐caprolactone by PEG. 相似文献
16.
Jean Coudane Elisabeth Laurent Michel Vert 《Macromolecular rapid communications》2004,25(21):1865-1869
Summary: The reaction of triphosgene with poly(ethylene glycol) yielded poly(ethylene glycol) dichloroformate. This difunctional cross‐linker was allowed to react with poly(ε‐caprolactone) bearing carbanionic sites obtained by activation with lithium diisopropylamide. The reaction resulted in the cross‐linking of poly(ε‐caprolactone) chains by poly(ethylene glycol) segments, giving copolymer networks that gel in both organic and aqueous media.
Schematic of the PCL‐g‐PEG copolymers synthesized here. 相似文献
17.
PCL/clay nanocomposites were prepared by microwave‐assisted in situ ROP of ε‐caprolactone in the presence of either unmodified clay (Cloisite® Na+) or clay modified by quaternary ammonium cations containing hydroxyl groups (Cloisite 30B). This PCL showed significantly improved monomer conversion and molecular weight compared with that produced by conventional heating. An intercalated structure was observed for the PCL/Cloisite Na+ nanocomposites, while a predominantly exfoliated structure was observed for the PCL/Cloisite 30B nanocomposites. Microwave irradiation proved to be an effective and efficient method for the preparation of PCL/clay nanocomposites.
18.
Hans R. Kricheldorf Gesa Behnken Gert Schwarz 《Journal of polymer science. Part A, Polymer chemistry》2006,44(10):3175-3183
A complex consisting of one Bi3+ ion and two 2‐mercaptoethanol units (BiME2) was used as initiator for the ring‐opening polymerization of ε‐caprolactone in bulk. A kinetic comparison showed that BiME2 is as reactive as initiator as Sn‐octanoate and more reactive than Bi‐hexanoate. The difference to BiHex3 decreased at higher temperatures and upon addition of an alcohol as coinitiator. When tetra(ethylene glycol) was used as coinitiator, it was completely incorporated into the poly(εCL) chain, so that telechelic polylactones having two OH‐endgroups were formed. In the absence of a coinitiator, 2‐mercaptoethanol or its disulfide were incorporated in the form of ester groups. Furthermore, it was found by MALDI‐TOF mass spectrometry that small amounts of cyclic oligolactones (detected up to a degree of polymerization of 17) were formed under all reaction conditions. Higher temperatures and longer times favored a higher content of cycles. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3175–3183, 2006 相似文献
19.
Porous poly(ε‐caprolactone) structures have been prepared by leaching of compression moulded salt‐containing polymer precipitates. Coagulation takes place when a PCL solution containing dispersed water‐soluble salt particles is precipitated into an excess of non‐solvent. Porous scaffolds are obtained after leaching of the compression moulded polymer‐salt precipitate. This process yields scaffolds with a very homogeneous pore morphology and independent control of pore size and porosity. 相似文献
20.
Tapas K. Paira Sanjib Banerjee Tarun K. Mandal 《Journal of polymer science. Part A, Polymer chemistry》2012,50(11):2130-2141
Well‐defined peptide‐poly(ε‐caprolactone) (Pep‐PCL) biohybrids were successfully synthesized by grafting‐from ring‐opening polymerization (ROP) of ε‐caprolactone (CL) using designed amine‐terminated sequence‐defined peptides as macroinitiators. MALDI‐TOF‐MS and 1H NMR analyses confirmed the successful attachment of peptide to the PCL chain. The gel permeation chromatography (GPC) measurement showed that the Pep‐PCL biohybrids with controllable molecular weights and low polydispersities (PDI <1.5) were obtained by this approach. The aggregation of Pep‐PCL hybrid molecules in THF solution resulted in the formation of micro/nanospheres as confirmed through FESEM, TEM, and DLS analyses. The circular dichroism study revealed that the secondary structure of peptide moiety was changed in the peptide‐PCL biohybrids. The crystallization and melting behavior of Pep‐PCL hybrids were somewhat changed compared with that of neat PCL of comparable molecular weight as revealed by DSC and XRD measurements. In Pep‐PCL biohybrids, extinction rings were observed in the PCL spherulites, in contrast with the normal spherulite morphology of the neat PCL. There was a substantial decrease (4–5 folds) in the spherulitic growth rate after the incorporation of peptide moiety at the end of PCL chain as measured by polarizing optical microscopy. Pseudomonas lipase catalyzed enzymatic degradation was studied for Pep‐PCL hybrids and neat PCL. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献