H‐shaped (ABCDE type) quintopolymer via click reaction [3 + 2] strategy

H‐shaped quintopolymer containing different five blocks: poly(ε‐caprolactone) (PCL), polystyrene (PS), poly(ethylene glycol) (PEG), and poly(methyl methacrylate) (PMMA) as side chains and poly(tert‐butyl acrylate) (PtBA) as a main chain was simply prepared from a click reaction between azide end‐functionalized PCL‐PS‐PtBA 3‐miktoarm star terpolymer and PEG–PMMA‐block copolymer with alkyne at the junction point, using Cu(I)/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as a catalyst in DMF at room temperature for 20 h. The H‐shaped quintopolymer was obtained with a number–average molecular weight (M_n) around 32,000 and low polydispersity index (M_w/M_n) 1.20 as determined by GPC analysis in THF using PS standards. The click reaction efficiency was calculated to have 60% from ¹H NMR spectroscopy. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4459–4468, 2008     

Synthesis and characterization of block copolymers by metal‐ and solvent‐free ring‐opening polymerization of cyclic carbonates initiated from PEG‐based surfactants

Ring‐opening polymerizations of trimethylene carbonate (TC) and 2,2‐dimethyltrimethylene carbonate (DTC) are initiated from hydroxyl‐terminated polyethylene glycol (PEG) and PEG‐based surfactants (Triton X‐100 or Triton X‐405) in the absence of any catalysts. The metal‐ and solvent‐free polymerizations proceed under melt at 150 °C, affording Triton X‐100‐block‐poly(TC) with M_n of 1400–5200 and Triton X‐100‐block‐poly(DTC) with M_n of 1800–7100 in excellent yields. The molecular weights and the comonomer composition of the resulting copolymers are controlled by the feed ratios of the monomers to the initiators, confirmed by gel permeation chromatography and ¹H NMR spectroscopy. The solubilities of the block copolymers composed of hydrophilic PEG segment and hydrophobic poly(TC) or poly(DTC) segment depend on both the compositions and the components. For example, Triton X‐100‐block‐poly (TC) (TC/EG = 9.5/9.5) and Triton X‐405‐block‐poly(TC) (TC/EG = 28/40, 46/40) milky suspend in water, while Triton X‐405‐block‐poly(TC) (TC/EG = 9.7/40) dissolves in water. A dynamic light scattering study reveals that the particle distribution of a copolymer, Triton X‐405‐block‐poly(TC) (TC/EG = 9.7/40) in water, has a monodisperse unimodal pattern ranging from 92 to 368 nm. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1985–1996, 2006     

Various polycarbonate graft copolymers via diels–alder click reaction

In this work, we used Diels–Alder click reaction for the preparation of various types of aliphatic polycarbonates (PCs). We first prepared a novel anthracene‐functionalized cyclic carbonate monomer, anthracen‐9‐ylmethyl 5‐methyl‐2‐oxo‐1,3‐dioxane‐5‐carboxylate (2), followed by ring‐opening polymerization of this monomer to prepare PC with pendant anthracene groups (PC‐anthracene) using 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU)/1‐(3,5‐bis(trifloromethyl)phenyl)‐3‐cyclohexylthiourea (TU) as the catalyst and benzyl alcohol as the initiator in CH₂Cl₂ at room temperature. Subsequently, the resulting PC‐anthracene (M_n,TDGPC = 6000 g/mol, M_w/M_n = 1.22) was grafted with a linear α‐furan protected‐maleimide terminated‐poly(methyl methacrylate) (PMMA‐MI) (M_n,GPC = 3100 g/mol, M_w/M_n = 1.31), or poly(ethylene glycol) (PEG‐MI) (M_n,GPC = 550 g/mol, M_w/M_n = 1.09), or a mixture of PMMA‐MI and PEG‐MI to yield well‐defined PC graft or hetero graft copolymers, PC‐g‐PMMA (M_n,TDGPC = 59000 g/mol, M_w/M_n = 1.22) or PC‐g‐PEG, or PC‐g‐(PMMA)‐co‐PC‐g‐(PEG) (M_n,TDGPC = 39900 g/mol, M_w/M_n = 1.16), respectively, using Diels–Alder click reaction in toluene at 110°C. The Diels–Alder grafting efficiencies were found to be over 97% using UV spectroscopy. Moreover, the structural analyses and the molecular weights of resulting graft copolymers were determined via ¹H NMR and triple detection GPC (TD‐GPC), respectively. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Polymer grafting onto polyurethane backbone via Diels–Alder reaction

The aliphatic polyurethane with pendant anthracene moieties (PU‐anthracene) was prepared from polycondensation of anthracen‐9‐yl methyl 3‐hydroxy‐2‐(hydroxymethyl)‐2‐methylpropanoate (anthracene diol), 1 with hexamethylenediisocyanate in the presence of dibutyltindilaurate in CH₂Cl₂ at room temperature for 10 days. Thereafter, the PU‐anthracene (M_n,GPC = 12,900 g/mol, M_w/M_n = 1.87, relative to PS standards) was clicked with a linear α‐furan protected‐maleimide terminated‐poly(methyl methacrylate) (PMMA‐MI) (M_n,GPC = 2500 g/mol, M_w/M_n = 1.33), or ‐poly(ethylene glycol) (PEG‐MI) (M_n,GPC = 550 g/mol, M_w/M_n = 1.09), to result in well‐defined PU‐graft copolymers, PU‐g‐PMMA (M_n,GPC = 23800 g/mol, M_w/M_n = 1.65, relative to PS standards) or PU‐g‐PEG (M_n,GPC = 11,600 g/mol, M_w/M_n = 1.45, relative to PS standards) using Diels–Alder reaction in dioxane/toluene at 105 °C. The Diels–Alder grafting efficiencies were found to be over 93–99% using UV spectroscopy. Moreover, the structural analyses and the thermal transitions of all copolymers were determined via ¹H NMR and DSC, respectively. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 521–527     

Novel,biodegradable, functional poly(ester‐carbonate)s by copolymerization of trans‐4‐hydroxy‐L‐proline with cyclic carbonate bearing a pendent carboxylic group

Water‐soluble poly(ester‐carbonate) having pendent amino and carboxylic groups on the main‐chain carbon is reported for the first time. This article describes the melt ring‐opening/condensation reaction of trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline (N‐CBz‐Hpr) with 5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one (MBC) at a wide range of molar fractions. The influence of reaction conditions such as catalyst concentration, polymerization time, and temperature on the number average molecular weight (M_n) and molecular weight distribution (M_w/M_n) of the copolymers was investigated. The polymerizations were carried out in bulk at 110 °C with 3 wt % stannous octoate as a catalyst for 16 h. The poly(ester‐carbonate)s obtained were characterized by Fourier transform infrared spectroscopy, ¹H NMR, differential scanning calorimetry, and gel permeation chromatography. The copolymers synthesized exhibited moderate molecular weights (M_n = 6000–14,700 g mol^?1) with reasonable molecular weight distributions (M_w/M_n = 1.11–2.23). The values of the glass‐transition temperature (T_g) of the copolymers depended on the molar fractions of cyclic carbonate. When the MBC content decreased from 76 to 12 mol %, the T_g increased from 16 to 48 °C. The relationship between the poly(N‐CBz‐Hpr‐co‐MBC) T_g and the compositions was in approximation with the Fox equation. In vitro degradation of these poly(N‐CBz‐Hpr‐co‐MBC)s was evaluated from weight‐loss measurements and the change of M_n and M_w/M_n. Debenzylation of 3 by catalytic hydrogenation led to the corresponding linear poly(ester‐carbonate), 4 , with pendent amino and carboxylic groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2303–2312, 2004     

Bioengineering functional copolymers. III. Synthesis of biocompatible poly[(N‐isopropylacrylamide‐co‐maleic anhydride)‐g‐poly(ethylene oxide)]/poly(ethylene imine) macrocomplexes and their thermostabilization effect on the activity of the enzyme penicillin G acylase

Stimuli‐responsive poly[(N‐isopropylacrylamide‐co‐maleic anhydride)‐g‐poly(ethylene oxide)]/poly(ethylene imine) macrobranched macrocomplexes were synthesized by (1) the radical copolymerization of N‐isopropylacrylamide and maleic anhydride with α,α′‐azobisisobutyronitrile as an initiator in 1,4‐dioxane at 65 °C under a nitrogen atmosphere, (2) the polyesterification (grafting) of prepared poly(N‐isopropylacrylamide‐co‐maleic anhydride) containing less than 20 mol % anhydride units with α‐hydroxy‐ω‐methoxy‐poly(ethylene oxide)s having different number‐average molecular weights (M_n = 4000, 10,000, or 20,000), and (3) the incorporation of macrobranched copolymers with poly(ethylene imine) (M_n = 60,000). The composition and structure of the synthesized copolymer systems were determined by Fourier transform infrared, ¹H and ¹³C NMR spectroscopy, and chemical and elemental analyses. The important properties of the copolymer systems (e.g., the viscosity, thermal and pH sensitivities, and lower critical solution temperature behavior) changed with increases in the molecular weight, composition, and length of the macrobranched hydrophobic domains. These copolymers with reactive anhydride and carboxylic groups were used for the stabilization of penicillin G acylase (PGA). The conjugation of the enzyme with the copolymers significantly increased the thermal stability of PGA (three times at 45 °C and two times at 65 °C). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1580–1593, 2003     

Synthesis of poly(p‐phenylene) macromonomers and multiblock copolymers

Rigid‐rod poly(4′‐methyl‐2,5‐benzophenone) macromonomers were synthesized by Ni(0) catalytic coupling of 2,5‐dichloro‐4′‐methylbenzophenone and end‐capping agent 4‐chloro‐4′‐fluorobenzophenone. The macromonomers produced were labile to nucleophilic aromatic substitution. The molecular weight of poly(4′‐methyl‐2,5‐benzophenone) was controlled by varying the amount of the end‐capping agent in the reaction mixture. Glass‐transition temperatures of the macromonomers increased with increasing molecular weight and ranged from 117 to 213 °C. Substitution of the macromonomer end groups was determined to be nearly quantitative by ¹H NMR and gel permeation chromatography. The polymerization of a poly(4′‐methyl‐2,5‐benzophenone) macromonomer [number‐average molecular weight (M_n) = 1.90 × 10³ g/mol; polydispersity (M_w)/M_n = 2.04] with hydroxy end‐capped bisphenol A polyaryletherketone (M_n = 4.50 × 10³ g/mol; M_w/M_n = 1.92) afforded an alternating multiblock copolymer (M_n = 1.95 × 10⁴ g/mol; M_w/M_n = 6.02) that formed flexible, transparent films that could be creased without cracking. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3505–3512, 2001     

Three‐arm star block copolymers of ε‐caprolactone and acrylic acid: Synthesis and micellization behavior

A series of well‐defined three‐arm star poly(ε‐caprolactone)‐b‐poly(acrylic acid) copolymers having different block lengths were synthesized via the combination of ring‐opening polymerization (ROP) and atom transfer radical polymerization (ATRP). First, three‐arm star poly(ε‐caprolactone) (PCL) (M_n = 2490–7830 g mol^?1; M_w/M_n = 1.19–1.24) were synthesized via ROP of ε‐caprolactone (ε‐CL) using tris(2‐hydroxyethyl)cynuric acid as three‐arm initiator and stannous octoate (Sn(Oct)₂) as a catalyst. Subsequently, the three‐arm macroinitiator transformed from such PCL in high conversion initiated ATRPs of tert‐butyl acrylate (^tBuA) to construct three‐arm star PCL‐b‐P^tBuA copolymers (M_n = 10,900–19,570 g mol^?1; M_w/M_n = 1.14–1.23). Finally, the three‐arm star PCL‐b‐PAA copolymer was obtained via the hydrolysis of the PtBuA segment in three‐arm star PCL‐b‐P^tBuA copolymers. The chain structures of all the polymers were characterized by gel permeation chromatography, proton nuclear magnetic resonance (¹H NMR), and Fourier transform infrared spectroscopy. The aggregates of three‐arm star PCL‐b‐PAA copolymer were studied by the determination of critical micelles concentration and transmission electron microscope. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Encapsulation of nanomaterials using an intermediary layer cross‐linkable ABC triblock copolymer

For the preparation of core‐shell nanoparticles containing functional nanomaterials, a photo‐cross‐linkable amphiphilic ABC triblock copolymer, poly(ethylene glycol)‐b‐poly(2‐cinnamoyloxyethyl methacrylate)‐b‐poly(methyl methacrylate) (PEG‐PCEMA‐PMMA), was synthesized. This triblock copolymer was then used to encapsulate Au nanoparticles or pyrene. The triblock copolymer of PEG‐b‐poly(2‐hydroxyethyl methacrylate)‐b‐PMMA (PEG‐PHEMA‐PMMA) (M_n = 15,800 g/mol, M_w/M_n = 1.58) was first synthesized by activators generated by electron transfer atom transfer radical polymerization. Its middle block was then functionalized with cinnamoyl chloride. The degrees of polymerization of the PEG, PHEMA, and PMMA blocks were 45, 13, and 98, respectively. PMMA‐tethered Au nanoparticles (with an average diameter of 3.0 nm) or pyrene was successfully encapsulated within the PEG‐PCEMA‐PMMA micelles. The intermediary layers of the micelles were then cross‐linked by UV irradiation. The spherical structures of the PEG‐PCEMA‐PMMA micelles containing Au nanoparticles or pyrene were not changed by the photo‐cross‐linking process and they showed excellent colloidal stability. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4963–4970, 2009     

Synthesis and characterization of UV‐curable ladder‐like polysilsesquioxane

Various ladder‐like structured poly(phenyl‐co‐methacryl silsesquioxane)s (LPMSQ)s with high molecular weight (M_w = 10,000 ～ 40,000) were synthesized by direct hydrolysis and polymerization in the presence of base catalyst at 25 °C. Synthesized LPMSQs mainly showed ladder‐like structure and photo‐cure reaction by 100 mW/cm² (360 nm) for 10 s without any photo‐cure initiators. Chemical composition and structural analysis of the obtained LPMSQs were characterized using ¹H NMR, ²⁹Si NMR, Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), and X‐ray diffraction (XRD). Physical properties of LPMSQs before and after photcuring were analyzed by Nanoindentation. Surface modulus increased to 8GPa and hardness of thin films increased from 100 to 400 MPa. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and characterization of model polybutadiene‐1,4‐b‐polydimethylsiloxane‐b‐polybutadiene‐1,4 copolymers

Model copolymers of poly(butadiene) (PB) and poly(dimethylsiloxane) (PDMS), PB‐b‐PDMS‐b‐PB, were synthesized by sequential anionic polymerization (high vacuum techniques) of 1,3‐butadiene and hexamethylciclotrisiloxane (D₃) on sec‐BuLi followed by chlorosilane‐coupling chemistry. The synthesized copolymers were characterized by nuclear magnetic resonance (¹H NMR), size‐exclusion chromatography (SEC), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). SEC and ¹H NMR results showed low polydispersity indexes (M_w/M_n) and variable siloxane compositions, whereas DSC and TGA experiments indicated that the thermal stability of the triblock copolymers depends on the PDMS composition. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2726–2733, 2007     

Preparation and microstructural analysis of poly(lactic‐alt‐glycolic acid)

Alternating copolymers of glycolic (G) and lactic (L) acid were prepared by the condensation of the preformed dimers: L_LG and L_racG. By size exclusion chromatography (THF, PS standards), poly(L_LG) exhibited a molecular weight (M_n) of 15.6 kg mol^?1, with a weight average molecular weight (M_w) of 26.9 kg mol^?1 and a PDI of 1.72. The M_n for poly(L_racG) was 9.2 kg mol^?1, with a M_w of 12.9 kg mol^?1 and a PDI of 1.40. The NMR spectra of poly(L_LG) were consistent with an isotactic microstructure. NMR spectra of the racemic poly(L_racG) were consistent with an atactic structure. The methylene region of the ¹H NMR spectrum showed a tetrad level of resolution of the nearby stereochemical relationships, for example, iii. Resonances for other groups in both the ¹H and ¹³C NMR spectra gave only a triad level of resolution. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4704–4711, 2008     

Titanium complexes of dialkanolamine ligands as initiators for living ring‐opening polymerization of ε‐caprolactone

The titanium complexes with one ( 1a , 1b , 1c ) and two ( 2a , 2b ) dialkanolamine ligands were used as initiators in the ring‐opening polymerization (ROP) of ε‐caprolactone. Titanocanes 1a and 1b initiated living ROP of ε‐caprolactone affording polymers whose number‐average molecular weights (M_n) increased in direct proportion to monomer conversion (M_n ≤ 30,000 g mol^?1) in agreement with calculated values, and were inversely proportional to initiator concentration, while the molecular weight distribution stayed narrow throughout the polymerization (M_w/M_n ≤ 1.2 up to 80% monomer conversion). ¹H‐NMR and MALDI‐TOF‐MS studies of the obtained poly(ε‐caprolactone)s revealed the presence of an isopropoxy group originated from the initiator at the polymer termini, indicating that the polymerization takes place exclusively at the Ti–OⁱPr bond of the catalyst. The higher molecular weight polymers (M_n ≤ 70,000 g mol^?1) with reasonable MWD (M_w/M_n ≤ 1.6) were synthesized by living ROP of ε‐caprolactone using spirobititanocanes ( 2a , 2b ) and titanocane 1c as initiators. The latter catalysts, according MALDI‐TOF‐MS data, afford poly(ε‐caprolactone)s with almost equal content of α,ω‐dihydroxyl‐ and α‐hydroxyl‐ω(carboxylic acid)‐terminated chains arising due to monomer insertion into “Ti–O” bond of dialkanolamine ligand and from initiation via traces of water, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1230–1240, 2010     

Synthesis and healing properties of poly(arylene ether sulfone)‐poly(alkyl disulfide) multiblock copolymers

A multiblock copolymer consisting of hard (poly(arylene ether sulfone)) and soft (poly(alkyl disulfide)) segments was successfully synthesized by oxidative coupling of the corresponding thiol‐terminated oligomers. Its structure was confirmed by ¹H and ¹³C NMR spectroscopy. The GPC data (M_w = 82,000, M_w/M_n = 2.7) and inherent viscosity (0.67 dL g⁻¹) indicated the formation of a high‐molecular‐weight multiblock copolymer, while AFM and DSC indicated a microphase‐separated morphology. Tensile testing of the multiblock copolymer films showed a large elongation at break, which is characteristic of microphase‐separated hard/soft multiblock copolymers. Over 90% of the elongation at break of damaged samples (notched or cut) was recovered by UV irradiation. The elongation recovery was proportional to the UV irradiation energy, and the high recovery was achieved by relatively weak irradiation (<170 J cm⁻²). The high content of disulfide bonds in the multiblock copolymer resulted in a lower self‐healing energy. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1358–1365     

Microwave‐improved polymerization of ϵ‐caprolactone initiated by carboxylic acids

The ring‐opening polymerization of ε‐caprolactone (ε‐CL), initiated by carboxylic acids such as benzoic acid and chlorinated acetic acids under microwave irradiation, was investigated; with this method, no metal catalyst was necessary. The product was characterized as poly(ε‐caprolactone) (PCL) by ¹H NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet spectroscopy, and gel permeation chromatography. The polymerization was significantly improved under microwave irradiation. The weight‐average molecular weight (M_w) of PCL reached 44,800 g/mol, with a polydispersity index [weight‐average molecular weight/number‐average molecular weight (M_w/M_n)] of 1.6, when a mixture of ε‐CL and benzoic acid (25/1 molar ratio) was irradiated at 680 W for 240 min, whereas PCL with M_w = 12,100 and M_w/M_n = 4.2 was obtained from the same mixture by a conventional heating method at 210 °C for 240 min. A degradation of the resultant PCL was observed during microwave polymerization with chlorinated acetic acids as initiators, and this induced a decrease in M_w of PCL. However, the degradation was hindered by benzoic acid at low concentrations. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 13–21, 2003     

Synthesis and characterization of a series of biodegradable and biocompatible PEG‐supported poly(lactic‐ran‐glycolic acid) amphiphilic barbell‐like copolymers

A series of multihydroxyl (2, 4, and 8) terminated poly(ethylene glycol)s and their biodegradable, biocompatible, and branched barbell‐like (PLGA)_n‐b‐PEG‐b‐(PLGA)_n (n = 1, 2, 4) copolymers have been synthesized. The lengths of the PLGA arms were varied by controlling the molar ratio of monomers to hydroxyl groups of PEG ([LA+GA]₀/[? OH]₀ = 23, 45, 90). Chemical structures of synthesized barbell‐like copolymers were confirmed by both ¹H and ¹³C‐NMR spectroscopies. Molecular weights were determined by ¹H‐NMR end‐group analysis and gel permeation chromatography. The result of hydrolytic degradation indicated that the rate of degradation increased with the increase of arm numbers or with the decrease of arm lengths. The thermal properties were evaluated by using differential scanning calorimetry and a thermogravimetric analysis. The results indicated that the thermal properties of barbell‐like copolymers depended on the structural variations. The morphology of (PLGA)_n‐PEG‐(PLGA)_n copolymers self‐assembly films were investigated by atomic force microscope, the results indicated that the microphase separation existed in (PLGA)_n‐PEG‐(PLGA)_n copolymers. Because of the favorable biodegradability and biocompatibility of the PLGA and PEG, these results may therefore create new possibilities for these novel structural amphiphilic barbell‐like copolymers as potential biomaterials. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3802–3812, 2008     

Waterborne polyesters partially based on renewable resources

A new experimental approach for preparing biobased, water‐soluble polyesters (PEs) via titanium(IV) n‐butoxide‐catalyzed bulk polycondensation is presented. In the described method polymers were obtained from isosorbide, maleic anhydride and poly(ethylene glycol) (PEG). The chemical structure of the synthesized PEs was confirmed using 2D NMR spectroscopy and by titration methods. Careful analysis of 2D NMR spectra viz. correlation spectra (COSY), heteronuclear single quantum correlation spectra (HSQC) and heteronuclear multiple‐bond correlation spectra (HMBC) allowed to accomplish the complete proton assignment of isosorbide, PEG, and unsaturated acid residues in the PEs. Moreover, by using NMR spectroscopy the transformation of maleic anhydride into fumaric acid ester and the absence of maleic acid ester units in the final polymer were proven. However, during polycondensation part of the unsaturated bonds has reacted in a Michael addition with isosorbide or PEG. Gel permeation chromatography measurements revealed that the unsaturated PEs have M_n values in the range 3000–5000 g/mol. These PEs, with a low content of carboxylic acid end groups, exhibited sufficient thermal resistance for practical applications, for example, as free radical curable coatings. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis,pH‐ and temperature‐induced micellization and gelation of doubly hydrophilic triblock copolymer of poly(N,N‐dimethylamino‐2‐ethylmethacrylate)‐b‐poly(ethylene glycol)‐b‐poly(N,N‐dimethylamino‐2‐ethylmethacrylate) in aqueous solutions

A doubly hydrophilic triblock copolymer of poly(N,N‐dimethylamino‐2‐ethyl methacrylate)‐b‐Poly(ethylene glycol)‐b‐poly(N,N‐dimethylamino‐2‐ethylmethacrylate) (PDMAEMA‐b‐PEG‐b‐PDMAEMA) with well‐defined structure and narrow molecular weight distribution (M_w/M_n = 1.21) was synthesized in aqueous medium via atom transfer radical polymerization (ATRP) of N,N‐dimethylamino‐2‐ethylmethacrylate (DMAEMA) initiated by the PEG macroinitiator. The macroinitiator and triblock copolymer were characterized with ¹H NMR and gel permeation chromatography (GPC). Fluorescence spectroscopy, dynamic light scattering (DSL), transmittance measurement, and rheological characterization were applied to investigate pH‐ and temperature‐induced micellization in the dilute solution of 1 mg/mL when pH > 13 and gelation in the concentrated solution of 25 wt % at pH = 14 and temperatures beyond 80 °C. The unimer of R_h = 3.7 ± 0.8 nm coexisted with micelle of R_h = 45.6 ± 6.5 nm at pH 14. Phase separation occurred in dilute aqueous solution of the triblock copolymer of 1 mg/mL at about 50 °C. Large aggregates with R_h = 300–450 nm were formed after phase separation, which became even larger as R_h = 750–1000 nm with increasing temperature. The gelation temperature determined by rheology measurement was about 80 °C at pH 14 for the 25 wt % aqueous solution of the triblock copolymer. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5869–5878, 2008     

Synthesis and NMR Characterization of Multi‐hydroxyl End‐groups PEG and PLGA‐PEG Barbell‐like Copolymers

Multi‐hydroxyl end‐groups poly(ethylene glycol) (PEG) was prepared from PEG and epichlorohydrin. Then, PEG‐supported poly(lactic‐ran‐glycolic acid) (PLGA)_n‐PEG‐(PLGA)_n (n=1, 2, 4) linear‐dendritic barbell‐like copolymers were synthesized through direct polycondensation under bulk condition from the multi‐hydroxyl end‐groups PEG, lactic acid and glycolic acid. Arm numbers were varied, with 2, 4 and 8, by using bis‐, tetra‐, and octa‐hydroxyl end‐groups PEG, respectively. The chemical structures, absolute number‐average molecular weight, the monomer units per single arm and the molar ratio of hydroxyl acid monomer units of the (PLGA)_n‐PEG‐(PLGA)_n barbell‐like copolymers were analyzed by NMR spectroscopy. The result indicated that the structures of the multi‐hydroxyl end‐groups PEG and (PLGA)_n‐PEG‐(PLGA)_n barbell‐like copolymers were consistent with design. Compared with the theoretical values, molecular weights determined by ¹H‐NMR end‐group analysis gave reasonably consistent values, but the values determined by gel permeation chromatography (GPC) were considerably less than theoretical values. The results indicated that (PLGA)_n‐PEG‐(PLGA)_n copolymers have linear‐dendritic structures.     

Ethylene glycol‐based ionic liquids via azide/alkyne click chemistry

A facile synthetic route for the preparation of dicationic ethylene glycol based‐ionic liquids (ILs) via the azide/alkyne “click” reaction is presented. The copper(I) catalyzed, microwave‐assisted azide/alkyne “click” reaction between diazido‐ethylene glycols and the corresponding alkyne containing IL‐head group enables a simple preparation of different sets of poly(ethylene glycol)‐based ILs. Beside tetra‐ and hexa(ethylene glycol)‐based ILs, also oligomeric (M_n = 400 g/mol) and polymeric ILs (M_n up to 1550 g/mol) could be prepared in good yield and with full conversion of the ionic head group. The prepared ILs were extensively characterized via NMR spectroscopy and ESI‐time‐of‐flight (TOF) mass spectroscopy, revealing the formation of multiply charged ions in the negative mode. Thermal stability proved to be exceptionally high (up to 300 °C) together with low glass‐transition temperatures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013