Synthesis of A<Subscript>2</Subscript>B<Subscript>2</Subscript> miktoarm star copolymers from a new heterobifunctional initiator by combination of ROP and ATRP

Abstract  

A new heterobifunctional initiator, 2,3-bis(2-bromo-2-methylpropionyloxy) succinic acid, was synthesized and used in preparation of A₂B₂ miktoarm star copolymers, (polystyrene)₂(poly(ε-caprolactone))₂, by combination of atom transfer radical polymerization (ATRP) and Controlled ring-opening polymerization (ROP). The structures of products were confirmed by the ¹H NMR, ¹³C NMR, FT–IR, elemental analysis, differential scanning calorimetry (DSC), and gel permeation chromatography (GPC). GPC traces show that the obtained polymers have a relatively narrow molecular weight distribution. The compositions of resulting miktoarm star copolymers were very close to theoretical.     

Ring‐opening polymerization of ε‐caprolactone with a divalent samarium bis(phosphido) complex

The ring‐opening polymerization of ε‐caprolactone initiated with a divalent samarium bis(phosphido) complex [Sm(PPh₂)₂] is reported. The polymerization proceeded under mild reaction conditions and resulted in polyesters with number‐average molecular weights of 8.2 × 10³ to 12.5 × 10³. The yield and molecular weight of poly(ε‐caprolactone)s were dependent on the experimental parameters, such as the monomer/initiator molar ratio, the monomer concentration, the reaction temperature, and the polymerization time. The obtained polymers were characterized with Fourier transform infrared, NMR, gel permeation chromatography, and differential scanning calorimetry. On the basis of an end‐group analysis of low‐molecular‐weight polymers by NMR spectroscopy, a coordination–insertion mechanism is proposed for the polymerization. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1558–1564, 2005     

Cationic polymerization of 2,4,4-trimethyl-2-oxazoline

Summary The cationic homopolymerization of 2,4,4-trimethyl-2-oxazoline using BF₃Et₂O as initiator at different initiator concentrations, temperatures, times and solvents of polymerization were carried out. The effect of these variables on the polymerization yield and viscosity of the polymers were studied. Polymers were characterized by IR.¹H NMR and¹³C NMR which support that the polymerization reaction occurs by ring opening of oxazoline through oxazolinium intermediates.     

Syntheses and characterizations of side-chain liquid crystalline poly(glycidyl ether)s with biphenyl mesogenic group

Summary Four three-armed poly(glycidyl ether)s with biphenyl mesogenic group and various lengths of spacer, new side-chain liquid crystalline polymers, were synthesized by cationic ring-opening polymerization of the corresponding monomers in the presence of 2,2-dihydroxymethylbutanol and BF₃·OEt₂ as initiator. The structures of the obtained poly(glycidyl ether)s were verified by ¹H and ¹³C NMR spectroscopy, and their liquid crystalline behaviors were studied by differential. scanning calorimetry (DSC and optical polarizing microscopy (OPM). Received: 5 January 1999/Revised version: 20 April 1999/Accepted: 26 April 1999     

Design of novel poly(methyl vinyl ether) containing AB and ABC block copolymers by the dual initiator strategy

A new set of block copolymers containing poly(methyl vinyl ether) (PMVE) on one hand and poly(tert-butyl acrylate), poly(acrylic acid), poly(methyl acrylate) or polystyrene on the other hand, have been prepared by the use of a novel dual initiator 2-bromo-(3,3-diethoxy-propyl)-2-methylpropanoate. The dual initiator has been applied in a sequential process to prepare well-defined block copolymers of poly(methyl vinyl ether) (PMVE) and hydrolizable poly(tert-butyl acrylate) (PtBA), poly(methyl acrylate) (PMA) or polystyrene (PS) by living cationic polymerization and atom transfer radical polymerization (ATRP), respectively. In a first step, the Br and acetal end groups of the dual initiator have been used to generate well-defined homopolymers by ATRP (resulting in polymers with remaining acetal function) and living cationic polymerization (PMVE with pendant Br end group), respectively. In a second step, those acetal functionalized polymers and PMVE-Br homopolymers have been used as macroinitiators for the preparation of PMVE-containing block copolymers. After hydrolysis of the tert-butyl groups in the PMVE-b-ptBA block copolymer, PMVE-b-poly(acrylic acid) (PMVE-b-PAA) is obtained. Chain extension of the AB diblock copolymers by ATRP gives rise to ABC triblock copolymers. The polymers have been characterized by MALDI-TOF, GPC and ¹H NMR.     

SYNTHESIS,CHARACTERIZATION, AND THERMAL STABILITY OF HOMOPOLYMER AND COPOLYMER OF SOME 3-ARYL-2-HYDROXYPROPYL METHACRYLATES

Three new hydroxypropyl methacrylates having three different aryl rings were synthesized by addition of 2,3-epoxypropyl aromatic hydrocarbon to methacrylic acid. The monomers prepared are 3-phenyl-2-hydroxypropyl methacrylate, 3-tolyl-2-hydroxypropyl methacrylate, (THPMA), and 3-naphtyl-2-hydroxypropyl methacrylate. The homopolymers of these monomers and two different copolymers, [poly(THPMA-co-BMA)], were obtained from polymerization at 60°C in 1,4-dioxane solution using AIBN as initiator. All the monomers and the polymers were characterized by FT-IR and ¹H and ¹³C NMR techniques. Solubility parameters of the polymers and average molecular weight of poly(THPMA) were determined. Thermal stabilities of the polymers were given as comparing with each other by using TGA curves. Thermal degradation of poly(THPMA60%-co-BMA40%) was studied in detail.     

Synthesis and characterization of poly(p‐phenylene)‐graft‐poly(ε‐caprolactone) copolymers by combined ring‐opening polymerization and cross‐coupling processes

2,5‐Dibromo‐1,4‐(dihydroxymethyl)benzene was used as initiator in ring‐opening polymerization of ε‐caprolactone in the presence of stannous octoate (Sn(Oct)₂) catalyst. The resulting poly(ε‐caprolactone) (PCL) macromonomer, with a central 2,5‐dibromo‐1,4‐diphenylene group, was used in combination with 1,4‐dibromo‐2,5‐dimethylbenzene for a Suzuki coupling in the presence of Pd(PPh₃)₄ as catalyst or using the system NiCl₂/bpy/PPh₃/Zn for a Yamamoto‐type polymerization. The poly(p‐phenylenes) (PPP) obtained, with PCL side chains, have solubility properties similar to those of the starting macromonomer, ie soluble in common organic solvents at room temperature. The new polymers were characterized by ¹H and ¹³C NMR and UV spectroscopy and also by GPC measurements. The thermal behaviour of the precursor PCL macromonomer and the final poly(p‐phenylene)‐graft‐poly(ε‐caprolactone) copolymers were investigated by thermogravimetric analysis and differential scanning calorimetry analyses and compared. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of poly(dimethylamino ethyl methacrylate)–poly(ethylene oxide)–poly(dimethylamino ethyl methacrylate) triblock copolymers

Novel, monodispersed, and well‐defined ABA triblock copolymers [poly(dimethylamino ethyl methacrylate)–poly(ethylene oxide)–poly(dimethylamino ethyl methacrylate)] were synthesized by oxyanionic polymerization with potassium tert‐butanoxide as the initiator. Gel permeation chromatography and ¹H‐NMR analysis showed that the obtained products were the desired copolymers with molecular weights close to calculated values. Because the poly(dimethylamino ethyl methacrylate) block was pH‐ and temperature‐sensitive, the aqueous solution behavior of the polymers was investigated with ¹H‐NMR and dynamic light scattering techniques at different pH values and at different temperatures. The micelle morphology was determined with transmission electron microscopy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Study on the geometric structure of poly[1-(trimethylsilyl)-1-propyne] by 13C and 29Si NMR spectroscopies

Summary The geometric structure of poly[1-(trimethylsilyl)-1-propyne] was investigated by ¹³C and ²⁹Si NMR spectroscopies. According to ¹³C NMR, the geometric structure varied with polymerization catalysts. NbCl₅ was inferred to produce more cis-rich polymer than TaCl₅. On the other hand, polymerization conditions such as solvent, temperature and cocatalyst hardly affected the geometric structure. The cis contents of polymers bearing bulkier substituents (-SiMe₂-nC₆H₁₃,-SiMe₂-CH₂SiMe₃) prepared with TaCl₅ were similar to that of poly (TMSP) with TaCl₅.     

Reversible addition-fragmentation chain transfer polymerization of styrene initiated by tetraethylthiuram disulfide

The RAFT polymerization of styrene in bulk was carried out using tetraethylthiuram disulfide (TETD) as an initiator and 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN) as a chain transfer agent at different temperatures. The results of the polymerization showed that TETD could initiate the RAFT polymerization of styrene in the living way. The kinetics of the polymerization showed first order. The molecular weights of the polymers increased linearly with conversions and were close to the theoretical values (M_n,th). The polydispersities of the polymers remained relatively narrow (<1.3). The structure of the polymer was characterized by ¹H NMR. The result showed that there were moieties of CPDN and TETD attained at the end of the polymer. Using these double functional end capped polymers, the chain-extension experiments were successfully carried out not only in the conventional RAFT polymerization way, but also under UV irradiation.     

ICAR ATRP of methyl methacrylate catalyzed by FeCl3·6H2O/succinic acid

In this work, methyl methacrylate (MMA) was polymerized by initiator for continuous activator regeneration (ICAR) atom transfer radical polymerization (ATRP) method to obtain low molecular weight living polymers. The ATRP initiator was ethyl 2‐bromoisobutyrate, the catalyst ligand complex system was FeCl₃·6H₂O/succinic acid, and the conventional radical initiator 2,2′‐azobisisobutyronitrile was used as a thermal radical initiator. Polymers with controlled molecular weight were obtained with ppm level of Fe catalyst complex at 90°C in N,N‐dimethylformamide. The polymer was characterized by nuclear magnetic resonance (NMR). The molecular weight and molecular weight distribution of the obtained poly (methyl methacrylate) were measured by gel permeation chromatography method. The kinetics results indicated that ICAR ATRP of MMA was a “living”/controlled polymerization, corresponding to a linear increase of molecular weights with the increasing of monomer conversion and a relatively narrow polydispersities index. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Poly(p-phenylene) graft copolymers with polytetrahydrofuran/polystyrene side chains

1,4-Dibromo-2,5-bis(bromomethyl)benzene was used as a bifunctional initiator in cationic ring opening polymerization (CROP) of tetrahydrofuran. The resulting macromonomer, with a central 2,5-dibromobenzene ring, was reacted in combination with 2,5-dihexylbenzene-1,4-diboronic acid by a Suzuki coupling, in the presence of Pd(PPh₃)₄ as catalyst, leading to a poly(p-phenylene) (PPP) with alternating polytetrahydrofuran (PTHF) and hexyl side chains. A polystyrene (PSt) based macromonomer with a central benzene ring bearing cyclic boronic acid propanediol diester groups, synthesized by atom transfer radical polymerization (ATRP), was also used as partner for PTHF in the cross-coupling reaction. A PPP with alternating PSt and PTHF side chains was obtained. PTHF macromonomer was also homopolymerized by a Yamamoto reaction. The resulting PPPs have high solubility in common organic solvents at room temperature. The new polymers were characterized by GPC, ¹H NMR, ¹³C NMR, IR and UV analysis. Thermal behavior of the precursor PTHF macromonomer and the final polyphenylenes were investigated by TGA and DSC analyses and compared.     

Synthesis of poly(ethylene glycol-b-styrene) block copolymers by reverse atom transfer radical polymerization

Reverse atom transfer radical polymerization (RATRP) of styrene (S) was carried out in bulk using polyazoester prepared by the reaction of polyethylene glycol with molecular weight of 3000 and 4,4′-azobis(4-cyanopentanoyl chloride) as initiator and CuCl₂/2,2′-bipyridine (bpy) catalyst system to yield poly(ethylene glycol-b-styrene) block copolymer. The block copolymers were characterized ¹H NMR, FT-IR spectroscopy and GPC. The ¹H NMR, and FT-IR spectra showed that formation of poly(ethylene glycol-b-styrene) block copolymer. The polydispersities of block copolymers were observed between from 1.49 and 1.98 GPC measurements.     

Synthesis of well‐defined comblike hydroxy‐functionalized atactic polystyrene promoted by metallocene/tin/poly(phenyl glycidyl ether)‐co‐formaldehyde

Well‐defined comblike atactic polystyrene functionalized with hydroxyl groups was synthesized via living/controlling radical polymerization promoted by metallocene complexes in the presence of poly(phenyl glycidyl ether)‐co‐formaldehyde as the initiator and Sn as a reducing agent. The effect of the polymerization conditions, such as the ratio of initiator to monomer, temperature, and polymerization time, and the structure of the metallocene complex on the polymerization process were investigated. The resulting polymers were characterized by gel permeation chromatography, multiangle laser light scattering, ¹H‐NMR, and ¹³C‐NMR. The results show that the polymer had a narrow molecular weight distribution in the range 1.1–1.4 and the number‐average molecular weight of the polymer linearly depended on the monomer conversion within the polymerization timescale, which confirmed that living radical polymerization characteristics prevailed in the polymerization process. Both the number of arms and the number of hydroxyl groups in each polymer molecule were about four, which suggested that they arose from the epoxy functional groups of the initiator. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Hyperbranched polymers from divinylbenzene and 1,3-diisopropenylbenzene through anionic self-condensing vinyl polymerization

Hyperbranched polymers were synthesized using anionic self-condensing vinyl polymerization (ASCVP) by forming ‘inimer’ (initiator within a monomer) in situ from divinylbenzene (DVB) and 1,3-diisopropenylbenzene (DIPB) using anionic initiators in THF at −40 °C. The reaction of equimolar amounts of DVB and nBuLi results in the formation of hyperbranched poly(divinylbenzene) through self-condensing vinyl polymerization (SCVP). The hyperbranched polymers were invariably contaminated with small amount of gel (<15%). No gelation was observed when using DIBP with anionic initiators. The presence of monomer-polymer equilibrium in the SCVP of DIPB restricts the growth of hyperbranched poly(DIPB). The inimer synthesized from DIPB at 35 °C undergoes intermolecular self-condensation to different extent depending on the nature of anionic initiator at −40 °C. The molecular weight of the hyperbranched polymers was higher when DPHLi was used as initiator. A small amount of styrene ([styrene]/[Li⁺]=1) was used to promote the chain growth by inducing cross-over reaction with styrene, and subsequent reaction of styryl anion with isopropenyl groups of inimer/hyperbranched oligomer. The hyperbranched polymers were soluble in organic solvents and exhibited broad molecular weight distribution (2<M_w/M_n<17).     

A new polymerization method and kinetics for acrylamide: Aqueous two‐phase polymerization

The concept of aqueous two‐phase polymerization and a new polymerization method for the preparation of water‐soluble polymers are presented. The phase diagram of poly(acrylamide) (PAAm)‐poly (ethylene glycol) (PEG)‐water two‐phase system was measured by the gel permeation chromatography (GPC). The aqueous two‐phase of PAAm‐PEG‐water system can be easily formed. The critical concentration of phase separation was affected by the molecular weight of PEG. The aqueous two‐phase polymerization of acrylamide (AAm) has been successfully carried out in the presence of PEG by using ammonium persulfate (APS) as the initiator. The polymerization behaviors with varying concentration of AAm, initiator and PEG, the polymerization temperature, the molecular weight of PEG, and emulsifier types were investigated. The activation energy of aqueous two‐phase polymerization of AAm was 132.3 kJ/mol. The relationship of initial polymerization rate (R_p0) with APS and AAm concentrations was R_p0 ∝ [APS]^0.72 [AAm]^1.28. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Bis(perfluoro-2-n-propoxyethyl)diacyl peroxide initiated homopolymerization of vinylidene fluoride (VDF) and copolymerization with perfluoro-n-propylvinylether (PPVE)

Vinylidenefluoride (VDF) has been homopolymerized and copolymerized with perfluoro-n-propylvinylether (PPVE) using bis(perfluoro-2-n-propoxyethyl)diacyl peroxide (BPPP) as the initiator in CF₂ClCFCl₂. The polymers obtained were characterized with ¹⁹F NMR and ¹H NMR spectroscopy, DSC and TGA. The ¹⁹F NMR spectra were used to determine the polymer microstructures and end groups. Both PVDF and poly(VDF–PPVE) were terminated on both chain ends by CF₃CF₂CF₂OCF(CF₃)∼ arising from the decomposition of the initiator. The concentration of end groups was used to assess the molecular weight of the polymers. Using the Fine–Ross method, the reactivity ratios of both monomers were determined (r_VDF ∼ 1.06, r_PPVE ∼ 0). The T_g of poly(PPVE) (−10.3 °C) was determined using the T_gs of VDF/PPVE copolymers with different compositions and the Flory–Fox equation. A new method to produce a modified PVDF or VDF copolymer for powder coatings with higher thermal stability was also developed.     

Kinetic study on the poly(methyl methacrylate) seeded soapless emulsion polymerization of styrene. I. Experimental investigation

In this work, methyl methacrylate (MMA) and styrene (ST) were used as monomers in the first stage and second stage of polymerization, respectively, and potassium persulfate (K₂S₂O₈) was used as the initiator to synthesize the poly(methyl methacrylate)-polystyrene (PMMA/PS) composite latex by the method of two-stage soapless emulsion polymerization, i.e., PMMA seeded soapless emulsion polymerization of styrene. The morphology of the latex particles was observed by transmission electron microscopy (TEM). It showed that the composite latex particles had a core–shell structure. The particlesize distribution of the composite latex was very uniform. The kinetic data of seeded soapless emulsion polymerization showed that the square root of polymer yield (Wp)^1/2 was proportional to the reaction time in the earlier period of the reaction. The slope of the line of (Wp)^1/2 vs. reaction time was independent of the content of the seed, but proportional to 0.5 power of the initiator concentration. The gel effect was apparent after monomer droplets disappeared. A glassy effect was found in the latter period of the reaction. The number-average molecular weight of the polymers increased but the weight-average molecular weight of the polymers decreased with decrease of the MMA/ST weight ratio. The number- and weight-average molecular weight increased with decreasing the temperature significantly. © 1995 John Wiley & Sons, Inc.     

Metathesis ring opening polymerization of 5,6-dimethylenebicyclo[2.2.1]hept-2-ene

5,6-Dimethylenebicyclo[2.2.1]hept-2-ene ( I ) polymerizes in the presence of the two-component ring opening metathesis polymerization (ROMP) initiators WCl₆/(CH₃)4Sn and MoCl₅/(CH₃)4Sn. The product polymers were insoluble in all of many solvents investigated and are presumably cross-linked. The product polymers were investigated by IR and solid state ¹³C NMR spectroscopy, which established that the material consisted predominantly of poly(1,4-(2,3-dimethylene-cyclopentylene)vinylene) ( II ). A possible alternative route to II via thermal dehydrochlorination of poly(1,4-(2,3-bis(chloromethyl)cyclopentylene) vinylene) ( IV ) was also examined.     

Grafted polytriphenylamines synthesized by atom transfer radical polymerization in tandem with oxidative polycondensation

Arylamine polymers are among the most studied conducting polymers due to a whole range of interesting properties and applications. In this paper, we describe the synthesis of soluble and processable electroactive poly(triphenylamine-g-oligostyrene) by two polymerization methods in tandem. In the first step, oligostyrene macromonomers with well-defined molecular weight, polydispersity and chain-end functionality were obtained by radical-controlled polymerization (i.e., atom transfer radical polymerization, ATRP) of styrene. The styrene oligomerization was carried out using a new triphenylamine-based initiator, [4-(diphenylamino)benzyl 2-bromo-2-methylpropanoate], cuprous bromide as co-initiator and bipyridine as ligand, at 100 °C, in bulk. Using two feed molar ratios of components: [styrene]₀:[initiator]₀:[CuBr]₀:[bipyridine]₀, two macromonomers with M _n = 9,900; M _w/M _n = 1.25 and M _n = 3,460; M _w/M _n = 1.22, respectively, were synthesized. The presence of triphenylamine moiety at one end of the macromonomer allowed the chemical and electrochemical polymerization of macromonomers to polytriphenylamine brushes having short oligostyrene grafts in every structural unit. The oligostyrene substituents confer processability and good solubility in common organic solvent characteristics for polystyrene while preserving the optoelectronic properties of arylamine-conjugated main chain. The chemical oxidative polymerization of macromonomer was carried out using iron (III) chloride dissolved in nitrobenzene. The redox behavior of the initiator, macromonomer and graft polymer was investigated by cyclic voltammetry. In all cases, it was observed that the reversible oxido-reduction of arylamine sites was accompanied by irreversible oxidative electropolymerization by free-para positions of triphenylamine substituents and deposition of thin films on working electrode. The structures of the initiator, macromonomers and graft copolymers were determined by Fourier transform infrared, ¹H and ¹³C NMR spectroscopy. The absorption and fluorescence spectroscopy have revealed absorption and emission maxima characteristics for triphenylamine group. DSC studies have confirmed glass transitions characteristics for styrene oligomers.