Synthesis of Hydroxyl‐Terminated Poly(vinylcarbazole‐ran‐styrene) Copolymers by Nitroxide‐Mediated Polymerization

A series of poly(vinylcarbazole‐ran‐styrene) copolymers with terminal hydroxyl groups were synthesized using nitroxide mediated polymerization (NMP) with the hydroxyl‐functional initiator VA‐086 and TEMPO as the mediator at 130 °C. Polymerizations were studied as a function of vinylcarbazole feed content, target molecular weight, and VA‐086/TEMPO ratio. The characterization of the copolymers was done by GPC and NMR. For feed concentrations of 40 mol‐% vinylcarbazole, copolymers with vinylcarbazole concentration up to 33 mol‐% could be obtained with narrow molecular weight distributions (PDI = 1.35) and exhibit pseudo‐“living” character up to conversions of about 20% if the target molecular weight was >100 kg · mol^?1. ¹H NMR indicated that the hydroxyl group was retained sufficiently with a functionality typically of about 0.7 hydroxyl groups per chain. Copolymers synthesized with higher vinylcarbazole feed content exhibited slower kinetics and were less controlled, resulting in much broader molecular weight distributions. The absence of control could be attributed to the absence of thermal initiation by vinylcarbazole which is advantageous toward controlling the radical concentration during the polymerization.

     

Nitroxide‐Mediated Radical Polymerization of N‐tert‐Butylacrylamide

The nitroxide‐mediated polymerization of N‐tert‐butylacrylamide (TBAM) in DMF at 120 °C using SG1/DEPN and AIBN has been investigated. Linear growth in number‐average molecular weight ( ) versus conversion and narrow molecular weight distributions (MWDs) with high livingness were obtained up to ≈8 000 g · mol^?1. For higher molecular weights, the MWDs gradually became broader with low molecular weight tailing, and deviated downwards from theoretical values. Quantitative analyses of MWDs, along with specifically designed conventional radical polymerizations at 120 °C, were consistent with chain transfer to monomer limiting the attainable . This finding can be equally applied to existing literature polymerizations of TBAM.

     

Synthesis,Characterization, and Thermal Properties of Block Copolymers Containing Poly(styrene‐co‐4‐vinylpyridine) and Poly(styrene‐co‐butyl acrylate) by Controlled Radical Polymerization

Radical polymerization of styrene and mixtures of styrene and 4‐vinylpyridine was performed in the presence of 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) producing polymers with controlled molecular weights and molecular weight distributions. The living nature of these polymers was confirmed by using them as macroinitiators in the block copolymerization of styrene and butyl acrylate. The thermal properties of the synthesized statistical diblock copolymers measured by differential scanning calorimetry indicated that a phase‐separated morphology was exhibited in most of the block copolymers. The results were confirmed by transmission electron microscopy (TEM) and small angle X‐ray scattering (SAXS) showing microphase‐separated morphology as is known for homo A‐B diblock polymers.

SAXS of a block copolymer synthesized from S/V 70:30 macroinitiators (03) with one detected T_g.     

Terpyridine‐Terminated Homo and Diblock Copolymer LEGO Units by Nitroxide‐Mediated Radical Polymerization

Summary: Novel block copolymers were synthesized in a controlled fashion by nitroxide‐mediated radical polymerization starting from a terpyridine‐modified alkoxyamine. An important feature for controlling the efficiency of the polymerization is the presence of excess nitroxide, responsible for the initial rate of deactivation, which eventually leads to a decrease of the polydispersity indices of the desired block copolymer. The materials obtained were characterized by means of ¹H NMR, UV‐vis spectroscopy, and GPC. The complexation of the terpyridine ligands resulted in the formation of A‐B‐[Ru]‐C, A‐B‐[Ru]‐B‐A, and A‐B‐[Fe]‐B‐A metallo‐supramolecular block copolymers.

Telechelic polymers bearing a terpyridine end‐group at the α‐position and a nitroxide at the ω‐position were prepared in a living fashion by nitroxide‐mediated polymerization.     

Network Formation in Nitroxide‐Mediated Radical Copolymerization of Styrene and Divinylbenzene in Miniemulsion

Summary: Polymer network formation in controlled/living radical crosslinking copolymerization of S/DVB initiated by a poly(S)‐TEMPO macroinitiator in aqueous miniemulsion at 125 °C is investigated. The crosslinking proceeded differently in miniemulsion (heterogeneous systems) and in bulk/solution (homogeneous systems), with markedly lower apparent pendant reactivity in miniemulsion. The relative rate of DVB consumption was lower in miniemulsion than in bulk/solution. It is proposed that the interface between the particle (monomer droplet at time = 0) and the aqueous phase may play an important role during the crosslinking process. The presence of tetradecane as a hydrophobe in the monomer droplets strongly influenced both the pendant reactivity and the molecular weight distributions in miniemulsion, whereas only small effects were observed in the corresponding bulk/solution polymerizations. It is believed that this is related to previous results of the hydrophobe promoting migration of poly(DVB) to the interface of toluene droplets in aqueous emulsion. The results suggest novel approaches towards control of polymer network development in crosslinking radical polymerizations.

Total (filled symbols) and intermolecular (open symbols) pendant conversions for TEMPO‐mediated radical copolymerization of S/DVB.     

Nitroxide‐Mediated Radical Polymerization with Bisaminooxy Compounds as Initiators – Controlled Biradical Polymerization

Summary: The bisaminooxy compounds Bis‐TEMPO and Bis‐TIPNO derived from 2,2,6,6‐tetramethyl‐piperidine‐1‐oxyl (TEMPO) and 2,2,5‐trimethyl‐4‐phenyl‐3‐azahexane‐3‐oxyl (TIPNO) were applied as “biradical initiators” for the nitroxide‐mediated radical polymerization (NMRP) of styrene and n‐butyl acrylate. It was shown by comparison with analogous alkoxyamines as unimolecular initiators and mixing experiments of mono‐ and biradical species, that in the case of the biradical initiators chain growth occurs at both sides under NMRP conditions. This enables a two‐step synthesis of A‐B‐A‐triblock copolymers. Kinetics and molecular mass development were investigated for the controlled biradical polymerization of styrene at different initiator concentrations, temperatures, and with addition of acetic anhydride as accelerator. For the controlled biradical polymerization of n‐butyl acrylate with Bis‐TIPNO, the effect of added free nitroxide relative to the initiator concentration was studied. The poly(styrene‐block‐n‐butyl acrylate‐block‐styrene) copolymers with higher block length prepared by this method show two glass transition temperatures, which indicates microphase separation of the polymer blocks.

Structure of poly(styrene‐block‐n‐butyl acrylate‐block‐styrene), synthesized by nitroxide‐mediated radical polymerization with Bis‐TIPNO as initiator.     

Gelation and Hollow Particle Formation in Nitroxide‐Mediated Radical Copolymerization of Styrene and Divinylbenzene in Miniemulsion

Network formation in the nitroxide‐mediated cross‐linking copolymerization of styrene and divinylbenzene (3 or 8.2 mol‐% relative to total monomer) using the nitroxide 2,2,6,6‐tetramethylpiperidinyl‐1‐oxy (TEMPO) at 125 °C can proceed markedly differently in aqueous miniemulsion compared to the corresponding solution polymerization depending on the organic‐phase composition. When the organic phase comprises 54 vol‐% of the hydrophobe tetradecane, gelation occurs at much lower conversion in miniemulsion than in solution, and at significantly lower conversion than predicted by Flory–Stockmayer gelation theory. This is proposed to be a result of an effect of the oil–water interface, whereby the concentration of polymer with pendant unsaturations is higher near the interface than in the particle interior.

     

Efficient Synthesis and Copolymerization of Poly(acrylic acid) and Poly(acrylic ester) Macromonomers: Manipulation of Steric Factors

Summary: Macromonomers have been prepared by polymerization of acrylic acid (AA) and tert‐butyl acrylate (tBA) in the presence of the addition‐fragmentation chain transfer (AFCT) agents, ethyl α‐(bromomethyl)acrylate (EBMA) and tert‐butyl α‐(bromomethyl)acrylate (BBMA). Chain transfer constants of 1.25 (EBMA) and 1.14 (BBMA) in the AA polymerization, and 2.42 (EBMA) and 1.75 (BBMA) in the tBA polymerization were obtained. The reduction in molecular weight with increasing concentration of AFCT agent and efficient introduction of 2‐carbalkoxy‐2‐propenyl ω‐end group was indicative of macromonomer formation. Polymerizations were retarded with increasing concentrations of AFCT agent and increases in the absolute concentration of EBMA slowed down the polymerization of AA but not tBA. The difference between EBMA and BBMA was less significant with tBA; more efficient macromonomer synthesis was indicated by less retardation and greater double bond retention at higher conversions. Copolymerizations of poly(AA) and poly(tBA) macromonomers with styrene indicated that the former was more reactive towards the St propagating radical. The results are rationalized in terms of the steric hindrance imposed by the tert‐butyl group. Poly(tBA) macromonomer was successfully hydrolyzed to give an alternative route to the poly(AA) macromonomer.

Reaction mechanism for macromonomer synthesis using AFCT.     

Synthesis of Blockcopolymers P3HT‐b‐PS Using a Combination of Grignard‐Metathesis and Nitroxide‐Mediated Radical Polymerization

The synthesis of π‐conjugated NMRP‐macroinitiators using GRIGNARD‐metathesis polymerization in combination with azide/alkyne‐“click” chemistry has been investigated. Alkoxyamine‐functionalized poly(3‐hexylthiophene)s (P3HTs) have been used for block copolymer preparations in presence of styrene. Molecular weight and molecular weight distribution of the polymers have been determined in SEC‐measurements, while end‐group determination was performed with MALDI‐ToF‐MS. The molecular weight of the P3HT macroinitiators was influenced by the amount of Ni‐catalyst during the GRIM reaction. Those macroinitiators have been used to prepare block copolymers in subsequent nitroxide‐mediated radical polymerization (NMRP). Thin‐layer‐morphologies of the block copolymers were investigated using tapping‐mode AFM. Short and disordered rods were observed, as well as continuous and parallel fibrils.

     

Semicrystalline Macromolecular Design by Nitroxide‐Mediated Polymerization

The syntheses of PODA‐b‐PMA and PODA‐grad‐PMA copolymers using NMP are reported for the first time. The gradient copolymerization of ODA and MA was performed in a semi‐batch system with a continuous addition of MA during ODA polymerization. The results showed that the semi‐batch NMP proceeded in a living fashion, producing well‐defined copolymers with narrow polydispersities and controlled molecular weights. The potentially semicrystalline copolymers were characterized by techniques such as ¹H NMR, SEC and DSC. Their surface crystallization has also been studied by AFM.

     

Synthesis and Characterization of Semicrystalline Polyethylene‐graft‐Poly(acrylic acid) Copolymers

Hydrophilic polyolefin materials were prepared by grafting tBA from PE macroinitiators bearing functionalized norbornene units capable of initiating an ATRP. This method produced semicrystalline graft copolymers (PE‐graft‐PtBA) with narrow molecular weight distributions (1.2–1.4) and tunable tBA content (2–21 mol‐%). Incorporation of tBA resulted in a decrease in crystallinity, but little change in the melting point of the products. Subsequently, the tBA moieties were converted into acrylic acid units through chemical and thermal means to generate PE‐graft‐PAA copolymers. The increased hydrophilicity of the resulting materials was verified by ATR‐IR, solid‐state ¹³C NMR spectroscopy, contact angle measurements, and TGA.

     

Hydrogen Abstraction Followed by Nitroxide‐Mediated Polymerization: Synthesis of 2,7‐Dibromofluorene‐Labeled Polystyrene

Chromophore end‐labeled polystyrene is synthesized using nitroxide‐mediated polymerization (NMP) by decomposing 2‐2′‐azoisobutyronitrile (AIBN) or benzoyl peroxide (BPO) in the presence of fluorene or fluorene derivatives. End‐labeling is dependent on the thermally produced radical species selectively abstracting a hydrogen atom from the 9‐position of the fluorene species prior to initiation of styrene. From gel permeation chromatography (GPC) data and UV–Vis analysis, it is found that AIBN initiation, compared to BPO, leads to a more controlled polymerization system, producing polymers with predictable molecular weights, narrower polydispersity index (PDI) values (<1.3), and higher amounts of fluorene end‐labeling. In terms of the reaction parameters, no consistent trend is observed as a function of the timing of styrene's addition or the temperature at which the hydrogen abstraction phase is performed. Analysis of the chromophore content by UV–Vis spectroscopy demonstrated that the presence of bromine atoms on the 2‐ and 7‐position of the fluorene species leads to higher percent labeling of the chromophore species, presumably due to a more facile abstraction of the hydrogen at the 9‐position.     

A Tandem Controlled Radical Polymerization Technique for the Synthesis of Poly(4‐vinylpyridine) Block Copolymers: Successive ATRP,SET‐NRC,and NMP

Poly(methyl methacrylate)‐block‐poly(4‐vinylpyridine), polystyrene‐block‐poly(4‐vinyl pyridine), and poly(ethylene glycol)‐block‐poly(4‐vinylpyridine) block copolymers are synthesized by successive atom transfer radical polymerization (ATRP), single‐electron‐transfer nitroxide‐radical‐coupling (SET‐NRC) and nitroxide‐mediated polymerization (NMP). This paper demonstrates that this new approach offers an efficient method for the preparation of 4‐vinylpyridine‐containing copolymers.

     

MALDI‐TOF Analysis of Halogen Telechelic Poly(methyl methacrylate)s and Poly(methyl acrylate)s Prepared by Atom Transfer Radical Polymerization (ATRP) or Single Electron Transfer‐Living Radical Polymerization (SET‐LRP)

Poly(methyl methacrylate)s (PMMA)s and poly(methyl acrylate)s (PMA)s are prepared by atom transfer radical polymerization (ATRP) or single electron transfer‐living radical polymerization (SET‐LRP) using methyl dichloroacetate (MDCA) and ethyl dibromoacetate (EDBA) as bifunctional initiators. The chain‐end functionality is determined by MALDI‐TOF mass spectrometry. The target PMMA (M_n = 2000 g mol^?1) and PMA (M_n = 2000 g mol^?1) samples obtained by ATRP of MMA and MA with MDCA as initiator have 12 and 81 mol% bis‐chloro end groups, respectively; those prepared by SET‐LRP have 57 and 100 mol% bis‐chloro end groups, respectively. The PMMAs obtained by ATRP or SET‐LRP with EDBA have no bromine end groups.

     

Synthesis and Thermosensitive Properties of Poly[(N‐vinylamide)‐co‐(vinyl acetate)]s and Their Hydrogels

Free radical copolymerization of water‐soluble N‐vinylamides such as N‐vinylacetamide (NVA) and N‐vinylformamide (NVF) with hydrophobic vinyl acetate (VAc) gave amphiphilic copolymers. The monomer reactivity ratios were determined as r₁ = 5.8 and r₂ = 0.68 (M₁ = NVA, M₂ = VAc) and r₁ = 6.2 and r₂ = 0.37 (M₁ = NVF, M₂ = VAc), respectively. The growing radical of the terminals of N‐vinylamides propagates more favorably for N‐vinylamide monomers than for VAc monomer, resulting in the possible formation of blocky copolymers. It is found that aqueous solutions of these amphiphilic copolymers exhibited a lower critical solution temperature (LCST), depending on their chemical composition, followed by coacervate formation above the LCST. Furthermore, thermosensitive hydrogels could be prepared by the free radical copolymerization of N‐vinylamide and VAc in the presence of the crosslinker butylenebis(N‐vinylacetamide) (Bis‐NVA). The swelling ratios of these hydrogels decreased with an immediate increase in temperature from 20 to 80 °C, and then reversibly increased with decreasing temperature. These hydrogels showed the same thermosensitive properties as linear copolymers of NVF and VAc.

Relationship between LCST and vinyl acetate content in poly(N‐vinylamide‐co‐VAc)s.     

Synthesis and Properties of Novel Fluorinated Poly(phenylene‐co‐imide)s

A new class of high‐performance materials, fluorinated poly(phenylene‐co‐imide)s, were prepared by Ni(0)‐catalytic coupling of 2,5‐dichlorobenzophenone with fluorinated dichlorophthalimide. The synthesized copolymers have high molecular weights ( = 5.74 × 10⁴–17.3 × 10⁴ g · mol^?1), and a combination of desirable properties such as high solubility in common organic solvent, film‐forming ability, and excellent mechanical properties. The glass transition temperature (T_gs) of the copolymers was readily tuned to be between 219 and 354 °C via systematic variation of the ratio of the two comonomers. The tough polymer films, obtained by casting from solution, had tensile strength, elongation at break, and tensile modulus values in the range of 66.7–266 MPa, 2.7–13.5%, and 3.13–4.09 GPa, respectively. The oxygen permeability coefficients ( ) and permeability selectivity of oxygen to nitrogen ( ) of these copolymer membranes were in the range of 0.78–3.01 barrer [1 barrer = 10^?10 cm³ (STP) cm/(cm² · s · cmHg)] and 5.09–6.25, respectively. Consequently, these materials have shown promise as engineering plastics and gas‐separation membrane materials.

     

Xanthate‐Mediated Controlled Radical Polymerization of N‐Vinylcarbazole

Summary: Well‐defined poly(N‐vinylcarbazole) [poly(NVC)] was synthesized by macromolecular design via interchange of the xanthates (MADIX)/reversible addition‐fragmentation chain transfer (RAFT) polymerization. The homopolymers with controlled molecular weights ( = 3 000–48 000) and low polydispersities indices ( = 1.15–1.20) were obtained by the polymerization of NVC with AIBN in the presence of O‐ethyl‐S‐(1‐phenylethyl) dithiocarbonate as a xanthate‐type chain transfer agent (CTA). Good control of the polymerization was confirmed by the linear first‐order kinetic plot, the molecular weight controlled by the monomer/CTA molar ratio, linear increase in the molecular weight with the conversion, and the ability to extend the chains by the second addition of the monomer.

Radical polymerization of NVC in the presence of CTA and plot of number‐average molecular weight (circles) and polydispersity (squares) as a function of conversion.     

Asymmetrically Substituted Poly(diitaconates) Obtained by Reversible Addition‐Fragmentation Chain Transfer (RAFT) Polymerization: Synthesis,Copolymerization Parameters,and Antimicrobial Activity

Asymmetrically substituted poly(diitaconate) copolymers are synthesized from 1‐((N‐tert‐butoxycarbonyl)‐2‐aminoethyl)‐4‐propyl diitaconate (PrIA) and different comonomers (N,N‐dimethyl‐acrylamide, DMAA; acrylic acid; or ((N‐tert‐butoxycarbonyl)‐2‐aminoethyl)methacrylate) by reversible addition–fragmentation chain transfer polymerization (RAFT). The RAFT copolymerization parameters of PrIA and DMAA are r_DMAA = 0.49 and r_PrIA = 0.17, compared to r_DMAA = 0.52 and r_PrIA = 0.54 obtained by free radical copolymerization (FRP). Thus, the RAFT process has a stronger trend to alternating polymerization than the FRP process. The polydispersity index of the RAFT copolymers is around 1.2–1.8, compared to 2.8–2.9 for the corresponding FRP copolymers. After removal of the tert‐butoxycarbonyl protective groups, antimicrobially active synthetic mimics of antimicrobial peptides are obtained. The thus activated poly(PrIA‐co‐DMAA) copolymers (repeat unit ratio 1:1) have an increasing activity against Escherichia coli and Staphylococcus aureus with increasing molar mass. The RAFT copolymers are slightly more active and less toxic than comparable FRP polymers, leading to a higher selectivity for bacteria over mammalian cells. Higher molar fractions of PrIA in poly(PrIA‐co‐DMAA) copolymers (up to 80 mol%) do not increase their antimicrobial activity; reduction of the BuIA content in poly(BuIA‐DMAA) (down to 10 mol%) leads to a loss of activity against both E. coli and S. aureus.     

Radically Crosslinkable Poly(acrylic acid)s From Poly[(tert‐butyl acrylate)‐co‐(3‐aminopropyl vinyl ether)]: Synthesis and Rheological Properties

Acrylic acid copolymers bearing radically polymerizable methacrylic and itaconic moieties are synthesized. Starting from copolymers of tBA and APVE, prepared at different ratios, methacrylic or itaconic amides are obtained via polymer‐analogous reaction. After acidic elimination of isobutylene, polymers with free carbon acids and staggered reactivity can be prepared. Varying amounts of attached acrylamide moieties allow the adjustment of network densities. Rheological properties in HEMA/water matrices during curing are evaluated.