Swelling of thin films. I. Acrylamide–N-isopropylacrylamide copolymers in water

The swelling curves of 6μ films of low conversion homopolymers and copolymers of acrylamide (AM) and N-isopropylacrylamide (NIPAM) were obtained in water by an optical microscope technique. Poly(AM) swelled appreciably faster than poly(NIPAM) but there was no apparent correlation between overall swelling rate and copolymer composition. A 57/43 (mole %) AM–NIPAM copolymer swelled fastest. Sequence distribution calculations indicated that its backbone structure tended toward comonomer alternation, which might reduce the extent of hydrogen bonding in the film. The amount of water sorbed during swelling, as approximated from increasing film thickness, was proportional to the square root of time and agreed well with previous work in the literature. Homopolymer films from runs of ca. 50% conversion consistently swelled slower than their low conversion counterparts, probably due to branching and increased entanglements. Heating also promoted slower film swelling due to a tightening of the film structure and/or a low degree of imidization. Monomer reactivity ratios and Alfrey-Price Q and e values for NIPAM were calculated. Cloud points of 5% aqueous solutions of the copolymers were measured and found to decrease with increasing NIPAM content.     

THERMOPROCESSIBLE HYDROGELS. I. SYNTHESIS AND PROPERTIES OF POLYACRYLAMIDES WITH PERFLUOROALKYL SIDE CHAINS

ABSTRACT

Copolymers composed of acrylamide (AM), N,N-dimethylacrylamide (DMAM), N-isopropylacrylamide (NIPAM) and 2-(N-ethyl-perfluorooctanesulfonamido) acrylamide (FOSA) were synthesized by free radical polymerization. The chemical structure of the resulting polymers was characterized with NMR spectroscopy and thermal properties were measured by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). ¹H-NMR spectra of the copolymers of NIPAM with FOSA showed that FOSA was incorporated quantitatively. The glass transition temperature (T_g) of the copolymers and the terpolymers decreased with increasing FOSA content. The T_gs, however, were higher than predicted for a random copolymer by the Fox equation, which was attributed to microphase separation of the hydrophobic, fluorinated species. Copolymers of AM and FOSA became discolored above 180°C due to formation of cyclic imide and nitrile moieties through cyclization or dehydration of amide groups. The equilibrium water sorption of the copolymers decreased with increasing FOSA content, but increasing FOSA suppressed the water desorption kinetics. Water sorption and thermal stability were improved by terpolymerization of AM, NIPAM, DMAM and FOSA.     

Interactions of sodium dodecyl sulfate with acrylamide –N-isopropylacrylamide) statistical copolymer

 Poly(N-isopropylacrylamide) (PNIPAM) precipitates out of water around 32 °C. This critical temperature is raised when hydrophilic acrylamide sequences are present on the polymer chain. We have used neutron scattering to study the structural properties of a statistical copolymer containing acrylamide and N-isopropylacrylamide segments at different temperatures and its interactions with an anionic surfactant, sodium dodecyl sulfate (SDS). At low temperatures, the copolymer behaves as a swollen polymer coil. With an increase in temperature, intermolecular attractions are observed, and close to the critical temperature of the copolymer, microphase separation is observed. Here, the structure consists of dense nodules of hydrophobic sequences stabilized by hydrophilic sequences. In the presence of a small amount of SDS, additional colloidal stability is observed: the nodule size is decreased. At high SDS concentration, the copolymer is completely solubilized at all temperatures studied and the structure of the polymer–surfactant complex resembles the “necklace” structure obtained for the homopolymer PNIPAM–SDS system. Received: 11 November 1999 Accepted: 15 December 1999     

Microphase separation of cationic poly(N-isopropylacrylamide) copolymers in water: Effect of the migration of charges

The structures of aqueous copolymer solutions have been examined through small angle neutron scattering. The copolymers contained mostly N-isopropylacrylamide (NIPAM) monomers. Poly (NIPAM) solutions have a lower critical solution temperature (LCST), above which the macromolecules separate from water. A small fraction of ionizable N,N-[(dimethylamino) propyl] methacrylamide (MADAP) monomers was introduced into the macromolecules. This had dramatic consequences on the solution behavior at temperatures above the LCST of PNIPAM, where phase separation would have been expected for the homopolymer. When all MADAP monomers were ionized, it was found that the solutions resisted the phase separation. At short spatial scales, the chains were collapsed but at large scales they formed branched aggregates that did not separate out of water. When only half of the MADAP monomers are ionized, the electrical charges were able to redistribute themselves along the chains. In this case, the rise in temperature caused a microphase separation where the electrical charges were relocated on a fraction of the chains that remained in solution.The other chains (or section of chains) formed large nodules of a polymer rich phase.     

Coil-to-globule transitions of interfacial copolymers in better than theta-solvents

Experimental studies of the coil-to-globule transitions exhibited in better than -solvents by interfacial copolymers ofN-isopropylacrylamide and acrylamide imply that a lower bound for the value of n in then-clusters of poly(N-isopropylacrylamide) (PNIPAM) is 3. The corresponding upper bound is therefore likely to be 5 or 6. Statistical copolymers of PNIPAM containing upwards of 0.75 mole fraction of acrylamide (whose homopolymer does not itself displayn-clustering) exhibited this transition, which disappeared at higher mole fractions of acrylamide. Interfacial homopolymers ofN-ethylacrylamide and its statistical copolymers withN-isopropylacrylamide exhibitedn-clustering at all compositions.     

Synthesis,characterization, and properties of copolymer of acrylamide and complex pseudorotaxane monomer consisting of cucurbit[6]uril with butyl ammonium methacrylate

The novel copolymers of acrylamide (AM) with complex pseudorotaxane monomer (BAMACB) of butyl ammonium methacrylate (BAMA) and cucurbit[6]uril (CB[6]) were prepared via free‐radical polymerization in aqueous solution. The copolymers containing pseudorotaxane (PAM/BAMACB) were characterized by ¹H‐NMR, FTIR, elemental analysis, TGA, and DSC. The glass transition temperature (T_g) of the copolymer PAM/BAMACB are higher than that of the copolymer of acrylamide and butyl ammonium methacrylate (PAM/BAMA) because of the enhanced rigidity and the bulky steric hindrance of BAMACB side chain in PAM/BAMACB. The molecular weights of copolymer PAM/BAMACB were obtained via static light scattering. The hydrodynamic radii of coils or aggregates were investigated by dynamic light scattering. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5999–6008, 2008     

Linear and comb‐like acrylonitrile/N‐isopropylacrylamide copolymers synthesized by the combination of RAFT polymerization and ATRP

We describe the synthesis of three novel thermoresponsive copolymers of acrylonitrile (AN) with N‐isopropylacrylamide (NIPAM) by a combination of reversible addition‐fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP). Linear copolymer polyacrylonitrile (PAN)‐b‐PNIPAM was directly prepared by RAFT polymerization. Comb‐like copolymers were synthesized by ATRP using brominated AN/2‐hydroxyethyl methacrylate copolymers as macroinitiators, which were prepared by RAFT polymerization. FT‐IR, NMR, and GPC were employed to characterize the synthesized copolymers. Results indicate that the polymerization processes can be well controlled and the resultant copolymers have well‐defined structures as well as narrow polydispersity. Then dense films were fabricated from these thermoresponsive copolymers and the surface wettability was evaluated by water contact angle measurements at different temperatures. It is found that the surface wettability is temperature‐dependant and both the transition temperature and decrement of water contact angle are affected by the copolymer shapes as well as the length of PNIPAM blocks. Considering the excellent fiber‐ and membrane‐forming properties of PAN‐based copolymers, the obtained thermoresponsive copolymers are latent materials for functional fibers and membranes. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 92–102, 2009     

Synthesis and Characterization of Poly(N-isopropylacrylamide) and Poly(vinyl acetate) Diblock Copolymers via MADIX Process

The synthesis of diblock copolymers of poly(N-isopropylacrylamide) (PNIPAM) and poly(vinyl acetate) (PVAc) was performed by macromolecular design via interchange of xanthates (MADIX) process. Following the preparation of methyl (isopropoxycarbonothioyl) sulfanyl acetate (MIPCTSA) as chain transfer agent, it was reacted with vinyl acetate to obtain PVAc macro-chain transfer agent. Then, block copolymerization was completed by successive addition of N-isopropylacrylamide (NIPAM). ¹H NMR spectroscopy confirmed the presence of both blocks in the copolymer structure, with the expected composition based on the feed ratio. Size Exclusion Chromatography (SEC) was used to investigate the relative values of molecular characteristics. Only 20% of PVAc was converted to block copolymer. The resultant block copolymer structures were further examined in terms of their morphologies as well as critical micelle concentration (CMC) by using ESEM and Fluorescence Excitation Spectroscopic techniques, respectively. Morphological characterization confirmed amphiphilic block copolymer formation with the existence of mainly ca. 100 nm well distributed micelles. The thermo responsive amphiphilic behavior of the block copolymer solutions were followed by Dynamic Light Scattering (DLS) technique.     

Synthesis and phase separation of amine-functional temperature responsive copolymers based on poly(N-isopropylacrylamide)

Free radical copolymerizations of N-isopropyl acrylamide (NIPAM) and cationic N-(3-aminopropyl) methacrylamide hydrochloride (APMH) were investigated to prepare amine-functional temperature responsive copolymers. The reactivity ratios for NIPAM and APMH were evaluated in media of different ionic strength (r_NIPAM = 0.7 and r_APMH = 0.7-1.2). Phase separation behavior of the random copolymers with only 5 mol% of the APMH was found to be suppressed in pure water at temperatures up to 45 °C due to electrostatic repulsion among the cationic amine groups randomly distributed along the copolymer chain. Alternate sequential addition of PNIPAM/APMH mixtures and pure NIPAM was used to provide increased control of the location of APMH units along the chain. Consequently (close to) homo-PNIPAM block(s) were formed as evidenced by its characteristic phase transition at 33 °C. The influences of the monomer feeding time and feeding interval time to the APMH distribution were investigated to prepare copolymers with thermo-induced phase separation under physiologically relevant temperature and to determine the extent of conjugation to poly(ethylene oxide).     

Tuning block copolymer phase behavior with a selectively associating homopolymer additive

We use polymer random phase approximation (RPA) theory to calculate the microphase separation transition (MST) spinodal for an AB + C diblock copolymer–homopolymer blend where the C homopolymers are strongly attracted to the A segment of the copolymers. Our calculations indicate that one can shift the MST spinodal value of the A ? B segmental interaction parameter (χ_ABN)_S to significantly lower values [i.e., (χ_ABN)_S < 10.5] upon the addition of a selectively attractive C homopolymer. For a sufficiently attractive C homopolymer, (χ_ABN)_S can be pushed to negative values, indicating microphase separation in what would appear to be a completely miscible diblock copolymer. Furthermore, we show that microphase separation can occur in diblock copolymer–homopolymer blends where the segmental interactions between all polymer constituents are attractive. By tuning the value of (χ_ABN)_S with a homopolymer additive, one is therefore able to tune the effective copolymer segregation strength and thus dramatically affect the blend phase behavior. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2083–2090, 2009     

Synthesis and characterization of well‐defined diblock and triblock copolymers of poly(N‐isopropylacrylamide) and poly(ethylene oxide)

Well‐defined diblock and triblock copolymers composed of poly(N‐isopropylacrylamide) (PNIPAM) and poly(ethylene oxide) (PEO) were successfully synthesized through the reversible addition–fragmentation chain transfer polymerization of N‐isopropylacrylamide (NIPAM) with PEO capped with one or two dithiobenzoyl groups as a macrotransfer agent. ¹H NMR, Fourier transform infrared, and gel permeation chromatography instruments were used to characterize the block copolymers obtained. The results showed that the diblock and triblock copolymers had well‐defined structures and narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight < 1.2), and the molecular weight of the PNIPAM block in the diblock and triblock copolymers could be controlled by the initial molar ratio of NIPAM to dithiobenzoate‐terminated PEO and the NIPAM conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4873–4881, 2004     

Water-soluble copolymers. XII. Copolymers of acrylamide with sodium-3-acrylamido-3-methylbutanoate: Synthesis and characterization

The copolymerization of acrylamide (AM) with sodium-3-acrylamido-3-methylbutanoate (NaAMB) has been studied. The value of r₁r₂ has been determined to be 0.56 for the AM–NaAMB pair. The molecular weights of the copolymers were relatively unaffected by monomer feed ratios. The copolymer microstructures, including run numbers and sequence distributions, were calculated from the reactivity ratios. The solution properties of the AM–NaAMB copolymers, as well as the NaAMB homopolymer, will be reported in a subsequent paper.     

Preparation and characterization of thermoresponsive isopropylacrylamide–hydroxyethylmethacrylate copolymer gels

A random copolymer of N-isopropylacrylamide and 2-hydroxyethylmeth-acrylate, poly(NIPAM-co-HEMA), having thermoresponsive character was prepared bya redox copolymerization method. Poly(ethylene glycol), PEG 4000 was included in the copolymerization recipe to increase the thermoresponsivity of copolymeric structure. Poly(NIPAM-co-HEMA) copolymer gels having more elastic character and higher mechanical strength relative to poly(NIPAM) gel could be achieved by the proposed copolymerization procedure. The equilibrium and dynamic response against the temperature were investigated for the gel matrices produced by changing the initial NIPAM/HEMA mol ratio and PEG 4000 concentration in the copolymerization mixture. The effective diffusion coefficient of water within the gel matrix was estimated for either swollen or shrunken states by applying an unsteady-state diffusion model on the dynamic swelling and shrinking behaviors of gel matrix prepared in the cylindrical form. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 527–541, 1998     

Highly active,thermo‐responsive polymeric catalytic system for reuse in aqueous and organic CuAAC reactions

Tris‐(benzyltriazolylmethyl)amine (TBTA) has been immobilized onto a styrenic monomer and subsequently copolymerized with N‐isopropyl acrylamide (NIPAM) to afford catalytically active thermo‐responsive copolymers for copper assisted click chemistry. P(TBTA‐co‐NIPAM) copolymers were synthesized with incorporation of between 2 and 10 ligand units per chain and tuneable molecular weight (28–148 kDa). A combination of ¹H NMR spectroscopy, size exclusion chromatography (SEC) and elemental analysis (EA) confirmed the controlled synthesis of these polymers and allowed for quantification of the degree of TBTA‐functionalized monomer incorporation. After loading with copper(I) bromide, this homogeneous catalyst system was added to a water/ethyl acetate two‐phase system. Using this biphasic system aqueous click reactions could be performed at room temperature, while organic click chemistry could be performed above the cloud point temperature of the catalyst system. The polymer catalyst system could be regenerated via extraction by making use of its lower critical solution temperature (LCST)‐behavior, and then reused for further copper(I) catalyzed azide‐alkyne cycloaddition (CuAAC) reactions. While a reduced catalytic activity is observed as a result of copper leaching in aqueous click reactions, the recycling experiments in the organic phase demonstrated that this copolymer supported system allows for efficient recycling and reuse. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Poly(N‐vinylpyrrolidone)–polydimethylsiloxane amphiphilic ABA triblock copolymers

Triblock copolymers of N‐vinylpyrrolidone (NVP) and polydimethylsiloxane (PDMS) were synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization using two different types of difunctional telechelic PDMS‐based dixanthate macroinitiators. The incorporation of PDMS into the triblock copolymers was evidenced by ¹H NMR spectroscopy and varied between 4 mol % and as high as 20 mol %, dependent on reaction time and monomer conversion. The copolymer homogeneity was characterized in terms of molecular weight distribution determined by GPC to estimate the level of control over the chain length. Monomodal molecular weight distributions were observed, and ¹H NMR spectroscopy indicated the copolymers had number average molecular weights (M_n) ranging between 28,000 and 160,000 g/mol. In addition, thin film phase separation and critical micelle concentrations for these copolymers were analyzed via transmission electron microscopy and surface tension measurements, respectively. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3387–3394     

Aqueous solution properties of pH‐responsive AB diblock acrylamido–styrenic copolymers synthesized via aqueous reversible addition–fragmentation chain transfer

Here we report the synthesis and solution characterization of a novel series of AB diblock copolymers with neutral, water‐soluble A blocks consisting of N,N‐dimethylacrylamide and pH‐responsive B blocks of N,N‐dimethylvinylbenzylamine. To our knowledge, this represents the first example of an acrylamido–styrenic block copolymer prepared directly in a homogeneous aqueous solution. The best blocking order [with poly(N,N‐dimethylacrylamide) as a macro‐chain‐transfer agent] yielded well‐defined block copolymers with minimal homopolymer impurities. The reversible aggregation of these block copolymers in aqueous media was studied with ¹H NMR spectroscopy and dynamic light scattering. Finally, an example of core‐crosslinked micelles was demonstrated by the addition of a difunctional crosslinking agent to a micellar solution of the parent block copolymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1724–1734, 2004     

Temperature-controlled release of catechol dye in thermosensitive phenylboronate-containing copolymers: A quantitative study

The reversible complex formation between two phenylboronic acid bearing copolymers and the catechol dye Alizarin Red S (ARS) was studied by dialysis experiments coupled with UV-visible spectroscopy. The first copolymer based on N-isopropylacrylamide (NIPAM) is thermosensitive, whereas the second one based on N,N-dimethylacrylamide (DMAM) is not. The investigation resulted in the quantitative determination of the host-guest binding constants at two different temperatures at pH 7.4 in phosphate buffer. Above the phase transition temperature Tp of the thermosensitive copolymer, the binding constant decreases by a factor of 6, twice more than in the case of the non-thermosensitive copolymer. This behaviour is related to the coil-to-globule transition of NIPAM-based copolymer, which above Tp expels the dye marker.     

Facile synthesis of thermoresponsive block copolymers of N-isopropylacrylamide using heterogeneous controlled/living nitroxide-mediated polymerizations in supercritical carbon dioxide

A new protocol for preparation of thermoresponsive poly(N-isopropylacrylamide, NIPAM) containing block copolymers is described. It involves two successive heterogeneous controlled/living nitroxide-mediated polymerizations (NMPs) in supercritical carbon dioxide (scCO₂) using N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)]nitroxide (SG1), as the nitroxide. Precipitation NMPs give narrow dispersity macroinitiators (MIs), and a first report of the controlled/living polymerization of N,N-dimethylacrylamide (DMA) in scCO₂ is described. The MI is then used in an inverse suspension NMP of NIPAM in scCO₂ resulting in the efficient preparation of block copolymers containing DMA, tert-butyl acrylate and styrene. Aqueous cloud point temperature analysis for poly(DMA)-b-poly(NIPAM) and poly(acrylic acid)-b-poly(NIPAM) shows a significant dependence on poly(NIPAM) chain length for a given AB block copolymer.     

Synergistic depression of volume phase transition temperature in copolymer microgels

Microgels consisting of poly-N,N-diethylacrylamide (PDEAAM) and copolymer microgels consisting of N,N-diethylacrylamide-co-N-isopropylacrylamide (PDEAAM-co-PNIPAM) have been synthesized via free radical polymerizations. The volume phase transition of the microgels in aqueous solution was investigated by means of dynamic light scattering. All samples revealed a volume phase transition upon heating and the size change was fully reversible. An unusual dependence of transition temperature on the composition of the copolymer microgels was observed and samples were obtained with a transition temperature that was lower than that of both corresponding homopolymer particles. This synergistic behavior could be caused by strong hydrogen bonding between the mono- and the disubstituted acrylamide repeating units at nearly equimolar composition of the microgel.     

Facile synthesis of triple‐stimuli (photo/pH/thermo) responsive copolymers of 2‐diazo‐1,2‐naphthoquinone‐mediated poly(N‐isopropylacrylamide‐co‐N‐hydroxymethylacrylamide)

A series of poly(N‐isopropylacrylamide‐co‐N‐hydroxymethylacrylamide) P(NIPAM‐co‐NHMA) copolymers were firstly synthesized via free radical polymerization. Then, the hydrophobic, photosensitive 2‐diazo‐1,2‐naphthoquinone (DNQ) molecules were partially and randomly grafted onto P(NIPAM‐co‐NHMA) backbone through esterification to obtain a triple‐stimuli (photo/pH/thermo) responsive copolymers of P(NIPAM‐co‐NHMA‐co‐DNQMA). UV‐vis spectra showed that the lower critical solution temperature (LCST) of P(NIPAM‐co‐NHMA) ascended with increasing hydrophilic comonomer NHMA molar fraction and can be tailored by pH variation as well. The LCST of the P(NIPAM‐co‐NHMA) went down firstly after DNQ modification and subsequently shifted to higher value after UV irradiation. Meanwhile, the phase transition profile of P(NIPAM‐co‐NHMA‐co‐DNQMA) could be triggered by pH and UV light as expected. Thus, a triple‐stimuli responsive copolymer whose solution properties could be, respectively, modulated by temperature, light, and pH, has been achieved. These stimuli‐responsive properties should be very important for controlled release delivery system. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2763–2773, 2009