A novel mucoadhesive polymer prepared by template polymerization of acrylic acid in the presence of poloxamer

A new mucoadhesive polymer was prepared by template polymerization of acrylic acid using poloxamer as a template polymer. FTIR results showed that the interpolymer complex was formed by hydrogen bonding between the carboxyl group of poly(acrylic acid) (PAA) and the ether group of poloxamer. The extent of hydrogen bonding in the PAA/poloxamer interpolymer complex increased as the ratio of PAA/poloxamer decreased. The T_g of PAA/poloxamer interpolymer complexes was matched well with the T_g calculated by Gordon‐Taylor's equation than that of their blends. This result suggests that the PAA and poloxamer in the interpolymer complexes are more compatible than their blends. The dissolution rate of PAA/poloxamer interpolymer complexes was much slower than that of their blends, and was dependent on the pH of the medium and the ratio of PAA/poloxamer. The adhesive bond strength of PAA/poloxamer interpolymer complexes to a plastic (polypropylene) plate was greater than their blends or a commercial product, Carbopol 971P NF. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1525–1530, 2001     

Poly(4-vinylpyridine)-based hydrogen bonded side-chain liquid crystal polymers

Novel liquid crystalline (LC) poly(4-vinylpyridine) (PVP)-based side-chain polymers were prepared from PVP and cyanobiphenyl (HOCnB) derivatives through intermolecular hydrogen-bonding between hydroxyl groups of the cyanobiphenyl derivatives and the nitrogen of PVP. PVP was used as a hydrogen bond acceptor polymer. A series of HOCnB having a linear alkoxy chain HOCnH_2n + 1O–(n = 2–6) have been used as H-bond donor. The existence of H-bonding was confirmed using FTIR spectroscopy. The polymeric complexes behave as LC polymers and exhibit stable mesophases. DSC and optical microscopy were used to investigate LC behaviour. All PVP–LC-complexes exhibited stable and homogeneous nematic phases. On increasing spacer length or concentration of the hydrogen bonded mesogenic unit in the complex, the clearing temperature and the temperature range of the nematic phase increased. The binary phase diagram of the polymeric complexes PVP–HOCnB showed complete miscibility over the entire range of composition. Molecular interactions of self-assembled SCLCP presented the idea that various LC-complexes could be prepared through mixing a functionalised polymer with various low molar mass mesogens.     

Formation of polymer-polymer complexes and blends in the system poly(acrylic acid)-poly(vinyl methyl ether)

The formation of a 1:1 polymer-polymer complex from poly(acrylic acid) and poly(vinyl methyl ether) has been detected by viscosity measurements in aqueous solution, and the glass transition temperature of the isolated complex has been determined. Infrared spectroscopy indicates that specific hydrogen bonding occurs between the components of the complex. Miscible blends of the two polymers can also be formed (at all compositions) and, although hydrogen bonding occurs, the structures of the blends are likely to be dissimilar to that of the complex.     

Supramolecular association of acid-terminated polydimethylsiloxanes. IV. NMR investigation of hydrogen bonding interactions and apparent molecular weight in the bulk state

Carbon-13 spin-lattice relaxation time measurements were used to probe the existence of hydrogen bonding interactions in bulk for a diacid-terminated oligosiloxane at temperatures well above its glass transition and melting temperatures. The behavior of the corresponding monoacid-terminated oligosiloxane, which can form dimers only, diester-terminated oligosiloxane, which cannot undergo any hydrogen bonding interactions, and two higher molecular weight covalent polymers, which serve as models for the supramolecular polymer, was also studied. The degree of association of the diacid-terminated oligosiloxane was estimated by investigating its transverse relaxation derived from ¹H NMR and comparing the results thus obtained with data from a series of polydimethylsiloxane samples with different molecular weights.     

A novel mucoadhesive polymer prepared by template polymerization of acrylic acid in the presence of poly (ethylene glycol)

A new mucoadhesive polymer was prepared by template polymerization of acrylic acid in the presence of poly(ethylene glycol) (PEG). FTIR results indicated that a polymer complex was formed between poly(acrylic acid) (PAA) and PEG through hydrogen bonding. The hydrogen bonding in the PAA/PEG polymer complex was stronger than that in the PAA/PEG blend, and became stronger as the molecular weight of PEG increased. Glass transition temperatures (T_g) of PAA in the PAA/PEG polymer complexes was shifted to a lower temperature than that of PAA in the PAA/PEG blend. However, they tended to become higher as the molecular weight of PEG increased. The dissolution rate of the PAA/PEG polymer complex was much slower than the PAA/PEG blend, and was dependent on pH and molecular weight of the PEG. The mucoadhesive force of the PAA/PEG polymer complexes was stronger than for the PAA/PEG blend or a commercial product, Carbopol 971P NF. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2749–2754, 1999     

A mucoadhesive polymer prepared by template polymerization of acrylic acid in the presence of poly(ethylene glycol) macromer

A new mucoadhesive polymer complex was prepared by the template polymerization of acrylic acid with poly(ethylene glycol) macromer (PEGM) as a template polymer. Fourier transform infrared results showed that the poly(acrylic acid) (PAA)/PEGM mucoadhesive polymer complex was formed by hydrogen bonding between the carboxyl groups of PAA and the ether groups of PEGM. The glass‐transition temperature of the PAA/PEGM mucoadhesive polymer complexes was shifted to a lower temperature as the repeating unit ratio of PAA/PEGM in the complex decreased. The dissolution rate of the PAA/PEGM mucoadhesive polymer complex was much slower than that of the PAA/poly(ethylene glycol) (PEG) mucoadhesive polymer complex and was dependent on the pH and molecular weight of PEGM. The mucoadhesive force of the PAA/PEGM mucoadhesive polymer complexes was stronger than that of commercial Carbopol 971P NF and almost the same as that of the PAA/PEG mucoadhesive polymer complex. The PAA/PEGM interpolymer complex seemed to be a better mucoadhesive polymer matrix than the PAA/PEG interpolymer complex. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1904–1910, 2002     

Blends of polybenzoxazine/poly(acrylic acid): hydrogen bonds and enhanced performances

This work focuses on exploring the role of the additional hydrogen bond donor moiety‐containing polymer poly(acrylic acid) (PAA) in the hydrogen bonds and properties of polybenzoxazines. Thorough studies showed that PAA could not only decrease the curing temperature of benzoxazine resin, but also give additional hydrogen bond donors that were beneficial to the hydrogen bonding interactions and performances of polybenzoxazine/PAA blends. As the hydrogen bonds varied, the glass transition temperature and tensile modulus of the polymer blends changed in accordance with the hydrogen bonds. The results revealed that the introduction of the hydrogen bond donor moiety‐containing polymer was beneficial for hydrogen bonding interactions, which could improve the performances of polybenzoxazines. This novel insight is anticipated to be of help to researchers in the development of more polybenzoxazines and polybenzoxazine blends with enhanced properties. © 2017 Society of Chemical Industry     

Theoretical study on the nature of the hydrogen bonds in an α-helical polymer and its model systems

The semi-empirical CNDO/2 SCF (self-consistent field) MO (molecular orbital) method using the tight-binding approximation for polymers was applied to polyglycine. The CNDO/2 calculations were also performed on model systems of this polymer. From the calculated results, the characteristics of the hydrogen bond in the α-helix were derived by comparison with those in the model systems. It was found that the hydrogen bond in the α-helix is very stable against proton transfer whereas the hydrogen bond in the model system is not so stable; this characteristic difference between the two systems is due to the coupling of two π-electron systems through hydrogen bonding in the α-helix.     

Stabilization of hydrophobic domains in hydrogel by intermolecular hydrogen bonds between carboxylic groups at the distal end of alkyl side-chain

The role of intermolecular hydrogen bond on the stability of hydrophobically associated domains of hydrogel, consisting of 12-acryloyloxydodecanoic acid (ADA; hydrophobic) or 6-acryloyloxyhexanoic acid (AHA; hydrophobic) and acrylic acid (AA; hydrophilic), carrying an alkyl side group terminated by carboxylic acid, was studied by swelling behavior in an organic solvent/water mixture. We chose propionic acid (PAc) and 1-propanol (PrOH) as organic solvents whose solubility parameter, log P, logarithmic partition equilibrium coefficient for octanol/water, is similar. The equilibrated swelling ratio of poly(ADA-co-AA) and poly(AHA-co-AA) gels by PAc was higher than by PrOH at a lower composition (ca. 5–15 mol%) and that of homo-polymer poly(AHA) gel by PAc was higher even at a high composition (up to ca. 70 mol%). The variation in swelling with solvent/water composition indicated a cross-over between the two solvent systems and this phenomenon did not depend on the alkyl side-chain length. Using Fourier transfer infrared spectroscopy, we observed the remarkable shift of the wavelength corresponding to the hydrogen bond in PAc aqueous solutions. Non-dissociated short alkanoic acid, which can penetrate hydrophobic domains and form hydrogen bonds with non-dissociated carboxylic groups of the polymer gel, favors the disruption of hydrophobic domains, causing swelling. Intermolecular hydrogen bonds between carboxylic groups of the alkyl side-chain are thus closely involved in the stability of hydrophobic domains in copolymer gel.     

Formation of interpolymer complexes between poly(monoethyl itaconate) and poly(N-vinyl-2-pyrrolidone)

This paper reports on the interpolymer complex formation and polymer blends between poly(monoethyl itaconate) (PMEI) and poly(N-vinyl-2-pyrrolidone) (PVP). The formation of the interpolymer complex was found to depend upon the solvent medium. Stoichiometry of the complexes prepared from methanol solutions, as calculated from elemental analysis, is close to 1 : 1. Specific interactions of PMEI/PVP complexes and blends of these polymers have been characterized by FTIR. Strong hydrogen bonding for complexes and blends has been found. A calorimetric study of the complexes and blends has been performed over a wide temperature range.     

Wasserabsorptionseigenschaften natürlicher polyionenkomplexe

As the cationic component of natural polymer polyionic complexes, polysaccharide chitosan or polypeptide polylysine, and as the anionic component, polysaccharide carboxymethyl cellulose (=CMC) or polypeptide poly(glutamic acid) (PGA) were used. The degree of chitosan/CMC or polylysine/PGA complex film swelling was minimum, when the amounts of the cationic and anionic groups in these polymers were balanced at 1 : 1 ratio. On the other hand, the degree of chitosan/PGA film swelling was minimum at the ratio with excess of PGA which is a linear flexible chain. Comparing the enthalpies estimated by DSC analysis, it was suggested that the larger quantity of water in the form of nonfreezable bound water was absorbed in the complex films with polysaccharide which is a chain of ring structure. Further, the compressive moduli of swollen complex films were high, when the complex consisted of polysaccharide components.     

The mechanism of the stereoregular polymerization of 2-vinylimidazole and 2-vinylbenzimidazole

Conformational energy calculations on poly(2-vinylimidazole) (PVI) and poly (2-vinylbenzimidazole) (FBI) indicated that the syndiotactic polymer would exhibit systematic intramolecular hydrogen bonding between side groups along the chain, while the isotactic polymers could not. This fact, together with our previous wor.k using solvent effects to produce highly syndiotactic poly(methacrylic acid) during radical polymerization, indicated that similar techniques could be applied in the radical polymerization, of 2-vinylimidazole and 2-vinylbenzimidazole. These mpnomers were polymerized over a wide temperature range using cobalt 60 gamma radiation as the initiator. The conditional probabilities obtained from NMR spectra of these polymers could be fit by second order Markov statistics (FBI) and extended second order Markov statistics (PVI). The difference reflects the effect of the bulkier benzimidazole side group. The nature of the conditional probabilities needed to fit the data for PVI suggest that the stereoregularity depended on the number of consecutive terminal r placements at the end of the growing radical. A marked solvent effect was observed was attributed to the hydrogen bonding strength of the solvent and its ability to disrupt the r directing polymer hydrogen bonding.     

The effect of fluorinated side chain attached on hard segment on the phase separation and surface topography of polyurethanes

It has been well established that polyurethanes exhibit a two-phase micro-structure due to the thermodynamic incompatibility between the soft segments and hard segments. In this work, we reported the effect of fluorinated side chain attached on hard segment on the phase separation and surface topography of polyurethanes. Two sets of fluorinated polyurethanes, namely, poly(ether urethane)s and poly(carbonate urethane)s containing various amounts of chain extender of fluorinated side chains, were investigated by DSC, XPS, DMA, AFM and FTIR. It was found that the phase separation in both bulk and surface increases in fluorinated poly(carbonate urethane)s and the phase mixing increases in fluorinated poly(ether urethane)s, with increasing amounts of fluorinated side chain. The increased degree of hydrogen bonding between hard segments and soft segments was observed by FTIR for fluorinated poly(ether urethane), which is believed to result in the enhanced phase mixing, and the enhanced association of domains with long-range order (hydrogen bonding) between hard segments was evident for fluorinated poly(carbonate urethane)s, which may correspond to the enhanced phase separation. The result is new and provides direct connection between surface topography and bulk phase separation of polyurethanes.     

Surface grafting of polymer onto carbon thin film

The surface grafting of polymers onto carbon thin film deposited on a glass plate was achieved by two methods: the graft polymerization initiated by initiating groups introduced onto the surface; and the trapping of polymer radicals by surface aromatic rings of the thin film. It was found that the radical and cationic graft polymerization of vinyl monomers are initiated by azo and acylium perchlorate groups introduced onto the surface, respectively, and the corresponding polymers are grafted onto the surface: the surface grafting of polymers were confirmed by the contact angle of the surface with water. In addition, the anionic ring-opening alternating copolymerization of epoxides with cyclic acid anhydrides was found to be initiated by potassium carboxylate groups on the carbon thin film to give the corresponding polyester-grafted carbon thin film. On the other hand, polymer radicals formed by the decomposition of azo polymer, such as poly(polydimethylsiloxane-azobiscyanopentanoate) and poly(polyoxyethylene-azobiscyanopentanoate), were successfully trapped by the surface aromatic rings of carbon thin film and polydimethylsiloxane and polyoxyethylene were grafted onto the surface. © 1995 John Wiley & Sons, Inc.     

Characteristics of poly(vinyl pyrrolidone)/poly(acrylic acid) interpolymer complex prepared by template polymerization of acrylic acid: Effect of reaction solvent and molecular weight of template

Poly(vinyl pyrrolidone) (PVP)/poly(acrylic acid) (PAA) interpolymer complexes were prepared, in ethanol or dimethylformamide (DMF), by template polymerization of acrylic acid in the presence of PVP (MW: 42.5 or 1100 K) used as the template. FTIR analysis showed that the complexes were formed through hydrogen bonding between the carboxyl groups of the PAA and the carbonyl groups of the PVP. The glass‐transition temperature (T_g) of the complex, prepared in ethanol, was higher than that of the component polymers, whereas the T_g of the complex, prepared in DMF, was located between that of the component polymers. The dissolution rate of the complex was affected by the molecular weight of the PVP and the reaction solvent. The release rate of ketoprofen from the complexes showed a pH dependency, and was slower at a lower pH. The ketoprofen release rate from the complex was controlled mainly by the dissolution rate of the complex above the pK_a of PAA (4.75) and by the diffusion rate below the pK_a. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2390–2394, 2004     

Non‐covalently crosslinked hydrogels displaying a unique combination of water‐absorbing,elastic and adhesive properties

BACKGROUND: Stringent requirements must be satisfied by biomedical adhesives, including biocompatibility, adhesion, cohesiveness and processability. The ability to change mechanical properties in response to environmental changes may also be desirable. In the present work the water‐absorbing, adhesive and mechanical properties of blends based on hydrogen bonding complexes between poly(N‐vinyl pyrrolidone), poly(ethylene glycol) (PEG) and poly[(methacrylic acid)‐co‐(ethyl acrylate)] were investigated. These blends, consisting of pharmaceutical‐grade components, exhibit pH‐sensitive swelling and dissolution, along with rubber‐like elasticity and bioadhesion. RESULTS: Polymer blend films remained intact at pH = 5.6 but underwent dissolution at pH = 7.4, the difference being attributed to deprotonation of acidic side‐chains, with loss of hydrogen bonding and development of charge repulsion. Sol release was primarily due to PEG. Films swelled at low pH instead of dissolving, in a manner that was pH‐dependent but PEG‐independent. Films displayed elastic properties comparable to cured elastomers when mildly swollen, with modulus and ultimate strength decreasing with increasing PEG content. Dry films were nearly tack‐free, but became more adhesive with increasing water content, up to a point where the film dissolved. CONCLUSION: Due to their biocompatibility and dissolution/mechanical properties, the bioadhesive polymer blends investigated may be suitable for numerous biomedical applications. Copyright © 2008 Society of Chemical Industry     

Interpolymer complex formation between form I helical and form II helical poly(l-proline) and poly(carboxylic acids)

Interpolymer complex formations between Form II helical poly(l-proline) [PLP(II)] and Form I helical poly(l-proline) [PLP(I)] and poly(carboxylic acids) such as polyacrylic acid (PAA), atatic polymethacrylic acid (at-PMAA), and syndiotatic polymethacrylic acid (st-PMAA) have been studied by FT-IR, X-ray diffraction, and light scattering measurements. It was found that the interpolymer complexes were formed via hydrogen bonding. The helical PLP(II) formed polymer complex more favorably with PAA and at-PMAA having a disordered structure than with st-PMAA having a ordered structure. In contrast, the helical PLP(I) formed polymer complex more favorably with st-PMAA than with PAA and at-PMAA. In addition, PLP(II) helix was destroyed on the complexation with PAA and at-PMAA, but the PLP(II) helix was perserved on the complexation with st-PMAA. However, the PLP(I) helix was all perserved on the complexation with poly(carboxylic acids). These findings could be explained in terms of molecular conformation of the complementary polymers associated with the complex formation. Received: 4 March 1997/Revised: 21 April 1997/Accepted: 28 April 1997     

The study of poly(styrene-co-p-(hexafluoro-2-hydroxylisopropyl)-α-methyl-styrene)/poly(propylene carbonate) blends by ESR spin probe and Raman

Different hydroxyl content poly(styrene-co-p-(hexafluoro-2-hydroxyisopropyl)-α-methylstyene) [PS(OH)] copolymers were synthesized and blends [noted for PP-X] with poly(propylene carbonate) [PPC] were prepared by casting from chloroform solution. The miscibility, micro heterogeneity and hydrogen bonding interaction of the component polymers were investigated by Differential Scanning Calorimetry (DSC), Electron Spin Resonance (ESR) spin probe method and Micro Raman spectroscopy. DSC results showed that the PP-2, PP-5, PP-8, PP-12 blends exhibited two distinct T_gs, indicating immiscibility, while the PP-20 and PP-27 blends were miscible with the existence of a single T_g. ESR results indicated that the probe molecule: Tempo couldn't give clear micro phase separation or miscibility information and thus was not sensitive to the investigated polymer blends system. On the contrary for all the blends spin probed with the probe molecules: Tempol and Tamine, two spectral components with different rates of motion: ‘fast’ and ‘slow’ motion were observed in different temperature range, which indicated the existence of micro heterogeneity on the molecular level; the more mobile PPC-rich micro phase and the more rigid PS(OH) rich micro phase. In addition, the scale of miscibility was progressively enhanced due to the increasing hydrogen bonding interaction between the hydroxyl in PS(OH) and the oxygen atoms in PPC. Meanwhile it was found that the degree of the probe molecule rotation detectable in the ESR spectrum was dependent on the polymer matrix rigidity and the strength of the hydrogen bonding between the probe molecule and the polymer matrix. Micro Raman substantiated the existence of the PS(OH)-rich micro phase and the PPC-rich micro phase. The hydrogen bonding strength between PS(OH) and PPC and the mixing level of the component polymers were increased gradually with the increase of hydroxyl content in the PS(OH) copolymer.     

超分子聚合物的自愈合行为

由于非共价键的选择性、可逆性和动态性,超分子聚合物非常适合作为自愈合材料应用,体现了感知和响应功能的智能特征。超分子聚合物的自愈合机理是通过非共价键相互作用实现的,即超分子结构的形成与解离。综述氢键型、?-?堆叠型、金属配位型、拓扑聚合物等类型的超分子聚合物的自愈合行为。     

Polyurethane elastomers through multi-hydrogen-bonded association of dendritic structures

A series of hydrogen bonding-rich polyurea/malonamide dendrons have been utilized as building blocks for the synthesis of novel dendritic polyurethane elastomers. Based on the resulting microstructure of soft segments reinforced by the rigid dendritic domains, the hydrogen bonding enforced phase separation of segmented polyurethanes was explored. DSC and FT-IR results indicate that a certain degree of phase separation between dendritic and poly(tetramethylene oxide) (PTMO) domains. The domain size of phase separation are less than 100 nm based on the results obtained from the atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS). The analysis of tensile measurements indicates that the incorporation of various contents of different dendrons as the hard segments allows these polymers to exhibit drastically different mechanical properties. Furthermore, low complex viscosity is observed at medium temperatures (above 130 °C) via the rheological analysis. With good mechanical properties at room temperature and low melt viscosity at medium temperatures, these thermoplastic elastomeric polyurethanes are suitable for applying in hot-melt process.