The prediction of hydrogen bonded polymer blend phase behavior using equilibrium constants determined from low molar mass analogues

Coleman, Michael M.; Guigley, Kevin S.; Painter, Paul C.

doi:10.1002/(sici)1521-3935(19990501)200:5<1167::aid-macp1167>3.3.co;2-s

Cited by 12 publications

(24 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We recently modified Dr. J. F. Graf's "Phase Calculator" program that accompanies our monograph, 2a to include affects of chain connectivity. 4 After choosing the appropriate equilibrium scheme (in this case that based on eqs 1 and 2) and inputting appropriate values of the molar volume (V i ), molar mass (M i ), solubility parameter (δ i ), self-association and interassociation equilibrium constants (K D , K A ), enthalpies of hydrogen bond formation (h D , h A ), and the intramolecular screening factor (γ), the program calculates the fraction of hydrogenbonded functional groups, the individual contributions to the free energy of mixing, phase diagrams, miscibility windows and miscibility maps, etc., as a function of temperature and composition. In this work, the following values of the various parameters were used.…”

Section: Cdomentioning

confidence: 99%

Infrared Spectroscopic Studies of Poly(styrene-co-methacrylic acid) Blends with Polytetrahydrofuran

et al. 2000

Self Cite

View full text Add to dashboard Cite

We recently reported the results of a comprehensive infrared study of the self-association of methacrylic acid copolymers. 1 Values of equilibrium constants that describe the number of hydrogen-bonded carboxylic acid dimers formed at equilibrium were determined and found to be a strong function of chain stiffness. In this note, we present some further spectroscopic results involving miscible blends of poly(tetrahydrofuran) (PTHF) with one of these random styrene-co-methacrylic acid copolymers that contains 9 mol % methacrylic acid (denoted STMAA{9}).At a given temperature, above the glass transition temperature and below the onset of anhydride formation, the carbonyl groups of STMAA{9} exist in a state of dynamic equilibrium, oscillating between isolated "free" (non-hydrogen-bonded) and hydrogen-bonded carboxylic acid dimers (there is also a transient "opendimer" intermediate state that has been detected in dilute solution studies, but not in polymer work 1 ). This equilibrium may be simply depicted as

show abstract

Section: Cdomentioning

confidence: 99%

Infrared Spectroscopic Studies of Poly(styrene-co-methacrylic acid) Blends with Polytetrahydrofuran

et al. 2000

Self Cite

View full text Add to dashboard Cite

show abstract

“…Painter et al reported that the K A for poly(vinylphenol) (PVPh)/PMMA blends is 37.5, whereas the K A for a corresponding model compound mixture, ethyl phenol/ethyl isobutyrate, is 172. The significant decrease in the K A of PVPh/PMMA blends was attributed to the effects of intramolecular screening and functional group accessibility caused by the chain connectivity. − Intramolecular screening occurs when the polymer chain bends back on itself; accordingly, the degree of interassociation hydrogen bonding in the polymer blend would be lower than in the model compound. On the other hand, the effect of functional group accessibility can be attributed to steric crowding and shielding; that is, the spacing between the functional groups along a polymer chain and the presence of bulky side groups would also significantly decrease the degree of interassociation hydrogen bonding .…”

Section: Resultsmentioning

confidence: 99%

Hydrogen Bond Interactions Mediate Hierarchical Self-Assembly of POSS-Containing Block Copolymers Blended with Phenolic Resin

et al. 2014

View full text Add to dashboard Cite

P o l y( me t h y l m et h a c r y l a t e ) -b -poly-(methacryloyl polyhedral oligomeric silsesquioxane) (PMMA-b-PMAPOSS) block copolymers of various compositions were prepared through anionic living polymerization. We employed differential scanning calorimetry, Fourier transform infrared spectroscopy, small-angle X-ray scattering, transmission electron microscopy, and wide-angle X-ray diffraction to investigate the miscibility, specific interactions, and hierarchical self-assembly of PMMA-b-PMAPOSS block copolymers blended with a phenolic resin. We found that the added phenolic resin interacted preferentially with the PMMA blocks through hydrogen bonding between the OH groups of the former and the CO groups of the PMAPOSS. In other words, the OH groups of the phenolic resin did not interact with the CO groups of the PMAPOSS blocks, resulting in their immiscibility. Accordingly, this phenolic/PMMA-b-PMAPOSS blend behaved as a blend of homopolymer C and immiscible A-b-B diblock copolymer, where C is immiscible with B but interacts favorably with A; therefore, it displayed an order−order phase transition with increased phenolic resin content. Hierarchical self-assembly led to the formation of hexagonally packed cylindrical or lamellar nanostructures through microphase separation of the diblock copolymer segment, with POSS aggregates packing into a hexagonal lattice oriented perpendicular to the direction of the nanostructures.

show abstract

“…Initially, this observation seems counterintuitive because of the expected hydrogen bonding between the hydroxyl group of PVPh and the carbonyl group of PAS. However, the polymer‐chain architecture is significantly different from the low molar mass molecule because of intramolecular screening and functional group accessibility12–17 caused by the chain connectivity. The intramolecular screening effect is caused by an increase in the number of contacts by the same polymer chain as a result of the self‐bending back of the polymer chain, and the number of interassociation hydrogen bonds per unit volume in the polymer blend will be less relative to the model compound.…”

Section: Introductionmentioning

confidence: 99%

Effect of inert diluent segment on the miscibility behavior of poly(vinylphenol) with poly(acetoxystyrene) blends

Kuo

Chang

2002

J Polym Sci B Polym Phys

View full text Add to dashboard Cite

Polymer blends of poly(vinylphenol) (PVPh) and poly(styrene-co-vinylphenol) with poly(p-acetoxystyrene) (PAS) were prepared by solution casting from tetrahydrofuran solution. The thermal properties and hydrogen bonding of the blends were investigated by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy. Although hydrogen bonding existed between the PVPh and PAS segments, the experimental results indicated that PVPh is immiscible with PAS as shown by the existence of two glass-transition temperatures over the entire composition range by DSC. This phenomenon is attributed to the strong self-association of PVPh, intramolecular screening, and functional group accessibility effects of the PVPh/PAS blend system. However, the incorporation of an inert diluent moiety such as styrene into the PVPh chain renders the modified polymer to be miscible with PAS. Copolymers containing between 16 and 51 mol % vinylphenol were fully miscible with PAS according to DSC studies. These observed results were caused by the reduction of the strong self-association of PVPh and the increase of the interassociation between PVPh and PAS segments with the incorporation of styrene on the PVPh chain. According to the Painter-Coleman association model, the interassociation equilibrium constant of PVPh/PAS blends was determined by a model compound and polymer blend. Good correlation between these two methods was obtained after considering the intramolecular screening and functional group accessibility effect in the polymer blend.

show abstract

The prediction of hydrogen bonded polymer blend phase behavior using equilibrium constants determined from low molar mass analogues

Cited by 12 publications

References 0 publications

Infrared Spectroscopic Studies of Poly(styrene-co-methacrylic acid) Blends with Polytetrahydrofuran

Infrared Spectroscopic Studies of Poly(styrene-co-methacrylic acid) Blends with Polytetrahydrofuran

Hydrogen Bond Interactions Mediate Hierarchical Self-Assembly of POSS-Containing Block Copolymers Blended with Phenolic Resin

Effect of inert diluent segment on the miscibility behavior of poly(vinylphenol) with poly(acetoxystyrene) blends

Contact Info

Product

Resources

About