Cloud Point Curves of Aqueous Solutions of Poly(N-ethylmethacrylamide)

1993 ◽  
Vol 58 (10) ◽  
pp. 2370-2382 ◽  
Author(s):  
Miloslav Bohdanecký ◽  
Jiří Horský ◽  
Vladimír Petrus ◽  
Libuše Mrkvičková ◽  
Karel Ulbrich

Aqueous solutions of poly(N-ethylmethacrylamide) have a lower critical solution temperature (LCST). Cloud point curves of five polydisperse samples (Mw . 10-6 = 0.06 to 2.04) in aqueous solutions at concentrations from 0.002 to 0.1 g/ml were obtained. The threshold concentration was found to be almost independent of the molecular weight. The threshold temperature decreases moderately with increasing M and the limiting value for infinite M obtained by the Shultz-Flory method is ΘLPE = 340.5 K. This value is lower by 2.5 K than the temperature ΘLη at which the intrinsic viscosity is proportional to the square root of the molecular weight. The difference cannot be assigned to experimental errors. The entropy-of-dilution parameter is negative (ψ = -2) and much higher than the value obtained from dilute solution properties. The differences in Θ and ψ values are discussed in terms of theory of polymer solutions where a higher-order interaction parameter is included.

2019 ◽  
Vol 10 (2) ◽  
pp. 260-266 ◽  
Author(s):  
Jin-Jin Li ◽  
Yin-Ning Zhou ◽  
Zheng-Hong Luo ◽  
Shiping Zhu

A polyelectrolyte-containing copolymer with a CO2/N2-switchable cloud point, resulting from the gas-induced alternation of hydrophilicity, was prepared.


2019 ◽  
Vol 20 (18) ◽  
pp. 4604 ◽  
Author(s):  
Ihsan ◽  
Nargis ◽  
Koyama

A series of N-substituted poly(Gly–alter–Val) peptides were successfully synthesized for the systematic evaluation of the micellization behavior of alternating peptides. Three-component polymerization employing an aldehyde, a primary ammonium chloride, and potassium isocyanoacetate afforded four alternating peptides in excellent yields. We investigated the dependence of the hydrophilic–lipophilic balance of alternating peptides on the micellization behavior. All the aqueous solutions of alternating peptides exhibited upper critical solution temperature (UCST) behaviors, strongly indicating that the alternating binary pattern would mainly contribute to the UCST behaviors. The cloud points of alternating peptides shifted to higher temperatures as the side chains became more hydrophilic, which is opposite to the trend of typical surfactants. Such unusual micellization behaviors appeared to be dependent on the quasi-stable structure of single polymer chains formed in water.


Polymers ◽  
2020 ◽  
Vol 12 (5) ◽  
pp. 1085
Author(s):  
Alina Amirova ◽  
Tatyana Kirila ◽  
Mikhail Kurlykin ◽  
Andrey Tenkovtsev ◽  
Alexander Filippov

Cross-linked derivatives of acylated branched polyethyleneimine containing 2-isopropyl-2-oxazoline units were investigated in chloroform and aqueous solutions using methods of molecular hydrodynamics, static and dynamic light scattering, and turbidity. The studied samples differed by the cross-linker content. The solubility of the polyethyleneimines studied worsened with the increasing mole fraction of the cross-linker. Cross-linked polyethyleneimines were characterized by small dimensions in comparison with linear analogs; the increase in the cross-linker content leads to a growth of intramolecular density. At low temperatures, the aqueous solutions of investigated samples were molecularly dispersed, and the large aggregates were formed due to the dehydration of oxazoline units and the formation of intermolecular hydrogen bonds. For the cross-linked polyethyleneimines, the phase separation temperatures were lower than that for linear and star-shaped poly-2-isopropyl-2-oxazolines. The low critical solution temperature of the solutions of studied polymers decreased with the increasing cross-linker mole fraction. The time of establishment of the constant characteristics of the studied solutions after the jump-like change in temperature reaches 3000 s, which is at least two times longer than for linear polymers.


Polymers ◽  
2019 ◽  
Vol 11 (6) ◽  
pp. 991 ◽  
Author(s):  
Alberto García-Peñas ◽  
Chandra Sekhar Biswas ◽  
Weijun Liang ◽  
Yu Wang ◽  
Pianpian Yang ◽  
...  

For the preparation of thermoresponsive copolymers, for e.g., tissue engineering scaffolds or drug carriers, a precise control of the synthesis parameters to set the lower critical solution temperature (LCST) is required. However, the correlations between molecular parameters and LCST are partially unknown and, furthermore, LCST is defined as an exact temperature, which oversimplifies the real situation. Here, random N-isopropylacrylamide (NIPAM)/dopamine methacrylamide (DMA) copolymers were prepared under a systematical variation of molecular weight and comonomer amount and their LCST in water studied by calorimetry, turbidimetry, and rheology. Structural information was deduced from observed transitions clarifying the contributions of molecular weight, comonomer content, end-group effect or polymerization degree on LCST, which were then statistically modeled. This proved that the LCST can be predicted through molecular structure and conditions of the solutions. While the hydrophobic DMA lowers the LCST especially the onset, polymerization degree has an important but smaller influence over all the whole LCST range.


1967 ◽  
Vol 40 (5) ◽  
pp. 1544-1552
Author(s):  
C. H. Baker ◽  
C. S. Clemson ◽  
G. Allen

Abstract The influence of pressure on a lower critical solution temperature is much more pronounced than on an upper critical solution temperature. Accordingly it is possible to control phase separation at a LCST phase boundary under isothermal conditions by merely adjusting the pressure on the system. An apparatus has been constructed to investigate the isothermal fractionation of polyisobutene in which precipitation is controlled by pressure. Two samples of polyisobutene of Mv=1.76×106 and 9.0×104 have been fractionated in isopentane solution so as to yield up to six and nine fractions respectively. The integral molecular weight distribution curves thus obtained are compared with those obtained from conventional fractionations at an UCST. The sensitivity of the method is poor with regard to the separation of low molecular weight fractions and degradation occurs at the higher temperatures to an appreciable extent.


1998 ◽  
Vol 511 ◽  
Author(s):  
C. H. Ryu ◽  
Y. C. Bae

ABSTRACTWe investigated phase behaviors of polyimide blends such as polyethermide(PEI)/polystyrene(PS), PEI/polyamideimide(PAI), PEI/polyethyleneoxide(PEO), and PAI/PEO systems. Our sample systems exhibited lower critical solution temperature(LCST) phase behaviors. In the PEI/PS system, phase transition occurred near or above the glass transition temperature(Tg) of PS and the critical temperature of the system increased with decreasing molecular weight of PS. For PEI/PAI and PEI/PEO systems, the critical temperature of PEI/PAI system is higher than that of PEI/PEO system. Phase transition temperatures of PAI/PEO systems appeared near or below the melting point of PEO.


2006 ◽  
Vol 18 (05) ◽  
pp. 222-228 ◽  
Author(s):  
CHUN-TE TAO ◽  
TAI-HORNG YOUNG

Poly N-isopropylacrylamide (PNIPAAm) is a well-known temperature-sensitive polymer. When the temperature is higher than the lower critical solution temperature (LCST), PNIPAAm aquous solution is cloudy (phase separation occurred). In contrast, when the temperature is lower than the LCST, PNIPAAm is soluble in water (a homogeneous solution). The lower critical solution temperature (LCST) in aqueous solution of PNIPAAm was about 32~33°C. We prepared nano-scaled PNIPAAm particles containing carboxylic group on their surfaces by introducing acrylic acid monomer. The carboxylic groups were applied to conjugate with the amino group of the CD34 antibody. This immuno-conjugate can be applied on targeting the human CD34 positive cells, peripheral blood progenitor cells included, for cell purification and drug controlled release. In order to the active responding of controlled release of the conjugate in the body influenced by temperature, we hope to estimate the shifting of the gel-collapse temperature or cloud point of the immuno-conjugates by dynamic light scattering (DLS) and UV absorption. The results show that the gel-collapse temperature of the nano-particle was not significantly affected by the content of AA between 1.5~5 mol%. However, cloud point of the solution was elevated by the conjugation of CD34 antibody to 37°C. When CD34-conjugated particle was subsequently incorporated with recombinant FLT3-ligand, which is a smaller molecule compare to CD34 antibody, cloud point of the solution was not affected.


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