Dilute Solution Properties of Low-temperature Polymerized Polyvinyl Chloride. I. Effects of Dissolution Temperature and Time

Kobayashi, Takashi

doi:10.1246/bcsj.35.637

Bulletin of the Chemical Society of Japan

1962

DOI: 10.1246/bcsj.35.637

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Dilute Solution Properties of Low-temperature Polymerized Polyvinyl Chloride. I. Effects of Dissolution Temperature and Time

Takashi Kobayashi¹

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1964

1993

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Cited by 9 publications

References 6 publications

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Solvent power of solvents for poly(vinyl chloride)

Moore

Hutchinson

1964

J of Applied Polymer Sci

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SynopsisOsmotic, viscometric, and initial phase separation studies of dilute solutions of poly-(vinyl chloride) in cyclohexanone, cyclopentanone, tetrahydrofuran, morpholine, nitrobenzene, and tetrahydropyran are reported together with some swelling measurements involving these solvents and dioxane, acetone, and methanol. Values of the polymersolvent interaction parameter X I obtained from osmotic and swelling measurements suggest the order of solvent power for poly(viny1 chloride) to be cyclohexanone > cyclopentanone > tetrahydrofuran > morpholine > nitrobenzene > tetrahydropyran. A similar order is suggested by the volumes of hexane required to cause initial phase separation.Values of intrinsic viscosity and of the viscosity slope constant k' give somewhat different orders of solvent power.The correlation of the volume of hexane required to cause initial phase separation with XI is d~-cussed and it is suggested that the polymer is solvated in solution. Other factors affecting the solvent power of solvents forpoly(viny1 chloride) would appear to include the bulk and the solubility parameter of the solvent.Reasons for differences in order are considered.

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Solvent power of solvents for poly(vinyl chloride)

Moore

Hutchinson

1964

J of Applied Polymer Sci

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Size exclusion chromatographic measurement of PVC molecular weight distributions

Pang¹,

Rudin²

1993

J of Applied Polymer Sci

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SYNOPSISAggregates that may exist in poly(viny1 chloride) (PVC) solutions at ambient temperatures compromise the accuracy of SEC measurements of molecular weight distributions. Aggregate-free solutions can be produced in 1,2,4-trichlorobenzene (TCB ) by controlling the dissolution time and temperature. SEC measurements were made in trichlorobenzene at 110°C after dissolution for 12 h at 120°C. An on-line continuous viscometer can be used to determine when aggregate-free solutions have been produced. The Mark-Houwink parameters ( K = 0.161 mL/g, (Y = 0.762) can be used for universal calibration procedures in TCB a t 110OC. Complete dissolution of the PVC affects the high molecular weight end of the molecular weight distribution. Measured M n values are not affected, but M i s are much higher than those estimated, for example, from room-temperature SEC analyses in tetrahydrofuran. Molecular weight distributions are also seen to be broader, especially for higher molecular weight PVCs.

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Unperturbed chain dimension of poly(vinyl chloride) polymerized at different temperatures

Nakajima

Kato

1966

Makromol. Chem.

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For ply(viny1 chlorides) polymerized a t various temperatures in a range of -15 to +50 "C., the @-point was determined in the system %trahydrofuran/water at 30 "C., according to the method proposed by ELIAS, and the unperturbed chain dimension in the @-solvent was investigated in relation to the structural factors, such as branching and stereoregularity of the polymer, as a function of the polymerization temperature-The unperturbed chain dimension of the polymer polymerized at lower temperature was found to be larger than that polymerized at higher temperature. This result is interpreted by that poly(viny1 chloride) is Fore syndiotactic and less branched with lower polymerization temperature, and that increase in the syndiotacticity leads to the increase of unperturbed dimension more effectively than the effect of short chain branching. ZUSAMMENFASSUNG: Fiir verschiedene Polyvinylchloridproben, die bei Temperaturen zwischen -15 und +50 "C polymerisiert waren, wurden die O-Gemische im System Tetrahydrofuran/Wasser bei 30°C ermittelt, und zwar nach der Methode von ELIAS. In diesen @-Losungsmitteln wurde die ungestorte Knaueldimension des Polyvinylchlorids untersucht, hinsichtlich der Beziehungen zwischen der Polymerisationstemperatur und strukturellen Eigenschaften wie Verzweigung und Stereoregularitat. Bei niedrigerer Polymerisationstemperatur ist die ungestorte Knaueldimension gro13er als bei hoherer. Dies wird dahingehend interpretiert, da13 das bei niedriger Temperatur erhaltene Polyvinylchlorid stiirker syndiotaktisch und weniger verzweigt ist, wobei die Zunahme des syndiotaktischen Anteils mit abnehmender Temperatur die ungestorte Knaueldimension starker beeinflufit als die Abnahme der Kurzkettenverzweigung.

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Dilute Solution Properties of Low-temperature Polymerized Polyvinyl Chloride. I. Effects of Dissolution Temperature and Time

Cited by 9 publications

References 6 publications

Solvent power of solvents for poly(vinyl chloride)

Solvent power of solvents for poly(vinyl chloride)

Size exclusion chromatographic measurement of PVC molecular weight distributions

Unperturbed chain dimension of poly(vinyl chloride) polymerized at different temperatures

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