Publisher Summary This chapter provides an overview of polymer-polymer compatibility. The term "polymer compatibility" refers to the total miscibility, on a molecular scale, of homo-polymers and of random copolymers with each other in various combinations. In the chapter, no distinction is made between polymers in the rubbery or glassy state. The chapter discusses the crystallizable polymers in which the polymer remains at least partially amorphous and in which the miscibility with other polymers are investigated in the amorphous state. The chapter briefly reviews methods for predicting compatibility and presents a method for predicting compatibility along with its limitations. It explains the prediction schemes for polymer-polymer compatibility. The experimental methods for determining solubility parameters of polymers involve studies of the polymers in solution or swollen by solvent, that is, the thermodynamics of the situation involves the entropy contribution to the polymer-solvent interaction parameter and it complicates the theoretical treatment. It often turns out that experimental solubility parameters for the same polymer vary a great deal, depending both on the method used and on the experimenter. The two methods used are (1) swelling of a cross-linked polymer, where it is assumed that the solubility parameter of the polymer is equal to that of the solvent which swells it most highly and (2) intrinsic viscosity of a soluble polymer sample, where the solubility parameter of the polymer is equal to that of the solvent in which its intrinsic viscosity is greatest. For the same polymer, these methods often give different results depending on the nature of the solvents, which may be non-polar, polar, or hydrogen bonding.

Polymer–Polymer Compatibility

https://onlinelibrary.wiley.com/doi/pdf/10.1002/pol.1969.160070214

Synthesis and mechanical behavior of interpenetrating polymer networks: Poly(ethyl acrylate) and polystyrene

Past differential scanning calorimetry and dielectric relaxation measurements have established that polystyrene (PS)-poly(vinyl methyl ether) (PVME) mixtures exhibit a degree of compatibility when cast from toluene, whereas they are incompatible when cast from chloroform or trichloroethylene. The present study reports that toluene-cast mixtures can be phase-separated by thermal treatment at temperatures exceeding 125°C. This is true for samples containing 20–80 wt-% PS. The temperature of phase separation varies with heating rate; isothermal heating times needed to cause phase separation increase rapidly as the temperature approaches 125°C. Reversibility of the phase separation process depends upon such factors as cooling rate, annealing time, treatment temperature, and thermal history. By annealing and/or slow cooling, all thermally phase-separated mixtures have been brought back to their original state of compatibility. That is, there is no evidence for true irreversiblity of phase separation in thermally treated samples. Quench-cooled samples remain phase-separated indefinitely at room temperature, but this is attributed to rapid cooling below the glass transition of the PS. Chloroform-cast and trichloroethylene-cast mixtures have not been brought to a compatible state by thermal treatment, even after lengthy annealing and slow cooling steps.

Thermally induced phase separation of polystyrene‐poly(vinyl methyl ether) mixtures

Vertraglichkeit im Sinne einer Tendenz zur molekularen Durchmischung und gegenseitigen Losung ist bei zwei polymeren Komponenten im Festzustand eine seltene Ausnahme. So liegt normalerweise nicht nur bei Mischungen, sondern sogar bei Pfropf- und Blockcopolymeren ein Zweiphasensystem vor. Es werden Moglichkeiten zum Nachweis der separaten Phasen diskutiert, und zwar unter Verwendung optischer Methoden und durch Bestimmung der Einfrier- und Schmelztemperaturen der Einzelphasen. Weiterhin werden Probleme der Herstellung zweiphasiger Mischungen und der dabei auftretenden Phasenverteilung — disperse und kontinuierliche Phase — behandelt.

Unverträglichkeit und Phasenbildung im festen Stoffzustand bei Polymermischungen, Pfropf- und Blockcopolymeren

Macro-azonitriles were prepared by the reaction of azobis-alcohol with diisocyanate of polyalkylene oxide and were used as initiators for the polymerization of various vinyl monomers such as vinyl acetate, styrene, methyl methacrylate and vinyl chloride, yielding block-copolymers consisting of polyalkylene oxide and polyvinyl sequences. These block copolymers were characterized by their dynamic properties. The polymers were found to possess two transition points, one arising from the polyalkylene oxide blocks and the other from the polyvinyl sequences. A thermoplastic elastomer was obtained from the block polymerization of styrene with poly(oxytetramethylene)glycol, whose intrinsic viscosity was 2.3 dl/g and the styrene content was 33.2 wt. –%, the ultimate strength and elongation being 57 kg/cm2 and 475%, respectively. The block copolymers of polystyrene and branched polyether were also synthesized and their viscoelastic properties were investigated.



Makro-Azonitrile wurden durch Reaktion von Azo-bis-alkoholen mit endstandig mit Diisocyanaten umgesetzten Polyalkylenoxiden synthetisiert und als Initiatoren fur die Polymerisation von verschiedenen Vinylmonomeren wie Vinylacetat, Styrol, Methylmethacrylat und Vinylchlorid verwendet. Es wurden Block-copolymere mit Polyalkylenoxid- und Polyvinylsequenzen erhalten. Die Blockcopolymeren wurden durch ihre mechanischen Eigenschaften charakterisiert. Fur die Polymeren wurden zwei Umwandlungspunkte gefunden, wobei einer dem Polyalkylenoxid-, der andere den Polyvinylsequenzen zuzuordnen ist. Ein thermoplastisches Elastomeres wurde durch Blockcopolymerisation von Styrol mit Polyoxytetramethylenglykol erhalten, dessen Grenzviskositat 2,3 dl/g war bei einem Styrolgehalt von 33,2%; Zugfestigkeit und Dehnung betrugen 57 kg/cm2 bzw. 475% . Auserdem wurden Blockcopolymere aus Styrol und verzweigten Polyathern synthetisiert und auf ihre viskoelastischen Eigenschaften untersucht.

Preparation of block copolymers with macro‐azonitrile as an initiator

The reaction of industrially available “prepolymers,” containing one or several isocyanate groups per chain, with tert-butyl hydroperoxide yielded long-chain peroxycarbamates. These were found able to initiate the polymerization of a wide variety of vinyl monomers as well as dienes leading to a new class of block polymers of very interesting physical properties. Polyether and polyester “prepolymers” with one, two, or three isocyanate functionalities were linked chemically to polystyrene, polymethyl methacrylate, poly-n-butyl acrylate, polyarylonitrile, and polyisoprene. The formation of block polymers was proved by both physical and chemical methods. Their mechanical properties were illustrated by means of torsional modulus–temperature curves. The effect of varying composition and of a crosslinking agent on the elastic modulus was examined. Tentative reaction mechanisms were also presented.

A new class of block polymers

Graft copolymers and polyblends of beta- vinylnaphthalene and ethylene oxide exhibiting modulus vs temperature minimum and rubbery properties at room temperature

Some unusual properties of graft copolymers and polyblends of β-vinylnaphthalene and ethylene oxide†

Graft and block copolymers of some vinyl aromatic hydrocarbons

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A new class of block polymers

Some unusual properties of graft copolymers and polyblends of β-vinylnaphthalene and ethylene oxide†

Graft and block copolymers of some vinyl aromatic hydrocarbons