A Novel Organic Intercalation System with Layered Polymer Crystals as the Host Compounds Derived from 1,3-Diene Carboxylic Acids

Abstract

A new type of organic intercalation system using poly(muconic acid) and poly(sorbic acid) crystals as the host compounds is described. The layered polymer crystals as the host are derived from benzyl-, dodecyl-, or naphthylmethylammonium salts of (Z,Z)-muconic or (E,E)-sorbic acids by topochemical polymerization. The subsequent solid-state hydrolysis of the resulting ammonium polymer crystals provides the corresponding carboxylic acid polymer crystals. When alkylamines are reacted with poly(muconic acid) or poly(sorbic acid) crystals dispersed in methanol at room temperature for a few hours, the intercalation proceeds to give layered ammonium polymer crystals via solid-state reactions, in which the polymers maintain a layered structure throughout. The interplanar spacing value of the polymer crystals changes according to the size of the guest molecules; that is, it exactly depends on the carbon number of the alkylamines used for each reaction of poly(muconic acid) or poly(sorbic acid) crystals. The stacking structure of alkyl chains with a tilt in the intercalated alkylammonium layers exists irrespective of the chemical and crystal structures of the host polymers. The intercalation of higher alkylamines into poly(muconic acid) crystals proceeds fast and quantitatively, while the conversion is dependent on the reaction conditions such as the structure and amount of the amine and the reaction time during the intercalation with poly(sorbic acid) crystals, due to the difference in the repeating layered structures of these polymer crystals. Some functional amines are also used as the guest molecules for this organic intercalation system.

Reinforcement of nitrile rubber by in situ formed zinc disorbate

“…It is believed that the exothermic peak is due to the polymerization of ZDS and the enthalpy for the polymerization of ZDS is approximately 477.4 J/g. Since SA is also reactive to rubber chains during vulcanization, the grafting of SA onto rubber chains is a competitive reaction to the formation of ZDS [27,28]. To optimize the formation of ZDS in the rubber compounds, the open mill compounded rubber compounds excluding DCP were heat treated at 120°C for 15 min.…”

Organic Intercalation of Unsaturated Amines into Layered Polymer Crystals and Solid-State Photoreactivity of the Guest Molecules in Constrained Interlayers

“…The corresponding saturated nalkylamines possessing an identical number of carbons in the alkyl chain were also used as the guest amines for comparison. 23 The results are summarized in Table I. Figure 1 shows the effects of the molar ratio of the used amine against the carboxylic acid ([-NH 2 ]/ [-CO 2 H]) in the host polymer on the conversion from the acid to the ammonium form during the intercalation of the saturated and unsaturated amines.…”

“…23 The PMA crystals, 50 mg, were dispersed in methanol solution (20 mL) of a desired amount of amine and stirred at room temperature for 1 h. The polymer crystals were isolated with a glass filter, washed with a small amount of fresh methanol (ca. 10 mL), and dried in vacuo.…”

“…For example, carboxylic groups orderly arrange along the polymer chains in a high density in a stacking distance of 5 Å in the polymer crystals as the organic intercalation host. 23,25,26 This structural feature is potentially used as a new kind of intercalation material for reactions; namely, the interlayer space of the layered crystals may function as the specific reaction vessel to give a stereospecific reaction product due to a reactivity different from that in isotropic medium. Especially, photochemical properties are of great interests because photoactive species are immobilized and restricted in a constrained interlayer space when they are intercalated into organic polymer crystals as the host.…”

“…[12][13][14][15] In contrast to a large number of studies on intercalation systems made of inorganic compounds or inorganic-organic hybrids, very few examples are known as an intercalation system consisting of organic compounds as both the host and guest. [16][17][18][19][20][21] We have previously demonstrated the fundamental features and mechanism of the intercalation of various alkylamines into poly(muconic acid) (PMA) as the organic host compound [21][22][23][24] (Scheme 1). Long-chain alkylamines are suitable as the guest molecules and the intercalation provides a new layered polymer crystal with an interlayer spacing different from that of the original PMA crystals.…”