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.

ABSTRACT:We have investigated the intercalation of several unsaturated amines using poly(muconic acid) crystals as the layered organic polymer host. Allyl-and oleylamines are intercalated into the polymer crystals in order to introduce an olefin moiety in the side chain of poly(muconic acid). The oleylammonium polymer crystals are alternatively obtained by the topochemical polymerization of oleylammonium muconate as the corresponding ammonium monomer crystals under photoirradiation in the crystalline state, while the photoirradiation of the allylammonium muconate crystals results in the formation of isomers. The inner double bond of the intercalated oleyl group has a low reactivity under UV irradiation, and the allyl group has no reactions. In contrast, diene and diyne moieties introduced into the side chain by the intercalation using 2,4-hexadienyl-, 2,4-tetradecyldienyl-, and 10,12-pentacosadiynylamines as the guest amines readily react to give a new type of the polymer crystal consisting of alternately stacked polymer nano-sheets. We have revealed that the intercalation of long-chain unsaturated amines proceeds in a high conversion, and the photoreactivity of the unsaturated functional groups in the side chain is determined by the kind of unsaturated groups and the stacking distance of the amine molecules in the layers.KEY WORDS Layered Polymer Crystals / Intercalation / Poly(muconic acid) / Solid-State Photoreaction / Polydiacetylene / Organic/inorganic nano-composites with an organized structure have attracted interests in the fundamental and applied fields of polymer chemistry and nanomaterial science. 1-3 A large number of inorganic solids with a two-dimensional structure such as clays, metal phosphonates or phosphites, graphite, and metal oxides have been reported, 4, 5 and the properties and functions of these layered materials are modified by combination with organic molecules as the guest compounds. [6][7][8][9][10][11] The combination of materials with a different nature efficiently induces a new property and function, which cannot be attained from an organic or inorganic compound alone. The structure and properties of the composites consisting of various types of clays and polymers have also been investigated. [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 21-24 (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. The organic intercalation system consisting of layered organic polymers and organic guest amines has some characteristics different fr...

From environmental protection point of view, use of recycled fibre has been increasing in Japanese paper and paperboard industry. Demand of used paper has been increasing not only in domestic but also overseas. Quality of recycled fibre which has been used in domestic is getting lower and papermaking condition has become worse. Even in such severe condition, paper chemicals i.e. sizing agent, paper strength agent have to work effectively.In this report, newly developed PAM based polymer which will keep high coagulation force and will give final paper strong dry strength is described. New type PAM based polymer make it possible to obtain good results under severe condition. This new polymer agent is not aqueous solution but it is high molar weight polymer dispersion. Higher level of paper strength is achieved when the new type polymer is added in wet-end, and onepass retention of fibre and sizing efficiency are also encouraged.