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

Abstract

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...

Triplet-State Photochemistry of Dissolved Organic Matter: Triplet-State Energy Distribution and Surface Electric Charge Conditions

“…Sorbic alcohol ( trans , trans -sorbic alcohol, 97%), sorbic acid ( trans , trans -sorbic acid, 99%), 2,4,6-trimethylphenol (TMP, 99%), furfuryl alcohol (FFA, 98%), gallic acid (GAC, 98%), 1,4-benzoquinone (98%), 1,4-naphthoquinone (97%), plumbagin (97%), sodium anthraquinone-2-sulfonate (98%), acetophenone (99%), 3-methoxyacetophenone (97%), trifluoroacetic acid (TFA, 99%), ammonium acetate (98%), acetic acid (99.7%), and phosphate salts (NaH 2 PO 4 , Na 2 HPO 4 (both 99%)) were purchased from Sigma-Aldrich. Benzophenone (99%), 4-benzoylbenzoic acid (99%), 2-hydroxyphenylacetic acid (OPAC, 98%), p -nitroacetophenone (PNAP, 98%), and pyridine (pyr, 99%) were obtained from Tokyo Chemical Industry Co., Ltd. Sorbic amine ( trans , trans -sorbic amine) was synthesized from trans , trans -sorbic acid according to the procedure proposed by Matsumoto and co-workers . All chemicals were used as received.…”

“…Benzophenone (99%), 4-benzoylbenzoic acid (99%), 2-hydroxyphenylacetic acid (OPAC, 98%), p-nitroacetophenone (PNAP, 98%), and pyridine (pyr, 99%) were obtained from Tokyo Chemical Industry Co., Ltd. Sorbic amine (trans,trans-sorbic amine) was synthesized from trans,trans-sorbic acid according to the procedure proposed by Matsumoto and co-workers. 43 All chemicals were used as received.…”

Orientational Control of Guest Molecules in an Organic Intercalation System by Host Polymer Tacticity

“…However, a limited number of examples have been reported as the intercalation systems consisting of only organic compounds 5. We have already demonstrated that a layered PMA is available as the host compound for the intercalation of various organic guests such as alkylamines,4 unsaturated amines,6 azo‐containing amines,7 and other functional amines,4 as well as the metal cations as the inorganic guests 8…”

Reactions of 1,3-Diene Compounds in the Crystalline State

“…Currently, topochemical polymerization is opened not only to the diacetylene library but also to the diene library, which is more popular and a larger collection. Diene polymerization has the potential of being applied to the construction of advanced organic materials in the solid state, because the topochemical polymerization of diacetylene and diene monomers provides different types of polymers, that is, conjugate and nonconjugate polymers, respectively (Scheme 8) [16,61]. The rules for diene polymerization are more sensitive to a slight change in the monomer crystal structure.…”