US EPA

7448654 

Journal Article 

Nonlinear organic reaction of 9-fluorenylmethyl carbamates as base amplifiers to proliferate aliphatic amines and their application to a novel photopolymer system 

Arimitsu, K; Ichimura, K 

2004 

Yes 

Journal of Materials Chemistry
ISSN: 0959-9428
EISSN: 1364-5501 

ROYAL SOC CHEMISTRY 

CAMBRIDGE 

14 

3 

336-343 

English 

10.1039/b311358b 

WOS:000188492100010 

A novel concept of base proliferation for improving the photosensitivity of base-sensitive materials is described by presenting the autocatalytic transformation of 9-fluorenylmethyl carbamates to aliphatic amines. A 9-fluorenylmethyl carbamate, as a base amplifier, was subjected to a base-catalysed fragmentation reaction to liberate the corresponding amine, which can then act as a catalyst for decomposing parent molecules, leading to autocatalytic decomposition. Consequently, the amine is generated from an equimolar amount of the carbamate using a catalytic amount of the same amine. 1-(9-Fluorenylmethoxycarbonyl)piperidine and 1-(9-fluorenylmethoxycarbonyl)cyclohexylamine were suitable as base amplifiers because of their thermal stability under neutral conditions and high base-catalytic reactivity. On the basis of the results, 1,3-bis[1-(9-fluorenylmethoxycarbonyl)-4-piperidyl]propane and 1,6-bis[(9-fluorenylmethoxy)carbonylamino]hexane were designed as base amplifiers which liberate aliphatic diamines to crosslink poly(glycidyl methacrylate) photochemically in the presence of a photobase generator. Addition of the base amplifiers resulted in a marked improvement of the photosensitivity characteristics of the polymer by a factor of 16 and 50, respectively. © the Owner Societies. 

Catalysis; Decomposition; Fluorine compounds; Photochemical reactions; Propane; Sensitivity analysis; Thermodynamic stability; Autocatalysis; Base-sensitive materials; Amines; 1 (9 fluorenylmethoxycarbonyl)cyclohexylamine; 1 (9 fluorenylmethoxycarbonyl)piperidine; 1,3 bis[1 (9 fluorenylmethoxycarbonyl) 4 piperidyl]propane; 1,6 bis[(9 fluorenylmethoxy)carbonylamino]hexane; 9 fluorenylmethylcarbamate; aliphatic amine; amine; carbamic acid derivative; cyclohexylamine derivative; hexane; methacrylic acid derivative; poly(glycidylmethacrylate); polymer; propane; unclassified drug; amplifier; article; biotransformation; catalysis; catalyst; chemical reaction; cross linking; decomposition; fragmentation reaction; photochemistry; photosensitivity; thermostability