化合物的反应性极高但在有些应用上需要延迟异氰酸盐ppt课件.pptVIP

;異氰酸鹽(Isocyanates, -NCO)和羥基(-OH)化合物的反應性極高，但在有些應用上需要延遲異氰酸鹽與羥基的反應，並在適當的步驟下適放異氰酸鹽官能基。 封閉型異氰酸鹽是異氰酸鹽和帶有活性氫的封閉劑(Blocked agegnt BH)反應生成一個弱鍵結的化合物；在一定溫度下釋放出(-NCO)官能基。 ;封閉型聚異氰酸鹽，對於水氣有良好的抵抗性及較佳的儲存性。 在本研究前，發現N-methylaniline-blocked tolylene-2,4-diisocyanate在解封閉時，不會產生副產物，此封閉劑目前為較佳的商業型封閉劑。 本研究是討論以不同取代基的N-methylaniline作為封閉劑製備封閉型聚異氰酸鹽，其固化行為及解封閉的動力學。;N-Methylaniline (Lancaster) Methyl 2-methylaminobenzoate(Lancaster) Methyl 4-methylaminobenzoate(Lancaster) N-methyl-o-anisidine (Aldrich) Nmethyl-p-anisidine (Aldrich) N-methyl-o-toludine(Aldrich) N-methyl-p-toludine (Aldrich) 2-chloro-N-methylaniline (Aldrich) 4-chloro-N-methylaniline(Aldrich) N-methyl-4-nitroaniline (Aldrich);4,4-Methylenebis(phenylisocyanate) (MDI; Lancaster) Phenyl isocyanate(Aldrich) Poly(tetrahydrofuran) (Terathane; Mn=2000;Aldrich) Dibutylamine (Fluka) Hydroxyl-terminated polybutadiene(HTPB; Mn=2500), obtained from Vikram SarabhaiSpace Centre, was used after drying for 2 hat 80 ℃ in vacuo. Toluene (Merck), methanol(Merck), and chloroform (Merck) were purifiedaccording to standard procedures.;PTHF;Sample;The electron-donating substituents rendered the nitrogen atom of N-methylaniline more basic for its easy attack on the partially positive carbon atom of the -NCO group, thereby increasing the rate of the blocking reaction. The slow blocking reaction of N-methylaniline substituted with electron-donating substituents at the ortho position may be attributed to the steric factor.;Urea:153.69 ppm urethane:154.39 ppm;Polyisocyanate 2;The use of phenol as a blocking agent for isocyanates is understandable because phenol is less nucleophilic toward isocyanate groups; as a result, the bond that forms between the carbonyl carbon of isocyanate and the oxygen atom of phenol is labile.;Variable-temperature 1H NMR spectra of blocked polyisocyanate 2, showing a frequency shift of (a) hydrogen-bonded urethane and (b) urea protons in CDCl3.;;FTIR spectrum of (A) blocked isocyanate 12, (B) blocked polyisocyanate 2 recorded at 140