39 2 Vol 39 No 2 2015 3 Journal of Jiangxi Normal University Natural Science Mar 2015 1000-5862 2015 02-0154-05 TDPA * 330022 4 4 - TDPA MPD PA 2 PI FT-IR WAXD DSC TGA FT-IR 2 PAA DSC TGA PI PI T g 280 6 Larc-I-TPI 259 TDPA TS 174 8 TB33 A DOI 10 16357 /j cnki issn1000-5862 2015 02 08 0 PI 1 Larc-I-TPI 4 4 - TDPA IDPA TDPA PI 13 1-2 PI PI 4 4 - PI 1967 PI TDPA sky bond 700 720 6234 3-4 PI 2 4 PI PI 20 70 PI T g 283 5-6 20 90 500 NASA 4 4 - IDPA PI Larc-I-TPI 1 1 IDPA 2 Ti /Ti 1 1 18 5 MPa204 232 22 9 MPa 4 4 - TDPA 20 8 MPa 7-8 14 MPD m p 64 ~ 65 N N- 9-12 MPD Larc-I-TPI DMAc GaH 2 24 h 0 4 nm 24 h PA 2014-12-20 51003044 2012 GJJ12193 20132BAB206035 KJLD13023 1975-
2 TDPA 155 m p 130 8 ~ 131 0 T-PI 2 1 5 PI Py 1 2 η inh 15 PAA DMAc 1 0 g dl - 1 T-1040 4-2006 1 3 PAA N 2 250 ml MPD 1 622 1 g 0 015 0 mol 50 ml DMAc TDPA 6 517 8 g 0 015 3 mol 30 min 0 ~ 20 7 ~ 8 h 2 h PAA TD- PA MPD PA 1 3 PAA 1 PAA PAA 7IDPA-PAA η inh TDPA MPD PA η inh / dl g - 1 IDPA-MPD η inh / dl g - 1 7 PAA-1 1 02 1 00 0 0 81 0 52 PAA-2 1 00 1 00 0 0 72 0 51 PAA-3 0 99 1 00 0 04 0 70 0 43 1 4 PI 180 1 h 220 1 h PAA DMAc 2 1 /Py 60 ± 5 18 h PI DMAc PI 24 h 3 ~ 4 120 35 ± 1 24 h C-PI 3 η inh = c - 1 lnt /t 0 AVA-TAR370 KBr 2 400 ~ 4 000 cm - 1 X- Bruker-XRF X- Cu Kα 2 1 PI 40 kv /30 ma 2θ = 4 ~ 90 4 PAA T-PI C-PI DSC TA-Q100 4 PAA 1 715 cm - 1 10 K min - 1 50 ~ 1 657 cm - 1 C O C O 400 TGA TA-CDR-1 1 780 cm - 1 20 ~ 800 C O 3 385 cm - 1 O H 10 K min - 1 CMT7105 N H PAA GB / 90 T-PI C-PI 1 780 1 722 cm - 1 1 780 1 728 cm - 1 2 C O O H N H PAA FT-IR 2 2 250 2 h 280 0 5 h 5 2 PI PI PAAs cm - 1 C O O H / N H C N PAA 1 780 1 715 1 657 715 3 385 1 355 T-PI 1 780 1 722 1 661 719-1 360 C-PI 1 780 1 728 1 664 719-1 363 2 2 PI X- WAXD X- WAXD PAA DMAc 0 5 mm 2 90 PAA PI T-PI WAXD 1
156 2015 13 3 PI TGA 4 PAA T-PI C-PI C-PI 5 /Py DMAc PAA PI 16 3 PI 2 3 PI 10 mg PI C-PI 5 ml 3 PI PI PI NMP DMF DMAc DMSO THF T-PI - - - - - - - - C-PI - - - - - - - - + + + - 2 4 PI DSC PA-T-PI-3 T-PI-1 T DSC g PI T g DSC 6 4 T-PI-2 PA T-PI-3 T g T- PI T g 283 9 T TDPA m 372 4 T-PI-1 T g 280 6 T-PI-1 PI PI 2 PA TD- T g Larc-I-TPI
2 TDPA 157 C-PI T g WAXD DSC 299 3 4 PI T-PI-1 T g 280 6 C-PI Polyimide T g / T d / T 5 / T 10 / R w /% C-PI 299 3 522 2 532 0 557 0 48 1 T g T-PI-1 280 6 510 5 512 3 522 8 58 6 T-PI-2 278 6 508 1 511 6 525 1 57 6 T-PI-3 283 9 513 1 515 3 522 8 57 9 3 6 2 5 TG PI DSC PA-PI 7 PA T- PI-3 T d 513 1 TDPA T-PI-1 T d 510 5 T- PI-2 T d 513 1 PI T- PI-2 1 M TDPA MPD TDPA DMAc PAA PAA PI PI PA PI TDPA PI TDPA PI C-PI TD- T d 500 TD- PA-PI Larc-I-TPI 4 1991 743-777 2 Kim K Ryou J H Klm Y Thermal imidization behavior of aromatic poly amic dialkyl ester precursors derived from biphenyltetracarboxylic dianhydride J Polymer Bulletin 1995 34 219-226 3 M 1998 177-201 4 McCracken J H DeGorski J G Gall W G Process for preparing benzophenone acids and anhydrides and anhydrides resulting therefrom US 3287373 P 1966-11-22 5 DeGorski E Sillion B DeGaudemaris G French institute of petroleum fuels and lubricants French Patent 1601094 P 1970-09 6 Pfeifer J Geigy A Homo and copolymer proess of their 7 PI TGA crosslinking and their use EP 162017B1 P 1985-11 2 7 Donald J P Terry L St Clair Pratt J R Thermoplastic adhesives based on 4 4 -isophthaloyl diphthalic anhydride 7 7 C-PI 522 2 T d T-PI-1 510 5 IDPA R NASA TM-101508 1988 C-PI 8 Progar D J Dezern J F Initial evaluation of novel poly-im-
158 2015 ide-imides and their copolymers as adhesives J J Adhes Sci Technol 1989 3 4 305-316 9 Tamai S Kuroki T Synthesis and characterization of thermally stable semicrystalline polyimide based on 3 4 - oxydianiline and 3 3 4 4 -biphenyltetracarboxylic dianhydride J Polymer 2002 42 2373-2378 10 Basset F Lefrant A Pascal T et al Crystalline polyimide particles generated via thermal imidization in a heterogeneous medium J Polymers for Advanced Technologies 1998 9 202-209 11 Inoue H Muramatu T Sasaki Y et al Preparation of polyimide powder J Journal of Applied Polymer Science 1996 61 929-933 12 Gall W G Process for preparing finely divided polyimide particles of high surface area US 3249588 P 1966-05- 03 13 Lovejoy E R Coupling polymerization of low molecular weight polyamide-acids to produce high molecular weight polyimides US 3511807 P 1970-05-12 14 4 4-236736 4 P 2013-10 4 4-384452 X P 2013-10 15 Goel R N Varma I K Varma D S Preparation and properties of polyimide fibers J J Appl Polym Sci 1979 24 1061-1067 16 J 2007 4 40-43 Ths Synthesis of Polyimide and the Properties of the Adhesive Film ZHAN Meidong HU Shuncheng SONG Cheng * SONG Caisheng College of Chemistry and Chemical Engineering Jiangxi Normal University Nanchang Jiangxi 33002 China Abstract A novel diketone anhydride poly ether ketone ether imides PI was synthesized via the conventional two-step by using 4 4 -terephthaloyldiphthalic anhydride TDPA and m-phenylenediamine MPD Polyimide acid PAA was end capped with the excess TDPA or small amount of phthalic anhydride PA and took the research of the influence to the thermodynamic property Research the two polyimide properties which prepared by thermal and chemical imidization The structure and properties of PI was characterized and measured by fourier transform infrared spectroscopy FT-IR wide-angle X-ray diffraction WAXD differential scanning calorimetric DSC thermal gravimetric analysis TGA and solubility tests FT-IR tests show that the two imidization ways both can make PAA form an imide ring structure DSC and TGA show that end-cap can improve Thermal properties of PI to some extent and the chemical imidization is superior to thermal imidization PI a Thermoplastic polyimide which T g is 280 6 above Larc-I-TPI 259 have good thermal and solvent preperties LSS tests show that PI has excellent adhesion properties Key words thermal imidization TDPA chemical imidization adhesion properties