V d . 18No. 3 CHINESE J O m OF (XEMWIRY m

Synthesis of novel poly (aryl ether amide) s containing the phtha- lazinone moiety

-

CHENG, LidBrbl;)'*" JIAN, X - G d ' ( R Q i 6 ) Uepartmeni of Materials Engineering , W h InstitLlte of Chemiud Techrwhgy , Wuhan , Hubei 43G074, China

5 Departmer~ of Polymer Science & Materials, Mian University of Technology, Dalian , Liaoning 116012, China

KeyworrLF cyclic d~amine, direct polymerization

Poly(ary1 ether amide)s, phthalazinone , hetero-

Jntrodudion

h g h - p e r f o ~ ~ ~ ~ ~ ~ e ar~natic p o l y ~ ~ ~ r s , such a~ a- matic plyamides and polyimides with high strength, d h e s s , and thermal stability and chemical resistance would provide some useful applications. But their limited solubility requires extreme synthesis and processing con- ditions. For example, poly ( p-phenylene terephthala- rmde), to form high-strength and high-modulus fibels

K ~ " L @ ) , must be processed frOm concentrated s ~ l f u - nc acid at elevated temperatures. ' Moreover, ammatic diarmnes which are commonly used for preparation of polyamides and plyimides, are light- and air-sensitive

materials and therefore difficult to punfy and handle. Furthennore, some ammatic diamines have been found to be carcinogenic, and special care must be taken in han- &ng these materials.2 To ovemme these limitations, structural modifications of the polymer backbone, such as the addition of bulky lated s u b s t i t ~ e n t s , ~ ~ flexible alkyl side chains,' noncoplanar biphenylene and organometallic complexati0n9 have been utilized to modify the polymer properties by the design and prepara- tion of new diamines.

phthalazinone and its derivatives have been known for almost a century . lo Until recently, ~ a y et OJ. f i t reported that Phthalazimne and its derivatives were bisphenol-like monomers which polymerize with the acti-

vated aryl dihalide monomers to give amorphous polymers with very high glass transition temperature and excellent themtability, which are soluble in common organic solvents. "-" Heterocyclic rings in poly ( aryl ether) s

generally increase mechanical and adhesive properties as weU as transition temperature ( T,) of the polymels, while retaining thermal stability and processability . Re- cently we have syntheized p l y ( aryl ether ketone) s and poly ( aryl ether sulfone ) s containing the phthalazinone

We first ported the synthesis of aromatic diamine and polyamides containing phthalazinone moi- ety." n e unique structural feature of the diamines lies in its unsymmetrical and "on-coplanar conformation. Of particular interests are to investigate the effect of the un- symmetrical and non-coplanar but still rigid diamine functionality on the pmperties of the polymers. In this paper, we describe the synthesis of two novel diamines

Received Novanber 2, 1999; accepted kember28 , 1999.

Pmject (No.59473019) supported by the National Natural Science Foundation of China.

Vol. 18 No. 3 2000 Chinese Journal of Chemistry 415

and a series of poly( aryl ether amide) s containing ph- thalazinone moiety.

Experimental

Mated and measurements

Unless specified otherwise, reagent-grade reactants and solvents were used as supplied. Pd-C( 5 % ) was ob- tained fmm Dalian Institute of Chemical Physics, Chi- nese Academy of Sciences. l-Methyl-2-pyrrolidinone and py-ridine purified on distillation under reduced pressure over calcium hydride and stored over mlecular sieves (48), Reagent-grade calcium chloride was dried under vacuum at 180"c: for 6 h prior to use. Triphenyl phos- phite was freshly vacuum-distilled before use. Dihydro- 4-( 4-hydroxyphenyl) ( 2 H ) phthalazin-l-one ( l a ) and dihydd-(4-hyd10~~-3,5-dimethylphenyl) ( 2 H ) phtha- lazin-1-one ( l b ) were prepared according to the reported method.",'s

'H and l3 C NMR spectra were obtained on a Jeol FX 9OQ or Bruker-400 instrument using tetramethylsi- lane as an internal reference. IR measurements were p e r f o d on Nicolet-20DXB spectrometer. Low and high-resolution mass spectra were obtained using Finni- gan MAT/SS220 and Kratos Concept H spectrometers, respectively. Melting points and the glass transition tem- peratures were obtained using a Serko 220C differential scanning calorimeter with a heating rate of 10Wmin in nitrogen. Intrinsic viscosities of al l polymers were mea-

sured using an Ubbelohde dilution viscometer.

synthesis ofmonomers

Preparation .f 2a A 5oomLtJuee-necked flask containing la (23.8 g, 0.1 mol) , p-chlomnitrobemne (34.6 g, 0.22 mol), potassium carbonate (33 g, 0.24 mol), DMAc (200 A), toluene (70 d), was e- quipped with a mechanical stirrer, a Dean-Stark trap, a water condenser, a thermometer, and a nitmgen inlet. Under an atmosphere of nitrogen, the mixture was heated and maintained at 1409: for 5-6 h to m v e all water by means of azeotropic distillation with toluene. The temperature was then increased to 15OT to remove toluene for 1 h and then cooled. 'zhe mixture was then poured into an ethanol-water mixture ( 1 : 1 V / V , 300 I&). 'Ihe precipitate was collected on a filter and crys-

tallized fmrn DMF to give yellow solid (44.2 g, yield: E%), mp, 235-2369:. JR (cm-'): 1112(w,N- N ) , 1262(m, C-0-C), 1346, 1509(s, NG). EI-MS ( m / z , relative intensity 96 ) : 480( M' ,100).

2b was prepared by the similar procedure of 2a. 2b: yellow solid, mp: 210--211"c, yield: 93%. IR (an-'): 1685(s, C = O ) , 1608(m, C = N ) , 1511, 1346(s, N q ) , l l l l ( m , N-N). EI-MS ( m / z , rela- tive intensity %): 508(M+, 100). ' H NMR (6, DM- SO-4): 8.55-7.60 ( m , 10H), 7.45-7.52 ( m , 2H), 7.05-7.13(m, 2H), 2.15(s, 6H, CH3).

Prepuratwn of 3a The dinirto compound 2a (33.6 g, 0.07 mol), Pd-C ( 5 % , 0.8 g) , and ethyl- glycoI monomethyl ether (500 &), were intmdud into a three-necked flask to which hydrazin monohydrate (175 mL) was added dmpwise over 1 h at reflw tmper- ature (about 105 "c: ) . After the addition was completed, the reaction was continued at reflux temperature for an- other 10 h. The mixture was then filtered and recrystal- lized from ethylglycol monomethyl ether to remove Pd-C . After cooling, the product was obtained as the pale yel- low crystals (mp: 260-261"c, yield: 95%) . IR (cm-'): 1104(w, N-N), 1224(m, C--0-C), 1606 (m, C = N ) , 1657(s, C = 01, 3336, 3368, 3403, 3432 ( m , N-H) . EI-MS ( m / z , relative intensity %): 420(M' , 100). HRMS: Calcd: 420. 1588, Found: 420. 1603, 'H M ( 6 , DMm-ds): 5 . 10 (bB, 4H, NH2), 6.65(d, . /=8 .65 Hz, 4H) , 6.85 (d , J = 8 . 6 4 H z , 2H), 6.99(d, J = 8 . 6 8 & , 2H), 7.26(d, 5 = 8 . 6 4 Hz, 2H), 7 .57(d, J = 8 . 7 2 Hz, 2H), 7.75(m, lH) , 7.90(m, 2H), 8.40(m, 1H).

3b was prepared by the analogous pmedure of 3a. 3b: pale yellow crystals ( mp: 282-2839: , yield: 91%). IR (cm-'): 3408, 3334(m, N-H), 2919(w, CH3), 1650(s, C = 0) , 1114(m, N-N). EI-MS ( m / z , relative intensity %>: 4 4 8 ( M + , l oo%) , 'H NMR (6, DMSO- d6) : 8.40( m , 1 H , H-8) , 7.80- 6.50(m, 13H, ArH), 5.20(brs, 2H, NH2), 4.61 (bE, 2H, NH2), 2 . 1 5 ( ~ , 6H, CH3).

Polymerization

A typical example of polycondensation is shown as follows :

Polymer 4a from 3a and terephthalic acid: A mix- ture of diamine 3a (1 . O W g, 2.5 mmol), terephthalic acid (0.418 g, 2 . 5 mmol), calcium chloride (0.45

416 Poly(ary1 ether amide) CHFJG & JLAN

g) , AMP ( 5 mL) , pyridine ( 1 . 4 mL) , and triphenyl phosptute ( 1.4 mL) , was heated with stirring at 100°C for 3 h under nitrcgen. ?he obtained polymer solution

stirring, producing fibrous precipitate. After being washed thoroughly with methanol and hot water, the p d u c t was collected on a filter, and dned at 1OOT under vacuum. ‘Ihe yield was 98%.

AU other polymers were prepared by similar manner as mentioned aboved.

was slowly poured into methanol (500 mL) with constant

Results and discussion

Two novel noncoplanar and asymmetric diamines:

1 , 2-dihydro-2-( 4-aminophenyl )4[ 4-( Caminophe- noxy)phenyl]-(2H)-phthalazin-l-one (3a) and 1,2-di- h y b 2 - ( 4-aminophenyl) 4[ 4-( 4-aminophenoxy)-3,5- dimethylphenyll-( 2H)-phthalazin-l-one (3b) ) , were synthesized on condensation of asymmetric heterocyclic bisphenol-like l a and l b with p-chloronitmbemne in presence of potassium carbonate respectively, giving cor- responding diNrto compounds 2a and 2b ( Scheme 1 ) , followed by reduction with hydrazine monohydrate/Pd- C. Unlike commonly used diamines, compound 3a and 3b are quite stable on exposure to li&t and air. The structures of the dinitro compounds 2 and diamine 3 w e confirmed by IT-IR, ‘H and 13C NMh, 2D-NMR, El- Ms, including HRMS. All the obtained data agree with the proposed structures.

R 1

H2NNH2 ‘ HZO Pd - C H2N

d 3

R 2 6 R=H: la, 2a, 30. R=CHs: lb, 2b, 3b.

‘Ihe direct polycondensation of the diamine 3 with the aromatic diacids was undertaken successflluy accord- ing ta the phosphorylation method first q o r t d by Ya- nlazaki for the synthesis of polyamides ( Scheme 2 ) . l9

Almost quantitative yields of the polyamides 4a-c were obtained. Spectroscopic data, together with intrinsic vis- mity and T , measurements, confinning the structures of polyamides, are given in Table 1. Almost all polyamides

Vol. 18 No. 3 2000 Chinese Joumal of Chemistq 417

were soluble in polar apmtic solvents such as NI", DMF, DMAc , DMSO and even in pyridine. Transparent

and flexible films were easily prepared by solution cast- ing from DMAc solution of each polymer 4 and 5.

TaMe 1 Synthesis and characterimtim data of the polymer (4a-c and 5a-c)

Polymer [q]" Yield(%) 'H NMR (&, 90 MHZ) IR (Cm-1) TKb

329

314

6.W-8.51(m,u)H,ArH), 10.21- 3310(m,N-H), 1658(s,amide I ) , 10.39( brs, 2H, NH) 1 W ( rn, C = N)

6.*8.65(m,ulH,ArH), 10.32- 3308(m,N-H), 1668(s,amide I), 10.49( IS ,2H, NH) 1607(m,C= N)

6.71-8.72(m,22H,ArH), 10.39- 3314(m,N-H), 1668(s,amide I ) , 10.48(lnS,W,NH) 1604(rn,C=N)

4a 1.43 98

4b 1.26 98

4c 1.51 % ND"

2.15(st6H,CH3), 6.81- 3305(m,NH), 1657(s,amide I ) ,

16U2(m,C= N) 291 5a 1.38 98 8.59( m, 18H, ArH) , 10.21-

10.49(bra,2H,NH)

2.15(s,6H,CH3), 6.- ND 3334(rn,NH), 1667(s,amide I).

1607(m,C= N) 5b 1.16 97 8.63( rn, 18H, ArH) , 10.19- 10.51 ( brs,ZH, NH)

ND ride I ) .

10.51 ( brs,2H, NH) a Measured at a amcentmiion of 0.5 fl in NMP at 25T; Fnnn DSC measuranent8 conducted at a rate of lOqC/min in nitragen

No T,was obeewed in Dsc trace.

In conclusion, novel amoqhous p l y ( aryl ether amide)s containing the phthalazinone moiety with high molecular weights were prepared using the phosphoryla- tion method. The polymers showed outstanding t h d stability, good solubility and film-forming property. Fur- ther preparation of a series of poly ( aryl ether amide ) containing the phthalazinone moiety is in pmgress.

Acknowledgments

The authors thank Prof. Wang, Z.Y. and Dr. Zheng, H. B. at Carleton University for recording the NMR spectra and HRMS.

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(I5911150 JIANG, X.H.; DONG, L.J . )