Synthesis and characterization of new organosoluble poly(ether imide)s derived from various novel bis(ether anhydride)s - Polyimides and Other High Temperature Polymers - page 47

hydroxyphenyl)-4-tert-butylcyclohexane (1C), 1,1-bis[4-hydroxyphenyl]cyclodo-

decane (1E) and 1,1-bis(4-hydroxyphenyl)-4-phenylcyclohexanon (1F) (Scheme
I) [5-8, 38-43]. The commercial diol, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)pro-
pane (1D), was purchased from TCI. The present study is concerned with the syn-
thesis and characterization of a series of new highly soluble poly(ether imide)s
based on new bis(ether anhydride)s such as 2,2'-dimethyl-4,4'-bis[4-(3,4-
dicarboxyphenoxy)]biphenyl dianhydride (4A, Scheme II) bearing noncoplanar
2,2'-dimethyl-4,4'-biphenylene unit, bis[4-(3,4-dicarboxyphenoxy)phenyl]diphenyl-
methane dianhydride (4B) containing kink diphenylmethylene linkage, 1,1-bis[4-
(4-dicarboxyphenoxy)phenyl]-4-tert-butylcyclohexane dianhydride (4C) bearing
bulky pendent tert-butylcyclohexylidene unit, 3,3',5,5'-tetramethyl-2,2-bis[4-(4-
dicarboxyphenoxy)phenyl]propane dianhydride (4D) bearing both flexible ether
and isopropylidene bridges between the phenylene units and tetramethyl substitu-
ents on the phenylene unit, 1,1-bis[4-(3,4-dicarboxyphenoxy)phenyl] cyclodo-
decane dianhydride (4E) bearing a bulky pendent alicyclic cyclododecane unit,
and 1,1-bis[4-(4-dicyanophenoxy)phenyl]-4-phenylcyclohexane dianhydride (4F)
bearing a 4-phenyl cyclohexylidene unit [38-43]. The effects of different units on
the polymer properties such as solubility, thermal and mechanical properties will
be discussed here [38-43].

2. EXPERIMENTAL

2.1. Materials [38-43]
The materials, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane (1D, Scheme II,
from TCI) and 4-nitrophthalonitrile (from TCI) were used without further purifi-
cation. N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc) and
pyridine were purified by distillation under reduced pressure over calcium hy-
dride before use. Acetic anhydride was purified by vacuum distillation.

2.2. Synthesis of diols, bis(ether dinitrile)s, bis(ether diacid)s
and bis(ether anhydride)s (Schemes I and II)
2.2.1. Synthesis of new diols (1A-1C, 1E and 1F, Scheme I)
The new diols (1A-1C, 1E and 1F, Scheme I) were synthesized by the procedures
in the previous studies as shown in Scheme I [5-8, 38-43].
2.2.2. Synthesis of bis(ether dinitrile)s (2A-2F, Scheme II) [38-43]
A typical procedure for synthesis of 2A (Scheme II) was as follows [38, 39]: In a
flask, 7.39 g (34.5 mmol) of 2,2'-dimethylbiphenyl-4,4'-diol (1A) and 12.2 g (70
mmol) of 4-nitrophthalonitrile were dissolved in 80 mL of dry DMF. Anhydrous
potassium carbonate (10.1 g, 73 mmol) was added and the suspension was stirred
at 170

C for two days. The reaction mixture was then poured into 500 mL of wa-
ter to give a pale-yellow solid product that was washed repeatedly with water and

°