CA1245799A - Polyetherimide-polyethersulphoneimide copolymers - Google Patents

Abstract

POLYETHERIMIDE-POLYETHERSULPHONEIMIDE COPOLYMERS
ABSTRACT OF THE DISCLOSURE

Polyetherimide-polyethersulphoneimide copolymers are provided by reacting an aromatic bis(ether anhydride), a diaminosulphone compound and an organic diamine.

Description

~9L5~99 POLYETHERIMIDE-POLYETHERSULPHONEIMIDE COPOLYMERS
BACKGROUND
Polyetherimides are amorphous, high performance engineering thermoplastics characterized by high heat resistance, high strength and modulus, good electrical properties which remain stable over a wlde range of temperatures and frequencies. Unmodified polyetherimide resin is transparent and exhibits inherent flame resistance and low smoke evolution wi-thout addi-tives.
Polyetherirnides are generally provided by eE~ecting reaction between certain aroma-tic bis(etheranhydride) and organic diamine. The resulting polymer exhibits high riyidity, creep resistance and high heat deflection temperatures due to the rigid aromatic imide function-ality while the ether moiety confers the necessary degree of chain flexibility for good melt processibility and flow behavior.
U.S. Patent 4,107,1g7 discloses polysulphoneimide compounds. These compounds are provided by reacting organic diamines with aromatic bis(sulfoneanhydrides3.
Although these compounds have the advantage of the rigid aromatic imide functionality, they suffer from the lack of those properties that are contributed to a polymer having an ether moiety.
SU~ARY OF THE INVENTION
The copolymers of the present invention contain repeating units of the following structural formulas:

7~

2 . 08 cu 03486 o o Il . Il O

--~3 ~ ~} O--~-- ~ C ~ N R 1 11 R2--' Il 11 0 o and O O II.
C C
N ~_z_~ N~R

Il 11 O o wherein Z is a member o~ the class consisting o~
h CH3 ~C)/ ' ~/~;\/- ' \~/~

/0~

c~3 Br ~r CH3 . Br Br and \or C ~ CH3 ) 2 ~0 c~3 ~r Br CH3 Br Br and ~ 2 ) divalent organic radicals of the general ` ~L;2 ~57~9

3 08CU 03~86 formula:

~O/~( x ) q ~O,~--where X is a member selected from the class consisting o~
divalent radicals of the formulas, O O
Il 11 CyH2y~~ -C-, ~S-, -O- and -S-where q is 0 or 1, y is a whole number from 1 to 5~ the divalent bonds of the -O-Z-O- radical being situated on the phthalic anhydride end groups, in the 3v3'-3,4'-,

4,31_ or the 4,4' -positions, and R is a divalent organic radical selected from the class consisting of (a) aromatic hydrocarbon radicals having from 6 to about 20 carbon atoms and halogenated derivatives thereof, (b) alkylene radicals and cycloalkylene radicals having from 2 to about 20 carbon atoms, C(2-8) alkylene ~erminated polydiorganosiloxane, and (c) divalent radicals included by the formula:

~/o ~___ Q ~ O /-~

where Q is a member selected from the class consisting of:

Il -O-, -C-, -S-, and -CXH2x , where x is a whole number from 1 to 5 inclusive and R1 and R2 are each divalent organic radical independentl~
selected from the class consisting of ~a) aromatic ~579~a 4 08Cu 03~86 hydrocarbon radicals having from 6 to ahout 20 c~rbon atoms and halogenated derivatives thereof, and (b) alky-lene radicals and cycloalkylene radicals having from 2 to about 20 carbon atoms, C(2_g) alkylene terminated polydi-organosiloxane and (c) divalent radicals included by theformula:

~ ~ - Q ~ O /__ where Q is a member selected from the class consisting of O
Il 11 .
-O , -C-~ -S-, -S-, and -C H~ -where x is a whole number from 1 to 5 inclusive.
DETAILS OF DESCRIPTION
The present invention relates to polyetherimide-polyethersulphoneimide copolymers. These copolymers contain basically two types of repeating polymeric units.
The first unit is the reaction product of a bis(ether anhydride) and a diaminosulphone compound. T~e second unit is the reaction product of a bis(ether anhydride) and a certain diamine compound.
The polyetherimide~polyethersulphoneimide copolymers of the present invention can be obtained by various methods.
One procedure involves the reaction of any aromatic bis-(ether anhydride~ of the formula:

~5i'75~
08Cu 03~86 O O
Il 11 O ~ Z~ - ~ C\O III.

Il 11 O , O
where Z is defined hereinabove with a diaminosulphone of ~he formula:

H~N-RI-S-R2-NH2 IV.

and a diamino compound of the formula:
H2N-R-NH2 V.
where ~r ~1 and R2 are independently se~ected rom the groups herein defined. In general, the reaction can be advantageously carried out employing well-known solvents, n e.g., o-dichlorobenzene~ m-cresol~toluene, etc., in which to effect interaction between the dianhydrides, the diaminosulphones of Formula IV and the diamines of Formula V, at a temperature of from about 100 ~C to about 250~C. Alternatively, these copolymers can be prepared by melt polymerization of any dianhydride of Formula III
with any diaminosulphone of Formula IV and diamine of Formula V while heating a mixture of the reactants to melt polymerization temperatures with concurrent intermixing. Generally, melt polymerization temper-atures between about 200 and 400C a~d pre~erably 2~0 to 300C can be employed. Any order of addition of chain stoppers ordinarily employed in melt polymerizations can be employed. The conditions of the reaction and the

5'743~

proportions of ingredients can be variecl depending on the desired molecular weight, intrinsic viscosity, and solvent resiskence. In general, equimolar amounts of the dianhydride and total diamine are employed for high molecular weight copolymers; however, in certain instances, a slight molar excess (about 1 to 5 mole percent) of either the diaminosulphone compound of Formula IV or the diamino compound of Formula V or mistures thereof can be employed, resultin~ in the production of copolymers having terminal amine groups.
Methods of making polyetherimides havin~ the repeating unit of Formula II are disclosed in U.S.
Patent Numbers Heath et al. 3,847,867; Williams 3,847,869; Takekoshi et al. 3,850,885; r,~hite 3,852,242 and 3,855,17E etc.
The aromatic bis(ether anhydride)s of Formula III include for example, 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]-propane dianydride;
4,4'-bis(2,3-dicarboxyphenoxy)dipehnyl ether dianhydride;
1,3-bis(2,3-dicarboxyphenoxy)benzene dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sufide dianhydride;
1,4-bis(2,3-dicarboxyphenoxy)benzene dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)benzophenone dianydride;
4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride; etc.
2,2-bis[4-(3,4-dicarboyxphenoxy)phenyl]-propane dianhydride;

~ ,~

579~
7 08Cu 03486 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride;
1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride;
4,4'-bis~3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride;
1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride;
4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride;
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)-diphenyl-2,2-propane dianhydride; etc. and mix~ures of such dianhydrides.
In addition, aromatic bis(ether anhydride)s also included by Formula III are shown by Roton, M.M.;
Florinski, F.S.; Bessonov, M.I.; Rudakov, A~ P.
(Institute of Hetervorganic Compounds, Academy of Sciences, U.S.S.R.), U.S.S.R. 257,010, Nov. 11, 1969, Appln. May 3, 1967. In addition, dianhydrides are shown by M. M. Koton, F. S. Florinski, Zh. Or~. Khin; 4(5), 774 ~1968)~
The diaminosulphones of Formula IV include for example, bis(aminopentamethylene) sulfone;
bis(aminohexamethylene) sulfone;
bis(aminoheptamethylene) sulfone;
bis~aminooctamethylene) sulfone;
bis(aminorindecamethylene) sulfone;
bis(aminotridecamethylene) sulfone;
bis(aminohexadecamethylene) sulfone;
bis(aminononadecamethylene) sul~one;
bis(aminocylopentamethylene) sulfone;
bis(aminocyclohexamethylene) sulfone;
bis(aminocycloheptamethylene) sulfone;
m-diaminophenyl sulfone p diaminophenyl sulfone;
aminophenyl, aminohexamethylene sulfone;
aminophenyl, aminoheptamethylene sulfone;

~L2~5~99 8 ~ 3~6 aminophenyl, aminooctamethylene sulfone, etc. and mixtures of such diaminosulfones.
The organic diamine of Formula V inelude, for example, S m-phenylenediamine, p-phenylenedlamine, ~,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine, 4t4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ether, l,S-diaminonaphthalene, 3,3' dimethylbenzidine, 3,3'-dimethoxybenzidine, 1S 2,4-bis(~-amino t-butyl)toluene, bis(p-~-amino-t-butylphenyl)ether bis(p ~-methyl-o-aminopentyl)benzine, 1,3-diamino-4-isopropylbenzene, 1,2~bis(3-aminopropoxy)ethane, m-xylylenediamine, p-xylylenediamine, 2~4-diaminotoluene, 2,6-diaminotoluene, bis(4-aminoxyclohexyl)methane, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-dodecanediamine, 2,2-dimethylpropylenediamine, octamethylenediamine, 3 methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 5-methylnonamethylenediamine, ~ 5799 08CU ~3~8~

1,4-cyclohexanediamine, 1,12-octadecanediamine, bis~3-aminopropyl)sulfide, N-methyl-bis(3-aminopropyl)amine hexamethylenediamine, heptamethylenediamine, nonamethylenediamine, decamethylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis~4-aminobutyl)tetramethyldisiloxane, etc., and mixtures of such diamines.
In producing the polyetherimide polyethersulphone-imide copolymers of the present invention, a diaminosul-phone of Formula IV and an organic diamine of Formula V
are utilized. The molar ratio of the diaminosulphone and organic diamine can vary depending on the desired proper-ties of the copolymers to be produced. The diaminosul-phone can constitute from about 5 to 95 mole percent of the total diamine moiety reacted, with the balance being the diamine of Formula V i.e., 95 to 5 mole percent.
Preferably, the diamino~ulphone is from about 10 to 90 mole ~ercent of the to~al diamine moiety, and particu-larly preferred copolymers are those in which the diaminosulphone moiety is from about 20 to 80 mole percent of the total diamine moiety.
By controlling the proportions of the polymeric units of Formulas I and II, each having predetermined properties, a copolymer can be produced having superior properties over a polymer containing only one of the polymeri~ units. In general, the highe~ proportion of the polymeric units of Formula I will result in a poly-ethersulphoneimide having a higher glass transition temp-eratur~. On the other hand, a polyetherimide polyether-sulphoneimide copolymer having a higher proportion of the polymeric ~nits of Formula II will have lower glass tran-sition temperatu~es.

~2~5'7~
08cu 03486 Copolymers having greater than 1, e.g. 10 to 10,000 or more polymeric units of Formula I and Formula II can be ormed. These polymers can be blended with various fillers such as finely divided silica, glass fibers~
carbon whis~ers, perlite, etc. The resulting filled compositions can, on a weight basis, have a proportion of from about 1 par~ to 200 parts of filler per hundred parts of copolymer. The blending of the filler with the copolymer can be achieved by adding the Eiller prior to forming the melt or directly to the melt~ Stirring can be effected with standard agitating means to facilitate blending the ingredients.
The novel copolymers of the present invention have application in a wide variety of physical shapes and form, including their use as films, molding compound~, coatings, etc. Thusl the compositions o~ the pre~ent ~nvention can be used in automobile and aviation applica-tions for decorative and protective purposes, as high - temperature electrical insulation, for motor slot lines, in transformers, as dielectric capacitors, a5 coil and cable wrappings, for containers and container linings, in laminating structures where films of the present composi-tion or where solutions of the claimed compositions of matter are appl ed to various heat-resistant Jr other type of materials such as asbestos, mica, glass fiber and the like and superposing the sheets one- upon ;-'e other and thereafter subjecting them to elevated temperatures and pressures to e~fect flow and cure of the resinous binder to yield cohesive laminated structures. Alterna-tively, solutions of the compositions herein describe~can be coated on electrical conductors such as copper, aluminum, etc., and thereafter the coated conductor can be heated at elevated temperatures to remove the sol~ent and to effect curing of the compositions thereon. If desired, an additionai overcoat may be applied to such '7~
1t ~ 86 insulated conductors including the use of polymeric coatings, such as polyamic;es, polyesters, silicones, polyvinylformal resins, epoxy resins, other polyimides, polytetrafluoroethylene, etc.
The copolymers herein disclosed and claimed may be suitably incorporated with other materials to modify the properties of the latter or in turn they may be modified by the incorporation of the materials. For example, th~y may be compounded with substances such as natural or synthetic rubbers, synthetic resins such as polycarbon-ates r polyamides, polysulphones, polyethersulphones, polyetheretherketones, polyamideimide~, polyphenylene oxide and polyesters such as polyethylene terephthalate and polybutlyene ~ereph~halate. The blend may also contain mixtures of the above synthetic resins. Because of the advantageous high temperature properties of these polymeric compositions, the incorporation of these polymers in other polymers which may not be so favorably disposed, for instance, polycarbonate resins, polypheny-lene oxide resins, polybutylene terephalate resins, etc.in amounts ranging from 5 to 75%, by weight, based on the total weight of the polvethersu1foneimide and the afore-said resins, can improve the properties of the resins in which the polyethersulfoneimides of the present invention are incorporated.
The present invention is Eurther illustrated by the following examples, which are not intended to be limiting.
Example I
To a suitable rea~tion vessel was charged ~5e~ of N-methyl pyrrolidone. Thereafter, 25 mole equivalPnts (m.eq.) of hexamethylene diamine, 25 m.eq. of diaminodi-phenylsulphone and 50 m.eq. of 2,2-bis[4-(2,3-dicarboxy-phenyoxy)phenyl]-propane dianhydride were added and m.xed. The polymer solutions were cast and films were 7~3~
12 ~8CU 034~6 obtained after heating at 250-29boC. The product polyethersulphoneimide had a Tg of 152C. The Tg was determined on the film using ~ differential scanning calorimeter.
~ 5 ~ 3~ ~
To a suitable reaction vessel was charged ~6~ of N-methyl pyrrolidone. Thereafter, 25 m.eq. of m-xylylene-diamine, 25 m.eq. of diaminodiphenylsulphone and S~ m.eqO
of 2,2-bis[4-(2,3-dicarboxy)phenyl]-prop,ane dianhydride were added and mixed. The polymer solutions were cast and films were obtained after heating at 250-29nc. The product polyethersulphoneimide had a Tg of 194C and ~as determined as in Example I.

Claims (10)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A polyetherimide polyethersulphoneimide copolymer consisting essentially of the polymeric units of the formulas:

I.

and II.

where Z is a member of the class consisting of (1):


1. Claim 1 continued:
   
   and and (2) divalent organic radicals of the general formula:
   
   where X is a member selected from the class consisting of divalent radicals of the formulas, -CYH2Y-, -O- and -S-where q is 0 or 1, y is a whole number from 1 to 5, the divalent bonds of the -O-Z-O- radical being situated on the phthalic anhydride end groups, in the 3,3'-3,4'-, 4,3'- or the 4,4'-positions, and R is a divalent organic radical selected from the class consisting of (a) aromatic hydrocarbon radicals having from 6-20 carbon atoms and halogenated derivatives thereof, (b) alkylene radicals and cycloalkylene radicals having from 2-20 carbon atoms, C(2-8) alkylene terminated polydiorganosiloxane, and (c) divalent radicals included by the formula:
   
   where Q is a member selected from the class consisting of:
   
   -O-, , -S- , and -CXH2X-, where x is a whole number from 1 to 5 inclusive and R1 and R2 are each a divalent organic radical selected from the class consisting of (a) aromatic hydrocarbon radicals having from 6 20 carbon atoms and halogenated derivatives thereof and (b) alkylene radicals and cycloalkylene radicals having from 2-20 carbon atoms and C(2-8) alkylene terminated polyorganosiloxane.
2. 2. The polyetherimide-polyethersulphoneimide copolymer of claim 1 wherein from 5 to 95 mole percent of the total diamine moiety is a diaminosulphone.
3. 3. The polyetherimide-polyethersulphoneimide copolymer of claim 2 wherein from 10 to 90 mole percent of the total diamine moiety is a diaminosulphone.
4. 4. The polyetherimide-polyethersulphoneimide copolymer of claim 3 wherein from 20 to 80 mole percent of the total diamine moiety is a diaminosulphone.
5. 5. The polyetherimide-polyethersulphoneimide copolymer of claim 1 wherein R1 and R2 are each selected from the group consisting of aromatic hydrocarbon radicals having from 6 to 18 carbon atoms.
6. 6. The polyetherimide-polyethersulphoneimide copolymer of claim 5 wherein R1 and R2 are aromatic hydrocarbon radicals having 6 carbon atoms.
7. 7. The polyetherimide-polyethersulphoneimide copolymer of claim 1 wherein said copolymer is blended with natural rubber, synthetic rubber and synthetic resins selected from the group consisting of polycarbonates, polyamides, polysulphones, polyetheretherketones, polyamide-imides, polyphenylene oxide, polyesters or mixtures thereof.
8. 8. The polyetherimide-polyethersulphoneimide copolymer of claim 7 wherein said copolymer is blended in amounts ranging from 5 to 75 percent by weight, based on the total weight of the blend.
9. 9. The polyetherimide-polyethersulphoneimide copolymer of claim 8 wherein said copolymer is blended with polycarbonate or a polyester.
10. 10. The polyetherimide-polyethersulphoneimide copolymer of claim 9 wherein said copolymer is blended with polyethylene terephthalate or polybutylene terephthalate.