CA2050182A1 - Polyetherimidesiloxane copolymer compositions containing high melt flow polyetherimide homopolymer - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Polyetherimide siloxane copolymer compositions are provide which contain amounts of a high melt flow polyetherimide homopolymer. The compositions exhibit enhanced levels of impact strength and tensile elongation. The compositions are useful for making molded articles.

Description

POLYETHERIMIDIESILOXANE COPOLYMER COMPûSITIONS
CONITAINING HIGH MELT FLOll POLYET~ERIMIDE HOMOPOLYMER
Norman E. ~urfee, Jr.
John A. Rock BA~I(GRQU~D~ ~ THE~ E~IQI~
E~L~
The present invention relates to polyetherimide homopolymer siloxane polyetherimide copolymer blends, and more particularly relates to siloxane polyetherimide compositions containing a small amount of high melt flow polyetherimide homopolymer.
Description ~f Related Art Flame resistan~ polyetherimide homopolymer/-siloxane polyetherimide copolymer blends are set forth in EP 307670 corresponding to Male, et. al., U.S, patent application 092,940 filed September 4, 1987; and EP 266~95 corresponding to U.S. patent application 925,916 filed November 3, 1986. Male, et . al ., U . S . patent appl i cati on 092, 940, di scl oses blends comprising (i) a polyetherimide tii) a si loxane polyetherimide oopolymer and a 15 per~luorocarbon, and diseloses that the siloxane polyetherimide copolymer is employed in an impact strength enhanci ng concentrati on; for exampl e, from about 2% to about 90% by wei ght of the bl end, and that the perfl uorocarbon polymer i s empl oyed i n a 20 flammability-retarding amount, typically from about 0 . 2% by wei ght to 20% by wei ght of the pol ymer bl end . EP 266915 publ i shed May 11, 1988 and U . S .
patent appl i cati on 925, 916 fi l ed November 3, 1986, disclose blends comprising (i3 a polyetherimide and 25 (ii) a siloxane polyetherimide copolymer in an impact strength enhancing concentration, for example from about 2% to about 90% by weight of the blend.
While the fore~oing discloses improving the impact .
.

, .

. 8CT-4821 - 2 ~
strength of polyetherimide compositions, there is a need to improve the impact strength and tensile elon~ation of siloxane-polyetherimide copolymer compositions.
Accordingly, one objeet of the present invention is to provide siloxane-polyetherimide compositions exhibiting improv~d levels o~ impact strength and tensile elongation.
~MMARY_OF THE I~YENTIQ~
The present invention involves polyetherimide~
siloxane copolymer compositions containing small amounts of high melt flow polyetherimide homopolymer to improve the impact strength and tensile elon~a~ion of the composition. The composition is useful as a molding resin ~or making molded ar~icles, wire coatings and extruded parts.
DETAILED DES~RIPTION OF THE INYE~TIO~
Preferably the polyetherimide resin has a relatively hi~h melt flow which is preferably at 1e~st 15 9/10 min., more preferably between 15 and 8Q 9/10 min., and most preferably between 20 and 60 g/10 mi n . as measured by ASTM D1238 modi fi ed by usi ng a wei ~ht of 6700 grams at a temperature of ` 650F. The high melt flow polyetherimide resin appears to improve the notched Izod impact and tensile elongation values of the blends.
The siloxane poly~therimide copolymers employed in the blends of this invention may be prepared in a manner similar to that used for polyetherimides, except that a portion or all of the organio diamine reactant is replaced by an amine-terminated 30 organosil~xane of the formula:

3 - Z ~
(I) 1~3 IH3 H2N-- (CH2)n--Si -- (O~Si)g-- (CH2)m--NH2 wherein n and m independently are integers from 1 to about 10, preferably from 1 to about 5, most preferably about 3, and 9 is an integer from 1 to 5 about 40, preferably from about 5 to abou~ 25, and most preferably from 8 to 12.
The siloxane polyetherimide copolymers employed in ~he compositions of ~he present invention are referred to as late addition siloxane polyetherimide copolymers which are made by first reac~ing the organic diamine of formula XII with excess bis(ether anhydride~ and to form anhydride terminated oligomers and then reacting the amine-terminated organosiloxane of formula I.
The diamine component of the siloxane polyetherimide copolymers generally contains from about 20 to 50 mole % of the amine-terminated organosiloxane of formula I and from about 50 to 80 mole % of the organic diamine of formula XII. In preferred copolymers, ~he diamine component contains from about 25 to about 40 mole %, most preferably about 35 to 40 mole % of the amine-~erminated organosiloxane.
The polyetherimides used for preparin~ the 25 blends of this invention contain repeating groups of the formula:

,;.

.~ , . . .

Z~

(II) O O
11 i! \

N\ \~)iT-~ /N--R

I' I
O O

wherein "a" is an integer greater than 1, e.g., from 10 to 10,000 or more; T is--O--or a group of the formul a:
(III~

_ O _ Z--O--wherein the divalent bonds of the --O-- or the --O--Z--O - group are in the 3,3'; 3 j4'; 4,3', or the 4,4' positions; Z is a member of the class consi sti ng of (A):
(IV~

C~ CH3 o CH3 . ' ,, :
, ;
, "

C~ CH3 , and CH3 C~3 Br Br C(CH3) Br Br and (B) divalent organic radicals of the general formul a:
(V) ~X~

where X i s a member sel ected from the group consi sti ng of di val ent radi cal s of the formul as:
(VI ) O O
Il 11 .
--CyH2y-- ~ --C - I --S-- I O--and S--where y is an integer from 1 to about 5; and R is a 10 di val ent organi G radi cal sel ected from the group consisting of (a3 aromatic hydroearbon radicals havi ng from 6 to about 20 carbon atoms and hal ogenated deri vati ves thereof, (b) al kyl ene . .-~. ~ . - .

. . .
- : ~
:~ .

radicals having from 2 to about 20 carbon atoms, cycloalkylene radicals having from 3 to about 20 carbon atoms, and (c) divalent radicals of the general formula:
(VII) ~Q~

where Q is a member selected from the group consisting of:
(VIII) O O
ii il --S ~ 0 ~ ,--C--,--S--, and -CXH2x ~ , !
o and x is an integer from 1 to about 5.
o In one embodiment, the polyetherimide may be a eopo~ymer which, in addition to the etherimide units described above, further contains polyimide repeating units of the formula:
(IX) O O
Il 11 .

/ ~ / \
\C/ C/

Il 1' O O

7 ;~
wherein R is as previously defined and M is selected from the group consi sti ng of:
(X) ;~i and ~1~B~

where B is--S--or ~ C-- . These polyetherimide 5 copolymers and their preparation are described by Williams, et. al. in U.S. Patent No. 3,983,093, incorporated herein by reference.
The polyetherimides can be prepared by any o~
the methods well known to those skilled in the art, o including the reaction of the aromatic bis(ether anhydride) of the formula:
(XI) O O
Il 11 .

0/ ~ ~ T {~(' \ O

Il 11 O O

with an organic diamine of the fo~mula:
~XII) 15 wherein T and R are defined as described above.
Bis(ether anhydride)s of formula XI include, for example, ~ .

1,3-bis(2,3-dicarboxyphenoxy~benzene dianhydride;
1,4-bis(2,3-dicarboxyphenoxy)benzene dianhydride;
1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride;
and 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride;

4,4'-bis~phthalic anhydride)ether.
A preferred class of aromatic bis(e~her anhydride)s included by formula XI includes compounds of formula XIII, XIV, and XV, which follow:
(XIIIJ

O

/ b~Y~,~O/~`~\C~

O O

(XIV) O O
Il 11 0\~ ~\0 O O

.
, i ~' _ g ~
(XV) O O
Il 11 0/;~ C\o O O

and mixtures ~hereof, where Y is selected from the group consistin~ of -- O - , - S -, Il l 11 C - , - C , and - S - .
!l Aromatic bis(ether anhydride)s of formula XIII
include, for example:
2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride IBPADA);
4,4'-bis(3,4-dicarboxyphenQxy)diphenyl ether dianhydride;
4,4'-bis(3,4-diearboxyphenoxy)diphenyl sulfid@
dianhydride;
4,4'-bis(3,4-dicarbsxyphenoxy)benzophenone dianhydride;
4,4'-bis(3,4~dicarboxyphenoxy)dipheny7 sulfone dianhydride, and mixtures thereof.
Aromatic bis(ether anhydride)s of formula XIV
include, for example:

-:
, .

. 8CT-4821 2,2-bis(4-(2,3-dirarboxyphenoxy)phenyl)propane dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride;
54,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide di anhydri de, 4,4'-bis(2,3-dicarboxyphenoxy)benzophenone di anhydri de;
4,4'-bis(2,3-dicarboxyphenoxy)di phenyl sul fone 0dianhydride; and mixtures thereof.
The aromatic bis(ether anhydride~s of formula XV may be, for example, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-diearboxy- .
phenoxy) diphenyl-2,2-propane dianhydride;
154-~2,3-dicarboxyphenoxy-4'-(3,4-dicarboxy-phenoxy)diphenyl ether dianhydride;
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dioarboxy-phenoxy) diphenyl sulfide dianhydride;
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxy-phenoxy)benzophenone dianhydride;
4-(2,3-dicarboxyphenoxy~-4'-(3,4-dicarboxy-phenoxy~diphenyl sulfone dianhydride, and mix~ures thereof.
When polyetherimide/polyimide copolymers are 2s employed, a di anhydri de, such as pyromel 1 i ti c anhydri de, i s used i n combi nati on wi th the bis(ether anhydride).
Some of the aromatic bis(ether anhydride)s of formula XI are shown in U.S. Pa~ent No. 3,972,902 (Darrell Heath and Joseph Wirth). As described therein, the bis(ether anhydride)s can be prepared by the hydrolysis, followed by dehydration, of the reaetion product of a nitrosubstituted phenyl dinitrile with a metal salt of dihydric phenol ": " , !
,.

compound in the presence of a dipolar, aprotic solvent.
Additional aromatic bis(ether anhydride)s also included by formula XI above are shown by Koton, M.M., Florinski, F.S., Bessonov, M.I. and Rudakov, A.P. (Institute of He~eroorganic Compounds, Academy of Scienoes, U.S.S.R.), U.S.S.R. patent Z57,010, November 11, 1969, Appl. May 3, 1967, and by M.M.
Koton, F.S. Florinski, Zh. Orq. Khin. 4(5~, 774 (~968).
The organic diamines of formula XII include, for example:
m-phenylenediamine (MPD~, p-phenylenediamine, 4,4'-diaminodiphenylpropane.
4,4'-diaminodiphenylmethane (oommonly named 4, 4' -methyl enedi ani 1 i ne), 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether (commonly named 4,4'-oxydianiline), 1,5-diaminonaphthalene, 3,3-diamethylbenzidine, 3,3-dimethoxybenzidine, 2,4-bis~beta-amino-t-butyl)toluene, bis(p-beta-amino-t-butylphenyl)ether, bis(p-beta-methyl-o-aminophenyl)benzene, 1,3-diamino-4-isopropylbenzene, 1,2-bis(3-aminopropoxy)ethane, benzidine, m-xylylenediamine, 2,4~diaminotoluene, 2,6-diaminotoluene, bis(4-aminocyclohexyl)methane, 3-methylheptamethylenediamine, . ~ .
~ .

.

~C~-48~1 4,4-dimethylheptamethylenediamine, 2,11-dodecanediamine, 2,2-dimethylpropylenediamine, oc~amethylenediamine, 3~methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptame~hylenediamine, 5-me~hylnonamethylenediamine, o 1,4-cyclohexanediamine, 1,12~octadecanediamine, bis(3-aminopropyl)sulfide, N-methyl-bis(3-aminopropyl)amine, hexame~hylenediamine, heptamethylenediamine, nonamethylenediamine, decamethylenediamine, and mixtures o~ such diamines.
Both the polyetherimides and the si loxane polyetherimide cnpolymers used in the blends of this invention may be prepared by any of the procedures conventionally used for preparing polyetherimides.
A presently preferred method of preparatian is described in U.S. Patent No. 4,417,044, which is 2s incorporated herein by reference.
Blending the polyetherimide resin with the polyetherimide-siloxane copolymer in the amounts of the present invention provides a blend which is primarily polyetherimide-siloxane copolymer but 30 whi ch exhi bi ts certai n improved properti es over either the polyether-siloxane copolymer or polyetherimide resin alone.
In addition to the polymeric ingre~ients, the blends may contain other materials, such as fillers, .
. , , , ~

additives, reinforcing agents, pigments and the like. These blends exhibit very low flammabilities.
The polyetherimide resin is employed in the present blends in small amounts whioh enhance the 5 impac~ streng~h and tensile elongation of the composition. Such concentration of the polyetherimide homopolymer can range from 1% ~o 10%
by weight based on the ~otal weight of the composition, more preferably from 2.5% to 7.5% by weight thereof, and most preferably from 5% to 7.5%
by weight thereof; preferably the polyetherimide-siloxane copolymer is presen~ at a level of from 99.0% to 90% by wei ght of the composition, more preferably from 97.5% to 92.5% by 15 weight thereof, and most preferably from 92.5% to 95% by weight of the composition.
The following examples illus~rate the present invention and are not meant to be limiting.
EXQMPLES
The following examples illustrate the present invention but are not meant to limit the 500pe thereof.
Examples A, B r C ~ D and E are comparati ve examples. Example A is 100% by weight of a polyetherimidesiloxane copolymer, and Example B is 100% by weight of a polyetherimide. Examples 1, 2, 3, 4, 5 and 6 illustrate the enhanced properties obtained by blending a small amount of a relatively high melt flow polyetherimide with a relatively large amount of a late addition polyetherimide-siloxane.
The following abbreviations were used in Table 1:
LA PEI/Si is a late addition polyetherimide-siloxane copolymer made by reacting BPADA, MPD, and an amine terminated organosiloxane of formula (I) . ~ :

, . 8CT-4821 wherein g=9, n=3 and m-3. The amine terminated organosiloxane (AT0) was present at a level of about 40 mole percent based on the total moles of amine terminated organosiloxanQ and organic diamine. The moles of BPADA employed was substantially equal to the combined moles o~ MPD and AT0.
PEI for examples for 1 to 4 is a polye~herimide made by reacting BPADA, MPD and having a melt flow value of 20 g/10 min.
TS - Tensile strength in pounds per square inch as determined according to ASTM D638.
TE = Tensi 1 e el ongati on in % as determined according to ASTM D638.
FM = Fl exural modul us i n Mpsi as determi ned according to ASTM D790.
NI - Notched Izod in ft-lb/in as determi ned according l:o ASTM D256.
MI = Mel t i ndex i n 9/10 min as determined accordi ng to ASTM D1238 modified by using a weight of 6700 grams at a temperature of 343.3C (650-F).

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n a:l w LLI ~ L~ ~ 1 ~ O

Claims (8)

1. A thermoplastic composition comprising:
(a) a polyetherimide-siloxane copolymer wherein said polyetherimide-siloxane copolymer is prepared by:
(i) reacting an aromatic diamine with excess bis(etheranhydride) to form anhydride terminated oligomers; and (ii) reacting the anhydride terminated oligomers with a siloxane diamine;
and (b) a tensile elongation improving amount of a high melt flow polyetherimide homopolymer present at a level of from 1% to 10% by weight based on the total weight of the composition.

2. The composition of claim 1 wherein said polyetherimide resin is present at a level of from 2.5% to 7.5% by weight based on the total weight of the composition.

3. The composition of claim 2 wherein said polyetherimide resin has a melt flow value of at least 15 g/10 min. as measured by ASTM D1238 modified by using a weight of 6700 grams at a temperature of 650°F.

4. The composition of claim 3 wherein said polyetherimide-siloxane copolymer is present at a level of from 92.5% to 97.5% by weight based on the total weight of the composition.

5. The composition of claim 4 wherein said polyetherimide homopolymer consists of repeating units of the formula:

a where T is -O- or a group of the formula -O-Z-O- wherein the divalent bonds of the -O-or the -O-Z-O- group are in the 3,3', 3,4', 4,3' or 4,4' positions; Z is a member of the class consisting of (A) ,,,, ,, and and (B) divalent organic radicals of the general formula:

where X is a member selected from the group consisting of divalent radicals of the formulas:

, ,, -O- and -S-where y is an integer from 1 to about 5; and R
is a divalent organic radical selected from the group consisting of (a) aromatic hydrocarbon radicals having from 6 to about 20 carbon atoms and halogenated derivatives thereof, (b) alkylene radicals having from 2 to about 20 carbon atoms, cycloalkylene radicals having from 3 to about 20 carbon atoms, and (c) divalent radicals of the general formula:

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

-S-, -O-,,, and -CxH2x-, and x is an integer from 1 to about 5.

6. The composition of claim 5 wherein said polyetherimide-siloxane copolymer has repeating units of the formula:

7. The composition of claim 6 wherein said polyetherimide resin has a melt flow of between 20 and 60 g/10 min. as measured by ASTM D1238 modified by using a weight of 6700 grams at a temperature of 650°F.

8. The invention as defined in any of the preceding claims including any further features of novelty disclosed.