CA1192689A - Polyetherimide blends - Google Patents
Polyetherimide blendsInfo
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- CA1192689A CA1192689A CA000425849A CA425849A CA1192689A CA 1192689 A CA1192689 A CA 1192689A CA 000425849 A CA000425849 A CA 000425849A CA 425849 A CA425849 A CA 425849A CA 1192689 A CA1192689 A CA 1192689A
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- polyetherimide
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Abstract
ABSTRACT OF THE DISCLOSURE
Disclosed are blends of two or more polyetherimides.
Such blends generally exhibit a high glass transition temperature, e.g., from about 125° to about 210°C, which makes the blends particularly suitable for automotive and appliance applications.
Disclosed are blends of two or more polyetherimides.
Such blends generally exhibit a high glass transition temperature, e.g., from about 125° to about 210°C, which makes the blends particularly suitable for automotive and appliance applications.
Description
_OLYETHERIMIDE BLENDS
This invention relates -to a class of poly-etherimide blends. The blends exhibi-t a high glass transition temperature, e.g., from abou-t 125 to 210 C, which makes -the blends particularly suitable for auto-motive and appliance applications. Preferred blends compri,se an aliphatic polyetherimide and an aroma-tic polyetherimide, i.e., blends of a polyetherimide formed from an aliphatic diami,ne and a polye-therimide formed from an aromatic diamine.
The blends of the invention include a polyetherimide of the formula:
O O
11 ij _ ~ N A - O --- Z - O- --A N - R- __ \C/ \C /
~ O
L a where a represents a whole number in excess of 1, e~g., ]5 10 to 10,000 or more, the group -O-A~ is selected from:
~ _0/~ --0'/'~ '~
~ 3 8CU-331() Rl being hydrogen, lower alkyl or lower alkoxy, preferably a polye-therimide includes the latter -O-A~
group where Rl is hydrogen such -that -the polye-therimide is oE the fo:rmu].a:
O O
- - N ~ ~ _ O - Z--- -~- C ~ ,N--- R - __ O O
_ _ a and -the divalent bonds of the -O-Z-O- radical are in the 3,3'; 3,4'; 4,3' or the 4,4' position;
Z is a member of the class consisting of (1) ~ ~ ~ 3 ~ 3 CH CE-I3 CH CH~ Br Br ~ ~ ~ ~ { ~ ~ ( 3 2 C
and (2) divalent organic radicals of the general formula:
(0~ (X)q ,~
where x is a member selected from the class consis-tiny of divalent radicals of -the formulas, O O
-C H2~-, -C-, -S~, -O-- and -S-, o where q is 0 or 1, y is a whole number from 1 to 5, and :R is a divalent organic radical selected from -the class consisting of (]) aromatic hydrocarbon radicals having from 6-20 carbon atoms and halogena-ted derivatives -thereof, (2) alkylene radical.s and cycloalkylene radicals having from 2-20 carbon atoms, C(2_8) alkylene terminated polydiorganosiloxane, and (3) divalent radicals included by the formula ~ ~ Q ~
where Q is a member selec-ted from the class consisting of O O
-O-, -C-, -S-, -S- and -CXH2 -o where x is a whole number from 1 to 5 inclusive.
Particularly preferred polye-therimides for the purposes of the present inven-tion include -those where -O-A~ and Z respectively are:
. ) \
~ 8CU-331 and R is selec-ted from hexame-thylene.
~ - CH2 _~ ~ )> _ C112 ~ 2 \~ O
and polyetherimides containing two or more of the R groups.
Po]yetherimides can be obtained by any of the methods well known to those skilled in the art including -the reaction o-f any aromatic bis(ether anhydrides) of -the formula O O
o\ ~Jo_ z_o r- /O
o o where Z is as defined hereinbefore with an organic diamine of the formula
This invention relates -to a class of poly-etherimide blends. The blends exhibi-t a high glass transition temperature, e.g., from abou-t 125 to 210 C, which makes -the blends particularly suitable for auto-motive and appliance applications. Preferred blends compri,se an aliphatic polyetherimide and an aroma-tic polyetherimide, i.e., blends of a polyetherimide formed from an aliphatic diami,ne and a polye-therimide formed from an aromatic diamine.
The blends of the invention include a polyetherimide of the formula:
O O
11 ij _ ~ N A - O --- Z - O- --A N - R- __ \C/ \C /
~ O
L a where a represents a whole number in excess of 1, e~g., ]5 10 to 10,000 or more, the group -O-A~ is selected from:
~ _0/~ --0'/'~ '~
~ 3 8CU-331() Rl being hydrogen, lower alkyl or lower alkoxy, preferably a polye-therimide includes the latter -O-A~
group where Rl is hydrogen such -that -the polye-therimide is oE the fo:rmu].a:
O O
- - N ~ ~ _ O - Z--- -~- C ~ ,N--- R - __ O O
_ _ a and -the divalent bonds of the -O-Z-O- radical are in the 3,3'; 3,4'; 4,3' or the 4,4' position;
Z is a member of the class consisting of (1) ~ ~ ~ 3 ~ 3 CH CE-I3 CH CH~ Br Br ~ ~ ~ ~ { ~ ~ ( 3 2 C
and (2) divalent organic radicals of the general formula:
(0~ (X)q ,~
where x is a member selected from the class consis-tiny of divalent radicals of -the formulas, O O
-C H2~-, -C-, -S~, -O-- and -S-, o where q is 0 or 1, y is a whole number from 1 to 5, and :R is a divalent organic radical selected from -the class consisting of (]) aromatic hydrocarbon radicals having from 6-20 carbon atoms and halogena-ted derivatives -thereof, (2) alkylene radical.s and cycloalkylene radicals having from 2-20 carbon atoms, C(2_8) alkylene terminated polydiorganosiloxane, and (3) divalent radicals included by the formula ~ ~ Q ~
where Q is a member selec-ted from the class consisting of O O
-O-, -C-, -S-, -S- and -CXH2 -o where x is a whole number from 1 to 5 inclusive.
Particularly preferred polye-therimides for the purposes of the present inven-tion include -those where -O-A~ and Z respectively are:
. ) \
~ 8CU-331 and R is selec-ted from hexame-thylene.
~ - CH2 _~ ~ )> _ C112 ~ 2 \~ O
and polyetherimides containing two or more of the R groups.
Po]yetherimides can be obtained by any of the methods well known to those skilled in the art including -the reaction o-f any aromatic bis(ether anhydrides) of -the formula O O
o\ ~Jo_ z_o r- /O
o o where Z is as defined hereinbefore with an organic diamine of the formula
2 R NH2 where R is as defined hereinbefore Aromatic bis(ether anhydride)s of the above formula include, for example, 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]-propane dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride, l/3-bis(2,3-dicarboxyphenoxy)benzene dianhydride; 4 J 4'-bis(2l3-dicarboxyphenoxy)diphenyl sulfide dianhydride; 1,4-bis(2,3-dicarboxyphenoxy)benzene dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ~e~
sulfone dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy) phenyl]propane dianhydride; 4,4'-bis(3,4-dicarboxy-phenoxy) diphenyl ether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride; 1,3-bis(3,4-dicarboxyphenoxy) benzene 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 mixture of such dianhydrides.
In addi-tion, aromatic bis(ether anhydride)s also included by the above formula are shown by Koton, M.M.; Florinski, F.S.; Bessonov, M.I.;
Rudakov, A.P. (Insti-tute of Heteroorganic compounds, Academy o-f Sciences, U S.S.R.), ~.S.S.R. Pa-ten-t No.
257,010, NGvember 11, 1969, Appl. May 3, 1967.
Organic diamines of -the above formula include, for example, m-phenylenediamine, p-phenyler-e-diamine, A,4'-diaminodiphenylpropane, ~,4'-diamino-diphenylmethane benzidine, 4,4'-diaminodiphenyl sulfide, ~,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, l,5-diaminonaphthalene, 3,3'-dimenthylbenzidine,
sulfone dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy) phenyl]propane dianhydride; 4,4'-bis(3,4-dicarboxy-phenoxy) diphenyl ether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride; 1,3-bis(3,4-dicarboxyphenoxy) benzene 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 mixture of such dianhydrides.
In addi-tion, aromatic bis(ether anhydride)s also included by the above formula are shown by Koton, M.M.; Florinski, F.S.; Bessonov, M.I.;
Rudakov, A.P. (Insti-tute of Heteroorganic compounds, Academy o-f Sciences, U S.S.R.), ~.S.S.R. Pa-ten-t No.
257,010, NGvember 11, 1969, Appl. May 3, 1967.
Organic diamines of -the above formula include, for example, m-phenylenediamine, p-phenyler-e-diamine, A,4'-diaminodiphenylpropane, ~,4'-diamino-diphenylmethane benzidine, 4,4'-diaminodiphenyl sulfide, ~,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, l,5-diaminonaphthalene, 3,3'-dimenthylbenzidine,
3,3'-dime-thoxybenzidine, 2,4-bis(~ -amino-t-bu-tyl)--toluene, bis(p-~ -amino-t-butylphenyl)ether, bis(p-~ -methyl-o-aminopentyl)benzene, 1,3-diamino-4-isopropyl-benzene, 1,2-bis(3-aminopropoxy)ethane, m-xylylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, bis(4-aminocyclohexyl)me-thane, 3-methylhep-tame-thylene-diamine, 4,4-dimethylheptame-thylenediamine, 2,11-dodecanediamine, 2,2-dimethylolpropylenediamine, octamethylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dime-thylhepta-methylenediamine, 3-methylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-cyclohexanediamine, 1,12-octadecanediamine, bis(3-aminopropyl)sulfide, N-methyl-bis(3-aminopropyl)amine, hexamethylenediamine, heptame-thylenediamine, nc,namethylenediamine, decame-thylenecliamine, his(3-aminoprc,pyl) tetrarnethylclisiloxarle, bis(~-aminobu-tyl) tetramethyLdis:iloxane, and the like.
The aromatic bis(ether anhydricle) used in making -the above-mentioned preferred polye-therimides is 2,2-bis[~-(3,4-dicarboxy phenoxy)phenyl]propane dianhydride (bisphenol A bisph-thalic anhydride) and -the diamines used are hexamethylene diamine, m-phenylene diamine, m-xylylene diamine, ~,~'-diaminocliphenylmethane and diamino diphenylsulfone~
In general, -the reactions can be advantageously carried out employing well-known solvents, e.g., o~
dichlorobenzene, m-cresol/-toluene, N-methyl-pyrrolidone, etc., in which to effect interaction between -the dianhydrides and the diamines, at -tempera-tures of from about 100 to abou-t 250C. Alternatively, the polyether-imides can be prepared by melt polymeriza-tion of any of -the above dianhydrides with any of the above diamine com-pounds while hea-ting the mixture of -the ingredients at elevated temperatures with concurrent intermixing.
Generallyl mel-t polymerization temperatures be-tween abou-t 200 to ~00C. and preferably 230 to 300C. can be emp~loyed.
The conditions of -the reac-tion and the proportions of ingredien-ts can be varied widely depending on the desired molecular weight, in-trinsic viscosity, and solvent resistance. In general~ equimolar amounts of diamine and dianhydride are employed for high molecular weigh-t polyetherimicles, however, in certain instances, a slight molar excess (about 1 to 5 mol percent) of diamine can be employed resulting in the produc-tion of polyetherimides having terminal amine groups. Monofunc-tional organic amines such as aniline, or organic anhydrides such as phthalic anhydride and maleic anhydride provide molecular weigh-t control. Low molecular weight polyetherimide can ~q~
be employed to -form copolymers. From 0.l to 50 mole percen-t of comonomers based on the to-tal moles of reac-tants can he employed. ~,enerally, use-Eul poly-.~, e-therimides have an in-tri.nsic viscGsity [~/~] grea-ter -than 0.2 deciliters per gram, preferably 0.35 to 0.60, or 0.7 deciii.ters per gram or even higher when measured in m-cresol a-t 25 C.
Included amon~ the many me-thods of making -the polye-therir,lides are those disclosed in U.S. Paten-t Nos.
3,8A7,867, issued November 12, 1974 to Heath et al, 3,847,869, issued No~ember 12, 1974 to Williams, 3,850,885, issued November 26, 1974 to Take]coshi e-t al, 3,852,242, issued November 26, 1974 -to White and 3l855,178, issued December 17, 197~ -to Whi-te, e-tc.
]5 In accordance with the present invention, blends of the polyetherimides are generally obtainable in all propor-tions of the polyetherimides relative to each o-ther. Consequently, blends comprising from abou-t 1 to about 99%~ by wei.gh-t of one polye-therimide and from abou-t 99 to abou-t 1%, by weight of another polye-therimide are included within -the scope of the invention as well as blends of three or more different polye-therimides containing a-t ieast about 1% by weight of each of -the contained polyetherimides. By controlling the proportions of the various polyetherimides relative to each other, blends having certain predetermined proper-ties which are improved over those of one or more components of -the blend alone may be readily obtained. In general, blends of polyetherimides have a good appearance and exhibit a high glass -transition -temperature such as from 125 to I-t is contemplated tha-t the polye-therimide blends of the present invention may also include additive materials such as fillers, stabilizers/ plasticizers, flexibilizers, surfac-tant agents, pigments, dyes, rein-forcements, flame retardants and diluents in conventional amounts .
Methods for forming polyether:Lmide blends may vary considerably Prior art blending -techniques are generally satisfactory. A preferred method comprises blending the polymers and additives such as reinforce-lnents in powder, granular or filamentous form, extruding the blencl, ancl choppinq -the ex-trudate into pellets sui-table for molding by means conventionally used -to mold normally solid thermoplastic composi-tions.
The polyetherimide blends of the presen-t invention have application in a wide variety of physical shapes and forms~ including -the use as films, molding compounds, coatings, etc. When used as films or when made in-to molded produc-ts, these blends, including laminated products prepared therefrom, not only possess good physical properties at room -tempera-ture bu-t they re-tain -their strength and excellent response to work-loading at eleva-ted temperatures for long periods of -time.
Films formed from -the blends of -this inven-tion may be used in applica-tion where films have been used previously.
Thus, the blends of the presen-t inven-tion can be used in automobile and aviation applications for decorative and protective purposes, and as high -tempera-ture electrical insulation for motor slot liners, transformers, dielectric capaci-tors, cable and coil wrappings (form wound coil insulation for motors), and for containers and con-tainer linings. The blends can also be used in laminated struc-tures where films or solutions of the blend are applied -to various heat-resis-tan-t or other type of materials such as asbestos, mica, glass fiber and the like, the shee-ts superimposed one upon -the other, and thereafter subjecting the sheets to elevated tempera-tures and pressures to effect flow and cure of the resinous binder to yield cohesive laminated structures. Films made from the subject polyetherimide blends can also serve in printed circuit applications.
_ g_ Al-ternatively, solutions of -the blends herein described can be coa-ted on elec-trical conduc-tors such as copper, aluminum, etc. and thereafter tl~e coa-te~ conductor can be hea-ted at elevated tempera-tures to remove the sol.vent and p:rovide a con-tinuous resinous composition -thereon. I:E desired, an additional overcoa-t may be applied -to such insula-ted conductors including -the use of polymeric coa-tings, such as polyamides, polyes-ters, silicones, polyvinylformal. resins, epoxy resins, polyimides, polytetrafluoroethylene, etc. The use of the blends of the presen-t inven-tion as overcoa-ts on other -types of insula-tion is no-t precluded.
O-ther applications which are con-templated for these blends include -their use as binders for asbestos fibers, carbon fibers, and o-ther fibrous ma-terials in making brake lininys In addition, moldi.ng compositions and molded articles may be formed from the polymeric blends of the invention by incorporating such fillers as asbes-tos, glass fibers, talc, clay, quar-tz powder, finely divded carbon, and metals, silica and the like into the blends prior to molding. Shaped ar-ticles may be molded under heat, or under heat and pressure, in accordance wi-th practices well known in the art.
The following examples illustrate specific polye-therimide blends in accordance with -the presen-t invention. It should be understood that the examples are given for the purpose of illus-tration and do not limit the invention. In -the examples, all parts and percentages are by weight unless o-therwise specified.
E MPLE I_ Binary polyetherimide blends according to -the invention ~"ere prepared, formed into blend films and then -tested for glass transition -tempera-ture.
A firs-t polyetherimide was prepared from -the reaction productof essentially equimolar amounts of 2,2-bis[4-(3,4-dicarboxy phenoxy)phenylj propane dianhydride and m-phenylene diamine produced at elevated temperature of abou-t 250 to about 300 C. and under nitrogen a-tmosphere. A test specimen for glass transition -temperature and the results are set :Eor-th in the :EoLlowin-~ '['able I.
A seconcl polyetherimide was prepared from the reac-tion product of hexamethylenediamine and 2,2-bis[4-(3,~--di.carboxy phenoxy)phenyl~ propane dianhydride and -Eormed in-to a test specimen as above. The glass transi.tion -temperature of this polyetherimide is also set forth in Table I.
About 90 parts of the firs-t polyetherimide in a N-methylpyrrolidone solution were mixed with abou-t 10 parts of -the second polye-therimide in a N-methylpyrrolidone solution and the polymer mixture was then solution cas-t -to form a fi.lm. The glass transition temperature of the blend film was measured and is given in Table I.
The above blending procedure was -then repeated so as to produce six additional blends having varying amounts of the first polyetherimide rela-tive -to the second polye-therimide. The glass transition tempera-ture for each of the additional blends is also se-t forth in Table I.
From the data, i-t can be observed -that blends containing from 50 to 70% of the firs-t polyetherimide and 50 to 30% of the second polyetherimide have a glass transition temperature in -the range of 165 to 190 C. which makes these blends particularly adap-table for autornotive and appliance applications.
. .
.
TABLE I
_ ____ __ ~irs-t Second Glass PolyetherirflidePolyetherimide Transition Con-tent Con-tent Temperature t%) (%) (C) ___ __ ___. ___.__ __ ___ ~20 1l 198 ,40 ~ 180 EXAMPLE II
Binary polyetherimide blends according -to -the invention were prepared, formed into blend films and then -tes-ted for glass -transi-tion temperature.
A firs-t polyetherimide was prepared from -the reaction product of essentially equimolar amounts of 2l2-bis[4-(3,4-dicarboxy phenoxy)phenyl] propane dianhydride and m-phenylene diamine produced a-t elevated tempera-ture of about 250 to about 300C. and under nitrogen atmosphere.
A tes-t specimen solution coated in the form of a film was tested for glass -transition tempera-ture and the resul-ts are set forth in the following Table II.
A second polyetherimide was prepared from the reaction product of m-xylene diamine and 2,2-bis[4-(3,4-dicarboxy phenoxy)phenyl] propane dianhydride and formed into a test specimen as above. The glass transitlon tempera-ture of -this polye-therimide is also set for-th in Table II.
~ second polyetherimide was prepared from -the reaction product of m-xylene diamine and 2,2-bis[4-(3,4-dicarboxy phenoxy)phenyll propane dianhydride and formed into a -test specimen as above, The glass transition temperature of this polye~,herimide is also set for-th in Table II.
About 90 parts oE -the first ~polyetherimide in a N-methylpyrrolidone solution were mixed with about 10 parts of the second polyetherimide in a N-methylpyrrolidone solution and the polymer mixture was then solution cas-t to form a film. The glass transition temperature of the blend was measured and is given in Table II.
The above blending procedure was then repeated so as -to produce six additional blends having varying amounts of the first polyetherimide relative to the second polye-therimide. The glass transition -temperature for each of the additional blends is also set for-th in Table II.
From -the data~ it can be observed -tha-t blends containing from 10 to 60% of the firs-t polyetherimide and 90 to 40%
oE -the second polye-therimide have a glass transition temperature in the range of 170 to 195C. which also ma~es -these blends par-ticularly adap-table for automo-tive and appliance applica-tions.
"~
.... _ _ . . _ _ .. _ _ . _ _ . _ _ _ _ _ _ _ _ .. _ _ . _ _ _ _ _ _ _ . ~ _ _ _ -- . ..... .. ., . _ . .. . .
8CU-33lO
TAsLE II
First Seconcl Glass Polyetherimide Polyetherimide Transi-tion Content Content Tempera-ture 5 (%) (%) (C) ._ _ ~ ~_ _ 222 Polyetherimide blends accorcding to -the invention were prepared from a polyetherimide homopolymer and a polyetherimide copolymer. The blends were formed into blend films and then tested for glass -transi-tlon temperature.
The polye-therimide homopolymer was prepared from the reaction product of essentially equimolar amounts of 2,2-bis[4-(3,4-dicarboxy phenoxy)phenyl~ propane dianhydride and m-phenylene diamine produced at elevated temperature of about 250 to about 300 C. and under nit.rogen atmosphere.
A test specimen solution coated in the form of a film was tested for glass transition -tempera-ture and the results are set forth in Table III.
The polyetheri~ide copolymer was prepared from the reaction product of essentially equimolar amounts of 30 2,2-bis[4-(3,4-dicarboxy phenoxy)phenyl] propane dianhydride and a mixture of equimolar amounts of 8CU~3310 m-phenylene diamine and hexamethylene diamine. About 50 parts of the polyetherirnide homopolymer were mixed in solution with abou-t 50 parts o-E -the polyetherimide copo].ymer and -the polymer mixture was then solution cast to form a film. The glass transition -temperature of the blencl :Eilm was measured and is given in Table III.
Ano-ther polyetherimide copolymer was prepared as above excep-t -that the molar ra-tio of m-phenylene diamine -to hexamethylene diamine was about three -to one. About 75 parts oE the polyetherimide homopolymer were mixed in solution with about 25 parts of the polyetherimide copolymer and the polymer mix-ture was then solution cas-t to Eorm a blend film. The glass transition tempera-ture oE the blend was measured and is given in Table III.
A iurther polyetherimide copolymer was prepared as above with the exception that the molar ratio oE m-phenylene diamine to hexame-thylene diamine was about one -to three. About 25 parts of the polyetherimide homopolymer were mixed in solution with about 75 par-ts of -the second polyetherimide copolymer and the polymer mixture was then solution cast to ~orm a blend film~ The glass transition temperature of the blend was measured and is given in Table III.
From the data presented in Table II, it can be observed that the polyetherimide homopolymer-copolymer blends have an excep-tionally high glass transition tempera-ture even at high aliphatic amine concentrations, i.e., at high hexamethylene diamine ratios. These high glass transition temperatures give the blends utility as coatings and insulation and as compression and injection molding compounds.
TABLE III
Polye-therimide Polye-therimide Ratio of G'ass Homopolymer Copolymer m-phenylene d:iamine Transi-tion Content Content to hex.~me-thylene diamine Temperature _ ( QO ) _ ( % ) __ to prepare copolymer tPo) 100 _ 223 25 3:1 211 50 1:1 203 75 1:3 19~3 ~ ___~__ ~ __~
Suhstitution of other polyetherimides for the polyetherimides of the blends of the above examples may result in the formulation of polyetherimide polymer blends having similar characteristics.
While -the present invention has been described with reference -to particular embodiments thereof, it will be unders-tood that numerous modifications may be made by those skilled in the art wi-thout actually departing from the spirit and scope of the invention as deEined in the appended claims.
The aromatic bis(ether anhydricle) used in making -the above-mentioned preferred polye-therimides is 2,2-bis[~-(3,4-dicarboxy phenoxy)phenyl]propane dianhydride (bisphenol A bisph-thalic anhydride) and -the diamines used are hexamethylene diamine, m-phenylene diamine, m-xylylene diamine, ~,~'-diaminocliphenylmethane and diamino diphenylsulfone~
In general, -the reactions can be advantageously carried out employing well-known solvents, e.g., o~
dichlorobenzene, m-cresol/-toluene, N-methyl-pyrrolidone, etc., in which to effect interaction between -the dianhydrides and the diamines, at -tempera-tures of from about 100 to abou-t 250C. Alternatively, the polyether-imides can be prepared by melt polymeriza-tion of any of -the above dianhydrides with any of the above diamine com-pounds while hea-ting the mixture of -the ingredients at elevated temperatures with concurrent intermixing.
Generallyl mel-t polymerization temperatures be-tween abou-t 200 to ~00C. and preferably 230 to 300C. can be emp~loyed.
The conditions of -the reac-tion and the proportions of ingredien-ts can be varied widely depending on the desired molecular weight, in-trinsic viscosity, and solvent resistance. In general~ equimolar amounts of diamine and dianhydride are employed for high molecular weigh-t polyetherimicles, however, in certain instances, a slight molar excess (about 1 to 5 mol percent) of diamine can be employed resulting in the produc-tion of polyetherimides having terminal amine groups. Monofunc-tional organic amines such as aniline, or organic anhydrides such as phthalic anhydride and maleic anhydride provide molecular weigh-t control. Low molecular weight polyetherimide can ~q~
be employed to -form copolymers. From 0.l to 50 mole percen-t of comonomers based on the to-tal moles of reac-tants can he employed. ~,enerally, use-Eul poly-.~, e-therimides have an in-tri.nsic viscGsity [~/~] grea-ter -than 0.2 deciliters per gram, preferably 0.35 to 0.60, or 0.7 deciii.ters per gram or even higher when measured in m-cresol a-t 25 C.
Included amon~ the many me-thods of making -the polye-therir,lides are those disclosed in U.S. Paten-t Nos.
3,8A7,867, issued November 12, 1974 to Heath et al, 3,847,869, issued No~ember 12, 1974 to Williams, 3,850,885, issued November 26, 1974 to Take]coshi e-t al, 3,852,242, issued November 26, 1974 -to White and 3l855,178, issued December 17, 197~ -to Whi-te, e-tc.
]5 In accordance with the present invention, blends of the polyetherimides are generally obtainable in all propor-tions of the polyetherimides relative to each o-ther. Consequently, blends comprising from abou-t 1 to about 99%~ by wei.gh-t of one polye-therimide and from abou-t 99 to abou-t 1%, by weight of another polye-therimide are included within -the scope of the invention as well as blends of three or more different polye-therimides containing a-t ieast about 1% by weight of each of -the contained polyetherimides. By controlling the proportions of the various polyetherimides relative to each other, blends having certain predetermined proper-ties which are improved over those of one or more components of -the blend alone may be readily obtained. In general, blends of polyetherimides have a good appearance and exhibit a high glass -transition -temperature such as from 125 to I-t is contemplated tha-t the polye-therimide blends of the present invention may also include additive materials such as fillers, stabilizers/ plasticizers, flexibilizers, surfac-tant agents, pigments, dyes, rein-forcements, flame retardants and diluents in conventional amounts .
Methods for forming polyether:Lmide blends may vary considerably Prior art blending -techniques are generally satisfactory. A preferred method comprises blending the polymers and additives such as reinforce-lnents in powder, granular or filamentous form, extruding the blencl, ancl choppinq -the ex-trudate into pellets sui-table for molding by means conventionally used -to mold normally solid thermoplastic composi-tions.
The polyetherimide blends of the presen-t invention have application in a wide variety of physical shapes and forms~ including -the use as films, molding compounds, coatings, etc. When used as films or when made in-to molded produc-ts, these blends, including laminated products prepared therefrom, not only possess good physical properties at room -tempera-ture bu-t they re-tain -their strength and excellent response to work-loading at eleva-ted temperatures for long periods of -time.
Films formed from -the blends of -this inven-tion may be used in applica-tion where films have been used previously.
Thus, the blends of the presen-t inven-tion can be used in automobile and aviation applications for decorative and protective purposes, and as high -tempera-ture electrical insulation for motor slot liners, transformers, dielectric capaci-tors, cable and coil wrappings (form wound coil insulation for motors), and for containers and con-tainer linings. The blends can also be used in laminated struc-tures where films or solutions of the blend are applied -to various heat-resis-tan-t or other type of materials such as asbestos, mica, glass fiber and the like, the shee-ts superimposed one upon -the other, and thereafter subjecting the sheets to elevated tempera-tures and pressures to effect flow and cure of the resinous binder to yield cohesive laminated structures. Films made from the subject polyetherimide blends can also serve in printed circuit applications.
_ g_ Al-ternatively, solutions of -the blends herein described can be coa-ted on elec-trical conduc-tors such as copper, aluminum, etc. and thereafter tl~e coa-te~ conductor can be hea-ted at elevated tempera-tures to remove the sol.vent and p:rovide a con-tinuous resinous composition -thereon. I:E desired, an additional overcoa-t may be applied -to such insula-ted conductors including -the use of polymeric coa-tings, such as polyamides, polyes-ters, silicones, polyvinylformal. resins, epoxy resins, polyimides, polytetrafluoroethylene, etc. The use of the blends of the presen-t inven-tion as overcoa-ts on other -types of insula-tion is no-t precluded.
O-ther applications which are con-templated for these blends include -their use as binders for asbestos fibers, carbon fibers, and o-ther fibrous ma-terials in making brake lininys In addition, moldi.ng compositions and molded articles may be formed from the polymeric blends of the invention by incorporating such fillers as asbes-tos, glass fibers, talc, clay, quar-tz powder, finely divded carbon, and metals, silica and the like into the blends prior to molding. Shaped ar-ticles may be molded under heat, or under heat and pressure, in accordance wi-th practices well known in the art.
The following examples illustrate specific polye-therimide blends in accordance with -the presen-t invention. It should be understood that the examples are given for the purpose of illus-tration and do not limit the invention. In -the examples, all parts and percentages are by weight unless o-therwise specified.
E MPLE I_ Binary polyetherimide blends according to -the invention ~"ere prepared, formed into blend films and then -tested for glass transition -tempera-ture.
A firs-t polyetherimide was prepared from -the reaction productof essentially equimolar amounts of 2,2-bis[4-(3,4-dicarboxy phenoxy)phenylj propane dianhydride and m-phenylene diamine produced at elevated temperature of abou-t 250 to about 300 C. and under nitrogen a-tmosphere. A test specimen for glass transition -temperature and the results are set :Eor-th in the :EoLlowin-~ '['able I.
A seconcl polyetherimide was prepared from the reac-tion product of hexamethylenediamine and 2,2-bis[4-(3,~--di.carboxy phenoxy)phenyl~ propane dianhydride and -Eormed in-to a test specimen as above. The glass transi.tion -temperature of this polyetherimide is also set forth in Table I.
About 90 parts of the firs-t polyetherimide in a N-methylpyrrolidone solution were mixed with abou-t 10 parts of -the second polye-therimide in a N-methylpyrrolidone solution and the polymer mixture was then solution cas-t -to form a fi.lm. The glass transition temperature of the blend film was measured and is given in Table I.
The above blending procedure was -then repeated so as to produce six additional blends having varying amounts of the first polyetherimide rela-tive -to the second polye-therimide. The glass transition tempera-ture for each of the additional blends is also se-t forth in Table I.
From the data, i-t can be observed -that blends containing from 50 to 70% of the firs-t polyetherimide and 50 to 30% of the second polyetherimide have a glass transition temperature in -the range of 165 to 190 C. which makes these blends particularly adap-table for autornotive and appliance applications.
. .
.
TABLE I
_ ____ __ ~irs-t Second Glass PolyetherirflidePolyetherimide Transition Con-tent Con-tent Temperature t%) (%) (C) ___ __ ___. ___.__ __ ___ ~20 1l 198 ,40 ~ 180 EXAMPLE II
Binary polyetherimide blends according -to -the invention were prepared, formed into blend films and then -tes-ted for glass -transi-tion temperature.
A firs-t polyetherimide was prepared from -the reaction product of essentially equimolar amounts of 2l2-bis[4-(3,4-dicarboxy phenoxy)phenyl] propane dianhydride and m-phenylene diamine produced a-t elevated tempera-ture of about 250 to about 300C. and under nitrogen atmosphere.
A tes-t specimen solution coated in the form of a film was tested for glass -transition tempera-ture and the resul-ts are set forth in the following Table II.
A second polyetherimide was prepared from the reaction product of m-xylene diamine and 2,2-bis[4-(3,4-dicarboxy phenoxy)phenyl] propane dianhydride and formed into a test specimen as above. The glass transitlon tempera-ture of -this polye-therimide is also set for-th in Table II.
~ second polyetherimide was prepared from -the reaction product of m-xylene diamine and 2,2-bis[4-(3,4-dicarboxy phenoxy)phenyll propane dianhydride and formed into a -test specimen as above, The glass transition temperature of this polye~,herimide is also set for-th in Table II.
About 90 parts oE -the first ~polyetherimide in a N-methylpyrrolidone solution were mixed with about 10 parts of the second polyetherimide in a N-methylpyrrolidone solution and the polymer mixture was then solution cas-t to form a film. The glass transition temperature of the blend was measured and is given in Table II.
The above blending procedure was then repeated so as -to produce six additional blends having varying amounts of the first polyetherimide relative to the second polye-therimide. The glass transition -temperature for each of the additional blends is also set for-th in Table II.
From -the data~ it can be observed -tha-t blends containing from 10 to 60% of the firs-t polyetherimide and 90 to 40%
oE -the second polye-therimide have a glass transition temperature in the range of 170 to 195C. which also ma~es -these blends par-ticularly adap-table for automo-tive and appliance applica-tions.
"~
.... _ _ . . _ _ .. _ _ . _ _ . _ _ _ _ _ _ _ _ .. _ _ . _ _ _ _ _ _ _ . ~ _ _ _ -- . ..... .. ., . _ . .. . .
8CU-33lO
TAsLE II
First Seconcl Glass Polyetherimide Polyetherimide Transi-tion Content Content Tempera-ture 5 (%) (%) (C) ._ _ ~ ~_ _ 222 Polyetherimide blends accorcding to -the invention were prepared from a polyetherimide homopolymer and a polyetherimide copolymer. The blends were formed into blend films and then tested for glass -transi-tlon temperature.
The polye-therimide homopolymer was prepared from the reaction product of essentially equimolar amounts of 2,2-bis[4-(3,4-dicarboxy phenoxy)phenyl~ propane dianhydride and m-phenylene diamine produced at elevated temperature of about 250 to about 300 C. and under nit.rogen atmosphere.
A test specimen solution coated in the form of a film was tested for glass transition -tempera-ture and the results are set forth in Table III.
The polyetheri~ide copolymer was prepared from the reaction product of essentially equimolar amounts of 30 2,2-bis[4-(3,4-dicarboxy phenoxy)phenyl] propane dianhydride and a mixture of equimolar amounts of 8CU~3310 m-phenylene diamine and hexamethylene diamine. About 50 parts of the polyetherirnide homopolymer were mixed in solution with abou-t 50 parts o-E -the polyetherimide copo].ymer and -the polymer mixture was then solution cast to form a film. The glass transition -temperature of the blencl :Eilm was measured and is given in Table III.
Ano-ther polyetherimide copolymer was prepared as above excep-t -that the molar ra-tio of m-phenylene diamine -to hexamethylene diamine was about three -to one. About 75 parts oE the polyetherimide homopolymer were mixed in solution with about 25 parts of the polyetherimide copolymer and the polymer mix-ture was then solution cas-t to Eorm a blend film. The glass transition tempera-ture oE the blend was measured and is given in Table III.
A iurther polyetherimide copolymer was prepared as above with the exception that the molar ratio oE m-phenylene diamine to hexame-thylene diamine was about one -to three. About 25 parts of the polyetherimide homopolymer were mixed in solution with about 75 par-ts of -the second polyetherimide copolymer and the polymer mixture was then solution cast to ~orm a blend film~ The glass transition temperature of the blend was measured and is given in Table III.
From the data presented in Table II, it can be observed that the polyetherimide homopolymer-copolymer blends have an excep-tionally high glass transition tempera-ture even at high aliphatic amine concentrations, i.e., at high hexamethylene diamine ratios. These high glass transition temperatures give the blends utility as coatings and insulation and as compression and injection molding compounds.
TABLE III
Polye-therimide Polye-therimide Ratio of G'ass Homopolymer Copolymer m-phenylene d:iamine Transi-tion Content Content to hex.~me-thylene diamine Temperature _ ( QO ) _ ( % ) __ to prepare copolymer tPo) 100 _ 223 25 3:1 211 50 1:1 203 75 1:3 19~3 ~ ___~__ ~ __~
Suhstitution of other polyetherimides for the polyetherimides of the blends of the above examples may result in the formulation of polyetherimide polymer blends having similar characteristics.
While -the present invention has been described with reference -to particular embodiments thereof, it will be unders-tood that numerous modifications may be made by those skilled in the art wi-thout actually departing from the spirit and scope of the invention as deEined in the appended claims.
Claims (9)
- Claim 1 continued:
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, where q is 0 or 1, y is a whole number from 1 to 5, and R is a divalent organic radical selected from the class consisting of (1) aromatic hydrocarbon radicals having from 6-10 carbon atoms and halogenated derivatives thereof, (2) alkylene radicals and cycloalkylene radicals having from 2-20 carbon atoms, and C(2-8)alkylene terminated polydiorganosiloxane, and (3) divalent radicals included by the formula:
where Q is a member selected from the class consisting of where x is a whole number from 1 to 5 inclusive;
wherein the glass transition temperatures of the component polyetherimides are different and the glass transition temperature of the blend lies between those of the component polyetherimides. - 2. A composition, comprising:
a blend of two or more polyetherimides selected from the class consisting of:
where Z is and R is selected from hexamethylene, wherein the glass transition temperatures of the component polyetherimides are different and the glass transition temperature of the blend lies between those of the component polyetherimides. - 3. A composition in accordance with claim 2 containing a first polyetherimide where R is
- 4. A composition in accordance with claim 3 containing a second polyetherimide where R is hexamethylene.
- 5. A composition in accordance with claim 3 containing a second polyetherimide where R is
- 6. A composition in accordance with claim 1 comprising a first and second polyetherimides each formed by the reaction of aromatic bis(ether anhydrides) of the formula with one or more organic diamines of the formula H2N - R - NH2 .
7. A composition in accordance with claim 6 wherein the bis ether anhydride of the first and second polyetherimide is of the formula - Claim 7 continued:
the diamine of the first polyetherimide is and the diamine of the second polyetherimide is selected from one or more of hexamethylene diamine, - 8. A composition in accordance with claim 7 where the diamine for the second polyetherimide is hexamethylene diamine and
- 9. A composition in accordance with claim 2 containing one or more fillers.
1. A composition comprising:
a blend of two or more polyetherimides selected from the class consisting of where a represents a whole number in excess of 1, the group -O-A? is selected from:
R' being hydrogen, lower alkyl or lower alkoxy, Z is a member of the class consisting of (1)
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Application Number | Priority Date | Filing Date | Title |
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CA000425849A CA1192689A (en) | 1983-04-14 | 1983-04-14 | Polyetherimide blends |
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CA000425849A CA1192689A (en) | 1983-04-14 | 1983-04-14 | Polyetherimide blends |
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-
1983
- 1983-04-14 CA CA000425849A patent/CA1192689A/en not_active Expired
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