CA1231189A - Polyetherimide blends - Google Patents

Abstract

POLYETHERIMIDE BLENDS

ABSTRACT OF THE DISCLOSURE
This invention is concerned with polyetherimide blends. More particularly the polyetherimide blend comprises a polyetherimide and a block copolymer of a vinyl aromatic hydrocarbon and a diene hydrocarbon, and a polyester to form a ternary blend.

Description

POLYETHERIMIDE BLENDS
BACKGROUND
The present invention relates to a class of polyetherimide blends comprising a polyetherimide, a block copolymer owe a vinyl aromatic hydrocarbon an a dine hydrocarbon and optionally a polyester.
Certain blends of polyetherimides and other polymers are known.
For example, U.S. Patent 4,14,1927 discloses a polyetherimide-polyester binary mixture. U.S. Patent 4,259,458 discloses a blend containing a polyarylate, a polyester, and at least one thermos plastic polymer selected from the group consisting of an aromatic polycarbonate, a styrenes resin, an alkyd acrylate resin, a polyp urethane, a vinyl chloride polymer, a poly(aryl ether), a copolyetherester block polymer or a polyhydroxyether.
SUMMARY OF THE INVENTION
In accordance with the present invention, a polyetherimide blend contains from 50 to 95 parts by weight of a polyetherimide, 0 to 45 parts by weight of a polyester and 5 to 20 parts by weight of a block copolymer of a vinyl aromatic compound and a dine compound.
DETAILED DESCRIPTION
2Q This invention relates to a class of polyetherimide blends comprised of the following elements: (1) a polyetherimde,

(2) a block copolymer of a vinyl aromatic hydrocarbon and a dine hydrocarbon and (3) optionally a polyester. These blends exhibit improved impact strengths, as compared to those of the individual components. Additionally, these blends show surprisingly good flexural properties in conjunction with significantly improved flow characteristics as the levels of either the polyester element or -the block copolymer of a vinyl aromatic hydrocarbon and a dine hydrocarbon element are increased.

I Cassius The blends of the invention include a polyether-imide ox the formula a where "a" represents a whole number in excess of 1, e.g.
10 to 10,000 or more, Z is a member selected Rome the class consisting of (1):

SHEA SHEA SHEA SHEA

SHEA By By SHEA By By C ( SHEA ) 2_/0/;

c~3 By By SHEA By Err and (2) diva lent organic radicals of the general formula:

OWE X ) q Ox I
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3 --where X is a Myra selected from eye class consisting of diva lent radical of the formulas, . O O
Syria 5-, -ox and -S-, O
where q is 0 or I y is a whole number prom 1 to S, and S dival@nt bonds of the ~0-Z-0-radical are situated on the phthalic android end groups, ego in the 3131, 3,4', 493' or the 4~4' positions and R is a diva lent organic radical selected f rum the at ass consisting of (1) aromatic hydrocarbon radicals having from 6 to about 20 carbon atoms and halogenated derivatives thereof, (2) alkaline radicals and cycloalkylene radicals having from about 2 to about 20 carbon atoms, C(2_8~ alkaline terminated polydiorganosiloxane, and (3) diva lent radicals of the formula:

lo Q I -where Q is a member selected from the class consisting of :
O O
_, S- and -CX~2x o where x is a whole number from 1 to 5 inclusive.
The polyetherimides own be obtained by any of the methods well known to those skilled in the art including the reaction of any aromatic bis~ether android) ox the formula:

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. 4 O O
11 i o\ ~()J~-Z-o_l~/ o C 'C
If I
o . o where Z it as defined above with an organic Damon of the formula H~.2N-R-NH2 where R is as defined above Aromatic bis(ether androids of the above formula include, for example 2,2-bis[4-(2,3~dicarboxyphenoxy)-phenyl]-propane dianhydride; 4,4'-bis~2~dicarboxyphen-oxy)diphenyl ether dianhydride; Boyce dicarboxy-phenoxy)benzene dianhydride; 4,4'-bis(2,3-dicarboxy-phenoxy)diphenyl sulfide dianhydride; 1,4-bis~2-dicar-boxyphenoxy)benzene dianhydride; 4,4'~bis(2,3-dicarboxy-phonics) benzophenone dianhydride; 4,4'-bis(2,3-dicar-~oxyphenoxy )diphenyl cellophane di~nhydride; 2t2-bisl4-~3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy~diphenyl ether dianhydride;
4t4'-bisl3,4-dicarboxyphenoxy)diphenyl sulfide Dunn-drive; 1,3-bis~3,4-dicarboxyphenoxy)benzene dianhydride;
1,4-bis~3,4-di~arboxyphenoxy)benzene dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)ben2Ophenone dianhydride; 4-(2,3-dicarboxyphenoxy)-4'(~,4-dicarboxyphenoxy)dipphenol-2,2-propane dianhydride; etc. and mixtures of such dianhydrides .
In addition, aromatic bis~ether androids included by the above formula are shown by Kitten, MUM.;
- Florinski, So Bessonov, MOE; Rudakov, ASP.
(Institute of Heteroorganic compounds r Academy ox Science, U.S.S.R.), U.S.S.R. 257,010, Nov. 11, 1969, I
kiwi Apply May 3, 1967. Such dianhydrides are also shown by MUM. Kitten, OOZE. Florins One ; I, 774 lg68) .
Organic dominoes of the above formula include, for example, m phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine, ~,4'-diaminodiphenyl sulfide, diamond-phenol cellophane 4,4'-diaminodiphenyl ether, 1,5 Damon-nap that one, 3, 3 ' -d ire thylbenz id i no, 3, 3 ' -dime thoxyben-zidine, 2r4-bis(~-amino-t-butyl)toluene, bis~p-~-amino-t-butylphenyl)ether, bistp-~-methyl-o-aminopentyl~ben-Zion 1,3-diamino-4-isopropylbenzene, 1,2 basemen-propoxy)ethane, m-xylylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 2,6-diamino-toluene bis(4-aminocy-~lohexyl)methane, 3-methylheptamethylenedi~mine, 4,4-dimethylheptamethylenediamine, 2,11-dodecanediamine, 2,2 dimethylpropylenediamine, octamethylenediamine, Matthew oxyhexamethylenediamine, 2,5-dimethylhexamethylene-Damon, 2,5-dimethylheptamethylenediamine, 3-methylhep-tamethylenediamine, 5-methylnonamethylenediamine, 1,4-cyclohexanediamine, 1,12-octadecanediamine, bis(3-amiilo-propyl)sulfide, N-methyl-bis ~3-aminopropyl)amine, hex-methylenediamine, heptamethylenediamine, nonamethylene-Damon, dec~methylenediamine, bis(3-aminopropyl) twitter-methyldisiloxane7 bis(4-amlnobutyl) tetramethyldisilox-anew and the like.
In general, the reactions can be advantageously carried out employing well known solvents, e.g., o-dichlorobenxene, m-cresol/toluene, etc. in which to effect interaction between the dianhydrides and the dominoes, at temperate of from about 100~C to about ~50C. Alternatively, the polyetherimides can be prepared by melt polymerization of any of the above Dan hydrides with any of the above Damon compounds US while heating the mixture of the ingredients at elevated I
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temperatures with concurrent intermixing Generally, melt polymerization temperatures between about 200~C to 400~C and preferably 230C to 300C can be employed.
The conditions of the reaction and the proportions of 5 ingredients can be varied widely depending on the desired molecular weight, intrinsic viscosity, and solvent resistance. In general, equimolar amounts of Damon and dianhydride are employed for high molecular weight polyetherimides, however, in certain instances, a slight molar excess (about 1 to 5 mole percent) of Damon can be employed resulting in the production of polyetherimides having terminal amine groups.
generally, useful polyetherimides have an intrinsic viscosity [I] greater than 0.2 deciliters per gram, preferably 0.35 to 0.60, or 0.7 deciliters per gram or even higher when measured in m-cresol at 25C.
The second component of the blends of this invent lion is a block copolymer of a vinyl aromatic hydrocar-bun and a dine hydrocarbon. These block copolymers are well known and are describer for instance, in Chemistry of Synthetic Elastomers, edited by Kennedy et at., Intrusions Publishers, Vol. 23, Part II (1969), pages 553-55g. Such block copolymers are also described, for example, by æelinskir U.S. Patent No.
3,251,905, and Holder et at., U S. Patent No.
3,23~,635.
In general, the block copolymer is represented by the formula, -A-B A, in which terminal blocks, A, which can be the same or different, are thermoplastic home-polymers or copolymers prepared from a vinyl aromatic compound wherein the aromatic moiety can be either moo-cyclic or polycyclic. Examples of such vinyl aromatic compounds include styrenes alpha-methyl styrenes vinyl Tulane, vinyl zillion, ethyl vinyl zillion, vinyl napth-thalene and the like, or mixtures thereof.

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The center block, I, is an elastom~ric polymer derived from a dine hydrocarbon, such as ethylene and battalion and conjugated dines, e.g., 1,3-butadiene, 2,3-dimethylbutadiene, isoprene, 1,3-pentadiene, and the S like, or mixtures thereof.
The ratio of the copolymers and the average mole-ular weights of each can vary broadly. Frequently however the molecular weight of center block, B, will be greater than that of the continued terminal blocks, which appear to be necessary for optimum impact strength and solvent resistance. The molecular. weigh of terming at block A, will preferably range from about 2,000 to about 100,000, while the molecular weight of center block, 8, is preferably from about 25,000 to about 1 outyell.
If desired, the block copolymers own be post-treated to hydrogenate the rubber portion of the Capella-men. Hydrogenation can be accomplished using convent tonal hydrogenation catalysts and reaction conditions.
With respect to the hydrogenated A-B-A block copolymers, it is preferred to form terminal block A
having average molecular weight of from about 4,000 to about 115,000 and center block B having an average molecular weight of from about 20,000 to about 450,000.
Still more preferably, the terminal block A will have an average molecular weight of from 8,000 to 60,000 while center block B still have an average molecular weight of prom S0,000 to aye.
The terminal block can comprise from 2 to 48~ by weight, preferably from 5 to 35~ by weight of the block copolymer.
Particularly preferred hydrogenated block Capella-mews are thus having a polybutadi~ne center block wherein from 35 to 55%, more preferably from 40 to 50 of the buttondown carbon atoms are vinyl side chains.

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Hydrogenated okay copolymers are described further by Jones, USE Pat. No. 3j431,323 and Delaware et at., U.S. Pat No. 3,670,054, which issued June 13, 1972.
S In preferred blends t the second component will key an A-B-A block copolym~r of the polystyrene-polybuta-diene-polystyrene or polystyrene-polyisoprene~polysty-none type wherein the polybutadiene or polyi~oprene portion Jan be either hydrogenated or non-hydrogena~ed.
Particularly preferred are the A-B-A block copolymers of the ~tyrene-ethylene-butylene-styrene (SUBS) type.
The above block copolymers of a vinyl aromatic hydrocarbon and a dine hydrocarbon are well known in the art. They are commercially available from Shell Chemical Company of Houston, Texas, under the trademark CRETAN Particularly preferred are the CREATING grades that are of the SUBS type. The KOWTOWING grades are available with varying styrene/rubber ratios, for example CREATING has a 14/86 styrene/rubber ratio while CREATING 1 has a 33/67 styrenes to rubber Russia .
The polyesters that can be employed in the blends of this invention are conventional or known polyesters made according to convent tonal or known methods. The polyesters include polymers formed from dicarboxylic acids containing a total of from about 2 to about 16 carbon atoms reacted with polyhydric alcohols such as glycols or dills containing from 2 to 12 carbon atoms.
Aliphatic dicarboxylic acids may contain a total ox from 2 to 16 carbon atoms Preferably, the acids are aureole or an alkyd substituted aromatic acids containing from 8 to 16 carbon atoms. Specific examples of linear aliphatic dicarboxylic acids include oxalic acid, Masonic acid, succinic acid! glutaric acid, adipic acid, plmelic acid, sub Eric acid azelaic acid, sebacic acid, anal the like.

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Specific examples of an aureole acid include the various isomers of phthalic acid, such as paraphthalic acid (terephthalic acid and naphthalic acid Specific examples of alkyd substituted aureole acids include the various isomers of dimethylphthalic acid such as dimethylisoph~halic acid,. dimethylorthoph~halic acid dimethylter~phthalic acid, the various isomers of diethylph~halic acid such as diethylisophthalic acid, diethylorthophthalic acid diethylterephthalic acid, the various isomers of dimethylnaphthalic acid such as 2,6-dimethylnaphthalic acid and 2,5-dimethylnaphthalic acid, and toe various isomers of dimethylnaphthalic acid such a 2,6-dimethylnaphthalic acid and 2,5-dimethylnaph-thalic acid, and the various isomers of diethylnaph-thalic acid. Particularly preferred is terephthalicacid. When two or more dicarboxylic acids are used, it it particularly preferred that at least 90 mole percent of the total acid moiety be terephthalic acid.
Generally an excess of 95 mole percent terephthalic is the most preferred.
It is well known to those skilled in the art that in lieu of the various dicarboxylic acids, the various divesters thereof may be utilized. Thus, alkyd divesters containing a total of from 2 to about 20 carbon atoms as well as alkyd substituted aureole divesters containing from about to to about 20 carbon atoms may be utilized.
Examples of divesters include the divesters of oxalic acid, Masonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sub Eric acid, azelaic acid, or sebacic acid, and the like Specific examples of various alkyd substituted aureole divesters include the various isomers of dimethylphthalate such a dim ethyl terephthalate, a preferred compound, the various isomers of diethylphthalate, the various isomers of dim ethyl--:
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naphthala'ce, and the various isomers of die~hylnaph-thalate .
The dills or glycols may ye straight chain or branched The dills may Allah be aliphatic or cycloali-phatic. Specific examples include ethylene glycol, propylene glycol, trim ethylene glyoolO 1,2-butanediol, 1, 3-butanediol, 1, 4-butanedioL, 2 utanediol, neopentyl gly~ol, cy~lohexanedimethanol, and the like.
Of the various glycols, those having from 2 to 8 carbon atoms are preferred with ethylene glycol being portico-laxly preferred. In lieu of the various glycols, another class of polyhydric alcohols, such as the glycol ethers containing from 4 to 12 carbon atoms, can be utilized as for example dim ethylene glycol and Dow-droxyethoxy ozone The polyesters employed in the blends of this invention can generally be made according Jo convent tonal melt polymerization, or melt and solid state polymerization technique.
The polyetherimide blends of the present invention can contain a broad rang of relative proportion of the polymer compounds These blends generally include come positions comprising:
1. polyetherimide.......... .5-95%
I polyester. Do 0-45 3. block copolymer of a vinyl aromatic hydrocarbon and a dine hydrocarbon.......... 5-20~
the percentages being by percent by weight of the total polymer weight By varying the relative proportions of the polyp etherimide blend, one can produce a broad spectrum of resins each having their respective properties For example, impact strength notched Issued values can range as low as 39 to greater than 180 joules per meter.

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A large number of resins can be produced with varying flexural properties Resins have been produced having an initial modulus ranging from 1.50 gegapasca1s to about 3~0 gegapascals.
Particularly preferred blends owe this invention contain polyetherimide to polyester to block copolymer in weight ratios of from about 75:20:5 to about 80:15:5.
Methods for forming the polyetherimide blends of the present invention may vary considerably. Prior art blending techniques are generally satisfactory. A
preferred method comprises blending the polymers, extra-ding the blend, and chopping the extradite into pellets suitable for molding by means conventionally used to mold normally solid thermoplastic compositions.
The polyetherimide blends of the present invention enable one to more specifically tailor a resin to its end use. These blends permit the manufacturer to make a less expensive product as well as make new products that were not previously envisioned The invention is further illustrated by the lot-lowing example, which is not intended to be limiting.
Example Blends were extruded in a 28 mm Werner Pfleiderer twin screw extrude. The temperature ranges were from 330C at the feed throat to 325~C at the die. After equilibrium had been achieved, the extradite was chopped into pellets. The pellets were injection molded at a temperature of 315~C and a mold temperature of 95C.
The molded specimens were then evaluated to determine standard mechanic eel properties.
Thy tables below list the proportions ox each come potent of the polyetherimide blend as well as the resulting properties. The Issued impact data was deter-mined from tests based on ASTM Method D-256. The heat deflection temperature (HUT) was determined from tests I

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based on ASTM Method ~-648, The flexural data was determined prom test based on ASTM Method D-790. the tensile data was based on STYMIE Method ~-63~. ~ardex Impact data was based on ASTM Method D~3029.
S The polyester that was used was CLEARTUFF~ 7202 This polyester it a polyethylene terephthalate resin having an intern to visc05ity of .72 and is currently available from The Goodyear Tire and Rubber Company of Akron, Ohio.
The block copolymer was CREATING 1651 which is a styrene-ethylene-butylene-styrene (SUBS) block copolymer and is commercially available from Shell Chemical Company of octane, Texas.
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Referring to the above test results, when SUBS is blended with polyetherimides in a weight ratio of 5 to US of SEWS to polyetherimide~ typical notched Issued values of 224 joules per meter, an initial modulus of 1.96 gegapascals and a tensile modulus of 2.53 gegapas~
eels are obtained. When the SUBS level was 5 weight percent, polyetherimide was 72~5 weight percent and PET
was at 22.5 weight percent, the notched Issued value was 57 joules per meter, the flexural modulus was 2.995 gegapascals and the tensile modulus was 2.79 gegapascals. Roy partial substitution of PET for the pol~ether~nide yields a resin which not only exhibits excellent notched Issued values but maintains desirable tensile strengths and flexural modulus The polyetherimide blends of the present invention are graphically illustrated in figure 1.
Figures 2-6 are enlargements of the area of the graph of Figure 1 which depicts the present invention.
Figure 2 illustrates the relationship between the relative proportions of components and notched Idea test results. The shaded area depicts blends having rota-lively high notched Issued values.
Figure-3 depicts the area of proportions associated with high heat distortion temperatures (HUT).
Figure 4 depicts the area of proportions associated with relatively high flexural modulus.
Figure 5 depicts the area of proportions associated with relatively high ~lexural strengths.
Figure 6 depicts the area of proportions associated with relatively high tensile strengths.
Modifications and variations of the present invent lion will be apparent to those skilled in the art in light of the above teachings. It is, therefore, to be understood that changes may be made in the particular " .

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Claims (7)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A polyetherimide blend comprising from (a) about 50 to about 95 parts by weight of a polyether-imide; (b) 9.4 to 45 parts by weight of a polyester resin; and (c) about 5 to about 20 parts by weight of a block copolymer of a vinyl aromatic compound (A) and a diene compound (B), of the A-B-A type, the center block being of higher molecular weight than that of the combined terminal blocks.

2. The polyetherimide blend of claim 1, wherein said polyetherimide is of the formula:

where "a" represents a whole number in excess of 1, e.g.
10 to 10,000 or more, Z is a member selected from the class consisting of (1):

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 divalent bonds of the -0-Z-0- radical are situated on the phthalic anhydride end groups, e.g., 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 (1) aromatic hydrocarbon radicals having from 6 to about 20 carbon atoms and halogenated derivatives thereof, (2) alkylene radicals and cycloalkylene radicals having from about 2 to about 20 carbon atoms, C(2-8) alkylene terminated polydiorganosiloxane, and (3) divalent radicals of the formula:

where Q is a member selected from the class consisting of , and -CxH2x-where x is a whole number from 1 to 5 inclusive.

3. The polyetherimide of claim 1 wherein said polyester is made from the reaction of dicarboxylic acid and diesters with a polyhydric alcohol, said dicar-boxylic acid selected from the group consisting of alkyl dicarboxylic acids having a total of from 2 to 16 carbon atoms, aryl or alkyl substituted aryl dicarboxylic acids containing a total of from 8 to about 16 carbon atoms, and combinations thereof, said diester having from 4 to 20 carbon atoms, an alkyl substituted aryl ester having from 10 to 20 carbon atoms, and combinations thereof, and wherein said polyhydric alcohol is selected from the group consisting of glycols having from 2 to 11 carbon atoms, from glycol ethers containing from 4 to 12 carbon atoms, and combinations thereof,

4. The polyetherimide blend of claim 1 wherein said polyester is polyethylene terephthalate or poly-butylene terephthalate.

5. The polyetherimide blend of claim 1 wherein the vinyl aromatic compound is styrene and the diene com-pound is selected from the group consisting of ethylene, butylene, isoprene and butadiene or mixtures thereof.

6. The polyetherimide blend of claim 5 wherein said diene compound is butylene and ethylene.

7. The polyetherimide blend of claim 4, 5 or 6, wherein the weight ratio of polyetherimide to polyester to block copolymer ranges from about 75:20:5 to about 80:15:5.