JPH049183B2 - - Google Patents

Description

Claim 1 Contains a blend of (a) an EPDM terpolymer and (b) a polyetherimide, wherein the amount of the EPDM terpolymer is equal to or less than the polyetherimide of the blend.
A composition that is from 0.1% to less than 20% by weight based on the total weight of the EPDM terpolymer. 2. The composition of claim 1, wherein the EPDM terpolymer contains 40-80% by weight ethylene, 1-10% by weight diene monomer, balance propylene. 3. The composition of claim 2, wherein the EPDM terpolymer contains 50-60% by weight ethylene and 2.6-9% diene monomer. 4. The composition according to claim 2 or 3, wherein the diene monomer is selected from 1,4-hexadiene, dicyclopentadiene, ethylidenenorbornene, methylenenorbornene, propenylnorbornene and methyltetrahydroindene. 5 Polyetherimide is the formula [In the formula, a represents an integer greater than 1, and the group -O-A
<ha

【formula】

【formula】

[Formula] (R' is hydrogen, lower alkyl group or lower alkoxy group), Z is (1)

【formula】 【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] and (2) General formula (X is the formula −CyH ₂ y−,

【formula】

[Formula] One member selected from the group consisting of divalent groups -O- and -S-, q is 0 or 1, and y is 1-4
R is a member of the group consisting of divalent organic groups (an integer of 20 alkylene and cycloalkylene groups, _C2 - _C8 alkylene-terminated polydiorganosiloxanes, and formula (3) (Q is -O-,

【formula】

[Formula] One member selected from the group consisting of -S- and -CxH ₂ x-, where x is an integer from 1 to 5). The composition according to claim 1, 2 or 3, wherein the composition has the following group. 6 Polyetherimide is the formula is a polyetherimide in which the divalent bond of -O-Z-O- is 3,3';3,4';4,3'; or 4,
A composition according to claim 5 in the 4' position. 7 Z is

【formula】 and R is

【formula】

【formula】

7. A composition according to claim 6, which is selected from the formula: 8 Polyetherimide is the formula 8. The composition according to claim 7, which is a polyetherimide. Description The present invention relates to a group of polyetherimide-EPDM terpolymer blends. Among other things, these blends have a notched impact strength that is higher than the notched impact strength associated with the polyetherimide component of the blend. The blending formula of the present invention is [In the formula, a represents an integer greater than 1, for example, an integer from 10 to 10,000 or more, and the group -O-A< is

【formula】

【formula】

[Formula] (In the formula, R' is hydrogen, a lower alkyl group, or a lower alkoxy group, and preferably polyetherimide is is a polyether amide, in which the divalent bonds of the -O-Z-O- group are 3,3';3,4';4,3' and 4,
The latter -O-A where R' is hydrogen as in the 4' position
<preferably containing a group), and Z is (1)

【formula】 【formula】

【formula】

【formula】

【formula】

【formula】

and (2) general formula (In the formula, X is the formula −C _y H _2y −,

【formula】

[Formula] One member selected from the group consisting of divalent groups -O- and -S-, q is 0 or 1, and y is 1
1 of the group consisting of divalent organic groups (an integer of ~5)
R is (1) an aromatic hydrocarbon group having 6 to 20 carbon atoms and its halogenated derivative, (2) an alkylene group and cycloalkylene group having 2 to 20 carbon atoms, C ₂ -C ₈ alkylene-terminated polydiorganosiloxane, and formula (3) (In the formula, Q is -O-,

【formula】

[Formula] is one member selected from the group consisting of -S - and C _x H _2x -, where x is an integer from 1 to 5)] Contains polyetherimide. Particularly preferred polyetherimides for the present invention are polyetherimides in which -O-A< and Z are respectively

【formula】

【formula】 and R is

【formula】

【formula】

A polyetherimide selected from the formula: Most preferred are polyetherimides in which R is metaphenylene. Blends of the present invention include EPDM-terpolymers derived from ethylene, propylene and dienes. EPDM terpolymer is ASTM-D-
1418-64, containing from about 0.1 to about 10 mole percent of olefinic unsaturation, containing ethylene and propylene in the backbone and dienes in the side chains. Contains terpolymers. Preferred EPDM polymers contain about 40 to about 80 weight percent ethylene and about 1 to about 10 weight percent diene monomer, with the balance of the polymer being propylene. Preferred polymers are from about 50 to about 60% by weight, such as 50% by weight ethylene, and from about 2.6 to about 60% by weight.
It contains about 90% by weight of diene monomer, for example 5.0% by weight. The diene monomer is preferably a non-conjugated diene. Examples of these non-conjugated diene monomers that can be used in EPDM terpolymers include 1,4-hexadiene, dichloropentadiene, ethylidenenorbornene, methylenenorbornene, propenylnorbornene, and methyltetrahydroindene. EPDM terpolymers generally range from about 10,000 to approx.
200,000, preferably from about 15,000 to about 100,000, most preferably from about 20,000 to about 60,000. The EPDM terpolymer has a Mooney viscosity of from about 5 to about 90, more preferably from about 10 to about 50, and most preferably from about 15 to about 25 at 100 DEG C. (1+8) minutes. Preferably, _{the N} of the EPDM terpolymer is about 350,000 or less, more preferably about 300,000 or less. _W of EPDM terpolymer is about 500000
It is preferably less than or equal to, more preferably about
350000 or less. Many brands of EPDM terpolymers are available on the market, and these brands generally vary in molecular weight and stabilizers added to the individual brand. representative
Vistalon for EPDM terpolymer
3708 (Exxon Chemical Company).
Vistaron 3708 is (1+8) at 100℃ (212〓)
Ethylene has a Mooney viscosity of about 45-55 in min.
53% by weight, about 3.5% by weight 1,4-hexadiene, and about 43.5% by weight propylene. Polyetherimide has the formula (wherein Z is as previously described) and an organic diamine of the formula H ₂ NR-R-NH ₂ (wherein R is as previously described). It can be obtained by any method well known to those skilled in the art. The aromatic bis(ether acid anhydride) of the above formula has
For example, 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propanedic anhydride;
4,4'-Bis(2,3-dicarboxyphenoxy)diphenyl ether diacid anhydride; 1,3-bis(2,3-dicarboxyphenoxy)benzenedic anhydride; 4,4' -bis(2,3-dicarboxyphenoxy)diphenylsulfide diacid anhydride; 1,4-bis(2,3-dicarboxyphenoxy)benzenedic anhydride; 4,4'-bis( 2,
3-dicarboxyphenoxy)benzophenone diacid anhydride; 4,4'-bis(2,3-dicarboxyphenoxy) diphenylsulfone diacid anhydride;
2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propanedic anhydride; 4,
4'-bis(3,4-dicarboxyphenoxy)diphenylether acid anhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether acid anhydride;
4-dicarboxyphenoxy)diphenylsulfide acid anhydride; 1,3-bis(3,4-dicarboxyphenoxy)benzenic anhydride; 1,4-
Bis(3,4-dicarboxyphenoxy)benzenic anhydride; 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone diacid anhydride; 4-
(2,3-dicarboxyphenoxy)-4'-(3,
4-dicarboxyphenoxy)diphenyl-2,
2-propanoic anhydride and the like and mixtures of such dianhydrides. Furthermore, the aromatic bis(ether acid anhydrides) included by the above formula also include Coton, M. M. ; Florinsky, F. S. ; Besonoff, M.
Ai. ; Rudakov, E. P. (Institute of Heteroorganic Compounds,
Academy of Science, USSR), filed on May 3, 1967, USSR Patent No. 11, November 1969.
No. 257010. Furthermore, di-acid anhydride is M. M. Cotton, F. S. Florinsky in Zh.Org.Khin.4(5), 774 (1968). Examples of organic diamines of the above general formula include m-phenylenediamine, p-phenylenediamine, 4,
4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminophenyl sulfone, 4,4'-diaminodiphenyl ether , 1,5-diaminonaphthalene, 3,
3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,4-bis(β-amino-t-butyl)toluene, bis(p-amino-t-butylphenyl)ether, bis(p-β- Methyl-o-
(aminopentyl)benzene, 1,3-diamino-
4-isopropylbenzene, 1,2-bis(3-
Aminopropoxy)ethane, m-xylylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, bis(4-aminocyclohexyl)methane, 3-methylheptamethylenediamine, 4,4 -dimethylheptamethylenediamine, 2,11-dodecanediamine, 2,2-dimethylpropylenediamine, octamethylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethyleneheptamethylene Diamine, 3-methylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-cyclohexanediamine, 1,12-octadecanediamine,
Bis(3-aminopropyl)sulfide, N-
Methyl-bis(3-amipropyl)amine, hexamethylenediamine, heptamethylenediamine,
nonamethylene diamine, decamethylene diamine,
Examples include bis(3-aminopropyl)tetramethyldisiloxane and bis(4-aminobutyl)tetramethyldisiloxane. Generally, the reaction is carried out using well-known solvents such as o-dichlorobenzene, m-cresol/toluene, etc. to effect the interaction between the dianhydride and the diamine at a temperature of about 100 to about 250°C. It can be done to advantage. Alternatively, it can be produced by melt polymerization of any of the above diamines and any of the above diacid anhydrides while heating the mixture at a high temperature in simultaneous mixing. Generally about 200-400℃, preferably 230℃
Melt polymerization temperatures of ~300°C can be used. The reaction conditions and proportions of each component are determined based on the desired molecular weight, intrinsic viscosity,
and solvent resistance can vary widely. Generally, equimolar amounts of diamine and dianhydride are used for high molecular weight polyetherimide, however in some cases there may be a slight excess (approximately 1
~5 mole %) of diamines can be used to effect the formation of polyetherimides with terminal amino groups. Generally useful polyetherimides have a 0.2
Intrinsic viscosity [η] with high dl/g warpage, preferably 0.35 to 0.60 dl/g or 0.7 dl/g or more
has. Many methods of making polyetherimides include Heath et al. U.S. Pat. No. 3,847,867, Williams et al.
No. 3850885, White No. 3852242 and No.
There is a method described in No. 3855178, etc. These methods are incorporated herein in their entirety by reference to teach, by way of example, general and specific methods for making polyetherimides suitable for the blends of this invention. EPDM terpolymers can be made in a number of ways well known to those skilled in the art. Representative examples for making these terpolymers are provided in U.S. Pat.
No. 3,280,082, British Patent No. 1,030,289 and French Patent No. 1,386,600, which are incorporated herein by reference. Although the amounts of polyetherimide and EPDM terpolymer in the blends of the present invention can vary considerably, generally the amount of EPDM terpolymer is small, e.g. based on the combined weight of the polyetherimide and EPDM terpolymer components of the blend. from 0.1% to less than 20% by weight, preferably about 0.1%
~15% by weight, most preferably about 1-10% by weight. In general, blends of polyetherimide and EPDM terpolymers can be made to provide desired physical properties by selecting the appropriate proportions of the blend components within limits. Generally, a higher proportion of polyetherimide provides better mechanical properties and a higher heat deflection temperature to the blend. Generally, the higher the proportion of EPDM terpolymer, the greater the notched impact strength of the blend. It is also contemplated that the polyetherimide-EPDM terpolymer blends of the present invention may contain additive materials such as fillers, stabilizers, plasticizers, softeners, flame retardants, and diluents in conventional amounts. It is also included that the blends of the present invention can contain one or more EPDM terpolymers and two or more polyetherimides, or can contain two or more EPDM terpolymers in combination with one or more polyetherimides. . The method of forming polyetherimide-EPDM terpolymer blends can vary considerably.
Prior art mixing methods are generally satisfactory. A preferred method is to mix the polymer and additives such as reinforcing agents in powder, particulate or filament form, extrude the blend, and cut the extrudate to form conventional solid thermoplastic compositions. pellets suitable for molding by means of The polyetherimide-EPDM terpolymer blends of the present invention have utility in a wide variety of physical forms, including applications such as films, molding compositions, coatings, and the like. When used as films or to make molded articles, these blends, including laminates made from them, not only have good physical properties at room temperature, but they also withstand high temperature working loads for long periods of time. Retain response and intensity. Films formed from the blends of the present invention can be used in applications for which films have traditionally been used. For example, the blends of the invention are used in automobiles and aircraft for decorative and protective purposes, and to form wound coil insulation for motor slot liners, transformers, dielectric capacitors, coil and cable packaging (motors, and containers and containers). Can be used as high temperature electrical insulation for linings). Blends also blend films or solutions of asbestos, mica,
The sheets are applied to various heat resistant or other types of materials such as glass fibers, etc., the sheets are layered on top of each other, and the seal is then subjected to high temperatures and pressures to cause the flow of the resin binder to harden and create a cohesive laminate structure. It can also be used in the form of a laminated structure. Films made from the polyetherimide-EPDM terpolymer blends of this invention can also be used for printed circuit applications. Alternatively, the solution of the blend described here may be copper,
It can be coated onto a dielectric, such as aluminum, and then the coated dielectric can be heated at an elevated temperature to remove the solvent and form a continuous resin composition thereon. If desired, additional overcoats may be applied to such insulated conductors including the use of polymeric coatings such as polyamides, polyesters, silicones, resins, epoxies, polyimides, polytetrafluoroethylene, and the like. The use of the blends of the invention as overcoats on other types of insulation is not excluded. Other applications anticipated for these blends include their use as binders for asbestos fibers, carbon fibers, and other fibrous materials in brake linings. Furthermore, molding compositions and molded articles can be formed from the polymer blends of the invention by incorporating fillers such as asbestos, glass fibers, talc, quartz powder, finely divided carbon, silica, etc. into the blend, preferably before molding. . Molded articles can be formed by heating, or under heat and pressure, in a manner well known to those skilled in the art. The following examples illustrate specific polyetherimide-EPDM terpolymers according to the invention. It is to be understood that the examples are illustrative and not limiting. In the examples, parts and percentages are by weight unless otherwise specified. EXAMPLES Polyetherimide-EPDM blends according to the invention were made, the blends were molded into specimens, and the specimens were tested for various physical properties. Polyetherimide has a temperature of about 250 under nitrogen atmosphere.
From essentially equimolar amounts of the reaction product of m-phenylenediamide and 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propanedic anhydride prepared at elevated temperature at ~300°C. I made it. The polymer is extruded at approximately 300℃ to form strands,
It was mechanically cut into pellets. The specimen is approx.
It was injection molded from pellets at a temperature of 362-371°C (approximately 658-700°C). The EPDM terpolymer used to form the blend was manufactured by Dupont de Nimoers & Company, Inc., Wilmington, Delaware under the trade name Nordel.
It was a terpolymer commercially available as 1560. This EPDM terpolymer is a hydrocarbon crystalline rubber characterized by high viscosity and high strength. Three mixtures of each component were then made, each mixture containing about 1%, about 5%, and about 10% EPDM terpolymer, respectively, with the balance of each mixture being polyetherimide. The blended mixture was then extruded in a Warner & Pfeidler extruder with a temperature profile varying from about 315-332°C. The formed extrudates were cut into pellets and the pellets were injection molded into test specimens at a temperature of about 321°C to 343°C. The impact strength of these test pieces as well as the polyetherimide test pieces was measured by a notched Izot test, and the results are shown in the table. The heat deflection temperature, flexural strength, flexural modulus and tensile properties of each sample were also measured and are shown in the table below. All three blends were opaque in appearance. EXAMPLES Used to make blends according to the invention
The example was repeated except that the EPDM terpolymer was a terpolymer sold under the trade designation Epcar 306G-8 by B.F. Gudrich Company of Akron, Ohio. This EPDM terpolymer has low molecular weight and low viscosity. Furthermore, increase the extruder temperature to about 315~
The molding temperature was 321-327°C. Not only the notched isot impact but also the heat deflection temperature, bending strength,
The results of flexural modulus and tensile properties are shown in the table.
All three blends were opaque in appearance. EXAMPLE A blend according to the invention was prepared at Uniroyal, Inc. of New York, New York under the trade name Royalene IM/
The method of the example was repeated except that an EPDM terpolymer commercially available as 7100 was used.
EPDM terpolymer is based on Royalene 539, a material with relatively high viscosity. Additionally, the extruder temperature profile was varied from about 315-327°C. The results of the notched isot impact strength, as well as the heat deflection temperature, flexural strength, flexural modulus and tensile properties of test specimens of the blend are shown in the table. All three blends were opaque in appearance.

EXAMPLE The method of the example was repeated except that an EPDM terpolymer marketed by Uniroyal Incorporated under the tradename Royalen IM7473 was used to make the blend according to the invention. This EPDM terpolymer is about 70% Royalene 100, which is a material with good resistance to low temperature impact.
and about 30% polypropylene with an MFI greater than about 7. Furthermore, the molding temperature is 327
It was ~349℃. The heat deflection temperature, flexural strength, flexural modulus, and tensile properties as well as the results of the notched iso impact test for test specimens of the blend are shown in the table. The blend was opaque in appearance. EXAMPLE The method of the example was repeated except that an EPDM terpolymer marketed by Uniroyal Incorporated under the tradename Royalen IM7473 was used to make the blend according to the invention. This EPDM terpolymer is about 70% Royalene 100 and about 30% polypropylene with an MI of about 2 to 6.
It is based on %. Additionally, the extruder temperature profile varied from about 315°C to about 327°C. The heat deflection temperature, flexural strength, flexural modulus, and tensile properties as well as the notched Izo impact test for test specimens of the blend are shown in the table. The blend was opaque in appearance. As evidenced by the above test results, all of the blends have significantly improved notched impact strength over polyetherimide alone. The best improvement in notched isot impact strength is Royalen.
Obtained with a blend containing about 10% of IM7473,
In this case, an increase of about 3.5 times was obtained. Notched Izot impact strength for all blends except for the example blend containing Nordel.
It exceeds 11.4cm・Kg/cm (approximately 2.1ft.1b/in),
The majority of the blends had notched impact strengths in excess of about 3.0 ft.1 b/in at 10% EPDM terpolymer content. The unnotched Izo impact strength of the blend was observed to be lower than that of the polyetherimide component alone, especially when the EPDM content was about 10%. The reduced unnotched impact strength is likely due to the formation of two phases within the blend, which may cause delamination upon impact, thus reducing impact strength. Furthermore, the heat deflection temperature for the blend did not change significantly over that of the polyetherimide component itself, while the flexural and tensile properties of the blend were slightly less than that of the polyetherimide. Overall, the blends according to the invention have improved notch sensitivity under the influence of tensile and flexural properties. Blends containing Royalene IM7100 are found to have the best overall balanced properties with adequate unnotched isot impact strength and flexural and tensile properties and significantly improved notched isot impact strength. . By substituting other polyetherimides and/or other EPDM terpolymers for the polyetherimides and/or terpolymers of the blends of each of the above examples, polyethers with similar properties such as improved notch sensitivity can be obtained. Imide
EPDM terpolymer formation can be done,
Such blends are considered within the scope of this invention. Although the invention has been described with reference to specific embodiments,
Many modifications can be made by those skilled in the art without departing from the scope of the invention as defined in the claims.