JPH049184B2 - - Google Patents

Description

Claim 1 Contains a blend of (a) polypropylene or a copolymer thereof (excluding a copolymer consisting of propylene and glycidyl ester of an α,β-unsaturated acid) and (b) polyetherimide, 1 to 15 of polypropylene or its copolymer blend
The composition consists of % by weight. 2 Blend is structural formula 2. A composition according to claim 1, comprising polypropylene having the formula: wherein b is an integer greater than 100. 3. The composition of claim 1, wherein the blend contains a polypropylene copolymer. 4 Polyetherimide is the formula [a represents an integer greater than 1, and the group -O-A< is

【formula】

【formula】

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

【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 of (1) an aromatic hydrocarbon group having 6 to 20 carbon atoms and its halogenated derivative, (2) 2 carbon atoms. alkylene and cycloalkylene groups having ~20, _C2 - _C8 alkylene-terminated polydiorganosiloxanes, and formula (3) (Q is -O-,

【formula】

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

【formula】 and R is

【formula】

【formula】

A composition according to claim 5, selected from the formula: 7 Polyetherimide is the formula 7. The composition according to claim 6, which is a polyetherimide. Description The present invention comprises (a) polyetherimide and (b) a small amount of
For example, it relates to a family of blends containing about 1 to 20% by weight of polypropylene or copolymers thereof.
Surprisingly, these blends not only have a notched isot impact strength of the polyetherimide component of the blend, but also a notched isot impact strength that is greater than that of other polyetherimide-polypropylene blends that do not contain small amounts of polypropylene. It has a high impact strength. The blend of the invention has the formula [In the formula, a is an integer greater than 1, e.g. 10 to 10000
or more, and the group -O-A< is

【formula】

【formula】

[Formula] (R' is hydrogen, a lower alkyl group, or a lower alkoxy group), and preferred polyetherimides are polyetherimides with the formula is a polyetherimide 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
＜Including groups, Z is (1)

【formula】 【formula】

【formula】

【formula】

【formula】

【formula】

and (2) general 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) (Q is -O-,

【formula】

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

[expression] and

【formula】 and R is

【formula】

【formula】

A polyetherimide selected from the formula: Most preferred are polyetherimides in which R is metaphenylene. The polypropylene used in the blend of the present invention is a so-called isotactic polypropylene as opposed to an atactic polypropylene, and has the structural formula (where b is an integer greater than 100).
Generally, the number average molecular weight of polypropylene is typically greater than about 100,000. This type of polypropylene is further described in Kirk Osomer's Encyclopedia of Chemical Technology, Volume 14, Vol.
pp. 282-307 (1967) and U.S. Pat.
3112300 and 3112301,
These are incorporated herein by reference. Polypropylene has low density (specific gravity approximately 0.90); high melting point (approximately 167°C); greater tensile strength, greater stiffness, and better stress cracking resistance than high-density polyethylene; high abrasion resistance; excellent dielectric properties; It features low creep; and a glossy surface that is highly resistant to acids, alkalis, solvents and other chemical attack. Propylene homopolymers and copolymers are produced industrially in many varieties and formulations. Available in molding and extrusion varieties, low, medium and high melt flow as well as medium or high impact types, heat and UV stable formulations, and resins with controlled crystallinity. Copolymers with ethylene or other alpha-olefin monomers, even in relatively small amounts, e.g., from about 1 to about 20% by weight, of other monomers modify the polypropylene structure, resulting in improved impact resistance and reduced brittleness. The present invention provides a polymer having a temperature of The polyetherimide for the blend of the present invention 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]propanoic anhydride; 4,4'-
Bis(3,4-dicarboxyphenoxy)diphenyl ether diacid anhydride; 4,4'-bis(3,4
-dicarboxyphenoxy)diphenylsulfidic anhydride; 1,3-bis(3,4-dicarboxyphenoxy)benzenedic anhydride; 1,4-
Bis(3,4-dicarboxyphenoxy)benzenic anhydride; 4,4-bis(3,4-dicarboxyphenoxy)benzophenonediaic anhydride; 4-
(2,3-dicarboxyphenoxy)-4-(3,
4-dicarboxyphenoxy)diphenyl-2,
2-propanedic anhydride and the like and mixtures of such dianhydrides. Furthermore, aromatic bis(ether acid anhydrides) or cotons, m. M. ;
Florinsky, F. S. ; Bennov, M.
Ai. ; Rudakov, A. P. (Institute of Heteroorganic Compounds,
Academy of Sciences, USSR)
It is shown in USSR Patent No. 257010, filed May 3, 1967, November 11, 1969. Furthermore, di-acid anhydride is M. M. Cotton, F. S. Florinsky, Zh.Org.Khin.4(5), 774 (1968). Examples of organic diamines of the above formula include m-phenylenediamine, P-phenylenediamine, 4,4'-
Diaminodiphenylpropane, 4,4'-diaminodiphenylmethanebenzidine, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1 , 5-diaminonaphthalene, 3,3'-
Dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,4-bis(β-amino-t-butyl)
Toluene, bis(p-β-amino-t-butylphenyl)ether, bis(p-β-methyl-o-
(aminopentyl)benzene, 1,3-diamino-
4-isopropylbenzene, 1,2-bis(3-
aminopropoxy)ethane, m-xylene diamine, p-xylene diamine, 2,4-diaminotoluene, 2,6-diaminotoluene, bis(3-
aminocyclohexyl)methane, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-dodecanediamine,
2,2-dimethylpropylenediamine, octamethylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine,
3-methylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-cyclohexanediamine, 1,12-octadecanediamine, bis(3-aminopropyl)sulfide, N-methyl-bis(3-aminopropyl)amine, Contains hexethylene diamine, heptamethylene diamine, nonamethylene diamine, decamethylene diamine, bis(3-aminopropyl)tetramethylenedisiloxane, bis(4-aminobutyl)tetramethyldisiloxane, and the like. Generally, the reaction is carried out at a temperature of about 100 to about 250°C using well-known solvents such as o-dichlorobenzene, m-cresol/toluene, etc. to effect the interaction between the dianhydride and the diamine. This can be done to your advantage. Alternatively, polyetherimide can be made by melt polymerization of any of the above dianhydrides and any of the above diamino compounds while simultaneously mixing and heating the mixture of each component at elevated temperatures. Generally about 200-400
Melt polymerization temperatures of 230-300°C can be used. The reaction conditions and proportions of each component can vary widely depending on the desired molecular weight, intrinsic viscosity, and solvent resistance. Generally, equimolar amounts of diamine and dianhydride are used for high molecular weight polyetherimides; however, in some cases, a slight excess (approximately 1-5 mole %) of diamine is used to remove the terminal amine groups. A polyetherimide can be produced with Generally useful polyetherimides, when measured in m-cresol at 25°C:
greater than 0.2 dl/g, preferably 0.35-0.60 or
It has an intrinsic viscosity [η] of 0.7 dl/g or more. Among the many methods of making polyetherimides are U.S. Pat. No. 3,847,867 to Heath et al., U.S. Pat.
No. 3,852,242 and White, No. 3,855,178. These descriptions are incorporated herein by reference in their entirety to teach, by way of example, general and specific methods of making polyetherimides suitable for the blends of the present invention. Suitable polypropylene and copolymers thereof as described above (excluding copolymers of propylene and glycidyl esters of α,β-unsaturated acids)
can be made by methods well known to those skilled in the art or are commercially available. Conventional methods for forming polypropylene and copolymers thereof are discussed in the aforementioned chapter of Karl Ohmer's Encyclopedia of Chemical Technology, cited above. For example, industrial polypropylene is generally made using a titanium trichloride composition and a solid crystalline hydrocarbon-insoluble catalyst made from an aluminum alkyl compound such as triethylaluminum or diethylaluminum chloride. Depending on the particular catalyst used and the polymerization conditions, the polymers produced may contain not only atactic but also isotactic, syndiotactic or so-called stereoblock molecules.
These can be selectively solvent extracted, if desired, to yield a product with a lower atactic content that crystallizes more completely. According to the invention, particularly useful blends of polyetherimide and polypropylene are obtained when the blend contains a small proportion of polypropylene. Such blends not only have a notched impact strength that is greater than that of the polyetherimide component of the blend, but also a notched impact strength that is greater than that of blends that do not contain a small proportion of propylene. have Therefore about 85 to about 99
Blends consisting of % by weight polyetherimide and from about 15% to about 1% by weight polypropylene are included within the scope of this invention. Blends of polyetherimide and polypropylene generally within the above ranges can be made to provide desired physical properties by selecting the appropriate proportions of the blend components. A relatively high proportion of polyetherimide within the range usually contributes high mechanical properties and high heat deflection temperatures to the blend. A high proportion of polypropylene within limits generally provides high impact strength to the blend. The unique properties of the blends of the invention are shown in the drawings,
The figure is a plot of notched impact strength versus polyetherimide content for a series of blends of polyetherimide and polypropylene. With regard to the drawings, the embodiments will be discussed in detail later. The polyetherimide-polypropylene blends of the present invention contain fillers, stabilizers, plasticizers, softeners, surfactants, pigments, dyes, reinforcing agents,
It is contemplated that additive materials such as flame retardants and diluents may also be included. In addition, the blend of the present invention comprises two or more polyetherimides, one or more polypropylene, and a copolymer (with the exception of propylene α, β
- except for copolymers consisting of glycidyl esters of unsaturated acids). The method of forming the polyetherimide-polypropylene type blends of this invention can vary considerably. Prior art mixing methods are generally satisfactory.
A preferred method is to mix additives such as reinforcing agents and polymers in the form of powders, particles or filaments;
The mixture is extruded and the extrudate is cut into pellets suitable for molding by means conventionally used for molding conventional solid thermoplastic resin compositions. The polyetherimide-polypropylene blends of the present invention have utility in a wide variety of physical forms, including use as films, molding compositions, coatings, and the like. Not only do these blends have good physical properties at room temperature when used as films or in molded articles, including the laminates made from them, but they also have excellent resistance to long-term elevated temperature working loads. Possess responses and their intensity. Films formed from the blends of the present invention are
Can be used in applications for which films have traditionally been used. For example, the present invention blends high temperature electrical insulation for motor slot liners, transformers, dielectric capacitors, cable and coil packaging (forming wound coil insulation for motors) in automobiles and aircraft for decorative and protective purposes. , and can be used for containers and container linings. Blends can also be used in laminated structures,
In this case, blended films and solutions are applied to various heat-resistant or other types of materials such as asbestos, mica, fiberglass, etc., the sheets are stacked on top of each other, and the sheets are then subjected to high temperature and pressure to cause the resin binder to flow. and cured to form a bonded laminated structure. Films made from the polyetherimide-polypropylene blends of this invention may also be used for printed circuit applications. Alternatively, a solution of the blend described herein can be coated onto a conductor such as copper, aluminum, etc., and the coated conductor can then be heated to an elevated temperature to remove the solvent and provide a continuous resin composition thereon. . If desired, additional overcoats can be applied to such insulated conductors, including the use of polymeric coatings such as polyamides, polyesters, silicones, polyvinyl formal resins, epoxy resins, polyimides, polytetrafluoroethylene, and the like. The use of the blends of the invention as overcoats on other types of insulation is not excluded. Other contemplated uses for these blends include their use as binders for asbestos fibers, carbon fibers and other fibrous materials in making brake linings. Furthermore, asbestos, glass fiber, talc,
Molding compositions and molded articles can be formed from the polymer blends of this invention by incorporating fillers such as quartz, powder, particulate carbon, silica, and the like. The molded article can be formed under heat or under heat and pressure by methods well known to those skilled in the art. The following examples demonstrate particular polyetherimide-polypropylene or polyetherimide-polypropylene copolymer blends according to the invention.
The examples are given by way of illustration and are not intended to limit the invention. In the examples, all parts and percentages are by weight unless otherwise specified. EXAMPLES A series of polyetherimide-polypropylene blends, several in accordance with the present invention and several outside the scope of the present invention, were made, the blends were formed into specimens, and the specimens were tested for various physical properties. The polyetherimide blend is made from m-phenylenediamine and 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propanedic acid, which is made at a high temperature of about 250 to about 300°C under a nitrogen atmosphere. The reaction products were made from essentially equimolar amounts of anhydride. The polymer was extruded at approximately 300°C to form strands and mechanically cut into pellets. A test piece of polyetherimide was heated to approximately 362 to 371℃ (approximately 685 to 700℃).
It was injection molded from pellets at a temperature of 〓). The physical properties of the polyetherimide are shown in column 1 of the table below. The polypropylene used in making the blend was a heat resistant polypropylene sold under the trade designation Polypropylene 6524 by Hercules Inc. of Wilmington, Del. According to the literature, this polypropylene alone has the properties shown in the bottom column of the table. About 90 parts of the polyetherimide described above was mixed with about 10 parts of polypropylene to form a blend. The mixture of two polymers is then heated to about 316°C.
(approximately 600〓) die temperature and approximately 304~332℃ (approximately 58
It was extruded in a Warner & Puchidler extruder with a temperature profile varying at ~630°). The resulting extrudate was cut into pellets, and the pellets were injection molded into test specimens in a batten field molding machine at a temperature of about 288-316°C (about 550-600°C). The impact strength of these specimens was measured by unnotched and notched Izot impact tests,
The results are shown in the table below. Heat deflection temperature of the blend,
Flexural and tensile properties were also measured and are shown in the table below. The above method of making blends was repeated to make test specimens of four additional blends varying the amount of polyetherimide to polypropylene. The heat deflection temperature, flexural and tensile properties as well as the results of unnotched and notched Izot impact tests for these blends are shown in the table below.

[Table] 5 From published data.
In the figure, the notched Izot impact strength values from the table are plotted against the relative concentrations of the components of the blend. It can be observed from the plot that small amounts of polypropylene give rise to significantly higher notched impact strength values. However, after this initial increase, the notched impact value drops significantly to about a 50:50 blend concentration, after which this value remains relatively constant. Of particular note is the fact that blends containing about 10% polypropylene have significant notched Izo impact strength over polyetherimide alone, plus blends containing about 30% polypropylene. EXAMPLE The basic procedure of the example was repeated except that a polypropylene copolymer marketed by Hercules under the trade name Polypropylene Copolymer 8501 was used. Furthermore, the extruder temperature profile is approximately 284-316℃.
(about 545 to 600〓), and the die temperature used was about 316℃ (about 600〓). As in the Examples, specimens of each blend were tested for notched and unnotched Izot impact strength as well as heat deflection temperature, flexural properties and tensile properties. Test results for each of these blends are shown in the table.

【table】

[Table] The above data presented in the table demonstrate that small amounts of polypropylene or copolymers thereof in blends with polyetherimide, for example about 10%, provide materials with unexpectedly high notched impact strength. ing. Specifically, the notched isot impact strength of the 10% polypropylene copolymer blend is about 18% greater than that of polyetherimide alone and about 95% greater than that of the blend containing 30% polypropylene copolymer. It can be observed that The use of other polyetherimides and/or other polypropylenes in place of polyetherimide and/or polypropylene in the blends of each of the above examples is also intended to result in the formulation of polymer blends with similar properties. and such blends are also considered within the scope of this invention. Although the invention has been described in terms of specific embodiments, those skilled in the art will recognize that many modifications can be made without departing from the scope of the invention as defined in the claims.