JPS60501009A - Polyetherimide-polypropylene blend - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Polyetherimide polyester Lipropylene blend The present invention comprises (a) a polyetherimide and (b) a small amount, e.g. about 1-20% by weight. A group of blends containing polypropylene or copolymers thereof. unexpected Also, these blends have a notched structure in the polyetherimide component of the blend. Other polyesters that do not contain small amounts of polypropylene as well as isot impact strength Notched Izo impact strength of -tellimide-polypropylene blend ) Has large notched izot impact strength.

The blend of the invention has the formula [In the formula, a represents an integer greater than 1, such as 10 to 10,000 or more. , the group -0-A or (H/ is hydrogen, lower alkyl group or lower alkoxy group ), and the preferred polyetherimide is polyether (2) Monotylimide is the formula is a polyetherimide, and the two combinations of -0-2-0- groups are 3, 3'; after R' is hydrogen as in the 3, 4'; 4, 3' and 4,4' positions. 10-A group, and 2 is (1) and (2) general formula ( (3) One member selected from the group consisting of divalent groups, q is O or 1, and y is 1 to 1. 1 negative of the group consisting of two organic groups (with a history number of 5), and R is (1) the number of carbon atoms aromatic hydrocarbon group having 6 to 20 and its halogenated derivative, (2) carbon atom Alkylene groups and cycloalkylene groups having 2 to 20 molecules, 02 to C8 alkylene groups, Kylene end-stopped polydiorganosiloxane, and formula (3) one member selected from the group J, where X is an integer from 1 to 5) Contains a polyetherimide containing two organic groups selected from the group consisting of divalent groups. do. Particularly preferred polyetherimides for the purposes of the present invention are -0-A (and and 2 respectively Ashi, R is A polyetherimide selected from R is Metafe (4) Special νRGO- Most preferred is a polyetherimide that is 50100.9(3)nylene.

The polypropylene used in the blend of the present invention is atactic polypropylene. So-called isotactic polypropylene with structural formula (wherein is an integer greater than 100). Generally the number of polypropylene The average molecular weight is typically greater than about 100,000. This kind of polypropylene In addition, Kirk Fist Osomer's Encyclopedia Beepia Fist Off-Chemical Techno Vol. 14, pp. 282-307 (1967) and U.S. Pat. No. 12300 and No. 3112301, which are cited here. Incorporate it into this.

Polypropylene has low density (specific gravity approximately 0.90); high melting point (approximately 167°C); Liethylene has superior tensile strength, greater stiffness, and better stress cracking resistance: High wear resistance; excellent dielectric properties; low creep; and acids, alkalis, solvents and It features a glossy surface that is highly resistant to other chemical attacks.

Globylene homopolymers and copolymers are produced industrially in many varieties and formulations. It is being Molding and extrusion varieties are available in low, medium and high melt flows only. medium- or high-impact, heat- and UV-stable formulations, and controlled crystallinity. Available in resin form with Relatively small amounts, example (5) and about 1 to about 20% by weight of ethylene or other alpha-olefins, among other monomers. Copolymerization with monomers modifies the polypropylene structure, improving impact resistance and reducing The present invention provides a polymer having a embrittlement temperature of

The polyetherimide for the blends of the invention has the formula: ) aromatic bis(ether acid anhydride) and the formula %formula% (wherein R is as defined above) with an organic diamine. The aromatic bis(ether anhydride) of the above formula can be obtained by any known method. , for example, 2゜2-bisC4-C2,3-dicarboxyphenoxy)phenyl] Lopanedic anhydride: 4,4'-bis(2,3-dicarboxyphenoxy)di Phenyl 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; ( 6) 4.4'-bis(2,3-dicarboxyphenoxy)penzophenone 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 ) diphenyl ether sialic anhydride: 4,4'-bis(3,4-dicarboxylic anhydride) cyphenoxy) diphenyl sulfide diacid anhydride; 1,3-bis(3,4-di carboxyphenoxy)benzenedic anhydride; 1,4-bis(3゜4-dicarbohydrate) 4゜4'-bis(3,4-dicarboxy) phenoxy)penzophenone diacid anhydride: 4-(2,3-dicarboxyphenoxy) c)-4-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane Di-acid anhydrides, etc. and mixtures of such di-acid anhydrides.

Furthermore, the aromatic bis(ether acid anhydride) hamataton contained by the above formula, M, M; 70 Lynskey, F. Nis; Pennov, M. I; Ruda Koff, nee.

He, (Institute of Heteroorganic Coy Bounds, Akade Filed on May 3, 1967 by Mii Obsciensis, USSR), 1969 It is shown in USSR Patent No. 257010 of November 11th. Furthermore, diacid anhydride flies M, M, Codon, F, Nis, Florinsky, Zh-Org, Kh In, 4(5), 774 (1968).

(7) Examples of organic diamines of the above formula include m-7, enylene diamine, P-phenylene diamine, Amine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodipheny lumethane, pentedine, 4,4'-diaminodiphenyl sulfide, 4. ．． 4 '-Diamino diphenyl sulfone, 4.4'-diaminodiphenyl ether, 1 , 5-diaminonaphthalene, 3,3'-dimethylbenzidine, 3,3'-dimeth Xybenzidine, 2゜4-bis(β-amino-t-butyl)toluene, bis(p -β-amino-t-butylphenyl)ether, bis(p-β-methyl-〇- aminopentyl)benzene, 1,3-diamino-4-isopropylbenzene, 1 , 2-bis(3-aminopropoxy)ethane, m-xylene diamine, p-xy Diamine, 2,4-diaminotoluene, 2,6-diaminotoluene, bis( 3-aminocyclohexyl)methane, 3-methylhbutamethylenediamine, 4. 4-dimethylhebutamethylenediamine, 2,11-dodecanediamine, 2,2- Dimethylp, propylene diamine, octadecanediazine, 3-methoxyhexame ethylenediamine, 2゜5-dimethylhexamethylenediamine, 2,5-dimethyl Hebutamethylene diamine, 3-methyl hebutamethylene diamine, 5-methyl nona Methylenediamine, 1,4-cyclohexanediamine, 1,12-octadecane Diamine, bis(3-aminopropyl) sulfide, N-methyl-bis(3- aminopropyl) amine, hexamethylene diamine, heptamethylene shea, gin , nonamethylene diamine, decamethylene diamine, bis(3-aminopropyl) Tetramethylenedisiloxane, bis(4-aminobutyl)tetramethyldisiloxane Including Sun et al.

Generally, the reaction is carried out at a temperature of about 100 to about 250°C and a phase between the dianhydride and the diamine. To carry out the interaction, well-known solvents such as 0-dichlorobenzene, m- This can be advantageously carried out using cresol/toluene or the like.

Alternatively, polyetherimide can be mixed simultaneously and heated the mixture of each component at high temperature. made by melt polymerization of any diacid anhydride mentioned above and any diamino compound mentioned above. be able to. Generally melting at about 200-400°C, preferably 230-300°C Polymerization temperatures can be used. The reaction conditions and proportions of each component are determined according to the desired molecular weight and intrinsic viscosity. and solvent resistance can vary widely. Generally high molecular weight polyether For imide, use equimolar amounts of diamine and dianhydride, however In some cases, a small excess (approximately 1 to 5 moles) of diamine may be used to remove the terminal amine groups. A polyetherimide having the following properties can be produced. Polyester is generally useful. Tellimide has a concentration as low as 0.2 tu/l when measured in m-cresol at 25°C. Intrinsic viscosity [η] of large, preferably 0.35 to 0.60 or more than 0.7 tU/ have

Among the many methods of making polyetherimides are U.S. Pat. No. 38 to Heath et al. 47.867, Williams No. 3847869, Takekoshi et al. No. 3850 No. 885, White No. 3852242 and No. 3855178 (9) including the method described. These descriptions are of polyethers suitable for the blends of the present invention. The general and special methods of manufacturing lumides are cited in their entirety for the purpose of teaching by example. Insert the section here.

Suitable polypropylenes and copolymers thereof, as described above, are well known to those skilled in the art. It can be made using the following methods or available on the market. polypropylene and A conventional example of a method for forming biso(D) copolymers is the aforementioned Karl-Ossomer method. As discussed in the aforementioned chapter of Encyclopedia Op Chemical Technology. It is. For example, industrial polypropylene is generally made from titanium trichloride compositions and Aluminum alkyl compounds such as triethylaluminum or diethylaluminum It is made using a solid crystalline hydrocarbon-insoluble catalyst made from mini chloride. Ru. Depending on the specific catalyst and polymerization conditions used, the polymer produced will have a Not only isotactic, syndiotactic, or so-called stereo May contain block molecules. If desired, these can be extracted with a selective solvent and thoroughly cleaned. It is possible to produce products with low atactic content that crystallize completely.

According to the invention, when the blend contains a small proportion of polypropylene, the polyether A particularly useful blend of tellimide and polypropylene is obtained. This blurring However, the notched impact strength of the polyetherimide component of the blend Not only has a notched impact strength, but also a small percentage of professionals (10) Blends that do not contain pyrene also have great notched impact strength. Ru. Thus, about 80 to about 99% by weight polyetherimide and about 20 to about 1% by weight % polypropylene, preferably about 85-95% polyetherimide and Blends of polypropylene containing about 15 to 5% by weight are included within the scope of this invention. It will be done.

Generally, blends of polyetherimide and polypropylene within the above ranges are to give the desired physical properties by selecting the appropriate proportions of the blend components. can be made. A relatively high proportion of polyetherimide within the range is usually blended contributes to high mechanical properties and high heat deflection temperatures. Polyps within limits A high proportion of lopyrene generally provides high impact strength to the blend.

The unique properties of the blends of the invention are illustrated in the drawings, which show polyetherimide and vs. polyetherimide content for a series of blends of polypropylene. Figure 2 is a plot of notched impact strength. Regarding the drawings, please refer to Example i. will be discussed in detail.

The polyetherimide-polypropylene blends of the present invention contain fillers in conventional amounts. Stabilizers, plasticizers, softeners, surfactants, pigments, dyes, tougheners, flame retardants, and rare It is contemplated that the scale may also contain additive materials such as diluents. In addition, the blend of the present invention is of two types. Also includes the above polyetherimides and one or more polypropylenes and copolymers thereof. intended to be possible.

How to form the polyetherimide-polypropylene type blends of the present invention? It is possible to change it. Prior art mixing methods are generally satisfactory. The preferred method is Additives such as reinforcing agents and polymers are mixed in the form of powders, particles or filaments. The mixture is extruded and the extrudate is cut to form a conventional solid thermoplastic composition. A pellet suitable for forming by means conventionally used for shaping. do.

The polyetherimide-polypropylene blend of the present invention can be used in film, molding compositions. It has applications in a wide variety of physical forms, including use as objects, coatings, etc. Fi When used as a lume or made into a molded article, these blends In addition to having good physical properties at room temperature, including laminates made from They possess excellent response to working loads and their strength at high temperatures for long periods of time. Main departure Films formed from light blends can be used in applications for which films are traditionally used. Can be used in For example, the blends of the invention may be used in automobiles and for decorative and protective purposes. and aircraft, motor slot liners, transformers, dielectric capacitors, cables. and the high temperature of the coil packaging (forming the winding coil insulation of the motor reservoir) Can be used for electrical insulation and containers and container linings. Bren It can also be used in laminated structures, in which case the blended film and solution are applied to various heat-resistant or other types of materials such as vests, mica, glass fibers, etc. The sheets are stacked on top of each other and then the sheets are subjected to high temperature and pressure to form a resin binder. flow and harden to form a cohesive laminated structure. Main train (12) Thin width GO-5 Made from polyetherimide-polypropylene blend of 010 (19(5) Ming) The film may also be used for printed circuit applications.

Alternatively, a solution of the blend shown here can be deposited onto a conductor such as copper, aluminum, etc. The coated conductor is then heated to high temperature to remove the solvent, and a continuous resin is applied on top of it. A composition can be provided. Polyamide, polyester, silicone as required Cone, polyvinyl formal resin, epoxy resin, polyimide, polytetraph Additional overcoats including the use of polymeric coatings such as fluoroethylene etc. Can be applied to insulated conductors. Oats on other types of insulation; - book as a coat This does not preclude the use of inventive blends.

Other intended uses for these blends include making brake linings. Its use as a binder for asbestos fibers, carbon fibers and other fiber materials. including the use of these. In addition, asbestos, glass fiber, and talc are added during blending before molding. By incorporating fillers such as quartz, powder, particulate carbon, silica, etc. Molding compositions and molded articles can be formed from bright polymer blends. Molded products are handled by those skilled in the art. It can be formed under heating or under heating and pressure by a method well known in the art.

The following examples illustrate the specific polyetherimide-polypropylene or polymer according to the invention. Figure 2 shows a rietherimide-polypropylene copolymer blend. Examples are illustrative. The present invention is not limited to the present invention. 2. In the examples, all parts are shown (1 3) Percentages are by weight unless otherwise specified.

Some series of polyether polymers according to the invention and some outside the scope of the invention Make a mid-polypropylene blend, mold the blend into specimens, and The seeds were tested for physical properties.

The blended polyetherimide is heated at high temperatures of about 250 to about 300°C under a nitrogen atmosphere. 2° with the m-phenylenediamine you made? -bis(4-(3,4-dicarboxif) from essentially equimolar amounts of the reaction product of phenoxy)phenyl]propanedic anhydride. Had made. The polymer is extruded at approximately 300'C to form strands and mechanically stabilized. Cut to let. Polyetherimide specimens were heated to a temperature of approximately 685-700'F. injection molded from pellets. The physical properties of polyetherimide are shown in Table 1 below. Shown in the column.

The polypropylene used to produce the blend was manufactured in Tsilmi, Prauea. Trade name Polypropylene 6 by Vercules Inc. It was a heat-resistant polypropylene commercially available under No. 524. This polypropylene monomer In Germany, according to the literature, it has the properties shown in the bottom column of Table ■. to form a blend About 90 parts of the above polyetherimide was mixed with about 10 parts of polypropylene. . The mixture of two polymers is then heated to a die temperature of about 600 below and about 580-630 Warner & Pfeidler extruder with temperature profile varying at T I pushed it out. Profit (14) The extrudate is cut into pellets, and the pellets are approximately 550T to 600T. at a temperature of The specimens were injection molded on a Tettenfield molding machine. The impact strength of these test pieces It was measured by unnotched and notched Izot impact tests, and the results are shown in Table I below. show. The heat deflection temperature, flexural properties and tensile properties of the blends were also measured and are shown in Table I below. Shown below.

The above method of producing a blend can be applied to polyetherimide to polypropylene. It was repeated to make four additional blend test specimens with varying amounts. These blurs If only the results of the unnotched and notched Izot impact tests for the The heating deflection temperature, bending properties and tensile properties are shown in Table 1 below.

(15) (16) In the drawing of Kaba BRGO-501009 (6), with notches from Table 1 The Izot impact strength values were plotted against the relative concentrations of the components of the blend.

The plot shows that a small amount of polypropylene results in significantly higher notched impact strength. It can be observed that However, after this initial rise, the notched impact value is approximately 5 It decreases markedly up to a blend concentration of 0:50, after which this value remains relatively constant. be. Particularly notable is that blends containing about 10% polypropylene - more than tellimide alone, plus a block containing about 30% polypropylene. It is a fact that the notched Izot impact strength is remarkable compared to the Lend.

Example ■ Commercially available under the trade name Polypropylene Copolymer 8501 by Vercules The basic procedure of Example I was repeated except that a polypropylene copolymer was used. Press further The exit temperature profile was varied from about 545-600 below, and the die temperature used was about 6 It was set to 00″F.

As in Example Regarding not only Isotsu impact strength but also heat deflection temperature, bending properties and tensile properties. Tested.

The test results for each of these blends are shown in Table ■.

(17) (18) From the above data shown in Table ■, it can be seen that a small amount of blend with polyetherimide, e.g. 10 inch polypropylene or its copolymer has an unexpectedly high notch. This proves that it provides a material with impact strength. In particular, 10 tips of polypropylene The notched isot impact strength of the polyetherimide monopolymer blend is It is about 18 inches larger than the German one and contains a 30-chipo-lipropylene copolymer. It can be observed that it is about 95 cm larger than that of Lend.

Polyetherimide and/or polypropylene in the blends of each of the above examples Alternatively, other polyetherimides and/or other polypropylenes may be used. It is intended to produce formulations of polymer blends with similar properties. Such blends are also considered within the scope of this invention.

Although the invention has been described in terms of specific embodiments, the invention may be understood as defined in the claims. It will be appreciated by those skilled in the art that many modifications may be made without departing from the scope.

polyetherimide international search report

Claims (1)

[Claims] 1 (a) a small proportion of polypropylene or its copolymer and +b) polyether A composition consisting of a blend of imides. 2. Polypropylene or its copolymer from about 1 to about 20% by weight of the blend The composition according to claim 1. 3 Blend is structural formula Contains polypropylene having the formula A composition according to claim 1. 4. Blend is structural formula (wherein is an integer greater than 100) The composition according to claim 2. 5. The set according to claim 2, wherein the blend contains a polypropylene copolymer. A product. 6. Polyetherimide is the formula (20) [a represents an integer greater than 1, and the group -○-A or (R/ is hydrogen, lower alkyl group or lower alkoxy group), and 2 is (1) and (2) general formula One member selected from the group consisting of divalent groups, q is O or (21) 1 and y is an integer from 1 to 4) is a member of the group consisting of two organic groups JP, R is (1) an aromatic hydrocarbon group having 6 to 20 carbon atoms and its (2) alkylene group having 2 to 20 carbon atoms and cycloa alkylene groups, 02-C8 alkylene-terminated polydiorganosiloxanes, and (3) Formula (X is an integer from 1 to 5) two organic groups selected from the group consisting of the valence group Q. Section 2, Section 3. The composition according to item 4 or 5. 7. Polyetherimide is the formula is a polyetherimide, and the two combinations of -0-2-0- groups are 3, 3'; 3, 4'; 4, 3' or 4,4' position according to claim 6 Composition. B, z is Deoshi, R is 8. A composition according to claim 7, selected from: 9. Polyetherimide is the formula 9. The composition according to claim 8, which is a polyetherimide. (1)