JPS60501007A - Blends of polyether and organosiloxane-polycarbonate block copolymers - 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 and Olga Nosiloxane-polycarbonate Blends of block copolymers The present invention relates to polyetherimide and organopolysiloxane and polycarbonate. Blends of block copolymers of. These blends are especially - exhibits a good combination of impact strength and bending properties with a relatively high proportion of tellimide, and Relatively high concentrations of block copolymers of ganopolysiloxane and polycarbonate exhibits sexual behavior.

The blend of the invention has the formula [In the formula, a represents an integer greater than 1, for example 10 to 1'OO00 or more, and the group -0 -A〈is (R1 is hydrogen, lower alkyl group or lower alkoxy group), and preferably Preferably, polyetherimide has the formula (2) As is the case with polyetherimide, R' is hydrogen, and the divalent bond of the -〇-zo- group The latter 10- Contains A group: Z is (1) and (2) One member selected from the group consisting of valence groups, 9 is 0 or 1, and y is 1 to 5. R is a member of the group consisting of two organic groups (an integer), and R has (1) 6 to 6 carbon atoms. Aromatic (3) with 20 symbol Showa GO-501007 (3) group hydrocarbons and their (2) an alkylene group having 2 to 20 carbon atoms and a halogenated derivative of Chloalkylene group, 02-C8 alkylene end-stopped polydiorganosiloxane, and (3) equation one member selected from the group consisting of two organic groups selected from the group consisting of polyetherimide. present invention Particularly preferred polyetherimides for this purpose are -〇-A〈and Z are H3 and R A polyetherimide selected from Polyether in which R is metaphenylene Most preferred is limide.

Also included in the blends of the invention are structural formulas (4) [wherein n is at least 1, preferably n is an integer equal to 1 to about 1000, b is equal to 1 to 200, c is equal to about 5 to about 200, preferably C is about 15 The ratio of C to C varies from about 0.05 to about 3, with an average value of ~90; When having an average value of about 15 to about 90, the ratio of b to C is about 0.067 to about 0.45 It is preferable that d is 1 or more, U is 1 to 4, and B is , T is hydrogen and one member selected from 10-0R3, R1 is hydrogen, 1 is one member selected from the group of valent hydrocarbon groups and halogenated monovalent hydrocarbon groups, and R Is 2 a group of monovalent hydrocarbon groups, halogenated monovalent hydrocarbon groups, and cyanoalkyl groups? R3 is a monovalent hydrocarbon group and a halogenated hydrocarbon group. Y is a member selected from the group consisting of hydrogen, a lower alkyl group, a halogen group, and one member selected from the group consisting of It also contains organopolysiloxane-polycarbonate copolymers.

(5) Groups represented by R include aryl groups and halogenated aryl groups, such as Phenyl, chlorophenyl, xylyl, tolyl groups, etc.: Aralkyl groups such as phenyl aliphatic, haloaliphatic and alicyclic groups such as alkyl, benzyl, etc. Alkenyl, cycloalkyl, haloalkyl groups (methyl, ethyl, furovir, (including robutyl, chlorohexyl group V), and all R1s are the same group. or can be two or more of the above-mentioned groups, R1 is a methyl group Preferably, R2 includes all groups included by R1 above except hydrogen. , R2 can all be the same group, or any of the above R, groups except hydrogen. R2 is preferably a methyl group.

R2 also includes all groups included by R1 excluding hydrogen, plus cyanoalkyl It also includes groups such as cyanethyl and cyanobutyl groups. included by its definition Examples of groups include hydrogen, methyl, ethyl, propyl, chloro, bromo, iodo, etc. There are only combinations of these, and Y is preferably hydrogen.

The hydrolytically stable copolymers used in the blends of the present invention also include carbonic acid precursors. Sars*XX*X and dihydric phenol polyester-substituted aryloxysilane Contains repeating copolymerized units of polydiorganosiloxane linked by elementary bonds , in which case the repeating copolymerized unit is the polydiorgano An average weight of 10 to about 75%, preferably about 40 to 70% by weight of the siloxane. contains. Copolymers of the type described above are described in US Pat. No. 3,189,662 (6) No. 1, which is incorporated herein by reference, is written on its own. or in combination with well-known modifiers to impart particularly desirable properties to the blend. can be done.

Polyetherimide has the formula (In the formula, Z is as described above) with any aromatic bis(ether acid anhydride) and formula %formula% (wherein R is the above-mentioned atom) with an organic diamine. It can be obtained by any known method.

The aromatic bis(ether acid anhydride) of the above formula includes, for example, 2゜2-bisC4-(2, 3-dicarboxyphenoxy)phenyl]propanedic anhydride; 4,4'-bis (2,3-')carboxyphenoxy)diphenyl ether diacid anhydride; 4゜3 -bis(2,3-dicarboxyphenoxy)benzenedic anhydride; 4,4'-bis(2,3-dicarboxyphenoxy)benzenedic anhydride; (-2,3-dicarboxyphenoxy)diphenyl sulfide diacid anhydride; 1.4-bis(2,3-dicarboxyphenoxy)benzenedic anhydride; 4.4 '-Bis(2,3-dicarboxyphenoxy)penzophenonediacid anhydride↓4, 4'-(2,3-dicarboxyphenoxy)diphenylsulfonedioic anhydride i 2,2-bisC4-(3,4-dicarboxyphenoxy)phenyl]propane Diacid anhydride; 4,4'-,bis(3,4-dicarboxyphenoxy)diphenyl Ether diacid anhydride: 4,4'-1:''(3,4-dicarboxyphenoxylene) c) Diphenyl sulfide diacid anhydride; 1,3-bis(3,4-dicarboxy phenoxy)benzenedic anhydride; 1,4-bis(3,4-dicarboxyphenol) xy)benzenedic anhydride: 4,4'-bis(3,4-dicarboxyphenoxy) ) Penzophenone diacid anhydride; 4-(2,3-dicarboxyphenoxy)-4' -(3,4-dicarboxyphenoxy)diphenyl-2゜2-propanedic anhydride and mixtures of such diacid anhydrides.

Furthermore, the aromatic bis(ether acid anhydride) included in the above formula includes codon, em, M: Florinskiy, F., Nis; Besonov, Ken Ai; Rudakov, Ni , Bee, (Institute of Heteroorganic Ivy Compounds, Aka Department of Science, Soviet Union) filed on May 3, 1967, 1969 It is shown in USSR Patent No. 2.57010 of November 11th. Also, diacid anhydride Zh, O, rg, Khin, 4 (51.

774 (196B) by M., M., Futon, F., Nis, Florinsky. is shown.

Examples of organic diamines of the above formula include m-phenylene diamine, p-phenylene diamine, and p-phenylene diamine. amine, 4;4'-diaminodiphenylpropane, 4;4'-diaminodiphenyl Methane, bench (8) gin, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphe Nilsulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminona Phthalne, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine , 2.4-bis(β-amino-butyl)toluene, bisCP-β-amino t-butylphenyl) ether, bis(p-β-methyl-〇-aminophenyl) 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(4-aminocyclo hexyl)methane, 3-methylhebutamethylenediamine, 4,4-dimethylhexyl Tamethylenediamine-2,11-dodecanediamine, 2゜2-dimethylpropylene diamine, octamethylene diamine, 3-methoxyhexamethylene diamine, 2.5-dimethylhexamethylenediamine, 2.5-dimethylhexamethylenediamine Amine, 3-methylhebutamethylenediamine, 5-methylnonamethylenediamine , 1,4-cyclohexanediamine, 1,12-octadecanediamine, bis( 3-aminopropyl) sulfide, N-methyl-bis(3-aminopropyl) Amine, hexamethylene diamine, heptamethylene diamine, nonamethylene diamine amine, dodecamethylenediamine, bis(3-aminopropyl)tetramethyldisiamine Includes loxane, bis(4-aminobutyl)tetramethyldisiloxane, etc.

(9) Generally, the reaction is carried out between a dianhydride and a diamine at a temperature of about 100 to about 250°C. well-known solvents, such as 0-dichlorobenzene, , m-cresol/toluene, etc. can be advantageously used.

Alternatively, polynye and thylimide can be mixed simultaneously and the mixture of each component heated at high temperature. Melt polymerization of the above arbitrary diacid and the above arbitrary diamine compound while heating. It can be made by Generally about 200-400°C, preferably 230-3 A melt polymerization temperature of 0.000C can be used. Chain terminators commonly used in melt polymerization You can use optional order. The reaction conditions and proportions of each component are based on the desired molecular weight and intrinsic viscosity. and can vary within a wide range depending on solvent resistance. High molecular weight polyester For the tellimide, equimolar amounts of diamino and dianhydride are generally used; However, in some cases a slight excess (approximately 1-5 mol%) of the diamine may be used. This can lead to the formation of polyetherimides with terminal amine groups. one Generally useful polyetherimides have a ．． greater than 2eit/y, preferably from 0.35 to 060 or 0.7 d7! /　 It has an intrinsic viscosity [η] of y or more.

Among the many producing polyetherimides is Heath et al., U.S. Pat. No. 67, Williams No. 3847869, Takekoshi et al. No. 3850885 , White Nos. 3,852,242 and 3,855,178. Contains -0 These statements are suitable for the blends of the invention (10) Teach by example general and special methods for making polyetherimides Therefore, it is fully quoted and incorporated herein.

A block copolymer of organopolysiloxane and polycarbonate has the formula (wherein Hal is a halogen group, preferably chlorine) A mixture of polydiorganosiloxane and dihydric phenol having the formula The reaction is carried out at a temperature in the range of 0°C to 100°C, preferably 20°C to 50°C, in the presence of and then the reaction product is heated until the copolymer formed achieves its highest intrinsic viscosity. It can be made by turning it into a sugen.

Halogen chain-terminated polydiorganosiloxanes are disclosed in Hunt Nord's U.S. Pat. 81366 and Hyde US Pat. Nos. 2,696,726 and 290,250 As taught in No. 7, diorganodihalosilanes such as dimethyldichlorosilane It can be made by conventional methods such as by controlled hydrolysis of orchids.

Another method that can be used is shown in Salael U.S. Pat. No. 2,421,653. Diorganodichlorosilane and cyclic polysilane in the presence of a metal catalyst such as ferric chloride. Equilibrating the mixture of diorganosiloxanes. /-Logen chain stop point Although there are no strict regulations regarding the various methods used to form resiloxanes, Generally, from about 0.4 to about 35% by weight of the halogen chain-terminated polysiloxane, preferably /10-gen chain-terminating polysiloxane, preferably formed in the range of about 1 to about 10% by weight. It has been found desirable to maintain the halogen content of the sun. Halogen chain stop Preferably, the stop polysiloxane is in the form of a chlorinated polydimethylsiloxane.

The dihydric phenol included in the above formula includes, for example, 2,2-bis(4-hydroxyphene). Nirure), -propane (bis-phenol A), 2,4'-dihydroxydife Nylmethane; bis-(2-hydroxyphenyl)-methane; bis=(4-hydro xyphenyl)-methane; 1.1-bis(4-hydroxyphenyl)-ethane; f, 2-bis-(4-hydroxyphenyl)-ethane; 1,1-bis-(4-hydroxyphenyl)-ethane; Droxy-2-chlorophenol)-ethane; 1,1-bis-(2,5-dimethyl -4-hydroxyphenyl)-ethane; 1,3-bis-(3-methyl-4-hydro) (roxyphenyl)-propane; 2,2-bis-.(3-isopropyl-4-hydro) (roxyphenyl)-propane, etc. Mixtures can also be used. Others are recommended to those skilled in the art. It will come.

According to the invention, a block copolymer of organopolysiloxane and polycarbonate and polyetherimide blur (12) The polymers are generally obtained in all proportions of the two polymers with respect to each other.

Thus, from about 1 to about 99% by weight of polyetherimide, and about 99% by weight of block copolymer. Blends consisting of ~1% by weight are included within the scope of this invention. polyetherimide By controlling the mutual ratio of block copolymer and block copolymer, polyetherimide The block copolymer has certain predetermined properties that are improved over that of the block or block copolymer alone. Blends with Generally polyetherimide and block Blends of polymers improve the impact strength of the blend while improving the impact strength of the blend. A small proportion of block copolymer to maintain the high strength properties of the etherimide component , for example, from about 1.0 to about 50% by weight.

The polyetherimide-block copolymer blends of the present invention may also be filled in conventional amounts. agents, stabilizers, plasticizers, softeners, surfactants, pigments, dyes, reinforcing agents, flame retardants and It is contemplated that other additives such as diluents may also be included. The blend of the present invention is one type The above block copolymers and two or more polyetherimides, or one or more polyetherimides, Also intended to include two or more block copolymers in combination with riethelimides do.

Methods for forming polyetherimide-block copolymer blends vary considerably. Ru. The prior art mixing method generally satisfies one condition. The preferred method is to use powders, particles or mixes additives and polymers such as reinforcing agents in the form of filaments and presses the blend. The usually solid thermoplastic composition (13) is prepared by extruding and cutting the extrudate. Pellets suitable for forming by means conventionally used for forming objects. It consists of making a cut.

The blends of the invention can be used in a wide range of applications, including use as films, molding compounds, coatings, etc. It has uses in the physical form of the surroundings.

When using it as a filler or making it into a molded product, the laminate made from it can be These blends not only have good physical properties at room temperature, but also They have excellent response to long-term high temperature work loads and retain their strength. hold Films formed from the blends of the present invention are similar to those conventionally used in films. It can be used for various purposes. For example, the blends of the invention can be used for decorative and protective purposes. for automobiles and aircraft, and for terrestrial slot liners, transformers, and dielectric keys. Capacitors, cables and coil packaging (shaped coil insulation for motors) high temperature electrical insulation for containers and container linings can be used for. Blend asbestos blend film or solution , mica, glass fiber, etc., or other types of materials, and The sheets are stacked on top of each other and the sheets are then subjected to high temperature and pressure to bind the resin binder. It can also be used in laminated structures if it is flowed and cured to form a cohesive laminated structure. Main departure Films made from bright blends can also be used for printed circuit applications.

Alternatively, solutions of the blends shown here can be used on conductive materials such as copper, aluminum, etc. The coated conductor is then heated to a high temperature to remove the solvent, and then the resin assembly is applied. Curing of the composition can be carried out. If desired, on such insulated conductors Polyamide, polyester, silicone, polyvinyl formal resin, epoxy Using polymer coatings such as resin, polyimide, polytetrafluoroethylene, etc. An overcoat may also be applied. Overcoat over other types of insulation This does not preclude the use of the blends according to the invention as a starter.

Other intended uses for these blends include in making brake linings; Use as a binder for asbestos fibers, carbon fibers, and other fiber materials including the route.

In addition, asbestos, glass fiber, talc, quartz, powder, and fine powder are blended before molding. molded from the polymer blends of the present invention with fillers such as carbon fibers and silica. Compositions and molded articles can be formed. Molded articles are well known to those skilled in the art. It can be molded under heat or under heat and pressure.

The following examples illustrate polyetherimides and organopolysiloxanes according to the invention. A special blend of polycarbonate block copolymers is shown. Examples are illustrative. This is provided for the purpose of illustration only, and is not intended to limit the invention. In an example, Parts and percentages are by weight unless otherwise specified.

Example ■ Polyetherimide and organopolysiloxane and polycarbonate according to the invention Make a blend of block copolymers of Tested for various physical properties (15) code table Sho GO-5010 (17 (,6) did.

The blended polyetherimide is heated at high temperatures of about 250 to about 300°C under a nitrogen atmosphere. essentially equimolar amounts of 2,2-bis[4-(3,4-dicarboxyphenol) prepared c) Reaction product of phenyl]propanedic acid anhydride and l1l-phenylenediamine Preformed from a composition. The polymer is extruded at approximately 300°C to form strands. , mechanically cut and pelletized.

The block copolymer of organopolysiloxane and polycarbonate used was It is marketed by Neral Electric Company under the trade name LR Resin. It was a copolymer.

About 90 parts of the above polyetherimide was mixed with about 10 parts of the block copolymer. two have a die of polymer blend at about 590°F and vary from about 570 to 610°F. Extruded in a Warner & Pfeidler extruder with a temperature profile of . The formed extrudate is cut into pellets and the pellets are placed in a battery at a temperature below about 610°C. The specimens were injection molded on a field molding machine. The impact strength of these test pieces was Measured by unnotched and notched Izot impact tests and Gardner impact tests. The results are shown in the table below. The flexural properties of the blends were also measured and shown in the table.

Example ■ To make a blend according to the invention, about 70 parts of polyetherimide is mixed with about 30 parts of copolymer. The method of Example I was repeated except that the blend was mixed with . Blend (18) From the above test results, it can be seen that the blend according to the invention is particularly effective relative to polyetherimide. High proportions of organopolysiloxane and polycarbonate provide a good combination of strength and bending properties. Relatively high concentrations of bonate block copolymers exhibit good bending properties.

In particular, blends containing about 90% polyetherimide (example blends) has a relatively high impact strength compared to the impact strength normally possessed by the polyetherimide component alone. Has a zigzag impact strength.

shown in this specification to obtain blends with similar properties to those shown in the examples. Many other polyetherimides and block copolymers can be used, such as.

Although the invention has been described with reference to particular examples thereof, as defined in the claims. It is understood that many modifications can be made by those skilled in the art without actually departing from the scope of the Probably.

Claims (1)

[Claims] 1. (a) polyetherimide and (b) organopolysiloxane-polycar A composition comprising a blend proportion of a bonate copolymer. 2. Polyetherimide is the formula [In the formula, a represents an integer greater than 1, and the group -0-A〈CR' is hydrogen, lower alkali is a kill group or a lower alkoxy group], and 2 is (1) and (2) general formula (20) One member selected from the group consisting of valence groups, q is 0 or 1, and y is 1 to 5. R is one member selected from the group consisting of two organic groups (an integer), and R is (1) carbon Aromatic hydrocarbon group having 6 to 2 atoms and halogenated derivative thereof, (2) Alkylene groups and cycloalkylene groups having 2 to 20 carbon atoms, ra~C8 Argylene end-stopped polydiorganosiloxane, and formula (3) one member selected from the group consisting of (2 organic groups selected from the group consisting of valent groups) according to claim 1. Composition of. 3 Polyetherimide is the formula (21) is a polyetherimide, and the divalent group of -　=　2-0- is 3, 3'; 3 , 4' i 4, 3' or 4.4' position' according to claim 2 Composition. H3 and R is A composition according to claim 3 selected from. 5 Polyetherimide is the formula 5. The composition according to claim 4, which is a polyetherimide. 6. Structural formula of organopolysiloxane-polycarbonate copolymer (where n is at least 1, preferably n is an integer equal to 1 to about 1000) Preferably, b is equal to 1 to about 200, C is equal to about 5 to about 200, and the ratio of b to C is can vary from about 005 to about 3, d is 1 or more, and U is an integer from 1 to 4. , T is hydrogen or a member selected from 10-0R3, R1 is hydrogen, monovalent carbide one member selected from the group of hydrogen groups and halogenated monovalent hydrocarbon groups, and R2 is 1 A group consisting of a valent hydrocarbon group, a halogenated monovalent hydrocarbon group, and a cyanoalkyl group The horse is a member selected from monovalent hydrocarbon groups and halogenated hydrocarbon groups. Y is one member selected from the group consisting of hydrogen, lower alkyl group, halogen group and and mixtures thereof) The composition according to item 1, 2, 3, 4 or 5. 7, R1 is hydrogen, aryl group, halogenated aryl group, aralkyl group, aliphatic, selected from haloaliphatic and alicyclic groups, R2 is an aryl group, a halogenated aryl groups, aralkyl groups, aliphatic, haloaliphatic, cycloaliphatic groups and cyanoalkyl groups. Y is hydrogen, methyl group, ethyl group, propyl group, chlorine, bromine, iodine and and combinations thereof. (23) 8, R1 is hydrogen, phenyl group, chloroethyl group, xylyl group, tolyl group, phenyl group, Nylethyl group, benzyl group, methyl group, ethyl group, propyl group, chlorobutyl group and cyclohexyl group color selection L, R, is phenyl group, chlorophenyl group, Silyl group, tolyl group, phenylethyl group, benzyl group, methyl group, ethyl group, Lopyl group, chlorobutyl group, cyclohexyl group, cyanoethyl group and cyanobu 8. A composition according to claim 7, wherein the composition is selected from chill groups. (1)