JPH05508683A - Molded articles containing polybenzazole 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] 11. The thermoplastic polymer block is composed of thermoplastic polyamide, poly(aromatic ether) ) or a copolymer of poly(aromatic ether) and polybenzazole, The invention as claimed in claim IO.

Specification A molded article containing a copolymer of polybenzazole ( PBZ) polymers and polymer compositions containing blocks of this polymer. do.

PBZ polymers, i.e. polybenzoxazole, polybenzothiazole and and polybenzimidazole, and their synthesis is described in detail in the following patents: ing. Wolfe et al., Liquid Crystalline Polymer Compositions, Processes and Products, U.S. Patent No. 4.703.103 (October 27, 1987): Wolfe et al., Liquid Crystalline Polymer Composite ions, Process and Products, U.S. Patent No. 4.53 No. 3.692 (August 6, 1985) HWolfe et al., LiquidCrys talline Po1y (2,6-Benzothiazole) Comp positions, Process and Products, U.S. Patent No. 4 ．． No. 533.724 (August 6, 1985); Wolfe, Liquid Crystalline Polymer Compositions, Pr cess and Products, U.S. Patent No. 4.533.693 (19 August 6, 1985); Evers, Thermooxidatively 5t able Articulated p-Benzobisoxazole a nd p-Benzobisthiazole Polymers, US Patent No. No. 4.359.567 (November 16, 1982), Tsai et al., Metho d of Making Heterocyclic BlockCopoly mer, U.S. Pat. No. 4,578,432 (March 1986, 258) and Enc. y.

Poly, Sci, & Eng, Polybenzothiazole s and Polybenzoxazoles.

601 (J, Wiley & 5ons 1988).

Polybenzazole polymers, and in particular “hard rod JPBZ polymers, Characterized by high tensile strength, high tensile modulus and high thermal stability. But many Polybenzazole polymers are difficult to process into viable products. hard and semi-hard The quality polybenzazole has a glass transition temperature of 1JEe at the temperature at which it is stable. It's sad. This polymer is usually spun from solution to form fibers, which are Cannot be blown or thermoformed.

It does not have the high tensile strength and modulus characteristic of azole polymers.

No. 4.810.735 and Hwang et al. ssing and Properties of Mo1ecular Com posite Fibers and Films” 23 Polymer E ng, & Sci, 784 (1983): Hwang et al., “Phas eRelationships, Processing and Prope rties’ B22 J, Macromol.

molded products have inferior properties in all directions than the corresponding thermoplastic resin alone, and has excellent properties in one direction and poor properties in the other direction. That's it Such compositions are effective for fibers, but not for molded articles.

strong properties with excellent properties in at least two directions and/or with virtually no phase separation; Materials that can be used to manufacture molded products containing a quantity of polybenzazole polymer Additional fees and methods are needed.

One embodiment of the present invention provides (a) a rigid rod or semi-rigid rod polybenzazole Pro Tsukukopo grows polymer blocks and (b) thermoplastic polymer blocks. reamer, wherein (1) each polybenzazole polymer block has an average of at least (2) also contains 5 monomer units and less than 10 monomer units; The copolymer is thermoplastic and can be compression molded with virtually no phase separation. It is a block copolymer characterized by:

A second aspect of the invention includes (1) an average of at least 5 monomer units per block; Rigid rod or semi-rigid rod polybenzazole polymer block containing and (2) such that the block copolymer is fluid at temperatures below its decomposition temperature. A block copolymer with thermoplastic polymer blocks of suitable size and ratio. solid particles in which the block copolymer has an average particle diameter of 1000 μm or less It is a block copolymer characterized by its child-like shape.

A third aspect of the invention is a briquette comprising the granular composition of the invention.

A fourth aspect of the invention provides a temperature at which the particulate composition is flowable and a temperature at which the particulate composition is compressed. the process of forming a solid particulate composition in a mold under sufficient pressure to conform to the shape of the mold A method for forming a molded article comprising: (1) a granular composition having (a) a flat surface per block; Polybenzazole polymer blocks containing uniformly at least 5 monomer units and and (b) suitable materials such that the block copolymer is fluid at temperatures below its decomposition temperature. A non-phase separated block copolymer that grows thermoplastic polymer blocks of specific sizes and ratios. (2) the particulate composition has an average particle diameter of 1000 μm or less; This method is characterized by:

A fifth aspect of the present invention is a molded article produced by the method of the present invention.

The granular composition and/or briquettes of the present invention can be used for processing the molded articles of the present invention. May be used in the method of the invention. Such moldings can be used as structural elements, such as circuit boards. or other purposes for which molded plastic products are useful.

The following terms used repeatedly in this specification have the meanings indicated below, unless otherwise specified. It has a taste and a preferred aspect.

AA-BB-polybenzazole (AA/B B-P BZ) - first aroma a group group (Ar'), a first and second azole ring condensed with the first aromatic group, and a valent organic moiety ( A polybenzazole polymer characterized by monomer units having DM). two The organic moiety (DM) should not interfere with the synthesis, processing, or use of the PBZ polymer. This is preferably the second aromatic group (Ar”). In some cases, it may be an alkyl group or a bond. The monomer unit is preferably is the first azo in the adjacent monomer unit due to the bond from the divalent organic group (DM). bonded to the 2-carbon of the ring. Monomers suitable for AA/BB-PBZ polymers The unit is preferably below (in the above formula, Z is the same as defined for the azole ring) and all others have the meaning given above) It is expressed as

AB-polybenzazole (AB-PBZ) - a first aromatic group and the first aromatic group A polyester characterized by a monomer unit having one azole ring fused with an aromatic group. benzazole polymer. This unit is an azole within one monomer unit. Bonded to the aromatic group of the adjacent monomer unit by a bond from the 2-carbon of the ring . Monomer units suitable for AB-PBZ polymers preferably have the following formula 2 (in the above formula , Z are as defined for the azole ring, and all others have the above meanings. ) It is expressed as

substance or ester. The acid group is preferably an acid or an acid nolide, more preferably an acid group. Preferred is carboxylic acid or chlorinated carboxylic acid.

0-amino basic moiety-bonded to an aromatic group; a amine group and (2) a hydro bonded to an aromatic group at the ortho position to the -class amine group. moieties consisting of xy, thiol or -class or secondary amine groups. This is preferably Contains hydroxy, thiol or some amine moieties, more preferably hydroxy or thiol moieties, most preferably hydroxy moieties. Second class a Min groups include aromatic or aliphatic groups, preferably alkyl groups. secondary amine The group preferably has no more than about 6 carbon atoms, more preferably no more than about 4 carbon atoms, and most preferably no more than about 4 carbon atoms. Contains about 1 or less.

Aromatic group (Ar) - any aromatic ring or ring system. Aromatic groups are mixed with The size does not matter unless it is so thick that it interferes with the reaction of the Preferably about 18 or less, more preferably about 12 or less, most preferably about 6 Contains the following carbon atoms: Each may be a heterocyclic ring, but preferably a carbocyclic ring. more preferably hydrocarbyl. When the aromatic group is a heterocycle, The atom is preferably nitrogen.

Unless otherwise indicated, each aromatic group represents one aromatic ring, a fused ring system, or a single aromatic group under the polymerization conditions. attached by a divalent moiety or by a bond that is inert with respect to the PBZ polymerization reagent in unfused ring systems containing two or more aromatic rings. Suitable divalent moieties include, for example, cal Bonyl group, sulfonyl group, oxygen atom, sulfur atom, alkyl group and/or perfluor Contains olorated alkyl groups. Each aromatic group is preferably one 6-membered ring.

Each aromatic group is stable in solvent acids and subsequent reactions of the moieties of which the aromatic group is a part may contain substituents that do not interfere with and do not undergo undesirable side reactions. good Examples of preferred substituents include halogen, alkoxy moieties or alkyl groups. better Preferred substituents are alkyl groups having up to about 6 carbon atoms or halogen.

Most preferably, each aromatic group contains only the substituents required below.

Decoupling group (D) - acid group or aromatic group with a deactivating group, e.g. An acid that binds to a bonyl or sulfonyl group and participates in an electrophilic aromatic substitution reaction. A divalent moiety that protects an acid group or an aromatic group from deactivation. decup Ring groups typically include, for example, ether groups, thio groups, aliphatic groups and/or aromatic groups. Contains groups.

The decoupling group is typically an electron withdrawing group, such as carbonyl or sulfonyl. Contains no groups. The decoupling group is preferably one bonded by an ether group. Contains the above aromatic groups.

The minimum decoupling required depends on the group being protected and the reaction conditions. . Reactions carried out in dehydrated protonic acid solutions are similar to reactions carried out in the presence of Lewis acids. also requires a lot of decoupling. Aromatic groups undergoing reactions are more numerous than acid groups. requires a lot of decoupling. For example, in the presence of a Lewis acid, the acid group Decoupled by a unilene ring, the aromatic group is connected to one ether or thio Decoupled by ether group. In a dehydrated protonic acid solution, two acids The decoupling group linking groups preferably contains at least two aromatic groups; This is more preferably linked by an ether group, which connects two aromatic groups. The decoupling group preferably includes at least an aromatic group and a first ether group. more preferably also a second ether group.

Decoupling and suitable decoupling groups include Co1quhoun “5yn thesis of PoLyether Ketones in Trifl uoromethane 5ulfonic Acid” 25 (2) Pol ymer Preprints 17-18 & Table [1 (1984 ) and Co1quhoun et al., “5 synthesis of Aromati c Po1yether Ketones in Trifluorometha ne 5ulfonic Ac1d' 29 Polymer 1902 (1 988).

Electron-deficient carbon groups (Q) - e.g. column 24 of U.S. Pat. No. 4,533,693. In a solvent acid, such as the groups shown in lines 59-66. -Amino basic moiety and anti- Any group containing a carbon atom forming an azole ring and orthoester, metal Carboxylate salts, cyano groups and trihalomethyl groups. Preferred electron-deficient carbon group are carboxylic acids and acid halides. Halogens in electron-deficient carbon groups are preferred. or chlorine, bromine or iodine, more preferably chlorine.

! Obon! - the presence in the solidified product of optionally independent anisotropic domains of the polymer; . In the molded article of the present invention, phase separation at the molecular level is unavoidable, and this product exhibits semi-crystalline properties. However, the phase-separated particles in the polymer composition of the present invention The domain size of the reamer is preferably less than an average of too angstroms. more preferably 500 angstroms or less, more preferably 200 angstroms 100 angstroms or less, even more preferably 100 angstroms or less, most preferably Preferably, it is 50 angstroms or less. Phase separation has known properties, e.g. opacity Determined by high-temperature, electron microscopy, small-angle X#i scattering, or small-angle light scattering. within the system The method for measuring phase separation is described in “Composites on a 　Mo1ecular　Level:　Phase　Re1ationship s.

Processing, and Properties” B22 J, M acromol, Sci, -Phys, 231°234-35 (1983 )It is described in.

Polybenzazole (PBZ) Polymer - Polybenzoxazole and Polyben Zobisoxazole (PBO), polybenzothiazole and polybenzobisthiazole sol (PBT) and polybenzimidazole or polybenzobisimidazole Polymers from the group of (FBI). “What is polybenzoxazole (PBO) J? Each monomer unit is attached to an aromatic group (this need not be a benzene ring). means a polymer containing an oxazole ring. Also, “polybenzoxazole ( PBO) J is poly(phenylene-benzo-bis-oxazole) and each monomer refers to other polymers whose units contain many oxazole rings fused to aromatic groups do. The same interpretation applies to polybenzothiazole (PBT) and polybenzimidazole. (FBI). The polybenzazole polymer used in the present invention is Preferably polybenzoxazole or polybenzothiazole, more preferably It is polybenzoxazole.

Hard Rod PBZ Polymer - Hwang's +Processing, 5tru tureand Properties of Liquid Crysta lline PBT Polymer’ Kansai Committee o f the 5ociety of Fiber 5science and T technology.

Japan, Po5t Symposium on Formation, 5t structure and Properties of High Module s and High Tenacity Fibers 23-26 (19 August 26, 1985) HEvers et al., “Articulated A11-Pa ra Polymers with 2.6-Benzeobisoxazol e, 2.6-Benzobisthiazole, and 2.6-Ben zobisimidazole Units in the Backbone ”14 Macromolecules925 (1981): Evers “Thermoxidatively 5table Articulate” dBenzobisoxazole and Benzobisthiazol e Polymers” 24 J, Poly.

Sci, Part A 1863 (1986) and Evers et al., Art iculated Para-Ordered Aromatic Heter ocyclic Polymers ContajningDiphenoxy benzene 5 structures, U.S. Patent No. 4.229.566 (1 October 21, 980) and “articulated” “internal” or “articulated” rigid rods such as J. PBZ polymer.

The internal rigid rod polymer is essentially straight with a permanent length comparable to its contour length It has a certain quality. It has essentially no angle of chain less than 150°. Segmental rigid lo Polymers are not straight lines but have a small number of parts with chain angles of less than 150°. Contains many more connected essentially straight sections. Hard rod P used in the present invention The BZ polymer is preferably an internal rigid rod polymer.

The acylation or step forming the block copolymer used in the present invention can be A non-oxidizing liquid acid suitable for carrying out sulfonation reactions or azole ring formation. This is dissolved It must not substantially oxidize the AB- and BB-PBZ monomers do not have. The solvent acid is preferably polyphosphoric acid or methanesulfonic acid and phosphorus pentoxide and/or or a dehydrating acid such as a mixture of polyphosphoric acids. Optimal PJ-content of polyphosphoric acid varies depending on the processing stage. Polyphosphoric acid used in the production of polybenzazole is initially preferably at least about 80 weight percent, more preferably at least It also contains about 85 weight percent P2os. The optimal P2O5 content is Somewhat low. for phosphorus pentoxide in a mixture of methanesulfonic acid and phosphorus pentoxide The weight ratio of methanesulfonic acid is preferably 20:1 or less at the beginning of the reaction, such as The ratio is preferably 5:1 or less. However, certain solvent acids, e.g. trifluorometa Although sulfonic acid does not contain dehydrating components like phosphorus pentoxide, Suitable for carrying out toacylation or sulfonation reactions.

The present invention provides a rigid rod or a block of semi-rigid benzazole polymer and a thermal Thermoplastic block copolymers containing blocks of plastic polymers are used. certain good Suitable block copolymers and methods for their preparation are described in Harris et al. ers Containing Polybenzoxazole.

Polybenzothiazole and Polybenzimidaz ole Mo1eties, International Application No. PCT/US89104464 (19 Filed on October 6, 1989), International Publication No. WO90103995 (April 1990) Published on March 19th and Harris et al.'s Thermop les tic Comp positions Containing Polybenzoxazole, Polybenzothiazoleand Polybenzimidaz ole Mo1ties and Process for MakingS haped Articles from Them, EPO application 90104 963.5 (March 16, 1990 mN), EPO Publication 03198803C19 It is described in detail in the September 26, 1990 Publication M).

or a semi-rigid polybenzazole block, most preferably a rigid rod block. be. Rigid and semi-rigid polybenzazole homopolymers are typically thermoplastic rather, they typically form liquid crystal solutions when dissolved in a solvent at relatively high concentrations. hard monomer units suitable for the production of rigid and semi-rigid polybenzazole monomer units. Kits are known in the art.

Rigid or semi-rigid polybenzazole blocks can also be AB-PBZ monomer units or AA/BB-PBZ monomer units or both. This is preferable or AA/BB-PBZ monomer units, more preferably essentially AA/BB - Contains PBZ monomer units. Semi-rigid AB-PBZ monomer unit odor Therefore, the directional group (Ar) preferably has (1) a single bond bonded to the 1-position and a bond bonded to the 3- and 4-positions. trivalent benzene having an azole ring fused to, or (2) a single bond to the 4-position and a 3 It is either a trivalent biphenyl group having an azole ring fused at the ゛ or 4゛ position. . In the hard AA/BB-PBZ monomer unit, the first aromatic group (Ar' ) is preferably a trivalent base having an azole ring fused at the 1,2- and 4,5-positions. It is a zene or naphthalene ring.

The divalent organic moiety (DM) is preferably a 1,4-phenylene moiety, a 4,4°-biphenylene moiety, It is a nylene moiety or a 2,5-biphenylene moiety. Rigid or semi-rigid polybenzo Azole blocks consist of non-rigid monomer units to form “segmented” semi-rigid structures. Contains a few. Rigid or semi-rigid polybenzazole blocks are polybenzoxa sol, polybenzothiazole, and/or polybenzimidazole monomer (Z = -O-, -S- or -NR-, respectively). this is preferable is essentially polybenzoxazole and/or polybenzothiazole monomer. It consists of knit (Z=-0- or -5-). This is more preferably poly It consists of a benzoxazole monomer unit (Z=-0-).

Most preferred monomer units for rigid or semi-rigid polybenzazole blocks An example of this is shown below.

Each rigid or semi-rigid polybenzazole block has an average of at least 5, preferably contains at least 8 monomer units. Each rigid or semi-rigid block is preferred or an average of 150 or less, more preferably 100 or less, most preferably 50 Contains the following monomer units.

Theoretically, larger units such as an average of at least 10 to 20 monomer units A block copolymer having a rigid or semi-rigid polybenzazole block is Polymers with smaller average rod lengths such as 5 to 10 monomer units It should have higher tensile strength and modulus than the polymer. However, smaller ports Block copolymers containing ribenzazole segments are often more fluid , and it is easier to obtain complete agglomeration under molding conditions. Therefore, specific made of a block copolymer with a small average rod length under the molding conditions of Shaped products have better physical properties.

thermoplastic block Thermoplastic blocks include polymers that are stable in solvent acids. This polymer is In a solvent acid solution containing polybenzazole blocks.

or by polymerization in another medium followed by reaction of the end groups in a solvent acid. It must be possible to bind to the polybenzazole block by binding the lock. No. The thermoplastic block is made of thermoplastic polybenzazole polymer or Thermoplastic acid-soluble polymers that are not benzazole or polybenzazole polymers remer monomer units and thermoplastic acid-soluble polymers that are not polybenzazoles. Contains random or sequential copolymers containing both remer monomer units .

The thermoplastic block preferably has an average formula weight of at least about 800. Its weight The degree of density is preferably at least about 1O1, more preferably at least about 20.

(A) Thermoplastic polybenzazole Thermoplastic polybenzazole polymers are known and described by Harris et al. moplastie Compositions Containing Po 1ybenzoxazole, Po1ybenzothiazole and Polybenzimidazole Molties and Processes s for Making 5haped Articles from Th em, EPO Application No. 90104963, 5 (filed March 16, 1990), EP O publication 0388803 (released September 26, 1990) and U, Buhl er's 5 pezialplaste 838-866 (Akademie-Ve rlag 1978). It is neither hard nor semi-hard; Typically does not form a liquid crystal solution. It consists of two groups, aliphatic polybenzazoles and combined polybenzazoles.

The bound polybenzazole preferably has the following formula (wherein X is a bond or a first is a divalent bond moiety, each Ar'' is an aromatic group, L is a non-linear group that is stable under the conditions under which the polymer is synthesized, processed and used. the law of nature, Other symbols have the meanings given above) It is expressed as

Each non-linear group (L) is (a) Metaaromatic group (Ar”), e.g. m-phenylene moiety, m-biphenylene moiety, 3.4′-biphenylene moiety, 3.3′-biphenylene moiety or 2.6- naphthalene part, (b) an aliphatic moiety, or (C) Contains two aromatic groups bonded by a second divalent bond moiety (X'). aroma The group group has the meaning and preferred embodiments given above for aromatic groups.

The -th and 20th divalent bond moieties (X and X') are synthesized by polymers, yellow atoms, or is an aliphatic group. Each is more preferably a sulfonyl moiety or an oxygen moiety.

Most preferably, the first divalent binding moiety (X) is a sulfonyl moiety; The valence bond moiety (X') is an oxygen atom. One or both of the divalent bond moieties is an aromatic group Two oxygen atoms, a sulfur atom, and a sulfonyl moiety bonded by an aliphatic moiety It is also within the scope of the present invention to include.

The non-linear group (L) or the first or second divalent bond moiety (X or X') is an aliphatic group , the aliphatic group preferably contains up to about 12 carbon atoms. The aliphatic group is It may be cyclic or branched. It is preferably an alkyl or halogenated alkyl It is le. Examples of suitable aliphatic groups are 1,2-cyclohexyl moieties and perfluorinated moieties. Contains a leuisopropylidene moiety. The high gas content of the bonded polybenzazole polymer Because of the lath transition temperature, aliphatic moieties within the bound polybenzazole polymer are Preferably, it is perfluorinated to provide temperature stability, e.g. It is ropylidene.

The monomer units in the bound polybenzazole preferably have the following formula (al 5(a) or the sulfonyl group is meta to the Z group and heterogeneous to the nitrogen atom. is its variant.

Aliphatic polybenzazoles contain aliphatic bonds within the polymer backbone.

The polymer may be an AB-PBZ polymer, but preferably AA/BB-PB It is a Z polymer. The monomer units in the aliphatic polybenzazole polymer are Preferably, the following formulas 6(a) and (b) (in the above formula, Ar is the above-mentioned aromatic group, and R 1 is an aliphatic group containing at least about 3 carbon atoms; the other symbols have the meanings given above. ) 01.

The size of the aliphatic group (R) does not matter. The aliphatic group preferably has no more than about 12 carbon atoms, more preferably no more than about 10, most preferably no more than about 8 carbon atoms. Contains elementary atoms. It may be cyclic or branched, but is preferably linear. . This means that block copolymers are not stable under the conditions under which they are synthesized, processed, and used. Must be.

Aliphatic groups may be fluorinated for good thermal stability. Aliphatic groups are preferred is alkyl or perfluoroalkyl. Linking aliphatic groups to the polymer backbone The bonds that do are preferably not to the same carbon atom or to adjacent carbon atoms.

The aliphatic AB-PBZ polymer broth is described in “TWO- Step 5 synthesis of Alkyl-and Alkenyl- benzoxazole Polymers”18 Macromolecule (1) Triphenylphosph as described in ES 616 (1985) Corresponding amide forms in the system of amine, hexachloroethane and pyridine (2) by thermal cyclization of the amide. fat Group AA/BB-PBZ polymer blocks are described in U.S. Pat. No. 4.533.693. AA- containing an aliphatic group attached to two electron deficient carbon groups as described known methods, such as by reacting PBZ monomers with BB-PBZ monomers. Synthesized by method.

Block copolymers are synthesized by known methods. Rigid and semi-rigid blocks and The thermoplastic blocks are then reacted to combine the blocks into block copolymers. Separately synthesized depending on the terminal group. Alternatively, one set of blocks can be formed in the reaction mixture. monomers for the second block copolymer are added to the mixture and the reaction continues. A block copolymer may also be formed.

(B) Thermoplastic non-polybenzazole polymers and copolymers and other suitable thermoplastics. Polymers include polyamide, thermoplastic polyimide, polyquinoxaline, polyquino phosphorus, poly(aromatic ether ketone) and/or poly(aromatic ether sulfone) ), or co-existence of these polymers with each other and/or with polybenzazole. Contains polymers. More preferred polymers are polyamide, poly(aromatically modified) ketones) or poly(aromatic ether sulfones) or each other and/or polybases. It is a copolymer with nzazole. A suitable thermoplastic block is International Publication No. , Wo 90103995 (published on April 9, 1990), pages 73-102. It is listed.

The polyamide polymer used in the present invention usually has the following formula (in the above formula, AI and A 2 is a polyamide block that does not interfere with the synthesis, processing or use of block copolymers. is a divalent organic moiety selected such that the lock is thermoplastic) It is represented by one of the following. Each divalent organic moiety (A' and A'') contains an aromatic group. However, preferably at least one is an aliphatic group.

The aliphatic divalent organic moiety preferably has no more than about 12 carbon atoms, more preferably no more than about 6 carbon atoms. Contains elementary atoms. The aliphatic divalent organic moiety is preferably saturated, more preferably aliphatic. It's Lukiru. Most preferably, the first divalent organic moiety (A1) is aromatic; The second divalent organic moiety (80 is aliphatic).

Poly(aromatic ketone) and poly(aromatic sulfone) preferably have the following formula 8(a) or Ha (bl 8(a) ÷Ar'-D-Ar-r+b8(b)+Ar-D-Ar-Y-τ- Y+b (in the above formula, each Ar is independently an aromatic group, and each independently represents the above decoupling group. is a ring group, each Y is independently a sulfonyl or carbonyl group, and T is a divalent group. It is the machine part, b is the number of repeating monomer units greater than 1) . Poly(aromatic ketone or sulfone) is more preferably represented by the following formula 8(C) or (d1 8 (c) ++Ar-J) n-Ar-Y+b8 (d) ++Ar-j +n-Ar-Y-T-y+b (in the above formula, n is the number of repeating units of 1 or more each J is independently an oxygen atom, a sulfur atom, or at least one J is oxygen or sulfur. The bond chosen to be a yellow atom) is represented by 01. Each J is more preferable is an oxygen atom or a bond in which at least one J is an oxygen atom . . Each n is more preferably at least 2.

Each divalent organic moiety (T) is dissolved in a solvent acid, preferably up to at least about 50'C, and up to Preferably up to at least about 100'C, most preferably at least about 200'C must be stable until More preferably each divalent organic moiety (T) is essentially It consists of an aromatic group or multiple aromatic groups bonded to a sulfur or oxygen atom. aromatic The group is most preferably a meta or paraphenylene group.

Copolymers of polyamide or poly(aromatic ether) and polybenzazole - is structurally equivalent to a homopolymer, but with at least one divalent moiety (A' , A'', Ar or T) is benzazole or benzo-bisazole It is substituted with two aromatic groups connected by a sol moiety. like that The copolymer is preferably a polybenzazole-poly(aromatic ether) copolymer. - is. Examples of copolymers include Aromatic Polyet of Dah et al. her KetonesHavingrmide, Am1de, Este r, Azo, Quinoxaline, Benzimidazole.

Benzoxazole or Benzothiazole Groups and a Method of Preparation, International (PCT) application WO36102368 (published April 24, 1986), and C of Harris et al. Opolymers Containing Polybenzoxazole .

Polybenzothiazole and Polybenzimidaz ole Mo1eties, International Application PCT/US89104464 (1989 International Publication W090103995 (Published on April 19, 1990) (open).

This copolymer is preferably of the formula It is expressed as This is more preferably expressed by the following formula 9(b) It is expressed as This is most preferably expressed by the following formula. The symbol for each of these formulas is Cultivate the same meaning as above.

Thermoplastic blocks are synthesized by methods common to the particular type of polymer chosen. be done. The thermoplastic polymer block includes (i) 0- to form an azole ring; by reaction of an amino basic moiety with an electron-deficient carbon group, or (ii) by bonding to an aromatic group. Fusing an aromatic group with an acid group to form a combined carbonyl or sulfonyl group The Riedel-Crafts reaction binds to rigid or semi-rigid polybenzazole blocks. will be combined. This reaction is similar to polyphosphoric acid or methanesulfonic acid/has Dehydration is carried out in a solvent acid. The end groups of the block cannot react in such an environment. should be chosen in such a way that they can

Block copolymers and their uses The proportion of polybenzazole to thermoplastic block is The body is chosen to be thermoplastic. Block copolymers consist of thermoplastic blocks 1 to 99 percent by weight of the thermoplastic block, preferably at least 10 weight percent, more preferably at least 30 weight percent, most preferably or at least 70 percent by weight. This is rigid or semi-rigid polybenzoa Preferably at least 3 weight percent and more preferably less than 3 weight percent of the sol block Contains at least 5% by weight. This block copolymer allows it to virtually decompose It must be fluid at temperatures that do not occur.

Block copolymers containing a high proportion of rigid or semi-rigid polybenzazoles can be When engineered, they often give excellent physical properties, but low proportions of polybenzoazole Block copolymers containing 100% Provides molded products with specific characteristics.

The ratio of rigid or semi-rigid polybenzazole blocks to thermoplastic blocks is , preferably the block copolymer flows and the particulate composition solidifies during molding. , has better physical properties than molded products made only from thermoplastic homopolymers. selected to give a molded article. This optimal ratio is used for block copolymers. Depending on the particular polymer and block size involved, one of ordinary skill in the art will It can be easily determined by experiment.

The average molecular weight of the block copolymer affects the flowability of the block copolymer as a whole. influence The average molecular weight is determined by the fact that the particulate composition hardens during molding and is a thermoplastic homopolymer. to provide molded products with better physical properties than molded products made from polymers alone. should be kept sufficiently low. The molecular weight can be adjusted by adjusting the stoichiometry of the reaction. , or by the use of chain terminators. U.S. Patent No. 4.703.103 As described, many different monofunctional substances have been used as chain terminators. However, monofunctional aromatic carboxylic acid derivatives such as benzoic acid or benzoyl chloride preferable. The optimum average molecular weight is determined by the specific polymer used in the block copolymer. , varies depending on the block size and block proportion, but can be determined experimentally by a person skilled in the art. Therefore, it can be determined easily.

The compositions and molded articles of the invention essentially consist of the block copolymers described above. or The compositions and molded articles of the invention are thermoplastics that are not part of the block copolymer. or polybenzazole polymers. This polymer is Preferably, the molded composition comprises a thermoplastic polymer in at least two dimensions. Selected to have better physical properties than the mer alone. This polymer is more preferred Alternatively, the composition is chosen so that it does not undergo phase separation during solidification or shaping. composition If the article comprises a thermoplastic polymer, this is preferably a block copolymer thermoplastic polymer. It is a homopolymer or copolymer with the same structure as the plastic block. in the composition The concentration of polybenzazole polymer is low enough that the composition is moldable Should.

The proportion of rigid or semi-rigid polybenzazole other than block copolymers is preferably is minimized. The composition most preferably comprises a rigid or semi-block copolymer. Contains no rigid polybenzazoles.

Block copolymers and polymer compositions containing them are usually prepared in solvent acid solutions or doped The dope is solidified by contacting the dope with a non-solvent diluent such as water. It will be done. The dope is usually at least plane isotropic (isotropic in two dimensions) and more preferably or optically when solidified to form a solidified product that is isotropic in three dimensions. Must be isotropic. The solidified product is most preferably optically phase separated. Not yet. Liquid crystal dopes tend to form phase-separated and anisotropic solidified products. It's across the street.

The optical isotropy and anisotropy of the dope are described in “Composites” by Hwang et al. n aMolecular Level: Phase Re1ationsh ips, Processing, andProperties″822(2 ), J, Macromol, Sci, Phys, 231.234-3 5 (1983), as determined by a number of methods known to those skilled in the art. be done. A simple method is that the solution is birefringent when observed under a microscope under crossed polarization conditions. The key is to see if there is a trend. Rigid rods, even in optically isotropic solutions The association of blocks appears to be on a molecular scale. However, optically isotropic phases The level of anisotropy and phase separation is preferably essentially small enough to give a block copolymer or polymer composition that is a molecular complex .

The point at which a given dope changes from isotropic to anisotropic phase depends on many factors, e.g. Concentration of polymer, solvent, size of hard rod PBZ block in polymer in dope It varies depending on the size, concentration, dope temperature, etc. Most easily adjusted parameters - is the concentration of block polymer and homopolymer. Enough to avoid anisotropy rejection It is convenient to synthesize the block copolymer in solution at a low concentration.

If an anisotropic dope is formed, dilute with solvent acid until an optically isotropic state is reached. be done.

The preferred concentration of polymer within the isotropic dope of the present invention is hard rod PBZ. Depends on the part of the polymer. The polymer in the dope is a hard rod PBZ block. When containing only 5 weight percent of dope, the concentration of polymer in the dope is such that the solvent acid dissolves. For example, it is 50% by weight or less. The polymer is a hard rod. When containing 30 weight percent of dope PBZ blocks, the dope is preferably a polymer Contains up to 15% by weight. Polymer hard rod PBZ block 50 weight If the dope contains less than 10 weight percent of the polymer, the dope preferably contains less than 10 weight percent of the polymer. include. If the polymer contains 70 weight percent hard rod PBZ blocks, the The polymer preferably contains no more than 6 weight percent polymer, more preferably 4 weight percent polymer. Including cents and below.

The solvent acid in the dope has the above meaning and preferred embodiments. block copolymer The most convenient solvent acids are those in which the compound is synthesized. However, block copolymers are synthesized in a first solvent acid, such as acid, and coagulated, and then It may be redissolved in a second solvent acid.

The dope contains other additives precipitated by the polymer, such as stabilizers or colorants. may be included. Preferably, such additives are minimal.

Polymerization by contacting the dope with a nonsolvent that coagulates the block copolymer - is recovered from the dope. The non-solvent is preferably aqueous. Non-solvent is basic may be slightly or slightly acidic, but preferably at the beginning of its use. It is neutral. Of course, a non-solvent tank is one in which the non-solvent in the tank has a constant flow of non-solvent. or even if it becomes more acidic when coagulating the dope, as long as a pH adjuster is added. good.

By crushing large coagulated particles of block copolymers and compositions containing them, It is difficult to form bright granular compositions. Therefore, the dope can be directly condensed into granular form. It is preferable to let it harden. This can be done in many ways.

For example, the dope may be frozen. Preferably the dope is less than O″C0 preferably -78°C or less, even more preferably -150°C or less, most preferably -150°C or less Freeze at below 190°C. A convenient temperature is liquid nitrogen temperature. frozen Dope is more easily ground than coagulated polymers and is suitable for grinding frozen solvent acids It is ground in a grinding device such as a ball mill or a grinding mill. Then the crushed dolphin The dope is placed in a relatively warm non-solvent bath to melt the dope and solidify the polymer. . The temperature of this bath must be above the freezing point of the dope. It is preferably less The temperature is at least 10°C, more preferably 50°C or higher. This temperature is room temperature. It is convenient to do so. Freezing-grinding and equipment for doing this are described in the following U.S. patents: , 2,216.094; 2.836.368: 3.453,221; 3,8 68.997: 4,069.161+ 3.936.517: 3.614. 001:　3.658゜259:　3. n3.592: 3.771,729: 4,072,026: and 4.273.294.

Alternatively, the dope may be sprayed into the coagulation bath in a fine mist. The coagulation bath is preferably agitated. Stirred. The powder obtained by either method preferably recovers the granular composition Filtered, +4 and dried. Spray extraction of polymers and Apparatus for doing so is disclosed in the following U.S. Patents: 3.953.401; 4.100.23 6+ 4.206.161 and 4.469.818.

The resulting granular product should have an average particle size small enough to be formed into a solid product. It is possible. This average particle diameter is preferably less than 500 μm, more preferably 10 Less than 0 μm, even more preferably less than 50 μm, most preferably less than 10 μm It is.

The particles preferably contain the same mixture of polymers and fractions found in the dope. It is a uniform material with a high degree of consistency. The polymer within the particle is preferably at least two dimensional. It is isotropic in the plane (plane isotropy), and more preferably isotropic in three dimensions.

The granular compositions of the invention may be shaped as is, but are preferably shaped to facilitate handling. It is compressed to form briquettes. The briquettes will fall apart when the pressure is released. formed by exposing powders to sufficient pressure to compress them together without causing It will be done. This pressure is preferably at least 50 psi, more preferably at least is also 500 psi, most preferably at least 2000 psi. Briquet The preferred size of the port is limited by implementation considerations. The size is suitable for the mold used. There must be. If it is too large, compress one briquette from the powder. It is difficult to

The granular composition of the invention is shaped by heating under pressure in a mold. The mold is , as simple as two heated surface plates to produce a flat black The shape of the part may be complex or complex. Molding only the granular composition in the mold The fibers may be combined into a granular composition such that the resulting molded article is a fiber-reinforced composite. May be mixed with Examples of suitable fibers include aramid fibers, carbon fibers, glass fibers, Including ramic fibers, quartz fibers and polybenzazole fibers. Also, granular composition , with particulate additives such as stabilizers, fillers, colorants, rubber modifiers or other additives. It may be molded with a mixture of

The temperature and pressure of molding are such that the individual particles of the particulate composition melt and form a single product. selected to be The optimum temperature, pressure and time of molding are determined by the polymer in the granular composition. Depends on the liquidity of the Contains long hard or semi-hard segments and is highly concentrated. Copolymers containing rigid and semi-rigid segments and having high average molecular weights are Contains short rigid or semi-rigid segments, with low concentration of rigid and semi-rigid segments higher molding temperatures and higher molding temperatures than similar copolymers containing Pressure and long molding times are usually required.

The temperature should be at least the glass transition temperature of the particulate composition.

This is preferably at least 5-10"C above the glass transition temperature of the particulate composition. . This is also the temperature below which substantial decomposition of the particulate composition occurs.

The preferred temperature will depend on the chemical and physical composition of the particulate composition. Poly(aromatic) -etherketone) block or polybenzazole/poly(aromatic etherketone) ) in block copolymers having less than 75 percent of any of the blocks , the temperature is preferably at least 250°C, more preferably at least 325°C, Most preferably at least 350°C. 75 piece amorphous polyamide block For block copolymers with less than 1 cent, the temperature is preferably lower (both 100″C1, preferably at least 150°C.Block copolymer In a particulate composition comprising a polybenzazole bound as a thermoplastic moiety of The molding temperature is preferably at least 200°C, more preferably at least 250°C. °C1 most preferably at least 350 °C. Block copolymer thermoplastic In a granular composition containing an aliphatic polybenzazole as a sexual moiety, the molding temperature is Preferably at least 200"C1, more preferably at least 230"C1 most Preferably it is at least 270°C. The thermoplastic part of the block copolymer and In granular compositions containing polybenzazole bound to preferably 500°C or less, more preferably 475°C or less, most preferably 450°C It is as follows. Aliphatic polybenzoazole as thermoplastic part of block copolymer The molding temperature is preferably 400°C or lower, more preferably 400°C or lower. The temperature is preferably 350°C or less, most preferably 300'C or less. Each granular composition The optimum temperature for will be readily determined by one skilled in the art.

The pressure causes the individual particles in the particulate composition to melt and solidify to form one product. It is a pressure that The preferred pressure depends on the physical and chemical composition of the particulate composition and the shaping It depends on the temperature at which it is carried out. This pressure is preferably applied to the powder to form the molded article. The pressure is as low as possible to obtain sufficient coagulation. thermoplastic block In block copolymers containing at least 75 percent preferably 50,000 psi or less, more preferably 10,000 psi or less, most preferably Preferably, it is 5000 psi or less. Pressure is usually low to obtain good coagulation. both 50psi, more typically at least 500psi, most commonly less At least 1000 psi. Optimal pressures are readily determined by those skilled in the art. Will.

The molded article may be annealed after molding if desired. This annealing is preferably performed on molded products. The process is carried out at a temperature above the glass transition temperature of the polymer within, but below its melting point. a Neiling is more preferably carried out at a temperature close to the melting point of the polymer. Annealing is under reduced pressure Alternatively, it may be carried out at superatmospheric pressure, but atmospheric pressure is convenient. Atmosphere is good for aryl Air or nitrogen is preferred, but as long as the polymer is stable under the annealing conditions. It can be carried out in any atmosphere. Annealing typically increases the tensile strength of the molded part, but , slightly decreases the tensile modulus of the molded article.

The product of this molding step comprises the block copolymer described above and particles of the granular composition. It is a molded product in which the two are fused together. Although the fusion of individual particles is not so complete, The molded article is preferably free of pores (pore space less than 1 percent). Inside the molded product The polymer is preferably at least flat isotropic, more preferably optically It is isotropic to all aromas. The molded article shows some crystalline zones.

The molded article is preferably made of a thermoplastic block similar to the block copolymer. It has physical properties that are superior to those of similar molded articles containing only mer. for example , this molded product has high tensile strength, tensile modulus, flexural modulus, dimensional stability and/or Has solvent resistance. The improvement in properties is preferably achieved in at least two perpendicular directions. preferably in all directions. In other words, improvement is not a single axis, but at least It is also biaxial. The improvement in properties need not be uniform in all directions, but is preferred. is uniform.

The molded article is preferably not optically phase separated. This is not a fiber. That's good preferably at least 10 mils, more preferably at least 1/8 inch thick. have The maximum thickness is mainly determined by heating the instrument scale and sample to the appropriate temperature. Limited in practical respects such as ability. As a structural material or electronic base material or a thermoplastic polymer corresponding to the thermoplastic part of the block copolymer is suitable. This may be used for other applications.

Example The following examples are illustrative of the invention and are not in any way limiting.

Parts and percentages are by weight unless otherwise indicated.

(a) 50% cispolybenzazole and 50% amorphous Particulate composition comprising a block copolymer of polyamide and (b) an amorphous polyamide , and molded articles made therefrom (al hard rod cis polybenzazole and and (b) amorphous polyamide polymer. Synthesize a dope containing Dope solvent acids include methanesulfonic acid, polyphosphoric acid and It is a mixture of phosphorus and phosphorus pentoxide.

The cispolybenzazole block in the block copolymer has a number average model shown in Table 1. 0.05 g/di concentration at 25°C in nomer units and methanesulfonic acid It has an internal viscosity (before being mixed into the block copolymer) shown in Table 1. Bro The amorphous polyamide block within the block copolymer contains 30 percent terephthaloy. a mixture containing isophthaloyl chloride and 70 percent isophthaloyl chloride and a suitable amounts of 4-phenoxyphenoxybenzoyl chloride and hexamethylene diamine. is the product of the reaction.

Block copolymers are produced by (1) decoupled halogenated carboxylic acids; and (2) decoupling the polybenzazole block. contacting a polyamide end-capped with ringed aromatic groups; (3) Equimolar and Synthesized by reacting with weight end-capped polymer. this The method is based on Harris et al.'s Copolymers Containing P o1ybenzoxazo\le.

Polybenzothiazole and Polybenzimidaz ole Mo1eties, International Application PCT/[JS89104464 (198 International Publication W090103995 (April 19, 1990) Publications) and U.S. Patent Application No. 407.973 (filed September 15, 1989). It is described in detail. The resulting block copolymer has approximately 50 weight percent comprising sporibenzazole and about 50 weight percent amorphous polyamide; Determined in methanesulfonic acid at 10,05 g/di concentration at °C and shown in Table 1 Has internal viscosity.

E, 1. Trademark 5el by DuPont de Nemours & Co. Amorphous polyamide sold as ar-PA was added to each dope. The phase weight ratio of polybenzazole to polyamide is approximately 15% polyben Zoazole - Add to about 85 percent amorphous polyamide.

The resulting dope is optically isotropic (not liquid crystalline). Amorphous porous in dope The total concentration of lyamide and block copolymer is 4 weight percent.

Each dope was frozen at a temperature of -290℃ to -200℃, and the particles of 10 to 2000 μm were frozen. Grind to a degree distribution. Place this crushed frozen dope in a stirred water bath at approximately room temperature. Add. The resulting precipitated granular composition is filtered, washed with water and dried. This is 1~ It has a particle size distribution of 250 μm.

Approximately 6 g of each powder was compressed at room temperature for approximately 10 hours at a pressure of 20,000 ps form a ket.

Each briquette was molded at the temperatures and times shown in Table 1 and for about 1/2 16 inches (0,16 cm) thick and approximately 2.5 inches (6,4 cm) in diameter form a disc with Each disc was tested as described in ASTM D-790. The test tests for bending strength and modulus. This is the strength shown in Table 1, It has elastic modulus and strain.

Example 2 - 10% cispolybenzazole and 90% poly(aromatic) etherketone) and moldings made therefrom Goods 10 weight percent cis polybenzazole and 90 weight percent poly(aromatic) form a dope containing a group of ether ketones). Dope solvent acid is methanesulfonate It is a mixture of phosphoric acid, polyphosphoric acid and phosphorus pentoxide.

The cispolybenzazole block in the block copolymer has a number-average model shown in Table 2. 0.05 g/dl at 25°C in nomer unit and methanesulfonic acid! 1 It has an internal viscosity (before being mixed into the block copolymer) shown in Table 2, as measured in degrees. Bu The poly(aromatic ether ketone) in the lock copolymer is oxybis(4-chlorinated) benzoyl) and 1,4-diphenoxybenzene.

Block copolymers are produced by (1) decoupled halogenated carboxylic acids; (2) aromatic electrophilic groups; Under conditions where oxidation occurs, the decoupled acid group-terminated polypeptide Oxybis(4-benzoyl chloride) and 1,4-diphenazole block Synthesized by reacting with noxybenzene and benzoic acid (terminator).

This method is based on the Copolymers Containing method of Harris et al. Po1ybenzoxazo\Ie.

Polybenzothiazole and Polybenzimidaz ole Mo1eties, International Application PCT/US89104464 (1989 International Publication W090103995 (Published on April 19, 1990) Details in U.S. Patent Application No. 407.973 (filed September 15, 1989) It is described in. The resulting block copolymer composition has approximately 10 weight percent Contains polybenzazole and about 90 weight percent poly(aromatic ketone). Mi, 25℃, 0.05g/dll! Measured in methanesulfonic acid at It has an internal viscosity of 2. Its concentration in the dope is about 8% by weight. be. The resulting dope is optically isotropic (not liquid crystalline).

Each dope was frozen at a temperature of -190°C to -200°C, with a thickness of 10 to 2000 μm. Grind to particle size distribution. This crushed frozen dope is placed in a stirred water tank at approximately room temperature. Add to. The resulting precipitated granular composition is filtered, washed with water and dried. Granular composition Some of the material is extracted with acetone or acetylacetone. This granular composition The material has a particle size distribution of 1 to 250 μm.

Approximately 6 g of each powder was compressed at room temperature under a pressure of 20,000 psi for approximately 10 hours to form a briquette. form a cut.

Each briquette was molded at the temperatures and times shown in Table 2 and for about 17 hours. 16 inches (0,16cn+) thick and approximately 2.5 inches (6,4cm) in diameter form a disk with Each disc is as described in ASTM D-790. The bending strength and modulus of elasticity are tested using the following tests. This is the strength shown in Table 2. , modulus of elasticity and strain.

Example 3 - Cis polybenzazole and thermoplastic polybenzazole/poly(aromatic etherketone) copolymer; A molded product produced from this was prepared by mixing cispolybenzazole and thermoplastic resin in the ratios shown in Table 3. Shaped dope containing ribenzazole/poly(aromatic ether ketone) copolymer to be accomplished. The dope solvent acid is a mixture of methanesulfonic acid, polyphosphoric acid and phosphorus pentoxide. It is a compound.

The cispolybenzazole block in the block copolymer has a number average model shown in Table 3. concentration of 0.05 g/di at 25°C in nomer unit and methanesulfonic acid. It has an internal viscosity (before mixing into the block copolymer) shown in Table 3, as measured in degrees. Bu Polybenzazole/poly(aromatic ether ketone) block in rock copolymer 4.6-Diamylsorcinol, oxybis(4- Product obtained by reacting benzoyl chloride) and 1,4-bis(phenoxy)benzene The block copolymer is (1) polybenzazole oligomer and 4.6 -Diamylsorcinol is a combination of this oligomer and 4,6-diamylsorcinol. reacting with 2 moles of oxybis(4-benzoyl chloride) per mole of , (2) the product of step 1 is ori- nated under conditions such that electrophilic aromatic substitution occurs. Approximately 1 mole of 1,4 per mole of sesame and 4.6 to cyamyl sorcinol combined - reacting with bis(phenoxy)benzene and benzoic acid (terminating agent); more synthesized. This method is based on Harris et al.'s Copolymers Co maintainingPolybenzoxazoVle, Polybenzot hiazole and PolybenzimidazoleMoietie s, International Application PCT/US89104464 (filed October 6, 1989), International publication W090103995 (published on April 19, 1990) and US patent application No. 407°973 (filed on September 15, 1989).

The obtained block copolymer composition has the following formula 10 (in the above formula, a is the number shown in Table 3). with the number of monomer units in the rigid rod polybenzazole block corresponding to Yes, b is the weight ratio of rigid rod polymer to thermoplastic polymer as shown in Table 3. is the number of monomer units in the thermoplastic block chosen to correspond to the ratio , C is such that the block copolymer has a molecular weight corresponding to the internal viscosity shown in Table 3. is the number of repeating units, and d is on average 1 for the monomer of the thermoplastic block. – is the number of repeating units within the unit) It has an average structure represented by . This is the measurable value at 25°C and 0.05g/di concentration. Measured in tansulfonic acid and having the proportion and internal viscosity of each polymer shown in Table 3. . Its concentration within the dope is 1-15 weight percent. dope obtained is optically isotropic (not liquid crystal).

Each dope was frozen at a temperature of -190℃ to -200℃, and the particles of 10 to 2000 μm were frozen. Grind to a degree distribution. Place this crushed frozen dope in a stirred water bath at approximately room temperature. Add. The resulting precipitated granular composition is filtered, washed with water and dried. granular composition Some of it is extracted with acetone or acetylacetone. This granular composition has grown a particle size distribution of 1 to 250 μm.

Approximately 9 g of each powder was compressed at room temperature for approximately 10 hours at a pressure of 20.0 OOpsi and briquette form a cut.

Each briquette was molded at the temperatures and times shown in Table 3 and for about 17 hours. 16 inches (0,16 cm) thick and approximately 2.5 inches (6,4 cm) in diameter form a disc with Each disc was tested as described in ASTM D-790. The test tests for bending strength and modulus. This is the strength shown in Table 3, Developing elastic modulus and strain.

Example 4 - Cis polybenzazole and thermoplastic polybenzazole/poly(aromatic etherketone) copolymer; The block copolymer obtained from the molded product has the formula 3 (where d is 0 on average). ．． 33 (the poly(aromatic ether ketone) content of the thermoplastic block increases) 4,6-diamylsorcinol, oxybis(4-salt) Adjusting the ratio of 1,4-bis(phenoxy)benzoyl) and 1,4-bis(phenoxy)benzene Repeat Example 3 with the following exceptions: The results are shown in Table 4.

Example 5 - 5% hard rod cispolybenzoxazole and 95% fat Granular compositions comprising block copolymers of aliphatic polybenzoxazole; The molded article 5 produced from this had an internal viscosity of 77 dl/g and 0 at each end. - is primarily terminated by an aminohydroxy moiety and is essentially a monomer of the formula consisting of mer units (excluding terminal groups) functional group-terminated rigid rod cis-polybenzoyl Produce a xazole block.

This functional end block was removed in a mixture of methanesulfonic acid and polyphosphoric acid with 4.6- React with diamylsorcinol dihydrochloride and sebacic acid. reaction mixture The concentration of solids in the product should be sufficiently concentrated to give a dope containing about 2% solids by weight. The ratio of monomer to functional end blocks is approximately 5 weight percent hard. rod blocks and about 95 weight percent aliphatic polybenzoxazole blocks. suitable for providing block copolymers containing blocks. Do not add stopper.

The resulting dope was frozen at liquid nitrogen temperature and placed in a 7-41bs ceramic bottle. Grind for 2 hours using a grinder. The frozen granular composition is added to the system at a pH of approximately 7. Contains crushed ice with addition of aqueous sodium hydroxide as necessary to maintain ~8. Coagulate in Brengu in phosphate buffer slurry. Precipitated granular composition filtered, washed twice in deionized water and once in acetone for several hours, and vacuumed in air. Dry in the oven to a certain weight.

The powders as shown in Table 1 were compressed for about 10 hours at about 20,000 pressure and room temperature. , forming briquettes.

Each briquette was molded at the temperatures and times shown in Table 1, and for about 17 hours. 16 inches (0,16 cm) thick and approximately 2.5 inches (6,4 cm) in diameter form a disc with Each disc was tested as described in ASTM D-790. The test tests for bending strength and modulus. This is the strength shown in Table 5, It has elastic modulus and strain.

Table 5 Example 6 - 5% hard rod cispolybenzoxazole and 95% fat Granular compositions comprising block copolymers of aliphatic polybenzoxazole; The molded article 5 produced therefrom has an internal viscosity of 1 dl/g and 0- It is mainly terminated by an aminohydroxy moiety, and is essentially a monomer represented by the following formula. A functional group-terminated rigid rod consisting of mer units (excluding terminal groups) of cis-polybenzoyl Produce a xazole block.

This functional end block was added to 4,6-diamylsorcinol dihydride in polyphosphoric acid. React with lochloride and sebacic acid. The concentration of solids in the reaction mixture is approximately 3 The concentration is sufficient to give a dope containing an amount of percent solids and no functional end blocks. The ratio of monomer to block is about 5 weight percent rigid rod block and about 95 weight percent Block copolymer containing percent aliphatic polybenzoxazole blocks suitable for giving. As a terminator, 2-aminophenol is reacted with sebacic acid. Add an amount equal to 5 weight percent of cyamyl sorcinol. poly that can be obtained The mer has an internal viscosity of 7.93 dl/g.

The resulting dope was frozen at liquid nitrogen temperature and placed in a ceramic bottle of 7.41 bS. Grind for 2 hours using a grinder. The frozen granular composition is added to the system at a pH of approximately 7. Contains crushed ice with addition of aqueous sodium hydroxide as necessary to maintain ~8. Coagulate in Brengu in phosphate buffer slurry. Precipitated granular composition Filter I7, wash several times in deionized water, filter and keep in constant air in a vacuum oven. Dry to weight.

7.3 g of powder was compressed for about 10 hours at about 20,000 pressure and room temperature, and form a ket.

Each briquette was molded for 3 minutes at 225°C and 20.000 psi, approx. /16 inches (0,16 cm) thick and approximately 2.5 inches (6,4 cm) in diameter form a disk with Each disc is as described in ASTM D-790. The bending strength and modulus of elasticity are tested using the following tests. This is 4,705ps It has a flexural strength of i and a flexural modulus of 371.000 psi.

abstract Contains blocks of polybenzazole polymers and blocks of thermoplastic polymers A granular composition containing a block copolymer is compression molded, and the thermoplastic polymer alone is used. A molded article is provided that has better physical properties than the manufactured molded article.

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Claims (11)

[Claims] 1. (a) Rigid rod or semi-rigid polybenzazole polymer blocks and (b) a block copolymer having a thermoplastic polymer block, comprising (1) Each polybenzazole polymer block has an average of at least 5 monomer units. (2) the block copolymer is thermoplastic; A block characterized in that it is flexible and can be compression molded without substantially causing phase separation. rock copolymer. 2. (1) A rigid block containing an average of at least 5 monomer units per block. (2) block copolymer block or semi-rigid polybenzazole polymer block; Suitable size and size such that the polymer is flowable at temperatures below its decomposition temperature. A block copolymer having a thermoplastic polymer block with a proportion of The copolymer is in the form of solid particles with an average particle diameter of 1000 μm or less. A block copolymer characterized by: 3. A briquette comprising the granular composition according to claim 2. 4. The temperature at which the granular composition is fluid and the granular composition solidifies and conforms to the shape of the mold. A method of forming a molded article comprising the step of molding a solid particulate composition in a mold under sufficient pressure to (1) the particulate composition comprises (a) an average of at least 5 molecules per block; polybenzazole polymer block containing nomeric units and (b) block copolymer of suitable size and proportions such that the remer is flowable at temperatures below its decomposition temperature. comprising a non-phase separated block copolymer having a thermoplastic polymer block; and (2) the granular composition is characterized in that it has an average particle diameter of 1000 μm or less. Method. 5. A molded article produced by the method according to claim 4. 6. All polybenzazole polymers in the block copolymer are polybenzo Any of the preceding claims, which is an oxazole or polybenzothiazole polymer. The invention described in . 7. Rigid or semi-rigid polybenzazole block is formed by the following formula (a) ▲ Mathematical formula, chemical There are formulas, tables, etc. ▼, (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, (c) ▲ Number There are formulas, chemical formulas, tables, etc. ▼, (d) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ( e)▲There are mathematical formulas, chemical formulas, tables, etc.▼, (f)▲There are mathematical formulas, chemical formulas, tables, etc. ▼(g) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The invention according to any of the preceding claims, comprising a nomer unit. 8. The thermoplastic block is (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (c) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, X is a bond or the first two is a valence bond moiety, each Ar, Ar1 and Ar3 are aromatic groups, and L is a polymer is a non-linear group that is stable under the conditions under which it is synthesized, processed and used; R1 is an aliphatic group containing at least about 3 carbon atoms, and each Z is an oxygen atom or sulfur atom) A thermoplastic polybenzazole containing a monomer unit represented by any one of The invention according to any of the preceding claims, which is a polymer. 9. L comprises two aromatic groups linked by a second divalent bonding moiety (X'), X and X' are each a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom; the law of nature, R1 is an alkyl group or a halogenated alkyl group containing up to about 12 carbon atoms; The invention according to claim 8. 10. The thermoplastic polymer block is made of the following polymers, polyamides, thermoplastic imide, polyquinoxaline, polyquinoline, poly(aromatic ether ketone) and / or poly(aromatic ether sulfone), or these polymers with each other and/or or a copolymer with polybenzazole. The invention according to any one of. 11. Thermoplastic polymer blocks include thermoplastic polyamide, poly(aromatic ether) ) or a copolymer of poly(aromatic ether) and polybenzazole, The invention according to claim 10.