JP2008144184A - Polyphenylene copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyphenylene maintaining excellent solubility and processability, and having a lower K and Tg, and a method for manufacturing it. <P>SOLUTION: A copolymer contains a structure shown by general formula (1) wherein -Ar- represents at least one repetitive unit of arylene or heteroarylene. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polyarylene copolymer having a substituted arylene repeating unit in the main chain. The polymers can be used as dielectric insulators and heat resistant plastics for electrical devices. The present invention also relates to an ionic composition comprising a polyarylene copolymer having an acid and a heterocyclic repeat unit. The ionic composition can be used as a polymer electrolyte.

  Polyarylene is of interest because the basic arylene units have excellent thermal and chemical stability. Polymers containing only phenylene units are known. One method for producing these is oxidative coupling of aromatic compounds such as benzene, as described in Non-Patent Document 1. This method involves the use of a chemical oxidant such as cupric chloride and a Lewis acid catalyst, and generally results in an indeterminate insoluble polyphenylene. Polyphenylene produced by the oxidation of benzene is said to have a low molecular weight with a branched chain.

Non-patent document 2 reports a polyphenylene having a clearer composition. The unsubstituted parent compound, polyphenylene, was insoluble in all solvents and did not melt. Phenyl-substituted polyphenylenes prepared by Diels-Alder cycloaddition of expensive monomers due to considerable purification are soluble in organic solvents and can be processed into films. These phenylene-substituted polyphenylenes have both para- and meta-position carnations in the main chain, but the ratio between the para-position and the meta-position is only inferred from the study of model compounds.
Substituted polyphenylene is disclosed in US Pat. Patent Document 1 discloses a rigid rod (that is, a 1,4 or para bond is dominant) polyphenylene which has become soluble by addition of an organic side group. The side groups are selected from electrically neutral (non-charged) groups that interact positively with the solvent.
The chemical and physical properties of substituted polyphenylenes, including thermal stability, glass transition temperature (T _g ) and dielectric constant (K), depend on the stabilizing group and the structure of the polymer backbone. While maintaining excellent solubility and workability, it has been desired to find a polyphenylene having a lower K and T _g. It is also desirable to provide a highly purified polyphenylene having a well-defined structure that can be produced from relatively inexpensive starting materials.

US Pat. No. 5,227,457 P. Kovacic, et al., Chem. Rev., 1987, 87, 357-379 J. K. Stille, Die Makromolekulare Chemie, 1972, 154, 49-61

  The practice of the present invention provides a copolymer comprising repeat units comprising an arylene aromatic nucleus, at least some of which are substituted with pendant organic groups. The aromatic nucleus is bonded to the polymer main chain at the meta (1,3) or para (1,4) position, and 1, 2 or 3 CH of the phenylene nucleus or ring is replaced by N It can be a heteroaromatic nucleus. An aromatic nucleus in which one CH is replaced by N is a pyridine nucleus, an aromatic nucleus in which two CH are replaced by N is a pyridine, pyrimidine or pyridazine nucleus, and three CHs are N The aromatic nucleus replaced with is a triazine nucleus.

上式中−Ａｒ−は、１種以上の下式で表されるアリーレン又はヘテロアリーレン繰返し単位である：

及び The copolymer of the present invention comprises a structure represented by the following general formula:

In the above formula, -Ar- is an arylene or heteroarylene repeating unit represented by one or more of the following formulas:

as well as

上式中、
芳香族ＣＨ基の１〜３個はＮにより任意に置き替えられていてよい； 式（１）中の繰返し単位の少なくとも０．１モル％及び好ましくは少なくとも１モル％が−Ａｒ−である；
アリーレンセグメントの数平均セグメント長さは２を超え、好ましくは３を超え、より好ましくは４を超え、パラ−アリーレンの繰返し単位が存在する場合には、その数平均セグメント長さは１〜約８の範囲である；
メタ−アリーレン繰返し単位が存在する場合には、その数平均セグメント長さは１を超える；
ｘは０〜４であり、ペンダント基（Ａ）は、−Ｆ、−ＣＮ、−ＣＨＯ、−ＣＯＲ、−ＣＲ＝ＮＲ’、−ＯＲ、−ＳＲ、−ＳＯ₂ Ｒ、−ＯＣＯＲ、−ＣＯ₂ Ｒ、−ＮＲＲ’、−Ｎ＝ＣＲＲ’、−ＮＲＣＯＲ’、−ＣＯＮＲＲ’及びＲから成る群より独立に選ばれ、前記Ｒ及びＲ’は、Ｈ、アルキル、置換アルキル、アリール、置換アリール、ヘテロアリール及び置換ヘテロアリールからなる群より独立に選ばれ、並びにＲ及びＲ’は一緒に結合していてよい；

In the above formula,
1-3 of the aromatic CH groups may be optionally replaced by N; at least 0.1 mol% and preferably at least 1 mol% of the repeating units in formula (1) are —Ar—;
The number average segment length of the arylene segment is greater than 2, preferably greater than 3, more preferably greater than 4, and when a para-arylene repeat unit is present, the number average segment length is from 1 to about 8 A range of
If a meta-arylene repeat unit is present, its number average segment length is greater than 1;
x is 0-4, pendant groups (A) are, -F, -CN, -CHO, -COR , -CR = NR ', - OR, -SR, -SO 2 R, -OCOR, -CO 2 R, —NRR ′, —N═CRR ′, —NRCOR ′, —CONRR ′ and R are independently selected, wherein R and R ′ are H, alkyl, substituted alkyl, aryl, substituted aryl, hetero Independently selected from the group consisting of aryl and substituted heteroaryl, and R and R ′ may be joined together;

Y is absent or is a divalent group selected from the group consisting of -Z-, -Z-Ph- and -Ph-Z-Ph-, wherein Z is -O-, -S-, -NR -, - O (CO) -, - O (CO 2) -, - (CO) NH (CO) -, - NR (CO) -, phthalimide, pyromellitimide, -CO -, - SO-, A divalent group selected from the group consisting of —SO ₂ —, —P (O) R—, —CH ₂ —, —CF ₂ —, and —CRR′—;
Ph is phenylene (ortho, meta or para-phenylene);
In the absence of Y, there are at least two substitutionally or isomerically different types of -Ar-repeat units;
At least 1 for every 100 repeating units, preferably at least 1 for every 10 repeating units, more preferably at least 1 for every 5 repeating units, most preferably at least 1 for every 2 repeating units And n represents a number average degree of polymerization and is greater than about 4, preferably from about 10 to 10,000, more preferably from about 20 to 1,000, and most preferably from about 50 to A number of 500.

上式中Ｒ’’は、Ｈ、アルキル、アリール、−ＯＨ、−ＮＨ₂ 、−ＳＨ、アルコキシ、アリーロキシ、チオアルキル、チオアリール、置換アルキル及び置換アリールである。 There are one or more -Ar- or -Y- type repeat units. Unrestricted examples of copolymers are (-Ar-/-Ar '-/-Y-) (-Ar-/-Ar'-/-Ar ''-/ Y-) (-Ar-/-YYY '). -) Etc.
Two adjacent side groups A may be cross-linked. Non-limiting examples of bridging groups include the following groups:

In the above formula, R ″ is H, alkyl, aryl, —OH, —NH ₂ , —SH, alkoxy, aryloxy, thioalkyl, thioaryl, substituted alkyl and substituted aryl.

Examples of alkyl groups —R useful in the practice of the present invention include, but are not limited to, methyl, ethyl, propyl, n-butyl, t-butyl, dodecanyl, trifluoromethyl, perfluoro-n-butyl, 2 2,2-trifluoroethyl, benzyl, 2-phenoxyethyl and the like.
Examples of aryl groups -R useful in the practice of this invention include, but are not limited to, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, naphthyl, biphenyl, 4-phenoxyphenyl, 4-fluorophenyl , 3-carbomethoxyphenyl, 4-carbomethoxyphenyl and the like.
Examples of alkoxy groups —OR useful in the practice of the present invention include, but are not limited to, methoxy, ethoxy, 2-methoxyethoxy, t-butoxy, and the like.
Examples of aryloxy groups —OR useful in the practice of the present invention include, but are not limited to, phenoxy, naphthoxy, phenylphenoxy, 4-methylphenoxy, and the like.

Examples of ketone groups —COR useful in the practice of this invention include, but are not limited to, acetyl, propionyl, t-butylcarbonyl, 2-ethylhexylcarbonyl, phenylcarbonyl (benzoyl), phenoxyphenylcarbonyl, 1-naphthyl. Examples include carbonyl, 2-naphthylcarbonyl, nicotinoyl, isonicotinoyl, 4-methylphenylcarbonyl, 2-fluorophenylcarbonyl, 3-fluorophenylcarbonyl, 4-fluorophenylcarbonyl and the like.
Examples of amine groups -NRR 'useful in the practice of the present invention include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.
The imine group -N = CRR 'useful in the practice of the present invention includes, but is not limited to, dimethylimino (R = R' = methyl), methylimino (R = H, R '= methyl), phenylimino ( R = H, R ′ = phenyl) and the like.

Examples of imine groups —CR═NR ′ useful in the practice of the present invention include, but are not limited to, phenyl-N-methylimino, methyl-N-methylimino, phenyl-N-phenylimino, and the like.
Examples of amide groups -CONRR 'useful in the practice of this invention include, but are not limited to, N, N-dimethylaminocarbonyl, N-butylaminocarbonyl, N-phenylaminocarbonyl, N, N-diphenylamino. Examples include carbonyl, N-phenyl-N-methylaminocarbonyl and the like.
Examples of amide groups —NRCOR ′ useful in the practice of the present invention include, but are not limited to, N-acetylamino, N-acetylmethylamino, N-benzoylamino, N-benzoylmethylamino, and the like.
Examples of ester groups —CO ₂ R useful in the practice of the present invention include, but are not limited to, methoxycarbonyl, benzoyloxycarbonyl, phenoxycarbonyl, naphthyloxycarbonyl, ethylcarboxy, and the like.

Examples of ester groups —OCOR useful in the practice of the present invention include, but are not limited to, phenylcarboxy, 4-fluorophenylcarboxy, 2-ethylphenylcarboxy, and the like.
Examples of thioether groups —SR useful in the practice of the present invention include, but are not limited to, thiomethyl, thiobutyl, thiophenyl, and the like.
Examples of sulfonyl groups —SO ₂ R useful in the practice of the present invention include, but are not limited to, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, tolylsulfonyl, and the like.

  Examples of repeating units -Ar- useful in the practice of this invention include, but are not limited to, phenylene (1,3- and 1,4-phenylene), 5-amino-1,3-phenylene, 4- Benzoyl-1,3-phenylene, 5-benzoyl-1,3-phenylene, 2-benzoyl-1,4-phenylene, 4,4′-biphenyldiyl, 2-carboxy-methyl-1,4-phenylene, 4-carboxymethyl-1,3-phenylene, 5-carboxymethyl-1,3-phenylene, 1,3-naphthalenediyl, 1,4-naphthalenediyl, 5-phenoxy-1,3-phenylene, 2-phenyl- 1,3-phenylene, 4-phenyl-1,3-phenylene, 5-phenyl-1,3-phenylene, 2-phenyl-1,4-phenylene, 2,6-pyridinedi , 2,4-pyridinediyl, 3,5-pyridinediyl, 3,6-pyridinediyl, 5,8-quinolinediyl, 2,4-toluene-diyl, there are 2,5-xylene-diyl and the like. Examples of isomers not specifically listed other than the 1,3-position and 1,4-position of the above-described arylene group include 2,4-quinolinediyl, 2,5-quinolinediyl, 2,6-quinolinediyl, and the like. One skilled in the art will recognize other Ar nuclei suitable for use in the present invention.

Preferred examples of Z include, but are not limited to, Z is -oxy-1,4-phenylene-2,2-isopropylidene-1,4-phenylene-oxy-; -oxy-4,4'- Diphenylmethane-oxy; -oxy-1,4-phenylene-2,2-hexafluoroisopropylidene-1,4-phenylene-oxy-;-carbonyloxy-1,4-phenylene-2,2-isopropylidene-1,4 Derived from bisphenol A, bisphenol AF and other bisphenols, such as -phenylene-oxycarbonyl-; Additional preferred examples of Z include: -hexafluoroisopropylidene-2,2-diyl; -isopropylidene-2,2-diyl; 2-phenyl-1,1,1-trifluoroethylidene-2,2'- There are giles, etc.
Preferred examples of -Ph-Z-Ph-type esters and amides include-(phenylene-CONH-phenylene-NHCO) -phenylene,-(phenylene-CONH-phenylene)-,-(phenylene-COO-phenylene-OCO ) -Phenylene-,-(phenylene-carbonyl) -phenylene-,-(phenylene-carbonyl-phenylene-oxo-phenylene-carbonyl-phenylene)-and the like.

When the polymer of the present invention is a block copolymer and Y is not present, the repeating unit Y can form an oligomer segment or a polymer segment. Unrestricted examples of the repeating unit Y include polyamide, polyarylate, polyarylene oxide, polycarbonate, polydimethylsiloxane, polyester, polyetherketone, polyphenylene, substituted polyphenylene, polyphenylene sulfide, polystyrene and the like.
Preferred Y units forming the block, - (phenylene -CONH- phenylene -NHCO) _m - phenylene, - (phenylene -CONH) _m - phenylene -, - (phenylene -COO- phenylene --OCO) _m - phenylene - ,-(Phenylene-carbonyl) _m -phenylene- and-(phenylene-carbonate-phenylene-2,2-isopropylidene-carbonate) _m -phenylene-.

In the present specification, polyarylene oxide means a general name of a polymer of the (—Ar—O—) _n type. The polyarylene oxide is not limited, but includes poly (2,6-dimethyl-1,4-phenylene oxide), poly (2,6-diphenyl-1,4-phenylene oxide), poly (oxy- 2,3,5,6-tetrafluorophenylene) and poly (oxy-2,6-pyridinediyl). As used herein, polyetherketone refers to the generic name of various polymers comprising phenylene, oxo and carbonyl repeat units, including but not limited to poly (oxy-1,4-phenylene-oxy-1). , 4-phenylene-carbonyl-1,4-phenylene), polyetheretherketone known as PEEK, and similar polymers such as PEK and PEKK. As used herein, a polyarylate is formed from terephthalic acid or isophthalic acid and a diol such as bisphenol A (2,2′-isopropylidenediphenol), resorcinol, hydroquinone, 4,4′-dihydroxybiphenyl, and the like. The general name of various polymers. The above general names are known to those skilled in the art.

Polyamides include, but are not limited to, 1,4-butanediamine, 1,6-hexanediamine, 4,4′-methylenedianiline, 1,3-phenylenediamine, 1,4-phenylenediamine, and the like. There are polymers formed by the usual condensation of diamines with diacids such as adipic acid, isophthalic acid, terephthalic acid, succinic acid and the like.
Polyesters include, but are not limited to, diols such as ethylene glycol, 1,6-hexane glycol, hydroquinone, propylene glycol, resorcinol, and the like, and adipic acid, isophthalic acid, terephthalic acid, succinic acid, and the like. There are polymers formed by normal condensation with acids.
As shown in structure (1), the polymers of the present invention are random or block copolymers. The slash (/) in and below the polymer structure (1) represents the most common arrangement of repeat units and includes random copolymers, block copolymers or other copolymer types. The polymer of the present invention may have an intermediate structure between completely random blocks and regular blocks, which may be divided into partial block co-polymers or blocky co-polymers. -polymer). The degree of reactivity and the degree of reactivity of the various monomers depends on the blockiness, and one skilled in the art can adjust the degree of blockiness of the product polymer in view of the various methods.
The polymers of the present invention can have end groups derived from monomers or specific end-capping groups added during the polymerization reaction. The end groups can be further modified by chemical transformations such as elimination of protecting groups or reactions in post-polymerization steps. The end groups can be used to form block copolymers with other monomers or polymers, or as crosslinking groups during the curing process.

The polymer in one embodiment of the present invention is a copolymer of meta-phenylene and para-phenylene units having a structure represented by the following general formula.

上式中ａはメタ−フェニレンブロックの数平均長さであり、及びｂはパラ−フェニレンブロックの数平均長さであり、ｎは鎖当たりのブロックの数平均数である。この型のコポリマーは１を超えるａを有し、１〜約８の範囲のｂを有する。ｂが約８を超える場合には、ポリマーは、本質的には剛性ロッド（rigid-rod）型ポリマーであり、通常のフレキシブルなポリマーに比して性質上異なる挙動を有する。剛性ロッドポリマーはフレキシブルポリマーであって、典型的には、繰返し単位が同様であっても異なるクラスのポリマーとして見なされる。特に、剛性ロッドポリマーは、溶融時及び溶液中で非常に高い粘度を有し、且つ非常に高い引張弾性率を有する。これらは非常に高い粘性を有するために、剛性ロッドポリマーの加工及び精製は困難である。本発明のポリマーはせいぜい半硬質（semi-rigid）であり、剛性ロッドポリマーの極度に高い粘性を持たない。しかしながら、本発明のポリマーは剛性ロッドポリフェニレンに比してより高い溶解性及び溶融流れ特性を有し、本発明のポリマーはポリフェニレンの化学的安定性及び熱安定性をも有し、Ｋが低くなるように及び水吸収性が低くなるように適切に側基が選ばれる。 In the above embodiment, since all the segments are arylene, Y does not exist and the segment length of the arylene segment is n.
Co-poly (meta-phenylene-/-para-phenylene) is a block copolymer represented by the following general formula:

Where a is the number average length of the meta-phenylene blocks, b is the number average length of the para-phenylene blocks, and n is the number average number of blocks per chain. This type of copolymer has a greater than 1 and b ranging from 1 to about 8. If b is greater than about 8, the polymer is essentially a rigid-rod type polymer and behaves differently in nature compared to normal flexible polymers. Rigid rod polymers are flexible polymers and are typically considered as different classes of polymers even though the repeat units are similar. In particular, the rigid rod polymer has a very high viscosity when melted and in solution and has a very high tensile modulus. Because they have a very high viscosity, the processing and purification of rigid rod polymers is difficult. The polymers of the present invention are at best semi-rigid and do not have the extremely high viscosity of rigid rod polymers. However, the polymer of the present invention has higher solubility and melt flow properties compared to rigid rod polyphenylene, and the polymer of the present invention also has the chemical and thermal stability of polyphenylene, resulting in lower K Thus, the side group is appropriately selected so that water absorbability is low.

  In order to reduce K and hygroscopicity to the lowest possible value while maintaining processability, it has been found desirable to reduce the number of side groups A and lower the polarity. For rigid rod-type polyphenylene, it is impossible to eliminate a large number of side groups without reducing the solubility to an impractical level. It has been found that by introducing flexible phenylene repeat units, particularly meta-phenylene repeat units, solubility and processability can be maintained with a smaller amount of solubilizing side groups. As a result, preferred meta-phenylene repeat units comprise at least about 10%, preferably at least about 20%, more preferably at least about 30%, and even more preferably at least about 40% of the total repeat units. Soluble copolymers are possible only if at least one of the two monomers has pendant side groups.

When the side group A is bonded only to the para-phenylene repeating unit, the polymer of the present invention has a structure represented by the following general formula.

Moreover, the structure represented by the following formula represents a case where each repeating unit has at most one side group A.

In another aspect of the invention, the copolymer comprises two different substituted meta-phenylene repeat units, the structure of which is represented by the following formula:

In another embodiment, the copolymer of the present invention has a structure represented by the following formula:

The following general structure indicates that the molar percentage of -Ar-repeat units is 80% and that the mole percentage of -Y-repeat units is 20%, and the sequence (random, block, etc.) is as described above. Not shown.

The specific structure of the formula below is a random copolymer of 1,4-phenylene (15 mol% of repeating units) and 1,3-phenylene (85 mol% of repeating units) with benzoyl addition.

Further, the specific structure of the formula below is an unlimited example of the polymer of the present invention.

上式中Ｘは塩素、臭素、ヨウ素又はスルホネートであり、好ましくは塩素である。
本発明の実施において有用なスルホネートの例には、制限するわけではないが、メタンスルホネート、フェニルスルホネート、トルエンスルホネート、トリフルオロメタンスルホネート及びフルオロスルホネートがある。 In the first formula, the benzoyl group is randomly substituted between the ortho position and the para position with respect to the carnation.
The polymers of the present invention are prepared from monomers selected from the following group:

In the above formula, X is chlorine, bromine, iodine or sulfonate, preferably chlorine.
Examples of sulfonates useful in the practice of the present invention include, but are not limited to, methane sulfonate, phenyl sulfonate, toluene sulfonate, trifluoromethane sulfonate, and fluorosulfonate.

The repeating units -Ar- and -Y- are derived from the corresponding dihalo, disulfonate or halosulfonate monomers. For example, 1,4-dichlorobenzene to 1,4-phenylene, 2,5-dichlorobenzophenone or 5-chloro-2-sulfoneoxymethylbenzophenone to 2-benzoyl-1,4-phenylene, and 5,8-dichloroquinoline 5,8-quinolinediyl is derived from
When Y is -Ph-Z-Ph- and Z is an amide, ester, imide, etc., the monomer XYX is a haloaryl acid such as chlorobenzoic acid, resorcinol, 1,4 Derived from diamines or diols such as butanediol, hexamethylenediamine and 1,4-phenylenediamine or haloarylamines or haloaryl alcohols such as meta-chloroaniline and meta-chlorophenol. Similarly, the monomer is derived from the condensation of a haloarylamine or haloaryl alcohol with a diacid such as adipic acid or terephthalic acid. When Y is an oligomer or polymer, the segment Y is derived from a haloaryl acid and a diacid and a diamine that are condensed to form a haloaryl endcapped polyamide, or is condensed to a haloarylene endcapped polyester. It is derived from a haloaryl acid forming a diacid and a diol. Other XYX type monomers are similarly prepared by condensation polymerization or addition polymerization of a haloaryl type endblocker.

で表されるダイマー、オリゴマー、ポリマー又はコポリマー化合物と、一般式：

で表される相補的に二官能性のモノマー、オリゴマー、ポリマー又はコポリマーとの反応により調製されるものであってもよく、上式中Ｅ及びＥ’は相補的に反応性の基である。反応性基Ｅを有するコポリマー化合物の一般式は、Ｅ−（−Ａｒ−／−Ａｒ’−）−Ｅ、Ｅ−（−Ａｒ−／−Ａｒ’−／−Ａｒ’’’−）−Ｅ及びＥ’−（−Ｙ−／−Ｙ’−）−Ｅ’等である。 Reduction using nickel (0) compounds as described in T. Kanbara, T. Kushida, N. Saito, I. Kuwajima, K. Kubota, and T. Yamamoto, Chemistry Letters, 1992, pages 583-586. The above-described monomers can be polymerized to form the polymers of the present invention by coupling or by nickel-catalyzed reductive coupling as described in above-mentioned 457 or US Pat. No. 5,241,044. .
The polymer of the present invention has the general formula:

A dimer, oligomer, polymer or copolymer compound represented by the general formula:

Wherein E and E ′ are complementary reactive groups. In the above formula, E and E ′ are complementary reactive groups. The general formula of the copolymer compound having a reactive group E is E-(-Ar-/-Ar '-)-E, E-(-Ar-/-Ar'-/-Ar '''-)-E and E '-(-Y-/-Y'-)-E 'and the like.

Complementary reactive groups E and E ′ can be selected as examples from the same column in Table 1.

Thus, if E is —ArCO ₂ H and E ′ is —OH, the polymer is a polyester. When E is -F or -ArF, the fluoro group needs to be activated so that it is nucleophilically substituted by an electron withdrawing group on the same ring. Unrestricted examples of active electron withdrawing groups are benzoyl, phenylsulfonyl, 2-benzoxyazolyl, 2-quinolinyl and 4-quinolinyl.
The reaction represented by the following formula illustrates the formation of a block copolymer from E-Ar-E and E'-YE '.

The reaction represented by the following formula is prepared from two monomers of the E-Ar-E block and the E-Ph-E and E'-Ph-E 'type in which the copolymer of the present invention forms an -Y-block. The case where it is done is illustrated.

When-((Ar) _l (Y) _m ) _n -is formed from E- (Ar) _l -E and E'-YE ', an additional derived from E and E' There may be bridging groups or additional fractions of repeating units Y. These are not explicitly represented in the formula-((Ar) ₁ (Y) _m ) _n- . For example, in Scheme 1 above, there are additional isophthaloyl units (part of repeat unit Y) and two additional amino-1,3-phenylene units (groups derived from E group). The polymer that is the product of Scheme 1 can be considered to have a Y equal to poly (isophthalamide-1,3-phenylene).
Other E and E ′ will be apparent to those skilled in the art. It is a general requirement that E does not interfere with the formation of the reactive oligomer E- (Ar) -E and that E and E ′ react appropriately. Common protecting groups are those used in the preparation of E- (Ar) -E and are not limited to alkyl ether groups, tetrahydropyranyl ether groups, 2-alkoxy-isopropylidene ether groups, esters Groups, amide groups, t-butyl carbonate groups, trialkylsilyl groups and the like.
About 0.1 mole% of Y gives properties of the polymer, the observable effects, such as changing the melt flow properties or T _g has both practical importance for example. Even meta-arylene repeat units on the order of 0.1 mol% have a significant effect on the overall polymer properties. However, for many practical applications it is desirable to have meta-arylene repeat units in an amount greater than 0.1%, preferably greater than about 1%. For example, a polymer in which 1% of the repeat units are meta-arylene units has different mechanical properties than a polymer that does not have meta-arylene repeat units. The polymer properties are more closely related to the weight percent of Y than the mole percent of Y, but a range of about 0.1 mole percent to 99 mole percent is convenient and sufficient for the purposes of the present invention.

  In general, the solubility of a polymer is increased by introducing irregularities in the polymer backbone. Since polyarylene is generally a low solubility polymer, the present invention is convenient for preparing copolymers of polyarylene. The polyarylene copolymer can have one or more types of arylene repeat units of differently substituted types (ie, different A pendant groups) or differently catenated types (ie, meta and para). Polyarylene copolymers also have repeating units other than arylene. Incorporation of one or more types of repeat units increases the disorder of the polymer backbone, thereby increasing solubility. The side group A of the polymer of the present invention increases the solubility of the polyarylene skeleton. Unsubstituted polyarylenes, including poly (1,4-phenylene), poly (1,3-phenylene) and poly (1,4-phenylene-co-1,3-phenylene) are all advanced in common organic solvents. It is insoluble in water and its solubility decreases rapidly with increasing molecular weight. Only very low molecular weight unsubstituted polyarylenes are prepared because the growing polymer precipitates in solution and once precipitated the polymer no longer grows.

The side groups increase the solubility by increasing the entropy of the polymer chain, i.e. allowing more possible conformation in solution. The more flexible the side groups, the greater the polymer solubility. However printing, flexible side groups which reduces the T _g of the polymer, reduce the modulus, in order to increase the coefficient of coefficient of thermal expansion (CTE), high T _g, is required high modulus, and low CTE Undesirable for many applications such as composite structures of wiring boards and aircraft wings.
A polymer having side groups randomly arranged along the polymer main chain has higher solubility than a polymer having side groups regularly arranged along the main chain. Thus, homopolymers having random copolymers with different side groups and random regiochemistry (ie, not all head-to-head or head-to-head bonds) are compared to head-to-head homopolymers, for example. And has a high solubility. The side groups of the present invention are preferably randomly or partially randomly arranged at possible positions on the polymer backbone.

  The insolubility of polyarylene is partly due to the very high degree of folding in the solid state. Side groups that prevent polymer folding increase solubility. The side group is preferably located in the ortho position relative to the carnation site. Groups in the ortho position relative to the carnation site have a large steric repulsion to adjacent monomer units. This steric repulsion reduces the degree of folding in the solid state and increases the solubility by returning the twist of adjacent repeating units to a normal plane. If adjacent repeat units both have a heterocyclic side group in the ortho position (eg, have a heterocyclic group in the 2 and 2 'positions relative to the bond connecting the repeat units). ), The steric repulsion and torsion angles become very large and the solubility increases correspondingly. The side group of the present invention preferably has a side group in the ortho position relative to the carnation site. The polymer of the present invention does not necessarily have an ortho-position side group, but when 5% or more of the repeating units have an ortho-position side group, more preferably at least 10% of the -Ar-repeat units are in the ortho-position. More preferably, at least 25% of -Ar- repeating units have a side group at the ortho position, more preferably at least 50% of -Ar- repeating units have a side group at the ortho position. The solubility increases.

Side groups having a polarity similar to that of the solvent generally increase the solubility of the polymer. Side groups that have a very different polarity from the solvent actually reduce the solubility. Solvents useful for dissolving the polyarylene copolymers of the present invention include, but are not limited to, anisole, cresol, N-cyclohexyl pyrrolidone, dichlorobenzene, dimethyl sulfoxide, N, N-dimethylacetamide, N, N- Examples include dimethylformamide, formamide, N-methylacetamide, methylbenzoate, N-methylpyrrolidone, phenol, and tetramethylurea.
Another advantage of the copolymer is that some repeating units comprise specific chemical groups useful for modifying the properties of the resulting polymer. For example, some repeating units have pendant ester groups that can interact with the surface to change adhesion. Introducing 10% to 20% flexible groups into other rigid rod structures can impart higher melt flow properties and elongation at break. Copolymers containing para-phenylene groups and increased strength, copolymers containing unsubstituted meta-phenylene groups, increased melt flow properties, esters or amines (or other moderately reactive groups) substituted phenylene groups (meta and Copolymers with increased adhesion, including / or para) are particularly useful as matrix resins in adhesives and composites.

The copolymer of the present invention can be used as a molding material by itself or together with a filler, which is not limited to carbon, silica, graphite, talc, calcium carbonate, calcium sulfate, rubber, There are chopped fibers. The copolymers of the present invention can also be used as matrix resins in organic matrix composites. For example, a composite material may be produced by coating a fiber tow or fabric with the copolymer of the present invention, then laying up the prepreg tape or fabric on a mold and uniting the prepreg by applying heat and / or pressure. The
Methods known to those skilled in the art can be used to form the copolymers of the present invention in the form of fibers, films or sheets, including but not limited to melt spinning, spinning from solution, drying jets. There are wet spinning, extrusion method, inflation method, casting method and molding method. The fibers, films or sheets can be further processed by rolling, stamping, secondary forming or other methods known to those skilled in the art.

The heterocyclic repeat unit is basic and is protonated by a Bronsted acid to form a complex with a Lewis acid. The relative pK _a of the acid and a heterocyclic group determines the degree of protonation. If acid than the conjugate acid of the heterocyclic group has from about 2 small pK _a (stronger acidic) proton when approximately equal moles essentially about 99% of the heterocyclic groups are present It becomes. Preferably _the pK _a of the Bronsted acid, 2 small at most than the pK _a of the conjugate acid of heterocyclic group, more preferably be one less, and is most preferably not exceed a value of a heterocyclic group. One skilled in the art would be able to identify acids that would protonate or complex a given heterocyclic group and calculate or measure the degree of protonation or association.
Once the protonated or complexed heterocyclic repeat unit becomes more polar, it increases the solubility of the polymer in highly polar solvents. Polyarylenes with mostly protonated heterocyclic repeat units are soluble in highly polar solvents including, but not limited to, ethanol, methanol, water, and the like.
Protonated polyarylenes with heterocyclic repeat units are hydrogen exchange resins, as hydrogen exchange membranes for fuel containers and batteries, as ion exchange membranes for deionization of salt solutions, as proton transfer membranes, and solids Useful as an acid catalyst.

Polyarylene having a useful heterocyclic repeating units in forming the ionic polymers by complexation with protonation or Lewis acid, pK _a in the range of about -1 to about 12, preferably about 1-8 It may have a heterocyclic group with _a pKa, most preferably _a pKa of about 2-7. PK _a of less than -1 are useful for use in non-aqueous environments. Polymers having a heterocyclic repeating units having a pK _a of more than 12 is useful as an anion-exchange resin.
Bronsted acids useful in the practice of the present invention include, but are not limited to, acetic acid, formic acid, hydrobromic acid, hydrochloric acid, hydrofluoric acid, hydroiodic acid, methanesulfonic acid, trifluoromethanesulfone. Examples include acids, toluenesulfonic acid, nitric acid, perchloric acid, phosphoric acid, polyphosphoric acid, sulfuric acid, sulfurous acid, and trifluoroacetic acid.
Unrestricted examples of Lewis acids useful in the practice of this invention include aluminum tribromide, aluminum trichloride, boron tribromide, boron trichloride, boron trifluoride, cupric chloride, ferric chloride, three Examples include gallium chloride, tantalum pentafluoride, titanium tetrachloride, titanium tetrafluoride, and zinc chloride.
The invention is further illustrated by the following several non-limiting and exemplary embodiments. The choice and amount of reagents, temperature, reaction time are exemplary and should not be considered limiting in any way. Other approaches are contemplated that fall within the scope of the present invention.

Example
Example 1
(1: 1) Copolymerization of 3,5-dichloropyridine and 2,5-dichlorobenzophenone A 100 ml round bottom flask placed under a nitrogen atmosphere was charged with bis (triphenylphosphine) nickel chloride (0.535 g, 0 .818 mmol), sodium iodide (0.66 g, 4.4 mmol), triphenylphosphine (3.11 g, 11.9 mmol), 2,5-dichlorobenzophenone (5.65 g, 22.5 mmol), 3,5- Dichloropyridine (3.33 g, 22.5 mmol), anhydrous N-methylpyrrolidinone (55 ml) and activated zinc fines (4.28 g, 65.5 mmol) were added. The mixture was stirred at 60 ° C. overnight and filtered using a 10 micron polypropylene filter. The dope was then coagulated in 300 ml ethanol and then filtered. The resulting polymer was treated with 5% HCl in ethanol, filtered, and then washed thoroughly with ethanol and acetone. The polymer was then treated with 10 ml of ethanol containing 1 ml of triethylamine, filtered and then dried to give 5.2 g of product.

Example 2
(3: 2) Copolymerization of 3,5-dichloropyridine and 2,5-dichlorobenzophenone A 100 ml round bottom flask placed under a nitrogen atmosphere was charged with bis (triphenylphosphine) nickel chloride (0.535 g, 0.818 mmol). ), Sodium iodide (0.66 g, 4.4 mmol), triphenylphosphine (3.11 g, 11.9 mmol), 2,5-dichlorobenzophenone (5.65 g, 22.5 mmol), 3,5-dichloropyridine (4 g, 27 mmol), anhydrous N-methylpyrrolidinone (55 ml) and activated zinc fines (4.28 g, 65.5 mmol) were added. The mixture was stirred at 60 ° C. overnight. An ethanol solution containing 10 ml of 36% HCl was added to the mixture. After stirring overnight, the mixture was poured into 100 ml of ethanol, filtered and then washed thoroughly with ethanol and acetone. The filtered solid was stirred with 20 ml ethanol containing 3 ml triethylamine and then filtered. The cake was washed with ethanol and acetone and then dried overnight at 120 ° C. under reduced pressure to give 5.87 g of product.

Example 3
(4: 1) Copolymerization of 3,5-dichloropyridine and 2,5-dichlorobenzophenone A 100 ml round bottom flask placed under a nitrogen atmosphere was charged with bis (triphenylphosphine) nickel chloride (0.535 g, 0.818 mmol). ), Sodium iodide (0.66 g, 4.4 mmol), triphenylphosphine (3.11 g, 11.9 mmol), 2,5-dichlorobenzophenone (2.26 g, 9 mmol), 3,5-dichloropyridine (6 .38 g, 36 mmol), anhydrous N-methylpyrrolidinone (55 ml) and activated zinc fines (4.28 g, 65.5 mmol) were added. The mixture was stirred at 60 ° C. overnight. An ethanol solution containing 10 ml of 36% HCl was added to the mixture. After stirring overnight, the mixture was poured into 100 ml of ethanol, filtered and then washed thoroughly with ethanol and acetone. The filtered solid was stirred with 20 ml ethanol containing 3 ml triethylamine and then filtered. The cake was washed with ethanol and acetone and then dried overnight at 120 ° C. under reduced pressure to yield 4.5 g of product.

Example 4
(4: 1) Copolymerization of 3,5-dichloropyridine and 2,5-dichloro-4'-phenoxybenzophenone A 100 ml round bottom flask placed under a nitrogen atmosphere was charged with bis (triphenylphosphine) nickel chloride (0. 535 g, 0.818 mmol), sodium iodide (0.66 g, 4.4 mmol), triphenylphosphine (3.11 g, 11.9 mmol), 2,5-dichloro-4′-phenoxybenzophenone (2.75 g, 8 mmol) ), 3,5-dichloropyridine (5.33 g, 36 mmol), anhydrous N-methylpyrrolidinone (55 ml) and activated zinc fines (4.28 g, 65.5 mmol). The mixture was stirred at 60 ° C. overnight. An ethanol solution containing 10 ml of 36% HCl was added to the mixture. After stirring overnight, the mixture was poured into 100 ml ethanol, filtered and then washed thoroughly with ethanol. The filtered solid was stirred with 20 ml of ethanol containing 3 ml of triethylamine and then filtered. The cake was washed with ethanol and then dried overnight at 120 ° C. under reduced pressure to give 4.39 g of product.

Example 5
(1: 1) Copolymerization of 1,3-dichlorobenzene and 2,5-dichlorobenzophenone A 100 ml round bottom flask placed under a nitrogen atmosphere was charged with bis (triphenylphosphine) nickel chloride (0.727 g, 1.11 mmol). ), Sodium iodide (0.89 g, 5.97 mmol), triphenylphosphine (3.93 g, 15 mmol), anhydrous N-methylpyrrolidinone (55.6 ml) and activated zinc fines (3.68 g, 56.33 mmol). added. After the solution turned red, 2,5-dichlorobenzophenone (5.02 g, 20 mmol) and 1,3-dichlorobenzene (2.94 g, 20 mmol) were added. The mixture was stirred at 65 ° C. overnight. Concentrated hydrochloric acid (7 ml) was carefully added. The polymer solution was poured into 200 ml of ethanol and then filtered. The cake was first refluxed with ethanol for 10 minutes, then refluxed in acetone for an additional 10 minutes, filtered and then dried under reduced pressure to give 5 g of product.

Example 6
(7: 3) Copolymerization of 1,3-dichlorobenzene and 2,5-dichlorobenzophenone A 100 ml round bottom flask placed under a nitrogen atmosphere was charged with bis (triphenylphosphine) nickel chloride (0.727 g, 1.11 mmol). ), Sodium iodide (0.89 g, 5.97 mmol), triphenylphosphine (3.93 g, 15 mmol), anhydrous N-methylpyrrolidinone (55.6 ml) and activated zinc fines (3.68 g, 56.33 mmol). added. After the solution turned red, 2,5-dichlorobenzophenone (3.01 g, 12 mmol) and 1,3-dichlorobenzene (4.12 g, 28 mmol) were added. The mixture was stirred at 65 ° C. overnight. Concentrated hydrochloric acid (7 ml) was carefully added. The polymer solution was poured into 200 ml of ethanol and then filtered. The cake was first refluxed with ethanol for 10 minutes, then refluxed for a further 10 minutes in acetone, filtered, and then dried under reduced pressure to give 4.3 g of product.

Example 7
(4: 1) Copolymerization of 1,3-dichlorobenzene and 2,5-dichlorobenzophenone A 100 ml round bottom flask placed under a nitrogen atmosphere was charged with bis (triphenylphosphine) nickel chloride (0.393 g, 0.6 mmol). ), Sodium iodide (0.63 g, 4.2 mmol), triphenylphosphine (2.36 g, 9 mmol), anhydrous N-methylpyrrolidinone (40 ml) and activated zinc fines (4.2 g, 64.2 mmol) were added. . After the solution turned red, 2,5-dichlorobenzophenone (2.26 g, 9 mmol) and 1,3-dichlorobenzene (5.29 g, 36 mmol) were added. The mixture was stirred at 65 ° C. overnight. Concentrated hydrochloric acid (8 ml) was carefully added. The polymer solution was poured into 200 ml of ethanol and then filtered. The cake was first refluxed with ethanol for 10 minutes, then refluxed in acetone for an additional 10 minutes, filtered, and then dried under reduced pressure to give 4.2 g (96%) of product.

Example 8
(9: 1) Copolymerization of 1,3-dichlorobenzene and 2,5-dichlorobenzophenone A 100 ml round bottom flask placed under a nitrogen atmosphere was charged with bis (triphenylphosphine) nickel chloride (0.727 g, 1.11 mmol). ), Sodium iodide (0.89 g, 5.97 mmol), triphenylphosphine (3.93 g, 15 mmol), anhydrous N-methylpyrrolidinone (55.6 ml) and activated zinc fines (3.68 g, 56.33 mmol). added. After the solution turned red, 2,5-dichlorobenzophenone (1 g, 4 mmol) and 1,3-dichlorobenzene (5.29 g, 36 mmol) were added. The mixture was stirred at 65 ° C. overnight. Concentrated hydrochloric acid (7 ml) was carefully added. The polymer solution was poured into 200 ml of ethanol and then filtered. The cake was first refluxed with ethanol for 10 minutes, then refluxed in acetone for an additional 10 minutes, filtered, and then dried under reduced pressure to give 5.3 g (95%) of product.

Example 9
(7: 1: 2) copolymerization of 1,3-dichlorobenzene and 1,4-dichlorobenzene and 2,5-dichlorobenzophenone Into a 100 ml round bottom flask placed under a nitrogen atmosphere, bis (triphenylphosphine) chloride was added. Nickel (0.818 g, 1.25 mmol), sodium iodide (1.01 g, 6.71 mmol), triphenylphosphine (4.43 g, 16.9 mmol), anhydrous N-methylpyrrolidinone (48 ml) and activated zinc fines ( 4.14 g, 63.4 mmol) was added. After the solution turned red, 2,5-dichlorobenzophenone (2.26 g, 9 mmol) and 1,4-dichlorobenzene (0.66 g, 4.5 mmol) and 1,3-dichlorobenzene (4.63 g, 31.5 mmol) was added. The mixture was stirred at 65 ° C. overnight. Concentrated hydrochloric acid (7 ml) was carefully added. The polymer solution was poured into 200 ml of ethanol and then filtered. The cake was first refluxed with ethanol for 10 minutes, then refluxed in acetone for an additional 10 minutes, filtered and then dried under reduced pressure to give 4 g (91%) of product.

Example 10
Copolymerization of 1,3-dichlorobenzene and 1,4-dichlorobenzene with 2,5-dichlorobenzophenone (8: 1: 1) A 100 ml round bottom flask placed under a nitrogen atmosphere was charged with bis (triphenylphosphine) chloride. Nickel (0.523 g, 0.8 mmol), sodium iodide (0.84 g, 5.6 mmol), triphenylphosphine (3.15 g, 12 mmol), anhydrous N-methylpyrrolidinone (53 ml) and activated zinc fines (5. 6 g, 85.6 mmol) was added. After the solution turned red, 2,5-dichlorobenzophenone (1.51 g, 6 mmol) and 1,4-dichlorobenzene (0.88 g, 6 mmol) and 1,3-dichlorobenzene (7.06 g, 48 mmol) Was added. The mixture was stirred overnight at 65 ° C. and coagulated in 200 ml ethanol containing 10% hydrochloric acid. The polymer solution was filtered, washed thoroughly with hot ethanol and hot acetone and then dried under reduced pressure. Yield was quantitative.

Example 11
Copolymer of 2,5-dichlorobenzophenone (85%) and 1,3-di (4-chloro) benzoyl-benzene (15%) A 2 liter three-necked round bottom flask equipped with a nitrogen inlet valve was charged with bis (tri Phenylphosphine) nickel chloride 10.66 g, sodium iodide 12.97 g, triphenylphosphine 53.38 g, activated zinc fine powder 54.01 g, 2,5-dichlorobenzophenone 127.5 g, 1,3-di (4-chloro) 34.69 g of benzoylbenzene and 815 ml of anhydrous N-methylpyrrolidone (NMP) were charged. The mixture was stirred at 60 ° C. for 16 hours under a nitrogen atmosphere. The polymer dope was diluted with 500 ml of NMP, coagulated with 4.0 liters of 10% hydrochloric acid / ethanol solution, and the resulting solution was stirred for 4 hours. The precipitated polymer was collected by filtration and then boiled continuously in 1.0 liter of ethanol and 1.0 liter of acetone for 1 hour. The solid was filtered again and then dried in a vacuum oven at 60 ° C. for 4 hours and then at 120 ° C. for 16 hours (Yield = 92%). MW _W = 52,300; 5 wt% reduction by thermogravimetric analysis (TGA) = 418 ° C .; glass transition temperature = 162 ° C .; intrinsic viscosity = 0.72 (40 ° C./0.05 M lithium bromide / NMP) The flexural modulus of the compression molded panel = 1.10 MSI; and the flexural strength of the compression molded panel = 12.7 KSI.

Example 12
Copolymer with 2,5-dichlorobenzophenone (80%), 1,3-dichlorobenzene (10%) and 4,3′-dichlorobenzanilide (10%) 1.0 liter three-neck equipped with a nitrogen inlet valve In a round bottom flask, 8.708 g of bis (triphenylphosphine) nickel chloride, 10.455 g of sodium iodide, 43.607 g of triphenylphosphine, 44.121 g of activated zinc fine powder, 98.03 g of 2,5-dichlorobenzophenone, 4, Charged 12.99 g of 3'-dichlorobenzanilide and 666 ml of anhydrous N-methylpyrrolidone (NMP). The mixture was stirred at 70 ° C. for 16 hours under a nitrogen atmosphere. The polymer dope was diluted with 500 ml of NMP, coagulated with 4.0 liters of 10% hydrochloric acid / ethanol solution, and the resulting solution was stirred for 4 hours. The precipitated polymer was collected by filtration and then washed successively in 100 ml hot ethanol and 100 ml hot acetone. The solid was filtered again and then dried in a vacuum oven at 60 ° C. for 4 hours and then at 120 ° C. for 16 hours (Yield = 95%). MW _W = 90,600; 5 wt% reduction by thermogravimetric analysis (TGA) = 470 ° C .; glass transition temperature = 172 ° C .; intrinsic viscosity = 1.26 (40 ° C./0.05 M lithium bromide / NMP) The flexural modulus of the compression molded panel = 1.20 MSI; and the flexural strength of the compression molded panel = 40.8 KSI.

Example 13
Copolymer of 2,5-dichlorobenzophenone (85%) and 3-chlorophenyl 4-chloro-benzoate (15%) A 250 ml round bottom flask was charged with 2.132 g of bis (triphenylphosphine) nickel chloride, sodium iodide. 56 g, 10.68 g of triphenylphosphine, 10.8 g of activated zinc fine powder, 25.51 g of 2,5-dichlorobenzophenone, 4.788 g of 3-chlorophenyl 4-chlorobenzoate, and 64 ml of anhydrous N-methylpyrrolidone (NMP) . The flask was equipped with a nitrogen inlet valve, and the mixture was stirred at 70 ° C. for 16 hours under a nitrogen atmosphere. The polymer dope was coagulated in 400 ml hydrochloric acid / ethanol solution and the resulting solution was then stirred for 4 hours. The precipitated polymer was collected by filtration and then boiled continuously in 100 ml ethanol and 100 ml acetone for 1 hour. The solid was filtered again and then dried in a vacuum oven at 60 ° C. for 4 hours and then at 120 ° C. for 16 hours (Yield = 90%). MW _W = 85,000; 5 wt% reduction by thermogravimetric analysis (TGA) = 444 ° C .; glass transition temperature = 159 ° C .; intrinsic viscosity = 1.16 (40 ° C./0.05 M lithium bromide / NMP) Met.

Example 14
Copolymer of 2,5-dichlorobenzophenone (50%) and 4,3'-dichlorobenzanilide (50%) A 100 liter round bottom flask was charged with 0.533 g of bis (triphenylphosphine) nickel chloride, sodium iodide 0 .64 g, 2.678 g of triphenylphosphine, 2.70 g of activated zinc fine powder, 3.752 g of 2,5-dichlorobenzophenone, 3.976 g of 4,3′-dichlorobenzanilide, and 41 ml of anhydrous N-methylpyrrolidone (NMP) Filled. The flask was equipped with a nitrogen inlet valve and the mixture was stirred at 65 ° C. for 16 hours under a nitrogen atmosphere. The polymer dope was coagulated in 250 ml of hydrochloric acid / ethanol solution and the resulting solution was then stirred for 4 hours. The precipitated polymer was collected by filtration and then boiled continuously in 100 ml ethanol and 100 ml acetone for 1 hour. The solid was filtered again and then dried in a vacuum oven at 60 ° C. for 4 hours and then at 120 ° C. for 16 hours (yield = 93%). MW _W = 40,500.

Example 15
Copolymer of 2,5-dichlorobenzophenone (50%), 1,4-dichlorobenzene (35%) and 3,3′-dichlorobenzanilide (15%) into a 100 liter round bottom flask, bis (triphenylphosphine) Nickel chloride 0.533 g, sodium iodide 0.64 g, triphenylphosphine 2.678 g, activated zinc fine powder 2.70 g, 2,5-dichlorobenzophenone 3.752 g, 1,4-dichlorobenzene, 3,3′-dichloro 1.193 g of benzanilide and 41 ml of anhydrous N-methylpyrrolidone (NMP) were charged. The flask was equipped with a nitrogen inlet valve and the mixture was stirred at 65 ° C. for 16 hours under a nitrogen atmosphere. The polymer dope was coagulated in 250 ml of hydrochloric acid / ethanol solution and the resulting solution was then stirred for 4 hours. The precipitated polymer was collected by filtration and then washed successively with 100 ml hot ethanol and 100 ml hot acetone. The solid was filtered again, then dried in a vacuum oven at 60 ° C. for 4 hours and then at 165 ° C. for 12 hours (Yield = 88%). MW _W = 47,200.

Example 16
Copolymer of 2,5-dichlorobenzophenone (90%) and 4,4'-di (4-chlorobenzoyl) diphenyl ether (10%) In a 250 liter round bottom flask, 1.998 g of bis (triphenylphosphine) nickel chloride Sodium iodide 2.399 g, triphenylphosphine 10.00 g, activated zinc fine powder 10.12 g, 2,5-dichlorobenzophenone 25.32 g, 4,4′-di (4-chlorobenzoyl) diphenyl ether 5.000 g, and Charged with 153 ml of anhydrous N-methylpyrrolidone (NMP). The flask was equipped with a nitrogen inlet valve and the mixture was stirred at 65 ° C. for 16 hours under a nitrogen atmosphere. The polymer dope was coagulated in 400 ml hydrochloric acid / ethanol solution and the resulting solution was then stirred for 4 hours. The precipitated polymer was collected by filtration and then washed successively with 100 ml hot ethanol and 100 ml hot acetone. The solid was filtered again and then dried in a vacuum oven at 60 ° C. for 4 hours and then at 170 ° C. for 16 hours (Yield = 91%). MW _W = 156,000; 5 wt% reduction by thermogravimetric analysis (TGA) = 507 ° C .; glass transition temperature = 170 ° C .; intrinsic viscosity = 2.18 (40 ° C./0.05 M lithium bromide / NMP) The flexural modulus of the compression molded panel = 0.811 MSI; and the flexural strength of the compression molded panel = 37.1 KSI.

Example 17
Film casting and protonation of the copolymer of Example 2 ((3: 2) copolymer from 3,5-dichloropyridine and 2,5-dichlorobenzophenone)
Polymer resin (4.0 g) was dissolved in formic acid (16 g). NMP (1 g) was poured onto a glass plate and passed under a blade to obtain a uniform film of the solution. The film was allowed to stand at room temperature for 2 hours and dried overnight at 70 ° C. under reduced pressure. The dried film was peeled from the glass plate and protonated in an acid bath containing a solution of sulfuric acid in methanol (1: 5, v: v). Protonation was performed at room temperature for 2.5 days. The film was then washed with methanol and stored in methanol. In each experiment, the film was washed with water and dried in air.

Example 18
From protonated 3,5-dichloropyridine and 2,5-dichlorobenzophenone (3: 2) produced the protonated copolymer film as a copolymer of film casting Example 17 (2.81 g) NMP (11.2 g This solution was used for film casting. The undried film was dried overnight at 50 ° C. under reduced pressure and then dried overnight at 70 ° C. under reduced pressure.

Example 19
3,5-dichloropyridine and 2,5-dichloro-benzophenone (3: 2) copolymer resin (2 g) from the protonated Example 17 the copolymer, of over a period of 4 days sulfate methanol (1: 5, v : Suspended in v). The resulting resin was filtered, washed with methanol and dried in air at room temperature. The partially air dried resin (2.9 g) showed strong acidity when tested with pH paper when wet.

Example 20
Activated Zinc Fine Powder Commercially available 325 mesh zinc fine powder is washed twice with (anhydrous) diethyl ether solution of hydrochloric acid and then twice with (anhydrous) diethyl ether and about 100-200 ° C. under inert atmosphere under reduced pressure. Activated zinc fine powder was obtained by drying for several hours. If agglomerates are formed during drying, the zinc fines are again sieved to -150 mesh. This material should be used immediately or stored under an inert atmosphere free of oxygen and moisture.

Example 21
Copoly- {1,4- (benzoylphenylene)}-{1,3- (5-methoxycarbonylphenylene)}-{1,3- (phenylene)}
In a 50 liter flask under a dry nitrogen atmosphere, anhydrous bis (triphenylphosphine) nickel chloride (II) (65 g; 0.099 mol), triphenylphosphine (343 g; 1.5 mol), fine activated zinc powder (412 g; 6. 3 mol), sodium iodide (63 g; 0.42 mol), and 4 liters of dry NMP were prepared and stirred at 50 ° C. for 5 minutes. A solution of 2,5-dichlorobenzophenone (1.000 g; 4.0 mol) and 1,3-dichlorobenzene (58 g; 0.39 mol) in 1.6 liters of dry NMP was heated to 50 ° C. and the mixture Was added with stirring. Then a solution of methyl-3,5-di-chlorobenzoate (122.5 g; 0.60 mol) in 500 ml NMP was slowly added to the mixture with vigorous stirring taking about 10 minutes. The temperature of the reaction mixture was monitored and maintained at a temperature below 95 ° C. with external cooling. After stirring at 60 ° C. overnight, the viscous polymer solution was diluted with 12 liters of fresh NMP and the residual zinc powder was dissolved by adding 60 ml of concentrated hydrochloric acid. After confirming that gas evolution ceased and all the zinc metal had dissolved, the mixture was poured into methanol to precipitate the polymer. The suspension was filtered and the precipitate was continuously extracted with methanol for 2 days and then with acetone for 1 day and dried in a vacuum oven at 120 ° C. overnight to be 767 g ( A polymer with a yield of 93%) was obtained. MW _W = 188,593.

Example 22
Copoly- {1,4- (benzoylphenylene)}-{1,3- (5-methoxycarbonylphenylene)}-{1,3- (5- (4-phenoxybenzoyl) phenylene)}
In a 3 liter flask under a dry nitrogen atmosphere, anhydrous bis (triphenylphosphine) nickel (II) chloride (12.0 g; 18.3 mmol), triphenylphosphine (70.0 g; 304 mmol), activated zinc fines (90. 0 g; 1,380 mmol), sodium iodide (10.0 g; 66.7 mmol), 2,5-dichlorobenzophenone (200 g; 796 mmol) and 3,5-dichloro-4′-phenoxybenzophenone (25 g; 73 mmol) in 700 ml NMP. ) Was prepared. A solution of chlorobenzene (3.87 g; 34.4 mmol) in 200 ml NMP was poured into the flask and the resulting mixture was immediately heated to 50 ° C. with vigorous stirring. After 15 minutes, a solution of methyl-3,5-di-chlorobenzoate (50.0 g; 244 mmol) and 3,5-dichloro-4′-phenoxybenzophenone (25 g; 73 mmol) in 100 ml of NMP was added dropwise. The temperature of the reaction mixture was monitored and maintained at a temperature below 95 ° C. with external cooling. After stirring at 60 ° C. overnight, the viscous polymer solution was diluted with 350 ml fresh NMP and the residual zinc powder was dissolved by adding 40 ml concentrated hydrochloric acid. After confirming that gas evolution ceased and all the zinc metal was dissolved, the mixture was poured into 4 liters of methanol to precipitate the polymer. The suspension was filtered and the precipitate was continuously extracted with 1: 1 methanol / acetone overnight, then dried in an oven to give 184 g (84% yield) of polymer. It was. MW _W = 104,722.
45 g of the resin is placed in a mold and heated at 300 ° C. under a pressure of 70,23 kg / cm ² (1,000 psi) for 1 hour to produce a compression test coupon (3.5 × 5.0 × 0.125). ) Was manufactured. This sample was cut into test pieces and the bending properties were measured according to ASTM-D-790, and the results shown in the table below were obtained.

Example 23
Copoly- {1,4- (benzoylphenylene)}-{1,3- (5-aminophenylene)}
Under a dry nitrogen atmosphere, anhydrous bis (triphenylphosphine) nickel (II) chloride (1.4 g; 2.1 mmol), triphenylphosphine (5.5 g; 21 mmol), activated zinc fine powder (8.0 g; 122 mmol), A mixture of sodium iodide (1.0 g; 6.7 mmol), 2,5-dichlorobenzophenone (19 g; 76 mmol), 3,5-dichloroaniline (1.4 g; 8.7 mmol) and 90 ml NMP was placed in a 250 ml flask. Filled. The mixture was heated to 65 ° C. and stirred vigorously. The temperature of the reaction mixture was monitored and maintained at a temperature below 100 ° C. with external cooling. After stirring overnight at 75 ° C., the viscous polymer solution was diluted with 180 ml fresh NMP and the residual zinc powder was dissolved by adding 30 ml concentrated hydrochloric acid. After confirming that gas evolution ceased and all the zinc metal was dissolved, 500 ml of isopropanol was added to the solution to precipitate the polymer. The suspension was filtered and the precipitate was washed four times with boiling methanol and then dried in a vacuum oven at 120 ° C. overnight to yield 184 g (84% yield) of polymer. MW _W = 104,722. The nitrogen content according to the basic analytical method was: theoretical 0.83%; experimental 0.98%.

Example 24
Copoly- {1,4- (benzoylphenylene)}-{1,3- (5-pyridinyl)}
Under a dry nitrogen atmosphere, anhydrous bis (triphenylphosphine) nickel (II) chloride (16.5 g; 25 mmol), triphenylphosphine (75 g; 336 mmol), activated zinc fine powder (101 g; 1,545 mmol), sodium iodide ( A mixture of 13 g; 87 mmol), 2,5-dichlorobenzophenone (240 g; 956 mmol), 3,5-dichloropyridine (35 g; 237 mmol) and 240 ml NMP was charged into a 5 liter flask. The mixture was heated to 60 ° C. and stirred vigorously. The temperature of the reaction mixture was monitored and maintained at 82-89 ° C. with external cooling. After stirring overnight, the viscous polymer solution was diluted with 900 ml fresh NMP and the residual zinc powder was dissolved by adding 100 ml concentrated hydrochloric acid. After confirming that gas evolution ceased and all the zinc metal was dissolved, the mixture was added to methanol to precipitate the polymer. The suspension was filtered and the precipitate was extracted continuously using methanol for 2 days and then with acetone for 1 day and dried in a 115 ° C. vacuum oven overnight to obtain 184 g ( A polymer with a yield of 97%) was obtained. MW _W = 211,498.
Although the invention has been described with reference to preferred and exemplary embodiments, the invention is not limited thereto. Those skilled in the art will appreciate that various modifications can be made without departing from the scope of the invention as defined in the claims.

上式中−Ａｒ−は、下式で表されるアリーレン又はヘテロアリーレン繰返し単位の少なくとも１種である：

及び

Preferred embodiments of the present invention are shown below.
1. a copolymer comprising a structure represented by the following general formula:

In the above formula, -Ar- is at least one arylene or heteroarylene repeating unit represented by the following formula:

as well as

In the above formula,
1-3 of the aromatic CH groups may be optionally replaced by N;
The number average segment length of the arylene segment is greater than 2 and the number average segment length of the para-arylene repeat unit ranges from 1 to about 8;
The number average segment length of the meta-arylene repeat unit is greater than 1;
x is 0-4, pendant groups (A) are, -F, -CN, -CHO, -COR , -CR = NR ', - OR, -SR, -SO 2 R, -OCOR, -CO 2 R, —NRR ′, —N═CRR ′, —NRCOR ′, —CONRR ′ and R are independently selected, wherein R and R ′ are H, alkyl, substituted alkyl, aryl, substituted aryl, hetero Independently selected from the group consisting of aryl and substituted heteroaryl, and R and R ′ may be joined together;
Y is absent or is a divalent group selected from the group consisting of -Z-, -Z-Ph- and -Ph-Z-Ph-, wherein Z is -O-, -S-, -NR -, - O (CO) -, - O (CO 2) -, - (CO) NH (CO) -, - NR (CO) -, phthalimide, pyromellitimide, -CO -, - SO-, A divalent group selected from the group consisting of —SO ₂ —, —P (O) R—, —CH ₂ —, —CF ₂ —, and —CRR′—;
Ph is phenylene (ortho, meta or para-phenylene);
If Y is not present, there are at least two different -Ar-repeat units;
For every 100 repeating units, at least one has a pendant side group A; and n is a number greater than about 4.

5. Ａが、アルキル、アリール、アルキルケトン、アリールケトン、アルコキシ、アリーロキシ、アルキルエステル、アリールエステル、アルキルアミド及びアリールアミドからなる群より選ばれる上記４記載のポリマー。
6. Ａが、アセチル、ベンゾイル、カルボメトキシ、ホルミル、フェノキシ、フェノキシベンゾイル及びフェニルからなる群より選ばれる上記５記載のポリマー。
7. メタ−フェニレン繰返し単位が繰返し単位の１０％を超える量を構成している上記４記載のポリマー。
8. メタ−フェニレン繰返し単位が繰返し単位の２０％を超える量を構成している上記４記載のポリマー。
9. メタ−フェニレン繰返し単位が繰返し単位の５０％を超える量を構成している上記４記載のポリマー。 2. The polymer according to 1 above, wherein A is selected from the group consisting of alkyl, aryl, alkyl ketone, aryl ketone, alkoxy, aryloxy, alkyl ester, aryl ester, alkylamide and arylamide.
3. The polymer according to 2 above, wherein A is selected from the group consisting of acetyl, benzoyl, carbomethoxy, formyl, phenoxy, phenoxybenzoyl and phenyl.
4. The polymer according to 1 above, wherein Y is absent and the polymer has a structure represented by the following formula:

5. The polymer according to 4 above, wherein A is selected from the group consisting of alkyl, aryl, alkyl ketone, aryl ketone, alkoxy, aryloxy, alkyl ester, aryl ester, alkylamide and arylamide.
6. The polymer according to 5 above, wherein A is selected from the group consisting of acetyl, benzoyl, carbomethoxy, formyl, phenoxy, phenoxybenzoyl and phenyl.
7. The polymer of claim 4 wherein the meta-phenylene repeat unit comprises more than 10% of the repeat unit.
8. The polymer of claim 4 wherein the meta-phenylene repeat unit comprises more than 20% of the repeat unit.
9. A polymer as described in 4 above, wherein the meta-phenylene repeat units comprise more than 50% of the repeat units.

11. Ｙが存在せず、且つポリマーが下式で表される構造を有する上記１記載のポリマー：

上式中Ａ’は、−Ｆ、−ＣＮ、−ＣＨＯ、−ＣＯＲ、−ＣＲ＝ＮＲ’、−ＯＲ、−ＳＲ、−ＳＯ₂ Ｒ、−ＯＣＯＲ、−ＣＯ₂ Ｒ、−ＮＲＲ’、−Ｎ＝ＣＲＲ’、−ＮＲＣＯＲ’、−ＣＯＮＲＲ’及びＲから成る群より独立に選ばれ、前記Ｒ及びＲ’は、Ｈ、アルキル、置換アルキル、アリール、置換アリール、ヘテロアリール及び置換ヘテロアリールからなる群より独立に選ばれ、並びにＲ及びＲ’は一緒に結合していてよい；並びにｎは４を超える数である。 10. The polymer according to 1 above, wherein Y is absent and the polymer has a structure represented by the following formula:

11. The polymer according to 1 above, wherein Y is absent and the polymer has a structure represented by the following formula:

In the above formula, A ′ is —F, —CN, —CHO, —COR, —CR═NR ′, —OR, —SR, —SO ₂ R, —OCOR, —CO ₂ R, —NRR ′, —N ═CRR ′, —NRCOR ′, —CONRR ′ and R independently selected from the group consisting of H, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl More independently selected, and R and R ′ may be joined together; and n is a number greater than 4.

上式中Ａ及びＡ’は、−Ｆ、−ＣＮ、−ＣＨＯ、−ＣＯＲ、−ＣＲ＝ＮＲ’、−ＯＲ、−ＳＲ、−ＳＯ₂ Ｒ、−ＯＣＯＲ、−ＣＯ₂ Ｒ、−ＮＲＲ’、−Ｎ＝ＣＲＲ’、−ＮＲＣＯＲ’、−ＣＯＮＲＲ’及びＲから成る群より独立に選ばれ、前記Ｒ及びＲ’は、Ｈ、アルキル、置換アルキル、アリール、置換アリール、ヘテロアリール及び置換ヘテロアリールからなる群より独立に選ばれ、並びにＲ及びＲ’は一緒に結合していてよい；並びにｎは４を超える数である。 12. The polymer of claim 11, wherein A ′ is selected from the group consisting of alkyl, aryl, alkyl ketone, aryl ketone, alkoxy, aryloxy, alkyl ester, aryl ester, alkylamide, and arylamide.
13. The polymer according to 11 above, wherein A ′ is selected from the group consisting of acetyl, benzoyl, carbomethoxy, formyl, phenoxy, phenoxybenzoyl and phenyl.
14. The polymer of claim 11, wherein the meta-arylene repeating unit constitutes an amount exceeding 40% of the repeating unit.
15. The polymer according to 1 above, wherein Y is absent and the polymer has a structure represented by the following general formula:

In the above formula, A and A ′ are —F, —CN, —CHO, —COR, —CR═NR ′, —OR, —SR, —SO ₂ R, —OCOR, —CO ₂ R, —NRR ′, -N = CRR ', -NRCOR', -CONRR 'and R, independently selected from the group consisting of H, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl And R and R ′ may be bonded together; and n is a number greater than 4.

上式中Ａ及びＡ’は、−Ｆ、−ＣＮ、−ＣＨＯ、−ＣＯＲ、−ＣＲ＝ＮＲ’、−ＯＲ、−ＳＲ、−ＳＯ₂ Ｒ、−ＯＣＯＲ、−ＣＯ₂ Ｒ、−ＮＲＲ’、−Ｎ＝ＣＲＲ’、−ＮＲＣＯＲ’、−ＣＯＮＲＲ’及びＲから成る群より独立に選ばれ、前記Ｒ及びＲ’は、Ｈ、アルキル、置換アルキル、アリール、置換アリール、ヘテロアリール及び置換ヘテロアリールからなる群より独立に選ばれ、並びにＲ及びＲ’は一緒に結合していてよい；並びにｎは４を超える数である。
17. Ａがメトキシカルボニルであり、且つＡ’がベンゾイルである上記１６記載のポリマー。
18. ポリマーがブロックコポリマーであり、且つ繰返し単位Ｙが、ポリアミド、ポリアリーレート、ポリアリーレンオキシド、ポリカーボネート、ポリジメチルシロキサン、ポリエステル、ポリエーテルケトン、ポリフェニレン、置換ポリフェニレン、ポリフェニレンスルフィド及びポリスチレンからなる群より選ばれるオリゴマー又はポリマーセグメントから選ばれる上記１記載のポリマー。 16. The polymer according to 1 above, wherein Y is absent and the polymer has a structure represented by the following formula:

In the above formula, A and A ′ are —F, —CN, —CHO, —COR, —CR═NR ′, —OR, —SR, —SO ₂ R, —OCOR, —CO ₂ R, —NRR ′, -N = CRR ', -NRCOR', -CONRR 'and R, independently selected from the group consisting of H, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl And R and R ′ may be bonded together; and n is a number greater than 4.
17. The polymer according to 16 above, wherein A is methoxycarbonyl and A ′ is benzoyl.
18. The polymer is a block copolymer and the repeating unit Y is selected from the group consisting of polyamide, polyarylate, polyarylene oxide, polycarbonate, polydimethylsiloxane, polyester, polyetherketone, polyphenylene, substituted polyphenylene, polyphenylene sulfide and polystyrene. 2. The polymer according to 1 above, which is selected from selected oligomers or polymer segments.

であり、且つ数平均セグメント長さｍが約８未満である上記１８記載のポリマー。
20. 繰返し単位の５０％未満が−Ａｒ−繰返し単位である上記１９記載のポリマー。 19. -Ar- is

The polymer of claim 18 wherein the number average segment length m is less than about 8.
20. The polymer as described in 19 above, wherein less than 50% of the repeating units are —Ar— repeating units.

である上記１８記載のポリマー。
22. Ｙが、−（フェニレン−ＣＯＮＨ−フェニレン−ＮＨＣＯ）−フェニレン、−（フェニレン−ＣＯＮＨ−フェニレン）−、−（フェニレン−ＣＯＯ−フェニレン−ＯＣＯ）−フェニレン−、−（フェニレン−カルボニル）−フェニレン−、及び−（フェニレン−カルボニル−フェニレン−オキソ−フェニレン−カルボニル−フェニレン）−からなる群より選ばれる上記１記載のポリマー。
23. 繰返し単位Ｙが、−（フェニレン−ＣＯＮＨ−フェニレン−ＮＨＣＯ）_m −フェニレン、−（フェニレン−ＣＯＮＨ）_m −フェニレン−、−（フェニレン−ＣＯＯ−フェニレン−ＯＣＯ）_m −フェニレン−、−（フェニレン−カルボニル）_m −フェニレン−及び−（フェニレン−カーボネート−フェニレン−２，２−イソプロピリデン−カーボネート）_m −フェニレン−からなる群より選ばれるブロックを形成している上記１記載のポリマー。
24. Ｙが−Ｐｈ−Ｚ−Ｐｈ−の構造を有し、前記Ｚが、−（ＣＯ）ＮＨ−、−（ＣＯ）Ｏ−、−Ｃ（＝ＮＣ₆ Ｈ₅）−、−（ＣＯ）−及び−ＳＯ₂ −からなる群より選ばれる二価の基である上記１記載のポリマー。 21. -Ar- is

19. The polymer according to 18 above.
22. Y is-(phenylene-CONH-phenylene-NHCO) -phenylene,-(phenylene-CONH-phenylene)-,-(phenylene-COO-phenylene-OCO) -phenylene-,-(phenylene-carbonyl) -phenylene 2. The polymer according to 1 above, selected from the group consisting of-and-(phenylene-carbonyl-phenylene-oxo-phenylene-carbonyl-phenylene)-.
23. repeating unit Y is - (phenylene -CONH- phenylene -NHCO) _m - phenylene, - (phenylene -CONH) _m - phenylene -, - (phenylene -COO- phenylene --OCO) _m - phenylene -, - (phenylene - carbonyl) _m - phenylene - and - (phenylene - carbonate - phenylene-2,2-isopropylidene - carbonate) _m - phenylene - polymers of claim 1, wherein the forming the block selected from the group consisting of.
24. Y has the structure of -Ph-Z-Ph-, wherein Z is, - (CO) NH -, - (CO) O -, - C (= NC 6 H 5) -, - (CO) _2. The polymer according to 1 above, which is a divalent group selected from the group consisting of — and —SO ₂ —.

上式中Ｐｈ’は１，２−、１，３−、又は１，４−フェニレンである。
26. 少なくとも１種のアリーレン繰返し単位−Ａｒ−が窒素含有ヘテロアリーレンである上記１記載のポリマー。
27. 上記２６記載のポリマー及び酸を含んでなるポリマー組成物。 25. Y has the structure of -Ph-Z-Ph-, wherein Z is, - (CO) OPh'O (CO ) -, - (CO) OPh'C (CH 3) 2 Ph'O (CO )-,-(CO) Ph'OPh '(CO)-, and the polymer according to 1 above, which is a divalent group selected from the group consisting of the following formulas:

In the above formula, Ph ′ is 1,2-, 1,3-, or 1,4-phenylene.
26. The polymer according to 1 above, wherein at least one arylene repeating unit -Ar- is a nitrogen-containing heteroarylene.
27. A polymer composition comprising the polymer according to 26 above and an acid.

29. Ａが、アセチル、ベンゾイル、カルボメトキシ、ホルミル、フェノキシ、フェノキシベンゾイル及びフェニルからなる群より選ばれる上記２８記載のポリマー。
30. 上記２８記載のポリマー及び酸を含んでなるポリマー組成物。
31. 前記酸が、酢酸、蟻酸、臭化水素、塩化水素、フッ化水素、ヨウ化水素、メタンスルホン酸、トリフルオロメタンスルホン酸、硝酸、過塩素酸、リン酸、ポリリン酸、硫酸、亜硫酸、トルエンスルホン酸及びトリフルオロ酢酸からなる群より選ばれる上記３０記載の組成物。 28. The polymer according to 1 above, wherein the polymer has a structure represented by the following formula:

29. The polymer as described in 28 above, wherein A is selected from the group consisting of acetyl, benzoyl, carbomethoxy, formyl, phenoxy, phenoxybenzoyl and phenyl.
30. A polymer composition comprising the polymer according to 28 and an acid.
31. The acid is acetic acid, formic acid, hydrogen bromide, hydrogen chloride, hydrogen fluoride, hydrogen iodide, methanesulfonic acid, trifluoromethanesulfonic acid, nitric acid, perchloric acid, phosphoric acid, polyphosphoric acid, sulfuric acid, sulfurous acid, 31. The composition according to 30 above, selected from the group consisting of toluenesulfonic acid and trifluoroacetic acid.

33. Ｅが、塩酸、アミン、アリールアルコール、アリールアミン、アリール酸塩化物、アリールカルボン酸、アリールフルオリド、カルボン酸、エポキシド、フルオリド、ヒドロキシ、イソシアネート及びシリルクロリドからなる群より選ばれる上記３２記載の方法。
34. Ｅ’が塩酸、アミン、アリールアルコール、アリールアミン、アリール酸塩化物、アリールカルボン酸、アリールフルオリド、カルボン酸、エポキシド、フルオリド、ヒドロキシ、イソシアネート及びシリルクロリドからなる群より選ばれる上記３２記載の方法。 32. An oligomer or polymer polyphenylene having a structure represented by the following formula reacts with a complementary divalent monomer E ′-(Y) _m -E ′, and E and E ′ are complementary 2. The method for producing a composition according to 1 above, which is a reactive group.

33. The 32 above, wherein E is selected from the group consisting of hydrochloric acid, amine, aryl alcohol, arylamine, aryl acid chloride, aryl carboxylic acid, aryl fluoride, carboxylic acid, epoxide, fluoride, hydroxy, isocyanate, and silyl chloride. the method of.
34. The 32 above, wherein E ′ is selected from the group consisting of hydrochloric acid, amine, aryl alcohol, arylamine, aryl acid chloride, aryl carboxylic acid, aryl fluoride, carboxylic acid, epoxide, fluoride, hydroxy, isocyanate and silyl chloride. the method of.

35. The method according to 32 above, wherein E is selected from the group consisting of aryl fluoride and fluoride, and E ′ is an alcohol anion.
36. The method according to 32 above, wherein E is selected from the group consisting of hydrochloric acid, aryl acid chloride, aryl carboxylic acid and carboxylic acid, and E ′ is selected from the group consisting of hydroxy and amine.
37. The method according to 32, wherein E is selected from the group consisting of amine, aryl alcohol, arylamine, and hydroxy, and E ′ is selected from the group consisting of hydrochloric acid, carboxylic acid, epoxide, isocyanate, and silyl chloride.
38. The method according to 32 above, wherein l is 1.
39. The method according to 32 above, wherein l is a number ranging from 2 to 200.
40. The method according to 32, wherein l is a number in the range of 1 to 10, and m is a number in the range of 1 to 100.

Claims (4)

Polymer represented by the following general formula:

In the above formula, A ′ is —F, —CN, —CHO, —COR, —CR═NR ′, —OR, —SR, —SO ₂ R, —OCOR, —CO ₂ R, —NRR ′, —N ═CRR ′, —NRCOR ′, —CONRR ′ and R independently selected from the group consisting of H, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl and substituted heteroaryl More independently selected, and R and R ′ may be bonded together; and n is a number greater than 4 and an amount of meta-phenylene repeat units greater than 20% of the repeat units. )   The polymer of claim 1 wherein the meta-phenylene repeat unit comprises more than 50% of the repeat unit.   The polymer of claim 1 wherein A 'is phenoxybenzoyl. An oligomer or polymer polyphenylene having a structure represented by the following formula is substituted with complementary divalent monomers E ′-(Y) _m -E ′ (wherein E and E ′ are complementary reactive groups). The method for producing a copolymer according to claim 1, comprising:

(In the formula, n is 1 to 10, m is 1 to 100, x is 0 to 4, E ′ is an acid chloride, amine, aryl alcohol, arylamine, aryl acid chloride, arylcarboxylic acid, aryl fluoride, carvone Selected from the group consisting of acids, epoxides, fluorides, hydroxys, isocyanates and silyl chlorides, and E is selected from the group consisting of amines, aryl alcohols, arylamines and hydroxys.)