JPH11209462A - Preparation of polyquinoline block copolymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the title composition capable of exhibiting chemical and physical properties which are not attained by a polyquinoline homopolymer by reacting a first reaction mixture obtained by the reaction of a specific three kinds of aromatic compounds, with a second mixture comprising three other aromatic compounds. SOLUTION: An aromatic compound (A) of formula I or formula II containing two ortho-aminocarbonyl functional groups connected to the aromatic nucleus, an aromatic compound (B) of formula III or the like containing two methyleneketone functional groups connected to the aromatic nucleus and an aromatic compound (C) of formula IV or the like containing one pair of one ortho-aminocarbonyl functional group and one methyleneketone functional group both connected to the aromatic nucleus are mixed in a ratio such that the total mole number of the component A is equal to the total mole number of the component B to obtain a first reaction mixture. A second reaction mixture comprising the components A, B and C which are not employed in the first step is added to and reacted with this reaction mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a mixture of a copolymer material containing a characteristic quinoline-type structure and polyquinoline polymers. The present invention further relates to a method for producing the above-mentioned polymer compound.

[0002]

BACKGROUND OF THE INVENTION U.S. Pat. No. 4,000,187 discloses polymer compositions consisting of recurring substituted quinoline groups and a process for preparing such polymers. As described in this patent, polyquinoline homopolymers can be prepared from the reaction of the following AA-type compounds (a) and BB-type compounds (b). (A) AA type compound group

[0003]

Embedded image Wherein R is hydrogen or aryl; and Ar,
Ar ′ and Ar ″ are aryl groups), wherein the aromatic aminocarbonyl has two sets of orthoaminocarbonyl functions attached to the aromatic nucleus. (B) BB type compound group

[0004]

Embedded image (Wherein R is hydrogen or aryl, R ′ is aryl, and Ar ″ and Ar ′ ″ are aryl groups).

[0005] Thereafter, the literature (JKStille, Macromolecules, 1981, 14, 870-880)
The related polyquinoline polymer has the formula:

[0006]

Embedded image Wherein R is hydrogen or aryl, R ′ is aryl, and Ar ′, Ar ″ and Ar ″
AB is an aryl group represented by
Prepared from a reaction with one compound selected from the AB type compound group consisting of an aromatic compound containing one methylene ketone functional group and a set of orthocarbonyl functional groups attached to an aromatic nucleus, selected from the group of type compounds It was reported that it was possible.

The methods disclosed in US Pat. No. 4,000,187 and the above-mentioned references relate to the preparation of various polyquinoline polymers with different physical properties. Most of the above-mentioned polymers are homopolymers. That is, a regularly repeating monomer that can be depicted mostly as -DDDDDD- or-(D) n-, where D represents a repeating monomer unit. Polymers containing body units. In such polymers, the monomer units are linked to two equal adjacent monomer units,
Consists of at least one quinoline moiety, with or without substituents. Most homopolymers are prepared by reacting a single AA compound with an equimolar amount of a single BB compound.

[0008] Some of the polyquinoline homopolymers previously disclosed or reported in the literature are rigid rod polyquinoline polymers. Rigid rod polymers, for example, have a rigid rod skeleton formed from a plurality of monomer units linked by parallel, covalent bonds, such as carbon-carbon covalent bonds, and between the monomer units. The long axis of all covalent bonds is defined as being substantially parallel, resulting in a polymer backbone that is linear and substantially linear. Hard rod polyquinolines have the following chain linkages:

[0009]

Embedded image Where X and Y indicate a direct covalent bond to an adjacent quinoline unit, or X and Y can be any group that allows a substantially linear bond to an adjacent quinoline group. Consists of quinoline units, which may or may not have substituents, which are linked in an extended polymer chain via a covalent bond as in For example, X and Y can be 1,4-phenylene or 4,4'-biphenyl. All polyquinoline homopolymers not included in the genus of rigid rod polyquinoline homopolymers are referred to as non-rigid rod polyquinoline homopolymers.

The specific AA used as starting material for the preparation of any specific polyquinoline homopolymer
The type, BB type and AB type compounds determine whether the resulting polymer is a rigid rod polyquinoline homopolymer or a non-rigid rod polyquinoline homopolymer. Accordingly, precursors of polyquinoline polymers are divided into compounds that can be precursors of rigid rod polyquinoline polymers or compounds that cannot be precursors of rigid rod polyquinoline polymers. Compounds that can be precursors of polyquinoline polymers are referred to as "hard rod precursor compounds", i.e., hard rod AA type compounds, hard rod BB type compounds, or hard rod AB type compounds. Similarly, compounds that cannot be precursors to rigid rod polyquinoline polymers are "non-rigid rod precursor compounds", ie, non-rigid rod AA, non-rigid rod BB, or non-rigid rod AB compounds. It is called a type compound. Certain combinations of rigid rod precursor compounds result in non-rigid rod polyquinoline homopolymers, for example,

[0011]

Embedded image Wherein the substituent Ph is defined as a phenyl group (C ₆ H ₅ ).

According to US Pat. No. 4,000,187, rigid rod polyquinoline homopolymers can be prepared by reacting a single rigid rod type AA compound with an equivalent amount of a single rigid rod type BB compound. Combinations in which at least one of the compounds in any other combination of AA and BB type compounds is a non-rigid rod compound will result in the formation of a non-rigid rod polyquinoline homopolymer. Similarly, the use of a rigid rod AB type compound results in a rigid rod polyquinoline homopolymer, while the use of a non-rigid rod AB type compound results in a non-rigid rod polyquinoline homopolymer.

[0013] Various rigid rod and non-rigid rod polyquinoline homopolymers are both disclosed in US Patent No. 4,000,187.
And can be prepared according to the methods disclosed in both the above references and the above-mentioned references. Such homopolymers exhibit a wide range of physical properties. The contrast between rigid rod polyquinoline homopolymers and non-rigid rod polyquinoline homopolymers is particularly striking. Most hard rod polyquinoline polymers dissolve only in strong acid solvents, exhibit particularly high melting points and decomposition temperatures, and cannot be melted.
In contrast, some non-rigid rod polyquinoline homopolymers dissolve in common organic solvents, exhibit a significantly lower glass transition temperature than in rigid rod polyquinoline homopolymers, and are melted to produce fibers, etc. It can be.

The number of different polyquinoline polymers that can be achieved is limited by the number of AA, BB, and AB type compounds. Further, the range of physical properties that can be achieved with polyquinoline homopolymers can be limited by the number of homopolymers that can be prepared. For example, rigid rod polyquinoline homopolymers are expected to be particularly useful in applications requiring excellent mechanical strength.
However, the applications of rigid rod polyquinoline homopolymers will be very limited due to the difficulty in processing such materials. There are no known rigid rod polyquinoline homopolymers that can be prepared from conventional organic solvents or melt processed.

Therefore, (1) other than homopolymers,
Polyquinoline polymers that can be used to prepare high quality, high temperature resistant moldable and laminate moldable resins, adhesive compositions, films, and fibers; (2) Chemical and physical properties not achievable with polyquinoline homopolymers Polyquinoline polymers expressing (3) a method for preparing a copolymer of polyquinoline polymers, (4) a method for preparing a multi-block polyquinoline copolymer, (5) a method for preparing a triblock polyquinoline copolymer, 6) It is desired to provide a method for preparing a mixture of polyquinoline polymers.

[0016]

The first means for solving the above problems is as follows: (a) In the primary stage, (1) one or more of the following AA type compounds, and one or more of the following BB type compounds Compounds and one or more of the following AB-type compounds; (2) one or more of the following AA-type compounds and one or more of the following three or more different AA-type compounds and BB-type compounds: The following BB type compounds; and (3) two or more of the following AB
When the AA type and BB type compounds are used in the type compounds, the total number of moles of the AA type compounds is
Preparing a primary reaction mixture of compounds selected from the group equal to the total number of moles of type compounds, and reacting the primary mixture for a selected time to provide a reacted primary mixture; And after this selection time, (b) in a second stage, to the reacted primary mixture, add a secondary mixture of compounds to provide a secondary reaction mixture, wherein the secondary mixture of compounds comprises: (1) One or more of the following AA type compounds,
One or more of the following BB-type compounds, and one or more of the following AB
Type compounds; (2) one or more of the following AA in which the number of different AA type compounds and BB type compounds is 3 or more
Type compounds and one or more of the following BB type compounds; and
(3) two or more of the following AB-type compounds, wherein the secondary mixture of the above-mentioned compounds includes at least one of the following AA-type, BB-type or the following AB-type compounds not used in the first step; A method for producing a polyquinoline block copolymer composition, comprising reacting a reaction mixture for a selected time, wherein a second means for solving the above-mentioned problem is:
(a) The following AA-type compounds consisting of one or more non-rigid rods, the following BB-type compounds consisting of one or more non-rigid rods, and zero or one or more of the following AB-type compounds are mixed. Wherein the total number of moles of said non-rigid rod AA type compounds is equal to the total number of moles of said non-rigid rod BB type compounds, and said mixture is reacted for a primary selection time; (b) After a first selection time, the reaction mixture is subjected to the following AA-type compounds consisting of one or more hard rods, the following BB-type compounds consisting of one or more hard rods and zero or more hard rods And (c) continuing the reaction for a secondary selection time to produce a polyquinoline block copolymer composition comprising: The third The stage is composed of (a) a mixture of the following AA type compounds composed of one or more hard rods, the following BB type compounds composed of one or more hard rods, and the following AB type compounds composed of one or more rigid rods: Wherein the total number of moles of said hard rod AA type compounds is equal to the total number of moles of said hard rod BB type compounds, and said mixture is reacted for a primary selection time; (b) After the primary selection time, the reaction mixture is subjected to one or more non-rigid rods of the following AA type compounds, one or more non-rigid rods of the following BB type compounds and one or more non-rigid rods A method for producing a polyquinoline block copolymer composition, comprising: adding the following AB-type compounds composed of hard rods; and (c) continuing the reaction for a second selection time. 4th to do Means comprising: (a) the following AA-type compounds comprising one or more non-rigid rods, the following BB-type compounds comprising one or more non-rigid rods, and the following consisting of zero or one or more non-rigid rods: AB type compounds are mixed, and the total number of moles of the non-rigid rod AA type compounds in the non-rigid rod B is mixed.
Equalizing the total number of moles of type B compounds and reacting the mixture for a primary selection time; (b) after said primary selection time, one or more hard A method for producing a polyquinoline block copolymer composition, comprising: adding the following AB type compounds consisting of a rod; and (c) continuing the reaction for a second selection time. The fifth means for (a)
The following AA-type compounds consisting of one or more hard rods:
The following BB type compounds composed of one or more hard rods and the following AB type compounds composed of zero or one or more hard rods are mixed, and the total number of moles of the hard rod AA type compounds is mixed with the above. Equalizing the total number of moles of hard rod BB type compounds and reacting the mixture for a primary selection time; (b) after said primary selection time, one or more Adding a compound of the following AB type comprising a non-rigid rod of (c), and (c) continuing the reaction for a secondary selection time, a method for producing a polyquinoline block copolymer composition, The sixth means for solving the above is that (a) the following AA type compounds comprising one or more non-rigid rods, the following BB type compounds comprising one or more non-rigid rods, and zero or one or more types Non-rigid rod The following AB type compounds are mixed, wherein the total number of moles of the non-rigid rod AA type compounds is equal to the total number of moles of the non-rigid rod BB type compounds, and the viscosity of the reaction mixture is Reacting the mixture until it indicates that the desired average molecular weight has been reached, (b) after the desired average molecular weight has been achieved, the following AA-type compounds consisting of one or more hard rods, The following BB type compounds composed of the above hard rods and the following AB composed of zero or one or more types of hard rods
A method for producing a polyquinoline block copolymer composition, comprising: adding a type compound to a reaction mixture; and (c) continuing the reaction for a second selection time. Seventh means are: (a) the following AA type compounds composed of one or more hard rods, the following BB type compounds composed of one or more rigid rods, and the following AB composed of zero or one or more rigid rods: Type compounds, wherein the total moles of the hard rod AA type compounds are equal to the total moles of the hard rod BB type compounds, and the viscosity of the reaction mixture is the desired average polymer molecular weight. Reacting this mixture until it indicates that the desired average molecular weight has been achieved,
The following AA type compounds comprising one or more non-rigid rods:
The following BB type compounds consisting of one or more non-rigid rods and the following AB consisting of zero or more non-rigid rods
A method for producing a polyquinoline block copolymer composition, comprising: adding a type compound; and (c) continuing the reaction for a second selection time. Means include: (a) the following AA type compounds consisting of one or more non-rigid rods, the following BB type compounds consisting of one or more non-rigid rods, and the following AB consisting of zero or more non-rigid rods: Type compounds, wherein the total moles of the non-rigid rod AA type compounds are equal to the total moles of the non-rigid rod BB type compounds, and the viscosity of the reaction mixture is a desired average. Reacting the mixture until it indicates that the polymer molecular weight has been reached, (b) after the desired average molecular weight has been achieved,
Adding to the reaction mixture the following AB-type compounds consisting of one or more hard rods; and (c)
A method for producing a polyquinoline block copolymer composition which is continued for the next selection time, wherein a ninth means for solving the above-mentioned problem is: (a) the following AA comprising one or more hard rods: Type compounds, the following BB type compounds composed of one or more hard rods, and the following AB type compounds composed of zero or one or more rigid rods are mixed, and a total of the hard rod AA type compounds is mixed therein. Reacting the reaction mixture until the number of moles equals the total number of moles of the hard rod BB type compounds and the viscosity of the mixture indicates that the desired average polymer molecular weight has been reached;
(b) after the desired average molecular weight is achieved, adding the following AB-type compounds consisting of one or more non-rigid rods to the reaction mixture; and (c) allowing the reaction to proceed for a second selection time. A method for producing a polyquinoline block copolymer composition, comprising: (a) the following AA-type compounds comprising one or more non-rigid rods: Mixing the following BB type compounds consisting of one or more non-rigid rods and the following AB type compounds consisting of zero or more non-rigid rods,
In this, the total number of moles of the non-rigid rod AA-type compounds is not made equal to the total number of moles of the non-rigid rod BB-type compounds. (B) after all of the non-rigid rod compounds have completely reacted, the following AA-type compounds comprising one or more rigid rods, comprising one or more rigid rods Adding to the reaction mixture the following AB-type compounds consisting of the following BB-type compounds and zero or more hard rods; and (c) continuing the reaction for a second selection time. An eleventh means for solving the above-mentioned problem is a method for producing a block copolymer composition, wherein (a) the following AA-type compounds comprising one or more hard rods, and one or more hard rods BB below Compounds, and zero or 1
The following AB type compounds composed of at least one kind of hard rod are mixed, and the total number of moles of the hard rod AA type compounds is not equal to the total number of moles of the hard rod BB type compounds. Reacting the mixture until all of the hard rod compounds have completely reacted; (b) after all of the hard rod compounds have completely reacted, comprise one or more non-rigid rods: AA type compounds, the following BB type compounds comprising one or more non-rigid rods and the following AB type compounds consisting of zero or more non-rigid rods are added to the reaction mixture; and (c) A method for producing a polyquinoline block copolymer composition comprising allowing the reaction to continue for a second selection time, wherein a twelfth means for solving the above-mentioned problems is as follows: ) Under one or more Mixing the AA compounds with one or more of the following AB compounds and forming a primary reaction mixture by reacting the mixture until all of the compounds are completely reacted; and (b) In a second stage, the reacted mixture is added to (1) one or more of the following A
A-type compounds, one or more of the following BB-type compounds, and 1
(2) one or more of the following AA compounds and one or more of the following BB compounds, wherein the number of the following different AA compounds and BB compounds is 3 or more: And (3) adding a secondary mixture selected from the group consisting of two or more of the following AB type compounds, wherein at least one of the AA, BB or AB type compounds in the secondary mixture is in the primary mixture. And the total number of the AA-type compounds and BB-type compounds in the secondary mixture is at least one, and the composite primary reacted mixture and the secondary mixture are selected. A method for producing a polyquinoline block copolymer composition comprising reacting for a set period of time, wherein a thirteenth means for solving the above-mentioned problem is (a)
In the first step, (1) mixing one or more of the following BB-type compounds with one or more of the following AB-type compounds, and reacting the mixture until all of the compounds are completely reacted; Forming a primary reaction mixture; and
(b) in a second stage, adding the reacted primary mixture to (1)
One or more of the following AA-type compounds, one or more of the following B-type compounds, and one or more of the following AB-type compounds; (2) The number of different following AA-type compounds and the following BB-type compounds is 3 One or more of the following AA-type compounds and one or more of the following BB-type compounds; and (3) two or more of the following ABs
Adding a secondary mixture selected from the group consisting of type compounds, wherein at least one of said AA, B in said secondary mixture
B or AB type compounds are not used in the primary mixture,
And in the secondary mixture, the AA-type compounds and A
A method for producing a polyquinoline block copolymer composition, wherein the total number of B-type compounds is one or more, and the combined primary reacted mixture and secondary mixture are reacted for a selected time. Yes, the first to solve the problem
The means (4) comprises (a) one or more of the following AA-type compounds,
One or more of the following BB-type compounds and zero or one or more of the following AB-type compounds are mixed, and the total number of moles of the AA-type compounds is made equal to the total number of moles of the BB-type compounds. Instead, reacting the mixture until the reaction is completed, (b) adding one or more of the following AB type compounds after the reaction is completed, and (c) completely reacting the reaction mixture. Reacting, the polyquinoline copolymer is a triblock copolymer having three polyquinoline segments, the primary segment is selected from the group consisting of polyquinoline homo-oligomer or polyquinoline co-oligomer, the remaining Are equal,
And selected from the group consisting of polyquinoline homo-oligomers and polyquinoline co-oligomers, but of a type different from the primary segment, wherein each of the secondary segments is 1
A method for producing a polyquinoline block copolymer composition characterized by being bonded to each end of the next segment, and a fifteenth means for solving the above-mentioned problem is
(a) The following AA type compounds composed of one or more hard rods, the following BB type compounds composed of one or more rigid rods, and the following AB type compounds composed of zero or one or more rigid rods are mixed. Wherein the total number of moles of the AA-type compounds is not equal to the total number of moles of the BB-type compounds, but the mixture is reacted until all of the hard rod compounds are completely reacted. (B) after all of the hard rod compounds have completely reacted, add the following AB type compounds consisting of one or more non-hard rods to the reaction mixture; (c) the reaction mixture Wherein the polyquinoline copolymer comprises a single rigid rod segment and two non-rigid rod segments, one of the non-rigid rod segments comprising the rigid rod segment. A method for producing a polyquinoline block copolymer composition characterized by being triblock copolymers bonded to each end of the above, wherein a sixteenth means for solving the above-mentioned problem is (a) A) AA type compounds comprising one or more non-rigid rods, BB type compounds comprising one or more non-rigid rods, and AB type compounds comprising zero or one or more non-rigid rods However, in this, the total number of moles of the non-rigid rod AA type compounds is not made equal to the total number of moles of the non-rigid rod BB type compounds. (B) after all of the non-hard rod compounds have completely reacted, add the following AB-type compounds comprising one or more hard rods to the reaction mixture. And (c) Fully reacting the reaction mixture, wherein the polyquinoline copolymers comprise a single non-rigid rod segment and two rigid rod segments, wherein each of the rigid rod segments is a respective one of the non-rigid rod segments. A method for producing a polyquinoline block copolymer composition characterized in that it is bonded to an end.

However, in the first to sixteenth means,
AA-type compounds have the formula:

[0018]

Embedded image Are aromatic compounds containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula:

[0019]

Embedded image Are aromatic compounds containing two methylene ketone functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula:

[0020]

Embedded image Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group attached to an aromatic nucleus selected from the group consisting of structures represented by the following formulas: Hydrogen or aryl, R ′ is aryl, Ar is an aromatic nucleus in which the position of attachment of each of the carbonyl and amino functional groups is ortho, and Ar ′ is that in which the positions of amino functional groups are ortho. Any aryl, Ar '' is any aryl; Ar '''' is an aryl group, wherein four of these bonds are occupied by a linkage of methylene carbonyl functionalities; ´´´
Is an aryl group in which the position of attachment of the set of carbonyl and amino functional groups is ortho.

[0021]

DETAILED DESCRIPTION OF THE INVENTION In one exemplary embodiment of the present invention,
Provided is a polyquinoline copolymer composition comprising a reaction product of a mixture of compounds selected from the group consisting of AA type, BB type and AB type compounds. Such mixtures include (1) one or more AA compounds, one or more BB compounds, and one or more AB compounds; (2) one or more AA compounds and one The above BB type compounds (the number of different AA type compounds and BB type compounds is 3
And (3) selected from the group consisting of two or more AB-type compounds.

AA-type compounds are aromatic compounds containing two sets of orthoaminocarbonyl functions attached to an aromatic nucleus. AA-type compounds useful in the practice of the present invention include:
formula:

[0023]

Embedded image Selected from the group consisting of:

The BB type compounds are composed of 2
Two methylene ketone functional group-containing aromatic compounds.
BB type compounds useful in the practice of the present invention have the formula:

[0025]

Embedded image Selected from the group consisting of the structures represented by

AB type compounds are aromatic compounds containing a set of orthoaminocarbonyl functions and one methylene ketone function attached to an aromatic nucleus. AB type compounds useful in the practice of the present invention have the formula:

[0027]

Embedded image Selected from the group consisting of the structures represented by

For the AA, BB and AB type compounds,
R is hydrogen or aryl, R 'is aryl, and Ar', Ar ", Ar""and Ar
“″ ″ ″ Is an aryl group.

The polyquinoline copolymers provided according to the present invention are random copolymers, block copolymers, or triblock copolymers. The copolymers can contain all rigid rod components, all non-rigid rod components, or both rigid and non-rigid rods.

In another exemplary embodiment of the present invention, there is provided a polyquinoline mixture composition, wherein the mixture comprises more than one polyquinoline homopolymer, or 1
Including polyquinoline copolymers, or both polyquinoline homopolymers and copolymers.

According to the present invention, polyquinoline polymer compositions, which have heretofore been unknown and consist of copolymers or mixtures, can be prepared, and the novel materials include those obtained from known polyquinoline homopolymers Have distinctly different chemical and physical properties, and this new polyquinoline polymer material can be applied to various fields. Polyquinoline copolymers and mixtures provided in accordance with the practice of the present invention include, for example, heat-stable laminated resins, adhesive compositions, coating materials, films, fibers, especially aluminum, steel, and titanium. Suitable for use as high temperature metal adhesives for alloys, and high temperature electrical insulators, foams, ablative materials and rocket nozzles.

The polyquinoline copolymers and homopolymers can be mixed or mixed with the copolymers to form the mixtures of the present invention and include AA, BB, and AB
Prepared from type compounds. AA, BB and AB
Type compounds are referred to herein as "precursor compounds" or "precursors" for the polyquinoline polymers of the present invention.

AA-type compounds useful in the practice of the present invention are aromatic aminocarbonyl compounds containing two sets of orthoaminoaldehyde or orthoaminoketone functional groups attached to the aromatic nucleus. The AA type compound has the formula:

[0034]

Embedded image Where R is hydrogen or aryl, Ar is any aryl where the position of attachment of each set of carbonyl and amino functions is ortho, and Ar ′ is the position of attachment of each set of carbonyl and amino functions. Any aryl that is ortho, and Ar ″ is any connected aryl group).

BB type compounds useful in the practice of the present invention are bismethylene ketone compounds having a methylene group adjacent to each ketone functional group. The BB type compounds have the formula:

[0036]

Embedded image Wherein R is hydrogen or aryl, R ′ is aryl, Ar ″ is as described above for AA type compounds, and Ar ″ ″ is an aryl group, and the four positions Is occupied by a linkage of the methylene carbonyl functional groups).

The AB-type compounds useful in the practice of the present invention are aromatic compounds containing an orthoaminocarbonyl function attached to an aromatic nucleus and one set of methylene ketone functions. The AB type compound has the formula:

[0038]

Embedded image Wherein R is hydrogen or aryl, R ′ is aryl, Ar ′, Ar ″ are as described above for AA and BB type compounds, and Ar ′
″ ″ Is an aryl group wherein the position of attachment of the set of carbonyl and amino functional groups is ortho)).

In accordance with the method taught in US Pat. No. 4,000,187, the polyquinoline materials provided in the practice of the present invention include aromatic amino acids as described above for AA, BB and AB type compounds. It is provided by reacting a carbonyl-containing compound with methylene ketone-containing compounds. The present invention results in a mixture of polyquinoline copolymers, polyquinoline block copolymers, polyquinoline triblock copolymers, or polyquinoline polymers.

The AA type compounds are, as described above,
Aromatic aminocarbonyl compounds containing two sets of ortho amino ketone functional groups. AA type compounds provided according to the practice of the present invention include rigid rod AA type compounds and non-rigid rod AA type compounds. Examples of such hard rod and non-hard rod AA type compounds are as follows. Hard rod AA type compound

[0041]

Embedded image Non-rigid rod AA type compound

[0042]

Embedded image Symbol G represents a divalent group selected from the group consisting of alkylene, arylene, aralkylene, alkalylene, oxygen, sulfur, sulfoxide, sulfone, dialkylsilicon, and diarylsilicon. Suitable derivatives of the AA-type compounds described above, such as acid salts, are also used in preparing the polyquinoline materials provided in accordance with the present invention. Each of the aminocarbonyl compounds listed above, that is, the aminocarbonyl compound of the general formula (1) or (2) can be substituted for the specific aminocarbonyl shown in the examples shown below, and satisfactory results can be obtained. Occurs.

Formulas (1) for AA type compounds and
The Ar substituent in (2) can be any aromatic nucleus where the position of attachment of each set of carbonyl and amino functional groups is ortho, including one aromatic nucleus and one polycyclic aromatic nucleus. In examples of AA-type compounds provided according to the practice of the present invention, the substituent Ar is selected from the group consisting of:

[0044]

Embedded image Can be represented by When the substituent R of the AA type compounds defined by the general formula (1) is aryl, it is typically phenyl (Ph).

In an exemplary embodiment of AA-type compounds provided by the practice of the present invention, the substituent Ar ′ in the general formula (2) for AA-type compounds is represented by the following group:

[0046]

Embedded image Can be represented by

In an exemplary embodiment of the AA type compounds provided by the practice of the present invention, the substituent Ar ″ in the general formula (2) has the following group:

[0048]

Embedded image Can be represented by

Within the above definition of substituent G, the most common constituents are: an alkylene group containing 1 to 12 carbon atoms, an arylene group containing 6 to 12 carbon atoms, 7-1
Aralkylene groups containing 4 carbons, alkalylene groups containing 7-10 carbons, O, S, SO, S
O ₂ , a dialkylsilicon group containing 1 to 5 carbons per alkyl group, and 6 per aryl group.
Is a diarylsilicon group containing two carbon atoms. The above definition of substituent G includes a cardo group, a non-limiting example of which is of the following formula:

[0050]

Embedded image Represented by

As also mentioned above, BB type compounds are methylene ketones containing two ketone functional groups with a methylene group adjacent to each ketone. The BB type compounds represented by the general formulas (3) to (7) provided according to the practice of the present invention include hard rod BB type compounds and non-hard rod BB type compounds. Examples of rigid rod and non-rigid rod type BB compounds are as follows: rigid rod BB type compounds

[0052]

Embedded image Non-hard rod BB type compound

[0053]

Embedded image Ar ″ of the BB type compounds is Ar ′ of the AA type compounds.
And, as evident from the preceding description of BB type compounds, Ar '' is a group of the following:

[0054]

Embedded image Can be represented by

When the substituent R 'or R of the BB type compounds is aryl, it is typically phenyl (Ph)
It is.

The substituent Ar ″ ″ of the BB type compounds is 4
A functional aromatic nucleus, two bifunctional aromatic nuclei not yet linked to each other or a tetrafunctional nucleus, for example one fused ring structure already linked to each other in some way Or a bicyclic structure, ie:

[0057]

Embedded image It is.

Symbol G is as described above for AA type compounds, and includes alkylene, arylene, aralkylene,
It represents a divalent group selected from the group consisting of alkalilene, oxygen, sulfur, sulfoxide, sulfone, dialkylsilicon, and diarylsilicon.

The above-mentioned BB type compounds, that is, each of the bismethylene ketones of the general formulas (3) to (7), can be substituted in place of the specific BB type compound shown in the following Examples, which is satisfactory. Produces a result.

As defined above, AB-type compounds provided in accordance with the present invention are aromatic compounds containing a set of orthoaminocarbonyl functions and one methylene ketone function attached to one aromatic nucleus. Group compounds. AB type compounds provided according to the practice of the present invention are represented by general formulas (8) to (11) and include hard rod AB type compounds and non-rigid rod AB type compounds. The hard rod and non-hard rod AB type compounds are as follows: Hard rod AB type compounds

[0061]

Embedded image Non-hard rod AB type compound

[0062]

Embedded image The symbol G is as defined above for AA type compounds, and includes alkylene, arylene, aralkylene, alkalylene, oxygen, sulfur, sulfoxide, sulfone,
It shows a divalent group selected from the group consisting of dialkyl silicon and diaryl silicon.

Suitable derivatives of the above AB-type compounds, such as acid salts, can also be used in preparing the polyquinoline copolymers and mixtures of the present invention. Each of the above AB type compounds, that is, any one AB compound of the general formulas (8) to (11) can be substituted for the specific AB compound shown in the following Examples, and satisfactory results can be obtained. Occurs.

Formula (8) for AB type compounds and
The substituent Ar ′ ″ in (9) can be any aromatic nucleus including one aromatic ring and one polycyclic aromatic nucleus. Substituents Ar ′ ″ provided according to the practice of the present invention include the following groups:

[0065]

Embedded image Can be represented by

When the substituent R or R 'of the AB type compounds is aryl, it is typically phenyl (P
h).

AB provided according to the practice of the invention
In an exemplary embodiment of the type compounds, the substituent Ar 'is group:

[0068]

Embedded image Can be represented by

AB provided in accordance with the practice of the present invention
In an exemplary embodiment of the type compounds, the substituent Ar ″ has the following group:

[0070]

Embedded image Can be represented by

All of the polyquinoline polymers of the present invention are prepared by reacting a mixture of various combinations of AA, BB, and AB type compounds in the presence of either an acid or base catalyst in a suitable solvent. Is generated. That is, the polymerization is all performed in solution. Thus, when it is stated herein that a mixture of various combinations of AA, BB, and AB type compounds reacts, it is understood that the reacting compounds are in a solution containing a suitable solvent and catalyst. In general, the solvents and catalysts used, reaction times and temperatures, and methods for isolating the novel polyquinoline copolymers are described in U.S. Pat.
No. 4,000,187 and recorded there by reference, Still
e, JK, Macromolecules, 1
981, 14, 870-880, which is analogous to the method used to prepare the polyquinoline homopolymers disclosed in US Pat.
However, compared to the previous work, the present invention provides the following: (a) the use of special combinations and selections of AA, BB and AB type compounds; (b) the careful use of each of the selected polyquinoline precursor compounds. Use of controlled amounts, (c) adding certain AA, BB and AB type compounds to the reaction mixture in a carefully prescribed order and at a controlled point in the reaction to produce any particular polyquinoline polymer And (d) preparing two or more different polyquinoline polymers, respectively, and then combining them into one mixture. Therefore, the method of the present invention
Critical in the successful preparation of the novel polyquinoline polymers.

Aromatic aminocarbonyl compounds, ie, AA-type compounds, which are suitable for the process of the present invention can be prepared in a variety of ways, but often by a combination of organic reactions including acylation, oxidation, and reduction. Prepared. The synthesis of 4,6-diaminoisophthalaldehyde is described in P. Ruggli and P. Hindemann, Helv. Chim. Acta., 20, 272 (1937), and for 2,5-diaminoterephthalaldehyde. In P. Ruggli and F. Brandt, Helve. Chim. Acta., 27,274 (1944),
For 4,6-dibenzoyl-m-phenylenediamine, L. Chardonnes and R. Ruitter, Helv. Chim. Acta., 38,393 (1955)
For 2,5-dibenzoyl-p-phenylenediamine, DA Kinsey and SGP Plant, Journal of Chemical Society (J. Chem. Soc.), 1
(1958), and for 2,2'-diaminoisophthalophenone, see JCESimpson, CMAtkinson
, C. Schofield and O. Stephenson, Journal of Chemical Society (J. Chem. Soc.), 646 (194
It is described in 5).

The conversion of the remaining carboxylic acid function to an amine by Hoffmann degradation of the amide after the Friedel-Craft reaction of the phthalic anhydride derivative is achieved by the two aminoketones of type AA provided by the practice of the present invention. A route to monomeric compounds. The Friedel-Crafts reaction of pyromellitic anhydride with benzene yields approximately equimolar amounts of two isomeric dibenzoylphthalic acids, which are separable on the basis of their solubility. Reaction of the acid with ammonia after conversion to pseudodibenzoylphthaloyl chloride yields the corresponding amides, which are smoothly exchanged for amines by the Hoffman reaction with sodium perchlorate.

A similar synthetic procedure is carried out starting from phthalic anhydride and diphenyl ether, and the resulting bis (carboxybenzoyl) diphenyl ether is converted to the corresponding amide.

After the preparation of the benzisoxazole from the aromatic nitro compound, this reductive cleavage of the benzisoxazole proved to be the most versatile and generally useful method for the synthesis of o-aminoketones. . 4,4 '
Reaction of -dinitrodiphenyl ether with phenylacetonitrile in the presence of a base gives bisbenzisoxazole, which can be converted to aminoketone by a platinum catalyst. This catalyst does not reduce the aryl ketone. Benzoisoxazole was obtained from p-bromonitrobenzene. This reduction of the benzoisoxazole ring was performed chemically to avoid removal of the bromine functionality. The conjugation of 2-benzoyl-4-bromoaniline was then achieved using nickel.

Methylene ketone compounds suitable for the process of the present invention, ie, BB type compounds, can be prepared by various methods, but are often conveniently effected by the Friedel Craft reaction of the acid chloride on the aromatic nucleus. Can be prepared. The synthesis of 1,4-diphenylacylbenzene is described in CLShilling, Jr., JA Reed and JKStill.
e, Macromolecules, 2,85
(1969) described the synthesis of 1,4-diphenylacetylbenzene by MAOgliaruso and EIBecker, Journal of Organic Chemistry (J. Org. Chem.), 30, 35.
54 (1965), 4,4'-diphenylacetylphenyl ether, 4,4'-diphenylacetylphenyl sulfide and 4,4'-diphenylacetylbiphenyl are available from HAOgliaruso, LA Shadov, and EI.
Becker, Journal of Organic Chemistry (J.O.
rg. Chem.), 28, 2725 (1963); p-diacetylbenzene is described in L. Berend and P. Herms, Journal of Practical Chemistry (J. Prakt. Chem.), 74, 134 (19).
06), 1,3-diacetylbenzene was obtained from J. Brown, Journal of Chemical Society (J. Chem. Soc.),
323 (1950), 4,4'-acetylphenyl ether was obtained from H. Kipper, Chemische Berichte (Chem.
r. ), 38,2491 (1905), 2,6-Diacetylpyridine is available from AP Terentev, EGRukhadze, IG Mochalin.
a, and VVRode, Zh.Vses.Khim.Obshch.im. DI Me
In 4, ndeleeva, 6,116 (1961), 4,4'-diacetyldiphenyl sulfide is disclosed in CMSmith, U.S. Pat.
No. 3,461 (1959), 4,4'-diacetyldiphenylsulfone is described in PFHu, Journal of Chemical Society (J. Chem. Soc.), 178 (1959).
´-Diacetylbiphenyl is available from H. Tani, F. Toda and
K.Matsumiya, Bulletin of Chemical Society in Japan (Bull.Chem.Soc.Jap.), 36,391 (1963),
Dibenzo [a, e] -cyclooctene-5,11- (6
H, 12H) dione is available from P. Yates, EG Lewars and PH
Mc Cabe, Canadian Journal of Chemistry (Can.
J. Chem. ), 48,788 (1970), and 1,10-diketo [2,2] metacyclophane are described in T. Hylton and V. Bo.
ekelheide, Journal of American Chemical Society (J. Amer. Chem. Soc.), 90,6887 (1968).

The Friedel-Crafts acylation or phenacylation of certain aromatics can be accomplished with pure bis (ketomethylene)
It is a suitable method for obtaining (BB type) compounds in high yield.
This method is particularly useful for the acylation of biphenyl, diphenyl ether, and diphenyl sulfide.
The coupling reaction of an acyl aromatic compound can be an effective method for producing bisacetyl monomers. The reaction of Grignard reagents with dinitrile has also been utilized in the synthesis of bis (ketomethylene) compounds, especially bis (deoxybenzoins).

The synthesis of AB-type compounds suitable for the process of the present invention is described, for example, in Eichinger, BE, Flory, PJ, Trans. Fadaday Soy.
c.), 1968, 64, 2035, 2053, 2061 and 2066, and Kwe
i, TK Patterson, GD, Wang, TT, Macromolecules, 1976, 9,780. Protection of the acetyl group is necessary because the reaction of the nitroaromatic with phenylacetonitrile takes place with a strong base. Following hydrogenation of the benzoisoxazole ring, removal of the ketone protecting group is performed.

The preparation of various AA, BB, AB type compounds is described in Stille, JK, Macromolecules.
es), 1981, 14,870-880.

In one embodiment of the present invention, polyquinoline copolymers are prepared. Polyquinoline copolymer is defined herein as any particular polyquinoline polymer resulting from the reaction of a mixture of various combinations of AA, BB, AB type compounds. However, single AA
Reaction between a single type compound and a single BB type compound, or a single AB
Excluding polyquinoline homopolymers produced by the reaction of the type compound. As an illustrative example, the polyquinoline copolymer is-(D) _n- (E) _o- (D) _p- (F) _q- (E) _r- (D) _s- (F) _t- (E ) _u-where D, E, and F represent different monomer units, the number of which varies from 2 to 100, but most often from 2 to 10. . The subscripts n, o, p, q, r, s, t and u indicate the number of repeating monomer units in each part of the polymer, which numbers vary from 1 to 100,000, usually 1 From1,000
Up to. The number of repeating monomer units in each moiety may be the same regardless of the nature of the monomer in any moiety, or may vary from moiety to moiety. It is clear that for the special case of polyquinoline homopolymers, there is a single monomer unit at-(D) _n- .

According to the present invention, a method for producing polyquinoline copolymers comprises the steps of preparing one of AA, BB and AB type compounds.
Reacting the mixture of the two combinations in a solution. Such mixture combinations include (1) 1
One or more AA compounds, one or more BB compounds and one or more AB compounds, (2) one or more AA compounds in which the number of different AA and BB compounds is 3 or more And one or more BB-type compounds, and (3) two or more AB-type compounds. These combinations are referred to herein as "No. (1), No. (2) and No. (3) mixture combinations". The minimum amount of each of the above AA, BB or AB type precursor compounds used in such a mixture depends on the precursor compounds, ie, the selected AA, BB
And at least 0.01% of the total moles of AB type compounds, but preferably 0.1%, and most preferably 1.0%.
%. For any particular polyquinoline copolymer, if at least 99.0 mole% of the total amount of all of the AA, BB and AB type compounds used is selected from the group of hard rod precursor compounds, It is considered a rigid rod polyquinoline copolymer.

-Random Copolymers-According to the present invention, the provided polyquinoline copolymers are prepared according to a method referred to herein as a "general method" for the production of polyquinoline copolymers. You. The general method of the present invention is as follows.

The selected AA, BB and AB type precursor compounds are mixed with a suitable acid or base catalyst in a suitable solvent or mixture of solvents (referred to herein as a "primary solvent system"). And warm the entire reaction mixture between 25 ° C and 250 ° C until the reaction is complete. Most typically, the reaction is started at room temperature and this temperature is slowly increased to about 13
Raise to 5 ° C. and maintain at this temperature with vigorous stirring until the reaction is complete or the desired average molar weight is achieved.

Acid and base catalysts and solvents useful in practicing the process of the present invention are described in US Pat. No. 4,000,187. For example, the acid catalysts can be either protic or Lewis acid. Hydrogen halide (fluoride, chloride, bromide or iodide), sulfuric acid such as sulfonic acid such as toluenesulfonic acid, phosphoric acid, polyphosphoric acid, trifluoroacetic acid, monoarylphosphoric acid, diarylphosphoric acid, etc. Boron fluoride, phosphorus pentafluoride, aluminum chloride, antimony trifluoride, antimony pentafluoride, antimony trichloride, tin chloride, etc. are examples of Lewis acid catalysts. The base catalysts can be either hydroxyl bases (hydroxyl groups) or Lewis bases. Sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide and the like are examples of hydroxylated base catalysts, while N-ethylmorpholine,
Triethylamine, 1,5-diazabicyclo [4,3
0] non-5-ene, 1,4-diazabicyclo [2,
2,2] octane and the like are examples of Lewis base catalysts.

A wide range of solvents are available for either acid or base catalyzed reactions. Under the reaction conditions described above, the solvent used in these reactions should not react with either an acid or base catalyst or any of the functional groups on the monomers, and this reaction has an adverse effect on the polymerization reaction. May have an effect. Benzene, chlorobenzene, 1-chloronaphthalene, tetralin, acetic acid, formic acid, for example m-
Phenols such as cresol, o-, m-, and p-dichlorobenzene (or mixtures thereof), polyphosphoric acid, and the like are solvents that can be used in the acid-catalyzed reaction. In cases such as formic acid and acetic acid, the formic acid and acetic acids are not strong enough at the reaction temperature to provide sufficient catalysis and reaction rate such that the high molecular weight polymer is formed within a convenient reaction time. Therefore, it is desirable to add a strong acid catalyst. Dimethyl sulfoxide, hexamethylphosphorictriamide, dimethylformamide, tetrahydrothiophenedoxide, dimethylacetamide, N-methylpyrrolidone, and the like are solvents that can be used in the base-catalyzed reaction.

The completion of the reaction can be determined in several ways, including by monitoring either the continuation of the reaction or the viscosity of the reaction mixture. Upon cooling to room temperature, the reaction mixture is poured into a secondary solvent or solvent mixture (referred to herein as a "secondary solvent system") to precipitate the product polyquinoline copolymer. Most typically, this secondary solvent system consists of ethanol and triethylamine. However, this secondary solvent system may be, but is not limited to, a good solvent system for certain product polyquinoline copolymers such as water, methanol, 2-propanol, 1-butanol, 2-butanol, and the like. It can be any solvent or mixture of solvents. When an acid catalyst or solvent is used in the initial reaction, the secondary solvent system may also include a base that partially or completely neutralizes the acid solvent or any acid catalyst in the reaction mixture, such bases Examples thereof include triethylamine, trimethylamine, pyridine, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium bicarbonate and the like.

The selection of certain special mixtures of AA, BB and AB type compounds is used to produce polyquinoline homopolymers. Thus, the reaction of any single AB-type compound, or alternatively, the reaction of any single AA-type compound with any single BB-type compound can be accomplished by reacting the polyquinoline homopolymers described in U.S. Patent No. 4,000,187. Causes generation.

-First Random Copolymer Method- In one embodiment of the present invention, certain polyquinoline copolymers are composed of one or more AA type compounds, one or more BB type compounds and one or more AB type compounds. It is produced by the reaction of any mixture containing the compound (No. 1 mixture combination). Any particular polyquinoline copolymer formed from such a mixture of precursor compounds is considered a random copolymer and is formed according to the general methods for making and isolating polyquinoline copolymers described above. Is done.

-Second Random Copolymer Method- In another embodiment of the present invention, certain polyquinoline copolymers contain only AA and BB type compounds,
It is produced by the reaction of any mixture (No. (2) mixture combination) in which the total number of A-type and BB-type compounds is 3 or more. Any particular polyquinoline copolymer formed from such a mixture of precursor compounds is considered a random copolymer and may be formed according to the general methods for making and isolating polyquinoline copolymers described above. You.

-Third Random Copolymer Method- In another embodiment of the present invention, some polyquinoline copolymers contain only AB type compounds, but the total number of AB type compounds is 2 or more. It is produced by the reaction of any mixture (No. (3) mixture combination). Any particular polyquinoline copolymer formed from such a mixture of precursor compounds is considered a random copolymer and is formed according to the general methods for making and isolating polyquinoline copolymers described above. You.

It is clear that polyquinoline copolymers have different chemical and physical properties than polyquinoline homopolymers, and that the properties of certain polyquinoline copolymers can result in useful reactions. is there. In an exemplary embodiment, a homopolymer film formed by reacting equivalent amounts of the following AA and BB type compounds produces a homopolymer referred to herein as homopolymer (1).

[0092]

Embedded image When the homopolymer (1) was examined by differential mechanical analysis, it showed a single tan δ with a Tmax of 275 ° C. T
defined as anδ = E1 / E2, where E1 is the dynamic modulus in the stress phase and E2 is the dynamic modulus that is π / 2 outside the stress phase. Similarly, the following 2
The homopolymer films formed by reacting the equivalents of the AA type and BB type compounds of
It produces a homopolymer called

Embedded image When examining homopolymer (2), it was found that Tmax was 37
At 0 ° C., a single tan δ was shown. Compared to the two homopolymers, the AA-type and BB-type compounds 4
The polyquinoline copolymer film produced by the equivalent reaction of all the seeds had a Tmax of 316 ° C. and exhibited a single tan δ. Therefore, this copolymer, homopolymers (1)
Or, it shows a property clearly different from either property of (2).

Block Copolymers Another embodiment of the present invention is in the preparation of polyquinoline block copolymers. Polyquinoline block copolymers are referred to as "blocks" in different polyquinoline oligomers covalently linked to each other, referred to as "blocks".
It is defined as a polymer containing one or more segments. Compared to polyquinoline random copolymers, polyquinoline block copolymers achieve a certain amount of control over the average number of repeating monomer units in each different type of block in the block copolymer It is produced in such a way that Any particular block may result from the reaction of a single AA compound with a single BB compound, or may result from the reaction of a single AB compound and from 2 to 1
It can be a homo-oligomer consisting of 0,000 recurring polyquinoline monomer units, most often an average of 5 to 1,000 recurring monomer units. Separately, any particular block may be a combination of AA, BB and AB described above as No. (1), No. (2) and No. (3) mixed combinations for the preparation of random copolymers. It can be a co-oligomer consisting of a portion of a polyquinoline copolymer prepared from a mixture of type compounds. Such co-oligomers have an average molecular weight of about 254 to about 250,000 daltons, typically about 1,000 to 100,000 daltons. Any particular block can be a rigid rod oligomer or a non-rigid rod oligomer, depending on the choice of AA, BB and AB type monomers selected from the mixture combination used. Therefore, any particular polyquinoline block copolymer,
It may contain only rigid rod blocks, only non-rigid rod blocks, or a combination of both.

It will be appreciated that the successful preparation of the block copolymer requires a polymer formation reaction and subsequent block chemical inertness without scrambling between the block portions. That is, if a particular multi-block polymer is formed, then each block must be inert to all intermolecular or intramolecular reactions that can result in block splitting and subsequent interblock melting. Must. As an illustrative example, esters are well known to undergo transesterification. Extraordinary care must be taken in producing and using the polyester block copolymers, or the block copolymers of interest will be converted to random copolymers. In contrast,
The polyquinoline block copolymers prepared according to the method of the present invention are essentially inert to any such interblock scrambling.

According to the present invention, a general method for preparing polyquinoline block copolymers is a multi-step process. In a first step, using an initial mixture of precursor compounds in solution with a suitable solvent or solvent mixture and a catalyst, one having a controlled average molecular weight and reactive groups at each end of the block. The next block is produced. In a second stage, additional precursor compounds are added into a secondary mixture of precursor compounds, some of which react with the reactive groups at the ends of the primary block,
Multi-block polymers are formed. According to the method of the present invention, an initial mixture of precursor compounds is used in the first stage to produce polyquinoline random copolymers, except that the primary product, primary block, does not precipitate from the reaction mixture. Under similar conditions as described above. Rather, in the second stage of the reaction, when the completion of the reaction of the initial mixture of precursor compounds reaches the desired degree, a second mixture of polyquinoline precursor compounds is added, and this second mixture is added to the first stage. Contains different types or different relative amounts of the precursor compounds as compared to those contained in the primary mixture used in and the reaction is continued. This reaction can be monitored by any convenient method. When the completion of the second stage reaches the desired degree, the reaction can be stopped and the product polyquinoline block copolymer is formed in a manner similar to that described above for the preparation of polyquinoline copolymers. Can be isolated by precipitation. Any particular polyquinoline block copolymer prepared by this two-step method will contain two different blocks. Alternatively, before the reaction product is precipitated at the end of the second stage, a third stage and even subsequent stages can be used, each stage being similar to the second stage, with additional different Add blocks of type, but usually the number of blocks will be two to four. This method can be used to produce polyquinoline block copolymers having only rigid rod blocks, only non-rigid rod segments, or both types of segments.

-Primary Block Copolymer Method- As an embodiment of the method for producing block copolymers of the present invention, the average molecular weight of the block composed of the polyquinoline block copolymer is determined under the specific reaction conditions. Controlled by selection and selection of the relative amounts of precursor compounds for each block. Thus, block copolymers are produced in a two-step process.

In the first stage of the two-stage process, the No. (1) of AA type compounds, BB type compounds, and AB type compounds
A primary block forming mixture consisting of a compound, No. (2) compound or No. (3) compound mixture combination is in a solution of a suitable solvent and catalyst. When both AA and BB compounds are in the mixture, the total moles of AA compounds is equal to the total moles of BB compounds. This mixture is reacted under similar reaction conditions as described above for the general method of preparing polyquinoline random copolymers. The reaction is performed by measuring the time of the reaction, monitoring the viscosity of the reaction, or any other convenient method of determining when the reaction has proceeded sufficiently to produce the desired average molecular weight polyquinoline segment. Monitored by using. In the preparation of any particular polyquinoline block copolymer, substantially shorter reaction times at lower temperatures result in substantially lower average molecular weights of the primary blocks, while allowing the reaction to continue for longer periods or at higher temperatures. This would result in a primary block with a somewhat higher average molecular weight.

In the second stage of the two-stage process, the AA type compounds, BB type compounds, and No.
The secondary block forming mixture consisting of the combination of (1) compound, No. (2) compound or No. (3) compound mixture is in a solution of a suitable solvent and catalyst. When both AA type and BB type compounds are in the mixture, the total number of moles of AA type compounds is equal to the total number of moles of BB type compounds, and 2
The secondary block-forming mixture contains different types and / or relative amounts of precursor compounds than are included in the secondary block-forming mixture. This secondary mixture is combined with the reacted 1
Add to the next block forming mixture and continue the reaction until the reaction is complete. According to the present method, the average molecular weight of the secondary block was determined in the first stage by the total moles of precursor compounds in the secondary block versus the total moles of precursor compounds in the primary block forming mixture. It will be determined in part by the average molecular weight of the block, and the degree of completion of the reaction as the polyquinoline block copolymer precipitates from solution. After completion of the second step, the product polyquinoline block copolymer can be isolated by precipitation as previously described. Alternatively, the reaction flow can be continued even by the third and subsequent steps, and additional different blocks can be added to the polyquinoline block copolymer before the reaction is terminated and the product is isolated. . The method can be used for the production of rigid rod blocks, non-rigid rod block segments or polyquinoline block copolymers having both types of segments.

In the above primary method for preparing polyquinoline block copolymers, the method relies on interfering with the first-stage reaction when the reaction is only partially completed, so that the building blocks It is difficult to control the average molecular weight.

-Secondary Block Copolymer Method- Another embodiment of the method for producing block copolymers of the present invention is a method for controlling the average molecular weight of blocks, which is used for preparing an initial block. The present invention relates to a method in which the relative amounts of the AA type and BB type compounds used in the next step are different and are continued until the initial reaction is completed. After completion of the first stage reaction, the reaction mixture is a polyether of known average molecular weight in which the reaction end groups are ready for further reaction when a secondary mixture of precursor compounds is added in the second stage. Contains quinoline oligomer. According to the method, in a first stage, an initial mixture, i.e. No. (1) consisting of one or more AA compounds, one or more BB compounds and zero or one or more BB compounds. )
A primary block-forming mixture consisting of a combination of compounds or No. (2) compounds is prepared. The total number of moles of AA type compounds is not equal to the total number of moles of BB type compounds. This primary mixture is reacted under similar reaction conditions as described above for the preparation of polyquinoline random copolymers. The reaction continues until completion.

In the preparation of any particular polyquinoline block copolymer by the secondary block copolymer method, the maximum average molecular weight of the initial block is determined by AA for BB-type compounds which are close to but not equal to 1.0. This is achieved by using a molar ratio of the type compounds. The number of reactive end groups in the prepared initial blocks is determined by the modified Carothers formula: DP = 1 + r / (1 + r-2rp) (where DP is the degree of polymerization and r is the two types of monomer) Is the molar ratio of the classes, r is taken to be less than or equal to 1, and P is the degree of reaction: P = number of groups reacted / number of groups originally present) It can be used to calculate from the molar ratio of AA type compounds to BB type compounds. In the second step, a secondary mixture consisting of a combination of AA type compounds, BB type compounds, and No. (1) compound, No. (2) compound or No. (3) mixture of AB type compounds is used. A next block forming mixture is prepared. The secondary block-forming mixture contains a different type or a different relative amount of precursor compounds than those contained in the primary block-forming mixture. The secondary block forming mixture is added to the reaction mixture, and the reaction is allowed to continue to completion. According to this method, when either the No. (1) or No. (2) mixture combination is used in the primary and secondary stages, the maximum molecular weight of the secondary block and polyquinoline block copolymer is: Obtained when the total number of moles of AA type compounds used in both the first and second stages is equal to the total number of moles of BB type compounds used in both the first and second stages. After completion of the second step, the product polyquinoline block copolymer can be isolated by precipitation, as described above. Separately, in a similar manner, the reaction stream is added in a third and subsequent stage to the polyquinoline block copolymer before the reaction is terminated and the product is separated off. Can be. This method can be used for the production of polyquinoline block copolymers having only rigid rod blocks, only non-rigid rod segments, or both types of segments.

-Tertiary Block Copolymer Method-Another embodiment of the present invention relates to a method for controlling the average molecular weight of the blocks, in which only the AA type compound or only the BB type compound is used together with the AB type compounds in the first step. Prepare the initial block and continue the initial reaction to completion. At the completion of the first-stage reaction, the reaction mixture is a polyether of known average molecular weight whose reaction end groups are ready for subsequent reactions when a secondary mixture of precursor compounds is added to the second stage. Contains quinoline oligomers. According to the present method, in a first step, an initial mixture of one or more AA-type compounds, or one or more BB-type compounds, and one or more AB-type compounds, is used as a polyquinoline random copolymer The reaction is carried out under similar reaction conditions as described above for the preparation of the class. This reaction is continued until completion.

In the preparation of any particular polyquinoline block copolymer, the maximum average molecular weight of the initial block is determined by the molar ratio of AB type compounds to AA type compounds,
Alternatively, this is achieved by using the larger molar ratio of the AB type compound to the BB type compound. The number of reactive end groups in the generated initial blocks can be calculated from the molar ratio using the modified Carothers equation described above.
If type AA compounds are used in the first step, then the reactive end groups will consist of orthoaminocarbonyl functions, while type BB compounds will be
If used in a step, then the reactive end groups would consist of methylene ketone functions. In the second stage, the secondary mixture, ie, the combination of No. (1) mixture of AA, BB or AB type compounds,
(2) Mixture combination, No. (3) A secondary block-forming mixture consisting of the mixture combination is prepared. In the secondary block forming mixture, the total number of BB type compounds and AB type compounds is 1 or more if AA type compounds are used in the primary mixture, and BB type compounds and AB type compounds The total number of compounds is one or more if BB type compounds are used in the primary mixture.
The secondary mixture also contains a different type or a different relative amount of precursor compounds than in the primary mixture. This secondary mixture is then added to the reacted primary mixture and the reaction is allowed to continue to completion.

According to the present method, the maximum molecular weight of the secondary block and polyquinoline block copolymer is such that the total number of AA type compounds used in both the primary and secondary stages is:
Obtained when equal to the total number of BB type compounds used in both the primary and secondary stages. After the completion of the second stage,
The product polyquinoline block copolymer can be isolated by precipitation as described above. Alternatively, the reaction is continued with the flow using even the third and subsequent stages,
As noted above, before the reaction is complete and before product isolation, additional different blocks can be added. This method can be used for the production of polyquinoline block copolymers having only rigid rod blocks, only non-rigid rod segments, or both types of segments.

-Triblock Copolymers- Another embodiment of the present invention is in the preparation of polyquinoline triblock copolymers. A polyquinoline triblock copolymer is defined as a polymer containing three segments of which two of the three segments are of similar or equal type, but not necessarily of similar or equal length. Thus, polyquinoline triblock copolymers are a segment of one type of block at the center of any given polymer chain, with different types of blocks covalently attached to each end of the primary block. A segment having two segments. The central block produced in any particular polyquinoline triblock copolymer is a homo-oligomer and a single A
Arising from the reaction of a compound of type A with a single compound of type BB and consisting of 2 to 10,000 recurring polyquinoline monomer units, most often consisting of an average of 5 to 1,000 recurring monomer units. Alternatively, the central block is a co-oligomer consisting of one segment of one polyquinoline copolymer prepared from a mixture of AA and BB type compounds, having an average molecular weight of 254 to 250,000 daltons, typically Has an average molecular weight of 1,000 to 100,000 daltons. Similarly, the end blocks in any particular polyquinoline triblock polymer may be homo-oligomers made with a single AB-type compound, or may be made using a mixture of two or more AB-type compounds. It can be a prepared co-oligomer.

[0106] Any particular block may be a rigid rod oligomer or a non-rigid rod oligomer, depending on the choice of AA, BB, and AB monomers selected. Thus, any particular polyquinoline triblock copolymer can contain only rigid rod blocks, or only non-rigid rod oligomers, or a combination of both. As an illustrative example, certain polyquinoline triblock copolymers have a single non-rigid rod block with two rigid rod blocks, one covalently bonded to each end of the rigid rod block. ing. Alternatively, certain polyquinoline triblock copolymers have a single non-rigid rod block with two rigid rod blocks, one covalently bonded to each end of the non-rigid rod block. ing.

According to the method of the present invention, polyquinoline triblock copolymers are prepared in a two-step process. First
In the step, one or more AA-type compounds in which the number of moles of AA-type compounds is not equal to the number of moles of BB-type compounds,
One or more BB-type compounds and zero, one or more AB-type compounds can be obtained under similar reaction conditions as described above for the general method for the preparation of polyquinoline random copolymers. React until the reaction is complete. 1
After the completion of the next reaction, one or more AB-type compounds are added to the reaction mixture and the reaction is continued until completion. The product polyquinoline triblock copolymer is then isolated by precipitation, as described in the process for preparing polyquinoline copolymers. One covalent bond to each end of the rigid rod block by the use of rigid rod type AA, rigid rod type BB, and rigid rod type AB compounds in the first stage and in the second stage the use of non-rigid rod type compounds To form a triblock polyquinoline copolymer having one non-rigid rod block with two non-rigid rod blocks joined together. Similarly, non-rigid rod type AA, non-rigid rod type BB, and non-rigid rod A
One is covalently attached to each end of the non-rigid rod block by the use of B-type compounds in the first stage and in the second stage by the use of rigid AB rod-type compounds.
This results in a triblock polyquinoline copolymer having one hard rod block with one hard rod block.

Polyquinoline Blend Composition In another embodiment, the invention is directed to a mixture of two or more different polyquinoline polymers, wherein the polyquinoline polymers are polyquinoline homopolymers, random copolymers, block copolymers. A polyquinoline mixture composition selected from the group of copolymers, triblock copolymers, or any other type of polyquinoline polymer.
As the name implies, polyquinoline mixtures are obtained by mixing selected polyquinoline polymers.

In one embodiment of the present invention, the polyquinoline mixture is prepared by dissolving the initially selected polyquinoline polymer in a solvent or mixture of solvents that sufficiently dissolves the polyquinoline polymer. Prepared. The total concentration of the polymers in the resulting solution varies from 0.01 weight percent to 25.0 weight percent, usually from 1.0 to 25.0 weight percent. Thereafter, the solvent is evaporated to yield the product polyquinoline mixture. Alternatively, a second solvent or solvent mixture is then added to the solution to rapidly precipitate the polyquinoline mixture from the resulting solvent mixture. The second solvent or solvent mixture used must be a solvent that is insoluble in the constituent polyquinoline polymers and can include water, ethanol, methanol, propanols, butanols, pyridine, triethylamine, and the like. According to the present method, in preparing a particular polyquinoline mixture, the product mixture can contain more than one phase attributable to some amount of phase separation of the constituent polymers.

For the preparation of mixtures of polyquinoline homopolymers and / or copolymers, universal solvents are:
m-cresol: 6 of di-m-cresyl phosphate
5:35 W / W% mixture. Other solvents are believed to be useful for preparing such polyquinoline mixtures, depending on the particular combination of polyquinoline homopolymers and / or copolymers used. For example, containing only hard rod segments, or polyquinoline homopolymers or copolymers mainly composed of hard rod segments,
It can be expected that it will be soluble in selected strong acids such as trichloromethanesulfonic acid, and thus trichloromethanesulfonic acid is a reasonable solvent for the preparation of the aforementioned mixture of predominantly rigid rod polymers. It can be predicted that there is. In contrast, polyquinoline homopolymers and copolymers that consist entirely of non-rigid rod segments or predominantly non-rigid rod segments can be dissolved in organic solvents such as chloroform, and
Chloroform can be expected to be a suitable solvent for the preparation of the non-rigid rod polyquinoline polymer mixture.

Thus, in another embodiment of the present invention, the polyquinoline mixtures are formed in a solvent or solvent mixture in which all of the polyquinoline polymers are sufficiently soluble in the resulting solution of the polymers in solution. Prepared by first dissolving the polyquinoline polymers selected so that the total concentration ranges from 0.01 weight percent, usually about 1.0 weight percent, to a concentration below which the solution becomes anisotropic. Is done. A second solvent, or mixture of solvents, is then added to this solution so as to rapidly precipitate the polyquinoline mixture from the resulting solvent mixture. The second solvent or solvent mixture used was:
The constituent polyquinoline polymers must be insoluble in water, ethanol, methanol, propanols,
Butanol, pyridine, triethylamine, and the like. Unlike this, this polymer solution
The film can be obtained by treating by spinning into a non-solvent to obtain the fibers or extruding through a slit or the like into the non-solvent.

Polyquinoline mixtures have different chemical and physical properties than single-component polyquinoline homopolymers or copolymers, and the properties of certain polyquinoline mixtures can be applied to useful applications. it can. As an illustrative example, the following formula:

[0113]

Embedded image The film of the polyquinoline homopolymer (1) represented by the formula, when examined by differential
x At 276 ° C. Similarly, the formula:

[0114]

Embedded image The film of polyquinoline homopolymer (2) represented by the formula, when examined by differential mechanical analysis, shows a single tan δ
x Shown at 369 ° C. In contrast, a polyquinoline mixture prepared as described above and consisting of a 50:50 mixture of (1) and (2) exhibited two tan δ with Tmax of 290 ° C and 366 ° C. Similarly, polyquinoline mixtures consisting of a 90:10 mixture of (1) and (2)
Two tan δ values with max 282 ° C and 356 ° C are shown. Thus, the polyquinoline mixtures exhibit properties distinctly different from those of either of the homopolymers (1) and (2).

The preferred embodiments of the present invention are summarized as follows.

[0116] 1. A method for producing a polyquinoline block copolymer, comprising: (a) in a primary step: (1) one or more AA-type compounds, one or more BB-type compounds, and one or more AB-type compounds; (2) one or more AA compounds and one or more BB compounds in which the number of different AA compounds and BB compounds is 3 or more; and (3) two or more ABs When the AA type and BB type compounds are used as the type compounds, a primary reaction mixture of compounds selected from the group in which the total number of moles of AA type compounds is equal to the total number of moles of BB type compounds And reacting the primary mixture for a selected time period to provide a reacted primary mixture; and, after the selected time period,
(B) in a second step, adding a secondary mixture of compounds to provide a secondary reaction mixture to the reacted primary mixture, wherein the secondary mixture of compounds comprises (1) one or more AA
Type compounds, one or more BB type compounds, and one or more AB type compounds; (2) one or more AA type compounds in which the number of different AA type compounds and BB type compounds is 3 or more And one or more BB type compounds; and (3) 2
At least one AB-type compound, wherein the secondary mixture of the compounds comprises at least one AA-type, BB-type or AB-type compound not used in the first stage, and the time during which the secondary reaction mixture is selected; 1. A method for producing a polyquinoline copolymer composition which is allowed to react for a period of time; A process for producing polyquinoline block copolymers, comprising: (a) one or more non-rigid rod AA-type compounds;
Mixing one or more non-rigid rod BB compounds and zero or more non-rigid rod AB compounds;
Wherein the total number of moles of non-rigid rod AA-type compounds is equal to the total number of moles of non-rigid rod BB-type compounds, and the mixture is reacted for a primary selection time period;
(B) after said first selection time period, one or more hard rod AA type compounds, one or more hard rod BB type compounds, and zero or one or more hard rod AB 2. A method for producing a polyquinoline copolymer composition, comprising adding type compounds and (c) continuing the reaction for a second selection time period; A method for producing a polyquinoline block copolymer, comprising: (a) one or more hard rod AA type compounds;
One or more hard rod BB type compounds and zero or more hard rod AB type compounds are mixed, and the total number of hard rod AA type compounds is hard rod B
Equal to the total number of moles of type B compounds, and the mixture is allowed to react for a primary selection time period; (b)
After a next selection time period, the reaction mixture may comprise one or more non-rigid rod AA compounds, one or more non-rigid rod BB compounds, and zero or more non-rigid rod AB compounds. 3. a process for producing a polyquinoline copolymer composition, which comprises adding the compounds and (c) continuing the reaction for a secondary selection time period; A process for producing polyquinoline block copolymers, comprising: (a) one or more non-rigid rod AA-type compounds;
Mixing one or more non-rigid rod BB compounds and zero or more non-rigid rod AB compounds;
Wherein the total number of moles of non-rigid rod AA-type compounds is equal to the total number of moles of non-rigid rod BB-type compounds, and the mixture is reacted for a primary selection time period;
(B) adding one or more hard rod AB-type compounds to the reaction mixture after the primary selection period, and (c) continuing the reaction for a secondary selection period. 4. A method for producing a polyquinoline copolymer composition; A method for producing a polyquinoline block copolymer, comprising: (a) one or more hard rod AA type compounds;
One or more hard rod BB type compounds and zero or more hard rod AB type compounds are mixed, and the total number of hard rod AA type compounds is hard rod B
Equal to the total number of moles of type B compounds, and the mixture is allowed to react for a primary selection time period; (b)
A polyquinoline copolymer comprising adding one or more non-rigid rod AB type compounds to the reaction mixture after a second selection time period, and (c) continuing the reaction for a second selection time period 5. a method for producing the composition; A process for producing polyquinoline block copolymers, comprising: (a) one or more non-rigid rod AA-type compounds;
Mixing one or more non-rigid rod BB compounds and zero or more non-rigid rod AB compounds;
Wherein the total moles of non-rigid rod AA compounds are equal to the total moles of non-rigid rod BB compounds, and the viscosity of the reaction mixture indicates that the desired average polymer molecular weight has been achieved. Reacting the mixture until
(B) After the desired average molecular weight is achieved, one or more hard rod AA compounds, one or more hard rod BB compounds, and zero or one or more hard rod AB compounds 6. a method for producing a polyquinoline copolymer composition, comprising: adding to the reaction mixture; and (c) continuing the reaction for a second selection time period. A method for producing a polyquinoline block copolymer, comprising: (a) one or more hard rod AA type compounds;
One or more hard rod BB type compounds and zero or more hard rod AB type compounds are mixed, and the total number of hard rod AA type compounds is hard rod B
Reacting the mixture until it is equal to the total number of moles of compounds of type B and the viscosity of the reaction mixture indicates that the desired average polymer molecular weight has been achieved; (b) the desired average molecular weight has been achieved , One or more non-rigid rod AA compounds, one or more non-rigid rod BB compounds, and zero or more non-rigid rod A
7. A method for producing a polyquinoline copolymer composition, comprising: adding a B-type compound to the reaction mixture; and (c) continuing the reaction for a second selection time period. A process for producing polyquinoline block copolymers, comprising: (a) one or more non-rigid rod AA-type compounds;
Mixing one or more non-rigid rod BB compounds and zero or more non-rigid rod AB compounds;
Wherein the total moles of non-rigid rod AA compounds are equal to the total moles of non-rigid rod BB compounds, and the viscosity of the reaction mixture indicates that the desired average polymer molecular weight has been achieved. Reacting the mixture until
(B) after the desired average molecular weight is achieved, adding one or more hard rod AB-type compounds to the reaction mixture; and (c) continuing the reaction for a secondary selection time period. 8. A method for producing a polyquinoline copolymer composition, A method for producing a polyquinoline block copolymer, comprising: (a) one or more hard rod AA type compounds;
One or more hard rod BB type compounds and zero or one or more hard rod AB type compounds are mixed, wherein the total number of moles of the non-hard rod AA type compounds is Reacting the mixture until the total number of moles is equal and the viscosity of the reaction mixture indicates that the desired average polymer molecular weight has been achieved; (b)
After the desired average molecular weight is achieved, one or more non-rigid rod AB-type compounds are added to the reaction mixture, and (c) allowing the reaction to continue for a secondary selection time period. 9. a method for producing a polymer composition; A process for producing polyquinoline block copolymers, comprising: (a) one or more non-rigid rod AA-type compounds, one or more non-rigid rod BB-type compounds, and zero or one or more non-rigid rods. Mixing rod AB type compounds, wherein the total number of moles of non-rigid rod AA type compounds is not equal to the total number of moles of non-rigid rod BB type compounds;
And reacting the mixture until all of the non-rigid rod compounds have completely reacted; (b) after all of the non-rigid rod compounds have completely reacted, one or more hard rod AA-type compounds Kind, one or more kinds of hard rods B
Adding a B-type compound and zero or one or more hard rod AB-type compounds to the reaction mixture; and (c) continuing the reaction for a secondary selection time period. Manufacturing method, 11. A process for producing polyquinoline block copolymers, comprising: (a) one or more hard rod AA-type compounds;
One or more hard rod BB type compounds and zero or one or more hard rod AB type compounds are mixed, and the total number of moles of the hard rod AA type compounds is equal to the total number of the hard rod BB type compounds. Reacting the mixture unequal to moles and until all of the hard rod compounds have completely reacted; (b) after all of the hard rod compounds have completely reacted, one or more non- Hard rod A
A-type compounds, one or more non-rigid rod BB-type compounds, and zero or more non-rigid rod AB-type compounds are added to the reaction mixture; and (c) a second selection time for said reaction 11. A method for producing a polyquinoline copolymer composition which is continued for a period. A method for producing polyquinoline block copolymers, comprising: (a) in the first stage, (1) one or more AA
Mixing the type compounds with one or more AB type compounds, forming a primary reaction mixture by completely reacting the mixture with all of the compounds, thereby providing a reacted mixture; and , (B) in a second stage, adding to the reacted mixture: (1) one or more AA-type compounds, one or more BB-type compounds, and one or more A-type compounds;
B-type compounds; (2) one or more AA-type compounds and one or more BB-type compounds in which the number of different AA-type compounds and BB-type compounds is 3 or more; and (3) two or more-types Adding a secondary mixture selected from the group consisting of AB-type compounds, wherein at least one AA in said secondary mixture;
BB or AB type compounds are not used in the primary mixture, and AA type compounds and B
12. A method for producing a polyquinoline copolymer composition, wherein the total number of B-type compounds is one or more, and the composite primary reacted mixture and secondary mixture are reacted for a selected time period; A method for producing polyquinoline block copolymers, comprising: (a) in a first stage, (1) one or more BB
Mixing the type compounds with one or more AB type compounds, forming a primary reaction mixture by completely reacting the mixture with all of the compounds, thereby providing a reacted mixture; and , (B) in a second stage, adding to the reacted mixture: (1) one or more AA-type compounds, one or more BB-type compounds, and one or more A-type compounds;
B-type compounds; (2) one or more AA-type compounds and one or more BB-type compounds in which the number of different AA-type compounds and BB-type compounds is 3 or more; and (3) two or more-types And adding a secondary mixture selected from the group consisting of AB type compounds of
A, BB or AB type compounds are not used in the primary mixture, and the total number of AA type compounds and BB type compounds in the secondary mixture is one or more, and 13. A process for producing a polyquinoline copolymer composition comprising reacting the reacted mixture and the secondary mixture for a selected time period; A process for producing polyquinoline triblock copolymers, comprising: (a) one or more AA-type compounds, one or more BB-type compounds, and zero or one or more ABs;
Mixing type compounds, wherein the total number of moles of AA type compounds is not equal to the total number of moles of BB type compounds, and reacting the mixture until the reaction is completed; (b)
14. After the completion of the reaction, a method for producing a polyquinoline triblock copolymer composition, which comprises adding one or more AB-type compounds and (c) completely reacting the reaction mixture. A method for producing polyquinoline triblock copolymers, comprising: (a) one or more hard rod AA type compounds, one or more hard rod BB type compounds, and zero or one or more hard rod AB Mixing the type compounds,
Reacting the mixture until the total number of moles of the AA type compounds is not equal to the total number of moles of the BB type compounds, and all of the hard rod compounds are completely reacted;
(B) adding one or more non-rigid rod AB-type compounds to the reaction mixture after all of the rigid rod compounds have completely reacted; and (c) completely reacting the reaction mixture. Consisting of a single rigid rod segment and two non-rigid rod segments consisting of
15. A method for producing a polyquinoline triblock copolymer composition, wherein the one non-rigid rod segment is bonded to each end of the rigid rod segment. A process for producing polyquinoline triblock copolymers, comprising: (a) one or more non-rigid rod AA compounds, one or more non-rigid rod BB compounds, and zero or one or more non-rigid rod BB compounds; The hard rod AB type compounds are mixed, wherein the total number of moles of the non-AA type compounds is not equal to the total number of moles of the non-BB type compounds, and all of the non-hard rod compounds are completely reacted. Reacting the mixture until: (b) after all of the non-rigid rod compounds have completely reacted, adding one or more rigid rod AB-type compounds to the reaction mixture; and (c) Consisting of a single non-rigid rod segment and two rigid rod segments consisting of completely reacting the reaction mixture, the rigid rod segments being connected to each end of the non-rigid rod segment. Method of manufacturing to have polyquinoline tri-block copolymer composition.

Other preferred embodiments of the present invention will be additionally described below. 1. A method for preparing a polyquinoline mixture composition,
(A) in a solvent mixture comprising one or more solvents,
All the selected polyquinoline polymers are sufficiently soluble, and the polyquinoline polymers are two or more polyquinoline polymers selected from the group consisting of polyquinoline homopolymers and polyquinoline copolymers Dissolving the solvent, and (b) evaporating the solvent from the resulting solution to produce a polyquinoline mixture composition, which comprises forming the polyquinoline mixture composition, a method of preparing a polyquinoline mixture composition, . A method for preparing a polyquinoline mixture composition,
(A) in a solvent mixture comprising one or more solvents,
The selected polyquinoline polymers are sufficiently soluble, and the polyquinoline polymers are two or more polyquinoline polymers selected from the group consisting of polyquinoline homopolymers and polyquinoline copolymers. 2. A method for preparing a polyquinoline mixture composition comprising: dissolving; and (b) adding one or more additional solvents to the product solution, and precipitating the polyquinoline mixture composition from solution. The method for preparing the polyquinoline mixture composition according to 1, wherein the solvent added for precipitating the polyquinoline mixture composition is a solvent that dissolves the selected polyquinoline polymers in an amount of less than about 0.1 gram per liter. 4. 4. The method for preparing a polyquinoline mixture composition according to the above 1, wherein the solvent added to precipitate the polyquinoline mixture composition is water; 5. the polyquinoline mixture prepared by the method of 1 above, wherein the solvent added to precipitate the polyquinoline mixture composition is an alcohol; The above 1 wherein the total concentration of the polyquinoline polymers in the working solution ranges from about 0.01% to about 50% by weight.
6. A polyquinoline mixture composition prepared by the method described in 7. above. A polyquinoline mixture composition prepared by the method of claim 1, wherein the total concentration of the polyquinoline polymers in the working solution ranges from about 0.01% by weight to a high concentration below which the solution becomes anisotropic. , 8. 2. A polyquinoline mixture composition prepared by the process of claim 1, wherein the total concentration of the polyquinoline polymers in the working solution ranges from about 1.0% by weight of polymer per liter of solution to a concentration at which the solution is anisotropic. Stuff.

[0118]

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

Example 1 Poly [(4-phenylquinoline-2,6-diyl) oxy (4-phenylquinoline-6,2-diyl] -1,4
-Phenyleneoxy 1,4-phenylene] -homopolymer (1) Preparation of 0.5223 g (1.279 mmol) of 4,4'-diamino-3,3'-dibenzoyldiphenyl ether and 0.3252 g of 4,4'-diacetyldiphenyl ether (1.279 g) (mmol), 8.1 g (32 mmol) of diphenyl phosphate and 1.5 g (14 mmol) of distilled m-cresol in a three-neck flask for polymerization (attached with an overhead stirrer and nitrogen inlet and outlet), and diphenyl phosphate started to melt. The mixture was warmed with dynamic bubbling of nitrogen. Agitation was initiated while continuing dynamic aeration for 20 minutes. 135-140 ° C
The oil bath was then lifted around the flask and then stirred vigorously for 48 hours while maintaining the flask at this temperature. The resulting clear and viscous yellow-orange solution was slowly placed in a stirred solution of 50 ml of triethylamine in 500 ml of ethanol to give a milky fibrous material. The fibrous polymer was suspended in a small amount (about 50 ml) of ethanol containing 10% v / v triethylamine, sheared with a blender, and collected by filtration. The polymer was continuously extracted with ethanol containing 10% v / v triethylamine in a Soxhlet apparatus for 24 hours. This is then air-dried and further dried at 105 ° C.
And dried at 0.1 mmHg for 4 hours. This polymer was redissolved in 30 ml of chloroform, and 30 ml of triethylamine was dissolved.
The precipitate was reprecipitated by slowly pouring into a stirred solution of 300 ml of ethanol. The reprecipitated fibrous polymer was suspended in about 50 ml of ethanol containing 5 ml of triethylamine, sheared with a blender and collected by filtration, air-dried and after drying at 105 ° C. and 0.1 mmHg for 4 hours, 0.69 g of polymer was obtained. Obtained. Dynamic mechanical analysis of the melt-bonded film (150 ° C, 20000 psi, 1 minute)
A single tan δ of x 276 ° C. was obtained.

Example 2 Poly [(4,4'-diphenylyl-6,6'-biquinolin-2,2'-diyl) -4,4'-biphenylene]
Preparation of homopolymer (2) In a 100 ml three-necked flask equipped with a mechanical stirrer and a nitrogen inlet and outlet, 3.0000 g (7.6440 mmol) of 3,3'-dibenzoylbenzidine, 4,4'-diacetyl 1.8215 g (7.6440 mmol) of biphenyl, 46.0 g (184 mmol) of diphenylphosphoric acid and 17 ml of freshly distilled m-cresol were added and nitrogen was dynamically bubbled through the resin flask and slowly added until the diphenylphosphoric acid began to melt. Slow stirring was started while vigorous nitrogen bubbling was continued for 20 minutes.The 135-140 ° C. oil bath was then lifted around the flask, and then the stirring speed was increased. The polymerization was maintained for a period of 48 hours, and an additional 100 ml of m-cresol was added in small portions during this 48 hour period to maintain efficient stirring. While hot, the deep red polymerization solution was poured into a stirred solution of 1 liter of ethanol containing 100 ml of triethylamine, and the resulting yellow, fibrous solid was reduced to 10% v / v.
v The suspension was suspended in a small amount (150 ml) of ethanol containing triethylamine and sheared with a blender. Next, the mixture was continuously extracted with ethanol containing 10% v / v triethylamine for 24 hours and dried under vacuum (105 ° C., 0.1 mmHg) for 24 hours.
A yellow fibrous polymer was obtained. Dynamic mechanical analysis of the cast film gave a single tan δ at Tmax of 369 ° C.

Example 3 Preparation of a Mixture of Homopolymers (1) and (2) A mixture of homopolymers (1) and (2) with varying proportions was prepared by mixing homopolymer (2) with m-cresol and di- m-
Prepared by slowly dissolving in a mixed solvent of cresyl phosphate 65:35. Solvent was fed to polymerization 3 with nitrogen inlet and outlet and mechanical stirrer
It was added to the dried homopolymer (2) in a one-necked flask. The flask was flushed with nitrogen for 20 minutes and then warmed to 85-95 ° C without stirring. 24 stirs
It did not start during -48 hours. The reason is that this gives the solvent time to swell the polymer. After stirring for at least 24 hours, the homogeneity of the solution was checked approximately every 12 hours at low magnification using an orthogonal polarizer. Only 24 hours after the appearance that the homopolymer (2) was completely dissolved, the flask was cooled and the solid homopolymer (1) was added to obtain the desired polymer ratio. In general, light microscopy indicated a homogeneous solution within 48 hours after addition of homopolymer (1), but stirring continued for an additional 24 hours. The polymer solution was then filtered through a 40-60 micron fritted glass filter using positive pressure. Using a mechanical stirrer and a three-neck flask for polymerization with a short diameter condenser,
The added m-cresol was vacuum distilled (aspirator pressure, oil bath temperature 150-160 ° C) to obtain the final polymer solution, which was used for film and fiber extraction or precipitation of mixed powder.

Example 4 Preparation of Polyquinoline Random Copolymer 0.687519 g of 3,3'-dibenzoylbenzidine (1.7518)
1mmol), 0.417330g of 4,4'-diacetylbiphenyl
(1.75136 mmol), 0.715331 g of 4,4'-diamino-3,3'-dibenzoyldiphenyl ether (1.75128 mmol
l) and 4,4'-diacetyldiphenyl ether
445430 g (1.75167 mmol) was added to diphenylphosphoric acid 21 g
And a 100 ml resin flask with mechanical stirrer (included nitrogen inlet and outlet) containing 8.1 g of freshly distilled m-cresol. The apparatus was warmed up slowly and flushed vigorously with nitrogen until the diphenylphosphate melted.
Aeration was performed for 20 minutes with stirring. The polymerization was then carried out as in Example 1 above (static nitrogen pressure, 135-140 ° C oil bath,
(Vigorous stirring) for 48 hours. This hot polymerization mixture is
Precipitated in 1 liter of 0% triethylamine / ethanol and shear filtered. The polymer was washed with a Soxhlet extractor using 10% triethylamine / ethanol.
After extraction for 4 hours, the mixture was dried in a vacuum (105 ° C., 0.1 mmHg) overnight. By dynamic mechanical analysis of cast film,
A single tan δ of Tmax 316.5 ° C was obtained.

Example 5 Preparation of Polyquinoline Block Copolymer Degree of Polymerization (DP) = 30 Blocks 3,3'-Dibenzoylbenzidine 2.99976 g (7.6448
mmol) and 4,4'-diacetylbiphenyl 1.720617
g (7.2207 mmol) was added to a 200 ml resin flask with a mechanical stirrer (with nitrogen inlet and outlet) containing 51 g of diphenylphosphoric acid and 17 ml of freshly distilled m-cresol. This device was used as described in Example 1 above.
For a minute and polymerization was carried out for 16 hours as described above. The DP at this stage is 30 when calculated from the Carothers equation using P = 0.959. The resin flask was cooled to room temperature and additional diphenyl phosphate 51
g with 4,4'-diamino-3,3'-dibenzoyldiphenyl ether 2.766466 g (6.7729 mmol) and 4,4'-diacetyldiphenyl ether 1.636142 g
(7.2207 mmol) was added. The apparatus was bubbled with nitrogen for 20 minutes and the polymerization continued at 135-140 ° C for an additional 24 hours. During this period, an additional 35 ml of m-cresol was added. The hot polymerization mixture was precipitated in 1 liter of 10% triethylamine / ethanol, cut, and extracted using a Soxhlet extractor using 10% triethylamine / ethanol for 24 hours. The polymer was dried under vacuum (0.1 mmHg, 105 ° C) for 12 hours and extracted with chloroform for another 24 hours. By extraction with chloroform,
Less than 7 wt% weight loss occurred. Finally, the polymer was dried under vacuum for 12 hours (0.1 mmHg, 10
5 ° C). Dynamic mechanical analysis (370 ° C,
30000 psi, 10 minutes), a single t of Tmax 308 ° C.
anδ was obtained.

Example 6 Preparation of Polyquinoline Block Copolymer Degree of Polymerization (DP) = 100 Blocks 4,179'-Diacetylbiphenyl 1.179532 g (4.9500 mm
ol) and 3,3'-dibenzoylbenzidine 1.962312
g (5.0000 mmol) was polymerized for 16 hours as in Example 1 above with 51 g of diphenylphosphoric acid and 17 ml of freshly distilled m-cresol. DP at this stage is P = 0.
Calculated from Carrosers equation using 995, 100
It is. After cooling the resin flask to room temperature, 1.098813 g (4.3211 mmol) of 4,4'-diacetyldiphenyl ether was added along with an additional 51 g of diphenylphosphoric acid and
1.744208 g (4.2702 mmol) of 4'-diamino-3,3'-dibenzoyldiphenyl ether were added. The polymerization was continued for an additional 48 hours as described above. The polymer was isolated as in Example 1 above. Dynamic mechanical analysis (370 ° C., 30000 psi, 10 minutes) of the melt-bonded film revealed a Tma of 308 ° C.
A single tan δ was obtained for x.

Example 7 Preparation of Polyquinoline Block Copolymer 1.179532 g of 4,4'-diacetylbiphenyl (4.9500 mm
ol) and 3,3'-dibenzoylbenzidine 1.962312
g (5.0000 mmol) were polymerized with 50 g of diphenylphosphoric acid and 17 ml of freshly distilled m-cresol for 16 hours as in Example 1 above. After cooling the resin flask, 3.33 g of 3-benzoyl-4-amino-4'-acetyldiphenyl ether (10.0 g) with an additional 51 g of diphenylphosphoric acid
mmol) was added and the polymerization was continued for another 48 hours as described above. The polymer is isolated as in Example 1 above. The resulting triblock copolymer has a rigid center block with DP = 50 and two flexible side blocks with DP dependent on the exact amount of flexible AB type monomer added in the second stage. Having. In many applications, the exact amount of AB monomer added is not as critical as the exact amount of AA and BB type monomers used in the first step of defining the mid-block DP.

Although the invention has been described in considerable detail with reference to examples thereof, it will be understood that modifications and improvements are valid within the concept and scope of the invention as defined in the appended claims. .

[0127]

According to the present invention, for example, high temperature for laminated resins, adhesive compositions, coating materials, films, fibers, especially aluminum, steel, and titanium alloys, which are heat stable. A method for producing metal adhesives, high-temperature electrical insulators, foams, ablative materials, and a polyquinoline block copolymer composition as a novel polyquinoline polymer material suitable for use as a rocket nozzle, etc. Can be provided.

Claims (16)

[Claims] (A) In the first stage, (1) one or more of the following AA type compounds, and one or more of the following B
B-type compounds and one or more of the following AB-type compounds; (2) one or more of the following AA-type compounds and 1 in which the number of different following AA-type compounds and BB-type compounds is 3 or more: Or more of the following BB-type compounds; and (3) two or more of the following AB-type compounds, wherein when the AA-type and BB-type compounds are used, the total number of moles of the AA-type compounds is Preparing a first reaction mixture of compounds selected from the group equal to the total number of moles of BB type compounds;
And reacting the primary mixture for a selected time to provide a reacted primary mixture; and, after the selection time, (b) in the secondary stage, A secondary mixture of compounds to provide the next reaction mixture is added, wherein the secondary mixture of compounds comprises: (1) one or more of the following AA-type compounds, one or more of the following B
B-type compounds and one or more of the following AB-type compounds; (2) one or more of the following AA-type compounds and one or more of the following three or more different AA-type compounds and BB-type compounds: The following BB type compounds; and (3) two or more of the following AB type compounds, wherein a secondary mixture of the above compounds is not used in at least one of the following AA type, BB type or primary stage A method for producing a polyquinoline block copolymer composition comprising the following AB compound and reacting a secondary reaction mixture for a selected time. However, AA type compounds have the formula: Is an aromatic compound containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: BB type compounds having the formula: Is an aromatic compound containing two methylene ketone functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group bound to an aromatic nucleus selected from the group consisting of the structures represented by Hydrogen or aryl, R 'is aryl, Ar is an aromatic nucleus where the position of attachment of each set of carbonyl and amino functional groups is ortho, and Ar'
Is any aryl where the attachment position of the amino functional groups is ortho, Ar ″ is any aryl, Ar ′ ″ is an aryl group, and four of these bonds are Occupied by a linkage, and Ar '''''is an aryl group in which the position of attachment of the set of carbonyl and amino functional groups is ortho. 2. (a) The following AA type compounds consisting of one or more non-rigid rods, the following BB type compounds consisting of one or more non-rigid rods, and zero or one or more of the following A
B type compounds are mixed, and the non-rigid rod AA is mixed therein.
Making the total number of moles of the type compounds equal to the total number of moles of the non-rigid rod BB type compounds and reacting the mixture for a primary selection time; (b) after the primary selection time, For the reaction mixture, the following AA type compounds consisting of one or more hard rods, the following BB type compounds consisting of one or more hard rods, and the following AB consisting of zero or more than one hard rods
A method for producing a polyquinoline block copolymer composition, comprising: adding type compounds; and (c) continuing the reaction for a second selection time.
However, AA type compounds have the formula: Is an aromatic compound containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing two methylene ketone functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group attached to an aromatic nucleus selected from the group consisting of structures represented by the following formulas: Hydrogen or aryl, R ′ is aryl, Ar is an aromatic nucleus in which the position of attachment of each of the carbonyl and amino functional groups is ortho, and Ar ′ is that in which the positions of amino functional groups are ortho Any aryl, Ar '' is any aryl, Ar '''' is an aryl group wherein four of these bonds are occupied by linkages of methylene carbonyl functionalities, and further, Ar '' ´´
Is an aryl group in which the position of attachment of the set of carbonyl and amino functional groups is ortho. (A) The following AA type compounds composed of one or more hard rods, the following BB type compounds composed of one or more rigid rods, and the following AB type compounds composed of one or more rigid rods And the hard rod A is mixed therein.
Making the total number of moles of the A-type compounds equal to the total number of moles of the hard rod BB-type compounds, and reacting the mixture for a first selection time; (b) after the first selection time, The following AA compounds comprising one or more non-rigid rods, the following BB compounds comprising one or more non-rigid rods, and the following AB compounds comprising one or more non-rigid rods And (c) continuing the reaction for a second selection time to produce a polyquinoline block copolymer composition.
However, AA type compounds have the formula: Is an aromatic compound containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: BB type compounds having the formula: Is an aromatic compound containing two methylene ketone functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group bound to an aromatic nucleus selected from the group consisting of the structures represented by Hydrogen or aryl, R 'is aryl, Ar is an aromatic nucleus where the position of attachment of each set of carbonyl and amino functional groups is ortho, and Ar'
Is any aryl where the attachment position of the amino functional groups is ortho, Ar ″ is any aryl, Ar ″ ″ is an aryl group, and four of these bonds are of the methylenecarbonyl functional group Ar '''''is an aryl group wherein the position of attachment of the set of carbonyl and amino functional groups is ortho. 4. (a) The following AA type compounds comprising one or more non-rigid rods, the following BB type compounds comprising one or more non-rigid rods, and zero or more non-rigid rods The following AB type compounds are mixed, wherein the total number of moles of the non-rigid rod AA type compounds is equal to the total number of moles of the non-rigid rod BB type compounds, and
Reacting the mixture for a primary selection time; (b) after the primary selection time, adding to the reaction mixture the following AB-type compounds consisting of one or more hard rods; (c) A method for producing a polyquinoline block copolymer composition, comprising continuing the reaction for a second selection time.
However, AA type compounds have the formula: Is an aromatic compound containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: BB type compounds having the formula: Is an aromatic compound containing two methylene ketone functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group bound to an aromatic nucleus selected from the group consisting of the structures represented by Hydrogen or aryl, R 'is aryl, Ar is an aromatic nucleus where the position of attachment of each set of carbonyl and amino functional groups is ortho, and Ar'
Is any aryl where the attachment position of the amino functional groups is ortho, Ar ″ is any aryl, Ar ″ ″ is an aryl group, and four of these bonds are of the methylenecarbonyl functional group Ar '''''is an aryl group wherein the position of attachment of the set of carbonyl and amino functional groups is ortho. 5. The following AA type compounds comprising one or more hard rods, the following BB type compounds comprising one or more hard rods, and the following AB type compounds comprising zero or more than one type of hard rods The compounds are mixed, and the total number of moles of the hard rod AA type compounds is mixed with the hard rod B.
Equalizing the total number of moles of the B-type compounds and reacting the mixture for a primary selection time; (b) after said primary selection time, one or more non- A method for producing a polyquinoline block copolymer composition, comprising: adding the following AB type compounds composed of hard rods; and (c) continuing the reaction for a second selection time.
However, AA type compounds have the formula: Is an aromatic compound containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: BB type compounds having the formula: Is an aromatic compound containing two methylene ketone functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group bound to an aromatic nucleus selected from the group consisting of the structures represented by Hydrogen or aryl, R 'is aryl, Ar is an aromatic nucleus where the position of attachment of each set of carbonyl and amino functional groups is ortho, and Ar'
Is any aryl where the attachment position of the amino functional groups is ortho, Ar ″ is any aryl, Ar ″ ″ is an aryl group, and four of these bonds are of the methylenecarbonyl functional group Ar '''''is an aryl group wherein the position of attachment of the set of carbonyl and amino functional groups is ortho. 6. (a) The following AA type compounds comprising one or more non-rigid rods, the following BB type compounds comprising one or more non-rigid rods, and zero or one or more non-rigid rods The following AB type compounds are mixed, wherein the total number of moles of the non-rigid rod AA type compounds is equal to the total number of moles of the non-rigid rod BB type compounds, and
Reacting the mixture until the viscosity of the reaction mixture indicates that the desired average molecular weight has been reached; (b) after the desired average molecular weight has been achieved, the following AA type comprising one or more hard rods Adding compounds, the following BB type compounds consisting of one or more hard rods and the following AB type compounds consisting of zero or more hard rods to the reaction mixture; and (c) secondary selecting the reaction. A method for producing a polyquinoline block copolymer composition which is continued for a time.
However, AA type compounds have the formula: Is an aromatic compound containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: BB type compounds having the formula: Is an aromatic compound containing two methylene ketone functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group attached to an aromatic nucleus selected from the group consisting of structures represented by the following formulas: Hydrogen or aryl, R ′ is aryl, Ar is an aromatic nucleus in which the position of attachment of each of the carbonyl and amino functional groups is ortho, and Ar ′ is that in which the positions of amino functional groups are ortho. Any aryl, Ar '' is any aryl; Ar '''' is an aryl group, wherein four of these bonds are occupied by a linkage of methylene carbonyl functionalities; ´´´
Is an aryl group in which the position of attachment of the set of carbonyl and amino functional groups is ortho. 7. (a) The following AA type compounds comprising one or more hard rods, the following BB type compounds comprising one or more hard rods, and the following AB type compounds comprising zero or one or more types of hard rods The compounds are mixed, and the total number of moles of the hard rod AA type compounds is mixed with the hard rod B.
Reacting the mixture to equal the total number of moles of type B compounds and until the viscosity of the reaction mixture indicates that the desired average polymer molecular weight has been reached; (b) the desired average molecular weight is achieved After that, the following AA type compounds composed of one or more non-rigid rods, the following BB type compounds composed of one or more non-rigid rods, and the following AB type compounds composed of zero or one or more non-rigid rods And (c) continuing the reaction for a second selection time. A method for producing a polyquinoline block copolymer composition.
However, AA-type compounds have the formula: Is an aromatic compound containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing two methylene ketone functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group attached to an aromatic nucleus selected from the group consisting of structures represented by the following formulas: Hydrogen or aryl, R ′ is aryl, Ar is an aromatic nucleus in which the position of attachment of each of the carbonyl and amino functional groups is ortho, and Ar ′ is that in which the positions of amino functional groups are ortho. Any aryl, Ar '' is any aryl; Ar '''' is an aryl group, wherein four of these bonds are occupied by a linkage of methylene carbonyl functionalities; ´´´
Is an aryl group in which the position of attachment of the set of carbonyl and amino functional groups is ortho. 8. (a) The following AA type compounds comprising one or more non-rigid rods, the following BB type compounds comprising one or more non-rigid rods, and zero or more non-rigid rods The following AB type compounds are mixed, wherein the total number of moles of the non-rigid rod AA type compounds is equal to the total number of moles of the non-rigid rod BB type compounds, and
Reacting the mixture until the viscosity of the reaction mixture indicates that the desired average polymer molecular weight has been reached; (b) after the desired average molecular weight has been achieved, the following AB type comprising one or more hard rods A method for producing a polyquinoline block copolymer composition comprising: adding compounds to the reaction mixture; and (c) continuing the reaction for a secondary selection time.
However, AA type compounds have the formula: Is an aromatic compound containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing two methylene ketone functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group bound to an aromatic nucleus selected from the group consisting of the structures represented by Hydrogen or aryl, R 'is aryl, Ar is an aromatic nucleus where the position of attachment of each set of carbonyl and amino functional groups is ortho, and Ar'
Is any aryl where the attachment position of the amino functional groups is ortho, Ar ″ is any aryl, Ar ″ ″ is an aryl group, and four of these bonds are of the methylenecarbonyl functional group Ar '''''is an aryl group wherein the position of attachment of the set of carbonyl and amino functional groups is ortho. 9. (a) The following AA type compounds comprising one or more hard rods, the following BB type compounds comprising one or more hard rods, and the following AB type comprising zero or one or more types of hard rods The compounds are mixed, and the total number of moles of the hard rod AA type compounds is mixed with the hard rod B.
Reacting the reaction mixture equal to the total number of moles of the B-type compounds and until the viscosity of the mixture indicates that the desired average polymer molecular weight has been reached; (b) the desired average molecular weight is achieved Then adding the following AB-type compounds comprising one or more non-rigid rods to the reaction mixture; and (c) continuing the reaction for a secondary selection time. A method for producing the composition.
However, AA type compounds have the formula: Is an aromatic compound containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: BB type compounds having the formula: Is an aromatic compound containing two methylene ketone functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group bound to an aromatic nucleus selected from the group consisting of the structures represented by Hydrogen or aryl, R 'is aryl, Ar is an aromatic nucleus where the position of attachment of each set of carbonyl and amino functional groups is ortho, and Ar'
Is any aryl where the attachment position of the amino functional groups is ortho, Ar ″ is any aryl, Ar ″ ″ is an aryl group, and four of these bonds are of the methylenecarbonyl functional group Ar '''''is an aryl group wherein the position of attachment of the set of carbonyl and amino functional groups is ortho. 10. A) The following AA type compounds comprising one or more non-rigid rods, the following BB type compounds comprising one or more non-rigid rods, and zero or one or more non-rigid rods The following AB type compounds are mixed, in which the total number of moles of the non-rigid rod AA type compounds is not equal to the total number of moles of the non-hard rod BB type compounds,
Reacting the mixture until all of the non-rigid rod compounds have completely reacted; (b) one or more rigid rods after all of the non-rigid rod compounds have completely reacted. The following AA compounds consisting of one or more hard rods and the following BB compounds consisting of one or more hard rods and the following AB consisting of zero or more hard rods
A method for producing a polyquinoline block copolymer composition comprising: adding type compounds to the reaction mixture; and (c) continuing the reaction for a secondary selection time.
However, AA type compounds have the formula: Is an aromatic compound containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing two methylene ketone functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group attached to an aromatic nucleus selected from the group consisting of structures represented by the following formulas: Hydrogen or aryl, R ′ is aryl, Ar is an aromatic nucleus in which the position of attachment of each of the carbonyl and amino functional groups is ortho, and Ar ′ is that in which the positions of amino functional groups are ortho. Any aryl, Ar '' is any aryl; Ar '''' is an aryl group, wherein four of these bonds are occupied by a linkage of methylene carbonyl functionalities; ´´´
Is an aryl group in which the position of attachment of the set of carbonyl and amino functional groups is ortho. 11. The following AA type compounds comprising one or more hard rods, the following BB type compounds comprising one or more hard rods, and the following AB type compounds comprising zero or one or more types of hard rods The compounds are mixed, and the total number of moles of the hard rod AA type compounds is not equal to the total number of moles of the hard rod BB type compounds. Reacting the mixture until it completely reacts; (b) after all of said hard rod compounds have completely reacted, the following AA-type compounds comprising one or more non-rigid rods, one or more non-rigid rods Adding to the reaction mixture the following BB type compounds consisting of hard rods and the following AB type compounds consisting of zero or more non-rigid rods; and (c) continuing the reaction for a second selection time From that Method of manufacturing that polyquinoline block copolymer composition.
However, AA type compounds have the formula: Is an aromatic compound containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: BB type compounds having the formula: Is an aromatic compound containing two methylene ketone functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group bound to an aromatic nucleus selected from the group consisting of the structures represented by Hydrogen or aryl, R 'is aryl, Ar is an aromatic nucleus where the position of attachment of each set of carbonyl and amino functional groups is ortho, and Ar'
Is any aryl where the attachment position of the amino functional groups is ortho, Ar ″ is any aryl, Ar ″ ″ is an aryl group, and four of these bonds are of the methylenecarbonyl functional group Ar '''''is an aryl group wherein the position of attachment of the set of carbonyl and amino functional groups is ortho. 12. (a) In the first stage, (1) one or more of the following AA type compounds are converted to one or more of the following A
Forming a primary reaction mixture by mixing with the B-type compounds and reacting the mixture until all of said compounds are completely reacted; and (b) in a second stage, adding the reacted mixture (1) one or more of the following AA type compounds, one or more of the following B
B-type compounds, and one or more of the following AB-type compounds; (2) one or more of the following AA-type compounds and one or more of the following AA-type compounds and BB-type compounds, the number of which is 3 or more: And (3) adding a secondary mixture selected from the group consisting of two or more of the following AB type compounds, wherein at least one of the AA, BB or AB type in the secondary mixture is added. The compounds are not used in the primary mixture, and in the secondary mixture, the total number of the AA-type compounds and the BB-type compounds is one or more. And reacting the secondary mixture for a selected period of time for the preparation of a polyquinoline block copolymer composition. Where A
The A-type compounds have the formula: Is an aromatic compound containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing two methylene ketone functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group attached to an aromatic nucleus selected from the group consisting of structures represented by the following formulas: Hydrogen or aryl, R ′ is aryl, Ar is an aromatic nucleus in which the position of attachment of each of the carbonyl and amino functional groups is ortho, and Ar ′ is that in which the positions of amino functional groups are ortho. Any aryl, Ar '' is any aryl; Ar '''' is an aryl group, wherein four of these bonds are occupied by a linkage of methylene carbonyl functionalities; ´´´
Is an aryl group in which the position of attachment of the set of carbonyl and amino functional groups is ortho. 13. (a) In the first stage, (1) one or more of the following BB type compounds are converted to one or more of the following A
Forming a primary reaction mixture by mixing with the B-type compounds and reacting the mixture until all of the compounds have completely reacted; and (b) in a second stage, the reacted primary The mixture contains (1) one or more of the following AA-type compounds, one or more of the following B
Type compounds and one or more of the following AB type compounds; (2) one or more of the following AA type compounds and one or more types in which the number of different following AA type compounds and the following BB type compounds is 3 or more: And (3) adding a secondary mixture selected from the group consisting of two or more of the following AB type compounds, wherein at least one of the AA, BB or AB type in the secondary mixture is added. The compounds are not used in the primary mixture, and in this secondary mixture, the total number of the AA type compounds and the AB type compounds is one or more, and the composite primary reacted mixture And reacting the secondary mixture for a selected period of time for the preparation of a polyquinoline block copolymer composition. However, AA type compounds have the formula: Is an aromatic compound containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: BB type compounds having the formula: Is an aromatic compound containing two methylene ketone functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group bound to an aromatic nucleus selected from the group consisting of the structures represented by Hydrogen or aryl, R 'is aryl, Ar is an aromatic nucleus where the position of attachment of each set of carbonyl and amino functional groups is ortho, and Ar'
Is any aryl where the attachment position of the amino functional groups is ortho, Ar ″ is any aryl, Ar ″ ″ is an aryl group, and four of these bonds are of the methylenecarbonyl functional group Ar '''''is an aryl group wherein the position of attachment of the set of carbonyl and amino functional groups is ortho. 14. (a) one or more of the following AA type compounds, one or more of the following BB type compounds, and zero or 1
A mixture of at least one of the following AB-type compounds,
(B) reacting the mixture until the reaction is completed without making the total number of moles of the A-type compounds equal to the total number of moles of the BB-type compounds; (C) completely reacting the reaction mixture, wherein the polyquinoline copolymer is a triblock copolymer having three polyquinoline segments, and The next segment is selected from the group consisting of polyquinoline homo-oligomer or polyquinoline co-oligomer, the remaining two segments being equal and selected from the group consisting of polyquinoline homo-oligomer and polyquinoline co-oligomer, Are different types, again characterized by a polysegment wherein each of the secondary segments is attached to each end of the primary segment. Method for producing a phosphorus block copolymer composition. However, AA type compounds have the formula: Is an aromatic compound containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: BB type compounds having the formula: Is an aromatic compound containing two methylene ketone functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group bound to an aromatic nucleus selected from the group consisting of the structures represented by Hydrogen or aryl, R 'is aryl, Ar is an aromatic nucleus where the position of attachment of each set of carbonyl and amino functional groups is ortho, and Ar'
Is any aryl where the attachment position of the amino functional groups is ortho, Ar ″ is any aryl, Ar ″ ″ is an aryl group, and four of these bonds are of the methylenecarbonyl functional group Ar '''''is an aryl group wherein the position of attachment of the set of carbonyl and amino functional groups is ortho. 15. (a) The following AA type compounds composed of one or more hard rods, the following BB type compounds composed of one or more rigid rods, and the following AB type composed of zero or one or more rigid rods The compounds are mixed, in which the total number of moles of the AA type compounds is not equal to the total number of moles of the BB type compounds, but all of the hard rod compounds are completely reacted. (B) after all of the hard rod compounds have completely reacted, add the following AB type compounds consisting of one or more non-hard rods to the reaction mixture, c) completely reacting the reaction mixture, wherein the polyquinoline copolymer comprises a single rigid rod segment and two non-rigid rod segments, wherein one of the non-rigid rod segments is Method for producing polyquinoline block copolymer composition characterized in that it is tri-block copolymers attached to each end of the rod segment. However, AA type compounds have the formula: Is an aromatic compound containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: BB type compounds having the formula: Is an aromatic compound containing two methylene ketone functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group attached to an aromatic nucleus selected from the group consisting of structures represented by the following formulas: Hydrogen or aryl, R ′ is aryl, Ar is an aromatic nucleus in which the position of attachment of each of the carbonyl and amino functional groups is ortho, and Ar ′ is that in which the positions of amino functional groups are ortho. Any aryl, Ar '' is any aryl; Ar '''' is an aryl group, wherein four of these bonds are occupied by a linkage of methylene carbonyl functionalities; ´´´
Is an aryl group in which the position of attachment of the set of carbonyl and amino functional groups is ortho. 16. (a) The following AA type compounds comprising one or more non-rigid rods, the following BB type compounds comprising one or more non-rigid rods, and zero or one or more non-rigid rods The following AB type compounds are mixed, in which the total number of moles of the non-rigid rod AA type compounds is not equal to the total number of moles of the non-hard rod BB type compounds,
Reacting the mixture until all of the non-rigid rod compounds are completely reacted; (b) one or more rigid rods after all of the non-rigid rod compounds are completely reacted. (C) completely reacting the reaction mixture, wherein the polyquinoline copolymers comprise a single non-rigid rod segment and two A method for producing a polyquinoline block copolymer composition comprising a hard rod segment, wherein each of the hard rod segments is bonded to each end of the non-hard rod segment. However, AA
The type compounds have the formula: Is an aromatic compound containing two orthoaminocarbonyl functional groups attached to an aromatic nucleus selected from the group consisting of structures represented by the formula: BB type compounds having the formula: Is an aromatic compound containing two methylene ketone functional groups bonded to an aromatic nucleus selected from the group consisting of structures represented by the formula: Is an aromatic compound containing one orthoaminocarbonyl functional group and one methylene ketone functional group attached to an aromatic nucleus selected from the group consisting of structures represented by the following formulas: Hydrogen or aryl, R ′ is aryl, Ar is an aromatic nucleus in which the position of attachment of each of the carbonyl and amino functional groups is ortho, and Ar ′ is that in which the positions of amino functional groups are ortho. Any aryl, Ar '' is any aryl; Ar '''' is an aryl group, wherein four of these bonds are occupied by a linkage of methylene carbonyl functionalities; ´´´
Is an aryl group in which the position of attachment of the set of carbonyl and amino functional groups is ortho.