JPH0532716A - Foramide group-containing copolymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain a copolymer having an excellent hue without causing gelatinization resulting from crosslinking reaction by treating a polyfunctional copolymer containing (substituted) succinic anhydride group with a diamine to introduce formamide group, etc., to the side chain. CONSTITUTION:A polyfunctional copolymer containing (substituted) succinic anhydride group as a functional group is treated with a diamine, polymer modifying reaction is carried out, formamide group or formamide group and a primary amino group are introduced into the side chain to give a copolymer containing (A) 20-99.8mol% repeating unit shown by formula I (R<1> and R<2> are H, 1-10C alkyl, etc.), (B) 50-0mol% repeating unit shown by formula II (R<3> and R<4> are H, 1-4C alkyl, etc.) and (C) 30-0.2mol% total amounts of (i) repeating units shown by formula III to formula V (R<6>, R<7> and R<12> are H, 1-10C alkyl, etc.; R<8> is single bond, methylene, etc.; R<9> and R<10> are H, 1-6C alkyl, etc.; R<11> is 1-12C alkylene; X<1> and X<2> are NH2 or NH-CHO) in the molecule or a salt thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copolymer having a formamide group and a method for producing the same, more specifically, a high molecular weight amino reagent, a functional polymer raw material, an adhesive raw material, a polymer compatibilizer, A novel copolymer having a formamide group, which can be used as a resin modifier, etc. and can give a copolymer having a primary amino group by hydrolysis, and a novel copolymer having a primary amino group obtained by hydrolysis. The present invention relates to a copolymer and an efficient production method thereof.

[0002]

2. Description of the Related Art Conventionally, a polymer compound having a primary amino group in the side chain has a high reaction activity of the amino group, that is, aldehyde, ketone, alkyl halide, isocyanate, thioisocyanate, active double bond. , Epoxy compound, cyanamide, guanidine, urea, acid,
Since it easily reacts with functional groups such as acid anhydrides and acyl halides, it is effectively used in various industrial fields. As a polymer compound having such a primary amino group in its side chain, there has hitherto been obtained by polymerization of polyvinylamine or allylamine hydrochloride by hydrolysis of poly-N-vinylacetamide or poly-N-vinylformamide. Polyallylamine and the like are known.

However, when a polymer compound is produced by these methods, a polymer or copolymer having a primary amino group can be obtained, but the molecular weight does not become larger than intended, and an amine or an amine precursor is used. Since the monomer (1) is radically polymerized, there are restrictions such as restrictions on the type of the monomer of the copolymerization partner, and sufficient performance may not be exhibited depending on the application.

Examples of copolymers having an amino group in the side chain include JP-A-2-135214 and JP2-13522.
No. 15, gazette of styrene-maleic anhydride copolymer.
It has been proposed to use a copolymer obtained by imidization with primary and secondary mixed diamines such as aminophenol and ethylaminoethylamine as a latent epoxy curing agent. This copolymer also has an ethylamino group in the side chain, but in this case, the side chain functional group obtained is a secondary amino group, and generally the secondary amino group is a primary amino group. It is less versatile as a functional group than a group, and is not desirable in this respect. Unintentionally,
As an example in which a primary amino group is considered to be partially introduced in the side chain, JP-A-64-70595 and JP-A-6-70595.
The copolymers described in 4-85246 and U.S. Pat. No. 4,137,185 can be mentioned. That is, a maleic anhydride-grafted ethylene-propylene copolymer obtained by grafting maleic anhydride onto an ethylene-propylene copolymer has at least 2 parts such as diethylenetriamine, ethylenediamine and hexamethylenediamine.
It is an imidized product obtained by reacting a polyamine having individual primary amino groups. However, in the reaction of a polyfunctional anhydride and a polyfunctional polyamine such as this maleic anhydride-grafted ethylene-propylene copolymer, it is generally considered that a considerable amount of crosslinking reaction occurs during and after the reaction. To be Further, if a crosslinking reaction occurs during the reaction, it is often observed that the viscosity of the reaction mixture increases, and eventually progresses to gelation, making it impossible to continue the reaction thereafter. Therefore, in these prior arts, the primary amine present after the imidization reaction was converted into acetic anhydride, n
-A device for end-capping with octenyl succinic anhydride is used.

Further, in Japanese Patent Laid-Open No. 2-36248,
It has also been suggested to react a polyolefin graft-modified with an unsaturated acid anhydride with a diamine, but there is no specific production method or product, and according to a known method, the present inventors From experience, crosslinking and gelation are inevitable.

As an example of reacting a maleic anhydride copolymer or a maleic anhydride-grafted ethylene-propylene copolymer with a primary diamine, JP-A-60-2407 is known.
49 gazette, the same 64-31864 gazette, the same 63-14.
6928, 63-235365, 63.
As disclosed in Japanese Patent Application Laid-Open No. 1997-1975, all of them are aimed at imide cross-linking of a non-hydroxyl group and two primary amino groups in a solventless resin. As a method of imidizing with a primary diamine to form a primary amino group on a side chain without causing a crosslinking reaction, gelation accompanying the crosslinking reaction is substantially negligible. Primary amino group /
It is theoretically possible to increase the molar ratio of succinic anhydride groups to carry out the imidization reaction, but it is not practical. Therefore,
The present inventors have previously proposed an improved production method that overcomes the drawbacks of the known art and a novel copolymer obtained by this method (see Japanese Patent Application No. 3-85736). ). Here, the present inventors have proposed a method in which a partial salt of a diamine and an acid is reacted with a succinic anhydride group-containing copolymer, and then a base is allowed to act to regenerate an amino group.

[0007]

Conventionally, a polyfunctional copolymer having a substituted or unsubstituted succinic anhydride group as a functional group is treated with a diamine to give a primary amino group by a polymer modification reaction. It has been considered technically difficult to obtain a copolymer having a good hue without causing gelation due to a crosslinking reaction when introduced into a side chain. The present invention has been made focusing on such conventional problems.

[0008]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems of the prior art, and found that repeating units derived from styrene, olefins or their derivatives, and dienes such as butadiene. A copolymer having a repeating unit derived from and a repeating unit grafted with an acid anhydride such as maleic anhydride is reacted with a salt of a specific primary diamine in the presence of a formyl group-containing compound such as formamide. Imidization and / or amidation, further deoxidation with a base, or imidation and / or a reaction product obtained by reacting the above copolymer with a primary diamine and a formyl group-containing compound such as formamide By amidation, a novel copolymer containing a formamide group can be obtained. Further, if the novel copolymer is hydrolyzed, the properties suitable for the above purpose can be obtained. It found that the can be obtained. The present invention has been completed based on such findings.

That is, the present invention has the general formula (I) in the molecule.
The repeating unit A represented by the formula A20-99.8 mol%, the general formula (I
The repeating unit B represented by I) is 50 to 0 mol%, and the general formula (II
The total amount of the repeating unit C represented by I), the repeating unit D represented by the general formula (IV) and the repeating unit E represented by the general formula (V) is 30 to 0.2 mol% (provided that the repeating unit is C is 0.2 mol% or more.)

[0010]

[Chemical 5]

[0011]

[Chemical 6]

[0012]

[Chemical 7]

(Wherein R ¹ , R ² , R ⁵ , R ⁶ and R ⁷
Are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
C3-C8 cycloalkyl group, C6-C10 aryl group, C2-C4 alkenyl group, C1-C4
Alkoxy group, C1-18 alkoxycarbonyl group, C1-17 alkylcarboxyl group, C1-6 alkylcarbonyl group, C6-8 arylcarbonyl group, halogen atom or nitrile group R ³ and R ⁴ are each independently a hydrogen atom and a carbon number of 1 to
4 represents an alkyl group, an alkenyl group having 2 to 4 carbon atoms or a halogen atom, R ⁸ does not exist or represents a methylene group or an ethylene group, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a carbon number of 1 indicates 6 alkyl group or an aryl group having 6 to 8 carbon atoms, R ¹¹ is an alkylene group having 1 to 12 carbon atoms, cycloalkylene group having 5 to 17 carbon atoms,
An arylene group having 6 to 12 carbon atoms, an arylalkylene group having 7 to 12 carbon atoms or a polyoxyalkylene group having 4 to 30 carbon atoms is shown, and R ¹² is a hydrogen atom or 1 carbon atom.
10 represents an alkyl group. n shows the integer of 1-10. Note that R ^{1 to} R ¹² may be the same or different for each repeating unit. Further, X ¹ and X ² each independently represent NH ₂ or NH—CHO. ) Containing a copolymer or a salt thereof.

In the present invention, the repeating unit A represented by the general formula (I) A20 to 99.8 mol% in the molecule, the general formula (II)
And the general formula (VI)
The repeating unit represented by C'30-0.2 mol%

[0015]

[Chemical 8]

In the copolymer containing (wherein R ^{5 to} R ¹⁰ , R ¹² and n are the same as above), the general formula (VII) H ₂ N—R ¹¹ —NH ₂ ... (VII) reacting a salt of a diamine represented by the formula (wherein R ¹¹ is the same as above) in the presence of at least one formyl group-containing compound selected from formamide, formic acid and derivatives thereof. The present invention provides a method for producing the above-mentioned copolymer or a salt thereof (method (a)), which comprises contacting with a base for deoxidation after the reaction.

The present invention further relates to a product obtained by reacting a diamine represented by the general formula (VII) with at least one formyl group-containing compound selected from formamide, formic acid and derivatives thereof, Repeating unit A represented by general formula (I) A20 to 99.8 mol% in the molecule, general formula (II)
And the general formula (VI)
The method for producing the above copolymer (method (b)) is characterized by reacting a copolymer containing the repeating unit C ′ of 30 to 0.2 mol% represented by Is hydrolyzed under acidic conditions, repeating units A20-99.8 mol% represented by the general formula (I) in the molecule, repeating units B50-0 represented by the general formula (II). Mol%, the total amount of the repeating unit D represented by the general formula (IV) and the repeating unit E represented by the general formula (V) is 30 to 0.2 mol% (wherein the repeating unit D is 0.2 mol% As described above, X ¹ and X ² are both NH _2. ) A method for producing a copolymer or a salt thereof (method (c)), and a copolymer or a salt thereof are provided.

The copolymer having a formamide group (including a salt thereof; the same applies hereinafter) of the present invention has a repeating unit A represented by the general formula (I) and a repeating unit B represented by the general formula (II). ，
A novel copolymer having a repeating unit C represented by the general formula (III), a repeating unit D represented by the general formula (IV) and a repeating unit E represented by the general formula (V) (provided that the repeating unit is B, D and E are not essential) and are random, block or graft copolymers thereof. The content ratio of each repeating unit in this copolymer is, as described above, based on the total amount of repeating units A, B, C, D and E,
Repeating unit A is 20 to 99.8 mol%, preferably 60 to 9
9 mol%, the repeating unit B is 50 to 0 mol%, preferably 4
0 to 0 mol%, the total amount of repeating units C, D and E is 30 to
0.2 mol% (provided that the repeating unit C is 0.2 mol% or more. The repeating units D and E may be 0).
Of the total amount of the repeating units C, D and E, the repeating unit C is preferably 20 to 1 mol%, and the repeating units D and E are each 2
It is preferably 0 mol% or less. Here, if the proportion of the total amount of repeating units C, D and E exceeds 30 mol%, it is difficult to obtain the obtained copolymer, and if it is less than 0.2 mol%, the formamide of the present invention is not obtained. The characteristics of the copolymer having a group are not sufficiently expressed. The copolymer of the present invention basically comprises the above repeating units A, B, C, D and E, but it may contain a small amount of other repeating units.

The molecular weight of the copolymer of the present invention is not particularly limited, but usually the viscosity average molecular weight is 30.
It is 00-500000. This was obtained by dissolving the formamide group-containing copolymer at 10% by weight in a good solvent such as toluene, xylene, cumene, tetralin, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, acetone and methylethylketone. Viscosity 10-500
This corresponds to a range of 00 cps.

The copolymer of the present invention is characterized in that the side chain of the repeating unit C has a formamide group or a primary amino group at the same time through an imide group or an amide group. In the copolymer of the present invention, the primary amino group has a sulfonic acid such as sulfuric acid, benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid. And the like, which forms a salt by binding with an acid such as halogeno acid, nitric acid, boric acid, phosphoric acid and the like.

The repeating unit A is represented by the general formula (I).
R in the formula¹And R ²Each independently (
Mari, R¹And R²May be the same or different)
Child, an alkyl group having 1 to 10 carbon atoms (preferably 1 carbon atom)
~ 4 alkyl group), C3-8 cycloalkyl group
(Preferably a cycloalkyl group having 3 to 6 carbon atoms), carbon
An aryl group having 6 to 10 carbon atoms (preferably an aryl group having 6 to 9 carbon atoms)
Reel group), alkenyl group having 2 to 4 carbon atoms (vinyl group,
(Allyl group, etc.), C1-C4 alkoxy group, C1
~ 18 alkoxycarbonyl group (preferably having 1 carbon atom)
~ 8 alkoxycarbonyl group), a C1-17 alkoxy group
Rukyi carboxyl group (preferably an alkyl group having 1 to 3 carbon atoms)
(Kill carboxyl group), alkylcarbo having 1 to 6 carbon atoms
Nyl group (preferably alkylcarbonyl having 1 to 4 carbon atoms)
Group), arylcarbonyl group having 6 to 8 carbon atoms, halogen
Indicates an atom (preferably chlorine or bromine) or a nitrile group
You In addition, R¹And R²Is the same for each repeating unit
It may be one or different. That is, the above general formula (I)
Is an ethylene unit (R¹And R²But
Both are hydrogen), and another one of repeating units A is
Ren unit (R¹Is hydrogen, R²Is a methyl group)
Also includes.

The repeating unit B is represented by the general formula (II).
However, in the formula, R³And R ^FourAre each independently hydrogen
Atoms, alkyl groups having 1 to 4 carbon atoms (methyl group, ethyl group
Etc.), alkenyl groups having 2 to 4 carbon atoms (vinyl group, allyl)
Group) or halogen atom (chlorine, bromine, etc.).
In addition, R³And R^FourAre the same for each repeating unit
It may or may not be the same as the above R¹And R²of
It is similar to the case. Further, the repeating unit C has the general formula (III)
Is represented, where R^Five~ R⁷Is the R¹, R
²In the same manner as above, hydrogen atom and C1-10
Rualkyl group (preferably alkyl group having 1 to 4 carbon atoms), charcoal
An alkenyl group having a prime number of 2 to 4 (vinyl group, allyl group, etc.),
A cycloalkyl group having 3 to 8 carbon atoms (preferably 3 carbon atoms)
~ 6 cycloalkyl group), aryl having 6 to 10 carbon atoms
Group (preferably aryl group having 6 to 9 carbon atoms), carbon number 1
~ 4 alkoxy groups, C1-C18 alkoxycarcs
Bonyl group (preferably alkoxycarbo having 1 to 8 carbon atoms)
Nyl group), an alkylcarboxyl group having 1 to 17 carbon atoms
(Preferably C1-C3 alkyl carboxyl
Group), an alkylcarbonyl group having 1 to 6 carbon atoms, and 6 carbon atoms
8 arylcarbonyl group (preferably having 1 to 4 carbon atoms)
Alkylcarbonyl group), halogen atom (preferably
Chlorine, bromine) or nitrile group. Also, R⁸Is
Non-existent (ie showing a mere bond) or methylene group
Or an ethylene group, R⁹And R^TenEach independently
Hydrogen atom, alkyl group having 1 to 6 carbon atoms (preferably carbon
An alkyl group having 1 to 2) or an aryl having 6 to 8 carbons
R group¹¹Is an alkylene group having 1 to 12 carbon atoms (preferred
More preferably methylene, ethylene, propylene, tetramethy
C1-C8 alkylene such as len and hexamethylene
Group), a cycloalkylene group having 5 to 17 carbon atoms (preferably
Is cyclohexylene, methylene cyclohexyl methylene
Such as cycloalkylene groups having 6 to 10 carbon atoms), 6 carbon atoms
To 12 arylene groups (preferably phenylene, oxy)
Diphenylene etc.), arylalkyle having 7 to 12 carbon atoms
Group (preferably an ant having 8 to 10 carbon atoms such as xylylene)
Alkylene group) or polyoxy having 4 to 30 carbon atoms
Sialkylene group (polyoxymethylene, polyoxypropylene
A polyoxyalkylene group having 4 to 15 carbon atoms such as
Show, R¹²Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
Group (preferably an alkyl group having 1 to 8 carbon atoms).
These R^Five~ R¹²Are the same for each repeating unit
It may or may not be the same as the above R¹And R²of
It is similar to the case. Further, n is 1 to 10 (preferably 1
~ 3) is an integer. Here, n is plural, that is, 2 or more.
When, each R exists by the number of n⁹, R^Ten, R¹¹Is the same
It may be the same or different.

The amino group-containing copolymer of the present invention can be produced by various methods without any particular limitation. According to the above-mentioned methods (a) and (b) of the present invention, further It can be manufactured efficiently. First, the copolymer containing the repeating units A, B and C ′, which is a raw material of the method of the present invention, is prepared by using a known method to prepare a monomer giving the repeating units represented by the general formulas (I) and (II). It is produced by radical polymerization or ionic polymerization, followed by graft reaction of a monomer giving the general formula (VI) by a known method. Specific examples of the monomer that gives the repeating unit A of the general formula (I) include various ones. For example, olefins such as ethylene, propylene, 1-butene, isobutylene, 1-octene, cyclopentene, cyclohexene, cyclooctene, etc. Cyclic olefins, styrenes such as styrene, α-methylstyrene, vinyltoluene, pt-butylstyrene (aromatic vinyl compounds), vinyl esters such as vinyl acetate, vinyl butyrate, vinyl stearate,
Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, halogeno olefins such as vinyl chloride and vinylidene chloride, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
Acrylic acid or methacrylic acid esters such as hexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate, octadecyl (meth) acrylate, methoxyethyl (meth) acrylate, nitriles such as acrylonitrile and methacrylonitrile , Vinyl vinyl ketone, phenyl vinyl ketone, and other vinyl ketones, and these can be used alone or in combination of two or more. Among these, examples of preferable monomers include ethylene, propylene, styrene, methyl vinyl ether, isobutylene, vinyl acetate, and (meth) acrylic acid esters. Further, hydrogenated products of polymers of isoprene and butadiene can also be used. Specific examples of the monomer that gives the repeating unit B of the general formula (II) include conjugated dienes such as butadiene, isoprene, and chloroprene.
These may be used alone or in combination of two or more. Preferred monomers include butadiene,
Mention may be made of isoprene. The repeating unit C ′ of the general formula (VI) is obtained by copolymerizing a monomer giving the repeating unit A and a monomer giving the repeating unit B by a known method,
The obtained copolymer is treated with a known peroxide, an initiator or the like to give maleic anhydride, methylmaleic anhydride, 1,2.
-It can be formed by grafting an unsaturated dicarboxylic acid anhydride such as dimethylmaleic acid, ethylmaleic anhydride, phenylmaleic anhydride or itaconic anhydride. The preferred grafting monomer is maleic anhydride. Here, the graft reaction proceeds by binding a grafting monomer such as maleic anhydride to the repeating unit A or B. As the raw material copolymer containing the repeating unit C ′ used in the present invention, a polymer commercially available as a polymer grafted with the unsaturated dicarboxylic acid anhydride (maleic acid-modified EPR or maleic acid-modified S
It is also possible to apply EBS, etc.).

From the above, the copolymer containing the repeating units A, B and C ′, which are the raw materials of the method of the present invention, will be exemplified.
Polyethylene, polypropylene, polyisoprene and its hydrogenated product, polybutadiene and its hydrogenated product, chloroprene rubber and its hydrogenated product, nitrile rubber and its hydrogenated product, ethylene-propylene copolymer, ethylene- (meth) acrylic acid ester Copolymer, styrene-isoprene copolymer and hydrogenated product thereof, styrene-
Polymers or copolymers such as butadiene copolymer and hydrogenated products thereof (note that in the case of the copolymer, it may be a random copolymer, a block copolymer, or an alternating copolymer) And a copolymer obtained by graft-reacting an anhydride of an unsaturated dicarboxylic acid such as maleic anhydride, methylmaleic anhydride, ethylmaleic anhydride, and itaconic anhydride. However, it should not be limited to these examples.

Further, according to the method (a) of the present invention, the copolymer containing the repeating units A, B and C ′ produced as described above is selected from formamide, formic acid and derivatives thereof. And reacting with a salt of a primary diamine represented by the general formula (VII) in the presence of at least one formyl group-containing compound. The formyl group-containing compound used here is formamide, formic acid or a derivative thereof as described above, and a commercially available product can be used. Derivatives of this formamide include N-methylformamide;
N-ethylformamide; N-butylformamide;
Nitrogen-substituted formamides such as N, N-dimethylformamide; N, N-diethylformamide; N-methylformanilide; N-ethylformanilide and the like can be mentioned. Examples of formic acid derivatives include formic acid esters such as methyl formate, ethyl formate, propyl formate and butyl formate, and salts of formic acid such as sodium formate, potassium formate and ammonium formate.

Specific examples of the diamine represented by the general formula (VII) include ethylenediamine; 1,3-diaminopropane; 1,4-diaminobutane; 1,5-diaminopentane; hexamethylenediamine; 7-diaminoheptane; 1,8-diaminooctane; 1,9-diaminononane; 1,10-diaminodecane; 2,2,5-trimethylhexanediamine; Aliphatic alkylenediamines, isophoronediamine; 1,3-bis (aminomethyl) cyclohexane; bis (4-aminocyclohexyl) methane; bisaminomethylhexahydro-4,
7-methaneindane; 1,4-cyclohexanediamine; 1,3-cyclohexanediamine; 2-methylcyclohexanediamine; 4-methylcyclohexanediamine; alicyclic such as bis (4-amino-3,5-dimethylcyclohexyl) methane Diamines, m-xylylenediamine; arylalkyldiamines such as p-xylylenediamine, p-phenylenediamine; aryldiamines such as 4,4′-diaminodiphenylether, polyoxypropylenediamine; polyoxyalkylenes such as polyoxyethylenediamine Diamine can be illustrated. Of these, particularly preferred are aliphatic and alicyclic diamines. This diamine may be either a partially neutralized salt (mono salt) or a completely neutralized salt (di salt), but a method using a partially neutralized salt is preferable because of high reaction efficiency. The diamine is preferably used as a partially neutralized salt of an acid, and it is desirable to select such an acid having an acid strength larger than that of the carboxylic acid. Specific examples include sulfonic acids such as sulfuric acid, benzene sulfonic acid, toluene sulfonic acid, and naphthalene sulfonic acid, halogeno acids such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, and hydroiodic acid, nitric acid, boric acid. , Phosphoric acid, etc. Of these, hydrochloric acid and toluenesulfonic acid are preferable.

In producing the salt of the diamine, the molar ratio of the diamine to the acid corresponds to a neutralization degree of 50 to 100% in terms of acid equivalent based on the total amino groups of the diamine. Used in. If it is less than 50%, crosslinking and gelation cannot be avoided during the imidization reaction. Again 100
When it exceeds%, the imidization reaction takes a long time, which is economically disadvantageous. The preferred range is 50-80%. The diamine salt can be easily prepared by a neutralization reaction between the corresponding diamine and the corresponding acid. For example, a diamine may be added dropwise to an alcohol solution of an acid, if necessary, concentrated, recrystallized with alcohol, isolated and used as a raw material, or the above-described formyl group-containing compound or 1,3-dimethyl-2- Imidazolidinone (DMI); N-methyl-2
-Pyrrolidone; dimethyl sulfoxide (DMSO); dimethyl sulfone; dioxane; 1,2-dimethoxyethane; hexamethylene phosphoric acid-triamide; partially neutralized salts of diamine and acid in an aprotic polar solvent such as tetramethylurea. It may be formed and used as it is in the reaction. In terms of operation, it is more efficient and preferable to form a salt in the formyl group-containing compound and use it in the reaction as it is.
In the method (a) of the present invention, the reaction product obtained as described above may then be contacted with a base for deoxidation.

As another method for obtaining the copolymer of the present invention, a product obtained by reacting the diamine represented by the general formula (VII) with the above-mentioned formyl group-containing compound is used as a reaction reagent. The method (b) of the present invention may be used in which the copolymer containing the repeating units A, B and C ′ is used for imidization or simultaneous amidation reaction. This reaction reagent is at least 1 mol per mol of the formyl group-containing compound,
Preferably 1.5 to 5 times the molar amount of diamine is 60 to 180
It is prepared by imidization or amide exchange at 2 ° C., preferably 80 to 150 ° C. for 2 to 5 hours. In this reaction, it is preferable to distill off water in the case of formic acid, alcohol in the case of formic acid ester, and ammonia or amine in the case of formamides. The product obtained here can be used as it is as the next imidization or amidation reagent, but the product usually contains unreacted diamine, which causes crosslinking and gelation. The problem arises. Therefore, the product is preferably heated under reduced pressure to distill off unreacted diamine, or in the case of a high-boiling diamine, it is preferable to remove the dihydrochloride by neutralizing once with hydrochloric acid or the like and recrystallizing.

The processes (a) and (b) of the present invention are carried out by using the copolymer of general formula (VI) for the copolymer containing the repeating units A, B and C '.
The reaction proceeds by reacting a salt of the diamine represented by I) with a formyl group-containing compound, or by reacting the above copolymer with a reaction product of the diamine and the formyl group-containing compound. Here, the imidization reaction can be carried out in a solvent-free molten state using a screw extruder or the like,
For the purpose of avoiding a local reaction and making the reaction uniform, it is desirable to use an inert solvent in addition to the formyl group-containing compound as a solvent. Inert solvents that can be used for such purposes include benzene, toluene, xylene, cumene,
Aromatic hydrocarbons such as cymene, ethyltoluene, propylbenzene, diethylbenzene, methylcyclopentane,
Alicyclic hydrocarbons such as cyclohexane, ethylcyclopentane, methylcyclohexane, 1,1-dimethylcyclohexane and ethylcyclohexane, aliphatic hydrocarbons such as hexane, heptane, octane, decane, methylheptane, 3-ethylhexane and trimethylpentane , 1,
3-dimethyl-2-imidazolidinone (DMI), tetramethylurea, dimethyl sulfone, dioxane, 1,2
Aprotic polar solvents such as -dimethoxyethane, hexamethylenephosphoric triamide, DMSO, N-methyl-2-pyrrolidone. The method (a) of the present invention,
In (b), since reaction substrates having considerably different polarities are reacted with each other, it is generally preferable to use a nonpolar solvent and a polar solvent at the same time.

The amount of the above-mentioned solvent used is not particularly limited and may be appropriately selected depending on the situation, but it is usually a copolymer containing repeating units A, B and C ′ (ie, substituted or substituted) used as a raw material. The weight ratio may be 0.3 to 20 times, preferably 1 to 10 times the weight of the polyfunctional copolymer having unsubstituted succinic anhydride as a functional group. If the amount is less than 0.3 times, the dilution effect may not be sufficient, and the reaction mixture may have a high viscosity and may be difficult. On the other hand, if the amount is more than 20 times, the effect corresponding to the amount used is not particularly improved, which is economically disadvantageous. The ratio of the inert solvent to the formyl group-containing compound as a solvent (inert solvent / formyl group-containing compound) is not particularly limited, but is 40 by weight.
/ 60 to 100/0 (100/0 is the case of the method (b)), preferably 50/50 to 95/5. In the present invention, when using a reaction product obtained by reacting a diamine and a formyl group-containing compound as a reaction substrate for imidization and amidation, it is not necessary to use the formyl group-containing compound as a solvent, In other cases (that is, in method (a)), it is essential (however, not as a solvent but as a reaction substrate) and used in the form of a mixed solvent with an inert solvent for dilution. As for the ratio, when the ratio of the formyl group-containing compound is increased according to the ratio of the functional group of the starting material used, the solubility of the substrate is better and the reaction rate tends to be higher.

The imidation reaction and amidation reaction in the methods (a) and (b) of the present invention do not require a catalyst, but when used, they are, for example, trimethylamine, triethylamine, tributylamine, N, N-dimethyl. Tertiary amines such as aniline, N, N-diethylaniline, 1,8-diazabicyclo (5.4.0) undecene-7 are preferred.

In the method of the present invention, the use ratio of the raw material copolymer, the diamine or its salt, and the formyl group-containing compound varies depending on the type and situation of the raw material used and cannot be uniquely determined. Is 1.0 mol based on the unneutralized amino group or unreacted amino group of the diamine, based on 1 mol of the substituted or unsubstituted succinic anhydride group (that is, repeating unit C ') contained in the raw material copolymer. -10 times, preferably 1.0
5 to 5.0 times. If it is less than 1.0 times, there will be succinic anhydride groups that remain without being imidized or amidated even after the completion of the reaction, and in the method (a), the primary amino acid regenerated in the deoxidation step. There is a possibility that a group reacts with the succinic anhydride group to cause gelation due to amide cross-linking, thereby overturning the effect of the present invention. On the other hand, when the molar ratio exceeds 10 times, the imidization or amidation reaction itself has the advantage of proceeding rapidly, but the economic disadvantage of requiring a large amount of reaction reagent is unavoidable.

The reaction temperature and the reaction time in the above methods (a) and (b) vary depending on the solvent and the presence of a catalyst used, but are usually 100 to 250 ° C., preferably 110 to 10.
It is 1 to 20 hours at 200 degreeC. If the reaction temperature is less than 100 ° C, there is a disadvantage that the reaction takes a long time, and if it exceeds 250 ° C, the reaction product may be colored and the introduced formamide group may be thermally decomposed. Therefore, when the above reaction is performed without a catalyst, at a relatively low temperature, or when the molar ratio of the reaction reagent to the raw material is reduced, the production rate of the repeating units C and D is high and The production rate is practically negligible. On the other hand, when the above reaction is carried out using the catalyst, at a high temperature, or when the molar ratio of the reaction reagent to the raw material is increased, the production rate of the repeating unit E increases.

The ratio of formamide groups to amino groups is substantially 10 when a reaction product of a diamine and a formyl group-containing compound is used as an imidizing or amidating reagent.
A copolymer with 0% formamide groups is obtained. When a salt of diamine is used, a copolymer in which formamide groups and amino groups are mixed is obtained, and the higher the reaction temperature and the longer the reaction time, the greater the formation rate of formamide groups.
Thus, under the above reaction conditions, (repeating unit C +
The ratio of repeating unit D) / repeating unit E is 100/0 to 30 /
70, the ratio of formamide group / amino group is 100/0
A 30/70 copolymer is obtained. The above composition of the copolymer of the present invention is, for example, the carbonyl carbon (W) of the imide ring appearing in the vicinity of a chemical shift of 176 to 180 ppm obtained by measuring a nuclear magnetic resonance ( ¹³ C-NMR) spectrum using isotope carbon. , Carbonyl carbon (Y) and 162 pp of amide appearing near 172 to 174 ppm
Carbonyl carbon (Z) of formamide group appearing near m
It can be known by the peak intensity ratio of.

In the method (a) of the present invention, the order of charging the reaction raw materials is not particularly limited, and the reaction can be carried out in various modes. Usually, a formyl group-containing compound (or another solvent thereof is added to another solvent). Dissolved), the powder or solution of the salt of the diamine and the acid is added and dissolved, and then the copolymer containing repeating units A, B and C ′ is gradually added,
Alternatively, the reverse order is taken. During this period,
The heating may be performed under reflux of the solvent (or the compound containing a formyl group). Also in the method (b) of the present invention, the order of charging the reaction raw materials is not particularly limited, and it can be carried out in various modes, but usually, a copolymer containing repeating units A, B and C ′ is used. Is uniformly dissolved in the solvent, and then the reaction product obtained by reacting the diamine with the formyl group-containing compound is gradually added, or the reverse order is adopted. The charging during this period may be performed under heating with reflux of the solvent. Since the imidation or amidation reaction of the raw material copolymer and the salt of diamine and the formyl group-containing compound, or the reaction product of the diamine and the formyl group-containing compound proceeds while generating water, the generated water is It will azeotrope with the solvent used. Therefore, the reaction can be efficiently progressed by removing the azeotropic water from the reaction system by means of a Dean-Stark water diverter or the like. Completion of the imidization or amidation reaction means that azeotropic water is no longer observed, and a portion of the reaction mixture is sampled to measure the infrared absorption spectrum at 1700.
This can be confirmed by the fact that the increase in carbonyl absorption intensity of imide around cm ^-1 is no longer observed.

The reaction mixture thus obtained contains a salt of the copolymer of the present invention in which a formamide group or a formamide group and a primary amino group are bound via an imide bond or an imide bond and an amide bond. . This reaction mixture as it is or after being thrown into a non-solvent such as methanol, isopropanol, isobutanol, hexane, or water as necessary to pulverize it, an aqueous solution of a base, or a methanol / water mixed solution of a base as required. It can be deoxidized by contact with and converted into a free amine. Specific examples of the base used for deoxidation include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia, methylamine, ethylamine, trimethylamine and triethylamine. Any water-soluble base may be used. Of these, sodium hydroxide, sodium carbonate, and sodium bicarbonate are preferable for economic reasons. According to the method (b) of the present invention, the salt of the copolymer is not formed, and thus the deoxidation as described above is unnecessary.

Purification of the copolymer containing only formamide groups is carried out by pouring the obtained reaction mixture into a non-solvent such as methanol, isopropanol, isobutanol, hexane and water, and recovering it by pulverizing it. This can be easily implemented. The method for converting the formamide group of the copolymer obtained as described above into a primary amino group is not particularly limited, and a known method may be used. For example, a method of dissolving a copolymer containing a formamide group in an appropriate solvent, or treatment with a mineral acid aqueous solution such as hydrochloric acid or hydrofluoric acid in a dispersed state or hydrolysis to give a corresponding primary amine Can be converted to salt. Preferably, a method of hydrolyzing under acidic conditions such as the method (c) of the present invention can be mentioned. In this method (c), the acidic conditions are not particularly limited, but usually pH 3 or less is preferable, and mineral acids such as hydrochloric acid and sulfuric acid are preferably used for this hydrolysis. The primary amine salt obtained here can be converted into a free primary amine by the same method as described above, if necessary.

[0038]

In the present invention, a partially neutralized salt of a diamine or a reaction product obtained by reacting a diamine with a compound having a formyl group, that is, a partial formamide of a diamine is used as an imidizing reagent in the present invention. This suppresses the reactivity of one end of the diamine, and the primary amine at the other end selectively participates in imidization or amidation, so that the desired copolymer can be obtained smoothly without causing crosslinking. It is supposed that Further, even when a partially neutralized salt of diamine is used, the fact that the product contains a formamide group means that the salt of the diamine causes a transamidation reaction with the formyl group-containing compound used as a solvent during the reaction. It is thought to be because. In the present invention, the formed formamide group acts as a protective group for the primary amine, and side reactions are avoided even during the imidization reaction under heating, so that a copolymer having a good hue can be obtained. The obtained copolymer containing a formamide group can be converted into an amino group as necessary, and when it is used as a polymer compatibilizer or a resin modifier, for example,
It is possible to change to a more active functional group by thermal decomposition.

[0039]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. Reference Example 1 (Preparation of partially neutralized p-toluenesulfonic acid salt of ethylenediamine) A flask having an internal capacity of 1 liter equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser was charged with 300 ml of methanol and p.
-Toluenesulfonic acid monohydrate 95 g (0.5 mol) was charged and dissolved. While cooling in an ice bath, a solution prepared by dissolving 150 g (2.5 mol) of ethylenediamine in 300 ml of methanol was added dropwise at such a rate that the temperature was kept at 10 to 20 ° C. After completion of the dropwise addition, the mixture was heated to 70 ° C. and then depressurized to remove methanol and unreacted ethylenedimiane, and 132.7 g of a white solid was deposited. The white solid obtained was taken out, made into a slurry with 300 ml of toluene, filtered, and washed twice with 100 ml of toluene, and the obtained white powder was dried under reduced pressure. Yield is 109.8
It was g. Table 1 shows the neutralization equivalent and the degree of neutralization of this white powder titrated with 0.5 N hydrochloric acid using bromophenol blue as an indicator.

Reference Example 2 (Preparation of partially neutralized hydrochloric acid salt of ethylenediamine) Reference Example 1 except that the same reaction vessel as in Reference Example 1 was used and 35% hydrochloric acid aqueous solution was used in place of p-toluenesulfonic acid.
A white powder of ethylenediamine monohydrochloride was obtained by the same procedure. The neutralization equivalents and degree of neutralization obtained in the same manner as in Reference Example 1 are shown in Table 1.

Reference Example 3 (Preparation of partially neutralized p-toluenesulfonic acid salt of hexamethylenediamine) Using the same reaction vessel as in Reference Example 1, 500 ml of dimethylformamide (DMF) was added to p-toluenesulfonic acid monohydrate. 95 g (0.5 mol) were dissolved at room temperature. Then, 52.2 g (0.45 mol) of hexamethylenediamine was gradually added and dissolved therein so that the temperature of the solution did not exceed 20 ° C to prepare a DMF solution of a partially neutralized salt of p-toluenesulfonic acid of hexamethylenediamine. did. Table 1 shows the neutralization equivalent and the degree of neutralization per solid content.

Reference Examples 4 and 5 A salt of a diamine and an acid was prepared in the same manner as in Reference Example 3 except that the kinds of the diamine and the acid used were changed. Table 1 shows the neutralization equivalent and the degree of neutralization of the obtained salt per solid content.

[0043]

[Table 1]

[0044]

[Table 2]

Reference Example 6 (Preparation of Reaction Product of Ethylenediamine and Formamide) Using the same reaction vessel as in Reference Example 1, ethylenediamine 30
45 g (1.0 mol) of formamide was gradually added dropwise to 0 g (5.0 mol) at room temperature, and then heated at 80 to 120 ° C. and reacted for 5 hours. During this period, generation of ammonia gas was observed. After completion of the reaction, unreacted ethylenediamine was distilled off at 61 ° C./88 mmHg to obtain a residue. The results obtained by neutralization titration of this residue are shown in Table 2.

Reference Example 7 (Preparation of Reaction Product of Hexamethylenediamine and DMF) In the same manner as in Reference Example 6, hexamethylenediamine was added to DM.
The reaction was carried out by dropping F. The reaction mixture was dissolved in a solvent (ethanol / water = 7/3 (volume ratio)), neutralized with 35% hydrochloric acid, concentrated and recrystallized. The needle crystals of hexamethylenediamine hydrochloride were removed by filtration, and the results obtained by potentiometric titration of the concentrated residue are shown in Table 2.

Reference Example 8 (Preparation of reaction product of 1,3-bis (aminomethyl) cyclohexanediamine and DMF) In the same manner as in Reference Example 7, 1,3-bis (aminomethyl)
DMF was added dropwise to cyclohexanediamine to carry out reaction and filtration. The results obtained by potentiometric titration are shown in Table 2.

Reference Example 9 (Preparation of Reaction Product of m-Xylylenediamine and Formic Acid) 272 g (2.0 mol) of m-xylylenediamine and formic acid 2
3 g (0.5 mol) was reacted at 120 ° C. for 10 hours while distilling off water with a Dean-Stark water divider. The obtained reaction product was treated in the same manner as in Reference Example 7 to obtain the desired reaction product. The results obtained by potentiometric titration are shown in Table 2.

[0049]

[Table 3]

Reference Example 10 (Preparation of Maleic Anhydride Grafted Polypropylene: Reference in Japanese Examined Patent Publication No. 56-9925) Weight average molecular weight (Mw) 60000, number average molecular weight (M
n) 100 parts by weight of crystalline polypropylene powder of 24000, 12 parts by weight of maleic anhydride and 4 parts by weight of dicumyl peroxide were mixed in advance, and the screw diameter was 30 mm, L
/ D = 28 extruder with barrel temperature set to 230 ° C., extrusion reaction was performed at screw rotation speed of 60 rpm, and the extruded graft product was crushed and then immersed in acetone to extract and remove unreacted maleic anhydride, and dried. Thus, a maleic anhydride-grafted polypropylene resin (1) was obtained. The obtained maleic anhydride graft amount was 4.5% by weight: the molecular weight by gel permeation chromatography (GPC) was Mw = 15000 and Mn = 6500 in terms of polystyrene.

Reference Example 11 By the same method as in Reference Example 10, maleic anhydride graft copolymers (2) to (10) shown in Table 3 were obtained.

[0052]

[Table 4]

Example 1 DMF was added to a flask having an internal volume of 1 liter equipped with a thermometer, a stirrer, a dropping funnel, and a Dean-Stark water separator.
0 ml and 120 g of maleic anhydride-grafted polypropylene (1) prepared in Reference Example 10 were charged, heated and dissolved at 140 ° C. under reflux of xylene. Next, a solution prepared by dissolving 17.8 g of the p-toluenesulfonate of ethylenediamine prepared in Reference Example 1 in 200 ml of DMF was gradually added dropwise to this flask over 3 hours. During this period, the reaction mixture was kept at the reflux temperature of xylene, and as a result of the imidization reaction, azeotropic water was removed to the outside of the reaction system by the Dean / Stark water divider. After continuing the reaction for 14 hours from the start of the dropwise addition of the ethylenediamine salt, the mixture was cooled and the reaction mixture was poured into 5 liters of methanol to collect the purified product as a precipitate. This precipitate was dissolved under heating with toluene to prepare a cast film, and the infrared absorption spectrum was measured.
Absorption based on imide ring at 0 cm ⁻¹ , absorption at 1660 cm ⁻¹ (shoulder) and formamide group at 1530 cm ⁻¹ , 1122, 1035, 1010, 685, 570
Absorption based on p-toluenesulfonic acid was observed at cm ^−1, and it was confirmed that a formamide group or a primary amino group was bonded to polypropylene through an imide bond in the form of p-toluenesulfonic acid. Further, this precipitate was added to water / methanol containing 8.0 g of potassium carbonate (volume ratio 1 /
1) After being immersed in the solution overnight, it was filtered off, washed thoroughly with water and methanol, and dried. The yield obtained was 121.1 g. The obtained copolymer is a pale yellowish white powder at 100 ° C.
Was dissolved in tetralin at 10% by weight, and the viscosity was measured by a B-type viscometer (100 ° C.) to find 180 cps. Moreover, when a xylene cast film was prepared and the IR spectrum was measured, it was 1122 cm ^-1 , 1035.
^{cm -1, 1010cm -1, 685cm -1} , 570cm -1
The absorption based on p-toluenesulfonic acid of No. 1 had disappeared. Further, 1768 cm ^-1, absorption of imide ring at 1700cm ^-1, 1660cm ^-1 (shoulder), 1530 cm
^-1 has absorption of formamide group, and 3400c
Absorption based on an amino group was observed at m ^-1 . On the other hand, C
Nuclear magnetic resonance with isotopic carbon measured in DCl ₃ ( ¹³
In the C-NMR spectrum, the carbonyl carbon peak of the imide ring has an intensity ratio of 2.00 to 176 to 180 ppm.
At 162 ppm, the carbonyl carbon peak of the formamide group appeared with an intensity ratio of 0.78.
The peak indicating the presence of the carbonyl carbon of the amide group of pm did not appear. From this, the functional group ratio (molar ratio) was ((III) + (IV)) /
(V) = 100/0, —NH—CHO group / NH ₂ group = 7
It was decided to be 8/22.

Example 2 10.8 g of p-toluenesulfonate of hexamethylenediamine prepared in Reference Example 3 was placed in the same reaction vessel as in Example 1.
50 g of DMF solution containing was charged and heated to 80 ° C.
60 g of a maleic anhydride modified product (2) (Mw = 50000, Mn = 48000, maleic anhydride graft amount 1%), which is a hydrogenated product of the styrene-butadiene copolymer produced in Reference Example 11, was placed in the reaction vessel. It was dissolved in 600 ml of xylene and gradually dropped from a dropping funnel. After the completion of the dropwise addition, a part of the reaction mixture was sampled and its IR spectrum was examined. As a result, the absorption based on the succinic anhydride ring at 1780 cm ^-1 was completely disappeared. Continue heating and raising the temperature, and continuously remove azeotropic water with the Dean-Stark water diverter, until water stops being produced for 8 hours, 1
The reaction was continued at 40 ° C. After the reaction was completed, the reaction mixture was concentrated to 400 ml under reduced pressure, and sodium carbonate 6.0 was added.
It was poured into 5 liters of a water / methanol (volume ratio 1/1) solution containing g, and the product was recovered as a precipitate. The precipitate was washed with methanol and dried to give the desired copolymer 59.1.
g was obtained. The obtained copolymer was a pale yellowish white powder and was soluble in xylene. It was dissolved in xylene at 10% by weight, and the viscosity was measured with a B-type viscometer (25 ° C.) to give 790 cp.
It was s. In addition, when a xylene cast film was prepared and the infrared absorption spectrum was measured, it was 1775 cm.
^-1, the absorption of the imide ring in 1702Cm ^-1, 1665 cm ^-1
(Shoulder), the absorption of the formamide groups in 1529Cm ^-1, the 3420Cm ^-1 absorption based on amino group (trace) was observed. On the other hand, ¹³ C measured in CDCl ₃
-In the NMR spectrum, the carbonyl carbon peak of the imide ring has an intensity ratio of 2.00 at 176 to 180 ppm, and
At 62 ppm, a carbonyl carbon peak of the formamide group appeared with an intensity ratio of 0.65. From this, the functional group ratio was ((III) + (IV)) /
(V) = 100/0, —NH—CHO group / NH ₂ group = 6
It was decided to be 5/35.

Example 3 90 g of maleic anhydride-grafted ethylene-propylene copolymer (3) prepared in Reference Example 11 and 500 ml of cumene were charged and dissolved in the same reaction vessel as in Example 1. The above solution was heated to 153 ° C., and hexaethylenediamine hydrochloride 1 prepared in Reference Example 2 was prepared under the reflux of cumene.
7.7 g was dissolved in 80 ml of DMF and added dropwise. While continuously removing the azeotropic water with a Dean-Stark water diverter, the reaction was continued for 9 hours until no more water was produced. After the reaction was completed, the reaction mixture was mixed with sodium carbonate 1 under reduced pressure.
It was poured into 5 liters of a water / methanol (volume ratio 1/1) solution containing 0 g, and the product was recovered as a precipitate. The precipitate was washed with methanol and dried to obtain the target copolymer 89.
7 g was obtained. The obtained copolymer was a white powder and was soluble in xylene, and was dissolved in xylene at 10% by weight, and the viscosity was measured with a B-type viscometer (25 ° C.) to find that it was 350 cps.
Met. In addition, when a xylene cast film was prepared and the infrared absorption spectrum was measured, it was 1775c.
m ^-1, the absorption of imide ring at 1700 cm ^-1, 1670 cm
The absorption of the formamide group was observed at ^-1 (shoulder) and 1529 cm ^-1 . Also, absorption based on an amino group was observed at 3435 cm ⁻¹ . On the other hand, in the ¹³ C-NMR spectrum measured in CDCl ₃ , 176 to 180 p
The carbonyl carbon peak of the imide ring has an intensity ratio of 2.
At 2,000, the peak of the carbonyl carbon of the formamide group is intensity ratio 1.09 at 162 ppm, 172 to 174 ppm
The carbonyl carbon peak of the amide group has an intensity ratio of 0.22.
Appeared in. From this, the functional group ratio was ((III) + (IV)) / (V) = 82 /
18, —NH—CHO group / NH ₂ group = 89/11 was determined.

Example 4 120 g of maleic anhydride-grafted polyethylene (6) of Reference Example 11 was used in place of the maleic anhydride-grafted polypropylene copolymer, and ethylenediamine of Reference Example 6 was used instead of the p-toluenesulfonate of ethylenediamine. And the reaction product of formamide (45.5 g) were used, and the reaction was performed in the same manner as in Example 1. As a result, 134.3 g of the desired copolymer was obtained. The obtained copolymer was a white powder and was soluble in tetralin / DMI.
It was dissolved in (volume ratio 1/1) at 10% by weight, and the viscosity was measured by a B-type viscometer (100 ° C.) to find 45 cps. The measured IR spectrum (KBr tablet method), 1780 cm ^-1, absorption of imide ring at 1772 cm ^-1, 1670 cm ^-1 (shoulder), 1532cm ^-1
The absorption of formamide group was observed. On the other hand, CDC
The ¹³ C-NMR spectrum measured in l _3, 176
The peak of the carbonyl carbon of the imide ring appeared at an intensity ratio of 2.00 at ˜180 ppm, and the peak of the carbonyl carbon of the formamide group appeared at an intensity ratio of 0.85 at 162 ppm. From this, the functional group ratio was ((III) + (IV)) / (V) = 100/0, -NH-C, as determined from the above NMR spectrum.
It was determined that HO group / NH ₂ group = 85/15.

Examples 5 to 10 As the salts of diamines or the reaction products of diamines and formyl group-containing compounds, those obtained in Reference Examples 1 to 9 were used, and raw material copolymers shown in Table 4 were used. The same procedure as in Examples 1 to 4 was carried out using the copolymer. The fourth result
Shown in the table. The viscosity of the obtained copolymer was measured in the same manner, and the results are shown in Table 4.

[0058]

[Table 5]

[0059]

[Table 6]

[0060]

[Table 7]

[0061]

[Table 8]

[0062]

[Table 9]

[0063]

[Table 10]

[0064]

[Table 11]

Example 11 13.0 g of the copolymer obtained in Example 3 was added to methanol 10
It was dissolved in 0 ml, and 50 g of 35% hydrochloric acid was added to uniformly mix and disperse the mixture, which was then left at room temperature for 2 days. The reaction mixture was concentrated under reduced pressure and poured into 500 ml of isopropanol to obtain a precipitate. 5.0 g of sodium carbonate was obtained.
Water / isopropanol (volume ratio 1/1) solution containing 30
Immerse in 0 ml. After soaking overnight, the precipitate was filtered off, washed thoroughly with water and isopropanol, and dried. The yield was 12.1 g. The obtained copolymer is
Light yellowish white powder dissolved in toluene at 10% by weight,
It was 395 cps as a result of measuring viscosity. The measured IR spectrum creates toluene cast film, 1772 cm ^-1, absorption of imide ring at 1700 cm ^-1, 1666 cm ^-1 (shoulder), 1530
There is the absorption of amide groups in cm ^-1, absorption based on amino group was observed in the 3430cm ^-1. On the other hand, CDCl ₃
In the ¹³ C-NMR spectrum measured in
At 80 ppm, the peak of the carbonyl carbon of the imide ring had an intensity ratio of 2.00, at 162 ppm there was no peak of the carbonyl carbon of the formamide group, and at 172 to 174 ppm the peak of the carbonyl carbon of the amide appeared with an intensity ratio of 0.20. . From this, the functional group ratio was (IV) / (V) = 83/17, -NH-CHO according to the above NMR spectrum measurement.
Group / NH ₂ group = 0/100 was determined.

Comparative Example 1 The same raw material as in Example 1 except that 5.0 g of ethylenediamine was used in place of p-toluenesulfonate of ethylenediamine and 200 ml of xylene was used in place of DMF. I tried to react using
P-Toluenesulfonate of ethylenediamine 17.8g
Was dissolved in 200 ml of DMF, and at the stage where 1/5 amount of ethylenediamine solution was added dropwise, the reaction mixture immediately became highly viscous and could not be stirred, and finally became an integrated lump, and the subsequent reaction could not be continued. there were. The product obtained by collecting a part of this massive reaction mixture, washing it with methanol, and drying it did not dissolve in xylene even when heated, and was clearly different from the product obtained in Example 1 above. It was judged that a crosslinked product was formed.

Comparative Example 2 800 ml of xylene and 16.5 g of ethylenediamine were charged into the same reaction vessel as in Example 1 and heated to 100 ° C. Then, 120 g of maleic anhydride-grafted polypropylene obtained in Reference Example 10 was added as a powder,
The heating and heating were continued, but when the distillation of azeotropic water started, the reaction mixture immediately became highly viscous and could not be stirred, and finally became an integrated lump, and it was impossible to continue the reaction thereafter. . The product obtained by collecting a part of this massive reaction mixture, washing it with methanol, and drying it did not dissolve in xylene even when heated, and was clearly different from the product obtained in Example 1 above. It was judged that a crosslinked product was formed.

Comparative Example 3 The same as Example 2 except that 4.5 g of hexaethylenediamine was used in place of the p-toluenesulfonic acid salt of ethylenediamine and 150 ml of xylene was used in place of DMF. An attempt was made to carry out the reaction using the raw materials, but a modified product of maleic anhydride (2) (Mw = 50,000, M which is a hydrogenated product of a styrene-butadiene copolymer).
n = 48,000, maleic anhydride graft amount 1%) 60
When azeotropic water distills in the process of heating and raising the temperature after the completion of dropwise addition of a solution of g dissolved in 600 ml of xylene, the reaction mixture immediately becomes highly viscous and cannot be stirred, and finally becomes an integrated lump. It was impossible to continue the reaction thereafter. Taking a portion of this bulk reaction mixture,
The product obtained by washing with methanol and then drying did not dissolve in xylene even when it was hot, and it was judged that a crosslinked product was formed, which was clearly different from the product obtained in Example 2 above.

Comparative Example 4 The reaction was tried using the same raw materials as in Example 1 except that 200 ml of DMI was used instead of DMF. The obtained copolymer was a brown powder which was soluble in xylene and 10% by weight in tetralin.
As a result of measuring the viscosity at ℃, it was 165 cps. Also,
As a result of measuring an IR spectrum by creating xylene cast film, 1770 cm ^-1, absorption of imide ring at 1700 cm ^-1, the 3350 cm ^-1 absorption based on amino group was observed.

[0070]

According to the present invention, a formamide group or a formamide group and a primary amino group can be introduced into a side chain of various polymers through an imide group or an amide group. A novel copolymer that can be used for a wide range of applications such as raw materials for functional polymers, adhesive raw materials, polymer compatibilizers, and resin modifiers, and that can give active primary amino groups by hydrolysis. Can be provided.

Claims (5)

[Claims] 1. A repeating unit A represented by the general formula (I) in an amount of 20 to 99.8 mol%, a repeating unit B represented by the general formula (II) in an amount of 50 to 0 mol% and a general formula (III) Repeating unit C represented, repeating unit D represented by general formula (IV) and general formula
Total amount of repeating unit E represented by (V) 30 to 0.2 mol%
(However, the repeating unit C is 0.2 mol% or more.) [Chemical 2] [Chemical 3] (In the formula, R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 3 to 8 carbon atoms.
Cycloalkyl group, C6-10 aryl group, C2-4 alkenyl group, C1-4 alkoxy group, C1-18 alkoxycarbonyl group, C1-17 alkylcarboxyl Group, an alkylcarbonyl group having 1 to 6 carbon atoms, an arylcarbonyl group having 6 to 8 carbon atoms, a halogen atom or a nitrile group, and R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , An alkenyl group having 2 to 4 carbon atoms or a halogen atom, R ⁸ does not exist or represents a methylene group or an ethylene group, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Represents a group or an aryl group having 6 to 8 carbon atoms, R ¹¹ represents an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group having 5 to 17 carbon atoms, and 6 to 6 carbon atoms.
12 represents an arylene group, an arylalkylene group having 7 to 12 carbon atoms or a polyoxyalkylene group having 4 to 30 carbon atoms, and R ¹² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. n shows the integer of 1-10. In addition, R
^{1 to} R ¹² may be the same or different for each repeating unit. Further, X ¹ and X ² each independently represent NH ₂ or NH—CHO. ) -Containing copolymer or a salt thereof. 2. A repeating unit A represented by the general formula (I) in an amount of 20 to 99.8 mol%, a repeating unit B represented by the general formula (II) in an amount of 50 to 0 mol% and a general formula (VI). Repeating unit represented: C'30-0.2 mol% (In the formula, R ^{5 to} R ¹⁰ , R ¹² and n are the same as above.) The copolymer containing the general formula (VII) H ₂ N—R ¹¹ —NH ₂ (VII) (Wherein R ¹¹ is the same as above), after reacting the salt of the diamine in the presence of at least one formyl group-containing compound selected from formamide, formic acid and their derivatives. The method for producing the copolymer or a salt thereof according to claim 1, wherein the method is carried out by contacting with a base for deoxidation. 3. A product obtained by reacting a diamine represented by the general formula (VII) with at least one formyl group-containing compound selected from formamide, formic acid and their derivatives, The repeating unit A represented by the formula (I) is 20 to 99.8 mol%, the repeating unit B is represented by the general formula (II) is 50 to 0 mol%, and the repeating unit C'30 is represented by the general formula (VI). The method for producing a copolymer according to claim 1, wherein a copolymer containing 0.2 mol% is reacted. 4. The copolymer represented by claim 1 is hydrolyzed under acidic conditions, and has the general formula (I) in the molecule.
The repeating unit A represented by the formula A20-99.8 mol%, the general formula (I
The repeating unit B represented by I) is 50 to 0 mol%, the general formula (I
The total amount of the repeating unit D represented by V) and the repeating unit E represented by the general formula (V) is 30 to 0.2 mol% (wherein the repeating unit D is 0.2 mol% or more, X ¹ And X ² are both NH
_{Is 2} . The manufacturing method of the copolymer containing these or its salt. 5. A repeating unit A20-99.8 mol% represented by the general formula (I) in the molecule, which is obtained by hydrolyzing the copolymer according to claim 1 under acidic conditions, The total amount of the repeating unit B represented by II) of 50 to 0 mol%, the repeating unit D of the general formula (IV) and the repeating unit E of the general formula (V) is 30 to 0.2 mol% ( However, the repeating unit D is 0.2 mol% or more, and both X ¹ and X ² are NH ₂ .
A copolymer containing or a salt thereof.