JPS63213522A - Novel piperazine-based copolyamide - Google Patents

Abstract

PURPOSE:To obtain the titled novel copolyamide soluble in aprotic amide solvents, having high glass transition point, a high starting point of thermal decomposition and excellent heat resistance, by copolymerizing a piperazine and a diaminodiphenyl compound with an aromatic dicarboxylic acid. CONSTITUTION:A diaminodiphenyl compound shown by formula I (Y is bifunctional organic group; R<1> and R<2> are 1-12C hydrocarbon; R<3> and R<4> are monofunctional organic group; n1 and n2 are 0 or 1-3 natural integer) is reacted with a piperazine shown by formula II (R<5>-R<12> are H or 1-12C hydrocarbon) and an aromatic dicarboxylic acid dihalide shown by formula III (R is 2-15C bifunctional aromatic group; X is chlorine, bromine, etc.) in a solvent to give the aimed copolyamide having main repeating units shown by formula IV and formula V in the molar ratio of the repeating units of 95/5-35/65.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a novel piperazine copolyamide that is soluble in aprotic amide solvents and has excellent heat resistance. More specifically, it is a novel copolyamide obtained by reacting a mixed diamine component consisting of a specific aromatic diamine compound and a piperazine compound with an aromatic dicarboxylic acid component. Since this copolyamide has excellent heat resistance as well as excellent water absorption, it can be used for various purposes by processing it into fibers, films, and forming into membranes, etc., using an appropriate method. For example, it is suitable for materials such as reverse osmosis membranes, ultrafiltration membranes, and microfilters that selectively permeate water.

(Prior Art) In recent years, heat-resistant polymer compounds such as polyamide, polyurethane, polyimide, and polyether are being considered as materials for reverse osmosis membranes, ultrafiltration membranes, microfilters, and the like.

In particular, various types of polyamides are being studied, and among them, a reverse osmosis anisotropic membrane (unexamined patent publication Showa 55-147
106) is attracting attention because of its excellent permselectivity and durability against chlorine.

(Problems to be Solved by the Invention) The membrane obtained from the piperazine copolyamide described in JP-A-55-147108 shows excellent permselectivity, but the acid component is difficult to synthesize and expensive. The disadvantage is that a heterocyclic dicarboxylic acid compound must be used. In addition, polyamide obtained by using a phthalic acid compound alone as an acid component can be made from N, N, which is usually used for film formation.
- It is poorly soluble in aprotic amide solvents such as dimethylacetamide and N-methylpyrrolidone, and only dissolves in protic solvents such as formic acid and metacresol, which are dangerous to handle. Attempts were made to produce a permselective membrane from the above copolyamide using these solvents, but it turned out that membrane formation was difficult because the above copolyamide was not sufficiently soluble in the above aprotic amide solvent.

(Means for solving the problem) As a result of intensive research on the solubility of copolyamides made of various aromatic diamine compounds and piperazine compounds in aprotic amide solvents, we found that The present invention was achieved by discovering that the solubility in a solvent largely depends on the chemical structure of the aromatic diamine compound used in combination.

This invention is a novel piperazine-based copolyamide soluble in an aprotic amide-based solvent obtained by reacting an aromatic dicarboxylic acid halide compound with a mixed diamine component mainly consisting of a specific diamine compound and a piperazine-based compound. It is.

That is, a piperazine-based copolyamide characterized in that the main repeating units are represented by the following general formulas (1) and (2), and the molar ratio of repeating units (1) and (2) is 9515 to 35/65. It is. Although the piperazine-based copolyacide contains a piperazine-based compound, N
- It is soluble in aprotic solvents such as methylpyrrolidone and N,N'-dimethylacetamide, and has a high glass transition point (Tg) and thermal decomposition initiation point (Td).

(However, R represents a divalent aromatic group having 2 to 15 carbon atoms, and Y represents a divalent organic group.

R', R", R', R", R', R@, R"
,R,R.

R represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R''% R' represents a monovalent organic group.

n* and n* represent O or a natural number from 1 to 3. )especially,
R1 and R1 of repeating unit (1) are hydrogen atoms, Y is -
C1,-,-c(CHs),-1-CH,CHs
+, -CH=CH, -1-NH-1-N (CH,)
+, -NHCO-1-〇-1-〇〇-1-3O, -1-
3O-1-8-1-8O, NH-, -0--lene and/
or trans-2,5-dimethylpiverazinylene, R
is a metaphenylene 7 group (substituted at 1,3-position) and/or a paraphenylene group (substituted at 1°4-position), it exhibits excellent solubility and thermal properties in aprotic amide solvents. show.

Furthermore, the copolyamide has a strong affinity for water (water absorption) due to piperazine. Its water absorption can be appropriately adjusted by adjusting the content of piperazine to be copolymerized, and copolyamides suitable for purposes can be designed and synthesized as desired.

Therefore, the present copolyamide is suitable for fields involving water, such as water absorbent fibers, reverse osmosis membranes, ultrafiltration membranes, microfilters, dialysis membranes, artificial kidneys, blood plasma separation membranes, and the like.

As mentioned above, this copolyamide has a high glass transition point (T
g) and the onset of thermal decomposition (Td), it is also possible to expose molded articles obtained from this copolyamide to high temperatures. For example, hot water can be used to sterilize membrane materials etc. obtained from the copolyamides of the invention.

Y of the copolyamide of the present invention is -CH, +, -Q-1-N
HCO-1-Co-, -8O,NH-, -8-1-CH
, CH, -1 (unspecified) etc. are preferred, especially -8 from the viewpoint of solubility in aprotic amide solvents and heat resistance.
O8- is preferred.

The substituents R' and R'' in repeating unit (1) are hydrogen atoms, lower alkyl groups (e.g., methyl, ethyl, isopropyl, n-propyl groups, etc.), aromatic groups (phenyl groups, benzyl groups, etc.), and cyano groups. , an acetyl group, a nitro group, etc., and a hydrogen atom is preferred from the viewpoint of solubility in aprotic amide solvents and strength of molded products.

R3 and R4 are halogen groups (e.g. chlorine, bromine, fluorine), lower alkyl groups (e.g. methyl, ethyl, isopropyl, n-propyl groups, etc.), lower alkoxy groups (
methoxy group, ethoxy group, etc.), aromatic group (phenyl group,
(benzyl group, etc.), cyan group, acetyl group, nitro group, etc., but a hydrogen atom is preferable from the viewpoint of solubility and strength in aprotic amide solvents.

The substitution R'-R'' in the repeating unit (2) includes a hydrogen atom, a lower alkyl group (eg, methyl, ethyl, isopropyl, n-propyl group, etc.), an aromatic group ('phenyl group, benzyl group, etc.), and the like. Preferably, R'-R
is a hydrogen atom or R' is a methyl group, the remainder is a hydrogen atom, or R3 and/or R'' is a methyl group, and the remainder are hydrogen atoms.

Examples of the substituent R in repeating unit (1) and (2) include phenylene, naphthylene, etc., and the bonding position thereof is not particularly limited. From the viewpoint of solubility in aprotic amide solvents, hydrogen atoms are preferred.

It is also possible to use a mixture of two or more different substituents R.

In the copolyamide of the present invention, the diamine repeating unit of repeating unit (1) is 35# of all diamine repeating units.
By containing 95 mol%, the solubility in aprotic amide solvents is significantly increased, and furthermore, fibers, films, etc., which are excellent in hydrophilicity and heat resistance are provided.

The fact that piperazine is copolymerized with the copolyamide of the present invention indicates that the infrared absorption spectrum shows a value of 2800 to 29
Absorption attributed to the methylene chain C-H of aliphatic C-H at 50 cm-' and 3 and 4p in the NMR spectrum
This can be confirmed from the absorption attributed to protons of -N-CH and - in pm.

The copolyamide of the present invention has the following general formulas (1') and (2).
') is substantially equal to the aromatic dicarboxylic acid halide represented by the following general formula (3'), and the ratio between the formulas (1°) and (2') is 9515 to 9515. It can be produced by reacting so that the ratio is 35/65.

(Y represents a divalent organic group. R', R- represents a hydrocarbon group having 1 to 12 carbon atoms, m R' % R' represents a monovalent organic group, n+ s n* represents 0 or a natural number from 1 to 3.) (Ta?'t,,R',R@,R),R",R・,R
, R, and R represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. ) IOC-R-COX (three (
However, X represents a halogen atom such as chlorine or bromine, and R represents a divalent aromatic group having 2 to 15 carbon atoms. ) The diamine compounds (1') and (2'') and the aromatic dicarboxylic acid halide compound (3') used to produce the copolyamide of the present invention are as follows.

As the compound represented by the general formula (1'), 3゜3'-
Diaminodiphenylmethane, 4,4'-diamino-3,
3'-dimethyldiphenylmethane, 4゜4''-diamino-3,3',5.5'-tetramethyldiphenylmethane, 4,4'-diamino-3-ethyldiphenylmethane, 4.4'-diamino-3,3'' -diethyldiphenylmethane, 4,4'-diamino-5,5',6.8'-
Tetramethyldiphenylmethane, 2,2'-bis(3-
aminophenyl)propane, 2.2'-bis(4-aminophenyl)propane, 4.4'-diaminodiphenylmethane, 4.4'-diaminodibenzyl, 4.4'-methylenebis(2-chloroaniline), 4 .4'-diamino-benzophenone, 3.4'-diaminodiphenyl ether, 2.4'-diaminodiphenyl ether, 4.
4'-diaminodiphenyl ether, 4.4'-diaminobenzanilide, 4.4'-diaminobenzenesulfoanilide, 3.3'-diaminodiphenyl sulfide, 4.4'-diaminodiphenylsulfide, 3.3'
-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3゜4'-diaminodiphenylsulfone, 3,3'-dinitro-4-4'-diaminodiphenylsulfone, etc. From the viewpoint of solubility in aprotic amide solvents and heat resistance, 4,4''-diamino-benzophenone, 4,4'-diaminobenzenesulfoanilide, 3,3-diaminodiphenylsulfide, 4,4''-
Diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 4,4-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, bis(
4-(3-aminophenoxy)phenyl]sulfone, bis(4-(4-aminophenoxy)phenyl)sulfone, 1゜3-bis(4-aminophenoxy)benzene, l
I4-bis(4-aminophenoxy)benzene, 2.2
-bis4-(4-aminophenoxy)phenyl)propane, etc., and particularly preferred are 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, and 3,4'-diaminodiphenylsulfone. .

Incidentally, when two or more of the above diamine compounds are used, they can be mixed in any proportion.

Examples of the compound represented by the general formula (2') include piperazine, 2-methylpiperazine, t(trans)-2,5-dimethylpiperazine, cis-2,5-dimethylpiperazine, 2,6-diethylpiperazine, 2, 3.5-) diethylpiperazine, 2,2°3.3.5.5.8.8-octamethylbiperazine, 2.2.5.5-tetramethylpiperazine, 2,2°3.5. 5, (3-hexamethylbiperazine, 2-ethylpiperazine, 2.5-diethylpiperazine, 2.3.5-triethylpiperazine, 2.
2,3,5゜5,6-hexaethylpiperazine, 2.3
．． 5.6-tetraethylpiperazine, 2-propylpiperazine, 2,6-dipropylpiperazine, 2,3.5-
Tripropylpiperazine, 2,3,5.8-tetra-n
-Propylpiperazine, 2-butylpiperazine, 2,5
-Z-n-butylpiperazine, 2,5-Z-tert-
Butylpiperazine, 2.3.5-tri-n-butylpiperazine, 2-pentylpiperazine, 2-decylpiperazine, 2,5-divinylpiperazine, 2,5-diphenylpiperazine, 2-phenylpiperazine, 2.3.5. 6
-Titraphenylbiperazine, 2-naphthylpiperazine, 2.5-dinaphthylpiperazine, 2-) IJ rubiperanone, 2,5-ditolylpiperazine, 2,3.5°6-
Citratolylpiperazine I and the like can be mentioned.

From the viewpoint of solubility in an aprotic amide solvent, preferred diamine compounds (2') are piperazine, 2-methylpiperazine, and t-2,5-dimethylpiperazine, with piperazine being particularly preferred.

In the diamine compound (2'), the diamine compounds mainly used are ta, but depending on the application, 2! ! It is also possible to use a mixture of one or more types.

The mixing ratio of the compound represented by the general formula (1') and the diamine compound represented by the general formula (2') has a great influence on the physical properties of the copolyamide produced, and the preferred range is 9515 to 35 molar ratio. /85.

When the amount of diamine compound (2') is more than 65 mol%,
The reaction system becomes heterogeneous, making it difficult to control the degree of polymerization and making it difficult to obtain a copolyamide with high viscosity. Furthermore, the solubility of the copolyamide in aprotonated amide solvents also deteriorates. A more preferable amount of diamine compound (2') is 10
to 60 mol%, particularly preferably 10 to 40 mol%
The range is mole %.

Aromatic dicarboxylic acid halide compound (3
') include phthalic acid, isophthalic acid, terephthalic acid,
4.4'-diphenyl dicarboxylic acid, 1,2-naphthalene dicarboxylic acid, 1.3-1 phthalene dicarboxylic acid, 1
, 4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1.

6-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3
Examples include halide compounds (chlorides, bromides, etc.) such as -naphthalene dicarboxylic acid, 2.8-1 phthalene dicarboxylic acid, and 2.7-naphthalene dicarboxylic acid. Among these, isophthalic acid dichloride and terephthalic acid dichloride are particularly preferred from the viewpoint of reactivity and solubility in aprotic amide solvents.

The above-mentioned aromatic dicarboxylic acid halide compounds can be mixed and used in any proportion.

From the viewpoint of solubility in the amide solvent, it is preferable to use isophthalic acid dichloride in an amount of 30 mol % or more based on the total acid components.

The copolyamide of the present invention can be synthesized by the following solution polymerization method.

As the solvent used in the solution polymerization method, various breeding solvents can be used, but aprotic amide solvents are preferably used.

Preferred solvents include N-methyl-2-pyrrolidone,
Hexamethylphosphoramide, N. Examples include N'-dimethylacetamide, N,N'-dimethylformamide, and mixtures thereof. Most preferred is N-methyl-2-pyrrolidone.

Further, a chlorine-based solvent such as methylene chloride, chloroform, 1,2-dichloroethane, 1.1.2-trichloroethane, 1.1,2,2-tetrachloroethanechlorobenzene is mixed with the amide-based solvent. It is also possible.

The above-mentioned solvents used in solution polymerization must be sufficiently dehydrated in advance by distillation or a dehydrating agent such as a molecular sieve.

The water content of the solvent used in the solution polymerization reaction of the present invention is 200p.
pm or less, preferably 100 ppm or less, particularly preferably 50 ppm or less.

Pyridine, α-picoline, β-picoline, γ-picoline, 2
- Pyridine compounds such as ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2-propylpyridine, 4-propylpyridine, N,N-dimethylaniline, N
, N-dialkylaniline compounds such as N-diethylaniline. Among them, pyridine, N, N-
Dimethylaniline and N,N-diethylaniline are preferred, and pyridine is particularly preferred from the standpoint of increasing the viscosity of the polymer and facilitating purification.

If an aliphatic tertiary amine compound such as triethylamine or N-methylmorpholine is used, the polymerization reaction system will become non-uniform, which is not preferred from the viewpoint of viscosity adjustment and purification of the copolyamide.

The water content of the acid scavenger used in the polymerization reaction of the present invention is 20
It is 0 ppm or less, preferably looppm or less, particularly preferably 50 ppm or less.

The acid scavenger used is purified by distillation in advance.
Furthermore, it is preferable to perform sufficient dehydration treatment using a sled sieve or the like.

In a general solution polymerization method, the mixture of the diamine compounds (1'') and (2') is dissolved in the amide solvent or the mixed solvent under a nitrogen stream.The concentration of the charged monomers in the solvent is 10 ~50% (wt monomer/VO party solvent), preferably 20-40%.Furthermore, a predetermined amount of the scavenger for hydrogen chloride generated during the reaction described above is added to the mixed system.Acid scavenging The amount of the agent added is not particularly limited, but basically it is preferably 1.0 to 3.0 times the mole of the theoretical amount of hydrogen chloride generated during the reaction, more preferably 1.0 to 2.0 times the mole. Since the amount of acid scavenger added depends on the type of acid scavenger, the amount cannot be limited.

For example, as follows. Even if the amount of pyridine and/or its derivatives added as an acid scavenger is 1 times the mole or more of the theoretically generated amount of hydrogen chloride, the viscosity of the resulting polymer will not decrease. On the other hand, if the amount is too large, pyridine acts as a poor solvent for the polymer, making the solution during the reaction non-uniform, resulting in high viscosity and hindering the purification process. Therefore, the ratio of the amount of pyridine to the amount of the reaction solvent needs to be 1/2 or less, preferably 1/3 or less.

Regarding the amount of the N,N-dialkylaniline compound added, it is preferably 1.0 to 1.2 times the mole of the theoretical amount of hydrogen chloride generated. If the amount added is less than 1.0, the effect as a hydrogen chloride scavenger will decrease, and as a result, the viscosity of the resulting copolyamide will also decrease. On the other hand, if it is 1.2 or more, the produced polymer becomes insolubilized in the reaction solvent, and the reaction system becomes non-uniform. As a result, the polymer becomes difficult to purify. Furthermore, the viscosity of the resulting polymer also tends to decrease with the amount added.

When the diamine compound is dissolved in a solution consisting of the above solvent and an acid scavenger to form a homogeneous solution, an appropriate solvent may be added or the solution may be heated to improve the solubility of the diamine compound. It is also possible to do so. The solvent for promoting solubility must be sufficiently dehydrated in advance by distillation or by using a drying agent. The heating temperature may be any temperature as long as the solvent used and the amine compound do not decompose, but room temperature is most preferred.

The solvent is then cooled to -10°C to 20°C, preferably -5°C to 10°C with a suitable refrigerant.

As the refrigerant, water and/or ethylene glycol are generally preferred, but the method is not particularly limited.

Next, the aromatic dicarboxylic acid halide is added to the cooled solvent consisting of the diamine compound, acid scavenger, and reaction solvent while stirring, and stirring is continued for an appropriate period of time. The aromatic dicarboxylic acid halide is in solid form when added!
! It can take any form, such as (powder, flake, pellet, etc.), a melted state dissolved in an appropriate solvent, or a melted state by heating, but it is preferably in a solid state. .

The aromatic dicarboxylic acid halide may be added to the solution at any rate as long as the temperature does not exceed 70° C. continuously, but it is preferable to add it as quickly as possible from the viewpoint of producing a high polymer. It is preferable that at least 90 mol % or more of the aromatic dicarboxylic acid halide compound is added to the total diamine component within 5 minutes. Otherwise, the viscosity of the copolyamide obtained exhibits very low values. Furthermore, the stirring speed during addition of the aromatic dicarboxylic acid halide influences the degree of polymerization of the resulting polymer, and the faster the stirring speed, the higher the degree of polymerization of the resulting polymer, which is preferable from the viewpoint of the physical properties of the polymer.

After addition of the aromatic dicarboxylic acid halide, stirring is continued for an additional approximately 30 minutes to 1 hour while cooling as described above. The stirring speed at this time may be any speed, but it is preferably as fast as possible.

After the reaction under cooling as described above, approximately 1
The polymerization reaction is continued for 2 hours. The stirring speed at this time may be any speed, but it is preferable to use it as fast as possible in order to obtain a polymer with high viscosity.

The mode of the polymerization reaction system generally depends on the type and concentration of the acid scavenger, but when the pyridine compounds and N,N-dialkylaniline compounds listed in the present invention are used as the acid scavenger, the reaction system The feature is that the reaction system becomes a transparent homogeneous solution during and after polymerization. Therefore, the viscosity of the produced copolyamide can be estimated from the viscosity of the polymerization reaction solution.

In addition, it is possible to continuously solidify and purify the polymer by introducing the polymerization reaction solution into the poor solvent of the polymer.
Very convenient. Furthermore, since the reaction system is constantly homogeneous during polymerization, a polymer with a high degree of polymerization can be obtained.

On the other hand, when an acid scavenger other than the present invention, for example, triethylamine, is used, the resulting polymer becomes insolubilized in the reaction system, and the reaction system becomes a heterogeneous solution during and after polymerization. For this reason,
Reactive terminals are easily deactivated, leading to a decrease in polymer viscosity. Furthermore, it is difficult to purify the polymer by the precipitation method described above, and when this is carried out, a good solvent for the polymer, such as N,N dimethylacetamide, N-methylpyrrolidone, etc., is added to the reaction system to produce a polymer. must be dissolved and the system homogenized before proceeding.

In addition, before, during, and after polymerization, an appropriate substance is added to the reaction system in order to neutralize hydrogen halide generated during 12 polymerization and/or to facilitate dissolution of the polymer in the reaction solvent. It is also possible.

Examples of such inorganic compounds are lithium chloride,
Preferred examples include calcium chloride, potassium chloride, lithium carbonate, lithium oxide, lithium hydroxide, calcium hydroxide, and calcium carbonate. Lithium chloride, calcium chloride, potassium chloride, etc. can be added before polymerization for the purpose of promoting dissolution of the polymer, but others are preferably added after polymerization for the purpose of neutralizing generated hydrogen halide. Further, as an organic compound that provides such effects, propylene oxide is a preferable example. The substances can be added before and/or after polymerization.

As other additives, a terminal capping agent can be used if necessary, and a compound having only one group that reacts with an amino group and a halide group is suitable as the terminal capping agent.

After the polymerization reaction, the resulting solution is mixed with methanol, water, etc., which are poor solvents for the polymer, and the polymer is taken out as a solid. Furthermore, the solid polymer must be repeatedly filtered and washed with water and methanol to remove as much as possible the solvent, acid scavenger, hydrochloric acid, oligomer, etc. adsorbed on the polymer. Thoroughly washed polymer at 130℃~
The copolyamide of the present invention can be obtained by vacuum drying at 150°C.

The amount of hydrochloric acid remaining in the polymer purified in this way is 50
It should be below 0 ppm, preferably below 200 ppm.

The present invention will be described in detail below, but the present invention is not limited to the following examples.

The copolyamide obtained in the present invention was subjected to quantitative and qualitative analysis using the following means.

Measurement of reduced viscosity: Measurements were carried out in a conventional manner as described below.

Solvent: N-methyl-2-pyrrolidone (manufactured by Mitsubishi Kasei)
Solution concentration: 0.5g/di! Measurement temperature: 30°C Viscosity tube: Ubbelohde viscometer Measurement of molecular weight distribution: High performance liquid chromatography (ALC manufactured by Waters)
/CPO20G) under the following conditions.

Pump: Waters 8000A Detector: Waters 401 type RI detector) Injector: Waters U8K) Column:
5hodex AD80M/S+MUD803/5AD
802/SX 2 total 4 columns Column temperature: 55°C Eluent: N,N-dimethylformamide + 0.1M
Lithium chloride injection amount = 70μ Party recorder: Waters M740 type data module Measurement of infrared absorption (IR) spectrum: Hitachi 270
Measurements were made using a -30 type infrared spectrophotometer under the following conditions.

Sample: Powder polymer form: KBr tablet Measurement of Hl and C'-NMR spectra: 300MHz NMRm constant '1trl (XL-300 manufactured by Varian)
) under the following conditions.

Solvent double hydrogenated dimethyl sulfoxide (d”
-DMSO) Measurement temperature: 50°C Measurement of glass transition point (Tg): Measurement was performed using a PerkinElmer DSCIB device under the following conditions.

Sample amount: Approximately 10■ Atmosphere: Argon Temperature rising rate = 20℃/min Measurement of thermal decomposition start point (Td) 1: Shimadzu ■Pyrolysis measurement device! Using DT-30,
Measurements were made under the following conditions.

Sample amount: Approximately 5 ml Atmosphere: Air Heating rate: 10°C/m1n (Example) Example 1: Synthesis of poly(isophthaloyl-4,4”-diaminodiphenylsulfone/piperazine (80/20)) copolymer Piperazi 71.72 g (0.02 mof), 4.
4'-diaminodiphenylsulfone 19.8g (0
, 08 soffi) under a nitrogen stream into a 500 rrl four-hole flask equipped with a nitrogen inlet tube, a thermometer, and a stirrer. Additionally, pyridine 18 is added to this system as an acid scavenger.
me (0.2 mof) and 200 mffi of N-methylpyrrolidone (NMP) as a reaction solvent to dissolve the monomer.

isophthalic acid dichloride while cooling the entire reaction system on ice.
(I PC) 20.48g (0,10 of
) was added within about 2 minutes under a nitrogen stream.

The reaction system was stirred for about 30 minutes under water cooling and then for about 1 hour at room temperature. At this time, the reaction system was a reddish transparent homogeneous solution.

Next, the reaction solution is added to 1500 mffi of methanol to precipitate the polymer. Next, a series of purification steps including pulverization of the produced polymer using a household mixer, filtration, and washing with water was repeated several times to remove unreacted substances in the polymer and remove the solvent.

Finally, the polymer was washed with methanol and dried at about 130° C. under vacuum for about 48 hours.

The yield of the obtained polymer was 92%, and the reduced viscosity (ηs
p/c) was 1.21.

The molecular weight distribution curve of this polymer is shown in Figure 1-1 (
Then, Mn+Mw was 31,000° and 47,000, respectively, and it was found that this polymer was a high molecular weight polymer.

Also this polymer! When R analysis (Fig. 1-2) was performed, 3120 ct-', 3080 cm-' and 84
Absorption of C-H bond of benzene ring at 0c■-1, 2930
cm-', C-H of piperazine at 2890 cm-'
Bond absorption, amide bond absorption from 11850 to 1890 cm-', and -5O8- absorption at 1155c+s-' were confirmed.

Furthermore, the H-NMR spectrum of this polymer is shown in Figure 1-
Shown in 3. -CH"- of piperazine at 3.58 ppm
Broad absorption due to 7.5-8.6 ppm of benzene rings and sharp multiple absorption due to benzene rings are observed.

Furthermore, two absorption lines with an area ratio of about 1:4 are observed at 10.84 and 10.73 ppm, which are attributed to different amide bonds.

The former peak is due to absorption of the secondary amide bond when 4°4'-diaminodiphenylsulfone is bonded to one end of the inphthaloyl group and piperazine is bonded to the other end.

The latter peak is due to the absorption of the secondary amide bond when 4°4'-diaminodiphenylsulfone is bonded to both ends of the isophthaloyl group.

It was thus revealed that this polymer is a high molecular weight copolymer in which the monomers used in the reaction are linked through amide bonds.

From the above H-NMR spectrum, the copolymerization ratio of piperazine to the total amount of diamine compounds was 19 mol%.

As a result of thermal analysis of this polymer, Tg and Td are each 330.
℃, 350℃.

The solubility of this polymer in N,N-dimethylacetamide and N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) was good, and transparent and tough films and membranes were formed from these solutions.

Example 2: Synthesis of poly(terephthaloyl-4,4'-diaminodiphenylsulfone 20)) copolymer The same procedure as in Example 1 was carried out except that terephthalic acid dichloride was used instead of isophthalic acid dichloride in Example 1. went. The reaction system was a reddish-brown homogeneous solution.

The yield of the obtained polymer was 95%, and the reduced viscosity was 0.9.
It was 6.

The molecular weight distribution curve of this polymer is as shown in Figure 2-1, and Mn and Mw are each 31,000.

47,000, indicating that this polymer is a high molecular weight polymer.

In addition, when IR analysis (Fig. 2-2) of this polymer was performed, it was found that 3120cm-', 3085cm-' and 8.
Absorption of C-H bond of benzene ring at 35cm-', 2
950ct-', absorption of C-H bond of piperazine at 2890cm-', absorption of amide bond at 18C35cm-', and absorption of amide bond at 1155cm-' SO. - absorption was confirmed.

Furthermore, the H-NMR spectrum of this polymer is shown in Figure 2-
Shown in 3. 3.55 ppm of piperazine
Broad absorption by 7.4~'7,6 p p
Many sharp absorptions due to benzene rings are observed at m17, 9 to 8.2 ppm.

Furthermore, two absorption lines with an area ratio of about 1:4 are observed at 10.83 and 10.89 ppm, which are attributed to different types of amide bonds.

The former peak is 4 at one end of the terephthaloyl group.

This is due to the absorption of the secondary amide bond when piperazine is bonded to the other end of 4'-diaminodiphenylsulfone.

The latter peak is 4 at both ends of the terephthaloyl group.

2 when 4'-diaminodiphenylsulfone is bonded
Due to absorption of class amide bonds.

In this way, it was revealed that this polymer is a high molecular weight copolymer in which the monomers used in the reaction are linked through amide bonds.

From the above H-NMR spectrum, the copolymerization ratio of piperazine to the total amount of diamine compounds was 20 mol%.

As a result of thermal analysis of this polymer, Tg does not appear and Td is 37.
It was 0°C.

The solubility of this polymer in N,N-dimethylacetamide and N-methyl-2-pyrrolidone was good, and transparent and tough films and membranes were formed from these solutions.

Example 3: Poly(inphthaloyl/terephthaloyl(5)
0150)-4.4'-diaminodiphenylsulfone/
Synthesis of piperazine (80/20) copolymer In Example 1, everything was carried out in the same manner as in Example 1, except that a mixed component of equal amounts of isophthalic acid dichloride and terephthalic acid dichloride was used instead of isophthalic acid dichloride. went.

The reaction system was a homogeneous solution, and the yield of the obtained polymer was 9
At 5%, the reduced viscosity was 1.06.

The molecular weight distribution curve of this polymer is as shown in Figure 3-1, and M n g M w is 32,000° and 4,200°, respectively.
It was found that this polymer was a high molecular weight polymer.

In addition, when IR analysis (Figure 3-2) of this polymer was performed, 3120c Kasumi-', 3085c■-1 and 835c
Absorption of C-H bond of benzene ring at m-', 2940c
s+-', C-H of piperazine at 2890ct-'
Bond absorption, amide bond absorption at 18θ5<em>', and -5O1- absorption at 1155 cm-' were confirmed.

Furthermore, the H-NMR spectrum of this polymer is shown in Figure 3-
Shown in 3. 3.55ppm of piperazine 10H”
- Broad absorption, 7.4-7.8 pprrs
Several absorptions are observed in the benzene ring at 7.9 to 8.2 ppm.

In addition, the area ratio assigned to different amide bonds of 10.84, 10.70, 10.731) pm is 2:
Three absorption lines of 2:1 are observed.

The peak at 10.84 ppm is due to absorption of the secondary amide bond when 4,49-diaminodiphenylsulfone is bonded to one end of the terephthaloyl group or isophthaloyl group and piperazine is bonded to the other end.

The peak at 10.70 ppm is due to absorption of the secondary amide bond when 4,4'-diaminodiphenylsulfone is bonded to both ends of the terephthaloyl group.

The peak at 10.73 ppm is due to absorption of the secondary amide bond when 4,4'-diaminodiphenylsulfone is bonded to the end of the inphthaloyl group.

It was thus revealed that this polymer is a high molecular weight copolymer in which the monomers used in the reaction are linked through amide bonds.

From the above H-NMR spectrum, the copolymerization ratio of piperazine to the total amount of diamine compounds was 20 mol%.

As a result of thermal analysis of this polymer, TglTd was 336, respectively.
℃, 365℃.

The solubility of this polymer in N,N-dimethylacetamide and N-methyl-2-pyrrolidone was good, and transparent and tough films and membranes were formed from these solutions.

Example 4: Synthesis of poly(isophthaloyl-4,41-diaminodiphenyl ether/piperazine (80/20)) copolymer In Example 1, 4.49-diaminophenyl ether was used instead of 4,4'-diaminodiphenyl sulfone. Everything was carried out in the same manner as in Example 1 except that . The reaction system was a grayish white homogeneous solution.

The reduced viscosity of the obtained polymer (ηsp/c) is 1.1
5, Tg and Td were 268°C and 345°C, respectively.

The IR spectrum measurement result is 3150.3050.83
Absorption of C-H in benzene ring in 5c-1, 2940.2
Absorption of C-H of piperazine at 870 cm-', 1850
The absorption of the amide bond was shown at cm-', and the absorption of the ether bond was shown at 1230c1-'.

Furthermore, transparent and tough films and membranes were obtained from NMP solutions of this polymer.

Examples 5 and 6: Synthesis of poly(isophthaloyl-4,4'-diaminodiphenylmethane/piperazine) copolymer In Example 1, 4,4''-diaminophenylmethane was used instead of 4,4'-diaminodiphenyl sulfone. The mixing molar ratio of piperazine was 20 mol% and 50 mol%.
The same procedure as in Example 1 was carried out except for the following.

The re-reaction system was a homogeneous solution, and the reduced viscosities of the obtained polymers were 2.30 and 0.70, respectively.

Further, Tg was 267°C and 258°C, respectively, and Td was 340°C and 333°C, respectively. As the piperazine mixing ratio increases, Tg and Td tend to decrease.

The IR spectrum measurement result is 3120°3050=81
C-H absorption of benzene ring at 5 cm-', 2920,2
Absorption of C-H of piperazine at 880 cm-', 165
00■-1 showed an amide bond, and no difference was observed in the absorption peak position between the two polymers.

Furthermore, transparent and tough films and membranes were obtained from NMP solutions of this polymer.

Examples 7 and 8: Synthesis of poly(inphthaloyl-4,41-aminobenzanilide/piperazine) copolymer In Examples 5 and 6, except that 4,4'-diaminobenzanilide was used instead of diaminodiphenyl ether. This was carried out in the same manner as in Examples 5 and 6. The reaction system before the addition of IPC is a heterogeneous solution due to insolubilization of the amine component, but with the addition of IPC, the reaction system becomes a homogeneous solution. The reduced viscosities of the obtained polymers were 1.33 and 1.65, respectively.

Further, Tg was 330°C and 291°C, respectively, and Td was 353°C and 350°C, respectively. As the piperazine mixing ratio increases, Tg and Td tend to decrease.

The IR spectrum measurement result is 3120°3050.82
C-H absorption of benzene ring at 5 cm-', 2930.2
Absorption of C-H of piperazine at 860 cm-', 186
Two types of amide bonds were shown at 0.1650 cm. No difference in absorption peak position was observed between both polymers.

Furthermore, transparent and tough films and membranes were obtained from NMP solutions of this polymer.

Example 8: Synthesis of poly(isophthaloyl-4,4'-7 minobenzulfoanilide/piperazine (80/20)) copolymer In Example 1, 4,4 was used instead of 4,4'-diaminodiphenylsulfone. The same procedure as in Example 1 was carried out except that '-aminobenzsulfoanilide was used.

The reduced viscosity of the obtained polymer was 0.39, TglTd
were 298°C and 330°C, respectively.

The IR spectrum measurement result is 3125°3080.83
C-H absorption of benzene ring at 5 cm-', 2925.
Absorption of C-H of piperazine at 2880 cm-', 186
Absorption of amide bond at 0 cm-', 1320.118
Absorption of sulfonamide group was shown at 0 cm-'. Furthermore, transparent and tough films and membranes were obtained from NMP solutions of this polymer.

Example 10: Poly(inphthaloyl-4,4'-diaminodiphenyl sulfide/piperazine (80/20)
) Synthesis of copolymer Example 1 was carried out in the same manner as in Example 1, except that 4,4'-diaminodiphenyl sulfide was used in place of 4,4'-diaminodiphenylsulfone.

The resulting polymer had a reduced viscosity of 0.91 and a TglTd of 267°C and 330°C, respectively.

The IR spectrum measurement result is 3110°3050.82
Absorption of C-H of benzene ring at 0 cm-': 2920,
Absorption of C-H of piperazine at 2870cw+-', I
Absorption of the amide bond was shown at E165 cm-'.

Furthermore, transparent and tough films and membranes were obtained from NMP solutions of this polymer.

Example 11: Synthesis of poly(isophthaloyl-4,4'-diaminophenylmethane/trans-2,5-dimethylpiperazine (80/20)) copolymer In Example 1, instead of piperazine, trans-
The same procedure as in Example 1 was carried out except that 2,5-dimethylpiperazine was used.

The reduced viscosity of the obtained polymer was 1.11, and Tg and Td
were 260°C and 356°C, respectively.

The IR spectrum measurement result is 3130°3050.83
C-H absorption of benzene ring at 5 cm-', 2920,
Absorption of C-H of piperazine at 2850c+s-', I
An amide bond was shown at EI80cm-'.

Furthermore, transparent and tough films and membranes were obtained from NMP solutions of this polymer.

Example 12: Synthesis of poly(inphthaloyl-4,4'-diaminobenzanilide/trans-2,5-dimethylpiperazine (80/20)) copolymer In Example 2, trans-
The same procedure as in Example 2 was carried out except that 2,5-dimethylpiperazine was used.

The reduced viscosity of the obtained polymer was 1.25, no Tg was observed, and the Tg was 368°C.

The IR spectrum measurement result is 3075.840cs+-
' Absorption of C-H in benzene ring, 2950°2880
C-H absorption of piperazine in cm-', 1880.1
An amide bond was shown at 870c-1.

Furthermore, transparent and tough films and membranes were obtained from NMP solutions of this polymer.

Example 13: Poly(isophthaloyl-bis(4-(4-
Aminophenoxy)phenyl)sulfone/piperazine(
80/20)) Synthesis of copolymer In Example 1, 4.
Instead of 4'-diaminodiphenylsulfone, bis(
Everything was carried out in the same manner as in Example 1 except that 4-(4-aminophenoxy)phenyl)sulfone was used.

The reduced viscosity of the obtained copolyamide was 1.32, and the glass transition point (Tg) and thermal decomposition initiation point (Td) were 267°C and 355°C, respectively.

The IR spectrum measurement result is 3120°3075.83
Absorption of C-H in benzene ring at 5c*-', 2925.2
Absorption of C-H of piperazine at 860 Cm-”, 1880
The absorption of the amide bond was observed at c■-1, the absorption of the ether bond at 1230 cm-', and the absorption of the -5O1- group at 1145e.Furthermore, transparent and tough films and membranes were obtained from the NMP solution of this polymer. Obtained.

Example 14: Poly(inphthaloyl-bis(4-(3-
Aminophenoxy)phenyl)sulfone/piperazine(
80/20)) Synthesis of copolymer In Example 1, 4.
Instead of 4'-diaminodiphenylsulfone, bis(
Everything was carried out in the same manner as in Example 1 except that 4-(3-aminophenoxy)phenyl)sulfone was used.

The resulting copolyamide had a reduced viscosity of 0.68, and Tg and Td of 228°C and 355°C, respectively.

The IR spectrum measurement result is 3100°3075.83
C-H absorption of benzene ring at 5 cm-', 2920.2
Absorption of C-H of piperazine at 880 cm-', 167
Absorption of amide bond at 0 cm-', absorption of ether bond at 1235 cm-', -8O1- at 1150 cs'''I
The absorption of the group was shown. Furthermore, transparent and tough films and membranes were obtained from NMP solutions of this polymer.

Example 15: Poly(inphthaloyl 1,4-bis(4)
-aminophenoxy)benzene/piperazine (80/2
0)) Synthesis of copolymer In Example 1, everything was carried out in the same manner as in Example 1, except that 1,4-bis(4-aminophenoxy)benzene was used instead of 4,4''-diaminodiphenylsulfone. went.

The reduced viscosity of the obtained copolyamide was O3θ3, and the Tg and Td were 242°C and 35B'C.

! The R spectrum measurement result is 3130°3080.83
C-H absorption of benzene ring at 5 cm-', 2930.2
Absorption of C-H of piperazine at 860w-', 1880
The absorption of the amide bond was shown at 1210 cm-', and the absorption of the ether bond was shown at 1210 cm-'.

Additionally, clear and tough films and membranes were obtained from NMP solutions of this polymer.

Example 1e: Poly(inphthaloyl-1,3-bis(4)
-aminophenoxy)benzene/piperazine (80/2
0)) Synthesis of copolymer In Example 1, everything was carried out in the same manner as in Example 1, except that 1,3-bis(4-aminophenoxy)benzene was used instead of 4,4'-diaminodiphenylsulfone. I went.

The resulting copolyamide had a reduced viscosity of 2.18, and Tg and Td of 226°C and 365°C, respectively.

The IR spectrum measurement result is 3150°3080.84
C-H absorption of benzene ring at 0 cm-', 2925,2
Absorption of C-H of piperazine at 860c-1, 1680
The absorption of the amide bond was shown at cm-', and the absorption of the ether bond was shown at 1210 cm-'.

Furthermore, transparent and tough films and membranes were obtained from NMP solutions of this polymer.

Example 17: Poly(terephthaloyl-1,3-bis(4)
-aminophenoxy)benzene/piperazine (80/2
0)) Synthesis of copolymer Example 1 except that in Example 16, terephthalic acid dichloride was used instead of isophthalic acid dichloride.
This was done in the same manner as in 6.

The reduced viscosity of the obtained copolyamide was 1.67, Tg was not detected, and Td was 360°C.

The IR spectrum measurement result is 3140°30130.8
C-H absorption of benzene ring at 40 cm-', 2925
．． Absorption of C-H of piperazine at 2880 cm-', 16
Absorption of amide bond at 60c-1, 1210cm-'
showed the absorption of ether bonds. Furthermore, transparent and tough films and membranes were obtained from NMP solutions of this polymer.

Example 18.19: Poly(inphthaloyl-2°2-bis4-(4-aminophenoxy)phenyl)benzene/
Piperazine (80/20)) Copolymer Synthesis Example 1, 20 mol% of 2,2-bis(4-(4-aminophenoxy)phenyl)propane was used instead of 4,4'-diaminodiphenylsulfone. , 50 mol%
Everything was carried out in the same manner as in Example 1 except for using the following.

The reduced viscosity of the obtained polymer was 0.95.

0.88, Tg is 232℃, 237℃ and T
d were 372°C and 340°C, respectively.

The IR spectrum measurement result is 3120°3050.83
C-H absorption of benzene ring at 0 cm-', 2950c
Absorption of methyl group at m', 2925°2880cm-'
The C-H absorption of piperazine was shown at , the amide bond absorption at 1830 cm'', and the ether bond absorption at 1230 cm''.

Note that no difference in absorption position was observed between the polymers.

Furthermore, transparent and tough films and membranes were obtained from NMP solutions of this polymer.

Comparative Example 1: Synthesis and solubility evaluation of poly(isophthaloylpiperazine) In a tall beaker of 21, 300 cc of water and 8.0 ml of piperazine were added.
6 g (0,10+aol) and sodium hydroxide IJ'
7. 8.40 g (0.20+5 ol) was added to make a homogeneous solution. While vigorously stirring the water-cooled reaction system, 20.3 g (0.10 ml) of isophthalic acid chloride dissolved in 300 cc of cyclohexanone was added to the water-cooled reaction system.
After stirring for a minute, the reaction product was obtained.

The reaction product was filtered, pulverized using a household mixer, and washed repeatedly to remove unreacted substances and salts. The purified product was vacuum dried at 130°C for about 16 hours.

The yield of the obtained polymer was 67%, and the logarithmic viscosity was ηInh.
= 0.91 (0.5 g/dffi sulfuric acid, 30°C) 0 This polymer also contains N,N-dimethylacetamide, N
Since the solubility in MP and the like was very poor, good films and membranes could not be obtained from this solution.

Comparative Example 2: Synthesis and film-forming property evaluation of poly(inphthaloyl-metaphenylenediamine/piperazine (80/20) JH & combination) Piperazine (0.01s+ol), metaphenylenediamine 4.32 g (0-04) mol), water Sodium oxide 4.80g (0.12m+ol), water 1
A homogeneous solution of 60 mff1 was placed in a 1 t tall beaker. Next, 150 mt of cyclohexanone was added to the solution, and the entire system was cooled with water.

While stirring the system with a homogenizer, a solution containing 10.15 g (0.05 mol) of isophthalic acid chloride and 75 m of cyclohexanone was added all at once.

After stirring for about 80 minutes, 300% of n-hexane was added to the system.
ne was added to precipitate the polymer. The filtered solid polymer was repeatedly ground using a home mixer and washed with water to remove unreacted substances, solvent, and salts.

The polymer was washed with methanol and dried at 100 degrees under vacuum for about 48 hours.

The yield of the obtained polymer was about 74%, and the logarithmic viscosity was η1n.
h= 1.34 (0.5g/d in sulfuric acid, 30°C)
Met. In addition, this polymer is N-methylpyrrolidone,
It is poorly soluble in N,N-dimethylacetamide, etc., and tough films and membranes cannot be obtained from it.

(Effects of the Invention) The novel piperazine copolyamide of the present invention as described above has excellent solubility in amide solvents that conventional piperazine copolyamides do not have, and has a higher glass transition point (Tg). and thermal decomposition onset point (Td).

body

[Brief explanation of the drawing]

FIG. 1-1 shows the molecular weight distribution curve of the polymer obtained in Example 1 determined by liquid chromatography. FIG. 1-2 shows an infrared absorption spectrum (IR spectrum) of the polymer obtained in Example 1. Figure 1-3 shows H-NMR of the polymer obtained in Example 1.
The spectrum is shown. FIG. 2-1 shows the molecular weight distribution curve of the polymer obtained in Example 2 determined by liquid chromatography. FIG. 2-2 shows the infrared absorption spectrum (IR spectrum) of the polymer obtained in Example 2. Figure 2-3 shows H-NMR of the polymer obtained in Example 2.
The spectrum is shown. FIG. 3-1 shows the molecular weight distribution curve of the polymer obtained in Example 3 determined by liquid chromatography. FIG. 3-2 shows an infrared absorption spectrum (IR spectrum) of the polymer obtained in Example 3. Figure 3-3 shows H-NMR of the polymer obtained in Example 3.
The spectrum is shown.

Claims (3)

[Claims] (1) The main repeating unit is the following general formula (1) and (2)
), and the molar ratio of the repeating units (1) and (2) is from 95/5 to 35/65. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (However, R is a divalent aromatic group having 6 to 15 carbon atoms, and Y is a divalent Indicates an organic group. R^1, R^2, R^5, R^6, R^7, R^8, R
^9, R^1^0, R^1^1, R^1^2 are hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, R^3, R
^4 represents a monovalent organic group. n_1 and n_2 represent 0 or a natural number from 1 to 3. ) (2) A patent claim characterized in that the divalent amine component species in the repeating unit (2) is piperazine nylene and/or 2-methylpiperazinylene and/or trans-2,5-dimethylpiperazinylene. A copolyamide according to range 1. (3) The copolyamide according to claim 2, wherein R in the repeating units (1) and (2) is metaphenylene and/or paraphenylene.