JPS61123631A - Production of aromatic polyamide copolymer - Google Patents

Abstract

PURPOSE:To produce the titled copolymer containing diamino compound units and acid chloride units arranged regularly and alternately in the molecular chain, on an industrial scale, by reacting a specific asymmetric aromatic diamino compound with an aromatic dicarboxylic acid chloride. CONSTITUTION:The objective copolymer can be produced by reacting an asymmetric aromatic diamino compound of formula I (Ar1 is bivalent aromatic residue; Ar2 and Ar3 are different bivalent aromatic residues; R1 and R2 are H, phenyl or <=10C alkyl) (e.g. the compound of formula II) with an aromatic dicarboxylic acid chloride of formula III (Ar4 is bivalent aromatic residue) (e.g. terephthaloyl chloride) in an aprotic amide solvent (e.g. N-methyl-2- pyrrolidone).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing aromatic polyamide copolymers with high regularity.

More specifically, it relates to a method for producing an aromatic polyamide copolymer in which 2m different aromatic diamine units and one or 2211 aromatic dicarboxylic acid units are alternately and regularly arranged in the molecular chain. It is something.

Prior Art Aromatic polyamides obtained from aromatic diamines and aromatic dicarboxylic acids have a high melting temperature.

High thermal decomposition temperature, high glass transition temperature, heat resistance 9
It is known to give molded products with excellent mulberry resistance and other chemical and physical properties. aRJ* (for example, substituted meta-phenylene iso-7-talamide fiber), which is made of aromatic polyamide and has excellent thermal properties, is useful as a heat-resistant, flame-retardant and flame-retardant fiber for protective clothing filter bags and the like. In addition, fibers made of aromatic polyamide and having excellent mechanical properties such as a large initial Young's modulus and strength (e.g., polyparaphenylene terephthalamide fibers) are used as rubber reinforcing materials for tire cords, belts, hoses, etc. 1. Plastics for composite materials Reinforcement material! Useful for ropes, bulletproof clothing, etc.

Also, certain copolymerized aromatic polyamides are useful as well. %, the copolymerized aromatic polyamide maintains the excellent properties of aromatic polyamide, and has the advantage of improving solubility and moldability (for example, Japanese Patent Publication No. 53
(Refer to Publication No.-32838).

By the way, the aromatic polyamide copolymer is obtained by polymerizing two or more aromatic diamine components and/or two or more aromatic dicarboxylic acid components. However, in these copolymers, 1, for example, the acid component is 11
When the diamine component is 2 mgk per chicken, in normal polymerization methods, due to the difference in reactivity of the two diamines and the random nature of the reaction, a complete alternating copolymer cannot be expected, but a random copolymer or a block. Copolymers and copolymers with intermediate polymer seafences are obtained.

(Peter A, Curnuck and Mic
ha@l E, B, Jon@g “A 5tudy of
5equence distribution in
anAromatic CopolyamideJ
Br, Polym, J1973.5.2l-32) The same applies to the reverse case, that is, when there are two acid components and the diluted base is 1 g. Random copolymers, block copolymers, and copolymers with polymer sea fences in between these have improved formability such as IWs properties compared to homopolymers, but their thermal properties are significantly lower than that of homopolymers. crystallinity may deteriorate.

There is a need for a copolymer that has improved these drawbacks, i.e., an aromatic polyamide copolymer that has excellent moldability such as solubility, and improved thermal properties and crystallinity. For this purpose, an alternating copolymer or a copolymer similar to the alternating copolymer having highly regular polymer sea fences is expected.

The following method can be considered as a method for synthesizing such a highly regular aromatic polyamide copolymer.

b) Two acid components (HOOC-T-COOH).

HOOC-8-Coon) and one diamine component (
HtN-*-NHt), the formula NA-NHCO-T-CONH-A-N+cIc
o-s-coα→+HN-A-NHCO-T-CONH
-A-NHCO-8-CO+n) acid component is IJiE (HOOC-T-COOH) ``t' Schiff If the in component is 2 components (&N-A-Kou + HJJ-B-corner 1, α- T-CONH-A-NHCO-T-COCJ +
H, N-B-NH1 → +C0-T-CONH-A-NH
CO-T-CONH-B-S÷However, in these methods, H,NA-NHCO-T-CONH-LA-NH,
, c*co-T-coNH-A-zuCo-T-Co(J
Because it is difficult to synthesize and purify the compound, and it is difficult to obtain high purity, a copolymer with a high degree of polymerization that can be processed into molded products such as fibers has not been obtained.

Object of the Invention The object of the present invention is to provide an aromatic polyamide in which two different aromatic diamine residues and 1 m or two aromatic dicarboxylic acid residues are alternately and regularly arranged in the molecular chain. An object of the present invention is to provide a method for industrially producing a copolymer.

Structure of the Invention The present invention relates to the general formula (A) H2N-Arc -NCO-Arl -CON-Ars
-NH.

[In the formula, Ar is a divalent aromatic residue s Ar1tArl
represent 21111 aromatic residues that are different from each other. R
, eR, may be the same or different and are selected from a hydrogen atom, a phenyl group, and an alkyl group having 10 or less carbon atoms. ] An asymmetric aromatic diamino compound represented by the general formula (B) C/COAr4 COCl ・・・・・・・・・
......CB) [Ar4 represents a divalent aromatic residue. This is a method for producing an aromatic polyamide copolymer having high regularity, which is characterized by reacting an aromatic dicarbonyl chloride represented by the following formula.

In the present invention, [the above general formula (A) used].

In the aromatic dicarboxylic acid chloride represented by CB), Art v 7g + Arm l Ar4 is L
- All of which represent divalent aromatic residues, as representative examples of such aromatic residues.

Examples include. Arm t
Ar4 1 house.

The residues may be the same as each other as long as they are mul-kr@. Among them, preferred as Ar1tAr are para-phenylene and meta-phenylene, and the most preferred is -(rough phenylene).

When one of Ar or Ar3 is an aromatic residue, it is most preferred that the residue is paraphenylene.

The hydrogen atom of the aromatic ring of these aromatic residues is a halogen group,
An alkyl group having 1 to 10 carbon atoms.

It may be substituted with a substituent such as an alkoxy group, an acetyl group, or a benzoyl group.

Further, Rt-Rt may be the same or different and are selected from a hydrogen atom, a phenyl group, and an alkyl group having 10 or less carbon atoms. Most preferred is a hydrogen atom.

In the present invention, it is preferable to use one type each of the above-mentioned aromatic diamine and aromatic dicarboxylic acid chloride, but two or more types can be used if necessary.

For example, when reacting using cico Qoc* as an aromatic dicarboxylic acid chloride as an aromatic diamine, a part of the aromatic diamine may be replaced with or, etc., and a part of the aromatic dicarboxylic acid may be replaced with, etc. May be replaced.

According to the present invention, as a polymerization method for reacting an asymmetric aromatic diamino compound represented by the general formula () with an aromatic dicarboxylic acid chloride represented by the general formula However, since the asymmetric aromatic diamine compound represented by the general formula is difficult to produce, a low-temperature solution polymerization method using a non-digton amide solvent for linking them is preferred. Such aprotic amide solvents include dimethylformamide (DMF), dimethylacetamide (D
MAC), N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU)s hexamethylphosphor 7
Examples include mido (HMPA). Among these women, N
M.P.

DMAC is preferred.

The reaction temperature is selected depending on the concentration of monomer or polymer, but is preferably in the range of 0°C to 100°C.

A polymer solution obtained by low-temperature solution polymerization is heated with water, and the precipitated polymer is separated and washed with water.

Although the polymer can be isolated and used after drying, generally the obtained polymer solution is directly subjected to spinning or molding. In that case, the hydrochloric acid by-produced by polymerization is converted into an alkali or alkaline earth metal oxide or hydroxide.

It is preferable to neutralize with a carbonate such as lithium oxide, lithium hydroxide, lithium carbonate, calcium oxide, calcium hydroxide, calcium carbonate, etc.

The asymmetric aromatic diamino compound of the general formula (2) used in the method of the present invention is expressed by the method separately proposed by the present inventors, that is, the general formula % [wherein Arl is the same as above] Compound and general formula % Formula % [In the formula, Arl is a divalent aromatic residue 1. R1 is selected from a hydrogen atom, a phenyl group, and an alkyl group having 10 or less carbon atoms. ] in an aprotic amide solvent with 0
The product after reacting below ℃.

Without separation, the general formula % formula % [wherein Ar3 is a divalent aromatic residue different from Arl,
R8 is selected from a hydrogen atom, a phenyl group, and an alkyl group having 10 or less vertical primes. ] to form an asymmetric aromatic dinitro compound represented by the general formula % [where Ar, t Arl I Arl are the same as above], and then catalytic reduction thereof.゛ Can be manufactured.

This compound is stable and can be easily purified to high purity by recrystallization.
An aromatic polyamide copolymer having a high regularity with a viscosity of 1 to 5) can be obtained. The obtained copolymer can be easily molded into molded products such as fibers and films.

Furthermore, the aromatic polyamide copolymer having high regularity obtained by the method of the present invention can be used as a lantern copolymer or block copolymer obtained by a conventional method, and a copolymer having a polymer sea fence intermediate between these □. In comparison, it maintains excellent solubility and has the advantage of excellent crystallinity.

EXAMPLES Comparative examples and examples of the present invention will be described in detail below. In addition, the value of the intrinsic viscosity (1, V,) of the polymer in this specification is 9
This is a value measured at 30° C. for a solution with a polymer concentration of 0.5 JI/# in 8% concentrated sulfuric acid.

Comparative Example 1 Flask KN-methyl-2-pyrrolidone (NMP) 560aI with anchor-shaped stirring blades that allow phonemes to flow inside
j, paraphenylenediamine 8.765 Jl
and 3,4-diaminodiphenyl ether 1 g, 2241
I linked it with. When the temperature of this solution was 30° C., 32.750 J of terephthalic acid chloride was added, and vigorous stirring was continued. The viscosity of the solution gradually increased, and 15 minutes after heating the bath liquid to 85°C, calcium hydroxide 11
．． A slurry consisting of 9 s'z tt and 40μ of NMP was added and stirring continued at 90°C. Stirring and heating were completed after 60 minutes, and a portion was sampled and mixed with water.

The resulting polymer precipitate was washed with water and dried to give an intrinsic viscosity of KC1.
,v,) were measured. 1. of the polymer. V.

When we measured this polymer with a temperature of 2.45 using a differential scanning calorimeter, we found that no clear crystallization behavior was observed;
Two melting pyrolysis peaks were observed at 1°C.

The NMP bath solution of the polymer obtained in this way was filtered and degassed, and NMP at room temperature was passed through a nozzle with a hole diameter of 0.2 x v and a number of holes of 5 using the so-called semi-dry and semi-wet spinning method.
It was spun into an aqueous #j solid bath containing vtX at a discharge rate of sml- and wound up at a speed of 6 m/-. The film was then washed with water and stretched on a dried filament hot plate at the temperature shown in Table 1 in a conventional manner.

At that time, the maximum draw ratio at which the fiber breaks at each temperature (
Strength and elongation of fibers obtained by stretching with MDR) and MDH 8096 tsuta-stretching double-rolling.

The initial Young's modulus is shown in Table 1.

Table 1 Example 1 560 N-methyl-2-pyrrolidone (NMP) was charged into a flask equipped with a stirrer and nitrogen was flowing inside, and 30.029 N of the following compound was dissolved therein.

When the temperature of this solution reached 30° C., 13.843 N of terephthalic chloride was added and vigorous stirring was continued. The viscosity of the solution increased slowly and a slurry consisting of 49m was added and stirring continued at 90°C. Stirring and heating were finished after 60 minutes, a part of it was sampled and mixed with water, and the obtained polymer precipitate was washed with water and dried to obtain an intrinsic viscosity [(LV,
) was measured. 1. of the polymer. V.

was 2.52. When this polymer was measured using a differential scanning calorimeter, it was found that a 400-450' CIC crystallization region was present, and one melting pyrolysis peak was observed at 523°C. From these facts, the thermal properties are improved compared to the polymer obtained by Comparative Example IK.

? : KK, N M of the polymer obtained in this way
After filtering and defoaming the bath liquid, it is passed through a nozzle with a hole diameter of 0.2 m + number of holes of 5 using the so-called semi-dry semi-wet spinning method.
NMP at room temperature was spun into an aqueous coagulation bath containing 30wt96 at a discharge rate sm/- and wound up at a rate of 9H/Ijll. Next, the threads, which had been washed with water and dried in a conventional manner, were stretched on a hot plate at the temperatures shown in Table 2. At that time, the maximum draw ratio (MDR) and M at which the fiber breaks at each temperature
The strength of the fiber obtained by winding it at a magnification of 80% of DH,
The elongation and initial Young's modulus are shown in the JIIZ table.

Comparing Tables 1 & 2 with Table 2, it is clear that the polymers rolled by the method of the present invention have a larger maximum fiber expansion force and provide 41 fibers with excellent strength. .

Effects of the Invention According to the method of the present invention as described above, an aromatic polyamide copolymer having a high degree of polymerization and a high degree of regularity can be obtained, and this copolymer has excellent solubility and heat resistance. It has excellent properties and crystallinity.

Therefore, this copolymer can be easily molded into fibers, films, etc., and the physical properties of the resulting molded products are also very good.

Claims (6)

[Claims] (1) General formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(A) [In the formula, Ar_1 is a divalent aromatic residue, Ar_2, Ar
_3 represents different divalent aromatic residues. R_1 and R_2 may be the same or different and are selected from a hydrogen atom, phenyl, and an alkyl group having 10 or less carbon atoms. ] An asymmetric aromatic diamino compound represented by the general formula (B) ClCO-Ar_4-COCl...
...(B) (Ar_4 represents a divalent aromatic residue) An aromatic polyamide copolymer with high regularity characterized by reacting with an aromatic dicarboxylic acid chloride represented by Manufacturing method. (2) The method for producing an aromatic polyamide copolymer according to claim (1), wherein Ar_1 and Ar_4 are both paraphenylene residues. (3) Either Ar_2 or Ar_3 is ▲ formula,
A method for producing an aromatic polyamide copolymer according to claim (1) or (2), wherein the chemical formula, table, etc. are ▼, and the other is a paraphenylene residue. (4) Ar_1, Ar_3 and Ar_4 are all paraphenylene residues, and Ar_3 is ▲Numerical formula, chemical formula, table, etc.▼ of the aromatic polyamide copolymer according to claim (3). Manufacturing method. (5) The method for producing an aromatic polyamide copolymer according to any one of claims (1) to (4), wherein R_1 and R_2 are all hydrogen atoms. (6) A method for producing an aromatic polyamide copolymer according to any one of claims (1) to (5), in which the reaction is carried out in an aprotic amide solvent.