KR910008373B1 - Nevel aromatic (amide-ester) monomer and preparation thereof - Google Patents

Abstract

Aromatic (amide-ester) nitro cpd. of formula (I) is prepd. by mixing a tert.-amine cpd. with p-aminophenol in a tert.-amide solvent, and condensing the reactant with p-aminobenzyl chloride, or dissolving p-aminophenol in an inorganic base soln., dissolving p- nitrobenzoyl chloride in a non-polar solvent, and interfacially condensing them. Aromatic (amide-ester) diamine cpd. of formula (II) is prepd. by heat-reacting (I) with H2 and reducing catalyst in an organic solvent. Pref. tert.-amine is selected from pyridine, picoline, quinoline or triethylamine.

Description

Novel aromatic amide-ester monomers and preparation method thereof

The present invention relates to a monomer which is a basic material of an aromatic and aromatic-aliphatic copolymerized polyamide-ester polymer having a new chemical structure, and a method for producing the same.

Fibers commercially available under the trade name "KEVLAR" from DuPont, USA, which are known so far as high strength and high modulus fibers, are described in US Pat. Nos. 3,600,350 and 3,671,542.

However, Kevlar-type wholly aromatic polyamide fibers have low fiber elongation and are extremely weak in durability when used in tire cords or other places of high friction due to fibrillation.

In addition, the use of high concentration of sulfuric acid during the liquid crystal spinning, such as processing is not easy, there is a problem in the corrosiveness of the device, risk of work and disposal of waste liquid.

On the other hand, aliphatic polyamides, which are flexible in molecular chains, that is, general nylon fibers, have high elongation, low fibrillation tendency, and are easy to process. have. In order to supplement these properties, Korean Patent Publication (B1) No. 1167 describes a method for producing an aromatic-aliphatic alternating co-condensation polyamide fiber, which does not have a tendency to fibrillation and has high heat resistance and high strength and high elastic modulus. As a fiber, the polymer hybrid fiber described in Korean Patent Publication (B1) No. 1186 has been made possible.

On the other hand, according to Japanese Patent Application No. 48-35117

또는

으로 나타낸 폴리아미드중합체와 이로부터 제조되는 HM-50이라는 상품명의 섬유류는 중합에서 얻어진 등방성중합 도우프를 직접 방사하여 고온열연신하는 방사방법이 가능하여, 생산공정을 훨씬 단순화하였다.

or

The polyamide polymer represented by the present invention and the fibres manufactured under the trade name HM-50 can be spun to directly spin the isotropic polymer-doped dope obtained in the polymerization, and to perform high-temperature heat stretching, thereby simplifying the production process.

The present inventors have focused on the fact that the structural properties of polymers have a great influence on the fiber production process. To prepare new fully aromatic and aromatic-aliphatic copolymerized poly (amide-ester) polymers, aromatic (amide-ester) monomers, which are starting materials for the production of polymers, ie aromatics (amide-esters) Diamine compounds were prepared.

Since the aromatic (amide-ester) diamine has a 1: 1 ratio of amide bonds and esters in the molecular chain, polymers prepared as starting materials are used in the polymer regardless of wholly aromatic polymer or aromatic-aliphatic copolymer. It becomes the polymer whose bond ratio of the amide bond and ester of a molecular chain is 3: 1.

The present invention adds a tertiary amine to a tertiary amide solvent, condenses P-nitrobenzoyl chloride and P-aminophenol, or dissolves P-aminophenol in an inorganic base solution, and adds P-nitrobenzoyl chloride to a nonpolar solvent. After dissolving, it is interfacially condensed to form an aromatic (amide-ester) nitro compound represented by the following structural formula (I),

Aromatic (amide-ester) diamine compound, which is a starting material in the preparation of a polymer, is prepared by the high pressure reaction in the presence of hydrogen in the presence of hydrogen using a reducing catalyst in an organic solvent,

Was synthesized.

In order to prepare the aforementioned aromatic (amide-ester) nitro compound (I), tertiary amide solvents are N, N-dimethylacetamide, N-methylpyrrolidone, N, N, N ', N'-tetramethyl In urea and N-methylcaprolactam alone or in mixtures of two or more thereof, tertiary amines may be selected from pyridine, picoline, quinoline and triethylamine.

Sodium carbonate and sodium hydroxide may be used as the inorganic base, and benzene, cyclohexanone, carbon tetrachloride, or the like may be used as the organic solvent.

The former aromatic (amide-ester) nitro compound (I) is used as a basic reactant of the synthesis of aromatic (amide-ester) diamine compound which is a polymerization starting material.

To prepare an aromatic (amide-ester) diamine compound represented by Structural Formula (II), the organic solvent may be N, N-dimethylacetamide, ethyl acetate, ethanol, methanol, N, N-dimethylformamide, N-methylpyrrolidone And acetone, and the reduction catalyst may also use palladium / C, RANEY nickel and platinum dioxide.

In order to synthesize an aromatic (amide-ester) diamine compound, the reaction temperature is 20 ° C.-250 ° C. and the reactor pressure is 1-50 atm.

According to the present invention, an aromatic (amide-ester) diamine compound (II) is used to add a wholly aromatic poly (amide-ester) and an aromatic-aliphatic poly (amide-ester) copolymer to which a tertiary amine is added as a reaction accelerator and alkali. The aromatic (amide-ester) diamine compound and aromatic and aliphatic diacid chloride were prepared by low-temperature polycondensation in a tertiary amide solvent in which a metal salt was dissolved.

The general formula is as follows.

Among the above-mentioned formula (Ⅲ) P- X is phenylene or _{- (CH 2) x -,} x is an integer, n is an integer of two or more of 2-10. In the general formula (III), the polymer synthesized when X is P-phenylene is represented by

When poly (amide-ester) terephthalamide is represented and X is-(CH ₂ ) _x- , X is made constant in one polymer by using one kind of aliphatic diacid chloride in one reaction.

Polymers synthesized according to the type of aliphatic diacid chloride used are poly (amide-ester) succinamide, poly (amide-ester) glutalamide, poly (amide-ester) adifamide, poly (amide-ester) Fimeramides, poly (amide-ester) suberamides, poly (amide-ester) azeramides, poly (amide-ester) sebacoamides, poly (amide-ester) nonanedi carboxylic acid amides and poly (amide-esters) Decanedicarboxylic acid amide.

In addition, in the polymerization solvent in which a metal salt is dissolved in a tertiary amide solvent and a tertiary amine is added as a reaction accelerator, the aromatic (amide-ester) diamine compound (II) of the above is added to the aromatic diacid chloride and aliphatic diacid chloride. As a result of polymerizing the lead at various mixing ratios, various kinds of polymers represented by the following formula (IV) were obtained.

은 0＜

＜1, m은 1-

, n은 2이상의 정수이다.In formula (IV), x is an integer of 2-10,

Is 0 <

<1, m is 1-

, n is an integer of 2 or more.

To prepare wholly aromatic poly (amide-ester) and aromatic-aliphatic poly (amide-ester) copolymers, the tertiary amide solvents are N, N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphor Single or two or more of amide, N, N-diethylacetamide, N-ethylpyrrolidone, N, N, N ', N'-tetramethylurea, N-methylcaprolactam and N-acetylpyrrolidone In the mixture, the alkali metal salt can be selected from lithium chloride and calcium chloride, and the tertiary amine can be selected from pyridine, picoline, quinoline and triethylamine.

The amount of the electroalkali metal salt and the tertiary amine can be used in 0-10% and 1-50% of the reaction mixture, respectively. Aromatic and aliphatic diacid chlorides used are derephthal chloride, succinyl chloride, adipoyl chloride, subveroyl chloride, glutaryl chloride, pimeroyl chloride, azeolayl chloride, sebacoyl Chloride, 1,9-nonanedicarboxylic acid chloride, 1,10-decadicarboxylic acid, and the like.

Hereinafter, the method for producing the aromatic (amide-ester) nitro compound (I) and the aromatic (amide-ester) diamine compound (II) according to the present invention and the prepared diamine compound as polymer starting materials are used in poly (amide-ester) air. The manufacturing method of coalescence (III) and (IV) is demonstrated by an Example.

Example 1

Synthesis of Aromatic (amide-ester) nitro Compound (I).

의 3구 구형 플라스크에 300㎖의 N,N-디메틸아세트아미드, 43.5㎖의 피리딘, 29.4g(0.27mol)의 파라아미노페놀을 함께 넣고 교반하여 용액을 만들었다.Capacity with stirrer, thermometer 1

300 ml of N, N-dimethylacetamide, 43.5 ml of pyridine, and 29.4 g (0.27 mol) of paraaminophenol were added together and stirred into a three-neck spherical flask.

The temperature of this solution was maintained at 30 ° C. where 100 g (0.54 mol) of para-nitrobenzoyl chloride were added and stirring continued for 1 hour.

200 ml of water was added to the reaction mixture to precipitate the product, followed by filtration and drying to recrystallize with N, N-dimethylformamide, 104 g (yield 95%) of dinitro compound 4- (4'-nitrobenzamido). -Phenyl-4 "-nitrobenzoate [4- (4-nitrobenzamido) -phenyl-4" -nitrobenzoate] was obtained.

Example 2

Compound (I) of Example 1 was synthesized via interfacial condensation.

의 3구 구형 플라스크에 29.4g(0.27mol)의 파라-아미노페놀과 86.9g(0.82mol)의 탄산나트륨 550㎖의 물에 용해시켰다.1.5 volume with stirrer and thermometer

In a three-neck spherical flask was dissolved in 29.4 g (0.27 mol) of para-aminophenol and 86.9 g (0.82 mol) of sodium carbonate 550 ml of water.

The temperature of this solution was maintained at 20 ° C. and 100.2 g (0.54 mol) of para-nitrobenzoyl chloride was dissolved in 250 ml of cyclohexanone, which was then temporarily added and stirred for 1 hour.

The reaction mixture was filtered, washed several times with water and ethanol, dried and recrystallized with N, N-dimethylformamide to give 102,3 g (yield 94%) of dinitro compound 4- (4'-nitrobenzamido) phenyl. -4 "-nitrobenzoate [4- (4-nitrobenzamido) -phenyl-4" -nitrobenzoate] was obtained.

Example 3

Synthesis of Aromatic (amide-ester) diamine Compound (II).

20 g (0.05 mol) of dinitro compound (I) obtained in Example 1, 3 g of raninickel, and 200 ml of N, N-dimethylacetamide were added to a high pressure reactor, and reacted for 3 hours at 100 ° C hydrogen pressure of 20 atm. . After completion of the reaction, the catalyst was filtered to remove the catalyst, 200 ml of water was added to precipitate the product, filtered and dried and recrystallized with N, N-dimethylacetamide to give 16.0 g (yield 94%) of 4-amine as a diamine. 4'-aminobenzamido) -phenyl-4 "-aminobenzoate [4- (4'-aminobenzamido) -phenyl-4" -aminobenzoate] was obtained.

Example 4

This is the case where palladium / C is used as a reduction catalyst in the preparation of the diamine compound (II) of Example 3.

20 g (0.05 mol) of dinitro compound (I) obtained in Example 1, 1 g of palladium / C, and 150 ml of ethyl acetate were placed in a high pressure reactor and reacted at 50 DEG C for 5 hours under hydrogen pressure of 5 atmospheres.

After completion of the reaction, the catalyst was filtered to remove the catalyst, 20 ml of water was added to precipitate the product, filtered and dried and recrystallized with N, N-dimethylacetamide to give 16.1 g (yield 94%) of 4-amine as a diamine compound. 4'-aminobenzamido) -phenyl-4 "-aminobenzoate [4- (4'-aminobenzamido) -phenyl-4" -aminobenzoate] was obtained.

Example 5

Polymerization of Poly (amide-ester) terephthalamide.

의 사구 구형 플라스크에 250㎖(2.69mol)의 N,N-디메틸아세트아미드, 9.5g(0.22mol)의 염화리튬 및 20.82g(0.06mol)의 디아민(Ⅱ)를 넣고 교반하여 용액을 만들었다. 이 용액의 온도를 25℃로 유지시키고 여기에 10㎖(0.12mol)의 피리딘을 첨가한 다음 12.18g(0.06mol)의 테레프탈로일클로리드를 일시에 가하여 격렬하게 교반하였다.Capacity with stirrer, thermometer and nitrogen inlet 1

250 mL (2.69 mol) of N, N-dimethylacetamide, 9.5 g (0.22 mol) of lithium chloride, and 20.82 g (0.06 mol) of diamine (II) were added and stirred into a four-necked globular flask. The temperature of this solution was maintained at 25 ° C., and 10 ml (0.12 mol) of pyridine was added thereto, followed by the addition of 12.18 g (0.06 mol) of terephthaloyl chloride at one time and stirring vigorously.

After the reaction mixture became a highly viscous solution in a few minutes, it was continuously stirred for 1 hour and left at room temperature for 1 day. An excess of water was added to the reaction mixture, and the mixture was pulverized with a mixer. The polymer was precipitated in a powder state and filtered to recover the polymer. The recovered polymer was washed several times with water and acetone and then dried in a vacuum dryer at 100 ° C. for at least 12 hours. The obtained polymer powder was light yellow and the intrinsic viscosity was measured at 5.12.

Example 6

When calcium chloride was used as the alkali metal salt in the polymer preparation of Example 5, 250 ml (2.69 mol) of N, N-dimethylacetamide, 8.88 g (0.08 mol) of calcium chloride and 20.82 g (0.06 mol) were used in the same apparatus as Example 5. ) Diamine compound (II) was added and stirred to form a solution.

The temperature of this solution was maintained at 25 ° C., and 11.5 mL (0.14 mol) of pyridine was added thereto, followed by the addition of 12.18 g (0.06 mol) of terephthaloyl chloride at a time and stirring vigorously.

The reaction mixture became a highly viscous solution in a few minutes and the mixture was stirred for 1 hour and left at room temperature for 1 day.

Hereinafter, the polymer powder obtained by recovering the polymer in the same manner as in Example 5 was pale yellow, and its inherent viscosity was measured to be 4.87.

Example 7

When N-methylpyrrolidone was used as a polymerization solvent in the preparation of the polymer of Example 5.

250 ml (2.59 mol) of N-methylpyrrolidone, 9.5 g (0.22 mol) of lithium chloride, and 20.82 g (0.06 mol) of diamine compound (II) were added and stirred in the same device as in Example 5 to prepare a solution. .

The temperature of this solution was maintained at 25 ° C., and 10 ml (0.12 mol) of pyridine was added thereto, followed by the addition of 12.18 g (0.06 mol) of terephthaloyl chloride at one time and stirring vigorously.

The reaction mixture became a highly viscous solution in a few minutes and the mixture was stirred for 1 hour and left at room temperature for 1 day. Hereinafter, the polymer obtained by recovering the polymer in the same manner as in Example 5 was pale yellow powder, and its inherent viscosity was measured to be 4.69.

Example 8

When the polymer of Example 5 used a 1: 2 mixture of hexamethylphosphoramide and N-methylpyrrolidone.

83.5 ml (0.48 mol) hexamethylphosphoramide, 166.5 ml (1.74 mol) N-methylpyrrolidone, 8.2 g (0.19 mol) lithium chloride and 20.82 g (0.06 mol) in the same device as Example 5. Diamine compound (II) was added to the solution to form a solution. The temperature of the solution was maintained at 25 ° C., and 18.5 mL (0.22 mol) of pyridine was added thereto, followed by the addition of 12.18 g (0.06 mol) of terephthaloyl chloride at one time and stirring vigorously.

The reaction mixture was turned into a highly viscous solution in a few minutes, and the mixture was stirred for one hour and left at room temperature for one day.

The polymer was recovered in the same manner as in Example 5 below, and the obtained polymer powder was light yellow with an inherent viscosity measured as 4.58.

Example 9

Polymerization of Poly (amide-ester) succinamides.

의 사구 구형 플라스크에 250㎖(2.69mol)의 N,N-디메틸아세트아미드, 5.5g(0.13mol)의 염화리튬 및 26.38g(0.076mol)의 디아민 화합물(Ⅱ)을 넣고 교반하여 용액을 만들었다. 이 용액의 온도를 20℃로 유지시키고 여기에 10㎖(0.12mol)의 피리딘을 첨가한 다음 11.78g(0.076mol)의 숙시닐클로리드를 일시에 가하여 격렬하게 교반하였다.Capacity with stirrer, thermometer and nitrogen inlet 1

250 mL (2.69 mol) of N, N-dimethylacetamide, 5.5 g (0.13 mol) of lithium chloride, and 26.38 g (0.076 mol) of diamine compound (II) were added and stirred into a four-necked globular flask. The temperature of this solution was maintained at 20 ° C. and 10 ml (0.12 mol) of pyridine was added thereto, followed by the addition of 11.78 g (0.076 mol) of succinyl chloride at once and vigorously stirring.

The reaction mixture became a highly viscous solution in a few minutes and the mixture was stirred for 1 hour and left at room temperature for 1 day. An excess of water was added to the reaction mixture, and the mixture was pulverized with a mixer. The polymer was precipitated in a powder state and filtered to recover the polymer.

The polymer obtained was washed several times with water and acetone, and then dried in a vacuum dryer at 100 ° C. for at least 12 hours. The polymer powder was brown, and its inherent viscosity was measured to be 3.12.

Example 10

Polymerization of Poly (amide-ester) adipamide.

의 사구 구형 플라스크에 250㎖(2.69mol)의 N,N-디메틸아세트아미드, 4.5g(0.11mol)의 염화리튬 및 28.47g(0.082mol)의 디아민 화합물(Ⅱ)을 넣어 교반하여 용액을 만들었다. 이 용액의 온도를 20℃로 유지시키고 여기에 10㎖(0.12mol)의 피리딘을 첨가한 다음 15.01g(0.082mol)의 아디포일클로리드를 가하여 격렬하게 교반하였다. 반응혼합물이 수분내에 고점성용액이 된 후 이를 1시간 동안 계속 교반한 후 상온에서 1일간 방치해두었다.Capacity with stirrer, thermometer and nitrogen inlet 1

250 mL (2.69 mol) of N, N-dimethylacetamide, 4.5 g (0.11 mol) of lithium chloride, and 28.47 g (0.082 mol) of diamine compound (II) were added and stirred into a four-necked globular flask. The temperature of this solution was maintained at 20 ° C., and 10 ml (0.12 mol) of pyridine was added thereto, followed by 15.01 g (0.082 mol) of adipoyl chloride, followed by vigorous stirring. After the reaction mixture became a highly viscous solution in a few minutes and stirred continuously for 1 hour, it was left at room temperature for 1 day.

An excess of water was added to the reaction mixture, and the mixture was pulverized with a mixer. The polymer was precipitated in a powder state and filtered to recover the polymer.

The polymer powder obtained by washing the recovered polymer with water and acetone several times and then vacuum drying at 100 DEG C for 12 hours or more was pale yellow, and its inherent viscosity was 3.21.

Example 11

Polymerization of Poly (amide-ester) suberamide.

의 사구 구형 플라스크에 250㎖(2.69mol)의 N,N-디메틸아세트아미드, 4.5g(0.11mol)의 염화리튬 및 30.41g(0.088mol)의 디아민 화합물(Ⅱ)을 넣고 교반하여 용액을 만들었다. 이 용액의 온도를 20℃로 유지시키고 여기에 10㎖(0.12mol)의 피리딘을 첨가한 다음 10.57g(0.088mol)의 수베로일클로리드를 가하여 격렬하게 교반하였다.Capacity with stirrer, thermometer and nitrogen inlet 1

250 mL (2.69 mol) of N, N-dimethylacetamide, 4.5 g (0.11 mol) of lithium chloride, and 30.41 g (0.088 mol) of diamine compound (II) were added to a four-necked globular flask of to form a solution. The temperature of this solution was maintained at 20 ° C., and 10 ml (0.12 mol) of pyridine was added thereto, followed by the addition of 10.57 g (0.088 mol) of suveroyl chloride, followed by vigorous stirring.

After the reaction mixture became a highly viscous solution in a few minutes, the reaction mixture was continuously stirred for 1 hour and left at room temperature for 1 day. An excess of water was added to the reaction mixture, and the mixture was pulverized with a mixer. The polymer was precipitated in a powder state and filtered to recover the polymer.

The polymer obtained was washed several times with water and acetone, and then dried in vacuo at 100 ° C. to obtain a light yellow powder. The specificity thereof was 2.85.

Table 1 is a table showing the intrinsic viscosity of the polymer other than Example 5-11 prepared according to the type and amount of diacid chloride.

TABLE 1

Example 12

Polymerization of Poly (amide-ester) terephthal-adipamide copolymers.

의 사구 구형 플라스크에 250㎖(2.69mol)의 N,N-디메틸아세트아미드, 7.6g(0.18mol)의 염화리튬 및 26.28g(0.076mol)의 디아민 화합물(Ⅱ)을 넣고 교반하여 용액을 만들었다.Capacity with stirrer, thermometer and nitrogen inlet 1

250 mL (2.69 mol) of N, N-dimethylacetamide, 7.6 g (0.18 mol) of lithium chloride, and 26.28 g (0.076 mol) of diamine compound (II) were added to a four-necked globular flask of to form a solution.

The temperature of the solution was kept at 20 ° C., and 10 ml (0.12 mol) of pyridine was added thereto, followed by 7.71 g (0.038 mol) of terephthaloyl chloride and 6.95 g (0.038 mol) of adipoyl chloride. Stir vigorously.

After the reaction mixture became a highly viscous solution in a few minutes and stirred continuously for 1 hour, it was left at room temperature for 1 day. The polymer powder obtained by recovering the polymer in the same manner as in Example 5 was pale yellow, and its inherent viscosity was measured to be 4.41.

Table 2 below shows the intrinsic viscosity (terephthal: adiph) of the product polymer according to the aromatic: aliphatic ratio of Example 12.

TABLE 2

The above-described embodiments are merely illustrative of the manufacturing method of the present invention and are not limited to the embodiments, and can be variously changed within the scope of the present invention.

The monomers prepared according to the present invention are used as starting materials in preparing aromatic and aromatic-aliphatic copolymerized polyamide-ester polymers having a new chemical structure, and the polymers thus prepared have excellent solubility in organic solvents. Therefore, it is possible to manufacture a high concentration polymer solution, which can bring about a simplified spinning process and a cost saving effect.

Claims (5)

Structural Formula (I)

Aromatic (amide-ester) nitro compound represented by. The aromatic represented by the above-mentioned structural formula (I), which is prepared by adding a tertiary amine and P-aminophenol together to a tertiary amide solvent and stirring the mixture, followed by condensation with P-nitrobenzoyl chloride. -Ester) nitro compound production method. Structural Formula (II)

Aromatic (amide-ester) diamine compound represented by Aromatic (amide-ester) represented by the above formula (II), characterized in that it is synthesized from the aromatic (amide-ester) nitro compound represented by the above formula (I) through a high-temperature pressurization reaction using hydrogen and a single catalyst in an organic solvent. ) Method for producing a diamine compound. Aromatic (amide-ester) nitro compound represented by the above formula (I), which is prepared by dissolving P-aminophenol in an inorganic base aqueous solution and dissolving P-nitrobenzoyl chloride in a nonpolar solvent to interfacially condense it. Manufacturing method.