KR890000033B1 - Preparation of aliphatic-aromatic amide copolymer - Google Patents

Abstract

A method for prepg. copolymer comprises (i) dissolving N,Ndianilidaliphatic amide, of formula (I) where n=2-9 integer, and p-phenylenediamine in amide polymn. solvent contg. CaCl2 or LiCl 1-5 wt.% and (ii) adding terephtharoyl chloride of same equiv. amts. of (I) and p-phenylenediamine to obtain the intrinsic viscosity of over 4.0.

Description

Process for preparing aliphatic-aromatic amide copolymer

First turning the poly (p- phenylene terephthalamide) and poly (p- phenylene ^{butyral-terephthalamide) -} weight of the aromatic amide copolymer-illustrated by comparing the tensile curve graph copolymers and aliphatic according to the invention .

2 is a graph showing intrinsic viscosity different from the increase in mole fraction of N, N-dianilidediphamide when synthesizing aliphatic-aromatic amide copolymers according to the present invention.

3 is a graph showing the degree of crystallinity according to the mole fraction of N, N- dianilide adipamide copolymer of the aliphatic-aromatic amide copolymer according to the present invention.

The present invention relates to aliphatic-aromatic amide copolymers, in particular, to introduce a new aliphatic repeating unit to the aramid polymer known to date, to compensate for the shortcomings of the existing aramid fibers, aliphatic-aromatic amide, aerial with increased strength and orientation rate It relates to a method for producing the coalescence.

Aramid polymers known to date and the fibers produced using the same have excellent performances compared to other polymers in physical properties such as chemical resistance, heat resistance, strength, and elastic modulus. In particular, the poly (p-phenylene terephthalamide) polymer described in US Pat. No. 3,671,542 and fibers using the same are developed under the trade name of "KEVLAR" developed by EI Dupont of the United States. It is one of the best physical properties among the known aramid polymer.

However, a serious drawback in using poly (p-phenyleneterephthalamide) is that it forms a rigid rod, as can be seen from the chemical structure of the polymer, and thus in the final product made of this polymer, i. In addition, the strength of the fiber axis in the longitudinal direction of the fiber shaft is very good, 20-30 g / D, whereas the physical properties of the fiber axis in the transverse direction are very weak, so that fibrillation occurs easily due to bending or friction. Because of these shortcomings, these materials are subject to considerable limitations in material development. For example, when a tire cord is made, the skin is easily peeled off due to repeated friction or bending during manufacturing or processing, and thus, the adhesion of the tire to the rubber is not only reduced, but also the strength is reduced.

Therefore, the poly (p-phenylene terephthalamide) to date has been considerably limited because of its use, and thus it is expected that the use range will be greatly expanded.

For this reason, various methods have been devised and studied to solve this problem.

Therefore, the present inventors have completed the present invention as a result of constant efforts to solve these shortcomings to produce a better polymer. That is, the present invention synthesizes a new polymer by using N, N-dianilide aliphatic amide and p-phenylenediamine as the diamine component of the monomer for synthesizing aramid polymer and adding the same equivalent of terephthaloyl chloride as the diamine component. It is an object of the present invention to provide a method for producing an aliphatic-aromatic amide copolymer which is much superior in general physical properties such as strength, orientation rate, fatigue resistance, and the like as compared with the conventional one.

Hereinafter, the present invention will be described in detail.

The present invention is a diamine component of the monomer for synthesizing aramid polymer and N, N- dianilide aliphatic amide represented by the following general formula (I)

(Where n is an integer from 2 to 9)

을 사용하고, 산성염화물 성분으로서는 테레프탈로일 클로라이드

를 사용하는 방법으로서, 상기 N,N-디아닐리드지방족아미드와 상기의 p-페닐렌디아민이 0,06:0.94 내지 0.19:0.81의 몰비로 혼합된 혼합물을, 염화리튬 또는 염화칼슘을 1 내지 5%함유하는 아미드계용매에 녹이고, 여기에다 테레프탈로일 클로라이드를 상기 p-페닐렌디아민 성분과 동일한 당량으로 첨가시켜서 고유점도가 4.0이상이 되는 지방족-방향족 아미드 공중합체를 제조하는 것을 특징으로 한다.p-phenylenediamine

The acid chloride component was used as terephthaloyl chloride.

As a method of using, the mixture of N, N- dianilide aliphatic amide and the p-phenylenediamine in a molar ratio of 0,06: 0.94 to 0.19: 0.81, 1 to 5% of lithium chloride or calcium chloride The aliphatic-aromatic amide copolymer having an intrinsic viscosity of 4.0 or more is prepared by dissolving in an amide solvent containing the same and adding terephthaloyl chloride in the same amount as the p-phenylenediamine component.

The present eruption is described in more detail as follows.

The present invention synthesizes N, N-dianilide aliphatic amide represented by the general formula (I) by reacting a fatty acid compound or a derivative thereof with aniline or a derivative thereof, and adds p-phenylenediamine in a molar ratio according to the present invention. The solution is polymerized with terephthalic acid chloride at a low temperature of 30 ° C. or lower, thereby preparing an aliphatic-aromatic amide copolymer in which a certain ratio of aliphatic chains is randomly contained but the regularity of the structure is perfect.

Synthesis of aliphatic-aromatic copolymers incorporating aliphatic chains into polyamides has been steadily studied until now. According to the synthesis and research, fibers made of aliphatic-aromatic copolymers prepared by introducing flexible aliphatic chains have been studied to some extent. Although it was possible to reduce the brillization, the physical properties, i.e., the strength was 10 to 15 g / D, which is lower than that of the wholly aromatic polyamide, were not practical, and the pyrolysis temperature was also lowered. (See US Pat. No. 3,453,244).

However, in the present invention, in introducing an aliphatic chain to the wholly aromatic polyamide, a partial aliphatic-aromatic random copolymer is not a complete alternating copolymer or a complete aliphatic-aromatic random copolymer. By forming a copolymer, it is possible not only to prevent the deterioration of physical properties and fibrillation, which is a problem mentioned above, but also to produce an aramid copolymer having superior strength in terms of strength and a faster orientation rate than a wholly aromatic polyamide.

This is easily compared with reference to the comparison graph as shown in FIG.

When explaining the production method of the present invention in detail as follows, first to synthesize the N, N- dianilide aliphatic amide of the diamine component represented by the general formula (I), represented by the following general formula (III) Fatty acid compounds,

Where n is an integer from 2 to 9

A dimethyl ester compound of a fatty acid represented by the following general formula (VI), or

Where n is an integer from 2 to 9

Chloride of Fatty Acids Represented by General Formula (Ⅴ)

Where n is an integer from 2 to 9

Reacting a fatty acid compound or a derivative thereof with aniline or a para-substituted product thereof, such as p-nitroaniline or p-phenylenediamine, to synthesize a compound having an aliphatic chain in the middle portion and an aromatic ring in each side thereof, and then The compound is prepared as an N, N-dianilide aliphatic amide compound through a nitrification reaction, a substitution reaction or a hydrogenation reaction.

The following method can be used as a specific example of the synthesis | combination of said N, N- diallylide aliphatic amide which is such a diamine component.

를 150내지 250℃에서, 1시간 30분 내지 5시간 30분 동안 반응시킨후 세척 및 건조시켜서 N,N-디페닐아디프아미드

를 제조한 다음, 이를 진한 황산용액에 용해시키고 여기에 0내지 10℃의 온도를 유지하면서 97%황산과 70%질산의 혼합물(1 : 1)을 서서히 적가하여 질소화반응을 시켜서 N,N-디니트로펜리아디프아미드

를 제조한다. 그 다음 이를 다시 세척하여 디메틸아세트아미드 등의 용매에서 10내지 1000psi 정도의 수소압력을 가하고 니켈촉매와 함께 80내지 130℃에서 3 내지 8시간 정도 수소화반응시켜서, N,N-디아닐리드아디프아미드를 제조한다. 이를 재결정법에 의하여 99%이상의 순도로 정제한다.2 moles or more of aniline and 1 mole of dimethyl adipate (adipic acid dimethyl ester:

N, N-diphenyladipamide by reacting at 150 to 250 ° C. for 1 hour 30 minutes to 5 hours 30 minutes, followed by washing and drying.

Was prepared, and then dissolved in a concentrated sulfuric acid solution and then slowly added dropwise to a mixture of 97% sulfuric acid and 70% nitric acid (1: 1) while maintaining a temperature of 0 to 10 ° C. to give a N, N- Dinitroperiadiamide

To prepare. After washing again, hydrogen pressure of about 10 to 1000 psi was applied in a solvent such as dimethylacetamide and hydrogenated with a nickel catalyst at 80 to 130 ° C. for about 3 to 8 hours to obtain N, N-dianilide adipamide. Manufacture. It is purified to 99% or more by recrystallization.

를 첨가하여 N,N-디니트로페닐아디프아미드를 합성하되 이때 산포집체로서 3급아민을 첨가시킨다. 그 다음 이 화합물을 정제하여 상기와 같은 방법으로 양쪽의 니트로기를 환원시키면 디아민 화합물이 제조되게 된다.As another method, two or more moles of p-nitroaniline are dissolved in a solvent such as dimethylacetamide at room temperature, and one mole of adipoyl chloride.

N, N-dinitrophenyladipamide was synthesized by adding a tertiary amine as an acid collector. Then, the compound is purified and the nitro groups on both sides are reduced in the same manner as above to prepare a diamine compound.

The diamine compound of the general formula (I) and p-phenylenediamine prepared by the above method are dissolved in an amide solvent in which lithium chloride or calcium chloride is dissolved in 1 to 5% at a concentration of about 3 to 10%, and then Terephthaloyl chloride is instantaneously added in the same amount as the sum of the compound of formula (I) and p-phenylenediamine at a temperature of 0 to 30 ° C. and a nitrogen atmosphere to prepare a polymer. In this case, dimethyl acetamide, N-methylpyrrolidone, and hexamethylphosphoramide are used as the amide solvent, and the reaction solvent is a tertiary amine such as pyridine and triethalamine as a ponip agent for an acid generated during the reaction. Or an oxide or carbonate of an alkali metal can be added from 0 to 20%.

The aliphatic-aromatic amide copolymer prepared by this method can be represented by the following general formula (II).

Where n is an integer from 2 to 9

단위는, 교대로 이어지는 규칙적이거나 완전히 무작위적인 반복단위가 아닌 부분적인 무작위적으로 반복되는 단위이며, p-페닐렌디아민과 N,N-디아닐리드지방족아미드의 혼합몰분율에 따라 고분자사슬중에 존재하는 단위수가 달라질 수 있다.In this case, the number of units of 1 is 6 to 19 mol%, and the number of units of m includes 94 to 81 mol%, but each unit is randomly present in the molecular chain. Mid-range alien chain

Units are units that are partly randomly repeated rather than alternating regular or completely randomly repeating units and are present in the polymer chain according to the mixed mole fraction of p-phenylenediamine and N, N-dianilide aliphatic amides. The number can vary.

The polymer prepared in this way is dissolved in concentrated sulfuric acid at a concentration of about 15 to 40% to form a thick liquid that can be spun in liquid crystal state, and then spun at a speed of 250 to 350 m / min through a spinning nozzle. As a result, when the intrinsic viscosity was 4.0 or more, a fiber having a strength of 15 to 28 g / D was obtained. In addition, the fiber has a high heat resistance of more than 400 ℃ and a high crystallinity of more than 40%, fibrillation is also significantly reduced compared to poly (p-phenylene terephthalamide) and was much superior in strength and the orientation rate of each crystal.

According to the method of the present invention, p-perylenediamine and N, N-dianilide aliphatic were reacted with terephthaloyl chloride while sequentially changing the mole fraction of p-phenylenediamine and N, N-dianilide aliphatic amide. When the amide ratio was 0.86: 0.14, the physical properties such as strength were better than those of the normal poly (p-phenylene terephthalamide), the orientation speed was faster, and the molar ratio of p-phenylenediamine and N, N-dianilide aliphatic amide was In the case of 0.81: 0.19 to 0.94: 0.06, similar results were found in the physical properties with poly (p-phenylene terephthalamide), but the orientation speed was high.

The present invention will be described in detail with reference to Examples.

Example 1

Into a three-necked flask equipped with a thermometer and a stirrer, 200 g of aniline and 20 g of dimethyl adipate were heated to 180 ° C. over 45 minutes, and methanol was released during the reaction, followed by further reaction at this temperature for about 3 hours. . When the reaction is complete, it is cooled to room temperature, the reaction is washed with methanol and dried. As a result of the test by the spectrometer (IR, NMR), it was confirmed that it was N, N- diphenyl adiamide.

The compound was added to 200 ml of sulfuric acid and maintained at 10 DEG C while adding a mixture of 15 g of 96% sulfuric acid and 15 g of 70% nitric acid, followed by filtration and washing with water and methanol and drying. As a result of the test by the spectrometer, the obtained product was confirmed to be N, N-dinitrophenadidiamide.

Example 2

350 ml of N-methylpyrrolidone and 10 g of N, N-dinitrophenyladipamide synthesized in Example 1 were dissolved in an autoclave, and 5.5 g of nickel catalyst and hydrogen pressure of 1000 psi were added thereto. The reaction is carried out for 6 hours while heated to 98 ℃, the product is purified by filtration and recrystallization.

Test by spectroscopy (IR.NMR) confirmed that it was N, N-dianilidediphamide.

Example 3

To a four-necked flask equipped with a thermometer, agitator, and nitrogen inlet, 240 ml of dimethylacetamide is added under a stream of nitrogen to dissolve 10 g of lithium chloride. In order to copolymerize p-phenylenediamine and N, N-dianilide adipamide in a molar ratio of 0.85: 0.15, 3.5 g of N, N-dianilidediphamide and 6.79 g of p-phenylenediamine were added. Dissolve.

Then 10 ml of pyridine is added and 15 g of terephthaloyl chloride is added instantaneously and the rotation speed of the stirrer is increased to about 400 times per minute. After about 3 minutes a powdery product is obtained.

After leaving for 5 hours under nitrogen atmosphere, it is washed with excess water and acetone and dried at 105 ° C.

The well-dried polymer was prepared with a 0.5% sulfuric acid (97%) solution, and the inherent viscosity was 6.0.

Again, this polymer is made of dope with 20% polymer concentration in 100% sulfuric acid, and is cooled with water while spinning at a speed of 260m / min through a nozzle of 0.06mm by applying nitrogen pressure of about 4kg at 75 ° C. The strength of the fiber thus produced is 24 g / D.

Comparative Example 1

Under the same conditions and methods as in Example 3, a copolymer was obtained using N, N-dianilide adipamide as the diamine component and terephthaloyl chloride as the acid chloride component. The intrinsic viscosity for the poly (p-phenylenebutyralterephthalamide) polymer is 3.2 and the strength of the fiber produced by spinning is 12 g / D.

Comparative Example 2

Poly (p-phenylene terephthalamide) was obtained using p-phenylenediamine as the diamine component and terephthaloyl chloride as the acid chloride component under the same conditions and methods as in Example 3. The polymer has an inherent viscosity of 5.8 and fiber strength of 22 g / D.

Example 4

The fibers prepared in Example 3 and Comparative Example 1 were stretched (speed 0.4 m / min) for 6 minutes at 280 ° C. under a nitrogen atmosphere and heat-treated.

As a result, the fiber produced according to the present invention was measured for elongation of about 12%, poly (p-phenylene terephthalamide) was about 11%, and poly (p-phenylbutyryl terephthalamide) copolymer was about 55%. As a result of measuring the load-tensile curve by INSTRON, the polymer according to the present invention was found to be excellent.

Example 5

A polymer was prepared in the same manner as in Example 3, except that the ratio of p-phenylenediamine and N, N-dianilidediphamide in the composition of the idamin component was sequentially synthesized from 0.95: 0.05 to 0.05: 0.95. To prepare a polymer and measure the intrinsic viscosity thereof (see FIG. 2).

On the other hand, as a result of measuring the crystallinity of the fiber heat-treated and stretched by an X-ray diffractometer, as shown in FIG. 3, the composition molar ratio of N, N-dianilide adipamide was found to be pure poly (p) between 0.05-0.45. It can be seen that the crystallinity of -phenylene terephthalamide) is greater.

Example 6

In the polymer prepared in Example 4, the molar ratio of p-phenylenediamine and N, N-dianilidediphamide was 0.86: 0.14 and the fibrillation of pure poly (p-phenylene terephthalamide) was observed. The degree of orientation is measured by a line diffractometer.

As a result of the fatigue resistance test under the same conditions and time, it was found that the polymer according to the present invention was much superior and the orientation was large.

Claims (4)

N, N-dianilide aliphatic amide and p-phenylenediamine represented by the following general formula (I) are dissolved in an amide-based polymerization solvent containing 1 to 5% of calcium chloride or lithium chloride, and then terephthaloyl chloride is added thereto. Method of producing an aliphatic-aromatic amide polymer, characterized in that the intrinsic viscosity is 4.0 or more by adding the same equivalent of the N, N- dianilide aliphatic amide and p-phenylenediamine combined.

Where n is an integer from 2 to 9 The method according to claim 1, wherein the molar ratio of N, N-dianilidealiphatic amide and p-phenylenediamine is 0.06: 0.94 to 0.19: 0.81. The method of claim 1, wherein the aliphatic-aromatic amide polymer is represented by the following general formula (II),

Where n is an integer from 2 to 9 In this case, the number of units of 1 is 6 to 19 mol%, the number of units of m comprises 94 to 81 mol%, wherein each unit is randomly present in the molecular chain. The method according to claim 1, wherein the amide polymerization solvent contains 0 to 20% of a tertiary amine or an alkali metal phase oxide or carbonate.

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