KR20080061176A - Preparation method of para-polyamid having high inherent viscosity and fast reaction time - Google Patents

Preparation method of para-polyamid having high inherent viscosity and fast reaction time Download PDF

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KR20080061176A
KR20080061176A KR1020060136174A KR20060136174A KR20080061176A KR 20080061176 A KR20080061176 A KR 20080061176A KR 1020060136174 A KR1020060136174 A KR 1020060136174A KR 20060136174 A KR20060136174 A KR 20060136174A KR 20080061176 A KR20080061176 A KR 20080061176A
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solution
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polyamide
chloride
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권순홍
박성호
김동환
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주식회사 효성
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides

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Abstract

A method for preparing para-polyamide polymer is provided to realize a high reaction rate and high intrinsic viscosity of para-polyamide by effectively removing hydrochloric acid while not adversely affecting the reactivity of para-phenylene diamine and terephthaloyl chloride. A method for preparing para-polyamide polymer comprises the steps of: mixing calcium chloride with N-methyl-2-pyrrolidone solvent to provide a polymerization solvent; dissolving a tertiary amine into the polymerization solvent to form a solution; dissolving paraphenylene diamine(PPD) into the polymerization solvent to form a solution, followed by cooling; and adding terephthaloyl chloride(TPC) to the solution in two portions, wherein terephthaloyl chloride is added in two portions at a weight ratio of 35:65.

Description

빠른 반응 속도로 높은 고유 점도의 파라 폴리 아미드 중합물을 제조하는 방법{Preparation method of para-polyamid having high inherent viscosity and fast reaction time}Preparation method of para-polyamid having high inherent viscosity and fast reaction time

본 발명은 방향족 폴리아미드 섬유의 원료로 사용되는 파라-폴리아미드 중합체의 제조방법에 관한 것이다. 구체적으로는 N-메틸-2-피롤리돈(N-methyl-2-pyrrolidone: 이하 “NMP”라 한다)에 염화칼슘(CaCl2) 및 3급 아민류를 용해시키고, 여기에 방향족 디아민과 방향족 디카르복실산 할라이드를 용해하여 중합시켜 짧은 반응 시간 내에 고유 점도 7.0 이상의 파라-폴리아미드 중합체를 제조하는 방법에 관한 것이다.The present invention relates to a process for the preparation of para-polyamide polymers used as raw materials for aromatic polyamide fibers. Specifically, calcium chloride (CaCl 2 ) and tertiary amines are dissolved in N-methyl-2-pyrrolidone (hereinafter referred to as “NMP”), and aromatic diamine and aromatic dicar are dissolved therein. A method of dissolving and polymerizing an acid halide to produce a para-polyamide polymer having an intrinsic viscosity of at least 7.0 in a short reaction time.

본 발명에 따르면, NMP/CaCl2의 혼합 용매에 3급 아민류를 용해시킨 후 파라페닐렌디아민(p-phenylene diamine, PPD)를 용해시켜 프리믹스(Premix)를 제조하고 테레프탈로일 클로라이드(terephthaloyl chloride, TPC)를 2차에 걸쳐 투입하여 폴리(파라-페닐렌 테레프탈아미드)(poly(p-phenylene terephthalamide), PPTA)를 제조한다. 이때 3급 아민류의 치환기에 따라 반응 시간은 단축되고 생성되는 중합체 의 고유 점도는 상승하게 된다. 반응 시간과 중합체의 고유 점도를 고려할 때 아민기의 주위에 입체적으로 큰 치환기를 가지는 것이 유리하다.According to the present invention, after dissolving tertiary amines in a mixed solvent of NMP / CaCl 2 , paraphenylenediamine (p-phenylene diamine, PPD) is dissolved to prepare a premix, and terephthaloyl chloride (terephthaloyl chloride, TPC) was added in two steps to prepare poly (para-phenylene terephthalamide) (poly (p-phenylene terephthalamide), PPTA). At this time, the reaction time is shortened according to the substituents of the tertiary amines and the inherent viscosity of the resulting polymer is increased. Considering the reaction time and the intrinsic viscosity of the polymer, it is advantageous to have three-dimensionally large substituents around the amine group.

고강도의 파라형 폴리아미드 섬유를 제조하기 위해서는 고유 점도 6.0이상의 고분자량의 중합물이 필수사항이다. 본 발명은 입체적으로 큰 치환기를 가지는 아민류를 첨가함으로써 반응시간 및 중합체의 고유 점도를 높이는 중합법을 제시하고 있다.In order to produce high strength para-type polyamide fibers, high molecular weight polymers having an intrinsic viscosity of 6.0 or higher are essential. The present invention proposes a polymerization method of increasing the reaction time and the intrinsic viscosity of a polymer by adding amines having three-dimensionally large substituents.

지금까지 파라형 방향족 디아민 및 파라형 방향족 디카르복실산 할라이드의 축중합체인 파라형 폴리 아미드류(이하, “파라형 폴리아미드류”라 한다)는 고강도, 고탄성율 및 고내열성을 지니고, -160℃에서도 섬유의 특성을 지니는 내한성을 가지고 있을 뿐만 아니라, 절연성, 내약품성 등이 모두 우수한 첨단의 소재인 것이 공지되어 있다.Until now, para-type polyamides (hereinafter referred to as “para-type polyamides”), which are condensers of para-type aromatic diamines and para-type aromatic dicarboxylic acid halides, have high strength, high modulus, and high heat resistance, -160 It is known that it is a high-tech material which not only has cold resistance which has the characteristic of a fiber at degrees C, but also excellent both insulation and chemical-resistance.

대표적인 파라형 폴리아미드 화합물로서는 폴리(파라-페닐렌 테레프탈아미드)(poly(p-phenylene terephthalamide): 이하 "PPTA"라 한다.)를 들 수 있다. 일반적으로, PPTA는 아미드계 용매 내에서 테레프탈로일 클로라이드(terephthaloyl chloride: TPC)와 파라페닐렌디아민(p-phenylene diamine: PPD)의 용액축합중합반응에 의하여 중합된다.Representative para-type polyamide compounds include poly (para-phenylene terephthalamide) (poly (p-phenylene terephthalamide): hereinafter referred to as "PPTA"). Generally, PPTA is polymerized by solution condensation polymerization of terephthaloyl chloride (TPC) and paraphenylenediamine (PPD) in an amide solvent.

[반응식][Scheme]

Figure 112006097524771-PAT00001
Figure 112006097524771-PAT00001

그런데, PPTA는 유기용매에 대한 용해도가 극히 낮기 때문에 고분자량의 중합체를 얻기 위해서는 용매의 선택, 단량체의 농도 등이 매우 중요하다. However, since PPTA has a very low solubility in organic solvents, solvent selection, monomer concentration, etc. are very important to obtain a high molecular weight polymer.

또한 이때 부산물로 생성되는 염산을 효과적으로 제거하는 것이 반응 속도 및 중합체의 고유 점도 상승에 영향을 주는데, 염산을 제거하기 위하여 아민류를 첨가하는 중합법이 알려져 있다. 이때 주로 사용되는 아민류는 피리딘과 같은 3급 아민류이다. 그러나 일반적인 3급 아민은 PPD와 같은 염기성을 가지고 PPD와 TPC의 반응에 저하시킨다는 문제점이 있다. In addition, the effective removal of hydrochloric acid generated as a by-product affects the reaction rate and the intrinsic viscosity of the polymer. A polymerization method of adding amines to remove hydrochloric acid is known. Mainly used amines are tertiary amines such as pyridine. However, the general tertiary amine has the same basicity as PPD and has a problem of lowering the reaction between PPD and TPC.

본 발명은 PPD와 TPC의 반응성을 저하시키지 않으면서 염산을 효과적으로 제거함으로써 반응속도 및 파라형 폴리아미드 중합체의 고유 점도를 높이는 제조방법을 제공하는 것을 목적으로 한다. It is an object of the present invention to provide a process for increasing reaction rate and intrinsic viscosity of para-type polyamide polymers by effectively removing hydrochloric acid without reducing the reactivity of PPD and TPC.

상기한 과제를 해결하기 위하여, 본 발명의 적절한 실시형태에 따르면, 파라 폴리아미드 중합체의 제조방법은 N-메틸-2-피롤리돈(NMP) 용매에 대하여 염화칼슘을 첨가하여 중합용매를 만드는 단계; 상기 중합용매에 3급 아민류를 용해시켜 용액을 제조하는 단계; 상기 중합용매에 파라페닐렌 디아민(PPD)을 용해시켜서 용액을 제조한 후 냉각하는 단계; 및 상기 용액에 테레프탈로일 클로라이드(TPC)를 두 번으로 나누어 첨가하는 단계를 포함하고, 상기 테레프탈로일 클로라이드는 35:65 의 중량비로 순차적으로 첨가될 수 있다. In order to solve the above problems, according to a preferred embodiment of the present invention, a method for preparing a para polyamide polymer is prepared by adding calcium chloride to an N-methyl-2-pyrrolidone (NMP) solvent to form a polymerization solvent; Preparing a solution by dissolving tertiary amines in the polymerization solvent; Dissolving paraphenylene diamine (PPD) in the polymerization solvent to prepare a solution and then cooling it; And adding terephthaloyl chloride (TPC) in two portions to the solution, and the terephthaloyl chloride may be sequentially added in a weight ratio of 35:65.

본 발명의 다른 적절한 실시 형태에 따르면, 상기 3급 아민류는 2,6-부티딘 또는 2,6-디-터트-부틸피리딘인 것을 특징으로 한다.According to another suitable embodiment of the present invention, the tertiary amines are characterized in that 2,6-butydine or 2,6-di-tert-butylpyridine.

본 발명의 또 다른 적절한 실시 형태에 따르면, 상기의 방법으로 제조되고, 고유 점도가 7.0 이상인 파라 폴리아미드 중합체로부터 제조된 폴리아미드 섬유를 제공한다.According to another suitable embodiment of the present invention, there is provided a polyamide fiber prepared by the above method and made from a para polyamide polymer having an intrinsic viscosity of at least 7.0.

이하, 본 발명을 보다 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in more detail.

본 발명에 따르면, 폴리아미드 중합체의 용해도를 높이기 위하여 N-메틸-2-피롤리돈(NMP)에 염화칼슘을 첨가하여 중합용매를 만들고, 상기 중합용매에 1～2중량%의 3급 아민류를 용해시키고, 이후 상기 중합용매에 방향족 디아민 대비 방향족 디카르복실산 할라이드를 1.002～1.005의 몰비로 투입하여 중합시켜서 고유점도 등의 물성이 향상된 파라 폴리아미드 중합체를 제조할 수 있다. According to the present invention, in order to increase the solubility of the polyamide polymer, calcium chloride is added to N-methyl-2-pyrrolidone (NMP) to make a polymerization solvent, and 1 to 2 wt% of tertiary amines are dissolved in the polymerization solvent. After that, the polydiamine polymer having improved physical properties such as intrinsic viscosity can be prepared by adding and polymerizing an aromatic dicarboxylic acid halide to an aromatic diamine in a molar ratio of 1.002 to 1.005.

본 발명은 폴리아미드 중합체의 용해도를 높이기 위하여, 중합용매인 NMP와 염화칼슘의 혼합용매를 NMP에 대하여 8~9 중량%의 염화칼슘을 첨가하여 제조였다.In order to improve the solubility of the polyamide polymer, the present invention was prepared by adding 8 to 9% by weight of calcium chloride to NMP as a mixed solvent of NMP and calcium chloride as a polymerization solvent.

본 발명에서 사용할 수 있는 3급 아민류는 2,6-부티딘, 2,6-디-터트-부틸피리딘 등이 있다. 입체적으로 큰 치환기를 가지는 아민류는 염기성을 가지는 아민기가 입체적으로 장애를 받아 염산에 비해 상대적으로 큰 TPC에는 영향을 주지 않으면서 염산은 효과적으로 제거함으로써 반응속도 및 고유점도를 높일 수 있는 것으로 해석된다.Tertiary amines usable in the present invention include 2,6-butydine, 2,6-di-tert-butylpyridine and the like. The amines having three-dimensionally large substituents are interpreted to be able to increase the reaction rate and intrinsic viscosity by effectively removing the hydrochloric acid without affecting the relatively large TPC compared to hydrochloric acid because the amine group having a basic three-dimensional obstacle.

본 발명에서 사용할 수 있는 방향족 디아민은 파라페닐렌 디아민, 4,4'-디아미노비페닐, 2-메틸-파라페닐렌디아민, 2-클로로-파라페닐렌디아민, 2,6-나프탈렌디아민, 1,5-나프탈렌디아민, 4,4'-디아미노벤즈아닐리드 등을 사용할 수 있다. Aromatic diamines that can be used in the present invention are paraphenylene diamine, 4,4'-diaminobiphenyl, 2-methyl-paraphenylenediamine, 2-chloro-paraphenylenediamine, 2,6-naphthalenediamine, 1 , 5-naphthalenediamine, 4,4'-diaminobenzanilide, and the like can be used.

본 발명에서 사용할 수 있는 방향족 디카르복실산 할라이드는 테레프탈로일 클로라이드(TPC), 4,4'-벤조일 클로라이드, 2-클로로테레프탈로일 클로라이드, 2,5-디클로로테레프탈로일 클로라이드, 2-메틸테레프탈로일 클로라이드, 2,6-나프탈렌카르복실산 클로라이드, 1,5-나프탈렌디카르복실산 클로라이드 등을 들 수 있다.Aromatic dicarboxylic acid halides that can be used in the present invention include terephthaloyl chloride (TPC), 4,4'-benzoyl chloride, 2-chloroterephthaloyl chloride, 2,5-dichloroterephthaloyl chloride, 2-methyl Terephthaloyl chloride, 2,6-naphthalenecarboxylic acid chloride, 1,5-naphthalenedicarboxylic acid chloride, etc. are mentioned.

본 발명은 상기한 NMP와 염화칼슘의 혼합용매에 파라-페닐렌디아민을 첨가한 후, 테레프탈로일 클로라이드(TPC)를 투입하여 중합시켜서 파라-폴리아미드 중합용액을 얻는다. In the present invention, para-phenylenediamine is added to the mixed solvent of NMP and calcium chloride, and then terephthaloyl chloride (TPC) is added to polymerize to obtain a para-polyamide polymerization solution.

본 발명에서 테레프탈로일 클로라이드는 35:65의 비율로 두 번에 나누어 첨가한다. 중합은 0 내지 40℃ 의 온도에서 실시하는 것이 바람직하다. 이때 중합 반응기는 한국특허출원 제2005-52422호에서 정의된 형태를 사용하는 것이 바람직하다.In the present invention, terephthaloyl chloride is added in two portions at a ratio of 35:65. It is preferable to perform superposition | polymerization at the temperature of 0-40 degreeC. In this case, the polymerization reactor is preferably used in the form defined in Korean Patent Application No. 2005-52422.

이하에서 본 발명은 제한되지 않는 실시예에 의거하여 더욱 구체적으로 설명된다. The invention is explained in more detail below on the basis of non-limiting examples.

실시예 및 비교예에서 판단기준으로 사용된 고유점도(Inherent Viscosity)는 하기와 같이 정의된다. 즉, 각각의 용액은 96% 황산 100ml에 파라 폴리아미드 중합 체 0.5g을 용해시키거나 96% 황산 용액 자체로 제조되며, 유동시간은 모세관 점도계로 30℃에서 측정하였다. 고유 점도는 하기 수학식 1에 따라 유동시간비로 계산한다.Inherent Viscosity used as a criterion in Examples and Comparative Examples is defined as follows. That is, each solution was dissolved 0.5 g of a para polyamide polymer in 100 ml of 96% sulfuric acid or prepared as a 96% sulfuric acid solution itself, and the flow time was measured at 30 ° C. with a capillary viscometer. Intrinsic viscosity is calculated by the flow time ratio according to the following equation (1).

[수학식 1][Equation 1]

고유점도 = ln(T/T0)/CIntrinsic Viscosity = ln (T / T 0 ) / C

[상기 수학식 1에서 T는 파라 폴리아미드/황산 용액의 유동시간을 나타내고, T0는 황산 자체의 유동시간을 나타낸다. C는 파라 폴리아미드/황산 용액중의 파라 폴리아미드중합체의 농도이다.][In Formula 1, T represents a flow time of the para polyamide / sulfuric acid solution, and T 0 represents a flow time of sulfuric acid itself. C is the concentration of para polyamide polymer in para polyamide / sulfuric acid solution.]

실시예 1 Example 1

냉각 재킷(Cooling Jacket)이 장착된 중합 반응기에 8.2 중량%의 염화칼슘, 2 중량%의 2,6-디-터트-부틸피리딘이 함유된 250kg의 NMP/염화 칼슘 혼합용액를 넣는다. In a polymerization reactor equipped with a cooling jacket, 250 kg of NMP / calcium chloride mixed solution containing 8.2% by weight of calcium chloride and 2% by weight of 2,6-di-tert-butylpyridine is added.

상기 혼합용액에 15kg의 PPD를 교반하면서 첨가하였다. 만들어진 혼합물을 15℃까지 냉각시켰다. 이어서, 냉각과 강한 교반을 계속하면서 30g의 TPC를 35:65의 비율로 2번으로 나누어 빠르게 첨가하였다. 15 kg of PPD was added to the mixed solution with stirring. The resulting mixture was cooled to 15 ° C. Subsequently, 30 g of TPC was added in two portions at a ratio of 35:65 rapidly while continuing cooling and vigorous stirring.

교반을 10분간 계속하면서 반응을 완성시켰다. 이때 최종 온도는 55℃ 이상이 되지 않도록 냉각하였다. 중합체는 혼합용매에 대하여 11 중량% 함유되어 있는 것이다. 크럼을 분쇄하고 중화하여 여과, 세정 및 건조하여 고유점도가 7.3인 PPTA 를 얻었다.The reaction was completed while stirring was continued for 10 minutes. At this time, the final temperature was cooled so as not to be 55 ℃ or more. The polymer is contained 11 wt% with respect to the mixed solvent. The crumb was ground, neutralized, filtered, washed and dried to give PPTA having an intrinsic viscosity of 7.3.

실시예 2Example 2

2 중량%의 2,6-부티딘을 첨가한 것 이외에는 실시 예1과 동일하게 실시하였다. 그 결과, 반응시간은 20분이었고, 고유점도가 7.1인 PPTA를 얻었다. It carried out similarly to Example 1 except having added 2 weight% of 2, 6-butydine. As a result, the reaction time was 20 minutes, and PPTA having an intrinsic viscosity of 7.1 was obtained.

비교예 1Comparative Example 1

2 중량%의 피리딘을 첨가한 것 이외에는 실시 예1과 동일하게 하여 PPTA를 얻었다. 그 결과 반응시간은 30분이었고, 고유점도는 6.2이었다.PPTA was obtained like Example 1 except having added 2 weight% of pyridine. As a result, the reaction time was 30 minutes and the intrinsic viscosity was 6.2.

본 발명에 따른 파라형 폴리아미드 중합체는 고유점도가 7.0 이상으로, 중합체가 얻어지는 시간이 20분 이내로 입체적인 장애가 없는 아민류를 사용하는 경우보다 빠른 반응시간과 높은 고유점도를 가지는 중합체를 얻을 수 있다.The para-type polyamide polymer according to the present invention has an intrinsic viscosity of 7.0 or more, and a polymer having a faster reaction time and a higher intrinsic viscosity can be obtained than in the case of using amines having no steric hindrance within 20 minutes of obtaining the polymer.

Claims (3)

파라 폴리아미드 중합체의 제조방법에 있어서,In the method for producing a para polyamide polymer, N-메틸-2-피롤리돈(NMP) 용매에 대하여 염화칼슘을 혼합하여 중합용매를 제조하는 단계; Preparing a polymerization solvent by mixing calcium chloride with an N-methyl-2-pyrrolidone (NMP) solvent; 상기 중합용매에 3급 아민류를 용해시켜 용액을 제조하는 단계; Preparing a solution by dissolving tertiary amines in the polymerization solvent; 상기 중합용매에 파라페닐렌 디아민(PPD)을 용해시켜 용액을 제조한 후 냉각하는 단계; 및 Dissolving paraphenylene diamine (PPD) in the polymerization solvent to prepare a solution and then cooling it; And 상기 용액에 테레프탈로일 클로라이드(TPC)를 두 번으로 나누어 첨가하는 단계를 포함하고, Adding terephthaloyl chloride (TPC) in two portions to the solution; 상기에서 테레프탈로일 클로라이드는 중량비 35:65로 순차적으로 첨가되는 것을 특징으로 하는 파라 폴리아미드 중합체의 제조방법. Terephthaloyl chloride is a method for producing a para polyamide polymer, characterized in that sequentially added in a weight ratio of 35:65. 제 1항에 있어서, 상기 3급 아민류는 2,6-부티딘 또는 2,6-디-터트-부틸피리딘인 것을 특징으로 하는 파라 폴리아미드 중합체의 제조방법.The method according to claim 1, wherein the tertiary amines are 2,6-butydine or 2,6-di-tert-butylpyridine. 제 1항의 제조방법으로 제조되고, 고유점도가 7.0 이상인 파라 폴리아미드 중합체로부터 제조되는 폴리아미드 섬유.A polyamide fiber made from a para polyamide polymer prepared by the process according to claim 1 and having an intrinsic viscosity of at least 7.0.
KR1020060136174A 2006-12-28 2006-12-28 Preparation method of para-polyamid having high inherent viscosity and fast reaction time KR20080061176A (en)

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