KR20030033623A - Copolyamide Resin Composition Containing Monmorillonite - Google Patents
Copolyamide Resin Composition Containing Monmorillonite Download PDFInfo
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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Abstract
Description
본 발명은 적층된 실리케이트의 구조를 갖는 몬모릴로나이트를 포함한 폴리아미드 수지의 조성물에 관한 것으로, 더욱 상세하게는 폴리아미드를 형성할 수 있는 단량체들과 몬모릴로나이트의 혼합물로부터 공중합 폴리아미드 수지조성물에 관한 것이다.The present invention relates to a composition of a polyamide resin comprising montmorillonite having a structure of laminated silicates, and more particularly to a copolymerized polyamide resin composition from a mixture of monomers and montmorillonite capable of forming a polyamide.
기계적 강도, 내약품성, 기체차단성 등의 우수한 장점을 갖는 폴리아미드는 자동차 부품, 전자제품, 식품포장용의 재료로 많이 사용되는 대표적인 엔지니어링 플라스틱이다. 최근에 이러한 특성을 더욱 개선하고 내흡습성, 치수안정성, 난연성 등의 성질을 폴리아미드에 부여하고자 하는 방법들이 몬모릴로나이트를 사용하여 시도되고 있다. 몬모릴로나이트가 갖는 층상규산염의 구조는 약 300∼ 1,000배에 이르는 외관비(aspect ratio)를 보유하며 또한 두께 방향으로는 나노미터(nanometer)의 치수를 가짐으로 인하여 폴리아미드 수지내에서 균일한 분산을 이루는 경우에 커다란 물성의 향상을 이룰 수 있는 방법을 제공하고 있다.Polyamide, which has excellent advantages such as mechanical strength, chemical resistance, and gas barrier property, is a representative engineering plastic that is widely used as a material for automobile parts, electronic products, and food packaging. Recently, montmorillonite has been attempted to further improve these properties and to impart properties such as hygroscopicity, dimensional stability, and flame retardancy to polyamides. The layered silicate structure of montmorillonite has an aspect ratio of about 300 to 1,000 times and has a dimension of nanometer in the thickness direction, resulting in uniform dispersion in the polyamide resin. In this case, it provides a way to achieve great improvements in physical properties.
미합중국 특허 제5,248,720호에서는 몬모릴로나이트를 폴리아미드 수지내에 균일한 분산을 하기 위해 팽윤화제를 사용하여 몬모릴로나이트의 층간거리를 크게 하는 공정이 필요하며 또한 이렇게 제조된 폴리아미드 나노복합체는 기체투과도와 기계적 강도 등은 증가하나 투명성, 연신성이 떨어지는 단점이 있다.U.S. Patent No. 5,248,720 requires a process to increase the interlaminar distance of montmorillonite using a swelling agent in order to uniformly disperse montmorillonite in the polyamide resin. It has the disadvantage of increasing transparency and low stretchability.
이러한 문제점을 개선하기 위한 미합중국 특허 제5,741,601호에서는 팽윤성이 큰 플루오로마이카를 사용함으로 별도의 전처리가 없어도 플루오로마이카가 폴리아미드 수지내에 균일하게 분산되는 나노복합체를 제조하는 방법을 제공하고 있다. 하지만 위의 방법은 비교적 간단한 제조공정을 제공함에도 불구하고 제조된 나노복합체가 연신성과 투명성이 감소하는 특성을 나타내므로 필름으로 가공하는 공정에서 연신성을 증가시키기 위한 공정이 요구되고 있다.US Patent No. 5,741,601 to improve this problem provides a method for producing a nanocomposite in which fluoromica is uniformly dispersed in a polyamide resin without any additional pretreatment by using fluoro mica with high swellability. However, although the above method provides a relatively simple manufacturing process, the prepared nanocomposite exhibits a property of decreasing elongation and transparency, and thus a process for increasing elongation in a film processing process is required.
본 발명의 목적은 상기한 문제점을 극복하기 위한 것으로, 몬모릴로나이트가 포함된 공중합 폴리아미드 수지의 나노복합체를 단량체들과 몬모릴로나이트의 혼합물로부터 제조함으로 분산성이 우수하여 기체차단성, 투명성이 뛰어나고 특히 저온에서의 연신성이 우수한 공중합 폴리아미드의 수지 조성물에 관한 것이다.An object of the present invention is to overcome the above problems, by preparing a nanocomposite of montmorillonite-containing copolymer polyamide resin from a mixture of monomers and montmorillonite, excellent dispersibility, excellent gas barrier properties, transparency and especially at low temperatures It relates to a resin composition of copolymerized polyamide having excellent stretchability.
즉, 폴리아미드를 형성할 수 있는 단량체들을 몬모릴로나이트와 함께 공중합하여 균일한 분산성을 갖는 나노복합체를 제조하는 방법과 매트릭스를 형성하는 폴리아미드를 공중합하여 매트릭스 수지의 투명성과 연신성을 향상시키며 또한 이렇게 제조된 나노복합체가 뛰어난 기체차단성을 보이는 공중합 폴리아미드 수지 조성물을 얻고자 하는 것이다.That is, a method of preparing a nanocomposite having homogeneous dispersibility by copolymerizing monomers capable of forming polyamide with montmorillonite and copolymerizing polyamide forming a matrix to improve transparency and stretchability of the matrix resin It is to obtain a copolymerized polyamide resin composition in which the prepared nanocomposite exhibits excellent gas barrier properties.
본 발명의 폴리아미드 수지는, MXD-6 나일론을 구성하는m-크실렌디아민, 아디프산이 100∼70중량% 이며 기타 폴리아미드를 형성할 수 있는 단량체가 0∼30중량%로 이루어진 MXD-6 나일론 혹은 폴리아미드 공중합물 100중량부와 몬모릴로나이트 0.5∼10 중량부로 구성되며, 이렇게 제조된 폴리아미드 수지내에 몬모릴로나이트의 분산성이 우수하며 기체차단성, 투명성, 저온에서의 연신성이 뛰어나다.The polyamide resin of the present invention is m -xylenediamine constituting the MXD-6 nylon, MXD-6 nylon consisting of 100 to 70% by weight of adipic acid and other monomers capable of forming polyamide 0 to 30% by weight Or it is composed of 100 parts by weight of polyamide copolymer and 0.5 to 10 parts by weight of montmorillonite, and excellent dispersibility of montmorillonite in the polyamide resin thus prepared, and excellent gas barrier property, transparency, elongation at low temperature.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
공중합 폴리아미드에서 MXD-6 나일론을 구성하는m-크실렌디아민, 아디프산이 투입하는 원료의 기준으로 100∼70중량% 이며 이때에 사용되는 두 원료는 각기 1:1 당량을 사용하게 된다. 기타 폴리아미드를 형성할 수 있는 단량체로는 ε-카프로락탐, 테트라메틸렌디아민, 헥사메틸렌디아민, 테레프탈산, 이소프탈산, 12-아미노도데카노산 등이 있으며 위의 성분이 공중합 폴리아미드 수지 중에서 0∼30중량%를 차지하며, 폴리아미드 공중합물 100중량부에 대하여 0.5∼10중량부의 몬모릴로나이트로 구성된다.In the copolyamide, m -xylenediamine and adipic acid, which constitute MXD-6 nylon, are 100 to 70% by weight based on the raw materials introduced. The two raw materials used are 1: 1 equivalents. Other monomers capable of forming polyamides include ε-caprolactam, tetramethylenediamine, hexamethylenediamine, terephthalic acid, isophthalic acid and 12-aminododecanoic acid. It comprises by weight and consists of 0.5 to 10 parts by weight of montmorillonite with respect to 100 parts by weight of polyamide copolymer.
기존의 몬모릴로나이트를 포함하는 폴리아미드의 나노복합체는 매트릭스 수지로 나일론6을 사용하여 기계적 성질의 강화, 내열성의 증강, 기체차단성의 증가 등의 물성의 향상을 이루었다. 그러나 나일론6의 나노복합체는 몬모릴로나이트가수지의 결정화를 촉진하는 핵제(Nucleating agent)로의 역할을 함에 따라 결정화 속도가 증가하는 특성을 보이게 된다.Conventional montmorillonite-containing polyamide nanocomposites have improved the physical properties of nylon 6 as a matrix resin by enhancing mechanical properties, enhancing heat resistance, and increasing gas barrier properties. However, the nanocomposite of nylon 6 has a characteristic of increasing the crystallization rate as it serves as a nucleating agent to promote the crystallization of montmorillonite resin.
사출가공시에는 결정화 속도의 증가가 작업성의 향상과 치수의 안정성 등에 주요하게 작용하지만 압출 연신의 공정에서는 투명성의 감소와 연신응력의 증가와 같은 문제가 일어나는 요인이 된다. 미합중국 특허 제5,741,601호에서도 플루오로마이카를 사용한 나노복합체는 필름으로 연신하는 과정에서 원단에 물을 함습시켜 연신성을 향상시키거나 혹은 연신을 한 축에 대해 진행하고 후에 다른 축에 대해 진행하는 방법으로 필름가공을 수행하고 있다. 하지만 이렇게 제조된 필름은 투명성이 감소하여 Haze가 증가하는 단점이 있게 된다.In the injection processing, the increase of the crystallization speed mainly plays a role in improving workability and dimensional stability, but in the extrusion stretching process, problems such as a decrease in transparency and an increase in stretching stress are caused. In US Pat. No. 5,741,601, nanocomposites using fluoromicas may be prepared by impregnating water in a fabric in the process of stretching to a film to improve stretchability or to perform stretching on one axis and later on another axis. Film processing is performed. However, the film thus produced has a disadvantage in that the transparency decreases and the Haze increases.
이러한 가공상의 문제를 해결하기 위해 본 발명에서는 나노복합체를 구성하는 매트릭스 수지를 공중합 폴리아미드로 변형하고자 하였다. 공중합 폴리아미드를 구성하는 단량체인m-크실렌디아민은 페닐렌 구조를 포함하고 있고 또한 페닐렌 구조의 치환 위치가 메타 위치에 있는 특징을 갖고 있다. 이러한 구조에 의해서m-크실렌디아민이 아디프산과의 반응으로 형성하는 MXD-6 나일론은 강직한 성질과 결정화 속도가 느려지는 특징을 가져 성형시 투명하며 연신성이 뛰어난 성질이 있다. 이러한 가공상의 장점이외에도 MXD-6 나일론은 산소, 습도 등에 가스에 대한 차단성이 우수하여 포장용 필름의 용도로 많이 사용되고 있다.In order to solve this processing problem, the present invention intends to transform the matrix resin constituting the nanocomposite into copolymer polyamide. The m -xylenediamine which is a monomer which comprises a copolymer polyamide contains the phenylene structure, and has the characteristic that the substitution position of a phenylene structure is in a meta position. Due to this structure, MXD-6 nylon, which m -xylenediamine is formed by the reaction with adipic acid, has a rigid property and a slow crystallization rate, and thus has transparency and excellent stretchability in molding. In addition to these processing advantages, MXD-6 nylon is used for packaging films because of its excellent barrier property against oxygen and humidity.
공중합 폴리아미드 수지 중 MXD-6 나일론을 형성하는m-크실렌디아민, 아디프산의 혼합물의 양이 전체 폴리아미드를 형성하는 원료 중 70중량% 보다 작으면 MXD-6 나일론의 특성이 작아지며 또한 공중합 폴리아미드의 고화속도가 느려져서중합 혹은 가공시에 작업성이 나빠지고 결정화도가 너무 작아져 오히려 기체차단성 등 원하는 성질을 얻기 어렵다.When the amount of the mixture of m -xylenediamine and adipic acid forming MXD-6 nylon in the copolymerized polyamide resin is less than 70% by weight of the raw material forming the total polyamide, the properties of the MXD-6 nylon are reduced and copolymerization is performed. Due to the low solidification rate of polyamide, the workability is poor during polymerization or processing, and the degree of crystallinity is too small to obtain desired properties such as gas barrier properties.
본 발명에서 사용되는 몬모릴로나이트는 외관비(길이/직경의 비율)가 300배 이상으로 매우 크며 또한 폴리아미드 수지와의 결합력이 강하므로 본 발명이 바라는 효과를 얻기에 유리하며 몬모릴로나이트가 폴리아미드 중합물 100중량부에 대하여 0.5∼10중량부의 양으로 사용된다. 0.5중량부 미만인 경우에는 본 발명이 바라는 효과를 얻기 어려우며 10중량부를 초과하는 경우에는 큰 값의 외관비를 갖는 몬모릴로나이트에 의해 중합물의 용융점도가 상승하므로 중합 및 가공시 어려움이 있다.The montmorillonite used in the present invention has an appearance ratio (length / diameter ratio) of more than 300 times and is very large, and also has a strong binding force with the polyamide resin, and thus it is advantageous to obtain the desired effect of the present invention. It is used in the quantity of 0.5-10 weight part with respect to a part. If it is less than 0.5 parts by weight it is difficult to obtain the desired effect of the present invention, if it exceeds 10 parts by weight montmorillonite having a large value of the appearance ratio increases the melt viscosity of the polymer there is a difficulty in polymerization and processing.
본 발명에서 사용되는 몬모릴로나이트는 층간거리가 10Å인 판상이 적층되어 있는 구조이거나 판간의 거리를 확대하여 그 팽윤성을 감소시켜 처리된 몬모릴로나이트이다. 판간의 거리를 확대하기 위해 사용된 처리제로는 ε-카프로락탐, 12-아미노도데카노산, 옥타데실아민, 탈로우의 암모늄이온 등이 사용될 수 있다.The montmorillonite used in the present invention is a structure in which platelets having an interlaminar distance of 10 Å are laminated or montmorillonite treated by expanding the distance between the plates to reduce its swelling property. As a treatment agent used to increase the distance between the plates, ε-caprolactam, 12-aminododecanoic acid, octadecylamine, tallow ammonium ion, and the like may be used.
본 발명에서 사용되는 폴리아미드 수지의 상대점도는 1.5∼3.5의 범위가 바람직하다. 상대점도가 1.5 미만의 경우에는 수지 조성물의 기계적 물성이 저하하여 원하는 특성을 얻기 어려우며 3.5을 초과하는 경우에는 수지 조성물의 가공성이 떨어지는 단점이 있다.The relative viscosity of the polyamide resin used in the present invention is preferably in the range of 1.5 to 3.5. If the relative viscosity is less than 1.5, the mechanical properties of the resin composition are lowered, so that it is difficult to obtain desired properties. If the relative viscosity is more than 3.5, the processability of the resin composition is poor.
이하에서 본 발명을 실시예를 들어 상세히 설명하지만, 본 발명의 구체적인 실시예를 설명하기 위한 것으로 본 발명이 실시예로 제한되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples. However, the present invention is not limited to the Examples.
(실시예 1)(Example 1)
40L 반응기에 ε-카프로락탐 1.0kg과m-크실렌디아민, 아디프산을 각기 4.34kg, 4.66kg을 투입한 뒤 몬모릴로나이트(Southern Clay Products사 Cloisite 15A, 125meq/100g) 300g과 물 2.0kg을 첨가하여 혼합물을 교반하며 온도를 250℃로 상승시켜 14kg/cm2으로 유지하고 1시간 동안 반응시켰다. 이어서 반응기내의 압력을 1시간 동안 서서히 제거하여 상압을 만든 뒤 -0.3kg/cm2의 압력으로 30분 동안 감압하여 중합을 완결시켰다. 중합이 완료된 뒤 5kg/cm2의 가압에 의해 중합물을 배출하여 이를 칩으로 제조하였고 95℃에서 12시간 물로 세척하여 미반응물을 제거한 뒤 100℃에서 진공건조를 하였다.Into a 40L reactor, 1.0 kg of ε-caprolactam, 4.34 kg and 4.66 kg of m -xylenediamine and adipic acid were added, and 300 g of montmorillonite (Closis 15A of Southern Clay Products, 125 meq / 100 g) and 2.0 kg of water were added. The mixture was stirred and the temperature was raised to 250 ° C. to maintain 14 kg / cm 2 and reacted for 1 hour. Subsequently, the pressure in the reactor was gradually removed for 1 hour to create an atmospheric pressure, and the polymerization was completed by reducing the pressure at -0.3 kg / cm 2 for 30 minutes. After the polymerization was completed, the polymer was discharged by pressurization of 5 kg / cm 2 to prepare a chip, which was washed with water at 95 ° C. for 12 hours to remove unreacted material, and then vacuum dried at 100 ° C.
건조된 칩의 열분석을 시차열분석기(DSC)를 이용하여 분석하였고 250℃의 온도에서 용융압출기을 이용하여 압출하여 150㎛의 시트를 제조하였다. 이때 냉각롤의 온도는 30℃로 유지하였으며 제조된 시트를 80℃에서 30초간 예열한 뒤 이축으로 동시에 연신하여 연신성과 투명성을 평가하였으며 그 결과를 <표 1>에 나타내었다.Thermal analysis of the dried chip was analyzed using a differential thermal analyzer (DSC) and extruded using a melt extruder at a temperature of 250 ℃ to prepare a sheet of 150㎛. At this time, the temperature of the cooling roll was maintained at 30 ℃ and the sheet was preheated at 80 ℃ for 30 seconds and then simultaneously stretched biaxially to evaluate the elongation and transparency and the results are shown in <Table 1>.
(비교예 1)(Comparative Example 1)
40L 반응기에 ε-카프로락탐 1.0kg과m-크실렌디아민, 아디프산을 각기 4.34kg, 4.66kg을 투입한 뒤 물 2.0kg을 첨가하여 몬모릴로나이트를 넣지 않고 혼합물을 교반하며 온도를 250℃로 상승시켜 14kg/cm2으로 유지하고 1시간 동안 반응시켰다. 이어서 반응기내의 압력을 1시간 동안 서서히 제거하여 상압을 만든 뒤 -0.3kg/cm2의 압력으로 30분 동안 감압하여 중합을 완결시켰다. 중합이 완료된 뒤 5kg/cm2의 가압에 의해 중합물을 배출하여 이를 칩으로 제조하였고 95℃에서 12시간 물로 세척하여 미반응물을 제거한 뒤 100℃에서 진공건조를 하였다.Into a 40L reactor, 1.0 kg of ε-caprolactam, 4.34 kg and 4.66 kg of m -xylenediamine and adipic acid were added, and 2.0 kg of water was added. The mixture was stirred without adding montmorillonite and the temperature was raised to 250 ° C. Maintained at 14kg / cm 2 and reacted for 1 hour. Subsequently, the pressure in the reactor was gradually removed for 1 hour to create an atmospheric pressure, and the polymerization was completed by reducing the pressure at -0.3 kg / cm 2 for 30 minutes. After the polymerization was completed, the polymer was discharged by pressurization of 5 kg / cm 2 to prepare a chip, which was washed with water at 95 ° C. for 12 hours to remove unreacted material, and then vacuum dried at 100 ° C.
건조된 칩을 실시예 1과 같은 방법으로 시트를 제조한 후 연신하여 연신성과 투명성을 평가하여 그 결과를 <표 1>에 나타내었다.The dried chip was prepared in the same manner as in Example 1, and then stretched to evaluate elongation and transparency, and the results are shown in Table 1.
(실시예 2)(Example 2)
40L 반응기에 AH-salts(Hexamethylenediamine adipate) 1.0kg과m-크실렌디아민, 아디프산을 각기 4.34kg, 4.66kg을 투입한 뒤 몬모릴로나이트(Southern Clay Products사 Cloisite 15A, 125meq/100g) 300g과 물 2.0kg을 첨가하여 혼합물을 교반하며 온도를 250℃로 상승시켜 14kg/cm2으로 유지하고 1시간 동안 반응시켰다. 이어서 반응기내의 압력을 1시간 동안 서서히 제거하여 상압을 만든 뒤 -0.3kg/cm2의 압력으로 30분 동안 감압하여 중합을 완결시켰다. 중합이 완료된 뒤 5kg/cm2의 가압에 의해 중합물을 배출하여 이를 칩으로 제조하였고 이를 100℃에서 진공건조를 하였다.Into a 40L reactor, 1.0 kg of AH-salts (Hexamethylenediamine adipate), 4.34 kg and 4.66 kg of m -xylenediamine and adipic acid were added respectively, followed by 300 g of montmorillonite (Closis 15A, 125 meq / 100 g) from Southern Clay Products and 2.0 kg of water. The mixture was stirred to increase the temperature to 250 ° C., maintained at 14 kg / cm 2 , and reacted for 1 hour. Subsequently, the pressure in the reactor was gradually removed for 1 hour to create an atmospheric pressure, and the polymerization was completed by reducing the pressure at -0.3 kg / cm 2 for 30 minutes. After the polymerization was completed, the polymer was discharged by pressurization of 5 kg / cm 2 , and the polymer was manufactured into chips, which were vacuum dried at 100 ° C.
건조된 칩을 실시예 1과 같은 방법으로 시트를 제조한 후 연신하여 연신성과 투명성을 평가하여 그 결과를 <표 1>에 나타내었다The dried chip was prepared in the same manner as in Example 1, and then stretched to evaluate elongation and transparency, and the results are shown in Table 1.
(실시예 3)(Example 3)
몬모릴로나이트(구네미네사 구니피아-F, 119meq/100g) 300g과 ε-카프로락탐 1.0kg을 처리조에 투입하고 85% 인산 41.16g을 물 1.0kg에 희석하여 첨가한 뒤 교반을 하면서 온도를 상승시켜 90℃에 도달하게 하였다. 교반기의 속도는 150rpm으로 하여 3시간 이상 교반하여 몬모릴로나이트가 물과 ε-카프로락탐의 분산매에 균일하게 분산되도록 하였다. 40L 반응기에m-크실렌디아민, 아디프산을 각기 4.34kg, 4.66kg을 투입한 뒤 물을 1kg 첨가한 뒤 반응기의 온도가 90℃에 이르도록 가열한 뒤 미리 제조된 처리조의 혼합물을 질소의 가압에 의해 이송하였다.300 g of montmorillonite (Geunminesa Gunipia-F, 119 meq / 100 g) and 1.0 kg of ε-caprolactam were added to the treatment tank, and 41.16 g of 85% phosphoric acid was added to 1.0 kg of water, and then the temperature was increased while stirring. It was allowed to reach ℃. The speed of the stirrer was stirred at 150 rpm for at least 3 hours so that montmorillonite was uniformly dispersed in the dispersion medium of water and ε-caprolactam. 4.34kg and 4.66kg of m -xylenediamine and adipic acid were added to the 40L reactor, 1kg of water was added, and the reactor was heated to 90 ° C. Transported by.
이송이 완료된 후 반응기의 혼합물을 교반하며 온도를 250℃로 상승시켜 14kg/cm2으로 유지하고 1시간 동안 반응시켰다. 이어서 반응기내의 압력을 1시간 동안 서서히 제거하여 상압을 만든 뒤 -0.3kg/cm2의 압력으로 30분 동안 감압하여 중합을 완결시켰다. 중합이 완료된 뒤 5kg/cm2의 가압에 의해 중합물을 배출하여 이를 칩으로 제조하였고 95℃에서 12시간 물로 세척하여 미반응물을 제거한 뒤 100℃에서 진공건조를 하였다.After the transfer was completed, the mixture of the reactor was stirred and the temperature was raised to 250 ° C. to maintain 14 kg / cm 2 and reacted for 1 hour. Subsequently, the pressure in the reactor was gradually removed for 1 hour to create an atmospheric pressure, and the polymerization was completed by reducing the pressure at -0.3 kg / cm 2 for 30 minutes. After the polymerization was completed, the polymer was discharged by pressurization of 5 kg / cm 2 to prepare a chip, which was washed with water at 95 ° C. for 12 hours to remove unreacted material, and then vacuum dried at 100 ° C.
건조된 칩을 실시예 1과 같은 방법으로 시트를 제조한 후 연신하여 연신성과 투명성을 평가하여 그 결과를 <표 1>에 나타내었다The dried chip was prepared in the same manner as in Example 1, and then stretched to evaluate elongation and transparency, and the results are shown in Table 1.
(비교예 2)(Comparative Example 2)
몬모릴로나이트(구네미네사 구니피아-F, 119meq/100g) 300g과 ε-카프로락탐 1,500g을 처리조에 투입하고 85% 인산 41.16g을 물 500g에 희석하여 첨가한 뒤 교반을 하면서 온도를 상승시켜 90℃에 도달하게 하였다. 교반기의 속도는 150rpm으로 하여 3시간 이상 교반하여 몬모릴로나이트가 물과 ε-카프로락탐의 분산매에 균일하게 분산되도록 하였다. 40L 반응기에 ε-카프로락탐 8.5kg과 물을 2kg 첨가한 뒤 반응기의 온도가 90℃에 이르도록 가열한 뒤 미리 제조된 처리조의 혼합물을 질소의 가압에 의해 이송하였다.300 g of montmorillonite (Gumine M. Gunipia-F, 119 meq / 100 g) and 1,500 g of ε-caprolactam were added to a treatment tank, and 41.16 g of 85% phosphoric acid was added to 500 g of water, and then the temperature was raised while stirring to increase the temperature. To reach. The speed of the stirrer was stirred at 150 rpm for at least 3 hours so that montmorillonite was uniformly dispersed in the dispersion medium of water and ε-caprolactam. After adding 8.5 kg of ε-caprolactam and 2 kg of water to the 40L reactor, the reactor was heated to reach a temperature of 90 ° C., and the mixture of the previously prepared treatment tank was transferred by pressurization of nitrogen.
이송이 완료된 후 반응기의 혼합물을 교반하며 온도를 250℃로 상승시켜 14kg/cm2으로 유지하고 1시간 동안 반응시켰다. 이어서 반응기내의 압력을 1시간 동안 서서히 제거하여 상압을 만든 뒤 -0.3kg/cm2의 압력으로 30분 동안 감압하여 중합을 완결시켰다. 중합이 완료된 뒤 5kg/cm2의 가압에 의해 중합물을 배출하여 이를 칩으로 제조하였고 95℃에서 12시간 물로 세척하여 미반응물을 제거한 뒤 100℃에서 진공건조를 하였다.After the transfer was completed, the mixture of the reactor was stirred and the temperature was raised to 250 ° C. to maintain 14 kg / cm 2 and reacted for 1 hour. Subsequently, the pressure in the reactor was gradually removed for 1 hour to create an atmospheric pressure, and the polymerization was completed by reducing the pressure at -0.3 kg / cm 2 for 30 minutes. After the polymerization was completed, the polymer was discharged by pressurization of 5 kg / cm 2 to prepare a chip, which was washed with water at 95 ° C. for 12 hours to remove unreacted material, and then vacuum dried at 100 ° C.
건조된 칩을 실시예 1과 같은 방법으로 시트를 제조한 후 연신하여 연신성과 투명성을 평가하여 그 결과를 <표 1>에 나타내었다The dried chip was prepared in the same manner as in Example 1, and then stretched to evaluate elongation and transparency, and the results are shown in Table 1.
(비교예 3)(Comparative Example 3)
40L 반응기에 ε-카프로락탐 4.0kg과m-크실렌디아민, 아디프산을 각기 2.9kg, 3.1kg을 투입한 뒤 몬모릴로나이트(Southern Clay Products사 Cloisite 15A, 125meq/100g) 300g과 물 2.0kg을 첨가하여 혼합물을 교반하며 온도를 250℃로 상승시켜 14kg/cm2으로 유지하고 1시간 동안 반응시켰다. 이어서 반응기내의 압력을 1시간 동안 서서히 제거하여 상압을 만든 뒤 -0.3kg/cm2의 압력으로 30분 동안 감압하여 중합을 완결시켰다. 중합이 완료된 뒤 5kg/cm2의 가압에 의해 중합물을 배출하여 이를 칩으로 제조하였고 95℃에서 12시간 물로 세척하여 미반응물을 제거한 뒤 100℃에서 진공건조를 하였다.Into a 40L reactor, 4.0 kg of ε-caprolactam, 2.9 kg and 3.1 kg of m -xylenediamine and adipic acid were added, and 300 g of montmorillonite (Closis 15A, 125meq / 100g, Southern Clay Products) and 2.0 kg of water were added. The mixture was stirred and the temperature was raised to 250 ° C. to maintain 14 kg / cm 2 and reacted for 1 hour. Subsequently, the pressure in the reactor was gradually removed for 1 hour to create an atmospheric pressure, and the polymerization was completed by reducing the pressure at -0.3 kg / cm 2 for 30 minutes. After the polymerization was completed, the polymer was discharged by pressurization of 5 kg / cm 2 to prepare a chip, which was washed with water at 95 ° C. for 12 hours to remove unreacted material, and then vacuum dried at 100 ° C.
건조된 칩을 실시예 1과 같은 방법으로 시트를 제조한 후 연신하여 연신성과 투명성을 평가하여 그 결과를 <표 1>에 나타내었다The dried chip was prepared in the same manner as in Example 1, and then stretched to evaluate elongation and transparency, and the results are shown in Table 1.
몬모릴로나이트가 포함된 공중합 폴리아미드 수지의 나노복합체를 단량체들과 몬모릴로나이트의 혼합물로부터 제조함으로써 분산성이 우수하여 기체차단성, 투명성이 뛰어나고 특히 저온에서의 연신성이 우수한 공중합 폴리아미드의 수지 조성물을 얻을 수 있게 되었다.By preparing nanocomposites of montmorillonite-containing copolymer polyamide resins from a mixture of monomers and montmorillonite, it is possible to obtain a resin composition of copolymer polyamide having excellent dispersibility and excellent gas barrier properties, transparency, and particularly excellent elongation at low temperatures. It became.
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