KR20010057495A - Polyamide Resin Composition and Manufacturing Method Thereof - Google Patents
Polyamide Resin Composition and Manufacturing Method Thereof Download PDFInfo
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- KR20010057495A KR20010057495A KR1019990060938A KR19990060938A KR20010057495A KR 20010057495 A KR20010057495 A KR 20010057495A KR 1019990060938 A KR1019990060938 A KR 1019990060938A KR 19990060938 A KR19990060938 A KR 19990060938A KR 20010057495 A KR20010057495 A KR 20010057495A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
Abstract
Description
본 발명은 적층된 실리케이트가 포함된 폴리아미드 수지를 제조하는데 사용되는 폴리아미드 수지 조성물 및 그 제조방법에 관한 것으로, 더욱 상세하게는 폴리아미드를 형성할 수 있는 단량체들과 적층된 실리케이트의 혼합물로부터 폴리아미드를 형성시켜 기계적 특성, 내열성, 연신성 및 기체차단성을 향상시키며 동시에 결정화속도를 향상시킨 폴리아미드 수지 제조용 폴리아미드 수지 조성물 및 그 제조방법에 관한 것이다.The present invention relates to a polyamide resin composition and a method for producing the polyamide resin comprising a laminated silicate, and more particularly, to a polyamide resin mixture from a mixture of laminated silicates and monomers capable of forming a polyamide. The present invention relates to a polyamide resin composition for producing a polyamide resin and a method for producing the same, wherein the amide is formed to improve mechanical properties, heat resistance, stretchability, and gas barrier properties, and at the same time improve crystallization rate.
폴리아미드 수지는 우수한 기계적 강도, 내약품성 등이 우수하지만 수분의 양에 따라 물성의 변화가 크며 비교적 열변형온도가 낮아 고온에서 사용이 제한되는 단점이 있으므로 이를 개선하기 위하여 적층된 실리케이트를 폴리아미드의 수지 내에 첨가하여 우수한 기계적 강도, 내약품성 등의 장점이 유지되도록 하고 흡습성, 치수안정성, 난연성, 기체차단성, 열변형온도가 개선된 수지를 제조하려는 방법들이 제안되고 있다.Polyamide resin has excellent mechanical strength, chemical resistance, etc., but the physical properties are largely changed according to the amount of moisture, and the heat resistance is relatively low. In order to maintain the advantages of excellent mechanical strength, chemical resistance and the like by adding in the resin, there are proposed methods for preparing a resin having improved hygroscopicity, dimensional stability, flame retardancy, gas barrier property, and heat deformation temperature.
미합중국 특허 5,102,948에 의하면 적층된 실리케이트의 일종인 몬모릴로나이트를 전처리하여 실리케이트의 층간거리를 확대한 뒤 폴리아미드 수지와 혼합시켜서 복합체를 얻는 방법을 제안하고 있으나, 이 방법은 몬모릴로나이트를 폴리아미드 수지 내에 미세하게 분산시키기 어려우며 또한 몬모릴로나이트를 전처리하는 단계와 전처리후에 ε-카프로락탐, 물과의 혼합, 그리고 압출기를 이용하여 처리된 몬모릴로나이트를 폴리아미드 수지와 혼합하는 공정으로 이루어지므로 제조공정의 단계가 복잡해지는 문제점이 있다.According to US Pat. No. 5,102,948, a method of pretreatment of montmorillonite, a kind of laminated silicates, to increase the interlayer distance of silicates and mixing with polyamide resins to obtain a composite is obtained, but this method finely disperses montmorillonite in polyamide resin. In addition, it is difficult to make the montmorillonite, and after the pretreatment, ε-caprolactam, mixing with water, and mixing the treated montmorillonite with the polyamide resin using an extruder, there is a problem of complicated manufacturing steps .
또 미합중국 특허 5,248,720는 적층된 실리케이트를 폴리아미드의 단량체와 혼합하여 중합하는 과정을 거쳐 복합체를 제조하는 방법으로서 이 방법은 적층된 실리케이트의 일종인 몬모릴로나이트를 전처리하거나 전처리하지 않은 몬모릴로나이트를 과량의 물에 분산시킨 뒤 ε-카프로락탐을 분산액에 첨가하여 중합하는 방법이다.In addition, US Pat. No. 5,248,720 is a method of preparing a composite by mixing a laminated silicate with a monomer of polyamide to prepare a composite. The method disperses montmorillonite, which is a kind of laminated silicate, or untreated pretreatment in excess water. It is a method of superposing | polymerizing by adding (epsilon) -caprolactam to a dispersion liquid after making it.
그러나 위의 방법은 몬모릴로나이트를 전처리하여 회수하는 단계가 별도로 필요하며, 몬모릴로나이트의 팽윤성이 커서 물에 분산시키기 위해서는 과량의 물을 사용해야 하므로 중합시켜서 얻는 폴리아미드의 수지 양에 비해 큰 용적의 반응기를 사용하여야 하기 때문에 반응기의 효율이 떨어지며 또한 반응시간이 길어지는 문제점이 있다.However, the above method requires a separate step of pretreatment and recovery of montmorillonite, and because the swellability of montmorillonite is large, an excessive amount of water must be used to disperse it in water. Therefore, a reactor having a large volume compared to the amount of polyamide resin obtained by polymerization should be used. Since there is a problem that the efficiency of the reactor is lowered and the reaction time is longer.
또한 적층된 실리케이트가 포함된 폴리아미드 수지는 통상의 폴리아미드 수지에 비해 향상된 기계적 성질을 가지지만 필름의 제조시 연신성이 떨어지기 때문에 투명성, 배향도가 나쁜 단점을 보이고 있다.In addition, polyamide resins including laminated silicates have improved mechanical properties compared to conventional polyamide resins, but show poor disadvantages in transparency and degree of orientation due to poor elongation in manufacturing films.
폴리아미드 수지의 연신성, 투명성을 증가시키기 위한 방법으로는 폴리아미드를 구성할 수 있는 단량체들을 공중합 시켜서 의한 공중합물을 얻는 방법이 있는바, 이 방법을 통하여 제조한 중합물은 중합물의 융점, 결정화도가 낮아져서유연성, 투명성, 연신성이 향상될 수 있다.As a method for increasing the elongation and transparency of the polyamide resin, there is a method of obtaining a copolymer by copolymerizing monomers that can form polyamide. The polymer prepared by this method has a melting point and crystallinity of the polymer. Can be lowered to improve flexibility, transparency, and stretchability.
그러나 공중합물의 경우에는 최종적으로 결정화 속도가 늦어지고 결정화도의 감소가 일어나서 강도와 기체 차단성 등의 물성이 저하되는 단점이 있다.However, in the case of the copolymer, there is a disadvantage in that the crystallization rate is finally lowered and the degree of crystallinity decreases, thereby lowering physical properties such as strength and gas barrier property.
본 발명은 향상된 결정화 속도를 가지며, 필름으로 제조할 때 우수한 연신성을 발휘하는 폴리아미드 수지 제조용 폴리아미드 수지 조성물과 그 제조방법을 제공하는데 목적을 둔 것이다.An object of the present invention is to provide a polyamide resin composition for producing polyamide resin and a method for producing the same, which have an improved crystallization rate and exhibit excellent stretchability when produced into a film.
본 발명은 몬모릴로나이트를 첨가하여 투명성과 연신성을 개선한 폴리아미드 수지 제조용 폴리아미드 수지 조성물 및 그 제조방법에 관한 것이다.The present invention relates to a polyamide resin composition for producing polyamide resin having improved clarity and stretchability by adding montmorillonite and a method for producing the same.
이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
폴리아미드 수지의 주성분인 ε-카프로락탐(나일론6) 70중량% 내지 99중량%와 폴리아미드 수지를 형성할수 있는m-크실렌디아민과 아디프산의 혼합물이 30 내지 1중량%로 이루어진 공중합물 100중량부에 대하여 적층된 실리케이트, 보다 바람직하게는 몬모릴로나이트 0.5-5.0중량부를 첨가하여 조성시킨 폴리아미드 수지 조성물 및 그 제조방법에 관한 것이다.Copolymer 100 consisting of 70 wt% to 99 wt% of ε-caprolactam (nylon 6), the main component of the polyamide resin, and a mixture of m -xylenediamine and adipic acid capable of forming a polyamide resin. The present invention relates to a polyamide resin composition laminated with respect to parts by weight, more preferably 0.5 to 5.0 parts by weight of montmorillonite, and a method for producing the same.
본 발명에서 사용되는 폴리아미드를 형성할 수 있는 단량체는 ε-카프로락탐,m-크실렌디아민, 아디프산등이 있다. 나일론6의 단량체인 ε-카프로락탐은 실리케이트의 적층된 구조에서 층간의 침투에 용이하며, 이것을 이용하여 적층된 실리케이트를 팽윤화하여 층간의 거리를 확대시키면 최종적으로 얻은 폴리아미드내의 실리케이트의 분산성이 향상된다.Monomers capable of forming the polyamide used in the present invention include ε-caprolactam, m -xylenediamine, adipic acid and the like. Ε-caprolactam, a monomer of nylon 6, is easy to penetrate between layers in a laminated structure of silicates, and the dispersibility of the silicates in the polyamide finally obtained by swelling the laminated silicates to increase the distance between the layers. Is improved.
m-크실렌디아민과 아디프산은 같은 몰수로 반응하여 MXD-6 나일론을 구성하며 동시에 ε-카프로락탐과 용융중합하여 폴리아미드 공중합물을 제조하게 된다. The m -xylenediamine and adipic acid react with the same mole number to form MXD-6 nylon, and at the same time, melt polymerization with ε-caprolactam to prepare a polyamide copolymer.
MXD-6 나일론은 주쇄 사슬 중 페닐렌 구조를 포함하고 있어 강직한 성질을 보이며 또한 페닐렌 구조의 치환 위치가 메타 위치에 있어 결정화 속도가 늦으므로 필름을 성형시킬 때 투명하며 연신성이 뛰어난 성질이 있다.MXD-6 nylon has a phenylene structure in the main chain, which shows rigidity and the crystallization rate is slow because the substitution position of the phenylene structure is in the meta position. have.
또 이러한 성질 이외에 산소, 습도 등 기체에 대한 차단성이 우수하여 포장용 필름의 용도로 많이 사용되고 있다.In addition to these properties, it has excellent barrier properties to gases such as oxygen and humidity, and is widely used for packaging films.
MXD-6 나일론 성분이 공중합된 폴리아미드 수지는 나일론6 수지에 비해 결정화 속도가 늦어져 투명성과 연신성이 향상된 물성을 가지게 된다.The polyamide resin copolymerized with the MXD-6 nylon component has a slower crystallization rate than the nylon 6 resin and thus has improved transparency and stretchability.
폴리아미드 수지 100중량부에 대해 MXD-6 나일론을 형성하는m-크실렌디아민과 아디프산의 혼합물양이 1중량%보다 작으면 원하는 공중합물의 성질을 얻기 어려우며 30중량%가 넘으면 결정화 속도가 너무 느려져 성형성이 나빠지고 결정화도가 너무 작아져 오히려 기체차단성 등 원하는 성질을 얻기 어렵다.When the amount of the mixture of m -xylenediamine and adipic acid that forms MXD-6 nylon is less than 1% by weight based on 100 parts by weight of polyamide resin, it is difficult to obtain the desired copolymer properties, and when it exceeds 30% by weight, the crystallization rate becomes too slow. The moldability deteriorates and the crystallinity becomes too small to obtain desired properties such as gas barrier properties.
본 발명에서 사용되는 적층된 실리케이트는 폴리아미드 공중합물의 기계적 강도, 내약품성, 기체차단성 등의 성질을 향상시키며 또한 공중합에 의해 늦어진 결정화 속도를 조절하는 역할을 하게 된다.The laminated silicates used in the present invention improve the mechanical strength, chemical resistance, gas barrier properties, etc. of the polyamide copolymer, and also serve to control the crystallization rate slowed by the copolymerization.
이러한 적층구조의 실리케이트로는 몬모릴로나이트, 사포나이트, 헥토라이트, 바이델라이트 등이 있으며 이중에서 몬모릴로나이트는 외관비(aspect ratio)가 1,000배정도로 매우 크며, 또한 폴리아미드 수지와의 결합력이 강하므로 본 발명이 바라는 효과를 얻기에 유리하다.As a silicate of such a laminated structure, montmorillonite, saponite, hectorite, Weidelite, etc. Among them, montmorillonite has a very large aspect ratio of about 1,000 times, and also has a strong bonding force with polyamide resin. It is advantageous to obtain this desired effect.
몬모릴로나이트는 폴리아미드 공중합물 100중량부에 대하여 0.5∼5중량부가 사용되며 0.5중량부 미만인 경우에는 본 발명이 바라는 효과를 얻기 어려우며, 5중량부를 초과하는 경우에는 큰 값의 외관비를 갖는 몬모릴로나이트에 의해 중합물의 용융점도가 상승하므로 중합 및 가공이 어렵게 된다.Montmorillonite is used in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the polyamide copolymer, and when it is less than 0.5 parts by weight, it is difficult to obtain the desired effect of the present invention. When it exceeds 5 parts by weight, montmorillonite has a large appearance ratio. Since the melt viscosity of the polymer increases, polymerization and processing become difficult.
본 발명에서 사용되는 몬모릴로나이트는 층간거리가 10Å인 판상이 적층되어 있는 있는 구조로 그 상태로 중합에 사용하면 폴리아미드 수지 내에서 분산성이 매우 좋지 않으므로 층간 사이를 침투할 수 있는 팽윤화제로 처리해서 층간 거리를 크게 하는 전처리과정이 필요하다.The montmorillonite used in the present invention has a structure in which plate-like layers having a distance of 10 하면 are laminated, and when used for polymerization in this state, dispersibility is very poor in a polyamide resin, so it is treated with a swelling agent that can penetrate between layers. There is a need for pretreatment to increase the interlayer distance.
본 발명에서는 조제조내에서 몬모릴로나이트를 ε-카프로락탐, 인산, 물과 반응시켜 전처리를 수행한 뒤 반응기로 이송하여 폴리아미드의 단량체들과 혼합하여 중합에 이용하는 방법으로 폴리아미드를 제조하였다.In the present invention, the polyamide was prepared by reacting montmorillonite with ε-caprolactam, phosphoric acid, and water in the preparation, followed by pretreatment, mixed with monomers of polyamide, and used for polymerization.
조제조에서의 전처리과정을 거치게 되면 별도의 회수과정이 필요하지 않으며 몬모릴로나이트의 분산매로 약 30배 내지 50배 사용되던 물의 양을 줄일 수 있는 장점이 있다.The pretreatment in the preparation process does not require a separate recovery process and has the advantage of reducing the amount of water used about 30 to 50 times as a dispersion medium of montmorillonite.
즉, 조제조에 몬모릴로나이트 100중량부에 대해 ε-카프로락탐 300 내지 1,000중량부, 물 150 내지 500중량부를 첨가하고 인산을 몬모릴로나이트의 이온교환능에 대하여 1당량 가한 뒤 교반하여 전처리를 수행하게 된다.That is, 300 to 1,000 parts by weight of ε-caprolactam and 150 to 500 parts by weight of water are added to 100 parts by weight of montmorillonite, and 1 equivalent of phosphoric acid is added to the ion exchange capacity of montmorillonite, followed by stirring to perform pretreatment.
전처리에 사용하는 ε-카프로락탐의 양이 300중량부 미만일 경우에는 팽윤화의 효과가 작아지며, 1,000중량부를 초과하여 사용할 경우는 조제조의 크기가 커지는 단점이 있고, 분산매인 물의 양과 ε-카프로락탐의 양이 몬모릴로나이트 100중량부에 대해 300 내지 1,000중량부가 되도록 하며 이때 조제조의 온도는 70∼140℃가 적당하다.When the amount of ε-caprolactam used in the pretreatment is less than 300 parts by weight, the effect of swelling is reduced, and when used in excess of 1,000 parts by weight, the size of the preparation is increased, and the amount of water and ε-caprolactam as a dispersion medium is increased. The amount of is to be 300 to 1,000 parts by weight based on 100 parts by weight of montmorillonite, the temperature of the preparation is preferably 70 ~ 140 ℃.
본 발명에서 폴리아미드 수지 조성물을 이용하여 폴리아미드 수지를 제조하는 중합 공정은 아래와 같다.In the present invention, a polymerization process for preparing a polyamide resin using the polyamide resin composition is as follows.
1) 조제조에 몬모릴로나이트, ε-카프로락탐, 인산, 물을 투입한 뒤 교반1) Montmorillonite, ε-caprolactam, phosphoric acid and water were added to the preparation, followed by stirring.
하며 가열하여 전처리를 수행한다.Preheating is performed by heating.
2) 반응기에 ε-카프로락탐과m-크실렌디아민, 아디프산을 원하는 조성비2) desired composition ratio of ε-caprolactam, m -xylenediamine and adipic acid in the reactor;
로 투입하고 물을 첨가하여 조제조의 온도와 같게 한다.Add water and add water to make it equal to the temperature of preparation.
이때 ε-카프로락탐의 양은 반응기와 조제조에 투입하는 양을 합하여In this case, the amount of ε-caprolactam is added to the reactor and the preparation
계산하며 전체적으로 원하는 조성의 공중합물에 해당하게 한다.Calculate and correspond to the copolymer of the desired composition as a whole.
3) 조제조의 혼합물을 이송하여 반응기로 이송한 뒤 가열하여 온도를 상3) Transfer the mixture of preparation to the reactor and heat it to raise the temperature.
승시키며 반응을 위해 가압 상태를 유지하고, 반응기의 압을 서서히 제And pressurized for reaction, slowly depressurizing the reactor
거하며 상압을 만든다.Dwells and creates atmospheric pressure.
4) 원하는 분자량 수준의 감압을 수행한 뒤 반응기에 가압을 하여 폴리아4) After carrying out the decompression of the desired molecular weight level and pressurizing the reactor,
미드 중합물을 배출한다.Drain the midpolymer.
5) 중합물을 최대한의 욕비로 미반응 물질을 추출한 뒤 건조하여 최종 폴5) Extract the unreacted material in the maximum bath ratio and dry it.
리아미드 수지를 얻는다.Obtain a riamide resin.
폴리아미드 수지의 상대점도는 1.8∼4.0의 범위가 바람직하다.The relative viscosity of the polyamide resin is preferably in the range of 1.8 to 4.0.
상대점도가 1.8 미만의 경우에는 기계적 물성이 분자량의 영향으로 저하되며 4.0을 초과하는 경우에는 가공성이 떨어지는 단점이 있다.If the relative viscosity is less than 1.8, the mechanical properties are lowered due to the influence of molecular weight, and when the relative viscosity is higher than 4.0, workability is inferior.
실시예 1Example 1
몬모릴로나이트(구네미네사 구니피아-F, 119meq/100g) 100g과 ε-카프로락탐 500g을 조제조에 투입하고 85% 인산 13.72g을 물 150g에 희석하여 첨가한 뒤 교반을 하면서 온도를 상승시켜 90℃에 도달하게 한다.100 g of montmorillonite (Geunminesa Gunipia-F, 119 meq / 100 g) and 500 g of ε-caprolactam were added to the preparation, and 13.72 g of 85% phosphoric acid was added to 150 g of water, and the temperature was raised to 90 ° C. while stirring. To reach.
교반기의 속도를 100rpm으로 하여 3시간 이상 교반하여 몬모릴로나이트의 팽윤화가 충분히 이루어지도록 하였다.The stirrer was stirred at 100 rpm for 3 hours or more to sufficiently swell the montmorillonite.
40L 반응기에 ε-카프로락탐 7.5kg,m-크실렌디아민 0.98kg, 아디프산 1.04kg과 물을 2kg 첨가한 뒤 반응기의 온도가 90℃에 이르도록 가열한 뒤 미리 제조된 조제조의 혼합물을 질소의 가압에 의해 이송한다.7.5 kg of ε-caprolactam, 0.98 kg of m -xylenediamine, 1.04 kg of adipic acid and 2 kg of water were added to the 40 L reactor, and the reactor was heated to 90 ° C. Transfer by pressurization.
이송이 완료되면 반응기의 혼합물을 교반하며 온도를 250℃로 상승시켜 14kg/cm2으로 유지하고 1시간 동안 반응시킨다.When the transfer is complete, the mixture of the reactor is stirred and the temperature is raised to 250 ° C. and maintained at 14 kg / cm 2 and reacted for 1 hour.
반응기내의 압력을 1시간 동안 서서히 제거하여 상압을 만든 뒤 0.3kg/cm2의 압력으로 30분 동안 감압하여 중합을 완결시킨다.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 0.3kg / cm 2 for 30 minutes.
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 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 용융압출기를 이용하여 압출하여 150μm의 시트를 제조하였다.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 150μm.
이때 냉각롤의 온도는 30℃로 유지하였으며 제조된 시트를 80℃에서 30초간 예열한 뒤 이축으로 각 4배씩 동시에 연신하여 연신성을 평가하였으며 그 결과를 표 1에 나타내었다.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 stretched four times at the same time by biaxially evaluated the elongation is shown in Table 1.
실시예 2Example 2
몬모릴로나이트(구네미네사 구니피아-F, 119meq/100g) 100g과 ε-카프로락탐 500g을 조제조에 투입하고 85% 인산 13.72g을 물 150g에 희석하여 첨가한 뒤 실시예1과 같이 전처리를 수행하였다.100 g of montmorillonite (Geunminesa gunipia-F, 119 meq / 100 g) and 500 g of ε-caprolactam were added to the preparation, and 13.72 g of 85% phosphoric acid was added to 150 g of water, followed by pretreatment as in Example 1.
40L 반응기에는 ε-카프로락탐 6.5kg,m-크실렌디아민 1.47kg, 아디프산 1.56kg과 물을 2kg 첨가한 뒤 반응기의 온도가 90℃에 이르면 실시예 1과 동일한 방법에 의해 폴리아미드 수지를 제조하여 성질을 평가하였다.In the 40L reactor, 6.5 kg of ε-caprolactam, 1.47 kg of m -xylenediamine, 1.56 kg of adipic acid and 2 kg of water were added, and then the polyamide resin was prepared in the same manner as in Example 1 when the temperature of the reactor reached 90 ° C. The properties were evaluated.
실시예 3Example 3
몬모릴로나이트(구네미네사 구니피아-F, 119meq/100g) 100g과 ε-카프로락탐 500g을 조제조에 투입하고 85% 인산 13.72g을 물 150g에 희석하여 첨가한 뒤 실시예1과 같이 전처리를 수행하였다.100 g of montmorillonite (Geunminesa gunipia-F, 119 meq / 100 g) and 500 g of ε-caprolactam were added to the preparation, and 13.72 g of 85% phosphoric acid was added to 150 g of water, followed by pretreatment as in Example 1.
40L 반응기에는 ε-카프로락탐 9.4kg,m-크실렌디아민 49g, 아디프산 52g과 물을 2kg 첨가한 뒤 반응기의 온도가 90℃에 이르면 실시예1과 동일한 방법에 의해 폴리아미드 수지를 제조하여 성질을 평가하였다.In the 40L reactor, 9.4 kg of ε-caprolactam, 49 g of m -xylenediamine, 52 g of adipic acid and 2 kg of water were added, and when the temperature of the reactor reached 90 ° C., a polyamide resin was prepared in the same manner as in Example 1 Was evaluated.
비교예 1Comparative Example 1
몬모릴로나이트(구네미네사 구니피아-F, 119meq/100g) 100g과 ε-카프로락탐 500g을 조제조에 투입하고 85% 인산 13.72g을 물 100g에 희석하여 첨가한 뒤 실시예1과 같이 전처리를 수행하였다.100 g of montmorillonite (Geunminesa gunipia-F, 119 meq / 100 g) and 500 g of ε-caprolactam were added to the preparation, and 13.72 g of 85% phosphoric acid was diluted and added to 100 g of water, followed by pretreatment as in Example 1.
40L 반응기에는 ε-카프로락탐 9.5kg과 물을 2kg 첨가한 뒤 반응기의 온도가 90℃에 이르면 실시예1과 동일한 방법에 의해 폴리아미드 수지를 제조하여 성질을 평가하였다.In the 40L reactor, 9.5 kg of ε-caprolactam and 2 kg of water were added, and when the temperature of the reactor reached 90 ° C., polyamide resin was prepared in the same manner as in Example 1 to evaluate properties.
비교예 2Comparative Example 2
몬모릴로나이트(구네미네사 구니피아-F, 119meq/100g) 100g과 ε-카프로락탐 500g을 조제조에 투입하고 85% 인산 13.72g을 물 100g에 희석하여 첨가한 뒤 실시예1과 같이 전처리를 수행하였다.100 g of montmorillonite (Geunminesa gunipia-F, 119 meq / 100 g) and 500 g of ε-caprolactam were added to the preparation, and 13.72 g of 85% phosphoric acid was diluted and added to 100 g of water, followed by pretreatment as in Example 1.
40L 반응기에 ε-카프로락탐 7.5kg, 헥사메틸렌디아민과 아디프산의 염을 2.0kg, 물 2kg을 첨가한 뒤 실시예1과 동일한 방법에 의해 폴리아미드 수지를 제조하여 성질을 평가하였다.7.5 kg of ε-caprolactam, 2.0 kg of hexamethylenediamine and adipic acid, and 2 kg of water were added to the 40L reactor, and polyamide resin was prepared in the same manner as in Example 1 to evaluate properties.
비교예 3Comparative Example 3
몬모릴로나이트(구네미네사 구니피아-F, 119meq/100g) 30g과 ε-카프로락탐 300g을 조제조에 투입하고 85% 인산 4.12g을 물 100g에 희석하여 첨가한 뒤 실시예1과 같이 전처리를 수행하였다.30 g of montmorillonite (Geunminesa gunipia-F, 119 meq / 100 g) and 300 g of ε-caprolactam were added to the preparation, and 4.12 g of 85% phosphoric acid was diluted and added to 100 g of water, followed by pretreatment as in Example 1.
40L 반응기에는 ε-카프로락탐 6.7kg,m-크실렌디아민 1.47kg, 아디프산 1.56kg과 물을 2kg 첨가한 뒤 반응기의 온도가 90℃에 이르면 실시예1과 동일한 방법에 의해 폴리아미드 수지를 제조하여 성질을 평가하였다.In a 40L reactor, 6.7 kg of ε-caprolactam, 1.47 kg of m -xylenediamine, 1.56 kg of adipic acid and 2 kg of water were added, and when the temperature of the reactor reached 90 ° C, a polyamide resin was prepared in the same manner as in Example 1. The properties were evaluated.
< 표 1 ><Table 1>
본 발명의 폴리아미드 수지 조성물로 중합시킨 폴리아미드 수지는 결정화 속도와 연신성이 함께 향상되며, 또 본 발명은 폴리아미드 수지 내에 몬모릴로나이트를 분산성이 좋게 혼합시킬 수 있다.The polyamide resin polymerized with the polyamide resin composition of the present invention improves crystallization rate and stretchability, and the present invention can mix montmorillonite in the polyamide resin with good dispersibility.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005012430A1 (en) * | 2003-07-10 | 2005-02-10 | Honeywell International, Inc. | Delamination-resistant, barrier polyamide compositions for 3-layer pet beverage bottles |
| KR100496381B1 (en) * | 2001-10-24 | 2005-06-17 | 주식회사 효성 | Copolyamide Resin Composition Containing Monmorillonite |
| KR100786589B1 (en) * | 2001-12-11 | 2007-12-21 | 주식회사 코오롱 | Polyamides composition and film thereof |
| CN116041695A (en) * | 2022-04-26 | 2023-05-02 | 湖南世博瑞高分子新材料有限公司 | Copolymerization barrier nylon and continuous synthesis method and application thereof |
-
1999
- 1999-12-23 KR KR1019990060938A patent/KR20010057495A/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100496381B1 (en) * | 2001-10-24 | 2005-06-17 | 주식회사 효성 | Copolyamide Resin Composition Containing Monmorillonite |
| KR100786589B1 (en) * | 2001-12-11 | 2007-12-21 | 주식회사 코오롱 | Polyamides composition and film thereof |
| WO2005012430A1 (en) * | 2003-07-10 | 2005-02-10 | Honeywell International, Inc. | Delamination-resistant, barrier polyamide compositions for 3-layer pet beverage bottles |
| CN116041695A (en) * | 2022-04-26 | 2023-05-02 | 湖南世博瑞高分子新材料有限公司 | Copolymerization barrier nylon and continuous synthesis method and application thereof |
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