KR101107585B1 - Method for preparing polyolefin-layered clay nanocomposites by high pressure method - Google Patents
Method for preparing polyolefin-layered clay nanocomposites by high pressure method Download PDFInfo
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Abstract
본 발명은 고압법에 의한 폴리올레핀-층상구조점토 나노복합체의 제조방법에 관한 것으로서, 더욱 상세하게는 폴리올레핀 수지와 층상구조점토를, 저비점 유기용매에 분산 및 가열하여 용해시킨 후 냉각하여 폴리올레핀-층상구조점토 나노복합체를 결정화시키고 유기용매를 제거하는 단계를 포함하여 이루어지되, 상기 가열이 밀폐된 고압반응기에서 이루어지는 것을 폴리올레핀-층상구조점토 나노복합체의 제조방법에 관한 것이다. The present invention relates to a method for producing a polyolefin-layered clay nanocomposite by a high pressure method, and more specifically, to a polyolefin-layered structure by dispersing a polyolefin resin and a layered clay in a low-boiling organic solvent, dissolving it by heating, and then cooling it. Crystallizing the clay nanocomposite and removing the organic solvent, wherein the heating is made in a closed high pressure reactor relates to a method for producing a polyolefin-layered clay nanocomposite.
본 발명에 의하면 새로운 제조방법인 고압법을 이용하여 폴리올레핀-층상구조점토 나노복합체를 간단하게 제조할 수 있고, 이에 따라 제조된 나노복합체에는 다량의 점토가 포함되어 있어 경제성이 탁월하며, 제조된 나노복합체는 기존의 나노복합체를 적용하던 분야에 다양하게 적용될 수 있다.According to the present invention, a polyolefin-layered clay nanocomposite can be easily produced by using a high pressure method, which is a novel manufacturing method. The nanocomposite thus prepared contains a large amount of clay, which is excellent in economic efficiency, and manufactured nano The complex can be applied in various fields to the conventional nanocomposites.
나노복합체, 층상점토, 폴리올레핀, 고압법, 유기용매 Nanocomposite, Layered Clay, Polyolefin, High Pressure Method, Organic Solvent
Description
본 발명은 폴리올레핀-층상구조점토 나노복합체의 제조방법에 관한 것으로, 지금까지 시도되지 않았던 새로운 제조방법인 고압법을 이용하여 폴리올레핀-층상구조점토 나노복합체를 간단하게 제조할 수 있는 방법에 관한 것이다.The present invention relates to a method for producing a polyolefin-layered clay nanocomposite, and to a method for producing a polyolefin-layered clay nanocomposite simply by using a high pressure method, which has not been attempted so far.
고분자와 점토의 복합체는 고분자 수지에 무기 강화제를 첨가함으로써 강성, 내열성 및 수치 안정성 등을 향상시킨 소재로서, 자동차 소재, 전기전자 부품, 비행기 내장재, 생활용품, 타이어, 접착제 등 많은 분야에 널리 이용되고 있다. 특히 층상구조점토를 이용하여 무기물을 나노 스케일로 분산시킨 나노복합체는 기존의 복합체에 비해 단위 부피당 접촉 면적이 넓기 때문에 무기물을 소량 첨가하여도 경량성, 내열성, 기계적 물성 등이 크게 향상되는 등 우수한 물성을 얻을 수 있다.Composites of polymers and clays are materials that improve stiffness, heat resistance and numerical stability by adding inorganic reinforcing agents to polymer resins, and are widely used in many fields such as automobile materials, electric and electronic parts, airplane interior materials, household goods, tires, adhesives, etc. have. Particularly, nanocomposites in which inorganic materials are dispersed on a nanoscale using layered clay have a larger contact area per unit volume than conventional composites. Thus, even when a small amount of inorganic material is added, light weight, heat resistance, and mechanical properties are greatly improved. Can be obtained.
통상 층상구조점토의 층간 구조 사이에 고분자를 삽입하는 방법은 용액법, 중합법 및 용융법으로 크게 3가지가 대표된다.In general, three methods of inserting a polymer between the interlaminar structures of layered clays include a solution method, a polymerization method, and a melting method.
중합법은 유기화된 층상실리케이트 같은 층상구조점토와 고분자의 원료인 단량체를 혼합하여 단량체의 일부를 층상구조점토의 층간에 침투시키고 이를 중합시켜 복합체를 얻는 방법으로 고분자 나노복합재료 제조에서 가장 널리 사용되는 방법이다. 이 방법으로 제조되는 고분자 나노복합재료로는 나일론계가 대표적이다. 상기한 중합법은 저분자량인 단량체를 층상구조점토의 층간에 삽입시키므로 비교적 쉽게 박리가 일어나 층상구조점토를 나노스케일로 분산시킬 수 있다는 장점이 있다. 그러나, 중합법에 사용 가능한 단량체가 한정되어 있고 제조공정이 다소 복잡한 점이 문제점으로 지적된다. Polymerization method is the most widely used in the production of polymer nanocomposites as a method of mixing a layered clay such as organic layered silica and monomers which are a raw material of the polymer to infiltrate a part of the monomer into the layered layered clay and polymerize it to obtain a composite. It is a way. Nylon is a typical polymer nanocomposite produced by this method. Since the polymerization method inserts a low molecular weight monomer between the layers of the layered clay, there is an advantage in that the peeling occurs relatively easily to disperse the layered clay on a nanoscale. However, it is pointed out that the problem is that the monomers usable in the polymerization method are limited and the manufacturing process is somewhat complicated.
용액법은 고분자를 용매에 녹여 용액을 만들고, 이를 유기화 층상구조점토와 혼합하는 것으로 이루어진다. 상기 용액법은 용액상태에서 고분자량의 고분자를 층상구조점토의 층간에 삽입시키기가 어렵고 최종제품을 얻기 위해서는 고형분을 용제와 분리시켜야 하는 단점이 있다. 즉, 용액법은 학술적인 관점에서 많이 시도되고 있으나 상업적인 대량생산이 불가능하다는 점이 문제점으로 지적되고 있다.The solution method consists of dissolving the polymer in a solvent to form a solution and mixing it with the organic layered clay. The solution method has a disadvantage in that it is difficult to insert a high molecular weight polymer between layers of layered clay in a solution state and to separate solids from a solvent in order to obtain a final product. That is, the solution method has been tried a lot from an academic point of view, but it is pointed out as a problem that commercial mass production is impossible.
용융법은 유기화 층상구조점토를 직접 고분자 수지와 용융상태에서 혼합하는 것으로 기존의 고분자 컴파운드법과 동일하게 압출기, 롤밀, 반바리 믹서 등의 가공설비를 이용할 수 있기 때문에 상업적인 면에서 가장 바람직하다고 볼 수 있다. 그러나 고분자물질을 고점도의 용융체 상태로 층간 삽입시키기가 매우 어려운 단점이 있다. 이를 해결하기 위하여, 유기화 층상구조점토의 선정, 고분자 수지와 층상구조점토의 친화력을 높여주는 상용화제 사용, 고분자 수지의 개질, 혼합조건 등의 다양한 연구를 통하여 폴리에틸렌, 폴리프로필렌, 폴리스티렌 등의 소수성 고분자 들도 용융법으로 나노복합 재료화 하는 기술이 개발되고 있다. 이와 같이 용융법은 제조공정이 단순하고, 그레이드의 다양화가 가능하여 앞으로 큰 발전이 기대되는 분야이나 나노스케일로 층상물질을 박리시키기 위해서는 고도의 기술개발이 필요하다.The melting method is the most preferable from the commercial point of view because it can mix the organic layered clay directly with the polymer resin in the molten state and can use the processing equipment such as extruder, roll mill, and short-barrier mixer in the same way as the existing polymer compound method. . However, there is a disadvantage in that it is very difficult to insert the polymer material into a high viscosity melt state. In order to solve this problem, hydrophobic polymers such as polyethylene, polypropylene, polystyrene, etc. are selected through various studies such as selection of organic layered clay, use of a compatibilizer to increase affinity between polymer resin and layered clay, modification of polymer resin, and mixing conditions. Also, a technique for forming nanocomposite materials by the melting method has been developed. As described above, the melting method is simple in the manufacturing process and can be diversified in grade, and thus, advanced technology development is required in order to peel the layered material on a nanoscale or in a field where great development is expected in the future.
한편, 중합법에 비해 고분자 용액에 유기화 층상구조점토를 침지시켜 용매에 의해 고분자 수지에 점토가 분산되도록 하는 용액법이나, 용융상태에서 고분자를 점토의 층간에 삽입시켜 기계적인 혼합이 일어 나도록하여 복합재료화 하는 용융법이 많이 사용된다. On the other hand, compared to the polymerization method, a solution method in which an organic layered clay is immersed in a polymer solution to disperse clay in a polymer resin by a solvent, or a polymer is mixed between layers of clay in a molten state to cause mechanical mixing. Many melting methods are used.
본 발명은 상기한 바와 같이 종래 기술에서의 문제점을 해결할 수 있는 고분자-층상구조점토 나노복합체를 제조할 수 있는 방법을 제공하기 위한 것으로, 지금까지 전혀 시도되지 않았던 새로운 제조방법인 고압법을 이용한 고분자-층상구조점토 나노복합체의 제조방법을 제공하는데 그 목적이 있다.The present invention is to provide a method for producing a polymer-layered clay nanocomposite that can solve the problems in the prior art as described above, a polymer using a high pressure method which is a novel manufacturing method that has not been tried at all Its purpose is to provide a method for preparing a layered clay nanocomposite.
상기한 목적을 달성하기 위한 일례로서 본 발명의 폴리올레핀-층상구조점토 나노복합체의 제조방법은, 유기화 층상구조점토 0.1 내지 45 중량%와 폴리올레핀 수지 55 내지 99.9 중량% 비율로 혼합하고, 유기용매 중에 상기 유기화 층상구조 점토와 폴리올레핀 수지의 혼합물을 1 내지 35 중량% 비율로 혼합한 다음, 가열하여 상기 폴리올레핀 수지를 용해시키는 단계와; 상기 용해물을 냉각하여 폴리올레핀-층상구조점토 나노복합체를 결정화시키고 유기용매를 제거시키는 단계를 포함하여 이루어지되, 상기 가열이 밀폐된 고압반응기에서 이루어지는 것을 특징으로 한다.As an example for achieving the above object, the method for producing a polyolefin-layered clay nanocomposite of the present invention is mixed with 0.1 to 45% by weight of organic layered clay and 55 to 99.9% by weight of a polyolefin resin, and the organic solvent Mixing the mixture of the organic layered clay and the polyolefin resin in a ratio of 1 to 35% by weight and then heating to dissolve the polyolefin resin; Cooling the melt to crystallize the polyolefin-layered clay nanocomposite and remove the organic solvent, characterized in that the heating is made in a closed high pressure reactor.
상기 가열은 압력 1 내지 15 bar와 온도 100 ~ 220 ℃ 범위의 조건을 구성하는 밀폐된 상태의 고압반응기에서 수행될 수 있다.The heating may be performed in a closed autoclave constituting a pressure of 1 to 15 bar and a temperature range of 100 to 220 ℃.
또한, 상기 가열 이전에 고압반응기 내의 공기를 제거하는 단계를 더 포함할 수 있다.In addition, the method may further include removing air in the high pressure reactor before the heating.
이하, 본 발명의 폴리올레핀-층상구조점토 나노복합체의 제조방법을 각 단계별로 구체적으로 설명하며, 도 1에는 본 발명의 폴리올레핀-층상구조점토 나노복합체의 제조 공정을 개략적으로 나타낸 순서도를 도시하였다.Hereinafter, a method for preparing a polyolefin-layered clay nanocomposite of the present invention will be described in detail for each step, and FIG. 1 is a flowchart schematically showing a manufacturing process of the polyolefin-layered clay nanocomposite of the present invention.
먼저, 폴리올레핀 수지와 유기화 층상구조점토를 저비점 유기용매에 분산시킨 다음 가열하여 용해시키는 단계이다. First, the polyolefin resin and the organic layered clay are dispersed in a low boiling organic solvent and then heated to dissolve.
상기 폴리올레핀 수지는 폴리에틸렌, 폴리프로필렌, 폴리에틸렌비닐아세테이트 및 이들의 공중합체 등 중에서 선택된 어느 하나를 사용할 수 있다.The polyolefin resin may be any one selected from polyethylene, polypropylene, polyethylene vinyl acetate, copolymers thereof, and the like.
상기 유기화 층상구조점토는 종횡비가 5 내지 2000 정도의 판상을 띠며, 대략 한 층의 두께가 1 ㎚ 정도인 것을 사용할 수 있을 것이다. 상기 층상구조점토는 친유기성의 알킬 암모늄 이온이나 알킬 포스포늄 이온과 같은 오늄이온 등으로 치 환된 유기화 층상구조점토를 사용할 수 있으며, 본 발명의 목적을 달성하는데 영향을 미치지 아니하는 것이면 당업계에서 널리 사용되는 것을 선택하여 사용할 수 있을 것이다.The organic layered clay may have a plate shape having an aspect ratio of about 5 to about 2000, and a layer having a thickness of about 1 nm. The layered clay may be an organic layered clay substituted with onium ions such as lipophilic alkyl ammonium ions or alkyl phosphonium ions, etc., if it does not affect the purpose of the present invention is widely used in the art You will be able to choose what is used.
상기 유기용매들은 상온에서는 폴리올레핀 수지에 대한 용해력이 없으나, 가열하여 온도가 상승하면 용해력을 나타내는 특징이 있다. The organic solvents do not have a dissolving ability to the polyolefin resin at room temperature, but is characterized by exhibiting dissolving power when the temperature rises by heating.
상기한 유기용매로는, 테트라히드로퓨란, 디옥산, BTX계 방향족탄화수소, 탄소수가 5 내지 12개인 알칸 및 시클로알칸 등 중에서 선택된 적어도 하나를 사용할 수 있으며, 이러한 유기용매는 사용되는 폴리올레핀 수지의 용융온도와 용해력을 고려하여 선택되어져야 할 것이다.As the organic solvent, at least one selected from tetrahydrofuran, dioxane, BTX-based aromatic hydrocarbons, alkanes having 5 to 12 carbon atoms, cycloalkanes, and the like may be used, and the organic solvent may be used at a melting temperature of the polyolefin resin used. It should be chosen in consideration of and the solvent power.
본 발명에 의하면, 폴리올레핀-층상구조점토 나노복합체 총 중량 중 유기화 층상구조점토는 0.1 내지 45 중량% 범위로 혼합할 수 있다. 본 발명에 의하면 기존의 경우 고분자-층상구조점토 나노복합체 중에서 점토의 함량이 평균 5 중량% 범위인 것과 비교하여 보다 고농도인 45 중량%까지의 점토가 나노복합체 내에 포함될 수 있는 효과를 가진다.According to the present invention, the organic layered clay in the total weight of the polyolefin-layered clay nanocomposites may be mixed in the range of 0.1 to 45% by weight. According to the present invention, the clay has a higher concentration of up to 45% by weight of clay in the nanocomposite as compared to the range of clay in the polymer-layered clay nanocomposite in the range of 5% by weight on average.
상기 유기용매 중 층상구조점토와 폴리올레핀 수지 혼합물인 고형성분 함량은 1 내지 35 중량% 비율로 혼합되도록 한다. 고형성분의 함량이 상기 범위를 초과하여 다량 포함되면 유기화 층상점토의 분산이 원활하게 이루어지지 않거나, 폴리올레핀의 분말화가 원활하게 이루어지지 않아 바람직하지 않은 경향이 있으므로, 이를 고려하여 유기용매 중 폴리올레핀 수지의 함량을 조절하도록 한다.The solid component content of the layered clay and the polyolefin resin mixture in the organic solvent is to be mixed in a ratio of 1 to 35% by weight. When the content of the solid component is included in a large amount exceeding the above range, since the organic layered clay is not smoothly dispersed or the polyolefin powder is not smoothly formed, it tends to be undesirable, so considering the polyolefin resin in the organic solvent Adjust the content.
상기 폴리올레핀 수지와 유기화된 층상구조점토는 유기용매에 분산된 후 가 열하여 폴리올레핀 수지가 유기용매에 균일하게 녹아들어갈 수 있도록 한다. 이때 상기 혼합물을 교반하면서 가열할 경우 폴리올레핀 수지가 빠르게 유기용매에 녹을 수 있을 것이다. 또한, 상기 가열은 사용된 폴리올레핀 수지의 융점 이상으로 가열하는데, 폴리에틸렌이나 폴리프로필렌 등을 사용할 경우 이들을 용해시키기 위하여 가열 온도를 100℃ 이상, 바람직하기로는 100 내지 220 ℃, 더욱 바람직하기로는 150 내지 220 ℃ 범위가 되도록 하는 것이 좋다. The polyolefin resin and the organic layered clay are dispersed in an organic solvent and then heated so that the polyolefin resin can be uniformly dissolved in the organic solvent. In this case, when the mixture is heated while stirring, the polyolefin resin may be rapidly dissolved in the organic solvent. In addition, the heating is heated above the melting point of the polyolefin resin used, in order to dissolve them when using polyethylene or polypropylene, the heating temperature is 100 ℃ or more, preferably 100 to 220 ℃, more preferably 150 to 220 It is good to be in the range of ℃.
본 발명의 폴리올레핀-층상구조점토 나노복합체의 제조방법은 밀폐된 반응기에서 수행되는 것이 보다 바람직한데, 유기용매를 끓는 온도 이상으로 가열하는 과정에서 기화된 용매가 배출되지 않으므로 반응기내 압력이 상승하므로, 이러한 압력상승을 견딜 수 있도록 고압반응기를 사용하는 것이 좋다. 이때 압력은 1 내지 15 bar 정도 범위가 될 수 있다.The method for preparing the polyolefin-layered clay nanocomposites of the present invention is more preferably carried out in a closed reactor, since the vaporized solvent is not discharged in the process of heating the organic solvent above the boiling temperature, so that the pressure in the reactor increases. It is recommended to use a high pressure reactor to withstand this pressure rise. At this time, the pressure may be in the range of about 1 to 15 bar.
본 발명은 상기와 같이 고온 및 고압의 조건에서 폴리올레핀 수지와 층상구조점토를 유기용매에 녹거나 분산되게 할 경우 폴리올레핀 수지와 유기용매가 모두 액상으로 분산된 상태에서 혼합되므로 단시간 내에 폴리올레핀 수지가 유기용매에 용해되고, 또한 층상구조점토 층간에 폴리올레핀 고분자의 삽입이 보다 용이하게 이루어지는 것을 확인하였다. In the present invention, when the polyolefin resin and the layered clay are dissolved or dispersed in the organic solvent under the conditions of high temperature and high pressure as described above, the polyolefin resin is mixed with the organic solvent in a short time because both the polyolefin resin and the organic solvent are dispersed in the liquid phase. It was confirmed that the polyolefin polymer was more easily dissolved in the interlaminar clay layer.
한편, 상기 가열 이전에 고압반응기 내의 공기를 제거하는 단계를 더 포함하면 산화과정을 억제할 수 있어 바람직하다. 필요에 따라 산화방지제를 첨가하는 것도 하나의 방법이 될 수 있을 것이다.On the other hand, further comprising the step of removing the air in the high-pressure reactor before the heating it is preferable to suppress the oxidation process. Adding antioxidants as needed may be one way.
상기와 같이 폴리올레핀 수지가 유기용매에 녹고, 층상구조점토가 분산되어 균일한 상태를 이룬 용해물을 냉각하여 폴리올레핀-층상구조점토 나노복합체를 결정화시키고 유기용매를 제거시키는 단계를 거친다. As described above, the polyolefin resin is dissolved in the organic solvent, and the layered clay is dispersed to cool the melt having a uniform state to crystallize the polyolefin-layered clay nanocomposite and to remove the organic solvent.
본 발명에서는 유기용매로서 상온에서 폴리올레핀 수지에 대한 용해력이 없는 유기용매를 사용하므로, 가열하여 온도가 상승하면 폴리올레핀 수지에 대한 용해력을 나타내나, 실온 부근 온도 이하에서는 용해력이 없으므로, 냉각하는 과정에서 폴리올레핀-층상구조점토 나노복합체와 유기용매의 분리가 쉽게 이루어진다.In the present invention, since the organic solvent that does not have a dissolving power to the polyolefin resin at room temperature is used as the organic solvent, when the temperature rises by heating, the solvent exhibits a dissolving power to the polyolefin resin, but does not have a dissolving power at or below room temperature, so the polyolefin during the cooling process -Separation of layered clay nanocomposites and organic solvents is easy.
폴리올레핀 수지를 용해시키기 위하여 가열하는 과정에서 용매의 증기압이 높아져 휘발이 심해지므로, 가열 및 냉각 과정에서 밀폐된 고압반응기를 사용함으로써 용매의 손실을 방지할 수 있다. Since the vapor pressure of the solvent is increased in the process of heating to dissolve the polyolefin resin to increase the volatilization, it is possible to prevent the loss of the solvent by using a closed high pressure reactor in the heating and cooling process.
즉, 상기 용해물을 냉각하는 과정에서 용해물 내의 폴리올레핀-층상구조점토 나노복합체의 대부분이 결정화되므로, 유기용매와 이들 폴리올레핀-층상구조점토 나노복합체 결정분말이 포함된 현탁액 상태가 된다. 이때, 냉각은 자연냉각이나 강제냉각 등 어떠한 방법을 채택하더라도 무방할 것이다. 상기 현탁액을 여과 및 건조하여 유기용매를 회수하고, 유기용매가 제거된 폴리올레핀-층상구조점토 나노복합체 결정분말은 분쇄하여 분말을 얻을 수 있다. 상기 여과는 여과필터를 이용하거나, 원심력을 이용하여 유기용매를 1단계로 제거한 후, 분말을 가열하거나 감압하는 방법으로 건조하여 유기용매를 2단계로 완전히 제거하는 것이 바람직할 것이다. 또한, 상기 분리 제거된 유기용매를 회수하여 재사용할 수 있을 것이다.That is, since the majority of the polyolefin-layered clay nanocomposites in the melt are crystallized in the course of cooling the melt, the organic solvent and the polyolefin-layered clay nanocomposite crystal powder are in a suspension state. In this case, the cooling may be any method such as natural cooling or forced cooling. The suspension may be filtered and dried to recover an organic solvent, and the polyolefin-layered clay nanocomposite crystal powder from which the organic solvent is removed may be pulverized to obtain a powder. The filtration may be preferably performed by using a filtration filter or centrifugal force to remove the organic solvent in one step, and then drying the powder by heating or depressurizing to completely remove the organic solvent in two steps. In addition, the separated organic solvent may be recovered and reused.
상기한 바와 같이, 본 발명에 의하면 새로운 제조방법인 고압법을 이용하여 폴리올레핀-층상구조점토 나노복합체를 간단하게 제조할 수 있다.As described above, according to the present invention, a polyolefin-layered clay nanocomposite can be easily produced by using a high pressure method which is a new production method.
또한, 본 발명에 의하여 제조된 나노복합체에는 다량의 점토가 포함되어 있어 경제성이 탁월하며, 제조된 나노복합체는 기존의 나노복합체를 적용하던 분야에 다양하게 적용될 수 있다.In addition, the nanocomposite prepared according to the present invention contains a large amount of clay, so it is excellent in economic efficiency, and the prepared nanocomposite may be variously applied to the field where the conventional nanocomposites were applied.
이하 본 발명을 다음의 실시예를 통하여 구체적으로 설명하겠는바, 다음 실시예에 의하여 본 발명이 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following examples, which are not intended to limit the present invention.
실시예 1: 고농도 점토를 포함한 폴리올레핀 나노복합체 제조Example 1 Preparation of Polyolefin Nanocomposites Containing High Concentration Clay
고압반응용기에 고밀도 폴리에틸렌(HDPE) 알갱이 420g과 유기화 층상구조점토 280g 시클로헥산 1300g을 넣고, 진공펌프로 공기를 제거하여 반응기 내부 압력을 0.01 기압으로 하였다. 반응기를 가열하여 180℃, 10 bar로 유지하며 1시간동안 계속 교반하여 폴리에틸렌 알갱이와 층상구조점토를 시클로헥산에 용해시켰다. 420 g of high density polyethylene (HDPE) granules and 1,280 g of organic layered clay 280 g of cyclohexane were placed in a high pressure reaction vessel, and air was removed by a vacuum pump to make the reactor internal pressure to 0.01 atm. The reactor was heated and maintained at 180 ° C. and 10 bar, and the mixture was continuously stirred for 1 hour to dissolve polyethylene grains and layered clay in cyclohexane.
상기 반응기에 냉매를 통과시켜 온도를 50℃로 냉각시켰다. 냉각과정에서 나노복합체는 결정화하여 입자상태가 되어 용액이 현탁액 상태로 변화되었다. The refrigerant was passed through the reactor to cool the temperature to 50 ° C. During the cooling process, the nanocomposite crystallized to a particle state, and the solution changed to a suspension state.
상기 현탁액을 1000 메쉬의 필터를 통과시켜 폴리에틸렌-층상구조점토 복합체의 분말 응집체와 시클로헥산 혼합물을 여과하여 분리하였으며, 분말 응집체를 건조기로 이송하여 잔존한 시클로헥산을 완전히 제거하였다. The suspension was passed through a 1000 mesh filter to separate the powder aggregate and the cyclohexane mixture of the polyethylene-layered clay composite by filtration, and the powder aggregate was transferred to a drier to completely remove the remaining cyclohexane.
건조기에서 발생하는 기체를 냉동 응축기를 통과시켜 응축시킨 용매를 회수하였다. 상기 응축 회수 용매와 여과시킨 용매를 전량 회수하여 재사용하였으며, 상기 분말 응집체를 50 마력의 분쇄기로 분쇄하여 균일한 폴리에틸렌-층상구조점토 나노복합체를 얻었다.The gas generated in the dryer was passed through a refrigerated condenser to recover the condensed solvent. The entire condensation recovery solvent and the filtered solvent were recovered and reused, and the powder aggregate was pulverized with a 50 hp pulverizer to obtain a uniform polyethylene-layered clay nanocomposite.
도 3에는 분말화된 폴리에틸렌-층상구조점토 나노복합체의 분말 사진을 나타내었으며, 도 4는 상기 폴리에틸렌-층상구조점토 나노복합체의 TEM 사진을 나타내었다. 도 4에 의하면 층상구조점토의 층간에 폴리에틸렌이 삽입되어져 있음을 확인할 수 있다.Figure 3 shows a powder picture of the powdered polyethylene-layered clay nanocomposite, Figure 4 shows a TEM picture of the polyethylene-layered clay nanocomposite. According to Figure 4 it can be seen that the polyethylene is inserted between the layers of the layered clay.
도 1은 본 발명의 폴리올레핀-층상구조점토 나노복합체의 제조 공정을 개략적으로 나타낸 순서도이다.1 is a flow chart schematically showing the manufacturing process of the polyolefin-layered clay nanocomposites of the present invention.
도 2는 본 발명의 폴리올레핀-층상구조점토 나노복합체 제조의 공정의 일례를 개략적으로 도시한 도면이다.2 is a view schematically showing an example of a process for preparing a polyolefin-layered clay nanocomposite of the present invention.
도 3은 본 발명의 실시예 1에 의하여 제조된 폴리에틸렌-층상구조점토 나노복합체의 분말 사진을 나타낸 것이다. Figure 3 shows a powder photograph of the polyethylene-layered clay nanocomposite prepared by Example 1 of the present invention.
도 4는 본 발명의 실시예 1에 의하여 제조된 폴리에틸렌-층상구조점토 나노복합체의 TEM 사진을 나타낸 것이다.Figure 4 shows a TEM picture of the polyethylene-layered clay nanocomposite prepared by Example 1 of the present invention.
<도면의 주요부에 대한 설명><Description of main parts of drawing>
1 - 고분자 수지 알갱이 2 - 층상구조점토 3 - 유기용매1-Polymer resin granules 2-Layered clay 3-Organic solvent
10 - 고압반응기 11 - 가열(또는 감압) 건조기 12 - 분말저장고10-high pressure reactor 11-heating (or reduced pressure) dryer 12-powder reservoir
13 - 용매회수용 냉각기 14 - 필터여과기(또는 원심분리기)13-Solvent recovery cooler 14-Filter filter (or centrifuge)
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| JPH09208823A (en) * | 1996-01-29 | 1997-08-12 | Toyota Central Res & Dev Lab Inc | Polyimide composite powder and method for producing the same |
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| KR100840600B1 (en) | 2006-12-27 | 2008-06-23 | 한국생산기술연구원 | Manufacturing method of functional film using nano clay-containing ultra high molecular weight polyethylene resin and functional film using same |
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| JPH09208823A (en) * | 1996-01-29 | 1997-08-12 | Toyota Central Res & Dev Lab Inc | Polyimide composite powder and method for producing the same |
| KR20070071959A (en) * | 2005-12-30 | 2007-07-04 | 한국생산기술연구원 | Nanocomposites of poly (1-butene) and organoclays and methods for their preparation |
| KR100840600B1 (en) | 2006-12-27 | 2008-06-23 | 한국생산기술연구원 | Manufacturing method of functional film using nano clay-containing ultra high molecular weight polyethylene resin and functional film using same |
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