KR101170962B1 - Manufacturing Method of Monodispersed Cross-Linked Particle Using 1 Step Process - Google Patents
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Abstract
종래의 단분산 가교 입자를 제조하는 방법은 분산중합공정을 통해 1차적으로 단분산 비가교 입자 단량체를 제조하고, 2차적으로 이를 가교제와 함께 팽윤 시켜 중합하는 2차 공정을 통해 제조하는 것이 일반적이었다.
본 발명은 분산중합, 유화중합의 1차 중합 공정에 사슬이동제를 이용하여 높은 가교도를 갖는 단분산 고분자 입자를 제조하는 방법에 관한 것으로, 구체적으로는 용매에 분산 안정제를 투입하여 반응용매를 제조하는 단계, 라디칼 중합성 단량체에 사슬이동제, 가교제 및 개시제를 첨가하여 단량체 용액을 제조하는 단계 및 상기 반응용매와 상기 단량체 용액을 혼합후 승온 및 교반하여 중합 시키는 단계를 포함하는 단분산 가교 입자의 제조방법에 관한 것이다.Conventional methods for producing monodisperse crosslinked particles have been generally prepared through a secondary process in which monodisperse non-crosslinked particle monomers are prepared first through a dispersion polymerization process and secondly swelled together with a crosslinking agent to polymerize. .
The present invention relates to a method for producing monodisperse polymer particles having a high degree of crosslinking by using a chain transfer agent in a primary polymerization process of dispersion polymerization and emulsion polymerization. Specifically, a reaction solvent is prepared by adding a dispersion stabilizer to a solvent. Step, preparing a monomer solution by adding a chain transfer agent, a crosslinking agent and an initiator to the radical polymerizable monomer, and a method of producing monodisperse crosslinked particles comprising the step of mixing the reaction solvent and the monomer solution, and then heating and stirring the monomer solution. It is about.
Description
본 발명은 유화중합과 분산중합에 역 요오드 변환 중합(Reverse Iodine Transfer Polymerization, RITP) 방법을 도입하여 별도의 2차 공정 없이 높은 가교밀도를 갖는 단분산 고분자 입자를 제조하는 방법에 관한 것이다.
The present invention relates to a method for preparing monodisperse polymer particles having high crosslinking density without a separate secondary process by introducing Reverse Iodine Transfer Polymerization (RITP) in emulsion polymerization and dispersion polymerization.
가교된 고분자 입자는 가교가 되지 않은 고분자 입자에 비해 높은 열 안정성, 용매 안정성 및 탄성도를 가지며, 이러한 고분자 가교 입자의 크기 및 단분산도를 조절함에 따라 적용 범위가 커져 다양한 산업적 핵심 재료로서 사용이 가능하다. 현재까지 이러한 고분자 입자들은 각종 필름들의 광 확산재료, 엘시디 스페이서(LCD SPACER), 도전볼 등 광학 및 전기 전자 분야뿐만 아니라 약품 전달 캡슐 입자, MRI 조형재 등과 같은 의학 분야까지 다양한 분야에서 적용되고 있다. 또한 각종 무기물을 표면 및 입자의 내부에 도입하여 촉매로도 활용할 수도 있으며, 또한 구형이기 때문에 은폐력이 높은 유기 안료, 도료, 잉크, 화장품뿐만 아니라 전파 차폐용 군용 장비 등의 분야에도 적용이 가능하다. The crosslinked polymer particles have higher thermal stability, solvent stability, and elasticity than uncrosslinked polymer particles, and the range of application is increased by controlling the size and monodispersity of the polymer crosslinked particles. It is possible. Until now, such polymer particles have been applied in various fields from optical and electrical and electronic fields such as light diffusing materials, LCD spacers, conductive balls of various films, as well as medical fields such as drug delivery capsule particles and MRI molding materials. In addition, various inorganic materials may be introduced into the surface and inside of particles to be used as catalysts, and since they are spherical, they may be applied to fields such as military equipment for radio wave shielding as well as organic pigments, paints, inks and cosmetics, which have high hiding power.
산업적으로 널리 쓰이고 있는 고분자 입자의 제조 방법에는 일반적으로, 현탁중합, 유화중합, 분산중합, 시드중합 등이 이용되고 있다. In general, suspension polymerization, emulsion polymerization, dispersion polymerization, seed polymerization and the like are used in the production of polymer particles widely used in industry.
현탁중합의 경우 단량체 혼합물을 분산안정제가 함유된 액상에 기계적, 물리적 방법에 의해 수십~ 수백 마이크론 크기로 단량체 액적을 분산시켜 중합함으로써 제조 할 수 있으나, 입도 크기의 분포가 넓어져 단분산 조절이 어렵다는 단점이 있다. In the case of suspension polymerization, the monomer mixture can be prepared by dispersing the monomer droplets in the liquid phase containing the dispersion stabilizer in the size of several tens to hundreds of microns by mechanical and physical methods. There are disadvantages.
유화중합의 경우 통상적으로 제조되는 입자의 크기가 1마이크론을 넘기가 어려우며, 가교입자를 제조하기 위해서는 통상 가교제의 함량이 5%이상을 넘지 않고 있다.In the case of emulsion polymerization, the size of particles generally produced is difficult to exceed 1 micron, and in order to prepare crosslinked particles, the content of the crosslinking agent is usually not more than 5%.
분산중합의 경우는 수 마이크론 크기의 높은 단분산성을 갖는 고분자 입자를 제조할 수 있는 방법으로 널리 쓰이고 있으며, 일반적으로 주로 유기용제상에서 중합을 진행한다. 연속상 내에 존재하는 안정제와 보조 안정제에 의해 안정화가 되어 중합반응이 진행됨에 따라 구형의 입자를 형성하게 된다. 한국공개특허 제2003-0056100호는 분산중합을 이용하여 가교 단량체를 단량체 전제 중향에 대하여 최소 10중량 퍼센트 이상 투입하여 높은 가교밀도를 갖는 마이크론 크기의 단분산 입자를 제조하는 방법을 소개하였다. 그러나 가교제가 들어간 분산중합의 경우 반응 매질 내에 형성되는 핵이 가교가 되어 있어 팽윤이 어려워, 단량체를 흡수하여 성장하기 어렵기 때문에, 침전되는 올리고머나 또 다른 입자의 핵들이 기존 입자위에 침전되어 연속적으로 적층되며, 가교로 인한 응집이 일어나 구형이 아닌 입자가 얻어지기 쉽다는 문제점이 있다.In the case of dispersion polymerization, it is widely used as a method for producing polymer particles having a high monodispersity of several microns. Generally, polymerization is mainly performed on an organic solvent. It is stabilized by a stabilizer and an auxiliary stabilizer present in the continuous phase, thereby forming spherical particles as the polymerization proceeds. Korean Laid-Open Patent Publication No. 2003-0056100 introduced a method for preparing micron-sized monodisperse particles having a high crosslinking density by dispersing a crosslinking monomer by at least 10% by weight based on monomer total weight. However, in the case of dispersion polymerization containing a crosslinking agent, the nuclei formed in the reaction medium are crosslinked, and swelling is difficult, and it is difficult to absorb and grow monomers. Thus, the nuclei of precipitated oligomers or other particles are precipitated on the existing particles and continuously There is a problem in that the particles are laminated and coagulation due to crosslinking occurs, so that non-spherical particles are easily obtained.
시드중합의 경우에는 수마이크론 크기의 높은 가교 밀도를 갖는 고분자 입자를 제조할 수 있는 방법으로, 분산중합이나 유화중합을 통해 1차적인 비가교 시드 입자를 제조 한 후 안정제가 포함되어 있는 물 수용액상에 단량체 및 가교제 혼합물과 함께 교반시켜 팽윤 및 중합 공정을 거쳐 입자를 형성하게 된다. 한국공개특허 10-2007-050818호는 1차 공정으로 시드 입자를 분산중합을 통하여 제조 한 후 2차공정으로 제조된 시드 입자를 단량체와 가교 단량체로 팽윤시켜 중합하는 다단계의 시드 중합 공정을 통해 가교 단량체의 함량이 전체 중량에 10%이상을 갖는 높은 가교 밀도를 갖는 단분산 입자의 제조하는 방법을 소개하였다. In the case of seed polymerization, a method capable of producing a polymer particle having a high crosslinking density of several microns is prepared. The first non-crosslinked seed particle is prepared through dispersion polymerization or emulsion polymerization, and then a water solution phase containing a stabilizer is used. The mixture is stirred with the monomer and crosslinking agent mixture to form particles through a swelling and polymerization process. Korean Patent Publication No. 10-2007-050818 discloses crosslinking through a multi-step seed polymerization process in which seed particles are prepared through dispersion polymerization in a first step and then swelled and polymerized seed particles prepared in a second step with a monomer and a crosslinking monomer. A method for producing monodisperse particles having a high crosslinking density having a monomer content of 10% or more in total weight has been introduced.
그러나 시드 입자의 세정 및 재 분산, 여러 단계에 걸친 팽윤 과정에 대부분 많은 시간이 소비되고 복잡한 공정이 필요하며, 그에 따른 제조비용 상승이 불가피 하다는 단점이 있다. However, the cleaning and redispersion of seed particles, the swelling process of several stages, most of the time is required to spend a lot of time and complicated processes, resulting in inevitable increase in manufacturing costs.
따라서, 단순한 1차 공정을 통해 나노미터 ~ 마이크로미터의 다양한 크기 범위와 단분산 입도 분포를 갖는 높은 가교밀도의 고분자 입자의 제조 방법은 알려지지 않은 실정이다.
Therefore, there is no known method for producing high crosslinking density polymer particles having various size ranges of monometer to micrometer and monodisperse particle size distribution through a simple primary process.
이에 본 발명자들은 상기 문제점을 해결하고자 연구, 노력한 결과 가교제를 사용한 중합 과정에 소량의 사슬이동제를 첨가하면 초기 반응 시에 입자들의 응집 및 비구형화를 효과적으로 억제한다는 사실을 발견하였으며 이를 분산중합과 유화중합에 적용하여, 높은 가교밀도를 갖는 구형의 고분자 입자를 통해 성공적으로 제조함으로써 본 발명을 완성하게 되었다. 즉, 본 발명은 별도의 2차 공정 없이 분산중합, 유화중합만의 1차 공정을 통해서 높은 가교도를 갖는 단분산 고분자 입자의 효율적인 제조 방법을 제공하는 것을 목적으로 한다.
Therefore, the present inventors have found that the addition of a small amount of chain transfer agent to the polymerization process using a crosslinking agent effectively inhibits the aggregation and non-spherization of the particles during the initial reaction. The present invention has been completed by successfully preparing through spherical polymer particles having a high crosslinking density. That is, an object of the present invention is to provide an efficient method for producing monodisperse polymer particles having a high degree of crosslinking through a primary process of dispersion polymerization and emulsion polymerization alone without a separate secondary process.
종래의 단분산 가교 입자를 제조하는 방법은 분산중합공정을 통해 1차적으로 단분산 비가교 입자 단량체를 제조하고, 2차적으로 이를 가교제와 함께 팽윤 시켜 중합하는 2차 공정을 통해 제조하는 것이 일반적이었다.Conventional methods for producing monodisperse crosslinked particles have been generally prepared through a secondary process in which monodisperse non-crosslinked particle monomers are prepared first through a dispersion polymerization process and secondly swelled together with a crosslinking agent to polymerize. .
본 발명은 분산중합과 유화중합의 1차 중합 공정에 사슬이동제를 이용하여 높은 가교도를 갖는 단분산 고분자 입자를 제조하는 방법에 관한 것으로, 구체적으로는 용매에 분산 안정제를 투입하여 반응용매를 제조하는 단계, 라디칼 중합성 단량체에 사슬이동제, 가교제 및 개시제를 첨가하여 단량체 용액을 제조하는 단계 및 상기 반응용매와 상기 단량체 용액을 혼합한 후 승온 및 교반하여 중합 시키는 단계를 포함하는 단분산 가교 입자의 제조방법에 관한 것이다.
The present invention relates to a method for producing monodisperse polymer particles having a high degree of crosslinking by using a chain transfer agent in a primary polymerization process of dispersion polymerization and emulsion polymerization. Specifically, a reaction solvent is prepared by adding a dispersion stabilizer to a solvent. Preparing a monomer solution by adding a chain transfer agent, a crosslinking agent, and an initiator to the radical polymerizable monomer, and mixing the reaction solvent with the monomer solution, followed by polymerization by heating and stirring. It is about a method.
본 발명의 단분산 가교 고분자 입자의 제조 방법은 기존에 알려진 고분자 현탁중합방법을 거치는 방법에 비해 제조된 입자의 크기와 단분산 조절이 가능하다는 장점이 있다. 또한 비가교 시드 입자의 제조 후 가교제가 첨가된 단량체와 함께 팽윤시켜 제조하는 2단계 시드 중합 공정 방법에 비해 제조 시간 및 생산 단가가 저렴하며, 현탁중합과, 시드중합 공정으로 얻어진 고분자 가교 입자에 비해 높은 내용제성과 열 안정성을 갖고 있어 기존의 공정보다 시간적, 비용적, 물성적 측면에서 유리하다. 따라서 단분산 가교 고분자 입자 및 이를 응용하는 광 확산재료, 엘시디 스페이서(LCD SPACER), 도전볼, 약품 전달 캡슐 입자, MRI 조형재 등의 분야에서 파급효과가 클 것으로 기대된다.
The method for producing monodisperse crosslinked polymer particles of the present invention has the advantage that the size and monodispersity of the prepared particles can be controlled as compared to a method known through a known polymer suspension polymerization method. In addition, the manufacturing time and production cost are lower than the two-step seed polymerization process prepared by swelling together with the monomer to which the crosslinking agent is added after the preparation of the non-crosslinked seed particles. It has high solvent resistance and thermal stability, which is advantageous in terms of time, cost, and physical properties over conventional processes. Therefore, the monodisperse crosslinked polymer particles, light diffusion material, LCD spacer, conductive ball, drug delivery capsule particles, MRI molding material and the like are expected to have a large ripple effect.
도 1은 실시예 1에서 제조한 단분산 가교 입자의 SEM 사진이다.
도 2는 실시예 10에서 제조한 단분산 가교 입자의 SEM 사진이다.
도 3은 비교예 1에서 제조한 입자의 SEM 사진이다.
도 4는 실시예 1과 비교예 2에서 얻어진 가교 입자의 입도 분포를 비교한 PSA 그래프이다.1 is a SEM photograph of the monodisperse crosslinked particles prepared in Example 1. FIG.
2 is a SEM photograph of the monodisperse crosslinked particles prepared in Example 10.
3 is a SEM photograph of the particles prepared in Comparative Example 1.
4 is a PSA graph comparing particle size distributions of the crosslinked particles obtained in Example 1 and Comparative Example 2. FIG.
본 발명은 분산중합과 유화중합의 1차 중합 공정에 사슬이동제를 이용하여 높은 가교도를 갖는 단분산 고분자 입자를 제조하는 방법에 관한 것으로, 구체적으로는 용매에 분산 안정제를 투입하여 반응용매를 제조하는 단계, 라디칼 중합성 단량체에 사슬이동제, 가교제 및 개시제를 첨가하여 단량체 용액을 제조하는 단계 및 상기 반응용매와 상기 단량체 용액을 혼합한 후 승온 및 교반하여 중합 시키는 단계를 포함하는 단분산 가교 입자의 제조방법에 관한 것이다.The present invention relates to a method for producing monodisperse polymer particles having a high degree of crosslinking by using a chain transfer agent in a primary polymerization process of dispersion polymerization and emulsion polymerization. Specifically, a reaction solvent is prepared by adding a dispersion stabilizer to a solvent. Preparing a monomer solution by adding a chain transfer agent, a crosslinking agent, and an initiator to the radical polymerizable monomer, and mixing the reaction solvent with the monomer solution, followed by polymerization by heating and stirring. It is about a method.
이하에서 본 발명에 따른 단분산 고분자 가교 입자의 제조방법을 보다 상세하게 설명한다.Hereinafter, a method for preparing monodisperse polymer crosslinked particles according to the present invention will be described in more detail.
상기 반응용매를 제조하는 단계에서는 용매에 분산 안정제를 반응기에 투입한 후, 승온 및 교반을 통해 분산 안정제를 용액에 완전히 용해시킨다. 상기 단계에서는 분산 안정제 뿐 아니라 계면활성제도 추가로 투입될 수 있다.In the step of preparing the reaction solvent, the dispersion stabilizer is added to the reactor in a solvent, and then the dispersion stabilizer is completely dissolved in the solution by heating and stirring. In this step, a surfactant may be added as well as a dispersion stabilizer.
상기 단량체 용액을 제조하는 단계는 라디칼 중합성 단량체에 사슬이동제, 가교제, 개시제를 첨가하여 교반을 통해 완전히 용해시키는 단계이다.The step of preparing the monomer solution is a step of adding a chain transfer agent, a crosslinking agent, an initiator to the radical polymerizable monomer to completely dissolve through stirring.
상기 반응용매와 단량체 용액을 혼합한 후 승온 및 교반하여 중합 시키는 단계는 중합을 통하여 가교된 단분산 고분자 입자를 제조하는 단계로, 상기 단계에서 제조된 단량체 용액을 반응용매에 투입하여 중합을 실시하여, 높은 단분산도와 가교도를 갖는 구형의 고분자 입자를 제조할 수 있다. 이 때 촉매를 추가로 적용하면 입자 수득률과 단분산도를 더욱 향상시킬 수 있다. 상기 중합온도와 교반 속도는 각각 30 ~ 85℃, 50 ~ 300rpm 범위에 있는 것이 바람직하다. 개시제, 라디칼 중합성 단량체의 양 및 반응 조건에 따라 단분산 고분자 가교 입자의 크기 조절이 가능하며 0.1 ~ 100㎛ 범위의 크기로 제조가 가능하다. 또한 상기 중합과정은 통상 12 ~ 24시간이 소요된다.The step of polymerization by mixing the reaction solvent and the monomer solution and then heating and stirring is to prepare a cross-dispersed monodisperse polymer particles through polymerization, the polymerization of the monomer solution prepared in the step into the reaction solvent , Spherical polymer particles having high monodispersity and crosslinking degree can be produced. In this case, further application of a catalyst may further improve particle yield and monodispersity. The polymerization temperature and the stirring speed are preferably in the range of 30 ~ 85 ℃, 50 ~ 300rpm, respectively. The size of the monodisperse polymer cross-linked particles can be controlled according to the amount of the initiator, the radical polymerizable monomer, and the reaction conditions, and can be manufactured in the range of 0.1 to 100 μm. In addition, the polymerization process usually takes 12 to 24 hours.
이하 본 발명에서 사용되는 구성성분을 구체적으로 설명한다.
Hereinafter, the components used in the present invention will be described in detail.
(1)사슬이동제(1) chain transfer agents
본 발명의 단분산 고분자 가교 입자의 제조에 사용될 수 있는 사슬이동제는 특별히 제한되지 않는다.The chain transfer agent that can be used in the preparation of the monodisperse polymer crosslinked particles of the present invention is not particularly limited.
사용가능한 사슬이동제로는, 유기 아이오딘, 무기 아이오딘 또는 분자 아이오딘 등을 사용하며, 더욱 구체적으로는 요오드, 포타슘아이오딘, 소디움아이오딘, 리튬아이오딘, 브롬아이오딘, 아이오딘모노크로라이드, 마그네슘아이오디드, 포스포러스트아이오디드, 및 알킬아이오디드로 이루어진 군에서 선택된 1종 이상의 화합물이 사용될 수 있다.Examples of the chain transfer agent that can be used include organic iodine, inorganic iodine or molecular iodine, and more specifically iodine, potassium iodine, sodium iodine, lithium iodine, bromine iodine, iodine monochloride At least one compound selected from the group consisting of, magnesium iodide, phosphorus iodide, and alkyl iodide may be used.
상기 사슬 이동제는 바람직하게는 라디칼 중합성 단량체 100 중량부에 대해서 0.001 ~ 50 중량부 사용될 수 있으며, 더욱 바람직하게는 0.01 ~ 0.1 중량부로 사용될 수 있다. 사슬 이동제의 사용량에 따라 입자의 구형도와 표면 거칠기를 조절할 수 있다.
The chain transfer agent may preferably be used in an amount of 0.001 to 50 parts by weight, and more preferably 0.01 to 0.1 parts by weight, based on 100 parts by weight of the radical polymerizable monomer. The sphericity and surface roughness of the particles can be adjusted according to the amount of chain transfer agent used.
(2) 라디칼 중합성 단량체(2) radically polymerizable monomers
본 발명의 단분산 고분자 가교 입자의 제조에 사용될 수 있는 라디칼 중합성 단량체는 특별히 제한되지 않는다. 사용가능한 라디칼 중합성 단량체로는, 구체적으로는 스티렌, p-메틸스티렌, m-메틸스티렌, p-에틸스티렌, m-에틸스티렌, p-클로로스티렌, m-클로로스티렌, p-클로로메틸스티렌, m-클로로메틸스티렌, 스티렌설포닉에시드, p-t-부톡시스티렌, m-t-부톡시스티렌, 플로로스티렌, 알파메틸스티렌, 비닐톨루엔, 클로로스티렌의 방향족 비닐계 단량체; 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 스테아릴(메타)아크릴레이트, 벤질(메타)아크릴레이트, 글리시딜(메타)아크릴레이트, 플루오르에틸아크릴레이트, 트리플루오르에틸메타크릴레이트, 펜타플루오르프로필메타크릴레이트, 플로로에틸메타크릴레이트, 헥사플루오르부틸(메타)아크릴레이트, 헥사플루오르이소프로필메타크릴레이트, 퍼플루오르알킬아크릴레이트, 옥타플루오르페닐메타크릴레이트 등의 (메타)아크릴레이트계 단량체; 및 비닐아세테이트, 비닐프로피오네이트, 비닐부틸레이트, 비닐에테르, 알릴부틸에테르, 알릴글리시딜에테르, (메타)아크릴산, 말레산과 같은 불포화 카르복시산, 알킬(메타)아크릴아미드, (메타)아크릴로니트릴의 시안화 비닐계 단량체 등을 들 수 있다. 본 발명에서는 상기 라디칼 중합성 단량체를 단독 혹은 2종 이상 혼합하여 사용할 수 있다. 본 발명에 있어서 (메타)아크릴레이트는 메타크릴레이트 또는 아크릴레이트를 의미한다.The radically polymerizable monomer which can be used for producing the monodisperse polymer crosslinked particles of the present invention is not particularly limited. Specific radical polymerizable monomers that can be used include styrene, p-methylstyrene, m-methylstyrene, p-ethylstyrene, m-ethylstyrene, p-chlorostyrene, m-chlorostyrene, p-chloromethylstyrene, aromatic vinyl monomers such as m-chloromethyl styrene, styrene sulfonic acid, pt-butoxy styrene, mt-butoxy styrene, fluoro styrene, alpha methyl styrene, vinyl toluene and chloro styrene; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylic Rate, fluoroethyl acrylate, trifluoroethyl methacrylate, pentafluoropropyl methacrylate, fluoroethyl methacrylate, hexafluorobutyl (meth) acrylate, hexafluoroisopropyl methacrylate, perfluoroalkyl acrylate (Meth) acrylate monomers such as octafluorophenyl methacrylate; And vinyl acetate, vinyl propionate, vinyl butyrate, vinyl ether, allyl butyl ether, allyl glycidyl ether, (meth) acrylic acid, unsaturated carboxylic acids such as maleic acid, alkyl (meth) acrylamide, (meth) acrylonitrile And vinyl cyanide monomers. In this invention, the said radically polymerizable monomer can be used individually or in mixture of 2 or more types. In the present invention, (meth) acrylate means methacrylate or acrylate.
특히, 라디칼 중합성 단량체는 (메타)아크릴레이트계 단량체 혹은 이와 공중합체를 형성할 수 있는 방향족 비닐계 단량체인 것이 바람직하다.In particular, the radically polymerizable monomer is preferably a (meth) acrylate monomer or an aromatic vinyl monomer capable of forming a copolymer thereof.
상기 라디칼 중합성 단량체의 사용량은 반응용매 및 단량체 용액 100 중량부에 대하여 1 ~ 50 중량부, 바람직하게는 5 ~ 20 중량부이다.
The radical polymerizable monomer is used in an amount of 1 to 50 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the reaction solvent and the monomer solution.
(3) 가교제(다관능성 가교 단량체) (3) crosslinking agent (polyfunctional crosslinking monomer)
가교제로 쓰이는 다관능성 가교 단량체로는 디비닐벤젠, 1,4-디비닐옥시부탄, 디비닐술폰, 디알릴프탈레이트, 디알릴아크릴아미드, 트리알릴(이소)시아누레이트, 트리알릴트리멜리테이트 등의 알릴 화합물, 헥산디올디아크릴레이트, 에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 트리메틸렌프로판트리메타크릴레이트, 1,3-부탄디올메타크릴레이트, 1,6-헥산디올디메타크릴레이트, 펜타에릴트리톨테트라(메타)아크릴레이트, 펜타에릴트리톨트리(메타)아크릴레이트, 펜타에릴트리톨디(메타)아크릴레이트, 트리메틸올프로판, 트리(메타)아크릴레이트, 디펜타에릴트리톨헥사(메타)아크릴레이트, 디펜타에릴트리톨펜타(메타)아크릴레이트, 글리세롤트리(메타)아크릴레이트, 알릴(메타)아크릴레이트 등을 들 수 있다. 본 발명에서는 상기 다관능성 가교 단량체를 단독 혹은 2종 이상 혼합하여 사용할 수 있다.Examples of the polyfunctional crosslinking monomer used as the crosslinking agent include divinylbenzene, 1,4-divinyloxybutane, divinyl sulfone, diallyl phthalate, diallyl acrylamide, triallyl (iso) cyanurate, triallyl trimellitate, and the like. Allyl compound, hexanediol diacrylate, ethylene glycol dimethacrylate, diethylene glycol methacrylate, triethylene glycol dimethacrylate, trimethylene propane trimethacrylate, 1,3-butanediol methacrylate, 1 , 6-hexanediol dimethacrylate, pentaaryl tritol tetra (meth) acrylate, pentaaryl tritol tri (meth) acrylate, pentaaryl tritol di (meth) acrylate, trimethylolpropane, tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, allyl (meth) acrylate Etc. can be mentioned. In this invention, the said polyfunctional crosslinking monomer can be used individually or in mixture of 2 or more types.
상기 2단계에서 투입되는 다관능성 가교 단량체는 라디칼 중합성 단량체 100 중량부에 대하여 1 ~ 100 중량부, 바람직하게는 5 ~ 30 중량부이며, 가교 단량체의 양에 따라 고분자 입자의 가교도가 결정된다.
The multifunctional crosslinking monomer added in
(4) 개시제(4) initiator
개시제로서는 벤조일퍼옥사이드, 라우릴퍼옥사이드, 큐멘하이드로퍼옥사이드, 메틸에틸케톤퍼옥사이드, t-부틸하이드로퍼옥사이드, t-부틸퍼옥시-2-에틸헥사노에이트, t-헥실퍼옥시-2-에틸헥사노에이트, 1,1,3,3-테트라메틸부틸퍼옥시-2-에틸헥사노에이트 등의 퍼옥사이드계; 2,2'-아조비스이소부티로니트릴, 2,2'-아조비스2,4-디메틸발레로니트릴, 2,2'-아조비스2-메틸이소부티로니트릴 등의 아조계 반응 개시제 및 암모늄퍼설페이트, 포타슘퍼설페이트, 소듐퍼설페이트, 암모늄바이설페이트, 소듐바이설페이트 등의 설페이트계 반응 개시제 및 이들의 혼합물을 사용할 수 있다.As an initiator, benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl hydroperoxide, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2- Peroxides such as ethylhexanoate and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate; Azo reaction initiators, such as 2,2'- azobisisobutyronitrile, 2,2'- azobis2, 4- dimethylvaleronitrile, and 2,2'- azobis 2-methylisobutyronitrile, and ammonium Sulfate-based reaction initiators such as persulfate, potassium persulfate, sodium persulfate, ammonium bisulfate, sodium bisulfate, and mixtures thereof can be used.
제2단계에서 투입되는 개시제의 사용량은 상기 반응용매 및 단량체 용액의 합계 100 중량부에 대하여 0.05 ~ 10 중량부, 바람직하게는 0.1 ~ 3 중량부가 될 수 있다.
The amount of the initiator added in the second step may be 0.05 to 10 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the total of the reaction solvent and the monomer solution.
(5) 분산안정제(5) dispersion stabilizer
분산안정제로서는 메틸셀룰로스, 에틸셀룰로스, 하이드록시프로필셀룰로스 등의 셀룰로스 유도체, 폴리비닐알콜, 폴리비닐메틸에테르, 폴리아크릴산, 폴리비닐아세테이트, 폴리비닐피롤리돈, 비닐피롤리돈과 비닐아세테이트의 공중합체 등을 들 수 있으며, 바람직하게는 폴리비닐피롤리돈과 폴리비닐알콜 등이 있다. 제 1단계에서 사용되는 분산안정제의 사용량은 상기 반응용매 및 단량체 용액의 합계 100 중량부에 대하여 0.5 ~ 15 중량부, 바람직하게는 1 ~ 6 중량부이다.
Examples of the dispersion stabilizer include cellulose derivatives such as methyl cellulose, ethyl cellulose and hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl methyl ether, polyacrylic acid, polyvinylacetate, polyvinylpyrrolidone, vinylpyrrolidone and vinyl acetate. Etc., Preferably, polyvinylpyrrolidone, polyvinyl alcohol, etc. are mentioned. The amount of the dispersion stabilizer used in the first step is 0.5 to 15 parts by weight, preferably 1 to 6 parts by weight, based on 100 parts by weight of the total of the reaction solvent and the monomer solution.
(6) 계면활성제(6) surfactant
계면활성제로는 일반적으로 유화중합 등에서 사용되는 것으로서 수용성으로 계면활성제의 역할을 수행할 수 있는 것이면 모두 사용될 수 있다. 특별히 한정되는 것은 아니나, 바람직하게는 나트륨도데실설페이트(SDS), 나트륨도데실벤젠설포네이트, 나트륨도데실나프탈렌설페이트, 디알킬벤젠알킬설페이트 및 설포네이트; 아비트산; 헥사데칸설포네이트 중에서 1 이상 선택될 수 있다. 보다 바람직하게는 유화제는, 나트륨도데실벤젠설포네이트, 디알킬벤젠알킬설포네이트, 헥사데칸설포네이트 중에서 1 이상 선택될 수 있으며, 유화중합의 종류인 무유화유화중합과, modified soap-free 유화중합일 경우 계면활성제는 첨가되지 않는다. 제 1단계에서 사용되는 계면활성제의 사용량은 상기 반응용매 및 단량체 용액의 합계 100 중량부에 대하여 0.05 ~ 15 중량부, 바람직하게는 0.1 ~ 1 중량부이다.
As the surfactant, generally used in emulsion polymerization and the like can be used as long as it can perform the role of the surfactant in water solubility. Although not specifically limited, Preferably sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate, sodium dodecyl naphthalene sulfate, dialkylbenzene alkyl sulfate, and sulfonate; Bibitic acid; One or more of hexadecanesulfonate may be selected. More preferably, the emulsifier may be at least one selected from sodium dodecylbenzenesulfonate, dialkylbenzenealkylsulfonate, and hexadecanesulfonate, and may be emulsified oil-free emulsion polymerization and modified soap-free emulsification. If combined, no surfactant is added. The amount of the surfactant used in the first step is 0.05 to 15 parts by weight, preferably 0.1 to 1 part by weight based on 100 parts by weight of the total of the reaction solvent and the monomer solution.
(7) 촉매(7) catalyst
촉매로는 하이드로 퍼옥사이드, 큐멘하이드로퍼옥사이드, 부틸하이드로퍼옥사이드, 하이드로메틸하이드로퍼옥사이드, 또는 아세틸하이드로퍼옥사이드 중에서 선택된 1종 또는 2종 이상이 사용될 수 있다. As the catalyst, one or two or more selected from hydroperoxide, cumene hydroperoxide, butyl hydroperoxide, hydromethylhydroperoxide, and acetyl hydroperoxide may be used.
상기 촉매는 바람직하게는 상기 라디칼 중합성 단량체 100중량부에 대해서 0.001 ~ 5 중량부로 사용될 수 있다. 촉매의 사용량이 너무 적으면 반응속도가 너무 느려, 입자 수득율이 크게 떨어지는 현상이 발생하고 너무 많으면 반응 속도가 빨라져 입자들이 뭉치는 현상이 발생하여 안정된 가교 입자를 얻을 수 없다. 더욱 바람직하게는 0.01 ~ 0.05 중량부로 사용될 수 있다.
The catalyst may preferably be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the radical polymerizable monomer. If the amount of the catalyst is too small, the reaction rate is too slow, and the yield of particles is greatly decreased. If the amount of the catalyst is too high, the reaction rate is increased, so that the particles are agglomerated, so that stable crosslinked particles cannot be obtained. More preferably 0.01 to 0.05 parts by weight can be used.
본 발명의 중합반응에도, 통상의 분산중합과 유화 중합반응에 사용되는 공지의 첨가제가 통상적인 용도와 방법으로 부가 사용될 수 있다. 부틸 알데히드, 클리클로로에틸렌, 퍼클로로에틸렌, 아세트알데히드 또는 머캅탄 등의 중합 조절제나 ph조절제, 가교 결합제, 스케일 방지제, 염료 및 안료 등이 필요에 따라 부가 될 수 있다.In addition to the polymerization reaction of the present invention, known additives used in conventional dispersion polymerization and emulsion polymerization can be added and used in conventional applications and methods. Polymerization regulators such as butyl aldehyde, cchlorethylene, perchloroethylene, acetaldehyde or mercaptan, ph regulators, crosslinking agents, anti-scaling agents, dyes and pigments and the like may be added as necessary.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하기로 하나, 하기한 실시예는 본 발명을 예증하기 위한 것일 뿐, 본 발명을 제한하는 것은 아님을 이해하여만 할 것이다.
Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples are merely to illustrate the present invention, but it should be understood that the present invention is not limited thereto.
실시예Example 1 One
(a) 반응용매 제조(a) Preparation of reaction solvent
교반기가 부착된 300ml 3구 분리형 반응기에서 메탄올 100g, 폴리비닐피롤리돈(K-90) 2g을 투입하였다. 10 ~ 30℃의 온도에서 100rpm 으로 30분 교반하여 메탄올에 폴리비닐피롤리돈을 완전히 용해시켜 반응용매를 제조하였다.In a 300 ml three-necked separate reactor equipped with a stirrer, 100 g of methanol and 2 g of polyvinylpyrrolidone (K-90) were added thereto. The reaction solvent was prepared by completely dissolving polyvinylpyrrolidone in methanol by stirring at 100 rpm for 30 minutes at a temperature of 10 to 30 ° C.
(b) 단량체 용액 제조(b) Preparation of monomer solution
교반기가 부착된 100ml 2구 분리형 반응기에서 라디칼 중합성 단량체로서 메틸메타크릴레이트 8g과 가교제인 다관능성 가교 단량체로서 에틸렌글리콜디메타크릴레이트 2g을 투입 하여 교반을 통해 완전히 용해시켰다. 개시제로서 2,2′-아조비스이소부틸로니트릴(AIBN) 0.2g, 사슬이동제로서 요오드 0.005g을 다관능성 투입한 후 상온에서 100rpm의 교반을 통해 완전히 용해시켜 단량체 용액을 제조하였다. In a 100 ml two-necked separate reactor equipped with a stirrer, 8 g of methyl methacrylate as a radical polymerizable monomer and 2 g of ethylene glycol dimethacrylate as a multifunctional crosslinking monomer as a crosslinking agent were added and completely dissolved by stirring. A monomer solution was prepared by completely dissolving 0.2 g of 2,2′-azobisisobutylonitrile (AIBN) as an initiator and 0.005 g of iodine as a chain transfer agent, followed by 100 rpm stirring at room temperature.
(c) 중합 실시 과정(c) Polymerization Process
상기 반응용매가 투입된 300ml 분리형 반응기의 내부에 질소를 계속적으로 충진시켜 반응기 내부의 산소를 제거하고 질소로 치환 시킨 후 200rpm으로 교반과 함께 반응기를 약 60℃로 승온 시켰다. 상기 제조된 단량체 용액과 촉매인 H2O2 1g을 반응기 내에 투입하여 12시간 가량 중합을 실시하였다. 12시간 후 제조된 입자를 세척하여 SEM 과 PSA(particle size analyzer)를 통해 입자의 표면과 단분산도를 확인하였다. SEM과 PSA의 결과를 각각 도 1, 도 4에 나타내었다.
Nitrogen was continuously charged into the 300 ml separation type reactor in which the reaction solvent was added to remove oxygen in the reactor, replaced with nitrogen, and the reactor was heated to about 60 ° C. with stirring at 200 rpm. The monomer solution prepared above and 1 g of H 2 O 2 , which is a catalyst, were charged into the reactor, and polymerization was performed for about 12 hours. After 12 hours, the prepared particles were washed, and the surface and monodispersity of the particles were checked by SEM and PSA (particle size analyzer). The results of SEM and PSA are shown in FIGS. 1 and 4, respectively.
실시예Example 2 2
용매로 메탄올 대신 에탄올을 사용한 것 이외에는 상기 실시예 1과 동일하게 진행하였다. The same procedure as in Example 1 was carried out except that ethanol was used instead of methanol.
실시예Example 3 3
라디칼 중합성 단량체를 메틸메타크릴레이트 대신 스티렌을 사용한 것 이외에는 상기 실시예 1과 동일하게 진행하였다. The radically polymerizable monomer was proceeded in the same manner as in Example 1 except that styrene was used instead of methyl methacrylate.
실시예Example 4 4
다관능성 가교 단량체로 에틸렌글리콜디메타크릴레이트 대신 다이비닐벤젠을 사용한 것 이외에는 상기 실시예 1과 동일하게 진행하였다.
The procedure was the same as in Example 1 except that divinylbenzene was used instead of ethylene glycol dimethacrylate as the polyfunctional crosslinking monomer.
실시예Example 5 5
다관능성 가교 단량체 에틸렌글리콜디메타크릴레이트 대신 알릴메타크릴레이트 사용한 것 이외에는 상기 실시예 1과 동일하게 진행하였다.
The procedure was the same as in Example 1 except that allyl methacrylate was used instead of the polyfunctional crosslinking monomer ethylene glycol dimethacrylate.
실시예Example 6 6
개시제 2,2′-아조비스이소부틸로니트릴(AIBN) 대신 벤조일퍼옥사이드(BPO)를 사용한 것 이외에는 상기 실시예 1과 동일하게 진행하였다.
The procedure was the same as in Example 1 except that benzoyl peroxide (BPO) was used instead of
실시예Example 7 7
단량체 용액에 용해된 요오드 0.005g 대신 0.001g을 투입한 것 이외에는 상기 실시예 1과 동일하게 진행하였다.
It proceeded in the same manner as in Example 1 except that 0.001 g was added instead of 0.005 g of iodine dissolved in the monomer solution.
실시예Example 8 8
사용된 사슬이동제를 요오드 대신 브롬아이오디드를 투입한 것 이외에는 상기 실시예 1과 동일하게 진행하였다.
The chain transfer agent was used in the same manner as in Example 1 except that bromine iodide was added instead of iodine.
실시예Example 9 9
H2O2를 사용하지 않고 반응을 실시한 것 이외에는 상기 실시예 1과 동일하게 진행하였다.
It proceeded in the same manner as in Example 1 except that the reaction was carried out without using H 2 O 2 .
실시예Example 10 10
(a) 반응용매 제조(a) Preparation of reaction solvent
교반기가 부착된 300ml 3구 분리형 반응기에서 메탄올 70g, 증류수 20g, 폴리비닐피롤리돈(K-90) 1g을 투입하였다. 상온 하의 온도에서 100rpm 으로 30분 교반하여 메탄올, 증류수 혼합 용매에 폴리비닐피롤리돈을 완전히 용해시켜 반응용매를 제조하였다.In a 300 ml three-neck separate reactor equipped with a stirrer, 70 g of methanol, 20 g of distilled water, and 1 g of polyvinylpyrrolidone (K-90) were added thereto. The reaction solvent was prepared by completely stirring polyvinylpyrrolidone in methanol and distilled water mixed solvent for 30 minutes at 100 rpm at room temperature.
(b) 단량체 용액 제조(b) Preparation of monomer solution
교반기가 부착된 100ml 2구 분리형 반응기에서 라디칼 중합성 단량체로서 메틸메타크릴레이트 8g과 가교제인 다관능성 가교 단량체로서 에틸렌글리콜디메타크릴레이트 2g을 투입 하여 교반을 통해 완전히 용해시켰다. 개시제로서 포타슘퍼설페이트(KPS) 0.1g, 사슬이동제로서 요오드 0.005g을 다관능성 투입한 후 상온에서 100rpm의 교반을 통해 완전히 용해시켜 단량체 용액을 제조하였다.In a 100 ml two-necked separate reactor equipped with a stirrer, 8 g of methyl methacrylate as a radical polymerizable monomer and 2 g of ethylene glycol dimethacrylate as a multifunctional crosslinking monomer as a crosslinking agent were added and completely dissolved by stirring. 0.1 g of potassium persulfate (KPS) as an initiator and 0.005 g of iodine as a chain transfer agent were multifunctionally added, and then completely dissolved by stirring at 100 rpm at room temperature to prepare a monomer solution.
(c) 중합 실시 과정(c) Polymerization Process
상기 반응용매가 투입된 300ml 분리형 반응기의 내부에 질소를 계속적으로 충진시켜 반응기 내부의 산소를 제거하고 질소로 치환 시킨 후 200rpm으로 교반과 함께 반응기를 약 60 ℃로 승온 시켰다. 상기 제조된 단량체 용액과 촉매인 H2O2 1g을 반응기 내에 투입하여 약 12시간에 걸쳐 modified soap-free 유화 중합을 실시하였다. SEM 분석을 실시하여 도 2에 나타내었다.
Nitrogen was continuously charged into the 300 ml separation reactor in which the reaction solvent was added to remove oxygen in the reactor, and replaced with nitrogen, and the reactor was heated to about 60 ° C. with stirring at 200 rpm. The prepared monomer solution and 1 g of H 2 O 2 , which is a catalyst, were charged into the reactor, and the modified soap-free emulsion polymerization was performed over about 12 hours. SEM analysis was performed to show in FIG. 2.
비교예Comparative example 1 One
사슬이동제인 요오드를 사용하지 않고 반응을 실시한 것 이외에는 상기 실시예 1과 동일하게 진행하였다. 제조된 입자를 세척하여 SEM 분석을 한 결과를 도 3에 나타내었다. 도 1, 도 2와는 달리 도 3의 경우 입자의 모양이 구형을 띄지 못하고 있으며 크기도 일정하지 않음을 확인할 수 있었다.
The same procedure as in Example 1 was carried out except that the reaction was carried out without using iodine which is a chain transfer agent. The result of SEM analysis by washing the prepared particles is shown in FIG. 3. Unlike FIG. 1 and FIG. 2, in the case of FIG. 3, the shape of the particles was not spherical and the size was not constant.
실험예Experimental Example : : PSAPSA 측정에 따른 입자 입도 분포 측정 Particle size distribution measurement by measurement
제조된 가교 입자는 PSA(Particle Size Analizer)의 측정을 통하여 고분자 입자의 입도 분포를 측정하였다. PSA를 측정하기 위해 반응시 첨가된 분산 안정제와 미반응 단량체를 세척과정을 통해 완전히 제거시킨 후 분석하였다. 상기 분석은 세척된 입자를 초당 3000개씩 분석 장비에 흘려주는 조건으로 이루어졌으며 각종 조건에 따른 입도분포와 단분산도를 측정하였다. 상기 결과에 따른 PSA의 그래프를 도 4에서 나타내었으며, 상기 실험 결과를 하기 표 1에 나타내었다. The prepared crosslinked particles measured particle size distribution of the polymer particles through measurement of PSA (Particle Size Analizer). In order to measure PSA, the dispersion stabilizer and the unreacted monomer added during the reaction were completely removed through a washing process and analyzed. The analysis was performed under conditions of flowing 3000 particles per second to the analysis equipment, and the particle size distribution and monodispersity according to various conditions were measured. The graph of the PSA according to the result is shown in Figure 4, the experimental results are shown in Table 1 below.
상기 표 1의 결과로부터, 본원 발명에 따른 요오드를 사용하는 경우, 많은 양(단량체 중량 대비 10%이상) 의 가교제를 단일의 반응용매 상을 갖는 분산중합 과정에 도입해도 높은 단분산도와 다양한 사이즈를 갖는 안정된 가교 입자를 제조할 수 있다는 사실을 확인할 수 있었다. 그러나 요오드가 도입되지 않은 상태에서 동일한 높은 가교제를 투입하여 분산중합을 실시 한 경우 뭉침 현상이 발생하여 안정된 구형의 입자를 얻을 수 없었으며, 요오드가 도입된 반응에서 촉매가 투입되지 않으면, 입자의 수득률과 단분산도가 크게 떨어진다는 사실을 확인하였으며, 이를 비교한 PSA 물, 메탄올, 에탄올 등의 팽윤 부여되지 않는 비상용성 용매를 사용한 경우 무기물 함량이 상대적으로 매우 낮게 나타남을 확인할 수 있었다.From the results of Table 1, when using iodine according to the present invention, even if a large amount of crosslinking agent (more than 10% by weight of monomer) is introduced into the dispersion polymerization process having a single reaction solvent phase, It was confirmed that stable crosslinked particles having However, when dispersion polymerization was carried out by adding the same high crosslinking agent without iodine, agglomeration occurred, and thus, a stable spherical particle could not be obtained. If the catalyst was not added in the reaction with iodine, the yield of particles was obtained. And it was confirmed that the monodispersity is greatly reduced, and compared with the non-swelling insoluble solvents such as PSA water, methanol, ethanol, it was confirmed that the inorganic content is relatively very low.
따라서 본 발명의 제조방법에 의하여 제조된 10% 이상의 높은 가교 밀도를 갖는 단분산 고분자 입자를 1차적인 중합 공정만을 통하여 제조 가능함을 알 수 있다.Therefore, it can be seen that the monodisperse polymer particles having a high crosslink density of 10% or more prepared by the production method of the present invention can be produced only through the primary polymerization process.
Claims (17)
스타일렌 또는 아크릴레이트 계의 라디칼 중합성 단량체 100중량부에 대해 사슬이동제로 요오드 또는 브롬아이오딘 화합물을 0.001 ~ 50 중량부로 첨가하고, 가교제 및 개시제를 첨가하여 단량체 용액을 제조하는 단계; 및
상기 반응용매와 상기 단량체 용액을 혼합한 후 승온 및 교반하여 분산 중합시키는 단계;
를 포함하는 단분산 가교 입자의 제조방법.
Preparing a reaction solvent by adding a dispersion stabilizer to a solvent;
Preparing a monomer solution by adding 0.001 to 50 parts by weight of an iodine or bromiodine compound as a chain transfer agent with respect to 100 parts by weight of a styrene or acrylate radically polymerizable monomer, and adding a crosslinking agent and an initiator; And
Mixing the reaction solvent with the monomer solution and then dispersing the mixture by heating and stirring;
Method for producing monodisperse crosslinked particles comprising a.
The method of claim 1, wherein the radical polymerizable monomer is styrene, p-methylstyrene, m-methylstyrene, p-ethylstyrene, m-ethylstyrene, p-chlorostyrene, m-chlorostyrene, p-chloromethyl styrene, m-chloromethylstyrene, styrenesulfonic acid, pt-butoxystyrene, mt-butoxystyrene, fluorostyrene, alphamethylstyrene, vinyltoluene, chlorostyrene, methyl (meth) acrylate, ethyl (meth) acrylate , Butyl (meth) acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, fluoroethyl acrylate, trifluoroethyl methacrylate , Pentafluoropropyl methacrylate, fluoroethyl methacrylate, hexafluorobutyl (meth) acrylate, hexafluoroisopropyl methacrylate, perfluoroalkyl acrylate, octafluorope Methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl ether, allyl butyl ether, allyl glycidyl ether, (meth) acrylic acid, maleic acid, alkyl (meth) acrylamide and (meth) acrylonitrile Method for producing monodisperse crosslinked particles, characterized in that at least one compound selected from the group consisting of.
The method of claim 1, wherein the radically polymerizable monomer is used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the total of the reaction solvent and the monomer solution.
The method for producing monodisperse crosslinked particles according to claim 1, wherein the crosslinking agent is used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the radical polymerizable monomer.
The method of claim 1, wherein the initiator is benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t- butyl hydroperoxide, t- butyl peroxy-2-ethyl hexanoate, t -Hexyl peroxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,2'-azobisisobutyronitrile, 2,2'- Selected from the group consisting of azobis2,4-dimethylvaleronitrile, 2,2'-azobis2-methylisobutyronitrile, ammonium persulfate, potassium persulfate, sodium persulfate, ammonium bisulfate and sodium bisulfate It is a 1 or more types of compound, The manufacturing method of monodisperse crosslinked particle | grains characterized by the above-mentioned.
The method of claim 1, wherein the initiator is 0.05 to 10 parts by weight based on 100 parts by weight of the total of the reaction solvent and the monomer solution.
The method of claim 1, wherein the dispersion stabilizer is methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl methyl ether, polyacrylic acid, polyvinylacetate, polyvinylpyrrolidone and vinylpyrrolidone-vinylacetate Method for producing monodisperse crosslinked particles, characterized in that at least one compound selected from the group consisting of copolymers.
The method of claim 1, wherein the dispersion stabilizer is 0.5 to 15 parts by weight based on 100 parts by weight of the total of the reaction solvent and the monomer solution.
The method for producing monodisperse crosslinked particles according to claim 1, further comprising adding a surfactant in the step of preparing the reaction solvent.
The group of claim 13, wherein the surfactant is sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate, sodium dodecyl naphthalene sulfate, dialkylbenzenealkylsulfate, sulfonate, abitic acid, and hexadecanesulfonate. Method for producing monodisperse crosslinked particles, characterized in that at least one compound selected from.
The method of claim 13, wherein the surfactant is 0.05 to 15 parts by weight based on 100 parts by weight of the total of the reaction solvent and the monomer solution.
The method of claim 1, wherein the catalyst is added in the step of mixing the reaction solvent and the monomer solution, but the catalyst is a group consisting of hydroperoxide, cumene hydroperoxide, butyl hydroperoxide, hydromethylhydroperoxide and acetyl hydroperoxide. Method for producing monodisperse crosslinked particles, characterized in that at least one compound selected from.
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