KR100740908B1 - Amphiphilic hybrid polymer containing hybrid nanoparticles and method for preparing same - Google Patents
Amphiphilic hybrid polymer containing hybrid nanoparticles and method for preparing same Download PDFInfo
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Abstract
본 발명은 하이브리드 나노입자를 함유하는 양친매성 하이브리드 폴리머 및 그의 제조방법에 관한 것으로서, 본 발명은 수산기를 갖는 친수성 폴리머 용액에 이소시아네이트기를 갖는 유기-무기 하이브리드 나노입자를 포함하는 용액을 적하한 후 상기 친수성 폴리머의 수산기와 상기 하이브리드 나노입자의 이소시아네이트기를 우레탄 반응시켜 반응혼합액을 제조한 다음, 상기 반응 혼합액을 과량의 증류수내에 공급하여 친수성 폴리머 내에 상기 하이브리드 나노입자가 우레탄 반응으로 도입된 양친매성 하이브리드 폴리머를 침전시킨 다음, 침전된 상기 양친매성 하이브리드 폴리머를 세척 및 건조하는 것을 특징으로 한다.The present invention relates to an amphiphilic hybrid polymer containing a hybrid nanoparticles and a method for producing the same, the present invention is dropping a solution containing an organic-inorganic hybrid nanoparticle having an isocyanate group in a hydrophilic polymer solution having a hydroxyl group and then the hydrophilic The reaction mixture was prepared by urethane reacting the hydroxyl group of the polymer and the isocyanate group of the hybrid nanoparticles, and then supplying the reaction mixture in excess distilled water to precipitate an amphiphilic hybrid polymer in which the hybrid nanoparticles were introduced into the hydrophilic polymer by urethane reaction. Then, the precipitated amphiphilic hybrid polymer is characterized in that the washing and drying.
본 발명에 따른 양친매성 하이브리드 폴리머는 열적, 기계적 물성이 향상되고, 뛰어난 수용성과 형태안정성을 동시에 구비하여 상처 보호 및 치유용 드레싱(Wound dressing), 생체조직배양용 담체(Scaffold) 등과 같은 의료용 소재로 특히 유용하다.Amphiphilic hybrid polymer according to the present invention is improved in thermal and mechanical properties, and has excellent water solubility and morphological stability at the same time as a medical material such as wound dressing (Wound dressing), biological tissue culture carrier (Scaffold), etc. Particularly useful.
Description
도 1은 실시예 1에서 제조한 양친매성 하이브리드 폴리비닐알코올(POSS 나노입자 함유)의 적외선 분광기(FT-IR) 스펙트라 분석 그래프이다.1 is an infrared spectrometer (FT-IR) spectra analysis graph of amphiphilic hybrid polyvinyl alcohol (containing POSS nanoparticles) prepared in Example 1. FIG.
도 2는 실시예 1에서 제조한 양친매성 하이브리드 폴리비닐알코올(POSS 나노입자 함유)의 시차주사열량계(DSC) 분석 그래프이다.FIG. 2 is a differential scanning calorimetry (DSC) analysis graph of amphiphilic hybrid polyvinyl alcohol (containing POSS nanoparticles) prepared in Example 1. FIG.
도 3은 실시예 1에서 제조한 양친매성 하이브리드 폴리비닐알코올(POSS 나노입자 함유)의 열중량분석기(TGA) 분석 그래프이다.Figure 3 is a thermogravimetric analysis (TGA) analysis of the amphiphilic hybrid polyvinyl alcohol (containing POSS nanoparticles) prepared in Example 1.
* 도면 중 주요 부분에 대한 부호 설명* Explanation of symbols on the main parts of the drawings
A : 실시예 1에서 사용한 폴리비닐알코올(PVA)의 분석 그래프A: Analysis graph of polyvinyl alcohol (PVA) used in Example 1
B : 실시예 1에서 사용한 폴리헤드랄 올리고머릭 실세스퀴옥산(Polyhedral Oligomeric Silsesquioxane : POSS)나노입자의 분석 그래프B: Analysis graph of polyhedral oligomeric silsesquioxane (POSS) nanoparticles used in Example 1
C : 실시예 1에서 제조한 양친매성 하이브리드 폴리비닐알코올(POSS 나노입자 함유)의 분석 그래프.C: Analysis graph of the amphiphilic hybrid polyvinyl alcohol (containing POSS nanoparticles) prepared in Example 1.
본 발명은 하이브리드 나노입자를 함유하는 양친매성 하이브리드 폴리머 및 그의 제조방법에 관한 것으로서, 구체적으로는 수용성 폴리머 내에 유기-무기 하이브리드 나노입자를 우레탄 반응에 의해 도입하여 상기 수용성 폴리머의 열적, 기계적 물성을 향상시킨 양친매성 하이브리드 폴리머 및 그의 제조방법에 관한 것이다.The present invention relates to an amphiphilic hybrid polymer containing a hybrid nanoparticles and a method for producing the same, specifically, organic-inorganic hybrid nanoparticles are introduced into a water-soluble polymer by a urethane reaction to improve thermal and mechanical properties of the water-soluble polymer. Amphipathic hybrid polymer and a method for producing the same.
친수성 폴리머의 일종인 폴리비닐알코올은 우수한 내용제성, 내유성, 내알칼리성, 산소저항성, 높은 인장 및 압축강도, 인장탄성률 및 내마모성을 지니는 반면 높은 수용성으로 인하여, 특히 상처보호치유드레싱(wound dressing) 이나 생체조직배양을 위한 담체(Scaffold) 등과 같은 의료용 소재로는 사용상에 많은 제약을 받아왔다. 본 발명에서는 이와 같은 문제점을 해결하기 위해서 수용성의 폴리머에 소수성 특성을 가지는 나노 입자를 도입하여 소수성의 하이브리드 나노 입자 함량에 따라 수용성을 달리하는 양친매성 유-무기 하이브리드 폴리머를 제조하고자 한다.Polyvinyl alcohol, a hydrophilic polymer, has excellent solvent resistance, oil resistance, alkali resistance, oxygen resistance, high tensile and compressive strength, tensile modulus and abrasion resistance, while high water solubility, in particular, wound dressing or bio dressing Medical materials such as scaffolds for tissue culture have been subject to many limitations in use. In the present invention, in order to solve such a problem, to introduce a nanoparticle having a hydrophobic property to the water-soluble polymer to produce an amphiphilic organic-inorganic hybrid polymer that varies in water solubility according to the hydrophobic hybrid nanoparticle content.
일반적으로 양친매성 고분자는 친수성 구역과 소수성 구역으로 이루어진 고분자를 칭하며 주로 양친매성 합성 공중합체가 있으며, 생체막을 구성하는 지질의 주된 성분인 인지질, 콜레스테롤 등도 양친매성 분자들이다. 현재까지 소수성의 하이브리드 나노입자를 이용한 양친매성 신규 고분자 물질의 개발은 미미한 실정이다.In general, an amphiphilic polymer refers to a polymer composed of a hydrophilic zone and a hydrophobic zone, and there are mainly amphiphilic synthetic copolymers. Phospholipids and cholesterol, which are major components of lipids constituting the biofilm, are amphiphilic molecules. To date, development of amphipathic novel high molecular materials using hydrophobic hybrid nanoparticles is insignificant.
친수성 폴리머 내에 소수성의 유기-무기 하이브리드 나노입자를 도입하는 종 래기술로서는 친수성 폴리머 용액과 상기 하이브리드 나노입자 용액을 단순히 혼합해 주는 방법이 사용되어 왔으나, 이 경우에는 균일한 혼합이 어려운 문제점이 있었다.As a conventional technique of introducing hydrophobic organic-inorganic hybrid nanoparticles into a hydrophilic polymer, a method of simply mixing a hydrophilic polymer solution and the hybrid nanoparticle solution has been used, but in this case, uniform mixing is difficult.
또 다른 종래기술로는 중합이 가능한 유기-무기 하이브리드 나노입자를 친수성 폴리머 중합공정 중에 투입하여 이들의 선상 중합체 또는 블록 공중합체를 합성하는 방법이 사용되어 왔으나, 이 경우에는 고분자량의 고분자 제조가 어렵고 상기 하이브리드 나노입자의 균일한 분산이 어려운 문제점이 있었다. 구체적으로 미국 특허 제7,067,606호에서는 폴리에틸렌글리콜 (polyethyleneglycol; 이하 "PEG"라 한다) 양쪽 말단에 소수성의 폴리헤드랄 올리고머릭 실세스퀴옥산(Polyhedral Oligomeric Silsesquioxane : 이하 "POSS"라 한다) 나노입자를 2당량 화학적 공유 결합으로 도입하여 양친매성의 하이브리드 폴리에틸렌글리콜을 제조하는 방법을 제안하고 있다. 하이브리드 나노입자량은 사용된 PEG 분자량 (Mw = 1000 ~ 10000 g/mol) 에 따라 약 20중량% 내지 70중량% 로 조절하였다. 그러나 상기 방법은 고분자량의 고분자 제조가 어렵고 POSS 나노입자의 균일 분산이 어려운 문제점이 있었다.As another conventional technique, a method of synthesizing linear polymers or block copolymers thereof by introducing polymerizable organic-inorganic hybrid nanoparticles during a hydrophilic polymer polymerization process has been used. The uniform dispersion of the hybrid nanoparticles was difficult. Specifically, in US Pat. No. 7,067,606, a hydrophobic polyhedral oligomeric silsesquioxane (hereinafter referred to as "POSS") nanoparticles at both ends of polyethylene glycol (hereinafter referred to as "PEG") 2 A method of preparing amphipathic hybrid polyethylene glycol by introducing equivalent chemical covalent bonds has been proposed. Hybrid nanoparticle amount was adjusted to about 20% to 70% by weight depending on the PEG molecular weight (Mw = 1000 to 10000 g / mol) used. However, the method has a problem in that it is difficult to manufacture a high molecular weight polymer and difficult to uniformly disperse the POSS nanoparticles.
본 발명은 앞서 언급하였듯이 높은 수용성으로 인하여 메디칼 소재로의 사용상에 많은 제약을 받아온 친수성 폴리머에 소수성의 하이브리드 나노입자를 도입함으로써 우수한 열적 및 기계적 특성뿐만 아니라 수용성이 용이하게 조절될 수 있는 양친매성 하이브리드 폴리머를 제공하는데 그 목적이 있다. As described above, the present invention introduces a hydrophobic hybrid nanoparticle into a hydrophilic polymer, which has been heavily constrained for use as a medical material due to its high water solubility. The purpose is to provide.
본 발명의 양친매성 하이브리드 폴리머는 친수성 폴리머 내에 도입된 소수성 의 하이브리드 나노입자 함량에 따라서 수용액상에서의 용해성의 조절이 가능하다.The amphiphilic hybrid polymer of the present invention can control the solubility in aqueous solution according to the content of hydrophobic hybrid nanoparticles introduced into the hydrophilic polymer.
본 발명은 친수성 폴리머 내에 유기-무기 하이브리드 나노입자를 우레탄 반응에 의해 도입시켜 열적, 기계적 성질이 향상된 양친매성 하이브리드 폴리머를 제조하는 방법을 제공하고자 한다.The present invention is to provide a method for preparing an amphiphilic hybrid polymer with improved thermal and mechanical properties by introducing organic-inorganic hybrid nanoparticles into the hydrophilic polymer by a urethane reaction.
또한, 본 발명은 상기 방법으로 제조되어 열적 기계적 성질이 우수하며, 양호한 수용성과 수용액 상에서의 형태안정성을 동시에 구비하여 각종 생활용품, 의료용 소재, 산업용 소재, 필터, 의류 등에 유용한 양친매성 하이브리드 폴리머를 제공하고자 한다.In addition, the present invention provides an amphiphilic hybrid polymer produced by the above method is excellent in thermal and mechanical properties, having good water solubility and morphological stability in aqueous solution at the same time useful for various household goods, medical materials, industrial materials, filters, clothing, etc. I would like to.
본 발명에 따른 하이브리드 나노입자를 함유하는 양친매성 하이브리드 폴리머의 제조방법은, 수산기를 갖는 친수성 폴리머 용액에 이소시아네이트기를 갖는 유기-무기 하이브리드 나노입자를 포함하는 용액을 적하한 후 상기 친수성 폴리머의 수산기와 상기 하이브리드 나노입자의 이소시아네이트기를 우레탄 반응시켜 반응혼합액을 제조한 다음, 상기 반응 혼합액을 과량의 증류수내에 공급하여 친수성 폴리머 내에 상기 하이브리드 나노입자가 우레탄 반응으로 도입된 양친매성 하이브리드 폴리머를 침전시킨 다음, 침전된 상기 양친매성 하이브리드 폴리머를 세척 및 건조하는 것을 특징으로 한다.In the method for producing an amphiphilic hybrid polymer containing hybrid nanoparticles according to the present invention, a solution containing an organic-inorganic hybrid nanoparticle having an isocyanate group is added dropwise to a hydrophilic polymer solution having a hydroxyl group, and then the hydroxyl group of the hydrophilic polymer and the The reaction mixture was prepared by urethane reaction of the isocyanate group of the hybrid nanoparticles, and then the reaction mixture was supplied in excess distilled water to precipitate an amphiphilic hybrid polymer in which the hybrid nanoparticles were introduced into the hydrophilic polymer in the urethane reaction. It is characterized in that for washing and drying the amphiphilic hybrid polymer.
또한, 본 발명에 따른 하이브리드 나노입자를 함유하는 양친매성 하이브리드 폴리머는, 고분자의 곁사슬 내에 하이브리드 나노입자가 우레탄 결합에 의해 도입되어 있는 것을 특징으로 한다.In addition, the amphiphilic hybrid polymer containing the hybrid nanoparticles according to the present invention is characterized in that the hybrid nanoparticles are introduced by a urethane bond into the side chain of the polymer.
이하, 첨부한 도면 등을 통하여 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
먼저, 본 발명에 따른 하이브리드 나노입자를 함유하는 양친매성 하이브리드 폴리머(이하 "양친매성 하이브리드 폴리머"로 약칭한다)는 아래와 같은 공정들을 거쳐 제조된다.First, an amphiphilic hybrid polymer containing hybrid nanoparticles according to the present invention (hereinafter, abbreviated as " amphiphilic hybrid polymer ") is prepared through the following processes.
먼저, 수산기를 갖는 친수성 폴리머 용액에 이소시아네이트기를 갖는 유기-무기 하이브리드 나노입자를 포함하는 용액을 적하한 후 상기 친수성 폴리머의 수산기와 상기 하이브리드 나노입자의 이소시아네이트기를 우레탄 반응시켜 반응혼합액을 제조한다.First, a solution containing organic-inorganic hybrid nanoparticles having an isocyanate group is added dropwise to a hydrophilic polymer solution having a hydroxyl group, followed by urethane reaction of the hydroxyl group of the hydrophilic polymer and the isocyanate group of the hybrid nanoparticles to prepare a reaction mixture.
이때, 유기-무기 하이브리드 나노입자는 폴리헤드랄 올리고머릭 실세스퀴옥산(Polyhedral Oligomeric Silsesquioxane) 나노입자 등이다.At this time, the organic-inorganic hybrid nanoparticles are polyhedral oligomeric silsesquioxane nanoparticles and the like.
상기 POSS 나노입자는 케이지(Cage) 구조를 갖고, 구조식은(RSiO1 .5)n 이다.The POSS nano-particles have a cage (Cage) structure, the following structural formula is a (RSiO 1 .5) n.
상기 구조식에서 n은 8, 10, 12 또는 16의 정수이고, R은 수소, 알킬, 알킬렌, 아릴, 아릴렌 또는 이들의 유도체이다.N is an integer of 8, 10, 12 or 16, and R is hydrogen, alkyl, alkylene, aryl, arylene or derivatives thereof.
또한, 수신기를 갖는 친수성 폴리머는 폴리비닐알코올, 셀룰로오스, 셀룰로오스 유도체, 키토산, 폴리펩티드 및 폴리라이신(Polylysine)으로 이루어진 그룹 중에서 선택된 1종이며, 보다 바람직하기로는 폴리비닐알코올이다.In addition, the hydrophilic polymer having a receiver is one selected from the group consisting of polyvinyl alcohol, cellulose, cellulose derivatives, chitosan, polypeptide and polylysine, and more preferably polyvinyl alcohol.
상기 폴리비닐알코올 평균분자량은 65,000g/몰 수준이고 가수분해율은 85.5~88.5% 수준인 것이 바람직하다.The polyvinyl alcohol average molecular weight is 65,000g / mole level and the hydrolysis rate is preferably 85.5 ~ 88.5% level.
다음으로는, 상기 반응 혼합액을 과량의 증류수내에 공급하여 친수성 폴리머내에 상기 하이브리드 나노입자가 우레탄 반응으로 도입된 양친매성 하이브리드 폴리머를 침전시킨다.Next, the reaction mixture is supplied in an excess of distilled water to precipitate the amphipathic hybrid polymer in which the hybrid nanoparticles are introduced into the hydrophilic polymer in the urethane reaction.
계속해서, 침전된 상기 양친매성 하이브리드 폴리머를 세척 및 건조하여 본 발명에 따른 양친매성 하이브리드 폴리머를 제조한다. Subsequently, the precipitated amphiphilic hybrid polymer is washed and dried to prepare an amphiphilic hybrid polymer according to the present invention.
상기 양친매성 하이브리드 폴리머 내에 하이브리드 나노입자의 도입함량은 0.1~99.9중량%로 조절한다. 소수성의 하이브리드 나노입자의 도입함량과 양친매성 하이브리드 폴리머의 수용성은 서로 비례한다.The introduction content of the hybrid nanoparticles in the amphiphilic hybrid polymer is adjusted to 0.1 ~ 99.9% by weight. The introduction of hydrophobic hybrid nanoparticles and the water solubility of the amphiphilic hybrid polymer are proportional to each other.
상기와 같은 방법으로 제조된 양친매성 하이브리드 폴리머는 고분자의 곁사슬 내에 하이브리드 나노입자가 우레탄 결합에 의해 도입되어 있는 것을 특징으로 한다.Amphiphilic hybrid polymer prepared by the above method is characterized in that the hybrid nanoparticles are introduced by the urethane bond in the side chain of the polymer.
상기 양친매성 하이브리드 폴리머의 형태는 나노입자, 나노섬유 또는 박막 등으로 가공될 수 있다.The amphiphilic hybrid polymer may be processed into nanoparticles, nanofibers, or thin films.
이하, 실시예를 통하여 본 발명을 더욱 구체적으로 살펴본다.Hereinafter, the present invention will be described in more detail with reference to Examples.
그러나, 본 발명은 하기 실시예에 의해 한정되는 것은 아니다.However, the present invention is not limited by the following examples.
실시예Example 1 One
먼저 평균 분자량이 65,000g/몰이고 가수분해율이 86%인 폴리비닐알코올 1g 을 응축기, 온도계, 셉텁가 설치된 4구 라운드 플라스크에 1 g 을 넣고 정제된 디메틸설폭사이드 19 g을 투입하여 5 wt%의 폴리비닐알코올 용액을 제조한 후 질소가스 분위기 하에서 균일한 용액을 얻어질 때까지 교반한다. 그리고 POSS 나노입자 0.327 g 과 촉매 (dibutyl tin dilaurate; DBTDL) 0.0130 g을 테트라하이드로퓨란 (THF) 용매 6.27 g에 용해 시켜 5 wt% 용액을 준비한다. 폴리비닐알코올 용액에 POSS 나노입자와 촉매의 혼합용액을 주사기로 이용하여 한 방울씩 적하한다. 이 때, 플라스크 내부 온도는 90℃로 유지하고, 질소분위기 하에서 12 시간 동안 반응을 시킨다. 반응 종료 후, 과량의 증류수에 반응혼합액을 침전시킨다. 얻어진 POSS 나노입자를 함유하는 양친매성 하이브리드 폴리비닐알코올 (Amphiphilic PVA-POSS hybrids) 을 n-헥산에 3번 세척을 한 다음, 하룻밤 동안 진공 건조하여 최종적으로 POSS 나노입자를 함유하는 양친매성 하이브리드 폴리비닐알코올을 제조하였다.First, 1 g of polyvinyl alcohol having an average molecular weight of 65,000 g / mol and a hydrolysis rate of 86% was placed in a four-necked round flask equipped with a condenser, a thermometer, and a septum, and 19 g of purified dimethyl sulfoxide was added. After preparing a polyvinyl alcohol solution, it is stirred under a nitrogen gas atmosphere until a uniform solution is obtained. A 5 wt% solution was prepared by dissolving 0.327 g of POSS nanoparticles and 0.0130 g of a catalyst (dibutyl tin dilaurate; DBTDL) in 6.27 g of a tetrahydrofuran (THF) solvent. To the polyvinyl alcohol solution was added dropwise dropwise using a mixed solution of POSS nanoparticles and catalyst as a syringe. At this time, the flask internal temperature is maintained at 90 ℃, the reaction is carried out for 12 hours under a nitrogen atmosphere. After the reaction is completed, the reaction mixture is precipitated in excess distilled water. Amphiphilic PVA-POSS hybrids containing the obtained POSS nanoparticles were washed three times in n-hexane, followed by vacuum drying overnight to finally obtain amphiphilic hybrid polyvinyl containing POSS nanoparticles. Alcohol was prepared.
상기와 같이 제조되어 POSS 나노입자를 함유하는 양친매성 하이브리드 폴리비닐알코올과 실시예 1에서 사용한 폴리비닐알코올 및 실시예 1에서 사용한 POSS 나노입자 각각의 적외선 분광기(FT-IR)스펙트라 분석 그래프는 도 1이고, 시차주사열량계(DSC) 분석 그래프는 도 2이고, 열중량분석기(TGA) 분석 그래프는 도 3이다.Amphipathic hybrid polyvinyl alcohol prepared as described above and the polyvinyl alcohol used in Example 1 and the infrared spectroscopy (FT-IR) spectra analysis graph of each of the POSS nanoparticles used in Example 1 is a graph of FIG. The differential scanning calorimetry (DSC) analysis graph is FIG. 2, and the thermogravimetric analyzer (TGA) analysis graph is FIG. 3.
상기 도 1 내지 도 3에서 A는 상기 폴리비닐알코올의 그래프이고, B는 상기 POSS 나노입자의 그래프이고, C는 양친매성 하이브리드 폴리비닐알코올의 그래프이다.1 to 3, A is a graph of the polyvinyl alcohol, B is a graph of the POSS nanoparticles, C is a graph of the amphipathic hybrid polyvinyl alcohol.
상기 실시예 1에서 양친매성 하이브리드 폴리비닐알코올의 반응 메카니즘은 아래와 같다.The reaction mechanism of the amphiphilic hybrid polyvinyl alcohol in Example 1 is as follows.
상기 반응 메카니즘에서 R은 사이클로헥실기 이다.In the reaction mechanism, R is a cyclohexyl group.
본 발명은 수용성 폴리머 내에 유기-무기 하이브리드 나노입자가 균일하게 분산되게 도입되어 있고, 고분자량을 갖는 양친매성 하이브리드 폴리머를 용이하게 제조할 수 있다.The present invention is introduced so that the organic-inorganic hybrid nanoparticles are uniformly dispersed in the water-soluble polymer, it can easily produce an amphiphilic hybrid polymer having a high molecular weight.
본 발명의 양친매성 하이브리드 폴리머는 우수한 열적 기계적 성질과 함께 수용액 상에서 양호한 형태안정성을 구비하여 의료용 소재, 각종 생활용품용 소재, 산업용 자재, 필터용 소재, 의류용 소재 등으로 유용하다.Amphiphilic hybrid polymers of the present invention have good morphological stability in aqueous solution with excellent thermal mechanical properties and are useful as medical materials, various household materials, industrial materials, filter materials, clothing materials and the like.
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| KR101208568B1 (en) * | 2011-06-30 | 2012-12-06 | 신슈 다이가쿠 | Nano capsule, medicine and food comprising the same |
| KR101269074B1 (en) | 2011-03-18 | 2013-05-29 | 강원대학교산학협력단 | Bridged organosilica precursor having amphiphilic polymeric chain and nano particle using thereof |
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| US20060134177A1 (en) | 2004-12-20 | 2006-06-22 | Yan Liu | Amphiphilic block copolymers and their use |
| US7067606B2 (en) | 2002-07-30 | 2006-06-27 | University Of Connecticut | Nonionic telechelic polymers incorporating polyhedral oligosilsesquioxane (POSS) and uses thereof |
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| KR101269074B1 (en) | 2011-03-18 | 2013-05-29 | 강원대학교산학협력단 | Bridged organosilica precursor having amphiphilic polymeric chain and nano particle using thereof |
| KR101208568B1 (en) * | 2011-06-30 | 2012-12-06 | 신슈 다이가쿠 | Nano capsule, medicine and food comprising the same |
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