KR100241808B1 - Process for preparing dressing for wound-treatment using sol-gel precursor - Google Patents
Process for preparing dressing for wound-treatment using sol-gel precursor Download PDFInfo
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- KR100241808B1 KR100241808B1 KR1019970062011A KR19970062011A KR100241808B1 KR 100241808 B1 KR100241808 B1 KR 100241808B1 KR 1019970062011 A KR1019970062011 A KR 1019970062011A KR 19970062011 A KR19970062011 A KR 19970062011A KR 100241808 B1 KR100241808 B1 KR 100241808B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/07—Stiffening bandages
- A61L15/12—Stiffening bandages containing macromolecular materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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Abstract
본 발명은 신규한 졸-겔프리커서 및 이를 이용한 상처치료용 드레싱의 제조방법에 관한 것으로 좀더 상세하게는 디올(diol)과 트리에톡시실릴프로필이소시아네이트(TESPI)를 합성하여 얻은 졸-겔프리커서 및 졸-겔프리커서를 메트릭스화 반응시킨 하이드로겔형 고분자 메트릭스를 겔화반응시켜 상처치료용 드레싱을 제조하는 방법에 관한 것이다.The present invention relates to a novel sol-gel precursor and a method for preparing a wound dressing using the same. More specifically, a sol-gel precursor obtained by synthesizing diol and triethoxysilylpropyl isocyanate (TESPI) And it relates to a method for producing a wound dressing by gelling the hydrogel-type polymer matrix that the sol-gel precursor matrix-reacted.
따라서, 본 발명의 목적은 디올(diol)과 트리에톡시실릴프로필이소시아네이트(TESPI)를 합성하여 얻은 신규한 졸-겔프리커서 및 졸-겔 방법을 이용하여 친수성과 생체적합성이 우수한 유기-무기 복합체를 여러 가지 상품형태로 제조함으로써 다양한 상처에 적용할 수 있는 상처치료용 드레싱의 새로운 제조방법을 제공함에 있다.Accordingly, an object of the present invention is an organic-inorganic complex having excellent hydrophilicity and biocompatibility using a novel sol-gel precursor and a sol-gel method obtained by synthesizing diol and triethoxysilylpropyl isocyanate (TESPI). It is to provide a new method of manufacturing a dressing for wound treatment that can be applied to a variety of wounds by manufacturing in various product forms.
본 발명에 의한 상처치료용 드레싱은 욕창과 정맥응혈과 같은 노인성 질환과 각종 교통 사고나 화상 환자들의 상처치료용으로 사용될 수 있다.The wound dressing according to the present invention can be used for the treatment of wounds of senile diseases such as pressure sores and venous coagulation and various traffic accidents or burn patients.
Description
본 발명은 신규한 졸-겔프리커서 및 이를 이용한 상처치료용 드레싱의 제조방법에 관한 것으로 좀더 상세하게는 디올(diol)과 트리에톡시실릴프로필이소시아네이트(TESPI)를 합성하여 얻은 졸-겔프리커서 및 졸-겔프리커서를 메트릭스화 반응시킨 하이드로겔형 고분자 메트릭스를 겔화반응시켜 상처치료용 드레싱을 제조하는 방법에 관한 것이다.The present invention relates to a novel sol-gel precursor and a method for preparing a wound dressing using the same. More specifically, a sol-gel precursor obtained by synthesizing diol and triethoxysilylpropyl isocyanate (TESPI) And it relates to a method for producing a wound dressing by gelling the hydrogel-type polymer matrix that the sol-gel precursor matrix-reacted.
기존의 졸-겔공정을 이용하는 반응으로 금속 알콕사이드 M(OR)n의 가수분해-축합반응을 이용해서 저온에서 유리나 세라믹을 합성하는데 많이 이용되었다. 이때 M으로는 Na, Ba, Cu, Al, Si, Ti, Ge, V, W, Y, Sn, In, Sb 등의 금속이나 반금속이 사용되며, R로는 메틸, 에틸, 프로필, 부틸기 등이 사용된다. 이중에서 알콕시 실란류가 가장 보편적으로 사용되며, TEOS(tetraethoxysilane)가 많이 사용되는데, 이는 TEOS가 실리콘 수지 제조공정에서 부산물로 얻어지기 때문에 가격이 싸고, 취급이 용이하기 때문이다. 그러나, 알콕시 실란류는 물에 녹지 않기 때문에 공통 용매로써 메탄올, 에탄올, 프로판올 등의 저급 알콜을 사용한다. 또한 여러 종류의 메탈 알콕사이드를 함께 사용함으로써 다양한 기능을 갖는 고성능 복합체를 얻을 수 있다.The reaction using a conventional sol-gel process has been widely used to synthesize glass or ceramic at low temperature by using a hydrolysis-condensation reaction of metal alkoxide M (OR) n . In this case, metals such as Na, Ba, Cu, Al, Si, Ti, Ge, V, W, Y, Sn, In, Sb or semimetals are used as M, and R, methyl, ethyl, propyl, butyl, etc. This is used. Among them, alkoxy silanes are most commonly used, and tetraethoxysilane (TEOS) is widely used because it is cheap and easy to handle because TEOS is obtained as a by-product in the silicone resin manufacturing process. However, since alkoxy silanes are insoluble in water, lower alcohols such as methanol, ethanol and propanol are used as common solvents. In addition, by using various kinds of metal alkoxide together, a high performance composite having various functions can be obtained.
무기, 유기금속 고분자 소재의 최근 연구 동향은 의료용, 전기 재료용, 광전자용, 우주 산업용, 세라믹 선구물질, 초강도 복합재료, 농약이나 의약품들의 조절 방출 등에 사용되는 합성 무기 고분자 소재 및 소재의 신합성법의 개발에 초점을 맞추고 있다. 한편, 상처치료용 드레싱의 경우, 단순히 상처의 노출을 막고 외부로부터 상처를 보호하는 역할 이외에 공기투과성과 습기흡수성이 우수하며 상처분비물의 조절이 가능하고, 박테리아의 번식을 막으며, 형태변형이 적은 다양한 상처치료용 드레싱의 개발이 요구되고 있다.Recent research trends on inorganic and organometallic polymer materials include new synthetic methods of synthetic inorganic polymer materials and materials used in medical, electrical, optoelectronic, aerospace, ceramic precursors, super-strength composites, controlled release of pesticides and pharmaceuticals. Focuses on the development of. On the other hand, in the case of wound dressings, in addition to merely preventing the exposure of the wound and protecting the wound from the outside, the air permeability and moisture absorption are excellent, the control of the wound secretion is possible, the growth of bacteria is prevented, and the morphological deformation is small. There is a need for development of various wound dressings.
일반적으로 상처(wound)란 화상, 창상, 외상, 또는 압력이나 물리적 자극으로 인한 피부의 구조적 층의 파괴를 의미한다. 이런 다양한 상처와 그 정도에 따른 효과적인 치료를 위한 드레싱의 이상적인 조건으로는 ① 상처와의 접촉면에서 적당한 습기의 유지 능력, ② 상처분비물(exudate)의 조절 능력, ③ 드레싱의 상처에 대한 부착과 제거의 용이성, ④ 외부와의 가스, 수증기 전달 능력, ⑤ 외부로부터의 단열의 가능성, ⑥ 박테리아의 침입에 대한 저항력, ⑦ 인체에 무독성, ⑧ 우수한 기계적 물성 등을 들 수 있다.Wound generally refers to the destruction of the structural layer of the skin due to burns, cuts, trauma or pressure or physical irritation. The ideal conditions for dressing for such various wounds and their effective treatment are as follows: ① ability to maintain adequate moisture in contact with the wound, ② ability to control the exudate, ③ attachment and removal of the dressing to the wound. Ease of use, ④ the ability to transfer gas to the outside, water vapor, ⑤ the possibility of heat insulation from the outside, ⑥ resistance to the invasion of bacteria, ⑦ non-toxic to the human body, ⑧ excellent mechanical properties.
대표적인 고분자 재료로 폴리우레탄을 들 수 있는데 생체적합성이 우수하고, 무엇보다도 폴리올(polyol)과 디이소시아네이트(diisocyanate)의 성질에 따라 다양한 물성 및 기계적 성질을 가지므로 상처의 형태에 따라 필름, 하이드로겔, 하이드로콜로이드, 폼 형태의 여러 분야의 연구가 진행중이다. 본원 발명과 유사한 선행기술로서 분자량이 500-1,000인 폴리에틸렌글리콜(PEG:polyethyleneglycol)을 이용한 졸-겔프리커서를 합성하여 전자분야의 고분자 소재로 개발하고자 발표한 사례(Characterization of the Crystallization Behavior fo the Ternary System PEO/Silica/Li salt, 한국고분자학회 1996 Proceeding; 한양대학교 화학공학과 권정옥, 노시태)가 있었으나 말단기가 에톡시 실릴그룹으로 치환된 폴리에틸렌글리콜(PEG)에 국한되어 있는 연구단계의 착상에 불과하고, 본원 발명과 같이 친수성과 소수성 졸겔 프리커서를 합성하여 필름 또는 연고형태의 드레싱을 개발한 사례는 없었다.Polyurethane is a representative polymer material, which has excellent biocompatibility and, above all, various physical and mechanical properties depending on the properties of polyol and diisocyanate. Research is underway in various fields, including hydrocolloid and foam forms. As a prior art similar to the present invention, a case was proposed to synthesize a sol-gel precursor using polyethylene glycol (PEG: polyethyleneglycol) having a molecular weight of 500-1,000 and develop it as a polymer material in the electronic field (Characterization of the Crystallization Behavior fo the Ternary System PEO / Silica / Li salt, Korea Proceedings of Polymer Society, 1996 Proceeding; Dept. of Chemical Engineering, Hanyang University, Jeong-Ok Kwon, No-Sae Tae) As in the present invention, there has been no case in which a hydrophilic and hydrophobic sol-gel precursor was synthesized to develop a dressing in the form of a film or an ointment.
이에 본 발명자들은 이러한 점에 착안하여 다양한 상처의 깊이와 종류에 적절한 드레싱의 개발을 위해 연구를 수행하던 중, 기존의 상처치료용 드레싱의 단점을 보완하고, 고품질의 드레싱을 개발하고 상품화를 위한 연구를 거듭한 끝에 본 발명을 완성하게 되었다.Therefore, the inventors of the present invention, while researching for the development of dressings suitable for various depths and types of wounds, to compensate for the shortcomings of the existing wound dressings, researches for developing and commercializing high-quality dressings After repeating the present invention was completed.
따라서, 본 발명의 목적은 디올(diol)과 트리에톡시실릴프로필이소시아네이트(TESPI)를 합성하여 얻은 신규한 졸-겔프리커서를 제공함에 있다.Accordingly, an object of the present invention is to provide a novel sol-gel precursor obtained by synthesizing diol and triethoxysilylpropyl isocyanate (TESPI).
본 발명의 또 다른 목적은 졸-겔 방법을 이용하여 친수성과 생체적합성이 우수한 유기-무기 복합체를 여러 가지 상품형태로 제조함으로써 다양한 상처에 적용할 수 있는 상처치료용 드레싱의 새로운 제조방법을 제공함에 있다.Still another object of the present invention is to provide a novel method for preparing a wound dressing that can be applied to various wounds by preparing an organic-inorganic complex having excellent hydrophilicity and biocompatibility in various product forms using a sol-gel method. have.
본 발명은 수분흡수 능력이 있고 생체재료로 많이 사용되는 PEG(poly(ethylene glycol))과 졸-겔 공정에 주로 이용되는 TESPI(triethoxysilylpropylisocyanate)를 이용하여 졸-겔 프리커서를 합성 후에 필름 형태의 드레싱과 연고 형태의 드레싱을 제조하고 다양한 범위의 수팽윤도 및 물성을 조절하였다. 또한 제조 공정의 단순화 및 최적 반응 조건을 설정하였다.The present invention is a dressing in the form of a film after synthesis of a sol-gel precursor by using PEG (poly (ethylene glycol)), which is widely used as a biomaterial, and TESPI (triethoxysilylpropylisocyanate), which is mainly used in a sol-gel process. Dressings in the form of the ointment were prepared and a variety of water swelling and physical properties were adjusted. In addition, the simplification of the manufacturing process and the optimum reaction conditions were set.
본 발명은 친수성과 생체적합성을 지닌 PEG와 졸-겔 공정을 적용하기 위해 TESPI를 도입하여 졸-겔 프리커서를 만들고 졸-겔 방법의 적용시 pH와 물의 양을 조절하고 용매를 제거후 50~60℃정도에서 완전히 겔화시켰다. 또한 소수성에 가까운 PPG(polypropylene glycol)과 PTMG(polytetramethylene)를 이용하여 졸-겔 공정에서 PEG와 하이브리드 시킴으로써 수행윤도 및 물성을 조절하였다.The present invention is to make a sol-gel precursor by introducing TESPI to apply PEG and sol-gel process having a hydrophilicity and biocompatibility, to adjust the amount of pH and water and remove the solvent when applying the sol-gel method 50 ~ It gelled completely at about 60 degreeC. In addition, the performance and physical properties were controlled by hybridizing with PEG in the sol-gel process using PPG (polypropylene glycol) and PTMG (polytetramethylene), which are almost hydrophobic.
(I) 졸-겔 프리커서의 합성반응식 및 목적 화합물(I) Synthesis scheme of sol-gel precursor and target compound
a. 친수성을 지닌 졸-겔 프리커서a. Hydrophilic Sol-Gel Precursor
b. 소수성(PPG)을 지니니 졸-겔 프리커서b. Sol-gel precursors with hydrophobicity (PPG)
c. 소수성(PTMG)을 지닌 졸-겔 프리커서c. Sol-gel precursors with hydrophobicity (PTMG)
(Ⅱ) (a)+약산 수용액→졸-겔 메트릭스(II) (a) + weak acid aqueous solution → sol-gel matrix
(Ⅲ)(Ⅱ)+50~60℃에서 겔화→필름 형태의 드레싱(III) gelling at (50) -60 ° C. → dressing in film form
(Ⅳ)(Ⅱ)+증류수를 가하여 적당히 수팽윤시킴→연고 형태의 드레싱(IV) (II) + Distilled water is added to make water swell properly → Ointment dressing
(Ⅴ)(a)+(b)or(c)+약산 수용액→수팽윤도 및 물성을 조절한 졸-겔 메트릭스(V) (a) + (b) or (c) + a weak acid aqueous solution → sol-gel matrix with controlled water swelling and physical properties
PEG는 분자량에 따라서 드레싱의 수팽윤도 및 물성에 크게 영향을 미치는데 분자량이 3000 이하의 경우에는 수팽윤도와 유연성이 떨어지므로 드레싱으로 사용하기에 부적합하고 4000 이상의 경우에는 졸-겔프리커서의 합성에 어려움이 있었다. 따라서 PEG의 분자량은 3400 정도가 가장 적당한 것으로 판명되었다(표 1).PEG greatly affects the water swelling and physical properties of the dressing, but the molecular weight of 3000 or less is not suitable for dressing because of poor water swelling and flexibility. There was a difficulty. Therefore, the molecular weight of PEG was found to be the most suitable about 3400 (Table 1).
수팽윤도의 측정에 있어서는 하이드로겔에 의해서 흡수된 물의 무게를 건조된 하이드로겔의 무게로 나눈 값으로 나타냈다.In the measurement of the water swelling degree, the weight of water absorbed by the hydrogel was expressed by dividing the weight of the dried hydrogel.
그리고 수팽윤도와 물성 조절을 위해 사용한 소수성을 지닌 PPG와 PTMG는 반응몰비를 다르게 함으로써 수팽윤도를 적절히 감소시킬 수 있었으며 물성의 향상을 가져왔다(표 2).In addition, PPG and PTMG with hydrophobicity used to control water swelling and physical properties were able to appropriately reduce water swelling by changing the reaction molar ratio (Table 2).
이상과 같이 본원 발명은 기존의 졸-겔방법을 이용하여 제조된 상처치료용 드레싱의 단점이 보완되어 물성이 개선된 새로운 의료용 소재를 제공함과 더불어 생산성이 우수한 공정을 개발함으로써 상품화시 수요가 급증하리라 예상된다.As described above, the present invention will supplement the shortcomings of the wound dressing prepared using the existing sol-gel method, thereby providing a new medical material with improved physical properties and developing a process with high productivity. It is expected.
이하 본 발명을 다음의 실시예 및 시험예를 통하여 보다 상세히 설명하지만, 본 발명이 이들 실시예 및 시험예에 국한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples and test examples, but the present invention is not limited to these examples and test examples.
[실시예 1]Example 1
[졸-겔 프리커서의 합성 및 최적화][Synthesis and Optimization of Sol-Gel Precursors]
졸-겔프리커서의 합성을 위해 먼저 반응에 사용된 용매로 THF(tetrahydrofuran)는 기존의 정제방법을 이용하였고 DMF(dimethylformamide)는 감압증류를 행하였다. 그리고 PEG와 PPG, PTMG는 100℃, 진공하에서 수분을 제거하였고, TESPI는 정제없이 사용하였다.For the synthesis of sol-gel precursors, THF (tetrahydrofuran) was used as the solvent used in the reaction, and conventional distillation was performed. DMF (dimethylformamide) was subjected to reduced pressure distillation. PEG, PPG, and PTMG removed moisture at 100 ° C. under vacuum, and TESPI was used without purification.
1) 친수성 고분자 폴리에틸렌글리콜을 이용한 졸-겔 프리커서의 합성1) Synthesis of Sol-gel Precursor Using Hydrophilic Polymer Polyethyleneglycol
테트라히드로퓨란(THF) 50ml에 용해된 분자량 3,000-4,000인 PEG(10g, 2.94mmol)용액을 THF(10ml)에 용해된 TESPI(1.46g, 5.88mmol)용액을 상온에서 서서히 첨가하였다. 반응 용액은 질소 분위기 하에서 온도를 70℃로 유지시키며 24시간 동안 교반하면서 반응시켰다. 용매를 증발시킨 후, 비용매인 에틸에테르에 침전시킨 후 진공하에서 4일 동안 건조하여 친수성의 졸-겔프리커서를 얻었다.A PEG (10 g, 2.94 mmol) solution with a molecular weight of 3,000-4,000 dissolved in 50 ml of tetrahydrofuran (THF) was slowly added at room temperature with TESPI (1.46 g, 5.88 mmol) dissolved in THF (10 ml). The reaction solution was reacted with stirring for 24 hours while maintaining the temperature at 70 ° C. under a nitrogen atmosphere. After evaporating the solvent, it was precipitated in non-solvent ethyl ether and dried in vacuo for 4 days to obtain a hydrophilic sol-gel precursor.
2) 소수성 고분자 폴리플로필렌글리콜을 이용한 졸-겔프리커서의 합성2) Synthesis of Sol-Gel Precursor Using Hydrophobic Polymer
THF 50ml에 용해된 PPG(10g, 5mmol)을 THF(10ml)에 용해된 TESPI(2.47g, 10mmol)용액을 상온에서 서서히 첨가하였다. 반응용액은 질소분위기 하에서 70℃로 유지시키며 4일간 교반하면서 반응시켜 소수성의 졸-겔프리커서를 얻었다.PPG (10 g, 5 mmol) dissolved in 50 ml of THF was slowly added to TESPI (2.47 g, 10 mmol) solution dissolved in THF (10 ml) at room temperature. The reaction solution was kept at 70 ° C. under a nitrogen atmosphere and reacted with stirring for 4 days to obtain a hydrophobic sol-gel precursor.
3) 소수성 고분자 폴리테트라메틸렌글리콜을 이용한 졸-겔프리커서의 합성3) Synthesis of Sol-Gel Precursor Using Hydrophobic Polymer Polytetramethylene Glycol
THF 50ml에 용해된 PTMG(10g, 5mmol)을 THF(10ml)에 용해된 TESPI(2.47g, 10mmol)용액을 상온에서 서서히 첨가하였다. 반응용액은 질소분위기 하에서 70℃로 유지시키며 4일간 교반하면서 반응시켜 소수성의 졸-겔프리커서를 얻었다.PTMG (10 g, 5 mmol) dissolved in 50 ml of THF was slowly added to TESPI (2.47 g, 10 mmol) solution dissolved in THF (10 ml) at room temperature. The reaction solution was kept at 70 ° C. under a nitrogen atmosphere and reacted with stirring for 4 days to obtain a hydrophobic sol-gel precursor.
4) 최적용매 및 반응온도 실험4) Optimal Solvent and Reaction Temperature Experiment
친수성 및 소수성 고분자의 반응용매로 THF, DMF를 적용한 결과, 졸-겔프리커서의 형성은 두가지 용매 모두가 잘 되었으나, DMF의 경우에는 용매증발시 어려움이 있었다.또한, 반응온도는 70℃ 정도가 최적온도이었다.As a result of applying THF and DMF as a reaction solvent for hydrophilic and hydrophobic polymers, sol-gel precursors were well formed in both solvents, but DMF had difficulty in evaporating solvents. Optimum temperature.
[실시예 2]Example 2
[졸-겔 공정을 통한 졸-겔 메트릭스의 제조][Preparation of Sol-Gel Matrix by Sol-Gel Process]
친수성 고분자 졸-겔 프리커서 5g을 THF, DMF, DCM(30ml)에 각각 용해한후 15M 염산 수용액(10ml)을 첨가하여 1시간 동안 상온에서 교반시켰다. 교반이 끝난 용액은 샤알레에 부어 상온에서 THF와 DCM은 3일간의 건조과정에서 2일 이내에 균열이 거의 없는 투명한 겔 필름 또는 코팅막이 형성되었다. 그러나 DMF는 5일간의 건조과정에서 3일 이내에 균열이 발생하지 않는 것으로 관찰되었다. 합성된 졸-겔프리커서의 용해도와 겔형성과정에서 적절한 용매의 증발속도를 고려할 때 DCM(디클로로메탄)은 증발속도가 빨라서 기포가 발생하고, DMF(디메틸포름알데히드)는 증발속도가 느리기 때문에 제조공정이 길어지는 단점이 있다. 합성된 졸-겔 프리커서의 용해도와 겔형성과정에서 적절한 용매의 증발속도를 고려할 때 THF(테트라히드로퓨란)이 가장 효과적인 용매로 확인되었다.5 g of hydrophilic polymer sol-gel precursors were dissolved in THF, DMF, and DCM (30 ml), respectively, and 15M aqueous hydrochloric acid solution (10 ml) was added thereto, followed by stirring at room temperature for 1 hour. After stirring, the solution was poured into a shaker, and THF and DCM at room temperature formed a transparent gel film or coating film with little cracking within 2 days of drying for 3 days. However, DMF was not observed to crack within 3 days after 5 days of drying. Considering the solubility of the synthesized sol-gel precursor and the evaporation rate of a suitable solvent in the gel formation process, DCM (dichloromethane) has a high evaporation rate and bubbles are produced, and DMF (dimethylformaldehyde) is prepared because of a slow evaporation rate. There is a disadvantage that the process is long. Considering the solubility of the synthesized sol-gel precursor and the evaporation rate of the appropriate solvent in the gel formation process, THF (tetrahydrofuran) was identified as the most effective solvent.
[실시예 3]Example 3
[졸-겔 메트릭스의 제조를 위한 공정의 단순화][Simplification of Process for Preparation of Sol-Gel Matrix]
졸-겔 공정을 통한 메트릭스의 제조의 경우, 졸-겔 프리커서의 합성 과정에서 2일, 건조과정에서 3일, 졸-겔 반응을 마친 후 상온에서 겔 형성과정에서 5일 정도가 소요된다. 그러나 이들의 제조공정이 장시간 소요되므로 본원 발명에서는 졸-겔 프리커서의 합성후 용매의 증발 및 건조과정을 생략했다. 즉 졸-겔프리커서를 합성한 후 바로 졸-겔 공정을 적용하기 위해 약산 용액을 첨가하여 1시간 정도 반응시킨 후 샤알레에 담아서 상온에서 건조시켰다.In the preparation of the matrix through the sol-gel process, it takes about 2 days in the synthesis process of the sol-gel precursor, 3 days in the drying process, and 5 days in the gel formation process at room temperature after the sol-gel reaction. However, since the preparation process takes a long time, the present invention omits the evaporation and drying process of the solvent after the synthesis of the sol-gel precursor. That is, after the synthesis of the sol-gel precursor, a weak acid solution was added and reacted for about 1 hour in order to apply the sol-gel process.
[실시예 4]Example 4
[필름 및 연고 형태의 드레싱 제조][Manufacture of dressings in film and ointment form]
필름 형태의 드레싱을 제조하기 위해서는 상온에서 건조된 메트릭스를 50~60℃ 정도의 온도로 오븐에 하루정도를 방치함으로서 상온에서 건조된 메트릭스 보다는 온도의 영향으로 인해 겔화가 진해되므로 우수한 물성을 지닌다. 또한 연고형태의 드레싱은 증류수에 메트릭스를 보관하여 수행윤도에 따라 연고 형태로 사용이 가능해진다.In order to produce a film-type dressing, the matrix dried at room temperature is left in the oven at a temperature of about 50 to 60 ° C. for about one day, and thus gelation is increased due to the influence of temperature rather than the matrix dried at room temperature. In addition, the dressing in the ointment form can be used in the form of ointment according to the performance of the matrix by storing the matrix in distilled water.
[실시예 5]Example 5
[졸-겔 공정에 있어서 수팽윤도 조절을 위한 친수성과 소수성의 결합][Combination of Hydrophilicity and Hydrophobicity for Control of Water Swelling in Sol-Gel Process]
졸-겔 메트릭스 제조시, 소수성을 지닌 PPG나 PTMG를 단순화된 졸-겔 공정에 적용하고 졸-겔 프리커서를 합성후 건조된 PEG를 이용한 졸-겔 프리커서를 몰비(PEG:PPG 또는 PTMG=1:1 또는 2:1)따라 삽입함으로써 수팽윤도를 조절하였다. 물론 PEG 졸-겔 프리커서의 삽입을 제외한 나머지 공정은 단순화된 졸-겔프리커서 공정과 동일하다.In preparing the sol-gel matrix, hydrophobic PPG or PTMG is applied to a simplified sol-gel process, the sol-gel precursor is synthesized, and the sol-gel precursor is dried using dried PEG (PEG: PPG or PTMG = The degree of water swelling was adjusted by insertion according to 1: 1 or 2: 1). Of course, except for the insertion of the PEG sol-gel precursor, the process is the same as the simplified sol-gel precursor process.
[시험예 1][Test Example 1]
[졸-겔프리커서의 합성 확인][Synthesis of Sol-Gel Precursor]
졸-겔 프리커서의 합성을 양성자 NMR(nucler magnetic resonance)을 통해서 확인하였다 PEG(-CH2CH2O-)의 양성자 피크가 3.65ppm에서 관찰되었고, TESPI의 경우에는 모두 5개의 피크가 나타나는데 0.63ppm에서 (EtO)3)Si-CH2CH2CH2-, 1.61ppm에서 (EtO)3Si-CH2CH2CH2-, 3.17ppm에서 (EtO)3)Si-CH2CH2CH2-, 1.24ppm에서 CH3CH2O-, 3.82ppm에서 CH3CH2O- 피크가 관찰되어진다. 또한 졸-겔 프리커서의 합성확인에 있어서 PEG와 TESPI의 결합을 나타내는 우레탄 결합(-NHCOO-)은 4.21ppm에서 확인되었다.Synthesis of the sol-gel precursor was confirmed by proton nucler magnetic resonance (NMR). The proton peak of PEG (-CH 2 CH 2 O-) was observed at 3.65 ppm, and in the case of TESPI, five peaks appeared. in ppm (EtO) 3) Si- CH 2 CH 2 CH 2 -, at 1.61ppm (EtO) 3 Si-CH 2 CH 2 CH 2 -, 3.17ppm in (EtO) 3) Si-CH 2 CH 2 CH 2 -, a CH 3 CH 2 O- peak in CH 3 CH 2 O-, 3.82ppm 1.24ppm in is observed. In addition, the urethane bond (-NHCOO-) which shows the bond of PEG and TESPI in the synthesis confirmation of the sol-gel precursor was confirmed at 4.21 ppm.
[시험예 2][Test Example 2]
[졸-겔 공정으로부터 얻어진 하이드로겔의 수팽윤도 측정][Measurement of Water Swelling of Hydrogel Obtained from Sol-Gel Process]
수팽윤도 측정시에는 하이드로겔을 넓이 1cm2정도로 손상이 가지않게 잘라서 3차 증류수(pH 7)에서 시간과 온도의 조건을 고정하여 측정하였다. 또한 수팽윤된 상태의 시편을 거즈에 잘 닦아서 표면에 물기가 없도록 하였다.In the water swelling measurement, the hydrogel was cut to a width of about 1 cm 2 without damage and was measured by fixing conditions of time and temperature in tertiary distilled water (pH 7). In addition, the water-swelled specimen was well wiped with gauze to keep the surface dry.
졸-겔방법을 도입하여 유기-무기 고분자복합체를 제조하여 새로운 상처치료용 드레싱을 개발함에 있어서 분자량 2,000~4,000 정도의 친수성 고분자인 폴리에틸렌글리콜(PEG), 소수성 고분자인 폴리플로필렌글리콜(PPG)과 폴리테트라메틸렌글리콜(PTMG) 등에 트리에톡시실릴프로필이소시아네이트(TESPI)를 이용한 졸-겔 프리커서를 제조하여 상처치료용 드레싱에 적용함으로서 고분자 메트릭스의 다양한 수팽윤도(4-16배) 및 물성으로 인하여 상처분비물의 조절이 용이하므로, 다양한 상처부위에 적용할 수 있으며 필름 및 연고 형태의 상품화 추진이 가능하고 제조공정을 단순화할 수 있다.Introducing the sol-gel method to produce organic-inorganic polymer composites to develop new wound dressings, polyethylene glycol (PEG), a hydrophilic polymer with a molecular weight of 2,000 to 4,000, and polyflophylene glycol (PPG), a hydrophobic polymer, Sol-gel precursors using triethoxysilylpropyl isocyanate (TESPI) using polytetramethylene glycol (PTMG), etc. are prepared and applied to wound dressings, resulting in various water swelling (4-16 times) and physical properties of the polymer matrix. It is easy to control the wound discharge, it can be applied to various wounds, it is possible to promote the commercialization of the film and ointment form and simplify the manufacturing process.
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