KR20030054566A - A poly amino alcohol phosphazene compound, and a process of preparing for the same - Google Patents

A poly amino alcohol phosphazene compound, and a process of preparing for the same Download PDF

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KR20030054566A
KR20030054566A KR1020010084742A KR20010084742A KR20030054566A KR 20030054566 A KR20030054566 A KR 20030054566A KR 1020010084742 A KR1020010084742 A KR 1020010084742A KR 20010084742 A KR20010084742 A KR 20010084742A KR 20030054566 A KR20030054566 A KR 20030054566A
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phosphazene
polymer
tetrahydrofuran
integer
solution
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김학용
소장로
이호근
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진비컨 주식회사
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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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/025—Polyphosphazenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/02—Applications for biomedical use

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Medicinal Preparation (AREA)

Abstract

PURPOSE: A polyamino alcohol phosphazene polymer and its preparation method are provided, to improve the binding affinity of the polymer to a polyvalent metal cation, an antigen and a drug by introducing a water-soluble amino alcohol group to a phosphazene polymer. CONSTITUTION: The polyamino alcohol phosphazene polymer comprises a repeating unit represented by the formula I, wherein R is -CH2-; n is an integer of 1-100; and x is an integer of 10-200. The method comprises the steps of dissolving poly(chlorophosphazene) in tetrahydrofuran; and adding a solution mixture of aminoethanol, triethylamine and tetrahydrofuran to the solution drop by drop, to react them. Preferably the polychloro phosphazene is obtained by polymerizing hexachloro phosphazene in the presence of an anhydrous aluminum polymerization catalyst.

Description

폴리아미노알코올포스파젠 고분자 및 그의 제조방법 {A poly amino alcohol phosphazene compound, and a process of preparing for the same}Polyamino alcohol phosphazene polymer and method for preparing the same {A poly amino alcohol phosphazene compound, and a process of preparing for the same}

본 발명은 폴리아미노알코올포스파젠 고분자 및 그의 제조방법에 관한 것이다. 보다 구체적으로 본 발명은 다가양이온금속, 항원, 약물 등과 결합이 가능하여 금속복합체, 면역보강제, 서방형제제, 하이드로겔, 각종전해질, 기능성 고분자, 생체분해성 고분자, 촉매 및 난연제 등으로 사용할 수 있는 폴리아미노알코올포스파젠 고분자 및 그의 제조방법에 관한 것이다.The present invention relates to a polyamino alcohol phosphazene polymer and a preparation method thereof. More specifically, the present invention can be combined with polycationic metals, antigens, drugs, and the like, and thus can be used as metal complexes, immune adjuvant, sustained-release agent, hydrogel, various electrolytes, functional polymers, biodegradable polymers, catalysts and flame retardants. Amino alcohol phosphazene polymer and its manufacturing method are related.

생체분해성 고분자의 핸드북(Handbook of biodegradable polymer), 9장[A.J. Domb, J. Kost and D.M. Wiseman] 에서는 일반적인 폴리포스파젠 고분자 화합물, 다시말해 수용성의 아미노알코올 그룹을 함유하지 않는 폴리포스파젠 고분자 화합물에 대해 상세하게 설명하고 있다.Handbook of biodegradable polymers, Chapter 9 [A.J. Domb, J. Kost and D.M. Wiseman] describes in detail the general polyphosphazene polymer compounds, that is, polyphosphazene polymer compounds that do not contain a water-soluble aminoalcohol group.

상기 폴리포스파젠 고분자 화합물은 통상적으로 헥사클로로포스파젠 (Hexachloro phosphazene)을 원료로 사용하여 제조된다. 헥사클로로포스파젠은 여러개의 반응기를 갖고 있어서, 반응중 가교결합을 할 수 있는 가능성이 매우 높고, 250℃ 정도의 온도에서 촉매없이 중합하여도 분자량이 2×106~10×106이고, 분자량 분포가 10 정도인 폴리포스파젠 고분자 화합물을 제조할 수 있다.The polyphosphazene polymer compound is typically prepared using hexachloro phosphazene (Hexachloro phosphazene) as a raw material. Since hexachlorophosphazene has several reactors, the possibility of crosslinking during the reaction is very high, and the molecular weight is 2 × 10 6 to 10 × 10 6 even when polymerized without a catalyst at a temperature of about 250 ° C. A polyphosphazene polymer compound having a distribution of about 10 can be prepared.

1992년에 발간된 마크로모레큐러스(Macromolecules) Vol 25, 1254-1258쪽에는 폴리(디클로로)포스파젠 화합물이 공지되어 있고, 1990년에 발간된 마크로모레큐러스(Macromolecules) Vol 23 14-21쪽에는 헥사클로로포스파젠을 용액 중합하여 분자량이 105정도이고 분자량분포가 매우 좁은 폴리포스파젠 고분자 화합물을 제조하는 내용이 기재되어 있다.The poly (dichloro) phosphazene compound is known from Macromolecules Vol 25, pages 1254-1258, published in 1992, and Macromolecules Vol 23 pages 14-21 published in 1990. Is a solution polymerization of hexachlorophosphazene to prepare a polyphosphazene polymer compound having a molecular weight of about 10 5 and a very narrow molecular weight distribution.

또한 1999년에 발간된 폴리머 인터내셔널(Polymer International) Vol 48, 627-629쪽에는 독소루비신(Doxorubicin)과 플래티늄(Platinum) 항암제가 부착된 폴리포스파젠 화합물이 기재되어 있고, 1999년에 발간된 J.A. 폴리머 사이언스(J.Appllied polymer sicience) Vol 71, 387-399쪽에는 설폰화폴리[비스 (3-메틸페녹시)포스파젠]으로 막을 제조하는 내용이 기재되어 있다.In addition, Polymer International Vol 48, 627-629, published in 1999, describes polyphosphazene compounds with doxorubicin and platinum anticancer agents, and published in J.A. J. Appllied polymer sicience Vol 71, pages 387-399, describes the preparation of membranes with sulfonated poly [bis (3-methylphenoxy) phosphazene].

미국특허 제 5,260,103호에서는 카보닐(Carbonyl)기와 다양한 형태의 알킬레이티드 3급 아미노(Alkylated tertiary amino) 그룹을 함유하는 폴리포스파젠 유도체를 제안하고 있고, 미국특허 제 6,015,563호에서는 벤젠환에 3개의 반응기가 있는 그룹이 결합된 폴리포스파젠 유도체를 합성한후, 이를 면역보강제로 사용하는방안을 제안하고 있고, 미국특허 제6,207,171호에서는 폴리포스파젠으로 마이크로스페어(Microsphere)를 제조하여 약물전달체로 활용하는 내용이 기재되어 있다.U.S. Patent No. 5,260,103 proposes a polyphosphazene derivative containing a carbonyl group and various types of alkylated tertiary amino groups, and U.S. Patent No. 6,015,563 provides three benzene rings. Synthesis of polyphosphazene derivatives in which a group having a reactor is combined and then proposed a method of using the same as an adjuvant, US Patent No. 6,207,171 prepared a micro-spare (polysphere) with polyphosphazene to be used as a drug carrier The content is described.

이상에서 살펴본 종래의 포스파젠 고분자들은 수용성의 아미노알코올 그룹을 함유하고 있지 않아서, 다가양이온금속, 항원, 약물 등과의 결합성이 부족한 문제점이 있었다. 그 결과 종래의 포스파젠 화합물 또는 그의 고분자들은 용도가 한정되어 다양한 산업분야에서 사용될 수 없는 한계가 있었다.Conventional phosphazene polymers described above do not contain a water-soluble aminoalcohol group, there is a problem in the lack of binding to polycationic metals, antigens, drugs and the like. As a result, conventional phosphazene compounds or polymers thereof have limitations that their use is limited and cannot be used in various industrial fields.

본 발명의 목적은 이와 같은 종래의 문제점을 해소할 수 있도록 항원, 약물, 다가양이온금속과의 결합성이 우수하여 다양한 산업분야에서 사용가능한 폴리아미노알코올포스파젠 고분자를 제공하기 위한 것이다.An object of the present invention is to provide a polyamino alcohol phosphazene polymer that can be used in a variety of industries by excellent binding to antigens, drugs, polycation metals to solve such a conventional problem.

본 발명은 포스파젠 고분자에 수용성의 아미노알코올 그룹을 도입함으로서 다가양이온금속, 항원, 약물 등과의 결합성을 개선하고자 한다. 또한 본 발명은 금속복합체, 면역보강제 및 서방형제제 등과 같이 다양한 산업분야에 유용한 폴리포스파젠 고분자를 제공하고자 한다.The present invention is intended to improve the binding properties of polycationic metals, antigens, drugs and the like by introducing a water-soluble amino alcohol group in the phosphazene polymer. In another aspect, the present invention is to provide a polyphosphazene polymer useful in a variety of industries, such as metal complexes, immune adjuvant and sustained release formulations.

도 1은 폴리아미노에탄올포스파젠 고분자의 31-P(인) 핵자기 공명 스펙트럼.1 is a 31-P (phosphorus) nuclear magnetic resonance spectrum of a polyaminoethanol phosphazene polymer.

이와 같은 과제들을 달성하기 위한 본 발명의 폴리아미노알코올포스파젠 고분자는 하기 일반식(Ⅰ)의 구조를 갖고 아미노알코올 그룹을 함유하는 것을 특징으로 한다.The polyamino alcohol phosphazene polymer of the present invention for achieving the above problems is characterized by having the structure of the general formula (I) and containing an amino alcohol group.

[상기 식(Ⅰ)에서 R은 CH2이고, n은 1~100의 정수이고, x는 10~200의 정수이다][Wherein R is CH 2 in the formula (I), n is an integer from 1 to 100, x is an integer from 10 to 200]

이하, 본 발명을 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

상기 일반식(Ⅰ)의 본 발명 헥사아미노알코올포스파젠 화합물은 (ⅰ)폴리클로로포스파젠 화합물을 테트라하이드로퓨란에 용해한 용액에 (ⅱ) 아미노에탄올, 트리에틸아민 및 테트라하이드로퓨란의 혼합용액을 적가한 후, 교반시키면서 반응시켜 제조할 수 있다.The hexaaminoalcohol phosphazene compound of the present invention of general formula (I) is added dropwise to (ii) a mixed solution of aminoethanol, triethylamine and tetrahydrofuran in a solution obtained by dissolving the (iii) polychlorophosphazene compound in tetrahydrofuran. After that, the mixture can be prepared by reacting with stirring.

상기 폴리클로로포스파젠은 고순도의 헥사클로로포스파젠을 고순도의 무수알루미늄 중합촉매 하에서 중합하여 제조하는 것이 바람직 하다.The polychlorophosphazene is preferably prepared by polymerizing high purity hexachlorophosphazene under a high purity anhydrous aluminum polymerization catalyst.

이때 원료인 헥사클로로포스파젠으로는 순도가 99.9% 수준인 것을 사용하며, 반응은 질소분위기에서 85℃로 72시간동안 실시하는 것이 바람직 하다.At this time, the hexachlorophosphazene is used as a raw material having a purity level of 99.9%, the reaction is preferably carried out for 72 hours at 85 ℃ in a nitrogen atmosphere.

다음으로는 상기 반응에 의해 얻어지는 노란색의 점성 고분자 화합물을 테트라하이드로퓨란 용매로 세척하고, 메탄올로 용해하여 용해된 용액을 얻는다.Next, the yellow viscous polymer compound obtained by the above reaction is washed with a tetrahydrofuran solvent, dissolved in methanol to obtain a dissolved solution.

계속해서 메탄올에 용해된 용액을 헥산에 침전시켜 폴리아미노알코올포스파젠 고분자를 제조하게 된다.Subsequently, the solution dissolved in methanol is precipitated in hexane to prepare a polyamino alcohol phosphazene polymer.

이와 같이 제조된 본 발명의 폴리아미노알코올포스파젠 고분자는 수용성의 아미노알코올 그룹을 함유하고 있어서, Cu, Fe, Pt, As, Mg, Al 등의 다가양이온금속과 쉽게 결합하여 금속복합체로 유용하다.Thus prepared polyamino alcohol phosphazene polymer of the present invention contains a water-soluble amino alcohol group, it is useful as a metal complex by easily bonding with a polycationic metal such as Cu, Fe, Pt, As, Mg, Al.

또한 항원과 쉽게 결합하여 면역보강제로도 유용하며, 약물과 쉽게 결합하여 서방형제제로도 유용하다.In addition, it is useful as an adjuvant by easily binding to the antigen, and also useful as a sustained release formulation by easily binding to the drug.

아울러 프로테인(Protein), 펩티드(Peptide), DNA 또는 RNA의 헥산, 폴리사차라이드(polysaccharide), 글리코프로테인(Glycoprotein), 글리코리피드(Glycolip -id), 세포, 박테리아, 바이러스, 이들의 유도체 또는 이들의 혼합물과 결합이 용이하여 하이드로겔, 각종전해질, 기능성 고분자, 생체분해성 고분자, 촉매 또는 난연제 등으로 유용하다.In addition, proteins, peptides, hexane, polysaccharides, glycoproteins, glycoproteins, glycolipids, cells, bacteria, viruses, derivatives thereof, or hexanes of DNA or RNA It is useful as a hydrogel, various electrolytes, functional polymers, biodegradable polymers, catalysts or flame retardants due to its ease of bonding with the mixture.

도 1은 폴리아미노에탄올포스파젠 고분자의 31-P(인) 핵자기 공명(NMR) 스펙트럼으로 -8.3ppm 부근에서 하나의 피크를 보인다.1 shows one peak in the vicinity of -8.3 ppm in 31-P (phosphorus) nuclear magnetic resonance (NMR) spectrum of a polyaminoethanol phosphazene polymer.

이하 실시예를 통하여 본 발명을 구체적으로 살펴본다. 그러나 본 발명이 하기 실시예에만 한정되는 것은 아니다.The present invention is described in detail through the following examples. However, the present invention is not limited only to the following examples.

실시예 1Example 1

먼저, 순도가 99.9%인 헥사클로로포스파젠 2.0g을 순도가 99.99%인 무수알루미늄의 중합촉매(1g) 하에서 255℃로 중합하여 폴리클로로포스파젠을 합성한다. 다음으로, 테트라하이드로퓨란(Tetrahydrofuran)에 앞서 합성된 폴리클로로포스파젠을 용해하여 용액을 제조한다. 한편, 테트라하이드로퓨란에 아미노에탄올 3cc와 트리에틸아민 12cc를 혼합하여 혼합용액을 제조한다. 이때 테트라하이드로퓨란과 트리에틸아민은 CaH2로 건조, 증류한 후 사용하고, 아미노에탄올로는 순도 99.9%인 것을 사용한다. 이와같이 제조된 혼합용액을 폴리클로로포스파젠이 용해된 용액에 20시간에 걸쳐 방울형태로 교반하면서 서서히 공급하고, 질소분위기 하에서 85℃로 72시간 동안 교반 및 반응시켜 노란색을 띠는 점성의 고분자 물질을 제조한다. 계속해서 제조된 노란색을 띠는 점성의 고분자 물질을 테트라하이드로퓨란으로 세척하고 메탄올에 용해하고, 용해된 용액만을 헥산에 침전시켜 폴리(아미노에탄올)포스파젠 고분자를 얻는다. 원료인 헥사클로로포스파젠에 대한 수율은 10% 이다.First, 2.0 g of hexachlorophosphazene having a purity of 99.9% is polymerized at 255 ° C under a polymerization catalyst (1 g) of anhydrous aluminum having a purity of 99.99% to synthesize polychlorophosphazene. Next, a solution is prepared by dissolving the polychlorophosphazene previously synthesized in tetrahydrofuran. Meanwhile, 3 cc of aminoethanol and 12 cc of triethylamine are mixed with tetrahydrofuran to prepare a mixed solution. At this time, tetrahydrofuran and triethylamine are used after drying and distilling with CaH 2 , and as aminoethanol, those having a purity of 99.9% are used. The mixed solution thus prepared was slowly supplied to the solution in which polychlorophosphazene was dissolved in a drop form over 20 hours, and stirred and reacted at 85 ° C. for 72 hours under a nitrogen atmosphere to give a yellow viscous polymer material. Manufacture. Subsequently, the yellowish viscous polymer material thus prepared is washed with tetrahydrofuran and dissolved in methanol, and only the dissolved solution is precipitated in hexane to obtain a poly (aminoethanol) phosphazene polymer. The yield for the raw material hexachlorophosphazene is 10%.

본 발명의 폴리아미노알코올포스파젠 고분자는 수용성의 아미노알코올 그룹을 함유하여 다가양이온금속, 항원, 약물 등과의 결합성이 우수하다. 그 결과 본 발명의 포스파젠 화합물은 금속복합체, 면역보강제 및 서방형제제 등의 다양한 산업분야에서 유용하게 사용될 수 있다.The polyaminoalcohol phosphazene polymer of the present invention contains a water-soluble aminoalcohol group and has excellent binding property with a polycation metal, an antigen, a drug and the like. As a result, the phosphazene compound of the present invention can be usefully used in various industrial fields such as metal complexes, immunoadjuvant and sustained release formulations.

Claims (3)

하기 일반식(Ⅰ)의 반복단위를 갖는 폴리아미노알코올포스파젠 고분자.Polyamino alcohol phosphazene polymer which has a repeating unit of the following general formula (I). [상기 식(Ⅰ)에서 R은 CH2이고, n은 1~100의 정수이고, x는 10~200의 정수이다][Wherein R is CH 2 in the formula (I), n is an integer from 1 to 100, x is an integer from 10 to 200] (ⅰ)폴리클로로포스파젠을 테트라하이드로퓨란에 용해한 용액에 (ⅱ) 아미노에탄올, 트리에틸아민 및 테트라하이드로퓨란의 혼합용액을 적가한 후, 이들을 반응시킴을 특징으로 하는 폴리아미노알코올포스파젠 고분자의 제조방법.(Iii) a solution of aminoethanol, triethylamine and tetrahydrofuran is added dropwise to a solution of polychlorophosphazene dissolved in tetrahydrofuran, followed by reaction of the polyamino alcohol phosphazene polymer. Manufacturing method. 2항에 있어서, 고순도의 헥사클로로포스파젠을 무수알루미늄 중합촉매 하에서 중합하여 폴리클로로포스파젠을 중합하는 것을 특징으로 하는 폴리아미노알코올포스파젠 고분자의 제조방법.The method for producing a polyaminoalcohol phosphazene polymer according to claim 2, wherein the high-purity hexachlorophosphazene is polymerized under anhydrous aluminum polymerization catalyst to polymerize polychlorophosphazene.
KR1020010084742A 2001-12-26 2001-12-26 A poly amino alcohol phosphazene compound, and a process of preparing for the same KR20030054566A (en)

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WO2021259848A1 (en) * 2020-06-26 2021-12-30 Covestro Deutschland Ag Polyurethanes based on side chain diol- and diaminopolyphosphazenes and their hydrogels

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US5104947A (en) * 1989-08-07 1992-04-14 Ethyl Corporation Polyphosphazenes and their synthesis
US5914231A (en) * 1995-08-17 1999-06-22 Universiteit Utrecht Introgene B.V. Poly(organo)phosphazenes for use in synthetic transfection systems

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Publication number Priority date Publication date Assignee Title
US5104947A (en) * 1989-08-07 1992-04-14 Ethyl Corporation Polyphosphazenes and their synthesis
US5914231A (en) * 1995-08-17 1999-06-22 Universiteit Utrecht Introgene B.V. Poly(organo)phosphazenes for use in synthetic transfection systems

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021259848A1 (en) * 2020-06-26 2021-12-30 Covestro Deutschland Ag Polyurethanes based on side chain diol- and diaminopolyphosphazenes and their hydrogels

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