KR900003916B1 - Bydrophilic terpolymer - Google Patents
Bydrophilic terpolymer Download PDFInfo
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- KR900003916B1 KR900003916B1 KR1019870008751A KR870008751A KR900003916B1 KR 900003916 B1 KR900003916 B1 KR 900003916B1 KR 1019870008751 A KR1019870008751 A KR 1019870008751A KR 870008751 A KR870008751 A KR 870008751A KR 900003916 B1 KR900003916 B1 KR 900003916B1
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- hydroxyethyl methacrylate
- pyrrolidone
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- methacrylate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
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Abstract
Description
[발명의 명칭][Name of invention]
친수성 터폴리머(Hydrophilic terpolymer)Hydrophilic terpolymer
[발명의 상세한 설명]Detailed description of the invention
본 발명은 친수성 터폴리머에 관한 것이다. 더욱 상세하게는 2-하이드록시에틸메타크릴레이트, N-비닐-2-피롤리돈 및 3-하이드록시프로필메타크릴레이트가 가교결합한 터폴리머에 관한 것이다.The present invention relates to a hydrophilic terpolymer. More specifically, it relates to a terpolymer cross-linked with 2-hydroxyethyl methacrylate, N-vinyl-2-pyrrolidone and 3-hydroxypropyl methacrylate.
본 발명의 상기 터폴리머는 아래 구조식과 같은 가교결합을 이루고 있다.The terpolymer of the present invention has a crosslink as shown in the following structural formula.
위의 구조식에서 x+y+z=1이 된다. 고분자의 기능과 용도는 다양하게 개발되고 있으며, 최근 특히 의료재료로서의 고분자의 기능이 각광을 받아 중요한 의의가 있다. 그중에서도 하이드로겔(hydrogel)을 의료용 재료로서 사용하는 추세가 더욱 늘고 있다. 하이드로겔의 의료용 재료로서 각광을 받고 있는것은 그것이 생물조직과 유사한 물성을 갖고 있기 때문이다. [참조 : S.D.Bruck.J.Biomed.Mater.Res., 7, 387 (1973)]In the structure above, x + y + z = 1. The function and use of the polymer has been variously developed, and recently, the function of the polymer as a medical material has been in the spotlight, and thus has an important significance. Among them, the trend of using hydrogel as a medical material is increasing. It is attracting attention as a medical material for hydrogels because it has properties similar to biological tissues. [Reference: S.D.Bruck.J.Biomed.Mater.Res., 7, 387 (1973)]
더우기 물의 함량이 많고 가공성이 있으며, 투과성이 커서, 중합과정에서 남은 개시제, 용매등을 쉽게 제공할 수 있어 하이드로겔을 생체내에 적용할 경우 거부반응을 줄이고, 적합성이 크기 때문에 매우 효과적이다. 하이드로겔은 여러가지 중합법과 기존고분자의 수식에 의해 제조할 수 있다.In addition, the water content and processability, and the permeability is large, it is easy to provide the initiator, solvent, etc. remaining in the polymerization process, it is very effective because the hydrogel is applied in vivo to reduce the rejection reaction, the suitability is large. Hydrogels can be prepared by various polymerization methods and modification of existing polymers.
합성고분자로서 이들을 예시하면 다음과 같다. 첫째 : 폴리하이드록시알킬메타크릴레이트를 들 수 있다. 이 가운데 폴리(2-하이드록시에틸메타크릴레이트)가 처음으로 개발되었다. [참조 : O.Wichterle and D, Lim, Nature, 185.167(1%0)] 둘째 : 폴리(아크릴아미드) 및 그 유도체로서 이들은 소량의 가교제를 포함한 아클리아미드를 라디칼중합하여 수득한다. [참조 : K.Kudela, A.stoy and R.Urbano a.European polymer J., 10.905(1974)] 세째 : 폴리(N-비닐-2-피롤리돈(P-NVP)으로서 이것은 물에 대한 용해도가 크고 독성이 적다. [참조 : G.Mohn, Acta Histochem., 9,76(1960)] 네째 : 폴리비닐알콜(PVA)로서 수용성 PVA를 포름알데히드로 가교시켜 수득한다. [참조 : R.H.Alder and C.Darby.U.S Armed Forces Medical Jounual., 11, 1349(1960)] 다섯째 :음이온의 고분자를 반응시켜 얻은 고분자간 전해질 복합체이다. [참조 : L.L.Markley, H.J.Bixler and R.A.cross, J.Biomed Mater Res., 2, 145(1968)]Examples of these as synthetic polymers are as follows. First: polyhydroxyalkyl methacrylate. Among these, poly (2-hydroxyethyl methacrylate) was first developed. [Reference: O. Wichterle and D, Lim, Nature, 185.167 (1% 0)] Second: poly (acrylamides) and derivatives thereof obtained by radical polymerization of acliamide with a small amount of crosslinking agent. [K.Kudela, A.stoy and R.Urbano a.European polymer J., 10.905 (1974)] Third: Poly (N-vinyl-2-pyrrolidone (P-NVP), which is solubility in water [G. Mohn, Acta Histochem., 9,76 (1960)] Fourth: Polyvinyl alcohol (PVA) obtained by crosslinking of water-soluble PVA with formaldehyde [RHAlder and C. Darby. US Armed Forces Medical Jounual., 11, 1349 (1960)] Fifth: It is an interpolymer electrolyte complex obtained by reacting anionic polymers. ., 2, 145 (1968)].
위에 열거한 하이드로겔 중에서도 의료용 재료로 가장 많이 시도되고 있는것은 폴리(2-하이드록시에틸메타크릴레이트)로서, 조직배양체, 약물운반체, 봉합사, 혈액정제제, 뼈형성체등에 이용되고 있는데 무엇보다도 의의가 있는것은 콘택트렌즈에 이용하는 것인데 여러가지 종류의 상품이 개발되어 시판되고 있다. 그러나 콘택트렌즈로 이용되려면 재료의 기계적 강도, 상체내의 접합성, 무독성, 재료의 투명도, 굴절율, 표면친수성, 기계투과성, 사용간이성, 연속창용성등 여러조건을 충족시켜 주지 않으면 안된다. 종래의 하이드로겔에 있어서는 이러한 여러조건을 전부 만족시켜 줄만한 것이 없었다.Among the hydrogels listed above, poly (2-hydroxyethyl methacrylate) is the most attempted medical material, and is used in tissue culture, drug carriers, sutures, blood tablets, and bone formations. It is used in contact lenses, and various kinds of products have been developed and marketed. However, in order to be used as a contact lens, the mechanical strength of the material, adhesion in the upper body, nontoxicity, material transparency, refractive index, surface hydrophilicity, mechanical permeability, simplicity of use, continuous creativity must be satisfied. In the conventional hydrogel, there was nothing to satisfy all of these conditions.
본 발명자들은 새로운 하이드로겔 개발을 위해 꾸준한 연구를 계속하고 본 발명을 완성하기에 이르렀다. 종래의 폴리(2-하이드록시에틸메타크릴레이트)로는 여러 결점이 따르기 때문에 본 발명자들은 그 개선을 위한 연구를 거듭하고, 폴리(2-하이드록시에틸메타크릴레이트)보다는 수분함유율이 낮지만 기계적 성질이 우수한 폴리(하이드록시프로필메타크릴레이트)를 사용하고, 또한 친수성이 우수한 폴리(N-비닐-2-피롤리돈)를 사용하고, 개시중합으로 터폴리머를 제조할 수 있었다.The present inventors have continued to research and develop the new hydrogel to complete the present invention. Because of the shortcomings with conventional poly (2-hydroxyethyl methacrylate), the present inventors have been intensively researched for improvement, and although the water content is lower than that of poly (2-hydroxyethyl methacrylate), mechanical properties Using this excellent poly (hydroxypropyl methacrylate) and using poly (N-vinyl-2-pyrrolidone) excellent in hydrophilicity, a terpolymer could be produced by initiation polymerization.
본 발명의 하이드로겔은 기계적 성질이 뛰어나고 수분함유율이 높아서 콘택트렌즈 재료로 매우 적합하다.The hydrogel of the present invention has excellent mechanical properties and high water content, making it very suitable as a contact lens material.
본 발명의 터폴리머는 다음과 같은 과정으로 중합시킨다.(1) 3-하이드록시프로필메타크릴레이트와 2-하이드록시에틸메타크릴레이트의 정제 및 처리 중합억제제인 하이드로퀴논을 첨가하여 질소가스를 주입하면서 감압증류한후 이를 사이클로헥산으로 추출한다. 여기에 다시 염화나트륨이 포화될때까지 첨가하고, 3-하이드록시프로필메타크릴레이트를 위층에서 분리하고 황산마그네슘으로 건조처리하여 순수한 3-하이드록시프로필메타크릴레이트를 수득한다. (2) N-비닐-2-피롤리돈 정제질소가수를 주입하면서 감압증류하여 정제한다. (3) 단량체의 혼합 : 하이드록시프로필메타크릴레이트, N-비닐-2-피롤리돈 및 하이드록시에틸메타크릴레이트를 적절한 비율로 혼합한다. (4) 개시제 : 개시제로 아자비즈이소부티로니트릴 0.2%를 사용한다. (5) 산소제거 : 단량체중의 산소를 제거하기 위하여 질소가스를 투과시킨다. (6) 중합반응 : 판몰드(mold)내에 1cc의 단량체를 채우고 실리콘 고무로 덮어 진공오븐속에 넣어 중합시킨다.The terpolymer of the present invention is polymerized by the following procedure. (1) Purification and treatment of 3-hydroxypropyl methacrylate and 2-hydroxyethyl methacrylate Hydrogenone, a polymerization inhibitor, is added to inject nitrogen gas. After distillation under reduced pressure, it is extracted with cyclohexane. To this was added again until the sodium chloride was saturated, 3-hydroxypropyl methacrylate was separated from the upper layer and dried over magnesium sulfate to obtain pure 3-hydroxypropyl methacrylate. (2) Purified by distillation under reduced pressure while injecting N-vinyl-2-pyrrolidone purified nitrogen. (3) Mixing of monomers: Hydroxypropyl methacrylate, N-vinyl-2-pyrrolidone and hydroxyethyl methacrylate are mixed in an appropriate ratio. (4) Initiator: 0.2% of azabizisobutyronitrile is used as an initiator. (5) Oxygen removal: Permeate nitrogen gas to remove oxygen from monomer. (6) Polymerization: 1cc of monomer is filled in a plate mold, covered with silicone rubber and placed in a vacuum oven to polymerize.
[제조실시예]Production Example
2-하이드록시에틸메타크릴레이트 4ml, 3-하이드록시프로필메타크릴레이트 2ml 및 N-비닐-2-피롤리돈 4ml를 반응기에 채우고 0.2중량%의 아자비스이소부티로니트릴을 개시제로 하고, 에틸렌글리콜디메타크릴레이트 0.5중량%를 가교결합제로 사용하여 55℃로에서 4시간 60℃에서 8시간 중합반응시키고, 75℃에서 12시간 숙성시켜 터폴리머(시료 1이라 함)를 수득한다. 함수율=80%, 산소투과율 : 32.5×10-11(ml cm/cm2sec mmHg), 인장강도 : 1.8×107(dym/cm2)4 ml of 2-hydroxyethyl methacrylate, 2 ml of 3-hydroxypropyl methacrylate and 4 ml of N-vinyl-2-pyrrolidone were charged to the reactor, and 0.2 wt% of azabisisobutyronitrile was used as an initiator, and ethylene Using 0.5 wt% of glycol dimethacrylate as a crosslinking agent, polymerization was carried out at 55 ° C. for 4 hours at 60 ° C. for 8 hours, and aged at 75 ° C. for 12 hours to obtain a terpolymer (called Sample 1). Water content = 80%, oxygen transmission rate: 32.5 × 10 -11 (ml cm / cm 2 sec mmHg), tensile strength: 1.8 × 10 7 (dym / cm 2 )
[비교실시예]Comparative Example
위에서 수득한 본 발명의 터폴리머(시료 1)를 종래의 폴리(2-하이드록시에틸메타크릴레이트)와 물성을 대비한 시험을 하고 그 결과를 표 1에 나타낸다.The terpolymer (Sample 1) of the present invention obtained above was tested against the conventional poly (2-hydroxyethyl methacrylate) in terms of physical properties, and the results are shown in Table 1.
[표 1]TABLE 1
위의 표 1에서 명백히 대비되는 바와같이 본 발명의 터폴리머는 종래의 폴리(2-하이드록시에틸메타크릴레이트)보다 함수율이 높과 투과율이 좋으며, 접속감각이 부드러워 콘택트렌즈 재료로 사용하는데 탁월한 효능을 발휘할 수 있다.As clearly contrasted in Table 1 above, the terpolymer of the present invention has a higher moisture content and better transmittance than conventional poly (2-hydroxyethyl methacrylate), and has excellent connection sensation, which is excellent for use as a contact lens material. Can exert.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019870008751A KR900003916B1 (en) | 1987-08-10 | 1987-08-10 | Bydrophilic terpolymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019870008751A KR900003916B1 (en) | 1987-08-10 | 1987-08-10 | Bydrophilic terpolymer |
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| Publication Number | Publication Date |
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| KR890003685A KR890003685A (en) | 1989-04-17 |
| KR900003916B1 true KR900003916B1 (en) | 1990-06-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1019870008751A KR900003916B1 (en) | 1987-08-10 | 1987-08-10 | Bydrophilic terpolymer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101863823B1 (en) * | 2016-12-29 | 2018-06-01 | 뉴바이오(주) | Hydrogel contact lenses composition, including copolymerized hydrophilic terpolymers and silicones |
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1987
- 1987-08-10 KR KR1019870008751A patent/KR900003916B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101863823B1 (en) * | 2016-12-29 | 2018-06-01 | 뉴바이오(주) | Hydrogel contact lenses composition, including copolymerized hydrophilic terpolymers and silicones |
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| KR890003685A (en) | 1989-04-17 |
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