KR20010095766A - A biodegradable poly(glycolide-paradioxanone) copolymer, and a process of preparing for the same - Google Patents
A biodegradable poly(glycolide-paradioxanone) copolymer, and a process of preparing for the same Download PDFInfo
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- KR20010095766A KR20010095766A KR1020000019111A KR20000019111A KR20010095766A KR 20010095766 A KR20010095766 A KR 20010095766A KR 1020000019111 A KR1020000019111 A KR 1020000019111A KR 20000019111 A KR20000019111 A KR 20000019111A KR 20010095766 A KR20010095766 A KR 20010095766A
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- glycolide
- copolymer
- paradioxanone
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- dioxane
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title description 13
- 230000008569 process Effects 0.000 title description 10
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims description 24
- VPVXHAANQNHFSF-UHFFFAOYSA-N 1,4-dioxan-2-one Chemical compound O=C1COCCO1 VPVXHAANQNHFSF-UHFFFAOYSA-N 0.000 claims description 21
- 150000005846 sugar alcohols Polymers 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 8
- 230000005855 radiation Effects 0.000 claims description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- JVWLUVNSQYXYBE-UHFFFAOYSA-N Ribitol Natural products OCC(C)C(O)C(O)CO JVWLUVNSQYXYBE-UHFFFAOYSA-N 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 6
- 229920001519 homopolymer Polymers 0.000 abstract description 5
- -1 poly(p-dioxane) Polymers 0.000 abstract 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 3
- 229920002469 poly(p-dioxane) polymer Polymers 0.000 abstract 3
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- 230000000630 rising effect Effects 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- 230000009477 glass transition Effects 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000002076 thermal analysis method Methods 0.000 description 9
- 229960003675 diethadione Drugs 0.000 description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 5
- 239000002250 absorbent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- 229920000954 Polyglycolide Polymers 0.000 description 2
- 206010052428 Wound Diseases 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000004204 blood vessel Anatomy 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- XZZXKVYTWCYOQX-UHFFFAOYSA-J octanoate;tin(4+) Chemical compound [Sn+4].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O XZZXKVYTWCYOQX-UHFFFAOYSA-J 0.000 description 2
- 229920002463 poly(p-dioxanone) polymer Polymers 0.000 description 2
- 239000000622 polydioxanone Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000001356 surgical procedure Methods 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000000560 biocompatible material Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 210000000265 leukocyte Anatomy 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 239000003356 suture material Substances 0.000 description 1
- 239000003106 tissue adhesive Substances 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D47/00—Looms in which bulk supply of weft does not pass through shed, e.g. shuttleless looms, gripper shuttle looms, dummy shuttle looms
- D03D47/28—Looms in which bulk supply of weft does not pass through shed, e.g. shuttleless looms, gripper shuttle looms, dummy shuttle looms wherein the weft itself is projected into the shed
- D03D47/32—Looms in which bulk supply of weft does not pass through shed, e.g. shuttleless looms, gripper shuttle looms, dummy shuttle looms wherein the weft itself is projected into the shed by liquid jet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D35/00—Filtering devices having features not specifically covered by groups B01D24/00 - B01D33/00, or for applications not specifically covered by groups B01D24/00 - B01D33/00; Auxiliary devices for filtration; Filter housing constructions
- B01D35/02—Filters adapted for location in special places, e.g. pipe-lines, pumps, stop-cocks
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D49/00—Details or constructional features not specially adapted for looms of a particular type
- D03D49/24—Mechanisms for inserting shuttle in shed
- D03D49/50—Miscellaneous devices or arrangements concerning insertion of weft and not otherwise provided for
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03J—AUXILIARY WEAVING APPARATUS; WEAVERS' TOOLS; SHUTTLES
- D03J1/00—Auxiliary apparatus combined with or associated with looms
- D03J1/04—Auxiliary apparatus combined with or associated with looms for treating weft
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polyesters Or Polycarbonates (AREA)
- Materials For Medical Uses (AREA)
Abstract
Description
본 발명은 수술용 봉합사, 의약 등의 서방형 매트릭스 등의 제조에 사용되며 탄성율이 낮아 유연성이 개선된 생분해성 폴리(글리콜라이드-파라다이옥산온)공중합체 및 그의 제조방법에 관한 것이다.The present invention relates to a biodegradable poly (glycolide-paradioxanone) copolymer used in the manufacture of sustained release matrices such as surgical sutures, medicines, and the like having low elastic modulus and improved flexibility, and a method of manufacturing the same.
생분해성 고분자 소재의 응용 중 가장 활발히 연구되고 있는 분야가 의약분야이며. 이중 외과용 의료용구 용도로 가장 많이 사용되는 것이 흡수성 수술용 봉합사이다. 봉합사란 수술부위의 봉합후 조직이 치유되는 기간동안 조직을 서로 접합시키는데 사용되는 의료용품으로, 조직접착제 및 외과용 스테플러와 더불어 중요한 의료용 접합재료이다. 봉합사는 재질의 종류, 물리적 형태, 생체분해 흡수성, 용도, 크기에 따라 다양하게 분류된다.The most active field of application of biodegradable polymer materials is medicine. Absorbent surgical sutures are most commonly used for surgical medical devices. Suture is a medical article used to bond tissues together during the healing period after the suture of the surgical site, and is an important medical bonding material together with a tissue adhesive and a surgical stapler. Sutures are classified according to the type of material, physical form, biodegradable absorbency, use, and size.
합성 흡수성 봉합사로는 여러가지 종류가 상업화되었는데 합사 (multifilament)형 봉합사는 모두 알파-하이드록시아세틱 산(α-hydroxyaceticacid)의 일종인 글리콜산과 젖산을 소재로하여 제조하고 있다.Various types of synthetic absorbent sutures have been commercialized. Multifilament sutures are all made of glycolic acid and lactic acid, which are a type of alpha-hydroxyacetic acid.
미국 아메리칸 시아나미드(American cyanamid)사는 세계최초로 폴리글리콜리드를 사용하여 흡수성 봉합사를 상품화 하였으며, 미국 에티콘(Ethicon)사는 폴리(글리콜라이드-락티드)를 1975년에 상품화 하였다. 또한 세계 세번째로 일본의 메디칼서플라이사가 폴리글리콜리드 수지를 사용하여 1987년부터 메디피트 (Medifit)라는 상품명으로 봉합사를 생산하게 되었다. 그러나 합사형 봉합사에 존재하는 섬유간 틈새는 박테리아 감염의 원인을 제공한다. 즉 섬유틈새에 끼인 박테리아는 백혈구에 의한 작용을 받지 않아 조직 감염을 확산시키는 역할을 하게 된다.American cyanamid commercialized absorbent sutures using polyglycolide for the first time in the world, and US (Ethicon) commercialized poly (glycolide-lactide) in 1975. In addition, the world's third Japanese medical supply company has been producing sutures under the trade name Medifit since 1987 using polyglycolide resins. However, interfibular gaps present in braided sutures provide the cause of bacterial infection. In other words, bacteria caught in the fissures are not affected by leukocytes, spreading tissue infection.
이런 문제점을 해결하기위해 여러 가지 모노필라멘트형 생체분해흡수성 봉합사 연구되고 있으며, 그중에 에티콘(Ethicon)사의 폴리다이옥산온과 아메리칸 시아나미드사의 글리콜라이드 공중합체가 1980년대에 들어 상품화 되었다. 에티콘사는 파라-다이옥산온을 촉매존재하에 개환중합하여 폴리다이옥산온을 제조하였다.To solve this problem, various monofilament-type biodegradable sutures have been studied. Among them, Ethicon's polydioxanone and American cyanamide's glycolide copolymer were commercialized in the 1980s. Eticon produced a polydioxanone by ring-opening polymerization of para-dioxanone in the presence of a catalyst.
용융방사에 의해 모노필라멘트형 봉합사로 제조되는 이 봉합사는 비교적 탄성률이 높아서 유연성이 낮으며, 다른 흡수성 봉합사에 비해 분해저항성이 커 생체 내에서 6주 정도의 장력 유지기간을 가지며 완전히 흡수되는데는 약 1년이 소요된다. 이 제품은 봉합사가 요구하는 일반적인 물성을 지녔으나 탄성률이 높아서 수술시 매듭을 형성하기가 어렵고 또한 작은 혈관의 접속과 같은 미세한 부분의 시술에 이용하기가 어렵고, 이와 같은 봉합사는 매듭안정성을 높이기 위해 많은 양의 매듭을 지어 사용하는데 이는 조직 반응을 유발하는 요인이 되기도 한다.This suture made of monofilament type suture by melt spinning has a high elastic modulus and low flexibility, and has a breakdown resistance compared to other absorbent sutures, and has a tension retention period of about 6 weeks in vivo and is completely absorbed about 1 It takes years. This product has the general physical properties required by sutures, but its high elastic modulus makes it difficult to form knots during surgery, and it is difficult to use in the treatment of minute parts such as the connection of small blood vessels. It is used in a positive knot, which can also cause tissue reactions.
그리고 상기의 봉합사는 조직통과성이 좋지 않아 시술시 불필요한 상처유발을 초래하며, 유연성이 낮아 매듭형성 능력이 떨어져 보다 많은 매듭을 필요로 하는 단점이 있다. 따라서 본 발명의 목적은 생체적합성이 우수하여 상기의 문제점을 최소화할 수 있고 생체적합성 재료 및 봉합사 제조에 적합한 물성을 갖는 소재를 제공하기 위한 것이다.In addition, the suture has a disadvantage in that tissue penetration is not good, causing unnecessary wound incidence during the procedure, and the flexibility is low and the knot formation ability is low, requiring more knots. Accordingly, an object of the present invention is to provide a material having excellent physical compatibility, which can minimize the above problems and has suitable physical properties for producing biocompatible materials and sutures.
본 발명은 상기 목적을 달성하기 위하여 글리콜라이드, 파라다이옥산온 및 1차 다가 알코올을 이용하여 세그멘티드 스타형 공중합체를 만들어 탄성률이 낮고 유연성이 우수한 고분자량의 공중합체 소재를 제공하고자 한다.The present invention is to provide a high molecular weight copolymer material having a low elastic modulus and excellent flexibility by making a segmented star copolymer using glycolide, paradioxanone and primary polyhydric alcohol in order to achieve the above object.
일반적으로, 스타형 고분자는 다관능기를 갖는 물질에 고분자 사슬이 결합되어있는 구조로서 고분자 사슬의 형태가 방사선 구조를 갖는다. 이러한 형태의 고분자는 동일한 분자량의 직쇄형 고분자에 비해 낮은 용융 점도를 나타낸다.In general, a star-type polymer is a structure in which a polymer chain is bonded to a material having a multifunctional group, and the polymer chain has a radiation structure. This type of polymer exhibits a lower melt viscosity compared to straight chain polymers of the same molecular weight.
따라서 본 발명에의한 세그멘티드 스타형 공중합체인 폴리(글리콜라이드-파라다이옥산온)은 동일한 분자량의 직쇄형 폴리(글리콜라이드-파라다이옥산온)에 비해 고 분자량을 얻기가 용이하며 이렇게 제조된 공중합체는 낮은 가공온도에서 방사가 용이하므로 방사시 열분해를 최소화 할 수 있어 보다 우수한 물성을 갖는 흡수성 봉합사 소재로 적합하고, 탄성률이 낮고 유연성이 우수한 봉합사를 제조 할 수 있다.Therefore, poly (glycolide-paradioxone), a segmented star copolymer according to the present invention, is easier to obtain a higher molecular weight than a straight chain poly (glycolide-paradioxone) of the same molecular weight and thus produced air Since the coalescence is easy to spin at a low processing temperature, it is possible to minimize pyrolysis during spinning, and thus it is suitable as an absorbent suture material having better physical properties, and it is possible to manufacture a suture having low elastic modulus and excellent flexibility.
본 발명은 생분해성 폴리(글리콜라이드-파라다이옥산온)공중합체 및 그의 제조방법에 관한 것이다.The present invention relates to biodegradable poly (glycolide-paradioxanone) copolymers and methods for their preparation.
더욱 구체적으로 본 발명은 다관능기를 갖는 물질에 고분자 사슬이 결합되어 고분자 사슬의 형태가 방사선 구조인 세그멘티드 스타형 구조를 갖고 분자량이 100,000 이상이고, 모듈러스가 3.6g/d 이하이고, 스티프니스(Stiffness) 값이 20 이하인 것을 특징으로 하는 생분해성 폴리(글리콜라이드-파라다이옥산온)공중합체에 관한 것이다.More specifically, the present invention has a segmented star-like structure in which a polymer chain is bonded to a material having a multifunctional group, and the polymer chain is in a radiation structure, having a molecular weight of 100,000 or more, a modulus of 3.6 g / d or less, and a stiffness ( Stiffness) is a biodegradable poly (glycolide- paradioxanone) copolymer, characterized in that 20 or less.
또한 본 발명은 개시제로 3개 이상의 히드록실기를 갖는 다가알콜을 사용하여 단량체인 파라다이옥산온과 글리콜라이드를 촉매 존재 하에서 개환 중합 함을 특징으로 하는 생분해성 폴리(글리콜라이드-파라다이옥산온)공중합체의 제조방법에 관한 것이다.In addition, the present invention is a biodegradable poly (glycolide- paradioxionone) air, characterized in that the ring-opening polymerization of the monomers paradioxanone and glycolide in the presence of a catalyst using a polyhydric alcohol having three or more hydroxyl groups as an initiator It relates to a method for producing the coalescence.
이하 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
먼저 본 발명은 파라다이옥산온과 글리콜라이드를 촉매 하에서 개환 중합할때 개시제로 3개 이상의 히드록실기를 갖는 다가알콜을 개시제로 사용하여 공중합체의 구조를 세그멘티드 스타형으로 함을 특징으로 한다.First, the present invention is characterized in that the copolymer structure is segmented star type using polyhydric alcohol having at least three hydroxyl groups as an initiator when the ring-opening polymerization of paradioxanone and glycolide under a catalyst. .
공중합체가 세그멘티드 스타형 구조를 이루는 메카니즘은 다관능기를 갖는 다가알콜과 글리콜라이드, 파라다이옥산온의 반응성 차이에 기인한다. 다시 말하면 반응초기에 모든 다가알콜이 파라다이옥산온과 우선 반응하여 작은 스타형 구조를 형성한다. 그런 다음 중합반응은 스타형 구조로 계속 유지한 상태로 글리콜라이드, 파라다이옥산온과의 반응에 의해 분자쇄가 성장하게 되며 최종적으로 스타형 구조의 공중합체를 얻을수 있다.The mechanism by which the copolymer forms a segmented star structure is due to the difference in reactivity between the polyhydric alcohol having polyfunctional groups, glycolide, and paradioxanone. In other words, at the beginning of the reaction, all polyhydric alcohols first react with paradioxanone to form a small star-like structure. Then, the polymerization reaction is maintained in a star-like structure, the molecular chain grows by reaction with glycolide and paradioxanone, and finally a star-shaped copolymer can be obtained.
본 발명을 더 자세히 설명하면 다음과 같다.The present invention is described in more detail as follows.
본 발명에 사용되는 단량체 구성은 글리콜라이드와 파라다이옥산온이다. 그러나 락타이드, ε-카프로락톤, 트리메틸렌 카보네이트 군중에서 선택된 단량체도 본 발명에 이용할 수 있다.Monomer configurations used in the present invention are glycolide and paradioxanone. However, monomers selected from lactide, ε-caprolactone, trimethylene carbonate crowds can also be used in the present invention.
본 발명에 사용되는 다가알콜은 적어도 3개 이상의 히드록실기를 갖는 물질이며, 다가알콜의 구조는 직쇄형이 바람직하나, 환상의 구조를 갖는 것도 사용 가능하다. 직쇄형 구조를 갖는 다가알콜로는 글리세롤, 펜타에리트리톨, 디펜타에리트리톨, 트리펜타에리트리톨, 솔비톨, 리비톨, 폴리비닐알콜 등이 사용 가능하다. 환상의 구조를 갖는 다가알콜로는 글루코오스, 프룩토오스등이 사용 가능하다.The polyhydric alcohol used in the present invention is a substance having at least three hydroxyl groups, and the structure of the polyhydric alcohol is preferably linear, but one having a cyclic structure can also be used. As the polyhydric alcohol having a linear structure, glycerol, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, ribitol, polyvinyl alcohol and the like can be used. As the polyhydric alcohol having a cyclic structure, glucose, fructose and the like can be used.
본 발명에 사용된 다가알콜은 가능한 개개의 히드록실기가 2차 히드록실기가 아닌 1차 히드록실기인 것이 바람직 하다. 다가알콜의 사용량은 전체 단량체 양에 대해 0.1∼0.6몰%, 바람직하게는 0.2∼0.5몰% 이다. 사용양이 0.1몰% 미만이면 스타형 구조의 공중합체를 얻을수 없고, 0.6몰% 를 초과하면 고분자량의 공중합체를 얻을 수 없다.It is preferable that the polyhydric alcohol used in the present invention is a primary hydroxyl group instead of a possible individual hydroxyl group as a secondary hydroxyl group. The amount of polyhydric alcohol used is 0.1 to 0.6 mol%, preferably 0.2 to 0.5 mol% with respect to the total monomer amount. If the amount used is less than 0.1 mol%, a copolymer having a star structure cannot be obtained, and if it exceeds 0.6 mol%, a high molecular weight copolymer cannot be obtained.
중합반응은 우선 파라다이옥산 단량체를 용융중합하여 폴리(p-다이옥산온)호모폴리머와 p-다이옥산온 단량체을 생성시킨 다음, 이 혼합물과 글리콜라이드를 반응 시킨다. 이때 촉매로는 옥탄산주석을 사용하고 단량체 : 촉매 몰비는10,000 : 1 ∼ 60,000 : 1, 바람직하게는 15,000 : 1 ∼ 40,000 : 1 로 하는 것이 좋다. p-다이옥산온 중합은 불활성 분위기 하에서 폴리(p-다이옥산온) 단일성분 고분자와 p-다이옥산온 단량체가 충분히 형성 될 수 있도록 장시간 반응 시킨다. 중합온도는 100∼130℃이고 바람직하게는 110℃ 이다. 중합반응은 폴리머와 단량체가 평형에 도달할때까지 진행 시킨다. 일반적으로 단량체와 폴리머 총중량에 대해 15∼30wt%의 단량체가 얻어진다. 이 반응은 온도에 의존하며, 보통 4∼8 시간이 소요된다. 온도를 110℃로 하는 경우에는 반응시간을 5~6시간으로 단축 할 수 있다.The polymerization reaction first melt-polymerizes a paradioxane monomer to produce a poly (p-dioxone) homopolymer and a p-dioxone monomer, and then reacts the mixture with glycolide. At this time, tin octanoate is used as the catalyst, and the monomer: catalyst molar ratio is preferably 10,000: 1 to 60,000: 1, preferably 15,000: 1 to 40,000: 1. p-dioxanone polymerization is allowed to react for a long time so that a poly (p-dioxone) monocomponent polymer and a p-dioxone monomer are sufficiently formed in an inert atmosphere. Polymerization temperature is 100-130 degreeC, Preferably it is 110 degreeC. The polymerization proceeds until the polymer and monomer reach equilibrium. Generally, 15-30 wt% of monomers are obtained, based on the total weight of monomers and polymers. This reaction is temperature dependent and usually takes 4 to 8 hours. When the temperature is 110 ° C, the reaction time can be shortened to 5-6 hours.
그런다음 폴리(p-다이옥산온)호모폴리머와 p-다이옥산온 단량체 혼합물에 글리콜라이드를 투입하고 온도를 승온 하면서 공중합체가 생성 될 때까지 충분히 반응한다. 일반적으로 이 중합의 반응온도는 120∼180℃ 이고 바람직하게는 120∼150℃이다. 반응온도가 이 범위내일 때 1∼4시간이면 중합이 종결된다.Then, glycolide is added to the poly (p-dioxionone) homopolymer and p-dioxone monomer mixture, and the temperature is raised to a sufficient reaction until the copolymer is formed. Generally, the reaction temperature of this polymerization is 120-180 degreeC, Preferably it is 120-150 degreeC. When the reaction temperature is within this range, the polymerization is terminated in 1 to 4 hours.
폴리(p-다이옥산온) 단일성분 고분자와 p-다이옥산온 단량체 혼합물에 투입되는 글리콜라이드 비는 보통 3∼25wt% 이고 바람직하게는 5∼20wt% 이다.The glycolide ratio added to the poly (p-dioxone) monocomponent polymer and p-dioxone monomer mixture is usually 3 to 25 wt%, preferably 5 to 20 wt%.
이하 실시예 및 비교실시예를 통하여 본 발명을 더욱 구체적으로 살펴본다. 그러나 본 발명이 아래 실시예에만 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited only to the following examples.
실시예 1Example 1
건조된 둥근 2구 250ml 플라스크에 질소 분위기 하에서 95g(0.9306몰)의 파라다이옥산온을 넣고, 개시제로 0.014g (0.0001몰)의 펜타에리트리톨을, 촉매로는톨루엔에 희석된 옥탄산 주석 0.0984ml(0.33M) 투입하여 25℃에서 16시간 건조한다. 그런 다음에 건조된 교반기를 부착하고 질소로 치환하며 이 과정을 4회 반복하고나서 이 반응물을 110℃에서 5시간 반응 한다. 그런 다음에 5g (0.04308몰)의 글리콜라이드를 첨가 시킨후 반응온도를 140℃까지 승온한 후 1시간 반응한다. 그 뒤에 반응온도를 다시 90℃로 하강한 후 65시간 반응시켜 세그멘티드 스타형인 폴리(글리콜라이드-파라다이옥산온)공중합체를 얻었다. 이렇게 회수된 폴리머는 80℃에서 48시간 동안 진공 건조하여 미반응 모노머를 제거하였다. 이 폴리머의 중합수율은 87.3%이었다. 고유점도는 25℃, 0.5g/dl 농도의 헥사플루오로이소프로필알콜(이하 "HFIP"라고 한다) 용액에서 2.7dl/g 이고 분자량은 150,000 이었다. 수소(1H) 핵자기 공명(NMR)으로부터 파라다이옥산온과 글리콜라이드의 몰비는 94/6 이었다. 시차주사 열분석으로 측정된 유리전이온도(Tg)와 용융온도는 각각 -9℃와 100℃이다. 얻어진 폴리(글리콜라이드-파라다이옥산온)공중합체를 분쇄기를 이용하여 5mm 이하의의 칩으로 만든 후 80℃에서 24시간 진공하에서 건조하였다. 칼-피숴(Karl-Fisher) 수분측정기로 측정된 수분율은 30ppm 이었다. 이 폴리머를 다음 조건으로 모노필라멘트를 제조 하였다. 단축 압출기를 사용 하였고, 사용된 방사구금은 직경이 1.4mm, 길이가 4.2mm로 L/D 비가 3인 4홀 방사구금을 이용하였다. 방사온도는 180℃, 홀당 토출량은 2.6g/분, 냉각 온도는 20℃, 냉각깊이는 100cm로 방사하고 연속하여 1차, 2차, 3차 연신 오븐에서 각각의 온도를 70℃, 80℃, 90℃하고 1차, 2차, 3차 연신비는 각각4.04배, 1.11배, 0.84배(총 연신비가 3.78배)로 연신하였다. 얻어진 모노필라멘트의 지름은 EP2 규격을 만족하는 0.248mm 이었다. 가공된 섬유는 신도 60%, 직선강도 5g/d, 모듈러스 3g/d, 스티프니스 (Stiffness) 20 이다.95 g (0.9306 mol) of paradioxanone was added to a dried round two-neck 250 ml flask under nitrogen atmosphere, 0.014 g (0.0001 mol) of pentaerythritol as an initiator, and 0.0984 ml (0.33 of tin octanoate diluted in toluene as a catalyst). M) It is added and dried at 25 ° C. for 16 hours. Then, the dried stirrer was attached and replaced with nitrogen, and the process was repeated four times, and then the reaction was reacted at 110 ° C. for 5 hours. Then, 5 g (0.04308 mole) of glycolide is added, and the reaction temperature is raised to 140 ° C. and then reacted for 1 hour. Thereafter, the reaction temperature was lowered to 90 ° C. and then reacted for 65 hours to obtain a segmented star poly (glycolide-paradioxone) copolymer. The polymer thus recovered was vacuum dried at 80 ° C. for 48 hours to remove unreacted monomers. The polymerization yield of this polymer was 87.3%. The intrinsic viscosity was 2.7 dl / g in a solution of hexafluoroisopropyl alcohol (hereinafter referred to as "HFIP") at a concentration of 0.5 g / dl and a molecular weight of 150,000. The molar ratio of paradioxanone and glycolide from hydrogen ( 1 H) nuclear magnetic resonance (NMR) was 94/6. The glass transition temperature (Tg) and melting temperature measured by differential scanning thermal analysis were -9 ℃ and 100 ℃, respectively. The obtained poly (glycolide-paradioxanone) copolymer was made into a chip of 5 mm or less using a grinder, and dried at 80 ° C. under vacuum for 24 hours. The moisture content measured by Karl-Fisher moisture meter was 30 ppm. This polymer was prepared monofilament under the following conditions. A single screw extruder was used, and the spinneret used was a four-hole spinneret having a diameter of 1.4 mm and a length of 4.2 mm with an L / D ratio of three. Spinning temperature is 180 ℃, discharge amount per hole is 2.6g / min, cooling temperature is 20 ℃, cooling depth is 100cm and it is continuously discharged at 70 ℃, 80 ℃, The primary, secondary and tertiary draw ratios were drawn at 90 DEG C and 4.04 times, 1.11 times and 0.84 times (total drawing ratio 3.78 times), respectively. The diameter of the obtained monofilament was 0.248 mm which satisfies EP2 standard. The processed fiber has 60% elongation, 5g / d linear strength, 3g / d modulus and 20 stiffness.
실시예 2Example 2
개시제로 0.68g (0.005몰)의 펜타에리트리톨을 사용한 것을 제외하고는 실시예 1과 동일한 공정 및 조건으로 폴리(글리콜라이드-파라다이옥산온)공중합체 및 모노필라멘트를 제조하였다. 폴리머의 중합수율은 89.3%이었다. 고유점도는 25℃, 0.5g/dl 농도의 HFIP 용액에서 2.0dl/g 이고 분자량은 110,000 이었다. 수소(1H) 핵자기 공명(NMR)으로부터 파라다이옥산온과 글리콜라이드의 몰비는 94/6 이었다. 시차주사 열분석으로 측정된 유리전이온도(Tg)와 용융온도는 각각 -9℃와 90℃ 였다. 얻어진 모노필라멘트의 지름은 0.246mm 이었다. 가공된 섬유는 신도 55% , 직선강도 4g/d , 모듈러스 3.5g/d, 스티프니스 18 이다.Poly (glycolide-paradioxanone) copolymer and monofilament were prepared in the same process and conditions as Example 1 except that 0.68 g (0.005 mol) of pentaerythritol was used as the initiator. The polymerization yield of the polymer was 89.3%. Intrinsic viscosity was 2.0 dl / g and molecular weight 110,000 in HFIP solution at a concentration of 0.5 g / dl at 25 ° C. The molar ratio of paradioxanone and glycolide from hydrogen ( 1 H) nuclear magnetic resonance (NMR) was 94/6. The glass transition temperature (Tg) and melting temperature measured by differential scanning thermal analysis were -9 ℃ and 90 ℃, respectively. The diameter of the obtained monofilament was 0.246 mm. The processed fibers are 55% elongated, linear strength 4g / d, modulus 3.5g / d, stiffness 18.
실시예 3Example 3
다가알콜로서 글리세놀 0.014g (0.00015 몰)을 사용한 것을 제외 하고는 실시예 1과 동일한 공정 및 조건으로 폴리(글리콜라이드-파라다이옥산온)공중합체 및 모노필라멘트를 제조하였다. 폴리머의 중합수율은 86.3%이었다. 고유점도는 25℃, 0.5g/dl 농도의 HFIP 용액에서 2.5dl/g 이고, 분자량은 130,000 이었다.수소(1H) 핵자기 공명(NMR)으로부터 파라다이옥산온과 글리콜라이드의 몰비는 95/5 이었다. 시차주사 열분석으로 측정된 유리전이온도(Tg)와 용융온도는 각각 -10℃와 100℃ 였다. 얻어진 모노필라멘트의 지름은 0.247mm 이었다. 모노필라멘트위 물성은 신도 56% , 직선강도 4.1g/d , 모듈러스 3.7g/d, 스티프니스 19 이다.Poly (glycolide-paradioxanone) copolymer and monofilament were prepared in the same process and conditions as Example 1 except that 0.014 g (0.00015 mol) of glycerol was used as the polyhydric alcohol. The polymerization yield of the polymer was 86.3%. The intrinsic viscosity was 2.5 dl / g in a HFIP solution at a concentration of 0.5 g / dl and a molecular weight of 130,000. The molar ratio of paradioxanone to glycolide from hydrogen ( 1 H) nuclear magnetic resonance (NMR) was 95/5. It was. The glass transition temperature (Tg) and melting temperature measured by differential scanning thermal analysis were -10 ℃ and 100 ℃, respectively. The diameter of the obtained monofilament was 0.247 mm. Physical properties on monofilament are 56% elongation, 4.1g / d linear strength, 3.7g / d modulus, and stiffness 19.
실시예 4Example 4
90g(0.8816몰)의 파라다이옥산온과 10g (0.0862몰)의 글리콜라이드을 사용한 것을 제외 하고는 실시예 1과 동일한 공정 및 조건으로 폴리(글리콜라이드-파라다이옥산온)공중합체 및 모노필라멘트를 제조하였다. 폴리머의 중합수율은 87.3%이었다. 고유점도는 25도, 0.5 g/dl 농도의 HFIP 용액에서 2.5 dl/g 이고 분자량은 130,000 이었다. 수소(1H) 핵자기 공명(NMR)으로부터 파라다이옥산온과 글리콜라이드의 몰비는 89/11 이었다. 시차주사 열분석으로 측정된 유리전이온도(Tg)와 용융온도는 각각 -8℃와 105℃ 였다. 얻어진 모노필라멘트의 지름은 0.249mm 이었다. 필라멘트의 물성은 신도 53% , 직선강도 4.4g/d , 모듈러스 3.1g/d, 스티프니스 18 이다.Poly (glycolide-paradioxanone) copolymer and monofilament were prepared in the same process and conditions as in Example 1 except that 90 g (0.8816 mole) of paradioxanone and 10 g (0.0862 mole) of glycolide were used. The polymerization yield of the polymer was 87.3%. The intrinsic viscosity was 2.5 dl / g and the molecular weight was 130,000 in a 25 degree, 0.5 g / dl HFIP solution. The molar ratio of paradioxanone and glycolide from hydrogen ( 1 H) nuclear magnetic resonance (NMR) was 89/11. The glass transition temperature (Tg) and melting temperature measured by differential scanning thermal analysis were -8 ℃ and 105 ℃, respectively. The diameter of the obtained monofilament was 0.249 mm. The properties of the filament are 53% elongation, 4.4g / d linear strength, 3.1g / d modulus and stiffness 18.
실시예 5Example 5
80g(0.7836몰)의 파라다이옥산온과 20g (0.1723몰)의 글리콜라이드을 사용한 것을 제외 하고는 실시예 1과 동일한 공정 및 조건으로 폴리(글리콜라이드-파라다이옥산온)공중합체 및 모노필라멘트를 제조하였다. 폴리머의 중합수율은 85.3%이었다. 고유점도는 25℃, 0.5g/dl 농도의 HFIP 용액에서 2.6dl/g 이고 분자량은 125,000 이었다. 수소(1H) 핵자기 공명(NMR)으로부터 파라다이옥산온과 글리콜라이드의 몰비는 79/21 이었다. 시차주사 열분석으로 측정된 유리전이온도(Tg)와 용융온도는 각각 -5℃와 110℃ 였다. 얻어진 모노필라멘트의 지름은 0.249mm 이었다. 모노필라멘트는 신도 52% , 직선강도 4.5g/d , 모듈러스 3.6g/d, 스티프니스 20이다.Poly (glycolide-paradioxanone) copolymer and monofilament were prepared in the same process and conditions as Example 1 except that 80 g (0.7836 mole) of paradioxanone and 20 g (0.1723 mole) of glycolide were used. The polymerization yield of the polymer was 85.3%. The intrinsic viscosity was 2.6 dl / g and the molecular weight was 125,000 in a HFIP solution at a concentration of 0.5 g / dl at 25 ° C. The molar ratio of paradioxanone and glycolide from hydrogen ( 1 H) nuclear magnetic resonance (NMR) was 79/21. The glass transition temperature (Tg) and melting temperature measured by differential scanning thermal analysis were -5 ℃ and 110 ℃, respectively. The diameter of the obtained monofilament was 0.249 mm. Monofilament has elongation 52%, linear strength 4.5g / d, modulus 3.6g / d, stiffness 20.
비교실시예 1Comparative Example 1
개시제로 1-도데카놀을 0.082g(0.00044몰)을 사용한 것을 제외하고는 실시예 1과 동일한 공정 및 조건으로 폴리(글리콜라이드-파라다이옥산온)공중합체 및 모노필라멘트를 제조하였다. 폴리머의 중합수율은 86.3%이었다. 고유점도는 25℃, 0.5g/dl 농도의 HFIP 용액에서 2.0dl/g 이고 분자량은 100,000 이었다. 수소(1H) 핵자기 공명(NMR)으로부터 파라다이옥산온과 글리콜라이드의 몰비는 94.5/4.5 이었다. 시차주사 열분석으로 측정된 유리전이온도(Tg)와 용융온도는 각각 -9℃와 100℃ 였다. 모노필라멘트의 지름은 0.246mm 이었다. 모노필라멘트의 신도는 40% , 직선강도 4.1g/d , 모듈러스 14 g/d, 스티프니스 40 이다.A poly (glycolide-paradioxanone) copolymer and monofilament were prepared in the same process and conditions as Example 1 except that 0.082 g (0.00044 mol) of 1-dodecanol was used as an initiator. The polymerization yield of the polymer was 86.3%. The inherent viscosity was 2.0 dl / g and molecular weight 100,000 in a 25 ° C., 0.5 g / dl HFIP solution. The molar ratio of paradioxanone and glycolide from hydrogen ( 1 H) nuclear magnetic resonance (NMR) was 94.5 / 4.5. The glass transition temperature (Tg) and melting temperature measured by differential scanning thermal analysis were -9 ℃ and 100 ℃, respectively. The diameter of the monofilament was 0.246 mm. The monofilament has an elongation of 40%, a linear strength of 4.1 g / d, a modulus of 14 g / d, and a stiffness of 40.
비교실시예 2Comparative Example 2
개시제로 0.1098g (0.0008몰)의 펜타에리트리톨을 사용한 것을 제외하고는 실시예 1과 동일한 공정 및 조건으로 폴리(글리콜라이드-파라다이옥산온)공중합체 및 모노필라멘트를 제조하였다. 폴리머의 중합수율은 84.3%이었다. 고유점도는 25℃, 0.5g/dl 농도의 HFIP 용액에서 2.0dl/g 이고 분자량은 90,000 이었다. 수소(1H) 핵자기 공명(NMR)으로부터 파라다이옥산온과 글리콜라이드의 몰비는 96/4 이었다. 시차주사 열분석으로 측정된 유리전이온도(Tg)와 용융온도는 각각 -9℃와 100℃ 였다. 얻어진 모노필라멘트의 지름은 0.248mm 이었다. 모노필라멘트의 신도는 40% , 직선강도 4.1g/d , 모듈러스 15 g/d, 스티프니스 42 이다Poly (glycolide-paradioxanone) copolymer and monofilament were prepared in the same process and conditions as Example 1 except that 0.1098 g (0.0008 mol) of pentaerythritol was used as the initiator. The polymerization yield of the polymer was 84.3%. The intrinsic viscosity was 2.0 dl / g and the molecular weight was 90,000 in a HFIP solution at a concentration of 25 ° C., 0.5 g / dl. The molar ratio of paradioxanone and glycolide was 96/4 from hydrogen ( 1 H) nuclear magnetic resonance (NMR). The glass transition temperature (Tg) and melting temperature measured by differential scanning thermal analysis were -9 ℃ and 100 ℃, respectively. The diameter of the obtained monofilament was 0.248 mm. Elongation of monofilament is 40%, linear strength 4.1g / d, modulus 15 g / d, stiffness 42
비교실시예 3Comparative Example 3
개시제로 0.817g (0.006몰)의 펜타에리트리톨(PEr)을 사용한 것을 제외하고는 실시예 1과 동일한 공정 및 조건으로 폴리(글리콜라이드-파라다이옥산온)공중합체를 제조하였다. 폴리머의 중합수율은 84.3%이었다. 고유점도는 25℃, 0.5g/dl 농도의 HFIP 용액에서 0.63dl/g 이고 분자량은 10,000 이었다. 수소(1H) 핵자기 공명(NMR)으로부터 파라다이옥산온과 글리콜라이드의 몰비는 95/5 이었다. 시차주사 열분석으로 측정된 유리전이온도(Tg)와 용융온도는 각각 -9℃와 90℃ 였다. 분자량이 낮아 섬유 형성이 되지 않았다.A poly (glycolide-paradioxone) copolymer was prepared in the same process and conditions as in Example 1, except that 0.817 g (0.006 mol) of pentaerythritol (PEr) was used as an initiator. The polymerization yield of the polymer was 84.3%. Intrinsic viscosity was 0.63 dl / g and molecular weight 10,000 in 25 degreeC, 0.5g / dl HFIP solution. Hydrogen (1 H) nuclear magnetic resonance on the mole ratio of para-dioxane and glycolide from (NMR) was 95/5. The glass transition temperature (Tg) and melting temperature measured by differential scanning thermal analysis were -9 ℃ and 90 ℃, respectively. Low molecular weight did not form fibers.
비교실시예 4Comparative Example 4
개시제로 펜타에리트리톨을 사용하지 않은 것을 제외하고는 실시예 1과 동일한 공정 및 조건으로 폴리(글리콜라이드-파라다이옥산온)공중합체 및 모노필라멘트를 제조하였다. 폴리머의 중합수율은 88.3%이었다. 고유점도는 25℃, 0.5 g/dl 농도의 HFIP 용액에서 1.90 dl/g 이고 분자량은 91,000 이었다. 수소 (1H) 핵자기 공명(NMR)으로부터 파라다이옥산온과 글리콜라이드의 몰비는 95.1/4.9 이었다. 시차주사 열분석으로 측정된 유리전이온도(Tg)와 용융온도는 각각 -9℃와 100℃ 였다. 얻어진 모노필라멘트의 지름은 0.247mm 이었다. 필라멘트의 물성은 신도 40% , 직선강도 4.1g/d , 모듈러스 18 g/d, 스티프니스 49 이다.Poly (glycolide-paradioxone) copolymer and monofilament were prepared in the same process and conditions as in Example 1 except that no pentaerythritol was used as the initiator. The polymerization yield of the polymer was 88.3%. The intrinsic viscosity was 1.90 dl / g and the molecular weight was 91,000 in a HFIP solution at 25 ° C., 0.5 g / dl concentration. The molar ratio of paradioxanone to glycolide from hydrogen ( 1 H) nuclear magnetic resonance (NMR) was 95.1 / 4.9. The glass transition temperature (Tg) and melting temperature measured by differential scanning thermal analysis were -9 ℃ and 100 ℃, respectively. The diameter of the obtained monofilament was 0.247 mm. The properties of the filament are 40% elongation, 4.1g / d linear strength, 18g / d modulus, and stiffness 49.
본 발명의 공중합체는 고분자 사슬 형태가 방사선 구조인 세그멘티드 스타형 구조를 갖고 있어서 탄성율이 낮고, 유연성이 우수하며, 직쇄형에 비해 낮은 용융점도를 갖는다. 그 결과 본 발명의 공중합체로 모노필라멘트 봉합사를 제조하면, 스티프니스가 낮아 수술시 매듭 형성이 쉽고 또한 작은 혈관의 접속과 같은 미세한 부분의 시술에 용이하며, 매듭안정성을 높이기 위해 많은 양의 매듭을 지어 사용하지 않아도 되므로 조직 반응을 유발하는 요인이 최소화된다. 그리고 상기의 봉합사는 조직통과성이 좋아 시술시 불필요한 상처유발을 초래하지 않으며, 유연성이 높아 매듭형성 능력이 우수하여 보다 많은 매듭을 필요로 하지 않는 장점이 있다.The copolymer of the present invention has a segmented star type structure in which the polymer chain form is a radiation structure, and thus has a low elastic modulus, excellent flexibility, and a low melt viscosity compared to the straight chain type. As a result, when the monofilament suture is manufactured from the copolymer of the present invention, it is easy to form a knot during surgery due to low stiffness, and is easy to perform fine parts such as connection of small blood vessels, and to form a large amount of knots to increase knot stability. This eliminates the need for minimal tissue triggering tissue reactions. In addition, the suture has good tissue permeability and does not cause unnecessary wound incidence during the procedure, and has the advantage of not requiring more knots due to its high flexibility and high knot formation ability.
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| WO2013094994A1 (en) * | 2011-12-19 | 2013-06-27 | Kim Hyoung Jin | Biodegradable poly para-dioxanone ligature, method for manufacturing the ligature, kit device using the ligature and method for using the kit device |
| KR101285444B1 (en) * | 2011-03-31 | 2013-07-12 | 한동희 | Mehtod of manufacturing biodegradable fiber and thereof fiber, kit device, method of using the kit device |
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| US4653497A (en) * | 1985-11-29 | 1987-03-31 | Ethicon, Inc. | Crystalline p-dioxanone/glycolide copolymers and surgical devices made therefrom |
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| US5939191A (en) * | 1993-06-11 | 1999-08-17 | United States Surgical Corporation | Coated gut suture |
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| KR101285444B1 (en) * | 2011-03-31 | 2013-07-12 | 한동희 | Mehtod of manufacturing biodegradable fiber and thereof fiber, kit device, method of using the kit device |
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