KR100817905B1 - Biodegradable aliphatic polyester resin compositionand preparation thereof on the excellence of bionics adapt - Google Patents
Biodegradable aliphatic polyester resin compositionand preparation thereof on the excellence of bionics adapt Download PDFInfo
- Publication number
- KR100817905B1 KR100817905B1 KR1020060059111A KR20060059111A KR100817905B1 KR 100817905 B1 KR100817905 B1 KR 100817905B1 KR 1020060059111 A KR1020060059111 A KR 1020060059111A KR 20060059111 A KR20060059111 A KR 20060059111A KR 100817905 B1 KR100817905 B1 KR 100817905B1
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- Prior art keywords
- aliphatic
- polyester resin
- weight
- aliphatic polyester
- resin composition
- Prior art date
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- 229920003232 aliphatic polyester Polymers 0.000 title claims description 49
- 239000004645 polyester resin Substances 0.000 title claims description 42
- 238000002360 preparation method Methods 0.000 title description 2
- 235000001968 nicotinic acid Nutrition 0.000 title 1
- 230000002745 absorbent Effects 0.000 claims abstract description 7
- 239000002250 absorbent Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 46
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 45
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 125000001931 aliphatic group Chemical group 0.000 claims description 24
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000003381 stabilizer Substances 0.000 claims description 16
- 150000002894 organic compounds Chemical class 0.000 claims description 15
- 239000001384 succinic acid Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- -1 alcohol aliphatic organic compound Chemical class 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 5
- 125000002524 organometallic group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 3
- 238000012643 polycondensation polymerization Methods 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 229920000728 polyester Polymers 0.000 abstract description 5
- 239000003937 drug carrier Substances 0.000 abstract description 3
- 239000011342 resin composition Substances 0.000 abstract description 3
- 244000005700 microbiome Species 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000001727 in vivo Methods 0.000 abstract 1
- 239000012567 medical material Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 12
- 238000006068 polycondensation reaction Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229920001225 polyester resin Polymers 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 150000005846 sugar alcohols Polymers 0.000 description 8
- 229920006167 biodegradable resin Polymers 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000001988 toxicity Effects 0.000 description 5
- 231100000419 toxicity Toxicity 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920000954 Polyglycolide Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000012091 fetal bovine serum Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- PXDRFTPXHTVDFR-UHFFFAOYSA-N propane;titanium(4+) Chemical compound [Ti+4].C[CH-]C.C[CH-]C.C[CH-]C.C[CH-]C PXDRFTPXHTVDFR-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- SCRCZNMJAVGGEI-UHFFFAOYSA-N 1,4-dioxane-2,5-dione;oxepan-2-one Chemical compound O=C1COC(=O)CO1.O=C1CCCCCO1 SCRCZNMJAVGGEI-UHFFFAOYSA-N 0.000 description 1
- WUBBRNOQWQTFEX-UHFFFAOYSA-N 4-aminosalicylic acid Chemical compound NC1=CC=C(C(O)=O)C(O)=C1 WUBBRNOQWQTFEX-UHFFFAOYSA-N 0.000 description 1
- BWKDAAFSXYPQOS-UHFFFAOYSA-N Benzaldehyde glyceryl acetal Chemical compound O1CC(O)COC1C1=CC=CC=C1 BWKDAAFSXYPQOS-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960004909 aminosalicylic acid Drugs 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000002473 artificial blood Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000004663 cell proliferation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 239000007758 minimum essential medium Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 108010094020 polyglycine Proteins 0.000 description 1
- 229920000232 polyglycine polymer Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003356 suture material Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- 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
- C08F4/00—Polymerisation catalysts
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
- C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
- C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
-
- C—CHEMISTRY; METALLURGY
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Emergency Medicine (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
이 발명은 생체내에서 수분과 미생물에 의해 최종적으로 물과 이산화탄소로 분해되는 생체적합성 수지 조성물에 관한 것으로 이 발명의 수지 조성물은 각종 성형가공성이 우수하고, 기계적 강도와 유연성 및 분해속도 조절이 가능하여 흡수성 봉합사, 약물전달체 및 각 종 의료용 재질로 사용이 가능하다.The present invention relates to a biocompatible resin composition which is finally decomposed into water and carbon dioxide by water and microorganisms in vivo. The resin composition of the present invention is excellent in various moldability, and can control mechanical strength, flexibility, and decomposition rate. Absorbable sutures, drug carriers and various medical materials can be used.
생분해성, 생체적합성, 폴리에스테르, 흡수사 Biodegradable, Biocompatible, Polyester, Absorbent
Description
이 발명은 생체적합성이 우수한 생분해성 지방족 폴리에스테르 수지 조성물 및 그 제조방법에 관한 것이다. 이 발명이 제안하는 폴리에스테르 수지 조성물은 체내에서 독성이 발현되지 않는 고분자량의 생분해성 지방족 폴리에스테르의 조성이다. 이 발명 폴리에스테르 수지 조성물은 생분해성이고 성형가공성이 우수하여 섬유, 필름 및 입체물의 형태로 사출하거나 압출할 수 있는 생분해성 지방족폴리에스테르 수지 조성물이다.The present invention relates to a biodegradable aliphatic polyester resin composition excellent in biocompatibility and a method for producing the same. The polyester resin composition proposed by the present invention is a composition of a high molecular weight biodegradable aliphatic polyester in which no toxicity is expressed in the body. The polyester resin composition of the present invention is a biodegradable aliphatic polyester resin composition which is biodegradable and has excellent moldability and can be injected or extruded in the form of fibers, films and solids.
종래에도 체내에서 독성이 발현되지 않는 고분자량의 생분해성 화합물로 지방족 폴리에스테르 수지 조성물이 의료분야의 수술용 봉합사, 인공혈관, 인공뼈, 약물전달체 등의 상품으로 제공되고 있다.Conventionally, aliphatic polyester resin compositions have been provided as commodities such as surgical sutures, artificial blood vessels, artificial bones, drug carriers, etc. as a high molecular weight biodegradable compound that does not express toxicity in the body.
의료분야에서 광범위하게 사용되는 수술용 봉합사의 재료는 천연고분자무질이나 폴리프로필렌류의 합성 고분자물질이 모두 사용되고 있다. 최근 수분, 미생물, 효소 등 체내 환경에서 분해되는 생분해성 고분자물질 의료 비품의 제공은 정밀하고, 복잡한 의료기술의 발전에 공헌하고 있다.Surgical suture materials widely used in the medical field are both natural polymer and polypropylene synthetic polymer materials. Recently, the provision of biodegradable high molecular weight medical equipments that decompose in the body environment such as moisture, microorganisms and enzymes contributes to the development of precise and complex medical technologies.
이러한 생분해성 고분자 물질로는 폴리글리콜라이드(Polyglycolide), 글리콜라이드(glycolide)와 트리메틸렌카보네이트(trimethylene carbonate)의 공중합체인 폴리글리코넷(polyglyconet), 락트산(Latic acid)과 글리콜릭산(glycolic acid)의 공중합체인 폴리그락틴(polyglactin) 및 폴리다옥사논(Polydioxanon), 클리코라이드-입실론-카프로락톤(glycolide-ε-caprolaction)의 공중합체인 폴리글리카프론(Polyglycapron)이 이용되고 있다.Such biodegradable polymers include polyglycolide, polyglyconet, a copolymer of glycolide and trimethylene carbonate, lactic acid and glycolic acid. Polyglycapron, which is a copolymer of polyglactin, polydioxanonone, and glycolide-epsilon-caprolactone, which is a copolymer, is used.
폴리글리콜라이드와 폴리그락틴은 연성 및 복원력이 부족하여 모노필라멘트로 봉합사를 만들면 사용할 수 없다. 이 물질은 결점을 보완하기 위하여 멀티필라멘트를 제조하고 편조하여 봉합사로 사용된다. Polyglycolide and polyglycine lack softness and resilience and cannot be used if sutures are made from monofilaments. This material is used as sutures to manufacture and braid multifilaments to compensate for shortcomings.
폴리락트산과 친수성인 폴리에틸렌글리콜을 블록공중합시킨 고분자물질로 흡수사를 제조하면 폴리에틸렌글리콜 공중합체의 함수율이 섬유강도를 약화시켜 적합하지 않고, 폴리락트산과 소수성인 폴리프로필렌글리콜을 블록공중합시킨 고분자물질로 제조된 흡수사는 체내 흡수성이 적어 적합하지 않다.When the absorbent yarn is made of a polymer material obtained by block copolymerization of polylactic acid and hydrophilic polyethylene glycol, the water content of the polyethylene glycol copolymer weakens the fiber strength and is not suitable. The absorbent sand thus prepared is not suitable due to its low absorption in the body.
미국특허 제 4,224,946호에 지방족/방향족 코폴리에스테르를 수술용 봉합사를 게시하고 있으나, 이 봉합사는 시술 후 분해과정에서 발암물질인 방향족 화합물이 잔류할 수 있다. 또한 가공시 냉각속도가 느려 흡수사의 제조 및 가공이 힘들고, 유연성과 신장율이 지나치고 인장강도가 적어 수술 봉합사로서 적당치 않다.U.S. Patent No. 4,224,946 discloses a surgical suture of aliphatic / aromatic copolyester, but the suture may retain aromatic compounds, which are carcinogens, during the degradation after the procedure. In addition, it is difficult to manufacture and process absorbent yarns due to the slow cooling rate during processing, excessive flexibility and elongation rate, and low tensile strength, which is not suitable as a surgical suture.
방향족화합물이 없는 지방족 폴리에스테르는 유연성 및 인장강도가 범용플라스틱인 폴리에틸렌과 폴리프로필렌과 비슷하고, 흡수사, 약물전달체, 인공뼈, 인공관절 류가 요구하는 의료용 고분자물질의 기계적 특성에 적합하여 생분해성 플라스틱의 재료로 사용되고 있는 추세이다. 하지만 우수한 물리적 성질과 가공성을 부여하기 위하여 평균 분자량 30,000이상인 중합물이 요구된다. 종래의 기술로는 이 분자량을 얻기위해 지방족 폴리에스테르 중합과정에서 Sn, Zn, Sb 류인 금속촉매 및 인계열 안정제를 다량 포함시키므로 체내에서 독성을 유발시킨다.Aliphatic polyesters without aromatic compounds are similar to polyethylene and polypropylene for flexibility and tensile strength, and are biodegradable because they are suitable for the mechanical properties of medical polymers required by absorbent sand, drug carriers, artificial bones, and artificial joints. It is being used as a material for plastics. However, in order to give excellent physical properties and processability, a polymer having an average molecular weight of 30,000 or more is required. In the prior art, in order to obtain this molecular weight, a large amount of Sn, Zn, Sb-based metal catalysts and phosphorus-based stabilizers are included in the aliphatic polyester polymerization process, thereby causing toxicity in the body.
이 발명은 새로운 구조와 특성을 가지는 생체적합성 화합물로 지방족 폴리에스테르 화합물을 제안한다. 이 발명은 최소 금속촉매의 존재하에 수평균 분자량 45,000~120,000 이고 중량평균 분자량 200,000~500,000인 폴리에스테르 수지 조성물 및 그 제조방법을 제안한다. 이 발명은 발암물질을 포함하지 않는 생분해성 지방족 폴리에스테르 수지 조성물을 제안한다. 이 발명은 독성 유발이 없는 생분해성 지방족 폴리에스테르 수지 조성물을 제안한다. 이 발명은 범용수지 수준의 기계적 성질 및 가공성을 가지는 생체적합성 지방족 폴리에스테르 수지 조성물을 제안한다. The present invention proposes an aliphatic polyester compound as a biocompatible compound having a novel structure and properties. The present invention proposes a polyester resin composition having a number average molecular weight of 45,000 to 120,000 and a weight average molecular weight of 200,000 to 500,000 in the presence of a minimum metal catalyst and a method of manufacturing the same. The present invention proposes a biodegradable aliphatic polyester resin composition containing no carcinogen. This invention proposes a biodegradable aliphatic polyester resin composition without causing toxicity. The present invention proposes a biocompatible aliphatic polyester resin composition having mechanical properties and processability at the general resin level.
고 분자량의 지방족 폴리에스테르 수지 (I) High Molecular Weight Aliphatic Polyester Resin (I)
이 발명의 연구자들은 최소 금속촉매의 존재하에 고 분자량의 지방족 폴리에스테르 수지(I)를 제조하기 위한 새로운 다가 알코올 유기화합물 촉매(II)를 제조하였다. 이 유기화합물 촉매는 아레우리틱산(Aleuritic acid)과 에틸렌글리콜을 반응시켜 주쇄가 길고 네 개의 수산화기를 가진 다관능 화합물로 주어졌다. 이 주쇄가 길고 네 개의 수산화기를 가진 다관능 화합물을 이 발명이 목적하는 지방족 폴리에스테르 수지(I) 축중합 반응을 유도하는 유기화합물 촉매(II)로 사용한다. 유기화합물 촉매(II)를 지방족 폴리에스테르 합성 단계의 에스테르화 반응에 첨가하면 지방족 폴리에스테르 중합과정에서 많은 반응 작용기가 고분자 사슬의 길이를 더욱 길게 연결한다. 이렇게 얻은 이 발명 지방족폴리에스테르 수지는 종래의 상용화된 지방족 폴리에스테르 수지 수준의 높은 분자량을 가지며, 더 나아가 이 발명 지방족 폴리에스테르 수지는 무독성, 생체적합성을 지니고 있으며, 고분자 사슬의 곁가지가 분자구조의 비결정 영역을 증가시킴에 의하여 우수한 생분해성도 지니고 있다.The researchers of this invention have prepared a new polyhydric alcohol organic compound catalyst (II) for producing a high molecular weight aliphatic polyester resin (I) in the presence of a minimum metal catalyst. This organic compound catalyst was given as a multifunctional compound having a long main chain and four hydroxyl groups by reacting eleuritic acid with ethylene glycol. The polyfunctional compound having a long main chain and four hydroxyl groups is used as an organic compound catalyst (II) for inducing an aliphatic polyester resin (I) polycondensation reaction desired in the present invention. When the organic compound catalyst (II) is added to the esterification reaction of the aliphatic polyester synthesis step, many reactive functional groups in the aliphatic polyester polymerization process connect the polymer chain longer. The aliphatic polyester resin thus obtained has a high molecular weight equivalent to that of conventional commercial aliphatic polyester resins, and furthermore, the aliphatic polyester resin of the present invention is nontoxic and biocompatible, and the side chains of the polymer chain are amorphous in molecular structure. Increasing the area also has good biodegradability.
다가 알코올 유기화합물 촉매(II)Polyhydric Alcohol Organic Compound Catalyst (II)
상기 고분자 지방족 폴리에스테르 수지(I)인 생분해성 수지 조성물의 제조를 위하여 다가 알코올 유기화합물 촉매(II)를 먼저 제조한다. 이 발명 다가 알코올 유기화합물 촉매(II)는 반응기에 아레우리틱산 1몰과 에틸렌글리콜을 1.2~1.8몰을 투입 후 테트라부틸렌티타네이트 촉매(IV) 조건 하에서 200℃까지 온도를 높이면서 반응물을 교반한다. 상기 반응 과정에서 온도를 높이면 부산물로 반응식 1에 인용된 물이 발생한다. 이 물을 제거하면 잔류하는 물질이 지방족 4가 알코올(III) 화합물이다. 이 화합물을 이 발명 다가 알코올 유기화합물 촉매(II)로 사용한다. 상기 과정에서 유기금속 촉매(IV)인 테트라부틸렌티타네이트의 첨가량은 아레우리틱산 1몰에 대해 0.1g 내지 0.15g 이다. 더욱 바람직하게는 0.12g 내지 0.13g 이다. To prepare a biodegradable resin composition which is the polymer aliphatic polyester resin (I), a polyhydric alcohol organic compound catalyst (II) is first prepared. In the polyhydric alcohol organic compound catalyst (II) of the present invention, 1.2 to 1.8 moles of aureic acid and ethylene glycol were added to a reactor, and the reactants were stirred while raising the temperature to 200 ° C. under tetrabutylene titanate catalyst (IV). do. Increasing the temperature in the reaction process generates water quoted in Scheme 1 as a by-product. When this water is removed, the remaining substance is an aliphatic tetrahydric alcohol (III) compound. This compound is used as this invention polyhydric alcohol organic compound catalyst (II). In the above process, the addition amount of tetrabutylene titanate, which is an organometallic catalyst (IV), is 0.1 g to 0.15 g per 1 mole of areuritic acid. More preferably, it is 0.12g-0.13g.
상기 다가 알코올 유기화합물 촉매(II) 제조시의 유의점은 에틸렌글리콜과 아레우리틱산의 몰비와 반응온도를 적절하게 조절함으로 아레우리틱산분자의 자가중합을 억제하고, 에틸렌글리콜이 아레우리틱산의 카르복실기에 결합할 수 있게 하는 것이다. 아레우리틱산분자의 자가중합이 많아지면 말단기가 감소되므로 촉매효과가 반감된다. 이 상태가 심각하면 지방족 폴리에스테르 합성시 수지의 겔화가 진행되고 반응기에서 수지의 토출과 최종 제품의 가공이 불가능하다. 하지만 반응식 1과 같이 아레우릭틱산의 카르복실기에 에틸렌글리콜이 제대로 반응하면 각각의 하이드록실기가 각기 다른 활성을 나타내며, 화합물 중간의 짧은 하이드록실기는 양쪽 긴 사슬로 인해 입체장애가 일어나고 이 장애는 관능기의 반응성을 저하시켜 수지 합성시 겔화 반응이 진행되지 않을 정도의 반응이 진행된다. 이러한 반응과정은 얻어지는 지방족 폴리에스테르 수지 사슬에 짧은 곁가지 사슬을 생성시키며, 이 부차 반응으로 수지합성의 반응속도가 증가 되고 지방족 폴리에스테르의 분자량 분포를 증가시켜, 추후 얻어지는 지방족 폴리에스테르 수지의 가공성을 향상시키며 분자구조내에 비결정 영역을 증가시켜 주어 생분해 기능도 좋아진다.In the preparation of the polyhydric alcohol organic compound catalyst (II), it is necessary to properly control the molar ratio of ethylene glycol and areuritic acid and the reaction temperature to suppress the autopolymerization of the areuritic acid molecules, and the ethylene glycol is a carboxyl group of the areuritic acid. To be able to combine. As the self-polymerization of the areuritic acid molecules increases, the end group decreases, thereby reducing the catalytic effect. If this condition is serious, the gelation of the resin proceeds during the synthesis of aliphatic polyester, and it is impossible to discharge the resin from the reactor and to process the final product. However, when ethylene glycol reacts properly to the carboxyl group of the areuric acid, as shown in Scheme 1, each hydroxyl group shows different activity, and the short hydroxyl group in the middle of the compound causes steric hindrance due to both long chains. Reaction is reduced so that the gelation reaction does not proceed when the resin is synthesized. This reaction process produces short side chains in the resulting aliphatic polyester resin chain, and the secondary reaction increases the reaction rate of the resin synthesis and increases the molecular weight distribution of the aliphatic polyester, thereby improving the processability of the resulting aliphatic polyester resin. It also increases biodegradation by increasing amorphous regions within the molecular structure.
지방족 폴리에스테르 수지의 주재료Main material of aliphatic polyester resin
이 발명 지방족 폴리에스테르 수지(I)는 상기 과정으로 합성한 주쇄가 긴 지방족 4가 알코올(III) 화합물을 지방족 폴리에스테르 수지(I) 축중합반응 과정에서 다가 알코올 유기화합물 촉매(II)로 사용한다. 지방족 폴리에스테르 수지의 주재료는 숙신산을 포함하는 지방족(환상 지방족을 포함) 디카르복실산(또는 그 무수물)과, 1,4-부탄디올의 혼합물이다. 이 발명의 바람직한 주재료는 다음 중 하나이다. ① 숙신산과 1,4-부탄디올. ② 숙신산과 에틸렌글리콜 ③ 숙신산과 기타 디카르복실산(탄소수가 2~3 이거나 5~10인 알킬렌기(환상 알킬렌기를 포함한다.)를 가지는 디카르복실산) 100:0 ～ 75:25 중량부의 혼합물과 1,4-부탄디올이다. The aliphatic polyester resin (I) of the present invention uses a long-chain aliphatic tetrahydric alcohol (III) compound synthesized in the above process as a polyhydric alcohol organic compound catalyst (II) in the aliphatic polyester resin (I) polycondensation reaction. . The main material of aliphatic polyester resin is a mixture of aliphatic (including cyclic aliphatic) dicarboxylic acid (or anhydride thereof) containing succinic acid and 1,4-butanediol. Preferred main materials of this invention are one of the following. ① Succinic acid and 1,4-butanediol. ② Succinic acid and ethylene glycol ③ Succinic acid and other dicarboxylic acids (dicarboxylic acids having 2 to 3 or 5 to 10 alkylene groups (including cyclic alkylene groups)) 100: 0 to 75:25 weight Mixture of parts and 1,4-butanediol.
이 발명은 2단계로 처리되는 지방족 폴리에스테르 수지 제조방법을 이해하므로 더욱 명확해질 것이다. This invention will become clearer as it understands the process for producing the aliphatic polyester resin processed in two steps.
제1단계는 지방족폴리에스테르 올리고머를 얻는 단계이다. 제1단계는 반응기에 숙신산을 포함하는 지방족(환상 지방족을 포함) 디카르복실산(또는 그 무수물)과 지방족(환상 지방족 포함) 글리콜 단량체를 투입한다. 180~200℃의 온도에서 에스테르 교환반응을 유도한다. 생성된 물질인 물 또는 메탄올을 제거한다. 이 과정의 화학반응은 반응식 2와 같다. 반응식 2에서 글리콜은 1,4-부탄디올이고, 디카르복실산은 숙신산이다.The first step is to obtain an aliphatic polyester oligomer. In the first step, an aliphatic (including cyclic aliphatic) dicarboxylic acid (or anhydride thereof) and aliphatic (including cyclic aliphatic) glycol monomer containing succinic acid is introduced into the reactor. Induce a transesterification reaction at a temperature of 180 ~ 200 ℃. The resulting material, water or methanol, is removed. The chemical reaction in this process is shown in Scheme 2. In Scheme 2 glycol is 1,4-butanediol and dicarboxylic acid is succinic acid.
반응식 2는 반응계 내에서 진행되는 화학반응의 대표적인 예이다. 반응식 2의 n은 반응식 1에서와 같이 정수 1~50이다.Scheme 2 is a representative example of a chemical reaction in the reaction system. N in Scheme 2 is an integer from 1 to 50 as in Scheme 1.
반응식 2에서 디카르복실산과 글리콜의 반응 몰비는 1:1.2 ~ 1:1.8이다. 상기 몰비가 1:1.2 미만이면 반응성이 줄고, 색상에 영향을 준다. 상기 몰비가 1:1.8을 초과하면 비용이 커진다. 대립 된 두 관점을 고려하면 반응식 2에서 바람직한 화합물의 몰비는 1:1.3이다.In Scheme 2, the reaction molar ratio of dicarboxylic acid and glycol is 1: 1.2 to 1: 1.8. If the molar ratio is less than 1: 1.2, the reactivity decreases and the color is affected. If the molar ratio exceeds 1: 1.8, the cost increases. Considering the two opposing aspects, the molar ratio of the preferred compound in Scheme 2 is 1: 1.3.
제2단계는 다가 알코올 유기화합물 촉매(II)를 이용하여 고분자량의 지방족 폴리에스테르 수지(I)를 얻는 단계이다.
주재료인 지방족 디카르복실산(환상지방족 포함) 1몰에 대해 제2단계 반응에서 반응식 1에 보인 긴 지방족 주쇄를 가진 4가 알코올(III) 화합물 0.1~2.0g을 가한 후 상기 제1단계 반응생성물인 폴리에스테르 올리고머와 함께 240~260℃의 온도 및 0.05~2torr의 진공하에서 120~360분 동안 축중합 반응을 유도하여 지방족 폴리에스테르 수지(I)를 제조한다. The second step is to obtain a high molecular weight aliphatic polyester resin (I) using a polyhydric alcohol organic compound catalyst (II).
The first stage reaction product was added to 0.1 mol / 2.0 g of a tetrahydric alcohol (III) compound having a long aliphatic main chain shown in Scheme 1 in one step with respect to 1 mole of aliphatic dicarboxylic acid (including cyclic aliphatic) as a main material. Aliphatic polyester resin (I) is prepared by inducing a condensation polymerization reaction for 120 to 360 minutes at a temperature of 240 to 260 ° C and a vacuum of 0.05 to 2 tor with phosphorus polyester oligomer.
즉, 제1단계에서 생성된 반응 생성물 및 미반응 디카르복실산이 각각 반응식 2와 같은 화학반응으로 계속하여 생성하는 물, 메탄올 또는 글리콜 등 물질을 제거하면서 인접분자와 반응하여 수평균 분자량 45,000 내지 120,000 중량평균 분자량 200,000 내지 500,000인 폴리에스테르 수지(I)를 생성한다. 이 때 사용되는 긴 지방족 주쇄를 갖는 4가 알코올(III) 화화물이 디카르복실산 1몰에 대해 2.0g을 초과하면 합성되는 지방족폴리에스테르의 겔화가 발생한다. 이러한 겔화 반응이 생기면 반응기에서 수지의 토출이 어렵고, 토출이 되어도 가공이 불가능해 진다. 이와 반대로 지방족 4가 알코올(III) 화화물 투입량이 지방족 디카르복실산 1몰에 대해 0.1g 미만이면 촉매로서 미약한 반응만이 이루어지므로 충분한 고분자량의 수지를 얻을 수 없다. 바람직하게는 4가 알코올(III) 화화물 투입량이 지방족 디카르복실산 1몰에 대해 0.5g~1.0g이다. 이 지방족 폴리에스테르 수지(I) 생성 반응의 한 예를 반응식 3에 보였다.That is, the reaction product and the unreacted dicarboxylic acid produced in the first step are reacted with adjacent molecules while removing substances such as water, methanol or glycol, which are continuously produced by the chemical reaction as in Scheme 2, respectively, and the number average molecular weight is 45,000 to 120,000. A polyester resin (I) having a weight average molecular weight of 200,000 to 500,000 is produced. When the tetrahydric alcohol (III) sulfide having a long aliphatic main chain used at this time exceeds 2.0 g per mole of dicarboxylic acid, gelation of the synthesized aliphatic polyester occurs. When such a gelling reaction occurs, it is difficult to discharge the resin from the reactor, and processing becomes impossible even when discharged. On the contrary, when the amount of aliphatic tetrahydric alcohol (III) compound is less than 0.1 g per 1 mole of aliphatic dicarboxylic acid, only a weak reaction is performed as a catalyst, and thus a sufficient high molecular weight resin cannot be obtained. Preferably, the amount of tetrahydric alcohol (III) sulfide added is 0.5 g to 1.0 g per 1 mole of aliphatic dicarboxylic acid. An example of this aliphatic polyester resin (I) production reaction is shown in Scheme 3.
반응식 3에서 A는 
이 발명은 상기 제2단계의 에스테르화 반응 또는 에스테르 교환반응의 초기 또는 말기에 유기금속 촉매(IV)가 첨가될 수 있다. 이때 촉매(IV)의 첨가량은 투입되는 지방족 디카르복실산 1몰에 대해 0.0001g~0.002g 이하이다. 상기 첨가량이 지방족 디카르복실산 1몰에 대해 0.0001g 미만이면 에스테르화 반응이 어려우며, 0.002g을 초과하면 이론량의 물, 메탄올 또는 글리콜은 쉽게 제거되나 촉매(IV)로부터 발현되는 독성으로 생체에 유해함으로 그 양을 준수하여야 한다. 유기금속 촉매(IV)로는 티타네이트가 포함된 유기 금속화합물을 사용하며, 더욱 바람직하게는 테트라부틸티타네이트, 테트라프로필티타네이트 중 선택된 어느 하나 또는 둘 이상의 촉매가 사용된다.In the present invention, the organometallic catalyst (IV) may be added at the beginning or the end of the esterification or transesterification reaction of the second step. At this time, the addition amount of the catalyst (IV) is 0.0001 g-0.002 g or less with respect to 1 mol of aliphatic dicarboxylic acid injected. If the added amount is less than 0.0001 g per 1 mole of aliphatic dicarboxylic acid, the esterification reaction is difficult. If the amount is more than 0.002 g, the theoretical amount of water, methanol or glycol is easily removed, but the toxicity expressed from the catalyst (IV) As harmful, the amount must be observed. As the organometallic catalyst (IV), an organometallic compound containing titanate is used, and more preferably any one or two or more catalysts selected from tetrabutyl titanate and tetrapropyl titanate are used.
또한, 상기 제2단계의 에스테르화 반응 또는 에스테르 교환반응의 초기 또는 말기에 사이 안정제가 첨가될 수 있다. 안정제의 첨가량은 중량비로 금속촉매의 첨가량 1에 대하여 안정제 0.5~1 정도이다. 안정제의 첨가량이 금속촉매 첨가량 대비 0.5 미만이면 안정제로서 효과를 얻을 수 없고 색상이 나빠지고, 반응 부산물인 테트라하이드로퓨란(Tetrahydrofuran)이 증가하여 생성물에 독성을 유발할 수 있다. 상기 안정제의 첨가량이 금속촉매 첨가량 대비 1 비율을 초과하면 반응속도가 길어지고 고분자량의 폴리에스테르를 얻기가 어렵다. 상기 안정제로서는 트리메틸포스페이트, 포스페릭산, 트리페닐포스페이트 등 포스페이트 계통의 안정제 하나 이상을 사용한다.In addition, a stabilizer may be added between the beginning or the end of the second esterification reaction or transesterification reaction. The amount of the stabilizer added is about 0.5 to 1 stabilizer relative to the amount 1 of the metal catalyst added in the weight ratio. If the amount of the stabilizer is less than 0.5 compared to the amount of the metal catalyst, the effect may not be obtained as a stabilizer, the color may deteriorate, and the reaction by-product tetrahydrofuran may increase, causing toxicity to the product. When the amount of the stabilizer is more than 1 ratio of the amount of the metal catalyst, the reaction rate is long and it is difficult to obtain a high molecular weight polyester. As the stabilizer, one or more stabilizers of a phosphate system such as trimethyl phosphate, phospheric acid, and triphenyl phosphate are used.
상기와 같이 이 발명의 폴리에스테르 수지는 2단계의 반응을 거쳐 고분자량 화 된 중합체이다. 상기와 같이 제공되는 이 발명 지방족 폴리에스테르 수지의 특성은 수평균 분자량 45,000~120,000 중량평균 분자량 200,000~500,000 DSC법으로 측정된 융점 50~120℃, 용융흐름지수 0.5g~30g/10분(190℃, 2160g)이다.As described above, the polyester resin of the present invention is a high molecular weight polymer through a two-step reaction. The characteristics of the present invention aliphatic polyester resin provided as described above is the number average molecular weight 45,000 ~ 120,000 weight average molecular weight 200,000 ~ 500,000 melting point 50 ~ 120 ℃ measured by DSC method, melt flow index 0.5g ~ 30g / 10 minutes (190 ℃ , 2160 g).
이 발명의 실시 예는 다음과 같다. 이 발명은 인용된 실시예에 의해 한정되지 아니하며 이 발명이 제시하는 기술범위 내에서 다양한 실시 예가 포함된다.An embodiment of this invention is as follows. The present invention is not limited to the exemplified embodiments and various embodiments are included within the technical scope of the present invention.
비교 실시예 1Comparative Example 1
500㎖ 삼각플라스크 내의 공기를 질소로 치환하였다. 삼각플라스크에 1,4-부탄디올 108g, 숙신산 118g을 투입하였다. 질소기류 중에서 온도를 높이고, 140~200℃에서 5시간 질소 공급을 중지하고, 20~2mmHg로 감압하고, 1.5시간 축합 에스테르화 반응을 유도하였다. 채취된 반응 결과물은 수평균분자량 4,900, 중량평균 분자량 11,200이었다. 계속 상압의 질소기류하에서 촉매 테트라이소프로필티탄 0.2g을 첨가하였다. 온도를 220℃로 높이고 15~0.2mmHg의 감압하에서 6시간 탈 글리콜 반응을 유도하였다. 반응 결과물은 수평균 분자량 16,100, 중량평균 분자량 44,100이었다. 채취된 반응 결과물 폴리에스테르 100중량부, 헥사메틸렌 디이소시아네이트 1.5중량부를 니이더에 넣고 작업온도 180~200℃에서 펠렛으로 만들었다. 펠렛 시료는 수평균 분자량 42,000 중량평균 분자량 205,900 DSC법으로 측정된 융점 118℃이었다.The air in the 500 ml Erlenmeyer flask was replaced with nitrogen. Into the Erlenmeyer flask, 108 g of 1,4-butanediol and 118 g of succinic acid were added. The temperature was raised in nitrogen stream, the nitrogen supply was stopped at 140-200 degreeC for 5 hours, the pressure was reduced to 20-2 mmHg, and the condensation esterification reaction was induced for 1.5 hours. The collected reaction products were number average molecular weight 4,900 and weight average molecular weight 11,200. Subsequently, 0.2 g of catalyst tetraisopropyltitanium was added under a nitrogen stream at atmospheric pressure. The temperature was raised to 220 ° C. and a deglycol reaction was induced for 6 hours under reduced pressure of 15˜0.2 mmHg. The reaction product was number average molecular weight 16,100 and weight average molecular weight 44,100. 100 parts by weight of the obtained reaction product polyester and 1.5 parts by weight of hexamethylene diisocyanate were placed in a kneader and pelletized at a working temperature of 180 to 200 ° C. The pellet sample was 118 degreeC of melting | fusing point measured by the number average molecular weight 42,000 weight average molecular weight 205,900 DSC method.
비교 실시예 2Comparative Example 2
500㎖ 삼각플라스크내의 공기를 질소로 치환하고, 숙신산 118g, 3-아미노-4-히드록시벤조익산 4g을 투입한 후 서서히 온도를 높이면서 에스테르화 반응시켜 물을 유출시켰다. 온도를 200℃로 유지하고 이론량의 물을 완전히 유출시킨 후 에틸렌글리콜 90g, 촉매 테트라부틸티타네이트 0.1g을 첨가하고 질소 기류 중에서 온도를 200℃로 높여 2시간 동안 반응시키면서 이론 량의 물을 유출시켰다. 다시 촉매 안티몬 아세테이트 0.1g, 디부틸틴옥사이드 0.2g, 테트라부틸티타네이트 0.07g, 안정제 트리메틸포스페이트 0.2g을 첨가하였다. 계속 온도를 높여 245℃에서 0.3torr로 감압하고 200분 축중합 반응을 유도하였다. 축중합 반응의 결과물은 용융흐름지수(190℃, 2,160g) 12g/10분, 수평균 분자량 32,000 중량평균 분자량 197,000 DSC법으로 측정된 융점 97℃이었다.The air in the 500 mL Erlenmeyer flask was replaced with nitrogen, 118 g of succinic acid and 4 g of 3-amino-4-hydroxybenzoic acid were added thereto, followed by esterification while gradually raising the temperature to allow water to flow out. Maintain the temperature at 200 ° C, completely drain the theoretical amount of water, add 90 g of ethylene glycol and 0.1 g of catalytic tetrabutyl titanate, and raise the theoretical amount of water while reacting for 2 hours by raising the temperature to 200 ° C in a nitrogen stream. I was. Again 0.1 g of catalyst antimony acetate, 0.2 g of dibutyltin oxide, 0.07 g of tetrabutyl titanate, and 0.2 g of stabilizer trimethylphosphate were added. The temperature was further increased to reduce the pressure to 0.3 torr at 245 ° C. and induce a 200-minute polycondensation reaction. The result of the polycondensation reaction was a melt flow index (190 DEG C, 2160 g) 12 g / 10 min, number average molecular weight 32,000 weight average molecular weight 197,000 DSC point measured by DSC method.
비교 실시예 3Comparative Example 3
500㎖ 삼각플라스크내의 공기를 질소로 치환하고 숙신산 118g, 아미노살리실산 12g을 투입하고 온도를 서서히 높이면서 에스테르화 반응을 유도하여 물을 유출시켰다. 200℃를 유지하고 이론량의 물을 유출시킨 후, 에틸렌글리콜 92g, 촉매 테트라부틸티타네이트 0.1g을 첨가하고, 질소 기류 중에서 200℃로 2시간 반응시켜 이론량의 물을 유출시켰다. 촉매 안티몬 아세테이트 0.1g, 디부틸틴옥사이드 0.2g, 테트라부틸티타네이트 0.07g, 안정제 트리메틸포스페이트 0.2g을 첨가하고 온도를 245℃로 높이고 0.3torr로 감압하고 150분 축중합 반응을 유도하였다. 반응 결과물은 용융흐름지수(190℃, 2,160g) 9g/10분, 수평균 분자량 33,000 중량평균 분자량 240,000 DSC법으로 측정된 융점 98℃이었다.The air in the 500 ml Erlenmeyer flask was replaced with nitrogen, 118 g of succinic acid and 12 g of aminosalicylic acid were added thereto, and the esterification reaction was induced while gradually raising the temperature to allow water to flow out. After maintaining 200 degreeC and flowing out theoretical amount of water, 92 g of ethylene glycol and 0.1 g of catalyst tetrabutyl titanate were added, it was made to react at 200 degreeC in nitrogen stream for 2 hours, and the theoretical amount of water was sent out. 0.1 g of catalyst antimony acetate, 0.2 g of dibutyltin oxide, 0.07 g of tetrabutyl titanate, and 0.2 g of stabilizer trimethylphosphate were added, the temperature was raised to 245 ° C, reduced to 0.3torr, and a 150 minute condensation polymerization reaction was induced. The reaction product was a melt flow index (190 ° C., 2160 g) of 9 g / 10 min, number average molecular weight 33,000 weight average molecular weight 240,000, and melting point 98 ° C. measured by DSC method.
비교 실시예 4Comparative Example 4
500㎖ 삼각플라스크 내부공기를 질소로 치환하고, 1,4-부탄디올 108g, 숙신산 100.3g, 아디프산 21.9g을 투입하였다. 질소기류 중에서 온도를 높여 200℃에서 2시간 질소 공급을 중지하고, 20~2mmHg로 감압하고, 0.5시간 축합에 의한 에스테르화 반응을 유도하였다. 상압의 질소기류하에 촉매 테트라이소프로필티탄 0.07g, 디부틸틴옥사이드 0.45g, 안정제 트리메틸포스페이트를 첨가하였다. 온도를 높여 250℃에서 15~0.2mmHg로 감압하고 3.2시간 탈 글리콜 반응을 유도하였다. 반응 결과물 폴리에스테르 100중량부와 헥사메틸렌 디이소시아네이트 1.5중량부를 니이더에서 작업온도 180~200℃에서 펠릿화를 하였다. 펠렛 시료는 수평균 분자량이 31,000 또는 중량평균 분자량이 84,000 DSC법으로 측정된 융점은 95℃이었다.The internal air of the 500 ml Erlenmeyer flask was replaced with nitrogen, and 108 g of 1,4-butanediol, 100.3 g of succinic acid and 21.9 g of adipic acid were added thereto. In nitrogen stream, the temperature was raised, nitrogen supply was stopped for 2 hours at 200 degreeC, the pressure was reduced to 20-2 mmHg, and the esterification reaction by condensation was induced for 0.5 hours. Under a nitrogen stream at atmospheric pressure, 0.07 g of catalyst tetraisopropyltitanium, 0.45 g of dibutyltin oxide, and stabilizer trimethylphosphate were added. Increasing the temperature was reduced to 15 ~ 0.2mmHg at 250 ℃ and induced a deglycol reaction for 3.2 hours. Reaction Product 100 parts by weight of polyester and 1.5 parts by weight of hexamethylene diisocyanate were pelletized in a kneader at a working temperature of 180 to 200 ° C. The pellet sample had a melting point of 95 ° C. as a number average molecular weight of 31,000 or a weight average molecular weight of 84,000 measured by DSC method.
실시예 1Example 1
내부를 질소로 치환 한 1000㎖ 삼각플라스크에 아레우릭틱산 304.43g, 에틸렌글리콜 78.16g, 촉매 테트라부틸렌티타네이트 0.12g을 투입하고 서서히 온도를 높여, 200℃에서 반응을 진행시키고 물을 유출시켰다. 이론적인 물 발생량의 물이 유출되고 반응이 끝나면 지방족 긴 주쇄를 가지는 4가 알코올 유기화합물 촉매(II)를 얻는다.Into a 1000 ml Erlenmeyer flask substituted with nitrogen inside, 304.43 g of areuretic acid, 78.16 g of ethylene glycol, and 0.12 g of catalyst tetrabutylene titanate were gradually heated to raise the temperature, and the reaction was allowed to proceed at 200 ° C. and water was discharged. When the theoretical amount of water is released and the reaction is completed, a tetravalent alcohol organic compound catalyst (II) having an aliphatic long main chain is obtained.
500㎖ 삼각플라스크의 내부를 질소로 치환하고, 주재료인 숙신산 118g, 1,4-부탄디올 117.16g을 투입하고, 서서히 200℃로 온도를 높이면서 촉매 테트라부틸렌티타네이트 0.001g을 첨가하고 3시간 동안 질소 기류 중에서 반응시키면서 이론 량의 물을 유출시켰다. The inside of the 500 ml Erlenmeyer flask was replaced with nitrogen, 118 g of succinic acid and 117.16 g of 1,4-butanediol were added thereto. Then, 0.001 g of catalyst tetrabutylene titanate was added while gradually raising the temperature to 200 ° C. for 3 hours. The theoretical amount of water was allowed to flow while reacting in a nitrogen stream.
상기 주재료가 존재하는 삼각플라스크에 상기 유기화합물 촉매(II) 0.6g, 촉매 테트라부틸렌티타네이트 0.001g, 안정제 트리메틸포스페이트 0.001g을 첨가하고, 온도를 높여 255℃에서 0.5torr로 감압하고 240분 동안 축중합 반응을 유도하였다. 축중합 반응으로 이 발명 생분해성 수지인 폴리에스테르 수지 조성물을 얻었다. 이 생분해성수지는 용융흐름지수(190℃, 2160g) 3.0g/10분, 수평균분자량 58,000 중량평균분자량 153,000이고, DSC법으로 측정된 융점 118℃이었다.0.6 g of the organic compound catalyst (II), 0.001 g of the catalyst tetrabutylene titanate, and 0.001 g of the stabilizer trimethyl phosphate were added to the Erlenmeyer flask in which the main material was present, and the temperature was increased to a pressure of 0.5 torr at 255 ° C. for 240 minutes. A polycondensation reaction was induced. The polycondensation reaction obtained the polyester resin composition which is this invention biodegradable resin. This biodegradable resin had a melt flow index (190 ° C, 2160g) of 3.0 g / 10 minutes, a number average molecular weight of 58,000 weight average molecular weight of 153,000, and a melting point of 118 ° C. measured by DSC method.
실시예 2Example 2
500㎖ 삼각플라스크 내부를 질소로 치환하고, 주재료인 1,4-부탄디올 117.16g, 숙신산 100.3g, 아디프산 21.9g을 투입하고, 서서히 가열하여 200℃로 승온시키면서 촉매 테트라부틸티타네이트 0.001g을 첨가하였다. 질소 기류 중에서 3시간 동안 반응시키면서 이론량의 물을 유출시켰다.
주 재료가 존재하는 삼각 플라스크에 실시예 1의 유기화합물 촉매 0.6g, 촉매 테트라부틸렌티타네이트 0.001g, 안정제 트리메틸포스페이트 0.001g을 첨가하였다. 반응 온도를 높여 255℃에서 0.5torr로 감압하고, 192분 동안 축중합 반응을 유도하였다. 축중합 반응으로 생분해성 수지인 폴리에스테르 수지 조성물을 얻었다. 이 생분해성수지는 용융흐름지수(190℃, 2160g) 6.0g/10분, 수평균 분자량 58,000 중량평균 분자량 153,000이고, DSC법으로 측정된 융점 95℃이었다.The inside of the 500 ml Erlenmeyer flask was replaced with nitrogen, 117.16 g of 1,4-butanediol as a main material, 100.3 g of succinic acid, and 21.9 g of adipic acid were added thereto, and then slowly heated to raise the temperature to 200 ° C. Added. The theoretical amount of water was allowed to flow while reacting for 3 hours in a nitrogen stream.
0.6 g of the organic compound catalyst of Example 1, 0.001 g of the catalyst tetrabutylene titanate, and 0.001 g of the stabilizer trimethyl phosphate were added to the Erlenmeyer flask containing the main material. The reaction temperature was increased to reduce the pressure to 0.5torr at 255 ° C, and the polycondensation reaction was induced for 192 minutes. The polycondensation reaction yielded the polyester resin composition which is a biodegradable resin. This biodegradable resin had a melt flow index (190 DEG C, 2160 g) of 6.0 g / 10 minutes, a number average molecular weight of 58,000 weight average molecular weight of 153,000, and a melting point of 95 DEG C measured by the DSC method.
실시예 3Example 3
500㎖ 삼각플라스크 내부를 질소로 치환하고, 주재료인 1,4-부탄디올 117.16g, 아디프산 146.14g을 투입하고 200℃로 서서히 온도를 높이면서 촉매 테트라부틸티타네이트 0.001g을 첨가하고, 질소 기류 중에서 3시간 동안 반응시켜 이론량의 물을 유출시켰다.
주재료가 존재하는 삼각 플라스크에 실시예 1의 유기화합물 촉매 0.8g, 촉매 테트라부틸렌티타네이트 0.001g, 안정제 트리메틸포스페이트 0.001g을 첨가하고 온도를 높여 반응온도 255℃에서 0.5torr로 감압하고 240분 동안 축중합 반응을 유도하였다. 축중합 반응으로 생분해성 수지인 폴리에스테르 수지 조성물을 얻었다. 이 생분해성수지는 용융흐름지수(190℃, 2160g) 0.8g/10분, 수평균 분자량 72,000이고, 중량평균 분자량 238,000이고, DSC법에 측정된 융점은 60℃이었다.The inside of the 500 ml Erlenmeyer flask was replaced with nitrogen, 117.16 g of 1,4-butanediol and 146.14 g of adipic acid were added as main materials, and 0.001 g of catalyst tetrabutyl titanate was added while gradually raising the temperature to 200 ° C. The reaction was allowed to react for 3 hours to drain the theoretical amount of water.
0.8 g of the organic compound catalyst of Example 1, 0.001 g of the catalyst tetrabutylene titanate, and 0.001 g of the stabilizer trimethyl phosphate were added to an Erlenmeyer flask containing the main material, and the temperature was raised to a pressure of 0.5 Torr at 255 DEG C for 240 minutes. A polycondensation reaction was induced. The polycondensation reaction yielded the polyester resin composition which is a biodegradable resin. This biodegradable resin had a melt flow index (190 DEG C, 2160 g) of 0.8 g / 10 minutes, a number average molecular weight of 72,000, a weight average molecular weight of 238,000, and a melting point of 60 DEG C measured by the DSC method.
실시예 4Example 4
비교 실시예 1 부터 4, 실시예 1 부터 3에서 얻은 지방족 폴리에스테르 수지를 각각 압출기에서 180~220℃로 녹이고, 연신비 6배, 직경 0.25mm인 모노필라멘트를 제조하였다. 제조된 모노필라멘트의 강도를 조사하여 표 1을 얻었다.The aliphatic polyester resins obtained in Comparative Examples 1 to 4 and Examples 1 to 3 were each melted at 180 to 220 ° C. in an extruder to prepare monofilaments having a draw ratio of 6 times and a diameter of 0.25 mm. Table 1 was obtained by examining the strength of the produced monofilament.
실시예 5Example 5
실시예 4에서 얻은 모노필라멘트 시료들을 길이 5cm로 절단해 에틸렌옥사이드 가스로 24시간 소독 후, Bulbecco's minimum essential medium 1리터에 비활성화시킨 10% fetal bovine serum(FBS)을 넣고, 2gm 의 sodium bicarbonate, 200mM L-glutamine, HEPES 5.75 Gm 과 항생제(penicilline 10000 U, Streptomycin 100mg, amphotericin B 25mg/ml)를 섞어 제조된, 배양액에 넣은 후 세포주 L929를 50.8x104개체 접종하고 5일 후 증식된 세포 수를 측정하고 대조군과 비교하여 표 2의 결과를 얻었다.The monofilament samples obtained in Example 4 were cut to a length of 5 cm, sterilized with ethylene oxide gas for 24 hours, and then added to 1 liter of Bulbecco's minimum essential medium, inactivated 10% fetal bovine serum (FBS), 2gm of sodium bicarbonate, 200mM L After inoculating 50.8 x 10 4 cells of L929 with 5929 x 10 cells, the number of proliferated cells was measured. The results in Table 2 were obtained in comparison with the control.
실시예 6Example 6
비교 실시예 1부터 4, 실시예 1 부터 3에서 얻은 지방족 폴리에스테르를 Hot press를 이용하여 작업온도 120℃~160℃의 범위에서 1.5톤의 압력을 가하여 100㎛의 필름을 제조하고, 깊이 30cm의 토양에 8주간 매립한 후 채취하여 무게분석법을 통하여 생분해도를 측정하였다. 표 3은 측정 결과이다.The aliphatic polyester obtained in Comparative Examples 1 to 4 and Examples 1 to 3 was subjected to a pressure of 1.5 tons at a working temperature of 120 ° C. to 160 ° C. using a hot press to produce a film having a thickness of 100 μm and having a depth of 30 cm. After landfilling for 8 weeks, the biodegradability was measured by gravimetric analysis. Table 3 shows the measurement results.
상기와 같이 이 발명에 의하면 지방족 폴리에스테르 합성에 있어 사슬 연장체로 각기 활성이 다른 하이드로실기를 가진 다관능 지방족알콜을 반응에 첨가하여 생성물을 얻음으로 종래 다관능성 단량체를 사용할 때 제기되는 저분자량의 폴리에스테르의 급격한 증가 및 겔 화의 문제를 해소하였다. 더 나아가 이 발명은 기존의 지방족 폴리에스테르 합성과정에서 사용되는 인체에 유해한 촉매를 거의 사용하지 않음으로 생체적합성이 우수한 수지를 얻고, 보다 높은 분자량의 지방족 폴리에스테르를 얻었다. 또한 이 발명은 제조된 지방족 폴리에스테르의 기계적 물성이 종래의 지방족 폴리에스테르와 거의 같다. 이 발명에서 제조되는 폴리에스테르 수지 조성물은 저비용으로 제조되므로 의료용 흡수성 봉합사류를 저 비용으로 제조할 수 있다.As described above, according to the present invention, low molecular weight polys raised when using a conventional multifunctional monomer are obtained by adding a polyfunctional aliphatic alcohol having a hydrosil group having different activity as a chain extension in the synthesis of aliphatic polyester to the reaction to obtain a product. The problem of rapid increase of ester and gelation was solved. Furthermore, the present invention obtains a resin having excellent biocompatibility and obtains a higher molecular weight aliphatic polyester by using almost no catalyst harmful to the human body used in the existing aliphatic polyester synthesis process. In addition, the present invention has almost the same mechanical properties as the conventional aliphatic polyester produced. Since the polyester resin composition produced in this invention is manufactured at low cost, medical absorbent sutures can be manufactured at low cost.
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| KR950014174A (en) * | 1993-11-18 | 1995-06-15 | 사또오 아키오 | Degradable Aliphatic Polyester Workpiece |
| US5880224A (en) | 1996-08-05 | 1999-03-09 | Mitsubishi Gas Chemical Company, Inc. | Aliphatic polyester carbonate and process for producing the aliphatic polyester carbonate |
| KR19990025900A (en) * | 1997-09-19 | 1999-04-06 | 이명환 | Manufacturing method of biodegradable polymer |
| JP2001081165A (en) | 1999-09-17 | 2001-03-27 | Agency Of Ind Science & Technol | Method for producing biodegradable polyester |
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| KR950014174A (en) * | 1993-11-18 | 1995-06-15 | 사또오 아키오 | Degradable Aliphatic Polyester Workpiece |
| US5880224A (en) | 1996-08-05 | 1999-03-09 | Mitsubishi Gas Chemical Company, Inc. | Aliphatic polyester carbonate and process for producing the aliphatic polyester carbonate |
| KR19990025900A (en) * | 1997-09-19 | 1999-04-06 | 이명환 | Manufacturing method of biodegradable polymer |
| JP2001081165A (en) | 1999-09-17 | 2001-03-27 | Agency Of Ind Science & Technol | Method for producing biodegradable polyester |
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