JP2009203404A - Biodegradable material rich in flexibility, and method for producing the same - Google Patents
Biodegradable material rich in flexibility, and method for producing the same Download PDFInfo
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- JP2009203404A JP2009203404A JP2008049255A JP2008049255A JP2009203404A JP 2009203404 A JP2009203404 A JP 2009203404A JP 2008049255 A JP2008049255 A JP 2008049255A JP 2008049255 A JP2008049255 A JP 2008049255A JP 2009203404 A JP2009203404 A JP 2009203404A
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- 239000000463 material Substances 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title description 4
- 150000002009 diols Chemical class 0.000 claims abstract description 39
- 229920003226 polyurethane urea Polymers 0.000 claims abstract description 33
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 23
- -1 aliphatic diamine Chemical class 0.000 claims abstract description 22
- 229920000229 biodegradable polyester Polymers 0.000 claims abstract description 22
- 239000004622 biodegradable polyester Substances 0.000 claims abstract description 22
- 150000004985 diamines Chemical class 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 40
- 239000004014 plasticizer Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical group CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 11
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical group COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 10
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229920001610 polycaprolactone Polymers 0.000 claims description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 229910001615 alkaline earth metal halide Chemical class 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 4
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 4
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 claims description 4
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 4
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000004626 polylactic acid Substances 0.000 claims description 4
- 229940104261 taurate Drugs 0.000 claims description 4
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 claims description 3
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 claims description 3
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical compound N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000954 Polyglycolide Polymers 0.000 claims description 3
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 3
- 239000000539 dimer Substances 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims description 3
- 229920000218 poly(hydroxyvalerate) Polymers 0.000 claims description 3
- 239000004633 polyglycolic acid Substances 0.000 claims description 3
- DJIHQRBJGCGSIR-UHFFFAOYSA-N 2-methylidene-1,3-dioxepane-4,7-dione Chemical compound C1(CCC(=O)OC(=C)O1)=O DJIHQRBJGCGSIR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000562 Poly(ethylene adipate) Polymers 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 36
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 33
- 239000012153 distilled water Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 235000011187 glycerol Nutrition 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 238000009864 tensile test Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 4
- 239000004632 polycaprolactone Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 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
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 description 1
- 229910001620 barium bromide Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ULEAQRIQMIQDPJ-UHFFFAOYSA-N butane-1,2-diamine Chemical compound CCC(N)CN ULEAQRIQMIQDPJ-UHFFFAOYSA-N 0.000 description 1
- RGTXVXDNHPWPHH-UHFFFAOYSA-N butane-1,3-diamine Chemical compound CC(N)CCN RGTXVXDNHPWPHH-UHFFFAOYSA-N 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007269 microbial metabolism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
本発明は、柔軟性に富む生分解性材料とその製造方法に関する。 The present invention relates to a biodegradable material rich in flexibility and a method for producing the same.
ポリウレタンウレアについては、現在までに種々の報告がなされている。 Various reports on polyurethaneurea have been made so far.
例えば非特許文献1は、LDI(リジンジイソシアネート)、ポリカプロラクトンジオール(PCL1250)、1,4ブタンジアミンを用いてポリウレタンウレアを製造しているが、破断時強度が大きく、破断時伸びが不十分であり、柔軟性が劣っていた。 For example, Non-Patent Document 1 manufactures polyurethaneurea using LDI (lysine diisocyanate), polycaprolactone diol (PCL1250), and 1,4 butanediamine, but has high strength at break and insufficient elongation at break. Yes, flexibility was inferior.
さらに、非特許文献2〜6は、ポリウレタン又はポリウレタンウレアを開示しているが、生分解性と柔軟性を両立させる材料は得られていなかった。
本発明は、生分解性材料であり、かつ、柔軟性に富むポリウレタンウレアを提供することを目的とする。 An object of this invention is to provide the polyurethane urea which is a biodegradable material and is rich in a softness | flexibility.
低分子量の生分解性ポリエステルをベースにジイソシアネートと側鎖を有するジアミンを組み合わせることで合成したセグメント化ポリウレタンウレアは弾性に富み、柔軟な材料となった。特にジアミンとして1,2-プロパンジアミンなどの側鎖を有するジアミンを用いることで、小さな引っ張り応力で大きな延伸性を示す材料が得られることを見出した。 Segmented polyurethaneurea synthesized by combining diisocyanate and side chain diamine based on low molecular weight biodegradable polyester was rich in elasticity and became a flexible material. In particular, it has been found that by using a diamine having a side chain such as 1,2-propanediamine as a diamine, a material having a large stretchability can be obtained with a small tensile stress.
本発明は、以下のポリウレタンウレアを提供するものである。
項1. 生分解性ポリエステルジオールとジイソシアネートとジアミンを反応させて得られるポリウレタンウレアであって、前記ジアミンが側鎖を有する脂肪族ジアミンであり、前記ジオールが生分解性ポリエステルセグメントを有する、セグメント化ポリウレタンウレア。
項2. 前記ジオールが、ポリ−ε−カプロラクトンジオール、ポリ乳酸ジオール、ポリグリコール酸ジオール、ポリ(ヒドロキシブチレート)ジオール、ポリ(ヒドロキシバリレート)ジオール、ポリ(ブチレンアジペート)、ポリ(ブチレンスクシネート)、ポリ(エチレンアジペート)、ポリ(エチレンスクシネート)、これらの共重合体、あるいはこれらとポリエチレングリコールの共重合体のジオールである、項1に記載のセグメント化ポリウレタンウレア。
項3. 前記ジアミンが1,2-プロパンジアミンである、項1または2に記載のセグメント化ポリウレタンウレア。
項4. 前記ジイソシアネートがリジンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、4,4‘−ジフェニルメタンジイソシアネート、トリレンジイソシアネート、トリジンジイソシアネート、キシリレンジイソシアネート、ナフタレンジイソシアネート、パラフェニレンジイソシアネート、テトラメチルキシレンジイソシアネート、ノルボルネンジイソシアネート、ダイマー酸ジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、水添キシリレンジイソシアネートからなる群から選択される、項1〜3のいずれかに記載のセグメント化ポリウレタンウレア。
項5. さらに可塑剤を含む、項1〜4のいずれかに記載のセグメント化ポリウレタンウレア。
項6. 可塑剤がグリセロールジアセタートラウラートである、項5に記載のセグメント化ポリウレタンウレア。
項7. 以下の工程を含む、項1に記載のセグメント化ポリウレタンウレアの製造方法
工程1:ジイソシアネートと生分解性ポリエステルジオールを反応させて、両末端イソシアネート基を持つプレポリマーを合成する;
工程2:ハロゲン化アルカリ金属塩あるいはハロゲン化アルカリ土類金属塩の存在下で側鎖を有する脂肪族ジアミンをさらに反応させて鎖長延長反応を行い、セグメント化ポリウレタンウレアを得る。
項8. ハロゲン化アルカリ土類金属塩が塩化カルシウムである、項7に記載のセグメント化ポリウレタンウレアの製造方法。
The present invention provides the following polyurethaneureas.
Item 1. A polyurethane urea obtained by reacting a biodegradable polyester diol, a diisocyanate and a diamine, wherein the diamine is an aliphatic diamine having a side chain, and the diol has a biodegradable polyester segment.
Item 2. The diol is poly-ε-caprolactone diol, polylactic acid diol, polyglycolic acid diol, poly (hydroxybutyrate) diol, poly (hydroxyvalerate) diol, poly (butylene adipate), poly (butylene succinate), Item 2. The segmented polyurethane urea according to Item 1, which is a diol of poly (ethylene adipate), poly (ethylene succinate), a copolymer thereof, or a copolymer of these with polyethylene glycol.
Item 3. Item 3. The segmented polyurethane urea according to Item 1 or 2, wherein the diamine is 1,2-propanediamine.
Item 4. The diisocyanate is lysine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, paraphenylene diisocyanate, tetramethylxylene diisocyanate, norbornene diisocyanate, dimer acid diisocyanate Item 4. The segmented polyurethane urea according to any one of Items 1 to 3, selected from the group consisting of trimethylhexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and hydrogenated xylylene diisocyanate.
Item 5. Item 5. The segmented polyurethane urea according to any one of Items 1 to 4, further comprising a plasticizer.
Item 6. Item 6. The segmented polyurethane urea according to Item 5, wherein the plasticizer is glycerol diacetator taurate.
Item 7. Method for producing segmented polyurethaneurea according to Item 1, comprising the following steps: Step 1: A diisocyanate and a biodegradable polyester diol are reacted to synthesize a prepolymer having both terminal isocyanate groups;
Step 2: A chain extension reaction is carried out by further reacting an aliphatic diamine having a side chain in the presence of an alkali metal halide salt or an alkaline earth metal halide salt to obtain a segmented polyurethane urea.
Item 8. Item 8. The method for producing a segmented polyurethane urea according to Item 7, wherein the halogenated alkaline earth metal salt is calcium chloride.
本発明によれば、生分解性材料であり、かつ、柔軟性に富むポリウレタンウレアを得ることができる。 According to the present invention, polyurethane urea which is a biodegradable material and has high flexibility can be obtained.
本発明のセグメント化ポリウレタンウレアは、(1)低分子量の生分解性ポリエステルジオール、(2)ジイソシアネート、(3)側鎖を有するジアミンを反応させて得ることができるものである。 The segmented polyurethane urea of the present invention can be obtained by reacting (1) a low molecular weight biodegradable polyester diol, (2) diisocyanate, and (3) a diamine having a side chain.
ここで、「セグメント化」とは、生分解性ポリエステルのセグメントをポリウレタンウレア内に含むことを意味する。 Here, “segmentation” means that a segment of biodegradable polyester is included in polyurethane urea.
生分解性ポリエステルジオールは、生分解性ポリエステルとジオールを反応させて得られ、両末端に水酸基を有するものである。生分解性ポリエステルとしては、ポリ−ε−カプロラクトン、ポリ乳酸、ポリグリコール酸、ポリ(ヒドロキシブチレート)、ポリ(ヒドロキシバリレート)などのヒドロキシカルボン酸のポリマーと、ポリ(ブチレンアジペート)、ポリ(ブチレンスクシネート)のような二塩基酸とジオールの縮合系ポリマーが挙げられる。 The biodegradable polyester diol is obtained by reacting a biodegradable polyester with a diol and has hydroxyl groups at both ends. Biodegradable polyesters include polymers of hydroxycarboxylic acids such as poly-ε-caprolactone, polylactic acid, polyglycolic acid, poly (hydroxybutyrate), poly (hydroxyvalerate), poly (butylene adipate), poly ( And a condensation polymer of a dibasic acid and a diol such as butylene succinate).
これらの生分解性ポリエステルのカルボン酸部分と反応して生分解性ポリエステルジオールを形成するためのジオールとしては、エチレングリコール、プロピレングリコール、ブチレングリコールなどの炭素数2〜6のアルキレングリコール、ジエチレングリコール、ジプロピレングリコール、ジブチレングリコールなどの炭素数4〜12のジアルキレングリコール、トリエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコールなどのポリアルキレングリコール、あるいはこれらの共重合体が挙げられる。 Diols for reacting with the carboxylic acid moiety of these biodegradable polyesters to form biodegradable polyester diols include alkylene glycols having 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, diethylene glycol, and the like. Examples thereof include C 4-12 dialkylene glycols such as propylene glycol and dibutylene glycol, polyalkylene glycols such as triethylene glycol, polyethylene glycol, polypropylene glycol and polybutylene glycol, and copolymers thereof.
ジイソシアネートとしては、芳香族ジイソシアネート、脂肪族ジイソシアネートのいずれも用いることができる。 As the diisocyanate, either an aromatic diisocyanate or an aliphatic diisocyanate can be used.
芳香族ジイソシアネートとしては、例えば、4,4‘−ジフェニルメタンジイソシアネート(MDI)、トリレンジイソシアネート(TDI)、トリジンジイソシアネート(TODI)、キシリレンジイソシアネート(XDI)、ナフタレンジイソシアネート(NDI)、パラフェニレンジイソシアネート(PPDI)、テトラメチルキシレンジイソシアネート(TMXDI)等が挙げられる。これらは単独でもしくは2種以上併せて用いることができる。 Examples of aromatic diisocyanates include 4,4′-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), tolidine diisocyanate (TODI), xylylene diisocyanate (XDI), naphthalene diisocyanate (NDI), and paraphenylene diisocyanate (PPDI). ), Tetramethylxylene diisocyanate (TMXDI) and the like. These may be used alone or in combination of two or more.
脂肪族ジイソシアネートとしては、例えば、ヘキサメチレンジイソシアネート(HDI)、イソホロンジイソシアネート(IPDI)、ノルボルネンジイソシアネート(NBDI)、リジンジイソシアネート(LDI)、ダイマー酸ジイソシアネート(DDI)、トリメチルヘキサメチレンジイソシアネート(TMDI)、ジシクロヘキシルメタンジイソシアネート(H12MDI)、水添キシリレンジイソシアネート(H6XDI)等が挙げられる。これらは単独でもしくは2種以上併せて用いることができる。 Examples of the aliphatic diisocyanate include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), lysine diisocyanate (LDI), dimer acid diisocyanate (DDI), trimethylhexamethylene diisocyanate (TMDI), and dicyclohexylmethane. Examples thereof include diisocyanate (H 12 MDI) and hydrogenated xylylene diisocyanate (H 6 XDI). These may be used alone or in combination of two or more.
側鎖を有する脂肪族ジアミンとしては、例えば、1,2-プロパンジアミン、1,2-ブタンジアミン、1,3-ブタンジアミン、イソホロンジアミン等が挙げられる。これらは単独でもしくは2種以上併せて、もしくは直鎖状ジアミンとの混合物として用いてもよい。 Examples of the aliphatic diamine having a side chain include 1,2-propanediamine, 1,2-butanediamine, 1,3-butanediamine, and isophoronediamine. You may use these individually or in combination of 2 or more types or as a mixture with linear diamine.
生分解性ポリエステルジオールは、3000以下の分子量が好ましく、例えば分子量1250のポリカプロラクトンジオール(PCL1250)やポリ乳酸ジオールなどが好ましく用いられる。 The biodegradable polyester diol preferably has a molecular weight of 3000 or less. For example, polycaprolactone diol (PCL1250) having a molecular weight of 1250 or polylactic acid diol is preferably used.
本発明のセグメント化ポリウレタンウレアは、ジイソシアネート2モルに対し、生分解性ポリエステルジオール0.3〜1.7モル程度、側鎖を有する脂肪族ジアミン1.7〜0.3モル程度、好ましくは、ジイソシアネート2モルに対し、生分解性ポリエステルジオール0.5〜1.5モル程度、側鎖を有する脂肪族ジアミン1.5〜0.5モル程度、より好ましくはジイソシアネート2モルに対し、生分解性ポリエステルジオール0.7〜1.3モル程度、側鎖を有する脂肪族ジアミン1.3〜0.7モル程度、特に好ましくは、ジイソシアネート2モルに対し、生分解性ポリエステルジオール1モル程度、側鎖を有する脂肪族ジアミン1モル程度の割合で使用する。 The segmented polyurethane urea of the present invention is about 0.3 to 1.7 mol of biodegradable polyester diol and about 1.7 to 0.3 mol of aliphatic diamine having a side chain, preferably 2 mol of diisocyanate, The biodegradable polyester diol is about 0.5 to 1.5 moles with respect to 2 moles of diisocyanate, and the aliphatic diamine having a side chain is about 1.5 to 0.5 moles, more preferably biodegradable with respect to 2 moles of diisocyanate. About 0.7 to 1.3 mol of polyester diol, about 1.3 to 0.7 mol of aliphatic diamine having a side chain, particularly preferably about 1 mol of biodegradable polyester diol to 2 mol of diisocyanate, side chain It is used at a ratio of about 1 mol of an aliphatic diamine having
本発明の好ましいセグメント化ポリウレタンウレアの部分構造を以下に示す。 A partial structure of a preferred segmented polyurethane urea of the present invention is shown below.
(式中、nは5〜25の整数を示す。)
セグメント化ポリウレタンウレアの数平均分子量は、好ましくは5000以上である。
(In the formula, n represents an integer of 5 to 25.)
The number average molecular weight of the segmented polyurethane urea is preferably 5000 or more.
セグメント化ポリウレタンウレアは、以下の(1)および(2)に示す2段階の反応で製造することができる::
(1)ジイソシアネート、生分解性ポリエステルジオールから両末端イソシアネート基を持つプレポリマーを合成する。反応はジイソシアネート2モルに対し、生分解性ポリエステルジオール0.3〜1.7モル程度を使用し、室温程度から100℃程度の温度下に30分から12時間程度反応させることにより有利に進行する。
(2)ハロゲン化アルカリ金属塩あるいはハロゲン化アルカリ土類金属塩の存在下で側鎖を有する脂肪族ジアミンで鎖長延長反応を行う。この反応は上記の混合比率で必要に応じて非プロトン性有機溶媒の存在下に室温から100℃程度の温度下に30分から12時間程度反応させることにより有利に進行する。
Segmented polyurethaneurea can be produced by the two-step reaction shown in the following (1) and (2):
(1) A prepolymer having both terminal isocyanate groups is synthesized from diisocyanate and biodegradable polyester diol. The reaction proceeds advantageously by using about 0.3 to 1.7 mol of biodegradable polyester diol per 2 mol of diisocyanate and reacting at about room temperature to about 100 ° C. for about 30 minutes to 12 hours.
(2) A chain extension reaction is performed with an aliphatic diamine having a side chain in the presence of an alkali metal halide salt or an alkaline earth metal halide salt. This reaction proceeds advantageously by reacting for about 30 minutes to 12 hours at room temperature to about 100 ° C. in the presence of an aprotic organic solvent as necessary at the above mixing ratio.
非プロトン性有機溶媒としては、酢酸エチル、アセトニトリル、テトラヒドロフラン、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミドなどが挙げられ、沸点および溶解性のバランスからN,N−ジメチルアセトアミドが好ましい。 Examples of the aprotic organic solvent include ethyl acetate, acetonitrile, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide and the like, and N, N-dimethylacetamide is preferred from the balance of boiling point and solubility.
ハロゲン化アルカリ金属塩としては、塩化ナトリウム、塩化カリウム、塩化リチウム、臭化ナトリウム、臭化カリウム、臭化リチウムなどが挙げられ、ハロゲン化アルカリ土類金属塩としては、塩化カルシウム、塩化マグネシウム、塩化バリウム、臭化カルシウム、臭化マグネシウム、臭化バリウムなどが挙げられる。 Examples of the alkali metal halide salt include sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, and lithium bromide. Examples of the alkaline earth metal halide salt include calcium chloride, magnesium chloride, and chloride. Examples include barium, calcium bromide, magnesium bromide, and barium bromide.
可塑剤としては、グリセリンエステル、脂肪酸エステル、マレイン酸エステル、フマル酸エステルなどが挙げられ、耐ブリードアウト性および生分解性からグリセロールジアセタートラウラートが好ましい。 Examples of the plasticizer include glycerin ester, fatty acid ester, maleic acid ester, and fumaric acid ester. Glycerol diacetator taurate is preferable in terms of bleed-out resistance and biodegradability.
以下、本発明を実施例を用いてより詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
なお、以下の実施例に記載されている測定項目は次の方法により測定した値である。
・分子量測定:ヘキサフルオロイソプロパノールを溶離液としたGPC測定によるポリメタクリル酸メチル換算値で求めた。
・引張試験:「JIS K 6251(2004)加硫ゴム及び熱可塑性ゴム-引張特性の求め方」に準じて行った。
100%応力とは100%伸度の時の応力の値を示す。
・引張試験サンプルは溶媒キャスティング法により形成したフィルムを使用した。フィルムは各ポリマー試料に可塑剤としてグリセロールジアセタートラウラートをそれぞれの割合加え合計1.0gにしたものをLDI,IPDI系はクロロホルム10mlに、HDI系はトリフルオロエタノール10mlに溶解した溶液をシャーレにキャストして溶媒を減圧下で蒸発させることにより作製した。
The measurement items described in the following examples are values measured by the following method.
-Molecular weight measurement: It calculated | required by the polymethylmethacrylate conversion value by GPC measurement which used hexafluoro isopropanol as an eluent.
-Tensile test: JIS K 6251 (2004) Vulcanized rubber and thermoplastic rubber-Performed according to the method for determining tensile properties.
100% stress indicates the value of stress at 100% elongation.
-A film formed by a solvent casting method was used as a tensile test sample. Films were prepared by adding glycerol diacetatorlaurate as a plasticizer to each polymer sample in a proportion of 1.0 g in total in a LDI, IPDI system in chloroform 10 ml, and HDI system in trifluoroethanol 10 ml in a petri dish. And the solvent was evaporated under reduced pressure.
(実施例1)
フラスコにポリカプロラクトンジオール「数平均分子量1250」(PCL1250) 10g(8mmol)、N,N-ジメチルアセトアミド(DMAc) 5mlを入れ50℃で溶解させた。リジンジイソシアネート(LDI) 3.4g(16mmol)を加えて、80℃で5時間反応させた。DMAc 10mlを加え、DMAc 10mlに溶解させた1,2-プロパンジアミン(1,2-PDA) 0.6g(8mmol)を滴下しながら80℃で1.5時間反応させた。
生成した重合物をDMAc 100mlで溶解し、蒸留水で沈殿させ、蒸留水で洗浄し精製した。重合物が12.9g(収率92.2%)得られた。重合物の物性は前述の方法により求めその結果を表1に示す。
(Example 1)
In a flask, 10 g (8 mmol) of polycaprolactone diol “number average molecular weight 1250” (PCL1250) and 5 ml of N, N-dimethylacetamide (DMAc) were added and dissolved at 50 ° C. Lysine diisocyanate (LDI) 3.4 g (16 mmol) was added and reacted at 80 ° C. for 5 hours. 10 ml of DMAc was added and reacted at 80 ° C. for 1.5 hours while adding 0.6 g (8 mmol) of 1,2-propanediamine (1,2-PDA) dissolved in 10 ml of DMAc.
The produced polymer was dissolved in 100 ml of DMAc, precipitated with distilled water, washed with distilled water and purified. 12.9 g (yield 92.2%) of the polymer was obtained. The physical properties of the polymer were determined by the method described above and the results are shown in Table 1.
(実施例2、3、4、5、6)
引張試験サンプルを調製する際に、表1の割合で可塑剤グリセロールジアセタートラウラートを配合した以外は実施例1と同様に試験を行った。
(Examples 2, 3, 4, 5, 6)
When preparing the tensile test sample, the test was performed in the same manner as in Example 1 except that the plasticizer glycerol diacetatoroulate was blended in the ratio shown in Table 1.
(実施例7)
フラスコにPCL1250 10g(8mmol)を入れ60℃で溶融させた。イソホロンジイソシアネート(IPDI) 3.6g(16mmol)を加えて、90℃で5時間反応させた。DMAc 10mlを加え、DMAc 10mlに溶解させた1,2-プロパンジアミン(1,2-PDA) 0.6g(8mmol)を滴下しながら80℃で1.5時間反応させた。生成した重合物をDMAcで溶解し、蒸留水で沈殿させ、蒸留水で洗浄し精製した。重合物が13.2g(収率93.0%)得られた。重合物の物性は前述の方法により求めその結果を表1に示す。
(Example 7)
A flask was charged with 10 g (8 mmol) of PCL1250 and melted at 60 ° C. 3.6 g (16 mmol) of isophorone diisocyanate (IPDI) was added and reacted at 90 ° C. for 5 hours. 10 ml of DMAc was added and reacted at 80 ° C. for 1.5 hours while adding 0.6 g (8 mmol) of 1,2-propanediamine (1,2-PDA) dissolved in 10 ml of DMAc. The produced polymer was dissolved in DMAc, precipitated with distilled water, washed with distilled water and purified. 13.2 g (yield 93.0%) of the polymer was obtained. The physical properties of the polymer were determined by the method described above and the results are shown in Table 1.
(実施例8、9、10、11)
引張試験サンプルを調製する際に、表1の割合で可塑剤グリセロールジアセタートラウラートを配合した以外は実施例7と同様に試験を行った。
(Examples 8, 9, 10, 11)
When preparing the tensile test sample, the test was performed in the same manner as in Example 7 except that the plasticizer glycerol diacetatorolaurate was blended in the ratio shown in Table 1.
(実施例12)
フラスコにPCL1250 10g(8mmol)、ポリエチレングリコール「数平均分子量400」(PEG400) 2g(5mmol)を入れ60℃で溶融させた。IPDI 5.8g(26mmol)を加えて、85℃で5時間反応させた。DMAc 15mlを加え、DMAc 10mlに溶解させた1,2-プロパンジアミン(1,2-PDA) 1.0g(13mmol)を滴下しながら80℃で1.5時間反応させた。生成した重合物をDMAc50mlで溶解し、蒸留水で沈殿させ、蒸留水で洗浄し精製した。重合物が17.9g(収率95.5%)得られた。重合物の物性は前述の方法により求めその結果を表1に示す。
(Example 12)
A flask was charged with 10 g (8 mmol) of PCL1250 and 2 g (5 mmol) of polyethylene glycol “number average molecular weight 400” (PEG400) and melted at 60 ° C. 5.8 g (26 mmol) of IPDI was added and reacted at 85 ° C. for 5 hours. 15 ml of DMAc was added, and 1.0 g (13 mmol) of 1,2-propanediamine (1,2-PDA) dissolved in 10 ml of DMAc was added dropwise and reacted at 80 ° C. for 1.5 hours. The produced polymer was dissolved in 50 ml of DMAc, precipitated with distilled water, washed with distilled water and purified. 17.9 g (yield 95.5%) of the polymer was obtained. The physical properties of the polymer were determined by the method described above and the results are shown in Table 1.
(実施例13、14、15、16、17)
引張試験サンプルを調製する際に、表1の割合で可塑剤グリセロールジアセタートラウラートを配合した以外は実施例12と同様に試験を行った。
(Examples 13, 14, 15, 16, 17)
When preparing the tensile test sample, the test was performed in the same manner as in Example 12 except that the plasticizer glycerol diacetatorolaurate was blended in the ratio shown in Table 1.
(実施例18)
フラスコにポリカプロラクトンジオール「数平均分子量2000」(PCL2000)10g(5mmol)、PEG400 2g(5mmol)を入れ60℃で溶融させた。IPDI 4.5g(20mmol)を加えて、85℃で5時間反応させた。DMAc 5mlを加え、DMAc 10mlに溶解させた1,2-プロパンジアミン(1,2-PDA) 0.7g(10mmol)を滴下しながら80℃で1.5時間反応させた。生成した重合物をDMAc50mlで溶解し、蒸留水で沈殿させ、蒸留水で洗浄し精製した。重合物が15.9g(収率92.2%)得られた。重合物の物性は前述の方法により求めその結果を表1に示す。
(Example 18)
In a flask, 10 g (5 mmol) of polycaprolactone diol “number average molecular weight 2000” (PCL2000) and 2 g (5 mmol) of PEG400 were put and melted at 60 ° C. IPDI 4.5g (20mmol) was added and reacted at 85 ° C for 5 hours. DMAc (5 ml) was added and reacted at 80 ° C. for 1.5 hours while 0.7 g (10 mmol) of 1,2-propanediamine (1,2-PDA) dissolved in 10 ml of DMAc was added dropwise. The produced polymer was dissolved in 50 ml of DMAc, precipitated with distilled water, washed with distilled water and purified. 15.9 g (yield 92.2%) of the polymer was obtained. The physical properties of the polymer were determined by the method described above and the results are shown in Table 1.
(実施例19、20、21、22、23)
引張試験サンプルを調製する際に、表1の割合で可塑剤グリセロールジアセタートラウラートを配合した以外は実施例18と同様に試験を行った。
(Examples 19, 20, 21, 22, 23)
When preparing the tensile test sample, the test was conducted in the same manner as in Example 18 except that the plasticizer glycerol diacetatorlaurate was blended in the ratio shown in Table 1.
(実施例24)
フラスコにPCL1250 5g(4mmol)を入れ60℃で溶融させた。ヘキサメチレンジイソシアネート(HDI) 1.2g(7.2mmol)を加えて、100℃で5時間反応させた。塩化カルシウム1.0g、DMAc 20mlを加え、DMAc 10mlに溶解させた1,2-プロパンジアミン(1,2-PDA) 0.3g(4mmol)を室温で30分滴下し、全て滴下後に昇温し80℃で1時間反応させた。生成した重合物をDMAc50mlで溶解し、蒸留水で沈殿させ、蒸留水で洗浄し精製した。重合物が5.9g(収率90.2%)得られた。重合物の物性は前述の方法により求めその結果を表1に示す。
(Example 24)
The flask was charged with 5 g (4 mmol) of PCL1250 and melted at 60 ° C. Hexamethylene diisocyanate (HDI) 1.2 g (7.2 mmol) was added and reacted at 100 ° C. for 5 hours. Add 1.0 g of calcium chloride and 20 ml of DMAc, add dropwise 0.3 g (4 mmol) of 1,2-propanediamine (1,2-PDA) dissolved in 10 ml of DMAc at room temperature for 30 minutes. For 1 hour. The produced polymer was dissolved in 50 ml of DMAc, precipitated with distilled water, washed with distilled water and purified. 5.9 g (yield 90.2%) of the polymer was obtained. The physical properties of the polymer were determined by the method described above and the results are shown in Table 1.
(実施例25、26、27)
引張試験サンプルを調製する際に、表1の割合で可塑剤グリセロールジアセタートラウラートを配合した以外は実施例24と同様に試験を行った。
(Examples 25, 26, 27)
When preparing the tensile test sample, the test was conducted in the same manner as in Example 24 except that the plasticizer glycerol diacetatorlaurate was blended in the ratio shown in Table 1.
(実施例28)
フラスコにPCL1250 10g(8mmol)、PEG400 2g(5mmol)を入れ60℃で溶融させた。HDI 3.9g(23mmol)を加えて、100℃で5時間反応させた。塩化カルシウム2.0g、DMAc 100mlを加え、DMAc 10mlに溶解させた1,2-プロパンジアミン(1,2-PDA) 1.0g(13mmol)を室温で30分滴下し、全て滴下後に昇温し80℃で1時間反応させた。生成した重合物をDMAc50mlで溶解し、蒸留水で沈殿させ、蒸留水で洗浄し精製した。重合物が15.1g(収率89.3%)得られた。重合物の物性は前述の方法により求めその結果を表1に示す。
(Example 28)
A flask was charged with 10 g (8 mmol) of PCL1250 and 2 g (5 mmol) of PEG400 and melted at 60 ° C. 3.9 g (23 mmol) of HDI was added and reacted at 100 ° C. for 5 hours. Add 2.0 g of calcium chloride and 100 ml of DMAc, add dropwise 1.0 g (13 mmol) of 1,2-propanediamine (1,2-PDA) dissolved in 10 ml of DMAc at room temperature for 30 minutes. For 1 hour. The produced polymer was dissolved in 50 ml of DMAc, precipitated with distilled water, washed with distilled water and purified. 15.1 g (yield 89.3%) of the polymer was obtained. The physical properties of the polymer were determined by the method described above and the results are shown in Table 1.
(実施例29、30、31)
引張試験サンプルを調製する際に、表1の割合で可塑剤グリセロールジアセタートラウラートを配合した以外は実施例28と同様に試験を行った。
(Examples 29, 30, 31)
When preparing the tensile test sample, the test was performed in the same manner as in Example 28 except that the plasticizer glycerol diacetator taurate was blended at the ratio shown in Table 1.
(実施例32)
フラスコにPCL2000 10g(5mmol)、PEG400 2g(5mmol)を入れ60℃で溶融させた。HDI 3.0g(18mmol)を加えて、100℃で5時間反応させた。塩化カルシウム2.0g、DMAc 100mlを加え、DMAc 10mlに溶解させた1,2-プロパンジアミン(1,2-PDA) 0.7g(10mmol)を室温で30分滴下し、全て滴下後に昇温し80℃で1時間反応させた。生成した重合物をDMAc50mlで溶解し、蒸留水で沈殿させ、蒸留水で洗浄し精製した。重合物が14.1g(収率89.4%)得られた。重合物の物性は前述の方法により求めその結果を表1に示す。
(Example 32)
The flask was charged with 10 g (5 mmol) of PCL2000 and 2 g (5 mmol) of PEG400 and melted at 60 ° C. HDI 3.0g (18mmol) was added, and it was made to react at 100 degreeC for 5 hours. Add 2.0 g of calcium chloride and 100 ml of DMAc, add 0.7 g (10 mmol) of 1,2-propanediamine (1,2-PDA) dissolved in 10 ml of DMAc for 30 minutes at room temperature, and heat up to 80 ° C For 1 hour. The produced polymer was dissolved in 50 ml of DMAc, precipitated with distilled water, washed with distilled water and purified. 14.1 g (yield 89.4%) of the polymer was obtained. The physical properties of the polymer were determined by the method described above and the results are shown in Table 1.
(実施例33、34、35)
引張試験サンプルを調製する際に、表1の割合で可塑剤グリセロールジアセタートラウラートを配合した以外は実施例32と同様に試験を行った。
(Examples 33, 34, 35)
When preparing the tensile test sample, the test was performed in the same manner as in Example 32 except that the plasticizer glycerol diacetatorlaurate was blended in the ratio shown in Table 1.
(比較例1)
フラスコにPCL1250 20g(16mmol)、DMAc 10mlを入れ50℃で溶解させた。LDI 6.8g(32mmol)を加えて、80℃で5時間反応させた。DMAc 10mlに溶解させた1,4-ブタンジアミン(1,4-BDA) 1.4g(16mmol)を滴下しながら80℃で1.5時間反応させた。生成した重合物をDMAc 100mlで溶解し、蒸留水で沈殿させ、蒸留水で洗浄し精製した。重合物が24.9g(収率88.3%)得られた。重合物の物性は前述の方法により求めその結果を表1に示す。
(Comparative Example 1)
In a flask, 20 g (16 mmol) of PCL1250 and 10 ml of DMAc were added and dissolved at 50 ° C. 6.8 g (32 mmol) of LDI was added and reacted at 80 ° C. for 5 hours. 1.4 g (16 mmol) of 1,4-butanediamine (1,4-BDA) dissolved in 10 ml of DMAc was added dropwise at 80 ° C. for 1.5 hours. The produced polymer was dissolved in 100 ml of DMAc, precipitated with distilled water, washed with distilled water and purified. 24.9 g (yield 88.3%) of the polymer was obtained. The physical properties of the polymer were determined by the method described above and the results are shown in Table 1.
(比較例2)
引張試験サンプルを調製する際に、表1の割合で可塑剤グリセロールジアセタートラウラートを配合した以外は比較例1と同様に試験を行った。
(Comparative Example 2)
When preparing the tensile test sample, the test was conducted in the same manner as in Comparative Example 1 except that the plasticizer glycerol diacetatorlaurate was blended in the ratio shown in Table 1.
(比較例3)
フラスコにPCL2000 5g(2.5mmol)を入れ60℃で溶融させた。HDI 0.8g(4.5mmol)を加えて、100℃で5時間反応させた。塩化カルシウム1.0g、DMAc 20mlを加え、DMAc 10mlに溶解させた1,4-ブタンジアミン(1,4-BDA) 0.2g(2.5mmol)を室温で30分滴下し、全て滴下後に昇温し80℃で1時間反応させた。生成した重合物をDMAc50mlで溶解し、蒸留水で沈殿させ、蒸留水で洗浄し精製した。重合物が5.6g(収率93.5%)得られた。重合物の物性は前述の方法により求めその結果を表1に示す。
(Comparative Example 3)
The flask was charged with 5 g (2.5 mmol) of PCL2000 and melted at 60 ° C. HDI 0.8g (4.5mmol) was added and reacted at 100 ° C for 5 hours. Add 1.0 g of calcium chloride and 20 ml of DMAc, add dropwise 0.2 g (2.5 mmol) of 1,4-butanediamine (1,4-BDA) dissolved in 10 ml of DMAc at room temperature for 30 minutes, and heat up after all the drops are added. The reaction was carried out at 0 ° C. for 1 hour. The produced polymer was dissolved in 50 ml of DMAc, precipitated with distilled water, washed with distilled water and purified. 5.6 g (yield 93.5%) of the polymer was obtained. The physical properties of the polymer were determined by the method described above and the results are shown in Table 1.
(比較例4、5、6)
引張試験サンプルを調製する際に、表1の割合で可塑剤グリセロールジアセタートラウラートを配合した以外は比較例3と同様に試験を行った。
(Comparative Examples 4, 5, 6)
When preparing the tensile test sample, the test was conducted in the same manner as in Comparative Example 3 except that the plasticizer glycerol diacetatorolaurate was blended at the ratio shown in Table 1.
(比較例7)
フラスコにPCL1250 10g(8mmol)を入れ60℃で溶融させた。HDI 2.7g(16mmol)を加えて、85℃で5時間反応させた。DMAc 5mlを加え、DMAc 10mlに溶解させた1,2-プロパンジアミン(1,2-PDA) 0.6g(8mmol)を滴下したところゲル化してしまった。
(Comparative Example 7)
A flask was charged with 10 g (8 mmol) of PCL1250 and melted at 60 ° C. 2.7 g (16 mmol) of HDI was added and reacted at 85 ° C. for 5 hours. When 5 ml of DMAc was added and 0.6 g (8 mmol) of 1,2-propanediamine (1,2-PDA) dissolved in 10 ml of DMAc was added dropwise, gelation occurred.
(表中の‘>‘で標記された数字は装置の測定限界に達したものでこの値以上であることを示す。)
試験例1:生分解試験方法
ISO14852に記載されている組成を持つ無機培養液500ml にポリマー試料200mg を分散させ、(財)化学物質評価研究機構より提供された標準活性汚泥30ml を加え、撹伴しながら二酸化炭素を除いた空気で曝気を行い、培養槽の排気をアルカリトラップ(0.025N水酸化ナトリウム水溶液)に通し、ポリマーの生分解および微生物の代謝により発生した二酸化炭素を捕捉した。発生二酸化炭素量は無機炭素量として全有機体炭素計(TOC-V CSH、島津製作所)を用いて約1ヶ月間、1週間ごとに測定した。ポリマー試料の生分解性は100% 分解した場合に発生する二酸化炭素量を理論値として、以下の式により評価した。
生分解(%)= 100 × 二酸化炭素量(測定値)/ 二酸化炭素量(理論値)
結果を表2に示す。
(The numbers marked with “>” in the table indicate that the measurement limit of the device has been reached and this value is exceeded.)
Test Example 1: Biodegradation test method
Disperse 200 mg of polymer sample in 500 ml of inorganic culture solution having the composition described in ISO 14852, add 30 ml of standard activated sludge provided by the Chemical Substance Evaluation Research Organization, and remove carbon dioxide while stirring. The aeration tank was aerated and the exhaust of the culture tank was passed through an alkali trap (0.025N sodium hydroxide aqueous solution) to capture carbon dioxide generated by polymer biodegradation and microbial metabolism. The amount of carbon dioxide generated was measured as an inorganic carbon amount every week for about one month using a total organic carbon meter (TOC-V CSH, Shimadzu Corporation). The biodegradability of the polymer sample was evaluated according to the following formula using the amount of carbon dioxide generated when 100% decomposed as a theoretical value.
Biodegradation (%) = 100 × carbon dioxide content (measured value) / carbon dioxide content (theoretical value)
The results are shown in Table 2.
Claims (8)
工程1:ジイソシアネートと生分解性ポリエステルジオールを反応させて、両末端イソシアネート基を持つプレポリマーを合成する;
工程2:ハロゲン化アルカリ金属塩あるいはハロゲン化アルカリ土類金属塩の存在下で側鎖を有する脂肪族ジアミンをさらに反応させて鎖長延長反応を行い、セグメント化ポリウレタンウレアを得る。 The process for producing a segmented polyurethaneurea according to claim 1, comprising the following steps: Step 1: A diisocyanate and a biodegradable polyester diol are reacted to synthesize a prepolymer having both terminal isocyanate groups;
Step 2: A chain extension reaction is carried out by further reacting an aliphatic diamine having a side chain in the presence of an alkali metal halide salt or an alkaline earth metal halide salt to obtain a segmented polyurethane urea.
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