JP4297352B2 - Multi-branched macromonomer having multiple hydroxyl groups - Google Patents
Multi-branched macromonomer having multiple hydroxyl groups Download PDFInfo
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- JP4297352B2 JP4297352B2 JP2004127980A JP2004127980A JP4297352B2 JP 4297352 B2 JP4297352 B2 JP 4297352B2 JP 2004127980 A JP2004127980 A JP 2004127980A JP 2004127980 A JP2004127980 A JP 2004127980A JP 4297352 B2 JP4297352 B2 JP 4297352B2
- Authority
- JP
- Japan
- Prior art keywords
- poly
- bho
- ethyl
- ether
- oxetane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims description 24
- -1 oxetane compound Chemical class 0.000 claims description 69
- 229920000642 polymer Polymers 0.000 claims description 30
- 229920000570 polyether Polymers 0.000 claims description 27
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 26
- 125000003566 oxetanyl group Chemical group 0.000 claims description 25
- 229920005862 polyol Polymers 0.000 claims description 25
- 150000003077 polyols Chemical class 0.000 claims description 25
- 238000012653 anionic ring-opening polymerization Methods 0.000 claims description 7
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 7
- QSGREIXRTDCBHO-UHFFFAOYSA-N [3-(hydroxymethyl)oxetan-3-yl]methanol Chemical compound OCC1(CO)COC1 QSGREIXRTDCBHO-UHFFFAOYSA-N 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 50
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- FNYWFRSQRHGKJT-UHFFFAOYSA-N 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane Chemical compound C1OCC1(CC)COCC1(CC)COC1 FNYWFRSQRHGKJT-UHFFFAOYSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 9
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 7
- 239000002274 desiccant Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 230000032050 esterification Effects 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000001226 reprecipitation Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 150000001450 anions Chemical group 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 5
- 235000002597 Solanum melongena Nutrition 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 150000003983 crown ethers Chemical class 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- BIDWUUDRRVHZLQ-UHFFFAOYSA-N 3-ethyl-3-(2-ethylhexoxymethyl)oxetane Chemical compound CCCCC(CC)COCC1(CC)COC1 BIDWUUDRRVHZLQ-UHFFFAOYSA-N 0.000 description 4
- JUXZNIDKDPLYBY-UHFFFAOYSA-N 3-ethyl-3-(phenoxymethyl)oxetane Chemical compound C=1C=CC=CC=1OCC1(CC)COC1 JUXZNIDKDPLYBY-UHFFFAOYSA-N 0.000 description 4
- 238000012656 cationic ring opening polymerization Methods 0.000 description 4
- 239000000412 dendrimer Substances 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 229920000587 hyperbranched polymer Polymers 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 3
- LMIOYAVXLAOXJI-UHFFFAOYSA-N 3-ethyl-3-[[4-[(3-ethyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(CC)COC2)C=CC=1COCC1(CC)COC1 LMIOYAVXLAOXJI-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 244000061458 Solanum melongena Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000021736 acetylation Effects 0.000 description 3
- 238000006640 acetylation reaction Methods 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- UACSZOWTRIJIFU-UHFFFAOYSA-N hydroxymethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCO UACSZOWTRIJIFU-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- UCBQKJQXUPVHFJ-UHFFFAOYSA-N 1-cyclopenta-2,4-dien-1-yl-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1C1C=CC=C1 UCBQKJQXUPVHFJ-UHFFFAOYSA-N 0.000 description 2
- UWFHYGTWXNRUDH-UHFFFAOYSA-N 3-ethyl-3-[4-[(3-ethyloxetan-3-yl)methoxy]butoxymethyl]oxetane Chemical compound C1OCC1(CC)COCCCCOCC1(CC)COC1 UWFHYGTWXNRUDH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- PFHLXMMCWCWAMA-UHFFFAOYSA-N [4-(4-diphenylsulfoniophenyl)sulfanylphenyl]-diphenylsulfanium Chemical compound C=1C=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1SC(C=C1)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 PFHLXMMCWCWAMA-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229920000736 dendritic polymer Polymers 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- HOXINJBQVZWYGZ-UHFFFAOYSA-N fenbutatin oxide Chemical compound C=1C=CC=CC=1C(C)(C)C[Sn](O[Sn](CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C1=CC=CC=C1 HOXINJBQVZWYGZ-UHFFFAOYSA-N 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- JWZVNQGIGRCDRU-UHFFFAOYSA-N (3-butan-2-yloxetan-3-yl)methanol Chemical compound CCC(C)C1(CO)COC1 JWZVNQGIGRCDRU-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- NLQMSBJFLQPLIJ-UHFFFAOYSA-N (3-methyloxetan-3-yl)methanol Chemical compound OCC1(C)COC1 NLQMSBJFLQPLIJ-UHFFFAOYSA-N 0.000 description 1
- FMUFFUZPAMYTLG-UHFFFAOYSA-N (3-propan-2-yloxetan-3-yl)methanol Chemical compound CC(C)C1(CO)COC1 FMUFFUZPAMYTLG-UHFFFAOYSA-N 0.000 description 1
- CUBVDBSVGQEYCB-UHFFFAOYSA-N (3-propyloxetan-3-yl)methanol Chemical compound CCCC1(CO)COC1 CUBVDBSVGQEYCB-UHFFFAOYSA-N 0.000 description 1
- AMONDPRIVREWOC-UHFFFAOYSA-N (3-tert-butyloxetan-3-yl)methanol Chemical compound CC(C)(C)C1(CO)COC1 AMONDPRIVREWOC-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- BGYBONWLWSMGNV-UHFFFAOYSA-N 1,4,7,10,13,16,19,22-octaoxacyclotetracosane Chemical compound C1COCCOCCOCCOCCOCCOCCOCCO1 BGYBONWLWSMGNV-UHFFFAOYSA-N 0.000 description 1
- XKEHLMZHBXCJGZ-UHFFFAOYSA-N 1,4,7,10,13,16,19-heptaoxacyclohenicosane Chemical compound C1COCCOCCOCCOCCOCCOCCO1 XKEHLMZHBXCJGZ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AWOGBOARESKNBA-UHFFFAOYSA-N 1-[(3-ethyloxetan-3-yl)methoxy]propan-2-ol Chemical compound CC(O)COCC1(CC)COC1 AWOGBOARESKNBA-UHFFFAOYSA-N 0.000 description 1
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- MJNGDTGKCWWIOP-UHFFFAOYSA-N 2-[(3-ethyloxetan-3-yl)methoxy]ethanol Chemical compound OCCOCC1(CC)COC1 MJNGDTGKCWWIOP-UHFFFAOYSA-N 0.000 description 1
- SNAGVRNJNARVRV-UHFFFAOYSA-N 2-[(3-ethyloxetan-3-yl)methoxymethyl]oxolane Chemical compound C1CCOC1COCC1(CC)COC1 SNAGVRNJNARVRV-UHFFFAOYSA-N 0.000 description 1
- DVSDTPMZVLDKRT-UHFFFAOYSA-N 2-[2-[(3-ethyloxetan-3-yl)methoxy]butoxy]ethanol Chemical compound OCCOCC(CC)OCC1(CC)COC1 DVSDTPMZVLDKRT-UHFFFAOYSA-N 0.000 description 1
- BXYWKXBAMJYTKP-UHFFFAOYSA-N 2-[2-[2-[2-(3-sulfanylpropanoyloxy)ethoxy]ethoxy]ethoxy]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOCCOCCOCCOC(=O)CCS BXYWKXBAMJYTKP-UHFFFAOYSA-N 0.000 description 1
- NDDNVEQCBHMWIX-UHFFFAOYSA-N 2-ethyl-3-(phenoxymethyl)oxetane Chemical compound CCC1OCC1COC1=CC=CC=C1 NDDNVEQCBHMWIX-UHFFFAOYSA-N 0.000 description 1
- CFMTUYVTICDMTL-UHFFFAOYSA-N 2-ethyl-3-[[2-[2-[(2-ethyloxetan-3-yl)methoxy]phenyl]phenoxy]methyl]oxetane Chemical compound CCC1OCC1COC1=CC=CC=C1C1=CC=CC=C1OCC1C(CC)OC1 CFMTUYVTICDMTL-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- CXURGFRDGROIKG-UHFFFAOYSA-N 3,3-bis(chloromethyl)oxetane Chemical compound ClCC1(CCl)COC1 CXURGFRDGROIKG-UHFFFAOYSA-N 0.000 description 1
- RVGLUKRYMXEQAH-UHFFFAOYSA-N 3,3-dimethyloxetane Chemical compound CC1(C)COC1 RVGLUKRYMXEQAH-UHFFFAOYSA-N 0.000 description 1
- HGCHXPWVBFSUDT-UHFFFAOYSA-N 3-(2-butoxyethoxymethyl)-3-ethyloxetane Chemical compound CCCCOCCOCC1(CC)COC1 HGCHXPWVBFSUDT-UHFFFAOYSA-N 0.000 description 1
- XVGDVJXJWSIGTH-UHFFFAOYSA-N 3-(chloromethyl)-2-ethyloxetane Chemical compound CCC1OCC1CCl XVGDVJXJWSIGTH-UHFFFAOYSA-N 0.000 description 1
- FEJVJGYJIPXMJD-UHFFFAOYSA-N 3-(cyclohexyloxymethyl)-3-ethyloxetane Chemical compound C1CCCCC1OCC1(CC)COC1 FEJVJGYJIPXMJD-UHFFFAOYSA-N 0.000 description 1
- RTSIZIWENWUGNX-UHFFFAOYSA-N 3-(dodecoxymethyl)-3-ethyloxetane Chemical compound CCCCCCCCCCCCOCC1(CC)COC1 RTSIZIWENWUGNX-UHFFFAOYSA-N 0.000 description 1
- WKXMZIDBVDIVME-UHFFFAOYSA-N 3-[(3-ethyloxetan-3-yl)methoxy]-2,2-bis[(3-ethyloxetan-3-yl)methoxymethyl]propan-1-ol Chemical compound C1OCC1(CC)COCC(CO)(COCC1(CC)COC1)COCC1(CC)COC1 WKXMZIDBVDIVME-UHFFFAOYSA-N 0.000 description 1
- MKNOYISMZFDLQP-UHFFFAOYSA-N 3-[1-[2-(oxetan-3-yl)butoxy]butan-2-yl]oxetane Chemical compound C1OCC1C(CC)COCC(CC)C1COC1 MKNOYISMZFDLQP-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- FVGDNYRHKDREFL-UHFFFAOYSA-N 3-ethyl-3-(1-phenoxyethoxymethyl)oxetane Chemical compound C=1C=CC=CC=1OC(C)OCC1(CC)COC1 FVGDNYRHKDREFL-UHFFFAOYSA-N 0.000 description 1
- PWGAXPBJOGFFMY-UHFFFAOYSA-N 3-ethyl-3-(2-methylpropoxymethoxymethyl)oxetane Chemical compound CC(C)COCOCC1(CC)COC1 PWGAXPBJOGFFMY-UHFFFAOYSA-N 0.000 description 1
- BQCKULHUFAYFSD-UHFFFAOYSA-N 3-ethyl-3-(2-phenoxyethoxymethyl)oxetane Chemical compound C=1C=CC=CC=1OCCOCC1(CC)COC1 BQCKULHUFAYFSD-UHFFFAOYSA-N 0.000 description 1
- CXGVNLOQKSDKPU-UHFFFAOYSA-N 3-ethyl-3-(octadecoxymethyl)oxetane Chemical compound CCCCCCCCCCCCCCCCCCOCC1(CC)COC1 CXGVNLOQKSDKPU-UHFFFAOYSA-N 0.000 description 1
- DILMQZOSIJKYHA-UHFFFAOYSA-N 3-ethyl-3-[(2,3,4,5,6-pentabromophenoxy)methyl]oxetane Chemical compound BrC=1C(Br)=C(Br)C(Br)=C(Br)C=1OCC1(CC)COC1 DILMQZOSIJKYHA-UHFFFAOYSA-N 0.000 description 1
- FQUZJULGTSCUDF-UHFFFAOYSA-N 3-ethyl-3-[(2,3,4,5,6-pentachlorophenoxy)methyl]oxetane Chemical compound ClC=1C(Cl)=C(Cl)C(Cl)=C(Cl)C=1OCC1(CC)COC1 FQUZJULGTSCUDF-UHFFFAOYSA-N 0.000 description 1
- PBXYBVUSKINNJL-UHFFFAOYSA-N 3-ethyl-3-[(2,3,4-tribromophenoxy)methyl]oxetane Chemical compound C=1C=C(Br)C(Br)=C(Br)C=1OCC1(CC)COC1 PBXYBVUSKINNJL-UHFFFAOYSA-N 0.000 description 1
- JCBNYALMACLNBI-UHFFFAOYSA-N 3-ethyl-3-[(3-fluorophenyl)methoxymethyl]oxetane Chemical compound FC1=CC(=CC=C1)COCC1(COC1)CC JCBNYALMACLNBI-UHFFFAOYSA-N 0.000 description 1
- PENKVNGNXDMJKV-UHFFFAOYSA-N 3-ethyl-3-[(4-methoxyphenyl)methoxymethyl]oxetane Chemical compound C=1C=C(OC)C=CC=1COCC1(CC)COC1 PENKVNGNXDMJKV-UHFFFAOYSA-N 0.000 description 1
- UXEOSBGULDWPRJ-UHFFFAOYSA-N 3-ethyl-3-[5-[(3-ethyloxetan-3-yl)methoxy]pentoxymethyl]oxetane Chemical compound C1OCC1(CC)COCCCCCOCC1(CC)COC1 UXEOSBGULDWPRJ-UHFFFAOYSA-N 0.000 description 1
- GBDPVIKGIRHANI-UHFFFAOYSA-N 3-ethyl-3-[6-[(3-ethyloxetan-3-yl)methoxy]hexoxymethyl]oxetane Chemical compound C1OCC1(CC)COCCCCCCOCC1(CC)COC1 GBDPVIKGIRHANI-UHFFFAOYSA-N 0.000 description 1
- KRISPYQCCVEVFA-UHFFFAOYSA-N 3-methoxy-3-methylpentane Chemical compound CCC(C)(CC)OC KRISPYQCCVEVFA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- WKJPCNYINDUTQL-UHFFFAOYSA-N C(C(C)C)C1(COC1)CO.C(CCC)C1(COC1)CO Chemical compound C(C(C)C)C1(COC1)CO.C(CCC)C1(COC1)CO WKJPCNYINDUTQL-UHFFFAOYSA-N 0.000 description 1
- YJMHOSVAHLCHNN-UHFFFAOYSA-N C1=CC=C(C=C1)CN2C=CC=C(C2C#N)N Chemical class C1=CC=C(C=C1)CN2C=CC=C(C2C#N)N YJMHOSVAHLCHNN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- JMMSLMMJRMCXPW-UHFFFAOYSA-N OC.OC.C1CC2CCC1C2 Chemical compound OC.OC.C1CC2CCC1C2 JMMSLMMJRMCXPW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- FWOHNFOTPCHCMT-UHFFFAOYSA-N carbonic acid;oxetane Chemical compound C1COC1.C1COC1.OC(O)=O FWOHNFOTPCHCMT-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- MZWHIEFYUAYOJU-UHFFFAOYSA-N hexanedioic acid;oxetane Chemical compound C1COC1.C1COC1.OC(=O)CCCCC(O)=O MZWHIEFYUAYOJU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- WCAOBJJSISYNMN-UHFFFAOYSA-N oxetane;terephthalic acid Chemical compound C1COC1.C1COC1.OC(=O)C1=CC=C(C(O)=O)C=C1 WCAOBJJSISYNMN-UHFFFAOYSA-N 0.000 description 1
- 150000002921 oxetanes Chemical class 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Polyethers (AREA)
Description
本発明は、複数の水酸基を有する多分岐マクロモノマー（ハイパーブランチ高分子）及び、その製造に関する。 The present invention relates to a hyperbranched macromonomer (hyperbranched polymer) having a plurality of hydroxyl groups and the production thereof.
近年、デンドリマーやハイパーブランチ高分子、スターポリマー、グラフトポリマー、ブラシポリマーなどのような線状ポリマーとは異なる構造を有するポリマーが、線状高分子とは異なる新機能や新性能を有することから注目を集めている。これらの中でもグラフトポリマーやブラシポリマーは、ポリマーとポリマーとの反応、あるいはポリマーとモノマーとの反応により合成される。即ち、ポリマー上に重合開始種を生成させ、そこからモノマーを重合させる方法、または生長ポリマーと停止機能を有するポリマー鎖とをカップリングさせる方法である。しかし、これらの方法は、幹や枝のホモポリマーの副生及び／又は枝の長さの不揃いなど、いくつかの欠点を伴う場合がある。 Recently, polymers with a different structure from linear polymers such as dendrimers, hyperbranched polymers, star polymers, graft polymers, and brush polymers have new functions and performances that differ from linear polymers. Collecting. Among these, graft polymers and brush polymers are synthesized by a reaction between a polymer and a polymer or a reaction between a polymer and a monomer. That is, a method in which a polymerization initiating species is generated on a polymer and a monomer is polymerized therefrom, or a growth polymer and a polymer chain having a stopping function are coupled. However, these methods may have some drawbacks, such as by-product of trunk and branch homopolymers and / or uneven branch lengths.
これら以外に、第三の方法ともいえるマクロモノマーが最近盛んに研究されるようになってきた。なお、マクロモノマーとは、分子量がある程度高く（通常、数１００〜１００００程度）、かつ重合することの出来る官能基を有するものである。このようなマクロモノマーの一次構造を制御して合成し、他のモノマーと共重合させることにより、枝の長さの揃ったグラフトポリマーなどを容易に合成することが可能である（例えば、非特許文献１参照）。なお、グラフトポリマーやブラシボリマーを合成するために用いるマクロモノマーの形状は、直鎖状である。 In addition to these, a macromonomer that can be said to be a third method has recently been actively studied. In addition, a macromonomer has a functional group which has high molecular weight to some extent (usually about several hundred to 10,000) and can be polymerized. By synthesizing such a macromonomer with a primary structure controlled and copolymerizing with other monomers, it is possible to easily synthesize a graft polymer having a uniform branch length (for example, non-patented). Reference 1). The macromonomer used for synthesizing the graft polymer or the brush polymer is linear.
一方、最近、マクロモノマーに多分岐構造であるデンドロン（デンドリマーのサブユニット）を導入し、側鎖にデンドリティック部位を有するポリデンドロンの合成の研究が行われている。例えば、コアに水酸基を有するポリエーチルデンドロンとクロロメチルスチレンとの反応によりデンドリティックマクロモノマーを合成し、その後、スチレンモノマーとラジカル共重合させることによりポリデンドロンが得られることが報告されている（例えば、非特許文献２参照）。また、メタクリロイル基を有する第二世代ポリエーテルデンドロンを合成し、単独でラジカル重合を行うことにより、重合度（Ｄ．Ｐ．）＝６．７のポリデンドロンが得られることが報告されている（例えば、非特許文献３参照）。
デンドロンと同様に多分岐構造を有するハイパーブランチ高分子をマクロモノマーとして用いたものも報告されている（例えば、非特許文献４参照）。
On the other hand, recently, dendrons (dendrimer subunits) having a multi-branched structure have been introduced into macromonomers, and studies have been conducted on the synthesis of polydendrons having a dendritic site in the side chain. For example, it has been reported that a polydendron can be obtained by synthesizing a dendritic macromonomer by the reaction of a polyethyldendron having a hydroxyl group in the core with chloromethylstyrene, and then radically copolymerizing with the styrene monomer ( For example, refer nonpatent literature 2). In addition, it has been reported that a polydendron having a degree of polymerization (DP) = 6.7 can be obtained by synthesizing a second generation polyether dendron having a methacryloyl group and carrying out radical polymerization alone. For example, refer nonpatent literature 3).
Similar to dendrons, those using hyperbranched polymers having a multi-branched structure as macromonomers have also been reported (for example, see Non-Patent Document 4).
また、（３−アルキル−３−ヒドロキシメチル）オキセタン類のアニオン開環重合により、分子内に１個のオキセタニル基と多数の水酸基を有するヘテロテレケリックハイパーブランチポリエーテルが得られることが報告されている（例えば、非特許文献５参照）。 In addition, it has been reported that heterotelechelic hyperbranched polyethers having one oxetanyl group and many hydroxyl groups in the molecule can be obtained by anion ring-opening polymerization of (3-alkyl-3-hydroxymethyl) oxetanes. (For example, refer nonpatent literature 5).
オキセタン化合物を用いたハイパーブランチ高分子の製造法ついては、オキセタン化合物と多官能性カルボン酸化合物との重付加反応による方法が知られている（例えば、特許文献１参照）。また、オキセタニル基とフェノール類との反応については、ビスオキセタン化合物とビスフェノール類から重付加共重合体を製造する方法が知られている（例えば、特許文献２参照）。 As a method for producing a hyperbranched polymer using an oxetane compound, a method based on a polyaddition reaction between an oxetane compound and a polyfunctional carboxylic acid compound is known (for example, see Patent Document 1). Moreover, about the reaction of an oxetanyl group and phenols, the method of manufacturing a polyaddition copolymer from a bisoxetane compound and bisphenol is known (for example, refer patent document 2).
ビニル基やエポキシ基等の重合性基を有する化合物又はカルボキシル基等の官能基を有する化合物と結合させることができる一級水酸基を複数個有する多分岐マクロモノマーを提供することである。 To provide a multi-branched macromonomer having a plurality of primary hydroxyl groups that can be bonded to a compound having a polymerizable group such as a vinyl group or an epoxy group or a compound having a functional group such as a carboxyl group.
上記の問題を解決するため本発明者らは、種々の検討を行った結果、水酸基を有するオキセタン化合物をアニオン開環重合させることにより分子内に１個のオキセタニル基と複数の水酸基とを有する多分岐ポリエーテルポリオール（多分岐ポリエーテルポリオールと称する）を得た後、この多分岐ポリエーテルポリオールを単独で、またはこの多分岐ポリエーテルポリオールと他のオキセタン化合物とを反応させて得られる複数の水酸基を有する多分岐マクロモノマー（多分岐マクロモノマーと称する）により上記課題を解決できることを見出した。また、この多分岐マクロモノマーを得るための製造方法を提供する。
以下、本発明を詳細に説明する。
In order to solve the above problem, the present inventors have conducted various studies. As a result, an anion ring-opening polymerization of an oxetane compound having a hydroxyl group results in a polyoxygen having one oxetanyl group and a plurality of hydroxyl groups in the molecule. After obtaining a branched polyether polyol (referred to as a multi-branched polyether polyol), the multi-branched polyether polyol alone or a plurality of the poly-branched polyether polyols obtained by reacting the multi-branched polyether polyol with another oxetane compound are obtained. It has been found that the above problems can be solved by a multibranched macromonomer having a hydroxyl group (referred to as a multibranched macromonomer). Moreover, the manufacturing method for obtaining this multibranched macromonomer is provided.
Hereinafter, the present invention will be described in detail.
本発明の多分岐ポリエーテルポリオールおよび多分岐マクロモノマーとその製造方法について説明する。 The multibranched polyether polyol and multibranched macromonomer of the present invention and the production method thereof will be described.
○水酸基を有するオキセタン化合物
多分岐ポリエーテルポリオールの合成に用いる水酸基を有するオキセタン化合物としては、下記式（１）が挙げられる。
Oxetane compound having a hydroxyl group Examples of the oxetane compound having a hydroxyl group used for the synthesis of a multi-branched polyether polyol include the following formula (1).
式（１）中のＲ1とＲ2は水酸基を有する炭素数１〜４のアルキル基を示しす。そして、Ｒ1とＲ2とが同一であっても異なっていてもよい。 R 1 and R 2 in the formula (1) represent a C 1-4 alkyl group having a hydroxyl group. R 1 and R 2 may be the same or different.
式（１）のＲ1としては、水酸基を有する炭素数１〜４のアルキル基であり、ヒドロキシメチル基が好ましい。また、Ｒ2としては水酸基を有する炭素数１〜４のアルキル基であり、ヒドロキシメチル基が好ましい。具体的には、３，３−ビス（ヒドロキシメチル）オキセタン等が挙げられる。 The R 1 in the formula (1), an alkyl group having 1 to 4 carbon atoms having a hydroxyl group, a hydroxymethyl group is preferable. R 2 is a C 1-4 alkyl group having a hydroxyl group, and is preferably a hydroxymethyl group. Specific examples include 3,3-bis (hydroxymethyl) oxetane.
○１個のオキセタニル基と複数の水酸基とを有する多分岐ポリエーテルポリオール
式（１）で表される化合物をアニオン開環重合させることにより分子内に１個のオキセタニル基と複数の水酸基とを有する多分岐ポリエーテルポリオールを合成することができる。
このアニオン開環重合の開始剤としては、アルカリ金属、アルカリ金属水酸化物、アルカリ金属アルコキシド、ジエチル亜鉛などの有機亜鉛、アルミニウムポルフィリン錯体、アルカリ金属アルコキシドとクラウンエーテルの併用系などを用いることができ、アルカリ金属アルコキシドとクラウンエーテルとの併用系が好適である。
○ Multi-branched polyether polyol having one oxetanyl group and a plurality of hydroxyl groups Having one oxetanyl group and a plurality of hydroxyl groups in the molecule by anionic ring-opening polymerization of the compound represented by formula (1) Multi-branched polyether polyols can be synthesized.
As an initiator of this anion ring-opening polymerization, alkali metals, alkali metal hydroxides, alkali metal alkoxides, organozinc such as diethyl zinc, aluminum porphyrin complexes, combined systems of alkali metal alkoxides and crown ethers can be used. A combined system of an alkali metal alkoxide and a crown ether is preferred.
このアニオン開環重合に用いるアルカリ金属アルコキシドとしては、ナトリウムメトキシド、カリウムメトキシド、ナトリウムエトキシド、カリウムエトキシド、ｔ−ブトキシナトリウム、およびｔ−ブトキシカリウム（ｔ−ＢｕＯＫ）等が挙げられる。 Examples of the alkali metal alkoxide used in this anion ring-opening polymerization include sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, t-butoxy sodium, and t-butoxy potassium (t-BuOK).
このアニオン開環重合に用いるクラウンエーテルとしては、１２−クラウン−４、１５−クラウン−５、１８−クラウン−６（１８−Ｃ−６）、シス−ジシクロヘキサノ−１８−クラウン−６、２１−クラウン−７、および２４−クラウン−８等が挙げられる。 As crown ethers used in this anion ring-opening polymerization, 12-crown-4, 15-crown-5, 18-crown-6 (18-C-6), cis-dicyclohexano-18-crown-6, 21 -Crown-7, 24-Crown-8, etc. are mentioned.
○複数の水酸基を有する多分岐マクロモノマー
本発明の多分岐マクロモノマーは、多分岐ポリエーテルポリオールを単独でアニオン重合することにより得ることができ、又は多分岐ポリエーテルポリオールを単独でカチオン重合することにより得ることができる。また、多分岐ポリエーテルポリオールと他のオキセタン化合物とをカチオン重合することにより得ることができる。
○ Multi-branched macromonomer having a plurality of hydroxyl groups The multi-branched macromonomer of the present invention can be obtained by anionic polymerization of a multi-branched polyether polyol alone, or a cationic polymerization of a multi-branched polyether polyol alone. Can be obtained. Further, it can be obtained by cationic polymerization of a multi-branched polyether polyol and another oxetane compound .
本発明の多分岐マクロモノマーは、多分岐ポリエーテルポリオール単独でアニオン重合することにより得ることができるが、このアニオン開環重合の開始剤として、アルカリ金属、アルカリ金属水酸化物、アルカリ金属アルコキシド、ジエチル亜鉛などの有機亜鉛、アルミニウムポルフィリン錯体、アルカリ金属アルコキシドとクラウンエーテルの併用系などを用いることができる。特に、アルカリ金属アルコキシドとクラウンエーテル併用系が好適であり、例えばｔ−ＢｕＯＫ／１８−Ｃ―６を用いて合成することができる。 The multibranched macromonomer of the present invention can be obtained by anionic polymerization with a multibranched polyether polyol alone. As an initiator of this anion ring-opening polymerization, an alkali metal, an alkali metal hydroxide, an alkali metal alkoxide, An organic zinc such as diethyl zinc, an aluminum porphyrin complex, a combined system of an alkali metal alkoxide and a crown ether, or the like can be used. In particular, an alkali metal alkoxide and crown ether combined system is suitable, and for example, it can be synthesized using t-BuOK / 18-C-6.
また、本発明の多分岐マクロモノマーは、多分岐ポリエーテルポリオールを単独でカチオン重合することにより得ることもできる。このときのカチオン開環重合の開始剤としては、プロトン酸、ルイス酸、光・熱によりカチオン（酸）を発生する光カチオン開始剤、及び熱カチオン開始剤などを挙げることができる。当該プロトン酸としては、硫酸、塩酸などの無機酸、メタンスルホン酸、トリフルオロ酢酸などの有機酸、クロロスルホン酸、フルオロスルホン酸、トリフルオロメタンスルホン酸などの超強酸が挙げられる。また、当該ルイス酸としては、トリフルオロホウ素、そのエーテル錯体、塩化アルミニウム、アルキル塩化アルミニウム、塩化チタンなどが挙げられる。当該光カチオン開始剤としては、ビス［４−（ジフェニルスルホニオ）フェニル］スルフィドビスヘキサフルオロホスフェート、ビス［４−（ジフェニルスルホニオ）フェニル］スルフィドビスヘキサフルオロアンチモネート、ビス［４−（ジフェニルスルホニオ）フェニル］スルフィドビステトラフルオロボレートなどのスルホニウム塩、ジフェニルヨードニウムヘキサフルロホスフェート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムテトラフルオロボレートなどのヨードニウム塩、フェニルジアゾニウムヘキサフルオロホスフェート、フェニルジアゾニウムヘキサフルオロアンチモネート、フェニルジアゾニウムテトラフルオロボレートなどのジアゾニウム塩、１−ベンジル−２−シアノピリジニウムヘキサフルオロホスフェート、１−ベンジル−２−シアノピリジニウムヘキサフルオロアンチモネート、１−ベンジル−２−シアノピリジニウムテトラフルオロボレートなどのアンモニウム塩、（２，４−シクロペンタジエン−１−イル）［（１−メチルエチル）ベンゼン］−Ｆｅ（II）ヘキサフルオロホス
フェート、（２，４−シクロペンタジエン−１−イル）［（１−メチルエチル）ベンゼン］−Ｆｅ（II）ヘキサフルオロアンチモネート、（２，４−シクロペンタジエン−１−イル）
［（１−メチルエチル）ベンゼン］−Ｆｅ（II）テトラフルオロボレートなどのフェロセン
などが挙げられる。
The multibranched macromonomer of the present invention can also be obtained by cationic polymerization of a multibranched polyether polyol alone. Examples of the initiator for cationic ring-opening polymerization include a protonic acid, a Lewis acid, a photocationic initiator that generates a cation (acid) by light and heat, and a thermal cationic initiator. Examples of the protonic acid include inorganic acids such as sulfuric acid and hydrochloric acid, organic acids such as methanesulfonic acid and trifluoroacetic acid, and super strong acids such as chlorosulfonic acid, fluorosulfonic acid, and trifluoromethanesulfonic acid. Examples of the Lewis acid include trifluoroboron, its ether complex, aluminum chloride, alkyl aluminum chloride, and titanium chloride. Examples of the photocation initiator include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, and bis [4- (diphenylsulfone). Nio) sulfonium salts such as phenyl] sulfide bistetrafluoroborate, iphenylonium salts such as diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate , Diazonium salts such as phenyldiazonium tetrafluoroborate, 1-benzyl-2-cyanopyridinyl Ammonium salts such as 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, (2,4-cyclopentadien-1-yl) [(1- Methylethyl) benzene] -Fe (II) hexafluorophosphate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) hexafluoroantimonate, (2,4- Cyclopentadien-1-yl)
Examples include ferrocene such as [(1-methylethyl) benzene] -Fe (II) tetrafluoroborate.
多分岐ポリエーテルポリオールと他のオキセタン化合物とをカチオン重合することにより得ることができる多分岐マクロモノマーは、先に記載したカチオン重合の開始剤を用いてカチオン開環重合を行うことにより合成することができる。これに用いるオキセタン化合物としては、オキセタン環を１個有するもの、オキセタン環を２個有するもの、オキセタン環を３個有するもの、またはオキセタン環を４個以上有するものが例示でき、好ましくはオキセタン環を１個有するものまたはオキセタン環を２個有するものであり、更に好ましくはオキセタン環を１個有するものである。 The multi-branched macromonomer that can be obtained by cationic polymerization of a multi-branched polyether polyol and another oxetane compound is synthesized by performing cationic ring-opening polymerization using the cationic polymerization initiator described above. Can do. Examples of the oxetane compound used for this include those having one oxetane ring, those having two oxetane rings, those having three oxetane rings, and those having four or more oxetane rings, and preferably having an oxetane ring. One having one or two oxetane rings, more preferably one having one oxetane ring.
オキセタン環を１個有するものとしては、トリメチレンオキシド、３，３−ジクロロメチルオキセタン、３，３−ジメチルオキセタン、３−３−ヒドロキシメチルオキセタン、３−メチル−３−ヒドロキシメチルオキセタン、３−エチル−３−ヒドロキシメチルオキセタン、３−エチル−３−フェノキシメチルオキセタン、３−ｎ−プロピル−３−ヒドロキシメチルオキセタン、３−イソプロピル−３−ヒドロキシメチルオキセタン、３−ｎ−ブチル−３−ヒドロキシメチルオキセタン、３−イソブチル−３−ヒドロキシメチルオキセタン、３−ｓｅｃ−ブチル−３−ヒドロキシメチルオキセタン、３−ｔｅｒｔ−ブチル−３−ヒドロキシメチルオキセタン、３−（メタ）アリルオキシメチル−３−エチルオキセタン、（３−エチル−３−オキセタニルメトキシ）メチルベンゼン、４−フルオロ−〔１−（３−エチル−３−オキセタニルメトキシ）メチル〕ベンゼン、４−メトキシ−〔１−（３−エチル−３−オキセタニルメトキシ）メチル〕ベンゼン、〔１−（３−エチル−３−オキセタニルメトキシ）エチル〕フェニルエーテル、イソブトキシメチル（３−エチル−３−オキセタニルメチル）エーテル、イソボルニルオキシエチル（３−エチル−３−オキセタニルメチル）エーテル、イソボルニル（３−エチル−３−オキセタニルメチル）エーテル、２−エチルヘキシル（３−エチル−３−オキセタニルメチル）エーテル、エチルジエチレングリコール（３−エチル−３−オキセタニルメチル）エーテル、ジシクロペンタジエン（３−エチル−３−オキセタニルメチル）エーテル、ジシクロペンテニルオキシエチル（３−エチル−３−オキセタニルメチル）エーテル、ジシクロペンテニル（３−エチル−３−オキセタニルメチル）エーテル、テトラヒドロフルフリル（３−エチル−３−オキセタニルメチル）エーテル、テトラブロモフェニル（３−エチル−３−オキセタニルメチル）エーテル、２−テトラブロモフェノキシエチル（３−エチル−３−オキセタニルメチル）エーテル、トリブロモフェニル（３−エチル−３−オキセタニルメチル）エーテル、２−トリブロモフェノキシエチル（３−エチル−３−オキセタニルメチル）エーテル、２−ヒドロキシエチル（３−エチル−３−オキセタニルメチル）エーテル、２−ヒドロキシプロピル（３−エチル−３−オキセタニルメチル）エーテル、ブトキシエチル（３−エチル−３−オキセタニルメチル）エーテル、ペンタクロロフェニル（３−エチル−３−オキセタニルメチル）エーテル、ペンタブロモフェニル（３−エチル−３−オキセタニルメチル）エーテル、ボルニル（３−エチル−３−オキセタニルメチル）エーテル等が挙げられる。更に好ましくは（カッコ内は商品名又は開発品名、東亞合成製）、３−エチル−３−（２−エチルヘキシロキシメチル）オキセタン（アロンオキセタンＯＸＴ−２１２（ＥＨＯＸ））、３−エチル−３−（シクロヘキシルオキシメチル）オキセタン（ＣＨＯＸ）、３−エチル−３−（ドデシロキシメチル）オキセタン（ＯＸＲ−１２）、３−エチル−３−（オクタデカシロキシメチル）オキセタン（ＯＸＲ−１８）、３−エチル−３−（フェノキシメチル）オキセタン（アロンオキセタンＯＸＴ−２１１（ＰＯＸ））、３−エチル−３−ヒドロキシメチルオキセタン（ＯＸＡ）等が挙げられる。これらは１種単独あるいは２種以上を組み合わせて用いることができる。 Those having one oxetane ring include trimethylene oxide, 3,3-dichloromethyl oxetane, 3,3-dimethyl oxetane, 3-3-hydroxymethyl oxetane, 3-methyl-3-hydroxymethyl oxetane, 3-ethyl. -3-hydroxymethyl oxetane, 3-ethyl-3-phenoxymethyl oxetane, 3-n-propyl-3-hydroxymethyl oxetane, 3-isopropyl-3-hydroxymethyl oxetane, 3-n-butyl-3-hydroxymethyl oxetane 3-isobutyl-3-hydroxymethyloxetane, 3-sec-butyl-3-hydroxymethyloxetane, 3-tert-butyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, ( 3-ethyl-3-o Cetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [ 1- (3-ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3 -Oxetanylmethyl) ete Dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromo Phenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromo Phenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3 − Ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether Etc. More preferably (in parentheses are trade names or developed product names, manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (Aron oxetane OXT-212 (EHOX)), 3-ethyl-3- (Cyclohexyloxymethyl) oxetane (CHOX), 3-ethyl-3- (dodecyloxymethyl) oxetane (OXR-12), 3-ethyl-3- (octadecyloxymethyl) oxetane (OXR-18), 3- Examples include ethyl-3- (phenoxymethyl) oxetane (Aron oxetane OXT-211 (POX)), 3-ethyl-3-hydroxymethyloxetane (OXA), and the like. These can be used alone or in combination of two or more.
オキセタン環を２個有するもの、オキセタン環を３個有するも、およびオキセタン環を４個以上有するものとしては、カーボネートビスオキセタン、アジペートビスオキセタン、テレフタレートビスオキセタン、シクロヘキサンジカルボン酸ビスオキセタン、ビス（３−エチル−３−メチルオキシ）ブタン、３，７−ビス（３−オキセタニル）−５−オキサ−ノナン、３，３’−（１，３−（２−メチレニル）プロパンジイルビス（オキシメチレン））ビス−（３−エチルオキセタン）、１，４−ビス〔（３−エチル−３−オキセタニルメトキシ）メチル〕ベンゼン、１，２−ビス［（３−エチル−３−オキセタニルメトキシ）メチル］エタン、１，３−ビス［（３−エチル−３−オキセタニルメトキシ）メチル］プロパン、エチレングリコールビス（３−エチル−３−オキセタニルメチル）エーテル、ジシクロペンテニルビス（３−エチル−３−オキセタニルメチル）エーテル、トリエチレングリコールビス（３−エチル−３−オキセタニルメチル）エーテル、テトラエチレングリコールビス（３−エチル−３−オキセタニルメチル）エーテル、トリシクロデカンジイルジメチレン（３−エチル−３−オキセタニルメチル）エーテル、トリメチロールプロパントリス（３−エチル−３−オキセタニルメチル）エーテル、１，４−ビス（３−エチル−３−オキセタニルメトキシ）ブタン、１，６−ビス（３−エチル−３−オキセタニルメトキシ）ヘキサン、ペンタエリスリトールトリス（３−エチル−３−オキセタニルメチル）エーテル、ペンタエリスリトールテトラキス（３−エチル−３−オキセタニルメチル）エーテル、ポリエチレングリコールビス（３−エチル−３−オキセタニルメチル）エーテル、ジペンタエリスリトールヘキサキス（３−エチル−３−オキセタニルメチル）エーテル、ジペンタエリスリトールペンタキス（３−エチル−３−オキセタニルメチル）エーテル、ジペンタエリスリトールテトラキス（３−エチル−３−オキセタニルメチル）エーテル、カプロラクトン変性ジペンタエリスリトールヘキサキス（３−エチル−３−オキセタニルメチル）エーテル、カプロラクトン変性ジペンタエリスリトールペンタキス（３−エチル−３−オキセタニルメチル）エーテル、ジトリメチロールプロパンテトラキス（３−エチル−３−オキセタニルメチル）エーテル、ＥＯ変性ビスフェノールＡビス（３−エチル−３−オキセタニルメチル）エーテル、ＰＯ変性ビスフェノールＡビス（３−エチル−３−オキセタニルメチル）エーテル、ＥＯ変性水添ビスフェノールＡビス（３−エチル−３−オキセタニルメチル）エーテル、ＰＯ変性水添ビスフェノールＡビス（３−エチル−３−オキセタニルメチル）エーテル、ＥＯ変性ビスフェノールＦ（３−エチル−３−オキセタニルメチル）エーテルなどを例示することができ、これらは１種単独あるいは２種以上を組み合わせて用いることができる。 Those having two oxetane rings, three oxetane rings, and those having four or more oxetane rings include carbonate bisoxetane, adipate bisoxetane, terephthalate bisoxetane, bisoxetane cyclohexanedicarboxylate, bis (3- Ethyl-3-methyloxy) butane, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis -(3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1, 3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethyleneglycol Rubis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl-3-oxetanylmethyl) ether, tetraethyleneglycolbis ( 3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3- D Ru-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl) -3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3- Til-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether and the like can be exemplified, and these are used singly or in combination of two or more. be able to.
更に好ましくは（カッコ内は商品名又は開発品名、東亞合成製）、１，４−ビス｛［（３−エチル−３−オキセタニル）メトキシ］メチル｝ベンゼン（アロンオキセタンＯＸＴ−１２１（ＸＤＯ））、ジ［１−エチル（３−オキセタニル）］メチルエーテル（アロンオキセタンＯＸＴ−２２１（ＤＯＸ））、オキセタニルシルセスキオキサン（ＯＸ−ＳＱ）、フェノールノボラックオキセタン（ＰＮＯＸ−１００９）、ノルボルナンジメタノールと３−エチル−３−クロロメチルオキセタン（以後ＯＸＣと略す）のエーテル化物（ＮＤＭＯＸ）、トリメチロールプロパンとＯＸＣのエーテル化物（ＴＭＰＯＸ）、ハイドロキノンとＯＸＣのエーテル化物（ＨＱＯＸ）、レゾルシノールとＯＸＣのエーテル化物（ＲＳＯＸ）、２，２’−ビフェノールとＯＸＣのエーテル化物（２，２’−ＢＰＯＸ）、４，４’−ビフェノールとＯＸＣのエーテル化物（４，４’−ＢＰＯＸ）、ビスフェノールＦとＯＸＣのエーテル化物（ＢｉｓＦＯＸ）、トリシクロデカンジメタノールとＯＸＣのエーテル化物、ＯＸＡとシリコンによるアルコキサイド（ＯＸ−ＳＣ）などが挙げられる。 More preferably (in parentheses are trade names or developed product names, manufactured by Toagosei Co., Ltd.), 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene (Aron oxetane OXT-121 (XDO)), Di [1-ethyl (3-oxetanyl)] methyl ether (Aron oxetane OXT-221 (DOX)), oxetanylsilsesquioxane (OX-SQ), phenol novolac oxetane (PNOX-1009), norbornane dimethanol and 3- Etherified product of ethyl-3-chloromethyloxetane (hereinafter abbreviated as OXC) (NDMOX), etherified product of trimethylolpropane and OXC (TMPOX), etherified product of hydroquinone and OXC (HQOX), etherified product of resorcinol and OXC (RSOX) ), 2,2'-Bife Ether and OXC (2,2'-BPOX), 4,4'-biphenol and OXC (4,4'-BPOX), bisphenol F and OXC etherified (BisFOX), tricyclode Examples include etherified products of candimethanol and OXC, and alkoxide (OX-SC) using OXA and silicon.
本発明の多分岐マクロモノマーは、多分岐構造であり、一般の線状高分子と比較して、優れた特性が期待できる。特に本発明の多分岐マクロモノマーは、各種溶媒に対する溶解性に優れる特徴がある。また、本発明で得られる多分岐マクロモノマーは、側鎖に一級の水酸基を有することから、各種機能を有する官能基を導入することができることから、機能の発現を考慮した分子設計が可能となる。例えば、光ラジカル重合基としてのメタクロイル基、アルカリ現像性基としてのカルボキシル基を導入することにより、アルカリ現像可能なネガ型感光性樹脂として使用することができる。 The multibranched macromonomer of the present invention has a multibranched structure and can be expected to have superior characteristics as compared with general linear polymers. In particular, the multibranched macromonomer of the present invention is characterized by excellent solubility in various solvents. In addition, since the multibranched macromonomer obtained in the present invention has a primary hydroxyl group in the side chain, a functional group having various functions can be introduced, so that a molecular design considering the expression of the function is possible. . For example, by introducing a methacryloyl group as a radical photopolymerizable group and a carboxyl group as an alkali developable group, it can be used as a negative photosensitive resin capable of alkali development.
○実施態様
式（１）をアニオン開環重合して得られる１個のオキセタニル基を有する多分岐ポリエーテルポリオールを単独で重合させることを特徴とする多分岐マクロモノマーの製造方法。
式（１）をアニオン開環重合して得られる１個のオキセタニル基を有する多分岐ポリエーテルポリオールと、オキセタン化合物とをカチオン重合することを特徴とする多分岐マクロモノマーの製造方法。
Embodiment A method for producing a multibranched macromonomer characterized by polymerizing a multibranched polyether polyol having one oxetanyl group obtained by anionic ring-opening polymerization of formula (1) alone.
Method for producing a multibranched macromonomer, wherein the hyperbranched polyether polyol having one oxetanyl group derived equation (1) by anionic ring-opening polymerization, that cationically polymerizing the oxetane compound.
＜実施例＞
実施例を述べて本発明をさらに詳しく説明するが、本発明はこれらの実施例によって限定されるものではない。なお、数平均分子量をＭｎ、質量平均分子量をＭｗ、分子量分布をＭｗ／Ｍｎ、重合度をＤ．Ｐ．、エステル化率をＤ．Ｅ．、反応率をＤ．Ｒ．、分岐度をＤ．Ｂ．、赤外線スペクトルをＩＲ、核磁気共鳴をＮＭＲ、ゲル浸透クロマトグラフィーをＧＰＣと略す。
<Example>
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The number average molecular weight is Mn, the mass average molecular weight is Mw, the molecular weight distribution is Mw / Mn, and the degree of polymerization is D.P. P. , The esterification rate E. , The reaction rate R. , The degree of branching B. IR spectrum is abbreviated as IR, nuclear magnetic resonance as NMR, and gel permeation chromatography as GPC.
＜合成例１＞
○３，３−ビス（ヒドロキシメチル）オキセタン（ＢＨＯ）の合成
３００ｍＬのナス型フラスコに、ペンタエリスリトールを０．３７ｍｏｌ、ジエチルカーボネートを０．５ｍｏｌ、および炭酸カリウムを３ｍｍｏｌ入れ、１１０℃で１２時間撹拌した後、更に室温下で１２時間撹拌した。その後、反応溶液中から副生成物であるエタノールと未反応のジエチルカーボネートとを常圧蒸留にて除去した。そして、粗生成物を減圧蒸留して精製し無色透明固体の３，３−ビス（ヒドロキシメチル）オキセタン（ＢＨＯ）を得た。
収量 １８ｇ（４２％）
沸点 １４７℃（１０７Ｐａ，文献値：１４８−１６０℃（１ｍｍＨｇ））
・ＩＲ（ｆｉｌｍ，ｃｍ-1）：３３１４（ＯＨ）、１１０９，１０５３（Ｃ−Ｏ−Ｃ ｅｔｈｅｒ）、９８３（Ｃ−Ｏ−Ｃ ｏｘｅｔａｎｅ ｒｉｎｇ）
・1Ｈ−ＮＭＲ（５００ＭＨｚ，ＤＭＳＯ−ｄ6，ＴＭＳ）δｐｐｍ：
３．５５（ｄ，４．０Ｈ，Ｊ＝５．４Ｈｚ）、４．２７（Ｓ，４．０Ｈ）、４．７５（ｔ，２．０Ｈ，Ｊ＝５．４Ｈｚ）
・13Ｃ−ＮＭＲ（１２５ＭＨｚ，ＤＭＳＯ−ｄ6，ＴＭＳ）δｐｐｍ：
４４．９（Ｃ）、６２．０（ＣＨ2）、７４．０（ＣＨ2）
<Synthesis Example 1>
Synthesis of 3,3-bis (hydroxymethyl) oxetane (BHO) In a 300 mL eggplant-shaped flask, 0.37 mol of pentaerythritol, 0.5 mol of diethyl carbonate, and 3 mmol of potassium carbonate were added and stirred at 110 ° C. for 12 hours. Then, the mixture was further stirred at room temperature for 12 hours. Thereafter, ethanol as a by-product and unreacted diethyl carbonate were removed from the reaction solution by atmospheric distillation. The crude product was purified by distillation under reduced pressure to obtain 3,3-bis (hydroxymethyl) oxetane (BHO) as a colorless and transparent solid.
Yield 18g (42%)
Boiling point 147 ° C. (107 Pa, literature value: 148-160 ° C. (1 mmHg))
IR (film, cm −1 ): 3314 (OH), 1109, 1053 (C—O—C ether), 983 (C—O—C oxetane ring)
1 H-NMR (500 MHz, DMSO-d 6 , TMS) δ ppm:
3.55 (d, 4.0H, J = 5.4 Hz), 4.27 (S, 4.0H), 4.75 (t, 2.0H, J = 5.4 Hz)
· 13 C-NMR (125MHz, DMSO-d 6, TMS) δppm:
44.9 (C), 62.0 (CH 2 ), 74.0 (CH 2 )
○ＢＨＯのアニオン開環重合（Ｐｏｌｙ（ＢＨＯ））：反応温度の検討
摺りつき試験管に、ＢＨＯを３ｍｍｏｌ、Ｐｏｔａｓｓｉｕｍ ｔｅｒｔ−ｂｕｔｏｘｉｄｅ（ｔ−ＢｕＯＫ）を１０ｍｏｌ％、１８−Ｃｒｏｗｎ−６（１８−Ｃ−６）を１０ｍｏｌ％、およびＮ−メチル−２−ピロリドン（ＮＭＰ）を０．６ｍＬ入れ、１２０℃で２４時間反応を行った。反応終了後、反応溶液を大量のメタノール中に入れ、沈殿した固体をろ過により回収した。得られた固体を６０℃で減圧乾燥して褐色粉末を得た。なお、得られた褐色粉末が種々の有機溶媒に不溶であることからアセチル化を行った（Ｐｏｌｙ（ＢＨＯ−Ａｃ））。
２０ｍＬ型ナスフラスコに、上記で得られたものを０．２ｇ、無水酢酸を３．２ｍＬ、およびピリジンを１．０ｍＬ入れ、３時間還流した。反応後、反応溶液をクロロホルムで希釈し、希塩酸と蒸留水とで洗浄を行い、有機層を無水硫酸マグネシウムで乾燥させた。乾燥剤をろ別後、溶媒を減圧留去することにより、褐色粘性液体を得た。
Ｐｏｌｙ（ＢＨＯ）を得るための反応温度が１３０℃、１４０℃、１６０℃、および１８０℃のものについても同様にアセチル化を行った。
アセチル化したものについて、収率（％）、分子量、分子量分布（Ｍｗ／Ｍｎ）および分岐度（Ｄ．Ｂ．）を測定した結果を表１に示した。なお、分岐度はオキセタン環の３位の４級炭素に起因する13Ｃ−ＮＭＲのシグナルの積分値から、下記に示す式により算出した（Ｙ．Ｃｈｅｎ，Ｍ．Ｂｅｄｎａｒｅｋ，Ｐ．Ｋｕｂｉｓａ，Ｓ．Ｐｅｎｃｚｅｋ，Ｊ．Ｐｏｌｙｍ．Ｃｈｅｍ．Ｐａｒｔ Ａ：Ｐｏｌｙｍ．Ｃｈｅｍ．，４０，１９９１（２００２））。
Ｔａｒｍｉｎａｌ：４１．６ｐｐｍ
Ｌｉｎｅａｒ（Ｌ）：４２．６ｐｐｍ
Ｓｅｍｉ−Ｄｅｎｄｒｉｔｉｃ（ＳＤ）：４３．７ｐｐｍ
Ｄｅｎｄｒｉｔｉｃ（Ｄ）：シグナル未検出
Ｄ．Ｂ．＝（２Ｄ＋ＳＤ）／（２／３（３Ｄ＋２ＳＤ＋Ｌ））
○ Anionic ring-opening polymerization of BHO (Poly (BHO)): Examination of reaction temperature In a rubbing test tube, 3 mmol of BHO, 10 wt% of potassium tert-butoxide (t-BuOK), 18-Crown-6 (18-C) -6) was added at 10 mol% and N-methyl-2-pyrrolidone (NMP) at 0.6 mL, and the reaction was carried out at 120 ° C for 24 hours. After completion of the reaction, the reaction solution was placed in a large amount of methanol, and the precipitated solid was collected by filtration. The obtained solid was dried under reduced pressure at 60 ° C. to obtain a brown powder. In addition, since the obtained brown powder was insoluble in various organic solvents, acetylation was performed (Poly (BHO-Ac)).
A 20 mL eggplant-shaped flask was charged with 0.2 g of the product obtained above, 3.2 mL of acetic anhydride, and 1.0 mL of pyridine, and refluxed for 3 hours. After the reaction, the reaction solution was diluted with chloroform, washed with dilute hydrochloric acid and distilled water, and the organic layer was dried over anhydrous magnesium sulfate. After filtering off the desiccant, the solvent was distilled off under reduced pressure to obtain a brown viscous liquid.
Acetylation was similarly carried out for those having reaction temperatures of 130 ° C., 140 ° C., 160 ° C., and 180 ° C. to obtain Poly (BHO).
Table 1 shows the results of measuring the yield (%), molecular weight, molecular weight distribution (Mw / Mn), and degree of branching (DB) of the acetylated product. The degree of branching was calculated from the integral value of 13 C-NMR signal due to the quaternary carbon at the 3-position of the oxetane ring by the following formula (Y. Chen, M. Bednarek, P. Kubisa, S. Penczek, J. Polym. Chem. Part A: Polym. Chem., 40, 1991 (2002)).
Terminal: 41.6ppm
Linear (L): 42.6 ppm
Semi-Dendric (SD): 43.7 ppm
Dendritic (D): no signal detected. B. = (2D + SD) / (2/3 (3D + 2SD + L))
反応温度が高くなるに従い収率および分子量は増加する傾向を示した。また、Ｄ．Ｂ．は分子量が増加するに従い高い値を示した。また、反応温度１２０℃で得られたもの（Ｒｕｎ １）及び反応温度１３０℃で得られたもの（Ｒｕｎ ２）についてＮＭＲを用いて分子量Ｍｎを算出したところ、Ｒｕｎ １では、ＧＰＣで測定したＭｎとＮＭＲで算出したＭｎの値（１２００）とほぼ同じであった。しかし、Ｒｕｎ １よりＤ．Ｂ．が大きいＲｕｎ ２では、ＮＭＲで算出したＭｎの値（３０００）の方がＧＰＣで測定したＭｎの値より高い値を示した。これは、分岐度が高い方がよりコンパクトな構造をとっていることを示唆している。 The yield and molecular weight tended to increase as the reaction temperature increased. In addition, D.C. B. Showed higher values as the molecular weight increased. Moreover, when molecular weight Mn was calculated using NMR about what was obtained at reaction temperature 120 degreeC (Run 1) and what was obtained at reaction temperature 130 degreeC (Run 2), in Run 1, Mn measured by GPC was calculated. And Mn calculated by NMR (1200) were almost the same. However, from Run 1, D.C. B. In Run 2, which has a large value, the value of Mn calculated by NMR (3000) was higher than the value of Mn measured by GPC. This suggests that a higher degree of branching has a more compact structure.
Ｒｕｎ ２で得られたものについてＩＲ及びＮＭＲを測定した結果を下記に示す。
・ＩＲ（ｆｉｌｍ，ｃｍ-1）：１７４２（Ｃ＝Ｏ）、１２３２（Ｃ−Ｏ−Ｃ ｅｓｔｅｒ），１１０９，１０５３（Ｃ−Ｏ−Ｃ ｅｔｈｅｒ）、９８３（Ｃ−Ｏ−Ｃ ｏｘｅｔａｎｅ ｒｉｎｇ）
・1Ｈ−ＮＭＲ（５００ＭＨｚ，ＤＭＳＯ−ｄ6，ＴＭＳ）δｐｐｍ：
１．９９（ｓ，３．１Ｈ），３．２６−３．３３（ｍ，２．０Ｈ），３．９６−４．０３（ｍ，２．１Ｈ），４．２５（ｓ，０．１６Ｈ），４．４６（ＡＢ ｑｕａｒｔｅｔ，０．３４Ｈ）
・13Ｃ−ＮＭＲ（１２５ＭＨｚ，ＤＭＳＯ−ｄ6，ＴＭＳ）δｐｐｍ：
１９・７（ＣＨ3），４１．６−４３．７（Ｃ），６１．７−６２．２（ＣＨ2）６８．８−６９．３（ＣＨ2），７４．６（ＣＨ2）、１６９．５（Ｃ）
The results of IR and NMR measurements on the product obtained with Run 2 are shown below.
IR (film, cm −1 ): 1742 (C═O), 1232 (C—O—C ester), 1109, 1053 (C—O—C ether), 983 (C—O—C oxetane ring)
1 H-NMR (500 MHz, DMSO-d 6 , TMS) δ ppm:
1.99 (s, 3.1H), 3.26-3.33 (m, 2.0H), 3.96-4.03 (m, 2.1H), 4.25 (s, 0.16H) ), 4.46 (AB quartet, 0.34H)
· 13 C-NMR (125MHz, DMSO-d 6, TMS) δppm:
19 · 7 (CH 3), 41.6-43.7 (C), 61.7-62.2 (CH 2) 68.8-69.3 (CH 2), 74.6 (CH 2), 169.5 (C)
Ｒｕｎ ２で得られたものにおいて４．２５ｐｐｍ付近にＳｉｎｇｌｅｔ及び４．４６ｐｐｍ付近にＡＢ ｑｕａｒｔｅｔのシグナルを確認した。このことは、ＢＨＯの両方の水酸基から重合が開始したものと、ＢＨＯの片方の水酸基から重合が開始したものとを含んでいることを示している。
このようにして得られる多分岐ポリエーテルポリオールであるＰｏｌｙ（ＢＨＯ）は、各種官能基を簡単に付与できるものとして使用することができる。
In the product obtained with Run 2, a singlet signal was confirmed near 4.25 ppm and an AB quartet signal was observed near 4.46 ppm. This indicates that the polymerization started from both hydroxyl groups of BHO and the polymerization started from one hydroxyl group of BHO.
Poly (BHO), which is a multi-branched polyether polyol obtained in this way, can be used as one that can easily impart various functional groups.
○ＢＨＯのアニオン開環重合（Ｐｏｌｙ（ＢＨＯ））：反応時間の検討
ナス型フラスコにＢＨＯを３ｍｍｏｌ、ｔ−ＢｕＯＫを１０ｍｏｌ％、１８−Ｃ−６を１０ｍｏｌ％、およびＮＭＰを０．６ｍＬ入れ、反応温度１８０℃で６時間反応させた。反応終了後、反応溶液を大量のメタノール中に入れ、沈殿した固体をろ過により回収した。得られた固体を６０℃で減圧乾燥して褐色粉末（Ｐｏｌｙ（ＢＨＯ））を得た。その後、上記に記載した方法でアセチル化を行った。
１２時間、２４時間、４８時間、及び７２時間の反応時間のものについても同様に操作して、分子量などの測定を行った。この結果を表２に記載した。
○ Anionic ring-opening polymerization of BHO (Poly (BHO)): Examination of reaction time 3 mmol of BHO, 10 mol% of t-BuOK, 10 mol% of 18-C-6, and 0.6 mL of NMP were placed in an eggplant type flask. The reaction was carried out at a reaction temperature of 180 ° C. for 6 hours. After completion of the reaction, the reaction solution was placed in a large amount of methanol, and the precipitated solid was collected by filtration. The obtained solid was dried under reduced pressure at 60 ° C. to obtain a brown powder (Poly (BHO)). Thereafter, acetylation was performed by the method described above.
The molecular weight and the like were measured in the same manner for the reaction times of 12 hours, 24 hours, 48 hours, and 72 hours. The results are shown in Table 2.
反応時間を増加させることにより収率および分子量ともに増加する傾向を示した。
得られたポリマーの分岐度は、０．４２〜０．５５であり分子量の増加と共に分岐度が増加した。
このようにして得られる多分岐ポリエーテルポリオールであるＰｏｌｙ（ＢＨＯ）は、各種官能基を簡単に付与できるものとして使用することができる。
The yield and molecular weight tended to increase with increasing reaction time.
The degree of branching of the obtained polymer was 0.42 to 0.55, and the degree of branching increased with increasing molecular weight.
Poly (BHO), which is a multi-branched polyether polyol obtained in this way, can be used as one that can easily impart various functional groups.
○ＢＨＯのアニオン開環重合（Ｐｏｌｙ（ＢＨＯ））：モノマー濃度の検討
ＢＨＯを３ｍｍｏｌ、ｔ−ＢｕＯＫを１０ｍｏｌ％、１８−Ｃ−６を１０ｍｏｌ％、そしてＮＭＰを加えてＢＨＯ濃度を１ｍｏｌ／Ｌに調製し、１８０℃で２４時間反応を行った。反応終了後、反応溶液を大量のメタノールに入れ、沈殿した固体をろ過により回収した。得られた固体を６０℃で減圧乾燥して褐色粉末（Ｐｏｌｙ（ＢＨＯ））を得た。この褐色粉末は、上記に記載した方法を用いてアセチル化した（Ｐｏｌｙ（ＢＨＯ−Ａｃ））。
ＢＨＯ濃度を３ｍｏｌ／Ｌ及び５ｍｏｌ／Ｌ等で同様の操作を行った。この結果を表３に記載した。
○ Anionic ring-opening polymerization of BHO (Poly (BHO)): Examination of monomer concentration BHO 3 mmol, t-BuOK 10 mol%, 18-C-6 10 mol%, and NMP added to bring the BHO concentration to 1 mol / L Prepared and reacted at 180 ° C. for 24 hours. After completion of the reaction, the reaction solution was put in a large amount of methanol, and the precipitated solid was collected by filtration. The obtained solid was dried under reduced pressure at 60 ° C. to obtain a brown powder (Poly (BHO)). This brown powder was acetylated using the method described above (Poly (BHO-Ac)).
The same operation was performed with BHO concentrations of 3 mol / L and 5 mol / L. The results are shown in Table 3.
ＢＨＯ濃度が増加することにより重合は進行した。しかし、ｂｕｌｋの場合は分子量分布が広がる傾向を示したことから、溶媒を用いて重合反応を行った方が良い。
このようにして得られる多分岐ポリエーテルポリオールであるＰｏｌｙ（ＢＨＯ）は、各種官能基を簡単に付与できるものとして使用することができる。
Polymerization proceeded as the BHO concentration increased. However, in the case of bulk, since the molecular weight distribution tends to be widened, it is better to perform the polymerization reaction using a solvent.
Poly (BHO), which is a multi-branched polyether polyol obtained in this way, can be used as one that can easily impart various functional groups.
○Ｐｏｌｙ（ＢＨＯ）の重合
２０ｍＬナス型フラスコにＰｏｌｙ（ＢＨＯ）（Ｍｎ＝１５００，Ｍｗ／Ｍｎ＝１．３０）を３ｍｍｏｌ、ｔ−ＢｕＯＫを１０ｍｏｌ％、１８−Ｃ−６を１０ｍｏｌ％、およびＮＭＰを０．６ｍＬ入れ、１８０℃で２４時間反応を行った。反応終了後、反応溶液を大量のメタノール中に注ぎ固体を沈殿させた。ろ過により固体を回収し、室温で減圧乾燥させて褐色粉末を得た（収率９７％）。
Ｍｎ＝３０００
Ｍｗ／Ｍｎ＝１．６０
得られた褐色粉末についてＧＰＣを測定した結果、低分子量側のピークは減少し、高分子量側に新しくピークが出現した。このことは、ポリマー同士が反応していることを示している。このことは、Ｐｏｌｙ（ＢＨＯ）の末端にオキセタニル基が存在することを示している。
このようにして得られる多分岐マクロモノマーは、各種官能基を簡単に付与できるものとして使用することができる。
Polymerization of Poly (BHO) In a 20 mL eggplant type flask, 3 mmol of Poly (BHO) (Mn = 1500, Mw / Mn = 1.30), 10 mol% of t-BuOK, 10 mol% of 18-C-6, and NMP Was added and reacted at 180 ° C. for 24 hours. After completion of the reaction, the reaction solution was poured into a large amount of methanol to precipitate a solid. The solid was collected by filtration and dried under reduced pressure at room temperature to obtain a brown powder (yield 97%).
Mn = 3000
Mw / Mn = 1.60
As a result of GPC measurement of the obtained brown powder, the peak on the low molecular weight side decreased, and a new peak appeared on the high molecular weight side. This indicates that the polymers are reacting with each other. This indicates that an oxetanyl group is present at the end of Poly (BHO).
The multibranched macromonomer thus obtained can be used as one that can easily impart various functional groups.
○Ｐｏｌｙ（ＢＨＯ−Ａｃ）のカチオン開環重合による分岐ポリマー（Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ−Ａｃ）−ＥＰＯ］）の合成
摺り付き試験管にＤ．Ｂ．＝０．３０のＰｏｌｙ（ＢＨＯ−Ａｃ）を０．３ｍｍｏｌ、表４に記載の仕込み比で３−エチル−３−（フェノキシメチル）オキセタン（ＥＰＯ、東亞合成(株)製）、およびクロロホルムを入れ、０℃に冷却した。その後、開始剤として三フッ化ホウ素エチルエーテル錯化合物を１０ｍｏｌ％を加え、０℃で２４時問反応を行った。その後、少量のピリジンを加えて反応を停止させた後、クロロホルムで反応溶液を希釈し、希塩酸と蒸留水とで洗浄し、有機層を無水硫酸マグネシウムで乾燥させた。乾燥剤をろ別後、貧溶媒にＲｕｎ １ではｎ−ヘキサンを、Ｒｕｎ ２およびＲｕｎ ３ではメタノールを用いて再沈精製を行い、室温で減圧乾燥させることにより白色ポリマーを得た。結果を表４に示す。
O Synthesis of branched polymer (Poly [poly (BHO-Ac) -EPO]) by cationic ring-opening polymerization of Poly (BHO-Ac). B. = 0.30 Poly (BHO-Ac) 0.3 mmol, 3-ethyl-3- (phenoxymethyl) oxetane (EPO, manufactured by Toagosei Co., Ltd.) and chloroform were charged at the charging ratio shown in Table 4. And cooled to 0 ° C. Thereafter, 10 mol% of boron trifluoride ethyl ether complex compound was added as an initiator, and the reaction was carried out at 0 ° C. for 24 hours. Then, after a small amount of pyridine was added to stop the reaction, the reaction solution was diluted with chloroform, washed with dilute hydrochloric acid and distilled water, and the organic layer was dried over anhydrous magnesium sulfate. After the desiccant was filtered off, reprecipitation purification was performed using n-hexane for Run 1 and methanol for Run 2 and Run 3 as poor solvents, and dried under reduced pressure at room temperature to obtain a white polymer. The results are shown in Table 4.
Ｒｕｎ １では、分子量はほとんど変化しなかったが、Ｒｕｎ ２及びＲｕｎ ３では、分子量が増加した。
Ｒｕｎ １，Ｒｕｎ ２及びＲｕｎ ３で得られたものについてＧＰＣを測定した結果、Ｒｕｎ １のものは、反応前とほとんど変化が認められなかった。このことは、カチオン重合が進行しなかったことを示している。しかし、Ｒｕｎ ２及びＲｕｎ ３のものでは，ピークが高分子量側へとシフトした。これは，ＥＰＯユニットがスペーサーの働きをしてＰｏｌｙ（ＢＨＯ−Ａｃ）のオキセタニル基近傍の立体障害が緩和して重合したと考えられる。このことから、Ｐｏｌｙ（ＢＨＯ−Ａｃ）は、共重合を行うことにより、末端オキセタニル基がカチオン開環重合できると考えられる。しかし、Ｄ．Ｂ．が０．１５〜０．１７のもののＰｏｌｙ（ＥＨＯ−Ａｃ）が単独で重合すること、Ｄ．Ｂ．が０．３０のもののＰｏｌｙ（ＥＨＯ−Ａｃ）が単独で重合しないことは、立体障害が高いためと考えられる。
このようにして得られる多分岐マクロモノマーは、各種官能基を簡単に付与できるものとして使用することができる。
In Run 1, the molecular weight hardly changed, but in Run 2 and Run 3, the molecular weight increased.
As a result of measuring GPC for those obtained in Run 1, Run 2 and Run 3, the change in Run 1 was almost unchanged from that before the reaction. This indicates that cationic polymerization did not proceed. However, for Run 2 and Run 3, the peak shifted to higher molecular weight. This is considered that the EPO unit worked as a spacer, and the steric hindrance in the vicinity of the oxetanyl group of Poly (BHO-Ac) was relaxed and polymerized. From this, it is considered that Poly (BHO-Ac) can undergo cationic ring-opening polymerization of the terminal oxetanyl group by performing copolymerization. However, D.C. B. Poly (EHO-Ac) having an A of 0.15 to 0.17 is polymerized alone; B. The reason why Poly (EHO-Ac) having an A of 0.30 does not polymerize alone is considered to be because of high steric hindrance.
The multibranched macromonomer thus obtained can be used as one that can easily impart various functional groups.
○Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ）−ＥＰＯ］の合成
ナス型フラスコに、Ｐｏｌｙ−［ｐｏｌｙ（ＢＨＯ−Ａｃ）−ＥＰＯ］を６ｍｍｍｏｌ、水酸化カリウムを６ｍｍｏｌ秤とり、水／ＴＨＦ（１ｍＬ／４ｍＬ）に溶解させ、５０℃、４８時間反応させた。反応終了後、１Ｎ塩酸水溶液中に入れ酸析を行った。析出した固体をろ過により回収し、ＴＨＦに溶解させ無水硫酸マグネシウムで乾燥させた。乾燥後、乾燥剤をろ別し、ｎ−ヘキサシを用いて再沈精製を行い、室温で減圧乾燥させることにより白色固体を得た。ＭｎおよびＭｗ／Ｍｎは、ＧＰＣ（ＤＭＦ）により測定した。
反応率（Ｄ．Ｒ．）＝１００％
収量１．５３ｇ（８０％）
Ｍｎ＝１４４００、Ｍｗ／Ｍｎ＝１．３１
・ＩＲ（ｆｉｌｍ，ｃｍ-1）：３２９１、１５９９、１４９７、１２４４、１１０５、１０３６．
・1Ｈ ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ3，ＴＭＳ）δｐｐｍ：０．６８−０．７９（ｍ，３Ｈ）、１．３５−１．４５（ｍ，２Ｈ）、３．１１−３．７４（ｍ、１２．２Ｈ）、３．８１−３．９７（ｍ，２Ｈ）、４．７８（ｂｒｓ，３Ｈ）、６．６８−６．８９（ｍ，３Ｈ）、６．９１−７．３２（ｍ，２Ｈ）．
○ Synthesis of Poly [poly (BHO) -EPO] In an eggplant type flask, 6-mmol of Poly- [poly (BHO-Ac) -EPO] and 6 mmol of potassium hydroxide were weighed and dissolved in water / THF (1 mL / 4 mL). And allowed to react at 50 ° C. for 48 hours. After completion of the reaction, acid precipitation was carried out in a 1N hydrochloric acid aqueous solution. The precipitated solid was collected by filtration, dissolved in THF, and dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off, reprecipitation purification was performed using n-hexaci and dried at room temperature under reduced pressure to obtain a white solid. Mn and Mw / Mn were measured by GPC (DMF).
Reaction rate (DR) = 100%
Yield 1.53 g (80%)
Mn = 14400, Mw / Mn = 1.31
IR (film, cm −1 ): 3291, 1599, 1497, 1244, 1105, 1036.
1 H NMR (600 MHz, CDCl 3 , TMS) δ ppm: 0.68-0.79 (m, 3H), 1.35-1.45 (m, 2H), 3.11-3.74 (m, 12.2H), 3.81-3.97 (m, 2H), 4.78 (brs, 3H), 6.68-6.89 (m, 3H), 6.91-7.32 (m, 2H).
○Ｐｏｌｙ（ＢＨＯ）へのメタクリロイル基の導入（Ｐｏｌｙ（ＢＨＯ−ＭＡ））
ナス型フラスコにＰｏｌｙ（ＢＨＯ）を１．６ｍｍｏｌ、メタクリル酸無水物を１６ｍｍｏｌ、ピリジンを１．０ｍＬ、および重合禁止剤としてヒドロキノンを少量入れ、９０℃で３時間撹拌した。反応終了後、反応溶液をクロロホルムで希釈し、希塩酸および蒸留水で洗浄後、有機層を無水硫酸マグネシウムで乾燥した。乾燥剤をろ別後、良溶媒としてクロロホルム、貧溶媒としてｎ−ヘキサンを用いて再沈精製を行うことにより褐色粘性ポリマーを得た。
エステル化率（Ｄ．Ｅ．）＝８３％
収量：０．１４ｇ（３４％）
・ＩＲ（ｆｉｌｍ，ｃｍ-1）：１７４２（Ｃ＝Ｏ），１２３２（Ｃ−Ｏ−Ｃ ｅｓｔｅｒ），１１０９，１０５３（Ｃ−Ｏ−Ｃ ｅｔｈｅｒ），９８３（Ｃ−Ｏ−Ｃ ｏｘｅｔａｎｅ ｒｉｎｇ）．
・1Ｈ−ＮＭＲ（５００ＭＨｚ，ＤＭＳＯ−ｄ6，ＴＭＳ）δｐｐｍ：１．９（Ｓ，４．９Ｈ），３．１６−３．６４（ｍ，４．０Ｈ）、４．００−４．４１（ｍ，４．０Ｈ）、５．５５（ｓ，１．６Ｈ）、６．０５（ｓ，１．６Ｈ）．
Ｐｏｌｙ（ＢＨＯ）はメタクリル酸無水物と反応してメタクリル酸エステル体とすることができた。
○ Introduction of methacryloyl group into Poly (BHO) (Poly (BHO-MA))
An eggplant-shaped flask was charged with 1.6 mmol of Poly (BHO), 16 mmol of methacrylic anhydride, 1.0 mL of pyridine, and a small amount of hydroquinone as a polymerization inhibitor, and stirred at 90 ° C. for 3 hours. After completion of the reaction, the reaction solution was diluted with chloroform, washed with dilute hydrochloric acid and distilled water, and the organic layer was dried over anhydrous magnesium sulfate. After filtering the desiccant, a brown viscous polymer was obtained by reprecipitation purification using chloroform as a good solvent and n-hexane as a poor solvent.
Esterification rate (DE) = 83%
Yield: 0.14 g (34%)
IR (film, cm −1 ): 1742 (C═O), 1232 (C—O—C ester), 1109, 1053 (C—O—C ether), 983 (C—O—C oxetane ring).
1 H-NMR (500 MHz, DMSO-d 6 , TMS) δ ppm: 1.9 (S, 4.9H), 3.16-3.64 (m, 4.0H), 4.00-4.41 (M, 4.0H), 5.55 (s, 1.6H), 6.05 (s, 1.6H).
Poly (BHO) was able to react with methacrylic anhydride to form a methacrylic ester.
上記に記載したＰｏｌｙ（ＢＨＯ）の重合して得られる多分岐マクロモノマーまたはＰｏｌｙ（ＢＨＯ）と他のオキセタン化合物とを重合して得られる多分岐マクロモノマーにおいて、Ｐｏｌｙ（ＢＨＯ）の代わりにＰｏｌｙ（ＥＨＯ）を用いても同様の多分岐マクロモノマーを得ることができる。 In the above-described multi-branched macromonomer obtained by polymerizing Poly (BHO) or the polybranched macromonomer obtained by polymerizing Poly (BHO) and another oxetane compound, instead of Poly (BHO), Poly (BHO) A similar multi-branched macromonomer can be obtained using EHO).
○Ｐｏｌｙ（ＢＨＯ）へのメタクリロイル基の導入（Ｐｏｌｙ（ＢＨＯ−ＭＡ））
ナス型フラスコにＰｏｌｙ（ＢＨＯ）を１．６ｍｍｏｌ、メタクリル酸無水物を１６ｍｍｏｌ、ピリジンを１ｍＬ、および重合禁止剤としてヒドロキノンを少量入れ、９０℃で４８時間撹拌した。反応終了後、反応溶液をクロロホルムで希釈し、希塩酸および蒸留水で洗浄後、有機層を無水硫酸マグネシウムで乾燥した。乾燥剤をろ別後、良溶媒としてクロロホルム、貧溶媒としてｎ−ヘキサンを用いて再沈精製を行うことにより褐色粘性ポリマーを得た。
この褐色粘性ポリマーの構造確認はＩＲおよび1Ｈ ＮＭＲにより行った。ＩＲスペクトルにおいて３３１１ｃｍ-1の水酸基に起因するピークが消失し、新たに１７４２ｃｍ-1にメタクリロイル基のνＣ＝Ｏ、１６３７ｃｍ-1にメタクリロイル基のνＣ＝Ｃの伸縮振動に起因するピークを認めた。また、1Ｈ ＮＭＲにおいて、１．９０ｐｐｍにメタクリロイル基のメチルプロトン、４．００〜４．４１ｐｐｍ付近にメタクリロイル基に隣接するメチレンプロトンおよび５．５５ｐｐｍと６．０２ｐｐｍにメタクリロイル基のビニルプロトンに起因するシグナルを認めた。更に、エステル化率を主鎖のメチレンプロトンの積分値を基準とし、メタクリロイル基のビニルプロトンの積分値から算出したところ、１００％であった。以上のことから、褐色粘性ポリマーはメタクリロイル基を１００％有するＰｏｌｙ（ＢＨＯ−ＭＡ）と決定した。
エステル化率（Ｄ．Ｅ．）＝１００％
収量：０．３７ｇ（８７％）
○ Introduction of methacryloyl group into Poly (BHO) (Poly (BHO-MA))
An eggplant-shaped flask was charged with 1.6 mmol of Poly (BHO), 16 mmol of methacrylic anhydride, 1 mL of pyridine, and a small amount of hydroquinone as a polymerization inhibitor, and stirred at 90 ° C. for 48 hours. After completion of the reaction, the reaction solution was diluted with chloroform, washed with dilute hydrochloric acid and distilled water, and the organic layer was dried over anhydrous magnesium sulfate. After filtering the desiccant, a brown viscous polymer was obtained by reprecipitation purification using chloroform as a good solvent and n-hexane as a poor solvent.
The structure of this brown viscous polymer was confirmed by IR and 1 H NMR. Peak due to the hydroxyl group of 3311cm -1 disappeared in the IR spectrum showed newly νC = O of methacryloyl group at 1742 cm -1, a peak caused by stretching vibration of νC = C methacryloyl group 1637 cm -1. Further, in 1 H NMR, it is caused by a methyl proton of a methacryloyl group at 1.90 ppm, a methylene proton adjacent to the methacryloyl group at around 4.00 to 4.41 ppm, and a vinyl proton of a methacryloyl group at 5.55 ppm and 6.02 ppm. A signal was observed. Furthermore, when the esterification rate was calculated from the integral value of the vinyl proton of the methacryloyl group based on the integral value of the methylene proton of the main chain, it was 100%. From the above, the brown viscous polymer was determined to be Poly (BHO-MA) having 100% methacryloyl group.
Esterification rate (DE) = 100%
Yield: 0.37 g (87%)
○Ｐｏｌｙ（ＢＨＯ−ＭＡ）の光架橋
Ｐｏｌｙ（ＢＨＯ−ＭＡ）を０．２０ｇ（６０ｗｔ％）、光ラジカル開始剤としてＩｒｇａｃｕｒｅ ９０７（Ｉｒｇ９０７）を０．００３２ｇ、反応希釈剤としてヒドロキシメチルメタクリレート（ＨＥＭＡ）を０．１３ｇ（４０ｗｔ％）、増感剤として２−エチルアントラキノン（２Ｅ−ＡＱ）を０．００３ｇ（１ｗｔ％）を秤取り、ＴＨＦを少量加え、均一になるまで混合した。この混合物をＫＢｒ板上に塗布し、２８５０ｃｍ-1存近の吸収度を約１とするようにフィルムを作製した。光反応における光源は、２５０Ｗ高圧水銀灯を用い、照度は２５４ｎｍで９ｍＷ／ｃｍ2とした。
紫外線照射を行なうとＩＲスペクトルにおけるメタクリロイル基のνＣ＝Ｃに起因する１６３７ｃｍ-1の吸収が減少し、照射５分後にはメタクリロイル基のνＣ＝Ｃの転化率（転化率は１６３７ｃｍ-1のメタクリロイル基に起因する吸収の減衰から算出した）は約３９％に達した。得られた硬化フィルムは、ＴＨＦに不溶となったことから、光ラジカル重合が速やかに進行し、架橋構造を形成したことが明らかとなった。
○ Photocrosslinking of Poly (BHO-MA) 0.20 g (60 wt%) of Poly (BHO-MA), 0.0032 g of Irgacure 907 (Irg907) as a photo radical initiator, and hydroxymethyl methacrylate (HEMA) as a reaction diluent 0.13 g (40 wt%) and 0.003 g (1 wt%) of 2-ethylanthraquinone (2E-AQ) as a sensitizer were weighed and a small amount of THF was added and mixed until uniform. This mixture was applied onto a KBr plate, and a film was prepared so that the absorbance near 2850 cm -1 was about 1. The light source in the photoreaction was a 250 W high pressure mercury lamp, and the illuminance was 254 nm and 9 mW / cm 2 .
When UV irradiation is performed, the absorption of 1637 cm −1 due to νC═C of the methacryloyl group in the IR spectrum decreases, and the conversion rate of νC═C of the methacryloyl group after 5 minutes of irradiation (the conversion rate is 1637 cm −1 methacryloyl group) (Calculated from the absorption attenuation due to) reached about 39%. Since the obtained cured film became insoluble in THF, it was revealed that photoradical polymerization proceeded rapidly and a crosslinked structure was formed.
○Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ）−ＥＰＯ］へのメタクリロイル基の導入（Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ−ＭＡ）−ＥＰＯ］）
Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ）−ＥＰＯ］を０．２ｇ、メタクリル酸無水物を１６ｍｍｏｌ、ピリジンを１ｍＬ、および重合禁止剤としてヒドロキノンを少量入れ、９０℃で５時間撹拌した。反応終了後、反応溶液をクロロホルムで希釈し、希塩酸および蒸留水で洗浄後、有機層を無水硫酸マグネシウムで乾燥した。乾燥剤をろ別後、良溶媒としてクロロホルム、貧溶媒としてメタノールを用いて再沈精製を行うことにより白色粘性ポリマーを得た。
この白色粘性ポリマーの構造確認は、ＩＲおよび1Ｈ ＮＭＲにより行った。即ち、３２９１ｃｍ-1の水酸基に起因するピークが消失し、新たに１７２３ｃｍ-1にメタクリロイル基のνＣ＝Ｏ、１６３７ｃｍ-1にメタクリロイル基のνＣ＝Ｃの伸縮振動に起因するピークが認められた。また、1Ｈ ＮＭＲにおいて、１．９０ｐｐｍにメタクリロイル基のメチルプロトン、４．００〜４．４１ｐｐｍ付近にメタクリロイル基に隣接するメチレンプロトンおよび５．５５ｐｐｍと６．０２ｐｐｍにメタクリロイル基のビニルプロトンに起因するシグナルが認められた。更に、エステル化率をＥＰＯユニットの芳香族プロトンの積分値を基準としてメタクリロイル基のビニルプロトンの積分値から算出したところ、１００％であった。以上のことから、白色粘性ポリマーはメタクリロイル基を１００％有するＰｏｌｙ［ｐｏｌｙ（ＢＨＯ−ＭＡ）−ＥＰＯ］と決定した。
エステル化率（Ｄ．Ｅ．）＝１００％
収量：０．３７ｇ（８７％）
・ＩＲ（ｆｉｌｍ，ｃｍ-1）：１７２３，１６３７，１５９９，１４９７，１２４４，１１０７，１０３７．
・1Ｈ−ＮＭＲ（５００ＭＨｚ，ＤＭＳＯ−ｄ6，ＴＭＳ）δｐｐｍ：１．９０（ｓ，６Ｈ），３．１６−３．６４（ｍ，４Ｈ），４．００−４．４１（ｍ，４Ｈ），５．５５（ｓ，２Ｈ），６．０５（ｓ，２Ｈ）．
-Introduction of methacryloyl group into Poly [poly (BHO) -EPO] (Poly [poly (BHO-MA) -EPO])
0.2 g of Poly [poly (BHO) -EPO], 16 mmol of methacrylic anhydride, 1 mL of pyridine, and a small amount of hydroquinone as a polymerization inhibitor were added and stirred at 90 ° C. for 5 hours. After completion of the reaction, the reaction solution was diluted with chloroform, washed with dilute hydrochloric acid and distilled water, and the organic layer was dried over anhydrous magnesium sulfate. After filtering off the desiccant, reprecipitation purification was performed using chloroform as a good solvent and methanol as a poor solvent to obtain a white viscous polymer.
The structure of this white viscous polymer was confirmed by IR and 1 H NMR. That is, the peak attributed to the hydroxyl group at 3291 cm −1 disappeared, and a new peak due to the stretching vibration of νC═O of the methacryloyl group at 1723 cm −1 and νC═C of the methacryloyl group at 1637 cm −1 was newly observed. Further, in 1 H NMR, it is caused by a methyl proton of a methacryloyl group at 1.90 ppm, a methylene proton adjacent to the methacryloyl group at around 4.00 to 4.41 ppm, and a vinyl proton of a methacryloyl group at 5.55 ppm and 6.02 ppm. A signal was observed. Furthermore, when the esterification rate was calculated from the integral value of the vinyl proton of the methacryloyl group based on the integral value of the aromatic proton of the EPO unit, it was 100%. From the above, the white viscous polymer was determined as Poly [poly (BHO-MA) -EPO] having 100% methacryloyl group.
Esterification rate (DE) = 100%
Yield: 0.37 g (87%)
IR (film, cm −1 ): 1723, 1637, 1599, 1497, 1244, 1107, 1037.
1 H-NMR (500 MHz, DMSO-d 6 , TMS) δ ppm: 1.90 (s, 6H), 3.16-3.64 (m, 4H), 4.00-4.41 (m, 4H) ), 5.55 (s, 2H), 6.05 (s, 2H).
○Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ−ＭＡ）−ＥＰＯ］の光架橋
Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ−ＭＡ）−ＥＰＯ］を０．２０ｇ（６０ｗｔ％）、光ラジカル開始剤としてＩｒｇ９０７を０．００３２ｇ、反応希釈剤としてＨＥＭＡを０．１３ｇ（４０ｗｔ％）、増感剤として２Ｅ−ＡＱを０．００３ｇ（１ｗｔ％）を秤取り、均一になるまで混合してサンプルを調製した。その後の操作は、実施例８と同様に行なった。
この結果、ＩＲスペクトルにおけるメタクリロイル基のνＣ＝Ｃに起因する１６３７ｃｍ-1の吸収が減少し、光照射５分後のメタクリロイル基のνＣ＝Ｃの転化率は約５４％であった。また、Ｐｏｌｙ（ＢＨＯ−ＭＡ）の場合と比べると、立ち上がりが遅く、重合後期もゆるやかに転化率が上昇する傾向を示した。なお、立ち上がりが遅いのは、単位重量あたりのメタクリロイル基の含有量が、Ｐｏｌｙ（ＢＨＯ−ＭＡ）よりもＰｏｌｙ［ｐｏｌｙ（ＢＨＯ−ＭＡ）−ＥＰＯ］の方が少ないため、Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ−ＭＡ）−ＥＰＯ］のフィルム内のメタクリロイル基同士の接触率が低下したものと考えられる。また重合後期も緩やかに転化率が上昇するのは、架橋構造が形成しても、架橋に関与しないＥＰＯユニット近傍でメタクリロイル基の分子運動が制限されなかったためと考えられる。得られた硬化フィルムは、ＴＨＦに不溶となったことから、光ラジカル重合が速やかに進行し、架橋構造を形成したことが明らかとなった。
○ Photo-crosslinking of Poly [poly (BHO-MA) -EPO] 0.20 g (60 wt%) of Poly [poly (BHO-MA) -EPO], 0.0032 g of Irg907 as a photoradical initiator, as a reaction diluent A sample was prepared by weighing 0.13 g (40 wt%) of HEMA and 0.003 g (1 wt%) of 2E-AQ as a sensitizer and mixing them until uniform. Subsequent operations were performed in the same manner as in Example 8.
As a result, the absorption at 1637 cm −1 due to νC═C of the methacryloyl group in the IR spectrum was reduced, and the conversion of νC═C of the methacryloyl group after light irradiation was about 54%. Moreover, compared with the case of Poly (BHO-MA), the rise was slow, and the conversion rate tended to increase gradually in the latter stage of polymerization. In addition, since the content of the methacryloyl group per unit weight is less in Poly [poly (BHO-MA) -EPO] than in Poly (BHO-MA), the rise is slow, so Poly [poly (BHO- MA) -EPO] is considered to have reduced the contact ratio between methacryloyl groups in the film. The reason why the conversion rate gradually increases also in the latter stage of polymerization is considered to be that even though a crosslinked structure is formed, the molecular movement of the methacryloyl group is not restricted in the vicinity of the EPO unit not involved in crosslinking. Since the obtained cured film became insoluble in THF, it was revealed that photoradical polymerization proceeded rapidly and a crosslinked structure was formed.
○Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ）−ＥＰＯ］へのアルカリ現像性基の導入（Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ−ＭＡ−ＣＡ）−ＥＰＯ］）
５０ｍＬナスフラスコに、Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ）−ＥＰＯ］を０．５４ｇ（５ｍｍｏｌ）、ピリジン１．１５ｇ（１５ｍｍｏ１）、メタクリル酸無水物を０．３７ｇ（２．５ｍｍｏｌ）と少量のヒドロキノンを加え、室温下、２４時間反応を行った。反応終了後の操作は実施例９と同様に行い、メタクリロイル基の導入率が４１％のＰｏｌｙ［ｐｏｌｙ（ＢＨＯ−ＭＡ）−ＥＰＯ］を得た。
更にカルボキシル基を導入するために、ナスフラスコにＰｏｌｙ［ｐｏｌｙ（ＢＨＯ−ＭＡ）−ＥＰＯ］を３ｍｍｏｌ、テトラヒドロフタル酸無水物（ＴＨＰＡ）を２ｍｍｏｌ、触媒としてＴＰＰを５ｍｏｌ％、１，４−ジオキサンを３ｍＬ秤とり、室温下、２４時間反応を行った。反応終了後、反応溶液をクロロホルムで希釈し、蒸留水で数回洗浄し、有機層を無水硫酸マグネシウムで乾燥させた。乾燥剤をろ別後、良溶媒としてクロロホルム、貧溶媒としてｎ−ヘキサンを用いて再沈精製を行い、白色ポリマー［Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ−ＭＡ−ＣＡ）−ＥＰＯ］］を得た。
この白色ポリマーの構造確認は、ＩＲ、1Ｈ ＮＭＲにより行った。ＩＲスペクトルにおいて、３３５１ｃｍ-1にカルボキシル基のνＯＨに起因するブロードなシグナルを確認した。さらに、1Ｈ ＮＭＲにおいて、新しく５．６１ｐｐｍ付近にＴＨＰＡのビニルプロトンに起因するピークが現れたことから、目的の付加反応が進行したことが示唆された。また、ＴＨＰＡの付加率は、1Ｈ ＮＭＲにより、主鎖のエチル基のメチレンプロトンを基準に、５．６１ｐｐｍのＴＨＰＡのビニルプロトンの積分比から算出し、Ｄ．Ｅ．＝５２％であった。以上の結果から、合成したものはメタクリロイル基を３５％、カルボキシル基を５２％、水酸基を１３％含有するＰｏｌｙ［ｐｏｌｙ（ＢＨＯ−ＭＡ−ＣＡ）−ＥＰＯ］と決定した。
エステル化率（Ｄ．Ｅ．）＝４３％
収量：０．７６ｇ（８５％）
・ＩＲ（ｃｍ-1）：３３４２，１７６５，１６３７，１５９９，１５００，１２４７，１１０５，１０３７．
・1Ｈ−ＮＭＲ（５００ＭＨｚ，ＤＭＳＯ−ｄ6，ＴＭＳ）δｐｐｍ：０．６０−０．７９（ｍ，３Ｈ）、１．２４−１．４２（ｍ，２Ｈ），１．８１（ｓ，２Ｈ），２．２４−２．６２（ｍ，０．３Ｈ），２．９６−３．４５（ｍ，５．８Ｈ），３．４６−３．７０（ｍ），３．９１−４．２１（ｍ，０．３Ｈ）、５．５５，６．００（ｓ，０．１Ｈ）、５，５９（ｓ，１．２Ｈ），６・６３−６．９０，７．０９−７．２２（ｍ），６．５５−７．２２（ｍ，２．１Ｈ）．
○ Introduction of alkali-developable group into Poly [poly (BHO) -EPO] (Poly [poly (BHO-MA-CA) -EPO])
To a 50 mL eggplant flask, 0.54 g (5 mmol) of Poly [poly (BHO) -EPO], 1.15 g (15 mmol) of pyridine, 0.37 g (2.5 mmol) of methacrylic anhydride and a small amount of hydroquinone were added. The reaction was carried out at room temperature for 24 hours. The operation after completion of the reaction was carried out in the same manner as in Example 9 to obtain Poly [poly (BHO-MA) -EPO] having a methacryloyl group introduction rate of 41%.
In order to further introduce a carboxyl group, 3 mmol of Poly [poly (BHO-MA) -EPO], 2 mmol of tetrahydrophthalic anhydride (THPA), 5 mol% of TPP as a catalyst, and 1,4-dioxane were added to the eggplant flask. 3 mL was weighed and reacted at room temperature for 24 hours. After completion of the reaction, the reaction solution was diluted with chloroform, washed several times with distilled water, and the organic layer was dried over anhydrous magnesium sulfate. After filtering off the desiccant, reprecipitation purification was performed using chloroform as a good solvent and n-hexane as a poor solvent to obtain a white polymer [Poly [poly (BHO-MA-CA) -EPO]].
The structure of the white polymer was confirmed by IR and 1 H NMR. In the IR spectrum, a broad signal attributable to νOH of the carboxyl group was confirmed at 3351 cm −1 . Furthermore, in 1 H NMR, a new peak due to the vinyl proton of THPA appeared in the vicinity of 5.61 ppm, suggesting that the target addition reaction proceeded. Further, the THPA addition rate was calculated from the integral ratio of 5.61 ppm THPA vinyl proton based on the methylene proton of the ethyl group in the main chain by 1 H NMR. E. = 52%. From the above results, the synthesized product was determined to be Poly [poly (BHO-MA-CA) -EPO] containing 35% methacryloyl group, 52% carboxyl group and 13% hydroxyl group.
Esterification rate (DE) = 43%
Yield: 0.76 g (85%)
IR (cm -1 ): 3342, 1765, 1637, 1599, 1500, 1247, 1105, 1037.
1 H-NMR (500 MHz, DMSO-d 6 , TMS) δ ppm: 0.60-0.79 (m, 3H), 1.24-1.42 (m, 2H), 1.81 (s, 2H) ), 2.24-2.62 (m, 0.3H), 2.96-3.45 (m, 5.8H), 3.46-3.70 (m), 3.91-4.21. (M, 0.3H), 5.55, 6.00 (s, 0.1H), 5,59 (s, 1.2H), 6.63-6.90, 7.09-7.22 ( m), 6.55-7.22 (m, 2.1H).
○熱的特性
Ｐｏｌｙ（ＢＨＯ）、Ｐｏｌｙ（ＢＨＯ−Ａｃ）、Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ−Ａｃ）−ＥＰＯ］、およびＰｏｌｙ［ｐｏｌｙ（ＢＨＯ）−ＥＰＯ］の熱的特性をＴＧ／ＤＴＡおよびＤＳＣを用いて測定した。
１０％重量減少温度（Ｔｄ10%）は、約５ｍｇのサンプルをＳｅｉｋｏ Ｉｎｓｔｒｕｍｅｎｔ製開放型アルミニウムパンに秤とり、Ｓｅｉｋｏ Ｉｎｓｔｒｕｍｅｎｔ ＥＸＳＴＥＲ ６０００／ＴＧ−ＤＴＡ ６２００を用いて、窒素気流下、１０℃／ｍｉｎの昇温速度（昇温設定：室温〜６００℃）で測定した。
ガラス転移温度（Ｔｇ）は、約５ｍｇのサンプルをＳｅｉｋｏ Ｉｎｓｔｒｕｍｅｎｔ製密閉型アルミニウムパンに秤とり、上記記載の装置を用いて、窒素気流下、１０℃／ｍｉｎの昇温速度（昇温設定：−７８〜２００℃）で測定した。
この結果を下記に示す。
○ Thermal properties Poly (BHO), Poly (BHO-Ac), Poly [poly (BHO-Ac) -EPO], and Poly [poly (BHO) -EPO] thermal properties using TG / DTA and DSC Measured.
The 10% weight loss temperature (Td 10% ) was obtained by weighing about 5 mg of sample into an open aluminum pan manufactured by Seiko Instrument and using Seiko Instrument EXSTER 6000 / TG-DTA 6200 at 10 ° C./min under a nitrogen stream. The measurement was performed at a heating rate (temperature setting: room temperature to 600 ° C.).
For the glass transition temperature (Tg), about 5 mg of a sample was weighed on a closed aluminum pan manufactured by Seiko Instrument, and the temperature was increased at a rate of 10 ° C./min (temperature setting: − 78-200 ° C).
The results are shown below.
○溶解性試験：有機溶媒
Ｐｏｌｙ（ＢＨＯ）（イと標記した）を２ｍｇサンプル瓶に秤とり、表６に記載の溶媒を２ｍＬ加えて、それぞれの溶解性試験を行った。また、室温で溶解しないサンプルは加熱した。また、Ｐｏｌｙ（ＢＨＯ−ＭＡ）（ロと標記）、Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ）−ＥＰＯ］（ハと標記）、Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ−ＭＡ）−ＥＰＯ］（ニと標記）、Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ−ＭＡ−ＣＡ）−ＥＰＯ］（ホと標記）についても同様に行なった。
この結果を下記に示す。なお、表に記載の「＋＋」は室温で可溶を、「＋」は加熱して可溶を、「±」は難溶を、「−」は不溶を示す。
○ Solubility test: Organic solvent Poly (BHO) (labeled as A) was weighed in a 2 mg sample bottle, and 2 mL of the solvent described in Table 6 was added to perform each solubility test. Samples that did not dissolve at room temperature were heated. Poly (BHO-MA) (labeled B), Poly [poly (BHO) -EPO] (marked C), Poly [poly (BHO-MA) -EPO] (marked D), Poly [poly ( The same procedure was performed for BHO-MA-CA) -EPO] (labeled E).
The results are shown below. In the table, “++” indicates solubility at room temperature, “+” indicates solubility upon heating, “±” indicates poor solubility, and “−” indicates insolubility.
○溶解性試験：水系溶媒
Ｐｏｌｙ（ＢＨＯ）（イと標記した）を２ｍｇサンプル瓶に秤とり、表７に記載の溶媒を２ｍＬ加えて、溶解性試験を行った。また、室温で溶解しないサンプルは加熱した。また、Ｐｏｌｙ［ｐｏｌｙ（ＢＨＯ−ＭＡ−ＣＡ）−ＥＰＯ］（ホと標記）についても同様に行なった。なお、テトラメチルアンモニウムハイドロオキシドをＴＭＡＨとする。
この結果を下記に示す。なお、表に記載の「＋＋」は室温で可溶を、「＋」は加熱して可溶を、「±」は難溶を、「−」は不溶を示す。
○ Solubility test: Aqueous solvent Poly (BHO) (labeled as A) was weighed into a 2 mg sample bottle, and 2 mL of the solvent described in Table 7 was added to conduct a solubility test. Samples that did not dissolve at room temperature were heated. Moreover, it carried out similarly about Poly [poly (BHO-MA-CA) -EPO] (it is marked with e). Tetramethylammonium hydroxide is TMAH.
The results are shown below. In the table, “++” indicates solubility at room temperature, “+” indicates solubility upon heating, “±” indicates poor solubility, and “−” indicates insolubility.
＜合成例２＞
○Ｐｏｌｙ（ＥＨＯ）の合成
１００ｍＬのナス型フラスコに３−エチル−３−ヒドロキシメチルオキセタン（ＥＨＯ）を１００ｍｍｏｌ、ｔ−ＢｕＯＫを１０ｍｏｌ％、１８−Ｃ−６を１０ｍｏｌ％、およびＮＭＰを２０ｍＬ入れ、１８０℃で２時間撹拌した。反応終了後、反応液を蒸留水中に入れ、希塩酸を用いて酸析を行い、析出した固体をろ過により回収した。この酸析物を、良溶媒にテトラヒドロフラン（ＴＨＦ）と貧溶媒にｎ−ヘキサンとを用いて再沈精製を行った後、減圧乾燥して、白色粉末を得た。
収量：８．０ｇ（６９％）
Ｍｎ：７００、Ｍｗ／Ｍｎ：１．２４
Ｄ．Ｂ．：０．１８
・ＩＲ（ｆｉｌｍ，ｃｍ-1）：３３６５（Ｏ−Ｈ），１１０９，１０５１（Ｃ−Ｏ−Ｃ ｅｔｈｅｒ），９９０（Ｃ−Ｏ−Ｃ ｏｘｅｔａｎｅ ｒｉｎｇ）
・1Ｈ−ＮＭＲ（５００ＭＨｚ，ＤＭＳＯ−ｄ6 ＴＭＳ）δｐｐｍ：
０．７８（ｍ，−ＣＨ3），１．２５（ｍ，−ＣＨ2ＣＨ3），１．６０（ｍ，−ＣＨ2ＣＨ3 ｅｎｄ ｇｒｏｕｐ），２．７０−３．３０（ｍ，−ＯＣＨ2，−ＣＨ2ＯＨ），３．４２（ｓ，−ＣＨ2Ｏ− ｅｎｄ ｇｒｏｕｐ），４．１６（ｓ，−ＣＨ2ＯＨ），４，４２（ＡＢ ｑｕａｒｔｅｔ，０．６６Ｈ，−ＣＨ2Ｏ− ｏｘｅｔａｎｅ ｒｉｎｇ）
・13Ｃ−ＮＭＲ（１２５ＭＨｚ，ＤＭＳＯ−ｄ6，ＴＭＳ）δｐｐｍ：
７．６０，８．０４，２２．０−２３．２，２６．５，４０．０，４３．３，６２．０，７１．６，７３．４，７７．１
白色粉末の各種分析データから分子中に１個のオキセタン環を有する多分岐マクロモノマー（Ｐｏｌｙ（ＥＨＯ））と決定した。
<Synthesis Example 2>
○ Synthesis of Poly (EHO) 100 mmol of 3-ethyl-3-hydroxymethyloxetane (EHO), 10 mol% of t-BuOK, 10 mol% of 18-C-6, and 20 mL of NMP were placed in a 100 mL eggplant-shaped flask, Stir at 180 ° C. for 2 hours. After completion of the reaction, the reaction solution was placed in distilled water, acidified using diluted hydrochloric acid, and the precipitated solid was collected by filtration. The acid precipitate was purified by reprecipitation using tetrahydrofuran (THF) as a good solvent and n-hexane as a poor solvent, and then dried under reduced pressure to obtain a white powder.
Yield: 8.0 g (69%)
Mn: 700, Mw / Mn: 1.24
D. B. : 0.18
IR (film, cm −1 ): 3365 (O—H), 1109, 1051 (C—O—C ether), 990 (C—O—C oxetane ring)
1 H-NMR (500 MHz, DMSO-d 6 TMS) δ ppm:
0.78 (m, -CH 3), 1.25 (m, -CH 2 CH 3), 1.60 (m, -CH 2 CH 3 end group), 2.70-3.30 (m, - OCH 2, -CH 2 OH), 3.42 (s, -CH 2 O- end group), 4.16 (s, -CH 2 OH), 4,42 (AB quartet, 0.66H, -CH 2 O-oxetane ring)
· 13 C-NMR (125MHz, DMSO-d 6, TMS) δppm:
7.60, 8.04, 22.0-23.2, 26.5, 40.0, 43.3, 62.0, 71.6, 73.4, 77.1
It was determined as a multi-branched macromonomer (Poly (EHO)) having one oxetane ring in the molecule from various analysis data of the white powder.
本発明の多分岐ポリエーテルポリオールまたは多分岐マクロモノマーは、この分子中に存在する水酸基にビニル基、（メタ）アクリレート基、エポキシ基又はカルボキシル基などを有する化合物を付加することが容易である。このことから、本発明の多分岐ポリエーテルポリオールまたは多分岐マクロモノマーを用いることにより多くの機能を有する多分岐マクロモノマーに誘導することができる。また、本発明の多分岐マクロモノマーは、溶解性が向上するなどの機能が期待できる。 In the multi-branched polyether polyol or the multi-branched macromonomer of the present invention, it is easy to add a compound having a vinyl group, a (meth) acrylate group, an epoxy group or a carboxyl group to the hydroxyl group present in the molecule. From this, the multibranched macromonomer having many functions can be derived by using the multibranched polyether polyol or the multibranched macromonomer of the present invention. In addition, the multibranched macromonomer of the present invention can be expected to have functions such as improved solubility.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0637014U (en) * | 1992-10-28 | 1994-05-17 | 本田技研工業株式会社 | Airbag device for passenger seat |
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|---|---|---|---|---|
| JP4639332B2 (en) * | 2005-02-09 | 2011-02-23 | 学校法人神奈川大学 | Dendritic polymer, radiation curable dendritic polymer, cured product, and production method thereof |
| GB202012564D0 (en) * | 2020-08-12 | 2020-09-23 | Univ Bath | Polymerisation processes |
| JP2023132798A (en) * | 2022-03-11 | 2023-09-22 | 三菱ケミカル株式会社 | Polyether polyol and polyester |
| JP2023132797A (en) * | 2022-03-11 | 2023-09-22 | 三菱ケミカル株式会社 | Polyether polyol and polyester |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0637014U (en) * | 1992-10-28 | 1994-05-17 | 本田技研工業株式会社 | Airbag device for passenger seat |
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