KR20230074948A - Covalently attached antioxidant to organic material, and method of preparing same - Google Patents
Covalently attached antioxidant to organic material, and method of preparing same Download PDFInfo
- Publication number
- KR20230074948A KR20230074948A KR1020210161052A KR20210161052A KR20230074948A KR 20230074948 A KR20230074948 A KR 20230074948A KR 1020210161052 A KR1020210161052 A KR 1020210161052A KR 20210161052 A KR20210161052 A KR 20210161052A KR 20230074948 A KR20230074948 A KR 20230074948A
- Authority
- KR
- South Korea
- Prior art keywords
- antioxidant
- butylphenol
- structural formula
- polyolefin
- compound represented
- Prior art date
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 81
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title abstract description 9
- 239000011368 organic material Substances 0.000 title abstract description 5
- VCJIGSOOIYBSFA-UHFFFAOYSA-N azido formate Chemical group [N-]=[N+]=NOC=O VCJIGSOOIYBSFA-UHFFFAOYSA-N 0.000 claims abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims description 38
- 229920000098 polyolefin Polymers 0.000 claims description 36
- -1 polypropylene Polymers 0.000 claims description 35
- 239000004743 Polypropylene Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 229920001155 polypropylene Polymers 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 229920005549 butyl rubber Polymers 0.000 claims description 12
- 239000005062 Polybutadiene Substances 0.000 claims description 11
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 11
- 229920002857 polybutadiene Polymers 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 9
- 239000005060 rubber Substances 0.000 claims description 9
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 238000006713 insertion reaction Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 6
- NFIDBGJMFKNGGQ-UHFFFAOYSA-N 2-(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC=CC=C1O NFIDBGJMFKNGGQ-UHFFFAOYSA-N 0.000 claims description 6
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 claims description 6
- DKUKYQHDSXMXBF-UHFFFAOYSA-N 2-butyl-6-ethylphenol Chemical compound CCCCC1=CC=CC(CC)=C1O DKUKYQHDSXMXBF-UHFFFAOYSA-N 0.000 claims description 6
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 claims description 6
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 claims description 6
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 claims description 6
- VLJSLTNSFSOYQR-UHFFFAOYSA-N 3-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(O)=C1 VLJSLTNSFSOYQR-UHFFFAOYSA-N 0.000 claims description 6
- CIRRFAQIWQFQSS-UHFFFAOYSA-N 6-ethyl-o-cresol Chemical compound CCC1=CC=CC(C)=C1O CIRRFAQIWQFQSS-UHFFFAOYSA-N 0.000 claims description 6
- 229920002943 EPDM rubber Polymers 0.000 claims description 6
- 229920000459 Nitrile rubber Polymers 0.000 claims description 6
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229920003049 isoprene rubber Polymers 0.000 claims description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 6
- 150000001540 azides Chemical class 0.000 claims description 5
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000000707 stereoselective effect Effects 0.000 claims description 5
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 4
- NGFPWHGISWUQOI-UHFFFAOYSA-N 2-sec-butylphenol Chemical compound CCC(C)C1=CC=CC=C1O NGFPWHGISWUQOI-UHFFFAOYSA-N 0.000 claims description 4
- 229910010082 LiAlH Inorganic materials 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-methyl phenol Natural products CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- JRPBSTGRRSTANR-UHFFFAOYSA-N 2,6-bis(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC=CC(CC(C)C)=C1O JRPBSTGRRSTANR-UHFFFAOYSA-N 0.000 claims description 3
- FHTGJZOULSYEOB-UHFFFAOYSA-N 2,6-di(butan-2-yl)phenol Chemical compound CCC(C)C1=CC=CC(C(C)CC)=C1O FHTGJZOULSYEOB-UHFFFAOYSA-N 0.000 claims description 3
- PZPVXSMCRLNVRD-UHFFFAOYSA-N 2,6-dibutylphenol Chemical compound CCCCC1=CC=CC(CCCC)=C1O PZPVXSMCRLNVRD-UHFFFAOYSA-N 0.000 claims description 3
- METWAQRCMRWDAW-UHFFFAOYSA-N 2,6-diethylphenol Chemical compound CCC1=CC=CC(CC)=C1O METWAQRCMRWDAW-UHFFFAOYSA-N 0.000 claims description 3
- WKMUONDKNHDXME-UHFFFAOYSA-N 2-butan-2-yl-6-ethylphenol Chemical compound CCC(C)C1=CC=CC(CC)=C1O WKMUONDKNHDXME-UHFFFAOYSA-N 0.000 claims description 3
- IJYMKBRMIMMBQW-UHFFFAOYSA-N 2-butan-2-yl-6-methylphenol Chemical compound CCC(C)C1=CC=CC(C)=C1O IJYMKBRMIMMBQW-UHFFFAOYSA-N 0.000 claims description 3
- LPDQFYFNOXVZEI-UHFFFAOYSA-N 2-butyl-6-(2-methylpropyl)phenol Chemical compound C(CCC)C1=C(C(=CC=C1)CC(C)C)O LPDQFYFNOXVZEI-UHFFFAOYSA-N 0.000 claims description 3
- KUNNUNBSGQSGDY-UHFFFAOYSA-N 2-butyl-6-methylphenol Chemical compound CCCCC1=CC=CC(C)=C1O KUNNUNBSGQSGDY-UHFFFAOYSA-N 0.000 claims description 3
- QXVWWADASQRJAU-UHFFFAOYSA-N 2-butyl-6-propan-2-ylphenol Chemical compound CCCCC1=CC=CC(C(C)C)=C1O QXVWWADASQRJAU-UHFFFAOYSA-N 0.000 claims description 3
- JLBMJOPTDAAHQS-UHFFFAOYSA-N 2-butyl-6-tert-butylphenol Chemical compound CCCCC1=CC=CC(C(C)(C)C)=C1O JLBMJOPTDAAHQS-UHFFFAOYSA-N 0.000 claims description 3
- KIDVZZUPJUNJEO-UHFFFAOYSA-N 2-ethyl-6-(2-methylpropyl)phenol Chemical compound CCC1=CC=CC(CC(C)C)=C1O KIDVZZUPJUNJEO-UHFFFAOYSA-N 0.000 claims description 3
- OTLDNWAMLMBKHT-UHFFFAOYSA-N 2-ethyl-6-propan-2-ylphenol Chemical compound CCC1=CC=CC(C(C)C)=C1O OTLDNWAMLMBKHT-UHFFFAOYSA-N 0.000 claims description 3
- BWVHLTNCVRBWKW-UHFFFAOYSA-N 2-methyl-6-(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC=CC(C)=C1O BWVHLTNCVRBWKW-UHFFFAOYSA-N 0.000 claims description 3
- KFETUQFRWIVAMU-UHFFFAOYSA-N 2-methyl-6-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(C)=C1O KFETUQFRWIVAMU-UHFFFAOYSA-N 0.000 claims description 3
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 3
- APIQWHVRWQYLFW-UHFFFAOYSA-N 2-tert-butyl-6-ethylphenol Chemical compound CCC1=CC=CC(C(C)(C)C)=C1O APIQWHVRWQYLFW-UHFFFAOYSA-N 0.000 claims description 3
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 claims description 3
- ZKSISJGIJFEBMS-UHFFFAOYSA-N 3-(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC=CC(O)=C1 ZKSISJGIJFEBMS-UHFFFAOYSA-N 0.000 claims description 3
- NBYBZLCUXTUWBA-UHFFFAOYSA-N 3-butan-2-ylphenol Chemical compound CCC(C)C1=CC=CC(O)=C1 NBYBZLCUXTUWBA-UHFFFAOYSA-N 0.000 claims description 3
- MQSXUKPGWMJYBT-UHFFFAOYSA-N 3-butylphenol Chemical compound CCCCC1=CC=CC(O)=C1 MQSXUKPGWMJYBT-UHFFFAOYSA-N 0.000 claims description 3
- CYEKUDPFXBLGHH-UHFFFAOYSA-N 3-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1 CYEKUDPFXBLGHH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 3
- 239000012448 Lithium borohydride Substances 0.000 claims description 3
- 229920002367 Polyisobutene Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 claims description 3
- 229920001903 high density polyethylene Polymers 0.000 claims description 3
- 239000004700 high-density polyethylene Substances 0.000 claims description 3
- 229920001684 low density polyethylene Polymers 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- 229920001179 medium density polyethylene Polymers 0.000 claims description 3
- 239000004701 medium-density polyethylene Substances 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- OLBCVFGFOZPWHH-UHFFFAOYSA-N propofol Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O OLBCVFGFOZPWHH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- 125000000486 o-cresyl group Chemical group [H]C1=C([H])C(O*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 9
- RIZMRRKBZQXFOY-UHFFFAOYSA-N ethion Chemical compound CCOP(=S)(OCC)SCSP(=S)(OCC)OCC RIZMRRKBZQXFOY-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000012790 confirmation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- KPYNPYLYIYBHEI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(3-hydroxypropyl)phenol Chemical compound CC(C)(C)C1=CC(CCCO)=CC(C(C)(C)C)=C1O KPYNPYLYIYBHEI-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 3
- IPBIPEHNUKRTBD-UHFFFAOYSA-N 2-butan-2-yl-6-butylphenol Chemical compound CCCCC1=CC=CC(C(C)CC)=C1O IPBIPEHNUKRTBD-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920000582 polyisocyanurate Polymers 0.000 description 2
- 239000011495 polyisocyanurate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/00—Use of organic ingredients
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Abstract
Description
본 발명은 유기물에 공유결합으로 연결되는 산화방지제 및 그의 제조방법에 관한 것으로, 상세하게는 사슬의 어느 하나의 말단에 아지도 포르메이트기를 갖고 상기 사슬의 다른 하나의 말단에 페놀 유도체 잔기를 가짐으로써 분산성이 향상되고 휘발되지 않아 유기물의 안정성을 향상시켜주는 산화방지제 및 그의 제조방법에 관한 것이다.The present invention relates to an antioxidant covalently linked to an organic substance and a method for producing the same, and more particularly, by having an azido formate group at one end of a chain and a phenol derivative residue at the other end of the chain It relates to an antioxidant that has improved dispersibility and does not volatilize, thereby improving the stability of organic matter, and a method for preparing the same.
고분자는 열, 산소, 빛 등 외부 영향에 의해, 고분자 내 존재하는 결합이 절단되고 라디칼이 생성되는 산화반응이 일어난다. 이러한 반응으로 사슬 절단이나 가교가 일어나 착색 및 물성 저하 등 고분자 본질의 성질이 저하된다. 이에 산화방지제를 투입하여 가공 및 사용 중 원치 않는 화학적 반응을 억제하는 것이 일반적이다.Polymers undergo an oxidation reaction in which bonds existing in the polymer are cleaved and radicals are generated by external influences such as heat, oxygen, and light. As a result of this reaction, chain scission or crosslinking occurs, resulting in degradation of the intrinsic properties of the polymer, such as coloration and degradation of physical properties. It is common to add antioxidants to suppress unwanted chemical reactions during processing and use.
1차 산화방지제는 라디칼 포착제로 주로 페놀계와 방향족 아민계를 사용하고, 2차 산화방지제는 생성된 과산화물을 환원시키는 과산화물 분해제로 포스파이트 화합물과 유황 화합물이 대표적으로 사용되고 있다. 특히, 페놀계 산화방지제는 1차 산화방지제 중에서도 가격이 저렴할 뿐 아니라 라디칼을 소모시키는 효과가 뛰어나 산업현장에서 널리 사용되고 있다. 초기 색상 안정성이 우수하나, 과량이 투입되는 경우 대기와 반응으로 최종 제품을 변색시키는 경우가 많아, 종류에 따라 최적농도를 첨가해야한다.Primary antioxidants mainly use phenols and aromatic amines as radical scavengers, and phosphite compounds and sulfur compounds are typically used as secondary antioxidants as peroxide decomposers that reduce generated peroxides. In particular, phenolic antioxidants are inexpensive among primary antioxidants and are widely used in industrial fields because of their excellent effect of consuming radicals. It has excellent initial color stability, but when an excessive amount is added, it often discolors the final product due to reaction with the atmosphere, so it is necessary to add the optimum concentration according to the type.
현재도 많이 사용되는 mono-phenol을 가진 butylated hydroxy toluene(BHT)는 1차 산화방지제로 가격이 저렴하고 수지와 상용성 및 분산성이 좋아 우수한 산화 방지 성능을 나타낸다. 그러나 산화에 의한 quinone 구조로의 변형으로 변색이 쉽고, 분자량이 작기 때문에 휘발성이 커 사용기간이 짧은 단점을 지닌다. 그래서 높은 분자량의 산화방지제가 개발되었으나 수지와의 상용성이 떨어지는 또 다른 문제점이 대두되었으며, 이를 alkylation으로 보완하여 현재는 Irganox1010, Irganox1076 등을 가장 보편화하여 사용되고 있다. 그러나 이도 고온 가공 시 색 안정성이 떨어지는 문제를 가지고 있다.Butylated hydroxy toluene (BHT) with mono-phenol, which is widely used today, is a primary antioxidant that is inexpensive and exhibits excellent antioxidant performance due to its good compatibility and dispersibility with resins. However, it is easily discolored due to transformation into a quinone structure by oxidation, and has a short shelf life due to high volatility due to its small molecular weight. Therefore, high molecular weight antioxidants have been developed, but another problem of poor compatibility with resins has emerged, and this has been supplemented with alkylation, and currently Irganox 1010 and Irganox 1076 are most commonly used. However, this also has a problem of poor color stability during high-temperature processing.
따라서, 고분자 내 산화방지제의 휘발성을 줄이고 수지와의 상용성과 분산성을 유지할 수 있는 산화방지제 및 그의 제조방법에 관한 연구가 필요하다. Therefore, there is a need for research on antioxidants capable of reducing the volatility of antioxidants in polymers and maintaining compatibility and dispersibility with resins and their preparation methods.
본 발명의 목적은 상기 문제점들을 해결하기 위한 것으로, 고분자 내 산화방지제의 휘발성을 줄이고 수지와의 상용성과 분산성을 유지할 수 있는 산화방지제 및 그의 제조방법을 제공하는데 있다.An object of the present invention is to solve the above problems, and to provide an antioxidant capable of reducing the volatility of the antioxidant in a polymer and maintaining compatibility and dispersibility with a resin and a method for preparing the same.
또한, 본 발명의 산화방지제를 사용함으로써 열적 안정성이 향상된 고분자 및 그의 제조방법을 제공하는데 있다.In addition, it is to provide a polymer with improved thermal stability and a manufacturing method thereof by using the antioxidant of the present invention.
본 발명의 일 측면에 따르면, 사슬의 어느 하나의 말단에 아지도 포르메이트기(
또한, 상기 산화방지제가 아래 구조식 1로 표시되는 것일 수 있다.In addition, the antioxidant may be represented by Structural Formula 1 below.
[구조식 1][Structural Formula 1]
상기 구조식 1에서,In Structural Formula 1,
R1은 원자가 결합 또는 C1 내지 C30의 알킬렌기이고,R 1 is a valence bond or a C1 to C30 alkylene group;
R2 및 R3은 서로 같거나 다르고, 각각 수소원자 또는 C1 내지 C30의 알킬기이다.R 2 and R 3 are the same as or different from each other, and each represents a hydrogen atom or a C1 to C30 alkyl group.
또한, 상기 페놀 유도체 잔기가 2-메틸페놀, 3-메틸페놀, 2,6-디메틸페놀, 2-에틸페놀, 3-에틸페놀, 2,6-에틸페놀, 2-부틸페놀, 3-부틸페놀, 2,6-부틸페놀, 2-sec-부틸페놀, 3-sec-부틸페놀, 2,6-di-sec-부틸페놀, 2-tert-부틸페놀, 3-tert-부틸페놀, 2,6-di-tert-부틸페놀, 2-이소프로필페놀, 3-이소프로필페놀, 2,6-디이소프로필페놀, 2-이소부틸페놀, 3-이소부틸페놀, 2,6-디이소부틸페놀, 2-메틸-6-에틸페놀, 2-메틸-6-이소프로필페놀, 2-메틸-6-부틸페놀, 2-메틸-6-sec-부틸페놀, 2-메틸-6-tert-부틸페놀, 2-메틸-6-이소부틸페놀, 2-에틸-6-에틸페놀, 2-에틸-6-이소프로필페놀, 2-에틸-6-부틸페놀, 2-에틸-6-sec-부틸페놀, 2-에틸-6-tert-부틸페놀, 2-에틸-6-이소부틸페놀, 2-부틸-6-에틸페놀, 2-부틸-6-이소프로필페놀, 2-부틸-6-부틸페놀, 2-부틸-6-sec-부틸페놀, 2-부틸-6-tert-부틸페놀 및 2-부틸-6-이소부틸페놀로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.In addition, the phenol derivative residue is 2-methylphenol, 3-methylphenol, 2,6-dimethylphenol, 2-ethylphenol, 3-ethylphenol, 2,6-ethylphenol, 2-butylphenol, 3-butylphenol , 2,6-butylphenol, 2-sec-butylphenol, 3-sec-butylphenol, 2,6-di-sec-butylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 2,6 -di-tert-butylphenol, 2-isopropylphenol, 3-isopropylphenol, 2,6-diisopropylphenol, 2-isobutylphenol, 3-isobutylphenol, 2,6-diisobutylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-isopropylphenol, 2-methyl-6-butylphenol, 2-methyl-6-sec-butylphenol, 2-methyl-6-tert-butylphenol, 2-methyl-6-isobutylphenol, 2-ethyl-6-ethylphenol, 2-ethyl-6-isopropylphenol, 2-ethyl-6-butylphenol, 2-ethyl-6-sec-butylphenol, 2 -Ethyl-6-tert-butylphenol, 2-ethyl-6-isobutylphenol, 2-butyl-6-ethylphenol, 2-butyl-6-isopropylphenol, 2-butyl-6-butylphenol, 2- It may include at least one selected from the group consisting of butyl-6-sec-butylphenol, 2-butyl-6-tert-butylphenol, and 2-butyl-6-isobutylphenol.
본 발명의 다른 하나의 측면에 따르면, 폴리올레핀 및 상기 산화방지제가 공유결합한 안정화된 폴리올레핀이 제공된다.According to another aspect of the present invention, a stabilized polyolefin in which a polyolefin and the antioxidant are covalently bonded is provided.
또한, 상기 산화방지제의 아지드(-N3)는 질소(N2)가 빠지면서 상기 폴리올레핀의 C-H 결합의 수소와 치환되어 공유결합한 것일 수 있다.In addition, the azide (-N 3 ) of the antioxidant may be covalently bonded by substitution with hydrogen of the CH bond of the polyolefin while nitrogen (N 2 ) is missing.
또한, 상기 안정화된 폴리올레핀이 아래 구조식 2로 표시되는 것일 수 있다.In addition, the stabilized polyolefin may be represented by Structural Formula 2 below.
[구조식 2][Structural Formula 2]
상기 구조식 2에서,In Structural Formula 2,
R1은 원자가 결합 또는 C1 내지 C30의 알킬렌기이고,R 1 is a valence bond or a C1 to C30 alkylene group;
R2 및 R3은 서로 같거나 다르고, 각각 수소원자 또는 C1 내지 C30의 알킬기이고,R 2 and R 3 are the same as or different from each other, and each represents a hydrogen atom or a C1 to C30 alkyl group;
R4 및 R5는 서로 같거나 다르고, 각각 수소원자 또는 C1 내지 C30의 알킬기이고,R 4 and R 5 are the same as or different from each other, and each represents a hydrogen atom or a C1 to C30 alkyl group;
m 및 n은 각각 독립적으로 반복단위의 반복수이다.m and n are each independently the repeating number of the repeating unit.
또한, 상기 폴리올레핀이 폴리프로필렌, 고밀도 폴리에틸렌, 중밀도 폴리에틸렌, 저밀도 폴리에틸렌, 초고분자 폴리에틸렌, 폴리1-부텐, 폴리부타디엔, 폴리스티렌, 폴리이소프렌, 폴리이소부틸렌, 폴리클로로프렌, 폴리1-펜텐, 폴리이소펜텐, 폴리1-헥센, 폴리1-헵텐, 폴리이소헵텐, 폴리1-노넨, 폴리1-데켄, 폴리비닐시클로헥산, 폴리터부틸에틸렌, 폴리다이엔, 에틸렌-α-올레핀 공중합체, 에틸렌-프로필렌 공중합체(EPR), 에틸렌-프로필렌-디엔 러버(EPDM), 스티렌 부타디엔 스티렌 공중합체(SBS), 스티렌 부타디엔 러버(SBR, styrene butadiene rubber), 입체규칙성 스티렌 부타디엔 러버(stereospecific SBR, stereospecific styrene butadiene rubber), 스티렌 부타디엔 스티렌 공중합체, 폴리클로로프렌 러버(CR, polychloroprene rubber), 시스-클로로부타디엔 러버(cis-chlorobutadiene rubber), 아크릴로니트릴 부타디엔 러버(NBR, acrylonitrile butadiene rubber), 부타디엔 러버(BR, butadiene rubber), 이소프렌 러버(IR, isoprene rubber), 이소부틸렌 이소프렌 러버(IIR, isobutylene isoprene rubber, butyl rubber) 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.In addition, the polyolefin is polypropylene, high density polyethylene, medium density polyethylene, low density polyethylene, ultra high molecular weight polyethylene, poly1-butene, polybutadiene, polystyrene, polyisoprene, polyisobutylene, polychloroprene, poly1-pentene, polyiso Pentene, poly1-hexene, poly1-heptene, polyisoheptene, poly1-nonene, poly1-decene, polyvinylcyclohexane, polyterbutylethylene, polydiene, ethylene-α-olefin copolymer, ethylene- Propylene copolymer (EPR), ethylene-propylene-diene rubber (EPDM), styrene butadiene styrene copolymer (SBS), styrene butadiene rubber (SBR), stereospecific styrene butadiene rubber (stereospecific SBR) rubber), styrene butadiene styrene copolymer, polychloroprene rubber (CR, polychloroprene rubber), cis-chlorobutadiene rubber, acrylonitrile butadiene rubber (NBR, butadiene rubber), butadiene rubber (BR) rubber), isoprene rubber (IR, isoprene rubber), isobutylene isoprene rubber (IIR, isobutylene isoprene rubber, butyl rubber), and at least one selected from the group consisting of copolymers thereof.
본 발명의 또 다른 하나의 측면에 따르면, (a) 반응식 1에 따라 구조식 11로 표시되는 화합물과 환원제를 반응시켜 구조식 12로 표시되는 화합물을 제조하는 단계; (b) 반응식 2에 따라 상기 구조식 12로 표시되는 화합물과 구조식 13으로 표시되는 화합물을 반응시켜 구조식 14로 표시되는 화합물을 제조하는 단계; 및 (c) 반응식 3에 따라 상기 구조식 14로 표시되는 화합물과 구조식 15로 표시되는 알칼리금속 아지드를 반응시켜 구조식 1로 표시되는 산화방지제를 제조하는 단계;를 포함하는 산화방지제의 제조방법이 제공된다.According to another aspect of the present invention, (a) preparing a compound represented by Structural Formula 12 by reacting a compound represented by Structural Formula 11 with a reducing agent according to Scheme 1; (b) reacting the compound represented by Structural Formula 12 with the compound represented by Structural Formula 13 according to Scheme 2 to prepare a compound represented by Structural Formula 14; and (c) reacting the compound represented by Structural Formula 14 with an alkali metal azide represented by Structural Formula 15 according to Scheme 3 to prepare an antioxidant represented by Structural Formula 1; do.
[반응식 1][Scheme 1]
[반응식 2][Scheme 2]
[반응식 3][Scheme 3]
상기 반응식 1 내지 3에서, In Schemes 1 to 3 above,
R1은 원자가 결합 또는 C1 내지 C30의 알킬렌기이고,R 1 is a valence bond or a C1 to C30 alkylene group;
R2 및 R3은 서로 같거나 다르고, 각각 수소원자 또는 C1 내지 C30의 알킬기이고,R 2 and R 3 are the same as or different from each other, and each represents a hydrogen atom or a C1 to C30 alkyl group;
R'은 서로 같거나 다르고, 각각 할로겐 원자, 
X1 내지 X3은 서로 같거나 다르고, 각각 할로겐 원자이고,X 1 to X 3 are the same as or different from each other, and each is a halogen atom;
M은 알칼리금속이다.M is an alkali metal.
또한, 상기 환원제가 수소화 리튬알루미늄(LiAlH4), 소듐 보로하이드라이드(NaBH4), 리튬 보로하이드라이드(LiBH4) 및 디보란(B2H6)으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.In addition, the reducing agent may include at least one selected from the group consisting of lithium aluminum hydride (LiAlH 4 ), sodium borohydride (NaBH 4 ), lithium borohydride (LiBH 4 ), and diborane (B 2 H 6 ). can
또한, 상기 산화방지제의 제조방법이 -50 내지 70 ℃의 온도에서 수행될 수 있다.In addition, the manufacturing method of the antioxidant may be carried out at a temperature of -50 to 70 ℃.
또한, 상기 환원제가 상기 구조식 11로 표시되는 화합물 100 몰을 기준으로 25 내지 400 몰 포함할 수 있다.In addition, the reducing agent may include 25 to 400 moles based on 100 moles of the compound represented by Structural Formula 11.
또한, 상기 구조식 13으로 표시되는 화합물이 상기 구조식 12로 표시되는 화합물 100 몰을 기준으로 10 내지 100 몰 포함할 수 있다.In addition, 10 to 100 moles of the compound represented by Structural Formula 13 may be included based on 100 moles of the compound represented by Structural Formula 12.
또한, 상기 알칼리금속 아지드가 상기 구조식 14로 표시되는 화합물 100 몰을 기준으로 50 내지 400 몰 포함할 수 있다.In addition, 50 to 400 moles of the alkali metal azide may be included based on 100 moles of the compound represented by Structural Formula 14.
본 발명의 또 다른 하나의 측면에 따르면, 사슬의 어느 하나의 말단에 아지도 포르메이트기(
또한, 상기 반응이 C-H 삽입 반응으로 수행되고, 상기 C-H 삽입 반응이 아래 반응식 4와 같이 같이 아지도포메이트의 질소가 싱글릿 나이트렌(singlet nitrene)이 되고, 상기 싱글릿 나이트렌이 폴리올레핀의 C-H 결합의 수소와 치환되어 공유결합되는 것일 수 있다.In addition, the reaction is performed as a C-H insertion reaction, and the nitrogen of azidoformate becomes singlet nitrene as shown in Scheme 4 below, and the singlet nitrene is a C-H bond of polyolefin. It may be substituted with hydrogen of and bonded covalently.
[반응식 4][Scheme 4]
또한, 상기 산화방지제가 상기 폴리올레핀과 상기 산화방지제의 합 100 중량부를 기준으로 0.1 내지 20 중량부 포함할 수 있다.In addition, the antioxidant may include 0.1 to 20 parts by weight based on 100 parts by weight of the sum of the polyolefin and the antioxidant.
또한, 상기 반응이 50 내지 300 ℃의 온도에서 수행되는 것일 수 있다.In addition, the reaction may be carried out at a temperature of 50 to 300 ℃.
본 발명의 산화방지제는 사슬의 어느 하나의 말단에 아지도 포르메이트기(
또한, 본 발명의 산화방지제가 공유결합된 고분자는 열적 안정성이 향상되는 효과가 있다.In addition, the polymer to which the antioxidant of the present invention is covalently bonded has an effect of improving thermal stability.
또한, 본 발명의 산화방지제는 기존 고분자에 용융 혼합만으로 바로 기능성 부여가 가능하기 때문에, 공유결합형 산화방지제라 할지라도 새로운 고분자를 중합하는 기술이나 반응기가 필요하지 않으며, 도입될 기능성기의 양을 비교적 간단하게 조절할 수 있다.In addition, since the antioxidant of the present invention can immediately impart functionality to an existing polymer only by melting and mixing, even a covalently bonded antioxidant does not require a new polymer polymerization technique or reactor, and the amount of the functional group to be introduced can be reduced. It can be adjusted relatively easily.
또한, 본 발명의 산화방지제가 촉매나 용매 사용 없이 대상 고분자 사슬에 C-H 삽입 반응을 통하여 결합되어 반응시간이 짧고 연속적인 용융상 공정이 적용 가능하여 간단하면서도 높은 경제성을 확보할 수 있다.In addition, since the antioxidant of the present invention is bonded to the target polymer chain through a C-H insertion reaction without using a catalyst or solvent, the reaction time is short and a continuous melt phase process can be applied, so that simple and high economic efficiency can be secured.
이 도면들은 본 발명의 예시적인 실시예를 설명하는데 참조하기 위함이므로, 본 발명의 기술적 사상을 첨부한 도면에 한정해서 해석하여서는 아니 된다.
도 1a는 제조예 1에 따라 제조된 OH-AO의 FT-IR 분석 결과를 나타낸 것이다.
도 1b는 제조예 1에 따라 제조된 OH-AO의 1H-NMR 분석 결과를 나타낸 것이다.
도 1c는 제조예 1에 따라 제조된 OH-AO의 13C-NMR 분석 결과를 나타낸 것이다.
도 2a는 제조예 2에 따라 제조된 CF-AO의 FT-IR 분석 결과를 나타낸 것이다.
도 2b는 제조예 2에 따라 제조된 CF-AO의 1H-NMR 분석 결과를 나타낸 것이다.
도 3a는 실시예 1에 따라 제조된 AF-AO의 FT-IR 분석 결과를 나타낸 것이다.
도 3b는 실시예 1에 따라 제조된 AF-AO의 1H-NMR 분석 결과를 나타낸 것이다.
도 4는 폴리프로필렌, 실시예 2 및 메탄올 침전 처리한 실시예 2의 FT-IR 분석 결과를 나타낸 것이다.
도 5는 폴리프로필렌, 실시예 2 및 비교예 2의 TGA 분석 결과를 나타낸 것이다.Since these drawings are for reference in explaining exemplary embodiments of the present invention, the technical spirit of the present invention should not be construed as being limited to the accompanying drawings.
Figure 1a shows the results of FT-IR analysis of OH-AO prepared according to Preparation Example 1.
Figure 1b shows the results of 1 H-NMR analysis of OH-AO prepared according to Preparation Example 1.
Figure 1c shows the results of 13 C-NMR analysis of OH-AO prepared according to Preparation Example 1.
Figure 2a shows the results of FT-IR analysis of CF-AO prepared according to Preparation Example 2.
Figure 2b shows the results of 1 H-NMR analysis of CF-AO prepared according to Preparation Example 2.
Figure 3a shows the results of FT-IR analysis of AF-AO prepared according to Example 1.
Figure 3b shows the results of 1 H-NMR analysis of AF-AO prepared according to Example 1.
Figure 4 shows the FT-IR analysis results of polypropylene, Example 2 and Example 2 treated with methanol precipitation.
5 shows the TGA analysis results of polypropylene, Example 2 and Comparative Example 2.
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 첨부된 도면을 참조하여 본 발명의 실시예를 상세히 설명하도록 한다.Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention.
그러나, 이하의 설명은 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명을 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다.However, the following description is not intended to limit the present invention to specific embodiments, and in describing the present invention, if it is determined that the detailed description of related known technologies may obscure the gist of the present invention, the detailed description will be omitted. .
본원에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.Terms used herein are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the terms "comprise" or "having" are intended to indicate that there is a feature, number, step, operation, component, or combination thereof described in the specification, but one or more other features or It should be understood that the presence or addition of numbers, steps, operations, elements, or combinations thereof is not precluded.
또한, 이하에서 사용될 제1, 제2 등과 같이 서수를 포함하는 용어는 다양한 구성요소들을 설명하는데 사용될 수 있지만, 상기 구성요소들은 상기 용어들에 의해 한정되지는 않는다. 상기 용어들은 하나의 구성요소를 다른 구성요소로부터 구별하는 목적으로만 사용된다. 예를 들어, 본 발명의 권리 범위를 벗어나지 않으면서 제1 구성요소는 제2 구성요소로 명명될 수 있고, 유사하게 제2 구성요소도 제1 구성요소로 명명될 수 있다.Also, terms including ordinal numbers such as first and second to be used below may be used to describe various components, but the components are not limited by the terms. These terms are only used for the purpose of distinguishing one component from another. For example, a first element may be termed a second element, and similarly, a second element may be termed a first element, without departing from the scope of the present invention.
또한, 어떤 구성요소가 다른 구성요소 상에 "형성되어" 있다거나 "적층되어" 있다고 언급된 때에는, 그 다른 구성요소의 표면 상의 전면 또는 일면에 직접 부착되어 형성되어 있거나 적층되어 있을 수도 있지만, 중간에 다른 구성요소가 더 존재할 수도 있다고 이해되어야 할 것이다.In addition, when a component is referred to as being “formed” or “layered” on another component, it may be formed or laminated directly on the front or one side of the surface of the other component, but intermediate It should be understood that other components may be further present.
이하, 본 발명의 유기물에 공유결합으로 연결되는 산화방지제 및 그의 제조방법에 대하여 상세히 설명하기로 한다. 다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구범위의 범주에 의해 정의될 뿐이다.Hereinafter, an antioxidant covalently linked to an organic material of the present invention and a method for preparing the same will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.
사슬의 어느 하나의 말단에 아지도 포르메이트기(
또한, 상기 산화방지제가 아래 구조식 1로 표시되는 것일 수 있다.In addition, the antioxidant may be represented by Structural Formula 1 below.
[구조식 1][Structural Formula 1]
상기 구조식 1에서,In Structural Formula 1,
R1은 원자가 결합 또는 C1 내지 C30의 알킬렌기이고,R 1 is a valence bond or a C1 to C30 alkylene group;
R2 및 R3은 서로 같거나 다르고, 각각 수소원자 또는 C1 내지 C30의 알킬기이다.R 2 and R 3 are the same as or different from each other, and each represents a hydrogen atom or a C1 to C30 alkyl group.
또한, 상기 페놀의 유도체가 2-메틸페놀, 3-메틸페놀, 2,6-디메틸페놀, 2-에틸페놀, 3-에틸페놀, 2,6-에틸페놀, 2-부틸페놀, 3-부틸페놀, 2,6-부틸페놀, 2-sec-부틸페놀, 3-sec-부틸페놀, 2,6-di-sec-부틸페놀, 2-tert-부틸페놀, 3-tert-부틸페놀, 2,6-di-tert-부틸페놀, 2-이소프로필페놀, 3-이소프로필페놀, 2,6-디이소프로필페놀, 2-이소부틸페놀, 3-이소부틸페놀, 2,6-디이소부틸페놀, 2-메틸-6-에틸페놀, 2-메틸-6-이소프로필페놀, 2-메틸-6-부틸페놀, 2-메틸-6-sec-부틸페놀, 2-메틸-6-tert-부틸페놀, 2-메틸-6-이소부틸페놀, 2-에틸-6-에틸페놀, 2-에틸-6-이소프로필페놀, 2-에틸-6-부틸페놀, 2-에틸-6-sec-부틸페놀, 2-에틸-6-tert-부틸페놀, 2-에틸-6-이소부틸페놀, 2-부틸-6-에틸페놀, 2-부틸-6-이소프로필페놀, 2-부틸-6-부틸페놀, 2-부틸-6-sec-부틸페놀, 2-부틸-6-tert-부틸페놀 및 2-부틸-6-이소부틸페놀로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있고, 바람직하게는 2,6-di-tert-부틸페놀을 포함할 수 있다. In addition, the derivatives of the phenol are 2-methylphenol, 3-methylphenol, 2,6-dimethylphenol, 2-ethylphenol, 3-ethylphenol, 2,6-ethylphenol, 2-butylphenol, 3-butylphenol , 2,6-butylphenol, 2-sec-butylphenol, 3-sec-butylphenol, 2,6-di-sec-butylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 2,6 -di-tert-butylphenol, 2-isopropylphenol, 3-isopropylphenol, 2,6-diisopropylphenol, 2-isobutylphenol, 3-isobutylphenol, 2,6-diisobutylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-isopropylphenol, 2-methyl-6-butylphenol, 2-methyl-6-sec-butylphenol, 2-methyl-6-tert-butylphenol, 2-methyl-6-isobutylphenol, 2-ethyl-6-ethylphenol, 2-ethyl-6-isopropylphenol, 2-ethyl-6-butylphenol, 2-ethyl-6-sec-butylphenol, 2 -Ethyl-6-tert-butylphenol, 2-ethyl-6-isobutylphenol, 2-butyl-6-ethylphenol, 2-butyl-6-isopropylphenol, 2-butyl-6-butylphenol, 2- It may contain at least one selected from the group consisting of butyl-6-sec-butylphenol, 2-butyl-6-tert-butylphenol and 2-butyl-6-isobutylphenol, preferably 2,6- di-tert-butylphenol.
본 발명의 다른 하나의 측면에 따르면, 폴리올레핀 및 상기 산화방지제가 공유결합한 안정화된 폴리올레핀이 제공된다.According to another aspect of the present invention, a stabilized polyolefin in which a polyolefin and the antioxidant are covalently bonded is provided.
또한, 상기 산화방지제의 아지드(-N3)는 질소(N2)가 빠지면서 상기 폴리올레핀의 C-H 결합의 수소와 치환되어 공유결합한 것일 수 있다.In addition, the azide (-N 3 ) of the antioxidant may be covalently bonded by substitution with hydrogen of the CH bond of the polyolefin while nitrogen (N 2 ) is missing.
또한, 상기 안정화된 폴리올레핀이 아래 구조식 2로 표시되는 것일 수 있다.In addition, the stabilized polyolefin may be represented by Structural Formula 2 below.
[구조식 2][Structural Formula 2]
상기 구조식 2에서,In Structural Formula 2,
R1은 원자가 결합 또는 C1 내지 C30의 알킬렌기이고,R 1 is a valence bond or a C1 to C30 alkylene group;
R2 및 R3은 서로 같거나 다르고, 각각 수소원자 또는 C1 내지 C30의 알킬기이고,R 2 and R 3 are the same as or different from each other, and each represents a hydrogen atom or a C1 to C30 alkyl group;
R4 및 R5는 서로 같거나 다르고, 각각 수소원자 또는 C1 내지 C30의 알킬기이고,R 4 and R 5 are the same as or different from each other, and each represents a hydrogen atom or a C1 to C30 alkyl group;
m 및 n은 각각 독립적으로 반복단위의 반복수이다.m and n are each independently the repeating number of the repeating unit.
또한, 상기 폴리올레핀이 폴리프로필렌, 고밀도 폴리에틸렌, 중밀도 폴리에틸렌, 저밀도 폴리에틸렌, 초고분자 폴리에틸렌, 폴리1-부텐, 폴리부타디엔, 폴리스티렌, 폴리이소프렌, 폴리이소부틸렌, 폴리클로로프렌, 폴리1-펜텐, 폴리이소펜텐, 폴리1-헥센, 폴리1-헵텐, 폴리이소헵텐, 폴리1-노넨, 폴리1-데켄, 폴리비닐시클로헥산, 폴리터부틸에틸렌, 폴리다이엔, 에틸렌-α-올레핀 공중합체, 에틸렌-프로필렌 공중합체(EPR), 에틸렌-프로필렌-디엔 러버(EPDM), 스티렌 부타디엔 스티렌 공중합체(SBS), 스티렌 부타디엔 러버(SBR, styrene butadiene rubber), 입체규칙성 스티렌 부타디엔 러버(stereospecific SBR, stereospecific styrene butadiene rubber), 스티렌 부타디엔 스티렌 공중합체, 폴리클로로프렌 러버(CR, polychloroprene rubber), 시스-클로로부타디엔 러버(cis-chlorobutadiene rubber), 아크릴로니트릴 부타디엔 러버(NBR, acrylonitrile butadiene rubber), 부타디엔 러버(BR, butadiene rubber), 이소프렌 러버(IR, isoprene rubber), 이소부틸렌 이소프렌 러버(IIR, isobutylene isoprene rubber, butyl rubber) 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.In addition, the polyolefin is polypropylene, high density polyethylene, medium density polyethylene, low density polyethylene, ultra high molecular weight polyethylene, poly1-butene, polybutadiene, polystyrene, polyisoprene, polyisobutylene, polychloroprene, poly1-pentene, polyiso Pentene, poly1-hexene, poly1-heptene, polyisoheptene, poly1-nonene, poly1-decene, polyvinylcyclohexane, polyterbutylethylene, polydiene, ethylene-α-olefin copolymer, ethylene- Propylene copolymer (EPR), ethylene-propylene-diene rubber (EPDM), styrene butadiene styrene copolymer (SBS), styrene butadiene rubber (SBR), stereospecific styrene butadiene rubber (stereospecific SBR) rubber), styrene butadiene styrene copolymer, polychloroprene rubber (CR, polychloroprene rubber), cis-chlorobutadiene rubber, acrylonitrile butadiene rubber (NBR, butadiene rubber), butadiene rubber (BR) rubber), isoprene rubber (IR, isoprene rubber), isobutylene isoprene rubber (IIR, isobutylene isoprene rubber, butyl rubber), and at least one selected from the group consisting of copolymers thereof.
본 발명은 (a) 반응식 1에 따라 구조식 11로 표시되는 화합물과 환원제를 반응시켜 구조식 12로 표시되는 화합물을 제조하는 단계; (b) 반응식 2에 따라 상기 구조식 12로 표시되는 화합물과 구조식 13으로 표시되는 화합물을 반응시켜 구조식 14로 표시되는 화합물을 제조하는 단계; 및 (c) 반응식 3에 따라 상기 구조식 14로 표시되는 화합물과 구조식 15로 표시되는 알칼리금속 아지드를 반응시켜 구조식 1로 표시되는 산화방지제를 제조하는 단계;를 포함하는 산화방지제의 제조방법을 제공한다.The present invention comprises (a) preparing a compound represented by Structural Formula 12 by reacting a compound represented by Structural Formula 11 with a reducing agent according to Scheme 1; (b) reacting the compound represented by Structural Formula 12 with the compound represented by Structural Formula 13 according to Scheme 2 to prepare a compound represented by Structural Formula 14; and (c) reacting the compound represented by Structural Formula 14 with an alkali metal azide represented by Structural Formula 15 according to Scheme 3 to prepare an antioxidant represented by Structural Formula 1; do.
[반응식 1][Scheme 1]
[반응식 2][Scheme 2]
[반응식 3][Scheme 3]
상기 반응식 1 내지 3에서, In Schemes 1 to 3 above,
R1은 원자가 결합 또는 C1 내지 C30의 알킬렌기이고,R 1 is a valence bond or a C1 to C30 alkylene group;
R2 및 R3은 서로 같거나 다르고, 각각 수소원자 또는 C1 내지 C30의 알킬기이고, R 2 and R 3 are the same as or different from each other, and each represents a hydrogen atom or a C1 to C30 alkyl group;
R'은 서로 같거나 다르고, 각각 할로겐 원자, 
X1 내지 X3은 서로 같거나 다르고, 각각 할로겐 원자이고,X 1 to X 3 are the same as or different from each other, and each is a halogen atom;
M은 알칼리금속이다.M is an alkali metal.
상기 할로겐 원자가 불소원자, 염소원자, 브롬원자 또는 요오드 원자이고, 바람직하게는 염소원자이다.The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom.
상기 구조식 13으로 표시되는 화합물은 포스겐(phosgene), 트리포스겐(triphosgene) 및 디페닐 카보네이트(diphenyl carbonate)로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있고, 바람직하게는 트리포스겐을 포함할 수 있다.The compound represented by Structural Formula 13 may include at least one selected from the group consisting of phosgene, triphosgene and diphenyl carbonate, preferably triphosgene. .
또한, 상기 환원제가 수소화 리튬알루미늄(LiAlH4), 소듐 보로하이드라이드(NaBH4), 리튬 보로하이드라이드(LiBH4) 및 디보란(B2H6)으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있고, 바람직하게는 수소화 리튬알루미늄을 포함할 수 있다.In addition, the reducing agent may include at least one selected from the group consisting of lithium aluminum hydride (LiAlH 4 ), sodium borohydride (NaBH 4 ), lithium borohydride (LiBH 4 ), and diborane (B 2 H 6 ). and may preferably include lithium aluminum hydride.
또한, 상기 산화방지제의 제조방법이 -50 내지 70 ℃의 온도에서 수행될 수 있고, 바람직하게는 -20 내지 25 ℃의 온도에서 수행될 수 있다. 상기 산화방지제의 제조방법이 -50 ℃ 미만의 온도에서 수행될 경우 각 단계의 반응이 진행되지 않아 구조식 1로 표시되는 산화방지제를 합성하기 어려우므로 바람직하지 않고, 70 ℃를 초과할 경우 부산물이 형성될 수 있어 바람직하지 않다. In addition, the method for preparing the antioxidant may be performed at a temperature of -50 to 70 °C, preferably at a temperature of -20 to 25 °C. When the method for preparing the antioxidant is performed at a temperature of less than -50 ° C, it is not preferable because it is difficult to synthesize the antioxidant represented by Structural Formula 1 because the reaction of each step does not proceed, and by-products are formed when the temperature exceeds 70 ° C. It can be undesirable
또한, 상기 환원제가 상기 구조식 11로 표시되는 화합물 100 몰을 기준으로 25 내지 400 몰 포함할 수 있다. 상기 환원제가 25 몰 미만으로 포함될 경우 상기 구조식 11로 표시되는 화합물의 산화가 잘 진행되지 않아 상기 구조식 12로 표시되는 화합물의 생성 수율이 떨어지므로 바람직하지 않고, 400 몰을 초과할 경우 필요 이상으로 과다하게 투입되어 경제적으로 비효율적이므로 바람직하지 않다In addition, the reducing agent may include 25 to 400 moles based on 100 moles of the compound represented by Structural Formula 11. When the reducing agent is included in an amount of less than 25 mol, the oxidation of the compound represented by Structural Formula 11 does not proceed well and the yield of the compound represented by Structural Formula 12 decreases, which is undesirable. When the amount exceeds 400 mol, it is excessively excessive. It is not desirable because it is economically inefficient
또한, 상기 구조식 13으로 표시되는 화합물이 상기 구조식 12로 표시되는 화합물 100 몰을 기준으로 10 내지 100 몰 포함할 수 있다. 상기 구조식 13으로 표시되는 화합물이 10 몰 미만으로 포함될 경우 상기 구조식 14로 표시되는 화합물의 생성 수율이 떨어지므로 바람직하지 않고, 100 몰을 초과할 경우 필요 이상으로 과다하게 투입되어 경제적으로 비효율적이므로 바람직하지 않다. In addition, 10 to 100 moles of the compound represented by Structural Formula 13 may be included based on 100 moles of the compound represented by Structural Formula 12. When the compound represented by the structural formula 13 is included in an amount of less than 10 moles, the yield of the compound represented by the structural formula 14 decreases, which is undesirable, and when the amount exceeds 100 moles, the amount of the compound represented by the structural formula 13 is excessively added, making it economically inefficient. not.
또한, 상기 알칼리금속 아지드가 상기 구조식 14로 표시되는 화합물 100 몰을 기준으로 50 내지 400 몰 포함할 수 있다. 상기 알칼리금속 아지드가 50 몰 미만으로 포함될 경우 상기 구조식 1로 표시되는 화합물(산화방지제)의 생성 수율이 떨어지므로 바람직하지 않고, 400 몰을 초과할 경우 필요 이상으로 과다하게 투입되어 경제적으로 비효율적이므로 바람직하지 않다. In addition, 50 to 400 moles of the alkali metal azide may be included based on 100 moles of the compound represented by Structural Formula 14. When the alkali metal azide is included in an amount of less than 50 moles, the yield of the compound (antioxidant) represented by Structural Formula 1 decreases, which is not preferable, and when it exceeds 400 moles, it is added more than necessary and is economically inefficient. don't
본 발명은 사슬의 어느 하나의 말단에 아지도 포르메이트기(
또한, 상기 반응이 C-H 삽입 반응으로 수행되고, 상기 C-H 삽입 반응이 아래 반응식 4와 같이 같이 아지도포메이트의 질소가 싱글릿 나이트렌(singlet nitrene)이 되고, 상기 싱글릿 나이트렌이 폴리올레핀의 C-H 결합의 수소와 치환되어 공유결합되는 것일 수 있다.In addition, the reaction is performed as a C-H insertion reaction, and the nitrogen of azidoformate becomes singlet nitrene as shown in Scheme 4 below, and the singlet nitrene is a C-H bond of polyolefin. It may be substituted with hydrogen of and bonded covalently.
[반응식 4][Scheme 4]
또한, 상기 산화방지제가 상기 폴리올레핀과 상기 산화방지제의 합 100 중량부를 기준으로 0.1 내지 20 중량부 포함할 수 있다. 상기 산화방지제가 0.1 중량부 미만으로 포함될 경우 산화방지제를 포함함으로써 발생하는 효과(고분자의 안정성)가 미미하여 바람직하지 않고, 20 중량부를 포함할 경우 상기 산화방지제가 과다하게 상기 폴리올레핀과 가교되어 상기 폴리올레핀의 특성을 떨어트릴 수 있어 바람직하지 않다. In addition, the antioxidant may include 0.1 to 20 parts by weight based on 100 parts by weight of the sum of the polyolefin and the antioxidant. When the antioxidant is included in an amount of less than 0.1 parts by weight, the effect (polymer stability) caused by including the antioxidant is insignificant, which is undesirable. It is undesirable because it can degrade the properties.
또한, 상기 반응이 50 내지 300 ℃의 온도에서 수행되는 것일 수 있고, 바람직하게는 80 내지 250 ℃의 온도에서 수행될 수 있다. 상기 반응이 50 ℃ 미만의 온도에서 수행될 경우 산화방지제의 아지도 포르메이트기가 분해하지 않아 C-H 삽입 반응이 일어나지 않아 본 발명의 산화방지제가 폴리올레핀에 공유결합함으로써 발생하는 효과(분산성 및 안정성)가 나타나지 않아 바람직하지 않고, 300 ℃를 초과할 경우 폴리올레핀이 산화반응으로 분해변성되거나 아지도 포르메이트기의 분해가 빠르게 일어나 니트렌-니트렌 반응을 일으켜 반응에 참여하는 반응기 수가 줄어 온도 상승에 따른 효과가 미미하여 바람직하지 않다. In addition, the reaction may be carried out at a temperature of 50 to 300 °C, preferably at a temperature of 80 to 250 °C. When the reaction is carried out at a temperature of less than 50 ° C., the azido formate group of the antioxidant does not decompose and the C-H insertion reaction does not occur, so the effect (dispersibility and stability) caused by the covalent bonding of the antioxidant of the present invention to polyolefin When the temperature exceeds 300 ℃, polyolefin is decomposed and modified by oxidation reaction or azido formate group is rapidly decomposed, resulting in a nitrene-nitrene reaction, which reduces the number of reactors participating in the reaction, resulting in the effect of temperature rise. is insignificant and undesirable.
[실시예] [Example]
이하, 본 발명의 바람직한 실시예를 들어 설명하도록 한다. 그러나 이는 예시를 위한 것으로서 이에 의하여 본 발명의 범위가 한정되는 것은 아니다.Hereinafter, a preferred embodiment of the present invention will be described. However, this is for illustrative purposes and the scope of the present invention is not limited thereby.
제조예 1: 2,6-di-tert-butyl-4-(3-hydroxypropyl)phenol(OH-AO) 합성Preparation Example 1: Synthesis of 2,6-di-tert-butyl-4-(3-hydroxypropyl)phenol (OH-AO)
3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionic Acid(COOH-AO, >98 %)는 TCI(Japan)에서 구매하였다. 질소 하에서 lithium aluminum hydride(0.607 g, 16 mmol)을 anhydrous tetrahydrofuran(THF, 10 mL)에 용해시키고 0 ℃에서 교반시켰다. Anhydrous THF(10 mL)에 용해시킨 COOH-AO(2.228 g, 8 mmol)를 LiAlH4 용액에 30분간 한 방울씩 천천히 첨가해주고, 0 ℃에서 4 시간 동안 반응시켰다. Thin Layer Chromatography(TLC)를 통해 반응의 진행과정을 관찰하였다. 4 시간 후, 반응 혼합물은 ammonium chloride(NH4Cl) 포화수용액(20 mL)과 ethyl acetate(AcOEt, 10 mL)를 사용하여 quenching 되었다. 유기층을 분리하고, hydrogen chloride(HCl)을 묽힌 수용액을 넣어 약산성으로 만들었다. 그 후, 남은 혼합물을 diethyl ether(3 x 40 mL)로 추출하였다. NaCl 포화수용액(brine)을 넣어 유기 ether 층을 분리하여 추출한 후, anhydrous magnesium sulfate(MgSO4)로 건조하고, 회전증발농축기로 용매를 증발시켜 oily crude product를 얻었다. 이렇게 얻어진 결과물을 n-hexane에 용해시킨 후, 재결정화 시켜 흰색 고체 결정인 OH-AO을 얻었다(1.716 g, yield 84%).3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionic Acid (COOH-AO, >98%) was purchased from TCI (Japan). Lithium aluminum hydride (0.607 g, 16 mmol) was dissolved in anhydrous tetrahydrofuran (THF, 10 mL) under nitrogen and stirred at 0 °C. COOH-AO (2.228 g, 8 mmol) dissolved in Anhydrous THF (10 mL) was slowly added dropwise to the LiAlH 4 solution dropwise over 30 minutes, followed by reaction at 0 °C for 4 hours. The progress of the reaction was observed through Thin Layer Chromatography (TLC). After 4 hours, the reaction mixture was quenched using a saturated aqueous solution of ammonium chloride (NH 4 Cl) (20 mL) and ethyl acetate (AcOEt, 10 mL). The organic layer was separated, and an aqueous solution diluted with hydrogen chloride (HCl) was added to make it weakly acidic. Then, the remaining mixture was extracted with diethyl ether (3 x 40 mL). The organic ether layer was separated and extracted by adding NaCl saturated aqueous solution (brine), dried with anhydrous magnesium sulfate (MgSO 4 ), and the solvent was evaporated using a rotary evaporator to obtain an oily crude product. After dissolving the obtained product in n-hexane, it was recrystallized to obtain OH-AO as a white solid crystal (1.716 g, yield 84%).
상기 제조예 1의 반응식을 아래 반응식 5에 나타내었다.The reaction scheme of Preparation Example 1 is shown in Scheme 5 below.
[반응식 5][Scheme 5]
제조예 2: 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propyl chloroformate(CF-AO) 합성Preparation Example 2: Synthesis of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propyl chloroformate (CF-AO)
Dichloromethane(CH2Cl2, 10 mL)에 상기 제조예 1에 따라 제조된 OH-AO(2.212 g, 8 mmol)을 녹인 용액에 diisopropylethylamine(1.034 g, 8 mmol)을 첨가한 후, 0 ℃, 질소 하에서 교반시켰다. 5분 후, 반응 혼합물에 triphosgene(1.187 g, 4 mmol)을 첨가한 뒤 0 ℃에서 1시간 정도 교반시키고, 상온에서 밤새 교반시켰다. TLC를 통해 반응의 진행과정을 관찰하였다. 반응 후, 차가운 물로 quenching 하고 CH2Cl2(3 x 40 mL)로 추출하였다. CH2Cl2 층은 DI-water(10 mL) 와 brine(5 mL)으로 세척하고, anhydrous MgSO4를 사용해 건조시킨 후, 회전증발농축기를 통해 용매를 제거해주었다. 얻어진 결과물은 AcOEt : hexane (1 : 10)을 사용하여 column chromatography를 통해 정제하고, 무색 오일 형태의 CF-AO를 얻었다(2.248 g, yield 86%). After adding diisopropylethylamine (1.034 g, 8 mmol) to a solution of OH-AO (2.212 g, 8 mmol) prepared according to Preparation Example 1 dissolved in dichloromethane (CH 2 Cl 2 , 10 mL), 0 ℃, nitrogen stirred under After 5 minutes, triphosgene (1.187 g, 4 mmol) was added to the reaction mixture, and the mixture was stirred at 0° C. for about 1 hour and then stirred at room temperature overnight. The progress of the reaction was observed through TLC. After the reaction, it was quenched with cold water and extracted with CH 2 Cl 2 (3 x 40 mL). The CH 2 Cl 2 layer was washed with DI-water (10 mL) and brine (5 mL), dried using anhydrous MgSO 4 , and then the solvent was removed using a rotary evaporator. The obtained product was purified through column chromatography using AcOEt : hexane (1 : 10) to obtain CF-AO in the form of a colorless oil (2.248 g, yield 86%).
상기 제조예 2의 반응식을 아래 반응식 6에 나타내었다.The reaction scheme of Preparation Example 2 is shown in Scheme 6 below.
[반응식 6][Scheme 6]
산화방지제 제조antioxidant manufacturing
실시예 1: 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propyl azidoformate(AF-AO) 합성Example 1: Synthesis of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propyl azidoformate (AF-AO)
Acetone(15 ml)에 상기 제조예 2에 따라 제조된 CF-AO(2.614 g, 8 mmol)을 녹인 용액에 DI-water(5 ml)에 녹인 sodium azide(1.042 g, 16 mmol) 용액을 0 ℃ 에서 한 방울씩 첨가하였다. 반응 혼합물은 0 ℃에서 2시간 동안 교반시켰다. TLC를 통해 반응이 끝난 것을 확인한 후, acetone을 증발시키고 증류수(20 ml)로 희석시켜 주었다. 반응 혼합물을 ethyl acetate(3 x 30 ml)로 추출하였고, 유기층은 물과 brine(5 ml)로 세척하여 주었다. Anhydrous MgSO4로 건조시키고, 용매(AcOEt)를 감압 하에서 증발시켜 노란색 오일 형태의 AF-AO를 얻었다(yield 100%).A solution of sodium azide (1.042 g, 16 mmol) dissolved in DI-water (5 ml) was added to a solution of CF-AO (2.614 g, 8 mmol) prepared according to Preparation Example 2 in acetone (15 ml) at 0 ° C. was added drop by drop. The reaction mixture was stirred at 0 °C for 2 hours. After confirming the completion of the reaction through TLC, acetone was evaporated and diluted with distilled water (20 ml). The reaction mixture was extracted with ethyl acetate (3 x 30 ml), and the organic layer was washed with water and brine (5 ml). After drying with Anhydrous MgSO 4 , the solvent (AcOEt) was evaporated under reduced pressure to obtain AF-AO in the form of a yellow oil (yield 100%).
상기 실시예 1의 반응식을 아래 반응식 7에 나타내었다.The reaction scheme of Example 1 is shown in Scheme 7 below.
[반응식 7][Scheme 7]
안정화된 폴리프로필렌 제조Manufacture of stabilized polypropylene
실시예 2Example 2
실시예 1에 따라 제조된 AF-AO(0.304 g)와 polypropylene(PP, HU300, 한화토탈, 37.696 g)을 internal melt mixer (Brabender Plasticorder 50 EHT)를 사용하여 175 ℃에서 10분 간 50 rpm으로 reactive melt mixing 하고, 실온으로 냉각시켜 실시예 2를 제조하였다.AF-AO (0.304 g) and polypropylene (PP, HU300, Hanwha Total, 37.696 g) prepared according to Example 1 were reactively reacted at 175 ° C. for 10 minutes at 50 rpm using an internal melt mixer (
비교예 1Comparative Example 1
Ethanox®310을 비교예 1로 사용하였다. 상기 Ethanox®310은 아래 구조식 3으로 표시되는 화합물이다.Ethanox®310 was used as Comparative Example 1. The Ethanox®310 is a compound represented by Structural Formula 3 below.
[구조식 3][Structural Formula 3]
비교예 2Comparative Example 2
Ethanox®310(비교예 1)(0.268 g)과 PP (37.732 g)를 Brabender melt mixer에서 175 ℃에서 10분 간 50 rpm으로 blending 하고, 실온으로 냉각시켜 비교예 2를 제조하였다. Comparative Example 2 was prepared by blending Ethanox® 310 (Comparative Example 1) (0.268 g) and PP (37.732 g) at 50 rpm for 10 minutes at 175 ° C. in a Brabender melt mixer and cooling to room temperature.
상기 실시예 2와 비교예 2의 폴리프로필렌과 산화방지제의 배합표를 아래 표 1에 정리하여 나타내었다.The polypropylene and antioxidant formulations of Example 2 and Comparative Example 2 are summarized in Table 1 below.
(UAO0.8)Example 2
(UAO0.8)
(AF-AO)Example 1
(AF-AO)
(Ethanox®310)Comparative Example 1
(Ethanox®310)
AF-AO의 히드록시 페닐(hydroxyl phenyl, HP) group은 1개이고 Ethanox®310의 HP group은 4개 존재하기 때문에 화학적 의미의 비교를 위해, HP 그룹의 몰수를 AF-AO는 0.912 mmol, Ethanox®310는 0.912의 1/4배인 0.228 mmol로 맞추어 진행하였다.Since AF-AO has one hydroxyl phenyl (HP) group and Ethanox®310 has four HP groups, for chemical comparison, the number of moles of HP group is 0.912 mmol for AF-AO and Ethanox® 310. 310 was adjusted to 0.228 mmol, which is 1/4 times that of 0.912.
[시험예] [Test Example]
시험예 1: 산화방지제(AF-AO)의 합성 확인Test Example 1: Confirmation of synthesis of antioxidant (AF-AO)
시험예 1-1: OH-AO의 합성 확인Experimental Example 1-1: Synthesis confirmation of OH-AO
도 1a는 제조예 1에 따라 제조된 OH-AO의 FT-IR 분석 결과를 나타낸 것이고, 도 1b는 제조예 1에 따라 제조된 OH-AO의 1H-NMR 분석 결과를 나타낸 것이고, 도 1c는 제조예 1에 따라 제조된 OH-AO의 13C-NMR 분석 결과를 나타낸 것이다.Figure 1a shows the results of FT-IR analysis of OH-AO prepared according to Preparation Example 1, Figure 1b shows the results of 1 H-NMR analysis of OH-AO prepared according to Preparation Example 1, Figure 1c is It shows the result of 13 C-NMR analysis of OH-AO prepared according to Preparation Example 1.
도 1a의 FT-IR에서 1706 cm-1 부근 신축진동이 나타나지 않는 것으로 보아, COOH-AO에 있는 carbonyl group이 사라진 것을 확인할 수 있다. 그리고 3630 cm-1에서 aromatic OH의 진동, 3434 cm-1에서 aliphatic OH의 진동 및 2975 cm-1에서 Ar-CH의 진동을 관찰할 수 있다. In the FT-IR of FIG. 1a, it can be seen that the stretching vibration around 1706 cm -1 does not appear, and it can be confirmed that the carbonyl group in COOH-AO has disappeared. And vibrations of aromatic OH at 3630 cm -1 , vibrations of aliphatic OH at 3434 cm -1 , and Ar-CH vibrations at 2975 cm -1 can be observed.
도 1b의 1H-NMR에서 3.42 내지 3.37 ppm, 2.48 내지 2.45 ppm, 1.68 내지 1.63 ppm은 각각 aliphatic 영역의 CH2, CH2, CH2 그룹 양성자를 나타냈으며, 4.44 내지 4.42 ppm에서 aliphatic OH의 양성자의 triplet 신호를 관찰할 수 있다. In the 1 H-NMR of FIG. 1b, 3.42 to 3.37 ppm, 2.48 to 2.45 ppm, and 1.68 to 1.63 ppm showed protons of CH 2 , CH 2 , and CH 2 groups in the aliphatic region, respectively, and protons of aliphatic OH at 4.44 to 4.42 ppm A triplet signal of can be observed.
도 1c의 13C-NMR에서는 carbonyl carbon에 해당하는 174.4 ppm의 신호가 사라짐을 확인할 수 있다. In the 13 C-NMR of FIG. 1c, it can be confirmed that the signal of 174.4 ppm corresponding to carbonyl carbon disappears.
따라서, 도 1a 내지 1c에 따르면, OH-AO이 성공적으로 합성되었음을 알 수 있다.Therefore, according to Figures 1a to 1c, it can be seen that OH-AO was successfully synthesized.
시험예 1-2: CF-AO의 합성 확인Test Example 1-2: Confirmation of the synthesis of CF-AO
도 2a는 제조예 2에 따라 제조된 CF-AO의 FT-IR 분석 결과를 나타낸 것이고, 도 2b는 제조예 2에 따라 제조된 CF-AO의 1H-NMR 분석 결과를 나타낸 것이다.Figure 2a shows the FT-IR analysis result of CF-AO prepared according to Preparation Example 2, Figure 2b shows the 1 H-NMR analysis result of CF-AO prepared according to Preparation Example 2.
도 2a에서, 1779 cm-1의 carbonyl group 신축 진동과 3638 cm-1의 aromatic OH group의 신축진동이 나타난 것을 확인할 수 있다. In Figure 2a, it can be seen that the carbonyl group stretching vibration of 1779 cm -1 and the stretching vibration of the aromatic OH group of 3638 cm -1 appeared.
도 2b의 1H-NMR에서 6.74 ppm에서 aromatic OH의 singlet이 나타난 것을 통해 hindered phenol chloroformate(CF-AO)의 형성을 확인하였고, 남은 모든 양성자 신호는 예상 영역에서 나타났다. 또한, 도 2b에서 COOH-AO의 aliphatic OH 양성자에 해당하는 4.44 ppm의 triplet peak가 사라진 것을 확인하였다.The formation of hindered phenol chloroformate (CF-AO) was confirmed through the appearance of a singlet of aromatic OH at 6.74 ppm in 1 H-NMR of FIG. 2b, and all remaining proton signals appeared in the expected region. In addition, in FIG. 2b, it was confirmed that the triplet peak at 4.44 ppm corresponding to aliphatic OH protons of COOH-AO disappeared.
따라서, 도 2a 및 2b에 따르면, OH-AO로부터 CF-AO가 성공적으로 합성된 것을 확인할 수 있다.Therefore, according to FIGS. 2a and 2b, it can be confirmed that CF-AO was successfully synthesized from OH-AO.
시험예 1-3: AF-AO의 합성 확인Test Example 1-3: Confirmation of AF-AO synthesis
도 3a는 실시예 1에 따라 제조된 AF-AO의 FT-IR 분석 결과를 나타낸 것이고, 도 3b는 실시예 1에 따라 제조된 AF-AO의 1H-NMR 분석 결과를 나타낸 것이다.Figure 3a shows the FT-IR analysis result of AF-AO prepared according to Example 1, Figure 3b shows the 1 H-NMR analysis result of AF-AO prepared according to Example 1.
도 3a에서, 3642 cm-1의 aromatic OH 신축진동, 2957 cm-1의 Ar-CH 신축진동, 2186 cm-1의 azide 신축진동 및 1730 cm-1의 carbonyl group 신축진동을 관찰할 수 있다. 특히, 도 3a의 2186 cm-1 absorption peak는 AF-AO의 azide functional group을 나타내는 중요한 신호이다.In Figure 3a, aromatic OH stretching vibration of 3642 cm -1 , Ar-CH stretching vibration of 2957 cm -1 , azide stretching vibration of 2186 cm -1 and carbonyl group stretching vibration of 1730 cm -1 can be observed. In particular, the 2186 cm −1 absorption peak in FIG. 3a is an important signal representing the azide functional group of AF-AO.
도 3b를 참고하면, 1H-NMR 신호 또한 예상 영역에서 나타난 것을 확인할 수 있다.Referring to FIG. 3B , it can be confirmed that the 1 H-NMR signal also appeared in the expected region.
따라서, 도 3a 및 3b에 따르면, CF-AO로부터 AF-AO가 성공적으로 합성된 것을 확인할 수 있다.Accordingly, according to FIGS. 3a and 3b , it can be confirmed that AF-AO was successfully synthesized from CF-AO.
시험예 2: PP와 산화방지제의 공유결합 형성 확인Test Example 2: Confirmation of Covalent Bond Formation between PP and Antioxidant
도 4는 폴리프로필렌(HU300), 실시예 2(UAO0.8) 및 메탄올 침전 처리한 실시예 2(UAO0.8(P))의 FT-IR 분석 결과를 나타낸 것이다.Figure 4 shows the FT-IR analysis results of polypropylene (HU300), Example 2 (UAO0.8) and Example 2 (UAO0.8(P)) treated with methanol precipitation.
도 4에 따르면, 실시예 2(UAO0.8)에서 1700 cm-1 부근 carbonyl 신축진동을 관찰할 수 있었으며, 2200 cm-1 부근 azide 진동은 사라진 것으로 보아, azidoformate기의 열분해 반응이 일어난 것을 확인할 수 있다.According to FIG. 4, in Example 2 (UAO0.8), carbonyl stretching vibration was observed around 1700 cm -1 , and the azide vibration around 2200 cm -1 disappeared, confirming that the thermal decomposition reaction of the azidoformate group occurred. there is.
실시예 2에서 폴리프로필렌과 산화방지제가 단순 blending인지 C-H 삽입 반응이 일어나 공유결합이 생겼는지 여부를 확인하기 위해, 실시예 1의 산화방지제(AF-AO)가 methanol에 녹는 것을 확인하고 실시예 2(UAO0.8)를 xylene(137 ℃)에 녹인 후, methanol에 침전시킨 후 43 ℃에서 건조시켜 UAO0.8(P)를 얻었다.In Example 2, in order to determine whether polypropylene and antioxidants were simply blended or whether a C-H insertion reaction occurred and a covalent bond was formed, it was confirmed that the antioxidant (AF-AO) of Example 1 was soluble in methanol, and Example 2 ( UAO0.8) was dissolved in xylene (137 ℃), precipitated in methanol and dried at 43 ℃ to obtain UAO0.8 (P).
상기 메탄올 침전 처리한 실시예 2(UAO0.8(P))에서도 1700 cm-1 부근 carbonyl 신축진동을 관찰할 수 있다. Carbonyl stretching vibration around 1700 cm -1 can be observed in Example 2 (UAO0.8 (P)) subjected to the methanol precipitation treatment.
따라서, 본 발명에 따른 산화방지제(AF-AO)가 폴리프로필렌과 물리적 혼합이 아닌 화학적으로 공유결합되어 있는 것을 확인할 수 있다.Therefore, it can be confirmed that the antioxidant (AF-AO) according to the present invention is chemically covalently bonded with polypropylene rather than physically mixed.
시험예 3: 산화방지제를 포함하는 폴리프로필렌의 열적 안정화 특성 확인Test Example 3: Confirmation of Thermal Stabilization Characteristics of Polypropylene Containing Antioxidant
도 5는 폴리프로필렌(HU300), 실시예 2(UAO0.8) 및 비교예 2(UA0.7)의 TGA 분석 결과를 나타낸 것이다. 상세하게는 산화방지제가 공유결합으로 연결된 샘플의 열적 안정화 특성이 향상되었는지 확인하기 위해, PP(HU300)를 일반 산화방지제인 Ethanox®310와 혼합한 비교예 2(UE0.7)와, 실시예 1(AF-AO)과 reactive melt mixing한 실시예 2(UAO0.8)의 TGA를 측정하여 비교하였다.5 shows the TGA analysis results of polypropylene (HU300), Example 2 (UAO0.8) and Comparative Example 2 (UA0.7). In detail, in order to check whether the thermal stabilization properties of the samples in which the antioxidants were covalently linked were improved, Comparative Example 2 (UE0.7) in which PP (HU300) was mixed with Ethanox®310, a general antioxidant, and Example 1 TGA of (AF-AO) and reactive melt mixing Example 2 (UAO0.8) were measured and compared.
도 5에 따르면, 일반 PP(HU300)의 경우 367 ℃에서 5 wt% loss가 일어나는 것을 확인할 수 있다. 또한, Ethanox®310을 blending한 비교예 2(UE0.7)의 경우 400 ℃, 실시예 1(AF-AO)과 reactive melt mixing한 실시예 2(UAO0.8)의 경우 410 ℃에서 5 wt% loss가 일어나는 것을 관찰할 수 있다.According to FIG. 5, in the case of general PP (HU300), it can be confirmed that 5 wt% loss occurs at 367 ° C. In addition, in the case of Comparative Example 2 (UE0.7) blended with Ethanox®310 at 400 ° C, and in the case of Example 1 (AF-AO) and Example 2 (UAO0.8) mixed with reactive melt, 5 wt% at 410 ° C. loss can be observed.
5 wt% loss가 일어나는 것을 기준으로 할 때, 비교예 2(UE0.7)의 경우 기존 PP보다 33 ℃ 높은 온도까지 견딜 수 있었고, 실시예 2(UAO0.8)는 비교예 2(UE0.7)보다는 10 ℃ 더 높은 온도, PP(HU300) 보다는 43 ℃ 높은 온도까지 안정화되는 것을 확인하였다. Based on the occurrence of 5 wt% loss, in the case of Comparative Example 2 (UE0.7), it was able to withstand up to 33 ℃ higher temperature than the existing PP, and Example 2 (UAO0.8) was comparable to Comparative Example 2 (UE0.7 ) and 43 ℃ higher than PP (HU300).
따라서 PP에 AF-AO가 삽입된 실시예 2(UAO0.8)가 PP나 PP에 Ethanox®310를 blending 한 비교예 2(UE0.7) 보다 더 높은 열적 안정화 효과를 보이는 것을 확인할 수 있다. Therefore, it can be confirmed that Example 2 (UAO0.8) in which AF-AO was inserted into PP showed a higher thermal stabilization effect than Comparative Example 2 (UE0.7) in which PP or PP was blended with Ethanox®310.
본 발명의 산화방지제는 비교적 높은 열적 특성을 가짐과 동시에 고분자 매트릭스에 공유결합으로 삽입되어 산화방지제의 휘발성 또한 방지되는 장점을 가지고 있다.The antioxidant of the present invention has the advantage of having relatively high thermal characteristics and at the same time preventing volatility of the antioxidant by being covalently incorporated into the polymer matrix.
본 발명의 범위는 상기 상세한 설명보다는 후술하는 특허청구범위에 의하여 나타내어지며, 특허청구범위의 의미 및 범위 그리고 그 균등 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.The scope of the present invention is indicated by the following claims rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts should be interpreted as being included in the scope of the present invention. do.
Claims (17)
상기 산화방지제가 아래 구조식 1로 표시되는 것을 특징으로 하는 산화방지제:
[구조식 1]
상기 구조식 1에서,
R1은 원자가 결합 또는 C1 내지 C30의 알킬렌기이고,
R2 및 R3은 서로 같거나 다르고, 각각 수소원자 또는 C1 내지 C30의 알킬기이다.According to claim 1,
An antioxidant characterized in that the antioxidant is represented by the following structural formula 1:
[Structural Formula 1]
In Structural Formula 1,
R 1 is a valence bond or a C1 to C30 alkylene group;
R 2 and R 3 are the same as or different from each other, and each represents a hydrogen atom or a C1 to C30 alkyl group.
상기 페놀 유도체 잔기가 2-메틸페놀, 3-메틸페놀, 2,6-디메틸페놀, 2-에틸페놀, 3-에틸페놀, 2,6-에틸페놀, 2-부틸페놀, 3-부틸페놀, 2,6-부틸페놀, 2-sec-부틸페놀, 3-sec-부틸페놀, 2,6-di-sec-부틸페놀, 2-tert-부틸페놀, 3-tert-부틸페놀, 2,6-di-tert-부틸페놀, 2-이소프로필페놀, 3-이소프로필페놀, 2,6-디이소프로필페놀, 2-이소부틸페놀, 3-이소부틸페놀, 2,6-디이소부틸페놀, 2-메틸-6-에틸페놀, 2-메틸-6-이소프로필페놀, 2-메틸-6-부틸페놀, 2-메틸-6-sec-부틸페놀, 2-메틸-6-tert-부틸페놀, 2-메틸-6-이소부틸페놀, 2-에틸-6-에틸페놀, 2-에틸-6-이소프로필페놀, 2-에틸-6-부틸페놀, 2-에틸-6-sec-부틸페놀, 2-에틸-6-tert-부틸페놀, 2-에틸-6-이소부틸페놀, 2-부틸-6-에틸페놀, 2-부틸-6-이소프로필페놀, 2-부틸-6-부틸페놀, 2-부틸-6-sec-부틸페놀, 2-부틸-6-tert-부틸페놀 및 2-부틸-6-이소부틸페놀로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것을 특징으로 하는 산화방지제.According to claim 1,
The phenol derivative residue is 2-methylphenol, 3-methylphenol, 2,6-dimethylphenol, 2-ethylphenol, 3-ethylphenol, 2,6-ethylphenol, 2-butylphenol, 3-butylphenol, 2 ,6-butylphenol, 2-sec-butylphenol, 3-sec-butylphenol, 2,6-di-sec-butylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 2,6-di -tert-butylphenol, 2-isopropylphenol, 3-isopropylphenol, 2,6-diisopropylphenol, 2-isobutylphenol, 3-isobutylphenol, 2,6-diisobutylphenol, 2- Methyl-6-ethylphenol, 2-methyl-6-isopropylphenol, 2-methyl-6-butylphenol, 2-methyl-6-sec-butylphenol, 2-methyl-6-tert-butylphenol, 2- Methyl-6-isobutylphenol, 2-ethyl-6-ethylphenol, 2-ethyl-6-isopropylphenol, 2-ethyl-6-butylphenol, 2-ethyl-6-sec-butylphenol, 2-ethyl -6-tert-butylphenol, 2-ethyl-6-isobutylphenol, 2-butyl-6-ethylphenol, 2-butyl-6-isopropylphenol, 2-butyl-6-butylphenol, 2-butyl- An antioxidant characterized by comprising at least one selected from the group consisting of 6-sec-butylphenol, 2-butyl-6-tert-butylphenol and 2-butyl-6-isobutylphenol.
상기 산화방지제의 아지드(-N3)는 질소(N2)가 빠지면서 상기 폴리올레핀의 C-H 결합의 수소와 치환되어 공유결합한 것을 특징으로 하는 안정화된 폴리올레핀.According to claim 4,
The stabilized polyolefin, characterized in that the azide (-N 3 ) of the antioxidant is substituted with hydrogen of the CH bond of the polyolefin and bonded covalently while nitrogen (N 2 ) is missing.
상기 안정화된 폴리올레핀이 아래 구조식 2로 표시되는 것을 특징으로 하는 안정화된 폴리올레핀:
[구조식 2]
상기 구조식 2에서,
R1은 원자가 결합 또는 C1 내지 C30의 알킬렌기이고,
R2 및 R3은 서로 같거나 다르고, 각각 수소원자 또는 C1 내지 C30의 알킬기이고,
R4 및 R5는 서로 같거나 다르고, 각각 수소원자 또는 C1 내지 C30의 알킬기이고,
m 및 n은 각각 독립적으로 반복단위의 반복수이다.According to claim 5,
The stabilized polyolefin, characterized in that the stabilized polyolefin is represented by the structural formula 2 below:
[Structural Formula 2]
In Structural Formula 2,
R 1 is a valence bond or a C1 to C30 alkylene group;
R 2 and R 3 are the same as or different from each other, and each represents a hydrogen atom or a C1 to C30 alkyl group;
R 4 and R 5 are the same as or different from each other, and each represents a hydrogen atom or a C1 to C30 alkyl group;
m and n are each independently the repeating number of the repeating unit.
상기 폴리올레핀이 폴리프로필렌, 고밀도 폴리에틸렌, 중밀도 폴리에틸렌, 저밀도 폴리에틸렌, 초고분자 폴리에틸렌, 폴리1-부텐, 폴리부타디엔, 폴리스티렌, 폴리이소프렌, 폴리이소부틸렌, 폴리클로로프렌, 폴리1-펜텐, 폴리이소펜텐, 폴리1-헥센, 폴리1-헵텐, 폴리이소헵텐, 폴리1-노넨, 폴리1-데켄, 폴리비닐시클로헥산, 폴리터부틸에틸렌, 폴리다이엔, 에틸렌-α-올레핀 공중합체, 에틸렌-프로필렌 공중합체(EPR), 에틸렌-프로필렌-디엔 러버(EPDM), 스티렌 부타디엔 스티렌 공중합체(SBS), 스티렌 부타디엔 러버(SBR, styrene butadiene rubber), 입체규칙성 스티렌 부타디엔 러버(stereospecific SBR, stereospecific styrene butadiene rubber), 스티렌 부타디엔 스티렌 공중합체, 폴리클로로프렌 러버(CR, polychloroprene rubber), 시스-클로로부타디엔 러버(cis-chlorobutadiene rubber), 아크릴로니트릴 부타디엔 러버(NBR, acrylonitrile butadiene rubber), 부타디엔 러버(BR, butadiene rubber), 이소프렌 러버(IR, isoprene rubber), 이소부틸렌 이소프렌 러버(IIR, isobutylene isoprene rubber, butyl rubber) 및 이들의 공중합체로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것을 특징으로 하는 안정화된 폴리올레핀.According to claim 4,
The polyolefin is polypropylene, high density polyethylene, medium density polyethylene, low density polyethylene, ultra high molecular weight polyethylene, poly1-butene, polybutadiene, polystyrene, polyisoprene, polyisobutylene, polychloroprene, poly1-pentene, polyisopentene, Poly1-hexene, poly1-heptene, polyisoheptene, poly1-nonene, poly1-decene, polyvinylcyclohexane, polyterbutylethylene, polydiene, ethylene-α-olefin copolymer, ethylene-propylene copolymer Polymer (EPR), ethylene-propylene-diene rubber (EPDM), styrene butadiene styrene copolymer (SBS), styrene butadiene rubber (SBR), stereospecific styrene butadiene rubber (SBR) , styrene butadiene styrene copolymer, polychloroprene rubber (CR), cis-chlorobutadiene rubber, acrylonitrile butadiene rubber (NBR), butadiene rubber (BR) , Isoprene rubber (IR, isoprene rubber), isobutylene isoprene rubber (IIR, isobutylene isoprene rubber, butyl rubber), and a stabilized polyolefin, characterized in that it comprises at least one member selected from the group consisting of copolymers thereof.
(b) 반응식 2에 따라 상기 구조식 12로 표시되는 화합물과 구조식 13으로 표시되는 화합물을 반응시켜 구조식 14로 표시되는 화합물을 제조하는 단계; 및
(c) 반응식 3에 따라 상기 구조식 14로 표시되는 화합물과 구조식 15로 표시되는 알칼리금속 아지드를 반응시켜 구조식 1로 표시되는 산화방지제를 제조하는 단계;를
포함하는 산화방지제의 제조방법:
[반응식 1]
[반응식 2]
[반응식 3]
상기 반응식 1 내지 3에서,
R1은 원자가 결합 또는 C1 내지 C30의 알킬렌기이고,
R2 및 R3은 서로 같거나 다르고, 각각 수소원자 또는 C1 내지 C30의 알킬기이고,
R'은 서로 같거나 다르고, 각각 할로겐 원자,
X1 내지 X3은 서로 같거나 다르고, 각각 할로겐 원자이고,
M은 알칼리금속이다.(a) preparing a compound represented by Structural Formula 12 by reacting a compound represented by Structural Formula 11 with a reducing agent according to Scheme 1;
(b) reacting the compound represented by Structural Formula 12 with the compound represented by Structural Formula 13 according to Scheme 2 to prepare a compound represented by Structural Formula 14; and
(c) preparing an antioxidant represented by Structural Formula 1 by reacting the compound represented by Structural Formula 14 with an alkali metal azide represented by Structural Formula 15 according to Scheme 3;
Method for producing an antioxidant comprising:
[Scheme 1]
[Scheme 2]
[Scheme 3]
In Schemes 1 to 3 above,
R 1 is a valence bond or a C1 to C30 alkylene group;
R 2 and R 3 are the same as or different from each other, and each represents a hydrogen atom or a C1 to C30 alkyl group;
R' are the same as or different from each other, each halogen atom,
X 1 to X 3 are the same as or different from each other, and each is a halogen atom;
M is an alkali metal.
상기 환원제가 수소화 리튬알루미늄(LiAlH4), 소듐 보로하이드라이드(NaBH4), 리튬 보로하이드라이드(LiBH4) 및 디보란(B2H6)으로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것을 특징으로 하는 산화방지제의 제조방법.According to claim 8,
Characterized in that the reducing agent includes at least one selected from the group consisting of lithium aluminum hydride (LiAlH 4 ), sodium borohydride (NaBH 4 ), lithium borohydride (LiBH 4 ) and diborane (B 2 H 6 ). Method for producing an antioxidant to be.
상기 산화방지제의 제조방법이 -50 내지 70 ℃의 온도에서 수행되는 것을 특징으로 하는 산화방지제의 제조방법.According to claim 8,
Method for producing an antioxidant, characterized in that the method for producing the antioxidant is carried out at a temperature of -50 to 70 ℃.
상기 환원제가 상기 구조식 11로 표시되는 화합물 100 몰을 기준으로 25 내지 400 몰 포함하는 것을 특징으로 하는 산화방지제의 제조방법.According to claim 8,
The method for producing an antioxidant, characterized in that the reducing agent comprises 25 to 400 mol based on 100 mol of the compound represented by the structural formula 11.
상기 구조식 13으로 표시되는 화합물이 상기 구조식 12로 표시되는 화합물 100 몰을 기준으로 10 내지 100 몰 포함하는 것을 특징으로 하는 산화방지제의 제조방법.According to claim 8,
A method for producing an antioxidant comprising 10 to 100 mol of the compound represented by Structural Formula 13 based on 100 mol of the compound represented by Structural Formula 12.
상기 알칼리금속 아지드가 상기 구조식 14로 표시되는 화합물 100 몰을 기준으로 50 내지 400 몰 포함하는 것을 특징으로 하는 산화방지제의 제조방법.According to claim 8,
A method for producing an antioxidant, characterized in that the alkali metal azide comprises 50 to 400 mol based on 100 mol of the compound represented by the structural formula 14.
포함하는 안정화된 폴리올레핀의 제조방법.An azido formate group at either end of the chain (
Method for producing a stabilized polyolefin comprising
상기 반응이 C-H 삽입 반응으로 수행되고,
상기 C-H 삽입 반응이 아래 반응식 4와 같이 같이 아지도포메이트의 질소가 싱글릿 나이트렌(singlet nitrene)이 되고, 상기 싱글릿 나이트렌이 폴리올레핀의 C-H 결합의 수소와 치환되어 공유결합되는 것을 특징으로 하는 안정화된 폴리올레핀의 제조방법:
[반응식 4]
The reaction is carried out as a CH insertion reaction,
As shown in Scheme 4 below, the CH insertion reaction is characterized in that the nitrogen of azidoformate becomes singlet nitrene, and the singlet nitrene is substituted with hydrogen of the CH bond of polyolefin to form a covalent bond. Process for preparing stabilized polyolefin:
[Scheme 4]
상기 산화방지제가 상기 폴리올레핀과 상기 산화방지제의 합 100 중량부를 기준으로 0.1 내지 20 중량부 포함하는 것을 특징으로 하는 안정화된 폴리올레핀의 제조방법.According to claim 14,
The method for producing a stabilized polyolefin, characterized in that the antioxidant comprises 0.1 to 20 parts by weight based on 100 parts by weight of the sum of the polyolefin and the antioxidant.
상기 반응이 50 내지 300 ℃의 온도에서 수행되는 것을 특징으로 하는 안정화된 폴리올레핀의 제조방법.According to claim 14,
Method for producing a stabilized polyolefin, characterized in that the reaction is carried out at a temperature of 50 to 300 ℃.
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Citations (4)
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|---|---|---|---|---|
| US3991131A (en) * | 1976-03-15 | 1976-11-09 | The Goodyear Tire & Rubber Company | Azidoformyl antioxidants |
| US4031068A (en) * | 1976-07-26 | 1977-06-21 | Uniroyal Inc. | Non-migratory sulfonyl azide antioxidants |
| JPH09316046A (en) * | 1996-05-28 | 1997-12-09 | Kuraray Co Ltd | Ethylenic aromatic compound bearing tertiary butoxycarbonylamino group and polymer thereof |
| KR20180018719A (en) * | 2015-06-15 | 2018-02-21 | 브라스켐 아메리카, 인크. | Long-chain branched polymer and manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3991131A (en) * | 1976-03-15 | 1976-11-09 | The Goodyear Tire & Rubber Company | Azidoformyl antioxidants |
| US4031068A (en) * | 1976-07-26 | 1977-06-21 | Uniroyal Inc. | Non-migratory sulfonyl azide antioxidants |
| JPH09316046A (en) * | 1996-05-28 | 1997-12-09 | Kuraray Co Ltd | Ethylenic aromatic compound bearing tertiary butoxycarbonylamino group and polymer thereof |
| KR20180018719A (en) * | 2015-06-15 | 2018-02-21 | 브라스켐 아메리카, 인크. | Long-chain branched polymer and manufacturing method |
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