JPS6353988B2 - - Google Patents
Info
- Publication number
- JPS6353988B2 JPS6353988B2 JP56100693A JP10069381A JPS6353988B2 JP S6353988 B2 JPS6353988 B2 JP S6353988B2 JP 56100693 A JP56100693 A JP 56100693A JP 10069381 A JP10069381 A JP 10069381A JP S6353988 B2 JPS6353988 B2 JP S6353988B2
- Authority
- JP
- Japan
- Prior art keywords
- tetrazole
- tert
- hydroxyphenyl
- derivative
- butyl
- 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
Links
- 230000003712 anti-aging effect Effects 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 150000003536 tetrazoles Chemical class 0.000 description 33
- -1 2-phenyl-5-(3',5'-di-methyl-4'-hydroxyphenyl)tetrazole Chemical compound 0.000 description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 14
- DOZRDZLFLOODMB-UHFFFAOYSA-N 3,5-di-tert-Butyl-4-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC(C=O)=CC(C(C)(C)C)=C1O DOZRDZLFLOODMB-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 11
- 239000005060 rubber Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012954 diazonium Substances 0.000 description 8
- 150000001989 diazonium salts Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 150000001448 anilines Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- UYGBSRJODQHNLQ-UHFFFAOYSA-N 4-hydroxy-3,5-dimethylbenzaldehyde Chemical compound CC1=CC(C=O)=CC(C)=C1O UYGBSRJODQHNLQ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 229920003049 isoprene rubber Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000001226 reprecipitation Methods 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 description 2
- OGIQUQKNJJTLSZ-UHFFFAOYSA-N 4-butylaniline Chemical compound CCCCC1=CC=C(N)C=C1 OGIQUQKNJJTLSZ-UHFFFAOYSA-N 0.000 description 2
- IMPPGHMHELILKG-UHFFFAOYSA-N 4-ethoxyaniline Chemical compound CCOC1=CC=C(N)C=C1 IMPPGHMHELILKG-UHFFFAOYSA-N 0.000 description 2
- HRXZRAXKKNUKRF-UHFFFAOYSA-N 4-ethylaniline Chemical compound CCC1=CC=C(N)C=C1 HRXZRAXKKNUKRF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 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
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000007855 nitrilimines Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- DHYHYLGCQVVLOQ-UHFFFAOYSA-N 3-bromoaniline Chemical compound NC1=CC=CC(Br)=C1 DHYHYLGCQVVLOQ-UHFFFAOYSA-N 0.000 description 1
- WMIQWIJPGVVMII-UHFFFAOYSA-N 3-butylaniline Chemical compound CCCCC1=CC=CC(N)=C1 WMIQWIJPGVVMII-UHFFFAOYSA-N 0.000 description 1
- WEZAHYDFZNTGKE-UHFFFAOYSA-N 3-ethoxyaniline Chemical compound CCOC1=CC=CC(N)=C1 WEZAHYDFZNTGKE-UHFFFAOYSA-N 0.000 description 1
- AMKPQMFZCBTTAT-UHFFFAOYSA-N 3-ethylaniline Chemical compound CCC1=CC=CC(N)=C1 AMKPQMFZCBTTAT-UHFFFAOYSA-N 0.000 description 1
- IPWGAPCYYMTTLT-UHFFFAOYSA-N 3-propylaniline Chemical compound CCCC1=CC=CC(N)=C1 IPWGAPCYYMTTLT-UHFFFAOYSA-N 0.000 description 1
- IOFKLPGWURTFMD-UHFFFAOYSA-N 3-tert-butyl-4-hydroxy-5-methylbenzaldehyde Chemical compound CC1=CC(C=O)=CC(C(C)(C)C)=C1O IOFKLPGWURTFMD-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- ARIREUPIXAKDAY-UHFFFAOYSA-N 4-butylbenzaldehyde Chemical compound CCCCC1=CC=C(C=O)C=C1 ARIREUPIXAKDAY-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- GEVILTWPAPSGDK-UHFFFAOYSA-N 4-hydroxy-2,3-dimethylbenzaldehyde Chemical compound CC1=C(C)C(C=O)=CC=C1O GEVILTWPAPSGDK-UHFFFAOYSA-N 0.000 description 1
- OAPDPORYXWQVJE-UHFFFAOYSA-N 4-propylaniline Chemical compound CCCC1=CC=C(N)C=C1 OAPDPORYXWQVJE-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 description 1
- 239000011976 maleic acid 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
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
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This invention relates to 2-substituted phenyl-5-(3',5'-di-alkyl-4'-hydroxyphenyl)tetrazole derivatives (hereinafter referred to as
It is abbreviated as "tetrazole derivative." ) and its derivatives. Polymers made of natural rubber (NR) or synthetic rubber such as butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), or acrylonitrile-butadiene-styrene resin (ABS), polyacrylonitrile, etc. Products undergo air oxidation deterioration at room temperature, thermal deterioration during heating, and oxidative deterioration in the presence of high oxygen levels. It is well known that polymer products are adversely affected by these deterioration phenomena, such as softening, hardening, or cracking. Conventionally, amine-based or phenol-based anti-aging agents have been developed as a countermeasure against this problem, but most of them have relatively small molecular weights, so they volatilize during use of polymer products. Alternatively, when it is immersed in an organic solvent such as gasoline, it is easily extracted, which has the disadvantage that its anti-aging effect is extremely diminished. Various countermeasures have been proposed in the past to compensate for these shortcomings, but all of them have advantages and disadvantages and have not yet been fully satisfactory. In view of the shortcomings of the prior art, it is an object of the present invention to improve known anti-aging agents and create a new anti-aging agent that has excellent anti-aging properties and is not extracted from polymeric products by organic solvents. The goal is to develop and provide new drugs. As a result of intensive research to achieve the above object, the inventors discovered a novel tetrazole derivative having a 3,5-di-alkyl-4-hydroxyphenyl group as a substituent, which was completely unknown until now. The present inventors have discovered that the present invention is an anti-aging agent with excellent anti-aging effects and non-extractability from polymeric products by organic solvents, and based on this knowledge, they have completed the present invention. The gist of this invention is as follows: 1. General formula [However, in the formula, R 1 and R 2 have 1 to 4 carbon atoms.
alkyl group, R 3 is hydrogen or has 1 to 4 carbon atoms
represents an alkyl group, a methoxy group, an ethoxy group, or a halogen. ] 2-substituted phenyl-5-(3',5'-
Di-alkyl-4'-hydroxyphenyl)tetrazole derivatives. 2 General formula [However, in the formula, R 1 and R 2 have 1 to 4 carbon atoms.
alkyl group, R 3 is hydrogen or has 1 to 4 carbon atoms
represents an alkyl group, a methoxy group, an ethoxy group, or a halogen. ] 2-substituted phenyl-5-(3',5'-
This is a polymer anti-aging agent consisting of a di-alkyl-4'-hydroxyphenyl)tetrazole derivative. The tetrazole derivative according to the present invention is a new compound, and representative examples thereof include 2-phenyl-5-(3',5'-di-methyl-4'-hydroxyphenyl)tetrazole, 2-phenyl-5- â(3â²â
Methyl-4'-hydroxy-5'-tert-butylphenyl)tetrazole, 2-phenyl-5-(3',
5â²-di-tert-butyl-4â²-hydroxyphenyl)
Tetrazole, 2-p-tolyl-5-(3',5'-
di-tert-butyl-4'-hydroxyphenyl)tetrazole, 2-p-methoxyphenyl-5-(3',
5â²-di-tert-butyl-4â²-hydroxyphenyl)
Tetrazole, 2-p-ethoxyphenyl-5-
(3',5'-di-tert-butyl-4'-hydroxyphenyl)tetrazole, 2-p-chlorophenyl-5
-(3',5'-di-tert-butyl-4'-hydroxyphenyl)tetrazole, 2-p-n butylphenyl-5-(3',5'-di-tert-butyl-4'-hydroxyphenyl) enyl)tetrazole, 2-m-tolyl-5-
(3',5'-di-tert-butyl-4'-hydroxyphenyl)tetrazole, 2-m-chlorophenyl-5
Examples include -(3',5'-di-tert-butyl-4'-hydroxyphenyl)tetrazole, but the present invention is not limited thereto. Next, the constituent elements of this invention will be specifically explained in detail. The tetrazole derivative according to this invention (1) is 3,
3, which is synthesized by reacting an allylsulfonylhydrazone of 5-di-alkyl-4-hydroxybenzaldehyde and a diazonium salt of an aniline derivative in a basic atmosphere;
As the allylsulfonylhydrazone of 5-di-alkyl-4-hydroxybenzaldehyde, for example, p-toluenesulfonylhydrazone of 3,5-di-methyl-4-hydroxybenzaldehyde, 3-methyl-4-hydroxy-5-tertiary p-toluenesulfonylhydrazone of butylbenzaldehyde, benzenesulfonylhydrazone of 3,5-di-tert-butyl-4-hydroxybenzaldehyde, p-toluenesulfonylhydrazone of 3,5-di-tert-butyl-4-hydroxybenzaldehyde, etc. These include, but are not limited to. Examples of diazonium salts of aniline derivatives include aniline, p-toluidine, m-toluidine, p-ethylaniline, m
-ethylaniline, p-propylaniline, m-
Propylaniline, p-butylaniline, m-butylaniline, p-anisidine, m-anisidine, p-phenetidine, m-phenetidine, p-
Examples include diazonium salts of various aniline derivatives such as chloroaniline, m-chloroaniline, p-bromoaniline, and m-bromoaniline, but are not limited thereto. In addition, examples of the basic atmosphere include, but are not limited to, organic bases such as pyridine, dimethylaniline, and diethylaniline, and alcoholic aqueous solutions of inorganic bases such as sodium hydroxide and potassium hydroxide. isn't it. The polymeric anti-aging agent comprising a tetrazole derivative according to (2) of this invention is obtained by (a) kneading into a target polymeric material, and then (b) subjecting it to heat treatment. There is no particular restriction on the polymeric material to be used in (a), and a wide variety of materials can be mentioned. For example, telekirik liquid type synthetic rubber with an average molecular weight of 500 to 8,000, or regular solid natural rubber (NR) with an average molecular weight of 8,000 or more.
and synthetic rubbers such as isoprene rubber (IR), butadiene rubber (BR), chloroprene rubber (CR), ethylene-propylene rubber (EPDM or EPM), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), or These blend rubbers, as well as diene compounds, modified polyolefins, acrylonitrile resins, maleic acid ester resins, acrylonitrile-butadiene-
These include synthetic resins such as styrene resin (ABS). The heat treatment step (b) can be carried out during heating work before normal polymer processing, during kneading or melt mixing using an internal mixer or kneading roll machine in the processing process, or during heat vulcanization. Examples include during injection molding. The characteristic values of typical tetrazole derivatives according to the present invention are shown in Table 1, and the identification values are shown in Table 2. Next, embodiments of the present invention will be described. (1) Production of tetrazole derivatives Allylsulfonium hydrazone (hereinafter referred to as "[H ãâ
It is abbreviated as. ) 1 mole and 1 mole of [H]
~10 preferably 3 to 5 organic bases, or 1 to 10 moles per mole of [H], preferably 3
0.5 to 10, preferably 1 to 4, per mole of [H] is added to an alcoholic aqueous solution in which ~6 mol of an inorganic base is dissolved, and the mixture is heated at a temperature range of -72 to 50°C, preferably -30 to 10°C. Separately prepared diazonium salt of aniline derivative* is added in an amount of 0.5 to 5 moles per mole of [H], preferably 1 to 5 moles.
A 2 molar alcoholic aqueous solution is added dropwise with stirring for a predetermined period of time, and the mixture is further stirred at the same temperature for a predetermined period of time to obtain a tetrazole derivative as crystals. *Preparation of diazonium salt of alinine derivative Per mol of specified aniline derivative [H]
0.5 to 10 moles, preferably 1 to 5 moles, in a solution dissolved in an aqueous solution of hydrochloric acid at a predetermined concentration and a predetermined amount of ethanol, add 0.5 to 5 moles of sodium nitrite per mole of [H], preferably 1 to 2 moles, in a predetermined amount of water. An aqueous solution of the diazonium salt of the aniline derivative is prepared by dropping the mixture into an aqueous solution with stirring at a temperature of 0 to 10° C. to obtain an alcoholic aqueous solution of the diazonium salt of the aniline derivative. (2) Production of a polymeric composition containing a polymeric anti-aging agent A tetrazole derivative is added to the desired polymeric material by mixing with a kneading roll machine or an internal mixer or by melt-mixing according to conventional known techniques. do. The amount added may be determined as appropriate depending on various conditions such as the type of polymer material used and the desired degree of anti-aging effect, and cannot be determined unambiguously. The proportion may be 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, per 100 parts by weight. If necessary, commonly used vulcanization accelerators, sulfur, antioxidants, plasticizers, flame retardants, fillers,
A filler and other additives can be mixed as appropriate. Next, heat treatment is performed using a predetermined heating means. The tetrazole derivative according to the present invention is converted into a nitrile imine derivative having a 3,5-di-alkyl-4-hydroxyphenyl group as a substituent, which has an anti-aging function, by heat treatment in a polymeric material. Then, the converted nitrile imine derivative can be used as C=C, -Câ¡N,
-OH, -CHO,
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ããšãæããã«ããŠããã[Formula] It was developed based on the technical idea that it can be an excellent reactive anti-aging agent because it binds to active methylene.
Therefore, when the anti-aging agent-containing polymer composition comprising the tetrazole derivative according to the present invention is used as a polymer product, the derivative having an anti-aging function does not volatilize, or the anti-aging agent does not volatilize. Since the derivative is not extracted from the composition even when it is in contact with a solvent, it has a higher It exhibits an extremely excellent feature of being able to exhibit a high degree of aging resistance as a molecular product. EXAMPLES Hereinafter, the effects of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 3,5-
0.1 mol [31.8 g] of p-toluenesulfonylhydrazone of di-methyl-4-hydroxybenzaldehyde and 400 ml of pyridine are charged and kept at a temperature of -15 to -10°C while stirring. Separately, add 0.1 mole [7.1 g] of sodium nitrite (97%) to a solution of 0.1 mole [9.3 g] of aniline dissolved in 26 ml of 35% aqueous hydrochloric acid solution and 160 ml of 50% ethanol.
An alcoholic aqueous solution of diazonium salt of aniline prepared by dissolving 40 ml of water in 40 ml of water was added dropwise while stirring at a temperature of 0 to 10°C. Add it dropwise into the flask over 3 hours while stirring. After the dropwise addition was completed, the mixture was further stirred at the same temperature for 3 hours. The precipitated crystals were separated, washed with pyridine, and dried under vacuum to obtain the desired product, 2-phenyl-5-(3',5'-di-methyl-4'-hydroxyphenyl)tetrazole. The yield and characteristic values of the obtained target product are shown in Table 1, and the identified values are shown in Table 2. Example 2 0.1 mol of p-toluenesulfonylhydrazone of 3-methyl-4-hydroxy-5-tert-butylbenzaldehyde was used instead of p-toluenesulfonylhydrazone of 3,5-di-methyl-4-hydroxybenzaldehyde in Example 1. [36.0g]
2-phenyl-5-(3'-methyl-4'-hydroxy-5'-tert-butylphenyl)tetrazole was obtained in exactly the same manner as in Example 1, except that The yield and characteristic values of the obtained tetrazole derivative are shown in Table 1, and the identification values are shown in Table 2. Examples 3 to 9 p-toluenesulfonylhydrazone of 3,5-di-tert-butyl-4-hydroxybenzaldehyde in place of p-toluenesulfonylhydrazone of 3,5-di-methyl-4-hydroxybenzaldehyde in Example 1 0.1 mole [40.2 g],
In addition, instead of aniline, a specified aniline derivative [in the case of aniline (Example 3), in the case of p-toluidine (Example 4), in the case of p-phenetidine (Example 5), in the case of p-chloroaniline (Example 6),
In the case of m-toluidine (Example 7), in the case of m-chloroaniline (Example 8), in the case of p-n butylaniline (Example 9)] Exactly the same as Example 1 except that 0.1 mol was used. Each tetrazole derivative was obtained. The yield and characteristic values of these obtained tetrazole derivatives are shown in Table-1, and the identification values are shown in Table-2. Example 10 In place of p-toluenesulfonylhydrazone of 3,5-di-methyl-4-hydroxybenzaldehyde in Example 1, 0.1 mol of benzenesulfonylhydrazone of 3,5-di-tert-butyl-4-hydroxybenzaldehyde [38.8 g] was carried out in exactly the same manner as in Example 1, to obtain 16.0 g of 2-phenyl-5-(3',5'-di-tert-butyl-4'-hydroxyphenyl)tetrazole (yield: 45.7
%) was obtained. Example 11 0.1 mol of p-toluenesulfonylhydrazone of 3,5-di-tert-butyl-4-hydroxybenzaldehyde was used instead of p-toluenesulfonylhydrazone of 3,5-di-methyl-4-hydroxybenzaldehyde in Example 1. (40.2g),
In addition, the procedure was carried out in exactly the same manner as in Example 1, except that 0.15 mol [14.0 g] of aniline, 39 ml of 35% aqueous hydrochloric acid solution, and 0.15 mol [10.7 g] of sodium nitrite (97%) were used. 19.1 g (yield 54.6%) of 5-(3',5'-di-tert-butyl-4'-hydroxyphenyl)tetrazole was obtained. Example 12 0.1 mol of p-toluenesulfonylhydrazone of 3,5-di-tert-butyl-4-hydroxybenzaldehyde was used instead of p-toluenesulfonylhydrazone of 3,5-di-methyl-4-hydroxybenzaldehyde in Example 1. [40.2g]
Also, instead of 400 ml of pyridine, add 0.4 mol [17.2 g] of sodium hydroxide (93%) to 160 ml of 90% ethanol.
2-phenyl-5-(3',5'-
4.0 g (yield: 11.5%) of di-tert-butyl-4'-hydroxyphenyl)tetrazole was obtained. Examples 13-18 In a 50 ml four-necked flask equipped with a thermometer, reflux condenser, and stirrer with a mercury seal, liquid polybutadiene [trade name: Polybd R-45HT (molecular weight approximately 2500): manufactured by Alco Chemical Co., Ltd.] 10.8 g [0.2
Mol unit], 3 ml of xylene, and Example 3~
0.01 mol of the corresponding tetrazole derivative obtained in step 8 was added to each, stirred at 160 to 170°C for 30 minutes, and then cooled to 120 to 130°C. After diluting and dissolving the resulting solution by adding 40 ml of xylene, add it little by little into 500 ml of methanol while stirring at room temperature. After stirring for another 30 minutes at room temperature, let it stand and it will settle at the bottom. Liquid rubber was obtained by decanting method. The liquid rubber obtained here was reacted with a tetrazole derivative. Furthermore, the obtained liquid rubber was dissolved in 40 ml of benzene based on the same method as above, and then reprecipitation purification was performed twice by adding it to 500 ml of methanol while stirring and precipitating it. The liquid rubber obtained here was dissolved in 40 ml of benzene, and the benzene was distilled off under reduced pressure to obtain a sticky brown liquid rubber that had reacted with the tetrazole derivative. Regarding the obtained liquid rubber, the identification value derived from the reacted corresponding tetrazole derivative and the reaction rate of each tetrazole derivative with respect to the liquid rubber were measured. The results are shown in Table-3. Comparative Example 1 Examples 13 to 18, except that 2.2 g (0.01 mol) of 2,6-di-tert-butyl-4-methylphenol was used in place of the corresponding tetrazole derivatives used in Examples 13 to 18 above. It was carried out in exactly the same manner as in 18. The results are shown in Table-3. As can be seen from Table 3, the novel tetrazole derivative according to the present invention can be chemically bonded to liquid rubber at a reaction rate of 61 to 85%, and can also be chemically bonded to liquid rubber by reprecipitation using a benzene-methanol system. In contrast, the 2,6-di-tert-butyl-4-methylphenol of the comparative example is not chemically bound to the liquid rubber and therefore cannot be extracted in the benzene-methanol system. It was confirmed that it had been completely extracted by the reprecipitation operation. Examples 19-27 Isoprene rubber [Product name: CALIFLEX IR
-307: manufactured by Ciel Chemical Co., Ltd.] To 100 parts by weight, 0.03 mol of the tetrazole derivative obtained in Examples 1 to 9, 4 parts by weight of tetramethylthiuram disulfide, and 4 parts by weight of zinc oxide were mixed using a kneading roll machine. The mixture was added and kneaded, and the kneaded product was press-vulcanized at 170°C for 15 minutes. For the obtained vulcanized rubber, acetone
The maximum oxygen absorption rate at 130°C was measured before Soxhlet extraction using a mixed solvent of 80 ml + methanol 120 ml and after extraction (24 hours under reflux) using an oxygen absorption measuring device [manufactured by Shibayama Kagaku Kikai] to determine the anti-aging effect. I looked into it. The results are shown in Table 4. Comparative Examples 2 to 3 In place of the respective corresponding tetrazole derivatives used in Examples 19 to 27 above, nothing (Comparative Example 2) or 2,6-di-tert-butyl-
The same procedure as in Examples 19 to 27 was carried out except that 6.6 g (0.03 mol) of 4-methylphenol was used (Comparative Example 3). The results are shown in Table 4. As can be seen from Table 4, the novel tetrazole derivative according to the present invention maintains its anti-aging effect even after solvent extraction of the vulcanizate to which it is added, whereas the anti-aging effect of Comparative Example 2, 6- Di-tert-butyl-4
- It is observed that the anti-aging effect of methylphenol is significantly reduced after solvent extraction of the vulcanizate to which it is added. Example 28 2-phenyl-5-(3',
5â²-di-tert-butyl-4â²-hydroxyphenyl)
3.5 g [0.01 mol] of tetrazole in nitrogen at 170
After heating and mixing at ~180°C for 30 minutes, a 0.1 mm sheet was produced using a pressure molding machine. The obtained sheet was subjected to Soxhlet extraction using acetone (under reflux).
After 72 hours), the infrared absorption spectrum of hydroxyl groups derived from the added tetrazole derivative and the reaction rate of the tetrazole derivative with this synthetic resin were measured. The results are shown in Table-5. Comparative Example 4 In place of the tetrazole derivative used in Example 28 above, 3.4 g [0.01 mol] of 2,2'-methylenebis(4-methyl-6-tert-butylphenol) was used.
The procedure was carried out in exactly the same manner as in Example 28, except that . The results are shown in Table-5. As can be seen from Table 5, the novel tetrazole derivative according to the present invention was chemically bonded to ABS resin with a reaction rate of 51.2% and could not be extracted by acetone, whereas the novel tetrazole derivative of the comparative example , 2'-methylenebis(4-methyl-6-tert-butylphenol) is not chemically bonded to the ABS resin and is therefore found to be completely extracted by acetone. Ta. As described above, 2-substituted phenyl-5-
The (3',5'-di-alkyl-4'-hydroxyphenyl)tetrazole derivative is a new compound, and as can be seen from the examples, this compound has been used as an anti-aging agent in polymeric materials. It has been revealed that when heat treated, it becomes non-extractable to organic solvents and provides excellent anti-aging effects.
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*1 In the structural formula
Claims (1)
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ãŒã«èªå°äœãããªãé«ååã®èåé²æ¢å€ã[Claims] 1. General formula [However, in the formula, R 1 and R 2 represent an alkyl group having 1 to 4 carbon atoms, and R 3 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, or a halogen. ] A 2-substituted phenyl-5-(3',5'-di-alkyl-4'-hydroxyphenyl)tetrazole derivative represented by: 2 General formula [However, in the formula, R 1 and R 2 represent an alkyl group having 1 to 4 carbon atoms, and R 3 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, or a halogen. ] A polymer anti-aging agent comprising a 2-substituted phenyl-5-(3',5'-di-alkyl-4'-hydroxyphenyl)tetrazole derivative represented by the following.
Priority Applications (1)
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JP10069381A JPS5899469A (en) | 1981-06-30 | 1981-06-30 | 2-substituted-phenyl-5-(3',5'-dialkyl-4'-hydroxyphenyl) tetrazole derivative and polymer stabilizing composition obtained by adding said derivative |
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JP10069381A JPS5899469A (en) | 1981-06-30 | 1981-06-30 | 2-substituted-phenyl-5-(3',5'-dialkyl-4'-hydroxyphenyl) tetrazole derivative and polymer stabilizing composition obtained by adding said derivative |
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JPS5899469A JPS5899469A (en) | 1983-06-13 |
JPS6353988B2 true JPS6353988B2 (en) | 1988-10-26 |
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1981
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