DE1795326A1 - Process for the production of ozone-resistant rubber articles - Google Patents
Process for the production of ozone-resistant rubber articlesInfo
- Publication number
- DE1795326A1 DE1795326A1 DE19681795326 DE1795326A DE1795326A1 DE 1795326 A1 DE1795326 A1 DE 1795326A1 DE 19681795326 DE19681795326 DE 19681795326 DE 1795326 A DE1795326 A DE 1795326A DE 1795326 A1 DE1795326 A1 DE 1795326A1
- Authority
- DE
- Germany
- Prior art keywords
- ozone
- tetrahydroquinoxaline
- carbon atoms
- methyl
- rubber
- 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.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims description 20
- 239000005060 rubber Substances 0.000 title claims description 14
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000000034 method Methods 0.000 title claims 6
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- -1 3,3,6-trimethyl-1,2,3,4-tetrahydroquinoxaline Chemical compound 0.000 claims description 5
- 229920003052 natural elastomer Polymers 0.000 claims description 5
- 229920001194 natural rubber Polymers 0.000 claims description 5
- 239000011814 protection agent Substances 0.000 claims description 5
- MESWFJSLPLHJQL-UHFFFAOYSA-N 3,3-dimethyl-2,4-dihydro-1h-quinoxaline Chemical compound C1=CC=C2NC(C)(C)CNC2=C1 MESWFJSLPLHJQL-UHFFFAOYSA-N 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- KVTRLSAIENMGBQ-UHFFFAOYSA-N 2,3,3-trimethyl-2,4-dihydro-1h-quinoxaline Chemical compound C1=CC=C2NC(C)(C)C(C)NC2=C1 KVTRLSAIENMGBQ-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- NNGSFBDCUNKGIM-UHFFFAOYSA-N 6-methyl-1,2,3,4-tetrahydroquinoxaline Chemical compound N1CCNC2=CC(C)=CC=C21 NNGSFBDCUNKGIM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OPNMXGHYRAFDMH-UHFFFAOYSA-N 2,2,3-trimethyl-1h-quinoxaline Chemical compound C1=CC=C2NC(C)(C)C(C)=NC2=C1 OPNMXGHYRAFDMH-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- OKEAMBAZBICIFP-UHFFFAOYSA-N 3-oxido-2,1,3-benzoxadiazol-3-ium Chemical compound C1=CC=CC2=[N+]([O-])ON=C21 OKEAMBAZBICIFP-UHFFFAOYSA-N 0.000 description 2
- 239000006237 Intermediate SAF Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- HORKYAIEVBUXGM-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoxaline Chemical class C1=CC=C2NCCNC2=C1 HORKYAIEVBUXGM-UHFFFAOYSA-N 0.000 description 1
- XXBQLHATYQHJQC-UHFFFAOYSA-N 1,2-dihydroquinoxaline Chemical compound C1=CC=C2N=CCNC2=C1 XXBQLHATYQHJQC-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- SXRFQDARJDXESM-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoxaline Chemical compound N1CCNC2=CC(OC)=CC=C21 SXRFQDARJDXESM-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- SDVAYLPWHJJFSO-UHFFFAOYSA-N CC1(CNC2=CC(=CCC2N1)C)C Chemical compound CC1(CNC2=CC(=CCC2N1)C)C SDVAYLPWHJJFSO-UHFFFAOYSA-N 0.000 description 1
- YRNYRGKLHOWCJJ-UHFFFAOYSA-N CC1(CNC2=CC=C(CC2N1)C)C Chemical compound CC1(CNC2=CC=C(CC2N1)C)C YRNYRGKLHOWCJJ-UHFFFAOYSA-N 0.000 description 1
- JAEVEIQBYNIEQS-UHFFFAOYSA-N CCOC1=CC=C2NCCNC2=C1 Chemical compound CCOC1=CC=C2NCCNC2=C1 JAEVEIQBYNIEQS-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 150000001204 N-oxides Chemical class 0.000 description 1
- 101150084242 NGEF gene Proteins 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 235000015111 chews Nutrition 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 150000004987 o-phenylenediamines Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/50—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to ring nitrogen atoms
- C07D241/52—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
- C08K5/3465—Six-membered rings condensed with carbocyclic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Verfahren zur Herstellung von ozonbeständigen Gummi-Artikein Die vorliegende Erfindung bezieht sich auf ozonbeständige Gummi-Artikel und Ozonschutzmittel, die für die Herstellung dieser ozonbeständigen Gummi-Artikel verwendet werden können, Aus natürlichem oder synthetischem Kautschuk durch Vulkanisation hergestellte Gebrauchsartikel bekommen bekanntlich Risse, wenn ihre Oberfläche unter mechanischer Beanspruchung steht und den Einflüssen der Atmosphäre ausgesetzt ist. Hierbei kann die mechanische Spannung sowohl zeitlich konstant (statisch) als auch periodisch (dynamisch) veränderlich sein. Ea ist bekannt, daß das in der Atmosphäre in kleinen Konzentrationen vorkommende Ozon für die Entstehung dieser Risse verantwortlich ist und daß insbesondere die Wahl der für den betreffenien Artikel verwendeten Elastomeren fUr die Beständigkeit gegner diese Art Rißbildung von großer Bedeutung ist. So sind bei spielsweise ganz oder weitgehend gesättigte lastomere, wie Siliconkautschuk oder Butylkautschuk, recht widerstandsfähig gegen solche Degradationserscheinungen. Im Gegensatz dazu si@@ gerede die Elastomer-Typen am rißenfällgsten, die in der Gummi - Industrie im größten Umfang gebraucht werden, nämlich naturkautschuk und synthetischer, ungesättigter Kautschuk wie z.B. Butadien-Sty@@ -Kautschuk.Method of Making Ozone Resistant Rubber Articles in The present Invention relates to ozone-resistant rubber articles and anti-ozone agents that can be used for the production of these ozone-resistant rubber articles, Consumer articles made from natural or synthetic rubber by vulcanization As is known, they get cracks when their surface is subjected to mechanical stress and is exposed to the influences of the atmosphere. The mechanical Voltage both constant over time (static) and periodically (dynamic) variable be. Ea is known to occur in small concentrations in the atmosphere Ozone is responsible for the formation of these cracks and that in particular the Choice of the elastomers used for the item concerned for durability opponents this type of cracking is of great importance. For example, they are whole or largely saturated lastomers, such as silicone rubber or butyl rubber, quite resistant to such degradation phenomena. In contrast to si @@ gerede the types of elastomers that are most susceptible to cracks are those in the rubber industry are used to the greatest extent, namely natural rubber and synthetic, unsaturated ones Rubber such as butadiene-sty @@ rubber.
Man sann nun die Vulkanisate aus den letztgenannten Elastomeren gegen die Ozonrißbildung schUtzen, wenn man Verbindungen der allgemeinen Formel einarbeitet, wie sie im französischen Patent 1.420.036 besehrieben sind, Jedoch ist die Schutzwirkung dieser Produkte nur gering.The vulcanizates of the last-mentioned elastomers could now be protected against ozone cracking by using compounds of the general formula incorporated, as described in the French patent 1.420.036, but the protective effect of these products is only slight.
Es wurde nun gefunden, daß sich Verbindungen der allgemeinen Formel wobei R1 Wasserstoff oder Methyl, R2 und R3 Kohlenwasserstoffreste bis zu 4 Kohlenstoffatomen, die auch zusammen einen alicyclischen Ring bilden können, und R4 und R5 Waeserstoff-oder Alkylreste mit 1 - 12 Kohlenstoffatomen oder Methoxy- oder Athoxy-Gruppen bedeuten und worin einer der Reste R4 und R5 für Wasserstoff steht, falls einer der Reste R4 und R5 für einen Alkylrest mit 2 - 12 Kohlenstoffatomen oder eine Methoxy- oder Äthoxy-Gruppe steht, in besonders guter Weise al Ozonschutzmittel für naturkautschuk und synthetischen ungesättigten Kautschuk eignen.It has now been found that compounds of the general formula where R1 is hydrogen or methyl, R2 and R3 are hydrocarbon radicals of up to 4 carbon atoms, which together can also form an alicyclic ring, and R4 and R5 are hydrogen or alkyl radicals with 1-12 carbon atoms or methoxy or ethoxy groups and in which one of the radicals R4 and R5 stand for hydrogen, if one of the radicals R4 and R5 stands for an alkyl radical with 2-12 carbon atoms or a methoxy or ethoxy group, are particularly suitable as ozone protection agents for natural rubber and synthetic unsaturated rubber.
Die durch die erfindungsgemäß verwendeten Verbindungen geschützen Gummiwaren zeigen bei statischer Prüfung größere Vorteile gegenüber solrhen, die mit Verbindungen dea oben erwähnten franzdsiechen Patentes 1 420 036 geschützt sind, d.h. der Beginn der Rißbildung wird noch stärker verzögert und das Wachstum der Risse weiter verlangsamt; ferner schü@@@ die erfindungsgemäßen Verbindungen die Gummi-Artikel auch gegen Sauerstoffangriff.Those protected by the compounds used according to the invention In static testing, rubber goods show greater advantages over solrhen with connections of the above mentioned French patent 1 420 036 are protected, i.e. the onset of cracking is delayed even more and the growth of the Cracks further slowed down; also schü @@@ the compounds according to the invention the Rubber articles also against oxygen attack.
Die erfindungsgemäß verwendeten Verbindungen lassen sich e@@@-wandfrei im Kautschuk einmischen. Es werden z. B. Dosierungen zwischen 0,1 und 5,0 Gew.-Tln., vorzugsweise zwischen 0,5 r.The compounds used according to the invention can be e @@@ - wall-free mix in the rubber. There are z. B. Dosages between 0.1 and 5.0 parts by weight., preferably between 0.5 r.
3,0 Gew.-Tln. gerechnet auf Elastomer, angewendet.3.0 parts by weight calculated on elastomer.
Die erfindungsgemäß verwendeten Ozonschutzmittel können in das zu schützende Polymere zusammen mit den üblichen Zusätae@ und somit auch in Kombination mit anderen Ozonschutzmittel eingemischt werden.The anti-ozone agents used according to the invention can be used in the to protective polymers together with the usual additives and thus also in combination mixed in with other anti-ozone agents.
Die erfindungsgemäß verwendeten Ozonschutzmittel können eingesetzt werden in Naturkautschuk und ungesättigten, aynthetischen Kautsehuken, die Doppelbindungen enthalten, so beispielsweise in Polymerisaten aus Butadien, Isopren, Ditr. butadien und ihren Homologen; ferner in Mischpolymerisaten konJugierten Diolefinen mit polymerisierbaren Vinylverbindu@@ wie z*B. Styrol, Methylstyrol, Divinylbenzol, Acrylnitril, Methacrylnitril, Acrylaten oder Methacrylaten sowie Mischpolymerisaten, die aus Isoolefinen, wie Isobutylen oder seinen Homologen, und geringen Mengen aus konjugierten Diolefinen erhalten werden. Weiterhin können solche Polymerisate geschützt werden, die aus Chlorbutadien erhalten werden, sowie Mischpolymerisate des Chlorbutadiene mit Mono- und/oder Diolefinen oder polymerisierbaren Vinylverbindungen.The anti-ozone agents used according to the invention can be used are found in natural rubber and unsaturated, synthetic chewing chews, the double bonds contained, for example in polymers of butadiene, isoprene, ditr. butadiene and their homologues; also in copolymers conjugated diolefins with polymerizable Vinyl connection @@ such as. Styrene, methylstyrene, divinylbenzene, acrylonitrile, Methacrylonitrile, acrylates or methacrylates and copolymers made from Isoolefins such as isobutylene or its homologues, and small amounts of conjugated Diolefins are obtained. Furthermore, such polymers can be protected, obtained from chlorobutadiene, as well as copolymers of chlorobutadiene with mono- and / or diolefins or polymerizable vinyl compounds.
Beispiele der erfindungsgemäß verwendeten Verbindungen enthält die Tabelle 1: Tabelle 1 3,3-Dimethyl-1,2,3,4-tetrahydrochinoxalin 3,3,6- bzw. 7-Trimethyl-1,2,3,4-tetrahydrochinoxalin 2,3,3-Trimethyl-1,2,3,4-tetrahydrochinoxalin 2,3,3,6- bzw. 7-Tetramethyl-1,2,3,4-tetrahydrochinoxalin 2,3,3,5-Tetramethyl-1,2,3,4-tetrahydrochinoxalin 2,3,3,5,7-Pentamethyl-1,2,3,4-tetrahydrochinoxalin 3-Äthyl-3-n-butyl-1,2,3,4-tetrahydrochinoxalin 3-Äthyl-3-n-butyl-6- bzw. 7-methyl-1,2,3,4-tetrahydrochinoxalin 3-Spiro-cyclohexyl-1,2,3,4-tetrahydrochinoxalin 3-Spiro-cyclohexyl-6- bzw. 7-methyl-1,2,3,4-tetrahydrochinoxalin 2-Methyl-3-spiro-cyclohexyl-1, 2, 3, 4-tetrahydrochinoxalin 3,3-Dimethyl-6- bzw. 7-tert. -butyl-1,2,3,4-tetrahydrochinoxalin 3,3-Dimethyl-6- bzw. 7-i-nonyl-1,2,3,4-tetrahydrochinoxalin 3,3-Dimethyl-6- bzw. 7-tert. -dodecyl-1,2,3,4-tetrahydrochinoxalin 3,3-Dimethyl-6- bzw. 7-methoxy-1,2,3,4-tetrahydrochinoxalin 3,3-Dimethyl-6- bzw. 7-äthoxy-1,2,3,4-tetrahydrochinoxalin Diese Verbindungen können erhalten werden1 indem man durch Addition von Enaminen bzw. Schiff'schen Basen, deren ß-Kohlenstoffatome doppelt alkyliert sind, Dihydrochinoxalin-di-N-oxide herstellt, aus denen durch katalytische Reduktion bei 20 - 30°C die N-Oxid-Sauerstoffe abreduziert, und bei 70 - 1500C anschließeud der Aminrest reduktiv abgespalten wird unter Bildung von Tetrahydrochinoxalinen. Table 1 contains examples of the compounds used according to the invention: Table 1 3,3-dimethyl-1,2,3,4-tetrahydroquinoxaline 3,3,6- or 7-trimethyl-1,2,3,4-tetrahydroquinoxaline 2, 3,3-trimethyl-1,2,3,4-tetrahydroquinoxaline 2,3,3,6- or 7-tetramethyl-1,2,3,4-tetrahydroquinoxaline 2,3,3,5-tetramethyl-1, 2,3,4-tetrahydroquinoxaline 2,3,3,5,7-pentamethyl-1,2,3,4-tetrahydroquinoxaline 3-ethyl-3-n-butyl-1,2,3,4-tetrahydroquinoxaline 3-ethyl -3-n-butyl-6- and 7-methyl-1,2,3,4-tetrahydroquinoxaline, 3-spiro-cyclohexyl-1,2,3,4-tetrahydroquinoxaline, 3-spiro-cyclohexyl-6 and 7, respectively -methyl-1,2,3,4-tetrahydroquinoxaline 2-methyl-3-spiro-cyclohexyl-1, 2, 3, 4-tetrahydroquinoxaline 3,3-dimethyl-6- or 7-tert. -butyl-1,2,3,4-tetrahydroquinoxaline 3,3-dimethyl-6- or 7-i-nonyl-1,2,3,4-tetrahydroquinoxaline 3,3-dimethyl-6- or 7-tert . -dodecyl-1,2,3,4-tetrahydroquinoxaline 3,3-dimethyl-6- or 7-methoxy-1,2,3,4-tetrahydroquinoxaline 3,3-dimethyl-6- or 7-ethoxy-1 , 2,3,4-tetrahydroquinoxaline These compounds can be obtained1 by adding enamines or Schiff's bases, the ß-carbon atoms of which are doubly alkylated, to produce dihydroquinoxaline di-N-oxides - 30 ° C the N-oxide oxygen is reduced, and at 70 - 1500C the amine residue is subsequently split off reductively with the formation of tetrahydroquinoxalines.
Die Verbindungen können auch durch Kondensation von o-Phenylendiaminen mit entsprechenden #-Halogenketonen zu Dihydrochiroxalinen und anschließende katalytische Reduktion erhalten werden. beispiel 1: Folgende Mischungen vom Typ Autoreifenlauffläche wurden auf dem Laborwalzwerk hergestellt: Ölverstreckter Styrol-Butadien- 100,0 Gew. -Tle.The compounds can also be obtained by condensation of o-phenylenediamines with the corresponding # -halogen ketones to give dihydrochiroxalines and subsequent catalytic reduction. Example 1: The following mixtures of the car tire tread type were produced on the laboratory rolling mill: Oil-extended styrene-butadiene 100.0 wt.
Kautschuk (37,5 Gew.-Tle. Öl auf 100,0 Gew.-Tle. Elastomer) Zinkoxid
5,0 ISAF-Ruß 55,0 " Mineralölweichmacher 4,0 " Paraffin 0,6 " Stearinsaure 2,0 I1
2-Benzothiazyl-N-cyclohexyl- 1,3 " sulfenamid schwefel 1,6 " Ozonschutzmittel (s.w.u.)
0 bsw. '2,0 Von diesen Mischungen wurden 0,4 x 4,5 x 4,5 cm bzw. 0,4 x 4,5 x 5,5
cm große prüfkörper vulkanisiert (Preßvulkanisation: 30 Minuten bei 151°C). Die
Prüfkörper wurden dann in einen Kunststoffrabmen so eingespannt, daß an der Oberfläche
Dehnungen von Jeweils 10, 20, 35 und 60 % resulierten. Die so gebogenen Prüfkörper
wurden in Südrichtung und ohne Abdeckung bewettert. In bestimmten, in der weiter
unten stehenden Tabelle angegebenen Abstand wurde die Rißbildung bewertet, und zwar
sowohl die Gesamtzahl der mit freiem Auge sichtbaren Risse als auch deren durchschnittliche
Länge gemäß folgendem Schema: Zehl der Risse Durchschnittliche Länge der Risse kein
Riß 1 - 3 Risse 0 ohne Befund 0 4 9 Risse 1 Risse eben sichtbar, 10 - 27 Risse 2
bis 1 mm 1 28 - 81 Risse 4 1 - 3 mm 2 8@ - 243 Risse 5 3 - 8 mm 3 @@ Risse 6 über
8 = 4
In den folgenden Tabellen sind die beiden Bewertungen du@
einen senkrechten Strich getrennt. Die Bewertung der Rißzahl steht stets zuerst.
a) ohne Zusatz
ISAF-Ruß 48,2 " Zinkoxid 5,0 n Mineralölweichmacher 4,0 Stearinsäure
3,0 Paraffin 0,6 Schwefel 2,2 n 2-Benzthiazyl-N-cyclohexyl-sulfenamid 0,6 Ozonschutzmittel
(s.w.u.) O bzw. 2,0 Von diesen Mischungen wurden Prüfkörper, wie in Beispiel 1 beschrieben,
vulkanisiert (Preßvulkanisation: 25 Minuten bei 143°C). Die Prüfbedingungen waren
wiederum wie in Beispiel 1 desgleichen erfolgte die Auswertung der Rißbildung analog
de@ Beispiel 1. a) ohne Zusatz
C11H16N2 (176) N ber. 15,92 ngef. 15,9
Das erhaltene
Produkt ist ein Gemisch bestehend aus 3,3-dimethyl-6-methyl-tetrahydro-chinoxalin
und 3, 3-dimethyl-7 methyl-tetrahydro-chinoxalin. Das Gemisch wird durch Chromatographie
in seine beiden Bestandteile aufgetrennt. In analoger Weise werden die in der Tabelle
zusammengestellten Verbindungen aus den entsprechenden Ausgangsmaterialien gewonnen:
Die Temperatur steigt auf 25 0C und gleichzeitig erfolgt Löeung.The temperature rises to 25 ° C. and dissolution takes place at the same time.
Nach 12 Stunden sind 100 g 2-Cyclohexyl-2-methyl-3,3-dimethyldihydrochinoxalin-di-N-oxid auskristallisiert. Die roten Kristalle schmelzen nach dem Umlösen aus Methanol von 129 -131°C. After 12 hours, 100 g of 2-cyclohexyl-2-methyl-3,3-dimethyldihydroquinoxaline di-N-oxide have crystallized out. The red crystals melt after dissolving in methanol at 129-131 ° C.
Ber. C = 67,2 H = 8,31 N = 13,95 Gef. C s 67,2 H z 8,6 N ~ 13,95.Ber. C = 67.2 H = 8.31 N = 13.95 Fd. C s 67.2 H z 8.6 N ~ 13.95.
Analog wird mit dem entsprechend substituierten Benzofuroxan das Ausgangsmaterial für IV gewonnen: Fp: 147 - 148° Rote Kristalle Beispiel 4: a) Zu einer Suspension von 33 g (0,3 Mol) O-Phenylendiamin in 150 ml Methanol gibt man 36 g (0,3 Mol) 2-Chlor-2-methylbutanon- (3) und erhitzt 4 Stunden zum Sieden. Anschließend kühlt man ab, gibt 20 ml 45 %ige wässrige NaOH-Löoung und 150 ml Wasser hinzu, saugt den ausgefallenen Niederschlag ab und wäscht mit Methanol/Wasser im Volumenverhältnis 1:1.The starting material for IV is obtained analogously with the correspondingly substituted benzofuroxan: Melting point: 147-148 ° Red crystals Example 4: a) 36 g (0.3 mol) of 2-chloro-2-methylbutanone are added to a suspension of 33 g (0.3 mol) of O-phenylenediamine in 150 ml of methanol (3) and heated to boiling for 4 hours. The mixture is then cooled, 20 ml of 45% strength aqueous NaOH solution and 150 ml of water are added, the precipitate which has separated out is filtered off with suction and washed with methanol / water in a volume ratio of 1: 1.
Man erhält 39 g (75 s der Theorie) 2,3,3-Trimethyl-3,4-dihydrochinoxalin als beigefarbene Kristalle, die nach dem Umlösen aus Benzol/Leichtbenzin bei 143 - 1480C schmelzen. 39 g (75 s of theory) of 2,3,3-trimethyl-3,4-dihydroquinoxaline are obtained as beige crystals, which after dissolving from benzene / light gasoline at 143 - Melting 1480C.
Analyse: C11 H14 N2 (174,2) berechnet: C 75,8 H 8,1 N 16,1 gefunden: C 75,7 H 8,2 N 16,1 b) Man gibt 20 g Raney-Nickel B" zu einer Lösung von 61 g 2,3,3-Trimethyl-3,4-dihydrochinoxalin in 300 ml Tetrahydro furan und reduziert im Autoklaven bei 1100C mit Wasserstoff. Analysis: C11 H14 N2 (174.2) calculated: C 75.8 H 8.1 N 16.1 found: C 75.7 H 8.2 N 16.1 b) 20 g of Raney nickel B ″ are added to a solution of 61 g of 2,3,3-trimethyl-3,4-dihydroquinoxaline in 300 ml tetrahydrofuran and reduced in an autoclave at 1100C with hydrogen.
Anschließend wird der Katalysator abfiltriert, das Lösung mittel wird im Vakuum abdestilliert und der ölige Rückstand in Leichtbenzin gelöst. Nach kurzem Stehen scheiden eich Kristalle ab, die abgesaugt und mit Leichtbenzin gewaschen werden. Man erhält 30 g 2,3,3-Trimethyl-1,2,3,4-tetrahydrochinoxalin als gelbliche Kristalle, die bei 65-670C schmelzen. The catalyst is then filtered off and the solution is medium is distilled off in vacuo and the oily residue is dissolved in light gasoline. To After a short period of standing, crystals separate out, which are suctioned off and washed with light gasoline will. 30 g of 2,3,3-trimethyl-1,2,3,4-tetrahydroquinoxaline are obtained as yellowish Crystals that melt at 65-670C.
Das Produkt ist identisch mit 2,3,3-Trimethyl-1,2,3,4-tetrahydrochinoxalin (Substanz Nr. III), das nach Beispiel 3 hergestellt wurde. The product is identical to 2,3,3-trimethyl-1,2,3,4-tetrahydroquinoxaline (Substance No. III), which was prepared according to Example 3.
Claims (6)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681795326 DE1795326C3 (en) | 1968-09-13 | 1968-09-13 | Process for the production of ozone-resistant rubber articles |
| ES371364A ES371364A1 (en) | 1968-09-13 | 1969-09-10 | Tetrahydroquinoxaline derivatives |
| US856796A US3661905A (en) | 1968-09-13 | 1969-09-10 | Tetrahydroquinoxaline derivatives |
| CS6200A CS161093B2 (en) | 1968-09-13 | 1969-09-11 | |
| FR6931088A FR2018055A1 (en) | 1968-09-13 | 1969-09-12 | |
| PL13379569A PL80198B1 (en) | 1968-09-13 | 1969-09-12 | |
| NL6913937.A NL156694B (en) | 1968-09-13 | 1969-09-12 | PROCESS FOR PREPARING TETRAHYDROQUINOXALINS FOR PROTECTING RUBBER AGAINST OZONE, PROCESS FOR PROTECTING RUBBER AGAINST OZONE, AND FORMED PREPARATION, WHOLLY OR PARTIALLY PROTECTED FROM RUBBER. |
| GB41353/69A GB1285060A (en) | 1968-09-13 | 1969-09-15 | Tetrahydroquinoxalines and their use as anti-ozonants |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681795326 DE1795326C3 (en) | 1968-09-13 | 1968-09-13 | Process for the production of ozone-resistant rubber articles |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1795326A1 true DE1795326A1 (en) | 1972-01-05 |
| DE1795326B2 DE1795326B2 (en) | 1974-09-26 |
| DE1795326C3 DE1795326C3 (en) | 1975-05-15 |
Family
ID=5708143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19681795326 Expired DE1795326C3 (en) | 1968-09-13 | 1968-09-13 | Process for the production of ozone-resistant rubber articles |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE1795326C3 (en) |
| PL (1) | PL80198B1 (en) |
-
1968
- 1968-09-13 DE DE19681795326 patent/DE1795326C3/en not_active Expired
-
1969
- 1969-09-12 PL PL13379569A patent/PL80198B1/pl unknown
Also Published As
| Publication number | Publication date |
|---|---|
| PL80198B1 (en) | 1975-08-30 |
| DE1795326C3 (en) | 1975-05-15 |
| DE1795326B2 (en) | 1974-09-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C3 | Grant after two publication steps (3rd publication) | ||
| E77 | Valid patent as to the heymanns-index 1977 | ||
| 8330 | Complete disclaimer |