MXPA97003995A - Stabilization of organic peroxide with deó-dicarbonilo or a-dicetone cicl compounds - Google Patents
Stabilization of organic peroxide with deó-dicarbonilo or a-dicetone cicl compoundsInfo
- Publication number
- MXPA97003995A MXPA97003995A MXPA/A/1997/003995A MX9703995A MXPA97003995A MX PA97003995 A MXPA97003995 A MX PA97003995A MX 9703995 A MX9703995 A MX 9703995A MX PA97003995 A MXPA97003995 A MX PA97003995A
- Authority
- MX
- Mexico
- Prior art keywords
- carbon atoms
- phenyl
- peroxide
- alkyl containing
- peroxydicarbonate
- Prior art date
Links
- 150000001451 organic peroxides Chemical class 0.000 title claims abstract description 24
- 150000001875 compounds Chemical class 0.000 title claims description 17
- 238000011105 stabilization Methods 0.000 title description 4
- -1 peroxy compound Chemical class 0.000 claims abstract description 76
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 38
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 33
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 73
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 58
- 125000000217 alkyl group Chemical group 0.000 claims description 53
- XYXGFHALMTXBQX-UHFFFAOYSA-L carboxylatooxy carbonate Chemical class [O-]C(=O)OOC([O-])=O XYXGFHALMTXBQX-UHFFFAOYSA-L 0.000 claims description 46
- 150000002978 peroxides Chemical class 0.000 claims description 31
- 229910052736 halogen Inorganic materials 0.000 claims description 19
- 150000002367 halogens Chemical class 0.000 claims description 19
- OMPJBNCRMGITSC-UHFFFAOYSA-N Incidol Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 239000003381 stabilizer Substances 0.000 claims description 14
- OSWDNIFICGLKEE-UHFFFAOYSA-N 2-acetylcyclopentan-1-one Chemical compound CC(=O)C1CCCC1=O OSWDNIFICGLKEE-UHFFFAOYSA-N 0.000 claims description 13
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 claims description 11
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 11
- YRKCREAYFQTBPV-UHFFFAOYSA-N Acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- OEKATORRSPXJHE-UHFFFAOYSA-N 2-acetylcyclohexan-1-one Chemical compound CC(=O)C1CCCCC1=O OEKATORRSPXJHE-UHFFFAOYSA-N 0.000 claims description 6
- FGSGHBPKHFDJOP-UHFFFAOYSA-N ethyl 2-oxocyclohexane-1-carboxylate Chemical compound CCOC(=O)C1CCCCC1=O FGSGHBPKHFDJOP-UHFFFAOYSA-N 0.000 claims description 6
- NZZIMKJIVMHWJC-UHFFFAOYSA-N Dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 claims description 4
- JHZPNBKZPAWCJD-UHFFFAOYSA-N ethyl 2-oxocyclopentane-1-carboxylate Chemical compound CCOC(=O)C1CCCC1=O JHZPNBKZPAWCJD-UHFFFAOYSA-N 0.000 claims description 4
- FFVHHWOJYFCNJP-UHFFFAOYSA-N ethyl 4-methyl-2-oxocyclohexane-1-carboxylate Chemical compound CCOC(=O)C1CCC(C)CC1=O FFVHHWOJYFCNJP-UHFFFAOYSA-N 0.000 claims description 4
- OLIMLCAPOJLCSD-UHFFFAOYSA-N (2-butan-2-yl-4-methyl-3-oxopentanoyl) 2-butan-2-yl-4-methyl-3-oxopentaneperoxoate Chemical compound CCC(C)C(C(=O)C(C)C)C(=O)OOC(=O)C(C(C)CC)C(=O)C(C)C OLIMLCAPOJLCSD-UHFFFAOYSA-N 0.000 claims description 3
- CRPTXKKKIGGDBX-UHFFFAOYSA-N (Z)-but-2-ene Chemical group [CH2]C=CC CRPTXKKKIGGDBX-UHFFFAOYSA-N 0.000 claims description 3
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 claims description 3
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 claims description 3
- 125000003890 2-phenylbutyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- ZQMIGQNCOMNODD-UHFFFAOYSA-N Diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- ZGPBOPXFOJBLIV-UHFFFAOYSA-N butoxycarbonyloxy butyl carbonate Chemical compound CCCCOC(=O)OOC(=O)OCCCC ZGPBOPXFOJBLIV-UHFFFAOYSA-N 0.000 claims description 3
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- CIISBNCSMVCNIP-UHFFFAOYSA-N cyclopentane-1,2-dione Chemical compound O=C1CCCC1=O CIISBNCSMVCNIP-UHFFFAOYSA-N 0.000 claims description 3
- LOGSONSNCYTHPS-UHFFFAOYSA-N cyclopentane-1,3-dione Chemical compound O=C1CCC(=O)C1 LOGSONSNCYTHPS-UHFFFAOYSA-N 0.000 claims description 3
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- CWINGZLCRSDKCL-UHFFFAOYSA-N ethoxycarbonyloxy ethyl carbonate Chemical compound CCOC(=O)OOC(=O)OCC CWINGZLCRSDKCL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000005394 methallyl group Chemical group 0.000 claims description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N Cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N Cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 2
- AKUHVUBQELUSIY-UHFFFAOYSA-N butan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)C AKUHVUBQELUSIY-UHFFFAOYSA-N 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 230000000979 retarding Effects 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 12
- OACYKCIZDVVNJL-UHFFFAOYSA-N 3-Methyl-1,2-cyclopentanedione Chemical compound CC1CCC(=O)C1=O OACYKCIZDVVNJL-UHFFFAOYSA-N 0.000 claims 2
- ITFSHNDTMCETFP-UHFFFAOYSA-N (3,5-diethyl-5-methylheptanoyl) 3,5-diethyl-5-methylheptaneperoxoate Chemical compound CCC(C)(CC)CC(CC)CC(=O)OOC(=O)CC(CC)CC(C)(CC)CC ITFSHNDTMCETFP-UHFFFAOYSA-N 0.000 claims 1
- RRVYBPVLSILURP-UHFFFAOYSA-N 3-Ethyl-1,2-cyclopentanedione Chemical compound CCC1CCC(=O)C1=O RRVYBPVLSILURP-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000000654 additive Substances 0.000 description 43
- 230000000996 additive Effects 0.000 description 43
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 38
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 14
- XYIBRDXRRQCHLP-UHFFFAOYSA-N Ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 12
- 201000008739 coronary artery disease Diseases 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- JJOYCHKVKWDMEA-UHFFFAOYSA-N ethyl cyclohexanecarboxylate Chemical compound CCOC(=O)C1CCCCC1 JJOYCHKVKWDMEA-UHFFFAOYSA-N 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 7
- 238000007792 addition Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 235000015096 spirit Nutrition 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000001419 dependent Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000000087 stabilizing Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PMJHHCWVYXUKFD-UHFFFAOYSA-N penta-1,3-diene Chemical compound CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SDKQRNRRDYRQKY-UHFFFAOYSA-N Dioxacarb Chemical compound CNC(=O)OC1=CC=CC=C1C1OCCO1 SDKQRNRRDYRQKY-UHFFFAOYSA-N 0.000 description 2
- 101700049241 MCDP Proteins 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N Tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 239000006069 physical mixture Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-Dichloroethene Chemical compound ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-Methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 1
- FZERHIULMFGESH-UHFFFAOYSA-N Acetanilide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N Dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethylsuccinimide Chemical compound CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N Nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N Phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N Sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N Vinyl bromide Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- NVNPRIOOIIFZJH-UHFFFAOYSA-M [O-]C(=O)OOC(=O)OC1=CC=CC=C1 Chemical class [O-]C(=O)OOC(=O)OC1=CC=CC=C1 NVNPRIOOIIFZJH-UHFFFAOYSA-M 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- UGAPHEBNTGUMBB-UHFFFAOYSA-N acetic acid;ethyl acetate Chemical compound CC(O)=O.CCOC(C)=O UGAPHEBNTGUMBB-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-M carbonochloridate Chemical compound [O-]C(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-M 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000002596 correlated Effects 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 1
- 230000004059 degradation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000008079 hexane Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- SQHSUOBKWACYNG-UHFFFAOYSA-N phenoxycarbonyloxy phenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OOC(=O)OC1=CC=CC=C1 SQHSUOBKWACYNG-UHFFFAOYSA-N 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001340 slower Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- UATJOMSPNYCXIX-UHFFFAOYSA-N symmetric Trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UATJOMSPNYCXIX-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
The present invention relates to organic peroxide compositions containing a cyclic compound-dicarbonyl or alpha-diketone, to retard the decomposition rate of the peroxy compound
Description
STABILIZATION OF ORGANIC PEROXIDE WITH COMPOSITIONS OF β-DICARBONYL OR α-DICETONE CYCLIC The present invention relates to organic peroxide compositions and more specifically to peroxydicarbonate and diacyl peroxide compositions, wherein a β-dicarbonyl compound or a cyclic α-diketone compound It has been added to retard the decomposition rate of the peroxide compound. Organic peroxides such as peroxydicarbonates and diacylperoxides are useful as free radical initiators in the polymerization or copolymerization of ethylenically unsaturated monomers. For example, organic peroxides are employed as initiators in the polymerization of vinyl halides, such as vinyl chloride or vinyl bromide; vinylidene halides such as vinylidene chloride; and other compounds containing polymerizable unsaturated units. The products of this well-known polymerization process have extensive commercial applications. The polymerization of vinyl halides or the copolymerization of vinyl halides with vinylidene halides is usually carried out in an aqueous medium, ie emulsion, solution or suspension polymerization. In these polymerizations, the monomer or monomer mixture is dispersed in water in the presence of a surfactant and subsequently the polymerization is initiated with an organic peroxide. This is a well-known reaction that has been widely reported. All organic peroxides are by nature harmful materials. Its usefulness depends on its ability to decompose into free radicals, illustrated by the following reaction: RO-OR '? RO * + R'O * The speed of this decomposition reaction at any given temperature depends on the structure of R and R '. The decomposition reaction is exothermic. If exothermic decomposition were to occur during production, storage or seizure, when the peroxides are in a concentrated form, excessive pressure development and / or fire or explosion may result. Consequently, many organic peroxides must be kept refrigerated. There have been several reports in recent years of the retardation of the decomposition rate of organic peroxides. The Journal of the American Chemical Sosiety (Journal of the American Chemical Society), Volume 72, pages 1254 to 1263 (1950), describes for example the use of ethyl acetoacetate, iodine, trinitrobenzene, acetanilide, nitro ethane, phenol, peroxide of hydrogen and tetralin, to retard the decomposition rate of diisopropyl peroxydicarbonate.
The patent of the U.S.A. No. 4,515,929 (1935) reports aqueous dispersions of organic peroxides including peroxy dicarbonates, which are stabilized against decomposition by the addition of diphenyl peroxydicarbonate or di (substituted alkyl) phenyl peroxydicarbonates. The patent of the U.S.A. No. 4,552,682 (1985) describes the use of phenolic antioxidants to retard the rate of degradation of aqueous organic peroxide dispersions. The use of phenolic antioxidants is undesirable because they result in discoloration. The patent of the U.S.A. No. 5,155,192 (1992) describes the use of organic hydroperoxides, for example terbutyl hydroperoxide, to retard the decomposition rate of peroxy dicarbonates. Research Disclosure, April 1995, on page 275, reports the thermal stabilization of dialkyl peroxydicarbonates, using unsaturated nitriles or unsaturated acetylenic compounds. The present invention relates to the use of certain non-peroxide compounds, which are effective to retard the decomposition of organic peroxides such as peroxydicarbonates and diacyl peroxides. Thus, one aspect of the present invention is a composition containing an organic peroxide compound selected from the group consisting of peroxydicarbonate and diacyl peroxide compounds and at least one cyclic alpha-diketone or β-dicarbonyl compound that slows down of peroxide decomposition. Another aspect of the present invention is the method for stabilizing a peroxydicarbonate or diacyl peroxide against decomposition, which comprises adding a β-dicarbonyl compound or a cyclic α-diketone compound in an amount effective to achieve stabilization. In particular, β-dicarbonyl compounds useful in the present invention include those of the formulas I, II and III:
R5-C (0) -CHR6-C (0) -R7 (III)
wherein m is 1-5, n is 1-6, i is 0-1, x is 0-2n, and is 0-2m, R1 is alkyl containing 1 to 22 carbon atoms, phenyl or phenyl substituted with one or more than alkyl containing 1 to 22 carbon atoms, halogen and hydroxy and Ra can be hydrogen wherein i is zero, R- * is alkyl having 1 to 22 carbon atoms, phenyl or phenyl substituted with one or more alkyl that contains 1 to 22 carbon atoms, halogen and hydroxy and when x is greater than
1, each occurrence of R2 may be the same or different and may be on the same or different ring carbon atoms; R3 is hydrogen, alkyl containing 1 to 22 carbon atoms, acyl containing 2 to 22 carbon atoms, phenyl or phenyl substituted with one or more of alkyl containing 1 to
22 carbon atoms, halogen and hydroxy; R * is alkyl containing 1 to 22 carbon atoms, phenyl or phenyl substituted with one or more of alkyl containing 1 to 22 carbon atoms, halogen and hydroxy and when y is greater than 1, each occurrence of R * may be same or different and can be in the same or different ring carbon atoms; R5 is hydrogen, alkyl having 1 to 22 carbon atoms, phenyl or phenyl substituted with one or more of alkyl containing 1 to 22 carbon atoms, halogen and hydroxy; R6 is hydrogen or alkyl containing 1 to 22 carbon atoms, phenyl or phenyl substituted with one or more of alkyl containing 1 to 22 carbon atoms, halogen and hydroxy; or R6 is -C (0) 0R8 or -C (0) R8 wherein RB is alkyl containing 1 to 22 carbon atoms; and R7 is phenyl or alkyl containing 1 to 22 carbon atoms. Cyclic -dicetone compounds useful in the present invention include formula (IV):
(R1),
wherein n, x and R2 are defined as with above. The present invention relates to compositions containing an organic peroxide, which is a peroxydicarbonate or a diacyl peroxide, and at least one β-dicarbonyl stabilizing compound or a cyclic α-diketone stabilizing compound for retarding the decomposition rate of the peroxide compound. ß-Dicarbonyl compounds useful in the present invention may be one of the following general formulas:
R! - C (O) - CHR * - C (O) - R (III)
In formula (I), n is 1-6, and preferably 3-5; x is zero up to 2n and i is 0-1; and R1 is phenyl, substituted phenyl or alkyl containing 1 to 22 carbon atoms and preferably 1 to 5 carbon atoms. The phrase "substituted phenyl" refers to phenyl substituted by alkyl containing 1 to 22 carbon atoms, halogen (ie, fluorine, chlorine, bromine and / or iodine), and / or hydroxy, or with any two or more of These groups. That is, when two or more of these substituents are present, they may be the same or different. The group R2 can be phenyl, substituted phenyl or alkyl containing 1 to 22 carbon atoms and preferably 1 to 5 carbon atoms.
In the formula (II), it is 1-5 and preferably 2-4, and it is zero up to 2m and R3 can be hydrogen, phenyl or substituted phenyl. Alternatively, R3 may be alkyl containing 1 to 22 carbon atoms and preferably 1 to 5 carbon atoms, or R3 may be acyl containing 2 to 22 carbon atoms. The substituent R * can be phenyl or substituted phenyl or alkyl containing 1 to 22 carbon atoms and preferably 1 to 5 carbon atoms. In the formula (III), Rs can be hydrogen, phenyl or substituted phenyl, or Rs can be alkyl containing 1 to 22 carbon atoms and preferably 1 to 5 carbon atoms. R7 can be phenyl or R7 can be alkyl containing 1 to 22 carbon atoms and preferably 1 to 5 carbon atoms. The group R6 can be hydrogen, phenyl or substituted phenyl or it can be alkyl containing 1 to 22 carbon atoms and preferably 1 to 5 carbon atoms. Also, R6 may be -C (0) 0R8 or -C (0) Rβ; in these cases, R8 is alkyl containing 1 to 22 carbon atoms and preferably 1 to 5 carbon atoms. Cyclic α-diketone compounds useful in the present invention are of the following general formula (IV):
In formula (IV) n, x and R2 are defined as above with respect to formula (I). In all cases the alkyl substituents can be straight chain cycloalkyl or cycloalkylalkyl; branched The cycloalkyl structure in the last two cases can optionally be substituted with alkyl. Preferred moieties useful in the present invention include cyclic ketone carboxylate compounds of Formula (I) such as ethyl-2-cyclopentanone carboxylate (wherein n is 3, i is 1, x is 0, and R 1 is ethyl), ethyl- 2-cyclohexanone carboxylate (where n is 4, i is 1, x is 0, and R1 is ethyl), methyl-2-cycloheptanone carboxylate (where n is 5, i is 1, x is 0, and R1 is methyl) ), and ethyl-4-methyl-2-cyclohexanone-1-carboxylate (wherein n is 4, i is 1, x is 1, R1 is ethyl and R2 is 4-methyl). Other preferred embodiments of Formula (I) useful in the present invention include cyclic β-diketones wherein one of the carbonyl groups is contained in a cyclic structure such as 2-acetylcyclopentanone (where n is 3, i is O, x is O, and R1 is methyl) and 2-acetyl ciciohexanone (wherein n is 4, i is 0, x is 0, and R1 is methyl). Preferred moieties useful in the present invention include compounds of Formula (II) such as 1,3-cyclohexanedione (m is 3, and is 0, and R 3 is H) and 1,3-cyclopentanedione (is 2, and is 0, and R3 is H). Additional preferred embodiments useful in the present invention include compounds of Formula (III).
Examples of these compounds include 2,4-pentadione (wherein Rs is methyl, R6 is H, and R7 is methyl) and dibenzoylmethane (R5 and
R7 is phenyl and R6 is -H). ß-dicarbonyl compound of the formulas (I), (II) or
(III) are commercially available and / or can be synthesized from commercially available starting materials by the use of familiar procedures to a person of ordinary skill in the art. Still more preferred embodiments useful in the present invention include compounds of Formula (IV) such as 3-methyl-1,2-cyclopentadione (wherein n is 3, x is 1, and R 2 is 3-methyl); 3-ethyl-l, 2-cyclopentanedione (wherein n is 3, x is 1 and R ** is 3-ethyl); 1,2-cyclohexanedione (where n is 4 and x is 0) and 1,2-cyclopentandione (where n is 3 and x is zero). Cyclic α-diketone compounds of the Formula (IV) are commercially available and / or can be synthesized from commercially available raw materials by the use of familiar procedures to a person skilled in the art. The amount of cyclic α-diketone or β-dicarbonyl for use in the compositions and methods of the present invention is an amount sufficient to retard the decomposition rate of the peroxide compound. The preferred amount of cyclic α-diketone or β-dicarbonyl is a concentration of 0.2 to 5.0% by weight of the peroxydicarbonate or diacyl peroxide present. The exact amount will vary depending on both the peroxide compound and the cyclic β-dicarbonyl or α-diketone used and the conditions under which the peroxide composition is exposed. The cyclic α-diketone can, if desired, be used in solution in an appropriate solvent. Suitable solvents for the cyclic α-diketone can be selected from alcohols, glycols and esters; an example is propylene glycol. Peroxide compounds with which this invention is particularly useful, are of the general structural formula (V): R '- (0) cC (0) -0-0-C (0) - (0) c-Rxo (V) wherein each c is 0 or 1, and R * and R ** ° each may be an aliphatic, cycloaliphatic or aromatic group with 1 to 22 carbon atoms, preferably 2 to 8 carbon atoms. When the subscripts c are zero, the compound is a diacyl peroxide and when the subscripts c are one, the compound is a peroxydicarbonate. R9 and R10 can be branched or unbranched, substituted or unsubstituted alkyl, alkenyl, cycloalkyl or aromatic groups. Examples of groups R9 and R10 include phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, isobutyl, hexyl, octyl, neopentyl, 2-ethylhexyl, capryl, lauryl, myristyl, cetyl, stearyl, allyl, methallyl, crotyl, cyclohexyl, 4-t-butylcyclohexyl , 4-t-amylcyclohexyl, benzyl, 2-phenylethyl, 2-phenylbutyl, alpha-carbethoxyethyl, β-methoxyethyl, 2-phenoxyethyl, 2-methoxyphenyl, 3-methoxyphenyl, 2-ethoxyethyl, 2-ethoxyphenyl, 3-methoxybutyl, -carbamyloxyethyl, 2-chloroethyl, 2-nitrobutyl, and 2-nitro-2-ethylpropyl. Specific examples of peroxydicarbonates include diethyl peroxydicarbonate, di-n-butyl peroxydicarbonate, disobbutylperoxydicarbonate and di-4-tert-butylcyclohexyl peroxydicarbonate. Preferably, the peroxydicarbonate is di-sec-butylperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate or diisopropyl peroxydicarbonate. Specific examples of diacyl peroxides include benzoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, diacetyl peroxide and di (3,5,5-trimethylhexanoyl) peroxide.
The peroxide compound may be symmetrical or asymmetric, ie R9 and R10 may be the same or different. The peroxide may be a homogeneous mixture containing symmetric peroxides, asymmetric peroxides such as isopropyl-sec-butyl-peroxydisarbonate, or 2-methylpropionyl-3-methylpentanoyl peroxide or a mixture of symmetric and asymmetric peroxides such as diisopropyl peroxydicarbonate mixtures, sec-butylperoxydicarbonate and isopropyl-sec-butyl-peroxydicarbonate as described in the US patent No. 4,269,726. The peroxydicarbonate compounds and diacyl peroxide compounds can be synthesized by conventional family techniques to a person of ordinary skill in the art. Peroxydicarbonates are typically prepared by reacting the corresponding alkyl chloroformate with aqueous sodium peroxide at low temperatures, 0 to 20 ° C. See U.S. Pat. No. 2,370,588 and the Journal of the American Chemical Society, Volume 72, page 1254 (1950). Diacyl peroxides are typically made from acid chlorides using synthetic techniques familiar to a person with ordinary skill in the art. Preferably, the peroxydicarbonates and diacyl peroxides with which this invention is useful include those which are liquids a? "C and most preferably a liquid at -5 ° C. Peroxydicarbonates and diacyl peroxides which are liquids haeta -20 ° are further preferred. C. The present invention is especially applicable to aqueous dispersions of peroxydicarbonates and diacyl peroxides which are useful as initiators in the polymerization of free radicals of ethylenically unsaturated materials, particularly in an aqueous medium, for example emulsion or suspension polymerization. it is prepared by dispersing it in water with a suitable dispersing aid, for example a surfactant or emulsifying agent Surfactants and emulsifying agents useful in the formulation of these dispersions are well known in the art and are quite numerous. present invention, the ß-dic compound arbonyl or the cyclic α-diketone compound or its solution can be added to the peroxide dispersion already formed, or to the water containing the surfactant or the peroxide before the dispersion is formed. Dispersions of the present invention generally contain from 20 to 70% by weight, preferably 30 to 60% by weight of the peroxydicarbonate or diacyl peroxide compound and 0.2 to 5% (by weight of peroxide) of the β-dicarbonyl or cyclic α-diketone . The manner of preparation of the peroxide dispersions is known to a person of ordinary skill in the art. A description of the peroxydicarbonate dispersions and their preparation can be found in U.S. Pat. No. 4,515,929; the U.S. Patent No. 3,825,509; the U.S. Patent No. 3,988,261 and the U.S. Patent. No. 4,092,470. The peroxide compositions of the present invention can also be prepared as physical mixtures in the form of liquids, granules, powders or flakes. A physical mixture according to the present invention can be prepared by mixing a liquid peroxide compound or a solution of a peroxide in a convenient solvent, with the desired amount of cyclic β-dicarbonyl or α-diketone in a conventional mixing apparatus. The resulting mixture is then granulated, pulverized or flaked if desired. The cyclic β-dicarbonyl or α-diketone may be added either (1) to the reaction mixture containing chloroformate or acid chloride prior to preparation of the peroxide compound or (2) to the unprocessed reaction mixture immediately after preparation of the peroxide compound. Either (1) or (2) will ensure that the two components are mixed as homogeneously as possible in order to receive the greatest possible benefit from the stabilizing effect of cyclic β-dicarbonyl or a-diketone. A solution of the present invention can be prepared by combining the desired amounts of the cyclic β-dicarbonyl compound or α-diketone or its solution and peroxide in a convenient solvent.
Suitable organic solvents include those normally employed for peroxydicarbonates or diacyl peroxides such as esters of phthalic acid, an example of which is dibutyl phthalate and aliphatic and aromatic hydrocarbons and mixtures of these hydrocarbons, examples of which are hexane, odorless mineral spirits, oils minerals, benzene, toluene, xylene, and (iso) paraffins such as isododecane. Other suitable solvents will be familiar to a person with ordinary skill in the art. Solutions according to the present invention preferably contain at least 10% and more preferably at least 25% by weight of a peroxydicarbonate or diacylperoxide compound. The peroxide compositions of the present invention exhibit numerous significant advantages. Mainly among these is improved thermal stability, both in response to exposure to raise the temperature and in response to a certain constant temperature. The thermal stability of self-reactive substances, in response to elevated temperatures, can be determined by measuring the SADT self-accelerating decomposition temperature (SADT - self accelerating deco position temperature). SADT is one of the recognized tests to determine the safe storage and transport of materials such as organic peroxides. [Recommendations on the transport of dangerous goods (Reccomendations on the Transport of Dangerous Goods), ninth edition, United Nations (United Nations), NY 1995, Section 11.3.5 page 264]. SADT can be correlated directly with the start temperature as measured in a differential thermal analyzer (DTA). The start temperature is the point at which uncontrolled thermal decomposition begins. The start temperature can be measured by determining the point at which the rate of temperature increase in a closed cell exceeds a certain pre-determined value. In addition, the start temperature can be measured by determining the point at which the rate of pressure increase in the closed cell exceeds a certain predetermined value. The thermal stability in response to a given constant temperature can be estimated by accelerated aging tests for example at 15 ° C. The cyclic α-dicarbonyl and α-diketone compounds of the present invention increase the start temperature of both peroxydicarbonates and diacylperoxides. Also, the β-dicarbonyl and cyclic α-diketone compounds do not impair the effectiveness of the peroxide as a polymerization initiator. The following examples are intended to illustrate the claimed invention and are in no way designed to limit its scope. Numerous additional embodiments within the scope and spirit of the claimed invention will be apparent to those skilled in the art. EXAMPLE 1 The start temperature is measured and compared for samples of pure di-2-ethylhexyl peroxydicarbonate, and samples of di-2-ethylhexyl peroxydicarbonate in the presence of each of several different β-dicarbonyl compounds. The liquid mixtures were prepared by dissolving the required amount of β-dicarbonyl in the peroxy di-carbonate. Using a type of Differential Thermal Analyzer (Radex Solo Thermal Analyzer, distributed on the market by Astra Scientific International, Pleasanton, CA.), with an isothermal retention temperature of 30'c for 15 minutes and then a temperature increase of 1" / minute at 130 ° C, the start temperature is measured for a sample of one gram of di-2-ethylhexyl peroxydicarbonate in a closed cell.The start temperature is measured both by noticing the point where the rate of increase (? T) of the sample temperature reached 0.2 ° C / minute and also the point where the rate of increase in pressure (ΔP) of the closed sample cell reached 0.0703 Kg / c 2 (1.0 psi) / minute. is the difference between the oven temperature and the sample temperature: P is the difference between a precalibrated reference pressure and the pressure developed in the sealed sample cell.The procedure is repeated with separate samples of the di-carbonate peroxide ior which in turn contains eti1-2-cyclohexanone carboxylate, 2-acetyl ciciohexanone, 2-acetyl cyclopentanone and 2,4-pentanedione. The results are illustrated in Table I. Results obtained with ethyl acetoacetate, which is described in the prior art, are included for comparison. The results show that the presence of a β-dicarbonyl compound according to the present invention increases the temperature at which the self-accelerating decomposition of peroxy dicarbonate will begin. This shows that the β-dicarbonyl compound is an effective stabilizer and is superior to ethyl acetoacetate. The results also show that the effect depends on the concentration, with the decomposition beginning at higher temperature when more ß-dicarbonyl compound is present.
TABLE I. STARTING TEMPERATURE FOR 98.3% OF DI-2-ETHYLEXIL PEROXIDICARBONATE ADDITIVE% by weight of Additive Temperature start ('C) By AT or A None 37.3 40.2 Ethyl acetoacetate 2.9 43.9 46.9 Ethyl-2- 0.9 49.1 50.8 cyclohexanone carboxylate Ethyl-2- 2.9 55.2 57.0 cyclohexanone carboxylate 2, -Pentandione 2.9 55.3 58.2 2-Acetyl 2.9 55.6 57.5 cyclohexanone 2-Acetyl 3.1 57.7 61.2 cyclopentanone EXAMPLE 2 The starting temperature for samples of di-2-ethylhexyl peroxydicarbonate diluted with alcohols Odorless minerals (WHO) and di-2-ethylhexyl peroxydicarbonate samples diluted in OMS in the presence of several different β-dicarbonyl compounds, were measured and compared. The liquid mixtures were prepared by dissolving the indicated amount of β-dicarbonyl compound in the peroxy dicarbonate solution. Using the same apparatus and method as described in Example 1, the start temperature for a sample of 1 gram of 82.5% di-2-ethylhexyl peroxydicarbonate diluted in OMS is measured. The procedure is repeated with separate samples of the above solution to which ethyl-2-cyclohexanone carboxylate, 2-acetyl cyclohexanone, 2-acetylcyclopentanone, methyl-2-cycloheptanone carboxylate, ethyl-2-oxocyclopentane carboxylate, dibenzoyl methane and ethyl-4-methyl-2-cyclohexanone-l-carboxylate. The results are illustrated in Table II. The results obtained with ethyl acetoacetate, which is described in the prior art, are included by comparison. As can be seen in Table II, the addition of a β-dicarbonyl compound according to the present invention increases the temperature at which the self-accelerating decomposition of peroxy dicarbonate will begin. The results also show that the effect is concentration dependent, with the decomposition of the peroxydicarbonate starting at a higher temperature when more ß-dicarbonyl compound is present.
TABLE II STARTING TEMPERATURE FOR 82.5% DI-2-ETHYLEXIL PEROXIDICARBQNATE IN WHO ADDITIVE% by weight of Additive Temperature beginning f ° C] By? T By AP None - 42.9 43.3 Ethyl acetoacetate 3.1 43.4 47.5 Ethyl-2- cycle hexanone carboxylate 0.2 43.1 46.0 Ethyl-2-cyclohexane carboxylate 0.5 47.5 48.0 Ethyl-2-cyclohexane carboxylate 1.0 50.0 51.6 Ethyl-2-cyclohexane carboxylate 2.4 55.1 54.7 Ethyl-2-cyclohexane carboxylate 5.0 58.6 57.4 TABLE II (Continued) .) START TEMPERATURE FOR 82.5% DI-2-ETHYLEXIL PEROXIDICARBONATE IN WHO ADDITIVE% by weight of Additive Temperature start (° C) By AT By AP 2-Acetyl ciciohexanone 1.0 51.9 51.5 2-Acetyl ciciohexanone 1.9 54.8 56.7 2- Acetyl cyclohexanone 3.0 57.5 57.1 2-Acetyl cyclopentanone 1.0 54.0 55.3 2-Acetyl cyclopentanone 1.9 57.4 57.9 2-Acetyl cyclopentanone 2.8 58.4 59.0 Methyl-2-cycloheptanone carboxylate ll 44.7 47.0 Ethyl-2-oxocyclopentane carboxylate ll 44.7 47.2 TABLE II (Cont.) TEMPERATURE OF IN ICIO FOR 82.5% OF DI-2-ETHYLEXIL PEROXIDICARBONATE IN WHO ADDITIVE% by weight of Additive Temperature start (° C) By? For AP Dibenzoyl methane 3.0 50.0 51.5 Ethyl-4-methyl-2-cyclohexanone-1-carboxylate 3.0 55.5 57.0 EXAMPLE 3 Starting temperatures for samples of di-sec-butyl peroxydicarbonate diluted in odorless mineral spirits (OMS) and di -sec-butyl peroxydicarbonate diluted in OMS in the presence of several different β-dicarbonyl compounds were measured and compared. The liquid mixtures were prepared by dissolving the indicated amount of β-dicarbonyl compound in the peroxy dicarbonate solution. The starting temperature is measured according to the procedure described in Example I. As can be seen in Table III, the addition of a β-dicarbonyl compound according to the present invention increases the temperature at which the self-accelerating decomposition of peroxy dicarbonate will start. The results also show that the effect is concentration dependent, with the reaction starting at higher temperature when more ß-dicarbonyl compound is present. The effect of ethyl acetoacetate is included for comparison. TABLE III STARTING TEMPERATURE FOR 75.5% OF DI-2-SEC-BUTIL PEROXIDICARBONATO IN WHO ADDITIVE% by weight of Additive Temperature beginning f "O By A By AP None 40.8 44.1 Ethyl Acetate-acetate 2.9 38.2 43.6 EtÍl-2-cycle hexanone carboxylate 1.1 46.8 47.3 Ethyl-2-cyclohexane carboxylate 3.0 52.3 51.5 2-Acetyl cyclohexanone 0.9 47.5 47.5 2-Acetyl cyclohexanone 2.8 52.5 53.3 2-Acetyl cyclopentanone 0.9 48.1 48.1 TABLE III (Cont.) START TEMPERATURE FOR 75.5% OF DI -2-SEC-BUTIL PEROXIDICARBONATO IN WHO ADDITIVE% by weight of Additive Temperature start ("O by AT by AP 2-Acetyl cyclopentanone 2.9 54.3 54.3 2, 4-pentadiene 3.0 50.5 51.6 EXAMPLE 4 The effect of the presence of various β-dicarbonyl compounds on the storage stability at 15 ° C for pure di-2-ethylhexyl peroxydicarbonate is determined as an accelerated aging test. The purity of the peroxydicarbonate is measured initially after 7 days, and after 14 days. The results are presented in Table IV. Ethyl acetoacetate is included as an example in the prior art. The initial purity values were corrected for the presence of the additive. A similar procedure was repeated with a mueetra of di-2-ethylhexyl peroxydicarbonate in OMS and a sample of di-sec-butyl peroxydicarbonate in OMS. The results are illustrated in Tables IV-A and IV-B, respectively. The initial purity values were corrected for the presence of the additive.
The results show that the presence of a β-dicarbonyl compound according to the present invention retards the decomposition rate of the peroxydicarbonate. TABLE IV PURITY AGAINST TIME TO 15 * C FOR DI-2-ETHYLEXIL PEROXIDICARBONATE PURE PURE
ADDITIVE% by weight of 7 14 Additive START DAYS DAYS None - 98.3 32.1 17.5 Ethyl acetoacetate 2.9 95.4 41.6 21.3 Ethyl-2-cyclone? hexanone carboxylate 1.1 97.3 70.4 30.4 Ethyl-2-cyclohexane carboxylate 2.9 95.4 88.0 61.6 2-Acetyl ciciohexanone 1.0 97.3 43.7 n.d 2-Acetyl ciciohexanone 2.9 95.2 58.8 n.d. 2-Acetyl cyclopentanone l.O 97.3 56.3 n.d.
TABLE IV (Cont.) PURITY AGAINST TIME TO 15 * C FOR DI-2-ETHYLEXIL PURE PEROXIDICARBONATE PURITY (%) ADDITIVE% by weight of 7 14 Additive HOME DAYS DAYS
2-Acetyl cyclopentanone 3.0 95.4 71.2 43.3
2,4-pentadiene 2.9 95.4 78.1 57.2 n.d. = not determined TABLE IV-A PURITY AGAINST TIME TO 15"C FOR DI-2-ETHYLEXIL PEROXIDICARBONATE IN WHO PURITY f%) API IVO% by weight of 7 14 AdJtj.vp HOME DAYS D AS
None 76.2 33.8 24.9
Ethyl hexanone carboxylate cycle 3.0 73.9 67.3 37.6
2-Acetyl cyclohexanone 2.9 74.0 57.4 28.32
2-Acetyl cyclopentanone 2.9 73.9 63.6 44.2 2, 4-pentadiene 3.0 73.9 61.0 44.9 TABLE IV-B PURITY AGAINST TIME TO 15 * C FOR DI-SEC-BUTIL PEROXIDICARBONATO IN WHO PUKEZA m ADDITIVE% by weight of 7 Additive HOME DAYS None - 75.5 49.6 Ethyl-2-cyclohexane carboxylate 3.1 73.2 60.8 2-Acetyl dicyclohexanone 3.2 73.1 53.3 2-Acetyl cyclopentanone 2.8 73.5 56.9 EXAMPLE 5 Starting temperatures for a sample of di- (3,5,5-trimethylhexanoyl) peroxide and samples of di- (3,5,5-trimethylhexanoyl) peroxide in the presence of several different β-dicarbonyl compounds was measured and compared. The liquid mixtures were prepared by dissolving the indicated amount of β-dicarbonyl compound in the peroxide. Using the procedure described in Example I, the start temperature for a 99% sample of di- (3,5,5-trimethylhexanoyl) peroxide is measured. The procedure is repeated as a separate sample from the previous product to which 2,4-pentanedione and ethyl-2-cyclohexanone carboxylate has been added. The results are shown in Table 5.
As can be seen in Table V, the addition of the β-dicarbonyl compound according to the present invention increases the temperature at which the self-accelerating decomposition of the diacyl peroxide will begin. TABLE V
STARTING TEMPERATURE FOR 99% OF DIF3.5.5-TRIMETHYL-HEXANOIL) ADDITIVE PEROXIDE% by weight of Additive Temperature start (° C) By AT By AP None - 68.2 67.7 2,4-pentadione 3.1 68.4 70.9 Ethyl-2-cyclohexane carboxylate 3.0 69.8 68.7 EXAMPLE 5 Starting temperatures for a sample of di- (3,5,5-trimethylhexanoyl) peroxide diluted in odorless mineral spirits (WHO) and samples of di- (3,5,5-trimethylhexanoyl) peroxide in WHO in the presence of several different β-dicarbonyl compounds was measured and compared. The liquid mixtures were prepared by dissolving the indicated amount of β-dicarbonyl compound in the peroxide solution.
Using the procedure described in Example I, the start temperature for a 60% sample of di- (3,5,5-trimethylhexanoyl) peroxide in OMS is measured. The procedure is repeated as separate samples of the above solution to which 2,4-pentanedione and ethyl-2-cyclohexanone carboxylate have been added. The results are shown in Table VI. As can be seen in Table VI, the addition of the β-dicarbonyl compound according to the present invention increases the temperature at which the self-accelerating decomposition of the diacyl peroxide solution will begin. TABLE VI STARTING TEMPERATURE FOR 60% OF DIf3r5.5-TRIMETHYLONANOIL) PEROXIDE IN WHO ADDITIVE% by weight of Additive Temperature start f * C) By A By A None - 74.9 76.1 2, 4-pentadione 3.0 76.3 78.1 Ethyl-2 -hexanone carboxylate 3.0 76.4 77.5 EXAMPLE 7. The start temperature is measured and compared for samples of pure di-2-ethylhexyl peroxydicarbonate, and sample of di-2-ethylhexyl peroxydicarbonate in the presence of each of several different cyclic α-diketone compounds. Liquid mixtures were prepared by dissolving in the peroxy dicarbonate a sufficient amount of a solution of the α-diketone in propylene glycol, to provide the indicated amount of α-diketone. Using a type of Differential Thermal Analyzer (Radex Solo Thermal Analyzer, distributed by Astra Scientific International, Pleasanton, CA.), with an isothermal retention temperature of 30 * C for 15 minutes and then a temperature increase of 1"/ minute up to 130 * C, the start temperature is measured for a sample of one gram of di-2-ethylhexyl peroxydicarbonate in a sealed cell.The start temperature is measured both by noticing the point where the rate of increase (? T) of the sample temperature reached 0.2 * C / minute and also the point where the rate of increase in pressure (? P) of the closed sample cell reaches 0.0703 Kg / cm2 (1.0 psi) / minute.? T is the difference between the oven temperature and the sample temperature: P is the difference between a precalibrated reference pressure and the pressure developed in the sealed sample cell.The procedure is repeated, with separate samples of the previous di-carbonate peroxide In turn, solve (in propylene glycol) 3-methyl-l, 2-cyclopentandione (MCDP), 3-ethyl-l, 2-cyclopentandione (ECDP), and 1,2-cyclohexanedione (CHD).
The results are shown in Table VII. Results obtained with ethyl ethoacetate described in the prior art are included for comparison. The results show that the presence of a compound according to the present invention increases the temperature at which the self-accelerating decomposition of peroxy dicarbonate will begin. This shows that the a-diketone cyclic compound is an effective stabilizer and is superior to ethyl acetoacetate. The results also show that the effect is dependent on concentration, with the composition starting at a higher temperature when more cyclic α-diketone compound is present. TABLE VII STARTING TEMPERATURE FOR DI-2-ETHYLEXIL PURE PEROXYDICARBONATE Purity% by weight of Start Temperature (° C) of Pure Additive sample% Additive E plicated by AT 97.7 None - 36.3 42.3 ECPD-50 ** 1.8 54.8 57.2
97. 4 None • 34.4 38.8 Ethylacetate-3.0 43.4 46.3 acetate MCPD-10 * 0.3 42.8 45.7 TABLE VII (Cont.) STARTING TEMPERATURE FOR DI-2-ETHYLEXIL PURE PEROXIDICARBONATE Purity% by weight Start Temperature (* C) of Pure Additive sample% Additive Employed Per A By AP MCPD-10 0.5 48.4 50.1 CHD-60 *** 0.6 42.3 44.9 CHD-60 1.8 48.4 49.0 CHD-60 3.0 51.3 52.1
* MCPD-10 = 10% solution of MCDP in propylene glycol. ** ECPD - 60 = 50% solution of ECPD in propylene glycol. *** CHD - 60 - 60% solution of CHD in propylene glycol. EXAMPLE 8 Starting temperatures for the samples of di-2-ethylhexyl peroxydicarbonate diluted with odorless mineral spirits (WHO) and sample of di-2-ethylhexyl peroxydicarbonate diluted in OMS in the presence of several different cyclic α-diketone compounds were measured and they compared. The liquid mixtures were prepared by dissolving in the peroxy dicarbonate solution a sufficient amount of a solution of ECPD, MCPD or CHD in propylene glycol, to provide the indicated amount of the cyclic α-diketone compound.
Using the same apparatus and procedure as described in Example 7, the start temperature is measured for a sample of 1 gram of di-2-ethylhexyl peroxydicarbonate diluted in OMS. The procedure is repeated with samples separated from the previous solution to which a solution of the cyclic α-diketone has been added. The results are shown in Table VIII. The results obtained with ethyl acetoacetate, which is described in the prior art, are included by comparison. As can be seen in Table VIII, the addition of a cyclic α-diketone compound according to the present invention increases the temperature at which the self-accelerating decomposition of the peroxy dicarbonate solution will begin. The results also show that the effect is concentration dependent, with decomposition starting at a higher temperature when more cyclic α-diketone compound is present. TABLE VTII START TEMPERATURE FOR DI-2-ETHYLEXEX PEROXIDICARBONATE IN WHO Purity% by weight Start Temperature ("Or Pure Additive shows% Additive Em lead By AT By AP
74. 9 None - 4 | .4 43.6 ECPD-50 * 0.2 44.9 46.3 'ECPD-50 0.4 48.5 48.5 TABLE VIII (Cont'd) START TEMPERATURE FOR DI-2-ETHYLEXIL PEROXIDICARBONATE IN WHO Purity% by weight of Start-up Temperature of Additive Pure sample % Additive Used By AT By AP E ECCPPDD - 5500 0.5 50.2 52.1 ECPD-50 0.9 54.1 54.8 ECPD-50 1.5 56.2 57.4 ECPD-50 2.5 57.0 58.9
75. 1 None 40.7 45.0 Ethylacetate-3.0 44.5 45.9 Acetate MCPD-10 ** 0.1 41.6 45.3 MCPD-10 0.3 47.0 49.3 MCPD-10 0.5 48.6 50.4 CHD-60 *** 0.6 46.9 49.0 CHD-60 1.2 50.9 52.5 CHD-60 1.9 53.0 53.9
* ECPD-50 - 50% solution of ECDP in propylene glycol. ** MCPD - 10 = 10% solution of MCPD in propylene glycol. *** CHD - 60 = 60% solution of CHD in propylene glycol.
The starting temperatures were measured and compared for the samples of di-2-ethylhexyl peroxydicarbonate diluted in odorless inerale alcohols (OMS) and di-eec-butyl peroxydicarbonate mueetrae diluted in OMS in the presence of several different coe- cyclic diketone. The liquid mixtures were prepared by dissolving in the peroxy dicarbonate solution, a sufficient amount of a solution of ECPD, MCPD or CHD in propylene glycol, to provide the indicated amount of the α-diketone compound. The start temperature is measured according to the procedure described in Example 7. As can be seen in Table IX, the presence of a cyclic α-diketone compound according to the present invention increases the temperature at which self-accelerating decomposition of the peroxy dicarbonate solution will start. The results also show that the effect depends on the concentration, with the reaction beginning at a higher temperature when more cyclic α-diketone is present. The effect of ethyl acetoacetate is included for comparison.
TABLE IX START TEMPERATURE FOR
DI-SEC-BUTIL PEROXIDICARBONATO IN WHO Purity% by weight of Start Temperature Í * C of Pure Additive sample% Additive Used by A By AP 76.2 None - 36.6 41.0 ECPD-50 * 1.5 52.5 53.0
70. 7 None 37.0 37.9 Ethylacetate-3.0 36.3 39.3 Acetate MCPD-10 ** 0.1 39.9 41.3 MCPD-10 0.3 44.2 46.7 MCPD-10 0.5 46.8 48.1 CHD-60 *** 0.6 43.6 45.0 CHD-60 1.8 50.0 50.7 CHD-60 3.0 52.8 53.8
* ECPD- 50 = 50% solution of ECDP in propylene glycol. ** MCPD - 10 = 10% solution of MCPD in propylene glycol. *** CHD - 60 = 60% solution of CHD in propylene glycol. EXAMPLE 10 The effect of the presence of ECDP on the storage stability at 15 ° C of pure di-2-ethylhexyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate dissolved in odorless mineral spirits (OMS) and di-sec-butyl peroxydicarbonate dissolved in WHO, is determined as an accelerated age test. The results are presented in Table X. The purity of the peroxydicarbonate is measured at the times indicated in Table X. The initial purity values in the Table were corrected for the presence of the additive. The results show that the presence of a cyclic α-diketone according to the present invention retards the decomposition rate of the peroxydicarbonate. TABLE X
PURITY AGAINST TIME AT 15 * C FOR VARIOUS PEROXIDICARBONATES (ECPD is added as a 50% solution in propylene glycol)
Peroxy-% by weight of Purity (%) Dicar- of Pure Additive Bonate Employee 7 14 21 Additive HOME DAYS AS AS
97. 7% Di-2- none 97.7 22.4 22.4 21.7 ethylhexyl-peroxydicarbonate (pure) ECDP-50 1.5 94.9 77.3 39.3 27.1
74. 9% Di-2- None 74.9 28.6 17.9 15.4 TABLE X (Cont.) PURITY AGAINST TIME AT 15 * C FOR VARIOUS PEROXIDICARBONATES (ECPD is added as a 50% solution in propylene glycol)
Peroxy-% by weight of Purity (%) Dicar- of Pure Additive Bonate Employee 7 14 21 Additive DAYS DAYS DAYS ethylhexyl-Peroxy-dicarbonate in WHO ECPP-50 1.5 72.7 58.8 37.7 23.1
76. 2% Di-2- none 76.2 19.9 17.7 - secbuti1-peroxydicarbonate in QMS ECDP-50 1.4 74-2 49.5 20.7 - EXAMPLE XJQ. Starting temperatures for a sample of pure di- (3, 5, 5-trimethylhexanoyl) epoxide and samples of pure di- (3,5,5-trimethylhexanoyl) peroxide in the presence of two different cyclic α-diketones were measured and they compared. This procedure was repeated for a sample of di- (3,5,5-trimethylhexanoyl) peroxide dissolved in odorless mineral spirits (OMS) and sample of di- (3,5,5-trimethylhexanoyl) peroxide dissolved in OMS in the presence of two different cyclic α-diketone compounds. The liquid mixtures were prepared by adding a sufficient amount of a solution of ECPD or CHD in propylene glycol to the diacyl peroxide to provide the indicated amount of the cyclic α-diketone compound. The procedure described in Example VII was followed. The results are shown in Table XI. As can be seen in Table XI, the presence of the cyclic α-diketone compound, according to the present invention, increases the temperature at which the self-accelerating decomposition of the diacyl peroxide or its solution in OMS will begin. TABLE XI STARTING TEMPERATURE FOR D F3.5.5-TRIMETHYL-HEXANOIL PEROXIDE Purity% by weight of Start Temperature ('O of Pure Additive sample.% Additive Read by AT By A 98.2 None 68. 2 67.7 CHD-60 * 3.0 70. 1 72. 3 ECPD-50 ** 2.6 70.8 74 .4 TABLE XI (Cont.) STARTING TEMPERATURE FOR DIf3.5.5-TRIMETHYLHEXANOIL PEROXIDE Purity% by weight of Start Temperature f'C) of Pure Additive sample. % Additive E plicated By AT By AP 60.1 (in OMS) None 74.9 76.1 CHD-60 * 2.0 76. 6 76. 6 ECPD-50 ** 1.5 77.0 77.0
* CHD- 60 = 60% solution of CHD in propylene glycol. ** ECPD - 50 = 50% solution of ECPD in propylene glycol.
Claims (24)
- CLAIMS 1.- A composition characterized because it comprises: a. an organic peroxide component selected from the group consisting of peroxydicarbonate compounds, diacyl peroxides and mixtures thereof; and b. a sufficient amount of a stabilizer to retard the decomposition rate of the organic peroxide component, wherein said stabilizer is selected from the group consisting of β-dicarbonyl compounds of the formulas I, II and III and compounds of the formula IV:
- R'-CfOJ-CHR'-CÍO-R7 (III) and mixtures thereof wherein m is 1-5, n is 1-6, i is 0-1, x is 0-2n, and is 0-2m, R1 is alkyl containing 22 carbon atoms, phenyl or substituate phenyl with one or more of alkyl containing 1 to 22 carbon atoms, halogen and hydroxy and R 1 can be hydrogen wherein i is zero; R2 is alkyl having 1 to 22 carbon atoms, phenyl or phenyl substituted with one or more of alkyl containing 1 to 22 carbon atoms, halogen and hydroxy and when x is greater than 1, each occurrence of R2 may be the same or different and may be on the same or different ring carbon atoms; R3 is hydrogen, alkyl containing 1 to 22 carbon atoms, acyl containing 2 to 22 carbon atoms, phenyl or phenyl substituted with one or more of alkyl containing 1 to 22 carbon atoms, halogen and hydroxy; R * is alkyl containing 1 to 22 carbon atoms, phenyl or phenyl substituted with one or more of alkyl containing 1 to 22 carbon atoms, halogen and hydroxy and when y is greater than 1, each occurrence of R * may be same or different and can be in the same or different ring carbon atoms; Rs is hydrogen, alkyl having 1 to 22 carbon atoms, phenyl or phenyl substituted with one or more of alkyl containing 1 to 22 carbon atoms, halogen or hydroxy; R6 is hydrogen or alkyl containing 1 to 22 carbon atoms, phenyl or phenyl substituted with one or more of alkyl containing 1 to 22 carbon atoms, halogen or hydroxy; or Rβ is -C (0) OR * or -C (0) R * wherein R * is alkyl containing 1 to 22 carbon atoms; and R7 is phenyl or alkyl containing 1 to 22 carbon atoms. - 2. A composition according to claim 1, characterized in that it comprises a β-dicarbonyl compound of the formula (I).
- 3. A composition according to claim 1, characterized in that it comprises a β-dicarbonyl compound of the formula (II).
- 4. A composition according to claim 1, characterized in that it comprises a β-dicarbonyl compound of the formula (III).
- 5. A composition according to claim 1, characterized in that it comprises a β-dicarbonyl compound of the formula (IV). J 10
- 6. A composition according to any of claims 1 to 5, characterized in that the organic peroxide compound comprises at least one compound of the formula (V): R9- (0) cC (0) -0-0- C (0) - (0) cR ** ° (V) Wherein R 'and R10 are independently aliphatic, cycloaliphatic or aromatic groups with 1 to 22 carbon atoms, and c is 0 or 1.
- 7. A composition according to claim 6, characterized in that in the formula (V) both 20 subscripts c are one.
- 8. A composition according to claim 6, characterized in that in the formula (V) both subscripts c are zero.
- 9. A composition according to claim 6, characterized by R9 and R10 independently are selected from the group consisting of phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, o-butyl hexyl, octyl, neopentyl, 2-ethylhexyl, capryl, lauryl, myristyl, cetyl, stearyl, allyl, methallyl, crotyl, cyclohexyl, 4-t-butylcyclohexyl, 4-t-amylcyclohexyl, benzyl, 2-phenylethyl, 2-phenylbutyl , α-carbetoxyethyl, β-methoxyethyl, 2-phenoxyethyl, 2-methoxyphenyl, 3-methoxyphenyl, 2-ethoxyethyl, 2-ethoxyphenyl, 3-methoxybutyl, 2-carbamyloxyethyl, 2-chloroethyl, 2-nitrobutyl, and 2-nitro -2-methylpropyl.
- 10. A composition according to claim 1, characterized in that the stabilizer is selected from the group comprising ethyl-2-cyclopentanone carboxylate, methyl-2-cycloheptanone carboxylate, ethyl-2-cyclohexanone carboxylate, 2-acetyl cyclopentanone, 2-acetyl cyclohexanone, ethyl-4-methyl-2- cyclohexanone-1-carboxylate, 1,3-cyclohexanedione, 1,3-cyclopentandione, 2,4-pentanedione, and dibenzoyl methane, 3-methyl-1, 2-cyclopentanedione, 3-ethyl-1, 2-cyclopentanedione, 1, 2-cyclohexanedione, 1,2-cyclopentandione, and their mixtures.
- 11. A composition according to claim 1, characterized in that the stabilizer comprises 0.2 to 5% by weight of the organic peroxide component.
- 12. A composition according to claim 1, characterized in that the organic peroxide component is selected from the group consisting of di-2-ethylhexyl peroxydicarbonate, di-sec-butylperoxydicarbonate, diethyl peroxydicarbonate, di-n-butyl-peroxydicarbonate, isopropyl -sec-butylperoxydicarbonate, di-4-tert-butylcyclohexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, benzoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, diacetyl peroxide, 2-methylpropionyl-3-methylpentanoyl peroxide, and di (3,5,5-tri ethylhexanoyl) peroxide and mixtures thereof.
- 13. The method for retarding the decomposition rate of an organic peroxide selected from the group consisting of peroxydicarbonate and diacyl peroxide compounds and their mixtures characterized in that it comprises adding to the organic peroxide a stabilizer in an amount effective to retard decomposition rate, wherein the stabilizer is selected from the group consisting of β-dicarbonyl compound of the formulas I, II and III and compounds of the formula IV: Rs-C (0) -CHR - * - C (0) -R, (III) (IV) and mixtures thereof wherein m is 1-5, n is 1-6, i is 0-1, x is 0-2n, and is 0-2m, Rl is alkyl containing 1 to 22 carbon atoms, phenyl or phenyl substituted with one or more of alkyl containing 1 to 22 carbon atoms, halogen and hydroxy and R 1 can be hydrogen wherein i is zero; R 2 is alkyl with 1 to 22 carbon atom, phenyl or phenyl substituted with one or more of alkyl containing 1 to 22 carbon atoms, halogen and hydroxy and when x is greater than 1, each occurrence of R 2 may be the same or different and may be on the same or different ring carbon atoms; R3 is hydrogen, alkyl containing 1 to 22 carbon atoms, acyl containing 2 to 22 carbon atoms, phenyl or phenyl substituted with one or more of alkyl containing 1 to 22 carbon atoms, halogen and hydroxy; R * is alkyl containing 1 to 22 carbon atoms, phenyl or phenyl substituted with one or more alkyl containing 1 to 22 carbon atoms, halogen and hydroxy and when and greater than 1, each occurrence of R4 may be the same or different and may be in the same or different ring carbon atoms; R5 is hydrogen, alkyl having 1 to 22 carbon atoms, phenyl or phenyl substituted with one or more of alkyl containing 1 to 22 carbon atoms, halogen and hydroxy; R ** is hydrogen or alkyl containing 1 to 22 carbon atoms, phenyl or phenyl substituted with one or more of alkyl containing 1 to 22 carbon atoms, halogen and hydroxy; or Rβ is -C (0) OR * or -C (0) Rβ wherein R * is alkyl containing 1 to 22 carbon atoms; and R7 is phenyl or alkyl containing 1 to 22 carbon atoms.
- 14. A method in accordance with the claim 13, characterized in that the peroxydicarbamate and diacyl peroxide compounds correspond to the formula (V): R9- (0) eC (0) -0-0-C (0) - (0) c-R10 (V) wherein R9 and R10 is independently aliphatic, cycloaliphatic or aromatic with 1 to 22 carbon atoms, and c is 0 or 1.
- 15. A method according to claim 14, characterized in that in the formula (V) both subscripts c are one.
- 16. A method according to claim 14, characterized in that in the formula (V) both subscripts c are zero.
- 17. A method in accordance with the claim 14, characterized in that R9 and R1D are independently selected from the group consisting of phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, isobutyl, hexyl, octyl, neopentyl, 2-ethylhexyl , capryl, lauryl, myristyl, cetyl, stearyl, allyl, methallyl, crotyl, cyclohexyl, 4-t-butylcyclohexyl, 4-t-amylcyclohexyl, benzyl, 2-phenylethyl, 2-phenylbutyl, α-carbetoxyethyl, β-methoxyethyl, 2 -phenoxyethyl, 2-methoxyphenyl, 3-methoxyphenyl, 2-ethoxyethyl, 2-ethoxyphenyl, 3-ethoxybutyl, 2-carbamyloxyethyl, 2-chloroethyl, 2-nitrobutyl, and 2-nitro-2-methylpropyl.
- 18. A method according to claim 13, characterized in that the stabilizer is selected from the group comprising eti1-2-cyclopentanone carboxylate, methyl-2-cycloheptanone carboxylate, ethyl-2-cyclohexanone carboxylate, 2-asethyl cyclopentanone, 2-acetyl. cyclohexanone, ethyl-4-methyl-2-cyclohexanone-1-carboxylate, 1,3-cyclohexanedione, 1,3-cyclopentandione, 2,4-pentanedione, and dibenzoyl methane, 3-methyl-1,2-cyclopentanedione, 3- ethyl-l, 2-cyclopentandione, 1,2-cyclohexanedione, 1,2-cyclopentandione, and their mixtures.
- 19. A method in accordance with the claim 13, characterized in that the stabilizer comprises 0.2 to 5% by weight of the organic peroxide component.
- 20. A method according to claim 13, characterized in that the stabilizer comprises a β-dicarbonyl compound of the formula (I).
- 21. A method according to claim 13, characterized in that the stabilizer comprises a β-dicarbonyl compound of the formula (II).
- 22. A method according to claim 13, characterized in that the stabilizer comprises a β-dicarbonyl compound of the formula (III).
- 23. A method according to claim 13, characterized in that the stabilizer comprises a β-dicarbonyl compound of the formula (IV).
- 24. A method in accordance with the claim 13, characterized in that the organic peroxide component is selected from the group consisting of di-2-ethylhexyl peroxydicarbonate, di-sec-butylperoxydicarbonate, diethyl peroxydicarbonate, di-n-butyl peroxydicarbonate, isopropyl-ee-t-butyl peroxydicarbonate, di-4 -tert-butylcyclohexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, benzoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, diacetyl peroxide, 2-methylpropionyl-3-methylpentanoyl peroxide, and di (3,5,5- trimethylhexanoyl) peroxide and mix thereof. The present invention relates to organic peroxide compositions containing a β-dicarbonyl compound or a cyclic α-diketone compound to retard the decomposition rate of the peroxide compound. R3 / f? Rp / 21 / 96.S. 53
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08656094 | 1996-05-31 | ||
| US08/656,094 US5714626A (en) | 1996-05-31 | 1996-05-31 | Organic peroxide stabilization with β-dicarbonyl compounds |
| US08/656,093 US5654464A (en) | 1996-05-31 | 1996-05-31 | Organic peroxide stabilization with cyclic α-diketone compounds |
| US08656093 | 1996-05-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MX9703995A MX9703995A (en) | 1998-06-30 |
| MXPA97003995A true MXPA97003995A (en) | 1998-10-30 |
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