NZ707590B2 - Process for recovering wastes of a polymeric composition including a peroxidic crosslinking agent - Google Patents
Process for recovering wastes of a polymeric composition including a peroxidic crosslinking agent Download PDFInfo
- Publication number
- NZ707590B2 NZ707590B2 NZ707590A NZ70759012A NZ707590B2 NZ 707590 B2 NZ707590 B2 NZ 707590B2 NZ 707590 A NZ707590 A NZ 707590A NZ 70759012 A NZ70759012 A NZ 70759012A NZ 707590 B2 NZ707590 B2 NZ 707590B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- crosslinking agent
- phenylenediamine
- peroxide
- wastes
- process according
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 96
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 49
- 150000002978 peroxides Chemical class 0.000 claims abstract description 19
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 229920000098 polyolefin Polymers 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 22
- 238000011049 filling Methods 0.000 claims description 14
- -1 butylhydroxyphenyl Chemical group 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001448 anilines Chemical group 0.000 claims description 7
- 150000002989 phenols Chemical class 0.000 claims description 7
- DMBHHRLKUKUOEG-UHFFFAOYSA-N Diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 5
- ZJNLYGOUHDJHMG-UHFFFAOYSA-N 1-N,4-N-bis(5-methylhexan-2-yl)benzene-1,4-diamine Chemical compound CC(C)CCC(C)NC1=CC=C(NC(C)CCC(C)C)C=C1 ZJNLYGOUHDJHMG-UHFFFAOYSA-N 0.000 claims description 4
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-N,4-N-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 claims description 4
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-N-(4-methylpentan-2-yl)-1-N-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 claims description 4
- FSWDLYNGJBGFJH-UHFFFAOYSA-N N,N'-Di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 claims description 4
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 claims description 4
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000004986 phenylenediamines Chemical group 0.000 claims description 4
- HLEKFSJNCHVOAA-UHFFFAOYSA-N (2,6-ditert-butylphenyl)methanol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1CO HLEKFSJNCHVOAA-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- HPGLJHGYYVLNTR-UHFFFAOYSA-N 4-N-(2-methylphenyl)-1-N-(4-methylphenyl)benzene-1,4-diamine Chemical compound C1=CC(C)=CC=C1NC(C=C1)=CC=C1NC1=CC=CC=C1C HPGLJHGYYVLNTR-UHFFFAOYSA-N 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 claims description 2
- APTGHASZJUAUCP-UHFFFAOYSA-N 1-N,4-N-di(octan-2-yl)benzene-1,4-diamine Chemical compound CCCCCCC(C)NC1=CC=C(NC(C)CCCCCC)C=C1 APTGHASZJUAUCP-UHFFFAOYSA-N 0.000 claims description 2
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-N-cyclohexyl-4-N-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 claims description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 1-Nonyl-4-phenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 2
- CXRXDDBPMBXXFT-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,4-dimethylhexane Chemical compound CC(C)(C)OOC(C)C(C)CC(C)(C)OOC(C)(C)C CXRXDDBPMBXXFT-UHFFFAOYSA-N 0.000 claims description 2
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 claims description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 2
- IDMODHRLVSNCOP-UHFFFAOYSA-N 2-(2,6-ditert-butylnonyl)phenol Chemical compound CCCC(C(C)(C)C)CCCC(C(C)(C)C)CC1=CC=CC=C1O IDMODHRLVSNCOP-UHFFFAOYSA-N 0.000 claims description 2
- YGBSNORLROWMAY-UHFFFAOYSA-N 2-tert-butyl-6-(3,3-dimethylbutyl)phenol Chemical compound CC(C)(C)CCC1=CC=CC(C(C)(C)C)=C1O YGBSNORLROWMAY-UHFFFAOYSA-N 0.000 claims description 2
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 claims description 2
- OHFCLJNYYRPINY-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butylphenyl)-2-hydroxypropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(O)CC1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1 OHFCLJNYYRPINY-UHFFFAOYSA-N 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- PIBIAJQNHWMGTD-UHFFFAOYSA-N 1-N,3-N-bis(4-methylphenyl)benzene-1,3-diamine Chemical compound C1=CC(C)=CC=C1NC1=CC=CC(NC=2C=CC(C)=CC=2)=C1 PIBIAJQNHWMGTD-UHFFFAOYSA-N 0.000 claims 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 claims 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 17
- 229920002943 EPDM rubber Polymers 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 8
- 229920001038 ethylene copolymer Polymers 0.000 abstract description 4
- 230000002028 premature Effects 0.000 abstract description 4
- 238000010791 quenching Methods 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 3
- 230000003078 antioxidant Effects 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 150000001993 dienes Chemical class 0.000 description 10
- 239000006057 Non-nutritive feed additive Substances 0.000 description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N Stearic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 8
- 239000004698 Polyethylene (PE) Substances 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 239000011241 protective layer Substances 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 6
- 230000000111 anti-oxidant Effects 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 229960003563 Calcium Carbonate Drugs 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 125000004432 carbon atoms Chemical group C* 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 239000010690 paraffinic oil Substances 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 3
- GQBHYWDCHSZDQU-UHFFFAOYSA-N 4-(2,4,4-trimethylpentan-2-yl)-N-[4-(2,4,4-trimethylpentan-2-yl)phenyl]aniline Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1NC1=CC=C(C(C)(C)CC(C)(C)C)C=C1 GQBHYWDCHSZDQU-UHFFFAOYSA-N 0.000 description 3
- PZZYQPZGQPZBDN-UHFFFAOYSA-N Aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000005673 monoalkenes Chemical class 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-Hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-Octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N Butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N Chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N Pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229920001198 elastomeric copolymer Polymers 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
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- 239000004014 plasticizer Substances 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- UVJHQYIOXKWHFD-UHFFFAOYSA-N 1,4-Cyclohexadiene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- RRRXUCMQOPNVAT-UHFFFAOYSA-N 1-ethenyl-4-(4-methylphenyl)benzene Chemical compound C1=CC(C)=CC=C1C1=CC=C(C=C)C=C1 RRRXUCMQOPNVAT-UHFFFAOYSA-N 0.000 description 1
- VVTGQMLRTKFKAM-UHFFFAOYSA-N 1-ethenyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=C)C=C1 VVTGQMLRTKFKAM-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-Vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- XUGNJOCQALIQFG-UHFFFAOYSA-N 2-ethenylquinoline Chemical compound C1=CC=CC2=NC(C=C)=CC=C21 XUGNJOCQALIQFG-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- NWNPESVXYXCGLH-UHFFFAOYSA-N 4-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C=C)C2 NWNPESVXYXCGLH-UHFFFAOYSA-N 0.000 description 1
- UGWOAPBVIGCNOV-UHFFFAOYSA-N 5-ethenyldec-5-ene Chemical compound CCCCC=C(C=C)CCCC UGWOAPBVIGCNOV-UHFFFAOYSA-N 0.000 description 1
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- 239000004155 Chlorine dioxide Substances 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N Di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
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- 150000003336 secondary aromatic amines Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N α-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
Abstract
process for recovering wastes of a polymeric composition including at least one peroxide-curable polymer and at least one peroxidic crosslinking agent, which comprises compounding the wastes with at least one antioxidant agent suitable for sulfur-vulcanized elastomeric compositions, at a temperature lower than the decomposition temperature of the at least one peroxide crosslinking agent. These above antioxidant agents are effective to quench the peroxide crosslinking agent, so as to avoid any substantial crosslinking of the composition during processing of the same. The compounding of the polymeric wastes with the antioxidant agent is carried out at a temperature lower than the decomposition temperature of the peroxide crosslinking agent, so as to avoid any premature activation of the crosslinking agent. This makes the process according to the present invention particularly suitable for compositions based on elastomeric polyolefins, more preferably for elastomeric ethylene copolymers such as ethylene-propylene copolymers (EPR) and ethylene-propylene-diene terpolymers (EPDM), which can be processed at relatively low temperatures, much lower than the decomposition temperatures of the most common peroxide crosslinking agents. re lower than the decomposition temperature of the at least one peroxide crosslinking agent. These above antioxidant agents are effective to quench the peroxide crosslinking agent, so as to avoid any substantial crosslinking of the composition during processing of the same. The compounding of the polymeric wastes with the antioxidant agent is carried out at a temperature lower than the decomposition temperature of the peroxide crosslinking agent, so as to avoid any premature activation of the crosslinking agent. This makes the process according to the present invention particularly suitable for compositions based on elastomeric polyolefins, more preferably for elastomeric ethylene copolymers such as ethylene-propylene copolymers (EPR) and ethylene-propylene-diene terpolymers (EPDM), which can be processed at relatively low temperatures, much lower than the decomposition temperatures of the most common peroxide crosslinking agents.
Description
PROCESS FOR RECOVERING WASTES OF A POLYMERIC
COMPOSITION INCLUDING A PEROXIDIC CROSSLINKING AGENT
DESCRIPTION
Background of the invention
The present invention relates to a process for recovering wastes of a
polymeric composition including a peroxidic crosslinking agent.
During the production of polymeric compositions including a peroxidic
crosslinking agent - to be used, for instance, for the manufacturing of coating layers
of electrical cables - remarkable amounts of wastes may result, e.g. because of
formulation errors, contaminations or other undesired events that may modify
composition and properties of the resulting polymeric material, making it
unsuitable for the intended purpose. This is particularly critical in the case of
polymeric compositions to be used for electrically insulating medium and/or high
voltage electrical cables, wherein the insulating layer must be substantially devoid
of any defects or impurities.
Polymeric wastes containing unreacted peroxidic crosslinking agent should
be discarded following expensive national standard routes. It is environmentally
preferable to recover such polymeric wastes, but the procedure poses several
problems mainly because of the presence of the peroxidic crosslinking agent, which
must be eliminated so as to avoid any undesired crosslinking of the composition
during the subsequent processing of the recovered material. It is worthwhile to note
that a direct recycling of the wastes to the production process of the composition is
not feasible, since it is practically impossible to determine with sufficient precision
the composition of the wastes, particularly as regards the peroxide content, a
parameter that shall be known with high accuracy to carry out the process for
manufacturing, for example, electrical cables in a reliable manner.
In patent application JP 62-20244 a method is disclosed for recycling an
uncrosslinked crystalline polyolefin resin composition containing an organic
peroxide by thermally decomposing the organic peroxide without causing the
crosslinking of the composition by: (i) applying pressure to the composition so as to
elevate the melting point of the crystalline polyolefin resin above the thermal
decomposition temperature of the peroxide; and (ii) heating the composition to a
temperature between the elevated melting point and the decomposition temperature.
US 4,123,584 (Southwire Co.) relates to a process for recovering scrap
thermosetting plastic compounds which comprises the steps of first hot-granulating
the fresh scrap compound before it has time to fully cure, allowing the granules to
cool, thereby arresting any further curing of the compound, then further processing
the granules into a fine powder. The fine powder can be reused directly or blended
with virgin material.
According to the Applicant, the above processes are substantially ineffective
and difficult to carry out on an industrial scale, since they require a very accurate
thermal control of the polymeric mass during the waste processing, a control that is
difficult to achieve particularly when large polymeric masses are to be treated.
Summary of the invention.
The Applicant has faced the problem of recovering wastes of a polymeric
composition including unreacted peroxidic crosslinking agent by a method that can
be carried out even on large amounts of wastes without requiring a complex multi-
step process and avoiding any even partial crosslinking of the material, so as to
allow a recycling of the recovered polymeric material to manufacture other articles,
preferably other electrical cable elements different from the insulating covering.
The Applicant has now found that the above problem can be solved by
adding, to the polymeric composition wastes, an antioxidant agent suitable for
certain elastomeric compositions. In particular, it has surprisingly found that a class
of antioxidant agents, generally defined as antioxidant agent suitable for sulfur-
vulcanized elastomeric compositions, is effective to quench the peroxide
crosslinking agent, so as to avoid any substantial crosslinking of the composition
during processing of the same. The addition of said at least one antioxidant agent is
carried out by compounding the polymeric wastes at a temperature lower than the
decomposition temperature of the peroxide crosslinking agent, so as to avoid any
premature activation of the crosslinking agent. This makes the process according to
the present invention particularly suitable for compositions based on elastomeric
polyolefins, more preferably for elastomeric ethylene copolymers such as ethylene-
propylene copolymers (EPR) and ethylene-propylene-diene terpolymers (EPDM),
which can be processed at relatively low temperatures, much lower than the
decomposition temperatures of the most common peroxide crosslinking agents.
Moreover, the Applicant has found that the so recovered polymeric
composition can be advantageously used in electric cable components such as
filling material for electrical cable cores or the like, where the mechanical and
electrical properties of such recovered polymeric composition is suitable. The
resultant cable is less expensive than an equivalent cable comprising a common
filling material because it contains waste material, but also because the Applicant
found that the composition recovered by the present process can be added with a
reduced amount of processing aids to be used as filling material.
Therefore, according to a first aspect, the present invention relates to a
process for recovering wastes of a polymeric composition including at least one
peroxide-curable polymer and at least one peroxidic crosslinking agent, which
comprises compounding the wastes with at least one antioxidant agent suitable for
sulfur-vulcanized elastomeric compositions, at a temperature lower than the
decomposition temperature of the at least one peroxide crosslinking agent.
For the purpose of the present description and of the claims that follow,
except where otherwise indicated, all numbers expressing amounts, quantities,
percentages, and so forth, are to be understood as being modified in all instances by
the term "about". Also, all ranges include any combination of the maximum and
minimum points disclosed and include any intermediate ranges therein, which may
or may not be specifically enumerated herein.
For the purposes of the present description and of the claims that follow, the
term "phr" means the parts by weight of a given component (or mixture of
components) of the polymeric composition per 100 parts by weight of the
polymer(s) contained therein.
Preferably, the peroxide-curable polymer is an elastomeric polyolefin.
As to the antioxidant agent suitable for sulfur-vulcanized elastomeric
compositions, it is preferably selected from primary antioxidants having reactive –
OH and/or –NH groups, such as hindered phenols or secondary aromatic amines.
With “primary antioxidant” it is meant an antioxidant which inhibits oxidation via a
chain termination reaction.
Preferably, the antioxidant agent is selected from: secondary phenylamines
and low molecular weight hindered phenols. With “low molecular weight“, it is
meant a molecular weight lower than 1000, preferably lower than 800. Secondary
phenylamines are, for example, secondary phenylenediamines, diphenylamines, or
derivatives thereof.
Secondary phenylenediamine suitable as antioxidants according to the
present invention may be selected, for example, from: N-phenyl-N'-iso-propyl-p-
phenylenediamine (IPPD), N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine
(6PPD), N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine (77PD), N,N'-bis-(1-
ethylmethylpentyl)-p-phenylenediamine (DOPD), N,N'-diphenyl-p-
phenylenediamine (DPPD), N,N'-ditolyl-p-phenylenediamine (DTPD), N,N'-di-ß-
naphthyl-p-phenylenediamine (DNPD), N,N'-bis-(1-methylheptyl)-p-
phenylenediamine, N,N'- di-sec-butyl-p-phenylenediamine (44PD), N-phenyl-N'-
cyclohexyl-p-phenylenediamine, N-phenyl-N'methylheptyl-p-phenylenediamine,
and mixtures thereof.
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) and N,N'-
ditolyl-p- phenylenediamine (DTPD) are particularly preferred.
Diphenylamine derivatives suitable as antioxidants according to the present
invention may be selected, for example, from: octylated diphenylamine (ODPA),
styrenated diphenylamine (SDPA), and mixtures thereof.
Hindered phenols suitable as antioxidants according to the present invention
may be selected, for example, from: 2,6-di-t-butyl-hydroxytoluene (BHT), 2,6-di-t-
butyl nonylphenol, 2,6-di-t-butylethylphenol, 4-nonylphenol, 3-(2,3-di-t-
butylhydroxyphenyl) propionic methyl ester, 3,5-di-t-butyl
hydroxyhydrocinnamic acid octadecyl ester, poly(dicyclopentadiene-co-p-cresol),
and mixtures thereof.
Poly(dicyclopentadiene-co-p-cresol) and 2,6-di-t-butyl-hydroxytoluene
(BHT) are particularly preferred.
Preferably, the antioxidant agent is mixed with the wastes to be recovered in
an amount of from 0.2 to 10 phr, more preferably of from 0.5 to 5 phr.
The molar amount of added antioxidant agent should be substantial equal or
in small excess with respect to the molar amount of peroxidic crosslinking agent
present in the polymeric composition. In case unreacted amounts of antioxidant
agent remain in the recovered polymeric composition, these are not detrimental for
the use of such composition, quite the reverse they could improve the antioxidant
characteristics thereof.
Preferably, the peroxide-curable polymer of the present invention may be
selected from:
(i) diene elastomeric polymers, generally having a glass transition temperature
(Tg) below 20°C, preferably from 0°C to –90°C;
(ii) chlorinated or chlorosulphonated polyethylenes;
(iii) elastomeric copolymers of at least one mono-olefin with at least one olefinic
comonomer or a derivative thereof;
(iv) polyester rubbers;
(v) polyurethane rubbers.
As regards the diene elastomeric polymers (i), they may be of natural origin
or may be obtained by solution polymerization, emulsion polymerization or gas-
phase polymerization of at least one conjugated diolefin, optionally in admixture
with at least one comonomer selected from monovinylarenes and/or polar
comonomers in an amount of not more than 60% by weight.
The conjugated diolefin generally contains from 4 to 12, preferably from 4
to 8, carbon atoms, and optionally may contain at least one halogen atom,
preferably chlorine or bromine. It may be selected preferably from the group
comprising: 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, 2,3-dimethyl-1,3-
butadiene, 1,3-pentadiene, 1,3-hexadiene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-
butadiene, or mixtures thereof. 1,3-butadiene, 2-chloro-1,3-butadiene and isoprene
are particularly preferred.
Monovinylarenes which may be optionally used as comonomers generally
contain from 8 to 20, preferably from 8 to 12, carbon atoms, and may be preferably
selected from: styrene, 1-vinylnaphthalene, α-methylstyrene, 3-methylstyrene, 4-
propylstyrene, 4-p-tolylstyrene, or mixtures thereof. Styrene is particularly
preferred.
Polar comonomers may be preferably selected from: vinylpyridine,
vinylquinoline, acrylic acid and alkylacrylic acid esters, nitriles or mixtures thereof,
such as, for example, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl
methacrylate, acrylonitrile, or mixtures thereof.
Preferably, the diene elastomeric polymer (i) may be selected from: cis-1,4-
polyisoprene (natural or synthetic, preferably natural rubber), 3,4-polyisoprene,
polybutadiene, polychloroprene, optionally halogenated isoprene/isobutene
copolymers, 1,3-butadiene/acrilonitrile copolymers (NBR), styrene/1,3-butadiene
copolymers (SBR), styrene/isoprene/1,3-butadiene copolymers, styrene/1,3-
butadiene/acrylonitrile copolymers, or mixtures thereof. Particularly preferred are
1,3-butadiene/acrilonitrile copolymers (NBR), available e.g. under the trade name
Krynac™ by Lanxess Deutschland GmbH.
As regards the chlorinated or chlorosulphonated polyethylenes (ii), they may
obtained by chlorination or chlorosulphonation of polyethylene.
Chlorination of polyethylene is generally carried out by radical reaction of
polyethylene with chlorine activated by means of UV radiation or by peroxides.
Chlorine content in the final polymer is generally from 25% to 45% by weight.
Commercial grades are available, e.g., under the tradename Tyrin™ by The Dow
Chemical Co.
Chlorosulphonation of polyethylene is generally carried out by dissolving
polyethylene in a chlorinated solvent and saturating said solution with chlorine and
sulphur dioxide under UV radiation. Chlorine content in the final polymer is
generally from 20% to 45% by weight, while sulphur content is generally from 0.8
to 2% by weight. Commercially grades are available, e.g., under the tradename
Hypalon™ by Du Pont Performance Elastomers LLC.
As regards the elastomeric copolymers (iii), they may be obtained by
copolymerization of at least one mono-olefin with at least one olefinic comonomer
or a derivative thereof. The monoolefins may be selected from: ethylene and α-
olefins generally containing from 3 to 12 carbon atoms, such as: propylene, 1-
butene, 1-pentene, 1-hexene, 1-octene, or mixtures thereof. The following are
preferred: copolymers of ethylene with an α-olefin, and optionally with a diene;
isobutene homopolymers or copolymers thereof with small amounts of a diene,
which are optionally at least partially halogenated. The diene optionally present
generally contains from 4 to 20 carbon atoms and is preferably selected from: 1,3-
butadiene, isoprene, 1,4-hexadiene, 1,4-cyclohexadiene, 5-ethylidenenorbornene,
-methylenenorbornene, vinylnorbornene, or mixtures thereof. Particularly
preferred are: ethylene/propylene copolymers (EPR), ethylene/propylene/diene
terpolymers (EPDM), polyisobutene, butyl rubbers, halobutyl rubbers, in particular
chlorobutyl or bromobutyl rubber; or mixtures thereof. Preferably, the EPR/EPDM
rubbers have the following monomer composition: 55-80% by weight, preferably
65-75% by weight, of ethylene; 20-45% by weight, preferably 25-35% by weight,
of propylene; 0-10% by weight, preferably 0-5% by weight, of a diene (preferably
5-ethylenenorbornene).
Alternatively, the peroxide-curable polymer is a thermoplastic polyolefin
such as:
(a) ethylene homopolymers or copolymers with at least one α-olefin, generally
containing from 3 to 12 carbon atoms, , such as: propylene, 1-butene, 1-pentene, 1-
hexene, 1-octene, or mixtures thereof, particularly low density polyethylene
(LDPE), linear low density polyethylene (LLDPE), medium density polyethylene
(MDPE), high density polyethylene (HDPE);
(b) ethylene copolymers with at least one ethylenically unsaturated ester such
as: ethylene/vinyl acetate copolymer (EVA), ethylene/methyl acrylate copolymer
(EMA), ethylene/ethyl acrylate copolymer (EEA), ethylene/butyl acrylate
copolymer (EBA); and mixtures thereof .
As regards the peroxidic crosslinking agent, it is preferably an organic
peroxide. Preferably, the peroxidic crosslinking agent has a decomposition
temperature equal to or greater than 90°C more preferably from 105°C to 145°C.
For example, the peroxidic crosslinking agent may be selected from:
dicumyl peroxide, t-butyl cumyl peroxide, bis(t-butylperoxyisopropyl) benzene,
bis(t-butylperoxy)2,5 dimethyl hexane, bis(t-butylperoxy)2,5 dimethyl hexyne, 2,4-
dimethyl-2,5-di(t-butylperoxy) hexane, di-t-butyl peroxide, and mixtures thereof.
Preferably, the peroxidic crosslinking agent is present in the polymeric
composition to be recovered in an amount of from 0.1 phr to 10 phr, more
preferably from 0.5 to 5 phr.
The polymeric composition to be recovered may possibly contain other
components, such as: fillers (e.g. carbon black, kaolin, calcium carbonate),
antioxidants, anti-ageing agents, plasticizers, lubricants, flame-retardants, voltage
stabilizers, water-tree retardants, etc.
The compounding of the wastes to be recovered with the antioxidant agent
according to the present invention is carried out at a temperature lower than the
decomposition temperature of the peroxide crosslinking agent, so as to avoid any
premature crosslinking of the polymeric material during the processing of the same.
Usually, the compounding temperature is lower than 150°C, preferably from 100°C
to 120°C.
The compounding can be carried out according to known techniques using a
mixing apparatus commonly used for such polymeric materials, e.g.: open mixers;
internal mixers having tangential rotors (Banbury) or interlocking rotors (Intermix);
Ko-Kneader continuous mixers (Buss); co-rotating or counter-rotating twin-screw
extruders.
To increase the processability of the wastes to be recovered, particularly
when fillers are to be added to obtain properties suitable for the application to
which the recovered polymeric material is intended, at least one processing aid is
preferably added to the polymeric wastes, selected e.g. from: naphthenic oils,
paraffinic oils, paraffinic waxes, stearic acid and salts or esters thereof. In this
respect, it should be noted that the antioxidant agent added to the polymeric wastes
can exert a certain lubricating action, therefore the amount of processing aid to be
added can be significantly lower than that expected. Moreover, the polymeric
wastes can already contain a certain amount of at least one processing aid, therefore
in some circumstances no additional processing aid is requested. When necessary,
the processing aid is preferably added in an amount of from 5 to 35 phr, more
preferably from 8 to 25 phr.
As already indicated above, the so recovered polymeric composition can be
advantageously used as filling material for electrical cable cores by extruding it
within the space surrounding the insulated conductors, since it is endowed with
suitable viscosity and does not crosslink during extrusion. To that purpose, the
polymeric composition is usually supplemented with at least one filler, such as
calcium carbonate, kaolin or the like.
According to another aspect, the present invention relates to a process for
recovering wastes of a polymeric composition including at least one peroxide-
curable polymer and at least one peroxidic crosslinking agent, which comprises
compounding the wastes with at least one antioxidant agent suitable for sulfur-
vulcanized elastomeric compositions, at a temperature lower than the
decomposition temperature of the at least one peroxide crosslinking agent. The at
least one antioxidant agent is selected from: secondary phenylamines, and low
molecular weight hindered phenols having a molecular weight lower than 1000
According to another aspect, the present invention relates to a cable
comprising at least one cable core and a component selected from a filling
material, a bedding and a dummy rod, wherein the component is made of a
recovered polymeric composition containing a product of reaction between a
peroxidic crosslinking agent and an antioxidant agent suitable for sulfur-vulcanized
elastomeric compositions. The at least one antioxidant agent is selected from:
secondary phenylamines, and low molecular weight hindered phenols having a
molecular weight lower than 1000.
The cable can be an electric, optic or optoelectric cable. The cable
component made of the recovered polymeric composition according to the
invention can be, for example, a filling material, a bedding or a dummy rod.
In particular, the cable of the invention comprises a protective layer
surrounding at least one electric cable core and a filling material made of a
recovered polymeric composition containing a product of reaction between a
peroxidic crosslinking agent and an antioxidant agent suitable for sulfur-vulcanized
elastomeric compositions.
Therefore, according to a further aspect, the present invention relates to the
use of a polymeric composition obtained from the process for recovering wastes as
described above, as filling material for electrical cable cores.
Particularly, the polymeric composition obtained from the process
according to the present invention can be used as filling material for a tripolar
electrical cable as illustrated in Figure 1 attached herewith (transversal cross
section).
With reference to Figure 1, the tripolar electrical cable (100), particularly
for medium voltage (MV) or high voltage (HV) applications, includes three cable
cores (1), wound together and surrounded by two protective layers (2) and (4). In
particular, the first protective layer (2) can be made from a metal tape (such as a
steel tape) or by an expanded polymeric material, as disclosed for instance in patent
application WO 98/52197. A second protective layer (4) is applied around and in
contact with the first protective layer (2). The second protective layer (4) is the
outermost external layer and is typically a polymeric sheath.
Each cable core (1) includes a metal conductor (10), an electrically
shielding layer (11) and a metal shield (12). The electrically shielding layer (11) is
constituted by an inner semiconductive layer, an electrically insulating layer and an
outer semiconductive layer (for sake of simplicity not specifically shown in Figure
1). The space surrounding the three cable cores (1) and delimited by the first
protective layer (2) is filled by a polymeric filling material (3), which is applied by
extrusion around the three wound cable cores (1).
The polymeric composition obtained from the process according to the
present invention may be advantageously used as polymeric filling material (3),
since it has a suitable viscosity to be extruded and to completely fill the voids
between the wound cable cores, and it does not show any crosslinking during
extrusion.
The following examples are provided to further illustrate the invention.
EXAMPLES 1-8.
The process according to the present invention was applied to recover a
waste of a polymeric composition typically used for electrical medium voltage
cable insulations having the following composition:
EPR rubber 100 phr
Kaolin 60 phr
Pb O 5 phr
ZnO 5 phr
Dicumyl peroxide 2.5 phr
Different commercial antioxidant agents were used:
Irganox™ 1010 (Ciba): pentaerythritol tetrakis(3-(3,5-di-tert-butyl
hydroxyphenyl)propionate) (CAS Registry No. 985843), typically used as
antioxidant for electrically insulating compositions, not for sulfur-vulcanized
elastomeric compositions (MW = 1178):
Lowinox™ CPL (Chemtura): poly(dicyclopentadiene-co-p-cresol)
(synonym: phenol, 4-methyl-, reaction products with dicyclopentadiene and
isobutene) (CAS Registry No. 686105), typically used as antioxidant for sulfur-
vulcanized elastomeric compositions (MW = 600-700):
Octamine™ (Chemtura): octylated diphenylamine (CAS Registry No.
266036), typically used as antioxidant for sulfur-vulcanized elastomeric
compositions:
H C C H
17 8 8 17
Vulkanox™ 4020 LG (Lanxess): N-(1,3-dimethylbutyl)-N'-phenyl-p-
phenylenediamine (CAS Registry No. 7938), typically used as antioxidant for
sulfur-vulcanized elastomeric compositions:
In each test, the polymeric waste was fed to a Banbury mixer in a granulated
form together with the antioxidant in the predetermined amounts. The
compounding was carried out with a mixer filling factor of 85%, a rotor speed of 50
rpm, a discharge temperature of the final composition of about 120°C.
The added amounts of antioxidants in the different tests are reported in
Table 1 (as parts by weight).
TABLE 1
Example 1 * 2 * 3 4 5 6 7 8
Waste mix 100 100 100 100 100 100 100 100
Irganox™ 1010 5.0 10.0 -- -- -- -- -- --
Lowinox™ CPL -- -- 5.0 10.0 -- -- -- --
Octamine™ -- -- -- 5.0 10.0 -- --
Vulkanox™ 4020 LG -- -- -- -- -- -- 5.0 10.0
* comparative
The resulting polymeric compositions were subjected to rheometric analysis
using a Moving Die Rheometer (MDR) from Monsanto, the tests being carried out
at 180°C for 15 minutes, with an oscillation frequency of 50 Hz and oscillation
amplitude of ± 3°.
The scorch time at 155°C was determined by means of a scorch
viscosimeter at 2’ + 22’, according to a standard technique.
As reference, the MDR and scorch characteristics were determined also on
the waste material as such, i.e. without adding any antioxidant (Ref. in Table 2).
The results are reported in Table 2.
TABLE 2
Ref. 1* 2* 3 4 5 6 7 8
0.43 0.31 0.16 0.28 0.23 0.27 0.18 0.22 0.16
M @180°C (dN · m) 10.22 2.11 0.67 0.86 0.35 0.88 0.32 0.30 0.19
t @180°C (min) 0:54 > 24 > 24 > 24 > 24 > 24 > 24 > 24 > 24
scorch t @155°C (min) 4:58 12:36 13:02 > 24 > 24 13:25 > 24 > 24 > 24
scorch t @155°C (min) 6:57 > 24 > 24 > 24 > 24 > 24 > 24 > 24 > 24
* comparative
M = minimum torque;
M = maximum torque;
t = time period to increase the torque value of 2 dN·m from the minimum
value M ;
scorch t = time necessary to increase the torque value of 3 dN·m from the
minimum value M ;
scorch t = time necessary to increase the torque value of 10 dN·m from
the minimum value M .
From the data reported in Table 2, it is apparent that, by adding the
antioxidant according to the present invention to the polymeric waste, the organic
peroxide present in the latter is almost completely quenched, as shown by the very
low values of M and the increased values of scorch time, with respect to the waste
material as such.
The compositions 1* and 2* containing an antioxidant for electrically
insulating compositions, not for sulfur-vulcanized elastomeric compositions,
showed scorch values (t ) unsuitable for a further use, and this is because such
antioxidant is not capable of quenching the unreacted peroxide included in these
compositions.
EXAMPLES 9-12.
The process according to the present invention was applied on the same
waste material of Examples 1-8 above, by compounding therein Vulkanox™ 4020
LG (Lanxess) in the amounts reported in Table 3 (parts by weight), by using the
same mixing process described for Examples 1-8. The compositions were also
added with relevant amounts of calcium carbonate as filler. Therefore, to improve
processability, it was necessary to supplement plasticizers and/or processing aids,
particularly a paraffinic oil, a paraffinic wax and stearic acid.
The compositions are reported in Table 3. The resulting polymeric
compositions were subjected to rheometric analysis (MDR) according to the same
method of Example 1-8. Moreover, Mooney ML(1+4) viscosity was measured at
100°C according to ISO Standard 289/1.
The results are reported in Table 4.
TABLE 3
Example 9 10 11 12
Waste mix 100 100 100 100
Vulkanox™ 4020 LG 3.0 6.0 3.0 6.0
Omyacarb™ 10 AV 225 225 225 225
Celtis™ 933 15 15 7.5 7.5
Riowax™ 721 10 10 10 10
Stearic acid 1.5 1.5 -- --
Omyacarb™ 10 AV (Omya) = calcium carbonate;
Celtis™ 933 (ENI) = paraffinic oil;
Riowax™ 721 (Lehmann & Voss & Co.): wax.
TABLE 4
Example 9 10 11 12
M @180°C (dN · m) 0.16 0.11 0.46 0.32
M @180°C (dN · m) 0.23 0.15 0.49 0.34
t @180°C (min) > 24 > 24 > 24 > 24
Mooney ML(1+4) viscosity 25 22.2 57.3 48.9
Scorch t @155°C (min) > 24 > 24 > 24 > 24
Scorch t @155°C (min) > 24 > 24 > 24 > 24
From Examples 9-12 it is apparent that the addition of the antioxidant agent
according to the present invention allowed to remarkably reduce the amount of
paraffinic oil and to eliminate stearic acid in the composition, which were added
along with the paraffinic wax to improve processability which was inevitably
reduced by the large amount of calcium carbonate filler incorporated into the
composition. An increase of the Mooney viscosity was observed because of the
reduction of the processing aids: it however remained within acceptable values for
the subsequent processing of the polymeric composition.
Claims (13)
1. A process for recovering wastes of a polymeric composition including at least one peroxide-curable polymer and at least one peroxidic crosslinking agent, which comprises compounding the wastes with at least one 5 antioxidant agent suitable for sulfur-vulcanized elastomeric compositions, at a temperature lower than the decomposition temperature of the at least one peroxide crosslinking agent; wherein the at least one antioxidant agent is selected from: secondary phenylamines, and 10 low molecular weight hindered phenols having a molecular weight lower than 1000.
2. The process according to claim 1, wherein the at least one antioxidant agent is selected from: 2,6-di-t-butyl-hydroxytoluene (BHT), 2,6-di-t- butyl nonylphenol, 2,6-di-t-butylethylphenol, 4-nonylphenol, 3-(2,3-di-t- 15 butylhydroxyphenyl) propionic methyl ester, 3,5-di-t-butyl hydroxyhydrocinnamic acid octadecyl ester, poly(dicyclopentadiene-co-p-cresol), and mixtures thereof.
3. The process according to claim 1, wherein the secondary phenylamines are selected from: secondary phenylenediamines, diphenylamines, 20 derivatives thereof, and mixtures thereof.
4. The process according to claim 3, wherein the secondary phenylenediamines are selected from: N-phenyl-N'-iso-propyl-p-phenylenediamine (IPPD), N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), N,N'-bis- (1,4-dimethylpentyl)-p-phenylenediamine (77PD), N,N'-bis-(1-ethyl 25 methylpentyl)-p-phenylenediamine (DOPD), N,N'-diphenyl-p-phenylenediamine (DPPD), N,N'-ditolyl-p-phenylenediamine (DTPD), N,N'-di-ß-naphthyl-p- phenylenediamine (DNPD), N,N'-bis-(1-methylheptyl)-p-phenylenediamine, N,N'- di-sec-butyl-p-phenylenediamine (44PD), N-phenyl-N'-cyclohexyl-p- phenylenediamine, N-phenyl-N'methylheptyl-p-phenylenediamine, and mixtures 5 thereof.
5. The process according to claim 1, wherein the antioxidant agent is compounded with the wastes to be recovered in an amount of from 0.2 to 10 phr, preferably from 0.5 to 5 phr.
6. The process according to claim 1, wherein the peroxide-curable 10 polymer is an elastomeric polyolefin.
7. The process according to claim 1, wherein the at least one peroxide- curable polymer is a thermoplastic polyolefin.
8. The process according to claim 1, wherein the at least one peroxidic crosslinking agent has a decomposition temperature equal to or greater than 90°C, 15 preferably from 105°C to 145°C.
9. The process according to claim 8, wherein the at least one peroxidic crosslinking agent is selected from: dicumyl peroxide, t-butyl cumyl peroxide, bis(t-butylperoxyisopropyl) benzene, bis(t-butylperoxy)2,5 dimethyl hexane, bis(t- butylperoxy)2,5 dimethyl hexyne, 2,4-dimethyl-2,5-di(t-butylperoxy) hexane, di-t- 20 butyl peroxide, and mixtures thereof.
10. The process according to claim 1, wherein the compounding of the wastes with the at least one antioxidant agent is carried out at a temperature lower than 150°C, preferably from 100°C to 120°C.
11. The process according to claim 1, wherein at least one processing 25 aid is added to the polymeric wastes.
12. Cable comprising at least one cable core and a component selected from a filling material, a bedding and a dummy rod, wherein the component is made of a recovered polymeric composition containing a product of reaction between a peroxidic crosslinking agent and an antioxidant agent suitable for sulfur- 5 vulcanized elastomeric compositions; wherein the at least one antioxidant agent is selected from: secondary phenylamines, and low molecular weight hindered phenols having a molecular weight lower than 1000. 10
13. Use of a polymeric composition obtained from the process for recovering wastes according to any one of claims from 1 to 11, as filling material for electrical cable cores.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/IB2012/056410 WO2014076520A1 (en) | 2012-11-14 | 2012-11-14 | Process for recovering wastes of a polymeric composition including a peroxidic crosslinking agent |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ707590A NZ707590A (en) | 2018-11-30 |
NZ707590B2 true NZ707590B2 (en) | 2019-03-01 |
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