CN103304716B - A kind of preparation method of liquid cis butadiene anti-aging agent - Google Patents
A kind of preparation method of liquid cis butadiene anti-aging agent Download PDFInfo
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- CN103304716B CN103304716B CN201310226445.7A CN201310226445A CN103304716B CN 103304716 B CN103304716 B CN 103304716B CN 201310226445 A CN201310226445 A CN 201310226445A CN 103304716 B CN103304716 B CN 103304716B
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- liquid
- aging agent
- antioxidant
- oxidation inhibitor
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- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 75
- 239000007788 liquid Substances 0.000 title claims abstract description 61
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 61
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 56
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 55
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims description 45
- 238000007254 oxidation reaction Methods 0.000 claims description 45
- 239000003112 inhibitor Substances 0.000 claims description 43
- -1 sulfur ethers Chemical class 0.000 claims description 35
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 10
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 8
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 claims description 8
- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical compound CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims description 6
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 4
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 4
- PAZXUKOJTOTKBK-UHFFFAOYSA-N n,n-dibutylhydroxylamine Chemical compound CCCCN(O)CCCC PAZXUKOJTOTKBK-UHFFFAOYSA-N 0.000 claims description 4
- ODHYIQOBTIWVRZ-UHFFFAOYSA-N n-propan-2-ylhydroxylamine Chemical compound CC(C)NO ODHYIQOBTIWVRZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 45
- 239000005060 rubber Substances 0.000 abstract description 45
- 230000032683 aging Effects 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 15
- 150000003568 thioethers Chemical class 0.000 abstract description 11
- 150000008301 phosphite esters Chemical class 0.000 abstract description 6
- 239000002530 phenolic antioxidant Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 30
- 239000000047 product Substances 0.000 description 25
- 239000003292 glue Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 239000004215 Carbon black (E152) Substances 0.000 description 13
- 229930195733 hydrocarbon Natural products 0.000 description 13
- 150000002430 hydrocarbons Chemical class 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 238000010092 rubber production Methods 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 244000286663 Ficus elastica Species 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 1
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N 1-Tetradecanol Natural products CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- UDFARPRXWMDFQU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)methylsulfanylmethyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CSCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 UDFARPRXWMDFQU-UHFFFAOYSA-N 0.000 description 1
- FANGQVKSFHFPBY-UHFFFAOYSA-N 2-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FANGQVKSFHFPBY-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 1
- CAPNUXMLPONECZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-2-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=C(O)C(C(C)(C)C)=C1 CAPNUXMLPONECZ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- WNFDFOPVGKYQOF-UHFFFAOYSA-N C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)P(O)(O)O Chemical compound C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)P(O)(O)O WNFDFOPVGKYQOF-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GQJDFTIOKVGUOF-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO Chemical class OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO GQJDFTIOKVGUOF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- OURRXQUGYQRVML-AREMUKBSSA-N [4-[(2s)-3-amino-1-(isoquinolin-6-ylamino)-1-oxopropan-2-yl]phenyl]methyl 2,4-dimethylbenzoate Chemical compound CC1=CC(C)=CC=C1C(=O)OCC1=CC=C([C@@H](CN)C(=O)NC=2C=C3C=CN=CC3=CC=2)C=C1 OURRXQUGYQRVML-AREMUKBSSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001993 dienes Chemical group 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000008297 liquid dosage form Substances 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229920000576 tactic polymer Polymers 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Abstract
The preparation method of a kind of liquid cis butadiene anti-aging agent of the present invention, belongs to anti-aging agent preparing technical field.Relate to a kind of liquified phenol kind antioxidant of preparation and a kind of thioether kind antioxidant, then with a kind of polyreaction terminator compound, add and be in harmonious proportion in still, stir, heat up, form liquid form mixt after mixing, be cooled to room temperature, obtain a kind of liquid cis butadiene anti-aging agent of the present invention.In described liquid anti-aging agent process, the cooperation of various material is counted in mass ratio, thioether kind antioxidant: phenolic antioxidant=1:0.40-0.63, thioether kind antioxidant: phosphite ester kind antioxidant=1:0.25-0.40; Thioether kind antioxidant: polyreaction terminator=1:0.10-0.20.Antiaging system of the present invention can significantly improve the Comprehensive Preventing aging resistance of rubber product.
Description
Technical field
The present invention is a kind of liquid nickel polymerized BR anti-aging agent of preparation, relate to a kind of liquified phenol kind antioxidant of preparation, have with other that material of liquid state is composite makes the complex antiager with liquid dosage form, it uses in synthesis nickel-system polybutadiene rubber, solve dust pollution and use safety problem in course of industrialization, and there is good ageing resistance.
Background technology
1,3-butadiene is raw material, C
6mixing-in fat hydrocarbon is as solvent, employing nickel naphthenate is Primary Catalysts, triisobutyl aluminium and boron trifluoride ethyl ether complex are the complex catalyst system of promotor, in C6 mixing-in fat hydrocarbon solvent, cause divinyl carry out coordinated anionic polymerization, add anti-aging agent after completing polyreaction, cohesion, nickel polymerized BR (being called for short NiBR) is made in drying, NiBR is diolefin series tactic polymer, molecular formula:
Due to the height nonsaturation of molecular structure, double bond position is caused to be very easy to be oxidized, form carbonyl oxygen carrier, especially under the effect being subject to hot oxygen, under the induction of residual catalyst spike, be easy to make in the middle of molecular chain, to produce reaction of propagation and the branching reaction that chain occurs then in active centre.Its result performance product appearance its colour changed into yellow, the rising of Mooney viscosity value, gel content rising, plasticity-reduce, and cause the physical and mechanical properties of its rubber unvulcanizate to be destroyed.
Anti-aging agent not only should have higher anti ageing property, and should be cheap, pollution-free, intermiscibility is good, the convenient feature used in course of industrialization, normally used Hinered phenols antioxidant has: 2, 6-di-tert-butyl-4-methy phenol (BHT), 2, 2 '-methylene-bis(4-ethyl-6-t-butyl phenol) (oxidation inhibitor 425), 2, 2 '-methylene-bis (4-methyl base-6-tert.-butyl phenol) (antioxidant 2246), 2, 2 '-methylene-bis (4, 6-DI-tert-butylphenol compounds), 2, 2 '-ethylene two (4, 6-DI-tert-butylphenol compounds), β-(4-hydroxyl-3, 5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid (antioxidant 1076), β-(4-hydroxyl-3, 5-di-tert-butyl-phenyl) the different monooctyl ester of propionic acid (oxidation inhibitor 1135), four (β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester (antioxidant 1010), two-3-(3-tertiary butyl-4-hydroxy-5-the aminomethyl phenyl of triglycol) propionic ester (oxidation inhibitor 245), phosphite ester kind antioxidant has: tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester (irgasfos 168), phosphorous acid (three nonyl phenyl) ester (antioxidant TNP P), diphosphorous acid pentaerythritol stearic acid ester 2 (oxidation inhibitor 619), two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites (oxidation inhibitor 626), thioether kind antioxidant has: two (3, 5-di-tert-butyl-4-hydroxyl benzyl) thioether, 2, 2 ' two (β-(3 of-sulfurous ethyl glycol, 5-di-tert-butyl-hydroxy phenyl) propionic ester), 2, 4-bis-(methylene-S-octyl group)-6-methylphenol (oxidation inhibitor 1520), 4, 4 '-thiobiss (2-methyl-6-tert-butylphenol), 2, 2 '-thiobiss (4-methyl-6-tert-butylphenol), 4, 4 '-thiobiss (2, 6-DI-tert-butylphenol compounds), 4, 4 '-thiobiss (6-tert-butyl-m-cresol), Tyox B (DLTDP), thio-2 acid two isotridecanol (DTDTP), thio-2 acid two (18) ester (DSTDP), the different tetradecyl alcohol ester of thio-2 acid two.
Single dose uses oxidation inhibitor to be difficult to meet the demands, the complementary performance of synergistic effect is utilized to reach the age inhibiting effect of expectation, foundation is with 1, 3-divinyl is the polymerization technology feature that nickel polymerized BR prepared by raw material, the cohesion of glue and drying process feature, the Changing Pattern of glue and rubber product mooney viscosity, the molecular weight of polymkeric substance divides Changing Pattern to study rubber product aging performance under various conditions, investigate the rubber product degree of dependence to anti-aging agent and terminator, optimized choice primary antioxidant, auxiliary antioxidant, terminator, and the preventing aging system formula that composition is best.
Adding anti-aging agent in production process prevents rubber chemical constitution and molecular structure in processing and storage process from changing exactly, keeps the fundamental property of product.Therefore, choice for use anti-aging agent is an important step during cis-1,4-polybutadiene rubber is produced.
China Synthetic Rubber Industry, 17(4 in 1994) disclose and replace 264 to use in cis-1,4-polybutadiene rubber with antioxidant 2246.
Petrochemical technology, 2001,8 (2) disclose the application of 1076 anti-aging agent in cis-1,4-polybutadiene rubber, and 1076 have good ageing resistance, and non-volatile, free from environmental pollution, are a kind of environment-friendly type anti-aging agent preferably.Its weak point is that ageing resistance is poor, especially variable color pessimum performance outstanding of phenolic antioxidant, and in addition, the use as solids oxidation inhibitor is inconvenient.
China Synthetic Rubber Industry, nineteen ninety-five, 18(1) disclose the anti-aging agent formula of cis-1,4-polybutadiene rubber, recommendation antioxidant 1010-168; Antioxidant 1076-TNPP binary antiaging system has good anti-aging effect.Its weak point does not have thioether kind antioxidant, uncontrollable cis-1,4-polybutadiene rubber product crosslinked aging in formula, makes it the rising of gel content and mooney viscosity.
Polymer Degradation and Stability49 (1995) discloses oxidation inhibitor 2,4-bis-(methylene-S-octyl group)-6-methylphenol and antioxidant 1076 makes complex antiager, and its anti ageing property is better than antioxidant 1010-168; Antioxidant 1076-TNPP binary antiaging system, especially with the addition of thioether kind antioxidant 1520, to a certain degree solves the crosslinked aging of cis-1,4-polybutadiene rubber product, makes it the problem of the rising of gel content and mooney viscosity.Its weak point does not have phosphite ester kind antioxidant, terminator in formula, and the comprehensive ageing resistance of cis-1,4-polybutadiene rubber product is poor, and especially anti-tarnishing ability is poor.
CN1919904 discloses a kind of preparation method of butadiene polymer oxidation inhibitor and the application in synthesis cis-1,4-polybutadiene rubber (being called for short BR), it adopts by a kind of bisphenols or Hinered phenols antioxidant and thioether kind antioxidant is raw material, and the proportioning according to regulation is carried out compound preparation and obtained a kind of novel antioxidant.Its weak point is inconvenient as the use of solids oxidation inhibitor, is the outstanding of the variable color pessimum performance of bisphenol compound antioxidant in addition.
CN101798405A discloses the nickel-system polybutadiene rubber complex antiager with anti-yellowing efficiency, containing sulfur type antioxidant by a kind of bisphenol monocarboxylic ester kind antioxidant, a kind of phosphite ester kind antioxidant with one is that raw material is made, and solves the variable color pessimum problem of bisphenol compound antioxidant.Its weak point is inconvenient as the use of solids oxidation inhibitor.
Above-mentioned disclosed cis-1,4-polybutadiene rubber anti-aging agent is all the oxidation inhibitor of solid powder state, have more than 95% to be solid powder oxidation inhibitor in numerous commodity oxidation inhibitor of the normally used Hinered phenols listed above-mentioned, phosphorous acid esters, thioether class, reason be to prepare the solid antioxidant with larger molecular weight, the antioxidant property had material choice wide in range; In addition, solid antioxidant is more convenient for commercialization manufacture, and especially in production process, product just can carry out refining purification by recrystallization method, obtain the finished product, many solid antioxidant commodity are for people's choice for use on a large scale, and compound preparation, derives the solid phase prod of a new generation then.Therefore, composite prod is still in the majority with solid antioxidant product all the time.
The use of liquid anti-aging agent in cis-1,4-polybutadiene rubber production process has a lot of advantages, as: the anti-aging agent that anti-aging agent joins production equipment by pail pack can be fed in raw material in storage tank with pump, mix with C6 mixing-in fat hydrocarbon, then measure anti-aging agent mixed solution to join in system and coordinate with glue; Liquid anti-aging agent can unrestrictedly mix with C6 mixing-in fat hydrocarbon, does not have crystallization and cause the filtering net of transfer line to block under any envrionment temperature.Compared with use solid powder oxidation inhibitor, save and move packed oxidation inhibitor to scaoffold by manpower, opening mouth is poured oxidation inhibitor into anti-aging agent and fed in raw material in storage tank, then mix with C6 mixing-in fat hydrocarbon; Solid anti-aging agent needs the solvent of more than 90% to dissolve usually, and nonetheless, transfer line also needs to do isothermal holding, otherwise has solid crystal in the winter time and separate out, the filtering net of blocking transfer line and affect device and normally run.By contrast, liquid anti-aging agent is used to alleviate the infringement to environment and human body of labour intensity and dust, the more important thing is that pouring oxidation inhibitor into anti-aging agent feeds in raw material in storage tank process, the C6 mixing-in fat hydrocarbon stream risen in tank mouth place and the oxidation inhibitor powder phase mutual friction of decline are easy to produce electrostatic and initiation fire and blast, for the Cis-Polybutadiene Rubber Plant with Class A anti-hazard classification, disaster hidden-trouble will be produced routine and bring serious threat.
In the Manufacture and application process of anti-aging agent, people are constantly overcoming traditional oxidation inhibitor application method and are using the defect that formulation exists, by selecting suitable oxidation inhibitor formulation, solve in industrialization anti-aging implementation process to environment, safety, HUMAN HEALTH bring many negative factors.In numerous commodity oxidation inhibitor of normally used Hinered phenols, phosphorous acid esters, thioether class, liquid antioxidant product is but for number is less, the leeway selected is very limited, unless planner customizes liquid antioxidant kind as required, and can be satisfied with the requirement of expection.In addition, the product purification means that liquid antioxidant is not applicable to, can only control impurity and by product, or investigate anti ageing property in product application process in product preparation.
Summary of the invention
The present invention prepares a kind of liquid cis butadiene anti-aging agent had containing polyreaction terminator, the continuity of polyreaction can not only be terminated fast, reduce less desirable disproportionation reaction, branching reaction, and the active centre of remaining catalyzer in rubber can be stopped, stop the generation of living radical, improve the stability of rubber product, comprehensive ageing resistance.
In cis-1,4-polybutadiene rubber production process, if divinyl be polymerized to without chain termination process, the time relying on the self termination of glue own to need is longer, and enter in the glue of glue tank and remained the activated catalyzer of tool, along with the shelf-time of glue in glue tank increases, macromole branching or crosslinking reaction can be there is, glue mooney viscosity is raised, the polyreaction terminator that tradition uses is ethanol, Virahol, due to the boiling point of ethanol and the boiling point of C6 mixing-in fat hydrocarbon solvent close, cause in the agglomeration process of glue, part ethanol is brought in the C6 mixing-in fat hydrocarbon solvent of recovery, as the solvent recycled, the poisoning of catalyst of next batch polyreaction can be caused undoubtedly, the carrying out of impact polymerization, finally have to abandon and the self termination of glue own can only be relied on.The present invention selects a kind of polyreaction terminator to mix with anti-aging agent, add at the end of polyreaction, serve the effect stopping in time polyreaction, make the molecular weight distribution of cis-1,4-polybutadiene rubber product in a close limit and reduce the generation of side chain, improve the stability of rubber product; Polyreaction terminator, in the agglomeration process of glue, can not be brought in the C6 mixing-in fat hydrocarbon solvent of recovery, but to remain in rubber and to produce collaborative anti-aging effect with anti-aging agent.
Polyreaction terminator is by 2, 2, 6, 6-tetramethylpiperidinol and a kind of hydroxylamine compound form, the continuity of polyreaction can not only be terminated fast, and the active centre of remaining catalyzer in rubber can be stopped, polyreaction terminator and complex antiager have good synergistic effect, especially hydroxylamine compound can suppress the oxidation stain of phenolic antioxidant to produce look dirt, final maintenance antiaging system good stability of the present invention, good to the anti ageing property of rubber, for the Comprehensive Preventing aging resistance of rubber product can be significantly improved in cis-1,4-polybutadiene rubber production process.
The present invention selects to prepare a kind of liquified phenol kind antioxidant, prepares a kind of liquid sulfur ethers oxidation inhibitor, then with one liquid phosphite ester kind antioxidant and polyreaction terminator composite, prepare a kind of liquid cis butadiene anti-aging agent.
The preparation method of a kind of liquid cis butadiene anti-aging agent of the present invention, carries out according to following step:
A kind of liquified phenol kind antioxidant and a kind of liquid sulfur ethers oxidation inhibitor being added with a kind of liquid phosphite kind antioxidant and a kind of polyreaction terminator is in proportion in harmonious proportion in still, stir, be warming up to 60-65 DEG C, stir 0.5h, form liquid form mixt after dissolving, be cooled to 30-35 DEG C and obtain a kind of liquid anti-aging agent of the present invention.
Wherein said liquid sulfur ethers oxidation inhibitor and the mixing ratio of liquified phenol kind antioxidant and liquid phosphite kind antioxidant and polyreaction terminator are counted in mass ratio, liquid sulfur ethers oxidation inhibitor: liquified phenol kind antioxidant=1:0.40-0.63, liquid sulfur ethers oxidation inhibitor: liquid phosphite kind antioxidant=1:0.25-0.40; Liquid sulfur ethers oxidation inhibitor: polyreaction terminator=1:0.10-0.20.
Wherein said liquified phenol kind antioxidant is: β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid isotridecanol;
Wherein said liquid sulfur ethers oxidation inhibitor is: 2,6-di-t-butyl-4-methylene radical-S-2-ethyl hexyl ethanoate base phenol;
Wherein said liquid phosphite kind antioxidant is: two (different tridecanol base) pentaerythritol diphosphites;
Wherein said polyreaction terminator is: hydroxylamine compound: 2,2,6,6-tetramethylpiperidinol (mass ratio)=1:0.10-1.0,
Wherein hydroxylamine compound refers to N, N-dibutylhydroxylamine or isopropylhydroxyla or diethyl hydroxylamine.
Advantage of the present invention
1, the use of liquid anti-aging agent in cis-1,4-polybutadiene rubber production process has a lot of advantages, as: the anti-aging agent that anti-aging agent joins production equipment by pail pack can be fed in raw material in storage tank, with C with pump
6mixing-in fat hydrocarbon mixes, then measures anti-aging agent mixed solution to join in system and coordinate with glue; Liquid anti-aging agent can unrestricted and C
6mixing-in fat hydrocarbon mixes, and does not have crystallization and cause the filtering net of transfer line to block under any envrionment temperature.Compared with use solid powder oxidation inhibitor, save and packed oxidation inhibitor moved to scaoffold by manpower, seal off mouth and pour oxidation inhibitor into anti-aging agent and feed in raw material in storage tank, then with C
6mixing-in fat hydrocarbon mixes; Solid anti-aging agent needs the solvent of more than 90% to dissolve usually, and nonetheless, transfer line also needs to do isothermal holding, otherwise has solid crystal in the winter time and separate out, the filtering net of blocking transfer line and affect device and normally run.By contrast, use liquid anti-aging agent to alleviate the infringement to environment and human body of labour intensity and dust, the more important thing is that pouring oxidation inhibitor into anti-aging agent feeds in raw material in storage tank process, the C that tank mouth rises
6mixing-in fat hydrocarbon stream and the oxidation inhibitor powder phase mutual friction of decline are easy to produce electrostatic and initiation fire and blast, and for the Cis-Polybutadiene Rubber Plant with Class A anti-hazard classification, disaster hidden-trouble will be produced routine and bring serious threat.
2, polyreaction terminator is 2, 2, 6, 6-tetramethylpiperidinol and a kind of hydroxylamine compound compound form, the continuity of polyreaction can not only be terminated fast, and the active centre of remaining catalyzer in rubber can be stopped, polyreaction terminator and complex antiager have good synergistic effect, especially hydroxylamine compound can suppress the oxidation stain of phenolic antioxidant to produce look dirt, final maintenance antiaging system good stability of the present invention, good to the anti ageing property of rubber, for the Comprehensive Preventing aging resistance of rubber product can be significantly improved in cis-1,4-polybutadiene rubber production process.
Embodiment
Hinered phenols antioxidant used in the present invention, thioether kind antioxidant, phosphite ester kind antioxidant and β-[3,5-di-tert-butyl-hydroxy phenyl] methyl propionate, isomerous tridecanol, di-nbutyltin oxide, 2, the different monooctyl ester of 6-DI-tert-butylphenol compounds, paraformaldehyde, thioacetic acid, dimethylamine, N, N-dibutylhydroxylamine, isopropylhydroxyla, diethyl hydroxylamine, 2,2,6,6-tetramethylpiperidinol, two (different tridecanol base) pentaerythritol diphosphites are commercially available industrial goods, and specification is industrial top grade product.
Following non-limiting example 1-3# or comparative example 1-2# is used for explaining and the present invention is described; instead of limit the invention; in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all belong to protection scope of the present invention.
The preparation method of β used in the present invention-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid isotridecanol, carries out according to following step:
90g β-[3 are added in the reactor with agitator, thermometer, the reflux exchanger being furnished with decompression vacuum pumping, nitrogen ingress pipe, 5-di-tert-butyl-hydroxy phenyl] methyl propionate, 65g isomerous tridecanol is, 0.35g di-nbutyltin oxide, after doing nitrogen replacement, nitrogen protection, stir and heat up, to 130 DEG C, insulation reaction 0.5h; Being decompressed to reacting kettle inner pressure is-0.05-0.06MPa, and temperature is 135-140 DEG C, insulation reaction 2h, constantly gets rid of by-product carbinol from reactor simultaneously; Reacting kettle inner pressure is-0.09-0.095MPa, temperature is 155-160 DEG C, insulation reaction 2h, constantly gets rid of by-product carbinol simultaneously from reactor, after reaction terminates, temperature is down to 100 DEG C, add 5g atlapulgite, insulated and stirred 0.5h, heat filtering removing atlapulgite at 100 DEG C, collected filtrate is β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid isotridecanol product.
2,6-di-t-butyl-4-methylene radical-S-2-ethyl hexyl ethanoate base phenol preparation method:
With in the GSHB type 1000mL glass reaction still of magnetic stirring apparatus, add 2,6 di t butyl phenol 206 grams, paraformaldehyde 36 grams, the different monooctyl ester of thioacetic acid 204 grams, after doing nitrogen replacement, nitrogen protection, add gas dimethylamine 4.5 grams, stir and be warming up to 60-65 DEG C, insulation reaction 2h; Be warming up to 95-100 DEG C, insulation reaction 2h; Be warming up to 130-135 DEG C, insulation reaction 2.5h, at 140-142 DEG C, pressure-0.095MPa maintains 0.5h, and reaction terminates.Be cooled to room temperature, obtain 2,6-di-t-butyl-4-methylene radical-S-2-ethyl hexyl ethanoate base phenol product.
Embodiment 1
Take 2,6-di-t-butyl-4-methylene radical-S-2-ethyl hexyl ethanoate base phenol 200 grams, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid isotridecanol 125 grams, two (different tridecanol base) pentaerythritol diphosphites 50 grams, N, N-dibutylhydroxylamine 20 grams, 2,2,6,6-tetramethylpiperidinol 2 grams, adds respectively and is in harmonious proportion in still, be warming up to 60-65 DEG C, stir 0.5h and mix rear formation liquid form mixt, be cooled to room temperature 30-35 DEG C, obtain 1# liquid anti-aging agent of the present invention.
Embodiment 2
Take 2,6-di-t-butyl-4-methylene radical-S-2-ethyl hexyl ethanoate base phenol 200 grams, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid isotridecanol 110 grams, two (different tridecanol base) pentaerythritol diphosphites 70 grams, diethyl hydroxylamine 10 grams, 2,2,6,6-tetramethylpiperidinol 10 grams, add respectively and be in harmonious proportion in still, be warming up to 60-65 DEG C, stir 0.5h and mix rear formation liquid form mixt, be cooled to room temperature 30-35 DEG C, obtain 2# liquid anti-aging agent of the present invention.
Embodiment 3
Take 2,6-di-t-butyl-4-methylene radical-S-2-ethyl hexyl ethanoate base phenol 200 grams, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid isotridecanol 80 grams, two (different tridecanol base) pentaerythritol diphosphites 80 grams, isopropylhydroxyla 25 grams, 2,2,6,6-tetramethylpiperidinol 15 grams, add respectively and be in harmonious proportion in still, be warming up to 60-65 DEG C, stir 0.5h and mix rear formation liquid form mixt, be cooled to room temperature 30-35 DEG C, obtain 3# liquid anti-aging agent of the present invention.
Comparative example 1
Take the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenmethyl)-4-aminomethyl phenyl acetic ester 200 grams, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 60 grams, Tyox B 240 grams, add in powder mixing tank, abundant mixing, makes and compares 1# anti-aging agent.
Comparative example 2
Take β-positive octadecyl ester of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid 160 grams, two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] thiodiethanol ester 240 grams, add in powder mixing tank, fully mix, make and compare 2# anti-aging agent.
Prepared by sample
Nickel polymerized BR glue 1000 grams is got from the polymerization end still of BR9000 production equipment, solid content is 17.3%, be added in the GSHB type 2000mL glass reaction still with magnetic stirring apparatus, add 0.346 gram, 1# liquid anti-aging agent of the present invention, at 60-65 DEG C, glue is fully stirred, oxidation inhibitor is made to be evenly dispersed in glue, continue to stir 3h at 60-65 DEG C, stop stirring, at 60-65 DEG C of standing 5h, then discharging, after 80-100 DEG C of hot water cohesion, 100 DEG C of roll-in dryings, makes 1# cis-1,4-polybutadiene rubber sample.Replace in the same way and use 2#, 3# liquid anti-aging agent of the present invention; Relatively 1#, 2# anti-aging agent makes 2# cis-1,4-polybutadiene rubber sample, 3# cis-1,4-polybutadiene rubber sample; Compare 1# cis-1,4-polybutadiene rubber sample, compare 2# cis-1,4-polybutadiene rubber sample.
Experimental technique:
1, the nickel polymerized BR glue 1000 grams not adding anti-aging agent is got, solid content is 17.3%, add in GSHB type 2000mL glass reaction still, add 1-3# liquid anti-aging agent of the present invention respectively and compare 0.346 gram, 1-2# anti-aging agent, at 60-65 DEG C, glue is fully stirred, oxidation inhibitor is made to be evenly dispersed in glue, continue to stir 3h at 60-65 DEG C, stop stirring, discharging after 60-65 DEG C of standing 5h, after 80-100 DEG C of hot water cohesion, 100 DEG C of roll-in dryings, make 1-3# cis-1,4-polybutadiene rubber sample; Relatively 1-2# cis-1,4-polybutadiene rubber sample.The Mooney viscosity of each sample is measured respectively by GB/T1232-1992
2, by 1-3# cis-1,4-polybutadiene rubber sample; Relatively print made by 1-2# cis-1,4-polybutadiene rubber sample, be placed in thermo-oxidative ageing case, by GB/T3512-1992, thermo-oxidative ageing test is carried out in (100 ± 1) DEG C, observe the time dependent degree of color of glue sample, with color difference meter, by GB/T1776-1995, test glue sample △ E value changing conditions or with the naked eye observe the color of glue sample in time; With automatic Mooney viscosity test instrument, measure the Mooney viscosity of rubber sample by GB/T1232-1992
change.
Experimental result
Table 1 is prepared in specimen, obtain the initial Mooney viscosity of each sample
The experimental result of table 1 is found out, the initial Mooney viscosity of 1-3# cis-1,4-polybutadiene rubber sample is made up lower than comparing the initial Mooney viscosity of 1-2# cis-1,4-polybutadiene rubber sample 2 numerical value of experimental technique 1, show that anti-aging agent of the present invention adds in glue, serve the effect stopping polyreaction in time, stop subsequent polymerisation reaction and generation that is crosslinked and branching reaction, improve the stability of rubber product.
Table 2 thermo-oxidative ageing test 72h, each sample value of chromatism △ E is along with the change of time
The test of table 3 thermo-oxidative ageing 96h, each sample Mooney viscosity (ML
1+4 100 DEG C) change
Table 2 experimental result shows, carries out thermo-oxidative ageing test 72 hours in (100 ± 1) DEG C, adds the appearance color of the 1-3# cis-1,4-polybutadiene rubber sample of anti-aging agent of the present invention significantly better than comparing 1-2# cis-1,4-polybutadiene rubber sample.
Table 3 experimental result shows, carries out thermo-oxidative ageing test 96 hours in (100 ± 1) DEG C, adds the Mooney viscosity of the 1-3# cis-1,4-polybutadiene rubber sample of anti-aging agent of the present invention
change be significantly less than contrast 1-2# cis-1,4-polybutadiene rubber sample.
Show thus, the present invention prepares a kind of liquid cis butadiene anti-aging agent had containing polyreaction terminator, the continuity of polyreaction can not only be terminated fast, reduce less desirable disproportionation reaction, branching reaction, and the active centre of remaining catalyzer in rubber can be stopped, stop the generation of living radical, improve the stability of rubber product, comprehensive ageing resistance.
Claims (5)
1. a preparation method for liquid cis butadiene anti-aging agent, is characterized in that carrying out according to following step:
A kind of liquified phenol kind antioxidant and a kind of liquid sulfur ethers oxidation inhibitor being added with a kind of liquid phosphite kind antioxidant and a kind of polyreaction terminator is in proportion in harmonious proportion in still, stir, be warming up to 60-65 DEG C, stir 0.5h, liquid form mixt is formed after dissolving, be cooled to 30-35 DEG C, obtain a kind of liquid cis butadiene anti-aging agent;
Wherein said liquid sulfur ethers oxidation inhibitor and the mixing ratio of liquified phenol kind antioxidant and liquid phosphite kind antioxidant and polyreaction terminator are counted in mass ratio, liquid sulfur ethers oxidation inhibitor: liquified phenol kind antioxidant=1:0.40-0.63, liquid sulfur ethers oxidation inhibitor: liquid phosphite kind antioxidant=1:0.25-0.40; Liquid sulfur ethers oxidation inhibitor: polyreaction terminator=1:0.10-0.20;
Wherein said liquified phenol kind antioxidant is: β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid isotridecanol.
2. the preparation method of a kind of liquid cis butadiene anti-aging agent according to claim 1, is characterized in that wherein said liquid sulfur ethers oxidation inhibitor is: 2,6-di-t-butyl-4-methylene radical-S-2-ethyl hexyl ethanoate base phenol.
3. the preparation method of a kind of liquid cis butadiene anti-aging agent according to claim 1, is characterized in that wherein said liquid phosphite kind antioxidant is: two (different tridecanol base) pentaerythritol diphosphites.
4. the preparation method of a kind of liquid cis butadiene anti-aging agent according to claim 1, is characterized in that wherein said polyreaction terminator is: hydroxylamine compound: 2,2,6,6-tetramethylpiperidinol (mass ratio)=1:0.10-1.0.
5. the preparation method of a kind of liquid cis butadiene anti-aging agent according to claim 1, is characterized in that wherein hydroxylamine compound refers to N, N-dibutylhydroxylamine or isopropylhydroxyla or diethyl hydroxylamine.
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| CN102181072A (en) * | 2011-02-24 | 2011-09-14 | 常州大学 | Preparation method of emulsion antioxidant |
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