CN102924748A - Preparation method of emulsion antioxidant product - Google Patents
Preparation method of emulsion antioxidant product Download PDFInfo
- Publication number
- CN102924748A CN102924748A CN2012104293394A CN201210429339A CN102924748A CN 102924748 A CN102924748 A CN 102924748A CN 2012104293394 A CN2012104293394 A CN 2012104293394A CN 201210429339 A CN201210429339 A CN 201210429339A CN 102924748 A CN102924748 A CN 102924748A
- Authority
- CN
- China
- Prior art keywords
- antioxidant
- emulsion
- preparation
- wingstay
- oxidation inhibitor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 69
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 67
- 239000000839 emulsion Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000010008 shearing Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 238000010790 dilution Methods 0.000 claims abstract description 13
- 239000012895 dilution Substances 0.000 claims abstract description 13
- -1 methylene di-sulfo ester compound Chemical class 0.000 claims abstract description 13
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims description 58
- 238000007254 oxidation reaction Methods 0.000 claims description 58
- 239000003112 inhibitor Substances 0.000 claims description 48
- 239000002131 composite material Substances 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000000047 product Substances 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 27
- 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 claims description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 13
- RZBBHEJLECUBJT-UHFFFAOYSA-N 6-methylheptyl 2-sulfanylacetate Chemical compound CC(C)CCCCCOC(=O)CS RZBBHEJLECUBJT-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- STLLXWLDRUVCHL-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)(C)CC)C(C)(C)CC)OC(=O)C=C)=C1O STLLXWLDRUVCHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 239000003945 anionic surfactant Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000002530 phenolic antioxidant Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 4
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000000344 soap Substances 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000012263 liquid product Substances 0.000 claims description 3
- 229940072033 potash Drugs 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- VYGSFTVYZHNGBU-UHFFFAOYSA-N trichloromethanesulfonic acid Chemical compound OS(=O)(=O)C(Cl)(Cl)Cl VYGSFTVYZHNGBU-UHFFFAOYSA-N 0.000 claims description 3
- ZRIHAIZYIMGOAB-UHFFFAOYSA-N butabarbital Chemical compound CCC(C)C1(CC)C(=O)NC(=O)NC1=O ZRIHAIZYIMGOAB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 20
- 239000002245 particle Substances 0.000 abstract description 4
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 229920002994 synthetic fiber Polymers 0.000 abstract description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 abstract 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 abstract 1
- 125000000129 anionic group Chemical group 0.000 abstract 1
- YZBVHXHKRXTLPG-UHFFFAOYSA-N buta-1,3-diene prop-2-enenitrile styrene Chemical compound C=CC1=CC=CC=C1.C=CC=C.C(C=C)#N.C=CC1=CC=CC=C1.C=CC=C.C(C=C)#N YZBVHXHKRXTLPG-UHFFFAOYSA-N 0.000 abstract 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 235000006708 antioxidants Nutrition 0.000 description 54
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 32
- 238000004945 emulsification Methods 0.000 description 21
- 239000004816 latex Substances 0.000 description 18
- 229920000126 latex Polymers 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 11
- 230000032683 aging Effects 0.000 description 9
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 230000006698 induction Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000002474 experimental method Methods 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
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006701 autoxidation reaction Methods 0.000 description 2
- 239000011324 bead Substances 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
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229940023462 paste product Drugs 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 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
- 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
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 description 1
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-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
- 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 206010023126 Jaundice Diseases 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
- 239000005062 Polybutadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 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
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 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 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 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 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Abstract
The invention provides a preparation method of an emulsion antioxidant product and belongs to the technical field of preparation of synthetic material antioxidant products. The emulsion antioxidant product is used for acrylonitrile butadiene styrene acrylonitrile butadiene styrene (ABS) grafting powder by means of an emulsion polymerization technology. Phenolic antioxygen Wingstay-L, an active ion radical trapping agent and a methylene di-sulfo ester compound are compounded according to the proportion to form a complex antioxidant, the complex antioxidant, isotridecyl alcohol polyoxyethylene ether or nonyl phenol polyoxyethylene ether and a dilution dispersing agent are mixed and stirred through a high speed shearing machine at the heating condition of 80-120 DEG C to form a homogeneous mixed liquid, and quantitative deionized water and an anionic surface active agent are added to continue to perform high speed shearing and stirring so as to obtain the antioxidant product having a water-soluble particle emulsion state, namely the emulsion antioxidant product.
Description
Technical field
The invention belongs to the preparing technical field of synthetic materials antioxidant product, be specifically related to a kind of preparation method of the New Emulsion antioxidant product for emulsion grafting polymerization explained hereafter ABS latex.
Background technology
Adopt emulsion grafting polymerization explained hereafter ABS latex, polymerization technique is to add the auxiliary agents such as emulsifying agent, water, polybutadiene latex, vinyl cyanide, styrene material monomer, initiator in polymeric kettle, stir and form microemulsion solution, finish at a certain temperature polyreaction.Then add terminator, oxidation inhibitor.Using of oxidation inhibitor is can be dispersed in the ABS latex as principle with it, and latex solution obtains ABS grafting powder after the cohesion dehydration, and oxidation inhibitor is dispersed in wherein uniformly, and the ageing resistance of ABS grafting powder directly affects the finished product.
For the device that adopts emulsion graft polymerization dry method blending explained hereafter ABS, because ABS grafting powder will pass through drying process, ABS powder particle after the cohesion has very large specific surface, drying is generally carried out under 110 ℃ to 130 ℃, has increased the duration of contact with warm air, with this understanding, the phenomenon of partial oxidation jaundice appears in powder particle easily, through high temperature screw rod granulation thermal ageing, its physical and mechanical properties is suffered again destruction in various degree, seriously affects its quality and use properties.
ABS grafting powder inevitably produces free polymer readical in the situation of being heated, it can contact with oxygen and form oxyradical and peroxylradicals, want to improve the resistance of oxidation of polymkeric substance, remove the material that produces radical, remove free radical, stop the carrying out of autoxidation chain reaction.Suitable oxidation inhibitor generally is composite and make by multiple compound with antioxygen, and usually by primary antioxidant, auxiliary antioxidant and the radical ion trapping agent of removing the material that produces radical form.Oxidation inhibitor commonly used has 2,6 di tert butyl 4 methyl 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) positive octadecyl ester of propionic acid (antioxidant 1076); Four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester (antioxidant 1010); Triglycol is two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) and 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).The thioether kind antioxidant has: two (3,5-di-tert-butyl-4-hydroxyl benzyl) thioether; 2,2
'-sulfurous ethyl glycol two (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester); 4,4
'-thiobis (2-methyl-6-tert-butylphenol); 2,2
'-thiobis (4-methyl-6-tert-butylphenol); 4,4
'-thiobis (2,6 di t butyl phenol); 4,4
'-thiobis (6-tertiary butyl meta-cresol); Tyox B (DLTDP); Thio-2 acid two isotridecanols (DTDTP); Thio-2 acid two (18) ester (DSTDP); Thio-2 acid two (14) ester.
Chinese Plastics, 2008, emulsion applications with anti-oxidant Irganox 245 and the composite system of DLTDP is disclosed in ABS latex 22(4), when being use, its weak point needs two kinds of oxidation inhibitor pressed powders are melted with the hot water that is higher than fusing point, use behind the reemulsification, so that production process is loaded down with trivial details, antioxidant component is difficult to Uniform Dispersion in emulsion in addition, so that can not be uniformly dispersed in ABS latex, the ABS powder antioxidant effect that the result obtains is bad.
In the ABS grafting powder production process, emulsion antioxidant is easy to use, the oxidation inhibitor adition process of having simplified, reduced the production cost of device, because this emulsion antioxygen and latex all are water-soluble substanceses, directly joined in the ABS latex, being convenient to latex mixes with the oxidation inhibitor emulsion, if oxidation inhibitor emulsification evenly, lastingly, then oxidation inhibitor can be evenly dispersed in the latex, can play good antioxygenation to ABS grafting powder; Otherwise, the bad dispersion effect that will directly affect in latex of oxidation inhibitor and water emulsifying effectiveness, and then affect the oxidation-resistance of rosin products.Therefore, solution aqueous emulsion type oxidation inhibitor dispersion effect is extremely important.
The production of aqueous emulsion type oxidation inhibitor has emulsion method and two kinds of producing and manufacturing technique of suspension method.Its difference is that suspension method is that oxidation inhibitor is dispersed in the aqueous phase liquid with insoluble solia particle; To be oxidation inhibitor stably disperse in the aqueous phase liquid with oil soluble liquid particulate independently emulsion method.
Suspension method is produced aqueous emulsion type oxidation inhibitor, needs to adopt ball mill and attritor,, as grinding medium composite antioxidant is constantly ground with stone, ceramic bead, stainless shot or other similar mechanically resistant materials; Emulsion method is produced aqueous emulsion type oxidation inhibitor, composite antioxidant and tensio-active agent, suitable organic solvent etc. are mixed, form liquid composition, adopt water screw or turbine type high-speed shearing machine to stir, fully mix and reach pre-emulsified effect, then add the continuation high speed shear such as deionized water, dispersion agent, stir and obtain product.
CN 101654540 discloses a kind of compound antioxidant preparation method for the ABS latex, take Wingstay-L and thioether oxidation inhibitor DLTDP as raw material, the rosin potash soap that adds deionized water and 80～90%, high speed homogenization emulsification prepares emulsion antioxidant, its weak point is that ageing resistance is poor, emulsion is unstable, easily condenses into the paste product.
CN101805458 discloses a kind of take DLTDP, 1076, Wingstay-L as raw material, prepares the method for emulsion composite antioxidant, and its weak point is that ageing resistance is poor, emulsion is unstable, easily condenses into the paste product.
Summary of the invention
The present invention adopts emulsion method production New Emulsion antioxidant product for overcoming above-mentioned deficiency of the prior art, is used for emulsion polymerization technique and produces ABS grafting powder.With phenolic antioxidant Wingstay-L and active ion base trapping agent and methylene bis monothioester compound composite composition composite antioxidant in proportion, with quantitative nonionogenic tenside and quantitative dilution dispersant, under heating condition, composite antioxidant is prepared into permanent liquid form mixt component, the employing high-speed shearing machine stirs, form the mixed solution of homogeneity state, add quantitative deionized water, continuing high speed shear after the quantitative anion surfactant stirs, obtain a kind of antioxidant product with water insoluble particulate emulsion state, both a kind of New Emulsion antioxidant product of the present invention.
The preparation method of a kind of emulsion antioxygen product of the present invention, carry out according to following step:
(1) preparation methylene bis monothioester compound: add in proportion formalin (mass concentration) and an acidic catalyst and the organic solvent of isooctyl mercaptoacetate and 37% in the reaction flask, stirring is warming up to reflux temperature, under reflux temperature, react, and constantly deviate from the water that reaction process generates, certain hour is carried out in reaction, and reaction is finished; The reaction mixture that obtains is washed to neutrality, and organic solvent is deviate from distillation, obtains water white transparency liquid product methylene bis monothioester compound;
(2) with phenolic antioxidant Wingstay-L and active ion base trapping agent and methylene bis monothioester compound composite composition composite antioxidant in proportion;
(3) with above-mentioned composite antioxidant and quantitative nonionogenic tenside and quantitative dilution dispersant;
(4) under 80-120 ℃ heating condition, composite antioxidant and nonionogenic tenside and dilution dispersion agent dissolve the permanent liquid form mixt component of rear formation mutually, adopt high-speed shearing machine to stir, and form the mixed solution of homogeneity state;
(5) mixed solution with step (4) the homogeneity state that forms is cooled to 40-45 ℃, add and continue high speed shear after quantitative deionized water and the quantitative anion surfactant and stir, obtaining the water miscible liquid oxidation inhibitor that Wingstay-L and active ion base trapping agent and methylene bis monothioester compound form, namely is New Emulsion antioxidant product of the present invention.
Wherein the described preparation methylene bis of step (1) monothioester compound is undertaken by following chemical reaction:
2HSCH
2COOC
8H
17+CH
2O?→?CH
2(S?CH
2COO?C
8H
17)
?2。
The described preparation methylene bis of step (1) monothioester compound wherein, the mixing ratio that adds various materials in the reaction flask is according to isooctyl mercaptoacetate: formaldehyde (mol ratio)=1:0.50-0.65; Isooctyl mercaptoacetate: an acidic catalyst (mass ratio)=1:0.005-0.015; Isooctyl mercaptoacetate: organic solvent (mass ratio)=1:0.8-1.2; Reflux temperature is 80-115 ℃; Reaction times is 2-4h; Organic solvent refers to C
6～C
8Aromatic hydrocarbon or C
8Straight-chain paraffin, isoparaffin, naphthenic hydrocarbon; Be specially toluene, hexanaphthene; An acidic catalyst refers to methylsulphonic acid, trifluoromethayl sulfonic acid, trichloromethane sulfonic acid.
Active ion base trapping agent described in the step (2) is 2-[1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl)-ethyl]-4,6-di-tert-pentyl-phenyl acrylate (is called for short: antioxidant GS); Shown in the following formula I of phenolic antioxidant Wingstay-L:
（Ⅰ）
The mixing ratio of the composite antioxidant described in the step (2) is according to, oxidation inhibitor Wingstay-L: antioxidant GS (mass ratio)=1:0.04-0.08; Oxidation inhibitor Wingstay-L: methylene bis monothioester compound (mass ratio)=1:1.8-2.6.
Nonionogenic tenside described in the step (3) is different tridecanol polyoxyethylene ether or polyoxyethylene nonylphenol ether;
The dilution dispersion agent is naphthenic rubber oil; Described quantitative nonionogenic tenside refers to: oxidation inhibitor Wingstay-L: nonionogenic tenside (mass ratio)=1:0.12-0.28; Described quantitative dilution dispersion agent refers to: oxidation inhibitor Wingstay-L: dilution dispersion agent (mass ratio)=1:0.3-0.7..
The permanent liquid form mixt component of formation described in the step (4) refers to the formation liquid form mixt and still keep original liquid state under 1-25 ℃ envrionment temperature, neither solidifies, do not become paste.
Anion surfactant described in the step (5) is the 25%(mass concentration) nilox resin acid potash soap liquid; Described quantitative anion surfactant refers to: oxidation inhibitor Wingstay-L: anion surfactant removes (mass ratio)=1:0.5-0.7; Described quantitative deionized water refers to: oxidation inhibitor Wingstay-L: deionized water (mass ratio)=1:1.8-2.2.
Advantage of the present invention
1, the present invention has used the composite composition composite antioxidant of phenolic antioxidant Wingstay-L and active ion base trapping agent and methylene bis monothioester compound, with nonionogenic tenside, anion surfactant, dilution dispersant, make a kind of antioxidant product with water insoluble particulate emulsion state, solvent with the polymer phase in the ABS latex, after the cohesion, the high efficiency composition antioxidant component can be dispersed in the ABS resin grafting powder uniformly, improve the usefulness of ABS resin oxidation inhibitor, effectively improved colour stability and the high high-temp stability of product.
2, the methylene bis monothioester compound antioxidant of the present invention preparation is liquid product, compares the sulphur content height, has improved the ageing resistance of composite antioxidant product of the present invention in ABS resin with traditional thioether oxidation inhibitor DTDTP.
3, composite antioxidant product of the present invention contains a small amount of active ion base trapping agent, the initial root that just can cut off chainpropagation in ABS resin generation autoxidation, prevented that alkyl diradical from further wearing out with the oxygen reaction, the oxidation induction period of ABS resin is prolonged, improved the oxidation resistant performance of ABS resin.
Embodiment
All raw materials used in the present invention are the commercial industrial product, and specification is industrial top grade product: oxidation inhibitor Wingstay-L, and outward appearance is white or off-white powder; Different tridecanol polyoxyethylene ether or different tridecanol and ethylene oxide condensate commodity E-1300 series by name; Naphthenic rubber oil man product are called KN4008; The polyoxyethylene nonylphenol ether commodity are called TX-10; Isooctyl mercaptoacetate, 37% formalin, an acidic catalyst, antioxidant GS, anti-oxidant Irganox 245, oxidation inhibitor DLTDP, anion surface activity, organic solvent.
One,
The preparation of methylene bis monothioester compound
Embodiment 1
Agitator is being housed, the reflux condensation mode water trap, add isooctyl mercaptoacetate 100g in the 500mL there-necked flask of thermometer, 37% formalin 79.5g, toluene 80g, methylsulphonic acid 1.0g, stirring is warming up to 110-115 ℃, under this temperature, carry out back flow reaction, meanwhile, constantly from reaction solution, deviate from water, back flow reaction 2.0h by the reflux condensation mode water trap, reaction is finished, reaction solution is cooled to 25-35 ℃, and washing is removed an acidic catalyst to reaction solution and is approached neutrality, and the toluene in the reaction solution is removed in distillation, obtain water white liquid, both methylene bis monothioester compound of the present invention.
Embodiment 2
Agitator is being housed, the reflux condensation mode water trap, add isooctyl mercaptoacetate 100g in the 500mL there-necked flask of thermometer, 37% formalin 95.4g, hexanaphthene 100g, trifluoromethayl sulfonic acid 0.5g, stirring is warming up to 79-81 ℃, under this temperature, carry out back flow reaction, meanwhile, constantly from reaction solution, deviate from water, back flow reaction 3.0h by the reflux condensation mode water trap, reaction is finished, reaction solution is cooled to 25-35 ℃, and washing is removed an acidic catalyst to reaction solution and is approached neutrality, and the hexanaphthene in the reaction solution is removed in distillation, obtain water white liquid, both methylene bis monothioester compound of the present invention.
Embodiment 3
Agitator is being housed, the reflux condensation mode water trap, add isooctyl mercaptoacetate 100g in the 500mL there-necked flask of thermometer, 37% formalin 103.3g, hexanaphthene 120g, trichloromethane sulfonic acid 1.5g, stirring is warming up to 96-98 ℃, under this temperature, carry out back flow reaction, meanwhile, constantly from reaction solution, deviate from water, back flow reaction 4.0h by the reflux condensation mode water trap, reaction is finished, reaction solution is cooled to 25-35 ℃, and washing is removed an acidic catalyst to reaction solution and is approached neutrality, and hexanaphthene in the reaction solution is removed in distillation, obtain colourless transparent liquid, both methylene bis monothioester compound of the present invention.
Two,
The preparation of New Emulsion antioxidant product
Embodiment 4
With 50g oxidation inhibitor Wingstay-L, 90g methylene bis monothioester compound, the composite composition composite antioxidant of 2g antioxidant GS, add in the beaker after composite antioxidant mixes with the different tridecanol polyoxyethylene ether of 20g KN4008,6g, be heated to 80 ℃, stir and melt evenly, homogeneous pre-emulsification 20-25min under high-speed shearing machine, temperature be down to 40-45 ℃ for subsequent use; With 25g 25% potassium rosinate, 90g deionized water mixed dissolution, and under high-shear, slowly add in the oil phase for preparing, add afterwards homogeneous pre-emulsification 20-30min under high-speed shearing machine; Slowly reduce velocity of shear after the emulsification, and at the low shearing speed borehole cooling to 25-30 ℃, obtain the New Emulsion antioxidant product.PH=9.5, viscosity 620cP.S.
Embodiment 5
With 50g oxidation inhibitor Wingstay-L, 100g methylene bis monothioester compound, the composite composition composite antioxidant of 3.0g antioxidant GS, add in the beaker after composite antioxidant mixes with the different tridecanol polyoxyethylene ether of 15g KN4008,10g, be heated to 110 ℃, stir and melt evenly, homogeneous pre-emulsification 20-25min under high-speed shearing machine, temperature be down to 40-45 ℃ for subsequent use; With 30g 25% potassium rosinate, 100g deionized water mixed dissolution, and under high-shear, slowly add in the oil phase for preparing, add afterwards homogeneous pre-emulsification 20-30min under high-speed shearing machine; Slowly reduce velocity of shear after the emulsification, and at the low shearing speed borehole cooling to 25-30 ℃, obtain the New Emulsion antioxidant product.PH=9.1, viscosity 680cP.S.
Embodiment 6
With 50g oxidation inhibitor Wingstay-L, 110g methylene bis monothioester compound, the composite composition composite antioxidant of 4.0g antioxidant GS, add in the beaker after composite antioxidant mixes with the different tridecanol polyoxyethylene ether of 30g KN4008,8g, be heated to 90 ℃, stir and melt evenly, homogeneous pre-emulsification 20-25min under high-speed shearing machine, temperature be down to 40-45 ℃ for subsequent use; With 28g 25% potassium rosinate, 95g deionized water mixed dissolution, and under high-shear, slowly add in the oil phase for preparing, add afterwards homogeneous pre-emulsification 20-30min under high-speed shearing machine; Slowly reduce velocity of shear after the emulsification, and at the low shearing speed borehole cooling to 25-30 ℃, obtain the New Emulsion antioxidant product.PH=10.0, viscosity 700cP.S.
Embodiment 7
With 50g oxidation inhibitor Wingstay-L, 120g methylene bis monothioester compound, the composite composition composite antioxidant of 2.5g antioxidant GS, add in the beaker after composite antioxidant mixes with 35g KN4008,12g polyoxyethylene nonylphenol ether, be heated to 100 ℃, stir and melt evenly, homogeneous pre-emulsification 10-15min under high-speed shearing machine, temperature be down to 40-45 ℃ for subsequent use; With 35g 25% potassium rosinate, 105g deionized water mixed dissolution, and under high-shear, slowly add in the oil phase for preparing, add afterwards homogeneous pre-emulsification 20-30min under high-speed shearing machine; Slowly reduce velocity of shear after the emulsification, and at the low shearing speed borehole cooling to 25-30 ℃, obtain the New Emulsion antioxidant product.PH=9.8, viscosity 630cP.S.
Embodiment 8
With 50g oxidation inhibitor Wingstay-L, 130g methylene bis monothioester compound, the composite composition composite antioxidant of 3.5g antioxidant GS, add in the beaker after composite antioxidant mixes with the different tridecanol polyoxyethylene ether of 25g KN4008,14g, be heated to 120 ℃, stir and melt evenly, homogeneous pre-emulsification 20-25min under high-speed shearing machine, temperature be down to 40-45 ℃ for subsequent use; With 30g 25% potassium rosinate, 110g deionized water mixed dissolution, and under high-shear, slowly add in the oil phase for preparing, add afterwards homogeneous pre-emulsification 20-30min under high-speed shearing machine; Slowly reduce velocity of shear after the emulsification, and at the low shearing speed borehole cooling to 25-30 ℃, obtain the New Emulsion antioxidant product.PH=9.2, viscosity 650cP.S.
Comparative Examples
According to new lake (Changzhou) petrochemical industry company limited ABS resin production technique, the composite antioxidant of Irganox245:DLTDP=1:1 is melted in hot water, add the potassium rosinate soap lye and make emulsion antioxygen, add-on is in the solid powder of Irganox245, DLTDP.
Three, ABS sample oxidation susceptibility test experiments method
1, oxidation induction period
With DSC200PC type differential scanning calorimetric analysis instrument, quality is placed aluminum dish for the ABS grafting powder sample of (15.0 ± 0.5) mg, with the logical people's nitrogen of (50 ± 5) mL/min, 20 ℃/min of control temperature rise rate is warming up to 160 ℃.Constant temperature 3min uses replacement of oxygen nitrogen, 160 ℃ of constant temperature, until the exothermic maximum signal occurs, the time of record is oxidation induction period min.
2, air oven aging test
With ABS grafting powder aluminum dish splendid attire, thickness is about 5mm, put into LR 016 A type thermo-oxidative ageing case and carry out air oven aging test, set 180 ℃ of senile experiment temperature, set ventilation condition, the appearance color changing conditions of regularly observing powder, when powder becomes Vandyke brown writing time min, be set as scorch time, the longer sample of scorch time shows that antioxygen property is all right.
Four, ABS preparation method of sample
Take by weighing the New Emulsion antioxidant product 0.2-0.4g that 50.0g ABS latex (new lake (Changzhou) petrochemical industry company limited produces, and resin content is 42%) is added in the beaker, quantitatively adds successively embodiment of the invention 4-8; Comparative Examples composite antioxidant 0.2-0.4g, under agitation as appropriate speed, be warming up to 60 ℃ stand-by; Other takes by weighing analytical reagent H
3PO
40.64g, MgSO
42.22g deionized water 102.33g places reflux 250mL flask is housed, and is warmed up to 90 ℃, stirring velocity 250 r/min; When mixed solution in the beaker is warming up to 90 ℃, add preheated ABS latex in the 2min; Temperature is kept 90 ℃, insulation 30min; After polymer beads is separated out fully, filter, deionized water wash is neutral to approaching, and 50-60 ℃ of vacuum-drying obtains adding the ABS grafting powder sample of oxidation inhibitor, 5 of embodiment; 2 of Comparative Examples.
Five, senile experiment result
Table 1 oxidation induction period and scorch time
| 50gABS latex adds the amount of oxidation inhibitor | Oxidation induction period (min) | Scorch time (min) |
| 0.20g embodiment 4 | 90 | 358 |
| 0.30g embodiment 5 | 95 | 375 |
| 0.20g embodiment 6 | 91 | 355 |
| 0.40g embodiment 7 | 98 | 389 |
| 0.20g embodiment 8 | 92 | 356 |
| 0.20g Comparative Examples | 65 | 270 |
| 0.40g Comparative Examples | 80 | 336 |
Can find out that from the test result of table 1 50gABS latex adds the emulsion antioxidant of 0.2-0.4g embodiment of the invention 4-8 preparation, 5 samples that obtain.Be 90-98 minute at 160 ℃ oxidation induction periods, be higher than 65-80 minute of Comparative Examples sample; At 180 ℃ air oven aging test, the scorch time of 5 samples that adds the emulsion antioxidant of embodiment of the invention 4-8 preparation was 355-389 minute, apparently higher than 270-336 minute of Comparative Examples.Can think that thus the antioxidant property of the New Emulsion antioxidant product that the present invention prepares is better than the employed oxidation inhibitor of Comparative Examples.
Claims (7)
1. the preparation method of an emulsion antioxygen product is characterized in that carrying out according to following step:
(1) preparation methylene bis monothioester compound: be that 37% formalin and an acidic catalyst and organic solvent add in the reaction flask in proportion with isooctyl mercaptoacetate and mass concentration, stirring is warming up to reflux temperature, under reflux temperature, react, and constantly deviate from the water that reaction process generates, certain hour is carried out in reaction, and reaction is finished; The reaction mixture that obtains is washed to neutrality, and organic solvent is deviate from distillation, obtains water white transparency liquid product methylene bis monothioester compound;
(2) with phenolic antioxidant Wingstay-L and active ion base trapping agent and methylene bis monothioester compound composite composition composite antioxidant in proportion;
(3) with above-mentioned composite antioxidant and quantitative nonionogenic tenside and quantitative dilution dispersant;
(4) under 80-120 ℃ heating condition, composite antioxidant and nonionogenic tenside and dilution dispersion agent dissolve the permanent liquid form mixt component of rear formation mutually, adopt high-speed shearing machine to stir, and form the mixed solution of homogeneity state;
(5) mixed solution with step (4) the homogeneity state that forms is cooled to 40-45 ℃, add and continue high speed shear after quantitative deionized water and the quantitative anion surfactant and stir, obtaining the water miscible liquid oxidation inhibitor that Wingstay-L and active ion base trapping agent and methylene bis monothioester compound form, namely is New Emulsion antioxidant product of the present invention.
2. the preparation method of a kind of emulsion antioxygen product according to claim 1, it is characterized in that the wherein described preparation methylene bis of step (1) monothioester compound, the mixing ratio that adds various materials in the reaction flask according to: isooctyl mercaptoacetate and formaldehyde mole ratio are 1:0.50-0.65; The mass ratio of isooctyl mercaptoacetate and an acidic catalyst is 1:0.005-0.015; The mass ratio of isooctyl mercaptoacetate and organic solvent is 1:0.8-1.2; Reflux temperature is 80-115 ℃; Reaction times is 2-4h; Organic solvent refers to C
6～C
8Aromatic hydrocarbon or C
8Straight-chain paraffin, isoparaffin, naphthenic hydrocarbon; An acidic catalyst refers to methylsulphonic acid, trifluoromethayl sulfonic acid, trichloromethane sulfonic acid.
3. the preparation method of a kind of emulsion antioxygen product according to claim 2 is characterized in that wherein the described organic solvent of step (1) is toluene or hexanaphthene.
4. the preparation method of a kind of emulsion antioxygen product according to claim 1, it is characterized in that the active ion base trapping agent described in the step (2) is 2-[1-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl)-and ethyl]-4,6-di-tert-pentyl-phenyl acrylate (is called for short: antioxidant GS); Shown in the following formula I of phenolic antioxidant Wingstay-L:
；
（Ⅰ）
The mixing ratio of the composite antioxidant described in the step (2) according to, oxidation inhibitor Wingstay-L and antioxidant GS mass ratio are 1:0.04-0.08; Oxidation inhibitor Wingstay-L is 1:1.8-2.6 with methylene bis monothioester compound quality ratio.
5. the preparation method of a kind of emulsion antioxygen product according to claim 1 is characterized in that the nonionogenic tenside described in the step (3) is different tridecanol polyoxyethylene ether or polyoxyethylene nonylphenol ether;
The dilution dispersion agent is naphthenic rubber oil; Described quantitative nonionogenic tenside refers to: oxidation inhibitor Wingstay-L and nonionogenic tenside mass ratio are 1:0.12-0.28; Described quantitative dilution dispersion agent refers to: oxidation inhibitor Wingstay-L is 1:0.3-0.7 with dilution dispersion agent mass ratio.
6. the preparation method of a kind of emulsion antioxygen product according to claim 1, it is characterized in that the permanent liquid form mixt component of the formation described in the step (4) refers to the formation liquid form mixt and still keep original liquid state under 1-25 ℃ envrionment temperature, neither solidify, do not become paste.
7. the preparation method of a kind of emulsion antioxygen product according to claim 1 is characterized in that the nilox resin acid potash soap liquid that the anion surfactant mass concentration described in the step (5) 25% is; Described quantitative anion surfactant refers to: it is 1:0.5-0.7 that oxidation inhibitor Wingstay-L and anion surfactant remove mass ratio; Described quantitative deionized water refers to: oxidation inhibitor Wingstay-L is that the deionized water quality is than being 1:1.8-2.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210429339.4A CN102924748B (en) | 2012-11-01 | 2012-11-01 | Preparation method of emulsion antioxidant product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210429339.4A CN102924748B (en) | 2012-11-01 | 2012-11-01 | Preparation method of emulsion antioxidant product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102924748A true CN102924748A (en) | 2013-02-13 |
| CN102924748B CN102924748B (en) | 2014-10-29 |
Family
ID=47639689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210429339.4A Active CN102924748B (en) | 2012-11-01 | 2012-11-01 | Preparation method of emulsion antioxidant product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102924748B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107778499A (en) * | 2017-11-16 | 2018-03-09 | 长春工业大学 | A kind of method that the water-based antioxidant of high-melting-point is prepared based on Dynamic Precipitation method room temperature |
| CN108239301A (en) * | 2016-12-23 | 2018-07-03 | 中国石油天然气股份有限公司 | Emulsion composite antioxidant and preparation method thereof |
| CN111909528A (en) * | 2020-06-18 | 2020-11-10 | 福建瑞森新材料股份有限公司 | Antioxidant emulsion capable of being emulsified and stabilized at normal temperature and preparation method thereof |
| CN113444527A (en) * | 2021-06-29 | 2021-09-28 | 江苏品和石油科技有限公司 | Preparation method of antioxidant stabilizer for lithium ion diaphragm pore-forming oil |
| WO2023202971A1 (en) * | 2022-04-20 | 2023-10-26 | Basf Se | An aqueous antioxidant suspoemulsion and a process for preparing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1643054A (en) * | 2002-03-15 | 2005-07-20 | 拜尔化学品股份公司 | Stabiliser combinations for polymer systems |
| CN101805458A (en) * | 2010-04-07 | 2010-08-18 | 天津力生化工有限公司 | Method for preparing emulsion composite antioxidant |
-
2012
- 2012-11-01 CN CN201210429339.4A patent/CN102924748B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1643054A (en) * | 2002-03-15 | 2005-07-20 | 拜尔化学品股份公司 | Stabiliser combinations for polymer systems |
| CN101805458A (en) * | 2010-04-07 | 2010-08-18 | 天津力生化工有限公司 | Method for preparing emulsion composite antioxidant |
Non-Patent Citations (1)
| Title |
|---|
| 杜飞，等: "双酚单丙烯酸酯类复合防老剂在氯丁橡胶中的应用", 《合成橡胶工业》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108239301A (en) * | 2016-12-23 | 2018-07-03 | 中国石油天然气股份有限公司 | Emulsion composite antioxidant and preparation method thereof |
| CN108239301B (en) * | 2016-12-23 | 2020-03-10 | 中国石油天然气股份有限公司 | Emulsion type composite antioxidant and preparation method thereof |
| CN107778499A (en) * | 2017-11-16 | 2018-03-09 | 长春工业大学 | A kind of method that the water-based antioxidant of high-melting-point is prepared based on Dynamic Precipitation method room temperature |
| CN111909528A (en) * | 2020-06-18 | 2020-11-10 | 福建瑞森新材料股份有限公司 | Antioxidant emulsion capable of being emulsified and stabilized at normal temperature and preparation method thereof |
| CN113444527A (en) * | 2021-06-29 | 2021-09-28 | 江苏品和石油科技有限公司 | Preparation method of antioxidant stabilizer for lithium ion diaphragm pore-forming oil |
| WO2023202971A1 (en) * | 2022-04-20 | 2023-10-26 | Basf Se | An aqueous antioxidant suspoemulsion and a process for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102924748B (en) | 2014-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102181072B (en) | Preparation method of emulsion antioxidant | |
| CN102924748B (en) | Preparation method of emulsion antioxidant product | |
| CN101137685A (en) | Suspension particle comprising tetrafluoroethylene polymer and manufacturing method thereof | |
| CN103172967B (en) | For the Solid mixture antioxidant and preparation method thereof of resin | |
| CN106947035A (en) | A kind of anti-dripping melt type organic sesqui siloxane fire retardant and preparation method and application | |
| CN110655664B (en) | Method for preparing polytetrafluoroethylene blend with high efficiency, environmental protection and low cost and product | |
| CN103880985B (en) | Hydrocarbon polymer is with dispersant and prepare the method for dispersion | |
| TWI480289B (en) | Basic stabilisation systems for emulsion polymerised rubbers | |
| CN108570222A (en) | White graphite alkene is modified polybutylene terephthalate (PBT) composite material and preparation method | |
| CN102267876A (en) | Preparation method of styrenated hindered phenol or styrenated phenol antioxidant product | |
| CN102633921A (en) | Preparation method of aqueous emulsion type polyvinyl chloride resin non-toxic terminator | |
| CN103288988B (en) | Styrol bisphenol-a derivative is as the preparation method of polrvinyl chloride terminator | |
| CN102492064A (en) | Preparation and application method of polyvinyl chloride (PVC) resin terminator | |
| CN104448665A (en) | Dedicated emulsion-type composite anti-oxidant for MBS (methyl methacrylate-butadiene-styrene) and preparation method of the dedicated emulsion-type composite anti-oxidant | |
| CN101503544B (en) | Heat resisting flame retardant resin composition with improved glossiness and preparation thereof | |
| CN106893300A (en) | Sulfur-bearing phosphate composite fire retardant PC/ABS alloy materials and preparation method thereof | |
| CN101503555B (en) | Heat resisting resin composition and preparation thereof | |
| CN101503543B (en) | Maleimide heat resisting composition and preparation method | |
| CN110483935A (en) | A kind of polypropylene macromolecular reinforcement nucleating agent and the preparation method and application thereof | |
| CN110982014A (en) | Halogen-free flame-retardant PVC material and preparation method thereof | |
| CN108329517A (en) | A kind of novel plastic processing emulsion composite antioxidant and preparation method thereof | |
| CN101503551B (en) | Maleimide heat resisting resin composition with improved glossiness and preparation thereof | |
| CN107629546A (en) | A kind of VOC free offset printing environment-friendly ink binder and preparation method | |
| CN108384131A (en) | White graphite alkene modified polystyrene composite material and preparation method thereof | |
| CN116655903A (en) | Organic alcohol type hyper-dispersant, preparation method thereof and ABS color master batch with high dispersibility |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210317 Address after: 223800 west side of Fumin Avenue, Suqian Economic and Technological Development Zone, Suqian City, Jiangsu Province Patentee after: Suqian first construction and installation Co.,Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20210416 Address after: 223600 room 6, 2 / F, 88 Changjiang Road, Miaotou Town, Shuyang County, Suqian City, Jiangsu Province Patentee after: JIANGSU GAOJING CONSTRUCTION ENGINEERING Co.,Ltd. Address before: 223800 west side of Fumin Avenue, Suqian Economic and Technological Development Zone, Suqian City, Jiangsu Province Patentee before: Suqian first construction and installation Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210617 Address after: 223800 Room 302, building 6B, Bawang mall, Sucheng District, Suqian City, Jiangsu Province Patentee after: Suqian Sumu Construction Engineering Co.,Ltd. Address before: 223600 room 6, 2 / F, 88 Changjiang Road, Miaotou Town, Shuyang County, Suqian City, Jiangsu Province Patentee before: JIANGSU GAOJING CONSTRUCTION ENGINEERING Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210806 Address after: 530000 No. 501, 5 / F, building 8, Nanning Wuyue Plaza, No. 7, Jinchuan Road, Xingning District, Nanning City, Guangxi Zhuang Autonomous Region Patentee after: Guangxi Huayi Intellectual Property Service Co.,Ltd. Address before: 223800 Room 302, building 6B, Bawang mall, Sucheng District, Suqian City, Jiangsu Province Patentee before: Suqian Sumu Construction Engineering Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211115 Address after: 463000 comprehensive service center of industrial cluster at the intersection of Binhe North Road and Yicheng Avenue, Yicheng District, Zhumadian City, Henan Province Patentee after: Haohan Chemical Co.,Ltd. Address before: 530000 No. 501, 5 / F, building 8, Nanning Wuyue Plaza, No. 7, Jinchuan Road, Xingning District, Nanning City, Guangxi Zhuang Autonomous Region Patentee before: Guangxi Huayi Intellectual Property Service Co.,Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method of lotion antioxidant product Effective date of registration: 20221110 Granted publication date: 20141029 Pledgee: Zhumadian Rural Commercial Bank Co.,Ltd. Pledgor: Haohan Chemical Co.,Ltd. Registration number: Y2022980021522 |