CN107540896A - Preparation method of easily-processed flame-retardant nitrile rubber - Google Patents
Preparation method of easily-processed flame-retardant nitrile rubber Download PDFInfo
- Publication number
- CN107540896A CN107540896A CN201610474925.9A CN201610474925A CN107540896A CN 107540896 A CN107540896 A CN 107540896A CN 201610474925 A CN201610474925 A CN 201610474925A CN 107540896 A CN107540896 A CN 107540896A
- Authority
- CN
- China
- Prior art keywords
- rubber
- nitrile rubber
- preparation
- flame
- flame retardant
- 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
- 239000003063 flame retardant Substances 0.000 title claims abstract description 87
- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 73
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims description 33
- 229920001971 elastomer Polymers 0.000 claims abstract description 61
- 239000005060 rubber Substances 0.000 claims abstract description 61
- 239000004014 plasticizer Substances 0.000 claims abstract description 59
- 239000000839 emulsion Substances 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 239000004816 latex Substances 0.000 claims abstract description 34
- 229920000126 latex Polymers 0.000 claims abstract description 34
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005865 alkene metathesis reaction Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000003292 glue Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 14
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000003795 chemical substances by application Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 30
- 239000008394 flocculating agent Substances 0.000 claims description 19
- 230000018044 dehydration Effects 0.000 claims description 16
- 238000006297 dehydration reaction Methods 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 14
- -1 methacryloxypropyl Chemical group 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 8
- VFIJBTVGUHVPPW-UHFFFAOYSA-N [Br].C=C Chemical compound [Br].C=C VFIJBTVGUHVPPW-UHFFFAOYSA-N 0.000 claims description 7
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 7
- 239000000344 soap Substances 0.000 claims description 7
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- UWTUEMKLYAGTNQ-UHFFFAOYSA-N 1,2-dibromoethene Chemical group BrC=CBr UWTUEMKLYAGTNQ-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- YFBWZSQNESHVPR-UHFFFAOYSA-N 1-(2,4,6-trimethylphenyl)-4,5-dihydroimidazole Chemical class CC1=CC(C)=CC(C)=C1N1C=NCC1 YFBWZSQNESHVPR-UHFFFAOYSA-N 0.000 claims 1
- 125000004093 cyano group Chemical group *C#N 0.000 claims 1
- FRQJRKIDWPMFNQ-UHFFFAOYSA-N dicyclohexyl-[1,3-dichloro-2-[(2-propan-2-yloxyphenyl)methylidene]cyclohexyl]phosphane Chemical compound ClC1C(C(CCC1)(P(C1CCCCC1)C1CCCCC1)Cl)=CC1=C(C=CC=C1)OC(C)C FRQJRKIDWPMFNQ-UHFFFAOYSA-N 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
- 239000000194 fatty acid Substances 0.000 claims 1
- 229930195729 fatty acid Natural products 0.000 claims 1
- 150000004665 fatty acids Chemical class 0.000 claims 1
- 150000002896 organic halogen compounds Chemical class 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 26
- 239000001301 oxygen Substances 0.000 abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 8
- 241001441571 Hiodontidae Species 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 230000001112 coagulating effect Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 19
- 239000003643 water by type Substances 0.000 description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 10
- 239000011591 potassium Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002955 isolation Methods 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 235000019504 cigarettes Nutrition 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 210000000481 breast Anatomy 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- UWTUEMKLYAGTNQ-OWOJBTEDSA-N (e)-1,2-dibromoethene Chemical class Br\C=C\Br UWTUEMKLYAGTNQ-OWOJBTEDSA-N 0.000 description 2
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical class ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 2
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000010057 rubber processing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- ITCAUAYQCALGGV-XTICBAGASA-M sodium;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Na+].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O ITCAUAYQCALGGV-XTICBAGASA-M 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- KFUSEUYYWQURPO-UHFFFAOYSA-N 1,2-dichloroethene Chemical compound ClC=CCl KFUSEUYYWQURPO-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- TXISDYBMZCVCNN-UHFFFAOYSA-N CC(C)OC1=C(C=C(CCCC2)C2P(C2CCCCC2)C2CCCCC2)C=CC=C1 Chemical compound CC(C)OC1=C(C=C(CCCC2)C2P(C2CCCCC2)C2CCCCC2)C=CC=C1 TXISDYBMZCVCNN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 229920006387 Vinylite Polymers 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical class Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 229920006335 epoxy glue Polymers 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a method for easily processing flame-retardant nitrile rubber, which comprises the steps of firstly dissolving nitrile rubber in a solvent to prepare a solution, adding an olefin metathesis catalyst and a rubber flame retardant, and removing a glue solution after reaction through the solvent to obtain a flame-retardant plasticizer; dispersing the plasticizer into water under the action of an emulsifier to form emulsion, mixing the emulsion with butyronitrile latex, and then coagulating, washing and drying to obtain the flame-retardant nitrile rubber product easy to process. The plasticizer product can reduce Mooney 0.7 unit/part of base rubber and improve oxygen index by 0.2 percent/part.
Description
Technical field
The present invention relates to a kind of preparation method of nitrile rubber, specifically a kind of nitrile rubber of the flame retardant type of easy processing
Preparation method.
Background technology
The flame resistant method of rubber materials mainly have additional fire retardant and with two methods of fire retardant blend rubber.Additional fire retardant
There are inorganic combustion inhibitor and organic fire-retardant, inorganic combustion inhibitor, which generally has cooling and iris action, common kind, aluminium hydroxide, hydrogen
Magnesia, boron system thing and molybdenum system thing etc.;For organic fire-retardant then based on brominated, chlorine or phosphorous organic compound, bromine class is fire-retardant
Agent can discharge hydrogen bromide in burning, serve as a barrier against oxygen.Exist in intelligence etc.《Flame retardant rubber is simply analysed》(world's rubber work
Industry, the phase page 39 of volume 31 the 4th) propose, 15 parts of Sb are added in SBR2O3With 30 parts of chlorinated paraffins or 5 parts of Sb2O3, 20 parts of chlorine
Fossil waxes and 25 parts of Al (OH)3, the preferable sizing material of anti-flammability can be obtained.Li Ang etc. exists《Rubber flame-retarded and its fire retardant》It is (extraordinary
Rubber, the phase page 25 of volume 23 the 3rd) in propose, by brominated phosphate, aromatic bromide, Sb2O3With 4 kinds of resistances of ammonium chloride
Combustion agent is used in combination, and is added in SBR, can be obtained the good sizing material of flame retardant effect.With 5~10 parts of dialkyl phenyl organic phosphates, 10
~15 parts of Sb2O3With the flame retardant agent of 3~10 parts of iodine, it is added in SBR, the good sizing material of flame retardant effect can be obtained.Fire retardant rubber
Glue is mainly the glue kind that some contain halogen, such as neoprene, polyvinyl chloride, epichlorohydrin rubber, chlorosulfonated polyethylene.
Inorganic combustion inhibitor has the shortcomings that dosage is big, and organic fire-retardant expense is again high, even if not considering these factors, additional resistance
Combustion agent is not easy to realize in the production process of rubber, and inorganic particle than more serious, will realize its mixing with rubber from reuniting
Higher energy is needed, generally requires and prolonged kneading repeatedly is carried out in mill or banbury and is kneaded.Mill is close
Refine in process, be typically necessary and add a certain amount of plasticizer.Typically plant the low molecule that can make sizing material that there is certain flexibility
Material, they can increase the plasticity of sizing material, mobility, adherence, in order to the technological operation such as die mould and shaping.And help
Disperse and reduce melting temperature in powdered compounding ingredient, improve the machinability of rubber.
For nitrile rubber because the polarity of its itrile group acts on, oil resistivity is preferable, is usually used in the neck such as sebific duct, adhesive tape, encapsulant
Domain, most commonly used petroleum plasticizer in rubber processing, mainly including aromatic naphtha, paraffin oil, naphthenic oil, heavy oil, paraffin, all
Intellectual circle, pitch, Petropols etc., do not apply to and nitrile rubber process systems.Nitrile rubber typically using phthalic acid two-
The Esters such as 2- ethylhexyls make plasticizer.A kind of dibasic acid ester plasticizer of CN200310108748.5 and its manufacture method,
It is characterized in that it by adipic acid and ether alcohol under the conditions of 115~125 DEG C and 84~97KPa vacuum decompressions, through esterification
Into.This plasticizer has that compatibility is good, volatilization loss is small, is not easy to be extracted the feature washed away, for improving polymeric material
Low-temperature flexibility have a significant effect, and the not performance of expendable material in itself.Especially suitable for as nitrile rubber, propylene
Acid esters rubber, epichlorohydrin rubber etc polar rubber, and can also be used for vinylite, celluosic resin etc..
The polyurethane prepolymer of CN97181179.2 low-monomer-contents, the polyurethane prepolymer of the low-monomer-content containing free NCO group
Thing, prepared from the diisocyanate of polyhydroxy-alcohol and differential responses activity, it is characterized in that the diisocyanate that relative response is slower
NCO group and rapid reaction diisocyanate NCO group ratio.Prepolymer is reacted by two benches to be prepared.This hair
Bright prepolymer is applied to adhered plastics product, metal and paper, especially membrane material.It is mostly this kind of plasticizer of patent report
Ester plasticizer, this kind of plasticizer are preferable to the compatibility of nitrile rubber, there is the effect preferably softened, but do not have flame retardant effect,
And easily separated out during product use.
The content of the invention
It is an object of the present invention to provide a kind of preparation method of easy processing flame retardant type nitrile rubber, will specifically have fire-retardant work(
The plasticizer of energy is added to the rubber product for the flame retardant type that easy processing is prepared in NBR latex by liquid phase calendering process.
The preparation method of the nitrile rubber of described easy processing flame retardant type, is concretely comprised the following steps:
1) flame retardant type plasticizer is prepared first, and nitrile rubber is dissolved in into preparation 0.1%w-20%w in solvent is preferably
1%w~15%w solution, in terms of 100 mass parts rubber, add the olefin metathesis of 0.5-1.5 parts, preferably 0.8-1.2 parts
Rubber flame-retarded dose of catalyst and 10-60 parts, preferably 15-35 parts, at 15-50 DEG C, preferably 20-25 DEG C isolation air and
Water, 0.5-5 hours are reacted, preferably 1-2 hours, reacted glue is deviate from through solvent, and it is 200-8000 scopes to obtain Mn
Flame retardant type plasticizer product;
2) obtained flame retardant type plasticizer product is added and mixed with emulsifying agent, water, plasticising agent emulsion is made in stirring;
3) latex and flame retardant type plasticising agent emulsion are added into condensing field, stirring, is 100 according to butt proportioning:(1~
50), preferably 100:(10~40), carry out mixing and be made into mixing latex, in the case where reaction temperature is 10 DEG C~80 DEG C, addition 1~
25 mass parts flocculating agents condense, scrubbed, centrifugal dehydration, drying, and easy processing flame retardant type nitrile rubber is made.
Easy processing flame retardant type nitrile rubber prepared by the present invention, after tested, 0.7 unit of basic glue Mooney/part is reduced, oxygen refers to
Number improves 0.2%/part.
Solvent of the present invention is the solvent that can dissolve nitrile rubber that alkene is free of in structure;Selected from chloroform, chlorobenzene,
Acetone, butanone etc..
Rubber flame-retarded dose of the present invention for the organic chloride monomer of the substituent of unsaturation containing alkene, its structural formula is:
RX;Wherein:R- contains the unsaturated olefin aliphatic segment of 2~18 carbon, can be vinyl, acrylic, isopropenyl,
Isopentene group, 3- pentenyls, 6- octenyls, tetramethyl-ethylene base, 1- heptenyls, methacryloxypropyl, metering system
Acyloxy, preferred vinyl;X is F, Cl, Br or I, preferably Br;
R in RX preferably comprises nitrile group, is easy to dissolve in polar solvent, improves the compatibility with nitrile rubber,
Intensified response activity;
Rubber flame-retarded dose of the present invention can be vinyl chloride, propylene dichloride nitrile, bromination acrylonitrile, bromine ethene, dichloro
Ethene, dibromoethylene and its isomer etc.;
Olefin metathesis catalyst of the present invention is a kind of Ru carbene complex catalyst, can be that dichloro is (o-
Isopropoxy benzylidene) (tricyclohexyl phosphine) conjunction ruthenium (II)Dichloro [o- isopropoxy benzene methylene
Base] [double (2,4,6- the trimethylphenyls) -2- imidazolines subunits of 1,3-] conjunction rutheniumDeng with identity function
Grubbs catalyst series or other there is the metal carbene catalyst of olefin metathesis function, preferablyOr
The present invention does not do particular determination to the species and dosage of used emulsifying agent and flocculating agent, and use is commonly used in the art
Auxiliary agent and dosage.Emulsifying agent can be the anion such as saturated or unsaturated fatty acid soaps, RA rosin acid as mentioned
Type emulsifying agent;Its dosage can be that 0.1~20 part, preferably 0.5~10 part is added in 100 parts of flame retardant type plasticizer products.
The present invention does not have particular/special requirement to the addition of described plasticising agent emulsion configuration process reclaimed water yet, as long as can make
Material forms emulsion state, and the addition of water is preferably 50~500 parts of water of addition in 100 parts of flame retardant type plasticizer products.
The present invention is not particularly limited to the temperature of described plasticising agent emulsion configuration process, as long as under agitation being capable of shape
It can be preferably 10-80 DEG C into emulsion, such as temperature.
Flocculating agent of the present invention can be CaCl2、MgSO4、Mg Cl2、Al2SO4、FeCl3、CuCl2、Ca(HSO4)2
Deng soluble metal salt and its mixture.Its dosage is preferably 1~25 mass parts flocculating agent of addition in 100 parts of NBR latexes,
Preferably 5~15 parts.
" part " being not specifically noted in the present invention each means mass parts.
The technical principle of foundation of the present invention is:
Formula (1) n > m
As shown in above-mentioned chemical equation (1), nitrile rubber is under olefin metathesis catalyst effect in the present invention
Molecular weight is reduced, and halogen flame retardant group is introduced in side base;The introducing accelerated degradation of unimolecule alkene is anti-in course of reaction
Should, functional group can be incorporated into side base and end group;If being not added with unimolecule alkene, metathesis reaction process is relatively slowly and between side base
The side reaction such as crosslinking aggravation;It is very fierce oxidation reaction that rubber burns under aerobic conditions, and chain chemical reaction,
Active HO- free free radicals are generated during burning, hydrocarbon and water are generated when HO- free radicals meet with rubber molecule.
Under aerobic conditions, hydrocarbon can continue to decompose and generation HO- free radicals, so as to form chain reaction, continues burning
Go down.Prevent rubber combustion or extinguish it that oxygen or reduction HO- number of free radical must be blocked.Flame retardant type plasticizer by
Thermal decomposition discharges halogen gas and hydrogen halides, and halogen can play a part of certain blocking oxygen;Halogenation Hydrogen Energy is free with HO-
Base reaction generation water and halide ion, halide ion can generate hydrogen halides with hydrocarbon reaction, and hydrogen halides can further disappear
Go out HO- free radicals, so as to reduce HO- number of free radical, burning velocity is slowed down until extinguishing.Simultaneously it is emphasized that should
Plasticizer is to be generated after nitrile rubber is degraded, and has identical composition with rubber base-material, is played during rubber processing soft
Change acts on, in later stage vulcanization process with base-material vulcanization crosslinking.
Embodiment
Material auxiliary agent needed for present invention specific implementation is as described below:
(1) nitrile rubber NBR3305, NBR2907, technical grade, Lanzhou Petrochemical;
(2) vinyl chloride, propylene dichloride nitrile, bromination acrylonitrile, vinylidene chloride, bromine ethene, trans- 1,2- dibromoethylenes,
SILVER REAGENT, lark prestige Science and Technology Ltd.;
(3) olefin metathesis catalyst:WithRuthenium carbone catalyst, 500mg/ bottles,
Purity >=98%w, lark prestige Science and Technology Ltd.;
(4) chloroform, chlorobenzene, acetone, butanone, SILVER REAGENT, lark prestige Science and Technology Ltd.;
(5) sodium soap, sodium abietate, aliphatic acid potassium, potassium rosinate, technical grade, Lanzhou Petrochemical;
(6)CaCl2、MgSO4、MgCl2、Al2(SO4)3, technical grade, Lanzhou Petrochemical;
Plasticizer is blended with nitrile rubber on a mill, tests crude rubber Mooney viscosity and oxygen index (OI);Rubber Mooney glues
Degree is tested according to GB/T 1232.1-2000, and rubber plastizing agent molecular weight is tested using GPC.Oxygen index (OI) is according to GB 10707-89
Test, oxygen index (OI) is high to represent that material is nonflammable, and oxygen index (OI) is low to represent that material easily burns, and oxygen index (OI) < 22 belongs to easy fuel wood
Material, oxygen index (OI) belong to combustible material between 22-27, and oxygen index (OI) > 27 belongs to nonflammable material.
" part " as described below is mass parts;Described " % " is mass percent, do not make specified otherwise according to
Rubber butt quality is 100 calculating.
Embodiment 1:
Nitrile rubber NBR3305 is dissolved in the solution of preparation 0.15% in chloroform solvent, in terms of 100 mass parts rubber,
Add 1.3 parts of olefin metathesis catalystWith 11.9 parts of rubber flame-retarded dose of propylene dichloride nitriles, 15.5
DEG C isolation air and water, reacts 0.53 hour, reacted glue is deviate from through solvent, obtains the flame retardant type plasticizer that Mn is 5500
Product;
Obtained flame retardant type plasticizer product 100g and 0.15g emulsifying agents sodium soap, 55g desalted waters are added and emulsified
Device, it is 75 DEG C to control temperature, stirring, plasticising agent emulsion is made;
Latex and plasticising agent emulsion are added into condensing field, stirring, is 100 according to butt proportioning:10, which carry out mixing, is made into
Latex is mixed, in the case where reaction temperature is 78 DEG C, adds 20 mass parts flocculating agent CaCl2Cohesion, scrubbed, centrifugal dehydration, drying,
Easy processing flame retardant type nitrile rubber is made.
After tested, Mooney viscosity is reduced to 45 by 55, and oxygen index (OI) brings up to 25.9% by 19.7%.
Comparative example 1:
Compared with Example 1, other conditions are identical, and difference is to be not added with fire retardant, are specially:By nitrile rubber
NBR3305 is dissolved in the solution of preparation 0.15% in chloroform solvent, in terms of 100 mass parts rubber, adds 1.3 parts of alkene subdivision
Solve catalystCompletely cut off air and water at 15.5 DEG C, react 0.53 hour, reacted glue is through solvent
Abjection, obtain the flame retardant type plasticizer product that Mn is 10800;
Obtained flame retardant type plasticizer product 100g and 0.15g emulsifying agents sodium soap, 55g desalted waters are added and emulsified
Device, it is 75 DEG C to control temperature, stirring, plasticising agent emulsion is made;
Latex and plasticising agent emulsion are added into condensing field, stirring, is 100 according to butt proportioning:10, which carry out mixing, is made into
Latex is mixed, in the case where reaction temperature is 78 DEG C, adds 20 mass parts flocculating agent CaCl2Cohesion, scrubbed, centrifugal dehydration, drying,
Easy processing flame retardant type nitrile rubber is made.
After tested, Mooney viscosity is reduced to 53 by 55, oxygen index (OI) 19.7%, does not improve.
Embodiment 2:
Nitrile rubber NBR3305 is dissolved in the solution of preparation 10% in acetone solvent, in terms of 100 mass parts rubber, added
Enter 0.98 part of olefin metathesis catalystWith 48 parts of rubber flame-retarded dose of vinylidene chlorides, 48.9
DEG C isolation air and water, reacts 4.5 hours, reacted glue is deviate from through solvent, obtains the flame retardant type plasticizer that Mn is 3200
Product;
Obtained flame retardant type plasticizer product 100g and 19g emulsifying agents sodium soap, 490g desalted waters are added into emulsifier,
It is 50 DEG C to control temperature, stirring, plasticising agent emulsion is made;
Latex and plasticising agent emulsion are added into condensing field, stirring, is 100 according to butt proportioning:30, which carry out mixing, is made into
Latex is mixed, in the case where reaction temperature is 55 DEG C, adds 20 mass parts flocculating agent MgSO4Cohesion, scrubbed, centrifugal dehydration, drying,
Easy processing flame retardant type nitrile rubber is made.
After tested, Mooney viscosity is reduced to 32 by 55, and oxygen index (OI) brings up to 27.2% by 19.7%.
Comparative example 2:
Compared with Example 2, other conditions are identical, and difference is to be not added with olefin metathesis catalyst, are specially:Will
Nitrile rubber NBR3305 is dissolved in the solution that 10%w is prepared in acetone solvent, in terms of 100 mass parts rubber, adds 48 parts of rubber
Fire retardant vinylidene chloride, completely cut off air and water at 48.9 DEG C, react 4.5 hours, reacted glue is deviate from through solvent, obtains
To the flame retardant type plasticizer product that Mn is 175000;
Obtained flame retardant type plasticizer product 100g and 19g emulsifying agents sodium soap, 490g desalted waters are added into emulsifier,
It is 50 DEG C to control temperature, stirring, plasticising agent emulsion is made;
Latex and plasticising agent emulsion are added into condensing field, stirring, is 100 according to butt proportioning:30, which carry out mixing, is made into
Latex is mixed, in the case where reaction temperature is 55 DEG C, adds 20 mass parts flocculating agent MgSO4Cohesion, scrubbed, centrifugal dehydration, drying,
Easy processing flame retardant type nitrile rubber is made.
After tested, Mooney viscosity 55, do not reduce, oxygen index (OI) brings up to 20.4% by 19.7%, has when condensing, drying
The white cigarette that 1,1- dichloroethylene decomposes.
Embodiment 3:
Nitrile rubber NBR2907 is dissolved in the solution of preparation 2.51% in chlorobenzene solvent, in terms of 100 mass parts rubber,
Add 1.41 parts of olefin metathesis catalystIt is empty in 25.5 DEG C of isolations with 25.2 parts of rubber flame-retarded dose of bromine ethene
Gas and water, react 2.55 hours, reacted glue is deviate from through solvent, obtains the flame retardant type plasticizer product that Mn is 520;
Obtained flame retardant type plasticizer product 100g and 10g emulsifying agents sodium abietate, 250g desalted waters are added into emulsifier,
It is 40 DEG C to control temperature, stirring, plasticising agent emulsion is made;
Latex and plasticising agent emulsion are added into condensing field, stirring, is 100 according to butt proportioning:25, which carry out mixing, is made into
Latex is mixed, in the case where reaction temperature is 55 DEG C, adds 20 mass parts flocculating agent MgSO4Cohesion, scrubbed, centrifugal dehydration, drying,
Easy processing flame retardant type nitrile rubber is made.
After tested, Mooney viscosity is reduced to 55 by 75, and oxygen index (OI) brings up to 25.8% by 19.7%.
Comparative example 3:
Compared with Example 3, other conditions are identical, and difference is to make using di-2-ethylhexyl phthalate
For plasticizer, it is specially:Plasticizer 100g and 10g sodium abietates emulsifying agent, 250g desalted waters are added into emulsifier, control temperature
Spend for 40 DEG C, stir, plasticising agent emulsion is made;
Latex and plasticising agent emulsion are added into condensing field, is 100 according to butt proportioning:25, which carry out mixing, is made into epoxy glue
Breast, in the case where reaction temperature is 55 DEG C, add 20 mass parts flocculating agent MgSO4Cohesion, scrubbed, centrifugal dehydration, drying, it is made easy
Process flame retardant type nitrile rubber.
After tested, Mooney viscosity is reduced to 53 by 75, and oxygen index (OI) drops to 16.8% by 19.7%, more inflammable.
Embodiment 4:
Nitrile rubber NBR2907 is dissolved in the solution of preparation 4.5% in butanone solvent, in terms of 100 mass parts rubber, added
Enter 0.59 part of olefin metathesis catalystWith 13 parts of rubber flame-retarded dose of bromine ethene, 15 DEG C completely cut off air and
Water, react 4.9 hours, reacted glue is deviate from through solvent, obtains the flame retardant type plasticizer product that Mn is 7300;
Obtained flame retardant type plasticizer product 100g and 18g emulsifying agents potassium rosinate, 450g desalted waters are added into emulsifier,
It is 60 DEG C to control temperature, stirring, plasticising agent emulsion is made;
Latex and plasticising agent emulsion are added into condensing field, stirring, is 100 according to butt proportioning:40, which carry out mixing, is made into
Latex is mixed, in the case where reaction temperature is 30 DEG C, adds 15 mass parts flocculating agent Al2(SO4)3Cohesion, scrubbed, centrifugal dehydration, do
It is dry, easy processing flame retardant type nitrile rubber is made.
After tested, Mooney viscosity is reduced to 41 by 75, and oxygen index (OI) brings up to 28.6% by 19.7%.
Comparative example 4:
Compared with Example 4, other conditions are identical, and difference is to use fire retardant 1,1- Bromofumes, without double
Key, it is specially:Nitrile rubber NBR2907 is dissolved in the solution of preparation 4.5% in butanone solvent, in terms of 100 mass parts rubber,
Add 0.59 part of olefin metathesis catalystWith 13 parts of rubber flame-retarded dose of 1,1- Bromofumes, completely cut off at 15 DEG C
Air and water, react 4.9 hours, reacted glue is deviate from through solvent, obtains the flame retardant type plasticizer product that Mn is 38000;
Obtained flame retardant type plasticizer product 100g and 18g emulsifying agents potassium rosinate, 450g desalted waters are added into emulsifier,
It is 60 DEG C to control temperature, stirring, plasticising agent emulsion is made;
Latex and plasticising agent emulsion are added into condensing field, stirring, is 100 according to butt proportioning:40, which carry out mixing, is made into
Latex is mixed, in the case where reaction temperature is 30 DEG C, adds 15 mass parts flocculating agent Al2(SO4)3Cohesion, scrubbed, centrifugal dehydration, do
It is dry, easy processing flame retardant type nitrile rubber is made.
After tested, Mooney viscosity is reduced to 69 by 75, and oxygen index (OI) brings up to 20.4% by 19.7%, has when condensing, drying
The white cigarette that 1,1- Bromofumes decompose.
Embodiment 5:
Nitrile rubber NBR3305 is dissolved in the solution of preparation 3.75% in chloroform solvent, in terms of 100 mass parts rubber,
Add 0.85 part of olefin metathesis catalystWith 12 parts of rubber flame-retarded dose of trans- 1,2- dibromoethylenes,
35 DEG C of isolation air and water, react 4 hours, and reacted glue is deviate from through solvent, obtain the flame retardant type plasticizer that Mn is 1700
Product;
By obtained flame retardant type plasticizer product 100g and 0.5g emulsifying agent aliphatic acid potassium, 400g desalted waters add emulsification
Device, it is 15 DEG C to control temperature, stirring, plasticising agent emulsion is made;
Latex and plasticising agent emulsion are added into condensing field, stirring, is 100 according to butt proportioning:7.8, which carry out mixing, is made into
Latex is mixed, in the case where reaction temperature is 12 DEG C, adds 1.5 mass parts flocculating agent Al2(SO4)3Cohesion, scrubbed, centrifugal dehydration,
Dry, easy processing flame retardant type nitrile rubber is made.
After tested, Mooney viscosity is reduced to 38 by 55, and oxygen index (OI) brings up to 29.3% by 19.7%.
Comparative example 5:
Compared with Example 5, other conditions are identical, and difference adds in using fire retardant in liquid phase compounding procedure
Enter, be specially:Nitrile rubber NBR3305 is dissolved in the solution of preparation 3.75% in chloroform solvent, with 100 mass parts rubber
Meter, add 0.85 part of olefin metathesis catalystCompletely cut off air and water at 35 DEG C, react 4 hours,
Reacted glue is deviate from through solvent, obtains the flame retardant type plasticizer product that Mn is 10300;
By obtained flame retardant type plasticizer product 100g and equivalent to 12 parts of rubber flame-retarded dose of trans- 1,2- dibromos second of plasticizer
Alkene and 0.5g emulsifying agent aliphatic acid potassium, 400g desalted waters add emulsifier, and it is 15 DEG C to control temperature, stirring, and plasticizer breast is made
Liquid;
Latex and plasticising agent emulsion are added into condensing field, stirring, is 100 according to butt proportioning:7.8, which carry out mixing, is made into
Latex is mixed, in the case where reaction temperature is 12 DEG C, adds 1.5 mass parts flocculating agent Al2(SO4)3Cohesion, scrubbed, centrifugal dehydration,
Dry, easy processing flame retardant type nitrile rubber is made.
After tested, Mooney viscosity is reduced to 49 by 55, and oxygen index (OI) brings up to 20.9% by 19.7%, has when condensing, drying
The white cigarette that dibromoethylene is decomposed.
Embodiment 6:
Nitrile rubber NBR3305 is dissolved in the solution that 19%w is prepared in chlorobenzene solvent, in terms of 100 mass parts rubber, added
Enter 0.95 part of olefin metathesis catalystIt is empty in 28 DEG C of isolations with 38 parts of rubber flame-retarded dose of vinyl chloride
Gas and water, react 3.23 hours, reacted glue is deviate from through solvent, obtains the flame retardant type plasticizer product that Mn is 900;
By obtained flame retardant type plasticizer product 100g and 0.2g emulsifying agent aliphatic acid potassium, 443g desalted waters add emulsification
Device, it is 78 DEG C to control temperature, stirring, plasticising agent emulsion is made;
Latex and plasticising agent emulsion are added into condensing field, stirring, is 100 according to butt proportioning:1.3, which carry out mixing, is made into
Latex is mixed, in the case where reaction temperature is 35 DEG C, adds 5.5 mass parts flocculating agent Al2(SO4)3Cohesion, scrubbed, centrifugal dehydration,
Dry, easy processing flame retardant type nitrile rubber is made.
After tested, Mooney viscosity is reduced to 49.5 by 55, and oxygen index (OI) brings up to 24.7% by 19.7%.
Comparative example 6:
Compared with Example 6, other conditions are identical, and difference is to make using di-2-ethylhexyl phthalate
For plasticizer, while fire retardant is added, be specially:By the di-2-ethylhexyl phthalate plasticizer 100g and 0.2g breasts
Agent aliphatic acid potassium, 443g desalted waters and be 38 parts of rubber flame-retarded dose of vinyl chloride relative to plasticizer quality, add emulsifier, control
Temperature processed is 78 DEG C, stirring, plasticising agent emulsion is made;
Latex and plasticising agent emulsion are added into condensing field, is 100 according to butt proportioning:1.3, which carry out mixing, is made into mixing
Latex, reaction temperature are 35 DEG C, add the cohesion of 5.5 mass parts flocculating agents, scrubbed, centrifugal dehydration, drying, easy processing are made
Flame retardant type nitrile rubber.
After tested, Mooney viscosity is reduced to 53 by 55, and oxygen index (OI) does not have significant change, and has vinyl chloride when cohesion, drying
The white cigarette of decomposition.
Embodiment 7:
Nitrile rubber NBR3305 is dissolved in the solution that 18%w is prepared in chlorobenzene solvent, in terms of 100 mass parts rubber, added
Enter 0.95 part of olefin metathesis catalystWith 43 parts of rubber flame-retarded dose of bromine ethene, 48 DEG C completely cut off air and
Water, react 3.5 hours, reacted glue is deviate from through solvent, obtains the flame retardant type plasticizer product that Mn is 550;
By obtained flame retardant type plasticizer product 100g and 0.29g emulsifying agent aliphatic acid potassium, 98g desalted waters add emulsification
Device, it is 63 DEG C to control temperature, stirring, plasticising agent emulsion is made;
Latex and plasticising agent emulsion are added into condensing field, stirring, is 100 according to butt proportioning:33, which carry out mixing, is made into
Latex is mixed, in the case where reaction temperature is 55 DEG C, adds 21 mass parts flocculating agent Ca (HSO4)2Cohesion, scrubbed, centrifugal dehydration, do
It is dry, easy processing flame retardant type nitrile rubber is made.
After tested, Mooney viscosity is reduced to 39 by 55, and oxygen index (OI) brings up to 28.7% by 19.7%.
Comparative example 7:
Compared with Example 7, other conditions are identical, and difference is urged first adding double decomposition in plasticizer preparation process
Agent has been reacted and then added fire retardant and reacted a period of time again, is specially:Nitrile rubber NBR3305 is dissolved in chlorobenzene
18%w solution is prepared in solvent, in terms of 100 mass parts rubber, adds 0.95 part of olefin metathesis catalyst48 DEG C isolation air and water reaction 2h, add 43 parts of rubber flame-retarded dose of bromine ethene, 48 DEG C completely cut off air and
Water, react 1.5 hours, reacted glue is deviate from through solvent, obtains the flame retardant type plasticizer product that Mn is 9500;
By obtained flame retardant type plasticizer product 100g and 0.29g emulsifying agent aliphatic acid potassium, 98g desalted waters add emulsification
Device, it is 63 DEG C to control temperature, stirring, plasticising agent emulsion is made;
Latex and plasticising agent emulsion are added into condensing field, stirring, is 100 according to butt proportioning:33, which carry out mixing, is made into
Latex is mixed, in the case where reaction temperature is 55 DEG C, adds 21 mass parts flocculating agent Ca (HSO4)2Cohesion, scrubbed, centrifugal dehydration, do
It is dry, easy processing flame retardant type nitrile rubber is made.
After tested, Mooney viscosity is reduced to 50 by 55, and oxygen index (OI) brings up to 21.3% by 19.7%.
Claims (17)
1. a kind of preparation method of the nitrile rubber of easy processing flame retardant type, is concretely comprised the following steps:
1) flame retardant type plasticizer is prepared, nitrile rubber is dissolved in the solution that 0.1%w-20%w is prepared in solvent, with 100 mass
Part rubber meter, add 0.5-1.5 parts olefin metathesis catalyst and rubber flame-retarded dose of 10-60 parts, completely cut off at 15-50 DEG C air and
Water, 0.5-5 hours are reacted, reacted glue is deviate from through solvent, obtains flame retardant type plasticizer product;
2) obtained flame retardant type plasticizer product is added and mixed with emulsifying agent, water, plasticising agent emulsion is made in stirring;
3) latex and flame retardant type plasticising agent emulsion are added into condensing field, stirring, is 100 according to butt proportioning:1~50, preferably
For 100:10~40, carry out mixing and be made into mixing latex, in the case where reaction temperature is 10 DEG C~80 DEG C, adds 1~25 mass parts and coagulate
Poly- agent cohesion, scrubbed, centrifugal dehydration, drying, is made easy processing flame retardant type nitrile rubber.
2. the preparation method of nitrile rubber as claimed in claim 1, it is characterised in that the Mn of prepared flame retardant type plasticizer
For 200-8000.
3. the preparation method of nitrile rubber as claimed in claim 1, it is characterised in that described solvent is to be free of alkene in structure
The solvent that can dissolve nitrile rubber.
4. the preparation method of nitrile rubber as claimed in claim 1, it is characterised in that described solvent be selected from chloroform, chlorobenzene,
Acetone or butanone.
5. the preparation method of nitrile rubber as claimed in claim 1, it is characterised in that prepared by described flame retardant type plasticizer
Cheng Zhong, in terms of 100 mass parts nitrile rubbers, add 0.8-1.2 part olefin metathesis catalysts.
6. the preparation method of nitrile rubber as claimed in claim 1, it is characterised in that prepared by described flame retardant type plasticizer
Cheng Zhong, in terms of 100 mass parts nitrile rubbers, add rubber flame-retarded dose of 15-35 parts.
7. the preparation method of nitrile rubber as claimed in claim 1, it is characterised in that described rubber flame-retarded dose be containing alkene not
The organohalogen compounds monomer of saturation substituent.
8. the preparation method of the nitrile rubber as described in claim 1 or 7, it is characterised in that rubber flame-retarded dose described of structure
Formula is:RX;Wherein:R- contains the unsaturated olefin aliphatic segment of 2~18 carbon;X is F, Cl, Br or I.
9. the preparation method of nitrile rubber as claimed in claim 8, it is characterised in that rubber flame-retarded dose described of structural formula
In R be selected from vinyl, acrylic, isopropenyl, isopentene group, 3- pentenyls, 6- octenyls, trimethyl-ethylene base, 1- heptan
Alkenyl, methacryloxypropyl or methacryloxy.
10. the preparation method of nitrile rubber as claimed in claim 8, it is characterised in that rubber flame-retarded dose described of structural formula
In R be vinyl.
11. the preparation method of nitrile rubber as claimed in claim 8, it is characterised in that rubber flame-retarded dose described of structural formula
In X be Br.
12. the preparation method of nitrile rubber as claimed in claim 8, it is characterised in that rubber flame-retarded dose described of structural formula
In R contain cyano group.
13. the preparation method of the nitrile rubber as described in claim 1 or 7, it is characterised in that described rubber flame-retarded dose is selected from
Vinyl chloride, propylene dichloride nitrile, bromination acrylonitrile, bromine ethene, dichloroethylene or dibromoethylene.
14. the preparation method of nitrile rubber as claimed in claim 1, it is characterised in that described olefin metathesis catalyst is
Metal carbene catalyst with olefin metathesis function.
15. the preparation method of nitrile rubber as claimed in claim 1, it is characterised in that described olefin metathesis catalyst choosing
Ruthenium (II) is closed from dichloro (o- isopropoxy benzylidene) (tricyclohexyl phosphine)Dichloro [o- isopropyl
Epoxide benzylidene] [1,3- double (2,4,6- trimethylphenyl) -2- imidazolines subunits] conjunction ruthenium
16. the preparation method of nitrile rubber as claimed in claim 1, it is characterised in that described emulsifying agent for saturation or not
The fatty acid soaps or RA rosin acid of saturation;Its dosage is that 0.1~20 part is added in 100 parts of flame retardant type plasticizer products.
17. the preparation method of nitrile rubber as claimed in claim 1, it is characterised in that described flocculating agent is selected from CaCl2、
MgSO4、Mg Cl2、Al2(SO4)3、FeCl3、CuCl2、Ca(HSO4)2In one kind or its mixture, its dosage be 100 parts of butyronitrile
1~25 mass parts are added in latex.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610474925.9A CN107540896B (en) | 2016-06-24 | 2016-06-24 | Preparation method of easily-processed flame-retardant nitrile rubber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610474925.9A CN107540896B (en) | 2016-06-24 | 2016-06-24 | Preparation method of easily-processed flame-retardant nitrile rubber |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107540896A true CN107540896A (en) | 2018-01-05 |
CN107540896B CN107540896B (en) | 2020-09-04 |
Family
ID=60959917
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610474925.9A Active CN107540896B (en) | 2016-06-24 | 2016-06-24 | Preparation method of easily-processed flame-retardant nitrile rubber |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107540896B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102603928A (en) * | 2011-01-11 | 2012-07-25 | 赞南科技(上海)有限公司 | Preparation method of hydrogenated nitrile rubber and degradation and hydrogenation method of butadiene type rubber |
US20120252982A1 (en) * | 2011-03-30 | 2012-10-04 | Zannan Scitech Co., Ltd. | Methods of modifying polymers with highly active and selective metathesis catalysts |
CN103339181A (en) * | 2011-02-03 | 2013-10-02 | 日本瑞翁株式会社 | Nitrile rubber composition, crosslinking nitrile rubber composition, and crosslinked rubber product |
-
2016
- 2016-06-24 CN CN201610474925.9A patent/CN107540896B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102603928A (en) * | 2011-01-11 | 2012-07-25 | 赞南科技(上海)有限公司 | Preparation method of hydrogenated nitrile rubber and degradation and hydrogenation method of butadiene type rubber |
CN103339181A (en) * | 2011-02-03 | 2013-10-02 | 日本瑞翁株式会社 | Nitrile rubber composition, crosslinking nitrile rubber composition, and crosslinked rubber product |
US20120252982A1 (en) * | 2011-03-30 | 2012-10-04 | Zannan Scitech Co., Ltd. | Methods of modifying polymers with highly active and selective metathesis catalysts |
Non-Patent Citations (2)
Title |
---|
粷谷信三: "用复分解催化剂促进橡胶化学反应", 《橡胶参考资料》 * |
陈光等: "《新材料概论》", 30 April 2013, 国防工业出版社 * |
Also Published As
Publication number | Publication date |
---|---|
CN107540896B (en) | 2020-09-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
RU2528677C2 (en) | Stabilisers for polymers containing aliphatically-bound bromine | |
CN109385071B (en) | TPU material with flame retardant property reaching vertical burning V0 grade and preparation method thereof | |
CN104448446B (en) | Preparation method of environment-friendly flame-retardant powdered styrene butadiene rubber | |
CN104448447B (en) | Preparation method of environment-friendly low-smoke flame-retardant powdered styrene butadiene rubber | |
CN107540896A (en) | Preparation method of easily-processed flame-retardant nitrile rubber | |
CN107118412A (en) | A kind of butadiene-styrene rubber composition of efficient halogen-free anti-inflaming and preparation method thereof | |
US2831839A (en) | Oxygen-containing chlorinated and brominated polymers | |
CN106188706A (en) | A kind of flame-retardant chloroprene rubber material and preparation method thereof | |
CN107540899A (en) | Preparation method of easily-processed flame-retardant styrene butadiene rubber | |
US3950456A (en) | Flame-retardant composition | |
CN107540765A (en) | Preparation method of flame-retardant plasticizer for nitrile rubber | |
US4052542A (en) | Halo-acetyl high green strength rubbers | |
CN107540897B (en) | Preparation method of flame-retardant softener for styrene butadiene rubber | |
CN107540893A (en) | Easily-processed flame-retardant nitrile rubber and preparation method thereof | |
US2545977A (en) | Flame resistant rubber compositions containing a chlorinated wax and a metal carbonate | |
CN107540898B (en) | Easily-processed flame-retardant styrene butadiene rubber and preparation method thereof | |
US2395070A (en) | Chlorine containing carbonic estersynthetic rubber composition | |
US2919256A (en) | Process for preparing rubber compositions containing clay having adsorbed petroleum hydrocarbons | |
CN109306035A (en) | A kind of environmental protection flame retardant NBR material and preparation method thereof | |
CN107841007A (en) | Preparation method of easily processed reinforced nitrile rubber | |
RU2277108C1 (en) | Rubber mix for production of waterproof materials (versions) | |
US1932624A (en) | Manufacture of adhesives | |
US3645958A (en) | Method of making shaped articles from fibers bonded with oil-resistant synthetic rubber | |
CN107841010A (en) | Preparation method of easy-to-process reinforced styrene butadiene rubber | |
US2287773A (en) | Rubberlike materials |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |